WO2024221426A1 - 二次电池和用电装置 - Google Patents

二次电池和用电装置 Download PDF

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Publication number
WO2024221426A1
WO2024221426A1 PCT/CN2023/091698 CN2023091698W WO2024221426A1 WO 2024221426 A1 WO2024221426 A1 WO 2024221426A1 CN 2023091698 W CN2023091698 W CN 2023091698W WO 2024221426 A1 WO2024221426 A1 WO 2024221426A1
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WIPO (PCT)
Prior art keywords
negative electrode
group
secondary battery
optionally
additive
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
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PCT/CN2023/091698
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English (en)
French (fr)
Inventor
张立美
陈培培
刘姣
任家墨
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Contemporary Amperex Technology Co Ltd
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Contemporary Amperex Technology Co Ltd
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Priority to EP23934618.2A priority Critical patent/EP4517860A4/en
Priority to KR1020257008860A priority patent/KR20250048369A/ko
Priority to PCT/CN2023/091698 priority patent/WO2024221426A1/zh
Priority to CN202380010051.XA priority patent/CN121195354A/zh
Priority to JP2024568595A priority patent/JP2025519071A/ja
Publication of WO2024221426A1 publication Critical patent/WO2024221426A1/zh
Priority to US18/949,733 priority patent/US20250079526A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0568—Liquid materials characterised by the solutes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0567—Liquid materials characterised by the additives
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0569—Liquid materials characterised by the solvents
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0025—Organic electrolyte
    • H01M2300/0028—Organic electrolyte characterised by the solvent
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0025—Organic electrolyte
    • H01M2300/0028—Organic electrolyte characterised by the solvent
    • H01M2300/0037—Mixture of solvents
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present application relates to the technical field of secondary batteries, and in particular to secondary batteries and electrical devices.
  • secondary batteries are widely used in energy storage power systems such as hydropower, thermal power, wind power and solar power stations, as well as in electronic equipment power supplies, power tools, electric bicycles, electric motorcycles, electric vehicles, military equipment, aerospace and other fields.
  • energy storage power systems such as hydropower, thermal power, wind power and solar power stations
  • electronic equipment power supplies power tools, electric bicycles, electric motorcycles, electric vehicles, military equipment, aerospace and other fields.
  • the present application provides a secondary battery and an electrical device, wherein the secondary battery includes a reasonably matched negative electrode plate and a non-aqueous electrolyte, and has excellent comprehensive functions in terms of fast charging performance, cycle performance and safety performance.
  • the present application provides a secondary battery, which includes a positive electrode sheet, a negative electrode sheet and a non-aqueous electrolyte; wherein the negative electrode sheet includes a negative electrode active material layer, the negative electrode active material layer includes a negative electrode active material, and the negative electrode active material includes a graphite material; the non-aqueous electrolyte includes a solvent, the solvent includes a first solvent, and the first solvent is a chain carboxylate;
  • the OI value of the negative electrode plate, the resistance value R of the negative electrode plate and the mass proportion W0 of the first solvent in the solvent satisfy the following relationship: 0.08/m ⁇ W0 ⁇ 100/(R ⁇ OI) ⁇ 5/m ⁇ ;
  • the OI value of the negative electrode plate refers to the ratio of the diffraction peak intensity of the 004 crystal plane of the graphite material to the diffraction peak intensity of the 110 crystal plane; the unit of R is m ⁇ .
  • the OI value of the negative electrode sheet reflects the degree of anisotropy in the grain arrangement direction in the negative electrode active material layer.
  • the negative electrode sheet has a suitable orientation degree and has a suitable directional selectivity in the active ion (such as lithium ion) embedding process, which can disperse the active ion embedding expansion (such as lithium embedding expansion) in different directions, thereby reducing the cycle expansion of the electrode sheet and the battery cell, which can effectively alleviate the problem of the aggravated expansion of the electrode sheet itself due to the poor interface stability between the chain carboxylic acid ester and the negative electrode, improve battery safety, and reduce the concentration polarization of active ions in the transmission process of the negative electrode sheet, and achieve a significant improvement in the fast charging capability of the battery in combination with the negative electrode sheet resistance value R. Therefore, by synergistically controlling the OI value, R and W0, the secondary battery can have excellent comprehensive functions in terms of fast charging performance, cycle performance and safety performance, and can take into account a shorter fast charging time, lower cycle expansion and higher cycle capacity retention rate.
  • the active ion such as lithium ion
  • the QI value By adjusting the QI value within a more appropriate range, it is more conducive to reducing the directional selectivity in the active ion embedding process, so that the active ions can be better embedded and expanded and dispersed in different directions; in addition, the active ion transport performance of the negative electrode can also be better improved.
  • W0 ⁇ 100/(R ⁇ OI) can be controlled within a more appropriate range, thereby achieving better comprehensive effects in terms of shorter fast charging time, lower cycle expansion and higher cycle capacity retention rate, and is more conducive to improving the active ion transport performance and electronic conduction performance of the negative electrode sheet.
  • the matching of the chain carboxylic acid ester in the non-aqueous electrolyte and the grain arrangement direction in the negative electrode active material layer is further regulated by W0 ⁇ 100/OI, which makes it easier to achieve the improvement of the comprehensive performance of fast charging performance, cycle performance and safety performance.
  • the secondary battery satisfies the following combination of characteristics: 6 ⁇ OI ⁇ 18, 10m ⁇ R ⁇ 20m ⁇ , and 20% ⁇ W0 ⁇ 80%;
  • the resistance value R of the negative electrode plate to be 10m ⁇ -20m ⁇
  • the mass proportion W0 of the chain carboxylic acid ester solvent in the solvent to be 20%-80% (further optionally 10%-60%)
  • the first solvent comprises a compound having a structure as shown in formula (1):
  • R1 and R2 are independently C1-3 alkyl or C1-3 haloalkyl
  • R 1 and R 2 are each independently C 1-3 alkyl or C 1-3 fluoroalkyl;
  • R1 and R2 are independently one of methyl, ethyl, propyl, fluoromethyl, fluoroethyl and fluoropropyl;
  • R1 and R2 are independently one of methyl, ethyl, fluoromethyl and fluoroethyl;
  • the first solvent includes one or more of the following compounds: methyl acetate, ethyl acetate, methyl difluoroacetate and ethyl difluoroacetate.
  • a first solvent with a smaller molecular size can be selected.
  • the first solvent has a lower viscosity, which is beneficial for the secondary battery to obtain better fast charging performance.
  • the non-aqueous electrolyte further includes a first additive; the first additive is diisocyanate.
  • the first additive comprises a compound having the following structure:
  • R 3 is an unsubstituted or Ra-substituted C 1-18 alkylene group
  • R 3 is C 2-10 alkylene, C 2-10 heteroalkylene, C 6-18 arylene, C 2-18 heteroarylene, C 3-18 alicyclic group or C 3-18 hetero alicyclic group, any of which is unsubstituted or substituted by Ra;
  • R 3 is an unsubstituted or Ra substituted C 2-10 alkylene group, an unsubstituted or Ra substituted C 3-18 divalent cycloalkyl group, or an unsubstituted or Ra substituted C 6-18 arylene group; further optionally, R 3 is a C 2-10 alkylene group, a C 6-18 divalent cycloalkyl group, or a C 6-18 arylene group; further optionally, R 3 is a C 4-10 alkylene group, a C 6-14 divalent cycloalkyl group, or a C 6-14 arylene group; further optionally, R 3 is a C 4-10 alkylene group, a C 6-10 divalent cycloalkyl group, or a C 6-10 arylene group; further optionally, R 3 is a C 4-8 hexylene group, a C 6-10 divalent cycloalkyl group containing a hexyl ring, or a C 6-10 arylene group containing
  • the first additive includes one or more of the following compounds: hexamethylene diisocyanate, 1,4-cyclohexanedimethyl diisocyanate, 1,3-phenylene diisocyanate and 2,4-diisocyanato-1-toluene.
  • the mass percentage of the first additive in the non-aqueous electrolyte is 0 to 11%
  • the mass percentage of the first additive in the non-aqueous electrolyte is 0.005% to 11%;
  • the mass proportion of the first additive in the non-aqueous electrolyte is 0.005% to 10%
  • the mass proportion of the first additive in the non-aqueous electrolyte is 0.01% to 10%
  • the mass proportion of the first additive in the non-aqueous electrolyte is 0.1% to 5%;
  • the mass proportion of the first additive in the non-aqueous electrolyte is 1% to 5%.
  • first solvent chain carboxylic acid ester
  • first solvent chain carboxylic acid ester
  • the amount W0 is not well matched with the OI value and resistance value R of the negative electrode sheet, it may aggravate the expansion problem of the negative electrode sheet itself, and may also affect the gas production problem at the interface, and may also cause the attenuation of the battery cell capacity and the deterioration of the battery cycle performance.
  • SEI solid electrolyte interface
  • the protective layer can assist the active ions to be embedded into the negative electrode active material layer of the negative electrode sheet, so that the active ion embedding expansion effect of the negative electrode sheet can be evenly conducted in all directions, thereby reducing the cycle expansion rate of the negative electrode sheet.
  • the first additive can also significantly improve the stability of the interface between the electrolyte and the negative electrode sheet, which can reduce the consumption of the electrolyte and the damage to the negative electrode structure during the cycle of the secondary battery, thereby significantly improving the cycle performance of the secondary battery.
  • the non-aqueous electrolyte further comprises a second additive;
  • the second additive comprises one or more of lithium monofluorophosphate, lithium difluorophosphate, lithium tetrafluoroborate, a compound represented by formula (3), and a fluorosulfonate;
  • a, b and c are each independently a positive integer, m is an integer selected from 1-3, n is an integer selected from 0-4, and q is 0 or 1;
  • Ma + is a metal ion with a positive charge of a;
  • any Y is independently a boron atom or a phosphorus atom;
  • X is a halogen atom;
  • any R is independently one of a substituted or unsubstituted C 1-10 alkylene group, a substituted or unsubstituted C 1-10 haloalkylene group, a substituted or unsubstituted C 6-20 arylene group, and a substituted or unsubstituted C 6-20 haloarylene group;
  • M in Ma+ includes one or more of Li, Na, K, Rb, Cs, Mg, Ca, Ba, Al, Fe, Cu and Ni;
  • a, b and c are each independently selected from 1, 2 or 3.
  • the second additive includes one or more of lithium difluorophosphate, lithium monofluorophosphate, lithium tetrafluoroborate, lithium fluorosulfonate, and sodium fluorosulfonate.
  • the mass percentage of the second additive in the non-aqueous electrolyte is 0.005% to 11%
  • the mass percentage of the second additive in the non-aqueous electrolyte is 0.005% to 11%;
  • the mass proportion of the second additive in the non-aqueous electrolyte is 0.005% to 10%
  • the mass proportion of the second additive in the non-aqueous electrolyte is 0.05% to 5%.
  • an inorganic-rich SEI film can be formed at the negative electrode, which can not only improve the fast charging performance of the secondary battery, but also further improve the cycle performance of the secondary battery.
  • the volume average particle size D v 50 of the negative electrode active material is ⁇ 6 ⁇ m; wherein D v 50 represents the particle size corresponding to when the cumulative volume distribution percentage of the substance or material reaches 50%;
  • the volume average particle size D v 50 of the negative electrode active material is 6 ⁇ m to 20 ⁇ m;
  • the volume average particle size D v 50 of the negative electrode active material is 15 ⁇ m to 20 ⁇ m.
  • the contact area between the negative electrode material and the electrolyte can be reduced, and the probability of side reactions with the solvent on the negative electrode surface can be reduced, which is more conducive to reducing the electrode expansion rate and can better improve the cycle performance of the battery cell.
  • the BET specific surface area of the negative electrode active material is 0.5 m 2 /g to 2.0 m 2 /g;
  • the negative electrode active material has a BET specific surface area of 0.8 m 2 /g to 1.5 m 2 /g.
  • the surface area of the negative electrode material can be reduced, thereby reducing the contact area between the negative electrode material and the electrolyte, thereby reducing the side reactions of the solvent on the negative electrode surface and better improving the cycle performance of the battery cell.
  • the graphite material includes one or more of artificial graphite and natural graphite; alternatively, the graphite material includes artificial graphite.
  • the weight percentage of the graphite material in the negative electrode active material is ⁇ 50%; optionally, the weight percentage of the graphite material in the negative electrode active material is ⁇ 80%; further optionally, the weight percentage of the graphite material in the negative electrode active material is 100%.
  • the secondary battery is a lithium ion secondary battery.
  • the present application provides an electrical device, which includes the secondary battery described in the first aspect of the present application.
  • FIG1 is a schematic diagram of a secondary battery according to an embodiment of the present application.
  • FIG2 is an exploded view of the secondary battery of one embodiment of the present application shown in FIG1 ;
  • FIG. 3 is a schematic diagram of an electrical device using a secondary battery as a power source according to an embodiment of the present application.
  • Numerical value " range" disclosed in the present application is limited in the form of lower limit and upper limit, and given range is limited by selecting a lower limit and an upper limit, and the selected lower limit and upper limit define the boundary of special range.
  • the scope limited in this way can be including end value or excluding end value, and any end value can be included or not included independently, and can be combined arbitrarily, that is, any lower limit can form a scope with any upper limit combination. For example, if the scope of 60-120 and 80-110 is listed for a specific parameter, it is understood that the scope of 60-110 and 80-120 is also expected.
  • the method includes steps (a) and (b), which means that the method may include steps (a) and (b) performed sequentially, or may include steps (b) and (a) performed sequentially.
  • the method may further include step (c), which means that step (c) may be added to the method in any order, for example, the method may include steps (a), (b) and (c), or may include steps (a), (c) and (b), or may include steps (c), (a) and (b), etc.
  • the words “have”, “include”, “contain” and “include” mentioned in this application can each independently represent an open or closed form.
  • the words “include” and “include” can also mean that other members or timing characteristics that are not listed can also be included or included, or can only include or include the listed members or timing characteristics.
  • Members include materials or components, structures, elements, instruments, etc.; non-limiting examples of timing characteristics include actions, conditions for the occurrence of actions, timing, states, etc.
  • the term "or” is inclusive.
  • the phrase “A or B” means “A, B, or both A and B”.
  • any of the following conditions satisfies the condition "A or B”: A is true (or exists) and B is false (or does not exist); A is false (or does not exist) and B is true (or exists); or both A and B are true (or exist).
  • A (such as B) means that B is a non-limiting example of A. Not limited to B.
  • the features or solutions corresponding to "and/or” include any one of two or more related listed items, and also include any and all combinations of the related listed items, wherein the arbitrary and all combinations include any two related listed items, any more related listed items, or a combination of all related listed items.
  • “A and/or B” means a group consisting of A, B, and “a combination of A and B”.
  • “comprising A and/or B” can mean “comprising A, comprising B, and comprising A and B”, and can also mean “comprising A, comprising B, or comprising A and B", which can be properly understood according to the sentence in which it is located.
  • multiple refers to a number greater than 2 or equal to 2.
  • one or more means one or greater than or equal to two. It is understood that when “any number” of items are involved, it refers to any suitable combination of multiple items, that is, the combination of "any number” of items is performed in a manner that does not conflict and can implement this application.
  • first”, “second”, etc. in “the first aspect”, “the second aspect”, etc. are used only for descriptive purposes and cannot be understood as indicating or implying relative importance or quantity, nor can they be understood as implicitly indicating the importance or quantity of the indicated technical features.
  • first”, “second”, etc. only serve the purpose of non-exhaustive enumeration and description, and it should be understood that they do not constitute a closed limitation on quantity.
  • the weight of the relevant components mentioned in the embodiment description of the present application can not only refer to the content of each component, but also represent the proportional relationship between the weights of the components. Therefore, as long as the content of the relevant components is proportionally enlarged or reduced according to the embodiment description of the present application, it is within the scope disclosed in the embodiment description of the present application. Furthermore, the weight described in the embodiment description of the present application can be a mass unit known in the chemical industry such as ⁇ g, mg, g, kg, etc.
  • the present application provides a secondary battery, which includes a positive electrode sheet, a negative electrode sheet and a non-aqueous electrolyte; wherein the negative electrode sheet includes a negative electrode active material layer, the negative electrode active material layer includes a negative electrode active material, and the negative electrode active material includes a graphite material; the non-aqueous electrolyte includes a solvent, the solvent includes a first solvent, and the first solvent is a chain carboxylic acid ester;
  • the OI value of the negative electrode plate, the resistance value R of the negative electrode plate and the mass proportion W0 of the first solvent in the solvent satisfy the following relationship: 0.08/m ⁇ W0 ⁇ 100/(R ⁇ OI) ⁇ 5/m ⁇ ;
  • the OI value of the negative electrode plate refers to the ratio of the diffraction peak intensity of the 004 crystal plane of the graphite material to the diffraction peak intensity of the 110 crystal plane; the unit of R is m ⁇ .
  • the electrode plate can be a positive electrode plate or a negative electrode plate
  • the "active material” in the electrode plate refers to a material that can reversibly embed and release active ions.
  • negative electrode active material refers to a material used for negative electrode plates that can reversibly embed and release active ions
  • positive electrode active material refers to a material used for positive electrode plates that can reversibly release and embed active ions.
  • active material and “active substance” have the same meaning and can be used interchangeably;
  • positive electrode active substance and “positive electrode active material” have the same meaning and can be used interchangeably;
  • negative electrode active substance and “negative electrode active material” have the same meaning and can be used interchangeably.
  • active material layer includes the positive active material layer of the positive electrode sheet and the negative active material layer of the negative electrode sheet, and may refer to the positive active material layer or the negative active material layer according to the detailed circumstances. It is understood that the positive active material layer contains positive active material, and the negative active material layer contains negative active material.
  • the OI value of the negative electrode sheet has a meaning known in the art.
  • the OI value of the negative electrode sheet refers to the ratio of the diffraction peak intensity of the 004 crystal plane of the graphite material in the negative electrode active material layer to the diffraction peak intensity of the 110 crystal plane, which can be used to characterize the orientation of the negative electrode active material layer and reflect the degree of anisotropy of the grain arrangement in the negative electrode active material layer.
  • the 004 crystal plane corresponds to a layer structure parallel to the graphite of the electrode sheet
  • the 110 crystal plane corresponds to a layer structure perpendicular to the graphite of the electrode sheet; the smaller the OI value, the more favorable it is for the diffusion of active ions (such as lithium ions) and the more favorable it is for reducing the expansion of the electrode sheet itself.
  • the OI value of the negative electrode sheet can be adjusted by, but not limited to, the following methods: at least one parameter selected from the group consisting of the OI value of graphite particles, the particle size of graphite particles (such as D v 50), the porosity of the negative electrode sheet, the compaction density of the negative electrode sheet, the type and content of the components of the negative electrode sheet, etc. This is achievable for those skilled in the art.
  • the negative electrode sheet resistance value R has a well-known meaning in the art.
  • R in the present application can be obtained by testing with a resistor meter, for example, a BER1300 multi-function sheet resistance meter can be used for testing.
  • the following method can be used for testing: cut the negative electrode sheet into a sample to be tested of a certain size (a small disc with a diameter of 40 mm); place the sample to be tested between two probes of a resistor meter (such as a BER1300 multi-function sheet resistance meter), and record the resistance test value; take multiple (such as at least 5) samples to be tested, and calculate the average value of the multiple samples to be tested as the test result of the negative electrode sheet resistance value R.
  • chain carboxylate has a meaning well known in the art.
  • the fast charging performance, cycle performance and safety performance of the secondary battery can be taken into account.
  • the OI value and W0 satisfy the above relationship 0.08/m ⁇ W0 ⁇ 100/(R ⁇ OI) ⁇ 5/m ⁇
  • the chain carboxylate in the non-aqueous electrolyte has the characteristics of low viscosity and conductivity, which can significantly enhance the conductivity of the battery and improve the low temperature performance and cycle stability of the battery.
  • the negative electrode plate has a suitable orientation degree and has a suitable directional selectivity in the process of active ion (such as lithium ion) embedding, which can disperse the active ion embedding expansion (such as lithium embedding expansion) in different directions, thereby reducing the cycle expansion of the plate and the battery cell, which can effectively alleviate the problem of aggravated expansion of the plate itself due to the poor interface stability between the chain carboxylate and the negative electrode, improve battery safety, and reduce the concentration polarization of active ions in the transmission process of the negative electrode plate, and achieve a significant improvement in the fast charging capability of the battery with the negative electrode plate resistance value R. Therefore, by synergistically controlling the OI value, R and W0, the secondary battery can have excellent comprehensive functions in terms of fast charging performance, cycle performance and safety performance, and can take into account a shorter fast charging time, lower cycle expansion and higher cycle capacity retention rate.
  • active ion such as lithium ion
  • the OI value of the negative electrode plate can also be any of the following values or an interval consisting of any two of the following values: 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, etc.
  • the OI value of the negative electrode plate can be selected from any of the following ranges: 6-15, 12-25, 6-18, 14-16, etc.
  • the QI value By adjusting the QI value within a more appropriate range, it is more conducive to reducing the directional selectivity in the active ion embedding process, so that the active ions can be better embedded and expanded and dispersed in different directions; in addition, the active ion transport performance of the negative electrode can also be better improved.
  • the resistance value R of the negative electrode plate can also be any of the following values or a range selected from any two of the following values: 1m ⁇ , 2m ⁇ , 3m ⁇ , 4m ⁇ , 5m ⁇ , 6m ⁇ , 8m ⁇ , 10m ⁇ , 12m ⁇ , 15m ⁇ , 16m ⁇ , 8m ⁇ , 20m ⁇ , 25 m ⁇ , 30m ⁇ , 35m ⁇ , 40m ⁇ , 45m ⁇ , 50m ⁇ , etc.
  • the resistance value R of the negative electrode plate can also be selected from any of the following ranges: 12m ⁇ to 18m ⁇ , 14m ⁇ to 16m ⁇ , 5m ⁇ to 20m ⁇ , 5m ⁇ to 18m ⁇ , 10m ⁇ to 18m ⁇ , etc.
  • the resistance value R of the negative electrode sheet can be adjusted by, but not limited to, the following methods: the compaction density of the negative electrode sheet, the porosity of the negative electrode sheet, the type and content of the components of the negative electrode sheet, etc.
  • the resistance value R of the negative electrode sheet can be adjusted by adjusting the type and/or content of the conductive agent in the negative electrode sheet.
  • W0 ⁇ 100/(R ⁇ OI) can be controlled within a more appropriate range, thereby achieving better comprehensive effects in terms of shorter fast charging time, lower cycle expansion and higher cycle capacity retention rate, and is more conducive to improving the active ion transport performance and electronic conduction performance of the negative electrode sheet.
  • the mass proportion of the first solvent in the solvent is denoted as W0.
  • W0 may also be any of the following percentages: 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, etc., and may also be selected from an interval consisting of any two of the above percentages, for example, 20% ⁇ W0 ⁇ 80%, 30% ⁇ W0 ⁇ 70%, 50% ⁇ W0 ⁇ 70%, 10% ⁇ W0 ⁇ 60%, 20% ⁇ W0 ⁇ 60%, etc.
  • the content W0 of the chain carboxylic acid ester (first solvent) in the solvent within a certain range, it is possible to enhance the conductivity of the battery while taking into account the fast charging performance, cycle performance and safety performance of the secondary battery, and to improve the low temperature performance and cycle stability of the secondary battery.
  • W0 ⁇ 100/OI may also be any of the following values or an interval consisting of any two of the following values: 0.67, 0.8, 1, 1.2, 1.3, 1.33, 1.33 ⁇ 0.01, 1.4, 1.5, 2, 2.5, 2.67, 2.67 ⁇ 0.01, 3, 4, 4.5, 4.67, 4.67 ⁇ 0.01, 5, 5.33, 5.33 ⁇ 0.01, 6, 7, 8, 9, 10, etc.
  • the matching of the chain carboxylic acid ester in the non-aqueous electrolyte and the grain arrangement direction in the negative electrode active material layer is further regulated by W0 ⁇ 100/OI, which makes it easier to achieve the improvement of the comprehensive performance of fast charging performance, cycle performance and safety performance.
  • the secondary battery has the following characteristics: 0.08/m ⁇ W0 ⁇ 100/(R ⁇ OI) ⁇ 5/m ⁇ .
  • W0 ⁇ 100/(R ⁇ OI) can also be any of the following values or an interval consisting of any two of the following values: 0.1/m ⁇ , 0.13/m ⁇ , 0.15/m ⁇ , 0.2m ⁇ , 0.3/m ⁇ , 0.4/m ⁇ , 0.5/m ⁇ , 0.6/m ⁇ , .8/m ⁇ , 1/m ⁇ , 1.2/m ⁇ , 1.4/m ⁇ , 1.5/m ⁇ , 1.6/m ⁇ , 1.8/m ⁇ , 2/m ⁇ , 2.2/m ⁇ , 2.4/m ⁇ , 2.5/m ⁇ , 2.6/m ⁇ , 2.8/m ⁇ , 3/m ⁇ , 3.5/m ⁇ , 3.6/m ⁇ , 3.8/m ⁇ , 4/m ⁇ , 4.5/m ⁇ , 4.8/m ⁇ , 5/m ⁇ , etc.
  • the resistance value R of the negative electrode plate is further synergistically controlled, so that W0 ⁇ 100/(R ⁇ OI) can be controlled within an appropriate range, which can better take into account the comprehensive performance of the secondary battery in terms of fast charging performance, cycle performance and safety performance.
  • the secondary battery satisfies the following characteristic combination: 6 ⁇ OI ⁇ 18, 10m ⁇ R ⁇ 20m ⁇ , and 20% ⁇ W0 ⁇ 80%. In some embodiments thereof, 12 ⁇ OI ⁇ 18, 10m ⁇ R ⁇ 20m ⁇ , and 10% ⁇ W0 ⁇ 60%.
  • the resistance value R of the negative electrode plate to be 10m ⁇ -20m ⁇
  • the mass proportion W0 of the chain carboxylic acid ester solvent in the solvent to be 20%-80% (further optionally 10%-60%)
  • 12 ⁇ OI ⁇ 18, 10m ⁇ R ⁇ 20m ⁇ , and 20% ⁇ W0 ⁇ 60% are examples of
  • 12 ⁇ OI ⁇ 18, 10m ⁇ R ⁇ 20m ⁇ , and 50% ⁇ W0 ⁇ 70% are provided.
  • the first solvent comprises a compound having a structure as shown in formula (1):
  • R1 and R2 are independently alkyl or halogenated alkyl. It can be seen that R1 and R2 do not form a ring, and the compound with the structure shown in formula (1) is a chain carboxylate.
  • R 1 and R 2 are each independently C 1-3 alkyl or C 1-3 haloalkyl.
  • R 1 and R 2 are each independently C 1-3 alkyl or C 1-3 fluoroalkyl.
  • the C 1-3 alkyl group may be a methyl group (which may be represented by Me, -CH 3 ), an ethyl group (which may be represented by Et, -CH 2 CH 3 ) or a propyl group
  • the propyl group may be a n-propyl group (which may be represented by 1-propyl group, n-Pr, n-propyl group, -CH 2 CH 2 CH 3 ) or an isopropyl group (which may be represented by 2-propyl group, i-Pr, i-propyl group, -CH(CH 3 ) 2 ).
  • the C 1-3 alkyl group may be a methyl group, an ethyl group or a n-propyl group. Further, further, the C 1-3 alkyl group may be a methyl group or an ethyl group.
  • the carbon atom in the C1-3 haloalkyl group may be 1, 2, or 3, that is, it may be a C1 haloalkyl group, a C2 haloalkyl group, or a C3 haloalkyl group.
  • the halogen atom in the C1-3 haloalkyl group may be fluorine.
  • the number of halogen atoms in the C1-3 haloalkyl group may be 1 or more. When the number of halogen atoms in the C1-3 haloalkyl group is more than one, it may be 2 to all alkyl hydrogen atoms are substituted.
  • the carbon atom in the C1-3 fluoroalkyl group may be 1, 2, or 3, that is, it may be a C1 fluoroalkyl group, a C2 fluoroalkyl group, or a C3 fluoroalkyl group.
  • the number of fluorine atoms in the C1-3 fluoroalkyl group may be 1 or more. When the number of fluorine atoms in the C1-3 fluoroalkyl group is more than one, it may be 2 to perfluorinated.
  • R1 and R2 are independently selected from the group consisting of methyl, ethyl, propyl, fluoromethyl, fluoroethyl and fluoropropyl.
  • R1 and R2 are independently selected from the group consisting of methyl, ethyl, fluoromethyl and fluoroethyl.
  • the number of fluorine atoms in the fluoromethyl group may be independently selected from 1, 2 or 3.
  • the number of fluorine atoms in the fluoroethyl group may be independently selected from 1, 2, 3, 4, 5 or 6, and further independently selected from 1, 2 or 3.
  • the number of fluorine atoms in the fluoropropyl group may be independently selected from 1, 2, 3, 4, 5, 6, 7, 8 or 9, and further independently selected from 1, 2 or 3.
  • a first solvent with a smaller molecular size can be selected.
  • the first solvent has a lower viscosity, which is beneficial for the secondary battery to obtain better fast charging performance.
  • the first solvent includes one or more of the following compounds, which may be selected from one or more of the following compounds:
  • the first solvent comprises one or more of the following compounds: methyl acetate, ethyl acetate, methyl difluoroacetate and ethyl difluoroacetate. In some embodiments thereof, the first solvent is selected from one or more of the following compounds: methyl acetate, ethyl acetate, methyl difluoroacetate and ethyl difluoroacetate.
  • the nonaqueous electrolyte further includes a first additive; the first additive is diisocyanate.
  • diisocyanate refers to a compound containing two isocyanate groups (—NCO).
  • chain carboxylic acid ester (first solvent) is conducive to improving the fast charging ability of the battery.
  • first solvent due to the compatibility factors between carboxylic acid ester and negative electrode sheet, if the amount W0 of the carboxylic acid ester does not match the OI value and resistance value R of the negative electrode sheet, it may aggravate the expansion problem of the negative electrode sheet itself, and may also affect the gas production problem at the interface, and may also cause the attenuation of the battery cell capacity and the deterioration of the battery cycle performance.
  • SEI solid electrolyte interface
  • the protective layer can assist the active ions to be embedded in the negative electrode active material layer of the negative electrode sheet, so that the active ion embedding expansion effect of the negative electrode sheet can be evenly conducted in all directions, thereby reducing the cycle expansion rate of the negative electrode sheet.
  • the first additive can also significantly improve the stability of the interface between the electrolyte and the negative electrode sheet, which can reduce the consumption of the electrolyte and the damage to the negative electrode structure during the cycle of the secondary battery, thereby significantly improving the cycle performance of the secondary battery.
  • the first additive comprises a compound having the following structure:
  • R 3 is an unsubstituted or Ra-substituted C 1-18 alkylene group
  • R 11 and R 12 are independently alkyl or halogenated alkyl.
  • R 11 and R 12 are independently C 1-3 alkyl or C 1-3 halogenated alkyl.
  • R 11 and R 12 are independently C 1-3 alkyl or C 1-3 fluoroalkyl.
  • R 11 and R 12 are independently selected from the group consisting of methyl, ethyl, propyl, fluoromethyl, fluoroethyl and fluoropropyl.
  • R 11 and R 12 are independently selected from the group consisting of methyl, ethyl, fluoromethyl and fluoroethyl.
  • the number of fluorine atoms in the fluoromethyl group may be independently selected from 1, 2 or 3.
  • the number of fluorine atoms in the fluoroethyl group may be independently selected from 1, 2, 3, 4, 5 or 6, and may further be independently selected from 1, 2 or 3.
  • the number of fluorine atoms in the fluoropropyl group may be independently selected from 1, 2, 3, 4, 5, 6, 7, 8 or 9, and may further be independently selected from 1, 2 or 3.
  • the number of carbon atoms in the "C 1-18 alkylene” is 1 to 16.
  • the number of carbon atoms in the "C 1-18 alkylene” can also be any of the following values or an interval consisting of any two of the following values: 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15 and 16.
  • the interval consisting of any two values is 1 to 16, 2 to 16, 4 to 16, 6 to 16, 1 to 14, 2 to 14, 4 to 14, 6 to 14, 1 to 10, 2 to 10, 4 to 10, 6 to 10, etc.
  • the number of carbon atoms of R 3 is 1 to 16. Further, the number of carbon atoms of R 3 can also be any of the following values or an interval consisting of any two of the following values: 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15 and 16. The interval consisting of any two values is 1 to 16, 2 to 16, 4 to 16, 6 to 16, 1 to 14, 2 to 14, 4 to 14, 6 to 14, 1 to 10, 2 to 10, 4 to 10, 6 to 10, etc.
  • R 3 is an unsubstituted or Ra-substituted C 2-10 alkylene group, an unsubstituted or Ra-substituted C 3-18 divalent cycloalkyl group, or an unsubstituted or Ra-substituted C 6-18 arylene group.
  • R 3 is a C 2-10 alkylene group, a C 6-18 divalent cycloalkyl group, or a C 6-18 arylene group; further alternatively, R 3 is a C 4-10 alkylene group, a C 6-14 divalent cycloalkyl group, or a C 6-14 arylene group; further alternatively, R 3 is a C 4-10 alkylene group, a C 6-10 divalent cycloalkyl group, or a C 6-10 arylene group; further alternatively, R 3 is a C 4-8 hexylene group, a C 6-10 divalent cycloalkyl group containing a hexyl ring, or a C 6-10 arylene group containing a benzene ring.
  • a halogen atom which may be one or more of fluorine, chlorine, bromine and iodine, and may further be fluorine
  • a halogen atom which may be one or more of fluorine, chlorine, bromine and iodine, and may further be fluorine
  • Ra is a halogen atom, which may be one or more of fluorine, chlorine, bromine and iodine, and may further be fluorine.
  • the number of Ra can be 0, one or more. When the number of Ra is 0, it corresponds to the "unsubstituted" situation. When the number of Ra is 1 or more, it corresponds to the "Ra substituted” situation.
  • the number of Ra can be 0.
  • the number of carbon atoms in R 3 can be as defined above.
  • R 3 is an unsubstituted C 1-18 alkylene group, an unsubstituted C 1-16 alkylene group, an unsubstituted C 2-14 alkylene group, and the like.
  • the number of Ra in R 3 , can be one or more.
  • Ra is a C 1-10 alkyl group, further a C 1-3 alkyl group, further a methyl group or an ethyl group. In some embodiments, Ra is a methyl group.
  • R 3 is C 2-10 alkylene, C 2-10 heteroalkylene, C 6-18 arylene, C 2-18 heteroarylene, C 3-18 alicyclic group or C 3-18 hetero alicyclic group, any of which may be unsubstituted or substituted with Ra; if not otherwise specified, in the case of "Ra substituted", the number of Ra may be 1 or more.
  • the C 6-18 arylene may be a C 6-14 arylene, and may further be a C 6-14 arylene.
  • hydrocarbon compound refers to a compound composed of carbon atoms and hydrogen atoms.
  • Hydrocarbon compounds can be saturated structures (i.e. saturated hydrocarbons) or unsaturated structures (i.e. unsaturated hydrocarbons), can contain ring structures (i.e. cyclic hydrocarbons) or not contain ring structures (i.e. chain hydrocarbons), can have aromaticity (i.e. aromatic hydrocarbons or aromatic hydrocarbons) or not have aromaticity (i.e. aliphatic hydrocarbons).
  • Hydrocarbons with saturated structures, i.e. saturated hydrocarbons can be alkanes or cycloalkanes. Alkanes do not contain ring structures, can be straight chain structures, or can contain branches.
  • Cycloalkanes contain ring structures, and the number of ring structures can be 1 or more, such as 1, 2 or 3. Cycloalkanes are saturated hydrocarbons containing ring structures, which are non-aromatic hydrocarbons. Hydrocarbons with aromaticity, i.e. aromatic hydrocarbons, contain aromatic ring structures. Unsaturated hydrocarbons can contain carbon-carbon double bonds, carbon-carbon triple bonds, etc. Unsaturated hydrocarbons can contain ring structures or not.
  • olefin refers to a chain hydrocarbon containing one or more carbon-carbon double bonds
  • cycloolefin refers to a cyclic hydrocarbon containing one or more carbon-carbon double bonds
  • alkyne refers to a chain hydrocarbon containing one or more carbon-carbon triple bonds
  • cycloalkyne refers to a cyclic hydrocarbon containing one or more carbon-carbon triple bonds
  • alkyne refers to a chain hydrocarbon containing one or more carbon-carbon triple bonds
  • cycloalkyne refers to a cyclic hydrocarbon containing one or more carbon-carbon triple bonds.
  • Alicyclic hydrocarbon refers to a non-aromatic hydrocarbon containing a ring structure, which may be saturated or unsaturated, and the carbon atoms constituting the unsaturated bonds may or may not be ring-forming atoms.
  • alicyclic hydrocarbons may include, but are not limited to, cycloalkanes, cycloalkene
  • hydrocarbyl refers to a monovalent residue formed by the loss of a hydrogen atom from a hydrocarbon compound containing a primary (normal) carbon atom, a secondary carbon atom, a tertiary carbon atom, a quaternary carbon atom, or a combination thereof.
  • C1-10 hydrocarbyl refers to a hydrocarbyl containing 1 to 10 carbon atoms, and each occurrence may be independently a C1 hydrocarbyl, a C2 hydrocarbyl, a C3 hydrocarbyl, a C4 hydrocarbyl, a C5 hydrocarbyl, a C6 hydrocarbyl, a C7 hydrocarbyl, a C8 hydrocarbyl, a C9 hydrocarbyl, or a C10 hydrocarbyl .
  • alkylene refers to a divalent hydrocarbon group derived from a hydrocarbon compound by removing two hydrogen atoms (or derived from a hydrocarbon group by losing another hydrogen atom), which has two monovalent radical centers, and may be a saturated branched structure or a saturated straight chain structure.
  • C1 - C10alkylene means that the hydrocarbon moiety contains 1 to 10 carbon atoms, and each occurrence may be independently C1alkylene , C2alkylene , C3alkylene, C4alkylene , C5alkylene , C6alkylene , C7alkylene , C8alkylene , C9alkylene or C10alkylene.
  • alkyl refers to a monovalent residue formed by the loss of a hydrogen atom from a saturated hydrocarbon containing a primary (normal) carbon atom, a secondary carbon atom, a tertiary carbon atom, a quaternary carbon atom, or a combination thereof.
  • a phrase containing the term, for example, " C1-10 alkyl” refers to an alkyl containing 1 to 10 carbon atoms, and each occurrence may be independently C1 alkyl, C2 alkyl, C3 alkyl, C4 alkyl, C5 alkyl, C6 alkyl, C7 alkyl, C8 alkyl, C9 alkyl or C10 alkyl.
  • Suitable examples include, but are not limited to, methyl (Me, -CH 3 ), ethyl (Et, -CH 2 CH 3 ), 1-propyl (n-Pr, n-propyl, -CH 2 CH 2 CH 3 ), 2-propyl (i-Pr, i-propyl, -CH(CH 3 ) 2 ), 1-butyl (n-Bu, n-butyl, -CH 2 CH 2 CH 2 CH 3 ), 2-methyl-1-propyl (i-Bu, i-butyl, -CH 2 CH(CH 3 ) 2 ), 2-butyl (s-Bu, s-butyl, -CH(CH 3 )CH 2 CH 3 ), 2-methyl-2-propyl (t-Bu, t-butyl, -C(CH 3 ) 3 ) , 1-pentyl (n-pentyl, -CH 2 CH 2 CH 2 CH 3 ), 2-pentyl (-CH( CH3
  • alkylene refers to a radical derived from an alkane by removing two hydrogen atoms (or in the case of an alkyl radical).
  • a divalent hydrocarbon group having two monovalent radical centers may be a saturated branched structure or a saturated straight chain structure.
  • C 1 to C 10 alkylene means that the alkyl portion contains 1 to 10 carbon atoms, and each occurrence may be independently C 1 alkylene (i.e., methylene), C 2 alkylene (i.e., ethylene), C 3 alkylene (i.e., propylene), C 4 alkylene (i.e., butylene), C 5 alkylene (i.e., pentylene), C 6 alkylene (i.e., hexylene), C 7 alkylene (i.e., heptylene), C 8 alkylene (i.e., octylene), C 9 alkylene (i.e., nonylene) or C 10 alkylene (i.e., decylene).
  • C 1 alkylene i.e., methylene
  • C 2 alkylene i.e., ethylene
  • C 3 alkylene i.e., propylene
  • C 4 alkylene i.e., butylene
  • Suitable examples include, but are not limited to, methylene (—CH 2 —), 1,1-ethyl (—CH(CH 3 )—), 1,2-ethyl (—CH 2 CH 2 —), 1,1-propyl (—CH(CH 2 CH 3 )—), 1,2-propyl (—CH 2 CH(CH 3 )—), 1,3-propyl (—CH 2 CH 2 CH 2 —), and 1,4-butyl (—CH 2 CH 2 CH 2 CH 2 —).
  • alkenyl refers to a monovalent residue formed by the loss of a hydrogen atom from an olefin compound of a chain structure, and the hydrogen atom may be located on a carbon-carbon double bond or on an alkyl substituent of the carbon-carbon double bond.
  • alkynyl refers to a monovalent residue formed by the loss of a hydrogen atom from an alkyne compound of a chain structure, and the hydrogen atom may be located on a carbon-carbon triple bond or on an alkyl substituent of the carbon-carbon triple bond.
  • C2-10 alkynyl refers to an alkynyl containing 2 to 10 carbon atoms, and each occurrence may be independently C2 alkynyl, C3 alkynyl, C4 alkynyl, C5 alkynyl, C6 alkynyl, C7 alkynyl, C8 alkynyl, C9 alkynyl or C10 alkynyl.
  • Suitable examples include, but are not limited to, ethynyl ( CH ⁇ C- ), propargyl ( CH ⁇ C - CH2- ), CH3 - C ⁇ C- , etc.
  • heteroalkyl means that at least one carbon atom is replaced by a heteroatom on the basis of an alkyl group; a heteroatom is a non-carbon hydrogen atom, which may be, but is not limited to, an N atom, an O atom, an S atom, a P atom, etc. O, N, and S are used as examples for illustration.
  • the resulting heteroalkyl group is an alkoxy group (e.g., -OCH 3 , etc.), an amino group (e.g., -NHCH 3 , -N(CH 3 ) 2 , etc.) or a thioalkyl group (e.g., -SCH 3 ).
  • the resulting heteroalkyl group is an alkoxyalkyl group (e.g., -CH 2 CH 2 -O-CH 3 , etc.), an alkylaminoalkyl group (e.g., -CH 2 NHCH 3 , -CH 2 N(CH 3 ) 2 , etc.) or an alkylthioalkyl group (e.g., -CH 2 -S-CH 3 ).
  • the resulting heteroalkyl group may be a hydroxyalkyl group (e.g., -CH 2 CH 2 -OH), an aminoalkyl group (e.g., -CH 2 NH 2 ), or a mercaptoamino group (e.g., -CH 2 CH 2 -SH).
  • heteroalkyl such as, for example, "C 1-10 heteroalkyl” refer to heteroalkyl groups containing from 1 to 10 carbon atoms, and each occurrence may be, independently of one another, a C 1 heteroalkyl group, a C 2 heteroalkyl group, a C 3 heteroalkyl group, a C 4 heteroalkyl group, a C 5 heteroalkyl group, a C 6 heteroalkyl group, a C 7 heteroalkyl group, a C 8 heteroalkyl group, a C 9 heteroalkyl group, or a C 10 heteroalkyl group.
  • alkoxy refers to a monovalent group formed by connecting an alkyl group to -O-.
  • a phrase containing this term, for example, "C 1-10 oxaalkyl” refers to an alkoxy group containing 1 to 10 carbon atoms, and each occurrence may be independently C 1 alkoxy, C 2 alkoxy, C 3 alkoxy, C 4 alkoxy, C 5 alkoxy, C 6 alkoxy, C 7 alkoxy, C 8 alkoxy, C 9 alkoxy or C 10 alkoxy. Suitable examples may include, but are not limited to, methoxy (CH 3 O-), ethoxy (CH 3 CH 2 O-) , and the like.
  • oxaalkyl refers to an alkyl group in which at least one carbon atom is replaced by an oxygen atom, and the oxygen atom may be located at the attachment site of the alkyl group or may not be located at the attachment site.
  • the number of oxygen atoms may be one or more. Taking one oxygen atom hybridization as an example, such as alkoxy, alkoxyalkyl, etc.
  • C 1-10 oxaalkyl refers to an oxaalkyl group containing 1 to 10 carbon atoms, and each occurrence may be independently C 1 oxaalkyl, C 2 oxaalkyl, C 3 oxaalkyl, C 4 oxaalkyl, C 5 oxaalkyl, C 6 oxaalkyl, C 7 oxaalkyl, C 8 oxaalkyl, C 9 oxaalkyl or C 10 oxaalkyl.
  • heteroalkylene is also referred to as "divalent heteroalkyl", which refers to a divalent heterohydrocarbon group having two monovalent radical centers derived from a heteroalkyl group by losing a hydrogen atom (the hydrogen atom may be located on a carbon atom or a heteroatom), or refers to an alkylene group in which at least one carbon atom is replaced by a heteroatom (any heteroatom may be located at the connection site of the alkylene group or may not be located at the connection site); the heteroatom may be, but is not limited to, an N atom, an O atom, an S atom, a P atom, etc.
  • C1-10 heteroalkylene refers to a heteroalkylene group containing 1 to 10 carbon atoms, and each occurrence may be independently C1 heteroalkylene, C2 heteroalkylene, C3 heteroalkylene, C4 heteroalkylene , C5 heteroalkylene, C6 heteroalkylene, C7 heteroalkylene, C8 heteroalkylene, C9 heteroalkylene or C10 heteroalkylene.
  • cycloalkyl refers to a monovalent residue formed by the loss of a cyclic or non-cyclic hydrogen atom of a saturated cycloalkane, which can form a monovalent attachment site directly on the ring or at the position of an alkyl substituent on the ring.
  • C3-10 cycloalkyl refers to a cycloalkyl containing 3 to 10 carbon atoms, each occurrence of which can be independently C3 cycloalkyl, C4 cycloalkyl, C5 cycloalkyl, C6 cycloalkyl, C7 cycloalkyl , C8 cycloalkyl, C9 cycloalkyl or C10 cycloalkyl.
  • the number of ring structures in a cycloalkyl group can be 1 or more, for example 1, 2 or 3.
  • the number of ring atoms in any ring structure may be 3 to 8, for example 3, 4, 5, 6, 7 or 8; Ding ring Pentyl ring Hexyl ring
  • the case where a monovalent attachment site is formed directly on the ring may include, but is not limited to: cyclopropyl Cyclobutyl Cyclopentyl Cyclohexyl
  • the formation of a monovalent attachment site from an alkyl substituent on the ring may include, but is not limited to (A C7 cycloalkyl group containing a hexyl ring).
  • the terminal Indicates the site of covalent bond attachment.
  • alicyclic group is also referred to as "divalent alicyclic group", which refers to a divalent residue derived from an alicyclic hydrocarbon by losing two hydrogen atoms on the ring or on the non-ring, and any of the lost hydrogen atoms may be on the ring or not on the ring, that is, a monovalent attachment site may be formed directly on the ring or at a hydrocarbon substituent position on the ring.
  • Alicyclic groups may include, but are not limited to, divalent cycloalkyl groups, divalent cycloalkenyl groups, divalent cycloalkynyl groups, and the like.
  • C 3-10 alicyclic group refers to an alicyclic group containing 3 to 10 carbon atoms, and each occurrence may be independently C 3 alicyclic group, C 4 alicyclic group, C 5 alicyclic group, C 6 alicyclic group, C 7 alicyclic group, C 8 alicyclic group, C 9 alicyclic group, or C 10 alicyclic group.
  • divalent cycloalkyl is also referred to as "cycloalkylene", which refers to a divalent saturated hydrocarbon group derived from a cycloalkane by removing two hydrogen atoms (or derived from a cycloalkyl by losing another hydrogen atom), having two monovalent group centers, and the position of any monovalent group center can be independently located on the ring or not on the ring.
  • C 3 - 10 divalent cycloalkyl refers to a divalent cycloalkyl group containing 3 to 10 carbon atoms, and each occurrence can be independently C 3 divalent cycloalkyl, C 4 divalent cycloalkyl, C 5 divalent cycloalkyl, C 6 divalent cycloalkyl, C 7 divalent cycloalkyl, C 8 divalent cycloalkyl, C 9 divalent cycloalkyl or C 10 divalent cycloalkyl.
  • the number of carbon atoms in the "divalent cycloalkyl" can be 3 to 10, and can be 3, 4, 5, 6, 7, 8, 9 or 10, for example, 6 to 10.
  • the number of ring structures in a divalent cycloalkyl group may be 1 or more, for example, 1, 2 or 3.
  • the number of ring atoms in any ring structure of a "divalent cycloalkyl group” may be 3 to 8, and may be 3, 4, 5, 6, 7 or 8.
  • a "C 6-10 divalent cycloalkyl group” refers to a divalent cycloalkyl group containing 6 to 10 carbon atoms, wherein the number of ring atoms in one ring structure is not particularly limited.
  • C 6-10 divalent cycloalkyl group containing a hexyl ring refers to a divalent cycloalkyl group containing a hexyl ring and containing 6 to 10 carbon atoms, for example, a divalent cyclohexyl group (such as a 1,4-position structure) 1,3-position structure Or 1,2-position structure ), wait.
  • divalent cycloalkenyl group is also referred to as “cycloalkenylene group”, which refers to a divalent unsaturated hydrocarbon group having two monovalent radical centers derived from a cycloalkene by removing two hydrogen atoms, and the position of any monovalent radical center can be independently located on the ring or not on the ring.
  • C 3-10 divalent cycloalkenyl group refers to a divalent cycloalkenyl group containing 3 to 10 carbon atoms, and each occurrence can be independently C 3 divalent cycloalkenyl group, C 4 divalent cycloalkenyl group, C 5 divalent cycloalkenyl group, C 6 divalent cycloalkenyl group, C 7 divalent cycloalkenyl group, C 8 divalent cycloalkenyl group, C 9 divalent cycloalkenyl group or C 10 divalent cycloalkenyl group.
  • heteroalicyclic group is also referred to as "divalent heteroalicyclic group", which means that at least one carbon atom of the hydrocarbon group is replaced by a heteroatom on the basis of the alicyclic group; the heteroatom may be located at the attachment site of the alicyclic group or not; the heteroatom may be located on the ring or not; the heteroatom may be, but is not limited to, an N atom, an O atom, an S atom, a P atom, etc. The heteroatom may be located at the attachment site of the alicyclic group (i.e., the end) or not.
  • C 3 - 10 heteroalicyclic group means a heteroalicyclic group containing 3 to 10 carbon atoms, and each occurrence may be independently C 3 heteroalicyclic group, C 4 heteroalicyclic group, C 5 heteroalicyclic group, C 6 heteroalicyclic group, C 7 heteroalicyclic group, C 8 heteroalicyclic group, C 9 heteroalicyclic group or C 10 heteroalicyclic group.
  • arylene refers to a divalent residue having two monovalent radical centers formed by losing two hydrogen atoms from an aromatic hydrocarbon (any of the lost hydrogen atoms may be independently located on the aromatic ring or may not be located on the aromatic ring).
  • C 6 - 14 arylene refers to an arylene containing 6 to 14 carbon atoms, and each occurrence may be independently C 6 arylene, C 7 arylene, C 8 arylene, C 9 arylene, C 10 arylene, C 11 arylene, C 12 arylene, C 13 arylene or C 14 arylene.
  • Suitable examples include, but are not limited to , arylene derived from the following aromatic rings: benzene, biphenyl , diphenylmethane, naphthalene, anthracene, phenanthrene, perylene, triphenylene or a hydrocarbon-substituted form of any of the foregoing, such as toluene, xylene, tetramethylbenzene, ethylbenzene, dimethylbiphenyl, etc.
  • heteroarylene is also referred to as "divalent heteroaryl", which means that at least one carbon atom is replaced by a heteroatom on the basis of an arylene; any heteroatom may be located at the attachment site of the arylene or not; any heteroatom may be located on the aromatic ring or not; the heteroatom may be, but is not limited to, an N atom, an O atom, an S atom, a P atom, etc.
  • C2-10 heteroarylene means a heteroarylene containing 2 to 10 carbon atoms , and each occurrence may be independently C2 heteroarylene, C3 heteroarylene, C4 heteroarylene, C5 heteroarylene, C6 heteroarylene, C7 heteroarylene, C8 heteroarylene, C9 heteroarylene or C10 heteroarylene.
  • R3 is any one of C1-8 alkylene, C6-14 arylene, -( Z1 ) p1 - CA- ( Z2 ) p2- and -( Z1 ) q1 - CA1- ( Z3 ) q3 - CA2- ( Z2 ) q2- , or a divalent group formed by replacing one or more hydrogen atoms in any of the foregoing divalent groups with a substituent Ra ; wherein Z1 , Z2 and Z3 are each independently a covalent bond or C1-3 alkylene, CA is a C4-14 divalent alicyclic group, CA1 and CA2 are each independently a C5-12 divalent alicyclic group, and p1, p2, q1, q2 and q3 are each independently 0 or 1.
  • Z 1 , Z 2 and Z 3 are each independently a covalent bond or a methylene group.
  • CA is a divalent cyclobutyl, a divalent cyclopentyl, a divalent cyclohexyl or
  • C A1 and C A2 are each independently a C 5-12 divalent alicyclic group; alternatively, C A1 and C A2 are each independently a C 4-6 divalent alicyclic group; further alternatively, C A1 and C A2 are each independently a divalent cyclopentyl group or a divalent cyclohexyl group; further alternatively, C A1 and C A2 are each independently a divalent cyclopentyl group.
  • R 3 is methylene, ethylene, propylene, butylene, pentylene, hexylene, phenylene, -CH 2 -Ph-CH 2 -, naphthylene, anthracene, -Ph-CH 2 -Ph-, -Ph-Ph-, divalent cyclobutyl, divalent cyclopentyl, divalent cyclohexyl, Or a divalent group formed by replacing one or more hydrogen atoms in any of the aforementioned divalent groups with a substituent Ra ; wherein Ph is a benzene ring.
  • Two of It means that two single bonds are introduced from any position on the ring to form two monovalent sites.
  • the two monovalent sites can be located in the same ring or in different rings, on different ring-forming atoms or on the same ring-forming atom. However, it is preferred that the two single bonds are introduced from different ring-forming atoms.
  • any Ra is independently a halogen atom or a C1-3 alkyl group; further optionally, any Ra is independently a fluorine atom, a methyl group or an ethyl group; further optionally, any Ra is independently a fluorine atom or a methyl group.
  • the first additive includes one or more of the following compounds: (1,4-phenylenediisocyanate, 1,4-diisocyanatobenzene), (1,3-phenylenediisocyanate, 1,3-diisocyanatobenzene), (1,3-bis(isocyanatomethyl)benzene, m-phenylenedimethyl isocyanate), (2,3,5,6-tetrafluorophenyl diisocyanate, 1,2,4,5-tetrafluoro-3,6- diisocyanatobenzene), (1,3-diisocyanato-2-methylbenzene), (2,4-diisocyanato-1-methylbenzene), (2,5-diisocyanato-1,3-dimethylbenzene), (1,4-diisocyanato-2,5-dimethylbenzene), (1,4-diisocyanato-2,3-dimethylbenzene), (1,4-diiso
  • the first additive is one or more of the following compounds: 1,4-phenylene diisocyanate, 1,3-phenylene diisocyanate, m-phenylenedimethyl isocyanate, 2,3,5,6-tetrafluorophenylene diisocyanate, 1,3-diisocyanato-2-toluene, 2,4-diisocyanato-1-toluene, 2,5-diisocyanato-1,3-xylene, 1,4-diisocyanato-2,5-xylene, 1,4-diisocyanato-2,3-xylene, 1,4-diisocyanato-2,3,5,6-tetramethylbenzene, 2,3-diisocyanato-1-ethylbenzene, 1,5-diisocyanatonaphthalene, 9,10-diisocyanatoanthracene, diphenylmethane diisocyanate, 3,3'
  • the first additive includes one or more of the following compounds: hexamethylene diisocyanate, 1,4-cyclohexane dimethyl diisocyanate, 1,3-phenylene diisocyanate, and 2,4-diisocyanate-1-toluene.
  • the first additive is selected from one or more of the following compounds: hexamethylene diisocyanate, 1,4-cyclohexane dimethyl diisocyanate, 1,3-phenylene diisocyanate, and 2,4-diisocyanate-1-toluene.
  • the mass proportion of the first additive in the non-aqueous electrolyte (which can be recorded as W1) is 0 to 11%.
  • W1 is 0, that is, the first additive is not added to the non-aqueous electrolyte.
  • the mass proportion W1 of the first additive in the non-aqueous electrolyte can also be any of the following percentages: 0, 0.005%, 0.01%, 0.015%, 0.02%, 0.05%, 0.1%, 0.5%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 10%, 11%, etc., and can also be selected from the interval consisting of any two of the above percentages, such as 0.005% to 11%, 0.005% to 10%, 0.1% to 5%, 1% to 5%, 0 to 1%, 0.1% to 1%, 0.01% to 10%, 1% to 10%, etc.
  • the non-aqueous electrolyte further comprises a second additive;
  • the second additive comprises one or more of lithium monofluorophosphate, lithium difluorophosphate, lithium tetrafluoroborate, a compound represented by formula (3), and a fluorosulfonate;
  • a, b and c are each independently a positive integer, m is an integer selected from 1-3, n is an integer selected from 0-4, and q is 0 or 1;
  • Ma + is a metal ion with a positive charge of a;
  • any Y is independently a boron atom or a phosphorus atom;
  • X is a halogen atom;
  • any R is independently one of a substituted or unsubstituted C1-10 alkylene group, a substituted or unsubstituted C1-10 haloalkylene group, a substituted or unsubstituted C6-20 arylene group, and a substituted or unsubstituted C6-20 haloarylene group.
  • the halogen atom in the haloalkylene group may be one or more of fluorine, chlorine, bromine and iodine, and may further be fluorine.
  • the number of halogen atoms in the haloalkylene group may be one or more.
  • the halogen atom in the halogenated arylene group may be one or more of fluorine, chlorine, bromine and iodine, and may further be fluorine.
  • the number of halogen atoms in the halogenated arylene group may be one or more.
  • any one R is independently one of Rc substituted or unsubstituted C 1-10 alkylene, Rc substituted or unsubstituted C 1-10 halogenated alkylene, Rc substituted or unsubstituted C 6-20 arylene, and Rc substituted or unsubstituted C 6-20 halogenated arylene.
  • R contains a substituent RC the number of RC can be 1 or more.
  • M in Ma+ includes one or more of Li, Na, K, Rb, Cs, Mg, Ca, Ba, Al, Fe, Cu, and Ni.
  • a, b, and c are each independently selected from 1, 2, or 3.
  • m is 1, 2, or 3.
  • n is 0 or 1-4, and further can be 0, 1, 2, 3 or 4.
  • the second additive includes one or more of lithium difluorophosphate, lithium monofluorophosphate, lithium tetrafluoroborate, lithium fluorosulfonate, and sodium fluorosulfonate. Further, it can be one or more of lithium difluorophosphate, lithium monofluorophosphate, lithium tetrafluoroborate, lithium fluorosulfonate, and sodium fluorosulfonate.
  • the mass proportion of the second additive in the non-aqueous electrolyte (which can be recorded as W2) is 0 to 11%.
  • the mass proportion of the second additive in the non-aqueous electrolyte W2 is any of the following percentages: 0, 0.005%, 0.01%, 0.015%, 0.02%, 0.05%, 0.1%, 0.5%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 10%, 11%, etc., and can also be selected from the interval consisting of any two of the above percentages, such as 0.005% to 11%, 0.01% to 11%, 0 to 10%, 0.005% to 10%, 0.01% to 10%, 0.05% to 10%, 0.05% to 5%, etc.
  • W2 is 0, that is, the second additive is not added to the non-aqueous electrolyte.
  • the introduction of the first additive diisocyanate may increase the impedance of the formed SEI film.
  • an inorganic-rich SEI film can be formed at the negative electrode, which can improve the fast charging performance of the secondary battery and further improve the cycle performance of the secondary battery.
  • the volume average particle size D v 50 of the negative electrode active material is ⁇ 6 ⁇ m; wherein D v 50 represents the particle size corresponding to when the cumulative volume distribution percentage of a substance or material reaches 50%; optionally, the volume average particle size D v 50 of the negative electrode active material is 6 ⁇ m to 20 ⁇ m; further optionally, the volume average particle size D v 50 of the negative electrode active material is 15 ⁇ m to 20 ⁇ m.
  • the D v 50 of the negative electrode active material can also be any of the following sizes: 6 ⁇ m, 8 ⁇ m, 10 ⁇ m, 12 ⁇ m, 15 ⁇ m, 16 ⁇ m, 18 ⁇ m, 20 ⁇ m, etc., and can also be an interval consisting of any two of the above sizes.
  • the volume cumulative distribution particle size D v N (wherein N represents any value selected from 0 to 100) can be used to characterize the particle size of a substance or material, which refers to the particle size corresponding to the cumulative volume distribution percentage of the substance or material reaching N%, and the volume proportion of particles less than or equal to D v N is N%.
  • D v N can be obtained from the volume cumulative distribution curve of the particle size of the substance or material. If there is no other explanation, the volume cumulative distribution curve starts from zero and accumulates from the small particle size side. Taking D v 50 as an example, D v 50 refers to the particle size corresponding to the cumulative volume distribution percentage of the substance or material reaching 50%.
  • D v 50 it means that the particle size of particles accounting for 50% of the volume of the substance or material is less than or equal to D v 50, and the particle size of particles accounting for 50% of the volume of the substance or material is greater than D v 50.
  • D v 50 can be referred to, and the particle size distribution can be conveniently measured using a laser particle size analyzer, such as the Mastersizer 2000E laser particle size analyzer and the LS-909 laser particle size analyzer (OMEC) from Malvern Instruments Ltd., UK.
  • a laser particle size analyzer such as the Mastersizer 2000E laser particle size analyzer and the LS-909 laser particle size analyzer (OMEC) from Malvern Instruments Ltd., UK.
  • the contact area between the negative electrode material and the electrolyte can be reduced, and the probability of side reactions with the solvent on the negative electrode surface can be reduced, which is more conducive to reducing the electrode expansion rate and can better improve the cycle performance of the battery cell.
  • the BET specific surface area of the negative electrode active material is 0.5 m 2 /g to 2.0 m 2 /g; optionally, the BET specific surface area of the negative electrode active material is 0.8 m 2 /g to 1.5 m 2 /g.
  • the BET specific surface area of the negative electrode active material can also be any of the following values or an interval consisting of any two of the following values: 0.5 m 2 /g, 0.6 m 2 /g, 0.8 m 2 /g, 1 m 2 /g, 1.5 m 2 /g, 1.8 m 2 /g, 2 m 2 /g, etc.
  • the BET specific surface area of the negative electrode active material can be obtained by testing (but not limited to) the following method: testing by nitrogen adsorption specific surface area analysis test method, and calculated by BET (Brunauer Emmett Teller) method, wherein the nitrogen adsorption specific surface area analysis test can be performed by the Tri Star II specific surface and pore analyzer of Micromeritics Company of the United States, and the test steps can refer to GB/T 19587-2004.
  • Sample to be tested negative electrode active material raw material; it can also be the negative electrode active material sampled from the negative electrode active material layer of the negative electrode sheet.
  • the test analysis method is as follows: dry the sample to be tested in a vacuum drying oven at 200°C for 2 hours; then use argon as the adsorption gas, and use the specific surface and pore analyzer to map the adsorption and desorption curve with a relative pressure P/ P0 of 0 to 0.99, P is the equilibrium adsorption pressure, P0 is the saturated vapor pressure, and the specific surface area of the negative electrode active material is calculated by the BET method.
  • the surface area of the negative electrode material can be reduced, thereby reducing the contact area between the negative electrode material and the electrolyte, thereby reducing the side reactions of the solvent on the negative electrode surface and better improving the cycle performance of the battery cell.
  • the negative electrode sheet in the secondary battery includes a negative electrode active material layer, the negative electrode active material layer includes a negative electrode active material, and the negative electrode active material includes a graphite material.
  • the negative electrode sheet includes a negative electrode current collector and a negative electrode film layer disposed on at least one surface of the negative electrode current collector, the negative electrode film layer includes a negative electrode active material layer, the negative electrode active material layer includes a negative electrode active substance, and the negative electrode active substance includes a graphite material.
  • the weight percentage of graphite material in the negative electrode active material is ⁇ 50%.
  • the weight percentage of graphite material in the negative electrode active material can also be any of the following percentages, or greater than or equal to any of the following percentages, or an interval from any of the following percentages to 100%, or an interval consisting of any two of the following percentages: 50%, 60%, 70%, 80%, 90%, 95%, 96%, 97%, 98%, 99%, etc.
  • the weight percentage of graphite material in the negative electrode active material is ⁇ 80%. In some embodiments, the weight percentage of graphite material in the negative electrode active material is 100%.
  • the negative electrode current collector has two surfaces opposite to each other in its thickness direction, and the negative electrode film layer is disposed on any one or both of the two opposite surfaces of the negative electrode current collector.
  • the negative electrode current collector may be a metal foil or a composite current collector.
  • copper foil may be used as the metal foil.
  • the composite current collector may include a polymer material base layer and a metal layer formed on at least one surface of the polymer material substrate.
  • the composite current collector may be obtained by forming a metal material on a polymer material substrate.
  • non-limiting examples of the metal material may include one or more of copper, copper alloy, nickel, nickel alloy, titanium, titanium alloy, silver and silver alloy.
  • non-limiting examples of the polymer material substrate may include one or more of substrates such as polypropylene (PP), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polystyrene (PS), polyethylene (PE), etc.
  • substrates such as polypropylene (PP), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polystyrene (PS), polyethylene (PE), etc.
  • the graphite material in the negative electrode active material may include one or more of artificial graphite and natural graphite.
  • the negative electrode active material may also include other negative electrode active materials for batteries known in the art.
  • the negative electrode active material may also include one or more of the following materials: soft carbon, hard carbon, silicon-based materials, tin-based materials, lithium titanate, etc.
  • the silicon-based material may include one or more of elemental silicon, silicon oxide compounds, silicon-carbon composites, silicon-nitrogen composites, and silicon alloys.
  • the tin-based material may include one or more of elemental tin, tin oxide compounds, and tin alloys.
  • negative electrode active materials for batteries may also be used, as long as they contain graphite materials.
  • These negative electrode active materials may use only one type of graphite material alone, or may use two or more in combination (at this time at least including graphite materials).
  • the negative electrode active material includes artificial graphite.
  • the negative electrode film layer may further optionally include a binder.
  • the binder may include one or more of styrene-butadiene rubber (SBR), polyacrylic acid (PAA), sodium polyacrylate (PAAS), polyacrylamide (PAM), polyvinyl alcohol (PVA), sodium alginate (SA), polymethacrylic acid (PMAA) and carboxymethyl chitosan (CMCS).
  • the negative electrode film layer may further include a conductive agent, which may include one or more of superconducting carbon, acetylene black, carbon black, Ketjen black, carbon dots, carbon nanotubes, graphene, and carbon nanofibers.
  • a conductive agent which may include one or more of superconducting carbon, acetylene black, carbon black, Ketjen black, carbon dots, carbon nanotubes, graphene, and carbon nanofibers.
  • the negative electrode film layer may further include other auxiliary agents, such as a thickener, etc.
  • auxiliary agents such as a thickener, etc.
  • thickeners may include sodium carboxymethyl cellulose (CMC-Na) and the like.
  • the negative electrode sheet can be prepared by the following method: the components for preparing the negative electrode sheet, such as the negative electrode active material, the conductive agent, the binder and any other components are dispersed in a solvent (a non-limiting example of the solvent is deionized water) to form a negative electrode slurry; the negative electrode slurry is coated on at least one side of the negative electrode current collector, and after drying, compaction (compacting can be performed by cold pressing), etc., the negative electrode sheet can be obtained.
  • the surface of the negative electrode current collector coated with the negative electrode slurry can be on a single surface of the negative electrode current collector or on both surfaces of the negative electrode current collector.
  • the solid content of the negative electrode slurry can be 40wt% to 60wt%.
  • the compacted density of the negative electrode sheet can be 1.4g/ cm3 to 1.95g/ cm3 , and can further be 1.5g/ cm3 to 1.8g/ cm3 .
  • wt% means weight percentage
  • the positive electrode plate includes a positive electrode current collector and a positive electrode film layer disposed on at least one surface of the positive electrode current collector, the positive electrode film layer includes a positive electrode active material layer, and further, the positive electrode active material layer includes a positive electrode active substance.
  • the positive electrode current collector has two surfaces opposite to each other in its thickness direction, and the positive electrode film layer is disposed on any one or both of the two opposite surfaces of the positive electrode current collector.
  • the positive electrode current collector may be a metal foil or a composite current collector.
  • aluminum foil may be used as the metal foil.
  • the composite current collector may include a polymer material base and a metal layer formed on at least one surface of the polymer material base.
  • the composite current collector may be formed by forming a metal material on a polymer material substrate; the metal material may include one or more of aluminum, aluminum alloy, nickel, nickel alloy, titanium, titanium alloy, silver and silver alloy, etc.; non-limiting examples of polymer material substrates include polypropylene (PP), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polystyrene Base materials such as polypropylene (PS) and polyethylene (PE).
  • PP polypropylene
  • PET polyethylene terephthalate
  • PBT polybutylene terephthalate
  • PS polypropylene
  • PE polyethylene
  • the positive electrode active material includes a lithium ion material; further, the secondary battery is a lithium ion secondary battery.
  • the secondary battery is a lithium-ion secondary battery.
  • a lithium-ion secondary battery utilizes the embedding and de-embedding of lithium ions in electrodes and the transmission in electrolytes to achieve the charging and discharging process.
  • the active ions in a lithium-ion secondary battery are lithium ions, but are not limited thereto.
  • the positive electrode active material may be a positive electrode active material for a battery known in the art.
  • the positive electrode active material may include one or more of the following materials or substances: lithium-containing phosphates of an olivine structure, lithium transition metal oxides, and their respective modified compounds.
  • the present application is not limited to these materials or substances, and other traditional materials or substances that can be used as positive electrode active materials for batteries may also be used.
  • These positive electrode active materials may be used alone or in combination of two or more.
  • lithium transition metal oxides may include, but are not limited to, one or more of lithium cobalt oxide, lithium nickel oxide, lithium manganese oxide, lithium nickel cobalt oxide, lithium manganese cobalt oxide, lithium nickel manganese oxide, lithium nickel cobalt manganese oxide, lithium nickel cobalt aluminum oxide, and their modified compounds.
  • Non-limiting examples of lithium cobalt oxides include LiCoO2 ; non-limiting examples of lithium nickel oxides include LiNiO2 ; non-limiting examples of lithium manganese oxides include LiMnO2 , LiMn2O4 , etc .; non-limiting examples of lithium nickel cobalt manganese oxides include LiNi1 / 3Co1 / 3Mn1 / 3O2 (also referred to as NCM333 ), LiNi0.5Co0.2Mn0.3O2 (also referred to as NCM523 ) , LiNi0.5Co0.25Mn0.25O2 (also referred to as NCM211 ) , LiNi0.6Co0.2Mn0.2O2 (also referred to as NCM622 ) , LiNi0.8Co0.1Mn0.1O2 (also referred to as NCM811 ) , etc.
  • Non-limiting examples of lithium nickel cobalt aluminum oxide include LiNi 0.85 Co 0.15 Al 0.05 O 2 .
  • Non-limiting examples of lithium phosphates with an olivine structure may include, but are not limited to, one or more of lithium iron phosphate, a composite material of lithium iron phosphate and carbon, lithium manganese phosphate, a composite material of lithium manganese phosphate and carbon, lithium iron manganese phosphate, and a composite material of lithium iron manganese phosphate and carbon.
  • Non-limiting examples of lithium iron phosphate include LiFePO 4 (also referred to as LFP); non-limiting examples of lithium manganese phosphate include LiMnPO 4 .
  • the positive electrode active material may include but is not limited to one or more of the following materials: lithium iron phosphate, lithium iron manganese phosphate, lithium cobalt oxide, lithium nickel oxide, lithium manganese oxide, lithium nickel manganese oxide, lithium nickel cobalt manganese oxide, lithium nickel cobalt aluminum oxide, sodium oxide and potassium oxide, and materials consisting of any of the foregoing substances and doping elements; further, the doping elements in any one of the positive electrode active materials independently include one or more of transition metal elements and non-transition metal elements.
  • the positive electrode film layer may also optionally include a binder.
  • the binder may include one or more of polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), vinylidene fluoride-tetrafluoroethylene-propylene terpolymer, vinylidene fluoride-hexafluoropropylene-tetrafluoroethylene terpolymer, tetrafluoroethylene-hexafluoropropylene copolymer, and fluorine-containing acrylate resin.
  • PVDF polyvinylidene fluoride
  • PTFE polytetrafluoroethylene
  • PTFE polytetrafluoroethylene
  • vinylidene fluoride-tetrafluoroethylene-propylene terpolymer vinylidene fluoride-hexafluoropropylene-tetrafluoroethylene terpolymer
  • the positive electrode film layer may further include a conductive agent.
  • the conductive agent may include one or more of superconducting carbon, acetylene black, carbon black, Ketjen black, carbon dots, carbon nanotubes, graphene, and carbon nanofibers.
  • the positive electrode sheet can be prepared by the following method: the components for preparing the positive electrode sheet, such as the positive electrode active material, the conductive agent, the binder and any other components are dispersed in a solvent to form a positive electrode slurry; the positive electrode slurry is coated on at least one side of the positive electrode collector, and after drying, compaction (compacting can be performed by cold pressing), etc., the positive electrode sheet can be obtained.
  • the type of solvent can include but is not limited to any one of the aforementioned embodiments, such as N-methylpyrrolidone (NMP).
  • NMP N-methylpyrrolidone
  • the surface of the positive electrode collector coated with the positive electrode slurry can be on a single surface of the positive electrode collector or on both surfaces of the positive electrode collector.
  • the solid content of the positive electrode slurry can be 40wt% to 80wt%.
  • the compacted density of the positive electrode sheet can be 3.0 to 3.6g/ cm3 , and can be optionally 3.3 to 3.5
  • the electrolyte has the function of conducting active ions between the positive electrode sheet and the negative electrode sheet.
  • the electrolyte in the present application includes an electrolyte solution.
  • the electrolyte is a non-aqueous electrolyte.
  • the non-aqueous electrolyte may include an electrolyte salt and a solvent.
  • the electrolyte salt may include an electrolyte lithium salt.
  • the electrolyte lithium salt may include one or more of lithium hexafluorophosphate (LiPF 6 ), lithium tetrafluoroborate (LiBF 4 ), lithium perchlorate (LiClO 4 ), lithium hexafluoroarsenate, lithium bisfluorosulfonyl imide (LiFSI), lithium bistrifluoromethanesulfonyl imide (LiTFSI), lithium trifluoromethanesulfonate, lithium difluorophosphate, lithium difluorooxalatoborate, lithium dioxalatoborate, lithium difluorodioxalatophosphate, and lithium tetrafluorooxalatophosphate.
  • LiPF 6 lithium hexafluorophosphate
  • LiBF 4 lithium tetrafluoroborate
  • LiClO 4 lithium perchlorate
  • LiClO 4 lithium hexafluoroarsenate
  • LiFSI lithium bis
  • the solvent is an organic solvent.
  • the solvent in the non-aqueous electrolyte includes a chain carboxylic acid ester (referred to as a first solvent).
  • a first solvent a chain carboxylic acid ester
  • the solvent in addition to the first solvent, may also include one or more of an ether solvent and a carbonate solvent.
  • the carbonate solvent may include one or more of carbonates and halogenated carbonates, such as ethylene carbonate (EC), propylene carbonate (PC), ethyl methyl carbonate (EMC), diethyl carbonate (DEC), dimethyl carbonate (DMC), and propylene carbonate (PC).
  • EC ethylene carbonate
  • PC propylene carbonate
  • EMC ethyl methyl carbonate
  • DEC diethyl carbonate
  • DMC dimethyl carbonate
  • PC propylene carbonate
  • PC propylene carbonate
  • DMC dipropyl carbonate
  • MPC methylpropyl carbonate
  • EPC ethylpropyl carbonate
  • the solvent in addition to the first solvent, may also include one or more of ethylene carbonate (EC), propylene carbonate (PC), ethyl methyl carbonate (EMC), diethyl carbonate (DEC), dimethyl carbonate (DMC), dipropyl carbonate (DPC), methyl propyl carbonate, ethyl propyl carbonate, butylene carbonate, fluoroethylene carbonate, 1,4-butyrolactone, cyclopentane sulfone, dimethyl sulfone, ethyl methyl sulfone and diethyl sulfone.
  • EC ethylene carbonate
  • PC propylene carbonate
  • EMC ethyl methyl carbonate
  • DMC diethyl carbonate
  • DPC dipropyl carbonate
  • methyl propyl carbonate ethyl propyl carbonate
  • butylene carbonate fluoroethylene carbonate
  • 1,4-butyrolactone 1,4-butyrolact
  • the solvent includes one or more of ethylene carbonate (EC) and ethyl methyl carbonate (EMC) in addition to the first solvent.
  • the solvent includes ethylene carbonate.
  • the solvent includes ethyl methyl carbonate.
  • the solvent includes ethylene carbonate and ethyl methyl carbonate, and further, the volume ratio of ethylene carbonate and ethyl methyl carbonate can be 3:7, but is not limited thereto.
  • the solvent is a combination of the first solvent, ethylene carbonate, and ethyl methyl carbonate.
  • the electrolyte may further include additives, such as negative electrode film-forming additives, positive electrode film-forming additives, and additives that can improve certain battery properties, such as additives that improve battery overcharge performance, additives that improve battery high or low temperature performance, etc.
  • additives such as negative electrode film-forming additives, positive electrode film-forming additives, and additives that can improve certain battery properties, such as additives that improve battery overcharge performance, additives that improve battery high or low temperature performance, etc.
  • the additive may include one or more of vinylene carbonate (VC), vinyl ethylene carbonate (VEC), fluoroethylene carbonate (FEC), difluoroethylene carbonate (DFEC), trifluoromethylethylene carbonate (TFPC), methylene methanedisulfonate (MMDS), 1-propylene-1,3-sultone (PST), vinyl sulfite (ES), propylene sulfite (PS), vinyl sulfate (DTD), succinonitrile (SN), adiponitrile (AND), sulfonate cyclic quaternary ammonium salt, tris(trimethylsilyl) phosphate (TMSP), tris(trimethylsilyl) borate (TMSB) and anisole.
  • VC vinylene carbonate
  • VEC vinyl ethylene carbonate
  • FEC fluoroethylene carbonate
  • DFEC difluoroethylene carbonate
  • TFPC trifluoromethylethylene carbonate
  • MMDS methylene methane
  • the additive includes one or more of a first additive and a second additive.
  • the additive includes a first additive.
  • the additive includes a second additive.
  • the additive includes a first additive and a second additive.
  • first additive and the second additive are as described above, including but not limited to the types and amounts.
  • the secondary battery further includes a separator.
  • the present application has no particular limitation on the type of separator, and any known porous separator with good chemical stability and mechanical stability can be selected.
  • the material of the isolation membrane may include one or more of glass fiber, non-woven fabric, polyethylene, polypropylene and polyvinylidene fluoride.
  • the isolation membrane may be a single-layer film or a multi-layer composite film, without particular limitation.
  • the materials of each layer may be the same or different, without particular limitation.
  • Electrode assembly electrochemical energy storage device, secondary battery
  • the positive electrode sheet, the negative electrode sheet, and the separator may be formed into an electrode assembly by a winding process or a lamination process.
  • the electrochemical energy storage device may include an outer package, which may be used to encapsulate the electrode assembly and the electrolyte.
  • the secondary battery may include an outer package, which may be used to encapsulate the electrode assembly and the electrolyte.
  • the outer packaging of the secondary battery may be a hard shell, such as a hard plastic shell, an aluminum shell, a steel shell, etc.
  • the outer packaging of the secondary battery may also be a soft package, such as a bag-type soft package.
  • the material of the soft package may be plastic, and further, non-limiting examples of plastic may include one or more of polypropylene, polybutylene terephthalate, and polybutylene succinate.
  • FIG1 is a secondary battery 5 of a square structure as an example.
  • the outer package may include a shell 51 and a cover plate 53.
  • the shell 51 may include a bottom plate and a side plate connected to the bottom plate, and the bottom plate and the side plate enclose a receiving cavity.
  • the shell 51 has an opening connected to the receiving cavity, and the cover plate 53 can be covered on the opening to close the receiving cavity.
  • the positive electrode sheet, the negative electrode sheet and the isolation film can form an electrode assembly 52 through a winding process or a lamination process.
  • the electrode assembly 52 is encapsulated in the receiving cavity.
  • the electrolyte is infiltrated in the electrode assembly 52.
  • the number of electrode assemblies 52 contained in the secondary battery 5 can be one or more, and those skilled in the art can select according to actual needs.
  • the secondary battery has one or more of the following effects:
  • Fast charging time fast charging time ⁇ 35min, further can be ⁇ 33min, further can be ⁇ 32min, further can be ⁇ 30min, further can be ⁇ 28min;
  • Negative electrode sheet expansion When cycled at 45°C to 80% SOH, the negative electrode sheet expansion rate is ⁇ 36%, further ⁇ 35.5%, further ⁇ 33%, further ⁇ 32%, further ⁇ 30%, further ⁇ 258%;
  • Cycle performance The number of cycles at 45°C to 80% SOH is ⁇ 800, further ⁇ 900, further ⁇ 950, further ⁇ 1000, further ⁇ 1100, further ⁇ 1150, further ⁇ 1200;
  • Gas production performance The expansion rate of 30D battery cells stored at 60°C is ⁇ 9%, further ⁇ 8%, further ⁇ 7.5%, further ⁇ 7%.
  • the secondary battery has excellent storage performance based on the comprehensive performance of excellent fast charging capability, cycle performance and safety performance.
  • the capacity retention rate of 30D storage at 60°C is ⁇ 85%, further ⁇ 88%, further ⁇ 90%, and further ⁇ 95%.
  • the fast charging time is ⁇ 35min
  • the expansion rate of the negative electrode plate when cycled at 45°C to 80% SOH is ⁇ 33%
  • the number of cycles corresponding to the cycle at 45°C to 80% SOH is ⁇ 900
  • the expansion rate of the battery cell when stored at 60°C for 30D is ⁇ 8%
  • the capacity retention rate when stored at 60°C for 30D is ⁇ 88%.
  • the fast charging time is ⁇ 33min
  • the expansion rate of the negative electrode plate when cycled at 45°C to 80% SOH is ⁇ 32%
  • the number of cycles corresponding to the cycle at 45°C to 80% SOH is ⁇ 1000
  • the expansion rate of the battery cell when stored at 60°C for 30D is ⁇ 8%
  • the capacity retention rate when stored at 60°C for 30D is ⁇ 90%.
  • the fast charging time is ⁇ 30min
  • the expansion rate of the negative electrode plate when cycled at 45°C to 80% SOH is ⁇ 30%
  • the number of cycles corresponding to the cycle at 45°C to 80% SOH is ⁇ 950
  • the expansion rate of the battery cell when stored at 60°C for 30D is ⁇ 8%
  • the capacity retention rate when stored at 60°C for 30D is ⁇ 90%.
  • the fast charging time is ⁇ 35min
  • the expansion rate of the negative electrode plate when cycled at 45°C to 80% SOH is ⁇ 32%
  • the number of cycles corresponding to the cycle at 45°C to 80% SOH is ⁇ 900
  • the expansion rate of the battery cell when stored at 60°C for 30D is ⁇ 7%
  • the capacity retention rate when stored at 60°C for 30D is ⁇ 88%.
  • the fast charging time is ⁇ 30min
  • the expansion rate of the negative electrode plate when cycled at 45°C to 80% SOH is ⁇ 30%
  • the number of cycles corresponding to the cycle at 45°C to 80% SOH is ⁇ 1000
  • the expansion rate of the battery cell when stored at 60°C for 30D is ⁇ 7%
  • the capacity retention rate when stored at 60°C for 30D is ⁇ 90%.
  • the fast charging time is ⁇ 32 min
  • the expansion rate of the negative electrode plate when cycled at 45°C to 80% SOH is ⁇ 33%
  • the number of cycles corresponding to the cycle at 45°C to 80% SOH is ⁇ 1100
  • the expansion rate of the battery cell when stored at 60°C for 30D is ⁇ 7.5%
  • the capacity retention rate when stored at 60°C for 30D is ⁇ 90%.
  • the fast charging time is ⁇ 28min
  • the expansion rate of the negative electrode plate when cycled at 45°C to 80% SOH is ⁇ 28%
  • the number of cycles corresponding to the cycle at 45°C to 80% SOH is ⁇ 1200
  • the expansion rate of the battery cell when stored at 60°C for 30D is ⁇ 7.5%
  • the capacity retention rate when stored at 60°C for 30D is ⁇ 95%.
  • the present application provides an electrical device, which includes the secondary battery described in the first aspect of the present application.
  • the secondary battery can be used as a power source for the electrical device, or as an energy storage unit for the electrical device.
  • the electrical device may include mobile devices, electric vehicles, electric trains, ships and satellites, energy storage systems, etc., but are not limited thereto.
  • the mobile device may be, for example, a mobile phone, a laptop computer, etc.;
  • the electric vehicle may be, for example, a pure electric vehicle, a hybrid electric vehicle, a plug-in hybrid electric vehicle, an electric bicycle, an electric scooter, an electric golf cart, an electric truck, etc., but are not limited thereto.
  • a secondary battery can be selected according to its usage requirements.
  • Fig. 3 is an example of an electric device 6.
  • the electric device is a pure electric vehicle, a hybrid electric vehicle, or a plug-in hybrid electric vehicle, etc.
  • a battery pack or a battery module may be used.
  • a device may be a mobile phone, a tablet computer, a notebook computer, etc. Such a device is usually required to be thin and light, and a secondary battery may be used as a power source.
  • Type of negative electrode active material The negative electrode active material having a certain volume average particle size D v 50 and BET specific surface area is selected according to Table 1.
  • negative electrode active material raw material it can also be the negative electrode active material sampled from the negative electrode active material layer of the negative electrode sheet.
  • the washed and wetted sample is taken for dispersion test.
  • Particle size type Test for volume average particle size D v 50.
  • Test process Take an appropriate amount of the sample to be tested (the sample concentration can meet the shading degree of 8% to 12%), add 20mL of anhydrous ethanol, and ultrasonically treat for 5 minutes (53KHz/120W) to completely disperse the sample. Then, measure the sample according to GB/T19077-2016/ISO 13320:2009 standard.
  • negative electrode active material raw material it can also be the negative electrode active material sampled from the negative electrode active material layer of the negative electrode sheet.
  • Test method The nitrogen adsorption specific surface area analysis test method was used and the result was calculated using the BET (Brunauer Emmett Teller) method.
  • the nitrogen adsorption specific surface area analysis test can be performed using the Tri Star II specific surface and pore analyzer from Micromeritics, USA. The test steps can refer to GB/T 19587-2004.
  • the detailed steps are as follows: dry the sample to be tested in a vacuum drying oven at 200°C for 2 hours; then use argon as the adsorption gas, and use a specific surface and pore analyzer to map the adsorption-desorption curve with a relative pressure P / P0 of 0 to 0.99, where P is the equilibrium adsorption pressure and P0 is the saturated vapor pressure, and the specific surface area of the negative electrode active material is calculated by the BET method.
  • the negative electrode active material artificial graphite, conductive agent carbon black, binder styrene butadiene rubber (SBR), and thickener sodium carboxymethyl cellulose (CMC-Na) are dissolved in solvent deionized water at a weight ratio of 90:4:4:2, and mixed evenly to prepare a negative electrode slurry (solid content of 48%); the negative electrode slurry is evenly coated on the double-side surface of the negative electrode current collector copper foil once or multiple times, and the negative electrode sheet is obtained after drying, cold pressing, and slitting.
  • the compaction density of the negative electrode sheet is 1.65g/ cm3 .
  • the OI value of the negative electrode sheet is regulated by at least one parameter selected from the group consisting of the OI value of the graphite particles, the D v 50 of the graphite particles, the porosity of the negative electrode sheet, the compaction density of the negative electrode sheet, the type and content of the components of the negative electrode sheet, and the like.
  • Test of the OI value of the negative electrode sheet an X-ray powder diffractometer (X'pert PRO) was used to test the intensities of the 004 crystal plane diffraction peak and the 110 crystal plane diffraction peak.
  • X'pert PRO X-ray powder diffractometer
  • Test of negative electrode sheet resistance R Use BER1300 multi-function electrode sheet resistance meter for testing. First, cut the negative electrode sheet into a sample of a certain size (a small disc with a diameter of 40mm); place the sample between two probes and record the test results. Take multiple ( ⁇ 5) samples to be tested and calculate the average value of the multiple samples to be tested as the test result.
  • LiPF6 lithium hexafluorophosphate
  • Lithium iron phosphate positive electrode material, conductive agent acetylene black, and binder polyvinylidene fluoride (PVDF) are added to solvent N-methylpyrrolidone (NMP) in a weight ratio of 90:5:5, and the mixture is stirred and mixed to obtain positive electrode slurry (solid content is 67%); the positive electrode slurry is then evenly coated on both sides of the positive electrode current collector, and the coating weight on one side is about 22.7 mg/ cm2 (such as 350 mg/1540.25 mm2 ); and then dried, cold pressed, and cut to obtain positive electrode sheets.
  • NMP solvent N-methylpyrrolidone
  • a conventional commercially available polypropylene film was used as the isolation film.
  • the positive electrode sheet (width 87mm ⁇ length 605mm), the separator (width 98mm ⁇ length 1896mm), and the negative electrode sheet (width 93mm ⁇ length 735mm) are stacked in order, so that the separator is between the positive and negative electrode sheets to play an isolating role, and then wound to obtain an electrode assembly; the electrode assembly is placed in a battery casing, and after drying, 12.0g of electrolyte (3Ah, injection coefficient 4.0g/Ah) is injected, and then a lithium-ion battery is obtained through processes such as formation and standing.
  • electrolyte 3Ah, injection coefficient 4.0g/Ah
  • Examples 2 to 41 and Comparative Examples 1-9 adopt the same method as Example 1, except that one or more parameters of the type of negative electrode active material, negative electrode OI value, resistance value R of the negative electrode plate, type and amount of the first solvent (chain carboxylic acid ester), type and amount of the first additive, type and amount of the second additive, D v 50 and specific surface area (BET) of the negative electrode active material can be found in Tables 1 and 2.
  • W0 is the mass proportion of the first solvent in the electrolyte solvent.
  • W1 is the mass proportion of the first additive in the electrolyte (non-aqueous electrolyte); W2 is the mass proportion of the second additive in the electrolyte (non-aqueous electrolyte).
  • the divided battery was subjected to 2.5V ⁇ 3.65V charge and discharge test.
  • the test steps are: first 3C constant current charge to 30% SOC, 2C constant current charge to 60% SOC, 1C constant current constant voltage charge to 80% SOC, cut-off current is 0.01C, stand for 5 minutes; 1C constant current discharge to 2.0V, stand for 5 minutes. Determine the time it takes for the battery to charge to 80% SOC.
  • SOC represents the remaining capacity of the battery, and its value range is 0-100%.
  • the lithium-ion battery is charged to 3.65V at a constant current of 0.5C, then charged at a constant voltage of 3.65 until the current is less than 0.05C, and then the lithium-ion battery is discharged to 2.5V at a constant current of 0.5C.
  • This is a charge and discharge process (i.e., 1 cycle).
  • the lithium-ion secondary battery is charged to 3.65V at a constant current of 0.33C, and then charged to a current of 0.05C at a constant voltage of 3.65V to fully charge the lithium-ion battery.
  • the volume of the battery is tested by the water displacement method, and the volume at this time is recorded as the volume before storage.
  • the lithium-ion battery is then stored at 60°C for 30 days. After the storage is completed, the lithium-ion secondary battery is placed in an environment of 25°C and the volume of the battery is tested by the water displacement method, and the volume at this time is recorded as the volume after storage.
  • the volume expansion rate of the battery is calculated according to the following formula:
  • Battery volume expansion rate (volume after storage/volume before storage-1) ⁇ 100%.
  • the lithium-ion battery is charged to 3.65V at a constant current of 0.33C, then charged at a constant voltage of 3.65 until the current is less than 0.05C, and then the lithium-ion battery is discharged to 2.5V at a constant current of 0.33C (the battery discharge capacity is recorded as C0).
  • the secondary batteries prepared in Examples 1 to 41 have achieved excellent comprehensive performance in terms of fast charging capability, low negative electrode plate expansion, and battery cycle performance.
  • the battery cell expansion rate in the high-temperature gas production test also reflects the gas production performance, which can be referred to the fast charging time, the expansion rate of the negative electrode plate when cycled to 80% SOH at 45°C, the number of cycles corresponding to the cycle to 80% SOH at 45°C, and the battery cell expansion rate data stored at 60°C for 30D.
  • the secondary batteries prepared in Examples 1 to 41 also have excellent storage performance (refer to the capacity retention rate stored at 60°C for 30D). rate data).
  • the W0 ⁇ 100/(R ⁇ OI) of Comparative Examples 1 to 9 is either less than 0.08 or greater than 5, resulting in that the comprehensive performance of the secondary battery in terms of fast charging capability, cycle performance and safety performance is significantly inferior to that of Examples 1 to 41.
  • Comparative Example 6 the OI value is slightly large, but W0 ⁇ 100/(R ⁇ OI) is too small; in Comparative Example 7, the negative electrode sheet resistance R value is slightly low, but W0 ⁇ 100/(R ⁇ OI) is too large; in Comparative Example 8, the R value is slightly high, but W0 ⁇ 100/(R ⁇ OI) is too small; in Comparative Example 9, the content of chain carboxylic acid ester (first solvent) is slightly high, but W0 ⁇ 100/(R ⁇ OI) is too large. As a result, Comparative Examples 6-9 failed to achieve excellent comprehensive effects in terms of fast charging capability, cycle performance and safety performance.
  • Comparative Examples 7 and 9 have shorter fast charging times, the cost is increased electrode expansion, significantly deteriorated cycle performance, significantly increased cell expansion after high-temperature gas production, and poor storage performance.
  • the present application is not limited to the above-mentioned embodiments.
  • the above-mentioned embodiments are only examples.
  • the embodiments that have the same structure as the technical idea and play the same effect are all included in the technical scope of the present application.
  • the above-mentioned embodiments only express several embodiments of the present application, and the description is relatively detailed, but it cannot be understood as a limitation on the scope of the patent.
  • various deformations that can be thought of by those skilled in the art are applied to the embodiments, and other methods of combining some of the constituent elements in the embodiments are also included in the scope of the present application.

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Abstract

本申请提供了一种二次电池，其中的负极活性物质包括石墨材料，其中的非水电解质包括链状羧酸酯；负极极片的OI值、负极极片的电阻值R与第一溶剂在溶剂中的质量占比W0满足0.08/mΩ≤W0×100/(R×OI)≤5/mΩ；其中，OI值指石墨材料004晶面与110晶面衍射峰强度的比值，R的单位为mΩ。

Description

二次电池和用电装置 技术领域
本申请涉及二次电池技术领域，特别涉及二次电池和用电装置。
背景技术
这里的陈述仅提供与本申请有关的背景信息，而不必然构成现有技术。
随着二次电池技术的发展，二次电池被广泛应用于水力、火力、风力和太阳能电站等储能电源系统，还被应用于电子设备电源、电动工具、电动自行车、电动摩托车、电动汽车、军事装备、航空航天等多个领域。随着科技和社会的发展，对二次电池的快充性能、循环性能、安全性能等方面提出了更高的综合性要求。
因此，目前有必要开发能够兼顾快充性能、循环性能和安全性能的二次电池新技术。
发明内容
鉴于上述问题，本申请提供了一种二次电池和用电装置，该二次电池包括合理搭配的负极极片及非水电解质，在快充性能、循环性能和安全性能方面具有优良的综合性功能。
第一方面，本申请提供了一种二次电池，其包括正极极片、负极极片和非水电解质；其中，所述负极极片包括负极活性材料层，所述负极活性材料层包括负极活性物质，所述负极活性物质包括石墨材料；所述非水电解质包括溶剂，所述溶剂包括第一溶剂，所述第一溶剂为链状羧酸酯；
所述负极极片的OI值、所述负极极片的电阻值R与所述第一溶剂在所述溶剂中的质量占比W0满足如下关系：0.08/mΩ≤W0×100/(R×OI)≤5/mΩ；
其中，所述负极极片的OI值是指所述石墨材料的004晶面衍射峰强度与110晶面衍射峰强度的比值；R的单位为mΩ。
负极极片的OI值反映了负极活性材料层中晶粒排列方向的各向异性程度，通过协同控制负极极片的OI值、负极极片的电阻值R与链状羧酸酯溶剂在溶剂中的质量占比W0，可以兼顾二次电池的快充性能、循环性能和安全性能。当OI值、R与W0满足上述关系时，一方面，非水电解质中的链状羧酸酯具有低黏度和导电性的特点，可以显著增强电池的电导率，还能改善电池的低温性能和循环稳定性，再一方面，负极极片具有合适的取向度，在活性离子(如锂离子)嵌入过程中具有合适的方向选择性，能够把活性离子嵌入膨胀(如嵌锂膨胀)分散到不同方向，从而降低极片和电芯的循环膨胀，可以有效缓解由于链状羧酸酯与负极的界面稳定性差而导致的极片自身膨胀被加剧的问题，提升电池安全性，还可以降低活性离子在负极极片传输过程中的浓差极化，与负极极片电阻值R搭配实现大幅度提升电池快充能力。因此，通过协同控制OI值、R与W0，能够使二次电池在快充性能、循环性能和安全性能方面具有优良的综合性功能，可以兼顾较短的快充时间，较低的循环膨胀以及较高的循环容量保持率。
在一些实施方式中，6≤OI≤25；可选地，6≤OI≤18；进一步可选地，12≤OI≤18。
通过调节QI值在较为合适的范围内，更有利于降低在活性离子嵌入过程中的方向选择性，从而更好地活性离子嵌入膨胀分散到不同方向；此外，还可以更好地提高负极极片的活性离子传输性能。
在一些实施方式中，1mΩ≤R≤50mΩ；可选地，5mΩ≤R≤30mΩ；进一步可选地，10mΩ≤R≤20mΩ。
通过将负极极片的电阻值R控制在一定的范围内，可以将W0×100/(R×OI)控制在更为合适的范围内，从而在较短的快充时间，较低的循环膨胀以及较高的循环容量保持率方面实现更好的综合效果，并更有利于提高负极极片的活性离子传输性能和电子传导性能。
在一些实施方式中，10％≤W0≤80％；
可选地，20％≤W0≤80％；进一步可选地，30％≤W0≤70％；更进一步可选地，50％≤W0≤70％；
另可选地，10％≤W0≤60％；进一步可选地，20％≤W0≤60％。
通过将第一溶剂在溶剂中的含量W0控制在一定的范围内，可以在兼顾二次电池的快充性能、循环性能和安全性能的基础上，更有利于增强电池的电导率，还可更有利于改善二次善电池的低温性能和循环稳定性。
在一些实施方式中，0.67≤W0×100/OI≤10；
可选地，1≤W0×100/OI≤10；进一步可选地，1≤W0×100/OI≤5；更进一步可选地，3≤W0×100/OI≤5；
另可选地，0.67≤W0×100/OI≤4；进一步可选地，1≤W0×100/OI≤4。
在控制W0×100/(R×OI)符合前述关系的基础上，通过W0×100/OI进一步调控非水电解质中链状羧酸酯与负极活性材料层中晶粒排列方向的搭配情况，更易实现快充性能、循环性能和安全性能综合性能的提升。
在一些实施方式中，0.1/mΩ≤W0×100/(R×OI)≤5/mΩ；可选地，0.1/mΩ≤W0×100/(R×OI)≤2/mΩ。
进一步控制W0×100/(R×OI)控制在上述范围内，对于整体性地综合改善快充性能、循环性能和安全性能更为有利。
在一些实施方式中，所述二次电池满足如下特征组合：6≤OI≤18，10mΩ≤R≤20mΩ，且20％≤W0≤80％；
可选地，12≤OI≤18，10mΩ≤R≤20mΩ，且10％≤W0≤60％；进一步可选地，20％≤W0≤60％；
另可选地，12≤OI≤18，10mΩ≤R≤20mΩ，且50％≤W0≤70％。
通过精细地协同控制负极极片的OI值为12～18、负极极片的电阻值R为10mΩ～20mΩ和链状羧酸酯溶剂在溶剂中的质量占比W0为20％～80％(进一步可选为10％～60％)，可以更好地实现快充性能、循环性能和安全性能的兼顾，更有利于使二次电池同时具有较优快充能力，较低的循环膨胀以及较高的循环容量保持率。
通过控制不同参数的取值情况，还可以进一步在某个或某些方面更具优势。比如，12≤OI≤18，10mΩ≤R≤20mΩ，且20％≤W0≤60％的情形中，可以在较优综合性能基础上还具有显著优异的低循环膨胀和循环性能。再比如，12≤OI≤18，10mΩ≤R≤20mΩ，且50％≤W0≤70％的情形中，在较优综合性能基础上，还可以在较短的快充时间和较低的循环膨胀方面具有明显优势。
在一些实施方式中，所述第一溶剂包括结构如式(1)所示的化合物：
其中，R1和R2分别独立地为C1-3烷基或C1-3卤代烷基；
可选地，R1和R2分别独立地为C1-3烷基或C1-3氟代烷基；
进一步可选地，R1和R2分别独立地为甲基、乙基、丙基、氟代甲基、氟代乙基和氟代丙基中的一种；
更进一步可选地，R1和R2分别独立地为甲基、乙基、氟代甲基和氟代乙基中的一种；
更进一步可选地，所述第一溶剂包括下述化合物中的一种或多种：乙酸甲酯、乙酸乙酯、二氟乙酸甲酯和二氟乙酸乙酯。
可以选择分子尺寸较小的第一溶剂，此时，第一溶剂粘度较低，有利于二次电池获得更好的快充性能。
在一些实施方式中，所述非水电解质还包括第一添加剂；所述第一添加剂为二异氰酸酯。
在一些实施方式中，所述第一添加剂包括结构如下的化合物：
其中，R3为未取代的或Ra取代的C1-18亚烃基；Ra包括下述取代基中的一种或多种：卤素原子、-CN、-NCO、-OH、-COOH、-SOOH、-OC(＝O)R11、R12OC(＝O)-、C1-10烷基、C2-10烯基、C2- 10炔基和C2-10氧杂烷基中的一种或多种；R11和R12分别独立地为烷基或卤代烷基；
可选地，R3为C2-10亚烷基、C2-10杂亚烷基、C6-18亚芳基、C2-18杂亚芳基、C3-18亚脂环基或C3-18杂亚脂环基，前述任一种基团为未取代的或者为Ra取代的；
另可选地，R3为未取代的或Ra取代的C2-10亚烷基、未取代的或Ra取代的C3-18二价环烷基或未取代的或Ra取代的C6-18亚芳基；进一步可选地，R3为C2-10亚烷基、C6-18二价环烷基或C6- 18亚芳基；更进一步可选地，R3为C4-10亚烷基、C6-14二价环烷基或C6-14亚芳基；更进一步可选地，R3为C4-10亚烷基、C6-10二价环烷基或C6-10亚芳基；更进一步可选地，R3为C4-8亚己基、含有己环的C6-10二价环烷基或含有苯环的C6-10亚芳基；
另可选地，所述第一添加剂包括下述化合物中的一种或多种：六亚甲基二异氰酸酯、1,4-环己烷二甲基二异氰酸酯、1,3-苯二异氰酸酯和2,4-二异氰酸-1-甲苯。
在一些实施方式中，所述第一添加剂在所述非水电解质中的质量占比为0～11％；
可选地，所述第一添加剂在所述非水电解质中的质量占比为0.005％～11％；
进一步可选地，所述第一添加剂在所述非水电解质中的质量占比为0.005％～10％；
更进一步可选地，所述第一添加剂在所述非水电解质中的质量占比为0.01％～10％；
更进一步可选地，所述第一添加剂在所述非水电解质中的质量占比为0.1％～5％；
更进一步可选地，所述第一添加剂在所述非水电解质中的质量占比为1％～5％。
链状羧酸酯(第一溶剂)的引入有利于提高电池的快充能力，然而，由于羧酸酯与负极极片的兼容性因素，如果其用量W0与负极极片的OI值、电阻值R之间的匹配性不佳，可能会加重负极极片自身存在的膨胀问题，也可能影响界面存在的产气问题，还可能造成电芯容量的衰减及电池循环性能的恶化。通过向非水电解质中引入第一添加剂，可以在负极极片表面形成具有保护作用的固体电解质界面(SEI)层，该保护层可以协助活性离子嵌入到负极极片的负极活性材料层中，使得负极极片的活性离子嵌入膨胀效应能够被均匀地传导到各个方向，从而减少负极极片的循环膨胀率。此外，第一添加剂还能显著提升电解液和负极极片界面的稳定性，可以降低二次电池循环过程中电解液的消耗和负极结构的破坏，从而显著改善二次电池的循环性能。
在一些实施方式中，所述非水电解质还包括第二添加剂；所述第二添加剂包括单氟磷酸锂、二氟磷酸锂、四氟硼酸锂、式(3)所示化合物和氟磺酸盐中的一种或多种；
式(3)中，a、b和c各自独立地为正整数，m为选自1-3的整数，n为选自0-4的整数，q为0或1；Ma+为带有a价正电荷的金属离子；任一个Y独立地为硼原子或磷原子；X为卤素原子；任一个R独立地为取代或未取代的C1-10亚烷基、取代或未取代的C1-10卤代亚烷基、取代或未取代的C6-20亚芳基、以及取代或未取代的C6-20卤代亚芳基中的一种；
可选地，任一个R独立地为Rc取代或未取代的C1-10亚烷基、Rc取代或未取代的C1-10卤代亚烷基、Rc取代或未取代的C6-20亚芳基、以及Rc取代或未取代的C6-20卤代亚芳基中一种；Rc取代的C1-10亚烷基中的取代基、Rc取代的C1-10卤代亚烷基中的取代基、Rc取代的C6-20亚芳基中的取代基和Rc取代的C6-20卤代亚芳基中的Rc取代基可以各自独立地包括下述取代基中的一种或多种：卤素原子、-CN、-NCO、-OH、-COOH、-SOOH、-OC＝(O)R41、-C＝(O)OR42、C1-10烷基、C2-10烯基、C2-10炔基和C2-10烷氧基；其中，R41和R42各自独立地为C1-6烷基；
可选地，在所述非水电解质中，Ma+中的M包括Li、Na、K、Rb、Cs、Mg、Ca、Ba、Al、Fe、Cu和Ni中的一种或多种；
可选地，a、b和c各自独立地为选自1、2或3。
在一些实施方式中，所述第二添加剂包括二氟磷酸锂、单氟磷酸锂、四氟硼酸锂、氟磺酸锂和氟磺酸钠中的一种或多种。
在一些实施方式中，所述第二添加剂在所述非水电解质中的质量占比为0.005％～11％；
可选地，所述第二添加剂在所述非水电解质中的质量占比为0.005％～11％；
进一步所述第二添加剂在所述非水电解质中的质量占比为0.005％～10％；
更进一步可选地，所述第二添加剂在所述非水电解质中的质量占比为0.05％～5％。
通过向非水电解质中引入第二添加剂，可以在负极形成富含无机物的SEI膜，既能改善二次电池的快充性能，又能进一步改善二次电池的循环性能。
在一些实施方式中，所述负极活性物质的体积平均粒径Dv50≥6μm；其中，Dv50表示物质或材料的累计体积分布百分数达到50％时对应的粒径；
可选地，所述负极活性物质的体积平均粒径Dv50为6μm～20μm；
进一步可选地，所述负极活性物质的体积平均粒径Dv50为15μm～20μm。
通过控制负极活性物质的粒径具有相对较大的粒径，可以减少负极材料与电解液的接触面积，降低在负极表面与溶剂发生副反应的概率，则更有利于降低极片膨胀率，可更佳地改善电芯的循环性能。
在一些实施方式中，所述负极活性物质的BET比表面积为0.5m2/g～2.0m2/g；
可选地，所述负极活性物质的BET比表面积为0.8m2/g～1.5m2/g。
通过控制负极活性物质的粒径具有一定的比表面积，可以减少负极材料的表面积，进而减少负极材料与电解液接触面积，从而减少溶剂在负极表面发生副反应，更好地改善电芯的循环性能。
在一些实施方式中，所述石墨材料包括人造石墨和天然石墨中的一种或多种；可选地，所述石墨材料包括人造石墨。
在一些实施方式中，所述石墨材料在所述负极活性物质中的重量百分比≥50％；可选地，所述石墨材料在所述负极活性物质中的重量百分比≥80％；进一步可选地，所述石墨材料在所述负极活性物质中的重量百分比为100％。
在一些实施方式中，所述二次电池为锂离子二次电池。
第二方面，本申请提供了一种用电装置，其包括本申请第一方面所述二次电池。
本申请的一个或多个实施例的细节在下面的附图和描述中提出。本申请的其他特征、目的和优点将从说明书、附图以及权利要求书变得明显。
附图说明
为了更好地描述和说明这里公开的那些申请的实施例或示例，可以参考一幅或多幅附图。用于描述附图的附加细节或示例不应当被认为是对所公开的申请、目前描述的实施例或示例以及目前理解的这些申请的最佳模式中的任何一者的范围的限制。而且在全部附图中，用相同的附图标号表示相同的部件。在附图中：
图1是本申请一实施例的二次电池的示意图；
图2是图1所示的本申请一实施例的二次电池的分解图；
图3是本申请一实施例的二次电池用作电源的用电装置的示意图。
附图标记说明：
5，二次电池；51，壳体；52，电极组件；53，盖板；6，用电装置。
具体实施方式
以下，适当地参照附图详细说明公开了本申请的二次电池和用电装置的一些实施方式。但是会有省略不必要的详细说明的情况。例如，有省略对已众所周知的事项的详细说明、实际相同结构的重复说明的情况。这是为了避免以下的说明不必要地变得冗长，便于本领域技术人员的理解。此外，附图及以下说明是为了本领域技术人员充分理解本申请而提供的，并不旨在限定权利要求书所记载的主题。
本申请所公开的数值“范围”以下限和上限的形式来限定，给定范围是通过选定一个下限和一个上限进行限定的，选定的下限和上限限定了特别范围的边界。这种方式进行限定的范围可以是包括端值或不包括端值的，任一个端值可以独立地被包括或不被包括，并且可以进行任意地组合，即任何下限可以与任何上限组合形成一个范围。例如，如果针对特定参数列出了60-120和80-110的范围，理解为60-110和80-120的范围也是预料到的。此外，如果列出的最小范围值1和2，且如果还列出了最大范围值3，4和5，则下面的范围可全部预料到：1-3、1-4、1-5、2-3、2-4和2-5。在本申请中，除非有其他说明，数值范围“a-b”表示a到b之间的任意实数组合的缩略表示，其中a和b都是实数。例如数值范围“0-5”表示本申请中已经全部列出了“0-5”之间的全部实数，“0-5”只是这些数值组合的缩略表示。另外，当表述某个参数为≥2的整数，则相当于公开了该参数为例如整数2、3、4、5、6、7、8、9、10、11、12等。比如，当表述某个参数为选自“2-10”的整数，相当于列出了整数2、3、4、5、6、7、8、9和10。
如果没有特别的说明，本申请的所有实施方式以及可选实施方式可以相互组合形成新的技术方案。
如果没有特别的说明，本申请的所有步骤可以顺序进行，也可以随机进行，可以优选是顺序进行的。例如，所述方法包括步骤(a)和(b)，表示所述方法可包括顺序进行的步骤(a)和(b)，也可以包括顺序进行的步骤(b)和(a)。例如，所述提到所述方法还可包括步骤(c)，表示步骤(c)可以任意顺序加入到所述方法，例如，所述方法可以包括步骤(a)、(b)和(c)，也可包括步骤(a)、(c)和(b)，也可以包括步骤(c)、(a)和(b)等。
如果没有特别的说明，本申请所提到的“具有”、“包括”、“含有”和“包含”各自独立地可以表示开放式，也可以是封闭式。例如，所述“包括”和“包含”可以表示还可以包括或包含没有列出的其他成员或时序特征，也可以仅包括或包含列出的成员或时序特征。成员例如材料或组分、结构、元件、仪器等；时序特征的非限制性性举例如动作、动作发生的条件、时机、状态等。
如果没有特别的说明，在本申请中，术语“或”是包括性的。举例来说，短语“A或B”表示“A，B，或A和B两者”。进一步地，以下任一条件均满足条件“A或B”：A为真(或存在)并且B为假(或不存在)；A为假(或不存在)而B为真(或存在)；或A和B都为真(或存在)。
在本申请中，如无其他说明，A(如B)，表示B为A中的一种非限制性示例，可以理解A 不限于为B。
在本申请中，如无其他说明，“和/或”对应的特征或方案包括两个或两个以上相关所列项目中任一个项目，也包括相关所列项目的任意的和所有的组合，所述任意的和所有的组合包括任意的两个相关所列项目、任意的更多个相关所列项目、或者全部相关所列项目的组合。例如，“A和/或B”表示A、B以及“A与B的组合”构成的组。其中，“包含A和/或B”可以表示“包含A，包含B，以及包含A与B”，还可以表示“包含A，包含B，或者包含A与B”，可根据所在语句恰当理解。
本申请中涉及“多个”、“多种”等，如无特别限定，指在数量上大于2或等于2。例如，“一种或多种”表示一种或大于等于两种。可以理解，涉及“任意多个”项目时，指的是任意合适的多个项目的组合，也即以不相冲突且能够实施本申请的方式进行“任意多个”项目的组合。
本申请中所使用的“其组合”、“其任意组合”、“其任意组合方式”等中包括所列项目中任两个或任两个以上项目的所有合适的组合方式。
本申请中，“合适的组合方式”、“合适的方式”、“任意合适的方式”等中所述“合适”，以能够实施本申请的技术方案为准。
本申请中，“优选”、“更好”仅为描述效果更好的实施方式或实施例，应当理解，并不构成对本申请保护范围的限制。如果一个技术方案中出现多处“优选”，如无特别说明，且无矛盾之处或相互制约关系，则每项“优选”各自独立。
本申请中，“可选地”、“可选的”、“可选”，指可有可无，也即指选自“有”或“无”两种并列方案中的任一种。如果一个技术方案中出现多处“可选”，如无特别说明，且无矛盾之处或相互制约关系，则每项“可选”各自独立。
本申请中，“进一步”、“更进一步”、“特别”等用于描述目的，表示内容上的差异，但并不应理解为对本申请保护范围的限制。
本申请中，“第一方面”、“第二方面”等中，术语“第一”、“第二”等仅用于描述目的，不能理解为指示或暗示相对重要性或数量，也不能理解为隐含指明所指示的技术特征的重要性或数量。而且“第一”、“第二”等仅起到非穷举式的列举描述目的，应当理解并不构成对数量的封闭式限定。
在本申请中，涉及数据范围的单位，如果仅在右端点后带有单位，则表示左端点和右端点的单位是相同的。比如，3～5h或3-5h均表示左端点“3”和右端点“5”的单位都是h(小时)。
本申请实施例说明书中所提到的相关成分的重量不仅仅可以指代各组分的含量，也可以表示各组分间重量的比例关系，因此，只要是按照本申请实施例说明书相关组分的含量按比例放大或缩小均在本申请实施例说明书公开的范围之内。进一步地，本申请实施例说明书中所述的重量可以是μg、mg、g、kg等化工领域公知的质量单位。
随着科技和社会的发展，对二次电池的快充性能、循环性能、安全性能等方面提出了更高的综合性要求。其中，电解液对二次电池上述综合性能的实现具有重要影响。相较于其他种类的酯类溶剂，链状羧酸酯具有更低的凝固点和更小的黏度，可以显著增强电池的电导率，改善电池的低温性能和循环稳定性。然而，链状羧酸酯与负极的界面稳定性较差，不仅会加重极片自身存在的膨胀问题，也会影响界面存在的产气问题，造成电芯容量衰减过快，电池的循环性能恶化。此外，此类电解液在经过长时间循环使用，特别是在高温和高压下极片膨胀问题会出现恶化，这会严重影响电芯的使用寿命，甚至带来安全问题。
针对上述存在的普遍技术问题，第一方面，本申请提供了一种二次电池，其包括正极极片、负极极片和非水电解质；其中，所述负极极片包括负极活性材料层，所述负极活性材料层包括负极活性物质，所述负极活性物质包括石墨材料；所述非水电解质包括溶剂，所述溶剂包括第一溶剂，所述第一溶剂为链状羧酸酯；
所述负极极片的OI值、所述负极极片的电阻值R与所述第一溶剂在所述溶剂中的质量占比W0满足如下关系：0.08/mΩ≤W0×100/(R×OI)≤5/mΩ；
其中，所述负极极片的OI值是指所述石墨材料的004晶面衍射峰强度与110晶面衍射峰强度的比值；R的单位为mΩ。
在本申请中，如无其他说明，电极极片可以为正极极片或负极极片，电极极片中的“活性物质”指能够可逆地嵌入与脱出活性离子能力的物质。如无其他说明，“负极活性物质”指用于负极极片的、能够可逆地嵌入与脱出活性离子能力的物质；“正极活性物质”指用于正极极片的、能够可逆地脱出与嵌入活性离子能力的物质。二次电池充电时，活性离子从正极脱出，经过电解质嵌入负极；而二次电池放电时，活性离子则从负极脱出，嵌入正极。活性离子没有特别限定， 可以为锂离子，此时对应锂离子二次电池。
在本申请中，“活性材料”和“活性物质”，具有相同含义，可以互换使用；“正极活性物质”与“正极活性材料”具有相同含义，可以互换使用；“负极活性物质”与“负极活性材料”具有相同含义，可以互换使用。
在本申请中，如无特别说明，“活性材料层”包括正极极片的正极活性材料层以及负极极片的负极活性材料层，根据详细的情形，可以指正极活性材料层或负极活性材料层。可以理解，正极活性材料层含有正极活性物质，负极活性材料层含有负极活性物质。
在本申请中，负极极片的OI值具有本领域公知的含义。负极极片的OI值是指负极活性材料层中石墨材料的004晶面衍射峰强度与110晶面衍射峰强度的比值，可用于表征负极活性材料层的取向性，可反映负极活性材料层中晶粒排列的各向异性程度。004晶面对应层结构平行于电极片的石墨，110晶面对应层结构垂直于电极片的石墨；OI值越小，表明对活性离子(如锂离子)扩散更有利，更有利于降低极片自身膨胀。可以通过X射线粉末衍射仪(非限制性例如X'pert PRO)测试004晶面衍射峰和110晶面衍射峰的强度，依据X射线衍射分析法通则以及石墨的点阵参数测定方法JIS K 0131-1996、JB/T4220-2011，得到X射线衍射谱图，然后根据OI＝I004/I110得到负极活性材料层的004晶面衍射峰与110晶面衍射峰的强度之比，其中，I004为004晶面衍射峰的强度，I110为110晶面衍射峰的强度。
在一些实施方式中，负极极片的OI值可以通过但不限于下述方式进行调节：石墨颗粒的OI值、石墨颗粒的粒径(如Dv50)、负极极片的孔隙率、负极极片的压实密度、负极极片的组分种类及含量等中的至少一种参数。这对本领域技术人员来说是可以实现的。
在本申请中，负极极片电阻值R具有本领域的公知含义。如无其他说明，本申请中的R可以使用电阻仪测试获得，例如可以采用BER1300多功能极片电阻仪进行测试。进一步地，可以采用如下方法进行测试：将负极极片裁成一定尺寸(直径为40mm的小圆片)的待测样品；将待测样品放置于电阻仪(如BER1300多功能极片电阻仪)两个探针之间，记录电阻值测试值；取多个(如至少5个)待测样品，并计算多个待测样品的平均值作为负极极片电阻值R的测试结果。
在本申请中，“链状羧酸酯”具有本领域公知的含义。链状羧酸酯是指具有酯基(-C(＝O)-O-)结构，且该羧酸酯中不含有环结构的一类羧酸酯有机化合物。在申请中，该链状羧酸酯作为溶剂发挥作用，被记为第一溶剂。可以理解，在-C(＝O)-O-的两侧连接的均为链式结构，而非环状结构，而且-C(＝O)-O-本身也不参与成环。可以理解，该链状羧酸酯在电芯中为液态。
通过协同控制负极极片的OI值与链状羧酸酯溶剂在溶剂中的质量占比W0，可以兼顾二次电池的快充性能、循环性能和安全性能。当OI值与W0满足上述关系0.08/mΩ≤W0×100/(R×OI)≤5/mΩ时，一方面，非水电解质中的链状羧酸酯具有低黏度和导电性的特点，可以显著增强电池的电导率，还能改善电池的低温性能和循环稳定性，再一方面，负极极片具有合适的取向度，在活性离子(如锂离子)嵌入过程中具有合适的方向选择性，能够把活性离子嵌入膨胀(如嵌锂膨胀)分散到不同方向，从而降低极片和电芯的循环膨胀，可以有效缓解由于链状羧酸酯与负极的界面稳定性差而导致的极片自身膨胀被加剧的问题，提升电池安全性，还可以降低活性离子在负极极片传输过程中的浓差极化，与负极极片电阻值R搭配实现大幅度提升电池快充能力。因此，通过协同控制OI值、R与W0，能够使二次电池在快充性能、循环性能和安全性能方面具有优良的综合性功能，可以兼顾较短的快充时间，较低的循环膨胀以及较高的循环容量保持率。
在本申请中，W0×100/(R×OI)值较大时，对电池快充能力较为有利；然而该值太大又容易导致极片自身膨太大，严重恶化电芯的循环和安全性能。当W0×100/(R×OI)过高时，有可能导致极片脱模，致使电芯无法工作。
在一些实施方式中，6≤OI≤25；可选地，6≤OI≤18；进一步可选地，12≤OI≤18。所述负极极片的OI值还可以为下述任一种数值或者选自下述任两种数值构成的区间：6、7、8、9、10、11、12、13、14、15、16、17、18、19、20、21、22、23、24、25等。所述负极极片的OI值可以选自下述任一种范围：6～15、12～25、6～18、14～16等。
通过调节QI值在较为合适的范围内，更有利于降低在活性离子嵌入过程中的方向选择性，从而更好地活性离子嵌入膨胀分散到不同方向；此外，还可以更好地提高负极极片的活性离子传输性能。
在一些实施方式中，1mΩ≤R≤50mΩ；可选地，5mΩ≤R≤30mΩ；进一步可选地，10mΩ≤R≤20mΩ。所述负极极片的电阻值R还可以为下述任一种数值或者选自下述任两种数值构成的区间：1mΩ、2mΩ、3mΩ、4mΩ、5mΩ、6mΩ、8mΩ、10mΩ、12mΩ、15mΩ、16mΩ、8mΩ、20mΩ、25 mΩ、30mΩ、35mΩ、40mΩ、45mΩ、50mΩ等。所述负极极片的电阻值R还可以选自下述任一范围：12mΩ～18mΩ、14mΩ～16mΩ、5mΩ～20mΩ、5mΩ～18mΩ、10mΩ～18mΩ等。
在一些实施方式中，负极极片的电阻值R可以通过但不限于下述方式进行调节：负极极片的压实密度、负极极片的孔隙率、负极极片的组分种类及含量等。例如可以调整负极极片中导电剂的种类和/或含量来调控负极极片的电阻值R。
通过将负极极片的电阻值R控制在一定的范围内，可以将W0×100/(R×OI)控制在更为合适的范围内，从而在较短的快充时间，较低的循环膨胀以及较高的循环容量保持率方面实现更好的综合效果，并更有利于提高负极极片的活性离子传输性能和电子传导性能。
在本申请中，所述第一溶剂在所述溶剂中的质量占比记为W0。
在一些实施方式中，10％≤W0≤80％。W0还可以为下述任一种百分数：10％、20％、30％、40％、50％、60％、70％、80％等，还可以选自上述任两种百分数构成的区间，例如，20％≤W0≤80％，30％≤W0≤70％，50％≤W0≤70％，10％≤W0≤60％，20％≤W0≤60％等。
通过将链状羧酸酯(第一溶剂)在溶剂中的含量W0控制在一定的范围内，可以在兼顾二次电池的快充性能、循环性能和安全性能的基础上，更有利于增强电池的电导率，还可更有利于改善二次善电池的低温性能和循环稳定性。
在一些实施方式中，0.67≤W0×100/OI≤10。W0×100/OI还可以为下述任一种数值或者选自下述任两种数值构成的区间：0.67、0.8、1、1.2、1.3、1.33、1.33±0.01、1.4、1.5、2、2.5、2.67、2.67±0.01、3、4、4.5、4.67、4.67±0.01、5、5.33、5.33±0.01、6、7、8、9、10等。
在一些实施方式中，1≤W0×100/OI≤10；可选地，1≤W0×100/OI≤5；进一步可选地，3≤W0×100/OI≤5。
在一些实施方式中，0.67≤W0×100/OI≤4；可选地，1≤W0×100/OI≤4。
在控制W0×100/(R×OI)符合前述关系的基础上，通过W0×100/OI进一步调控非水电解质中链状羧酸酯与负极活性材料层中晶粒排列方向的搭配情况，更易实现快充性能、循环性能和安全性能综合性能的提升。
在本申请中，所述二次电池具有如下特征：0.08/mΩ≤W0×100/(R×OI)≤5/mΩ。对于本申请提供的二次电池而言，W0×100/(R×OI)还可以为下述任一种数值或者选自下述任两种数值构成的区间：0.1/mΩ、0.13/mΩ、0.15/mΩ、0.2mΩ、0.3/mΩ、0.4/mΩ、0.5/mΩ、0.6/mΩ、.8/mΩ、1/mΩ、1.2/mΩ、1.4/mΩ、1.5/mΩ、1.6/mΩ、1.8/mΩ、2/mΩ、2.2/mΩ、2.4/mΩ、2.5/mΩ、2.6/mΩ、2.8/mΩ、3/mΩ、3.5/mΩ、3.6/mΩ、3.8/mΩ、4/mΩ、4.5/mΩ、4.8/mΩ、5/mΩ等。
在一些实施方式中，0.1/mΩ≤W0×100/(R×OI)≤5/mΩ。
在一些实施方式中，0.1/mΩ≤W0×100/(R×OI)≤2/mΩ。
在协同控制负极极片的取向度和第一溶剂(链状羧酸酯)在溶剂中的含量基础上，进一步协同控制负极极片的电阻值R，可以将W0×100/(R×OI)控制在合适的范围内，可以更好地在兼顾二次电池的快充性能、循环性能和安全性能的综合性能。
在一些实施方式中，所述二次电池满足如下特征组合：6≤OI≤18，10mΩ≤R≤20mΩ，且20％≤W0≤80％。在其中的一些实施方式中，12≤OI≤18，10mΩ≤R≤20mΩ，且10％≤W0≤60％。
通过精细地协同控制负极极片的OI值为12～18、负极极片的电阻值R为10mΩ～20mΩ和链状羧酸酯溶剂在溶剂中的质量占比W0为20％～80％(进一步可选为10％～60％)，可以更好地实现快充性能、循环性能和安全性能的兼顾，更有利于使二次电池同时具有较优快充能力，较低的循环膨胀以及较高的循环容量保持率。
在一些实施方式中，12≤OI≤18，10mΩ≤R≤20mΩ，20％≤W0≤60％。
在一些实施方式中，12≤OI≤18，10mΩ≤R≤20mΩ，且50％≤W0≤70％。
通过控制不同参数的取值情况，还可以进一步在某个或某些方面更具优势。比如，12≤OI≤18，10mΩ≤R≤20mΩ，且20％≤W0≤60％的情形中，可以在较优综合性能基础上还具有显著优异的低循环膨胀和循环性能。再比如，12≤OI≤18，10mΩ≤R≤20mΩ，且50％≤W0≤70％的情形中，在较优综合性能基础上，还可以在较短的快充时间和较低的循环膨胀方面具有明显优势。
在一些实施方式中，所述第一溶剂包括结构如式(1)所示的化合物：
R1和R2分别独立地为烷基或卤代烷基。可见，R1和R2不成环，如式(1)所示结构的化合物为一种链状羧酸酯。
可选地，R1和R2分别独立地为C1-3烷基或C1-3卤代烷基。
可选地，R1和R2分别独立地为C1-3烷基或C1-3氟代烷基。
其中，C1-3烷基可以为甲基(可记为Me、-CH3)、乙基(可记为Et、-CH2CH3)或丙基，丙基可以为正丙基(可记为1-丙基、n-Pr、n-丙基、-CH2CH2CH3)或异丙基(可记为2-丙基、i-Pr、i-丙基、-CH(CH3)2)。进一步地，C1-3烷基可以为甲基、乙基或正丙基。更进一步地，进一步地，C1-3烷基可以为甲基或乙基。
其中，C1-3卤代烷基中的碳原子可以为1、2、或3，也即可以为C1卤代烷基、C2卤代烷基或C3卤代烷基。C1-3卤代烷基中的卤素原子可以为氟。C1-3卤代烷基中卤素原子的个数可以为1个或多个。C1-3卤代烷基中卤素原子的个数为多个时，可以为2个至烷基氢原子全部被取代。
其中，C1-3氟代烷基中的碳原子可以为1、2、或3，也即可以为C1氟代烷基、C2氟代烷基或C3氟代烷基。C1-3氟代烷基中氟原子的个数可以为1个或多个。C1-3氟代烷基中氟原子的个数为多个时，可以为2个至全氟取代。
在一些实施方式中，R1和R2分别独立地为甲基、乙基、丙基、氟代甲基、氟代乙基和氟代丙基中的一种，可选地，R1和R2分别独立地为甲基、乙基、氟代甲基和氟代乙基中的一种。氟代甲基中的氟原子个数可以独立地为1、2或3个。氟代乙基中的氟原子个数可以独立地为1、2、3、4、5或6个，进一步可以独立地为1、2或3个。氟代丙基中的氟原子个数可以独立地为1、2、3、4、5、6、7、8或9个，进一步可以独立地为1、2或3个。
可以选择分子尺寸较小的第一溶剂，此时，第一溶剂粘度较低，有利于二次电池获得更好的快充性能。
在一些实施方式中，所述第一溶剂包括下述化合物中的一种或多种，其中可以选自下述化合物中的一种或多种：CH3CH2-OC(＝O)-CH3(也即乙酸乙酯)、CH3-OC(＝O)-CH3(也即乙酸甲酯)、CH3CH2-OC(＝O)-CH2CH3(也即丙酸乙酯)、CH3-OC(＝O)-CH2CH3(也即丙酸甲酯)、CH3CH2-OC(＝O)-CH2F、CH3CH2-OC(＝O)-CHF2、CH3CH2-OC(＝O)-CF3、CH3-OC(＝O)-CH2F、CH3-OC(＝O)-CHF2、CH3-OC(＝O)-CF3、CF3-OC(＝O)-CH3和CHF2-OC(＝O)-CH3；
也即，所述第一溶剂包括下述化合物中的一种或多种，其中可以选自下述化合物中的一种或多种：

在一些实施方式中，所述第一溶剂包括下述化合物中的一种或多种：乙酸甲酯、乙酸乙酯、二氟乙酸甲酯和二氟乙酸乙酯。在其中的一些实施方式中，所述第一溶剂选自下述化合物中的一种或多种：乙酸甲酯、乙酸乙酯、二氟乙酸甲酯和二氟乙酸乙酯。
在一些实施方式中，所述非水电解质还包括第一添加剂；所述第一添加剂为二异氰酸酯。
在本申请中，二异氰酸酯指含有两个异氰酸酯基(-NCO)的化合物。
链状羧酸酯(第一溶剂)的引入有利于提高电池的快充能力，然而，由于羧酸酯与负极极片的兼容性因素，如果其用量W0与负极极片的OI值、电阻值R之间的匹配性不佳，可能会加重负极极片自身存在的膨胀问题，也可能影响界面存在的产气问题，还可能造成电芯容量的衰减及电池循环性能的恶化。通过向非水电解质中引入添加剂二异氰酸酯(记为第一添加剂)，可以在负极极片表面形成具有保护作用的固体电解质界面(SEI)层，该保护层可以协助活性离子嵌入到负极极片的负极活性材料层中，使得负极极片的活性离子嵌入膨胀效应能够被均匀地传导到各个方向，从而减少负极极片的循环膨胀率。此外，第一添加剂还能显著提升电解液和负极极片界面的稳定性，可以降低二次电池循环过程中电解液的消耗和负极结构的破坏，从而显著改善二次电池的循环性能。
在一些实施方式中，所述第一添加剂包括结构如下的化合物：
其中，R3为未取代的或Ra取代的C1-18亚烃基；Ra可以包括下述取代基中的一种或多种，其中可以选自下述取代基中的一种或多种：卤素原子(可以为氟、氯、溴和碘中的一种或多种，进一步可以为氟)、-CN、-NCO、-OH、-COOH、-SOOH、-OC(＝O)R11、R12OC(＝O)-、C1-10烷基、C2-10烯基、C2-10炔基和C2-10氧杂烷基中的一种或多种；R11和R12分别独立地为烷基或卤代烷基。如无其他说明，“Ra取代的”情形中，Ra的个数可以为1个或多个。
在取代基Ra中，R11和R12分别独立地为烷基或卤代烷基。可选地，R11和R12分别独立地为C1-3烷基或C1-3卤代烷基。进一步可选地，R11和R12分别独立地为C1-3烷基或C1-3氟代烷基。
在一些实施方式中，R11和R12分别独立地为甲基、乙基、丙基、氟代甲基、氟代乙基和氟代丙基中的一种，可选地，R11和R12分别独立地为甲基、乙基、氟代甲基和氟代乙基中的一种。氟代甲基中的氟原子个数可以独立地为1、2或3个。氟代乙基中的氟原子个数可以独立地为1、2、3、4、5或6个，进一步可以独立地为1、2或3个。氟代丙基中的氟原子个数可以独立地为1、2、3、4、5、6、7、8或9个，进一步可以独立地为1、2或3个。
在一些实施方式中，在“R3为未取代的或Ra取代的C1-18亚烃基”的基础上，“C1-18亚烃基”中的碳原子数为1～16，进一步地，“C1-18亚烃基”中的碳原子数还可以为下述任一种数值或选自下述任两种数值构成的区间：1、2、3、4、5、6、7、8、9、10、11、12、13、14、15和16。其在，任两种数值构成的区间如1～16，2～16，4～16，6～16，1～14，2～14，4～14，6～14，1～10，2～10，4～10，6～10等。
在一些实施方式中，在“R3为未取代的或Ra取代的C1-18亚烃基”的基础上，R3的碳原子数为1～16，进一步地，R3的碳原子数还可以为下述任一种数值或选自下述任两种数值构成的区间：1、2、3、4、5、6、7、8、9、10、11、12、13、14、15和16。其在，任两种数值构成的区间如1～16，2～16，4～16，6～16，1～14，2～14，4～14，6～14，1～10，2～10，4～10，6～10等。
在一些实施方式中，R3为未取代的或Ra取代的C2-10亚烷基、未取代的或Ra取代的C3-18二价环烷基或未取代的或Ra取代的C6-18亚芳基。可选地，R3为C2-10亚烷基、C6-18二价环烷基或C6-18亚芳基；进一步可选地，R3为C4-10亚烷基、C6-14二价环烷基或C6-14亚芳基；更进一步可选地，R3为C4-10亚烷基、C6-10二价环烷基或C6-10亚芳基；更进一步可选地，R3为C4-8亚己基、含有己环的C6-10二价环烷基或含有苯环的C6-10亚芳基。
在一些实施方式中，Ra选自下述取代基中的一种或多种：卤素原子(可以为氟、氯、溴和碘中的一种或多种，进一步可以为氟)、-CN、-NCO、-OH、-COOH、-SOOH、-OC(＝O)R11、R12OC(＝O)-、C1-10烷基、C2-10烯基、C2-10炔基和C2-10氧杂烷基中的一种或多种。在其中的一些实施例中，Ra选自下述取代基中的一种或多种：卤素原子(可以为氟、氯、溴和碘中的一种或多种，进一步可 以为氟)、-CN、-NCO、-OH、-COOH、-SOOH、-OC(＝O)R11、R12OC(＝O)-和C2-10氧杂烷基中的一种或多种。
在一些实施方式中，Ra为卤素原子，可以为氟、氯、溴和碘中的一种或多种，进一步可以为氟。
在R3中，Ra的个数可以为0个、一个或多个。Ra的个数为0时，对应于“未取代的”情形。Ra的个数为1个或多个时，对应于“Ra取代的”情形。
在一些实施方式中，在R3中，Ra的个数可以为0个。此时，R3的碳原子数可以如前文所定义。例如，R3为未取代的C1-18亚烃基，未取代的C1-16亚烃基，未取代的C2-14亚烃基等等。
在一些实施方式中，在R3中，Ra的个数可以为一个或多个。
在一些实施例中，Ra为C1-10烷基，进一步可以为C1-3烷基，进一步可以为甲基或乙基。在一些实施例中，Ra为甲基。
在一些实施方式中，R3为C2-10亚烷基、C2-10杂亚烷基、C6-18亚芳基、C2-18杂亚芳基、C3-18亚脂环基或C3-18杂亚脂环基，前述任一种基团可以为未取代的或者为Ra取代的；如无其他说明，“Ra取代的”情形中，Ra的个数可以为1个或多个。其中的C6-18亚芳基可以为C6-14亚芳基，进一步可以为C6-14亚芳基。
在本申请中，没有特别写明“取代的”情形时，指“未取代的”情形。
在本申请中，术语“烃”化合物指由碳原子和氢原子组成的化合物。烃化合物可以为饱和结构(即饱和烃)，也可以为不饱和结构(即不饱和烃)，可以含有环结构(即环烃)，也可以不含有环结构(即链烃)，可以具有芳香性(即芳烃或芳香族烃)，也可以不具有芳香性(即脂肪族烃)。饱和结构的烃，也即饱和烃，可以为烷烃或环烷烃。烷烃中不含有环结构，可以为直链结构，也可以含有支链。环烷烃中含有环结构，环结构的个数可以为1个或多个，例如1、2或3个。环烷烃为含有环结构的饱和烃，其为非芳香族烃。具有芳香性的烃，也即芳烃，其中含有芳环结构。不饱和烃中可以含有碳碳双键、碳碳叁键等。不饱和烃中可以含有环结构，也可以不含环结构。如无其他说明，“烯烃”指含有一个或多个碳碳双键的链烃，“环烯烃”指含有一个或多个碳碳双键的环烃，“炔烃”指含有一个或多个碳碳叁键的链烃，“环炔烃”指含有一个或多个碳碳叁键的环烃。“脂环烃”指含有环结构的非芳香性烃，可以为饱和的或不饱和的，构成不饱和键的碳原子可以为成环原子，也可以不为成环原子，例如，脂环烃可以包括但不限于环烷烃、环烯烃、环炔烃等。
在本申请中，术语“烃基”是指包含伯(正)碳原子、或仲碳原子、或叔碳原子、或季碳原子、或其组合的烃化合物失去一个氢原子生成的一价残基。包含该术语的短语，例如，“C1～10烃基”是指包含1至10个碳原子的烃基，每次出现时，可以互相独立地为C1烃基、C2烃基、C3烃基、C4烃基、C5烃基、C6烃基、C7烃基、C8烃基、C9烃基或C10烃基。
在本申请中，术语“亚烃基”是指在烃化合物基础上除去两个氢原子衍生形成的(或者在烃基的基础上再失去一个氢原子衍生形成的)具有两个单价基团中心的二价烃基，其可以是饱和的支链结构或饱和的直链结构。例如，“C1～C10亚烃基”是指烃基部分包含1至10个碳原子，每次出现时，可以互相独立地为C1亚烃基、C2亚烃基、C3亚烃基、C4亚烃基、C5亚烃基、C6亚烃基、C7亚烃基、C8亚烃基、C9亚烃基或C10亚烃基。
在本申请中，术语“烷基”是指包含伯(正)碳原子、或仲碳原子、或叔碳原子、或季碳原子、或其组合的饱和烃失去一个氢原子生成的一价残基。包含该术语的短语，例如，“C1～10烷基”是指包含1至10个碳原子的烷基，每次出现时，可以互相独立地为C1烷基、C2烷基、C3烷基、C4烷基、C5烷基、C6烷基、C7烷基、C8烷基、C9烷基或C10烷基。合适的实例包括但不限于：甲基(Me、-CH3)、乙基(Et、-CH2CH3)、1-丙基(n-Pr、n-丙基、-CH2CH2CH3)、2-丙基(i-Pr、i-丙基、-CH(CH3)2)、1-丁基(n-Bu、n-丁基、-CH2CH2CH2CH3)、2-甲基-1-丙基(i-Bu、i-丁基、-CH2CH(CH3)2)、2-丁基(s-Bu、s-丁基、-CH(CH3)CH2CH3)、2-甲基-2-丙基(t-Bu、t-丁基、-C(CH3)3)、1-戊基(n-戊基、-CH2CH2CH2CH2CH3)、2-戊基(-CH(CH3)CH2CH2CH3)、3-戊基(-CH(CH2CH3)2)、2-甲基-2-丁基(-C(CH3)2CH2CH3)、3-甲基-2-丁基(-CH(CH3)CH(CH3)2)、3-甲基-1-丁基(-CH2CH2CH(CH3)2)、2-甲基-1-丁基(-CH2CH(CH3)CH2CH3)、1-己基(-CH2CH2CH2CH2CH2CH3)、2-己基(-CH(CH3)CH2CH2CH2CH3)、3-己基(-CH(CH2CH3)(CH2CH2CH3))、2-甲基-2-戊基(-C(CH3)2CH2CH2CH3)、3-甲基-2-戊基(-CH(CH3)CH(CH3)CH2CH3)、4-甲基-2-戊基(-CH(CH3)CH2CH(CH3)2)、3-甲基-3-戊基(-C(CH3)(CH2CH3)2)、2-甲基-3-戊基(-CH(CH2CH3)CH(CH3)2)、2,3-二甲基-2-丁基(-C(CH3)2CH(CH3)2)、3,3-二甲基-2-丁基(-CH(CH3)C(CH3)3和辛基(-(CH2)7CH3)。
在本申请中，术语“亚烷基”是指在烷烃基础上除去两个氢原子衍生形成的(或者在烷基的 基础上再失去一个氢原子衍生形成的)具有两个单价基团中心的二价烃基，其可以是饱和的支链结构或饱和的直链结构。例如，“C1～C10亚烷基”是指烷基部分包含1至10个碳原子，每次出现时，可以互相独立地为C1亚烷基(也即亚甲基)、C2亚烷基(也即亚乙基)、C3亚烷基(也即亚丙基)、C4亚烷基(也即亚丁基)、C5亚烷基(也即亚戊基)、C6亚烷基(也即亚己基)、C7亚烷基(也即亚庚基)、C8亚烷基(也即亚辛基)、C9亚烷基(也即亚壬基)或C10亚烷基(也即亚癸基)。合适的实例包括但不限于：亚甲基(-CH2-)、1,1-乙基(-CH(CH3)-)、1,2-乙基(-CH2CH2-)、1,1-丙基(-CH(CH2CH3)-)、1,2-丙基(-CH2CH(CH3)-)、1,3-丙基(-CH2CH2CH2-)和1,4-丁基(-CH2CH2CH2CH2-)。
在本申请中，术语“烯基”是指链状结构的烯烃化合物失去一个氢原子生成的一价残基，该氢原子可以位于碳碳双键上，也可以位于碳碳双键的烷基取代基上。包含该术语的短语，例如，“C2～10烯基”是指包含2至10个碳原子的烯基，每次出现时，可以互相独立地为C2烯基、C3烯基、C4烯基、C5烯基、C6烯基、C7烯基、C8烯基、C9烯基或C10烯基。合适的实例包括但不限于：乙烯基(CH2＝CH-)、烯丙基(CH2＝CH-CH2-)、CH3-CH＝CH-等。
在本申请中，术语“炔基”是指链状结构的炔烃化合物失去一个氢原子生成的一价残基，该氢原子可以位于碳碳叁键上，也可以位于碳碳叁键的烷基取代基上。包含该术语的短语，例如，“C2～10炔基”是指包含2至10个碳原子的炔基，每次出现时，可以互相独立地为C2炔基、C3炔基、C4炔基、C5炔基、C6炔基、C7炔基、C8炔基、C9炔基或C10炔基。合适的实例包括但不限于：乙炔基(CH≡C-)、炔丙基(CH≡C-CH2-)、CH3-C≡C-等。
本申请中，术语“杂烷基”是指在烷基的基础上至少一个碳原子被杂原子所替代；杂原子为非碳氢原子，可以为但不限于N原子、O原子、S原子、P原子等。以下以O、N、S为例进行说明。例如，如果烷基中连接至相邻基团的碳原子被杂原子O、N、S代替，所得到的杂烷基分别是烷氧基(例如，-OCH3等)、氨基(例如，-NHCH3、-N(CH3)2等)或硫代烷基(例如，-SCH3)。如果烷基中不与相邻基团直接相连的碳原子被杂原子O、N、S代替，所得到的杂烷基分别是烷氧基烷基(例如，-CH2CH2-O-CH3等)、烷氨基烷基(例如，-CH2NHCH3、-CH2N(CH3)2等)或烷硫基烷基(例如、-CH2-S-CH3)。如果烷基的末端碳原子被杂原子代替，所得到的杂烷基可以是羟基烷基(例如，-CH2CH2-OH)、氨基烷基(例如，-CH2NH2)或巯基氨基(例如，-CH2CH2-SH)。包含该术语“杂烷基”的短语，例如，“C1-10杂烷基”是指包含1至10个碳原子的杂烷基，每次出现时，可以互相独立地为C1杂烷基、C2杂烷基、C3杂烷基、C4杂烷基、C5杂烷基、C6杂烷基、C7杂烷基、C8杂烷基、C9杂烷基或C10杂烷基。
在本申请中，术语“烷氧基”指烷基与-O-连接形成的一价基团。包含该术语的短语，例如，“C1-10氧杂烷基”是指包含1至10个碳原子的烷氧基，每次出现时，可以互相独立地为C1烷氧基、C2烷氧基、C3烷氧基、C4烷氧基、C5烷氧基、C6烷氧基、C7烷氧基、C8烷氧基、C9烷氧基或C10烷氧基。合适的示例可以包括但不限于甲氧基(CH3O-)、乙氧基(CH3CH2O-)等。
在本申请中，术语“氧杂烷基”指在烷基的基础上至少一个碳原子被氧原子所替代，该氧原子可以位于烷基的连接位点处，也可以不位于连接位点处。氧原子的个数可以为1个或多个。以一个氧原子杂化为例，如烷氧基、烷氧基烷基等。包含该术语的短语，例如，“C1-10氧杂烷基”是指包含1至10个碳原子的氧杂烷基，每次出现时，可以互相独立地为C1氧杂烷基、C2氧杂烷基、C3氧杂烷基、C4氧杂烷基、C5氧杂烷基、C6氧杂烷基、C7氧杂烷基、C8氧杂烷基、C9氧杂烷基或C10氧杂烷基。
在本申请中，术语“杂亚烷基”也称为“二价杂烷基”，是指在杂烷基的基础上再失去一个氢原子衍生形成的具有两个单价基团中心的二价杂烃基(该氢原子可以位于碳原子上，也可以位于杂原子上)，或者指在亚烷基的基础上至少一个碳原子被杂原子所替代(任一个杂原子可以位于亚烷基的连接位点处，也可以不位于连接位点处)；杂原子可以为但不限于N原子、O原子、S原子、P原子等。包含该术语的短语，例如，“C1-10杂亚烷基”是指包含1至10个碳原子的杂亚烷基，每次出现时，可以互相独立地为C1杂亚烷基、C2杂亚烷基、C3杂亚烷基、C4杂亚烷基、C5杂亚烷基、C6杂亚烷基、C7杂亚烷基、C8杂亚烷基、C9杂亚烷基或C10杂亚烷基。
在本申请中，术语“环烷基”，是指饱和环烷烃失去一个环上的或非环上的氢原子生成的一价残基，既可以直接在环上形成单价的连接位点，也可以在环上的烷基取代基位置形成单价的连接位点。包含该术语的短语，例如，“C3-10环烷基”是指包含3至10个碳原子的环烷基，每次出现时，可以互相独立地为C3环烷基、C4环烷基、C5环烷基、C6环烷基、C7环烷基、C8环烷基、C9环烷基或C10环烷基。环烷基中的环结构个数可以为1个或多个，例如1、2或3个。环烷基中 任一个环结构的成环原子数可以为3～8，例如3、4、5、6、7或8；例如丙环丁环戊环己环庚环或辛环。直接在环上形成单价连接位点的情形可以包括但不限于：环丙基环丁基环戊基环己基和环庚基。从环上的烷基取代基位置形成单价连接位点的情形可以包括但不限于(一种含有己环的C7环烷基)。
本申请中，如无其他说明，结构式中位于末端的表示共价键的连接位点。
在本申请中，术语“亚脂环基”也称为“二价脂环基”，是指在脂环烃基础上失去两个环上的或非环上的氢原子衍生形成的二价残基，所失去的任一个氢原子既可以在环上，也可以不在环上，也即既可以直接在环上形成单价的连接位点，也可以在环上的烃基取代基位置形成单价的连接位点。亚脂环基可以包括但不限于二价环烷基、二价环烯基、二价环炔基等。包含该术语的短语，例如，“C3-10亚脂环基”是指包含3至10个碳原子的亚脂环基，每次出现时，可以互相独立地为C3亚脂环基、C4亚脂环基、C5亚脂环基、C6亚脂环基、C7亚脂环基、C8亚脂环基、C9亚脂环基或C10亚脂环基。
在本申请中，术语“二价环烷基”也称为“亚环烷基”，是指在环烷烃基础上除去两个氢原子衍生形成的(或者在环烷基的基础上再失去一个氢原子衍生形成的)具有两个单价基团中心的二价饱和烃基，任一个单价基团中心的位置可以独立地位于环上或者不位于环上。包含该术语的短语，例如，“C3-10二价环烷基”是指包含3至10个碳原子的二价环烷基，每次出现时，可以互相独立地为C3二价环烷基、C4二价环烷基、C5二价环烷基、C6二价环烷基、C7二价环烷基、C8二价环烷基、C9二价环烷基或C10二价环烷基。“二价环烷基”中的碳原子数可以为3～10个，可以为3、4、5、6、7、8、9或10个，例如可以为6～10个。二价环烷基中的环结构个数可以为1个或多个，例如1、2或3个。“二价环烷基”中任一个环结构的成环原子数可以为3～8，可以为3、4、5、6、7或8。非限制性示例，“C6-10二价环烷基”指含有6～10个碳原子数的二价环烷基，其中一个环结构的成环原子数没有特别限制。“含有己环的C6-10二价环烷基”是指含有己环且含有6～10个碳原子的二价环烷基，例如，二价环己基(如1,4-位结构1，3-位结构或1,2-位结构)、等。
在本申请中，术语“二价环烯基”也称为“亚环烯基”，是指在环烯烃基础上除去两个氢原子衍生形成的具有两个单价基团中心的二价不饱和烃基，任一个单价基团中心的位置可以独立地位于环上或者不位于环上。包含该术语的短语，例如，“C3-10二价环烯基”是指包含3至10个碳原子的二价环烯基，每次出现时，可以互相独立地为C3二价环烯基、C4二价环烯基、C5二价环烯基、C6二价环烯基、C7二价环烯基、C8二价环烯基、C9二价环烯基或C10二价环烯基。
在本申请中，术语“杂亚脂环基”也称为“二价杂脂环基”，是指在亚脂环基的基础上至少一个烃基部位的碳原子被杂原子所替代；该杂原子可以位于亚脂环基的连接位点处，也可以不位于连接位点处；该杂原子可以位于环上，也可以不位于环上；杂原子可以为但不限于N原子、O原子、S原子、P原子等。该杂原子可以位于亚脂环基的连接位点处(也即末端)，也可以不位于连接位点处。包含该术语的短语，例如，“C3-10杂亚脂环基”是指包含3至10个碳原子的杂亚脂环基，每次出现时，可以互相独立地为C3杂亚脂环基、C4杂亚脂环基、C5杂亚脂环基、C6杂亚脂环基、C7杂亚脂环基、C8杂亚脂环基、C9杂亚脂环基或C10杂亚脂环基。
本申请中，术语“亚芳基”是指在芳烃的基础上失去两个氢原子形成的具有两个单价基团中心的二价残基(失去的任一个氢原子可以独立地位于芳环上，也可以不位于芳环上)。亚芳基可 以为单环亚芳基、或稠环亚芳基、或多环亚芳基，对于多环的环种，至少一个是芳族环系。例如，“C6-14亚芳基”是指包含6至14个碳原子的亚芳基，每次出现时，可以互相独立地为C6亚芳基、C7亚芳基、C8亚芳基、C9亚芳基、C10亚芳基、C11亚芳基、C12亚芳基、C13亚芳基或C14亚芳基。合适的实例包括但不限于衍生自下述芳环的亚芳基：苯、联苯、二苯甲撑、萘、蒽、菲、二萘嵌苯、三亚苯或前述任一种的烃基取代形式，如甲苯、二甲苯、四甲苯、乙苯、二甲基联苯等。
在本申请中，术语“杂亚芳基”也称为“二价杂芳基”，是指在亚芳基的基础上至少一个碳原子被杂原子所替代；任一个杂原子可以位于亚芳基的连接位点处，也可以不位于连接位点处；任一个杂原子可以位于芳环上，也可以不位于芳环上；杂原子可以为但不限于N原子、O原子、S原子、P原子等。包含该术语的短语，例如，“C2-10杂亚芳基”是指包含2至10个碳原子的杂亚芳基，每次出现时，可以互相独立地为C2杂亚芳基、C3杂亚芳基、C4杂亚芳基、C5杂亚芳基、C6杂亚芳基、C7杂亚芳基、C8杂亚芳基、C9杂亚芳基或C10杂亚芳基。
在一些实施方式中，R3为C1-8亚烷基、C6-14亚芳基、-(Z1)p1-CA-(Z2)p2-和-(Z1)q1-CA1-(Z3)q3-CA2-(Z2)q2-中的任一种，或前述任一种二价基团中的一个或多个氢原子被取代基Ra取代形成的二价基团；其中，Z1、Z2和Z3各自独立地为一个共价键或C1-3亚烷基，CA为C4-14二价脂环基，CA1和CA2各自独立地为C5-12二价脂环基，p1、p2、q1、q2和q3各自独立地为0或1。
在一些实施方式中，Z1、Z2和Z3各自独立地为一个共价键或亚甲基。
在一些实施方式中，CA为二价环丁基、二价环戊基、二价环己基或
在一些实施方式中，CA1和CA2各自独立地为C5-12二价脂环基；可选地，CA1和CA2各自独立地为C4-6二价脂环基；进一步可选地，CA1和CA2各自独立地为二价环戊基或二价环己基；更进一步可选地，CA1和CA2各自独立地为二价环戊基。
在一些实施方式中，R3为亚甲基、亚乙基、亚丙基、亚丁基、亚戊基、亚己基、亚苯基、-CH2-Ph-CH2-、亚萘基、亚蒽基、-Ph-CH2-Ph-、-Ph-Ph-、二价环丁基、二价环戊基、二价环己基、或前述任一种二价基团中的一个或多个氢原子被取代基Ra取代形成的二价基团；其中，Ph为苯环。
在本申请中，中的两个表示从环上的任意位置引出两个单键从而形成两个单价位点，这个两个单价位点可以位于相同的环，也可以位于不同的环，可以位于不同的成环原子，也可以位于同一个成环原子，但可以优选两个单键从不同的成环原子引出。
在一些实施方式中，任一个Ra独立地为卤素原子或C1-3烷基；进一步可选地，任一个Ra独立地为氟原子、甲基或乙基；更进一步可选地，任一个Ra独立地为氟原子或甲基。
在一些实施方式中，所述第一添加剂包括如下化合物中的一种或多种：(1,4-苯二异氰酸酯，1,4-diisocyanatobenzene)、(1,3-苯二异氰酸酯，1,3-diisocyanatobenzene)、(1,3-bis(isocyanatomethyl)benzene，间苯二甲基异氰酸酯)、(2,3,5,6-四氟苯二异氰酸酯，1,2,4,5-tetrafluoro-3,6- diisocyanatobenzene)、(1,3-二异氰酸-2-甲苯，1,3-diisocyanato-2-methylbenzene)、(2,4-二异氰酸-1-甲苯，2,4-diisocyanato-1-methylbenzene)、(2,5-二异氰酸根合-1,3-二甲苯，2,5-diisocyanato-1,3-dimethylbenzene)、(1,4-二异氰酸根合-2,5-二甲苯，1,4-diisocyanato-2,5-dimethylbenzene)、(1,4-二异氰酸根合-2,3-二甲苯，1,4-diisocyanato-2,3-dimethylbenzene)、(1,4-二异氰酸根合-2,3,5,6-四甲苯，1,4-diisocyanato-2,3,5,6-tetramethylbenzene)、(2,3-二异氰酸-1-乙苯，1-ethyl-2,3-diisocyanatobenzene)、(1,5-二异氰酸萘，1,5-diisocyanatonaphthalene)、(9,10-二异氰酸蒽，9,10-diisocyanatoanthracene)、(二苯基甲烷二异氰酸酯，bis(4-isocyanatophenyl)methane)、(3,3'-二甲基-4,4'-联苯二异氰酸酯，4,4'-diisocyanato-3,3'-dimethyl-1,1'-biphenyl)、(3,3'-二甲氧基-4,4'-联苯二异氰酸酯，4,4'-diisocyanato-3,3'-dimethoxy-1,1'-biphenyl)、(环己烷-1,4- 二异氰酸酯，1,4-diisocyanatocyclohexane)、(1,4-环己烷二甲基二异氰酸酯，1,4-bis(isocyanatomethyl)cyclohexane)、(1,2-环己烷二甲基二异氰酸酯，1,2-bis(isocyanatomethyl)cyclohexane)、(环戊烷-1,3-二异氰酸酯，1,3-diisocyanatocyclopentane)、(1,2-环丁烷二甲基二异氰酸酯，1,2-bis(isocyanatomethyl)cyclobutane)、(9,10-二异氰酸十四氢蒽，9,10-diisocyanatotetradecahydroanthracene)、(1,3,3-三甲基环己烷-1,5-二异氰酸酯，1,5-diisocyanato-1,3,3-trimethylcyclohexane)、(2,5-diisocyanato-1,1,3-trimethylcyclohexane)、(2,3,5,6-四甲基环己烷-1,4-二异氰酸酯，1,4-diisocyanato-2,3,5,6-tetramethylcyclohexane)、(1-异氰酸基-4-(异氰酸基甲基)-1-甲基环己烷，1-isocyanato-3-(isocyanatomethyl)-1-methylcyclohexane)、(5-isocyanato-1-(isocyanatomethyl)-1,3,3-trimethylcyclohexane，异佛尔酮二异氰酸酯，Isophorone diisocyanate)、(4,4-二异氰酸酯二环己基甲烷，二环已基甲烷-4,4'-二异氰酯，bis(4-isocyanatocyclohexyl)methane)、 (二异氰酸甲酯)、(1,4-二异氰酸丁酯，1,4-diisocyanatobutane)、(1,4-二异氰酸戊酯，1,4-diisocyanatopentane)、(六亚甲基二异氰酸酯，hexamethylene diisocyanate，HMDI)等。
在一些实施方式中，所述第一添加剂下述化合物中的一种或多种：1,4-苯二异氰酸酯、1,3-苯二异氰酸酯、间苯二甲基异氰酸酯、2,3,5,6-四氟苯二异氰酸酯、1,3-二异氰酸-2-甲苯、2,4-二异氰酸-1-甲苯、2,5-二异氰酸根合-1,3-二甲苯、1,4-二异氰酸根合-2,5-二甲苯、1,4-二异氰酸根合-2,3-二甲苯、1,4-二异氰酸根合-2,3,5,6-四甲苯、2,3-二异氰酸-1-乙苯、1,5-二异氰酸萘、9,10-二异氰酸蒽、二苯基甲烷二异氰酸酯、3,3'-二甲基-4,4'-联苯二异氰酸酯、3,3'-二甲氧基-4,4'-联苯二异氰酸酯、环己烷-1,4-二异氰酸酯、1,4-环己烷二甲基二异氰酸酯、1,2-环己烷二甲基二异氰酸酯、环戊烷-1,3-二异氰酸酯、1,2-环丁烷二甲基二异氰酸酯、9,10-二异氰酸十四氢蒽、1,3,3-三甲基环己烷-1,5-二异氰酸酯、1,1,3-三甲基环己烷-2,5-二异氰酸酯、2,3,5,6-四甲基环己烷-1,4-二异氰酸酯、1-异氰酸基-4-(异氰酸基甲基)-1-甲基环己烷、异佛尔酮二异氰酸酯、4,4-二异氰酸酯二环己基甲烷、亚甲基二异氰酸酯、1,4-二异氰酸丁酯、1,4-二异氰酸戊酯和六亚甲基二异氰酸酯。进一步地，所述第一添加剂可以选自上述列举的二异氰酸酯中的一种或多种。
在一些实施方式中，所述第一添加剂包括下述化合物中的一种或多种：六亚甲基二异氰酸酯、1,4-环己烷二甲基二异氰酸酯、1,3-苯二异氰酸酯和2,4-二异氰酸-1-甲苯。在其中的一些实施方式中，所述第一添加剂选自下述化合物中的一种或多种：六亚甲基二异氰酸酯、1,4-环己烷二甲基二异氰酸酯、1,3-苯二异氰酸酯和2,4-二异氰酸-1-甲苯。
在一些实施方式中，所述第一添加剂在所述非水电解质中的质量占比(可记为W1)为0～11％。当W1为0时，也即在非水电解质中不添加第一添加剂。所述第一添加剂在所述非水电解质中的质量占比W1还可以为下述任一种百分数：0、0.005％、0.01％、0.015％、0.02％、0.05％、0.1％、0.5％、1％、2％、3％、4％、5％、6％、7％、8％、10％、11％等，还可以选自上述任两种百分数构成的区间，例如0.005％～11％、0.005％～10％、0.1％～5％、1％～5％、0～1％、0.1％～1％、0.01％～10％、1％～10％等。
在一些实施方式中，所述非水电解质还包括第二添加剂；所述第二添加剂包括单氟磷酸锂、二氟磷酸锂、四氟硼酸锂、式(3)所示化合物和氟磺酸盐中的一种或多种；
式(3)中，a、b和c各自独立地为正整数，m为选自1-3的整数，n为选自0-4的整数，q为0或1；Ma+为带有a价正电荷的金属离子；任一个Y独立地为硼原子或磷原子；X为卤素原子；任一个R独立地为取代或未取代的C1-10亚烷基、取代或未取代的C1-10卤代亚烷基、取代或未取代的C6-20亚芳基、以及取代或未取代的C6-20卤代亚芳基中的一种。
在本申请中，卤代亚烷基中的卤素原子可以为氟、氯、溴和碘中的一种或多种，进一步可以为氟。卤代亚烷基中的卤素原子个数可以为1个或多个。
在本申请中，卤代亚芳基中的卤素原子可以为氟、氯、溴和碘中的一种或多种，进一步可以为氟。卤代亚芳基中的卤素原子个数可以为1个或多个。
在一些实施方式中，任一个R独立地为Rc取代或未取代的C1-10亚烷基、Rc取代或未取代的C1- 10卤代亚烷基、Rc取代或未取代的C6-20亚芳基、以及Rc取代或未取代的C6-20卤代亚芳基中的一种。Rc取代的C1-10亚烷基中的取代基、Rc取代的C1-10卤代亚烷基中的取代基、Rc取代的C6-20亚芳基中的取代基和Rc取代的C6-20卤代亚芳基中的Rc取代基可以各自独立地包括下述取代基中的一种或多种：卤素原子、-CN、-NCO、-OH、-COOH、-SOOH、-OC＝(O)R41、-C＝(O)OR42、C1-10烷基、C2- 10烯基、C2-10炔基和C2-10烷氧基；其中，R41和R42各自独立地为C1-6烷基，例如甲基、乙基等。其中，Rc取代的C1-10亚烷基中的取代基、Rc取代的C1-10卤代亚烷基中的取代基、Rc取代的C6-20亚 芳基中的取代基和Rc取代的C6-20卤代亚芳基中的Rc取代基可以各自独立地选自下述取代基中的一种或多种：卤素原子、-CN、-NCO、-OH、-COOH、-SOOH、-OC＝(O)R41、-C＝(O)OR42、C1-10烷基、C2-10烯基、C2-10炔基和C2-10烷氧基；其中，R41和R42各自独立地为C1-6烷基，例如甲基、乙基等。在本申请中，如无其他说明，R中含有取代基RC时，RC的个数可以为1个或多个。
在一些实施方式中，在所述非水电解质中，Ma+中的M包括Li、Na、K、Rb、Cs、Mg、Ca、Ba、Al、Fe、Cu和Ni中的一种或多种。
在一些实施方式中，a、b和c各自独立地为选自1、2或3。
在一些实施方式中，m为1、2或3。
在一些实施方式中，n为0或1-4，进一步可以为0、1、2、3或4。
在一些实施方式中，所述第二添加剂包括二氟磷酸锂、单氟磷酸锂、四氟硼酸锂、氟磺酸锂和氟磺酸钠中的一种或多种。进一步地，可以为二氟磷酸锂、单氟磷酸锂、四氟硼酸锂、氟磺酸锂和氟磺酸钠中的一种或多种。
在一些实施方式中，所述第二添加剂在所述非水电解质中的质量占比(可记为W2)为0～11％。所述第二添加剂在所述非水电解质中的质量占比W2为下述任一种百分数：0、0.005％、0.01％、0.015％、0.02％、0.05％、0.1％、0.5％、1％、2％、3％、4％、5％、6％、7％、8％、10％、11％等，还可以选自上述任两种百分数构成的区间，例如0.005％～11％、0.01％～11％、0～10％、0.005％～10％、0.01％～10％、0.05％～10％、0.05％～5％等。当W2为0时，也即非水电解质中不添加第二添加剂。
第一添加剂二异氰酸酯的引入有可能加大形成的SEI膜的阻抗。通过向非水电解质中引入第二添加剂，可以在负极形成富含无机物的SEI膜，既能改善二次电池的快充性能，又能进一步改善二次电池的循环性能。
在一些实施方式中，所述负极活性物质的体积平均粒径Dv50≥6μm；其中，Dv50表示物质或材料的累计体积分布百分数达到50％时对应的粒径；可选地，所述负极活性物质的体积平均粒径Dv50为6μm～20μm；进一步可选地，所述负极活性物质的体积平均粒径Dv50为15μm～20μm。所述负极活性物质的Dv50还可以为下述任一种尺寸6μm、8μm、10μm、12μm、15μm、16μm、18μm、20μm等，还可以为上述任两种尺寸构成的区间。
在本申请的上下文中，可采用体积累计分布粒径DvN(其中，N表示选自0～100的任意数值)来表征物质或材料的粒径尺寸，指物质或材料的累计体积分布百分数达到N％时所对应的粒径，粒径小于等于DvN的体积占比为N％。DvN可以从物质或材料粒径的体积累积分布曲线上获得，如无其他说明，体积累积分布曲线自小粒径侧从零开始累计。以Dv50为例，Dv50是指物质或材料的累计体积分布百分数达到50％时所对应的粒径。以Dv50为例，表示占物质或材料体积50％的颗粒粒径小于等于Dv50，且占物质或材料体积50％的颗粒粒径大于Dv50。本领域技术人员可以理解Dv50的含义，而且可以采用本领域公知的仪器及方法进行测定。例如可以参照GB/T 19077-2016粒度分布激光衍射法，采用激光粒度分析仪方便地测定，如英国马尔文仪器有限公司的Mastersizer 2000E型激光粒度分析仪、LS-909激光粒度仪(欧美克)。
通过控制负极活性物质的粒径具有相对较大的粒径，可以减少负极材料与电解液的接触面积，降低在负极表面与溶剂发生副反应的概率，则更有利于降低极片膨胀率，可更佳地改善电芯的循环性能。
在一些实施方式中，所述负极活性物质的BET比表面积为0.5m2/g～2.0m2/g；可选地，所述负极活性物质的BET比表面积为0.8m2/g～1.5m2/g。所述负极活性物质的BET比表面积还可以为下述任一种数值或者选自下述任两种数值构成的区间：0.5m2/g、0.6m2/g、0.8m2/g、1m2/g、1.5m2/g、1.8m2/g、2m2/g等。
在本申请中，负极活性物质的BET比表面积可以采用(但不限于)如下的方法测试获得：采用氮气吸附比表面积分析测试方法测试，并用BET(Brunauer EmmettTeller)法计算得出，其中氮气吸附比表面积分析测试可以通过美国Micromeritics公司的Tri StarII型比表面与孔隙分析仪进行，测试步骤可以参照GB/T 19587-2004。待测样品：负极活性物质原料；还可以为负极极片的负极活性材料层中取样得到的负极活性物质。测试分析方法如下：将待测样品在真空干燥箱200℃下干燥2小时；然后采用氩气作为吸附气体，通过比表面与孔隙分析仪测绘相对压力P/P0为0～0.99的吸脱附曲线，P为平衡吸附压力，P0为饱和蒸汽压，通过BET方法计算出负极活性物质的比表面积。
通过控制负极活性物质的粒径具有一定的比表面积，可以减少负极材料的表面积，进而减少负极材料与电解液接触面积，从而减少溶剂在负极表面发生副反应，更好地改善电芯的循环性能。
负极极片
本申请中，二次电池中的负极极片包括负极活性材料层，所述负极活性材料层包括负极活性物质，所述负极活性物质包括石墨材料。
在一些实施方式中，负极极片包括负极集流体以及设置在负极集流体至少一个表面上的负极膜层，所述负极膜层包括负极活性材料层，所述负极活性材料层包括负极活性物质，所述负极活性物质包括石墨材料。
在一些实施方式中，石墨材料在负极活性物质中的重量百分比≥50％。石墨材料在负极活性物质中的重量百分比还可以为下述任一种百分数，或者大于等于下述任一种百分数，或者为下述任一种百分数至100％的区间，或者为下述任两种百分数构成的区间：50％、60％、70％、80％、90％、95％、96％、97％、98％、99％等。在一些实施方式中，石墨材料在负极活性物质中的重量百分比≥80％。在一些实施方式中，石墨材料在负极活性物质中的重量百分比为100％。
作为非限制性示例，负极集流体具有在其自身厚度方向相对的两个表面，负极膜层设置在负极集流体相对的两个表面中的任意一者或两者上。
在一些实施方式中，所述负极集流体可采用金属箔片或复合集流体。例如，作为金属箔片，可以采用铜箔。复合集流体可包括高分子材料基层和形成于高分子材料基材至少一个表面上的金属层。复合集流体可通过将金属材料形成在高分子材料基材上而得到。所述负极集流体中，该金属材料的非限制性示例可以包括铜、铜合金、镍、镍合金、钛、钛合金、银及银合金等中的一种或多种。所述负极集流体中，该高分子材料基材的非限制性示例可以包括聚丙烯(PP)、聚对苯二甲酸乙二醇酯(PET)、聚对苯二甲酸丁二醇酯(PBT)、聚苯乙烯(PS)、聚乙烯(PE)等基材中的一种或多种。
在一些实施方式中，负极活性物质中的石墨材料可以包括人造石墨和天然石墨中的一种或多种。负极活性物质还可以包括本领域公知的用于电池的其他负极活性物质。作为非限制性示例，负极活性物质还可以包括以下材料中的一种或多种：软炭、硬炭、硅基材料、锡基材料和钛酸锂等。所述硅基材料可以包括单质硅、硅氧化合物、硅碳复合物、硅氮复合物以及硅合金中的一种或多种。所述锡基材料可包括单质锡、锡氧化合物以及锡合金中的一种或多种。但本申请并不限定于这些材料，还可以使用其他可被用作电池负极活性物质的传统材料，只要其中含有石墨材料。这些负极活性物质可以仅单独使用石墨材料一种，也可以将两种以上组合使用(此时至少包括石墨材料)。
在一些实施例中，负极活性物质包括人造石墨。
在一些实施方式中，负极膜层还可选地包括粘结剂。所述粘结剂可包括丁苯橡胶(SBR)、聚丙烯酸(PAA)、聚丙烯酸钠(PAAS)、聚丙烯酰胺(PAM)、聚乙烯醇(PVA)、海藻酸钠(SA)、聚甲基丙烯酸(PMAA)及羧甲基壳聚糖(CMCS)中的一种或多种。
在一些实施方式中，负极膜层还可选地包括导电剂。导电剂可包括超导碳、乙炔黑、炭黑、科琴黑、碳点、碳纳米管、石墨烯及碳纳米纤维中的一种或多种。
在一些实施方式中，负极膜层还可选地包括其他助剂，例如增稠剂等。增稠剂的非限制性示例可以包括羧甲基纤维素钠(CMC-Na)等。
在一些实施方式中，可以通过以下方式制备负极极片：将上述用于制备负极极片的组分，例如负极活性物质、导电剂、粘结剂和任意其他组分分散于溶剂(溶剂的非限制性示例如去离子水)中，形成负极浆料；将负极浆料涂覆在负极集流体的至少一侧表面上，经烘干、压实(压实可以采用冷压方式)等工序后，即可得到负极极片。负极浆料所涂覆的负极集流体表面可以为负极集流体的单个表面上，也可以为负极集流体的两个表面上。负极浆料的固含量可以为40wt％～60wt％。负极极片的压实密度可以为1.4g/cm3～1.95g/cm3，进一步可选为1.5g/cm3～1.8g/cm3。
在本申请中，wt％表示重量百分含量。
正极极片
在本申请中，正极极片包括正极集流体以及设置在正极集流体至少一个表面上的正极膜层，该正极膜层包括正极活性材料层，进一步地，正极活性材料层包括正极活性物质。
作为非限制性示例，正极集流体具有在其自身厚度方向相对的两个表面，正极膜层设置在正极集流体相对的两个表面的其中任意一者或两者上。
在一些实施方式中，所述正极集流体可采用金属箔片或复合集流体。例如，作为金属箔片，可采用铝箔。复合集流体可包括高分子材料基层和形成于高分子材料基层至少一个表面上的金属层。复合集流体可通过将金属材料形成在高分子材料基材上而形成；金属材料可以包括铝、铝合金、镍、镍合金、钛、钛合金、银及银合金等中的一种或多种；高分子材料基材的非限制性示例包括聚丙烯(PP)、聚对苯二甲酸乙二醇酯(PET)、聚对苯二甲酸丁二醇酯(PBT)、聚苯乙 烯(PS)、聚乙烯(PE)等材质的基材。
在本申请的一些实施方式中，所述正极活性物质包括锂离子材料；进一步地，所述二次电池为锂离子二次电池。
在本申请的一些实施方式中，所述二次电池为锂离子二次电池。锂离子二次电池利用锂离子在电极的嵌入与脱嵌以及在电解质中的传输实现充放电过程。通常而言，锂离子二次电池中的活性离子为锂离子，但不限于此。
正极活性物质可采用本领域公知的用于电池的正极活性物质。作为非限制性示例，正极活性物质可包括以下材料或物质中的一种或多种：橄榄石结构的含锂磷酸盐、锂过渡金属氧化物及其各自的改性化合物。但本申请并不限定于这些材料或物质，还可以使用其他可被用作电池正极活性物质的传统材料或物质。这些正极活性物质可以仅单独使用一种，也可以将两种以上组合使用。其中，锂过渡金属氧化物的非限制性示例可包括但不限于锂钴氧化物、锂镍氧化物、锂锰氧化物、锂镍钴氧化物、锂锰钴氧化物、锂镍锰氧化物、锂镍钴锰氧化物、锂镍钴铝氧化物及其改性化合物等中的一种或多种。锂钴氧化物的非限制性示例包括LiCoO2；锂镍氧化物的非限制性示例包括LiNiO2；锂锰氧化物的非限制性示例包括LiMnO2、LiMn2O4等；锂镍钴锰氧化物的非限制性示例包括LiNi1/3Co1/3Mn1/3O2(也可以简称为NCM333)、LiNi0.5Co0.2Mn0.3O2(也可以简称为NCM523)、LiNi0.5Co0.25Mn0.25O2(也可以简称为NCM211)、LiNi0.6Co0.2Mn0.2O2(也可以简称为NCM622)、LiNi0.8Co0.1Mn0.1O2(也可以简称为NCM811)等。锂镍钴铝氧化物的非限制性示例包括LiNi0.85Co0.15Al0.05O2。橄榄石结构的含锂磷酸盐的非限制性示例可包括但不限于磷酸铁锂、磷酸铁锂与碳的复合材料、磷酸锰锂、磷酸锰锂与碳的复合材料、磷酸锰铁锂、磷酸锰铁锂与碳的复合材料中的一种或多种。磷酸铁锂的非限制性示例包括LiFePO4(也可以简称为LFP)；磷酸锰锂的非限制性示例包括LiMnPO4。
在一些实施方式中，所述正极活性物质可以包括但不限于下述材料中的一种或多种：磷酸铁锂、磷酸锰铁锂、锂钴氧化物、锂镍氧化物、锂锰氧化物、锂镍锰氧化物、锂镍钴锰氧化物、锂镍钴铝氧化物、钠氧化物和钾氧化物，以及前述任一种物质与掺杂元素构成的材料；进一步地，任一种正极活性物质中的掺杂元素独立地包括过渡金属元素和非过渡金属元素中的一种或多种。
在一些实施方式中，正极膜层还可选地包括粘结剂。作为非限制性示例，所述粘结剂可以包括聚偏氟乙烯(PVDF)、聚四氟乙烯(PTFE)、偏氟乙烯-四氟乙烯-丙烯三元共聚物、偏氟乙烯-六氟丙烯-四氟乙烯三元共聚物、四氟乙烯-六氟丙烯共聚物及含氟丙烯酸酯树脂中的一种或多种。
在一些实施方式中，正极膜层还可选地包括导电剂。作为非限制性示例，所述导电剂可以包括超导碳、乙炔黑、炭黑、科琴黑、碳点、碳纳米管、石墨烯及碳纳米纤维中的一种或多种。
在一些实施方式中，可以通过以下方式制备正极极片：将上述用于制备正极极片的组分，例如正极活性物质、导电剂、粘结剂和任意其他的组分分散于溶剂中，形成正极浆料；将正极浆料涂覆在正极集流体的至少一侧表面上，经烘干、压实(压实可以采用冷压方式)等工序后，即可得到正极极片。溶剂的种类可以包括但不限于前述实施方式中的任一种，例如N-甲基吡咯烷酮(NMP)。正极浆料所涂覆的正极集流体表面可以为正极集流体的单个表面上，也可以为正极集流体的两个表面上。正极浆料的固含量可以为40wt％～80wt％。正极极片的压实密度可以为3.0～3.6g/cm3，可选为3.3～3.5g/cm3。
电解质
电解质具有在正极极片和负极极片之间传导活性离子的作用。本申请中的电解质包括电解液。
在一些实施方式中，所述电解液为非水电解质。所述非水电解质可以包括电解质盐和溶剂。在锂离子二次电池中，电解质盐可以包括电解质锂盐。
在一些实施方式中，电解质锂盐可包括六氟磷酸锂(LiPF6)、四氟硼酸锂(LiBF4)、高氯酸锂(LiClO4)、六氟砷酸锂、双氟磺酰亚胺锂(LiFSI)、双三氟甲磺酰亚胺锂(LiTFSI)、三氟甲磺酸锂、二氟磷酸锂、二氟草酸硼酸锂、二草酸硼酸锂、二氟二草酸磷酸锂及四氟草酸磷酸锂中的一种或多种。
在一些实施方式中，该溶剂为有机溶剂。
在本申请中，非水电解质中的溶剂包括链状羧酸酯(记为第一溶剂)。第一溶剂的定义如前所述。
在一些实施方式中，除包括第一溶剂外，所述溶剂还可以包括醚类溶剂和碳酸酯类溶剂中的一种或多种。上述碳酸酯类溶剂可以包括碳酸酯及卤代碳酸酯中的一种或多种，作为非限制性示例，例如碳酸乙烯酯(EC)、碳酸丙烯酯(PC)、碳酸甲乙酯(EMC)、碳酸二乙酯(DEC)、碳酸二甲酯 (DMC)、碳酸二丙酯(DPC)、碳酸甲丙酯(MPC)、碳酸乙丙酯(EPC)以及前述任一种的氟代物中的一种或多种。
在另一些实施方式中，所述溶剂除包括第一溶剂外，还可以包括碳酸乙烯酯(EC，ethylene carbonate)、碳酸丙烯酯(PC)、碳酸甲乙酯(EMC)、碳酸二乙酯(DEC)、碳酸二甲酯(DMC)、碳酸二丙酯(DPC)、碳酸甲丙酯、碳酸乙丙酯、碳酸亚丁酯、氟代碳酸亚乙酯、1,4-丁内酯、环丁砜、二甲砜、甲乙砜及二乙砜中的一种或多种。
在一些实施方式中，所述溶剂除包括第一溶剂外，还包括碳酸乙烯酯(EC)和碳酸甲乙酯(EMC)中的一种或多种。在一些实施例中，所述溶剂包括碳酸乙烯酯。在一些实施例中，所述溶剂包括碳酸甲乙酯。在一些实施例中，所述溶剂包括碳酸乙烯酯和碳酸甲乙酯，进一步地，碳酸乙烯酯和碳酸甲乙酯的体积比可以为3:7，但不限于此。
在一些实施例中，所述溶剂为第一溶剂、碳酸乙烯酯和碳酸甲乙酯的组合。
在一些实施方式中，所述电解液还可选地包括添加剂。例如添加剂可以包括负极成膜添加剂、正极成膜添加剂，还可以包括能够改善电池某些性能的添加剂，例如改善电池过充性能的添加剂、改善电池高温或低温性能的添加剂等。
在一些实施方式中，所述添加剂可以包括碳酸亚乙烯酯(VC)、碳酸乙烯亚乙酯(VEC)、氟代碳酸乙烯酯(FEC)、二氟碳酸乙烯酯(DFEC)、三氟甲基碳酸乙烯酯(TFPC)、甲烷二磺酸亚甲酯(MMDS)、1-丙烯-1,3-磺酸内酯(PST)、亚硫酸乙烯酯(ES)、亚硫酸丙烯酯(PS)、硫酸乙烯酯(DTD)、丁二腈(SN)、己二腈(AND)、磺酸酯环状季铵盐、三(三甲基硅烷)磷酸酯(TMSP)、三(三甲基硅烷)硼酸酯(TMSB)及苯甲醚中的一种或多种。
在一些实施方式中，所述添加剂包括第一添加剂和第二添加剂中的一种或多种。
在一些实施方式中，所述添加剂包括第一添加剂。
在一些实施方式中，所述添加剂包括第二添加剂。
在一些实施方式中，所述添加剂包括第一添加剂和第二添加剂。
第一添加剂和第二添加剂的定义如前所述，包括但不限于种类和用量。
隔离膜
在一些实施方式中，二次电池中还包括隔离膜。本申请对隔离膜的种类没有特别的限制，可以选用任意公知的具有良好的化学稳定性和机械稳定性的多孔结构隔离膜。
在一些实施方式中，隔离膜的材质可包括玻璃纤维、无纺布、聚乙烯、聚丙烯及聚偏二氟乙烯中的一种或多种。隔离膜可以是单层薄膜，也可以是多层复合薄膜，没有特别限制。在隔离膜为多层复合薄膜时，各层的材料可以相同或不同，没有特别限制。
电极组件、电化学储能装置、二次电池
在一些实施方式中，正极极片、负极极片和隔离膜可通过卷绕工艺或叠片工艺制成电极组件。
在一些实施方式中，电化学储能装置可包括外包装。该外包装可用于封装上述电极组件及电解质。
在一些实施方式中，二次电池可包括外包装。该外包装可用于封装上述电极组件及电解质。
在一些实施方式中，二次电池的外包装可以是硬壳，例如硬塑料壳、铝壳、钢壳等。二次电池的外包装也可以是软包，例如袋式软包。软包的材质可以是塑料，进一步地，塑料的非限制性示例可以包括聚丙烯、聚对苯二甲酸丁二醇酯以及聚丁二酸丁二醇酯等中的一种或多种。
本申请对二次电池的形状没有特别的限制，其可以是圆柱形、方形或其他任意的形状。例如，图1是作为一个示例的方形结构的二次电池5。
在一些实施方式中，参照图2，外包装可包括壳体51和盖板53。其中，壳体51可包括底板和连接于底板上的侧板，底板和侧板围合形成容纳腔。壳体51具有与容纳腔连通的开口，盖板53能够盖设于所述开口，以封闭所述容纳腔。正极极片、负极极片和隔离膜可经卷绕工艺或叠片工艺形成电极组件52。电极组件52封装于所述容纳腔内。电解液浸润于电极组件52中。二次电池5所含电极组件52的数量可以为一个或多个，本领域技术人员可根据实际需求进行选择。
在一些实施方式中，所述二次电池具有如下的一种或多种效果：
快充时间：快充时间≤35min，进一步可以≤33min，更进一步可以≤32min，更进一步可以≤30min，更进一步可以≤28min；
负极极片膨胀：45℃循环至80％SOH负极极片膨胀率≤36％，进一步可以≤35.5％，更进一步可以≤33％，更进一步可以≤32％，更进一步可以≤30％，更进一步可以≤258％；
循环性能：45℃循环至80％SOH对应的圈数≥800，进一步可以≥900，更进一步可以≥950，更进一步可以≥1000，更进一步可以≥1100，更进一步可以≥1150，更进一步可以≥1200；
产气性能：60℃存储30D电芯膨胀率≤9％，进一步可以≤8％，更进一步可以≤7.5％，更进一步可以≤7％。
在一些实施方式中，所述二次电池在具有优良的快充能力、循环性能和安全性能的综合性能基础上，还具有优良的存储性能。在一些实施例中，60℃存储30D容量保持率≥85％，进一步可以≥88％，更进一步可以≥90％，更进一步可以≥95％。
一些实施例中，快充时间≤35min，45℃循环至80％SOH负极极片膨胀率≤33％，45℃循环至80％SOH对应的圈数≥900，60℃存储30D电芯膨胀率≤8％，进一步地，还满足60℃存储30D容量保持率≥88％。
一些实施例中，快充时间≤33min，45℃循环至80％SOH负极极片膨胀率≤32％，45℃循环至80％SOH对应的圈数≥1000，60℃存储30D电芯膨胀率≤8％，进一步地，还满足60℃存储30D容量保持率≥90％。
一些实施例中，快充时间≤30min，45℃循环至80％SOH负极极片膨胀率≤30％，45℃循环至80％SOH对应的圈数≥950，60℃存储30D电芯膨胀率≤8％，进一步地，还满足60℃存储30D容量保持率≥90％。
一些实施例中，快充时间≤35min，45℃循环至80％SOH负极极片膨胀率≤32％，45℃循环至80％SOH对应的圈数≥900，60℃存储30D电芯膨胀率≤7％，进一步地，还满足60℃存储30D容量保持率≥88％。
一些实施例中，快充时间≤30min，45℃循环至80％SOH负极极片膨胀率≤30％，45℃循环至80％SOH对应的圈数≥1000，60℃存储30D电芯膨胀率≤7％，进一步地，还满足60℃存储30D容量保持率≥90％。
一些实施例中，快充时间≤32min，45℃循环至80％SOH负极极片膨胀率≤33％，45℃循环至80％SOH对应的圈数≥1100，60℃存储30D电芯膨胀率≤7.5％，进一步地，还满足60℃存储30D容量保持率≥90％。
一些实施例中，快充时间≤28min，45℃循环至80％SOH负极极片膨胀率≤28％，45℃循环至80％SOH对应的圈数≥1200，60℃存储30D电芯膨胀率≤7.5％，进一步地，还满足60℃存储30D容量保持率≥95％。
第二方面，本申请提供了一种用电装置，其包括本申请第一方面所述二次电池。
所述二次电池可以用作所述用电装置的电源，也可以用作所述用电装置的能量存储单元。所述用电装置可以包括移动设备、电动车辆、电气列车、船舶及卫星、储能系统等，但不限于此。其中，移动设备例如可以是手机、笔记本电脑等；电动车辆例如可以是纯电动车、混合动力电动车、插电式混合动力电动车、电动自行车、电动踏板车、电动高尔夫球车、电动卡车等，但不限于此。
作为所述用电装置，可以根据其使用需求来选择二次电池。
图3是作为一个示例的用电装置6。该用电装置为纯电动车、混合动力电动车、或插电式混合动力电动车等。为了满足该用电装置对二次电池的高功率和高能量密度的需求，可以采用电池包或电池模块。
作为另一个示例的装置可以是手机、平板电脑、笔记本电脑等。该装置通常要求轻薄化，可以采用二次电池作为电源。
以下，说明本申请的一些实施例。下面描述的实施例是示例性的，仅用于解释本申请，而不能理解为对本申请的限制。实施例中未注明技术或条件的，按照上文中的描述进行，或者按照本领域内的文献所描述的技术或条件或者按照产品说明书进行。所用试剂或仪器未注明生产厂商者，均为可以通过市购获得的常规产品，或者可通过市购产品按照常规方式合成。
实施例1.
1.负极极片的制备
1.1.负极活性物质的种类根据表1选取，选取具有一定体积平均粒径Dv50和BET比表面积的负极活性物质。
(1)粒径测试
样本制备：负极活性物质原料；还可以为负极极片的负极活性材料层中取样得到的负极活性物质。为了避免干燥过程的团聚影响粒度的测试，取洗涤后湿润样品进行分散测试。
粒径尺寸类型：体积平均粒径Dv50的测试。
设备型号：马尔文3000(MasterSizer 3000)激光粒度仪，参考标准流程：GB/T19077-2016/ISO 13320:2009。
测试流程：取待测样品适量(样品浓度满足8％～12％遮光度即可)，加入20mL无水乙醇，超声处理5min(53KHz/120W)，使样品完全分散，之后按照GB/T19077-2016/ISO 13320:2009标准对样品进行测定。
(2)负极活性物质的BET比表面积测试
样本制备：负极活性物质原料；还可以为负极极片的负极活性材料层中取样得到的负极活性物质。
测试方法：采用氮气吸附比表面积分析测试方法测试，并用BET(Brunauer EmmettTeller)法计算得出，其中氮气吸附比表面积分析测试可以通过美国Micromeritics公司的Tri StarII型比表面与孔隙分析仪进行，测试步骤可以参照GB/T 19587-2004。
详细步骤如下：将待测样品在真空干燥箱200℃下干燥2小时；然后采用氩气作为吸附气体，通过比表面与孔隙分析仪测绘相对压力P/P0为0～0.99的吸脱附曲线，P为平衡吸附压力，P0为饱和蒸汽压，通过BET方法计算出负极活性物质的比表面积。
1.2.负极极片的制备
将负极活性物质人造石墨、导电剂碳黑、粘结剂丁苯橡胶(SBR)、增稠剂羧甲基纤维素钠(CMC-Na)按照重量比为90:4:4:2溶于溶剂去离子水中，混合均匀后制备成负极浆料(固含量为48％)；将负极浆料一次或多次均匀涂覆在负极集流体铜箔的双侧表面上，经过烘干、冷压、分切得到负极极片。负极极片的压实密度为1.65g/cm3。
其中，通过石墨颗粒的OI值、石墨颗粒的Dv50、负极极片的孔隙率、负极极片的压实密度、负极极片的组分种类及含量等中的至少一种参数调控负极极片OI值。
负极极片OI值的测试：采用X射线粉末衍射仪(X'pert PRO)测试004晶面衍射峰和110晶面衍射峰的强度，依据X射线衍射分析法通则以及石墨的点阵参数测定方法JIS K 0131-1996、JB/T4220-2011，得到X射线衍射谱图，然后根据OI＝I004/I110得到负极活性材料层的004晶面衍射峰与110晶面衍射峰的强度之比，其中，I004为004晶面衍射峰的强度，I110为110晶面衍射峰的强度。
负极极片电阻值R的测试：采用BER1300多功能极片电阻仪进行测试。首先将负极极片裁成一定尺寸(直径为40mm的小圆片)的待测样品；将待测样品放置于两个探针之间，记录测试结果。取多个(≥5)待测样品，并计算多个待测样品的平均值作为测试结果。
2、电解液(非水电解质)的配制
在氩气气氛手套箱中(H2O<0.1ppm，O2<0.1ppm)，将碳酸乙烯酯(EC)和碳酸甲乙酯(EMC)按照体积比3:7混合均匀。向其中加入基于溶剂总重量计60wt％的乙酸甲酯。随后加入六氟磷酸锂(LiPF6)溶解于有机溶剂中，使LiPF6的浓度为12.5wt％，搅拌均匀，得到电解液。
3、正极极片的制备
将磷酸铁锂正极材料、导电剂乙炔黑、粘结剂聚偏二氟乙烯(PVDF)按重量比为90:5:5加入溶剂N-甲基吡咯烷酮(NMP)中，充分搅拌混合均匀后得到正极浆料(固含量为67％)；之后将正极浆料均匀涂覆于正极集流体的双侧表面上，单侧涂布重量约为22.7mg/cm2(如350mg/1540.25mm2)；再经过烘干、冷压、分切，得到正极极片。
4、隔膜
以常规市售聚丙烯膜作为隔离膜。
5、二次电池的组装
将正极极片(宽87mm×长605mm)、隔离膜(宽98mm×长1896mm)、负极极片(宽93mm×长735mm)按顺序叠好，使隔离膜处于正、负极片之间起到隔离的作用，然后卷绕得到电极组件；将电极组件置于电池壳体中，干燥后注入电解液12.0g(3Ah，注液系数4.0g/Ah)，再经过化成、静置等工艺制得锂离子电池。
实施例2～41及对比例1-9采用与实施例1基本相同的方法，区别之处在于负极活性物质的种类、负极OI值、负极极片的电阻值R、第一溶剂(链状羧酸酯)的种类及用量、第一添加剂的种类及用量、第二添加剂的种类及用量、负极活性物质的Dv50与比表面积(BET)中的一个或多个参数，可参阅表1和表2。
表1.

表1中，W0为第一溶剂在电解液溶剂中的质量占比。
表2.

表1中，W1为第一添加剂在电解液(非水电解质)中的质量占比；W2为第二添加剂在电解液(非水电解质)中的质量占比。
测试分析方法
1、快充性能测试
在25℃下，将分容后的电池进行2.5V～3.65V充放电测试。测试步骤为：先3C恒流充电到30％SOC，2C恒流充电到60％SOC，1C恒流恒压充电到80％SOC，截止电流为0.01C，静置5min；1C恒流放电到2.0V，静置5min。测定电池充电至80％SOC的时间。
其中，SOC表示电池剩余容量情况，其取值范围为0～100％，当SOC＝0时表示电池放电完全，当SOC＝100％时表示电池完全充满。
2、极片膨胀率测试(45℃循环至80％SOH极片膨胀率)
在45℃下，将锂离子电池以0.5C恒流充电至3.65V，然后以3.65恒压充电至电流小于0.05C，然后将锂离子电池以0.5C恒流放电至2.5V，此为一个充放电过程(也即，1圈)。采用万分尺(Mitutoyo293-100、精度为0.01mm)测量负极极片的厚度L0。如此反复进行充电和放电，记录容量保持率为80％时负极极片的厚度L1；45℃循环至80％SOH负极极片膨胀率＝(L1/L0-1)×100％。
3、循环性能测试
在45℃下，将锂离子电池以0.5C恒流充电至3.65V，然后以3.65恒压充电至电流小于0.05C，然后将锂离子电池以0.5C恒流放电至2.5V，此为一个充放电过程(也即，1圈)。如此反复进行充电和放电，记录容量保持率为80％时的循环圈数。记为“45℃循环至80％SOH对应的圈数”。
4、产气性能测试
以0.33C的恒定电流对锂离子二次电池充电至3.65V，再以3.65V恒定电压充电至电流为0.05C，将锂离子电池充满电。采用排水法测试电池的体积，此时体积记为存储前体积。之后将锂离子电池置于60℃下存储30天，待存储结束后，将锂离子二次电池置于25℃环境下，采用排水法测试电池的体积，此时体积记为存储后体积。按照下式计算电池的体积膨胀率：
电池体积膨胀率＝(存储后体积/存储前体积-1)×100％。
记为“60℃存储30D电芯膨胀率”。该数值越低，反映了产气量越低，该数值越低，产气性能越好。
5、存储性能测试
在25℃下，将锂离子电池以0.33C恒流充电至3.65V，然后以3.65恒压充电至电流小于0.05C，然后将锂离子电池以0.33C恒流放电至2.5V(电池放电容量记录为C0)。将满充后的电池放置于60℃烘箱中搁置30天，取出电池，将电池放置于25℃环境中，进行0.33C放电，放电容量记录为C1；容量保持率＝(C1/C0)×100％，记为“60℃存储30D容量保持率”。
测试分析结果
测试结果可参阅表3。
实施例1～41制备的二次电池在快充能力、低负极极片膨胀以及电池循环性能方面取得了优良的综合性能，其中，高温产气测试中的电芯膨胀率还反映了产气性能，可参考快充时间、45℃循环至80％SOH负极极片膨胀率、45℃循环至80％SOH对应的圈数和60℃存储30D电芯膨胀率数据。此外，实施例1～41制备的二次电池还具有优良的存储性能(可参考60℃存储30D容量保持 率数据)。
对比例1～9的W0×100/(R×OI)或小于0.08，或大于5，导致二次电池在快充能力、循环性能和安全性能方面的综合性能均明显劣于实施例1～41。
对比例1～5中的OI值、负极极片电阻值R与W0，虽然单个参数的取值均可用于本申请技术方案，然而，其组合关系不符合0.08≤W0×100/(R×OI)≤5，导致难以兼顾较优的快充能力、低极片膨胀、低产气电芯膨胀以及较优的循环性能，在快充能力、低极片膨胀、低电芯膨胀以及较优的循环性能中至少一种性能参数明显不佳或并未改善。其中，对比例1中，W0×100/(R×OI)大于5，负极极片脱模，导致电芯无法工作。对比例2的负极极片膨胀明显较大，对比例3的电芯膨胀明显较大，对比例4-5的快充能力显著变差。
对比例6中OI值略大，但W0×100/(R×OI)过小；对比例7中负极极片电阻R值略低，但W0×100/(R×OI)过大；对比例8中R值略高，但W0×100/(R×OI)过小；对比例9中链状羧酸酯(第一溶剂)含量略高，但W0×100/(R×OI)过大，结果对比例6-9中均未能在快充能力、循环性能和安全性能方面实现优良的综合效果。
对比例7和对比例9虽然具有较短的快充时间，然而其代价是加重了极片膨胀，循环性能显著恶化，高温产气后的电芯膨胀明显变大，存储性能也不佳。
对比例8虽然在极片膨胀有所抑制，然而，牺牲了快充能力，而且循环性能显著恶化，而且产气后电芯膨胀仍较大。
表3.

以上所述实施例的各技术特征可以进行任意的组合，为使描述简洁，未对上述实施例中的各个技术特征所有可能的组合都进行描述，然而，只要这些技术特征的组合不存在矛盾，都应当认为是本说明书记载的范围。
需要说明的是，本申请不限定于上述实施方式。上述实施方式仅为示例，在本申请的技术方案范围内具有与技术思想实质相同的构成、发挥相同作用效果的实施方式均包含在本申请的技术范围内。以上所述实施例仅表达了本申请的几种实施方式，其描述较为详细，但并不能因此而理解为对专利范围的限制。此外，在不脱离本申请主旨的范围内，对实施方式施加本领域技术人员能够想到的各种变形、将实施方式中的一部分构成要素加以组合而构筑的其它方式也包含在本申请的范围内。应当指出的是，对于本领域的普通技术人员来说，在不脱离本申请构思的前提下，还可以做出若干变形和改进，这些都属于本申请的保护范围。因此，本申请的保护范围应以所附权利要求为准，说明书及附图可用于解释权利要求的内容。

Claims (20)

  1. 一种二次电池，其包括正极极片、负极极片和非水电解质；其中，所述负极极片包括负极活性物质，所述负极活性物质包括石墨材料；所述非水电解质包括溶剂，所述溶剂包括第一溶剂，所述第一溶剂为链状羧酸酯；
    所述负极极片的OI值、所述负极极片的电阻值R与所述第一溶剂在所述溶剂中的质量占比W0满足如下关系：0.08/mΩ≤W0×100/(R×OI)≤5/mΩ；
    其中，所述负极极片的OI值是指所述石墨材料的004晶面衍射峰强度与110晶面衍射峰强度的比值；R的单位为mΩ。
  2. 根据权利要求1所述的二次电池，其中，6≤OI≤25；
    可选地，6≤OI≤18；
    进一步可选地，12≤OI≤18。
  3. 根据权利要求1或2所述的二次电池，其中，1mΩ≤R≤50mΩ；
    可选地，5mΩ≤R≤30mΩ；
    进一步可选地，10mΩ≤R≤20mΩ。
  4. 根据权利要求1～3中任一项所述的二次电池，其中，10％≤W0≤80％；
    可选地，20％≤W0≤80％；进一步可选地，30％≤W0≤70％；更进一步可选地，50％≤W0≤70％；
    另可选地，10％≤W0≤60％；进一步可选地，20％≤W0≤60％。
  5. 根据权利要求1～4中任一项所述的二次电池，其中，0.67≤W0×100/OI≤10；
    可选地，1≤W0×100/OI≤10；进一步可选地，1≤W0×100/OI≤5；更进一步可选地，3≤W0×100/OI≤5；
    另可选地，0.67≤W0×100/OI≤4；进一步可选地，1≤W0×100/OI≤4。
  6. 根据权利要求1～5中任一项所述的二次电池，其中，
    0.1/mΩ≤W0×100/(R×OI)≤5/mΩ；
    可选地，0.1/mΩ≤W0×100/(R×OI)≤2/mΩ。
  7. 根据权利要求1～6中任一项所述的二次电池，其中，
    6≤OI≤18，10mΩ≤R≤20mΩ，且10％≤W0≤80％；
    可选地，12≤OI≤18，10mΩ≤R≤20mΩ，且10％≤W0≤60％；进一步可选地，20％≤W0≤60％；
    另可选地，12≤OI≤18，10mΩ≤R≤20mΩ，且50％≤W0≤70％。
  8. 根据权利要求1～7中任一项所述的二次电池，其中，所述第一溶剂包括结构如式(1)所示的化合物：
    其中，R1和R2分别独立地为C1-3烷基或C1-3卤代烷基；
    可选地，R1和R2分别独立地为C1-3烷基或C1-3氟代烷基；
    进一步可选地，R1和R2分别独立地为甲基、乙基、丙基、氟代甲基、氟代乙基和氟代丙基中的一种；
    更进一步可选地，R1和R2分别独立地为甲基、乙基、氟代甲基和氟代乙基中的一种；
    更进一步可选地，所述第一溶剂包括下述化合物中的一种或多种：乙酸甲酯、乙酸乙酯、二氟乙酸甲酯和二氟乙酸乙酯。
  9. 根据权利要求1～8中任一项所述的二次电池，其中，所述非水电解质还包括第一添加剂；所述第一添加剂为二异氰酸酯。
  10. 根据权利要求1～8中任一项所述的二次电池，其中，所述第一添加剂包括结构如下的化合物：O＝C＝N-R3-N＝C＝O    式(2)；
    其中，R3为未取代的或Ra取代的C1-18亚烃基；Ra包括下述取代基中的一种或多种：卤素原子、-CN、-NCO、-OH、-COOH、-SOOH、-OC(＝O)R11、R12OC(＝O)-、C1-10烷基、C2-10烯基、C2- 10炔基和C2-10氧杂烷基中的一种或多种；R11和R12分别独立地为烷基或卤代烷基；
    可选地，R3为C2-10亚烷基、C2-10杂亚烷基、C6-18亚芳基、C2-18杂亚芳基、C3-18亚脂环基或C3-18杂亚脂环基，前述任一种基团为未取代的或者为Ra取代的；
    另可选地，R3为未取代的或Ra取代的C2-10亚烷基、未取代的或Ra取代的C3-18二价环烷基或未取代的或Ra取代的C6-18亚芳基；进一步可选地，R3为C2-10亚烷基、C6-18二价环烷基或C6- 18亚芳基；更进一步可选地，R3为C4-10亚烷基、C6-14二价环烷基或C6-14亚芳基；更进一步可选地，R3为C4-10亚烷基、C6-10二价环烷基或C6-10亚芳基；更进一步可选地，R3为C4-8亚己基、含有己环的C6-10二价环烷基或含有苯环的C6-10亚芳基；
    另可选地，所述第一添加剂包括下述化合物中的一种或多种：六亚甲基二异氰酸酯、1,4-环己烷二甲基二异氰酸酯、1,3-苯二异氰酸酯和2,4-二异氰酸-1-甲苯。
  11. 根据权利要求8～10中任一项所述的二次电池，其中，所述第一添加剂在所述非水电解质中的质量占比为0～11％；
    可选地，所述第一添加剂在所述非水电解质中的质量占比为0.005％～11％；
    进一步可选地，所述第一添加剂在所述非水电解质中的质量占比为0.005％～10％；
    更进一步可选地，所述第一添加剂在所述非水电解质中的质量占比为0.01％～10％；
    更进一步可选地，所述第一添加剂在所述非水电解质中的质量占比为0.1％～5％；
    更进一步可选地，所述第一添加剂在所述非水电解质中的质量占比为1％～5％。
  12. 根据权利要求1～11中任一项所述的二次电池，其中，所述非水电解质还包括第二添加剂；所述第二添加剂包括单氟磷酸锂、二氟磷酸锂、四氟硼酸锂、式(3)所示化合物和氟磺酸盐中的一种或多种；
    式(3)中，a、b和c各自独立地为正整数，m为选自1-3的整数，n为选自0-4的整数，q为0或1；Ma+为带有a价正电荷的金属离子；任一个Y独立地为硼原子或磷原子；X为卤素原子；任一个R独立地为取代或未取代的C1-10亚烷基、取代或未取代的C1-10卤代亚烷基、取代或未取代的C6-20亚芳基、以及取代或未取代的C6-20卤代亚芳基中的一种；
    可选地，任一个R独立地为Rc取代或未取代的C1-10亚烷基、Rc取代或未取代的C1-10卤代亚烷基、Rc取代或未取代的C6-20亚芳基、以及Rc取代或未取代的C6-20卤代亚芳基中一种；Rc取代的C1-10亚烷基中的取代基、Rc取代的C1-10卤代亚烷基中的取代基、Rc取代的C6-20亚芳基中的取代基和Rc取代的C6-20卤代亚芳基中的Rc取代基可以各自独立地包括下述取代基中的一种或多种：卤素原子、-CN、-NCO、-OH、-COOH、-SOOH、-OC＝(O)R41、-C＝(O)OR42、C1-10烷基、C2-10烯基、C2-10炔基和C2-10烷氧基；其中，R41和R42各自独立地为C1-6烷基；
    可选地，在所述非水电解质中，Ma+中的M包括Li、Na、K、Rb、Cs、Mg、Ca、Ba、Al、Fe、Cu和Ni中的一种或多种；
    可选地，a、b和c各自独立地为选自1、2或3。
  13. 根据权利要求12所述的二次电池，其中，所述第二添加剂包括二氟磷酸锂、单氟磷酸锂、四氟硼酸锂、氟磺酸锂和氟磺酸钠中的一种或多种。
  14. 根据权利要求12～13中任一项所述的二次电池，其中，所述第二添加剂在所述非水电解质中的质量占比为0.005％～11％；
    可选地，所述第二添加剂在所述非水电解质中的质量占比为0.005％～11％；
    进一步所述第二添加剂在所述非水电解质中的质量占比为0.005％～10％；
    更进一步可选地，所述第二添加剂在所述非水电解质中的质量占比为0.05％～5％。
  15. 根据权利要求1～14中任一项所述的二次电池，其中，所述负极活性物质的体积平均粒径Dv50≥6μm；其中，Dv50表示物质或材料的累计体积分布百分数达到50％时对应的粒径；
    可选地，所述负极活性物质的体积平均粒径Dv50为6μm～20μm；
    进一步可选地，所述负极活性物质的体积平均粒径Dv50为15μm～20μm。
  16. 根据权利要求1～15中任一项所述的二次电池，其中，所述负极活性物质的BET比表面积为0.5m2/g～2.0m2/g；
    可选地，所述负极活性物质的BET比表面积为0.8m2/g～1.5m2/g。
  17. 根据权利要求1～16中任一项所述的二次电池，其中，所述石墨材料包括人造石墨和天然石墨中的一种或多种；
    可选地，所述石墨材料包括人造石墨。
  18. 根据权利要求1～17中任一项所述的二次电池，其中，所述石墨材料在所述负极活性物质中的重量百分比≥50％；
    可选地，所述石墨材料在所述负极活性物质中的重量百分比≥80％；
    进一步可选地，所述石墨材料在所述负极活性物质中的重量百分比为100％。
  19. 根据权利要求1～18中任一项所述的二次电池，其中，所述二次电池为锂离子二次电池。
  20. 一种用电装置，其包括权利要求1～19中任一项所述的二次电池。
PCT/CN2023/091698 2023-04-28 2023-04-28 二次电池和用电装置 Ceased WO2024221426A1 (zh)

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