WO2024021020A1 - 电解液、二次电池、电池模块、电池包和用电装置 - Google Patents

电解液、二次电池、电池模块、电池包和用电装置 Download PDF

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WO2024021020A1
WO2024021020A1 PCT/CN2022/108958 CN2022108958W WO2024021020A1 WO 2024021020 A1 WO2024021020 A1 WO 2024021020A1 CN 2022108958 W CN2022108958 W CN 2022108958W WO 2024021020 A1 WO2024021020 A1 WO 2024021020A1
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Prior art keywords
lithium
electrolyte
optionally
battery
solvent
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PCT/CN2022/108958
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English (en)
French (fr)
Inventor
王瀚森
刘成勇
谢张荻
黄圣源
胡波兵
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Contemporary Amperex Technology Co Ltd
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Contemporary Amperex Technology Co Ltd
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Priority to EP22952468.1A priority Critical patent/EP4481875A4/en
Priority to PCT/CN2022/108958 priority patent/WO2024021020A1/zh
Priority to KR1020247022461A priority patent/KR20240116813A/ko
Priority to CN202280085677.2A priority patent/CN118489173A/zh
Priority to JP2024539867A priority patent/JP7815453B2/ja
Publication of WO2024021020A1 publication Critical patent/WO2024021020A1/zh
Priority to US18/755,332 priority patent/US20240347776A1/en
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    • 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
    • H01M10/052—Li-accumulators
    • 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
    • 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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
    • 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
    • H01M2300/0034—Fluorinated solvents
    • 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 lithium batteries, and in particular to an electrolyte, a secondary battery, a battery module, a battery pack and an electrical device.
  • Secondary batteries have been widely used in many fields such as consumer electronics, electric vehicles, and energy storage. For common lithium-ion secondary batteries, improvements in energy density have come close to reaching the theoretical limit. In order to meet future scenarios with higher energy density requirements, including high-endurance electric vehicles, electric aircraft, etc., it is necessary to develop secondary batteries with greater energy density potential, such as metallic lithium secondary batteries that match lithium metal anodes with high-voltage cathodes such as ternary. Battery.
  • metallic lithium anode has high reactivity and easily reacts spontaneously with the electrolyte to form a solid electrolyte interface layer (SEI) with poor mechanical strength and chemical stability, causing dendrite-like growth morphology, so the cycle ability is poor. Good, but there are safety risks, and lifespan failure caused by rapid lithium source consumption.
  • SEI solid electrolyte interface layer
  • the design and optimization of electrolyte is crucial.
  • the electrolyte in the prior art has a systemic "transient" overcharge problem in metallic lithium anode secondary batteries, which may bring about difficult battery management difficulties and safety risks.
  • This application was made in view of the above-mentioned problems, and its purpose is to provide an electrolyte that can avoid overcharging, thereby improving the cycle stability and safety of lithium-ion secondary batteries and extending the cycle life.
  • the present application provides an electrolyte and a secondary battery, a battery module, a battery pack and an electrical device including the electrolyte.
  • a first aspect of the application provides an electrolyte solution including:
  • the first solvent as shown in Formula I;
  • R 1 is selected from C1-C6 fluorinated alkyl
  • R 2 is selected from a hydrogen atom, a C1-C6 alkyl group and a C1-C6 fluorinated alkyl group;
  • n 1 or 2;
  • the second solvent is one or more compounds selected from Formula II and Formula III;
  • R 3 to R 10 are each independently selected from a hydrogen atom, a fluorine atom, a C1-C6 alkyl group and a C1-C6 fluorinated alkyl group.
  • the electrolyte of the present application can avoid the "transient" overcharge problem of secondary batteries in long cycles and improve cycle stability and safety.
  • the electrolyte of the present application has high oxidation stability and can improve the cycle life of metal or alloy negative electrode secondary batteries.
  • R 1 is selected from C1-C3 fluorinated alkyl group, optionally fluoromethyl; and/or, R 2 is selected from hydrogen atom, C1-C3 Alkyl and C1-C3 fluorinated alkyl are optionally selected from hydrogen atoms, methyl, fluoromethyl, ethyl and fluoroethyl.
  • R 3 to R 8 are each independently selected from a hydrogen atom, a fluorine atom and a C1-C6 fluorinated alkyl group, optionally selected from a hydrogen atom, a fluorine atom and a C1 -C3 fluorinated alkyl group; and/or in the formula III, R 9 to R 10 are each independently selected from a hydrogen atom, a fluorine atom, a C1-C6 alkyl group and a C1-C6 fluorinated alkyl group.
  • R 9 to R 10 are each independently selected from hydrogen atoms and fluorine atom.
  • first and second solvents can make the electrolyte have higher oxidation stability, avoid overcharging, and improve cycle life.
  • the weight ratio of the first solvent to the second solvent is 0.5 to 3, optionally 0.7 to 1.5, more optionally 0.9 to 1.1. Keeping the weight ratio of the two solvents within the above range can avoid overcharging, ensure good dissolution of the electrolyte salt in the electrolyte, and make the electrolyte have better antioxidant capacity and longer cycle life.
  • the electrolyte further includes an antioxidant; optionally, the antioxidant is selected from at least one of lithium nitrate and lithium perchlorate. Adding antioxidants helps further improve cycle life.
  • the concentration of the antioxidant is 0.5% to 3% by weight, optionally 0.7% to 1.5% by weight, more optionally 0.9% to 1.1% by weight, based on the total electrolyte solution. Weight scale.
  • the addition of antioxidants can further increase the critical voltage value of oxidation stability and further improve the cycle life.
  • the content of antioxidants within the above range can fully exert the above effects while avoiding excessive impact on the normal transmission of lithium ions, resulting in reduced cycle life.
  • the electrolyte further includes a fluorine-containing electrolyte salt
  • the fluorine-containing electrolyte salt is selected from the group consisting of lithium bisfluorosulfonyl imide, lithium hexafluorophosphate, lithium tetrafluoroborate, lithium hexafluoroarsenate, At least one of lithium bistriflate, lithium trifluoromethanesulfonate, lithium difluorophosphate, lithium difluoroborate, lithium difluorodioxalate and lithium tetrafluoroxalate, more optionally , the fluorine-containing electrolyte salt is lithium bisfluorosulfonimide.
  • the use of the above electrolyte salts can help improve the stability of the negative electrode interface and improve cycle performance.
  • the concentration of the fluoroelectrolyte salt is 0.5M to 3M, optionally 1M. This concentration of electrolyte salts helps further improve cycle performance.
  • a second aspect of the application provides a secondary battery, including the electrolyte of the first aspect of the application.
  • a third aspect of the present application provides a battery module including the secondary battery of the second aspect of the present application.
  • a fourth aspect of the application provides a battery pack, including the battery module of the third aspect of the application.
  • a fifth aspect of the present application provides an electrical device, including at least one selected from the secondary battery of the second aspect of the present application, the battery module of the third aspect, or the battery pack of the fourth aspect of the present application.
  • the electrolyte of the present application can improve the cycle stability of lithium-ion secondary batteries, increase cycle life, avoid overcharging, and improve battery safety performance.
  • Figure 1 is a cycle life diagram of a secondary battery containing a prior art electrolyte.
  • Figure 2 shows the oxidation stability test results of the electrolyte in the prior art.
  • Figure 3 shows the oxidation stability test results of conventional ether electrolytes and fluorine-containing electrolytes.
  • FIG. 4 is a cycle life diagram of a secondary battery including an electrolyte solution according to an embodiment of the present application.
  • Figure 5 is a cycle voltage-capacity curve of the secondary battery of Comparative Example 1.
  • FIG. 11 is a schematic diagram of a secondary battery according to an embodiment of the present application.
  • FIG. 12 is an exploded view of the secondary battery according to the embodiment of the present invention shown in FIG. 11 .
  • Figure 13 is a schematic diagram of a battery module according to an embodiment of the present application.
  • Figure 14 is a schematic diagram of a battery pack according to an embodiment of the present application.
  • FIG. 15 is an exploded view of the battery pack according to one embodiment of the present application shown in FIG. 14 .
  • FIG. 16 is a schematic diagram of a power consumption device using a secondary battery as a power source according to an embodiment of the present application.
  • Ranges disclosed herein are defined in terms of lower and upper limits. A given range is defined by selecting a lower limit and an upper limit that define the boundaries of the particular range. Ranges defined in this manner may be inclusive or exclusive of the endpoints, and may be arbitrarily combined, that is, any lower limit may be combined with any upper limit to form a range. For example, if ranges of 60-120 and 80-110 are listed for a particular parameter, understand that ranges of 60-110 and 80-120 are also expected. Furthermore, if the minimum range values 1 and 2 are listed, and if the maximum range values 3, 4, and 5 are listed, then the following ranges are all expected: 1-3, 1-4, 1-5, 2- 3, 2-4 and 2-5.
  • the numerical range “a-b” represents an abbreviated representation of any combination of real numbers between a and b, where a and b are both real numbers.
  • the numerical range “0-5" means that all real numbers between "0-5" have been listed in this article, and "0-5" is just an abbreviation of these numerical combinations.
  • a certain parameter is an integer ⁇ 2
  • 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.
  • step (c) means that step (c) may be added to the method in any order.
  • the method may include steps (a), (b) and (c). , may also include steps (a), (c) and (b), may also include steps (c), (a) and (b), etc.
  • condition "A or B” is satisfied by any of the following conditions: 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).
  • Secondary batteries have been widely used in many fields such as consumer electronics, electric vehicles, and energy storage. For common lithium-ion secondary batteries, improvements in energy density have come close to reaching the theoretical limit. In order to meet future application scenarios that require higher energy density, including high-endurance electric vehicles and electric aircraft, secondary batteries with greater energy density potential have been developed, such as metal or alloy anode ion secondary batteries.
  • a secondary battery containing an electrolyte of the prior art performs well within a certain cycle number range (as shown in Figure 1) during a long cycle.
  • an electrolyte of the prior art e.g., LiFSI-DME-TTE system
  • the overcharge phenomenon occurs when the charging capacity exceeds the rated capacity, but the discharge capacity remains normal or only slightly decreases (around 40-65 cycles). If the cycle continues after this number of cycles, the above-mentioned overcharge phenomenon will gradually weaken until it disappears. Restore normal circulation.
  • this application provides an electrolyte that can avoid the above-mentioned "transient" overcharge problem, improve the safety of metal or alloy negative electrode secondary batteries, and improve cycle performance.
  • an electrolyte solution including:
  • the first solvent as shown in Formula I:
  • R 1 is selected from C1-C6 fluorinated alkyl
  • R 2 is selected from a hydrogen atom, a C1-C6 alkyl group and a C1-C6 fluorinated alkyl group;
  • n 1 or 2;
  • the second solvent is one or more compounds selected from Formula II and Formula III;
  • R 3 to R 10 are each independently selected from a hydrogen atom, a fluorine atom, a C1-C6 alkyl group and a C1-C6 fluorinated alkyl group.
  • the electrolyte of the present application can effectively avoid the above-mentioned "transient" overcharge problem in long-term cycles of secondary batteries, especially lithium-ion secondary batteries with metal or alloy negative electrodes, thereby improving the cycle stability and safety of the battery; at the same time , the electrolyte of the present application also has high oxidation stability, and can improve the cycle life of metal or alloy negative electrode secondary batteries.
  • the inventor found that the intrinsic antioxidant capacity of ether electrolytes in the prior art is not too bad, for example, in the scanning voltammogram (LSV) test of Li-Al batteries, the The oxidation stability window of the methyl ether (DME)-1,1,2,2-difluoroethyl-2,2,3,3-difluoropropyl ether (TTE) electrolyte system can reach 5.3V (see Figure 2 ); however, when this electrolyte is applied to, for example, Li-NMC811 cells for long cycles, the aforementioned "transient" overcharge problem will occur without exception (see, for example, Comparative Example 3 and Figure 7 below).
  • the electrolyte of the present application has good oxidation resistance and can effectively avoid the occurrence of the "transient" overcharge phenomenon.
  • R 1 is selected from C1-C3 fluorinated alkyl, optionally fluoromethyl. In some embodiments, R 1 is more optionally monofluoromethyl or difluoromethyl.
  • R 2 is selected from a hydrogen atom, a C1-C3 alkyl group and a C1-C3 fluorinated alkyl group, optionally selected from a hydrogen atom, a methyl group, a fluorinated alkyl group, Methyl, ethyl and fluoroethyl.
  • R2 is more optionally selected from a hydrogen atom, methyl, monofluoromethyl, difluoromethyl, ethyl, monofluoroethyl, and difluoroethyl.
  • the first solvent of Formula I is selected from the following compounds:
  • the first solvent of formula I is selected from at least one of formulas I-1 to I-16, and formulas I-60 to I-71; more optionally, formulas I-2 and I - at least one of 65.
  • an ether with a smaller carbon chain length for example, a C1-3 alkyl group
  • an ether with an alkyl group with a longer carbon chain and/or a higher fluorine content for example, ethers with a not too high fluorine content (for example, monofluoro or difluoro).
  • the first solvent gives the electrolyte a higher boiling point and higher oxidation stability, which can improve its positive electrode side oxidation stability; at the same time, the first solvent has good dissolving ability for electrolyte salts (for example, bisfluorosulfonimide
  • the dissolved concentration of lithium (LiFSI) in the first solvent can reach 2M or even higher).
  • the electrolyte oxidation stability of the Li-Al half-cell LSV test reached at least about 5.3V (see Figure 3).
  • the second solvent represented by formula II and formula III does not dissolve or slightly dissolves the electrolyte lithium salt, and can be miscible with the first solvent in any ratio without phase separation.
  • R 3 to R 8 are each independently selected from a hydrogen atom, a fluorine atom and a C1-C6 fluorinated alkyl group.
  • R 3 to R 8 are each independently selected from a hydrogen atom, a fluorine atom and a C1-C3 fluorinated alkyl group.
  • R 3 to R 8 are each independently selected from a hydrogen atom, a fluorine atom and a fluoromethyl group.
  • the solvent of Formula II is selected from the following compounds:
  • the second solvent of Formula II is selected from at least one of difluorobenzene and fluoromethylbenzene, optionally selected from difluorobenzene and trifluoromethylbenzene. At least one, more optionally at least one selected from the compounds of formulas II-7, II-8, II-9 and II-12.
  • R 9 to R 10 are each independently selected from a hydrogen atom, a fluorine atom, a C1-C6 alkyl group and a C1-C6 fluorinated alkyl group. In some embodiments, optionally, R 9 to R 10 are each independently selected from a hydrogen atom, a fluorine atom, a C1-C3 alkyl group and a C1-C3 fluorinated alkyl group. In some embodiments, more optionally, each of R 9 to R 10 is independently selected from a hydrogen atom or a fluorine atom.
  • one or more hydrogen atoms of the alkyl group are each independently substituted with a fluorine atom.
  • the solvent of Formula III is selected from the following compounds:
  • the second solvent of Formula III is selected from fluoromethoxybenzene, optionally selected from at least one of the compounds of Formula III-1, III-2 and III-3. In some embodiments, the second solvent of Formula III is a compound of Formula III-3.
  • the second solvent is a compound of Formula III.
  • the first solvent and the second solvent are combined to avoid overcharging.
  • the second solvent has a benzene ring structure, and its large conjugated ⁇ bond helps to inhibit the solvent molecules from losing electrons during the electrochemical process, thereby helping to improve the antioxidant capacity of the electrolyte; the benzene ring is directly connected to the oxygen atom , the electron cloud of the oxygen atom will also be attracted and added to the conjugated bond of the benzene ring, and its oxidation resistance will be further improved.
  • the weight ratio of the first solvent to the second solvent is 0.5 to 3, optionally 0.7-1.5, more optionally 0.9-1.1. In some embodiments, the weight ratio of the first solvent to the second solvent is 1. Keeping the weight ratio of the two solvents within the above range can avoid the occurrence of transient overcharge and ensure good dissolution of the electrolyte salt in the electrolyte. At the same time, the electrolyte has better antioxidant capacity and a longer life. cycle life.
  • the electrolyte solution of the present application also includes an antioxidant; optionally, the antioxidant is selected from at least one of lithium nitrate and lithium perchlorate. In some embodiments, the antioxidant is lithium nitrate.
  • antioxidant additives can change the local solvation structure at the interface between the positive electrode and the electrolyte: its anionic part (such as nitrate and perchlorate) can During the charging process, it is attracted to the electric double layer on the surface of the ternary positive electrode and combines more closely with the active ions (for example, in the case of lithium-ion batteries, lithium ions), reducing the solvent molecules around the active ions in the double electric layer.
  • the degree of participation thereby reduces the contact between solvent molecules and the ternary positive electrode, reduces the catalytic oxidation of solvent molecules by transition metals, further protects the positive electrode, and improves cycle life.
  • the concentration of the antioxidant is 0.5% to 3% by weight, optionally 0.7% to 1.5% by weight, more optionally 0.9% to 1.1% by weight, based on the electrolyte Total weight.
  • the addition of antioxidants can further increase the critical voltage value of oxidation stability and further improve the cycle life.
  • the content of antioxidants within the above range can fully exert the above effects while avoiding excessive impact on the normal transmission of lithium ions, resulting in reduced cycle life.
  • the electrolyte of the present application also includes a fluorine-containing electrolyte salt.
  • the fluorine-containing electrolyte salt is selected from the group consisting of lithium bisfluorosulfonyl imide, lithium hexafluorophosphate, lithium tetrafluoroborate, and lithium hexafluoroarsenate. , at least one of lithium bistriflate, lithium triflate, lithium difluorophosphate, lithium difluoroborate, lithium difluorodioxalate and lithium tetrafluoroxalate.
  • the fluorine-containing electrolyte salt is lithium bisfluorosulfonimide.
  • the above-mentioned fluorine-containing electrolyte salt has good solubility in the electrolyte of the present invention (especially in the first solvent), and can be decomposed on the surface of a metal or alloy negative electrode (for example, a lithium metal negative electrode) to form an SEI group rich in inorganic fluorine points, improving the stability of the negative electrode interface is conducive to further improving the cycle life of metal or alloy negative electrode secondary batteries.
  • a metal or alloy negative electrode for example, a lithium metal negative electrode
  • the concentration of the fluoroelectrolyte salt is 0.5M to 3M, optionally 1M.
  • the cycle life of the secondary battery can be improved by using the above concentration.
  • the electrolyte optionally further includes additives.
  • additives may include negative electrode film-forming additives, positive electrode film-forming additives, and may also include additives that can improve certain properties of the battery, such as additives that improve battery overcharge performance, additives that improve battery high-temperature or low-temperature performance, etc.
  • a secondary battery including the above-mentioned electrolyte.
  • the secondary battery is a lithium ion secondary battery.
  • the secondary battery is a secondary battery with a metal or alloy negative electrode.
  • the secondary battery is a metallic lithium anode secondary battery, which may be a metallic lithium anode-lithium transition metal oxide cathode secondary battery.
  • the secondary battery provided by the present invention includes the electrolyte of the present application, the cycle is more stable, there is no overcharge phenomenon, and a longer cycle life can be achieved at the same time.
  • a secondary battery typically includes a positive electrode plate, a negative electrode plate, an electrolyte and a separator.
  • active ions are inserted and detached back and forth between the positive and negative electrodes.
  • the electrolyte plays a role in conducting ions between the positive and negative electrodes.
  • the isolation film is placed between the positive electrode piece and the negative electrode piece. It mainly prevents the positive and negative electrodes from short-circuiting and allows ions to pass through.
  • the positive electrode sheet 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 selected from lithium transition metal oxides and/or lithium-containing phosphates with an olivine structure.
  • the cathode active material is selected from lithium transition metal oxides.
  • the lithium transition metal oxide is selected from lithium cobalt oxide, lithium nickel oxide, lithium manganese oxide, lithium nickel manganese oxide, lithium nickel cobalt manganese oxide, lithium nickel cobalt aluminum oxide, or its combination.
  • lithium transition metal oxides may include, but are not limited to, lithium cobalt oxides (such as LiCoO 2 ), lithium nickel oxides (such as LiNiO 2 ), lithium manganese oxides (such as LiMnO 2 , LiMn 2 O 4 ), lithium nickel cobalt Oxide, lithium manganese cobalt oxide, lithium nickel manganese oxide, lithium nickel cobalt manganese oxide (such as LiNi 1/3 Co 1/3 Mn 1/3 O 2 (also referred to as NCM 333 ), LiNi 0.5 Co 0.2 Mn 0.3 O 2 (can also be abbreviated to NCM 523 ), LiNi 0.5 Co 0.25 Mn 0.25 O 2 (can also be abbreviated to NCM 211 ), LiNi 0.6 Co 0.2 Mn 0.2 O 2 (can also be abbreviated to NCM 622 ), LiNi 0.8 Co 0.1 Mn 0.1 O 2 (can also be abbreviated to NCM 811 ), LiNi 0.96 Co 0.02 Mn 0.
  • lithium-containing phosphates with an olivine structure may include, but are not limited to, lithium iron phosphate (such as LiFePO 4 (also referred to as LFP)), composites of lithium iron phosphate and carbon, lithium manganese phosphate (such as LiMnPO 4 ), phosphoric acid At least one of a composite material of lithium manganese and carbon, a composite material of lithium manganese iron phosphate, or a composite material of lithium manganese iron phosphate and carbon.
  • lithium iron phosphate such as LiFePO 4 (also referred to as LFP)
  • composites of lithium iron phosphate and carbon such as LiMnPO 4
  • LiMnPO 4 lithium manganese phosphate
  • phosphoric acid At least one of a composite material of lithium manganese and carbon, a composite material of lithium manganese iron phosphate, or a composite material of lithium manganese iron phosphate and carbon.
  • the positive electrode current collector has two surfaces facing each other in its own 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.
  • positive electrode film layers are provided on both sides of the positive electrode current collector.
  • the positive electrode current collector may be a metal foil or a composite current collector.
  • the metal foil aluminum foil can be used.
  • 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 base layer.
  • the composite current collector can be formed by forming metal materials (aluminum, aluminum alloys, nickel, nickel alloys, titanium, titanium alloys, silver and silver alloys, etc.) on polymer material substrates (such as polypropylene (PP), polyterephthalate It is formed on substrates such as ethylene glycol ester (PET), polybutylene terephthalate (PBT), polystyrene (PS), polyethylene (PE), etc.).
  • PP polypropylene
  • PBT polybutylene terephthalate
  • PS polystyrene
  • PE polyethylene
  • the cathode active material may be a cathode active material known in the art for batteries.
  • the cathode active material may include at least one of the following materials: an olivine-structured lithium-containing phosphate, a lithium transition metal oxide, and their respective modified compounds.
  • the present application is not limited to these materials, and other traditional materials that can be used as positive electrode active materials of batteries can also be used. Only one type of these positive electrode active materials may be used alone, or two or more types may be used in combination.
  • the positive electrode film layer optionally further includes a binder.
  • the binder may include polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), vinylidene fluoride-tetrafluoroethylene-propylene terpolymer, vinylidene fluoride-hexafluoropropylene-tetrafluoroethylene At least one of ethylene terpolymer, tetrafluoroethylene-hexafluoropropylene copolymer and fluorine-containing acrylate resin.
  • the positive electrode film layer optionally further includes a conductive agent.
  • the conductive agent may include at least one 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 dispersing the above-mentioned components for preparing the positive electrode sheet, such as positive active material, conductive agent, binder and any other components in a solvent (such as N -methylpyrrolidone) to form a positive electrode slurry; the positive electrode slurry is coated on the positive electrode current collector, and after drying, cold pressing and other processes, the positive electrode piece can be obtained.
  • a solvent such as N -methylpyrrolidone
  • 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 selected from the group consisting of pure metals, intermetallic alloys, or metal-nonmetal alloys.
  • the metal is selected from lithium (Li), tin (Sn), zinc (Zn), aluminum (Al), magnesium (Mg), silver (Ag), gold (Au), gallium (Ga) , indium (In), foil (Pt) or combinations thereof.
  • the non-metal is selected from boron (B), carbon (C), silicon (Si), or combinations thereof.
  • the negative electrode current collector has two opposite surfaces in its own 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.
  • 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 base material.
  • the composite current collector can be formed by forming metal materials (copper, copper alloy, nickel, nickel alloy, titanium, titanium alloy, silver and silver alloy, etc.) on a polymer material substrate (such as polypropylene (PP), polyterephthalate It is formed on substrates such as ethylene glycol ester (PET), polybutylene terephthalate (PBT), polystyrene (PS), polyethylene (PE), etc.).
  • PP polypropylene
  • PBT polybutylene terephthalate
  • PS polystyrene
  • PE polyethylene
  • the negative electrode film layer optionally further includes a binder.
  • the binder can be selected from styrene-butadiene rubber (SBR), polyacrylic acid (PAA), polysodium acrylate (PAAS), polyacrylamide (PAM), polyvinyl alcohol (PVA), sodium alginate (SA), poly At least one of methacrylic acid (PMAA) and carboxymethyl chitosan (CMCS).
  • the negative electrode film layer optionally further includes a conductive agent.
  • the conductive agent may be selected from at least one of superconducting carbon, acetylene black, carbon black, Ketjen black, carbon dots, carbon nanotubes, graphene and carbon nanofibers.
  • the negative electrode film layer optionally includes other auxiliaries, such as thickeners (such as sodium carboxymethylcellulose (CMC-Na)) and the like.
  • thickeners such as sodium carboxymethylcellulose (CMC-Na)
  • the negative electrode sheet can be prepared by dispersing the above-mentioned components for preparing the negative electrode sheet, such as negative active materials, conductive agents, binders and any other components in a solvent (such as deionized water) to form a negative electrode slurry; the negative electrode slurry is coated on the negative electrode current collector, and after drying, cold pressing and other processes, the negative electrode piece can be obtained.
  • a solvent such as deionized water
  • the secondary battery further includes a separator film.
  • a separator film There is no particular restriction on the type of isolation membrane in this application. Any well-known porous structure isolation membrane with good chemical stability and mechanical stability can be used.
  • the isolation membrane can use, but is not limited to, polyethylene porous membranes, polypropylene porous membranes, polyimide porous membranes, and porous membranes formed by composites of multiple polymers.
  • the isolation film can be a single-layer film or a multi-layer composite film, with no special restrictions.
  • the materials of each layer can be the same or different, and there is no particular limitation.
  • the positive electrode piece, the negative electrode piece and the separator film can be made into an electrode assembly through a winding process or a lamination process.
  • the secondary battery may include an outer packaging.
  • the outer packaging can be used to package the above-mentioned electrode assembly and 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 bag, such as a bag-type soft bag.
  • the material of the soft bag may be plastic, and examples of the plastic include polypropylene, polybutylene terephthalate, polybutylene succinate, and the like.
  • This application has no particular limitation on the shape of the secondary battery, which can be cylindrical, square or any other shape.
  • a battery module including the above-mentioned secondary battery.
  • a battery pack including the battery module described above.
  • an electrical device including at least one selected from the above-mentioned secondary battery, battery module or battery pack.
  • FIG. 11 shows a square-structured secondary battery 5 as an example.
  • the outer package may include a housing 51 and a cover 53 .
  • the housing 51 may include a bottom plate and side plates connected to the bottom plate, and the bottom plate and the side plates enclose a receiving cavity.
  • the housing 51 has an opening communicating with the accommodation cavity, and the cover plate 53 can cover the opening to close the accommodation cavity.
  • the positive electrode piece, the negative electrode piece and the isolation film can be formed into the electrode assembly 52 through a winding process or a lamination process.
  • the electrode assembly 52 is packaged in the containing cavity.
  • the electrolyte soaks into 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 specific actual needs.
  • secondary batteries can be assembled into battery modules, and the number of secondary batteries contained in the battery module can be one or more. The specific number can be selected by those skilled in the art according to the application and capacity of the battery module.
  • FIG. 13 is a battery module 4 as an example.
  • a plurality of secondary batteries 5 may be arranged in sequence along the length direction of the battery module 4 .
  • the plurality of secondary batteries 5 can be fixed by fasteners.
  • the battery module 4 may further include a housing having a receiving space in which a plurality of secondary batteries 5 are received.
  • the above-mentioned battery modules can also be assembled into a battery pack.
  • the number of battery modules contained in the battery pack can be one or more. Those skilled in the art can select the specific number according to the application and capacity of the battery pack.
  • the battery pack 1 may include a battery box and a plurality of battery modules 4 disposed in the battery box.
  • the battery box includes an upper box 2 and a lower box 3 .
  • the upper box 2 can be covered with the lower box 3 and form a closed space for accommodating the battery module 4 .
  • Multiple battery modules 4 can be arranged in the battery box in any manner.
  • the present application also provides an electrical device, which includes at least one of the secondary battery, battery module, or battery pack provided by the present application.
  • the secondary battery, battery module, or battery pack may be used as a power source for the electrical device, or may be used as an energy storage unit for the electrical device.
  • the electric device may include mobile devices (such as mobile phones, laptops, etc.), electric vehicles (such as pure electric vehicles, hybrid electric vehicles, plug-in hybrid electric vehicles, electric bicycles, electric scooters, and electric golf carts). , electric trucks, etc.), electric trains, ships and satellites, energy storage systems, etc., but are not limited to these.
  • a secondary battery, a battery module or a battery pack can be selected according to its usage requirements.
  • Figure 16 is an electrical device as an example.
  • the electric device is a pure electric vehicle, a hybrid electric vehicle, a plug-in hybrid electric vehicle, etc.
  • a battery pack or battery module can be used.
  • the device may be a mobile phone, a tablet, a laptop, etc.
  • the device is usually required to be thin and light, and a secondary battery can be used as a power source.
  • Equal masses of the first solvent of formula I-2 and the second solvent of formula III-3 are mixed and stirred to obtain a colorless, transparent and homogeneous mixed solvent.
  • the cathode active material LiNi 0.8 Co 0.1 Mn 0.1 O 2 (NCM 811 ), conductive agent acetylene black, and binder PVDF in a mass ratio of 98:1:1.
  • NMP solvent N-methylpyrrolidone
  • the positive electrode slurry solid content is 70% by weight
  • the positive electrode surface capacity is 3.5mAh/cm 2 .
  • the 50 ⁇ m lithium foil was rolled onto one surface of the 12 ⁇ m copper foil, and then cut into a 41mm*51mm rectangle as a negative electrode piece.
  • the secondary battery prepared in this way has a rated capacity of 140mAh.
  • the ambient temperature of the cell cycle is set to 25°C, and the secondary battery obtained in 1.5 above is charged and discharged using a Xinwei cycle tester at a rate of 0.5C (i.e. 70mA).
  • the cut-off voltages of charge and discharge are set to 4.3V and 2.8V respectively.
  • the aluminum foil is the positive electrode, cut it into a disc with a diameter of 1cm2 , and the polyethylene porous film of the same size is the isolation film, inject 20 ⁇ l of the electrolyte prepared in the previous item 1, and assemble it into a test piece.
  • Button Battery
  • Example 1 to prepare electrolytes and secondary batteries, and conduct corresponding tests; the difference lies in that the first and second solvents in these examples are different.
  • Example 1 to prepare electrolytes and secondary batteries, and perform corresponding tests; the difference lies in that the mass ratios of the first and second solvents in these examples are different.
  • a conventional ether electrolyte solution in the prior art was prepared as follows, and tested with reference to Example 1.
  • the oxidation stability of the electrolyte is 4V.
  • the oxidation stability of the electrolyte is 4V.
  • serious overcharging begins in the first cycle of the cycle.
  • the battery cell with a rated capacity of 140mAh only reaches the cut-off voltage after charging 450mAh, indicating that the electrolyte has undergone obvious oxidation and decomposition.
  • the fluorine-containing ether electrolyte in the prior art was prepared as follows, and tested with reference to Example 1.
  • the oxidation stability of the electrolyte is 5.4V.
  • a slight overcharge phenomenon occurs in the range of about 50-70 cycles during the cycle, but the discharge capacity is less affected in this range and can recover on its own. Life span is 146 cycles.
  • a prior art local highly concentrated electrolyte solution was prepared as follows and tested with reference to Example 1.
  • a prior art local highly concentrated electrolyte solution was prepared as follows and tested with reference to Example 1.
  • the oxidation stability of the electrolyte is 5.3V.
  • overcharging occurs in the range of about 45-55 cycles during the cycle.
  • the discharge capacity is less affected in this range and can recover on its own.
  • the cycle life is 135 laps.
  • Table 1 shows the electrolyte solutions and performance test results in the above-mentioned Examples 1-16 and Comparative Examples 1-4.
  • solvent mass ratio here means the mass ratio of the first solvent to the second solvent.
  • the electrolyte of the present application can effectively avoid the above-mentioned "one-time” overcharge problem of secondary batteries in long cycles, and also has a relatively high oxidation stability critical voltage (that is, high oxidation stability) , and can improve cycle life.
  • the conventional ether electrolyte of Comparative Example 1 is difficult to cycle normally in the metallic lithium negative electrode-ternary positive electrode secondary battery; as can be seen from Comparative Example 2, when using a fluorine-containing solvent alone, although the oxidation stability can be improved, it cannot solve the long cycle problem. overcharging problem.
  • Example 17 The difference between Example 17 and Example 1 is that after preparing a colorless and transparent solution with a concentration of 1M, lithium nitrate powder is added thereto so that the weight ratio of the solution to lithium nitrate is 99:1, and is added to the solution to fully Stir to form a colorless and transparent electrolyte, which is the required electrolyte.
  • Example 18 The difference between Examples 18-25 and Example 17 lies in the weight ratio of the first and/or second solvent.
  • Example 26 and Example 17 The difference between Example 26 and Example 17 is that the first and second solvents are different respectively.
  • the difference between Examples 27-32 and Example 26 is that the weight ratio of the first and second solvents is different.
  • the difference between Example 33 and Example 17 is that the first and second solvents are different respectively.
  • the difference between Examples 34-39 and Example 33 is that the weight ratio of the first and second solvents is different.
  • a conventional ether electrolyte containing antioxidant additives was prepared as follows and tested with reference to Example 1.
  • the electrolyte's oxidation stability critical voltage is 5.1V.
  • a relatively obvious overcharge phenomenon occurred in the range of approximately 35-60 cycles during the cycle, and the discharge capacity was significantly affected in this range, with a cycle life of 92 cycles. .
  • a fluoroether electrolyte containing antioxidant additives was prepared as follows and tested with reference to Example 1.
  • the oxidation stability of the electrolyte is 5.4V.
  • a slight overcharge phenomenon occurs in the range of 100-170 cycles during the cycle, but the discharge capacity is less affected in this range and can recover on its own.
  • Table 2 below shows the electrolyte solutions and their performance test data in Examples 17-46 and Comparative Examples 5-6.
  • the electrolyte with added antioxidants in addition to preventing overcharge, also improves the oxidation stability of the electrolyte and increases the cycle life. It can be seen from Comparative Examples 3-4 that the use of a combination of conventional ether solvents and antioxidants cannot prevent overcharging, while the combination of fluorine-containing ether solvents and antioxidants can improve the antioxidant properties and cycle life. There is also no way to avoid overcharging.
  • Example 53-58 and Example 26 lies in the different antioxidant concentrations.
  • the difference between Examples 59-64 and Example 33 lies in the concentration of antioxidants.
  • Example 65-70 The difference between Examples 65-70 and Example 17 lies in the addition of antioxidants and their concentrations.
  • Example 71-72 and Example 17 lies in the different electrolyte salt concentrations.
  • the difference between Examples 73-74 and Example 26 lies in the different electrolyte salt concentrations.
  • the difference between Examples 75-76 and Example 33 lies in the different electrolyte salt concentrations.
  • the difference between Examples 77-78 and Examples 71-72 is that the antioxidants are different.
  • Table 3 below shows the electrolytes of Examples 47-78 and their performance test results.
  • the best performance can be achieved when the weight ratio of the first solvent to the second solvent is 1, the antioxidant additive content is 1%, and the electrolyte salt concentration is 1M.

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Abstract

本申请提供了一种电解液，包括：如式I所示的第一溶剂和选自式II、式III的中的一种或几种的第二溶剂，其中，R1选自C1-C6的氟代链烷基，R2选自氢原子、C1-C6的链烷基或C1-C6的氟代链烷基，n表示1或2，R3至R10各自独立地选自氢原子、氟原子、C1-C6的链烷基或C1-C6的氟代链烷基。本申请的电解液可改善电池的循环稳定性和安全性。本申请还涉及包括上述电解液的二次电池、电池模块、电池包和用电装置。

Description

电解液、二次电池、电池模块、电池包和用电装置 技术领域
本申请涉及锂电池技术领域，尤其涉及一种电解液、二次电池、电池模块、电池包和用电装置。
背景技术
二次电池已经被广泛应用到消费电子产品、电动车以及储能等诸多领域。对于常见的锂离子二次电池，人们对其能量密度的改善已经接近达到理论极限。为了满足未来包括高续航电动车、电动飞机等更高能量密度需求的场景应用，需要开发更具能量密度潜力的二次电池，例如，金属锂负极与三元等高压正极匹配的金属锂二次电池。然而，金属锂负极具有较高的反应活性，易与电解液自发反应生成机械强度、化学稳定性均不佳的固态电解质界面层(SEI)，引发枝晶状的生长形貌，因此循环能力不好，并存在安全风险，和快速的锂源消耗造成的寿命衰竭。
提高金属锂电池的循环能力，电解液的设计与优化至关重要。然而，现有技术中的电解液在金属锂负极二次电池中发生系统性的“一过性”过充问题，其可能带来难以遏制的电池管理难度与安全风险。
发明内容
本申请是鉴于上述课题而进行的，其目的在于，提供一种电解液，其能够避免过充现象，从而改善锂离子二次电池的循环稳定性和安全性，同时可延长循环寿命。
为了达到上述目的，本申请提供了一种电解液和包括该电解液的二次电池、电池模块、电池包和用电装置。
本申请的第一方面提供了一种电解液，包括：
第一溶剂，如式I所示；
Figure PCTCN2022108958-appb-000001
其中，
R 1选自C1-C6的氟代链烷基；
R 2选自氢原子、C1-C6的链烷基和C1-C6的氟代链烷基；
n表示1或2；和
第二溶剂，选自式II和式III的化合物中的一种或几种；
Figure PCTCN2022108958-appb-000002
其中，
R 3至R 10各自独立地选自氢原子、氟原子、C1-C6的链烷基和C1-C6的氟代链烷基。本申请的电解液可避免二次电池在长循环中的“一过性”过充问题，改善循环稳定性和安全性。此外，本申请的电解液具有较高氧化稳定性，能够提高金属或合金负极二次电池的循环寿命。
在任意实施方式中，所述式I中，R 1选自C1-C3的氟代链烷基，可选地为氟代甲基；和/或，R 2选自氢原子、C1-C3的链烷基和C1-C3的氟代链烷基，可选地选自氢原子、甲基、氟代甲基、乙基和氟代乙基。
在任意实施方式中，所述式II中，R 3至R 8各自独立地选自氢原子、氟原子和C1-C6的氟代链烷基，可选地选自氢原子、氟原子和C1-C3的氟代链烷基；和/或所述式III中，R 9至R 10各自独立地选自氢原子、氟原子、C1-C6的链烷基和C1-C6的氟代链烷基，可选地选自氢原子、氟原子、C1-C3的链烷基和C1-C3的氟代链烷基；更可选地，R 9至R 10各自独立地选自氢原子和氟原子。
进一步选择上述第一和第二溶剂可使电解液具备较高氧化稳定性，避免过充，并改善循环寿命。
在任意实施方式中，所述第一溶剂与第二溶剂的重量比值为0.5至3，可选地为0.7至1.5，更可选地为0.9至1.1。使两种溶剂的重量比值在上述范围内，可以避免过充，保证电解质盐在电解液中的良好溶解，并使电解液具备较好的抗氧化能力以及较长的循环寿命。
在任意实施方式中，所述电解液还包括抗氧化剂；可选地，所述抗氧化剂选自硝酸锂、高氯酸锂中的至少一种。添加抗氧化剂有助于进一步提高循环寿命。
在任意实施方式中，所述抗氧化剂的浓度是0.5重量％至3重量％，可选地为0.7重量％至1.5重量％，更可选地为0.9重量％至1.1重量％，基于电解液总重量计。抗氧化剂的添加可以进一步提高氧化稳定性临界电压值，同时进一步提高循环寿命。同时抗氧化剂的含量在上述范围内，可以充分发挥以上功效，同时避免过量影响锂离子正常传输，导致循环寿命降低。
在任意实施方式中，所述电解液还包括含氟电解质盐，可选地，所述含氟电解质盐选自双氟磺酰亚胺锂、六氟磷酸锂、四氟硼酸锂、六氟砷酸锂、双三氟甲磺酰亚胺锂、三氟甲磺酸锂、二氟磷酸锂、二氟草酸硼酸锂、二氟二草酸磷酸锂及四氟草酸磷酸锂中的至少一种，更可选地，所述含氟电解质盐是双氟磺酰亚胺锂。采用上述电解质盐有助于提高负极界面稳定性，改善循环性能。
在任意实施方式中，所述含氟电解质盐的浓度是0.5M至3M，可选地为1M。该浓度的电解质盐有助于进一步改善循环性能。
本申请的第二方面提供一种二次电池，包括本申请第一方面的电解液。
本申请的第三方面提供一种电池模块，包括本申请的第二方面的二次电池。
本申请的第四方面提供一种电池包，包括本申请的第三方面的电池模块。
本申请的第五方面提供一种用电装置，包括选自本申请第二方面的二次电池、第三方面的电池模块或第四方面的电池包中的至少一种。
本申请的电解液能够改善锂离子二次电池的循环稳定性，提高循 环寿命，避免过充现象，改善电池安全性能。
附图说明
图1为包含现有技术电解液的二次电池的循环寿命图。
图2为现有技术电解液的氧化稳定性测试结果。
图3为常规醚类电解液与含氟电解液的氧化稳定性测试结果。
图4为包括本申请一实施方式的电解液的二次电池的循环寿命图。
图5为对比例1的二次电池的循环电压-容量曲线。
图6为包括对比例2的二次电池的循环寿命图。
图7为包括对比例3的电解液的二次电池的循环寿命图。
图8为包括对比例4的电解液的二次电池的循环寿命图。
图9为包括对比例5的电解液的二次电池的循环寿命图。
图10为包括对比例6的电解液的二次电池的循环寿命图。
图11是本申请一实施方式的二次电池的示意图。
图12是图11所示的本申请一实施方式的二次电池的分解图。
图13是本申请一实施方式的电池模块的示意图。
图14是本申请一实施方式的电池包的示意图。
图15是图14所示的本申请一实施方式的电池包的分解图。
图16是本申请一实施方式的二次电池用作电源的用电装置的示意图。
附图标记说明：
1电池包；2上箱体；3下箱体；4电池模块；5二次电池；51壳体；52电极组件；53顶盖组件
具体实施方式
以下，适当地参照附图详细说明具体公开了本申请的电解液、二次电池、电池模块、电池包和电学装置的实施方式。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“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，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，和如果列出了最大范围值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”表示本文中已经全部列出了“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。
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，本申请的所有技术特征以及可选技术特征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，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“包括”和“包含”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组分，也可以仅包括或包含列出的组分。
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”。更具体地，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)。
二次电池已经被广泛应用到消费电子产品、电动车以及储能等诸多领域。对于常见的锂离子二次电池，人们对其能量密度的改善已经接近达到理论极限。为了满足未来包括高续航电动车、电动飞机等更高能量密度需求的场景应用，开发了更具能量密度潜力的二次电池，例如，金属或合金负极离子二次电池。
然而，已知金属或合金负极具有较高的反应活性，不易形成良好的固态电解质界面层(SEI)，引发枝晶状的生长形貌，因此循环能力不理想，存在安全风险，并且快速消耗活性离子造成的寿命衰竭。
提高金属和合金负极二次电池的循环能力，电解液的设计至关重要。很多醚类电解液，特别是基于醚类的局部高浓电解液，在近年来被应用于金属负极二次电池体系，并获得良好效果。
然而，发明人在对现有技术的醚类电解液的进一步评估过程中发现，现有的局部高浓电解液用在金属负极二次电池(例如，金属-锂过渡金属氧化物电池)时，二次电池在长循环(即，超过50圈的循环)过程中会发生系统性的过充问题。不同于已知的电池过充现象，这种过充现象是“一过性”的。换言之，这样的过充问题仅在循环过程中短时间内(或一定循环圈数范围内)出现，随后又恢复正常循环状态。举例来说，如图1所示，包含有现有技术的电解液(如，LiFSI-DME-TTE体系)的二次电池在长循环过程中，在一定循环圈数范围内(如图1所示，40-65圈左右)发生充电容量超过额定容量，但是放电容量保持正常或者仅仅略微下降的过充现象；而在此圈数范围之后继续循环则上述过充现象又逐渐减弱，直至消失而恢复正常循环状态。发明人基于目前研究认为，这种“一过性”过充现象可能不会 明显缩短电芯循环寿命，也不会导致性能跳水——但也正因为如此，使其具有一定的隐蔽性，不易被发现。
但是，金属负极二次电池中的这种一过性过充问题却非常值得重视。特别值得一提的是，尽管单个电芯的“一过性”过充似乎影响甚微，但在电池模组产品中包括众多串联组装的同款电芯，这样大量的电芯在循环过程中发生此种一过性过充，就势必造成电压超出安全范围、发热、气体和电池副反应——可以想见，此时，该过充问题就可能造成难以遏制的电池管理难度与安全风险。因此，这种“一过性”过充问题虽然隐蔽，但亟待解决。而在本申请之前，现有技术中并未认识到这种特殊过充现象的存在，更没有认识到其在电池安全管理中的潜在危害性。
为解决上述问题，本申请提供一种电解液，其能够避免上述“一过性”过充问题，提高金属或合金负极二次电池的安全性，并改善循环性能。
电解液
本申请的一个实施方式中，提出了一种电解液，包括：
第一溶剂，如式I所示：
Figure PCTCN2022108958-appb-000003
其中，
R 1选自C1-C6的氟代链烷基；
R 2选自氢原子、C1-C6的链烷基和C1-C6的氟代链烷基；
n表示1或2；和
第二溶剂，选自式II和式III化合物中的一种或几种；
Figure PCTCN2022108958-appb-000004
其中，
R 3至R 10各自独立地选自氢原子、氟原子、C1-C6的链烷基和C1-C6的氟代链烷基。
本申请的电解液能够有效避免二次电池，特别是金属或合金负极的锂离子二次电池长循环中的上述“一过性”过充问题，从而改善电池的循环稳定性和安全性；同时，本申请的电解液还具有较高氧化稳定性，并可提高金属或合金负极二次电池的循环寿命。
不希望囿于任何理论，发明人发现，现有技术中的醚类电解液本征的抗氧化能力并不太差，例如，在Li-Al电池的扫描伏安曲线(LSV)测试中的二甲醚(DME)-1,1,2,2-二氟乙基-2,2,3,3-二氟丙基醚(TTE)电解液体系的氧化稳定窗口可达5.3V(参见图2)；但是，该电解液应用于例如Li-NMC811电芯进行长循环却会无一例外的发生前述“一过性”过充问题(参见，例如，下文中对比例3和图7)。而本申请的电解液具有良好的耐氧化性，并可有效避免该“一过性”过充现象的发生。
在一些实施方式中，所述式I中，R 1选自C1-C3的氟代链烷基，可选地为氟代甲基。在一些实施方式中，R 1更可选地为一氟代甲基或二氟代甲基。在一些实施方式中，所述式I中，R 2选自氢原子、C1-C3的链烷基和C1-C3的氟代链烷基，可选地选自氢原子、甲基、氟代甲基、乙基和氟代乙基。在一些实施方式中，R 2更可选地选自氢原子、甲基、一氟代甲基、二氟代甲基、乙基、一氟代乙基和二氟代乙基。
在一些实施方式中，所述式I的第一溶剂选自以下化合物：
Figure PCTCN2022108958-appb-000005
Figure PCTCN2022108958-appb-000006
Figure PCTCN2022108958-appb-000007
Figure PCTCN2022108958-appb-000008
在一些实施方式中，所述式I的第一溶剂选自式I-1至I-16，和式I-60至I-71中的至少一种；更可选为式I-2和I-65中的至少一种。
作为本申请中的第一溶剂，相较于具有碳链较长和/或含氟量较高的链烷基的醚，更优选碳链长度较小(例如，C1-3的链烷基)，含氟量不太高(例如，一氟代或二氟代)的醚。第一溶剂使电解液具备较高沸点和较高氧化稳定性，可提高其正极侧氧化稳定性；同时，第一溶剂对电解质盐具有良好的溶解能力(举例而言，双氟磺酰亚胺锂(LiFSI)在第一溶剂中溶解浓度可达到2M甚至更高)。同时，单独使用第一溶剂并在1M的双氟磺酰亚胺锂盐浓度下，Li-Al半电池LSV测试的电解液氧化稳定性至少达到约5.3V(参见图3)。
式II和式III所示的第二溶剂，其不溶解或微溶解电解质锂盐，并且可以与第一溶剂以任意比例互溶，而不会出现分相现象。
在一些实施方式中，所述式II中，R 3至R 8各自独立地选自氢原子、氟原子和C1-C6的氟代链烷基。可选地，R 3至R 8各自独立地选自氢原子、氟原子和C1-C3的氟代链烷基。在一些实施方式中，所述式II中，R 3至R 8各自独立地选自氢原子、氟原子和氟代甲基。
在一些实施方式中，所述式II的溶剂选自以下化合物：
Figure PCTCN2022108958-appb-000009
Figure PCTCN2022108958-appb-000010
在一些实施方式中，所述式II的第二溶剂选自二氟代苯、氟代甲基苯中的至少一种，可选地选自二氟代苯和三氟代甲基苯中的至少一种，更可选地选自式II-7、II-8、II-9和II-12的化合物中的至少一种。
在一些实施方式中，所述式III中，R 9至R 10各自独立地选自氢原子、氟原子、C1-C6的链烷基和C1-C6的氟代链烷基。在一些实施方式中，可选地，R 9至R 10各自独立地选自氢原子、氟原子、C1-C3的链烷基和C1-C3的氟代链烷基。在一些实施方式中，更可选地，R 9至R 10各自独立地选自氢原子或氟原子。
在本文所述的氟代链烷基中，链烷基的一个或多个氢原子各自独立地被氟原子取代。
在一些实施方式中，式III的溶剂选自以下化合物：
Figure PCTCN2022108958-appb-000011
Figure PCTCN2022108958-appb-000012
在一些实施方式中，所述式III的第二溶剂选自氟代甲氧基苯，可选地选自式III-1、III-2和III-3的化合物中的至少一种。在一些实施方式中，所述式III的第二溶剂是式III-3的化合物。
在一些实施方式中，所述第二溶剂为式III的化合物。
本申请中，第一溶剂与第二溶剂配合，可避免过充现象的发生。另外，第二溶剂具有苯环结构，其共轭大π键有助于抑制溶剂分子在电化学过程中失去电子，进而有助于提高电解液的抗氧化能力；在苯环与氧原子直接相连时，则氧原子的电子云也会被吸引，加入苯环的共轭键中，其耐氧化能力也会进一步提高。
在一些实施方式中，所述第一溶剂与第二溶剂的重量比值为0.5至3，可选地为0.7-1.5，更可选地为0.9-1.1。在一些实施方式中，所述第一溶剂与第二溶剂的重量比值为1。使两种溶剂的重量比值在上述范围内，可以避免一过性过充现象的发生，并且保证电解质盐在电解液中的良好溶解，同时使电解液具备较好的抗氧化能力以及较长的循环寿命。
在一些实施方式中，本申请的电解液还包括抗氧化剂；可选地，所述抗氧化剂选自硝酸锂、高氯酸锂中的至少一种。在一些实施方式中，所述抗氧化剂是硝酸锂。将第一、第二溶剂与抗氧化剂三者配合使用，可更有效避免金属锂负极二次电池，特别是金属锂负极-三元正极二次电池长循环过程中的过充现象。加入上述抗氧化添加剂(特别是与电解液中的氟醚类化合物组合)，可以在正极与电解液的界面 处改变局部的溶剂化结构：其阴离子部分(如，硝酸根和高氯酸根)可以在充电过程中被吸引到三元正极表面的双电层中，并且与活性离子(例如，在锂离子电池的情况下，锂离子)较紧密地结合，降低双电层中活性离子周围溶剂分子的参与程度，从而减少溶剂分子与三元正极接触，减少溶剂分子被过渡金属催化氧化，并进一步保护正极，提高循环寿命。
在一些实施方式中，所述抗氧化剂的浓度是0.5重量％至3重量％，可选地为0.7重量％至1.5重量％，更可选地为0.9重量％至1.1重量％，基于电解液的总重量计。抗氧化剂的添加可以进一步提高氧化稳定性临界电压值，同时进一步提高循环寿命。同时抗氧化剂的含量在上述范围内，可以充分发挥以上功效，同时避免过量影响锂离子正常传输，导致循环寿命降低。
在一些实施方式中，本申请的电解液还包括含氟电解质盐，可选地，所述含氟电解质盐选自双氟磺酰亚胺锂、六氟磷酸锂、四氟硼酸锂、六氟砷酸锂、双三氟甲磺酰亚胺锂、三氟甲磺酸锂、二氟磷酸锂、二氟草酸硼酸锂、二氟二草酸磷酸锂及四氟草酸磷酸锂中的至少一种。在一些实施方式中，可选地，所述含氟电解质盐是双氟磺酰亚胺锂。上述含氟电解质盐在本发明的电解液中(特别是第一溶剂中)有良好的溶解性，并且可在金属或合金负极(例如，金属锂负极)表面分解形成富含无机氟的SEI组分，改善负极界面稳定性，有利于进一步改善金属或合金负极二次电池的循环寿命。
在一些实施方式中，所述含氟电解质盐的浓度是0.5M至3M，可选地为1M。采用上述浓度可改善二次电池的循环寿命。
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。
二次电池、电池模块、电池包和用电装置
本申请的另一个实施方式中，提出了一种二次电池，包括上文所 述的电解液。
在一些实施方式中，所述二次电池是锂离子二次电池。
在一些实施方式中，所述二次电池是金属或合金负极的二次电池。在一些实施方式中，所述二次电池是金属锂负极二次电池，可选为金属锂负极-锂过渡金属氧化物正极二次电池。
本发明提供的二次电池，由于包括本申请的电解液，循环更稳定，无过充现象，同时可以实现更长的循环寿命。
通常情况下，二次电池包括正极极片、负极极片、电解质和隔离膜。在电池充放电过程中，活性离子在正极极片和负极极片之间往返嵌入和脱出。电解质在正极极片和负极极片之间起到传导离子的作用。隔离膜设置在正极极片和负极极片之间，主要起到防止正负极短路的作用，同时可以使离子通过。
[正极极片]
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的正极膜层，所述正极膜层包括选自锂过渡金属氧化物和/或橄榄石结构的含锂磷酸盐的正极活性材料。在一些实施方式中，所述正极活性材料选自锂过渡金属氧化物。在一些实施方式中，所述锂过渡金属氧化物选自锂钴氧化物、锂镍氧化物、锂锰氧化物、锂镍锰氧化物、锂镍钴锰氧化物、锂镍钴铝氧化物或其组合。
锂过渡金属氧化物的示例可包括但不限于锂钴氧化物(如LiCoO 2)、锂镍氧化物(如LiNiO 2)、锂锰氧化物(如LiMnO 2、LiMn 2O 4)、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(如LiNi 1/3Co 1/3Mn 1/3O 2(也可以简称为NCM 333)、LiNi 0.5Co 0.2Mn 0.3O 2(也可以简称为NCM 523)、LiNi 0.5Co 0.25Mn 0.25O 2(也可以简称为NCM 211)、LiNi 0.6Co 0.2Mn 0.2O 2(也可以简称为NCM 622)、LiNi 0.8Co 0.1Mn 0.1O 2(也可以简称为NCM 811)、LiNi 0.96Co 0.02Mn 0.02O 2(也可以简称为Ni 96)、锂镍钴铝氧化物(如LiNi 0.85Co 0.15Al 0.05O 2)及其改性化合物等中的至少一种。
橄榄石结构的含锂磷酸盐的示例可包括但不限于磷酸铁锂(如LiFePO 4(也可以简称为LFP))、磷酸铁锂与碳的复合材料、磷酸锰 锂(如LiMnPO 4)、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至少一种。
作为示例，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，所述正极集流体的两侧均设置有正极膜层。
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(铝、铝合金、镍、镍合金、钛、钛合金、银及银合金等)形成在高分子材料基材(如聚丙烯(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)等的基材)上而形成。
在一些实施方式中，正极活性材料可采用本领域公知的用于电池的正极活性材料。作为示例，正极活性材料可包括以下材料中的至少一种：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，还可以使用其他可被用作电池正极活性材料的传统材料。这些正极活性材料可以仅单独使用一种，也可以将两种以上组合使用。
在一些实施方式中，正极膜层还可选地包括粘结剂。作为示例，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至少一种。
在一些实施方式中，正极膜层还可选地包括导电剂。作为示例，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至少一种。
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，例如正极活性材料、导电剂、粘结剂和任意其他的组分分散于溶剂(例如N-甲基吡咯烷酮)中，形成正极浆料； 将正极浆料涂覆在正极集流体上，经烘干、冷压等工序后，即可得到正极极片。
[负极极片]
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，所述负极膜层包括选自以下的负极活性材料：纯金属、金属间合金，或金属-非金属合金。在一些实施方式中，所述金属选自锂(Li)、锡(Sn)、锌(Zn)、铝(Al)、镁(Mg)、银(Ag)、金(Au)、镓(Ga)、铟(In)、箔(Pt)或其组合。在一些实施方式中，述非金属选自硼(B)、碳(C)、硅(Si)或其组合。
这些负极活性材料可以仅单独使用一种，也可以将两种以上组合使用。
作为示例，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(铜、铜合金、镍、镍合金、钛、钛合金、银及银合金等)形成在高分子材料基材(如聚丙烯(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)等的基材)上而形成。
在一些实施方式中，负极膜层还可选地包括粘结剂。所述粘结剂可选自丁苯橡胶(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)中的至少一种。
在一些实施方式中，负极膜层还可选地包括导电剂。导电剂可选自超导碳、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至少一种。
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(如羧甲基纤维素钠(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，例如负极活性材料、导电剂、粘结剂和任意其他组分分散于溶剂(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上，经烘干、冷压等工序后，即可得到负极极片。
[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，隔离膜可以使用但不限于聚乙烯多孔膜，聚丙烯多孔膜，聚酰亚胺多孔膜以及多种聚合物复合形成的多孔膜。
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。
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，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，作为塑料，可列举出聚丙烯、聚对苯二甲酸丁二醇酯以及聚丁二酸丁二醇酯等。
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。
本申请的再一个实施方式中，提出了一种电池模块，包括上文所述的二次电池。
本申请的再一个实施方式中，提出了一种电池包，包括上文所述的电池模块。
本申请的再一个实施方式中，提出了一种用电装置，包括选自上文所述的二次电池、电池模块或电池包中的至少一种。
以下适当参照附图对本申请的二次电池、电池模块、电池包和用电装置进行说明。
图11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12，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具体实际需求进行选择。
在一些实施方式中，二次电池可以组装成电池模块，电池模块所含二次电池的数量可以为一个或多个，具体数量本领域技术人员可根据电池模块的应用和容量进行选择。
图13是作为一个示例的电池模块4。参照图13，在电池模块4中，多个二次电池5可以是沿电池模块4的长度方向依次排列设置。当然，也可以按照其他任意的方式进行排布。进一步可以通过紧固件将该多个二次电池5进行固定。
可选地，电池模块4还可以包括具有容纳空间的外壳，多个二次电池5容纳于该容纳空间。
在一些实施方式中，上述电池模块还可以组装成电池包，电池包所含电池模块的数量可以为一个或多个，具体数量本领域技术人员可根据电池包的应用和容量进行选择。
图14和图15是作为一个示例的电池包1。参照图14和图15，在电池包1中可以包括电池箱和设置于电池箱中的多个电池模块4。电池箱包括上箱体2和下箱体3，上箱体2能够盖设于下箱体3，并形成用于容纳电池模块4的封闭空间。多个电池模块4可以按照任意的方式排布于电池箱中。
另外，本申请还提供一种用电装置，所述用电装置包括本申请提供的二次电池、电池模块、或电池包中的至少一种。所述二次电池、电池模块、或电池包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(例如手机、笔记本电脑等)、电动车辆(例如纯电动车、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)、电气列车、船舶及卫星、储能系统等，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、电池模块或电池包。
图16是作为一个示例的用电装置。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。
实施例
以下，说明本申请的实施例。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。实施例中未注明具体技术或条件的，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。
实施例1
1.制备
1.1电解液的制备：
取等质量的式I-2的第一溶剂与式III-3的第二溶剂混合并搅拌得到无色透明均质的混合溶剂。取0.935g双氟磺酰亚胺锂盐，加入5ml前述混合溶剂之中，充分搅拌，形成1M浓度的无色透明溶液，即为所需的电解液。
1.2正极极片的制备：
将正极活性材料LiNi 0.8Co 0.1Mn 0.1O 2(NCM 811)、导电剂乙炔黑、粘结剂PVDF按质量比98:1:1混合，加入溶剂N-甲基吡咯烷酮(NMP)搅拌至体系呈均一状，获得正极浆料(固含量为70重量％)；将正极浆料以约25mg/cm 2的负载量均匀地双面涂覆在正极集流体铝箔上，室温晾干后转移至烘箱继续干燥，然后裁切成40mm*50mm的长方形做为正极极片，正极面容量为3.5mAh/cm 2。
1.3负极极片的制备：
将50μm锂箔通过辊压方式覆于12μm铜箔的一个表面，然后裁切成41mm*51mm的长方形作为负极极片备用。
1.4隔离膜：
选用聚乙烯多孔膜，裁切成45mm*55mm的长方形备用。
1.5二次电池组装：
取一片裁剪好的正极与两片裁剪好的负极进行匹配，中间使用上述隔离膜隔绝正负极，并包裹于铝塑膜袋中组成叠片干电芯。注入0.3g前述配置好的电解液，将铝塑膜袋进行真空热压封装，在室温下静置至少6小时后，即可开始进行下文中2.1中的循环测试。如此方法制备的二次电池额定容量为140mAh。
2.测试
2.1二次电池循环测试：
电芯循环的环境温度设定为25℃，使用新威循环测试仪以0.5C的倍率(即70mA)对上文1.5中得到的二次电池进行充放电循环。充放电的截止电压分别设定为4.3V与2.8V。当放电容量衰减到首圈放电容量的80％时，认为电池寿命截止——此时的循环圈数即为循环寿命。
同时，在循环过程中，圈数与其对应的被测电池的循环充放容量和库伦效率(CE)见图4。由图4可见，电池的循环寿命为171圈；并且在整个寿命周期内，没有出现充电容量明显高于额定容量的过充现象。
2.2电解液氧化稳定性的Li-Al半电池LSV测试
取50μm前述1.3中制备的负极，铝箔为正极，裁成直径1cm 2的圆片，相同大小的聚乙烯多孔膜为隔离膜，注入20μl前述第1项中配制好的电解液，组装成待测纽扣电池。
使用Solartron电化学工作站，在开路电压至6V的电压区间内，以5mV/s的扫速进行扫描伏安曲线(LSV)测试，记录该纽扣电池的电流响应。当电流密度达到10μA/cm 2时，其对应的电压为该电解液的氧化稳定性临界电压值。
经过该方法测定，实施例1所得到的电解液的氧化稳定性为5.4V。
实施例2-9
参考实施例1制备电解液、二次电池，并进行相应测试；区别在于，这些实施例中第一和第二溶剂不同。
实施例10-17
参考实施例1制备电解液、二次电池，并进行相应测试；区别在于，这些实施例中第一和第二溶剂的质量比的比值不同。
对比例1
按照下文制备现有技术中常规醚类电解液，并参考实施例1进行测试。
取0.935g双氟磺酰亚胺锂盐，加入5ml乙二醇二甲醚(DME)溶剂中，充分搅拌，形成1M浓度的无色透明电解液用于氧化稳定性测试与液态金属锂二次电池的长循环测试。
经测试，该电解液的氧化稳定性为4V。参见图5，在液态金属锂二次电池中，循环第1圈就开始严重过充，额定容量140mAh的电芯充电450mAh才到达截止电压，说明电解液已经发生明显氧化分解。
对比例2
按照下文制备现有技术中含氟醚类电解液，并参考实施例1进行测试。
取0.935g双氟磺酰亚胺锂盐，加入5ml式I-2的溶剂中，充分搅拌，形成1M浓度的无色透明电解液用于氧化稳定性测试与液态金属锂二次电池的长循环测试。
经测试，该电解液的氧化稳定性为5.4V。参见图6，在液态金属锂二次电池中，循环过程中在约50-70圈数区间出现了轻微的过充现象，但是该区间内放电容量受到的影响较小，并可自行恢复，循环寿命为146圈。
对比例3
按照下文制备现有技术的局部高浓电解液，并参考实施例1进行测试。
取等质量的乙二醇二甲醚(DME)与1,1,2,2-二氟乙基-2,2,3,3-二氟丙基醚(TTE)混合搅拌，形成无色透明均一液体备用。取0.935g双氟磺酰亚胺锂盐，加入5ml前述混合溶剂之中，充分搅拌，形成1M浓度的无色透明溶液。用于后续性能测试与电芯循环。
经测试，该电解液的氧化稳定性为5.3V。参见图7，在液态金属锂二次电池中，循环过程中在约40-60圈数区间出现了较为明显的过充现象，但是该区间内放电容量受到的影响较小，并可自行恢复，循环寿命为110圈。
对比例4
按照下文制备现有技术的局部高浓电解液，并参考实施例1进行测试。
取等质量的乙二醇二乙醚(DEE)与1,2-(1,1,2,2-四氟乙氧基)-乙烷(TFE)混合搅拌，形成无色透明均一液体备用。取0.935g双氟磺酰亚胺锂盐，加入5ml前述混合溶剂之中，充分搅拌，形成1M浓度的无色透明溶液。用于后续性能测试与电芯循环。
经测试，该电解液的氧化稳定性为5.3V。参见图8，在液态金属锂二次电池中，循环过程中在约45-55圈数区间出现了过充现象，但是该区间内放电容量受到的影响较小，并可自行恢复，循环寿命为135圈。
下表1中示出了上述实施例1-16和对比例1-4中的电解液及性能测试结果。
表1
Figure PCTCN2022108958-appb-000013
Figure PCTCN2022108958-appb-000014
*此处“溶剂质量比”意为第一溶剂与第二溶剂的质量比。下文中相同表述表示同意含义。
由表1可见，本申请的电解液可有效避免二次电池在长循环中的上述“一过性”过充问题，并且还具有较的氧化稳定性临界电压(也即，高氧化稳定性)，并可提高循环寿命。对比例1的常规醚类电解液在金属锂负极-三元正极二次电池中难以正常循环；由对比例2可见，单独使用含氟溶剂时，尽管可以提高氧化稳定性，但无法解决长循环中的过充问题。
实施例17-25
实施例17与实施例1的区别在于，在配制得到1M浓度的无色透明溶液后，向其中加入硝酸锂粉末，使所述溶液与硝酸锂的重量比为99:1，加入溶液中，充分搅拌，形成无色透明的电解液，即为所需 的电解液。
实施例18-25与实施例17的区别在于第一和/或第二溶剂重量比不同。
实施例26-39
实施例26与实施例17的区别在于第一和第二溶剂分别不同，实施例27-32与实施例26的区别在于第一和第二溶剂的重量比不同。实施例33与实施例17的区别在于第一和第二溶剂分别不同，实施例34-39与实施例33的区别在于第一和第二溶剂的重量比不同。
实施例40-46
实施例40-46与实施例17-25的区别在于加入的抗氧化剂不同。
对比例5
按照下文制备含抗氧化添加剂的常规醚类电解液，并参考实施例1进行测试。
取0.935g双氟磺酰亚胺锂盐，加入5ml乙二醇二甲醚(DME)溶剂中，再加入其总质量1％的硝酸锂粉末，充分搅拌，形成含抗氧化添加剂的1M浓度的无色透明电解液用于氧化稳定性测试与液态金属锂二次电池的长循环测试。
经测试，该电解液的氧化稳定性临界电压为5.1V。参见图9，在液态金属锂二次电池中，循环过程中在约35-60圈数区间出现了较为明显的过充现象，且放电容量在该区间受到较为明显的影响，循环寿命为92圈。
对比例6
按照下文制备含抗氧化添加剂的氟醚类电解液，并参考实施例1进行测试。
取0.935g双氟磺酰亚胺锂盐，加入5ml式I-2的溶剂中，再加入其总质量1％的硝酸锂粉末，充分搅拌，形成含抗氧化添加剂的1M浓度的无色透明电解液用于氧化稳定性测试与液态金属锂二次电池的长循环测试。
经测试，该电解液的氧化稳定性为5.4V。参见图10，在液态金 属锂二次电池中，循环过程中在100-170圈数区间出现了轻微的过充现象，但是该区间内放电容量受到的影响较小，并可自行恢复，循环寿命为159圈。
下表2示出了实施例17-46和对比例5-6中的电解液及其性能测试数据。
表2
Figure PCTCN2022108958-appb-000015
Figure PCTCN2022108958-appb-000016
由表2可见，添加了抗氧化剂的电解液，除了不会发生过充之外，还改善了电解液的氧化稳定性并提高了循环寿命。由对比例3-4可见，使用常规醚类溶剂与抗氧化剂的组合不能实现避免过充的效果，而采用含氟醚类溶剂与抗氧化剂的组合，尽管可以改善抗氧化性和循环寿命，但也无法避免过充。
实施例47-52
实施例47-52与实施例17的区别在于加入的抗氧化剂的浓度不同。
实施例53-64
实施例53-58与实施例26的区别在于抗氧化剂浓度不同。实施例59-64与实施例33的区别在于抗氧化剂的浓度不同。
实施例65-70
实施例65-70与实施例17的区别在于加入的抗氧化剂及其浓度不同。
实施例71-78
实施例71-72与实施例17的区别在于电解质盐浓度不同。实施例73-74与实施例26的区别在于电解质盐浓度不同。实施例75-76与实施例33的区别在于电解质盐浓度不同。实施例77-78与实施例71-72的区别在于抗氧化剂不同。
下表3示出了实施例47-78的电解液及其性能测试结果。
表3
Figure PCTCN2022108958-appb-000017
Figure PCTCN2022108958-appb-000018
由表3可见，采用上述浓度范围的抗氧化剂能够进一步改善氧化稳定性并延长的循环寿命。
综上可见，当第一溶剂和第二溶剂的重量比为1，抗氧化添加剂含量为1％，且电解质盐浓度为1M时，可实现最佳性能。
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。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。

Claims (12)

  1. 一种电解液，包括：
    第一溶剂，如式I所示：
    Figure PCTCN2022108958-appb-100001
    其中，
    R 1选自C1-C6的氟代链烷基；
    R 2选自氢原子、C1-C6的链烷基和C1-C6的氟代链烷基；
    n表示1或2；和
    第二溶剂，选自式II和式III化合物中的一种或几种；
    Figure PCTCN2022108958-appb-100002
    其中，
    R 3至R 10各自独立地选自氢原子、氟原子、C1-C6的链烷基和C1-C6的氟代链烷基。
  2. 根据权利要求1所述的电解液，其中所述式I中，R 1选自C1-C3的氟代链烷基，可选地为氟代甲基；和/或，R 2选自氢原子、C1-C3的链烷基和C1-C3的氟代链烷基，可选地选自氢原子、甲基、氟代甲基、乙基和氟代乙基。
  3. 根据权利要求1或2所述的电解液，其中所述式II中，R 3至R 8各自独立地选自氢原子、氟原子和C1-C6的氟代链烷基，可选地选自氢原子、氟原子和C1-C3的氟代链烷基；和/或
    式III中，R 9至R 10各自独立地选自氢原子、氟原子和C1-C6的链烷基，可选地选自氢原子、氟原子、C1-C3的链烷基和C1-C3的氟代链烷基；更可选地，R 9至R 10各自独立地选自氢原子或氟原子。
  4. 根据权利要求1至3中任一项所述的电解液，其中所述第一 溶剂与第二溶剂的重量比值为0.5至3，可选地为0.7至1.5，更可选地为0.9至1.1。
  5. 根据权利要求1至4中任一项所述的电解液，还包括抗氧化剂；可选地，所述抗氧化剂选自硝酸锂、高氯酸锂中的至少一种。
  6. 根据权利要求5所述的电解液，所述抗氧化剂的浓度是0.5重量％至3重量％，可选地为0.7重量％至1.5重量％，更可选地为0.9重量％至1.1重量％，基于电解液总重量计。
  7. 根据权利要求1至6中任一项所述的电解液，还包括含氟电解质盐，可选地，所述含氟电解质盐选自双氟磺酰亚胺锂、六氟磷酸锂、四氟硼酸锂、六氟砷酸锂、双三氟甲磺酰亚胺锂、三氟甲磺酸锂、二氟磷酸锂、二氟草酸硼酸锂、二氟二草酸磷酸锂和四氟草酸磷酸锂中的至少一种，更可选地，所述含氟电解质盐是双氟磺酰亚胺锂。
  8. 根据权利要求7所述的电解液，所述含氟电解质盐的浓度是0.5M至3M，可选地为1M。
  9. 一种二次电池，包括权利要求1至8中任一项所述的电解液。
  10. 一种电池模块，包括权利要求9所述的二次电池。
  11. 一种电池包，包括权利要求10所述的电池模块。
  12. 一种用电装置，包括选自权利要求9所述的二次电池、权利要求10所述的电池模块或权利要求11所述的电池包中的至少一种。
PCT/CN2022/108958 2022-07-29 2022-07-29 电解液、二次电池、电池模块、电池包和用电装置 Ceased WO2024021020A1 (zh)

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