WO2024187927A1 - 电池和用电装置 - Google Patents

电池和用电装置 Download PDF

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Publication number
WO2024187927A1
WO2024187927A1 PCT/CN2024/070831 CN2024070831W WO2024187927A1 WO 2024187927 A1 WO2024187927 A1 WO 2024187927A1 CN 2024070831 W CN2024070831 W CN 2024070831W WO 2024187927 A1 WO2024187927 A1 WO 2024187927A1
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Prior art keywords
positive electrode
active material
electrode active
battery
optionally
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English (en)
French (fr)
Inventor
尚义博
秦一鸣
徐晓富
潘坚福
裴人杰
张新羽
刘倩
叶永煌
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Contemporary Amperex Technology Co Ltd
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Contemporary Amperex Technology Co Ltd
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Priority to EP24769625.5A priority Critical patent/EP4611068A4/en
Publication of WO2024187927A1 publication Critical patent/WO2024187927A1/zh
Priority to US19/222,515 priority patent/US20250293252A1/en
Anticipated expiration legal-status Critical
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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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • 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
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • 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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/364—Composites as mixtures
    • 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
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • 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
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • 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
    • H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
    • 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
    • H01M2004/028—Positive electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2220/00—Batteries for particular applications
    • H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
    • 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 a battery and an electrical device.
  • secondary batteries are widely used in energy storage power systems such as hydropower, thermal power, wind power and solar power stations, as well as 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, as well as power tools, electric bicycles, electric motorcycles, electric vehicles, military equipment, aerospace and other fields.
  • secondary batteries have made great progress, higher requirements are put forward for their cycle performance, charging speed and service life.
  • the present application is made in view of the above-mentioned problems, and its purpose is to provide a battery and an electrical device that improve the fast charging performance and cycle performance of the battery.
  • the first aspect of the present application provides a battery, comprising a positive electrode plate, the positive electrode plate comprising a first positive electrode active material and a second positive electrode active material; wherein,
  • the first positive electrode active material includes a compound Li a Ni b Co c M1 d M2 e Of E g ; wherein,
  • M1 includes one or two elements of Mn and Al;
  • M2 includes one or more elements selected from the group consisting of Zr, Zn, Cu, Cr, Mg, Fe, V, Ti, Sr, Sb, Y, W, and Nb;
  • E includes one or more elements selected from N, F, S and Cl;
  • the second positive electrode active material includes a compound LixHyMn1 -zQzP1 - mGmO4 - nDn , wherein:
  • H includes one or more selected from Zn, Al, Na, K, Mg, Nb, Mo and W. Elements;
  • Q comprises one or more elements selected from Zn, Al, Na, K, Mg, Mo, W, Ti, V, Zr, Fe, Ni, Co, Ga, Sn, Sb, Nb and Ge;
  • G includes one or more elements selected from B, Si, N, S, F, Cl and Br;
  • D comprises one or more elements selected from S, F, Cl and Br;
  • the battery meets the following requirements:
  • A represents the mass percentage of the second positive electrode active material in the two positive electrode active materials
  • B represents the proportion of the charging capacity of the second positive electrode active material less than 3.7V in the entire charging capacity measured by the single particle microelectrode method
  • C represents the proportion of the battery's charging capacity less than 3.7V in the total charging capacity
  • R represents the resistance of the positive electrode at 25°C, in ⁇ .
  • the present application defines a combination of a first positive electrode active material and a second positive electrode active material.
  • the proportion of the battery's charging capacity in the low SOC range of less than 3.7V in the total charging capacity is increased, and the tolerance boundary of the charging rate in the low SOC range is improved.
  • the proportion of the charging capacity in the high SOC range in the total charging capacity is maintained, and the deterioration of the tolerance boundary of the charging rate in the high SOC range is alleviated, thereby improving the battery's fast charging performance and the battery's cycle performance.
  • A is 0.1 to 0.5, optionally 0.1 to 0.3, more optionally 0.2 to 0.3; and/or,
  • C is 0.05 to 0.23, optionally 0.09 to 0.16; and/or,
  • 0 ⁇ R ⁇ 1 can be selected as 0.1 to 0.6, and more preferably as 0.2 to 0.4.
  • A, B, and C within the above range can further improve the charge rate tolerance boundary in the low SOC interval, and make the charge rate tolerance boundary in the high SOC interval more suitable, thereby further improving the fast charging performance and/or cycle performance of the battery;
  • R within the above range can obtain a lower overpotential, which is beneficial to improving the rate performance of the battery and making the charging process go smoothly.
  • Q includes one or more elements of Fe, Ti, V, Ni, Co and Mg; and/or,
  • G includes one or more elements of B, Si, N and S; and/or,
  • x is from 0.977 to 1;
  • y is from 0 to 0.001;
  • z is 0.1 to 0.9 or 0.001 to 0.6, optionally 0.3 to 0.7; and/or,
  • m is 0 to 0.001 or 0.001 to 0.1;
  • n is 0 to 0.001 or 0.001 to 0.1.
  • the proportion of the battery's charging capacity in the low SOC range of less than 3.7V in the total charging capacity can be further increased, and the charging rate tolerance boundary in the low SOC range can be further improved.
  • the proportion of the charging capacity in the high SOC range in the total charging capacity can be maintained, and the deterioration of the charging rate tolerance boundary in the high SOC range can be alleviated, thereby further improving the battery's fast charging performance and/or cycle performance.
  • a in the first positive electrode active material, a is 0.9 to 1.1; and/or,
  • d is from 0.003 to 0.4;
  • b is 30% to 99.5%, optionally 50% to 99%, more preferably 55% to 88%; and/or,
  • c is 0.2% to 52%, optionally 0.5% to 49.5%, and more optionally 5% to 35%.
  • the Ni content within the above range can improve the fast charging performance and/or cycle performance of the battery.
  • the Co content within the above range can improve the fast charging performance and/or cycle performance of the battery.
  • the D v 50 particle size of the single crystal particles or quasi-single crystal particles is 1.5 to 4.5 ⁇ m, and 2 to 4.1 ⁇ m; and/or,
  • the D v 99 particle size of the single crystal particles or quasi-single crystal particles is ⁇ 18 ⁇ m, and may be 6.4 to 17.5 ⁇ m, and may be 6.5 to 13.5 ⁇ m; and/or,
  • the BET specific surface area of the first positive electrode active material is 0.42 to 1.2 m 2 /g, and may be 0.5 to 1 m 2 /g.
  • the D v 50 particle size, D v 99 particle size, and BET specific surface area within the above ranges are beneficial to increasing the active sites of the positive electrode active material, improving the fast charging performance and power of the battery, helping to reduce the side reactions of the positive electrode active material, and improving the cycle performance of the battery.
  • the first positive electrode active material is a polycrystalline material and satisfies:
  • the secondary particles have a Dv50 particle size of 6 to 14 ⁇ m, optionally 7 to 13 ⁇ m; and/or,
  • the Dv99 particle size of the secondary particles is ⁇ 30 ⁇ m, optionally 14.2 to 28.8 ⁇ m, more preferably 15.4 to 26.7 ⁇ m; and/or,
  • the primary particles have a particle size of 50 to 800 nm, optionally 50 to 600 nm; and/or,
  • the BET specific surface area of the first positive electrode active material is 0.8 to 1.2 m 2 /g, and optionally 0.8 to 1.1 m 2 /g.
  • the secondary particle D v 50 particle size, secondary particle D v 99 particle size, primary particle size, and BET specific surface area within the above ranges are beneficial to increasing the active sites of the positive electrode active material, improving the fast charging performance and power of the battery, helping to reduce the side reactions of the positive electrode active material, and improving the cycle performance of the battery.
  • the second positive electrode active material is a single crystal or a quasi-single crystal material and satisfies:
  • the single crystal particles or quasi-single crystal particles have a D v 50 particle size of 0.2 to 1.6 ⁇ m, and optionally 0.25 to 1.49 ⁇ m; and/or,
  • the single crystal particles or quasi-single crystal particles have a D v 99 particle size of 5.2 to 33.8 ⁇ m, and optionally 6.1 to 25.7 ⁇ m; and/or,
  • the BET specific surface area of the second positive electrode active material is 11.3 to 14.1 m 2 /g, and optionally 12 to 13.7 m 2 /g.
  • the second positive electrode active material is a single crystal or quasi-single crystal material
  • the above-mentioned ranges of D v 50 particle size, D v 99 particle size, and BET specific surface area are beneficial to increasing the active sites of the positive electrode active material. Improving the fast charging performance and power of the battery will help reduce the side reactions of the positive electrode active materials and improve the battery's cycle performance.
  • the first positive electrode active material has a layered structure; and/or the second positive electrode active material has an olivine structure.
  • the first positive electrode active material includes a core and a coating layer coating the core, the core is a compound Li a Ni b Co c M1 d M2 e Of E g ; and/or,
  • the second positive electrode active material includes a core and a coating layer coating the core, wherein the core is a compound Li x H y Mn 1-z Q z P 1-m G m O 4-n D n ;
  • the coating layers in the first positive electrode active material and the second positive electrode active material independently include one or more of pyrophosphate, phosphate and carbon.
  • the coating layer in the first positive electrode active material and/or the second positive electrode active material is beneficial to protecting the core, thereby reducing the occurrence of side reactions and improving the cycle performance of the battery.
  • the coating layer accounts for 0.5% to 2.2% by mass of the second positive electrode active material, optionally 1% to 1.9%, and more optionally 1.2% to 1.5%;
  • the coating layer in the second positive electrode active material is carbon
  • the second aspect of the present application also provides an electrical device, comprising the battery of the first aspect of the present application.
  • FIG. 1 is a schematic diagram of a secondary battery according to an embodiment of the present application.
  • FIG. 2 is an exploded view of the secondary battery according to the embodiment of the present application shown in FIG. 1 .
  • FIG. 3 is a schematic diagram of a battery module according to an embodiment of the present application.
  • FIG. 4 is a schematic diagram of a battery pack according to an embodiment of the present application.
  • FIG. 5 is an exploded view of the battery pack shown in FIG. 4 according to an embodiment of the present application.
  • FIG. 6 is a schematic diagram of an electric device using a secondary battery as a power source according to an embodiment of the present application.
  • “Scope” disclosed in the present application is limited in the form of lower limit and upper limit, and a 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 a special range.
  • the scope limited in this way can be including end values or not including end values, and can be arbitrarily combined, that is, any lower limit can be combined with any upper limit to form a scope. 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 numerical range "a-b" represents the abbreviation of any real number combination between a and b, wherein a and b are real numbers.
  • the numerical range "0-5" means that all real numbers between "0-5" are listed in this document, and "0-5" is just an abbreviation of these numerical combinations.
  • a parameter is expressed as an integer ⁇ 2, it is equivalent to disclosing that the parameter is, for example, an integer of 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, etc.
  • a 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.
  • a method may also 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 term "or” is inclusive.
  • the phrase “A or B” means “A, B, or both A and B”. More specifically, 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).
  • D v 50 particle size refers to a particle size at which the volume accumulation is 50% from the smaller particle size side in a volume-based particle size distribution.
  • D v 99 particle size refers to a particle size at which the volume accumulation is 99% from the small particle size side in a volume-based particle size distribution.
  • single crystal or single crystal-like material particle refers to a single particle (ie, a primary particle).
  • second particles and “polycrystalline material particles” generally have similar meanings, which refer to particles formed by agglomeration of more than 100 primary particles having an average particle size in the range of 50-800 nm.
  • the positive electrode active material is a polycrystalline material; otherwise, it is a single crystal or quasi-single crystal material.
  • Secondary batteries also known as rechargeable batteries or storage batteries, refer to batteries that can continue to be used by recharging the active materials after the battery is discharged.
  • a secondary battery includes a positive electrode sheet, a negative electrode sheet, a separator and an electrolyte.
  • active ions such as lithium ions
  • the separator is arranged between the positive electrode sheet and the negative electrode sheet, mainly to prevent the positive and negative electrodes from short-circuiting, while allowing active ions to pass through.
  • the electrolyte is between the positive electrode sheet and the negative electrode sheet, mainly to conduct active ions.
  • One embodiment of the present application provides a battery, comprising a positive electrode sheet, wherein the positive electrode sheet comprises a first positive electrode active material and a second positive electrode active material; wherein,
  • the first positive electrode active material includes a compound Li a Ni b Co c M1 d M2 e Of E g ; wherein,
  • M1 includes one or two elements of Mn and Al;
  • M2 includes one or more elements selected from the group consisting of Zr, Zn, Cu, Cr, Mg, Fe, V, Ti, Sr, Sb, Y, W, and Nb;
  • E includes one or more elements selected from N, F, S and Cl;
  • the second positive electrode active material includes a compound LixHyMn1 -zQzP1 - mGmO4 - nDn , wherein:
  • H includes one or more elements selected from Zn, Al, Na, K, Mg, Nb, Mo and W;
  • G includes one or more elements selected from B, Si, N, S, F, Cl and Br;
  • D comprises one or more elements selected from S, F, Cl and Br;
  • the battery meets the following requirements:
  • A represents the mass percentage of the second positive electrode active material in the two positive electrode active materials
  • B represents the proportion of the charging capacity of the second positive electrode active material less than 3.7V in the entire charging capacity measured by the single particle microelectrode method
  • C represents the proportion of the battery's charging capacity less than 3.7V in the total charging capacity
  • R represents the resistance of the positive electrode at 25°C, in ⁇ .
  • the diffusion coefficient of the first positive electrode active material is small in the low SOC range below 3.7V, resulting in a narrower charge rate tolerance margin in the low SOC range of the battery, which affects the fast charging performance of the battery.
  • the present application combines the first positive electrode active material with the second positive electrode active material and defines 0.1 to 0.75
  • the proportion of the battery's charging capacity in the low SOC range of less than 3.7V in the total charging capacity is increased, and the charging rate tolerance boundary in the low SOC range is improved.
  • the proportion of the charging capacity in the high SOC range in the total charging capacity is maintained, and the deterioration of the charging rate tolerance boundary in the high SOC range is alleviated, thereby improving the battery's fast charging performance and the battery's cycle performance.
  • It can be 0.1, 0.2, 0.23, 0.3, 0.32, 0.38, 0.4, 0.43, 0.45, 0.49, 0.5, 0.52, 0.53, 0.6, 0.7, 0.73, 0.75, and ranges consisting of any of the above values.
  • A is 0.1 to 0.5, optionally 0.1 to 0.3, and more optionally 0.2 to 0.3, for example, it can be 0.1, 0.2, 0.3, 0.4, 0.5, and any range thereof; and/or,
  • B is 0.4 to 0.6, and may be 0.5 to 0.6, for example, 0.4, 0.45, 0.48, 0.5, 0.55, 0.57, 0.6, and any range thereof; and/or,
  • C is 0.05 to 0.23, and may be 0.09 to 0.16, for example, 0.09, 0.1, 0.13, 0.16, 0.18, 0.2, 0.21, 0.23, and any range thereof; and/or,
  • 0 ⁇ R ⁇ 1 can be selected as 0.1 to 0.6, more can be selected as 0.2 to 0.4, for example, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6 and the range consisting of any of the above values.
  • a capacity-voltage curve of a discharge process is measured, where the X-axis represents the charging capacity, the Y-axis represents the voltage, the maximum value of the Y-axis represents the full charge voltage V1, the minimum value represents the full discharge voltage V2, and V2 ⁇ 3.7V ⁇ V1.
  • the capacity corresponding to the voltage 3.7V in the curve is Q1, and the capacity Q2 corresponding to the full discharge voltage V2 is the "entire charging capacity”.
  • Q2-Q1 represents "charging capacity less than 3.7V”
  • Q1 represents "charging capacity in a high SOC interval”.
  • the charging capacity less than 3.7V and the entire charging capacity of the second positive electrode active material are determined by a single-particle microelectrode method, which is a commonly used method in the field.
  • the single-particle microelectrode method mainly includes a microelectrode, a microscope, a micromanipulator and an electrochemical workstation.
  • the microelectrode is moved by a micromanipulator in combination with a microscope to make the microelectrode contact with a single particle of the second positive electrode active material.
  • an electrochemical test is performed at a certain temperature using a single particle as a working electrode, a lithium strip as a counter electrode and a reference electrode, and a certain electrolyte to obtain a capacity-voltage curve of the discharge process.
  • A, B, and C within the above range can further improve the charge rate tolerance boundary in the low SOC interval, and make the charge rate tolerance boundary in the high SOC interval more suitable, thereby further improving the fast charging performance and/or cycle performance of the battery;
  • G includes one or more elements of B, Si, N and S; and/or,
  • x is 0.977 to 1, for example, 0.977, 0.98, 0.985, 0.99, 0.992, 0.994, 1, and any range thereof; and/or,
  • y is 0 to 0.001, for example, 0, 0.0005, 0.001, and any range thereof;
  • z is 0.1 to 0.9 or 0.001 to 0.6, and can be 0.3 to 0.7, for example, 0.001, 0.005, 0.01, 0.05, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9 and any range thereof; and/or,
  • m is 0 to 0.001 or 0.001 to 0.1, for example, 0, 0.0005, 0.001, 0.005, 0.01, 0.02, 0.04, 0.05, 0.07, 0.08, 0.1 and any range thereof; and/or,
  • n is 0 to 0.001 or 0.001 to 0.1, for example, may be 0, 0.0005, 0.001, 0.005, 0.01, 0.02, 0.04, 0.05, 0.07, 0.08, 0.1, or a range consisting of any of the above values.
  • the proportion of the battery's charging capacity in the low SOC range of less than 3.7V in the total charging capacity can be further increased, and the charging rate tolerance boundary in the low SOC range can be further improved.
  • the proportion of the charging capacity in the high SOC range in the total charging capacity can be maintained, and the deterioration of the charging rate tolerance boundary in the high SOC range can be alleviated, thereby further improving the battery's fast charging performance and/or cycle performance.
  • a in the first positive electrode active material, a is 0.9 to 1.1, for example, 0.75, 0.8, 0.85, 0.9, 0.95, 1, 1.1, 1.2, and any range thereof; and/or,
  • d is 0.003 to 0.4, for example, 0.003, 0.005, 0.008, 0.01, 0.03, 0.04, 0.05, 0.07, 0.1, 0.13, 0.15, 0.2, 0.24, 0.26, 0.3, 0.33, 0.35, 0.38, 0.4, and any range thereof; and/or,
  • b is 30% to 99.5%, optionally 50% to 99%, more optionally 55% to 88%, for example, it can be 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 0.95, 0.995 and any range thereof; and/or,
  • c is 0.2% to 52%, optionally 0.5% to 49.5%, and more optionally 5% to 35%, for example, it can be 0.002, 0.005, 0.008, 0.01, 0.03, 0.06, 0.08, 0.1, 0.15, 0.2, 0.25, 0.3, 0.35, 0.4, 0.45, 0.48, 0.5, 0.52 and the range consisting of any of the above values.
  • the Ni content within the above range can improve the fast charging performance and/or cycle performance of the battery.
  • the Co content within the above range can improve the fast charging performance and/or cycle performance of the battery.
  • the first cathode material is a single crystal or quasi-single crystal material and satisfies:
  • the D v 50 particle size of the single crystal particles or quasi-single crystal particles is 1.5 to 4.5 ⁇ m, and can be 2 to 4.1 ⁇ m, for example, 1.5 ⁇ m, 2 ⁇ m, 2.5 ⁇ m, 3 ⁇ m, 3.2 ⁇ m, 3.5 ⁇ m, 4 ⁇ m, 4.2 ⁇ m, 4.5 ⁇ m, and any range thereof; and/or,
  • the D v 99 particle size of the single crystal particles or quasi-single crystal particles is ⁇ 18 ⁇ m, and may be 6.4 to 17.5 ⁇ m, or more preferably 6.5 to 13.5 ⁇ m, for example, 1 ⁇ m, 2 ⁇ m, 3 ⁇ m, 4 ⁇ m, 5 ⁇ m, 5.5 ⁇ m, 6 ⁇ m, 6.4 ⁇ m, 7 ⁇ m, 7.5 ⁇ m, 8 ⁇ m, 8.5 ⁇ m, 9 ⁇ m, 9.5 ⁇ m, 10 ⁇ m, 10.4 ⁇ m, 11 ⁇ m, 11.6 ⁇ m, 12 ⁇ m, 12.5 ⁇ m, 13 ⁇ m, 13.6 ⁇ m, 14 ⁇ m, 14.5 ⁇ m, 15 ⁇ m, 15.5 ⁇ m, 16 ⁇ m, 16.4 ⁇ m, 17 ⁇ m, 17.5 ⁇ m, 18 ⁇ m, or any range thereof; and/or,
  • the BET specific surface area of the first positive electrode active material is 0.42 to 1.2 m 2 /g, and can be optionally 0.5 to 1 m 2 /g, for example, 0.42 m 2 /g , 0.47 m 2 /g, 0.5 m 2 /g, 0.55 m 2 /g, 0.58 m 2 /g, 0.6 m 2 /g, 0.65 m 2 /g, 0.68 m 2 /g, 0.7 m 2 /g, 0.75 m 2 /g , 0.8 m 2 /g, 0.85 m 2 /g, 0.9 m 2 /g , 0.95 m 2 /g , 1.0 m 2 /g, 1.1 m 2 /g, 1.2 m 2 /g, and ranges consisting of any of the above numerical values.
  • the D v 50 particle size, D v 99 particle size, and BET specific surface area within the above range are beneficial to increasing the active sites of the positive electrode active material, improving the fast charging performance and power of the battery, helping to reduce the side reactions of the positive electrode active material, and improving the cycle performance of the battery.
  • the first positive electrode active material is a polycrystalline material and satisfies:
  • the Dv50 particle size of the secondary particles is 6 to 14 ⁇ m, and can be 7 to 13 ⁇ m, for example, 6 ⁇ m, 7 ⁇ m, 8 ⁇ m, 9 ⁇ m, 10 ⁇ m, 11 ⁇ m, 12 ⁇ m, 13 ⁇ m, 14 ⁇ m, and any range thereof; and/or,
  • the Dv99 particle size of the secondary particles is less than 30 ⁇ m, and may be 14.2 to 28.8 ⁇ m, and more preferably 15.4 to 26.7 ⁇ m, for example, 6 ⁇ m, 10 ⁇ m, 11 ⁇ m, 13 ⁇ m, 15 ⁇ m, 17 ⁇ m, 18 ⁇ m, 20 ⁇ m, 21 ⁇ m, 22 ⁇ m, 24 ⁇ m, 26 ⁇ m, 27 ⁇ m, 28 ⁇ m, 29 ⁇ m, and any range thereof; and/or,
  • the particle size of the primary particles is 50 to 800 nm, and can be 50 to 600 nm, for example, 50 nm, 55 nm, 60 nm, 65 nm, 70 nm, 80 nm, 90 nm, 100 nm, 120 nm, 150 nm, 200 nm, 240 nm, 260 nm, 300 nm, 350 nm, 400 nm, 450 nm, 500 nm, 550 nm, 600 nm, 650 nm, 700 nm, 750 nm, 800 nm, and any range consisting of the above values; and/or,
  • the BET specific surface area of the first positive electrode active material is 0.8 to 1.2 m 2 /g, and may be 0.8 to 1.1 m 2 /g, for example, 0.85 m 2 /g, 0.9 m 2 /g, 0.95 m 2 /g, 0.98 m 2 /g, 1.0 m 2 /g, 1.05 m 2 /g, 1.1 m 2 /g, 1.2 m 2 /g, and ranges consisting of any of the above values.
  • the secondary particle D v 50 particle size, the secondary particle D v 99 particle size, the primary particle size, and the BET specific surface area within the above range are beneficial to increasing the active sites of the positive electrode active material, improving the fast charging performance and power of the battery, helping to reduce the side reactions of the positive electrode active material, and improving the cycle performance of the battery.
  • the second positive electrode active material is a single crystal or a quasi-single crystal material and satisfies:
  • the D v 50 particle size of the single crystal particles or quasi-single crystal particles is 0.2 to 1.6 ⁇ m, and can be 0.25 to 1.49 ⁇ m, for example, 0.3 ⁇ m, 0.4 ⁇ m, 0.5 ⁇ m, 0.6 ⁇ m, 0.7 ⁇ m, 0.8 ⁇ m, 0.9 ⁇ m, 1.0 ⁇ m, 1.1 ⁇ m, 1.2 ⁇ m, 1.3 ⁇ m, 1.4 ⁇ m, 1.5 ⁇ m, 1.6 ⁇ m, and any range thereof; and/or,
  • the D v 99 particle size of the single crystal particles or quasi-single crystal particles is 5.2 to 33.8 ⁇ m, and can be 6.1 to 25.7 ⁇ m, for example, 5.2 ⁇ m, 5.5 ⁇ m, 6 ⁇ m, 6.5 ⁇ m, 7 ⁇ m, 7.5 ⁇ m, 8 ⁇ m, 8.5 ⁇ m, 9 ⁇ m, 9.5 ⁇ m, 10 ⁇ m, 10.5 ⁇ m, 11 ⁇ m, 12 ⁇ m, 13 ⁇ m, 14 ⁇ m, 15 ⁇ m, 16 ⁇ m, 18 ⁇ m, 20 ⁇ m, 22 ⁇ m, 24 ⁇ m, 26 ⁇ m, 28 ⁇ m, 30 ⁇ m, 31 ⁇ m, 33 ⁇ m, 33.8 ⁇ m, and any range thereof; and/or,
  • the BET specific surface area of the second positive electrode active material is 11.3 to 14.1 m 2 /g, and can be 12 to 13.7 m 2 /g, for example, 11.3 m 2 /g, 11.5 m 2 /g, 12 m 2 /g, 12.5 m 2 /g, 12.8 m 2 /g, 13 m 2 /g, 13.6 m 2 /g, 14 m 2 /g, 14.1 m 2 /g, or ranges consisting of any of the above values.
  • the D v 50 particle size, D v 99 particle size, and BET specific surface area within the above ranges are beneficial to increasing the active sites of the positive electrode active material, improving the fast charging performance and power of the battery, helping to reduce the side reactions of the positive electrode active material, and improving the cycle performance of the battery.
  • the crystal form can be determined by conventional methods in the art, such as testing the sample using a scanning electron microscope, adjusting the magnification so that there are more than 10 agglomerated particles in the field of view, measuring the number of primary particles constituting each agglomerated particle, and measuring the length of the primary particles with a ruler as the particle size, sorting the particle size of the primary particles in each agglomerated particle from large to small, removing 1/10 of the largest particle size data and 1/10 of the smallest particle size data, and According to the data, the average of the remaining particle size data is taken as the average particle size of the primary particles in the agglomerated particles.
  • the sample is judged to be a polycrystalline material, otherwise, it is judged to be a single crystal or quasi-single crystal material.
  • the average particle size of the primary particles is taken as the particle size of the primary particles of the polycrystalline material.
  • the D v 50 particle size and the D v 99 particle size can be measured by conventional methods in the art, for example, according to the method in the national standard GB/T 19077-2016 "Particle Size Distribution Laser Diffraction Method".
  • the BET specific surface area is the BET specific surface area at 25°C.
  • the BET specific surface area can be determined using conventional methods in the art, for example, according to the method in the national standard GB/T 19587-2004 "Determination of the specific surface area of solid substances by gas adsorption BET method".
  • the first cathode active material has a layered structure; and/or the second cathode active material has an olivine structure.
  • the first positive electrode active material includes a core and a coating layer coating the core, the core is a compound Li a Ni b Co c M 1 d M 2 e Of E g ; and/or,
  • the second positive electrode active material includes a core and a coating layer coating the core, wherein the core is a compound Li x H y Mn 1-z Q z P 1-m G m O 4-n D n ;
  • the coating layers in the first positive electrode active material and the second positive electrode active material independently include one or more of pyrophosphate, phosphate and carbon.
  • the coating layer in the first positive electrode active material and/or the second positive electrode active material is beneficial to protecting the core, thereby reducing the occurrence of side reactions and improving the cycle performance of the battery.
  • the coating layer accounts for 0.5% to 2.2% by mass of the second positive electrode active material, optionally 1% to 1.9%, and more optionally 1.2% to 1.5%;
  • the coating layer in the second positive electrode active material is carbon
  • the battery includes a negative electrode sheet, 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, and the negative electrode film layer contains a negative electrode active material;
  • the coating area density of the negative electrode active material is 9 to 11 mg/cm2, optionally 9.5 to 10.5 mg/ cm2 , and more optionally 10.0 to 10.4 mg/cm2; and/or,
  • the density of the negative electrode film layer is 1.55 to 1.75 g/cm 3 , and can be 1.6 to 1.7 g/cm 3 , and can be 1.64 to 1.69 g/cm 3 .
  • the coating surface density of the negative electrode active material within the above range is conducive to improving the fast charge rate performance of the battery, improving the charging CB of the battery, and alleviating the lithium plating problem of the negative electrode sheet.
  • the density of the negative electrode film layer within the above range is conducive to improving the lithium insertion capacity of the negative electrode sheet and the contact between the negative electrode active material and the conductive agent, thereby improving the fast charge rate performance and/or cycle performance of the battery.
  • coating area density of negative electrode active material refers to the weight of negative electrode active material contained in a unit area of a negative electrode sheet.
  • the positive electrode sheet generally includes a positive electrode current collector and a positive electrode film layer disposed on at least one surface of the positive electrode current collector, and the positive electrode film layer includes the first positive electrode active material and the second positive electrode active material mentioned above.
  • 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 (aluminum, aluminum alloy, nickel, nickel alloy, titanium, titanium alloy, silver and silver alloy, etc.) on a polymer material substrate (such as a substrate of polypropylene (PP), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polystyrene (PS), polyethylene (PE), etc.).
  • PP polypropylene
  • PET polyethylene terephthalate
  • PBT polybutylene terephthalate
  • PS polystyrene
  • PE polyethylene
  • the positive electrode film layer may also optionally include a binder.
  • the binder may include at least one 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, for example, 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 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 in the following manner: 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 (such as N-methylpyrrolidone) to form a positive electrode slurry; the positive electrode slurry is coated on the positive electrode collector, and after drying, cold pressing and other processes, the positive electrode sheet can be obtained.
  • a solvent such as N-methylpyrrolidone
  • the negative electrode plate includes a negative electrode current collector and a negative electrode film layer arranged on at least one surface of the negative electrode current collector, and the negative electrode film layer includes a negative electrode active material.
  • 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.
  • a metal foil a copper foil may 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 substrate.
  • the composite current collector may be formed by forming a metal material (copper, copper alloy, nickel, nickel alloy, titanium, titanium alloy, silver and silver alloy, etc.) on a polymer material substrate (such as a substrate of polypropylene (PP), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polystyrene (PS), polyethylene (PE), etc.).
  • PP polypropylene
  • PET polyethylene terephthalate
  • PBT polybutylene terephthalate
  • PS polystyrene
  • PE polyethylene
  • the negative electrode active material may adopt the negative electrode active material for the battery known in the art.
  • the negative electrode active material may include at least one of the following materials: artificial graphite, natural graphite, soft carbon, hard carbon, silicon-based materials, tin-based materials, lithium titanate, etc.
  • the silicon-based material may be selected from at least one of elemental silicon, silicon oxide compounds, silicon-carbon composites, silicon-nitrogen composites, and silicon alloys.
  • the tin-based material may be selected from at least one of elemental tin, tin oxide compounds, and tin alloys.
  • the present application is not limited to these materials, and other traditional materials that can be used as negative electrode active materials for batteries may also be used. These negative electrode active materials may be used alone or in combination of two or more.
  • the negative electrode film layer may further include a binder.
  • the binder may be selected from at least one 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 also optionally include 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 may optionally include other additives, such as a thickener (eg, sodium carboxymethyl cellulose (CMC-Na)).
  • a thickener eg, sodium carboxymethyl cellulose (CMC-Na)
  • the negative electrode sheet can be prepared in the following manner: 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 (such as deionized water) to form a negative electrode slurry; the negative electrode slurry is coated on the negative electrode collector, and after drying, cold pressing and other processes, the negative electrode sheet can be obtained.
  • a solvent such as deionized water
  • the electrolyte plays the role of conducting ions between the positive electrode and the negative electrode.
  • the present application has no specific restrictions on the type of electrolyte, which can be selected according to needs.
  • the electrolyte can be liquid, gel or all-solid.
  • the electrolyte is liquid and includes an electrolyte salt and a solvent.
  • the electrolyte salt can be selected from at least one of lithium hexafluorophosphate, lithium tetrafluoroborate, lithium perchlorate, lithium hexafluoroarsenate, lithium bis(fluorosulfonyl)imide, lithium bis(trifluoromethanesulfonyl)imide, lithium trifluoromethanesulfonate, lithium difluorophosphate, lithium difluorooxalatoborate, lithium dioxalatoborate, lithium difluorodioxalatophosphate, and lithium tetrafluorooxalatophosphate.
  • the solvent can be selected from at least one of ethylene carbonate, propylene carbonate, ethyl methyl carbonate, diethyl carbonate, dimethyl carbonate, dipropyl carbonate, methyl propyl carbonate, ethyl propyl carbonate, butylene carbonate, fluoroethylene carbonate, methyl formate, methyl acetate, ethyl acetate, propyl acetate, methyl propionate, ethyl propionate, propyl propionate, methyl butyrate, ethyl butyrate, 1,4-butyrolactone, cyclopentane sulfone, dimethyl sulfone, methyl ethyl sulfone and diethyl sulfone.
  • the electrolyte may further include additives.
  • the additives may include 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 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 can be selected from at least one of glass fiber, non-woven fabric, polyethylene, polypropylene and polyvinylidene fluoride.
  • the isolation membrane can be a single-layer film or a multi-layer composite film, without particular limitation.
  • the materials of each layer can be the same or different, without particular limitation.
  • 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 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 examples of the plastic include 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 specific actual needs.
  • secondary batteries may be assembled into a battery module.
  • the number of secondary batteries contained in the battery module may be one or more, and the specific number may be selected by those skilled in the art according to the application and capacity of the battery module.
  • FIG3 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. Of course, they may also be arranged in any other manner. Further, the plurality of secondary batteries 5 may be fixed by fasteners.
  • the battery module 4 may further include a housing having a storage space, a plurality of secondary The battery 5 is accommodated in the accommodation space.
  • the battery modules described above may also be assembled into a battery pack.
  • the battery pack may contain one or more battery modules, and the specific number may be selected by those skilled in the art according to the application and capacity of the battery pack.
  • FIG4 and FIG5 are battery packs 1 as an example.
  • 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 body 2 and a lower box body 3, and the upper box body 2 can be covered on the lower box body 3 to form a closed space for accommodating the battery modules 4.
  • the plurality of battery modules 4 can be arranged in the battery box in any manner.
  • the battery may include but is not limited to a secondary battery, a battery module, and a battery pack.
  • the present application also provides an electrical device, which includes at least one of the secondary battery, battery module, or battery pack provided in the present application.
  • the secondary battery, battery module, or battery pack 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 (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, electric golf carts, electric trucks, etc.), electric trains, ships and satellites, energy storage systems, etc., but are not limited thereto.
  • a secondary battery, a battery module or a battery pack can be selected according to its usage requirements.
  • Fig. 6 is an example of an electric device.
  • 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.
  • the first positive electrode active material was purchased from Guangdong Brunp Recycling Technology Co., Ltd.
  • Second positive electrode active material purchased from Shenzhen Defang Nanotechnology Co., Ltd.
  • Isolation membrane Polyethylene (PE) porous polymer film is used.
  • Ethylene carbonate (EC), diethyl carbonate (DEC) and dimethyl carbonate (DMC) were mixed at a volume ratio of 1:1:1, and then LiPF 6 and fluoroethylene carbonate (FEC) were uniformly dissolved in the above solution to obtain an electrolyte.
  • the concentration of LiPF 6 was 1 mol/L
  • the content of fluoroethylene carbonate (FEC) was 5 wt.%.
  • Examples 2-41 and Comparative Examples 1-2 are similar to those of Example 1, and the different product parameters are detailed in Table 1. Among them:
  • A represents the mass percentage of the second positive electrode active material in the two positive electrode active materials
  • B represents the second positive electrode active material measured by single particle microelectrode method.
  • C represents the proportion of the battery's charging capacity less than 3.7V in the total charging capacity
  • R represents the resistance of the positive electrode at 25°C ( ⁇ ).
  • the first positive electrode active material is a layered structure, all purchased from Guangdong Brunp Recycling Technology Co., Ltd.; the second positive electrode active materials of Examples 1-38 are olivine-type, all purchased from Shenzhen Defang Nano Technology Co., Ltd.
  • the slurry is transferred to a spray drying device for spray drying and granulation, the drying temperature is set to 250° C., and dried for 4 hours to obtain particles.
  • a protective atmosphere of nitrogen (90 volume %) + hydrogen (10 volume %) the above powder is sintered at 700° C. for 10 hours.
  • the positive electrode active material can be detected for element content by inductively coupled plasma emission spectroscopy (ICP).
  • the preparation method of the second positive electrode active material is the same as that of Example 1-36, except that the amount of high-purity Li 2 CO 3 is changed to 0.4885 mol, Mo(SO 4 ) 3 is replaced by MgSO 4 , the amount of FeSO 4 .
  • H 2 O is changed to 0.68 mol, 0.02 mol of Ti(SO 4 ) 2 is added when preparing doped manganese oxalate, and H 4 SiO 4 is replaced by HNO 3 .
  • ICP Inductively coupled plasma optical emission spectroscopy
  • the preparation method of the second positive electrode active material is the same as that of Example 1-36, except that the amount of high-purity Li 2 CO 3 is changed to 0.496 mol, Mo(SO 4 ) 3 is replaced by W(SO 4 ) 3 , and H 4 SiO 4 is replaced by H 2 SO 4.
  • the element content of the positive electrode active material can be detected by inductively coupled plasma emission spectroscopy (ICP).
  • the test was performed using a BER1300 film resistor meter.
  • the test steps are as follows:
  • the positive electrode sheet is made into a disc with a diameter of 22 mm;
  • the particles of the second positive active material (Dv50 particle size of 0.25-1.49 ⁇ m) were dispersed on a cover glass washed successively with a washing solution (a 98 wt % H 2 SO 4 aqueous solution and a 30 wt % hydrogen peroxide solution mixed in a volume ratio of 3:1) and deionized water.
  • a washing solution a 98 wt % H 2 SO 4 aqueous solution and a 30 wt % hydrogen peroxide solution mixed in a volume ratio of 3:1
  • the microelectrode is a platinum wire encapsulated by a glass capillary.
  • the diameter of the platinum wire is 10 ⁇ m.
  • the radius ratio of the glass capillary to the platinum wire is less than 5.
  • the end face of the platinum wire is polished into a needle tip shape.
  • the platinum wire and the copper wire are connected by conductive silver glue.
  • the microelectrode needs to be placed in a 0.5 mol/L H 2 SO 4 aqueous solution for cyclic voltammetry scanning.
  • the scanning speed is 50 mV/s and the scanning potential range is -0.22 V to 1.22 V (vs. SCE) to remove the impurities remaining on the microelectrode.
  • the single-particle microelectrode test device mainly includes a microelectrode, a microscope, a micromanipulator and an electrochemical workstation.
  • the microelectrode is moved by the micromanipulator in combination with the microscope to make the microelectrode contact with a single particle of the second positive electrode active material.
  • the single particle is used as the working electrode
  • the lithium strip is used as the counter electrode and the reference electrode
  • ethylene carbonate (EC) and propylene carbonate (PC) (volume ratio 1:1) containing 1 mol/L LiPF 6 are used as the electrolyte for electrochemical testing;
  • the electrochemical test temperature is 25°C, and the constant current is charged to 4.4V at 0.33C and then switched to constant voltage charging.
  • the soft-pack laminated battery was tested, and the operation was as follows: the test environment temperature was 25°C, and it was charged to 4.4V at a constant current of 0.33C and then switched to constant voltage charging. When the charging current decreased to 0.05C, the constant voltage charging ended, and then it was discharged at 0.33C to a full discharge voltage of 2.5V. This process was repeated 3 times, and the capacity-voltage curve of the third discharge process was taken.
  • the X-axis represents the charging capacity
  • the Y-axis represents the voltage.
  • the charging capacity corresponding to the voltage of 3.7V is Q1, and the full discharge voltage of 2.5V corresponds to the entire charging capacity Q2.
  • single crystal/quasi-single crystal particle means a single particle (ie, a primary particle).
  • second particles and “polycrystalline material particles” generally have similar meanings, which refer to particles formed by agglomeration of more than 100 primary particles having an average particle size in the range of 50-800 nm.
  • the positive electrode active material is tested by scanning electron microscope, and the sample and magnification are adjusted so that there are more than 10 agglomerated particles in the field of view, and the number of primary particles constituting each agglomerated particle is measured, and the size of the primary particle in the length direction is measured with a ruler and recorded as the particle size, and the particle size of the primary particles in each agglomerated particle is sorted from large to small, and 1/10 of the maximum particle size data and 1/10 of the minimum particle size data are removed, and the average of the remaining particle size data is taken as the average particle size of the primary particles in the agglomerated particle.
  • the positive electrode active material is determined to be a polycrystalline material, otherwise, it is determined to be a single crystal or quasi-single crystal material.
  • the average particle size of the primary particles of the polycrystalline material was recorded as the particle size of the primary particles.
  • the Dv50 particle size and Dv99 particle size of single crystal particles or quasi-single crystal particles and secondary particles were determined according to the method in the national standard GB/T 19077-2016 "Laser diffraction method for particle size distribution", wherein deionized water was used as the solvent and ultrasonic treatment was performed for 5 minutes before the test.
  • the test environment temperature is 25°C.
  • the national standard GB/T 19587-2004 “Gas Absorption The BET specific surface area of the powder was determined by the method in “Determination of specific surface area of solid substances by BET method", wherein the powder was placed in a vacuum oven and dried at 200°C for ⁇ 2h before the test, and the required amount of powder was >20g.
  • the specific process is as follows: the soft-pack laminated battery is charged with C1 to a full charge voltage of 4.4V or a negative electrode voltage of 0V, and the battery SOC value at the end of charging is obtained, and then discharged at 0.33C to a full discharge voltage of 2.5V; the above process is repeated according to the charging rate from small to large, and the SOC value at the end of charging at different rates can be obtained.
  • the SOC value at the end of charging is fitted with the corresponding rate value to obtain the relationship between the SOC and the rate value at the end of charging.
  • the attenuation degree of the battery cell 100% ⁇ Dn/D3
  • a disc-shaped negative electrode current collector with an area of 10 mm2 and a thickness of d1 (mm), and weigh it m1 (g); take a negative electrode current collector with the same material and thickness, with a length of 10 mm and a width of 200 mm, and coat the negative electrode slurry on both sides of the negative electrode current collector, dry it, and cold press it at 30-40°C to obtain a negative electrode sheet, which includes the negative electrode current collector and the negative electrode slurry coated on the negative electrode current collector.
  • the negative electrode film layer on the negative electrode current collector starting from one end of the electrode sheet, take 10 mm2 discs at lengths of 1m, 3m, 5m, 7m, and 9m respectively, weigh the weight m2-m6 (g) of each disc and calculate the average weight m s (g) of the disc, measure the thickness d2-d6 (mm) of each disc and calculate the average thickness d s (mm) of the disc; calculate the density (g/cm 3 ) of the negative electrode film layer according to the following formula.
  • the positive electrode sheet and the negative electrode sheet are respectively assembled into button batteries (the negative electrode adopts a metal lithium sheet);
  • the test conditions of the positive electrode sheet button battery are: at 25°C, 0.1C charge and discharge, 2.5-4.45V, the capacity of the positive electrode sheet button battery is obtained, divided by the mass of the positive electrode active material, and the gram capacity Q1 (mAh/g) of the positive electrode active material is obtained;
  • the test conditions of the negative electrode sheet button battery are: at 25°C, 0.1C charge and discharge, 0.005-2.0V, the capacity of the negative electrode sheet button battery is obtained, divided by the mass of the negative electrode active material, and the gram capacity Q2 (mAh/g) of the negative electrode active material is obtained.
  • a disc-shaped positive electrode current collector with an area of 10 mm2 and weigh its weight m1 (g); take a disc-shaped positive electrode current collector with an area of 10 mm2 and weigh its weight m1 (g). 2 , weighing its weight m12 (g); taking a positive electrode collector of the same material and thickness with a length of 10m and a width of 200mm, coating the aforementioned positive electrode slurry on the front and back sides of the positive electrode collector, drying and cold pressing to obtain a positive electrode plate, which includes a positive electrode collector and a positive electrode film layer coated on the positive electrode collector, and the content of positive electrode active material in the positive electrode film layer is W1; taking a negative electrode collector of the same material and thickness with a length of 10m and a width of 200mm, coating the aforementioned negative electrode slurry on the front and back sides of the negative electrode collector, drying and cold pressing to obtain a negative electrode plate, which includes a negative electrode collector and a negative electrode film layer coated on the negative electrode collector,
  • the weight of each positive electrode disc is recorded as m2-m6 (g) and the average weight of the positive electrode disc is calculated as m s1 (g)
  • the weight of each negative electrode disc is recorded as m7-m11 (g)
  • the average weight of the negative electrode disc is calculated as m s2 (g).
  • Charging CB value (m s2 /10-m12/10) ⁇ Q2 ⁇ W2 / [(m s1 /10-m1/10) ⁇ Q1 ⁇ W1]
  • the cycled soft-pack laminated battery of item (8) was charged at a constant current of 0.33C to a full charge voltage of 4.4V, and then switched to constant voltage charging.
  • the charging current was reduced to 0.05C, the charging junction
  • the battery was disassembled at 2% relative humidity to observe whether there was silvery white metal precipitation on the surface of the negative electrode. If so, it was lithium deposition, otherwise there was no lithium deposition.
  • the battery made of the positive electrode active material in the embodiment of the present application has better fast charging performance and longer cycle life;

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Abstract

一种电池和用电装置，电池包括正极极片，正极极片包含第一正极活性材料和第二正极活性材料；并且满足式（I），其中A表示所述第二正极活性材料在两种正极活性材料中的质量百分比； B表示采用单颗粒微电极法测定的所述第二正极活性材料的小于3.7V充电容量在整个充电容量中的占比； C表示所述电池的小于3.7V充电容量在整个充电容量中的占比； R表示所述正极极片在25℃下的电阻，单位为Ω。

Description

一种电池和用电装置
本申请要求2023年3月10日提交的中国专利申请202310229296.3的优先权，其全部内容通过引入并入本文。
技术领域
本申请涉及锂电池技术领域，尤其涉及一种电池和用电装置。
背景技术
近年来，随着二次电池的应用范围越来越广泛，二次电池广泛应用于水力、火力、风力和太阳能电站等储能电源系统，以及电动工具、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。由于二次电池取得了极大的发展，因此对其循环性能、充电速度和使用寿命等提出了更高的要求。
发明内容
本申请是鉴于上述课题而进行的，其目的在于，提供一种电池和用电装置，提高了电池的快充性能和循环性能。
为了达到上述目的，本申请第一方面提供了一种电池，包括正极极片，正极极片包含第一正极活性材料和第二正极活性材料；其中，
第一正极活性材料包括化合物LiaNibCocM1dM2eOfEg；其中，
M1包括Mn和Al的一种或两种元素；
M2包括Zr、Zn、Cu、Cr、Mg、Fe、V、Ti、Sr、Sb、Y、W和Nb中的一种或多种元素；
E包括N、F、S和Cl中的一种或多种元素；
0.75≤a≤1.2；0<b<1；0<c<1；0<d<1；0≤e≤0.2；1≤f≤2.5，0≤g≤1，且f+g≤3；
第二正极活性材料包括化合物LixHyMn1-zQzP1-mGmO4-nDn，其中，
H包括选自Zn、Al、Na、K、Mg、Nb、Mo和W中的一种或多 种元素；
Q包括选自Zn、Al、Na、K、Mg、Mo、W、Ti、V、Zr、Fe、Ni、Co、Ga、Sn、Sb、Nb和Ge中的一种或多种元素；
G包括选自B、Si、N、S、F、Cl和Br中的一种或多种元素；
D包括选自S、F、Cl和Br中的一种或多种元素；
x为0.9至1.1；y为0至0.1；z为0.001至0.9；m为0至0.1；n为0至0.1；
并且，电池满足：
其中，
A表示第二正极活性材料在两种正极活性材料中的质量百分比；
B表示采用单颗粒微电极法测定的第二正极活性材料的小于3.7V充电容量在整个充电容量中的占比；
C表示电池的小于3.7V充电容量在整个充电容量中的占比；
R表示正极极片在25℃下的电阻，单位为Ω。
由此，本申请通过第一正极活性材料和第二正极活性材料组合，并限定在0.1至0.75之间，提高了电池的小于3.7V低SOC区间充电容量在充电总容量中的占比，改善了低SOC区间充电倍率的耐受边界，同时维持了高SOC区间充电容量在充电总容量中的占比，缓解了高SOC区间充电倍率耐受边界的恶化，从而提高了电池的快充性能，提高了电池的循环性能。
在任意实施方式中，
可选地，
由此，可以获得更加适宜的低SOC区间充电倍率耐受边界和高SOC区间充电倍率耐受边界，从而进一步提高电池的快充性能和/或循环性能。
在任意实施方式中，A为0.1至0.5，可选为0.1至0.3，更可选为0.2至0.3；和/或，
B为0.4至0.6，可选为0.5至0.6；和/或，
C为0.05至0.23，可选为0.09至0.16；和/或，
0<R<1，可选为0.1至0.6，更可选为0.2至0.4。
上述范围内的A、B、C能够进一步改善低SOC区间充电倍率耐受边界，同时使高SOC区间充电倍率耐受边界更加合适，从而进一步提高电池的快充性能和/或循环性能；
上述范围内的R能够获得较低的过电位，有利于提高电池的倍率性能，使充电过程顺利进行。
在任意实施方式中，第二正极活性材料中，Q包括Fe、Ti、V、Ni、Co和Mg中的一种或多种元素；和/或，
G包括B、Si、N和S中的一种或多种元素；和/或，
x为0.977至1；和/或，
y为0至0.001；和/或，
z为0.1至0.9或者0.001至0.6，可选为0.3至0.7；和/或，
m为0至0.001或者0.001至0.1；和/或，
n为0至0.001或者0.001至0.1。
由此，通过包括上述Q和G元素的第二正极活性材料可以进一步提高电池小于3.7V低SOC区间充电容量在充电总容量中的占比，进一步改善低SOC区间充电倍率耐受边界，同时维持高SOC区间充电容量在充电总容量中的占比，缓解高SOC区间充电倍率耐受边界恶化，从而进一步提高电池的快充性能和/或循环性能。
在任意实施方式中，第一正极活性材料中，a为0.9至1.1；和/或，
d为0.003至0.4；和/或，
b为30％至99.5％，可选为50％至99％，更可选为55％至88％；和/或，
c为0.2％至52％，可选为0.5％至49.5％，更可选为5％至35％。
上述范围内的Ni含量能够提高电池的快充性能和/或循环性能。
上述范围的Co含量能够提高电池的快充性能和/或循环性能。
在任意实施方式中，第一正极材料为单晶或类单晶材料，并且满足：
单晶颗粒或类单晶颗粒的Dv50粒径为1.5至4.5μm，可选为2 至4.1μm；和/或，
单晶颗粒或类单晶颗粒的Dv99粒径≤18μm，可选为6.4至17.5μm，更可选为6.5至13.5μm；和/或，
第一正极活性材料的BET比表面积为0.42至1.2m2/g，可选为0.5至1m2/g。
第一正极活性材料为单晶或类单晶材料时，上述范围的Dv50粒径、Dv99粒径、BET比表面积有利于增加正极活性材料的活性点位，提高电池的快充性能和功率，有助于减少正极活性材料的副反应，提高电池的循环性能。
在任意实施方式中，第一正极活性材料为多晶材料，并且满足：
二次颗粒的Dv50粒径为6至14μm，可选为7至13μm；和/或，
二次颗粒的Dv99粒径<30μm，可选为14.2至28.8μm，更可选为15.4至26.7μm；和/或，
一次颗粒的粒径为50至800nm，可选为50至600nm；和/或，
第一正极活性材料的BET比表面积为0.8至1.2m2/g，可选为0.8至1.1m2/g。
第一正极活性材料为多晶材料时，上述范围的二次颗粒Dv50粒径、二次颗粒Dv99粒径、一次颗粒粒径、BET比表面积有利于增加正极活性材料的活性点位，提高电池的快充性能和功率，有助于减少正极活性材料的副反应，提高电池的循环性能。
在任意实施方式中，第二正极活性材料为单晶或类单晶材料，并且满足：
单晶颗粒或类单晶颗粒的Dv50粒径为0.2至1.6μm，可选为0.25至1.49μm；和/或，
单晶颗粒或类单晶颗粒的Dv99粒径为5.2至33.8μm，可选为6.1至25.7μm；和/或，
第二正极活性材料的BET比表面积为11.3至14.1m2/g，可选为12至13.7m2/g。
第二正极活性材料为单晶或类单晶材料时，上述范围的Dv50粒径、Dv99粒径、BET比表面积有利于增加正极活性材料的活性点位， 提高电池的快充性能和功率，有助于减少正极活性材料的副反应，提高电池的循环性能。
在任意实施方式中，第一正极活性材料为层状结构；和/或，第二正极活性材料为橄榄石结构。
在任意实施方式中，第一正极活性材料包括内核和包覆内核的包覆层，内核为化合物LiaNibCocM1dM2eOfEg；和/或，
第二正极活性材料包括内核和包覆内核的包覆层，内核为化合物LixHyMn1-zQzP1-mGmO4-nDn；
可选地，第一正极活性材料和第二正极活性材料中的包覆层独立地包括焦磷酸盐、磷酸盐和碳中的一种或多种。
由此，第一正极活性材料和/或第二正极活性材料中的包覆层有利于保护内核，从而减少副反应的发生，提高电池的循环性能。
在任意实施方式中，包覆层在第二正极活性材料中的质量占比为0.5％至2.2％，可选为1％至1.9％，更可选为1.2％至1.5％；
可选地，第二正极活性材料中的包覆层为碳。
本申请的第二方面还提供一种用电装置，包括本申请第一方面的电池。
附图说明
图1是本申请一实施方式的二次电池的示意图。
图2是图1所示的本申请一实施方式的二次电池的分解图。
图3是本申请一实施方式的电池模块的示意图。
图4是本申请一实施方式的电池包的示意图。
图5是图4所示的本申请一实施方式的电池包的分解图。
图6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池、电池模块和用电装置的实施方式。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，方法包括步骤(a)和(b)，表示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，提到方法还可包括步骤(c)，表示步骤(c)可以任意顺序加入到方法，例如，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，“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)。
如果没有特别的说明，在本申请中，术语“Dv50粒径”是指在体积基准的粒度分布中，从小粒径侧起，达到体积累积50％的粒径。
如果没有特别的说明，在本申请中，术语“Dv99粒径”是指在体积基准的粒度分布中，从小粒径侧起，达到体积累积99％的粒径。
如果没有特别的说明，在本申请中，术语“单晶或类单晶材料颗粒”是指单个颗粒(即一次颗粒)。
如果没有特别的说明，在本申请中，术语“二次颗粒”和“多晶材料颗粒”通常具有类似的含义，其意指由超过100个平均粒径在50-800nm范围内的一次颗粒团聚形成的颗粒。
如果没有特别的说明，在本申请中，如果采集的50％以上(包括50％)数量的团聚颗粒中的一次颗粒的数量和平均粒径符合上述“多晶材料颗粒”的定义，则其为该正极活性材料为多晶材料，否则其为单晶或类单晶材料。
[二次电池]
二次电池又称为充电电池或蓄电池，是指在电池放电后可通过充电的方式使活性材料激活而继续使用的电池。
通常情况下，二次电池包括正极极片、负极极片、隔离膜及电解液。在电池充放电过程中，活性离子(例如锂离子)在正极极片和负极极片之间往返嵌入和脱出。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，同时可以使活性离子通过。电解液在正极极片和负极极片之间，主要起到传导活性离子的作用。
本申请的一个实施方式提供一种电池，包括正极极片，正极极片包含第一正极活性材料和第二正极活性材料；其中，
第一正极活性材料包括化合物LiaNibCocM1dM2eOfEg；其中，
M1包括Mn和Al的一种或两种元素；
M2包括Zr、Zn、Cu、Cr、Mg、Fe、V、Ti、Sr、Sb、Y、W和Nb中的一种或多种元素；
E包括N、F、S和Cl中的一种或多种元素；
0.75≤a≤1.2；0<b<1；0<c<1；0<d<1；0≤e≤0.2；1≤f≤2.5，0≤g≤1，且f+g≤3；
第二正极活性材料包括化合物LixHyMn1-zQzP1-mGmO4-nDn，其中，
H包括选自Zn、Al、Na、K、Mg、Nb、Mo和W中的一种或多种元素；
Q包括选自Zn、Al、Na、K、Mg、Mo、W、Ti、V、Zr、Fe、Ni、Co、Ga、Sn、Sb、Nb和Ge中的一种或多种元素；
G包括选自B、Si、N、S、F、Cl和Br中的一种或多种元素；
D包括选自S、F、Cl和Br中的一种或多种元素；
x为0.9至1.1；y为0至0.1；z为0.001至0.9；m为0至0.1；n为0至0.1；
并且，电池满足：
其中，
A表示第二正极活性材料在两种正极活性材料中的质量百分比；
B表示采用单颗粒微电极法测定的第二正极活性材料的小于3.7V充电容量在整个充电容量中的占比；
C表示电池的小于3.7V充电容量在整个充电容量中的占比；
R表示正极极片在25℃下的电阻，单位为Ω。
第一正极活性材料在小于3.7V低SOC区间的扩散系数较小，导致电池的低SOC区间充电倍率耐受边界较窄，影响了电池的快充性能。虽然机理尚不明确，但本申请人意外地发现：本申请通过第一正极活性材料和第二正极活性材料相组合，并限定在0.1至0.75 之间，提高了电池的小于3.7V低SOC区间充电容量在充电总容量中的占比，改善了低SOC区间充电倍率耐受边界，同时维持了高SOC区间充电容量在充电总容量中的占比，缓解了高SOC区间充电倍率耐受边界的恶化，从而提高了电池的快充性能，提高了电池的循环性能。
在一些实施方式中，
可选地，
例如可以为0.1、0.2、0.23、0.3、0.32、0.38、0.4、0.43、0.45、0.49、0.5、0.52、0.53、0.6、0.7、0.73、0.75以及上述任意数值组成的范围。
由此，可以获得更加适宜的低SOC区间充电倍率耐受边界和高SOC区间充电倍率耐受边界，从而进一步提高电池的快充性能和/或循环性能。
在一些实施方式中，A为0.1至0.5，可选为0.1至0.3，更可选为0.2至0.3，例如可以为0.1、0.2、0.3、0.4、0.5以及上述任意数值组成的范围；和/或，
B为0.4至0.6，可选为0.5至0.6，例如可以为0.4、0.45、0.48、0.5、0.55、0.57、0.6以及上述任意数值组成的范围；和/或，
C为0.05至0.23，可选为0.09至0.16，例如可以为0.09、0.1、0.13、0.16、0.18、0.2、0.21、0.23以及上述任意数值组成的范围；和/或，
0<R<1，可选为0.1至0.6，更可选为0.2至0.4，例如0.1、0.2、0.3、0.4、0.5、0.6以及上述任意数值组成的范围。
在一些实施方式中，测取放电流程的容量-电压曲线，X轴表示充电容量，Y轴表示电压，Y轴的最大值表示满充电压V1、最小值表示满放电压V2，并且V2<3.7V<V1，曲线中的电压3.7V对应的容量为Q1，满放电压V2对应的容量Q2为“整个充电容量”，Q2-Q1表示“小于3.7V充电容量”，Q1表示“高SOC区间充电容量”。
在一些实施方式中，B表示在25℃下采用单颗粒微电极法测定的第二正极活性材料的小于3.7V充电容量在整个充电容量中的占比。
在一些实施方式中，C表示在25℃下测定的电池小于3.7V充电 容量在整个充电容量中的占比。
在一些实施方式中，第二正极活性材料的小于3.7V充电容量和整个充电容量均采用单颗粒微电极法测定，单颗粒微电极法是本领域的常用方法，例如具体为：单颗粒微电极法主要包括微电极、显微镜、微操作手和电化学工作站，通过微操作手结合显微镜来移动微电极，使微电极与第二正极活性材料的单个颗粒接触，然后，以单个颗粒为工作电极、以锂带为对电极和参比电极、采用一定的电解液在一定的温度下进行电化学测试，以获得放电流程的容量-电压曲线。
在一些实施方式中，电池的小于3.7V充电容量和整个充电容量可采用本领域的常规方法测定，例如充放电循环三次，由第三次放电流程的容量-电压曲线来获得电池的小于3.7V充电容量和整个充电容量。
在一些实施方式中，R可采用本领域的常规方法和设备测定，例如采用BER1300膜片电阻仪进行测试，测试温度为25℃。
上述范围内的A、B、C能够进一步改善低SOC区间充电倍率耐受边界，同时使高SOC区间充电倍率耐受边界更加合适，从而进一步提高电池的快充性能和/或循环性能；
上述范围内的R能够获得较低的过电位，有利于提高电池的倍率性能，使充电过程顺利进行。
在一些实施方式中，第二正极活性材料中，Q包括Fe、Ti、V、Ni、Co和Mg中的一种或多种元素；和/或，
G包括B、Si、N和S中的一种或多种元素；和/或，
x为0.977至1，例如可以为0.977、0.98、0.985、0.99、0.992、0.994、1以及上述任意数值组成的范围；和/或，
y为0至0.001，例如可以为0、0.0005、0.001以及上述任意数值组成的范围；和/或，
z为0.1至0.9或者0.001至0.6，可选为0.3至0.7，例如可以为0.001、0.005、0.01、0.05、0.1、0.2、0.3、0.4、0.5、0.6、0.7、0.8、0.9以及上述任意数值组成的范围；和/或，
m为0至0.001或者0.001至0.1，例如可以为0、0.0005、0.001、 0.005、0.01、0.02、0.04、0.05、0.07、0.08、0.1以及上述任意数值组成的范围；和/或，
n为0至0.001或者0.001至0.1，例如可以为0、0.0005、0.001、0.005、0.01、0.02、0.04、0.05、0.07、0.08、0.1以及上述任意数值组成的范围。
由此，通过包括上述Q和G元素的第二正极活性材料可以进一步提高电池小于3.7V低SOC区间充电容量在充电总容量中的占比，进一步改善低SOC区间充电倍率耐受边界，同时维持高SOC区间充电容量在充电总容量中的占比，缓解高SOC区间充电倍率耐受边界恶化，从而进一步提高电池的快充性能和/或循环性能。
在一些实施方式中，第一正极活性材料中，a为0.9至1.1，例如可以为0.75、0.8、0.85、0.9、0.95、1、1.1、1.2以及上述任意数值组成的范围；和/或，
d为0.003至0.4，例如可以为0.003、0.005、0.008、0.01、0.03、0.04、0.05、0.07、0.1、0.13、0.15、0.2、0.24、0.26、0.3、0.33、0.35、0.38、0.4以及上述任意数值组成的范围；和/或，
b为30％至99.5％，可选为50％至99％，更可选为55％至88％，例如可以为0.3、0.4、0.5、0.6、0.7、0.8、0.9、0.95、0.995以及上述任意数值组成的范围；和/或，
c为0.2％至52％，可选为0.5％至49.5％，更可选为5％至35％，例如可以为0.002、0.005、0.008、0.01、0.03、0.06、0.08、0.1、0.15、0.2、0.25、0.3、0.35、0.4、0.45、0.48、0.5、0.52以及上述任意数值组成的范围。
上述范围内的Ni含量能够提高电池的快充性能和/或循环性能。
上述范围的Co含量能够提高电池的快充性能和/或循环性能。
在一些实施方式中，第一正极材料为单晶或类单晶材料，并且满足：
单晶颗粒或类单晶颗粒的Dv50粒径为1.5至4.5μm，可选为2至4.1μm，例如可以为1.5μm、2μm、2.5μm、3μm、3.2μm、3.5μm、4μm、4.2μm、4.5μm以及上述任意数值组成的范围；和/或，
单晶颗粒或类单晶颗粒的Dv99粒径≤18μm，可选为6.4至17.5μm，更可选为6.5至13.5μm，例如可以为1μm、2μm、3μm、4μm、5μm、5.5μm、6μm、6.4μm、7μm、7.5μm、8μm、8.5μm、9μm、9.5μm、10μm、10.4μm、11μm、11.6μm、12μm、12.5μm、13μm、13.6μm、14μm、14.5μm、15μm、15.5μm、16μm、16.4μm、17μm、17.5μm、18μm以及上述任意数值组成的范围；和/或，
第一正极活性材料的BET比表面积为0.42至1.2m2/g，可选为0.5至1m2/g，例如可以为0.42m2/g、0.47m2/g、0.5m2/g、0.55m2/g、0.58m2/g、0.6m2/g、0.65m2/g、0.68m2/g、0.7m2/g、0.75m2/g、0.8m2/g、0.85m2/g、0.9m2/g、0.95m2/g、1.0m2/g、1.1m2/g、1.2m2/g以及上述任意数值组成的范围。
第一正极活性材料为单晶或类单晶材料时，上述范围内的Dv50粒径、Dv99粒径、BET比表面积有利于增加正极活性材料的活性点位，提高电池的快充性能和功率，有助于减少正极活性材料的副反应，提高电池的循环性能。
在一些实施方式中，第一正极活性材料为多晶材料，并且满足：
二次颗粒的Dv50粒径为6至14μm，可选为7至13μm，例如6μm、7μm、8μm、9μm、10μm、11μm、12μm、13μm、14μm以及上述任意数值组成的范围；和/或，
二次颗粒的Dv99粒径<30μm，可选为14.2至28.8μm，更可选为15.4至26.7μm，例如可以为6μm、10μm、11μm、13μm、15μm、17μm、18μm、20μm、21μm、22μm、24μm、26μm、27μm、28μm、29μm以及上述任意数值组成的范围；和/或，
一次颗粒的粒径为50至800nm，可选为50至600nm，例如可以为50nm、55nm、60nm、65nm、70nm、80nm、90nm、100nm、120nm、150nm、200nm、240nm、260nm、300nm、350nm、400nm、450nm、500nm、550nm、600nm、650nm、700nm、750nm、800nm以及上述任意数值组成的范围；和/或，
第一正极活性材料的BET比表面积为0.8至1.2m2/g，可选为0.8至1.1m2/g，例如可以为0.85m2/g、0.9m2/g、0.95m2/g、0.98m2/g、 1.0m2/g、1.05m2/g、1.1m2/g、1.2m2/g以及上述任意数值组成的范围。
第一正极活性材料为多晶材料时，上述范围内的二次颗粒Dv50粒径、二次颗粒Dv99粒径、一次颗粒粒径、BET比表面积有利于增加正极活性材料的活性点位，提高电池的快充性能和功率，有助于减少正极活性材料的副反应，提高电池的循环性能。
在一些实施方式中，第二正极活性材料为单晶或类单晶材料，并且满足：
单晶颗粒或类单晶颗粒的Dv50粒径为0.2至1.6μm，可选为0.25至1.49μm，例如可以为0.3μm、0.4μm、0.5μm、0.6μm、0.7μm、0.8μm、0.9μm、1.0μm、1.1μm、1.2μm、1.3μm、1.4μm、1.5μm、1.6μm以及上述任意数值组成的范围；和/或，
单晶颗粒或类单晶颗粒的Dv99粒径为5.2至33.8μm，可选为6.1至25.7μm，例如5.2μm、5.5μm、6μm、6.5μm、7μm、7.5μm、8μm、8.5μm、9μm、9.5μm、10μm、10.5μm、11μm、12μm、13μm、14μm、15μm、16μm、18μm、20μm、22μm、24μm、26μm、28μm、30μm、31μm、33μm、33.8μm以及上述任意数值组成的范围；和/或，
第二正极活性材料的BET比表面积为11.3至14.1m2/g，可选为12至13.7m2/g，例如可以为11.3m2/g、11.5m2/g、12m2/g、12.5m2/g、12.8m2/g、13m2/g、13.6m2/g、14m2/g、14.1m2/g以及上述任意数值组成的范围。
第二正极活性材料为单晶或类单晶材料时，上述范围的Dv50粒径、Dv99粒径、BET比表面积有利于增加正极活性材料的活性点位，提高电池的快充性能和功率，有助于减少正极活性材料的副反应，提高电池的循环性能。
在一些实施方式中，晶型可以采用本领域的常规方法测定，例如采用扫描电镜对样品测试，调整放大倍数使视野内具有大于10个的团聚颗粒，计量组成每个团聚颗粒的一次颗粒数量，并用标尺测量一次颗粒长度方向的尺寸记为粒径，将每个团聚颗粒中的一次颗粒的粒径由大至小排序，去除1/10的粒径最大数据和1/10的粒径最小的数 据，剩余粒径数据取平均值作为该团聚颗粒中一次颗粒的平均粒径。如果50％以上(包括50％)数量的团聚颗粒中的一次颗粒的数量和平均粒径符合前述“多晶材料颗粒”的定义，则判定该样品为多晶材料，否则，判定为单晶或类单晶材料。将一次颗粒的平均粒径作为多晶材料的一次颗粒的粒径。
在一些实施方式中，Dv50粒径和Dv99粒径可以采用本领域的常规方法测定，例如按照国家标准GB/T 19077-2016《粒度分布激光衍射法》中的方法测定。
在一些实施方式中，BET比表面积为在25℃下的BET比表面积。
在一些实施方式中，BET比表面积可以采用本领域的常规方法测定，例如按照国家标准GB/T 19587-2004《气体吸附BET法测定固态物质比表面积》中的方法测定。
在一些实施方式中，第一正极活性材料为层状结构；和/或，第二正极活性材料为橄榄石结构。
在一些实施方式中，第一正极活性材料包括内核和包覆内核的包覆层，内核为化合物LiaNibCocM1dM2eOfEg；和/或，
第二正极活性材料包括内核和包覆内核的包覆层，内核为化合物LixHyMn1-zQzP1-mGmO4-nDn；
可选地，第一正极活性材料和第二正极活性材料中的包覆层独立地包括焦磷酸盐、磷酸盐和碳中的一种或多种。
由此，第一正极活性材料和/或第二正极活性材料中的包覆层有利于保护内核，从而减少副反应的发生，提高电池的循环性能。
在一些实施方式中，包覆层在第二正极活性材料中的质量占比为0.5％至2.2％，可选为1％至1.9％，更可选为1.2％至1.5％；
可选地，第二正极活性材料中的包覆层为碳。
在一些实施方式中，电池包括负极极片，负极极片包括负极集流体和设置在负极集流体至少一个表面上的负极膜层，负极膜层包含负极活性材料；其中，
负极活性材料的涂覆面密度为9至11mg/cm，可选为9.5至10.5mg/cm2，更可选为10.0至10.4mg/cm；和/或，
负极膜层的密度为1.55至1.75g/cm3，可选为1.6至1.7g/cm3，更可选为1.64至1.69g/cm3。
负极活性材料的涂覆面密度在上述范围内有利于改善电池的快充倍率性能，改善电池的充电CB，缓解负极极片的析锂问题。负极膜层的密度在上述范围内有利于改善负极极片的嵌锂能力和负极活性材料与导电剂之间的接触性，从而改善电池的快充倍率性能和/或循环性能。
在一些实施方式中，“负极活性材料的涂覆面密度”是指单位面积负极极片所含有的负极活性材料重量。
[正极极片]
正极极片通常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，正极膜层包含上述的第一正极活性材料和第二正极活性材料。
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，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，正极膜层还可选地包括粘结剂。作为示例，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，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，负极膜层包括负极活性材料。
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，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，负极活性材料可采用本领域公知的用于电池的负极活性材料。作为示例，负极活性材料可包括以下材料中的至少一种：人造石墨、天然石墨、软炭、硬炭、硅基材料、锡基材料和钛酸锂等。硅基材料可选自单质硅、硅氧化合物、硅碳复合物、硅氮复合物以及硅合金中的至少一种。锡基材料可选自单质锡、锡氧化合物以及锡合金中的至少一种。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材料的传统材料。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。
在一些实施方式中，负极膜层还可选地包括粘结剂。作为示例，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。作为示例， 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。
[电解质]
电解质在正极极片和负极极片之间起到传导离子的作用。本申请对电解质的种类没有具体的限制，可根据需求进行选择。例如，电解质可以是液态的、凝胶态的或全固态的。
在一些实施方式中，电解质为液态的，且包括电解质盐和溶剂。
在一些实施方式中，电解质盐可选自六氟磷酸锂、四氟硼酸锂、高氯酸锂、六氟砷酸锂、双氟磺酰亚胺锂、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，溶剂可选自碳酸亚乙酯、碳酸亚丙酯、碳酸甲乙酯、碳酸二乙酯、碳酸二甲酯、碳酸二丙酯、碳酸甲丙酯、碳酸乙丙酯、碳酸亚丁酯、氟代碳酸亚乙酯、甲酸甲酯、乙酸甲酯、乙酸乙酯、乙酸丙酯、丙酸甲酯、丙酸乙酯、丙酸丙酯、丁酸甲酯、丁酸乙酯、1,4-丁内酯、环丁砜、二甲砜、甲乙砜及二乙砜中的至少一种。
在一些实施方式中，电解液还可选地包括添加剂。作为示例，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。
[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，隔离膜的材质可选自玻璃纤维、无纺布、聚乙烯、聚丙烯及聚偏二氟乙烯中的至少一种。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。
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。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能够盖设于开口，以封闭容纳腔。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3是作为一个示例的电池模块4。参照图3，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4和图5是作为一个示例的电池包1。参照图4和图5，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。
本申请中，电池可以包括但不限于二次电池、电池模块和电池包。
另外，本申请还提供一种用电装置，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。二次电池、电池模块、或电池包可以用作用电装置的电源，也可以用作用电装置的能量存储单元。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6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。
[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)第一正极活性材料：购买自广东邦普循环科技有限公司。
(2)第二正极活性材料：购买自深圳市德方纳米科技股份有限公司。
(3)正极极片的制备：将第一正极活性材料、第二正极活性材料、聚偏二氟乙烯(PVDF)和导电碳按照63:27:5:5的质量比加入到N-甲基吡咯烷酮(NMP)中，在干燥房中搅拌制成均匀的浆料，控制粘度为3000～10000mPa·S，在正极集流体铝箔上涂敷上述的浆料，经过烘干处理，制成正极极片。
(4)负极极片的制备：将石墨、羧甲基纤维素钠(CMC)、丁苯橡胶(SBR)、导电碳按照90:2:3:5的质量比加入到去离子水中，，搅拌制成均匀的浆料，控制粘度为3000～10000mPa·S，在负极集流体铜箔上涂敷上述的负极浆料，经过烘干处理，制成负极极片。
(5)隔离膜：采用聚乙烯(PE)多孔聚合薄膜。
(6)电解液的制备：将碳酸乙烯酯(EC)、碳酸二乙酯(DEC)和碳酸二甲酯(DMC)按体积比1:1:1混合，然后将LiPF6、氟代碳酸乙烯酯(FEC)均匀溶解在上述溶液中，得到电解液。该电解液中，LiPF6的浓度为1mol/L，氟代碳酸乙烯酯(FEC)的含量为5wt.％。
(7)软包叠片电池的制备：将上述的正极极片、负极极片和隔膜按照Z字型叠片结构制成相应电芯，将电芯在90℃的环境下真空烘干12h，随后进行正负极的极耳超声焊接，正极采用铝极耳，负极采用镍极耳，正负极的极耳位于电芯同侧，将极耳焊接后的电芯装入合适尺寸的铝塑膜中进行顶侧封装，封装常规温度为145℃，注液，静置，化成，老化，排气，二封，容量测试即可得到制备好的软包叠片电池。
实施例2-41和对比例1-2与实施例1的二次电池制备方法相似，不同的产品参数详见表1。其中：
A表示第二正极活性材料在两种正极活性材料中的质量百分比；
B表示采用单颗粒微电极法测定的第二正极活性材料的小于 3.7V充电容量在整个充电容量中的占比；
C表示电池的小于3.7V充电容量在整个充电容量中的占比；
R表示正极极片在25℃下的电阻(Ω)。
表1中，第一正极活性材料为层状结构，均购买自广东邦普循环科技有限公司；实施例1-38的第二正极活性材料为橄榄石型，均购买自深圳市德方纳米科技股份有限公司。
实施例39第二正极活性材料的制备方法
制备掺杂的草酸锰：将1.3mol的MnSO4﹒H2O、0.7mol的FeSO4﹒H2O在混料机中充分混合6小时。将混合物转移至反应釜中，并加入10L去离子水和2mol二水合草酸(以草酸计)。将反应釜加热至80℃，以600rpm的转速搅拌6小时，反应终止(无气泡产生)，得到Fe掺杂的草酸锰悬浮液。然后过滤悬浮液，将滤饼在120℃下烘干，之后进行研磨，得到中值粒径Dv50为100nm左右的Fe掺杂的草酸锰颗粒。
制备掺杂的磷酸锰锂：取1mol上述草酸锰颗粒、0.497mol碳酸锂、0.001mol的Mo(SO4)3、含有0.999mol磷酸的浓度为85％的磷酸水溶液、0.001mol的H4SiO4、0.0005mol的NH4HF2和0.005mol蔗糖加入到20L去离子水中。将混合物转入砂磨机中充分研磨搅拌10小时，得到浆料。将浆料转移到喷雾干燥设备中进行喷雾干燥造粒，设定干燥温度为250℃，干燥4小时，得到颗粒。在氮气(90体积％)+氢气(10体积％)保护气氛中，将上述粉料在700℃下烧结10小时。正极活性材料可用电感耦合等离子体发射光谱(ICP)进行元素含量的检测。
实施例40第二正极活性材料的制备方法
除了将高纯Li2CO3的量改变为0.4885mol，将Mo(SO4)3换成MgSO4，将FeSO4﹒H2O的量改变为0.68mol，在制备掺杂的草酸锰时还加入0.02mol的Ti(SO4)2，并将H4SiO4换成HNO3之外，其他与实施例1-36第二正极活性材料的制备方法相同。正极活性材料可用 电感耦合等离子体发射光谱(ICP)进行元素含量的检测。
实施例41第二正极活性材料的制备方法
除了将高纯Li2CO3的量改变为0.496mol，将Mo(SO4)3换成W(SO4)3，将H4SiO4换成H2SO4之外，其他与实施例1-36第二正极活性材料的制备方法相同。正极活性材料可用电感耦合等离子体发射光谱(ICP)进行元素含量的检测。







电池测试
(1)正极极片的电阻测定：
采用BER1300膜片电阻仪进行测试，测试步骤如下：
a)将正极极片制成直径为22mm的圆片；
b)将制备好的圆片放入BER1300仪器的测试平台上进行测试，测试压力为0.4吨，测试温度为25℃，测试时间为10s，所得到的电阻数值即为正极极片的电阻。
(2)第二正极活性材料小于3.7V充电容量在整个充电容量中的占比的测定(单颗粒微电极法)：
将第二正极活性材料的颗粒(Dv50粒径为0.25-1.49μm)分散在依次用洗液(98wt％浓度的H2SO4水溶液和30wt％浓度的双氧水以体积比3:1混合)和去离子水清洗过的盖玻片上。
微电极为玻璃毛细管包封的铂丝，铂丝的直径为10μm，玻璃毛细管与铂丝的半径比值小于5，铂丝的端面打磨成针尖形，铂丝和导线铜丝之间通过导电银胶导通。测试前，需将微电极置于0.5mol/L的H2SO4水溶液中进行循环伏安扫描，扫描速度为50mV/s，扫描电势范围为-0.22V～1.22V(vs.SCE)，以去除微电极上残留的杂质。
单颗粒微电极测试装置主要包括微电极、显微镜、微操作手和电化学工作站，通过微操作手结合显微镜来移动微电极，使微电极与第二正极活性材料的单个颗粒接触，然后，以单个颗粒为工作电极，以锂带为对电极和参比电极，以含有1mol/L LiPF6的碳酸亚乙酯(EC)和碳酸丙烯酯(PC)(体积比1:1)为电解液进行电化学测试；电化学测试温度为25℃，以0.33C恒流充电至4.4V后转为恒压充电，当充电电流减小至0.05C时，恒压充电结束，随后以0.33C放电至满放电压2.5V，取放电流程的容量-电压曲线，X轴表示充电容量，Y轴表示电压，电压3.7V对应的充电容量为Q3，满放电压2.5V对应整个充电容量Q4，按照如下公式计算电压小于3.7V的充电容量在整个充电容量中的占比B。
B(％)＝100×(Q4-Q3)/Q4
(3)电池小于3.7V充电容量在整个充电容量中的占比的测定：
对软包叠片电池进行测试，操作如下：测试环境温度为25℃，以0.33C恒流充电至4.4V后转为恒压充电，当充电电流减小至0.05C时，恒压充电结束，随后0.33C放电至满放电压2.5V，按此流程重复3次，取第3次放电流程的容量-电压曲线，X轴表示充电容量，Y轴表示电压，电压3.7V对应的充电容量为Q1，满放电压2.5V对应整个充电容量Q2，按照如下公式计算电池小于3.7V充电容量在整个充电容量中的占比C。
C(％)＝100×(Q2-Q1)/Q2
(4)晶体类型及多晶材料的一次颗粒粒径的测试：
如果没有特别的说明，在本申请中，术语“单晶/类单晶颗粒”意指单个颗粒(即一次颗粒)。
如果没有特别的说明，在本申请中，术语“二次颗粒”和“多晶材料颗粒”通常具有类似的含义，其意指由超过100个平均粒径在50-800nm范围内的一次颗粒团聚形成的颗粒。
采用扫描电镜对正极活性材料进行测试，调整样品和放大倍数使视野内具有大于10个的团聚颗粒，计量组成每个团聚颗粒的一次颗粒数量，并用标尺测量一次颗粒长度方向的尺寸记为粒径，将每个团聚颗粒中的一次颗粒的粒径由大至小排序，去除1/10的粒径最大数据和1/10的粒径最小的数据，剩余粒径数据取平均值作为该团聚颗粒中一次颗粒的平均粒径。如果50％以上(包括50％)数量的团聚颗粒中的一次颗粒的数量和平均粒径符合上述“多晶材料颗粒”的定义，则判定该正极活性材料为多晶材料，否则，判定为单晶或类单晶材料。
记录多晶材料的一次颗粒的平均粒径作为一次颗粒的粒径。
(5)粒度分布测试：
按照国家标准GB/T 19077-2016《粒度分布激光衍射法》中的方法测定单晶颗粒或类单晶颗粒、二次颗粒的Dv50粒径和Dv99粒径，其中，溶剂使用去离子水，测试前超声处理5分钟。
(6)BET比表面积的测试：
测试环境温度为25℃，按照国家标准GB/T 19587-2004《气体吸 附BET法测定固态物质比表面积》中的方法测定粉末的BET比表面积，其中，测试前将粉末置于真空烘箱中在200℃干燥≥2h，粉末需求量称取＞20g。
(7)10％～80％SOC充电时间的测试：
在25℃恒温环境中，对软包叠片电池进行不同倍率(C1<C2<C3<C4<……<Cn)的充电测试，测试过程中充电倍率由小至大，充电过程中需同时监测软包叠片电池的全电电压和软包叠片电池的负极电压。具体过程如下：软包叠片电池以C1充电至满充电压4.4V或负极电压为0V，获得充电结束时电池SOC值，然后以0.33C放电至满放电压2.5V；按照由小至大的充电倍率重复上述过程，可得到不同倍率充电结束时SOC值，将充电结束时SOC值与对应的倍率值进行拟合，得到充电结束时SOC与倍率值之间的关系式，将20％SOC、30％SOC、40％SOC、50％SOC、60％SOC、70％SOC、80％SOC代入关系式中，得到相应的倍率C20％、C30％、C40％、C50％、C60％、C70％、C80％，按照下式计算出10％～80％SOC充电时间(min)；
10％～80％SOC充电时间＝(60/C20％+60/C30％+……+60/C80％)×10％。
(8)循环寿命测试：
将电池在25℃恒温环境中，以0.5C由2.5V充电至4.25-4.3V，然后在4.25-4.3V下恒压充电至电流≤0.05mA，静置5分钟，然后以0.5C放电至2.5V，记录电池首次循环的放电容量为D1；重复上述操作，每次循环的放电容量记为Dn(n＝2,3……)；按照如下公式计算电芯的衰减程度(State of health SOH)，记录衰减程度至80％SOH时的循环圈数n。
电芯的衰减程度＝100％×Dn/D3
(9)负极膜层密度的测试：
室温环境下，取面积10mm2、厚度d1(mm)的圆片形负极集流体，称其重量m1(g)；取同样材质和厚度的负极集流体长10m、宽200mm，在负极集流体的正反两面涂覆前述的负极浆料，经干燥、在30-40T下冷压，得到负极极片，其包括负极集流体和涂布在 负极集流体上的负极膜层；从极片一端开始，分别在1m、3m、5m、7m、9m长度处取10mm2圆片，称量各圆片的重量m2-m6(g)并计算圆片的平均重量ms(g)，测量各圆片的厚度d2-d6(mm)并计算圆片的平均厚度ds(mm)；按照如下公式计算负极膜层的密度(g/cm3)。
(10)充电CB数据的测试：
正极极片和负极极片分别装配成扣式电池(负极采用金属锂片)；正极极片扣式电池的测试条件：25℃下，0.1C充放电，2.5～4.45V，得到正极极片扣式电池的容量，除以正极活性材料质量，得到正极活性材料的克容量Q1(mAh/g)；负极极片扣式电池的测试条件：25℃下，0.1C充放电，0.005～2.0V，得到负极极片扣式电池的容量，除以负极活性材料质量，得到负极活性材料的克容量Q2(mAh/g)。
室温环境下，取面积10mm2的圆片形正极集流体，称其重量m1(g)；取面积10mm2的圆片形负极集流体，称其重量m12(g)；取同样材质和厚度的正极集流体长10m、宽200mm，在正极集流体的正反两面涂覆前述的正极浆料，经干燥、冷压，得到正极极片，其包括正极集流体和涂布在正极集流体上的正极膜层，正极膜层中的正极活性材料含量为W1；取同样材质和厚度的负极集流体长10m、宽200mm，在负极集流体的正反两面涂覆前述的负极浆料，经干燥、冷压，得到负极极片，其包括负极集流体和涂布在负极集流体上的负极膜层，负极膜层中的负极活性材料含量为W2；从正极极片/负极极片的一端开始，分别在1m、3m、5m、7m、9m长度处取10mm2圆片，正极的各圆片重量记为m2-m6(g)并计算正极圆片的平均重量ms1(g)，负极的各圆片重量记为m7-m11(g)并计算负极圆片的平均重量ms2(g)。
按照如下公式计算充电CB值。
充电CB值＝(ms2/10-m12/10)×Q2×W2/[(ms1/10-m1/10)×Q1×W1]
(11)析锂情况的测试：
将上述第(8)项的循环后软包叠片电池以0.33C恒流充电至满充电压4.4V，转为恒压充电，当充电电流减小至0.05C时，充电结 束，将电池在2％相对湿度下进行拆解，观察负极表面是否有银白色金属析出，若有则为析锂，否则无析锂。
表2：实施例1-41与对比例1-2的性能测试结果

根据上述结果可知：
与对比例1-2相比，本申请实施例正极活性材料所制电池的快充性能更好，循环寿命更长；
与实施例20-23、26相比，本申请实施例1、4-11、13-18、31-38的正极材料所制电池的快充性能进一步提高，循环寿命进一步延长；
与实施例2-3相比，本申请实施例1、4-11、13-18、31-38的正极材料所制电池的快充性能进一步提升；
与实施例12、19、24-25、27-28相比，本申请实施例1、4-11、13-18、31-38的正极材料所制电池的循环寿命进一步延长。
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. 一种电池，包括正极极片，所述正极极片包含第一正极活性材料和第二正极活性材料；其中，
    所述第一正极活性材料包括化合物LiaNibCocM1dM2eOfEg；其中，
    所述M1包括Mn和Al的一种或两种元素；
    所述M2包括Zr、Zn、Cu、Cr、Mg、Fe、V、Ti、Sr、Sb、Y、W和Nb中的一种或多种元素；
    所述E包括N、F、S和Cl中的一种或多种元素；
    0.75≤a≤1.2；0<b<1；0<c<1；0<d<1；0≤e≤0.2；1≤f≤2.5，0≤g≤1，且f+g≤3；
    所述第二正极活性材料包括化合物LixHyMn1-zQzP1-mGmO4-nDn，其中，
    所述H包括选自Zn、Al、Na、K、Mg、Nb、Mo和W中的一种或多种元素；
    所述Q包括选自Zn、Al、Na、K、Mg、Mo、W、Ti、V、Zr、Fe、Ni、Co、Ga、Sn、Sb、Nb和Ge中的一种或多种元素；
    所述G包括选自B、Si、N、S、F、Cl和Br中的一种或多种元素；
    所述D包括选自S、F、Cl和Br中的一种或多种元素；
    所述x为0.9至1.1；所述y为0至0.1；所述z为0.001至0.9；所述m为0至0.1；所述n为0至0.1；
    并且，所述电池满足：
    其中，
    A表示所述第二正极活性材料在两种正极活性材料中的质量百分比；
    B表示采用单颗粒微电极法测定的所述第二正极活性材料的小于3.7V充电容量在整个充电容量中的占比；
    C表示所述电池的小于3.7V充电容量在整个充电容量中的占比；
    R表示所述正极极片在25℃下的电阻，单位为Ω。
  2. 根据权利要求1所述的电池，其中，
    可选地，
  3. 根据权利要求1或2所述的电池，其中，
    所述A为0.1至0.5，可选为0.1至0.3，更可选为0.2至0.3；和/或，
    所述B为0.4至0.6，可选为0.5至0.6；和/或，
    所述C为0.05至0.23，可选为0.09至0.16；和/或，
    0<R<1，可选为0.1至0.6，更可选为0.2至0.4。
  4. 根据权利要求1至3中任一项所述的电池，其中，所述第二正极活性材料中，所述Q包括Fe、Ti、V、Ni、Co和Mg中的一种或多种元素；和/或，
    所述G包括B、Si、N和S中的一种或多种元素；和/或，
    所述x为0.977至1；和/或，
    所述y为0至0.001；和/或，
    所述z为0.1至0.9或者0.001至0.6，可选为0.3至0.7；和/或，
    所述m为0至0.001或者0.001至0.1；和/或，
    所述n为0至0.001或者0.001至0.1。
  5. 根据权利要求1至4中任一项所述的电池，其中，所述第一正极活性材料中，所述a为0.9至1.1；和/或，
    所述d为0.003至0.4；和/或，
    所述b为30％至99.5％，可选为50％至99％，更可选为55％至88％；和/或，
    所述c为0.2％至52％，可选为0.5％至49.5％，更可选为5％至 35％。
  6. 根据权利要求1至5中任一项所述的电池，其中，所述第一正极材料为单晶或类单晶材料，并且满足：
    单晶颗粒或类单晶颗粒的Dv50粒径为1.5至4.5μm，可选为2至4.1μm；和/或，
    单晶颗粒或类单晶颗粒的Dv99粒径≤18μm，可选为6.4至17.5μm，更可选为6.5至13.5μm；和/或，
    所述第一正极活性材料的BET比表面积为0.42至1.2m2/g，可选为0.5至1m2/g。
  7. 根据权利要求1至5中任一项所述的电池，其中，所述第一正极活性材料为多晶材料，并且满足：
    二次颗粒的Dv50粒径为6至14μm，可选为7至13μm；和/或，
    二次颗粒的Dv99粒径<30μm，可选为14.2至28.8μm，更可选为15.4至26.7μm；和/或，
    一次颗粒的粒径为50至800nm，可选为50至600nm；和/或，
    所述第一正极活性材料的BET比表面积为0.8至1.2m2/g，可选为0.8至1.1m2/g。
  8. 根据权利要求1至7中任一项所述的电池，其中，所述第二正极活性材料为单晶或类单晶材料，并且满足：
    单晶颗粒或类单晶颗粒的Dv50粒径为0.2至1.6μm，可选为0.25至1.49μm；和/或，
    单晶颗粒或类单晶颗粒的Dv99粒径为5.2至33.8μm，可选为6.1至25.7μm；和/或，
    所述第二正极活性材料的BET比表面积为11.3至14.1m2/g，可选为12至13.7m2/g。
  9. 根据权利要求1至8中任一项所述的电池，其中，所述第一 正极活性材料为层状结构；和/或，所述第二正极活性材料为橄榄石结构。
  10. 根据权利要求1至9中任一项所述的电池，其中，
    所述第一正极活性材料包括内核和包覆所述内核的包覆层，所述内核为化合物LiaNibCocM1dM2eOfEg；和/或，
    所述第二正极活性材料包括内核和包覆所述内核的包覆层，所述内核为化合物LixHyMn1-zQzP1-mGmO4-nDn；
    可选地，所述第一正极活性材料和第二正极活性材料中的包覆层独立地包括焦磷酸盐、磷酸盐和碳中的一种或多种。
  11. 根据权利要求10所述的电池，其中，所述包覆层在所述第二正极活性材料中的质量占比为0.5％至2.2％，可选为1％至1.9％，更可选为1.2％至1.5％；
    可选地，所述第二正极活性材料中的包覆层为碳。
  12. 一种用电装置，包括权利要求1至11中任一项所述的电池。
PCT/CN2024/070831 2023-03-10 2024-01-05 电池和用电装置 Ceased WO2024187927A1 (zh)

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