# US 12,191,459 B2 · Secondary battery, battery module, battery pack, and electric apparatus

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- Number: US 12,191,459 B2
- Document ID: US12191459B2
- Status: Granted
- Kind: B2
- Application number: 18/607,120
- Filed: 2024-03-15
- Published: 2024-08-22
- Granted: 2025-01-07
- Earliest claimed: 2022-04-01
- Assignees: Contemporary Amperex Technology (Hong Kong) Limited
- Applicants: Contemporary Amperex Technology (Hong Kong) Limited
- Inventors: Peipei Chen; Limei Zhang; Yao Jiang; Jiao Liu
- Web page: https://patentgrep.com/patent/US12191459B2

## CPC

- H01M 10/0525: Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
- H01M 10/4235: {Safety or regulating additives or arrangements in electrodes, separators or electrolyte (H01M10/4242 takes precedence)}
- C01B 25/45: containing plural metal, or metal and ammonium
- H01M 4/136: Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
- H01M 4/366: {as layered products}
- H01M 4/5825: {Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines}
- H01M 4/587: for inserting or intercalating light metals
- H01M 4/625: {Carbon or graphite}
- H01M 10/052: Li-accumulators
- H01M 10/0567: characterised by the additives
- H01M 10/0568: characterised by the solutes
- H01M 10/0569: characterised by the solvents
- C01P 2002/52: containing elements as dopants
- C01P 2004/86: Thin layer coatings, i.e. the coating thickness being less than 0.1 time the particle radius
- C01P 2006/40: Electric properties
- H01M 2004/028: {Positive electrodes}
- H01M 2220/20: Batteries in motive systems, e.g. vehicle, ship, plane
- H01M 2300/0025: Organic electrolyte
- Y02E 60/10: Energy storage using batteries
- H01M: PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- C01B: NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; {METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C}
- C01P: INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- Y02E: REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION

## Abstract

A secondary battery includes a positive electrode plate and a non-aqueous electrolyte. The positive electrode plate includes a positive electrode active material including a core and a shell enveloping the core. A chemical formula of the core is Li1+xMn1−yAyP1−zRzO4, where the first coating layer includes a crystalline pyrophosphate LiaMP2O7 and/or Mb(P2O7)c, the second coating layer includes a crystalline phosphate XPO4, and the third coating layer is carbon. The non-aqueous electrolyte includes a first additive including one or more selected from a group consisting of compounds represented by formula 1 and compounds represented by formula 2.

## Claims

### Claim 1

A secondary battery, comprising a positive electrode plate and a non-aqueous electrolyte, wherein:
the positive electrode plate comprises a positive electrode active material with a core-shell structure, the positive electrode active material comprising a core and a shell enveloping the core;
a chemical formula of the core is Li1+xMn1−yAyP1−zRzO4, wherein x is any value in the range of −0.100 to 0.100, y is any value in the range of 0.001-0.500, z is any value in the range of 0.001-0.100, A is one or more elements selected from a group consisting of Zn, Al, Na, K, Mg, Mo, W, Ti, V, Zr, Fe, Ni, Co, Ga, Sn, Sb, Nb, and Ge, R is one or more elements selected from a group consisting of B, Si, N, and S, and values of x, y, and z satisfy the following condition: making the entire core electrically neutral;
the shell comprises a first coating layer enveloping the core, a second coating layer enveloping the first coating layer, and a third coating layer enveloping the second coating layer; wherein
the first coating layer comprises a crystalline pyrophosphate LiaMP2O7 and/or Mb(P2O7)c, wherein 0≤a≤2, 1≤b≤4, 1≤c≤6, values of a, b, and c satisfy the following condition: making the crystalline pyrophosphate LiaMP2O7 and/or Mb(P2O7)c electrically neutral, and each M in the crystalline pyrophosphate LiaMP2O7 and/or Mb(P2O7), is independently one or more elements selected from a group consisting of Fe, Ni, Mg, Co, Cu, Zn, Ti, Ag, Zr, Nb, and Al,
the second coating layer comprises a crystalline phosphate XPO4, wherein X is one or more elements selected from a group consisting of Li, Fe, Ni, Mg, Co, Cu, Zn, Ti, Ag, Zr, Nb, and Al, and
the third coating layer is carbon; and
the non-aqueous electrolyte comprises a first additive, the first additive comprising one or more selected from a group consisting of compounds represented by formula 1 and compounds represented by formula 2,
wherein:
R1 and R2 each independently represent any one of a hydrogen atom, a halogen atom, a C1-C6 alkyl group, a C1-C6 haloalkyl group, a C1-C6 alkoxy group, a C2-C6 alkenyl group, or a C2-C6 alkynyl group; and
R3, R4, R5, and R6 each independently represent any one of a hydrogen atom, a halogen atom, a C1-C6 alkyl group, a C1-C6 haloalkyl group, a C1-C6 alkoxy group, a C2-C6 alkenyl group, a C2-C6 alkynyl group, or a C2-C6 alkynyloxy group, and R3, R4, R5, and R6 do not all represent a hydrogen atom.

### Claim 2 (depends on 1)

The secondary battery according to claim 1, wherein:
R1 and R2 each independently represent any one of a hydrogen atom, a halogen atom, a C1-C4 alkyl group, a C1-C4 haloalkyl group, a C1-C4 alkoxy group, a C2-C4 alkenyl group, or a C2-C4 alkynyl group; and/or
R3, R4, R5, and R6 each independently represent any one of a hydrogen atom, a halogen atom, a C1-C4 alkyl group, a C1-C4 haloalkyl group, a C1-C4 alkoxy group, a C2-C4 alkenyl group, a C2-C4 alkynyl group, or a C2-C4 alkynyloxy group, and R3, R4, R5, and R6 do not all represent a hydrogen atom.

### Claim 3 (depends on 1)

The secondary battery according to claim 1, wherein the first additive comprises at least one of the following compounds:

### Claim 4 (depends on 1)

The secondary battery according to claim 1, wherein, based on a total weight of the non-aqueous electrolyte, a percentage of the first additive is W1% by weight, W1 being 0.01 to 20.

### Claim 5 (depends on 1)

The secondary battery according to claim 1, wherein the first additive is represented by any one of the following compounds:

### Claim 6 (depends on 1)

The secondary battery according to claim 1, wherein the non-aqueous electrolyte further comprises a second additive, the second additive comprising one or more selected from a group consisting of ethylene sulfate, lithium difluorophosphate, lithium difluorooxalate phosphate, and lithium difluorooxalate borate.

### Claim 7 (depends on 6)

The secondary battery according to claim 6, wherein, based on a total weight of the non-aqueous electrolyte, a percentage of the second additive is W2% by weight, W2 being 0.01 to 20.

### Claim 8 (depends on 7)

The secondary battery according to claim 7, wherein, based on the total weight of the non-aqueous electrolyte, the percentage of the first additive is W1% by weight, W1 being 0.01 to 20, and A is a mass ratio of W2/W1, A being 0.1 to 10.

### Claim 9 (depends on 1)

The secondary battery according to claim 1, wherein the non-aqueous electrolyte further comprises a third additive, the third additive comprising one or more selected from a group consisting of a chain sulfate compound, a sulfite compound, a sultone compound containing an unsaturated bond, a disulfonic acid compound, a nitrile compound, an aromatic compound, an isocyanate compound, a phosphazene compound, a cyclic anhydride compound, a phosphite compound, a phosphate compound, and a borate compound.

### Claim 10 (depends on 1)

The secondary battery according to claim 1, wherein the non-aqueous electrolyte further comprises an organic solvent and an electrolytic salt.

### Claim 11 (depends on 1)

The secondary battery according to claim 1, wherein:
based on a weight of the core, a coating amount of the first coating layer is C1% by weight, C1 being greater than 0 and less than or equal to 6; and/or
based on the weight of the core, a coating amount of the second coating layer is C2% by weight, C2 being greater than 0 and less than or equal to 6; and/or
based on the weight of the core, a coating amount of the third coating layer is C3% by weight, C3 being greater than 0 and less than or equal to 6.

### Claim 12 (depends on 11)

The secondary battery according to claim 11, wherein:
based on a total weight of the non-aqueous electrolyte, a percentage of the first additive is W1% by weight, W1 being 0.01 to 20, and Q is a ratio of W1/(C1+C2+C3), Q being 0.05 to 1.

### Claim 13 (depends on 1)

The secondary battery according to claim 1, wherein:
the crystalline pyrophosphate in the first coating layer has an interplanar spacing in a range of 0.293-0.470 nm and an included angle in a range of 18.00°-32.00° in the [111] crystal orientation; and
the crystalline phosphate in the second coating layer has an interplanar spacing in a range of 0.244-0.425 nm and an included angle in a range of 20.00°-37.00° in the [111] crystal orientation.

### Claim 14 (depends on 1)

The secondary battery according to claim 1, wherein:
a ratio of y to 1−y in the core is in a range of 1:10 to 1:1; and/or
a ratio of z to 1−z in the core is in a range of 1:9 to 1:999.

### Claim 15 (depends on 1)

The secondary battery according to claim 1, wherein carbon in the third coating layer is a mixture of SP2 carbon and SP3 carbon.

### Claim 16 (depends on 1)

The secondary battery according to claim 1, wherein:
a thickness of the first coating layer is 1 nm to 10 nm; and/or
a thickness of the second coating layer is 2 nm to 15 nm; and/or
a thickness of the third coating layer is 2 nm to 25 nm.

### Claim 17 (depends on 1)

The secondary battery according to claim 1, wherein based a weight of the positive electrode active material:
a percentage of element manganese is in a range of 10%-35% by weight; and
a percentage of element phosphorus is in a range of 12%-25% by weight.

### Claim 18 (depends on 1)

The secondary battery according to any claim 1, wherein a lattice change rate of the positive electrode active material with the core-shell structure before and after complete lithium deintercalation or intercalation is lower than 4%.

### Claim 19 (depends on 1)

The secondary battery according to claim 1, wherein a Li/Mn antisite defect concentration of the positive electrode active material with the core-shell structure is lower than 4%.

### Claim 20 (depends on 1)

The secondary battery according to claim 1, wherein a compacted density of the positive electrode active material with the core-shell structure under a pressure of 3 T is greater than 2.2 g/cm3.

### Claim 21 (depends on 1)

The secondary battery according to claim 1, wherein a valence state of surface oxygen of the positive electrode active material with the core-shell structure is lower than −1.90.

### Claim 22 (depends on 1)

A battery module, comprising the secondary battery according to claim 1.

### Claim 23 (depends on 22)

A battery pack, comprising the battery module according to claim 22.

### Claim 24 (depends on 1)

An electric apparatus, comprising the secondary battery according to claim 1.