# US 12,183,917 B2 · Secondary battery comprising positive electrode plate and non-aqueous electrolyte solution

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- Number: US 12,183,917 B2
- Document ID: US12183917B2
- Status: Granted
- Kind: B2
- Application number: 18/736,563
- Filed: 2024-06-07
- Published: 2024-09-26
- Granted: 2024-12-31
- Earliest claimed: 2022-04-01
- Assignees: Contemporary Amperex Technology (Hong Kong) Limited
- Applicants: Contemporary Amperex Technology (Hong Kong) Limited
- Inventors: Limei Zhang; Peipei Chen; Yao Jiang; Jiao Liu
- Web page: https://patentgrep.com/patent/US12183917B2

## CPC

- 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 4/58: 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
- 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 10/0525: Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
- H01M 10/0567: characterised by the additives
- H01M 10/0569: characterised by the solvents
- 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 10/0568: characterised by the solutes
- H01M 2004/028: {Positive electrodes}
- H01M 2220/20: Batteries in motive systems, e.g. vehicle, ship, plane
- H01M 2300/0037: Mixture of solvents
- 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}
- Y02E: REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION

## Abstract

Provided are a secondary battery, a battery module, a battery pack and an electrical apparatus. The secondary battery includes a positive electrode plate and a non-aqueous electrolyte solution. A positive electrode active material includes an inner core and a shell cladding the inner core. The inner core includes Li1+xMn1−yAyP1−zRzO4. The shell includes a first cladding layer cladding the inner core and a second cladding layer cladding the first cladding layer. The first cladding layer includes pyrophosphate MP2O7 and phosphate XPO4. The second cladding layer includes carbon. The non-aqueous electrolyte solution includes a first additive. The first additive includes one or more compounds in a group consisting of a compound shown in Formula 1, a compound shown in Formula 2 and a compound shown in Formula 3. The rate performance, cycling performance and high temperature stability of a lithium manganese phosphate secondary battery are increased.

## Claims

### Claim 1

A secondary battery, comprising a positive electrode plate and a non-aqueous electrolyte solution, wherein
the positive electrode plate comprises a positive electrode active material, the positive electrode active material comprises an inner core and a shell cladding the inner core, and
the inner core comprises Li1+xMn1−yAyP1−zRzO4, wherein x=−0.100-0.100, y=0.001-0.500, z=0.001-0.100, A is selected from one or more elements in a group consisting of Zn, Al, Na, K, Mg, Mo, W, Ti, V, Zr, Fe, Ni, Co, Ga, Sn, Sb, Nb and Ge, and optionally one or more elements in a group consisting of Fe, Ti, V, Ni, Co and Mg, and R is selected from one or more elements in a group consisting of B, Si, N and S;
the shell comprises a first cladding layer cladding the inner core, and a second cladding layer cladding the first cladding layer, wherein
the first cladding layer comprises pyrophosphate MP2O7 and phosphate XPO4, wherein M and X are each independently selected from one or more elements in a group consisting of Li, Fe, Ni, Mg, Co, Cu, Zn, Ti, Ag, Zr, Nb and Al,
and the second cladding layer comprises carbon;
the non-aqueous electrolyte solution comprises a first additive, and the first additive comprises one or more compounds in a group consisting of a compound shown in Formula 1, a compound shown in Formula 2 and a compound shown in Formula 3:
R1 and R2 each independently represent any one of F, C1-C6 fluoroalkyl, C1-C6 alkyl, C1-C6 alkoxy, C2-C6 alkenyl, C2-C6 alkynyl and C6-C10 aryl, and at least one of R1 and R2 represents any one of F or C1-C6 fluoroalkyl;
R3 and R4 each independently represent any one of F, C1-C6 fluoroalkyl, C1-C6 alkyl, C1-C6 alkoxy, C2-C6 alkenyl and C2-C6 alkynyl, and at least one of R3 and R4 represents any one of F or C1-C6 fluoroalkyl;
R5 and R6 each independently represent any one of F, C1-C6 fluoroalkyl, C1-C6 alkyl, C1-C6 alkoxy, C2-C6 alkenyl, C2-C6 alkynyl, carbonyl, O—, ═O, —−BF3 and —O—BF3;
M in each chemical formula each independently represents one of alkali metals and alkaline-earth metals; and
n is 0, 1 or 2.

### Claim 2 (depends on 1)

The secondary battery according to claim 1, wherein
R1 and R2 each independently represent any one of F, C1-C3 fluoroalkyl, C1-C3 alkyl, C1-C3 alkoxy, C2-C3 alkenyl, C2-C3 alkynyl, phenyl, benzyl and methylphenyl, and at least one of R1 and R2 represents any one of F or C1-C3 fluoroalkyl; and/or
R3 and R4 each independently represent any one of F, C1-C3 fluoroalkyl, C1-C3 alkyl, C1-C3 alkoxy, C2-C3 alkenyl and C2-C3 alkynyl, and at least one of R3 and R4 represents any one of F and C1-C3 fluoroalkyl and/or
R5 and R6 each independently represent any one of F, C1-C3 fluoroalkyl, C1-C3 alkyl, C1-C3 alkoxy, C2-C6 alkenyl, C2-C6 alkynyl, carbonyl, O—, ═O, —−BF3 and —O−BF3; and/or
M in each chemical formula each independently represents one of Li, Na and K.

### Claim 3 (depends on 1)

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

### Claim 4 (depends on 1)

The secondary battery according to claim 1, wherein the first additive comprises any one or more of the following compounds:

### Claim 5 (depends on 1)

The secondary battery according to claim 1, wherein
the non-aqueous electrolyte solution further comprises a second additive, and the second additive comprises one or more of compounds in a group consisting of a cyclic carbonate compound containing unsaturated bonds, a halogen-substituted cyclic carbonate compound, a sulfate compound, a sulfite compound, a sultone compound, 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 6 (depends on 5)

The secondary battery according to claim 5, wherein based on a total weight of the non-aqueous electrolyte solution, a content of the first additive is W1 wt %, and W1 is 0.01 to 20, and;
the W1/W2 is defined as M, and M is 0.001 to 20.

### Claim 7 (depends on 1)

The secondary battery according to claim 1, wherein the non-aqueous electrolyte solution further comprises an organic solvent and an electrolyte salt,
the organic solvent comprises one or more of a cyclic carbonate compound, a chain carbonate compound and a carboxylate compound, and further comprises one or more components in a group consisting of dimethyl carbonate, diethyl carbonate, dipropyl carbonate, ethyl methyl carbonate, methyl propyl carbonate, ethyl propyl carbonate, ethylene carbonate, propylene carbonate, butene carbonate, gamma-butyrolactone, methyl formate, ethyl formate, methyl acetate, ethyl acetate, propyl acetate, methyl propionate, ethyl propionate, butyl propionate and tetrahydrofuran.

### Claim 8 (depends on 1)

The secondary battery according to claim 1, wherein
based on the weight of the inner core, the cladding amount of the first cladding layer is C1 wt %, and C1 is greater than 0 and less than or equal to 7, and optionally 4 to 5.6; and/or
based on the weight of the inner core, the cladding amount of the second cladding layer is C2 wt %, and C2 is greater than 0 and less than or equal to 6, and optionally 3 to 5.

### Claim 9 (depends on 4)

The secondary battery according to claim 4, wherein
based on a weight of the inner core, the cladding amount of the first cladding layer is C1 wt %, and C1 is greater than 0 and less than or equal to 7; and/or
based on the weight of the inner core, the cladding amount of the second cladding layer is C2 wt %, and C2 is greater than 0 and less than or equal to 6;
wherein a relational expression W1/(C1+C2) between a content W1 of the first additive and the cladding amount C1 of the first cladding layer as well as the cladding amount C2 of the second cladding layer is C, and C is 0.001 to 2.

### Claim 10 (depends on 1)

The secondary battery according to claim 1, wherein
the weight ratio of pyrophosphate to phosphate in the first cladding layer is 1:3 to 3:1, and optionally 1:3 to 1:1.

### Claim 11 (depends on 1)

The secondary battery according to claim 1, wherein
the interplanar spacing of phosphate in the first cladding layer is 0.345 to 0.358 nm, and an included angle between crystal orientations (111) is 24.25° to 26.45°; and
an interplanar spacing of pyrophosphate in the first cladding layer is 0.293 to 0.326 nm, and an included angle between crystal orientations (111) is 26.41° to 32.57°.

### Claim 12 (depends on 1)

The secondary battery according to claim 1, wherein
in the inner core, a ratio of y to 1-y is 1:10 to 10:1; and/or
in the inner core, a ratio of z to 1-z is 1:9 to 1:999, and optionally 1:499 to 1:249.

### Claim 13 (depends on 1)

The secondary battery according to claim 1, wherein
a crystallinity of pyrophosphate and phosphate is each independently 10% to 100%, and optionally 50% to 100%.

### Claim 14 (depends on 1)

The secondary battery according to claim 1, wherein
A is selected from at least two of Fe, Ti, V, Ni, Co and Mg.

### Claim 15 (depends on 1)

The secondary battery according to claim 1, wherein
a Li/Mn antisite defect concentration of the positive electrode active material is 4% or less, and optionally 2% or less.

### Claim 16 (depends on 1)

The secondary battery according to claim 1, wherein
a lattice change rate of the positive electrode active material is 6% or less, and optionally 4% or less.

### Claim 17 (depends on 1)

The secondary battery according to claim 1, wherein
a surface oxygen valence state of a positive electrode active material is −1.88 or less, and optionally −1.98 to −1.88.

### Claim 18 (depends on 1)

The secondary battery according to claim 1, wherein
a compacted density of the positive electrode active material at 3 tons (T) is 2.0 g/cm3 or more, and optionally 2.2 g/cm3 or more.

### Claim 19 (depends on 1)

A battery module, comprising a plurality of the secondary batteries according to claim 1.

### Claim 20 (depends on 19)

A battery pack, comprising a plurality of the battery modules according to claim 19.