Secondary battery, battery module, battery pack, and electric apparatus
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 Li 1+x Mn 1−y A y P 1−z R z O 4 , where the first coating layer includes a crystalline pyrophosphate Li a MP 2 O 7 and/or M b (P 2 O 7 ) c , the second coating layer includes a crystalline phosphate XPO 4 , 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.
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 Li 1+x Mn 1−y A y P 1−z R z O 4 , 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 Li a MP 2 O 7 and/or M b (P 2 O 7 ) 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 Li a MP 2 O 7 and/or M b (P 2 O 7 ) c electrically neutral, and each M in the crystalline pyrophosphate Li a MP 2 O 7 and/or M b (P 2 O 7 ), 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 XPO 4 , 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:
R 1 and R 2 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
R 3 , R 4 , R 5 , and R 6 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 R 3 , R 4 , R 5 , and R 6 do not all represent a hydrogen atom.
2. The secondary battery according to claim 1 , wherein:
R 1 and R 2 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
R 3 , R 4 , R 5 , and R 6 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 R 3 , R 4 , R 5 , and R 6 do not all represent a hydrogen atom.
3. The secondary battery according to claim 1 , wherein the first additive comprises at least one of the following compounds:
4. 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.
5. The secondary battery according to claim 1 , wherein the first additive is represented by any one of the following compounds:
6. 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.
7. 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.
8. 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.
9. 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.
10. The secondary battery according to claim 1 , wherein the non-aqueous electrolyte further comprises an organic solvent and an electrolytic salt.
11. 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.
12. 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.
13. 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.
14. 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.
15. The secondary battery according to claim 1 , wherein carbon in the third coating layer is a mixture of SP2 carbon and SP3 carbon.
16. 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.
17. 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.
18. 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%.
19. 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%.
20. 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/cm 3 .
21. 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.
22. A battery module, comprising the secondary battery according to claim 1 .
23. A battery pack, comprising the battery module according to claim 22 .
24. An electric apparatus, comprising the secondary battery according to claim 1 .