Secondary battery, battery module, battery pack, and electric device
View Patent ↗Provided are a secondary battery, a battery module, a battery pack, and an electric device. The secondary battery includes: a positive electrode sheet and a non-aqueous electrolyte, where the positive electrode sheet includes a cathode active material with a core-shell structure, and the cathode active material includes a core and a shell covering the core; the core has a chemical formula of 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 a crystalline pyrophosphate M b (P 2 O 7 ) c , the second coating layer includes a crystalline phosphate XPO 4 , and the third coating layer is carbon; and the non-aqueous electrolyte includes a first lithium salt and a first additive, where the first lithium salt includes one or more selected from the group consisting of LiN(C m F 2m+1 SO 2 )(C n F 2n+1 SO 2 ) and Li(FSO 2 ) 2 N, where m and n each are a positive integer.
1. A secondary battery, comprising: a positive electrode sheet and a non-aqueous electrolyte, wherein
the positive electrode sheet comprises a cathode active material with a core-shell structure, and the cathode active material comprises a core and a shell covering the core;
the core has a chemical formula of Li 1+x Mn 1-y A y P 1-z R z O 4 , wherein x is any value in a range of −0.100 to 0.100, y is any value in a range of 0.001 to 0.500, and z is any value in a range of 0.001 to 0.100; A is one or more selected from the 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 selected from the group consisting of B, S1, N, and S;
the shell comprises a first coating layer covering the core, a second coating layer covering the first coating layer, and a third coating layer covering the second coating layer,
wherein the first coating layer comprises a crystalline pyrophosphate Li a MP 2 O 7 and/or a crystalline pyrophosphate M b (P 2 O 7 ) c , wherein 0≤a≤2, 1≤b≤4, and 1≤c≤6; values of a, b, and c meet the following condition: keeping the crystalline pyrophosphate Li a MP 2 O 7 or M b (P 2 O 7 ) c electrically neutral; and M in each of the crystalline pyrophosphates Li a MP 2 O 7 and M b (P 2 O 7 ) c is independently one or more selected from the 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 selected from the 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 lithium salt and a first additive,
wherein the first lithium salt comprises one or more selected from the group consisting of LiN(C m F 2m+1 SO 2 )(C n F 2n+1 SO 2 ) and Li(FSO 2 ) 2 N, wherein m and n each are a positive integer; and
the first additive comprises one or more selected from the group consisting of compounds shown in Formula 1
wherein R 1 is any one selected from the group consisting of C 2 -C 10 alkylene, C 2 -C 10 heteroalkylene, C 6 -C 15 arylene, C 2 -C 15 heteroarylene, C 3 -C 15 alicyclylene, and C 3 -C 18 heteroalicyclylene that each are or are not substituted by one or more R a groups;
R a comprises one or more selected from the group consisting of a halogen atom, —CN, —NCO, —OH, —COOH, —SOOH, —COOR b , C 2 -C 10 alkyl, C 2 -C 10 alkenyl, C 2 -C 10 alkynyl, and C 2 -C 10 oxaalkyl; and R b is any C 1 -C 10 alkyl.
2. The secondary battery according to claim 1 , wherein
R 1 is any one selected from the group consisting of C 2 -C 10 alkylene, C 2 -C 10 oxaalkylene, C 2 -C 10 azaalkylene, phenylene, naphthylene, anthracenylene, cyclobutylene, cyclopentylene, cyclohexylene, biphenylene, and methylenediphenylene that each are or are not substituted by one or more R a groups; and/or
R a comprises one or more selected from the group consisting of a halogen atom, —CN, and C 2 -C 3 alkyl; and/or
there is 0, 1, 2, 3, or 4 R a groups in a compound shown in Formula 1.
3. The secondary battery according to claim 1 , wherein the first additive comprises at least one selected from the group consisting of the following compounds:
4. The secondary battery according to claim 1 , wherein m and n each independently selected from the group consisting of 0, 1, 2, and 3.
5. The secondary battery according to claim 1 , wherein
based on a total weight of the non-aqueous electrolyte,
a content of the first lithium salt is set as W1 wt %, and W1 is 0.1 to 48; and/or,
a content of the first additive is set as W2 wt %, and W2 is 0.01 to 20.
6. The secondary battery according to claim 5 , wherein based on a weight of the core, a coating amount of the first coating layer is set as C1 wt %, and C1 is 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 set as C2 wt %, and C2 is 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 set as C3 wt %, and C3 is greater than 0 and less than or equal to 6; and
a ratio of (W1+W2)/(C1+C2+C3) is defined as Q, and Q is 0.1 to 10.
7. The secondary battery according to claim 1 , wherein the non-aqueous electrolyte further comprises a second lithium salt, and the second lithium salt comprises one or more selected from the group consisting of lithium difluorophosphate (LiDFP), lithium difluoro(bisoxalato)phosphate (LiDFBOP), lithium difluoro(oxalato)borate (LIODFB), lithium bis(oxalato)borate (LiBOB), LiPF 6 , LiBF 4 , and LiAsF 6 .
8. The secondary battery according to claim 7 , wherein based on a total weight of the non-aqueous electrolyte, a content of the second lithium salt is set as W3 wt %, and W3 is 0.01 to 20.
9. The secondary battery according to claim 8 , wherein (W2+W3)/W1 is defined as N, and N is 0.01 to 2.
10. The secondary battery according to claim 1 , wherein the non-aqueous electrolyte further comprises a second additive, and the second additive comprises one or more selected from the group consisting of an unsaturated bond-containing cyclic carbonate compound, a halogen-substituted saturated 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 phosphonitrile compound, a cyclic anhydride compound, a phosphite compound, a phosphate compound, and a borate compound.
11. The secondary battery according to claim 1 , wherein the non-aqueous electrolyte further comprises an organic solvent; and
the organic solvent comprises one or more selected from the group consisting of a cyclic carbonate compound, a chain carbonate compound, and a carboxylate compound.
12. The secondary battery according to claim 1 , wherein
based on a weight of the core, a coating amount of the first coating layer is set as C1 wt %, and C1 is 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 set as C2 wt %, and C2 is 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 set as C3 wt %, and C3 is greater than 0 and less than or equal to 6.
13. The secondary battery according to claim 1 , wherein
for the crystalline pyrophosphate in the first coating layer, an interplanar crystal spacing is in a range of 0.293 nm to 0.470 nm and an angle of a crystal orientation ( 111 ) is in a range of 18.00° to 32.00°; and
for the crystalline phosphate in the second coating layer, an interplanar crystal spacing is in a range of 0.244 nm to 0.425 nm and an angle of a crystal orientation ( 111 ) is in a range of 20.00° to 37.00°.
14. The secondary battery according to claim 1 , wherein in the core, a ratio of y to 1−y is 1:10 to 1:1.
15. The secondary battery according to claim 1 , wherein in the core, a ratio of z to 1−z is 1:9 to 1:999.
16. The secondary battery according to claim 1 , wherein the carbon of the third coating layer is a mixture of SP2-hybridized carbon and SP3-hybridized carbon.
17. The secondary battery according to claim 1 , wherein
the first coating layer has a thickness of 1 nm to 10 nm; and/or
the second coating layer has a thickness of 2 nm to 15 nm; and/or
the third coating layer has a thickness of 2 nm to 25 nm.
18. The secondary battery according to claim 1 , wherein based on a weight of the cathode active material,
a manganese content is in a range of 10 wt % to 35 wt %;
a phosphorus content is in a range of 12 wt % to 25 wt %.
19. The secondary battery according to claim 1 , wherein
a lattice change rate of the cathode active material with the core-shell structure before and after complete lithium deintercalation is 4% or less; and/or
a Li/Mn antisite defect concentration of the cathode active material with the core-shell structure is 4% or less; and/or
a compacted density of the cathode active material with the core-shell structure at 3 T is 2.2 g/cm 3 or more; and/or
a surface oxygen valence state of the cathode active material with a core-shell structure is −1.90 or less.
20. A battery module comprising the secondary battery according to claim 1 .
21. A battery pack comprising the battery module according to claim 20 .
22. An electric device comprising at least one selected from the group consisting of the secondary battery according to claim 1 .