Secondary battery, battery module, battery pack, and electric device
Provided are a secondary battery, a battery module, a battery pack, and an electric device. The secondary battery includes a cathode piece and a non-aqueous electrolyte. The cathode active material includes a core and a shell covering the core. The core includes Li 1+x Mn 1−y A y P 1−z R z O 4 . The shell includes: a first cladding layer covering the core, and a second cladding layer covering the first cladding layer. The first cladding layer includes pyrophosphate MP 2 O 7 and phosphate XPO 4 , and the second cladding layer contains carbon. The non-aqueous electrolyte includes a first lithium salt and a first additives, the first lithium salt is 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, in which, m and n represent positive integers. The first additive includes one or more of a compound represented by: O═C═N—R 1 —N═C═O.
1 . A secondary battery, comprising a cathode piece and a non-aqueous electrolyte, wherein,
the cathode piece comprises a cathode active material, and the cathode active material comprises a core and a shell covering the core,
the core comprises Li 1+x Mn 1−y A y P 1−z R z O 4 , wherein x=−0.100 to 0.100, y=0.001 to 0.500, z=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, and R is one or more selected from the group consisting of B, Si, N and S;
the shell comprises: a first cladding layer covering the core, and a second cladding layer covering the first cladding layer, wherein,
the first cladding layer comprises pyrophosphate MP 2 O 7 and phosphate XPO 4 , wherein M and X are each independently one or more selected from the group consisting of Li, Fe, Ni, Mg, Co, Cu, Zn, Ti, Ag, Zr, Nb, and Al;
the second cladding layer comprises carbon;
the non-aqueous electrolyte comprises a first lithium salt and a first additive;
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, in which, m and n represent positive integers; and
the first additive comprises one or more of a compound represented by Formula 1,
O═C═N—R 1 —N═X═O Formula 1,
in which, R 1 represents any one of a C 2 -C 10 alkylene, a C 2 -C 10 heteroalkylene, a C 6 -C 18 arylene, a C 2 -C 18 heteroarylene, a C 3 -C 18 alicyclylene, a C 3 -C 18 heteroalicyclylene, which are substituted by one or more R a or are unsubstituted, and
R a comprises one or more selected from a halogen atom, —CN, —NCO, —OH, —COOH, —SOOH, a —COOR b , a C 2 -C 10 alkyl, a C 2 -C 10 alkenyl, a C 2 -C 10 alkynyl, a C 2 -C 10 oxaalkyl, and R b is any one selected from C 1 -C 10 alkyls.
2 . The secondary battery according to claim 1 , wherein R 1 represents any one of a C 2 -C 10 alkylene, a C 2 -C 10 oxaalkylene, a C 2 -C 10 azaalkylene, phenylene, naphthylene, anthrylene, cyclobutylene, cyclopentylene, cyclohexylene, biphenylene, methylenediphenylene, which are substituted by one or more Ra or are unsubstituted;
the R a comprises one or more selected from halogen atoms, —CN, C 2 -C 3 alkyl; and/or
a number of R a in the compound represented by the Formula 1 is 0, 1, 2, 3, or 4.
3 . The secondary battery according to claim 1 , wherein the first additive comprises one or more of the following compounds:
4 . The secondary battery according to claim 1 , wherein m and n each independently represent 0, 1, 2, 3, or 4;
and/or, the first lithium salt is any one selected from LiN(CF 3 SO 2 )(FSO 2 ), Li(CF 3 SO 2 ) 2 N, and LiN(C 4 F 9 SO 2 )(FSO 2 ); and the first additive is any one selected from the following compounds:
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 W1 wt. %, W1 is between 0.1 and 48; and
a content of the first additive is W2 wt. %, W2 is between 0.01 and 20.
6 . The secondary battery according to claim 5 , wherein based on a weight of the core, a coating amount of the first cladding layer is C1 wt. %, C1 is greater than 0 and less than or equal to 7, and/or based on the weight of the core, the coating amount of the second cladding layer is C2 wt. %, C2 is greater than 0 and less than or equal to 6; and
a ratio of (W1+W2)/(C1+C2) is defined as Q, and Q is between 0.1 and 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 of lithium difluorophosphate, lithium difluorodioxalate phosphate, lithium difluorooxalate borate, lithium bisoxalate borate, LiPF 6 , and LiBF 4 .
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 W3 wt. %, W3 is between 0.01 and 20.
9 . 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 of the group consisting of a cyclic carbonate compound containing an unsaturated bond, 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 phosphazene compound, a cyclic anhydride compound, a phosphorous acid ester compound, a phosphate ester compound, and a borate ester compound.
10 . The secondary battery according to claim 1 , wherein the non-aqueous electrolyte further comprises an organic solvent, wherein
the organic solvent comprises one or more of a cyclic carbonate compound, a chain carbonate compound, and a carboxylate compound.
11 . The secondary battery according to claim 1 , wherein
based on a weight of the core, a coating amount of the first cladding layer is C1 wt. %, C1 is greater than 0 and less than or equal to 7; and/or,
based on the weight of the core, a coating amount of the second cladding layer is C2 wt. %, C2 is greater than 0 and less than or equal to 6.
12 . The secondary battery according to claim 1 , wherein
a weight ratio of pyrophosphate to phosphate in the first cladding layer is between 1:3 and 3:1.
13 . The secondary battery according to claim 1 , wherein
an interplanar spacing of phosphate in the first cladding layer is 0.345-0.358 nm, and an included angle of a crystal direction (111) is 24.25°-26.45°; and
an interplanar spacing of pyrophosphate in the first cladding layer is 0.293-0.326 nm, and the included angle of the crystal direction (111) is 26.41°-32.57°.
14 . The secondary battery according to claim 1 , wherein
a ratio of y to 1-y in the core is between 1:10 and 10:1.
15 . The secondary battery according to claim 1 , wherein
a ratio of z to 1-z in the core is between 1:9 and 1:999.
16 . The secondary battery according to claim 1 , wherein
crystallinities of pyrophosphate and phosphate are independently between 10% and 100%.
17 . The secondary battery according to claim 1 , wherein
the A is at least two selected from Fe, Ti, V, Ni, Co, and Mg.
18 . The secondary battery according to claim 1 , wherein
the cathode active material has a concentration of Li/Mn antisite defect of less than 4%; and/or
the cathode active material has a lattice change rate of less than 6%; and/or
the cathode active material has a surface oxygen valence state of less than − 1 . 88 ; and/or
the cathode active material has a compacted density at 3 tons of above 2.0 g/cm 3 .
19 . A battery module, comprising the secondary battery according to claim 1 .
20 . A battery pack, comprising the battery module according to claim 19 .
21 . An electric device, comprising at least one selected from the secondary battery according to claim 1 .