Non-aqueous electrolyte and preparation method thereof, and secondary battery and electric apparatus containing same
This application provides a non-aqueous electrolyte and a preparation method thereof, and a secondary battery and an electric apparatus containing the same. The non-aqueous electrolyte contains the non-aqueous solvent and lithium ions, first cations, and first anions dissolved therein, where the first cation is a metal cation Me n+ other than the lithium ion, n representing a chemical valence of the metal cation; the first anion is a tetrafluoroborate anion BF 4 − ; mass concentration of the first cations in the non-aqueous electrolyte is D1 ppm, and mass concentration of the first anions in the non-aqueous electrolyte is D2 ppm, both based on total mass of the non-aqueous electrolyte; and the non-aqueous electrolyte satisfies that D1 is 0.1 to 1250 and that D1/D2 is 0.02 to 2. The non-aqueous electrolyte in this application enables the secondary battery to have good cycling performance, safety performance, and kinetic performance.
1. A non-aqueous electrolyte containing a non-aqueous solvent and lithium ions, first cations, first anions, and second anions dissolved therein, wherein the first cations comprise a metal cation Me n+ other than the lithium ion, n representing a chemical valence of the metal cation, Me n+ represents at least one of Ni 2+ , Co 2+ , Mn 2+ , A 13+ , and Fe 2+ ; the first anions comprise a tetrafluoroborate anion BF 4 − ; the second anions comprise at least one of perchlorate anion ClO 4 − , NO 3 − , and SO 4 2− ; a mass concentration of the first cations in the non-aqueous electrolyte is D1 ppm, and a mass concentration of the first anions in the non-aqueous electrolyte is D2 ppm, both based on a total mass of the non-aqueous electrolyte; and the non-aqueous electrolyte satisfies: D1 is 0.1 to 1250, D2 is 1 to 2000, and D1/D2 is 0.02 to 2.
2. The non-aqueous electrolyte according to claim 1 , wherein a difference between a standard reduction potential of Me n+ and a standard reduction potential of Li + is 1.0 V or more, and Me n+ represents at least one of Ni 2+ , Co 2+ , Al 3+ , and Fe 2+ .
3. The non-aqueous electrolyte according to claim 2 , wherein the second anions comprise NO 3 − .
4. The non-aqueous electrolyte according to either claim 1 , wherein
D1 is 100 to 1250;
D1/D2 is 0.35 to 2.
5. The non-aqueous electrolyte according to claim 1 , wherein the second anions further comprise bis(trifluoromethanesulfonyl)imide anion N(SO 2 CF 3 ) 2 − ;
a mass concentration of the second anions in the non-aqueous electrolyte is D3 ppm based on the total mass of the non-aqueous electrolyte;
D3 is 1 to 3000;
D2/D3 is 0.25 to 20.
6. The non-aqueous electrolyte according to claim 1 , wherein the non-aqueous electrolyte further contains third anions, wherein the third anions comprise hexafluorophosphate anion PF 6 − , bis(fluorosulfonyl)imide anion N(SO 2 F) 2 − , or a combination thereof;
a mass percentage of the third anions in the non-aqueous electrolyte is 8% to 20%, based on the total mass of the non-aqueous electrolyte.
7. The non-aqueous electrolyte according to claim 6 , wherein the non-aqueous electrolyte further contains fourth anions, wherein the fourth anions comprise at least one of difluoroxalate borate anion DFOB − , dioxalate borate anion BOB − , hexafluoroarsenate anion AsF 6 − , trifluoromethanesulfonate anion CF 3 SO 3 − , difluorophosphate anion PO 2 F 2 − , difluorodioxalate phosphate anion DODFP − , and tetrafluoroxalate phosphate anion OTFP − ; and
a mass percentage of the fourth anions in the non-aqueous electrolyte is 2% or less, based on the total mass of the non-aqueous electrolyte.
8. The non-aqueous electrolyte according to claim 7 , wherein the fourth anions comprise difluorophosphate anions PO 2 F 2 − ; and
a mass ratio β of the difluorophosphate anions PO 2 F 2 − and the third anions is 0.01 to 0.15.
9. The non-aqueous electrolyte according to claim 7 , wherein the fourth anions comprise at least one of difluoroxalate borate anion DFOB − , dioxalate borate anion BOB − , hexafluoroarsenate anion AsF 6 − , trifluoromethanesulfonate anion CF 3 SO 3 − , difluorodioxalate phosphate anion DODFP − , and tetrafluoroxalate phosphate anion OTFP − .
10. The non-aqueous electrolyte according to claim 1 , wherein the non-aqueous solvent comprises a cyclic carbonate compound and a linear carbonate compound, wherein in the non-aqueous electrolyte, a mass percentage of the cyclic carbonate compound is E1 and a mass percentage of the linear carbonate compound is E2, both based on the total mass of the non-aqueous electrolyte;
E1 is 5% to 40%; and
E2 is 40% to 85%.
11. The non-aqueous electrolyte according to claim 10 , wherein the non-aqueous solvent further comprises an ether compound, and the ether compound comprises at least one of tetrahydrofuran, 2-methyltetrahydrofuran, 1,3-dioxolane, ethylene glycol monomethyl ether, dimethoxyethane, tetraethylene glycol dimethyl ether, dimethoxymethane, and diglyme; and
a mass percentage of the ether compound in the non-aqueous electrolyte is E3, based on the total mass of the non-aqueous electrolyte; and E3 is 0.1% to 40%.
12. The non-aqueous electrolyte according to claim 11 , wherein the non-aqueous solvent further comprises an ether compound, and the ether compound comprises at least one of tetrahydrofuran, 2-methyltetrahydrofuran, 1,3-dioxolane, ethylene glycol monomethyl ether, tetraethylene glycol dimethyl ether, dimethoxymethane, and diglyme.
13. The non-aqueous electrolyte according to claim 1 , wherein the non-aqueous electrolyte further contains a first additive, wherein the first additive is fluoroethylene carbonate;
a mass concentration of the first additive in the non-aqueous electrolyte is D4 ppm, based on the total mass of the non-aqueous electrolyte;
D4 is 1 to 30000; and
D4/D2 is 5 to 500.
14. The non-aqueous electrolyte according to claim 1 , wherein the non-aqueous electrolyte further contains a second additive, wherein the second additive comprises at least one of vinylidene carbonate, lithium oxalate, vinyl sulfate, and 1,3-propane sultone; and
a mass percentage of the second additive in the non-aqueous electrolyte is 5% or less, based on the total mass of the non-aqueous electrolyte.
15. A secondary battery comprising a positive electrode plate, a negative electrode plate, and a non-aqueous electrolyte, wherein the non-aqueous electrolyte is the non-aqueous electrolyte according to claim 1 .
16. The secondary battery according to claim 15 , wherein the positive electrode plate comprises a layered material having a molecular formula of Li a Ni b Co c Mn d Al e M f O g A h , M represents transition metal site doping cation, A represents oxygen site doping anion, 0.8≤a≤1.2, 0≤b≤1, 0≤c≤1, 0≤d≤1, 0≤e≤1, 0≤f≤0.2, 0≤g≤2,0≤h≤2, b+c+d+e+f+f=1, and g+h=2;
M is selected from at least one of Si, Ti, Mo, V, Ge, Se, Zr, Nb, Ru, Pd, Sb, Ce, Te, and W;
A is selected from at least one of F, N, P, and S.
17. An electric apparatus comprising the secondary battery according to claim 15 .
18. A preparation method of non-aqueous electrolyte, comprising:
mixing a non-aqueous solvent, a lithium salt, a soluble Me salt, soluble tetrafluoroborate, and an additive to uniformity to obtain a non-aqueous electrolyte, wherein Me represents a metal element other than element lithium;
wherein the non-aqueous electrolyte contains the non-aqueous solvent and lithium ions, first cations, first anions, and second anions dissolved therein, wherein the first cations comprise is a metal cation Me n+ other than the lithium ion, n representing a chemical valence of the metal cation, Me n+ represents at least one of Ni 2+ , Co 2+ , Mn 2+ , Al 3+ , and Fe 2− , the first anions comprise is a tetrafluoroborate anion BF 4 − ; the second anions comprise at least one of perchlorate anion ClO 4 − , NO 3 − , and SO 4 2− a mass concentration of the first cations in the non-aqueous electrolyte is D1 ppm, and a mass concentration of the first anions in the non-aqueous electrolyte is D2 ppm, both based on total mass of the non-aqueous electrolyte; and the non-aqueous electrolyte satisfies: D1 is 0.1 to 1250, D2 is 1 to 2000, and D1/D2 is 0.02 to 2.
19. The preparation method according to claim 18 , wherein a difference between a standard reduction potential of Me n− and a standard reduction potential of Li + is 1.0 V or more, and Me n+ represents at least one of Ni 2+ , Co 2+ , Al 3+ , and Fe 2+ .
20. The preparation method according to claim 18 , wherein
the soluble Me salt comprises at least one of Me(BF 4 ) n , Me(ClO 4 ) n , Me[N(SO 2 CF 3 ) 2 ] n , Me(NO 3 ) n , Me(SO 4 ) n/2 , Me(PF 6 ) n , Me[N(SO 2 F) 2 ] n , Me(DFOB) n , Me(BOB) n , Me(AsF 6 ) n , Me(CF 3 SO 3 ) n , Me(PO 2 F 2 ) n , Me(DODFP) n , and Me(OTFP) n ;
the soluble tetrafluoroborate comprises at least one of Me(BF 4 ) n and LiBF 4 ;
the non-aqueous solvent comprises a cyclic carbonate compound and a linear carbonate compound;
the lithium salt comprises a first lithium salt, the first lithium salt comprising lithium hexafluorophosphate, lithium bis(fluorosulfonyl)imide, or a combination thereof, and the lithium salt further comprises a second lithium salt, the second lithium salt comprising at least one of lithium difluoro(oxalato)borate, lithium bis(oxalato)borate, lithium perchlorate, lithium bis(trifluoromethanesulfonyl)imide, lithium hexafluoroarsenate, lithium trifluoromethanesulfonate, lithium difluorophosphate, lithium difluorobis(oxalato)phosphate, and lithium tetrafluoro(oxalato)phosphate; and
the additive comprises at least one of a first additive and a second additive, wherein the first additive is fluoroethylene carbonate, and the second additive comprises at least one of vinylidene carbonate, lithium oxalate, vinyl sulfate, and 1,3-propane sultone.