Non-aqueous electrolyte and preparation method thereof, and secondary battery and electric apparatus containing same
Provided are 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 a 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 difluorooxalate borate anion DFOB − ; 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 0.5 to 870 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, and first anions dissolved therein, wherein 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 difluorooxalate borate anion DFOB − ; 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 0.5 to 870 and that D1/D2 is 0.02 to 2;
wherein Me n+ represents at least one of Ni 2+ , Co 2+ , Mn 2+ , Al 3+ , and Fe 2+ .
2 . The non-aqueous electrolyte according to claim 1 , wherein
D1 is 100 to 870;
D1/D2 is 0.3 to 2; and/or
D2 is 1 to 3000.
3 . The non-aqueous electrolyte according to claim 1 , wherein the non-aqueous electrolyte further contains second anions, wherein the second anion is a tetrafluoroborate anion BF 4 − , and mass concentration of the second anions in the non-aqueous electrolyte is D3 ppm based on the total mass of the non-aqueous electrolyte.
4 . The non-aqueous electrolyte according to claim 1 , wherein the non-aqueous electrolyte further contains third anions, wherein the third anion comprises at least one of perchlorate anion ClO 4 − , bis(trifluoromethanesulfonyl)imide anion N(SO 2 CF 3 ) 2 − , NO 3 − , and SO 4 2− and optionally comprises at least one of NO 3 − and SO 4 2− ; and mass concentration of the third anions in the non-aqueous electrolyte is D4 ppm based on the total mass of the non-aqueous electrolyte.
5 . The non-aqueous electrolyte according to claim 1 , wherein the non-aqueous electrolyte further contains fourth anions, wherein the fourth anion comprises hexafluorophosphate anion PFC, bis(fluorosulfonyl)imide anion N(SO 2 F) 2 − , or a combination thereof.
6 . The non-aqueous electrolyte according to claim 5 , wherein the non-aqueous electrolyte further contains fifth anions, wherein the fifth anion comprises at least one of 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.
7 . The non-aqueous electrolyte according to claim 6 , wherein the fifth anions comprise difluorophosphate anions PO 2 F 2 .
8 . 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, mass percentage of the cyclic carbonate compound is E1 and 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%.
9 . The non-aqueous electrolyte according to claim 8 , wherein the non-aqueous solvent further comprises an ether compound, wherein 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 mass percentage of the ether compound in the non-aqueous electrolyte is E3 based on the total mass of the non-aqueous electrolyte.
10 . 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, and mass concentration of the first additive in the non-aqueous electrolyte is D5 ppm based on the total mass of the non-aqueous electrolyte.
11 . 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.
12 . A preparation method of non-aqueous electrolyte, the preparation method comprising:
mixing a non-aqueous solvent, a lithium salt, a soluble Me salt, soluble difluorooxalate borate, and an optional 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, and first anions dissolved therein, wherein 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 difluorooxalate borate anion DFOB − ; 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 0.5 to 870 and that D1/D2 is 0.02 to 2.
13 . The preparation method according to claim 12 , wherein a difference between a standard reduction potential of Me n+ and a standard reduction potential of Li + is 1.0 V or more.
14 . The preparation method according to claim 12 , wherein
the soluble Me salt comprises at least one of Me(DFOB) n , Me(BF 4 ) n , Me(ClO 4 ) n , Me[N(SO 2 CF 3 ) 2 ] n , Me(NO 3 ) n/2 , Me(SO 4 ) n/2 , Me(PF 6 ) n , Me[N(SO 2 F) 2 ] 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 difluorooxalate borate comprises at least one of Me(DFOB) n and LiDFOB;
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 optionally, the lithium salt further comprises a second lithium salt, the second lithium salt comprising at least one of lithium bis(oxalato)borate, lithium tetrafluoroborate, lithium bis(trifluoromethanesulfonyl)imide, lithium perchlorate, lithium hexafluoroarsenate, lithium trifluoromethanesulfonate, lithium difluorophosphate, lithium difluorobis(oxalato)phosphate, and lithium tetrafluoro(oxalato)phosphate; and/or
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.
15 . The preparation method according to claim 12 , wherein Men+represents at least one of Ni 2+ , Co 2+ , Mn 2+ , Al 3+ , and Fe 2+ .
16 . The preparation method according to claim 12 , wherein the non-aqueous solvent further comprises an ether compound selected from at least one of tetrahydrofuran, 2-methyltetrahydrofuran, 1,3-dioxolane, ethylene glycol monomethyl ether, dimethoxyethane, tetraethylene glycol dimethyl ether, dimethoxymethane, and diglyme.
17 . 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 or an anon-aqueous electrolyte obtained by using the preparation method according to claim 12 .
18 . The secondary battery according to claim 17 , 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.
19 . An electric apparatus comprising the secondary battery according to claim 17 .