ELECTROLYTE SOLUTION AND SECONDARY BATTERY CONTAINING SAME, BATTERY MODULE, BATTERY PACK, AND ELECTRICAL DEVICE
An electrolyte solution, a battery module, a battery pack, and an electrical device are disclosed. The electrolyte solution includes a solvent and a fluorine-containing lithium salt. An electrochemical stability coefficient of the electrolyte solution is x=S F /(S F +4S H ), ranging from 0.18 to 0.6, optionally 0.25 to 0.55, where S F and S H are measurable by a specified measurement method. The secondary battery that employs the electrolyte solution is of high electrochemical stability, and the electrolyte solution improves the storage performance and cycle performance of the secondary battery.
1 . An electrolyte solution, comprising a solvent and a fluorine-containing lithium salt, wherein an electrochemical stability coefficient of the electrolyte solution is x=S F /(S F +4S H ), ranging from 0.18 to 0.6, optionally 0.25 to 0.55, wherein
S F is a peak area of fluorine except fluorine corresponding to a lithium salt and fluorine corresponding to 4-fluoropyridine in a chemical shift range of −280 ppm to 80 ppm observed in fluorine nuclear magnetic resonance NMR spectroscopy for a mixture of the electrolyte solution and the 4-fluoropyridine mixed at a mass ratio of 1:1, and a peak area of the fluorine corresponding to the 4-fluoropyridine in a chemical shift range of −102 ppm to −104 ppm is normalized to 1;
S H is a peak area of hydrogen except hydrogen corresponding to deuterated acetonitrile and 4-fluoropyridine in a chemical shift range of 0.5 ppm to 10 ppm observed in hydrogen nuclear magnetic resonance NMR spectroscopy for a mixture of the electrolyte solution and the 4-fluoropyridine mixed at a mass ratio of 1:1, and a peak area of the hydrogen corresponding to the 4-fluoropyridine in a chemical shift range of 7.0 ppm to 7.2 ppm and a chemical shift range of 8.45 ppm to 8.65 ppm is normalized to 1; and
the electrolyte solution contains neither the deuterated acetonitrile nor the 4-fluoropyridine.
2 . The electrolyte solution according to claim 1 , wherein the electrolyte solution comprises a first solvent and a second solvent;
the first solvent is one or more selected from a fluoroether, a fluorocarbonate ester, a fluorocarboxylate ester, a fluorobenzene, or a fluorosulfone;
optionally, the first solvent is one or more of
wherein R 1 , R 3 , R 5 , and R 13 each are independently selected from C 1 to C 6 fluoroalkanes; R 2 , R 4 , R 6 , R 14 , R 15 , and R 16 each are independently selected from C 1 to C 6 alkanes or C 1 to C 6 fluoroalkanes;
R 7 to R 12 each are independently selected from a C 1 to C 6 fluoroalkane, fluorine, or hydrogen; at least one of R 7 to R 12 is selected from fluorine or a fluoroalkane; and at least one of R 15 or R 16 is selected from C 1 to C 6 fluoroalkanes;
further optionally, the first solvent is one or more of
the second solvent is one or more selected from a non-fluorinated carbonate ester, a non-fluorinated carboxylate ester, a non-fluorinated ether, or a non-fluorinated sulfone;
optionally, the second solvent is one or more of
wherein R 1 ′, R 2 ′, R 3 ′, R 13 ′, R 14 ′, and R 16 ′ each are independently selected from C 1 to C 6 alkanes; and R 4 ′ and R 15 ′ each are independently selected from a C 1 to C 6 alkane or hydrogen; and
optionally, the second solvent is one or more of ethyl methyl carbonate, dimethyl carbonate, diethyl carbonate, ethylene carbonate, propylene carbonate, methyl formate, methyl acetate, ethyl acetate, propyl acetate, methyl propionate, ethyl propionate, or propyl propionate.
3 . The electrolyte solution according to claim 2 , wherein a mass percent y 1 of the first solvent is 10% to 100%, optionally 45% to 100%, and further optionally 80% to 100%, based on a total mass of the first solvent and the second solvent.
4 . The electrolyte solution according to claim 2 , wherein a mass percent y 2 of the second solvent is 0% to 90%, optionally 0% to 55%, and further optionally 0% to 20%, based on a total mass of the first solvent and the second solvent.
5 . The electrolyte solution according to claim 3 , wherein the mass percent y 1 of the first solvent and a mass percent y 2 of the second solvent satisfy: y 1 /y 2 ≥0.82, optionally y 1 /y 2 ≥2.33, further optionally y 1 /y 2 ≥4, and still further optionally y 1 /y 2 ≥5.67.
6 . The electrolyte solution according to claim 1 , wherein the electrolyte solution further comprises a film-forming additive, and the film-forming additive is one or more selected from a chain or cyclic sulfate ester, a chain or cyclic sulfonate ester, a chain or cyclic carbonate ester, a polycyclic sulfate ester, or a polycyclic sulfonate ester;
optionally, the film-forming additive is one or more of
and
further optionally, the film-forming additive is one or more of
7 . The electrolyte solution according to claim 6 , wherein a mass percent of the film-forming additive is 0.1% to 10%, optionally 0.5% to 7%, and further optionally 1% to 5%, based on a total mass of the first solvent and the second solvent.
8 . The electrolyte solution according to claim 6 , wherein the film-forming additive comprises 0.5% to 1.0%
0.5% to 2.5%
0.5% to 2%
or 0.5% to 2%
based on a total mass of the first solvent and the second solvent.
9 . The electrolyte solution according to claim 1 , wherein the lithium salt comprises one or more of lithium hexafluorophosphate or lithium bis(fluorosulfonyl)imide.
10 . The electrolyte solution according to claim 1 , wherein a concentration of the lithium salt is 0.7 to 2.5 mol/L, and optionally 1 to 1.5 mol/L.
11 . The electrolyte solution according to claim 1 , wherein an acidity of the electrolyte solution is less than or equal to 50 ppm, and a purity of each solvent in use is greater than or equal to 99.8%.
12 . A secondary battery, wherein the secondary battery comprises the electrolyte solution according to claim 1 .
13 . The secondary battery according to claim 12 , wherein
a mass percent of Mn in a positive active material of the secondary battery is greater than or equal to 25%, based on a total mass of the positive active material;
optionally, the positive active material is one or more of LiM p Mn 2-p O 4 , LiN q Mn 1-q PO 4 , or Li 1+t Mn 1-w LwO 2+t , wherein 0≤p≤1, 0≤q≤0.5, 0≤t≤1, 0≤w≤0.5; and
M, N, and L each independently represent one or more of Ni, Co, Fe, Cr, V, Ti, Zr, La, Ce, Rb, P, W, Nb, Mo, Sb, B, Al, or Si;
further optionally, the positive active material is one or more of LiM p Mn 2-p O 4 or Li 1+t Mn 1-w LwO 2+t ; and
further optionally, the positive active material is one or more of LiNi 0.5 Mn 1.5 O 4 , LiNi 0.5 Co 0.2 Mn 0.3 O 2 , LizMnO 3 , or LiMnPO 4 .
14 . The secondary battery according to claim 12 , wherein particles of the positive active material are monocrystalline or quasi-monocrystalline.
15 . The secondary battery according to claim 12 , wherein a particle diameter of the positive active material is 1 to 20 μm, and optionally 3 to 15 μm.
16 . The secondary battery according to claim 12 , wherein a specific surface area of the positive active material is not greater than 1.5 m 2 /g, and optionally is 0.1 m 2 /g to 1 m 2 /g.
17 . A battery module, comprising the secondary battery according to claim 12 .
18 . A battery pack, comprising the battery module according to claim 17 .
19 . An electrical device, comprising at least one of the secondary battery according to claim 12 .