CN116914257A - Nonaqueous electrolyte and secondary battery thereof - Google Patents
Nonaqueous electrolyte and secondary battery thereof Download PDFInfo
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- CN116914257A CN116914257A CN202311087834.6A CN202311087834A CN116914257A CN 116914257 A CN116914257 A CN 116914257A CN 202311087834 A CN202311087834 A CN 202311087834A CN 116914257 A CN116914257 A CN 116914257A
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- sodium
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- 239000011255 nonaqueous electrolyte Substances 0.000 title claims abstract description 26
- ISAKRJDGNUQOIC-UHFFFAOYSA-N Uracil Chemical class O=C1C=CNC(=O)N1 ISAKRJDGNUQOIC-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000001257 hydrogen Substances 0.000 claims abstract description 21
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 21
- KBVUALKOHTZCGR-UHFFFAOYSA-M sodium;difluorophosphinate Chemical compound [Na+].[O-]P(F)(F)=O KBVUALKOHTZCGR-UHFFFAOYSA-M 0.000 claims abstract description 19
- -1 uracil compound Chemical class 0.000 claims abstract description 16
- 229940035893 uracil Drugs 0.000 claims abstract description 13
- 125000001183 hydrocarbyl group Chemical group 0.000 claims abstract description 12
- 150000002431 hydrogen Chemical class 0.000 claims abstract description 11
- 125000004093 cyano group Chemical group *C#N 0.000 claims abstract description 10
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000000654 additive Substances 0.000 claims abstract description 9
- 230000000996 additive effect Effects 0.000 claims abstract description 9
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims abstract description 7
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 7
- 150000002367 halogens Chemical class 0.000 claims abstract description 7
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims abstract description 7
- 159000000000 sodium salts Chemical class 0.000 claims abstract description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 4
- 239000003960 organic solvent Substances 0.000 claims abstract description 4
- 150000001412 amines Chemical class 0.000 claims abstract description 3
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 3
- 239000003792 electrolyte Substances 0.000 claims description 18
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 10
- 239000008151 electrolyte solution Substances 0.000 claims description 9
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 8
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 8
- 229910052708 sodium Inorganic materials 0.000 claims description 8
- 239000011734 sodium Substances 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 8
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 6
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 5
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 5
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims description 4
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 4
- HHRQHBSHDGPCRL-UHFFFAOYSA-N [O-2].[Mn+2].[Fe+2].[Ni+2].[O-2].[O-2] Chemical compound [O-2].[Mn+2].[Fe+2].[Ni+2].[O-2].[O-2] HHRQHBSHDGPCRL-UHFFFAOYSA-N 0.000 claims description 4
- HNAGHMKIPMKKBB-UHFFFAOYSA-N 1-benzylpyrrolidine-3-carboxamide Chemical compound C1C(C(=O)N)CCN1CC1=CC=CC=C1 HNAGHMKIPMKKBB-UHFFFAOYSA-N 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 239000011572 manganese Substances 0.000 claims description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 3
- UHOPWFKONJYLCF-UHFFFAOYSA-N 2-(2-sulfanylethyl)isoindole-1,3-dione Chemical compound C1=CC=C2C(=O)N(CCS)C(=O)C2=C1 UHOPWFKONJYLCF-UHFFFAOYSA-N 0.000 claims description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 2
- 239000004215 Carbon black (E152) Substances 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- 229920001774 Perfluoroether Polymers 0.000 claims description 2
- OBNCKNCVKJNDBV-UHFFFAOYSA-N butanoic acid ethyl ester Natural products CCCC(=O)OCC OBNCKNCVKJNDBV-UHFFFAOYSA-N 0.000 claims description 2
- 150000008282 halocarbons Chemical group 0.000 claims description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 2
- 125000000717 hydrazino group Chemical group [H]N([*])N([H])[H] 0.000 claims description 2
- 229930195733 hydrocarbon Natural products 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- BAZAXWOYCMUHIX-UHFFFAOYSA-M sodium perchlorate Chemical compound [Na+].[O-]Cl(=O)(=O)=O BAZAXWOYCMUHIX-UHFFFAOYSA-M 0.000 claims description 2
- 229910001488 sodium perchlorate Inorganic materials 0.000 claims description 2
- 229910001495 sodium tetrafluoroborate Inorganic materials 0.000 claims description 2
- XGPOMXSYOKFBHS-UHFFFAOYSA-M sodium;trifluoromethanesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C(F)(F)F XGPOMXSYOKFBHS-UHFFFAOYSA-M 0.000 claims description 2
- 150000003949 imides Chemical class 0.000 claims 1
- 239000006259 organic additive Substances 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 8
- 239000007789 gas Substances 0.000 abstract description 5
- 230000002195 synergetic effect Effects 0.000 abstract description 3
- 238000006864 oxidative decomposition reaction Methods 0.000 abstract description 2
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- 229910001415 sodium ion Inorganic materials 0.000 description 10
- 238000003860 storage Methods 0.000 description 8
- 125000001153 fluoro group Chemical group F* 0.000 description 6
- 125000006273 (C1-C3) alkyl group Chemical group 0.000 description 4
- 238000007600 charging Methods 0.000 description 4
- 229940125904 compound 1 Drugs 0.000 description 4
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 description 4
- 229910021385 hard carbon Inorganic materials 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000007774 positive electrode material Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 description 3
- 239000012752 auxiliary agent Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- 239000002000 Electrolyte additive Substances 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000006258 conductive agent Substances 0.000 description 2
- 238000010280 constant potential charging Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000011268 mixed slurry Substances 0.000 description 2
- 125000001297 nitrogen containing inorganic group Chemical group 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 239000011356 non-aqueous organic solvent Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- VCCATSJUUVERFU-UHFFFAOYSA-N sodium bis(fluorosulfonyl)azanide Chemical compound FS(=O)(=O)N([Na])S(F)(=O)=O VCCATSJUUVERFU-UHFFFAOYSA-N 0.000 description 2
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 2
- FSSPGSAQUIYDCN-UHFFFAOYSA-N 1,3-Propane sultone Chemical compound O=S1(=O)CCCO1 FSSPGSAQUIYDCN-UHFFFAOYSA-N 0.000 description 1
- 125000001731 2-cyanoethyl group Chemical group [H]C([H])(*)C([H])([H])C#N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- UBQYURCVBFRUQT-UHFFFAOYSA-N N-benzoyl-Ferrioxamine B Chemical compound CC(=O)N(O)CCCCCNC(=O)CCC(=O)N(O)CCCCCNC(=O)CCC(=O)N(O)CCCCCN UBQYURCVBFRUQT-UHFFFAOYSA-N 0.000 description 1
- 229910020808 NaBF Inorganic materials 0.000 description 1
- 229910020892 NaBOB Inorganic materials 0.000 description 1
- 229910021201 NaFSI Inorganic materials 0.000 description 1
- 241001460678 Napo <wasp> Species 0.000 description 1
- QXZNUMVOKMLCEX-UHFFFAOYSA-N [Na].FC(F)(F)S(=O)(=O)NS(=O)(=O)C(F)(F)F Chemical compound [Na].FC(F)(F)S(=O)(=O)NS(=O)(=O)C(F)(F)F QXZNUMVOKMLCEX-UHFFFAOYSA-N 0.000 description 1
- WFSRWJJESXWWSH-UHFFFAOYSA-N [O-2].[Fe+2].[Mn+2].[Ni+2].[Na+] Chemical compound [O-2].[Fe+2].[Mn+2].[Ni+2].[Na+] WFSRWJJESXWWSH-UHFFFAOYSA-N 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 239000006256 anode slurry Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 229910021383 artificial graphite Inorganic materials 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- VEWLDLAARDMXSB-UHFFFAOYSA-N ethenyl sulfate;hydron Chemical compound OS(=O)(=O)OC=C VEWLDLAARDMXSB-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- YLKTWKVVQDCJFL-UHFFFAOYSA-N sodium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Na+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F YLKTWKVVQDCJFL-UHFFFAOYSA-N 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- FVCJARXRCUNQQS-UHFFFAOYSA-N trimethylsilyl dihydrogen phosphate Chemical compound C[Si](C)(C)OP(O)(O)=O FVCJARXRCUNQQS-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0567—Liquid materials characterised by the additives
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0025—Organic electrolyte
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Secondary Cells (AREA)
Abstract
The invention provides a nonaqueous electrolyte and a secondary battery thereof. The nonaqueous electrolyte comprises sodium salt, an organic solvent and an additive, wherein the additive comprises sodium difluorophosphate and uracil compounds, and the structure of the uracil compounds is shown as follows. Wherein R is 1 ‑R 3 Each independently selected from hydrogen, halogen, nitro-containing groups, amine-containing groups, hydrazine-containing groups, cyano-containing groups, carbonyl-containing groups, C1-C6 hydrocarbyl groups, or C1-C6 halogenated hydrocarbyl groups, X is selected from C or N. The invention can effectively inhibit the oxidative decomposition of the non-aqueous electrolyte, improve the high-temperature cycle performance, reduce the gas production of the secondary battery and improve the low-temperature discharge performance of the secondary battery through the synergistic effect between the sodium difluorophosphate and the uracil compound.
Description
Technical Field
The invention relates to the technical field of secondary batteries, in particular to a non-aqueous electrolyte and a secondary battery thereof.
Background
The basic constituent unit of the secondary battery includes a negative electrode, a positive electrode, a separator (porous polymer material), and an electrolyte. Secondary batteries are also called rechargeable batteries, and generally have characteristics such as high reversibility, large difference in potential between positive and negative electrodes, and the like. Among them, sodium ion batteries have been widely accepted in the market because of their excellent resource controllability, environmental friendliness, and the like. The positive electrode material of the main sodium ion battery on the market is mainly layered oxide, on one hand, the layered oxide has higher energy density, and on the other hand, the layered oxide has similar structure with the layered oxide of the lithium battery, and the feasibility of mass production is realized. Although sodium ion batteries have made a great progress in the development of positive electrode materials, there are many problems such as release of substances having catalytic activity at high voltage and cracking and pulverization of the material surface during circulation, which bring about destruction of active ingredients in the electrolyte, and therefore, in the pursuit of high energy density, there is a need for development of an electrolyte additive capable of improving the high voltage layered oxide.
Disclosure of Invention
The invention aims to provide a nonaqueous electrolyte and a secondary battery thereof, wherein the additive of the nonaqueous electrolyte comprises sodium difluorophosphate and uracil compounds, and can effectively inhibit oxidative decomposition of the nonaqueous electrolyte through the synergistic effect between the sodium difluorophosphate and the uracil compounds, improve the high-temperature cycle performance of the secondary battery, reduce the gas production of the secondary battery and improve the low-temperature discharge performance of the secondary battery.
In order to achieve the above object, the present invention provides a nonaqueous electrolytic solution comprising a sodium salt, an organic solvent and an additive, the additive comprising sodium difluorophosphate and a uracil compound, the uracil compound having a structure as shown below,
wherein the R is 1 ～R 3 Each independently selected from hydrogen, halogen, nitro-containing groups, amine-containing groups, hydrazine-containing groups, cyano-containing groups, carbonyl-containing groups, C1-C6 hydrocarbyl groups, or C1-C6 halogenated hydrocarbyl groups, X is selected from C or N.
Compared with the prior art, the additive in the nonaqueous electrolyte provided by the invention comprises sodium difluorophosphate and uracil compounds, wherein the sodium difluorophosphate can improve SEI, naF-rich substances can be formed on the SEI surface, and the internal resistance of an interface is reduced. The uracil compound has uracil structure, so that the interface stability of the positive electrode material can be improved, and the high-temperature storage performance of the electrolyte is improved. Sodium difluorophosphate and uracil compounds are simultaneously added into non-aqueous electrolyte as additives, so that the characteristics of the original electrolyte are maintained, a synergistic effect is generated, fluorine atoms in sodium difluorophosphate can synergistically stabilize electrons of nitrogen-containing substances in uracil compounds, the electron cloud density of active hydrogen in uracil compounds is reduced, the decomposition gas production of the electrolyte is greatly slowed down, and the safety and the cycle performance of the electrolyte of the secondary battery are improved. Therefore, the nonaqueous electrolyte can maintain stable SEI under long-time circulation conditions, thereby improving the high-temperature circulation performance of the secondary battery and improving the low-temperature discharge performance of the secondary battery.
Preferably, X is selected from C, R 1 Selected from halogen, nitro-containing group, amino-containing group, C1-C6 hydrocarbon group or C1-C6 halogenated hydrocarbon group, R 2 And R is 3 Each independently selected from hydrogen or a C1-C6 hydrocarbyl group.
Preferably, X is selected from C, R 1 Selected from fluorine atoms, nitro-containing groups, amino-containing groups, C1-C3 alkyl groups or trifluoromethyl groups, R 2 And R is 3 Each independently selected from hydrogen or C1-C3 alkyl.
Preferably, X is selected from C, R 1 Selected from fluorine atoms, nitro groups, amino groups, ethyl groups or trifluoromethyl groups, R 2 And R is 3 Each independently selected from hydrogen or methyl.
Preferably, X is selected from N, R 1 Selected from hydrogen, halogen, hydrazino-containing groups, cyano-containing groups, R 2 Selected from hydrogen, carbonyl-containing groups, cyano-containing groups or C1-C6 hydrocarbon radicals, R 3 Selected from hydrogen or C1-C6 hydrocarbyl.
Preferably, X is selected from N, R 1 Selected from hydrogen, fluorine atoms, hydrazine-containing groups, cyano-containing groups, R 2 Selected from hydrogen, carbonyl-containing groups, cyano-containing groups or C1-C3-alkyl groups, R 3 Selected from hydrogen or C1-C3 alkyl.
Preferably, X is selected from N, R 1 Selected from hydrogen, fluorine atoms, hydrazine groups, cyano groups, R 2 Selected from hydrogen, carbonyl, cyanoethyl or methyl, R 3 Selected from hydrogen or methyl.
Preferably, the uracil compound is at least one selected from the group consisting of compounds 1 to 12,
preferably, the uracil compound accounts for 0.1% -2% of the total mass of the non-aqueous electrolyte. Specifically but not limited to 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 1%, 1.2%, 1.4%, 1.6%, 1.8%, 2%.
Preferably, the mass percentage of the sodium difluorophosphate in the nonaqueous electrolyte is 1% -5%, and specifically but not limited to 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5% and 5%.
Preferably, the nonaqueous electrolytic solution of the present invention further comprises an auxiliary agent selected from one or more of Vinylene Carbonate (VC), fluoroethylene carbonate (FEC), trimethylsilyl phosphate (TMSP), 1, 3-Propane Sultone (PS) and vinyl sulfate (DTD).
Preferably, the auxiliary agent accounts for 0.1-5% of the total mass of the nonaqueous electrolyte, and particularly but not limited to 0.1%, 0.5%, 1.0%, 1.5%, 2.0%, 2.5%, 3.0%, 3.5%, 4.0%, 4.5% and 5.0%.
Preferably, the sodium salt is selected from sodium hexafluorophosphate (NaPF 6 ) Sodium perchlorate (NaClO), sodium tetrafluoroborate (NaBF) 4 ) Sodium triflate (NaCF) 3 SO 3 ) At least one of sodium bis (trifluoromethylsulfonyl) imide (NaTFSI), sodium bis (oxalato) borate (NaBOB), sodium Difluoro (DFOB) oxalato borate (NaDFOB), sodium difluoro (NaDFOP) bisoxalato phosphate (NaFSI) and sodium bis (fluorosulfonyl) imide.
Preferably, the mass percentage of the sodium salt in the nonaqueous electrolyte is 6.5% -15.5%, specifically but not limited to 6.5%, 7.0%, 7.5%, 8.0%, 8.5%, 9.0%, 10.0%, 11.0%, 12.0%, 12.5%, 13.0%, 13.5%, 14.0%, 14.5%, 15.0%, 15.5%.
Preferably, the nonaqueous solvent is selected from at least one of Ethylene Carbonate (EC), dimethyl carbonate (DMC), diethyl carbonate (DEC), ethylmethyl carbonate (EMC), propylene Carbonate (PC), butyl acetate (n-Ba), γ -butyrolactone (γ -Bt), propyl propionate (n-PP), ethyl Propionate (EP), ethyl butyrate (Eb) and fluoroether. Preferably, the nonaqueous solvent is at least one selected from the group consisting of Ethylene Carbonate (EC), dimethyl carbonate (DMC), diethyl carbonate (DEC), ethylmethyl carbonate (EMC), and Propylene Carbonate (PC).
Preferably, the nonaqueous organic solvent of the present invention accounts for 60% -90% of the total mass of the nonaqueous electrolyte, specifically but not limited to 60%, 65%, 70%, 72%, 75%, 78%, 80%, 82%, 84%, 86%, 88%, 90%, preferably 70% -90%.
The second aspect of the invention provides a secondary battery, which comprises a positive electrode, a negative electrode and an electrolyte, wherein the electrolyte is the non-aqueous electrolyte, and the positive electrode comprises nickel-iron-manganese oxide.
Preferably, the chemical formula of the nickel-iron-manganese oxide is NaNi x Fe y Mn z M (1-x-y-z) O 2 Wherein M is independently selected from at least one of Mg, cu, zn, al, sn, B, ga, cr, sr and Ti, 0<x<1，0<y<1，0<z<1，x+y+z≤1。
Preferably, the negative electrode comprises a negative electrode material comprising any one of graphite, artificial graphite, hard carbon, natural graphite and mesophase microspheres, preferably hard carbon.
Detailed Description
For a better description of the objects, technical solutions and advantageous effects of the present invention, the present invention will be further described with reference to specific examples. It should be noted that the following implementation of the method is a further explanation of the present invention and should not be taken as limiting the present invention. Those not explicitly stated in the examples may be performed under conventional conditions or conditions suggested by the manufacturer. The reagents or apparatus used were conventional products available commercially without the manufacturer's attention.
Example 1
(1) Preparation of nonaqueous electrolyte
In a glove box filled with argon (O) 2 ＜1ppm，H 2 In O < 1 ppm), propylene Carbonate (PC), ethylene carbonate (DEC) and diethyl carbonate (DMC) were mixed in a weight ratio PC:DEC:DMC=1:1:1 to obtain 86.5g of a nonaqueous organic solvent, followed by adding 0.5g of Compound 1 and 1g of sodium difluorophosphate (NaPO) 2 F 2 ) After being dissolved and fully stirred, 12g of sodium hexafluorophosphate is added, and the electrolyte is obtained after uniform mixing.
(2) Preparation of the positive electrode
Sodium nickel iron manganese oxide ternary material NaNi 1/3 Fe 1/3 Mn 1/3 O 2 Uniformly mixing the adhesive PVDF and the conductive agent SuperP according to the mass ratio of 95:1:4 to prepare secondary battery anode slurry with certain viscosity, coating the mixed slurry on two sides of an aluminum foil, and drying and rolling to obtain the anode plate.
(3) Preparation of negative electrode
Preparing slurry from hard carbon, a conductive agent SuperP and an adhesive PVDF according to the mass ratio of 97:1:2, uniformly mixing, coating the mixed slurry on two sides of an aluminum foil, and drying and rolling to obtain the negative plate.
(4) Preparation of sodium ion batteries
And (3) manufacturing the positive electrode, the diaphragm and the negative electrode into square battery cells in a lamination mode, packaging by adopting polymers, filling the prepared non-aqueous electrolyte of the secondary battery, and manufacturing the secondary battery with the capacity of 1000mAh through the working procedures of formation, capacity division and the like.
The composition of the electrolytes of examples 1 to 23 and comparative examples 1 to 5 is shown in Table 1, wherein the electrolyte formulation procedure of examples 2 to 23 and comparative examples 1 to 5 is the same as that of example 1.
Table 1: composition of the electrolytes of examples and comparative examples
The sodium ion batteries manufactured in examples 1 to 23 and comparative examples 1 to 5 were respectively subjected to high temperature cycle performance, high temperature storage performance, thickness expansion rate and low temperature discharge performance under the following test conditions, and the test results are shown in table 2.
High temperature cycle performance test
And placing the secondary battery in an environment of 45 ℃ and standing for 30min to enable the sodium ion battery to reach constant temperature. At a current of 1CConstant current charging to 4.2V, constant voltage charging to current of 0.05C at 4.2V, constant current discharging to current of 4.2V at 1C, and initial discharge capacity of the recording battery of C 0 This is a charge-discharge cycle. Then charging and discharging for 400 weeks at 45 ℃ at 1C/1C, recording the discharge capacity of the last circle as C 1 The capacity retention is calculated as follows.
Capacity retention = C 1 /C 0 *100％
High temperature storage test
The secondary battery was placed in an environment of 25℃and charged to 4.2V at a constant current of 0.5C and then charged at a constant voltage until the current reached 0.05C, and then discharged to 2.0V at a constant current of 0.5C, and the discharge capacity was recorded as C at this time 0 . Then the battery is charged to 4.2V with a constant current of 0.5C and then charged to 0.05C with a constant voltage, and the thickness of the battery is recorded as D 0 . Placing the battery in a constant temperature oven at 60 ℃ for 30 days, taking out the battery, and recording the thickness D of the battery 1 . Then after the battery was left to stand in an environment of 25 ℃ for 2 hours, the battery was discharged to 2.0V at a constant current of 0.5C in an environment of 25 ℃, and the discharge capacity was recorded as C at this time 1 Then charging to 4.2V at constant current of 0.5C, then charging to 0.05C at constant voltage, and discharging to 2.0V at constant current of 0.5C. The discharge capacity at this time was recorded as C 2 。
Capacity retention = C 1 /C 0 *100％
Capacity recovery rate=c 2 /C 0 *100％
Thickness expansion ratio= ((D) 1 -D 0 )/D 0 )*100％
Low temperature discharge test
Low temperature discharge test: the secondary battery was charged and discharged 0.3C/0.3C at once under normal temperature (25 ℃ C.) conditions (the discharge capacity of the battery was recorded as C) 0 ) The upper limit voltage is 4.2V; then the battery was charged to 4.2V under a constant current and constant voltage of 0.5C, the battery was placed in an oven at-20 ℃ for 4 hours, and 0.3C discharge (discharge capacity recorded as C) was performed on the battery at-20 ℃ 1 ) Cut-off voltage of 3.0V, recalculated lowDischarge rate at temperature.
Low temperature discharge rate= (C 1 /C 0 )*100％
Table 2: secondary battery performance test results
From the test results of Table 2, it is understood that the high temperature cycle, high temperature storage, battery gas production and low temperature discharge performance of examples 1 to 23 are all at superior levels relative to comparative examples 1 to 5. The additive for the non-aqueous electrolyte comprises sodium difluorophosphate and uracil compounds, wherein the sodium difluorophosphate can improve interface transmission resistance of SEI, the uracil compounds can improve interface stability of a positive electrode material, high-temperature storage performance of the electrolyte is improved, meanwhile, the two electrolyte additives are added, characteristics of original electrolyte are reserved, a new characteristic is induced, fluorine atoms in the sodium difluorophosphate cooperate with electrons of nitrogen-containing substances in the uracil, so that electron cloud density of active hydrogen in the uracil is reduced, decomposition gas production of the electrolyte is greatly slowed down, and safety and cycle performance of the sodium ion battery electrolyte are improved. Therefore, the nonaqueous electrolyte can keep stable SEI (solid electrolyte interface film) under the long-time circulation condition, further improves the high-temperature circulation performance of the sodium ion battery, and can improve the low-temperature discharge performance of the sodium ion battery.
As is evident from the comparison of examples 1 to 12, the compound 1 has the best high and low temperature performance when used in combination with sodium difluorophosphate, because the compound 1 contains more nitrogen and amino groups, thus forming more nitrogen-containing inorganic substances deposited on the surface of hard carbon in the formation stage, and because the solubility of the nitrogen-containing inorganic substances in carbonate solvents is small, the continuous dissolution and formation process of SEI is slowed down, thus exhibiting better cell performance. Meanwhile, comparison of examples 1, 16-17 and example 18 also shows that the sodium ion battery of the invention has better electrochemical performance when the carbonate solvent is adopted.
Examples 21-23 have better high temperature storage performance than examples 1 and 19 due to the addition of the adjuvants.
Comparative example 1 contained only the auxiliary agent VC, and was inferior in the overall high-low temperature property to example 21; comparative example 2 contains sodium difluorophosphate only, which has poor high-temperature storage and high-temperature cycle performance, and comparative example 3 contains uracil compound only, which has poor low-temperature discharge performance; the absence of sodium difluorophosphate in comparative example 4, the low temperature discharge was slightly inferior, and the absence of compound 1 in comparative example 5, the high temperature cycle and high temperature storage performance were inferior.
Finally, it should be noted that the above embodiments are only for illustrating the technical solution of the present invention and not for limiting the scope of the present invention, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that the present invention can be modified or substituted without departing from the spirit and scope of the technical solution of the present invention.
Claims (10)
1. A non-aqueous electrolyte comprises sodium salt, organic solvent and additive, wherein the additive comprises sodium difluorophosphate and uracil compound, the structure of uracil compound is shown as follows,
wherein the R is 1 ～R 3 Each independently selected from hydrogen, halogen, nitro-containing groups, amine-containing groups, hydrazine-containing groups, cyano-containing groups, carbonyl-containing groups, C1-C6 hydrocarbyl groups, or C1-C6 halogenated hydrocarbyl groups, X is selected from C or N.
2. The nonaqueous electrolytic solution according to claim 1, characterized in thatThe X is selected from C, R 1 Selected from halogen, nitro-containing group, amino-containing group, C1-C6 hydrocarbon group or C1-C6 halogenated hydrocarbon group, R 2 And R is 3 Each independently selected from hydrogen or a C1-C6 hydrocarbyl group.
3. The nonaqueous electrolyte according to claim 1, wherein X is selected from N, R 1 Selected from hydrogen, halogen, hydrazino-containing groups, cyano-containing groups, R 2 Selected from hydrogen, carbonyl-containing groups, cyano-containing groups or C1-C6 hydrocarbon radicals, R 3 Selected from hydrogen or C1-C6 hydrocarbyl.
4. The nonaqueous electrolyte according to any one of claims 1 to 3, wherein the uracil compound is at least one compound selected from the group consisting of compounds 1 to 12,
5. the nonaqueous electrolytic solution according to any one of claims 1 to 3, wherein the uracil compound is 0.1 to 2% by mass of the total nonaqueous electrolytic solution.
6. The nonaqueous electrolytic solution according to claim 1 to 3, wherein the mass percentage of the sodium difluorophosphate in the nonaqueous electrolytic solution is 1% to 5%.
7. The nonaqueous electrolytic solution according to any one of claims 1 to 3, wherein the sodium salt is at least one selected from the group consisting of sodium hexafluorophosphate, sodium perchlorate, sodium tetrafluoroborate, sodium trifluoromethylsulfonate, sodium bistrifluoromethylsulfonylimide, sodium bisoxalato borate, sodium difluorooxalato borate, sodium difluorobisoxalato phosphate and sodium bisfluorosulfonyl imide.
8. The nonaqueous electrolytic solution according to any one of claims 1 to 3, wherein the organic solvent is at least one selected from the group consisting of ethylene carbonate, dimethyl carbonate, diethyl carbonate, methylethyl carbonate, propylene carbonate, butyl acetate, γ -butyrolactone, propyl propionate, ethyl butyrate and fluoroether.
9. A secondary battery comprising a positive electrode, a negative electrode, and an electrolyte, wherein the electrolyte is the nonaqueous electrolyte according to any one of claims 1 to 9, and the positive electrode comprises iron-nickel-manganese oxide.
10. The secondary battery according to claim 9, wherein the nickel-iron-manganese oxide has a chemical formula of NaNi x Fe y Mn z M (1-x-y-z) O 2 Wherein M is independently selected from at least one of Mg, cu, zn, al, sn, B, ga, cr, sr and Ti, 0<x<1，0<y<1，0<z<1，x+y+z≤1。
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