CN117154220A - Electrolyte for sodium ion battery and sodium ion battery thereof - Google Patents
Electrolyte for sodium ion battery and sodium ion battery thereof Download PDFInfo
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- CN117154220A CN117154220A CN202311097141.5A CN202311097141A CN117154220A CN 117154220 A CN117154220 A CN 117154220A CN 202311097141 A CN202311097141 A CN 202311097141A CN 117154220 A CN117154220 A CN 117154220A
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- Prior art keywords
- electrolyte
- ion battery
- sodium ion
- additive
- sodium
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- 239000003792 electrolyte Substances 0.000 title claims abstract description 69
- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 57
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 239000000654 additive Substances 0.000 claims abstract description 45
- 230000000996 additive effect Effects 0.000 claims abstract description 40
- 239000002904 solvent Substances 0.000 claims abstract description 24
- -1 amine compound Chemical class 0.000 claims abstract description 18
- 150000003839 salts Chemical class 0.000 claims abstract description 16
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 5
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 12
- 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 12
- 239000000463 material Substances 0.000 claims description 12
- 229910052708 sodium Inorganic materials 0.000 claims description 12
- 239000011734 sodium Substances 0.000 claims description 12
- 239000013538 functional additive Substances 0.000 claims description 9
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 8
- 150000001412 amines Chemical class 0.000 claims description 8
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-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
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 7
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 6
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 6
- 229910052710 silicon Inorganic materials 0.000 claims description 6
- 239000010703 silicon Substances 0.000 claims description 6
- FSSPGSAQUIYDCN-UHFFFAOYSA-N 1,3-Propane sultone Chemical compound O=S1(=O)CCCO1 FSSPGSAQUIYDCN-UHFFFAOYSA-N 0.000 claims description 5
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 claims description 5
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 claims description 4
- 229910019142 PO4 Inorganic materials 0.000 claims description 4
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 claims description 4
- 229910021385 hard carbon Inorganic materials 0.000 claims description 4
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 4
- 239000010452 phosphate Substances 0.000 claims description 4
- 229940090181 propyl acetate Drugs 0.000 claims description 4
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 claims description 4
- GWAOOGWHPITOEY-UHFFFAOYSA-N 1,5,2,4-dioxadithiane 2,2,4,4-tetraoxide Chemical compound O=S1(=O)CS(=O)(=O)OCO1 GWAOOGWHPITOEY-UHFFFAOYSA-N 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 3
- XXYVTWLMBUGXOK-UHFFFAOYSA-N [Na].FS(=N)F Chemical compound [Na].FS(=N)F XXYVTWLMBUGXOK-UHFFFAOYSA-N 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 229910021383 artificial graphite Inorganic materials 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- VUPKGFBOKBGHFZ-UHFFFAOYSA-N dipropyl carbonate Chemical compound CCCOC(=O)OCCC VUPKGFBOKBGHFZ-UHFFFAOYSA-N 0.000 claims description 3
- VEWLDLAARDMXSB-UHFFFAOYSA-N ethenyl sulfate;hydron Chemical compound OS(=O)(=O)OC=C VEWLDLAARDMXSB-UHFFFAOYSA-N 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 229910021382 natural graphite Inorganic materials 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 229920000447 polyanionic polymer Polymers 0.000 claims description 3
- XCXLEIPEAAEYTF-UHFFFAOYSA-M sodium fluorosulfate Chemical compound [Na+].[O-]S(F)(=O)=O XCXLEIPEAAEYTF-UHFFFAOYSA-M 0.000 claims description 3
- 229910021384 soft carbon Inorganic materials 0.000 claims description 3
- 229910052717 sulfur Inorganic materials 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 claims description 2
- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical compound [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 150000002596 lactones Chemical class 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 2
- 206010016766 flatulence Diseases 0.000 abstract description 2
- 125000000524 functional group Chemical group 0.000 abstract description 2
- 229910021645 metal ion Inorganic materials 0.000 abstract description 2
- 239000001301 oxygen Substances 0.000 abstract description 2
- 238000002161 passivation Methods 0.000 abstract description 2
- 238000000034 method Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- 239000012528 membrane Substances 0.000 description 7
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000007774 positive electrode material Substances 0.000 description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 5
- 239000004698 Polyethylene Substances 0.000 description 5
- 229910001416 lithium ion Inorganic materials 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- 239000004743 Polypropylene Substances 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- 239000006258 conductive agent Substances 0.000 description 4
- 238000011056 performance test Methods 0.000 description 4
- 229920001155 polypropylene Polymers 0.000 description 4
- 159000000000 sodium salts Chemical class 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 239000002033 PVDF binder Substances 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 210000004027 cell Anatomy 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 210000001787 dendrite Anatomy 0.000 description 3
- 239000011267 electrode slurry Substances 0.000 description 3
- 239000008151 electrolyte solution Substances 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000007773 negative electrode material Substances 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000006183 anode active material Substances 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 2
- 230000002687 intercalation Effects 0.000 description 2
- 238000009830 intercalation Methods 0.000 description 2
- 238000004537 pulping Methods 0.000 description 2
- 238000004080 punching Methods 0.000 description 2
- 239000002994 raw material Substances 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
- KBVUALKOHTZCGR-UHFFFAOYSA-M sodium;difluorophosphinate Chemical compound [Na+].[O-]P(F)(F)=O KBVUALKOHTZCGR-UHFFFAOYSA-M 0.000 description 2
- KZNICNPSHKQLFF-UHFFFAOYSA-N succinimide Chemical compound O=C1CCC(=O)N1 KZNICNPSHKQLFF-UHFFFAOYSA-N 0.000 description 2
- ZPFAVCIQZKRBGF-UHFFFAOYSA-N 1,3,2-dioxathiolane 2,2-dioxide Chemical compound O=S1(=O)OCCO1 ZPFAVCIQZKRBGF-UHFFFAOYSA-N 0.000 description 1
- ONLCJOKGIFUOJN-UHFFFAOYSA-N 1-[bis(2,5-dioxopyrrol-1-yl)methoxy-(2,5-dioxopyrrol-1-yl)methyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C(N1C(C=CC1=O)=O)OC(N1C(C=CC1=O)=O)N1C(=O)C=CC1=O ONLCJOKGIFUOJN-UHFFFAOYSA-N 0.000 description 1
- DCERHCFNWRGHLK-UHFFFAOYSA-N C[Si](C)C Chemical compound C[Si](C)C DCERHCFNWRGHLK-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000002000 Electrolyte additive Substances 0.000 description 1
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- OJOUOVMLFBIHRQ-UHFFFAOYSA-M P(=O)([O-])(O)O.C(C(=O)O)(=O)F.C(C(=O)O)(=O)F.C(C(=O)O)(=O)F.C(C(=O)O)(=O)F.[Na+] Chemical compound P(=O)([O-])(O)O.C(C(=O)O)(=O)F.C(C(=O)O)(=O)F.C(C(=O)O)(=O)F.C(C(=O)O)(=O)F.[Na+] OJOUOVMLFBIHRQ-UHFFFAOYSA-M 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- FCCCRBDJBTVFSJ-UHFFFAOYSA-N butanehydrazide Chemical compound CCCC(=O)NN FCCCRBDJBTVFSJ-UHFFFAOYSA-N 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 150000005676 cyclic carbonates Chemical class 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- JFCQEDHGNNZCLN-UHFFFAOYSA-N glutaric acid Chemical compound OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 238000006864 oxidative decomposition reaction Methods 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 125000004436 sodium atom Chemical group 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 229960002317 succinimide Drugs 0.000 description 1
- ZQDZSGHAIZKNHJ-UHFFFAOYSA-N trisodium difluoro oxalate borate Chemical compound [Na+].[Na+].[Na+].[O-]B([O-])[O-].FOC(=O)C(=O)OF ZQDZSGHAIZKNHJ-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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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 application discloses electrolyte for a sodium ion battery and the sodium ion battery thereof, and relates to the technical field of sodium ion batteries. The application provides an electrolyte for a sodium ion battery and the sodium ion battery, wherein the electrolyte for the sodium ion battery comprises electrolyte salt, a nonaqueous solvent and an additive, wherein the additive structure comprises a naphthenic amine compound additive except for a positive and negative film-forming additive, and is rich in various functional groups, so that an excellent ionic passivation film can be formed on the surface of an electrode, metal ions can be complexed, oxygen free radicals can be captured, an anode active site can be passivated, flatulence at high temperature can be restrained, and the high and low temperature performance of the battery can be improved.
Description
Technical Field
The application relates to the technical field of sodium ion batteries, in particular to electrolyte for a sodium ion battery and the sodium ion battery thereof.
Background
The lithium ion battery is favored by new energy markets because of the advantages of high energy density, high energy conversion efficiency, high safety performance, long cycle performance, environmental friendliness and the like. However, the reserve of lithium resources is limited, the crust content is only 0.006%, and the distribution on the earth is uneven, and in recent years, the price of lithium ores is continuously increased, so that the production cost of the lithium ion battery is driven to be high. While sodium and lithium are both alkali metal elements, and sodium atoms have very similar physicochemical properties to lithium atoms and are similar in the mechanism of deintercalation/intercalation. In recent years, sodium ion batteries have been widely studied. On the one hand, the content of sodium element in crust is up to 2.64%, and the resource is rich. On the other hand, the sodium element is uniformly distributed, the exploitation cost is low, and the raw materials used for the electrolyte of the sodium ion battery are basically consistent with those of the lithium ion battery. In combination, the production cost of sodium ion batteries is far lower than that of lithium ion batteries.
However, the positive electrode material of the sodium ion battery has strong alkalinity, and reacts with carbonic ester in the electrolyte to promote the decomposition of the carbonic ester; in addition, trace water in the electrolyte reacts with the solvent and the electrolyte, so that the electrolyte is decomposed in the storage and working processes of the battery, gas is generated, the internal pressure of the battery is increased, the shell is deformed, the battery expands, gas is out, and even the risk of leakage occurs; in addition, the generated gas is filled between the positive electrode and the negative electrode, so that the electrical contact of each component in the battery is poor, the impedance is increased, and the battery performance is reduced. In addition, as the radius of sodium ions is larger, the intercalation property in the carbon material is inferior to that of lithium ions, and as charge and discharge are carried out, the decomposition of the electrolyte produces gas to degrade the electrical contact property of each component in the battery, so that a small part of deposition occurs to form dendrites, and when dendrites grow too fast, the dendrites possibly penetrate through a diaphragm, thereby causing potential safety hazards. Therefore, the problem of decomposing electrolyte to produce gas is a necessary problem in the commercialized application process of the sodium ion battery.
Aiming at the problems, the prior solution mainly comprises the measures of anode material modification (such as doping, surface coating and the like), cathode material (such as surface modification, process optimization), electrolyte regulation and control and the like. However, the modification cost of the anode and cathode materials is high, and the addition of functional additives to the electrolyte is the most economically viable route.
Disclosure of Invention
In order to solve the problems of long time consumption, high cost, slow effect and the like in the modification of the anode and cathode ends in the prior art, the application provides electrolyte for a sodium ion battery and the sodium ion battery thereof.
In order to solve the problems, the application provides a technical scheme.
In a first aspect, the application provides an electrolyte for a sodium ion battery, comprising electrolyte salt and a nonaqueous solvent for dissolving the electrolyte salt, the electrolyte further comprises additives, the additives comprise a positive electrode film-forming additive, a negative electrode film-forming additive and a functional additive containing naphthenamines, the functional additive containing naphthenamines has at least one of compounds shown as a formula I and a formula II,
R1-R10 in the formula I and the formula II are H, N, S, O and silicon base or silicon base derivatives thereof, or are one or more of alkyl groups with 1-7 carbon atoms and derivatives thereof.
Preferably, the electrolyte contains 0.01 to 10 percent of functional additive containing naphthenic amine in mass percent.
Preferably, the electrolyte contains 0.2-2% of the functional additive containing the naphthenic amine in percentage by mass.
Preferably, the electrolyte salt, the nonaqueous solvent and the additive in the electrolyte solution account for 8 to 20 percent by mass: 70% -90%:0.01% -10%.
Preferably, the electrolyte salt, the nonaqueous solvent and the additive in the electrolyte solution account for 10 to 15 percent by mass: 80% -85%:2% -5%.
Preferably, the electrolyte salt is one or more of sodium hexafluorophosphate, sodium difluorosulfimide, sodium fluorosulfonate, sodium difluorooxalato borate, sodium bisoxalato borate and sodium difluorooxalato phosphate, and the nonaqueous solvent is one or more of ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, dipropyl carbonate of methyl ethyl carbonate, ethyl acetate, methyl acetate, ethyl propionate, propyl acetate and propyl propionate.
Preferably, the positive electrode film-forming additive is one or more of propane sultone, methane disulfonic acid methylene ester and 1, 3-propylene sultone, and the negative electrode film-forming additive is one or more of vinyl sulfate, vinylene carbonate and fluoroethylene carbonate.
In a second aspect, the application provides a sodium ion battery, which is provided with a positive electrode, a negative electrode, a diaphragm and an electrolyte, wherein the electrolyte is the electrolyte provided by any embodiment of the application, the material of the positive electrode is one or more of a layered oxide material and a polyanion material, and the material of the negative electrode is one or more of artificial graphite, natural graphite, soft carbon, hard carbon, silicon carbon and silica.
The beneficial effects are that: the application provides an electrolyte for a sodium ion battery and the sodium ion battery, wherein the electrolyte for the sodium ion battery comprises electrolyte salt, a nonaqueous solvent and an additive, wherein the additive structure comprises a naphthenic amine compound additive except for a positive and negative electrode film forming additive, and the naphthenic amine compound additive is rich in various functional groups, so that an excellent ionic passivation film can be formed on the surface of an electrode, metal ions can be complexed, oxygen free radicals can be captured, positive electrode active sites can be passivated, flatulence at high temperature can be restrained, and the high and low temperature performance of the battery can be improved.
Drawings
Fig. 1 is a flowchart of a method for manufacturing a sodium ion battery according to an embodiment of the present application.
Detailed Description
The present application will be further described with reference to the following examples, in which technical terms and comparative examples are used in the same sense as those of the concepts related to the field of sodium ion batteries. The chemical reagents used in the following examples and comparative examples were all conventional chemical reagents unless otherwise specified. Furthermore, the following detailed description of the examples and comparative examples is not to be construed as limiting the application in any way, and any limited number of modifications which may be made within the scope of the claims hereof.
English abbreviations and Chinese meanings appearing in the embodiments of the present application
VC: vinylene carbonate; FEC: fluoroethylene carbonate; PS: propane sultone; DTD: vinyl sulfate; MMDS: methane sulfonyl dimethyl ester; TMSP: tri (trimethyl) silicon-based phosphate; PST:1, 3-propenesulfonic acid lactone; naDFOB: sodium difluoro oxalate borate; naDFOP: sodium tetrafluorooxalate phosphate; naDFP: sodium difluorophosphate; EC: ethylene carbonate; PC: propylene carbonate; DMC: dimethyl carbonate; DEC: diethyl carbonate; EMC: methyl ethyl carbonate; naPF6: sodium hexafluorophosphate; naFSI: sodium bis (fluorosulfonyl) imide; HF: hydrogen fluoride; naTFSI: sodium bis (trifluoromethylsulfonyl) imide.
In a first aspect, the application provides an electrolyte for a sodium ion battery, comprising 8% -20% of electrolyte salt and 70% -90% of nonaqueous solvent for dissolving the electrolyte salt, the electrolyte further comprising 0.01% -10% of additive, the additive comprises positive electrode film-forming additive, negative electrode film-forming additive and additive containing naphthene amine, the additive containing naphthene amine is at least one of compounds shown as formula I and formula II,
R1-R10 in the formula I and the formula II are H, N, S, O and silicon base or silicon base derivatives thereof, or are one or more of alkyl groups with 1-7 carbon atoms and derivatives thereof; specifically, the additive is a compound containing naphthenic amine, and the compound containing naphthenic amine is selected from at least one of the following compounds, wherein the compounds I-1, I-2, II-1, II-2 and II-3 are respectively succinimide, bissuccinimide glutarate, maleimide, 4-maleimide butyrylhydrazine and bismaleimidomethyl ether.
In the embodiment, the electrolyte contains 0.01-10% of the functional additive containing the naphthenic amine in percentage by mass.
In the embodiment, the electrolyte salt, the nonaqueous solvent and the additive in the electrolyte solution account for 10 to 15 percent by mass: 80% -85%:2% -5%.
In this embodiment, the electrolyte salt is one or more of sodium hexafluorophosphate, sodium difluorosulfimide, sodium fluorosulfonate, sodium difluorooxalato borate, sodium bisoxalato borate, sodium difluorooxalato phosphate, the nonaqueous solvent is one or more of Ethylene Carbonate (EC), propylene Carbonate (PC), dimethyl carbonate (DMC), diethyl carbonate (DEC), ethyl Methyl Carbonate (EMC) dipropyl carbonate, ethyl Acetate (EA), methyl Acetate (MA), ethyl Propionate (EP), propyl Acetate (PA), propyl Propionate (PP), and specifically, the nonaqueous solvent used in the present application includes two or more of the above solvents, the positive electrode film-forming additive is one or more of propane sultone, methylene methane disulfonate, 1, 3-propenesulfonolide, and the negative electrode film-forming additive is one or more of ethylene sulfate, ethylene carbonate, and fluoroethylene carbonate.
In another alternative embodiment, the electrolyte contains 0.2-2% of the functional additive containing the naphthenic amine in percentage by mass.
In a second aspect, the application provides a sodium ion battery, comprising a positive plate, a negative plate and a diaphragm. The application provides a sodium ion battery for verifying the performance of electrolyte additives, wherein electrolyte is prepared according to test requirements, and then the electrolyte is injected into the sodium ion battery. The sodium ion battery not only comprises electrolyte to be verified, but also comprises a positive electrode, a negative electrode and a diaphragm.
The positive electrode active material of the sodium ion battery used in the present application includes all commonly used materials such as one or more of layered oxides, polyanions, and the like.
In a further embodiment, the positive electrode is an aluminum foil sheet coated with a layered oxide, the positive electrode sheet comprising a positive active material that intercalates or deintercalates sodium ions, a conductive agent, a current collector, and a binder.
The present application does not strictly limit the type of the anode active material, and all the anode active materials commonly used at present can meet the requirements of the present application. Specifically, the negative electrode plate comprises one or more of natural graphite, artificial graphite, hard carbon, soft carbon, silicon oxygen and the like, and the negative electrode plate comprises a negative electrode active material capable of embedding or extracting sodium ions, a conductive agent, a current collector and a binder.
The mass fraction of the sodium salt and the solvent in the electrolyte is not particularly limited, and can be limited by referring to the mass fraction of the sodium salt and the solvent in the electrolyte commonly used for sodium ion batteries, or can be determined according to factors such as the positive electrode material, the negative electrode material, the diaphragm, the cell design and development requirements of the sodium ion batteries. In a specific embodiment of the present application, the concentration of the electrolyte sodium salt in the solvent is 0 to 5mol/L, and further, in a preferred embodiment, the concentration of the electrolyte sodium salt in the solvent is 0.5 to 1.5mol.
The present application does not strictly limit the selection range of the separator, and the separator commonly used at present meets the requirements of the present application, for example: one of polypropylene membrane (PP), polyethylene membrane (PE), polyethylene/polypropylene double-layer composite membrane, polyimide electrospun membrane (PI), polypropylene/polyethylene/polypropylene three-layer composite membrane (PP/PE/PP), ceramic membrane, PVDF rubberized membrane, etc., and specific test mode and results are shown in the following embodiments.
The electrochemical properties of the electrolyte according to the present application are described below by way of data of examples and comparative examples.
The electrolyte used in this example and comparative example was prepared by the following method: controlling the water content in the glove box to be not more than 10ppm, fully stirring and uniformly mixing a cyclic carbonate solvent Propylene Carbonate (PC), a linear carbonate solvent methyl ethyl carbonate (EMC) and a linear carbonate solvent dimethyl carbonate (DEC) according to the mass ratio of 2:2:1, and purifying by using a molecular sieve to remove impurities and water; under the condition of room temperature, adding 1.0mol/L sodium hexafluorophosphate (NaPF 6) into the mixed solvent, stirring while adding, adding a proper amount of additive after uniformly mixing, and fully and uniformly mixing to obtain the sample liquid. Specific examples are shown in table 1 below:
table 1: solvent, lithium salt and additive ratio in electrolyte sample
The positive electrode active materials of the sodium ion batteries used in the present examples and comparative examples were layered oxide/hard carbon soft pack batteries.
Referring to fig. 1, in a preferred embodiment, the present application provides a method for preparing a sodium ion battery, comprising the following steps:
s1: preparing a positive plate; dispersing one or more positive electrode active materials, a conductive agent and a binder polyvinylidene fluoride (PVDF) into a proper amount of N-methyl pyrrolidone according to the mass ratio of 96:2:2, and then fully and uniformly stirring the materials according to the pulping step. Uniformly coating the uniformly dispersed positive electrode slurry on an aluminum foil, and baking, rolling, slitting and punching to obtain the positive electrode plate.
S2: preparing a negative electrode sheet; the specific manufacturing process of the negative plate comprises the following steps: one or more negative electrode active materials, a conductive agent, styrene Butadiene Rubber (SBR) and sodium carboxymethylcellulose (CMC) are selected, all raw materials are dispersed into water according to the mass ratio of 97:1:1:1, and the uniformly dispersed negative electrode slurry is prepared according to a pulping process. And uniformly coating the negative electrode slurry on a copper foil, and baking, rolling, slitting and punching to obtain the negative electrode plate.
S3: and assembling the obtained positive plate, negative plate and diaphragm to obtain a battery cell, packaging the battery cell, injecting electrolyte, sealing again, and performing the procedures of formation, capacity division and the like to obtain the sodium ion battery.
Sodium ion battery performance test
The electrolytes of examples and comparative examples and sodium ion batteries were tested and compared for performance differences using the following methods:
(1) 60 ℃ high-temperature storage performance test
Charging sodium ion battery to 4.0V at room temperature with 1C constant current and constant voltage, cutting off current to 0.05C, making it in full state, testing and recording thickness D of sodium ion battery 0 Then placing into a 60 ℃ incubator for storage for 7 days, immediately testing the thickness of the sodium ion battery after storage and marking as D 1 。
Thickness expansion ratio ε= (D) 1 -D 0 )/D 0 *100％
The above performance test results are shown in table 2:
table 2: sodium ion battery electrical performance test results:
comparing the results shown in Table 2, the following correlation results can be obtained: after the additive containing the naphthenic amine compound is added, the gas production performance of the battery is obviously inhibited after the battery is stored at a high temperature of 60 ℃ for 7 days, but the addition amount of the additive is not easy to be excessively large, and excessive additive can cause that the material has thicker film forming thickness, increased impedance, reduced film forming uniformity and poor stability when in oxidative decomposition, thereby causing gas production to be aggravated. Meanwhile, the material can be used together with other positive and negative film forming additives to further improve the high-temperature performance of the sodium ion battery.
Claims (8)
1. An electrolyte for a sodium ion battery is characterized by comprising electrolyte salt and a nonaqueous solvent for dissolving the electrolyte salt, and further comprising additives, wherein the additives comprise a positive electrode film-forming additive, a negative electrode film-forming additive and a functional additive containing naphthenic amine, the functional additive containing naphthenic amine is at least one of compounds shown as a formula I and a formula II,
formula I:formula II: />
R1-R10 in the formula I and the formula II are H, N, S, O and silicon base or silicon base derivatives thereof, or are one or more of alkyl groups with 1-7 carbon atoms and derivatives thereof.
2. The electrolyte for a sodium ion battery according to claim 1, wherein the additive contains 0.01-10% by mass of the additive.
3. The electrolyte for a sodium ion battery according to claim 2, wherein the additive contains 0.2-2% by mass of the additive.
4. The electrolyte for a sodium ion battery according to claim 1, wherein the electrolyte salt, the nonaqueous solvent and the additive in the electrolyte are in a mass ratio of 8% -20%:70% -90%:0.01% -10%.
5. The electrolyte for the sodium ion battery according to claim 4, wherein the electrolyte salt, the nonaqueous solvent and the additive in the electrolyte are in a mass ratio of 10% -15%:80% -85%:2% -5%.
6. The electrolyte for a sodium ion battery according to claim 1, wherein the electrolyte salt is one or more of sodium hexafluorophosphate, sodium difluorosulfimide, sodium fluorosulfonate, sodium difluorooxalato borate, sodium bisoxalato borate and sodium difluorooxalato phosphate, and the nonaqueous solvent is one or more of ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl methyl carbonate, dipropyl carbonate, ethyl acetate, methyl acetate, ethyl propionate, propyl acetate and propyl propionate.
7. The electrolyte for a sodium ion battery according to claim 6, wherein the positive film-forming additive is one or more of propane sultone, methane disulfonic acid methylene ester, 1, 3-propenesulfonic acid lactone, and the negative film-forming additive is one or more of vinyl sulfate, vinylene carbonate, fluoroethylene carbonate.
8. A sodium ion battery, characterized in that the sodium ion battery is provided with a positive electrode, a negative electrode, a diaphragm and an electrolyte, wherein the electrolyte is the electrolyte of any one of claims 1-7, the material of the positive electrode is one or more of a layered oxide material and a polyanion material, and the material of the negative electrode is one or more of artificial graphite, natural graphite, soft carbon, hard carbon, silicon carbon and silicon oxygen.
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