CN114156543B - Sodium ion battery electrolyte, sodium ion battery and preparation method - Google Patents
Sodium ion battery electrolyte, sodium ion battery and preparation method Download PDFInfo
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- CN114156543B CN114156543B CN202111639648.XA CN202111639648A CN114156543B CN 114156543 B CN114156543 B CN 114156543B CN 202111639648 A CN202111639648 A CN 202111639648A CN 114156543 B CN114156543 B CN 114156543B
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- sodium
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- sodium ion
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- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 53
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 239000003792 electrolyte Substances 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title abstract description 9
- 239000000654 additive Substances 0.000 claims abstract description 22
- 230000000996 additive effect Effects 0.000 claims abstract description 22
- 239000002904 solvent Substances 0.000 claims abstract description 19
- 159000000000 sodium salts Chemical class 0.000 claims abstract description 10
- 239000003960 organic solvent Substances 0.000 claims abstract description 7
- -1 sodium hexafluorophosphate Chemical compound 0.000 claims description 20
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 12
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 12
- 239000002033 PVDF binder Substances 0.000 claims description 12
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 12
- 239000002002 slurry Substances 0.000 claims description 12
- 239000011734 sodium Substances 0.000 claims description 11
- 229910052708 sodium Inorganic materials 0.000 claims description 11
- 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 9
- 229910021385 hard carbon Inorganic materials 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 8
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- ZUHZGEOKBKGPSW-UHFFFAOYSA-N tetraglyme Chemical compound COCCOCCOCCOCCOC ZUHZGEOKBKGPSW-UHFFFAOYSA-N 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- ZMVMBTZRIMAUPN-UHFFFAOYSA-H [Na+].[V+5].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O Chemical compound [Na+].[V+5].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O ZMVMBTZRIMAUPN-UHFFFAOYSA-H 0.000 claims description 6
- 239000011230 binding agent Substances 0.000 claims description 6
- 239000011248 coating agent Substances 0.000 claims description 6
- 238000000576 coating method Methods 0.000 claims description 6
- 239000006258 conductive agent Substances 0.000 claims description 6
- 238000005520 cutting process Methods 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 239000007773 negative electrode material Substances 0.000 claims description 6
- 239000007774 positive electrode material Substances 0.000 claims description 6
- 239000013543 active substance Substances 0.000 claims description 5
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 claims description 5
- 239000003365 glass fiber Substances 0.000 claims description 5
- 239000010439 graphite Substances 0.000 claims description 5
- 229910002804 graphite Inorganic materials 0.000 claims description 5
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 4
- 238000007789 sealing Methods 0.000 claims description 4
- 229910001152 Bi alloy Inorganic materials 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- CHQMXRZLCYKOFO-UHFFFAOYSA-H P(=O)([O-])([O-])F.[V+5].[Na+].P(=O)([O-])([O-])F.P(=O)([O-])([O-])F Chemical compound P(=O)([O-])([O-])F.[V+5].[Na+].P(=O)([O-])([O-])F.P(=O)([O-])([O-])F CHQMXRZLCYKOFO-UHFFFAOYSA-H 0.000 claims description 3
- 229910001128 Sn alloy Inorganic materials 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 239000012300 argon atmosphere Substances 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 239000011889 copper foil Substances 0.000 claims description 3
- 239000011888 foil Substances 0.000 claims description 3
- DCYOBGZUOMKFPA-UHFFFAOYSA-N iron(2+);iron(3+);octadecacyanide Chemical class [Fe+2].[Fe+2].[Fe+2].[Fe+3].[Fe+3].[Fe+3].[Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] DCYOBGZUOMKFPA-UHFFFAOYSA-N 0.000 claims description 3
- 239000004005 microsphere Substances 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 229910021384 soft carbon Inorganic materials 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 claims description 2
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 2
- 239000004698 Polyethylene Substances 0.000 claims description 2
- 239000004743 Polypropylene Substances 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 2
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 2
- 125000001153 fluoro group Chemical group F* 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 239000012528 membrane Substances 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 239000000178 monomer Substances 0.000 claims description 2
- 229920000573 polyethylene Polymers 0.000 claims description 2
- 238000006116 polymerization reaction Methods 0.000 claims description 2
- 229920001155 polypropylene Polymers 0.000 claims description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 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
- 238000005303 weighing Methods 0.000 claims 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 claims 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 claims 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 abstract description 15
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 abstract description 8
- 238000000034 method Methods 0.000 abstract description 7
- 239000002000 Electrolyte additive Substances 0.000 abstract description 3
- 238000006243 chemical reaction Methods 0.000 abstract description 3
- 239000004210 ether based solvent Substances 0.000 abstract description 3
- 230000003647 oxidation Effects 0.000 abstract description 3
- 238000007254 oxidation reaction Methods 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 238000004807 desolvation Methods 0.000 abstract description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- 229910001416 lithium ion Inorganic materials 0.000 description 4
- 239000007789 gas Substances 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 230000006978 adaptation Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 238000010406 interfacial reaction Methods 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 235000012431 wafers Nutrition 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 229940021013 electrolyte solution Drugs 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000011244 liquid electrolyte Substances 0.000 description 1
- 238000011160 research Methods 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
- H01M10/0569—Liquid materials characterised by the solvents
-
- 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
- H01M10/05—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
- H01M10/058—Construction or manufacture
-
- 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
- H01M2300/0028—Organic electrolyte characterised by the solvent
-
- 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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The invention relates to the technical field of sodium ion batteries, in particular to a sodium ion battery electrolyte, a sodium ion battery and a preparation method, wherein the sodium ion battery electrolyte comprises an organic solvent, electrolyte sodium salt and an additive, and an ether solvent adopted by the sodium ion battery electrolyte has excellent reduction stability and lower desolvation energy, can form a thinner SEI film on the surface of a negative electrode, improves the interface stability of the sodium ion battery and ensures faster interface reaction kinetics of sodium ions; the carbonate electrolyte additive can participate in the formation of SEI films on the surfaces of the positive electrode and the negative electrode, so that the oxidation stability of the ether-based electrolyte is improved, and the cycle stability and the cycle efficiency of the battery are improved; in addition, the ether-based solvent hardly generates gas in the battery circulation process, so that the safety problem caused by the gas expansion of the battery is reduced.
Description
Technical Field
The invention relates to the technical field of sodium ion batteries, in particular to sodium ion battery electrolyte, a sodium ion battery and a preparation method.
Background
The lithium ion battery is a main energy storage product in the fields of consumer electronic products, electric automobiles and the like at present due to higher energy density and excellent cycle stability, but the lithium metal resources are limited and unevenly distributed, and the price rises year by year, so that the lithium ion battery cannot meet the huge energy storage market demands in the future. The sodium ion battery has a similar working principle with the lithium ion battery, and compared with metal lithium, the sodium ion battery has the advantages of abundant metal sodium resources, wide distribution and low price. Sodium ion batteries have more excellent high-low temperature performance and faster interfacial reaction kinetics than ion batteries, and have been attracting attention in recent years.
At present, the sodium ion battery also has the problems of low energy density, insignificant production cost advantages and the like. In order to improve the performance of all aspects of sodium-ion batteries, most of the work surrounds the development and modification development of positive and negative electrode materials, and relatively little research is conducted on electrolyte solutions of sodium-ion batteries. However, the electrolyte is an important component of the battery, and is a key factor for determining the thermodynamics and dynamics of the interface reaction of the electrolyte of the electrode, the stability of the electrolyte, the sodium ion transmission capacity, the impedance, the stability and other properties of the interface film generated on the surface of the electrode are closely related to the performance of the capacity of the anode and cathode materials, the whole cycle life of the battery and other properties. Optimizing the composition of the electrolyte of the sodium-ion battery is therefore critical to improving the performance of the sodium-ion battery in all aspects.
The method is beneficial to successful application of carbonate electrolyte in lithium ion batteries, more organic liquid electrolytes are mainly carbonate-based electrolyte which is researched in the field of sodium ion batteries at present, but the carbonate-based electrolyte is incompatible with graphite in the sodium ion batteries, and is easy to expand gas in the battery cycle process, and poor in dynamic performance is shown in the cathodes of various sodium ion batteries. The ether-based electrolyte is low in cost compared with the carbonate-based electrolyte, is compatible with commercial graphite cathodes, and shows superior interfacial reaction kinetics performance to carbonate in various sodium ion battery cathodes such as alloyed cathodes, carbon-based cathodes, and metallic sodium cathodes. However, the electrochemical stability of the ether-based electrolyte at the positive electrode end is poor, and the composition of the ether-based electrolyte needs to be further optimized to improve the performance of the sodium ion battery.
It should be noted that the foregoing description of the background art is only for the purpose of facilitating a clear and complete description of the technical solutions of the present application and for the convenience of understanding by those skilled in the art. The above-described solutions are not considered to be known to the person skilled in the art simply because they are set forth in the background section of the present application.
Disclosure of Invention
The purpose of the invention is that: aiming at the problems in the background technology, an improved scheme of the sodium ion battery is provided, so that the oxidation stability of the ether electrolyte can be improved, and the electrochemical performance of the sodium ion battery is further improved.
In order to achieve the above object, the present invention provides a sodium ion battery electrolyte comprising an organic solvent, an electrolyte sodium salt and an additive; the organic solvent comprises one or more of the compounds shown in the formula (1); the additive comprises one or more of the components shown in the formulas (2) and (3);
wherein n is selected from one or a combination of more than one of ethylene glycol monomers with polymerization number of 1-5;
wherein R1 is selected from one of unsubstituted H atom or methyl (-CH 3) or F atom;
wherein R2 and R3 are independently selected from one of alkyl groups having 1 to 2 carbon atoms.
Preferably, the organic solvent is one or more of ethylene glycol dimethyl ether, diethylene glycol dimethyl ether and tetraethylene glycol dimethyl ether.
Preferably, the additive formula (2) is one or more of ethylene carbonate, propylene carbonate, fluoroethylene carbonate.
Optionally, the additive formula (3) is one or more of dimethyl carbonate, diethyl carbonate and ethylmethyl carbonate.
Preferably, the volume percentage of the additive in the solvent is 0.01% -1%.
Preferably, the electrolyte sodium salt comprises one or more of sodium hexafluorophosphate, sodium tetrafluoroborate, sodium hexafluoroarsenate, sodium perchlorate, sodium bis-fluorosulfonyl imide, sodium bis-trifluoromethanesulfonyl imide, sodium bis-oxalato borate, sodium difluoro-oxalato borate.
Preferably, the concentration of the electrolyte sodium salt is 0.2-3.0mol/L.
The invention also provides a sodium ion battery, which comprises a positive plate containing positive electrode active materials, a negative plate containing negative electrode active materials, a diaphragm and the electrolyte.
Preferably, the positive electrode active material is one or more of sodium vanadium phosphate, sodium vanadium fluorophosphate, layered oxide and Prussian blue analogues, the negative electrode material is one or more of graphite, hard carbon, porous carbon, soft carbon, mesophase carbon microspheres, tin alloy, bismuth alloy and metallic sodium, and the separator comprises polyethylene, polypropylene, glass fiber separator and polytetrafluoroethylene.
The invention also provides a preparation method of the sodium ion battery, which comprises the following steps:
step 1, preparing a positive plate, namely fully stirring and mixing positive plate active substances of sodium vanadium phosphate, a conductive agent (Super P) and a binder of polyvinylidene fluoride (PVDF) in a proper amount of solvent N-methyl pyrrolidone (NMP) according to a preset mass ratio to form uniform slurry, coating the slurry on a current collector aluminum foil, drying at 70 ℃, and then cutting into wafers with preset diameters to obtain the positive plate;
step 2, preparing a negative plate, namely fully stirring and mixing a negative active substance Hard Carbon (HC), a conductive agent (Super P) and a binder polyvinylidene fluoride (PVDF) in a proper amount of solvent N-methyl pyrrolidone (NMP) according to a preset mass ratio to form uniform slurry, coating the slurry on a current collector copper foil, drying at 70 ℃, and then cutting into wafers with preset diameters to obtain the negative plate;
step three, taking a glass fiber membrane as a battery diaphragm;
step four, preparing electrolyte, namely weighing one or more of the solvents ethylene glycol dimethyl ether, diethylene glycol dimethyl ether and tetraethylene glycol dimethyl ether in an argon atmosphere glove box with water and oxygen content less than or equal to 0.1ppm, adding an additive and sodium salt (sodium hexafluorophosphate), dissolving and fully stirring, and uniformly mixing to obtain the electrolyte, wherein the concentration of the sodium hexafluorophosphate is 0.2-3.0mol/L, and the additive is Ethylene Carbonate (EC) accounting for 0.5% of the volume of the solvent;
and fifthly, placing the positive plate into a positive shell of the button cell, placing a diaphragm, dripping a proper amount of electrolyte, placing the negative plate, placing a gasket and an elastic sheet, covering the negative shell, and sealing by using a cell sealing machine to obtain the sodium ion cell.
The scheme of the invention has the following beneficial effects:
in the electrolyte of the sodium ion battery, the ether-based solvent has excellent reduction stability and lower desolvation energy, a thinner SEI film can be formed on the surface of the negative electrode, the interface stability of the sodium ion battery is improved, and the interface reaction kinetics of the sodium ion is ensured to be faster; the carbonate electrolyte additive can participate in the formation of SEI films on the surfaces of the positive electrode and the negative electrode, so that the oxidation stability of the ether-based electrolyte is improved, and the cycle stability and the cycle efficiency of the battery are improved; in addition, the ether-based solvent hardly generates gas in the battery circulation process, so that the safety problem caused by the gas expansion of the battery is reduced;
other advantageous effects of the present invention will be described in detail in the detailed description section which follows.
Detailed Description
In order to make the technical problems, technical solutions and advantages to be solved by the present invention more apparent, the following detailed description will be made with reference to specific embodiments. It will be apparent that the described embodiments are some, but not all, embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention. In addition, the technical features of the different embodiments of the present invention described below may be combined with each other as long as they do not collide with each other.
Example 1:
example 1 of the present invention provides a method for preparing a sodium ion battery.
Preparation of a positive plate:
and fully stirring and mixing the positive plate active material sodium vanadium phosphate, a conductive agent (Super P) and a binder polyvinylidene fluoride (PVDF) in a proper amount of solvent N-methyl pyrrolidone (NMP) according to a mass ratio of 7:2:1 to form uniform slurry, coating the slurry on a current collector aluminum foil, drying at 70 ℃, and cutting into a preset positive plate.
Preparing a negative plate:
the preparation method comprises the steps of fully stirring and mixing a negative electrode active substance Hard Carbon (HC), a conductive agent (Super P) and a binder polyvinylidene fluoride (PVDF) in a mass ratio of 90:5:5 in a proper amount of solvent N-methylpyrrolidone (NMP) to form uniform slurry, coating the slurry on a current collector copper foil, drying at 70 ℃, and cutting into preset negative electrode plates.
A diaphragm:
the glass fiber film is used as a battery separator.
Preparation of electrolyte:
in an argon atmosphere glove box with water and oxygen content less than or equal to 0.1ppm, single-solvent diethylene glycol dimethyl ether is weighed, an additive and sodium salt (sodium hexafluorophosphate) are added, the additive and the sodium hexafluorophosphate are dissolved and fully stirred, and electrolyte is obtained after uniform mixing, wherein the concentration of the sodium hexafluorophosphate is 1mol/L, and the additive is Ethylene Carbonate (EC) accounting for 0.5% of the solvent volume ratio.
Preparation of sodium ion battery:
and assembling and sealing the positive plate, the negative plate, the diaphragm and the electrolyte to form the sodium ion battery.
Example 2:
example 2 of the present invention provides another method of preparing a sodium ion battery, which differs from example 1 mainly in that the additive used accounts for 0.2% of the solvent volume ratio.
Example 3:
example 3 of the present invention provides another method of preparing a sodium ion battery, which differs from example 1 primarily in that the additive used comprises 0.7% by volume of the solvent.
Example 4:
example 4 of the present invention is a comparative example, and differs from the example mainly in that the additive used accounts for 0% of the solvent volume ratio.
The sodium ion batteries prepared in each example were subjected to performance evaluations, including capacity retention, cycle efficiency, and rate capability.
Capacity retention test:
charging a sodium ion battery to 3.9V at a constant current of 0.2 ℃ in a constant temperature box at 25 ℃, standing for 3 minutes, discharging to 2.0V at a constant current, standing for three minutes, and circulating for 3 times; and (3) starting to charge to 3.9V at a constant current of 1C, standing for 3 minutes, discharging to 2.0V at a constant current, recording the specific discharge capacity as C1, standing for three minutes, and circulating 300 times according to the system, wherein the specific discharge capacity recorded at the last time is C300. 10 cells were tested in each group and averaged. Wherein the cyclic capacity retention (%) = (C300/C1) ×100%.
And (3) cycle efficiency test:
charging a sodium ion battery to 3.9V at a constant current of 0.2C in a constant temperature box at 25 ℃, recording the charging specific capacity C0 at the moment, and standing for 3 minutes; then constant-current discharge is carried out until the voltage reaches 2.0V, the discharge specific capacity D0 at the moment is recorded, and the discharge specific capacity D0 is left for three minutes; the cycle was repeated 100 times according to this regimen, C0 and D0 were recorded for each cycle, and the per cycle efficiency (%) = (D0/C0) ×100% was calculated, 10 cells were tested for each group, and the average was taken.
And (3) multiplying power performance test:
in a constant temperature box at 25 ℃, the sodium ion batteries are respectively circulated for 10 times according to current densities of 0.2C, 0.5C, 1C, 2C, 5C, 10C and 0.2C, the discharge specific capacity value of each circulation is recorded, 10 batteries are tested in each group, the average value is taken, and the discharge specific capacity values under different multiplying factors are compared.
Table 1: results of Performance test of various embodiments
As can be seen from the performance results of the table, the addition of the carbonate as the ether electrolyte additive can effectively improve the cycling stability and the cycling efficiency of the sodium ion battery, and is closely related to the volume ratio of the additive to the solvent.
While the foregoing is directed to the preferred embodiments of the present invention, it will be appreciated by those skilled in the art that various modifications and adaptations can be made without departing from the principles of the present invention, and such modifications and adaptations are intended to be comprehended within the scope of the present invention.
Claims (4)
1. The sodium ion battery electrolyte is characterized by comprising an organic solvent, electrolyte sodium salt and an additive; the organic solvent consists of one or more of the compounds shown in the formula (1); the additive consists of one or more of the components shown in the formulas (2) and (3);
（1）
wherein n is selected from one or a combination of more than one of ethylene glycol monomers with polymerization number of 1-5;
（2）
wherein R1 is selected from one of unsubstituted H atom or methyl (-CH 3) or F atom;
（3）
wherein R2 and R3 are independently selected from one of alkyl groups with 1-2 carbon atoms;
the negative electrode material of the sodium ion battery is one or more of graphite, hard carbon, porous carbon, soft carbon, mesophase carbon microspheres, tin alloy, bismuth alloy and metallic sodium; the positive electrode active material is one or more of sodium vanadium phosphate, sodium vanadium fluorophosphate, layered oxide and Prussian blue analogues; the organic solvent is one or more of ethylene glycol dimethyl ether, diethylene glycol dimethyl ether and tetraethylene glycol dimethyl ether; the additive formula (2) is one or more of ethylene carbonate, propylene carbonate and fluoroethylene carbonate; the additive formula (3) is one or more of dimethyl carbonate, diethyl carbonate and ethylmethyl carbonate; the electrolyte sodium salt comprises one or more of sodium hexafluorophosphate, sodium tetrafluoroborate, sodium hexafluoroarsenate, sodium perchlorate, sodium bis (fluorosulfonyl) imide, sodium bis (trifluoromethanesulfonyl) imide, sodium bis (oxalato) borate and sodium difluoro (oxalato) borate; the volume percentage of the additive in the solvent is 0.01-1%.
2. A sodium ion battery electrolyte according to claim 1, wherein the concentration of the electrolyte sodium salt is 0.2-3.0mol/L.
3. A sodium ion battery comprising a positive electrode sheet containing a positive electrode active material, a negative electrode sheet containing a negative electrode active material, a separator, and the electrolyte according to any one of claims 1 to 2; the positive electrode active material is one or more of sodium vanadium phosphate, sodium vanadium fluorophosphate, layered oxide and Prussian blue analogues, the negative electrode material is one or more of graphite, hard carbon, porous carbon, soft carbon, mesophase carbon microspheres, tin alloy, bismuth alloy and metallic sodium, and the separator comprises polyethylene, polypropylene, glass fiber separator and polytetrafluoroethylene.
4. A method of making a sodium ion battery according to claim 3, comprising the steps of:
step 1, preparing a positive plate, namely fully stirring and mixing positive plate active substances of sodium vanadium phosphate, a conductive agent (Super P) and a binder of polyvinylidene fluoride (PVDF) in a proper amount of solvent N-methyl pyrrolidone (NMP) according to a preset mass ratio to form uniform slurry, coating the slurry on a current collector aluminum foil, drying at 70 ℃, and then cutting into preset positive plates;
step 2, preparing a negative electrode plate, namely fully stirring and mixing a negative electrode active substance Hard Carbon (HC), a conductive agent (Super P) and a binder polyvinylidene fluoride (PVDF) in a proper amount of solvent N-methyl pyrrolidone (NMP) according to a preset mass ratio to form uniform slurry, coating the slurry on a current collector copper foil, drying at 70 ℃, and then cutting into the preset negative electrode plate;
step three, taking a glass fiber membrane as a battery diaphragm;
step four, preparing electrolyte, namely weighing one or more of the solvents ethylene glycol dimethyl ether, diethylene glycol dimethyl ether and tetraethylene glycol dimethyl ether in an argon atmosphere glove box with water and oxygen content less than or equal to 0.1ppm, adding an additive and sodium salt (sodium hexafluorophosphate), dissolving and fully stirring, and uniformly mixing to obtain the electrolyte, wherein the concentration of the sodium hexafluorophosphate is 0.2-3.0mol/L, and the additive is Ethylene Carbonate (EC) accounting for 0.5% of the volume of the solvent;
and fifthly, assembling and sealing the positive plate, the negative plate, the diaphragm and the electrolyte to form the sodium ion battery.
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| CN115207471B (en) * | 2022-08-04 | 2023-09-12 | 大连中比动力电池有限公司 | Sodium ion battery electrolyte |
| CN115602924A (en) * | 2022-09-01 | 2023-01-13 | 中国石油大学（华东）（Cn） | Flame-retardant sodium-ion battery electrolyte and application thereof |
| CN115602926B (en) * | 2022-12-16 | 2023-04-28 | 河北省科学院能源研究所 | High-temperature-resistant electrolyte and preparation method and application thereof |
| CN117096280A (en) * | 2023-09-21 | 2023-11-21 | 东营昆宇电源科技有限公司 | Preparation method of novel high-voltage positive electrode of sodium ion battery and secondary sodium ion battery |
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