CN117352851A - Electrolyte of low-temperature high-pressure sodium ion battery and sodium ion battery - Google Patents
Electrolyte of low-temperature high-pressure sodium ion battery and sodium ion battery Download PDFInfo
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- CN117352851A CN117352851A CN202311542535.7A CN202311542535A CN117352851A CN 117352851 A CN117352851 A CN 117352851A CN 202311542535 A CN202311542535 A CN 202311542535A CN 117352851 A CN117352851 A CN 117352851A
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- Prior art keywords
- sodium
- ion battery
- electrolyte
- sodium ion
- dimethyl ether
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- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 71
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 69
- 239000003792 electrolyte Substances 0.000 title claims abstract description 52
- ZUHZGEOKBKGPSW-UHFFFAOYSA-N tetraglyme Chemical compound COCCOCCOCCOCCOC ZUHZGEOKBKGPSW-UHFFFAOYSA-N 0.000 claims abstract description 26
- 159000000000 sodium salts Chemical class 0.000 claims abstract description 20
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical group COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000003960 organic solvent Substances 0.000 claims abstract description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 16
- 239000011734 sodium Substances 0.000 claims description 13
- 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
- 229910052782 aluminium Inorganic materials 0.000 claims description 12
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 12
- 229910052799 carbon Inorganic materials 0.000 claims description 12
- 239000011888 foil Substances 0.000 claims description 12
- 229910052708 sodium Inorganic materials 0.000 claims description 12
- -1 sodium tetrafluoroborate Chemical compound 0.000 claims description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 6
- 239000011889 copper foil Substances 0.000 claims description 6
- 239000007774 positive electrode material Substances 0.000 claims description 6
- 229910001495 sodium tetrafluoroborate Inorganic materials 0.000 claims description 5
- 229910000863 Ferronickel Inorganic materials 0.000 claims description 4
- 239000006258 conductive agent Substances 0.000 claims description 4
- LBSANEJBGMCTBH-UHFFFAOYSA-N manganate Chemical compound [O-][Mn]([O-])(=O)=O LBSANEJBGMCTBH-UHFFFAOYSA-N 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 239000011230 binding agent Substances 0.000 claims description 3
- VCCATSJUUVERFU-UHFFFAOYSA-N sodium bis(fluorosulfonyl)azanide Chemical compound FS(=O)(=O)N([Na])S(F)(=O)=O VCCATSJUUVERFU-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 2
- 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 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 claims description 2
- DWYMPOCYEZONEA-UHFFFAOYSA-L fluoridophosphate Chemical compound [O-]P([O-])(F)=O DWYMPOCYEZONEA-UHFFFAOYSA-L 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
- XWQGIDJIEPIQBD-UHFFFAOYSA-J sodium;iron(3+);phosphonato phosphate Chemical compound [Na+].[Fe+3].[O-]P([O-])(=O)OP([O-])([O-])=O XWQGIDJIEPIQBD-UHFFFAOYSA-J 0.000 claims description 2
- 239000011152 fibreglass Substances 0.000 claims 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 abstract description 24
- 230000008021 deposition Effects 0.000 abstract description 11
- 238000007254 oxidation reaction Methods 0.000 abstract description 8
- 230000003647 oxidation Effects 0.000 abstract description 7
- 238000013329 compounding Methods 0.000 abstract description 6
- 230000002441 reversible effect Effects 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract description 3
- 238000002360 preparation method Methods 0.000 description 19
- 230000000052 comparative effect Effects 0.000 description 14
- 238000000034 method Methods 0.000 description 12
- 238000000151 deposition Methods 0.000 description 11
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- 238000001465 metallisation Methods 0.000 description 5
- 238000011056 performance test Methods 0.000 description 5
- 238000011065 in-situ storage Methods 0.000 description 4
- 229910052786 argon Inorganic materials 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 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 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 239000011268 mixed slurry Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- 238000007614 solvation Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 229910020808 NaBF Inorganic materials 0.000 description 1
- 229910021201 NaFSI Inorganic materials 0.000 description 1
- 229920002125 Sokalan® Polymers 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
- 239000006230 acetylene black Substances 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000003273 ketjen black Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 230000035807 sensation Effects 0.000 description 1
- 239000000661 sodium alginate Substances 0.000 description 1
- 235000010413 sodium alginate Nutrition 0.000 description 1
- 229940005550 sodium alginate Drugs 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
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 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
- XGPOMXSYOKFBHS-UHFFFAOYSA-M sodium;trifluoromethanesulfonate Chemical group [Na+].[O-]S(=O)(=O)C(F)(F)F XGPOMXSYOKFBHS-UHFFFAOYSA-M 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 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
-
- 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
Abstract
The invention relates to a low-temperature high-pressure sodium ion battery electrolyte and a sodium ion battery, wherein the electrolyte comprises sodium salt and an organic solvent, and the organic solvent is selected from diethylene glycol dimethyl ether or a combination of diethylene glycol dimethyl ether and tetraethylene glycol dimethyl ether. According to the low-temperature high-pressure sodium ion battery electrolyte provided by the invention, through the compounding of the sodium salt and the organic solvent, sodium metal can be subjected to high coulomb efficiency reversible deposition on a pure current collector in a wide temperature range, meanwhile, the oxidation stability of the electrolyte is improved, the raw materials are simple, the sources are wide, the cost is low, and the prepared negative-electrode-free sodium ion battery has high energy density and high working voltage in a wide temperature range, particularly in a low temperature range, and has excellent electrochemical performance.
Description
Technical Field
The invention relates to the technical field of sodium ion batteries, in particular to low-temperature high-pressure sodium ion battery electrolyte and a sodium ion battery.
Background
The widespread use of renewable energy sources (e.g., solar, wind, biomass) and the rapid development of the electric automobile market and portable consumer electronics have greatly driven the development of secondary battery systems with high specific energy and low cost. The lithium ion battery is paid attention to because of the advantages of high energy density, long cycle life and the like, but the cost of the lithium ion battery is increased year by year because of low lithium reserves and uneven resource distribution. Sodium reserves are abundant, and sodium ion batteries would be an economic and efficient option for next generation electrical energy storage.
However, due to the relatively large atomic size and weight of sodium, current sodium ion batteries generally have lower energy densities than lithium batteries. One solution is to manufacture high-energy sodium metal batteries from ultra-thin sodium metal, but it is difficult to process and mold to produce ultra-thin sodium metal cathodes due to the softness and high viscosity of sodium metal. In addition, sodium metal has poor air stability and is not conducive to mass production. The cathode-free sodium ion battery can electrochemically form a sodium metal cathode in situ in the first charging process, and active sodium ions are completely from the cathode material, so that the manufacturing process is simplified, the cathode quality is reduced, and the energy density of the whole battery is improved. However, the existing negative-electrode-free sodium-ion battery electrolyte is difficult to realize reversible sodium metal deposition at low temperature, and has extremely low coulombic efficiency at low temperature, so that the low-temperature capacity is rapidly attenuated. In addition, the existing sodium ion battery electrolyte has poor oxidation stability and low working voltage, cannot be matched with a high-voltage positive electrode, and is difficult to further improve the energy density of the non-negative sodium ion full battery.
Therefore, it is important to provide a new electrolyte to increase the energy density and operating voltage of the negative-electrode-free sodium ion battery at low temperature.
Disclosure of Invention
In order to solve the technical problems, the invention provides the low-temperature high-voltage sodium ion battery electrolyte and the sodium ion battery, and the low-temperature high-voltage sodium ion battery electrolyte provided by the invention can enable sodium metal to be uniformly deposited on the surface of a negative electrode current collector in a wide temperature range, improves the coulomb efficiency of the negative electrode, has excellent oxidation stability, enables the sodium ion battery to have high energy density and high working voltage at low temperature, has excellent electrochemical performance, and solves the problems of poor deposition reversibility and low working voltage of sodium metal in the conventional electrolyte at low temperature. The preparation method of the sodium ion battery has simple process and low cost, can deposit sodium metal in situ in the battery, avoids the problems of unstable electrode materials, difficult storage and the like caused by the sensitivity of the sodium metal to water and oxygen, and is suitable for large-scale production.
In a first aspect, the invention provides a low temperature, high pressure sodium ion battery electrolyte comprising a sodium salt and an organic solvent selected from the group consisting of diethylene glycol dimethyl ether, or a combination of diethylene glycol dimethyl ether and tetraethylene glycol dimethyl ether.
According to the low-temperature high-pressure sodium ion battery electrolyte provided by the invention, through the compounding of the sodium salt and the organic solvent, sodium metal can be subjected to high coulomb efficiency reversible deposition on a pure current collector in a wide temperature range, meanwhile, the oxidation stability of the electrolyte is improved, the raw materials are simple, the sources are wide, the cost is low, and the prepared negative-electrode-free sodium ion battery has high energy density and high working voltage in a wide temperature range, particularly in a low temperature range, and has excellent electrochemical performance. Specifically:
according to the low-temperature high-pressure sodium ion battery electrolyte provided by the invention, through selection and compounding of sodium salt and organic solvent, the solvation structure of the electrolyte is changed, so that sodium metal can be uniformly deposited on the surface of a pure negative electrode current collector in a wide temperature range, high coulombic efficiency of a negative electrode is realized, and the oxidation resistance of the electrolyte can be improved, so that a negative-electrode-free sodium ion battery using the electrolyte has excellent electrochemical performances of high energy density, high working voltage and the like in a wide temperature range, especially in a low temperature range.
As a preferred technical solution of the present invention, when the organic solvent is selected from the group consisting of diethylene glycol dimethyl ether and tetraethylene glycol dimethyl ether, the volume ratio of diethylene glycol dimethyl ether and tetraethylene glycol dimethyl ether is (1-9): (1-9), for example, 1:1, 1:3, 1:6, 1:9, 2:1, 2:3, 2:9, 3:1, 3:2, 4:1, 4:3, 4:9, 5:1, 5:3, 5:6, 5:9, 6:1, 7:1, 7:3, 8:1, 8:3, 8:9, 9:1, 9:2, 9:4, etc.
As a preferable technical scheme of the invention, the volume ratio of the diethylene glycol dimethyl ether to the tetraethylene glycol dimethyl ether is (1-9): 1.
As a preferable technical scheme of the invention, the volume ratio of the diethylene glycol dimethyl ether to the tetraethylene glycol dimethyl ether is 4:1.
As bookIn a preferred embodiment of the invention, the sodium salt is selected from sodium tetrafluoroborate (NaBF) 4 ) Sodium perchlorate (NaClO) 4 ) Any one or a combination of at least two of sodium bis (trifluoromethylsulfonyl) imide (NaTFSI) or sodium bis (fluorosulfonyl) imide (NaFSI), preferably sodium tetrafluoroborate.
According to the invention, through compounding of the sodium salt and the organic solvent, the solvation structure of the electrolyte is changed, so that sodium metal can be uniformly deposited on the surface of a pure current collector in a wide temperature range, reversible deposition can be performed, the coulombic efficiency of a negative electrode can be further improved, meanwhile, the oxidation resistance of the electrolyte can be improved, and the prepared sodium ion battery has excellent electrochemical performances such as low temperature, high pressure, high energy density and the like.
As a preferable embodiment of the present invention, the concentration of the sodium salt in the electrolyte is 0.05 to 3mol/L, for example, 0.1mol/L, 0.2mol/L, 0.5mol/L, 0.8mol/L, 1mol/L, 1.5mol/L, 2mol/L, 2.5mol/L, etc.
As a preferable technical scheme of the invention, the concentration of the sodium salt in the electrolyte is 0.5-2mol/L.
When the concentration of sodium salt in the electrolyte is within the preferred range of the invention, the prepared negative-electrode-free sodium ion battery has excellent electrochemical properties of wide temperature range (-40-25 ℃), particularly low-temperature high-pressure high-energy density and the like, and is beneficial to the further industrial development of the sodium ion battery.
In a second aspect, the invention provides a low-temperature high-voltage sodium ion battery, which comprises a positive electrode plate, a negative electrode plate, a diaphragm and the low-temperature high-voltage sodium ion battery electrolyte of the first aspect.
According to the invention, the low-temperature high-voltage sodium ion battery is prepared by using the low-temperature high-voltage sodium ion battery electrolyte, a sodium metal negative electrode is generated in situ in the battery charging process, and meanwhile, the high-oxidation stability is realized, so that the negative electrode-free high-voltage high-specific energy sodium ion battery with high energy density in a wide temperature range is prepared, and the battery can stably operate at a high working voltage of 4.2V and a low temperature of minus 40 ℃.
As a preferable technical scheme of the invention, the positive electrode plate comprises a positive electrode current collector, a positive electrode active material, a conductive agent and a binder.
As a preferable embodiment of the present invention, the positive electrode active material is selected from any one or a combination of at least two of sodium ferromanganate, sodium ferronickel manganate, sodium vanadium phosphate, sodium ferric pyrophosphate, sodium vanadium fluorophosphate, and sodium ferric fluorophosphate.
As a preferred embodiment of the present invention, the positive electrode active material is selected from sodium nickel iron manganate.
As a preferable technical scheme of the invention, the conductive agent is selected from any one or a combination of at least two of Super P, acetylene black, ketjen black, conductive graphite, carbon nano tube, graphene or carbon fiber.
As a preferable technical scheme of the invention, the binder is selected from any one or a combination of at least two of polyvinylidene fluoride, polytetrafluoroethylene, polyacrylic acid, sodium alginate, carboxymethyl cellulose, sodium carboxymethyl cellulose and styrene-butadiene rubber.
As a preferable technical scheme of the invention, the positive electrode current collector is selected from any one or a combination of at least two of copper foil, aluminum foil, carbon-coated copper foil and carbon-coated aluminum foil.
As a preferable technical scheme of the invention, the composition of the negative electrode plate comprises a negative electrode current collector.
As a preferable technical scheme of the invention, the negative electrode current collector is selected from any one or a combination of at least two of copper foil, carbon-coated copper foil, aluminum foil and carbon-coated aluminum foil.
As a preferred embodiment of the present invention, the separator is selected from any one or a combination of at least two of Celgard2500 separator, celgard 2325 separator or glass fiber separator.
Compared with the prior art, the technical scheme provided by the embodiment of the invention has the following advantages:
1. according to the low-temperature high-pressure sodium ion battery electrolyte provided by the invention, through the compounding of the sodium salt and the organic solvent, sodium metal can be subjected to high coulomb efficiency reversible deposition on a pure current collector in a wide temperature range, meanwhile, the oxidation stability of the electrolyte is improved, the raw materials are simple, the sources are wide, the cost is low, and the prepared negative-electrode-free sodium ion battery has high energy density and high working voltage in a wide temperature range, particularly in a low temperature range, and has excellent electrochemical performance.
2. The preparation method of the sodium ion battery has simple process and low cost, can deposit sodium metal in situ in the battery, avoids the problems of unstable electrode materials, difficult storage and the like caused by the sensitivity of the sodium metal to water and oxygen, and is suitable for large-scale production.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate embodiments consistent with the invention and together with the description, serve to explain the principles of the invention.
In order to more clearly illustrate the embodiments of the invention or the technical solutions of the prior art, the drawings which are used in the description of the embodiments or the prior art will be briefly described, and it will be obvious to a person skilled in the art that other drawings can be obtained from these drawings without inventive effort.
FIG. 1 is a graph showing that the half cell obtained in example 1 was measured at 0.2mA cm -2 Coulombic efficiency cycle diagram at 25 ℃;
FIG. 2 is a graph showing that the half cell obtained in example 1 was measured at 0.2mA cm -2 A sodium metal deposition charge-discharge curve graph at 25 ℃;
FIG. 3 is a graph showing that the half cell obtained in example 1 was measured at 0.2mA cm -2 Coulombic efficiency cycle diagram at-40 deg.c;
FIG. 4 is a graph showing that the half cell obtained in example 1 was measured at 0.2mA cm -2 A sodium metal deposition charge-discharge curve graph at-40 ℃;
fig. 5 is a graph showing the specific capacity voltage at-40 ℃ of the low-temperature high-voltage negative-electrode-free sodium ion full battery obtained in example 1.
Detailed Description
In order that the above objects, features and advantages of the invention will be more clearly understood, a further description of the invention will be made. It should be noted that, without conflict, the embodiments of the present invention and features in the embodiments may be combined with each other.
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention, but the present invention may be practiced otherwise than as described herein; it will be apparent that the embodiments in the specification are only some, but not all, embodiments of the invention.
Preparation example 1
The preparation example provides a low-temperature high-pressure sodium ion battery electrolyte and a preparation method thereof, and the preparation method comprises the following steps:
in a glove box filled with argon, adding molecular sieves into diethylene glycol dimethyl ether and tetraethylene glycol dimethyl ether respectively to remove water sufficiently, and then mixing the organic solvents according to a volume ratio of 4:1; and adding sodium tetrafluoroborate into the organic solvent to ensure that the concentration of sodium salt is 1mol/L, and completely dissolving to obtain the low-temperature high-pressure sodium ion battery electrolyte.
Example 1
The embodiment provides a low-temperature high-voltage sodium ion half-cell, a full-cell and a preparation method thereof, wherein the preparation method comprises the following steps:
(1) Preparing a positive electrode plate: mixing 8 parts by weight of sodium ferronickel manganate, 1 part by weight of SP conductive agent and 1 part by weight of PVDF binder, grinding uniformly, adding N-methyl-2-pyrrolidone serving as a solvent into the mixture, stirring fully until no granular sensation exists, obtaining mixed slurry, coating the mixed slurry on a carbon-coated aluminum foil, drying and rolling to obtain a sodium ferronickel manganate positive plate;
(2) Preparing a negative electrode plate: carbon-coated aluminum foil is used as a negative current collector, and is placed in an air plasma cleaner to be treated for 120 seconds with 240W power for drying at the temperature of 70 ℃ in vacuum for standby in order to increase the sodium deposition performance;
(3) Assembling a sodium ion half cell: the CR2032 button cell is assembled in a glove box filled with argon, metal sodium is used as a negative electrode, carbon-coated aluminum foil is used as a positive electrode, celgard2500 is used as a diaphragm, and the low-temperature high-pressure sodium ion cell electrolyte prepared in preparation example 1 is assembled into a carbon-coated aluminum foil Na half cell.
(4) Assembling the low-temperature high-voltage negative-electrode-free sodium ion full battery: in a glove box filled with argon, the positive pole piece of the sodium nickel iron manganese oxide obtained in the step (1) is used as a positive pole, the carbon-coated aluminum foil obtained in the step (2) is used as a negative pole, celgard2500 is used as a diaphragm, and the low-temperature high-pressure sodium ion battery electrolyte prepared in the preparation example 1 is assembled into the carbon-coated aluminum foil sodium nickel iron manganese oxide full battery.
Performance test 1
The sodium-ion half cell prepared in example 1 was subjected to cycle performance test:
the half cells prepared in example 1 were placed in an incubator at-40℃and 25℃respectively, and left standing for 2 hours at 0.2mA cm -2 Is deposited by current density discharge of 0.5mAh cm -2 Then charged to 1.0V at the same current density, and thus cycled for 50 weeks, resulting in coulombic efficiencies and charge-discharge deposition overpotential as shown in fig. 1-4.
Wherein FIG. 1 is a graph showing that the half cell obtained in example 1 was at 0.2mA cm -2 FIG. 2 is a chart showing coulombic efficiency cycle at 25℃for half-cell obtained in example 1 at 0.2mA cm -2 FIG. 3 is a graph showing the charge and discharge curves of sodium metal deposition at 25℃for the half cell obtained in example 1 at 0.2mA cm -2 FIG. 4 is a chart showing coulombic efficiency cycle at-40℃for half-cell obtained in example 1 at 0.2mA cm -2 And a charge-discharge curve graph of sodium metal deposition at-40 ℃.
As can be seen from fig. 1 to 4, the sodium ion half cell prepared in example 1 of the present invention has a high coulombic efficiency of 99.6% at 25 ℃ and 99.9% at-40 ℃, indicating that the electrolyte prepared in preparation 1 of the present invention is an electrolyte capable of stably depositing sodium metal over a wide temperature range.
Performance test 2
The low-temperature high-voltage negative-electrode-free sodium ion full battery prepared in example 1 was tested:
at a current density of 30mA/g, the low-temperature high-voltage sodium ion full battery is circulated for 3 times in a voltage interval of 2.0-4.2V at 25 ℃ to form a stable solid electrolyte interface film, and then is charged and discharged in a potential interval of 2.0-4.2V at-40 ℃.
Fig. 5 is a graph showing the specific capacity voltage at-40 ℃ of the low-temperature high-voltage negative-electrode-free sodium ion full battery obtained in example 1. As can be seen from the graph, the low-temperature high-voltage negative-electrode-free sodium ion full battery obtained in example 1 has a relatively high energy density in a wide temperature range, and the low-temperature high-voltage negative-electrode-free sodium ion full battery has a high energy density of 338Wh/kg at-40 ℃ based on the mass of the positive electrode active material.
Preparation examples 2 to 11 and comparative preparation examples 1 to 8
The present preparation example (comparative preparation example) provides a low-temperature high-pressure sodium ion battery electrolyte and a preparation method thereof, which is the same as preparation example 1, except that the composition and content of organic solvent and sodium salt in the electrolyte are as shown in the following table 1:
TABLE 1
Examples 2 to 11 and comparative examples 1 to 8
The sodium-ion battery electrolytes obtained in preparation examples 2 to 11 (examples 2 to 11) and comparative preparation examples 1 to 8 (comparative examples 1 to 8) were assembled into sodium-ion half cells and full cells, respectively, according to the method described in example 1.
Performance test 3
1. The deposition efficiency of the half cells obtained in examples 1 to 11 and comparative examples 1 to 8 was tested:
the half cells obtained in examples 1 to 11 and comparative examples 1 to 8 were placed in an incubator at 25℃and-40℃respectively, and left standing for 2 hours at 0.2mA/cm 2 Is deposited by current density discharge of 0.5mAh/cm 2 Then at 0.2mA/cm 2 The current density was charged to 1.0V and the charge capacity at this time was recorded.
The deposition efficiencies of the half cells obtained in examples 1 to 11 and comparative examples 1 to 8 are shown in table 2, in which deposition efficiency=charge capacity/discharge capacity.
2. The discharge capacities of the full cells obtained in examples 1 to 11 and comparative examples 1 to 8 were tested:
1) The full cells obtained in examples 1 to 11 and comparative examples 1 to 8 were placed in an incubator at 25℃for 2 hours, charged to 4.2V at a current density of 30mA/g, then discharged to 2.0V at a current density of 30mA/g, and the discharge capacity at this time was recorded, and the results are shown in Table 2;
2) The full cells obtained in examples 1 to 11 and comparative examples 1 to 8 were placed in an incubator at-40℃and allowed to stand for 2 hours, charged to 4.2V at a current density of 7.5mA/g, then discharged to 2.0V at a current density of 7.5mA/g, and the discharge capacity at this time was recorded, and the results are shown in Table 2;
table 2 shows the results of the performance tests of half cells and full cells obtained in examples 1 to 11 and comparative examples 1 to 8:
TABLE 2
As can be seen from Table 2, the deposition efficiency of the prepared sodium ion half-cell at-40 ℃ is up to 99.9% by selecting and compounding the organic solvent and sodium salt in the electrolyte, and the prepared sodium ion full-cell has a high working voltage of 4.2V at-40 ℃ and a discharge capacity of up to 104mAh g -1 The negative electrode-free sodium ion full battery prepared by the electrolyte provided by the invention has excellent electrochemical properties such as low temperature, high pressure, high energy density and the like. As can be seen from the comparison of examples 1 to 7, when the electrolyte is diethylene glycol dimethyl ether, or when the content of diethylene glycol dimethyl ether in the electrolyte is higher than that of tetraethylene glycol dimethyl ether, the obtained sodium ion battery has more excellent low-temperature high-pressure high-energy density; as can be seen from the comparison of the examples 1 and the examples 8 to 10, when the concentration of sodium salt in the electrolyte is 0.5 to 2mol/L, the obtained sodium ion battery has more excellent electrochemical properties such as low temperature, high pressure, high energy density and the like; from comparative examples 1 to 5, it is understood that when the sodium salt is replaced with sodium trifluoromethane sulfonate or sodium hexafluorophosphate, a sodium ion battery is obtainedLow temperature and high pressure performance is poor; as is clear from comparative examples 6 to 8, when the solvent is tetraethyleneglycol dimethyl ether, the low-temperature high-voltage performance of the obtained sodium ion battery is deteriorated.
It should be noted that in this document, relational terms such as "first" and "second" and the like are used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Moreover, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation, an element defined by the phrase "comprising one … …" does not exclude the presence of other like elements in a process, method, article, or apparatus that comprises the element.
The foregoing is only a specific embodiment of the invention to enable those skilled in the art to understand or practice the invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown and described herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. A low-temperature high-pressure sodium ion battery electrolyte, which is characterized by comprising sodium salt and an organic solvent, wherein the organic solvent is selected from diethylene glycol dimethyl ether or a combination of diethylene glycol dimethyl ether and tetraethylene glycol dimethyl ether.
2. The electrolyte of claim 1 wherein when the organic solvent is selected from the group consisting of diethylene glycol dimethyl ether and tetraethylene glycol dimethyl ether, the volume ratio of diethylene glycol dimethyl ether to tetraethylene glycol dimethyl ether is (1-9): (1-9).
3. Electrolyte according to claim 2, characterized in that the volume ratio of diethylene glycol dimethyl ether to tetraethylene glycol dimethyl ether is (1-9): 1, preferably 4:1.
4. The electrolyte according to any one of claims 1 to 3, wherein the sodium salt is selected from any one or a combination of at least two of sodium tetrafluoroborate, sodium perchlorate, sodium bis (trifluoromethylsulfonyl) imide or sodium bis (fluorosulfonyl) imide, preferably sodium tetrafluoroborate.
5. The electrolyte according to any one of claims 1 to 4, wherein the concentration of the sodium salt in the electrolyte is 0.05 to 3mol/L.
6. The electrolyte of claim 5 wherein the concentration of the sodium salt in the electrolyte is 0.5-2mol/L.
7. A low temperature, high voltage sodium ion battery comprising a positive electrode sheet, a negative electrode sheet, a separator, and the low temperature, high voltage sodium ion battery electrolyte of any one of claims 1-6.
8. The low-temperature high-voltage sodium ion battery according to claim 7, wherein the positive electrode sheet comprises a positive electrode current collector, a positive electrode active material, a conductive agent and a binder;
preferably, the positive electrode active material is selected from any one or a combination of at least two of sodium ferromanganate, sodium ferronickel manganate, sodium vanadium phosphate, sodium ferric pyrophosphate, sodium vanadium fluorophosphate or sodium ferric fluorophosphate.
9. The low temperature, high voltage sodium ion battery of claim 7, wherein the composition of the negative electrode tab comprises a negative electrode current collector;
preferably, the negative electrode current collector is selected from any one or a combination of at least two of copper foil, carbon coated copper foil, aluminum foil or carbon coated aluminum foil.
10. The low temperature, high pressure sodium ion battery of claim 7, wherein the separator is selected from any one or a combination of at least two of a Celgard2500 separator, a Celgard 2325 separator, or a fiberglass separator.
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