CN116417678A - Lithium/sodium fluorocarboxylate electrolyte and lithium/sodium ion battery containing same - Google Patents
Lithium/sodium fluorocarboxylate electrolyte and lithium/sodium ion battery containing same Download PDFInfo
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- CN116417678A CN116417678A CN202310586014.5A CN202310586014A CN116417678A CN 116417678 A CN116417678 A CN 116417678A CN 202310586014 A CN202310586014 A CN 202310586014A CN 116417678 A CN116417678 A CN 116417678A
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- Prior art keywords
- lithium
- sodium
- electrolyte
- fluorocarboxylate
- carbonate
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- 239000003792 electrolyte Substances 0.000 title claims abstract description 82
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 58
- 239000011734 sodium Substances 0.000 title claims abstract description 39
- 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 title claims abstract description 36
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 36
- 229910052708 sodium Inorganic materials 0.000 title claims abstract description 36
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 32
- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 30
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 34
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims abstract description 33
- 239000000654 additive Substances 0.000 claims abstract description 30
- 239000000047 product Substances 0.000 claims abstract description 25
- 230000000996 additive effect Effects 0.000 claims abstract description 23
- 239000003960 organic solvent Substances 0.000 claims abstract description 23
- 239000007787 solid Substances 0.000 claims abstract description 17
- 239000002253 acid Substances 0.000 claims abstract description 11
- 238000002360 preparation method Methods 0.000 claims abstract description 11
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 9
- 238000001914 filtration Methods 0.000 claims abstract description 9
- 239000002904 solvent Substances 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims abstract description 3
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 13
- -1 fluoroalkyl phosphate Chemical compound 0.000 claims description 11
- 229910013870 LiPF 6 Inorganic materials 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 238000004821 distillation Methods 0.000 claims description 8
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 7
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 7
- 239000010439 graphite Substances 0.000 claims description 7
- 229910002804 graphite Inorganic materials 0.000 claims description 7
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 claims description 7
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 7
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 claims description 5
- 229910021385 hard carbon Inorganic materials 0.000 claims description 5
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims description 4
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 4
- 229910019142 PO4 Inorganic materials 0.000 claims description 4
- 150000005678 chain carbonates Chemical class 0.000 claims description 4
- 239000002131 composite material Substances 0.000 claims description 4
- 150000005676 cyclic carbonates Chemical class 0.000 claims description 4
- 239000003063 flame retardant Substances 0.000 claims description 4
- 239000007773 negative electrode material Substances 0.000 claims description 4
- 239000010452 phosphate Substances 0.000 claims description 4
- 239000007774 positive electrode material Substances 0.000 claims description 4
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 claims description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 3
- 229910015015 LiAsF 6 Inorganic materials 0.000 claims description 3
- 229910013684 LiClO 4 Inorganic materials 0.000 claims description 3
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 2
- 229910013063 LiBF 4 Inorganic materials 0.000 claims description 2
- 229910010941 LiFSI Inorganic materials 0.000 claims description 2
- 229910020808 NaBF Inorganic materials 0.000 claims description 2
- 229910021201 NaFSI Inorganic materials 0.000 claims description 2
- HFCVPDYCRZVZDF-UHFFFAOYSA-N [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O Chemical compound [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O HFCVPDYCRZVZDF-UHFFFAOYSA-N 0.000 claims description 2
- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical compound [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 0.000 claims description 2
- GLMOMDXKLRBTDY-UHFFFAOYSA-A [V+5].[V+5].[V+5].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O Chemical compound [V+5].[V+5].[V+5].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O GLMOMDXKLRBTDY-UHFFFAOYSA-A 0.000 claims description 2
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000011737 fluorine Substances 0.000 claims description 2
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- VDVLPSWVDYJFRW-UHFFFAOYSA-N lithium;bis(fluorosulfonyl)azanide Chemical compound [Li+].FS(=O)(=O)[N-]S(F)(=O)=O VDVLPSWVDYJFRW-UHFFFAOYSA-N 0.000 claims description 2
- 239000000463 material Substances 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 239000004745 nonwoven fabric Substances 0.000 claims description 2
- 229920006254 polymer film Polymers 0.000 claims description 2
- 239000002153 silicon-carbon composite material Substances 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 description 2
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 2
- 229910021384 soft carbon Inorganic materials 0.000 claims description 2
- 239000012002 vanadium phosphate Substances 0.000 claims description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims 1
- 239000003365 glass fiber Substances 0.000 claims 1
- 229910003002 lithium salt Inorganic materials 0.000 description 13
- 159000000000 sodium salts Chemical class 0.000 description 12
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 10
- SULCYVPOJZHGRY-UHFFFAOYSA-M [Li+].[O-]C(F)=O Chemical compound [Li+].[O-]C(F)=O SULCYVPOJZHGRY-UHFFFAOYSA-M 0.000 description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000005303 weighing Methods 0.000 description 6
- 239000010405 anode material Substances 0.000 description 5
- KMOFAUACKFPRPG-UHFFFAOYSA-M lithium 2,2,3,3,4,4,4-heptafluorobutanoate Chemical group [Li]OC(=O)C(F)(F)C(F)(F)C(F)(F)F KMOFAUACKFPRPG-UHFFFAOYSA-M 0.000 description 5
- WCXIRBYEIYUFJL-UHFFFAOYSA-M lithium;2,2,3,3,3-pentafluoropropanoate Chemical group [Li+].[O-]C(=O)C(F)(F)C(F)(F)F WCXIRBYEIYUFJL-UHFFFAOYSA-M 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- LRMSQVBRUNSOJL-UHFFFAOYSA-N 2,2,3,3,3-pentafluoropropanoic acid Chemical compound OC(=O)C(F)(F)C(F)(F)F LRMSQVBRUNSOJL-UHFFFAOYSA-N 0.000 description 4
- 229920001721 polyimide Polymers 0.000 description 4
- PXUULQAPEKKVAH-UHFFFAOYSA-M 2,2,3,3,4,4,5,5,6,6,6-undecafluorohexanoate Chemical compound [O-]C(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F PXUULQAPEKKVAH-UHFFFAOYSA-M 0.000 description 3
- 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 description 3
- SCFXKMFVFQSCKX-UHFFFAOYSA-L barium(2+);4-octylphenolate Chemical compound [Ba+2].CCCCCCCCC1=CC=C([O-])C=C1.CCCCCCCCC1=CC=C([O-])C=C1 SCFXKMFVFQSCKX-UHFFFAOYSA-L 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 239000010406 cathode material Substances 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- YPJUNDFVDDCYIH-UHFFFAOYSA-N perfluorobutyric acid Chemical compound OC(=O)C(F)(F)C(F)(F)C(F)(F)F YPJUNDFVDDCYIH-UHFFFAOYSA-N 0.000 description 3
- SCWLIHXXYXFUFV-UHFFFAOYSA-M sodium;2,2,3,3,3-pentafluoropropanoate Chemical compound [Na+].[O-]C(=O)C(F)(F)C(F)(F)F SCWLIHXXYXFUFV-UHFFFAOYSA-M 0.000 description 3
- 239000004952 Polyamide Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 229920006267 polyester film Polymers 0.000 description 2
- KQNSPSCVNXCGHK-UHFFFAOYSA-N [3-(4-tert-butylphenoxy)phenyl]methanamine Chemical compound C1=CC(C(C)(C)C)=CC=C1OC1=CC=CC(CN)=C1 KQNSPSCVNXCGHK-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- CXZGQIAOTKWCDB-UHFFFAOYSA-N perfluoropentanoic acid Chemical compound OC(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F CXZGQIAOTKWCDB-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- YSHHTXWLHYSYJP-UHFFFAOYSA-M sodium;2,2,3,3,4,4,4-heptafluorobutanoate Chemical compound [Na+].[O-]C(=O)C(F)(F)C(F)(F)C(F)(F)F YSHHTXWLHYSYJP-UHFFFAOYSA-M 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
Classifications
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- 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
- H01M10/0568—Liquid materials characterised by the solutes
-
- 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
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- 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
- H01M10/056—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
- H01M10/42—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
-
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Secondary Cells (AREA)
Abstract
The invention provides a lithium/sodium fluorocarboxylate electrolyte and a lithium/sodium ion battery containing the same, which are characterized in that the electrolyte comprises, by weight, 0.5% -5% of lithium/sodium fluorocarboxylate, 2% -10% of lithium/sodium salt, 0.5% -2% of additive and 80% -95% of organic solvent, and the preparation process of the lithium/sodium fluorocarboxylate comprises the following steps: the preparation method comprises the steps of uniformly mixing fluorocarboxylic acid and lithium hydroxide/sodium in a molar ratio of 1:1-1:1.02, reacting completely at a temperature of 70-90 ℃, then distilling the reaction product under reduced pressure to remove a solvent, crystallizing to separate out solid, repeatedly filtering, and finally drying the product within a temperature range of 70-90 ℃ to obtain the lithium/sodium fluorocarboxylate.
Description
Technical Field
The invention relates to the technical field of lithium/sodium ion batteries, in particular to a lithium/sodium fluorocarboxylate electrolyte and a lithium/sodium ion battery containing the same.
Background
Lithium/sodium ion batteries are widely used in various fields as green and environment-friendly energy sources. The electric vehicle is widely accepted by various circles in the future as an environment-friendly energy-saving direction instead of the fuel oil vehicle, and meanwhile, the demand of the lithium/sodium ion battery is exponentially increased. Therefore, the lithium/sodium ion battery is also coming into the golden period of blowout development as the most potential power battery in electric vehicles and oil-electricity hybrid electric vehicles. The lithium/sodium ion battery is to be introduced to the market as industrialization, and technicians are also required to have higher and more severe requirements on the characteristics of the lithium/sodium ion battery, such as energy density, stability, storage property, production cost and the like.
The lithium ion battery consists of a positive electrode material, a negative electrode material, electrolyte and a diaphragm, all the structures work in a coordinated manner, and each component can have a great influence on the performance of the battery. The electrolyte plays roles of ion transmission and charge conduction between the anode and the cathode, and is used as a bridge for communicating the anode material and the cathode material. In general, lithium ion battery electrolytes are composed of an organic solvent, lithium/sodium salts, and additives. After the battery is assembled, the electrolyte is soaked on the surface of the anode material, and under the condition of low potential in the first charge and discharge process, the organic solvent, the lithium salt and the additive are reduced and decomposed on the surface of the anode material to form a solid electrolyte interface film (SEI film), wherein the SEI film is a key ring of the battery performance, and plays a key role in the charge and discharge cycle performance of the battery. The SEI film comprises organic components (R-CO) 3 Li) and an inorganic component (mainly LiF, li 2 CO 3 ) Part of lithium ions are consumed in the forming process, so that the irreversible capacity of the first charge and discharge is increased, and the charge and discharge efficiency of the electrode material is reduced. During cycling, SEI is continuously increased to consume electrolyte to cause accelerated capacity attenuation, so that the stability of SEI film is beneficial to batteryPerformance and lifetime are very important. In addition, a common LiPF 6 The electrolyte lithium salt has poor thermal stability, and the degradation of battery performance is easy to cause after decomposition.
Therefore, in order to develop lithium/sodium salt having thermal stability, a more stable SEI film is constructed, and it is necessary to reduce the migration rate of lithium/sodium ions while preventing decomposition of lithium/sodium salt from affecting battery performance and service life, aiming at the existing lithium/sodium ion battery system.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides the lithium/sodium fluorocarboxylate electrolyte and the lithium/sodium ion battery containing the electrolyte, and the addition of the lithium/sodium fluorocarboxylate enables the SEI film of the lithium/sodium ion battery to have better stability, so that the lithium/sodium ion battery with excellent performance and longer service life is obtained.
The invention aims to provide a lithium/sodium fluorocarboxylate electrolyte and a lithium/sodium ion battery containing the same, which are characterized in that the electrolyte comprises lithium/sodium fluorocarboxylate, lithium/sodium salt, an additive and an organic solvent, wherein the lithium/sodium fluorocarboxylate has the following structural formula:
[R-COO] - Li + or (b)
[R-COO] - Na + ，
Wherein R is-C 1 ～-C 17 R contains at least 1 fluorine.
Preferably, the preparation flow of the lithium/sodium salt of the fluorocarboxylate is as follows:
(1) Dissolving solid lithium hydroxide/sodium in deionized water to obtain lithium hydroxide/sodium solution, weighing fluorocarboxylic acid and lithium hydroxide/sodium, uniformly mixing in a molar ratio of 1:1-1:1.02, and reacting for 4-6 hours at 70-90 ℃;
(2) Then placing the reaction product in the step (1) into a flask, and distilling under reduced pressure at 70-90 ℃ to remove the solvent;
(3) Crystallizing the reduced pressure distillation product in (2) to separate out solid;
(4) Repeatedly filtering the crystallized product in the step (3);
(5) Drying the filtered product in the step (4) at the temperature of 70-90 ℃ to obtain lithium/sodium fluorocarboxylate.
Preferably, the lithium/sodium salt is LiPF 6 /NaPF 6 、LiClO 4 /NaClO 4 、LiBF 4 /NaBF 4 、LiAsF 6 /NaAsF 6 One of LiFSI/NaFSI.
Preferably, the additives include film forming additives and flame retardant additives.
Preferably, the film forming additive is at least one of vinylene carbonate and fluoroethylene carbonate.
Preferably, the flame retardant additive is one or more of an organic phosphide, an organic fluoride and a fluoroalkyl phosphate.
Preferably, the organic solvent is composed of a chain carbonate and a cyclic carbonate, the chain carbonate is at least one of dimethyl carbonate (DMC), diethyl carbonate (DEC) and ethylmethyl carbonate (EMC), and the cyclic carbonate is at least one of Ethylene Carbonate (EC) and Propylene Carbonate (PC).
Preferably, the content of the lithium/sodium salt of the fluorocarboxylate is 0.5-5% of the electrolyte, the content of the lithium/sodium salt is 2-10% of the electrolyte, the content of the additive is 0.5-2% of the electrolyte, and the content of the organic solvent is 80-95% of the electrolyte.
Preferably, the lithium/sodium ion battery comprises a positive electrode, a negative electrode, a separator and the lithium/sodium fluorocarboxylate electrolyte.
Preferably, the positive electrode material is one or more of lithium iron phosphate/sodium vanadium phosphate, lithium manganate, lithium cobaltate and lithium nickel cobalt manganate, the negative electrode material is at least one of graphite, hard carbon, soft carbon, silicon-carbon composite, silicon-oxygen composite and metal lithium/sodium material, and the separator is at least one of a porous polymer film, a non-woven fabric separator and an inorganic composite film.
The beneficial effects of the invention are as follows: the lithium/sodium fluorocarboxylate contains-COO group, -COO and-OCO in the existing SEI film 2 The group is more difficult to decompose and has better thermal stability than the group, and meanwhileThe bond sum energy of lithium/sodium ions is smaller, which is beneficial to improving the migration speed of lithium/sodium ions on the SEI film, so that a more stable SEI film can be constructed. And the lithium/sodium salt of the fluorocarboxylic acid of the present application is compared to the conventional LiPF 6 Has better heat stability compared with LiClO 4 Has better safety compared with LiAsF 6 The lithium/sodium salt has lower toxicity, can be used as lithium/sodium ion battery electrolyte together with common lithium/sodium salt, can obviously improve the safety and the cycle service life of the lithium/sodium ion battery, and has simple preparation flow of the lithium/sodium salt of the fluorocarboxylic acid, lower cost and easy realization of industrial production.
Detailed Description
Control group 1
The lithium ion battery comprises lithium salt, an additive and an organic solvent, wherein the lithium salt is LiPF (lithium ion power filter) by weight 6 The electrolyte comprises 5% of electrolyte, the additive is vinylene carbonate and organic phosphide comprises 1% of electrolyte, and the organic solvent is DMC, EMC and EC which comprise 94% of electrolyte.
The lithium ion battery comprises a positive electrode, a negative electrode, a diaphragm and electrolyte, wherein the positive electrode material is lithium iron phosphate, the negative electrode material is graphite, and the diaphragm is a porous polyimide film.
Control group 2
A sodium ion battery, the electrolyte comprises sodium salt, additive and organic solvent, the sodium salt is NaPF by weight 6 5% of the electrolyte, 1.5% of the electrolyte, and 93.5% of the electrolyte, EC and PC as organic solvents.
The sodium ion battery comprises an anode, a cathode and a diaphragm electrolyte, wherein the anode material is sodium vanadium phosphate, the cathode material is hard carbon, and the diaphragm is a porous polyimide film.
Example 1
The electrolyte comprises lithium fluorocarboxylate, lithium salt, an additive and an organic solvent, wherein the lithium fluorocarboxylate is lithium pentafluoropropionate, and the structural formula is as follows:
[CF 3 -CF 2 -COO] - Li +
the preparation process of the lithium pentafluoropropionate is as follows:
(1) Adding 7.3g of anhydrous lithium hydroxide into 120ml of deionized water, stirring to dissolve the solid completely, then weighing 50g of pentafluoropropionic acid, slowly adding into the solution, uniformly mixing, and reacting for 4 hours at 70 ℃;
(2) Subsequently placing the reaction product in (1) in a flask, and distilling off the solvent under reduced pressure at 70 ℃;
(3) Crystallizing the reduced pressure distillation product in (2) to separate out solid;
(4) Repeatedly filtering the crystallized product in the step (3);
(5) The filtered product of (4) was dried at 70℃for 12 hours to obtain lithium pentafluoropropionate.
Calculated by weight, the content of lithium pentafluoropropionate is 0.5% of the electrolyte, and the lithium salt is LiPF 6 The electrolyte comprises 5% of electrolyte, the additive is vinylene carbonate and organic phosphide comprises 1% of electrolyte, and the organic solvent is DMC, EMC and EC comprises 93.5% of electrolyte.
The lithium ion battery comprises a positive electrode, a negative electrode, a diaphragm and lithium pentafluoropropionate electrolyte, wherein the positive electrode is made of lithium iron phosphate, the negative electrode is made of graphite, and the diaphragm is made of porous polyimide film.
Example 2
The electrolyte comprises lithium fluorocarboxylate, lithium salt, an additive and an organic solvent, wherein the lithium fluorocarboxylate is lithium heptafluorobutyrate, and the structural formula is as follows:
[CF 3 -CF 2 -CF 2 -COO] - Li +
the preparation process of the lithium heptafluorobutyrate is as follows:
(1) Adding 11.2g of anhydrous lithium hydroxide into 160ml of deionized water, stirring to dissolve the solid completely, then weighing 100g of heptafluorobutyric acid, slowly adding into the solution, uniformly mixing, and reacting for 4 hours at 70 ℃;
(2) Subsequently placing the reaction product in (1) in a flask, and distilling off the solvent under reduced pressure at 70 ℃;
(3) Crystallizing the reduced pressure distillation product in (2) to separate out solid;
(4) Repeatedly filtering the crystallized product in the step (3);
(5) The filtered product of (4) was dried at 70℃for 12 hours to obtain lithium heptafluorobutyrate.
Calculated by weight, the content of lithium heptafluorobutyrate is 0.5% of the electrolyte, and the lithium salt is LiPF 6 The electrolyte comprises 10% of the electrolyte, the additive is vinylene carbonate and organic fluoride comprises 1% of the electrolyte, and the organic solvent is DMC, EMC and EC comprising 88.5% of the electrolyte.
The lithium ion battery comprises a positive electrode, a negative electrode, a diaphragm and lithium heptafluorobutyrate electrolyte, wherein the positive electrode is made of lithium iron phosphate, the negative electrode is made of graphite, and the diaphragm is made of a porous polyamide film.
Example 3
The electrolyte comprises lithium fluorocarboxylate, lithium salt, an additive and an organic solvent, wherein the lithium fluorocarboxylate is lithium nonafluoropentanoate, and the structural formula is as follows:
[CF 3 -CF 2 -CF 2 -CF 2 -COO] - Li +
the preparation process of the lithium nonafluorovalerate is as follows:
(1) Adding 9.07g of anhydrous lithium hydroxide into 160ml of deionized water, stirring to dissolve the solid completely, then weighing 100g of nonafluorovaleric acid, slowly adding into the solution, uniformly mixing, and reacting for 4 hours at the temperature of 80 ℃;
(2) Subsequently placing the reaction product in (1) in a flask, and distilling off the solvent under reduced pressure at 80 ℃;
(3) Crystallizing the reduced pressure distillation product in (2) to separate out solid;
(4) Repeatedly filtering the crystallized product in the step (3);
(5) The filtered product of (4) was dried at 80℃for 12 hours to obtain lithium nonafluoropentanoate.
Calculated by weight, the content of lithium nonafluoropentanoate is 0.5% of the electrolyte, and the lithium salt is LiPF 6 Accounting for 6% of the electrolyte, addThe additive is fluoroethylene carbonate and fluoroalkyl phosphate accounting for 2% of the electrolyte, and the organic solvent is DMC, EMC and EC accounting for 91.5% of the electrolyte.
The lithium ion battery comprises a positive electrode, a negative electrode, a diaphragm and lithium nonafluoropentanoate electrolyte, wherein the positive electrode is made of lithium iron phosphate, the negative electrode is made of graphite, and the diaphragm is made of a porous polyamide film.
Example 4
The electrolyte comprises lithium fluorocarboxylate, lithium salt, an additive and an organic solvent, wherein the lithium fluorocarboxylate is perfluorohexanoic acid lithium salt, and the structural formula is as follows:
[CF 3 -CF 2 -CF 2 -CF 2 -CF 2 -COO] - Li +
the preparation process of the lithium perfluorohexanoate comprises the following steps:
(1) 7.626g of anhydrous lithium hydroxide is added into 160ml of deionized water and stirred to dissolve the solid completely, then 100g of perfluorohexanoic acid is weighed and added into the solution slowly and mixed uniformly, and the mixture reacts for 4 hours at the temperature of 85 ℃;
(2) Subsequently placing the reaction product in (1) in a flask, and distilling off the solvent under reduced pressure at 90 ℃;
(3) Crystallizing the reduced pressure distillation product in (2) to separate out solid;
(4) Repeatedly filtering the crystallized product in the step (3);
(5) The filtered product of (4) was dried at 90℃for 12 hours to obtain lithium perfluorohexanoate.
Calculated by weight, the content of the lithium perfluorohexanoate is 0.5% of the electrolyte, and the lithium salt is LiPF 6 10% of the electrolyte, 0.5% of the electrolyte, and 89% of DMC, EMC and EC.
The lithium ion battery comprises a positive electrode, a negative electrode, a diaphragm and a perfluoro lithium caproate electrolyte, wherein the positive electrode is made of lithium iron phosphate, the negative electrode is made of graphite, and the diaphragm is made of a porous polyester film.
Example 5
The electrolyte comprises sodium salt of fluorocarboxylic acid, sodium salt, additive and organic solvent, wherein the sodium salt of fluorocarboxylic acid is sodium salt of pentafluoropropionic acid, and the structural formula is as follows:
[CF 3 -CF 2 -COO] - Na +
the preparation process of the sodium pentafluoropropionate is as follows:
(1) Adding 24.4g of anhydrous sodium hydroxide into 160ml of deionized water, stirring to dissolve the solid completely, then weighing 100g of pentafluoropropionic acid, slowly adding into the solution, uniformly mixing, and reacting for 4 hours at 70 ℃;
(2) Subsequently placing the reaction product in (1) in a flask, and distilling off the solvent under reduced pressure at 70 ℃;
(3) Crystallizing the reduced pressure distillation product in (2) to separate out solid;
(4) Repeatedly filtering the crystallized product in the step (3);
(5) The filtered product of (4) was dried at 70℃for 12 hours to give sodium pentafluoropropionate.
Calculated by weight, the content of sodium salt of the pentafluoropropionate is 0.5 percent of that of the electrolyte, and the sodium salt is NaPF 6 5% of the electrolyte, 1.5% of the electrolyte, and 93% of the electrolyte, EC and PC, respectively.
The sodium ion battery comprises an anode, a cathode, a diaphragm and a sodium pentafluoropropionate electrolyte, wherein the anode is made of sodium vanadium phosphate, the cathode is made of hard carbon, and the diaphragm is made of a porous polyimide film.
Example 6
The electrolyte comprises sodium salt of fluorocarboxylic acid, lithium salt, additives and organic solvent, wherein the sodium salt of fluorocarboxylic acid is sodium salt of heptafluorobutyric acid, and the structural formula is:
[CF 3 -CF 2 -CF 2 -COO] - Na +
the preparation process of sodium heptafluorobutyrate is as follows:
(1) Adding 18.7g of anhydrous sodium hydroxide into 160ml of deionized water, stirring to dissolve the solid completely, then weighing 100g of heptafluorobutyric acid, slowly adding into the solution, uniformly mixing, and reacting for 6 hours at 70 ℃;
(2) Subsequently placing the reaction product in (1) in a flask, and distilling off the solvent under reduced pressure at 70 ℃;
(3) Crystallizing the reduced pressure distillation product in (2) to separate out solid;
(4) Repeatedly filtering the crystallized product in the step (3);
(5) The filtered product of (4) was dried at 70℃for 12 hours to give sodium heptafluorobutyrate.
Calculated by weight, the content of sodium heptafluorobutyric acid salt is 0.5% of electrolyte, and the sodium salt is NaPF 6 8% of the electrolyte, 1.5% of the electrolyte is ethylene carbonate and fluoroalkyl phosphate as additives, and 90% of the electrolyte is EC and PC as organic solvents.
The sodium ion battery comprises an anode, a cathode, a diaphragm and sodium heptafluorobutyrate electrolyte, wherein the anode material is sodium vanadium phosphate, the cathode material is hard carbon, and the diaphragm is a porous polyester film.
Performance test: the lithium/sodium ion batteries of examples 1-6 and control groups 1-2 are respectively charged and discharged for 3 times at 25 ℃ with a constant current of 1C to obtain the standard capacity C of the battery 1 Then standard charging is carried out, after charging is completed, the battery is stored for 28 days under the condition of 25 ℃, and then discharge is carried out according to standard discharge multiplying power, thus obtaining discharge capacity C 2 The 1C charge-discharge capacity retention rate was
TABLE 1C charge-discharge capacity retention rates of examples and control groups
As can be seen from comparison of the data of the control group and the examples, the 1C charge-discharge capacity retention rate of the lithium/sodium ion battery containing the lithium/sodium salt of fluorocarboxylic acid is higher, and the performance of the lithium/sodium ion battery in the present invention is better.
Claims (10)
1. The lithium/sodium fluorocarboxylate electrolyte is characterized by comprising lithium/sodium fluorocarboxylate, lithium/sodium salt, an additive and an organic solvent, wherein the lithium/sodium fluorocarboxylate has the structural formula:
wherein R is-C 1 ～-C 17 R contains at least 1 fluorine.
2. The lithium/sodium salt electrolyte of claim 1, wherein the preparation process of the lithium/sodium salt electrolyte of the fluorinated carboxylic acid is as follows:
(1) Dissolving solid lithium hydroxide/sodium in deionized water to obtain lithium hydroxide/sodium solution, uniformly mixing fluorocarboxylic acid and lithium hydroxide/sodium in a molar ratio of 1:1-1:1.02, and reacting for 4-6 hours at 70-90 ℃;
(2) Then placing the reaction product in the step (1) into a flask, and distilling under reduced pressure at 70-90 ℃ to remove the solvent;
(3) Crystallizing the reduced pressure distillation product in (2) to separate out solid;
(4) Repeatedly filtering the crystallized product in the step (3);
(5) Drying the filtered product in the step (4) at the temperature of 70-90 ℃ to obtain lithium/sodium fluorocarboxylate.
3. The lithium/sodium fluorocarboxylate electrolyte according to claim 1, wherein the lithium/sodium salt is LiPF 6 /NaPF 6 、LiClO 4 /NaClO 4 、LiBF 4 /NaBF 4 、LiAsF 6 /NaAsF 6 One of LiFSI/NaFSI.
4. The lithium/sodium fluorocarboxylate electrolyte according to claim 1, wherein the additives comprise a film-forming additive and a flame retardant additive.
5. The lithium/sodium fluorocarboxylate electrolyte according to claim 4, wherein the film-forming additive is at least one of vinylene carbonate and fluoroethylene carbonate.
6. The lithium/sodium fluorocarboxylate electrolyte of claim 4, wherein the flame retardant additive is one or more of an organic phosphide, an organic fluoride, and a fluoroalkyl phosphate.
7. The lithium/sodium fluorocarboxylate electrolyte according to claim 1, wherein the organic solvent is composed of a chain carbonate and a cyclic carbonate, the chain carbonate is at least one of dimethyl carbonate (DMC), diethyl carbonate (DEC) and methylethyl carbonate (EMC), and the cyclic carbonate is at least one of Ethylene Carbonate (EC) and Propylene Carbonate (PC).
8. The lithium/sodium salt electrolyte of claim 1, wherein the lithium/sodium salt of the fluorocarboxylic acid is 0.5-5% by weight of the electrolyte, the lithium/sodium salt is 2-10% by weight of the electrolyte, the additive is 0.5-2% by weight of the electrolyte, and the organic solvent is 80-95% by weight of the electrolyte.
9. A lithium/sodium ion battery comprising a positive electrode, a negative electrode, a separator, and the lithium/sodium fluorocarboxylate electrolyte of any one of claims 1 to 8.
10. The lithium/sodium ion battery of claim 9, wherein the positive electrode material is one or more of lithium iron phosphate/sodium vanadium phosphate, lithium manganate, lithium cobaltate and lithium nickel cobalt manganate, the negative electrode material is at least one of graphite, hard carbon, soft carbon, silicon carbon composite, silicon oxygen composite and metal lithium/sodium material, and the separator is at least one of a porous polymer film, a non-woven fabric separator, an inorganic composite film and a glass fiber separator.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010238504A (en) * | 2009-03-31 | 2010-10-21 | Sanwa Yuka Kogyo Kk | Nonaqueous electrolyte solution |
| JP2022070145A (en) * | 2020-10-26 | 2022-05-12 | 旭化成株式会社 | Method for producing fluorinated carboxylate |
| CN115312868A (en) * | 2022-09-19 | 2022-11-08 | 苏州德加能源科技有限公司 | High-voltage-resistant electrolyte and application thereof in lithium/sodium ion battery |
| CN116057036A (en) * | 2020-09-08 | 2023-05-02 | 大金工业株式会社 | Fluorine-containing carboxylate compound |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010238504A (en) * | 2009-03-31 | 2010-10-21 | Sanwa Yuka Kogyo Kk | Nonaqueous electrolyte solution |
| CN116057036A (en) * | 2020-09-08 | 2023-05-02 | 大金工业株式会社 | Fluorine-containing carboxylate compound |
| JP2022070145A (en) * | 2020-10-26 | 2022-05-12 | 旭化成株式会社 | Method for producing fluorinated carboxylate |
| CN115312868A (en) * | 2022-09-19 | 2022-11-08 | 苏州德加能源科技有限公司 | High-voltage-resistant electrolyte and application thereof in lithium/sodium ion battery |
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