CN114665152A - Electrolyte containing fluoroalkyl borate compound and battery composed of electrolyte - Google Patents
Electrolyte containing fluoroalkyl borate compound and battery composed of electrolyte Download PDFInfo
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- CN114665152A CN114665152A CN202210352711.XA CN202210352711A CN114665152A CN 114665152 A CN114665152 A CN 114665152A CN 202210352711 A CN202210352711 A CN 202210352711A CN 114665152 A CN114665152 A CN 114665152A
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- electrolyte
- carbonate
- halogenated
- battery
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- 239000003792 electrolyte Substances 0.000 title claims abstract description 53
- -1 fluoroalkyl borate compound Chemical class 0.000 title claims abstract description 21
- 150000001875 compounds Chemical class 0.000 claims abstract description 9
- 239000003960 organic solvent Substances 0.000 claims abstract description 7
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 12
- 229910001416 lithium ion Inorganic materials 0.000 claims description 12
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 8
- 150000004649 carbonic acid derivatives Chemical class 0.000 claims description 8
- 239000010439 graphite Substances 0.000 claims description 8
- 229910002804 graphite Inorganic materials 0.000 claims description 8
- 229910052744 lithium Inorganic materials 0.000 claims description 8
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 7
- 150000001733 carboxylic acid esters Chemical class 0.000 claims description 7
- 150000007942 carboxylates Chemical class 0.000 claims description 5
- 239000002131 composite material Substances 0.000 claims description 5
- 239000007773 negative electrode material Substances 0.000 claims description 5
- GETTZEONDQJALK-UHFFFAOYSA-N (trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=CC=C1 GETTZEONDQJALK-UHFFFAOYSA-N 0.000 claims description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 4
- 229920001774 Perfluoroether Polymers 0.000 claims description 4
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 claims description 4
- 239000011737 fluorine Substances 0.000 claims description 4
- 229910052731 fluorine Inorganic materials 0.000 claims description 4
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 3
- GOYDNIKZWGIXJT-UHFFFAOYSA-N 1,2-difluorobenzene Chemical compound FC1=CC=CC=C1F GOYDNIKZWGIXJT-UHFFFAOYSA-N 0.000 claims description 2
- JXUKFFRPLNTYIV-UHFFFAOYSA-N 1,3,5-trifluorobenzene Chemical compound FC1=CC(F)=CC(F)=C1 JXUKFFRPLNTYIV-UHFFFAOYSA-N 0.000 claims description 2
- HNAGHMKIPMKKBB-UHFFFAOYSA-N 1-benzylpyrrolidine-3-carboxamide Chemical compound C1C(C(=O)N)CCN1CC1=CC=CC=C1 HNAGHMKIPMKKBB-UHFFFAOYSA-N 0.000 claims description 2
- MMZYCBHLNZVROM-UHFFFAOYSA-N 1-fluoro-2-methylbenzene Chemical compound CC1=CC=CC=C1F MMZYCBHLNZVROM-UHFFFAOYSA-N 0.000 claims description 2
- MLBWTXHUVGBPNL-UHFFFAOYSA-N 1-pyridin-4-ylheptan-1-one Chemical compound CCCCCCC(=O)C1=CC=NC=C1 MLBWTXHUVGBPNL-UHFFFAOYSA-N 0.000 claims description 2
- HFZLSTDPRQSZCQ-UHFFFAOYSA-N 1-pyrrolidin-3-ylpyrrolidine Chemical compound C1CCCN1C1CNCC1 HFZLSTDPRQSZCQ-UHFFFAOYSA-N 0.000 claims description 2
- KALSHRGEFLVFHE-UHFFFAOYSA-N 2,4-dichloro-1-(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=C(Cl)C=C1Cl KALSHRGEFLVFHE-UHFFFAOYSA-N 0.000 claims description 2
- UHOPWFKONJYLCF-UHFFFAOYSA-N 2-(2-sulfanylethyl)isoindole-1,3-dione Chemical compound C1=CC=C2C(=O)N(CCS)C(=O)C2=C1 UHOPWFKONJYLCF-UHFFFAOYSA-N 0.000 claims description 2
- FPBJCOIQZLWHFK-UHFFFAOYSA-N 4,4-difluoro-5-methyl-1,3-dioxolan-2-one Chemical compound CC1OC(=O)OC1(F)F FPBJCOIQZLWHFK-UHFFFAOYSA-N 0.000 claims description 2
- DSMUTQTWFHVVGQ-UHFFFAOYSA-N 4,5-difluoro-1,3-dioxolan-2-one Chemical compound FC1OC(=O)OC1F DSMUTQTWFHVVGQ-UHFFFAOYSA-N 0.000 claims description 2
- OYOKPDLAMOMTEE-UHFFFAOYSA-N 4-chloro-1,3-dioxolan-2-one Chemical compound ClC1COC(=O)O1 OYOKPDLAMOMTEE-UHFFFAOYSA-N 0.000 claims description 2
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 claims description 2
- PNFFMCPDTFIXPD-UHFFFAOYSA-N CC(C)OC(=O)C(C)F Chemical compound CC(C)OC(=O)C(C)F PNFFMCPDTFIXPD-UHFFFAOYSA-N 0.000 claims description 2
- LEMDBKVETNBUKM-UHFFFAOYSA-N CCCOC(=O)C(F)CC Chemical compound CCCOC(=O)C(F)CC LEMDBKVETNBUKM-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
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 2
- IJMWOMHMDSDKGK-UHFFFAOYSA-N Isopropyl propionate Chemical compound CCC(=O)OC(C)C IJMWOMHMDSDKGK-UHFFFAOYSA-N 0.000 claims description 2
- QPJVMBTYPHYUOC-UHFFFAOYSA-N Methyl benzoate Natural products COC(=O)C1=CC=CC=C1 QPJVMBTYPHYUOC-UHFFFAOYSA-N 0.000 claims description 2
- RJUFJBKOKNCXHH-UHFFFAOYSA-N Methyl propionate Chemical compound CCC(=O)OC RJUFJBKOKNCXHH-UHFFFAOYSA-N 0.000 claims description 2
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 claims description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 2
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims description 2
- STSCVKRWJPWALQ-UHFFFAOYSA-N TRIFLUOROACETIC ACID ETHYL ESTER Chemical compound CCOC(=O)C(F)(F)F STSCVKRWJPWALQ-UHFFFAOYSA-N 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- WLLOZRDOFANZMZ-UHFFFAOYSA-N bis(2,2,2-trifluoroethyl) carbonate Chemical compound FC(F)(F)COC(=O)OCC(F)(F)F WLLOZRDOFANZMZ-UHFFFAOYSA-N 0.000 claims description 2
- OBNCKNCVKJNDBV-UHFFFAOYSA-N butanoic acid ethyl ester Natural products CCCC(=O)OCC OBNCKNCVKJNDBV-UHFFFAOYSA-N 0.000 claims description 2
- CRBXQJHBOIIYLY-UHFFFAOYSA-N butyl 2-fluoropropanoate Chemical compound CCCCOC(=O)C(C)F CRBXQJHBOIIYLY-UHFFFAOYSA-N 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- LEGITHRSIRNTQV-UHFFFAOYSA-N carbonic acid;3,3,3-trifluoroprop-1-ene Chemical compound OC(O)=O.FC(F)(F)C=C LEGITHRSIRNTQV-UHFFFAOYSA-N 0.000 claims description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 2
- ONLLXDPBECIJCM-UHFFFAOYSA-N ethyl 2-fluorobutanoate Chemical compound CCOC(=O)C(F)CC ONLLXDPBECIJCM-UHFFFAOYSA-N 0.000 claims description 2
- ODMITNOQNBVSQG-UHFFFAOYSA-N ethyl 2-fluoropropanoate Chemical compound CCOC(=O)C(C)F ODMITNOQNBVSQG-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
- 229910021385 hard carbon Inorganic materials 0.000 claims description 2
- JMMWKPVZQRWMSS-UHFFFAOYSA-N isopropanol acetate Natural products CC(C)OC(C)=O JMMWKPVZQRWMSS-UHFFFAOYSA-N 0.000 claims description 2
- 229940011051 isopropyl acetate Drugs 0.000 claims description 2
- GWYFCOCPABKNJV-UHFFFAOYSA-N isovaleric acid Chemical compound CC(C)CC(O)=O GWYFCOCPABKNJV-UHFFFAOYSA-N 0.000 claims description 2
- GBPVMEKUJUKTBA-UHFFFAOYSA-N methyl 2,2,2-trifluoroethyl carbonate Chemical compound COC(=O)OCC(F)(F)F GBPVMEKUJUKTBA-UHFFFAOYSA-N 0.000 claims description 2
- MHAIQPNJLRLFLO-UHFFFAOYSA-N methyl 2-fluoropropanoate Chemical compound COC(=O)C(C)F MHAIQPNJLRLFLO-UHFFFAOYSA-N 0.000 claims description 2
- PMGBATZKLCISOD-UHFFFAOYSA-N methyl 3,3,3-trifluoropropanoate Chemical compound COC(=O)CC(F)(F)F PMGBATZKLCISOD-UHFFFAOYSA-N 0.000 claims description 2
- 229940095102 methyl benzoate Drugs 0.000 claims description 2
- 229940017219 methyl propionate Drugs 0.000 claims description 2
- 229910021421 monocrystalline silicon Inorganic materials 0.000 claims description 2
- PYLWMHQQBFSUBP-UHFFFAOYSA-N monofluorobenzene Chemical compound FC1=CC=CC=C1 PYLWMHQQBFSUBP-UHFFFAOYSA-N 0.000 claims description 2
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 claims description 2
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Inorganic materials O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 claims description 2
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 229910001414 potassium ion Inorganic materials 0.000 claims description 2
- HERCSPPGAAQXBN-UHFFFAOYSA-N propan-2-yl 2-fluoroacetate Chemical compound CC(C)OC(=O)CF HERCSPPGAAQXBN-UHFFFAOYSA-N 0.000 claims description 2
- IRWIXUQVVIFUPL-UHFFFAOYSA-N propyl 2-fluoroacetate Chemical compound CCCOC(=O)CF IRWIXUQVVIFUPL-UHFFFAOYSA-N 0.000 claims description 2
- LXPTXVYIIYSSHU-UHFFFAOYSA-N propyl 2-fluoropropanoate Chemical compound CCCOC(=O)C(C)F LXPTXVYIIYSSHU-UHFFFAOYSA-N 0.000 claims description 2
- 229940090181 propyl acetate Drugs 0.000 claims description 2
- HUAZGNHGCJGYNP-UHFFFAOYSA-N propyl butyrate Chemical compound CCCOC(=O)CCC HUAZGNHGCJGYNP-UHFFFAOYSA-N 0.000 claims description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 2
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 229910001415 sodium ion Inorganic materials 0.000 claims description 2
- 229910021384 soft carbon Inorganic materials 0.000 claims description 2
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000008151 electrolyte solution Substances 0.000 claims 1
- 230000014759 maintenance of location Effects 0.000 abstract description 6
- 238000007600 charging Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 239000000463 material Substances 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- 238000010277 constant-current charging Methods 0.000 description 4
- 239000006245 Carbon black Super-P Substances 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 description 2
- 125000005910 alkyl carbonate group Chemical group 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000006258 conductive agent Substances 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000008014 freezing Effects 0.000 description 2
- 238000007710 freezing Methods 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000005486 organic electrolyte Substances 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical group [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 239000002174 Styrene-butadiene Substances 0.000 description 1
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000010280 constant potential charging Methods 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229940125753 fibrate Drugs 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 238000012812 general test Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 238000004537 pulping Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- YZYKZHPNRDIPFA-UHFFFAOYSA-N tris(trimethylsilyl) borate Chemical compound C[Si](C)(C)OB(O[Si](C)(C)C)O[Si](C)(C)C YZYKZHPNRDIPFA-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/54—Electrolytes
- H01G11/58—Liquid electrolytes
- H01G11/64—Liquid electrolytes characterised by 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
- H01M10/052—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
- H01M10/056—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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Manufacturing & Machinery (AREA)
- General Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Power Engineering (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Secondary Cells (AREA)
Abstract
The invention discloses an electrolyte containing a fluoroalkyl borate compound and a battery consisting of the electrolyte. The electrolyte comprises an electrolyte, an organic solvent and a fluorinated alkyl borate compound shown as a formula I. The electrolyte is added with the compound shown in the formula I, so that when the electrolyte is used in a battery, the multi-aspect performance of the battery is improved, the 3C discharge rate at normal temperature in the battery is more than 79.5 percent at the 3C charge rate, the 1C discharge rate at-20 ℃ is more than 80.8 percent at the normal temperature, the capacity retention rate of 3C charge/1C discharge cycle at 800 times of normal temperature cycle is more than 82.6 percent, the capacity retention rate of 3C charge/1C discharge cycle at high temperature of 45 ℃ is more than 81.8 percent at 800 times of high temperature 3C charge/1C discharge cycle, and the comprehensive performance is excellent.
Description
Technical Field
The invention belongs to the technical field of electrochemical energy storage, and particularly relates to electrolyte containing fluoroalkyl borate compounds and a battery comprising the electrolyte.
Background
Currently, organic electrolyte materials used in the lithium battery industry are mainly alkyl carbonate compounds and LiPF6Lithium salt system, the performance of which is greatly reduced at high temperature (above 60 ℃), while the power battery for electric automobile requires a higher working temperature range (about-30 to 80 ℃); moreover, the alkyl carbonate organic electrolyte material has high flammability, so that the safety has great hidden trouble; especially in the field of hybrid and all-electric automotive applications, long-term cycling problems and safety are important factors that limit the practical application of these materials.
The electrolyte is an important component of the lithium ion battery, and plays a role in transmitting lithium ions between the positive electrode and the negative electrode. The safety, charge-discharge cycle, working temperature range and charge-discharge capacity of the battery are all important in relation to the electrochemical performance of the electrolyte. The traditional functional components in the electrolyte play a key role in prolonging the service life of the battery, but no long-term effective measure is provided for delaying or inhibiting the generation of lithium dendrites, so that the safety performance of the battery and the service life of charge-discharge cycles are greatly influenced.
CN106033824B discloses an electrolyte containing tris (trimethylsilyl) borate, and a high-voltage lithium ion battery containing the electrolyte has excellent normal-temperature cycle performance, high-temperature storage performance and low-temperature discharge performance. However, the oxidation potential of this substance is low, and it is difficult to satisfy the requirement of stable charge and discharge of the battery at a voltage of 4.3V or more.
The requirement of the battery on high energy density and high temperature and high voltage stability is higher and higher, so that it is important to develop an electrolyte for improving the stable circulation of the battery under the voltage of more than 4.3V.
Disclosure of Invention
The invention aims to provide an electrolyte containing a fluoroalkyl borate compound and a battery comprising the electrolyte.
An electrolyte containing a fluoroalkyl borate compound, the electrolyte comprising an electrolyte, an organic solvent, and a fluoroalkyl borate compound represented by formula I:
the electrolyte comprises XClO4、XPF6、XBF4、XTFSI、XFSI、XBOB、XODFB,XCF3SO3Or XAsF6Any one or a combination of at least two of them; wherein X is Li, Na or K.
The organic solvent includes any one of carbonate, carboxylate, fluorocarboxylate, propionate, fluoroether or aromatic hydrocarbon or a combination of at least two thereof.
The carbonate includes a halogenated carbonate and/or a non-halogenated carbonate; the non-halogenated carbonate comprises any one or the combination of at least two of ethylene carbonate, propylene carbonate, diethyl carbonate, dimethyl carbonate or ethyl methyl carbonate; the halogenated carbonate comprises any one or the combination of at least two of fluoroethylene carbonate, difluoroethylene carbonate, difluoropropylene carbonate, ethyl trifluoroacetate, trifluoroethyl methyl carbonate, trifluoromethyl ethylene carbonate, 4-trifluoromethyl ethylene carbonate, chloroethylene carbonate, bis (2,2, 2-trifluoroethyl) carbonate, methyl trifluoropropionate, 3,3, 3-trifluoro ethyl acetate, 2-trifluoromethyl methyl benzoate, 4,4, 4-trifluoro ethyl butyrate or 1,1,1,3,3, 3-hexafluoroisopropyl acrylate.
The carboxylic ester comprises halogenated carboxylic ester and/or non-halogenated carboxylic ester; the non-halogenated carboxylic acid ester comprises any one or a combination of at least two of propyl butyrate, propyl acetate, isopropyl acetate, butyl propionate, isopropyl propionate, ethyl butyrate, methyl propionate, ethyl propionate or propyl propionate; the halogenated carboxylic acid ester comprises any one or a combination of at least two of propyl fluorobutyrate, propyl fluoroacetate, isopropyl fluoroacetate, butyl fluoropropionate, isopropyl fluoropropionate, ethyl fluorobutyrate, methyl fluoropropionate, ethyl fluoropropionate and propyl fluoropropionate.
The fluorine ether is a fluorine ether having 7 or less carbon atoms.
The aromatic hydrocarbon comprises halogenated aromatic hydrocarbon and/or non-halogenated aromatic hydrocarbon; the halogenated aromatic hydrocarbon comprises any one or the combination of at least two of monofluorobenzene, difluorobenzene, 1,3, 5-trifluorobenzene, trifluorotoluene, 2-fluorotoluene or 2, 4-dichlorotrifluorotoluene.
The weight percentage of the electrolyte in the electrolyte is 8-49%; the weight percentage of the organic solvent in the electrolyte is 1-85%; the fluorine-containing alkyl borate compound shown in the formula I accounts for 0.01-50% of the electrolyte.
A battery comprises the electrolyte.
The battery comprises a lithium ion battery, a sodium ion battery, a potassium ion battery or a super capacitor; the negative electrode material of the lithium ion battery comprises any one or the combination of at least two of graphite, soft carbon, hard carbon, a composite material of monocrystalline silicon and graphite, a composite material of silicon oxide and graphite, and lithium titanate or niobium pentoxide.
The invention has the beneficial effects that: the electrolyte is added with the compound shown in the formula I, so that when the electrolyte is used in a battery, the multi-aspect performance of the battery is improved, the 3C discharge rate at normal temperature in the battery is more than 79.5 percent at the 3C charge rate, the 1C discharge rate at-20 ℃ is more than 80.8 percent at the normal temperature, the capacity retention rate of 3C charge/1C discharge cycle at 800 times of normal temperature cycle is more than 82.6 percent, the capacity retention rate of 3C charge/1C discharge cycle at high temperature of 45 ℃ is more than 81.8 percent at 800 times of high temperature 3C charge/1C discharge cycle, and the comprehensive performance is excellent.
Detailed Description
In order that the invention may be more fully understood, reference will now be made to the following description. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
The general test platform used in the examples is as follows: the anode of the experiment adopts a binder PVDF-S5130, a composite conductive agent Super-P/KS-6 (the mass ratio of Super-P: KS-6 is 2: 1), a 622 nickel cobalt manganese ternary anode material or a lithium cobaltate anode material and a solvent NMP (N-methyl-2-pyrrolidone), and the cathode adopts C-P15, a conductive agent Super-P solvent CMC, H2O and SBR (styrene butadiene rubber) are used as raw materials, slurry is prepared by adopting a wet pulping process respectively, the viscosity of a positive electrode is adjusted to 10000-13000 mPa & s, the viscosity of a negative electrode is adjusted to 1500-3000 mPa & s, the designed N/P ratio is 1.12, the capacity is 1671mAh, a lithium ion soft package battery is prepared by coating, slicing, rolling, slitting, drying at 140 ℃ for 8h, sticking an adhesive tape, rolling a battery core and drying at 80 ℃ for 48h, then the lithium ion soft package battery is prepared by injecting and sealing the lithium ion battery according to different electrolyte formulas, standing for 24h, forming, primary final sealing, aging and secondary final sealing, and then the battery is tested in cycle performance and safety performance.
The fluorochemical silane substituent compounds used in examples 1-7 were custom-made (99.5% purity) from Shijiazhuang Santa Clay chemical.
The electrolyte compositions of examples 1 to 11 and comparative examples 1 and 2 are shown in table 1.
The compositions of the electrolytes provided in examples 1 to 11 and comparative examples 1 and 2 were all in weight ratio and each contained 1% VC and 1% PS, as shown in table 1.
TABLE 1 (all in the table are weight ratios)
The electrolytes described in examples 1-10 and comparative example 1 were added to a 1.67Ah lithium ion battery containing a graphite negative electrode material (fir P15), NCM622 nickel cobalt manganese ternary material;
the following tests were performed:
(1) charge rate performance: the 1C current is 1.67A, and the 3C current is 5.01A; the charge and discharge potential range is 2.75V-4.35V. The charging rate of the 3C at the normal temperature is a ratio of a capacity C2 of the 3C constant current charging to a 1C constant current charging capacity C1.
(2) Cycle performance: the range of charging and discharging potential is 2.75V-4.35V, the charging current is 3C (5.01A) to 4.35V, the constant voltage charging of 4.35V is carried out until the cut-off current is less than or equal to 0.02C (0.0334A), after standing for 5 minutes, 1C (1.67A) is discharged to 2.75V, and the standing is carried out for 5 minutes; thus, the charge and discharge are cycled.
(3) Low-temperature discharge performance: the 1C (1.67A) discharge capacity at 25 ℃ was C1, and after full charge at 4.35V and freezing at-20 ℃ for 4 hours, the discharge was 1C (1.67A) to 2.75V, and the discharge capacity was C2. The discharge rate at-20 ℃ was C2/C1.
The electrolyte described in example 11 and comparative example 2 was added to a battery whose negative electrode material was a silicon-carbon negative electrode material (fibrate S420) and whose positive electrode material was 4.5V lithium cobalt oxide to prepare a 1.85Ah lithium ion battery;
the following tests were performed:
(1) charge rate performance: the 1C current is 1.85A, and the 3C current is 5.55A; the charge and discharge potential range is 2.75V-4.50V. The charging rate of the 3C at the normal temperature is a ratio of a capacity C2 of the 3C constant current charging to a 1C constant current charging capacity C1.
(2) Cycle performance: the range of charging and discharging potential is 2.75V-4.50V, the charging current is 3C (5.55A) to 4.50V, the charging is carried out at 4.50V with constant voltage until the cut-off current is less than or equal to 0.02C (0.037A), after standing for 5 minutes, 1C (1.85A) is discharged to 2.75V, and the standing is carried out for 5 minutes; thus, the charge and discharge are cycled.
(3) Low-temperature discharge performance: the 1C (1.85A) discharge capacity at 25 ℃ at room temperature was designated as C1, and after full charge at 4.5V and freezing at-20 ℃ for 4 hours, the discharge was 1C (1.85A) to 2.75V, and the discharge capacity was designated as C2. The discharge rate at-20 ℃ was C2/C1.
The test results are summarized in tables 2 to 4.
TABLE 2
TABLE 3
TABLE 4
As can be seen from the analysis of the data in tables 2 to 4, when the electrolyte disclosed by the invention is used in a battery, the multi-aspect performance of the battery is improved by adding the compound shown in the formula I, the 3C discharge rate of the battery obtained by the invention at normal temperature is more than 79.5%, the 1C discharge rate of the battery at 20 ℃ is more than 80.8%, the capacity retention rate of the 3C charge/1C discharge cycle of the battery subjected to 800 cycles at normal temperature is more than 82.6%, the capacity retention rate of the battery subjected to 800 cycles at high temperature of 45 ℃ is more than 81.8%, and the comprehensive performance is excellent.
As can be seen from the analysis of comparative example 1 and example 5, the performance of comparative example 1 is inferior to that of example 5, and the electrolyte added with the compound shown in formula I can improve the comprehensive performance of the battery. Analysis of comparative example 2 and example 11 revealed similar results. The electrolyte added with the compound shown in the formula I is proved to be beneficial to taking a silicon-containing material or graphite as a negative electrode and the charge-discharge cycle performance and the low-temperature discharge performance of a ternary material or a cobalt acid lithium battery.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (10)
2. the fluoroalkyl borate containing electrolyte of claim 1 wherein said electrolyte comprises XClO4、XPF6、XBF4、XTFSI、XFSI、XBOB、XODFB,XCF3SO3Or XAsF6Any one or a combination of at least two of them; wherein X is Li, Na or K.
3. The fluoroalkyl borate compound containing electrolyte of claim 1, wherein the organic solvent comprises any one of carbonate, carboxylate, fluorocarboxylate, propionate, fluoroether, or aromatic hydrocarbon or a combination of at least two thereof.
4. The fluoroalkyl borate containing compound electrolyte of claim 1 wherein said carbonate comprises a halogenated carbonate and/or a non-halogenated carbonate; the non-halogenated carbonate comprises any one or the combination of at least two of ethylene carbonate, propylene carbonate, diethyl carbonate, dimethyl carbonate or ethyl methyl carbonate; the halogenated carbonate comprises any one or the combination of at least two of fluoroethylene carbonate, difluoroethylene carbonate, difluoropropylene carbonate, ethyl trifluoroacetate, trifluoroethyl methyl carbonate, trifluoromethyl ethylene carbonate, 4-trifluoromethyl ethylene carbonate, chloroethylene carbonate, bis (2,2, 2-trifluoroethyl) carbonate, methyl trifluoropropionate, 3,3, 3-trifluoro ethyl acetate, 2-trifluoromethyl methyl benzoate, 4,4, 4-trifluoro ethyl butyrate or 1,1,1,3,3, 3-hexafluoroisopropyl acrylate.
5. The fluoroalkyl borate containing compound electrolyte of claim 1 wherein said carboxylate comprises halogenated carboxylate and/or non-halogenated carboxylate; the non-halogenated carboxylic acid ester comprises any one or a combination of at least two of propyl butyrate, propyl acetate, isopropyl acetate, butyl propionate, isopropyl propionate, ethyl butyrate, methyl propionate, ethyl propionate or propyl propionate; the halogenated carboxylic acid ester comprises any one or a combination of at least two of propyl fluorobutyrate, propyl fluoroacetate, isopropyl fluoroacetate, butyl fluoropropionate, isopropyl fluoropropionate, ethyl fluorobutyrate, methyl fluoropropionate, ethyl fluoropropionate and propyl fluoropropionate.
6. The electrolytic solution containing a fluoroalkyl borate compound according to claim 1, wherein the fluoroether is a fluoroether having 7 or less carbon atoms.
7. The fluoroalkyl borate containing compound electrolyte of claim 1 wherein said aromatic hydrocarbon comprises halogenated aromatic hydrocarbons and/or non-halogenated aromatic hydrocarbons; the halogenated aromatic hydrocarbon comprises any one or the combination of at least two of monofluorobenzene, difluorobenzene, 1,3, 5-trifluorobenzene, trifluorotoluene, 2-fluorotoluene or 2, 4-dichlorotrifluorotoluene.
8. The fluoroalkyl borate containing compound electrolyte of claim 1 wherein the weight percentage of said electrolyte in said electrolyte is 8-49%; the weight percentage of the organic solvent in the electrolyte is 1-85%; the fluorine-containing alkyl borate compound shown in the formula I accounts for 0.01-50% of the electrolyte.
9. A battery comprising the electrolyte of any one of claims 1-8.
10. The battery of claim 1, wherein the battery comprises a lithium ion battery, a sodium ion battery, a potassium ion battery, or a supercapacitor; the negative electrode material of the lithium ion battery comprises any one or the combination of at least two of graphite, soft carbon, hard carbon, a composite material of monocrystalline silicon and graphite, a composite material of silicon oxide and graphite, and lithium titanate or niobium pentoxide.
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