CN118136964A - Electrolyte, secondary battery and electricity utilization device - Google Patents
Electrolyte, secondary battery and electricity utilization device Download PDFInfo
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- CN118136964A CN118136964A CN202410576481.4A CN202410576481A CN118136964A CN 118136964 A CN118136964 A CN 118136964A CN 202410576481 A CN202410576481 A CN 202410576481A CN 118136964 A CN118136964 A CN 118136964A
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- 239000003792 electrolyte Substances 0.000 title claims abstract description 113
- 230000005611 electricity Effects 0.000 title description 3
- 239000002904 solvent Substances 0.000 claims abstract description 103
- 239000002608 ionic liquid Substances 0.000 claims abstract description 50
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 48
- GKTNLYAAZKKMTQ-UHFFFAOYSA-N n-[bis(dimethylamino)phosphinimyl]-n-methylmethanamine Chemical compound CN(C)P(=N)(N(C)C)N(C)C GKTNLYAAZKKMTQ-UHFFFAOYSA-N 0.000 claims abstract description 42
- 229920001774 Perfluoroether Polymers 0.000 claims abstract description 38
- 238000000034 method Methods 0.000 claims abstract description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 44
- 229910003002 lithium salt Inorganic materials 0.000 claims description 39
- 159000000002 lithium salts Chemical class 0.000 claims description 39
- -1 methoxyethyl Chemical group 0.000 claims description 35
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 26
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 20
- 150000001450 anions Chemical class 0.000 claims description 12
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- 150000001768 cations Chemical class 0.000 claims description 6
- GRPIQKZLNSCFTB-UHFFFAOYSA-N n-[bis(dimethylamino)-fluoroimino-$l^{5}-phosphanyl]-n-methylmethanamine Chemical compound CN(C)P(=NF)(N(C)C)N(C)C GRPIQKZLNSCFTB-UHFFFAOYSA-N 0.000 claims description 4
- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 claims description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 3
- DKQPXAWBVGCNHG-UHFFFAOYSA-N 2,2,4,4,6,6-hexafluoro-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound FP1(F)=NP(F)(F)=NP(F)(F)=N1 DKQPXAWBVGCNHG-UHFFFAOYSA-N 0.000 claims description 3
- XNZZEQCBAGUFMT-UHFFFAOYSA-N 2,2,4,4,6-pentafluoro-6-phenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound FP1(F)=NP(F)(F)=NP(F)(OC=2C=CC=CC=2)=N1 XNZZEQCBAGUFMT-UHFFFAOYSA-N 0.000 claims description 3
- CBTAIOOTRCAMBD-UHFFFAOYSA-N 2-ethoxy-2,4,4,6,6-pentafluoro-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound CCOP1(F)=NP(F)(F)=NP(F)(F)=N1 CBTAIOOTRCAMBD-UHFFFAOYSA-N 0.000 claims description 3
- 229910000733 Li alloy Inorganic materials 0.000 claims description 3
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 claims description 3
- 125000005448 ethoxyethyl group Chemical group [H]C([H])([H])C([H])([H])OC([H])([H])C([H])([H])* 0.000 claims description 3
- KLKFAASOGCDTDT-UHFFFAOYSA-N ethoxymethoxyethane Chemical compound CCOCOCC KLKFAASOGCDTDT-UHFFFAOYSA-N 0.000 claims description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- 150000003949 imides Chemical class 0.000 claims description 3
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 3
- 239000001989 lithium alloy Substances 0.000 claims description 3
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 claims description 3
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 3
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 3
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 claims description 3
- 125000006225 propoxyethyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])OC([H])([H])C([H])([H])* 0.000 claims description 3
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- VDFVNEFVBPFDSB-UHFFFAOYSA-N 1,3-dioxane Chemical compound C1COCOC1 VDFVNEFVBPFDSB-UHFFFAOYSA-N 0.000 claims description 2
- 229910001486 lithium perchlorate Inorganic materials 0.000 claims description 2
- OBTWBSRJZRCYQV-UHFFFAOYSA-N sulfuryl difluoride Chemical group FS(F)(=O)=O OBTWBSRJZRCYQV-UHFFFAOYSA-N 0.000 claims description 2
- SYRDSFGUUQPYOB-UHFFFAOYSA-N [Li+].[Li+].[Li+].[O-]B([O-])[O-].FC(=O)C(F)=O Chemical compound [Li+].[Li+].[Li+].[O-]B([O-])[O-].FC(=O)C(F)=O SYRDSFGUUQPYOB-UHFFFAOYSA-N 0.000 claims 1
- DEUISMFZZMAAOJ-UHFFFAOYSA-N lithium dihydrogen borate oxalic acid Chemical compound B([O-])(O)O.C(C(=O)O)(=O)O.C(C(=O)O)(=O)O.[Li+] DEUISMFZZMAAOJ-UHFFFAOYSA-N 0.000 claims 1
- 210000001787 dendrite Anatomy 0.000 abstract description 17
- 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 abstract description 12
- 230000000694 effects Effects 0.000 abstract description 12
- 239000003063 flame retardant Substances 0.000 abstract description 12
- 230000002401 inhibitory effect Effects 0.000 abstract description 4
- 230000008569 process Effects 0.000 abstract description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 23
- 229910001416 lithium ion Inorganic materials 0.000 description 23
- 238000007614 solvation Methods 0.000 description 8
- 230000008021 deposition Effects 0.000 description 6
- 230000009286 beneficial effect Effects 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 210000004027 cell Anatomy 0.000 description 4
- 239000008151 electrolyte solution Substances 0.000 description 4
- 230000000670 limiting effect Effects 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 3
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000001276 controlling effect Effects 0.000 description 3
- 230000001351 cycling effect Effects 0.000 description 3
- 239000011267 electrode slurry Substances 0.000 description 3
- 229940021013 electrolyte solution Drugs 0.000 description 3
- 239000007774 positive electrode material Substances 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 125000001153 fluoro group Chemical group F* 0.000 description 2
- 238000002955 isolation Methods 0.000 description 2
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 description 2
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 2
- 229910021437 lithium-transition metal oxide Inorganic materials 0.000 description 2
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 description 2
- ILXAVRFGLBYNEJ-UHFFFAOYSA-K lithium;manganese(2+);phosphate Chemical compound [Li+].[Mn+2].[O-]P([O-])([O-])=O ILXAVRFGLBYNEJ-UHFFFAOYSA-K 0.000 description 2
- 238000004768 lowest unoccupied molecular orbital Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000011356 non-aqueous organic solvent Substances 0.000 description 2
- 235000021317 phosphate Nutrition 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 125000004191 (C1-C6) alkoxy group Chemical group 0.000 description 1
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 description 1
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 1
- 229910013063 LiBF 4 Inorganic materials 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- 229910000572 Lithium Nickel Cobalt Manganese Oxide (NCM) Inorganic materials 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- VIEVWNYBKMKQIH-UHFFFAOYSA-N [Co]=O.[Mn].[Li] Chemical compound [Co]=O.[Mn].[Li] VIEVWNYBKMKQIH-UHFFFAOYSA-N 0.000 description 1
- QTHKJEYUQSLYTH-UHFFFAOYSA-N [Co]=O.[Ni].[Li] Chemical compound [Co]=O.[Ni].[Li] QTHKJEYUQSLYTH-UHFFFAOYSA-N 0.000 description 1
- FBDMTTNVIIVBKI-UHFFFAOYSA-N [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] Chemical compound [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] FBDMTTNVIIVBKI-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- VHSLGFZDYCMVHY-UHFFFAOYSA-N boric acid;oxalyl difluoride Chemical compound OB(O)O.FC(=O)C(F)=O VHSLGFZDYCMVHY-UHFFFAOYSA-N 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 238000004807 desolvation Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000004210 ether based solvent Substances 0.000 description 1
- 230000003090 exacerbative effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000003273 ketjen black Substances 0.000 description 1
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 description 1
- 229910002102 lithium manganese oxide Inorganic materials 0.000 description 1
- FRMOHNDAXZZWQI-UHFFFAOYSA-N lithium manganese(2+) nickel(2+) oxygen(2-) Chemical compound [O-2].[Mn+2].[Ni+2].[Li+] FRMOHNDAXZZWQI-UHFFFAOYSA-N 0.000 description 1
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 description 1
- VLXXBCXTUVRROQ-UHFFFAOYSA-N lithium;oxido-oxo-(oxomanganiooxy)manganese Chemical compound [Li+].[O-][Mn](=O)O[Mn]=O VLXXBCXTUVRROQ-UHFFFAOYSA-N 0.000 description 1
- URIIGZKXFBNRAU-UHFFFAOYSA-N lithium;oxonickel Chemical compound [Li].[Ni]=O URIIGZKXFBNRAU-UHFFFAOYSA-N 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000005677 organic carbonates Chemical class 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 239000012453 solvate Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000002459 sustained effect Effects 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-M triflate Chemical compound [O-]S(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-M 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
- H01M10/052—Li-accumulators
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0025—Organic electrolyte
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Secondary Cells (AREA)
Abstract
The application discloses electrolyte, a secondary battery and an electric device, and relates to the technical field of batteries. The electrolyte comprises a fluoroether solvent, a pyrrole-type ionic liquid and a phosphazene solvent. The electrolyte provided by the application has the effect of inhibiting the growth of dendrites of the lithium metal cathode when being used for a secondary power utilization device, is intrinsically flame-retardant, thereby improving the cycle life and the safety performance of the lithium metal secondary battery, is suitable for the existing battery process system, and has the characteristics of convenience and economy.
Description
Technical Field
The application relates to the technical field of batteries, in particular to electrolyte, a secondary battery and an electric device.
Background
Lithium metal has the lowest electrochemical potential (-3.04V vs. SHE), the ultrahigh theoretical specific capacity (mAh. G -1) and the low density (0.534 g. Cm -3) at the same time, and is an ideal anode for the next-generation high-energy-density battery.
However, it encounters a great obstacle in practical use: on the one hand, lithium metal cannot generate stable SEI in commercial electrolyte, and uneven lithium deposition leads to continuous growth of dendrite and dead lithium, continuous consumption of electrolyte and active lithium, low coulombic efficiency and cycle life; on the other hand, the sustained growth of dendrites tends to puncture the separator causing internal shorting of the cell and releasing a large amount of heat, while the organic commercial electrolyte contains a large amount of flammable non-aqueous organic solvents further exacerbating the combustion or even explosion of the cell. Therefore, there is a strong need to develop an electrolyte suitable for use in secondary batteries.
Disclosure of Invention
In view of the above, the present application provides an electrolyte, which has an effect of inhibiting dendrite growth of a lithium metal negative electrode and is intrinsically flame retardant, a secondary battery, and an electric device.
The first aspect of the application provides an electrolyte, which comprises a fluoroether solvent, a pyrrole-type ionic liquid and a phosphazene solvent.
In some embodiments of the application, the phosphazene solvent comprises a fluorophosphazene;
and/or the phosphazene solvent accounts for 0.1 to 20 percent of the electrolyte by mass;
And/or the pyrrole type ionic liquid accounts for 5-60% of the electrolyte by mass.
In some embodiments of the present application, the fluoroether solvent accounts for 5-60% of the electrolyte by mass;
and/or the phosphazene solvent comprises at least one of hexafluoro-cyclotriphosphazene, ethoxy pentafluoro-cyclotriphosphazene and phenoxy pentafluoro-cyclotriphosphazene;
And/or the viscosity of the electrolyte is 2.0 cP-8.5 cP;
and/or the conductivity of the electrolyte is 5.0 mS/cm-8.5/mS/cm.
In some embodiments of the present application, the fluoroether solvent is selected from 1, 2-tetrafluoroethyl ether 1, 2-tetrafluoroethyl-2, 2-trifluoroethyl ether, 1, 2-tetrafluoroethyl-2, 3-tetrafluoropropyl ether 1, 2-tetrafluoroethyl-2, 2-trifluoroethyl ether 1, 2-tetrafluoroethyl-2, 3-tetrafluoropropyl ether.
In some embodiments of the application, the cation of the pyrrole-type ionic liquid comprises a structure represented by formula 1,
The method comprises the steps of (1),
Wherein R1 and R2 are each independently selected from one of methyl, ethyl, n-propyl, n-butyl, isopropyl, isobutyl, sec-butyl, tert-butyl, methoxyethyl, ethoxyethyl, and propoxyethyl;
And/or the anions of the pyrrole type ionic liquid comprise one or more of difluoro-sulfonyl imide anions, bis-trifluoro-methanesulfonimide anions, trifluoro-methanesulfonate anions, dinitrile amine anions, tetrafluoroborate anions, hexafluorophosphate anions, perchlorate anions, dioxalate borate anions and difluorooxalate borate anions.
In some embodiments of the present application, the electrolyte further includes a lithium salt, wherein the lithium salt accounts for 5-40% of the electrolyte by mass;
And/or the electrolyte further comprises lithium salt, wherein the concentration of the lithium salt in the electrolyte is more than 3.0M/L.
In some embodiments of the application, the lithium salt is selected from at least one of lithium hexafluorophosphate, lithium tetrafluoroborate, lithium dioxaborate, lithium difluorooxalato borate, lithium perchlorate, lithium bistrifluoromethylsulfonate imide, lithium bistrifluoromethylsulfonyl imide, and lithium 2,2- (trifluoromethyl) sulfonyl-N-cyanamide.
In some embodiments of the application, the electrolyte further comprises an ether solvent selected from any one or a combination of at least two of ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethoxymethane, bis (2-methoxyethyl) ether, 1, 4-dioxane, 1, 3-dioxolane, and tetrahydrofuran.
A second aspect of the present application provides a secondary battery including a positive electrode, a negative electrode, and the electrolyte; the negative electrode includes at least one of lithium metal and lithium alloy.
In a third aspect, the present application provides an electrical device comprising the electrolyte.
A fourth aspect of the present application provides an electric device including the secondary battery.
The beneficial effects are that:
The invention provides the electrolyte which has the effect of inhibiting the growth of dendrites of the lithium metal cathode when being used for a secondary power utilization device, and is intrinsically flame-retardant, so that the cycle life and the safety performance of the lithium metal secondary battery are improved.
Detailed Description
The following description will clearly and fully describe the technical solutions of the embodiments of the present application, and it is apparent that the described embodiments are only some embodiments of the present application, not all embodiments. All other embodiments, which can be made by a person skilled in the art without making any inventive effort, are intended to be within the scope of the present application. Furthermore, it should be understood that the detailed description is presented herein for purposes of illustration and description only, and is not intended to limit the application.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. The term "and/or" as used herein includes any and all combinations of one or more of the associated listed items.
In the present application, unless otherwise indicated, terms of orientation such as "upper" and "lower" are used to generally refer to upper and lower positions of the device in actual use or operation; while "inner" and "outer" are for the outline of the device. In addition, in the description of the present application, the term "comprising" means "including but not limited to". The terms first, second, third and the like are used merely as labels, and do not impose numerical requirements or on the order of construction.
In the present application, "and/or" describing the association relationship of the association object means that there may be three relationships, for example, a and/or B may mean: a alone, a and B together, and B alone. Wherein A, B may be singular or plural.
In the present application, "at least one" means one or more, and "a plurality" means two or more. "one or more," "at least one of the following," or the like, refer to any combination of these items, including any combination of single item(s) or plural items(s). For example, "at least one (individual) of a, b, or c," or "at least one (individual) of a, b, and c," may each represent: a, b, c, a-b (i.e., a and b), a-c, b-c, or a-b-c, wherein a, b, c may be single or multiple, respectively.
Various embodiments of the application may exist in a range of forms; it should be understood that the description in a range format is merely for convenience and brevity and should not be construed as a rigid limitation on the scope of the application; it is therefore to be understood that the range description has specifically disclosed all possible sub-ranges and individual values within that range. For example, it should be considered that a description of a range from 1 to 6 has specifically disclosed sub-ranges, such as from 1 to 3, from 1 to 4, from 1 to 5, from 2 to 4, from 2 to 6, from 3 to 6, etc., as well as single numbers within the range, such as1, 2,3, 4, 5, and 6, wherever applicable. In addition, whenever a numerical range is referred to herein, it is meant to include any reference number (fractional or integer) within the indicated range.
It is understood that lithium metal has both the lowest electrochemical potential (-3.04V vs. SHE), the ultra-high theoretical specific capacity (mAh g -1), and the low density (0.534 g cm -3), and is an ideal anode for the next generation of high energy density batteries.
However, lithium metal cannot generate a stable SEI film in commercial electrolyte, taking electrolyte comprising lithium hexafluorophosphate and organic carbonate as an example, SEI generated by decomposition of the electrolyte on a lithium negative electrode has the problem of porosity and looseness, the electrolyte and the lithium metal cannot be blocked, and the lithium metal is continuously consumed by reaction with the electrolyte in the circulation process; and the organic components in SEI are mainly, can not adapt to huge volume change in the lithium deposition process, and have the problem of easy breakage, the surface of fresh lithium leaks to cause uneven interface potential distribution, so that dendrite formation of uneven lithium deposition further causes volume increase, and interface degradation causes low coulombic efficiency and cycle life. In addition, how to solve the contradiction between the flame retardant property and the cycle property of the secondary battery is also a problem to be solved by researchers.
In view of the above, the present application provides an electrolyte suitable for an electric device, which has an effect of inhibiting dendrite growth of a lithium metal negative electrode and is intrinsically flame retardant; the lithium metal secondary battery with the electrolyte has higher cycle life and flame retardant property.
In a first aspect, embodiments of the present application provide an electrolyte comprising a lithium salt, an ether solvent, a fluoroether solvent, a pyrrole-type ionic liquid, and a phosphazene-type solvent. Wherein the lithium salt is used for providing lithium ions. The pyrrole type ionic liquid, the fluoroether solvent and the phosphazene solvent are cooperatively matched, so that the electrolyte has good flame retardance, and has higher cycle life and safety performance when being used for an electric device.
The fluoroether solvent in the present application means an ether solvent in which at least one hydrogen atom is replaced with a fluorine atom. Ionic liquids refer to liquids that are composed entirely of ions. Pyrrole-type ionic liquids refer to ionic liquids whose cations are derived from pyrrolidine and its derivatives.
In the electrolyte, the pyrrole type ionic liquid has low vapor pressure, high thermal stability and incombustibility; the fluoroether solvent and the phosphazene solvent have excellent flame retardance, and the flame retardance of the electrolyte can be effectively improved through the synergistic effect of the fluoroether solvent, the phosphazene solvent and the phosphazene solvent, and the safety performance of the secondary battery is improved.
It is understood that the solvent in the electrolyte is mainly used as a carrier for transporting lithium ions, and solvates lithium salt in the electrolyte to ensure the transportation of lithium ions. The pyrrole type ionic liquid plays a role in regulating and controlling lithium deposition, the reduction potential of cations is lower than that of lithium ions, the pyrrole type ionic liquid competes with the lithium ions to be adsorbed around the dendrites when dendrites exist, and the dendrite growth is inhibited due to the fact that the lithium ions are discharged through larger steric hindrance, anions of the pyrrole type ionic liquid participate in solvation of the lithium ions and formation of SEI, and meanwhile, the ionic liquid has incombustibility due to low vapor pressure and high thermal stability.
When the electrolyte provided by the application is used for a lithium metal secondary battery, due to the charge effect between anions and cations, anions are more distributed in the inner layer of a lithium ion solvation sheath compared with solvent molecules, the LUMO energy level (lowest unoccupied molecular orbital) of the anions of the lithium salt and the ionic liquid is lower than that of the solvent molecules, and the anions are preferentially reduced on the surface of a lithium metal negative electrode to form an SEI film with high inorganic component content. The cationic reduction potential of the pyrrole-type ionic liquid is lower than that of lithium ions, the pyrrole-type ionic liquid and the lithium ions are in competition adsorption around the dendrites when the dendrites exist, and the lithium ions are discharged by means of steric hindrance, so that dendrite growth is inhibited, and the effects of regulating and controlling lithium deposition and improving the safety and the cycling stability of the secondary battery can be further achieved.
Meanwhile, the ether solvent plays a role of competing with anions for solvation, is beneficial to the solvation/desolvation process of lithium ions, reduces the interface transfer impedance of lithium ions, is beneficial to uniform deposition of lithium, and can be used for stably forming a film on lithium metal. The fluoroether solvent does not participate in lithium ion solvation, can regulate and control the size of a lithium ion solvation structure, improves lithium ion transmission kinetics, and plays roles of reducing the viscosity of electrolyte and increasing wettability.
In addition, the phosphazene solvent has weak solvation capability, can promote the interaction of lithium ions and anions, has higher thermal decomposition temperature and flame retardant effect, and can release phosphorus to capture active groups to inhibit combustion reaction at high temperature.
In some embodiments of the present application, the lithium salt, ether solvent, fluoroether solvent, pyrrole-type ionic liquid and phosphazene solvent high concentration system (for example, the lithium salt concentration is more than 3M/L, that is, the lithium salt concentration in the electrolyte is more than 3.0M/L), and the high concentration lithium salt (for example, the lithium salt concentration is more than 3M/L) in the electrolyte can reduce the volatility of the inflammable solvent, so as to further improve the safety and the cycle performance of the secondary lithium battery of the present application.
In some embodiments of the application, the phosphazene machine solvent comprises a fluorophosphazene. The fluorinated phosphazene refers to a phosphazene compound substituted by fluorine-containing elements. The fluoro phosphazene is decomposed at the cathode to generate LiF and defluorinated phosphazene, the LiF has high mechanical property, the SEI stability is improved to inhibit dendrite growth, the defluorinated phosphazene is ring-opening polymerized at the anode to form a protective film, and the anode stability is improved. Illustratively, the phosphazene solvent comprises: any one or a combination of at least two of hexafluoro-cyclotriphosphazene, ethoxy-pentafluoro-cyclotriphosphazene and phenoxy-pentafluoro-cyclotriphosphazene.
In some embodiments of the application, the lithium salt is present in an amount of 5% to 40% by mass, preferably 10% to 30% by mass, based on the total mass of the electrolyte. It will be appreciated that too high a lithium salt content, for example above 40%, the viscosity of the electrolyte is too high, resulting in a lower conductivity; too low a lithium salt content, for example below 5%, the lithium ion content in the electrolyte is less, resulting in a lower conductivity.
Illustratively, the lithium salt comprises from 5% to 10% by mass based on the total mass of the electrolyte; or the mass ratio of the lithium salt is 10% -15%; or the mass ratio of the lithium salt is 15% -20%; or the mass ratio of the lithium salt is 20-25%, or the mass ratio of the lithium salt is 25-30%; or the mass ratio of the lithium salt is 30% -35%; or the mass ratio of the lithium salt is 35-40%. For another example, the lithium salt may be present in a mass ratio of 5%, or 8%, or 10%, or 12%, or 15%, or 18%, or 20%, or 23%, or 25%, or 28%, or 30%, or 32%, or 34%, or 35%, or 36%, or 38%, or 40%, based on the total mass of the electrolyte.
In some embodiments of the application, the ether solvent is present in an amount of 5% to 60% by mass, preferably 10% to 45% by mass, based on the total mass of the electrolyte. It will be appreciated that too high an ether non-aqueous solvent content, e.g. above 60%, does not form high concentrations of lithium salts; the content of the ether nonaqueous solvent is too low, for example, less than 5%, and the lithium salt cannot be dissociated.
Illustratively, the mass ratio of the ether solvent is 5% -10%; or the mass ratio of the lithium salt is 10% -15%; or the mass ratio of the ether solvent is 15% -20%; or the mass ratio of the ether solvent is 20-25%, or the mass ratio of the ether solvent is 25-30%; or the mass ratio of the ether solvent is 30% -35%; or the mass ratio of the ether solvent is 35-40%; or the mass ratio of the ether solvent is 40% -50%; or the mass ratio of the ether solvent is 50-60%. For another example, the ether solvent may be 5%, or 8%, or 10%, or 12%, or 15%, or 18%, or 20%, or 23%, or 25%, or 28%, or 30%, or 35%, or 40%, or 45%, or 50%, or 55%, or 60% by mass based on the total mass of the electrolyte. In some embodiments of the application, the fluoroether solvent is present in an amount of 5% to 60% by mass, preferably 10% to 45% by mass, based on the total mass of the electrolyte. It is understood that if the fluoroether solvent content in the electrolyte is too high, for example, higher than 60%, lithium salts are easily precipitated; if the fluoroether content in the electrolyte is too low, for example, less than 5%, the effect of adding the fluoroether solvent to the electrolyte is not desirable.
Illustratively, the mass ratio of the fluoroether solvent is 5% -10%; or the mass ratio of the fluoroether solvent is 10-15%; or the mass ratio of the fluoroether solvent is 15% -20%; or the mass ratio of the fluoroether solvent is 20-25%, or the mass ratio of the fluoroether solvent is 25-30%; or the mass ratio of the fluoroether solvent is 30% -35%; or the mass ratio of the fluoroether solvent is 35-40%; or the mass ratio of the fluoroether solvent is 40% -50%; or the mass ratio of the fluoroether solvent is 50-60%. For another example, the fluoroether solvent may be 5%, or 8%, or 10%, or 12%, or 15%, or 18%, or 20%, or 23%, or 25%, or 28%, or 30%, or 35%, or 40%, or 45%, or 50%, or 55%, or 60% by mass based on the total mass of the electrolyte.
In some embodiments of the application, the phosphazene solvent is present in an amount of 5 to 60 percent by mass, preferably 2 to 15 percent by mass, based on the total mass of the electrolyte. It will be appreciated that too high a level of phosphazene-based nonaqueous solvent, e.g. above 60%, the viscosity of the electrolyte is too great, resulting in a lower conductivity; if the phosphazene type nonaqueous solvent is too low, for example, less than 5%, the effect of adding the phosphazene type solvent to the electrolyte is not ideal.
Illustratively, the phosphazene solvent accounts for 5-10 percent by mass; or the mass ratio of the phosphazene solvent is 10-15 percent; or the mass ratio of the phosphazene solvent is 15-20 percent; or the mass ratio of the phosphazene solvent is 20-25%, or the mass ratio of the phosphazene solvent is 25-30%; or the mass ratio of the phosphazene solvent is 30-35 percent; or the mass ratio of the phosphazene solvent is 35-40 percent; or the mass ratio of the phosphazene solvent is 40-50%; or the mass ratio of the phosphazene solvent is 50-60 percent. For another example, the phosphazene solvent is 5%, or 8%, or 10%, or 12%, or 15%, or 18%, or 20%, or 23%, or 25%, or 28%, or 30%, or 35%, or 40%, or 45%, or 50%, or 55%, or 60% by mass based on the total mass of the electrolyte.
In some embodiments of the application, the pyrrole-type ionic liquid is present in an amount of 5% to 60% by mass, preferably 10% to 45% by mass, based on the total mass of the electrolyte. It is understood that if the pyrrole-type ionic liquid content in the electrolyte is too high, for example, higher than 60%, the viscosity of the electrolyte is easily excessive, so that the conductivity of the electrolyte is small; if the content of the pyrrole-type ionic liquid in the electrolyte is too low, for example, less than 5%, the effect of adding the pyrrole-type ionic liquid into the electrolyte is not ideal.
Illustratively, the mass ratio of the pyrrole-type ionic liquid is 5% -10% based on the total mass of the electrolyte; or the mass ratio of the pyrrole-type ionic liquid is 10% -15%; or the mass ratio of the pyrrole-type ionic liquid is 15% -20%; or the mass ratio of the pyrrole-type ionic liquid is 20-25%, or the mass ratio of the pyrrole-type ionic liquid is 25-30%; or the mass ratio of the pyrrole-type ionic liquid is 30% -35%; or the mass ratio of the pyrrole-type ionic liquid is 35% -40%; or the mass ratio of the pyrrole-type ionic liquid is 40% -50%; or the mass ratio of the pyrrole-type ionic liquid is 50% -60%. For another example, the pyrrole-type ionic liquid may be 5%, or 8%, or 10%, or 12%, or 15%, or 18%, or 20%, or 23%, or 25%, or 28%, or 30%, or 35%, or 40%, or 45%, or 50%, or 55%, or 60% by mass based on the total mass of the electrolyte.
In some embodiments of the application, the viscosity of the electrolyte is 2.0 cP to 8.5 cP. Further, the viscosity of the electrolyte is 3.0 cP-7.2 cP. Illustratively, the viscosity of the electrolyte is 2.0 cP, 2.5 cP, or 3.0 cP, or 3.5 cP, or 4.0 cP, or 4.5 cP, or 5.0 cP, or 5.9 cP, or 6.1 cP, or 6.7 cP, or 7.2 cP, or 7.5 cP, or 7.8 cP, or 8.0 cP, or 8.2 cP, or 8.5 cP.
In some embodiments of the application, the electrolyte has an electrical conductivity of 5.0 mS/cm to 8.5 mS/cm. Further, the conductivity of the electrolyte is 5.9 mS/cm-7.5/mS/cm. Illustratively, the viscosity of the electrolyte is 5.0 cP, 5.2 cP, or 5.5 cP, or 5.7 cP, or 5.9 cP, or 6.1 cP, or 6.3 cP, or 6.5 cP, or 6.7 cP, or 6.9 cP, or 7.2 cP, or 7.3 cP, or 7.5 cP, or 7.8 cP, or 8.0 cP, or 8.2 cP, or 8.5 cP.
In some embodiments of the application, the lithium salt is selected from any one or a combination of at least two of lithium hexafluorophosphate (LiPF 6), lithium tetrafluoroborate (LiBF 4), lithium dioxaborate (LiBOB), lithium difluorooxalato borate (liodbb), lithium perchlorate (LiClO 4), lithium bis (trifluoromethanesulfonic acid) imide (LiTFSI), lithium bis (trifluoromethanesulfonyl) imide (LiFSI), and lithium 2,2- (trifluoromethyl) sulfonyl-N-cyanamide (LiTFSAM).
In some embodiments of the application, the ether-based nonaqueous organic solvent is selected from any one or a combination of at least two of ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethoxymethane, bis (2-methoxyethyl) ether, 1, 4-dioxane, 1, 3-dioxane and tetrahydrofuran.
In some embodiments of the present application, the fluoroether solvent is selected from 1, 2-tetrafluoroethyl ether 1, 2-tetrafluoroethyl-2, 2-trifluoroethyl ether, 1, 2-tetrafluoroethyl-2, 3-tetrafluoropropyl ether 1, 2-tetrafluoroethyl-2, 2-trifluoroethyl ether 1, 2-tetrafluoroethyl-2, 3-tetrafluoropropyl ether.
In some embodiments of the application, the pyrrole-type ionic liquid cation comprises a structure represented by formula I,
1 (1)
Wherein R1 and R2 each independently comprise one or more of C1-C6 alkyl and C1-C6 alkoxy.
Alternatively, R1, R2 each independently comprises one or more of methyl, ethyl, n-propyl, n-butyl, isopropyl, isobutyl, sec-butyl, tert-butyl, methoxyethyl, ethoxyethyl, propoxyethyl.
The pyrrole-type ionic liquid anions comprise: comprises any one or a combination of at least two of difluoro sulfonimide anions, bis trifluoro methanesulfonimide anions, trifluoro methanesulfonate, dinitrile amine radicals, tetrafluoroborate, hexafluorophosphate, perchlorate, dioxalate borate or difluorooxalate borate.
In a second aspect, the present application provides a method for producing an electrolytic solution, comprising the steps of,
(1) Mixing lithium salt, ionic liquid and ether solvent in preset proportion under inert atmosphere (H 2O＜0.01ppm,O2 is less than 0.01 ppm) to obtain premixed liquid. Illustratively, the lithium salt, ionic liquid and ethereal solvent are stirred and mixed uniformly at 35 ℃.
(2) And adding a fluoroether solvent and a phosphazene solvent with preset contents into the premixed liquid to obtain the lithium metal secondary battery electrolyte. Illustratively, the fluoroether solvent and the phosphazene solvent are sequentially added into the premixed liquid at 35 ℃ and uniformly mixed to obtain the electrolyte.
It can be understood that the fluoroether solvent and the phosphazene solvent have weaker capability of dissolving the lithium salt, can be mutually dissolved with the solvent, and are added after the lithium salt and the ionic liquid are dissolved in the ether solvent, thereby being beneficial to improving the stability of the electrolyte.
A third aspect of the present application provides a secondary battery including a positive electrode, a negative electrode, and an electrolyte; the negative electrode includes at least one of lithium metal and lithium alloy. Wherein the electrolyte comprises a fluoroether solvent, a pyrrole-type ionic liquid and a phosphazene solvent. The above description of the electrolyte is specifically described, and will not be described herein. For the secondary battery taking lithium metal as the negative electrode, as the cationic reduction potential of the pyrrole-type ionic liquid is lower than that of lithium ions, the pyrrole-type ionic liquid competes with the lithium ions to be adsorbed around the dendrites when the dendrites exist, and the dendrite growth is inhibited by means of steric hindrance of the pyrrole-type ionic liquid, so that the effects of regulating and controlling lithium deposition and improving the safety and the cycling stability of the secondary battery can be further achieved. Meanwhile, the fluoroether solvent can regulate and control the size of a lithium ion solvation structure, improve lithium ion transmission dynamics, play roles in reducing the viscosity of electrolyte and increasing wettability, and is beneficial to improving the cycle stability of the battery. In addition, pyrrole-type ionic liquid, fluoroether solvent and phosphazene solvent all have excellent flame retardance. Experiments prove that the electrolyte comprising the fluoroether solvent, the pyrrole-type ionic liquid and the phosphazene solvent has higher cycle life and safety performance when being used for an electric device, and effectively solves the problem of contradiction between the flame retardant performance and the cycle performance of the secondary battery.
In some embodiments, the secondary battery includes a positive electrode tab including a positive electrode current collector and a positive electrode film layer disposed on at least one surface of the positive electrode current collector, the positive electrode film layer including a positive electrode active material.
In some embodiments, the positive electrode active material includes lithium-containing phosphates, lithium transition metal oxides, and their respective modifying compounds. The lithium transition metal oxide includes, but is not limited to, lithium cobalt oxide, lithium nickel oxide, lithium manganese oxide, lithium nickel cobalt oxide, lithium manganese cobalt oxide, lithium nickel manganese oxide, lithium nickel cobalt manganese oxide. The lithium-containing phosphate includes, but is not limited to, at least one of lithium iron phosphate, a composite of lithium iron phosphate and carbon, lithium manganese phosphate, a composite of lithium manganese phosphate and carbon.
A fourth aspect of the present application provides an electric device comprising the electrolyte; or the electricity consumption device comprises the secondary battery. Hereinafter, embodiments of the present application are described. The following examples are illustrative only and are not to be construed as limiting the application. The examples are not to be construed as limiting the specific techniques or conditions described in the literature in this field or as per the specifications of the product. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
Example 1
(1) Preparation of electrolyte
In an argon atmosphere glove box (H 2O<0.01ppm,O2 <0.01 ppm), 10 parts by mass of lithium dioxaborate, 25 parts by mass of N-methoxyethyl-N-methylpyrrolidine dinitrile amine salt (Py 1EOEN (CN) 2), 25 parts by mass of ethylene glycol dimethyl ether were taken and mixed at 35 ℃, and the above-prepared solution was mixed with 25 parts by mass of 1, 2-tetrafluoroethyl-2, 3-tetrafluoropropyl ether and 15 parts by mass of fluorocyclotriphosphazene at 35 ℃ to obtain an electrolyte of example 1.
(2) Preparation of positive pole piece
Mixing 96wt% of positive electrode active material lithium cobaltate, 2wt% of conductive agent ketjen black and 2wt% of binder polyvinylidene fluoride, adding N-methyl pyrrolidone, stirring and dispersing to obtain positive electrode slurry. And then coating the positive electrode slurry on an aluminum foil, and drying, cold pressing, cutting and preparing the positive electrode plate after the positive electrode slurry is finished.
(3) Preparation of negative pole piece
Lithium metal was used as the negative electrode tab.
(4) Isolation film
Polyethylene film is used as isolating film.
(5) Battery preparation
And the positive pole piece, the isolating film and the negative pole piece are sequentially stacked, so that the isolating film is positioned in the middle of the positive pole and the negative pole to play a role in isolation. And placing the bare cell in an outer package, injecting the prepared electrolyte, and performing the procedures of packaging, liquid injection, formation, exhaust and the like to obtain the lithium ion battery.
Examples 2 to 6, and comparative examples 1 to 3 only differ in electrolyte solutions, and refer to table 1.
Performance test:
(1) Electrolyte viscosity test
The viscosity of the electrolyte is measured at 25 ℃ by using a Bowler-femto DV2TLV viscometer according to the GB/T10247-2008 standard, and the rotor is LV-1.
(2) Electrolyte conductivity test
The conductivity of the 25℃electrolyte was measured at 25℃using a OrionStarA222 conductivity meter.
(3) Electrolyte flame retardant property test
Step 1: 1mL of the electrolyte was taken in a steel vessel at 25℃in a non-closed environment. Step 2: the electrolyte is burned by using blue external flame of a high temperature windproof lighter at 1000 ℃ and timing is started. Step 3: the application of the flame was suspended every 5 seconds, and it was observed whether the electrolyte itself produced a visible flame. Step 4: repeating the step 3 for n times until the electrolyte generates visible flame. Step 5: flame retardant timeWherein n is the number of times step 3 is repeated, and the flame retardant time is in seconds(s).
(4) Cycling stability test of batteries
The battery was allowed to stand at 25℃for 30min, discharged to 2.75V at a constant current of 1C, charged to 4.3V at a constant current of 1C after 5min of standing, charged to a cutoff current of 0.05C at a constant voltage, discharged to 2.75V at a constant current of 1C after 5min of standing, and the test cell capacity was noted as initial capacity (C0). After standing for 5min, repeating the above steps for the same battery, and recording the discharge capacity (Cn) of the battery after the nth cycle, and recording the number of cycles when the battery cycle capacity retention rate Pn (pn=cn/c0×100%) is 80%.
TABLE 1
From examples 1 to 6 in table 1, it is apparent that the electrolyte solutions contain both the fluoroether solvent, the pyrrole-type ionic liquid and the phosphazene solvent, and that the electrolyte solutions having high flame retardancy can be obtained.
In addition, as can be seen from examples 1 and 6, the addition of the ether solvent to the electrolyte of the present application can significantly increase the cycle number of the battery, so that the obtained electrolyte has high conductivity, good flame retardant effect and cycle number.
Furthermore, it is known from the combination of comparative examples 1 to 3 that the fluoroether-based solvent, the pyrrole-based ionic liquid, the ether-based solvent and the phosphazene-based solvent have a synergistic effect in improving the flame retardancy and the cycle number of the electrolyte.
The foregoing has outlined the detailed description of the embodiments of the present application, and the detailed description of the principles and embodiments of the present application is provided herein by way of example only to facilitate the understanding of the method and core concepts of the present application; meanwhile, as those skilled in the art will have variations in the specific embodiments and application scope in light of the ideas of the present application, the present description should not be construed as limiting the present application.
Claims (10)
1. An electrolyte is characterized by comprising a fluoroether solvent, an pyrrole-type ionic liquid and a phosphazene solvent.
2. The electrolyte of claim 1 wherein the phosphazene solvent comprises a fluorophosphazene;
and/or the phosphazene solvent accounts for 0.1 to 20 percent of the electrolyte by mass;
And/or the pyrrole type ionic liquid accounts for 5-60% of the electrolyte by mass.
3. The electrolyte according to claim 1, wherein the fluoroether solvent accounts for 5-60% of the electrolyte by mass;
and/or the phosphazene solvent comprises at least one of hexafluoro-cyclotriphosphazene, ethoxy pentafluoro-cyclotriphosphazene and phenoxy pentafluoro-cyclotriphosphazene;
And/or the viscosity of the electrolyte is 2.0 cP-8.5 cP;
and/or the conductivity of the electrolyte is 5.0 mS/cm-8.5/mS/cm.
4. The electrolyte of claim 1, wherein, the fluoroether solvent is selected from 1, 2-tetrafluoroethyl ether 1, 2-tetrafluoroethyl-2, 2-trifluoroethyl ether, 1, 2-tetrafluoroethyl-2, 3-tetrafluoropropyl ether 1, 2-tetrafluoroethyl-2, 2-trifluoroethyl ether 1, 2-tetrafluoroethyl-2, 3-tetrafluoropropyl ether.
5. The electrolyte of claim 1, wherein the cation of the pyrrole-type ionic liquid comprises a structure represented by formula 1,
The method comprises the steps of (1),
Wherein R1 and R2 are each independently selected from one of methyl, ethyl, n-propyl, n-butyl, isopropyl, isobutyl, sec-butyl, tert-butyl, methoxyethyl, ethoxyethyl, and propoxyethyl;
And/or the anions of the pyrrole type ionic liquid comprise one or more of difluoro-sulfonyl imide anions, bis-trifluoro-methanesulfonimide anions, trifluoro-methanesulfonate anions, dinitrile amine anions, tetrafluoroborate anions, hexafluorophosphate anions, perchlorate anions, dioxalate borate anions and difluorooxalate borate anions.
6. The electrolyte of claim 1, further comprising a lithium salt, wherein the lithium salt comprises 5-40% by mass of the electrolyte;
And/or the electrolyte further comprises lithium salt, wherein the concentration of the lithium salt in the electrolyte is more than 3.0M/L.
7. The electrolyte of claim 6 wherein the lithium salt is selected from at least one of lithium hexafluorophosphate, lithium tetrafluoroborate, lithium dioxalate borate, lithium difluorooxalate borate, lithium perchlorate, lithium bistrifluoromethylsulfonate imide, and lithium 2,2- (trifluoromethyl) sulfonyl-N-cyanamide.
8. The electrolyte of claim 1, further comprising an ether solvent selected from any one or a combination of at least two of ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethoxymethane, bis (2-methoxyethyl) ether, 1, 4-dioxane, 1, 3-dioxane, and tetrahydrofuran.
9. A secondary battery comprising a positive electrode, a negative electrode, and the electrolyte according to any one of claims 1 to 8; the negative electrode includes at least one of lithium metal and lithium alloy.
10. An electric device, characterized in that it comprises the electrolyte according to any one of claims 1 to 8; or the electricity-using device includes the secondary battery according to claim 9.
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| WO2009028567A1 (en) * | 2007-08-27 | 2009-03-05 | Bridgestone Corporation | Nonaqueous electrolyte solution for battery and nonaqueous electrolyte battery comprising the same |
| CN109860712A (en) * | 2019-03-29 | 2019-06-07 | 山东海容电源材料股份有限公司 | A kind of fire-retardant nonaqueous electrolytic solution of high safety |
| US20220336859A1 (en) * | 2021-04-07 | 2022-10-20 | Global Graphene Group, Inc. | Method of producing flame-resistant quasi-solid electrolytes and lithium batteries containing same |
| CN114421000A (en) * | 2022-01-20 | 2022-04-29 | 惠州亿纬锂能股份有限公司 | A lithium metal secondary battery electrolyte |
| CN117352849A (en) * | 2023-10-27 | 2024-01-05 | 深圳欣视界科技有限公司 | Electrolyte, secondary battery and electricity utilization device |
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