CN116565306A - High-migration-number composite solid electrolyte and preparation method and application thereof - Google Patents
High-migration-number composite solid electrolyte and preparation method and application thereof Download PDFInfo
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- CN116565306A CN116565306A CN202310237004.0A CN202310237004A CN116565306A CN 116565306 A CN116565306 A CN 116565306A CN 202310237004 A CN202310237004 A CN 202310237004A CN 116565306 A CN116565306 A CN 116565306A
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- 239000002131 composite material Substances 0.000 title claims abstract description 65
- 239000007784 solid electrolyte Substances 0.000 title claims abstract description 57
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000001301 oxygen Substances 0.000 claims abstract description 36
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 36
- 229920000642 polymer Polymers 0.000 claims abstract description 24
- 239000012784 inorganic fiber Substances 0.000 claims abstract description 22
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 14
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 14
- 239000007787 solid Substances 0.000 claims abstract description 14
- 239000000835 fiber Substances 0.000 claims description 30
- 239000003792 electrolyte Substances 0.000 claims description 21
- 229910052744 lithium Inorganic materials 0.000 claims description 17
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 16
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 16
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 15
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 15
- 239000000654 additive Substances 0.000 claims description 14
- 230000000996 additive effect Effects 0.000 claims description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 11
- 239000006185 dispersion Substances 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 9
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 9
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- 239000002033 PVDF binder Substances 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- MCVFFRWZNYZUIJ-UHFFFAOYSA-M lithium;trifluoromethanesulfonate Chemical compound [Li+].[O-]S(=O)(=O)C(F)(F)F MCVFFRWZNYZUIJ-UHFFFAOYSA-M 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- -1 polyethylene terephthalate Polymers 0.000 claims description 6
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 6
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 5
- 238000001291 vacuum drying Methods 0.000 claims description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- 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 description 4
- 239000004014 plasticizer Substances 0.000 claims description 4
- 239000002243 precursor Substances 0.000 claims description 4
- 229910003480 inorganic solid Inorganic materials 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims description 2
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 2
- 239000004696 Poly ether ether ketone Substances 0.000 claims description 2
- 239000004695 Polyether sulfone Substances 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- 229920002873 Polyethylenimine Polymers 0.000 claims description 2
- 239000004642 Polyimide Substances 0.000 claims description 2
- 229920003235 aromatic polyamide Polymers 0.000 claims description 2
- 229920002678 cellulose Polymers 0.000 claims description 2
- 239000001913 cellulose Substances 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 239000003431 cross linking reagent Substances 0.000 claims description 2
- 239000003063 flame retardant Substances 0.000 claims description 2
- 229920001002 functional polymer Polymers 0.000 claims description 2
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 claims description 2
- 229910001486 lithium perchlorate Inorganic materials 0.000 claims description 2
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 claims 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 claims description 2
- IGILRSKEFZLPKG-UHFFFAOYSA-M lithium;difluorophosphinate Chemical compound [Li+].[O-]P(F)(F)=O IGILRSKEFZLPKG-UHFFFAOYSA-M 0.000 claims description 2
- 229910044991 metal oxide Inorganic materials 0.000 claims description 2
- 229910052755 nonmetal Inorganic materials 0.000 claims description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 2
- 229920005569 poly(vinylidene fluoride-co-hexafluoropropylene) Polymers 0.000 claims description 2
- 229920002401 polyacrylamide Polymers 0.000 claims description 2
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 2
- 229920006393 polyether sulfone Polymers 0.000 claims description 2
- 229920002530 polyetherether ketone Polymers 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 2
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 2
- 229920001721 polyimide Polymers 0.000 claims description 2
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 2
- 229920001451 polypropylene glycol Polymers 0.000 claims description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 2
- 239000000758 substrate Substances 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- ZJPPTKRSFKBZMD-UHFFFAOYSA-N [Li].FS(=N)F Chemical compound [Li].FS(=N)F ZJPPTKRSFKBZMD-UHFFFAOYSA-N 0.000 claims 1
- JJYJSKHTGGQVMD-UHFFFAOYSA-N [Li].[SH2]=N.FC(F)F.FC(F)F Chemical compound [Li].[SH2]=N.FC(F)F.FC(F)F JJYJSKHTGGQVMD-UHFFFAOYSA-N 0.000 claims 1
- 239000012298 atmosphere Substances 0.000 claims 1
- 229920013636 polyphenyl ether polymer Polymers 0.000 claims 1
- 230000001681 protective effect Effects 0.000 claims 1
- 238000013508 migration Methods 0.000 abstract description 18
- 230000005012 migration Effects 0.000 abstract description 18
- 229910010272 inorganic material Inorganic materials 0.000 abstract description 4
- 239000011147 inorganic material Substances 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 3
- 230000003321 amplification Effects 0.000 abstract 1
- 238000003199 nucleic acid amplification method Methods 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 11
- SMBQBQBNOXIFSF-UHFFFAOYSA-N dilithium Chemical compound [Li][Li] SMBQBQBNOXIFSF-UHFFFAOYSA-N 0.000 description 9
- 239000012300 argon atmosphere Substances 0.000 description 8
- 150000002500 ions Chemical class 0.000 description 8
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 5
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 description 5
- 229910001416 lithium ion Inorganic materials 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- NCZYUKGXRHBAHE-UHFFFAOYSA-K [Li+].P(=O)([O-])([O-])[O-].[Fe+2].[Li+] Chemical compound [Li+].P(=O)([O-])([O-])[O-].[Fe+2].[Li+] NCZYUKGXRHBAHE-UHFFFAOYSA-K 0.000 description 4
- 238000001000 micrograph Methods 0.000 description 4
- 210000004027 cell Anatomy 0.000 description 3
- VWYHCWVXCWCOPV-UHFFFAOYSA-L dilithium trifluoromethanesulfonate Chemical compound [Li+].[Li+].[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F VWYHCWVXCWCOPV-UHFFFAOYSA-L 0.000 description 3
- 238000002955 isolation Methods 0.000 description 3
- 239000011244 liquid electrolyte Substances 0.000 description 3
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 3
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 230000009471 action Effects 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
- 238000013459 approach Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 239000011267 electrode slurry Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000003203 everyday effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229920006380 polyphenylene oxide Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
-
- 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
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0085—Immobilising or gelification of electrolyte
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Electrochemistry (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Dispersion Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Physics & Mathematics (AREA)
- Materials Engineering (AREA)
- Secondary Cells (AREA)
Abstract
The invention relates to a high migration number composite solid electrolyte and a preparation method and application thereof, wherein the high migration number composite solid electrolyte comprises inorganic fibers containing oxygen vacancies, polymers and lithium salts, the addition of the inorganic fibers containing the oxygen vacancies can improve the ion conductivity and migration number of the composite solid electrolyte, fibrous inorganic materials can provide larger specific surface area, the amplification of the promotion effect is facilitated, and a solid battery using the composite solid electrolyte shows good electrochemical performance and cycle stability.
Description
Technical Field
The invention relates to the technical field of solid electrolytes, in particular to a high-migration-number composite solid electrolyte, and a preparation method and application thereof.
Background
Lithium ion batteries have been attracting attention since the first advent, have been developed over the last three decades, and have been widely used in the production and life from the everyday consumer scenarios of electronic products, electric car lights, to large-scale power station storage. The current lithium ion battery mainly uses organic liquid electrolyte, but with the decreasing of marginal effect, the current lithium ion battery based on liquid electrolyte can not meet the actual requirement of continuous development, besides the energy density of the lithium ion battery gradually approaches to the safety boundary, the safety risk of inflammability and easy leakage of the lithium ion battery is more and more not ignored, the liquid electrolyte is replaced by solid electrolyte, the production and application of the solid lithium battery are realized, the energy density of the battery is further improved, the safety of the battery is improved, and the battery is further promoted to be applied to electric automobile, airplane, ship and power station level electric energy storage.
The existing solid electrolyte can be mainly divided into polymer solid electrolyte and inorganic solid electrolyte, wherein the polymer solid electrolyte has the advantages of low cost, flexibility and low processing difficulty, but also has the defects of low ion conductivity and low migration number, the reduced ion conductivity influences the normal use of the composite solid electrolyte at room temperature, the lower migration number can influence the stability of an interface between an electrode and the electrolyte, the rapid growth of lithium dendrites is caused, the existing mainstream technical means is to add inorganic materials to prepare the composite solid electrolyte, the improvement measures can improve the ion conductivity of the composite solid electrolyte, but the problem of low migration number of the composite solid electrolyte still lacks an effective strategy, so that the novel composite solid electrolyte is urgently required to be developed, and has high ion conductivity and high migration number.
Disclosure of Invention
The invention aims to provide a high-migration-number composite solid electrolyte, a preparation method and application thereof, and solves the problems in the background technology.
In order to achieve the above purpose, the present invention provides the following technical solutions: an inorganic ceramic composite solid state electrolyte comprising: inorganic fibers containing oxygen vacancies, polymers, and lithium salts.
In some embodiments of the present invention, the oxygen vacancy-containing inorganic fibers are selected from oxygen vacancy-containing single or multi-metal oxide fibers, oxygen vacancy-containing non-metal oxygen-containing compound fibers, and oxygen vacancy-containing inorganic solid state electrolyte fibers, preferably oxygen vacancy-containing titanium oxide fibers and oxygen vacancy-containing silicon oxide fibers. The inorganic fiber content of the oxygen-containing vacancy is 1-60% by weight, preferably 10-30% by weight. The diameter of the inorganic fiber containing oxygen vacancies is 0.05 μm to 2. Mu.m, preferably 0.1 μm to 0.5. Mu.m.
In some embodiments of the invention, the polymer is one or more of polyethylene glycol, polyethylene oxide, polyvinylpyrrolidone, polypropylene oxide, polyethylene imine, polyacrylamide, polymethyl methacrylate, polyethylene terephthalate, polyvinylidene fluoride, poly (vinylidene fluoride-co-hexafluoropropylene), polyacrylonitrile, polyimide, polyethersulfone, polyphenylene oxide, polyaramid, polyetheretherketone, cellulose, and the like. Polyethylene oxide and polyvinylidene fluoride are preferred. The content of the polymer in the composite solid electrolyte is 5% to 95%, preferably 40% to 70%.
In some embodiments of the invention, the lithium salt is at least one of lithium dioxalate borate, lithium difluorosulfonimide, lithium difluorophosphate, lithium difluorooxalato borate, lithium trifluoromethane sulfonate, lithium tetrafluoroborate, lithium hexafluorophosphate, lithium bistrifluoromethylsulfonimide, and lithium perchlorate. Preferred are lithium bis (trifluoromethylsulfonyl) imide, lithium dioxaborate and lithium trifluoromethylsulfonate. The molar ratio of the lithium salt to the polymer repeating units is 1:1 to 1:20, preferably 1:1 to 1:14.
The invention also provides a preparation method of the high-mobility composite solid electrolyte, which is characterized by comprising the following steps of: in a dry environment, inorganic fibers containing oxygen vacancies, a polymer, lithium salt and an additive are mixed with an organic solvent to obtain a precursor dispersion liquid, the precursor dispersion liquid is coated on a planar substrate, and the composite solid electrolyte is obtained by drying under normal pressure and then vacuum drying.
The oxygen vacancy-containing inorganic fibers, polymers, and lithium salts comprise the high mobility composite solid state electrolyte as claimed in any one of claims 1 to 4.
The additive comprises one or more of polymer plasticizer, cross-linking agent, negative electrode film-forming agent, positive electrode film-forming agent, antifreezing additive, flame retardant additive, overcharge-preventing additive, functional polymer and inorganic additive. The additive accounts for 0% -20% of the total weight of the composite solid electrolyte, and preferably 5% -10%.
The organic solvent comprises at least one of acetonitrile, tetrahydrofuran, dichloromethane, chloroform, N-dimethylformamide, N-dimethylacetamide and N-methylpyrrolidone. The mass ratio of the organic solvent to the polymer is 6:1-25:1, preferably 15:1-20:1.
The drying temperature is 20-45 ℃, preferably 30-35 ℃ and the drying time is 4-72 h, preferably 12-24 h under normal pressure; the vacuum drying and drying temperature is 30-120 ℃, preferably 40-60 ℃ for 4-72 hours, preferably 12-24 hours.
The invention also provides a solid-state lithium battery, which is characterized by comprising the high-migration-number composite solid-state electrolyte prepared by the high-migration-number composite solid-state electrolyte or the preparation method of the high-migration-number composite solid-state electrolyte.
Compared with the prior art, the invention has the following beneficial effects:
the high migration number composite solid electrolyte provided by the invention has the advantages that the inorganic fiber containing oxygen vacancies, the polymer and the lithium salt are compounded, the inorganic fiber has larger length-diameter ratio, the mechanical strength of the polymer is improved, the flexibility of the polymer is not obviously lost, the characteristics of hardness and softness are shown, meanwhile, the dissociation of the lithium salt can be promoted, the ion conductivity is improved, the anions are anchored, the migration number of the composite electrolyte is improved, and the fibrous inorganic material can provide larger specific surface area to further promote the action of the oxygen vacancies in the inorganic material due to the coulomb interaction of the oxygen vacancies and the anions in the lithium salt;
the preparation method of the high-mobility composite solid electrolyte provided by the invention has simple process and is suitable for large-scale production;
the high-mobility composite solid electrolyte provided by the invention is applied to a solid lithium battery, has good cycling stability, and has great application potential in the field of solid lithium batteries.
Drawings
Other features, objects and advantages of the present invention will become more apparent upon reading of the detailed description of non-limiting embodiments, given with reference to the accompanying drawings in which:
FIG. 1 is an X-ray diffraction spectrum of a titanium oxide fiber using titanium oxide fibers and oxygen-containing vacancies in example 1 and comparative example 1 of the present invention;
FIG. 2 is a scanning electron microscope image of a titanium oxide fiber containing oxygen vacancies used in example 1 of the present invention;
FIG. 3 is a scanning electron microscope image of comparative example 1 of the present invention using titanium oxide fibers;
FIG. 4 is a scanning electron microscope image of a silicon oxide fiber containing oxygen vacancies used in example 2 of the present invention;
FIG. 5 is a scanning electron microscope image of comparative example 2 in which silica fibers were used according to the present invention;
FIG. 6 is a cycle curve at 0.5mA/cm2 of current for a lithium-lithium symmetric cell containing a high mobility composite solid electrolyte prepared in example 1 of the present invention;
FIG. 7 is a charge and discharge curve of the lithium-iron phosphate soft pack battery containing the high mobility composite solid state electrolyte prepared in example 1 of the present invention at the first and 100 th weeks at C/3 current density;
FIG. 8 is a cycle curve at 1mA/cm2 of a current for a lithium-lithium symmetric cell containing a high mobility composite solid electrolyte prepared in example 2 of the present invention;
fig. 9 is a charge and discharge curve of a lithium-ternary nickel cobalt manganese 811 oxide pouch cell prepared in example 2 of the present invention containing a high mobility solid state electrolyte at C/3 current density at the first and 100 th weeks.
Detailed Description
Example 1
Under the condition of argon atmosphere, adding 30 mass percent of titanium oxide fibers containing oxygen vacancies, fully dispersing in 12g of acetonitrile, adding 13.6mmol of lithium bistrifluoromethane sulfonate and 0.6g of polyethylene oxide until the titanium oxide fibers are completely dissolved, adding 10 percent of ethylene carbonate as a plasticizer, drying the obtained dispersion liquid at 30 ℃ for 24 hours under the argon atmosphere, and then drying at 40 ℃ for 24 hours under the vacuum condition to obtain the high-mobility composite solid electrolyte, wherein the ion conductivity at room temperature is 1.1mS/cm, and the mobility number is 0.78. The composite solid electrolyte is applied to a lithium-lithium symmetrical battery and a lithium-lithium iron phosphate soft package battery to obtain the battery containing the polymer solid electrolyte.
Example 2
Under the condition of argon atmosphere, adding 10 mass percent of silicon oxide fiber containing oxygen vacancies, fully dispersing the silicon oxide fiber in 9g of N-methylpyrrolidone, adding 0.17mmol of lithium dioxalate borate, 0.5mmol of lithium trifluoromethane sulfonate and 0.6g of polyvinylidene fluoride until the silicon oxide fiber is completely dissolved, adding 5 percent of fluoroethylene carbonate as a negative film forming agent, drying the obtained dispersion liquid for 12 hours at 35 ℃ in the argon atmosphere, and then drying the dispersion liquid for 12 hours at 60 ℃ in the vacuum condition to obtain the high-migration-number composite solid electrolyte, wherein the ion conductivity at room temperature is 0.8mS/cm and the migration number is 0.8, and the composite solid electrolyte is applied to a lithium-lithium symmetrical battery and a lithium-ternary nickel cobalt manganese 811 oxide soft package battery to obtain the battery containing the polymer solid electrolyte.
Comparative example 1
Under the condition of argon atmosphere, adding 30 mass percent of titanium oxide fiber, fully dispersing in 12g of acetonitrile, adding 13.6mmol of lithium bistrifluoromethane sulfonate and 0.6g of polyethylene oxide until the lithium bistrifluoromethane sulfonate and the polyethylene oxide are completely dissolved, adding 10 percent of ethylene carbonate as a plasticizer, drying the obtained dispersion liquid for 24 hours at 30 ℃ under the argon atmosphere, and then drying for 24 hours at 40 ℃ under the vacuum condition to obtain the high migration number composite solid electrolyte, wherein the ion conductivity at room temperature is 0.3mS/cm and the migration number is 0.32.
Comparative example 2
Under the condition of argon atmosphere, adding 10 mass percent of silicon oxide fiber, fully dispersing in 9g of N-methyl pyrrolidone, adding 0.17mmol of lithium dioxalate borate, 0.5mmol of lithium trifluoromethane sulfonate and 0.6g of polyvinylidene fluoride until the silicon oxide fiber is completely dissolved, adding 5 mass percent of fluoroethylene carbonate as a negative electrode film forming agent, drying the obtained dispersion liquid for 12 hours at 35 ℃ under the argon atmosphere, and then drying for 12 hours at 60 ℃ under the vacuum condition to obtain the high-migration-number composite solid electrolyte, wherein the ionic conductivity at room temperature is 0.2mS/cm and the migration number is 0.24.
The effect of inorganic fibers containing oxygen vacancies on the composite solid electrolyte performance was analyzed as follows:
the difference between the phases is described in example 1 and comparative example 1 using the X-ray diffraction spectra of the titanium oxide fiber and the titanium oxide fiber containing oxygen vacancies (fig. 1), the titanium oxide being anatase-phase titanium oxide and the titanium oxide fiber containing oxygen vacancies being Magneli-phase tetratitanium heptaoxide.
Scanning electron microscope pictures of the inorganic fibers used in the example 1, the comparative example 1, the example 2 and the comparative example 2 are respectively shown in fig. 2 to 5, and the morphology of the inorganic fibers used in the example 1 and the comparative example 1 is similar.
By comparing the electrolytes prepared in example 1 and comparative example 1, example 2 and comparative example 2, respectively, it was found that under the same experimental conditions, the morphology of the inorganic fibers was similar, the difference was only whether the inorganic fibers contained oxygen vacancies, and that the composite solid electrolyte using the titanium oxide fibers containing oxygen vacancies was found to exhibit higher ionic conductivity and migration number, indicating that the use of the titanium oxide fibers containing oxygen vacancies and the silicon oxide fibers containing oxygen vacancies was favorable for improving the ionic conductivity and migration number of the composite solid electrolyte, and it was reasonably speculated that all the inorganic fibers containing oxygen vacancies were likely to improve the ionic conductivity and migration number of the composite solid electrolyte.
The solid-state batteries prepared in the examples were each tested according to the following method:
the method comprises the steps of taking metallic lithium as a negative electrode, taking a prepared high migration number composite solid electrolyte as a positive electrode isolation film, taking a positive electrode plate of lithium iron phosphate or ternary nickel cobalt manganese 811 oxide as a positive electrode, assembling a soft package battery, preparing a positive electrode plate, uniformly mixing the positive electrode powder of the lithium iron phosphate or ternary nickel cobalt manganese 811, the composite solid electrolyte and conductive carbon black in a mass ratio of 93:3:4 in acetonitrile or N-methylpyrrolidone to obtain positive electrode slurry, further coating the slurry on the surface of a carbon-coated aluminum foil, vacuum drying to obtain the positive electrode plate, taking the metallic lithium as the positive electrode and the negative electrode of a lithium-lithium symmetrical battery, taking the prepared high migration number composite solid electrolyte as the positive electrode isolation film and the positive electrode isolation film, assembling the button battery, and carrying out charge and discharge tests on the assembled battery by using a LAND battery charge and discharge instrument.
Example battery performance test results:
the composite solid electrolyte prepared in example 1 is subjected to lithium-lithium symmetric battery cycle test, and is charged and discharged under 0.5mA/cm < 2 >, the result is shown in fig. 6, the battery is cycled for 500 hours without obvious voltage polarization increase, which shows that the composite solid electrolyte has good stability to lithium metal, and further, the composite solid electrolyte prepared in example 1 is subjected to lithium-lithium iron phosphate soft-pack battery cycle test, and the result is shown in fig. 7, the initial cycle coulomb efficiency of the lithium-lithium iron phosphate soft-pack battery is as high as 98%, and the initial cycle discharge specific capacity is 153.1mAh/g; after 100 weeks circulation under the condition of C/3, the specific discharge capacity is 152.6mAh/g, and the 100 weeks circulation capacity retention rate is as high as 99.6%.
The lithium-lithium symmetric battery cycle test is carried out on the composite solid electrolyte prepared in the example 2, the lithium-lithium symmetric battery is charged and discharged under the condition of 1mA/cm < 2 >, the result is shown in figure 8, the lithium-lithium symmetric battery is stable in cycle within 600 hours, the lithium metal stability of the composite solid electrolyte is good, further, the lithium-lithium iron phosphate soft-packed battery cycle test is carried out on the composite solid electrolyte prepared in the example 2, the result is shown in figure 9, the initial cycle coulomb efficiency of the lithium-ternary nickel cobalt manganese 811 oxide soft-packed battery is up to 96%, and the initial cycle discharge specific capacity is 199.5mAh/g; after 100 weeks circulation under the condition of C/3, the specific discharge capacity is 187.4mAh/g, and the 100 weeks circulation capacity retention rate is as high as 93.9%.
Therefore, the solid-state battery using the high-mobility composite solid-state electrolyte has the advantages of excellent performance, simple preparation method and process and suitability for large-scale production, and has great application value in the field of solid-state lithium batteries.
It will be readily appreciated by those skilled in the art that the foregoing description is merely a preferred embodiment of the invention and is not intended to limit the invention, but any modifications, equivalents, improvements or alternatives falling within the spirit and principles of the invention are intended to be included within the scope of the invention.
Claims (10)
1. A high mobility composite solid state electrolyte comprising:
inorganic fibers containing oxygen vacancies, polymers, and lithium salts.
2. The high mobility composite solid state electrolyte of claim 1 wherein: the oxygen-vacancy containing inorganic fibers are selected from the group consisting of oxygen-vacancy containing single or multi-metal oxide fibers, oxygen-vacancy containing non-metal oxygen-containing compound fibers and oxygen-vacancy containing inorganic solid electrolyte fibers, preferably oxygen-vacancy containing titanium oxide fibers and oxygen-vacancy containing silicon oxide fibers. The inorganic fiber content of the oxygen-containing vacancy is 1-60% by weight, preferably 10-30% by weight. The diameter of the inorganic fiber containing oxygen vacancies is 0.05 μm to 2. Mu.m, preferably 0.1 μm to 0.5. Mu.m.
3. The high mobility composite solid state electrolyte of claim 1 wherein: the polymer is one or more of polyethylene glycol, polyethylene oxide, polyvinylpyrrolidone, polypropylene oxide, polyethyleneimine, polyacrylamide, polymethyl methacrylate, polyethylene terephthalate, polyvinylidene fluoride, poly (vinylidene fluoride-co-hexafluoropropylene), polyacrylonitrile, polyimide, polyether sulfone, polyphenyl ether, polyaramid, polyether ether ketone, cellulose and the like. Polyethylene oxide and polyvinylidene fluoride are preferred. The content of the polymer in the composite solid electrolyte is 5% to 95%, preferably 40% to 70%.
4. The high mobility composite solid state electrolyte of claim 1 wherein: the lithium salt is at least one of lithium dioxalate borate, lithium difluorosulfimide, lithium difluorophosphate, lithium difluorooxalato borate, lithium trifluoromethane sulfonate, lithium tetrafluoroborate, lithium hexafluorophosphate, lithium bistrifluoromethane sulfimide and lithium perchlorate. Preferred are lithium bis (trifluoromethylsulfonyl) imide, lithium dioxaborate and lithium trifluoromethylsulfonate. The molar ratio of the lithium salt to the polymer repeating units is 1:1 to 1:20, preferably 1:1 to 1:14.
5. The preparation method of the high-migration-number composite solid electrolyte is characterized by comprising the following steps of: in a protective atmosphere environment, inorganic fibers containing oxygen vacancies, a polymer, lithium salt and an additive are mixed with an organic solvent to obtain a precursor dispersion liquid, the precursor dispersion liquid is coated on a planar substrate, and the composite solid electrolyte is obtained by drying under normal pressure and then vacuum drying.
6. A method of preparing a high mobility composite solid state electrolyte as defined in claim 5, wherein the oxygen vacancy-containing inorganic fibers, polymers and lithium salts comprise the high mobility composite solid state electrolyte as defined in any one of claims 1 to 4.
7. The method for preparing the high-mobility composite solid electrolyte according to claim 5, wherein the additive comprises one or more of a polymer plasticizer, a cross-linking agent, a negative electrode film-forming agent, a positive electrode film-forming agent, an antifreezing additive, a flame retardant additive, an overcharge-preventing additive, a functional polymer and an inorganic additive. The additive accounts for 0% -20% of the total weight of the composite solid electrolyte, and preferably 5% -10%.
8. The method for preparing a high mobility composite solid electrolyte as claimed in claim 5, wherein the organic solvent comprises at least one of acetonitrile, tetrahydrofuran, dichloromethane, chloroform, N-dimethylformamide, N-dimethylacetamide, and N-methylpyrrolidone. The mass ratio of the organic solvent to the polymer is 6:1-25:1, preferably 15:1-20:1.
9. The method for preparing a high mobility composite solid electrolyte as claimed in claim 5, wherein the drying temperature is 20-45 ℃, preferably 30 ℃ under normal pressure, and the time is 4-72 hours, preferably 12-24 hours; the vacuum drying and drying temperature is 30-120 ℃, preferably 40-60 ℃ for 4-72 hours, preferably 12-24 hours.
10. A solid-state lithium battery comprising the high-mobility composite solid-state electrolyte according to any one of claims 1 to 4 or the high-mobility composite solid-state electrolyte produced by the method for producing a high-mobility composite solid-state electrolyte according to any one of claims 5 to 9.
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