CN110828754B - Inorganic fast ion conductor nano fiber and preparation method and application thereof - Google Patents
Inorganic fast ion conductor nano fiber and preparation method and application thereof Download PDFInfo
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- CN110828754B CN110828754B CN201911143176.1A CN201911143176A CN110828754B CN 110828754 B CN110828754 B CN 110828754B CN 201911143176 A CN201911143176 A CN 201911143176A CN 110828754 B CN110828754 B CN 110828754B
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- 239000010416 ion conductor Substances 0.000 title claims abstract description 47
- 239000002121 nanofiber Substances 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 35
- 238000009987 spinning Methods 0.000 claims abstract description 80
- 239000002131 composite material Substances 0.000 claims abstract description 69
- 239000002243 precursor Substances 0.000 claims abstract description 37
- 239000003792 electrolyte Substances 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 16
- 238000005245 sintering Methods 0.000 claims abstract description 14
- 238000004519 manufacturing process Methods 0.000 claims abstract description 12
- 239000007784 solid electrolyte Substances 0.000 claims description 52
- 239000010408 film Substances 0.000 claims description 47
- 239000000243 solution Substances 0.000 claims description 37
- 229920000642 polymer Polymers 0.000 claims description 27
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-dimethylformamide Substances CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 26
- 238000003756 stirring Methods 0.000 claims description 25
- 238000010438 heat treatment Methods 0.000 claims description 23
- 239000012528 membrane Substances 0.000 claims description 22
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 21
- 238000001816 cooling Methods 0.000 claims description 19
- 239000000835 fiber Substances 0.000 claims description 19
- 229910003002 lithium salt Inorganic materials 0.000 claims description 17
- 159000000002 lithium salts Chemical class 0.000 claims description 17
- 239000002002 slurry Substances 0.000 claims description 16
- 229910052744 lithium Inorganic materials 0.000 claims description 15
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 12
- 239000003960 organic solvent Substances 0.000 claims description 10
- 239000010409 thin film Substances 0.000 claims description 10
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 9
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 9
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 9
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 9
- 238000005507 spraying Methods 0.000 claims description 9
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 8
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 8
- 230000032683 aging Effects 0.000 claims description 8
- 239000011248 coating agent Substances 0.000 claims description 8
- 238000000576 coating method Methods 0.000 claims description 8
- 229910001416 lithium ion Inorganic materials 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- 239000011259 mixed solution Substances 0.000 claims description 8
- 150000003839 salts Chemical class 0.000 claims description 8
- 229960000583 acetic acid Drugs 0.000 claims description 7
- 239000012362 glacial acetic acid Substances 0.000 claims description 7
- -1 lithium hexafluorophosphate Chemical compound 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- 239000002033 PVDF binder Substances 0.000 claims description 5
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 5
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims description 4
- 229920002689 polyvinyl acetate Polymers 0.000 claims description 4
- 239000011118 polyvinyl acetate Substances 0.000 claims description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 3
- 150000003949 imides Chemical class 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
- 229910001486 lithium perchlorate Inorganic materials 0.000 claims description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 3
- 229910052715 tantalum Inorganic materials 0.000 claims description 3
- 229910011244 Li3xLa2/3-xTiO3 Inorganic materials 0.000 claims description 2
- 229910011245 Li3xLa2/3−xTiO3 Inorganic materials 0.000 claims description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- 239000004793 Polystyrene Substances 0.000 claims description 2
- 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 2
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 claims description 2
- 239000011159 matrix material Substances 0.000 claims description 2
- LGRLWUINFJPLSH-UHFFFAOYSA-N methanide Chemical compound [CH3-] LGRLWUINFJPLSH-UHFFFAOYSA-N 0.000 claims description 2
- 229910052758 niobium Inorganic materials 0.000 claims description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 2
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 2
- 229920001451 polypropylene glycol Polymers 0.000 claims description 2
- 229920002223 polystyrene Polymers 0.000 claims description 2
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 2
- 239000004800 polyvinyl chloride Substances 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 239000000758 substrate Substances 0.000 claims description 2
- 125000001889 triflyl group Chemical group FC(F)(F)S(*)(=O)=O 0.000 claims description 2
- QGVDSWMSHDZOMW-UHFFFAOYSA-N 1,3,2-dioxathiolane Chemical compound C1COSO1 QGVDSWMSHDZOMW-UHFFFAOYSA-N 0.000 claims 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims 1
- 229910052797 bismuth Inorganic materials 0.000 claims 1
- 230000009286 beneficial effect Effects 0.000 abstract description 5
- 230000003068 static effect Effects 0.000 abstract description 4
- 239000005518 polymer electrolyte Substances 0.000 description 13
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 12
- 238000005516 engineering process Methods 0.000 description 7
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 238000010998 test method Methods 0.000 description 5
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- UJVRJBAUJYZFIX-UHFFFAOYSA-N nitric acid;oxozirconium Chemical compound [Zr]=O.O[N+]([O-])=O.O[N+]([O-])=O UJVRJBAUJYZFIX-UHFFFAOYSA-N 0.000 description 3
- 239000005279 LLTO - Lithium Lanthanum Titanium Oxide Substances 0.000 description 2
- 229910020721 Li0.33La0.557TiO3 Inorganic materials 0.000 description 2
- 229910002984 Li7La3Zr2O12 Inorganic materials 0.000 description 2
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 238000001523 electrospinning Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- 230000002269 spontaneous effect Effects 0.000 description 2
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 2
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 1
- 229910009274 Li1.4Al0.4Ti1.6 (PO4)3 Inorganic materials 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- GQOQEIGQPCWXLJ-UHFFFAOYSA-N O1OS1.C=C Chemical compound O1OS1.C=C GQOQEIGQPCWXLJ-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 1
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 229910003480 inorganic solid Inorganic materials 0.000 description 1
- 239000011244 liquid electrolyte Substances 0.000 description 1
- 229910000664 lithium aluminum titanium phosphates (LATP) Inorganic materials 0.000 description 1
- 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 1
- 235000019837 monoammonium phosphate Nutrition 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/403—Manufacturing processes of separators, membranes or diaphragms
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0565—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
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/431—Inorganic material
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/44—Fibrous material
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- 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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- Condensed Matter Physics & Semiconductors (AREA)
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Abstract
The invention provides an inorganic fast ion conductor nanofiber and a preparation method and application thereof, wherein the preparation method of the inorganic fast ion conductor nanofiber comprises the following steps: carrying out airflow bubble spinning on the spinning precursor solution, and then carrying out high-temperature sintering to obtain the inorganic fast ion conductor nanofiber; the inorganic fast ion conductor nanofiber prepared by the airflow bubble spinning method has the advantages of simple preparation process, high production efficiency, capability of avoiding being carried out under high-voltage static of ten thousand volts, and potential safety hazard reduction; the composite all-solid-state electrolyte film prepared by the inorganic fast ion conductor nano-fiber has higher mechanical property and ionic conductivity, and is beneficial to improving the dynamic property and the cycle service life of the solid-state battery.
Description
Technical Field
The invention belongs to the field of fibers, and relates to an inorganic fast ion conductor nanofiber, a preparation method and application thereof, in particular to an inorganic fast ion conductor nanofiber, a composite all-solid-state electrolyte film, a preparation method and application thereof, and further relates to a preparation method of the inorganic fast ion conductor nanofiber.
Background
The lithium ion battery is popular with the new energy automobile industry due to the characteristics of high energy density, low self-discharge rate, high cycle efficiency, long cycle life and the like, and is greatly developed. However, the current lithium ion battery technology is not mature, and the problem of unstable safety still exists. The annual increase of the new energy automobile sales is accompanied by the increase of safety accidents, wherein the spontaneous combustion of the battery accounts for a higher reason than the accidents. The cause of spontaneous combustion is thermal runaway due to a large amount of heat released from a lithium ion battery in a short time after internal or external short circuits occur, and the temperature rises very sharply. Commercial lithium ion batteries generally employ an organic liquid electrolyte, which is ignited at high temperature, and eventually causes the batteries to catch fire or explode.
Compared with the traditional lithium ion battery, the electrolyte used by the all-solid-state lithium battery is a solid electrolyte, and the most outstanding advantage is safety. The all-solid-state electrolyte has the characteristics of incombustibility, high temperature resistance, no corrosion and no volatilization, avoids the phenomena of electrolyte leakage, electrode short circuit and the like in the traditional lithium ion battery, reduces the sensitivity of the battery pack to the temperature and eradicates potential safety hazards. Meanwhile, the insulating property of the all-solid-state electrolyte enables the all-solid-state electrolyte to well separate the anode and the cathode of the battery, so that the all-solid-state electrolyte can be used as a diaphragm while the anode and the cathode are prevented from being in contact with each other to generate short circuit. Common solid electrolytes are classified into polymeric solid electrolytes and inorganic solid electrolytes, but they have respective advantages and disadvantages.
Therefore, it is necessary to provide a composite all-solid electrolyte thin film having high production efficiency, high ionic conductivity and good mechanical properties.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide an inorganic fast ion conductor nanofiber and a preparation method and application thereof, in particular to an inorganic fast ion conductor nanofiber, a composite all-solid-state electrolyte film and a preparation method and application thereof, wherein the preparation method of the inorganic fast ion conductor nanofiber by adopting an airflow bubble spinning method has the advantages of simple preparation process and high production efficiency, can be carried out under the high-voltage static of tens of thousands of volts, and reduces the potential safety hazard; the composite all-solid-state electrolyte film prepared by the inorganic fast ion conductor nano-fiber has higher mechanical property and ionic conductivity, and is beneficial to improving the dynamic property and the cycle service life of the solid-state battery.
One of the objectives of the present invention is to provide a method for preparing inorganic fast ion conductor nanofibers, which comprises: and (3) carrying out airflow bubble spinning on the spinning precursor solution, and then carrying out high-temperature sintering to obtain the inorganic fast ion conductor nanofiber.
In the invention, the preparation of the inorganic fast ion conductor nano-fiber by adopting the airflow bubble spinning method has the advantages of simple preparation process and high production efficiency, can be carried out under high-voltage static of ten thousand volts, and reduces the potential safety hazard; the composite all-solid-state electrolyte film prepared by the inorganic fast ion conductor nano-fiber has higher mechanical property and ionic conductivity, and is beneficial to improving the dynamic property and the cycle service life of the solid-state battery.
In the present invention, the preparation method of the spinning precursor solution comprises: and adding metal salt and a high molecular polymer into an organic solvent, mixing and aging to obtain the spinning precursor solution.
In the present invention, the chemical formula of the metal salt includes Li3xLa2/3-xTiO3、Li1+yAlyTi2-y(PO4)3Or Li7- zLa3Zr2-zMzO12Any one or a combination of at least two of (a) 0.04 < x < 0.2 (e.g., x can be 0.04, 0.05, 0.08, 0.1, 0.12, 0.15, 0.17, 0.2, etc.), 0.1 < y < 0.6 (e.g., 0.1, 0.15, 0.2, 0.25, 0.3, 0.35, 0.4, 0.45, 0.5, 0.55, 0.6, etc.), 0 < z < 2 (e.g., 0, 0.2, 0.5, 0.7, 1, 1.2, 1.5, 1.7, 2, etc.), and M is any one of Ta, Nb, or Bi.
In the present invention, the concentration of the metal salt in the spinning precursor solution is 0.05 to 2.5mol/L, for example, 0.05mol/L, 0.2mol/L, 0.5mol/L, 0.7mol/L, 1mol/L, 1.2mol/L, 1.5mol/L, 1.7mol/L, 2mol/L, etc.
In the present invention, the high molecular polymer includes any one or a combination of at least two of polyvinylpyrrolidone, polyvinyl alcohol, polyvinyl butyral, polyvinyl acetate, polyvinylidene fluoride, polyethylene oxide, and polyacrylonitrile.
In the present invention, the number average molecular weight of the high molecular polymer is 20 to 150 ten thousand, for example, 20 ten thousand, 30 ten thousand, 40 ten thousand, 50 ten thousand, 60 ten thousand, 70 ten thousand, 80 ten thousand, 90 ten thousand, 100 ten thousand, 110 ten thousand, 120 ten thousand, 130 ten thousand, 140 ten thousand, 150 ten thousand, or the like.
In the present invention, the concentration of the polymer in the spinning precursor solution is 0.03 to 0.20Kg/L, such as 0.03Kg/L, 0.05Kg/L, 0.08Kg/L, 0.10Kg/L, 0.12Kg/L, 0.15Kg/L, 0.18Kg/L, 0.20Kg/L, etc.
In the present invention, the organic solvent includes any one of ethanol, ethylene glycol, isopropyl alcohol, acetylacetone, glacial acetic acid, or N, N-dimethylformamide, or a combination of at least two thereof.
In the present invention, the mixing is performed under stirring conditions.
In the present invention, the temperature of the aging is 15 to 40 ℃, for example, 15 ℃, 18 ℃, 20 ℃, 22 ℃, 25 ℃, 27 ℃, 30 ℃, 32 ℃, 35 ℃, 37 ℃, 40 ℃ and the like.
In the present invention, the aging time is 6 to 12 hours, such as 6 hours, 7 hours, 8 hours, 9 hours, 10 hours, 11 hours, 12 hours and the like.
In the present invention, the air bubble spinning comprises: applying a gas flow to the spinning precursor solution generates bubbles, and then the generated bubbles are broken and stretch-jetted.
In the present invention, the flow rate for generating the bubbles is 2 to 10L/min, for example, 2L/min, 3L/min, 4L/min, 5L/min, 6L/min, 7L/min, 8L/min, 9L/min, 10L/min, etc.
In the present invention, the gas flow rate in the gas field at which the bubbles collapse is 400-1200L/min, such as 400L/min, 500L/min, 600L/min, 700L/min, 800L/min, 900L/min, 1000L/min, 1100L/min, 1200L/min, etc.
In the present invention, the spinning pitch of the bubble air spinning is 10 to 25cm, for example, 10cm, 12cm, 15cm, 17cm, 20cm, 22cm, 25cm, etc.
In the present invention, the high-temperature sintering is performed in a high-temperature furnace.
In the invention, the preparation method further comprises drying the fiber obtained by air bubble spinning.
In the present invention, the drying temperature is 50 to 100 ℃, for example, 50 ℃, 55 ℃, 60 ℃, 65 ℃, 70 ℃, 75 ℃, 80 ℃, 85 ℃, 90 ℃, 95 ℃, 100 ℃ and the like.
In the present invention, the drying time is 5 to 15 hours, such as 5 hours, 6 hours, 7 hours, 8 hours, 9 hours, 10 hours, 11 hours, 12 hours, 13 hours, 14 hours, 15 hours and the like.
In the present invention, the high-temperature sintering includes: firstly, heating from 25 ℃ to 500 ℃ at a heating rate of 2-5 ℃/min (such as 2 ℃/min, 2.5 ℃/min, 3 ℃/min, 3.5 ℃/min, 4 ℃/min, 4.5 ℃/min, 5 ℃/min and the like), and keeping the temperature for 1-2h (such as 1h, 1.2h, 1.5h, 1.7h, 2h and the like); secondly, heating up from 500 ℃ to 700 plus 1000 ℃ (e.g. 700 ℃, 750 ℃, 800 ℃, 850 ℃, 900 ℃, 950 ℃, 1000 ℃ and the like) at a heating rate of 5-10 ℃/min (e.g. 5 ℃/min, 6 ℃/min, 7 ℃/min, 8 ℃/min, 9 ℃/min, 10 ℃/min and the like), and preserving heat for 2-6h (e.g. 2h, 2.5h, 3h, 3.5h, 4h, 4.5h, 5h, 5.5h, 6h and the like); thirdly, cooling from 700-1000 deg.C (e.g., 700 deg.C, 750 deg.C, 800 deg.C, 850 deg.C, 900 deg.C, 950 deg.C, 1000 deg.C, etc.) to 25 deg.C at a cooling rate of 5-10 deg.C/min (e.g., 5 deg.C/min, 6 deg.C/min, 7 deg.C/min, 8 deg.C/min, 9 deg.C/min, 10 deg.C/min, etc.).
As a preferred technical scheme of the invention, the preparation method comprises the following steps:
(1) dissolving metal salt and high molecular polymer in an organic solvent under the condition of stirring, and aging for 6-12h at 15-40 ℃ to obtain the spinning precursor solution.
(2) And (2) performing air flow bubble spinning on the spinning precursor solution obtained in the step (1), applying 2-10L/min air flow to the spinning precursor solution to generate bubbles, then breaking the generated bubbles in an air flow field of 400-1200L/min, stretching and spraying, wherein the spinning interval is 10-25cm, and then drying at 50-100 ℃ for 5-15h to obtain the spinning fiber.
(3) And (3) sintering the spinning fiber obtained in the step (2) in a high-temperature furnace in three steps, wherein in the first step, the temperature is increased from 25 ℃ to 500 ℃ at the temperature increase rate of 2-5 ℃/min, and the temperature is kept for 1-2 h. Secondly, heating from 500 ℃ to 700 ℃ at the heating rate of 5-10 ℃/min, and preserving the heat for 2-6 h. And thirdly, cooling from 1000 ℃ to 25 ℃ at the cooling rate of 5-10 ℃/min from 700-.
The second purpose of the invention is to provide the inorganic fast ion conductor nano fiber prepared by the preparation method of the first purpose.
The third objective of the present invention is to provide a composite all-solid electrolyte film, which comprises a high molecular polymer, a lithium salt and the second objective of the inorganic fast ion conductor nanofibers.
In the invention, the lithium salt has high ionic conductivity and wide electrochemical window, but the solid/solid interface contact between the lithium salt and the electrode is poor, and the application of the lithium salt is restricted by the problems of sensitivity to humidity and air and the like; the high molecular polymer has good flexibility and solid/solid interface contact between electrodes, but the ionic conductivity is low, and the electrochemical window is narrow; the composite all-solid electrolyte film obtained by matching the two electrolyte films has the characteristics of high ionic conductivity, good electrochemical stability, good mechanical property, easy molding and the like.
In the present invention, the composite all-solid electrolyte thin film includes, by mass, 10 to 80% (e.g., 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, etc.) of a high molecular polymer, 0 to 50% (e.g., 0%, 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, etc.) of a lithium salt, and 5 to 90% (e.g., 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, etc.) of an inorganic fast ion conductor nanofiber.
In the present invention, the data molecular weight of the high molecular polymer is 20 to 150 ten thousand, for example, 20 ten thousand, 30 ten thousand, 40 ten thousand, 50 ten thousand, 60 ten thousand, 70 ten thousand, 80 ten thousand, 90 ten thousand, 100 ten thousand, 110 ten thousand, 120 ten thousand, 130 ten thousand, 140 ten thousand, 150 ten thousand, or the like.
In the invention, the high molecular polymer comprises any one or a combination of at least two of polyethylene oxide, polypropylene oxide, polyacrylonitrile, polyvinyl chloride, polystyrene, polyvinylidene fluoride, polyvinyl acetate, polyvinylpyrrolidone, polymethyl methacrylate, polyethylene glycol polyacrylate or ethylene dioxy sulfide.
In the present invention, the lithium salt includes any one of lithium perchlorate, lithium bistrifluoromethylsulfonyl imide, lithium trifluoromethanesulfonyl, lithium difluorosulfonyl imide, lithium fluoroalkylphosphate, lithium bis (trifluoromethanesulfonyl) methide, lithium dioxalate borate, lithium hexafluorophosphate, lithium hexafluoroarsenate, or lithium tetrafluoroborate, or a combination of at least two thereof.
In the present invention, the thickness of the composite all-solid electrolyte thin film is 10 to 200 μm, for example, 10 μm, 30 μm, 50 μm, 70 μm, 100 μm, 120 μm, 150 μm, 170 μm, 200 μm, or the like.
A fourth object of the present invention is to provide a method for producing the composite all-solid electrolyte thin film according to the third object, the method comprising: adding inorganic fast ion conductor nano-fiber into a mixed solution of a high molecular polymer and a lithium salt, mixing to obtain a slurry, then coating the slurry on a matrix, and curing to obtain the composite all-solid-state electrolyte film.
In the present invention, the mixing means is stirring.
In the invention, the substrate is a PET release film.
In the present invention, the curing temperature is 50 to 100 ℃, for example, 50 ℃, 60 ℃, 70 ℃, 80 ℃, 90 ℃, 100 ℃ and the like.
In the present invention, the curing time is 12 to 24 hours, such as 12 hours, 15 hours, 18 hours, 20 hours, 22 hours, 25 hours and the like.
In the present invention, the method for preparing the mixed solution of the high molecular polymer and the lithium salt includes: dissolving a high molecular polymer and a lithium salt in an organic solvent, and mixing to obtain a mixed solution of the high molecular polymer and the lithium salt.
In the present invention, the organic solvent includes any one of N, N-dimethylformamide, acetonitrile, ethanol, acetone, dimethylsulfoxide, or N-methylpyrrolidone, or a combination of at least two thereof.
In the present invention, the mixing means is stirring.
The fifth purpose of the invention is to provide the application of the composite all-solid electrolyte film as the third purpose in the lithium ion battery.
Compared with the prior art, the invention has the following beneficial effects:
the method for preparing the inorganic fast ionic conductor nano-fiber by adopting the airflow bubble spinning method has the advantages of simple preparation process, high production efficiency, capability of avoiding the operation under the high-voltage static of ten thousand volts and potential safety hazard reduction; the composite all-solid electrolyte film prepared by the inorganic fast ion conductor nano-fiber has higher mechanical property and ion conductivity (the ion conductivity of the electrolyte film is as high as 3.2 multiplied by 10 at 25℃)-4S/cm), which is beneficial to improving the dynamic performance and the cycle service life of the solid-state battery.
Drawings
FIG. 1 is a graph of the change in conductivity with time in example 1.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
The embodiment provides a preparation method of an inorganic fast ion conductor nanofiber, which comprises the following steps:
(1) adding 1.68mol/L lithium nitrate, 0.6mol/L lanthanum nitrate and 0.4mol/L zirconyl nitrate, dissolving in 30mL N, N-dimethylformamide and 6mL glacial acetic acid, stirring, adding 0.06kg/L polyvinylpyrrolidone (average molecular weight 130,0000), stirring at room temperature for 6h to obtain uniform Li7La3Zr2O12(LLZO) precursor solution;
(2) performing air flow bubble spinning on the spinning precursor solution obtained in the step (1), applying 5L/min air flow to the spinning precursor solution to generate bubbles, then breaking the generated bubbles in a 600L/min air flow field, stretching and spraying, wherein the spinning distance is 15cm, and then drying at 70 ℃ for 12h to obtain spinning fibers;
(3) sintering the spinning fiber obtained in the step (2) in a high-temperature furnace in three steps, wherein in the first step, the temperature is increased from 25 ℃ to 500 ℃ at the temperature increase rate of 5 ℃/min, and the temperature is kept for 1 h; secondly, heating from 500 ℃ to 800 ℃ at a heating rate of 10 ℃/min, and preserving heat for 3 hours; and thirdly, cooling from 800 ℃ to 25 ℃ at a cooling rate of 5 ℃/min to obtain the inorganic fast ion conductor nanofiber.
The embodiment also provides a preparation method of the composite all-solid electrolyte film, which comprises the following steps:
(1) adding 5g of lithium bis (trifluoromethyl) sulfonyl imide, 10g of polyethylene oxide (average molecular weight 60,0000) and 1.7g of inorganic fast ion conductor nano-fiber into 150mL of acetonitrile in sequence, stirring uniformly, and then stirring at 50 ℃ for 2h to obtain the composite polymer electrolyte slurry with certain viscosity.
(2) After bubbles are eliminated in vacuum, the composite polymer electrolyte slurry is coated on a release film by utilizing a coating technology, and then the release film is dried in vacuum for 24 hours at the temperature of 60 ℃ to obtain a composite solid electrolyte film with the thickness of 100 mu m.
And (3) placing the composite solid electrolyte film between two stainless steel blocking electrodes, and packaging into a button cell. Adopting a multi-channel electrochemical workstation with strong power transmission to carry out alternating current impedance test, wherein the test frequency is 0.1 Hz-10 MHz, the impedance Rb of the composite solid polymer electrolyte film body is measured, and the formula sigma is L/Rb .And S, (sigma is the ionic conductivity, L is the thickness of the composite solid electrolyte film, and S is the contact area of the electrode), so as to obtain the ionic conductivity of the composite solid electrolyte film. The ionic conductivities at different temperatures are shown in FIG. 1, in which the ionic conductivity of the electrolyte thin film at 25 ℃ is 3.2X 10-4S/cm。
Example 2
The embodiment provides a preparation method of an inorganic fast ion conductor nanofiber, which comprises the following steps:
(1) adding 1.56mol/L lithium nitrate, 0.6mol/L lanthanum nitrate, 0.3mol/L zirconyl nitrate and 0.1mol/L tantalum oxynitrate to dissolve in 30mL N, N-dimethylformamide and 6mL glacial acetic acid, then adding 0.06kg/L polyvinylpyrrolidone (average molecular weight 130,0000), stirring at room temperature for 6h to obtain uniform Li6.5La3Zr1.5Ta0.5O12(LLZTO) precursor solution;
(2) performing air flow bubble spinning on the spinning precursor solution obtained in the step (1), applying 4L/min air flow to the spinning precursor solution to generate bubbles, then breaking the generated bubbles in a 600L/min air flow field, stretching and spraying, wherein the spinning distance is 15cm, and then drying at 70 ℃ for 12h to obtain spinning fibers;
(3) sintering the spinning fiber obtained in the step (2) in a high-temperature furnace in three steps, wherein in the first step, the temperature is increased from 25 ℃ to 500 ℃ at the temperature increase rate of 5 ℃/min, and the temperature is kept for 1 h; secondly, heating from 500 ℃ to 800 ℃ at a heating rate of 10 ℃/min, and preserving heat for 3 hours; and thirdly, cooling from 800 ℃ to 25 ℃ at a cooling rate of 5 ℃/min to obtain the inorganic fast ion conductor nanofiber.
The embodiment also provides a preparation method of the composite all-solid electrolyte film, which comprises the following steps:
(1) sequentially adding 150mL of acetonitrile into 10g of lithium trifluoromethanesulfonimide, 10g of polyvinylidene fluoride (with the average molecular weight of 50,0000) and 2.3g of inorganic fast ion conductor nanofiber, uniformly stirring, and then stirring at 50 ℃ for 2h to obtain the composite polymer electrolyte slurry with certain viscosity.
(2) After bubbles are eliminated in vacuum, the composite polymer electrolyte slurry is coated on a release film by utilizing a coating technology, and then the release film is dried in vacuum for 24 hours at the temperature of 60 ℃ to obtain a composite solid electrolyte film with the thickness of 100 mu m.
The same conductivity test method as that of example 1 was used in this example, and the test results showed that the conductivity was measured at 25 ℃The conductivity of the electrolyte film was 3.0X 10-4S/cm。
Example 3
The embodiment provides a preparation method of an inorganic fast ion conductor nanofiber, which comprises the following steps:
(1) adding 1.68mol/L lithium nitrate, 0.4mol/L aluminum nitrate, 1.6mol/L titanium isopropoxide, 5mL nitric acid, 3mol/L ammonium dihydrogen phosphate and 2mol/L citric acid into 25mL deionized water, uniformly mixing, then adding 0.05kg/L polyvinyl alcohol (average molecular weight is 20,0000), stirring at room temperature for 6h to obtain uniform Li1.4Al0.4Ti1.6(PO4)3(LATP) precursor solution;
(2) performing air flow bubble spinning on the spinning precursor solution obtained in the step (1), applying 5L/min air flow to the spinning precursor solution to generate bubbles, then breaking the generated bubbles in an air flow field of 500L/min, stretching and spraying, wherein the spinning distance is 15cm, and then drying at 60 ℃ for 12h to obtain spinning fibers;
(3) sintering the spinning fiber obtained in the step (2) in a high-temperature furnace in three steps, wherein in the first step, the temperature is increased from 25 ℃ to 500 ℃ at the temperature increase rate of 5 ℃/min, and the temperature is kept for 1 h; secondly, heating from 500 ℃ to 800 ℃ at a heating rate of 10 ℃/min, and preserving heat for 3 hours; and thirdly, cooling from 800 ℃ to 25 ℃ at a cooling rate of 5 ℃/min to obtain the inorganic fast ion conductor nanofiber.
The embodiment also provides a preparation method of the composite all-solid electrolyte film, which comprises the following steps:
(1) 5g of lithium perchlorate, 10g of polyacrylonitrile (average molecular weight of 15,0000) and 2.7g of inorganic fast ion conductor nanofiber are sequentially added into 100mLN, N-dimethylformamide to be uniformly stirred, and then the mixture is stirred for 3 hours at 50 ℃ to obtain the composite polymer electrolyte slurry with certain viscosity.
(2) After bubbles are eliminated in vacuum, the composite polymer electrolyte slurry is coated on a release film by utilizing a coating technology, and then the release film is dried in vacuum for 24 hours at the temperature of 60 ℃ to obtain a composite solid electrolyte film with the thickness of 200 mu m.
Book-keeping deviceExample the same conductivity test method as in example 1 was used, and it was found that the conductivity of the electrolyte thin film was 2.9X 10 at 25 ℃ as a result of the test-4S/cm。
Example 4
The embodiment provides a preparation method of an inorganic fast ion conductor nanofiber, which comprises the following steps:
(1) adding lithium nitrate with the concentration of 0.4mol/L, lanthanum nitrate with the concentration of 0.56mol/L and tetrabutyl titanate with the concentration of 1.0mol/L into a mixed solution of 30ml of N, N-dimethylformamide and 6ml of glacial acetic acid, uniformly stirring, then adding 0.05kg/L of polyvinylpyrrolidone (average molecular weight of 20,0000), and stirring for 4 hours at room temperature to obtain uniform Li0.33La0.557TiO3(LLTO) precursor solution;
(2) performing air flow bubble spinning on the spinning precursor solution obtained in the step (1), applying 5L/min air flow to the spinning precursor solution to generate bubbles, then breaking the generated bubbles in an air flow field of 500L/min, stretching and spraying, wherein the spinning distance is 15cm, and then drying at 60 ℃ for 12h to obtain spinning fibers;
(3) and (3) calcining the spinning fiber obtained in the step (2) in an air atmosphere, keeping the temperature at 700 ℃, heating at a rate of 5 ℃/min, keeping the temperature for 3h, and then cooling to room temperature at a rate of 5 ℃/min to obtain the inorganic fast ion conductor nanofiber.
The embodiment also provides a preparation method of the composite all-solid electrolyte film, which comprises the following steps:
(1) 5g of lithium bistrifluoromethylsulfonyl imide, 10g of polyethylene oxide (average molecular weight 150,0000) and 2.7g of inorganic fast ion conductor nanofiber are sequentially added into 100mL of acetonitrile to be uniformly stirred, and then the mixture is stirred for 2 hours at 50 ℃ to obtain composite polymer electrolyte slurry with certain viscosity.
(2) After bubbles are eliminated in vacuum, the composite polymer electrolyte slurry is coated on a release film by utilizing a coating technology, and then the release film is dried in vacuum for 24 hours at the temperature of 60 ℃ to obtain a composite solid electrolyte film with the thickness of 150 mu m.
This example was conducted using the same conductivity test as in example 1According to the method, the conductivity of the electrolyte film is 2.7 multiplied by 10 at 25 DEG C-4S/cm。
Example 5
The embodiment provides a preparation method of an inorganic fast ion conductor nanofiber, which comprises the following steps:
(1) adding 1.68mol/L lithium nitrate, 0.6mol/L lanthanum nitrate and 0.4mol/L zirconyl nitrate, dissolving in 30mL N, N-dimethylformamide and 6mL glacial acetic acid, stirring, adding 0.06kg/L polyvinylpyrrolidone (average molecular weight 150,0000), stirring at room temperature for 6h to obtain uniform Li7La3Zr2O12(LLZO) precursor solution;
(2) performing air flow bubble spinning on the spinning precursor solution obtained in the step (1), applying 2L/min air flow to the spinning precursor solution to generate bubbles, then breaking the generated bubbles in a 400L/min air flow field, stretching and spraying, wherein the spinning distance is 10cm, and then drying at 100 ℃ for 5 hours to obtain spinning fibers;
(3) sintering the spinning fiber obtained in the step (2) in a high-temperature furnace in three steps, wherein in the first step, the temperature is increased from 25 ℃ to 500 ℃ at the temperature increase rate of 2 ℃/min, and the temperature is kept for 2 hours; secondly, heating from 500 ℃ to 700 ℃ at a heating rate of 5 ℃/min, and keeping the temperature for 6 hours; and thirdly, cooling from 700 ℃ to 25 ℃ at a cooling rate of 5 ℃/min to obtain the inorganic fast ion conductor nanofiber.
The embodiment also provides a preparation method of the composite all-solid electrolyte film, which comprises the following steps:
(1) adding 5g of lithium bis (trifluoromethyl) sulfonyl imide, 10g of polyethylene oxide (average molecular weight is 20,0000) and 1.7g of inorganic fast ion conductor nano-fiber into 150mL of acetonitrile in sequence, stirring uniformly, and then stirring at 50 ℃ for 2h to obtain the composite polymer electrolyte slurry with certain viscosity.
(2) After bubbles are eliminated in vacuum, the composite polymer electrolyte slurry is coated on a release film by utilizing a coating technology, and then is dried in vacuum for 24 hours at 50 ℃ to obtain a composite solid electrolyte film with the thickness of 50 mu m.
The same conductivity test method as in example 1 was used in this example, and the test results revealed that the conductivity of the electrolyte thin film was 2.5X 10 at 25 ℃-4S/cm。
Example 6
The embodiment provides a preparation method of an inorganic fast ion conductor nanofiber, which comprises the following steps:
(1) adding 0.4mol/L lithium nitrate, 0.56mol/L lanthanum nitrate and 1.0mol/L tetrabutyl titanate, adding 30ml of mixed solution of N, N-dimethylformamide and 6ml of glacial acetic acid, stirring uniformly, then adding 0.05kg/L polyvinylpyrrolidone, stirring at room temperature for 4h to obtain uniform Li0.33La0.557TiO3(LLTO) precursor solution;
(2) performing air flow bubble spinning on the spinning precursor solution obtained in the step (1), applying 10L/min air flow to the spinning precursor solution to generate bubbles, then breaking the generated bubbles in a 1200L/min air flow field, stretching and spraying, wherein the spinning distance is 25cm, and then drying at 50 ℃ for 15h to obtain spinning fibers;
(3) sintering the spinning fiber obtained in the step (2) in a high-temperature furnace in three steps, wherein in the first step, the temperature is increased from 25 ℃ to 500 ℃ at the temperature increase rate of 5 ℃/min, and the temperature is kept for 1 h; secondly, heating from 500 ℃ to 1000 ℃ at a heating rate of 5 ℃/min, and keeping the temperature for 2 hours; and thirdly, cooling the temperature from 1000 ℃ to 25 ℃ at a cooling rate of 5 ℃/min to obtain the inorganic fast ion conductor nanofiber.
The embodiment also provides a preparation method of the composite all-solid electrolyte film, which comprises the following steps:
(1) and sequentially adding 5g of lithium bis (trifluoromethyl) sulfonyl imide, 10g of polyethylene oxide and 1.7g of inorganic fast ion conductor nano-fiber into 150mL of acetonitrile, uniformly stirring, and then stirring at 50 ℃ for 2h to obtain the composite polymer electrolyte slurry with certain viscosity.
(2) After bubbles are eliminated in vacuum, the composite polymer electrolyte slurry is coated on a release film by utilizing a coating technology, and then the release film is dried in vacuum at 100 ℃ for 12 hours to obtain a composite solid electrolyte film with the thickness of 10 mu m.
The same conductivity test method as in example 1 was used in this example, and the test results revealed that the conductivity of the electrolyte thin film was 2.8X 10 at 25 ℃-4S/cm。
Comparative example 1
The only difference from example 1 is that the air bubble spinning method was replaced with the electrospinning method, and the remaining manufacturing method was the same as example 1.
The comparative example was conducted by the same conductivity test method as in example 1, and the test results showed that the conductivity of the electrolyte thin film was 1.3X 10 at 25 deg.C-4S/cm; as can be seen from a comparison of example 1 and comparative example 1, when the air bubble spinning method is replaced with the electrospinning method, the conductivity of the electrolyte membrane may be lowered.
The applicant declares that the above description is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be understood by those skilled in the art that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are within the scope and disclosure of the present invention.
Claims (24)
1. The composite all-solid-state electrolyte film is characterized by comprising a first high molecular polymer, lithium salt and inorganic fast ion conductor nano fibers; the preparation method of the inorganic fast ion conductor nanofiber comprises the following steps: carrying out airflow bubble spinning on the spinning precursor solution, and then carrying out high-temperature sintering to obtain the inorganic fast ion conductor nanofiber;
the air bubble spinning comprises the following steps: applying airflow to the spinning precursor solution to generate bubbles, and then breaking the generated bubbles and stretching and spraying the bubbles; the gas flow rate for generating the bubbles is 2-10L/min, and the gas flow rate in the gas field for breaking the bubbles is 400-1200L/min; the spinning distance of the bubble air flow spinning is 10-25 cm;
the preparation method of the spinning precursor solution comprises the following steps: adding metal salt and a second high molecular polymer into an organic solvent, mixing and aging to obtain a spinning precursor solution;
the concentration of metal salt in the spinning precursor solution is 0.05-2.5mol/L, the concentration of a second high molecular polymer in the spinning precursor solution is 0.03-0.20kg/L, the aging temperature is 15-40 ℃, and the aging time is 6-12 h;
the chemical formula of the metal salt includes Li3xLa2/3-xTiO3、Li1+yAlyTi2-y(PO4)3Or Li7-zLa3Zr2-zMzO12Wherein x is more than 0.04 and less than 0.2, y is more than 0.1 and less than 0.6, z is more than 0 and less than 2, and M is any one of Ta, Nb or Bi.
2. The composite all-solid electrolyte membrane according to claim 1, wherein the second high molecular polymer includes any one of polyvinyl pyrrolidone, polyvinyl alcohol, polyvinyl butyral, polyvinyl acetate, polyvinylidene fluoride, polyethylene oxide, or polyacrylonitrile, or a combination of at least two thereof.
3. The composite all-solid electrolyte membrane according to claim 1, wherein the number average molecular weight of the second high molecular polymer is 20 to 150 ten thousand.
4. The composite all-solid electrolyte membrane according to claim 1, wherein the organic solvent comprises ethanol, ethylene glycol, isopropyl alcohol, acetylacetone, glacial acetic acid, orN,N-dimethylformamide, either alone or in combination of at least two.
5. The composite all-solid electrolyte membrane according to claim 1, wherein the mixing is performed under stirring conditions.
6. The composite all-solid electrolyte membrane according to claim 1, wherein said high-temperature sintering is performed in a high-temperature furnace.
7. The composite all-solid electrolyte membrane according to claim 1, wherein the preparation method further comprises drying the fiber obtained by air bubble spinning.
8. The composite all-solid electrolyte membrane according to claim 7, wherein the drying temperature is 50 to 100 ℃.
9. The composite all-solid electrolyte membrane according to claim 7, wherein the drying time is 5 to 15 hours.
10. The composite all-solid electrolyte membrane according to claim 1, wherein said high-temperature sintering comprises: firstly, heating from 25 ℃ to 500 ℃ at a heating rate of 2-5 ℃/min, and preserving heat for 1-2 h; secondly, heating from 500 ℃ to 700 ℃ at the heating rate of 5-10 ℃/min, and preserving heat for 2-6 h; thirdly, cooling from 700-1000 ℃ to 25 ℃ at a cooling rate of 5-10 ℃/min.
11. The composite all-solid electrolyte membrane according to claim 1, wherein the preparation method comprises the steps of:
(1) dissolving metal salt and a second high molecular polymer in an organic solvent under the stirring condition, and aging for 6-12h at 15-40 ℃ to obtain the spinning precursor solution;
(2) performing air flow bubble spinning on the spinning precursor solution obtained in the step (1), applying 2-10L/min air flow to the spinning precursor solution to generate bubbles, then breaking the generated bubbles in an air flow field of 400-1200L/min, stretching and spraying, wherein the spinning interval is 10-25cm, and then drying at 50-100 ℃ for 5-15h to obtain spinning fibers;
(3) sintering the spinning fiber obtained in the step (2) in a high-temperature furnace in three steps, wherein in the first step, the temperature is increased from 25 ℃ to 500 ℃ at the temperature increase rate of 2-5 ℃/min, and the temperature is kept for 1-2 h; secondly, heating from 500 ℃ to 700 ℃ at the heating rate of 5-10 ℃/min, and preserving heat for 2-6 h; and thirdly, cooling from 1000 ℃ to 25 ℃ at the cooling rate of 5-10 ℃/min from 700-.
12. The composite all-solid electrolyte film according to claim 1, wherein the composite all-solid electrolyte film comprises 10-80% by mass of the first high molecular polymer, 0-50% by mass of the lithium salt, and 5-90% by mass of the inorganic fast ion conductor nanofibers.
13. The composite all-solid electrolyte membrane according to claim 1, wherein the number average molecular weight of the first high molecular polymer is 20 to 150 ten thousand.
14. The composite all-solid electrolyte membrane according to claim 1, wherein the first high molecular polymer includes any one of polyethylene oxide, polypropylene oxide, polyacrylonitrile, polyvinyl chloride, polystyrene, polyvinylidene fluoride, polyvinyl acetate, polyvinylpyrrolidone, polymethyl methacrylate, polyethylene glycol acrylate, or ethylenedioxysulfide, or a combination of at least two thereof.
15. The composite all solid electrolyte membrane according to claim 1, wherein the lithium salt comprises any one of lithium perchlorate, lithium bistrifluoromethylsulfonyl imide, lithium triflyl, lithium bifluorosulfonimide, lithium fluoroalkylphosphate, lithium bis (trifluoromethanesulfonyl) methide, lithium dioxalate borate, lithium hexafluorophosphate, lithium hexafluoroarsenate, or lithium tetrafluoroborate, or a combination of at least two thereof.
16. The composite all-solid electrolyte membrane according to claim 1, characterized in that the thickness of the composite all-solid electrolyte membrane is 10 to 200 μm.
17. The method for producing a composite all-solid electrolyte membrane according to any one of claims 1 to 16, characterized by comprising: adding inorganic fast ion conductor nano-fiber into a mixed solution of a first high molecular polymer and lithium salt, mixing to obtain slurry, coating the slurry on a substrate, and curing to obtain the composite all-solid-state electrolyte film.
18. The method for producing a composite all-solid electrolyte membrane according to claim 17, wherein the mixing is performed by stirring.
19. The method for preparing a composite all-solid electrolyte film according to claim 17, wherein the matrix is a PET release film.
20. The method for producing a composite all-solid electrolyte membrane according to claim 17, wherein the temperature of the curing is 50 to 100 ℃.
21. The method for preparing a composite all-solid electrolyte membrane according to claim 17, wherein the curing time is 12 to 24 hours.
22. The method for producing a composite all-solid electrolyte thin film according to claim 17, wherein the method for producing the mixed solution of the first high molecular polymer and the lithium salt comprises: dissolving the first high molecular polymer and lithium salt in an organic solvent, and mixing to obtain a mixed solution of the first high molecular polymer and the lithium salt.
23. The method of preparing a composite all-solid electrolyte membrane according to claim 22, wherein the organic solvent comprisesN,N-Dimethylformamide, acetonitrile, ethanol, acetone, dimethyl sulfoxide orN-any one or a combination of at least two of methylpyrrolidone.
24. Use of the composite all-solid electrolyte membrane according to any one of claims 1 to 16 as a separator in a lithium ion battery.
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