CN112194372A - Glass-ceramic composite film solid garnet electrolyte and preparation method thereof - Google Patents
Glass-ceramic composite film solid garnet electrolyte and preparation method thereof Download PDFInfo
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- CN112194372A CN112194372A CN202011068151.2A CN202011068151A CN112194372A CN 112194372 A CN112194372 A CN 112194372A CN 202011068151 A CN202011068151 A CN 202011068151A CN 112194372 A CN112194372 A CN 112194372A
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- 239000003792 electrolyte Substances 0.000 title claims abstract description 39
- 239000007787 solid Substances 0.000 title claims abstract description 38
- 239000002223 garnet Substances 0.000 title claims abstract description 32
- 239000002131 composite material Substances 0.000 title claims abstract description 30
- 239000002241 glass-ceramic Substances 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 238000003756 stirring Methods 0.000 claims abstract description 32
- 238000010438 heat treatment Methods 0.000 claims abstract description 31
- 239000002002 slurry Substances 0.000 claims abstract description 31
- 239000000758 substrate Substances 0.000 claims abstract description 31
- 239000013078 crystal Substances 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 12
- -1 lithium alkoxide Chemical class 0.000 claims abstract description 10
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052715 tantalum Inorganic materials 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 8
- 150000002603 lanthanum Chemical class 0.000 claims abstract description 7
- 238000004528 spin coating Methods 0.000 claims abstract description 7
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims abstract description 7
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000010409 thin film Substances 0.000 claims description 26
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 10
- 229910001416 lithium ion Inorganic materials 0.000 claims description 10
- 239000010408 film Substances 0.000 claims description 8
- 239000011858 nanopowder Substances 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 7
- AZVCGYPLLBEUNV-UHFFFAOYSA-N lithium;ethanolate Chemical compound [Li+].CC[O-] AZVCGYPLLBEUNV-UHFFFAOYSA-N 0.000 claims description 4
- BGGIUGXMWNKMCP-UHFFFAOYSA-N 2-methylpropan-2-olate;zirconium(4+) Chemical compound CC(C)(C)O[Zr](OC(C)(C)C)(OC(C)(C)C)OC(C)(C)C BGGIUGXMWNKMCP-UHFFFAOYSA-N 0.000 claims description 3
- KJCMWTYCZCEVBS-UHFFFAOYSA-N COCCO[La] Chemical group COCCO[La] KJCMWTYCZCEVBS-UHFFFAOYSA-N 0.000 claims description 3
- JLRJWBUSTKIQQH-UHFFFAOYSA-K lanthanum(3+);triacetate Chemical compound [La+3].CC([O-])=O.CC([O-])=O.CC([O-])=O JLRJWBUSTKIQQH-UHFFFAOYSA-K 0.000 claims description 3
- JILPJDVXYVTZDQ-UHFFFAOYSA-N lithium methoxide Chemical compound [Li+].[O-]C JILPJDVXYVTZDQ-UHFFFAOYSA-N 0.000 claims description 3
- HAUKUGBTJXWQMF-UHFFFAOYSA-N lithium;propan-2-olate Chemical compound [Li+].CC(C)[O-] HAUKUGBTJXWQMF-UHFFFAOYSA-N 0.000 claims description 3
- XPGAWFIWCWKDDL-UHFFFAOYSA-N propan-1-olate;zirconium(4+) Chemical compound [Zr+4].CCC[O-].CCC[O-].CCC[O-].CCC[O-] XPGAWFIWCWKDDL-UHFFFAOYSA-N 0.000 claims description 3
- KWUQLGUXYUKOKE-UHFFFAOYSA-N propan-2-ol;tantalum Chemical compound [Ta].CC(C)O.CC(C)O.CC(C)O.CC(C)O.CC(C)O KWUQLGUXYUKOKE-UHFFFAOYSA-N 0.000 claims description 3
- NGCRLFIYVFOUMZ-UHFFFAOYSA-N 2,3-dichloroquinoxaline-6-carbonyl chloride Chemical group N1=C(Cl)C(Cl)=NC2=CC(C(=O)Cl)=CC=C21 NGCRLFIYVFOUMZ-UHFFFAOYSA-N 0.000 claims description 2
- BSDOQSMQCZQLDV-UHFFFAOYSA-N butan-1-olate;zirconium(4+) Chemical group [Zr+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] BSDOQSMQCZQLDV-UHFFFAOYSA-N 0.000 claims description 2
- LZWQNOHZMQIFBX-UHFFFAOYSA-N lithium;2-methylpropan-2-olate Chemical group [Li+].CC(C)(C)[O-] LZWQNOHZMQIFBX-UHFFFAOYSA-N 0.000 claims description 2
- LVNAMAOHFNPWJB-UHFFFAOYSA-N methanol;tantalum Chemical compound [Ta].OC.OC.OC.OC.OC LVNAMAOHFNPWJB-UHFFFAOYSA-N 0.000 claims description 2
- PVZMSIQWTGPSHJ-UHFFFAOYSA-N butan-1-ol;tantalum Chemical compound [Ta].CCCCO.CCCCO.CCCCO.CCCCO.CCCCO PVZMSIQWTGPSHJ-UHFFFAOYSA-N 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- 238000001354 calcination Methods 0.000 abstract description 2
- 238000005265 energy consumption Methods 0.000 abstract description 2
- 238000005516 engineering process Methods 0.000 description 7
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 3
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 3
- BZRSOWBAZCOWRN-UHFFFAOYSA-N butan-1-ol;tantalum Chemical compound [Ta].CCCCO BZRSOWBAZCOWRN-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 2
- 238000001755 magnetron sputter deposition Methods 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 239000005486 organic electrolyte Substances 0.000 description 2
- 229910052594 sapphire Inorganic materials 0.000 description 2
- 239000010980 sapphire Substances 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- OXWOCAKCADBNHB-UHFFFAOYSA-N methanol;tantalum Chemical compound [Ta].OC OXWOCAKCADBNHB-UHFFFAOYSA-N 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- KPTHYRHRERDAFO-UHFFFAOYSA-N propan-2-ol;tantalum Chemical compound [Ta].CC(C)O KPTHYRHRERDAFO-UHFFFAOYSA-N 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 235000012431 wafers Nutrition 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C10/00—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition
-
- 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
- H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
- H01M10/0562—Solid materials
-
- 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
- H01M2300/0088—Composites
-
- 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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- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- General Physics & Mathematics (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Ceramic Engineering (AREA)
- Inorganic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
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Abstract
The invention discloses a glass-ceramic composite film solid garnet electrolyte and a preparation method thereof, comprising the following steps: adding lithium alkoxide into ethylene glycol monomethyl ether, and adding Li6.4La3Zr1.4Ta0.6O12Adding zirconium alcohol, organic lanthanum salt and tantalum alcohol according to the stoichiometric ratio, stirring to dissolve the solid, adding water, heating, stirring until the solution is gelatinous, and stopping heating and stirring to obtain gel LLZTO; adding the crystal LLZTO into the gel LLZTO, and stirring uniformly to obtain slurry; dropping the slurry on the substrate, and performing spin coating to obtain the substrate coated with the slurry; placing in a muffle furnace, heating to 500-; obtaining the glass-ceramic composite film solid garnet electrolyte. The method of the invention obviously reduces the production energy consumption, and has low calcining temperature and short time. Simple operation, high production efficiency and room-temperature conductivity up to 10‑5S/cm。
Description
Technical Field
The invention belongs to the technical field of novel energy, and particularly relates to a glass-ceramic composite thin film solid garnet electrolyte and a preparation method thereof.
Background
Since fossil energy is exhausted and pollutes the environment ecology, research and development of novel energy technologies with high specific energy and environmental friendliness are receiving much attention. Lithium ion batteries have higher specific energy than other secondary batteries and have been widely used in power sources for portable electric devices and electric vehicles. In addition, since a liquid organic electrolyte is used, combustion and explosion of the battery may be caused under extreme conditions. The solid electrolyte is used for replacing liquid organic electrolyte, so that the lithium ion battery can avoid the safety problem, and the lithium metal cathode and the high-voltage anode material are matched, so that higher specific energy and longer charge-discharge cycle life can be realized. The solid garnet-type LLZTO electrolyte has the advantages of high conductivity, stable metallic lithium and the like. However, due to the high preparation temperature (about 1200 ℃) and the long time consumption (24-36h) and the difficulty in preparing a thin layer at high temperature, grain boundaries exist in the electrolyte, lithium dendrites can grow in the circulation process to cause short circuit of the battery, and the production and application are limited.
Chinese patent CN110137567A teaches that precursor powders of different particle sizes can be mixed together more tightly during tabletting to produce dense garnet electrolytes at low temperatures. But the sintering temperature still reaches 1100 ℃, and the sintering time is 15 h.
The Chinese patent CN111430787A utilizes the magnetron sputtering technology to use garnet electrolyte as the target sputtering layer film electrolyte, which not only has high technical requirement, but also has room temperature conductivity of only 10-7S/cm。
Chinese patent CN111183543A discloses a ceramic-polymer composite membrane electrolyte, which can be made into a membrane electrolyte, but the preparation process is complicated and still contains flammable organic substances, and there is still a hidden danger in safety. Therefore, a method for preparing a glass-ceramic composite thin film solid garnet electrolyte with low temperature, high speed and safe preparation process is needed.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a glass-ceramic composite thin film solid garnet electrolyte.
The second purpose of the invention is to provide a preparation method of the glass-ceramic composite thin film solid garnet electrolyte.
The technical scheme of the invention is summarized as follows:
a preparation method of a glass-ceramic composite thin film solid garnet electrolyte comprises the following steps:
(1) adding lithium alkoxide into ethylene glycol monomethyl ether according to the molar ratio of 1 (50-500), and then adding Li6.4La3Zr1.4Ta0.6O12Adding zirconium alcohol, organic lanthanum salt and tantalum alcohol according to the stoichiometric ratio, stirring to dissolve a solid, adding water which is 0.1-20 molar times of lithium ions, heating to 30-150 ℃, stirring until the solution is gelatinous, and stopping heating and stirring; the gel-like Li6.4La3Zr1.4Ta0.6O12Referred to as gel LLZTO;
(2) nanoarset-type Li, to be abbreviated as crystalline LLZTO6.4La3Zr1.4Ta0.6O12Adding cubic crystal nanopowder into gel LLZTO, wherein the molar ratio of crystal LLZTO to gel LLZTO is (1-100):100, and stirring to obtain slurry;
(3) dropping the slurry on the substrate, fixing the substrate on a spin coater, and spin-coating at the rotation speed of 100-6000rpm for 5-200 seconds to obtain the substrate coated with the slurry;
(4) placing the substrate coated with the slurry in a muffle furnace, heating to 400 ℃ from room temperature, preserving heat for 1-60min to remove organic matters, then heating to 700 ℃ from 500 ℃ and preserving heat for 1-30min, and naturally cooling to room temperature;
(5) repeating the steps (3) and (4) for 1-30 times to obtain the glass-ceramic composite thin film solid garnet electrolyte.
Step (1) is preferably: in mole ratioAdding lithium alkoxide into ethylene glycol monomethyl ether according to the proportion of 1:250, and then adding Li6.4La3Zr1.4Ta0.6O12Adding zirconium alcohol, organic lanthanum salt and tantalum alcohol according to the stoichiometric ratio, stirring to dissolve a solid, adding water which is 5 molar times of lithium ions, heating to 80 ℃, stirring until the solution is gelatinous, and stopping heating and stirring; the gel-like Li6.4La3Zr1.4Ta0.6O12Abbreviated as gel LLZTO.
Step (2) is preferably: nanoarset-type Li, to be abbreviated as crystalline LLZTO6.4La3Zr1.4Ta0.6O12Adding cubic crystal nanopowder into gel LLZTO at a molar ratio of crystal LLZTO to gel LLZTO of 10:100, and stirring to obtain slurry.
Step (3) is preferably: the slurry was dropped on a substrate, the substrate was fixed on a spin coater, and spin-coated at 3000rpm for 20 seconds to obtain a substrate coated with the slurry.
Step (4) is preferably: and (3) placing the substrate coated with the slurry in a muffle furnace, heating to 400 ℃ from room temperature at the speed of 3 ℃/min, preserving the heat for 30min to remove organic matters, heating to 600 ℃ at the speed of 5 ℃/min, preserving the heat for 5min, and naturally cooling to room temperature.
The lithium alkoxide is lithium tert-butoxide, lithium methoxide, lithium ethoxide or lithium isopropoxide.
The zirconium alkoxide is zirconium n-butoxide, zirconium tert-butoxide or zirconium n-propoxide.
The organic lanthanum salt is 2-methoxy ethyoxyl lanthanum or lanthanum acetate.
The tantalum alcohol is tantalum alcohol, tantalum butanol, tantalum methanol or tantalum isopropanol.
The glass-ceramic composite thin film solid garnet electrolyte prepared by the method.
The invention has the advantages that:
(1) the method of the invention obviously reduces the production energy consumption, the calcination temperature is 700 ℃ at most, and the maximum time is 30 minutes.
(2) The production technology threshold and the production efficiency of the film electrolyte are reduced: the common high-requirement technologies for preparing the film electrolyte by using a magnetron sputtering technology, a vapor deposition technology, a pulse laser deposition technology and the like are avoided, and a larger area can be prepared in unit time by spin coating, so that the production efficiency is improved.
(3) The current major thin film electrolyte has a room temperature conductivity of primarily 10-7S/cm, the room temperature conductivity of the glass-ceramic composite thin film solid garnet electrolyte can reach 10-5S/cm。
Drawings
FIG. 1 is a graph of the room temperature conductivity of a glass-ceramic composite thin film solid garnet electrolyte. Parallel electrode test, room temperature conductivity 0.87 x 10-5S/cm。
FIG. 2 is a schematic structural diagram of a glass-ceramic composite thin film solid garnet electrolyte.
FIG. 3 is a surface SEM representation of a glass-ceramic composite thin film solid state garnet electrolyte.
FIG. 4 is a side SEM representation of a glass-ceramic composite thin film solid state garnet electrolyte. The resulting film thickness is about 800 nm.
Detailed Description
Nano garnet type Li6.4La3Zr1.4Ta0.6O12Cubic crystal nanopowders were purchased from the institute for mineral and metallurgy of sand, llc.
The substrate is made of sapphire glass, magnesium oxide, glass or silicon wafers.
The present invention will be further illustrated by the following specific examples.
Example 1
A preparation method of a glass-ceramic composite thin film solid garnet electrolyte comprises the following steps:
(1) adding tert-butyl alcohol lithium into ethylene glycol monomethyl ether according to the mol ratio of 1:250, and then adding Li6.4La3Zr1.4Ta0.6O12Adding zirconium n-propoxide, 2-methoxyethoxy lanthanum and tantalum ethoxide according to the stoichiometric ratio, stirring to dissolve the solid, adding water which is 5 molar times of lithium ions, heating to 80 ℃, stirring until the solution is gelatinous, and stopping heating and stirring; the gel-like Li6.4La3Zr1.4Ta0.6O12Referred to as gel LLZTO;
(2) nanoarset-type Li, to be abbreviated as crystalline LLZTO6.4La3Zr1.4Ta0.6O12Adding the cubic crystal nano powder into the gel LLZTO, wherein the molar ratio of the crystal LLZTO to the gel LLZTO is 10:100, and uniformly stirring to obtain slurry;
(3) dropping the slurry on a substrate made of sapphire glass, fixing the substrate on a spin coater, and spin-coating at the rotating speed of 3000rpm for 20 seconds to obtain the substrate coated with the slurry;
(4) placing the substrate coated with the slurry in a muffle furnace, heating to 400 ℃ from room temperature at a speed of 3 ℃/min, preserving heat for 30min to remove organic matters, heating to 600 ℃ at a speed of 5 ℃/min, preserving heat for 5min, and naturally cooling to room temperature;
(5) repeating the steps (3) and (4) for 5 times to obtain the glass-ceramic composite thin film solid garnet electrolyte. See fig. 1, 2, 3, 4.
Example 2
A preparation method of a glass-ceramic composite thin film solid garnet electrolyte comprises the following steps:
(1) adding lithium methoxide into ethylene glycol monomethyl ether according to the mol ratio of 1:50, and then adding Li6.4La3Zr1.4Ta0.6O12Adding zirconium n-butyl alcohol, 2-methoxyethoxy lanthanum and tantalum butanol according to the stoichiometric ratio, stirring to dissolve solids, adding water which is 0.1 molar time of lithium ions, heating to 150 ℃, stirring until the solution is gelatinous, and stopping heating and stirring; the gel-like Li6.4La3Zr1.4Ta0.6O12Referred to as gel LLZTO;
(2) nanoarset-type Li, to be abbreviated as crystalline LLZTO6.4La3Zr1.4Ta0.6O12Adding cubic crystal nano powder into the gel LLZTO, wherein the molar ratio of the crystal LLZTO to the gel LLZTO is 1:100, and uniformly stirring to obtain slurry;
(3) dropping the slurry on a magnesium oxide substrate, fixing the substrate on a spin coater, and spin-coating at the rotating speed of 100rpm for 200 seconds to obtain the substrate coated with the slurry;
(4) placing the substrate coated with the slurry in a muffle furnace, heating to 300 ℃ from room temperature, preserving heat for 60min to remove organic matters, heating to 500 ℃ and preserving heat for 30min, and naturally cooling to room temperature;
(5) repeating the steps (3) and (4) for 1 time to obtain the glass-ceramic composite thin film solid garnet electrolyte.
The film thickness is about 1000 nm.
Parallel electrode test, room temperature conductivity 1.2 x 10-6S/cm。
The surface of the glass-ceramic composite thin film solid garnet electrolyte was similar to that of example 1.
Example 3
A preparation method of a glass-ceramic composite thin film solid garnet electrolyte comprises the following steps:
(1) adding lithium ethoxide into ethylene glycol monomethyl ether according to the mol ratio of 1:500, and then adding Li6.4La3Zr1.4Ta0.6O12Adding zirconium tert-butoxide, lanthanum acetate and tantalum isopropoxide according to the stoichiometric ratio, stirring to dissolve the solid, adding water which is 20 molar times of lithium ions, heating to 30 ℃, stirring until the solution is gelatinous, and stopping heating and stirring; the gel-like Li6.4La3Zr1.4Ta0.6O12Referred to as gel LLZTO;
(2) nanoarset-type Li, to be abbreviated as crystalline LLZTO6.4La3Zr1.4Ta0.6O12Adding cubic crystal nano powder into the gel LLZTO, wherein the molar ratio of the crystal LLZTO to the gel LLZTO is 100:100, and uniformly stirring to obtain slurry;
(3) dropping the slurry on a glass substrate, fixing the substrate on a spin coater, and spin-coating at the rotating speed of 6000rpm for 5 seconds to obtain the substrate coated with the slurry;
(4) placing the substrate coated with the slurry in a muffle furnace, heating to 400 ℃ from room temperature, preserving heat for 1min to remove organic matters, heating to 700 ℃ and preserving heat for 1min, and naturally cooling to room temperature;
(5) repeating the steps (3) and (4) for 30 times to obtain the glass-ceramic composite thin film solid garnet electrolyte.
The film thickness was about 600 nm.
Parallel electrode test, room temperature conductivity 2.4 x 10-6S/cm。
The surface of the glass-ceramic composite thin film solid garnet electrolyte was similar to that of example 1.
The lithium isopropoxide is used to replace the lithium ethoxide in the embodiment, and the tantalum methoxide is used to replace the tantalum isopropoxide in the embodiment, and other properties of the prepared glass-ceramic composite thin film solid garnet electrolyte are similar to those of the embodiment.
The invention discloses an application of a glass-ceramic composite thin film solid garnet electrolyte, which comprises the following steps: the lithium ion battery is used in a thin film all-solid-state lithium battery.
Claims (10)
1. A preparation method of a glass-ceramic composite film solid garnet electrolyte is characterized by comprising the following steps:
(1) adding lithium alkoxide into ethylene glycol monomethyl ether according to the molar ratio of 1 (50-500), and then adding Li6.4La3Zr1.4Ta0.6O12Adding zirconium alcohol, organic lanthanum salt and tantalum alcohol according to the stoichiometric ratio, stirring to dissolve a solid, adding water which is 0.1-20 molar times of lithium ions, heating to 30-150 ℃, stirring until the solution is gelatinous, and stopping heating and stirring; the gel-like Li6.4La3Zr1.4Ta0.6O12Referred to as gel LLZTO;
(2) nanoarset-type Li, to be abbreviated as crystalline LLZTO6.4La3Zr1.4Ta0.6O12Adding cubic crystal nanopowder into gel LLZTO, wherein the molar ratio of crystal LLZTO to gel LLZTO is (1-100):100, and stirring to obtain slurry;
(3) dropping the slurry on the substrate, fixing the substrate on a spin coater, and spin-coating at the rotation speed of 100-6000rpm for 5-200 seconds to obtain the substrate coated with the slurry;
(4) placing the substrate coated with the slurry in a muffle furnace, heating to 400 ℃ from room temperature, preserving heat for 1-60min to remove organic matters, then heating to 700 ℃ from 500 ℃ and preserving heat for 1-30min, and naturally cooling to room temperature;
(5) repeating the steps (3) and (4) for 1-30 times to obtain the glass-ceramic composite thin film solid garnet electrolyte.
2. The method as claimed in claim 1, wherein the step (1) is: adding lithium alkoxide into ethylene glycol monomethyl ether according to the mol ratio of 1:250, and then adding Li6.4La3Zr1.4Ta0.6O12Adding zirconium alcohol, organic lanthanum salt and tantalum alcohol according to the stoichiometric ratio, stirring to dissolve a solid, adding water which is 5 molar times of lithium ions, heating to 80 ℃, stirring until the solution is gelatinous, and stopping heating and stirring; the gel-like Li6.4La3Zr1.4Ta0.6O12Abbreviated as gel LLZTO.
3. The method as claimed in claim 1, wherein the step (2) is: nanoarset-type Li, to be abbreviated as crystalline LLZTO6.4La3Zr1.4Ta0.6O12Adding cubic crystal nanopowder into gel LLZTO at a molar ratio of crystal LLZTO to gel LLZTO of 10:100, and stirring to obtain slurry.
4. The method as claimed in claim 1, wherein the step (3) is: the slurry was dropped on a substrate, the substrate was fixed on a spin coater, and spin-coated at 3000rpm for 20 seconds to obtain a substrate coated with the slurry.
5. The method as claimed in claim 1, wherein the step (4) is: and (3) placing the substrate coated with the slurry in a muffle furnace, heating to 400 ℃ from room temperature at the speed of 3 ℃/min, preserving the heat for 30min to remove organic matters, heating to 600 ℃ at the speed of 5 ℃/min, preserving the heat for 5min, and naturally cooling to room temperature.
6. The process according to claim 1 or 2, characterized in that the lithium alkoxide is lithium tert-butoxide, lithium methoxide, lithium ethoxide or lithium isopropoxide.
7. The process according to claim 1 or 2, characterized in that the zirconium alkoxide is zirconium n-butoxide, zirconium tert-butoxide or zirconium n-propoxide.
8. The process as claimed in claim 1 or 2, characterized in that the organic lanthanum salt is 2-methoxyethoxy lanthanum or lanthanum acetate.
9. The method according to claim 1 or 2, wherein the tantalum alkoxide is tantalum ethoxide, tantalum butoxide, tantalum methoxide or tantalum isopropoxide.
10. A glass-ceramic composite thin film solid garnet electrolyte prepared by the method of claims 1 to 9.
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