CN111430787B - Composite film solid electrolyte and preparation method and application thereof - Google Patents
Composite film solid electrolyte and preparation method and application thereof Download PDFInfo
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- CN111430787B CN111430787B CN202010141689.5A CN202010141689A CN111430787B CN 111430787 B CN111430787 B CN 111430787B CN 202010141689 A CN202010141689 A CN 202010141689A CN 111430787 B CN111430787 B CN 111430787B
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- 239000002131 composite material Substances 0.000 title claims abstract description 78
- 239000007784 solid electrolyte Substances 0.000 title claims abstract description 74
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000003792 electrolyte Substances 0.000 claims abstract description 74
- 239000000919 ceramic Substances 0.000 claims abstract description 65
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 58
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 58
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 54
- 238000004544 sputter deposition Methods 0.000 claims abstract description 52
- 239000000654 additive Substances 0.000 claims abstract description 45
- 230000000996 additive effect Effects 0.000 claims abstract description 45
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 30
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 28
- 238000000034 method Methods 0.000 claims abstract description 25
- 239000000463 material Substances 0.000 claims abstract description 11
- 238000000151 deposition Methods 0.000 claims abstract description 9
- 230000008021 deposition Effects 0.000 claims abstract description 3
- 239000010408 film Substances 0.000 claims description 99
- 239000010409 thin film Substances 0.000 claims description 42
- 239000000843 powder Substances 0.000 claims description 41
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 32
- 239000000758 substrate Substances 0.000 claims description 30
- 239000013077 target material Substances 0.000 claims description 28
- 229910052786 argon Inorganic materials 0.000 claims description 16
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 14
- -1 lithium hexafluorophosphate Chemical compound 0.000 claims description 14
- 238000003825 pressing Methods 0.000 claims description 12
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 9
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 9
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 claims description 8
- 229910001947 lithium oxide Inorganic materials 0.000 claims description 8
- IGILRSKEFZLPKG-UHFFFAOYSA-M lithium;difluorophosphinate Chemical compound [Li+].[O-]P(F)(F)=O IGILRSKEFZLPKG-UHFFFAOYSA-M 0.000 claims description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 6
- 229910019142 PO4 Inorganic materials 0.000 claims description 6
- 229910052758 niobium Inorganic materials 0.000 claims description 4
- 229910052715 tantalum Inorganic materials 0.000 claims description 4
- 229910010252 TiO3 Inorganic materials 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- 229910021529 ammonia Inorganic materials 0.000 claims description 3
- 229910052733 gallium Inorganic materials 0.000 claims description 3
- 229910052738 indium Inorganic materials 0.000 claims description 3
- 229910001386 lithium phosphate Inorganic materials 0.000 claims description 3
- 229910052706 scandium Inorganic materials 0.000 claims description 3
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 claims description 3
- 229910005313 Li14ZnGe4O16 Inorganic materials 0.000 claims description 2
- 238000003980 solgel method Methods 0.000 claims description 2
- 238000003746 solid phase reaction Methods 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 15
- 238000005245 sintering Methods 0.000 description 9
- XRNHBMJMFUBOID-UHFFFAOYSA-N [O].[Zr].[La].[Li] Chemical compound [O].[Zr].[La].[Li] XRNHBMJMFUBOID-UHFFFAOYSA-N 0.000 description 8
- CEMTZIYRXLSOGI-UHFFFAOYSA-N lithium lanthanum(3+) oxygen(2-) titanium(4+) Chemical compound [Li+].[O--].[O--].[O--].[O--].[Ti+4].[La+3] CEMTZIYRXLSOGI-UHFFFAOYSA-N 0.000 description 7
- 239000011812 mixed powder Substances 0.000 description 7
- FVXHSJCDRRWIRE-UHFFFAOYSA-H P(=O)([O-])([O-])[O-].[Ge+2].[Al+3].[Li+].P(=O)([O-])([O-])[O-] Chemical compound P(=O)([O-])([O-])[O-].[Ge+2].[Al+3].[Li+].P(=O)([O-])([O-])[O-] FVXHSJCDRRWIRE-UHFFFAOYSA-H 0.000 description 6
- CVJYOKLQNGVTIS-UHFFFAOYSA-K aluminum;lithium;titanium(4+);phosphate Chemical compound [Li+].[Al+3].[Ti+4].[O-]P([O-])([O-])=O CVJYOKLQNGVTIS-UHFFFAOYSA-K 0.000 description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 5
- 229910052802 copper Inorganic materials 0.000 description 5
- 239000010949 copper Substances 0.000 description 5
- 238000011161 development Methods 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- 238000011160 research Methods 0.000 description 5
- 229910001220 stainless steel Inorganic materials 0.000 description 5
- 239000010935 stainless steel Substances 0.000 description 5
- 238000000427 thin-film deposition Methods 0.000 description 5
- 239000010416 ion conductor Substances 0.000 description 4
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- GNTXTNSKHHBKIB-UHFFFAOYSA-N [O-2].[Ti+4].[Zr+4].[La+3].[Li+].[O-2].[O-2].[O-2].[O-2].[O-2] Chemical compound [O-2].[Ti+4].[Zr+4].[La+3].[Li+].[O-2].[O-2].[O-2].[O-2].[O-2] GNTXTNSKHHBKIB-UHFFFAOYSA-N 0.000 description 3
- KZGIKPHEKSDETK-UHFFFAOYSA-N [O].[Ti].[Zr].[La].[Li] Chemical compound [O].[Ti].[Zr].[La].[Li] KZGIKPHEKSDETK-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000000498 ball milling Methods 0.000 description 3
- 238000001354 calcination Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000001755 magnetron sputter deposition Methods 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- WVDJDYHWHDLSAZ-UHFFFAOYSA-N [O].[Ti].[La].[Li] Chemical compound [O].[Ti].[La].[Li] WVDJDYHWHDLSAZ-UHFFFAOYSA-N 0.000 description 2
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 2
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium dioxide Chemical compound O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 239000011244 liquid electrolyte Substances 0.000 description 2
- 229910000664 lithium aluminum titanium phosphates (LATP) Inorganic materials 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 235000019837 monoammonium phosphate Nutrition 0.000 description 2
- 238000005457 optimization Methods 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 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 description 1
- 239000002227 LISICON Substances 0.000 description 1
- 239000002228 NASICON Substances 0.000 description 1
- NRJJZXGPUXHHTC-UHFFFAOYSA-N [Li+].[O--].[O--].[O--].[O--].[Zr+4].[La+3] Chemical compound [Li+].[O--].[O--].[O--].[O--].[Zr+4].[La+3] NRJJZXGPUXHHTC-UHFFFAOYSA-N 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 description 1
- 239000010406 cathode material Substances 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
- 210000001787 dendrite Anatomy 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000002001 electrolyte material Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 229940119177 germanium dioxide Drugs 0.000 description 1
- IAQLJCYTGRMXMA-UHFFFAOYSA-M lithium;acetate;dihydrate Chemical compound [Li+].O.O.CC([O-])=O IAQLJCYTGRMXMA-UHFFFAOYSA-M 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000011224 oxide ceramic Substances 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Images
Classifications
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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
- 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
- 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
- H01M10/058—Construction or manufacture
-
- 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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The invention belongs to the field of lithium ion batteries, and provides a preparation method and application of a composite film solid electrolyte. The composite film solid electrolyte comprises a multiphase composite electrolyte film which is formed by carrying out co-sputtering treatment and deposition growth on an electrolyte source ceramic target and a lithium source additive target in an inert atmosphere or a nitrogen source atmosphere; or the lithium ion battery comprises an electrolyte source ceramic film layer and a lithium source additive film layer combined with one surface of the electrolyte source ceramic film layer, the electrolyte source ceramic film layer and the lithium source additive film layer form a basic unit, and the basic unit is sequentially combined in a laminated mode from the electrolyte source ceramic film layer to the lithium source additive film layer in the extending direction. The composite solid electrolyte film has the advantages of small interface resistance, wide potential window, high ionic conductivity, low electronic conductivity and the like, and the preparation method has simple process and obvious effect and is an ideal solid electrolyte material.
Description
Technical Field
The invention belongs to the field of lithium ion batteries, and particularly relates to a composite film solid electrolyte and a preparation method and application thereof.
Background
As a novel green energy source, the lithium ion battery is widely applied to a plurality of fields such as mobile power supplies, mobile phones, notebook computers, electric vehicles and the like due to the advantages of high working voltage, environmental protection, no pollution, light weight, no memory effect and the like. Meanwhile, with the strong support of the country on the new energy automobile industry, the market demand of the lithium ion battery is increasing. The traditional liquid lithium ion battery becomes a hot point of industrial research due to the existence of serious potential safety hazard, the composition of the traditional liquid lithium ion battery contains flammable organic liquid electrolyte, and due to the poor thermal stability and the existence of the organic liquid electrolyte with low ignition point, the lithium ion battery is very easy to cause ignition and explosion accidents when the lithium ion battery is improperly used. Although the development of new flame retardant materials and the design of safer battery management systems can solve some problems to some extent, they still cannot meet the application requirements of the market for high energy density lithium batteries, especially the urgent requirements of the rapidly developing electric automobile industry for battery safety.
The solid lithium battery has small size and light weight, particularly the solid electrolyte has good mechanical strength, can well inhibit the generation of lithium dendrite, enables high-capacity metal to be taken as a negative electrode, and is beneficial to realizing the high energy density of the solid lithium battery; the solid electrolyte has better electrochemical stability and incombustibility, and can be more suitable for a ternary cathode material with high voltage and high capacity; the design of the battery system can be simplified due to the non-flowability of the electrolyte material.
At present, the all-solid-state thin-film lithium battery is the latest field of lithium ion battery development, the thickness of the all-solid-state thin-film lithium battery can reach millimeter or even micron level, the all-solid-state thin-film lithium battery not only has light weight, high capacity density and long service life, but also can be designed according to the product requirements, can be assembled on substrates made of different materials, has wide working temperature window, high safety coefficient and the like, and has a plurality of advantages. The development mainly focuses on the aspects of advanced film forming technology research, new battery structure research, novel anode and cathode thin film research, high ionic conductivity solid electrolyte research and the like.
However, in actual production, it is found that the conductivity, stability and compatibility of the existing solid electrolyte are still to be improved, the existing preparation method is low in efficiency and high in cost, and the battery performance is still to be improved compared with a liquid lithium ion battery. Therefore, the development of a novel solid electrolyte film is the key of the development of the field of solid film lithium batteries by improving the preparation technology of the film.
Disclosure of Invention
The invention aims to overcome the defects in the prior art, and provides a composite film solid electrolyte and a preparation method thereof, so as to solve the technical problems of poor conductivity, stability and compatibility of the conventional solid electrolyte, low efficiency, high cost and the like of the preparation method.
In order to achieve the object of the present invention, in one aspect, the present invention provides a composite thin film solid electrolyte. The composite film solid electrolyte comprises a multiphase composite electrolyte film which is formed by carrying out co-sputtering treatment and deposition growth on an electrolyte source ceramic target and a lithium source additive target in an inert atmosphere or a nitrogen source atmosphere; or
The lithium ion battery comprises an electrolyte source ceramic film layer and a lithium source additive film layer combined with one surface of the electrolyte source ceramic film layer, wherein the electrolyte source ceramic film layer and the lithium source additive film layer form a basic unit, and the basic unit is sequentially combined in a laminated mode from the electrolyte source ceramic film layer to the lithium source additive film layer in the extending direction.
In another aspect, a method for preparing a composite thin film solid electrolyte is provided. The preparation method of the composite film solid electrolyte comprises the following steps:
co-sputtering the electrolyte source ceramic target and the lithium source additive target in an inert atmosphere or a nitrogen source atmosphere to obtain a multiphase composite electrolyte film;
or
The electrolyte source ceramic target material is sputtered in inert atmosphere or nitrogen source atmosphere to grow electrolyte source ceramic film on the substrate, and the electrolyte source ceramic film is then sputtered
Sputtering the lithium source additive target material in an inert atmosphere or a nitrogen source atmosphere to grow a lithium source additive film on the electrolyte source ceramic film; then the
And alternately repeating the step of growing the electrolyte source ceramic film layer and the step of growing the lithium source additive film layer at least once.
In another aspect, the present invention provides a lithium ion battery. The lithium ion battery comprises the composite film solid electrolyte.
Compared with the prior art, the composite film solid electrolyte has the advantages of small interface resistance, wide potential window, high ionic conductivity, low electronic conductivity and the like.
The composite film solid electrolyte provided by the invention not only can enable the prepared composite film solid electrolyte to have the optimization, but also has the advantages that the process conditions of the preparation method are easy to control, the stable performance of the prepared composite film solid electrolyte can be effectively ensured, and the efficiency is high
The lithium ion battery contains the composite film solid electrolyte, so that the energy density is high, and the cycle performance is improved.
Drawings
FIG. 1 is a schematic structural view of a composite thin film solid electrolyte according to an embodiment of the present invention;
FIG. 2 is a Nyquist impedance plot of a composite thin film solid electrolyte prepared in accordance with example one;
FIG. 3 is a Nyquist impedance plot for a composite thin film solid electrolyte prepared in example two;
FIG. 4 is a Nyquist impedance plot for a composite thin film solid electrolyte prepared in example III;
FIG. 5 is a Nyquist impedance plot for the multilayer composite thin film solid electrolyte prepared in example IV.
FIG. 6 is a Nyquist impedance plot for the multilayer composite thin film solid electrolyte prepared in example five.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
In one aspect, embodiments of the present invention provide a composite thin film solid electrolyte. In one embodiment, the composite thin film solid electrolyte comprises a multiphase composite electrolyte thin film which is deposited and grown by carrying out co-sputtering treatment on an electrolyte source ceramic target and a lithium source additive target in an inert atmosphere or a nitrogen source atmosphere. In a preferred embodiment, the multiphase composite thin film solid electrolyte has a thickness of 0.1 to 10 μm. The room-temperature ionic conductivity of the multiphase composite film solid electrolyte is 10-1To 10-6Siemens per centimeter.
In another embodiment, the structure of the composite thin film solid electrolyte is as shown in fig. 1, and comprises an electrolyte source ceramic film layer 1 and a lithium source additive film layer 2 bonded to one surface of the electrolyte source ceramic film layer 1, and the electrolyte source ceramic film layer 1 and the lithium source additive film layer 2 form a basic unit, and the basic units are sequentially laminated and bonded from the electrolyte source ceramic film layer 1 to the lithium source additive film layer 2 in the extending direction to form a multilayer structure of the composite thin film solid electrolyte. In a preferred embodiment, the electrolyte sourceThe thickness of the ceramic film layer 1 can be controlled to be 0.1-10 μm, and the thickness of the lithium source additive film layer 2 can be controlled to be 0.05-0.1 μm. In addition, the total thickness of the composite thin film solid electrolyte of the multilayer structure is 0.1 to 10 μm. The electron conductivity of the multilayer structure of the composite film solid electrolyte at room temperature is measured to be 10-10To 10-16Siemens per centimeter.
In one embodiment, the electrolyte source ceramic contained in the electrolyte source ceramic target in each of the above embodiments includes a lithium ion conductor Li of NASICON type1+xTi2-xMx(PO4)3、Li1+xGe2-xMx(PO4)3Perovskite type lithium ion conductor Li3yLa(2/3)-yTiO3(0<x<0.16), LISICON type lithium ion conductor Li14ZnGe4O16Or garnet-type lithium ion conductor Li5La3N2O12At least one of (N ═ Ta, Nb); wherein, the 0.1<x<0.7，0<y<0.16, M is at least one of Al, Ga, In and Sc, and N is at least one of Ta and Nb.
The electrolyte source ceramic target material can be prepared by the following method:
the ceramic powder is prepared by adopting a solid-phase reaction method or a sol-gel method, the prepared ceramic powder is uniformly paved on the surface of a substrate, then the powder is subjected to dry pressing treatment to obtain a powder target material, and then the powder target material is sintered in an atmosphere to obtain a ceramic block target material.
In another embodiment, the lithium source additive contained in the lithium source additive target material in each of the above embodiments includes at least one of lithium hexafluorophosphate, lithium difluorophosphate, lithium phosphate, lithium carbonate, lithium oxide, lithium hydroxide, and a metallic lithium material.
Since the composite thin film solid electrolyte has the above-mentioned components or structure, it has the advantages of small interface resistance, wide potential window, high ionic conductivity, low electronic conductivity, and the like.
In one aspect, embodiments of the present invention provide a method for preparing the composite thin film solid electrolyte described above based on the structural features of the composite thin film solid electrolyte described above.
In one embodiment, the preparation method of the composite thin film solid electrolyte comprises the following steps:
co-sputtering the electrolyte source ceramic target and the lithium source additive target in an inert atmosphere or a nitrogen source atmosphere to obtain the multiphase composite electrolyte film.
In the co-sputtering process, a mixture film is deposited and grown on a substrate by the electrolyte source ceramic target and the lithium source additive target, namely the multiphase composite electrolyte film. In one embodiment, the power of the co-sputtering process satisfies: the ratio of the power for sputtering the electrolyte source ceramic target to the power for sputtering the lithium source target is 4: 1-1: 4. in another embodiment, the temperature of the substrate is controlled to be 0 ℃ to 800 ℃ during the co-sputtering process. The inert atmosphere or the nitrogen source atmosphere is a sputtering atmosphere constructed by at least one or more of nitrogen, argon and ammonia. The quality of a deposited and grown mixture film is improved, the corresponding electrochemical performance is improved, and the thickness of the controller is adjusted by controlling the sputtering condition of the co-sputtering treatment.
In one embodiment, in combination with the structure of the composite thin film solid electrolyte shown in fig. 1, the method for preparing the composite thin film solid electrolyte includes the following steps:
s01: the electrolyte source ceramic target material is sputtered under inert atmosphere or nitrogen source atmosphere to grow an electrolyte source ceramic film layer 1 on a substrate, and then
S02: sputtering the lithium source additive target material in an inert atmosphere or a nitrogen source atmosphere to grow a lithium source additive film layer 2 on the electrolyte source ceramic film layer; then the
S03: the step of growing the electrolyte source ceramic membrane layer 1 and the step of growing the lithium source additive membrane layer 2 are alternately repeated at least once in sequence.
Here, in the sputtering process in step S01 and step S02, the electrolyte source ceramic film layer 1 and the lithium source additive film layer 2 are conventionally deposited and grown on the substrate. In one embodiment, the temperature of the substrate is controlled to be 0 ℃ to 800 ℃ during the sputtering process in steps S01 and S02. In a preferred embodiment, the sputtering power for sputtering the electrolyte source ceramic film layer 1 is 50W-200W, and the sputtering power for sputtering the lithium source additive film layer 2 is 30W-90W. In addition, the inert atmosphere or the nitrogen source atmosphere is a sputtering atmosphere constructed by at least one or more of nitrogen, argon and ammonia. By controlling the sputtering conditions of the sputtering treatment, the quality of the deposited and grown electrolyte source ceramic film layer 1 and the lithium source additive film layer 2 is improved, the electrochemical performance related to the corresponding layer structure is improved, and the thickness of the controller is adjusted.
In addition, the electrolyte source ceramic target material in each of the above embodiments is prepared as the electrolyte source ceramic described above, and the lithium source additive target material is also prepared as the lithium source additive described above.
Therefore, the composite thin film solid electrolyte not only can enable the prepared composite thin film solid electrolyte to have the optimization, but also has the advantages of easily controlled process conditions of the preparation method, capability of effectively ensuring stable performance of the prepared composite thin film solid electrolyte and high efficiency.
On the other hand, the embodiment of the invention also provides a lithium ion battery. The lithium ion battery is an all-solid-state lithium ion battery. Thus, the lithium ion battery naturally includes necessary components such as a positive electrode, a negative electrode, and a separator and a solid electrolyte. Wherein the solid electrolyte is the above-mentioned thin film solid electrolyte. The other components may be conventional components contained in conventional lithium ion batteries. Thus, the lithium ion battery has high energy density and good cycle performance improvement due to the fact that the lithium ion battery contains the thin film solid electrolyte.
The composite thin film solid electrolyte of the embodiments of the present invention, the preparation method and the application thereof, etc. are illustrated by a plurality of specific examples below.
Example one
The embodiment provides a preparation method of a multilayer composite thin film solid electrolyte. The multilayer composite thin film solid electrolyte is prepared according to a method comprising the following steps:
1) preparing a lithium lanthanum zirconium oxygen block target and a lithium hexafluorophosphate powder target: adding lithium carbonate, lanthanum oxide and zirconium oxide into a ball mill according to the molar ratio of 7:3:2, ball-milling for 4h, calcining the obtained mixed powder in air at 900 ℃ for 6h, adding 20% of lithium carbonate, sintering at 600 ℃ for 6h to obtain lithium lanthanum zirconium oxygen ceramic solid electrolyte powder with excellent performance, pressing the prepared lithium lanthanum zirconium oxygen powder into a blank, and sintering at 1100 ℃ in an oxygen atmosphere to obtain a lithium lanthanum zirconium oxygen block target;
respectively and uniformly paving lithium hexafluorophosphate powder with the purity of 99.99 percent in a copper tray with the diameter of 70mm in an argon glove box, and carrying out unidirectional dry pressing on the powder material by using a 5T unidirectional press machine to prepare a lithium hexafluorophosphate target material;
2) using the lithium lanthanum zirconium oxygen block target as a first sputtering source, wherein the distance between a substrate and the target is 50mm and is 1.0 multiplied by 10-2In the mixed atmosphere of high-purity argon and nitrogen in millibar, depositing a lithium lanthanum zirconium oxygen film on a stainless steel substrate by a radio frequency magnetron sputtering method; then using the lithium hexafluorophosphate powder target as a second sputtering source, and arranging the distance between the substrate and the target on the substrate of the existing lithium lanthanum zirconium oxide film to be 50mm at 1.0 multiplied by 10-2And (3) depositing a lithium hexafluorophosphate film in a mixed atmosphere of high-purity argon and nitrogen in millibar, and alternately and repeatedly carrying out the first sputtering treatment and the second sputtering treatment to prepare the multilayer composite film electrolyte. During the thin film deposition, the substrate temperature was maintained at 100 ℃.
And (3) performance testing: carrying out AC impedance test on the multilayer composite film electrolyte prepared in the step 2) in a glove box at the temperature of 25 ℃, wherein the test result is shown in figure 2, and the fitting result shows that the ionic conductivity is 5.37 multiplied by 10-7S/cm, electron conductivity of 2.85X 10-10S/cm, ion conductivity/electron conductivity 1.884 × 104。
Example two
The second embodiment provides a preparation method of a multilayer composite thin film solid electrolyte. The multilayer composite thin film solid electrolyte is prepared according to a method comprising the following steps:
1) preparing a lithium lanthanum titanium oxide block target material and a lithium difluorophosphate powder target material: adding lithium carbonate, lanthanum oxide and titanium dioxide into a ball mill according to the molar ratio of 0.33:0.56:1, carrying out ball milling for 4h, calcining the obtained mixed powder in air at 900 ℃ for 6h, adding 10% of lithium carbonate, sintering at 600 ℃ for 6h to obtain lithium lanthanum titanium oxide ceramic solid electrolyte powder with excellent performance, pressing the prepared lithium lanthanum titanium oxide powder into a blank, and sintering at 1100 ℃ in an oxygen atmosphere to obtain a lithium lanthanum titanium oxide block target;
uniformly laying lithium difluorophosphate powder with the purity of 99.98% in a copper tray with the diameter of 70mm in an argon glove box, and performing unidirectional dry pressing on the powder material by using a 5T unidirectional press to prepare a lithium difluorophosphate powder target;
2) the lithium lanthanum titanium oxide block target is used as a first sputtering source, the distance between a substrate and the target is 50mm and is 1.0 multiplied by 10-2In the mixed atmosphere of high-purity argon and nitrogen in millibar, depositing a lithium lanthanum titanium oxide film on a stainless steel substrate by a radio frequency magnetron sputtering method; then using the lithium difluorophosphate powder target as a second sputtering source, and on the substrate of the existing lithium lanthanum titanium oxide film, the distance between the substrate and the target is 50mm, and is 1.0 multiplied by 10-2And (3) depositing a lithium difluorophosphate film in a mixed atmosphere of high-purity argon and nitrogen in millibar, and alternately and repeatedly carrying out the first sputtering treatment and the second sputtering treatment to prepare the multilayer composite film electrolyte. During the thin film deposition, the substrate temperature was maintained at 100 ℃.
And (3) performance testing: carrying out AC impedance test on the multilayer composite film electrolyte prepared in the step 2) in a glove box at the temperature of 25 ℃, wherein the test result is shown in figure 3, and the fitting result shows that the ionic conductivity is 2.39 multiplied by 10-6S/cm, electron conductivity of 4.65X 10-7S/cm, ion conductivity/electron conductivity 0.513 × 103。
EXAMPLE III
The third embodiment provides a preparation method of a multilayer composite thin film solid electrolyte. The multilayer composite thin film solid electrolyte is prepared according to a method comprising the following steps:
1) preparing a lithium lanthanum zirconium titanium oxide block target and a lithium carbonate powder target: preparing lithium lanthanum zirconium oxygen powder and lithium lanthanum titanium oxygen powder by adopting the methods of the first embodiment and the second embodiment, uniformly mixing the lithium lanthanum zirconium oxygen powder and the lithium lanthanum titanium oxygen powder to obtain mixed powder, pressing the obtained lithium lanthanum zirconium titanium oxygen mixed powder into a blank, and sintering at 1100 ℃ in an oxygen atmosphere to obtain a lithium lanthanum zirconium titanium oxygen block target;
uniformly laying lithium carbonate powder in a copper tray with the diameter of 70mm in an argon glove box, and performing unidirectional dry pressing on a lithium carbonate powder material by using a 5T unidirectional press machine to prepare a lithium carbonate powder target;
2) the lithium lanthanum zirconium titanium oxygen block target material is used as a first sputtering source, the distance between a substrate and the target is 50mm and is 1.0 multiplied by 10-2In the mixed atmosphere of high-purity argon and nitrogen in millibar, depositing a lithium lanthanum zirconium titanium oxide film on a stainless steel substrate by a radio frequency magnetron sputtering method; then using the lithium carbonate powder target as a second sputtering source, and on the substrate with the existing lithium lanthanum zirconium titanium oxide film, the distance between the substrate and the target is 50mm, and is 1.0 multiplied by 10-2And (3) depositing a lithium carbonate film in a mixed atmosphere of high-purity argon and nitrogen in millibar, and alternately and repeatedly carrying out the first sputtering treatment and the second sputtering treatment to prepare the multilayer composite film electrolyte. During the thin film deposition, the substrate temperature was maintained at 300 ℃.
And (3) performance testing: carrying out AC impedance test on the multilayer composite film electrolyte prepared in the step 2) in a glove box at the temperature of 25 ℃, wherein the test result is shown in figure 4, and the fitting result shows that the ionic conductivity is 2.83 multiplied by 10-6S/cm, electron conductivity of 5.10X 10-10S/cm, ion conductivity/electron conductivity 5.549 × 103。
Example four
The fourth embodiment provides a preparation method of the composite film solid electrolyte. The composite thin film solid electrolyte is prepared according to a method comprising the following steps:
1) preparing a lithium aluminum titanium phosphate block target and a lithium hexafluorophosphate target: adding a proper amount of absolute ethyl alcohol into lithium acetate dihydrate, stirring at normal temperature to prepare a solution, adding a proper amount of absolute ethyl alcohol into lithium nitrate nonahydrate, stirring at normal temperature to prepare a solution, adding a small amount of deionized water into ammonium dihydrogen phosphate, stirring at 40 ℃ to prepare a solution, adding a proper amount of absolute ethyl alcohol into butyl titanate, stirring at normal temperature to prepare a solution, and mixing the solutions to obtain a white precipitate; drying the white precipitate sample in a vacuum drying oven at 120 ℃ for several hours, taking out, grinding into powder, placing in a muffle furnace at 900 ℃ and sintering for 3 hours to obtain white titanium aluminum lithium phosphate powder; pressing the obtained lithium titanium aluminum phosphate powder into a blank, and sintering at 900 ℃ in an air atmosphere to obtain a lithium titanium aluminum phosphate block target;
respectively and uniformly paving lithium hexafluorophosphate powder with the purity of 99.99 percent in a copper tray with the diameter of 70mm in an argon glove box, and carrying out unidirectional dry pressing on the powder material by using a 5T unidirectional press machine to prepare a lithium hexafluorophosphate powder target material;
2) taking the titanium aluminum lithium phosphate block target material prepared in the step 1) and the lithium hexafluorophosphate powder target material as sputtering sources, wherein the distance between the substrate and the target is 50mm and is 1.0 multiplied by 10 on a stainless steel substrate-2In the mixed atmosphere of high-purity argon and nitrogen in millibar, adopting lithium aluminum titanium phosphate: the composite electrolyte film was prepared by co-sputtering lithium hexafluorophosphate at a power ratio of 2: 1. During the thin film deposition, the substrate temperature was maintained at 300 ℃.
And (3) performance testing: performing an alternating current impedance test on the composite film electrolyte prepared in the step 2) in a glove box at the temperature of 25 ℃, wherein the test result is shown in figure 5, and the fitting result shows that the ionic conductivity is 6.47 multiplied by 10-6S/cm, electron conductivity of 2.34X 10-14S/cm, ion conductivity/electron conductivity 2.765 × 108。
EXAMPLE five
The fifth embodiment provides a preparation method of the composite film solid electrolyte. The composite thin film solid electrolyte is prepared according to a method comprising the following steps:
1) preparing a lithium aluminum germanium phosphate block target and a lithium oxide powder target: lithium carbonate, aluminum hydroxide, germanium dioxide and ammonium dihydrogen phosphate are mixed according to a molar ratio of 1.5: 0.5: 1.5: 3, adding the mixture into a ball mill for ball milling for 4h, calcining the obtained mixed powder in air at 700 ℃ for 2h, re-grinding the mixed powder, sintering the mixed powder at 1400 ℃ for 6h to obtain germanium aluminum lithium phosphate powder, pressing the obtained germanium aluminum lithium phosphate powder into a blank, and sintering the blank at 900 ℃ in air atmosphere to obtain a germanium aluminum lithium phosphate block target;
uniformly laying lithium oxide powder in a copper tray with the diameter of 70mm in an argon glove box, and performing unidirectional dry pressing on the powder material by using a 5T unidirectional press to prepare a lithium oxide powder target;
2) taking the germanium aluminum lithium phosphate block target material and the lithium oxide powder target material prepared in the step 1) as sputtering sources, wherein the distance between the substrate and the target is 50mm and is 1.0 multiplied by 10 on a stainless steel substrate-2In the mixed atmosphere of high-purity argon and nitrogen in millibar, adopting lithium aluminum germanium phosphate: the composite electrolyte film was prepared by co-sputtering lithium oxide at a power ratio of 1: 1. During the thin film deposition, the substrate temperature was maintained at 300 ℃.
And (3) performance testing: carrying out AC impedance test on the multilayer composite film electrolyte prepared in the step 2) in a glove box at the temperature of 25 ℃, wherein the test result is shown in figure 6, and the fitting result shows that the ionic conductivity is 4.22 multiplied by 10-6S/cm, electron conductivity of 1.25X 10-12S/cm, ion conductivity/electron conductivity 3.376 × 106。
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (4)
1. A composite thin film solid electrolyte characterized by:
the composite solid electrolyte comprises a multiphase composite film solid electrolyte which is formed by carrying out co-sputtering treatment deposition growth on an electrolyte source ceramic target and a lithium source additive target in an inert atmosphere or a nitrogen source atmosphere, wherein the ratio of the power for sputtering the electrolyte source ceramic target to the power for sputtering the lithium source additive target is 4: 1-1: 4; or
The lithium ion battery comprises an electrolyte source ceramic film layer and a lithium source additive film layer combined with one surface of the electrolyte source ceramic film layer, wherein the electrolyte source ceramic film layer and the lithium source additive film layer form a basic unit, the basic unit is sequentially laminated and combined in the extending direction from the electrolyte source ceramic film layer to the lithium source additive film layer, and the electrolyte source ceramic film layer is made of a materialThe lithium source additive film layer is made of a lithium source additive target material; wherein the electrolyte source ceramic contained in the electrolyte source ceramic target material comprises Li1+xTi2-xMx(PO4)3、Li1+xGe2-xMx(PO4)3、Li3yLa（2/3）-yTiO3、Li14ZrGe4O16Or Li5La3N2O12At least one of; wherein, 0.1<x<0.7，0<y<0.16, M is at least one of Al, Ga, In and Sc, and N is at least one of Ta and Nb; the lithium source additive contained in the lithium source additive target material comprises at least one of lithium hexafluorophosphate, lithium difluorophosphate, lithium phosphate, lithium carbonate, lithium oxide, lithium hydroxide and a metallic lithium material;
the total thickness of the composite film solid electrolyte is 0.1-10 mu m;
the room-temperature ionic conductivity of the composite film solid electrolyte is 10-1To 10-6Siemens per centimeter; the room-temperature electronic conductivity of the composite film solid electrolyte is 10-10To 10-16Siemens per centimeter.
2. The composite thin film solid electrolyte of claim 1, wherein said electrolyte source ceramic target is prepared according to the following method:
the ceramic powder is prepared by adopting a solid-phase reaction method or a sol-gel method, the prepared ceramic powder is uniformly laid on the surface of a substrate, then dry pressing treatment is carried out on the ceramic powder to obtain a powder target material, and then the powder target material is sintered in an atmosphere to obtain a ceramic block target material.
3. A preparation method of a composite film solid electrolyte comprises the following steps:
co-sputtering the electrolyte source ceramic target and the lithium source additive target in an inert atmosphere or a nitrogen source atmosphere to obtain the multiphase composite electrolyte film, wherein the ratio of the power for sputtering the electrolyte source ceramic target to the power for sputtering the lithium source target is 4: 1-1: 4;
or
The electrolyte source ceramic target material is sputtered in inert atmosphere or nitrogen source atmosphere to grow electrolyte source ceramic film on the substrate, and the electrolyte source ceramic film is then sputtered
Sputtering the lithium source additive target material in an inert atmosphere or a nitrogen source atmosphere to grow a lithium source additive film on the electrolyte source ceramic film; then the
The step of growing the electrolyte source ceramic film layer and the step of growing the lithium source additive film layer are alternately and repeatedly carried out at least once in sequence, wherein the electrolyte source ceramic contained in the electrolyte source ceramic target comprises Li1+xTi2-xMx(PO4)3、Li1+xGe2-xMx(PO4)3、Li3yLa（2/3）-yTiO3、Li14ZnGe4O16Or Li5La3N2O12At least one of; wherein, 0.1<x<0.7，0<y<0.16, M is at least one of Al, Ga, In and Sc, and N is at least one of Ta and Nb; the lithium source additive contained in the lithium source additive target comprises at least one of lithium hexafluorophosphate, lithium difluorophosphate, lithium phosphate, lithium carbonate, lithium oxide, lithium hydroxide and a metallic lithium material, the sputtering power for sputtering and growing the electrolyte source ceramic film layer is 50W-200W, and the sputtering power for sputtering and growing the lithium source additive film layer is 30W-90W;
wherein the total thickness of the composite film solid electrolyte is 0.1-10 μm;
the inert atmosphere or the nitrogen source atmosphere is at least one or more of nitrogen, argon and ammonia;
in the sputtering process, the temperature of the substrate is controlled to be 0-800 ℃.
4. A lithium ion battery, characterized by: comprising the composite thin film solid electrolyte as claimed in any one of claims 1 to 2.
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