CN108365259A - A kind of lithium ion solid electrolyte and the preparation method and application thereof - Google Patents
A kind of lithium ion solid electrolyte and the preparation method and application thereof Download PDFInfo
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- CN108365259A CN108365259A CN201810128024.3A CN201810128024A CN108365259A CN 108365259 A CN108365259 A CN 108365259A CN 201810128024 A CN201810128024 A CN 201810128024A CN 108365259 A CN108365259 A CN 108365259A
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- solid electrolyte
- lithium
- lithium ion
- ion
- germanium
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- 239000007784 solid electrolyte Substances 0.000 title claims abstract description 152
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 102
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 101
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 229910052732 germanium Inorganic materials 0.000 claims abstract description 110
- 239000002228 NASICON Substances 0.000 claims abstract description 63
- -1 germanium ion Chemical class 0.000 claims abstract description 63
- 238000007747 plating Methods 0.000 claims abstract description 52
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 48
- 239000003792 electrolyte Substances 0.000 claims abstract description 30
- 239000007787 solid Substances 0.000 claims abstract description 24
- 238000000576 coating method Methods 0.000 claims abstract description 10
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 32
- 229910052782 aluminium Inorganic materials 0.000 claims description 27
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 27
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 18
- SMBQBQBNOXIFSF-UHFFFAOYSA-N dilithium Chemical compound [Li][Li] SMBQBQBNOXIFSF-UHFFFAOYSA-N 0.000 claims description 18
- 239000002985 plastic film Substances 0.000 claims description 17
- 229920006255 plastic film Polymers 0.000 claims description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000004411 aluminium Substances 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 10
- 229910052759 nickel Inorganic materials 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 8
- 239000002002 slurry Substances 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 7
- 238000005498 polishing Methods 0.000 claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- 229910009496 Li1.5Al0.5Ge1.5 Inorganic materials 0.000 claims description 6
- 239000002041 carbon nanotube Substances 0.000 claims description 6
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 6
- 238000004140 cleaning Methods 0.000 claims description 6
- 238000001659 ion-beam spectroscopy Methods 0.000 claims description 6
- 239000004576 sand Substances 0.000 claims description 6
- 238000003836 solid-state method Methods 0.000 claims description 6
- ZXMGHDIOOHOAAE-UHFFFAOYSA-N 1,1,1-trifluoro-n-(trifluoromethylsulfonyl)methanesulfonamide Chemical compound FC(F)(F)S(=O)(=O)NS(=O)(=O)C(F)(F)F ZXMGHDIOOHOAAE-UHFFFAOYSA-N 0.000 claims description 5
- 238000000498 ball milling Methods 0.000 claims description 5
- 210000005069 ears Anatomy 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 238000005538 encapsulation Methods 0.000 claims description 3
- 150000002500 ions Chemical class 0.000 claims description 2
- 238000001755 magnetron sputter deposition Methods 0.000 claims description 2
- 238000000623 plasma-assisted chemical vapour deposition Methods 0.000 claims description 2
- 238000007740 vapor deposition Methods 0.000 claims description 2
- 238000003466 welding Methods 0.000 claims description 2
- 229910021131 SiyP3−yO12 Inorganic materials 0.000 claims 1
- 238000000227 grinding Methods 0.000 claims 1
- 238000007789 sealing Methods 0.000 claims 1
- 239000011248 coating agent Substances 0.000 abstract description 6
- 230000009467 reduction Effects 0.000 abstract description 5
- 210000001787 dendrite Anatomy 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 3
- 238000005516 engineering process Methods 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 47
- 210000004027 cell Anatomy 0.000 description 28
- 230000004044 response Effects 0.000 description 12
- 238000001453 impedance spectrum Methods 0.000 description 6
- 239000010410 layer Substances 0.000 description 6
- 230000005611 electricity Effects 0.000 description 5
- 238000007731 hot pressing Methods 0.000 description 5
- 238000007599 discharging Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000001069 Raman spectroscopy Methods 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- LRESCJAINPKJTO-UHFFFAOYSA-N bis(trifluoromethylsulfonyl)azanide;1-ethyl-3-methylimidazol-3-ium Chemical compound CCN1C=C[N+](C)=C1.FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F LRESCJAINPKJTO-UHFFFAOYSA-N 0.000 description 3
- 125000004122 cyclic group Chemical group 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 150000002466 imines Chemical class 0.000 description 3
- 239000002608 ionic liquid Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229910000927 Ge alloy Inorganic materials 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 2
- 238000000157 electrochemical-induced impedance spectroscopy Methods 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000005486 organic electrolyte Substances 0.000 description 2
- IBZJNLWLRUHZIX-UHFFFAOYSA-N 1-ethyl-3-methyl-2h-imidazole Chemical class CCN1CN(C)C=C1 IBZJNLWLRUHZIX-UHFFFAOYSA-N 0.000 description 1
- IMSODMZESSGVBE-UHFFFAOYSA-N 2-Oxazoline Chemical compound C1CN=CO1 IMSODMZESSGVBE-UHFFFAOYSA-N 0.000 description 1
- 206010007247 Carbuncle Diseases 0.000 description 1
- 239000002227 LISICON Substances 0.000 description 1
- NPGXALYHLQTILN-UHFFFAOYSA-N N1=CC=CC2=CC=CC=C12.C(C)N1CN(C=C1)C Chemical class N1=CC=CC2=CC=CC=C12.C(C)N1CN(C=C1)C NPGXALYHLQTILN-UHFFFAOYSA-N 0.000 description 1
- 229910020484 P3-yO12 Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 239000002223 garnet Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 239000010416 ion conductor Substances 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- NBVXSUQYWXRMNV-UHFFFAOYSA-N monofluoromethane Natural products FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0561—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
- H01M12/00—Hybrid cells; Manufacture thereof
- H01M12/08—Hybrid cells; Manufacture thereof composed of a half-cell of a fuel-cell type and a half-cell of the secondary-cell type
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0065—Solid electrolytes
- H01M2300/0068—Solid electrolytes inorganic
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Physics & Mathematics (AREA)
- Materials Engineering (AREA)
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Conductive Materials (AREA)
Abstract
A kind of lithium ion solid electrolyte and the preparation method and application thereof, belongs to battery technology field.The lithium ion solid electrolyte includes NASICON type lithium ion solid electrolyte pieces and Ge films containing tetravalence germanium ion, and the Ge films are plated in the NASICON type lithium ion solid electrolyte pieces surface containing tetravalence germanium ion, and coating film thickness is 10 ~ 200 nm.On the one hand the present invention inhibits germanic reduction, protects electrolyte by plating certain thickness Ge films on the surfaces solid electrolyte LAGP；On the other hand so that electrolyte and lithium metal contact are closer, reduce solid state battery interface impedance.In addition, the protected solid electrolyte in the surface can also effectively inhibit the production of Li dendrite, to improve the cyclical stability and coulombic efficiency of battery, the effect for reducing interface impedance and improving interface stability is played to solid state battery.
Description
Technical field
The present invention relates to battery technology fields, and in particular to a kind of lithium ion solid electrolyte and preparation method thereof with answer
With.
Background technology
Lithium ion battery is because high specific energy density is widely paid close attention to and used.Current most of lithium ion batteries
Lithium ion is transmitted using organic electrolyte.But there are security risks for these organic electrolytes, it may occur however that leakage, burning and it is quick-fried
The problems such as fried.In addition, the lithium battery using lithium metal as cathode is during circulating battery, cathode Li dendrite can grow and can
Electrolyte layer can be pierced through, battery short circuit is caused, to which the safety accidents such as burn or explode occur.In order to fundamentally solve this
Problem, researcher use solid electrolyte as lithium ion conductor.Solid electrolyte higher, electrochemistry with lithium ion conductivity
The advantages that window is wide, high mechanical strength.Now widely used solid electrolyte have it is following several, including Ca-Ti ore type,
NASICON types, LISICON types and carbuncle type.In these electrolyte, sulphur system electrolyte is unstable in air, and it is more difficult to prepare.
And in remaining oxide electrolyte, perovskite type electrolyte and lithium metal are unstable, and titanic can be restored by lithium.And garnet
Type electrolyte is widely studied recently, but studies have reported that the electrolyte is in air and unstable, surface can generate one layer
Lithium carbonate film.NASICON type solid electrolytes LAGP has higher lithium ion conductivity（10-4S/cm）Wider electrification
Learn window（6V vs Li/Li+）, and it is highly stable in air, therefore it is commonly used for solid-state lithium-air battery.But
Germanic in LAGP can be reduced into zeroth order or germanous by lithium metal.
Invention content
The technical issues of solution：There is the NASICON type lithium ions containing tetravalence germanium ion in for the above-mentioned prior art
Germanic in solid electrolyte can be reduced into zeroth order or germanous, and the boundary of solid electrolyte and lithium piece by lithium metal
The technical problems such as face impedance is big, the present invention provide a kind of lithium ion solid electrolyte and the preparation method and application thereof, can press down
Keep contact of the electrolyte with lithium metal closer while germanic reduction processed, can also effectively inhibit the production of Li dendrite.
Technical solution：A kind of lithium ion solid electrolyte includes the NASICON type lithium ion solids containing tetravalence germanium ion
Electrolyte sheet and Ge films, the Ge films are plated in the NASICON type lithium ion solid electrolyte pieces surface containing tetravalence germanium ion, plating
Film thickness is 10 ~ 200 nm.
Preferably, the quality of the NASICON type lithium ion solid electrolyte pieces containing tetravalence germanium ion be 0.1 ~
1.0 mg。
Preferably, the NASICON type lithium ion solid electrolytes containing tetravalence germanium ion are
Li1.5Al0.5Ge1.5P3O12、Li1.4Al0.4Ge1.6O12Or Li1+x+yAlx(Ti,Ge)2-xP3-yO12, wherein 0<x<2, 0<y<3.
Another technical solution of the present invention is the preparation method of the lithium ion solid electrolyte, the preparation method
Include that the NASICON type lithium ion solid electrolyte pieces containing tetravalence germanium ion, the preparation side are prepared by conventional solid-state method
Method is further comprising the steps of：By the NASICON type lithium ion solid electrolyte piece sand for surface paper polishing containing tetravalence germanium ion
Then polishing is cleaned by ultrasonic 20 ~ 120 min, by the NASICON type lithium ions containing tetravalence germanium ion after cleaning in ethanol
Solid electrolyte sheet is put into 40 ~ 80 DEG C of 0.5 ~ 12 h of baking in baking oven；Then by the NASICON containing tetravalence germanium ion after drying
Type lithium ion solid electrolyte piece plates Ge films, and film plating process includes vapor deposition, magnetron sputtering, ion beam sputtering, atomic deposition, CVD
Or PECVD, finally obtain the NASICON type lithium ion solid electrolytes containing tetravalence germanium ion of surface plating Ge.
Preferably, the film plating process is ion beam sputtering, specific coating process is as follows：Four will be contained after drying
It is true that the NASICON type lithium ion solid electrolyte pieces of valence germanium ion are put into 2 ~ 35 min of plated film, cavity in Gatan682 plated film instrument
Reciprocal of duty cycle is higher than 10-3Pa, beam energy are set as 6 ~ 7 eV, and electric current is set as 250 ~ 350 μ A, finally obtain surface plating Ge's
NASICON type lithium ion solid electrolytes containing tetravalence germanium ion.
Another technical solution of the present invention is lithium ion solid electrolyte answering in the solid state battery of lithium an- ode
With.
Preferably, another technical solution of the present invention is lithium ion solid electrolyte in solid-state lithium-air battery and consolidates
Application in state lithium-lithium Symmetrical cells.
Preferably, the present invention another technical solution be lithium ion solid electrolyte in solid-state lithium-air battery
Using steps are as follows for concrete application：
By carbon nanotube and ruthenic oxide by high energy ball mill ball milling mixing, obtained mixing material is dispersed in step 1
[C2C1im][NTf2] in and stir and form slurry, which contains tetravalence as what anode was coated uniformly on surface plating Ge
On the NASICON type lithium ion solid electrolytes of germanium ion, plus plate current-collecting body is using the aluminium pole ears for welding aluminium net；
Metal lithium sheet is attached to solid electrolyte another side as battery cathode by step 2, and negative current collector uses nickel lug；
Then step 3 coats solid-state lithium-air battery, positive pole-face trepanning with aluminum plastic film, and use hot press that aluminum plastic film is close
Envelope, finally obtains solid-state lithium-air battery.
Preferably, the present invention another technical solution be lithium ion solid electrolyte in solid-state lithium-lithium Symmetrical cells
In application, steps are as follows for concrete application：
Stick lithium metal in the NASICON type lithium ion solid electrolytes two sides containing tetravalence germanium ion of the surfaces step 1 plating Ge
Piece；
The battery that step 2 aluminum plastic films encapsulation steps one obtain is whole, is used in combination nickel lug as collector, with hot press hot pressing
20 ~ 60 min seal aluminum plastic film, finally obtain solid-state lithium-lithium Symmetrical cells.
Advantageous effect：On the one hand the present invention is pressed down by plating certain thickness Ge films on the surfaces solid electrolyte LAGP
Germanic reduction is made, electrolyte is protected；On the other hand so that electrolyte and lithium metal contact are closer, reduce solid state battery circle
Face impedance.In addition, the protected solid electrolyte in the surface can also effectively inhibit the production of Li dendrite, to improve battery
Cyclical stability and coulombic efficiency.The application makes it be melted in solid electrolyte on piece without heating lithium piece, only need to be in solid
Bath surface uniformly plates last layer nanometer germanium film, you can effectively inhibit reacting between solid electrolyte and lithium metal, and
Interface impedance can be greatly reduced, the guard method of this simple solid electrolyte helps to push solid-state lithium metal battery
In following large-scale use.
Description of the drawings
Fig. 1 is that LAGP solid electrolyte sheets of the present invention surface plating germanium is front and back contacts comparison structure schematic diagram, figure with lithium
Middle a is closer to be contacted with lithium after solid electrolyte plated film, and b is germanium ion variation of valence before and after solid electrolyte plated film in figure
Figure；
Fig. 2 is the pattern and chemical composition analysis figure of LAGP solid electrolytes of the present invention surface plating germanium, and a is non-plated film in figure
Solid electrolyte, b are solid electrolyte after plated film, and c is plated film solid electrolyte cross-sectional scans electron microscope, and d is plated film solid electricity
Matter surface scan electron microscope is solved, e is that plated film solid electrolyte surface etches XPS figures, and f is solid electrolyte Raman before and after plated film
Figure；
Fig. 3 is the electrochemical impedance spectrogram and cyclic curve figure of lithium in embodiment 3-lithium Symmetrical cells, and a is solid electricity before and after plated film
Solve matter and assemble lithium-lithium Symmetrical cells electrochemical impedance spectroscopy, b be plated film solid electrolyte assemble silver-colored blocking electrode Symmetrical cells and
Lithium-lithium Symmetrical cells, c are solid electrolyte assembling lithium-lithium Symmetrical cells charging and discharging curve figure before and after plated film, and d is plated film solid
Electrolyte assembles lithium-lithium Symmetrical cells charging and discharging curve figure under different current densities；
Fig. 4 is lithium in embodiment 3-front and back electrochemical impedance spectrogram of lithium Symmetrical cells cycle, and a is solid electrolyte group before plated film
Impedance spectrum before dress lithium-lithium Symmetrical cells circular response, b are solid electrolyte assembling lithium-lithium Symmetrical cells circular response before plated film
Impedance spectrum afterwards, c are impedance spectrum before solid electrolyte assembling lithium-lithium Symmetrical cells circular response after plated film, and d is solid electricity after plated film
It solves matter and assembles impedance spectrum after lithium-lithium Symmetrical cells circular response；
Fig. 5 is the front and back shape appearance figure of solid electrolyte cycle before and after present invention plating germanium, before a is solid electrolyte circular response after plated film
Surface scan electron microscope, b and c are solid electrolyte circular response rear surface scanning electron microscope (SEM) photograph after plated film, and d is non-plated film solid electricity
Matter table circular response front surface scanning electron microscope (SEM) photograph is solved, e and f are non-plated film solid electrolyte circular response rear surface scanning electron microscope
Figure；
Fig. 6 is solid electrolyte XPS characterizations before and after present invention plating germanium, and a is non-plated film solid electrolyte circular response front surface XPS
Figure, b scheme for non-plated film solid electrolyte circular response rear surface XPS, and c is solid electrolyte sheet circular response front surface after plated film
XPS schemes, and d is solid electrolyte circular response rear surface XPS figures after plated film；
Fig. 7 is solid-state lithium-air battery cyclic curve figure in embodiment 4, and a is the solid-state lithium-air battery schematic diagram, and b is plated film
Front and back solid electrolyte assembles solid-state lithium-air battery electrochemical impedance spectroscopy, and c is solid electrolyte assembling solid-state lithium sky after plated film
Pneumoelectric pond charge and discharge cycles curve, d are that non-plated film solid electrolyte assembles solid-state lithium-air battery charge and discharge cycles curve.
Specific implementation mode
The invention will be further described in the following with reference to the drawings and specific embodiments, so that those skilled in the art are more preferable
Ground understands the present invention, but the invention is not limited in following embodiments.
Embodiment 1
A kind of lithium ion solid electrolyte includes NASICON type lithium ion solid electrolyte pieces and Ge containing tetravalence germanium ion
Film, the Ge films are plated in the NASICON type lithium ion solid electrolyte pieces surface containing tetravalence germanium ion, coating film thickness 10
nm.The quality of the NASICON type lithium ion solid electrolyte pieces containing tetravalence germanium ion is 0.1 mg.It is described to contain tetravalence
The NASICON type lithium ion solid electrolytes of germanium ion are Li1.4Al0.4Ge1.6O12。
The preparation method of the lithium ion solid electrolyte, preparation method include containing four by conventional solid-state method preparation
The NASICON type lithium ion solid electrolyte pieces Li of valence germanium ion1.4Al0.4Ge1.6O12, the preparation method further includes following step
Suddenly：By the NASICON type lithium ion solid electrolyte pieces Li containing tetravalence germanium ion1.4Al0.4Ge1.6O12Sand for surface paper is polished
Polishing, is then cleaned by ultrasonic 20 min, by the NASICON type lithium ion solids containing tetravalence germanium ion after cleaning in ethanol
Electrolyte sheet is put into 40 DEG C of 0.5 h of baking in baking oven；Then the NASICON type lithium ions containing tetravalence germanium ion after drying are consolidated
Body electrolyte sheet plates Ge films, and film plating process is ion beam sputtering, and specific coating process is as follows：Germanic will be contained after drying
The NASICON type lithium ion solid electrolyte pieces of ion are put into 2 min of plated film, chamber vacuum degree in Gatan682 plated film instrument and are higher than
10-3Pa, beam energy are set as 6 eV, and electric current is set as 250 μ A, and finally obtain surface plating Ge contains tetravalence germanium ion
NASICON type lithium ion solid electrolytes.
Application of the lithium ion solid electrolyte in solid-state lithium-air battery, steps are as follows for concrete application：
Step 1 carbon nanotubes and ruthenic oxide are according to 8:1 mass ratio is by high energy ball mill in 500 rpm rotating speeds ball millings 2
Hour, obtained mixing material takes 5 mg to be dispersed in 0.5mL [C2C1im][NTf2] ionic liquid（1- ethyl-3-methylimidazole quinolines
It is double（Trifluoromethyl sulfonyl）Imines, 1-ethyl-3-methyl imidazolium bis
(trifluoromethylsulfonyl)imide）In and stir 12 hours and form slurries, take slurry 0.3mg as anode
It is coated uniformly on the NASICON type lithium ion solid electrolytes containing tetravalence germanium ion of the surface plating Ge, welds aluminium net
Aluminium pole ears as plus plate current-collecting body；
Thickness is 0.5mm by step 2, and the metal lithium sheet of a diameter of 12 mm is attached to solid electrolyte another side and is born as battery
Pole, nickel lug is as negative current collector；
Step 3 then with aluminum plastic film coat solid-state lithium-air battery, positive pole-face trepanning, aperture be 10 mm, film thickness 0.1mm,
And use hot press（PFS-300 hand pressure seal mouth machines）Hot pressing 20min seals aluminum plastic film, finally obtains solid-state lithium-air battery.
Embodiment 2
A kind of lithium ion solid electrolyte includes NASICON type lithium ion solid electrolyte pieces and Ge containing tetravalence germanium ion
Film, the Ge films are plated in the NASICON type lithium ion solid electrolyte pieces surface containing tetravalence germanium ion, coating film thickness 200
nm.The quality of the NASICON type lithium ion solid electrolyte pieces containing tetravalence germanium ion is 1.0 mg.It is described to contain tetravalence
The NASICON type lithium ion solid electrolytes of germanium ion are Li1.4Al0.4Ge1.6O12。
The preparation method of the lithium ion solid electrolyte, the preparation method include being contained by conventional solid-state method preparation
There are the NASICON type lithium ion solid electrolyte pieces of tetravalence germanium ion, the preparation method further comprising the steps of：Four will be contained
The NASICON type lithium ion solid electrolyte piece sand for surface paper sanding and polishings of valence germanium ion, are then cleaned by ultrasonic in ethanol
The NASICON type lithium ion solid electrolyte pieces containing tetravalence germanium ion after cleaning are put into 80 DEG C of bakings in baking oven by 120 min
12 h；Then the NASICON type lithium ion solid electrolyte pieces containing tetravalence germanium ion after drying are plated into Ge films, film plating process
For ion beam sputtering, specific coating process is as follows：By the NASICON type lithium ion solids containing tetravalence germanium ion after drying
Electrolyte sheet is put into 35 min of plated film in Gatan682 plated film instrument, and chamber vacuum degree is higher than 10-3Pa, beam energy are set as 7
EV, electric current are set as 350 μ A, finally obtain the NASICON type lithium ion solids electrolysis containing tetravalence germanium ion of surface plating Ge
Matter.
Application of the lithium ion solid electrolyte in solid-state lithium-air battery, steps are as follows for concrete application：
Step 1 carbon nanotubes and ruthenic oxide are according to 10:1 mass ratio is by high energy ball mill in 800 rpm rotating speed ball millings
6 hours, obtained mixing material take 5mg to be dispersed in 0.5mL [C2C1im][NTf2] ionic liquid（1- ethyl -3- methyl miaows
Oxazoline is double（Trifluoromethyl sulfonyl）Imines, 1-ethyl-3-methyl imidazolium bis
(trifluoromethylsulfonyl)imide）In and stir 24 hours and form slurries, take slurry 1mg as anode
On the even NASICON type lithium ion solid electrolytes containing tetravalence germanium ion coated in surface plating Ge, aluminium net is welded
Aluminium pole ears are as plus plate current-collecting body；
Thickness is 0.8mm by step 2, and the metal lithium sheet of a diameter of 16 mm is attached to solid electrolyte another side and is born as battery
Pole, nickel lug is as negative current collector；
Step 3 then with aluminum plastic film coat solid-state lithium-air battery, positive pole-face trepanning, aperture be 12 mm, film thickness 0.3mm,
And use hot press（PFS-300 hand pressure seal mouth machines）Hot pressing 60min seals aluminum plastic film, finally obtains solid-state lithium-air battery.
Embodiment 3
A kind of lithium ion solid electrolyte includes NASICON type lithium ion solid electrolyte pieces and Ge containing tetravalence germanium ion
Film, the Ge films are plated in the NASICON type lithium ion solid electrolyte pieces surface containing tetravalence germanium ion.It is wherein described to contain four
The NASICON type lithium ion solid electrolyte pieces of valence germanium ion are LAGP（Li1.5Al0.5Ge1.5P3O12）Solid electrolyte sheet.Fig. 1
Be that LAGP solid electrolyte sheets of the present invention surface plating germanium is front and back contacts comparison structure schematic diagram with lithium, and a is solid electricity in figure
Solution matter plated film after contact with lithium it is closer, in figure b be solid electrolyte plated film before and after germanium ion variation of valence figure.As shown,
Contacted with lithium closer after LAGP solid electrolyte sheet plated films, tetravalence germanium ion is reduced into when LAGP pieces are contacted with lithium before plated film
Divalent germanium ion or zeroth order germanium ion, germanic ionic valence condition is constant when LAGP pieces are contacted with lithium after plated film.
The lithium ion solid electrolyte preparation method is as follows：LAGP is prepared by conventional solid-state method
（Li1.5Al0.5Ge1.5P3O12）The quality of solid electrolyte sheet, the LAGP solid electrolyte sheets is 0.75 mg, by LAGP solids
Electrolyte sheet sand for surface paper sanding and polishing, is then cleaned by ultrasonic 30 min in ethanol, by the LAGP solid electrolytics after cleaning
Matter piece is put into 60 DEG C of 2 h of baking in baking oven；Then the LAGP solid electrolyte sheets after drying are put into Gatan682 plated film instrument and are plated
10 min of film, chamber vacuum degree are higher than 10-3 Pa, beam energy are set as 7 eV, and electric current is set as 300 μ A, and coating film thickness is
60 nm finally obtain the NASICON type lithium ion solid electrolytes containing tetravalence germanium ion of surface plating Ge.After plated film
The specific pattern of LAGP solid electrolytes and chemical composition analysis figure are referring to Fig. 2, and before plated film, LAGP solid electrolyte sheets are white；
After plated film, LAGP solid electrolyte sheets surface covers one layer of grey germanium film.Cross-sectional scans Electronic Speculum shows that the thickness of germanium film is
60 nm or so.And positive electron microscope, the film are unformed germanium film.Raman collection of illustrative plates shows that plating germanium film is in 270 and 150
cm-1There are two the peaks of unformed germanium film in broad peak and document to be consistent.
Application of the lithium ion solid electrolyte prepared in the present embodiment in lithium-lithium Symmetrical cells.Made by the present invention
The LAGP solid electrolyte sheets of standby surface plating Ge prepare lithium-lithium Symmetrical cells, including the LAGP pieces of aluminum plastic film, surface plating Ge,
Lithium foil, nickel set fluid, steps are as follows for concrete application：
Stick lithium metal in the NASICON type lithium ion solid electrolytes two sides containing tetravalence germanium ion of the surfaces step 1 plating Ge
Piece；
The battery that step 2 aluminum plastic films encapsulation steps one obtain is whole, is used in combination nickel lug as collector, uses hot press（PFS-
300 hand pressure seal mouth machines）30 min of hot pressing seals aluminum plastic film, finally obtains solid-state lithium-lithium Symmetrical cells.
The LAGP pieces that above-mentioned surface is plated to Ge change the LAGP pieces for not plating Ge in surface into, other steps are constant, are prepared into and do not plate
Solid-state lithium-lithium Symmetrical cells of germanium are as a comparison.
The electrochemical impedance spectrogram and cyclic curve figure of the lithium of preparation-lithium Symmetrical cells are with reference to Fig. 3, by that can be seen in figure
Go out, the Symmetrical cells impedance for not plating germanium is 2506 ohm, and 147 ohm are reduced to after plating germanium, this shows that plating germanium can effectively drop
Low interface impedance.In addition, the electrolyte sheet of plating germanium surveys impedance to gold electrode assembling Symmetrical cells, there is one section long in low-frequency range
Tail represents lithium ion diffusion impedance.And it is then very short in low-frequency range to the Symmetrical cells of lithium, the two comparison shows that germanium film can be with
Effectively pass through lithium ion.If germanium film can not be by lithium ion, should be similar with to gold electrode to the impedance of lithium battery.
Germanium film electrolyte electrochemical performance is plated in Fig. 3 c and d.As shown, after plating germanium, charge and discharge overpotential under same current
It is substantially reduced.The electrolyte of plating germanium film can stablize 200 hours of cycle.In order to test the stability of plating germanium film, we
Have studied the impedance spectrum and XPS spectrum before and after charge and discharge.As shown in figure 4, not plating the impedance of the Symmetrical cells of the LAGP pieces assembling of germanium
300,000 ohm are increased to after 2506 ohmic discharges before electric discharge.And it is 147 Europe after plating germanium, before the impedance discharging of Symmetrical cells
Nurse increases to 1150 ohm after electric discharge.It compares and finds out, after plating germanium, the impedance for the preceding Symmetrical cells that discharge just has been obviously reduced；
In addition, the impedance of plating germanium sample is increased seldom after electric discharge, this is the result shows that plating germanium electrolyte is stable to lithium.Fig. 5 is
Solid electrolyte recycles front and back shape appearance figure before and after plating germanium.Non- plated film LAGP pieces surface, cycle have many fragments to be formed later.And it plates
The LAGP pieces surface of film, cycle form many small flower-shaped products later, it should be Li-Ge alloy interlayers.In order to accurately analyze
Germanium variation of valence, we test the XPS spectrum of Germanium in electrolyte.From Fig. 6 to find out, germanic peak position exists in LAGP
32.3eV or so, after cycle, germanium is reduced to divalent and elemental Germanium.And the peak of the preceding Ge of LAGP electric discharges of germanium is plated on the left sides 29.2eV
The right side, the peak of corresponding elemental Germanium, and Ge position of the peak position of Ge in 26eV or so, corresponding Li-Ge alloys after discharging.These knots
Fruit shows that the stability for plating germanium electrolyte significantly improves, and interface impedance is also substantially reduced, and is conducive to the raising of solid state battery performance.
Embodiment 4
A kind of lithium ion solid electrolyte includes NASICON type lithium ion solid electrolyte pieces and Ge containing tetravalence germanium ion
Film, the Ge films are plated in the NASICON type lithium ion solid electrolyte pieces surface containing tetravalence germanium ion.It is wherein described to contain four
The NASICON type lithium ion solid electrolyte pieces of valence germanium ion are LAGP（Li1.5Al0.5Ge1.5P3O12）Solid electrolyte sheet.
The lithium ion solid electrolyte preparation method is as follows：LAGP is prepared by conventional solid-state method
（Li1.5Al0.5Ge1.5P3O12）The quality of solid electrolyte sheet, the LAGP solid electrolyte sheets is 0.75 mg, by LAGP solids
Electrolyte sheet sand for surface paper sanding and polishing, is then cleaned by ultrasonic 30 min in ethanol, by the LAGP solid electrolytics after cleaning
Matter piece is put into 60 DEG C of 2 h of baking in baking oven；Then the LAGP solid electrolyte sheets after drying are put into Gatan682 plated film instrument and are plated
10 min of film, chamber vacuum degree are higher than 10-3 Pa, beam energy are set as 7 eV, and electric current is set as 300 μ A, and coating film thickness is
60 nm finally obtain the NASICON type lithium ion solid electrolytes containing tetravalence germanium ion of surface plating Ge.After plated film
The specific pattern of LAGP solid electrolytes and chemical composition analysis figure are referring to Fig. 2, and before plated film, LAGP solid electrolyte sheets are white；
After plated film, LAGP solid electrolyte sheets surface covers one layer of grey germanium film.Cross-sectional scans Electronic Speculum shows that the thickness of germanium film is
60 nm or so.And positive electron microscope, the film are unformed germanium film.Raman collection of illustrative plates shows that plating germanium film is in 270 and 150
cm-1There are two the peaks of unformed germanium film in broad peak and document to be consistent.
Application of the lithium ion solid electrolyte prepared in the present embodiment in solid-state lithium-air battery.Concrete application step
It is as follows：Carbon nanotube and ruthenic oxide are according to 9:1 mass ratio is by high energy ball mill in 2 hours of 700 rpm rotating speeds ball millings.
Obtained mixing material takes 5mg to be dispersed in 0.5mL [C2C1im][NTf2] ionic liquid（1- ethyl-3-methylimidazoles quinoline is double（Three
Methyl fluoride sulfonyl）Imines, 1-ethyl-3-methyl imidazolium bis (trifluoromethylsulfonyl)
imide）In and stir 12 hours and form slurries.It slurry 1mg is taken as anode is coated uniformly on surface and plate Ge and contain four
On the NASICON type lithium ion solid electrolytes of valence germanium ion, the aluminium pole ears of aluminium net are welded as plus plate current-collecting body；By thickness
Metal lithium sheet for 0.5mm, a diameter of 14 mm is attached to solid electrolyte another side as battery cathode, and nickel lug is as cathode
Collector；Then solid-state lithium-air battery is coated with aluminum plastic film, positive pole-face trepanning, aperture is 12 mm, film thickness 0.1mm, and is used
Hot press（PFS-300 hand pressure seal mouth machines）Hot pressing 30min seals aluminum plastic film, finally obtains solid-state lithium-air battery.
The solid-state lithium-air battery of preparation is referring to Fig. 7, and the solid-state lithium-air battery is using carbon nanotube/gel as just
Pole, plating germanium LAGP is as electrolyte layer and lithium as cathode.The impedance of impedance spectrum comparison display plating germanium solid state battery is obviously dropped
It is low.In addition, the cycle 30 that the interface stablized allows plating germanium electrolyte lithium air cell to stablize is enclosed；And the battery of germanium is not plated
Battery capacity just decays much after nine circle of cycle.These are the result shows that the LAGP solid electrolyte sheets of plating germanium can use lithium metal
As cathode, and effectively provide the chemical property of battery.
Can to sum up it illustrate, the protection of surface coating designed by the application contains germanic solid electrolyte sheet, and one
Aspect inhibits germanic reduction, protects electrolyte；On the other hand so that electrolyte and lithium metal contact are closer, reduce solid-state
Cell interface impedance.In addition, the program can also be extended to the high-energy densities systems such as solid-state lithium air, lithium-sulfur cell, also may be used
, using in the solid state battery of lithium an- ode, to play reduction interface impedance applied to other to solid state battery and raising interface be steady
Qualitative effect.It can significantly reduce battery impedance, the cyclical stability and coulombic efficiency for improving battery.
Claims (9)
1. a kind of lithium ion solid electrolyte, which is characterized in that include the NASICON type lithium ion solids containing tetravalence germanium ion
Electrolyte sheet and Ge films, the Ge films are plated in the NASICON type lithium ion solid electrolyte pieces surface containing tetravalence germanium ion, plating
Film thickness is 10 ~ 200 nm.
2. a kind of lithium ion solid electrolyte according to claim 1, which is characterized in that described containing tetravalence germanium ion
The quality of NASICON type lithium ion solid electrolyte pieces is 0.1 ~ 1.0 mg.
3. a kind of lithium ion solid electrolyte according to claim 1 or 2, which is characterized in that it is described containing germanic from
The NASICON type lithium ion solid electrolytes of son are Li1.5Al0.5Ge1.5P3O12、Li1.4Al0.4Ge1.6O12Or Li1+x+yAlx(Ti,
Ge)2-xSiyP3-yO12, wherein 0<x<2, 0<y<3.
4. based on a kind of preparation method of lithium ion solid electrolyte described in claim 1, the preparation method includes passing through
Conventional solid-state method prepares the NASICON type lithium ion solid electrolyte pieces containing tetravalence germanium ion, which is characterized in that the preparation
Method is further comprising the steps of：NASICON type lithium ion solid electrolyte piece sand for surface paper containing tetravalence germanium ion is beaten
Grinding and polishing light, then in ethanol be cleaned by ultrasonic 20 ~ 120 min, by the NASICON types lithium containing tetravalence germanium ion after cleaning from
Sub- solid electrolyte sheet is put into 40 ~ 80 DEG C of 0.5 ~ 12 h of baking in baking oven；Then by after drying containing tetravalence germanium ion
NASICON type lithium ion solid electrolyte pieces plate Ge films, and film plating process is heavy including vapor deposition, magnetron sputtering, ion beam sputtering, atom
Product, CVD or PECVD finally obtain the NASICON type lithium ion solid electrolytes containing tetravalence germanium ion of surface plating Ge.
5. a kind of preparation method of lithium ion solid electrolyte according to claim 4, which is characterized in that the plated film side
Method is ion beam sputtering, and specific coating process is as follows：The NASICON type lithium ions containing tetravalence germanium ion after drying are consolidated
Body electrolyte sheet is put into 2 ~ 35 min of plated film in Gatan682 plated film instrument, and chamber vacuum degree is higher than 10-3 Pa, beam energy are set
It is set to 6 ~ 7 eV, electric current is set as 250 ~ 350 μ A, finally obtains the NASICON type lithiums containing tetravalence germanium ion of surface plating Ge
Ion solid electrolyte.
6. the application based on a kind of lithium ion solid electrolyte described in claim 1 in the solid state battery of lithium an- ode.
7. symmetrical in solid-state lithium-air battery and solid-state lithium-lithium based on a kind of lithium ion solid electrolyte described in claim 1
Application in battery.
8. application of the lithium ion solid electrolyte according to claim 7 in solid-state lithium-air battery, which is characterized in that
Steps are as follows for concrete application：
By carbon nanotube and ruthenic oxide by high energy ball mill ball milling mixing, obtained mixing material is dispersed in step 1
[C2C1im][NTf2] in and stir and form slurry, which contains tetravalence as what anode was coated uniformly on surface plating Ge
On the NASICON type lithium ion solid electrolytes of germanium ion, plus plate current-collecting body is using the aluminium pole ears for welding aluminium net；
Metal lithium sheet is attached to solid electrolyte another side as battery cathode by step 2, and negative current collector uses nickel lug；
Then step 3 coats solid-state lithium-air battery, positive pole-face trepanning with aluminum plastic film, and use hot press that aluminum plastic film is close
Envelope, finally obtains solid-state lithium-air battery.
9. application of the lithium ion solid electrolyte according to claim 7 in solid-state lithium-lithium Symmetrical cells, feature exist
In steps are as follows for concrete application：
Stick lithium metal in the NASICON type lithium ion solid electrolytes two sides containing tetravalence germanium ion of the surfaces step 1 plating Ge
Piece；
Battery that step 2 aluminum plastic films encapsulation steps one obtain is whole, is used in combination nickel lug as collector, with hot press by aluminium
Plastic film sealing finally obtains solid-state lithium-lithium Symmetrical cells.
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| CN111370627A (en) * | 2020-03-27 | 2020-07-03 | 中国人民解放军军事科学院防化研究院 | Direct compounding method of metal lithium electrode and inorganic solid electrolyte ceramic diaphragm |
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| CN111370627A (en) * | 2020-03-27 | 2020-07-03 | 中国人民解放军军事科学院防化研究院 | Direct compounding method of metal lithium electrode and inorganic solid electrolyte ceramic diaphragm |
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