CN104810545B - Phosphate lithium fast-ionic conductor material and preparation method thereof - Google Patents
Phosphate lithium fast-ionic conductor material and preparation method thereof Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 70
- 239000010416 ion conductor Substances 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 title abstract description 7
- 239000000843 powder Substances 0.000 claims abstract description 83
- 239000011521 glass Substances 0.000 claims abstract description 57
- 238000000034 method Methods 0.000 claims abstract description 47
- 239000004020 conductor Substances 0.000 claims abstract description 23
- 229910021131 SiyP3−yO12 Inorganic materials 0.000 claims abstract description 11
- 238000010438 heat treatment Methods 0.000 claims description 36
- 238000001816 cooling Methods 0.000 claims description 32
- 238000000465 moulding Methods 0.000 claims description 21
- 238000010791 quenching Methods 0.000 claims description 18
- 238000000137 annealing Methods 0.000 claims description 16
- 230000008569 process Effects 0.000 claims description 15
- 230000000171 quenching effect Effects 0.000 claims description 13
- 238000000748 compression moulding Methods 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 4
- 239000006112 glass ceramic composition Substances 0.000 claims description 3
- 238000007569 slipcasting Methods 0.000 claims description 3
- 238000009987 spinning Methods 0.000 claims description 3
- 238000010345 tape casting Methods 0.000 claims description 3
- 238000005096 rolling process Methods 0.000 claims 1
- 150000002500 ions Chemical class 0.000 abstract description 22
- 238000007493 shaping process Methods 0.000 abstract 1
- 239000002241 glass-ceramic Substances 0.000 description 38
- 229910052744 lithium Inorganic materials 0.000 description 35
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 34
- 238000001035 drying Methods 0.000 description 33
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium oxide Inorganic materials O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 description 27
- 238000002156 mixing Methods 0.000 description 27
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 26
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 24
- 238000001238 wet grinding Methods 0.000 description 24
- 229910019142 PO4 Inorganic materials 0.000 description 22
- 238000012360 testing method Methods 0.000 description 22
- 229910001416 lithium ion Inorganic materials 0.000 description 20
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 18
- 238000000498 ball milling Methods 0.000 description 18
- 239000007784 solid electrolyte Substances 0.000 description 18
- 239000002228 NASICON Substances 0.000 description 14
- 238000004321 preservation Methods 0.000 description 14
- 229910017677 NH4H2 Inorganic materials 0.000 description 13
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 13
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 13
- 229910001679 gibbsite Inorganic materials 0.000 description 13
- 238000000227 grinding Methods 0.000 description 13
- 239000007788 liquid Substances 0.000 description 13
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 13
- 229910052808 lithium carbonate Inorganic materials 0.000 description 13
- 229910052757 nitrogen Inorganic materials 0.000 description 12
- 230000000903 blocking effect Effects 0.000 description 11
- 229910052681 coesite Inorganic materials 0.000 description 11
- 229910052906 cristobalite Inorganic materials 0.000 description 11
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 11
- 239000010931 gold Substances 0.000 description 11
- 229910052737 gold Inorganic materials 0.000 description 11
- 239000000377 silicon dioxide Substances 0.000 description 11
- 229910052682 stishovite Inorganic materials 0.000 description 11
- 239000000126 substance Substances 0.000 description 11
- 229910052905 tridymite Inorganic materials 0.000 description 11
- 238000004364 calculation method Methods 0.000 description 10
- 238000004146 energy storage Methods 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 239000013078 crystal Substances 0.000 description 9
- 238000003754 machining Methods 0.000 description 9
- 238000003825 pressing Methods 0.000 description 9
- 239000012535 impurity Substances 0.000 description 8
- 238000001144 powder X-ray diffraction data Methods 0.000 description 8
- 239000000919 ceramic Substances 0.000 description 7
- 238000000354 decomposition reaction Methods 0.000 description 6
- 239000003792 electrolyte Substances 0.000 description 6
- 239000000156 glass melt Substances 0.000 description 6
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- 239000013590 bulk material Substances 0.000 description 4
- 238000002425 crystallisation Methods 0.000 description 4
- 230000008025 crystallization Effects 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- 229910009496 Li1.5Al0.5Ge1.5 Inorganic materials 0.000 description 3
- 229910010293 ceramic material Inorganic materials 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000009776 industrial production Methods 0.000 description 3
- 229910001386 lithium phosphate Inorganic materials 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- JLDSOYXADOWAKB-UHFFFAOYSA-N aluminium nitrate Chemical compound [Al+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O JLDSOYXADOWAKB-UHFFFAOYSA-N 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 238000009694 cold isostatic pressing Methods 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 238000007731 hot pressing Methods 0.000 description 2
- 239000011244 liquid electrolyte Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000013500 performance material Substances 0.000 description 2
- -1 polytetrafluoroethylene Polymers 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 238000012876 topography Methods 0.000 description 2
- 238000007514 turning Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910000733 Li alloy Inorganic materials 0.000 description 1
- 229910010084 LiAlH4 Inorganic materials 0.000 description 1
- 229910010954 LiGe2(PO4)3 Inorganic materials 0.000 description 1
- 229910010951 LiH2 Inorganic materials 0.000 description 1
- 229910011122 LiM2(PO4)3 Inorganic materials 0.000 description 1
- 229910000857 LiTi2(PO4)3 Inorganic materials 0.000 description 1
- 229910003249 Na3Zr2Si2PO12 Inorganic materials 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910052849 andalusite Inorganic materials 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229910001598 chiastolite Inorganic materials 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- 238000002484 cyclic voltammetry Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 1
- 229910000388 diammonium phosphate Inorganic materials 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 238000001453 impedance spectrum Methods 0.000 description 1
- 229910052850 kyanite Inorganic materials 0.000 description 1
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 description 1
- 239000012280 lithium aluminium hydride Substances 0.000 description 1
- 229910000032 lithium hydrogen carbonate Inorganic materials 0.000 description 1
- WMFOQBRAJBCJND-UHFFFAOYSA-M lithium hydroxide Inorganic materials [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 1
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Inorganic materials [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000005486 organic electrolyte Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910052851 sillimanite Inorganic materials 0.000 description 1
- 239000002203 sulfidic glass Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 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
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Secondary Cells (AREA)
- Glass Compositions (AREA)
Abstract
The invention provides a kind of phosphate lithium fast-ionic conductor material and preparation method thereof, specifically, Li is prepared the invention provides one kind1+x+y+zAlxGe2‑xSiyP3‑yO12+z/2The method of fast ion conducting material, the described method comprises the following steps：A powder that there is above-mentioned element to match is provided, described powder is glass powder or amorphous powder；It is molded described powder, the vitreum being molded；The vitreum of the shaping is annealed, described fast ion conducting material is obtained；Wherein, 0 ＜ x≤2,0≤y≤0.4,0≤z≤0.5.It is convenient that the preparation method of the present invention has, high yield rate, and the features such as being adapted to preparation of industrialization, the material of preparation has extraordinary electric property.
Description
Technical Field
The invention belongs to the field of solid-state ionic materials, and particularly relates to a component design and a preparation method of a fast lithium ion conductor material.
Background
Lithium ion batteries have been applied and developed relatively late as a chemical energy storage mode, but they are regarded as one of the most competitive electrochemical energy storage technologies due to their characteristics of light weight, high specific energy/specific power, long life, and the like, and are increasingly widely used in various energy storage links. The batch production of the lithium ion batteries of different systems lays a good technical foundation for the application of the lithium ion batteries in an energy storage system. At present, the lithium ion battery has the conditions of long service life, safety, reliability, low maintenance cost, high conversion efficiency and the like, breaks through the difficulty of large-scale integrated application along with the progress of the battery management system technology, gradually develops into an ideal power supply of a novel chemical energy storage technology, can be used for frequency modulation, phase modulation and voltage regulation of a smart power grid, and ensures the quality of new energy power.
In the future, how to greatly improve the cycle life and capacity of the chemical energy storage battery on the existing basis is advanced, the problem of safety is thoroughly solved to be the most critical breakthrough point in the field development, and after the chemical energy storage battery is applied to local energy storage and a smart grid, the importance of the safety of the battery is more and more important, especially when the capacity is enlarged to megawatt level. The large-scale application of the energy storage battery can be promoted only if the potential safety hazard of the energy storage battery is thoroughly solved. The urgent need for high-safety rechargeable batteries in the field of energy storage has greatly driven the development of all-solid-state lithium batteries, and solid-state lithium batteries using solid electrolytes instead of conventional liquid organic electrolytes are attracting more and more attention.
The solid electrolyte has excellent safety performance because of being non-combustible and stable to the electrode, and simultaneously removes the possibility of capacity attenuation caused by side reaction with the electrode. The electrolyte has wide use temperature range and long service life, and is an ideal substitute for liquid electrolyte. In addition, the diaphragm can completely replace the diaphragm in the lithium battery, thereby further simplifying the structure of the battery, facilitating the production and the use of the battery, breaking through the limitation of the shape of the battery and enabling the battery to be designed into various shapes. Finally, it can be applied to other systems besides lithium batteries, such as lithium air batteries, lithium sulfur batteries, etc., and is a very potential material. However, since the mobility rate of carriers in the solid electrolyte is lower than the charge transfer rate and the diffusion rate, which is a rate control step in the electrochemical reaction, the preparation of the solid electrolyte having higher ionic conductivity is a key point for practical application of the solid lithium battery.
NASICON-type material LiM2(PO4)3(M = Ti, Ge, etc.) is an oxide system phosphate solid electrolyte material with high ionic conductivity. Unlike sulfide solid electrolytes, it can be used stably in air. The parent body is NaZr2P3O12The structure is made of PO4Tetrahedron and MO6The octahedron shares a top angle to form the hollow sphere,each MO6Octahedron connected six POs4Tetrahedron, each PO4Tetrahedrally connecting four MOs6Octahedron. Li+Transported in the framework gap by defect transitions.
Currently, LiM is prepared2(PO4)3The method for preparing the ceramic material is mainly a traditional high-temperature sintering method, but the material prepared by the method has low density, a plurality of internal defects and unsatisfactory phase purity, so that the ionic conductivity of the material is different from the practical application level.
In conclusion, a lithium fast ion conductor material which has high density, high room temperature conductivity and simple preparation method for air stability and is suitable for industrial production is not provided in the field.
Disclosure of Invention
The invention aims to provide a lithium fast ion conductor material which has high density, high room temperature conductivity and simple preparation method for air stability and is suitable for industrial production.
In a first aspect of the invention, there is provided a method for preparing Li1+x+y+zAlxGe2-xSiyP3-yO12+z/2A method of fast ion conductor material comprising the steps of:
providing a powder with the element ratio, wherein the powder is glass powder or amorphous powder;
molding the powder to obtain a molded glass body;
annealing the formed glass body to obtain the fast ion conductor material;
wherein x is more than 0 and less than or equal to 2, y is more than or equal to 0 and less than or equal to 0.4, z is more than or equal to 0 and less than or equal to 0.5, preferably, x is more than 0 and less than 2, y is more than 0 and less than 0.4, z is more than 0 and less than 0.5, more preferably, x =0.5, and z is more than or equal to 0.01 and less than or equal to 0.1.
In another preferred embodiment, before the annealing step, the method further comprises: and carrying out cold isostatic pressing treatment on the formed glass body.
In another preferred example, the powder is pretreated before being molded; preferably, the pretreatment is selected from the group consisting of: heat treatment, powder particle optimization, or a combination thereof.
In another preferred embodiment, the glass powder is formed by a process selected from the group consisting of: compression molding, tape casting molding, extrusion molding, spinning molding, roll forming, turning blank molding, slip casting molding and near net size molding.
In another preferred embodiment, when the process is press forming, the pressure of the press forming process is 100 to 500MPa, and more preferably 200 to 400 MPa.
In another preferred embodiment, the annealing step includes: preserving heat at 450-700 ℃; and/or
And preserving heat at 850-950 ℃.
In another preferred embodiment, the annealing step includes: preserving the heat for 2-14 h at 450-700 ℃; and/or preserving the heat for 4-24 hours at 850-950 ℃.
In another preferred example, when the powder is glass powder, the preparation method comprises the following steps:
providing a high-temperature molten mass with the element proportion;
quenching the molten mass to obtain quenched glass;
and crushing the quenched glass to obtain glass powder.
In another preferred embodiment, the quenching step is performed in liquid nitrogen or water.
In another preferred example, the crushing step is carried out under ball milling conditions; preferably, the ball milling pot is selected from the following group: an agate ball milling jar, a stainless steel ball milling jar, a nylon ball milling jar, a polyurethane ball milling jar, or a polytetrafluoroethylene ball milling jar; the ball milling balls are selected from the following groups: agate balls, stainless steel balls, zirconia balls, or combinations thereof.
In another preferred embodiment, the high-temperature melt is prepared by the following method:
(1) li source, Al source, P source, Si source and Ge source are mixed according to Li1+x+y+zAlxGe2-xSiyP3-yO12+z/2Stoichiometric ratio, wherein x, y, z are as defined above;
(2) heating the mixture, preserving heat, cooling, and crushing to obtain powder;
(3) and heating the powder, and preserving heat to obtain the high-temperature molten mass.
In another preferred embodiment, the Li source is selected from the group consisting of: li2CO3LiOH and hydrate thereof, LiHCO3、CH3COOLi、CHOOLi、Li3PO4、LiAlH4、LiH2PO4、LiNO3Or a combination thereof.
In another preferred embodiment, the Al source is selected from the group consisting of: al (OH)3、Al2O3、Al(PO3)3、AlPO4、Al(NO3)3、Al2SiO5、3Al2O3·2SiO2Al powder, Al alkoxide, or combinations thereof; wherein, the alcohol refers to alcohol with 1-8 carbons.
In another preferred embodiment, the P source is selected from the group consisting of: NH (NH)4H2PO4、(NH4)2HPO4、P2O5、Al(PO3)3、AlPO4、H3PO4Or a combination thereof.
In another preferred embodiment, the Ge source is selected from the group consisting of: GeO2Ge, or a combination thereof.
In another preferred embodiment, the Si source is selected from the group consisting of: SiO 22、Si、H2SiO3，3Al2O3·2SiO2、Al2SiO5Or a combination thereof.
In another preferred example, in the step (2), the heat preservation temperature is 500-900 ℃.
In another preferred example, in the step (2), the pulverization is performed under ball milling conditions, preferably under wet milling conditions.
In another preferred example, in the step (3), the heating temperature is 1300-1600 ℃.
In another preferred example, the holding time in the step (2) is 1-3 h.
In another preferred example, the holding time in the step (3) is 1-3 h.
In another preferred embodiment, the mixing in step (1) is performed under ball milling conditions, preferably, the ball milling conditions include: adding dispersant and ball milling.
In a second aspect of the present invention, a fast ion conductor material is provided, which has an element ratio shown as the following formula:
Li1+x+y+zAlxGe2-xSiyP3-yO12+z/2
wherein,
x is more than 0 and less than or equal to 2, preferably, x is more than 0 and less than 2, and more preferably, x = 0.5;
y is more than or equal to 0 and less than or equal to 0.4, preferably, y is more than 0 and less than 0.4, and more preferably, y is more than 0 and less than 0.2;
z is more than or equal to 0 and less than or equal to 0.5, preferably more than 0 and less than or equal to 0.5, and more preferably more than or equal to 0.01 and less than or equal to 0.1.
In another preferred embodiment, the conductive material is prepared by the method according to the first aspect of the present invention.
In another preferred embodiment, the material is free or substantially free of a hetero-phase.
In another preferred embodiment, the substantial absence refers to the absence of a hetero-phase peak in the XRD pattern of the material.
In another preferred embodiment, the conductor material is a glass-ceramic material.
In another preferred embodiment, the room temperature ionic conductivity of the conductor material is 8 × 10-5～5×10-3S/cm, preferably 1 × 10-4～1×10-3S/cm。
In another preferred embodiment, the porosity of the conductive material is 0 to 15%, preferably 0 to 6%.
In another preferred example, the decomposition voltage of the material is ≥ 6V (relative to lithium metal).
In a third aspect of the invention, there is provided an article comprising a conductive material according to the second aspect of the invention, or a conductive material prepared by a process according to the first aspect of the invention.
In another preferred embodiment, the article is selected from the group consisting of: lithium ion batteries, electrochromic devices.
It is to be understood that within the scope of the present invention, the above-described features of the present invention and those specifically described below (e.g., in the examples) may be combined with each other to form new or preferred embodiments. Not to be reiterated herein, but to the extent of space.
Drawings
FIG. 1 is a powder XRD pattern of the ceramic lithium fast ion bulk material in comparative example 1, the main crystal phase is NASICON structure, and there is no impurity phase.
FIG. 2 is a powder XRD pattern of lithium fast ion bulk material for glass ceramics in comparative example 2, the main crystal phase is NASICON structure and has no impurity phase.
FIG. 3 is a powder XRD pattern of the lithium fast ion bulk material for glass ceramics in example 4, and the main crystal phase is NASICON structure and has no impurity phase.
FIG. 4 is the powder XRD pattern of the lithium fast ion bulk material for glass ceramics in example 7, and the main crystal phase is NASICON structure and has no impurity phase.
FIG. 5SEM topography: (a) cross-sectional SEM morphology of ceramic bulk sample in comparative example 2 (b) cross-sectional SEM morphology of glass-ceramic bulk sample in example 1 (c) cross-sectional SEM morphology of glass-ceramic bulk sample in example 4 (d) cross-sectional SEM morphology of glass-ceramic bulk sample in example 7. From the microscopic compactness, (a) and (d) have larger porosities than (b) and (c).
FIG. 6 is a graph showing the room temperature AC impedance of the product of comparative example 2, from which it can be seen that the room temperature ionic conductivity is 8.4 × 10- 5S/cm。
FIG. 7 is a graph of the room temperature AC impedance of the product of example 1, from which it can be seen that the room temperature ionic conductivity is 2.1 × 10- 4S/cm。
FIG. 8 is a graph of the room temperature AC impedance of the product of example 4, from which it can be seen that the room temperature ionic conductivity is 8.1 × 10- 4S/cm。
FIG. 9 shows Li in example 41.65Al0.5Ge1.5Si0.1P2.9O12.025Room temperature cyclic voltammogram of a glass ceramic/Li cell.
FIG. 10 shows Li/Li in example 41.65Al0.5Ge1.5Si0.1P2.9O12.025Room temperature ac impedance profile of glass ceramic/Li cell.
Detailed Description
The inventor of the present invention has conducted extensive and intensive studies for a long time, and unexpectedly found that a glass block having a compact surface and no cracks can be easily prepared by completely cooling the glass ceramic immediately after the glass ceramic is formed by high-temperature quenching, then preparing glass powder, and finally performing press molding and annealing on the powder, and a compact and stable-performance material can be well prepared by subsequent cold isostatic press molding and annealing. Based on the above findings, the inventors have completed the present invention.
Term(s) for
As used herein, the term "room temperature ionic conductivity" is used interchangeably with the term "room temperature total conductivity" and both refer to the conductivity of a body at room temperature.
As used herein, the term "fast lithium ion conductor material" or "fast lithium ion material" refers to a class of solid state substances that have a conductivity of lithium ions of the material at the temperature used that is comparable to or close to the level of ionic conductivity of molten salts or liquid electrolytes, with a conductivity activation energy of less than 0.5eV, and may also be referred to as "fast lithium ion conductor material", "fast lithium ion material" or "fast ion conductor material".
The term "glass-ceramic" refers to microcrystalline glass, a polycrystalline solid produced by controlled crystallization of glass, which is different from conventional ceramic materials in that the crystallization of a conductive crystalline phase from a glass matrix can result in a significant increase in electrical conductivity.
The term "glass" refers to a glassy electrolyte, as opposed to a crystalline electrolyte. The crystal electrolyte is affected by the grain boundary effect, and the lithium ion conductivity is not high. Glass is amorphous solid, basically has isotropy, ion diffusion channels are also isotropic, and the connection of the diffusion channels among particles is easier than that of crystalline materials.
The terms "NASICON phase" or "phase with NASICON structure" are used interchangeably and refer to a widely studied class of solid electrolyte materials, the parent of which is Na3Zr2Si2PO12Therein is provided withNa of (2)+By conversion to Li+And can be applied to lithium ion solid electrolytes.
Phosphate lithium fast ion conductor material
Prior art LiTi2(PO4)3System or Li (Ge, Ti) (PO)4)3The solid electrolyte material of the system has better electrical properties, such as room temperature conductivity and the like. However, the stability of the above materials and the lithium battery positive electrode material is not good, and the solid electrolyte material is easily to fail. Accordingly, the present invention provides a Li1+x+y+zAlxGe2-xSiyP3-yO12+z/2A solid electrolyte material having improved chemical and electrochemical stability.
Specifically, the material provided by the invention has the following element proportion as shown in the following formula:
Li1+x+y+zAlxGe2-xSiyP3-yO12+z/2
wherein,
x is more than 0 and less than or equal to 2, preferably, x is more than 0 and less than 2, and more preferably, x = 0.5;
y is more than or equal to 0 and less than or equal to 0.4, preferably, y is more than 0 and less than 0.4, and more preferably, y is more than 0 and less than 0.2;
z is more than or equal to 0 and less than or equal to 0.5, preferably more than 0 and less than or equal to 0.5, and more preferably more than or equal to 0.01 and less than or equal to 0.1.
In another preferred embodiment, the material is free or substantially free of a hetero-phase.
Preferably, the material is a glass-ceramic material, which is more dense than prior art ceramic materials and has significantly improved grain boundary conductivity, thus increasing the overall ionic conductivity.
The conductor material has L in the prior artiTi2(PO4)3System or Li (Ge, Ti) (PO)4)3The ion conductivity at room temperature is similar to that of the system, and in another preferred example, the ion conductivity at room temperature of the material is 8 × 10-5～5×10- 3S/cm, preferably 1 × 10-4～1×10-3S/cm。
Preparation of lithium phosphate fast ion conductor material
The invention also provides a method for preparing the material. In the prior art, the method for preparing the lithium phosphate fast ion conductor material needs to anneal the quenched glass at medium and high temperature, such as 500 ℃, and the process is easy to cause the phenomenon that the glass cracks due to stress, and finally influences the material performance.
The invention is that the medium-high temperature annealing is not carried out immediately after the high-temperature quenching forms the glass, but the glass is cooled completely immediately, then the preparation of the glass powder is carried out, and finally the compression molding and annealing of the powder are carried out.
Specifically, the invention provides a high-temperature glass melt with the element proportion;
quenching the glass melt to obtain a quenched glass melt;
crushing the quenched glass melt to obtain glass powder;
molding the glass powder to obtain a molded glass body;
annealing the formed glass body to obtain the lithium fast ion conductor material;
wherein x is more than 0 and less than or equal to 2, y is more than or equal to 0 and less than or equal to 0.4, z is more than or equal to 0 and less than or equal to 0.5, preferably, x is more than 0 and less than 2, y is more than 0 and less than 0.4, z is more than 0 and less than 0.5, more preferably, x =0.5, y is more than 0 and less than 0.4, and z is more than or equal to 0.01 and less than or equal to 0.1.
In another preferred embodiment, the quenching step is performed in liquid nitrogen or water.
In another preferred example, the crushing step is carried out under ball milling conditions; preferably, the ball milling pot is selected from the following group: an agate ball milling jar, a stainless steel ball milling jar, or a polytetrafluoroethylene ball milling jar; the ball milling balls are selected from the following groups: agate balls, stainless steel balls, zirconia balls, or combinations thereof.
In another preferred embodiment, before the annealing step, the method further comprises: and carrying out cold isostatic pressing treatment on the formed glass body.
Preferably, the glass powder is formed by a process selected from the group consisting of: compression molding, tape casting molding, extrusion molding, spinning molding, roll forming, turning blank molding, slip casting molding and near net size molding.
In another preferred embodiment, the pressure of the pressing process is 100 to 500MPa, and more preferably 200 to 400 MPa.
In the present invention, a preferred annealing step comprises: preserving heat at 400-650 ℃; and/or preserving heat at 650-950 ℃; preferably, the annealing step comprises: preserving heat for 2-14 h at 400-650 ℃; and/or preserving the heat for 4-24 hours at 650-950 ℃.
In the present invention, the high-temperature glass melt may be obtained by any conventional method, for example, by:
(1) li source, Al source, P source, Si source and Ge source are mixed according to Li1+x+y+zAlxGe2-xSiyP3-yO12+z/2Stoichiometric ratio, wherein x, y, z are as defined above;
(2) heating the mixture, preserving heat, cooling, and crushing to obtain powder;
(3) and heating the powder, and preserving heat to obtain the high-temperature glass melt.
The invention has the advantages that the solid electrolyte material with higher density and room temperature lithium ion conductivity can be prepared without adopting special heat treatment process methods such as hot pressing, plasma discharge sintering (SPS) and the like. First, from the material composition point of view, the LiGe does not contain Ti2(PO4)3The base solid electrolyte material has excellent electrochemical stability and chemical stability. Secondly, from the aspect of the preparation method, the preparation method of the invention is different from the method frequently adopted in the prior patent or article, the method is not easy to cause the block material to crack due to stress, is easier to operate, and is suitable for large-scale preparation.
The main advantages of the invention include:
1. provides a catalyst having Li1+x+y+zAlxGe2-xSiyP3-yO12+z/2The solid electrolyte material has high compactness and high room temperature lithium ion conductivity.
2. Compared with the lithium fast ion conductor in the prior art, the material provided by the invention has more excellent electrochemical stability and chemical stability. For all solid-state lithium ion batteries, metallic lithium or alloys of lithium are the best choice for the negative electrode material. Then, for a solid electrolyte with high lithium ion conductivity, a material with a decomposition voltage higher than 5V with respect to metallic lithium would be particularly suitable for a secondary power source of high power density.
3. Compared with the prior art that the glass is formed by high-temperature quenching and then immediately subjected to medium-high temperature annealing so as to eliminate the stress in the glass, and then subjected to subsequent heat treatment process of nucleation and crystallization, or the process that the block is crushed on the basis, then subjected to compression molding again and then subjected to crystallization treatment, the preparation method disclosed by the invention has the advantages that the process is simple, the problem of product cracks frequently occurring in the prior art can be well solved, and the compact and stable-performance material is prepared.
4. The invention does not adopt heat treatment process methods such as hot pressing and plasma discharge sintering (SPS) which have great difficulty and special requirements on equipment, has simple method, is easier to carry out large-scale preparation and is suitable for industrial production.
5. The preparation method of the invention can be adopted to conveniently prepare solid electrolyte materials with various shapes, and has low defective rate.
6. The product of the invention has long service life, wide applicable temperature range and wide application field.
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. The experimental procedures, in which specific conditions are not noted in the following examples, are generally carried out under conventional conditions or conditions recommended by the manufacturers. Unless otherwise indicated, percentages and parts are by weight.
The general method comprises the following steps:
LiGe2(PO4)3the ceramic solid electrolyte may be prepared by a conventional method in the art.
Comparative example 1:
mixing Li2CO3：Al(OH)3：GeO2：NH4H2PO4According to Li1.5Al0.5Ge1.5P3O12Proportioning according to stoichiometric ratio, uniformly mixing and drying, heating the powder to 600 ℃, preserving heat for 2h, cooling, grinding under the condition of wet grinding and drying, pressing the powder into a shape under 300MPa cold isostatic pressure, preserving heat for 20h at 900 ℃, furnace-cooling to obtain the ceramic lithium fast ion block material, wherein the obtained sample powder is of a pure NASICON structure, as shown in figure 1, machining the ceramic block, using gold as a blocking electrode, carrying out an alternating current impedance test at room temperature, and obtaining the ionic conductivity of the sample through calculation when the test frequency is 1 MHz-0.1 Hz., and the ionic conductivity of the sample at room temperature is 5.6 × 10-5S/cm. Its powder XRD pattern is as followsAs shown in FIG. 1, the main crystal phase has a NASICON structure and no impurity phase.
Comparative example 2:
mixing Li2CO3：Al(OH)3：GeO2：NH4H2PO4According to Li1.5Al0.5Ge1.5P3O12Proportioning according to stoichiometric ratio, uniformly mixing and drying, heating the powder to 650 ℃, preserving heat for 2h, cooling, crushing and drying under the wet grinding condition, heating the powder to 1350 ℃, preserving heat for 2h, pouring into liquid nitrogen to quench after the heat preservation, crushing and drying under the wet grinding condition after the product is cooled, pressing and forming glass powder under 300MPa, preserving heat for 6h at 500 ℃, preserving heat for 6h at 850 ℃, cooling along with a furnace to obtain a glass ceramic lithium fast ion block material, wherein the obtained sample powder is a pure NASICON structure as shown in figure 2, machining the glass ceramic block, using gold as a blocking electrode, performing alternating current impedance test at room temperature, obtaining the ionic conductivity of the sample by calculation at the test frequency of 1 MHz-0.1 Hz., and obtaining the room-temperature alternating current impedance graph of the product as shown in figure 6, wherein the room-temperature ionic conductivity of the product is 8.4 × 10-5S/cm. The powder XRD pattern is shown in figure 2, the main crystal phase is NASICON structure, and has no impurity phase.
Example 1:
mixing Li2CO3：Al(OH)3：GeO2：SiO2：NH4H2PO4According to Li1.61Al0.5Ge1.5Si0.01P2.99O12.05Proportioning according to a stoichiometric ratio, uniformly mixing and drying. Heating the powder to 700 ℃, preserving heat for 2h, cooling, grinding under the wet grinding condition and drying. Then heating the powder to 1400 ℃, preserving the heat for 2 hours, and pouring the heated powder into liquid nitrogen for quenching. After cooling, the product is crushed and dried under the wet grinding condition, and the glass powder is pressed and formed under 300 MPa. The block is firstly insulated for 6h at 520 ℃, then insulated for 6h at 900 ℃, and cooled along with the furnace to obtain the glass ceramic lithium fast ion block material. Glass is prepared byAfter the ceramic block is machined, gold is used as a blocking electrode, an alternating current impedance test is carried out at room temperature, the test frequency is 1 MHz-0.1 Hz., the ionic conductivity of the sample is obtained by calculation, the room temperature alternating current impedance diagram of the product is shown in figure 7, and the room temperature ionic conductivity of the product is 2.1 × 10-4S/cm。
Example 2:
mixing Li2CO3：Al(OH)3：GeO2：SiO2：NH4H2PO4According to Li1.62Al0.5Ge1.5Si0.02P2.98O12.05Proportioning according to stoichiometric ratio, uniformly mixing and drying, heating the powder to 750 ℃, preserving heat for 2h, cooling, crushing and drying under the wet grinding condition, heating the powder to 1450 ℃, preserving heat for 2h, pouring into liquid nitrogen to quench after the heat preservation, crushing and drying under the wet grinding condition after the product is cooled, pressing and molding the glass powder under 300MPa, preserving heat for 4h at 550 ℃ and then preserving heat for 6h at 900 ℃, cooling along with a furnace to obtain a glass ceramic lithium fast ion block material, machining the glass ceramic block, taking gold as a blocking electrode, carrying out alternating current impedance test at room temperature, and obtaining the ionic conductivity of the sample by calculation at the test frequency of 1 MHz-0.1 Hz., wherein the ionic conductivity at room temperature is 3.5 × 10-4S/cm。
Example 3:
mixing Li2CO3：Al(OH)3：GeO2：SiO2：NH4H2PO4According to Li1.6Al0.5Ge1.5Si0.05P2.95O12.025Proportioning according to a stoichiometric ratio, uniformly mixing and drying. Heating the powder to 800 ℃, preserving heat for 2h, cooling, grinding under the wet grinding condition and drying. And then heating the powder to 1500 ℃, preserving the heat for 2 hours, and pouring the heated powder into liquid nitrogen for quenching after the heat preservation is finished. Cooling, grinding under wet grinding, and dryingThe method comprises the steps of performing compression molding on glass powder under 300MPa, performing heat preservation on a block at 580 ℃ for 8 hours, performing heat preservation at 900 ℃ for 12 hours, and performing furnace cooling to obtain a glass ceramic lithium fast ion block material, machining the glass ceramic block, using gold as a blocking electrode, performing alternating current impedance test at room temperature, and calculating to obtain the ionic conductivity of a sample at the test frequency of 1 MHz-0.1 Hz., wherein the ionic conductivity at the room temperature is 5.6 × 10-4S/cm。
Example 4:
mixing Li2CO3：Al(OH)3：GeO2：SiO2：NH4H2PO4According to Li1.65Al0.5Ge1.5Si0.1P2.9O12.025Proportioning according to stoichiometric ratio, uniformly mixing and drying, heating the powder to 800 ℃, preserving heat for 2h, crushing and drying under the wet grinding condition after cooling, heating the powder to 1550 ℃, preserving heat for 2h, pouring into liquid nitrogen for quenching after the heat preservation, crushing and drying under the wet grinding condition after cooling the product, pressing and forming glass powder under 300MPa, preserving heat for 12h at 580 ℃, preserving heat for 8h at 900 ℃, and cooling along with a furnace to obtain a glass ceramic lithium fast ion block material, wherein the obtained sample powder is a pure NASICON structure, as shown in figure 3, the glass ceramic block is mechanically processed, gold is used as a blocking electrode, an alternating current impedance test is carried out at room temperature, the test frequency is 1 MHz-0.1 Hz., the ionic conductivity of the sample is obtained through calculation, and the room temperature alternating current impedance graph of the product is shown in figure 8, and can be seen from the graph, the room temperature ionic conductivity is 8.1 × 10-4S/cm. The powder XRD pattern is shown in FIG. 4, the main crystal phase is NASICON structure, and has no impurity phase.
FIG. 9 and FIG. 10 are Li1.65Al0.5Ge1.5Si0.1P2.9O12.025And the chemical stability of the battery using the same as an electrolyte.
Fig. 9 clearly shows that the electrolyte has a decomposition voltage higher than 6V, while the redox peaks corresponding to-0.5V and 0.4V correspond to the deposition and decomposition of metallic lithium, which is the solid electrolyte material with the highest decomposition voltage (relative to metallic lithium) among the oxides reported in the literature so far.
As can be seen from FIG. 10, the impedance spectrum of the battery did not substantially change over the course of one month, indicating that Li1.65Al0.5Ge1.5Si0.1P2.9O12.025No chemical reaction occurs between the glass ceramic and the metallic lithium, and good chemical stability can be shown when the metallic lithium is used as a negative electrode.
The results show that the prepared product has good thermodynamic and chemical stability, high conductivity and decomposition voltage, and has great potential to be applied to solid electrolytes of all-solid-state lithium ion secondary batteries.
Example 5:
mixing Li2CO3：Al(OH)3：GeO2：SiO2：NH4H2PO4According to Li1.72Al0.5Ge1.5Si0.2P2.8O12.01Proportioning according to stoichiometric ratio, uniformly mixing and drying, heating the powder to 800 ℃, preserving heat for 2h, cooling, grinding and drying under the wet grinding condition, heating the powder to 1400 ℃, preserving heat for 2h, pouring into liquid nitrogen to quench after the heat preservation, grinding and drying under the wet grinding condition after the product is cooled, pressing and molding the glass powder under 300MPa, preserving heat for 10h at 620 ℃, preserving heat for 10h at 900 ℃, cooling along with a furnace to obtain a glass ceramic lithium fast ion block material, machining the glass ceramic block, taking gold as a blocking electrode, carrying out alternating current impedance test at room temperature, obtaining the ionic conductivity of the sample by calculation at the test frequency of 1 MHz-0.1 Hz., wherein the ionic conductivity at room temperature is 2.1 × 10-4S/cm。
Example 6:
mixing Li2CO3：Al(OH)3：GeO2：SiO2：NH4H2PO4According to Li1.82Al0.5Ge1.5Si0.3P2.7O12.01Proportioning according to stoichiometric ratio, uniformly mixing and drying, heating the powder to 800 ℃, preserving heat for 2h, cooling, grinding and drying under the wet grinding condition, heating the powder to 1500 ℃, preserving heat for 2h, pouring into liquid nitrogen to quench after the heat preservation, grinding and drying under the wet grinding condition after the product is cooled, pressing and forming glass powder under 300MPa, preserving heat for 4h at 640 ℃, preserving heat for 16h at 900 ℃, cooling along with a furnace to obtain a glass ceramic lithium fast ion block material, machining the glass ceramic block, taking gold as a blocking electrode, carrying out alternating current impedance test at room temperature, and obtaining the ionic conductivity of a sample by calculation at the test frequency of 1 MHz-0.1 Hz., wherein the ionic conductivity at room temperature is 1.3 × 10-4S/cm。
Example 7:
mixing Li2CO3：Al(OH)3：GeO2：SiO2：NH4H2PO4According to Li1.92Al0.5Ge1.5Si0.4P2.6O12.01Proportioning according to stoichiometric ratio, uniformly mixing and drying, heating the powder to 800 ℃, preserving heat for 2h, cooling, crushing and drying under the wet grinding condition, heating the powder to 1550 ℃, preserving heat for 2h, pouring into liquid nitrogen for quenching after the completion, crushing and drying under the wet grinding condition after the product is cooled, pressing and forming glass powder under 300MPa, preserving heat for 8h at 580 ℃, preserving heat for 20h at 900 ℃, cooling along with a furnace to obtain a glass ceramic lithium fast ion block material, wherein the obtained sample powder is a pure NASICON structure, as shown in figure 4, machining the glass ceramic block, taking gold as a blocking electrode, carrying out alternating current impedance test at room temperature, and obtaining the ionic conductivity of the sample through calculation at the test frequency of 1 MHz-0.1 Hz., wherein the ionic conductivity at room temperature is 8.5 × 10-5S/cm. The powder XRD pattern is shown in figure 4The main crystal phase is shown to be a NASICON structure and free of impurity phases.
Example 8:
mixing Li2CO3：Al(OH)3：GeO2：SiO2：NH4H2PO4According to Li1.55Al0.4Ge1.6Si0.1P2.9O12.025Proportioning according to stoichiometric ratio, uniformly mixing and drying, heating the powder to 700 ℃, preserving heat for 2h, cooling, grinding and drying under the wet grinding condition, heating the powder to 1550 ℃, preserving heat for 2h, pouring into liquid nitrogen to quench after the heat preservation, grinding and drying under the wet grinding condition after the product is cooled, pressing and forming glass powder under 300MPa, preserving heat for 8h at 550 ℃, preserving heat for 12h at 900 ℃, cooling along with a furnace to obtain a glass ceramic lithium fast ion block material, machining the glass ceramic block, taking gold as a blocking electrode, carrying out alternating current impedance test at room temperature, obtaining the ionic conductivity of the sample by calculation at the test frequency of 1 MHz-0.1 Hz., wherein the ionic conductivity at room temperature is 6.1 × 10-4S/cm。
Example 9:
mixing Li2CO3：Al(OH)3：GeO2：SiO2：NH4H2PO4According to Li1.61Al0.46Ge1.54Si0.1P2.9O12.025Proportioning according to a stoichiometric ratio, uniformly mixing and drying. Heating the powder to 850 ℃ and preserving the temperature for 2h, grinding and drying under the wet grinding condition after cooling. And then heating the powder to 1550 ℃, preserving the heat for 2 hours, and pouring the powder into liquid nitrogen for quenching after the heat preservation is finished. After cooling, the product is crushed and dried under the wet grinding condition, and the glass powder is pressed and formed under 300 MPa. The block is firstly insulated for 8h at 550 ℃, then insulated for 12h at 900 ℃, and cooled along with the furnace to obtain the glass ceramic lithium fast ion block material. Machining glass ceramic block, using gold as blocking electrode, and making it be at room tempPerforming alternating current impedance test, wherein the test frequency is 1 MHz-0.1 Hz. to obtain the ionic conductivity of the sample by calculation, and the ionic conductivity at room temperature is 3.7 × 10-4S/cm。
Comparative example 3:
mixing Li2CO3：Al(OH)3：GeO2：SiO2：NH4H2PO4According to Li1.5Al0.5Ge1.5P3O12Proportioning according to a stoichiometric ratio, uniformly mixing and drying. Heating the powder to 750 ℃, preserving heat for 2h, grinding and drying under the wet grinding condition after cooling. And heating the powder to 1350 ℃, preserving heat for 2h, pouring into a mold subjected to heat preservation treatment at 500 ℃ quickly after the heat preservation is finished, and quickly compacting to obtain the glass with a certain shape. The mold was then immediately placed into a furnace with glass for 500 ℃ annealing for 2 h. After cooling, the block glass is kept at 600 ℃ for 6h, then kept at 900 ℃ for 6h, and cooled along with the furnace to obtain the glass ceramic lithium fast ion block material, but obvious cracks appear, namely the yield of the glass ceramic prepared by the method is low.
Comparative example 4
Mixing Li2CO3：Al(OH)3：GeO2：SiO2：NH4H2PO4According to Li1.55Al0.4Ge1.6Si0.1P2.9O12.025Proportioning according to a stoichiometric ratio, uniformly mixing and drying. Heating the powder to 700 ℃, preserving heat for 3h, cooling, grinding under the wet grinding condition and drying. And heating the powder to 1450 ℃, preserving heat for 4 hours, quickly pouring the powder into a mold subjected to heat preservation treatment at 550 ℃, and quickly compacting to obtain the glass with a certain shape. The mold was then immediately placed into a furnace with glass for a 490 ℃ anneal for 2 hours. After cooling, the block glass is kept at 580 ℃ for 6h, then kept at 850 ℃ for 6h, and cooled along with the furnace to obtain the glass ceramic lithium fast ion block material, but obvious cracks appear, namely the yield of the glass ceramic prepared by the method is low.
And (3) detection by a scanning electron microscope:
the SEM topography is shown in FIG. 5: (a) cross-sectional SEM morphology of ceramic bulk sample in comparative example 2 (b) cross-sectional SEM morphology of glass-ceramic bulk sample in example 1 (c) cross-sectional SEM morphology of glass-ceramic bulk sample in example 4 (d) cross-sectional SEM morphology of glass-ceramic bulk sample in example 7.
From the microscopic compactness, (a) and (d) have larger porosities than (b) and (c).
All documents referred to herein are incorporated by reference into this application as if each were individually incorporated by reference. Furthermore, it should be understood that various changes and modifications of the present invention can be made by those skilled in the art after reading the above teachings of the present invention, and these equivalents also fall within the scope of the present invention as defined by the appended claims.
Claims (16)
1. Preparation of Li1+x+y+zAlxGe2-xSiyP3-yO12+z/2A method of fast ion conductor material comprising the steps of:
providing powder with the element proportion, wherein the powder is glass powder;
molding the powder to obtain a molded glass body;
annealing the formed glass body to obtain the fast ion conductor material;
wherein x is more than 0 and less than or equal to 2, y is more than or equal to 0 and less than or equal to 0.4, and z is more than or equal to 0 and less than or equal to 0.5;
the glass powder is prepared by the following method:
providing a high-temperature molten mass with the element proportion;
quenching the molten mass to obtain quenched glass;
crushing the quenched glass to obtain glass powder;
and the high-temperature melt is prepared by the following method:
(1) li source, Al source, P source, Si source and Ge source are mixed according to Li1+x+y+zAlxGe2-xSiyP3-yO12+z/2Stoichiometric ratio, wherein x, y, z are as defined above;
(2) heating the mixture, preserving heat, cooling, and crushing to obtain powder;
(3) and heating the powder, and preserving heat to obtain the high-temperature molten mass.
2. The method of claim 1, wherein 0 < x < 2, 0 < y < 0.4, and 0 < z < 0.5.
3. The method of claim 1, wherein x is 0.5 and z is 0.01. ltoreq. z.ltoreq.0.1.
4. The method of claim 1, wherein the glass powder is formed by a process selected from the group consisting of: compression molding, tape casting molding, vehicle blank molding, slip casting molding and near net size molding.
5. The method of claim 1, wherein the annealing step comprises: preserving heat at 450-700 ℃; and/or
And preserving heat at 850-950 ℃.
6. The method of claim 1, wherein the glass powder is formed by a process selected from the group consisting of: rolling and spinning.
7. The method of claim 1, wherein the glass powder is formed by a press forming process.
8. A fast ion conductor material, characterized in that the material has the following element ratio:
Li1+x+y+zAlxGe2-xSiyP3-yO12+z/2
wherein,
0＜x≤2；
0≤y≤0.4；
0≤z≤0.5；
and the material is prepared by the method of claim 1.
9. The conductive material of claim 8, wherein 0 < x < 2, 0 < y < 0.4, 0 < z < 0.5.
10. The conductive material of claim 8, wherein x is 0.5 and 0.01. ltoreq. z is 0.1.
11. The conductive material of claim 8, wherein said conductive material is a glass-ceramic material.
12. The conductive material of claim 8, wherein said conductive material has a room temperature ionic conductivity of 8 × 10-5～5×10-3S/cm。
13. The conductive material of claim 8, wherein said conductive material has a room temperature ionic conductivity of 1 × 10-4～1×10-3S/cm。
14. The conductive material according to claim 8, wherein the porosity of the conductive material is 0 to 15%.
15. The conductive material according to claim 8, wherein the porosity of the conductive material is 0 to 6%.
16. An article comprising the conductive material of claim 8, or comprising the conductive material prepared by the method of claim 1.
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