CN114497714B - Preparation method of garnet type solid electrolyte with high ion conductivity - Google Patents
Preparation method of garnet type solid electrolyte with high ion conductivity Download PDFInfo
- Publication number
- CN114497714B CN114497714B CN202210158203.8A CN202210158203A CN114497714B CN 114497714 B CN114497714 B CN 114497714B CN 202210158203 A CN202210158203 A CN 202210158203A CN 114497714 B CN114497714 B CN 114497714B
- Authority
- CN
- China
- Prior art keywords
- source
- solid electrolyte
- ion conductivity
- type solid
- lithium
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000007784 solid electrolyte Substances 0.000 title claims abstract description 62
- 239000002223 garnet Substances 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title abstract description 12
- 239000000843 powder Substances 0.000 claims abstract description 78
- 238000000498 ball milling Methods 0.000 claims abstract description 22
- 238000010438 heat treatment Methods 0.000 claims abstract description 22
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 21
- 238000001816 cooling Methods 0.000 claims abstract description 19
- 239000000463 material Substances 0.000 claims abstract description 17
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 14
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 7
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 7
- 239000000126 substance Substances 0.000 claims abstract description 5
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 31
- 238000000034 method Methods 0.000 claims description 27
- 238000005245 sintering Methods 0.000 claims description 27
- 150000002500 ions Chemical class 0.000 claims description 19
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 8
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 claims description 8
- 238000003825 pressing Methods 0.000 claims description 7
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims description 6
- IVORCBKUUYGUOL-UHFFFAOYSA-N 1-ethynyl-2,4-dimethoxybenzene Chemical compound COC1=CC=C(C#C)C(OC)=C1 IVORCBKUUYGUOL-UHFFFAOYSA-N 0.000 claims description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 4
- YXEUGTSPQFTXTR-UHFFFAOYSA-K lanthanum(3+);trihydroxide Chemical compound [OH-].[OH-].[OH-].[La+3] YXEUGTSPQFTXTR-UHFFFAOYSA-K 0.000 claims description 4
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 claims description 4
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 4
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 4
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 4
- 238000004321 preservation Methods 0.000 claims description 2
- 239000013078 crystal Substances 0.000 abstract description 26
- 239000003792 electrolyte Substances 0.000 abstract description 9
- 230000006911 nucleation Effects 0.000 abstract description 4
- 238000010899 nucleation Methods 0.000 abstract description 4
- 230000001737 promoting effect Effects 0.000 abstract 1
- 238000007670 refining Methods 0.000 abstract 1
- 239000002994 raw material Substances 0.000 description 27
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 22
- 235000015895 biscuits Nutrition 0.000 description 21
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 13
- 238000005303 weighing Methods 0.000 description 12
- 239000004570 mortar (masonry) Substances 0.000 description 11
- 239000002001 electrolyte material Substances 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- 238000001035 drying Methods 0.000 description 6
- 238000001453 impedance spectrum Methods 0.000 description 6
- 238000001354 calcination Methods 0.000 description 5
- 238000000227 grinding Methods 0.000 description 5
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- 229910001416 lithium ion Inorganic materials 0.000 description 4
- 210000001787 dendrite Anatomy 0.000 description 3
- 238000004146 energy storage Methods 0.000 description 3
- 239000011244 liquid electrolyte Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000012876 topography Methods 0.000 description 3
- 230000002159 abnormal effect Effects 0.000 description 2
- 210000004027 cell Anatomy 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000005764 inhibitory process Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 229910005191 Ga 2 O 3 Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910021193 La 2 O 3 Inorganic materials 0.000 description 1
- 208000012868 Overgrowth Diseases 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000010416 ion conductor Substances 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000009766 low-temperature sintering Methods 0.000 description 1
- 229910052987 metal hydride Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- -1 nickel metal hydride Chemical class 0.000 description 1
- 239000005486 organic electrolyte Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- OSYUGTCJVMTNTO-UHFFFAOYSA-D oxalate;tantalum(5+) Chemical compound [Ta+5].[Ta+5].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O OSYUGTCJVMTNTO-UHFFFAOYSA-D 0.000 description 1
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 229910001936 tantalum oxide Inorganic materials 0.000 description 1
- ZIRLXLUNCURZTP-UHFFFAOYSA-I tantalum(5+);pentahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[Ta+5] ZIRLXLUNCURZTP-UHFFFAOYSA-I 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 229910001928 zirconium oxide 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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0065—Solid electrolytes
- H01M2300/0068—Solid electrolytes inorganic
- H01M2300/0071—Oxides
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The invention discloses a preparation method of garnet type solid electrolyte with high ion conductivity, which is characterized in that the garnet type solid electrolyte is prepared according to a chemical formula Li 7 La 3 Zr 2‑ x M x O 12 Ball milling is carried out on the powder materials of a lithium source, a lanthanum source, a zirconium source and an M source, then presintering is carried out, the powder materials are pressed into round green sheets, and the green sheets are kept at a low temperature for 0.5-3 h; then continuously heating to a high temperature section and cooling to obtain the garnet type solid electrolyte with high ion conductivity, wherein the temperature of the high temperature section is at least 50 ℃ higher than that of the low temperature section; x is more than or equal to 0.2 and less than or equal to 0.75. The garnet type solid electrolyte with high ion conductivity prepared by the invention has the advantages of promoting the nucleation speed of crystals, refining primary grains, homogenizing the grain size inside the solid electrolyte, reducing the grain boundary inside the crystals, improving the compactness of the material and greatly improving the ion conductivity of the electrolyte.
Description
Technical Field
The invention belongs to the technical field of preparation of oxide solid electrolytes, and particularly relates to a method for preparing garnet-type solid electrolytes with high ion conductivity.
Background
Currently available commercial batteries (e.g., lead acid, nickel metal hydride, lithium ion, and flow batteries) are unable to meet the stringent or ever-increasing energy density requirements of portable electronic devices, electric vehicles, and power grid energy storage systems. Although liquid electrolytes have the advantages of high conductivity and good wettability of the electrode surface, problems of insufficient electrochemical and thermal stability, low ion selectivity and poor safety of liquid electrolytes are exposed when current commercial batteries are used in high power and high energy density energy storage devices. After frequent spontaneous combustion events from electric vehicles, the safety of high energy density energy storage devices is being put on higher demands. Thus, development of a device with higher energy densityBatteries with longer cycle life and higher safety levels are urgent. Since lithium metal has the highest theoretical specific capacity (3860 mAh g -1 ) Minimum electrochemical potential (-3.04V vs. standard hydrogen electrode) and light weight (ρ=0.53 g cm) -3 ) Therefore, the use of lithium metal cathodes instead of other cathodes is considered to be effective in improving the energy density of the battery, and importantly, the growth of lithium dendrites in liquid organic electrolytes and the easy volatilization, flammability and leakage of organic solvents present potential safety hazards, which prevent the direct application of lithium metal in practical production. Therefore, the research and development of solid electrolyte to replace inflammable and explosive organic liquid electrolyte has extremely high research and commercial value.
Li having a cubic garnet structure among many electrolytes 7 La 3 Zr 2 O 12 The (LLZO) solid electrolyte has the following advantages: (1) Ion conductivity at room temperature can reach 10 -4 S cm -1 (2) good thermal stability, and can work in a wide temperature range; (3) Can replace a diaphragm to be used, and has good mechanical property and processability; (4) the safety is good, and the fuel is not burnt. Garnet-type solid electrolytes are thus currently popular materials for lithium metal solid state battery electrolytes.
Currently, the main method for preparing the LLZO solid electrolyte is a conventional solid phase sintering method, and in many patents (for example, CN 109935901 A,CN 113363562A and CN 109888374A), the LLZO solid electrolyte is prepared by a method of maintaining a temperature at a fixed temperature for a certain period of time. However, there are certain problems in preparing LLZO by this method of maintaining a constant temperature for a certain period of time. If sintering is continued at low temperature, it may occur that the ionic conductivity is only 10 -6 S cm -1 Even though the fired LLZO has an ionic conductivity of about 10 -4 S cm -1 But also results in smaller grain sizes, larger grain boundary concentrations and voids, resulting in a severe decrease in the ionic conductivity of the material. If sintering is continuously carried out under the high-temperature condition, not only the energy consumption is high, but also the grain size can overgrow, the abnormal growth condition of the grain is generated, the serious crystal penetration phenomenon is generated, and the method is characterized in thatAnd the relative density and mechanical strength of the material are reduced, and cracks are generated even at grain boundaries, so that the ionic conductivity of the material is seriously reduced.
Disclosure of Invention
In view of the problems in the prior art, an object of the present invention is to provide a method for preparing a garnet-type solid electrolyte with high ion conductivity by sintering, which is a garnet-structured lithium-ion-type solid electrolyte Li 7 La 3 Zr 2-x M x O 12 The method has higher lithium ion conductivity and stability on the metallic lithium cathode, can obviously homogenize garnet-type solid electrolyte grains, improves the density of the material, has simpler preparation method and can be produced in a large scale.
In order to achieve the above purpose, the invention adopts the following technical scheme:
a preparation method of a garnet type solid electrolyte with high ion conductivity comprises the following steps:
according to chemical formula Li 7 La 3 Zr 2-x M x O 12 Ball milling is carried out on the powder materials of the lithium source, the lanthanum source, the zirconium source and the M source, and then presintering is carried out for 8-10.5 hours at 800-950 ℃ to obtain primary sintered powder; pressing the primary sintered powder into round green sheets, and preserving the temperature of the green sheets for 0.5-3 h at a low temperature section; then continuously heating to a high temperature section and cooling to obtain the garnet type solid electrolyte with high ion conductivity, wherein the temperature of the low temperature section is 950-1200 ℃, the temperature of the high temperature section is 1000-1350 ℃, and the temperature of the high temperature section is at least 50 ℃ higher than the temperature of the low temperature section; the M source is an Al source, a Ga source, a Y source, an In source, a Ti source, a Hf source, a Nb source, a Ta source, a Cr source, a Mo source or a W source, and x is more than or equal to 0.2 and less than or equal to 0.75.
Further, x is more than or equal to 0.2 and less than or equal to 0.5.
Further, the lithium source is one of lithium carbonate, lithium hydroxide, lithium acetate and lithium nitrate.
Further, the lanthanum source is one of lanthanum oxide, lanthanum hydroxide and lanthanum nitrate.
Further, the zirconium source is one of zirconia, zirconium hydroxide and zirconium nitrate.
Further, the M source is Al, ga, Y, in, ti, hf, nb, ta, cr, mo or an oxide of W.
Further, the primary sintered powder is pressed into round green sheets under the pressure of 300-500 MPa.
Further, the blank sheet is placed in a muffle furnace to be heated to a high temperature section at a heating rate of 1-20 ℃/min.
Further, furnace cooling is adopted for cooling.
Compared with the prior art, the invention has the following beneficial technical effects:
according to the invention, the garnet type solid electrolyte is prepared by a dynamic sintering method, the temperature is kept for a period of time at a low temperature to promote the nucleation of crystal grains, then the temperature is raised to a high temperature section by a dynamic temperature raising method, the crystal grains can slowly grow in the temperature raising process, and immediately cooled along with a furnace after reaching the high temperature section, so that overgrowth of the crystal grains is prevented, the grain size inside the solid electrolyte is homogenized, the integrity of the crystal grains is improved, the aim of improving the ionic conductivity of the solid electrolyte is finally realized, and the garnet type solid electrolyte with excellent preparation performance plays a key role in the success of all-solid lithium batteries. The invention adopts staged heating, can promote the nucleation speed of crystals, refine primary grains, homogenize the grain size in the solid electrolyte, reduce the grain boundary in the crystals, thereby improving the material density and greatly improving the ion conductivity of the electrolyte. The invention adopts the traditional simple solid-phase sintering preparation process, and the method is simple and easy to operate, has lower cost and can be used for mass production. Compared with unmodified garnet-type solid electrolyte materials, the method can remarkably homogenize the grain size inside the solid electrolyte, reduce the grain boundary inside the crystal and sinter the garnet-type Li 7 La 3 Zr 2-x M x O 12 The crystal grains of the solid electrolyte are homogenized, the density is increased, the ionic conductivity can be greatly increased, and the lithium ion conductivity is improved by 5.7-8.2 times at 25 ℃.
Drawings
FIG. 1 shows comparative example 1 of the present invention at constant temperature at low temperatureSintered Li 7 La 3 Zr 1.5 Ta 0.5 O 12 Microcosmic topography of the solid electrolyte;
FIG. 2 is a constant temperature sintered Li at a high temperature of comparative example 2 7 La 3 Zr 1.5 Ta 0.5 O 12 Microcosmic topography of the solid electrolyte;
FIG. 3 is Li prepared by the dynamic sintering method of example 3 7 La 3 Zr 1.75 Ta 0.25 O 12 Microcosmic topography of the solid electrolyte;
FIG. 4 is an electrochemical impedance spectrum at 25℃of the electrolyte material prepared in comparative example 1;
FIG. 5 is an electrochemical impedance spectrum at 25℃of the electrolyte material prepared in comparative example 2;
FIG. 6 is an electrochemical impedance spectrum at 25℃of the electrolyte material prepared in example 3;
FIG. 7 is an electrochemical impedance spectrum at 25℃of the electrolyte material prepared in example 4;
FIG. 8 is an electrochemical impedance spectrum at 25℃of the electrolyte material prepared in example 5;
FIG. 9 is a diagram of Li|Au/Li in example 3 of the present invention 7 La 3 Zr 1.75 Ta 0.25 O 12 Au|li symmetric cell performance plot.
Detailed Description
The technical solution of the present invention will be clearly and completely described in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some, but not all embodiments of the present invention, and the embodiments of the present invention are not limited thereto. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without any inventive effort, are intended to be within the scope of the invention.
The invention relates to a preparation method of garnet type solid electrolyte with high ion conductivity, and the structural expression is Li 7 La 3 Zr 2-x M x O 12 (M is Al, ga, Y, in, ti, hf, nb, ta, cr, mo, W; x is more than or equal to 0.2 and less than or equal to 0.75), and the solid electricity is promoted by adopting a dynamic temperature-rising sintering methodThe nucleation speed of the crystals in the electrolyte refines primary grains, the grain size is uniform, and the grain boundaries in the crystals are reduced, so that the material density is improved, the ion conductivity of the electrolyte is improved, the inhibition capability of the electrolyte on lithium dendrites is improved, and the cycling stability of the lithium metal battery is improved.
Specifically, the preparation method of the garnet-type solid electrolyte with high ion conductivity comprises the following steps:
(1) According to chemical formula Li 7 La 3 Zr 2-x M x O 12 Ball milling is carried out on the powder materials of the lithium source, the lanthanum source, the zirconium source and the M source to obtain raw powder;
(2) Presintering the raw powder at 800-950 ℃ for 8-10.5 h to obtain primary sintered powder;
(3) Pressing the primary sintered powder into round green sheets under the pressure of 300-500 MPa;
(4) Heating the blank sheet to 950-1200 ℃ in a lower temperature section in a muffle furnace, and preserving the temperature for 0.5-3 h;
(5) Placing the green sheet into a muffle furnace, heating to a high temperature of 1000-1350 ℃ at a heating rate of 1-20 ℃/min, immediately cooling along with a furnace body without a heat preservation time, wherein the temperature of the high temperature section is at least 50 ℃ higher than that of the low temperature section, and finally obtaining Li 7 La 3 Zr 2-x M x O 12 A solid electrolyte. Wherein M is one of Al source, ga source, Y source, in source, ti source, hf source, nb source, ta source, cr source, mo source and W source, x is more than or equal to 0.2 and less than or equal to 0.75, and preferably, x is more than or equal to 0.2 and less than or equal to 0.5.
The lithium source is one of lithium carbonate, lithium hydroxide, lithium acetate and lithium nitrate.
The lanthanum source is one of lanthanum oxide, lanthanum hydroxide and lanthanum nitrate.
The zirconium source is one of zirconium oxide, zirconium hydroxide and zirconium nitrate.
The tantalum source is one of tantalum oxide, tantalum oxalate and tantalum hydroxide.
The lithium source is required to be in excess, and the mass of the excess is 10 to 15% of the mass of the lithium source calculated according to the chemical formula.
The garnet type solid electrolyte with high ion conductivity prepared by the method has uniform grain size, and the lithium ion conductivity is improved by 5.7-8.2 times at 25 ℃.
The following examples are for preparing a garnet solid electrolyte of high ionic conductivity:
example 1
According to Li 7 La 3 Zr 1.75 Nb 0.25 O 12 0.15mol La was weighed out 2 O 3 ，0.7mol LiOH·H 2 O,0.175mol ZrO 2 And 0.0125mol Nb 2 O 5 To compensate for volatilization of Li element in crystal structure at high temperature, lioh.h in raw material 2 The O excess is 15% of the mass calculated as stoichiometric. Mixing and ball-milling the raw materials in an isopropanol ball-milling medium at a rotating speed of 380r/min for 20 hours, and drying the raw materials in an oven at 80 ℃ for 24 hours to obtain powder. The obtained powder is ground to be uniform by a mortar, and calcined at 800 ℃ for 10.5 hours to obtain the presintered product mother powder. Weighing a certain mass of mother powder, placing the mother powder in a die with the diameter of 15mm, placing the die on a workbench of a tablet press, applying pressure of 350MPa, maintaining the pressure for 5min, and demolding and taking out the molded complete biscuit. Embedding the biscuit sheet with mother powder, placing in an alumina crucible, keeping the temperature in a muffle furnace to 1150 ℃ for 2 hours, heating at a heating rate of 2 ℃/min, sintering, ending after the temperature rises to 1250 ℃, and cooling along with the furnace to obtain Li 7 La 3 Zr 1.75 Nb 0.25 O 12 A solid electrolyte.
Example 2
According to Li 7 La 3 Zr 1.60 Hf 0.40 O 12 0.15mol La was weighed out 2 O 3 ，0.7mol LiOH·H 2 O,0.16mol ZrO 2 And 0.02mol HfO 2 To compensate for volatilization of Li element in crystal structure at high temperature, lioh.h in raw material 2 The O excess is 15% of the mass calculated as stoichiometric. Mixing and ball-milling the raw materials in an isopropanol ball-milling medium at a rotating speed of 380r/min for 20 hours, and drying the raw materials in an oven at 80 ℃ for 24 hours to obtain powder. The obtained powder is ground to be uniform by a mortar, and calcined at 950 ℃ for 8.5 hours to obtain the presintered product mother powder. Weighing mother powder with certain massPlacing the blank sheet into a die with the diameter of 15mm, placing the die on a workbench of a tablet press, applying pressure of 350MPa, maintaining the pressure for 5min, demolding, and taking out the molded blank sheet completely. Embedding the biscuit sheet with mother powder, placing in an alumina crucible, preserving heat in a muffle furnace to 1200 ℃ for 1h, sintering at a heating rate of 2.5 ℃/min, ending after the temperature rises to 1250 ℃, and cooling along with the furnace to obtain Li 7 La 3 Zr 1.60 Hf 0.40 O 12 A solid electrolyte.
Example 3
According to Li 7 La 3 Zr 1.75 Ta 0.25 O 12 0.15mol La was weighed out 2 O 3 ，0.7mol LiOH·H 2 O,0.175mol ZrO 2 And 0.0125mol Ta 2 O 5 To compensate for volatilization of Li element in crystal structure at high temperature, lioh.h in raw material 2 O is 15% of the total mass. The raw materials are mixed and ball-milled in isopropanol ball-milling medium at a rotating speed of 380r/min for 20 hours and then dried in an oven at 80 ℃ for 24 hours. Grinding the obtained powder to be uniform by using a mortar, calcining at 900 ℃ for 9 hours to obtain a presintered product mother powder, weighing a certain mass of mother powder, placing the mother powder in a die with the diameter of 15mm, placing the die on a workbench of a tablet press, applying 400MPa of pressure and maintaining the pressure for 5 minutes, and demoulding and taking out the finished biscuit. Embedding the biscuit sheet with mother powder, placing in an alumina crucible, preserving heat in a muffle furnace to 950 ℃ for 3h, sintering at a heating rate of 2 ℃/min, ending after the temperature rises to 1150 ℃, and cooling along with the furnace to obtain Li 7 La 3 Zr 1.75 Ta 0.25 O 12 A solid electrolyte.
Example 4
According to Li 7 La 3 Zr 1.5 Ta 0.5 O 12 0.15mol La was weighed out 2 O 3 ，0.7mol LiOH·H 2 O,0.150mol ZrO 2 And 0.0125mol Ta 2 O 5 To compensate for volatilization of Li element in crystal structure at high temperature, lioh.h in raw material 2 O is 15% of the total mass. Mixing and ball milling raw materials in isopropanol ball milling medium at 380r/min for 20h, and then carrying out 8Drying in an oven at 0 ℃ for 24 hours. Grinding the obtained powder to be uniform by using a mortar, calcining at 900 ℃ for 9 hours to obtain a presintered product mother powder, weighing a certain mass of mother powder, placing the mother powder in a die with the diameter of 15mm, placing the die on a workbench of a tablet press, applying 400MPa of pressure and maintaining the pressure for 5 minutes, and demoulding and taking out the finished biscuit. Embedding the biscuit sheet with mother powder, placing in an alumina crucible, preserving heat in a muffle furnace to 1100 ℃ for 1h, sintering at a heating rate of 2 ℃/min, ending after the temperature rises to 1200 ℃, and cooling along with the furnace to obtain Li 7 La 3 Zr 1.75 Ta 0.25 O 12 A solid electrolyte.
Example 5
According to Li 7 La 3 Zr 1.80 Y 0.20 O 12 0.15mol La was weighed out 2 O 3 ，0.7mol LiOH·H 2 O,0.18mol ZrO 2 And 0.01mol Y 2 O 3 To compensate for volatilization of Li element in crystal structure at high temperature, lioh.h in raw material 2 O is 10% of the total mass. The raw materials are mixed and ball-milled in isopropanol ball-milling medium at a rotating speed of 380r/min for 20 hours and then dried in an oven at 80 ℃ for 24 hours. Grinding the obtained powder to be uniform by using a mortar, calcining at 900 ℃ for 10.5 hours to obtain a presintered product mother powder, weighing the mother powder with a certain mass, placing the mother powder in a die with the diameter of 15mm, placing the die on a workbench of a tablet press, applying 400MPa of pressure and maintaining the pressure for 5 minutes, and demoulding and taking out the molded complete biscuit. Embedding the biscuit sheet with mother powder, placing in an alumina crucible, keeping the temperature in a muffle furnace to 990 ℃ for 4 hours, sintering at a heating rate of 4 ℃/min, ending after the temperature rises to 1250 ℃, and cooling along with the furnace to obtain Li 7 La 3 Zr 1.80 Y 0.20 O 12 A solid electrolyte.
Example 6
According to Li 7 La 3 Zr 1.70 Nb 0.30 O 12 0.15mol La was weighed out 2 O 3 ，0.7mol LiOH·H 2 O,0.17mol ZrO 2 And 0.015mol Nb 2 O 5 To compensate for volatilization of Li element in crystal structure at high temperature, raw materialsLiOH H in (B) 2 The O excess is 15% of the mass calculated as stoichiometric. Mixing and ball-milling the raw materials in an isopropanol ball-milling medium at a rotating speed of 380r/min for 20 hours, and drying the raw materials in an oven at 80 ℃ for 24 hours to obtain powder. The obtained powder is ground to be uniform by a mortar, and calcined at 800 ℃ for 10.5 hours to obtain the presintered product mother powder. Weighing a certain mass of mother powder, placing the mother powder in a die with the diameter of 15mm, placing the die on a workbench of a tablet press, applying pressure of 350MPa, maintaining the pressure for 5min, and demolding and taking out the molded complete biscuit. Embedding the biscuit sheet with mother powder, placing in an alumina crucible, keeping the temperature in a muffle furnace to 1050 ℃ for 1.5h, sintering at a heating rate of 5 ℃/min, ending after the temperature rises to 1250 ℃, and cooling along with the furnace to obtain Li 7 La 3 Zr 1.70 Nb 0.30 O 12 A solid electrolyte.
Example 7
The same procedure as in example 1 was followed, except that the green sheet was embedded with the mother powder, placed in an alumina crucible, kept at 1200℃for 0.5 hours in a muffle furnace, and sintered at a rate of 7.5℃per minute, and then the green sheet was heated to 1350 ℃.
Example 8
The procedure was as in example 3, except that the green sheet was embedded with the mother powder, placed in an alumina crucible, kept at 1050℃for 1.75 hours in a muffle furnace, and sintered at a heating rate of 5℃per minute, and then ended after the temperature was raised to 1300 ℃.
Example 9
The same procedure as in example 3 was followed, except that the green sheet was embedded with the mother powder, placed in an alumina crucible, kept at 1150℃for 45 minutes in a muffle furnace, and sintered at a heating rate of 13℃per minute, and then ended after the temperature was raised to 1280 ℃.
Example 10
According to Li 7 La 3 Zr 1.25 Al 0.75 O 12 0.15mol La was weighed out 2 O 3 ，0.7mol LiOH·H 2 O,0.125mol ZrO 2 And 0.0375mol Al 2 O 3 To compensate for volatilization of Li element in crystal structure at high temperature, lioh.h in raw material 2 Excess of O is15% of the mass calculated as stoichiometric. Mixing and ball-milling the raw materials in an isopropanol ball-milling medium at a rotating speed of 380r/min for 20 hours, and drying the raw materials in an oven at 80 ℃ for 24 hours to obtain powder. The obtained powder is ground to be uniform by a mortar, and calcined at 850 ℃ for 8 hours to obtain the presintered product mother powder. Weighing a certain mass of mother powder, placing the mother powder in a die with the diameter of 15mm, placing the die on a workbench of a tablet press, applying 300MPa pressure and maintaining the pressure for 5min, and demolding and taking out the molded complete biscuit. Embedding the biscuit sheet with mother powder, placing in an alumina crucible, preserving heat in a muffle furnace to 950 ℃ for 0.5h, sintering at a heating rate of 1 ℃/min, ending after the temperature rises to 1000 ℃, and cooling along with the furnace to obtain Li 7 La 3 Zr 1.25 Al 0.75 O 12 A solid electrolyte.
Example 11
According to Li 7 La 3 Zr 1.40 Ga 0.60 O 12 0.15mol La was weighed out 2 O 3 ，0.7mol LiOH·H 2 O,0.140mol ZrO 2 And 0.03mol Ga 2 O 3 To compensate for volatilization of Li element in crystal structure at high temperature, lioh.h in raw material 2 The O excess is 15% of the mass calculated as stoichiometric. Mixing and ball-milling the raw materials in an isopropanol ball-milling medium at a rotating speed of 380r/min for 20 hours, and drying the raw materials in an oven at 80 ℃ for 24 hours to obtain powder. The obtained powder is ground to be uniform by a mortar, and calcined at 870 ℃ for 9.5 hours to obtain the presintered product mother powder. Weighing a certain mass of mother powder, placing the mother powder in a die with the diameter of 15mm, placing the die on a workbench of a tablet press, applying 500MPa pressure and maintaining the pressure for 5min, and demolding and taking out the molded complete biscuit. Embedding the biscuit with mother powder, placing in an alumina crucible, keeping the temperature in a muffle furnace to 1050 ℃ for 3h, sintering at a heating rate of 20 ℃/min, ending when the temperature is up to 1350 ℃, and cooling along with the furnace to obtain Li 7 La 3 Zr 1.40 Ga 0.60 O 12 A solid electrolyte.
Example 12
According to Li 7 La 3 Zr 1.70 Cr 0.30 O 12 Is of stoichiometric ratio of (2)Weighing 0.15mol of La 2 O 3 ，0.7mol LiOH·H 2 O,0.17mol ZrO 2 And 0.015mol Cr 2 O 3 To compensate for volatilization of Li element in crystal structure at high temperature, lioh.h in raw material 2 The O excess is 15% of the mass calculated as stoichiometric. Mixing and ball-milling the raw materials in an isopropanol ball-milling medium at a rotating speed of 380r/min for 20 hours, and drying the raw materials in an oven at 80 ℃ for 24 hours to obtain powder. The obtained powder is ground to be uniform by a mortar, and calcined at 920 ℃ for 10 hours to obtain the presintered product mother powder. Weighing a certain mass of mother powder, placing the mother powder in a die with the diameter of 15mm, placing the die on a workbench of a tablet press, applying 450MPa of pressure, maintaining the pressure for 5min, and demolding and taking out the molded complete biscuit. Embedding the biscuit sheet with mother powder, placing in an alumina crucible, keeping the temperature in a muffle furnace to 1050 ℃ for 2.5h, sintering at a heating rate of 10 ℃/min, ending after the temperature rises to 1250 ℃, and cooling along with the furnace to obtain Li 7 La 3 Zr 1.70 Cr 0.30 O 12 A solid electrolyte.
Example 13
The difference from example 12 is that Cr In example 12 was replaced with In.
Example 14
The difference from example 12 is that Cr in example 12 is replaced with Ti.
Example 15
The difference from example 12 is that Cr in example 12 is replaced with Mo.
Example 16
The difference from example 12 is that Cr in example 12 is replaced with W.
Example 17
Unlike example 1, la in example 1 was used 2 O 3 Instead of lanthanum hydroxide.
Example 18
Unlike example 1, la in example 1 was used 2 O 3 Instead of lanthanum nitrate.
Example 19
In contrast to example 1, liOH. Cndot. In example 1H 2 O is replaced with lithium carbonate.
Example 20
In contrast to example 1, liOH H in example 1 was 2 O is replaced with lithium acetate.
Example 21
In contrast to example 1, liOH H in example 1 was 2 O is replaced with lithium nitrate.
Example 22
The difference from example 1 is that ZrO in example 1 was used 2 And replaced with zirconium hydroxide.
Example 23
The difference from example 1 is that ZrO in example 1 was used 2 And replaced with zirconium nitrate.
Comparative example 1
Comparative example 1 is constant temperature sintered Li at low temperature 7 La 3 Zr 1.5 Ta 0.5 O 12 Preparation of solid electrolyte:
according to Li 7 La 3 Zr 1.5 Ta 0.5 O 12 0.15mol La was weighed out 2 O 3 ，0.7mol LiOH·H 2 O,0.15mol ZrO 2 And 0.025mol Ta 2 O 5 To compensate for volatilization of Li element in crystal structure at high temperature, lioh.h in raw material 2 O is 15% of the total mass. The raw materials are mixed and ball-milled in isopropanol ball-milling medium at a rotating speed of 380r/min for 20 hours and then dried in an oven at 80 ℃ for 24 hours. Grinding the obtained powder to be uniform by using a mortar, calcining at 900 ℃ for 10 hours to obtain a presintered product mother powder, weighing a certain mass of mother powder, placing the mother powder in a die with the diameter of 15mm, placing the die on a workbench of a tablet press, applying 400MPa of pressure and maintaining the pressure for 5 minutes, and demoulding and taking out the finished biscuit. Embedding the biscuit slice with mother powder, placing in an alumina crucible, sintering in a muffle furnace at 1000 ℃ for 12h, cooling along with the furnace, and obtaining Li after low-temperature sintering 7 La 3 Zr 1.5 Ta 0.5 O 12 A solid electrolyte.
Comparative example 2
Comparative example 2 is constant temperature sintered Li at high temperature 7 La 3 Zr 1.5 Ta 0.5 O 12 Preparation of solid electrolyte:
according to Li 7 La 3 Zr 1.5 Ta 0.5 O 12 0.15mol La was weighed out 2 O 3 ，0.7mol LiOH·H 2 O,0.15mol ZrO 2 And 0.025mol Ta 2 O 5 To compensate for volatilization of Li element in crystal structure at high temperature, lioh.h in raw material 2 O is 10% of the total mass. The raw materials are mixed and ball-milled in isopropanol ball-milling medium at a rotating speed of 380r/min for 20 hours and then dried in an oven at 80 ℃ for 24 hours. Grinding the obtained powder to be uniform by using a mortar, calcining at 900 ℃ for 10 hours to obtain a presintered product mother powder, weighing a certain mass of mother powder, placing the mother powder in a die with the diameter of 15mm, placing the die on a workbench of a tablet press, applying 400MPa of pressure and maintaining the pressure for 5 minutes, and demoulding and taking out the finished biscuit. Embedding the biscuit slice with mother powder, placing in an alumina crucible, sintering in a muffle furnace at 1200deg.C for 6h, cooling with the furnace, and obtaining Li after sintering at high temperature 7 La 3 Zr 1.5 Ta 0.5 O 12 A solid electrolyte.
The prepared solid electrolyte samples were subjected to microstructure analysis using a TM 3000 Scanning Electron Microscope (SEM), as shown in fig. 1, 2, and 3.
FIG. 1 is comparative example 1, li sintered at constant temperature at low temperature 7 La 3 Zr 1.5 Ta 0.5 O 12 The microscopic morphology of the solid electrolyte can be seen that the electrolyte has fine and uneven grain size, no crystal growth, many irregular and very obvious holes among grains, many grain boundaries among grains and many defects in the material body.
FIG. 2 is a constant temperature sintered Li of comparative example 2 under high temperature conditions 7 La 3 Zr 1.5 Ta 0.5 O 12 The solid electrolyte, as can be seen from the figure, has non-uniform grain size and part of the grains grow excessively, showing abnormal grain growth phenomenon. Both sintering methods of comparative example 1 and comparative example 2 resulted in low ionic conductivity and low relative density of the prepared electrolyte materials.
FIG. 3 is a diagram of example 3, li prepared by the dynamic sintering method 7 La 3 Zr 1.75 Ta 0.25 O 12 A solid electrolyte. As can be seen from the figure, the crystal grains are uniform in size, closely arranged, low in grain boundary concentration and free of obvious holes.
The electrolyte materials prepared in examples 3, 4 and 5 were subjected to ion conductivity analysis at 25 c by electrochemical workstations for comparison with examples 1 and 2, and ac impedance spectra thereof are shown in fig. 4, 5, 6, 7 and 8, and it can be seen that all the prepared samples showed a clear semicircle in the high frequency region and a tail in the low frequency region, indicating that the materials belong to the ion conductor. The ionic conductivities of the electrolytes prepared in comparative examples 1 and 2, example 3, example 4 and example 5 were 1.01X10, respectively, in that order, were calculated -4 ,1.36×10 -4 ，7.73×10 -4 ，8.31×10 -4 And 7.56X10 -4 S cm -1 . As can be seen by comparison, the solid electrolyte prepared by the dynamic sintering method has the highest ionic conductivity, and the conductivity is improved by 5.7-8.2 times. The sintering method is shown to be capable of effectively improving the ion conductivity of the garnet-type solid electrolyte.
To verify the stability of the solid electrolyte material prepared in example 3 to lithium metal, li|au/Li was assembled 7 La 3 Zr 1.75 Ta 0.25 O 12 The/au|li symmetric cell was tested as shown in fig. 9. As can be seen from the cycle chart, li prepared by dynamic sintering method 7 La 3 Zr 1.75 Ta 0.25 O 12 Can be at 0.2mA cm -2 The mixture was stably circulated at 25℃for 200 hours. Indicating the prepared Li 7 La 3 Zr 1.75 Ta 0.25 O 12 The solid electrolyte has a certain effect on the inhibition of lithium dendrites, and meanwhile, the solid electrolyte has excellent stability on lithium metal.
The above examples are only preferred embodiments of the present invention and are not intended to limit the embodiments of the present invention, and those skilled in the art will readily understand that any modifications, variations, equivalents, improvements and the like, which fall within the spirit and principle of the present invention, are included in the protection scope of the present invention, and the protection scope of the present invention is therefore defined by the following claims.
Claims (4)
1. A method for preparing a garnet-type solid electrolyte with high ion conductivity, which is characterized by comprising the following steps:
according to chemical formula Li 7 La 3 Zr 2-x M x O 12 Ball milling is carried out on the powder materials of the lithium source, the lanthanum source, the zirconium source and the M source, and then presintering is carried out for 8-10.5 hours at 800-950 ℃ to obtain primary sintered powder; pressing the primary sintered powder into round green sheets, and sintering the green sheets at a low temperature for 0.5-3 h; then continuously heating to a high temperature section, and immediately cooling along with a furnace body without heat preservation sintering to obtain the garnet type solid electrolyte with high ion conductivity, wherein the temperature of the low temperature section is 950-1200 ℃, the temperature of the high temperature section is 1000-1350 ℃, and the temperature of the high temperature section is at least 50 ℃ higher than the temperature of the low temperature section; the M source is an Al source, a Ga source, a Y source, an In source, a Ti source, a Hf source, a Nb source, a Ta source, a Cr source, a Mo source or a W source, and x is more than or equal to 0.2 and less than or equal to 0.75;
placing the blank sheet into a muffle furnace, and heating to a high temperature section at a heating rate of 1-20 ℃/min;
the cooling adopts furnace-following cooling;
0.2≤x≤0.5；
the M source is Al, ga, Y, in, ti, hf, nb, ta, cr, mo or an oxide of W;
pressing the primary sintered powder under the pressure of 300-500 MPa to form a round green sheet.
2. The method for preparing a garnet-type solid electrolyte having high ion conductivity according to claim 1, wherein the lithium source is one of lithium carbonate, lithium hydroxide, lithium acetate and lithium nitrate.
3. The method for preparing a garnet-type solid electrolyte having high ion conductivity according to claim 1, wherein the lanthanum source is one of lanthanum oxide, lanthanum hydroxide and lanthanum nitrate.
4. The method for preparing a garnet-type solid electrolyte having high ion conductivity according to claim 1, wherein the zirconium source is one of zirconia, zirconium hydroxide and zirconium nitrate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210158203.8A CN114497714B (en) | 2022-02-21 | 2022-02-21 | Preparation method of garnet type solid electrolyte with high ion conductivity |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210158203.8A CN114497714B (en) | 2022-02-21 | 2022-02-21 | Preparation method of garnet type solid electrolyte with high ion conductivity |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114497714A CN114497714A (en) | 2022-05-13 |
| CN114497714B true CN114497714B (en) | 2023-11-17 |
Family
ID=81482933
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210158203.8A Active CN114497714B (en) | 2022-02-21 | 2022-02-21 | Preparation method of garnet type solid electrolyte with high ion conductivity |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114497714B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115532219B (en) * | 2022-08-30 | 2024-03-22 | 上海交通大学 | Salt lake lithium extraction adsorbent based on garnet type solid electrolyte powder and preparation and application thereof |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103626487A (en) * | 2013-11-26 | 2014-03-12 | 中国科学院福建物质结构研究所 | Method for preparing yttrium aluminium garnet transparent ceramic with composite structure |
| WO2018139373A1 (en) * | 2017-01-30 | 2018-08-02 | セントラル硝子株式会社 | Method for producing electrode laminate for all-solid-state lithium batteries, electrode composite body for all-solid-state lithium batteries and method for producing same |
| CN108899581A (en) * | 2018-07-26 | 2018-11-27 | 上海电力学院 | A kind of preparation method of high-compactness carbuncle type inorganic solid electrolyte material |
| CN109037759A (en) * | 2017-06-09 | 2018-12-18 | 中国科学院上海硅酸盐研究所 | Prepare the sintering method of fine and close carbuncle type lithium ion solid electrolyte |
| RU2682325C1 (en) * | 2018-07-02 | 2019-03-19 | Федеральное государственное бюджетное учреждение науки Федеральный исследовательский центр "Кольский научный центр Российской академии наук" (ФИЦ КНЦ РАН) | METHOD FOR PRODUCING Li7La3Zr2O12 SOLID ELECTROLYTE DOPED WITH ALUMINUM |
| RU2685305C1 (en) * | 2018-05-28 | 2019-04-17 | Федеральное государственное автономное образовательное учреждение высшего образования "Дальневосточный федеральный университет" (ДВФУ) | Method of obtaining transparent ceramics of yttrium-aluminum garnet |
| CN112573574A (en) * | 2020-12-08 | 2021-03-30 | 北京工业大学 | Method for preparing garnet type solid electrolyte by regulating and controlling content of lithium vacancy |
| JP2021072283A (en) * | 2019-10-25 | 2021-05-06 | 国立大学法人信州大学 | Solid electrolyte, solid electrolyte battery and method for manufacturing the same |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108727025A (en) * | 2017-04-17 | 2018-11-02 | 中国科学院上海硅酸盐研究所 | Lithium garnet composite ceramics, Its Preparation Method And Use |
| US11673196B2 (en) * | 2018-12-24 | 2023-06-13 | University Of Science And Technology Beijing | Metal material sintering densification and grain size control method |
| US20220045355A1 (en) * | 2020-08-10 | 2022-02-10 | Corning Incorporated | Garnet-mgo composite thin membrane and method of making |
-
2022
- 2022-02-21 CN CN202210158203.8A patent/CN114497714B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103626487A (en) * | 2013-11-26 | 2014-03-12 | 中国科学院福建物质结构研究所 | Method for preparing yttrium aluminium garnet transparent ceramic with composite structure |
| WO2018139373A1 (en) * | 2017-01-30 | 2018-08-02 | セントラル硝子株式会社 | Method for producing electrode laminate for all-solid-state lithium batteries, electrode composite body for all-solid-state lithium batteries and method for producing same |
| CN109037759A (en) * | 2017-06-09 | 2018-12-18 | 中国科学院上海硅酸盐研究所 | Prepare the sintering method of fine and close carbuncle type lithium ion solid electrolyte |
| RU2685305C1 (en) * | 2018-05-28 | 2019-04-17 | Федеральное государственное автономное образовательное учреждение высшего образования "Дальневосточный федеральный университет" (ДВФУ) | Method of obtaining transparent ceramics of yttrium-aluminum garnet |
| RU2682325C1 (en) * | 2018-07-02 | 2019-03-19 | Федеральное государственное бюджетное учреждение науки Федеральный исследовательский центр "Кольский научный центр Российской академии наук" (ФИЦ КНЦ РАН) | METHOD FOR PRODUCING Li7La3Zr2O12 SOLID ELECTROLYTE DOPED WITH ALUMINUM |
| CN108899581A (en) * | 2018-07-26 | 2018-11-27 | 上海电力学院 | A kind of preparation method of high-compactness carbuncle type inorganic solid electrolyte material |
| JP2021072283A (en) * | 2019-10-25 | 2021-05-06 | 国立大学法人信州大学 | Solid electrolyte, solid electrolyte battery and method for manufacturing the same |
| CN112573574A (en) * | 2020-12-08 | 2021-03-30 | 北京工业大学 | Method for preparing garnet type solid electrolyte by regulating and controlling content of lithium vacancy |
Non-Patent Citations (2)
| Title |
|---|
| Two-step sintering strategy to prepare dense Li- Garnet electrolyte ceramics with high Li+ conductivity;Xiao Huang;《Ceramics International》;20171228;第1页第1行至第19页第1行 * |
| 两步烧结法合成钇铝石榴石透明陶瓷;陈智慧;李江涛;胡章贵;徐久军;;无机材料学报(第01期);全文 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114497714A (en) | 2022-05-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110233250B (en) | Preparation method of single crystal particle ternary cathode material | |
| CN106848392A (en) | Suppress solid electrolyte of lithium dendrite growth in all-solid-state battery and preparation method thereof | |
| CN110931738B (en) | Complex-phase high-voltage cathode material and preparation method thereof | |
| CN108793987B (en) | Lithium ion conductive oxide solid electrolyte and preparation method thereof | |
| CN113353985B (en) | Lithium ion battery positive electrode material, preparation method thereof, positive electrode of lithium ion battery and lithium ion battery | |
| WO2022222410A1 (en) | Solid electrolyte for lithium ion battery, and preparation method therefor | |
| CN115275329A (en) | Preparation method and application of garnet type solid electrolyte | |
| CN113809320A (en) | Quaternary polycrystalline positive electrode material, and preparation method and application thereof | |
| CN110128140A (en) | A kind of ytterbium aluminium codope carbuncle type Li7La3Zr2O12Lithium Ionic Conducting Materials and preparation method thereof | |
| CN114497714B (en) | Preparation method of garnet type solid electrolyte with high ion conductivity | |
| CN112573574A (en) | Method for preparing garnet type solid electrolyte by regulating and controlling content of lithium vacancy | |
| CN111786014A (en) | Garnet type solid electrolyte powder with superfine particle size and preparation method thereof | |
| CN111689773B (en) | Method for preparing LLZO solid electrolyte by microwave rapid sintering | |
| CN116143200B (en) | High-compaction micron monocrystal lithium-rich manganese-based positive electrode material, preparation method and lithium battery | |
| CN114447420B (en) | Cerium doped garnet type LLZO solid electrolyte for inhibiting growth of lithium dendrites and preparation method thereof | |
| CN115413273B (en) | Ceramic powder material, sintered body, and battery | |
| CN116014103A (en) | High-nickel ternary positive electrode material and preparation method and application thereof | |
| CN113161607A (en) | Preparation method of high-conductivity solid-state battery electrolyte for battery of energy storage charging system | |
| CN114725495A (en) | Easy-to-sinter garnet type solid electrolyte and preparation method thereof | |
| CN108417824A (en) | A kind of preparation method of high-performance lithium battery negative material carbon cladding lithium titanate | |
| CN114361578A (en) | Modified NASICON type oxide ceramic electrolyte and preparation method and application thereof | |
| CN113964390A (en) | Halogen ion doped LLZO solid electrolyte and preparation method thereof | |
| CN114243004B (en) | Garnet type solid electrolyte capable of effectively inhibiting lithium dendrites and preparation method thereof | |
| CN115417667B (en) | Nd 2 O 3 Doped Na-beta (beta') -Al 2 O 3 Solid electrolyte ceramic material and preparation method thereof | |
| CN116178012B (en) | High-entropy pomegranate Dan Gutai electrolyte ceramic and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |