CN117393844A - Preparation method of solid electrolyte - Google Patents
Preparation method of solid electrolyte Download PDFInfo
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- CN117393844A CN117393844A CN202311523595.4A CN202311523595A CN117393844A CN 117393844 A CN117393844 A CN 117393844A CN 202311523595 A CN202311523595 A CN 202311523595A CN 117393844 A CN117393844 A CN 117393844A
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- solid electrolyte
- lithium
- sintering
- llzto
- electrolyte
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- 239000007784 solid electrolyte Substances 0.000 title claims abstract description 126
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 62
- 238000005245 sintering Methods 0.000 claims abstract description 62
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 35
- 239000012298 atmosphere Substances 0.000 claims abstract description 33
- 239000002243 precursor Substances 0.000 claims abstract description 33
- 239000007787 solid Substances 0.000 claims abstract description 33
- 238000000034 method Methods 0.000 claims abstract description 31
- 239000011261 inert gas Substances 0.000 claims abstract description 24
- 238000000498 ball milling Methods 0.000 claims abstract description 21
- 229910052715 tantalum Inorganic materials 0.000 claims abstract description 18
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000000203 mixture Substances 0.000 claims abstract description 17
- 238000001035 drying Methods 0.000 claims abstract description 13
- 239000002904 solvent Substances 0.000 claims abstract description 13
- 238000002156 mixing Methods 0.000 claims abstract description 11
- 238000007493 shaping process Methods 0.000 claims abstract description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 78
- 229910052786 argon Inorganic materials 0.000 claims description 39
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 33
- 239000003792 electrolyte Substances 0.000 claims description 24
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 12
- 239000007789 gas Substances 0.000 claims description 12
- 239000001301 oxygen Substances 0.000 claims description 12
- 229910052760 oxygen Inorganic materials 0.000 claims description 12
- 239000000126 substance Substances 0.000 claims description 12
- 239000001257 hydrogen Substances 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 229910021193 La 2 O 3 Inorganic materials 0.000 claims description 4
- 238000003825 pressing Methods 0.000 claims description 3
- 238000000465 moulding Methods 0.000 claims description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims 2
- 239000001569 carbon dioxide Substances 0.000 claims 1
- 229910002092 carbon dioxide Inorganic materials 0.000 claims 1
- 238000010304 firing Methods 0.000 claims 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- 239000002223 garnet Substances 0.000 abstract description 4
- 230000009286 beneficial effect Effects 0.000 abstract description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 49
- 239000000919 ceramic Substances 0.000 description 40
- 239000012535 impurity Substances 0.000 description 15
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 12
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 10
- 229910001416 lithium ion Inorganic materials 0.000 description 10
- 239000000843 powder Substances 0.000 description 10
- 150000002500 ions Chemical class 0.000 description 9
- 239000013078 crystal Substances 0.000 description 8
- 235000012431 wafers Nutrition 0.000 description 8
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 229910052746 lanthanum Inorganic materials 0.000 description 6
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 229910052726 zirconium Inorganic materials 0.000 description 6
- 239000012300 argon atmosphere Substances 0.000 description 4
- 238000012512 characterization method Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 150000002431 hydrogen Chemical class 0.000 description 4
- 239000011812 mixed powder Substances 0.000 description 4
- 230000003287 optical effect Effects 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 230000001681 protective effect Effects 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- PQVSTLUFSYVLTO-UHFFFAOYSA-N ethyl n-ethoxycarbonylcarbamate Chemical compound CCOC(=O)NC(=O)OCC PQVSTLUFSYVLTO-UHFFFAOYSA-N 0.000 description 3
- GLXDVVHUTZTUQK-UHFFFAOYSA-M lithium hydroxide monohydrate Substances [Li+].O.[OH-] GLXDVVHUTZTUQK-UHFFFAOYSA-M 0.000 description 3
- 229940040692 lithium hydroxide monohydrate Drugs 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000011324 bead Substances 0.000 description 2
- UBAZGMLMVVQSCD-UHFFFAOYSA-N carbon dioxide;molecular oxygen Chemical compound O=O.O=C=O UBAZGMLMVVQSCD-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000001307 helium Substances 0.000 description 2
- 229910052734 helium Inorganic materials 0.000 description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 229910052743 krypton Inorganic materials 0.000 description 2
- DNNSSWSSYDEUBZ-UHFFFAOYSA-N krypton atom Chemical compound [Kr] DNNSSWSSYDEUBZ-UHFFFAOYSA-N 0.000 description 2
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 2
- 229910052754 neon Inorganic materials 0.000 description 2
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 230000002829 reductive effect Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 229910052724 xenon Inorganic materials 0.000 description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 229910018068 Li 2 O Inorganic materials 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000009766 low-temperature sintering Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 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
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 229910001251 solid state electrolyte alloy Inorganic materials 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000002203 sulfidic glass Substances 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- 238000002207 thermal evaporation Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
- H01M10/0562—Solid materials
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
-
- 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
-
- 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
- H01M2300/0085—Immobilising or gelification of electrolyte
-
- 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)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Conductive Materials (AREA)
- Secondary Cells (AREA)
Abstract
The invention discloses a preparation method of solid electrolyte, which comprises the steps of adding excessive precursor of lithium element into a pre-prepared solid electrolyte blank, mixing with a solvent, performing ball milling treatment, and then drying; shaping the mixture obtained after drying; then sintering the molded body in a sintering atmosphere containing inert gas to obtain a solid electrolyte; wherein the prepared solid electrolyte is a tantalum doped garnet type solid electrolyte. The solid electrolyte prepared by the method has higher ionic conductivity, can improve the performance of the whole battery, and is beneficial to the commercial application of lithium metal solid batteries.
Description
Technical Field
The invention relates to a preparation method of a solid electrolyte. And more particularly, to a method for preparing a tantalum-doped garnet-type solid electrolyte having high lithium ion conductivity, a solid electrolyte prepared by the method, and a solid lithium metal battery comprising the solid electrolyte.
Background
The lithium ion battery has the advantages of long cycle life, high energy density and the like, and is one of the most important energy storage devices in daily life. In recent years, with the rapid development of electric vehicles, there is a demand for higher energy density and safety performance of batteries. The solid lithium metal battery uses lithium metal as a negative electrode, and adopts solid electrolyte to replace the traditional diaphragm and electrolyte, so that the energy density of the battery is greatly improved, and the spontaneous combustion and explosion risks of the battery can be remarkably reduced.
Currently common solid electrolytes are oxide solid electrolytes, sulfide solid electrolytes, composite solid electrolytes, emerging halide solid electrolytes, and the like. Among them, the oxide solid electrolyte has the longest research time and the greatest commercialization probability. For example, studies have shown that garnet-type LLZO solid state electrolyte (Li 7 La 3 Zr 2 O 12 ) After Ta is doped, the lithium ion conductivity can be greatly improved, so that the research on tantalum doped LLZTO solid electrolyte is more extensive.
In the prior art, preparation of LLZTO still has many challenges, such as low density of ceramic plates, low ionic conductivity and the like. The LLZTO lithium ion conductivity obtained by the conventional normal pressure sintering means is about 0.5mS/cm, and is still lower in commercial use of the lithium battery, and the LLZTO lithium ion conductivity is far from reaching the theoretical value. In order to achieve the commercial use standard, it is necessary to further increase the lithium ion conductivity of the electrolyte to 0.8mS/cm or more.
Therefore, a method capable of sintering LLZTO solid electrolyte with higher ionic conductivity is designed, which is particularly critical for the commercial application of lithium metal solid batteries.
Disclosure of Invention
The invention aims to solve the technical problem that the lithium ion conductivity of a ceramic wafer is low when LLZTO solid electrolyte is sintered by air at present.
In order to solve the technical problems, the invention provides a preparation method of a high-conductivity solid electrolyte ceramic wafer. The method uses simple cold press sintering, prepares the solid electrolyte ceramic chip by controlling the excessive lithium and the sintering atmosphere environment, has simple preparation process and is beneficial to industrial production and application. Oxygen vacancies may be generated in the solid electrolyte when sintered in a protective atmosphere comprising an inert gas, thereby increasing the ionic conductivity of the ceramic sheet.
The first aspect of the present invention provides a method for preparing a solid electrolyte, comprising the steps of:
(1) Adding excessive precursor of lithium element into the prepared solid electrolyte blank, mixing with solvent, ball milling, and drying;
(2) Shaping the mixture obtained in step (1);
(3) Sintering the molded body obtained in step (2) in a sintering atmosphere containing an inert gas to obtain a solid electrolyte, wherein
The solid electrolyte is a tantalum doped garnet-type solid electrolyte.
In some embodiments, the tantalum doped garnet-type solid electrolyte prepared according to the method of the present invention has the formula Li 7-x La 3 Zr 2-x Ta x O 12 Wherein 0 is<x is not more than 1, preferably not less than 0.5 and not more than 0.6.
In some embodiments, the sintering atmosphere in step (3) comprises 50% or more by volume of inert gas, preferably 80% or more by volume, more preferably 95% or more by volume. In the present invention, the inert gas is selected from helium (He), neon (Ne), argon (Ar), krypton (Kr), xenon (Xn), and the like.
In some embodiments, the inert gas in the sintering atmosphere comprises argon, preferably the inert gas consists of argon.
In some embodiments, the sintering atmosphere in step (3) further comprises one or more gases selected from the group consisting of hydrogen, nitrogen, oxygen, carbon dioxide.
In some particularly preferred embodiments, the sintering atmosphere in step (3) consists of an inert gas, preferably argon.
In some embodiments, in step (1), the excess ratio of the number of moles of the precursor of the added lithium element to the molar content of the lithium element in the solid electrolyte is 30% or more, preferably 40% or more.
In some embodiments, in step (2), the shaping is performed by cold pressing at a pressure of 15 to 20MPa.
In some embodiments, in step (3), the sintering temperature is 1000 to 1500 ℃, preferably 1050 to 1200 ℃, more preferably 1100 to 1150 ℃.
In some embodiments, the method for preparing a solid electrolyte blank used in step (1) comprises the steps of:
(a1) According to the chemical composition of the solid electrolyte, mixing the precursor of each element and the precursor of the optional excessive lithium element with a solvent, performing ball milling treatment, and then drying;
(a2) Presintering the mixture obtained in step (a 1) to obtain the solid electrolyte blank.
In some embodiments, the precursor of each element may be an oxide, hydroxide, or salt of the corresponding element. In some preferred embodiments, the precursors of each element include a lithium source, a lanthanum source, a zirconium source, and a tantalum source; preferably, the precursor of each element comprises LiOH.H 2 O、La 2 O 3 、ZrO 2 And Ta 2 O 5 。
In some embodiments, the molar excess ratio of the precursor of the lithium element in step (a 1) is 1% to 20%, preferably 5% to 15%.
In some embodiments, the burn-in temperature in step (a 2) is lower than the sintering temperature in step (3). Specifically, the burn-in temperature is 700 to 1000 ℃, preferably 800 to 900 ℃.
The second aspect of the present invention provides a solid electrolyte prepared by the preparation method of the first aspect of the present invention.
In some embodiments, the solid state electrolyte of the present invention is a tantalum doped garnet type solid state electrolyte, preferably having the formula Li 6.4 La 3 Zr 1.4 Ta 0.6 O 12 。
In some embodiments, the solid state electrolyte of the present invention has an ionic conductivity of 0.8mS/cm or more, preferably 1.0mS/cm or more.
A third aspect of the present invention provides the use of a solid state electrolyte according to the second aspect of the present invention as described above in a solid state lithium metal battery.
A fourth aspect of the invention provides a solid state lithium metal battery comprising the solid state electrolyte of the second aspect of the invention described above.
Advantageous effects of the invention
The invention adjusts and controls the molar ratio of the excessive lithium in the sintering process, and sinters the ceramic chip in a protective atmosphere (such as argon atmosphere) containing inert gas, and the prepared solid electrolyte ceramic chip has higher ionic conductivity (such as more than 1 multiplied by 10) -3 S/cm) 2-5 times higher than conventional air sintering (about 1-5X 10) -4 S/cm). Higher lithium ion conductivity can improve the performance of the full cell, such as: better cycle performance, higher capacity retention, higher charge and discharge efficiency, and greater charge and discharge rate.
Drawings
Fig. 1 shows exemplary optical pictures of solid electrolyte LLZTO ceramic sheets prepared under different sintering atmospheres in example 5 of the present invention. The sintering atmosphere from left to right is as follows: (A) air; (B) nitrogen; (C) oxygen; (D) argon+hydrogen; (E) argon+oxygen; (F) argon.
Fig. 2 shows exemplary impedance test charts of solid electrolytes prepared according to examples and comparative examples of the present invention. The left round mark is an air sintered LLZTO ceramic plate; the right triangle is marked by LLZTO ceramic plate sintered in argon.
Fig. 3 shows optical pictures of LLZTO ceramic sheets sintered under different lithium excess conditions in example 4 of the present invention. (A) is sintering in argon, and (B) is sintering in air. The lithium excess ratios from left to right were 10%, 20%, 30%, 40%, respectively.
Fig. 4 shows an XRD pattern of a solid electrolyte LLZTO ceramic sheet prepared according to an embodiment of the invention. The preparation condition is sintering in argon, and the excess of lithium is 40%.
Fig. 5 shows SEM images of solid electrolyte LLZTO ceramic sheets prepared according to examples and comparative examples of the present invention. (A) and (B) are surface SEM images, and (C) and (D) are cross-sectional SEM images. The preparation conditions are sintering in argon, wherein (A) and (C) are excessive lithium by 40%, and (B) and (D) are excessive lithium by 10%.
Detailed Description
The invention is further illustrated by the following detailed description. Unless otherwise defined, terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. The numerical limits or ranges stated herein include the endpoints, and specifically include all values and subranges within the numerical limits or ranges.
The first aspect of the present invention provides a method for preparing a solid electrolyte, comprising the steps of:
(1) Adding excessive precursor of lithium element into the prepared solid electrolyte blank, mixing with solvent, ball milling, and drying;
(2) Shaping the mixture obtained in step (1);
(3) Sintering the molded body obtained in step (2) in a sintering atmosphere containing an inert gas to obtain a solid electrolyte, wherein
The solid electrolyte is a tantalum doped garnet-type solid electrolyte.
In some embodiments of the present invention, the tantalum doped garnet-type solid electrolyte prepared according to the method of the present invention has the formula Li 7-x La 3 Zr 2-x Ta x O 12 Wherein 0 is<x is not more than 1, preferably not less than 0.5 and not more than 0.6.
In some particularly preferred embodiments, the tantalum doped garnet-type solid electrolyte prepared according to the method of the present invention has the formula Li 6.4 La 3 Zr 1.4 Ta 0.6 O 12 。
In some embodiments of the present invention, the sintering atmosphere in step (3) contains 50% by volume or more of inert gas, preferably 80% by volume or more, more preferably 95% by volume or more. In the present invention, the inert gas refers to a gas simple substance corresponding to group 0 element of the periodic table, and includes helium (He), neon (Ne), argon (Ar), krypton (Kr), xenon (Xn), and the like. The inert gas has very low chemical reactivity, can be used as a protective gas under the high-temperature condition, does not basically react with the solid electrolyte or any precursor or intermediate product thereof under the preparation condition of the invention, can avoid potential side reactions in the preparation process, and ensures that the prepared solid electrolyte has an ideal lattice structure.
In some embodiments of the invention, the inert gas in the sintering atmosphere comprises argon, preferably the inert gas consists of argon. The expression "consisting of argon" means that the argon used is commercially available industrial or laboratory argon, with a purity of more than 99%, more than 99.9%, or more than 99.99%, but may still contain unavoidable impurities.
In some embodiments of the invention, the sintering atmosphere in step (3) further comprises one or more gases selected from the group consisting of hydrogen, nitrogen, oxygen, carbon dioxide. The content of the gas other than the inert gas in the sintering atmosphere is 50% by volume or less, preferably 20% by volume or less, and more preferably 5% by volume or less.
In the method for producing a solid electrolyte of the present invention, the lithium source needs to be provided in excess. In the context of the present invention, "excess" means that the number of moles of lithium element precursor charged during the preparation is greater than the molar content of lithium element in the solid electrolyte calculated on the basis of the chemical composition of the solid electrolyte in terms of the number of moles of other element precursors (e.g., lanthanum source, zirconium source, tantalum source, etc.). For example, the tantalum-doped garnet-type solid electrolyte prepared by the invention has the chemical formula of Li 7-x La 3 Zr 2-x Ta x O 12 If the mole ratio Li of lithium, lanthanum, zirconium and tantalum in lithium source, lanthanum source, zirconium source and tantalum source is La: zr: ta=M: 3:2-x, the mole ratio M of lithium in lithium source is greater than 7-x; the percentage excess was calculated as (M- (7-x))/(7-x).
In some particularly preferred embodiments, the sintering atmosphere in step (3) consists of an inert gas, preferably argon. That is, the sintering atmosphere does not contain other gases than inert gases.
In some embodiments of the present invention, in step (1), the excess ratio of the number of moles of the precursor of the added lithium element to the molar content of the lithium element in the solid electrolyte is 30% or more, preferably 40% or more. According to the studies of the present invention, it was found that the provision of an excessive amount of lithium source not only compensates for volatilization of lithium components during high-temperature sintering, but also further improves ion conductivity of the prepared solid electrolyte in the case that the excessive amount of lithium source is 30% or more, preferably 40% or more.
In some embodiments of the invention, in step (2), the shaping is performed by cold pressing at a pressure of 15 to 20MPa. For example, the powder after ball milling and drying may be placed in a circular mold having a diameter of 15mm and pressed under a pressure of 15 to 20MPa to obtain a molded disc.
In some embodiments of the invention, in step (3), the sintering temperature is 1000 to 1500 ℃, preferably 1050 to 1200 ℃, more preferably 1100 to 1150 ℃. In some embodiments of the invention, in step (3), the rate of temperature increase is from 5 to 20 ℃/min, preferably 10 ℃/min; the sintering time is 6 to 24 hours, preferably 12 hours.
In some embodiments of the present invention, the method for preparing a solid electrolyte blank used in step (1) includes the steps of:
(a1) According to the chemical composition of the solid electrolyte, mixing the precursor of each element and the precursor of the optional excessive lithium element with a solvent, performing ball milling treatment, and then drying;
(a2) Presintering the mixture obtained in step (a 1) to obtain the solid electrolyte blank.
In some embodiments of the invention, the precursor of each element may be an oxide, hydroxide or salt (e.g., nitrate) of the corresponding element. For example, as a lithium source, lithium hydroxide monohydrate (lioh.h 2 O) as lanthanum source, la can be used 2 O 3 As a result ofAs zirconium source, zrO may be used 2 . As a tantalum source, ta may be used 2 O 5 . The precursor may be pre-treated according to the actual circumstances, for example, when La is used 2 O 3 In this case, it is necessary to calcine at 900 ℃ or higher for 12 hours or longer in advance to remove the water. In some preferred embodiments, the precursor of each element comprises LiOH H 2 O、La 2 O 3 、ZrO 2 And Ta 2 O 5 。
In some embodiments of the invention, the molar excess ratio of the precursor of the lithium element in step (a 1) is between 1% and 20%, preferably between 5% and 15%. In the preparation of the solid electrolyte blank, the definition of the excess amount of lithium element is the same as above, i.e., the number of moles of the lithium element precursor charged in step (a 1) is larger than the molar content of lithium element in the solid electrolyte blank calculated on the basis of the chemical composition of the solid electrolyte in terms of the number of moles of the other element precursors (e.g., lanthanum source, zirconium source, tantalum source, etc.).
In some embodiments of the invention, the burn-in temperature in step (a 2) is lower than the sintering temperature in step (3). Specifically, the burn-in temperature in step (a 2) is 700 to 1000 ℃, preferably 800 to 900 ℃. In some embodiments of the invention, the rate of temperature increase in step (2 a) is from 5 to 20 ℃/min, preferably 10 ℃/min; the burn-in time is 6 to 24 hours, preferably 12 hours. The atmosphere used in the burn-in process is not particularly limited, and air may be used for the purpose of convenience of operation and cost reduction.
In addition, in some embodiments of the present invention, in the two ball milling steps (step (a 1) and step (1)), the solid-to-liquid ratio of the solid (i.e., precursor or blank) to the solvent may be 1:1 to 5, the ball-to-material ratio may be 1:1 to 10, the ball milling time may be 1 to 24 hours, the drying temperature may be 50 to 200 ℃, and the drying time may be 2 to 24 hours. In addition, the solvent may be isopropyl alcohol.
In an exemplary embodiment of the invention, the chemical formula is Li 6.4 La 3 Zr 1.4 Ta 0.6 O 12 Is prepared from solid electrolyteThe method comprises the following steps:
(a1) According to the chemical composition of the solid electrolyte and the excessive lithium source of 10%, the precursor of each element is treated with LiOH H 2 O:La 2 O 3 :ZrO 2 :Ta 2 O 5 After mixing a molar ratio of =7.04:1.5:1.4:0.3 with a solvent, ball milling treatment is performed, followed by drying;
(a2) Presintering the mixture obtained in step (a 1) at 900 ℃ to obtain a solid electrolyte blank;
(1) Adding a precursor LiOH H of 40% molar excess lithium element into the solid electrolyte blank prepared in the step (a 2) 2 O, mixing with a solvent, performing ball milling treatment, and then drying;
(2) Cold press molding the mixture obtained in the step (1);
(3) Sintering the molded body obtained in the step (2) in an argon sintering atmosphere to obtain a compound having the formula Li 6.4 La 3 Zr 1.4 Ta 0.6 O 12 Is a solid electrolyte of (a).
The inventor researches and discovers that in the preparation method of the solid electrolyte, after the solid electrolyte blank is prepared in advance, the secondary ball milling is carried out, so that the powder particle size is finer, the pressed and sintered LLZTO is denser, and the ion conductivity is higher. The primary purpose of low-temperature sintering after the first ball milling of the prepared blank is to phase the powder and obtain LLZTO phase. The 10% excess lithium source added in the first ball mill can make up for the loss of lithium when the powder is calcined at 900 degrees. In the step, if the excessive proportion of the lithium source is insufficient, the sintered LLZTO powder has poor phase formation, and cannot fully generate LLZTO phase, so that the final solid electrolyte product is affected; if the excess ratio of the lithium source is too large, more impurity phases are introduced. The second ball milling for preparing the solid electrolyte aims at refining phase powder with large impurity phase and coarse grain and lower activity in LLZTO phase of the solid electrolyte blank, and improving the sintering activity of the subsequent ceramic plate; and the excessive lithium source is further added during secondary balling, so that the complementary lithium hydroxide and the phase powder to be reacted are fully mixed, and the full reaction during secondary sintering is facilitated. SEM and XRD characterization prove that the solid electrolyte with large LLZTO crystal grain, less crystal boundary, no air hole and no other impurity phase can be generated by supplementing 40% of excessive lithium source in the secondary spherical ink sintering process.
The preparation method of the solid electrolyte can improve the ion conductivity of the solid electrolyte. Specifically, the solid electrolyte prepared according to the method of the present invention has an ion conductivity of 0.8mS/cm or more, preferably 1.0mS/cm or more. The reason is that the LLZTO solid electrolyte sintered in argon has higher density, less grain boundary and more complete crystal structure.
The second aspect of the present invention provides a solid electrolyte obtained by the production method according to the first aspect of the present invention.
In some embodiments of the present invention, the solid state electrolyte of the present invention is a tantalum doped garnet type solid state electrolyte, preferably having the formula Li 7-x La 3 Zr 2-x Ta x O 12 Wherein 0 is<x is not more than 1, preferably not less than 0.5 and not more than 0.6.
In some particularly preferred embodiments, the tantalum doped garnet-type solid electrolyte according to the invention has the formula Li 6.4 La 3 Zr 1.4 Ta 0.6 O 12 。
The solid state electrolyte of the second aspect of the present invention has ion conductivity superior to that of the solid state electrolyte of the prior art. In some embodiments of the present invention, the solid state electrolyte of the present invention has an ionic conductivity of 0.8mS/cm or more, preferably 1.0mS/cm or more.
A third aspect of the present invention provides the use of a solid state electrolyte according to the second aspect of the present invention as described above in a solid state lithium metal battery.
In a fourth aspect, the invention provides a solid state lithium metal battery. In some embodiments, the solid state lithium metal battery of the present invention comprises the solid state electrolyte of the second aspect of the present invention described above. The materials of the other parts of the lithium battery except the solid electrolyte and the preparation method thereof are not particularly limited, and conventional materials and preparation methods in the art may be used.
Examples
The present invention is described in detail below by way of examples, which are not intended to limit the present invention. The experimental methods in the following examples are conventional methods unless otherwise specified.
EXAMPLE 1 preparation of LLZTO solid electrolyte blank
To prepare the chemical formula Li 6.4 La 3 Zr 1.4 Ta 0.6 O 12 The following raw materials are weighed according to the stoichiometric ratio and the molar ratio of the lithium source excess of 10 percent: lithium hydroxide monohydrate (LiOH H) 2 O) 3.3198g, lanthanum oxide (La) 2 O 3 ) 5.4948g, zirconia (ZrO 2 ) 1.9396g and tantalum oxide (Ta 2 O 5 )1.4945g。
And putting the weighed precursor powder of each element into a zirconia ball milling tank, adding 9-10mL of isopropanol and 50g of zirconia ball milling beads, performing wet ball milling for 3 hours at 500rpm, and uniformly mixing to obtain mixed powder. Then the mixed powder is placed in an oven and dried at 80 ℃ to completely remove the solvent isopropanol.
And (3) placing the powder into a muffle furnace for presintering, heating from 50 ℃ to 900 ℃ at a heating rate of 10 ℃/min, preserving heat for 12 hours, cooling to 500 ℃ at a cooling rate of 10 ℃/min, naturally cooling to room temperature, and taking out to obtain presintered LLZTO solid electrolyte blank.
The LLZTO solid electrolyte blanks prepared as described above were used as starting materials in the subsequent examples for the preparation of LLZTO solid electrolytes, unless otherwise specified
EXAMPLE 2 preparation of LLZTO solid electrolyte
Weighing 10g of presintered LLZTO solid electrolyte blank, and weighing lithium hydroxide monohydrate (LiOH.H according to the required Li excess molar ratio 2 O), putting the mixture into a zirconia ball milling tank, adding 8-10mL of isopropyl alcohol and 50g of zirconia ball milling beads, performing wet ball milling for 8 hours at 500rpm, and uniformly mixing to obtain mixed powder. Then the mixed powder is placed in an oven and dried at 80 ℃ to completely remove the solvent isopropanol.
1.1g of the dried powder is weighed and placed in a circular die with the diameter of 15mm, and tabletting is carried out under the pressure of 15-20 MPa, so that a formed wafer is obtained. And then taking the crucible as a carrier, putting the formed wafer into a muffle furnace, heating from 50 ℃ to 1150 ℃ at a heating rate of 10 ℃/min under a corresponding sintering atmosphere, preserving heat for 12 hours, cooling to 500 ℃ at a cooling rate of 5 ℃/min, naturally cooling to room temperature, and taking out to obtain the LLZTO solid electrolyte.
Example 3 characterization of LLZTO solid electrolyte
Polishing the surface of the sintered LLZTO ceramic plate to be smooth, and then soaking the LLZTO ceramic plate in dilute hydrochloric acid for 30 seconds to remove Li on the surface 2 CO 3 And placing the mixture into a glove box for standby after impurities such as LiOH and the like.
The diameter and thickness of the LLZTO ceramic plates were measured using a micrometer.
In order to test the ion conductivity of the LLZTO solid electrolyte, a layer of Ag is evaporated on two sides of the LLZTO electrolyte sheet by a thermal evaporation film plating instrument to form an Ag/LLZTO/Ag blocking system, and a button cell is used for packaging. An ac impedance test was performed using a Metrohm Autolab with an ac voltage of 10mV and a frequency of 1-10 mhz. After measuring the ac impedance of the solid electrolyte ceramic sheet, the ionic conductivity σ is calculated by the formula σ=l/RS, where L is the ceramic sheet thickness, R is the ceramic sheet ac impedance, and S is the ceramic sheet single-sided area.
In addition, XRD and SEM tests were performed on a portion of LLZTO ceramic sheets.
The XRD tester was MiniFlex, japan, with a scan angle of 10-60℃and a scan rate of 8℃per minute.
The SEM tester was zeiss Sigma 300, and the solid electrolyte obtained by sintering was directly tested. The test contents include surface SEM and cross-section SEM.
EXAMPLE 4 Effect of molar excess ratio of lithium on conductivity of LLZTO solid electrolyte
In order to determine the influence of different sintering conditions on parameters such as conductivity and the like of the LLZTO ceramic plate, the conductivity rule of lithium ions of the LLZTO ceramic plate sintered under different molar excess ratios of lithium is firstly examined.
A LLZTO solid state electrolyte was prepared according to the method of example 2 above. Wherein, relative to the molar content of lithium element in LLZTO solid electrolyte blank, a newly added lithium source (LiOH. H 2 The molar excess of O) was 10%, 20%, 30% and 40%, respectively. Air and argon were used for the sintering atmosphere, respectively. After completion of the preparation of the LLZTO solid electrolyte, various parameters of the obtained LLZTO ceramic sheet were measured according to the method of example 3. The results are listed in table 1.
TABLE 1 LLZTO ceramic wafer parameters and conductivity prepared under different lithium excess conditions
Furthermore, optical pictures of LLZTO ceramic sheets sintered under different lithium excess conditions as described above are shown in fig. 3. Fig. 3 (a) shows, in order from left to right, LLZTO solid electrolytes with molar ratios of lithium excess of 10%, 20%, 30%, 40% sintered in argon; fig. 3 (B) shows LLZTO solid electrolytes with molar ratios of 10%, 20%, 30%, 40% of lithium excess sintered in air, in order from left to right. As can be seen from fig. 3, the LLZTO solid electrolytes obtained after sintering are round sheets with regular appearance. The LLZTO solid electrolyte sintered in argon was white in color and did not change significantly with increasing molar excess of lithium. In contrast, the color of LLZTO solid electrolyte sintered in argon gradually turns yellow and deep with increasing molar excess of lithium, and the increase of impurities in the electrolyte can be indicated from the side.
By comparing the characterization data of the solid electrolyte sintered in the air and argon atmosphere, it can be found that the ionic conductivity of the LLZTO ceramic plate is in a trend of continuously rising along with the increase of the lithium excess ratio during the sintering in the argon atmosphere; at a lithium excess ratio of 40%The ionic conductivity of (2) is highest. While the ionic conductivity of LLZTO ceramic sheets is always at a lower level even if the lithium excess ratio increases when sintered in an air atmosphere, and does not rise with the increase of the lithium excess ratio. The reason for this is that excessive lithium element may undergo side reactions with the sintering atmosphere to produce LiCO 3 、LiOH、Li 3 Impurities such as N cannot be compatible with LLZTO crystalline phase structure, thereby affecting the structure and ionic conductivity of the solid electrolyte.
As shown in the XRD pattern of FIG. 4, the LLZTO solid electrolyte sintered in argon gas at a lithium excess ratio of 40% showed characteristic peaks of LLZTO crystal phase, indicating the formation of a lithium ion-exchange resin with the chemical formula Li 6.4 La 3 Zr 1.4 Ta 0.6 O 12 Is a LLZTO solid electrolyte. No other characteristic peaks than LLZTO phases are shown in the XRD pattern, indicating that there are substantially no other impurity phases in the solid electrolyte and that the excess lithium precursor does not affect the crystal structure of the solid electrolyte.
As shown in the SEM image of fig. 5, at a Li excess of 40%, the synthesized LLZTO has large crystal grains, few grain boundaries, and no pores, indicating that it is substantially free of impurities, relative to a Li excess ratio of 10%. And when the Li excess ratio is low, the Li element in the solid electrolyte obtained by sintering is insufficient due to the loss caused by volatilization of the lithium source, possibly affecting the crystal structure.
Further experiments by the inventors have shown that if the Li excess ratio is further increased, the lithium-containing impurity phase (e.g. LiOH. H in the sintered LLZTO ceramic plate 2 O、LiOH、Li 2 O, etc.) will increase and the ionic conductivity will decrease. Therefore, in the present invention, the most preferable lithium excess ratio is 40%.
EXAMPLE 5 Effect of sintering atmosphere on conductivity of LLZTO solid electrolyte
To further determine the effect of different sintering atmospheres on parameters such as conductivity of LLZTO ceramic wafers, the conductivity of lithium ions of LLZTO ceramic wafers sintered in different sintering atmospheres was examined using a lithium excess ratio of 40%.
A LLZTO solid state electrolyte was prepared according to the method of example 2 above. Wherein, relativelyMolar content of lithium element in LLZTO solid electrolyte blank, newly added lithium source (LiOH. H 2 The molar excess of O) was 40%. The sintering atmosphere used was air, argon, nitrogen, oxygen, a mixed gas of argon (95 vol%) and hydrogen (5 vol%), and a mixed gas of argon (95 vol%) and oxygen (5 vol%), respectively. After completion of the preparation of the LLZTO solid electrolyte, various parameters of the obtained LLZTO ceramic sheet were measured according to the method of example 3. The results are listed in table 2.
TABLE 2 LLZTO ceramic wafer parameters and conductivity prepared under different sintering atmospheres
Further, an optical picture of LLZTO ceramic sheets sintered in the above different atmospheres is shown in fig. 1, the sintering atmospheres being in order: (A) air; (B) nitrogen; (C) oxygen; (D) argon+hydrogen; (E) argon+oxygen; (F) argon. As can be seen from fig. 1, the LLZTO solid electrolytes obtained after sintering are round sheets with regular appearance shapes, but there is a certain difference in color. The LLZTO solid electrolyte sintered in argon (F) was white in color; the LLZTO solid electrolyte sintered in argon and hydrogen (D) is substantially white in color; the LLZTO solid electrolyte sintered in other atmospheres is darker in color and yellow, which can be laterally indicated by the increase of impurities in the electrolyte.
FIG. 2 shows an exemplary impedance test chart of an air-sintered LLZTO ceramic plate, marked on the left with circles, an air-sintered LLZTO ceramic plate; the right triangle is marked by LLZTO ceramic plate sintered in argon.
From the characterization data of the solid-state electrolytes sintered under the above different atmospheres, respectively, it can be found that the ionic conductivity of LLZTO ceramic sheets is significantly better than that of sintered in air when sintered in an inert gas atmosphere using, for example, argonThe condition is as follows. In addition, the ionic conductivity of LLZTO ceramic plates sintered in pure nitrogen and pure oxygen atmospheres is similar to that of air, because more Li may be generated in nitrogen atmospheres 3 An N impurity; liCO is produced in large amounts in an oxygen atmosphere 3 Impurities such as LiOH and the like affect the density and the ion conductivity of LLZTO. When argon is mixed with a reducing gas such as hydrogen, the ionic conductivity of the resulting solid electrolyte is similar to that of a pure argon atmosphere; when the argon is mixed with the oxidizing gas (oxygen), even if the content of the oxygen is only 5 percent, the ion conductivity of the obtained solid electrolyte is obviously reduced, which proves that the preparation of LLZTO crystals is promoted and LiCO can be inhibited under the atmosphere of argon and trace reduction 3 Impurities such as LiOH are generated on the surface of LLZTO; the oxidizing atmosphere (oxygen) promotes the formation of impurities and does not have an inhibitory effect.
In summary, the invention can prepare the tantalum doped garnet type solid electrolyte with high ion conductivity by sintering in a protective atmosphere containing inert gas and regulating and controlling the molar ratio of excess lithium in the sintering process, thereby being beneficial to the commercialization application of lithium metal solid batteries.
The exemplary embodiments of the present invention have been described above by way of example, but the present invention is not limited thereto. It will be appreciated by those skilled in the art that the above examples are for illustrative purposes only and that the detailed description and examples should not be construed as limiting the scope of the invention. The embodiments can be changed and modified within the scope of the gist of the present invention, and such changes and modifications are intended to be within the scope of the present invention.
Claims (16)
1. A method of preparing a solid electrolyte, the method comprising the steps of:
(1) Adding excessive precursor of lithium element into the prepared solid electrolyte blank, mixing with solvent, ball milling, and drying;
(2) Shaping the mixture obtained in step (1);
(3) Sintering the molded body obtained in step (2) in a sintering atmosphere containing an inert gas to obtain a solid electrolyte, wherein
The solid electrolyte is a tantalum doped garnet-type solid electrolyte.
2. The method of claim 1, wherein the tantalum-doped garnet-type solid electrolyte has the formula Li 7-x La 3 Zr 2-x Ta x O 12 Wherein 0 is<x is not more than 1, preferably not less than 0.5 and not more than 0.6.
3. The production method according to claim 1 or 2, wherein the sintering atmosphere in step (3) contains 50% by volume or more of inert gas, preferably 80% by volume or more, more preferably 95% by volume or more.
4. A method of preparation according to any one of claims 1 to 3, wherein the inert gas comprises argon, preferably the inert gas consists of argon.
5. The method according to any one of claims 1 to 4, wherein the sintering atmosphere in step (3) further comprises one or more gases selected from the group consisting of hydrogen, nitrogen, oxygen, and carbon dioxide.
6. The production method according to any one of claims 1 to 5, wherein in the step (1), the excess ratio of the number of moles of the precursor of the added lithium element to the molar content of the lithium element in the solid electrolyte is 30% or more, preferably 40% or more.
7. The method according to any one of claims 1 to 6, wherein in the step (2), the molding is performed by cold pressing at a pressure of 15 to 20MPa.
8. The method according to any one of claims 1 to 7, wherein in step (3) the sintering temperature is 1000 to 1500 ℃, preferably 1050 to 1200 ℃, more preferably 1100 to 1150 ℃.
9. The production method according to any one of claims 1 to 8, wherein the production method of the solid electrolyte blank in step (1) comprises the steps of:
(a1) According to the chemical composition of the solid electrolyte, mixing the precursor of each element and the precursor of the optional excessive lithium element with a solvent, performing ball milling treatment, and then drying;
(a2) Presintering the mixture obtained in step (a 1) to obtain the solid electrolyte blank.
10. The method according to claim 9, wherein the precursor of each element comprises LiOH H 2 O、La 2 O 3 、ZrO 2 And Ta 2 O 5 。
11. The production method according to claim 9 or 10, wherein the molar excess ratio of the precursor of the lithium element in step (a 1) is 1 to 20%, preferably 5 to 15%.
12. The method according to any one of claims 9 to 11, wherein the pre-firing temperature in step (a 2) is lower than the sintering temperature in step (3), preferably 700 to 1000 ℃, more preferably 800 to 900 ℃.
13. A solid electrolyte, characterized in that the solid electrolyte is prepared by the preparation method according to any one of claims 1 to 12.
14. The solid state electrolyte according to claim 13, characterized in that the ionic conductivity of the solid state electrolyte is 0.8mS/cm or more, preferably 1.0mS/cm or more.
15. Use of the solid state electrolyte of claim 13 or 14 in a solid state lithium metal battery.
16. A solid state lithium metal battery comprising the solid state electrolyte of claim 13 or 14.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117976969A (en) * | 2024-03-28 | 2024-05-03 | 深圳欣界能源科技有限公司 | Method for producing solid electrolyte containing oxygen vacancy and solid battery |
| CN118198480A (en) * | 2024-05-13 | 2024-06-14 | 深圳欣界能源科技有限公司 | Flexible solid electrolyte membrane and preparation method thereof, solid battery and preparation method thereof, and power utilization device |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110053002A1 (en) * | 2009-09-03 | 2011-03-03 | Ngk Insulators, Ltd. | Ceramic material and preparation method therefor |
| JP2013219017A (en) * | 2012-02-21 | 2013-10-24 | Ngk Insulators Ltd | Method for restoring ion conductivity of solid electrolyte ceramic material |
| CN110176627A (en) * | 2019-06-18 | 2019-08-27 | 济宁克莱泰格新能源科技有限公司 | It can inhibit the lithium lanthanum zirconium oxygroup solid electrolyte material and its preparation method and application of Li dendrite |
| CN114447420A (en) * | 2021-12-09 | 2022-05-06 | 电子科技大学长三角研究院(湖州) | Cerium-doped garnet-type LLZO solid electrolyte for inhibiting growth of lithium dendrites and preparation method thereof |
| US20220200048A1 (en) * | 2019-09-11 | 2022-06-23 | Zhejiang University | Ion conductor with high room-temperature ionic conductivity and preparation method thereof |
| CN116864789A (en) * | 2023-07-31 | 2023-10-10 | 楚能新能源股份有限公司 | Garnet type lithium ion solid electrolyte and preparation method and application thereof |
| CN116914236A (en) * | 2023-06-02 | 2023-10-20 | 常州工学院 | Solid electrolyte modified by lithium-philic alloy interface layer, application and preparation method thereof |
-
2023
- 2023-11-14 CN CN202311523595.4A patent/CN117393844A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110053002A1 (en) * | 2009-09-03 | 2011-03-03 | Ngk Insulators, Ltd. | Ceramic material and preparation method therefor |
| JP2013219017A (en) * | 2012-02-21 | 2013-10-24 | Ngk Insulators Ltd | Method for restoring ion conductivity of solid electrolyte ceramic material |
| CN110176627A (en) * | 2019-06-18 | 2019-08-27 | 济宁克莱泰格新能源科技有限公司 | It can inhibit the lithium lanthanum zirconium oxygroup solid electrolyte material and its preparation method and application of Li dendrite |
| US20220200048A1 (en) * | 2019-09-11 | 2022-06-23 | Zhejiang University | Ion conductor with high room-temperature ionic conductivity and preparation method thereof |
| CN114447420A (en) * | 2021-12-09 | 2022-05-06 | 电子科技大学长三角研究院(湖州) | Cerium-doped garnet-type LLZO solid electrolyte for inhibiting growth of lithium dendrites and preparation method thereof |
| CN116914236A (en) * | 2023-06-02 | 2023-10-20 | 常州工学院 | Solid electrolyte modified by lithium-philic alloy interface layer, application and preparation method thereof |
| CN116864789A (en) * | 2023-07-31 | 2023-10-10 | 楚能新能源股份有限公司 | Garnet type lithium ion solid electrolyte and preparation method and application thereof |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117976969A (en) * | 2024-03-28 | 2024-05-03 | 深圳欣界能源科技有限公司 | Method for producing solid electrolyte containing oxygen vacancy and solid battery |
| CN117976969B (en) * | 2024-03-28 | 2024-08-13 | 深圳欣界能源科技有限公司 | Method for producing solid electrolyte containing oxygen vacancy and solid battery |
| CN118198480A (en) * | 2024-05-13 | 2024-06-14 | 深圳欣界能源科技有限公司 | Flexible solid electrolyte membrane and preparation method thereof, solid battery and preparation method thereof, and power utilization device |
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