CN114678587B - Preparation method of solid electrolyte, lanthanum titanium oxide compound and preparation method thereof - Google Patents
Preparation method of solid electrolyte, lanthanum titanium oxide compound and preparation method thereof Download PDFInfo
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- -1 lanthanum titanium oxide compound Chemical class 0.000 title claims abstract description 103
- 239000007784 solid electrolyte Substances 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 56
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 55
- 238000005245 sintering Methods 0.000 claims abstract description 54
- 238000000034 method Methods 0.000 claims abstract description 52
- 238000002156 mixing Methods 0.000 claims abstract description 29
- 239000000203 mixture Substances 0.000 claims abstract description 22
- 239000000126 substance Substances 0.000 claims abstract description 6
- 238000002441 X-ray diffraction Methods 0.000 claims abstract description 3
- 239000002245 particle Substances 0.000 claims description 35
- 239000002002 slurry Substances 0.000 claims description 24
- 150000001875 compounds Chemical class 0.000 claims description 22
- 239000000843 powder Substances 0.000 claims description 20
- 229910052746 lanthanum Inorganic materials 0.000 claims description 19
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 19
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 15
- 239000010936 titanium Substances 0.000 claims description 14
- 229910052719 titanium Inorganic materials 0.000 claims description 13
- 239000000463 material Substances 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 9
- 238000000889 atomisation Methods 0.000 claims description 2
- 238000001238 wet grinding Methods 0.000 claims description 2
- 229910015015 LiAsF 6 Inorganic materials 0.000 claims 1
- 229910013063 LiBF 4 Inorganic materials 0.000 claims 1
- 229910013684 LiClO 4 Inorganic materials 0.000 claims 1
- 229910013870 LiPF 6 Inorganic materials 0.000 claims 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims 1
- 239000002994 raw material Substances 0.000 abstract description 22
- 239000012535 impurity Substances 0.000 abstract description 13
- 229910010252 TiO3 Inorganic materials 0.000 abstract description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 239000002699 waste material Substances 0.000 abstract description 4
- 238000010923 batch production Methods 0.000 abstract description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 32
- 230000008569 process Effects 0.000 description 22
- 239000000047 product Substances 0.000 description 21
- 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 18
- 239000012071 phase Substances 0.000 description 18
- 239000004408 titanium dioxide Substances 0.000 description 16
- 238000000634 powder X-ray diffraction Methods 0.000 description 13
- 239000004576 sand Substances 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 10
- 229910001416 lithium ion Inorganic materials 0.000 description 9
- 238000003801 milling Methods 0.000 description 9
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 8
- 230000009286 beneficial effect Effects 0.000 description 8
- 239000002105 nanoparticle Substances 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 7
- LSYIMYXKHWXNBV-UHFFFAOYSA-N lanthanum(3+) oxygen(2-) titanium(4+) Chemical compound [O-2].[La+3].[Ti+4] LSYIMYXKHWXNBV-UHFFFAOYSA-N 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 238000001514 detection method Methods 0.000 description 6
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 6
- 229910052808 lithium carbonate Inorganic materials 0.000 description 6
- CEMTZIYRXLSOGI-UHFFFAOYSA-N lithium lanthanum(3+) oxygen(2-) titanium(4+) Chemical compound [Li+].[O--].[O--].[O--].[O--].[Ti+4].[La+3] CEMTZIYRXLSOGI-UHFFFAOYSA-N 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 238000010532 solid phase synthesis reaction Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 238000005303 weighing Methods 0.000 description 6
- 238000005265 energy consumption Methods 0.000 description 5
- 239000007791 liquid phase Substances 0.000 description 5
- 229910011244 Li3xLa2/3-xTiO3 Inorganic materials 0.000 description 4
- 229910011245 Li3xLa2/3−xTiO3 Inorganic materials 0.000 description 4
- 230000002776 aggregation Effects 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 229910003480 inorganic solid Inorganic materials 0.000 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 description 4
- 239000011244 liquid electrolyte Substances 0.000 description 4
- 238000001694 spray drying Methods 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 3
- 238000005054 agglomeration Methods 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 239000011324 bead Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000004146 energy storage Methods 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 229910003002 lithium salt Inorganic materials 0.000 description 3
- 159000000002 lithium salts Chemical class 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- 229910052726 zirconium Inorganic materials 0.000 description 3
- 229910020717 Li0.33La0.56TiO3 Inorganic materials 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000003980 solgel method Methods 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 229910000552 LiCF3SO3 Inorganic materials 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- RJEIKIOYHOOKDL-UHFFFAOYSA-N [Li].[La] Chemical compound [Li].[La] RJEIKIOYHOOKDL-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 229910002113 barium titanate Inorganic materials 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 239000000306 component Substances 0.000 description 1
- 239000008358 core component Substances 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- YXEUGTSPQFTXTR-UHFFFAOYSA-K lanthanum(3+);trihydroxide Chemical compound [OH-].[OH-].[OH-].[La+3] YXEUGTSPQFTXTR-UHFFFAOYSA-K 0.000 description 1
- 229910001540 lithium hexafluoroarsenate(V) Inorganic materials 0.000 description 1
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 1
- 229910001486 lithium perchlorate Inorganic materials 0.000 description 1
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 description 1
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 229910001251 solid state electrolyte alloy Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 150000003608 titanium Chemical class 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/003—Titanates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/003—Titanates
- C01G23/005—Alkali titanates
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
-
- 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
- H01M2300/002—Inorganic electrolyte
-
- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Electrochemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Manufacturing & Machinery (AREA)
- General Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Physics & Mathematics (AREA)
- Materials Engineering (AREA)
- Secondary Cells (AREA)
- Conductive Materials (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The application provides a preparation method of a solid electrolyte, a lanthanum titanium oxide compound, a preparation method thereof and a lithium battery, wherein the method comprises the steps of mixing the lanthanum titanium oxide compound with a lithium source to obtain a mixture; sintering the mixture to obtain a lithium lanthanum titanium oxide compound with a perovskite structure, namely a solid electrolyte, wherein the chemical formula of the lanthanum titanium oxide compound is La 2/3‑xTiO3, wherein X is 0< 0.16, and an X-ray diffraction pattern of the lanthanum titanium oxide compound contains characteristic diffraction peaks at 2 theta angles of 32+/-1 degrees, 40+/-1 degrees and 46+/-1 degrees. The lithium lanthanum titanium oxide compound prepared by the method has good phase singleness, no generation of impurity phase, improves the purity and crystallinity of the product, and simultaneously reduces the loss and waste of lithium raw materials, thereby reducing the production cost and realizing batch production.
Description
Technical Field
The application relates to the field of green energy, in particular to a preparation method of a solid electrolyte, a lanthanum titanium oxide compound and a lithium battery.
Background
Currently, in face of sustainable development requirements of energy sources and ecological environments, development of an energy storage system which has higher energy density and is environment-friendly has important significance. Lithium ion batteries (LB) have taken the dominant role of energy storage devices since commercialization. Lithium ion batteries have been widely used in most electronic products, including as large energy storage devices in electric automobiles. Most of widely used lithium ion batteries adopt liquid electrolytes, and the liquid electrolytes have hidden danger in safety, so that the application of the lithium ion batteries is endangered. Compared with the liquid electrolyte, the inorganic solid electrolyte has the outstanding advantages of incombustibility, which just compensates the defects of the liquid electrolyte, and in addition, the higher mechanical strength can effectively inhibit the penetration of lithium dendrites during the battery cycle process, so that the application of lithium metal is possible. This has led researchers to put more focus on the investigation of inorganic solid state electrolytes.
The biggest impediment to the current practice of most inorganic solid state electrolytes is their very low conductivity for use, far from the commercially required conductivity of 10 -3 S/cm. While perovskite type ABO 3 (a=la, sr or Ca; b=al or Ti) inorganic solid electrolyte, li may be introduced into perovskite at a site to form a lithium lanthanum titanium oxide solid electrolyte. The total conductivity of the lithium lanthanum titanium oxide solid electrolyte is mainly controlled by the conductivity of a crystal boundary, and the ionic conductivity of the lithium lanthanum titanium oxide solid electrolyte at room temperature is as high as more than 10 -3 S/cm and is close to the level of commercial electrolyte. The lithium lanthanum titanium oxide compound solid electrolyte also has the advantages of stable structure, simple preparation process, wide component variable range and the like.
The research shows that different lithium lanthanum titanium oxide compound synthesis methods have certain influence on the structure acquisition of the electrolyte, so that the synthesis of the stable single-phase lithium lanthanum titanium oxide compound is very important, and whether the lithium lanthanum titanium oxide compound solid electrolyte can be widely popularized and applied is determined. Common methods for synthesizing lithium lanthanum titanium oxide mainly comprise a sol-gel method, a liquid phase precipitation method and a solid phase method, wherein expensive alkoxide is used in the synthesis process of the sol-gel method, so that the preparation cost is high, the method is only suitable for laboratory researches, the other liquid phase precipitation method has some defects in the synthesis process, such as difficulty in controlling the dissolution process of titanium salt by using a technical means and inapplicability to industrial production, and compared with the solid phase method, the solid phase method is the first choice process of a mass production process due to simple equipment requirement and low raw material cost.
However, the process for synthesizing the lithium lanthanum titanium oxide compound by the solid phase method in the current market is difficult to realize batch production, and mainly has the following reasons that 1) the lithium source participates in the reaction for too long, the long-time high-temperature calcination can cause higher energy consumption and volatilization loss of lithium salt, single phase instability of the lithium lanthanum titanium oxide compound is caused, an impurity phase is generated, the purity and the precision of the finally obtained product are lower, and the application requirements of the lithium lanthanum titanium oxide compound solid electrolyte in a lithium ion battery cannot be met, and 2) the lithium source is often added according to the experience of technicians in the actual production due to higher loss of the lithium source in the reaction process, so that the single-phase stable lithium lanthanum titanium oxide compound cannot be produced in batch.
Disclosure of Invention
The application provides a preparation method of a solid electrolyte, a lanthanum titanium oxide compound and a preparation method thereof, which improve the purity and crystallinity of a product, reduce the loss and waste of lithium raw materials and realize the mass production of the solid electrolyte.
In a first aspect, the present application provides a lanthanum titanyl compound comprising:
mixing lanthanum titanium oxide compound with a lithium source to obtain a mixture;
Sintering the mixture to obtain a lithium lanthanum titanium oxide compound with a perovskite structure, namely the solid electrolyte;
the lanthanum titanium oxide compound has a chemical formula of La 2/3-xTiO3, wherein 0< x <0.16.
Alternatively, in some embodiments of the application, the total molar ratio of the lanthanum titanium oxide compound to the lithium lanthanum titanium oxide compound is (5-3 x): (6x+5), where 0< x <0.16, and the lithium source is added in an amount of 1.05 to 1.10 times the molar amount of lithium in the lithium lanthanum titanium oxide compound.
Optionally, in some embodiments of the application, the sintering is performed at a temperature of 900 ℃ to 1000 ℃ and/or for a time of 8 hours to 20 hours.
Optionally, in some embodiments of the application, the lanthanum titanium oxide has a particle size of 5 μm to 15 μm, and/or,
The particle size of the lithium source is 5-15 mu m.
In a second aspect, the application provides a lanthanum titanium oxide compound, which has a chemical formula of La 2/3-xTiO3, wherein 0< x <0.16.
Alternatively, in some embodiments of the application, the X-ray diffraction pattern of the lanthanum titanium oxide compound contains characteristic diffraction peaks at 2-theta angles of 32 + -1 degrees, 40 + -1 degrees, and 46 + -1 degrees.
In a third aspect, the present application provides a method for preparing a lanthanum titanium oxide compound, comprising:
Mixing a lanthanum source compound with micron-sized particle size with a titanium source compound with micron-sized particle size to obtain a mixture;
wet-pulverizing the mixture to obtain slurry containing mixed particles with nanoscale particle sizes;
drying the slurry to obtain dry powder;
sintering the dry powder to obtain the lanthanum titanium oxide compound.
Alternatively, in some embodiments of the application, the molar ratio of the lanthanum source compound to the titanium source compound is (1-5): 2-4.
Optionally, in some embodiments of the application, the sintering temperature is 900 ℃ to 1200 ℃, and/or the sintering time is 10 hours to 48 hours, and/or a sintering aid is also added to the raw materials during the mixing, and/or the sintering aid is an oxide.
Optionally, in some embodiments of the application, the mixing is wet mixing, the mass percent concentration of solids in the mixture is 12% -13%, and/or the drying is spray drying.
Accordingly, the fourth aspect of the application provides a lithium battery comprising the solid electrolyte prepared by the preparation method, or comprising the lanthanum titanium oxide compound prepared by the preparation method.
The method has the advantages of simple process, capability of greatly shortening the time for the lithium source to participate in the reaction, avoiding the loss and waste of lithium raw materials caused by long-time high-temperature sintering, reducing the cost and loss of the lithium raw materials in the process of synthesizing the perovskite type solid electrolyte, effectively preventing the formation of impurity phases, and solving the problem that the conventional solid phase method for preparing the perovskite type solid electrolyte cannot stably form the lithium lanthanum titanium oxide compound with a single phase because the lithium source cannot be quantitatively added, and the batch production of the perovskite type solid electrolyte cannot be realized.
The lithium lanthanum titanium oxide compound prepared by the method has good phase singleness, no generation of impurity phase, and the crystallinity and purity of the product are improved, so that the electrochemical performance of the lithium lanthanum titanium oxide compound is improved, and the conductivity of the lithium lanthanum titanium oxide compound solid electrolyte is further improved.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings that are needed in the description of the embodiments will be briefly described below, it being obvious that the drawings in the following description are only some embodiments of the present application, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is an X-ray powder diffraction (XRD) pattern of a lanthanum titanium oxide compound prepared in accordance with the present application;
FIG. 2 is an X-ray powder diffraction (XRD) pattern of a lithium lanthanum titanium oxide compound prepared in accordance with the present application;
FIG. 3 is XRD standard card JCPDS No.87-0935.
Detailed Description
The following description of the embodiments of the present application will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present application, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the application without making any inventive effort, are intended to fall within the scope of the application. Furthermore, it should be understood that the detailed description is presented herein for purposes of illustration and description only, and is not intended to limit the application. In the present application, unless otherwise indicated, terms of orientation such as "upper", "lower", "left" and "right" are generally used to refer to the directions of the upper, lower, left and right sides of the device in actual use or operation, and are specifically shown in the drawings.
The application provides a preparation method of a solid electrolyte, a lanthanum titanium oxide compound, a preparation method thereof and a lithium battery, and the preparation method and the lithium battery are respectively described in detail below. It should be noted that the following description order of the embodiments is not intended to limit the preferred order of the embodiments of the present application. In the following embodiments, the descriptions of the embodiments are focused on, and for the part that is not described in detail in a certain embodiment, reference may be made to the related descriptions of other embodiments.
Embodiments of the present application provide a method of preparing a solid electrolyte, comprising:
Mixing lanthanum titanium oxide compound with lithium source to obtain mixed material, sintering the mixed material to obtain lithium lanthanum titanium oxide compound with perovskite structure, i.e. solid electrolyte, wherein the chemical formula of lanthanum titanium oxide compound is La 2/3-xTiO3, wherein x is 0.16, the value of x can be 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 0.10, 0.11, 0.12, 0.13, 0.14, 0.15, etc., of course, the value of x can be any other value in the range of 0-0.16. The chemical formula of the lithium lanthanum titanium oxide compound is Li 3xLa2/3-xTiO3. In other embodiments, the perovskite type solid electrolyte prepared by the method has the highest lithium ion conductivity of Li 0.33 La0.56TiO3 and the conductivity of 10 -3 S/cm. Since it is known from the cubic perovskite structure of Li 3xLa2/3- xTiO3 that Ti atoms octahedral coordinated with oxygen atoms occupy the cube corners and the cube center is occupied or vacant by La 3+, li ions, the ionic conductivity is directly affected by the concentration of vacancies and the interaction force between lithium ions and the coordination framework, the highest lithium ion conductivity in the perovskite solid electrolyte is Li 0.33La0.56TiO3. Of course, the method can also be used for preparing the lithium 0.55La0.35TiO3 which has compatible stability for different anode materials.
In the preparation method, the special lanthanum titanium oxide compound is used as a raw material, and the lanthanum titanium oxide compound is a novel material prepared by the preparation method of the lanthanum titanium oxide compound provided by the application, and the specific preparation method is described in detail below. The lithium source may be any lithium salt selected from LiPF6、LiBF4、LiClO4、LiAsF6、LiCF3SO3、LiN(CF3SO2)2、Li CO and the like, and the above lithium salts are commercially available.
In some embodiments, after the solid electrolyte is obtained, the particle size of the lithium lanthanum titanium oxide compound may be controlled within a desired range by sanding or other grinding means according to customer requirements.
In some embodiments, the total lanthanum titanium oxide to lithium lanthanum titanium oxide molar ratio is (5-3 x): (6x+5), where 0< x <0.16, i.e., lanthanum titanium oxide is added according to the molar ratio of lithium, lanthanum, titanium of lithium lanthanum titanium oxide Li 3xLa2/3-xTiO3, 3x (2/3-x): 1. The amount of the lithium source added is 1.05 to 1.10 times the molar amount of lithium in the lithium lanthanum titanyl compound. I.e. 5 to 10 percent of the excess of the lithium source according to the molar ratio of the lithium lanthanum titanium oxide compound Li 3xLa2/3-xTiO3. Because the preparation method of the application sinters the prefabricated lanthanum titanium oxide compound and the lithium source to form the lithium lanthanum titanium oxide compound, the time for the lithium source to participate in the reaction is shortened, so the application can realize accurate and controllable addition of the lithium source, namely small excessive addition, rather than large excessive addition by experience, thereby being beneficial to forming a stable single-phase product, avoiding the waste of the lithium source and reducing the addition cost of the lithium source. Experiments prove that the addition amount of the lithium source is smaller than that of the lithium source in the prior art, but the yield is not obviously reduced. In other embodiments, the lanthanum titanium oxide has a particle size of 5 μm to 15 μm and the lithium source has a particle size of 5 μm to 15 μm. The particle sizes of the lanthanum titanium oxide compound and the lithium source adopt the size parameters, which is beneficial to increasing the reactivity of the product, thereby being beneficial to improving the crystallinity of the final product. For example, in a specific example, the lanthanum titanium oxide compound may have an average particle size of 5 μm, 6 μm, 7 μm, 8 μm, 9 μm, 10 μm, 11 μm, 12 μm, 13 μm, 14 μm or 15 μm, or any other particle size in the range of 5 μm to 15 μm. The average particle diameter of the lithium source may be 5 μm, 6 μm, 7 μm, 8 μm, 9 μm, 10 μm, 11 μm, 12 μm, 13 μm, 14 μm or 15 μm, or any other particle diameter size in the range of 5 μm to 15 μm.
In other embodiments of the present application, the lanthanum titanyl compound is mixed with the lithium source and then sintered, wherein the sintering may be performed using a process parameter of 900 ℃ to 1000 ℃ and/or a sintering time of 8 hours to 20 hours. Because the sintering temperature of the existing related process is 900-1200 ℃, the sintering time is 10-30 h. The solid phase method of the application has low sintering temperature and short sintering time. In a specific example, the sintering temperature may be any of 900 ℃, 920 ℃, 950 ℃, 980 ℃, or 1000 ℃, or any other temperature within the range of 900 ℃ to 1000 ℃, the sintering time may be 8 hours, 9 hours, 12 hours, 14 hours, 16 hours, 18 hours, or 20 hours, or any other temperature within the range of 8 hours to 20 hours. The control of the sintering process parameters is beneficial to the formation of grain gaps in the reaction process and the improvement of the conductivity of the solid electrolyte, and is beneficial to the formation of single-phase products, thereby being beneficial to the improvement of the crystallinity of the products.
In other embodiments of the present application, a lanthanum titanyl compound is provided having the formula La 2/3-xTiO3, wherein 0< x <0.16. In the X-ray powder diffraction pattern, 3 main characteristic diffraction peaks and 4 secondary peaks appear at diffraction angles 2θ of 20 ° -80 °. The 2 theta angles of the 3 main characteristic diffraction peaks are respectively at 32 + -1 degree, 40 + -1 degree and 46 + -1 degree, and the 5 secondary peaks are respectively at 27 + -1 degree, 30 + -1 degree, 58 + -1 degree, 68 + -1 degree and 77 + -1 degree. In other embodiments, the lanthanum element, the titanium element and the oxygen element are mixed according to the following mass percentage, wherein the lanthanum element is 30% -50%, the titanium element is 10% -30% and the oxygen element is 10% -35%. And mixing and sintering to obtain the lanthanum titanium oxide compound.
In other embodiments of the present application, there is provided a method for preparing a lanthanum titanyl compound, comprising:
Mixing a lanthanum source compound with micron-sized particle size with a titanium source compound with micron-sized particle size to obtain a mixture;
wet-pulverizing the mixture to obtain slurry containing mixed particles with nanoscale particle size;
drying the slurry to obtain dry powder;
and sintering the dry powder to obtain the lanthanum titanium oxide compound.
Because the nanoscale particle size is small, particle aggregation phenomenon is easy to occur in the crushing process during mixing, heat conduction is not uniform, so that local high temperature is easy to generate, partial raw materials in a local high temperature region are easy to oxidize and lose, chemical reaction is easy to generate impurities, the impurities can cause impurity phases in the subsequent sintering process, and the purity of a product is influenced. In addition, the nanoscale particle size is too small, and the two raw materials are not easy to mix uniformly during crushing, so that the raw materials cannot fully react during subsequent sintering, the uniformity of the crystal structure of the product is affected, and impurity phases are also generated. In addition, the nano-scale particle size is smaller, and if the mixture is required to be uniform, the required energy consumption is higher, so that the aim of saving the energy consumption in industrial production is not facilitated.
The application adopts the micron-sized raw materials for mixing and has the advantages that the grain diameter of the two micron-sized raw materials is moderate, and the interface effect between the tiny grains ensures that the two micron-sized raw materials can be mixed uniformly with lower energy consumption. Agglomeration among particles is not easy to occur in the mixing and subsequent crushing processes, and local high-temperature phenomenon caused by particle agglomeration is avoided. The two micron-sized raw materials are crushed into the nanometer-sized particle size after being uniformly mixed, so that the mixed raw materials can be crushed into a mixture with uniform particle size, a more uniform phase crystal structure can be obtained in the subsequent sintering process, the reaction activity of the product is improved, the generation of impurity phases caused by the non-uniform particle sizes of the two raw materials in sintering is avoided, and the crystallinity of the sintered product is improved.
In the above method, after the slurry is dried, the liquid phase in the slurry evaporates, leaving a solid phase. The solvent used to prepare the slurry is water. Because the two different types of mixed particles in the slurry have uniform particle sizes, the forces between the solid and liquid phases are relatively uniform and the liquid phase can be vaporized uniformly, leaving behind a fluffy solid, i.e., dry powder. The nano particles in the dry powder have uniform gaps, but not compact structures, so that the dry powder is in a loose structure as a whole, is not easy to agglomerate, and can avoid agglomeration in the sintering process, thereby avoiding the generation of local high-temperature areas, adverse chemical reactions and impurity phases in the sintering process to a certain extent.
Because the fluffy dry powder is formed in the last step, uniform gaps exist among the solid nano particles in the dry powder, and enough air exists in the gaps, so that sintering can be performed in a sufficient oxygen-containing atmosphere, and the sintering can be uniformly performed into a stable single phase, and the purer lanthanum titanium oxide compound is obtained. In addition, when the lanthanum titanium oxide compound is used as a precursor to prepare the lithium lanthanum titanium oxide compound with a perovskite structure, the reaction activity is increased because the purity of the lanthanum titanium oxide compound is higher, the lithium source can fully contact and fully react with the surrounding lanthanum titanium oxide compound, and no larger lithium source loss occurs in the reaction process.
In addition, the nano-scale raw materials are expensive, and if the nano-scale raw materials are directly selected, the cost burden is greatly increased, and the preparation method not only reduces the synthesis temperature, but also improves the purity of the product.
In a specific example, the grinding may be a sanding process, and specifically, the mixed materials may be placed in a sanding device to perform wet grinding, so as to grind the materials into slurry with a particle size of nanometer. It will be appreciated by those skilled in the art that any conventional grinding process for processing materials into nano-sized slurries may be used, for example, ball milling processes for performing the above-described processing functions may be used. The drying treatment can be carried out by selecting a drying device suitable for the material, for example, slurry can be spray-dried, and powdery material can be dried. In another embodiment, a sintering aid is also added to the raw materials during mixing to inhibit grain growth and facilitate promotion of sintering densification. The sintering aid is oxide. The sintering aid may be selected from any of alumina, calcium oxide, magnesium oxide, most preferably alumina.
And sintering the slurry to obtain the lanthanum titanium oxide compound. Lanthanum titanium oxide is used to prepare perovskite type solid electrolyte. In some embodiments, sintering may employ process parameters of 900-1200 ℃ sintering temperature, and/or 10-48 hours sintering time. In a specific example, the sintering temperature may be any of 900 ℃, 950 ℃, 1000 ℃, 1150 ℃, or 1200 ℃, or any of the temperatures in the range of 900 ℃ to 1200 ℃ may be employed. The sintering time can be any time of 10h, 20h, 30h, 35h, 40h, 45h or 48h, and any other time in the range of 10h-48h can be adopted. The control of the sintering process parameters is beneficial to forming single-phase lanthanum titanium oxide products and improving the crystallinity of the lanthanum titanium oxide products, thereby being beneficial to improving the crystallinity of the solid electrolyte.
In other embodiments of the present application, the lanthanum source compound may be selected from, but is not limited to, any of lanthanum oxide, lanthanum nitrate, lanthanum hydroxide, and most preferably lanthanum oxide. The titanium source compound may be selected from, but is not limited to, one of titanium dioxide, lithium titanate, barium titanate compound, most preferably titanium dioxide. In other embodiments, the molar ratio of lanthanum source compound to titanium source compound is (1-5): 2-4.
In other embodiments of the application, the lanthanum titanyl compound is prepared by mixing by wet mixing, the mass percent concentration of solids in the mixture is 12% -13%, and/or drying is atomization drying. In the method, wet mixing is carried out, raw materials are prepared into slurry, and the dispersibility of the nanoscale solid particles is improved, so that the lanthanum source compound and the titanium source compound are fully mixed, and the impurity phase generated by the product is avoided.
In other embodiments of the present application, a lithium battery is provided that is composed of a solid electrolyte and an electrode, wherein the solid electrolyte is prepared by the method for preparing a solid electrolyte provided in the above embodiments. Solid state electrolytes are the core components of lithium batteries and are key factors affecting the performance of lithium batteries. According to the embodiment, through improvement of the preparation process of the solid electrolyte, the crystallinity of the lithium lanthanum titanium oxide compound product is improved, so that the electrochemical performance of the lithium lanthanum titanium oxide compound is improved, the conductivity of the solid electrolyte is further improved, and meanwhile, the energy consumption and the cost are reduced, so that the conductivity of a lithium battery is improved, and the preparation cost of the lithium battery is reduced.
The technical effects of the present application will be further elucidated with reference to the specific examples.
Example 1
The embodiment provides a preparation method of lanthanum titanium oxide compound, which comprises the following steps:
16.214g of lanthanum oxide (La O) and 16.14g of titanium dioxide were taken as raw materials. 0.4g of sintering aid alumina is added into the raw material, and oxygen element is provided by lanthanum oxide and titanium dioxide. Wherein the mol ratio of lanthanum oxide to titanium dioxide is 1:4.
Step one, lanthanum oxide, titanium dioxide and aluminum oxide are mixed through mixing equipment to obtain a mixture, and pretreatment is not needed.
Preparing the mixture into water-based slurry with the solid content of 12%, and pouring the water-based slurry into a sand mill for sand milling, wherein the sand milling treatment adopts the following technological parameters that the diameter of zirconium beads is 0.2mm, the rotating speed is 1200 r/min, and the sand milling time is 3h.
And thirdly, carrying out spray drying on the ground slurry to obtain fluffy dry powder.
And fourthly, placing the fluffy dry powder into a muffle furnace for sintering at the temperature of 1000 ℃ for 10 hours, cooling the muffle furnace to obtain lanthanum titanium oxide compound which is white powder and has the particle size of 5 mu m.
The lanthanum titanium oxide compound prepared in this example was subjected to X-ray powder diffraction test, and the test result is shown in FIG. 1. As can be seen from fig. 1, there are main characteristic diffraction peaks at 2θ angles of 32 °,40 ° and 46 °. Minor peaks at 27 °, 30 °, 58 °, 68 ° and 77 °.
Example 2
The embodiment provides a preparation method of lanthanum titanium oxide compound, which comprises the following steps:
16.214g of lanthanum nitrate (La (NO)) and 5.992g of titanium dioxide (TiO) were taken as starting materials. The oxygen element is provided by titanium dioxide. Wherein, the mol ratio of lanthanum nitrate and titanium dioxide is mixed according to the proportion of 2:3.
Step one, mixing the lanthanum nitrate and the titanium dioxide through mixing equipment to obtain a mixture without pretreatment.
And secondly, preparing the mixture into water-based slurry with the solid content of 11%, pouring the water-based slurry into a sand mill for sand milling, wherein the sand milling treatment adopts the following technological parameters that the diameter of zirconium beads is 0.2mm, the rotating speed is 1200 revolutions per minute, and the sand milling time is 1h.
And thirdly, carrying out spray drying on the ground slurry to obtain fluffy dry powder.
And fourthly, placing the fluffy dry powder into a muffle furnace for sintering at 900 ℃ for 15 hours, cooling the muffle furnace to obtain lanthanum titanium oxide compound which is white powder with the particle size of 7 mu m.
The lanthanum titanium oxide compound prepared in this example was subjected to X-ray powder diffraction test, and the test result is shown in FIG. 1.
Example 3
The embodiment provides a preparation method of lanthanum titanium oxide compound, which comprises the following steps:
16.214g of lanthanum oxide (La O) and 2.56g of titanium dioxide (TiO) were taken as starting materials. The oxygen element is provided by titanium dioxide. Wherein, the mol ratio of lanthanum oxide to titanium dioxide is mixed according to the proportion of 3:2.
Step one, mixing the lanthanum oxide and the titanium dioxide through mixing equipment to obtain a mixture without pretreatment.
And secondly, preparing the mixture into water-based slurry with the solid content of 11%, pouring the water-based slurry into a sand mill for sand milling, wherein the sand milling treatment adopts the following technological parameters that the diameter of zirconium beads is 0.8mm, the rotating speed is 1200 revolutions per minute, and the sand milling time is 2 hours.
And thirdly, carrying out spray drying on the ground slurry to obtain fluffy dry powder.
And fourthly, placing the fluffy dry powder into a muffle furnace for sintering at the temperature of 1200 ℃ for 20 hours, cooling the muffle furnace to obtain lanthanum titanium oxide compound which is white powder and has the particle size of 5 mu m.
The lanthanum titanium oxide compound prepared in this example was subjected to X-ray powder diffraction test, and the test result is shown in FIG. 1.
Example 4
The present embodiment provides a method for preparing a solid electrolyte, which includes the steps of:
Step one, weighing lanthanum titanium oxide compound according to the proportion of the mole ratio of lithium, lanthanum and titanium of the lithium lanthanum titanium oxide compound being 7:11:20, and weighing micron-sized lithium carbonate according to the proportion of 5% excess lithium carbonate.
And step two, uniformly mixing the weighed materials, and sintering at 900 ℃ for 10 hours to obtain a target product, namely the lithium lanthanum titanium oxide compound, namely the solid electrolyte.
The lithium lanthanum titanium oxide compound prepared in this example was subjected to X-ray powder diffraction detection, and the detection result is shown in fig. 2. Comparing the diffraction pattern of FIG. 2 with the XRD standard card JCPDS No.87-0935 shown in FIG. 3, it can be seen that the crystal form of the lithium lanthanum titanium oxide compound represented in FIG. 2 accords with the standard card JCPDS No.87-0935. In addition, compared with the standard peak shown in FIG. 3, no impurity peak is generated in FIG. 2, which shows that no impurity is generated in the product lithium lanthanum titanium oxide compound, and furthermore, as can be seen from FIG. 2, the diffraction peak is sharp, and the crystallinity of the lithium lanthanum titanium oxide compound obtained in the embodiment is high according to the area ratio of the sharp peak to the broad scattered peak.
The conductivity of the lithium lanthanum titanium oxide compound prepared in this example was measured and found to be 2.13X 10 -3 S/cm.
In conclusion, the lithium lanthanum titanium oxide compound prepared by the embodiment has higher crystallinity and high purity, so that the electrochemical performance of the lithium lanthanum titanium oxide compound is improved, and the conductivity of the solid electrolyte is improved.
Example 5
The present embodiment provides a method for preparing a solid electrolyte, which includes the steps of:
Step one, weighing lanthanum titanium oxide compound according to the proportion of the mole ratio of lithium, lanthanum and titanium of the lithium lanthanum titanium oxide compound being 7:11:20, and weighing micron-sized lithium carbonate according to the proportion of 10 percent excess lithium carbonate.
And step two, uniformly mixing the weighed materials, and sintering at 1000 ℃ for 10 hours to obtain the target product lithium lanthanum titanium oxide compound, namely the solid electrolyte.
The lithium lanthanum titanium oxide compound prepared in this example was subjected to X-ray powder diffraction detection, and the detection result is shown in fig. 2.
The conductivity of the lithium lanthanum titanium oxide compound prepared in this example was measured and found to be 1.78X10 -3 S/cm.
Example 6
The present embodiment provides a method for preparing a solid electrolyte, which includes the steps of:
Step one, weighing lanthanum titanium oxide compound according to the proportion of the mole ratio of lithium, lanthanum and titanium of the lithium lanthanum titanium oxide compound being 7:11:20, and weighing micron-sized lithium carbonate according to the proportion of the excess of 7.5% of lithium carbonate.
And step two, uniformly mixing the weighed materials, and sintering for 10 hours at 950 ℃ to obtain the target product lithium lanthanum titanium oxide compound, namely the solid electrolyte.
The lithium lanthanum titanium oxide compound prepared in this example was subjected to X-ray powder diffraction detection, and the detection result is shown in fig. 2.
The conductivity of the lithium lanthanum titanium oxide compound prepared in this example was measured and found to be 1.211 X10 -3 S/cm.
Of course, the above-described embodiments should not be construed as limiting the application.
While the application has been described in detail and with reference to specific examples thereof, the principles and embodiments of the application are described herein, and the above examples are provided to assist in understanding the method and core concepts of the application, and further, to those skilled in the art, in light of the teachings of the application, the application should not be construed as limited in scope to the specific embodiments and applications described herein.
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| CN114197048A (en) * | 2021-12-08 | 2022-03-18 | 电子科技大学长三角研究院(湖州) | Single crystal film with two-dimensional electron gas and preparation method thereof |
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