CN114162862A - Lithium lanthanum zirconium oxygen-based powder body with hollow structure and preparation method thereof - Google Patents
Lithium lanthanum zirconium oxygen-based powder body with hollow structure and preparation method thereof Download PDFInfo
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- 239000000843 powder Substances 0.000 title claims abstract description 63
- XRNHBMJMFUBOID-UHFFFAOYSA-N [O].[Zr].[La].[Li] Chemical compound [O].[Zr].[La].[Li] XRNHBMJMFUBOID-UHFFFAOYSA-N 0.000 title claims abstract description 56
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000002243 precursor Substances 0.000 claims abstract description 24
- 238000005469 granulation Methods 0.000 claims abstract description 20
- 230000003179 granulation Effects 0.000 claims abstract description 20
- 239000007921 spray Substances 0.000 claims abstract description 20
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 17
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000001354 calcination Methods 0.000 claims abstract description 14
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 14
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 14
- 150000001875 compounds Chemical class 0.000 claims abstract description 13
- 238000002156 mixing Methods 0.000 claims abstract description 6
- 239000000203 mixture Substances 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 13
- 239000002245 particle Substances 0.000 claims description 11
- 239000002994 raw material Substances 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 5
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims description 4
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 3
- 229910052758 niobium Inorganic materials 0.000 claims description 3
- 239000010955 niobium Substances 0.000 claims description 3
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 3
- 229910052715 tantalum Inorganic materials 0.000 claims description 3
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 3
- IVORCBKUUYGUOL-UHFFFAOYSA-N 1-ethynyl-2,4-dimethoxybenzene Chemical compound COC1=CC=C(C#C)C(OC)=C1 IVORCBKUUYGUOL-UHFFFAOYSA-N 0.000 claims description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 2
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052796 boron Inorganic materials 0.000 claims description 2
- 229910052733 gallium Inorganic materials 0.000 claims description 2
- YXEUGTSPQFTXTR-UHFFFAOYSA-K lanthanum(3+);trihydroxide Chemical compound [OH-].[OH-].[OH-].[La+3] YXEUGTSPQFTXTR-UHFFFAOYSA-K 0.000 claims description 2
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 claims description 2
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 2
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 2
- 238000010298 pulverizing process Methods 0.000 claims description 2
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 2
- 239000003792 electrolyte Substances 0.000 abstract description 12
- NRJJZXGPUXHHTC-UHFFFAOYSA-N [Li+].[O--].[O--].[O--].[O--].[Zr+4].[La+3] Chemical compound [Li+].[O--].[O--].[O--].[O--].[Zr+4].[La+3] NRJJZXGPUXHHTC-UHFFFAOYSA-N 0.000 abstract description 10
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 5
- 229910001416 lithium ion Inorganic materials 0.000 description 5
- 239000000463 material Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 3
- 239000005486 organic electrolyte Substances 0.000 description 3
- 239000007784 solid electrolyte Substances 0.000 description 3
- 238000009987 spinning Methods 0.000 description 3
- 229910002984 Li7La3Zr2O12 Inorganic materials 0.000 description 2
- 238000000498 ball milling Methods 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 229910003002 lithium salt Inorganic materials 0.000 description 2
- 159000000002 lithium salts Chemical class 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002121 nanofiber Substances 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 238000010587 phase diagram Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910021525 ceramic electrolyte Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000002223 garnet Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 239000011244 liquid electrolyte Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G25/00—Compounds of zirconium
- C01G25/006—Compounds containing, besides zirconium, two or more other elements, with the exception of oxygen or hydrogen
-
- 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
- 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
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Inorganic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- General Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention relates to the technical field of lithium lanthanum zirconium oxide based oxides, in particular to a lithium lanthanum zirconium oxide based powder body with a hollow structure and a preparation method thereof. The preparation method of the lithium lanthanum zirconium oxygen-based powder body comprises the following steps: mixing and crushing compounds containing a lithium source, a lanthanum source, a zirconium source and doping elements to obtain lithium lanthanum zirconium oxygen-based precursor powder; carrying out spray granulation and calcination on the lithium lanthanum zirconium oxygen-based precursor powder to obtain lithium lanthanum zirconium oxygen-based powder; wherein the conditions of the spray granulation are as follows: the inlet temperature is 160-. According to the invention, the lithium lanthanum zirconium oxygen-based powder with a hollow structure is successfully prepared by optimizing the preparation process, and the lithium lanthanum zirconium oxygen-based powder is used for preparing the solid-state battery electrolyte, so that the density of an electrolyte layer can be reduced, and the obtained battery has lighter mass per unit volume, thereby indirectly improving the specific capacity of the battery.
Description
Technical Field
The invention relates to the technical field of lithium lanthanum zirconium oxide based oxides, in particular to a lithium lanthanum zirconium oxide based powder body with a hollow structure and a preparation method thereof.
Background
Lithium ion batteries are widely used in portable electronic products such as mobile phones and notebook computers, and energy storage devices such as new energy electric vehicles due to their advantages of high energy density, long service life, environmental friendliness, and the like, and have attracted much attention. Among several large elements of lithium ion batteries, the electrolyte, which is an indispensable constituent of the lithium ion battery, largely determines the performance of the lithium ion battery.
At present, the electrolyte used in commercial lithium ion batteries is mainly liquid organic electrolyte, and although the electrolyte has high ionic conductivity, the electrolyte has the defects of easy leakage, easy corrosion, easy decomposition at high temperature and the like, and the potential safety hazards caused by the electrolyte, such as spontaneous combustion, explosion and the like, are not inconstant; meanwhile, in the process of charging and discharging, lithium dendrite and the like are easily formed on the surface of an electrode material by the liquid organic electrolyte, so that the large-scale application of the liquid organic electrolyte in the chemical field is further limited. Therefore, the solid electrolyte is adopted to replace the traditional liquid electrolyte, and the method has very important significance for developing the all-solid-state lithium battery with high safety, high energy density and wide temperature use range.
In the solid electrolyte material reported at present, the lithium lanthanum zirconium oxygen conductivity with cubic garnet structure can reach 10-3The magnitude of S/cm is close to the practical requirement of conductivity, and the chemical formula of the material can be written as Li7La3Zr2O12(abbreviated as LLZO). In the preparation of inorganic ceramic electrolytes and the currently studied more rigid and flexible composite electrolytes, LLZO is widely studied due to its good thermal stability and electrochemical stability, and is a material with great application prospects.
CN108417889A discloses a method for preparing lithium lanthanum zirconium oxide based oxide powder, which adopts soluble lithium acetate as lithium source, water as solvent medium and ZrO with high specific surface area2As a coating template of lithium salt, LLZO powder was prepared by simple mechanical ball milling and dry calcination. CN111732432A discloses a spherical lithium lanthanum zirconium oxygen powder material, which comprises Li7La3Zr2O12The ceramic comprises a matrix ceramic and a compound containing doping elements such as at least one of aluminum, yttrium, niobium, molybdenum, antimony, tantalum and tungsten, wherein the particle size of the spherical lithium lanthanum zirconium oxide powder is 20-80 mu m. CN107162049A discloses a method for preparing lithium lanthanum zirconium oxide based oxide nano material, which comprises: (1) preparing a spinning solution containing a precursor; (2) spinning the spinning solution to obtain precursor fiber; (3) carrying out high-temperature calcination treatment on the precursor fiber so as to obtain the lithium lanthanum zirconium oxide based oxide nanofiber; (4) and crushing the lithium lanthanum zirconium oxide based oxide nano-fiber to obtain the lithium lanthanum zirconium oxide based oxide nano-material. However, since the LLZO itself has a high density, the battery quality is high when the solid electrolyte layer with the same thickness is prepared, and if the density of the object can be reduced under the same volume, the energy density of the solid battery can be further improved, and the hollow-structure LLZO powder provides a solution. The LLZO disclosed in the above-mentioned patent document has not reported an effective means for realizing the hollow structure.
In view of this, the invention is particularly proposed.
Disclosure of Invention
The invention aims to provide a preparation method of a lithium lanthanum zirconium oxygen-based powder body, the lithium lanthanum zirconium oxygen-based powder body prepared by the method has a hollow structure, the lithium lanthanum zirconium oxygen-based powder body with the hollow structure is used for preparing a solid battery electrolyte, the density of an electrolyte layer can be reduced, the obtained battery has lighter mass under unit volume, and thus the specific capacity of the battery is indirectly improved; another object of the present invention is to provide a lithium lanthanum zirconium oxygen based powder body prepared by the above method.
Specifically, the invention provides the following technical scheme:
the invention provides a preparation method of a (hollow structure) lithium lanthanum zirconium oxygen-based powder body, which comprises the following steps:
mixing and crushing compounds containing a lithium source, a lanthanum source, a zirconium source and doping elements to obtain lithium lanthanum zirconium oxygen-based precursor powder;
carrying out spray granulation and calcination on the lithium lanthanum zirconium oxygen-based precursor powder to obtain lithium lanthanum zirconium oxygen-based powder;
wherein the conditions of the spray granulation are as follows: the inlet temperature is 160-; the calcination is carried out at 850-1000 ℃ for 1-10 h.
The invention discovers that after the lithium lanthanum zirconium oxygen-based precursor powder is obtained by adopting a blending mode, the pure-phase lithium lanthanum zirconium oxygen-based powder with a hollow structure is hopeful to be prepared by combining spray granulation and calcination processes.
The conditions of spray granulation are further controlled as above, the control of the shape of the precursor can be realized, and the problems of uneven proportioning and difficult uniform mixing treatment caused by the reaction of lithium salt and water in the air are avoided; further controlling the calcination to be carried out under the above conditions, so that the finally obtained powder can maintain the shape structure frame of the precursor to the maximum extent, and a hole structure is gradually formed inside the powder, thereby forming the shape characteristics of the hollow net nest structure; so as to prepare the pure-phase lithium lanthanum zirconium oxygen-based powder body with a hollow structure.
In order to further regulate and control the shape and appearance of the lithium lanthanum zirconium oxygen-based powder, the preparation method is optimized, and specifically comprises the following steps:
preferably, the compound comprising a lithium source, a lanthanum source, a zirconium source and a doping element is mixed according to Li: la: zr ═ 7: 3: 2 to obtain a mixture;
wherein the proportion of the doping elements is 0.5-3.0 wt% of the total weight of the raw materials.
In the above technical solutions, the raw material refers to a compound including a lithium source, a lanthanum source, a zirconium source, and a doping element.
Further, the mixture is pulverized to a particle size of 50 μm or less.
The invention also discovers that the raw materials are mixed and then crushed to the particle size of below 50 mu m, so that the uniformity of the particles can be kept, and the uniform mixing among the raw materials is facilitated.
Preferably, the pulverization is carried out in a solvent; preferably, the solvent is water.
The crushing means includes, but is not limited to, grinding, ball milling, sand milling, and the like, according to common knowledge.
Preferably, the lithium source is one or more selected from lithium carbonate, lithium hydroxide, lithium nitrate and lithium acetate.
Preferably, the lanthanum source is selected from one or more of lanthanum oxide, lanthanum hydroxide and lanthanum nitrate.
Preferably, the zirconium source is selected from one or two of zirconium oxide and zirconium hydroxide.
Preferably, the doping element is one or more selected from aluminum, gallium, boron, niobium and tantalum.
As a preferred technical scheme, the preparation method comprises the following steps:
(1) a compound comprising a lithium source, a lanthanum source, a zirconium source and a doping element is reacted according to Li: la: zr ═ 7: 3: 2 into water to obtain a mixture;
wherein, the proportion of the doping elements is 0.5 to 3.0 weight percent of the total weight of the raw materials;
(2) crushing the mixture to obtain lithium lanthanum zirconium oxygen-based precursor powder with the particle size of below 50 mu m;
(3) performing spray granulation on the lithium lanthanum zirconium oxygen-based precursor powder, and then calcining for 1-10h at 850-;
wherein the conditions of the spray granulation are as follows: the inlet temperature is 160-.
Thus, the invention prepares the lithium lanthanum zirconium oxygen-based powder body with a hollow structure.
The invention also provides a lithium lanthanum zirconium oxygen-based powder body which is prepared by the preparation method.
Preferably, the lithium lanthanum zirconium oxygen-based powder body is of a hollow structure.
The invention has the beneficial effects that:
according to the invention, the lithium lanthanum zirconium oxygen-based powder with a hollow structure is successfully prepared by optimizing the preparation process, and the lithium lanthanum zirconium oxygen-based powder is used for preparing the solid-state battery electrolyte, so that the density of an electrolyte layer can be reduced, and the obtained battery has lighter mass per unit volume, thereby indirectly improving the specific capacity of the battery.
Drawings
FIG. 1 is a phase diagram of a lithium lanthanum zirconium oxygen based powder body of the present invention;
fig. 2 is an SEM image of the lithium lanthanum zirconium oxygen based powder of the present invention.
Detailed Description
The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention.
The examples do not show the specific techniques or conditions, according to the technical or conditions described in the literature in the field, or according to the product specifications. The reagents or instruments used are conventional products available from regular distributors, not indicated by the manufacturer.
Example 1
This example provides a lithium lanthanum zirconium oxygen-based powder, which is prepared by the following steps:
(1) a compound comprising a lithium source, a lanthanum source, a zirconium source and a doping element is reacted according to Li: la: zr ═ 7: 3: 2 into water to obtain a mixture;
wherein, the proportion of the doping elements accounts for 1.0 wt% of the total weight of the raw materials;
(2) crushing the mixture to a particle size of less than 20 microns to obtain lithium lanthanum zirconium oxygen-based precursor powder;
(3) performing spray granulation on the lithium lanthanum zirconium oxygen-based precursor powder, and calcining for 6 hours at 1000 ℃ to obtain lithium lanthanum zirconium oxygen-based powder;
wherein the conditions of the spray granulation are as follows: the inlet temperature is 190 ℃, the outlet temperature is 100 ℃, and the rotating speed is 12000 r/min.
The phase diagram of the lithium lanthanum zirconium oxygen-based powder body of the embodiment is shown in fig. 1, and the SEM diagram is shown in fig. 2.
Example 2
This example provides a lithium lanthanum zirconium oxygen-based powder, which is prepared by the following steps:
(1) a compound comprising a lithium source, a lanthanum source, a zirconium source and a doping element is reacted according to Li: la: zr ═ 7: 3: 2 into water to obtain a mixture;
wherein, the proportion of the doping elements accounts for 1.5 wt% of the total weight of the raw materials;
(2) crushing the mixture to a particle size of less than 50 mu m to obtain lithium lanthanum zirconium oxygen-based precursor powder;
(3) performing spray granulation on the lithium lanthanum zirconium oxygen-based precursor powder, and then calcining for 1h at 950 ℃ to obtain lithium lanthanum zirconium oxygen-based powder;
wherein the conditions of the spray granulation are as follows: the inlet temperature is 220 ℃, the outlet temperature is 90 ℃, and the rotating speed is 8000 r/min.
Example 3
This example provides a lithium lanthanum zirconium oxygen-based powder, which is prepared by the following steps:
(1) a compound comprising a lithium source, a lanthanum source, a zirconium source and a doping element is reacted according to Li: la: zr ═ 7: 3: 2 into water to obtain a mixture;
wherein, the proportion of the doping elements accounts for 3.0 wt% of the total weight of the raw materials;
(2) crushing the mixture to a particle size of less than 50 mu m to obtain lithium lanthanum zirconium oxygen-based precursor powder;
(3) performing spray granulation on the lithium lanthanum zirconium oxygen-based precursor powder, and calcining for 10 hours at 1000 ℃ to obtain lithium lanthanum zirconium oxygen-based powder;
wherein the conditions of the spray granulation are as follows: the inlet temperature is 160 ℃, the outlet temperature is 85 ℃, and the rotating speed is 15000 r/min.
Example 4
This example provides a lithium lanthanum zirconium oxygen-based powder, which is prepared by the following steps:
(1) a compound comprising a lithium source, a lanthanum source, a zirconium source and a doping element is reacted according to Li: la: zr ═ 7: 3: 2 into water to obtain a mixture;
wherein, the proportion of the doping elements accounts for 0.5 wt% of the total weight of the raw materials;
(2) crushing the mixture to obtain lithium lanthanum zirconium oxygen-based precursor powder with the particle size of less than 40 mu m;
(3) performing spray granulation on the lithium lanthanum zirconium oxygen-based precursor powder, and then calcining for 1h at 850 ℃ to obtain lithium lanthanum zirconium oxygen-based powder;
wherein the conditions of the spray granulation are as follows: the inlet temperature is 160 ℃, the outlet temperature is 90 ℃, and the rotating speed is 15000 r/min.
Although the invention has been described in detail hereinabove with respect to a general description and specific embodiments thereof, it will be apparent to those skilled in the art that modifications or improvements may be made thereto based on the invention. Accordingly, such modifications and improvements are intended to be within the scope of the invention as claimed.
Claims (10)
1. A preparation method of lithium lanthanum zirconium oxygen-based powder is characterized by comprising the following steps:
mixing and crushing compounds containing a lithium source, a lanthanum source, a zirconium source and doping elements to obtain lithium lanthanum zirconium oxygen-based precursor powder;
carrying out spray granulation and calcination on the lithium lanthanum zirconium oxygen-based precursor powder to obtain lithium lanthanum zirconium oxygen-based powder;
wherein the conditions of the spray granulation are as follows: the inlet temperature is 160-; the calcination is carried out at 850-1000 ℃ for 1-10 h.
2. The method according to claim 1, wherein the compound comprising a lithium source, a lanthanum source, a zirconium source and a doping element is mixed in a ratio of Li: la: zr ═ 7: 3: 2 to obtain a mixture;
wherein the proportion of the doping elements is 0.5-3.0 wt% of the total weight of the raw materials.
3. The production method according to claim 2, wherein the mixture is pulverized to a particle size of 50 μm or less.
4. The production method according to any one of claims 1 to 3, wherein the pulverization is carried out in a solvent; preferably, the solvent is water.
5. The method according to any one of claims 1 to 4, wherein the lithium source is selected from one or more of lithium carbonate, lithium hydroxide, lithium nitrate and lithium acetate.
6. The preparation method according to any one of claims 1 to 5, wherein the lanthanum source is selected from one or more of lanthanum oxide, lanthanum hydroxide and lanthanum nitrate.
7. A method according to any one of claims 1 to 6, wherein the zirconium source is selected from one or both of zirconium oxide and zirconium hydroxide.
8. The method according to any one of claims 1 to 7, wherein the doping element is selected from one or more of aluminum, gallium, boron, niobium and tantalum.
9. The method of claim 1, comprising the steps of:
(1) a compound comprising a lithium source, a lanthanum source, a zirconium source and a doping element is reacted according to Li: la: zr ═ 7: 3: 2 into water to obtain a mixture;
wherein, the proportion of the doping elements is 0.5 to 3.0 weight percent of the total weight of the raw materials;
(2) crushing the mixture to obtain lithium lanthanum zirconium oxygen-based precursor powder with the particle size of below 50 mu m;
(3) performing spray granulation on the lithium lanthanum zirconium oxygen-based precursor powder, and then calcining for 1-10h at 850-;
wherein the conditions of the spray granulation are as follows: the inlet temperature is 160-.
10. A lithium lanthanum zirconium oxygen based powder characterized in that it is prepared by the preparation method according to any one of claims 1 to 9;
preferably, the lithium lanthanum zirconium oxygen-based powder body is of a hollow structure.
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