CN115307434B - Alumina crucible and preparation method and use thereof - Google Patents
Alumina crucible and preparation method and use thereof Download PDFInfo
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- CN115307434B CN115307434B CN202210993235.XA CN202210993235A CN115307434B CN 115307434 B CN115307434 B CN 115307434B CN 202210993235 A CN202210993235 A CN 202210993235A CN 115307434 B CN115307434 B CN 115307434B
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 title claims abstract description 81
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000000843 powder Substances 0.000 claims abstract description 75
- 238000005245 sintering Methods 0.000 claims abstract description 71
- 239000007784 solid electrolyte Substances 0.000 claims abstract description 45
- 238000000034 method Methods 0.000 claims abstract description 37
- 239000000919 ceramic Substances 0.000 claims abstract description 34
- YQNQTEBHHUSESQ-UHFFFAOYSA-N lithium aluminate Chemical compound [Li+].[O-][Al]=O YQNQTEBHHUSESQ-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910021525 ceramic electrolyte Inorganic materials 0.000 claims abstract description 3
- 239000002001 electrolyte material Substances 0.000 claims abstract description 3
- 239000010410 layer Substances 0.000 claims description 33
- 238000010438 heat treatment Methods 0.000 claims description 29
- 238000001816 cooling Methods 0.000 claims description 14
- 239000002245 particle Substances 0.000 claims description 14
- 230000000630 rising effect Effects 0.000 claims description 14
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 13
- 229910052744 lithium Inorganic materials 0.000 claims description 13
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 12
- 238000010146 3D printing Methods 0.000 claims description 11
- 238000005498 polishing Methods 0.000 claims description 9
- 229910010093 LiAlO Inorganic materials 0.000 claims description 8
- 238000004321 preservation Methods 0.000 claims description 8
- 229910010199 LiAl Inorganic materials 0.000 claims description 7
- 238000000280 densification Methods 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 239000002994 raw material Substances 0.000 claims description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 6
- 239000002344 surface layer Substances 0.000 claims description 6
- 238000007873 sieving Methods 0.000 claims description 4
- 238000003837 high-temperature calcination Methods 0.000 claims description 3
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims description 3
- KTUFCUMIWABKDW-UHFFFAOYSA-N oxo(oxolanthaniooxy)lanthanum Chemical compound O=[La]O[La]=O KTUFCUMIWABKDW-UHFFFAOYSA-N 0.000 claims description 3
- 229920000642 polymer Polymers 0.000 claims description 3
- 238000000498 ball milling Methods 0.000 claims description 2
- 238000001354 calcination Methods 0.000 claims description 2
- 229910018068 Li 2 O Inorganic materials 0.000 description 18
- 229910003249 Na3Zr2Si2PO12 Inorganic materials 0.000 description 15
- 238000004519 manufacturing process Methods 0.000 description 8
- 239000002002 slurry Substances 0.000 description 8
- 238000007639 printing Methods 0.000 description 7
- 150000002500 ions Chemical class 0.000 description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- 229910010293 ceramic material Inorganic materials 0.000 description 5
- 239000003792 electrolyte Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 4
- 244000137852 Petrea volubilis Species 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000011049 filling Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- -1 sodium zirconium silicon phosphorus oxide Chemical compound 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- 239000005279 LLTO - Lithium Lanthanum Titanium Oxide Substances 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 239000002228 NASICON Substances 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- RJEIKIOYHOOKDL-UHFFFAOYSA-N [Li].[La] Chemical compound [Li].[La] RJEIKIOYHOOKDL-UHFFFAOYSA-N 0.000 description 2
- CVJYOKLQNGVTIS-UHFFFAOYSA-K aluminum;lithium;titanium(4+);phosphate Chemical compound [Li+].[Al+3].[Ti+4].[O-]P([O-])([O-])=O CVJYOKLQNGVTIS-UHFFFAOYSA-K 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 229910052593 corundum Inorganic materials 0.000 description 2
- 239000010431 corundum Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000001493 electron microscopy Methods 0.000 description 2
- 229910000664 lithium aluminum titanium phosphates (LATP) Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 239000011241 protective layer Substances 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000009770 conventional sintering Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- PBCFLUZVCVVTBY-UHFFFAOYSA-N tantalum pentoxide Inorganic materials O=[Ta](=O)O[Ta](=O)=O PBCFLUZVCVVTBY-UHFFFAOYSA-N 0.000 description 1
Classifications
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F27—FURNACES; KILNS; OVENS; RETORTS
- F27B—FURNACES, KILNS, OVENS OR RETORTS IN GENERAL; OPEN SINTERING OR LIKE APPARATUS
- F27B14/00—Crucible or pot furnaces
- F27B14/08—Details specially adapted for crucible or pot furnaces
- F27B14/10—Crucibles
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/10—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on aluminium oxide
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F27—FURNACES; KILNS; OVENS; RETORTS
- F27B—FURNACES, KILNS, OVENS OR RETORTS IN GENERAL; OPEN SINTERING OR LIKE APPARATUS
- F27B14/00—Crucible or pot furnaces
- F27B14/08—Details specially adapted for crucible or pot furnaces
- F27B14/10—Crucibles
- F27B14/12—Covers therefor
-
- 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
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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
- H01M6/00—Primary cells; Manufacture thereof
- H01M6/22—Immobilising of electrolyte
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/60—Aspects relating to the preparation, properties or mechanical treatment of green bodies or pre-forms
- C04B2235/602—Making the green bodies or pre-forms by moulding
- C04B2235/6026—Computer aided shaping, e.g. rapid prototyping
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
- C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
- C04B2235/6562—Heating rate
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- C—CHEMISTRY; METALLURGY
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- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
- C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
- C04B2235/6567—Treatment time
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F27—FURNACES; KILNS; OVENS; RETORTS
- F27B—FURNACES, KILNS, OVENS OR RETORTS IN GENERAL; OPEN SINTERING OR LIKE APPARATUS
- F27B14/00—Crucible or pot furnaces
- F27B14/08—Details specially adapted for crucible or pot furnaces
- F27B14/10—Crucibles
- F27B2014/102—Form of the crucibles
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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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- Condensed Matter Physics & Semiconductors (AREA)
- Physics & Mathematics (AREA)
- Compositions Of Oxide Ceramics (AREA)
- Conductive Materials (AREA)
Abstract
The invention provides an alumina crucible, which comprises a crucible body, wherein the crucible body comprises a pot body and a cover body, the pot body and the cover body are made of alumina, at least the inner surfaces of the pot body and the cover body contain lithium aluminum oxide layers, the alumina crucible can realize sintering of LLZO ceramic electrolyte materials without mother powder and achieve conductivity similar to that of the traditional method, the invention also provides a preparation method of the alumina crucible, the method can prepare alumina slave crucibles with customized sizes, and the alumina crucible can be applied to preparation of solid electrolyte ceramic sheets.
Description
Technical Field
The invention relates to an alumina crucible, and in particular relates to a preparation method and application thereof.
Background
The Lithium Lanthanum Zirconium Oxide (LLZO) solid electrolyte is widely researched by virtue of the advantages of high lithium ion conductivity, wide electrochemical stability window and the like. LLZO solid electrolytes are typically prepared by sintering at temperatures above 1100 ℃ for long periods of time, and researchers often use the same composition of "mother powder" to cover the LLZO to compensate for lithium loss in the electrolyte sheet due to the significant loss of lithium element during this process. However, after the mother powder is used, a great amount of lithium is lost, and the mother powder cannot be reused, which leads to the increase of the production cost of the LLZO solid electrolyte. The Wen Zhao silver team researches the influence of different materials and crucibles with different sizes on the sintering effect of LLZO, explains the defect caused by the fact that the lithium atmosphere in the sintering environment is absorbed by the crucible in the sintering process of the LLZO solid electrolyte due to the reaction of Al 2O3 and Li 2 O, causes the reduction of the ion conductivity and the density of the solid electrolyte, and in addition, the excessive crucible volume also dilutes the concentration of the lithium atmosphere in the environment, and finally proposes that the crucible made of materials which do not react with Li 2 O such as MgO or platinum can realize good sintering effect without mother powder.
However, the platinum crucible is high in price, and the MgO crucible is higher in cost, difficult in production process and higher in energy consumption compared with the traditional corundum crucible.
Disclosure of Invention
In view of the above-mentioned drawbacks of the prior art, an object of the present invention is to provide an alumina crucible, a preparation method and use thereof, for solving the problem of lithium loss when sintering LLZO solid electrolyte in the corundum crucible in the prior art, and the problem of high production cost caused by using other crucibles.
In order to achieve the above and other related objects, the invention provides an alumina crucible, comprising a crucible body, wherein the crucible body comprises a pot body and a cover body, the pot body and the cover body are made of alumina, and at least the inner surfaces of the pot body and the cover body are covered with a lithium aluminum oxide layer.
The crucible body is preferably cylindrical, the crucible body is composed of a crucible bottom plate and a crucible side wall, the crucible side wall is arranged on the periphery of the crucible bottom plate in a surrounding mode to form a pot body accommodating cavity, optionally, a step for placing the cover body is formed on the inner side face of the crucible side wall, and optionally, the top of the cover body is flush with the top of the crucible side wall in a covering state.
Preferably, the lithium aluminum oxide layer comprises a surface layer LiAlO 2 layer and an inner layer LiAl 5O8 layer.
Preferably, the average particle size of the lithium aluminum oxide layer is 3-10 μm.
Preferably, the pan body and the cover body are obtained through 3D printing.
The invention also provides a preparation method of the alumina crucible, which comprises the following steps:
S1, preparing a crucible by taking alumina as a raw material;
s2, performing heat treatment on the crucible obtained in the step S1 to obtain the alumina crucible.
Preferably, in step S1, the surface morphology of the crucible is loose and porous, and the particle size of Al 2O3 particles of the crucible is below 5 μm.
Preferably, in step S1, the crucible is printed in 3D, and is obtained through a degumming and densification process.
Preferably, in step S2, the heat treatment comprises any one of the following methods:
a. Suspending the crucible in the step S1 above Li 2 O powder, and sintering in a high-temperature sintering furnace;
b. the LLZO powder was placed inside the crucible of step S1 and sintered in a high temperature sintering furnace.
The invention also provides an application of the alumina crucible in the preparation of the solid electrolyte ceramic wafer.
The invention also provides a preparation method of the LLZO solid electrolyte ceramic plate, which comprises the following steps:
1) Preparing a LLZO green body from the LLZO powder;
2) And (3) placing the LLZO green body obtained in the step (1) into the alumina crucible, placing into a high-temperature sintering furnace for sintering, cooling along with the furnace, taking out, and polishing to obtain the LLZO solid electrolyte ceramic sheet.
Preferably, the LLZO green body in the step 1) is prepared by mixing Al 2O3 powder with LLZO powder, sieving, and tabletting in a tabletting mold to obtain the LLZO green body;
preferably, in the step 2), the temperature of the high-temperature sintering furnace is 1200-1300 ℃, the heating rate is 2-10 DEG Cmin -1, and the sintering heat preservation time is 20 min-2 h.
As described above, the alumina crucible of the invention, and the preparation method and use thereof, have the following beneficial effects:
1) The alumina crucible provided by the invention can be used for realizing sintering of LLZO ceramic electrolyte materials without mother powder, and the solid electrolyte prepared by the alumina crucible without mother powder sintering can achieve the performance similar to that of the solid electrolyte prepared by the traditional mother powder coverage sintering method.
2) The alumina crucible provided by the invention can be repeatedly utilized, and lithium loss is avoided in the process of sintering the LLZO solid electrolyte, so that the production cost of the LLZO solid electrolyte ceramic material is effectively reduced, and the alumina crucible can be applied to sintering preparation of other ceramic materials with volatile elements.
3) The invention also prepares the custom-sized alumina crucible by 3D printing technology.
Drawings
FIG. 1 shows a schematic diagram I a. A schematic diagram and b. A digital photograph of an alumina crucible of the present invention.
FIG. 2 shows a schematic diagram II of an alumina crucible of the present invention. The crucible comprises a pot body 1, a cover body 2, a crucible bottom plate 11, a crucible side wall 12, a protrusion 111, a first inner side surface 121, a second inner side surface 122 and a second inner side surface.
FIG. 3 shows the microscopic morphology of the alumina crucible prior to heat treatment, a. Surface microscopic morphology, b. Cross-sectional microscopic morphology.
FIG. 4 shows XRD patterns of an alumina crucible after heat treatment, a. The crucible was suspended above Li 2 O powder, incubated at 1250℃for 40min, b. The crucible was suspended above Li 2 O powder, incubated at 1250℃for 2h.
FIG. 5 shows the microscopic morphology of the alumina crucible after heat treatment, a. The microscopic morphology of the crucible surface was incubated for 40min at 1250℃with Li 2 O powder, b. The microscopic morphology of the crucible surface was incubated for 2h at 1250℃with Li 2 O powder, C. The microscopic morphology of the crucible section was incubated for 40min at 1250℃with Li 2 O powder, d. The microscopic morphology of the crucible section was incubated for 2h at 1250℃with Li 2 O powder.
FIG. 6 shows XRD spectra of the surfaces of alumina crucibles subjected to heat preservation for 2 hours at 1250℃with Li 2 O powder, after polishing off 10, 20 and 70 μm, respectively.
FIG. 7 shows the room temperature ionic conductivity and relative density of LLZO sintered without the mother powder of the alumina crucible of the present invention, a. LLZO heat-treated crucible, b. Li 2 O heat-treated crucible.
Detailed Description
Other advantages and effects of the present invention will become apparent to those skilled in the art from the following disclosure, which describes the embodiments of the present invention with reference to specific examples. The invention may be practiced or carried out in other embodiments that depart from the specific details, and the details of the present description may be modified or varied from the spirit and scope of the present invention.
Please refer to fig. 1-7. It should be noted that, the illustrations provided in the present embodiment merely illustrate the basic concept of the present invention by way of illustration, and only the components related to the present invention are shown in the drawings and are not drawn according to the number, shape and size of the components in actual implementation, and the form, number and proportion of the components in actual implementation may be arbitrarily changed, and the layout of the components may be more complex.
The invention provides an alumina crucible which comprises a crucible body, wherein the crucible body comprises a pot body 1 and a cover body 2, the pot body 1 and the cover body 2 are made of alumina, and at least the inner surfaces of the pot body 1 and the cover body 2 are covered with a lithium aluminum oxide layer.
The alumina crucible is made of alumina, and at least the inner surfaces of the pot body 1 and the cover body 2 are covered with a lithium aluminum oxide layer, so that the alumina crucible is not only suitable for preparing ceramic materials with volatile elements by sintering without mother powder at high temperature, but also can ensure the repeated use stability of the crucible.
In the alumina crucible, a crucible body is in a cylindrical shape, the crucible body 1 consists of a crucible bottom plate 11 and a crucible side wall 12, the crucible side wall 12 is arranged on the periphery of the crucible bottom plate 11 in a surrounding manner to form a pot body accommodating cavity, optionally, a step for placing a cover body is formed on the inner side surface of the crucible side wall 12, and optionally, the top of the cover body 2 is flush with the top of the crucible side wall 12 in a covering state.
The crucible side wall 12 is formed by steps for placing a cover body on two inner side surfaces with different diameters, the steps comprise a first inner side surface 121 and a second inner side surface 122, the first inner side surface 121 is integrally connected with the crucible bottom plate 11, the diameter of the first inner side surface 121 is smaller than that of the second inner side surface 122, and the diameter of the cover body 2 is larger than that of the first inner side surface 121 and smaller than that of the second inner side surface 122.
A plurality of cylindrical protrusions 111 are uniformly provided on the inner side surface of the crucible bottom plate 11. As shown in fig. 1b, the 4 small cylindrical protrusions 111 are provided, so that the ceramic plate can be heated more uniformly when the ceramic plate is subsequently applied to sintering the electrolyte ceramic plate, and the possibility that the ceramic plate and the bottom of the crucible are bonded together is reduced.
In the alumina crucible, the lithium aluminum oxide layer comprises a surface layer LiAlO 2 layer and an inner layer LiAl 5O8 layer. The average particle diameter of the lithium aluminum oxide layer is 3-10 mu m. And 3D printing the pot body and the cover body.
The second aspect of the present invention provides a method for preparing an alumina crucible, comprising the steps of:
S1, preparing a crucible by taking alumina as a raw material;
s2, performing heat treatment on the crucible obtained in the step S1 to obtain the alumina crucible.
In the step S1, the surface appearance of the crucible is loose and porous, and the particle size of Al 2O3 particles of the crucible is less than 5 mu m. In a preferred embodiment of the present invention, the particle size of Al 2O3 particles in the crucible is 1 μm or less. The porous crucible is convenient for heat treatment to obtain the alumina crucible with better performance.
In the step S1, the crucible is printed in 3D mode and is obtained through degumming and densification processes. The Al 2O3 ceramic slurry was printed out of the crucible by a 3D printer. The 3D printing process comprises the specific process of importing predesigned crucible three-dimensional model data into a 3D printer, wherein the model design needs to adapt to the size and the number of electrolyte sheets, and a compact sintering space is ensured to maintain the concentration of lithium atmosphere in the sintering process. And placing the Al 2O3 ceramic slurry on a printing platform, operating a 3D printer (the laser wavelength is 355 nm) to sequentially solidify the ceramic slurry layer by layer, and printing out the crucible. The curing depth of the paste was set to about 400 μm by adjusting the light intensity so that the thickness of the printed layer was set to 100 μm (about 1/3-1/4 of the curing depth) for securing the bonding force between layers and printing efficiency. And taking out the crucible paper after the model is printed, wiping the crucible paper clean, and flushing out the slurry remained on the surface by using ethanol. The 3D printer is manufactured by using a Yi Tai Lai laser technology company CeraBuilder to 100 and Al 2O3 ceramic slurry purchased from the Yi Tai Lai laser technology company.
And (3) degumming, namely placing the crucible prepared in the step (S1) in a box furnace, respectively preserving heat at 250-350 ℃ and 510-610 ℃ for more than or equal to 1h, and enabling the temperature rising rate to be less than or equal to 5 DEG Cmin -1 to decompose and separate the solidified polymer in the crucible to obtain the degummed crucible. In the preferred embodiment of the invention, the crucible is placed in a box furnace and incubated at 300 ℃ and 560 ℃ for 2 hours, respectively, at a rate of 2 DEG Cmin -1.
The densification is that the degummed crucible is cooled and transferred into a high-temperature sintering furnace, heated to 1200-1400 ℃, the temperature rising rate is less than or equal to 5 DEG Cmin -1, kept for 1-4 hours, cooled along with the furnace and taken out to obtain the densification crucible. In the preferred embodiment of the invention, the degummed crucible is cooled and transferred to a high temperature sintering furnace, heated to 1300 ℃, and the temperature rising rate is 2 DEG Cmin -1 and kept for 2 hours.
In the method for producing an alumina crucible of the present invention, in step S2, the heat treatment is any one of the following methods:
a. Suspending the crucible in the step S1 above Li 2 O powder, and sintering in a high-temperature sintering furnace;
b. the LLZO powder was placed inside the crucible of step S1 and sintered in a high temperature sintering furnace.
The crucible prepared in the step S1 is subjected to heat treatment to form a compact protective layer on the surface layer of the crucible, wherein the protective layer is a lithium aluminum oxide layer.
In the method a, the sintering conditions are all 1100-1300 ℃ and are kept for 40 min-5 h, and the temperature rising rate is 1-10 DEG Cmin -1. In a preferred embodiment of the invention, the sintering condition is kept at 1250 ℃ for 2 hours, and the temperature rising rate is 5 DEG Cmin -1. Suspending the crucible at the position about 1-2cm above Li 2 O powder, using a high-temperature sintering furnace to keep the temperature at 1250 ℃ for 2 hours, and taking out the crucible after cooling along with the furnace at the temperature rising rate of 5 DEG Cmin -1 to obtain the alumina crucible. When suspended, the crucible mouth is downward and is suspended above Li 2 O powder in a back-off state.
In the method b, the sintering conditions are all 1100-1300 ℃ and are kept for 40 min-5 h, and the temperature rising rate is 1-10 DEG Cmin -1. In a preferred embodiment of the invention, the sintering condition is kept at 1250 ℃ for 2 hours, and the temperature rising rate is 5 DEG Cmin -1. Filling LLZO powder into a crucible, preserving heat for 2 hours at 1250 ℃ by using a high-temperature sintering furnace, cooling with the furnace, and taking out to obtain the alumina crucible, wherein the temperature rising rate is 5 DEG Cmin -1.
In method b, the LLZO powder includes a doped element-containing LLZO powder. For example LLZTO powder (Ta doped LLZO).
The preparation method of the alumina crucible comprises the steps of carrying out heat treatment on the prepared crucible with loose and porous surface morphology, so that a compact lithium aluminum oxide layer is formed on the surface layer of the crucible, and the repeated use stability of the crucible is ensured.
The third aspect of the invention provides an application of the alumina crucible in the preparation of a solid electrolyte ceramic wafer.
The fourth aspect of the present invention provides a method for preparing a LLZO solid electrolyte ceramic wafer, comprising the steps of:
1) Preparing a LLZO green body from the LLZO powder;
2) And (3) placing the LLZO green body obtained in the step (1) into the alumina crucible, placing into a high-temperature sintering furnace for sintering, cooling along with the furnace, taking out, and polishing to obtain the LLZO solid electrolyte ceramic sheet.
In the preparation method of the LLZO solid electrolyte ceramic plate, the preparation of the LLZO green body in the step 1) comprises the steps of mixing Al 2O3 powder with the LLZO powder, sieving, adding the mixture into a tabletting mold, and tabletting to obtain the LLZO green body. Adding 2wt% of Al 2O3 powder serving as a sintering aid into LLZO powder, mixing, sieving with a 400-mesh screen, weighing a certain amount of mixed powder, pouring into a tabletting mold, applying a certain pressure, maintaining the pressure for two minutes, and taking out to obtain a LLZO green body.
LLZO powder was prepared by mixing raw material LiOH H 2O、La2O3、ZrO2 in elemental stoichiometric ratio (additional 20% excess LiOH H 2 O was added to compensate for lithium volatilization during high temperature calcination) in isopropanol, ball milling at 600rpm for 6H, and calcination at 950℃for 6H. If Ta-doped LLZO powder is prepared, ta 2O5 with stoichiometric ratio is doped into the raw materials. Other element doped LLZO powders can be prepared in a similar manner.
The temperature of the high-temperature sintering furnace in the step 2) is 1200-1300 ℃, the heating rate is 2-10 DEG Cmin -1, and the sintering heat preservation time is 20 min-2 h. In the preferred embodiment of the invention, the temperature of the high-temperature sintering furnace is 1250 ℃, the temperature rising rate is 5 DEG Cmin -1, and the heat preservation time is 40min.
The sintering in the step 2) is mother powder-free sintering.
The specific process comprises the steps of putting the LLZO green compact prepared in the step 1) into an alumina crucible without covering mother powder, using a high-temperature sintering furnace to keep the temperature at 1250 ℃ for 40min, cooling the green compact with the furnace, taking out the green compact, and sequentially polishing the green compact by using 800-mesh abrasive paper, 1500-mesh abrasive paper and 2000-mesh abrasive paper until a smooth LLZO surface is obtained.
The alumina crucible of the invention is also suitable for ceramic materials with volatilization of elements such as lithium or sodium in the sintering process, such as perovskite electrolyte Lanthanum Lithium Titanate (LLTO), NASICON solid electrolyte titanium aluminum lithium phosphate (LATP), sodium zirconium silicon phosphorus oxide (NZSP) and the like, so that the sintering without mother powder is realized, and the production cost is reduced.
Example 1
3D printing of the crucible:
Al 2O3 ceramic slurry was prepared, and a designed three-dimensional model of a crucible (taking a prepared crucible suitable for accommodating 1 piece of LLZO green compact pressed by a 0.5 inch mold as an example) was introduced into a 3D printer, wherein the crucible body was a cylinder, the height of the crucible body was 3.5mm, the thickness of the crucible bottom plate 11 was 1mm, the outer diameter of the crucible side wall 12 was 24mm, the diameter of the first side inner side 121 was 16mm, the height of the cylindrical cavity formed by the first side 121 and the crucible bottom plate 11 was 1.5mm, the diameter of the second inner side 122 was 20mm, the diameter of the lid 2 was 19mm, and the thickness of the lid 2 was 1mm. And placing the Al 2O3 ceramic slurry on a printing platform, operating a 3D printer (the laser wavelength is 355 nm) to sequentially solidify the ceramic slurry layer by layer, setting the thickness of a printing layer to be 100 mu m, and printing out the crucible. The remaining printing paste on the crucible surface was cleaned by wiping with paper and assisted with an air gun. And then the crucible is put into a small box furnace for degumming, so that the solidified polymer is decomposed and separated in the air, the degumming process is to keep the temperature at 300 ℃ and 560 ℃ for 2 hours respectively, and the heating rate is 2 DEG Cmin -1. Cooling along with the furnace, taking out, transferring into a high-temperature sintering furnace, heating to 1300 ℃ to densify the crucible, keeping the temperature for 2 hours at a heating rate of 2 DEG Cmin -1, cooling along with the furnace, and taking out. The crucible shown in FIG. 1b was obtained.
The crucible was subjected to a morphology observation by an electron microscope (JSM-7800F, japan electronics Co., ltd.) to obtain a surface and cross-sectional morphology map shown in FIG. 2.
As can be seen from fig. 3, the average particle size of Al 2O3 particles is less than 1 μm, and the more porous structure contributes to the formation of a dense lithium aluminum oxide layer upon subsequent heat treatment of Li 2 O.
Example 2
The crucible was heat treated in the same manner as in example 1 using data 3D printing:
Suspending the printed crucible at 1-2cm above about 0.2g of Li 2 O powder, preserving heat for 40min at 1250 ℃ by using a high-temperature sintering furnace, cooling along with the furnace, and taking out to obtain the alumina crucible at a temperature rising rate of 5 DEG Cmin -1.
XRD testing (Bruker D2 Powder X-ray Diffractometer, germany) was performed on the alumina crucible to obtain the phase analysis results shown in FIG. 4 a.
The alumina crucible was observed for morphology by electron microscopy (JSM-7800F, japanese electric Co., ltd.) to obtain the surface and cross-sectional morphology shown in FIGS. 5a and c.
Example 3
The crucible was heat treated in the same manner as in example 1 using data 3D printing:
Suspending the printed crucible at 1-2cm above about 0.2g of Li 2 O powder, preserving heat for 2 hours at 1250 ℃ by using a high-temperature sintering furnace, cooling along with the furnace, and taking out to obtain the alumina crucible at a temperature rising rate of 5 DEG Cmin -1.
XRD testing (Bruker D2 Powder X-ray Diffractometer, germany) was performed on the alumina crucible to obtain the phase analysis results shown in FIG. 4 b.
The alumina crucible was observed for morphology by electron microscopy (JSM-7800F, japanese electric Co., ltd.) to obtain the surface and cross-sectional morphology shown in FIGS. 5b and d.
As can be seen from examples 2-3 and FIG. 4, with increasing heat treatment time, the LiAlO 2 signal increased, the signals of LiAl 5O8 and Al 2O3 decreased, and the signal of Al 2O3 of the alumina crucible treated for 2 hours was very small, which means that alumina within tens of microns below the crucible surface had been almost completely converted to lithium aluminum oxide.
As shown in examples 2-3 and FIG. 5, the surface morphology of the alumina crucible is more similar to that of 5a and 5b with the increase of the treatment time, and the alumina crucible is a dense LiAlO 2 layer with the particle size distribution of about 3-10 μm. However, from the cross-sectional views (5 c and 5 d) it can be seen that the thickness of the dense layer increases from about 5 μm for 40min of treatment to about 15 μm for 2h, consistent with the XRD results of FIG. 4.
Example 4
An alumina crucible was prepared by performing the same method as in example 1 and data 3D printing crucible, and performing heat treatment in the same manner as in example 3. The alumina crucible surface was polished to 10, 20 and 70 μm, respectively, and then subjected to XRD test, and the results are shown in FIG. 6.
From example 4 and fig. 6, it is found that the signal (22.3 °, 33.4 °, 34.7 °) representing LiAlO 2 is greatly reduced by comparing the initial surface with the result of polishing by 10 μm, and the signal (32 °, 37.7 °, 45.9 °) of LiAl 5O8 is slightly enhanced relatively under the result that the shielding of the surface layer is polished off. When the total of 20 μm is polished off, the signal of LiAlO 2 is completely lost, the signal of LiAl 5O8 is still strongest, and the signal of Al 2O3 starts to appear. Finally, when the total 70 μm was polished off, the signal of LiAl 5O8 completely disappeared, leaving only the signal of Al 2O3. This data further demonstrates that the upper dense layer in the cross-sectional view of fig. 5 (5 c and 5 d) is LiAlO 2.
Example 5
The crucible was 3D printed with the same procedure as in example 1 and heat-treated by filling LLZO powder into the crucible, maintaining the temperature at 1250 ℃ for 2 hours using a high temperature sintering furnace at a heating rate of 5°cmin -1, cooling with the furnace, and taking out to obtain an alumina crucible.
Ta doped LLZO solid electrolyte green body is prepared by adopting a traditional solid phase sintering method and has a chemical formula of Li 6.4La3Zr1.4Ta0.6O12 (LLZTO). The raw material LiOH H 2O、La2O3、ZrO2、Ta2O5 was mixed in elemental stoichiometric ratio (additional 20% excess LiOH H 2 O was added to compensate for lithium volatilization during high temperature calcination) in isopropanol, ball milled at 600rpm for 6H and calcined at 950 ℃ for 6H to give LLZTO powder. Subsequently, 2wt% of Al 2O3 powder was added to LLZO powder as a sintering aid, and after mixing, it was sieved with a 400-mesh sieve, about 0.4g of the powder was weighed and poured into a tabletting mold having a diameter of 0.5 inch, and the pressure was maintained for 2 minutes under a pressure of 4MPa (about 300MPa actually applied to the tablet) of the press, and a LLZTO solid electrolyte green compact having a diameter of 1.27cm was obtained after taking out.
The LLZTO green compact is put into an alumina crucible prepared in the embodiment without covering the mother powder, and is insulated for 40min at 1250 ℃ by a high-temperature sintering furnace, the heating rate is 5 DEG Cmin -1, and the alumina crucible is taken out after being cooled along with the furnace. Sequentially polishing with 800, 1500 and 2000 mesh sand paper until LLZTO solid electrolyte ceramic sheets with smooth surfaces are obtained.
And (3) carrying out metal spraying on two sides of the LLZTO solid electrolyte ceramic plate, and detecting the ion conductivity and the density of the ceramic plate. The results are shown in FIG. 7 a.
Example 6
An alumina crucible was prepared by performing the same method as in example 1 and data 3D printing crucible, and performing heat treatment in the same manner as in example 3.
A Ta-doped LLZO green body was prepared by the same method as in example 5, to prepare LLZTO solid electrolyte green body.
The prepared LLZTO solid electrolyte green compact is put into an alumina crucible prepared in the embodiment without covering the mother powder, and is preserved for 40min at 1250 ℃ by a high-temperature sintering furnace, the heating rate is 5 DEG Cmin -1, and the alumina crucible is taken out after being cooled along with the furnace. Sequentially polishing with 800, 1500 and 2000 mesh sand paper until LLZTO solid electrolyte ceramic sheets with smooth surfaces are obtained.
And (3) carrying out metal spraying on two sides of the LLZTO solid electrolyte ceramic plate, and detecting the ion conductivity and the density of the ceramic plate. The results are shown in FIG. 7 b.
As can be seen from examples 5 to 6 and FIG. 7, the alumina crucible prepared by the different heat treatment methods in example 5 and example 6 was similar to LLZTO solid electrolyte ceramic sheet obtained by sintering LLZTO solid electrolyte, and the ion conductivity at room temperature was 2.8X10- -4S cm-1 (average value) and the relative density was 91.5% (average value). The LLZTO solid electrolyte prepared by the method is ideal as the basic performance parameter of the solid electrolyte applied to the all-solid lithium battery.
From the above data, it is understood that the method of heat treating the crucible by filling the LLZO powder into the crucible in example 5 is similar to the method of heat treating the crucible by suspending the crucible above the Li 2 O powder in example 6. Meanwhile, the LLZTO solid electrolyte ceramic sheet sintered by the aluminum oxide crucible without the mother powder has the performance similar to that of the conventional method, and compared with the conventional platinum crucible without the mother powder, the aluminum oxide crucible has lower cost.
Example 7
The crucible was 3D printed using the same procedure as in example 1 and heat treated (using commercial sodium zirconium silicon phosphorus oxygen NZSP (Na 3Zr2Si2PO12) powder) by suspending the crucible 1-2cm above about 0.2g NZSP powder, holding the temperature at 1250 ℃ for 2 hours using a high temperature sintering furnace at a rate of 5°cmin -1, cooling the crucible with the furnace, and removing the crucible to obtain NZSP treated alumina crucible.
NZSP a green body was obtained by pressing NZSP powder, weighing about 0.4g of NZSP powder, pouring the powder into a tabletting mold with a diameter of 0.5 inch, maintaining the pressure of 4MPa (about 300MPa actually applied to the tablet) on the press surface for 2 minutes, and taking out the powder to obtain NZSP solid electrolyte green body with a diameter of 1.27cm.
The NZSP solid electrolyte green compact was put into the NZSP treated alumina crucible prepared in this example, without covering the mother powder, and was heat-preserved at 1200 ℃ for 6 hours using a high temperature sintering furnace at a heating rate of 5 ° Cmin -1, and taken out after cooling with the furnace. Sequentially polishing with 800, 1500 and 2000 mesh sand paper until NZSP solid electrolyte ceramic sheets with smooth surfaces are obtained.
And (3) performing metal spraying on two sides of the NZSP solid electrolyte ceramic plate, and performing density and ion conductivity tests. The measured properties of ion conductivity and density of NZSP solid electrolyte ceramic sheets of example 7 were similar to those obtained when sintering without the mother powder using conventional sintering methods.
In summary, the alumina crucible of the invention enables the cheap Al 2O3 crucible to be applied to the method for sintering solid electrolyte without mother powder, can obtain LLZO solid electrolyte with performance similar to that of the traditional method for covering and sintering mother powder, reduces the production cost of the LLZO solid electrolyte, and is also suitable for sintering other ceramic materials, such as perovskite electrolyte Lanthanum Lithium Titanate (LLTO), NASICON solid electrolyte titanium aluminum lithium phosphate (LATP), sodium zirconium silicon phosphorus oxide (NZSP) and the like, which volatilize lithium or sodium and other elements in the sintering process, thereby realizing the sintering without mother powder and reducing the production cost. Therefore, the invention effectively overcomes various defects in the prior art and has high industrial utilization value.
The above embodiments are merely illustrative of the principles of the present invention and its effectiveness, and are not intended to limit the invention. Modifications and variations may be made to the above-described embodiments by those skilled in the art without departing from the spirit and scope of the invention. Accordingly, it is intended that all equivalent modifications and variations of the invention be covered by the claims, which are within the ordinary skill of the art, be within the spirit and scope of the present disclosure.
Claims (6)
1. The alumina crucible is characterized by comprising a crucible body, wherein the crucible body comprises a pot body and a cover body, the pot body and the cover body are made of alumina, at least the inner surfaces of the pot body and the cover body are covered with a lithium aluminum oxide layer, the lithium aluminum oxide layer comprises a surface layer LiAlO 2 layer and an inner layer LiAl 5O8 layer, the crucible body is cylindrical, the pot body consists of a crucible bottom plate and a crucible side wall, the crucible side wall is arranged around the periphery of the crucible bottom plate to form a pot body accommodating cavity, the inner side surface of the crucible side wall is provided with a step for placing the cover body, in a covering state, the top of the cover body is level with the top of the crucible side wall, a plurality of cylindrical protrusions are uniformly arranged on the inner side surface of the crucible bottom plate, and the pot body and the cover body are obtained through 3D printing;
The preparation method of the alumina crucible comprises the following steps:
S1, preparing a crucible by taking alumina as a raw material;
s2, performing heat treatment on the crucible prepared in the step S1 to prepare an alumina crucible;
In the step S1, the surface morphology of the crucible is loose and porous, and the average grain diameter of Al 2O3 particles is less than 5 mu m;
In the step S1, 3D printing is adopted for the crucible, and degumming and densification are carried out, wherein the degumming is that the crucible prepared in the step S1 is placed in a box-type furnace, heat preservation is carried out at 250-350 ℃ and 510-610 ℃ respectively, the heat preservation time is more than or equal to 1h, the heating rate is less than or equal to 5 ℃ min -1, the solidified polymer in the crucible is decomposed and separated to obtain a degummed crucible, the densification is that the degummed crucible is placed in a high-temperature sintering furnace, the crucible is heated to 1200-1400 ℃, the heating rate is less than or equal to 5 ℃ min -1, the heat preservation is carried out for 1-4 hours, and the crucible is taken out after cooling along with the furnace, so that the densification crucible is obtained;
In the step S2, the heat treatment comprises the following steps of placing LLZO powder inside the crucible in the step S1, and sintering in a high-temperature sintering furnace, wherein the prepared crucible with loose and porous surface morphology is subjected to heat treatment to form a compact lithium aluminum oxide layer on the surface of the crucible, so that the repeated use stability of the crucible is ensured;
Preparing LLZO powder, namely mixing a raw material LiOH H 2O、La2O3、ZrO2 into isopropanol according to an element stoichiometric ratio, adding 20% excess LiOH H 2 O for compensating volatilization of lithium in a high-temperature calcination process, ball-milling for 6H at a speed of 600 rpm, and calcining for 6H at 950 ℃ to obtain LLZO powder;
the alumina crucible can realize non-mother powder sintering of LLZO ceramic electrolyte materials.
2. The alumina crucible of claim 1, wherein the average particle size of the particles of the lithium aluminum oxide layer is 3-10 μm.
3. The alumina crucible of claim 1, including any one of the following features:
b1. The sintering conditions are all 1100-1300 ℃ and the temperature is kept for 40 min-5 h, and the temperature rising rate is 1-10 ℃ min -1;
b2. The LLZO powder includes a doped element-containing LLZO powder.
4. Use of the alumina crucible of any one of claims 1 to 3 in the preparation of a solid electrolyte ceramic wafer.
5. The preparation method of the LLZO solid electrolyte ceramic chip is characterized by comprising the following steps of:
1) Preparing a LLZO green body from the LLZO powder;
2) Placing the LLZO green body obtained in the step 1) into the alumina crucible according to any one of claims 1-3, sintering in a high-temperature sintering furnace, cooling along with the furnace, taking out, and polishing to obtain the LLZO solid electrolyte ceramic sheet.
6. The method for preparing LLZO solid electrolyte ceramic plate according to claim 5, wherein the preparation of the LLZO green body in step 1) comprises mixing Al 2O3 powder with LLZO powder, sieving, and tabletting in a tabletting mold to obtain LLZO green body;
And/or, in the step 2), the temperature of the high-temperature sintering furnace is 1200-1300 ℃, the temperature rising rate is 2-10 ℃ min -1, and the sintering heat preservation time is 20 min-2 h.
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