CN115307434A - Alumina crucible and preparation method and application thereof - Google Patents
Alumina crucible and preparation method and application thereof Download PDFInfo
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- CN115307434A CN115307434A CN202210993235.XA CN202210993235A CN115307434A CN 115307434 A CN115307434 A CN 115307434A CN 202210993235 A CN202210993235 A CN 202210993235A CN 115307434 A CN115307434 A CN 115307434A
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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 70
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 238000005245 sintering Methods 0.000 claims abstract description 73
- 239000000843 powder Substances 0.000 claims abstract description 70
- 239000007784 solid electrolyte Substances 0.000 claims abstract description 48
- 238000000034 method Methods 0.000 claims abstract description 45
- 239000000919 ceramic Substances 0.000 claims abstract description 33
- YQNQTEBHHUSESQ-UHFFFAOYSA-N lithium aluminate Chemical compound [Li+].[O-][Al]=O YQNQTEBHHUSESQ-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000000463 material Substances 0.000 claims abstract description 5
- 238000010438 heat treatment Methods 0.000 claims description 37
- 239000010410 layer Substances 0.000 claims description 31
- 102000020897 Formins Human genes 0.000 claims description 27
- 108091022623 Formins Proteins 0.000 claims description 27
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 21
- 238000001816 cooling Methods 0.000 claims description 18
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 13
- 238000004519 manufacturing process Methods 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 12
- 239000002245 particle Substances 0.000 claims description 10
- 238000000227 grinding Methods 0.000 claims description 8
- 238000005498 polishing Methods 0.000 claims description 8
- 229910010093 LiAlO Inorganic materials 0.000 claims description 7
- 238000010146 3D printing Methods 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 6
- 238000000280 densification Methods 0.000 claims description 5
- 239000002344 surface layer Substances 0.000 claims description 5
- 229910010199 LiAl Inorganic materials 0.000 claims description 4
- 238000004321 preservation Methods 0.000 claims description 4
- 229920000642 polymer Polymers 0.000 claims description 3
- 238000007873 sieving Methods 0.000 claims description 3
- 229910021525 ceramic electrolyte Inorganic materials 0.000 abstract description 2
- 239000002001 electrolyte material Substances 0.000 abstract description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 12
- 229910052744 lithium Inorganic materials 0.000 description 12
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 8
- 239000002002 slurry Substances 0.000 description 8
- 238000007639 printing Methods 0.000 description 7
- 229910010293 ceramic material Inorganic materials 0.000 description 6
- 239000003792 electrolyte Substances 0.000 description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- 244000137852 Petrea volubilis Species 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 229910052593 corundum Inorganic materials 0.000 description 3
- 239000010431 corundum Substances 0.000 description 3
- 238000011049 filling Methods 0.000 description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 3
- 229910052737 gold Inorganic materials 0.000 description 3
- 239000010931 gold Substances 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- -1 sodium zirconium silicon phosphorus oxygen 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
- 229910021193 La 2 O 3 Inorganic materials 0.000 description 2
- 229910018068 Li 2 O Inorganic materials 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
- 229910052782 aluminium Inorganic materials 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
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000009770 conventional sintering Methods 0.000 description 2
- 238000001493 electron microscopy Methods 0.000 description 2
- 238000003837 high-temperature calcination Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910000664 lithium aluminum titanium phosphates (LATP) Inorganic materials 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 238000000634 powder X-ray diffraction Methods 0.000 description 2
- 239000011241 protective layer Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 241001643623 Enteles Species 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- RJEIKIOYHOOKDL-UHFFFAOYSA-N [Li].[La] Chemical compound [Li].[La] RJEIKIOYHOOKDL-UHFFFAOYSA-N 0.000 description 1
- XRNHBMJMFUBOID-UHFFFAOYSA-N [O].[Zr].[La].[Li] Chemical compound [O].[Zr].[La].[Li] XRNHBMJMFUBOID-UHFFFAOYSA-N 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 229910000659 lithium lanthanum titanates (LLT) Inorganic materials 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Images
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 peculiar to 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 peculiar to 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
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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
- C04B2235/60—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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- 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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- 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
-
- 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 peculiar to crucible or pot furnaces
- F27B14/10—Crucibles
- F27B2014/102—Form of the crucibles
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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 materials, and at least the inner surfaces of the pot body and the cover body contain a lithium-aluminum oxide layer; the alumina crucible can realize the sintering of the LLZO ceramic electrolyte material without mother powder and achieve the conductivity similar to that of the traditional method; the invention also provides a preparation method of the alumina crucible, which can prepare alumina crucible with customized size, and the alumina crucible of the invention can be applied to the preparation of solid electrolyte ceramic plates.
Description
Technical Field
The invention relates to an alumina crucible, a preparation method and application thereof.
Background
The Lithium Lanthanum Zirconium Oxygen (LLZO) solid electrolyte is an oxide solid electrolyte which is widely researched by virtue of the advantages of high lithium ion conductivity, wide electrochemical stability window and the like. The LLZO solid electrolytes are generally prepared by sintering at temperatures above 1100 ℃ for long periods of time, and since the loss of lithium element is severe during this process, researchers have generally covered the LLZO with a "mother powder" of the same composition to compensate for the loss of lithium in the electrolyte sheet. However, after the mother powder is used, lithium in the mother powder is greatly lost and cannot be reused, which causes the production cost of the LLZO solid electrolyte to be increased. Wen Zhao silver ball group studied the effect of different materials and different size crucibles on the LLZO sintering effect, explaining the Al-based sintering of corundum crucibles used in conventional sintering methods during the sintering of LLZO solid electrolytes 2 O 3 With Li 2 The reaction of O causes the lithium atmosphere in the sintering environment to be absorbed by the crucible to cause deficiency, the ion conductivity and the compactness of the solid electrolyte are reduced, in addition, the excessive crucible volume can also dilute the concentration of the lithium atmosphere in the environment, and finally, the adoption of MgO or platinum which can not react with Li is proposed 2 The crucible made of the material with O reaction can realize good sintering effect without mother powder.
However, the price of the platinum crucible is high, and compared with the traditional corundum crucible, the MgO crucible has higher cost, more difficult production process and higher energy consumption.
Disclosure of Invention
In view of the above-mentioned disadvantages of the prior art, the present invention aims to provide an alumina crucible, a method for preparing the same, and a use thereof, which are used to solve the problems of lithium loss when sintering a LLZO solid electrolyte using a corundum crucible in the prior art, and high production costs caused by using other crucibles.
In order to achieve the above and other related objects, the present 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 aluminum oxide materials, and at least the inner surfaces of the pot body and the cover body are covered with lithium aluminum oxide layers.
Preferably, the crucible body is cylindrical; the pot body consists of a crucible bottom plate and a crucible side wall, and the crucible side wall is arranged around the crucible bottom plate to form a pot body containing cavity; optionally, a step for placing the cover body is formed on the inner side surface of the side wall of the crucible; optionally, in a closed state, the top of the cover body is flush with the top of the side wall of the crucible.
Preferably, the lithium aluminum oxide layer includes a superficial layer of LiAlO 2 Layer and lining of LiAl 5 O 8 A layer.
Preferably, the average particle diameter of the lithium aluminum oxide layer is 3 to 10 μm.
Preferably, the pot body and the cover body are obtained by 3D printing.
The invention also provides a preparation method of the alumina crucible, which comprises the following steps:
s1, preparing a crucible by using aluminum oxide as a raw material;
s2, carrying out heat treatment on the crucible prepared in the step S1 to prepare the alumina crucible.
Preferably, in step S1, the crucible has a loose and porous surface, and the crucible has Al 2 O 3 The particle diameter is less than 5 μm.
Preferably, in step S1, the crucible is printed in 3D, and is obtained through degumming and densification processes.
Preferably, in step S2, the heat treatment includes any one of the following methods:
a. suspending the crucible of step S1 from Li 2 Sintering the powder above the O powder in a high-temperature sintering furnace;
b. the LLZO powder is 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 a solid electrolyte ceramic chip.
The invention also provides a preparation method of the LLZO solid electrolyte ceramic chip, which comprises the following steps:
1) Preparing a green LLZO from the LLZO powder;
2) Putting the LLZO green body obtained in the step 1) into the alumina crucible, sintering in a high-temperature sintering furnace, cooling along with the furnace, taking out, and grinding and polishing to obtain the LLZO solid electrolyte ceramic chip.
Preferably, the preparation of the green LLZO in step 1) is: mixing Al 2 O 3 Mixing the powder and the LLZO powder, sieving, adding into a tabletting mold, and tabletting to obtain a LLZO green body;
preferably, the temperature of the high-temperature sintering furnace in the step 2) is 1200-1300 ℃, and the heating rate is 2-10 ℃ for min -1 And the sintering heat preservation time is 20 min-2 h.
As described above, the alumina crucible of the present invention, the preparation method and the use thereof have the following beneficial effects:
1) The aluminum oxide crucible can realize the sintering of the LLZO ceramic electrolyte material without mother powder, and the solid electrolyte prepared by sintering the aluminum oxide crucible without the mother powder can achieve the performance similar to that of the solid electrolyte prepared by the traditional mother powder covering sintering method.
2) The alumina crucible can be repeatedly used, lithium loss can not be caused in the process of sintering the LLZO solid electrolyte, 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 alumina crucible with customized size by 3D printing technology.
Drawings
FIG. 1 shows a schematic view I of an alumina crucible of the present invention: a. a schematic diagram; b. digital photos.
FIG. 2 shows a schematic view II of an alumina crucible of the present invention. Wherein: 1. a pan body; 2. a cover body; 11. a crucible bottom plate; 12. a crucible side wall; 111. a protrusion; 121. a first inner side; 122. a second inner side surface.
FIG. 3 shows the micro-morphology of the alumina crucible before heat treatment: a. surface micro-topography; b. and (4) microscopic cross-sectional morphology.
Figure 4 shows the XRD spectrum of the alumina crucible after heat treatment: a. the crucible is suspended from Li 2 Keeping the temperature above the O powder at 1250 ℃ for 40min; b. the crucible is suspended from Li 2 And keeping the temperature above the O powder at 1250 ℃ for 2h.
FIG. 5 shows the microstructure of the alumina crucible after heat treatment: a. via Li 2 The micro-morphology of the surface of the crucible is that O powder is insulated for 40min at 1250 ℃; b. via Li 2 The micro-morphology of the surface of the crucible is that O powder is insulated for 2 hours at 1250 ℃; c. via Li 2 The microscopic appearance of the cross section of the crucible is that O powder is insulated at 1250 ℃ for 40min; d. via Li 2 And the microscopic appearance of the section of the crucible is formed by insulating the O powder at 1250 ℃ for 2h.
FIG. 6 shows a reaction product of Li 2 The XRD spectrogram of the O powder after being polished to 10 microns, 20 microns and 70 microns on the surface of an alumina crucible which is kept at 1250 ℃ for 2 hours.
FIG. 7 shows the room temperature ionic conductivity and relative density of the mother powder-free sintered LLZO of the alumina crucible of the present invention: a. a crucible heat treated with LLZO; b. via Li 2 O heat treated crucible.
Detailed Description
The embodiments of the present invention are described below with reference to specific embodiments, and other advantages and effects of the present invention will be easily understood by those skilled in the art from the disclosure of the present specification. The invention is capable of other and different embodiments and of being practiced or of being carried out in various ways, and its several details are capable of modification in various respects, all without departing from the spirit and scope of the present invention.
Please refer to fig. 1-7. It should be noted that the drawings provided in the present embodiment are only for illustrating the basic idea of the present invention, and the components related to the present invention are only shown in the drawings rather than drawn according to the number, shape and size of the components in actual implementation, and the type, quantity and proportion of the components in actual implementation may be changed freely, and the layout of the components may be more complicated.
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 aluminum oxide crucible is made of aluminum oxide, and at least one layer of lithium aluminum oxide layer covers the inner surfaces of the pot body 1 and the cover body 2, so that the aluminum oxide crucible is suitable for high-temperature mother powder-free sintering preparation of ceramic materials with volatile elements in the aluminum oxide crucible, and the stability of the crucible in repeated use can be ensured.
In the alumina crucible, the crucible body is cylindrical; the pot body 1 consists of a crucible bottom plate 11 and a crucible side wall 12, and the crucible side wall 12 is arranged around the crucible bottom plate 11 to form a pot body containing cavity; optionally, a step for placing the cover body is formed on the inner side surface of the side wall 12 of the crucible; optionally, in the closed position, the top of the lid 2 is flush with the top of the crucible side wall 12.
The crucible side wall 12 is formed with a step for placing a cover body by two inner side surfaces with different diameters, and includes 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, and the diameter of the first inner side surface 121 is smaller than that of the second inner side surface 122; the diameter of the lid body 2 is larger than the diameter of the first inner side surface 121 and smaller than or equal to the diameter of the second inner side surface 122.
A plurality of cylindrical protrusions 111 are uniformly arranged on the inner side surface of the crucible bottom plate 11. As shown in fig. 1b, 4 small cylindrical protrusions 111 are provided, so that the ceramic sheet can be heated more uniformly when being applied to sintering the electrolyte ceramic sheet later, and the possibility that the ceramic sheet is bonded with the bottom of the crucible is reduced.
In the alumina crucible, the lithium-aluminum oxide layer comprises LiAlO on the surface layer 2 Layer and lining of LiAl 5 O 8 A layer. The average particle diameter of the lithium aluminum oxide layer is 3-10 mu m. The pot body and the cover body are obtained through 3D printing.
The second aspect of the present invention provides a method for preparing an alumina crucible, comprising the steps of:
s1, preparing a crucible by using aluminum oxide as a raw material;
s2, carrying out heat treatment on the crucible prepared in the step S1 to prepare the alumina crucible.
Wherein, in the step S1, the surface appearance of the crucible is loose and porous, and the crucible is Al 2 O 3 The particle diameter is less than 5 μm. In a preferred embodiment of the invention, al of the crucible 2 O 3 The particle diameter is less than 1 μm. The crucible with loose porous structure is convenient for heat treatment to obtain alumina with better performanceA crucible.
In the step S1, the crucible is printed in 3D mode and is obtained through degumming and densification processes. Mixing Al 2 O 3 The ceramic slurry was printed out of the crucible by a 3D printer. The specific process of the 3D printing process is as follows: and (3) introducing pre-designed crucible three-dimensional model data into a 3D printer, wherein the model design needs to be adapted to the size and the number of electrolyte sheets, and a compact sintering space is ensured to maintain the concentration of the lithium atmosphere in the sintering process. Mixing Al 2 O 3 And (3) placing the ceramic slurry on a printing platform, operating a 3D printer (with the laser wavelength of 355 nm) to sequentially solidify the ceramic slurry layer by layer, and printing a crucible. The curing depth of the paste is about 400 μm by adjusting the light intensity so that a single laser scan, and the print layer thickness is set to 100 μm (about 1/3-1/4 curing depth) in order to secure the bonding force between layers and the printing efficiency. And taking out the crucible after printing according to the model, wiping the crucible with paper, and washing residual slurry on the surface with ethanol. Wherein, the 3D printer adopts the model to be: ceraBuilder 100, a trade name for the etaley laser technology; al (Al) 2 O 3 Ceramic slurries were purchased from entele laser technologies.
Degumming is carried out by placing the crucible prepared in the step S1 into a box type furnace, respectively preserving heat at 250-350 ℃ and 510-610 ℃, preserving heat for more than or equal to 1h, and raising temperature rate for less than or equal to 5 ℃ for min -1 And decomposing and separating the solidified polymer in the crucible to obtain the degumming crucible. In a preferred embodiment of the invention, the crucible is placed in a box furnace and is kept at 300 ℃ and 560 ℃ for 2h respectively, and the heating rate is 2 ℃ for min -1 。
Densification is realized by cooling the degummed crucible and transferring the degummed crucible into a high-temperature sintering furnace, heating to 1200-1400 ℃, and raising the temperature at a rate of less than or equal to 5 ℃ for min -1 Keeping the temperature for 1-4 h, cooling along with the furnace, and taking out to obtain the densified crucible. In a preferred embodiment of the invention, the degummed crucible is cooled and transferred to a high-temperature sintering furnace, heated to 1300 ℃ and heated at a rate of 2 ℃ for min -1 And keeping the temperature for 2 hours.
In the method for manufacturing an alumina crucible of the present invention, in step S2, the heat treatment is any one of the following methods:
a. suspending the crucible of step S1 from Li 2 O powder overSintering in a high-temperature sintering furnace;
b. the LLZO powder is placed inside the crucible of step S1 and sintered in a high temperature sintering furnace.
Wherein, 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, and the protective layer is a lithium aluminum oxide layer.
In the method a, the sintering conditions are all that the temperature is kept at 1100-1300 ℃ for 40 min-5 h, and the heating rate is 1-10 ℃ for min -1 . In the preferred embodiment of the invention, the sintering condition is 1250 ℃ for 2h, and the heating rate is 5 ℃ for min -1 . The specific process of the method a comprises the following steps: suspending the crucible in Li 2 Keeping the temperature of the O powder at a position 1-2cm above the O powder at 1250 deg.C for 2h in a high-temperature sintering furnace at a heating rate of 5 deg.C for min -1 And taking out the aluminum oxide crucible after cooling along with the furnace to obtain the aluminum oxide crucible. When the crucible is suspended, the crucible opening is downward and suspended in Li in a reversed buckling state 2 O above the powder.
In the method b, the sintering conditions are all that the temperature is kept at 1100-1300 ℃ for 40 min-5 h, and the heating rate is 1-10 ℃ for min -1 . In the preferred embodiment of the invention, the sintering condition is 1250 ℃ for 2h, and the heating rate is 5 ℃ for min -1 . The specific process of the method b is as follows: filling LLZO powder into crucible, maintaining at 1250 deg.C for 2 hr in high temperature sintering furnace, and heating at 5 deg.C for min -1 And taking out the aluminum oxide crucible after cooling along with the furnace to obtain the aluminum oxide crucible.
In the method b, the LLZO powder includes a doping element-containing LLZO powder. For example, LLZTO powder (Ta doped LLZO).
The preparation method of the alumina crucible comprises the following steps: the crucible with loose and porous surface appearance is subjected to heat treatment, so that a compact lithium-aluminum oxide layer is formed on the surface layer of the crucible, and the stability of the crucible in repeated use is ensured.
The third aspect of the invention provides an application of the alumina crucible in the preparation of a solid electrolyte ceramic chip.
The fourth aspect of the invention provides a preparation method of a LLZO solid electrolyte ceramic chip, which comprises the following steps:
1) Preparing a green LLZO from the LLZO powder;
2) Putting the LLZO green body obtained in the step 1) into the alumina crucible, sintering in a high-temperature sintering furnace, cooling along with the furnace, taking out, and grinding and polishing to obtain the LLZO solid electrolyte ceramic chip.
In the preparation method of the LLZO solid electrolyte ceramic chip, the preparation of the LLZO green body in the step 1) comprises the following steps: mixing Al 2 O 3 Mixing the powder with LLZO powder, sieving, adding into a tabletting mold, and tabletting to obtain LLZO green body. The specific process is as follows: adding 2wt% Al to the LLZO powder 2 O 3 And the powder is used as a sintering aid, the powder is sieved by a 400-mesh screen after mixing, a certain amount of mixed powder is weighed and poured into a tabletting mold, a certain pressure is applied, the pressure is maintained for two minutes under the pressure, and the LLZO green body is obtained after being taken out.
Preparation of LLZO powder: raw material LiOH. H 2 O、La 2 O 3 、ZrO 2 Mixing in stoichiometric ratio (addition of 20% excess LiOH. H) 2 O to compensate for volatilization of lithium during high temperature calcination) was ball-milled in isopropanol at 600rpm for 6 hours and calcined at 950 ℃ for 6 hours to obtain LLZO powder. If Ta-doped LLZO powder is prepared, ta is doped into the raw material in a stoichiometric ratio 2 O 5 And (4) finishing. In the same way, other element doped LLZO powder can also be prepared.
The temperature of the high-temperature sintering furnace in the step 2) is 1200-1300 ℃, and the heating rate is 2-10 ℃ for min -1 And the sintering heat preservation time is 20 min-2 h. In a preferred embodiment of the invention, the high-temperature sintering furnace has a temperature of 1250 ℃ and a heating rate of 5 ℃ for min -1 The heat preservation time is 40min.
The sintering in the step 2) is mother powder-free sintering.
The specific process is as follows: putting the LLZO green body prepared in the step 1) into an alumina crucible without covering mother powder, and preserving the heat for 40min at 1250 ℃ by using a high-temperature sintering furnace at the heating rate of 5 ℃ for min -1 And taking out after furnace cooling, and sequentially grinding and polishing by using 800, 1500 and 2000-mesh sand paper respectively until a smooth LLZO surface is obtained.
The alumina crucible is also suitable for perovskite electrolyte Lithium Lanthanum Titanate (LLTO), NASICON solid electrolyte lithium titanium aluminum phosphate (LATP), sodium zirconium silicon phosphorus oxygen (NZSP) and other ceramic materials with elements such as lithium or sodium volatilizing in the sintering process, realizes sintering without mother powder, and reduces the production cost.
Example 1
3D printing of the crucible:
preparing Al 2 O 3 Ceramic slurry, a three-dimensional model of the designed crucible (taking as an example a crucible prepared to accommodate 1 sheet of green LLZO pressed from a 0.5 inch die) was introduced in a 3D printer: the crucible body is the cylinder, and the crucible body is high 3.5mm, and 11 thick 1mm of crucible bottom plate, and the external diameter of crucible lateral wall 12 is 24mm, and the diameter of first side medial surface 121 is 16mm, and the cylindrical cavity height that first side 121 and crucible bottom plate 11 formed is 1.5mm, and the diameter of second medial surface 122 is 20mm, 2 diameters 19mm of lid, and 2 thicknesses of lid are 1mm. Mixing Al 2 O 3 The ceramic slurry was placed on a printing platform, a 3D printer (laser wavelength 355 nm) was operated to sequentially cure the ceramic slurry layer by layer, the thickness of the printing layer was set to 100 μm, and the crucible was printed out. The residual printing paste on the surface of the crucible was cleaned by wiping with paper and air gun assistance. Placing the crucible into a small box furnace for degumming to decompose and separate the solidified polymer in the crucible in the air, wherein the degumming process comprises respectively keeping the temperature at 300 ℃ and 560 ℃ for 2h, and the heating rate is 2 ℃ for min -1 . Cooling with the furnace, taking out, transferring to a high temperature sintering furnace, heating to 1300 deg.C to densify the crucible, and heating at a rate of 2 deg.C for min -1 Keeping the temperature for 2 hours, and taking out after cooling along with the furnace. A crucible as shown in figure 1b is obtained.
The crucible was subjected to morphology observation by an electron microscope (JSM-7800F, japan Electron Ltd.) to obtain a surface and cross-sectional morphology chart shown in FIG. 2.
As can be seen from FIG. 3, al 2 O 3 The average particle size of the particles is less than 1 mu m, and the loose structure is beneficial to the subsequent Li 2 And a compact lithium aluminum oxide layer is generated during the heat treatment of O.
Example 2
The crucible was 3D printed using the same method as in example 1 and data, and heat treated:
the printed crucible was suspended in about 0.2g of Li 2 1-2c above O powderKeeping the temperature of the m position at 1250 ℃ for 40min by using a high-temperature sintering furnace, and keeping the temperature rise rate at 5 ℃ for min -1 And taking out the aluminum oxide crucible after cooling along with the furnace to obtain the aluminum oxide crucible.
XRD testing (Bruker D2 Powder X-ray diffraction instrument, germany) was performed on the alumina crucible, resulting in phase analysis as shown in FIG. 4 a.
The alumina crucible was observed for morphology by electron microscopy (JSM-7800F, japan Electron Co., ltd.) to obtain surface and cross-sectional morphologies as shown in FIGS. 5a and c.
Example 3
The crucible was 3D printed using the same method as in example 1 and data, and heat treated:
the printed crucible was suspended in about 0.2g of Li 2 Keeping the temperature 1-2cm above the O powder at 1250 deg.C for 2h in a high temperature sintering furnace at a heating rate of 5 deg.C for min -1 And taking out the aluminum oxide crucible after cooling along with the furnace to obtain the aluminum oxide crucible.
XRD testing (Bruker D2 Powder X-ray diffraction, germany) was performed on the alumina crucible, resulting in phase analysis as shown in figure 4 b.
The alumina crucible was observed for morphology by electron microscopy (JSM-7800F, japan Electron Co., ltd.) to obtain surface and cross-sectional morphologies as shown in FIGS. 5b and d.
From examples 2 to 3 and FIG. 4, it can be seen that: liAlO with increasing heat treatment time 2 Signal enhancement, liAl 5 O 8 With Al 2 O 3 For 2h of Al in the alumina crucible 2 O 3 The signal of (a) is very small, which means that the alumina within tens of microns below the crucible surface has almost been completely converted to lithium aluminum oxide.
From examples 2 to 3 and FIG. 5, it can be seen that: along with the increase of the treatment time, the appearance of the surface of the alumina crucible is similar to that of the alumina crucible 5a and 5b, and the alumina crucible is dense LiAlO with the grain diameter distribution of about 3-10 mu m 2 And (3) a layer. However, from the cross-sectional views (5 c and 5 d) it can be seen that the thickness of the dense layer thickened from about 5 μm for 40min of treatment to about 15 μm for 2h, consistent with the XRD results of FIG. 4.
Example 4
The crucible was 3D-printed in the same manner as in example 1, and heat-treated in the same manner as in example 3 to obtain an alumina crucible. The surfaces of the alumina crucibles were polished to 10, 20 and 70 μm, respectively, and then XRD test was performed, and the results are shown in FIG. 6.
From example 4 and fig. 6, it can be seen that: the results of comparing the initial surface with those after polishing 10 μm were found to represent LiAlO 2 Is greatly reduced (22.3 deg., 33.4 deg., 34.7 deg.), and LiAl is removed because of the surface layer shading 5 O 8 Is slightly enhanced relative to (32 °, 37.7 °, 45.9 °). Further grinding off LiAlO at a total of 20 μm 2 The signal of (A) disappears completely, liAl 5 O 8 The signal of (1) is still strongest, al 2 O 3 The signal of (a) starts to appear. Finally, when a total of 70 μm is ground off, liAl 5 O 8 The signal of (A) disappears completely, leaving only Al 2 O 3 Of the signal of (1). This data further demonstrates that the upper dense layer is LiAlO in the cross-sectional views of FIG. 5 (5 c and 5 d) 2 。
Example 5
The crucibles were 3D printed using the same method as in example 1 and heat treated: filling LLZO powder into crucible, maintaining at 1250 deg.C for 2 hr in high temperature sintering furnace, and heating at 5 deg.C for min -1 And taking out the aluminum oxide crucible after cooling along with the furnace to obtain the aluminum oxide crucible.
Preparing a Ta-doped LLZO solid electrolyte green body: has a chemical formula of Li 6.4 La 3 Zr 1.4 Ta 0.6 O 12 (LLZTO), synthesized by conventional solid phase sintering method. Raw material LiOH. H 2 O、La 2 O 3 、ZrO 2 、Ta 2 O 5 Mixing in stoichiometric ratio (addition of 20% excess LiOH. H) 2 O to compensate for volatilization of lithium during high temperature calcination) was ball milled in isopropanol at 600rpm for 6h and calcined at 950 ℃ for 6h to obtain LLZTO powder. Subsequently 2wt% Al was added to the LLZO powder 2 O 3 The powder was used as a sintering aid, mixed and sieved through a 400 mesh sieve, and about 0.4g of the powder was weighed and poured into a tablet forming die having a diameter of 0.5 inch, and the pressure was maintained at a pressure of 4MPa (about 300MPa actually applied to the tablet) on the press surfaceTaking out the obtained product for 2min to obtain a LLZTO solid electrolyte green body with the diameter of 1.27cm.
The LLZTO green body was placed in the alumina crucible prepared in this example, without covering the mother powder, and the temperature was maintained at 1250 ℃ for 40min in a high temperature sintering furnace at a rate of 5 ℃ for 5 min -1 And taking out after cooling along with the furnace. Sequentially grinding and polishing by using 800, 1500 and 2000-mesh sand paper respectively until obtaining the LLZTO solid electrolyte ceramic chip with a smooth surface.
Spraying gold on the two sides of the LLZTO solid electrolyte ceramic sheet, and detecting the ionic conductivity and the density of the LLZTO solid electrolyte ceramic sheet. The results are shown in FIG. 7 a.
Example 6
The crucible was 3D-printed in the same manner as in example 1, and heat-treated in the same manner as in example 3 to obtain an alumina crucible.
Ta-doped LLZO green bodies were prepared in the same manner as in example 5 to obtain green LLZTO solid electrolyte bodies.
The obtained LLZTO solid electrolyte green body is put into the alumina crucible prepared in the embodiment, without covering mother powder, and is heat preserved for 40min at 1250 ℃ by using a high temperature sintering furnace, and the heating rate is 5 ℃ for min -1 And taking out after cooling along with the furnace. Sequentially grinding and polishing by using 800, 1500 and 2000-mesh sand paper respectively until obtaining the LLZTO solid electrolyte ceramic chip with a smooth surface.
Spraying gold on the two sides of the LLZTO solid electrolyte ceramic sheet, and detecting the ionic conductivity and the density of the LLZTO solid electrolyte ceramic sheet. The results are shown in FIG. 7 b.
From examples 5 to 6 and FIG. 7, it can be seen that: example 5 and example 6 alumina crucibles prepared by different heat treatment methods for sintering the LLZTO solid electrolyte to obtain LLZTO solid electrolyte ceramic sheets with similar performance and room temperature ionic conductivity of 2.8 × 10 -4 S cm -1 (average value), 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 all-solid-state lithium battery.
From the above data, it can be seen that: EXAMPLE 5 method and apparatus for filling heat-treated crucible with LLZO powderExample 6 use of crucible-suspended Li 2 The performance of the alumina crucible obtained by the method of heat treatment above O powder is similar. Meanwhile, the LLZTO solid electrolyte ceramic sheet sintered by the alumina crucible without mother powder has the mother powder sintering performance similar to that of the traditional method, and compared with the prior platinum crucible sintering technology without mother powder, the alumina crucible of the invention has lower cost.
Example 7
The crucible was 3D printed in the same manner as in example 1 and data, and heat treated (using commercial sodium zirconium silicon phosphorus oxygen NZSP (Na) 3 Zr 2 Si 2 PO 12 ) Powder heat-treating it), specifically: suspending the crucible above NZSP powder of about 0.2g by 1-2cm, and maintaining the temperature at 1250 deg.C for 2h in a high-temperature sintering furnace at a temperature rise rate of 5 deg.C for min -1 And cooling along with the furnace and then taking out to obtain the NZSP treated alumina crucible.
The NZSP green compact was pressed from NZSP powder and about 0.4g of the NZSP powder was weighed into a 0.5 inch diameter tablet die and held at a pressure of 4MPa (about 300MPa actually applied to the tablet) on the press for 2min and removed to give a NZSP solid electrolyte green compact having a diameter of 1.27cm.
The NZSP solid electrolyte green body is put into the NZSP treated alumina crucible prepared in the embodiment, the mother powder is not required to be covered, a high-temperature sintering furnace is used for preserving heat for 6 hours at 1200 ℃, and the temperature rise rate is 5 ℃ for min -1 And taking out after cooling along with the furnace. Sequentially grinding and polishing by using 800, 1500 and 2000-mesh sand paper respectively until the NZSP solid electrolyte ceramic chip with a smooth surface is obtained.
And (4) spraying gold on the two sides of the NZSP solid electrolyte ceramic sheet, and testing the density and the ionic conductivity. The ion conductivity, density, and other properties of the NZSP solid electrolyte ceramic sheet of example 7 were measured to be similar to those of the electrolyte obtained when no mother powder was sintered using a conventional sintering method.
As described above, the alumina crucible of the present invention is made of inexpensive Al 2 O 3 The crucible is applied to the mother powder-free sintering solid electrolyte method, and can obtain the LLZO solid electrolyte with the performance similar to that of the traditional mother powder covering sintering method, and the production cost of the LLZO solid electrolyte is reducedMeanwhile, the preparation method of the alumina crucible 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 oxygen (NZSP) and other ceramic materials with elements such as lithium or sodium volatilizing in the sintering process, so that the sintering without mother powder is realized, and the production cost is reduced. Therefore, the invention effectively overcomes various defects in the prior art and has high industrial utilization value.
The foregoing embodiments are merely illustrative of the principles and utilities of the present invention and are not intended to limit the invention. Any person skilled in the art can modify or change the above-mentioned embodiments without departing from the spirit and scope of the present invention. Accordingly, it is intended that all equivalent modifications or changes which can be made by those skilled in the art without departing from the spirit and technical spirit of the present invention be covered by the claims of the present invention.
Claims (10)
1. An alumina crucible comprises a crucible body, and is characterized in that the crucible body comprises a pot body and a cover body; the pot body and the cover body are made of aluminum oxide materials, and at least the inner surfaces of the pot body and the cover body are covered with lithium aluminum oxide layers.
2. The alumina crucible of claim 1, wherein the crucible body is cylindrical; the pot body consists of a crucible bottom plate and a crucible side wall, and the crucible side wall is arranged around the crucible bottom plate to form a pot body containing cavity; optionally, a step for placing the cover body is formed on the inner side surface of the side wall of the crucible; optionally, in a closed state, the top of the cover body is flush with the top of the side wall of the crucible;
and/or the lithium aluminum oxide layer comprises a surface layer LiAlO 2 Layer and lining of LiAl 5 O 8 A layer;
and/or the average particle size of the lithium aluminum oxide layer is 3-10 mu m;
and/or the pot body and the cover body are obtained by 3D printing.
3. A method for producing an alumina crucible as claimed in any one of claims 1 to 2, characterized by comprising the steps of:
s1, preparing a crucible by using aluminum oxide as a raw material;
s2, carrying out heat treatment on the crucible prepared in the step S1 to prepare the alumina crucible as claimed in any one of claims 1 to 2.
4. The method for preparing the alumina crucible as claimed in claim 3, wherein in the step S1, the crucible surface appearance is loose and porous, and Al 2 O 3 The average particle diameter of the particles is less than 5 mu m;
and/or in the step S1, the crucible is printed in 3D mode and is obtained through degumming and densification processes.
5. The method for preparing the alumina crucible as claimed in claim 4, wherein the degumming is carried out by placing the crucible prepared in the step S1 into a box furnace, respectively keeping the temperature at 250-350 ℃ and 510-610 ℃, keeping the temperature for more than or equal to 1h, and keeping the temperature rise rate at less than or equal to 5 ℃ for min -1 Decomposing and separating the solidified polymer in the crucible to obtain a degumming crucible;
and/or, the densification is to place the degummed crucible in a high-temperature sintering furnace, heat the crucible to 1200-1400 ℃, and increase the temperature rate to be less than or equal to 5 ℃ for min -1 Keeping the temperature for 1-4 h, cooling along with the furnace, and taking out to obtain the densified crucible.
6. The method of claim 3, wherein the heat treatment in step S2 comprises any one of the following methods:
a. suspending the crucible of step S1 from Li 2 Sintering the powder above the O powder in a high-temperature sintering furnace;
b. the LLZO powder is placed inside the crucible of step S1 and sintered in a high temperature sintering furnace.
7. The method for producing an alumina crucible according to claim 6, characterized by comprising any one of the following methods:
a1. the sintering conditions are all that the temperature is kept at 1100-1300 ℃ for 40 min-5 h, and the heating rate is 1-10 ℃ for min -1 ；
b1. The sintering conditions are all that the temperature is kept at 1100-1300 ℃ for 40 min-5 h, and the heating rate is 1-10 ℃ for min -1 ；
b2. The LLZO powder comprises a doping element containing LLZO powder.
8. Use of the alumina crucible according to any one of claims 1 to 2 in the manufacture of a solid electrolyte ceramic sheet.
9. The preparation method of the LLZO solid electrolyte ceramic chip is characterized by comprising the following steps:
1) Preparing a green LLZO from the LLZO powder;
2) Placing the LLZO green body obtained in the step 1) into an alumina crucible disclosed by any one of claims 1-2, sintering in a high-temperature sintering furnace, taking out after furnace cooling, and grinding and polishing to obtain the LLZO solid electrolyte ceramic chip.
10. The method of manufacturing the LLZO solid electrolyte ceramic sheet according to claim 9, wherein: the preparation of the LLZO green compact in the step 1) comprises the following steps: mixing Al 2 O 3 Mixing the powder and the LLZO powder, sieving, adding into a tabletting mold, and tabletting to obtain a LLZO green body;
and/or, the temperature of the high-temperature sintering furnace in the step 2) is 1200-1300 ℃, and the heating rate is 2-10 ℃ for min -1 And the sintering heat preservation time is 20 min-2 h.
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| CN115814565A (en) * | 2022-11-30 | 2023-03-21 | 攀钢集团攀枝花钢铁研究院有限公司 | Potassium-sodium absorption method and absorbent for preparing vanadium-nitrogen alloy by pushed slab kiln calcination |
| CN115814565B (en) * | 2022-11-30 | 2024-05-31 | 攀钢集团攀枝花钢铁研究院有限公司 | Potassium-sodium absorption method and absorbent for preparing vanadium-nitrogen alloy by pushed slab kiln calcination |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115814565A (en) * | 2022-11-30 | 2023-03-21 | 攀钢集团攀枝花钢铁研究院有限公司 | Potassium-sodium absorption method and absorbent for preparing vanadium-nitrogen alloy by pushed slab kiln calcination |
| CN115814565B (en) * | 2022-11-30 | 2024-05-31 | 攀钢集团攀枝花钢铁研究院有限公司 | Potassium-sodium absorption method and absorbent for preparing vanadium-nitrogen alloy by pushed slab kiln calcination |
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