CN114394841A - Sagger for sintering lithium battery material and preparation method thereof - Google Patents
Sagger for sintering lithium battery material and preparation method thereof Download PDFInfo
- Publication number
- CN114394841A CN114394841A CN202210028335.9A CN202210028335A CN114394841A CN 114394841 A CN114394841 A CN 114394841A CN 202210028335 A CN202210028335 A CN 202210028335A CN 114394841 A CN114394841 A CN 114394841A
- Authority
- CN
- China
- Prior art keywords
- lithium
- transition layer
- sagger
- coating
- intermediate transition
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- 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
- C04B35/66—Monolithic refractories or refractory mortars, including those whether or not containing clay
-
- 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
- C04B35/03—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 magnesium oxide, calcium oxide or oxide mixtures derived from dolomite
- C04B35/04—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 magnesium oxide, calcium oxide or oxide mixtures derived from dolomite based on magnesium 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
- C04B35/01—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
- C04B35/01—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
- C04B35/16—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 silicates other than clay
-
- 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
- C04B35/16—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 silicates other than clay
- C04B35/18—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 silicates other than clay rich in aluminium oxide
- C04B35/185—Mullite 3Al2O3-2SiO2
-
- 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
- C04B35/16—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 silicates other than clay
- C04B35/18—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 silicates other than clay rich in aluminium oxide
- C04B35/195—Alkaline earth aluminosilicates, e.g. cordierite or anorthite
-
- 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
- C04B35/44—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 aluminates
- C04B35/443—Magnesium aluminate spinel
-
- 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
- C04B35/48—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 zirconium or hafnium oxides, zirconates, zircon or hafnates
-
- 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
- F27D—DETAILS OR ACCESSORIES OF FURNACES, KILNS, OVENS, OR RETORTS, IN SO FAR AS THEY ARE OF KINDS OCCURRING IN MORE THAN ONE KIND OF FURNACE
- F27D5/00—Supports, screens, or the like for the charge within the furnace
- F27D5/0006—Composite supporting structures
- F27D5/0012—Modules of the sagger or setter type; Supports built up from them
-
- 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
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3201—Alkali metal oxides or oxide-forming salts thereof
-
- 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
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3205—Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
- C04B2235/3206—Magnesium oxides or oxide-forming salts thereof
-
- 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
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/34—Non-metal oxides, non-metal mixed oxides, or salts thereof that form the non-metal oxides upon heating, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3427—Silicates other than clay, e.g. water glass
-
- 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
- C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
- C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Ceramic Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- General Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Inorganic Chemistry (AREA)
- Composite Materials (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Compositions Of Oxide Ceramics (AREA)
- Furnace Charging Or Discharging (AREA)
Abstract
The invention relates to a sagger for sintering a lithium battery material and a preparation method thereof. The sagger comprises a substrate, an intermediate transition layer and a volatile coating; middle processThe transition layer comprises ZrSiO accounting for 0.1-30 wt% of the total mass of the intermediate transition layer40.1 to 60 wt% of Mg2Zr14O50.1 to 50 weight percent of MgO, 0.1 to 60 weight percent of KMgO or 0.1 to 40 weight percent of K4Zr5O12At least two of; the volatile coating comprises 0.1-20 wt% of lithium source, 0-50 wt% of binder and 40-80 wt% of filler; the volatilization coating is used for providing a lithium-rich sintering atmosphere for the lithium battery material in the sintering process, and the filler volatilizes CO in the sintering process2. The high-density intermediate transition layer can effectively prevent the materials at the high-temperature section from contacting with the base material of the crucible to generate a low-solubility phase in the sintering process so as to damage the sagger structure; the generation of lithium deficient phases is prevented by employing a lithium containing coating to provide a lithium rich sintering atmosphere for the lithium battery material.
Description
Technical Field
The invention relates to the technical field of lithium battery material preparation devices, in particular to a sagger for sintering a lithium battery material and a preparation method thereof.
Background
Due to the excellent performance of the lithium battery, the lithium battery has wide application prospects in the fields of computers, mobile phones, new energy automobiles and energy storage. At present, both the anode material and the solid electrolyte material of the lithium battery can form an ideal material structure by high-temperature calcination so as to meet the application requirements of the lithium battery. In the industrial mass production process, the lithium battery material precursor is placed in a sagger (usually cordierite, mullite, corundum and the like), and is calcined by a high-temperature solid phase method to produce ternary cathode materials such as NCM, NCA and the like or oxide solid electrolyte materials such as LATP, LLZO, LLTO and the like. However, at high temperatures, Al in the saggars2O3、SiO2Can react with Li in lithium battery material2O reaction to produce LiAlSiO4、LiAlO2And LiAl5O8And (c) a compound such as a quaternary ammonium compound. For positive electrode materials, Al in the saggar2O3And the nickel aluminate spinel can also react with NiO, CoO and MnO in the lithium battery material to form products such as nickel aluminate spinel solid solution and the like, so that the corrosion of the inner wall of the sagger is caused. Because the thermal expansion coefficients of the reaction product and the phase in the original sagger are different, the eroded layer can be cracked and peeled off, and the service life of the sagger is shortened. Erosion of the sagger material typically begins with the substrate portion. For example, SiO in a mullite sagger2The higher the content, the easier it is for the alkali oxide Li to be active in nature2The corrosion of O penetrates and exfoliation occurs. Li2After entering the sagger, the O reacts with the mullite (including the combination phase of the mullite grains and the mullite) in the sagger to generate Al2O3-SiO2-Li2O low-soluble phase, wherein the low-soluble phase migrates from the surface layer of the sagger to the bottom layer of the sagger along the microcracks of the sagger, so that the substrate on the inner surface is lost and is in a void shape;and the deep part of the bottom is filled with a large amount of low-soluble phase and is continuously distributed, so that the high-temperature strength of the bottom of the sagger is sharply reduced to generate collapse.
To address this problem, many sagger manufacturers choose to reduce SiO in order to increase the service life of the sagger2And (4) content. However, corundum (Al)2O3) Due to the large thermal expansion coefficient (8.8 multiplied by 10)-6℃-1) Reduction of SiO2Content of Al2O3The increase of the material proportion inevitably leads to the reduction of the thermal shock resistance of the material. Therefore, the conventional sagger cannot guarantee the thermal shock resistance of the sagger while considering the service life of the sagger.
Disclosure of Invention
The embodiment of the invention provides a sagger for sintering a lithium battery material and a preparation method thereof. The sagger innovatively adopts a three-layer structure of a substrate, a middle transition layer and a volatile coating; the high-density intermediate transition layer can effectively prevent the materials at the high-temperature section from contacting with the base material of the crucible to generate a low-solubility phase in the sintering process so as to damage the sagger structure; the generation of lithium deficient phases is prevented by providing a lithium rich sintering atmosphere for lithium battery materials by using a Li containing volatile coating.
In a first aspect, embodiments of the present invention provide a sagger for sintering a lithium battery material, including a substrate, an intermediate transition layer, and a volatile coating;
the intermediate transition layer comprises ZrSiO accounting for 0.1-30 wt% of the total mass of the intermediate transition layer40.1 to 60 wt% of Mg2Zr14O50.1 to 50 weight percent of MgO, 0.1 to 60 weight percent of KMgO or 0.1 to 40 weight percent of K4Zr5O12At least two of;
the volatile coating comprises a lithium source accounting for 0.1-20 wt% of the total mass of the volatile coating, a binder accounting for 0-50 wt% of the total mass of the volatile coating, and a filler accounting for 40-80 wt%; the volatilization coating is used for providing a lithium-rich sintering atmosphere for the lithium battery material in the sintering process, and the filler volatilizes CO in the sintering process2。
Preferably, the material of the substrate comprises: mullite (3 Al)2O3·2SiO2) Cordierite ((Mg, Fe)3+)2Al4Si5O18) Corundum (Al)2O3) Spinel (MgAl)2O4) One or more of the above;
in the volatile coating, the lithium source includes: one or more of lithium carbonate, lithium bicarbonate, lithium hydroxide, lithium phosphate, lithium oxalate, lithium acetate, lithium fluoride, lithium manganate and lithium sulfide; the binder comprises one or more of styrene butadiene rubber, polyvinylpyrrolidone, polyvinyl alcohol, polyvinyl butyral, carboxymethyl cellulose, polyacrylic acid, polytetrafluoroethylene, polymethyl methacrylate and polyvinylidene fluoride; the filler includes: one or more of carbon powder, potato starch, corn starch or glucose.
Preferably, the intermediate transition layer at least comprises Mg2Zr14O5KMgO or K4Zr5O12One kind of (1).
Further preferably, the intermediate transition layer comprises at least Mg2Zr14O5。
In a second aspect, an embodiment of the present invention provides a preparation method of the sagger for sintering a lithium battery material, where the preparation method includes:
mixing mullite (3 Al)2O3·2SiO2) Material, cordierite ((Mg, Fe)3+)2Al4Si5O18) Material, corundum (Al)2O3) Material, spinel (MgAl)2O4) Mixing the materials according to the mass ratio of 0-50%, 0-60%, 0-50% and 0-40% to obtain a powder material of the substrate;
adding a binder which accounts for 0.5 to 1.5 percent of the total mass of the powder material into the powder material of the substrate and granulating;
placing the granulated material in a static pressure die, carrying out static pressure forming under the pressure of 120MPa-200MPa, and drying the formed biscuit at the temperature of 80-95 ℃;
according to the mass ratio, the material contains 0.1 to 30 weight percent of ZrSiO40.1 to 60 wt% of Mg2Zr14O50.1 to 50 weight percent of MgO, 0.1 to 60 weight percent of KMgO or 0.1 to 40 weight percent of K4Zr5O12Adding a binder which accounts for 1-2% of the total mass of the powder materials of the intermediate transition layer into at least two powder materials of the intermediate transition layer, and preparing into water-based slurry according to the solid content accounting for 50-80%;
coating the water-based slurry on the surface of the biscuit, heating to 1300-1800 ℃ at a heating rate of 0.2-2 ℃/min, and preserving heat for 12-20 hours to prepare a bowl body with an intermediate transition layer;
adding 0.1-20 wt% of lithium source, 0-50 wt% of binder and 40-80 wt% of filler into water, uniformly mixing to form coating slurry, coating or spraying the coating slurry on a pot body with an intermediate transition layer, and drying to obtain the sagger for sintering the lithium battery material.
Preferably, the water-based slurry is coated on the surface of the biscuit to a coating thickness of 3cm-5 cm.
Preferably, the lithium source includes: one or more of lithium carbonate, lithium bicarbonate, lithium hydroxide, lithium phosphate, lithium oxalate, lithium acetate, lithium fluoride, lithium manganate and lithium sulfide;
the binder comprises one or more of styrene butadiene rubber, polyvinylpyrrolidone, polyvinyl alcohol, polyvinyl butyral, carboxymethyl cellulose, polyacrylic acid, polytetrafluoroethylene, polymethyl methacrylate and polyvinylidene fluoride;
the filler includes: one or more of carbon powder, potato starch, corn starch or glucose.
Preferably, after each burning of the lithium battery material in the sagger, the preparation method further comprises:
and preparing the coating slurry again, coating or spraying the coating slurry on the pot body with the intermediate transition layer, and drying.
The sagger for sintering the lithium battery material is innovatively in a three-layer structure of the substrate, the intermediate transition layer and the volatile coating. Wherein, the volatile coating is formed by spraying or coating again after each sintering, thereby avoiding impurity contamination possibly introduced after the sintering of the traditional crucible. In the process of sintering the lithium battery material by using the sagger, the sagger disclosed by the invention adopts segmented protection for the sintering process, the sintered material and the substrate of the sagger can be isolated at the low-temperature sintering stage through the volatilization coating, the phenomenon that impurity elements enter the sintered material or are adhered after sintering is prevented, and the lithium-rich sintering atmosphere can be provided for the lithium battery material through the volatilization of Li in the volatilization coating, so that the generation of a lithium-deficient phase is prevented. After the volatile coating volatilizes at the high-temperature section of sintering, the intermediate transition layer with high density can effectively prevent the material from contacting with the substrate material of the crucible to generate low-solubility phase in the high-temperature section of the sintering process and damage the sagger structure, and effectively prolong the service life of the sagger.
Drawings
The technical solutions of the embodiments of the present invention are further described in detail with reference to the accompanying drawings and embodiments.
FIG. 1 is a flow chart of a method of making a sagger of an embodiment of the present invention.
Detailed Description
The invention is further illustrated by the following figures and specific examples, but it should be understood that these examples are for the purpose of illustration only and are not to be construed as in any way limiting the present invention, i.e., as in no way limiting its scope.
The invention provides a sagger for sintering a lithium battery material, which comprises the following components: the coating comprises a substrate, an intermediate transition layer and a volatile coating;
the material of the substrate includes: mullite (3 Al)2O3·2SiO2) Cordierite ((Mg, Fe)3+)2Al4Si5O18) Corundum (Al)2O3) Spinel (MgAl)2O4) One or more of the above;
the intermediate transition layer comprises ZrSiO 0.1-30 wt% of the total mass of the intermediate transition layer40.1 to 60 wt% of Mg2Zr14O50.1 to 50 weight percent of MgO, 0.1 to 60 weight percent of KMgO or 0.1 to 40 weight percent of KMgOwt% of K4Zr5O12At least two of them. Preferably, the intermediate transition layer comprises at least Mg2Zr14O5KMgO or K4Zr5O12One kind of (1). More preferably, the intermediate transition layer comprises at least Mg2Zr14O5. Because of the Li resistance of these three materials2O is highly corrosive, e.g. Mg2Zr14O5The density of the material is 5.673g/cm3，K4Zr5O12The density of the material was 4.176g/cm3The high-density intermediate transition layer material is adopted, so that the material can be effectively prevented from contacting with the base material, the thermal shock resistance of the whole material of the crucible is ensured, and meanwhile, the Li is avoided2O and SiO2Form low-solubility phase and prolong the service life of the crucible
The volatile coating comprises a lithium source accounting for 0.1-20 wt% of the total mass of the volatile coating, a binder accounting for 0-50 wt% of the total mass of the volatile coating, and a filler accounting for 40-80 wt%. In the volatile coating, the lithium source comprises: one or more of lithium carbonate, lithium bicarbonate, lithium hydroxide, lithium phosphate, lithium oxalate, lithium acetate, lithium fluoride, lithium manganate and lithium sulfide; the binder comprises one or more of styrene butadiene rubber, polyvinylpyrrolidone, polyvinyl alcohol, polyvinyl butyral, carboxymethyl cellulose, polyacrylic acid, polytetrafluoroethylene, polymethyl methacrylate and polyvinylidene fluoride; the filler comprises: one or more of carbon powder, potato starch, corn starch or glucose. The volatilization coating is used for providing a lithium-rich sintering atmosphere for the lithium battery material in the sintering process, and the filler volatilizes CO in the sintering process2So that after sintering, the volatile coating is no longer present. Thus, after each firing of the lithium battery material in the sagger, the volatile coating needs to be prepared again.
Fig. 1 is a flowchart of a method for manufacturing a sagger for sintering a lithium battery material according to an embodiment of the present invention. As shown in fig. 1, the preparation method mainly comprises the following steps:
specifically, the binder comprises one or more of styrene butadiene rubber, polyvinylpyrrolidone, polyvinyl alcohol, polyvinyl butyral, carboxymethyl cellulose, polyacrylic acid, polytetrafluoroethylene, polymethyl methacrylate and polyvinylidene fluoride;
preferably, the binder comprises one or more of styrene butadiene rubber, polyvinylpyrrolidone, polyvinyl alcohol, polyvinyl butyral, carboxymethyl cellulose, polyacrylic acid, polytetrafluoroethylene, polymethyl methacrylate and polyvinylidene fluoride;
the intermediate transition layer powder material at least comprises Mg2Zr14O5KMgO or K4Zr5O12One of (1); more preferably, the intermediate transition layer powder material at least comprises Mg2Zr14O5。
wherein the coating thickness of the water-based slurry coated on the surface of the biscuit is 3cm-5 cm.
And 160, adding 0.1-20 wt% of lithium source, 0-50 wt% of binder and 40-80 wt% of filler into water, uniformly mixing to form coating slurry, coating or spraying the coating slurry on a pot body with an intermediate transition layer, and drying to obtain the sagger for sintering the lithium battery material.
Wherein the lithium source comprises: one or more of lithium carbonate, lithium bicarbonate, lithium hydroxide, lithium phosphate, lithium oxalate, lithium acetate, lithium fluoride, lithium manganate and lithium sulfide;
the binder comprises one or more of styrene butadiene rubber, polyvinylpyrrolidone, polyvinyl alcohol, polyvinyl butyral, carboxymethyl cellulose, polyacrylic acid, polytetrafluoroethylene, polymethyl methacrylate and polyvinylidene fluoride;
the filler comprises: one or more of carbon powder, potato starch, corn starch or glucose.
Further, after the lithium battery material is fired in the saggar every time, the outermost volatile coating layer is volatilized and lost, so that the preparation method further comprises the following steps:
and after the lithium battery material is fired in the sagger every time, coating slurry is prepared again, and the coating slurry is coated or sprayed on the sagger body with the intermediate transition layer, dried and re-formed into a volatile coating.
The sagger for sintering the lithium battery material is innovatively in a three-layer structure of the substrate, the intermediate transition layer and the volatile coating. Wherein, the volatile coating is formed by spraying or coating again after each sintering, thereby avoiding impurity contamination possibly introduced after the sintering of the traditional crucible. In the process of sintering the lithium battery material by using the sagger, the sagger disclosed by the invention adopts segmented protection for the sintering process, the sintered material and the substrate of the sagger can be isolated at the low-temperature sintering stage through the volatilization coating, the phenomenon that impurity elements enter the sintered material or are adhered after sintering is prevented, and the lithium-rich sintering atmosphere can be provided for the lithium battery material through the volatilization of Li in the volatilization coating, so that the generation of a lithium-deficient phase is prevented. After the volatile coating volatilizes at the high-temperature section of sintering, the intermediate transition layer with high density can effectively prevent the material from contacting with the substrate material of the crucible to generate low-solubility phase in the high-temperature section of the sintering process and damage the sagger structure, and effectively prolong the service life of the sagger.
To better understand the technical solution provided by the present invention, the following description is given of a specific example of preparing a sagger by applying the method provided by the above embodiment of the present invention.
Examples 1 to 5
The refractory powder material purchased in the market: mullite (3 Al)2O3·2SiO2) Cordierite ((Mg, Fe)3+)2Al4Si5O18) Corundum (Al)2O3) Spinel (MgAl)2O4) The raw materials were prepared in the saggars of examples 1 to 5, respectively, while adjusting the mass ratio shown in Table 1.
| Mullite (wt%) | Cordierite (wt%) | Corundum (wt%) | Spinel (wt%) | |
| Example 1 | 20 | 20 | 20 | 40 |
| Example 2 | 40 | 20 | 20 | 20 |
| Example 3 | 10 | 30 | 30 | 30 |
| Example 4 | 50 | 40 | 0 | 10 |
| Example 5 | 30 | 30 | 40 | 0 |
TABLE 1
For each of the raw materials for preparation of the sagger of examples 1 to 5, polyvinyl alcohol was added in an amount of 0.5 wt% based on the weight of the powder to granulate the powder. And pouring the granulated refractory material powder into an isostatic pressing die, and carrying out isostatic pressing on the powder under the pressure of 120 MPa. And drying the formed biscuit at 80 ℃.
Use of 20 wt% ZrSiO4，20wt％Mg2Zr14O5，20wt％MgO，20wt％KMgO，20wt％K4Zr5O12As a powder material of the intermediate transition layer, a binder polyvinyl butyral accounting for 2 wt% of the powder weight of the intermediate transition layer is added, and water system slurry is prepared according to the solid content of 60%. The water system slurry is coated on the surface of a biscuit, and the thickness is 5 cm.
And drying the biscuit at 80 ℃, heating to 1800 ℃ at a heating rate of 0.5 ℃/min, and preserving heat for 15 hours to obtain the fired substrate with the intermediate transition layer.
Adding 5 wt% of lithium source, 15 wt% of polyvinylpyrrolidone and 80 wt% of potato starch into water, uniformly mixing to form slurry, coating the slurry on the surface of a fired substrate with an intermediate transition layer, and drying to obtain the sagger of the embodiment 1-5 of the invention.
Examples 6 to 10
The raw materials were prepared in the same saggar preparation as in example 1.
For each of the raw materials for preparing the saggars of examples 6 to 10, polyvinyl alcohol was added in an amount of 0.5 wt% based on the weight of the powder to granulate the powder. And pouring the granulated refractory material powder into an isostatic pressing die, and carrying out isostatic pressing on the powder under the pressure of 150 MPa. And drying the formed biscuit at 80 ℃.
Using ZrSiO4，Mg2Zr14O5，MgO，KMgO，K4Zr5O12As the powder material of the intermediate transition layer, the mixture ratio is shown in Table 2, and the adhesive polyvinyl butyral accounting for 2 wt% of the weight of the powder of the intermediate transition layer is added to prepare water system slurry according to the solid content of 60%. The aqueous slurries were applied to the surfaces of the biscuits from examples 6-10, respectively, to a thickness of 5 cm.
| ZrSiO4(wt％) | Mg2Zr14O5(wt％) | MgO(wt％) | KMgO(wt％) | K4Zr5O12(wt％) | |
| Example 6 | 20 | 20 | 20 | 20 | 20 |
| Example 7 | 10 | 30 | 20 | 30 | 10 |
| Example 8 | 5 | 5 | 40 | 20 | 30 |
| Example 9 | 5 | 10 | 50 | 5 | 30 |
| Example 10 | 15 | 15 | 50 | 5 | 15 |
TABLE 2
And drying the biscuit at 80 ℃, heating to 1800 ℃ at a heating rate of 0.5 ℃/min, and preserving heat for 15 hours to obtain the fired substrate with the intermediate transition layer.
Adding 5 wt% of lithium source, 15 wt% of carboxymethyl cellulose and 80 wt% of potato starch into water, uniformly mixing to form slurry, coating the slurry on the surface of a fired substrate with an intermediate transition layer, and drying to obtain the sagger of the embodiment 6-10 of the invention.
Examples 11 to 15
The raw materials were prepared in the same saggar preparation as in example 1.
For each of the raw materials for producing the saggars of examples 11 to 15, polyvinyl butyral was added in an amount of 0.5 wt% based on the weight of the powder to granulate the powder. And pouring the granulated refractory material powder into an isostatic pressing die, and carrying out isostatic pressing on the powder under the pressure of 150 MPa. And drying the formed biscuit at 80 ℃.
Using the same mass ratio as in example 6, with ZrSiO4，Mg2Zr14O5，MgO，KMgO，K4Zr5O12As a powder material of the intermediate transition layer, binder carboxymethyl cellulose accounting for 2 wt% of the weight of the powder of the intermediate transition layer is added, and water system slurry is prepared according to the solid content of 50%. The aqueous slurries were applied to the surfaces of the biscuits from examples 6-10, respectively, to a thickness of 3 cm.
And drying the biscuit at 80 ℃, heating to 1800 ℃ at a heating rate of 0.5 ℃/min, and preserving heat for 15 hours to obtain the fired substrate with the intermediate transition layer.
Adding a lithium source, a binder and a filler into water, specifically mixing uniformly to form slurry as shown in Table 3, coating the slurry on the surface of a fired substrate with an intermediate transition layer, and drying to obtain the sagger of the invention.
| Lithium source | Binder | Filler material | |
| Example 11 | Lithium carbonate 10 wt% | Polyvinyl alcohol 10 wt% | Potato starch 80 wt% |
| Example 12 | Lithium carbonate 15 wt% | Polyvinylpyrrolidone 5% by weight | Potato starch 80 wt% |
| Example 13 | Lithium oxalate 15 wt% | Polyvinyl alcohol 10 wt% | 75 wt% of glucose |
| Example 14 | 10 wt% of lithium bicarbonate | Polyvinyl alcohol 10 wt% | Glucose 80 wt% |
| Example 15 | 5 wt% of lithium bicarbonate | Polyvinyl alcohol 15 wt% | 80 wt% of carbon powder |
TABLE 3
Comparative examples 1 to 5
The refractory powder material purchased in the market: mullite (3 Al)2O3·2SiO2) Cordierite ((Mg, Fe)3+)2Al4Si5O18) Corundum (Al)2O3) Spinel (MgAl)2O4) The raw materials were prepared in the saggars of comparative examples 1 to 5, respectively, by adjusting the mass ratio shown in Table 4.
| Mullite (wt%) | Cordierite (wt%) | Corundum (wt%) | Spinel (wt%) | |
| Comparative example 1 | 20 | 20 | 20 | 40 |
| Comparative example 2 | 40 | 20 | 20 | 20 |
| Comparative example 3 | 10 | 30 | 30 | 30 |
| Comparative example 4 | 50 | 40 | 0 | 10 |
| Comparative example 5 | 30 | 30 | 40 | 0 |
TABLE 4
For the raw materials for the preparation of the sagger of comparative examples 1 to 5, polyvinyl alcohol was added in an amount of 0.5 wt% based on the weight of the powder to granulate the powder. And pouring the granulated refractory material powder into an isostatic pressing die, and carrying out isostatic pressing on the powder under the pressure of 120 MPa. And drying the biscuit at 80 ℃, heating to 1800 ℃ at a heating rate of 0.5 ℃/min, and preserving heat for 15 hours to obtain the fired matrix crucible.
The service conditions and the service lives of the crucibles according to the above examples and comparative examples were examined. The test results are shown in table 5.
| Group of | Service life (times) | Description of test results |
| Example 1 | 23 | No falling off and no crack |
| Example 2 | 21 | No falling off and no crack |
| Example 3 | 24 | No falling off and no crack |
| Example 4 | 23 | No falling off and no crack |
| Example 5 | 21 | No falling off and no crack |
| Example 6 | 24 | No falling off and no crack |
| Example 7 | 25 | No falling off and no crack |
| Example 8 | 22 | No falling off and no crack |
| Example 9 | 23 | No falling off and no crack |
| Example 10 | 23 | No falling off and no crack |
| Example 11 | 21 | No falling off and no crack |
| Example 12 | 24 | No falling off and no crack |
| Example 13 | 22 | No falling off and no crack |
| Example 14 | 21 | No falling off and no crack |
| Example 15 | 25 | No falling off and no crack |
| Comparative example 1 | 4 | 4 th occurrence of cracks |
| Comparative example 2 | 5 | 5 th occurrence of cracks |
| Comparative example 3 | 3 | No. 3, occurrence of cracks |
| Comparative example 4 | 4 | 4 th occurrence of cracks |
| Comparative example 5 | 4 | 4 th occurrence of cracks |
TABLE 5
The sagger has the advantages that the materials and the structure of the sagger are improved, the segmented protection is adopted in the sintering process, and the service life of the sagger is effectively prolonged.
The above-mentioned embodiments are intended to illustrate the objects, technical solutions and advantages of the present invention in further detail, and it should be understood that the above-mentioned embodiments are merely exemplary embodiments of the present invention, and are not intended to limit the scope of the present invention, and any modifications, equivalent substitutions, improvements and the like made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (10)
1. The sagger for sintering the lithium battery material is characterized by comprising a substrate, an intermediate transition layer and a volatile coating;
the intermediate transition layer comprises ZrSiO accounting for 0.1-30 wt% of the total mass of the intermediate transition layer40.1 to 60 wt% of Mg2Zr14O50.1 to 50 weight percent of MgO, 0.1 to 60 weight percent of KMgO or 0.1 to 40 weight percent of K4Zr5O12At least two of;
the volatile coatingComprises 0.1-20 wt% of lithium source, 0-50 wt% of binder and 40-80 wt% of filler; the volatilization coating is used for providing a lithium-rich sintering atmosphere for the lithium battery material in the sintering process, and the filler volatilizes CO in the sintering process2。
2. The sagger of claim 1, wherein the material of the base comprises: mullite (3 Al)2O3·2SiO2) Cordierite ((Mg, Fe)3+)2Al4Si5O18) Corundum (Al)2O3) Spinel (MgAl)2O4) One or more of the above;
in the volatile coating, the lithium source includes: one or more of lithium carbonate, lithium bicarbonate, lithium hydroxide, lithium phosphate, lithium oxalate, lithium acetate, lithium fluoride, lithium manganate and lithium sulfide; the binder comprises one or more of styrene butadiene rubber, polyvinylpyrrolidone, polyvinyl alcohol, polyvinyl butyral, carboxymethyl cellulose, polyacrylic acid, polytetrafluoroethylene, polymethyl methacrylate and polyvinylidene fluoride; the filler includes: one or more of carbon powder, potato starch, corn starch or glucose.
3. Sagger according to claim 1, characterized in that said intermediate transition layer comprises at least Mg2Zr14O5KMgO or K4Zr5O12One kind of (1).
4. Sagger according to claim 3, characterized in that said intermediate transition layer comprises at least Mg2Zr14O5。
5. The method for preparing the sagger for sintering the lithium battery material according to claim 1, wherein the method comprises the following steps:
mixing mullite (3 Al)2O3·2SiO2) Material, cordierite ((M)g,Fe3+)2Al4Si5O18) Material, corundum (Al)2O3) Material, spinel (MgAl)2O4) Mixing the materials according to the mass ratio of 0-50%, 0-60%, 0-50% and 0-40% to obtain a powder material of the substrate;
adding a binder which accounts for 0.5 to 1.5 percent of the total mass of the powder material into the powder material of the substrate and granulating;
placing the granulated material in a static pressure die, carrying out static pressure forming under the pressure of 120MPa-200MPa, and drying the formed biscuit at the temperature of 80-95 ℃;
according to the mass ratio, the material contains 0.1 to 30 weight percent of ZrSiO40.1 to 60 wt% of Mg2Zr14O50.1 to 50 weight percent of MgO, 0.1 to 60 weight percent of KMgO or 0.1 to 40 weight percent of K4Zr5O12Adding a binder which accounts for 1-2% of the total mass of the powder materials of the intermediate transition layer into at least two powder materials of the intermediate transition layer, and preparing into water-based slurry according to the solid content accounting for 50-80%;
coating the water-based slurry on the surface of the biscuit, heating to 1300-1800 ℃ at a heating rate of 0.2-2 ℃/min, and preserving heat for 12-20 hours to prepare a bowl body with an intermediate transition layer;
adding 0.1-20 wt% of lithium source, 0-50 wt% of binder and 40-80 wt% of filler into water, uniformly mixing to form coating slurry, coating or spraying the coating slurry on a pot body with an intermediate transition layer, and drying to obtain the sagger for sintering the lithium battery material.
6. The method according to claim 5, wherein the aqueous slurry is applied to the surface of the green body at a thickness of 3cm to 5 cm.
7. The production method according to claim 5,
the lithium source includes: one or more of lithium carbonate, lithium bicarbonate, lithium hydroxide, lithium phosphate, lithium oxalate, lithium acetate, lithium fluoride, lithium manganate and lithium sulfide;
the binder comprises one or more of styrene butadiene rubber, polyvinylpyrrolidone, polyvinyl alcohol, polyvinyl butyral, carboxymethyl cellulose, polyacrylic acid, polytetrafluoroethylene, polymethyl methacrylate and polyvinylidene fluoride;
the filler includes: one or more of carbon powder, potato starch, corn starch or glucose.
8. The method of claim 5, wherein after each firing of the lithium battery material in the sagger, the method further comprises:
and preparing the coating slurry again, coating or spraying the coating slurry on the pot body with the intermediate transition layer, and drying to form the volatile coating.
9. The preparation method according to claim 5, wherein the intermediate transition layer powder material at least comprises Mg2Zr14O5KMgO or K4Zr5O12One kind of (1).
10. The method according to claim 9, wherein the intermediate transition layer powder material at least comprises Mg2Zr14O5。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210028335.9A CN114394841B (en) | 2022-01-11 | 2022-01-11 | Sagger for sintering lithium battery material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210028335.9A CN114394841B (en) | 2022-01-11 | 2022-01-11 | Sagger for sintering lithium battery material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114394841A true CN114394841A (en) | 2022-04-26 |
| CN114394841B CN114394841B (en) | 2022-09-27 |
Family
ID=81230708
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210028335.9A Active CN114394841B (en) | 2022-01-11 | 2022-01-11 | Sagger for sintering lithium battery material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114394841B (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2014118339A (en) * | 2012-12-19 | 2014-06-30 | Kyodo Fine Ceramics Co Ltd | Ceramic coated sagger for producing lithium ion positive electrode active material |
| CN105698542A (en) * | 2016-03-21 | 2016-06-22 | 武汉理工大学 | Lithium battery high-temperature corrosion resistance laminar saggar and preparation method thereof |
| JP2019121601A (en) * | 2018-01-08 | 2019-07-22 | 朱 性宇Ｘｉｎｇｙｕ Ｚｈｕ | Lithium ion battery electrode material firing pot and protective layer of the same |
| CN110451944A (en) * | 2019-05-21 | 2019-11-15 | 湖南太子新材料科技有限公司 | A kind of the anode material of lithium battery saggar and its manufacturing method of high finished product rate |
| CN110590341A (en) * | 2019-09-29 | 2019-12-20 | 武汉科技大学 | Sagger for sintering sol-combined lithium battery positive electrode material and preparation method thereof |
| CN112456990A (en) * | 2020-12-16 | 2021-03-09 | 河北汉唐鼎为科技有限公司 | Sagger special for synthesizing lithium battery positive electrode material and preparation method thereof |
-
2022
- 2022-01-11 CN CN202210028335.9A patent/CN114394841B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2014118339A (en) * | 2012-12-19 | 2014-06-30 | Kyodo Fine Ceramics Co Ltd | Ceramic coated sagger for producing lithium ion positive electrode active material |
| CN105698542A (en) * | 2016-03-21 | 2016-06-22 | 武汉理工大学 | Lithium battery high-temperature corrosion resistance laminar saggar and preparation method thereof |
| JP2019121601A (en) * | 2018-01-08 | 2019-07-22 | 朱 性宇Ｘｉｎｇｙｕ Ｚｈｕ | Lithium ion battery electrode material firing pot and protective layer of the same |
| CN110451944A (en) * | 2019-05-21 | 2019-11-15 | 湖南太子新材料科技有限公司 | A kind of the anode material of lithium battery saggar and its manufacturing method of high finished product rate |
| CN110590341A (en) * | 2019-09-29 | 2019-12-20 | 武汉科技大学 | Sagger for sintering sol-combined lithium battery positive electrode material and preparation method thereof |
| CN112456990A (en) * | 2020-12-16 | 2021-03-09 | 河北汉唐鼎为科技有限公司 | Sagger special for synthesizing lithium battery positive electrode material and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 单峙霖等: "锂电池正极材料烧成用匣钵材料性能的研究", 《耐火材料》 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114394841B (en) | 2022-09-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP2019121601A (en) | Lithium ion battery electrode material firing pot and protective layer of the same | |
| CN112624765B (en) | Sagger for sintering lithium transition metal oxide and preparation method thereof | |
| CN110746805B (en) | Coating for lithium ion battery anode material sintering saggar and preparation method thereof | |
| CN108341666B (en) | Casket-like bowl and preparation method thereof | |
| JP5241868B2 (en) | sheath | |
| CN105698542A (en) | Lithium battery high-temperature corrosion resistance laminar saggar and preparation method thereof | |
| JP2009292704A (en) | Sagger for producing positive electrode active material of lithium ion battery | |
| CN111233482A (en) | High-temperature-resistant sagger and preparation method thereof | |
| CN112010661B (en) | Sagger for lithium battery positive electrode material and preparation method thereof | |
| CN107892581B (en) | High-strength corrosion-resistant zirconia corundum honeycomb ceramic body and preparation method thereof | |
| CN109956760A (en) | A kind of nickelic ternary material sintering saggar and preparation method thereof | |
| CN109400137A (en) | Anode material of lithium battery firing fire-clay crucible and preparation method thereof | |
| KR101159102B1 (en) | Furnace for Manufacture of Lithium-Metal Oxide and Process for Preparing the Same | |
| CN207716877U (en) | Electrode material of lithium battery preparation saggar | |
| CN109851337A (en) | A kind of high temperature dichroite-mullite refractory slab and preparation method thereof | |
| CN110903074A (en) | High-temperature oxidation-resistant coating on surface of silicon carbide substrate and preparation method thereof | |
| JP2003165767A (en) | Spinel refractory and use of the same | |
| CN114394841B (en) | Sagger for sintering lithium battery material and preparation method thereof | |
| CN115340409B (en) | Sagger coating for lithium battery positive electrode material and preparation method of sagger coating | |
| CN111718207A (en) | Preparation method of modified cordierite-mullite refractory material | |
| CN109534805B (en) | Forsterite-corundum sagger for sintering lithium battery powder and preparation method thereof | |
| CN115353372A (en) | Sagger for sintering lithium battery positive electrode material and preparation method thereof | |
| CN111102844A (en) | Preparation method of sagger for sintering lithium battery positive electrode material | |
| CN113480300B (en) | Mullite composite sagger and preparation method thereof | |
| JP4446633B2 (en) | Coating agent for firing jig and firing jig |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |