CN111233447A - Preparation method of high-durability kiln furniture for positive electrode material of lithium-ion battery - Google Patents
Preparation method of high-durability kiln furniture for positive electrode material of lithium-ion battery Download PDFInfo
- Publication number
- CN111233447A CN111233447A CN202010044845.6A CN202010044845A CN111233447A CN 111233447 A CN111233447 A CN 111233447A CN 202010044845 A CN202010044845 A CN 202010044845A CN 111233447 A CN111233447 A CN 111233447A
- Authority
- CN
- China
- Prior art keywords
- layer
- kiln furniture
- lithium
- durability
- positive electrode
- 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.)
- Pending
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
- C04B35/01—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
- C04B35/10—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
- C04B35/101—Refractories from grain sized mixtures
- C04B35/106—Refractories from grain sized mixtures containing zirconium oxide or zircon (ZrSiO4)
-
- 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
- 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
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3217—Aluminum oxide or oxide forming salts thereof, e.g. bauxite, alpha-alumina
- C04B2235/3222—Aluminates other than alumino-silicates, e.g. spinel (MgAl2O4)
-
- 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
- C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
- C04B2235/3232—Titanium oxides or titanates, e.g. rutile or anatase
-
- 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
- C04B2235/3463—Alumino-silicates other than clay, e.g. mullite
- C04B2235/3481—Alkaline earth metal alumino-silicates other than clay, e.g. cordierite, beryl, micas such as margarite, plagioclase feldspars such as anorthite, zeolites such as chabazite
-
- 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
- C04B2235/349—Clays, e.g. bentonites, smectites such as montmorillonite, vermiculites or kaolines, e.g. illite, talc or sepiolite
-
- 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
- C04B2235/44—Metal salt constituents or additives chosen for the nature of the anions, e.g. hydrides or acetylacetonate
- C04B2235/442—Carbonates
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
- C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
- C04B2235/6562—Heating rate
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
- C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
- C04B2235/6567—Treatment time
-
- 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
-
- 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
- C04B2235/9669—Resistance against chemicals, e.g. against molten glass or molten salts
- C04B2235/9692—Acid, alkali or halogen resistance
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Ceramic Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Furnace Charging Or Discharging (AREA)
Abstract
The invention discloses a preparation method of high-durability kiln furniture for a lithium battery power battery anode material, wherein the inner layer and the outer layer of the kiln furniture are made of different materials respectively; laminating and molding the substrate layer of the outer layer and the anti-corrosion layer of the inner layer, and then sintering; the laminating and integral forming technology is adopted to realize the one-step forming of the substrate layer and the anti-corrosion layer, and ensure that the blank has strong binding force, high yield and low cost; the design of the inner layer and the outer layer can obtain good heat resistance by utilizing the outer layer, can also obtain strong alkali resistance by utilizing the inner layer, and achieves the balance of the weight and the corrosion resistance of the kiln furniture on the premise of not sacrificing the mechanical strength.
Description
Technical Field
The invention relates to the technical field of lithium batteries, in particular to a preparation method of high-durability kiln furniture for a lithium battery power battery anode material.
Background
With the further improvement of the standard of the lithium-ion battery new energy automobile for the endurance mileage, the capacity of the power battery is correspondingly required to be higher, so that the improvement of the performance of the positive electrode material which plays a decisive role in the capacity of the power battery becomes a crucial part. At present, a high-nickel ternary system is preferred for a high-end power battery, and in order to meet the maximum pursuit of new energy automobile manufacturers on the energy density of the power battery, various well-known anode material manufacturers have great improvement on a material system corresponding to an anode material and a preparation process compared with a conventional power ternary system, and the improvement is mainly highlighted in two aspects: one is that the ternary system goes to nickelization (such as 811 systems or higher); and secondly, lithium hydroxide with stronger activity and higher alkalinity is introduced to replace the lithium carbonate as a lithium source material. Due to the changes of the two aspects, the high-temperature kiln furniture for bearing the anode material to be fired faces the challenge of severe high-temperature strong-alkali corrosion resistance, the service life of the traditional sagger under the condition is only 2-3 times, the production consumption cost of the anode material is increased, the production control difficulty of an anode material plant is increased, the labor intensity of production workers is increased, the production efficiency is reduced, and even the anode material is polluted due to corrosion and falling of the sagger material to influence the performance of the battery. Therefore, the development of the kiln furniture with high durability, which meets the requirements of the current lithium electrokinetic anode material process system, plays a very important role in improving the quality of the anode material and controlling the cost.
The container used in the process of synthesizing the lithium battery anode material is generally a corundum, mullite, quartz or cordierite high-temperature resistant container. The most of cordierite and corundum containers are used, the conventional ternary system anode material system and process including the subsequent 622 or 811 system can be basically and synchronously satisfied by properly increasing the high-aluminum raw material in the sagger material, but with the upgrade of the new generation high-nickel ternary process, the traditional sagger which simply increases the aluminum content and the alkaline refractory raw material is gradually not adapted for two reasons: firstly, if the raw material components with high aluminum content are increased greatly, the weight of the saggar per se is overlarge (the weight of the saggar with the specification of 330 x 100 exceeds 8 kilograms), the bearing pressure of the kiln sticks is overlarge, and the load capacity is reduced, and the serious consequences of 'broken sticks and arch furnace' are caused; secondly, lithium hydroxide is adopted as a lithium source in the novel process system, so that the activity is stronger, the alkalinity is higher, the pH value of the ternary precursor system is higher than 13, the corrosion condition to the sagger in the high-temperature sintering process is greatly increased, and the pure alumina with the content of 99 percent cannot meet the requirement of alkaline corrosion resistance. Therefore, the material system of the sagger must be redesigned, and the manufacturing process of the sagger is improved, so that the requirements of corrosion resistance and the requirements of kiln heat engineering on the weight, the size and the like of the sagger are met. Therefore, it is necessary to invent a preparation method of high-durability kiln furniture for the positive electrode material of the lithium-ion power battery, which can effectively reduce the dead weight and has excellent corrosion resistance.
Disclosure of Invention
The purpose of the invention is as follows: in order to overcome the defects in the prior art, the invention provides the preparation method of the high-durability kiln furniture for the positive electrode material of the lithium battery power battery, which can effectively reduce the dead weight and has excellent anti-corrosion performance.
The technical scheme is as follows: in order to achieve the purpose, the invention discloses a preparation method of high-durability kiln furniture for a lithium-ion power battery anode material, wherein the inner layer and the outer layer of the kiln furniture are made of different materials respectively; and laminating the substrate layer of the outer layer and the anti-corrosion layer of the inner layer for molding, and then carrying out sintering treatment.
Further, the anti-corrosion layer is arranged at the bottom of the inner side of the substrate layer and is 3-5mm thick.
Further, the substrate layer is a mixture of cordierite, mullite and kaolin.
Further, the mass fractions of the cordierite, the mullite and the kaolin are 35%, 40% and 25%, respectively.
Furthermore, the raw material of the anti-corrosion layer before sintering is a mixture of a high-aluminum high-temperature resistant material, a slightly alkaline high-temperature resistant material and an auxiliary reaction material; the auxiliary reaction material comprises any one or combination of more of zirconia, titanium dioxide, activated alumina and light magnesia powder.
Further, the high-aluminum-based high-temperature resistant material includes plate-shaped corundum.
Further, the more basic refractory material comprises an aluminum magnesium spinel.
Furthermore, the proportion of the raw materials of the anti-corrosion layer is 40 wt.% of the plate-shaped corundum powder; 18 wt.% of fused magnesia-alumina spinel micropowder; 10 wt.% of activated alumina powder, 10 wt.% of kaolin, 7 wt.% of zirconia powder, 4 wt.% of titanium dioxide, 7 wt.% of light activated magnesia powder and 3 wt.% of barium carbonate.
Further, the preparation steps of the kiln furniture are,
fully and uniformly mixing the raw materials of the substrate layer according to the proportion required by the process, and adding water for ageing treatment;
weighing the raw materials of the anti-corrosion layer according to the proportion required by the process, and uniformly mixing the raw materials in a wet ball milling mode to prepare powder;
step three, drying the powder in the step two, and then ageing the powder;
step four, integrally forming the base layer material and the corrosion-resistant layer material prepared in the step one and the step three in a laminating mode;
step five, drying the wet embryo body obtained in the step four;
and step six, putting the semi-finished product obtained in the step five into a kiln, and finishing the firing process according to a heat treatment temperature curve required by the process to finally obtain a finished kiln furniture product.
Further, the heat treatment process in the kiln furniture sintering process comprises the following steps:
(1)0～150℃，0.5℃/min；
(2)150～600℃，0.25℃/min；
(3)600～1200℃，0.5℃/min；
(4) keeping the temperature at 1200 ℃ for 4 hours;
(5)1200～1400℃，0.25℃/min；
(6) preserving heat for 6 hours at 1400 ℃;
(7) slowly cooling along with the furnace.
Has the advantages that: according to the preparation method of the high-durability kiln furniture for the lithium-ion power battery anode material, the inner layer and the outer layer of the kiln furniture are made of different materials respectively; laminating and molding the substrate layer of the outer layer and the anti-corrosion layer of the inner layer, and then sintering; the laminating and integral forming technology is adopted to realize the one-step forming of the substrate layer and the anti-corrosion layer, and ensure that the blank has strong binding force, high yield and low cost; the design of the inner layer and the outer layer can obtain good heat resistance by utilizing the outer layer, can also obtain strong alkali resistance by utilizing the inner layer, and achieves the balance of the weight and the corrosion resistance of the kiln furniture on the premise of not sacrificing the mechanical strength.
Drawings
FIG. 1 is a flow chart of kiln furniture preparation;
FIG. 2 is a sectional view of a kiln furniture structure;
FIG. 3 is a temperature profile of the firing process.
Detailed Description
The present invention will be further described with reference to the accompanying drawings.
A preparation method of high-durability kiln furniture for a lithium battery anode material is disclosed, wherein the inner layer and the outer layer of the kiln furniture are made of different materials respectively; laminating and molding the substrate layer of the outer layer and the anti-corrosion layer of the inner layer, and then sintering; the laminating treatment ensures that the blank has strong binding force, high yield and low cost; the design of the inner layer and the outer layer can obtain good heat resistance by utilizing the outer layer and strong alkali resistance by utilizing the inner layer, thereby achieving the balance of the weight and the performance of the kiln furniture. The anti-corrosion layer is specifically arranged at the bottom of the inner side of the substrate layer, and the thickness of the anti-corrosion layer is 3-5 mm; as shown in fig. 2, the hatched portions represent the portions of the base layer and the black striped portions inside the base layer represent the corrosion resistant layer.
The base layer is a mixture of cordierite, mullite and kaolin, the mixture is mixed according to the mass fractions of 35%, 40% and 25%, the weight of the sagger can be controlled between 5Kg and 6Kg after the sagger and subsequent anti-corrosion layer materials are integrally pressed and fired, the requirement of a high-temperature kiln on the weight of the sagger is completely met, the safe and reliable operation of the kiln is ensured under the condition that the anode material is sufficiently loaded, and the severe result of breakage of the stick is avoided.
The raw material of the anti-corrosion layer before sintering is a mixture of a high-aluminum high-temperature resistant material, a slightly-alkaline high-temperature resistant material and an auxiliary reaction material; the auxiliary reaction material comprises any one or combination of more of zirconia, titanium dioxide, activated alumina and light magnesia powder.
The core principle of the design of the anti-corrosion material system is that the anti-alkali product is generated in situ through a high-aluminum material system (plate-shaped corundum), a alkalescent material (magnesia-alumina spinel), a sagger sintering process reactive material system (zirconia, titanium dioxide, activated alumina, light magnesia powder) through a high-temperature reaction: magnesium aluminate spinel, magnesium zirconium composite oxide; the granularity and the mass fraction of each component are as follows:
40 wt.% of plate-shaped corundum powder (40-70 microns); 18 wt.% of fused magnesia-alumina spinel micropowder (40-70 microns); 10 wt.% of activated alumina powder (5-10 micrometers), 10 wt.% of kaolin (5-10 micrometers), 7 wt.% of zirconia powder (chemical zirconium, 5-10 micrometers), 4 wt.% of titanium dioxide (1-5 micrometers), 7 wt.% of light activated magnesium oxide powder (10-40 micrometers), and 3 wt.% of barium carbonate.
The preparation steps of the kiln furniture are shown as the attached figure 1:
fully and uniformly mixing the raw materials of the substrate layer according to the proportion required by the process, and adding water for ageing treatment, wherein the ageing time is more than 24 hours;
weighing the raw materials of the anti-corrosion layer according to the proportion required by the process, and uniformly mixing the raw materials in a wet ball milling mode to prepare powder; for example, the total weight of the corrosion-resistant material is weighed to be 10 kg, and correspondingly 10 kg of water is placed in a ball mill for full ball milling and mixing for more than 24 hours, so that the qualified particle size and uniform mixing are ensured;
step three, placing the powder in the step two in a drying room for drying treatment, monitoring the water content of a material system through a tester, stopping drying when the water content of the material system reaches 3% -6%, and then placing the powder in a bag with a plastic lining for ageing;
step four, integrally forming the base layer material and the corrosion-resistant layer material prepared in the step one and the step three in a laminating mode; the anti-corrosion material is arranged at the bottom of the sagger, and the thickness of the anti-corrosion material is controlled within 3-5 mm;
placing the wet embryo body obtained in the step four in a drying room for drying treatment for 24 hours;
and step six, putting the semi-finished product obtained in the step five into a track kiln furnace, and finishing the firing process according to a heat treatment temperature curve required by the process to finally obtain a sagger kiln furniture finished product.
The heat treatment process of the kiln furniture firing process is shown as the attached figure 3:
(1) 0-150 ℃ and 0.5 ℃/min; the aim is to slowly remove the water in the green body and prevent drying cracking;
(2) 0.25 ℃/min at the temperature of 150-600 ℃; aims to slowly remove organic components in the green body and prevent the gas from being violently volatilized to generate cracking;
(3) 600-1200 ℃ and 0.5 ℃/min; the purpose is to complete the primary sintering of the low-melting-point component;
(4) keeping the temperature at 1200 ℃ for 4 hours; the purpose is to realize the full in-situ chemical reaction of the components of the corrosion-resistant layer;
(5) 1200-1400 ℃ and 0.25 ℃/min; the purpose is to realize uniform sintering of the substrate layer and the corrosion-resistant layer;
(6) preserving heat for 6 hours at 1400 ℃; the purpose is to realize sufficient sintering of the substrate layer and the corrosion-resistant layer and ensure that the bonding strength meets the design requirement;
(7) slowly cooling along with the furnace; the substrate layer and the corrosion-resistant layer are prone to shrinkage cracking due to inconsistent thermal expansion coefficients, and a slow cooling rate is beneficial to reducing the internal stress level.
Performance comparison test conditions
Note: the corrosion performance test is 811 series ternary anode material, and lithium source material adopts lithium hydroxide.
The phenomenon that the sagger with the anti-corrosion layer peels and corrodes for the first time is shown in the 25 th time, and compared with the sagger without the anti-corrosion layer, the sagger with the anti-corrosion layer peels and corrodes for the 5 th time, the corrosion resistance of the sagger is greatly improved; meanwhile, the performances of the sagger with the anti-corrosion layer in the aspects of thermal shock resistance, normal-temperature fracture resistance and high-temperature fracture resistance are not weakened.
And (4) conclusion: the sagger with the anti-corrosion layer obviously enhances the strong alkali corrosion resistance, greatly improves the capability of sintering the lithium hydroxide series high-nickel ternary cathode material (811) by the sagger, provides a solid guarantee for producing the high-quality high-nickel ternary cathode material by a cathode material factory, greatly saves the consumption of kiln furniture of the cathode material, and has great market application and popularization values.
The above description is only of the preferred embodiments of the present invention, and it should be noted that: it will be apparent to those skilled in the art that various modifications and adaptations can be made without departing from the principles of the invention and these are intended to be within the scope of the invention.
Claims (10)
1. A preparation method of high-durability kiln furniture for a lithium-ion power battery anode material is characterized by comprising the following steps of: the inner layer and the outer layer of the kiln furniture are made of different materials respectively; and laminating the substrate layer of the outer layer and the anti-corrosion layer of the inner layer for molding, and then carrying out sintering treatment.
2. The method for manufacturing high-durability kiln furniture for the positive electrode material of a lithium-ion power battery according to claim 1, characterized in that: the anti-corrosion layer is arranged at the bottom of the inner side of the substrate layer and is 3-5mm thick.
3. The method for manufacturing high-durability kiln furniture for the positive electrode material of a lithium-ion power battery according to claim 1, characterized in that: the substrate layer is a mixture of cordierite, mullite and kaolin.
4. The method for manufacturing high-durability kiln furniture for the positive electrode material of a lithium-ion power battery according to claim 3, characterized in that: the mass fractions of the cordierite, the mullite and the kaolin are respectively 35%, 40% and 25%.
5. The method for manufacturing high-durability kiln furniture for the positive electrode material of a lithium-ion power battery according to claim 1, characterized in that: the raw material of the anti-corrosion layer before sintering is a mixture of a high-aluminum high-temperature resistant material, a slightly-alkaline high-temperature resistant material and an auxiliary reaction material; the auxiliary reaction material comprises any one or combination of more of zirconia, titanium dioxide, activated alumina and light magnesia powder.
6. The method for manufacturing high-durability kiln furniture for the positive electrode material of a lithium-ion power battery according to claim 5, characterized in that: the high-aluminum high-temperature resistant material comprises plate-shaped corundum.
7. The method for manufacturing high-durability kiln furniture for the positive electrode material of a lithium-ion power battery according to claim 6, characterized in that: the more basic refractory material comprises an aluminum magnesium spinel.
8. The method for manufacturing high-durability kiln furniture for the positive electrode material of a lithium-ion power battery according to claim 7, characterized in that: the raw material proportion of the anti-corrosion layer is 40 wt.% of the plate-shaped corundum powder; 18 wt.% of fused magnesia-alumina spinel micropowder; 10 wt.% of activated alumina powder, 10 wt.% of kaolin, 7 wt.% of zirconia powder, 4 wt.% of titanium dioxide, 7 wt.% of light activated magnesia powder and 3 wt.% of barium carbonate.
9. The method for manufacturing high-durability kiln furniture for the positive electrode material of a lithium-ion power battery according to claim 1, characterized in that: the preparation steps of the kiln furniture are as follows,
fully and uniformly mixing the raw materials of the substrate layer according to the proportion required by the process, and adding water for ageing treatment;
weighing the raw materials of the anti-corrosion layer according to the proportion required by the process, and uniformly mixing the raw materials in a wet ball milling mode to prepare powder;
step three, drying the powder in the step two, and then ageing the powder;
step four, integrally forming the base layer material and the corrosion-resistant layer material prepared in the step one and the step three in a laminating mode;
step five, drying the wet embryo body obtained in the step four;
and step six, putting the semi-finished product obtained in the step five into a kiln, and finishing the firing process according to a heat treatment temperature curve required by the process to finally obtain a finished kiln furniture product.
10. The method for manufacturing high-durability kiln furniture for the positive electrode material of a lithium-ion power battery according to claim 1, characterized in that: the heat treatment process in the kiln furniture firing process comprises the following steps:
(1)0～150℃，0.5℃/min；
(2)150～600℃，0.25℃/min；
(3)600～1200℃，0.5℃/min；
(4) keeping the temperature at 1200 ℃ for 4 hours;
(5)1200～1400℃，0.25℃/min；
(6) preserving heat for 6 hours at 1400 ℃;
(7) slowly cooling along with the furnace.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010044845.6A CN111233447A (en) | 2020-01-16 | 2020-01-16 | Preparation method of high-durability kiln furniture for positive electrode material of lithium-ion battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010044845.6A CN111233447A (en) | 2020-01-16 | 2020-01-16 | Preparation method of high-durability kiln furniture for positive electrode material of lithium-ion battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN111233447A true CN111233447A (en) | 2020-06-05 |
Family
ID=70871166
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010044845.6A Pending CN111233447A (en) | 2020-01-16 | 2020-01-16 | Preparation method of high-durability kiln furniture for positive electrode material of lithium-ion battery |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111233447A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112680037A (en) * | 2020-12-24 | 2021-04-20 | 湖北华联耐火材料有限公司 | Anticorrosive paint and sagger coated with same |
| CN112759377A (en) * | 2021-02-07 | 2021-05-07 | 山东万乔集团有限公司 | Sagger for roasting lithium battery positive electrode material and preparation method thereof |
| CN113200752A (en) * | 2021-04-02 | 2021-08-03 | 武汉科技大学 | Shaft kiln furnace lining for roasting lithium battery anode material and preparation method thereof |
| CN115043650A (en) * | 2022-08-15 | 2022-09-13 | 天津巴莫科技有限责任公司 | Casket-like bowl and preparation method thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103502182A (en) * | 2011-03-30 | 2014-01-08 | 东京窑业株式会社 | Heat treatment vessel for lithium-containing compound and method for producing same |
| CN105130389A (en) * | 2015-08-26 | 2015-12-09 | 湖北天鸿耐火材料有限公司 | Strong-alkali corrosion-resistant high-temperature-resistant container for cathode material of lithium battery, interface layer of container and preparation method for container |
| 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 |
| CN108101558A (en) * | 2017-12-25 | 2018-06-01 | 浙江大学 | Compound saggar, preparation method and applications |
| CN108373324A (en) * | 2018-03-28 | 2018-08-07 | 广东山摩新材料科技有限公司 | A kind of lightweight saggar and preparation method thereof for anode material of lithium battery roasting |
| CN110540418A (en) * | 2019-09-20 | 2019-12-06 | 湖南金铠新材料科技有限公司 | Sagger special for sintering lithium battery positive electrode material and preparation method thereof |
-
2020
- 2020-01-16 CN CN202010044845.6A patent/CN111233447A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103502182A (en) * | 2011-03-30 | 2014-01-08 | 东京窑业株式会社 | Heat treatment vessel for lithium-containing compound and method for producing same |
| CN105130389A (en) * | 2015-08-26 | 2015-12-09 | 湖北天鸿耐火材料有限公司 | Strong-alkali corrosion-resistant high-temperature-resistant container for cathode material of lithium battery, interface layer of container and preparation method for container |
| 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 |
| CN108101558A (en) * | 2017-12-25 | 2018-06-01 | 浙江大学 | Compound saggar, preparation method and applications |
| CN108373324A (en) * | 2018-03-28 | 2018-08-07 | 广东山摩新材料科技有限公司 | A kind of lightweight saggar and preparation method thereof for anode material of lithium battery roasting |
| CN110540418A (en) * | 2019-09-20 | 2019-12-06 | 湖南金铠新材料科技有限公司 | Sagger special for sintering lithium battery positive electrode material and preparation method thereof |
Non-Patent Citations (3)
| Title |
|---|
| PENGTAO ZHAI ET.AL: "Interactions between mullite saggar refractories and Li-ion battery cathode materials during calcination", 《JOURNAL OF THE EUROPEAN CERAMIC SOCIETY》 * |
| 刘波: "锂离子电池正极材料匣钵的应用研究", 《中国优秀硕士论文电子期刊网》 * |
| 陈洋 等: "堇青石-莫来石质匣钵材料抗热震性和抗侵蚀性研究", 《硅酸盐通报》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112680037A (en) * | 2020-12-24 | 2021-04-20 | 湖北华联耐火材料有限公司 | Anticorrosive paint and sagger coated with same |
| CN112759377A (en) * | 2021-02-07 | 2021-05-07 | 山东万乔集团有限公司 | Sagger for roasting lithium battery positive electrode material and preparation method thereof |
| CN113200752A (en) * | 2021-04-02 | 2021-08-03 | 武汉科技大学 | Shaft kiln furnace lining for roasting lithium battery anode material and preparation method thereof |
| CN115043650A (en) * | 2022-08-15 | 2022-09-13 | 天津巴莫科技有限责任公司 | Casket-like bowl and preparation method thereof |
| CN115043650B (en) * | 2022-08-15 | 2022-11-15 | 天津巴莫科技有限责任公司 | Casket-like bowl and preparation method thereof |
| WO2024036648A1 (en) * | 2022-08-15 | 2024-02-22 | 天津巴莫科技有限责任公司 | Sagger and preparation method therefor |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111233447A (en) | Preparation method of high-durability kiln furniture for positive electrode material of lithium-ion battery | |
| CN109467422A (en) | Dedicated high circulation special cermacis crucible of a kind of lithium electricity and preparation method thereof | |
| JP2019121601A (en) | Lithium ion battery electrode material firing pot and protective layer of the same | |
| CN113372105B (en) | Double-layer structure sagger for lithium battery positive electrode material and preparation method of sagger | |
| CN112028650A (en) | Sagger for lithium ion battery anode material | |
| CN108101558B (en) | Composite sagger, preparation method and application thereof | |
| CN105698542A (en) | Lithium battery high-temperature corrosion resistance laminar saggar and preparation method thereof | |
| CN112010661B (en) | Sagger for lithium battery positive electrode material and preparation method thereof | |
| CN112225558B (en) | Gradient composite technology ceramic tile for glass kiln field and preparation method thereof | |
| CN107892581B (en) | High-strength corrosion-resistant zirconia corundum honeycomb ceramic body and preparation method thereof | |
| CN105645977A (en) | Air brick for special steel refining and preparation method thereof | |
| CN110746180A (en) | Sintered aluminum-chromium-zirconium sliding plate brick for copper smelting anode furnace and preparation method thereof | |
| CN114230371B (en) | Composite coating for improving corrosion resistance of sagger surface and prolonging service life | |
| CN115340392B (en) | Sagger for long-life lithium battery positive electrode material and preparation method thereof | |
| CN114195533A (en) | Sagger for lithium ion battery anode material and preparation method thereof | |
| CN108610024A (en) | A kind of saggar and preparation method thereof for anode material for lithium-ion batteries roasting | |
| CN110207499A (en) | Anode material of lithium battery sintering saggar based on magnesium aluminate spinel colloidal sol and preparation method thereof | |
| CN106365647A (en) | Castable | |
| CN108083823B (en) | Composite sagger, preparation method and application thereof | |
| CN106365654A (en) | Anti lithium-ion electric material erosion fire-clay crucible added with ZrN-SiAlON | |
| CN108083824B (en) | Corrosion-resistant sagger, preparation method and application thereof | |
| CN111718207A (en) | Preparation method of modified cordierite-mullite refractory material | |
| CN115340409B (en) | Sagger coating for lithium battery positive electrode material and preparation method of sagger coating | |
| CN112094127B (en) | Manufacturing process of kyanite tailing series sagger | |
| CN114315392B (en) | Fluid stirring purification jointed board preparation material and fluid stirring purification jointed board preparation process |
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 | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20200605 |