CN111102844A - Preparation method of sagger for sintering lithium battery positive electrode material - Google Patents
Preparation method of sagger for sintering lithium battery positive electrode material Download PDFInfo
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- 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
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
- C04B35/56—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides
- C04B35/565—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides based on silicon carbide
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- 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
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- 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
- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
- C04B35/628—Coating the powders or the macroscopic reinforcing agents
- C04B35/62802—Powder coating materials
- C04B35/62828—Non-oxide ceramics
- C04B35/62831—Carbides
- C04B35/62834—Silicon carbide
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- 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
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—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
- C04B2235/48—Organic compounds becoming part of a ceramic after heat treatment, e.g. carbonising phenol resins
- C04B2235/483—Si-containing organic compounds, e.g. silicone resins, (poly)silanes, (poly)siloxanes or (poly)silazanes
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F27—FURNACES; KILNS; OVENS; RETORTS
- F27M—INDEXING SCHEME RELATING TO ASPECTS OF THE CHARGES OR FURNACES, KILNS, OVENS OR RETORTS
- F27M2003/00—Type of treatment of the charge
- F27M2003/04—Sintering
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Abstract
The invention relates to the technical field of sagger kiln furniture preparation, in particular to a preparation method of a sagger for sintering a lithium battery anode material, which comprises the following steps: s1, mixing raw materials; s2, forming; s3, drying; s4, preheating; and S5, sintering. The sagger prepared by the method has the advantages of good corrosion resistance, super-long service life, smaller thermal expansion coefficient, excellent thermal shock stability and certain strength, and the positive electrode material is easy to peel off when contacting with the sagger, so that the sagger is not peeled, does not drop slag and is pollution-free in the using process; the energy-saving and consumption-reducing brick has the inherent advantages of energy saving and consumption reduction, and is an ideal substitute for the mullite sagger at present; the sintering process is suitable for lithium cobaltate, ternary materials, lithium manganate, lithium iron phosphate and other lithium battery positive electrode materials, the sintering process can resist high temperature of more than 1200 ℃, and the service life of the sintering process is 20 times that of domestic saggars and 3-4 times that of similar saggars abroad.
Description
Technical Field
The invention relates to the technical field of sagger kiln furniture preparation, in particular to a preparation method of a sagger for sintering a lithium battery positive electrode material.
Background
The sagger is made up by using refractory clay material and making it into various specifications through high-temp. roasting. The sagger is one of important kiln furniture for sintering the lithium battery anode material. The anode materials of various batteries are firstly put into a saggar and then put into a kiln for roasting.
Sagger used in China can be classified into acid-resistant sagger and alkali-resistant sagger on the aspect of erosion resistance. The acid-resistant sagger is mainly a silicon-aluminum sagger, and the raw materials generally used by the sagger are acid materials, so that the sagger has a good resistance effect on the erosion of the acid materials; the alkali-resistant sagger is mainly characterized in that a part of alkaline oxide or alkaline material is added into a refractory material, so that the sagger has good erosion resistance on the alkaline material, and the service life of the sagger is prolonged. Currently, saggers used domestically are mainly from four countries, japan, germany, korea and china. Among them, the sagger in japan is the most excellent in the use of the sagger material, and in germany, the saggers in korea and china are slightly weak in this respect. For example, in the process of using the saggar material for sintering the lithium ion battery cathode material, the common lithium battery cathode material such as the saggars in Japan and Germany is used for more than 35-40 times, the saggars in China and Korea are used for about 30-40 times, and the difference in the aspect is not great, but in the lithium cobaltate or ternary cathode material with relatively serious erosion, the saggar in Japan and Germany is far superior to that of the national saggar manufacturers in terms of erosion resistance and thermal shock stability. The following key common problems occur in the use process of the sagger for the lithium battery positive electrode material:
(1) the service life of the sagger material is short.
The sagger used in the process of synthesizing the lithium ion battery anode material is generally a corundum-based, mullite-based, quartz-based and cordierite-based high-temperature resistant sagger. Cordierite and corundum sagger are the most used. However, the raw materials used for synthesizing the lithium ion cathode material can be decomposed in the synthesis process to generate lithium oxide with strong permeability and reactivity to corrode the high-temperature resistant sagger, and on the other hand, when the sagger material is rapidly cooled after high temperature, cracks are easily generated on the sagger along with the increase of the using times, the thermal shock stability of the sagger is damaged, and the service life of the high-temperature resistant sagger can be greatly reduced. The general cordierite high-temperature resistant sagger has excellent erosion resistance and thermal shock stability, can be used for more than 100 times under the oxidizing atmosphere of 1350 ℃, but has the service life of only about 5-6 times even under the temperature of 1000 ℃ when being used for high-temperature solid-phase synthesis of lithium cobaltate; the use temperature of the mullite high-temperature resistant sagger is as high as 1760 ℃, and when the mullite high-temperature resistant sagger is used for high-temperature solid-phase synthesis of lithium cobaltate, the service life of the high-temperature solid-phase synthesis lithium cobaltate is only about 4-5 times; the use temperature of the corundum high-temperature resistant sagger is up to 1700 ℃, the service life of the corundum high-temperature resistant sagger is only about 5 times when the corundum high-temperature resistant sagger is used for high-temperature solid-phase synthesis of lithium cobaltate, and the service life of the quartz high-temperature resistant sagger is only about 2 times when the quartz high-temperature resistant sagger is used for synthesizing lithium cobaltate. According to statistics, if manufacturers for synthesizing lithium cobaltate by high-temperature solid phase in China directly use the high-temperature resistant saggars as kilns for production, the average cost spent on replacing the high-temperature resistant saggars per year reaches billions of yuan, and meanwhile, the high-temperature resistant saggars cause great harm to the environment and do not meet the requirements of sustainable development. On the other hand, because the scale of the current lithium cobaltate synthesis factory in China is small and the economic strength is not strong, the high-temperature resistant saggars which do not have high anti-corrosion performance are generally used, and the existing high-temperature resistant saggar kiln can not be replaced in large batch.
(2) The sagger material has poor erosion resistance
The corrosion resistance is an important index for the use of saggars for lithium battery positive electrode materials. Eutectic corrosion principle of lithium ion battery: the lithium battery anode material for roasting is mostly in a fine powder shape, the permeability is strong, lithium ions in the material belong to strong alkaline substances, and the strong alkaline substances have strong corrosivity on the saggar material. The conventional sagger material for roasting the lithium battery cathode material is basically used for roasting the lithium battery cathode material by simply changing the shape of a sagger of a common roasted product, and the sagger material is used for roasting the lithium battery cathode material. For example: in order to produce LiMnO2, which is in increasing demand, a mixture of a lithium compound (lithium hydroxide or lithium nitrate) and a manganese compound (manganese oxide, manganese hydroxide or manganese carbonate) as raw materials is charged into a sintering container (generally called a sagger or a beaker) made of a heat-resistant ceramic material, and the sintering is carried out under a temperature condition of about 1000 ℃. The following phenomena occur when LiMnO2 is produced at this sintering temperature: in this sintering process, the lithium compound is melted, and further, lithium element derived from the compound is evaporated under high temperature conditions and impregnated into the heat-resistant ceramic material constituting the container for sintering, and the microscopic structure of the sagger is destroyed, so that the sagger cannot be used many times.
(3) Poor thermal shock stability of sagger material
In the use process of the sagger material, the sagger generates cracks, peels off and even cracks due to the rapid change of the environmental temperature, the destructive effect limits the heating and cooling rates of the sagger material and the kiln, and also limits the strengthening of the operation of the kiln, and the sagger material and the kiln are one of the main reasons for quick damage.
The expansion or contraction of the sagger material occurs with the rise and fall of the temperature, and if the contraction and expansion are restrained and can not develop freely, the stress can be generated in the sagger material, the stress is called thermal stress, and the stress is generated not only under the mechanical constraint, but also when the temperature gradient occurs in the homogeneous material and the thermal expansion coefficient of each phase of the solid of the heterogeneous material is different.
The sagger material is a heterogeneous brittle material, and has poor thermal shock stability due to large thermal expansion, small thermal conductivity and elastic modulus and poor ability of resisting thermal stress damage. Particularly, after one cycle is finished, sometimes due to the requirement of industrial production, cold air and air are directly introduced into the kiln in the cooling process of the kiln, which puts higher requirements on the thermal shock stability of the sagger material. Although the shape of the sagger material is not the essential attribute of the material, the sagger material also has important influence on the thermal shock stability of the product, the poor appearance structure can cause stress concentration and serious uneven temperature distribution of the sagger material, the thermal shock resistance of the sagger material is weakened, and finally, the uniformity of the anode material is caused by uneven reaction temperature of the anode reaction raw material of the lithium battery. Factors actually affecting the thermal shock resistance of the refractory are complex, and one factor cannot be considered singly, and the influence of the factors must be considered comprehensively.
(4) The sagger material has low strength
The kiln furniture is typically stacked or grilled inside the kiln. Each piece of kiln furniture bears the weight of the kiln furniture and the weight of the green body, and is also subjected to mechanical acting force during loading and unloading, so that the kiln furniture needs to have enough mechanical strength.
At high temperatures, the neutral action causes plastic deformation of the kiln furniture, particle displacement and structural changes, so that the kiln furniture requires sufficient high-temperature mechanical strength, a high refractoriness under load and creep resistance, which on the one hand is dependent on its shape, structural dimensions and on the other hand on the conditions of use and, more importantly, on the properties of the material itself. This is true of the sagger material, which can have good mechanical strength even under high temperature load while maintaining its own strength.
(5) The sagger material peels off, falls off slag and is easy to pollute products
In the using process of the saggar, during the synthesis process of the Li-and Co-containing cathode material, the Li-containing compound is corroded on the saggar before the Co-containing compound to form a composite compound and precipitate out of the composite compound, so that the peeling phenomenon is generated, and the product is polluted.
Therefore, in order to meet the demand of the lithium battery cathode material which is increasingly demanded, a novel sagger must be developed, so that the sagger has good erosion resistance, a small thermal expansion coefficient, excellent thermal shock stability and certain strength, the cathode material is easy to peel off when contacting with the sagger, the sagger does not peel off, the sagger does not drop slag, and the product is not easy to pollute. In view of the above problems, a sagger for a lithium battery positive electrode material is developed to have the excellent performance close to or as described above, and has important significance and industrial value.
Disclosure of Invention
In view of the above problems, an object of the present invention is to provide a method for preparing a sagger for firing a lithium battery positive electrode material, wherein the sagger prepared by the method has good corrosion resistance, an ultra-long service life, a small thermal expansion coefficient, excellent thermal shock stability and a certain strength, and the positive electrode material is easy to peel off when contacting with the sagger, and the sagger does not peel or fall slag and is pollution-free in the using process. The specific technical scheme is as follows:
a preparation method of a sagger for firing a lithium battery anode material comprises the following steps:
s1, mixing raw materials, namely uniformly mixing high-purity silicon carbide and an adhesive according to the proportion of the raw materials until the surfaces of dried granular materials are wetted, detecting whether the mixed materials reach the standard, and forcibly kneading the materials into a mass by hands to obtain a qualified non-sticky hand, thus obtaining a mixture.
S2, molding, namely after the surface of the mixture is modified (polyether modified polydimethylsilane and α -SiC micropowder are fully mixed according to a certain proportion, heating is carried out at 1200 ℃, a layer of nano SiC is generated on the surface of α -SiC micropowder, and the sintering temperature of the recrystallized silicon carbide material is effectively reduced), and the mixture is prepared into a sagger green body by adopting a grouting molding method or an extrusion molding method.
And S3, drying, namely placing the sagger green body prepared in the step S2 in a drying room at the temperature of 60-65 ℃ for drying for 24 hours.
S4, preheating, namely placing the sagger green body processed by the sagger green body processed in the step S3 into a drying furnace, heating to 500 ℃ within 20-30 minutes, and preserving heat for 30-60 minutes to remove crystal water in the matrix material.
S5, sintering, namely conveying the sagger green body subjected to the preheating treatment in the step S4 into a calcining furnace to perform evaporation-condensation recrystallization at the calcining temperature of 2000-2500 ℃ under the protection of vacuum or inert atmosphere, so as to realize complete phase change from a β phase to a α phase, and generate particle intergrowth at particle contact positions to form a sintered body, and naturally cooling and discharging the sintered body out of the kiln to obtain a sagger finished product.
Furthermore, the raw materials in step S1 are mixed in a ratio of high-purity silicon carbide to binder of 100 (8-15).
Further, the ratio of high purity silicon carbide to binder was 100: 9.
Further, the binder is a silicone resin.
Further, in the high purity silicon carbide of step S1, the SiC content is 99% or more.
Further, the fineness of the high-purity silicon carbide in the step S1 is below 10 μm.
Further, the density of the raw sagger in the step S2 is 2.73g/cm 3.
More preferably, the calcination temperature in step S5 is 2420 ℃.
Further, the inert atmosphere in step S5 is an argon atmosphere.
The invention has the following advantages:
the density and strength of the silicon carbide product are greatly improved by adopting the organic silicon adhesive and a unique sintering process. The organosilicon adhesive can generate silicon carbide in situ with carbon during high-temperature sintering, liquefy and fill gaps, generate a crosslinking effect, and improve the density and strength of the final recrystallized silicon carbide.
The high-purity silicon carbide sagger prepared by the recrystallization technology is introduced into the lithium battery positive electrode material production industry, the advantages of corrosion resistance, super-long service life, no peeling, slag falling and no pollution in the using process of the silicon carbide are fully utilized, and the high-purity silicon carbide sagger is combined with the inherent advantages of small self heat capacity (the molar heat capacity is 27.69J/mol.K, and the mullite is 368J/mol.K), strong heat radiation capability and energy conservation and consumption reduction, and is an ideal substitute of the existing mullite sagger.
The method is suitable for sintering lithium cobaltate, ternary materials, lithium manganate, lithium iron phosphate and other lithium battery positive electrode materials. The sagger has no problems of peeling, slag falling, pollution of firing materials and the like in the using process, can resist high temperature of more than 1200 ℃, and has the service life which is 20 times that of the domestic sagger and 3-4 times that of the similar saggers abroad.
Drawings
FIG. 1 is a graph of the morphology of a high purity silicon carbide sagger made in accordance with the present invention before use and after 115 reuses (523 materials);
FIG. 2 is a table showing the composition analysis of the dense protective layer on the sagger made by the present invention;
FIG. 3 shows XRD spectra before and after use of the lower layer of the inner surface of the sagger prepared by the invention
Detailed Description
The present invention will be described in further detail with reference to examples.
The first embodiment is as follows:
a preparation method of a sagger for firing a lithium battery anode material comprises the following steps:
s1, mixing raw materials, namely uniformly mixing high-purity silicon carbide and an adhesive according to the proportion of 100:12 until the surfaces of dried granular materials are wetted, detecting whether the mixed materials reach the standard, and forcibly kneading the materials into a mass by hands to obtain a qualified non-sticky hand, thus obtaining a mixture; wherein the SiC content of the high-purity silicon carbide is more than 99 percent, and the fineness of the high-purity silicon carbide is less than 10 mu m.
And S2, forming, namely after surface modification is carried out on the mixture, preparing the mixture into a sagger green body by adopting a grouting forming method or an extrusion forming method. The density of the green sagger was 2.75g/cm 3.
And S3, drying, namely placing the sagger green body prepared in the step S2 in a drying room at 62 ℃ for drying for 24 hours.
S4, preheating, namely placing the sagger green body processed by the sagger green body processed in the step S3 into a drying furnace, heating to 500 ℃ within 30 minutes, and preserving heat for 35 minutes to remove crystal water in the matrix material.
S5, sintering, namely conveying the sagger green body subjected to the preheating treatment in the step S4 into a calcining furnace to perform evaporation-condensation recrystallization at the calcining temperature of 2420 ℃ under the protection of vacuum or argon atmosphere, so as to realize complete phase change from a β phase to a α phase, and generate particle intergrowth at particle contact positions to form a sintered body, and naturally cooling and discharging the sintered body out of the kiln to obtain a sagger finished product.
Example two:
a preparation method of a sagger for firing a lithium battery anode material comprises the following steps:
s1, mixing raw materials, namely uniformly mixing high-purity silicon carbide and an adhesive according to the proportion of 100:9 until the surfaces of dried granular materials are wetted, detecting whether the mixed materials reach the standard, and forcibly kneading the materials into a mass by hands to obtain a qualified non-sticky hand, thus obtaining a mixture; wherein the SiC content of the high-purity silicon carbide is more than 99 percent, and the fineness of the high-purity silicon carbide is less than 10 mu m.
And S2, forming, namely after surface modification is carried out on the mixture, preparing the mixture into a sagger green body by adopting a grouting forming method or an extrusion forming method. The density of the green sagger was 2.73g/cm 3.
And S3, drying, namely placing the sagger green body prepared in the step S2 in a drying room at 65 ℃ for drying for 24 hours.
S4, preheating, namely placing the sagger green body processed by the sagger green body processed in the step S3 into a drying furnace, heating to 500 ℃ within 25 minutes, and preserving heat for 50 minutes to remove crystal water in the matrix material.
S5, sintering, namely conveying the sagger green body subjected to the preheating treatment in the step S4 into a calcining furnace to perform evaporation-condensation recrystallization at the calcining temperature of 2420 ℃ under the protection of vacuum or argon atmosphere, so as to realize complete phase change from a β phase to a α phase, and generate particle intergrowth at particle contact positions to form a sintered body, and naturally cooling and discharging the sintered body out of the kiln to obtain a sagger finished product.
According to the invention, by utilizing the characteristics of high mechanical strength, high temperature resistance, good thermal shock resistance, good oxidation resistance, corrosion resistance, low thermal expansion coefficient, high thermal conductivity and the like of silicon carbide, SiC powder synthesized by an Acheson method is used as a raw material, and after the raw material of the coarse and fine SiC powder is molded, evaporation-condensation recrystallization is carried out under the protection of high temperature (2420 ℃) and vacuum or argon atmosphere, and particles are intergrown at particle contact positions to form a sintered body. Therefore, the recrystallized silicon carbide has no shrinkage and no liquid phase in the sintering process, and finally forms a high-purity silicon carbide product which has a network skeleton structure with a plurality of holes and communicated pores and has certain strength. It does not have any shrinkage during sintering and therefore has a high porosity.
After long-term use, the sagger prepared by the method has no problems of peeling, slag falling, pollution to fired materials and the like, has the service life of more than 100 times (the ternary material 523), and far exceeds the traditional mullite sagger and cordierite sagger in the market.
As can be seen from comparison of FIG. 1, after 125 times of use, the high-purity silicon carbide sagger has no surface peeling and slag falling, and after artificial damage, observation of the side surface shows that a thin layer of about 0.1mm is generated on the surface of the sagger, the thin layer is composed of a compact protective layer and is composed of lithium carbonate, lithium silicate and SiC compound through elemental analysis, and the analysis result is shown in FIG. 2. The reason for this is that the lithium carbonate and lithium silicate are generated by the reaction of SiC and alkaline lithium salt in a long service life, and the lithium salt generated by the reaction can permeate into and be firmly adsorbed on the inner surface of the sagger due to the many micropores of the high-purity silicon carbide, so that the sagger has a good corrosion resistance.
In addition, neither lithium carbonate nor lithium silicate can continuously corrode the high-purity silicon carbide at the lower layer of the inner surface, and the protective layer can well inhibit Li from permeating into the sagger during the reaction, thereby playing a role in corrosion resistance. The inner surface underlayer composition was measured by XRD and found to be pure high purity silicon carbide, not corroded, as shown in fig. 2.
In conclusion, the high-purity silicon carbide sagger has the advantages of corrosion resistance, super-long service life, no peeling and slag falling in the using process, no pollution and the like, and is combined with the inherent advantages of small heat capacity (the molar heat capacity is 27.69J/mol.K, and the mullite is 368J/mol.K) of silicon carbide, strong heat radiation capability, energy conservation and consumption reduction, and is an ideal substitute of the existing mullite sagger.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (9)
1. A preparation method of a sagger for firing a lithium battery anode material is characterized by comprising the following steps:
s1, mixing raw materials, namely uniformly mixing high-purity silicon carbide and an adhesive according to the proportion of the raw materials until the surfaces of dried granular materials are wetted, detecting whether the mixed materials reach the standard, and forcibly kneading the materials into a mass by hands to obtain a qualified non-sticky hand, thus obtaining a mixture;
s2, forming, namely after surface modification is carried out on the mixture, preparing the mixture into a sagger green body by adopting a grouting forming method or an extrusion forming method;
s3, drying, namely placing the sagger green body prepared in the step S2 in a drying room at the temperature of 60-65 ℃ for drying for 24 hours;
s4, preheating, namely placing the sagger green body processed by the sagger green body processed in the step S3 into a drying furnace, heating to 500 ℃ within 20-30 minutes, and preserving heat for 30-60 minutes to remove crystal water in the matrix material;
s5, sintering, namely conveying the sagger green body subjected to the preheating treatment in the step S4 into a calcining furnace to perform evaporation-condensation recrystallization at the calcining temperature of 2000-2500 ℃ under the protection of vacuum or inert atmosphere, so as to realize complete phase change from a β phase to a α phase, and generate particle intergrowth at particle contact positions to form a sintered body, and naturally cooling and discharging the sintered body out of the kiln to obtain a sagger finished product.
2. The method for preparing the sagger for firing the lithium battery positive electrode material as claimed in claim 1, wherein the raw material ratio in the step S1 is that the ratio of the high-purity silicon carbide to the binder is 100 (8-15).
3. The method for preparing a sagger for firing a lithium battery positive electrode material as claimed in claim 2, wherein the ratio of the high purity silicon carbide to the binder is 100: 9.
4. The method for producing the sagger for firing a positive electrode material of a lithium battery as claimed in any one of claims 1 to 3, wherein the binder is a silicone resin.
5. The method for preparing a sagger for firing a lithium battery positive electrode material as claimed in claim 1, wherein the SiC content of the high purity silicon carbide of step S1 is 99% or more.
6. The method for preparing the sagger for firing the lithium battery positive electrode material as claimed in claim 1, wherein the fineness of the high purity silicon carbide in the step S1 is less than 10 μm.
7. The method of producing a sagger for firing a positive electrode material of a lithium battery as claimed in claim 1, wherein the density of the green sagger in the step S2 is 2.73g/cm 3.
8. The method for preparing a sagger for sintering a lithium battery positive electrode material as claimed in claim 1, wherein the calcining temperature in step S5 is 2420 ℃.
9. The method for preparing a sagger for firing a positive electrode material of a lithium battery as claimed in claim 1, wherein the inert gas atmosphere in the step S5 is argon gas atmosphere.
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| CN113968737A (en) * | 2021-11-05 | 2022-01-25 | 湖南太子新材料科技有限公司 | Sagger for preparing lithium battery electrode material |
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| CN113968737A (en) * | 2021-11-05 | 2022-01-25 | 湖南太子新材料科技有限公司 | Sagger for preparing lithium battery electrode material |
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