CN109081687B - High thermal shock resistance ceramic crucible suitable for calcining lithium battery anode material and preparation method thereof - Google Patents
High thermal shock resistance ceramic crucible suitable for calcining lithium battery anode material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a high thermal shock resistance ceramic crucible suitable for calcining a lithium battery anode material and a preparation method thereof, wherein the ceramic crucible material comprises the following chemical components: SiO 22 45～60wt%、Al2O3 25～35wt%、Li2O 3～5wt%、ZrO2 3～8wt%、MgO1～3wt%、TiO2 1 to 5 wt%. The crucible blank is obtained by burdening, ball milling, sieving, filter pressing and dehydration, vacuum pugging, punch forming and drying, and finally the sintering is carried out in a reducing atmosphere. The crucible disclosed by the invention is low in production cost and good in forming performance, effectively improves the thermal shock resistance and the alkali resistance of a product, can well meet the alkali resistance use requirement of a calcined lithium battery anode material, and is favorable for promoting the technical progress and the application development of the crucible industry, so that the crucible has a wide market prospect.
Description
Technical Field
The invention belongs to the technical field of refractory materials, and particularly relates to a high thermal shock resistance ceramic crucible suitable for calcining a lithium battery anode material and a preparation method thereof.
Background
The ceramic crucible is an important component of refractory materials, is a container for melting and calcining, solid-liquid heating and reaction, is a foundation for ensuring smooth chemical reaction, and is also an essential article for preparing high-purity oxides.
The synthesis of the lithium battery anode material needs a crucible, and at present, the crucible material for calcining the lithium battery anode material mainly comprises a mullite-cordierite crucible, is low in price and easy to obtain, and is widely used. However, the crucible has fatal defects, and the structure of the crucible is porous, is not resistant to alkali corrosion, and has short service life and instability; meanwhile, the particles are coarse and easy to fall off when in use, thereby polluting the anode material of the lithium battery. The use times of the crucible is low, and a lot of solid waste is generated, so that the environment is polluted and the crucible is difficult to treat. Under the current environmental protection pressure and the lithium battery price competition pressure, enterprises have to search for new crucible materials, and the development of crucibles with alkali corrosion resistance, compactness, high thermal shock resistance and long service life is urgent.
Disclosure of Invention
The invention aims to provide a high thermal shock resistant ceramic crucible which has good thermal shock resistance, strong alkali resistance, high breaking strength, low cost, long service life and no environmental pollution and is suitable for calcining a lithium battery anode material, and a preparation method thereof.
In order to solve the technical problems, the technical scheme of the invention is as follows: high thermal shock resistance ceramic crucible suitable for calcining lithium battery anode materialThe crucible is characterized in that: adopts natural mineral raw materials and industrial chemical raw materials, and comprises the following chemical components in percentage by weight: SiO 22 45～60wt%、Al2O3 20～35wt%、Li2O 3～5wt%、ZrO2 3～8wt%、MgO1～3wt%、TiO2 1～5 wt%。
The ZrO2The adopted raw material is 8 mol% of yttria stabilized zirconia powder which is used as an alkali-resisting agent; the TiO is2The raw material used is titanium oxide powder having an average particle diameter of 100nm or less, and is used as a sintering aid.
The flexural strength of the crucible is 70-80 MPa, and the expansion coefficient is alpha（800～20℃）≤1.0×10-6The temperature is higher than or equal to 98.5 percent, the thermal shock resistance is more than or equal to 25 times of air cooling at the temperature of 1000-20 ℃ and no crack occurs.
The preparation method of the ceramic crucible with high thermal shock resistance is characterized by comprising the following steps:
the method comprises the following steps: crushing the crucible raw material to the particle size of D90=45 microns by using ball milling equipment;
step two: mixing the materials according to the chemical composition percentage of the formula, performing mixing, ball milling, sieving, filter pressing and dehydration, performing vacuum pugging, punch forming and drying to obtain a crucible blank;
step three: and sintering in a reducing atmosphere.
And in the first step, the ball milling equipment is an air flow mill or a Raymond mill.
And the ball milling time in the second step is 3-5 h.
The firing system in the third step is to slowly fire from room temperature to 1290-1330 ℃ for 9-10 h, preserve heat for 1-2 h, and naturally cool to room temperature.
The invention has the following beneficial effects:
(1) the high-performance low-expansion crucible product has the advantages of low production cost, good forming performance, high thermal shock resistance and high production qualification rate;
(2) the alkali-resisting agent is introduced into the blank, so that the alkali-resisting performance is obviously improved;
(3) the high-performance low-expansion crucible has the rupture strength of 70-80MPa, coefficient of expansion of alpha（800～20℃）≤1×10-6The temperature is higher than or equal to 98.5 percent, the thermal shock resistance is not less than 25 times of air cooling at the temperature of 1000-20 ℃, and the crack is avoided, so the method has wide market prospect.
Detailed Description
The present invention will be described in further detail with reference to specific embodiments.
The chemical composition and preparation process parameters of the high thermal shock resistance ceramic crucible suitable for calcining the lithium battery anode material in the embodiment of the invention are shown in the following table.
The preparation method of the high thermal shock resistance ceramic crucible suitable for calcining the lithium battery anode material comprises the following steps:
the crucible raw material provided by the invention is prepared by firstly grinding hard materials and soft materials to the particle size of D90=45 microns through an air flow mill or a Raymond mill, then mixing the materials according to a formula, performing ball milling, sieving, filter pressing and dehydration, vacuum pugging, punch forming and drying to obtain a crucible blank, and finally sintering. The firing is carried out by adopting a reducing flame slow firing process, namely, the firing is carried out slowly from room temperature to the porcelain forming temperature by adopting reducing atmosphere, and the ceramic crucible is naturally cooled to the room temperature after heat preservation, so that the ceramic crucible product with high thermal shock resistance, which is suitable for calcining the lithium battery anode material, is obtained.
The performance indexes of the high thermal shock resistance ceramic crucible for calcining the lithium battery anode material in the embodiment of the invention are shown in the following table.
The performance index testing method comprises the following steps:
1. the alkalinity resistance test method comprises the steps of taking a sintered crucible product, placing the crucible product into 10% sodium hydroxide solution, slightly boiling for 1h at 105 ℃, and comparing the mass of a residual sample after corrosion with the initial mass of the sample to obtain the alkalinity resistance of the crucible material;
2. the expansion coefficient is measured by a thermal expansion coefficient meter, and the model is DIL402 PC;
3. the flexural strength is measured by a digital display type engineering ceramic bending strength tester, and the model is GWQ-20000;
4. the thermal shock resistance is achieved by burning the sample to 1000 ℃ by an electric kiln, keeping the temperature for 1 hour, taking out the sample after the temperature is uniform, and cooling the sample by an electric fan to see whether the sample is cracked or not.
Claims (4)
1. The utility model provides a high thermal shock resistance ceramic crucible suitable for calcine lithium cell cathode material which characterized in that: adopts natural mineral raw materials and industrial chemical raw materials, and comprises the following chemical components in percentage by weight: SiO 22 45～60wt%、Al2O3 20～35wt%、Li2O 3～5wt%、ZrO2 3～8wt%、MgO1～3wt%、TiO2 1～5 wt%；
The ZrO2The adopted raw material is 8 mol% of yttria stabilized zirconia powder which is used as an alkali-resisting agent; the TiO is2The adopted raw material is titanium oxide powder with the average grain diameter of less than 100nm, and the titanium oxide powder is used as a sintering aid;
the flexural strength of the crucible is 70-80 MPa, and the expansion coefficient is alpha（800～20℃）≤1.0×10-6The temperature is higher than or equal to 98.5 percent, the thermal shock resistance is more than or equal to 25 times of air cooling at the temperature of 1000-20 ℃, and the crack is avoided;
the preparation method of the ceramic crucible with high thermal shock resistance comprises the following steps:
the method comprises the following steps: crushing the crucible raw material to the particle size of D90=45 microns by using ball milling equipment;
step two: mixing the materials according to the chemical composition percentage of the formula, performing mixing, ball milling, sieving, filter pressing and dehydration, performing vacuum pugging, punch forming and drying to obtain a crucible blank;
step three: and sintering in a reducing atmosphere.
2. The ceramic crucible of claim 1, wherein: and in the first step, the ball milling equipment is an air flow mill or a Raymond mill.
3. The ceramic crucible of claim 1, wherein: and the ball milling time in the second step is 3-5 h.
4. The ceramic crucible of claim 1, wherein: the firing system in the third step is to slowly fire from room temperature to 1290-1330 ℃ for 9-10 h, preserve heat for 1-2 h, and naturally cool to room temperature.
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