阅读说明：本技术 一种复合尖晶石莫来石陶瓷耐火材料及其制备方法 (Composite spinel-mullite ceramic refractory material and preparation method thereof ) 是由 王家邦 王膑 陆静娟 田丰 谢峰 顾耀成 尹述伟 陈惠子 陆觉田 陈哲宁 于 2021-08-04 设计创作，主要内容包括：本发明涉及复合材料领域,尤其是涉及一种复合尖晶石莫来石陶瓷耐火材料及其制备方法,所述复合尖晶石莫来石陶瓷耐火材料的原料包括以下重量比的成分：轻烧镁粉9-25份、工业氧化铝50-100份和石英粉8-20份。其制备方法包括以下步骤：按照配比称取各成分,混匀,加入矿热炉,在2200-2500℃电弧加热熔融5-15分钟,然后倾斜矿热炉倒入水槽中快速冷却,捞出干燥。现有用尖晶石和莫来石做原料制备的复合耐火材料匣钵,在锂电池正极材料烧结过程中抗腐蚀性差,本申请通过改变原料,并限定原料中各成分的用量,最终提供的复合尖晶石莫来石陶瓷耐火材料中不仅保持了原耐火性和抗热震性能,且增强了抗锂离子耐腐蚀性能。(The invention relates to the field of composite materials, in particular to a composite spinel mullite ceramic refractory material and a preparation method thereof, wherein the raw materials of the composite spinel mullite ceramic refractory material comprise the following components in percentage by weight: 9-25 parts of light-burned magnesium powder, 50-100 parts of industrial alumina and 8-20 parts of quartz powder. The preparation method comprises the following steps: weighing the components according to the proportion, mixing uniformly, adding into a submerged arc furnace, heating and melting for 5-15 minutes at the temperature of 2200-. The composite refractory material sagger prepared by taking spinel and mullite as raw materials is poor in corrosion resistance in the sintering process of a lithium battery anode material.)

1. The composite spinel mullite ceramic refractory material is characterized by comprising the following raw materials in percentage by weight: 9-25 parts of light-burned magnesium powder, 50-100 parts of industrial alumina and 8-20 parts of quartz powder.

2. The composite spinel mullite ceramic refractory of claim 1, wherein the raw materials comprise the following components in weight ratio: 9-21 parts of light-burned magnesium powder, 70-80 parts of industrial alumina and 8-20 parts of quartz powder.

3. The composite spinel mullite ceramic refractory of claim 1, wherein the raw materials comprise the following components in weight ratio: 12-21 parts of light-burned magnesium powder, 70-80 parts of industrial alumina and 8.4-18 parts of quartz powder.

4. The composite spinel mullite ceramic refractory of claim 1, wherein the raw materials comprise the following components in weight ratio: 15-21 parts of light-burned magnesium powder, 70-75 parts of industrial alumina and 8.4-16 parts of quartz powder.

5. The composite spinel mullite ceramic refractory of any one of claims 1-4, wherein the light-burned magnesia powder has MgO content of 95% or more and SiO content₂Less than or equal to 1.2 percent, less than or equal to 0.8 percent of CaO and less than or equal to 3 percent of burning vector;

al in the industrial alumina₂O₃＞98％，Na₂O＜0.5％；

SiO in the quartz powder₂＞99％，Fe₂O₃＜0.03％。

6. The composite spinel mullite ceramic refractory of any one of claims 1-4, wherein the light-burned magnesite powder has a particle size of 200 mesh.

7. The composite spinel mullite ceramic refractory of any one of claims 1-4, wherein the alumina has a particle size of 200 mesh.

8. The composite spinel mullite ceramic refractory of any one of claims 1 through 4, wherein the quartz powder has a particle size of 200 mesh.

9. The preparation method of the composite spinel mullite ceramic refractory material is characterized by comprising the following steps of: weighing the components according to the formula of any one of claims 1 to 8, mixing, adding into a submerged arc furnace, arc-heating and melting at 2200-.

10. Use of the composite spinel mullite ceramic refractory of claims 1-8 in the preparation of a sagger.

Technical Field

The invention relates to the field of materials, and relates to a composite spinel-mullite ceramic refractory material and a preparation method thereof.

Background

Mullite (A3S 2 for short), also called monel, kyanite, mullite, sillimanite, is a series of minerals composed of aluminosilicates, with the chemical formula: 3Al₂O₃·2SiO₂The structure is arranged in a chain shape, and the crystal is long columnar and needle-shaped extending along the C axis and belongs to an orthorhombic system. Has high refractoriness of 1800 ℃ (1810 ℃ decomposes into corundum and liquid phase) and good erosion resistance to acid slag at high temperature. Mullite is a high-quality refractory material and has the characteristics of uniform expansion, good thermal shock resistance, good high-temperature load resistance, good creep resistance, high hardness, good chemical corrosion resistance, good wear resistance, good spalling resistance and the like.

Spinel (Spinel), meaning a sharp-cornered crystal, is a mineral composed of magnesium-aluminum oxide, and has the chemical formula of MgO₂O₃(abbreviated as MA) having a melting point of 2135 ℃.

In recent years, mullite (3A 1) has been used in the pyrometallurgical, cement, glass and steel industries₂O₃·2SiO₂) And magnesium aluminate spinel (MA) have evolvedThere is a great interest. This is due to the superior properties of these two materials, especially their high melting points (1819 ℃ and 2135 ℃ for mullite and magnesia alumina spinel, respectively), low thermal expansion, high thermal shock resistance and resistance to slag erosion. Magnesium aluminate spinel (MA) belongs to cubic system, mullite belongs to orthorhombic system, and the thermal expansion and the elastic modulus of the magnesium aluminate spinel (MA) are different (the thermal expansion coefficient of spinel is 8.9 multiplied by 10)^-6K, coefficient of thermal expansion of mullite is 5.3X 10^-6K) and the mullite is added into the spinel material to play a complex phase toughening role.

At present, the preparation method of the composite spinel mullite refractory raw material is to add spinel into mullite, wherein the ratio of mullite to magnesia-alumina spinel is 100: 0. 80: 20. 60: 40. 50: 50. 40: 60. 20: 80 and 0: 100, along with the increase of the spinel content and the reduction of mullite, the refractory performance of the mullite-spinel composite material is obviously improved, and the mullite-spinel composite material has good volume stability (permanent line change is less than-0.8 percent), high refractory performance (more than 1700 ℃), high thermal shock resistance (no crack in air cooling from 1000 ℃ to room temperature, and thermal shock times more than 100 times), and high refractoriness under load (1560 and 1680 ℃).

Although the refractory performance of the composite material is improved, the performance of the composite material in lithium ion corrosion resistance is still poor, and the service life of a sagger adopting the composite material can be reflected.

Disclosure of Invention

In order to improve the lithium ion corrosion resistance of the conventional sagger prepared from spinel, mullite particles and powder, the application provides a novel composite spinel-mullite ceramic refractory material and a preparation method thereof.

In a first aspect, the present application provides a new composite spinel mullite ceramic refractory material, which adopts the following technical scheme:

the composite spinel mullite ceramic refractory material comprises the following raw materials in percentage by weight: 9-25 parts of light-burned magnesium powder, 50-100 parts of industrial alumina and 8-20 parts of quartz powder.

Preferably, the raw materials comprise the following components in percentage by weight: 9-21 parts of light-burned magnesium powder, 70-80 parts of industrial alumina and 8-20 parts of quartz powder.

Further preferably, the raw materials comprise the following components in percentage by weight: 12-21 parts of light-burned magnesium powder, 70-80 parts of industrial alumina and 8.4-18 parts of quartz powder.

Most preferably, the raw materials comprise the following components in percentage by weight: 15-21 parts of light-burned magnesium powder, 70-75 parts of industrial alumina and 8.4-16 parts of quartz powder.

The composite spinel mullite ceramic refractory material comprises the following raw materials:

MgO in the light-burned magnesium powder is more than or equal to 95 percent, and SiO in the light-burned magnesium powder₂Less than or equal to 1.2 percent, less than or equal to 0.8 percent of CaO and less than or equal to 3 percent of burning vector;

al in the industrial alumina₂O₃＞98％，Na₂O＜0.5％；

SiO in the quartz powder₂＞99％，Fe₂O₃＜0.03％。

Preferably, the first and second electrodes are formed of a metal,

the grain diameter of the light-burned magnesium powder is 200 meshes;

the grain diameter of the alumina is 200 meshes;

the particle size of the quartz powder is 200 meshes.

In a second aspect, the present application provides a method for preparing a composite spinel mullite ceramic refractory material:

a preparation method of a composite spinel-mullite ceramic refractory material comprises the following steps: weighing the components according to the proportion, mixing uniformly, adding into a submerged arc furnace, heating and melting for 5-15 minutes at the temperature of 2200-.

In the method; the problems of incompact sintering due to 6.9 percent generated in the process of generating spinel by the reaction of magnesia and alumina, cordierite phase generated by low-temperature eutectic in the sintering process, forsterite phase (large expansion coefficient) generated by decomposing cordierite at 1460 ℃ and the like can be avoided by the electric melting method.

The water cooling method is used for rapid cooling, the molten components are cracked when meeting water to form particles, and meanwhile, the uniform distribution of spinel and mullite components is ensured, the growth of spinel and mullite grains is prevented, and the microcrystalline structure is ensured. The melting point of spinel is 2135 ℃, the temperature of mullite is 1860 ℃, when natural cooling is adopted, spinel is firstly separated out, crystal grains are continuously grown along with continuous separation of spinel, then the mullite is separated out, phase splitting is easily generated, and therefore, the components are not uniform.

In a third aspect, the application provides an application of the composite spinel mullite ceramic refractory material in preparation of saggars. The composite ceramic refractory material can be crushed into different particle sizes according to requirements.

In summary, the present application has the following beneficial effects:

1. the composite refractory material sagger prepared by taking spinel and mullite as raw materials is poor in corrosion resistance in the sintering process of a lithium battery anode material.

2. The composite spinel mullite ceramic refractory material provided by the application is subjected to corrosion resistance reaction performance investigation through chemical thermodynamics and chemical reaction power, the corrosion resistance is tested by adopting the chemical reaction of the composite spinel mullite ceramic refractory material, the electric-melting spinel ceramic refractory material, the mullite ceramic refractory material and a high-nickel LNCM battery anode material (811 raw material), and the lithium ion corrosion resistance of the ceramic refractory material is determined mainly through the size change of a sample. The results show that: the corrosion resistance of the composite spinel mullite ceramic refractory material is between that of an electric smelting spinel ceramic refractory material and that of an electric smelting mullite ceramic refractory material, and the higher the spinel proportion is, the better the lithium ion corrosion resistance is.

Detailed Description

The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention.

The raw material sources are as follows:

light-burned magnesium powder, available from yingkoxin Yao magnesium industries, ltd;

commercial alumina powder available from aluminum industries, ltd, zhong aluminum;

high-purity quartz powder purchased from Jiangsu Runsha solar materials science and technology Limited;

mullite, available from fluvial-south china engineering materials ltd;

spinel, available from Henan Te engineering materials GmbH, lot number AM-70.

Example 1: composite spinel mullite ceramic refractory material

1. Raw materials: the weight ratio of the light-burned magnesium powder, the industrial alumina powder and the high-purity quartz powder is 15: 70: 14, the particle size of each component was 200 mesh. (the weight units are kg, g or mg).

2. Preparation method

1) Weighing industrial alumina powder, light-burned magnesium powder and high-purity quartz powder according to the proportion, and premixing for 30 minutes;

2) adding the premixed powder into an ore smelting furnace, heating and melting by adopting an electric arc, wherein the final melting temperature is 2500 ℃, and continuing to heat and melt for 10 minutes after melting;

3) guiding the melt into a 304 stainless steel tank with circulating water cooling, wherein the circulating water directly impacts the melt poured into the submerged arc furnace to rapidly cool the melt, and meanwhile, part of the melt is granulated (is cracked to form granules when meeting water);

4) after the melt is poured into the furnace, the circulating cooling water is continuously cooled for 15 minutes, the stainless steel groove is lifted out, and the spinel-mullite grains are drained and sent to a drying kiln for drying.

The spinel-mullite composite refractory material can be crushed according to needs, for example, the spinel-mullite composite refractory material is crushed by a crusher, 0-1 mm particles and 1-2 mm particles are separated after crushing, and part of 0-1 mm particles are taken out and ground into 320 meshes of powder.

Wherein the crystal phase ratio of spinel to mullite is 50: 50.

example 2: composite spinel mullite ceramic refractory material

The difference from example 1 is that the starting materials: the weight ratio of the light-burned magnesia powder to the high-purity quartz powder is 9: 71.4: 19.6.

wherein the crystal phase ratio of spinel to mullite is 30: 70.

example 3: composite spinel mullite ceramic refractory material

The difference from example 1 is that the starting materials: the weight ratio of the light-burned magnesium powder, the industrial alumina powder and the high-purity quartz powder is 21: 70.6: 8.4.

wherein the crystal phase ratio of spinel to mullite is 70: 30.

example 4: composite spinel mullite ceramic refractory material

The difference from example 1 is that the starting materials: the weight ratio of the light-burned magnesium powder, the industrial alumina powder and the high-purity quartz powder is 18: 70: 12.

wherein the crystal phase ratio of spinel to mullite is 60: 40.

example 5: composite spinel mullite ceramic refractory material

The difference from example 1 is that the starting materials: the weight ratio of the light-burned magnesium powder, the industrial alumina powder and the high-purity quartz powder is 12: 70: 18.

wherein the crystal phase ratio of spinel to mullite is 40: 60.

example 6: composite spinel mullite ceramic refractory material

The same as example 1 except that in the preparation method, the temperature of electric melting heating was 2400 ℃.

Comparative example 1: directly adopts the electrocast spinel refractory raw material and the electrocast mullite refractory raw material to be directly mixed according to the proportion

The mixture ratio of the spinel and the mullite is the same as that in the example 1, and the raw materials are spinel: mullite is 50: 50.

comparative example 2: directly adopts the raw materials of the fused spinel refractory and the fused mullite refractory to be mixed according to the proportion

The mixture ratio of the spinel and the mullite prepared is the same as that of the example 2, and the raw materials are spinel: the mullite is 30: 70.

comparative example 3: directly adopts the raw materials of the fused spinel refractory and the fused mullite refractory to be mixed according to the proportion

The mixture ratio of the spinel and the mullite prepared is the same as that in example 3, and the raw materials are spinel: the mullite is 70: 30.

experimental example 1: test for fire resistance and Corrosion resistance

1. See examples 1-5, comparative example 1, comparative example 2, comparative example 3, comparative example 4 (spinel alone) and comparative example 5 (mullite alone).

2. The detection method comprises the following steps:

the corrosion resistance is tested by adopting the chemical reaction of composite spinel mullite and a high-nickel LNCM battery positive electrode material (811 raw material), and the lithium ion corrosion resistance is determined mainly by the change of the sample size.

According to the mass ratio of a composite spinel mullite refractory raw material to a high-nickel LNCM battery anode material (811 raw material) of 70: 30, adding yellow dextrin accounting for 3 percent of the total mass of the mixed materials as a binding agent, carrying out dry milling for 2 hours in a ball mill, and adding deionized water for wet milling for 10 minutes. Pressing the mixed raw materials into a wafer with the diameter of 30mm under 50MPa, and putting the wafer into an oven for 24 hours at the temperature of 110 ℃. The dried sample was obtained, heat-treated at 800 ℃ to 1100 ℃ for 4 hours, and the change in the diameter size of the wafer sample before and after the heat treatment was measured with a vernier caliper.

3. As a result:

table 1: measurement of swelling size

Note that the spinel and mullite in the above proportion are in the ratio of crystal phase contents

Table 1 the results show that:

when spinel or mullite is used alone, spinel hardly expands at 800 ℃, mullite expands 1.9%, (30.58/30 ═ 1.019) to 1100 ℃ at a maximum of 2.2% (30.7/30 ═ 1.022), and mullite expands to 4.3% (31.29/30 ═ 1.043), so that mullite reacts more easily than spinel and has poor surface lithium ion corrosion performance.

The performance of the composite spinel mullite ceramic refractory material prepared by the method is between that of pure spinel and that of mullite, and the corrosion resistance is better along with the increase of the content of spinel.

Samples with the same spinel and mullite contents were compared: as can be seen from the expansion size, comparative example 1 is larger than example 1 under different temperature conditions, and example 2, refractory material 3 prepared from composite spinel mullite is also smaller than comparative examples 2 and 3.

The results show that: compared with a single mullite product, the composite spinel mullite ceramic refractory material provided by the method has the advantage that the corrosion resistance is greatly improved, so that a foundation is laid for prolonging the service life of a product.

Although the invention has been described in detail hereinabove by way of general description, specific embodiments and experiments, it will be apparent to those skilled in the art that many modifications and improvements can be made thereto based on the invention. Accordingly, such modifications and improvements are intended to be within the scope of the invention as claimed.