阅读说明：本技术 基于钛铁渣的锂离子电池正极材料烧结用匣钵及其制备方法 (Sagger for sintering lithium ion battery anode material based on titanium-iron slag and preparation method thereof ) 是由 张寒 赵惠忠 张毅 吴晓青 贺辉华 于 2021-09-29 设计创作，主要内容包括：本发明涉及一种基于钛铁渣的锂离子电池正极材料烧结用匣钵及其制备方法。其技术方案是：将钛铁渣球磨至粒度≤100μm,机压成型,在1430～1450℃热处理,破碎,筛分,得到粒度为0.2～1mm的物料A、粒度为60～80μm的物料B和粒度≤40μm的物料C；将物料B、物料C、ρ-氧化铝微粉和糊精搅拌,得混合细粉料；将物料A与混合细粉料搅拌,加水搅拌,困料,成型,干燥,在1400～1420℃条件下热处理4～5小时,制得基于钛铁渣的锂离子电池正极材料烧结用匣钵。本发明资源化循环利用率高、工艺简单和生产成本低,其制品烧结性能优良、抗侵蚀性能强和热震稳定性好。(The invention relates to a sagger for sintering a lithium ion battery anode material based on ferrotitanium slag and a preparation method thereof. The technical scheme is as follows: ball-milling ferrotitanium slag until the granularity is less than or equal to 100 mu m, mechanically pressing for molding, performing heat treatment at 1430-1450 ℃, crushing, and screening to obtain a material A with the granularity of 0.2-1 mm, a material B with the granularity of 60-80 mu m, and a material C with the granularity of less than or equal to 40 mu m; stirring the material B, the material C, the rho-alumina micro powder and dextrin to obtain mixed fine powder; and stirring the material A and the mixed fine powder, adding water, stirring, ageing, molding, drying, and carrying out heat treatment at 1400-1420 ℃ for 4-5 hours to obtain the sagger for sintering the lithium ion battery anode material based on the ferrotitanium slag. The invention has the advantages of high recycling cyclic utilization rate, simple process, low production cost, excellent product sintering performance, strong erosion resistance and good thermal shock stability.)

1. A preparation method of a sagger for sintering a lithium ion battery anode material based on titanium-iron slag is characterized by comprising the following steps:

firstly, ball-milling ferrotitanium slag until the granularity is less than or equal to 100 mu m, and performing mechanical compression molding under the condition of 20-25 MPa; placing the molded blank in a resistance furnace, carrying out heat treatment for 1-1.5 hours at 1430-1450 ℃, crushing, and screening to obtain a material A with the particle size of 0.2-1 mm, a material B with the particle size of 60-80 mu m and a material C with the particle size of less than or equal to 40 mu m in sequence;

secondly, adding the material B, the material C, the rho-alumina micro powder and the dextrin into a stirrer according to the mass ratio of the material B to the material C to the rho-alumina micro powder to the dextrin of 100 to (65-70) to (5-8) to (6.5-7.5), and premixing for 25-30 minutes to prepare mixed fine powder;

thirdly, adding the material A and the mixed fine powder into a stirrer according to the mass ratio of the material A to the mixed fine powder of 100: 75-80, and mixing for 15-20 minutes to prepare a mixture;

fourthly, adding water accounting for 4.0-4.5 wt% of the mixture into the mixture, and stirring for 20-25 minutes to obtain a raw blank;

and fifthly, ageing the green blank material for 12-15 hours at 25-30 ℃ under a sealing condition, carrying out mechanical pressing forming under the condition of 45-50 MPa, drying for 10-12 hours at 100-120 ℃, placing the dried green blank material in a resistance furnace, and carrying out heat treatment for 4-5 hours at 1400-1420 ℃ to prepare the saggar for sintering the lithium ion battery anode material based on the ferrotitanium slag.

2. The method for preparing the sagger for sintering the lithium ion battery cathode material based on the ferrotitanium slag as claimed in claim 1, wherein the ferrotitanium slag is a byproduct generated by smelting ferrotitanium, and the ferrotitanium slag comprises the following main chemical components: al (Al)₂O₃78-80 wt% of TiO₂8-10 wt% of CaO, 8-9 wt% of Fe₂O₃The content is less than or equal to 0.2 wt%; SiO 2₂The content is less than or equal to 0.2 wt%; the volume density of the ferrotitanium slag is 3.22-3.25 g/cm³And the water absorption rate of the ferrotitanium slag is less than or equal to 6 wt%.

3. The method for preparing the sagger for sintering the lithium ion battery cathode material based on the ferrotitanium slag as claimed in claim 1, wherein the Al of the fine rho-alumina powder₂O₃The content is more than or equal to 98.5 wt%, and the granularity of the rho-alumina micro powder is 60-70 mu m.

4. The method for preparing the sagger for sintering the lithium ion battery cathode material based on the ferrotitanium slag as claimed in claim 1, wherein the dextrin is chemically pure.

5. A sagger for sintering a lithium ion battery cathode material based on titanium and iron slag, which is characterized in that the sagger for sintering the lithium ion battery cathode material based on titanium and iron slag is prepared according to any one of claims 1 to 4 by the preparation method of the sagger for sintering the lithium ion battery cathode material based on titanium and iron slag.

Technical Field

The invention belongs to the technical field of saggars for sintering lithium ion battery anode materials. In particular to a sagger for sintering a lithium ion battery anode material based on titanium-iron slag and a preparation method thereof.

Background

Sagger is an important container in the preparation process of the lithium ion battery anode material, belongs to a typical functional refractory material, and the use temperature of the sagger changes according to the sintering of the lithium ion battery anode material, and is within the range of 800-1100 ℃ (Zhai green, Liuming poplar, Wensui, and the like_xCo_yMn_zO₂Influence of performance of the material for a positive electrode material, refractory, 2021, 55 (2): 102 to 106). Under the influence of factors such as corrosion of a lithium ion battery anode material, thermal stress in the process of cyclic reciprocating use, other mechanical stress and the like, the service life of the sagger is short, the use times are low, and the development of the lithium ion battery anode material is restricted (Chenyang, Duncong, Dingjun, and the like, "research on thermal shock resistance and corrosion resistance of cordierite-mullite sagger materials", silicate notification, 2019, 38 (5): 1550-1555).

At present, the sagger for sintering the lithium ion battery anode material mainly uses cordierite, mullite and spinel as main raw materials, is prepared by sintering after being pressed and molded by a semidry method machine (single-faced Lin Zhao, Huizhou, Jiang Wen Tao, etc. 'research on the performance of the sagger material for sintering the lithium battery anode material', a refractory material 2020, 54(4) is 305-309), and has the main problems that:

(1) the sintering performance of the sagger is poor, and the erosion resistance of the sagger is further influenced. Due to a ternary system (Al) of cordierite, mullite and spinel₂O₃-SiO₂MgO), and obvious volume change is easy to generate in the high-temperature sintering process to form cracks, so that the sintering densification degree of the material is reduced, and the sintering of the saggar is influenced.

(2) During the preparation of the anode material of the lithium ion battery, the anode material is a strong alkaline component (LiOH or Li)₂CO₃) Easily combined with SiO in sagger material₂The components (such as cordierite and mullite) react to form eucryptite and cause volume expansion to cause structural spalling and damage the service performance of the saggar (Hua Jing, Ningcao, Xiao national Qing, etc.' mullite-cordieritePreparation and erosion mechanism of sagger, silicate science, 2020, 48 (6): 931 to 938).

(3) The cost of the synthetic refractory raw materials such as cordierite, mullite, spinel and the like is high, and the development cost of the sagger is increased.

The main components (chemical components and phase components) of the ferrotitanium slag are common components in the field of refractory industry, the resource attribute of the ferrotitanium slag is obvious (Lixuetong, Chaokou, Weichongyang, and the like. "the influence of the addition of the ferrotitanium slag on the slag resistance of a high-alumina bauxite castable", ceramics science and newspaper, 2017, 38 (2): 163-167), the basic premise of preparing the refractory material is met, and the ferrotitanium slag is mainly applied to the preparation of refractory raw materials or replaces the high-alumina bauxite to prepare the high-alumina refractory material at present and is mostly used in the field of steel industry (such as steel ladles, tundishes, and the like).

Disclosure of Invention

The invention aims to overcome the defects of the prior art and provides a preparation method of a sagger for sintering the lithium ion battery anode material based on the titanium-iron slag, which has the advantages of high cyclic utilization rate of industrial solid waste resources, simple process and low production cost.

In order to achieve the purpose, the invention adopts the technical scheme that:

firstly, ball-milling ferrotitanium slag until the granularity is less than or equal to 100 mu m, and performing mechanical compression molding under the condition of 20-25 MPa; and then placing the molded blank in a resistance furnace, carrying out heat treatment for 1-1.5 hours at 1430-1450 ℃, crushing, and screening to obtain a material A with the particle size of 0.2-1 mm, a material B with the particle size of 60-80 mu m and a material C with the particle size of less than or equal to 40 mu m in sequence.

And secondly, adding the material B, the material C, the rho-alumina micro powder and the dextrin into a stirrer according to the mass ratio of the material B to the material C to the rho-alumina micro powder to the dextrin of 100 to (65-70) to (5-8) to (6.5-7.5), and premixing for 25-30 minutes to prepare mixed fine powder.

And thirdly, adding the material A and the mixed fine powder into a stirrer according to the mass ratio of the material A to the mixed fine powder of 100 to (75-80), and mixing for 15-20 minutes to obtain a mixture.

And fourthly, adding water accounting for 4.0-4.5 wt% of the mixture into the mixture, and stirring for 20-25 minutes to obtain a raw blank.

And fifthly, ageing the green blank material for 12-15 hours at 25-30 ℃ under a sealing condition, carrying out mechanical pressing forming under the condition of 45-50 MPa, drying for 10-12 hours at 100-120 ℃, placing the dried green blank material in a resistance furnace, and carrying out heat treatment for 4-5 hours at 1400-1420 ℃ to prepare the saggar for sintering the lithium ion battery anode material based on the ferrotitanium slag.

The ferrotitanium slag is a byproduct generated in ferrotitanium alloy smelting, and the ferrotitanium slag mainly comprises the following chemical components: al (Al)₂O₃78-80 wt% of TiO₂8-10 wt% of CaO, 8-9 wt% of Fe₂O₃The content is less than or equal to 0.2 wt%; SiO 2₂The content is less than or equal to 0.2 wt%; the volume density of the ferrotitanium slag is 3.22-3.25 g/cm³And the water absorption rate of the ferrotitanium slag is less than or equal to 6 wt%.

Al of the rho-alumina micropowder₂O₃The content is more than or equal to 98.5 wt%, and the granularity of the rho-alumina micro powder is 60-70 mu m.

The dextrin is chemically pure.

Due to the adoption of the technical scheme, compared with the prior art, the invention has the following positive effects:

1. the invention selects the ferrotitanium slag as the main raw material, realizes high recycling rate of industrial solid waste resources, and obviously reduces the production cost of the sagger for sintering the lithium ion battery anode material based on the ferrotitanium slag (such as about 3700 yuan/ton of mullite, about 3800 yuan/ton of spinel and only 1700 yuan/ton of ferrotitanium slag).

2. Firstly, ball-milling, mechanically pressing, thermally treating and screening ferrotitanium slag to obtain a material A, a material B and a material C with three different particle sizes in sequence; stirring the material B, the material C, the rho-alumina micro powder and dextrin, mixing the mixture with the material A, adding water, stirring, ageing, molding, and carrying out heat treatment at 1400-1420 ℃ for 4-5 hours to prepare the sagger for sintering the lithium ion battery anode material based on the titanium-iron slag. The preparation process is simple, special equipment requirements are not needed, no solid or gas waste is generated in the preparation process, and the process is environment-friendly.

3. The invention adopts the two-step calcination reaction of the components of the ferrotitanium slag. Namely, the two-time heat treatment technology is adopted, the growth of phase crystal grains is promoted, the solid-solid self-combination of the material is enhanced, and the thermal shock resistance of the sagger for sintering the lithium ion battery anode material based on the titanium iron slag is effectively improved.

The sagger detection for sintering the lithium ion battery anode material based on the ferrotitanium slag, which is prepared by the invention, comprises the following steps: the bulk density is 2.37-2.45 g/cm³(ii) a The retention rate of the residual rupture strength of the 1100 ℃ circulating water cooling 5 times of thermal shock stability experiment is 81.8-83.6%; the corrosion index of a slag resistance experiment of a static crucible method at 1100 ℃ for 5h is 1.1-1.4%.

Therefore, the sagger for sintering the lithium ion battery anode material based on the titanium-iron slag has the characteristics of high cyclic utilization rate of industrial solid waste resources, simple process and low production cost, and the prepared sagger for sintering the lithium ion battery anode material based on the titanium-iron slag has excellent sintering performance, strong erosion resistance and good thermal shock stability.

Detailed Description

The invention is further described with reference to specific embodiments, without limiting its scope.

In order to avoid repetition, the materials related to this specific embodiment are described in a unified manner, which is not described in the embodiments again:

the ferrotitanium slag is a byproduct generated in ferrotitanium alloy smelting, and the ferrotitanium slag mainly comprises the following chemical components: al (Al)₂O₃78-80 wt% of TiO₂8-10 wt% of CaO, 8-9 wt% of Fe₂O₃The content is less than or equal to 0.2 wt%; SiO 2₂The content is less than or equal to 0.2 wt%; the volume density of the ferrotitanium slag is 3.22-3.25 g/cm³And the water absorption rate of the ferrotitanium slag is less than or equal to 6 wt%.

Al of the rho-alumina micropowder₂O₃The content is more than or equal to 98.5 wt%, and the granularity of the rho-alumina micro powder is 60-70 mu m.

The dextrin is chemically pure.

Example 1

A sagger for sintering a lithium ion battery anode material based on titanium-iron slag and a preparation method thereof. The preparation method of the embodiment comprises the following specific steps:

firstly, ball-milling ferrotitanium slag until the granularity is less than or equal to 100 mu m, and performing mechanical compression molding under the condition of 20-25 MPa; and then placing the molded blank in a resistance furnace, carrying out heat treatment for 1-1.5 hours at 1430-1440 ℃, crushing, and screening to obtain a material A with the granularity of 0.2-1 mm, a material B with the granularity of 60-80 mu m and a material C with the granularity of less than or equal to 40 mu m in sequence.

And secondly, adding the material B, the material C, the rho-alumina micro powder and the dextrin into a stirrer according to the mass ratio of the material B to the material C to the rho-alumina micro powder to the dextrin of 100 to (65-66) to (6-7) to (7.3-7.5), and premixing for 25-30 minutes to prepare mixed fine powder.

And thirdly, adding the material A and the mixed fine powder into a stirrer according to the mass ratio of the material A to the mixed fine powder of 100 to (75-77), and mixing for 15-20 minutes to obtain a mixture.

And fourthly, adding water accounting for 4.0-4.1 wt% of the mixture into the mixture, and stirring for 20-25 minutes to obtain a raw blank.

And fifthly, ageing the green blank material for 12-15 hours at 25-30 ℃ under a sealing condition, carrying out mechanical pressing forming under the condition of 45-50 MPa, drying for 10-12 hours at 100-120 ℃, placing the dried green blank material in a resistance furnace, and carrying out heat treatment for 4-5 hours at 1400-1405 ℃ to prepare the saggar for sintering the lithium ion battery anode material based on the ferrotitanium slag.

The sagger detection for sintering the lithium ion battery anode material based on the ferrotitanium slag, which is prepared by the invention, comprises the following steps: the bulk density is 2.37-2.42 g/cm³(ii) a The retention rate of the residual rupture strength of the 1100 ℃ circulating water cooling 5 times of thermal shock stability experiment is 82.2-83.5%; the corrosion index of a slag resistance experiment of a static crucible method at 1100 ℃ for 5h is 1.2-1.4%.

Example 2

A sagger for sintering a lithium ion battery anode material based on titanium-iron slag and a preparation method thereof. The preparation method of the embodiment comprises the following specific steps:

firstly, ball-milling ferrotitanium slag until the granularity is less than or equal to 100 mu m, and performing mechanical compression molding under the condition of 20-25 MPa; and then placing the molded blank body in a resistance furnace, carrying out heat treatment for 1-1.5 hours at the temperature of 1435-1450 ℃, crushing, and screening to obtain a material A with the granularity of 0.2-1 mm, a material B with the granularity of 60-80 mu m and a material C with the granularity of less than or equal to 40 mu m in sequence.

And secondly, adding the material B, the material C, the rho-alumina micro powder and the dextrin into a stirrer according to the mass ratio of the material B to the material C to the rho-alumina micro powder to the dextrin of 100 to (68-70) to (5-7) to (6.5-7.1), and premixing for 25-30 minutes to prepare mixed fine powder.

And thirdly, adding the material A and the mixed fine powder into a stirrer according to the mass ratio of the material A to the mixed fine powder of 100 to (76-80), and mixing for 15-20 minutes to obtain a mixture.

And fourthly, adding water accounting for 4.0-4.3 wt% of the mixture into the mixture, and stirring for 20-25 minutes to obtain a raw blank.

And fifthly, ageing the green blank material for 12-15 hours at 25-30 ℃ under a sealing condition, carrying out mechanical pressing forming under the condition of 45-50 MPa, drying for 10-12 hours at 100-120 ℃, placing the dried green blank material in a resistance furnace, and carrying out heat treatment for 4-5 hours at 1410-1420 ℃ to prepare the saggar for sintering the lithium ion battery anode material based on the ferrotitanium slag.

The sagger detection for sintering the lithium ion battery anode material based on the ferrotitanium slag, which is prepared by the invention, comprises the following steps: the bulk density is 2.39-2.43 g/cm³(ii) a The retention rate of the residual rupture strength of the 1100 ℃ circulating water cooling 5 times of thermal shock stability experiment is 81.8-82.5%; the corrosion index of a slag resistance experiment of a static crucible method at 1100 ℃ for 5h is 1.1-1.2%.

Example 3

A sagger for sintering a lithium ion battery anode material based on titanium-iron slag and a preparation method thereof. The preparation method of the embodiment comprises the following specific steps:

firstly, ball-milling ferrotitanium slag until the granularity is less than or equal to 100 mu m, and performing mechanical compression molding under the condition of 20-25 MPa; and then placing the molded blank body in a resistance furnace, carrying out heat treatment for 1-1.5 hours at 1435-1445 ℃, crushing, and screening to obtain a material A with the granularity of 0.2-1 mm, a material B with the granularity of 60-80 mu m and a material C with the granularity of less than or equal to 40 mu m in sequence.

And secondly, adding the material B, the material C, the rho-alumina micro powder and the dextrin into a stirrer according to the mass ratio of the material B to the material C to the rho-alumina micro powder to the dextrin of 100 to (65-69) to (6-8) to (6.8-7.4), and premixing for 25-30 minutes to prepare mixed fine powder.

And thirdly, adding the material A and the mixed fine powder into a stirrer according to the mass ratio of the material A to the mixed fine powder of 100 to (75-78), and mixing for 15-20 minutes to obtain a mixture.

And fourthly, adding water accounting for 4.2-4.5 wt% of the mixture into the mixture, and stirring for 20-25 minutes to obtain a raw blank.

And fifthly, ageing the green blank material for 12-15 hours at 25-30 ℃ under a sealing condition, carrying out mechanical pressing forming under the condition of 45-50 MPa, drying for 10-12 hours at 100-120 ℃, placing the dried green blank material in a resistance furnace, and carrying out heat treatment for 4-5 hours at 1400-1410 ℃ to obtain the saggar for sintering the lithium ion battery anode material based on the ferrotitanium slag.

The sagger detection for sintering the lithium ion battery anode material based on the ferrotitanium slag, which is prepared by the invention, comprises the following steps: the bulk density is 2.44-2.45 g/cm³(ii) a The retention rate of the residual rupture strength of the 1100 ℃ circulating water cooling 5 times of thermal shock stability experiment is 83.3-83.6%; the corrosion index of a slag resistance experiment of a static crucible method at 1100 ℃ for 5h is 1.1-1.3%.

Example 4

A sagger for sintering a lithium ion battery anode material based on titanium-iron slag and a preparation method thereof. The preparation method of the embodiment comprises the following specific steps:

firstly, ball-milling ferrotitanium slag until the granularity is less than or equal to 100 mu m, and performing mechanical compression molding under the condition of 20-25 MPa; and then placing the molded blank body in a resistance furnace, carrying out heat treatment for 1-1.5 hours at 1445-1450 ℃, crushing, and screening to obtain a material A with the granularity of 0.2-1 mm, a material B with the granularity of 60-80 mu m and a material C with the granularity of less than or equal to 40 mu m in sequence.

And secondly, adding the material B, the material C, the rho-alumina micro powder and the dextrin into a stirrer according to the mass ratio of the material B to the material C to the rho-alumina micro powder to the dextrin of 100 to (68-70) to (5-6) to (6.6-7.2), and premixing for 25-30 minutes to prepare mixed fine powder.

And thirdly, adding the material A and the mixed fine powder into a stirrer according to the mass ratio of the material A to the mixed fine powder of 100 to (77-80), and mixing for 15-20 minutes to obtain a mixture.

And fourthly, adding water accounting for 4.2-4.4 wt% of the mixture into the mixture, and stirring for 20-25 minutes to obtain a raw blank.

And fifthly, ageing the green blank material for 12-15 hours at 25-30 ℃ under a sealing condition, carrying out mechanical pressing forming under the condition of 45-50 MPa, drying for 10-12 hours at 100-120 ℃, placing the dried green blank material in a resistance furnace, and carrying out heat treatment for 4-5 hours at 1405-1420 ℃ to prepare the saggar for sintering the lithium ion battery anode material based on the ferrotitanium slag.

The sagger detection for sintering the lithium ion battery anode material based on the ferrotitanium slag, which is prepared by the invention, comprises the following steps: the bulk density is 2.38-2.42 g/cm³(ii) a The retention rate of the residual rupture strength of the 1100 ℃ circulating water cooling 5 times of thermal shock stability experiment is 81.9-83.4%; the corrosion index of a slag resistance experiment of a static crucible method at 1100 ℃ for 5h is 1.2-1.3%.

Compared with the prior art, the specific implementation mode has the following positive effects:

1. the embodiment selects the ferrotitanium slag as the main raw material, realizes high recycling rate of industrial solid waste resources, and obviously reduces the production cost of the sagger for sintering the lithium ion battery anode material based on the ferrotitanium slag (such as about 3700 yuan/ton of mullite, about 3800 yuan/ton of spinel and only 1700 yuan/ton of ferrotitanium slag).

2. Firstly, ball milling, mechanical compression molding, heat treatment and screening are carried out on ferrotitanium slag to obtain a material A, a material B and a material C with three different particle sizes in sequence; stirring the material B, the material C, the rho-alumina micro powder and dextrin, mixing the mixture with the material A, adding water, stirring, ageing, molding, and carrying out heat treatment at 1400-1420 ℃ for 4-5 hours to prepare the sagger for sintering the lithium ion battery anode material based on the titanium-iron slag. The preparation process is simple, special equipment requirements are not needed, no solid or gas waste is generated in the preparation process, and the process is environment-friendly.

3. The specific embodiment is implemented by a two-step calcination reaction of the ferrotitanium slag components. Namely, the two-time heat treatment technology is adopted, the growth of phase crystal grains is promoted, the solid-solid self-combination of the material is enhanced, and the thermal shock resistance of the sagger for sintering the lithium ion battery anode material based on the titanium iron slag is effectively improved.

The sagger for sintering the lithium ion battery anode material based on the ferrotitanium slag prepared by the specific embodiment is used for detection: the bulk density is 2.37-2.45 g/cm³(ii) a The retention rate of the residual rupture strength of the 1100 ℃ circulating water cooling 5 times of thermal shock stability experiment is 81.8-83.6%; the corrosion index of a slag resistance experiment of a static crucible method at 1100 ℃ for 5h is 1.1-1.4%.

Therefore, the specific implementation mode has the characteristics of high cyclic utilization rate of industrial solid waste resources, simple process, low production cost, strong erosion resistance and good thermal shock stability. The characteristics of (1); the prepared sagger for sintering the lithium ion battery anode material based on the titanium-iron slag has excellent sintering performance, strong erosion resistance and good thermal shock stability.