阅读说明：本技术 一种低能耗高镍三元材料的制备方法 (Preparation method of low-energy-consumption high-nickel ternary material ) 是由 李佳军 钱飞鹏 赵春阳 于 2020-12-29 设计创作，主要内容包括：本发明公开了一种低能耗高镍三元材料的制备方法,工艺简单,实用性强,批量化生产可实现全自动；首先选用高镍低钴前躯体,工业1级碳酸锂作为原料,成本更低；采用固相掺杂纳米级金属元素有益于稳定材料的晶体结构,使之在充放电过程中不易破坏,并有效降低烧结残余碱量,提高充放电性能；使用空气氧气各半的进气条件,相对纯氧成本更低,又能保证材料在合成过程中的催化作用；采用大容量匣钵,更多的装载带来了产量的提升,生产过程中下层匣钵的气体挥发不充分,较上层可以减少装载来达到性能的平衡。(The invention discloses a preparation method of a low-energy-consumption high-nickel ternary material, which has the advantages of simple process, strong practicability and full automation in batch production; firstly, a high-nickel low-cobalt precursor and industrial grade-1 lithium carbonate are selected as raw materials, so that the cost is lower; the solid phase doped nano-scale metal elements are beneficial to stabilizing the crystal structure of the material, so that the material is not easy to damage in the charging and discharging process, the residual alkali amount in sintering is effectively reduced, and the charging and discharging performance is improved; the air intake condition of each half of air and oxygen is used, so that the cost is lower than that of pure oxygen, and the catalytic action of the material in the synthesis process can be ensured; the large-capacity saggars are adopted, more loading brings improvement of yield, gas volatilization of the saggars on the lower layer is insufficient in the production process, and the loading can be reduced compared with the saggars on the upper layer to achieve balance of performance.)

1. The preparation method of the low-energy-consumption high-nickel ternary material is characterized by comprising the following steps of:

s1, weighing a proper amount of high-nickel precursor and lithium carbonate, and doping the metal element A in a quantitative proportion, wherein the proportion of the lithium carbonate to the high-nickel precursor is 1.02-1.1: 1. the addition amount of the metal element A is 0.1-0.5% of the theoretical product mass;

s2, putting the weighed raw materials into a high-speed mixer for fully mixing, wherein the mixing time is as follows: 25-40min, rotation speed: 300-;

s3, placing the qualified mixed material in a roller furnace for calcination, and setting a temperature rise section: 4-6 h; and (3) a constant temperature section: 8-14 h; a cooling section: 4-6 h; constant temperature: 880-950 degrees; simultaneously, introducing air and oxygen, wherein the air inflow is as follows: 100 to 200m³Monitoring the oxygen concentration of the kiln to be more than 40 percent;

and S4, crushing the qualified sintering materials, batching, sieving, removing iron, and packaging to obtain the high-nickel ternary cathode material.

2. The method for preparing the low-energy-consumption high-nickel ternary material as claimed in claim 1, wherein the molecular formula of the high-nickel precursor is Ni_0.55C0_0.15Mn_0.3(OH)₂The particle D50 was controlled to be 9 to 11 μm.

3. The method for preparing the ternary material with low energy consumption and high nickel content as claimed in claim 1, wherein the lithium carbonate particles D50 are 7-9 μm.

4. The method for preparing the low-energy-consumption high-nickel ternary material as claimed in claim 1, wherein the metal element A is any one or more of nanoscale aluminum, titanium, magnesium, zirconium or niobium.

5. The method for preparing the low-energy-consumption high-nickel ternary material as claimed in claim 1, wherein the roller furnace in S3 is a double-pushing four-row roller furnace.

6. The method for preparing a low-energy-consumption high-nickel ternary material according to claim 1, wherein a sagger with the size of S3 is used: 830 × 100mm, load upper layer: 6-10 kg; 5-7 kg of the lower layer, and respectively measuring the alkali content of the upper layer and the lower layer after sintering.

Technical Field

The invention relates to a preparation method of a low-energy-consumption high-nickel ternary material.

Background

The lithium ion battery anode material mainly comprises lithium cobaltate, lithium manganate, lithium iron phosphate and ternary material (lithium nickel cobalt manganese). The ternary material (nickel cobalt lithium manganate) occupies the largest share of the lithium ion battery positive electrode material market by virtue of the advantages of good cycle performance, high capacity, high energy density and the like. The ternary material is a composite metal oxide (LiNixC0yMn1-x-yO2) mainly composed of three metal elements of nickel, cobalt and manganese. The anode material is divided into 333, 523, 622, 811 and other different types according to different proportions, wherein the 523 ternary anode material has the largest market demand.

The conventional ternary material adopts a high-temperature solid phase method, a high-quality lithium source, a precursor and trace dopants are fully mixed and then sintered at high temperature, and the sintering process is assisted by compressed air or high-purity oxygen for catalysis. The air input, the air displacement, the bowl loading amount, the sintering temperature curve and the sintering time need to be well controlled in the sintering process of the kiln. Each link affects the energy consumption of the product.

The lithium source accounts for 40% of the cost of the raw materials of the whole product, and the price of the high-quality lithium source is 3000-; cobalt is a metal substance with the highest cost in the ternary material, the proportion of the ternary material (LiNi0.5C00.2Mn0.3O2) to cobalt is higher than that of a nickel product, and the cost of a precursor is also higher;

in the sintering process, in order to control the discharge of impurity gases, the exhaust amount is increased, the bowl loading amount is controlled, the product needs enough atmosphere to ensure the performance of the material in the synthesis process, and the air inflow amount is also increased. This results in a limited yield and a large energy consumption.

Disclosure of Invention

The invention aims to overcome the defects of high cost and high energy consumption of ternary materials in the prior art and provide a preparation method of a low-energy-consumption high-nickel ternary material.

In order to solve the technical problems, the invention provides the following technical scheme:

selecting a high-nickel ternary precursor with a molecular formula of Ni0.55C00.15Mn0.3(OH)2, and controlling the particle D50 to be 9-11 mu m; a technical grade 1 lithium carbonate (main content 99.4%) was controlled to have a particle D50 of 7 to 9 μm. As a relatively high cost-effective raw material.

The industrial grade 1 is used for the raw material lithium source, so that the quality of the product is ensured, and the cost of the material is reduced; high nickel ternary material (LiNi)_0.55C0_0.15Mn_0.3O₂) Comparative ternary (LiNi)_0.5C0_0.2Mn_0.3O₂) The nickel content is increased and the cobalt content is reduced. The material has higher energy density and capacity exertion, and the cost of the material is reduced; the atmosphere control in the sintering process can be realized by combining 50% of oxygen and 50% of air, the necessary oxygen concentration in the material synthesis process is given, the loading capacity is improved by using a large-size saggar, different loading capacities of an upper layer and a lower layer can be flexibly utilized, the pushing speed of a kiln is accelerated to reduce the sintering period, and the like, so that the sintering energy consumption is reduced; the mixing process can meet the control of the electrochemical performance and alkali amount of the material by doping one or more metal oxides in a small amount.

The preparation method comprises the following steps: weighing a proper amount of high-nickel precursor and lithium carbonate, and doping metal elements (nano-scale metal oxides such as aluminum, titanium, magnesium, zirconium, niobium and the like) in a quantitative proportion. Wherein the ratio of the lithium source to the high-nickel precursor is 1.02-1.1: 1. the addition amount of the metal element A is 0.1-0.5% of the theoretical product quality.

Putting the weighed raw materials into a high-speed mixer for fully mixing for the following time: 25-40min, rotation speed: 300-.

Placing the qualified mixed material in a roller furnace (double-pushing four rows) for calcining, and setting a temperature rise section: 4-6 h; and (3) a constant temperature section: 8-14 h; a cooling section: 4-6 h. Constant temperature: 880 to 950 degrees. Simultaneously, introducing air and oxygen, wherein the air inflow is as follows: 100 to 200m³And h, monitoring the oxygen concentration of the kiln to be more than 40 percent. The size of the used sagger is as follows: 830 × 100mm, load upper layer: 6-10 kg; 5-7 kg of the lower layer, and respectively measuring the alkali content of the upper layer and the lower layer after sintering.

And crushing the qualified sintering materials, combining, sieving, removing iron, and packaging to obtain the high-nickel ternary cathode material.

Has the advantages that: the invention has simple process and strong practicability, and can realize full automation in batch production; firstly, a high-nickel low-cobalt precursor and industrial grade-1 lithium carbonate are selected as raw materials, so that the cost is lower; the solid phase doped nano-scale metal elements are beneficial to stabilizing the crystal structure of the material, so that the material is not easy to damage in the charging and discharging process, the residual alkali amount in sintering is effectively reduced, and the charging and discharging performance is improved; the air intake condition of each half of air and oxygen is used, so that the cost is lower than that of pure oxygen, and the catalytic action of the material in the synthesis process can be ensured; the large-capacity saggars are adopted, more loading brings improvement of yield, gas volatilization of the saggars on the lower layer is insufficient in the production process, and the loading can be reduced compared with the saggars on the upper layer to achieve balance of performance.

Drawings

The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention. In the drawings:

FIG. 1 is a scanning electron microscope for testing after sampling the finished product of example 1;

FIG. 2 is a scanning electron microscope for testing after sampling the finished product of example 2;

FIG. 3 is a scanning electron microscope for testing after sampling the finished product of example 3.

Detailed Description

The preferred embodiments of the present invention will be described in conjunction with the accompanying drawings, and it will be understood that they are described herein for the purpose of illustration and explanation and not limitation.

Example 1

Respectively putting a high-nickel ternary precursor Ni0.55C00.15Mn0.3(OH)2 into a raw material bin of a high-mixing metering system, wherein D50 is 9-11 mu m, industrial grade 1 lithium carbonate is required, and D50 is 7-9 mu m.

The metering standard values of the precursor and the lithium carbonate are set to be 210.4kg and 89.2kg respectively, and the deviation of the metering result and the standard value required by starting metering cannot exceed 0.15%. The weighed additive, nano-alumina, 420g was added manually. The rotation speed was set at 400rpm, the lithium content was measured after 30 minutes of mixing, and if the mixture failed, additional mixing was carried out for 10 minutes.

The mixed raw materials are transferred to a bowl loading metering system through spiral conveying, and the loading of the upper layer sagger is set to be 10kg, and the loading of the lower layer sagger is set to be 7 kg. The size of the sagger is as follows: 830 x 100 mm.

Sending the loaded sagger into a double-layer four-row atmosphere roller wayIn the furnace, the kiln is set to be heated to 500 ℃ for 2 hours, heated to 930 ℃ for 4 hours, kept at 930 ℃ for 12 hours, naturally cooled, and the whole sintering period is 24 hours. And (3) introducing air and half of oxygen simultaneously in the sintering process, and totally introducing air: 200m³H, opening strong exhaust, and the oxygen concentration in the furnace is as follows: 50 percent. The alkali content of the upper and lower layers after the material was discharged was measured, and the results are shown in Table 1.

After cooling, the material is sent into a rotary wheel mill for coarse crushing and then is sent to a machine for fine crushing, and the granularity D50 is controlled: 9 to 15 μm. And conveying the crushed materials to a gas mixing bin mixing batch, introducing dry air, and starting mixing for 10 minutes. And finally, sieving the mixture by a 400-mesh vibrating screen, removing iron, and packaging to obtain a material, wherein a ton bag or a small bag can be selected for free switching. The whole post-treatment process is in a dry and closed environment, and the environmental dew point is required to be within 10. The finished product obtained was tested by scanning electron microscopy (see FIG. 1) and half-cell performance testing (0.1C, 2.75-4.3V) after sampling, the results of which are shown in Table 1.

Example 2:

respectively putting a high-nickel ternary precursor Ni0.55C00.15Mn0.3(OH)2 into a raw material bin of a high-mixing metering system, wherein D50 is 9-11 mu m, industrial grade 1 lithium carbonate is required, and D50 is 7-9 mu m.

The metering standard values of the precursor and the lithium carbonate are set to be 210.4kg and 89.2kg respectively, and the deviation of the metering result and the standard value required by starting metering cannot exceed 0.15%. The weighed additive, nano-alumina, 420g was added manually. The rotation speed was set at 400rpm, the lithium content was measured after 30 minutes of mixing, and if the mixture failed, additional mixing was carried out for 10 minutes.

The mixed raw materials are transferred to a bowl loading metering system through spiral conveying, and the loading of the upper layer sagger is set to be 9kg, and the loading of the lower layer sagger is set to be 6 kg. The size of the sagger is as follows: 830 x 100 mm.

And (3) feeding the loaded sagger into a double-layer four-row atmosphere roller furnace, heating the sagger to 500 ℃ for 2 hours, heating the sagger to 920 ℃ for 4 hours, keeping the temperature at 920 ℃ for 12 hours, and naturally cooling the sagger, wherein the whole sintering period is 24 hours. And (3) introducing air and half of oxygen simultaneously in the sintering process, and totally introducing air: 200m³H, opening strong exhaust, and the oxygen concentration in the furnace is as follows: 50 percent. The alkali content of the upper and lower layers after the material was discharged was measured, and the results are shown in Table 1.

After cooling, the material is sent into a rotary wheel mill for coarse crushing and then is sent to a machine for fine crushing, and the granularity D50 is controlled: 9 to 15 μm. And conveying the crushed materials to a gas mixing bin mixing batch, introducing dry air, and starting mixing for 10 minutes. And finally, sieving the mixture by a 400-mesh vibrating screen, removing iron, and packaging to obtain a material, wherein a ton bag or a small bag can be selected for free switching. The whole post-treatment process is in a dry and closed environment, and the environmental dew point is required to be within 10. The finished product obtained was tested by scanning electron microscopy (see FIG. 2) and half-cell performance testing (0.1C, 2.75-4.3V) after sampling, the results of which are shown in Table 1.

Example 3:

respectively putting a high-nickel ternary precursor Ni0.55C00.15Mn0.3(OH)2 into a raw material bin of a high-mixing metering system, wherein D50 is 9-11 mu m, industrial grade 1 lithium carbonate is required, and D50 is 7-9 mu m.

The metering standard values of the precursor and the lithium carbonate are set to be 210.4kg and 89.2kg respectively, and the deviation of the metering result and the standard value required by starting metering cannot exceed 0.15%. The weighed additive, nano-alumina, 420g was added manually. The rotation speed was set at 400rpm, the lithium content was measured after 30 minutes of mixing, and if the mixture failed, additional mixing was carried out for 10 minutes.

And transferring the mixed raw materials to a bowl loading metering system through spiral conveying, and respectively setting the loading of an upper layer of sagger to be 8kg and the loading of a lower layer of sagger to be 5 kg. The size of the sagger is as follows: 830 x 100 mm.

And (3) feeding the loaded sagger into a double-layer four-row atmosphere roller furnace, heating the sagger to 500 ℃ for 2 hours, heating the sagger to 910 ℃ for 4 hours, keeping the temperature of the sagger at 910 ℃ for 12 hours, and naturally cooling the sagger, wherein the whole sintering period is 24 hours. And (3) introducing air and half of oxygen simultaneously in the sintering process, and totally introducing air: 200m³H, opening strong exhaust, and the oxygen concentration in the furnace is as follows: 50 percent. The alkali content of the upper and lower layers of the material after discharge was measured, and the results of the obtained finished product after sampling by a scanning electron microscope (see fig. 2) are shown in table 1.

After cooling, the material is sent into a rotary wheel mill for coarse crushing and then is sent to a machine for fine crushing, and the granularity D50 is controlled: 9 to 15 μm. And conveying the crushed materials to a gas mixing bin mixing batch, introducing dry air, and starting mixing for 10 minutes. And finally, sieving the mixture by a 400-mesh vibrating screen, removing iron, and packaging to obtain a material, wherein a ton bag or a small bag can be selected for free switching. The whole post-treatment process is in a dry and closed environment, and the environmental dew point is required to be within 10. The finished product obtained was tested by scanning electron microscopy (see FIG. 3) and half-cell performance testing (0.1C, 2.75-4.3V) after sampling, the results of which are shown in Table 1.

Table 1 results of half cell performance testing of examples 1-3

And (4) conclusion: according to different sagger loading amounts, the less the yield, the better the sintering performance and the higher the crystal integrity. The difference of the upper layer and the lower layer is obvious, and the loading amount of the upper layer and the lower layer can be adjusted according to different conditions in actual production.

Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.