CN117303337A - A kind of doping preparation method of lithium iron manganese phosphate composite cathode material - Google Patents

A kind of doping preparation method of lithium iron manganese phosphate composite cathode material Download PDF

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CN117303337A
CN117303337A CN202311187803.8A CN202311187803A CN117303337A CN 117303337 A CN117303337 A CN 117303337A CN 202311187803 A CN202311187803 A CN 202311187803A CN 117303337 A CN117303337 A CN 117303337A
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doping
lithium iron
lithium
manganese phosphate
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闫俊杰
薛娟娟
王勇
刘春祥
张家晟
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Shandong Goldencell Electronics Technology Co Ltd
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Abstract

The invention belongs to the technical field of lithium battery anode materials, and particularly relates to a preparation method for doping a lithium manganese iron phosphate anode material. The invention discloses a doping preparation method of a lithium iron manganese phosphate composite anode material, which comprises the steps of 1) preparing a lattice doped type manganese iron phosphate precursor by coprecipitation of soluble manganese sources, iron sources, phosphorus sources and first doping agents with different contents. 2) And (3) dehydrating the precursor prepared in the step (1), and grinding the dehydrated precursor, the lithium source, the composite carbon source and the second doping agent to prepare mixed slurry. 3) And (3) spray-drying, sintering and air-powder the mixed slurry to prepare the lithium iron manganese phosphate composite anode material. According to the preparation method, the doping element quantity of the first doping agent is determined according to the manganese element content, the original lattice parameter is changed through element doping, a lithium ion diffusion channel is increased, and the ion conductivity is improved. The second doping agent has good high temperature resistance, ensures good doping property, can inhibit the growth of primary particle size in the material sintering process, ensures the preparation of small-particle-size materials, and shortens the diffusion path of lithium ions.

Description

一种磷酸锰铁锂复合正极材料掺杂制备方法A kind of doping preparation method of lithium iron manganese phosphate composite cathode material

技术领域Technical field

本发明属于一种锂电池正极材料技术领域，具体为一种磷酸锰铁锂正极材料掺杂制备方法。The invention belongs to the technical field of lithium battery cathode materials, and is specifically a doping and preparation method of lithium iron manganese phosphate cathode materials.

技术背景technical background

磷酸锰铁锂属于磷酸铁锂与磷酸锰锂混掺的产物，在结构方面与磷酸铁锂相同，晶型方面均为有序规整的橄榄石型结构，因此和磷酸铁锂一样具有较高的结构稳定性。锰元素相较于贵重金属钴和镍价格便宜，原料制备成本较低。再加上类似铁锂的高安全性能，高热稳定性等优点，可以说是兼具磷酸铁锂和磷酸锰锂优点，同时还可以弥补了磷酸铁锂能量密度低的短板，因此也被誉为“磷酸铁锂的升级版”。Lithium iron manganese phosphate is a product of mixing lithium iron phosphate and lithium manganese phosphate. Its structure is the same as that of lithium iron phosphate. In terms of crystal form, it is an ordered and regular olivine structure. Therefore, it has the same high electrochemical properties as lithium iron phosphate. Structural stability. Manganese is cheaper than the precious metals cobalt and nickel, and the cost of raw material preparation is low. Coupled with the high safety performance and high thermal stability similar to lithium iron, it can be said that it has the advantages of lithium iron phosphate and lithium manganese phosphate, and can also make up for the shortcomings of low energy density of lithium iron phosphate, so it is also known as It is an "upgraded version of lithium iron phosphate".

磷酸锰铁锂理论容量与磷酸铁锂相同，为170mAh/g；但磷酸锰铁锂材料电压平台为4.1V，远高于磷酸铁锂的3.4V，平台电压提升了20%，从而促使相同的电池能力密度较磷酸铁锂材料提升20％。The theoretical capacity of lithium iron manganese phosphate is the same as that of lithium iron phosphate, which is 170mAh/g; however, the material voltage platform of lithium iron manganese phosphate is 4.1V, which is much higher than the 3.4V of lithium iron phosphate. The platform voltage is increased by 20%, thus promoting the same The battery capacity density is 20% higher than that of lithium iron phosphate material.

磷磷酸锰铁锂电导率比磷酸铁锂更低，充放电倍率性能也更差。且磷酸锰铁锂中有锰元素含量较高，高温过程中会导致锰的大量溶出进而使得高温循环寿命变短。目前常规操作是通过类似铁锂的掺杂、包覆、纳米化来改善材料电导率和循环问题。但是一般的掺杂和纳米化处理等改性方法很难大幅度改善此类问题。The conductivity of lithium iron phosphorus manganese phosphate is lower than that of lithium iron phosphate, and the charge and discharge rate performance is also worse. Moreover, lithium iron manganese phosphate has a high content of manganese, which will cause a large amount of manganese to dissolve during the high-temperature process, thereby shortening the high-temperature cycle life. At present, the conventional operation is to improve the material conductivity and cycle problems through doping, coating and nanonization of iron and lithium. However, general modification methods such as doping and nanotechnology are difficult to significantly improve such problems.

发明内容Contents of the invention

本发明的目的是针对现有技术中存在的上述缺点进行改进，提供一种一种磷酸锰铁锂复合正极材料掺杂制备方法。The purpose of the present invention is to improve the above-mentioned shortcomings existing in the prior art and provide a doping preparation method of lithium iron manganese phosphate composite cathode material.

为实现上述目的，本发明技术方案如下：In order to achieve the above objects, the technical solutions of the present invention are as follows:

本发明磷酸锰铁锂复合正极材料掺杂制备方法，包含以下步骤：The doping preparation method of lithium iron manganese phosphate composite cathode material of the present invention includes the following steps:

（1）将不同含量可溶性锰源、铁源、磷源、第一掺杂剂，共沉淀制备晶格掺杂型磷酸锰铁前驱体。(1) Co-precipitate soluble manganese source, iron source, phosphorus source and first dopant with different contents to prepare lattice-doped iron manganese phosphate precursor.

（2）将步骤（1）将制备前驱体脱水后与锂源、复合碳源、第二掺杂剂，砂磨制备混合浆料。(2) Dehydrate the precursor prepared in step (1) with the lithium source, composite carbon source, and second dopant, and sand grind to prepare a mixed slurry.

（3）将混合浆料喷雾干燥、烧结、气粉制备磷酸锰铁锂复合正极材料。 (3) Spray dry, sinter and air powder the mixed slurry to prepare lithium iron manganese phosphate composite cathode material.

根据所述的制备方法，步骤（1）中，所述的可溶性锰源、铁源、第一掺杂剂中锰元素、铁元素、掺杂元素原子摩尔比为（0.6-0.9）：（0.4-0.1）：（0.006-0.009）。According to the preparation method, in step (1), the atomic molar ratio of manganese element, iron element, and doping element in the soluble manganese source, iron source, and first dopant is (0.6-0.9): (0.4 -0.1): (0.006-0.009).

根据所述的制备方法步骤（1）中，所述的第一掺杂剂为硫酸镁、硝酸铝、硫酸钠中的一种或多种混合物。According to step (1) of the preparation method, the first dopant is one or more mixtures of magnesium sulfate, aluminum nitrate, and sodium sulfate.

根据所述的制备方法，步骤（1）中，所述的共沉淀反应温度为90-120℃，反应pH为1-4。According to the preparation method, in step (1), the co-precipitation reaction temperature is 90-120°C, and the reaction pH is 1-4.

根据所述的制备方法，步骤（2）中，所述的第二掺杂剂为纳米氧化钛和纳米氧化铝中的一种或两种混合物。According to the preparation method, in step (2), the second dopant is one or a mixture of nano titanium oxide and nano aluminum oxide.

根据所述的制备方法，步骤（2）中，所述的第二掺杂剂粒度D50-N为30-60nm。According to the preparation method, in step (2), the second dopant particle size D50-N is 30-60 nm.

根据所述的制备方法，步骤（2）中，所述的混合浆料粒度D50为120-300nm。According to the preparation method, in step (2), the particle size D50 of the mixed slurry is 120-300 nm.

根据所述的制备方法，步骤（2）中，所述的碳源为无水葡萄糖、可溶性淀粉、PEG、柠檬酸、酚醛树脂等的两种或多种的组合。According to the preparation method, in step (2), the carbon source is a combination of two or more types of anhydrous glucose, soluble starch, PEG, citric acid, phenolic resin, etc.

根据所述的制备方法，其特征在于，所述的烧结温度为750-850℃。According to the preparation method, the sintering temperature is 750-850°C.

根据所述的制备方法，步骤（3）中， 所述的气粉粒度D50为0.5-1.0um。According to the preparation method, in step (3), the particle size D50 of the air powder is 0.5-1.0um.

本发明技术方案有益效果为：The beneficial effects of the technical solution of the present invention are:

本发明制备方法根据锰元素含量确定第一掺杂剂掺杂元素量，通过元素掺杂改变原有的晶格参数，增加锂离子扩散通道，提高离子电导率。第二掺杂剂耐高温性能较好，并根据第二掺杂剂粒度确定砂磨粒度，保证良好掺杂性的同时可以抑制材料烧结过程中一次粒径的生长，保证制备小粒径材料，缩短锂离子扩散路径。结合复合碳源包覆进一步提高了材料的离子导率和电子电导率，极大改善材料倍率性能。The preparation method of the present invention determines the doping element amount of the first dopant based on the manganese element content, changes the original lattice parameters through element doping, increases lithium ion diffusion channels, and improves ion conductivity. The second dopant has better high temperature resistance, and the sanding particle size is determined according to the particle size of the second dopant. This ensures good doping properties while inhibiting the growth of primary particle size during the sintering process of the material, ensuring the preparation of small particle size materials. Shorten the lithium ion diffusion path. Combined with composite carbon source coating, the ionic conductivity and electronic conductivity of the material are further improved, greatly improving the rate performance of the material.

本发明在原有的磷酸铁锂产线稍加改造均能实现，设备成本低，易于产业化。The present invention can be implemented in the original lithium iron phosphate production line with slight modifications, has low equipment cost and is easy to be industrialized.

附图说明Description of the drawings

图1为实施例1制得的磷酸锰铁锂正极材料放电曲线图。Figure 1 is a discharge curve of the lithium iron manganese phosphate cathode material prepared in Example 1.

图2为实施例2制得的锂磷酸锰铁锂正极材料倍率性能曲线图。Figure 2 is a rate performance curve of the lithium manganese iron phosphate cathode material prepared in Example 2.

图3为实施例3制得的锂磷酸锰铁锂正极材料和对比例制得材料的EIS对比图。Figure 3 is an EIS comparison chart of the lithium manganese iron phosphate cathode material prepared in Example 3 and the material prepared in the comparative example.

实施方式Implementation

下面结合具体实施例进一步描述本发明，在不脱离本发明上述技术思想情况下，根据本领域普通技术知识和惯用手段做出的各种替换或变更，均包括在本发明的范围内。The present invention will be further described below with reference to specific embodiments. Without departing from the above-mentioned technical ideas of the present invention, various substitutions or changes made based on common technical knowledge and conventional means in the art are all included in the scope of the present invention.

本发明磷酸锰铁锂复合正极材料掺杂制备方法，包含以下步骤：The doping preparation method of lithium iron manganese phosphate composite cathode material of the present invention includes the following steps:

（1）将可溶性锰源、铁源、磷源、第一掺杂剂混合，可溶性锰源、铁源、第一掺杂剂中锰元素、铁元素、掺杂元素原子摩尔比为（0.6-0.9）：（0.4-0.1）：（0.006-0.009），共沉淀制备晶格掺杂型磷酸锰铁前驱体，共沉淀反应温度为90-120℃，反应pH为1-4；其中第一掺杂剂为硫酸镁、硝酸铝、硫酸钠中的一种或多种混合物；(1) Mix the soluble manganese source, iron source, phosphorus source and first dopant. The atomic molar ratio of manganese element, iron element and doping element in the soluble manganese source, iron source and first dopant is (0.6- 0.9): (0.4-0.1): (0.006-0.009), coprecipitation to prepare lattice-doped iron manganese phosphate precursor, the coprecipitation reaction temperature is 90-120°C, and the reaction pH is 1-4; among which the first doped The impurity is one or more mixtures of magnesium sulfate, aluminum nitrate, and sodium sulfate;

（2）将步骤（1）将制备前驱体脱水，然后加入锂源、复合碳源、第二掺杂剂，第二掺杂剂为纳米氧化钛和纳米氧化铝中的一种或两种混合物，所述第二掺杂剂粒度D50-N为30-60nm，碳源为无水葡萄糖、可溶性淀粉、PEG、柠檬酸、酚醛树脂等的两种或多种的组合，然后砂磨制备混合浆料，混合浆料粒度D50为120-300nm；(2) Dehydrate the precursor prepared in step (1), and then add a lithium source, a composite carbon source, and a second dopant. The second dopant is one or a mixture of nanotitanium oxide and nanoalumina. , the second dopant particle size D50-N is 30-60nm, the carbon source is a combination of two or more types of anhydrous glucose, soluble starch, PEG, citric acid, phenolic resin, etc., and then sanded to prepare a mixed slurry Material, the particle size D50 of the mixed slurry is 120-300nm;

（3）将混合浆料喷雾干燥，然后烧结，烧结温度为750-850℃，最后气流粉碎，气气流粉碎后颗粒的粒度D50为0.5-1.0um，最终获得磷酸锰铁锂复合正极材料。 (3) The mixed slurry is spray-dried, then sintered at a sintering temperature of 750-850°C, and finally air-pulverized. The particle size D50 of the air-pulverized particles is 0.5-1.0um, and finally the lithium iron manganese phosphate composite cathode material is obtained.

以三个实施例对本发明进行进一步的说明The present invention is further illustrated with three embodiments.

实施例Example

一种磷酸锰铁锂复合正极材料掺杂制备方法，步骤包括：A doping preparation method of lithium iron manganese phosphate composite cathode material, the steps include:

（1）将1014g一水硫酸锰、1112g七水硫酸亚铁、1150g磷酸二氢铵、1.3g硝酸铝，磷酸调节pH至2.1，反应温度100℃制备晶格掺杂型前驱体。(1) Prepare lattice doping precursor by adjusting 1014g manganese sulfate monohydrate, 1112g ferrous sulfate heptahydrate, 1150g ammonium dihydrogen phosphate, 1.3g aluminum nitrate, and phosphoric acid to 2.1, and the reaction temperature is 100°C.

（2）将步骤（1）所得脱水后前驱体1000g、250g碳酸锂锂、1.5g纳米二氧化钛（D50-N=50nm）、60g无水葡萄糖、30gPEG-1000砂磨制备D50为200nm的混合浆料。(2) Sand grind 1000g of the dehydrated precursor obtained in step (1), 250g of lithium carbonate, 1.5g of nano-titanium dioxide (D50-N=50nm), 60g of anhydrous glucose, and 30g of PEG-1000 to prepare a mixed slurry with a D50 of 200nm. .

（3）将步骤（2）所得浆料喷雾干燥，780℃-10h烧结，气粉至D50为0.7um得到最终磷酸锰铁锂复合正极材料(3) Spray dry the slurry obtained in step (2), sinter at 780℃-10h, and air-powder it to D50 of 0.7um to obtain the final lithium iron manganese phosphate composite cathode material.

产品性能检测：材料1C放电容量140mAh/gProduct performance testing: Material 1C discharge capacity 140mAh/g

实施例Example

一种磷酸锰铁锂复合正极材料掺杂制备方法，步骤包括：A doping preparation method of lithium iron manganese phosphate composite cathode material, the steps include:

（1）将1183g一水硫酸锰、834g七水硫酸亚铁、1150g磷酸二氢铵、0.89g硝酸镁，磷酸调节pH至1.5，反应温度100℃制备晶格掺杂型前驱体。(1) Prepare lattice doping precursor by adjusting 1183g manganese sulfate monohydrate, 834g ferrous sulfate heptahydrate, 1150g ammonium dihydrogen phosphate, 0.89g magnesium nitrate, and phosphoric acid to 1.5, and the reaction temperature is 100°C.

（2）将步骤（1）所得脱水后前驱体1000g、250g碳酸锂锂、1.5g纳米二氧化钛（D50-N=30nm）、60g无水葡萄糖、30gPEG-1000砂磨制备D50为150nm的混合浆料。(2) Sand grind 1000g of the dehydrated precursor obtained in step (1), 250g of lithium lithium carbonate, 1.5g of nano-titanium dioxide (D50-N=30nm), 60g of anhydrous glucose, and 30g of PEG-1000 to prepare a mixed slurry with a D50 of 150nm. .

（3）将步骤（2）所得浆料喷雾干燥，780℃-10h烧结，气粉至D50为0.8um得到最终磷酸锰铁锂复合正极材料(3) Spray dry the slurry obtained in step (2), sinter at 780℃-10h, and air-powder it to D50 of 0.8um to obtain the final lithium iron manganese phosphate composite cathode material.

产品性能检测：材料5C放电容量113.2mAh/g，获得如图2所示的磷酸锰铁锂正极材料正极材料倍率性能曲线图。Product performance testing: The 5C discharge capacity of the material is 113.2mAh/g, and the rate performance curve of the lithium iron manganese phosphate cathode material cathode material is obtained as shown in Figure 2.

实施例Example

一种磷酸锰铁锂复合正极材料掺杂制备方法，步骤包括：A doping preparation method of lithium iron manganese phosphate composite cathode material, the steps include:

（1）将1014g一水硫酸锰、1112g七水硫酸亚铁、1150g磷酸二氢铵、1.0g硝酸铝，磷酸调节pH至2.1，反应温度100℃制备晶格掺杂型前驱体。(1) Prepare lattice doping precursor by adjusting 1014g manganese sulfate monohydrate, 1112g ferrous sulfate heptahydrate, 1150g ammonium dihydrogen phosphate, 1.0g aluminum nitrate, and phosphoric acid to 2.1, and the reaction temperature is 100°C.

（2）将步骤（1）所得脱水后前驱体1000g、250g碳酸锂锂、1.8g纳米三氧化二铝（D50-N=50nm）、60g无水葡萄糖、30g可溶性淀粉，砂磨制备D50为200nm的混合浆料。(2) Combine 1000g of the dehydrated precursor obtained in step (1), 250g of lithium carbonate, 1.8g of nano-aluminum trioxide (D50-N=50nm), 60g of anhydrous glucose, and 30g of soluble starch, and prepare a D50 of 200nm by sanding of mixed slurry.

（3）将步骤（2）所得浆料喷雾干燥，800℃-10h烧结，气粉至D50为0.7um得到最终磷酸锰铁锂复合正极材料(3) Spray dry the slurry obtained in step (2), sinter at 800℃-10h, and air-powder it to D50 of 0.7um to obtain the final lithium iron manganese phosphate composite cathode material.

产品性能检测：材料制备电池阻抗降低，锂离子扩散系数提高。Product performance testing: The material preparation battery impedance is reduced and the lithium ion diffusion coefficient is increased.

对比例Comparative ratio

一种磷酸锰铁锂正极材料制备方法，步骤包括： A method for preparing lithium iron manganese phosphate cathode material, the steps include:

（1）将1014g一水硫酸锰、1112g七水硫酸亚铁、1150g磷酸二氢铵，磷酸调节pH至2.1，反应温度100℃制备晶格掺杂型前驱体。(1) Prepare a lattice doping precursor by adjusting 1014g manganese sulfate monohydrate, 1112g ferrous sulfate heptahydrate, 1150g ammonium dihydrogen phosphate, phosphoric acid to 2.1, and the reaction temperature is 100°C.

（2）将步骤（1）所得脱水后前驱体1000g、250g碳酸锂锂、60g无水葡萄糖、30gPEG-1000砂磨制备D50为200nm的混合浆料。(2) Sand grind 1000g of the dehydrated precursor obtained in step (1), 250g of lithium carbonate, 60g of anhydrous glucose, and 30g of PEG-1000 to prepare a mixed slurry with a D50 of 200nm.

（3）将步骤（2）所得浆料喷雾干燥，780℃-10h烧结，气粉至D50为0.7um得到最终磷酸锰铁锂复合正极材料。(3) Spray dry the slurry obtained in step (2), sinter at 780℃-10h, and air-powder it to D50 of 0.7um to obtain the final lithium iron manganese phosphate composite cathode material.

将实施例3获得的成品与对比例获得成品进行过测试，获得如图3所示的材料的EIS对比图。The finished product obtained in Example 3 and the finished product obtained in the Comparative Example were tested, and the EIS comparison chart of the material as shown in Figure 3 was obtained.

本发明制备方法根据锰元素含量确定第一掺杂剂掺杂元素量，通过元素掺杂改变原有的晶格参数，增加锂离子扩散通道，提高离子电导率。第二掺杂剂耐高温性能较好，并根据第二掺杂剂粒度确定砂磨粒度，保证良好掺杂性的同时可以抑制材料烧结过程中一次粒径的生长，保证制备小粒径材料，缩短锂离子扩散路径。结合复合碳源包覆进一步提高了材料的离子导率和电子电导率，极大改善材料倍率性能。The preparation method of the present invention determines the doping element amount of the first dopant based on the manganese element content, changes the original lattice parameters through element doping, increases lithium ion diffusion channels, and improves ion conductivity. The second dopant has better high temperature resistance, and the sanding particle size is determined according to the particle size of the second dopant. This ensures good doping properties while inhibiting the growth of primary particle size during the sintering process of the material, ensuring the preparation of small particle size materials. Shorten the lithium ion diffusion path. Combined with composite carbon source coating, the ionic conductivity and electronic conductivity of the material are further improved, greatly improving the rate performance of the material.

本发明在原有的磷酸铁锂产线稍加改造均能实现，设备成本低，易于产业化。The present invention can be realized in the original lithium iron phosphate production line with slight modifications, has low equipment cost and is easy to be industrialized.

Claims (10)

1. The doping preparation method of the lithium iron manganese phosphate composite anode material is characterized by comprising the following steps of:
(1) Mixing a soluble manganese source, an iron source, a phosphorus source and a first doping agent, and coprecipitating to prepare a lattice doped ferromanganese phosphate precursor;
(2) Dehydrating the precursor prepared in the step (1), adding a lithium source, a composite carbon source and a second doping agent, and sanding to prepare mixed slurry;
(3) And (3) spray-drying, sintering and air-powder the mixed slurry to prepare the lithium iron manganese phosphate composite anode material.
2. The method for preparing the lithium iron manganese phosphate composite positive electrode material according to claim 1, which is characterized in that: in the step (1), the atomic mole ratio of the manganese element, the iron element and the doping element in the soluble manganese source, the iron source and the first doping agent is (0.6-0.9): (0.4-0.1): (0.006-0.009).
3. The method for preparing the lithium iron manganese phosphate composite positive electrode material according to claim 1, which is characterized in that: in the step (1), the first dopant is one or a mixture of more of magnesium sulfate, aluminum nitrate and sodium sulfate.
4. The method for preparing the lithium iron manganese phosphate composite positive electrode material according to claim 1, which is characterized in that: in the step (1), the coprecipitation reaction temperature is 90-120 ℃ and the reaction pH is 1-4.
5. The method for preparing the lithium iron manganese phosphate composite positive electrode material according to claim 1, which is characterized in that: in the step (2), the second dopant is one or a mixture of two of nano titanium oxide and nano aluminum oxide.
6. The method for preparing the lithium iron manganese phosphate composite positive electrode material according to claim 1, which is characterized in that: in the step (2), the second dopant particle size D50-N is 30-60nm.
7. The method for preparing the lithium iron manganese phosphate composite positive electrode material according to claim 1, which is characterized in that: in the step (2), the particle size D50 of the mixed slurry is 120-300nm.
8. The method for preparing a lithium iron manganese phosphate composite anode material according to claim 1, wherein in the step (2), the carbon source is a combination of two or more of anhydrous glucose, soluble starch, PEG, citric acid, phenolic resin and the like.
9. The method for preparing a lithium iron manganese phosphate composite positive electrode material according to claim 1, wherein in the step (3), the sintering temperature is 750-850 ℃.
10. The method for preparing lithium iron manganese phosphate composite anode material according to claim 1, wherein in the step (3), the particle size D50 of the gas-powder particles is 0.5-1.0um.
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