锂离子电池正极材料LiFePO_4前驱体的制备及合成LiFePO_4/C的性能研究
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摘要
橄榄石型LiFePO4作为锂离子电池正极材料因其理论容量高、平台特性好、原料丰富、价格低廉、环境友好、安全性能好等优点而受到人们的广泛关注。但是该材料倍率性能差,以及振实密度小,严重限制了LiFePO4的实际应用。本文采用均匀沉淀法和氧化沉淀转化法制备前驱体FePO4,然后合成LiFePO4/C。研究了物理性能和电化学性能的关系。
采用均匀沉淀法制备LiFePO4/C前驱体磷酸铁,比较了尿素添加量、表面活性剂对FePO4结构、形貌以及LiFePO4电化学性能的影响。结果表明：未添加表面活性剂,最优情况下合成LiFePO4的首次放电比容量为141.9mAh/g,倍率性能差。添加表面活性剂PEG制备的LiFePO4/C在O.1C倍率下放电比容量为151.5mAh/g,1C倍率下的放电比容量为122.5mAh/g,振实密度达1.17cm3/g。
研究了制备LiFePO4前驱体磷酸铁的新方法-氧化沉淀转化法：在pH=9.5的条件下制备纳米磷酸亚铁悬浊液,然后在pH=2的条件下将其氧化制备获得磷酸铁。结果表明：制备的磷酸铁形貌为类球形,尺寸为100nm左右。以该磷酸铁为前驱体合成的LiFePO4/C在O.1C倍率下首次放电比容量为139.8mAh/g,2C倍率下放电容量为123.2mAh/g,具有优良的倍率性能。
以商业化磷酸铁为原料,研究不同碳源制备的LiFePO4/C的物理性能和电化学性能的关系。结果表明：碳含量在6%-11%之间,振实密度和倍率性能都随碳含量增加而升高。随着比表面积的增大,材料的倍率性能先升高后降低。
Olive-type LiFePO4/C has gained much attention as its high theoretical capacity, flat voltage platform, rich resources, lower price, environmentally friendliness and good safety performance. But its poor rate performance and low tap density restrict its practical application. Homogeneous precipitation method and oxidized precipitate transformation method are adopted to prepare precursor FePO4, and then prepare LiFePO4/C. The relationship between physical performance and electrochemical performance is also investigated.
Homogeneous precipitation method is adopted to prepare FePO4 precursor, here the influence of urea amount and surfactant on the structure, morphology as well as electrochemical performance of LiFePO4 is investigated and the results show that at the optimized condition without surfactant, the first discharge capacity is 141.9mAh/g and poor rate performance. The discharge capacity of LiFePO4/C prepared with surfactant PEG reached 151.5mAh/g at 0.1 C rate, and the discharge capacity of 122.5mAh/g is reached at 1C rate, the tap density is 1.17cm3/g.
A new method-oxidized precipitate transformation method is put forward to prepare FePO4 precursor. The suspension of Fe3(PO4)2 is prepared at pH=9.5, and then the suspension is oxidized to prepare FePO4 at pH=2. The results show that the particle size of sphere FePO4 is about 100nm. The discharge capacity of LiFePO4/C prepared with FePO4 is 139.8mAh/g at 0.1C rate, and 123.2mAh/g at 2C, showing a well rate performance.
The relationship between physical performance and electrochemical performance of LiFePO4/C prepared with FePO4 as raw material is studied, the results show that the tap density and rate performance increase in the range of 6%-11%of carbon content. The rate performance first increases and then decreases as the specific surface area increases.
采用均匀沉淀法制备LiFePO4/C前驱体磷酸铁,比较了尿素添加量、表面活性剂对FePO4结构、形貌以及LiFePO4电化学性能的影响。结果表明：未添加表面活性剂,最优情况下合成LiFePO4的首次放电比容量为141.9mAh/g,倍率性能差。添加表面活性剂PEG制备的LiFePO4/C在O.1C倍率下放电比容量为151.5mAh/g,1C倍率下的放电比容量为122.5mAh/g,振实密度达1.17cm3/g。
研究了制备LiFePO4前驱体磷酸铁的新方法-氧化沉淀转化法：在pH=9.5的条件下制备纳米磷酸亚铁悬浊液,然后在pH=2的条件下将其氧化制备获得磷酸铁。结果表明：制备的磷酸铁形貌为类球形,尺寸为100nm左右。以该磷酸铁为前驱体合成的LiFePO4/C在O.1C倍率下首次放电比容量为139.8mAh/g,2C倍率下放电容量为123.2mAh/g,具有优良的倍率性能。
以商业化磷酸铁为原料,研究不同碳源制备的LiFePO4/C的物理性能和电化学性能的关系。结果表明：碳含量在6%-11%之间,振实密度和倍率性能都随碳含量增加而升高。随着比表面积的增大,材料的倍率性能先升高后降低。
Olive-type LiFePO4/C has gained much attention as its high theoretical capacity, flat voltage platform, rich resources, lower price, environmentally friendliness and good safety performance. But its poor rate performance and low tap density restrict its practical application. Homogeneous precipitation method and oxidized precipitate transformation method are adopted to prepare precursor FePO4, and then prepare LiFePO4/C. The relationship between physical performance and electrochemical performance is also investigated.
Homogeneous precipitation method is adopted to prepare FePO4 precursor, here the influence of urea amount and surfactant on the structure, morphology as well as electrochemical performance of LiFePO4 is investigated and the results show that at the optimized condition without surfactant, the first discharge capacity is 141.9mAh/g and poor rate performance. The discharge capacity of LiFePO4/C prepared with surfactant PEG reached 151.5mAh/g at 0.1 C rate, and the discharge capacity of 122.5mAh/g is reached at 1C rate, the tap density is 1.17cm3/g.
A new method-oxidized precipitate transformation method is put forward to prepare FePO4 precursor. The suspension of Fe3(PO4)2 is prepared at pH=9.5, and then the suspension is oxidized to prepare FePO4 at pH=2. The results show that the particle size of sphere FePO4 is about 100nm. The discharge capacity of LiFePO4/C prepared with FePO4 is 139.8mAh/g at 0.1C rate, and 123.2mAh/g at 2C, showing a well rate performance.
The relationship between physical performance and electrochemical performance of LiFePO4/C prepared with FePO4 as raw material is studied, the results show that the tap density and rate performance increase in the range of 6%-11%of carbon content. The rate performance first increases and then decreases as the specific surface area increases.
引文
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