磷酸铁锂正极材料的制备及性能强化研究进展

doi:10.19964/j.issn.1006-4990.2021-0212

摘要/Abstract

摘要：

橄榄石型磷酸铁锂是目前应用十分广泛的锂离子电池正极材料之一,具有成本低、安全性高、环境友好、循环寿命长和工作电压稳定的特点。近年来,随着CTP技术、刀片电池技术等取得的突破性进展,磷酸铁锂的商业化程度得到了大幅提高。但磷酸铁锂存在电子导电性较差和离子扩散系数低的缺陷,严重限制了锂离子电池的电化学容量,因此开展磷酸铁锂制备工艺和性能强化研究对磷酸铁锂的性能提升具有重要意义。对比了磷酸铁锂电池与其他正极材料锂离子电池的性能差异和发展现状,系统总结了磷酸铁锂正极材料制备与强化的改性方法及相关研究进展与挑战,并提出了未来的发展方向与研究思路。

关键词: 磷酸铁锂, 锂离子电池, 正极材料, 性能强化

Abstract:

Olivine LiFePO₄ is one of the most widely used cathode materials for lithium-ion batteries,with characteristics of low cost,high safety,environment-friendly,long cycle life and stable operating voltage.In recent years,with the breakthrough of CTP technology and blade battery technology,its commercialization progress has been greatly improved.However,LiFePO₄ has the defects of poor electronic conductivity and low ion diffusion coefficient,which seriously limits the electrochemical capacity of lithium-ion battery.It is of great significance to study on the preparation process and performance enhancement of LiFePO₄. In this paper,the differences of performance and development status of LiFePO₄ and other cathode materials for lithium-ion batteries were compared.The modification methods of preparation and strengthening of LiFePO₄ cathode materials and related research progress and challenges were systematically summarized,and the future development direction and research ideas were put forward.

Key words: lithium iron phosphate, lithium-ion batteries, cathode materials, performance enhancement

中图分类号:

TQ131.11

张婷,林森,于建国. 磷酸铁锂正极材料的制备及性能强化研究进展[J]. 无机盐工业, 2021, 53(6): 31-40.

Zhang Ting,Lin Sen,Yu Jianguo. Research progress in synthesis and performance enhancement of LiFePO₄ cathode materials[J]. Inorganic Chemicals Industry, 2021, 53(6): 31-40.

图/表 7

表1

图1

图2

图3

表2

磷酸铁锂制备方法优缺点

制备方法		优点	缺点
固相法	高温固相法	1）成本较低,步骤简单,流程可靠;2）铁、磷、锂含量易于通过配料控制;3）循环和低温性能良好。	1）耗时长、能耗高,需惰性和还原性气氛保护;2）所得产物易出现氧化态的三价铁;3）颗粒团聚严重,产物颗粒较大,纯度较低,尺寸分布不均匀, 批次一致性差,电化学性能相对较差。4）出气量大,氧分压难以保证; 5）表面能高,加工性能不好;F.容易存在氨气污染问题。
	碳热还原法	1）原料廉价易得、化学稳定性好;2）能耗低,制备工艺简单。	1）操作复杂生产周期长,能耗大,产生废气;2）对原料要求高;混料的均匀性影响非常大;3）原料磷酸铁的成分难于控制一致。
	微波加热法	1）能量高效利用;2）循环性能较好、形貌规则;3）合成温度较低、时间较短;4）避免惰性气体的使用。	反应迅速,产物易发生团聚,不利于电化学性能的改善。
液相法	水热/溶剂热法	1）能耗低,合成效率高;2）产品粒度均一,一次稳定性好;3）可直接合成单晶型磷酸铁锂,便于直接分析本征性质;4）技术成熟。	1）产品结构不一,堆积密度和压实密度较小;2）高温高压下,设备要求高;3）水热法产品易发生替代错位影响性能;4）仍需经高温烧结碳包覆;5）成本高,需投资建设锂回收装置。
	溶胶凝胶法	可实现纳米级别的均匀混合,可同时实现碳包覆。	1）耗时长;2）工艺条件难控制;3）工业化存在较大难度。
	共沉淀法喷雾干燥法	1）工艺过程易控制,合成周期短,能耗低; 2）颗粒粒度小且分布均匀。颗粒均匀、粒径小、循环稳定性好。	1）共沉淀过程中的pH不易控制且容易出现偏析;2）合成的材料性能不稳定为工业化难点。

表2

图4

图5

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项目	电压平台/ V	理论比容量/ （mA·h·g^-1）	理论密度/ （g·cm^-3）	循环寿命	安全性	热稳定性	过渡金属资源	原料成本
LiCoO₂	3.9^[3]	274^[3,7-8]	5.1^[9]	较长	低	不稳定	贫乏	高
LiMn₂O₄	2.8,4.0^[3,4]	148^[6]	4.2^[9]	短	较低	较稳定	较丰富	较低
LiNi_1-_x-yMn_xCo_yO₂ （x+y<1）	3.8^[3]	275^[3]	—	较短	低	不稳定	较丰富	较高
LiFePO₄	3.45^[5,6]	170^[6]	3.68^[9]	长	高	稳定	丰富	低

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