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

Abstract

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

CLC Number:

TQ131.11

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.

Figures/Tables 7

Table 1

Fig.1

Fig.2

Fig.3

Table 2

Advantages and disadvantages of preparation methods of lithium iron phosphate"

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。

Table 2

Fig.4

Fig.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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Research progress in synthesis and performance enhancement of LiFePO4 cathode materials