火焰喷雾热解制备锂离子电池三元正极材料研究进展

doi:10.16085/j.issn.1000-6613.2023-0284

摘要/Abstract

摘要：

电化学储能技术的发展与电动汽车的大规模应用可有效降低碳排放；锂离子电池能量密度高，循环寿命长，是锂电储能技术与电动汽车的核心部件，其容量的提升主要受到正极材料的限制；锂离子电池三元正极材料具有污染小、成本低、性能高、容量大等方面的优点。传统液相法和高温固相法制备三元正极材料步骤烦琐、耗时长，不利于工业放大；火焰喷雾热解方法（flame spray pyrolysis，FSP）可一步制备三元正极材料，合成效率高，合成过程中无废液产生，对环境友好且易于工业化放大生产，近年来受到广泛关注。本文综述了近几年FSP方法制备三元正极材料的研究进展，首先简要介绍了FSP的发展简史、基本原理、典型装置和主要优势，其次展开分析了前体溶液组成、温度条件以及退火条件等制备条件对三元正极材料组成、结构、微观形貌以及电化学性能的影响，然后简述了FSP在三元正极材料改性和沉积技术方面的最新研究进展，最后展望了FSP制备三元正极材料的未来发展趋势。

关键词: 火焰喷雾热解, 锂离子电池, 三元正极材料, 电化学性能

Abstract:

The development of electrochemical energy storage technologies and the large-scale application of electric vehicles are critical for the reduction of carbon emissions. Lithium-ion batteries are the core components of electric energy storage technologies and electric vehicles with high energy density and long cycle life, yet their capacity is mainly limited by cathode materials. Ternary cathode materials have the advantages of light pollution, low cost, high performance and large capacity. However, the conventional wet chemistry and high-temperature solid-state methods are usually multi-step procedures and time-consuming, which are the major hurdlers for commercialization. The flame spray pyrolysis (FSP) method has attracted wide attention, given that it can produce ternary cathode materials in one step without waste produced during the synthesis process and thus has little impact on the environment. The present study reviewed the research progress in the preparation of ternary cathode materials by FSP method in recent years. Firstly, the history, advantages, basic principles and typical devices of FSP were briefly introduced. Secondly, the effects of precursor solution composition, synthesis temperature and annealing conditions on the composition, structure, morphology and electrochemical properties of ternary cathode materials were analyzed. Then, the recent research progress in the modification and deposition technologies of terpolymer cathode materials was briefly described. Finally, the future development trend of ternary cathode materials prepared by FSP was prospected.

Key words: flame spray pyrolysis, lithium-ion battery, ternary cathode material, electrochemical performance

中图分类号:

TK02

陈国徽, 王君雷, 李世龙, 李金宇, 徐运飞, 罗俊潇, 王昆. 火焰喷雾热解制备锂离子电池三元正极材料研究进展[J]. 化工进展, 2024, 43(2): 971-983.

CHEN Guohui, WANG Junlei, LI Shilong, LI Jinyu, XU Yunfei, LUO Junxiao, WANG Kun. Progress in synthesis of ternary cathode materials for lithium-ion batteries by flame spray pyrolysis[J]. Chemical Industry and Engineering Progress, 2024, 43(2): 971-983.

图/表 15

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制备方法	电极材料	反应温度和时间	后处理温度和时间	总耗时	文献
固相法	NCA	540℃预烧结6h	720℃退火24h	30h	[11]
共沉淀法	NCM111	480℃加热5h	900℃退火10h	15h	[12]
溶胶-凝胶法	NCM811	480℃分解有机组分5h	750℃退火15h	20h	[13]
水热法	NCM811	500℃下氧化5h	800℃退火10h	15h	[14]
火焰喷雾热解	NCM111	燃烧过程毫秒级	700℃退火3h	3h	[15]

制备方法	电极材料	反应温度和时间	后处理温度和时间	总耗时	文献
固相法	NCA	540℃预烧结6h	720℃退火24h	30h	[11]
共沉淀法	NCM111	480℃加热5h	900℃退火10h	15h	[12]
溶胶-凝胶法	NCM811	480℃分解有机组分5h	750℃退火15h	20h	[13]
水热法	NCM811	500℃下氧化5h	800℃退火10h	15h	[14]
火焰喷雾热解	NCM111	燃烧过程毫秒级	700℃退火3h	3h	[15]

产物	添加剂	退火条件	工作电压	初始放电比容量	电化学循环性能	来源
NCM111	无	900℃，2h	3.0～4.3V	0.1C，163.3mAh/g	1C下循环100次，保持率85.5%	[41]
NCM111	无	750℃，2h	3.0～4.7V	1C，180.0mAh/g	1C下循环500次，保持率80.0%	[50]
NCM111	无	800℃，3h	2.8～4.5V	18mA/g，168.0mAh/g	18mA/g下循环30次，保持率71.4%	[15]
NCA	尿素	800℃，10h	2.7～4.3V	0.1C，155.0mAh/g	0.2C下循环50次，保持率92.0%	[20]
NCA	柠檬酸	800℃，9h	2.7～4.3V	0.1C，143.0mAh/g	0.1C下循环20次，保持率92.0%	[57]
NCM811	尿素	875℃，1/3h	2.7～4.3V	0.1C，198.3mAh/g	1C下循环100次，保持率83.3%	[19]
NCM811	无	750℃，18h	2.8～4.3V	0.1C，185.5mAh/g	0.5C下循环45次，保持率81.1%	[52]
NCM811	无	825℃，20h	2.7～4.3V	0.1C，186.5mAh/g	0.33C下循环100次，保持率73.0%	[56]
NCM811	镝盐	800℃，12h	2.8～4.3V	0.1C，197.4mAh/g	1C下循环50次，保持率91.6%	[63]

产物	添加剂	退火条件	工作电压	初始放电比容量	电化学循环性能	来源
NCM111	无	900℃，2h	3.0～4.3V	0.1C，163.3mAh/g	1C下循环100次，保持率85.5%	[41]
NCM111	无	750℃，2h	3.0～4.7V	1C，180.0mAh/g	1C下循环500次，保持率80.0%	[50]
NCM111	无	800℃，3h	2.8～4.5V	18mA/g，168.0mAh/g	18mA/g下循环30次，保持率71.4%	[15]
NCA	尿素	800℃，10h	2.7～4.3V	0.1C，155.0mAh/g	0.2C下循环50次，保持率92.0%	[20]
NCA	柠檬酸	800℃，9h	2.7～4.3V	0.1C，143.0mAh/g	0.1C下循环20次，保持率92.0%	[57]
NCM811	尿素	875℃，1/3h	2.7～4.3V	0.1C，198.3mAh/g	1C下循环100次，保持率83.3%	[19]
NCM811	无	750℃，18h	2.8～4.3V	0.1C，185.5mAh/g	0.5C下循环45次，保持率81.1%	[52]
NCM811	无	825℃，20h	2.7～4.3V	0.1C，186.5mAh/g	0.33C下循环100次，保持率73.0%	[56]
NCM811	镝盐	800℃，12h	2.8～4.3V	0.1C，197.4mAh/g	1C下循环50次，保持率91.6%	[63]

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