磷酸锰铁锂正极材料改性研究进展

doi:10.19799/j.cnki.2095-4239.2023.0771

储能科学与技术 ›› 2024, Vol. 13 ›› Issue (3): 770-787.doi: 10.19799/j.cnki.2095-4239.2023.0771

磷酸锰铁锂正极材料改性研究进展

文志朋¹(), 潘凯¹(), 韦毅¹, 郭佳文¹, 覃善丽¹, 蒋雯¹, 吴炼²^,³(), 廖欢¹

^1.广西产研院新型功能材料研究所有限公司，广西南宁 530200
^2.广西大学，广西石化资源加工及过程强化技术重点实验室，广西南宁 530004
^3.广东省科学院化工研究所，广东广州 510665

收稿日期:2023-10-30 修回日期:2023-11-20 出版日期:2024-03-28 发布日期:2024-03-28
通讯作者: 潘凯,吴炼 E-mail:wenzhipeng_01@sina.com;pankai_09@sina.com;wulian@gdcri.com
作者简介:文志朋（1987—），男，硕士，高级工程师，主要研究方向为化工新能源材料，E-mail：wenzhipeng_01@sina.com；
基金资助:
广西科技基地与人才专项(桂科AD23026031);广西科技基地与人才专项(桂科AD23023009);广西石化资源加工及过程强化技术重点实验室开放课题(2022K013);南宁市重大科技专项(20221021);南宁市重大科技专项(20231036)

Research progress in lithium manganese iron phosphate cathode material modification

Zhipeng WEN¹(), Kai PAN¹(), Yi WEI¹, Jiawen GUO¹, Shanli QIN¹, Wen JIANG¹, Lian WU²^,³(), Huan LIAO¹

^1.Institute of New Functional Materials of GIIT Co. LTD. , Nanning 530200, Guangxi, China
^2.Guangxi Key Laboratory of Petrochemical Resource Processing and Process Intensification Technology, Guangxi University, Nanning 530004, Guangxi, China
^3.Institute of Chemical Engineering, Guangdong Academy of Sciences, Guangzhou 510665, Guangdong, China

Received:2023-10-30 Revised:2023-11-20 Online:2024-03-28 Published:2024-03-28
Contact: Kai PAN, Lian WU E-mail:wenzhipeng_01@sina.com;pankai_09@sina.com;wulian@gdcri.com

摘要/Abstract

摘要：

正极材料是决定锂离子电池性能的关键材料之一，直接影响电池的能量密度、循环寿命、倍率性能及安全性能。橄榄石型LiMnFePO₄具有能量密度高、成本低、环境友好、安全稳定等优点，被认为是一种很有前途的锂离子电池正极材料。然而，LiMnFePO₄具有橄榄石结构磷酸盐基化合物电子电导率低、Li⁺一维扩散速率慢等固有缺陷，严重阻碍了其在高性能锂离子电池中的大规模应用。如何提升LiMnFePO₄的导电子/离子性能，是当前需要解决的关键问题。本文全面综述了LiMnFePO₄正极材料的结构特征、合成方法及其导电性能提升的研究进展，着重介绍了表面包覆、形貌控制和离子掺杂等方法对提升LiMnFePO₄正极材料导电性能的效果及其作用机理，虽然上述三类改性方法均可一定程度地优化材料颗粒间电子/离子传输路径，实现LiMnFePO₄正极材料导电性能的提升。但是单独采用这些方法依然难以从根本上解决LiMnFePO₄导电性差的问题。为进一步提升LiMnFePO₄正极材料的综合性能，本文在总结当前研究进展的基础上，对LiMnFePO₄未来的研究思路和发展方向进行了展望。提出了通过杂原子掺杂优质碳材料包覆、短b轴形貌控制以及离子掺杂等方法联合改性的策略。该策略有望进一步提升LiMnFePO₄正极材料的导电性能，获得高容量、高倍率、高稳定性的LiMnFePO₄正极材料。

关键词: 磷酸锰铁锂, 导电性能, 表面包覆, 形貌控制, 离子掺杂

Abstract:

Cathode materials are vital for lithium-ion batteries (LIBs) because they determine their performance by directly affecting the energy density, cycle life, rate, and safety of these batteries. Olivine-type LiMnFePO₄ is a commercial LIB cathode material with good market prospects due to its high energy density, low cost, environmental compatibility, stability, and safety. However, the inherent shortcomings of LiMnFePO₄, such as low electronic and ionic conductivity, seriously hinder its large-scale commercial application in high-performance LIBs. Thus, improving the electron and ion conductivity of LiMnFePO₄ is an urgent problem to solve. This review comprehensively discusses the structural characteristics, synthesis methods, and the recent research progress in LiMnFePO₄ cathode materials. Improving the conductivity of LiMnFePO₄ cathode materials by surface coating, morphology control, and ion doping is discussed. Although these three modification methods can optimize the electron and ion transport path in the LiMnFePO₄ matrix, the problem of poor electronic and ionic conductivity is difficult to solve via a single method. To improve the comprehensive performance of LiMnFePO₄ cathode materials, this paper summarizes the current research progress and proposes future research directions for LiMnFePO₄. The modification strategy of combining carbon-doped heteroatom coating, control of the short b-axis morphology, and ion doping is considered an effective remedy for the poor electronic and ionic conductivity and can endow LiMnFePO₄ cathode materials with high capacity and high stability.

Key words: lithium manganese iron phosphate, conductivity, surface coating, morphology control, ion doping

中图分类号:

O 646.54

文志朋, 潘凯, 韦毅, 郭佳文, 覃善丽, 蒋雯, 吴炼, 廖欢. 磷酸锰铁锂正极材料改性研究进展[J]. 储能科学与技术, 2024, 13(3): 770-787.

Zhipeng WEN, Kai PAN, Yi WEI, Jiawen GUO, Shanli QIN, Wen JIANG, Lian WU, Huan LIAO. Research progress in lithium manganese iron phosphate cathode material modification[J]. Energy Storage Science and Technology, 2024, 13(3): 770-787.

图/表 13

图1

图2

表1

LiMn1-x Fe x PO4 材料制备方法"

分类	制备方法	技术简介	优点	缺点
固相法	高温固相法	将煅烧分解后可产生挥发性气体的锂源、磷源、铁源、锰源等混合均匀，干燥后在惰性气体保护下烧结，再通过粉碎、筛分除铁等步骤得到磷酸锰铁锂正极材料	工艺简单，过程易控，比较容易实现大规模工业生产	合成周期长，能耗大，尺寸较大且分布不均匀
固相法	碳热还原法	采用还原性的碳源，在高温条件下将Fe³⁺还原为Fe²⁺，再将二价铁源与其他原料混合，经煅烧、研磨得到磷酸锰铁锂成品	采用廉价三价铁源代替昂贵的二价铁源，可大幅降低生产成本	需严格控制碳源的用量，过多或过少都会产生杂质，降低材料的性能

液相法	水热法/溶剂热法	原材料加入溶剂或水中溶解，在高温高压的条件下反应，然后经干燥、研磨、煅烧等步骤得到磷酸锰铁锂正极材料	产品结晶度高、粒径尺寸可控，电化学性能优良	高温高压的反应条件对设备要求严格，环保压力大
	溶胶-凝胶法	各种原料一起溶解在水或者乙醇中，搅拌较长的时间使各组分形成均匀的溶胶，再通过升高温度使体系发生凝胶化，再经过高温焙烧后得到成品	产品颗粒粒径均匀且细小，不易团聚，制备过程简单且能耗较低	需要控制的影响因素多，干燥、焙烧时间较长，合成周期长
	共沉淀法	可溶性亚铁盐、锰盐、锂盐、磷酸盐等原材料溶于溶剂中，通过调控体系的pH值或加入沉淀剂，使反应物在溶液中形成沉淀，再经离心、洗涤、干燥、煅烧后，得到LiMnFeO₄成品	产物粒径均匀，材料廉价易得，合成工艺简单，热处理温度低，周期短	纳米级沉淀过滤困难，后续废液处理困难，环保压力大
	喷雾干燥	原材料通过液相混合、球磨混合等方式充分混合均匀后，用压力喷雾干燥机进行造粒并直接烧结制备出LiMnFeO₄成品	产品颗粒球形度高，振实密度高	较难得到均一的包覆层

其他方法	静电纺丝法	利用高压电场将电极材料前驱体与有机高分子物质混合液拉伸成极细的纤维，再经高温煅烧后得到纤维状LiMnFeO₄材料	制备过程简单，纤维状LiMnFeO₄材料具有较高的比表面积和孔隙度	设备成本较高，有机高分子物质容易受到氧化、水解等因素的影响，其稳定性较差
其他方法	模板法	模板法是以模板为主体构型去控制、影响和修饰最终产物的形貌，控制尺寸进而改善材料性能的一种合成方法	能够控制、影响和修饰目标物质的形貌	反应条件苛刻、设备要求高、后处理工序复杂

表1

图3

图4

图5

表2

LiMn1-x Fe x PO4 表面包覆改性提升导电性能概述"

材料	合成方法	包覆材料	倍率性能/(mAh/g)	参考文献
LiMn_0.5Fe_0.5PO₄@C	水热法	碳	156.4(0.05 C)、151(0.1 C)、147.6(0.2 C)、145.7(0.5 C)、137.3(1 C)、134.5(5 C)	[22]
LiMn_0.6Fe_0.4PO₄@C	喷雾干燥和高温煅烧	碳	153.8(0.1 C)、114.0(5 C)、95.5(10 C)	[23]
LiMn_0.6Fe_0.4PO₄@C	湿法球磨和高温固相	碳	164.7(0.1 C)、137.7(1 C)、	[24]
LiMn_0.5Fe_0.5PO₄/C	生物衍生琼脂辅助溶胶-凝胶法	碳	143(1 C)、123(2 C)、 96(5 C)、88(10 C)	[25]
LiMn_0.9Fe_0.1PO₄/C	机械化学活化辅助高温碳热还原	碳	155(0.1 C)、140(1 C)、 122.9(2 C)	[27]
LiMn_0.7Fe_0.3 PO₄@GO	高温碳热还原	石墨烯	116(10 C)、83(30 C)	[28]
LiFe_0.25Mn_0.75PO₄/C/ rGO	砂磨辅助喷雾干燥	碳和还原石墨烯	143.8(1 C)、139.8(2 C)	[29]
LiFe_0.4Mn_0.6PO₄/C/rGO	溶剂热法	碳和还原石墨烯	159.5(0.05 C)、118.7(10 C)	[30]
LiMn_0.8Fe_0.2PO₄/C	喷雾热解法	碳	151(0.1 C)、133(1 C)	[32]
LiMn_0.8Fe_0.2PO₄@N-C	溶剂热法	掺N碳	154.7(0.1 C)、110.0(5 C)	[34]
LiFe_0.8Mn_0.2PO₄@N-C	溶胶-凝胶和静电纺丝	掺N碳	169.9(0.1 C)、93(5 C)	[35]
LiMn_0.8Fe_0.2PO₄@N-C	生物矿化法	掺N石墨烯	168.8(0.05 C)	[36]
LiMn_0.5Fe_0.5PO₄@N/S	溶剂热法	掺N/S碳	166.83(0.1 C)、96.47(5 C)	[38]
LiMn_0.8Fe_0.2PO₄@N/S-C	溶剂热法	掺N/S碳	159.2(0.1 C)、145.7(1 C)、117.3(5 C)	[39]
LiMn_0.8Fe_0.2PO₄@N/S-C	溶剂热法	掺N/S碳	156.4(0.1 C)、149.2(1 C)、116.4(5 C)	[40]
LiMn_0.8Fe_0.2PO₄@P-C	溶胶-凝胶和水热法	掺P碳	157.8(0.2 C)、93.6(10 C)	[41]
LiMn_0.75Fe_0.25PO₄@F-C	溶剂热法	掺F碳	161.3(0.2 C)、130.0(20 C)	[42]
LiMn_0.8Fe_0.2PO₄@B-C	溶胶-凝胶法	掺B碳涂层	151.1(0.1 C)、132.5(1 C)、102.5 (5 C)、82.3(10 C)、	[43]
LiFe_0.8Mn_0.2PO₄@B/P-C	溶胶-凝胶和水热法	B/P双掺杂碳包覆	159.6(0.1 C)、97.1(20 C)	[44]
LiMn_0.5Fe_0.5PO₄@LiAlO₂@C	溶剂热法	LiAlO₂和碳	137.6(0.05 C)、113.2(5 C)	[45]
0.9LiMn_0.9Fe_0.1PO₄·0.1Na₃V₂(PO₄)₂F₃/C	溶剂热法	Na₃V₂(PO₄)₂F₃和碳	125.5(1 C)、106.4(3 C)	[46]
LiMn_0.5Fe_0.5PO₄@C-3Li₃VO₄	湿式球磨法	Li₃VO₄和碳	156(0.1 C)、144(1 C)、125(10C)	[47]
C/LiMn_0.5Fe_0.5PO₄@Li_0.33La_0.56TiO₃(3%)	高温煅烧	Li_0.33La_0.56TiO₃和碳	146(0.05 C)、131.3(5 C)	[48]
LiMn_0.5Fe_0.5PO₄@/NS-C@ Li₂ZrO₃(1%)	溶剂热合成和煅烧	Li₂ZrO₃和掺N/S碳	166.8(0.1 C)、118.9(5 C)	[49]
C/ LiFe_0.5Mn_0.5PO₄@Li₂SiO₃(1%)	固相反应和原位镀膜法	Li₂SiO₃和碳	157.6(0.1 C)、106.3(10 C)	[50]
LiMn_0.8Fe_0.2PO₄@Li₃PO₄/C	固相法结合冷冻干燥法	Li₃PO₄和碳	150(0.1 C)、144(1 C)、136(5 C)	[51]

表2

图6

图7

表3

图8

图9

表4

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材料	合成方法	形貌	倍率性能/(mAh/g)	参考文献
LiMn_0.8Fe_0.2PO₄/C	溶剂热法	纳米椭球	150.9(0.05 C)、134.6(1 C)、107.5(5 C)	[54]
LiMn_0.8Fe_0.2PO₄	固相法	微米球	122(0.2 C)、118(0.5 C)、113(1 C)、109(2 C)、106(3 C)	[55]
LiMn_0.5Fe_0.5PO₄	高温固相法	纳米球	141(0.1 C)	[56]
LiFe_0.1Mn_0.9PO₄	溶剂热法	纺锤状纳米	129.7(0.1 C)	[57]
LiMn_0.6Fe_0.4PO₄	水热法	纳米棒	106.4(0.1 C)	[58]
LiFe_0.5Mn_0.5PO₄/C	溶剂热法	纳米棒	157(0.2 C)、119(5 C)	[59]
LiMn_0.8Fe_0.2PO₄/C	溶剂热法	纳米棒	140(0.1 C)	[60]
LiMn_0.8Fe_0.2PO₄@C	喷雾干燥法	微纳球	144.9(0.1 C)、140.2(0.2 C)、125.2(5 C)、110.5(10 C)	[61]
LiMn_0.8Fe_0.2PO₄	机械化学液相活化	微纳球	159(0.1 C)、130(10 C)	[52]
LiMn_0.6Fe_0.4PO₄	共沉淀法、喷雾干燥法、高温烧结法	微纳球	156(0.1 C)、147(1 C)、133(10 C)	[62]
LiMn_0.8Fe_0.2PO₄/C	高温固相法、液相法、喷雾干燥法	微纳球	162.5(0.1 C)、101.2(10 C)	[63]

掺杂元素	最佳掺杂量	倍率性能/(mAh/g)	参考文献
Na⁺	Li_0.97Na_0.03Mn_0.8Fe_0.2PO₄/C	141.7(0.05C)、125.0(1C) 、89.5(5C)	[64]
Na⁺	Li_0.98Na_0.02Fe_0.65Mn_0.35PO₄/C	136.3(0.1C)	[65]
K⁺	Li_0.97K_0.03Fe_0.95Mn_0.05PO₄/C	145.07(5C)	[66]
Mg²⁺	LiFe_0.48Mn_0.48Mg_0.04PO₄	152.2 (0.1C)、146.3 (10C)、107.8 (20C)	[67]
Mg²⁺	LiMn_0.6Fe_0.39Mg_0.01PO₄/C	159.6 (0.2C) 、124.5 (10C)	[68]
Mg²⁺	LiMn_0.8Fe_0.19Mg_0.01PO₄/C	146.6 (0.1C) 、116.0 (5C)	[69]
Mg²⁺	LiFe_0.7Mn_0.25Mg_0.05PO₄/C	163.2 (0.1C)、155.2 (0.2C) 、149.1 (0.5C) 、142.0 (1C)	[70]
Co²⁺	LiMn_0.7Fe_0.3PO₄-1%Co/C	165 (0.1C) 、154 (1C) 、150 (5C)、147(10C)	[71]
Ni²⁺	LiMn_0.6Fe_0.38Ni_0.02PO₄/C	159.3 (0.2C)、149.8 (1C) 、143.5 (2C) 、135.7 (5C)、125.1 (10C) 、115.4 (15C)	[72]
Ni²⁺	LiMn_0.8Fe_0.19Ni_0.01PO₄/C	157.3(0.5C)、119.1(10C)、102.5(20C)	[73]
Ca²⁺	LiFe_0.497Mn_0.5Ca_0.03PO₄@C	162.6 (0.1C) 、105.7 (10C)、53.1 (50C)	[74]
Zn²⁺	LiMn_0.9Fe_0.05Zn_0.05PO₄/C	151.3 (0.1C) 、128.4 (1C)	[75]
Cr³⁺	LiFe_0.4Mn_0.595Cr_0.005PO₄/C	164.0 (0.1C) 、156.2 (0.5C) 、147.5 (2C)、139.3 (5C)	[76]
V³⁺	LiMn_0.8Fe_0.155V_0.03□_0.015PO₄(□为Fe空位)	155 (0.1C)	[77]
Y³⁺	LiFe_0.5Mn_0.49Y_0.01PO₄@C	160 (0.1C) 、44.89 (10C)	[78]
Ti⁴⁺	LiMn_0.6Fe_0.38Ti_0.02PO₄/C	143.5 (1C) 、126.8 (10C)	[53]
Nb⁵⁺	LiFe_0.5Mn_0.5PO₄/C-1%Nb	152 (0.1C) 、115 (5C)	[79]

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磷酸锰铁锂正极材料改性研究进展

Research progress in lithium manganese iron phosphate cathode material modification

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