氟掺杂改性LiMn0.5Fe0.5PO4正极材料及其电化学性能

doi:10.16085/j.issn.1000-6613.2023-1224

化工进展 ›› 2024, Vol. 43 ›› Issue (1): 302-309.DOI: 10.16085/j.issn.1000-6613.2023-1224

• 专栏：化工过程强化 • 上一篇

氟掺杂改性LiMn_0.5Fe_0.5PO₄正极材料及其电化学性能

于松民¹(), 金洪波², 杨明虎³, 余海峰², 江浩¹^,²()

^1.华东理工大学材料科学与工程学院超细材料制备与应用教育部重点实验室，上海 200237
^2.华东理工大学化工学院上海多级结构纳米材料工程技术研究中心，上海 200237
^3.安徽聚合辐化化工有限公司，安徽滁州 233200

收稿日期:2023-07-18 修回日期:2023-08-13 出版日期:2024-01-20 发布日期:2024-02-05
通讯作者: 江浩
作者简介:于松民（1998—），男，硕士研究生，研究方向为磷酸锰铁锂材料制备与改性。E-mail：742703361@qq.com。
基金资助:
国家自然科学基金(21975074)

Synthesis and modification of F-doped olivine LiFe_0.5Mn_0.5PO₄ cathode materials for Li-ion batteries

YU Songmin¹(), JIN Hongbo², YANG Minghu³, YU Haifeng², JIANG Hao¹^,²()

^1.Key Laboratory for Ultrafine Materials of Ministry of Education, School of Materials Science and Engineering, East China University of Science and Technology, Shanghai 200237, China
^2.Shanghai Engineering Research Center of Multistage Structural Nanomaterials, College of Chemical Engineering, East China University of Science and Technology, Shanghai 200237, China
^3.AnHui Polymeric Chemicals Co. , Ltd. , Chuzhou 233200, Anhui, China

Received:2023-07-18 Revised:2023-08-13 Online:2024-01-20 Published:2024-02-05
Contact: JIANG Hao

摘要/Abstract

摘要：

目前磷酸铁锂材料由于其较低的能量密度难以满足使用需求。磷酸锰铁锂具有比磷酸铁锂更高的能量密度，同时兼顾磷酸铁锂低成本和晶体结构稳定性的特点。然而缓慢的锂离子扩散动力学和Mn³⁺引起的Jahn-Teller效应导致材料的循环和倍率性能差，限制了磷酸锰铁锂实际应用。本工作通过引入F离子掺杂，构筑沿b轴取向生长的110nm纳米颗粒磷酸锰铁锂正极材料，探究了它们的基本物理化学性质与电化学性能，发现沿b轴取向生长并暴露的(010)晶面能够显著提升锂离子扩散动力学。此外，F离子引入显著增强了Li—O键以及PO₄^3-骨架结构，提高锂离子嵌入和脱出过程中晶体结构稳定性。因此，在0.1C和5C电流下，改性磷酸锰铁理正极材料可逆放电比容量分别为153mA·h/g和106mA·h/g。相比于未改性材料，1C循环750次后比容量保持率从90.6%提升到96.4%。

关键词: 电化学, 磷酸锰铁锂, 正极, 锂离子电池, 氟掺杂

Abstract:

At present, LiFePO₄ materials is difficult to meet the demand of high energy density. LiMn _x Fe_1-_x PO₄ (LMFP) cathode materials exhibit higher energy density compared with LiFePO₄, while maintain the advantage of low cost and high stability of olivine structure. However, the inferior rate and cycle performance limit its practical application, which is ascribed by poor Li-ion diffusion kinetic and Jahn-Teller effect of Mn³⁺. In this work, a F-doping strategy was proposed to construct 110nm nanoparticles of LMFP with highly ordered b-axis orientation. The basic physicochemical properties and electrochemical properties of materials were explored, finding that the exposed (010) crystal face acted as Li-ion diffusion channel can significantly improve the Li-ion transport efficiency, while the doped F ions can increase the Li—O bond distance and the PO₄^3- binding energy to enhance the stability of crystal structure. Therefore, the reversible specific discharge capacity of the F-doped LMFP was 153mA·h/g and 106mA·h/g at 0.1C and 5C, respectively. After 750 cycles at 1C, the capacity retention increased from 90.6% to 96.4% compared with the unmodified material.

Key words: electrochemistry, lithium iron manganese phosphate (LiMn_0.5Fe_0.5PO₄), cathode, lithium-ion battery, F-doping

中图分类号:

TB32

于松民, 金洪波, 杨明虎, 余海峰, 江浩. 氟掺杂改性LiMn_0.5Fe_0.5PO₄正极材料及其电化学性能[J]. 化工进展, 2024, 43(1): 302-309.

YU Songmin, JIN Hongbo, YANG Minghu, YU Haifeng, JIANG Hao. Synthesis and modification of F-doped olivine LiFe_0.5Mn_0.5PO₄ cathode materials for Li-ion batteries[J]. Chemical Industry and Engineering Progress, 2024, 43(1): 302-309.

图/表 5

图1 不同比例F离子掺杂LiFe0.5Mn0.5PO4/C样品分析

图2 不同F掺杂量样品形貌及粒径分布图

图3 LMFP/C-1%F样品的形貌表征（a）晶面示意图；（b）、（c）高分辨TEM图像;（d）TEM-EDS图

图4 LMFP/C与LMFP/C-1%F的电化学性能（a）0.2mV/s下的CV曲线；（b）在0.1C下首圈充放电曲线；（c）不同F掺杂量样品的倍率性能；（d）LMFP/C与LMFP/C-1%F循环性能；（e）LMFP/C-1%F 1000圈循环过程中充电/放电曲线

图5 LMFP/C-1%F和LMFP/C的电化学性能（a）、（b）在不同扫描速率下的CV曲线；（c）Ip-v1/2线性关系；（d）奈奎斯特图；（e）低频区域Z′与ω-1/2的线性拟合；（f）GITT得到的Li+扩散系数

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氟掺杂改性LiMn_0.5Fe_0.5PO₄正极材料及其电化学性能

Synthesis and modification of F-doped olivine LiFe_0.5Mn_0.5PO₄ cathode materials for Li-ion batteries

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