In-situ Li3PO4 Coating of Li-Rich Mn-Based Cathode Materials for Lithium-ion Batteries

doi:10.6023/A20070330

Acta Chimica Sinica ›› 2020, Vol. 78 ›› Issue (12): 1426-1433.DOI: 10.6023/A20070330 Previous Articles Next Articles

Special Issue: 纪念南开大学化学学科创建100周年

Article

磷酸锂原位包覆富锂锰基锂离子电池正极材料

刘九鼎^a, 张宇栋^a, 刘俊祥^a, 李金翰^a, 邱晓光^a, 程方益^a,b,c

a 南开大学化学学院先进能源材料化学教育部重点实验室天津 300071;
b 南开大学新能源转化与存储交叉科学中心天津 300071;
c 南开大学高效储能教育部工程研究中心天津 300071

投稿日期:2020-07-28 发布日期:2020-10-12
通讯作者: 程方益 E-mail:fycheng@nankai.edu.cn
基金资助:
项目受科技部重点研发计划（No.2016YFA0202503）和国家自然科学基金（Nos.21925503，21835004）资助.

In-situ Li₃PO₄ Coating of Li-Rich Mn-Based Cathode Materials for Lithium-ion Batteries

Liu Jiuding^a, Zhang Yudong^a, Liu Junxiang^a, Li Jinhan^a, Qiu Xiaoguang^a, Cheng Fangyi^a,b,c

a Key Laboratory of Advanced Energy Materials Chemistry (Ministry of Education), College of Chemistry, Nankai University, Tianjin 300071, China;
b Renewable Energy Conversion and Storage Center, Nankai University, Tianjin 300071, China;
c Engineering Research Center of High-efficiency Energy Storage (Ministry of Education), Nankai University, Tianjin 300071, China

Received:2020-07-28 Published:2020-10-12
Supported by:
Project supported by the Ministry of Science and Technology of the People's Republic of China (No. 2016YFA0202503) and the National Natural Science Foundation of China (Nos. 21925503, 21835004).

1. Supporting Information-A20070330.pdf(1450KB)

Abstract

Lithium-rich manganese-based oxides (LRMO) are promising cathode materials to build next generation lithium-ion batteries because of high capacity and low cost. However, the severe capacity fade and voltage decay, which originate from surface oxygen loss, side reactions and irreversible phase transformation, restrict their practical application. Proposed approaches to address these issues include electrolyte modification, synthesis condition optimization, tuning elemental composition, bulk doping and surface coating. Surface coating has been proved to be an effective method to stabilize the interface between LRMO and electrolyte. Herein, we report a facile approach to synthesize Li₃PO₄-coated LRMO (LRMO@LPO) by in-situ carbonate-phosphate precipitate conversion reaction. The formation of Li₃PO₄ layer and its contribution to enhanced electrochemical performance are investigated in detail. Transmission electron microscopy (TEM) reveals that the surface of carbonate precursor converts to Ni₃(PO₄)₂ after reacting with Na₂HPO₄ solution, which finally transforms to Li₃PO₄ coating layer with thickness below 30 nm during calcination process. Quinoline phosphomolybdate gravimetric method gives the optimal Li₃PO₄ coating content of 0.56%. The modified LRMO@LPO sample exhibits improved cycling stability (191.1 mAh·g^-1 after 175 cycles at 0.5C between 2.0~4.8 V and 81.8% capacity retention) and suppressed voltage decay (1.09 mV per cycle), compared with bare LRMO material (72.9% capacity retention, 1.78 mV per cycle). The electrodes are studied by galvanostatic intermittent titration technique, electrochemical impedance spectroscopy, TEM and inductively coupled plasma atomic emission spectrometry. The results suggest efficient mitigation of phase transformation and dissolution of transition metal in LRMO@LPO. As a coating material with lithium-ion conductivity, Li₃PO₄ not only acts as a physical barrier to inhibit side reaction between the electrolyte and LRMO, but also promotes lithium ion transport at the surface region of cathode. The in-situ surface modification approach simplifies the traditional post coating process, and may provide new insight to build stable and low cost Li-rich cathode for lithium-ion batteries.

Key words: Li-rich Mn-based cathode materials, lithium ion battery, Li₃PO₄, in-situ coating, precipitate conversion

Cite this article

Liu Jiuding, Zhang Yudong, Liu Junxiang, Li Jinhan, Qiu Xiaoguang, Cheng Fangyi. In-situ Li₃PO₄ Coating of Li-Rich Mn-Based Cathode Materials for Lithium-ion Batteries[J]. Acta Chimica Sinica, 2020, 78(12): 1426-1433.

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磷酸锂原位包覆富锂锰基锂离子电池正极材料

In-situ Li₃PO₄ Coating of Li-Rich Mn-Based Cathode Materials for Lithium-ion Batteries

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