Citation: 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. doi: 10.6023/A20070330 shu

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

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

Corresponding author: Cheng Fangyi, fycheng@nankai.edu.cn
Received Date: 28 July 2020
Available Online: 9 October 2020
Fund Project: the National Natural ScienceFoundation of China 21925503the Mistry of Science and Technology of the People's Republic of China 206YFA0202503Project supported by the Mistry of Science and Technology of the People's Republic of China (No.206YFA0202503) and the National Natural ScienceFoundation of China (Nos. 21925503, 21835004)the National Natural ScienceFoundation of China 21835004

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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.
- Li-rich Mn-based cathode materials,
- lithium ion battery,
- Li₃PO₄,
- in-situ coating,
- precipitate conversion
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In-situ Li₃PO₄ Coating of Li-Rich Mn-Based Cathode Materials for Lithium-ion Batteries