Acta Physico-Chimica Sinica

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An Optimized Synthetic Process for the Substitution of Cobalt in Nickel-Rich Cathode Materials

Feng Wu1,2, Qing Li1,2, Lai Chen1,2, Zirun Wang1, Gang Chen1,2, Liying Bao1, Yun Lu1,2, Shi Chen1, Yuefeng Su1,2   

  1. 1 School of Materials Science and Engineering, Beijing Key Laboratory of Environmental Science and Engineering, Beijing Institute of Technology, Beijing 100081, China;
    2 Beijing Institute of Technology Chongqing Innovation Center, Chongqing 401120, China
  • Received:2020-07-06 Revised:2020-08-07 Accepted:2020-08-18 Published:2020-08-24
  • Supported by:
    The project was supported by the National Key R&D Program of China (2016YFB0100301), the National Natural Science Foundation of China (21875022, 51802020, U1664255), the Science and Technology Innovation Foundation of Beijing Institute of Technology Chongqing Innovation Center (2020CX5100006), the Beijing Institute of Technology Research Fund Program for Young Scholars, and the Young Elite Scientists Sponsorship Program by CAST (2018QNRC001).

Abstract: High-performance rechargeable lithium ion batteries have been widely applied in electrochemical energy storage fields, such as, energy storage grids, portable electronic devices, and electric vehicles (EVs). However, the energy density of lithium ion batteries needs to be increased, and the cost of battery materials could be further reduced for wider commercial applications. An Ni-rich cathode, LiNixMnyCo1−xyO2 (x>0.8), with high specific capacity is the most promising material for next-generation Li-ion batteries. LiNixMnyCo1−xyO2 (x>0.8) contains three transition metal elements, Ni, Mn, and Co, respectively. The role of Ni2+ is to provide high capacity for recharge The role of Mn4+ is to stabilize the lattice structure during charging-discharging cycling. Crucially, the role of Co3+ in Ni-rich materials is to improve the electrical conductivity and inhibit cation disorder in the lattice during electrochemical cycling. However, Co is both in shortage and expensive, which limits its worldwide commercial application. This work investigates substituting Co with other abundant and cheap transition metals. Transition metal ions Cr3+, Cd2+, and Zr4+ can replace Co3+ in Ni-rich cathode materials. LiNi0.8Cr0.1Mn0.1O2, LiNi0.8Cd0.1Mn0.1O2, and LiNi0.8Zr0.1Mn0.1O2 were synthesized by a co-precipitation method. Zr was found to be the best candidate for replacing Co in Ni-rich cathode materials. This study investigated Zr4+-doped Co-free Ni-rich materials. Initially, a carbonate co-precipitation process was used to synthesize Ni0.8Zr0.1Mn0.1CO3. This is due to that Zr3+/Zr4+ ions are not precipitated in the strong alkali solution, and the pH during hydroxide co-precipitation and carbonate co-precipitation processes are approximately 11 and 8, respectively. Therefore, the carbonate co-precipitation synthesis method was chosen. Ni0.8Zr0.1Mn0.1CO3 was synthesized by carbonate co-precipitation at pH=7.6, 7.8, 8.0, and 8.2. After electrochemical analysis, pH=7.8 was identified as the optimal value. The next stage of the research involved completing an electrochemical performance comparison on two lithium sources. The following lithium sources were added to the precursor; LiOH·H2O, and a 1:1 mixture of LiOH·H2O and Li2CO3. The lithium source with the 1:1 mixture, exhibited better performance for the Ni-rich cathode, LiNi0.8Zr0.1Mn0.1O2. In this study, the ideal doping amount of Zr in Ni-rich materials was 0.05. In conclusion, by careful control of co-precipitation pH and Li source, the Zr doped cobalt free Ni-rich cathode LiNi0.85Mn0.1Zr0.05O2 delivered a discharge capacity of 179.9 mAh∙g−1 at 0.2C. This was achieved between the voltage range of 2.75–4.3 V, with an 80 cycle capacity retention of 96.52%.

Key words: Lithium ion battery, Nickle-rich cathode material, Cobalt free, Cycling stability


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