Abstract：There is a growing interest in cobalt-free nickel-manganese layered oxides as a new cathode material. Eliminating cobalt reduces costs and improves energy density, making it ideal for the increasing demands of electronic devices and electric vehicles. Due to the lack of cobalt, doping with manganese can partially suppress the multiple-phase transitions of nickel oxide materials. Experimental results show that the battery's rate performance at room temperature and above is comparable to that of nickel-cobalt-manganese (NCM) batteries. However, under low-temperature conditions, its performance is inferior to that of NCM ternary batteries. The peaks A and D in the battery's incremental capacity curve of open-circuit voltage constitute a voltage region of kinetic barriers. The underlying reason is that low temperature weakens the tolerance of the lithium-ion diffusion coefficient. Subsequent analysis under coupled electro thermal conditions indicates that capacity and energy metrics are more sensitive to charge rate (C-rate), whereas internal resistance and efficiency exhibit greater temperature sensitivity. A comprehensive electrochemical model is warranted to better understand cobalt-free batteries' temperature-dependent behavior. The insufficient simulation accuracy of the parameters of the traditional P2D model is particularly evident when modeling cobalt-free nickel-manganese system batteries at low temperatures. The simulation accuracy is very low using the parameters obtained through electrochemical parameter identification at low temperatures. Furthermore, the correlation between the electrochemical parameters of the battery and its external performance remains unclear. Therefore, the sensitivity of battery C-rate and state of charge (SOC) is studied for multi-dimensional electrochemical parameters using the one-at-a-time (OAT) sensitivity analysis method. Results show that parameters, such as solid-phase diffusion coefficients in both cathode and anode electrodes, reaction rate constants, particle radius, and liquid-phase diffusion coefficient, have a significant impact on battery performance and are closely correlated with C-rate and SOC. The significantly enhanced sensitivity of electrochemical parameters at low temperatures makes parameter identification more challenging. This paper extracts high-sensitivity electrochemical parameters by analyzing the results of multiple models at temperatures above 5℃. It employs temperature-dependent fitting equations, such as the Arrhenius equation, to calculate reliable electrochemical parameters, improving cobalt-free battery modeling accuracy over a wide temperature range. The root mean square error (RMSE) is within 20 mV over the temperature range of -5℃ to 50℃. A robust correlation is established between internal electrochemical parameters and external electrical performance. The study demonstrates that diffusion-related parameters strongly correlate with battery capacity and energy, while charge transfer-related parameters are susceptible to the temperature of electrochemical reactions. This paper provides a solid foundation for future investigations into the state of health diagnosis of cobalt-free batteries and the development of advanced battery management systems.
张彩萍, 乔波, 张琳静, 刘梦, 陈泽平. 宽温域无钴锂离子电池电化学建模及参数灵敏度研究[J]. 电工技术学报, 2025, 40(17): 5652-5666.
Zhang Caiping, Qiao Bo, Zhang Linjing, Liu Meng, Chen Zeping. Research on Electrochemical Modeling and Parameter Sensitivity of Cobalt-Free Lithium-Ion Battery with Wide Temperature Range. Transactions of China Electrotechnical Society, 2025, 40(17): 5652-5666.
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