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Investigation of the Li-Co antisite exchange in Fe-substituted LiCoPO4 cathode for high-voltage lithium ion batteries

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Liu,  Zigeng
Research Department Schlögl, Max Planck Institute for Chemical Energy Conversion, Max Planck Society;

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Citation

Wu, X., Meledina, M., Barthel, J., Liu, Z., Tempel, H., Kungl, H., et al. (2019). Investigation of the Li-Co antisite exchange in Fe-substituted LiCoPO4 cathode for high-voltage lithium ion batteries. Energy Storage Materials, 22, 138-146. doi:10.1016/j.ensm.2019.07.004.


Cite as: http://hdl.handle.net/21.11116/0000-0006-7965-1
Abstract
Carbon coated olivine Pnma LiCoPO4 (LCP/C) and Fe-substituted LiCo0.8Fe0.2PO4 (LCFP/C) were synthesized by a solvothermal method and their structural features and electrochemical properties were investigated. The electrochemical performance of LCFP/C is better than that of LCP/C, owing to the partial substitution of Co by Fe which effectively suppresses the increasement of antisite exchange between Li+ and Co2+ ions within the structure during cycling, despite a similar amount of Li-Co antisite exchange in pristine LCP/C and LCFP/C samples. Furthermore, direct visualization of Co in Li sites in the pristine samples and after 50 cycles was achieved through high-resolution scanning transmission electron microscopy for both LCP/C and LCFP/C. It was found that LCP/C locally formed a new cation-ordered structure after cycling due to the Li-Co antisite exchange, while the structure of LCFP/C remains almost the same. This study provides direct evidence that Fe substitution reduced the Li-Co exchange and improved the electrochemical cycling life of the LiCoPO4 cathode for high-voltage lithium ion batteries.