Tuning polaronic redox behavior in olivine phosphate
Literature Information
Yue Gu, Mouyi Weng, Gaofeng Teng, Hua Zeng, Jianshu Jie, Weiji Xiao, Jiaxin Zheng, Feng Pan
In order to understand and improve the conductivity of LiFePO4, lots of attempts have been made both experimentally and theoretically. Here we performed hybrid density functional theory calculations to systematically investigate the electronic structures with polaronic redox behavior of polyanionic intercalation compounds similar to LiFePO4, such as in XMPO4 (X = Li, Na; M = Mn, Fe, Co, Ni). It is proved that the replacement of Li ions does not eliminate the polaronic redox behavior of Fe ions during delithiation and hence does not lead to a significant improvement in electronic conductivity. By contrast, replacing Fe with Mn, Co or Ni can tune the polaronic redox behavior during delithiation by varying degrees. For Ni, the polaronic redox behavior has almost disappeared, and band gaps disappear during delithiation, indicating a better electronic conductivity. For Mn or Co, the polaronic redox behavior is still obvious with little improvement in the electronic conductivity. This study provides important clues to improve the electronic conductivity of LiFePO4-like cathode materials.
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Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.










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