Comparison of LiVPO4F to Li4Ti5O12 as Anode Materials for Lithium-Ion Batteries
2013
Ma, Rui | Shao, Lianyi | Wu, Kaiqiang | Shui, Miao | Wang, Dongjie | Pan, Jianguo | Long, Nengbing | Ren, Yuanlong | Shu, Jie
In this paper, we reported on a comparison of LiVPO₄F to Li₄Ti₅O₁₂ as anode materials for lithium-ion batteries. Combined with powder X-ray diffraction, scanning electron microscopy, high-resolution transmission electron microscopy, galvanostatic discharge/charge tests and in situ X-ray diffraction technologies, we explore and compare the insertion/extraction mechanisms of LiVPO₄F based on the V³⁺/V²⁺/V⁺ redox couples and Li₄Ti₅O₁₂ based on the Ti⁴⁺/Ti³⁺ redox couple cycled in 1.0–3.0 V and 0.0–3.0 V. The electrochemical results indicate that both LiVPO₄F and Li₄Ti₅O₁₂ are solid electrolyte interphase free materials in 1.0–3.0 V. The insertion/extraction mechanisms of LiVPO₄F and Li₄Ti₅O₁₂ are similar with each other in 1.0–3.0 V as proved by in situ X-ray diffraction. It also demonstrates that both samples possess stable structure in 0.0–3.0 V. Additionally, the electrochemical performance tests of LiVPO₄F and Li₄Ti₅O₁₂ indicate that both samples cycled in 0.0–3.0 V exhibit much higher capacities than those cycled in 1.0–3.0 V but display worse cycle performance. The rate performance of Li₄Ti₅O₁₂ far exceeds that of LiVPO₄F in the same electrochemical potential window. In particular, the capacity retention of Li₄Ti₅O₁₂ cycled in 1.0–3.0 V is as high as 98.2% after 20 cycles. By contrast, Li₄Ti₅O₁₂ is expected to be a candidate anode material considering its high working potential, structural zero-strain property, and excellent cycle stability and rate performance.
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