Preparation, Structure, and Electrochemistry of Layered Polyanionic Hydroxysulfates: LiMSO4OH (M = Fe, Co, Mn) Electrodes for Li-Ion Batteries

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• 作者：Chinmayee V. Subban ; Mohamed Ati ; Gwena毛lle Rousse ; Artem M. Abakumov ; Gustaaf Van Tendeloo ; Rapha毛l Janot ; Jean-Marie Tarascon
• 刊名：The Journal of the American Chemical Society
• 出版年：2013
• 出版时间：March 6, 2013
• 年：2013
• 卷：135
• 期：9
• 页码：3653-3661
• 全文大小：436K
• 年卷期：v.135,no.9(March 6, 2013)
• ISSN：1520-5126

文摘

The Li-ion rechargeable battery, due to its high energy density, has driven remarkable advances in portable electronics. Moving toward more sustainable electrodes could make this technology even more attractive to large-volume applications. We present here a new family of 3d-metal hydroxysulfates of general formula LiMSO₄OH (M = Fe, Co, and Mn) among which (i) LiFeSO₄OH reversibly releases 0.7 Li⁺ at an average potential of 3.6 V vs Li⁺/Li⁰, slightly higher than the potential of currently lauded LiFePO₄ (3.45 V) electrode material, and (ii) LiCoSO₄OH shows a redox activity at 4.7 V vs Li⁺/Li⁰. Besides, these compounds can be easily made at temperatures near 200 掳C via a synthesis process that enlists a new intermediate phase of composition M₃(SO₄)₂(OH)₂ (M = Fe, Co, Mn, and Ni), related to the mineral caminite. Structurally, we found that LiFeSO₄OH is a layered phase unlike the previously reported 3.2 V tavorite LiFeSO₄OH. This work should provide an impetus to experimentalists for designing better electrolytes to fully tap the capacity of high-voltage Co-based hydroxysulfates, and to theorists for providing a means to predict the electrochemical redox activity of two polymorphs.