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Preparation, Structure, and Electrochemistry of Layered Polyanionic Hydroxysulfates: LiMSO4OH (M=Fe, Co, Mn) Electrodes for Li-ion Batteries
Abstract£ºThe 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¡ãC 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.[ À´×Ô¿ÆÑмÒ×å ï®µç³ØÊÀ½ç ]
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