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焦磷酸锂铬作为锂离子电池的插入材料。

Lithium chromium pyrophosphate as an insertion material for Li-ion batteries.

作者信息

Reichardt Martin, Sallard Sébastien, Novák Petr, Villevieille Claire

机构信息

Electrochemical Energy Storage Section, Paul Scherrer Institut, 5232 Villigen-PSI, Switzerland.

出版信息

Acta Crystallogr B Struct Sci Cryst Eng Mater. 2015 Dec 1;71(Pt 6):661-7. doi: 10.1107/S2052520615017539.

Abstract

Lithium chromium pyrophosphate (LiCrP2O7) and carbon-coated LiCrP2O7 (LiCrP2O7/C) were synthesized by solid-state and sol-gel routes, respectively. The materials were characterized by X-ray diffraction (XRD), thermogravimetric analysis (TGA), scanning electron microscopy (SEM) and conductivity measurements. LiCrP2O7 powder has a conductivity of ~ 10(-8) S cm(-1), ~ 10(4) times smaller than LiCrP2O7/C (~ 10(-4) S cm(-1)). LiCrP2O7/C is electrochemically active, mainly between 1.8 and 2.2 V versus Li(+)/Li (Cr(3+)/Cr(2+) redox couple), whereas LiCrP2O7 has limited electrochemical activity. LiCrP2O7/C delivers a reversible specific charge up to ~ 105 mAh g(-1) after 100 cycles, close to the theoretical limit of 115 mAh g(-1). Operando XRD experiments show slight peak shifts between 2.2 and 4.8 V versus Li(+)/Li, and a reversible amorphization between 1.8 and 2.2 V versus Li(+)/Li, suggesting an insertion reaction mechanism.

摘要

分别通过固态法和溶胶 - 凝胶法合成了焦磷酸锂铬(LiCrP₂O₇)和碳包覆的LiCrP₂O₇(LiCrP₂O₇/C)。通过X射线衍射(XRD)、热重分析(TGA)、扫描电子显微镜(SEM)和电导率测量对材料进行了表征。LiCrP₂O₇粉末的电导率约为10⁻⁸ S cm⁻¹,比LiCrP₂O₇/C(约10⁻⁴ S cm⁻¹)小约10⁴倍。LiCrP₂O₇/C具有电化学活性,主要在相对于Li⁺/Li(Cr³⁺/Cr²⁺氧化还原对)的1.8至2.2 V之间,而LiCrP₂O₇的电化学活性有限。LiCrP₂O₇/C在100次循环后可提供高达约105 mAh g⁻¹的可逆比电荷,接近115 mAh g⁻¹的理论极限。原位XRD实验表明,相对于Li⁺/Li,在2.2至4.8 V之间有轻微的峰位移,在相对于Li⁺/Li的1.8至2.2 V之间有可逆的非晶化,这表明存在嵌入反应机制。

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