Reversible Electrochemical Lithium Cycling in a Vanadium(IV)- and Niobium(V)-Based Wadsley–Roth Phase
Reversible Electrochemical Lithium Cycling in a Vanadium(IV)- and Niobium(V)-Based Wadsley–Roth Phase
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钒 (IV) 和铌 (V) 基 Wadsley-Roth 相中的可逆电化学锂循环
DOI：
10.1021/acs.chemmater.2c03465
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发表时间：
2023
影响因子：
8.6
通讯作者：
Sparks, Taylor D.
中科院分区：
文献类型：
--
作者：
Lawrence, Erick A.;Davenport, Matthew A.;Devi, Reshma;Cai, Zijian;Avdeev, Maxim;Belnap, Jonathan R.;Liu, Jue;Alnaser, Husain;Ho, Alice;Sparks, Taylor D.
快速充电仍然是锂离子电池最大的安全挑战之一，因为如果锂化得太快，石墨阳极上会出现锂树枝晶生长。对高速阳极的研究突出了Wadsley-Roth(WR)剪切相家族中的材料。与传统的Nb和W的WR组分相比，V的相对丰度使V基相具有吸引力。然而，与V氧化还原相关的高电压和较差的可逆性使得富V的WR相比富Nb和W的相少被研究。在这里，我们展示了一种新的富V的Wadsley-Roth相，V7Nb6O29，与其他富V的WR相相比，它在228次循环后具有优异的倍率性能和80%的容量保持率，平均电压为1.76V vs Li/Li+。单晶X-射线衍射谱显示，Ap_4/m空间群具有重复的V4+和Nb5+八面体的2×2×∞和3×3×∞块。结合中子对分布函数分析、X射线吸收光谱和密度泛函理论计算表明，V氧化还原是容量的主要来源，循环稳定性是由V4+在材料中采用的稳定八面体配位提供的。
Fast charging remains one of the greatest safety challenges in Li-ion batteries due to Li-dendrite growth occurring on graphite anodes if they are lithiated too quickly. The search for high-rate anodes has highlighted materials in the Wadsley–Roth (WR) shear phase family. The relative abundance of V compared with traditional WR compositions of Nb and W makes V-based phases attractive. However, the high voltage and poor reversibility typically associated with V redox have made V-rich WR phases less studied than Nb- and W-rich phases. Here, we show that a new V-rich Wadsley–Roth phase, V7Nb6O29, achieves excellent rate capability and 80% capacity retention after 228 cycles with a relatively low average voltage of 1.76 V vs Li/Li+compared with other V-rich WR phases. Single-crystal X-ray diffraction reveals aP4/mspace group with repeating 2 × 2 × ∞ and 3 × 3 × ∞ blocks of V4+and Nb5+octahedra. Combined neutron pair distribution function analysis, X-ray absorption spectroscopy, and density functional theory calculations show that V redox is the primary source of capacity and that cycling stability is provided by the stable octahedral coordination adopted by V4+in the material.
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