Thiometallate-mediated polysulfide chemistry and lithium stabilization for stable anode-free lithium-sulfur batteries
Thiometallate-mediated polysulfide chemistry and lithium stabilization for stable anode-free lithium-sulfur batteries
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DOI：
10.1016/j.xcrp.2022.100808
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发表时间：
2022-03
影响因子：
8.9
通讯作者：
S. Nanda;Hooman Yaghoobnejad Asl;A. Bhargav;A. Manthiram
中科院分区：
文献类型：
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作者：
S. Nanda;Hooman Yaghoobnejad Asl;A. Bhargav;A. Manthiram
要实现高能量锂硫电池（Li- s）的长寿命，需要提高锂电镀和剥离的可逆性。可溶性多硫化物中间体的形成，通过还原成绝缘的Li2S和Li2S2来降解锂金属阳极，在Li-S系统中造成了一个独特的问题。本研究表明，引入四硫钼酸铵（NH4）2MoS4)和四硫钨酸铵（NH4）2WS4作为阴极添加剂，通过(1)与多硫化物络合并作为多硫化物缓冲液，从而减轻了腐蚀穿梭效应；(2)在锂表面形成稳定的钝化Mo/ w富集固体电解质界面（SEI）层，稳定了锂的沉积。由此产生的锂电沉积的稳定性使无阳极全电池的循环提高了近3倍。这项工作表明，硫金属酸盐配合物和多硫化物之间丰富的化学性质可以用来解决实现现实的锂硫电池以及更普遍的金属-硫电池的艰巨挑战。
Achieving long life with energy-dense lithium-sulfur (Li-S) batteries requires improving the reversibility of Li plating and stripping. The formation of soluble polysulfide intermediates, which degrade the Li-metal anode by reducing into insulating Li2S and Li2S2, create a unique problem in the Li-S system. Here, we show that the introduction of ammonium tetrathiomolybdate ((NH4)2MoS4) and ammonium tetrathiotungstate ((NH4)2WS4) as cathode additives stabilize Li deposition by (1) complexing with polysulfides and acting as a polysulfide buffer, thereby mitigating the corrosive shuttle effect and (2) forming a stable and passivating Mo/W-enriched solid-electrolyte interphase (SEI) layer on the Li surface. The resulting stabilization of Li electrodeposition enables a nearly 3-fold improvement in the cycle of anode-free full cells. This work demonstrates that the rich chemistry between thiometallate complexes and polysulfide species can be exploited to solve the formidable challenges with achieving a realistic Li-S battery and, more generally, metal-chalcogen batteries.