Probing the electrochemical behaviour of lithium imide as an electrolyte for solid-state batteries.

EES batteries Pub Date : 2025-04-02 eCollection Date: 2025-06-09 DOI:10.1039/d5eb00058k
Jeremy P Lowen, Teresa Insinna, Tharigopala V Beatriceveena, Mark P Stockham, Bo Dong, Sarah J Day, Clare P Grey, Emma Kendrick, Peter R Slater, Paul A Anderson, Joshua W Makepeace
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Abstract

All-solid-state batteries utilising a Li-metal anode have long promised to be the next-generation of high-performance energy storage device, with a step-change in energy density, cycling stability and cell safety touted as potential advantages compared to conventional Li-ion battery cells. A key to enabling this technology is the development of solid-state electrolytes with the elusive combination of high ionic conductivity, wide electrochemical stability and the ability to form a conductive and stable interface with Li metal. Presently, oxide and sulfide-based materials, particularly garnet and argyrodite-type structures, have proved most promising for this application. However, these still suffer from a number of challenges, including resistive lithium metal interfaces, poor lithium dendrite suppression (at high current density) and low voltage stability. Here we report the first application of lithium imide, an antifluorite-structured material, as a solid electrolyte in a Li-metal battery. Low-temperature synthesis of lithium imide produces promising Li-ion conductivity, reaching >1 mS cm-1 at 30 °C using a modest post-synthetic mechanochemical treatment, as well as displaying at least 5 V stability vs. Li+/Li. In situ electrochemical operation of lithium imide with Li-metal electrodes reveals an apparent 1000-fold increase in its measured conductivity, whilst appearing to remain an electronic insulator. It is postulated that stoichiometry variation at the grain boundary may contribute to this conductivity improvement. Furthermore, the material is shown to possess impressive resistance to hard shorting under high current density conditions (70 mA cm-2) as well as the ability to operate in Li-metal battery cells. These results not only highlight the promising performance of lithium imide, but also its potential to be the basis for a new family of antifluorite based solid electrolytes.

探测亚胺锂作为固态电池电解质的电化学行为。
长期以来,使用锂金属阳极的全固态电池一直被认为是下一代高性能储能设备,与传统锂离子电池相比,它在能量密度、循环稳定性和电池安全性方面具有阶梯式变化,被誉为潜在优势。实现这项技术的关键是固态电解质的开发,这种电解质具有高离子电导率、广泛的电化学稳定性以及与锂金属形成导电和稳定界面的能力。目前,氧化物和硫化物基材料,特别是石榴石和银辉石类型的结构,已被证明是最有前途的应用。然而,这些仍然面临许多挑战,包括电阻锂金属界面,锂枝晶抑制差(在高电流密度下)和低电压稳定性。本文报道了亚胺锂作为固体电解质在锂金属电池中的首次应用,这是一种反萤石结构材料。低温合成亚胺锂产生了很有前途的锂离子电导率,在30°C下,使用适度的合成后机械化学处理,达到>.1 mS cm-1,并且与Li+/Li相比,具有至少5 V的稳定性。用锂金属电极对亚胺锂进行原位电化学操作,发现其测量电导率明显增加了1000倍,同时看起来仍然是电子绝缘体。据推测,晶界的化学计量学变化可能有助于电导率的提高。此外,该材料在高电流密度条件下(70毫安厘米-2)具有令人印象深刻的抗硬短路能力,并且能够在锂金属电池中工作。这些结果不仅突出了亚胺锂的良好性能,而且它有可能成为一个新的反萤石基固体电解质家族的基础。
本文章由计算机程序翻译,如有差异,请以英文原文为准。
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