Dan-Thien Nguyen , Venkateshkumar Prabhakaran , Libor Kovarik , Grant Alexander , Jordi Cabana , Justin G. Connell , Jian Zhi Hu , Vaithiyalingam Shutthanandan , Bhuvaneswari Modachur Sivakumar , Karl T. Mueller , Vijayakumar Murugesan
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引用次数: 0
摘要
设计在重复离子插入和提取过程中保持化学和结构稳定的阴极材料是开发多价电池的一大挑战。传统的金属氧化物阴极的循环稳定性受到多价阳离子缓慢扩散和界面寄生反应的挑战,包括阴极电解质相间层(CEI)。了解阴极-电解质界面上的反应,尤其是由非均匀表面层引起的反应,是阴极材料和电解质的关键设计参数。在这项研究中,我们采用了多模态分析方法,包括原位和非原位 X 射线光电子能谱 (XPS)、高分辨率透射电子显微镜 (TEM) 和电化学阻抗能谱 (EIS),来研究高压氧化镁钒 (MgV2O4) 尖晶石阴极在 Mg2+ 插入/萃取过程中的表面反应以及随后的 CEI 结构和化学演变。研究结果表明,氧化镁钒阴极中存在的非均一表面层推动了双(三氟甲烷磺酰)亚胺(TFSI-)阴离子的分解,导致 CEI 层的形成。CEI 层可抑制 Mg2+ 离子转移过程。伴随着这种反应性驱动的降解,氧化镁钒阴极发生粉碎,形成纳米颗粒簇。这一过程可能会产生新的插层位点并缩短 Mg2+ 阳离子的扩散路径,从而提高循环能力。这项研究表明,控制表面化学计量和工程形态特性是高性能多价电池阴极的关键设计参数。
Structural and chemical evolutions of a magnesium vanadium oxide cathode under electrochemical cycling in magnesium batteries
The design of cathode materials that remain chemically and structurally stable during repetitive ion insertion and extraction poses a significant challenge in developing multivalent batteries. The cycling stability of traditional metal oxide-based cathode is challenged by sluggish diffusion of multivalent cations and parasitic reactivity at interfacial regimes, including the cathode electrolyte interphase layer (CEI). Understanding the reactions at the cathode-electrolyte interface, particularly those induced by non-stoichiometric surface layers, is a crucial design parameter for both cathode materials and electrolytes. In this study, we employed multimodal analysis, including in situ and ex situ X-ray photoelectron spectroscopy (XPS), high resolution transmission electron microscopy (TEM) and electrochemical impedance spectroscopy (EIS) to examine the surface reactions and subsequent structural and chemical evolutions of the CEI on high voltage magnesium vanadium oxide (MgV2O4) spinel cathode during the Mg2+ insertion/extraction processes. The results revealed that the presence of non-stoichiometric surface layers in the magnesium vanadium oxide cathode drive the decomposition of bis(trifluoromethanesulfonyl)imide (TFSI-) anion, leading to the formation of the CEI layer. The CEI layer could inhibit the Mg2+ ion transfer processes. Accompanying this reactivity-driven degradation, the magnesium vanadium oxide cathode undergoes pulverization, forming clusters of nanosized particles. This process likely improves cycling ability by creating new intercalation sites and shortening the diffusion pathway for the Mg2+ cations. This study demonstrates that controlling surface stoichiometry and engineering morphological properties are critical design parameters for high performance cathodes for multivalent batteries.
期刊介绍:
Nano Energy is a multidisciplinary, rapid-publication forum of original peer-reviewed contributions on the science and engineering of nanomaterials and nanodevices used in all forms of energy harvesting, conversion, storage, utilization and policy. Through its mixture of articles, reviews, communications, research news, and information on key developments, Nano Energy provides a comprehensive coverage of this exciting and dynamic field which joins nanoscience and nanotechnology with energy science. The journal is relevant to all those who are interested in nanomaterials solutions to the energy problem.
Nano Energy publishes original experimental and theoretical research on all aspects of energy-related research which utilizes nanomaterials and nanotechnology. Manuscripts of four types are considered: review articles which inform readers of the latest research and advances in energy science; rapid communications which feature exciting research breakthroughs in the field; full-length articles which report comprehensive research developments; and news and opinions which comment on topical issues or express views on the developments in related fields.