Tailoring sulfidation and derivatization of Prussian blue analogues towards electrochemically stable metal sulfides/carbon nanohybrids

将普鲁士蓝类似物的硫化和衍生化调整为电化学稳定的金属硫化物/碳纳米杂化物

• 批准号: 463914313
• 负责人: Dr. Samantha Husmann
• 金额: --
• 依托单位: Leibniz-Institut für Neue Materialien gGmbH (INM)
• 依托单位国家: 德国
• 项目类别: Research Grants
• 财政年份: 2021
• 资助国家: 德国
• 起止时间: 2020-12-31 至 2021-12-31
• 项目状态: 已结题
• 来源: https://gepris.dfg.de/gepris/projekt/463914313?language=en
• 关键词: Tailoring; sulfidation; derivatization; Prussian; blue

Advanced battery electrode materials require careful design on a nanoscale. Often, even slight changes in morphology and composition result in great changes in the efficiency and stability. Therefore, it is fundamental to correlate synthesis parameters with material performance and resulting electrochemical metrics. Only by this way, we can establish a knowledge platform rather than relying on empiric trial-and-error. A great example for the challenges in nanoengineering of materials are metal sulfides. Metal sulfides have a huge potential as battery electrodes due to their inherent high theoretical capacity. However, while performing in such application, they face fast capacity drop that leads to an overall inefficient device. This is because they undergo great volumetric variation during charge/discharge cycles, causing particle aggregation, electrode cracking, besides other effects that compromise material stability. In addition, metal sulfides in general are not conductive being often combined with carbon additives to improve charge mobility. The lack of proper interaction or blending of these components result in a diminished conductivity along the cycles hindering the electrode performance. To capitalize metal sulfides capacity with a long-term stability and efficiency, material structure must be carefully considered.The present application focuses on Prussian blue and analogues (PBA - M[M’(CN)6]) as precursors for metal sulfide preparation. PBA are cheap, easy to prepare and are water and air stable, different from many metal oxide and sulfides precursors. Acting as both metal and carbon source, they can be converted into metal oxides, porous carbon or hybrids between those. By adding a sulfur source, they can produce metal sulfides with high porosity. Currently there are no consistent studies on the precursor character and treatment parameters in the resulting derivative with studies often limited to one sample-one treatment. Preliminary work by the applicant demonstrates the feasibility of the project and the same time shows the complex relation between synthesis parameters and resulting properties. This proposal aims to fill the gap of the link between derivatization parameters and electrochemical properties of metal sulfides produced from PBA. The project involves a systematic derivatization/sulfidation of PBA under different conditions, where morphology, composition and structure are carefully characterized. By doing so, we will be able to design a PBA-derived metal sulfide that can fulfill electrode requirements for a long-term stable battery. This will be demonstrated by tuning derivative properties through synthesis control and evaluating their electrochemical performance as battery cathodes in combination with post-mortem analysis to elucidate material transformations within testing. The project is an important milestone for the development of the applicant as an independent researcher.

先进的电池电极材料需要在纳米级上进行精心设计。通常，即使是形态和组成的微小变化也会导致效率和稳定性的巨大变化。因此，将合成参数与材料性能和所得电化学度量相关联是至关重要的。只有这样，我们才能建立一个知识平台，而不是依靠经验试错。材料纳米工程挑战的一个很好的例子是金属硫化物。金属硫化物由于其固有的高理论容量而具有作为电池电极的巨大潜力。然而，当在这样的应用中执行时，它们面临快速的容量下降，这导致整体效率低下的设备。这是因为它们在充电/放电循环期间经历很大的体积变化，导致颗粒聚集、电极破裂以及损害材料稳定性的其他影响。此外，金属硫化物通常不导电，通常与碳添加剂组合以改善电荷迁移率。这些组分缺乏适当的相互作用或混合导致沿着循环的导电性降低，从而阻碍电极性能。本申请集中于普鲁士蓝和类似物（PBA-M [M ′（CN）6]）作为金属硫化物制备的前体。PBA价格便宜，易于制备，并且是水和空气稳定的，不同于许多金属氧化物和硫化物前体。作为金属和碳源，它们可以转化为金属氧化物、多孔碳或它们之间的混合物。通过添加硫源，它们可以产生具有高孔隙率的金属硫化物。目前还没有一致的研究前体的特点和处理参数，在所产生的衍生物的研究往往限于一个样本一个处理。申请人的初步工作证明了该项目的可行性，同时显示了合成参数与所得性能之间的复杂关系。 该提案旨在填补衍生化参数与PBA产生的金属硫化物的电化学性质之间的联系的差距。该项目涉及PBA在不同条件下的系统衍生/硫化，其中仔细表征形态，组成和结构。通过这样做，我们将能够设计出一种PBA衍生的金属硫化物，可以满足长期稳定电池的电极要求。这将通过合成控制调整衍生物特性并评价其作为电池阴极的电化学性能，结合事后分析来阐明测试中的材料转化来证明。该项目是申请人发展为独立研究人员的重要里程碑。