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.

高级电池电极材料需要在纳米级上进行仔细的设计。通常，即使形态和组成的略有变化也会导致效率和稳定性发生巨大变化。因此，将合成参数与材料性能和产生的电化学指标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，而不是依靠经验性的反复试验。一个很好的例子是，金属硫化物的纳米工程挑战具有巨大的潜力，因为它们继承了高理论能力。但是，在此应用程序中执行时，它们面临的快速下降会导致整体无效的设备。这是因为它们在电荷/放电周期期间经历了巨大的体积变化，导致颗粒聚集，电极裂纹，除了其他损害材料稳定性的效果。此外，金属硫化物通常并非导电与碳添加剂相结合以提高电荷迁移率。这些组件缺乏适当的相互作用或混合，导致沿循环阻碍电极性能的循环的电导率降低。为了使金属硫化物的能力具有长期稳定性和效率，必须仔细考虑材料结构。目前的应用集中于普鲁士蓝色和类似物（PBA -M [M'（CN）6]）作为金属硫化物制备的前体。 PBA便宜，易于准备，并且是水和空气稳定的，与许多金属氧化物和硫化物前体不同。它们可以作为金属和碳源，可以转化为金属氧化物，多孔碳或杂种。通过添加硫源，它们可以产生高孔隙率的金属硫化物。当前，在由此产生的导数中，没有关于前体特征和治疗参数的一致研究，而研究通常仅限于一种样本一项治疗。适用的初步工作证明了项目的可行性，同一时间显示了综合参数与结果属性之间的复杂关系。该建议旨在填补来自PBA产生的金属硫化物的衍生参数和电化学特性之间的联系的空白。该项目涉及在不同条件下PBA的系统衍生化/硫化，其中仔细表征了形态，组成和结构。通过这样做，我们将能够设计出PBA衍生的金属硫化物，以满足长期稳定电池的电子需求。这将通过通过合成控制来调整导数特性，并评估其作为电池阴极的电化学性能与验尸后分析结合使用，以阐明测试中的材料转换。该项目是作为独立研究人员开发的重要里程碑。