钠对普鲁士蓝类似物中水动力学的影响

IF 7.2 2区材料科学 Q2 CHEMISTRY, PHYSICAL

Chemistry of Materials Pub Date : 2024-11-16 DOI:10.1021/acs.chemmater.4c02326

Ida Nielsen, Alexandra Ulander, Fanni Juranyi, Simon Rosenqvist Larsen, Maths Karlsson, William R. Brant, Mikael S. Andersson

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引用次数: 0

摘要

普鲁士蓝类似物（PBA）是钠离子电池的一种有趣的阴极材料，尤其是铁基无空位 PBA Na2-xFe[Fe(CN)6]-zH2O。然而，水的存在对 PBA 作为电极材料的应用具有相反的作用：水提供了结构稳定性，确保钠萃取和插入过程中体积变化最小，然而，水会与电解质发生反应，导致不必要的副反应。因此，必须用另一种兼容的小分子取代水，以确保最佳性能。要做到这一点，深入了解水的动力学至关重要。我们利用准弹性中子散射（QENS）对两种样品进行了研究：Na1.90(9)Fe0.90(7)2+Fe0.10(3)3+[Fe2+(CN)6]-2.12(2)H2O 和 Na0.34(5)Fe3+[Fe2.66(5)+(CN)6]-0.360(4)H2O 。结果表明，水的动力学与钠的含量密切相关。研究发现，水在多孔框架中的球形空腔内扩散，高钠含量样品的半径为 2.6 Å，低钠含量样品的半径为 1.8 Å，这与晶体结构中的孔隙大小一致。除了在孔隙内扩散的水之外，研究还发现一小部分水表现出嘎嘎作响或旋转运动，这表明这些水与钠离子发生了强烈的相互作用和结合。这些结果从根本上揭示了水在 PBA 中的作用，为使用与非水电池系统兼容的另一种小分子代替水并同时确保结构稳定性奠定了基础。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

Impact of Sodium on the Water Dynamics in Prussian Blue Analogues

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Impact of Sodium on the Water Dynamics in Prussian Blue Analogues

Prussian blue analogues (PBAs) are interesting cathode materials for sodium-ion batteries, especially the iron-based, [Fe(CN)₆]ⁿ⁻ vacancy-free PBA Na_2–xFe[Fe(CN)₆]·zH₂O. However, the presence of water has an opposing role in the application of PBAs as electrode materials: the water provides structural stability ensuring minimum volume changes during sodium extraction and insertion, however, water can react with the electrolyte leading to unwanted side reactions. Therefore, water must be replaced with another compatible small molecule to ensure optimal performance. To achieve this, insights into the dynamics of water are crucial. Two samples with compositions of Na_1.90(9)Fe_0.90(7)²⁺Fe_0.10(3)³⁺[Fe²⁺(CN)₆]·2.12(2)H₂O and Na_0.34(5)Fe³⁺[Fe^2.66(5)+(CN)₆]·0.360(4)H₂O were investigated using quasi-elastic neutron scattering (QENS). The results show that the water dynamics strongly depend on the sodium content. The water was found to diffuse within a spherical cavity in the porous framework with a radius of 2.6 Å for the high sodium-containing sample and 1.8 Å for the low sodium-containing sample consistent with the pore sizes in the crystal structures. In addition to the water diffusing within the pores, it was found that a small fraction of the water exhibits a rattling or rotational motion suggesting that this water strongly interacts and binds to the sodium ions. For the high sodium-containing sample, this rattling or rotational motion transforms into quantum rotational tunneling of the water below 75 K. These results give new fundamental insight into the role of water in PBAs, laying the groundwork for substituting water with another small molecule compatible with nonaqueous battery systems while also ensuring structural stability.

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来源期刊

Chemistry of Materials 工程技术-材料科学：综合

CiteScore

14.10

自引率

5.80%

发文量

929

审稿时长

1.5 months

期刊介绍： The journal Chemistry of Materials focuses on publishing original research at the intersection of materials science and chemistry. The studies published in the journal involve chemistry as a prominent component and explore topics such as the design, synthesis, characterization, processing, understanding, and application of functional or potentially functional materials. The journal covers various areas of interest, including inorganic and organic solid-state chemistry, nanomaterials, biomaterials, thin films and polymers, and composite/hybrid materials. The journal particularly seeks papers that highlight the creation or development of innovative materials with novel optical, electrical, magnetic, catalytic, or mechanical properties. It is essential that manuscripts on these topics have a primary focus on the chemistry of materials and represent a significant advancement compared to prior research. Before external reviews are sought, submitted manuscripts undergo a review process by a minimum of two editors to ensure their appropriateness for the journal and the presence of sufficient evidence of a significant advance that will be of broad interest to the materials chemistry community.