New Mn and V-rich Phosphate Fluoride Obtained by Topochemical Reaction for Na-ion Batteries Positive Electrode

IF 7.2 2区材料科学 Q2 CHEMISTRY, PHYSICAL

Chemistry of Materials Pub Date : 2024-10-04 DOI:10.1021/acs.chemmater.4c01833

Gaël Minart, Mathieu Duttine, Antonella Iadecola, Jean-Paul Salvetat, François Weill, Sonia Buffière, Romain Wernert, Jacob Olchowka, Laurence Croguennec

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Abstract

A new positive electrode material, Na_2.85Mn_0.4V_1.6(PO₄)₂F_2.4O_0.6, is synthesized via a topochemical reaction in an ionic liquid medium, starting with a tailored precursor Mn_0.2(VO)_0.8PO₄·2H₂O. Its structural and chemical characterization was conducted using a comprehensive set of techniques including X-ray diffraction, X-ray absorption, and electron paramagnetic resonance spectroscopies, as well as inductively coupled plasma optical emission spectroscopy and electron probe microanalysis. These analyses not only allowed to determine the composition and structure but also shed light on the synthesis reaction mechanism. The resulting active material exhibits promising electrochemical performance, delivering a high capacity of 108 mA h/g at a rate of C/20 with an average potential of 3.75 V vs Na⁺/Na. Even at a higher rate of 1C, a specific capacity of 90 mA h/g is maintained and an excellent capacity retention of 94% is demonstrated after 200 cycles at C/5. In addition, XAS analysis conducted on materials recovered at different states of charge reveals the redox activity of both manganese and vanadium centers. More generally, this work showcases the feasibility of synthesizing stable Na-deficient polyanionic phases within the Na_zMn_xV_2–x(PO₄)₂F_3–yO_y (0 ≤ x, y ≤ 2, and z ≤ 3.6) material family.

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通过拓扑化学反应获得的新型富锰和富钒氟化磷，可用于钠离子电池正极

从定制的前驱体 Mn0.2(VO)0.8PO4-2H2O开始，在离子液体介质中通过拓扑化学反应合成了一种新型正极材料 Na2.85Mn0.4V1.6(PO4)2F2.4O0.6。对其结构和化学特性的分析采用了一整套技术，包括 X 射线衍射、X 射线吸收和电子顺磁共振光谱，以及电感耦合等离子体光学发射光谱和电子探针显微分析。这些分析不仅确定了材料的组成和结构，还揭示了合成反应机理。所制备的活性材料具有良好的电化学性能，在 C/20 速率下可提供 108 mA h/g 的高容量，对 Na+/Na 的平均电位为 3.75 V。即使在更高的 1C 速率下，也能保持 90 mA h/g 的比容量，而且在 C/5 速率下循环 200 次后，容量保持率高达 94%。此外，对在不同电荷状态下回收的材料进行的 XAS 分析显示了锰和钒中心的氧化还原活性。更广泛地说，这项工作展示了在 NazMnxV2-x(PO4)2F3-yOy （0 ≤ x，y ≤ 2，z ≤ 3.6）材料家族中合成稳定的缺 Na 多阴离子相的可行性。

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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.