Activating reversible multi-electron reaction of Na3(VO)2(PO4)2F cathode via Fe/F dual-doping for high-energy and stable sodium storage

IF 18.9 1区 材料科学 Q1 CHEMISTRY, PHYSICAL Energy Storage Materials Pub Date : 2024-12-14 DOI:10.1016/j.ensm.2024.103960
Qiang Fu, Fangxiang Song, Changhui Mu, Qingqing Wu, Keliang Wang, Song Li, Xianquan Ao
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Abstract

Na3(VO)2(PO4)2F cathode has garnered extensive interest for its stable structure, abundant Na+ migration channels, and high working voltage, though higher energy densities are sought for commercial applications. This study enhances energy density by activating multi-electron reactions through the partial substitution of V4+ and dangling O2− with Fe3+ and F⁻, respectively, using a straightforward hydrothermal method. This substitution successfully activates the V3+/V4+ redox couple, facilitating multi-electron reactions. The modified cathode, Na₃(VO)1.8Fe0.2(PO4)2F1.2 (N(VO)1.8Fe0.2PF1.2), exhibits a reversible specific capacity of 213.3 mAh g−1 at 50 mA g−1. Characterization techniques, including in situ X-ray diffraction and ex-situ X-ray photoelectron spectroscopy, confirm that the activated V3+/V4+ redox reaction proceeds via a solid-solution mechanism. Density functional theory analysis suggests that Na3(VO)1.8Fe0.2(PO4)2F1.2 offers improved electronic conductivity and structural stability, elucidating the origins of low Na+ migration energy barriers and ideal diffusion kinetics. When paired with a hard carbon (HC) anode, the full cell (HC//N(VO)1.8Fe0.2PF1.2) achieves a reversible capacity of 196.6 mAh g−1 and an energy density of 287.0 Wh kg−1 at 50 mA g−1, demonstrating exceptional long-term cyclic stability with a capacity retention of 94.7% after 200 cycles at 500 mA g−1. This study opens new avenues for the commercial application of sodium-ion batteries (SIBs) cathodes.
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通过Fe/F双掺杂激活Na3(VO)2(PO4)2F阴极的可逆多电子反应,实现高能量和稳定的钠存储
Na3(VO)2(PO4)2F阴极由于其稳定的结构、丰富的Na+迁移通道和高工作电压而获得了广泛的兴趣,尽管更高的能量密度仍在寻求商业应用。本研究通过简单的水热法,分别用Fe3+和F⁻部分取代V4+和悬空O2−来激活多电子反应,从而提高了能量密度。这种取代成功激活了V3+/V4+氧化还原对,促进了多电子反应。改性后的阴极Na₃(VO)1.8Fe0.2(PO4)2F1.2 (N(VO)1.8Fe0.2 pf1.2)在50 mA g−1时的可逆比容量为213.3 mAh g−1。表征技术,包括原位x射线衍射和非原位x射线光电子能谱,证实了活化的V3+/V4+氧化还原反应是通过固溶机制进行的。密度泛函理论分析表明,Na3(VO)1.8Fe0.2(PO4)2F1.2具有更好的电子导电性和结构稳定性,阐明了低Na+迁移能垒和理想扩散动力学的起源。当与硬碳(HC)阳极配对时,全电池(HC//N(VO)1.8Fe0.2PF1.2)在50 mA g- 1下达到196.6 mAh g- 1的可逆容量和287.0 Wh kg - 1的能量密度,在500 mA g- 1下200次循环后表现出优异的长期循环稳定性,容量保持率为94.7%。本研究为钠离子电池(SIBs)阴极的商业化应用开辟了新的途径。
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来源期刊
Energy Storage Materials
Energy Storage Materials Materials Science-General Materials Science
CiteScore
33.00
自引率
5.90%
发文量
652
审稿时长
27 days
期刊介绍: Energy Storage Materials is a global interdisciplinary journal dedicated to sharing scientific and technological advancements in materials and devices for advanced energy storage and related energy conversion, such as in metal-O2 batteries. The journal features comprehensive research articles, including full papers and short communications, as well as authoritative feature articles and reviews by leading experts in the field. Energy Storage Materials covers a wide range of topics, including the synthesis, fabrication, structure, properties, performance, and technological applications of energy storage materials. Additionally, the journal explores strategies, policies, and developments in the field of energy storage materials and devices for sustainable energy. Published papers are selected based on their scientific and technological significance, their ability to provide valuable new knowledge, and their relevance to the international research community.
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