Abstract
Vanadium bronzes have been well-demonstrated as promising cathode materials for aqueous zinc-ion batteries. However, conventional single-ion pre-intercalated V2O5 nearly reached its energy/power ceiling due to the nature of micro/electronic structures and unfavourable phase transition during Zn2+ storage processes. Here, a simple and universal in-situ anodic oxidation method of quasi-layered CaV4O9 in a tailored electrolyte was developed to introduce dual ions (Ca2+ and Zn2+) into bilayer δ-V2O5 frameworks forming crystallographic ultra-thin vanadium bronzes, Ca0.12Zn0.12V2O5·nH2O. The materials deliver transcendental maximum energy and power densities of 366 W h kg−1 (478 mA h g−1 @ 0.2 A g−1) and 6627 W kg−1 (245 mA h g−1 @ 10 A g−1), respectively, and the long cycling stability with a high specific capacity up to 205 mA h g−1 after 3000 cycles at 10 A g−1. The synergistic contributions of dual ions and Ca2+ electrolyte additives on battery performances were systematically investigated by multiple in-/ex-situ characterisations to reveal reversible structural/chemical evolutions and enhanced electrochemical kinetics, highlighting the significance of electrolyte-governed conversion reaction process. Through the computational approach, reinforced “pillar” effects, charge screening effects and regulated electronic structures derived from pre-intercalated dual ions were elucidated for contributing to boosted charge storage properties.
摘要
钒青铜是一种极具潜力的水系锌离子电池正极材料. 然而, 传统 的单离子预插层V2O5材料由于自身结构的限制和储锌过程中发生不可 逆的相变使其储锌能力接近上限. 本文采用原位阴极氧化法将准层状 材料CaV4O9在特定的电解液中将双离子(Ca2+, Zn2+)引入δ-V2O5晶体 骨架中, 形成超薄钒青铜材料Ca0.12Zn0.12V2O5·nH2O. 该材料表现出超 高的能量密度(366 W h kg−1)和功率密度(6627 W kg−1), 并在大电流 10 A g−1下循环3000圈后可逆比容量仍高达205 mA h g−1. 通过多种原 位/非原位表征, 系统地揭示了材料与Ca2+电解液添加剂的协同作用, 使结构、电化学可逆性和反应动力学得到有效提升, 并凸显了电解液 调控对转化反应过程的重要性. 经过理论计算, 阐明了双离子预嵌入衍 生的“支柱”增强效应、电荷屏蔽效应和调控电子结构对增强电荷储存 性能的作用.
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Acknowledgements
This work was supported by the Engineering and Physical Sciences Research Council (EPSRC, EP/V027433/1) of UK, the National Key Research and Development Program of China (2018YFA0704502 and 2017YFA0700103), the National Natural Science Foundation of China (21703248), the Strategic Priority Research Program of the Chinese Academy of Sciences (XDB20000000), and the Royal Society (RGSR1211080, IESR2212115) of UK.
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Li J and He G designed the project; Li J synthesised the materials, carried out the characterisation and wrote the original draft; Hong N fabricated the batteries and performed the electrochemical evaluation and helped draft the original manuscript; Luo N performed DFT calculations, Dong H and Kang L contributed to TEM and ex-situ characterisations; Peng Z and Jia G helped with electrochemical data analysis. He G directed the project; Chai G, Wang M and He G supervised the project and acquired the funding. All authors contributed to the general discussion and manuscript revision.
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Experimental details and supporting data are available in the online version of the paper.
Guanjie He is an associate professor in materials chemistry, leader for the Advanced Functional Materials Research Group, University of Lincoln and an Honorary Lecturer at University College London (UCL). He received his PhD degree in 2018 from the Department of Chemistry, UCL. His research focuses on materials for electrochemical energy storage and conversion applications, especially electrode materials in aqueous electrolyte systems.
Guoliang Chai has been a Professor at Fujian Institute of Research on the Structure of Matter (FJIRSM), Chinese Academy of Sciences (CAS) since 2016. He received his PhD degree in 2012 from FJIRSM, CAS. After that, he worked as a postdoc at Tokyo Institute of Technology from 2012 to 2014, and UCL as a research associate from 2014 to 2016. His current research interests focus on electrochemical catalysis, energy storage materials, and first-principles simulations.
Min Wang is a professor at Qinghai Institute of Salt Lakes, CAS. She is a member of expert panel for the Ministry of Science and Technology of China, National Torch Program, Lithium Branch of China Non-ferrous Metals Industry Association, China Patent Technology Examination. Her research interest includes comprehensive development and industrialisation of potassium, lithium, boron, magnesium resources in salt lake in terms of thermal energy storage, lithium extraction technologies and formulation of salt lake chemical industrial standards.
Jianwei Li received his BSc degree (2012) in material physics from Sun-yat Sen University and PhD degree from UCL under co-supervision of Prof. Ivan Parkin and Prof. Claire Carmalt in 2021. His research interest includes inorganic material design and synthesis, structural-functional studies and charge storage mechanism for rechargeable aqueous ion batteries.
Ningyun Hong received his BSc degree from Henan University in 2017 and MSc degree from Qinghai Institute of Salt Lakes, CAS in 2021. He is currently a PhD candidate at Tianjin University of Technology under the supervision of Prof. Yicheng Wu. His present research interest focuses on the design and synthesis of advanced cathode materials for sodium ion batteries.
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Li, J., Hong, N., Luo, N. et al. In-situ electrochemical modification of pre-intercalated vanadium bronze cathodes for aqueous zinc-ion batteries. Sci. China Mater. 65, 1165–1175 (2022). https://doi.org/10.1007/s40843-021-1893-2
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DOI: https://doi.org/10.1007/s40843-021-1893-2