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Fundamental understanding and practical challenges of anionic redox activity in Li-ion batteries

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  • Gaurav Assat

    (Collège de France, Chimie du Solide et de l’Energie—UMR CNRS 8260
    Réseau sur le Stockage Electrochimique de l’Energie (RS2E)—FR CNRS 3459
    Sorbonne Universités, UPMC Université Paris 06)

  • Jean-Marie Tarascon

    (Collège de France, Chimie du Solide et de l’Energie—UMR CNRS 8260
    Réseau sur le Stockage Electrochimique de l’Energie (RS2E)—FR CNRS 3459
    Sorbonne Universités, UPMC Université Paris 06)

Abstract

Our increasing dependence on lithium-ion batteries for energy storage calls for continual improvements in the performance of their positive electrodes, which have so far relied solely on cationic redox of transition-metal ions for driving the electrochemical reactions. Great hopes have recently been placed on the emergence of anionic redox—a transformational approach for designing positive electrodes as it leads to a near-doubling of capacity. But questions have been raised about the fundamental origins of anionic redox and whether its full potential can be realized in applications. In this Review, we discuss the underlying science that triggers a reversible and stable anionic redox activity. Furthermore, we highlight its practical limitations and outline possible approaches for improving such materials and designing new ones. We also summarize their chances for market implementation in the face of the competing nickel-based layered cathodes that are prevalent today.

Suggested Citation

  • Gaurav Assat & Jean-Marie Tarascon, 2018. "Fundamental understanding and practical challenges of anionic redox activity in Li-ion batteries," Nature Energy, Nature, vol. 3(5), pages 373-386, May.
  • Handle: RePEc:nat:natene:v:3:y:2018:i:5:d:10.1038_s41560-018-0097-0
    DOI: 10.1038/s41560-018-0097-0
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    2. Laura Albero Blanquer & Florencia Marchini & Jan Roman Seitz & Nour Daher & Fanny Bétermier & Jiaqiang Huang & Charlotte Gervillié & Jean-Marie Tarascon, 2022. "Optical sensors for operando stress monitoring in lithium-based batteries containing solid-state or liquid electrolytes," Nature Communications, Nature, vol. 13(1), pages 1-14, December.
    3. Li, Qingmeng & Han, Ning & Chai, Jiali & Zhang, Wei & Du, Jiakai & Tian, Hao & Liu, Hao & Wang, Guoxiu & Tang, Bohejin, 2023. "Strategies to improve metal-organic frameworks and their derived oxides as lithium storage anode materials," Energy, Elsevier, vol. 282(C).
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    6. Gang Zhou & Peifang Wang & Bin Hu & Xinyue Shen & Chongchong Liu & Weixiang Tao & Peilin Huang & Lizhe Liu, 2022. "Spin-related symmetry breaking induced by half-disordered hybridization in BixEr2-xRu2O7 pyrochlores for acidic oxygen evolution," Nature Communications, Nature, vol. 13(1), pages 1-10, December.
    7. Kit McColl & Robert A. House & Gregory J. Rees & Alexander G. Squires & Samuel W. Coles & Peter G. Bruce & Benjamin J. Morgan & M. Saiful Islam, 2022. "Transition metal migration and O2 formation underpin voltage hysteresis in oxygen-redox disordered rocksalt cathodes," Nature Communications, Nature, vol. 13(1), pages 1-8, December.
    8. Sulay Saha & Prashant Kumar Gupta & Raj Ganesh S. Pala, 2021. "Stabilization of non‐native polymorphs for electrocatalysis and energy storage systems," Wiley Interdisciplinary Reviews: Energy and Environment, Wiley Blackwell, vol. 10(2), March.
    9. Shunsuke Sasaki & Souvik Giri & Simon J. Cassidy & Sunita Dey & Maria Batuk & Daphne Vandemeulebroucke & Giannantonio Cibin & Ronald I. Smith & Philip Holdship & Clare P. Grey & Joke Hadermann & Simon, 2023. "Anion redox as a means to derive layered manganese oxychalcogenides with exotic intergrowth structures," Nature Communications, Nature, vol. 14(1), pages 1-11, December.
    10. Zijian Cai & Bin Ouyang & Han-Ming Hau & Tina Chen & Raynald Giovine & Krishna Prasad Koirala & Linze Li & Huiwen Ji & Yang Ha & Yingzhi Sun & Jianping Huang & Yu Chen & Vincent Wu & Wanli Yang & Chon, 2024. "In situ formed partially disordered phases as earth-abundant Mn-rich cathode materials," Nature Energy, Nature, vol. 9(1), pages 27-36, January.
    11. Kai Wang & Zhenqi Gu & Zhiwei Xi & Lv Hu & Cheng Ma, 2023. "Li3TiCl6 as ionic conductive and compressible positive electrode active material for all-solid-state lithium-based batteries," Nature Communications, Nature, vol. 14(1), pages 1-10, December.
    12. Ho-Young Jang & Donggun Eum & Jiung Cho & Jun Lim & Yeji Lee & Jun-Hyuk Song & Hyeokjun Park & Byunghoon Kim & Do-Hoon Kim & Sung-Pyo Cho & Sugeun Jo & Jae Hoon Heo & Sunyoung Lee & Jongwoo Lim & Kisu, 2024. "Structurally robust lithium-rich layered oxides for high-energy and long-lasting cathodes," Nature Communications, Nature, vol. 15(1), pages 1-11, December.
    13. Xuelong Wang & Liang Yin & Arthur Ronne & Yiman Zhang & Zilin Hu & Sha Tan & Qinchao Wang & Bohang Song & Mengya Li & Xiaohui Rong & Saul Lapidus & Shize Yang & Enyuan Hu & Jue Liu, 2023. "Stabilizing lattice oxygen redox in layered sodium transition metal oxide through spin singlet state," Nature Communications, Nature, vol. 14(1), pages 1-13, December.
    14. Qi Liang & Peirong Li & Yue Zhao & Supeng Chen & Jixiang Yin & Yingchun Lyu & Qiang Li & Qinghao Li, 2023. "Investigation on the Origin of Sluggish Anionic Redox Kinetics in Cation-Disordered Cathode," Energies, MDPI, vol. 16(18), pages 1-12, September.
    15. Ziyao Gao & Chenglong Zhao & Kai Zhou & Junru Wu & Yao Tian & Xianming Deng & Lihan Zhang & Kui Lin & Feiyu Kang & Lele Peng & Marnix Wagemaker & Baohua Li, 2024. "Kirkendall effect-induced uniform stress distribution stabilizes nickel-rich layered oxide cathodes," Nature Communications, Nature, vol. 15(1), pages 1-11, December.
    16. Annika Ahlberg Tidblad & Kristina Edström & Guiomar Hernández & Iratxe de Meatza & Imanol Landa-Medrano & Jordi Jacas Biendicho & Lluís Trilla & Maarten Buysse & Marcos Ierides & Beatriz Perez Horno &, 2021. "Future Material Developments for Electric Vehicle Battery Cells Answering Growing Demands from an End-User Perspective," Energies, MDPI, vol. 14(14), pages 1-26, July.
    17. Fangqing Wang & Peichao Zou & Yangyang Zhang & Wenli Pan & Ying Li & Limin Liang & Cong Chen & Hui Liu & Shijian Zheng, 2023. "Activating lattice oxygen in high-entropy LDH for robust and durable water oxidation," Nature Communications, Nature, vol. 14(1), pages 1-11, December.
    18. Yi Pei & Qing Chen & Meiyu Wang & Pengjun Zhang & Qingyong Ren & Jingkai Qin & Penghao Xiao & Li Song & Yu Chen & Wen Yin & Xin Tong & Liang Zhen & Peng Wang & Cheng-Yan Xu, 2022. "A medium-entropy transition metal oxide cathode for high-capacity lithium metal batteries," Nature Communications, Nature, vol. 13(1), pages 1-13, December.
    19. Qingyuan Li & De Ning & Deniz Wong & Ke An & Yuxin Tang & Dong Zhou & Götz Schuck & Zhenhua Chen & Nian Zhang & Xiangfeng Liu, 2022. "Improving the oxygen redox reversibility of Li-rich battery cathode materials via Coulombic repulsive interactions strategy," Nature Communications, Nature, vol. 13(1), pages 1-13, December.

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