Review
Materials Science, Multidisciplinary
Muhammad Mominur Rahman, Feng Lin
Summary: Oxide electrodes in alkali-ion batteries involve redox reactions of both transition metal cations and oxygen ions, enabling increased capacity and energy density. However, challenges such as oxygen evolution, voltage hysteresis, and structural transformations still exist and require further investigation. Understanding and mitigating these challenges will be crucial for the development of next-generation batteries utilizing oxygen redox.
Article
Engineering, Environmental
Zhaoguo Liu, Shiyong Chu, Jianghua Wu, Chen Cheng, Liang Zhang, Shaohua Guo, Haoshen Zhou
Summary: This study successfully improves the reversible redox performance, structural stability, and sodium ion diffusion capability of cathode materials by introducing Ru substitution, leading to a significant advancement in the electrochemical performance of sodium-ion batteries.
CHEMICAL ENGINEERING JOURNAL
(2022)
Article
Chemistry, Multidisciplinary
Yangyang Lai, Huixian Xie, Peng Li, Biao Li, Along Zhao, Laibing Luo, Zewen Jiang, Yongjin Fang, Shengli Chen, Xinping Ai, Dingguo Xia, Yuliang Cao
Summary: This study investigates the activation mechanism of the anionic redox reaction (ARR) in cathode materials for Li/Na-ion batteries by designing Mg/Li/Zn-substituted NaxMnO2 and LixMnO2 cathode materials. Experimental results and theoretical calculations reveal that the activation of ARR is only observed in Li-substituted LixMnO2, while all Mg/Li/Zn-substituted NaxMnO2 cathode materials show ARR activities. The study proposes an ion-migration mechanism to explain the different ARR behaviors between NaxMnO2 and LixMnO2, providing insights for the development of high-capacity metal oxide cathode materials for LIBs/SIBs.
ADVANCED MATERIALS
(2022)
Article
Chemistry, Multidisciplinary
Xiayan Jian, Qiuyu Shen, Xudong Zhao, Junteng Jin, Yao Wang, Shengwei Li, Xuanhui Qu, Lifang Jiao, Yongchang Liu
Summary: This study reports a new type of ultrathin VOPO4 nanosheets as cathodes for sodium-ion batteries, achieving higher capacity and rate performance through redox reactions and ClO4- insertion/extraction. The mechanism of anionic redox reactions is elucidated, opening up a new avenue for high-energy phosphate cathodes for SIBs.
ADVANCED FUNCTIONAL MATERIALS
(2023)
Article
Chemistry, Physical
Natalia Voronina, Min-Young Shin, Hee-Jae Kim, Najma Yaqoob, Olivier Guillon, Seok Hyun Song, Hyungsub Kim, Hee-Dae Lim, Hun-Gi Jung, Younghak Kim, Han-Koo Lee, Kug-Seung Lee, Koji Yazawa, Kazuma Gotoh, Payam Kaghazchi, Seung-Taek Myung
Summary: Oxygen-redox-based cathode materials have potential as high-capacity and stable electrodes for sodium-ion batteries. By doping with Ni, the layered oxide cathode material Na-0.75[Li0.15Ni0.15Mn0.7]O-2 exhibits improved capacity and cycling stability.
ADVANCED ENERGY MATERIALS
(2022)
Article
Chemistry, Multidisciplinary
Chunliu Xu, Weibo Hua, Qinghua Zhang, Yuan Liu, Rongbin Dang, Ruijuan Xiao, Jin Wang, Zhao Chen, Feixiang Ding, Xiaodong Guo, Chao Yang, Liangrong Yang, Junmei Zhao, Yong-Sheng Hu
Summary: A Na superionic conductor Na3MnTi(PO4)(3) with desirable cycling stability and high safety is considered as a promising cathode for Na-ion batteries. However, the voltage hysteresis caused by Mn2+ ions has led to significant capacity loss. Through the sodium excess strategy, the voltage hysteresis can be suppressed, resulting in improved kinetic properties and increased reversible capacity. Based on these findings, a Na3.6Mn1.15Ti0.85(PO4)(3) cathode with high energy density was developed, surpassing most phosphate cathodes and demonstrating great potential for applications in Na-ion batteries.
ADVANCED FUNCTIONAL MATERIALS
(2023)
Article
Chemistry, Physical
Bertan Ozdogru, Hannah Dykes, Darrell Gregory, Damien Saurel, Vijayakumar Murugesan, Montse Casas-Cabanas, O. Ozgur Capraz
Summary: The mechanical response of sodium iron phosphate cathodes during cycling shows significant dependance on the applied scan rate, with asymmetrical strain generation at slower rates attributed to the formation of cathode-electrolyte interface layers. The combination of in situ strain measurements with a mathematical model provides new insight into the electrochemically induced mechanical deformations in Na-ion cathode electrodes, with factors such as capacity-dependent intercalation strains, rate-dependent mismatch strains, and time-dependent irreversible strains affecting the strain generation.
JOURNAL OF POWER SOURCES
(2021)
Article
Chemistry, Multidisciplinary
Yuqi Wu, Ke Zhou, Fucheng Ren, Yang Ha, Ziteng Liang, Xuefan Zheng, Zhenyu Wang, Wu Yang, Maojie Zhang, Mingzeng Luo, Corsin Battaglia, Wanli Yang, Lingyun Zhu, Zhengliang Gong, Yong Yang
Summary: This study reports a stable lithium-rich Li2RuO3 cathode in all-solid-state lithium batteries by forming a passivating solid electrolyte interphase, which efficiently suppresses side reactions and interfacial impedance. The Li2RuO3/sulfide electrolyte interface exhibits exceptional stability and allows for a high reversible capacity and prolonged cycling stability.
ENERGY & ENVIRONMENTAL SCIENCE
(2022)
Article
Multidisciplinary Sciences
Fang Fu, Xiang Liu, Xiaoguang Fu, Hongwei Chen, Ling Huang, Jingjing Fan, Jiabo Le, Qiuxiang Wang, Weihua Yang, Yang Ren, Khalil Amine, Shi-Gang Sun, Gui-Liang Xu
Summary: A strategy of stabilizing the structure and promoting anionic redox through configurational entropy and ion-diffusion structural tuning is reported for Mn-rich layered cathodes in Na-based batteries. The developed P2-type layered cathodes possess improved structural and thermal stability, faster anionic redox kinetics, and higher capacity retention.
NATURE COMMUNICATIONS
(2022)
Article
Chemistry, Multidisciplinary
Zhonghan Wu, Youxuan Ni, Sha Tan, Enyuan Hu, Lunhua He, Jiuding Liu, Machuan Hou, Peixin Jiao, Kai Zhang, Fangyi Cheng, Jun Chen
Summary: This article presents a new cathode material for sodium-ion batteries, Na0.7Li0.03[Mg0.15Li0.07Mn0.75]O2, which exhibits high specific capacity and low strain characteristic over a wide voltage range. The dual-site substitution of Li ions in transition-metal and alkali-metal positions enables a balance between capacity and stability.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Green & Sustainable Science & Technology
P. Vahdatkhah, O. Voznyy, S. K. Sadrnezhaad
Summary: The reversibility of anionic and cationic redox in Co-free concentration-gradient LLO was improved by integrating oxygen vacancies and high Ni/Mn ratio on LLO's surface, resulting in enhanced capacity of the cathode. This work provided a practical approach for resolving the capacity decay of Co-free LLOs by engineering the cathode/electrolyte interface and structure.
MATERIALS TODAY SUSTAINABILITY
(2023)
Review
Chemistry, Physical
Xueqian Ji, Qing Xia, Yuxing Xu, Hailan Feng, Pengfei Wang, Qiangqiang Tan
Summary: This review systematically summarizes the lithium storage mechanism of layered lithium-rich manganese-based materials, addressing the challenges of voltage and capacity decay. Various modifications in recent years, including component improvement, coating, doping, and surface treatment, are also discussed. Future research directions and challenges for the development of high performance Li-rich Mn-based materials are presented.
JOURNAL OF POWER SOURCES
(2021)
Review
Chemistry, Multidisciplinary
Mingzhe Chen, Yunfei Liu, Yanyan Zhang, Guichuan Xing, Yuxin Tang
Summary: The high capacity of lithium-rich oxides has led to investigations on both cationic and anionic redox processes. The focus has recently shifted towards anionic redox behavior as a new direction for achieving higher-energy cathodes for lithium-ion batteries. However, practical issues such as voltage decay and irreversible oxygen loss have motivated researchers to design novel lithium-rich sulfides/selenides. This perspective provides an in-depth discussion on the development of these materials, their lithium storage mechanism, and the potential for higher energy densities, as well as outlining the main challenges for their application in next-generation lithium-ion batteries.
CHEMICAL COMMUNICATIONS
(2022)
Article
Chemistry, Multidisciplinary
Yang Yu, Jicheng Zhang, Rui Gao, Deniz Wong, Ke An, Lirong Zheng, Nian Zhang, Christian Schulz, Xiangfeng Liu
Summary: In this study, Na/Mn anti-site defects were found to be the main factors triggering oxygen anion redox (OAR), and OAR activity and reversibility were enhanced by Ho doping. Ho doping increased the Na/Mn anti-site defects, allowing more O lone-pair electrons to participate in charge compensation. Moreover, Ho enlarged the O-O bond and O-TM-O angle, maintaining the single-electron oxygen hole configuration and inhibiting O-O shortening. Additionally, Ho induced the splitting of the TM 3d orbital energy band and generated low energy orbitals of Mn e(g)* and Ni e(g)*, promoting the transition of O lone-pair electrons and Ni e(g)* orbital electrons, and activating the redox activity of anions and cations. After regulation, the capacity increased from 146.8 to 184.9 mA h g(-1) and the capacity retention increased from 40.3 to 90.0%.
ENERGY & ENVIRONMENTAL SCIENCE
(2023)
Article
Materials Science, Multidisciplinary
Meichen Guo, Wu Tang, Yan Hong, Bangshuai Wei, Jiahui Hu, Fei Yu, Cong Fan
Summary: The researchers proposed the surface self-carbonization of organic electrodes to overcome the dissolution challenge faced by small-molecule organic cathodes in sodium-ion batteries (SIBs). They successfully formed a carbon layer on the surface of NTCDI-DAQ particles, eliminating dissolution without affecting the electrochemical properties. NTCDI-DAQ@C exhibited excellent discharge capacity and cycling stability, making it one of the best-performing small-molecule organic cathodes reported for SIBs.
SCIENCE CHINA-MATERIALS
(2023)
Article
Chemistry, Multidisciplinary
Robert A. House, Helen Y. Playford, Ronald Smith, Jennifer Holter, Ian Griffiths, Ke-Jin Zhou, Peter G. Bruce
Summary: By presenting neutron PDF data, it was demonstrated that the charged O-redox cathode material contains molecular O-2, which could potentially increase the energy density of Li-ion batteries.
ENERGY & ENVIRONMENTAL SCIENCE
(2022)
Article
Chemistry, Physical
Weixin Song, Miguel A. Perez-Osorio, John-Joseph Marie, Emanuela Liberti, Xiaonan Luo, Colum O'Leary, Robert A. House, Peter G. Bruce, Peter D. Nellist
Summary: Li-rich metal oxides undergo distinct oxygen redox processes in the bulk and surface during charge and discharge cycles, as observed through oxygen shift measurements. The recovery of oxygen shift after discharge is incomplete in the bulk but occurs close to the surface, accompanied by a phase change. The altered oxygen sublattice potentially explains the voltage profile changes in subsequent cycles.
Article
Chemistry, Multidisciplinary
Georgina L. Gregory, Hui Gao, Boyang Liu, Xiangwen Gao, Gregory J. Rees, Mauro Pasta, Peter G. Bruce, Charlotte K. Williams
Summary: Polymers with specific properties can help overcome challenges in all-solid-state batteries, resulting in improved capacity retention.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Public, Environmental & Occupational Health
Y. Alsaidi, A. Thompson, V Spilchuk, R. A. House, A. Adisesh
Summary: Hand arm vibration syndrome (HAVS) is caused by hand transmitted vibration. This study evaluated the prevalence and utility of testing for cryoglobulins and cold agglutinins in patients with HAVS symptoms. The results suggest that routine testing for cryoglobulins and cold agglutinins is not recommended due to negligible positivity rates.
OCCUPATIONAL MEDICINE-OXFORD
(2022)
Article
Multidisciplinary Sciences
Kit McColl, Robert A. House, Gregory J. Rees, Alexander G. Squires, Samuel W. Coles, Peter G. Bruce, Benjamin J. Morgan, M. Saiful Islam
Summary: Lithium-rich disordered rocksalt cathodes show high capacities due to redox chemistry on both transition-metal ions and oxygen ions, making them promising candidates for next-generation lithium-ion batteries. However, the atomic-scale mechanisms governing oxygen-ion redox in disordered structures are not fully understood. This study reveals that transition metal migration is necessary for the formation of molecular oxygen trapped in the bulk of disordered rocksalt Li2MnO2F. The presence of irreversible transition metal migration results in voltage hysteresis between charge and discharge, which should be suppressed to improve the performance of disordered rocksalt cathodes.
NATURE COMMUNICATIONS
(2022)
Article
Chemistry, Physical
Rory C. McNulty, Kieran D. Jones, Conrad Holc, Jack W. Jordan, Peter G. Bruce, Darren A. Walsh, Graham N. Newton, Hon Wai Lam, Lee R. Johnson
Summary: Understanding and eliminating degradation of the electrolyte solution is crucial in developing high energy density lithium-air batteries. The use of acetonitrile provides similar stability to current glyme ethers, but the mechanism for its degradation is unknown. By studying the degradation of acetonitrile in the lithium-air battery, a correlation between H2O concentration and deviation from the ideal electron/oxygen ratio is revealed. Acetamide is identified as the major degradation product, and a new degradation pathway involving lithium hydroperoxide is proposed.
ADVANCED ENERGY MATERIALS
(2023)
Article
Energy & Fuels
Robert A. House, Gregory J. Rees, Kit McColl, John-Joseph Marie, Mirian Garcia-Fernandez, Abhishek Nag, Ke-Jin Zhou, Simon Cassidy, Benjamin J. Morgan, M. Saiful Islam, Peter G. Bruce
Summary: Oxide ions in transition metal oxide cathodes can store charge at high voltage. However, during charging, the oxidized oxide ions form trapped O-2, resulting in undesirable voltage hysteresis. By studying ribbon-ordered Na-0.6[Li0.2Mn0.8]O-2, the authors discovered the delocalized electron holes on oxide ions before O-2 formation. The understanding of these hole states is crucial for realizing reversible high-voltage O-redox cathodes.
Article
Chemistry, Physical
Dominic Spencer-Jolly, Varnika Agarwal, Christopher Doerrer, Bingkun Hu, Shengming Zhang, Dominic L. R. Melvin, Hui Gao, Xiangwen Gao, Paul Adamson, Oxana Magdysyuk, Patrick S. Grant, Robert A. House, Peter G. Bruce
Summary: Ag-carbon composite interlayers have been proven effective in enabling Li-free cycling of solid-state batteries. Li intercalates electrochemically into graphite on charge, subsequently reacting chemically with Ag to form Li-Ag alloys. Discharge does not reverse this process, instead passing through Li-deficient Li-Ag phases. At higher charging rates, Li intercalation outpaces chemical reactions with Ag, resulting in delayed Li-Ag phase formation and increased Li metal deposition at the current collector. Li dendrites are not suppressed at and above 2.5 mA•cm-2, and Ag nanoparticles are not more effective than a graphite interlayer. Instead, Ag in the carbon interlayer promotes more uniform Li and Li-Ag formation during charge.
Article
Chemistry, Physical
Yasaman Shirazi Moghadam, Yang Hu, Abdel El Kharbachi, Stephanie Belin, Thomas Diemant, Jun Chen, Robert A. House, Peter G. Bruce, Maximilian Fichtner
Summary: In this work, synchrotron operando X-ray absorption spectroscopy (XAS) was used to study the chemical and structural evolution of Mn and Ti in Li-rich disordered rocksalt (DRS) cathode compounds for Li-ion batteries. The results provide insights into the development of Mn double-redox reactions in the DRS cathodes from initial cycles to prolonged cycling and elucidate the impacts of the reduced Mn redox activity and the increased local ordering on the cycling stability.
CHEMISTRY OF MATERIALS
(2023)
Article
Chemistry, Physical
Hyun-Wook Lee, Ja-Yeong Kim, Joo-Eun Kim, Yun-Joo Jo, Daniel Dewar, Sixie Yang, Xiangwen Gao, Peter G. Bruce, Won-Jin Kwak
Summary: The use of redox mediators (RMs) to decompose Li2O2 is an effective method to improve the efficiency and cyclability of lithium-oxygen batteries. However, the reactivity of different RMs with singlet oxygen (O-1(2)) and its impact on the electrochemical behavior of RMs have not been investigated. This study categorizes the reactivity of RMs with O-1(2) and examines its effects on the Li2O2 decomposition kinetics of RMs.
JOURNAL OF MATERIALS CHEMISTRY A
(2023)
Article
Chemistry, Physical
Max Jenkins, Daniel Dewar, Tammy Nimmo, Chloe Chau, Xiangwen Gao, Peter G. Bruce
Summary: One of the important challenges in long cycle life Li-O-2 batteries is the degradation of solvents, even stable ethers like CH3O(CH2CH2O)CH3 decompose to form Li2CO3. The accumulation of Li2CO3 in the pores of gas diffusion electrode during cycling leads to polarization and capacity fading. This work investigates the build-up and distribution of Li2CO3 in the porous gas diffusion electrode during cycling and its connection to cell failure. The study also demonstrates that the removal of Li2CO3 by a redox mediator can partially restore cell performance and extend the cycle life of Li-O(2) battery.
FARADAY DISCUSSIONS
(2023)
