Article
Chemistry, Multidisciplinary
Hiroaki Kobayashi, Yu Fukumi, Hiroto Watanabe, Reona Iimura, Naomi Nishimura, Toshihiko Mandai, Yoichi Tominaga, Masanobu Nakayama, Tetsu Ichitsubo, Itaru Honma, Hiroaki Imai
Summary: Ultraporous and ultrasmall cubic spinel MgMn2O4 (MMO) is fabricated through a freeze-dry assisted room-temperature alcohol reduction process. Heat-treatment removes surface hydroxy groups and activates MMO, increasing its discharge capacity from 160 mAh g(-1) to 270 mAh g(-1), close to the theoretical value. The ultraporous, ultrasmall particles stabilize the metastable cubic spinel phase, promoting Mg2+ insertion/deintercalation and reversible transformation between cubic spinel and cubic rock-salt phases.
Article
Nanoscience & Nanotechnology
Hiroaki Kobayashi, Kouta Samukawa, Masanobu Nakayama, Toshihiko Mandai, Itaru Honma
Summary: The developed cubic MgMn2O4 spinel nanoparticles exhibit superior reversible capacity compared to tetragonal MgMn2O4 at room temperature, providing a promising cathode material for magnesium rechargeable batteries.
ACS APPLIED NANO MATERIALS
(2021)
Article
Chemistry, Multidisciplinary
Naoto Kitamura, Tomoya Imura, Naoya Ishida, Chiaki Ishibashi, Yasushi Idemoto
Summary: In this study, the cycle performance and coulombic efficiency of MgMn2O4 were significantly improved by surface modification with Zr. The Zr modification suppressed unexpected reactions and reduced structural distortion, demonstrating the significant potential of surface modification as a method for obtaining high-performance MRBs.
Article
Chemistry, Multidisciplinary
Kohei Shimokawa, Taruto Atsumi, Norihiko L. Okamoto, Tomoya Kawaguchi, Susumu Imashuku, Kazuaki Wagatsuma, Masanobu Nakayama, Kiyoshi Kanamura, Tetsu Ichitsubo
Summary: This study demonstrates a design concept for high-performance cathode materials by selecting an element to destabilize the rocksalt-type structure and utilizing the defect-spinel-type structure, leading to excellent cycle performance of magnesium rechargeable batteries.
ADVANCED MATERIALS
(2021)
Article
Chemistry, Physical
X. Zhang, D. Li, Q. Ruan, L. Liu, B. Wang, F. Xiong, C. Huang, P. K. Chu
Summary: This paper provides a comprehensive overview of vanadium-based cathode materials for rechargeable magnesium batteries (RMBs), including vanadium oxides, vanadates, vanadium chalcogenides, and vanadium-based phosphates. The structure, electrochemical properties, optimization strategies, structure-performance relationship, and reaction mechanisms of various vanadium-based cathode materials are described. The challenges, prospective, and future research directions of vanadium-based electrode materials are discussed.
MATERIALS TODAY ENERGY
(2023)
Review
Chemistry, Physical
Fanfan Liu, Tiantian Wang, Xiaobin Liu, Li-Zhen Fan
Summary: This review summarizes the recent progress in the development of key materials for RMBs, including cathodes, anodes, and electrolytes. It discusses the potential applications and challenges of various materials in Mg batteries.
ADVANCED ENERGY MATERIALS
(2021)
Article
Chemistry, Physical
Carmen Miralles, Teresa Lana-Villarreal, Roberto Gomez
Summary: Rechargeable magnesium batteries offer higher safety and lower cost compared to lithium batteries, and spinel-type materials like MgMn2O4 show promise as positive electrode candidates. This study synthesized MgMn2O4 with a tetragonal structure using a simple and low-cost method, and tested its performance in aqueous media. The results reveal that the charge/discharge process in aqueous media involves the co-intercalation of Mg2+ and water molecules. The study also demonstrates that doping with nickel can improve the capacity retention and cycling performance of MgMn2O4.
Article
Chemistry, Physical
Zhaohui Yang, Fei Wang, Pengyu Meng, Jiayan Luo, Chaopeng Fu
Summary: Rechargeable aluminum-ion batteries with organic positive electrode materials have attracted attention due to their advantages of design flexibility and sustainable energy storage chemistry. However, challenges including high solubility, low active center utilization, and low electrical conductivity need to be addressed. This review summarizes recent advances in the development of organic positive electrodes for Al-ion batteries, and discusses strategies to improve their performance. Challenges and future research directions towards high-performance Al/organic batteries are also discussed.
ENERGY STORAGE MATERIALS
(2022)
Review
Materials Science, Multidisciplinary
Xiaomin Han, Ying Bai, Ran Zhao, Yu Li, Feng Wu, Chuan Wu
Summary: This review provides a comprehensive overview of the development and properties of electrolytes in rechargeable aluminum batteries (RABs). Various types of electrolytes, including ionic liquids, high temperature salts, organic electrolytes, aqueous electrolytes, and polymer electrolytes, are discussed. The focus is on the properties and compositions of ionic liquid electrolytes, which are the most commonly used electrolytes in RABs, as well as the electrode/electrolyte interfaces in different electrolyte environments. This review aims to guide the selection of appropriate electrolytes and clarify the energy storage mechanism of RABs.
PROGRESS IN MATERIALS SCIENCE
(2022)
Article
Chemistry, Multidisciplinary
Ebrahim Abouzari-Lotf, Raheleh Azmi, Zhenyou Li, Shirin Shakouri, Zhi Chen, Zhirong Zhao-Karger, Svetlana Klyatskaya, Julia Maibach, Mario Ruben, Maximilian Fichtner
Summary: In this study, a copper-porphyrin with meso-functionalized ethynyl groups demonstrated reversible two- and four-electron storage at a fast rate. The cathode showed specific discharge capacity of 155 mAh g(-1) at high current density and maintained >70 mAh g(-1) even at 4000 mA g(-1) after 500 cycles, indicating potential for practical cathodes in multivalent metal batteries.
Article
Chemistry, Multidisciplinary
Seokhun Kim, Vaiyapuri Soundharrajan, Sungjin Kim, Balaji Sambandam, Vinod Mathew, Jang-Yeon Hwang, Jaekook Kim
Summary: NHVO, a unique structured layered oxide electrode material synthesized by a microwave method, exhibits remarkable electrochemical reversibility and high specific capacity, making it suitable for high energy ARZIB cathodes and offering new opportunities for developing high energy ARZIB electrodes.
Review
Chemistry, Physical
Yan Lu, Cong Wang, Qiang Liu, Xiaoyan Li, Xinyu Zhao, Zaiping Guo
Summary: This review focuses on electrolyte design for reliable Mg-S batteries, covering efficient salt construction, suitable solvent selection, and strategies for combating corrosivity of Mg electrolytes. It not only provides an understanding of the electrochemistry, but also explores potential strategies for high-performance sulfur-based cathodes and magnesium anodes, offering a comprehensive insight into Mg-S systems. Perspectives on possible research directions for constructing high-performance practical Mg-S batteries are also shared.
Review
Chemistry, Physical
Kok Long Ng, Brohath Amrithraj, Gisele Azimi
Summary: This review focuses on summarizing reported cathode materials and their charge storage mechanisms in nonaqueous rechargeable Al batteries (RABs). It critically discusses the implications of overall cell chemistries on actual battery performance metrics, outlines the fundamental and practical limitations of existing RAB chemistries, and emphasizes the importance of accurately elucidating the underlying charge storage mechanism. The ion migration kinetics in existing electrodes are discussed, and design guidelines for enhancing their performance are provided.
Review
Chemistry, Multidisciplinary
Jinlei Zhang, Zeyu Chang, Zhonghua Zhang, Aobing Du, Shanmu Dong, Zhenjiang Li, Guicun Li, Guanglei Cui
Summary: This review explores various material design strategies to enhance the performance of rechargeable Mg-based batteries, with a focus on both cathode and anode materials. It comprehensively examines different concepts and summarizes the advances towards Mg-S and Mg-Se batteries. Analyzing the pros and cons of these strategies provides valuable insights for future research in Mg-based batteries and other multivalent-ion battery chemistries.
Review
Energy & Fuels
Meiyu Shi, Tianlin Li, Han Shang, Dewen Zhang, Huayan Qi, Tianlong Huang, Zelin Xie, Jiqiu Qi, Fuxiang Wei, Qingkun Meng, Bin Xiao, Qing Yin, Yongzhi Li, Danyang Zhao, Xiaolan Xue, Yanwei Sui
Summary: Rechargeable magnesium ion batteries (RMIBs) have attracted attention due to their abundant resources, low cost, environmental friendliness, and high volumetric capacities. The interaction between highly polarized Mg2+ ions and cathode materials hinders the diffusion kinetics, therefore, the design and synthesis of high-performance cathode materials is crucial for RMIBs development. In this review, we extensively overview different types of inorganic cathodes for RMIBs, emphasizing on their structural characteristics, charge storage mechanisms, electrochemical properties, and optimization strategies. This comprehensive review aims to present important research works, challenges, and future directions for inorganic cathodes in RMIBs, encouraging further research efforts in this field.
JOURNAL OF ENERGY STORAGE
(2023)
Article
Chemistry, Multidisciplinary
Yuichi Okazaki, Seiji Oda, Akihiko Takamatsu, Shogo Kawaguchi, Hirofumi Tsukasaki, Shigeo Mori, Shunsuke Yagi, Hidekazu Ikeno, Ikuya Yamada
Summary: The rational design of highly active catalysts for the oxygen evolution reaction (OER) is important for energy-conversion applications. Postspinel-structured oxides, CaB2O4, exhibit higher OER activities due to their lower charge-transfer resistances. A density-functional-theory calculation suggests a novel mechanism of lattice oxygen pairing with adsorbed oxygen, which results in the lowest theoretical OER overpotential.
Article
Chemistry, Physical
Ikuya Yamada, Fumito Toda, Shogo Kawaguchi, Shunsuke Yagi
Summary: This study investigates the physical and electrochemical properties of BaFe12-xCoxO19 solid solution and its catalytic activity in the oxygen evolution reaction (OER). Co and Fe doping into BaFe12O19 and BaCo12O19 increases the OER activity, with maximum activity observed at x = 5 and 10 compositions. The nonsystematic change in activity for intermediate compositions suggests a competition of factors affecting OER activity.
ACS APPLIED ENERGY MATERIALS
(2022)
Article
Materials Science, Ceramics
Hayato Takemitsu, Yoshihiro Hayashi, Hiroto Watanabe, Toshihiko Mandai, Shunsuke Yagi, Yuya Oaki, Hiroaki Imai
Summary: This study prepared conductive mixtures as positive electrode active materials in rechargeable Mg batteries. High specific surface area and high conductivity are key parameters for practical room-temperature operation.
JOURNAL OF SOL-GEL SCIENCE AND TECHNOLOGY
(2022)
Article
Nanoscience & Nanotechnology
Xiatong Ye, Hongyi Li, Takuya Hatakeyama, Hiroaki Kobayashi, Toshihiko Mandai, Norihiko L. Okamoto, Tetsu Ichitsubo
Summary: Rechargeable magnesium batteries are promising candidates for future batteries due to their abundant resources and high energy density. This study compares the reaction behavior of different MnO2 cathodes in two electrolytes and highlights the importance of interfacial stability for practical applications.
ACS APPLIED MATERIALS & INTERFACES
(2022)
Article
Chemistry, Multidisciplinary
Hiroaki Kobayashi, Yu Fukumi, Hiroto Watanabe, Reona Iimura, Naomi Nishimura, Toshihiko Mandai, Yoichi Tominaga, Masanobu Nakayama, Tetsu Ichitsubo, Itaru Honma, Hiroaki Imai
Summary: Ultraporous and ultrasmall cubic spinel MgMn2O4 (MMO) is fabricated through a freeze-dry assisted room-temperature alcohol reduction process. Heat-treatment removes surface hydroxy groups and activates MMO, increasing its discharge capacity from 160 mAh g(-1) to 270 mAh g(-1), close to the theoretical value. The ultraporous, ultrasmall particles stabilize the metastable cubic spinel phase, promoting Mg2+ insertion/deintercalation and reversible transformation between cubic spinel and cubic rock-salt phases.
Article
Chemistry, Analytical
Yasushi Idemoto, Mina Takamatsu, Chiaki Ishibashi, Naoya Ishida, Toshihiko Mandai, Naoto Kitamura
Summary: Mg1.33V1.67-xMnxO4 (x= 0.1 to 0.4) was synthesized for the first time using a solid-phase method under high vacuum conditions. The crystal structures were confirmed to be spinel with Fd3(-)m space group through powder X-ray diffraction analysis, and the chemical compositions were found to be uniform through STEM observation and elemental analysis. Charge and discharge cycle tests revealed that the discharge capacity depended on the cycle number, Mn composition, and working temperature. Among them, Mg1.33V1.57Mn0.1O4 (x=0.1) exhibited the highest discharge capacity of 256 mAh g(-1) at the 13th cycle, while the initial capacity was only 73 mAh g(-1) at 90 degrees C. The local structure was analyzed using EXAFS spectra, which showed that Mg1.33V1.57Mn0.1O4 had the smallest lattice distortion due to Mn at 16d sites, and XAFS spectra indicated a significant change in the oxidation state of V during the charge/discharge cycles. The particularly stable crystal structure and large contribution of charge compensation by V may contribute to the excellent charge-discharge performance of Mg1.33V1.57Mn0.1O4.
JOURNAL OF ELECTROANALYTICAL CHEMISTRY
(2023)
Article
Chemistry, Physical
Toshihiko Mandai, Hiroko Naya, Hyuma Masu
Summary: The electrolyte material for high-energy-density rechargeable batteries should have sufficient stability against metallic negative electrodes. Weakly coordinating anion (WCA)-based electrolytes have shown excellent performance due to their strong interaction with metal cations. In this study, the valency of paired cation species was found to affect the transport properties and electrochemical characteristics of the electrolytes, with divalent electrolytes exhibiting higher conductivity than monovalent electrolytes. The combination of magnesium cations and [B(HFIP)4]- anion showed outstanding performance in ethereal solutions.
JOURNAL OF PHYSICAL CHEMISTRY C
(2023)
Article
Chemistry, Physical
Toshihiko Mandai, Masaru Yao, Keitaro Sodeyama, Akiko Kagatsume, Yoshitaka Tateyama, Hiroaki Imai
Summary: Rechargeable magnesium batteries (RMBs) have the potential to be a sustainable energy storage technology due to the abundance of magnesium metal and its excellent energy storage properties. However, to compete with lithium-ion batteries, their energy density needs to be improved. This study explores the use of different organic solvent-based electrolytes to design anodically stable ether-based electrolyte solutions for RMB applications. Anodically stable electrolytes were successfully developed by combining suitable fluorinated glyme-based solvents with appropriate conducting salts, achieving a remarkable anodic limit and suppressing corrosion of current collectors. However, these electrolytes were not suitable for RMBs with high-voltage oxide-based cathodes due to catalytic decomposition during charging.
JOURNAL OF PHYSICAL CHEMISTRY C
(2023)
Article
Chemistry, Physical
Naomi Nishimura, Kazumasa Masaki, Wei Tan, Reona Iimura, Hiroaki Kobayashi, Kei Nishikawa, Toshihiko Mandai, Hidetoshi Somekawa, Yoichi Tominaga
Summary: To improve the cycle performance of Mg metal batteries, a polymer coating (PSTFSI-Mg) was applied on the surface of spinel-type MgMn2O4 cathode. The polymer coating promoted electron transfer between particles, as confirmed by transmission electron microscopy. Density functional theory calculations revealed that the polymer reduced the energy gap between the valence band maximum of MgMn2O4 and the highest occupied molecular orbital level of the electrolyte, thus suppressing electrolyte degradation.
JOURNAL OF PHYSICAL CHEMISTRY C
(2023)
Article
Energy & Fuels
Chao Zhang, Jun Cheng, Yiming Chen, Maria K. Y. Chan, Qiong Cai, Rodrigo P. Carvalho, Cleber F. N. Marchiori, Daniel Brandell, C. Moyses Araujo, Ming Chen, Xiangyu Ji, Guang Feng, Kateryna Goloviznina, Alessandra Serva, Mathieu Salanne, Toshihiko Mandai, Tomooki Hosaka, Mirna Alhanash, Patrik Johansson, Yun-Ze Qiu, Hai Xiao, Michael Eikerling, Ryosuke Jinnouchi, Marko M. Melander, Georg Kastlunger, Assil Bouzid, Alfredo Pasquarello, Seung-Jae Shin, Minho M. Kim, Hyungjun Kim, Kathleen Schwarz, Ravishankar Sundararaman
Summary: New materials for electrochemical energy storage and conversion play a crucial role in the electrification and sustainable development of modern societies. Molecular modelling, based on the principles of quantum mechanics and statistical mechanics and empowered by machine learning techniques, allows us to understand, control, and design electrochemical energy materials with atomic precision.
JOURNAL OF PHYSICS-ENERGY
(2023)
Article
Chemistry, Physical
Takahiro Okuo, Toshihiko Mandai, Hiroyasu Masunaga, Noboru Ohta, Hidetoshi Matsumoto
Summary: In this study, magnesiated perfluorosulfonated ionomer (Nafion-Mg) gel electrolytes swollen in magnesium bis(trifluoromethanesulfonyl)amide/triglyme (Mg(TFSA)(2)/G3) solutions were prepared and characterized. The swollen Nafion gel electrolytes exhibited good ionic conductivity and reversible Mg deposition/dissolution behavior. This is the first study on the structural and electrochemical characterization of magnesium ion-exchanged Nafion swollen in a Mg(TFSA)(2)/glyme solution.
JOURNAL OF PHYSICAL CHEMISTRY C
(2023)
Article
Chemistry, Physical
Toshihiko Mandai, Mariko Watanabe
Summary: The compatibility of rechargeable magnesium batteries with atmospheric conditions (except moisture) has not been thoroughly studied. In this study, we investigated the impact of atmospheric conditions on the electrochemical dissolution-deposition behavior of magnesium in non-aqueous electrolytes. Oxygen, even in trace amounts in the electrolyte, was found to be a detrimental impurity for reversible magnesium electrochemistry.
JOURNAL OF MATERIALS CHEMISTRY A
(2023)
Article
Chemistry, Multidisciplinary
Shigeto Hirai, Shunsuke Yagi, He-Chan Oh, Yoshiki Sato, Wei Liu, En-Pei Liu, Wei-Tin Chen, Akira Miura, Masanori Nagao, Tomoya Ohno, Takeshi Matsuda
Summary: This study successfully developed an OER catalyst with high intrinsic activity and stability under acidic conditions by preventing lattice collapse after repeated OER cycling. The substitution of Ir-sites with Mn in BaIrO3 and OER cycling led to a remarkable activity enhancement by a factor of 28 and an overall improvement in stability.
Article
Chemistry, Multidisciplinary
Wencong Wang, Wei Liu, Masao Kamiko, Shunsuke Yagi
Summary: This study investigates the oxygen reduction reaction (ORR) catalytic activity of an "oxygen-excess" perovskite catalyst La1-xSrxMnO3+delta and finds that it has higher activity and stability compared to a regular perovskite. Sr substitution can affect the formation of Mn4+ ions and modulate cation vacancies, thus changing the length of the Mn-O bond.
NEW JOURNAL OF CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Wei Liu, Masao Kamiko, Ikuya Yamada, Shunsuke Yagi
Summary: This paper presents an electrochemical deposition method to obtain cobalt oxides with controllable crystallinity on carbon paper. The study investigates the influence of the crystallinity of cobalt oxides on the activity of the oxygen evolution reaction (OER). The results show that cobalt oxides in an amorphous state exhibited higher catalytic activity and better stability compared to those in a crystalline state.
