Review
Chemistry, Multidisciplinary
Xu Liu, Alessandro Mariani, Henry Adenusi, Stefano Passerini
Summary: Non-flammable ionic liquid electrolytes (ILEs) are potential candidates for safer and longer-lasting lithium metal batteries (LMBs), but their high viscosity and inadequate Li+ transport restrict their practical use. Recently, diluting ILEs with non-solvating and low-viscosity co-solvents has been employed to overcome these challenges. The resulting locally concentrated ionic liquid electrolytes (LCILEs) exhibit lower viscosity, faster Li+ transport, and improved compatibility with lithium metal anodes, making them promising options for next-generation high-energy-density LMBs. This article provides a summary of the progress made in the development of LCILEs, including their physicochemical properties, solution structures, and applications in LMBs with various high-energy cathode materials. Furthermore, future research directions for LCILEs are outlined to enhance our understanding and achieve better cell performance.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Physical
Thuy Duong Pham, Abdullah Bin Faheem, So Yeon Chun, Jung-Rae Rho, Kyungwon Kwak, Kyung-Koo Lee
Summary: This study shows the potential for enhancing the performance of lithium metal batteries (LMBs) by modulating the ion solvation structures in the electrolyte through mixing different salts. A highly promising electrolyte system with improved conductivity, Coulombic efficiency, and stability of solid-electrolyte interface layer is proposed, offering a new avenue towards commercial LMBs.
ADVANCED ENERGY MATERIALS
(2021)
Article
Chemistry, Multidisciplinary
Xu Liu, Alessandro Mariani, Thomas Diemant, Xu Dong, Po-Hua Su, Stefano Passerini
Summary: A new electrolyte for low-temperature lithium metal batteries is proposed, which shows good performance in sub-zero conditions. By using this electrolyte, dendrite-free operation of lithium metal anodes at -20℃ and 0.5 mA cm(-2) with a Coulombic efficiency of 98.9% is achieved.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Review
Chemistry, Physical
Xiao Tang, Shuyao Lv, Kun Jiang, Guohui Zhou, Xiaomin Liu
Summary: Ionic liquid-based electrolytes have been developed in lithium-ion batteries to enhance safety and performance. This review summarizes the recent progress in the physiochemical properties, interphase formation ability, and electrochemical performance of ionic liquids and ionic liquid-based electrolytes. The applications of different types of ionic liquid-based electrolytes are discussed in detail. The challenges and perspectives for further development of ionic liquid-based electrolytes in lithium-ion batteries are also presented.
JOURNAL OF POWER SOURCES
(2022)
Article
Chemistry, Multidisciplinary
Xu Liu, Thomas Diemant, Alessandro Mariani, Xu Dong, Maria Enrica Di Pietro, Andrea Mele, Stefano Passerini
Summary: This article proposes a new low-flammability locally concentrated ionic liquid electrolyte (LCILE) for Li/sulfurized polyacrylonitrile (SPAN) batteries. The LCILE forms stable electrolyte/electrode interfaces on both the lithium-metal anodes (LMAs) and SPAN cathodes, leading to improved battery performance and cycling stability.
ADVANCED MATERIALS
(2022)
Article
Chemistry, Multidisciplinary
Xu Liu, Alessandro Mariani, Thomas Diemant, Maria Enrica Di Pietro, Xu Dong, Andrea Mele, Stefano Passerini
Summary: Trifluoromethoxybenzene as a cosolvent in locally concentrated ionic liquid electrolytes (LCILEs) can enhance the protective electrode/electrolyte interphases (EEIs) in lithium metal batteries, leading to stable cycling of the batteries.
ADVANCED MATERIALS
(2023)
Article
Chemistry, Physical
Xu Liu, Alessandro Mariani, Maider Zarrabeitia, Maria Enrica Di Pietro, Xu Dong, Giuseppe Antonio Elia, Andrea Mele, Stefano Passerini
Summary: Organic cations significantly influence the electrochemical performance of lithium metal batteries by affecting the coordination of FSI- and the formation of solid-electrolyte interphase (SEI). Two different LCILEs with organic cations Pyr(14)(+) and Emim(+) show differences in viscosity, Li+ transport rate, and lithium plating/stripping efficiency, resulting in improved capacity and retention in Li/EmiBE/LiNi0.8Mn0.1Co0.1O2 cells compared to PyrBE-based cells.
ENERGY STORAGE MATERIALS
(2022)
Article
Multidisciplinary Sciences
Guorui Cai, John Holoubek, Mingqian Li, Hongpeng Gao, Yijie Yin, Sicen Yu, Haodong Liu, Tod A. Pascal, Ping Liu, Zheng Chen
Summary: This study demonstrates an electrolyte system using monodentate dibutyl ether as the solvent, which achieves the characteristics of avoiding dendrite growth and achieving high Coulombic efficiency at various temperatures. This research provides solvent-based design criteria for Li-sulfur pouch cells in a wide temperature range.
PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA
(2022)
Article
Chemistry, Multidisciplinary
Mingsheng Qin, Ziqi Zeng, Xiaowei Liu, Yuanke Wu, Renjie He, Wei Zhong, Shijie Cheng, Jia Xie
Summary: This study successfully ameliorates graphite exfoliation-induced cell failure in propylene carbonate-based electrolyte by utilizing trifluoromethylbenzene as both electrolyte and surfactant, and constructing stable anion-induced solid electrolyte interphase at low concentration of lithium salt.
Article
Polymer Science
Jihae Han, Mayu Osugi, Namie Ikeda, Kenta Fujii
Summary: In this study, a lithium salt-concentrated organogel was prepared via one-step gelation. The organogel exhibited efficient polymer network formation and good electrochemical properties, making it a promising quasi-solid electrolyte material for lithium-ion capacitors.
Article
Chemistry, Physical
Gregorio Guzman-Gonzalez, Marta Alvarez-Tirado, Jorge L. Olmedo-Martinez, Matias L. Picchio, Nerea Casado, Maria Forsyth, David Mecerreyes
Summary: This article demonstrates the use of single-component electrolytes in lithium batteries based on new lithium borate ionic liquids at room temperature. The optimized lithium ionic liquids (LiILs) show high ionic conductivity, lithium transference numbers, and electrochemical stability. These LiILs also exhibit high compatibility with lithium-metal electrodes, resulting in excellent electrochemical performance in lithium-metal battery cells.
ADVANCED ENERGY MATERIALS
(2023)
Article
Engineering, Environmental
Jifang Fu, Yufeng Xu, Linna Dong, Liya Chen, Qi Lu, Mengmeng Li, Xingfa Zeng, Sanwei Dai, Guorong Chen, Liyi Shi
Summary: The study synthesized a series of multiclaw-shaped octasilsesquioxanes functionalized ionic liquids for developing novel hybrid solid polymer electrolytes with high ionic conductivity. These electrolytes exhibit high electrochemical stability and ionic conductivity, showing promising cycling performance and rate capability in Li/LiFePO 4 cells.
CHEMICAL ENGINEERING JOURNAL
(2021)
Article
Nanoscience & Nanotechnology
Saki Sawayama, Asuka Morinaga, Hideyuki Mimura, Masayuki Morita, Yu Katayama, Kenta Fujii
Summary: This study proposes a molecular design for safer lithium-ion batteries in nonflammable concentrated electrolytes. By introducing a small molecular additive, acetonitrile, into TFEP-based electrolytes, the battery electrode reaction is improved with reversible charge/discharge behavior observed. Visualizing lithium-ion complexes at the molecular level, it is revealed that the addition of acetonitrile triggers a change in Li-ion structures, leading to the formation of specific Li-ion-ordered structures linked via FSA anions.
ACS APPLIED MATERIALS & INTERFACES
(2021)
Review
Chemistry, Multidisciplinary
Peng Fan, Hao Liu, Vladimir Marosz, Nia T. Samuels, Steven L. Suib, Luyi Sun, Libing Liao
Summary: There is an urgent demand for developing all solid-state lithium-ion batteries with high energy density and safety. The core technology in solid-state batteries is the solid-state electrolyte, and composite polymer electrolytes are considered as one of the most promising candidates due to their comprehensive performance. Recent representative CPEs with synthetic fillers and natural clay-based fillers show great potential for high-performance LIBs.
ADVANCED FUNCTIONAL MATERIALS
(2021)
Article
Chemistry, Multidisciplinary
Zhenyu Guo, Gang Cheng, Zhen Xu, Fei Xie, Yong-Sheng Hu, Cecilia Mattevi, Maria-Magdalena Titirici, Maria Crespo Ribadeneyra
Summary: Na-based dual-ion batteries (DIBs) are a post-lithium technology with advantages of fast charging, cost-effectiveness, and abundant raw materials. The performance of a Na-DIB in different electrolyte systems was studied, and a highly concentrated and fluorine-rich carbonate-based formulation was optimized to achieve better performance compared to literature.
Article
Chemistry, Physical
Saki Sawayama, Riko Ochi, Tsubasa Kawaguchi, Yu Katayama, Masayuki Morita, Kenta Fujii
Summary: We present highly concentrated electrolytes prepared with a fluorinated acetate solvent, which allows for a favorable electrode reaction in Li-ion batteries. The electrolyte consisting of 2,2,2-trifluoroethyl acetate (TFEAc) solvent and 3.2 mol dm(-3) LiFSA salt demonstrated improved charge-discharge behavior on the graphite negative electrode compared to an analogous electrolyte. The lower activation energy (E-a) of the graphite electrode reaction in the concentrated LiFSA/TFEAc electrolyte contributes to its kinetically unique behavior.
ACS APPLIED ENERGY MATERIALS
(2023)
Article
Chemistry, Physical
Zhuanfang Jing, Yongquan Zhou, Toshio Yamaguchi, Koji Ohara, Jianming Pan, Guangguo Wang, Fayan Zhu, Hongyan Liu
Summary: This study provides insights into the structure and recognition sequence of alkali metal ions (Li+, Na+, K+, Rb+, and Cs+) by 18-crown-6 in aqueous solutions. It is found that Li+, Na+, and K+ are located inside the crown ether, while Rb+ and Cs+ are located outside. The recognition sequence of alkali metal ions by 18-crown-6 in water is different from that in the gas phase, indicating the significant influence of the solvation medium on cation recognition.
JOURNAL OF PHYSICAL CHEMISTRY B
(2023)
Article
Chemistry, Physical
Kazutaka Ikeda, Takuya Kimura, Koji Ohara, Toyoto Sato, Hidetoshi Ohshita, Atsushi Sakuda, Akitoshi Hayashi
Summary: Sodium solid electrolytes are considered preferable to lithium solid electrolytes for all-solid-state lithium-ion batteries. The heat treatment of Na3PS4 glass ceramics can greatly enhance the ionic conductivity, with vacancies in the ceramic material playing a crucial role in promoting Na ion conduction. The control of vacancies in solid electrolytes is essential for the design of practical all-solid-state sodium batteries.
JOURNAL OF PHYSICAL CHEMISTRY C
(2023)
Article
Chemistry, Physical
Satoshi Hiroi, Futoshi Utsuno, Hiroyuki Higuchi, Atsutaka Kato, Mari Yamamoto, Masanari Takahashi, Koji Ohara
Summary: In order to prevent volume change in all-solid-state batteries, an effective binder is needed to improve contact between the solid electrolyte and the electrode active material. The polymerization of the sulfide solid electrolyte Li3PS4 shows promise in achieving this. Analysis of the local structure reveals the presence of disulfide bonds and a polymer chain structure containing Li ions. This polymer could be used as a Li-ion conductive binder in sheet-type all-solid-state batteries with low resistance and high capacity retention.
JOURNAL OF PHYSICAL CHEMISTRY C
(2023)
Article
Chemistry, Physical
Ayuko Kitajou, Satoshi Hiroi, Koji Ohara, Kazutaka Ikeda, Takuma Nanami, Shunsuke Muto
Summary: The xLiF-LiCrO2 series, prepared using the dry ball-milling method, showed improved electro-chemical properties compared to milled-LiCrO2. LiF addition changed the oxidation state of Cr, increasing the rechargeable capacity. The dry ball-milling treatment split the Li-O(F) correlation and changed the dispersion state of Li and Cr in the particles. The reversible capacity and the number of reacted electrons increased with the increasing x in xLiF-LiCrO2, and the charge-discharge reaction proceeded through Cr3+/Cr6+ redox couples.
JOURNAL OF PHYSICAL CHEMISTRY C
(2023)
Article
Chemistry, Physical
Hiroki Yamada, Hirofumi Horikawa, Chokkalingam Anand, Koji Ohara, Toshiaki Ina, Akihiko Machida, Satoshi Tominaka, Tatsuya Okubo, Zhendong Liu, Kenta Iyoki, Toru Wakihara
Summary: To understand the crystallization mechanism of zeolites, the role of the structure-directing agent and its interaction with an amorphous aluminosilicate matrix need to be clarified. This study analyzes the evolution of the aluminosilicate precursor, which causes the nucleation of zeolite, using atom-selective methods. The results reveal the formation of a crystalline-like coordination environment around Cs cations, supporting the conventional hypothesis of a pre-nucleation crystalline structure in zeolite formation.
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
(2023)
Article
Chemistry, Physical
Yu Chikaoka, Naomasa Nakata, Kenta Fujii, Saki Sawayama, Riko Ochi, Etsuro Iwama, Naohisa Okita, Yuta Harada, Yuki Orikasa, Wako Naoi, Katsuhiko Naoi
Summary: In this study, a dual-salt electrolyte system was developed for achieving high capacity and rapid charge-discharge in Mg2+ secondary batteries. The results showed that the use of the dual-salt system improved the Mg2+ insertion/extraction at the cathode/electrolyte interface and enhanced the electrochemical performance of nanoscale cathodes.
ACS APPLIED ENERGY MATERIALS
(2023)
Article
Materials Science, Multidisciplinary
Hiroki Yamada, Koji Ohara, Satoshi Hiroi, Atsushi Sakuda, Kazutaka Ikeda, Takahiro Ohkubo, Kengo Nakada, Hirofumi Tsukasaki, Hiroshi Nakajima, Laszlo Temleitner, Laszlo Pusztai, Shunsuke Ariga, Aoto Matsuo, Jiong Ding, Takumi Nakano, Takuya Kimura, Ryo Kobayashi, Takeshi Usuki, Shuta Tahara, Koji Amezawa, Yoshitaka Tateyama, Shigeo Mori, Akitoshi Hayashi
Summary: Controlling Li ion transport in glasses is crucial for developing all-solid-state batteries. Li3PS4 glass, a solid electrolyte candidate, shows a dynamic coupling effect between Li+ cation mobility and PS43- anion libration, known as the paddlewheel effect. Additionally, it exhibits a coordinated cation diffusion effect (cation-cation interactions) that enhances Li ion transport. The correlation between Li+ ions in the glass structure can be determined by evaluating their valence oscillations, providing insights for the development of new solid electrolytes.
ENERGY & ENVIRONMENTAL MATERIALS
(2023)
Article
Physics, Condensed Matter
Katariina Pussi, Keying Ding, Bernardo Barbiellini, Koji Ohara, Hiroki Yamada, Chuka Onuh, James McBride, Arun Bansil, Ray K. Chiang, Saeed Kamali
Summary: We discuss the atomic structure of Mn-doped cobalt ferrite nanoparticles using a combination of atomic pair distribution functions, high energy X-ray diffraction, and high-resolution transmission electron microscopy measurements. Cobalt ferrite nanoparticles are promising materials for metal-air battery applications. However, the poor electronic conductivity of cobalt ferrite at ambient temperatures limits its bifunctional catalytic performance in oxygen electrocatalysis. Our study reveals that the introduction of Mn ions promotes the conductivity of the cobalt ferrite electrode.
Article
Chemistry, Physical
Yili Cao, Yong Xu, Sergii Khmelevskyi, Maxim Avdeev, Chin-Wei Wang, Shixin Hu, Koji Ohara, Yuanhua Xia, Xin Chen, Qiang Li, Jinxia Deng, Jun Miao, Kun Lin, Xianran Xing
Summary: An alternative strategy to tailor thermal expansion in a family of kagomé metals was proposed, utilizing thermodynamic phase stability instead of altering chemical composition. The study demonstrated an isotropic zero thermal expansion property in high-quality cubic ingots, with magnetic ordering changing from antiferromagnetic to ferromagnetic. The magnetic compensation effect resulted in large magnetic compensation for lattice thermal expansion.
CHEMISTRY OF MATERIALS
(2023)
Article
Chemistry, Physical
Zhuanfang Jing, Yongquan Zhou, Toshio Yamaguchi, Koji Yoshida, Kazutaka Ikeda, Koji Ohara, Guangguo Wang
Summary: Ionhydration plays a crucial role in various fields, but the nature of ion hydration at the molecular level remains inconsistently understood. This study combines neutron scattering, wide-angle X-ray scattering, and molecular dynamics to systematically quantify the hydration ability of alkali metal and halide ions based on static and dynamic hydration numbers. The static hydration number is determined from positional information, while the dynamic hydration number measures the average number of water molecules in the first coordination shell of an ion over a residence time. These hydration numbers provide valuable insights for understanding different natural phenomena.
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
(2023)
Article
Chemistry, Inorganic & Nuclear
Takanori Itoh, Qiuyi Yuan, Chulho Song, Koji Ohara, Satoshi Hiroi, Toru Ishigaki, Masaki Matsui
Summary: The correlation among crystal and local structure, phase transition, and Li-ion conduction of the solid electrolyte LLZ was investigated. The results showed the existence of Li site defects in LLZ and the coexistence of tetragonal and cubic phases at high temperatures. The Li-ion diffusion mechanism was discussed based on factors such as atomic displacement parameters, electric density, and local structure.
JOURNAL OF SOLID STATE CHEMISTRY
(2023)
Article
Chemistry, Physical
Keke Chai, Yongquan Zhou, Xingmei Lu, Toshio Yamaguchi, Koji Ohara, Hongyan Liu, Fayan Zhu
Summary: Choline chloride-carboxylic acid deep eutectic solvents (DESs) have shown great potential as green solvents for various applications. The study investigated the structures of choline chloride/formic acid (FA) and choline chloride/acetic acid (AA) DESs using various techniques. The results revealed the presence of hydrogen bonds and carbon-hydrogen bonds in the DESs, and showed that the interaction between Ch(+) and FA and the Cl- bridge significantly affected the melting point of the DESs.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2023)
Article
Materials Science, Multidisciplinary
Mohammad Kassem, Chris J. J. Benmore, Andrey Tverjanovich, Takeshi Usuki, Maxim Khomenko, Daniele Fontanari, Anton Sokolov, Koji Ohara, Maria Bokova, Shinji Kohara, Eugene Bychkov
Summary: Antimony sesquisulfide Sb2S3 is an outstanding advanced functional material in various rapidly growing applications. The high optical and electric contrast between the crystalline and amorphous states of Sb2S3 is due to the different short and intermediate range order. Substitution with anions (Se) or cations (Bi) can further improve the material's performance.
JOURNAL OF MATERIALS CHEMISTRY C
(2023)
Article
Chemistry, Multidisciplinary
Hirokazu Masai, Shinji Kohara, Toru Wakihara, Yuki Shibazaki, Yohei Onodera, Atsunobu Masuno, Sohei Sukenaga, Koji Ohara, Yuki Sakai, Julien Haines, Claire Levelut, Philippe Hebert, Aude Isambert, David A. Keen, Masaki Azuma
Summary: Densified amorphous silica (SiO2) fabricated from siliceous zeolite (SZ) remains permanently densified, unlike densified glassy SiO2 (GS) fabricated by cold compression. The topology of the densified SZ retains the characteristics of crystalline SZ, while the densified GS relaxes to pristine GS after thermal annealing. These findings suggest the possibility of designing new functional amorphous materials by tuning the topology of the initial zeolitic crystalline phases.
COMMUNICATIONS CHEMISTRY
(2023)
