Article
Chemistry, Physical
Yuki Sasaki, Kaname Yoshida, Tadahiro Kawasaki, Akihide Kuwabara, Yoshio Ukyo, Yuichi Ikuhara
Summary: Aqueous zinc-based batteries are expected to be low-cost and high energy density, however, dendrite formation during charging remains a major issue. In situ TEM observations revealed that dendrite growth from the zinc anode causes short-circuiting and cycle degradation in zinc-based batteries. Characterization of electrochemical zinc deposition is crucial for realizing long life rechargeable zinc-based batteries.
JOURNAL OF POWER SOURCES
(2021)
Article
Chemistry, Physical
Ming Li, Lingbing Ran, Ruth Knibbe
Summary: This study explores the importance of zinc batteries for battery technology advancement and the effects of applied current and electrolyte flow rate on the early stage of Zn dendrite formation. The research reveals a square root relationship between time and Zn dendrite lateral growth, with higher applied current resulting in longer incubation time.
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
(2021)
Article
Nanoscience & Nanotechnology
L. Geng, Q. Liu, J. Zhao, H. Ye, H. Sun, X. Zhang, P. Zhang, T. Yang, Y. Su, H. Li, D. Zhu, J. Yao, J. Chen, P. Jia, J. Yan, L. Zhang, Y. Tang, J. Huang
Summary: The growth mechanism of Cu nanoparticles during electrochemical deposition was characterized, revealing a hierarchical agglomeration growth mechanism and a self-limiting grain growth mechanism. These findings are important for tailoring the size and shape of nanoparticles.
MATERIALS TODAY NANO
(2022)
Article
Chemistry, Physical
Maoni Lu, Daochuan Jiang, Xiaoxing Zhou, Sichen Li, Xinghao Li, Ping Chen, Zhenjie Sun, Junnan Hao, Manzhou Zhu, Peng Li
Summary: By using a defective zinc-based metal-organic framework (DZ-MOF) multifunctional layer as a protective layer, dendrite growth, hydrogen evolution, and corrosion reactions in zinc ion batteries can be effectively addressed to improve the stability and cycle life of the batteries.
JOURNAL OF MATERIALS CHEMISTRY A
(2023)
Article
Chemistry, Physical
Yanshuai Li, Tianpin Wu, Yifei Yuan, Jun Lu
Summary: A thorough understanding of the underlying mechanism of advanced cathode materials is vital due to recent developments in secondary ion batteries for high-energy-density applications. In situ transmission electron microscopy (TEM) techniques capable of high spatial and temporal resolution in operando analysis of dynamic battery systems have attracted significant interest. However, the complex electrochemical reaction mechanisms of cathode materials have not been extensively investigated using in situ TEM due to technical difficulties in implementation.
Article
Chemistry, Analytical
Xuelin Zhang, Yufan Zhou, Ying Chen, Ming Li, Haitao Yu, Xinxin Li
Summary: Transmission electron microscopy (TEM) is an effective method for analyzing and characterizing material structures. However, it is limited to static structures at room temperature in a high-vacuum environment. A microchip based on MEMS technology has been developed to address this limitation, allowing real-time study of material structure evolution and chemical processes in gas and high-temperature environments. Tests show that the microchip ensures high-temperature uniformity and achieves high resolution even in a flowing atmosphere.
Article
Electrochemistry
Baiyu Guo, Jingzhao Chen, Zaifa Wang, Yong Su, Hui Li, Hongjun Ye, Liqiang Zhang, Yongfu Tang, Jianyu Huang
Summary: Research on lithium selenium (Li-Se) all-solid-state batteries (ASSBs) found that they have better electronic conductivity than lithium sulfur (Li-S) batteries. By using in situ transmission electron microscopy (TEM) technique, the electrochemistry of Li-Se ASSBs was investigated at different temperatures. It was discovered that polyselenides were absent during discharge and charge of Li-Se ASSBs, and the discharge products of Li2Se cannot be decomposed at room temperature, while (LiSe)-Se-2 can be easily decomposed at high temperatures. These studies provide new understanding of Li2Se electrochemistry and an important strategy to boost the performance of Li-Se ASSBs for energy storage applications.
ELECTROCHIMICA ACTA
(2022)
Article
Chemistry, Physical
Kazuki Uchiyama, Takashi Yamamoto, Yasuaki Einaga
Summary: Silicon carbide (SiC) has excellent properties but lacks sufficient electrical conductivity for electrochemical applications, leading to the exploration of boron-doped SiC (SiC:B). The electrochemical properties of SiC:B were evaluated and found to have reactivity and sensitivity comparable to that of glassy carbon electrodes.
Article
Chemistry, Physical
Lin Geng, Qiunan Liu, Jingzhao Chen, Peng Jia, Hongjun Ye, Jitong Yan, Liqiang Zhang, Yongfu Tang, Jianyu Huang
Summary: By conducting in situ observations of the early stage of electrochemical Na deposition, this research revealed an important electrochemical Ostwald ripening (EOR) phenomenon which dictates the early stage of Na deposition. Through two types of EOR, we gained a deeper understanding of the Na deposition mechanism.
Article
Nanoscience & Nanotechnology
Lei Xu, Youran Hong, Jiangwei Wang, Langli Luo
Summary: Nanoscale solid-state transformations of metals and alloys during electrochemical processes play a critical role in various applications such as corrosion, electrochemical machining, and alkali metal batteries. Using in situ transmission electron microscopy, a unique phase transformation of Ag nanowire alloyed with Li was demonstrated, featuring a surface reaction of electrochemical lithiation of Ag followed by a fast redistribution of Ag into small nanoparticles embedded in Li2O.
SCRIPTA MATERIALIA
(2021)
Article
Chemistry, Multidisciplinary
Yanshuai Li, Yongfu Tang, Xiaomei Li, Wei Tu, Liqiang Zhang, Jianyu Huang
Summary: In-situ transmission electron microscopy with a microelectromechanical systems (MEMS) heating device was used to investigate electrochemical reactions in HT-Na-S batteries, revealing that the sulfur cathode is fully discharged to Na2S rather than Na2S2 at high temperatures, with swift and highly reversible electrochemical reactions.
Article
Electrochemistry
Jialong Wang, Md Monirul Islam, Scott W. Donne
Summary: This study describes a modified Swagelok electrochemical cell to characterize individual electrode behavior in the non-aqueous Li-LiMn2O4 system. The outcomes include variations in lithium negative electrode potential with applied current, lithium corrosion and passivation in the electrolyte, and LiMn2O4 dissolution with cycling, revealing Mn(III) as the dissolution product. The application of this technique to other systems, such as electrode materials and electrolytes, is also discussed.
ELECTROCHIMICA ACTA
(2021)
Article
Nanoscience & Nanotechnology
Fei He, Nannan Xia, Yan Zheng, Yixin Zhang, Huailin Fan, Delong Ma, Qianhe Liu, Xun Hu
Summary: By coupling impregnation and electrochemical activation, an efficient, stable, and robust Ru-based electrocatalyst with ultrasmall and well-distributed Ru nanoparticles was developed, showing superior performance compared to Pt-based and Ru-based catalysts.
ACS APPLIED MATERIALS & INTERFACES
(2021)
Article
Materials Science, Multidisciplinary
Vesna Srot, Rainer Straubinger, Felicitas Predel, Peter A. van Aken
Summary: This study introduces a new methodology based on focused ion beam (FIB) for preparing clean and artifact-free specimens on micro-electro-mechanical-system (MEMS) chips for in-situ electrical and electro-thermal experiments in a (scanning) transmission electron microscope ((S)TEM). By adopting an alternative geometry, the lamellae are directly attached to a MEMS chip after the lift-out procedure and then further treated or thinned to electron transparency. The quality of the produced lamellae on a chip is comparable to that of a classical FIB-prepared sample, as demonstrated by high-resolution STEM imaging and analytical techniques. Various sample preparation parameters and the performance of in-situ prepared samples have been evaluated through electrical-biasing experiments.
MICROSCOPY AND MICROANALYSIS
(2023)
Article
Engineering, Environmental
Kab In Kim, Jae Kwan Bae, Emilio Audasso, Albert Won Cho, Young Bae Jun, Hyun Seo Park, Seong-Cheol Jang, Yong Soo Cho, Han Sung Kim, Sun-Hee Choi, Sung Pil Yoon
Summary: This study introduces a novel in situ method for replenishing the electrolyte in molten carbonate fuel cells (MCFCs) using gaseous electrolyte precursors (EP). The method demonstrates sustainable long-term operation and stable performance of MCFCs, offering enhanced durability and making them more viable for energy applications.
CHEMICAL ENGINEERING JOURNAL
(2023)
Article
Nanoscience & Nanotechnology
Keiji Shimoda, Kentaro Kuratani, Shunsuke Kobayashi, Tomonari Takeuchi, Miwa Murakami, Akihide Kuwabara, Hikari Sakaebe
Summary: Amorphous transition-metal polysulfides have potential applications as positive electrode materials in rechargeable lithium-ion batteries. This study investigates the redox reactions of sulfur anions during lithiation of amorphous TiS4 using experimental and theoretical methods. The results show the changes in sulfur valence states in the Li4TiS4 composition, and the conversion of a-TiS4 to metallic Ti and Li2S during deep lithiation.
ACS APPLIED MATERIALS & INTERFACES
(2022)
Article
Chemistry, Physical
Shenghan Gao, Cedric Tassel, Susumu Fujii, Hiroki Ubukata, Tong Zhu, Datong Zhang, Thibault Broux, Takashi Saito, Chengchao Zhong, Emre Yoruk, Kentaro Yamamoto, Akihide Kuwabara, Yoshiharu Uchimoto, Hiroshi Kageyama
Summary: The high-pressure synthesis of a Na3H(ZnH4) antiperovskite is reported in this study, containing the (ZnH4)(2-) polyanion with unique structural features. The presence of heavily distorted HNa6 octahedra and off-centered hydride anion in the B site are distinct characteristics. Theoretical analysis suggests a pressure-induced phase transition from P4/ncc to I4/mcm, involving concerted motion between the B-site single anion and the A-site tetrahedral polyanion.
CHEMISTRY OF MATERIALS
(2022)
Article
Chemistry, Inorganic & Nuclear
Chengchao Zhong, Yui Ishii, Cedric Tassel, Tong Zhu, Daichi Kato, Kosuke Kurushima, Yukihiro Fujibayashi, Takashi Saito, Takafumi Ogawa, Akihide Kuwabara, Shigeo Mori, Hiroshi Kageyama
Summary: In this study, the crystal structure of Sillen-Aurivillius layered perovskite oxyhalide Bi4NbO8Br was revisited, and it was found that the polarization in the material originates from the stereochemically active Bi3+ lone pair electrons and the octahedral off-centering of Nb5+ cations. The revised structure suggests that Sillen-Aurivillius compounds have potential as ferroelectric materials, similar to Aurivillius-type ferroelectrics.
INORGANIC CHEMISTRY
(2022)
Article
Chemistry, Physical
Shusuke Kasamatsu, Yuichi Motoyama, Kazuyoshi Yoshimi, Ushio Matsumoto, Akihide Kuwabara, Takafumi Ogawa
Summary: A scheme for ab initio configurational sampling in multicomponent crystalline solids using Behler-Parinello type neural network potentials (NNPs) is proposed, which allows bypassing the structural relaxation procedure and is applicable to complex systems.
JOURNAL OF CHEMICAL PHYSICS
(2022)
Article
Microscopy
Kaname Yoshida, Yuki Sasaki, Akihide Kuwabara, Yuichi Ikuhara
Summary: A novel setup for in situ observation of electrochemical reactions in liquids using atmospheric scanning electron microscopy (SEM) is proposed. The setup consists of a working electrode (WE) on an electrochemical chip and two other electrodes inserted into a liquid electrolyte, allowing precise control of electrochemical reactions using an external potentiostat/galvanostat. The proposed system was successfully used to deposit copper from a CuSO4 aqueous solution while acquiring nanoscale images and reliable electrochemical data.
Correction
Nanoscience & Nanotechnology
Shunsuke Kobayashi, Hideaki Watanabe, Takeharu Kato, Fuminori Mizuno, Akihide Kuwabara
ACS APPLIED MATERIALS & INTERFACES
(2023)
Article
Microscopy
Kaname Yoshida, Hsin-Hui Huang, Tomohiro Miyata, Yohei K. Sato, Hiroshi Jinnai
Summary: The mechanisms of electron irradiation damage to epoxy resin samples were evaluated using electron diffraction patterns and electron energy-loss spectra. The electron diffraction patterns showed three indistinct halo rings, with one ring corresponding to an intermolecular distance of approximately 6.4 angstrom rapidly degrading, possibly due to cross-linking between molecular chains. The degree of electron irradiation damage changed with the accelerating voltage, and the tolerance dose limit of the epoxy resin improved at higher accelerating voltages. Changes in low-loss electron energy-loss spectra indicated significant mass loss of the epoxy resin in the early stage of electron irradiation.
Article
Chemistry, Physical
Susumu Fujii, Yuta Shimizu, Junji Hyodo, Akihide Kuwabara, Yoshihiro Yamazaki
Summary: This study presents a machine learning approach to accelerate the exploration and discovery of unconventional proton-conducting inorganic solid electrolytes. By considering dopant dissolution and hydration reactions, the machine learning models provide quantitative predictions and physical interpretations for synthesizable host-dopant combinations with hydration capabilities. Utilizing these insights, two unconventional proton conductors are discovered. This study demonstrates an efficient approach for exploring novel inorganic materials.
ADVANCED ENERGY MATERIALS
(2023)
Article
Chemistry, Physical
Yoshiki Izumi, Fumitaka Takeiri, Kei Okamoto, Takashi Saito, Takashi Kamiyama, Akihide Kuwabara, Genki Kobayashi
Summary: Hydride ion conductors, especially the fluorite-type LaH3-delta series, have shown high conductivity around room temperature. However, their non-stoichiometric nature poses challenges for their use as solid electrolytes. In this study, Sr-substituted LaH3-delta with slight O2- incorporation was synthesized, demonstrating H- conductivity at room temperature. This achievement is a significant milestone in the development of electrochemical devices that utilize its strong reducing ability.
ADVANCED ENERGY MATERIALS
(2023)
Article
Microscopy
Kaname Yoshida, Yuki Sasaki, Akihide Kuwabara, Yuichi Ikuhara
Summary: In this paper, we review notable points from observations of electrochemical reactions in a liquid electrolyte using liquid-phase electron microscopy. In-situ microscopic observations of electrochemical reactions are crucial for addressing various battery issues. Two methods, liquid-phase (scanning) transmission electron microscopy and liquid-phase scanning electron microscopy, are discussed and their advantages and disadvantages are summarized.
Article
Multidisciplinary Sciences
Kousuke Ooe, Takehito Seki, Kaname Yoshida, Yuji Kohno, Yuichi Ikuhara, Naoya Shibata
Summary: Zeolites are widely used in industries for their unique porous atomic structures, but their local atomic structures are difficult to observe directly due to low electron irradiation resistance. A low-electron-dose imaging technique called optimum bright-field scanning transmission electron microscopy (OBF STEM) has been developed, which allows for high-resolution observation of zeolite structures. In this study, the researchers successfully visualized the atomic sites in two types of zeolite and characterized the complex local atomic structure. This research contributes to the understanding of local atomic structures in electron beam-sensitive materials.
Article
Chemistry, Inorganic & Nuclear
Nur Ika Puji Ayu, Fumitaka Takeiri, Takafumi Ogawa, Akihide Kuwabara, Masato Hagihala, Takashi Saito, Takashi Kamiyama, Genki Kobayashi
Summary: New solid compounds A(3-x)GaO(4)H(1-y) (A = Sr, Ba 0.15, y SIM;0.3) have been synthesized, which are the first oxyhydrides containing gallium ions. The compounds adopt an anti-perovskite structure consisting of hydride-anion-centered HA(6) octahedra with tetrahedral GaO4 polyanions, showing partial defect in A- and H-sites. The thermodynamic stability and band gap of stoichiometric Ba3GaO4H are supported by formation energy calculations, and annealing Ba powder suggests H- desorption and O2-/H- exchange reactions.
DALTON TRANSACTIONS
(2023)
Article
Chemistry, Inorganic & Nuclear
Koji Okada, Susumu Fujii, Cedric Tassel, Shenghan Gao, Hiroki Ubukata, Wenli Pan, Kentaro Yamamoto, Yoshiharu Uchimoto, Akihide Kuwabara, Hiroshi Kageyama
Summary: Unlike perovskite oxides, antiperovskites M(3)HCh and M(3)FCh (M = Li, Na; Ch = S, Se, Te) mostly maintain their ideal cubic structure due to anionic size flexibility and low-energy phonon modes that promote their ionic conductivity. This study demonstrates the synthesis of potassium-based antiperovskites K3HTe and K3FTe, which maintain a cubic symmetry and can be prepared at ambient pressure, unlike most other M(3)HCh and M(3)FCh compounds that require high pressure synthesis. A systematic comparison of cubic M3HTe and M3FTe (M = Li, Na, K) reveals a contraction in telluride anions in the order of K, Na, Li, with a pronounced contraction in the Li system.
DALTON TRANSACTIONS
(2023)
Article
Chemistry, Inorganic & Nuclear
Kazuki Shitara, Akihide Kuwabara, Naoyoshi Nunotani, Muhammad Radzi Iqbal Bin Misran, Miki Inada, Tomoki Uchiyama, Yoshiharu Uchimoto, Nobuhito Imanaka
Summary: The ionic conduction mechanism in M2+-doped lanthanum oxybromide (LaOBr) was investigated through theoretical calculations and experimental analyses. The presence of dopant ions resulted in significant changes in the positions of La3+ ions, which were experimentally supported. The migration of Br- ions was found to be more probable than that of O2- ions. The evaluation of association and migration energies showed good agreement with experimental results.
DALTON TRANSACTIONS
(2023)
