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論文

Electron storage performance of hybrid materials comprising polyoxometalates and carbon nanohorns as cathode-active materials

若松 勝洋*; 関原 輝昇*; 山口 慶彦*; 松島 諒*; 松村 大樹; Kuila, T.*; 吉川 浩史*

Batteries & Supercaps (Internet), 6(1), p.e202200385_1 - e202200385_8, 2023/01

 被引用回数:2 パーセンタイル:29.01(Electrochemistry)

Nanohybrid materials comprising polyoxometalates (POMs) and nanocarbons have attracted considerable attention as electrode-active materials for rechargeable lithium-ion batteries (LIBs). These materials exhibit multi-electron redox reactions, resulting in an improved battery capacity. This study focuses on carbon nanohorns (CNHs) as a nanocarbon material and evaluates the battery performance using POM/CNH hybrids as cathode-active materials. X-ray absorption fine structural analysis was performed to investigate the reaction mechanism of these hybrids. POM/oxidized CNH (CNHox) hybrid materials maintain high capacities at high current densities as the high surface area availability of CNHox leads to high electrical double-layer capacitances. These findings show an improved performance of the as-developed material when compared with those reported in previous papers and can contribute toward an improved design of cathode-active materials for high-performance supercapacitors.

論文

General synthesis of single-atom catalysts for hydrogen evolution reactions and room-temperature Na-S batteries

Lai, W.-H.*; Wang, H.*; Zheng, L.*; Jiang, Q.*; Yan, Z.-C.*; Wang, L.*; 吉川 浩史*; 松村 大樹; Sun, Q.*; Wang, Y.-X.*; et al.

Angewandte Chemie; International Edition, 59(49), p.22171 - 22178, 2020/12

 被引用回数:77 パーセンタイル:95.81(Chemistry, Multidisciplinary)

Herein, we report a comprehensive strategy to synthesize a full range of single-atom metals on carbon matrix, including V, Mn, Fe, Co, Ni, Cu, Ge, Mo, Ru, Rh, Pd, Ag, In, Sn, W, Ir, Pt, Pb, and Bi. The extensive applications of various single-atom catalysts (SACs) are manifested via their ability to electro-catalyze typical hydrogen evolution reactions (HER) and conversion reactions in novel room-temperature sodium sulfur batteries (RT-Na-S). The enhanced performances for these electrochemical reactions arisen from the ability of different single active atoms on local structures to tune their electronic configuration. Significantly, the electrocatalytic behaviors of diverse SACs, assisted by density functional theory calculations, are systematically revealed by in situ synchrotron X-ray diffraction and in situ transmission electronic microscopy, providing a strategic library for the general synthesis and extensive applications of SACs in energy conversion and storage.

論文

Porous metal-organic frameworks containing reversible disulfide linkages as cathode materials for lithium-ion batteries

清水 剛志*; Wang, H.*; 松村 大樹; 光原 圭*; 太田 俊明*; 吉川 浩史*

ChemSusChem, 13(9), p.2256 - 2263, 2020/05

 被引用回数:24 パーセンタイル:77.17(Chemistry, Multidisciplinary)

Three porous disulfide-ligand-containing metal-organic frameworks (DS-MOFs) and two nonporous coordination polymers with disulfide ligands (DS-CPs) with various structural dimensionalities were used as cathode active materials in lithium batteries. Charge/discharge performance examinations revealed that only porous DS-MOF-based batteries exhibited significant capacities close to the theoretical values, which was ascribed to the insertion of electrolyte ions into the DS-MOFs. Battery reactions were probed by instrumental analyses. The dual redox reactions of metal ions and disulfide ligands in the MOFs resulted in higher capacities, and the presence of reversible electrochemically dynamic S-S bonds stabilized the cycling performance. Thus, the strategy of S-S moiety trapping in MOFs and the obtained correlation between the structural features and battery performance could contribute to the design of high-performance MOF-based batteries and the practical realization of Li-S batteries.

論文

Zeolitic vanadomolybdates as high-performance cathode-active materials for sodium-ion batteries

Zhang, Z,*; Wang, H.*; 吉川 浩史*; 松村 大樹; 畑尾 秀哉*; 石川 理史*; 上田 渉*

ACS Applied Materials & Interfaces, 12(5), p.6056 - 6063, 2020/02

 被引用回数:6 パーセンタイル:31.09(Nanoscience & Nanotechnology)

Developing new cathode-active materials for rechargeable batteries is important to fulfill the growing demands of energy transformation, storage, and utilization. Zeolitic transition-metal oxides based on vanadomolybdate, constructed by pentagon metal-oxygen clusters as building blocks and metal ions as linkers in a trigonal symmetry, are good candidates for cathodes of Na rechargeable batteries. The material is activated via amorphization of the crystal structure in the ab plane during discharging process, keeping the molecular structure of the building blocks stable, which causes high specific capacity and good cycle performance.

論文

In situ X-ray absorption fine structure studies of amorphous and crystalline polyoxovanadate cluster cathodes for lithium batteries

Wang, H.*; 磯部 仁*; 松村 大樹; 吉川 浩史*

Journal of Solid State Electrochemistry, 22(7), p.2067 - 2071, 2018/07

 被引用回数:15 パーセンタイル:40.22(Electrochemistry)

Amorphous and crystalline MetfV10 electrodes for lithium ion batteries were prepared by mixing MetfV10 with different binders: polyvinylidenefluoride (PVDF) or polytetrafluoroethylene (PTFE). The reaction mechanism was studied using in situ X-ray absorption fine structure (XAFS) and impedance measurements. The X-ray absorption near-edge structure (XANES) results exhibited a 10-electron reduction per the formula of MetfV10 during discharge, resulting in a large capacity. Extended X-ray absorption fine structure (EXAFS) analyses suggested a slight expansion in the molecular size of MetfV10. The impedance measurements reveal that an increase of discharge capacities for the amorphous cathode is due to lower resistance than in the crystalline cathode. This study presents a rational selection of amorphous or crystalline cathode materials for high power and high energy density lithium batteries.

論文

Rechargeable batteries based on stable redox reactions of disulfide included in a metal-organic framework as ligands

清水 剛志*; Wang, H.*; 谷藤 尚貴*; 松村 大樹; 吉村 真史*; 中西 康次*; 太田 俊明*; 吉川 浩史*

Chemistry Letters, 47(5), p.678 - 681, 2018/05

 被引用回数:9 パーセンタイル:33.87(Chemistry, Multidisciplinary)

Disulfide, which is a sub-group of organosulfides, has been studied as a promising cathode active material. Herein, to improve battery performance, we inserted disulfide into Cu-based metal organic framework (MOF) as a ligand. As a result, the disulfide inserted MOF exhibited a high capacity based on dual redox reactions of Cu ions and disulfide ligands, and a stable cycle performance. The S $$K$$-edge X-ray absorption fine structure analyses revealed a reversible cleavage and formation of S-S bond in the MOF during discharge and charge process.

論文

Preparation of $$gamma$$-LiV$$_{2}$$O$$_{5}$$ from polyoxovanadate cluster Li$$_{7}$$[V$$_{15}$$O$$_{36}$$(CO$$_{3}$$)] as a high-performance cathode material and its reaction mechanism revealed by ${{it operando}}$ XAFS

Wang, H.*; 磯部 仁*; 清水 剛志*; 松村 大樹; 伊奈 稔哲*; 吉川 浩史*

Journal of Power Sources, 360, p.150 - 156, 2017/08

 被引用回数:13 パーセンタイル:41.36(Chemistry, Physical)

$$gamma$$-phase LiV$$_{2}$$O$$_{5}$$, which shows superior electrochemical performance as cathode material in Li-ion batteries, was prepared by annealing the polyoxovanadate cluster Li$$_{7}$$[V$$_{15}$$O$$_{36}$$(CO$$_{3}$$)]. The reaction mechanism was studied using ${{it operando}}$ X-ray absorption fine structure (XAFS), powder X-ray diffraction (PXRD), and X-ray photoelectron spectroscopy (XPS) analyses. The X-ray absorption near edge structure (XANES) and XPS results reveal that $$gamma$$-LiV$$_{2}$$O$$_{5}$$ undergoes two-electron redox reaction per V$$_{2}$$O$$_{5}$$ pyramid unit, resulting in a large reversible capacity of 260 Ah/kg. The extended X-ray absorption fine structure (EXAFS) and PXRD analyses also suggest that the V-V distance slightly increases, due to the reduction of V$$^{5+}$$ to V$$^{4+}$$ during Li ion intercalation as the material structure is maintained. As a result, $$gamma$$-Li$$_{x}$$V$$_{2}$$O$$_{5}$$ shows highly reversible electrochemical reaction with x = 0.1-1.9.

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