TY - JOUR
T1 - Proton-Driven Intercalation and Ion Substitution Utilizing Solid-State Electrochemical Reaction
AU - Fujioka, Masaya
AU - Wu, Chuanbao
AU - Kubo, Naoki
AU - Zhao, Gaoyang
AU - Inoishi, Atsushi
AU - Okada, Shigeto
AU - Demura, Satoshi
AU - Sakata, Hideaki
AU - Ishimaru, Manabu
AU - Kaiju, Hideo
AU - Nishii, Junji
N1 - Funding Information:
This research has been partially supported by a Grant-in-Aid for Young Scientists and Grant-in-Aid for Challenging Exploratory Research from the Japan Society for the Promotion of Science (JSPS; Grant No. 15K17711 and 86000149), Iketani Science and Technology Foundation, Nanotech Career-up Alliance (CUPAL), Environment and Materials and the Cooperative Research Program of the Network Joint Research Center for Materials and Devices from the Ministry of Education, Culture, Sports, Science and Technology (MEXT) and the Dynamic Alliance for Open Innovation Bridging Human from MEXT. The authors thank Prof. S. Noro (Hokkaido University) for the experimental help with IR spectroscopy measurements. The authors also thank N. Kawai (Hokkaido University) for the preparation of the sample for TEM analysis.
Funding Information:
This research has been partially supported by a Grant-in-Aid for Young Scientists and Grant-in-Aid for Challenging Exploratory Research from the Japan Society for the Promotion of Science (JSPS; Grant No. 15K17711 and 86000149), Iketani Science and Technology Foundation Nanotech Career-up Alliance (CUPAL), Environment and Materials and the Cooperative Research Program of the Network Joint Research Center for Materials and Devices from the Ministry of Education, Culture Sports, Science and Technology (MEXT) and the Dynamic Alliance for Open Innovation Bridging Human from MEXT. The authors thank Prof. S. Noro (Hokkaido University) for the experimental help with IR spectroscopy measurements. The authors also thank N. Kawai (Hokkaido University) for the preparation of the sample for TEM analysis.
Publisher Copyright:
© 2017 American Chemical Society.
PY - 2017/12/13
Y1 - 2017/12/13
N2 - The development of an unconventional synthesis method has a large potential to drastically advance materials science. In this research, a new synthesis method based on a solid-state electrochemical reaction was demonstrated, which can be made available for intercalation and ion substitution. It was referred to as proton-driven ion introduction (PDII). The protons generated by the electrolytic dissociation of hydrogen drive other monovalent cations along a high electric field in the solid state. Utilizing this mechanism, Li+, Na+, K+, Cu+, and Ag+ were intercalated into a layered TaS2 single crystal while maintaining high crystallinity. This liquid-free process of ion introduction allows the application of high voltage around several kilovolts to the sample. Such a high electric field strongly accelerates ion substitution. Actually, compared to conventional solid-state reaction, PDII introduced 15 times the amount of K into Na super ionic conductor (NASICON)-structured Na3-xKxV2(PO4)3. The obtained materials exhibited a thermodynamically metastable phase, which has not been reported so far. This concept and idea for ion introduction is expected to form new functional compounds and/or phases.
AB - The development of an unconventional synthesis method has a large potential to drastically advance materials science. In this research, a new synthesis method based on a solid-state electrochemical reaction was demonstrated, which can be made available for intercalation and ion substitution. It was referred to as proton-driven ion introduction (PDII). The protons generated by the electrolytic dissociation of hydrogen drive other monovalent cations along a high electric field in the solid state. Utilizing this mechanism, Li+, Na+, K+, Cu+, and Ag+ were intercalated into a layered TaS2 single crystal while maintaining high crystallinity. This liquid-free process of ion introduction allows the application of high voltage around several kilovolts to the sample. Such a high electric field strongly accelerates ion substitution. Actually, compared to conventional solid-state reaction, PDII introduced 15 times the amount of K into Na super ionic conductor (NASICON)-structured Na3-xKxV2(PO4)3. The obtained materials exhibited a thermodynamically metastable phase, which has not been reported so far. This concept and idea for ion introduction is expected to form new functional compounds and/or phases.
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U2 - 10.1021/jacs.7b09328
DO - 10.1021/jacs.7b09328
M3 - Article
C2 - 29144128
AN - SCOPUS:85038245030
SN - 0002-7863
VL - 139
SP - 17987
EP - 17993
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
IS - 49
ER -