Proton-Driven Intercalation and Ion Substitution Utilizing Solid-State Electrochemical Reaction

Masaya Fujioka, Chuanbao Wu, Naoki Kubo, Gaoyang Zhao, Atsushi Inoishi, Shigeto Okada, Satoshi Demura, Hideaki Sakata, Manabu Ishimaru, Hideo Kaiju, Junji Nishii

Research output: Contribution to journalArticle

3 Citations (Scopus)

Abstract

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.

Original languageEnglish
Pages (from-to)17987-17993
Number of pages7
JournalJournal of the American Chemical Society
Volume139
Issue number49
DOIs
Publication statusPublished - Dec 13 2017

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Intercalation
Protons
Substitution reactions
Ions
Electric fields
Monovalent Cations
Metastable phases
Materials science
Solid state reactions
Hydrogen
Positive ions
Single crystals
Liquids
Electric potential
Research

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

Cite this

Proton-Driven Intercalation and Ion Substitution Utilizing Solid-State Electrochemical Reaction. / Fujioka, Masaya; Wu, Chuanbao; Kubo, Naoki; Zhao, Gaoyang; Inoishi, Atsushi; Okada, Shigeto; Demura, Satoshi; Sakata, Hideaki; Ishimaru, Manabu; Kaiju, Hideo; Nishii, Junji.

In: Journal of the American Chemical Society, Vol. 139, No. 49, 13.12.2017, p. 17987-17993.

Research output: Contribution to journalArticle

Fujioka, M, Wu, C, Kubo, N, Zhao, G, Inoishi, A, Okada, S, Demura, S, Sakata, H, Ishimaru, M, Kaiju, H & Nishii, J 2017, 'Proton-Driven Intercalation and Ion Substitution Utilizing Solid-State Electrochemical Reaction', Journal of the American Chemical Society, vol. 139, no. 49, pp. 17987-17993. https://doi.org/10.1021/jacs.7b09328
Fujioka, Masaya ; Wu, Chuanbao ; Kubo, Naoki ; Zhao, Gaoyang ; Inoishi, Atsushi ; Okada, Shigeto ; Demura, Satoshi ; Sakata, Hideaki ; Ishimaru, Manabu ; Kaiju, Hideo ; Nishii, Junji. / Proton-Driven Intercalation and Ion Substitution Utilizing Solid-State Electrochemical Reaction. In: Journal of the American Chemical Society. 2017 ; Vol. 139, No. 49. pp. 17987-17993.
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