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Selective metathesis synthesis of MgCr2S4 by control of thermodynamic driving forces
| Title: | Selective metathesis synthesis of MgCr2S4 by control of thermodynamic driving forces |
| Authors: | Miura, Akira Browse this author →KAKEN DB | | Ito, Hiroaki Browse this author | | Bartel, Christopher J. Browse this author | | Sun, Wenhao Browse this author | | Rosero-Navarro, Nataly Carolina Browse this author | | Tadanaga, Kiyoharu Browse this author →KAKEN DB | | Nakata, Hiroko Browse this author | | Maeda, Kazuhiko Browse this author | | Ceder, Gerbrand Browse this author |
| Issue Date: | 1-May-2020 |
| Publisher: | Royal Society of Chemistry |
| Journal Title: | Materials horizons |
| Volume: | 7 |
| Issue: | 5 |
| Start Page: | 1310 |
| End Page: | 1316 |
| Publisher DOI: | 10.1039/c9mh01999e |
| Abstract: | MgCr2S4 thiospinel is predicted to be a compelling Mg-cathode material, but its preparation via traditional solid-state synthesis methods has proven challenging. Wustrow et al. [Inorg. Chem., 2018, 57, 14] found that the formation of MgCr2S4 from MgS + Cr2S3 binaries requires weeks of annealing at 800 degrees C with numerous intermediate regrinds. The slow reaction kinetics of MgS + Cr2S3 -> MgCr2S4 can be attributed to a miniscule thermodynamic driving force of Delta H = -2 kJ mol(-1). Here, we demonstrate that the double ion-exchange metathesis reaction, MgCl2 + 2NaCrS(2) -> MgCr2S4 + 2NaCl, has a reaction enthalpy of Delta H = -47 kJ mol(-1), which is thermodynamically driven by the large exothermicity of NaCl formation. Using this metathesis reaction, we successfully synthesized MgCr2S4 nanoparticles (<200 nm) from MgCl2 and NaCrS2 precursors in a KCl flux at 500 degrees C in only 30 minutes. NaCl and other metathesis byproducts are then easily washed away by water. We rationalize the selectivity of MgCr2S4 in the metathesis reaction from the topology of the DFT-calculated pseudo-ternary MgCl2-CrCl3-Na2S phase diagram. Our work helps to establish metathesis reactions as a powerful alternative synthesis route to inorganic materials that have otherwise small reaction energies from conventional precursors. |
| Type: | article (author version) |
| URI: | http://hdl.handle.net/2115/81117 |
| Appears in Collections: | 工学院・工学研究院 (Graduate School of Engineering / Faculty of Engineering) > 雑誌発表論文等 (Peer-reviewed Journal Articles, etc)
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Submitter: 三浦 章
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