TY - JOUR
T1 - Exceptional Flux Growth and Chemical Transformation of Metastable Orthorhombic LiMnO2 Cuboids into Hierarchically-Structured Porous H1.6Mn1.6O4 Rods as Li Ion Sieves
AU - Hayashi, Fumitaka
AU - Kurokawa, Shoichi
AU - Shiiba, Hiromasa
AU - Wagata, Hajime
AU - Yubuta, Kunio
AU - Oishi, Shuji
AU - Nishikiori, Hiromasa
AU - Teshima, Katsuya
N1 - Funding Information:
This work was supported by the Center of Innovation Program, Global Aqua Innovation Center for Increasing Water- Sustainability and Improving Living Standards in the World from Japan Science and Technology Agency (JST).
Publisher Copyright:
© 2016 American Chemical Society.
Copyright:
Copyright 2017 Elsevier B.V., All rights reserved.
PY - 2016/11/2
Y1 - 2016/11/2
N2 - Selective lithium uptake from seawater and lake brine is an important challenge in energy and environmental science. H1.6Mn1.6O4 with pseudospinel-type structure is a highly selective adsorbent for Li ions, but it is difficult to prepare large, highly crystalline H1.6Mn1.6O4 crystals with porous structure due to its thermodynamic metastability. Herein we demonstrate simple chemical processes that transform flux-grown, idiomorphic orthorhombic LiMnO2 (o-LiMnO2) cuboids of micrometer size into hierarchically structured H1.6Mn1.6O4 rods. We have optimized the flux growth conditions such as the Mn source, holding temperature, and solute concentration in order to yield large, single-phase o-LiMnO2 particles. The use of MnO under very low solute concentration (1 mol %) and high temperature (1000 °C) is critical to obtaining the single-phase, idiomorphic o-LiMnO2 cuboids. The metastability of o-LiMnO2 is confirmed by ab initio density functional theory calculation in comparison with other lithium manganates such as LiMn2O4 and Li2MnO3. The successive calcination and acid treatment allow the transformation of o-LiMnO2 into H1.6Mn1.6O4 rods with porous structure. The resultant H1.6Mn1.6O4 shows high Li+ adsorption capacity (∼5.6 mmol g-1), high Li+/Na+ selectivity, and good durability compared with existing H1.6Mn1.6O4 adsorbents.
AB - Selective lithium uptake from seawater and lake brine is an important challenge in energy and environmental science. H1.6Mn1.6O4 with pseudospinel-type structure is a highly selective adsorbent for Li ions, but it is difficult to prepare large, highly crystalline H1.6Mn1.6O4 crystals with porous structure due to its thermodynamic metastability. Herein we demonstrate simple chemical processes that transform flux-grown, idiomorphic orthorhombic LiMnO2 (o-LiMnO2) cuboids of micrometer size into hierarchically structured H1.6Mn1.6O4 rods. We have optimized the flux growth conditions such as the Mn source, holding temperature, and solute concentration in order to yield large, single-phase o-LiMnO2 particles. The use of MnO under very low solute concentration (1 mol %) and high temperature (1000 °C) is critical to obtaining the single-phase, idiomorphic o-LiMnO2 cuboids. The metastability of o-LiMnO2 is confirmed by ab initio density functional theory calculation in comparison with other lithium manganates such as LiMn2O4 and Li2MnO3. The successive calcination and acid treatment allow the transformation of o-LiMnO2 into H1.6Mn1.6O4 rods with porous structure. The resultant H1.6Mn1.6O4 shows high Li+ adsorption capacity (∼5.6 mmol g-1), high Li+/Na+ selectivity, and good durability compared with existing H1.6Mn1.6O4 adsorbents.
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U2 - 10.1021/acs.cgd.6b00223
DO - 10.1021/acs.cgd.6b00223
M3 - Article
AN - SCOPUS:84994309222
VL - 16
SP - 6178
EP - 6185
JO - Crystal Growth and Design
JF - Crystal Growth and Design
SN - 1528-7483
IS - 11
ER -