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Title: High magnesium mobility in ternary spinel chalcogenides

Abstract

Magnesium batteries appear a viable alternative to overcome the safety and energy density limitations faced by current lithium-ion technology. Furthermore, the development of a competitive magnesium battery is plagued by the existing notion of poor magnesium mobility in solids. We demonstrate by using ab initio calculations, nuclear magnetic resonance, and impedance spectroscopy measurements that substantial magnesium ion mobility can indeed be achieved in close-packed frameworks (~ 0.01-0.1 mS cm -1 at 298 K), specifically in the magnesium scandium selenide spinel. Our theoretical predictions also indicate that high magnesium ion mobility is possible in other chalcogenide spinels, opening the door for the realization of other magnesium solid ionic conductors and the eventual development of an all-solid-state magnesium battery.

Authors:
ORCiD logo [1];  [2]; ORCiD logo [3];  [4];  [5]; ORCiD logo [6];  [6];  [5]; ORCiD logo [7];  [3]
  1. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Materials Science Division; Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States). Dept. of Materials Science and Engineering
  2. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Materials Science Division; Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States). Dept. of Materials Science and Engineering; Shanghai Jiao Tong Univ. (China). Shanghai Jiao Tong Univ. Joint Inst.
  3. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Materials Science Division; Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States). Dept. of Materials Science and Engineering; Univ. of California, Berkeley, CA (United States). Dept. of Materials Science and Engineering
  4. Argonne National Lab. (ANL), Argonne, IL (United States). Chemical Sciences and Engineering Division
  5. Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States). Dept. of Materials Science and Engineering
  6. Univ. of California, Berkeley, CA (United States). Dept. of Materials Science and Engineering
  7. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Materials Science Division
Publication Date:
Research Org.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); USDOE Office of Science - Office of Basic Energy Sciences - Joint Center for Energy Storage Research (JCESR)
OSTI Identifier:
1417619
Alternate Identifier(s):
OSTI ID: 1427174
Grant/Contract Number:
AC02-05CH11231; AC02-06CH11357; 3F-31144
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Nature Communications
Additional Journal Information:
Journal Volume: 8; Journal Issue: 1; Journal ID: ISSN 2041-1723
Publisher:
Nature Publishing Group
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; 25 ENERGY STORAGE; batteries

Citation Formats

Canepa, Pieremanuele, Bo, Shou-Hang, Sai Gautam, Gopalakrishnan, Key, Baris, Richards, William D., Shi, Tan, Tian, Yaosen, Wang, Yan, Li, Juchuan, and Ceder, Gerbrand. High magnesium mobility in ternary spinel chalcogenides. United States: N. p., 2017. Web. doi:10.1038/s41467-017-01772-1.
Canepa, Pieremanuele, Bo, Shou-Hang, Sai Gautam, Gopalakrishnan, Key, Baris, Richards, William D., Shi, Tan, Tian, Yaosen, Wang, Yan, Li, Juchuan, & Ceder, Gerbrand. High magnesium mobility in ternary spinel chalcogenides. United States. doi:10.1038/s41467-017-01772-1.
Canepa, Pieremanuele, Bo, Shou-Hang, Sai Gautam, Gopalakrishnan, Key, Baris, Richards, William D., Shi, Tan, Tian, Yaosen, Wang, Yan, Li, Juchuan, and Ceder, Gerbrand. Fri . "High magnesium mobility in ternary spinel chalcogenides". United States. doi:10.1038/s41467-017-01772-1. https://www.osti.gov/servlets/purl/1417619.
@article{osti_1417619,
title = {High magnesium mobility in ternary spinel chalcogenides},
author = {Canepa, Pieremanuele and Bo, Shou-Hang and Sai Gautam, Gopalakrishnan and Key, Baris and Richards, William D. and Shi, Tan and Tian, Yaosen and Wang, Yan and Li, Juchuan and Ceder, Gerbrand},
abstractNote = {Magnesium batteries appear a viable alternative to overcome the safety and energy density limitations faced by current lithium-ion technology. Furthermore, the development of a competitive magnesium battery is plagued by the existing notion of poor magnesium mobility in solids. We demonstrate by using ab initio calculations, nuclear magnetic resonance, and impedance spectroscopy measurements that substantial magnesium ion mobility can indeed be achieved in close-packed frameworks (~ 0.01-0.1 mS cm -1 at 298 K), specifically in the magnesium scandium selenide spinel. Our theoretical predictions also indicate that high magnesium ion mobility is possible in other chalcogenide spinels, opening the door for the realization of other magnesium solid ionic conductors and the eventual development of an all-solid-state magnesium battery.},
doi = {10.1038/s41467-017-01772-1},
journal = {Nature Communications},
number = 1,
volume = 8,
place = {United States},
year = {Fri Nov 24 00:00:00 EST 2017},
month = {Fri Nov 24 00:00:00 EST 2017}
}

Journal Article:
Free Publicly Available Full Text
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Cited by: 2works
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  • Magnesium batteries appear a viable alternative to overcome the safety and energy density limitations faced by current lithium-ion technology. The development of a competitive magnesium battery is plagued by the existing notion of poor magnesium mobility in solids. Here we demonstrate by using ab initio calculations, nuclear magnetic resonance, and impedance spectroscopy measurements that substantial magnesium ion mobility can indeed be achieved in close-packed frameworks (similar to 0.01-0.1 mS cm(-1) at 298 K), specifically in the magnesium scandium selenide spinel. Our theoretical predictions also indicate that high magnesium ion mobility is possible in other chalcogenide spinels, opening the door formore » the realization of other magnesium solid ionic conductors and the eventual development of an all-solid-state magnesium battery.« less
  • The purpose of this work was to study under high pressures (up to 10 GPa) and at room temperature the electrical resistance of binary and ternary chalcogenides with structures of the NiAs and spinel type: CoS, FeS, Cr/sub 2/S/sub 3/, CoCr/sub 2/S/sub 4/, CdCr/sub 2/S/sub 4/ and FeIn/sub 2/Se/sub 4/. The materials were identified by methods of differential-thermal and x-ray phase analyses. The resistance of the polycrystalline powdered substances was measured at room temperature in 7-9 samples of each compound employing solid-phase high-pressure apparatus.
  • Transport of cations in magnesium aluminate spinel due to an applied electric field at approximately 1000 /sup 0/C has been measured by observing changes in elemental concentrations near the cathode and anode surfaces using ion backscattering techniques. The results indicate that magnesium ions are the mobile species at 1000 /sup 0/C and that these ions combine with ambient oxygen at the cathode surface to form a MgO layer. Quantitative interpretation of the data leads to the conclusion that the ionic transference number of spinel becomes approximately 0.5 after treatment in an electric field.
  • We report that ternary metal oxides of type (Me) 2O 3 with the primary metal (Me) constituent being Fe (66 atomic (at.) %) along with the two Lanthanide elements Tb (10 at.%) and Dy (24 at.%) can show excellent semiconducting transport properties. Thin films prepared by pulsed laser deposition at room temperature followed by ambient oxidation showed very high electronic conductivity (>5 × 10 4 S/m) and Hall mobility (>30 cm 2/V-s). These films had an amorphous microstructure which was stable to at least 500 °C and large optical transparency with a direct band gap of 2.85 ± 0.14 eV.more » This material shows emergent semiconducting behavior with significantly higher conductivity and mobility than the constituent insulating oxides. In conclusion, since these results demonstrate a new way to modify the behaviors of transition metal oxides made from unfilled d- and/or f-subshells, a new class of functional transparent conducting oxide materials could be envisioned.« less
  • We have observed magnetic circular dichroism (MCD) in the soft x-ray absorption spectra of the semiconducting ferromagnet CdCr{sub 2}Se{sub 4} and the metallic ferromagnets CuCr{sub 2}S{sub 4} and CuCr{sub 2}Se{sub 4}. The Cr 2p x-ray absorption and MCD spectra show that the d-electron occupancies of the Cr atom in the Cu based Cr sulfide and selenide are not much different from that in the CdCr{sub 2}Se{sub 4} in spite of the different formal valencies Cr{sup 3.5+} and Cr{sup 3+}, respectively. The observed Cu 2p MCD spectra show the existence of small magnetic moments on the Cu sites which are alignedmore » antiparallel to the Cr 3d moment in CuCr{sub 2}S{sub 4} and CuCr{sub 2}Se{sub 4}, consistent with band-structure calculation.« less