Synthesis and Characterization of MgCr2S4 Thiospinel as a Potential Magnesium Cathode

Wustrow, Allison E.; Key, Baris; Phillips, Patrick J.; Sa, Niya; Lipton, Andrew S.; Klie, Robert F.; Vaughey, John T.; Poeppelmeier, Kenneth R.

doi:10.1021/acs.inorgchem.8b01417

Synthesis and Characterization of MgCr2S4 Thiospinel as a Potential Magnesium Cathode

Journal Article · Wed May 23 04:00:00 EDT 2018 · Inorganic Chemistry

DOI:https://doi.org/10.1021/acs.inorgchem.8b01417· OSTI ID:1573919

Wustrow, Allison E. ^[1]; Key, Baris ^[2]; Phillips, Patrick J. ^[3]; Sa, Niya ^[4]; ^[5]; Klie, Robert F. ^[6]; Vaughey, John T. ^[4]; Poeppelmeier, Kenneth R. ^[1]

Northwestern University
ARGONNE NATL LAB
University of Illinois at Chicago
Argonne National Laboratory
BATTELLE (PACIFIC NW LAB)
UNIVERSITY OF ILLINOIS

Magnesium-ion batteries are a promising energy storage technology because of their higher theoretical energy density and lower cost of raw materials. Among the major challenges has been the identification of cathode materials that demonstrate capacities and voltages similar to lithium-ion systems. Thiospinels represent an attractive choice for new Mg-ion cathode materials owing to their interconnected diffusion pathways and demonstrated high cation mobility in numerous systems. Reported magnesium thiospinels, however, contain redox inactive metals such as scandium or indium, or have low voltages, such as MgTi2S4. This article describes the direct synthesis and structural and electrochemical characterization of MgCr2S4, a new thiospinel containing the redox active metal chromium and discusses its physical properties and potential as a magnesium battery cathode. However, as chromium(III) is quite stable against oxidation in sulfides, removing magnesium from the material remains a significant challenge. Early attempts at both chemical and electrochemical demagnesiation are discussed.

Research Organization:: Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)

Sponsoring Organization:: USDOE

DOE Contract Number:: AC05-76RL01830

OSTI ID:: 1573919

Report Number(s):: PNNL-SA-147559

Journal Information:: Inorganic Chemistry, Journal Name: Inorganic Chemistry Journal Issue: 57 Vol. 2018

Country of Publication:: United States

Language:: English

References (33)

Quest for Nonaqueous Multivalent Secondary Batteries: Magnesium and Beyond Muldoon, John; Bucur, Claudiu B.; Gregory, Thomas Chemical Reviews, Vol. 114, Issue 23 https://doi.org/10.1021/cr500049y	journal	October 2014
Mg rechargeable batteries: an on-going challenge Yoo, Hyun Deog; Shterenberg, Ivgeni; Gofer, Yosef Energy & Environmental Science, Vol. 6, Issue 8, p. 2265-2279 https://doi.org/10.1039/c3ee40871j	journal	January 2013
NMR Studies of Cathode Materials for Lithium-Ion Rechargeable Batteries Grey, Clare P.; Dupré, Nicolas Chemical Reviews, Vol. 104, Issue 10 https://doi.org/10.1021/cr020734p	journal	October 2004
The Study of Reversible Magnesium Deposition by In Situ Scanning Tunneling Microscopy Aurbach, D.; Cohen, Y.; Moshkovich, M. Electrochemical and Solid-State Letters, Vol. 4, Issue 8 https://doi.org/10.1149/1.1379828	journal	January 2001
Quantitatively Predict the Potential of MnO ₂ Polymorphs as Magnesium Battery Cathodes Ling, Chen; Zhang, Ruigang; Mizuno, Fuminori ACS Applied Materials & Interfaces, Vol. 8, Issue 7 https://doi.org/10.1021/acsami.5b11460	journal	February 2016
The new JEOL JEM-ARM200CF at the University of Illinois at Chicago: The new JEOL JEM-ARM200CF at the University of Illinois at Chicago Klie, R. F.; Gulec, A.; Guo, Z. Crystal Research and Technology, Vol. 49, Issue 9 https://doi.org/10.1002/crat.201300200	journal	September 2013
Intercalation and Push-Out Process with Spinel-to-Rocksalt Transition on Mg Insertion into Spinel Oxides in Magnesium Batteries Okamoto, Shinya; Ichitsubo, Tetsu; Kawaguchi, Tomoya Advanced Science, Vol. 2, Issue 8 https://doi.org/10.1002/advs.201500072	journal	June 2015
The electronic structure of the metastable layer compound Fang, C. M.; Bruggen, C. F. van; Groot, R. A. de Journal of Physics: Condensed Matter, Vol. 9, Issue 46 https://doi.org/10.1088/0953-8984/9/46/015	journal	November 1997
TiS2 nanotubes as the cathode materials of Mg-ion batteries Tao, Zhan-Liang; Xu, Li-Na; Gou, Xing-Long Chemical Communications, Issue 18 https://doi.org/10.1039/b403855j	journal	January 2004
Untersuchungen �ber tern�re Chalkogenide. II. �ber Die Struktur einiger Chromthiospinelle Hahn, Harry Zeitschrift f�r anorganische und allgemeine Chemie, Vol. 264, Issue 2-4 https://doi.org/10.1002/zaac.19512640213	journal	March 1951
Solid-state magnesium-25 n.m.r. spectroscopy Dupree, R.; Smith, M. E. Journal of the Chemical Society, Chemical Communications, Issue 22 https://doi.org/10.1039/c39880001483	journal	January 1988
Structural Evolution of Reversible Mg Insertion into a Bilayer Structure of V ₂ O ₅ · n H ₂ O Xerogel Material Sa, Niya; Kinnibrugh, Tiffany L.; Wang, Hao Chemistry of Materials, Vol. 28, Issue 9 https://doi.org/10.1021/acs.chemmater.6b00026	journal	April 2016
A systematic study of ²⁵ Mg NMR in paramagnetic transition metal oxides: applications to Mg-ion battery materials Lee, Jeongjae; Seymour, Ieuan D.; Pell, Andrew J. Physical Chemistry Chemical Physics, Vol. 19, Issue 1 https://doi.org/10.1039/C6CP06338A	journal	January 2017
Electrolyte Solutions for Rechargeable Magnesium Batteries Based on Organomagnesium Chloroaluminate Complexes Aurbach, Doron; Gizbar, Haim; Schechter, Alex Journal of The Electrochemical Society, Vol. 149, Issue 2, p. A115-A121 https://doi.org/10.1149/1.1429925	journal	January 2002
Improved capacity retention in rechargeable 4 V lithium/lithium-manganese oxide (spinel) cells Gummow, R. J.; de Kock, A.; Thackeray, M. M. Solid State Ionics, Vol. 69, Issue 1, p. 59-67 https://doi.org/10.1016/0167-2738(94)90450-2	journal	April 1994
Prototype systems for rechargeable magnesium batteries Aurbach, D.; Lu, Z.; Schechter, A. Nature, Vol. 407, Issue 6805, p. 724-727 https://doi.org/10.1038/35037553	journal	October 2000
Direct Observation of Reversible Magnesium Ion Intercalation into a Spinel Oxide Host Kim, Chunjoong; Phillips, Patrick J.; Key, Baris Advanced Materials, Vol. 27, Issue 22 https://doi.org/10.1002/adma.201500083	journal	April 2015
EXPGUI , a graphical user interface for GSAS Toby, Brian H. Journal of Applied Crystallography, Vol. 34, Issue 2 https://doi.org/10.1107/S0021889801002242	journal	April 2001
Chemical intercalation of magnesium into solid hosts Bruce, Peter G.; Krok, Franciszek; Nowinski, Jan Journal of Materials Chemistry, Vol. 1, Issue 4 https://doi.org/10.1039/jm9910100705	journal	January 1991
High magnesium mobility in ternary spinel chalcogenides Canepa, Pieremanuele; Bo, Shou-Hang; Sai Gautam, Gopalakrishnan Nature Communications, Vol. 8, Issue 1 https://doi.org/10.1038/s41467-017-01772-1	journal	November 2017
Electrochemical and Spectroscopic Analysis of Mg ²⁺ Intercalation into Thin Film Electrodes of Layered Oxides: V ₂ O ₅ and MoO ₃ Gershinsky, Gregory; Yoo, Hyun Deog; Gofer, Yosef Langmuir, Vol. 29, Issue 34 https://doi.org/10.1021/la402391f	journal	August 2013
Reversible Magnesium Intercalation into a Layered Oxyfluoride Cathode Incorvati, Jared T.; Wan, Liwen F.; Key, Baris Chemistry of Materials, Vol. 28, Issue 1 https://doi.org/10.1021/acs.chemmater.5b02746	journal	December 2015
Europium chromium sulfide, EuCr2S4, and some isotypic compounds Omloo, W. P. F. A. M.; Bommerson, J. C.; Heikens, H. H. Physica Status Solidi (a), Vol. 5, Issue 2 https://doi.org/10.1002/pssa.2210050208	journal	May 1971
Prediction of A 2 B X 4 metal-chalcogenide compounds via first-principles thermodynamics Zhang, X.; Stevanović, V.; d’Avezac, M. Physical Review B, Vol. 86, Issue 1 https://doi.org/10.1103/PhysRevB.86.014109	journal	July 2012
Evaluation of sulfur spinel compounds for multivalent battery cathode applications Liu, Miao; Jain, Anubhav; Rong, Ziqin Energy & Environmental Science, Vol. 9, Issue 10 https://doi.org/10.1039/C6EE01731B	journal	January 2016
Chromium chalcogenides prepared at high pressure and the crystal growth of chromium sesquisulfide Sleight, Arthur W.; Bither, Tom A. Inorganic Chemistry, Vol. 8, Issue 3 https://doi.org/10.1021/ic50073a032	journal	March 1969
A high capacity thiospinel cathode for Mg batteries Sun, Xiaoqi; Bonnick, Patrick; Duffort, Victor Energy & Environmental Science, Vol. 9, Issue 7 https://doi.org/10.1039/C6EE00724D	journal	January 2016
Study on electrochemically deposited Mg metal Matsui, Masaki Journal of Power Sources, Vol. 196, Issue 16 https://doi.org/10.1016/j.jpowsour.2010.11.141	journal	August 2011
Preparation and Electrical Properties of Some Thiospinels Bouchard, R. J.; Russo, P. A.; Wold, A. Inorganic Chemistry, Vol. 4, Issue 5 https://doi.org/10.1021/ic50027a019	journal	May 1965
Atomic Structural Studies on Thin Single-Crystalline Misfit-Layered Nanotubes of TbS-CrS ₂ Panchakarla, Leela S.; Lajaunie, Luc; Tenne, Reshef The Journal of Physical Chemistry C, Vol. 120, Issue 29 https://doi.org/10.1021/acs.jpcc.5b05811	journal	August 2015
Lanthanide-Based Functional Misfit-Layered Nanotubes Panchakarla, Leela S.; Popovitz-Biro, Ronit; Houben, Lothar Angewandte Chemie International Edition, Vol. 53, Issue 27 https://doi.org/10.1002/anie.201404189	journal	June 2014
Physical Properties and Cation Arrangement of Oxides with Spinel Structures I. Cation Arrangement in Spinels Verwey, E. J. W.; Heilmann, E. L. The Journal of Chemical Physics, Vol. 15, Issue 4 https://doi.org/10.1063/1.1746464	journal	April 1947
Comparative Study of LiNi _0.5 Mn _1.5 O ₄ _- _δ and LiNi _0.5 Mn _1.5 O ₄ Cathodes Having Two Crystallographic Structures: Fd 3̄ m and P 4 ₃ 32 Kim, J. -H.; Myung, S. -T.; Yoon, C. S. Chemistry of Materials, Vol. 16, Issue 5 https://doi.org/10.1021/cm035050s	journal	March 2004

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