Evaluation of sulfur spinel compounds for multivalent battery cathode applications

Liu, Miao; Jain, Anubhav; Rong, Ziqin; Qu, Xiaohui; Canepa, Pieremanuele; Malik, Rahul; Ceder, Gerbrand; Persson, Kristin A.

doi:10.1039/c6ee01731b

Title: Evaluation of sulfur spinel compounds for multivalent battery cathode applications

Journal Article · Wed Aug 17 00:00:00 EDT 2016 · Energy & Environmental Science

DOI:https://doi.org/10.1039/c6ee01731b· OSTI ID:1474969

Liu, Miao ^[1]; Jain, Anubhav ^[1]; Rong, Ziqin ^[2]; Qu, Xiaohui ^[1]; Canepa, Pieremanuele ^[3]; Malik, Rahul ^[2]; Ceder, Gerbrand ^[4]; Persson, Kristin A. ^[5]

Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Electrochemical Technologies Group
Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States). Dept. of Materials Science and Engineering
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Materials Sciences Division
Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States). Dept. of Materials Science and Engineering; Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Materials Sciences Division; Univ. of California, Berkeley, CA (United States). Dept. of Materials Science and Engineering
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Electrochemical Technologies Group; Univ. of California, Berkeley, CA (United States). Dept. of Materials Science and Engineering

The rapid growth of portable consumer electronics and electric vehicles demands new battery technologies with greater energy stored at a reduced cost. Energy storage solutions based on multivalent metals, such as Mg, could significantly increase the energy density as compared to lithium-ion based technology. Here, we employ density functional theory calculations to systematically evaluate the performance, such as thermodynamic stability, ion diffusivity and voltage, of a group of 3d transition-metal sulfur-spinel compounds (21 in total) for multivalent cathode applications. Based on our calculations, Cr₂S₄, Ti₂S₄ and Mn₂S₄ spinel compounds exhibit improved Mg²⁺ mobility (diffusion activation energy <650 meV) relative to their oxide counterparts, however the improved mobility comes at the expense of lower voltage and thereby lower theoretical specific energy. Ca²⁺ intercalating into Cr₂S₄ spinel exhibits a low diffusion activation barrier of 500 meV and a voltage of ~2 V, revealing a potential cathode for use in Ca rechargeable batteries.

View Accepted Manuscript (DOE)

Cite

Export

Save

Research Organization:: Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities Division; USDOE Office of Energy Efficiency and Renewable Energy (EERE)

Grant/Contract Number:: AC02-05CH11231; AC02-06CH11357; EDCBEE

OSTI ID:: 1474969

Journal Information:: Energy & Environmental Science, Vol. 9, Issue 10; Related Information: © 2016 The Royal Society of Chemistry.; ISSN 1754-5692

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

Citation Metrics:

Cited by: 99 works

Citation information provided by
Web of Science

References (50)

Understanding the Initial Stages of Reversible Mg Deposition and Stripping in Inorganic Nonaqueous Electrolytes Canepa, Pieremanuele; Gautam, Gopalakrishnan Sai; Malik, Rahul Chemistry of Materials, Vol. 27, Issue 9 https://doi.org/10.1021/acs.chemmater.5b00389	journal	April 2015
Spinel electrodes for lithium batteries — A review Thackeray, M. M.; de Picciotto, L. A.; de Kock, A. Journal of Power Sources, Vol. 21, Issue 1 https://doi.org/10.1016/0378-7753(87)80071-X	journal	August 1987
Generalized Gradient Approximation Made Simple Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868 https://doi.org/10.1103/PhysRevLett.77.3865	journal	October 1996
Phase Diagram of Mg Insertion into Chevrel Phases, Mg _x Mo ₆ T ₈ (T = S, Se). 2. The Crystal Structure of Triclinic MgMo ₆ Se ₈ Levi, E.; Lancry, E.; Mitelman, A. Chemistry of Materials, Vol. 18, Issue 16 https://doi.org/10.1021/cm060715m	journal	August 2006
Phosphates as Lithium-Ion Battery Cathodes: An Evaluation Based on High-Throughput ab Initio Calculations Hautier, Geoffroy; Jain, Anubhav; Ong, Shyue Ping Chemistry of Materials, Vol. 23, Issue 15 https://doi.org/10.1021/cm200949v	journal	August 2011
Materials Design Rules for Multivalent Ion Mobility in Intercalation Structures Rong, Ziqin; Malik, Rahul; Canepa, Pieremanuele Chemistry of Materials, Vol. 27, Issue 17 https://doi.org/10.1021/acs.chemmater.5b02342	journal	August 2015
A review on the problems of the solid state ions diffusion in cathodes for rechargeable Mg batteries Levi, E.; Levi, M. D.; Chasid, O. Journal of Electroceramics, Vol. 22, Issue 1-3 https://doi.org/10.1007/s10832-007-9370-5	journal	December 2007
The Principles Determining the Structure of Complex Ionic Crystals Pauling, Linus Journal of the American Chemical Society, Vol. 51, Issue 4 https://doi.org/10.1021/ja01379a006	journal	April 1929
First-principles evaluation of multi-valent cation insertion into orthorhombic V ₂ O ₅ Gautam, Gopalakrishnan Sai; Canepa, Pieremanuele; Malik, Rahul Chemical Communications, Vol. 51, Issue 71 https://doi.org/10.1039/C5CC04947D	journal	January 2015
Mg Intercalation in Layered and Spinel Host Crystal Structures for Mg Batteries Emly, Alexandra; Van der Ven, Anton Inorganic Chemistry, Vol. 54, Issue 9 https://doi.org/10.1021/acs.inorgchem.5b00188	journal	April 2015
Elucidating the structure of the magnesium aluminum chloride complex electrolyte for magnesium-ion batteries Canepa, Pieremanuele; Jayaraman, Saivenkataraman; Cheng, Lei Energy & Environmental Science, Vol. 8, Issue 12 https://doi.org/10.1039/C5EE02340H	journal	January 2015
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
Phase stability and nondilute Li diffusion in spinel ${Li}_{1 + x} {Ti}_{2} O_{4}$ Bhattacharya, Jishnu; Van der Ven, Anton Physical Review B, Vol. 81, Issue 10 https://doi.org/10.1103/PhysRevB.81.104304	journal	March 2010
Spinel compounds as multivalent battery cathodes: a systematic evaluation based on ab initio calculations Liu, Miao; Rong, Ziqin; Malik, Rahul Energy & Environmental Science, Vol. 8, Issue 3 https://doi.org/10.1039/C4EE03389B	journal	January 2015
Interlayer-Expanded Molybdenum Disulfide Nanocomposites for Electrochemical Magnesium Storage Liang, Yanliang; Yoo, Hyun Deog; Li, Yifei Nano Letters, Vol. 15, Issue 3 https://doi.org/10.1021/acs.nanolett.5b00388	journal	February 2015
Phase Diagram of Mg Insertion into Chevrel Phases, Mg _x Mo ₆ T ₈ (T = S, Se). 1. Crystal Structure of the Sulfides Levi, E.; Lancry, E.; Mitelman, A. Chemistry of Materials, Vol. 18, Issue 23 https://doi.org/10.1021/cm061656f	journal	November 2006
Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set Kresse, G.; Furthmüller, J. Physical Review B, Vol. 54, Issue 16, p. 11169-11186 https://doi.org/10.1103/PhysRevB.54.11169	journal	October 1996
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
Thermal stabilities of delithiated olivine MPO4 (M=Fe, Mn) cathodes investigated using first principles calculations Ong, Shyue Ping; Jain, Anubhav; Hautier, Geoffroy Electrochemistry Communications, Vol. 12, Issue 3 https://doi.org/10.1016/j.elecom.2010.01.010	journal	March 2010
First-Principles Prediction of Insertion Potentials in Li-Mn Oxides for Secondary Li Batteries Aydinol, M. K. Journal of The Electrochemical Society, Vol. 144, Issue 11 https://doi.org/10.1149/1.1838099	journal	January 1997
Rechargeable Mg Batteries with Graphene-like MoS2 Cathode and Ultrasmall Mg Nanoparticle Anode Liang, Yanliang; Feng, Rujun; Yang, Siqi Advanced Materials, Vol. 23, Issue 5 https://doi.org/10.1002/adma.201003560	journal	December 2010
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
Spinel Electrodes from the Li-Mn-O System for Rechargeable Lithium Battery Applications Thackeray, M. M. Journal of The Electrochemical Society, Vol. 139, Issue 2 https://doi.org/10.1149/1.2069222	journal	January 1992
Commentary: The Materials Project: A materials genome approach to accelerating materials innovation Jain, Anubhav; Ong, Shyue Ping; Hautier, Geoffroy APL Materials, Vol. 1, Issue 1 https://doi.org/10.1063/1.4812323	journal	July 2013
The reaction of lithium with CuCr2S4—lithium intercalation and copper displacement/extrusion Bodenez, V.; Dupont, L.; Laffont, L. Journal of Materials Chemistry, Vol. 17, Issue 30 https://doi.org/10.1039/b703895j	journal	January 2007
Lithium insertion into manganese spinels Thackeray, M. M.; David, W. I. F.; Bruce, P. G. Materials Research Bulletin, Vol. 18, Issue 4, p. 461-472 https://doi.org/10.1016/0025-5408(83)90138-1	journal	April 1983
Particle Size Dependence of the Ionic Diffusivity Malik, Rahul; Burch, Damian; Bazant, Martin Nano Letters, Vol. 10, Issue 10 https://doi.org/10.1021/nl1023595	journal	October 2010
Ab initio study of lithium intercalation in metal oxides and metal dichalcogenides Aydinol, M. K.; Kohan, A. F.; Ceder, G. Physical Review B, Vol. 56, Issue 3 https://doi.org/10.1103/PhysRevB.56.1354	journal	July 1997
Rechargeable batteries with aqueous electrolytes Beck, Fritz; Rüetschi, Paul Electrochimica Acta, Vol. 45, Issue 15-16 https://doi.org/10.1016/S0013-4686(00)00344-3	journal	May 2000
The Coupling between Stability and Ion Pair Formation in Magnesium Electrolytes from First-Principles Quantum Mechanics and Classical Molecular Dynamics Rajput, Nav Nidhi; Qu, Xiaohui; Sa, Niya Journal of the American Chemical Society, Vol. 137, Issue 9, p. 3411-3420 https://doi.org/10.1021/jacs.5b01004	journal	February 2015
Li−Fe−P−O ₂ Phase Diagram from First Principles Calculations Ong, Shyue Ping; Wang, Lei; Kang, Byoungwoo Chemistry of Materials, Vol. 20, Issue 5 https://doi.org/10.1021/cm702327g	journal	February 2008
What factors determine cation coordination numbers? Brown, I. D. Acta Crystallographica Section B Structural Science, Vol. 44, Issue 6 https://doi.org/10.1107/S0108768188007712	journal	December 1988
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
Formation enthalpies by mixing GGA and GGA $+$ $U$ calculations Jain, Anubhav; Hautier, Geoffroy; Ong, Shyue Ping Physical Review B, Vol. 84, Issue 4 https://doi.org/10.1103/PhysRevB.84.045115	journal	July 2011
Analysis of Charged State Stability for Monoclinic LiMnBO ₃ Cathode Kim, Jae Chul; Li, Xin; Moore, Charles J. Chemistry of Materials, Vol. 26, Issue 14 https://doi.org/10.1021/cm5014174	journal	July 2014
Atoms, molecules, solids, and surfaces: Applications of the generalized gradient approximation for exchange and correlation Perdew, John P.; Chevary, J. A.; Vosko, S. H. Physical Review B, Vol. 46, Issue 11 https://doi.org/10.1103/PhysRevB.46.6671	journal	September 1992
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
Structure of the cubic intercalate Mg x TiS2 Lightfoot, Philip; Krok, Franciszek; Nowinski, Jan L. Journal of Materials Chemistry, Vol. 2, Issue 1 https://doi.org/10.1039/jm9920200139	journal	January 1992
A climbing image nudged elastic band method for finding saddle points and minimum energy paths Henkelman, Graeme; Uberuaga, Blas P.; Jónsson, Hannes The Journal of Chemical Physics, Vol. 113, Issue 22, p. 9901-9904 https://doi.org/10.1063/1.1329672	journal	December 2000
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
Ion-Exchange Mechanism of Layered Transition-Metal Oxides: Case Study of LiNi _0.5 Mn _0.5 O ₂ Gwon, Hyeokjo; Kim, Sung-Wook; Park, Young-Uk Inorganic Chemistry, Vol. 53, Issue 15 https://doi.org/10.1021/ic501069x	journal	July 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
Pressure-Temperature Study of Sulfospinels Tressler, R. E.; Hummel, F. A.; Stubican, V. S. Journal of the American Ceramic Society, Vol. 51, Issue 11 https://doi.org/10.1111/j.1151-2916.1968.tb12637.x	journal	November 1968
Mg Desolvation and Intercalation Mechanism at the Mo ₆ S ₈ Chevrel Phase Surface Wan, Liwen F.; Perdue, Brian R.; Apblett, Christopher A. Chemistry of Materials, Vol. 27, Issue 17 https://doi.org/10.1021/acs.chemmater.5b01907	journal	August 2015
The Intercalation Phase Diagram of Mg in V ₂ O ₅ from First-Principles Sai Gautam, Gopalakrishnan; Canepa, Pieremanuele; Abdellahi, Aziz Chemistry of Materials, Vol. 27, Issue 10 https://doi.org/10.1021/acs.chemmater.5b00957	journal	May 2015
Self-Consistent Equations Including Exchange and Correlation Effects Kohn, W.; Sham, L. J. Physical Review, Vol. 140, Issue 4A, p. A1133-A1138 https://doi.org/10.1103/PhysRev.140.A1133	journal	November 1965
Phosphates as Lithium-Ion Battery Cathodes: An Evaluation Based on High-Throughput Ab Initio Calculations Hautier, Geoffroy; Jain, Anubhav; Ong, Shyue Ping ECS Meeting Abstracts, Vol. MA2011-02, Issue 12 https://doi.org/10.1149/ma2011-02/12/668	journal	August 2011
Understanding the Initial Stages of Reversible Mg Deposition and Stripping in Inorganic Non-Aqueous Electrolytes Canepa, Pieremanuele; Gautam, Gopalakrishnan Sai; Malik, Rahul arXiv https://doi.org/10.48550/arxiv.1504.07409	text	January 2015
The intercalation phase diagram of Mg in V$_2$O$_5$ from first principles Gautam, Gopalakrishnan Sai; Canepa, Pieremanuele; Abdellahi, Aziz arXiv https://doi.org/10.48550/arxiv.1505.07731	text	January 2015
Elucidating the Structure of the Magnesium Aluminum Chloride Complex electrolyte for Magnesium-ion batteries Canepa, Pieremanuele; Jayaraman, Saivenkataraman; Cheng, Lei arXiv https://doi.org/10.48550/arxiv.1511.02504	text	January 2015

Cited By (15)

Paving the Path toward Reliable Cathode Materials for Aluminum-Ion Batteries Wu, Feng; Yang, Haoyi; Bai, Ying Advanced Materials, Vol. 31, Issue 16 https://doi.org/10.1002/adma.201806510	journal	February 2019
Fervent Hype behind Magnesium Batteries: An Open Call to Synthetic Chemists-Electrolytes and Cathodes Needed Muldoon, John; Bucur, Claudiu B.; Gregory, Thomas Angewandte Chemie International Edition, Vol. 56, Issue 40 https://doi.org/10.1002/anie.201700673	journal	August 2017
Sulfur‐ and Selenium‐Containing Compounds Potentially Exhibiting Al Ion Conductivity Meutzner, Falk; Zschornak, Matthias; Kabanov, Artem A. Chemistry – A European Journal, Vol. 25, Issue 36 https://doi.org/10.1002/chem.201901438	journal	May 2019
Microstructure Characteristics of Cathode Materials for Rechargeable Magnesium Batteries Li, Zhuo; Han, Lu; Wang, Yongfei Small, Vol. 15, Issue 32 https://doi.org/10.1002/smll.201900105	journal	March 2019
Magnesium Storage Performance and Mechanism of 2D‐Ultrathin Nanosheet‐Assembled Spinel MgIn ₂ S ₄ Cathode for High‐Temperature Mg Batteries Zhang, Yong; Konya, Masashi; Kutsuma, Ayaka Small, Vol. 15, Issue 36 https://doi.org/10.1002/smll.201902236	journal	July 2019
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
Analysis of Minerals as Electrode Materials for Ca-based Rechargeable Batteries Torres, A.; Luque, F. J.; Tortajada, J. Scientific Reports, Vol. 9, Issue 1 https://doi.org/10.1038/s41598-019-46002-4	journal	July 2019
Ab initio study of Li, Mg and Al insertion into rutile VO ₂ : fast diffusion and enhanced voltages for multivalent batteries Kulish, Vadym V.; Koch, Daniel; Manzhos, Sergei Physical Chemistry Chemical Physics, Vol. 19, Issue 33 https://doi.org/10.1039/c7cp04360k	journal	January 2017
Exploring the sodium ion storage mechanism of gallium sulfide (Ga ₂ S ₃ ): a combined experimental and theoretical approach Wang, Pei; Liu, Miao; Mo, Fangjie Nanoscale, Vol. 11, Issue 7 https://doi.org/10.1039/c8nr09356c	journal	January 2019
Towards Al ³⁺ Mobility in Crystalline Solids: Critical Review and Analysis Nestler, Tina; Fedotov, Stanislav; Leisegang, Tilmann Critical Reviews in Solid State and Materials Sciences, Vol. 44, Issue 4 https://doi.org/10.1080/10408436.2018.1490248	journal	April 2019
On the Reliability of Half-Cell Tests for Monovalent (Li ⁺ , Na ⁺ ) and Divalent (Mg ²⁺ , Ca ²⁺ ) Cation Based Batteries Tchitchekova, D. S.; Monti, D.; Johansson, P. Journal of The Electrochemical Society, Vol. 164, Issue 7 https://doi.org/10.1149/2.0411707jes	journal	January 2017
Insertion of Mono- vs. Bi- vs. Trivalent Atoms in Prospective Active Electrode Materials for Electrochemical Batteries: An ab Initio Perspective Kulish, Vadym; Koch, Daniel; Manzhos, Sergei Energies, Vol. 10, Issue 12 https://doi.org/10.3390/en10122061	journal	December 2017
Mg6MnO8 as a Magnesium-Ion Battery Material: Defects, Dopants and Mg-Ion Transport Kuganathan, Navaratnarajah; Gkanas, Evangelos I.; Chroneos, Alexander Energies, Vol. 12, Issue 17 https://doi.org/10.3390/en12173213	journal	August 2019
Copper sulfide nanoparticles as high-performance cathode materials for Mg-ion batteries Kravchyk, Kostiantyn V.; Widmer, Roland; Erni, Rolf ETH Zurich https://doi.org/10.3929/ethz-b-000347619	text	January 2019
On the Balance of Intercalation and Conversion Reactions in Battery Cathodes Hannah, Daniel C.; Gautam, Gopalakrishnan Sai; Canepa, Pieremanuele arXiv https://doi.org/10.48550/arxiv.1804.06704	text	January 2018

Similar Records

Spinel compounds as multivalent battery cathodes: A systematic evaluation based on ab initio calculations

Journal Article · Tue Dec 16 00:00:00 EST 2014 · Energy & Environmental Science · OSTI ID:1474969

Liu, Miao; Rong, Ziqin; Malik, Rahul; +4 more

Expanding the Material Search Space for Multivalent Cathodes

Journal Article · Thu Sep 22 00:00:00 EDT 2022 · ACS Applied Materials and Interfaces · OSTI ID:1474969

Rutt, Ann; Shen, Jimmy-Xuan; Horton, Matthew; +3 more

2D Ni_0.25Mn_0.75O₂: A high-performance cathode for multivalent ion batteries

Journal Article · Sat Oct 23 00:00:00 EDT 2021 · Computational Materials Science · OSTI ID:1474969

Liepinya, Diana; Shepard, Robert; Smeu, Manuel

Related Subjects

25 ENERGY STORAGE
36 MATERIALS SCIENCE

Title: Evaluation of sulfur spinel compounds for multivalent battery cathode applications

Citation Formats

References (50)

Cited By (15)

Similar Records

Related Subjects