Temperature-Dependent Reaction Pathways in FeS2: Reversibility and the Electrochemical Formation of Fe3S4

Whang, Grace; Ashby, David S.; Lapp, Aliya S.; Hsieh, Yi-Chieh; Butts, Danielle M.; Kolesnichenko, Igor V.; Wu, Pu-Wei; Lambert, Timothy N.; Talin, A. Alec; Dunn, Bruce S.

doi:10.1021/acs.chemmater.2c00291

Temperature-Dependent Reaction Pathways in FeS₂: Reversibility and the Electrochemical Formation of Fe₃S₄

Journal Article · Thu Jun 09 00:00:00 EDT 2022 · Chemistry of Materials

DOI:https://doi.org/10.1021/acs.chemmater.2c00291· OSTI ID:1872065

^[1]; Ashby, David S. ^[2]; Lapp, Aliya S. ^[2]; Hsieh, Yi-Chieh ^[3]; ^[1]; ^[4]; ^[3]; ^[4]; ^[2]; ^[1]

Univ. of California, Los Angeles, CA (United States)
Sandia National Lab. (SNL-CA), Livermore, CA (United States)
National Chiao Tung Univ., Hsinchu (Taiwan)
Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)

The present study has used a variety of characterization techniques to determine the products and reaction pathways involved in the rechargeable Li–FeS₂ system. We revisit both the initial lithiation and subsequent cycling of FeS₂ employing an ionic liquid electrolyte to investigate the intermediate and final charge products formed under varying thermal conditions (room temperature to 100 °C). The detection of Li₂S and hexagonal FeS as the intermediate phases in the initial lithiation and the electrochemical formation of greigite, Fe₃S₄, as a charge product in the rechargeable reaction differ significantly from previous reports. The conditions for Fe₃S₄ formation are shown to be dependent on both the temperature (~60 °C) and the availability of sulfur to drive a FeS to Fe₃S₄ transformation. Upon further cycling, Fe₃S₄ transforms to a lower sulfur content iron sulfide phase, a process which coincides with the loss of sulfur based on the new reaction pathways established in this work. The connection between sulfur loss, capacity fade, and charge product composition highlights the critical need to retain sulfur in the active material upon cycling.

View Accepted Manuscript (DOE)

Research Organization:: Sandia National Laboratories (SNL-NM), Albuquerque, NM (United States); Sandia National Laboratories,, Livermore, CA

Sponsoring Organization:: USDOE National Nuclear Security Administration (NNSA)

Grant/Contract Number:: NA0003525

OSTI ID:: 1872065

Report Number(s):: SAND2022-7862J; 707210

Journal Information:: Chemistry of Materials, Journal Name: Chemistry of Materials Journal Issue: 12 Vol. 34; ISSN 0897-4756

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

References (47)

Beyond Intercalation-Based Li-Ion Batteries: The State of the Art and Challenges of Electrode Materials Reacting Through Conversion Reactions Cabana, Jordi; Monconduit, Laure; Larcher, Dominique Advanced Materials, Vol. 22, Issue 35 https://doi.org/10.1002/adma.201000717	journal	August 2010
Ionic Liquid Enabled FeS ₂ for High-Energy-Density Lithium-Ion Batteries Evans, Tyler; Piper, Daniela Molina; Kim, Seul Cham Advanced Materials, Vol. 26, Issue 43 https://doi.org/10.1002/adma.201402103	journal	September 2014
Solid State Enabled Reversible Four Electron Storage Yersak, Thomas A.; Macpherson, H. Alex; Kim, Seul Cham Advanced Energy Materials, Vol. 3, Issue 1 https://doi.org/10.1002/aenm.201200267	journal	August 2012
Influence of Iron Sulfide Nanoparticle Sizes in Solid‐State Batteries** Dewald, Georg F.; Liaqat, Zainab; Lange, Martin Alexander Angewandte Chemie, Vol. 133, Issue 33 https://doi.org/10.1002/ange.202106018	journal	July 2021
Reaction pathways in the Fe–S system below 100°C Benning, Liane G.; Wilkin, Rick T.; Barnes, H. L. Chemical Geology, Vol. 167, Issue 1-2 https://doi.org/10.1016/S0009-2541(99)00198-9	journal	June 2000
Electrochemical lithiation and passivation mechanisms of iron monosulfide thin film as negative electrode material for lithium-ion batteries studied by surface analytical techniques Liao, Feng; Światowska, Jolanta; Maurice, Vincent Applied Surface Science, Vol. 283 https://doi.org/10.1016/j.apsusc.2013.07.039	journal	October 2013
Perfect reversibility of the lithium insertion in FeS2: The combined effects of all-solid-state and thin film cell configurations Pelé, V.; Flamary, F.; Bourgeois, L. Electrochemistry Communications, Vol. 51 https://doi.org/10.1016/j.elecom.2014.12.009	journal	February 2015
Structure analyses of Fe-substituted Li2S-based positive electrode materials for Li-S batteries Takeuchi, Tomonari; Kageyama, Hiroyuki; Taguchi, Noboru Solid State Ionics, Vol. 320 https://doi.org/10.1016/j.ssi.2018.03.028	journal	July 2018
Alkylammonium-Intercalated 2D Mackinawite FeS as Electrode Materials for Rechargeable Batteries Lim, Hyungsub; Pham, Duy Tho; Jung, Jong Hyun Chemistry of Materials, Vol. 32, Issue 21 https://doi.org/10.1021/acs.chemmater.0c02308	journal	October 2020
Local Structure Evolution and Modes of Charge Storage in Secondary Li–FeS ₂ Cells Butala, Megan M.; Mayo, Martin; Doan-Nguyen, Vicky V. T. Chemistry of Materials, Vol. 29, Issue 7 https://doi.org/10.1021/acs.chemmater.7b00070	journal	March 2017
In Situ Chemical Imaging of Solid-Electrolyte Interphase Layer Evolution in Li–S Batteries Nandasiri, Manjula I.; Camacho-Forero, Luis E.; Schwarz, Ashleigh M. Chemistry of Materials, Vol. 29, Issue 11 https://doi.org/10.1021/acs.chemmater.7b00374	journal	May 2017
In Situ UV–Vis Analysis of Polysulfide Shuttling in Ionic Liquid-Based Li-FeS₂ Batteries Lapp, Aliya S.; Whang, Grace; Bhandarkar, Austin The Journal of Physical Chemistry C, Vol. 126, Issue 11 https://doi.org/10.1021/acs.jpcc.1c10074	journal	March 2022
Sulfur-Embedded FeS ₂ as a High-Performance Cathode for Room Temperature All-Solid-State Lithium–Sulfur Batteries Mwizerwa, Jean Pierre; Zhang, Qiang; Han, Fudong ACS Applied Materials & Interfaces, Vol. 12, Issue 16 https://doi.org/10.1021/acsami.0c01607	journal	March 2020
Unraveling the Reaction Mechanism of FeS ₂ as a Li-Ion Battery Cathode Zou, Jian; Zhao, Jun; Wang, Bojun ACS Applied Materials & Interfaces, Vol. 12, Issue 40 https://doi.org/10.1021/acsami.0c14082	journal	September 2020
Elucidating the Mechanism of Li Insertion into Fe_1–xS/Carbon via In Operando Synchrotron Studies Li, Chengping; Sarapulova, Angelina; Pfeifer, Kristina ACS Applied Materials & Interfaces, Vol. 12, Issue 47 https://doi.org/10.1021/acsami.0c15500	journal	November 2020
Stable Cycling of Lithium Batteries Utilizing Iron Disulfide Nanoparticles Schorr, By Noah B.; Kolesnichenko, Igor V.; Merrill, Laura C. ACS Applied Nano Materials, Vol. 4, Issue 11 https://doi.org/10.1021/acsanm.1c02178	journal	November 2021
Activating Li ₂ S as the Lithium-Containing Cathode in Lithium–Sulfur Batteries Ye, Hualin; Li, Matthew; Liu, Tongchao ACS Energy Letters, Vol. 5, Issue 7 https://doi.org/10.1021/acsenergylett.0c00936	journal	June 2020
Transitional Metal Catalytic Pyrite Cathode Enables Ultrastable Four-Electron-Based All-Solid-State Lithium Batteries Wan, Hongli; Liu, Gaozhan; Li, Yanle ACS Nano, Vol. 13, Issue 8 https://doi.org/10.1021/acsnano.9b04538	journal	July 2019
Charge Transport and Electrochemical Properties of Colloidal Greigite (Fe ₃ S ₄ ) Nanoplatelets Paolella, Andrea; George, Chandramohan; Povia, Mauro Chemistry of Materials, Vol. 23, Issue 16 https://doi.org/10.1021/cm201531h	journal	August 2011
High-Purity Fe ₃ S ₄ Greigite Microcrystals for Magnetic and Electrochemical Performance Li, Guowei; Zhang, Baomin; Yu, Feng Chemistry of Materials, Vol. 26, Issue 20 https://doi.org/10.1021/cm501493m	journal	October 2014
Nonaqueous Liquid Electrolytes for Lithium-Based Rechargeable Batteries Xu, Kang Chemical Reviews, Vol. 104, Issue 10, p. 4303-4418 https://doi.org/10.1021/cr030203g	journal	October 2004
Chemistry of Iron Sulfides Rickard, David; Luther, George W. Chemical Reviews, Vol. 107, Issue 2 https://doi.org/10.1021/cr0503658	journal	February 2007
Ultimate Limits to Intercalation Reactions for Lithium Batteries Whittingham, M. Stanley Chemical Reviews, Vol. 114, Issue 23 https://doi.org/10.1021/cr5003003	journal	October 2014
Electrochemical Insertion of Lithium into Pyrite from Nonaqueous Electrolytes at Room Temperature: An in Situ Fe K-Edge X-ray Absorption Fine Structure Study Tryk, Donald A.; Kim, Sunghyun; Hu, Yining The Journal of Physical Chemistry, Vol. 99, Issue 11 https://doi.org/10.1021/j100011a047	journal	March 1995
An iron-57 Moessbauer study of the intermediates formed in the reduction of iron disulfide in the lithium/iron disulfide battery system Jones, C. H. W.; Kovacs, P. E.; Sharma, R. D. The Journal of Physical Chemistry, Vol. 95, Issue 2 https://doi.org/10.1021/j100155a053	journal	January 1991
Lithium Insertion into Transition-Metal Monosulfides: Tuning the Position of the Metal 4s Band Kim, Youngsik; Goodenough, John B. The Journal of Physical Chemistry C, Vol. 112, Issue 38 https://doi.org/10.1021/jp8038847	journal	August 2008
Magnetic properties of sedimentary greigite (Fe ₃ S ₄ ): An update Roberts, Andrew P.; Chang, Liao; Rowan, Christopher J. Reviews of Geophysics, Vol. 49, Issue 1 https://doi.org/10.1029/2010RG000336	journal	January 2011
Electric cars and batteries: how will the world produce enough? Castelvecchi, Davide Nature, Vol. 596, Issue 7872 https://doi.org/10.1038/d41586-021-02222-1	journal	August 2021
Performance and cost of materials for lithium-based rechargeable automotive batteries Schmuch, Richard; Wagner, Ralf; Hörpel, Gerhard Nature Energy, Vol. 3, Issue 4 https://doi.org/10.1038/s41560-018-0107-2	journal	April 2018
Cutting cobalt Dean, Nicky; Wright, Allison Nature Energy, Vol. 5, Issue 11, p. 825-825 https://doi.org/10.1038/s41560-020-00731-3	journal	November 2020
High-purity iron pyrite (FeS ₂ ) nanowires as high-capacity nanostructured cathodes for lithium-ion batteries Li, Linsen; Cabán-Acevedo, Miguel; Girard, Steven N. Nanoscale, Vol. 6, Issue 4 https://doi.org/10.1039/C3NR05851D	journal	January 2014
Electroanalytical study of the viability of conversion reactions as energy storage mechanisms Ponrouch, Alexandre; Cabana, Jordi; Dugas, Romain RSC Adv., Vol. 4, Issue 68 https://doi.org/10.1039/C4RA05189K	journal	January 2014
Exploiting XPS for the identification of sulfides and polysulfides Fantauzzi, Marzia; Elsener, Bernhard; Atzei, Davide RSC Advances, Vol. 5, Issue 93 https://doi.org/10.1039/C5RA14915K	journal	January 2015
The redox mechanism of FeS ₂ in non-aqueous electrolytes for lithium and sodium batteries Zhang, Sheng S. Journal of Materials Chemistry A, Vol. 3, Issue 15 https://doi.org/10.1039/C5TA00623F	journal	January 2015
FeS ₂ microspheres with an ether-based electrolyte for high-performance rechargeable lithium batteries Hu, Zhe; Zhang, Kai; Zhu, Zhiqiang Journal of Materials Chemistry A, Vol. 3, Issue 24 https://doi.org/10.1039/C5TA02169C	journal	January 2015
Superconductivity and magnetism in iron sulfides intercalated by metal hydroxides Zhou, Xiuquan; Eckberg, Christopher; Wilfong, Brandon Chemical Science, Vol. 8, Issue 5 https://doi.org/10.1039/C6SC05268A	journal	January 2017
Energy efficiency: a critically important but neglected factor in battery research Eftekhari, Ali Sustainable Energy & Fuels, Vol. 1, Issue 10 https://doi.org/10.1039/C7SE00350A	journal	January 2017
Adapting FeS₂ micron particles as an electrode material for lithium-ion batteries via simultaneous construction of CNT internal networks and external cages Lu, Jianhao; Lian, Fang; Guan, Liangliang Journal of Materials Chemistry A, Vol. 7, Issue 3 https://doi.org/10.1039/C8TA09955C	journal	January 2019
Synthesis, modular composition, and electrochemical properties of lamellar iron sulfides Horwitz, Noah E.; Shevchenko, Elena V.; Park, Jehee Journal of Materials Chemistry A https://doi.org/10.1039/D0TA00689K	journal	January 2020
Greigite (Fe ₃ S ₄ ) is thermodynamically stable: Implications for its terrestrial and planetary occurrence Subramani, Tamilarasan; Lilova, Kristina; Abramchuk, Mykola Proceedings of the National Academy of Sciences, Vol. 117, Issue 46 https://doi.org/10.1073/pnas.2017312117	journal	November 2020
Fe K-edge x-ray absorption spectroscopy of corrosion phases of archaeological iron: results, limitations, and the need for complementary techniques Simon, Hayley; Cibin, Giannantonio; Freestone, Ian Journal of Physics: Condensed Matter, Vol. 33, Issue 34 https://doi.org/10.1088/1361-648X/ac08b6	journal	July 2021
Reinvestigation of Lithium Reaction Mechanisms in FeS[sub 2] Pyrite at Ambient Temperature Shao-Horn, Yang; Osmialowski, Steve; Horn, Quinn C. Journal of The Electrochemical Society, Vol. 149, Issue 12 https://doi.org/10.1149/1.1516772	journal	January 2002
Electrochemistry of Pyrite-Based Cathodes for Ambient Temperature Lithium Batteries Fong, Rosamaría Journal of The Electrochemical Society, Vol. 136, Issue 11 https://doi.org/10.1149/1.2096426	journal	January 1989
Elucidating the Electrochemical Activity of Electrolyte-Insoluble Polysulfide Species in Lithium-Sulfur Batteries Klein, Michael J.; Goossens, Karel; Bielawski, Christopher W. Journal of The Electrochemical Society, Vol. 163, Issue 9 https://doi.org/10.1149/2.0051610jes	journal	January 2016
Greigite: a true intermediate on the polysulfide pathway to pyrite Hunger, Stefan; Benning, Liane G. Geochemical Transactions, Vol. 8, Issue 1 https://doi.org/10.1186/1467-4866-8-1	journal	March 2007
FeS2 encapsulated with mesoporous carbon for high-performance lithium-ion batteries Liu, Heguang; Jing, Ruixuan; Wang, Zilu MRS Communications, Vol. 11, Issue 4 https://doi.org/10.1557/s43579-021-00048-6	journal	June 2021
The structure of disordered mackinawite Wolthers, Mariëtte; Van der Gaast, Sjierk J.; Rickard, David American Mineralogist, Vol. 88, Issue 11-12 https://doi.org/10.2138/am-2003-11-1245	journal	November 2003

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