Understanding the Electrochemical Performance of FeS2 Conversion Cathodes

Ashby, David S.; Horner, Jeffrey S.; Whang, Grace; Lapp, Aliya S.; Roberts, Scott A.; Dunn, Bruce; Kolesnichenko, Igor V.; Lambert, Timothy N.; Talin, A. Alec

doi:10.1021/acsami.2c01021

Understanding the Electrochemical Performance of FeS₂ Conversion Cathodes

Journal Article · Mon Jun 06 00:00:00 EDT 2022 · ACS Applied Materials and Interfaces

DOI:https://doi.org/10.1021/acsami.2c01021· OSTI ID:1883186

^[1]; Horner, Jeffrey S. ^[2]; ^[3]; Lapp, Aliya S. ^[1]; ^[2]; ^[3]; ^[2]; ^[2]; ^[1]

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

Conversion cathodes represent a viable route to improve rechargeable Li⁺ battery energy densities, but their poor electrochemical stability and power density have impeded their practical implementation. Here, we explore the impact cell fabrication, electrolyte interaction, and current density have on the electrochemical performance of FeS₂/Li cells by deconvoluting the contributions of the various conversion and intercalation reactions to the overall capacity. By varying the slurry composition and applied pressure, we determine that the capacity loss is primarily due to the large volume changes during (de)lithiation, leading to a degradation of the conductive matrix. Through the application of an external pressure, the loss is minimized by maintaining the conductive matrix. Further, we determine that polysulfide loss can be minimized by increasing the current density (>C/10), thus reducing the sulfur formation period. Analysis of the kinetics determines that the conversion reactions are rate-limiting, specifically the formation of metallic iron at rates above C/8. While focused on FeS₂, our findings on the influence of pressure, electrolyte interaction, and kinetics are broadly applicable to other conversion cathode systems.

View Accepted Manuscript (DOE)

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

Sponsoring Organization:: USDOE Laboratory Directed Research and Development (LDRD) Program; USDOE National Nuclear Security Administration (NNSA)

Grant/Contract Number:: NA0003525

OSTI ID:: 1883186

Report Number(s):: SAND2022-6490J; 706093

Journal Information:: ACS Applied Materials and Interfaces, Journal Name: ACS Applied Materials and Interfaces Journal Issue: 23 Vol. 14; ISSN 1944-8244

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

References (39)

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
High‐Safety and High‐Energy‐Density Lithium Metal Batteries in a Novel Ionic‐Liquid Electrolyte Sun, Hao; Zhu, Guanzhou; Zhu, Yuanmin Advanced Materials, Vol. 32, Issue 26 https://doi.org/10.1002/adma.202001741	journal	May 2020
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
Defect Engineering for Expediting Li–S Chemistry: Strategies, Mechanisms, and Perspectives Shi, Zixiong; Li, Matthew; Sun, Jingyu Advanced Energy Materials, Vol. 11, Issue 23 https://doi.org/10.1002/aenm.202100332	journal	May 2021
Silicon-Based Anodes for Lithium-Ion Batteries: From Fundamentals to Practical Applications Feng, Kun; Li, Matthew; Liu, Wenwen Small, Vol. 14, Issue 8 https://doi.org/10.1002/smll.201702737	journal	January 2018
Accelerated polysulfide redox kinetics revealed by ternary sandwich-type S@Co/N-doped carbon nanosheet for high-performance lithium-sulfur batteries Zhong, Mei-e; Guan, Jindiao; Feng, Qiuju Carbon, Vol. 128 https://doi.org/10.1016/j.carbon.2017.11.084	journal	March 2018
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
Carbon shelled porous SnO2-δ nanosheet arrays as advanced anodes for lithium-ion batteries Jia, Rong; Yue, Jili; Xia, Qiuying Energy Storage Materials, Vol. 13 https://doi.org/10.1016/j.ensm.2018.02.009	journal	July 2018
Improving poisoning resistance of electrocatalysts via alloying strategy for high-performance lithium-sulfur batteries Song, Xueqin; Tian, Da; Qiu, Yue Energy Storage Materials, Vol. 41 https://doi.org/10.1016/j.ensm.2021.05.028	journal	October 2021
Highly densified NCM-cathodes for high energy Li-ion batteries: Microstructural evolution during densification and its influence on the performance of the electrodes Schmidt, Denny; Kamlah, Marc; Knoblauch, Volker Journal of Energy Storage, Vol. 17 https://doi.org/10.1016/j.est.2018.03.002	journal	June 2018
Avoiding Fracture in a Conversion Battery Material through Reaction with Larger Ions Boebinger, Matthew G.; Yeh, David; Xu, Michael Joule, Vol. 2, Issue 9 https://doi.org/10.1016/j.joule.2018.05.015	journal	September 2018
Systematical electrochemical study on the parasitic shuttle-effect in lithium-sulfur-cells at different temperatures and different rates Busche, Martin Rolf; Adelhelm, Philipp; Sommer, Heino Journal of Power Sources, Vol. 259 https://doi.org/10.1016/j.jpowsour.2014.02.075	journal	August 2014
FeS2 nanocrystals prepared in hierarchical porous carbon for lithium-ion battery Xu, Xin; Cai, Tingwei; Meng, Zhen Journal of Power Sources, Vol. 331 https://doi.org/10.1016/j.jpowsour.2016.09.015	journal	November 2016
Highly efficient sol-gel synthesis for ZnS@N, S co-doped carbon nanosheets with embedded heterostructure for sodium ion batteries Yang, Kaiwen; Guo, Qiubo; Li, Honglei Journal of Power Sources, Vol. 402 https://doi.org/10.1016/j.jpowsour.2018.09.046	journal	October 2018
Review of energy storage systems for electric vehicle applications: Issues and challenges Hannan, M. A.; Hoque, M. M.; Mohamed, A. Renewable and Sustainable Energy Reviews, Vol. 69 https://doi.org/10.1016/j.rser.2016.11.171	journal	March 2017
A review of multi-criteria decision making approaches for evaluating energy storage systems for grid applications Baumann, Manuel; Weil, Marcel; Peters, Jens F. Renewable and Sustainable Energy Reviews, Vol. 107 https://doi.org/10.1016/j.rser.2019.02.016	journal	June 2019
Understanding Conversion-Type Electrodes for Lithium Rechargeable Batteries Yu, Seung-Ho; Feng, Xinran; Zhang, Na Accounts of Chemical Research, Vol. 51, Issue 2 https://doi.org/10.1021/acs.accounts.7b00487	journal	January 2018
Polysulfide-Blocking Microporous Polymer Membrane Tailored for Hybrid Li-Sulfur Flow Batteries Li, Changyi; Ward, Ashleigh L.; Doris, Sean E. Nano Letters, Vol. 15, Issue 9 https://doi.org/10.1021/acs.nanolett.5b02078	journal	August 2015
Electrochemical Modeling of GITT Measurements for Improved Solid-State Diffusion Coefficient Evaluation Horner, Jeffrey S.; Whang, Grace; Ashby, David S. ACS Applied Energy Materials, Vol. 4, Issue 10 https://doi.org/10.1021/acsaem.1c02218	journal	October 2021
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
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
Ultrafine Iron Pyrite (FeS ₂ ) Nanocrystals Improve Sodium–Sulfur and Lithium–Sulfur Conversion Reactions for Efficient Batteries Douglas, Anna; Carter, Rachel; Oakes, Landon ACS Nano, Vol. 9, Issue 11 https://doi.org/10.1021/acsnano.5b04700	journal	October 2015
Electrospun FeS ₂ @Carbon Fiber Electrode as a High Energy Density Cathode for Rechargeable Lithium Batteries Zhu, Yujie; Fan, Xiulin; Suo, Liumin ACS Nano, Vol. 10, Issue 1 https://doi.org/10.1021/acsnano.5b07081	journal	December 2015
Robust Pitaya-Structured Pyrite as High Energy Density Cathode for High-Rate Lithium Batteries Xu, Xijun; Liu, Jun; Liu, Zhengbo ACS Nano, Vol. 11, Issue 9 https://doi.org/10.1021/acsnano.7b03530	journal	August 2017
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
Confined Synthesis of FeS ₂ Nanoparticles Encapsulated in Carbon Nanotube Hybrids for Ultrastable Lithium-Ion Batteries Xu, Lei; Hu, Yanjie; Zhang, Haoxuan ACS Sustainable Chemistry & Engineering, Vol. 4, Issue 8 https://doi.org/10.1021/acssuschemeng.6b00741	journal	July 2016
Electrochemical Windows of Room-Temperature Ionic Liquids from Molecular Dynamics and Density Functional Theory Calculations Ong, Shyue Ping; Andreussi, Oliviero; Wu, Yabi Chemistry of Materials, Vol. 23, Issue 11 https://doi.org/10.1021/cm200679y	journal	June 2011
Ionic Liquid Electrolytes for Lithium–Sulfur Batteries Park, Jun-Woo; Ueno, Kazuhide; Tachikawa, Naoki The Journal of Physical Chemistry C, Vol. 117, Issue 40 https://doi.org/10.1021/jp408037e	journal	September 2013
Promise and reality of post-lithium-ion batteries with high energy densities Choi, Jang Wook; Aurbach, Doron Nature Reviews Materials, Vol. 1, Issue 4 https://doi.org/10.1038/natrevmats.2016.13	journal	March 2016
Circumventing huge volume strain in alloy anodes of lithium batteries Li, Hongyi; Yamaguchi, Takitaro; Matsumoto, Shingo Nature Communications, Vol. 11, Issue 1 https://doi.org/10.1038/s41467-020-15452-0	journal	April 2020
Ultra-high-voltage Ni-rich layered cathodes in practical Li metal batteries enabled by a sulfonamide-based electrolyte Xue, Weijiang; Huang, Mingjun; Li, Yutao Nature Energy, Vol. 6, Issue 5 https://doi.org/10.1038/s41560-021-00792-y	journal	March 2021
Revisiting metal fluorides as lithium-ion battery cathodes Hua, Xiao; Eggeman, Alexander S.; Castillo-Martínez, Elizabeth Nature Materials, Vol. 20, Issue 6 https://doi.org/10.1038/s41563-020-00893-1	journal	January 2021
Understanding the conversion mechanism and performance of monodisperse FeF2 nanocrystal cathodes Xiao, Albert W.; Lee, Hyeon Jeong; Capone, Isaac Nature Materials, Vol. 19, Issue 6 https://doi.org/10.1038/s41563-020-0621-z	journal	February 2020
Charting the complete elastic properties of inorganic crystalline compounds de Jong, Maarten; Chen, Wei; Angsten, Thomas Scientific Data, Vol. 2, Issue 1 https://doi.org/10.1038/sdata.2015.9	journal	March 2015
Solvothermal synthesis of pyrite FeS₂nanocubes and their superior high rate lithium storage properties Liu, W. L.; Rui, X. H.; Tan, H. T. RSC Adv., Vol. 4, Issue 90 https://doi.org/10.1039/C4RA08527B	journal	September 2014
Sol–gel encapsulated lithium polysulfide catholyte and its application in lithium–sulfur batteries Smith, Leland C.; Malati, Peter; Fang, Jonathan Materials Horizons, Vol. 3, Issue 2 https://doi.org/10.1039/C5MH00228A	journal	January 2016
Conversion cathodes for rechargeable lithium and lithium-ion batteries Wu, Feixiang; Yushin, Gleb Energy & Environmental Science, Vol. 10, Issue 2 https://doi.org/10.1039/C6EE02326F	journal	January 2017
Challenges and prospects of nanosized silicon anodes in lithium-ion batteries Zhao, Xiuyun; Lehto, Vesa-Pekka Nanotechnology, Vol. 32, Issue 4 https://doi.org/10.1088/1361-6528/abb850	journal	October 2020
Mechanism and Solution for the Capacity Fading of Li/FeS ₂ Battery Zhang, Sheng S.; Tran, Dat T. Journal of The Electrochemical Society, Vol. 163, Issue 5 https://doi.org/10.1149/2.0041606jes	journal	January 2016

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