Anode–Free Lithium–Sulfur Cells Enabled by Rationally Tuning Lithium Polysulfide Molecules

Ren, Yuxun; Bhargav, Amruth; Shin, Woochul; Sul, Hyunki; Manthiram, Arumugam

doi:10.1002/anie.202207907

Title: Anode–Free Lithium–Sulfur Cells Enabled by Rationally Tuning Lithium Polysulfide Molecules

Journal Article · Thu Jul 07 00:00:00 EDT 2022 · Angewandte Chemie (International Edition)

DOI:https://doi.org/10.1002/anie.202207907· OSTI ID:2217438

Ren, Yuxun ^[1]; Bhargav, Amruth ^[1]; Shin, Woochul ^[1]; Sul, Hyunki ^[1];

^[1]

University of Texas, Austin, TX (United States)

The two major barriers of practical lithium–sulfur batteries are the poor reversibility of lithium-metal anode and sluggish kinetics of sulfur cathode. Here, we report a simple yet cogent, molecular tailoring approach for lithium polysulfides, enabling a synergistic enhancement of anode reversibility and cathode kinetics. In this study, we show that SnI₄ coordinates with lithium polysulfides to form soluble complexes, resulting in a Li₂SnS₃-rich anode interphase layer. As Li₂SnS₃ is stable against parasitic reactions and has a lower ionic resistance over cycling, the Li plating/stripping efficiency is greatly improved. In addition, the formation of soluble complexes between SnI₄ and lithium polysulfides play a non-negligible role in suppressing the clustering behavior of lithium polysulfide molecules, resulting in a significant enhancement in sulfur conversion kinetics under lean electrolyte conditions. The synergistic improvement is validated in anode-free, lean-electrolyte pouch cells with a Li₂S cathode that displays capacity retention of 78 % after 100 cycles.

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Research Organization:: Univ. of Texas, Austin, TX (United States)

Sponsoring Organization:: USDOE Office of Energy Efficiency and Renewable Energy (EERE), Office of Sustainable Transportation. Vehicle Technologies Office (VTO); USDOE

Grant/Contract Number:: EE0007762

OSTI ID:: 2217438

Alternate ID(s):: OSTI ID: 1882752; OSTI ID: 1976284

Journal Information:: Angewandte Chemie (International Edition), Vol. 61, Issue 35; ISSN 1433-7851

Publisher:: WileyCopyright Statement

Country of Publication:: United States

Language:: English

References (43)

Rational design of spontaneous reactions for protecting porous lithium electrodes in lithium–sulfur batteries Ren, Y. X.; Zeng, L.; Jiang, H. R. Nature Communications, Vol. 10, Issue 1 https://doi.org/10.1038/s41467-019-11168-y	journal	July 2019
Activating Inert Metallic Compounds for High‐Rate Lithium–Sulfur Batteries Through In Situ Etching of Extrinsic Metal Zhao, Meng; Peng, Hong‐Jie; Zhang, Ze‐Wen Angewandte Chemie International Edition, Vol. 58, Issue 12 https://doi.org/10.1002/anie.201812062	journal	March 2019
Coatable Li ₄ SnS ₄ Solid Electrolytes Prepared from Aqueous Solutions for All-Solid-State Lithium-Ion Batteries Choi, Young Eun; Park, Kern Ho; Kim, Dong Hyeon ChemSusChem, Vol. 10, Issue 12 https://doi.org/10.1002/cssc.201700409	journal	May 2017
A New Class of Ionically Conducting Fluorinated Ether Electrolytes with High Electrochemical Stability Amanchukwu, Chibueze V.; Yu, Zhiao; Kong, Xian Journal of the American Chemical Society, Vol. 142, Issue 16 https://doi.org/10.1021/jacs.9b11056	journal	April 2020
Reclaiming Inactive Lithium with a Triiodide/Iodide Redox Couple for Practical Lithium Metal Batteries Jin, Cheng‐Bin; Zhang, Xue‐Qiang; Sheng, Ou‐Wei Angewandte Chemie International Edition, Vol. 60, Issue 42 https://doi.org/10.1002/anie.202110589	journal	September 2021
Atomic Tungsten on Graphene with Unique Coordination Enabling Kinetically Boosted Lithium–Sulfur Batteries Wang, Peng; Xi, Baojuan; Zhang, Zhengchunyu Angewandte Chemie, Vol. 133, Issue 28 https://doi.org/10.1002/ange.202104053	journal	June 2021
An Organodiselenide Comediator to Facilitate Sulfur Redox Kinetics in Lithium–Sulfur Batteries Zhao, Meng; Chen, Xiang; Li, Xi‐Yao Advanced Materials, Vol. 33, Issue 13 https://doi.org/10.1002/adma.202007298	journal	February 2021
Approaching Ultrastable High‐Rate Li–S Batteries through Hierarchically Porous Titanium Nitride Synthesized by Multiscale Phase Separation Lim, Won‐Gwang; Jo, Changshin; Cho, Ara Advanced Materials, Vol. 31, Issue 3 https://doi.org/10.1002/adma.201806547	journal	September 2018
Phosphorous Pentasulfide as a Novel Additive for High-Performance Lithium-Sulfur Batteries Lin, Zhan; Liu, Zengcai; Fu, Wujun Advanced Functional Materials, Vol. 23, Issue 8 https://doi.org/10.1002/adfm.201200696	journal	June 2012
A reflection on lithium-ion battery cathode chemistry Manthiram, Arumugam Nature Communications, Vol. 11, Issue 1 https://doi.org/10.1038/s41467-020-15355-0	journal	March 2020
Surface Gelation on Disulfide Electrocatalysts in Lithium–Sulfur Batteries Li, Xi‐Yao; Feng, Shuai; Zhao, Meng Angewandte Chemie International Edition, Vol. 61, Issue 7 https://doi.org/10.1002/anie.202114671	journal	December 2021
Organosulfides: An Emerging Class of Cathode Materials for Rechargeable Lithium Batteries Wang, Dan-Yang; Guo, Wei; Fu, Yongzhu Accounts of Chemical Research, Vol. 52, Issue 8 https://doi.org/10.1021/acs.accounts.9b00231	journal	July 2019
A safe and efficient lithiated silicon-sulfur battery enabled by a bi-functional composite interlayer Ren, Y. X.; Zeng, L.; Zhao, C. Energy Storage Materials, Vol. 25 https://doi.org/10.1016/j.ensm.2019.10.012	journal	March 2020
Shielding Polysulfide Intermediates by an Organosulfur‐Containing Solid Electrolyte Interphase on the Lithium Anode in Lithium–Sulfur Batteries Wei, Jun‐Yu; Zhang, Xue‐Qiang; Hou, Li‐Peng Advanced Materials, Vol. 32, Issue 37 https://doi.org/10.1002/adma.202003012	journal	August 2020
Lithium-Sulfur Batteries: Attaining the Critical Metrics Bhargav, Amruth; He, Jiarui; Gupta, Abhay Joule, Vol. 4, Issue 2 https://doi.org/10.1016/j.joule.2020.01.001	journal	February 2020
A Cobalt‐ and Manganese‐Free High‐Nickel Layered Oxide Cathode for Long‐Life, Safer Lithium‐Ion Batteries Cui, Zehao; Xie, Qiang; Manthiram, Arumugam Advanced Energy Materials, Vol. 11, Issue 41 https://doi.org/10.1002/aenm.202102421	journal	October 2021
Lithium degradation in lithium–sulfur batteries: insights into inventory depletion and interphasial evolution with cycling Nanda, Sanjay; Manthiram, Arumugam Energy & Environmental Science, Vol. 13, Issue 8 https://doi.org/10.1039/D0EE01074J	journal	January 2020
The role of polysulfide dianions and radical anions in the chemical, physical and biological sciences, including sulfur-based batteries Steudel, Ralf; Chivers, Tristram Chemical Society Reviews, Vol. 48, Issue 12 https://doi.org/10.1039/C8CS00826D	journal	January 2019
Modeling of lithium-sulfur batteries incorporating the effect of Li2S precipitation Ren, Y. X.; Zhao, T. S.; Liu, M. Journal of Power Sources, Vol. 336 https://doi.org/10.1016/j.jpowsour.2016.10.063	journal	December 2016
Highly Solvating Electrolytes for Lithium–Sulfur Batteries Gupta, Abhay; Bhargav, Amruth; Manthiram, Arumugam Advanced Energy Materials, Vol. 9, Issue 6 https://doi.org/10.1002/aenm.201803096	journal	December 2018
Reclaiming Inactive Lithium with a Triiodide/Iodide Redox Couple for Practical Lithium Metal Batteries Jin, Cheng‐Bin; Zhang, Xue‐Qiang; Sheng, Ou‐Wei Angewandte Chemie, Vol. 133, Issue 42 https://doi.org/10.1002/ange.202110589	journal	September 2021
Rechargeable Lithium–Sulfur Batteries Manthiram, Arumugam; Fu, Yongzhu; Chung, Sheng-Heng Chemical Reviews, Vol. 114, Issue 23 https://doi.org/10.1021/cr500062v	journal	July 2014
Photoluminescence of antimony(III) and bismuth(III) chloride complexes in solution Nikol, Hans; Vogler, Arnd Journal of the American Chemical Society, Vol. 113, Issue 23 https://doi.org/10.1021/ja00023a081	journal	November 1991
Dual‐Solvent Li‐Ion Solvation Enables High‐Performance Li‐Metal Batteries Wang, Hansen; Yu, Zhiao; Kong, Xian Advanced Materials, Vol. 33, Issue 25 https://doi.org/10.1002/adma.202008619	journal	May 2021
Atomic Tungsten on Graphene with Unique Coordination Enabling Kinetically Boosted Lithium–Sulfur Batteries Wang, Peng; Xi, Baojuan; Zhang, Zhengchunyu Angewandte Chemie International Edition, Vol. 60, Issue 28 https://doi.org/10.1002/anie.202104053	journal	June 2021
Direct observation of lithium polysulfides in lithium–sulfur batteries using operando X-ray diffraction Conder, Joanna; Bouchet, Renaud; Trabesinger, Sigita Nature Energy, Vol. 2, Issue 6 https://doi.org/10.1038/nenergy.2017.69	journal	May 2017
Tailoring Lithium Polysulfide Coordination and Clustering Behavior through Cationic Electrostatic Competition Gupta, Abhay; Bhargav, Amruth; Manthiram, Arumugam Chemistry of Materials, Vol. 33, Issue 9 https://doi.org/10.1021/acs.chemmater.1c00893	journal	April 2021
Sulfide‐Based Solid‐State Electrolytes: Synthesis, Stability, and Potential for All‐Solid‐State Batteries Zhang, Qing; Cao, Daxian; Ma, Yi Advanced Materials, Vol. 31, Issue 44 https://doi.org/10.1002/adma.201901131	journal	August 2019
Delineating the Lithium–Electrolyte Interfacial Chemistry and the Dynamics of Lithium Deposition in Lithium–Sulfur Batteries Nanda, Sanjay; Manthiram, Arumugam Advanced Energy Materials, Vol. 11, Issue 11 https://doi.org/10.1002/aenm.202003293	journal	January 2021
Insights into the Electrochemical Stability and Lithium Conductivity of Li ₄ MS ₄ (M = Si, Ge, and Sn) Chen, Fengjiao; Cheng, Songqi; Liu, Jian-Bo ACS Applied Materials & Interfaces, Vol. 13, Issue 19 https://doi.org/10.1021/acsami.1c03227	journal	April 2021
Amorphous Lithium Sulfide as Lithium‐Sulfur Battery Cathode with Low Activation Barrier Lodovico, Lucas; Milad Hosseini, Seyed; Varzi, Alberto Energy Technology, Vol. 7, Issue 12 https://doi.org/10.1002/ente.201801013	journal	March 2019
Organosulfur Compounds Enable Uniform Lithium Plating and Long-Term Battery Cycling Stability Boateng, Bismark; Han, Yupei; Zhen, Cheng Nano Letters, Vol. 20, Issue 4 https://doi.org/10.1021/acs.nanolett.0c00074	journal	March 2020
Evoking High-Donor-Number-Assisted and Organosulfur-Mediated Conversion in Lithium–Sulfur Batteries Gupta, Abhay; Bhargav, Amruth; Manthiram, Arumugam ACS Energy Letters, Vol. 6, Issue 1 https://doi.org/10.1021/acsenergylett.0c02461	journal	December 2020
High-Performance Anode-Free Li–S Batteries with an Integrated Li ₂ S–Electrocatalyst Cathode He, Jiarui; Bhargav, Amruth; Manthiram, Arumugam ACS Energy Letters, Vol. 7, Issue 2 https://doi.org/10.1021/acsenergylett.1c02569	journal	January 2022
Anode-free, Lean-Electrolyte Lithium-Sulfur Batteries Enabled by Tellurium-Stabilized Lithium Deposition Nanda, Sanjay; Bhargav, Amruth; Manthiram, Arumugam Joule, Vol. 4, Issue 5 https://doi.org/10.1016/j.joule.2020.03.020	journal	May 2020
Artificial dual solid-electrolyte interfaces based on in situ organothiol transformation in lithium sulfur battery Guo, Wei; Zhang, Wanying; Si, Yubing Nature Communications, Vol. 12, Issue 1 https://doi.org/10.1038/s41467-021-23155-3	journal	May 2021
Activating Inert Metallic Compounds for High‐Rate Lithium–Sulfur Batteries Through In Situ Etching of Extrinsic Metal Zhao, Meng; Peng, Hong‐Jie; Zhang, Ze‐Wen Angewandte Chemie, Vol. 131, Issue 12 https://doi.org/10.1002/ange.201812062	journal	January 2019
Degradation mechanism of hybrid tin-based perovskite solar cells and the critical role of tin (IV) iodide Lanzetta, Luis; Webb, Thomas; Zibouche, Nourdine Nature Communications, Vol. 12, Issue 1 https://doi.org/10.1038/s41467-021-22864-z	journal	May 2021
Unifying the clustering kinetics of lithium polysulfides with the nucleation behavior of Li ₂ S in lithium–sulfur batteries Gupta, Abhay; Manthiram, Arumugam Journal of Materials Chemistry A, Vol. 9, Issue 22 https://doi.org/10.1039/D1TA02779D	journal	January 2021
Li2S-based anode-free full batteries with modified Cu current collector Chen, Jie; Xiang, Jingwei; Chen, Xin Energy Storage Materials, Vol. 30 https://doi.org/10.1016/j.ensm.2020.05.009	journal	September 2020
Surface Gelation on Disulfide Electrocatalysts in Lithium–Sulfur Batteries Li, Xi‐Yao; Feng, Shuai; Zhao, Meng Angewandte Chemie, Vol. 134, Issue 7 https://doi.org/10.1002/ange.202114671	journal	December 2021
Achieving three-dimensional lithium sulfide growth in lithium-sulfur batteries using high-donor-number anions Chu, Hyunwon; Noh, Hyungjun; Kim, Yun-Jung Nature Communications, Vol. 10, Issue 1 https://doi.org/10.1038/s41467-018-07975-4	journal	January 2019
Mixed Cationic and Anionic Redox in Ni and Co Free Chalcogen-Based Cathode Chemistry for Li-Ion Batteries Nagarajan, Sudhan; Hwang, Sooyeon; Balasubramanian, Mahalingam Journal of the American Chemical Society, Vol. 143, Issue 38 https://doi.org/10.1021/jacs.1c06828	journal	September 2021

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Title: Anode–Free Lithium–Sulfur Cells Enabled by Rationally Tuning Lithium Polysulfide Molecules

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