Unraveling Shuttle Effect and Suppression Strategy in Lithium/Sulfur Cells by In Situ/Operando X-ray Absorption Spectroscopic Characterization

Jia, Lujie; Wang, Jian; Ren, Shuaiyang; Ren, Guoxi; Jin, Xiang; Kao, Licheng; Feng, Xuefei; Yang, Feipeng; Wang, Qi; Pan, Ludi; Li, Qingtian; Liu, Yi‐sheng; Wu, Yang; Liu, Gao; Feng, Jun; Fan, Shoushan; Ye, Yifan; Guo, Jinghua; Zhang, Yuegang

doi:10.1002/eem2.12152

Unraveling Shuttle Effect and Suppression Strategy in Lithium/Sulfur Cells by In Situ/Operando X-ray Absorption Spectroscopic Characterization

Journal Article · Thu Nov 05 00:00:00 EST 2020 · Energy & Environmental Materials

DOI:https://doi.org/10.1002/eem2.12152· OSTI ID:1838431

Jia, Lujie ^[1]; ^[2]; Ren, Shuaiyang ^[1]; Ren, Guoxi ^[3]; Jin, Xiang ^[4]; Kao, Licheng ^[5]; Feng, Xuefei ^[5]; ^[5]; Wang, Qi ^[2]; Pan, Ludi ^[6]; Li, Qingtian ^[7]; Liu, Yi‐sheng ^[5]; Wu, Yang ^[4]; Liu, Gao ^[5]; Feng, Jun ^[5]; Fan, Shoushan ^[4]; Ye, Yifan ^[5]; ^[5]; Zhang, Yuegang ^[4]

Tsinghua Univ., Beijing (China); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Chinese Academy of Sciences (CAS), Suzhou (China)
Chinese Academy of Sciences (CAS), Shanghai (China)
Tsinghua Univ., Beijing (China)
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
State Key Laboratory of Low‐Dimensional Quantum Physics and Department of Physics Tsinghua University Beijing100084China
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Chinese Academy of Sciences (CAS), Shanghai (China)

The polysulfides shuttle effect represents a great challenge in achieving high capacity and long lifespan of lithium/sulfur (Li/S) cells. A comprehensive understanding of the shuttle-related sulfur speciation and diffusion process is vital for addressing this issue. Herein, we employed in situ/operando X-ray absorption spectroscopy (XAS) to trace the migration of polysulfides across the Li/S cells by precisely monitoring the sulfur chemical speciation at the cathodic electrolyte-separator and electrolyte-anode interfaces, respectively, in a real-time condition. After we adopted a shuttle-suppressing strategy by introducing an electrocatalytic layer of twinborn bismuth sulfide/bismuth oxide nanoclusters in a carbon matrix (BSOC), we found the Li/S cell showed greatly improved sulfur utilization and longer life span. The operando S K-edge XAS results revealed that the BSOC modification was bi-functional: trapping polysulfides and catalyzing conversion of sulfur species simultaneously. We elucidated that the polysulfide trapping-and-catalyzing effect of the BSOC electrocatalytic layer resulted in an effective lithium anode protection. Finally, our results could offer potential stratagem for designing more advanced Li/S cells.

View Accepted Manuscript (DOE)

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

Sponsoring Organization:: National Key R&D Program of China; National Natural Science Foundation of China (NSFC); USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC02-05CH11231

OSTI ID:: 1838431

Journal Information:: Energy & Environmental Materials, Journal Name: Energy & Environmental Materials Journal Issue: 2 Vol. 4; ISSN 2575-0356

Publisher:: Wiley - Zhengzhou UniversityCopyright Statement

Country of Publication:: United States

Language:: English

References (60)

Facile Solid-State Growth of 3D Well-Interconnected Nitrogen-Rich Carbon Nanotube-Graphene Hybrid Architectures for Lithium-Sulfur Batteries Ding, Yuan-Li; Kopold, Peter; Hahn, Kersten Advanced Functional Materials, Vol. 26, Issue 7 https://doi.org/10.1002/adfm.201504294	journal	December 2015
Ultrathin MnO ₂ /Graphene Oxide/Carbon Nanotube Interlayer as Efficient Polysulfide-Trapping Shield for High-Performance Li-S Batteries Kong, Weibang; Yan, Lingjia; Luo, Yufeng Advanced Functional Materials, Vol. 27, Issue 18 https://doi.org/10.1002/adfm.201606663	journal	March 2017
Leaf-Like Graphene-Oxide-Wrapped Sulfur for High-Performance Lithium-Sulfur Battery Yuan, Shouyi; Guo, Ziyang; Wang, Lina Advanced Science, Vol. 2, Issue 8 https://doi.org/10.1002/advs.201500071	journal	June 2015
Tuning Transition Metal Oxide-Sulfur Interactions for Long Life Lithium Sulfur Batteries: The “Goldilocks” Principle Liang, Xiao; Kwok, Chun Yuen; Lodi-Marzano, Fernanda Advanced Energy Materials, Vol. 6, Issue 6 https://doi.org/10.1002/aenm.201501636	journal	December 2015
Tungsten Disulfide Catalysts Supported on a Carbon Cloth Interlayer for High Performance Li-S Battery Park, Jungjin; Yu, Byeong-Chul; Park, Joong Sun Advanced Energy Materials, Vol. 7, Issue 11 https://doi.org/10.1002/aenm.201602567	journal	January 2017
Tailored Reaction Route by Micropore Confinement for Li-S Batteries Operating under Lean Electrolyte Conditions Wang, Hui; Adams, Brian D.; Pan, Huilin Advanced Energy Materials, Vol. 8, Issue 21 https://doi.org/10.1002/aenm.201800590	journal	May 2018
MoN Supported on Graphene as a Bifunctional Interlayer for Advanced Li‐S Batteries Tian, Da; Song, Xueqin; Wang, Maoxu Advanced Energy Materials, Vol. 9, Issue 46 https://doi.org/10.1002/aenm.201901940	journal	November 2019
Porous Hollow Carbon@Sulfur Composites for High-Power Lithium-Sulfur Batteries Jayaprakash, N.; Shen, J.; Moganty, Surya S. Angewandte Chemie International Edition, Vol. 50, Issue 26, p. 5904-5908 https://doi.org/10.1002/anie.201100637	journal	May 2011
High areal capacity flexible sulfur cathode based on multi-functionalized super-aligned carbon nanotubes Jia, Lujie; Wang, Jian; Chen, Zijin Nano Research, Vol. 12, Issue 5 https://doi.org/10.1007/s12274-019-2356-1	journal	March 2019
MnS decorated N/S codoped 3D graphene which used as cathode of the lithium-sulfur battery Li, Zhongtao; Xu, Rongfei; Deng, Shenzhen Applied Surface Science, Vol. 433 https://doi.org/10.1016/j.apsusc.2017.10.050	journal	March 2018
Binder-free polymer encapsulated sulfur–carbon nanotube composite cathodes for high performance lithium batteries Kong, Weibang; Sun, Li; Wu, Yang Carbon, Vol. 96 https://doi.org/10.1016/j.carbon.2015.10.062	journal	January 2016
The synergetic interaction between LiNO3 and lithium polysulfides for suppressing shuttle effect of lithium-sulfur batteries Zhang, Liang; Ling, Min; Feng, Jun Energy Storage Materials, Vol. 11 https://doi.org/10.1016/j.ensm.2017.09.001	journal	March 2018
Single-atom catalyst boosts electrochemical conversion reactions in batteries Wang, Jian; Jia, Lujie; Zhong, Jun Energy Storage Materials, Vol. 18 https://doi.org/10.1016/j.ensm.2018.09.006	journal	March 2019
MOF-derived Cobalt Sulfide Grown on 3D Graphene Foam as an Efficient Sulfur Host for Long-Life Lithium-Sulfur Batteries He, Jiarui; Chen, Yuanfu; Manthiram, Arumugam iScience, Vol. 4 https://doi.org/10.1016/j.isci.2018.05.005	journal	June 2018
Sulfur-graphene composite for rechargeable lithium batteries Wang, Jia-Zhao; Lu, Lin; Choucair, Mohammad Journal of Power Sources, Vol. 196, Issue 16, p. 7030-7034 https://doi.org/10.1016/j.jpowsour.2010.09.106	journal	August 2011
Liquid electrolyte lithium/sulfur battery: Fundamental chemistry, problems, and solutions Zhang, Sheng S. Journal of Power Sources, Vol. 231, p. 153-162 https://doi.org/10.1016/j.jpowsour.2012.12.102	journal	June 2013
Sulfur/three-dimensional graphene composite for high performance lithium–sulfur batteries Xu, Chunmei; Wu, Yishan; Zhao, Xuyang Journal of Power Sources, Vol. 275 https://doi.org/10.1016/j.jpowsour.2014.11.007	journal	February 2015
Simultaneous optimization of surface chemistry and pore morphology of 3D graphene-sulfur cathode via multi-ion modulation Wang, Jian; Cheng, Shuang; Li, Wanfei Journal of Power Sources, Vol. 321 https://doi.org/10.1016/j.jpowsour.2016.04.120	journal	July 2016
Dense integration of graphene and sulfur through the soft approach for compact lithium/sulfur battery cathode Li, Hongfei; Yang, Xiaowei; Wang, Xiaomin Nano Energy, Vol. 12 https://doi.org/10.1016/j.nanoen.2015.01.007	journal	March 2015
Nucleophilic substitution between polysulfides and binders unexpectedly stabilizing lithium sulfur battery Ling, Min; Zhang, Liang; Zheng, Tianyue Nano Energy, Vol. 38 https://doi.org/10.1016/j.nanoen.2017.05.020	journal	August 2017
Robust electrical “highway” network for high mass loading sulfur cathode Wang, Jian; Cheng, Shuang; Li, Wanfei Nano Energy, Vol. 40 https://doi.org/10.1016/j.nanoen.2017.08.020	journal	October 2017
Effective electrostatic confinement of polysulfides in lithium/sulfur batteries by a functional binder Zhang, Liang; Ling, Min; Feng, Jun Nano Energy, Vol. 40 https://doi.org/10.1016/j.nanoen.2017.09.003	journal	October 2017
X-ray Absorption Spectroscopic Characterization of the Synthesis Process: Revealing the Interactions in Cetyltrimethylammonium Bromide-Modified Sulfur–Graphene Oxide Nanocomposites Ye, Yifan; Kawase, Ayako; Song, Min-Kyu The Journal of Physical Chemistry C, Vol. 120, Issue 19 https://doi.org/10.1021/acs.jpcc.6b00751	journal	May 2016
Powering Lithium–Sulfur Battery Performance by Propelling Polysulfide Redox at Sulfiphilic Hosts Yuan, Zhe; Peng, Hong-Jie; Hou, Ting-Zheng Nano Letters, Vol. 16, Issue 1 https://doi.org/10.1021/acs.nanolett.5b04166	journal	December 2015
Revealing the Electrochemical Charging Mechanism of Nanosized Li ₂ S by in Situ and Operando X-ray Absorption Spectroscopy Zhang, Liang; Sun, Dan; Feng, Jun Nano Letters, Vol. 17, Issue 8 https://doi.org/10.1021/acs.nanolett.7b02381	journal	July 2017
Freeze-Dried Sulfur–Graphene Oxide–Carbon Nanotube Nanocomposite for High Sulfur-Loading Lithium/Sulfur Cells Hwa, Yoon; Seo, Hyeon Kook; Yuk, Jong-min Nano Letters, Vol. 17, Issue 11 https://doi.org/10.1021/acs.nanolett.7b03831	journal	October 2017
In Situ X-ray Absorption Spectroscopic Investigation of the Capacity Degradation Mechanism in Mg/S Batteries Xu, Yan; Ye, Yifan; Zhao, Shuyang Nano Letters, Vol. 19, Issue 5 https://doi.org/10.1021/acs.nanolett.8b05208	journal	March 2019
SnO ₂ /Reduced Graphene Oxide Interlayer Mitigating the Shuttle Effect of Li–S Batteries Hu, Nana; Lv, Xingshuai; Dai, Ying ACS Applied Materials & Interfaces, Vol. 10, Issue 22 https://doi.org/10.1021/acsami.8b03255	journal	May 2018
Toward More Reliable Lithium–Sulfur Batteries: An All-Graphene Cathode Structure Fang, Ruopian; Zhao, Shiyong; Pei, Songfeng ACS Nano, Vol. 10, Issue 9 https://doi.org/10.1021/acsnano.6b04019	journal	August 2016
All-MXene-Based Integrated Electrode Constructed by Ti ₃ C ₂ Nanoribbon Framework Host and Nanosheet Interlayer for High-Energy-Density Li–S Batteries Dong, Yanfeng; Zheng, Shuanghao; Qin, Jieqiong ACS Nano, Vol. 12, Issue 3 https://doi.org/10.1021/acsnano.7b07672	journal	February 2018
Challenges and Prospects of Lithium–Sulfur Batteries Manthiram, Arumugam; Fu, Yongzhu; Su, Yu-Sheng Accounts of Chemical Research, Vol. 46, Issue 5 https://doi.org/10.1021/ar300179v	journal	June 2012
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
Graphene Oxide as a Sulfur Immobilizer in High Performance Lithium/Sulfur Cells Ji, Liwen; Rao, Mumin; Zheng, Haimei Journal of the American Chemical Society, Vol. 133, Issue 46, p. 18522-18525 https://doi.org/10.1021/ja206955k	journal	November 2011
Sulfur Speciation in Li–S Batteries Determined by Operando X-ray Absorption Spectroscopy Cuisinier, Marine; Cabelguen, Pierre-Etienne; Evers, Scott The Journal of Physical Chemistry Letters, Vol. 4, Issue 19 https://doi.org/10.1021/jz401763d	journal	September 2013
X-ray Absorption Spectra of Dissolved Polysulfides in Lithium–Sulfur Batteries from First-Principles Pascal, Tod A.; Wujcik, Kevin H.; Velasco-Velez, Juan The Journal of Physical Chemistry Letters, Vol. 5, Issue 9 https://doi.org/10.1021/jz500260s	journal	April 2014
Hollow Carbon Nanofiber-Encapsulated Sulfur Cathodes for High Specific Capacity Rechargeable Lithium Batteries Zheng, Guangyuan; Yang, Yuan; Cha, Judy J. Nano Letters, Vol. 11, Issue 10, p. 4462-4467 https://doi.org/10.1021/nl2027684	journal	October 2011
Amphiphilic Surface Modification of Hollow Carbon Nanofibers for Improved Cycle Life of Lithium Sulfur Batteries Zheng, Guangyuan; Zhang, Qianfan; Cha, Judy J. Nano Letters, Vol. 13, Issue 3, p. 1265-1270 https://doi.org/10.1021/nl304795g	journal	February 2013
Graphene-Based Three-Dimensional Hierarchical Sandwich-type Architecture for High-Performance Li/S Batteries Chen, Renjie; Zhao, Teng; Lu, Jun Nano Letters, Vol. 13, Issue 10 https://doi.org/10.1021/nl4016683	journal	September 2013
A Long-Life, High-Rate Lithium/Sulfur Cell: A Multifaceted Approach to Enhancing Cell Performance Song, Min-Kyu; Zhang, Yuegang; Cairns, Elton J. Nano Letters, Vol. 13, Issue 12 https://doi.org/10.1021/nl402793z	journal	November 2013
Sulfur Nanocrystals Confined in Carbon Nanotube Network As a Binder-Free Electrode for High-Performance Lithium Sulfur Batteries Sun, Li; Li, Mengya; Jiang, Ying Nano Letters, Vol. 14, Issue 7 https://doi.org/10.1021/nl501486n	journal	June 2014
High-Rate, Ultralong Cycle-Life Lithium/Sulfur Batteries Enabled by Nitrogen-Doped Graphene Qiu, Yongcai; Li, Wanfei; Zhao, Wen Nano Letters, Vol. 14, Issue 8 https://doi.org/10.1021/nl5020475	journal	July 2014
Balancing surface adsorption and diffusion of lithium-polysulfides on nonconductive oxides for lithium–sulfur battery design Tao, Xinyong; Wang, Jianguo; Liu, Chong Nature Communications, Vol. 7, Issue 1 https://doi.org/10.1038/ncomms11203	journal	April 2016
A highly efficient polysulfide mediator for lithium–sulfur batteries Liang, Xiao; Hart, Connor; Pang, Quan Nature Communications, Vol. 6, Issue 1 https://doi.org/10.1038/ncomms6682	journal	January 2015
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
A highly ordered nanostructured carbon–sulphur cathode for lithium–sulphur batteries Ji, Xiulei; Lee, Kyu Tae; Nazar, Linda F. Nature Materials, Vol. 8, Issue 6, p. 500-506 https://doi.org/10.1038/nmat2460	journal	May 2009
Li–O₂ and Li–S batteries with high energy storage Bruce, Peter G.; Freunberger, Stefan A.; Hardwick, Laurence J. Nature Materials, Vol. 11, Issue 1, p. 19-29 https://doi.org/10.1038/nmat3191	journal	January 2012
Graphene-enveloped sulfur in a one pot reaction: a cathode with good coulombic efficiency and high practical sulfur content Evers, Scott; Nazar, Linda F. Chem. Commun., Vol. 48, Issue 9 https://doi.org/10.1039/C2CC16726C	journal	January 2012
Understanding the degradation mechanism of rechargeable lithium/sulfur cells: a comprehensive study of the sulfur–graphene oxide cathode after discharge–charge cycling Feng, Xuefei; Song, Min-Kyu; Stolte, Wayne C. Phys. Chem. Chem. Phys., Vol. 16, Issue 32 https://doi.org/10.1039/C4CP01341G	journal	January 2014
Twinborn TiO ₂ –TiN heterostructures enabling smooth trapping–diffusion–conversion of polysulfides towards ultralong life lithium–sulfur batteries Zhou, Tianhong; Lv, Wei; Li, Jia Energy & Environmental Science, Vol. 10, Issue 7 https://doi.org/10.1039/C7EE01430A	journal	January 2017
A three-dimensional self-assembled SnS ₂ -nano-dots@graphene hybrid aerogel as an efficient polysulfide reservoir for high-performance lithium–sulfur batteries Luo, Liu; Chung, Sheng-Heng; Manthiram, Arumugam Journal of Materials Chemistry A, Vol. 6, Issue 17 https://doi.org/10.1039/C8TA01089G	journal	January 2018
In situ extracted poly(acrylic acid) contributing to electrospun nanofiber separators with precisely tuned pore structures for ultra-stable lithium–sulfur batteries Zhu, Xiaobo; Ouyang, Yue; Chen, Jiawei Journal of Materials Chemistry A, Vol. 7, Issue 7 https://doi.org/10.1039/C8TA11397A	journal	January 2019
Advances in Li–S batteries Ji, Xiulei; Nazar, Linda F. Journal of Materials Chemistry, Vol. 20, Issue 44, p. 9821-9826 https://doi.org/10.1039/b925751a	journal	January 2010
High “C” rate Li-S cathodes: sulfur imbibed bimodal porous carbons He, Guang; Ji, Xiulei; Nazar, Linda Energy & Environmental Science, Vol. 4, Issue 8 https://doi.org/10.1039/c1ee01219c	journal	January 2011
Challenges in the development of advanced Li-ion batteries: a review Etacheri, Vinodkumar; Marom, Rotem; Elazari, Ran Energy & Environmental Science, Vol. 4, Issue 9 https://doi.org/10.1039/c1ee01598b	journal	January 2011
Porous carbon nanofiber–sulfur composite electrodes for lithium/sulfur cells Ji, Liwen; Rao, Mumin; Aloni, Shaul Energy & Environmental Science, Vol. 4, Issue 12, p. 5053-5059 https://doi.org/10.1039/c1ee02256c	journal	January 2011
Flexible self-supporting graphene–sulfur paper for lithium sulfur batteries Jin, Jun; Wen, Zhaoyin; Ma, Guoqiang RSC Advances, Vol. 3, Issue 8 https://doi.org/10.1039/c2ra22808d	journal	January 2013
Catalytic oxidation of Li ₂ S on the surface of metal sulfides for Li−S batteries Zhou, Guangmin; Tian, Hongzhen; Jin, Yang Proceedings of the National Academy of Sciences, Vol. 114, Issue 5 https://doi.org/10.1073/pnas.1615837114	journal	January 2017
Understanding the electrochemical reaction mechanism of VS ₂ nanosheets in lithium-ion cells by multiple in situ and ex situ x-ray spectroscopy Zhang, Liang; Sun, Dan; Wei, Qiulong Journal of Physics D: Applied Physics, Vol. 51, Issue 49 https://doi.org/10.1088/1361-6463/aadde7	journal	September 2018
Understanding the Charging Mechanism of Lithium-Sulfur Batteries Using Spatially Resolved Operando X-Ray Absorption Spectroscopy Gorlin, Yelena; Patel, Manu U. M.; Freiberg, Anna Journal of The Electrochemical Society, Vol. 163, Issue 6 https://doi.org/10.1149/2.0631606jes	journal	January 2016
Fingerprinting Lithium-Sulfur Battery Reaction Products by X-ray Absorption Spectroscopy Wujcik, Kevin H.; Velasco-Velez, Juan; Wu, Cheng Hao Journal of The Electrochemical Society, Vol. 161, Issue 6 https://doi.org/10.1149/2.078406jes	journal	January 2014

Similar Records

The synergetic interaction between $\mathrm{LiNO_3}$ and lithium polysulfides for suppressing shuttle effect of lithium-sulfur batteries

Journal Article · Thu Sep 20 20:00:00 EDT 2018 · Energy Storage Materials · OSTI ID:1559789

Beyond the Polysulfide Shuttle and Lithium Dendrite Formation: Addressing the Sluggish Sulfur Redox Kinetics for Practical High-Energy Li-S Batteries

Journal Article · Tue Aug 11 20:00:00 EDT 2020 · Angewandte Chemie (International Edition) · OSTI ID:1710199

Related Subjects

25 ENERGY STORAGE
in situ/operando
lithium/sulfur cell
shuttle effect
sulfur speciation
x-ray absorption spectroscopy

Unraveling Shuttle Effect and Suppression Strategy in Lithium/Sulfur Cells by In Situ/Operando X-ray Absorption Spectroscopic Characterization

Citation Formats

References (60)

Similar Records

Related Subjects