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Title: Redox-Active Supramolecular Polymer Binders for Lithium–Sulfur Batteries That Adapt Their Transport Properties in Operando

Abstract

π-Stacked perylene bisimide (PBI) molecules are implemented here as highly networked, redox-active supramolecular polymer binders in sulfur cathodes for lightweight and energy-dense Li-S batteries. We show that the in operando reduction and lithiation of these PBI binders sustainably reduces Li-S cell impedance relative to nonredox active conventional polymer binders. This lower impedance enables high-rate cycling in Li-S cells with excellent durability, a critical step toward unlocking the full potential of Li-S batteries for electric vehicles and aviation.

Authors:
 [1];  [2];  [2];  [3]
  1. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Joint Center for Energy Storage Research
  2. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Energy Technologies Area; Univ. of California, Berkeley, CA (United States). Dept. of Chemical and Biomolecular Engineering
  3. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Joint Center for Energy Storage Research; Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Molecular Foundry
Publication Date:
Research Org.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1377549
Grant/Contract Number:  
AC02-05CH11231
Resource Type:
Accepted Manuscript
Journal Name:
Chemistry of Materials
Additional Journal Information:
Journal Volume: 28; Journal Issue: 20; Journal ID: ISSN 0897-4756
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 25 ENERGY STORAGE

Citation Formats

Frischmann, Peter D., Hwa, Yoon, Cairns, Elton J., and Helms, Brett A. Redox-Active Supramolecular Polymer Binders for Lithium–Sulfur Batteries That Adapt Their Transport Properties in Operando. United States: N. p., 2016. Web. doi:10.1021/acs.chemmater.6b03013.
Frischmann, Peter D., Hwa, Yoon, Cairns, Elton J., & Helms, Brett A. Redox-Active Supramolecular Polymer Binders for Lithium–Sulfur Batteries That Adapt Their Transport Properties in Operando. United States. https://doi.org/10.1021/acs.chemmater.6b03013
Frischmann, Peter D., Hwa, Yoon, Cairns, Elton J., and Helms, Brett A. Tue . "Redox-Active Supramolecular Polymer Binders for Lithium–Sulfur Batteries That Adapt Their Transport Properties in Operando". United States. https://doi.org/10.1021/acs.chemmater.6b03013. https://www.osti.gov/servlets/purl/1377549.
@article{osti_1377549,
title = {Redox-Active Supramolecular Polymer Binders for Lithium–Sulfur Batteries That Adapt Their Transport Properties in Operando},
author = {Frischmann, Peter D. and Hwa, Yoon and Cairns, Elton J. and Helms, Brett A.},
abstractNote = {π-Stacked perylene bisimide (PBI) molecules are implemented here as highly networked, redox-active supramolecular polymer binders in sulfur cathodes for lightweight and energy-dense Li-S batteries. We show that the in operando reduction and lithiation of these PBI binders sustainably reduces Li-S cell impedance relative to nonredox active conventional polymer binders. This lower impedance enables high-rate cycling in Li-S cells with excellent durability, a critical step toward unlocking the full potential of Li-S batteries for electric vehicles and aviation.},
doi = {10.1021/acs.chemmater.6b03013},
journal = {Chemistry of Materials},
number = 20,
volume = 28,
place = {United States},
year = {2016},
month = {10}
}

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Cited by: 15 works
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Works referenced in this record:

Li–O2 and Li–S batteries with high energy storage
journal, January 2012

  • Bruce, Peter G.; Freunberger, Stefan A.; Hardwick, Laurence J.
  • Nature Materials, Vol. 11, Issue 1, p. 19-29
  • DOI: 10.1038/nmat3191

Advances in Li–S batteries
journal, January 2010

  • Ji, Xiulei; Nazar, Linda F.
  • Journal of Materials Chemistry, Vol. 20, Issue 44, p. 9821-9826
  • DOI: 10.1039/b925751a

Nanostructured sulfur cathodes
journal, January 2013

  • Yang, Yuan; Zheng, Guangyuan; Cui, Yi
  • Chemical Society Reviews, Vol. 42, Issue 7, p. 3018-3032
  • DOI: 10.1039/c2cs35256g

Rechargeable Lithium–Sulfur Batteries
journal, July 2014

  • Manthiram, Arumugam; Fu, Yongzhu; Chung, Sheng-Heng
  • Chemical Reviews, Vol. 114, Issue 23
  • DOI: 10.1021/cr500062v

The synergetic effect of lithium polysulfide and lithium nitrate to prevent lithium dendrite growth
journal, June 2015

  • Li, Weiyang; Yao, Hongbin; Yan, Kai
  • Nature Communications, Vol. 6, Issue 1
  • DOI: 10.1038/ncomms8436

The use of elemental sulfur as an alternative feedstock for polymeric materials
journal, April 2013

  • Chung, Woo Jin; Griebel, Jared J.; Kim, Eui Tae
  • Nature Chemistry, Vol. 5, Issue 6
  • DOI: 10.1038/nchem.1624

Inverse Vulcanization of Elemental Sulfur to Prepare Polymeric Electrode Materials for Li–S Batteries
journal, February 2014

  • Simmonds, Adam G.; Griebel, Jared J.; Park, Jungjin
  • ACS Macro Letters, Vol. 3, Issue 3
  • DOI: 10.1021/mz400649w

Amphiphilic Surface Modification of Hollow Carbon Nanofibers for Improved Cycle Life of Lithium Sulfur Batteries
journal, February 2013

  • Zheng, Guangyuan; Zhang, Qianfan; Cha, Judy J.
  • Nano Letters, Vol. 13, Issue 3, p. 1265-1270
  • DOI: 10.1021/nl304795g

A highly ordered nanostructured carbon–sulphur cathode for lithium–sulphur batteries
journal, May 2009

  • Ji, Xiulei; Lee, Kyu Tae; Nazar, Linda F.
  • Nature Materials, Vol. 8, Issue 6, p. 500-506
  • DOI: 10.1038/nmat2460

Hydroxylated Graphene-Sulfur Nanocomposites for High-Rate Lithium-Sulfur Batteries
journal, April 2013


Graphene Oxide as a Sulfur Immobilizer in High Performance Lithium/Sulfur Cells
journal, November 2011

  • Ji, Liwen; Rao, Mumin; Zheng, Haimei
  • Journal of the American Chemical Society, Vol. 133, Issue 46, p. 18522-18525
  • DOI: 10.1021/ja206955k

A Long-Life, High-Rate Lithium/Sulfur Cell: A Multifaceted Approach to Enhancing Cell Performance
journal, November 2013

  • Song, Min-Kyu; Zhang, Yuegang; Cairns, Elton J.
  • Nano Letters, Vol. 13, Issue 12
  • DOI: 10.1021/nl402793z

Lithium–Sulfur Battery Cathode Enabled by Lithium–Nitrile Interaction
journal, December 2012

  • Guo, Juchen; Yang, Zichao; Yu, Yingchao
  • Journal of the American Chemical Society, Vol. 135, Issue 2
  • DOI: 10.1021/ja309435f

Strong Lithium Polysulfide Chemisorption on Electroactive Sites of Nitrogen-Doped Carbon Composites For High-Performance Lithium-Sulfur Battery Cathodes
journal, February 2015

  • Song, Jiangxuan; Gordin, Mikhail L.; Xu, Terrence
  • Angewandte Chemie, Vol. 127, Issue 14
  • DOI: 10.1002/ange.201411109

Review—The Importance of Chemical Interactions between Sulfur Host Materials and Lithium Polysulfides for Advanced Lithium-Sulfur Batteries
journal, January 2015

  • Pang, Quan; Liang, Xiao; Kwok, C. Y.
  • Journal of The Electrochemical Society, Vol. 162, Issue 14
  • DOI: 10.1149/2.0171514jes

Nano-cellular carbon current collectors with stable cyclability for Li–S batteries
journal, January 2013

  • Chung, Sheng-Heng; Manthiram, Arumugam
  • Journal of Materials Chemistry A, Vol. 1, Issue 34
  • DOI: 10.1039/c3ta11819c

A graphene foam electrode with high sulfur loading for flexible and high energy Li-S batteries
journal, January 2015


Polysulfide Shuttle Study in the Li/S Battery System
journal, January 2004

  • Mikhaylik, Yuriy V.; Akridge, James R.
  • Journal of The Electrochemical Society, Vol. 151, Issue 11, p. A1969-A1976
  • DOI: 10.1149/1.1806394

Challenges Facing Lithium Batteries and Electrical Double-Layer Capacitors
journal, September 2012

  • Choi, Nam-Soon; Chen, Zonghai; Freunberger, Stefan A.
  • Angewandte Chemie International Edition, Vol. 51, Issue 40
  • DOI: 10.1002/anie.201201429

Porosity Blocking in Highly Porous Carbon Black by PVdF Binder and Its Implications for the Li–S System
journal, October 2014

  • Lacey, Matthew J.; Jeschull, Fabian; Edström, Kristina
  • The Journal of Physical Chemistry C, Vol. 118, Issue 45
  • DOI: 10.1021/jp508137m

Discharge Process of the Sulfur Cathode with a Gelatin Binder
journal, January 2008

  • Huang, Yaqin; Sun, Jing; Wang, Weikun
  • Journal of The Electrochemical Society, Vol. 155, Issue 10
  • DOI: 10.1149/1.2967191

Stable cycling of lithium sulfide cathodes through strong affinity with a bifunctional binder
journal, January 2013

  • Seh, Zhi Wei; Zhang, Qianfan; Li, Weiyang
  • Chemical Science, Vol. 4, Issue 9
  • DOI: 10.1039/c3sc51476e

Layer-by-Layer Assembled C/S Cathode with Trace Binder for Li–S Battery Application
journal, November 2015

  • Wang, Qian; Yan, Na; Wang, Meiri
  • ACS Applied Materials & Interfaces, Vol. 7, Issue 45
  • DOI: 10.1021/acsami.5b08887

Polyamidoamine dendrimer-based binders for high-loading lithium–sulfur battery cathodes
journal, January 2016


Multidimensional Polycation β-Cyclodextrin Polymer as an Effective Aqueous Binder for High Sulfur Loading Cathode in Lithium–Sulfur Batteries
journal, November 2015

  • Zeng, Fanglei; Wang, Weikun; Wang, Anbang
  • ACS Applied Materials & Interfaces, Vol. 7, Issue 47
  • DOI: 10.1021/acsami.5b08537

Sulfur-Infiltrated Micro- and Mesoporous Silicon Carbide-Derived Carbon Cathode for High-Performance Lithium Sulfur Batteries
journal, June 2013

  • Lee, Jung Tae; Zhao, Youyang; Thieme, Sören
  • Advanced Materials, Vol. 25, Issue 33
  • DOI: 10.1002/adma.201301579

Functional, water-soluble binders for improved capacity and stability of lithium–sulfur batteries
journal, October 2014


Carbon nanofiber–sulfur composite cathode materials with different binders for secondary Li/S cells
journal, March 2012


Enhanced Cyclability for Sulfur Cathode Achieved by a Water-Soluble Binder
journal, July 2011

  • He, Min; Yuan, Li-Xia; Zhang, Wu-Xing
  • The Journal of Physical Chemistry C, Vol. 115, Issue 31
  • DOI: 10.1021/jp2043416

Optimization of mesoporous carbon structures for lithium–sulfur battery applications
journal, January 2011

  • Li, Xiaolin; Cao, Yuliang; Qi, Wen
  • Journal of Materials Chemistry, Vol. 21, Issue 41
  • DOI: 10.1039/c1jm12979a

Understanding the Role of Different Conductive Polymers in Improving the Nanostructured Sulfur Cathode Performance
journal, October 2013

  • Li, Weiyang; Zhang, Qianfan; Zheng, Guangyuan
  • Nano Letters, Vol. 13, Issue 11
  • DOI: 10.1021/nl403130h

Functional organogels from highly efficient organogelator based on perylene bisimide semiconductor
journal, January 2006

  • Li, Xue-Qing; Stepanenko, Vladimir; Chen, Zhijian
  • Chem. Commun., Issue 37
  • DOI: 10.1039/B611422A

Supramolecular Perylene Bisimide-Polysulfide Gel Networks as Nanostructured Redox Mediators in Dissolved Polysulfide Lithium–Sulfur Batteries
journal, September 2015


Three-Dimensional Growth of Li 2 S in Lithium–Sulfur Batteries Promoted by a Redox Mediator
journal, December 2015


The Use of Redox Mediators for Enhancing Utilization of Li 2 S Cathodes for Advanced Li–S Battery Systems
journal, February 2014

  • Meini, Stefano; Elazari, Ran; Rosenman, Ariel
  • The Journal of Physical Chemistry Letters, Vol. 5, Issue 5
  • DOI: 10.1021/jz500222f

The Application of Redox Targeting Principles to the Design of Rechargeable Li-S Flow Batteries
journal, October 2015

  • Li, Jingfa; Yang, Liuqing; Yang, Shiliu
  • Advanced Energy Materials, Vol. 5, Issue 24
  • DOI: 10.1002/aenm.201501808

Rylene and Related Diimides for Organic Electronics
journal, December 2010

  • Zhan, Xiaowei; Facchetti, Antonio; Barlow, Stephen
  • Advanced Materials, Vol. 23, Issue 2, p. 268-284
  • DOI: 10.1002/adma.201001402

Spectroscopic and Theoretical Study of (CF 3 SO 2 ) 2 N - (TFSI - ) and (CF 3 SO 2 ) 2 NH (HTFSI)
journal, May 1998

  • Rey, I.; Johansson, P.; Lindgren, J.
  • The Journal of Physical Chemistry A, Vol. 102, Issue 19
  • DOI: 10.1021/jp980375v

Spectroscopic characterization of the conformational states of the bis(trifluoromethanesulfonyl)imide anion (TFSI−)
journal, January 2005

  • Herstedt, M.; Smirnov, M.; Johansson, P.
  • Journal of Raman Spectroscopy, Vol. 36, Issue 8
  • DOI: 10.1002/jrs.1347

Solvate Structures and Spectroscopic Characterization of LiTFSI Electrolytes
journal, September 2014

  • Seo, Daniel M.; Boyle, Paul D.; Sommer, Roger D.
  • The Journal of Physical Chemistry B, Vol. 118, Issue 47
  • DOI: 10.1021/jp505006x

Determination of the Kinetic Parameters of Mixed-Conducting Electrodes and Application to the System Li[sub 3]Sb
journal, January 1977

  • Weppner, W.
  • Journal of The Electrochemical Society, Vol. 124, Issue 10
  • DOI: 10.1149/1.2133112

High-Capacity Micrometer-Sized Li2 S Particles as Cathode Materials for Advanced Rechargeable Lithium-Ion Batteries
journal, September 2012

  • Yang, Yuan; Zheng, Guangyuan; Misra, Sumohan
  • Journal of the American Chemical Society, Vol. 134, Issue 37, p. 15387-15394
  • DOI: 10.1021/ja3052206

New insight into the discharge process of sulfur cathode by electrochemical impedance spectroscopy
journal, April 2009


Investigations of lithium–sulfur batteries using electrochemical impedance spectroscopy
journal, May 2013


Works referencing / citing this record:

A Robust, Water-Based, Functional Binder Framework for High-Energy Lithium-Sulfur Batteries
journal, June 2017

  • Lacey, Matthew J.; Österlund, Viking; Bergfelt, Andreas
  • ChemSusChem, Vol. 10, Issue 13
  • DOI: 10.1002/cssc.201700743

A Toolbox for Lithium-Sulfur Battery Research: Methods and Protocols
journal, June 2017


Molecular understanding of polyelectrolyte binders that actively regulate ion transport in sulfur cathodes
journal, December 2017


Synergistic Effect between Poly(3,4-ethylenedioxythiophene)-poly(styrene sulfonate) Coated Sulfur Nano-Composites and Poly(vinylidene difluoride) on Lithium-Sulfur Battery
journal, January 2018

  • Liu, Jianchao; Li, Ruhong; Chen, Tianrui
  • Journal of The Electrochemical Society, Vol. 165, Issue 3
  • DOI: 10.1149/2.0551803jes

A Review of Functional Binders in Lithium-Sulfur Batteries
journal, October 2018

  • Yuan, Hong; Huang, Jia-Qi; Peng, Hong-Jie
  • Advanced Energy Materials, Vol. 8, Issue 31
  • DOI: 10.1002/aenm.201802107

A robust network binder with dual functions of Cu 2+ ions as ionic crosslinking and chemical binding agents for highly stable Li–S batteries
journal, January 2018

  • Liu, Jie; Sun, Minghao; Zhang, Qian
  • Journal of Materials Chemistry A, Vol. 6, Issue 17
  • DOI: 10.1039/c8ta01138a

Rational Design of Binders for Stable Li‐S and Na‐S Batteries
journal, December 2019


Housing Sulfur in Polymer Composite Frameworks for Li–S Batteries
journal, February 2019