Journal Home > Volume 16 , Issue 6
Nano Research 2023, 16(6): 8313-8320 https://doi.org/10.1007/s12274-022-5017-8
Research Article | Open Access | Issue | Published: 24 October 2022

The role of polysulfide-saturation in electrolytes for high power applications of real world Li-S pouch cells

Show Author's Information Tom Boenke1,2,§( ),  Sebastian Kirchhoff1,2,§,  Florian S. Reuter1,2,  Florian Schmidt1,2,  Christine Weller1,2,  Susanne Dörfler2( ),  Kai Schwedtmann3,  Paul Härtel2,  Thomas Abendroth2,  Holger Althues2,  Jan J. Weigand3,  Stefan Kaskel1,2
Technische Universität Dresden, Chair of Inorganic Chemistry I, Bergstr. 66, 01069 Dresden, Germany
Fraunhofer Institute for Material and Beam Technology (IWS), Winterbergstr. 28, 01277 Dresden, Germany
Technische Universität Dresden, Chair of Inorganic Molecular Chemistry, Mommsenstraße 4, 01069 Dresden, Germany

§ Tom Boenke and Sebastian Kirchhoff contributed equally to this work.

Keywords:
high power, pouch cell, lithium-sulfur, polysulfide solubility, electrolyte characterization
Topics:
Lithium sulfur batteries
Cite this article:
Boenke T, Kirchhoff S, Reuter FS, et al. The role of polysulfide-saturation in electrolytes for high power applications of real world Li-S pouch cells. Nano Research, 2023, 16(6): 8313-8320. https://doi.org/10.1007/s12274-022-5017-8
Download citation
EndNote(RIS)
BibTeX

1054

Views

106

Downloads

Citations

2

Crossref

4

WoS

2

Scopus

0

CSCD

Abstract Full text Electronic supplementary material About this article

The lithium-sulfur (Li-S) technology is the most promising candidate for next-generation batteries due to its high theoretical specific energy and steady progress for applications requiring lightweight batteries such as aviation or heavy electric vehicles. For these applications, however, the rate capability of Li-S cells requires significant improvement. Advanced electrolyte formulations in Li-S batteries enable new pathways for cell development and adjustment of all components. However, their rate capability at pouch cell level is often neither evaluated nor compared to state of the art (SOTA) LiTFSI/dimethoxyethane/dioxolane (LITFSI: lithium-bis(trifluoromethylsulfonyl)imide) electrolyte. Herein, the combination of the sparingly polysulfide (PS) solvating hexylmethylether/1,2-dimethoxyethane (HME/DME) electrolyte and highly conductive carbon nanotube Buckypaper (CNT-BP) with low porosity was evaluated in both coin and pouch cells and compared to dimethoxyethane/dioxolane reference electrolyte. An advanced sulfur transfer melt infiltration was employed for cathode production with CNT-BP. The Li+ ion coordination in the HME/DME electrolyte was investigated by nuclear magnetic resonance (NMR) and Raman spectroscopy. Additionally, ionic conductivity and viscosity was investigated for the pristine electrolyte and a polysulfide-statured solution. Both electrolytes, DME/DOL-1/1 (DOL: 1,3-dioxolane) and HME/DME-8/2, are then combined with CNT-BP and transferred to multi-layered pouch cells. This study reveals that the ionic conductivity of the electrolyte increases drastically over state of (dis)charge especially for DME/DOL electrolyte and lean electrolyte regime leading to a better rate capability for the sparingly polysulfide solvating electrolyte. The evaluation in prototype cells is an important step towards bespoke adaption of Li-S batteries for practical applications.


menu
Abstract
Full text
Outline
Electronic supplementary material
About this article

The role of polysulfide-saturation in electrolytes for high power applications of real world Li-S pouch cells

Show Author's information Tom Boenke1,2,§( ), Sebastian Kirchhoff1,2,§, Florian S. Reuter1,2, Florian Schmidt1,2, Christine Weller1,2, Susanne Dörfler2( ), Kai Schwedtmann3, Paul Härtel2, Thomas Abendroth2, Holger Althues2, Jan J. Weigand3, Stefan Kaskel1,2
Technische Universität Dresden, Chair of Inorganic Chemistry I, Bergstr. 66, 01069 Dresden, Germany
Fraunhofer Institute for Material and Beam Technology (IWS), Winterbergstr. 28, 01277 Dresden, Germany
Technische Universität Dresden, Chair of Inorganic Molecular Chemistry, Mommsenstraße 4, 01069 Dresden, Germany

§ Tom Boenke and Sebastian Kirchhoff contributed equally to this work.

Abstract

The lithium-sulfur (Li-S) technology is the most promising candidate for next-generation batteries due to its high theoretical specific energy and steady progress for applications requiring lightweight batteries such as aviation or heavy electric vehicles. For these applications, however, the rate capability of Li-S cells requires significant improvement. Advanced electrolyte formulations in Li-S batteries enable new pathways for cell development and adjustment of all components. However, their rate capability at pouch cell level is often neither evaluated nor compared to state of the art (SOTA) LiTFSI/dimethoxyethane/dioxolane (LITFSI: lithium-bis(trifluoromethylsulfonyl)imide) electrolyte. Herein, the combination of the sparingly polysulfide (PS) solvating hexylmethylether/1,2-dimethoxyethane (HME/DME) electrolyte and highly conductive carbon nanotube Buckypaper (CNT-BP) with low porosity was evaluated in both coin and pouch cells and compared to dimethoxyethane/dioxolane reference electrolyte. An advanced sulfur transfer melt infiltration was employed for cathode production with CNT-BP. The Li+ ion coordination in the HME/DME electrolyte was investigated by nuclear magnetic resonance (NMR) and Raman spectroscopy. Additionally, ionic conductivity and viscosity was investigated for the pristine electrolyte and a polysulfide-statured solution. Both electrolytes, DME/DOL-1/1 (DOL: 1,3-dioxolane) and HME/DME-8/2, are then combined with CNT-BP and transferred to multi-layered pouch cells. This study reveals that the ionic conductivity of the electrolyte increases drastically over state of (dis)charge especially for DME/DOL electrolyte and lean electrolyte regime leading to a better rate capability for the sparingly polysulfide solvating electrolyte. The evaluation in prototype cells is an important step towards bespoke adaption of Li-S batteries for practical applications.

Keywords: high power, pouch cell, lithium-sulfur, polysulfide solubility, electrolyte characterization

References(52)

[1]

Armand, M.; Tarascon, J. M. Building better batteries. Nature 2008, 451, 652–657.
DOI Google Scholar
[2]
Wild, M.; Offer, G. J. Lithium-Sulfur Batteries; John Wiley & Sons: Chichester, 2019.
DOI
[3]

Dörfler, S.; Walus, S.; Locke, J.; Fotouhi, A.; Auger, D. J.; Shateri, N.; Abendroth, T.; Härtel, P.; Althues, H.; Kaskel, S. Recent progress and emerging application areas for lithium-sulfur battery technology. Energy Technol. 2021, 9, 2000694.
DOI Google Scholar
[4]

Boenke, T.; Härtel, P.; Dörfler, S.; Abendroth, T.; Schwotzer, F.; Althues, H.; Kaskel, S. Sulfur transfer melt infiltration for high-power carbon nanotube sheets in lithium-sulfur pouch cells. Batteries Supercaps 2021, 4, 989–1002.
DOI Google Scholar
[5]

Qu, C.; Chen, Y. Q.; Yang, X. F.; Zhang, H. Z.; Li, X. F.; Zhang, H. M. LiNO3-free electrolyte for Li-S battery: A solvent of choice with low Ksp of polysulfide and low dendrite of lithium. Nano Energy 2017, 39, 262–272.
DOI Google Scholar
[6]

Dörfler, S.; Althues, H.; Härtel, P.; Abendroth, T.; Schumm, B.; Kaskel, S. Challenges and key parameters of lithium-sulfur batteries on pouch cell level. Joule 2020, 4, 539–554.
DOI Google Scholar
[7]

Cleaver, T.; Kovacik, P.; Marinescu, M.; Zhang, T.; Offer, G. Perspective-commercializing lithium sulfur batteries: Are we doing the right research? J. Electrochem. Soc. 2018, 165, A6029–A6033.
DOI Google Scholar
[8]

Mikhaylik, Y. V.; Akridge, J. R. Polysulfide shuttle study in the Li/S battery system. J. Electrochem. Soc. 2004, 151, A1969–A1976.
DOI Google Scholar
[9]

Varzi, A.; Thanner, K.; Scipioni, R.; Di Lecce, D.; Hassoun, J.; Dörfler, S.; Altheus, H.; Kaskel, S.; Prehal, C.; Freunberger, S. A. Current status and future perspectives of lithium metal batteries. J. Power Sources 2020, 480, 228803.
DOI Google Scholar
[10]

Fotouhi, A.; Auger, D. J.; O’Neill, L.; Cleaver, T.; Walus, S. Lithium-sulfur battery technology readiness and applications—A review. Energies 2017, 10, 1937.
DOI Google Scholar
[11]

Ji, X. L.; Lee, K. T.; Nazar, L. F. A highly ordered nanostructured carbon-sulphur cathode for lithium-sulphur batteries. Nat. Mater. 2009, 8, 500–506.
DOI Google Scholar
[12]

Bauer, I.; Thieme, S.; Brückner, J.; Althues, H.; Kaskel, S. Reduced polysulfide shuttle in lithium-sulfur batteries using Nafion-based separators. J. Power Sources 2014, 251, 417–422.
DOI Google Scholar
[13]

Pang, Q.; Liang, X.; Shyamsunder, A.; Nazar, L. F. An in vivo formed solid electrolyte surface layer enables stable plating of Li metal. Joule 2017, 1, 871–886.
DOI Google Scholar
[14]

Cheng, X. B.; Huang, J. Q.; Zhang, Q. Review-Li metal anode in working lithium-sulfur batteries. J. Electrochem. Soc. 2018, 165, A6058–A6072.
DOI Google Scholar
[15]

Zhang, S. S. Role of LiNO3 in rechargeable lithium/sulfur battery. Electrochim. Acta 2012, 70, 344–348.
DOI Google Scholar
[16]

Aurbach, D.; Pollak, E.; Elazari, R.; Salitra, G.; Kelley, C. S.; Affinito, J. On the surface chemical aspects of very high energy density, rechargeable Li-sulfur batteries. J. Electrochem. Soc. 2009, 156, A694–A702.
DOI Google Scholar
[17]

Schneider, H.; Weiß, T.; Scordilis-Kelley, C.; Maeyer, J.; Leitner, K.; Peng, H. J.; Schmidt, R.; Tomforde, J. Electrolyte decomposition and gas evolution in a lithium-sulfur cell upon long-term cycling. Electrochim. Acta 2017, 243, 26–32.
DOI Google Scholar
[18]

Vijayakumar, M.; Govind, N.; Walter, E.; Burton, S. D.; Shukla, A.; Devaraj, A.; Xiao, J.; Liu, J.; Wang, C. M.; Karim, A. et al. Molecular structure and stability of dissolved lithium polysulfide species. Phys. Chem. Chem. Phys. 2014, 16, 10923–10932.
DOI Google Scholar
[19]

Kang, N.; Lin, Y. X.; Yang, L.; Lu, D. P.; Xiao, J.; Qi, Y.; Cai, M. Cathode porosity is a missing key parameter to optimize lithium-sulfur battery energy density. Nat. Commun. 2019, 10, 4597.
DOI Google Scholar
[20]

Zhao, M.; Li, B. Q.; Peng, H. J.; Yuan, H.; Wei, J. Y.; Huang, J. Q. Lithium-sulfur batteries under lean electrolyte conditions: Challenges and opportunities. Angew. Chem., Int. Ed. 2020, 59, 12636–12652.
DOI Google Scholar
[21]

Cheng, L.; Curtiss, L. A.; Zavadil, K. R.; Gewirth, A. A.; Shao, Y. Y.; Gallagher, K. G. Sparingly solvating electrolytes for high energy density lithium-sulfur batteries. ACS Energy Lett. 2016, 1, 503–509.
DOI Google Scholar
[22]

Cuisinier, M.; Cabelguen, P. E.; Adams, B. D.; Garsuch, A.; Balasubramanian, M.; Nazar, L. F. Unique behaviour of nonsolvents for polysulphides in lithium-sulphur batteries. Energy Environ. Sci. 2014, 7, 2697–2705.
DOI Google Scholar
[23]

Weng, W.; Pol, V. G.; Amine, K. Ultrasound assisted design of sulfur/carbon cathodes with partially fluorinated ether electrolytes for highly efficient Li/S batteries. Adv. Mater. 2013, 25, 1608–1615.
DOI Google Scholar
[24]

Dokko, K.; Tachikawa, N.; Yamauchi, K.; Tsuchiya, M.; Yamazaki, A.; Takashima, E.; Park, J. W.; Ueno, K.; Seki, S.; Serizawa, N. et al. Solvate ionic liquid electrolyte for Li-S batteries. J. Electrochem. Soc. 2013, 160, A1304–A1310.
DOI Google Scholar
[25]

Azimi, N.; Xue, Z.; Bloom, I.; Gordin, M. L.; Wang, D. H.; Daniel, T.; Takoudis, C.; Zhang, Z. C. Understanding the effect of a fluorinated ether on the performance of lithium-sulfur batteries. ACS Appl. Mater. Interfaces 2015, 7, 9169–9177.
DOI Google Scholar
[26]

Weller, C.; Thieme, S.; Härtel, P.; Althues, H.; Kaskel, S. Intrinsic shuttle suppression in lithium-sulfur batteries for pouch cell application. J. Electrochem. Soc. 2017, 164, A3766–A3771.
DOI Google Scholar
[27]

Weller, C.; Pampel, J.; Dörfler, S.; Althues, H.; Kaskel, S. Polysulfide shuttle suppression by electrolytes with low-density for high-energy lithium-sulfur batteries. Energy Technol. 2019, 7, 1900625.
DOI Google Scholar
[28]

Yanagi, M.; Ueno, K.; Ando, A.; Li, S. L.; Matsumae, Y.; Liu, J. L.; Dokko, K.; Watanabe, M. Effects of polysulfide solubility and Li ion transport on performance of Li-S batteries using sparingly solvating electrolytes. J. Electrochem. Soc. 2020, 167, 070531.
DOI Google Scholar
[29]

Nakanishi, A.; Ueno, K.; Watanabe, D.; Ugata, Y.; Matsumae, Y.; Liu, J. L.; Thomas, M. L.; Dokko, K.; Watanabe, M. Sulfolane-based highly concentrated electrolytes of lithium bis(trifluoromethanesulfonyl)amide: Ionic transport, Li-ion coordination, and Li-S battery performance. J. Phys. Chem. C 2019, 123, 14229–14238.
DOI Google Scholar
[30]

Liu, T.; Li, H. J.; Yue, J. M.; Feng, J. N.; Mao, M. L.; Zhu, X. Z.; Hu, Y. S.; Li, H.; Huang, X. J.; Chen, L. Q. et al. Ultralight electrolyte for high-energy lithium-sulfur pouch cells. Angew. Chem., Int. Ed. 2021, 60, 17547–17555.
DOI Google Scholar
[31]

Di Lecce, D.; Marangon, V.; Du, W. J.; Brett, D. J. L.; Shearing, P. R.; Hassoun, J. The role of synthesis pathway on the microstructural characteristics of sulfur-carbon composites: X-ray imaging and electrochemistry in lithium battery. J. Power Sources 2020, 472, 228424.
DOI Google Scholar
[32]

Kensy, C.; Schwotzer, F.; Dörfler, S.; Althues, H.; Kaskel, S. Impact of carbon porosity on sulfur conversion in Li-S battery cathodes in a sparingly polysulfide solvating electrolyte. Batteries Supercaps 2021, 4, 823–833.
DOI Google Scholar
[33]

Yuan, Z.; Peng, H. J.; Huang, J. Q.; Liu, X. Y.; Wang, D. W.; Cheng, X. B.; Zhang, Q. Hierarchical free-standing carbon-nanotube paper electrodes with ultrahigh sulfur-loading for lithium-sulfur batteries. Adv. Funct. Mater. 2014, 24, 6105–6112.
DOI Google Scholar
[34]

Chung, S. H.; Chang, C. H.; Manthiram, A. Robust, ultra-tough flexible cathodes for high-energy Li-S batteries. Small 2016, 12, 939–950.
DOI Google Scholar
[35]

Fang, R. P.; Li, G. X.; Zhao, S. Y.; Yin, L. C.; Du, K.; Hou, P. X.; Wang, S. G.; Cheng, H. M.; Liu, C.; Li, F. Single-wall carbon nanotube network enabled ultrahigh sulfur-content electrodes for high-performance lithium-sulfur batteries. Nano Energy 2017, 42, 205–214.
DOI Google Scholar
[36]

Dibden, J. W.; Smith, J. W.; Zhou, N.; Garcia-Araez, N.; Owen, J. R. Predicting the composition and formation of solid products in lithium-sulfur batteries by using an experimental phase diagram. Chem. Commun. 2016, 52, 12885–12888.
DOI Google Scholar
[37]

Zhang, T.; Marinescu, M.; O’Neill, L.; Wild, M.; Offer, G. Modeling the voltage loss mechanisms in lithium-sulfur cells: The importance of electrolyte resistance and precipitation kinetics. Phys. Chem. Chem. Phys. 2015, 17, 22581–22586.
DOI Google Scholar
[38]

Schmidt, F.; Korzhenko, A.; Härtel, P.; Reuter, F. S.; Ehrling, S.; Dörfler, S.; Abendroth, T.; Althues, H.; Kaskel, S. Influence of external stack pressure on the performance of Li-S pouch cell. J. Phys. Energy 2022, 4, 014004.
DOI Google Scholar
[39]

Kawase, A.; Shirai, S.; Yamoto, Y.; Arakawa, R.; Takata, T. Electrochemical reactions of lithium-sulfur batteries: An analytical study using the organic conversion technique. Phys. Chem. Chem. Phys. 2014, 16, 9344–9350.
DOI Google Scholar
[40]

Ueno, K.; Tatara, R.; Tsuzuki, S.; Saito, S.; Doi, H.; Yoshida, K.; Mandai, T.; Matsugami, M.; Umebayashi, Y.; Dokko, K. et al. Li+ solvation in glyme-Li salt solvate ionic liquids. Phys. Chem. Chem. Phys. 2015, 17, 8248–8257.
DOI Google Scholar
[41]

Kaiser, M. R.; Chou, S.; Liu, H. K.; Dou, S. X.; Wang, C. S.; Wang, J. Z. Structure–property relationships of organic electrolytes and their effects on Li/S battery performance. Adv. Mater. 2017, 29, 1700449.
DOI Google Scholar
[42]

Yu, Z. A.; Wang, H. S.; Kong, X.; Huang, W.; Tsao, Y.; Mackanic, D. G.; Wang, K. C.; Wang, X. C.; Huang, W. X.; Choudhury, S. et al. Molecular design for electrolyte solvents enabling energy-dense and long-cycling lithium metal batteries. Nat. Energy 2020, 5, 526–533.
DOI Google Scholar
[43]

Ren, X. D.; Zou, L. F.; Cao, X.; Engelhard, M. H.; Liu, W.; Burton, S. D.; Lee, H.; Niu, C. J.; Matthews, B. E.; Zhu, Z. H. et al. Enabling high-voltage lithium-metal batteries under practical conditions. Joule 2019, 3, 1662–1676.
DOI Google Scholar
[44]

Zou, Q. L.; Lu, Y. C. Solvent-dictated lithium sulfur redox reactions: An operando UV–vis spectroscopic study. J. Phys. Chem. Lett. 2016, 7, 1518–1525.
DOI Google Scholar
[45]

Cataldo, F. A revision of the Gutmann donor numbers of a series of phosphoramides including TEPA. Eur. Chem. Bull. 2015, 4, 92–97.
DOI Google Scholar
[46]
Reichardt, C.; Welton, T. Solvents and Solvent Effects in Organic Chemistry; Wiley-VCH: Weinheim, 2003.
DOI
[47]

Andersen, A.; Rajput, N. N.; Han, K. S.; Pan, H. L.; Govind, N.; Persson, K. A.; Mueller, K. T.; Murugesan, V. Structure and dynamics of polysulfide clusters in a nonaqueous solvent mixture of 1,3-dioxolane and 1,2-dimethoxyethane. Chem. Mater. 2019, 31, 2308–2319.
DOI Google Scholar
[48]

Hippauf, F.; Nickel, W.; Hao, G. P.; Schwedtmann, K.; Giebeler, L.; Oswald, S.; Borchardt, L.; Doerfler, S.; Weigand, J. J.; Kaskel, S. The importance of pore size and surface polarity for polysulfide adsorption in lithium sulfur batteries. Adv. Mater. Interfaces 2016, 3, 1600508.
DOI Google Scholar
[49]

Moon, H.; Mandai, T.; Tatara, R.; Ueno, K.; Yamazaki, A.; Yoshida, K.; Seki, S.; Dokko, K.; Watanabe, M. Solvent activity in electrolyte solutions controls electrochemical reactions in Li-ion and Li-sulfur batteries. J. Phys. Chem. C 2015, 119, 3957–3970.
DOI Google Scholar
[50]

Zhang, C.; Ueno, K.; Yamazaki, A.; Yoshida, K.; Moon, H.; Mandai, T.; Umebayashi, Y.; Dokko, K.; Watanabe, M. Chelate effects in glyme/lithium bis(trifluoromethanesulfonyl)amide solvate ionic liquids. I. Stability of solvate cations and correlation with electrolyte properties. J. Phys. Chem. B 2014, 118, 5144–5153.
DOI Google Scholar
[51]

Pang, Q.; Shyamsunder, A.; Narayanan, B.; Kwok, C. Y.; Curtiss, L. A.; Nazar, L. F. Tuning the electrolyte network structure to invoke quasi-solid state sulfur conversion and suppress lithium dendrite formation in Li-S batteries. Nat. Energy 2018, 3, 783–791.
DOI Google Scholar
[52]

Zheng, J. M.; Lochala, J. A.; Kwok, A.; Deng, Z. D.; Xiao, J. Research progress towards understanding the unique interfaces between concentrated electrolytes and electrodes for energy storage applications. Adv. Sci. 2017, 4, 1700032.
DOI Google Scholar
File
5017_ESM.pdf (816.2 KB)
Publication history
Copyright
Acknowledgements
Rights and permissions

Publication history

Received: 12 April 2022
Revised: 29 August 2022
Accepted: 05 September 2022
Published: 24 October 2022
Issue date: June 2023

Copyright

© The Author(s) 2022

Acknowledgements

Acknowledgements

The research was financed by the German Ministry of Education and Research (BMBF) in the project “HiPoLiS” (No. 03XP0178A). The authors thank Kelly Henze and Peter Fleischer (Fraunhofer IWS) for electrode preparation and cell assembly, Susann Kleber (Fraunhofer IWS) for Raman spectroscopy, and Nelly Weiß and Friedrich Schwotzer (TU Dresden) for TEM and SEM analysis.

Rights and permissions

Copyright: © 2022 by the author(s). This article is an open access article distributed under Creative Commons Attribution License (CC BY 4.0), visit https://creativecommons.org/licenses/by/4.0/.

Return