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Title: Polysulfide-Shuttle Control in Lithium-Sulfur Batteries with a Chemically/Electrochemically Compatible NaSICON-Type Solid Electrolyte

Authors:
 [1];  [2];  [2];  [1]
  1. Electrochemical Energy Laboratory, Materials Science and Engineering Program, The University of Texas at Austin, Austin TX 78712 USA
  2. Ceramatec, Inc, Salt Lake City UT 84119 USA
Publication Date:
Sponsoring Org.:
USDOE
OSTI Identifier:
1401474
Grant/Contract Number:
AR0000377
Resource Type:
Journal Article: Publisher's Accepted Manuscript
Journal Name:
Advanced Energy Materials
Additional Journal Information:
Journal Volume: 6; Journal Issue: 24; Related Information: CHORUS Timestamp: 2017-10-20 17:02:18; Journal ID: ISSN 1614-6832
Publisher:
Wiley Blackwell (John Wiley & Sons)
Country of Publication:
Germany
Language:
English

Citation Formats

Yu, Xingwen, Bi, Zhonghe, Zhao, Feng, and Manthiram, Arumugam. Polysulfide-Shuttle Control in Lithium-Sulfur Batteries with a Chemically/Electrochemically Compatible NaSICON-Type Solid Electrolyte. Germany: N. p., 2016. Web. doi:10.1002/aenm.201601392.
Yu, Xingwen, Bi, Zhonghe, Zhao, Feng, & Manthiram, Arumugam. Polysulfide-Shuttle Control in Lithium-Sulfur Batteries with a Chemically/Electrochemically Compatible NaSICON-Type Solid Electrolyte. Germany. doi:10.1002/aenm.201601392.
Yu, Xingwen, Bi, Zhonghe, Zhao, Feng, and Manthiram, Arumugam. 2016. "Polysulfide-Shuttle Control in Lithium-Sulfur Batteries with a Chemically/Electrochemically Compatible NaSICON-Type Solid Electrolyte". Germany. doi:10.1002/aenm.201601392.
@article{osti_1401474,
title = {Polysulfide-Shuttle Control in Lithium-Sulfur Batteries with a Chemically/Electrochemically Compatible NaSICON-Type Solid Electrolyte},
author = {Yu, Xingwen and Bi, Zhonghe and Zhao, Feng and Manthiram, Arumugam},
abstractNote = {},
doi = {10.1002/aenm.201601392},
journal = {Advanced Energy Materials},
number = 24,
volume = 6,
place = {Germany},
year = 2016,
month = 8
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record at 10.1002/aenm.201601392

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  • Formation of soluble polysulfide (PS), which is a key feature of lithium sulfur (Li–S) batteries, provides a fast redox kinetic based on a liquid–solid mechanism; however, it imposes the critical problem of PS shuttle. Here, we address the dilemma by exploiting a solvent-swollen polymeric single-ion conductor (SPSIC) as the electrolyte medium of the Li–S battery. The SPSIC consisting of a polymeric single-ion conductor and lithium salt-free organic solvents provides Li ion hopping by forming a nanoscale conducting channel and suppresses PS shuttle according to the Donnan exclusion principle when being employed for Li–S batteries. The organic solvents at the interfacemore » of the sulfur/carbon composite and SPSIC eliminate the poor interfacial contact and function as a soluble PS reservoir for maintaining the liquid–solid mechanism. Furthermore, the quasi-solid-state SPSIC allows the fabrication of a bipolar-type stack, which promises the realization of a high-voltage and energy-dense Li–S battery.« less
  • The effects of mild oxidation (burning) of 2 synthetic graphites on the reversible (Q{sub R}) and irreversible (Q{sub IR}) capacities, anode-degradation rate (on cycling) in three different electrolytes and graphite-surface topology have been studied. STM images of both modified graphites show nanochannels having an opening of a few nanometers and up to tens of nanometers. It is believed that these nanochannels are formed at the zigzag and armchair faces between two adjacent crystallites and in the vicinity of defects and impurities. Mild burn-off was found to improve performance in Li/Li{sub x}C cells: Q{sub R} is increased by 10--30%, Q{sub IR}more » is generally decreased (for less than 6% burn-off) and Li{sub x}C{sub 6} anode degradation rate is much lower. Performance improvement is attributed to the formation of a solid electrolyte interface (SEI) chemically bonded to the surface carboxylic groups at the zigzag and armchair faces, and to accommodation of extra lithium at the zigzag, armchair, and other edge sites and nanovoids.« less
  • The shuttling of polysulfide ions between the electrodes in a lithium-sulfur battery is a major technical issue limiting the self-discharge and cycle life of this high-energy rechargeable battery. Although there have been attempts to suppress the shuttling process, there has not been a direct measurement of the rate of shuttling. We report here a simple and direct measurement of the rate of the shuttling (that we term “shuttle current”), applicable to the study of any type of lithium-sulfur cell. We demonstrate the effectiveness of this measurement technique using cells with and without lithium nitrate (a widely-used shuttle suppressor additive). Wemore » present a phenomenological analysis of the shuttling process and simulate the shuttle currents as a function of the state-of-charge of a cell. We also demonstrate how the rate of decay of the shuttle current can be used to predict the capacity fade in a lithium-sulfur cell due to the shuttle process. As a result, we expect that this new ability to directly measure shuttle currents will provide greater insight into the performance differences observed with various additives and electrode modifications that are aimed at suppressing the rate of shuttling of polysulfide ions and increasing the cycle life of lithium-sulfur cells.« less
  • Li-S battery is a complicated system with many challenges existing before its final market penetration. While most of the reported work for Li-S batteries is focused on the cathode design, we demonstrate in this work that the anode consumption accelerated by corrosive polysulfide solution also critically determines the Li-S cell performance. To validate this hypothesis, ionic liquid (IL) N-methyl-N-butylpyrrolidinium bis(trifluoromethylsulfonyl)imide (Py14TFSI) has been employed to modify the properties of SEI layer formed on Li metal surface in Li-S batteries. It is found that the IL-enhanced passivation film on the lithium anode surface exhibits much different morphology and chemical compositions, effectivelymore » protecting lithium metal from continuous attack by soluble polysulfides. Therefore, both cell impedance and the irreversible consumption of polysulfides on lithium metal are reduced. As a result, the Coulombic efficiency and the cycling stability of Li-S batteries have been greatly improved. After 120 cycles, Li-S battery cycled in the electrolyte containing IL demonstrates a high capacity retention of 94.3% at 0.1 C rate. These results unveil another important failure mechanism for Li-S batteries and shin the light on the new approaches to improve Li-S battery performances.« less