<i>In situ</i>optical spectroscopy characterization for optimal design of lithium–sulfur batteries

Zhang, Li; Qian, Tao; Zhu, Xingyu; Hu, Zhongli; Wang, Mengfan; Zhang, Liya; Jiang, Tao; Tian, Jing‐Hua; Yan, Chenglin

doi:10.1039/c9cs00381a

Cited by 153 publications

(106 citation statements)

References 49 publications

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“…The formation of PS during cycling in ether‐based electrolytes has already been reported by several groups, both by Raman spectroscopy and other techniques . It is commonly accepted that the high voltage plateau at 2.4–2.3 V is related to the

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ring opening and long‐chain PS Li 2 S n ( n =5–8) formation, whereas short‐chain PS Li 2 S n ( n =1–4) are the main species involved in the second plateau at 2.1 V . Our results for a DME based electrolyte show similar behavior (Figures S1, S2); upon discharge, the voltage profile begins with a slope at 2.34 V, the absence of the first plateau being due to the high solubility of S 8 and its chemical reduction in the electrolyte.…”

Section: Figuresupporting

confidence: 86%

S_{8}

ring opening and long‐chain PS Li 2 S n ( n =5–8) formation, whereas short‐chain PS Li 2 S n ( n =1–4) are the main species involved in the second plateau at 2.1 V .…”

Section: Figurementioning

confidence: 78%

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Monitoring Polysulfide Solubility and Diffusion in Fluorinated Ether‐Based Electrolytes by Operando Raman Spectroscopy

Bouchal

Boulaoued

Johansson

2020

Batteries & Supercaps

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Polysulfide (PS) solubility is a key property of LiÀ S battery electrolytes for the conversion reaction(s) at the electrolyteelectrode interface. When PSs shuttle between the composite C/S cathode and the lithium metal anode, however, this leads to a continuous loss of active material and thus rapid capacity fading. In order to restrict the shuttle effect, fluorinated ethers have recently been proposed as a remedy; by only sparsely dissolving PSs they physically block the diffusion. We show here how the diffusion of PSs in fluorinated ethers, as monitored by operando Raman spectroscopy, is selective and that only shortchain PS (S 2À 4 ) are soluble and diffuse. This fundamental observation can be used to further leverage the practical performance of LiÀ S batteries by novel electrolyte design.For a more sustainable future without fossil energy, the electrification of vital markets such as transportation and largescale grid storage is a key, but they require high energy density batteries for longer driving ranges and smarter storage capabilities. [1][2][3] Although current lithium-ion battery cells can reach up to ca. 300 W · h · kg À 1 these can hardly satisfy the fastexpanding demand, [4] why the development of batteries with even higher energy density, longer cycle-life and acceptable levels of safety is critically needed. [3,5,6] Lithium-sulfur (LiÀ S) batteries are considered as one of the most promising rechargeable battery technologies due to that sulfur is abundant and non-toxic, and meets the requirements of renewable and clean energy development. [5,6] Today, LiÀ S battery cells can deliver 400-500 W · h · kg À 1 , but only with a relatively short cycle-life, which considerably restricts any largescale commercialization. [7] The electrochemical reactions of LiÀ S batteries involve complicated conversion reactions based on multi-electron transfer, generating a series of intermediate soluble polysulfide (PS) species Li 2 S n (4 � n � 8). [8] The PS intermediates not only dissolve into the electrolyte, causing severe loss of active material, but also shuttle between the anode and the cathode without performing useful work. This shuttling results in low Coulombic efficiency, relatively short cycle-life, and increased internal cell resistance. [9,10] Therefore, the control of PS solubility and diffusion are keys to achieve more performant LiÀ S batteries.Several approaches have been used to tackle the shuttling; [9] mainly by protecting the lithium surface by e. g. adding LiNO 3 to the electrolyte, [11][12][13][14] but this is at the expense of reduced cell voltage and is seriously plagued by gradual decay upon cycling. Another approach is to trap the PS in or close to the C/S composite cathode. [9,15] Yet, another approach, and the one we target here, is to use electrolytes that sparsely dissolve PS e. g. highly concentrated [16] or fluorinated etherbased electrolytes. [17][18][19][20][21][22][23][24] Sulfur and PS solubility in fluorinated ethers are several orders of magnitude lower as compared to linear g...

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S_{8}

Section: Figuresupporting

confidence: 86%

S_{8}

ring opening and long‐chain PS Li 2 S n ( n =5–8) formation, whereas short‐chain PS Li 2 S n ( n =1–4) are the main species involved in the second plateau at 2.1 V .…”

Section: Figurementioning

confidence: 78%

Monitoring Polysulfide Solubility and Diffusion in Fluorinated Ether‐Based Electrolytes by Operando Raman Spectroscopy

Bouchal

Boulaoued

Johansson

2020

Batteries & Supercaps

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“…Importantly, the publication of Liu et al. indicates that for elucidating the chemistry of Li‐S, and consequently developing new materials, in situ analysis can be compelling; thereby, a key for some of the open questions …”

Section: Energy Storage Applicationsmentioning

confidence: 99%

TMDs beyond MoS₂ for Electrochemical Energy Storage

Soares

Mukherjee

Singh

2020

Chemistry A European J

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Atomically thin sheets of two‐dimensional (2D) transition metal dichalcogenides (TMDs) have attracted interest as high capacity electrode materials for electrochemical energy storage devices owing to their unique properties (high surface area, high strength and modulus, faster ion diffusion, and so on), which arise from their layered morphology and diversified chemistry. Nevertheless, low electronic conductivity, poor cycling stability, large structural changes during metal‐ion insertion/extraction along with high cost of manufacture are challenges that require further research in order for TMDs to find use in commercial batteries and supercapacitors. Here, a systematic review of cutting‐edge research focused on TMD materials beyond the widely studied molybdenum disulfide or MoS2 electrode is reported. Accordingly, a critical overview of the recent progress concerning synthesis methods, physicochemical and electrochemical properties is given. Trends and opportunities that may contribute to state‐of‐the‐art research are also discussed.

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“…To this end, the development of various in situ techniques and electrochemical methods can provide the in‐depth understanding of redox mechanism in Li–S chemistry, thereby providing guidance for the optimal design of Li–S batteries. [ 13 ]…”

Section: Introductionmentioning

confidence: 99%

Optimizing Redox Reactions in Aprotic Lithium–Sulfur Batteries

Zhou

Lei

et al. 2020

Advanced Energy Materials

140

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The lithium–sulfur battery is regarded as one of the promising energy‐storage devices beyond lithium‐ion battery due to its overwhelming energy density. The aprotic Li–S electrochemistry is hampered by issues arising from the complex solid–liquid–solid conversion process. Recently, tremendous efforts have been made to optimize the electrochemical reaction in Li–S batteries through rationally designing compositions and structures of cathodes. However, a deep and comprehensive understanding of the actual mechanisms of Li–S batteries and their impact on the performance is still insufficient. The vigorous development of various electrochemical analysis and in situ techniques establish a bridge between the microstructure of components and the macroscopic electrochemical performance, thus providing more scientific guidance for the optimal design of Li–S batteries. In this review, based on insights into the mechanism of aprotic Li–S electrochemistry with the aid of in situ characterization and electrochemical methods, the advanced innovations in optimizing Li–S batteries are systematically summarized, including the materials design, cathode configurations optimization, and electrolyte engineering, with the aim to gain a comprehensive understanding of cathodic redox processes and thus achieve high‐performance Li–S batteries. The current status and possible future directions of the field are accordingly outlined.

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In situoptical spectroscopy characterization for optimal design of lithium–sulfur batteries

Abstract: Recent advances in optimal design of lithium–sulfur batteries with the aid of in situ optical spectroscopic techniques, including Raman, infrared and ultraviolet-visible spectroscopies, are systematically summarized.

Cited by 153 publications

References 49 publications

Monitoring Polysulfide Solubility and Diffusion in Fluorinated Ether‐Based Electrolytes by Operando Raman Spectroscopy

Monitoring Polysulfide Solubility and Diffusion in Fluorinated Ether‐Based Electrolytes by Operando Raman Spectroscopy

TMDs beyond MoS₂ for Electrochemical Energy Storage

Optimizing Redox Reactions in Aprotic Lithium–Sulfur Batteries

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In situoptical spectroscopy characterization for optimal design of lithium–sulfur batteries

Abstract: Recent advances in optimal design of lithium–sulfur batteries with the aid of in situ optical spectroscopic techniques, including Raman, infrared and ultraviolet-visible spectroscopies, are systematically summarized.

Cited by 153 publications

References 49 publications

Monitoring Polysulfide Solubility and Diffusion in Fluorinated Ether‐Based Electrolytes by Operando Raman Spectroscopy

Monitoring Polysulfide Solubility and Diffusion in Fluorinated Ether‐Based Electrolytes by Operando Raman Spectroscopy

TMDs beyond MoS2 for Electrochemical Energy Storage

Optimizing Redox Reactions in Aprotic Lithium–Sulfur Batteries

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Product

Resources

About

TMDs beyond MoS₂ for Electrochemical Energy Storage