Polysulfide Chemistry in Sodium–Sulfur Batteries and Related Systems— A Computational Study by G3X(MP2) and PCM Calculations

Steudel, Ralf; Steudel, Yana

doi:10.1002/chem.201203397

Cited by 56 publications

(105 citation statements)

References 98 publications

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“…Our assignment of the PS species is based mainly on reports on PS in solution and various in situ characterization studies (Table S1). The peak with a high intensity at 397 cm −1 is assigned to

S_{6}^{2 -}

and this corresponds well to the calculated value by Steudel et al . The peak at 502 cm −1 can be attributed to long‐chain PS,

{normalS}_{n}^{2 -}

( n =7 or 8) .…”

Section: Figuresupporting

confidence: 90%

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_{6}^{2 -}

and this corresponds well to the calculated value by Steudel et al . The peak at 502 cm −1 can be attributed to long‐chain PS,

{normalS}_{n}^{2 -}

( n =7 or 8) .…”

Section: Figuresupporting

confidence: 90%

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

Bouchal

Boulaoued

Johansson

2020

Batteries & Supercaps

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show abstract

“…It features a very high alkaline metal storage capacity per weight and is a promising material for cathodes of rechargeable batteries, including lithium-sulfur (Li-S) [9] and sodium-sulfur (Na-S) systems. [10] Sulfur-containing functional groups lead to a high molar refraction and are thus utilized for the synthesis of materials with high refractive indexes. [11] Sulfur-rich materials also exhibit high transparency in the IR region, which enables their application in IR optical materials.…”

Section: Introductionmentioning

confidence: 99%

Recent Approaches for the Direct Use of Elemental Sulfur in the Synthesis and Processing of Advanced Materials

2015

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Elemental sulfur is an abundant and inexpensive material obtained as a by-product of natural-gas and petroleum refining operations. Recently, the need for the development of new energy-storage systems brought into light the potential of sulfur as a high-capacity cathode material in secondary batteries. Sulfur-containing materials were also shown to have useful IR optical properties. These developments coupled with growing environmental concerns related to the global production of excess elemental sulfur have led to a keen interest in its utilization as a feedstock in materials applications. This Minireview focuses on the recent developments on physical and chemical methods for directly processing elemental sulfur to produce functional composites and polymers.

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“…Nevertheless, these polysulfides are solid, not rechargeable and electronically non-conductive. 21 The cut-off potential during charge exceeds 2.08 V (i.e the Na2S5 phase region) and reaches nominally 2.6 V.…”

Section: Operation Of It Nas Cellmentioning

confidence: 99%

An Electrochemical Study on the Cathode of the Intermediate Temperature Tubular Sodium-Sulfur (NaS) Battery

Nikiforidis

Jongerden²,

Jongerden³

et al. 2019

J. Electrochem. Soc.

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The development of low-cost energy storage schemes is imminent in light of the ever-growing demand of electricity. Sodium-sulfur (NaS) batteries offer low-cost technology for energy storage applications due to the intrinsically high capacities of elemental sodium and sulfur as well as their abundant resources. Operating this battery technology on the intermediate range (130-200°C) can lead to lower material costs, mitigate thermal management and safety issues and enhance cycle life. Herein, an electrochemical study (in the form of different carbonaceous materials) on the cathode of the IT NaS cell is performed at 150°C and a concentration range of 1.5 to 3 M sodium pentasulfide dissolved in tetraglyme, showing a robust long term performance (42 days of continuous cycling) with a volumetric energy density of 83 Wh L-1. Most importantly, the cell was eligible for a tenfold volume scale-up considerably enhancing its capacity (790 mAh) but in the same time somewhat hindered by mass transport, especially during the end of the discharge process as manifested by electrochemical impedance spectroscopy.

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Polysulfide Chemistry in Sodium–Sulfur Batteries and Related Systems— A Computational Study by G3X(MP2) and PCM Calculations

Cited by 56 publications

References 98 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

Recent Approaches for the Direct Use of Elemental Sulfur in the Synthesis and Processing of Advanced Materials

An Electrochemical Study on the Cathode of the Intermediate Temperature Tubular Sodium-Sulfur (NaS) Battery

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