Rational design of sulphur host materials for Li–S batteries: correlating lithium polysulphide adsorptivity and self-discharge capacity loss

Hart, Connor J.; Cuisinier, Marine; Liang, Xiao; Kundu, Dipan; Garsuch, Arnd; Nazar, Linda F.

doi:10.1039/c4cc08980d

Cited by 213 publications

(182 citation statements)

References 16 publications

Supporting

Mentioning

177

Contrasting

Unclassified

Order By: Relevance

“…On full discharge, the electrolyte is rendered completely colourless, indicating effective conversion to insoluble reduced species, Li 2 S 2 and Li 2 S. A test of the polysulfide adsorption by the MnO 2 nanosheets was conducted by electrochemical titration to measure the degree of residual LiPS in solution after contact, confirming the strong binding ( Supplementary Fig. 4) 38 . ARTICLE nanosheets with LiPSs was determined from Mn 3p 3/2 and S2p X-ray photoelectron spectroscopy (XPS) analysis.…”

Section: Resultsmentioning

confidence: 99%

A highly efficient polysulfide mediator for lithium–sulfur batteries

et al. 2015

Self Cite

View full text Add to dashboard Cite

The lithium-sulfur battery is receiving intense interest because its theoretical energy density exceeds that of lithium-ion batteries at much lower cost, but practical applications are still hindered by capacity decay caused by the polysulfide shuttle. Here we report a strategy to entrap polysulfides in the cathode that relies on a chemical process, whereby a hostmanganese dioxide nanosheets serve as the prototype-reacts with initially formed lithium polysulfides to form surface-bound intermediates. These function as a redox shuttle to catenate and bind 'higher' polysulfides, and convert them on reduction to insoluble lithium sulfide via disproportionation. The sulfur/manganese dioxide nanosheet composite with 75 wt% sulfur exhibits a reversible capacity of 1,300 mA h g À 1 at moderate rates and a fade rate over 2,000 cycles of 0.036%/cycle, among the best reported to date. We furthermore show that this mechanism extends to graphene oxide and suggest it can be employed more widely.

show abstract

Section: Resultsmentioning

confidence: 99%

A highly efficient polysulfide mediator for lithium–sulfur batteries

et al. 2015

Self Cite

View full text Add to dashboard Cite

show abstract

“…Super P carbon, which exhibits a 42% loss under the same conditions). 69 Furthermore, the thiosulfatepolythionate conversion may also account in part for the excellent properties of another Li-S host material, graphene oxide, based on observation of the same thiosulfate and polythionate groups on the GO surface after contact with polysulfides. 66 The GO is proposed to function in the same manner by oxidizing the polysulfides to surface thiosulfate groups while undergoing partial reduction to graphene.…”

Section: Lewis Acid-base Interaction With Polysulfidesmentioning

confidence: 99%

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

Pang

Liang

Kwok

et al. 2015

J. Electrochem. Soc.

Self Cite

298

199

View full text Add to dashboard Cite

This overview details the recently recognized importance of strong chemical interactions between sulfur host materials and lithium polysulfides/sulfide to improve the performance of Li-S batteries, especially with respect to cycle life. Sulfur hosts consisting of: functionally modified surfaces, metal oxides and carbides that rely on either polar interactions or the thiosulfate mechanism for sulfide binding, metal-organic frameworks that exhibit Lewis-acid behavior, and functional polymers are reviewed. We summarize a variety of studies that explore the nature and strength of the interaction of these materials with polysulfides and its effect on cycle life, showing that capacity fading is reduced to as low as 0.03% per cycle with effective functional cathode host surfaces. The ever-growing demand and consumption of energy as well as the depletion of fossil fuels and its associated environmental pollution have driven scientists to pursue renewable energy alternatives. Photovoltaic panels and wind farms are being installed worldwide. However, to fully utilize the electricity generated by these inherently intermittent sources, rechargeable battery systems are a vital part of the system, enabling grid-scale electric storage and benefitting electric and hybrid-electric vehicular transport. 1Amongst all the rechargeable battery systems that have serviced mankind for decades, lithium-ion batteries (LIBs) have dominated the commercial battery market, owing to their high cell voltage, low self-discharge rate, and stable cycling performance.2-4 However, the applications of these batteries have been somewhat limited due to their low energy density (100-220 W·h·kg −1 ) and high cost. 5,6 These battery systems -which consist of a graphite anode and a lithium metal oxide cathode and rely on a Li-ion intercalation mechanismare very attractive for the electric vehicle market. Nonetheless, they do not enable a long driving range unless very large battery packs are utilized, which comes at very high cost and weight. Thus the goal of traveling 500 km per charge is still unattainable. Electrochemical systems that offer a higher capacity and energy density as well as a longer life-time at a lower cost are becoming promising options, but are definitely challenging to bring into practice.Lithium-sulfur (Li-S) batteries are considered as one of the most promising candidates for the next-generation energy storage systems, because of their high theoretical energy density and the natural abundance of sulfur.7-10 A conventional Li-S cell consists of a lithium metal anode and an elemental sulfur cathode in an ether-based electrolyte. The coupling of the high-capacity electrodes of lithium (3840 mA·h·g −1 ) and sulfur (1675 mA·h·g −1 ) affords an average cell voltage of 2.2 V and a theoretical energy density of 2570 W·h·kg −1 . The reversible conversion reaction between sulfur and lithium sulfide (Li 2 S) is accompanied by a series of intermediate lithium polysulfides (LiPSs, Li 2 S n , 2 ≤ n ≤ 8). The electrochemical reactions of Li-S batte...

show abstract

“…7 Subsequent reduction of polysulfides to form final Li 2 S 2 and Li 2 S product was thus rendered more difficult because of the repulsion between the polar polysulfides and the generally nonpolar conductive surface. 51,52 The limited redox efficiency of the polysulfides would thus lead to low sulfur utilization and slow electrochemical kinetics. 2,7 Therefore, development of nanostructure design alone is insufficient and kinetically unfavorable to promote charge transfer, especially for the polysulfide redox in the sulfur cathode.…”

Section: Polymer-based Functional Additives To Promote Polysulfide Rementioning

confidence: 99%

“…[44][45][46][47][48][49][50] However, in general, the polysulfides still tend to disengage from the cathode because both the sulfur host materials and the physical wrapping layers are usually "sulfiphobic". 51,52 In some recent studies, researchers have come to realize that an ideal confinement barrier should have a "sulfiphilic" surface and also be conductive for the absorbed polysulfides. 53 Thus, the attention on designing host materials for sulfur cathodes has extended from physical confinement to surface chemistry.…”

mentioning

confidence: 99%

Review—From Nano Size Effect to In Situ Wrapping: Rational Design of Cathode Structure for High Performance Lithium−Sulfur Batteries

Chen

Shen

Wang

et al. 2017

J. Electrochem. Soc.

View full text Add to dashboard Cite

Rechargeable Li-S batteries have become attractive for next-generation energy storage technology due to their high specific energy, low cost, and materials earth abundance. However, the Li-S technology has not been successfully commercialized because of several outstanding challenges including fast capacity fading, low Coulombic efficiency, and limited rate capability. Over the past few years, considerable efforts have been devoted to solving the challenges associated with the sulfur cathode. In this mini review, we summarize our recent advances in Li-S cathodes, such as the understanding of the nano-size effect in sulfur materials, the design of polymer functional additives, and the realization of a novel in situ wrapping approach for Li-S cathodes. The current Li-S technology calls for a rational design of the Li-S cathode that can lead to excellent overall performance of Li-S batteries. Sulfur is a promising cathode material, which is highly earth abundant and with a theoretical specific capacity as high as 1672 mAh g −1 . When the sulfur cathode couples with a lithium metal anode to assemble rechargeable lithium-sulfur (Li-S) batteries, their theoretical specific energy density can reach 2600 Wh kg −1 , which is 3-5 folds higher than those of state-of-the-art Li-ion batteries.1-3 Because of the high energy density and low cost, rechargeable Li-S batteries are promising for applications not only in consumer electronics but also in energy storage and electric vehicles. [4][5][6] Although the research on Li-S batteries has been ongoing for over three decades, two major challenges still remain in this field: one is the low specific capacity due to high electrical resistivity of elementary S and the solid reduction products ((Li 2 S 2 and Li 2 S)) in the cathodes; the other is the fast capacity fading owing to the shuttle effect, i.e. polysulfide intermediates formed during discharge/charge cycles dissolve in the electrolyte, diffuse to the anode, react with Li metal, and form insoluble Li 2 S 2 and Li 2 S at the anodic region, leading to the loss of lithium metal and sulfur cathodic materials. 7,8 In the past few years, researches have mainly focused on designing nanostructured sulfur host materials to address challenges related to poor electrical conductivity of S/Li 2 S 2 /Li 2 S.9-19 A quantum leap for the nanostructure approach was the utilization of ordered mesoporous carbon CMK-3 to trap sulfur, as reported by Nazar et al. in 2009. 20 The conductive mesoporous carbon framework precisely constrains the growth of sulfur within its channels and thus enables fast electronic and ionic transport. Following this work, Cui et al. designed a series of sulfur nanostructures with complicated host materials demonstrating excellent electrochemical performances.9 Various nanostructured host materials, including but not limited to carbon/sulfur, 11,14,16,17,21 polymer/sulfur, [22][23][24] and metal oxide/sulfur composites 12,25,26 have been investigated. These nanostructures provide new merits and opportunities: (1)...

show abstract

Rational design of sulphur host materials for Li–S batteries: correlating lithium polysulphide adsorptivity and self-discharge capacity loss

Cited by 213 publications

References 16 publications

A highly efficient polysulfide mediator for lithium–sulfur batteries

A highly efficient polysulfide mediator for lithium–sulfur batteries

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

Review—From Nano Size Effect to In Situ Wrapping: Rational Design of Cathode Structure for High Performance Lithium−Sulfur Batteries

Contact Info

Product

Resources

About