Strong Sulfur Binding with Conducting Magnéli-Phase TinO2n–1 Nanomaterials for Improving Lithium–Sulfur Batteries

Tao, Xinyong; Wang, Jianguo; Ying, Zhuogao; Cai, Qiuxia; Zheng, Guangyuan; Gan, Yongping; Huang, Hui; Xia, Yang; Liang, Chao; Zhang, Wenkui; Cui, Yi

doi:10.1021/nl502331f

Cited by 647 publications

(486 citation statements)

References 49 publications

(68 reference statements)

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“…Tao et al has also studied the Ti 4 O 7 material and provided understanding of LiPSs binding via DFT calculations. 56 Using the Ti 4 O 7 (1−20) surface as an test substrate, the optimized geometry indicated that the small sulfur clusters S x (x = 1,2,4) are preferentially bonded to low coordinated Ti sites.…”

Section: Polar-polar Chemical Interactions 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.

293

199

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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...

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Section: Polar-polar Chemical Interactions 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.

293

199

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“…25,59,60 Compared to the inorganic additives as reported in other studies, we demonstrated that polymer-based additives can also exhibit remarkable enhanced redox efficiency of the polysulfides. Poly(2,2,6,6-tetramethyl-1-piperidinyloxy-4-yl methacrylate) (PTMA), which is a stable free radical polymer reported to be potential organic electrode materials, 86 can behave as an efficient additive for high performance Li-S batteries once it was activated via in situ electrochemical oxidation (Fig.…”

Section: Polymer-based Functional Additives To Promote Polysulfide Rementioning

confidence: 51%

“…25,60 As subsequently reported by various other groups, the use of metal oxides, 2D metal carbides/carbonitrides, or doped carbon materials as sulfur hosts or functional additives can also help to suppresses the polysulfide shuttle and improve the polysulfide redox kinetics, often simultaneously. 21,[60][61][62][63][64][65][66][67][68][69][70][71] The downside of adding these inactive materials is the reduction in energy density of the final product the Li-S battery, and the requirement of high specific surface area of the these additives also brings the challenge of materials dispersibility in long and repeated cycles. Although there are still many obstacles to overcome, development of functional additives based on special surface chemistry will be beneficial for Li-S cathodes in the near future.…”

mentioning

confidence: 90%

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.

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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)...

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“…[76][77][78] Nazar's group firstly reported that Ti 4 O 7 has a high affinity for lithium polysulphides due to the contained polar O-Ti-O units. 78 The presence of strong metal oxide-polysulfide interactions has been proved by X-ray photoelectron spectroscopy (XPS), X-ray absorption near-edge structure (XANES) and lithium polysulphides adsorption studies.…”

Section: Nanostructured Metal Oxides Application In Li-s Batteriesmentioning

confidence: 99%

“…Following on Cui's group reported that, compared with the TiO 2 -S, the Ti 4 O 7 -S cathodes exhibited a higher reversible capacity and improved cycling performance. 77 The superiorities of Ti 4 O 7 -S cathodes could be attributed to the strong adsorption of sulfur species on the low-coordinated Ti sites of Ti 4 O 7 , which was revealed by density functional theory (DFT).…”

Section: Nanostructured Metal Oxides Application In Li-s Batteriesmentioning

confidence: 99%

Recent development of metal compound applications in lithium–sulphur batteries

Lai

2017

J. Mater. Res.

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Lithium-sulphur (Li-S) batteries are one of the most promising candidates for the next generation of energy storage systems to alleviate the energy crisis. However, Li-S batteries' commercialization faces the challenges of low active materials utilization, poor cycling life, and low energy density. Recently, tremendous progress has been achieved in improving the electrode performances and tap density by using the nanostructured metal compounds in Li-S batteries. In this review, we not only present the latest various nanostructured metal compounds applications in Li-S batteries, including metal oxides, metal sulphides, metal carbides, metal nitrides, and metal organic frameworks, but also we focus on the interaction mechanisms between these polar metal compounds with polysulphides. The issues and bottlenecks of these metal compounds are concluded and the corresponding available solutions to address these issues are proposed. This systematic discussion and proposed strategies can offer avenues to the practical application of Li-S batteries in the near future.

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Strong Sulfur Binding with Conducting Magnéli-Phase Ti_nO_2n–1 Nanomaterials for Improving Lithium–Sulfur Batteries

Cited by 647 publications

References 49 publications

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

Recent development of metal compound applications in lithium–sulphur batteries

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