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Journal ArticleDOI

A 3D hybrid of chemically coupled nickel sulfide and hollow carbon spheres for high performance lithium–sulfur batteries

01 Sep 2017-Advanced Functional Materials (Wiley)-Vol. 27, Iss: 33, pp 1702524
TL;DR: In this paper, a unique sulfur host hybrid material comprising nanosized nickel sulfide (NiS) uniformly distributed on 3D carbon hollow spheres (C-HS) is fabricated using an in situ thermal reduction and sulfidation method.
Abstract: Lithium–sulfur batteries are a promising next-generation energy storage device owing to their high theoretical capacity and the low cost and abundance of sulfur. However, the low conductivity and loss of active sulfur material during operation greatly limit the rating capabilities and cycling stability of lithium–sulfur batteries. In this work, a unique sulfur host hybrid material comprising nanosized nickel sulfide (NiS) uniformly distributed on 3D carbon hollow spheres (C-HS) is fabricated using an in situ thermal reduction and sulfidation method. In the hybrid material, the nanosized NiS provides a high adsorption capability for polysulfides and the C-HS serves as a physical confinement for polysulfides and also a 3D electron transfer pathway. Moreover, NiS has strong chemical coupling with the C-HS, favoring fast charge transfer and redox kinetics of the sulfur electrode. With a sulfur loading of up to 2.3 mg cm−2, the hybrid material-based lithium–sulfur batteries offer a capacity decay as low as 0.013% per cycle and a capacity of 695 mA h g−1 at 0.5 C after 300 cycles. This unique 3D hybrid material with strong chemical coupling provides a promising sulfur host for high performance lithium–sulfur batteries.
Citations
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Journal ArticleDOI
TL;DR: Insightful insights gathered in the process of studying TMS are provided, and valuable guidelines for engineering other kinds of nanomaterial catalysts for energy conversion and storage technologies are described.
Abstract: Heterogenous electrocatalysts based on transition metal sulfides (TMS) are being actively explored in renewable energy research because nanostructured forms support high intrinsic activities for both the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER). Herein, it is described how researchers are working to improve the performance of TMS-based materials by manipulating their internal and external nanoarchitectures. A general introduction to the water-splitting reaction is initially provided to explain the most important parameters in accessing the catalytic performance of nanomaterials catalysts. Later, the general synthetic methods used to prepare TMS-based materials are explained in order to delve into the various strategies being used to achieve higher electrocatalytic performance in the HER. Complementary strategies can be used to increase the OER performance of TMS, resulting in bifunctional water-splitting electrocatalysts for both the HER and the OER. Finally, the current challenges and future opportunities of TMS materials in the context of water splitting are summarized. The aim herein is to provide insights gathered in the process of studying TMS, and describe valuable guidelines for engineering other kinds of nanomaterial catalysts for energy conversion and storage technologies.

899 citations

Journal ArticleDOI
TL;DR: A variety of strategies such as structural tuning, composition control, doping, hybrid structures, heterostructures, defect control, temperature effects and porosity effects on metal sulfide nanocrystals are discussed and how they are exploited to enhance performance and develop future energy materials.
Abstract: In recent years, nanocrystals of metal sulfide materials have attracted scientific research interest for renewable energy applications due to the abundant choice of materials with easily tunable electronic, optical, physical and chemical properties. Metal sulfides are semiconducting compounds where sulfur is an anion associated with a metal cation; and the metal ions may be in mono-, bi- or multi-form. The diverse range of available metal sulfide materials offers a unique platform to construct a large number of potential materials that demonstrate exotic chemical, physical and electronic phenomena and novel functional properties and applications. To fully exploit the potential of these fascinating materials, scalable methods for the preparation of low-cost metal sulfides, heterostructures, and hybrids of high quality must be developed. This comprehensive review indicates approaches for the controlled fabrication of metal sulfides and subsequently delivers an overview of recent progress in tuning the chemical, physical, optical and nano- and micro-structural properties of metal sulfide nanocrystals using a range of material fabrication methods. For hydrogen energy production, three major approaches are discussed in detail: electrocatalytic hydrogen generation, powder photocatalytic hydrogen generation and photoelectrochemical water splitting. A variety of strategies such as structural tuning, composition control, doping, hybrid structures, heterostructures, defect control, temperature effects and porosity effects on metal sulfide nanocrystals are discussed and how they are exploited to enhance performance and develop future energy materials. From this literature survey, energy conversion currently relies on a limited range of metal sulfides and their composites, and several metal sulfides are immature in terms of their dissolution, photocorrosion and long-term durability in electrolytes during water splitting. Future research directions for innovative metal sulfides should be closely allied to energy and environmental issues, along with their advanced characterization, and developing new classes of metal sulfide materials with well-defined fabrication methods.

685 citations

Journal ArticleDOI
TL;DR: In this paper, an in situ constructed VO2-VN binary host was proposed for Li-S batteries, which combines the merits of ultrafast anchoring (VO2) with electronic conducting (VN) to accomplish smooth immobilization-diffusion-conversion of LiPSs.
Abstract: Lithium–sulfur (Li–S) batteries are deemed as one of the most promising next-generation energy storage systems. However, their practical application is hindered by existing drawbacks such as poor cycling life and low Coulombic efficiency due to the shuttle effect of lithium polysulfides (LiPSs). We herein present an in situ constructed VO2–VN binary host which combines the merits of ultrafast anchoring (VO2) with electronic conducting (VN) to accomplish smooth immobilization–diffusion–conversion of LiPSs. Such synchronous advantages have effectively alleviated the polysulfide shuttling, promoted the redox kinetics, and hence improved the electrochemical performance of Li–S batteries. As a result, the sulfur cathode based on the VO2–VN/graphene host exhibited an impressive rate capability with ∼1105 and 935 mA h g−1 at 1C and 2C, respectively, and maintained long-term cyclability with a low capacity decay of 0.06% per cycle within 800 cycles at 2C. More remarkably, favorable cyclic stability can be attained with a high sulfur loading (13.2 mg cm−2). Even at an elevated temperature (50 °C), the cathodes still delivered superior rate capacity. Our work emphasizes the importance of immobilization–diffusion–conversion of LiPSs toward the rational design of high-load and long-life Li–S batteries.

421 citations

Journal ArticleDOI
TL;DR: This Review summarizes the commonly used routes to build 3D TMD architectures and highlights their applications in electrochemical energy storage and conversion, including batteries, supercapacitors, and electrocatalytic hydrogen evolution.
Abstract: Transition metal dichalcogenides (TMDs) have attracted considerable attention in recent years due to their unique properties and promising applications in electrochemical energy storage and conversion. However, the limited number of active sites and blocked ion and mass transport severely impair the electrochemical performance of TMDs. Construction of three-dimensional (3D) architectures from TMD nanomaterials has been proven an effective strategy to solve the aforementioned problems due to their large specific surface area and short ion and mass transport distance. Here, we summarize the commonly used routes to build 3D TMD architectures and highlight their applications in electrochemical energy storage and conversion, including batteries, supercapacitors, and electrocatalytic hydrogen evolution. Moreover, the challenges and outlooks in this research area are also discussed.

363 citations

References
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Journal ArticleDOI
TL;DR: This review aims to summarize major developments in the field of lithium-sulfur batteries, starting from an overview of their electrochemistry, technical challenges and potential solutions, along with some theoretical calculation results to advance the understanding of the material interactions involved.
Abstract: Due to their high energy density and low material cost, lithium–sulfur batteries represent a promising energy storage system for a multitude of emerging applications, ranging from stationary grid storage to mobile electric vehicles. This review aims to summarize major developments in the field of lithium–sulfur batteries, starting from an overview of their electrochemistry, technical challenges and potential solutions, along with some theoretical calculation results to advance our understanding of the material interactions involved. Next, we examine the most extensively-used design strategy: encapsulation of sulfur cathodes in carbon host materials. Other emerging host materials, such as polymeric and inorganic materials, are discussed as well. This is followed by a survey of novel battery configurations, including the use of lithium sulfide cathodes and lithium polysulfide catholytes, as well as recent burgeoning efforts in the modification of separators and protection of lithium metal anodes. Finally, we conclude with an outlook section to offer some insight on the future directions and prospects of lithium–sulfur batteries.

1,816 citations

Journal ArticleDOI
TL;DR: In this review, recent developments on nanostructured sulfur cathodes and mechanisms behind their operation are presented and discussed and progress on novel characterization of sulfurCathodes is summarized, as it has deepened the understanding of sulfur cathode and will guide further rational design of sulfur electrodes.
Abstract: Rechargeable Li/S batteries have attracted significant attention lately due to their high specific energy and low cost. They are promising candidates for applications, including portable electronics, electric vehicles and grid-level energy storage. However, poor cycle life and low power capability are major technical obstacles. Various nanostructured sulfur cathodes have been developed to address these issues, as they provide greater resistance to pulverization, faster reaction kinetics and better trapping of soluble polysulfides. In this review, recent developments on nanostructured sulfur cathodes and mechanisms behind their operation are presented and discussed. Moreover, progress on novel characterization of sulfur cathodes is also summarized, as it has deepened the understanding of sulfur cathodes and will guide further rational design of sulfur electrodes.

1,727 citations

Journal ArticleDOI
TL;DR: It is shown that the problem of sulfur loss can be effectively diminished by controlling the sulfur as smaller allotropes in the confined space of a conductive microporous carbon matrix.
Abstract: The lithium–sulfur battery holds a high theoretical energy density, 4–5 times that of today’s lithium-ion batteries, yet its applications have been hindered by poor electronic conductivity of the sulfur cathode and, most importantly, the rapid fading of its capacity due to the formation of soluble polysulfide intermediates (Li2Sn, n = 4–8). Despite numerous efforts concerning this issue, combatting sulfur loss remains one of the greatest challenges. Here we show that this problem can be effectively diminished by controlling the sulfur as smaller allotropes. Metastable small sulfur molecules of S2–4 were synthesized in the confined space of a conductive microporous carbon matrix. The confined S2–4 as a new cathode material can totally avoid the unfavorable transition between the commonly used large S8 and S42–. Li–S batteries based on this concept exhibit unprecedented electrochemical behavior with high specific capacity, good cycling stability, and superior rate capability, which promise a practicable bat...

1,443 citations

Journal ArticleDOI
TL;DR: The propelling redox reaction is not limited to Li-S system, and it is foresee the reported strategy herein can be applied in other high-power devices through the systems with controllable redox reactions.
Abstract: Lithium–sulfur (Li–S) battery system is endowed with tremendous energy density, resulting from the complex sulfur electrochemistry involving multielectron redox reactions and phase transformations. Originated from the slow redox kinetics of polysulfide intermediates, the flood of polysulfides in the batteries during cycling induced low sulfur utilization, severe polarization, low energy efficiency, deteriorated polysulfide shuttle, and short cycling life. Herein, sulfiphilic cobalt disulfide (CoS2) was incorporated into carbon/sulfur cathodes, introducing strong interaction between lithium polysulfides and CoS2 under working conditions. The interfaces between CoS2 and electrolyte served as strong adsorption and activation sites for polar polysulfides and therefore accelerated redox reactions of polysulfides. The high polysulfide reactivity not only guaranteed effective polarization mitigation and promoted energy efficiency by 10% but also promised high discharge capacity and stable cycling performance dur...

1,216 citations

Journal ArticleDOI
TL;DR: This work reports a different strategy based on an inherently polar, high surface area metallic oxide cathode host and shows that it mitigates polysulphide dissolution by forming an excellent interface with Li2S and provides experimental evidence for surface-mediated redox chemistry.
Abstract: In lithium-sulfur batteries, many porous conductive carbon materials are proposed to confine soluble polysulfides, but the efficiency is generally low. Here, the authors use a Magneli phase of titanium oxide as the cathode host and electron conduit, which binds the lithium (poly)sulfides well, leading to excellent battery performance.

1,090 citations