Graphene sheet-encased silica/sulfur composite cathode for improved cyclability of lithium-sulfur batteries

Journal of Solid State Electrochemistry - The “shuttle effect” of polysulfides is a serious issue, resulting in a decrease in the life-cycle of lithium-sulfur (Li-S) batteries. To...     

Concrete-like high sulfur content cathodes with enhanced electrochemical performance for lithium-sulfur batteries

Nowadays,lithium-sulfur batteries have attracted numerous attention due to their high specific capacity,high energy density,low cost and environmental benignancy.However,there are some critical challenges to be overcome such as low electronic conductivity and capacity fading caused by shuttle effect.Many attempts have been conducted to improve the electrochemical performance by designing effective sulfur hosts.In this paper,we synthesize a concrete-like sulfur/carbon cathode with high sulfur content(84%)by using 3D macroporous hosts with high pore volume.Sophisticated strategies of using polarized carbon framework and polymer coating are applied to synergistically control the dissolution of polysulfides so that the capacity retention and high rate performance can be remarkably enhanced.As a result,the composite exhibits a specific discharge capacity of 820 mAhg~(-1)at a discharge current of 800 mAg~(-1)(approximate to 0.5 C)after 100 cycles,calculated on the integrated mass of composite,which is superior to most report results.     

High capacity vertical aligned carbon nanotube/sulfur composite cathodes for lithium-sulfur batteries

Binder free vertical aligned (VA) CNT/sulfur composite electrodes with high sulfur loadings up to 70 wt% were synthesized delivering discharge capacities higher than 800 mAh g(-1) of the total composite electrode mass.     

Recent advances in cathodes for all-solid-state lithium-sulfur batteries

Lithium-sulfur (Li-S) batteries have been regarded as the candidate for the next-generation energy storage system due to the high theoretical specific capacity (1675 mAh/g), energy density (2600 Wh/kg) and the abundance of elemental sulfur, but the application of Li-S batteries is impeded by a series of problems. Recently, all-solid-state Li-S batteries (ASSLSBs) have drawn great attention because many drawbacks such as safety issues caused by metallic lithium anodes and organic liquid electrolytes can be overcome through the use of solid-state electrolytes (SEs). However, not only the problems brought by sulfur cathodes still exist, but more trouble arouses from the interfaces between SEs and cathodes, hampering the practical application of ASSLSBs. Therefore, in order to deal with the problems, enormous endeavors have been done on ASSLSB cathodes during the past few decades, including engineering of cathode active materials, cathode host materials, cathode binder materials and cathode structures. In this review, the electrochemical mechanism and existing problems of ASSLSBs are briefly introduced. Subsequently, the strategies for developing cathode materials and designing cathode structures are presented. Then there follows a brief discussion of SE problems and expectations, and finally, the challenges and perspectives of ASSLSBs are summarized.     

In-situ polymerized cross-linked binder for cathode in lithium-sulfur batteries

Volume expansion and polysulfide shuttle effect are the main barriers for the commercialization of lithium-sulfur(Li-S) battery.In this work,we in-situ polymerized a cross-linked binder in sulfur cathode to solve the aforementioned problems using a facile method under mild conditions.Polycarbonate diol(PCDL),triethanolamine(TEA) and hexamethylene diisocyanate(HDI) were chosen as precursors to prepare the cross-linked binder.The in-situ polymerized binder(PTH) builds a strong network in sulfur cathode,which could restrain the volume expansion of sulfu r.Moreover,by adopting functional groups of oxygen atoms and nitrogen atoms,the binder could effectively facilitate transportation of Li-ion and adsorb polysulfide chemically.The Li-S battery with bare sulfur and carbon/sulfur composite cathodes and cross-linked PTH binder displays much better electrochemical performance than that of the battery with PVDF.The PTH-bare S cathode with a mass loading of 5.97 mg/cm^2 could deliver a capacity of 733.3 mAh/g at 0.2 C,and remained 585.5 mAh/g after 100 cycles.This in-situ polymerized binder is proved to be quite effective on restraining the volume expansion and suppressing polysulfide shuttle effect,then improving the electrochemical performance of Li-S battery.     

Vanadium-based compounds and heterostructures as functional sulfur catalysts for lithium-sulfur battery cathodes

Lithium-sulfur(Li-S) batteries have attracted wide attention for their high theoretical energy density, low cost, and environmental friendliness. However, the shuttle effect of polysulfides and the insulation of active materials severely restrict the development of Li-S batteries. Constructing conductive sulfur scaffolds with catalytic conversion capability for cathodes is an efficient approach to solving above issues.Vanadium-based compounds and their heterostructures have recently emerged as f...     

Increasing sulfur utilization in lithium-sulfur batteries by a Co-MOF-74@MWCNT interlayer

To improve lithium-sulfur battery performance,Co-MOF-74 has been applied for the first time as an interlayer with multiwalled carbon nanotubes(MWCNTs).Co-MOF-74...     

Confining sulfur in double-shelled hollow carbon spheres for lithium-sulfur batteries

Going into their shell: A novel carbon-sulfur nanocomposite has been synthesized by confining sulfur in double-shelled "soft" carbon hollow spheres with high surface area and porosity. This carbon-sulfur nanocomposite shows outstanding electrochemical performance when evaluated as a cathode material for lithium-sulfur batteries.     

Natural nitrogen-doped multiporous carbon from biological cells as sulfur stabilizers for lithium-sulfur batteries

In this context,we firstly synthesized a novel nitrogen-doped multiporous carbon material from renewable biological cells through a facile chemical activation with K₂CO₃.After sulfur impregnation,the carbon/sulfur composite achieved a sulfur content of about 67 wt%.The C/S composite as the cathode of lithium-sulfur batteries exhibited a discharge capacity of 1410 mAh/g and good capacity retention of 912 mAh/g at 0.1C.These outstanding results were attributed to the synergy effect of microporous carbon and natural doping nitrogen atoms.We believe that the facile approach for the synthesis of nitrogen-doped multiporous carbon from the low-cost and sustainable biological resources will not only be applied in lithium-sulfur batteries,but also in other electrode materials.     

Engineering the morphology/porosity of oxygen-doped carbon for sulfur host as lithium-sulfur batteries

Despite the intriguing merits of lithium-sulfur(Li-S)systems,they still suffer from the notoriousshuttling-effectof polysulfides.Herein,carbon materials with ...     

TiN nanocrystal anchored on N-doped graphene as effective sulfur hosts for high-performance lithium-sulfur batteries

Lithium-sulfur(Li-S)batteries have become prospective candidates for next-generation energy storage owing to the high energy density and low cost.However,the sluggish kinetics of the electrochemical reaction and shuttle effect result in a rapid capacity decay.Herein,a titanium nitride nanocrystal/Ndoped graphene(TiN@NG)composite is developed to host elemental sulfur.The TiN nanoparticles decorated on graphene sheets attract Li polysulfides(LiPSx)and catalyze the electrochemical reduction and oxidation of LiPSx in the discharge and charge processes,respectively.These two effects effectively restrain the dissolution of the LiPSx and accelerate the electrochemical reactions,thereby,alleviating the shuttle effect.As a result,the cathode composed of TiN@NG/S delivers a remarkable reversible capacity(1390 mA h g^-1 at 0.1 C)and excellent cycling performance(730 mA h g^-1 after 300 cycles).We believe that this work can bring some inspiration for designing high-performance Li-S batteries.     

Surface modification of hollow capsule by Dawson-type polyoxometalate as sulfur hosts for ultralong-life lithium-sulfur batteries

Reasonable construction of sulfur host with high conductivity, large sulfur storage gap, strong chemical adsorption, and fast oxidation–reduction kinetics of polysulfide is very significant for its practical use in lithium-sulfur batteries (LSBs). In this paper, the surface modification of MIL-88A(Fe) is carried out by Dawson-type polyoxometalate (POM), and a hollow capsule shell material with P₂W₁₈, Fe₃O₄, and C components is synthesized by the subsequent carbonization process. When applied as the sulfur host, the hollow capsule shell material can efficiently improve the conductivity of sulfur electrode and restrain the volumetric change of active sulfur while charging and discharging. On this foundation, electrochemical analysis and density functional theory (DFT) calculation show that the P₂W₁₈ on the outer layer of the capsule shell have effective electrocatalytic activity and potent chemical bond on the lithium polysulfides (LiPSs), which is helpful to block the shuttle effect. Therefore, the as-assembled LSBs display the outstanding specific capacity and prominent cycle stability. Specifically, it delivers an excellent reversible capacity of 1063 mAh/g after 100 cycles of charge–discharge at a rate of 0.5 C, accounting for a preservation by 96% in comparison to that of the initial cycle. Moreover, even after 2000 cycles at 1 C, the reversible specific capacity of 585 mAh/g can still be maintained with an average decay rate of only 0.021%.     

Well-dispersed sulfur anchored on interconnected polypyrrole nanofiber network as high performance cathode for lithium-sulfur batteries

Preparation of novel sulfur/polypyrrole (S/PPy) composite consisting well-dispersed sulfur particles anchored on interconnected PPy nanowire network was demonstrated. In such hybrid structure, the as-prepared PPy clearly displays a three-dimensionally cross-linked and hierarchical porous structure, which was utilized in the composite cathode as a conductive network trapping soluble polysulfide intermediates and enhancing the overall electrochemical performance of the system. Benefiting from this unique structure, the S/PPy composite demonstrated excellent cycling stability, resulting in a discharge capacity of 931 mAh g⁻¹ at the second cycle and retained about 54% of this value over 100 cycles at 0.1 C. Furthermore, the S/PPy composite cathode exhibits a good rate capability with a discharge capacity of 584 mAh g⁻¹ at 1  C.     

Nitrogen-doped microporous carbon with narrow pore size distribution as sulfur host to encapsulate small sulfur molecules for highly stable lithium-sulfur batteries

Journal of Solid State Electrochemistry - Lithium-sulfur (Li-S) battery with high theoretical energy density has been considered as an important energy storage system. However, its application has...     

Uncovering the solid-phase conversion mechanism via a new range of organosulfur polymer composite cathodes for lithium-sulfur batteries

The sulfur cathodes operating via solid phase conversion of sulfur have natural advantages in suppressing polysulfide dissolution and lowering the electrolyte dosage,and thus realizing significant improvements in both cycle life and energy density.To realize an ideal solid-phase conversion of sulfur,a deep understanding of the regulation path of reaction mechanism and a corresponding intentional material and/or cathode design are highly essential.Herein,via covalently fixing of sulfur onto the t...     

Techniques for realizing practical application of sulfur cathodes in future Li-ion batteries

The development of lithium-sulfur batteries is associated with many problems. These problems include polysulfide dissolution, the shuttle phenomenon, the low electric and ionic conductivity of S, and the volume change that occurs during charge and discharge. In this review, various elemental techniques for overcoming these problems are summarized from the standpoints of the supporting materials. These techniques include preventing polysulfide dissolution from the cathodes through physical and chemical adsorption on the supporting materials, the use of electrolytes that do not dissolve polysulfides via the coordination of Li⁺ and solvents, and the use of ion-exchange polymers to permeate Li⁺ selectively. The following approaches to enable practical applications of S cathodes in future Li-ion batteries are introduced: the utilization of Li-free anode materials, such as C and Si; the use of Li₂S cathodes, which are prepared via a pre-lithiation process; and increasing the areal capacity of the S cathode by using a suitable current collector such as Al foam, thus providing a large amount of space for Li⁺ to migrate and the electron-conductive path. The utilization of an Al foam current collector is one of the promising approaches to creating a cost-effective Li-ion battery owing to the established mass production of Al foam for use in NiMH batteries; such Li-ion battery can achieve an unprecedentedly high areal capacity of 21.9 mAh cm^?2. Owing to the resulting areal capacity, the possibility of developing a lithium-sulfur battery with an energy density greater than 200 Wh kg^?1 has been demonstrated. Consequently, the combination of these approaches, as introduced in this review, would help create a bright, sustainable society.     

Electrochemical evaluation of different graphene/sulfur composite synthesis routes in all-solid-state lithium-sulfur batteries

Journal of Solid State Electrochemistry - The preparation of different cathode composites with intimate contact between the components is of great importance to obtain batteries with better...     

Quaternized polymer binder for lithium-sulfur batteries:The effect of cation structure on battery performance

Lithium-sulfur (Li-S) batteries are great candidates for energy storage systems,but need to overcome the issues of low sulfur utilization and polysulfide shuttling for use in large-scale commercial applications.Recently,quaternized polymers have received much attention for their polysulfide trapping properties due to electrostatic interaction.In this work,we report a series of polyarylether sulfone (PSF) binders with different cation structures including imidazolium (Im),triethylammonium (Tr),and morpholinium(Mo).The ability of the these quaternized binders and the conventional poly(vinylidene fluoride) or PVDF binder to capture polysulfide increases in the order of PVDF PSF-Mo PSF-TrPSF-Im.The delocalized charge on the imidazolium cation may promote the interaction between PSF-Im and polysulfide as indicated by an X-ray photoelectron spectroscopic study.The PSF-Im based cathodes showed the highest capacity retention (77%at 0.2 C after 100 cycles and 84%at 0.5 C after 120 cycles),and the best rate capability.This work demonstrates the importance of the cation structure in the design of efficient quaternized binders for high performance Li-S batteries.     

Core-shell meso/microporous carbon host for sulfur loading toward applications in lithium-sulfur batteries

Lithium-sulfur(Li-S) batteries belong to one of the promising technologies for high-energy-density rechargeable batteries.However,sulfur cathodes suffer from inherent problems of its poor electronic conductivity and the shuttling of highly dissoluble lithium polysulfides generated during the cycles.Loading sulfur into porous carbons has been proved to be an effective approach to alleviate these issues.Mesoporous and microporous carbons have been widely used for sulfur accommodation,but mesoporous carbons have poor sulfur confinement,whereas microporous carbons are impeded by low sulfur loading rates.Here,a core-shell carbon,combining both the merits of mesoporous carbon with large pore volume and microporous carbon with effective sulfur confinement,was prepared by coating the mesoporous CMK-3 with a microporous carbon(MPC) shell and served as the carbon host(CMK-3 @MPC) to accommodate sulfur.After sulfur infusion,the as-obtained S/(CMK-3@MPC) cathode delivered a high initial capacity of up to 1422 mAh·g~(-1) and sustained 654 mAh·g~(-1) reversible specific capacity after 36 cycles at 0.1 C.The good performance is ascribed to the unique core-shell structure of the CMK-3@MPC matrix,in which sulfur can be effectively confined within the meso/microporous carbon host,thus achieving simultaneously high electrochemical utilization.