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1.
Lithium–sulfur battery is recognized as one of the most promising energy storage devices, while the application and commercialization are severely hindered by both the practical gravimetric and volumetric energy densities due to the low sulfur content and tap density with lightweight and nonpolar porous carbon materials as sulfur host. Herein, for the first time, conductive CoOOH sheets are introduced as carbon‐free sulfur immobilizer to fabricate sulfur‐based composite as cathode for lithium–sulfur battery. CoOOH sheet is not only a good sulfur‐loading matrix with high electron conductivity, but also exhibits outstanding electrocatalytic activity for the conversion of soluble lithium polysulfide. With an ultrahigh sulfur content of 91.8 wt% and a tap density of 1.26 g cm?3, the sulfur/CoOOH composite delivers high gravimetric capacity and volumetric capacity of 1199.4 mAh g?1‐composite and 1511.3 mAh cm?3 at 0.1C rate, respectively. Meanwhile, the sulfur‐based composite presents satisfactory cycle stability with a slow capacity decay rate of 0.09% per cycle within 500 cycles at 1C rate, thanks to the strong interaction between CoOOH and soluble polysulfides. This work provides a new strategy to realize the combination of gravimetric energy density, volumetric energy density, and good electrochemical performance of lithium–sulfur battery.  相似文献   

2.
One of the critical challenges to develop advanced lithium‐sulfur (Li‐S) batteries lies in exploring a high efficient stable sulfur cathode with robust conductive framework and high sulfur loading. Herein, a 3D flexible multifunctional hybrid is rationally constructed consisting of nitrogen‐doped carbon foam@CNTs decorated with ultrafine MgO nanoparticles for the use as advanced current collector. The dense carbon nanotubes uniformly wrapped on the carbon foam skeletons enhance the flexibility and build an interconnected conductive network for rapid ionic/electronic transport. In particular, a synergistic action of MgO nanoparticles and in situ N‐doping significantly suppresses the shuttling effect via enhanced chemisorption of lithium polysulfides. Owing to these merits, the as‐built electrode with an ultrahigh sulfur loading of 14.4 mg cm?2 manifests a high initial areal capacity of 10.4 mAh cm?2, still retains 8.8 mAh cm?2 (612 mAh g?1 in gravimetric capacity) over 50 cycles. The best cycling performance is achieved upon 800 cycles with an extremely low decay rate of 0.06% at 2 C. Furthermore, a flexible soft‐packaged Li‐S battery is readily assembled, which highlights stable electrochemical characteristics under bending and even folding. This cathode structural design may open up a potential avenue for practical application of high‐sulfur‐loading Li‐S batteries toward flexible energy‐storage devices.  相似文献   

3.
As one important component of sulfur cathodes, the carbon host plays a key role in the electrochemical performance of lithium‐sulfur (Li‐S) batteries. In this paper, a mesoporous nitrogen‐doped carbon (MPNC)‐sulfur nanocomposite is reported as a novel cathode for advanced Li‐S batteries. The nitrogen doping in the MPNC material can effectively promote chemical adsorption between sulfur atoms and oxygen functional groups on the carbon, as verified by X‐ray absorption near edge structure spectroscopy, and the mechanism by which nitrogen enables the behavior is further revealed by density functional theory calculations. Based on the advantages of the porous structure and nitrogen doping, the MPNC‐sulfur cathodes show excellent cycling stability (95% retention within 100 cycles) at a high current density of 0.7 mAh cm‐2 with a high sulfur loading (4.2 mg S cm‐2) and a sulfur content (70 wt%). A high areal capacity (≈3.3 mAh cm‐2) is demonstrated by using the novel cathode, which is crucial for the practical application of Li‐S batteries. It is believed that the important role of nitrogen doping promoted chemical adsorption can be extended for development of other high performance carbon‐sulfur composite cathodes for Li‐S batteries.  相似文献   

4.
A CO2 in water nanoparticle stabilized Pickering emulsion is used to template micrometer sized hollow porous nitrogen doped carbon particles for high rate performance lithium sulfur battery. For the first time, nanoparticles serve the dual role of an emulsion stabilizer and a pore template for the shell, directly utilizing in situ generated CO2 bubbles as template for the core. The minimalistic nature of this method does not require expensive surfactants or additional core templates. Upon polymerization of melamine formaldehyde onto CO2, a robust polymer/silica composite shell is formed and transformed into a porous shell upon washing. The micrometer‐sized hollow morphology in combination with its nitrogen rich porous shell demonstrates impressive rate capabilities of 670 and 500 mAh g?1 even at a high rate of 7C and 9C, respectively. This material also possesses excellent cycle durability, exhibiting a low capacity decay of 0.088%/cycle over 300 cycles. Measurement of the shuttle current and impedance provides interesting insight into the polysulfide mass transfer mechanism of hollow structured sulfur hosts.  相似文献   

5.
Lithium–sulfur (Li–S) batteries present one of the most promising energy storage systems owing to their high energy density and low cost. However, the commercialization of Li–S batteries is still hindered by several technical issues; the notorious polysulfide shuttling and sluggish sulfur conversion kinetics. In this work, unique hierarchical Fe3‐xC@C hollow microspheres as an advanced sulfur immobilizer and promoter for enabling high‐efficiency Li–S batteries is developed. The porous hollow architecture not only accommodates the volume variation upon the lithiation–delithiation processes, but also exposes vast active interfaces for facilitated sulfur redox reactions. Meanwhile, the mesoporous carbon coating establishes a highly conductive network for fast electron transportation. More importantly, the defective Fe3‐xC nanosized subunits impose strong LiPS adsorption and catalyzation, enabling fast and durable sulfur electrochemistry. Attributed to these structural superiorities, the obtained sulfur electrodes exhibit excellent electrochemical performance, i.e., high areal capacity of 5.6 mAh cm?2, rate capability up to 5 C, and stable cycling over 1000 cycles with a low capacity fading rate of 0.04% per cycle at 1 C, demonstrating great promise in the development of practical Li–S batteries.  相似文献   

6.
Issues with the dissolution and diffusion of polysulfides in liquid organic electrolytes hinder the advance of lithium–sulfur batteries for next‐generation energy storage. To trap and re‐utilize the polysulfides without hampering lithium ion conductivity, a bio‐inspired, brush‐like interlayer consisting of zinc oxide (ZnO) nanowires and interconnected conductive frameworks is proposed. The chemical effect of ZnO on capturing polysulfides has been conceptually confirmed, initially by using a commercially available macroporous nickel foam as a conductive backbone, which is then replaced by a free‐standing, ultra‐light micro/mesoporous carbon (C) nanofiber mat for practical application. Having a high sulfur loading of 3 mg cm?2, the sulfur/multi‐walled carbon nanotube composite cathode with a ZnO/C interlayer exhibits a reversible capacity of 776 mA h g?1 after 200 cycles at 1C with only 0.05% average capacity loss per cycle. A good cycle performance at a high rate can be mainly attributed to the strong chemical bonding between ZnO and polysulfides, fast electron transfer, and an optimized ion diffusion path arising from a well‐organized nanoarchitecture. These results herald a new approach to advanced lithium–sulfur batteries using brush‐like chemi‐functional interlayers.  相似文献   

7.
Herein, high‐content N‐doped carbon nanotube (CNT) microspheres (HNCMs) are successfully synthesized through simple spray drying and one‐step pyrolysis. HNCM possesses a hierarchically porous architecture and high‐content N‐doping. In particular, HNCM800 (HNCM pyrolyzed at 800 °C) shows high nitrogen content of 12.43 at%. The porous structure derived from well‐interconnected CNTs not only offers a highly conductive network and blocks diffusion of soluble lithium polysulfides (LiPSs) in physical adsorption, but also allows sufficient sulfur infiltration. The incorporation of N‐rich CNTs provides strong chemical immobilization for LiPSs. As a sulfur host for lithium–sulfur batteries, good rate capability and high cycling stability is achieved for HNCM/S cathodes. Particularly, the HNCM800/S cathode delivers a high capacity of 804 mA h g?1 at 0.5 C after 1000 cycles corresponding to low fading rate (FR) of only 0.011% per cycle. Remarkably, the cathode with high sulfur loading of 6 mg cm?2 still maintains high cyclic stability (capacity of 555 mA h g?1 after 1000 cycles, FR 0.038%). Additionally, CNT/Co3O4 microspheres are obtained by the oxidation of CNTs/Co in the air. The as‐prepared CNT/Co3O4 microspheres are employed as an anode for lithium‐ion batteries and present excellent cycling performance.  相似文献   

8.
To achieve a high sulfur loading is critical for high‐energy lithium–sulfur batteries. However, high sulfur loading, especially at a low electrolyte/sulfur ratio (E/S), usually causes low sulfur utilization, mainly caused by the slow redox kinetics of polysulfides and the passivation of the discharge product, poor electrically/ionically conducting Li2S. Herein, by using cobalt‐based metal organic frameworks (Co‐MOFs) as precursors, a Co, N‐doped carbonaceous composite (Co, N‐CNTs (carbon nanotubes)‐CNS (carbon nanosheet)/CFC (carbon fiber cloth)) is fabricated with hierarchically ordered structure, which consists of a free‐standing 3D carbon fiber skeleton decorated with a vertical 2D carbon nanosheets array rooted by interwoven 1D CNTs. As an effective polysulfides host, the hierarchically ordered 3D conductive network with abundant active sites and voids can effectively trap polysulfides and provide fast electron/ions pathways to convert them. In addition, Co and N heteroatoms can strengthen the interaction with polysulfides and accelerate its reaction kinetics. More importantly, the interwoven CNTs with Co, N‐doping can induce 3D Li2S deposition instead of conventional 2D deposition, which benefits improving sulfur utilization. Therefore, for Co, N‐CNTs‐CNS/CFC electrodes, even at a high sulfur loading of 10.20 mg cm?2 with a low E/S of 6.94, a high reversible areal capacity of 7.42 mAh cm?2 can be achieved with excellent cycling stability.  相似文献   

9.
The lithium–sulfur (Li–S) battery is regarded as the most promising rechargeable energy storage technology for the increasing applications of clean energy transportation systems due to its remarkable high theoretical energy density of 2.6 kWh kg?1, considerably outperforming today's lithium‐ion batteries. Additionally, the use of sulfur as active cathode material has the advantages of being inexpensive, environmentally benign, and naturally abundant. However, the insulating nature of sulfur, the fast capacity fading, and the short lifespan of Li–S batteries have been hampered their commercialization. In this paper, a functional mesoporous carbon‐coated separator is presented for improving the overall performance of Li–S batteries. A straightforward coating modification of the commercial polypropylene separator allows the integration of a conductive mesoporous carbon layer which offers a physical place to localize dissolved polysulfide intermediates and retain them as active material within the cathode side. Despite the use of a simple sulfur–carbon black mixture as cathode, the Li–S cell with a mesoporous carbon‐coated separator offers outstanding performance with an initial capacity of 1378 mAh g?1 at 0.2 C, and high reversible capacity of 723 mAh g?1, and degradation rate of only 0.081% per cycle, after 500 cycles at 0.5 C.  相似文献   

10.
Hollow nanostructures are one of promising sulfur host materials for lithium–sulfur (Li–S) batteries, but the ineffective contact among discrete particles usually generates overall poor electrical conductivity and low volumetric energy density. A new interfused hollow nitrogen‐doped carbon (HNPC) material, derived from imidazolium‐based ionic polymer (ImIP)‐encapsulated zeolitic imidazolate framework‐8 (ZIF‐8), is reported. A novel method for ZIF‐8 disassembly induced by the decomposition of the ImIP shell is proposed. The unique structural superiority gives the resultant electrodes remarkable cycling stability, high rate capability, and large volumetric energy density. A stable reversible discharge capacity over 562 mA h g?1 at 2 C is achieved after prolonged cycling for 800 cycles and the average capacity decay per cycle is as low as 0.035%. The electrochemical performance achieved greatly surpasses that of ZIF‐8‐derived carbon matrices and conventional nitrogen‐doped carbon materials. This proposed methodology opens a new avenue for the design of hollow‐structured carbon nanoarchitectures with target functionalities.  相似文献   

11.
Hollow structures are often used to relieve the intrinsic strain on metal oxide electrodes in alkali‐ion batteries. Nevertheless, one common drawback is that the large interior space leads to low volumetric energy density and inferior electric conductivity. Here, the von Mises stress distribution on a mesoporous hollow bowl (HB) is simulated via the finite element method, and the vital role of the porous HB structure on strain‐relaxation behavior is confirmed. Then, N‐doped‐C coated mesoporous α‐Fe2O3 HBs are designed and synthesized using a multistep soft/hard‐templating strategy. The material has several advantages: (i) there is space to accommodate strains without sacrificing volumetric energy density, unlike with hollow spheres; (ii) the mesoporous hollow structure shortens ion diffusion lengths and allows for high‐rate induced lithiation reactivation; and (iii) the N‐doped carbon nanolayer can enhance conductivity. As an anode in lithium‐ion batteries, the material exhibits a very high reversible capacity of 1452 mAh g?1 at 0.1 A g?1, excellent cycling stability of 1600 cycles (964 mAh g?1 at 2 A g?1), and outstanding rate performance (609 mAh g?1 at 8 A g?1). Notably, the volumetric specific capacity of composite electrode is 42% greater than that of hollow spheres. When used in potassium‐ion batteries, the material also shows high capacity and cycle stability.  相似文献   

12.
Despite their high theoretical specific capacity (1675 mA h g?1), the practical application of Li–S batteries remains limited because the capacity rapidly degrades through severe dissolution of lithium polysulfide and the rate capability is low because of the low electronic conductivity of sulfur. This paper describes novel hierarchical yolk–shell microspheres comprising 1D bamboo‐like N‐doped carbon nanotubes (CNTs) encapsulating Co nanoparticles (Co@BNCNTs YS microspheres) as efficient cathode hosts for Li–S batteries. The microspheres are produced via a two‐step process that involves generation of the microsphere followed by N‐doped CNTs growth. The hierarchical yolk–shell structure enables efficient sulfur loading and mitigates the dissolution of lithium polysulfides, and metallic Co and N doping improves the chemical affinity of the microspheres with sulfur species. Accordingly, a Co@BNCNTs YS microsphere‐based cathode containing 64 wt% sulfur exhibits a high discharge capacity of 700.2 mA h g?1 after 400 cycles at a current density of 1 C (based on the mass of sulfur); this corresponds to a good capacity retention of 76% and capacity fading rate of 0.06% per cycle with an excellent rate performance (752 mA h g?1 at 2.0 C) when applied as cathode hosts for Li–S batteries.  相似文献   

13.
Lithium–sulfur (Li–S) batteries are promising energy storage systems due to their large theoretical energy density of 2600 Wh kg?1 and cost effectiveness. However, the severe shuttle effect of soluble lithium polysulfide intermediates (LiPSs) and sluggish redox kinetics during the cycling process cause low sulfur utilization, rapid capacity fading, and a low coulombic efficiency. Here, a 3D copper, nitrogen co‐doped hierarchically porous graphitic carbon network developed through a freeze‐drying method (denoted as 3D Cu@NC‐F) is prepared, and it possesses strong chemical absorption and electrocatalytic conversion activity for LiPSs as highly efficient sulfur host materials in Li–S batteries. The porous carbon network consisting of 2D cross‐linked ultrathin carbon nanosheets provides void space to accommodate volumetric expansion upon lithiation, while the Cu, N‐doping effect plays a critical role for the confinement of polysulfides through chemical bonding. In addition, after sulfuration of Cu@NC‐F network, the in situ grown copper sulfide (CuxS) embedded within CuxS@NC/S‐F composite catalyzes LiPSs conversion during reversible cycling, resulting in low polarization and fast redox reaction kinetics. At a current density of 0.1 C, the CuxS@NC/S‐F composites' electrode exhibits an initial capacity of 1432 mAh g?1 and maintains 1169 mAh g?1 after 120 cycles, with a coulombic efficiency of nearly 100%.  相似文献   

14.
The main obstacles that hinder the development of efficient lithium sulfur (Li–S) batteries are the polysulfide shuttling effect in sulfur cathode and the uncontrollable growth of dendritic Li in the anode. An all‐purpose flexible electrode that can be used both in sulfur cathode and Li metal anode is reported, and its application in wearable and portable storage electronic devices is demonstrated. The flexible electrode consists of a bimetallic CoNi nanoparticle‐embedded porous conductive scaffold with multiple Co/Ni‐N active sites (CoNi@PNCFs). Both experimental and theoretical analysis show that, when used as the cathode, the CoNi and Co/Ni‐N active sites implanted on the porous CoNi@PNCFs significantly promote chemical immobilization toward soluble lithium polysulfides and their rapid conversion into insoluble Li2S, and therefore effectively mitigates the polysulfide shuttling effect. Additionally, a 3D matrix constructed with porous carbonous skeleton and multiple active centers successfully induces homogenous Li growth, realizing a dendrite‐free Li metal anode. A Li–S battery assembled with S/CoNi@PNCFs cathode and Li/CoNi@PNCFs anode exhibits a high reversible specific capacity of 785 mAh g?1 and long cycle performance at 5 C (capacity fading rate of 0.016% over 1500 cycles).  相似文献   

15.
3D metal carbide@mesoporous carbon hybrid architecture (Ti3C2Tx@Meso‐C, TX ≈ FxOy) is synthesised and applied as cathode material hosts for lithium‐sulfur batteries. Exfoliated‐metal carbide (Ti3C2Tx) nanosheets have high electronic conductivity and contain rich functional groups for effective trapping of polysulfides. Mesoporous carbon with a robust porous structure provides sufficient spaces for loading sulfur and effectively cushion the volumetric expansion of sulfur cathodes. Theoretical calculations have confirmed that metal carbide can absorb sulfur and polysulfides, therefore extending the cycling performance. The Ti3C2Tx@Meso‐C/S cathodes have achieved a high capacity of 1225.8 mAh g?1 and more than 300 cycles at the C/2 current rate. The Ti3C2Tx@Meso‐C hybrid architecture is a promising cathode host material for lithium‐sulfur batteries.  相似文献   

16.
We demonstrate in this paper facile synthesis of CoS2 and NiS2 hollow spheres with various interiors through a solution‐based route. The obtained CoS2 microspheres constructed by nanosheets display a three‐dimensional architecture with solid, yolk‐shell, double‐shell, and hollow interiors respectively, with continuous changes in specific surface areas and pore‐size distributions. Especially, the CoS2 hollow spheres demonstrate excellent supercapacitive performance including high specific capacitance, good charge/discharge stability and long‐term cycling life, owing to the greatly improved faradaic redox reaction and mass transfer. Furthermore, CoS2 hollow spheres exhibit superior electrocatalytic activity for disulfide/thiolate (T2/T?) redox electrolyte in dye‐sensitized solar cells (DSCs). Therefore, this work provides a promising approach for the design and synthesis of structure tunable materials with largely enhanced supercapacitor behavior, which can be potentially applied in energy storage devices.  相似文献   

17.
Rational design of sulfur host materials with high electrical conductivity and strong polysulfides (PS) confinement is indispensable for high‐performance lithium–sulfur (Li–S) batteries. This study presents one type of new polymer material based on main‐chain imidazolium‐based ionic polymer (ImIP) and carbon nanotubes (CNTs); the polymer composites can serve as a precursor of CNT/NPC‐300, in which close coverage and seamless junction of CNTs by N‐doped porous carbon (NPC) form a 3D conductive network. CNT/NPC‐300 inherits and strengthens the advantages of both high electrical conductivity from CNTs and strong PS entrapping ability from NPC. Benefiting from the improved attributes, the CNT/NPC‐300‐57S electrode shows much higher reversible capacity, rate capability, and cycling stability than NPC‐57S and CNTs‐56S. The initial discharge capacity of 1065 mA h g?1 is achieved at 0.5 C with the capacity retention of 817 mA h g?1 over 300 cycles. Importantly, when counter bromide anion in the composite of CNTs and ImIP is metathesized to bis(trifluoromethane sulfonimide), heteroatom sulfur is cooperatively incorporated into the carbon hosts, and the surface area is increased with the promotion of micropore formation, thus further improving electrochemical performance. This provides a new method for optimizing porous properties and dopant components of the cathode materials in Li–S batteries.  相似文献   

18.
The rational combination of conductive nanocarbon with sulfur leads to the formation of composite cathodes that can take full advantage of each building block; this is an effective way to construct cathode materials for lithium–sulfur (Li–S) batteries with high energy density. Generally, the areal sulfur‐loading amount is less than 2.0 mg cm?2, resulting in a low areal capacity far below the acceptable value for practical applications. In this contribution, a hierarchical free‐standing carbon nanotube (CNT)‐S paper electrode with an ultrahigh sulfur‐loading of 6.3 mg cm?2 is fabricated using a facile bottom–up strategy. In the CNT–S paper electrode, short multi‐walled CNTs are employed as the short‐range electrical conductive framework for sulfur accommodation, while the super‐long CNTs serve as both the long‐range conductive network and the intercrossed mechanical scaffold. An initial discharge capacity of 6.2 mA·h cm?2 (995 mA·h g?1), a 60% utilization of sulfur, and a slow cyclic fading rate of 0.20%/cycle within the initial 150 cycles at a low current density of 0.05 C are achieved. The areal capacity can be further increased to 15.1 mA·h cm?2 by stacking three CNT–S paper electrodes—resulting in an areal sulfur‐loading of 17.3 mg cm?2—for the cathode of a Li–S cell. The as‐obtained free‐standing paper electrode are of low cost and provide high energy density, making them promising for flexible electronic devices based on Li–S batteries.  相似文献   

19.
Multifunctional Ti4O7 particles with interconnected‐pore structure are designed and synthesized using porous poly(styrene‐b ‐2‐vinylpyridine) particles as a template. The particles can work efficiently as a sulfur‐host material for lithium–sulfur batteries. Specifically, the well‐defined porous Ti4O7 particles exhibit interconnected pores in the interior and have a high‐surface area of 592 m2 g?1; this shows the advantage of mesopores for encapsulating of sulfur and provides a polar surface for chemical binding with polysulfides to suppress their dissolution. Moreover, in order to improve the conductivity of the electrode, a thin layer of carbon is coated on the Ti4O7 surface without destroying its porous structure. The porous Ti4O7 and carbon‐coated Ti4O7 particles show significantly improved electrochemical performances as cathode materials for Li–S batteries as compared with those of TiO2 particles.  相似文献   

20.
Noble metal nanostructures are grown inside hollow mesoporous silica microspheres using “ship‐in‐a‐bottle” growth. Small Au seeds are first introduced into the interior of the hollow microspheres. Au nanorods with synthetically tunable longitudinal plasmon wavelengths and Au nanospheres are obtained through seed‐mediated growth within the microspheres. The encapsulated Au nanocrystals are further coated with Pd or Pt shells. The microsphere‐encapsulated bimetallic core/shell nanostructures can function as catalysts. They exhibit high catalytic performance and their stability is superior to that of the corresponding unencapsulated core/shell nanostructures in the catalytic oxidation of o‐phenylenediamine with hydrogen peroxide. Therefore, these hollow microsphere‐encapsulated metal nanostructures are promising as recoverable and efficient catalysts for various liquid‐phase catalytic reactions.  相似文献   

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