Hierarchical Hollow Research Articles

Stabilizing sulfur doped manganese oxide active sites with phosphorus doped hierarchical nested square carbon for efficient asymmetric supercapacitor

The introduction of heteroatom species into hollow carbon lattice networks (HCLN) and metallic oxides have been exploited as an effective approach to enhance the performance of the electrochemical electrodes. Herein, square hierarchical P-doped porous carbon/S-doped manganese oxide (S-Mn5O8@PPC) is designed via a solvothermal, chemical vapor deposition and wet chemical growth method from the solid-state gas-steaming operation of zinc of square acids, offering a unique nested hierarchical and stable integrated structure. As a result, the as-fabricated S-Mn5O8@PPC and PPC demonstrated impressive electrochemical capacitance of 1819.8F g−1 and 325.1F g−1 at 1 A g−1, respectively, which both superior than the Mn5O8@PPC and porous carbon (PC, 1604.0F g−1 and 193.2F g−1). Especially, the specific capacitance of the PPC is preferred to that of most non-metallic heteroatom-doped MOFs-derived carbons. More importantly, two supercapacitor (SC) electrodes - square hierarchical P-doped porous carbon (PPC) and S-doped manganese oxide coated PPC - are further self-assembled a hybrid SC device, which possesses a wide voltage of 0–1.6 V, outstanding electrochemical capacitance of 154.8F g−1, impressive energy storage performance and a reliable capacitive stability (87.24% after 5000 cycles), apart from the ideal energy density and power density (55.1 W h kg−1 at 800.0 W kg−1). Such excellent features originate from the large specific surface area of the porous hierarchical hollow structure, the doping of heterogeneous P and S, the dispersive loading of manganese oxide, and harmonious matching of positive and negative electrodes.

Synergistically induced dual-interfacial interactions in iron-nickel sulfides heterojunction encapsulated by N, S-codoped carbon matrix heightened ion-transport kinetics for sodium-storage

Exploring bimetallic sulfides of diverse metal species with well-defined nanoarchitectures and distinctive interfacial interactions is indispensable for advanced sodium-storage systems in achieving rapid electron/ion transfer kinetics, optimizing structural durability, and enhancing electrochemical energy storage. In this regard, the fabrication of a spindle-like hierarchical hollow nanocage with the dual heterointerfaces was reported utilizing N, S co-doped carbon support encapsulating hollow FeS2/NiS heterojunction (FeS2/NiS@N,S-C) through the critical steps of facile dopamine self-polymerization, followed by hydrolyzation, carbonization and further sulphuration. Benefiting from the great superiorities of superior conductivity, excellent structural robustness, abundant active reaction sites, efficient charge transport pathways, as well as fast ion-migration kinetics bestowed by creating an synergistically induced dual interfacial interaction in the ingenious nanoarchitecture, the FeS2/NiS@N,S-C composites render a significantly optimized comprehensive performance of Na+-storage, yielding a highly competitive capacity of 598.0 mAh g−1 after 600 cycles at 1.0 A g−1, and desirable cycle stability with supernormal rate capability (362.6 mAh g−1 after 1950 cycles at 20.0 A g−1), one of the best performances for FeS2- or NiS based heterojunctions. Meanwhile, the redox mechanism involving initial intercalation reaction and following conversion stage was uncovered detailly by a set of ex-situ experimental characterizations. Theoretical evidences drawn from density functional theory calculations illustrate that the formation of dual heterointerfaces in FeS2/NiS@N,S-C composites enables good conductivity, optimizes Na+ adsorption energy, and reduces activation energy for Na+ migration, which facilitates ion/electron migration and enhances reaction kinetics of the electrode.

Silver nanoparticles embedded in phosphorus and nitrogen-doped hierarchical hollow porous carbon for efficient supercapacitor and electrocatalytic water oxidation

Supercapacitor (SC) and oxygen evolution reaction (OER) require highly efficient multifunctional catalysts prepared from non-noble metals and heteroatoms. In this work, we have developed silver (Ag) decorated on phosphorus (P), nitrogen (N) -doped hollow porous carbon (HPC) prepared through hydrothermal followed by pyrolysis method. The prepared bifunctional electrocatalyst was studied through different characterization techniques. As-prepared HPC-UD, P-HPC-UD, and Ag@P-HPC-UD integrate high-level P-doping, large specific surface areas (up to 1452, 1247, and 528 m2 g−1), and hierarchical multipores of cross-linked micro and mesopore channels. As a result, the Ag and P modified the active sites and electronic structure of the HPC bifunctional catalyst, which is beneficial for the electrocatalytic process. As a result, the Ag@P-HPC-UD catalyst provides an outstanding specific capacitance value of 388 F g−1 at 0.5 A g−1 when used as a SC electrode. Furthermore, the Ag@P-HPC-UD electrocatalyst exhibited efficient OER behavior with a lower overpotential of 165 mV at 10 mA cm−2 current density and a lower Tafel value of 55.46 mV dec−1, which is remarkably superior to commercial RuO2 electrocatalyst. Therefore, the Ag@P-HPC-UD electrocatalyst pathway for a new revolution in developing a highly impressive carbon-based electrode towards both SC and electrocatalytic OER performance.

The porous hollow cobalt-based oxides encapsulated with bimetallic PdAu Nanoparticles of electrochemical biosensor for highly sensitive pesticides detection

Efficient and portable electrochemical biosensors are received to evaluation of pesticides in the environment, which can make great significance for food safety. In this study, the Co-based oxides with a kind of hierarchical porous hollow and nanocages were constructed, in which the materials (Co3O4-NC) were encapsulated with PdAu nanoparticles (NPs). Due to the unique porous structure, the changeable valence state of cobalt and the synergistic effect of bimetallic PdAuNPs, PdAu@Co3O4-NC possessed excellent electron pathways, and showed more exposed active sites. Accordingly, the porous Co-based oxides have been applied to construct an acetylcholinesterase (AChE) electrochemical biosensor, which showed good performance for organophosphorus pesticides (OPs) detection. The optimum biosensing platform based on nanocomposites was applied to exhibit highly sensitive determination of omethoate and chlorpyrifos, with the relative low detection limit of 6.125 × 10−15 M and 5.10 × 10−13 M, respectively. And a wide detection range of 6.125 × 10−15 ∼ 6.125 × 10−6 M and 5.10 × 10−13 ∼ 5.10 × 10−6 M for these two pesticides were achieved. Therefore, the PdAu@Co3O4-NC may represent a powerful tool for ultrasensitive sensing of OPs, and have great potential application.

The Facile Synthesis of Hollow CuS Microspheres Assembled from Nanosheets for Li-Ion Storage and Photocatalytic Applications.

Herein, well-defined hollow CuS microspheres assembled from nanosheets were successfully synthesized through a facile solvothermal method. Hollow CuS microspheres have an average diameter of 1.5 μm; moreover, the primary CuS nanosheets have an ultrathin thickness of about 10 nm and are bound by {0001} polar facets. When used as anodes for lithium-ion batteries (LIBs), hollow CuS microspheres exhibit excellent electrochemical properties, including a large discharge capacity (610.1 mAh g-1 at 0.5 C), an excellent rate capability (207.6 and 143.4 mAh g-1 at 1 and 5 C), and a superior cyclic stability (196.3 mAh g-1 at 1 C after 500 cycles). When used as photocatalysts for Rhodamine B (RhB), hollow CuS microspheres can degrade more than 99% of the initial RhB within 21 min. These excellent Li-ion storage properties and photocatalytical performances are attributed to their unique hierarchical hollow structure.

A MOF-to-MOF conversion assisted formation of hierarchical hollow Zn–Co1–xS/C@C composite for efficient potassium-ion storage

Hollow structured composite can enhance the structural stability of metal sulfide anode by accommodating its volume variation, while the performance is still hindered by its poor electron/ion conductivity. Herein, we develop a hierarchical hollow structure to achieve superior electrochemical performance, from which a MOF-to-MOF conversion is utilized to generate hollow Zn–Co1-xS/C composite followed with additional carbon coating layer. For potassium storage, as-prepared hollow Zn–Co1-xS/C@C composite displays high capacities of 375 mA h g−1 after 100 cycles at 0.2 A g−1 and 201 mA h g−1 after 500 cycles at 1 A g−1. Moreover, it also manifests outstanding rate capability of 200 mA h g−1 at 10 A g−1, outperforming hollow Co1-xS@C and majority of the reported cobalt-based anodes. With illustration by kinetics analysis and theoretical calculation, both of Zn doping and internal carbon matrix are conductive to promote the charge transportation ability of Co1-xS, thus accounting for the good cycling behavior and excellent rate capacity of hierarchical hollow Zn–Co1-xS/C@C composite.

Viscoelastic polyacrylate with hierarchical hollow zeolite for sound insulation

AbstractAcoustic materials embed with inorganic fillers in viscoelastic polymers have promising applications in industrial settings. However, optimizing the sound insulation of composites by adjusting the microstructure of nanofillers remains a challenge. In this study, we synthesize adjustable hollow hierarchical Zeolite Socony Mobil #5 (ZSM‐5) which can be used as nanofillers in a sound insulation nanocomposite based on the polyacrylate (PA). The results show that the nanocomposites with 0.5 wt% hierarchical hollow ZSM‐5 can increase the sound transmission loss (STL) by 33.4%. The maximum STL value reaches as high as 40 dB. The damping properties of the nanocomposites were also improved by adding ZSM‐5 into the PA matrix. When the loading of hollow ZSM‐5 is 0.5 wt%, the storage modulus increased by 44%, as high as 4486.7 MPa. This strategy opens up a promising way for the sound insulation of composites based on controllable inorganic nanofillers.

Interface-induced electron transfer in sandwich-like hierarchical hollow CoP@NC hybrid for boosted hydrogen evolution reaction in alkaline electrolyte

It is necessary to develop an effective non-noble metal electrocatalyst to promote the slow kinetics of alkaline electrolytes. Here, a self-sacrificing template method is developed to construct sandwich-like layered hollow structures CoP@NC (H-CoP@NC) for promoting hydrogen evolution kinetics. The hierarchical hollow nanostructures give greater contact area between catalyst and electrolyte, shorten ion/electron transport distances, and expose more active sites. More importantly, the introduction of nitrogen-doped carbon (NC) can effectively prevent the aggregation of CoP and improve the electron transfer rate during phosphorylation. The overpotential of the catalyst H-CoP@NC is only 173 mV at a current density of 10 mA/cm2. The excellent catalytic activity can be attributed to the unique structure and the doping of heteroatom. This work provides a new method for designing hollow nanomaterials.

Excellent NO2 gas sensor based on the oxygen inhibiting effect of Ni3+-doped WO3

Due to the intrinsic properties of wide band gap and the 5d shell being vacant, WO3 still has the disadvantages of low response dynamics, slow response/recovery speed and high detection limit for real-time gas monitoring. To address such issues, the Ni3+ doped WO3 hierarchical hollow structure composed of irregular nanosheets was achieved and the content of adsorbed oxygen was adjusted by Ni3+ doping to further improve the gas sensing performance of WO3. In comparison to pure WO3, the 3 wt%Ni-WO3 sensor exhibited remarkable response value (396), short response/recovery speed (13 s/6 s) and low detection limit (510 ppt) at 160 ℃. The impressive gas properties could be attributed to the reduced band gap and oxygen inhibiting effect of Ni3+ doping, which provides more NO2 adsorption sites and making it easier for NO2 to capture more electrons in the conduction band by restraining the oxygen ions chemisorbed on the surface. The unique sensing characteristics of the Ni3+ doped WO3 suggest its wonderful potential applications in environmental pollution gas detection. The mechanism of oxygen inhibiting effect induced by Ni3+ doping was also discussed in detail

Regulating Hollow Carbon Cage Supported NiCo Alloy Nanoparticles for Efficient Electrocatalytic Hydrogen Evolution Reaction.

The NiCo alloy is one of the most promising alternatives to the noble-metal electrocatalysts for the hydrogen evolution reaction (HER); however, its performance is largely restricted by insufficient active sites and low surface area. Here, we fabricated a hierarchical hollow carbon cage supported NiCo alloy (denoted as HC NiCo/C) and a bulk NiCo alloy (denoted as NiCo) by reduction of a partially ZIF-67 etched ZIF-67@NiCo-LDH (LDH = layered double hydroxide) precursor and a fully ZIF-67 etched NiCo-LDH precursor, respectively. The as-prepared HC NiCo/C, in which the Ni29Co71 alloy nanocrystals with an average 6 nm size were encapsulated in graphitic carbon layers, provided a vastly increased electrochemically active surface area (ca. 13 times than the NiCo) and abundant catalytic active sites, which resulted in a higher HER performance with an overpotential of 99 mV than the 198 mV for NiCo at 10 mA cm-2. Detailed experimental results suggested that only the HC NiCo/C possessed the active alloy surface composed of unsaturated Ni0 and Co0 atoms, and both the metal-support interaction and alloying effect influenced the electronic structure of Co and Ni in HC NiCo/C, whereas the NiCo exhibited pure Ni surface. Theoretical calculations further revealed the Ni29Co71 alloy surface in HC NiCo/C possessed the appropriate adsorption energy of the intermediate state (adsorbed H*). This work provided new insight into the construction of the stable small-sized bimetallic alloy nanocatalysts by regulating the reduction precursors.

Pea‐like MoS2@NiS1.03–carbon heterostructured hollow nanofibers for high‐performance sodium storage

AbstractThe rational synergy of chemical composition and spatial nanostructures of electrode materials play important roles in high‐performance energy storage devices. Here, we designed pea‐like MoS2@NiS1.03–carbon hollow nanofibers using a simple electrospinning and thermal treatment method. The hierarchical hollow nanofiber is composed of a nitrogen‐doped carbon‐coated NiS1.03 tube wall, in which pea‐like uniformly discrete MoS2 nanoparticles are enclosed. As a sodium‐ion battery electrode material, the MoS2@NiS1.03–carbon hollow nanofibers have abundant diphasic heterointerfaces, a conductive network, and appropriate volume variation‐buffering spaces, which can facilitate ion diffusion kinetics, shorten the diffusion path of electrons/ion, and buffer volume expansion during Na+ insertion/extraction. It shows outstanding rate capacity and long‐cycle performance in a sodium‐ion battery. This heterogeneous hollow nanoarchitectures designing enlightens an efficacious strategy to boost the capacity and long‐life stability of sodium storage performance of electrode materials.

Exploring novel p-n core/shell structure in single α-Fe2O3 nanorods of hierarchical hollow microspheres for ultrasensitive acetone gas sensor

Fabricating metal oxide sensors with super-sensitivity and good distinguishing properties for gases is a challenge due to the difficulties in controlling vacancy-type structural defects of nanomaterials and the data processing. In this paper, we reported the fabrication of hierarchical α-Fe2O3 hollow microsphere (HFHM)-based sensor using a facile and scalable method with uniform-micro spherical carbon templates, as well as the data analysis using artificial intelligence (AI). The shell of the unique hollow microspheres was built by connecting many α-Fe2O3 nanorods, so the superstructures have 0D, 1D, and 3D structural features. In these α-Fe2O3 nanorods, positron annihilation measurements revealed abundant oxygen-vacancy clusters (11 atoms), nanopores (0.53 nm) and p-n core/shell structure. The HFHM-based sensors, hence, exhibited an extremely high sensitivity toward acetone (Response = 320 (200 ppm), limited detection (DL) ∼ 250 ppt) and ethanol (Response = 300 (200 ppm), DL ∼ 500 ppt), as well as a super-fast response time (1–2 s). In particular, by using the Principal Component Analysis (PCA), an applied AI tool, we were able to significantly improve the distinguishing and selective abilities of acetone and ethanol (high-response gas groups) as well as H2, CO and NH3 (low-response gas groups).

In situ N-doped carbon nanotubes modified NiS2 hierarchical hollow microspheres for boosting sodium storage performance

Engineering novel electrode materials with distinctive architectures has a significant influence on tuning the structural/electrochemical properties for boosting the sodium storage performance. Herein, starting from metal-organic framework (MOF), we report an in situ catalytic method with chemical transformation strategy to fabricate NiS2 hierarchical hollow microspheres (HMs) with continuous N-doped carbon nanotubes (NCNTs) networks (NiS2@NCNTs HMs). Benefitting from the hierarchical hollow structure and three-dimensional (3D) NCNTs networks as well as the robust structural stability, the prepared NiS2@NCNTs HMs indicates excellent Na+ storage performance. More specifically, the composite shows a high reversible capacity of 626.6 mA h g−1 at 0.2 A g−1 for Na+ storage and retains 333.3 mA h g−1 at 5.0 A g−1, remarkably higher than those of the previously reported NiS2-based anode materials. In particular, it maintains a stable reversible capacity of 343.0 mA h g−1 even at 3.0 A g−1 over 3000 cycles. The in situ catalytic NCNTs on MOF precursors strategy for hierarchical structural composites can be extended to other novel electrodes for high performance energy storage devices.

Hierarchical MoS2 hollow microspheres with high piezoelectric catalytic performance prepared by the soft-template method

Hierarchical MoS2 hollow microspheres with high piezoelectric catalytic performance prepared by the soft-template method

Hierarchical hollow CuO/Cu2O and Cu2O/Cu/C derived from metal–organic framework for non-enzymatic oxidation toward glucose

Constructing copper-based oxide composite with ingenious architecture is attracting enormous attention due to the synergistic effect of components and enhanced performance resulted from structure. Herein, hierarchical hollow CuO/Cu2O and Cu2O/Cu/C are prepared via calcining hierarchical tubular metal–organic framework (MOF) in air atmosphere and Ar atmosphere, respectively. With calcining in air atmosphere, the obtained hierarchical hollow CuO/Cu2O is constructed by nanosheets which is composed of particles in diameter of 20–30 nm. In Ar atmosphere, the synthesized hierarchical hollow Cu2O/Cu/C is constructed by larger particles in diameter of about 65 nm. And these differences in component and building unit are ascribed to different dominant reaction involved in calcination of MOF at different atmospheres. Notably, the hollow structure of parent MOF is perfectly remained, which contributes to the enhancement of copper-based oxide composites in electrocatalytic oxidation toward glucose. The hierarchical hollow CuO/Cu2O and Cu2O/Cu/C can be applied as an excellent glucose sensor with higher sensitivity, wider detection range and lower limitation of detection. Selecting suitable MOF as sacrificed template being calcined in effective atmosphere, provides a facile strategy for constructing derivant with functional structures and increased properties.

MOF templated to construct hierarchical ZnIn2S4-In2S3 hollow nanotube for enhancing photocatalytic performance

3D (Three-dimensional) hollow porous structured materials received a lot of attention due to their significant benefits in photocatalytic reactions. In this study, 3D ZnIn2S4-In2S3 hollow hierarchical porous nanotubes were synthesized by a one-step MOF (metal–organic framework) templating strategy as efficient catalysts for photocatalytic hydrogen evolution in water. The dynamic process between the internal collapse of In-MIL-68 and the growth of ZnIn2S4 crystals with attached outer edges led to the one-step in situ preparation of hollow ZnIn2S4-In2S3 heterojunction catalysts. Crucially, In-MIL-68 simultaneously induced the formation of In2S3 hollow porous nanotubes and the construction of ZnIn2S4-In2S3 hierarchical heterojunction with ultrathin nanosheets. The optimal photocatalytic efficiency was obtained by adjusting the relative composition of the two-component heterojunction, and the optimized ZnIn2S4-In2S3-10 showed hydrogen evolution efficiency of 5.01 mmol·h−1·g−1 under visible light irradiation in the absence of co-catalysts and a high AQY (the apparent quantum yield) of 16.23 % at 420 nm, which was noticeably higher than the photocatalytic efficiency of the one-component and two-step synthesized In2S3-ZnIn2S4. Both theoretical and experimental results demonstrated that the construction of heterojunction and the forming of hollow porous nanotubes enhanced visible light absorption and promoted the separation and transfer of photogenerated carriers, thereby increasing the photocatalytic activity of the prepared materials. Meanwhile, ZnIn2S4-In2S3 hierarchical hollow nanotubes exhibited good stability and reusability, offering a new way to fabricate MOF-based hollow hierarchical photocatalysts.

Temperature-dependent synthesis of SnO2 or Sn embedded in hollow porous carbon nanofibers toward customized lithium-ion batteries

Lithium-ion batteries (LIBs) have been widely used as grid-level energy storage systems to power electric vehicles, hybrid electric vehicles, and portable electronic devices. However, it is a big challenge to develop high-capacity electrode materials with large energy storage and ultrafast charging capability simultaneously due to the sluggish charge carrier transport in bulk materials and fragments of active materials. To address this issue, composite electrodes of SnO2 nanodots and Sn nanoclusters embedded in hollow porous carbon nanofibers (denoted as SnO2@HPCNFs and Sn@HPCNFs) were respectively constructed programmatically for customized LIBs. Highly interconnected carbon nanofiber networks served as fast electron transport pathways. Additionally, the hierarchical hollow and porous structure facilitated rapid Li-ion diffusion and alleviated the volume expansion of Sn and SnO2. SnO2@HPCNFs delivered a remarkably high capacity of 899.3 mA h g−1 at 0.1 A g−1 due to enhanced Li adsorption and high ionic diffusivity. Meanwhile, Sn@HPCNFs displayed fast charging capability and superior high rate performance of 238.8 mA h g−1 at 5 A g−1 (∼10 C) due to the synergetic effect of enhanced Li-ion storage in the bulk pores of Sn and improved electronic conductivity. The investigation of the electrochemical behaviors of SnO2 and Sn by tailoring the carbonization temperature provides new insight into constructing high-capacity anode materials for high-performance energy storage devices.

Hierarchical Porous Carbon Spheres Loaded CoOX (CoOx/HPCS) for Efficient Oxygen Reduction Reaction in Alkaline Media

AbstractThe development of efficient non‐noble metal catalysts for oxygen reduction reaction (ORR) in alkaline media is vital for wide application of numerous energy conversion devices. In this work, the CoOx/HPCS catalysts are demonstrated to show excellent activity toward ORR with more positive peak potential, initial potential, and half‐wave potential than pure HPCS. Moreover, the CoOx/HPCS exhibits a long‐term stability and a stronger methanol resistance compared to 20% Pt/C. The outstanding ORR activity for CoOx/HPCS is owing to its excellent characteristics, like: 1) a good conductivity of the carbon matrix to improve the electron transfer ability; 2) the rich hierarchical hollow carbon matrix and high surface area conducive to providing more accessible active sites and improving mass transportation; 3) the defect caused by oxygen vacancy beneficial for enhancing catalytic activity; 4) the synergistic effect between CoOx and HPCS support being crucial for ORR, thence enhancing the electrochemical performance of CoOx/HPCS.

Hierarchical dandelion-like CoS2 hollow microspheres: self-assembly and controllable microwave absorption performance.

The emerging electromagnetic radiation and interference problems have promoted the rapid development of microwave absorption materials (MAMs). However, it remains a severe challenge to construct high-performance microwave absorption materials with broadband, lightweight and corrosion resistance within low filling contents. Herein, hierarchical dandelion-like CoS2 hollow microspheres were reasonably constructed via a solvothermal-hydrothermal etching-in situ vulcanization process. The structure morphology, composition and electromagnetic performance of all samples have been thoroughly tested. The research results demonstrated that the structure morphology of the prepared samples with a volume ratio of 1 : 1 between ethanol and H2O remained intact without serious damage. Notably, the as-obtained hierarchical dandelion-like CoS2 hollow microspheres (25 wt%) exhibited excellent microwave absorption capacity with a minimum reflection loss (RLmin) of -47.3 dB and the corresponding effective absorption bandwidth (EAB) of 8.4 GHz at 3.3 mm. Moreover, the broadest effective absorption bandwidth (EAB, RL < -10 dB) reached 9.0 GHz (9.0-18.0 GHz) at the matching thickness of 3.2 mm. The unparalleled multiple features including hierarchical hollow structure, tunable complex permittivity as well as the enhanced impedance matching endowed CoS2 great promise as high-performance microwave absorbers for solving the problem of electromagnetic pollution.

Hierarchical carbon hollow nanospheres coupled with ultra-small molybdenum carbide as sulfiphilic sulfur hosts for lithium-sulfur batteries.

Lithium-sulfur (Li-S) batteries are an attractive candidate to replace the current state-of-the-art lithium-ion batteries due to their promising theoretical capacity of 1675 mA h g-1 and energy density of 2500 W h kg-1. However, the lithium polysulfide (LiPS) shuttle effect and the slow sulfur redox kinetics seriously decrease the utilization of sulfur and deteriorate battery performance. Here, hierarchical carbon hollow nanospheres containing intimately coupled molybdenum carbide nanocrystals were synthesized as a sulfiphilic sulfur host. The sufficient interior void space accommodates the sulfur and physically confines LiPSs, while the in situ introduced molybdenum carbide nanoparticles can chemically immobilize LiPSs and catalytically accelerate their redox transformations. As a result, the Li-S batteries with this synergistic effect achieve an excellent rate capability of 566 mA h g-1 at 2C and a long cycle stability over 300 cycles at 1C.