Two-Step Catalytic Against Polysulfide Shuttling to Enhance Redox Conversion for Advanced Lithium-Sulfur Batteries.

The development of lithium-sulfur batteries is seriously hindered by the shuttle effect of lithium polysulfides (LiPSs) and the low electrical conductivity of sulfur. To solve these problems, efficient catalysts can be used to improve the conversion rate of LiPSs and the conductivity of sulfur cathode. Herein, annealed melamine foam supported MoSe2 (NCF@MoSe2) is used as interlayer and the MoSe2/MoP heterojunction obtained by phosphating MoSe2 is further used as the catalyst material for metal fusion with a sulfur element. The interlayer can not only improve the electrical conductivity and effectively adsorb and catalyze LiPSs, but more importantly, the MoSe2/MoP heterojunction can also effectively adsorb and catalyze LiPSs, so that the batteries have a dual inhibition shuttling effect strategy. Furthermore, the rapid anchor-diffusion transition of LiPSs, and the suppression of shuttling effects by catalyst materials are elucidated using theoretical calculations and in situ Raman spectroscopy. The two-step catalytic strategy exhibits a high reversibility of 983 mAh g-1 after 200 cycles at 0.5 C and a high-rate capacity of 889 mAh g-1 at 5 C. This work provides a feasible solution for the rational design of interlayer and heterojunction materials and is also conducive to the development of more advanced Li-S batteries.

P-Doped NiTe2 with Te-Vacancies in Lithium-Sulfur Batteries Prevents Shuttling and Promotes Polysulfide Conversion.

Lithium-sulfur (Li-S) batteries have been hindered by the shuttle effect and sluggish polysulfide conversion kinetics. Here, a P-doped nickel tellurium electrocatalyst with Te-vacancies (P⊂NiTe2- x ) anchored on maize-straw carbon (MSC) nanosheets, served as a functional layer (MSC/P⊂NiTe2- x ) on the separator of high-performance Li-S batteries. The P⊂NiTe2- x electrocatalyst enhanced the intrinsic conductivity, strengthened the chemical affinity for polysulfides, and accelerated sulfur redox conversion. The MSC nanosheets enabled NiTe2 nanoparticle dispersion and Li+ diffusion. In situ Raman and ex situ X-ray absorption spectra confirmed that the MSC/P⊂NiTe2- x restrained the shuttle effect and accelerated the redox conversion. The MSC/P⊂NiTe2- x -based cell has a cyclability of 637 mAh g-1 at 4 C over 1800 cycles with a degradation rate of 0.0139% per cycle, high rate performance of 726 mAh g-1 at 6 C, and a high areal capacity of 8.47 mAh cm-2 under a sulfur configuration of 10.2 mg cm-2 , and a low electrolyte/sulfur usage ratio of 3.9. This work demonstrates that vacancy-induced doping of heterogeneous atoms enables durable sulfur electrochemistry and can impact future electrocatalytic designs related to various energy-storage applications.

ZnS-SnS@NC Heterostructure as Robust Lithiophilicity and Sulfiphilicity Mediator toward High-Rate and Long-Life Lithium-Sulfur Batteries.

Lithium-sulfur (Li-S) batteries are severely hindered by the low sulfur utilization and short cycling life, especially at high rates. One of the effective solutions to address these problems is to improve the sulfiphilicity of lithium polysulfides (LiPSs) and the lithiophilicity of the lithium anode. However, it is a great challenge to simultaneously optimize both aspects. Herein, by incorporating the merits of strong absorbability and high conductivity of SnS with good catalytic capability of ZnS, a ZnS-SnS heterojunction coated with a polydopamine-derived N-doped carbon shell (denoted as ZnS-SnS@NC) with uniform cubic morphology was obtained and compared with the ZnS-SnS2@NC heterostructure and its single-component counterparts (SnS@NC and SnS2@NC). Theoretical calculations, ex situ XANES, and in situ Raman spectrum were utilized to elucidate rapid anchoring-diffusion-transformation of LiPSs, inhibition of the shuttling effect, and improvement of the sulfur electrochemistry of bimetal ZnS-SnS heterostructure at the molecular level. When applied as a modification layer coated on the separator, the ZnS-SnS@NC-based cell with optimized lithiophilicity and sulfiphilicity enables desirable sulfur electrochemistry, including high reversibility of 1149 mAh g-1 for 300 cycles at 0.2 C, high rate performance of 661 mAh g-1 at 10 C, and long cycle life with a low fading rate of 0.0126% each cycle after 2000 cycles at 4 C. Furthermore, a favorable areal capacity of 8.27 mAh cm-2 is maintained under high sulfur mass loading of 10.3 mg cm-2. This work furnishes a feasible scheme to the rational design of bimetal sulfides heterostructures and boosts the development of other electrochemical applications.

Melamine Foam Derived 2H/1T MoS2 as Flexible Interlayer with Efficient Polysulfides Trapping and Fast Li+ Diffusion to Stabilize Li-S Batteries.

Lithium-sulfur (Li-S) batteries featuring high-energy densities are identified as a hopeful energy storage system but are strongly impeded by shuttle effect and sluggish redox chemistry of sulfur cathodes. Herein, annealed melamine foam loaded 2H/1T MoS2 (CF@2H/1T MoS2) is prepared as a multifunctional interlayer to inhibit the shuttle effect, improve redox kinetics, and reduce the charge-discharge polarization of Li-S batteries. The CF@2H/1T MoS2 becomes fragmented structures after assembling the cell, which not only benefits to adsorb and catalyze LiPSs but also to significantly buffer the volume expansion due to a large number of gaps between fragmented structures. Meanwhile, the batteries based on CF@2H/1T MoS2 interlayer delivers high areal capacity of 5.1 mAh cm-2 under high sulfur mass loading of 7.6 mg cm-2 at 0.2 C. Importantly, the experiments of in situ Raman spectra demonstrate that the CF@2H/1T MoS2 can obviously inhibit the shuttle effect by effectively adsorbing and catalyzing LiPSs. This novel design idea and low-cost melamine foam raw material open up a new way for the application of high-energy density Li-S batteries.

Design and facile synthesis of defect-rich C-MoS2/rGO nanosheets for enhanced lithium-sulfur battery performance.

We report a simple one-step hydrothermal strategy for the fabrication of a C-MoS2/rGO composite with both large surface area and high porosity for the use as advanced electrode material in lithium-sulfur batteries. Double modified defect-rich MoS2 nanosheets are successfully prepared by introducing reduced graphene oxide (rGO) and amorphous carbon. The conductibility of the cathodes can be improved through the combination of amorphous carbon and rGO, which could also limit the dissolution of polysulfides. After annealing at different temperatures, it is found that the C-MoS2/rGO-6-S composite annealed at 600 °C yields a noticeably enhanced performance of lithium-sulfur batteries, with a high specific capacity of 572 mAh·g-1 at 0.2C after 550 cycles, and 551 mAh·g-1 even at 2C, much better than that of MoS2-S nanosheets (249 mAh·g-1 and 149 mAh·g-1) and C-MoS2/rGO-S composites (334 mAh·g-1 and 382 mAh·g-1). Our intended electrode design protocol and annealing process may pave the way for the construction of other high-performance metal disulfide electrodes for electrochemical energy storage.

Bi-Metal Phosphide NiCoP: An Enhanced Catalyst for the Reduction of 4-Nitrophenol.

Porous phosphide NixCoyP composite nanomaterials are successfully synthesized at different Ni/Co ratios (=0, 0.5, 1, and 2) to reduce 4-nitrophenol. The X-ray diffraction and X-ray photoelectron spectroscopy results demonstrate that the products are CoP, NiCoP/CoP, NiCoP, and NiCoP/Ni2P when the Ni/Co ratio is 0, 0.5, 1, and 2, respectively. The products exhibit different catalytic performance for reduction of 4-nitrophenol at room temperature. Among them, the pure NiCoP delivers a better catalytic efficiency with k app = 677.4 × 10 - 2   min - 1 and k = 338.7   ( Lg - 1 min - 1 ) , due to the synergy between Ni and Co atoms. The sequence of catalytic efficiency of different samples is CoP < NiCoP/CoP < NiCoP/Ni2P < NiCoP.

Influence of different aluminum salts on the photocatalytic properties of Al doped TiO2 nanoparticles towards the degradation of AO7 dye.

Three kinds of Al-TiO2 samples and pure TiO2 samples were synthesized via a modified polyacrylamide gel route using different aluminum salts, including Al2(SO4)3∙18H2O, AlCl3, and Al(NO3)3∙9H2O under identical conditions. The influence of different aluminum salts on the phase purity, morphologies, thermal stability of anatase and photocatalytic properties of the as-prepared Al-TiO2 nanoparticles were studied. The energy gap (Eg) of Al-TiO2 nanoparticles decreases due to Al ion doping into TiO2. The photocatalytic activities of the Al-TiO2 samples were investigated by the degradation of acid orange 7 dye in aqueous solution under simulated solar irradiation. The Al-TiO2 nanoparticles prepared from Al(NO3)3∙9H2O exhibit the best photocatalytic activity among the four kinds of samples, followed in turn by the Al-TiO2 nanoparticles prepared with AlCl3, Al2(SO4)3∙18H2O and pure TiO2. The different performances are attributed to complex effects of Eg, particle size, surface morphology, phase purity and the defect sites of the Al-TiO2 nanoparticles.