Electrodeposition of the manganese-doped nickel-phosphorus catalyst with enhanced hydrogen evolution reaction activity and durability

Hydrogen technology is widely considered a novel clean energy source, and electrolysis is an effective method for hydrogen evolution. Therefore, efficient hydrogen evolution reaction (HER) catalysts are urgently needed to replace precious metal catalysts and meet ecological and environmental protection standards. Herein, Ni–Mn–P electrocatalysts are synthesized using facile electrodeposition technology. The influence of the Mn addition on the catalytic behavior is studied by the comprehensive analysis of catalytic performance and morphology of the catalysts. Among them, the Ni–Mn–P0.01 catalyst exhibits small coral-like structures, greatly improving the adsorption and desorption of hydrogen ions and reducing the overpotential hydrogen evolution. Consequently, overpotential at 10 mA cm^?2 electric current density is 113 mV, and the value of the Tafel slope achieves 74 mV/dec. Furthermore, the Ni–Mn–P catalyst shows long-time (20 h) stability at current densities of 10 and 60 mA/cm². The results confirm that the synergistic effect of Ni, Mn, and P accelerates the electrochemical reaction. Meanwhile, the addition of manganese element can change the micromorphology of the catalyst, thereby exposing more active sites to participate in the reaction, enhancing water ionization, improving the catalytic performance. This study opens a new way toward improving the activity of the catalyst by adjusting Mn concentration during the electrodeposition process.     

Design of Ti4+-doped Li3V2(PO4)3/C fibers for lithium energy storage

In this work, we propose a facile approach to fabricate Ti⁴⁺-doped Li₃V₂(PO₄)₃/C (abbreviated as C-LVTP) nanofibers using an electrospinning route followed by a high temperature treatment. In this designed nanocomposite, the ultrafine LVTP dots are homogeneously dispersed into one-dimensional carbon nanofibers and the Ti⁴⁺ doping does not destroy the crystal structure of monoclinic Li₃V₂(PO₄)₃. Compared to the undoped Li₃V₂(PO₄)₃/C (abbreviated as C-LVP), the as-fabricated C-LVTP fibers present higher reversible capacity, superior high-rate capability as well as better cyclic property. Especially, the C-LVT_7%P cathode delivers not only high capacities of 187.2 and 160.3 mAh g^?1 at 0.5 and 10 C respectively, but also stable cyclic property with the reversible capacity of 135.8 mAh g^?1 at 20 C following 500-cycle spans. The good battery characteristics of C-LVT_7%P can be mainly ascribed to Ti⁴⁺ doping, which can increase the electrical conductivity and Li⁺ diffusion coefficient.     

Influence of surfactants on rheological behaviors of polyacrylonitrile/dimethyl sulfoxide/silicon blending polymer solutions

KH550, KH560, CTAB, and F127 were adopted to modify silicon (Si) to improve the dispersity and stability of Si in the polyacrylonitrile/dimethyl sulfoxide (PAN/DMSO) polymer solutions. The influence of surfactants on rheological behaviors of PAN/DMSO/Si blending polymer solutions was investigated by an advanced solution and melt rotation rheometer. The homogeneity and stability were also studied. The results showed that the surfactants could change the viscosity dependence of blending polymer solutions on shear rate, temperature and storage time by increase the steric hindrance of Si. Among the four solutions, PAN/DMSO/Si blending polymer solution with F127 exhibited the lowest viscosity, activation energy and the smallest structural viscosity index and exhibited the trend close to the Newtonian fluids. Moreover, PAN/DMSO/Si blending polymer solution with F127 exhibited the best dispersity and stability, indicating its best physical properties and machinability.     

Thermal desorption and pyrolysis direct analysis in real time mass spectrometry of Nafion membrane

Perfluorosulfonic acid ionomer membranes have been widely used as proton conducting membranes in various electrochemical processes such as polymer electrolyte fuel cells and water electrolysis. While their thermal stability has been studied by thermogravimetry and analysis of low molecular weight products, their decomposition mechanism is little understood. In this study a newly developed methodology of thermal desorption and pyrolysis in combination with direct analysis in real time mass spectrometry is applied for Nafion membrane. An ambient ionization source and a high-resolution time-of-flight mass spectrometer enabled unambiguous assignment of gaseous products. Thermal decomposition is initiated by side chain detachment above 350°C, which leaves carbonyls on the main chain at the locations of the side chains. Perfluoroalkanes are released above 400°C by main chain scission and their further decomposition products dominate above 500 °C. DFT calculation of reaction energies and barrier heights of model compounds support proposed decomposition reactions.     

Synergistic effect of bulk phase doping and layered-spinel structure formation on improving electrochemical performance of Li-Rich cathode material

In this study, La was doped into the lithium layer of Li-rich cathode material and formed a layered-spinel hetero-structure. The morphology, crystal structure, element valence and kinetics of lithium ion migration were studied by field emission scanning electron microscope (FESEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and electrochemical impedance spectroscopy (EIS). The La doped lithium-rich cathode material exhibited similar initial discharge capacity of 262.8 mAh g^?1 at 0.1 C compared with the undoped material, but the discharge capacity retention rate can be obviously improved to 90% after 50 cycles at 1.0 C. Besides that, much better rate capability and Li⁺ diffusion coefficient were observed. The results revealed that La doping not only stabilized the material structure and reduced the Li/Ni mixing degree, but also induced the generation of spinel phase to provide three-dimensional diffusion channels for lithium ion migration. Moreover, the porous structure of the doped samples also contributed to the remarkable excellent electrochemical performance. All of these factors combined to significantly improve the electrochemical performance of the material.     

Determination of optical and structural properties of lithium silicate ceramics with different ratios of Sm doped

In this study, the synthesis and luminescence characterization of Samarium (Sm³⁺) doped lithium metasilicate (Li₂SiO₃) phosphor ceramic were investigated. It was presented and discussed the results obtained on the luminescence and other optical studies such as X-ray diffraction (XRD), optical absorption and luminescence properties of Li₂SiO₃:Sm³⁺ phosphor ceramic. The Li₂SiO₃ compound was shown a characteristic phase in XRD. The doping in the lithium compound was not having a significant effect on the basic crystal structure of the material. The maximum photoluminescence (PL) emission for Sm³⁺ doped Li₂SiO₃ was observed at 554, 583, 641, 725 nm and bore resemblance to the visible region of the spectrum. The glow curves of all synthesized materials have a complex peak structure after being irradiated with a ⁹⁰Sr–⁹⁰Y beta source. In addition, the peak between 400 and 600 nm was seen in the radioluminescence (RL) spectrum because of a wide peak thought to be caused by silicate.     

Structural Aspects of P2-Type Na0.67Mn0.6Ni0.2Li0.2O2 (MNL) Stabilization by Lithium Defects as a Cathode Material for Sodium-Ion Batteries

A known strategy for improving the properties of layered oxide electrodes in sodium-ion batteries is the partial substitution of transition metals by Li. Herein, the role of Li as a defect and its impact on sodium storage in P2-Na_0.67Mn_0.6Ni_0.2Li_0.2O₂ is discussed. In tandem with electrochemical studies, the electronic and atomic structure are studied using solid-state NMR, operando XRD, and density functional theory (DFT). For the as-synthesized material, Li is located in comparable amounts within the sodium and the transition metal oxide (TMO) layers. Desodiation leads to a redistribution of Li ions within the crystal lattice. During charging, Li ions from the Na layer first migrate to the TMO layer before reversing their course at low Na contents. There is little change in the lattice parameters during charging/discharging, indicating stabilization of the P2 structure. This leads to a solid-solution type storage mechanism (sloping voltage profile) and hence excellent cycle life with a capacity of 110 mAh g^-1 after 100 cycles. In contrast, the Li-free compositions Na_0.67Mn_0.6Ni_0.4O₂ and Na_0.67Mn_0.8Ni_0.2O₂ show phase transitions and a stair-case voltage profile. The capacity is found to originate from mainly Ni³⁺/Ni⁴⁺ and O^2-/O^2-δ redox processes by DFT, although a small contribution from Mn⁴⁺/Mn⁵⁺ to the capacity cannot be excluded.     

Interlayer Engineering of Molybdenum Trioxide toward High‐Capacity and Stable Sodium Ion Half/Full Batteries

Orthorhombic molybdenum trioxide (MoO₃) is one of the most promising anode materials for sodium‐ion batteries because of its rich chemistry associated with multiple valence states and intriguing layered structure. However, MoO₃ still suffers from the low rate capability and poor cycle induced by pulverization during de/sodiation. An ingenious two‐step synthesis strategy to fine tune the layer structure of MoO₃ targeting stable and fast sodium ionic diffusion channels is reported here. By integrating partially reduction and organic molecule intercalation methodologies, the interlayer spacing of MoO₃ is remarkably enlarged to 10.40 Å and the layer structural integration are reinforced by dimercapto groups of bismuththiol molecules. Comprehensive characterizations and density functional theory calculations prove that the intercalated bismuththiol (DMcT) molecules substantially enhanced electronic conductivity and effectively shield the electrostatic interaction between Na⁺ and the MoO₃ host by conjugated double bond, resulting in improved Na⁺ insertion/extraction kinetics. Benefiting from these features, the newly devised layered MoO₃ electrode achieves excellent long‐term cycling stability and outstanding rate performance. These achievements are of vital significance for the preparation of sodium‐ion battery anode materials with high‐rate capability and long cycling life using intercalation chemistry.     

Enhance cycling performance of LiMn2O4 cathode by Sr2+ and Cr3+ doping

Spinel LiSr_0·1Cr_0·1Mn_1·8O₄ was synthesised by high temperature solid state method in order to enhance the electrochemical performance. The LiSr_0·1Cr_0·1Mn_1·8O₄ (LSCMO) materials were characterised by X-ray diffraction (XRD), scanning electron microscopy (SEM) and electrochemical tests. The XRD and SEM studies confirm that LSCMO had spinel crystal structure with a space group of Fd3m, and the particle of LSCMO shows irregular shape. The cyclic voltammetry data illustrated that the heavy current charge–discharge performance of LMO was improved by Sr²⁺ and Cr³⁺ doping. The galvanostatic charge–discharge of LSCMO cathode materials was measured at 1, 5, 10 and 20 C. The results indicated that LSCMO improved the capacity retention.