Neutron powder diffraction as a characterization tool of solid oxide fuel cell materials

Neutron diffraction is a powerful tool for the characterization of materials and, particularly, oxides. Oxide materials find applications in solid oxide fuel cells (SOFCs) as solid electrolytes as well as anode and cathode materials. As a structural probe, neutrons are specially suitable for the crystallographic study of oxides, given the comparable scattering factors of O and other heavier elements, allowing its precise localization in the crystal structure. Many problems can be addressed by neutrons, related to the octahedral tilting in perovskites, phase transitions, order–disorder phenomena, presence of anionic vacancies, etc. Neutrons make possible an accurate determination of the thermal factors and provide a visualization of the diffusion paths in ionic conductors. Neutrons allow the localization of light atoms such as hydrogen, and make possible the distinction between neighbouring elements, typically Fe and Mn. In this work we will describe some recent applications of this technique in the field of solid electrolytes and electrode materials, including some examples from our group.     

Hydrogen-oxygen (air) fuel cell with nafion and platinum: Calculating overall characteristics,comparing the performance of a cathode with polymeric electrolyte with a hydrophobized cathode with liquid electrolyte

Results of calculating the major overall characteristics of both an individual cathode and the whole hydrogen-oxygen (air) fuel cell with Nafion and platinum are shown. The effect of varying the parameters of both the active layer and the polymeric-electrolyte membrane on the overall characteristics of such a fuel cell is analyzed. The mechanisms of operation of active layers of hydrophobized cathodes and cathodes containing Nafion are compared. These two electrode types demonstrate a qualitative difference in the current generation mechanisms. As a result, the current in cathodes with Nafion increases more actively with the increase in over-potential (in proportion with exp [η₀/2], where η₀ is the cathodic overpotential) as compared with the case of hydrophobized cathodes (here the current ～ exp[η₀/4]). This explains the fact that a fuel cell with Nafion demonstrates so high power characteristics as compared with a fuel cell with hydrophobized electrodes and liquid electrolyte.     

Lanthanum-strontium cuprate: A promising cathodic material for solid oxide fuel cells

Samples of lanthanum-strontium cuprate LaSrCuO_3.61 are synthesized by a solid-phase method at 1473 K, in air. Electron diffraction patterns reveal low-intensity satellites whose position is described in the reciprocal space by the (3 + 2)-dimensional space group I4/mmm(αα0, α-α0)00mg. Using a five-layer cell LaSrCuO_4-δ|YSZ|LaSrCuO_4-δ|YSZ|LaCuO_4-δ prepared by isostatic hot pressing, the ionic component of conductivity of LaSrCuO_4-δ is determined (σ_{1179 K} = 3.8 × 10^?3 S cm^?1), which is commensurate with other mixed conductors based on complex oxides of cobalt and iron.     

Integrating trace Ti-doping and LiYO2-coating to stabilize Ni-rich cathodes for lithium-ion batteries

Ni-rich layered cathodes have become the promising candidates for the next-generation high-energy Li-ion batteries due to their high energy density and competitive cost. However, they suffer from rapid capacity fading due to the structural and interfacial instability upon long-term operation. Herein, the Ti-doped and LiYO₂-coated Ni-rich layered cathode has been synthesized via a facile one-step sintering strategy, which significantly restrains the interfacial parasitic side reactions and enhances the structural stability. Specifically, the trace Ti⁴⁺ doping greatly stabilizes the lattice oxygen and alleviates the Li/Ni disorder while the LiYO₂ coating layer can prevent the erosion of the cathode by the electrolyte during cycles. As a result, the Ti-NCM83@LYO delivers a high specific capacity of 135 mAh g⁻¹ even at 10C and there is almost no capacity loss at 1C for 100 cycles. This work provides a simple one-step dual-modification strategy to meet the commercial requirements of Ni-rich cathodes.     

Production of long,laminar plasma jets at atmospheric pressure with multiple cathodes

Plasma jets from conventional non‐transferred arc plasma devices are usually operated in turbulent flows at atmospheric pressure. In this paper, a novel non‐transferred arc plasma device with multiple cathodes is introduced to produce long, laminar plasma jets at atmospheric pressure. A pure helium atmosphere is used to produce a laminar plasma jet with a maximum length of >60 cm. The influence of gas components, arc currents, anode nozzle diameter, and gas flow rate on the jet characteristics is experimentally studied. The results reveal that the length of the plasma jet increases with increasing helium content and arc current but decreases with increasing nozzle diameter. As the gas flow rate increases, the length of the plasma jet initially increases and then decreases. Accordingly, the plasma jet is transformed from a laminar state to a transitional state and finally to a turbulent state. Furthermore, the anode arc root behaviours corresponding to different plasma jet flows are studied. In conclusion, the multiple stationary arc roots that exist on the anode just inside the nozzle entrance are favourable for the generation of a laminar plasma jet in this device.     

Sulfur Encapsulated in a TiO2‐Anchored Hollow Carbon Nanofiber Hybrid Nanostructure for Lithium–Sulfur Batteries

A hollow carbon nanofiber hybrid nanostructure anchored with titanium dioxide (HCNF@TiO₂) was prepared as a matrix for effective trapping of sulfur and polysulfides as a cathode material for Li–S batteries. The synthesized composites were characterized and examined by X‐ray diffraction, nitrogen adsorption–desorption measurements, field‐emission scanning electron microscopy, scanning transmission electron microscopy, and electrochemical methods such as galvanostatic charge/discharge, rate performance, and electrochemical impedance spectroscopy tests. The obtained HCNF@TiO₂–S composite showed a clear core–shell structure with TiO₂ nanoparticles coating the surface of the HCNF and sulfur homogeneously distributed in the coating layer. The HCNF@TiO₂–S composite exhibited much better electrochemical performance than the HCNF–S composite, which delivered an initial discharge capacity of 1040 mA h g^?1 and maintained 650 mAh g^?1 after 200 cycles at a 0.5 C rate. The improvements of electrochemical performances might be attributed to the unique hybrid nanostructure of HCNF@TiO₂ and good dispersion of sulfur in the HCNF@TiO₂–S composite.     

Accurate Control of Initial Coulombic Efficiency for Lithium-rich Manganese-based Layered Oxides by Surface Multicomponent Integration

Low initial Coulombic efficiency (ICE) is an obstacle for practical application of Li-rich Mn-based layered oxides (LLOs), which is closely related with the irreversible oxygen evolution owing to the overoxidized reaction of surface labile oxygen. Here we report a NH₄F-assisted surface multicomponent integration technology to accurately control the ICE, by which oxygen vacancies, spinel-layered coherent structure, and F-doping are skillfully integrated on the surface of treated LLOs microspheres. Though the regulation on the removed amount of labile oxygen by surface integrated structure, the ICE of LLOs cathodes can adjust from starting value to 100 %. X-ray absorption spectroscopy, refined X-ray diffraction, and scanning transmission electron microscopy show that the removed labile oxygen mainly comes from Li₂MnO₃-like structure. Even operating at a high cut-off voltage of 5 V, the capacity retention of integrated sample at 200 mA g⁻¹ is still larger than 98 % after 100 cycles.     

Design Concepts of Transition Metal Dichalcogenides for High-Performance Aqueous Zn-Ion Storage

Aqueous Zn-ion batteries (AZIBs) are considered as promising large-scale energy storage devices due to their high safety and low cost. Transition metal dichalcogenides (TMDs) as the potential aqueous Zn-storage cathode materials are under the research spotlight because of their facile 2D ion-transport channels and weak electrostatic interactions with Zn²⁺. In this concept article, we summarize the intrinsic structural features and aqueous Zn-storage mechanisms of the TMDs-based electrodes. More significantly, the latest design concepts of TMDs materials for high-performance AZIBs are discussed in detail from three aspects of interlayer expansion engineering, phase transition engineering, and structure defects engineering. Finally, the current challenges facing TMDs cathodes and possible remedies are outlined for future developments towards efficient, rapid, and stable aqueous Zn-ion storage.     

LiMn<Subscript>2</Subscript>O<Subscript>4</Subscript> and LiCoO<Subscript>2</Subscript> composite cathode materials obtained by mechanical activation

New composite cathode materials xLiMn₂O₄/(1 ? x) LiCoO₂(x = 0.7, 0.6, 0.5 и 0.4) were obtained by mechanical activation. According to scanning electron microscopy data, the process was accompanied by pronounced dispersion and fine mixing of the initial components. In the course of the preparation and electrochemical cycling of the composites, LiMn₂O₄ and LiCoO₂ partially reacted, leading to the replacement of manganese with cobalt in the structure of spinel, which was detected by powder X-ray diffraction (XRD), IR and X-ray photoelectron spectroscopy (XPS), and cyclic chronopotentiometry. The specific discharge capacity of composites was ～100 mAh/g.