Chemical durability and surface alteration of lanthanide zirconates (A2Zr2O7: A = La-Yb)

Chemical durability of lanthanide zirconates (A₂Zr₂O₇) (A = La-Yb) under near-field environments is important for evaluating their application as potential nuclear waste forms. In this work, A₂Zr₂O₇ (A = La-Yb) are synthesized by spark plasma sintering with controlled microstructure and their chemical durability are evaluated in a nitric acid solution (pH = 1). Scanning transmission electron microscopy analysis reveals an amorphous passivation film either enriched with Zr or lanthanide. The complex chemistry of the passivation films can be correlated with a transition in corrosion mechanisms from a preferential release of lanthanide in La₂Zr₂O₇ to a preferential release of Zr in Er₂Zr₂O₇ and Yb₂Zr₂O₇. These results suggest a dominant mechanism of incongruent dissolution and surface reorganization for the formation of passivation films. Strong correlations are identified between the leaching rates and cation ionic size, ionic potential, electronegativity differences between A-site cation and Zr, and bonding valence sum of oxygen, suggesting important impacts of structural and bonding characteristics in controlling chemical durability of lanthanide zirconates.     

Spray pressure variation effect on the properties of CdS thin films for photodetector applications

Herein, we report the photosensing property of CdS thin films. CdS thin films were coated onto glass substrates via a spray pyrolysis method using different spray pressures. Prepared films were characterized using X-ray diffraction (XRD), scanning electron microscopy (SEM), and optical and photoluminescence spectroscopy. XRD analysis demonstrated the growth of crystalline CdS films with crystallite sizes varying from 26 to 29 nm depending on the pressure. The SEM and EDAX analyses revealed nearly-stoichiometric CdS films with smooth surfaces and slight variation in grain morphology due to pressure changes. Optical measurements showed a direct bandgap varying from 2.37 eV to 2.42 eV due to pressure changes. A photodetector was also fabricated using the grown CdS films; the fabricated photodetector exhibited good performance depending on the spray pressure. A spray pressure of 1.5 GPa resulted in high photoresponsivity and external quantum efficiency.     

Optimized microwave absorption properties by tailoring the morphology of carbon coated TiC nanoparticles by N2 pressure

Increasing the dielectric loss capacity plays an important role in enhancing the electromagnetic absorption performance of materials. It remains a challenge to simultaneously introduce multiple types of dielectric losses in the material. In this work, we show that the atomic and interfacial dipole polarizations can be simultaneously enhanced by substituting N species into both carbon coating layers and bulk TiC lattices of a core-shell TiC@C material. Additionally, substitution of N species results more exposed TiC(111) facets and refines the TiC grain sizes in the bulk material, which is beneficial for enhancing the scattering of the external electromagnetic waves. The maximum reflection loss of the N substituted TiC@C material is measured as ?47.1 dB with an effective absorbing bandwidth of 4.83 GHz at 1.9 mm, which illustrates a valuable way to further tuning the electromagnetic absorption performance of this type of materials.     

Effect of LiTFSI and LiFSI on Cycling Performance of Lithium Metal Batteries Using Thermoplastic Polyurethane/Halloysite Nanotubes Solid Electrolyte

All-solid-state lithium batteries(ASSLB) are promising candidates for next-generation energy storage devices.Nevertheless,the large-scale commercial application of high energy density AS S LB with the polymer electrolyte still faces challenges.In this study,a thin solid polymer composite electrolyte(SPCE) is prepared through a facile and cost-effective strategy with an infiltration of thermoplastic polyurethane(TPU),lithium salt(LiTFSI or LiFSI),and halloysite nanotubes(HNTs) in a porous framework of polyethylene separator(PE)(TPU-HNTs-LiTFSI-PE or TPU-HNTs-LiFSI-PE).The composition,electrochemical performance,and especially the effect of anions(TFSI~-and FSI~-) on cycling performance are investigated.The results reveal that the flexible TPU-HNTs-LiTFSI-PE and TPU-HNTs-LiFSI-PE with a thickness of 34 μm exhibit wide electrochemical windows of 4.9 and 5.1 V(vs.Li+/Li) at 60℃,respectively.Reduction in FSI~-tends to form more LiF and sulfur compounds at the interface between TPU-HNTs-LiFSI-PE and Li metal anode,thus enhancing the interfacial stability.As a result,cell composed of TPU-HNTs-LiFSI-PE exhibits a smaller increase in interfacial resistance of solid electrolyte interphase(SEI) with a distinct decrease in charge-transfer resistance during cycling.Li|Li symmetric cell with TPU-HNTs-LiFSI-PE could keep its stable overpotential profile for nearly 1300 h with a low hysteresis of approximately39 mV at a current density of 0.1 mA cm~(-2),while a sudden voltage rise with internal cell impedance-surge signals was observed within 600 h for cell composed of TPU-HNTs-LiTFSI-PE.The initial capacities of NCMITPU-HNTs-LiTFSIPEILi and NCMITPU-HNTs-LiFSI-PEILi cells were 149 and 114 mAh g~(-1),with capacity retention rates of 83.52% and89.99% after 300 cycles at 0.5 C,respectively.This study provides a valuable guideline for designing flexible SPCE,which shows great application prospect in the practice of ASSLB.     

Enhanced electrochemical performance of LiNi0.8Co0.1Mn0.1O2 via titanium and boron co-doping

Titanium and boron are simultaneously introduced into LiNi_0.8Co_0.1Mn_0.1O₂ to improve the structural stability and electrochemical performance of the material. X-ray diffraction studies reveal that Ti⁴⁺ ion replaces Li⁺ ion and reduces the cation mixing; B³⁺ ion enters the tetrahedron of the transition metal layers and enlarges the distance of the [LiO₆] layers. The co-doped sample has spherical secondary particles with elongated and enlarged primary particles, in which Ti and B elements distribute uniformly. Electrochemical studies reveal the co-doped sample has improved rate performance (183.1 mAh·g^-1 at 1 C and 155.5 mAh·g^-1 at 10 C) and cycle stability (capacity retention of 94.7% after 100 cycles at 1 C). EIS and CV disclose that Ti and B co-doping reduces charge transfer impedance and suppresses phase change of LiNi_0.8Co_0.1Mn_0.1O_2.     

Electrochemical performance of in situ LiFePO4 modified by N-doped graphene for Li-ion batteries

LiFePO₄ modified by N-doped graphene (NG) with a three-dimensional conductive network structure was synthesized via a one-step in situ hydrothermal method. The effects of N amount of NG on the phase structure, morphology, and electrochemical properties of LiFePO₄ are investigated in this study. X-ray diffraction (XRD) results show that doping suitable N amounts in NG do not alter the crystal structure of LiFePO_4, and scanning electron microscopy (SEM) images show that NG can slightly reduce the particle size of LiFePO₄. The high-resolution transmission electron microscopy (HRTEM) results show that the LiFePO₄ particles are well covered and connected by NG. The electrochemical performance confirms that LiFePO₄ modified by 20% N-doped graphene (named LFP/NG-4) displays a perfect specific capacity of 166.6 mAh·g^?1 at a rate of 0.2C and can reach 125 mAh·g^?1 at a rate of 5 C. Electrochemical impedance spectroscopy (EIS) results illustrate that the charge transfer resistance value of the LFP/NG-4 composite is only 58.6 Ω, which is very low compared with LiFePO₄. Cyclic voltammetry (CV) tests indicate that the addition of 20% N-doped graphene can effectively reduce electrode polarization and improve reversibility. The LFP/NG-4 composite with a three-dimensional conductive network structure can be regarded as a promising cathode material for Li-ion batteries.     

Speciation of copper in high chloride concentrations,in the context of corrosion of copper canisters

Canisters with a cast iron insert for mechanical strength and a 50-mm thick copper shell as corrosion protection are planned to be used for disposal of spent nuclear fuel in Sweden and Finland. Chloride can be considered “beneficial”, as it promotes active dissolution of copper rather than passivation (which might result in pitting), but a high concentration of chloride in solution would increase the driving force for corrosion through the formation of soluble copper chloro complexes. Thermodynamic calculations are performed in this study with the PHREEQC software and three of its accompanying databases, and a comparison with experimental data is performed to select the database to be used when evaluating repository performance. The activity coefficient models are given special attention. For the assessment of chloride-assisted corrosion of a KBS-3 canister, chloride concentrations pessimistically up to 5 mol/kg are used (in Finland and Sweden, the groundwater and bentonite porewater chloride concentrations are not expected to exceed 1 mol/kg). The resulting copper solubilities are then considered in different mass transport cases.     

Corrosion behaviour of Mg-Gd-Y-Zn-Ag alloy components with different sizes after cooling

The corrosion behaviour of Mg-6Gd-3Y-1Zn-0.3Ag (wt.%) alloy components with different sizes after cooling was investigated. The alloys in the small components (SC) cooled fast, which were composed of α-Mg matrix and coarse long-period stacking ordered (LPSO) phases. The alloys in the large components (LC) cooled slowly, and there were thin lamellar LPSO phases precipitating inside the grains, except for α-Mg matrix and coarse LPSO phases. The hydrogen evolution test revealed that the corrosion rate of LC sample was higher than that of SC sample. Electrochemical impedance spectroscopy (EIS) test showed that the surface film on LC alloys provided worse protection. The corrosion morphologies indicated that the precipitation of the thin lamellar LPSO phases in LC sample caused severe micro-galvanic corrosion, which accelerated the rupture of the surface film.     

防气窜固井技术研究

从气窜机理、气窜预测方法、提高水泥浆防气窜性能、防气窜固井工艺技术四个方面进行研究,为固井防气窜提供理论依据,进而提升防气窜固井技术。     

Energy conversion performances during biomass air gasification process under microwave irradiation

Biomass gasification technology under microwave irradiation is a new and novel method, and the energy conversion performances during the process play a guiding role in improving the energy conversion efficiencies and developing the gasification simulation models. In order to improve the energy utilization efficiency of microwave biomass gasification system, this study investigated and presented the energy conversion performances during biomass gasification process under microwave irradiation, and these were materialized through detailing (a) the energy conversion performance in the microwave heating stage, and (b) the energy conversion performance in the microwave assisted biomass gasification stage. Different forms of energies in the biomass microwave gasification process were calculated by the method given in this study based on the experimental data. The results showed that the useful energy (energy in silicon carbide (SiC), 18.73 kJ) accounted for 31.22% of the total energy input (electrical energy, 60.00 kJ) in the heating stage, and the useful energy (energy in the products, 758.55 kJ) accounted for 63.41% of the total energy input (electrical and biomass energy, 1196.28 kJ) in the gasification stage. During the whole biomass gasification process under microwave irradiation, the useful energy output (energy in the products, 758.55 kJ) accounted for 60.38% of the total energy input (electrical and biomass energy, 1256.28 kJ), and the energy in the gas (523.40 kJ) product played a dominate role in product energy (758.55 kJ). The energy loss mainly included the heat loss in the gas flow (89.20 kJ), magnetron loss (191.80 kJ) and microwave dissipation loss (198.00 kJ), which accounted for 7.10%, 15.27% and 15.76% of the total energy, respectively. The contents detailed in this study not only presented the energy conversion performances during microwave assisted gasification process but also supplied important data for developing gasification simulation models.