Current and further trajectories in designing functional materials for solid oxide electrochemical cells:A review of other reviews

Complex oxides are an important class of materials with enormous potential for electrochemical appli-cations.Depending on their composition and structure,such complex oxides can exhibit either a single conductivity(oxygen-ionic or protonic,or n-type,or p-type electronic)or a combination thereof gener-ating distinct dual-conducting or even triple-conducting materials.These properties enable their use as diverse functional materials for solid oxide fuel cells,solid oxide electrolysis cells,permeable membranes,and gas sensors.The literature review shows that the field of solid oxide materials and related electro-chemical cells has a significant level of research engagement,with over 8,000 publications published since 2020.The manual analysis of such a large volume of material is challenging.However,by examining the review articles,it is possible to identify key patterns,recent achievements,prospects,and remaining obstacles.To perform such an analysis,the present article provides,for the first time,a comprehensive summary of previous review publications that have been published since 2020,with a special focus on solid oxide materials and electrochemical systems.Thus,this study provides an important reference for researchers specializing in the fields of solid state ionics,high-temperature electrochemistry,and energyconversiontechnologies.

Characteristics of inclusions in high-Al steel during electroslag remelting process

The characteristics of inclusions in high-A1 steel refmed by electroslag remelting （ESR） were investigated by image analysis, scanning electron microscopy （SEM）, and energy-dispersive spectrometry （EDS）. The results show that the size of almost all the inclusions observed in ESR ingots is less than 5 μm. Inclusions smaller than 3 μm take nearly 75% of the total inclusions observed in each ingot. Inclu- sions observed in ESR ingots are pure AIN as dominating precipitates and some fine spherical Al2O3 inclusions with a size of 1 μm or less. It is also found that protective gas operation and slag deoxidation treatment during ESR process have significant effects on the number of inclusions smaller than 2μm but little effects on that of inclusions larger than 2 μm. Thermodynamic calculations show that AIN inclusions are unable to precipitate in the liquid metal pool under the present experimental conditions, while the precipitation of AlN inclusions could take place at the solidifying front due to the microsegregation orAl and N in liquid steel during solidification.

CONJUGATE MODEL FOR HEAT AND MASS TRANSFER OF POROUS WALL IN THE HIGH TEMPERATURE GAS FLOW

Heat and mass transfer of a porous permeable wall in a high temperature gas dynamical flow is considered. Numerical simulation is conducted on the ground of the conjugate mathematical model which includes filtration and heat transfer equations in a porous body and boundary layer equations on its surface. Such an approach enables one to take into account complex interaction between heat and mass transfer in the gasdynamical flow and in the structure subjected to this flow. The main attention is given to the impact of the intraporous heat transfer intensity on the transpiration cooling efficiency.

Structural,electronic,optical,elastic properties and Born effective charges of monoclinic HfO_2 from first-principles calculations

First-principles calculations of structural, electronic, optical, elastic, mechanical properties, and Born effective charges of monoclinic HfO2 are performed with the plane-wave pseudopotential technique based on the density-functional theory. The calculated structural properties are consistent with the previous theoretical and experimental results. The electronic structure reveals that monoclinic HfO2 has an indirect band gap. The analyses of density of states and Mulliken charges show mainly covalent nature in Hf-O bonds. Optical properties, including the dielectric function, refractive index, extinction coefficient, reflectivity, absorption coefficient, loss function, and optical conductivity each as a function of photon energy are calculated and show an optical anisotropy. Moreover, the independent elastic constants, bulk modulus, shear modulus, Young＇s modulus, Poisson＇s ratio, compressibility, Lam6 constant, sound velocity, Debye temperature, and Born effective charges of monoclinic HfO2 are obtained, which may help to understand monoclinic HfO2 for future work.

A High-Spectral-Resolution Laser Raman System and Its Application in Shock–Compressed Benzene

Raman measurements play an important role in examining the molecular changes associated with shock-induced structural and chemical changes in condensed materials.We combine a high spectra-resolution Raman system with a two-stage light gas gun to provide better quality data than the transient Raman system used previously.Representative measurements are presented for the shock compression of benzene.The high spectral resolution data have provided an insight into molecular changes that could not be obtained from time-resolved methods.

Towards high-performance tubular-type protonic ceramic electrolysis cells with all-Ni-based functional electrodes

Protonic ceramic electrolysis cells(PCECs),which permit high-temperature electrolysis of water,exhibit various advantages over conventional solid oxide electrolysis cells(SOECs),including cost-effectiveness and the potential to operate at low-/intermediate-temperature ranges with high performance and efficiency.Although many efforts have been made in recent years to improve the electrochemical characteristics of PCECs,certain challenges involved in scaling them up remain unresolved.In the present work,we present a twin approach of combining the tape-calendering method with all-Ni-based functional electrodes with the aim of fabricating a tubular-designed PCEC having an enlarged electrode area(4.6 cm^2).This cell,based on a 25μm-thick BaCe0.5Zr0.3Dy0.2O3-δ proton-conducting electrolyte,a nickelbased cermet and a Pr1.95Ba0.05NiO4+δ oxygen electrode,demonstrates a high hydrogen production rate(19 m L min^-1 at 600℃),which surpasses the majority of results reported for traditional button-or planar-type PCECs.These findings increase the scope for scaling up solid oxide electrochemical cells and maintaining their operability at reducing temperatures.

Shear viscosity of aluminum studied by shock compression considering elasto-plastic effects

The strength always exists before the material melts. In this paper, the viscoelastic-plastic model is applied to improve the finite difference method, and the numerical solutions for the disturbance amplitude damping behavior of the sinusoidal shock front in a flyer-impact experiment are obtained. When the aluminum is shocked to 101 GPa, the effect of elasto-plasticity on the zero-amplitude point of the oscillatory damping curve is the same as that of viscosity when η= 700 Pa.s, and the real shear viscosity coefficient of the shocked aluminum is determined to be about 2800±100 Pa.s. Comparing the experiment data with the numerical results of the viscoelastic-plastic model, we find that the aluminum is close to melting at 101 GPa.

Modeling the interaction of nitrate anions with ozone and atmospheric moisture

The molecular dynamics method is used to investigate the interaction between one-six nitrate anions and water clusters absorbing six ozone molecules. The infrared（IR） absorption and reflection spectra are reshaped significantly, and new peaks appear at Raman spectra due to the addition of ozone and nitrate anions to the disperse water system. After ozone and nitrate anions are captured, the average（in frequency） IR reflection coefficient of the water disperse system increased drastically and the absorption coefficient fell.

Preparation of Ni/C core-shell composite powders by electroless plating method

Ni/C core-shell composite powders were prepared by electroless nickel-plating. The effects of concentration of NiSO4,bathing temperature,ratio of hydrazine hydrate to NiSO4,pH of the solution,amounts of complexing reagent and surfactant,bath load of activated carbon and reaction time,and so on,on the preparation of Ni/C core-shell composite powders were studied. The results show that the principal factors for Ni/C composite powders preparation are bathing temperature,ratio of hydrazine hydrate to NiSO4 and pH of the solution. The optimum conditions are plating at 90 ℃ with pH10.7 and molar ratio of N2H4·H2O to Ni2+of 3.0. The plated nickel powders are observed to be sphere-like in morphology with size about 100 nm. The maximum dielectric loss of Ni/C core-shell composite powders is about 0.35,and its magnetic loss was low with value about 0 in 2-16 GHz.

Elastic Constants of Na and K from Non-parameter Perturbation Calculation

Combining a linear muffin-tin orbital method, which can be used to calculate the total energy and pressure of solids in a self-consistent manner, with a generalized elastic energy equation, a non-parameter perturbation method has been proposed to compute the elastic constant for cubic metals. The pressure dependence of the shear modulus and bulk modulus forNa and K was calculated. It was found that the computed results agree well with experiments.

Restudy of Grüneisen Parameter of Iron in the Pressure Range of 90-160 Gpa

The Hugoniot equation-of-state(EOS)of porous iron with an average initial density of 6.904g/cm^(3) has been measured in the pressure range from 90 to 160GPa,and a good straight fitting D=2.997+1.603u has accordingly been obtained,where D is the shock wave velocity and u the particle velocity,both in units of km/s.Combining this with the Hugoniot EOS of non-porous iron,the Grüneisen EOS and the Rankine-Hugoniot energy conservation relation,and taking the possible solid-liquid transition correction,we have calculated the Grüneisen parameterγof iron and obtained the resultγ0ρ0=γρ=const,withγ0=1.945 andρ0=7.856g/cm^(3),ρbeing the density.

Electrical Resistivity of Silane Multiply Shock-Compressed to 106 GPa

Since Wigner et al. proposed that hydrogen would become metallic under sufficient pressure compres- sions in 1935,scientists have paid their attention on making metallic hydrogen at high pressures, and con- siderable progresses were made in theoretical and ex- perimental researches. Nellis et al. observed that the electrical resistivity of fluid hydrogen declined by several orders of magnitude when liquid hydrogen was multiply shocked to 140 GPa, and concluded that fluid hydrogen underwent metallization phase tran- sition from semiconductor to metal in their experi- ments. Although further researches should be carried out to distinguish the highly conductive state and the metallic state of fluid hydrogen, researchers have made great efforts to find new technical approaches to de- crease the threshold pressure for hydrogen metalliza- tion. For this purpose, hydrogen-rich compounds at- tract much attention. Some researchers believed that non-hydrogen elements in those compounds may re- duce, to some extent, the activation energy of met- allization by the effect of chemical pre-compression. Silane, a typical hydrogen-rich compound of group IV hydrides, has been the subject of most of the theoretical and experimental research so far, and it was also expected to be a potential candidate for a high-To superconductor at high pressure research.[61 Compared to hydrocarbons,[71 the chemical bonds in the silane molecule are theoretically more sensitive to pressure and temperature. At sufficiently high pres- sure and temperature, the fluid silane possibly be- comes some metallic alloy consisting of hydrogen and silicon elements. Theoretical calculations showed thatthe metallic transition for the silane system may oc- cur even below 100 GPa, while there are also some other later articles that claimed that silane would re- main an insulator up to around 200 GPa and became metallic and supconducting at 220 GPa with a theo- retical Tc of 16 K. Recently, Eremets et al. have re- ported that silane can transform to metal at 50 GPa, even to superconductor of Tc = 17K at 96GPa and 120GPa. The interesting question is whether tile Inetallization transition could occur under lower pres- sure by inulti-shock compression. Nellis et al. mea- sured the electrical conductivities of hydrocarbons shock-compressed to pressures from 20 GPa to 60 GPa, while for silane, experimental data of electrical resis- tivity under shock compression are scarce. In this Let- ter, the electrical resistivity of silane under nmltiply shock compression is obtained, and the experimental technique and data treatment are briefly described.

Solidification characteristics of high Nb-containing γ-TiAl-based alloys with different aluminum contents

The effect of A1 content on the microstructure and solidification characteristics of Ti-A1-Nb-V-Cr alloys in as-cast and isothermally treated states was investigated using X-ray diffraction （XRD）, scanning electron microscopy （SEM） equipped with energy dispersive spectroscope （EDS）, and transmission electron microscopy （TEM）. The typical solidification characteristics are due to the joint influence of both the crystal temperature range and the solidification path. The wide crystallization temperature range contributes to obtaining coarse dendrites in the as-cast Ti47A17Nb2.5V1.0Cr （at%） alloy solidifying through the peritectic reaction. The β-solidifying Ti46A17Nb2.5V1.0Cr （at%） alloy with the narrow crystallization temperature range is attributed to the formation of a homogeneous finegrained microstructure. However, the crystallization temperature range of Ti48A17Nb2.5V1.0Cr （at%） alloy is equivalent to that of Ti46A17Nb2.5V1.0Cr alloy, but it is solidified by peritectic reaction, leading to the formation of finer dendrites.

High-temperature transport properties of BaSn_(1−x)Sc_(x)O_(3−δ) ceramic materials as promising electrolytes for protonic ceramic fuel cells

Protonic ceramic fuel cells(PCFCs)offer a convenient means for electrochemical conversion of chemical energy into electricity at intermediate temperatures with very high efficiency.Although BaCeO_(3)-and BaZrO_(3)-based complex oxides have been positioned as the most promising PCFC electrolytes,the design of new protonic conductors with improved properties is of paramount importance.Within the present work,we studied transport properties of scandium-doped barium stannate(Sc-doped BaSnO_(3)).Our analysis included the fabrication of porous and dense BaSn_(1−x)Sc_(x)O_(3−δ)ceramic materials(0≤x≤0.37),as well as a comprehensive analysis of their total,ionic,and electronic conductivities across all the experimental conditions realized under the PCFC operation:both air and hydrogen atmospheres with various water vapor partial pressures(p(H2O)),and a temperature range of 500–900℃.This work reports on electrolyte domain boundaries of the undoped and doped BaSnO_(3)for the first time,revealing that pure BaSnO_(3)exhibits mixed ionic–electronic conduction behavior under both oxidizing and reducing conditions,while the Sc-doping results in the gradual improvement of ionic(including protonic)conductivity,extending the electrolyte domain boundaries towards reduced atmospheres.This latter property makes the heavilydoped BaSnO_(3)representatives attractive for PCFC applications.

Electrolyte materials for protonic ceramic electrochemical cells:Main limitations and potential solutions

Solid oxide fuel cells(SOFCs)and electrolysis cells(SOECs)are promising energy conversion devices,on whose basis green hydrogen energy technologies can be developed to support the transition to a carbon-free future.As compared with oxygen-conducting cells,the operational temperatures of protonic ceramic fuel cells(PCFCs)and electrolysis cells(PCECs)can be reduced by several hundreds of degrees(down to low-and intermediatetemperature ranges of 400–700C)while maintaining high performance and efficiency.This is due to the distinctive characteristics of charge carriers for proton-conducting electrolytes.However,despite achieving outstanding lab-scale performance,the prospects for industrial scaling of PCFCs and PCECs remain hazy,at least in the near future,in contrast to commercially available SOFCs and SOECs.In this review,we reveal the reasons for the delayed technological development,which need to be addressed in order to transfer fundamental findings into industrial processes.Possible solutions to the identified problems are also highlighted.

The C_ν for calculating the shock temperatures of water below 80 GPa

The shock temperatures of water under 35-50 GPa are firstly measured by the optical pyrometry technique. Cν is a constant below 51 GPa (Cν=7.07R), and increases with the temperature above 51 GPa (Cν=(5.76+3.84×10-4T)R). From our calculation, the dissociation has little effect on Cν. But the electron is essential to the Cν calculation.

Clean source of soft X-ray radiation formed in supersonic Ar gas jets by high-contrast femtosecond laser pulses of relativistic intensity

In this work,we optimized a clean,versatile,compact source of soft X-ray radiation(Ex-ray∼3 keV)with an yield per shot up to 7×10^11 photons/shot in a plasma generated by the interaction of high-contrast femtosecond laser pulses of relativistic intensity(Ilas∼10^18-10^19 W/cm^2)with supersonic argon gas jets.Using high-resolution X-ray spectroscopy approaches,the dependence of main characteristics(temperature,density and ionization composition)and the emission efficiency of the X-ray source on laser pulse parameters and properties of the gas medium was studied.The optimal conditions,when the X-ray photon yield reached a maximum value,have been found when the argon plasma has an electron temperature of Te∼185 eV,an electron density of Ne∼7×10^20 cm^-3 and an average charge of Z∼14.In such a plasma,a coefficient of conversion to soft X-ray radiation with energies Ex-ray∼3.1(±0.2)keV reaches 8.57×10^-5,and no processes leading to the acceleration of electrons to MeV energies occur.It was found that the efficiency of the X-ray emission of this plasma source is mainly determined by the focusing geometry.We confirmed experimentally that the angular distribution of the X-ray radiation is isotropic,and its intensity linearly depends on the energy of the laser pulse,which was varied in the range of 50-280 mJ.We also found that the yield of X-ray photons can be notably increased by,for example,choosing the optimal laser pulse duration and the inlet pressure of the gas jet.

Performance of Pr_(2)(Ni,Cu)O_(4+δ) electrodes in protonic ceramic electrochemical cells with unseparated and separated gas spaces

The Ln_(2)NiO_(4+δ)-based layered phases have attracted much attention as components for high-performance protonic ceramic fuel cells(PCFCs)and electrolysis cells(PCECs)enabling energy conversion with good efficiency and low pollution.The present paper aims at rationally engineering the Cu-doped Pr_(2)NiO_(4+δ)materials and analysing their electrode behaviour for reversible protonic ceramic cells operating in both PCFC and PCEC modes.Complex oxides of Pr_(2)Ni_(1-x)CuxO_(4+δ)(x=0,0.1,0.2 and 0.3)were synthesised using the citrate-nitrate method.The obtained materials were characterised considering their crystalline structures,as well as thermal,thermomechanical and electrotransport properties.A special interest was focused on the quality of an electrode/electrolyte interface governing the electrochemical performance of the cells fabricated.It is shown that a copper doping of x=0.2 has a positive impact on the thermomechanical compatibility of the Ba(Ce,Zr)O_(3)-based electrolytes,providing a better adhesion to these electrolytes at low-temperature sintering and resulting in a decrease of the polarisation resistance of the air electrodes.A reversible protonic ceramic cell demonstrates a power density of~340 m W cm^(-2) and a hydrogen output flux of~3.8 ml cm^(-2) min^(-1) at 750℃.The presented results propose modernised alkaline-earth-element-free and cobalt-free electrodes that can be successfully used in the electrochemical cells based on the-state-of-the-art proton-conducting electrolytes.

Novel materials for solid oxide fuel cells cathodes and oxygen separation membranes:Fundamentals of oxygen transport and performance

In the field of modern hydrogen energy,obtaining pure hydrogen and syngas and then being able to use them for green energy production are significant problems.Developing solid oxide fuel cells(SOFC)and catalytic membranes for oxygen separation as well as materials for these devices is one of the most likely ways to solve these problems.In this work,the authors’recent studies in this field are reviewed;the fundamentals of developing materials for SOFC cathodes and oxygen separation membranes’permselective layers based on research of their oxygen mobility and surface reactivity are presented.Ruddlesden-Popper phases Ln_(2-x)Ca_(x)NiO_(4+δ)(LnCNO)and perovskite-fluorite nanocomposites PrNi_(0.5)Co_(0.5)O_(3-δ)-Ce_(0.9)Y_(0.1)O_(2-δ)(PNC-YDC)were studied by isotope exchange of oxygen with C_(18)O_(2)and^(18)O_(2)in flow and closed reactors.For LnCNO a high oxygen mobility was shown(D*~10^(-7)cm^(2)/s at 700℃),being provided by the cooperative mechanism of oxygen migration involving both regular and highly-mobile interstitial oxygen.For PNC-YDC dominated a wide fast diffusion channel via fluorite phase and interphases due to features of the redistribution of cations resulting in superior oxygen mobility(D*~10^(-8)cm^(2)/s at 700℃).After optimization of composition and nanodomain structure of these materials,as cathodes of SOFC they provided a high power density,while for asymmetric supported oxygen separation membranes-a high oxygen permeability.

Hugoniot equation of state of olivine and its geodynamic implications

Large olivine samples were hot-pressed synthesized for shock wave experiments. The shock wave experiments were carried out at pressure range between 11 and 42 GPa. Shock data on olivine sample yielded a linear relationship between shock wave velocity D and particle velocity u described by D=3.56(?0.13)+2.57(?0.12)u. The shock temperature is determined by an energy relationship which is approximately 790°C at pressure 28 GPa. Due to low temperature and short experimental duration, we suggest that no phase change occurred in our sample below 30 GPa and olivine persisted well beyond its equilibrium boundary in metastable phase. The densities of metastable olivine are in agreement with the results of static compression. At the depth shallower than 410 km, the densities of metastable olivine are higher than those of the PREM model, facilitating cold slab to sink into the mantle transition zone. However, in entire mantle transition zone, the shock densities are lower than those of the PREM model, hampering cold slab to flow across the "660 km" phase boundary.