Crystal structure prediction aims to predict stable and easily experimentally synthesized materials,which accelerates the discovery of new materials.It is worth noting that the stability of materials is the basis for ...Crystal structure prediction aims to predict stable and easily experimentally synthesized materials,which accelerates the discovery of new materials.It is worth noting that the stability of materials is the basis for ensuring high performance and reliable application of materials.Among which,the thermodynamic and molecular dynamics stability is especially important.Therefore,this paper proposes a method to predict stable crystal structures using formation energy and Lennard-Jones potential as evaluation indicators.Specifically,we use graph neural network models to predict the formation energy of crystals,and employ empirical formulas to calculate the Lennard-Jones potential.Then,we apply Bayesian optimization algorithms to search for crystal structures with low formation energy and Lennard-Jones potential approaching zero,in order to ensure the thermodynamic stability and dynamics stability of materials.In addition,considering the impact of the bonding situation between atoms in the crystal on the structural stability,this article uses contact map to analyze the atomic bonding situation of each crystal to screen out more stable materials.Finally,the experimental results show that the method we proposed can not only reduce the time for crystal structure prediction,but also ensure the stability of crystal materials.展开更多
Based on density function theory （DFT） and the local density approximation （LDA）, the formation energy and transition levels of native point defects in LaBr3 were calculated under Br-rich conditions. From the calc...Based on density function theory （DFT） and the local density approximation （LDA）, the formation energy and transition levels of native point defects in LaBr3 were calculated under Br-rich conditions. From the calculated results, the following conclusions have been obtained： ① The dominant defect type is the triply positive lanthanum interstitial under p-type conditions. ② The triply negative lanthanum vacancy plays the most important role in n-type LaBr3.③ Neutral and singly positive bromine antisites are more stable in the middle of the band gap. ④ The singly positive （negative） bromine antisite can be a potential com- pensation source in n-type （p-type） LaBr3. ⑤ All the transition levels in LaBr3 belong to deep levels. The optimized geometric structures of bromine interstitials and antisites show that there is no formation of Br-Br covalent bond.展开更多
β-β″-Al2O3precursor powder was successfully prepared by a solid-phase sintering method with Li2CO3, Na2CO3 （as the sources of Li20 and Na20, respectively） and β″-Al2O3 powder as the raw materials. The precursor...β-β″-Al2O3precursor powder was successfully prepared by a solid-phase sintering method with Li2CO3, Na2CO3 （as the sources of Li20 and Na20, respectively） and β″-Al2O3 powder as the raw materials. The precursor was characterized by X-ray diffraction （XRD） and scan- ning electron microscope （SEM）. The results indicate that the amount of Na20 in the raw materials has a great effect on the formation of β″-Al2O3 in the β-β″-Al2O3 precursor. When Na20 content is 10 wt%, the content of β″-Al2O3 phase reaches the maximum value of 86.24 wt% in the precursor. The β-β″-Al2O3 ceramic was prepared from β-β″-Al2O3 precursor powder by isostatic pressing and burying sintering process. The conductive property of the β-β″-Al2O3 ceramic was examined by electrochemical impedance spectroscopy （EIS） method, and the density was measured by the Archimedes method. The results reveal that when 10 wt% Na20 was added, the sample exhibits the best performance with the lowest resistivity of 4.51.cm and the highest density of 3.25 g.cm 3. A solid electrolyte battery of PtlSnQ, Na2SnO3113 β-β″-Al2O3 Na CrO2, Cr2lO3 Pt was assembled by the β-β″-Al2O3 electrolyte tube to measure the open potential of the resulting battery, and the formation free energy of sodium stannate was calculated In the temperature range of 1273-773 K, the relationship between formation free energy of sodiumstannate and temperature was generated as follows：△GNa2SnO3 0=-1040.83＋0.2221T±7.54.展开更多
A β”/β-Al_2O_3 solid electrolyte was prepared and used in a Na conentration galvanic cell: (-)O_2(in Ar),SnO_2,Na_2SnO_3|β"/β-Al_2O_3]NaCrO_2,Cr_2O_3,O_2(in Ar)(+).The emf measurements were carried out in te...A β”/β-Al_2O_3 solid electrolyte was prepared and used in a Na conentration galvanic cell: (-)O_2(in Ar),SnO_2,Na_2SnO_3|β"/β-Al_2O_3]NaCrO_2,Cr_2O_3,O_2(in Ar)(+).The emf measurements were carried out in temperature range of 912—1223 K:E=652.1— 0.2092 T+2.3(mV).Using this equation and cited free energies of formation of NaCrO_2, Cr_2O_3 and SnO_2,the molar free energy of formation of Na_2 SnO_3 may be calculated by ΔG°=-1050+0.2544 T±5.4(kJ mol^(-1)).展开更多
It was revealed that an average energy of special boundaries is proportional to APB energy in the alloys with the L12 superstructure. This fact proves the appearance of the GAPBs in the planes of location of special b...It was revealed that an average energy of special boundaries is proportional to APB energy in the alloys with the L12 superstructure. This fact proves the appearance of the GAPBs in the planes of location of special boundaries in coincidence sites of ordered alloys. It was determined that the more energy of special boundaries in ordered alloys, the more energy of complex stacking fault. There is a correlation between the distribution of special boundaries as a function its relative energy and ordering energy: the more ordering energy, the more degree of washed away of distribution. The correlation between average relative energy of special boundaries and ordering energy was detected: the more ordering energy, the more average energy of special boundaries. The reverse dependence between ordering energy and average number of special boundaries in grains limited by boundaries of general type was discovered.展开更多
The standard Gibbs free energy of formation of magnesium ferrite was determined by means of two types of solid state electrochemical cells： one using MgZr4（PO4）6 （MZP） as the solid electrolyte and the other using...The standard Gibbs free energy of formation of magnesium ferrite was determined by means of two types of solid state electrochemical cells： one using MgZr4（PO4）6 （MZP） as the solid electrolyte and the other using CaF2 as the solid electrolyte. The first cell was operated in the range of 950 to 1100 K. The second cell was operated in the range of 1125 to 1200 K. The reversibility of the cell EMFs was confirmed by microcoulometric titration. The Gibbs energy changes of magnesium ferrite relative to component oxides were calculated based on EMF measurements and are given by following expressions, respectively： AG1 = -3579-15 T （J/mol） and AGⅡ =6258-24.3 T （J/mol）. The results obtained from two different cells are consistent with each other. The results also are in agreement with Rao＇ s and Tretjakov＇s data in the measured temperature range. When the Gibbs free energies of formation of MgO and Fe203 were substituted in the reaction, the Gibbs free energies of formation of MgFe204 was obtained in two temperature ranges and the for mations are shown as follows： AG 1Formation =-1427394＋360.5 T （J/mol） and AGⅡ Formition =-1417557＋351.2 T （J/mol）.展开更多
Perovskite materials have made a great progress in terms of the power conversion efficiency(PCE), rising from 3.8% to 25.2%. To obtain pinhole-free, superior crystal, and high-quality perovskite films with less defect...Perovskite materials have made a great progress in terms of the power conversion efficiency(PCE), rising from 3.8% to 25.2%. To obtain pinhole-free, superior crystal, and high-quality perovskite films with less defect, intermediates transformation is important, which has been clearly studied and widely applied.In this review, we systematically summarize the commonly formed intermediates and detailedly analyze their mechanisms from five aspects:(1) Solvent-induced intermediate;(2) HI-induced intermediate;(3)CH3NH2-induced intermediate;(4) MAAc-induced intermediate;(5) other intermediates. Finally, we also provide some prospects on high-quality perovskite fabrication based on using intermediates prudently.展开更多
Defects in materials significantly alter their electronic and structural properties,which affect the per-formance of electronic devices,structural alloys,and functional materials.However,calculating all the possible d...Defects in materials significantly alter their electronic and structural properties,which affect the per-formance of electronic devices,structural alloys,and functional materials.However,calculating all the possible defects in complex materials with conventional Density Functional Theory(DFT)can be compu-tationally prohibitive.To enhance the efficiency of these calculations,we interfaced Density Functional Tight Binding(DFTB)with the Clusters Approach to Statistical Mechanics(CASM)software package for the first time.Using SiC and ZnO as representative examples,we show that DFTB gives accurate results and can be used as an efficient computational approach for calculating and pre-screening formation ener-gies/convex hulls.Our DFTB+CASM implementation allows for an efficient exploration(up to an order of magnitude faster than DFT)of formation energies and convex hulls,which researchers can use to probe other complex systems.展开更多
Oxygen vacancy formation and migration in La0.9Sr0.1Ga0.8Mg0.2O3-5 （LSGM） with various crystal symmetries （cubic, rhombohedral, orthorhombic, and monoclinic） are studied by employing first-principles calculations ...Oxygen vacancy formation and migration in La0.9Sr0.1Ga0.8Mg0.2O3-5 （LSGM） with various crystal symmetries （cubic, rhombohedral, orthorhombic, and monoclinic） are studied by employing first-principles calculations based on density functional theory （DFT）. It is shown that the cubic LSGM has the smallest band gap, oxygen vacancy formation energy, and migration barrier, while the other three structures give rise to much larger values for these quantities, implying the best oxygen ion conductivity of the cubic LSGM among the four crystal structures. In out calculations, one oxygen vacancy migration pathway is considered in the cubic and rhombohedral structures due to all the oxygen sites being equivalent in them, while two vacancy migration pathways with different migration barriers are found in the orthorhombic and monoclinic symmetries owing to the existence of nonequivalent O1 and 02 oxygen sites. The migration energies along the migration pathway linking the two 02 sites are obviously lower than those along the pathway linking the O1 and 02 sites. Considering the phase transitions at high temperatures, the results obtained in this paper can not only explain the experimentally observed different behaviours of the oxygen ionic conductivity of LSGM with different symmetries, but also predict the rational crystal structures of LSGM for solid oxide fuel cell applications.展开更多
A density functional theory(DFT)study was employed to investigate the mechanical property,thermal conductivity,Debye temperature,electronic structure and defect chemistry of(Gd_(1-x)Sm_(x))_(2)Zr_(2)O_(7).All the(Gd_(...A density functional theory(DFT)study was employed to investigate the mechanical property,thermal conductivity,Debye temperature,electronic structure and defect chemistry of(Gd_(1-x)Sm_(x))_(2)Zr_(2)O_(7).All the(Gd_(1-x)Sm_(x))_(2)Zr_(2)O_(7) compounds exhibit an excellent structural and mechanical stability(Gd_(0.25)Sm_(0.75))_(2)Zr_(2)O_(7) has the lowest Young’s modulus of 213.7 GPa,the largest Possion’s ratio of 0.292,the lowest Debye temperature of 491.8 K and the lowest thermal conductivity.The calculated thermal conductivities of(Gd_(1-x)Sm_(x))_(2)Zr_(2)O_(7) are 1.17-1.21 W/(m·K)by the Clark’s model and 1.32-1.36 W/(m·K)by the Cahall’s model,respectively.The formation energies of O vacancies at 48f site are negative,which increase with the Sm content,however,the formation energies of O vacancies at 8b site are almost invariable.In addition,Sm partly occupying the Gd-site reduces distinctly the formation energies of defects such as A-site vacancies,cation antisite defects,anion Frenkel pairs of oxygen at 8b site and cation interstitials,which suggests that Sm-doped Gd_(2)Zr_(2)O_(7),especially equimolar GdSmZr_(2)O_(7),has a better irradiation tolerance.After the 16 MeVTa-ion irradiation at a fluence of 1×10^(14) or 2×10^(14) ions/cm^(2),the crystal structure of GdSmZr_(2)O_(7) transforms from pyrochlore to a defect fluorite without obvious amorphous phase.展开更多
The electrochemical formation processes of holmium-cobalt alloys on cobaltcathode in molten HoCl_3-KCl were investigated by cyclic voltammetry and open current potential-timecurve alter potentiostatic electrolysis. Th...The electrochemical formation processes of holmium-cobalt alloys on cobaltcathode in molten HoCl_3-KCl were investigated by cyclic voltammetry and open current potential-timecurve alter potentiostatic electrolysis. The structure of Ho-Co alloys' films deposited on cobaltelectrode by potentiostatic electrolysis was characterized by X-ray diffraction. The standard Gibbsfree energies of formation for the intermetallic compounds of Ho and Co were determined. Thediffusion coefficient and diffusion activation energy of Ho atom in the alloy phase were calculatedto be 10^(-10) -10^(-11) cm^2/s and 96.0 kJ/mol, respectively, from the current-time curve atpotential step.展开更多
SnSb has attracted a great attention in recent investigations as an anode material for Li ion batteries. The formation energies and electronic properties of the Li intercalations in SnSb have been calculated within th...SnSb has attracted a great attention in recent investigations as an anode material for Li ion batteries. The formation energies and electronic properties of the Li intercalations in SnSb have been calculated within the framework of local density functional theory and the first-principles pseudopotential technique. The changes of volumes, band structures, charge density analysis and the electronic density of states for the Li intercalations are presented. The results show that the average Li intercalation formation energy per Li atom is around 2.7 eV.展开更多
First-principles calculations have been performed to study the lithium intercalations in MoS2. The formation energies, changes of volumes, electronic structures and charge densities of the lithium intercalations in Mo...First-principles calculations have been performed to study the lithium intercalations in MoS2. The formation energies, changes of volumes, electronic structures and charge densities of the lithium intercalations in MoS2 are presented. Our calculations show that during lithium intercalations in MoS2, the lithium intercalation formation energies per lithium atom are between 2.5 eV to 3.0 eV. The volume expansions of MoS2 due to lithium intercalations are relatively small展开更多
The electrochemical alloying of Y-Cu system in molten NaCl-KCl-YCl_3 has been investi- gated.The free energy changes of the formation reactions of the intermetallic compounds,in- cluding YCu_6 ,YCu_4 YCu_2 ,Yfu(973—1...The electrochemical alloying of Y-Cu system in molten NaCl-KCl-YCl_3 has been investi- gated.The free energy changes of the formation reactions of the intermetallic compounds,in- cluding YCu_6 ,YCu_4 YCu_2 ,Yfu(973—103 K),were determined by means of electrode potential-time curves of the working electrode after potentiostatic electrolysis.The results in- dicate that the potential-time method is simple and reliable.展开更多
In this paper it has theoretically proved that the relationship of the molar atomic standard free energies of formation of binary intermediate compounds to the molar fraction of component is a quasi-parabola which is ...In this paper it has theoretically proved that the relationship of the molar atomic standard free energies of formation of binary intermediate compounds to the molar fraction of component is a quasi-parabola which is called a quasi-parabolic regula- tion.展开更多
Based on the Miedema model and Extended Miedema theory,the formation energies of different solute components in Er-X binary system and Al-Er-X ternary systems were calculated.The results show that the variation of erb...Based on the Miedema model and Extended Miedema theory,the formation energies of different solute components in Er-X binary system and Al-Er-X ternary systems were calculated.The results show that the variation of erbium content has little influence on the chance rate of the formation Al-Er compound in the Al-Mg-Mn-Zr-Er system.The calculated formation energies in the Er-X binary system and Al-Er-X ternary systems indicate that Al3Er phase can take priority of depositing,Al-Er-Zr ternary compounds may also found which agrees with the experimental results in references.The consistency of calculation and experiment proves that the intermetallic compounds in the Al-Mg-Mn-Zr-Er system can be predicted directly by calculating the formation energies of the reactions in Er-X binary system and Al-Er-X ternary systems with the Miedema model and Extended Miedema theory.展开更多
Aiming at the technology of hydraulic fracturing assisted oil displacement which combines hydraulic fracturing,seepage and oil displacement,an experimental system of energy storage and flowback in fracturing assisted ...Aiming at the technology of hydraulic fracturing assisted oil displacement which combines hydraulic fracturing,seepage and oil displacement,an experimental system of energy storage and flowback in fracturing assisted oil displacement process has been developed and used to simulate the mechanism of percolation,energy storage,oil displacement and flowback of chemical agents in the whole process.The research shows that in hydraulic fracturing assisted oil displacement,the chemical agent could be directly pushed to the deeper area of the low and medium permeability reservoirs,avoiding the viscosity loss and adhesion retention of chemical agents near the pay zone;in addition,this technology could effectively enlarge the swept volume,improve the oil displacement efficiency,replenish formation energy,gather and exploit the scattered residual oil.For the reservoir with higher permeability,this measure takes effect fast,so to lower cost,and the high pressure hydraulic fracturing assisted oil displacement could be adopted directly.For the reservoir with lower permeability which is difficult to absorb water,hydraulic fracturing assisted oil displacement with surfactant should be adopted to reduce flow resistance of the reservoir and improve the water absorption capacity and development effect of the reservoir.The degree of formation energy deficit was the main factor affecting the effective swept range of chemical agents.Moreover,the larger the formation energy deficit was,the further the seepage distance of chemical agents was,accordingly,the larger the effective swept volume was,and the greater the increase of oil recovery was.Formation energy enhancement was the most important contribution to enhanced oil recovery(EOR),which was the key to EOR by the technology of hydraulic fracturing assisted oil displacement.展开更多
Low permeability tight sandstone reservoirs have a high filtrational resistance and a very low fluid flow rate.As a result,the propagation speed of the formation pressure is low and fluid flow behaves as a non-Darcy f...Low permeability tight sandstone reservoirs have a high filtrational resistance and a very low fluid flow rate.As a result,the propagation speed of the formation pressure is low and fluid flow behaves as a non-Darcy flow,which typically displays a highly non-linear behavior.In this paper,the characteristics and mechanism of pressure propagation in this kind of reservoir are revealed through a laboratory pressure propagation experiment and through data from an actual tight reservoir development.The main performance mechanism is as follows:A new pressure cage concept is proposed based on the pressure variation characteristics of the laboratory experiments.There are two methods of energy propagation in the actual water injection process:one is that energy is transmitted to the deep reservoir by the fluid flowing through the reservoir,and the other is that energy is transmitted by the elasticity of the reservoir.For one injection well model and one production well model,the pressure distribution curve between the injection and production wells,as calculated by the theoretical method,has three section types,and they show an oblique“S”shape with a straight middle section.However,the actual pressure distribution curve is nonlinear,with an obvious pressure advance at the front.After the injection pressure increases to a certain level,the curve shape is an oblique and reversed“S”shape.Based on the research,this paper explains the deep-seated reasons for the difference in pressure distribution and proposes that it is an effective way to develop low permeability tight reservoirs using the water injection supplement energy method.展开更多
By using the first-principles calculation, we studied the mechanisms of point defects in Y4AI209 （YAM）, a promising ternary oxide with excellent optical and thermal properties. It is found that the predominant nativ...By using the first-principles calculation, we studied the mechanisms of point defects in Y4AI209 （YAM）, a promising ternary oxide with excellent optical and thermal properties. It is found that the predominant native defect species is closely dependent on the chemical potentials of each constituent. In the case of O-rich condition, the oxygen interstitial has the very low defect formation energy, followed by the anti-site defects and AI vacancy; in the case of AI-rich condition, the oxygen vacancy yields the lowest defect formation energy, followed by the anti-site defects and AI interstitial. The present result shows that in all the possible chemical potential ranges, anti-site defects have relatively low defect formation energy and might exist in high concentration in YAM. Furthermore, AIy anti-site has relatively lower defect formation energy than the YAt anti- site throughout. The behaviors of defect complexes under non-stoichiometric condition, such as the AI203 or Y203 excess, are also investigated. The results provide helpful guide to optimize the experimental synthesizing of YAM.展开更多
Highly active and durable electrocatalysts towards oxygen reduction reaction(ORR)are imperative for the commercialization application of proton exchange membrane fuel cells.By manipulating ligand effect,structural con...Highly active and durable electrocatalysts towards oxygen reduction reaction(ORR)are imperative for the commercialization application of proton exchange membrane fuel cells.By manipulating ligand effect,structural control,and strain effect,we report here the precise preparation of Mo-doped Pt_(3)Co alloy nanowires(Pt_(3)Co-Mo NWs)as the efficient catalyst towards ORR with high specific activity(0.596 mA cm^(−2))and mass activity(MA,0.84 A mg^(−1)_(Pt)),much higher than those of undoped counterparts.Besides activity,Pt_(3)Co-Mo NWs also demonstrate excellent structural stability and cyclic durability even after 50,000 cycles,again surpassing control samples without Mo dopants.According to the strain maps and DFT calculations,Mo dopants could modify the electronic structure of both Pt and Co to achieve not only optimized oxygen-intermediate binding energy on the interface but also increased the vacancy formation energy of Co,together leading to enhanced activity and durability.This work provides not only a facile methodology but also an in-depth investigation of the relationship between structure and properties to provide general guidance for future design and optimization.展开更多
基金supported by the Nature Science Foundation of China(Nos.61671362 and 62071366)。
文摘Crystal structure prediction aims to predict stable and easily experimentally synthesized materials,which accelerates the discovery of new materials.It is worth noting that the stability of materials is the basis for ensuring high performance and reliable application of materials.Among which,the thermodynamic and molecular dynamics stability is especially important.Therefore,this paper proposes a method to predict stable crystal structures using formation energy and Lennard-Jones potential as evaluation indicators.Specifically,we use graph neural network models to predict the formation energy of crystals,and employ empirical formulas to calculate the Lennard-Jones potential.Then,we apply Bayesian optimization algorithms to search for crystal structures with low formation energy and Lennard-Jones potential approaching zero,in order to ensure the thermodynamic stability and dynamics stability of materials.In addition,considering the impact of the bonding situation between atoms in the crystal on the structural stability,this article uses contact map to analyze the atomic bonding situation of each crystal to screen out more stable materials.Finally,the experimental results show that the method we proposed can not only reduce the time for crystal structure prediction,but also ensure the stability of crystal materials.
基金Supported by the National Nature Science Foundation of China(11275142)
文摘Based on density function theory （DFT） and the local density approximation （LDA）, the formation energy and transition levels of native point defects in LaBr3 were calculated under Br-rich conditions. From the calculated results, the following conclusions have been obtained： ① The dominant defect type is the triply positive lanthanum interstitial under p-type conditions. ② The triply negative lanthanum vacancy plays the most important role in n-type LaBr3.③ Neutral and singly positive bromine antisites are more stable in the middle of the band gap. ④ The singly positive （negative） bromine antisite can be a potential com- pensation source in n-type （p-type） LaBr3. ⑤ All the transition levels in LaBr3 belong to deep levels. The optimized geometric structures of bromine interstitials and antisites show that there is no formation of Br-Br covalent bond.
基金financially supported by the National Natural Science Foundation of China (No.51234009)
文摘β-β″-Al2O3precursor powder was successfully prepared by a solid-phase sintering method with Li2CO3, Na2CO3 （as the sources of Li20 and Na20, respectively） and β″-Al2O3 powder as the raw materials. The precursor was characterized by X-ray diffraction （XRD） and scan- ning electron microscope （SEM）. The results indicate that the amount of Na20 in the raw materials has a great effect on the formation of β″-Al2O3 in the β-β″-Al2O3 precursor. When Na20 content is 10 wt%, the content of β″-Al2O3 phase reaches the maximum value of 86.24 wt% in the precursor. The β-β″-Al2O3 ceramic was prepared from β-β″-Al2O3 precursor powder by isostatic pressing and burying sintering process. The conductive property of the β-β″-Al2O3 ceramic was examined by electrochemical impedance spectroscopy （EIS） method, and the density was measured by the Archimedes method. The results reveal that when 10 wt% Na20 was added, the sample exhibits the best performance with the lowest resistivity of 4.51.cm and the highest density of 3.25 g.cm 3. A solid electrolyte battery of PtlSnQ, Na2SnO3113 β-β″-Al2O3 Na CrO2, Cr2lO3 Pt was assembled by the β-β″-Al2O3 electrolyte tube to measure the open potential of the resulting battery, and the formation free energy of sodium stannate was calculated In the temperature range of 1273-773 K, the relationship between formation free energy of sodiumstannate and temperature was generated as follows：△GNa2SnO3 0=-1040.83＋0.2221T±7.54.
文摘A β”/β-Al_2O_3 solid electrolyte was prepared and used in a Na conentration galvanic cell: (-)O_2(in Ar),SnO_2,Na_2SnO_3|β"/β-Al_2O_3]NaCrO_2,Cr_2O_3,O_2(in Ar)(+).The emf measurements were carried out in temperature range of 912—1223 K:E=652.1— 0.2092 T+2.3(mV).Using this equation and cited free energies of formation of NaCrO_2, Cr_2O_3 and SnO_2,the molar free energy of formation of Na_2 SnO_3 may be calculated by ΔG°=-1050+0.2544 T±5.4(kJ mol^(-1)).
基金B.V.Konovalova., N.A. Koneva and E.V.Kozlov acknowledge the INTAS for the partial support of this research under INTAS97-319
文摘It was revealed that an average energy of special boundaries is proportional to APB energy in the alloys with the L12 superstructure. This fact proves the appearance of the GAPBs in the planes of location of special boundaries in coincidence sites of ordered alloys. It was determined that the more energy of special boundaries in ordered alloys, the more energy of complex stacking fault. There is a correlation between the distribution of special boundaries as a function its relative energy and ordering energy: the more ordering energy, the more degree of washed away of distribution. The correlation between average relative energy of special boundaries and ordering energy was detected: the more ordering energy, the more average energy of special boundaries. The reverse dependence between ordering energy and average number of special boundaries in grains limited by boundaries of general type was discovered.
基金the National Natural Science Foundation of China (No.50572024) the Education Ministry Foundation for Returning Overseas Scholar of China.
文摘The standard Gibbs free energy of formation of magnesium ferrite was determined by means of two types of solid state electrochemical cells： one using MgZr4（PO4）6 （MZP） as the solid electrolyte and the other using CaF2 as the solid electrolyte. The first cell was operated in the range of 950 to 1100 K. The second cell was operated in the range of 1125 to 1200 K. The reversibility of the cell EMFs was confirmed by microcoulometric titration. The Gibbs energy changes of magnesium ferrite relative to component oxides were calculated based on EMF measurements and are given by following expressions, respectively： AG1 = -3579-15 T （J/mol） and AGⅡ =6258-24.3 T （J/mol）. The results obtained from two different cells are consistent with each other. The results also are in agreement with Rao＇ s and Tretjakov＇s data in the measured temperature range. When the Gibbs free energies of formation of MgO and Fe203 were substituted in the reaction, the Gibbs free energies of formation of MgFe204 was obtained in two temperature ranges and the for mations are shown as follows： AG 1Formation =-1427394＋360.5 T （J/mol） and AGⅡ Formition =-1417557＋351.2 T （J/mol）.
基金funded by the National Natural Science Foundation of China (51902148, 61704099, 51801088 and 11664001)the Fundamental Research Funds for the Central Universities (lzujbky-2020-61, lzujbky-2019-88 and lzujbky-2020-kb06)the Special Funding for Open and Shared Large-Scale Instruments and Equipments of Lanzhou University (LZU-GXJJ-2019C023 and LZU-GXJJ-2019C019)。
文摘Perovskite materials have made a great progress in terms of the power conversion efficiency(PCE), rising from 3.8% to 25.2%. To obtain pinhole-free, superior crystal, and high-quality perovskite films with less defect, intermediates transformation is important, which has been clearly studied and widely applied.In this review, we systematically summarize the commonly formed intermediates and detailedly analyze their mechanisms from five aspects:(1) Solvent-induced intermediate;(2) HI-induced intermediate;(3)CH3NH2-induced intermediate;(4) MAAc-induced intermediate;(5) other intermediates. Finally, we also provide some prospects on high-quality perovskite fabrication based on using intermediates prudently.
基金supported by the U.S.Department of Energy,Na-tional Energy Technology Laboratory(NETL),under Award No.DE-FE0030582.
文摘Defects in materials significantly alter their electronic and structural properties,which affect the per-formance of electronic devices,structural alloys,and functional materials.However,calculating all the possible defects in complex materials with conventional Density Functional Theory(DFT)can be compu-tationally prohibitive.To enhance the efficiency of these calculations,we interfaced Density Functional Tight Binding(DFTB)with the Clusters Approach to Statistical Mechanics(CASM)software package for the first time.Using SiC and ZnO as representative examples,we show that DFTB gives accurate results and can be used as an efficient computational approach for calculating and pre-screening formation ener-gies/convex hulls.Our DFTB+CASM implementation allows for an efficient exploration(up to an order of magnitude faster than DFT)of formation energies and convex hulls,which researchers can use to probe other complex systems.
基金supported by the National Natural Science Foundation of China (Grant No.10974183)
文摘Oxygen vacancy formation and migration in La0.9Sr0.1Ga0.8Mg0.2O3-5 （LSGM） with various crystal symmetries （cubic, rhombohedral, orthorhombic, and monoclinic） are studied by employing first-principles calculations based on density functional theory （DFT）. It is shown that the cubic LSGM has the smallest band gap, oxygen vacancy formation energy, and migration barrier, while the other three structures give rise to much larger values for these quantities, implying the best oxygen ion conductivity of the cubic LSGM among the four crystal structures. In out calculations, one oxygen vacancy migration pathway is considered in the cubic and rhombohedral structures due to all the oxygen sites being equivalent in them, while two vacancy migration pathways with different migration barriers are found in the orthorhombic and monoclinic symmetries owing to the existence of nonequivalent O1 and 02 oxygen sites. The migration energies along the migration pathway linking the two 02 sites are obviously lower than those along the pathway linking the O1 and 02 sites. Considering the phase transitions at high temperatures, the results obtained in this paper can not only explain the experimentally observed different behaviours of the oxygen ionic conductivity of LSGM with different symmetries, but also predict the rational crystal structures of LSGM for solid oxide fuel cell applications.
基金Project supported by the National Natural Science Foundation of China(51621091,51321061,51021002)the National Science and Technology Major Project(2017-Ⅵ-0020-0093)。
文摘A density functional theory(DFT)study was employed to investigate the mechanical property,thermal conductivity,Debye temperature,electronic structure and defect chemistry of(Gd_(1-x)Sm_(x))_(2)Zr_(2)O_(7).All the(Gd_(1-x)Sm_(x))_(2)Zr_(2)O_(7) compounds exhibit an excellent structural and mechanical stability(Gd_(0.25)Sm_(0.75))_(2)Zr_(2)O_(7) has the lowest Young’s modulus of 213.7 GPa,the largest Possion’s ratio of 0.292,the lowest Debye temperature of 491.8 K and the lowest thermal conductivity.The calculated thermal conductivities of(Gd_(1-x)Sm_(x))_(2)Zr_(2)O_(7) are 1.17-1.21 W/(m·K)by the Clark’s model and 1.32-1.36 W/(m·K)by the Cahall’s model,respectively.The formation energies of O vacancies at 48f site are negative,which increase with the Sm content,however,the formation energies of O vacancies at 8b site are almost invariable.In addition,Sm partly occupying the Gd-site reduces distinctly the formation energies of defects such as A-site vacancies,cation antisite defects,anion Frenkel pairs of oxygen at 8b site and cation interstitials,which suggests that Sm-doped Gd_(2)Zr_(2)O_(7),especially equimolar GdSmZr_(2)O_(7),has a better irradiation tolerance.After the 16 MeVTa-ion irradiation at a fluence of 1×10^(14) or 2×10^(14) ions/cm^(2),the crystal structure of GdSmZr_(2)O_(7) transforms from pyrochlore to a defect fluorite without obvious amorphous phase.
文摘The electrochemical formation processes of holmium-cobalt alloys on cobaltcathode in molten HoCl_3-KCl were investigated by cyclic voltammetry and open current potential-timecurve alter potentiostatic electrolysis. The structure of Ho-Co alloys' films deposited on cobaltelectrode by potentiostatic electrolysis was characterized by X-ray diffraction. The standard Gibbsfree energies of formation for the intermetallic compounds of Ho and Co were determined. Thediffusion coefficient and diffusion activation energy of Ho atom in the alloy phase were calculatedto be 10^(-10) -10^(-11) cm^2/s and 96.0 kJ/mol, respectively, from the current-time curve atpotential step.
基金This work was supported by the Natural Science Foundation of Fujian Province under grant No.E032001.
文摘SnSb has attracted a great attention in recent investigations as an anode material for Li ion batteries. The formation energies and electronic properties of the Li intercalations in SnSb have been calculated within the framework of local density functional theory and the first-principles pseudopotential technique. The changes of volumes, band structures, charge density analysis and the electronic density of states for the Li intercalations are presented. The results show that the average Li intercalation formation energy per Li atom is around 2.7 eV.
基金This work was supported by the National Natural Science Foundation of China under Grant No.10374076by the Natural Science Foundation of Fujian Province under Grant Nos.E0410025 and E032001.
文摘First-principles calculations have been performed to study the lithium intercalations in MoS2. The formation energies, changes of volumes, electronic structures and charge densities of the lithium intercalations in MoS2 are presented. Our calculations show that during lithium intercalations in MoS2, the lithium intercalation formation energies per lithium atom are between 2.5 eV to 3.0 eV. The volume expansions of MoS2 due to lithium intercalations are relatively small
文摘The electrochemical alloying of Y-Cu system in molten NaCl-KCl-YCl_3 has been investi- gated.The free energy changes of the formation reactions of the intermetallic compounds,in- cluding YCu_6 ,YCu_4 YCu_2 ,Yfu(973—103 K),were determined by means of electrode potential-time curves of the working electrode after potentiostatic electrolysis.The results in- dicate that the potential-time method is simple and reliable.
文摘In this paper it has theoretically proved that the relationship of the molar atomic standard free energies of formation of binary intermediate compounds to the molar fraction of component is a quasi-parabola which is called a quasi-parabolic regula- tion.
基金Projects(2006AA03A207,2007AA03Z514)supported by the National High-tech Research and Development Program of China
文摘Based on the Miedema model and Extended Miedema theory,the formation energies of different solute components in Er-X binary system and Al-Er-X ternary systems were calculated.The results show that the variation of erbium content has little influence on the chance rate of the formation Al-Er compound in the Al-Mg-Mn-Zr-Er system.The calculated formation energies in the Er-X binary system and Al-Er-X ternary systems indicate that Al3Er phase can take priority of depositing,Al-Er-Zr ternary compounds may also found which agrees with the experimental results in references.The consistency of calculation and experiment proves that the intermetallic compounds in the Al-Mg-Mn-Zr-Er system can be predicted directly by calculating the formation energies of the reactions in Er-X binary system and Al-Er-X ternary systems with the Miedema model and Extended Miedema theory.
基金Supported by the National Natural Science Foundation of China(52074087,51804076)Postdoctoral Natural Science Foundation of China(2021M690528).
文摘Aiming at the technology of hydraulic fracturing assisted oil displacement which combines hydraulic fracturing,seepage and oil displacement,an experimental system of energy storage and flowback in fracturing assisted oil displacement process has been developed and used to simulate the mechanism of percolation,energy storage,oil displacement and flowback of chemical agents in the whole process.The research shows that in hydraulic fracturing assisted oil displacement,the chemical agent could be directly pushed to the deeper area of the low and medium permeability reservoirs,avoiding the viscosity loss and adhesion retention of chemical agents near the pay zone;in addition,this technology could effectively enlarge the swept volume,improve the oil displacement efficiency,replenish formation energy,gather and exploit the scattered residual oil.For the reservoir with higher permeability,this measure takes effect fast,so to lower cost,and the high pressure hydraulic fracturing assisted oil displacement could be adopted directly.For the reservoir with lower permeability which is difficult to absorb water,hydraulic fracturing assisted oil displacement with surfactant should be adopted to reduce flow resistance of the reservoir and improve the water absorption capacity and development effect of the reservoir.The degree of formation energy deficit was the main factor affecting the effective swept range of chemical agents.Moreover,the larger the formation energy deficit was,the further the seepage distance of chemical agents was,accordingly,the larger the effective swept volume was,and the greater the increase of oil recovery was.Formation energy enhancement was the most important contribution to enhanced oil recovery(EOR),which was the key to EOR by the technology of hydraulic fracturing assisted oil displacement.
基金supported by the National Science and Technology Major Project Fueling Shale Gas Development Demonstration Project[grant number 2016ZX05060]the Science and Technology Innovation Foundation of CNPC[grant number 2016D-5007-0208].
文摘Low permeability tight sandstone reservoirs have a high filtrational resistance and a very low fluid flow rate.As a result,the propagation speed of the formation pressure is low and fluid flow behaves as a non-Darcy flow,which typically displays a highly non-linear behavior.In this paper,the characteristics and mechanism of pressure propagation in this kind of reservoir are revealed through a laboratory pressure propagation experiment and through data from an actual tight reservoir development.The main performance mechanism is as follows:A new pressure cage concept is proposed based on the pressure variation characteristics of the laboratory experiments.There are two methods of energy propagation in the actual water injection process:one is that energy is transmitted to the deep reservoir by the fluid flowing through the reservoir,and the other is that energy is transmitted by the elasticity of the reservoir.For one injection well model and one production well model,the pressure distribution curve between the injection and production wells,as calculated by the theoretical method,has three section types,and they show an oblique“S”shape with a straight middle section.However,the actual pressure distribution curve is nonlinear,with an obvious pressure advance at the front.After the injection pressure increases to a certain level,the curve shape is an oblique and reversed“S”shape.Based on the research,this paper explains the deep-seated reasons for the difference in pressure distribution and proposes that it is an effective way to develop low permeability tight reservoirs using the water injection supplement energy method.
基金supported by the National Natural Science Foundation of China under Grant Nos.50672102,50832008 and 51032006
文摘By using the first-principles calculation, we studied the mechanisms of point defects in Y4AI209 （YAM）, a promising ternary oxide with excellent optical and thermal properties. It is found that the predominant native defect species is closely dependent on the chemical potentials of each constituent. In the case of O-rich condition, the oxygen interstitial has the very low defect formation energy, followed by the anti-site defects and AI vacancy; in the case of AI-rich condition, the oxygen vacancy yields the lowest defect formation energy, followed by the anti-site defects and AI interstitial. The present result shows that in all the possible chemical potential ranges, anti-site defects have relatively low defect formation energy and might exist in high concentration in YAM. Furthermore, AIy anti-site has relatively lower defect formation energy than the YAt anti- site throughout. The behaviors of defect complexes under non-stoichiometric condition, such as the AI203 or Y203 excess, are also investigated. The results provide helpful guide to optimize the experimental synthesizing of YAM.
基金financially supported by the Natural Sciences and Engineering Research Council of Canada(NSERC),through the Discovery Grant Program(RGPIN-2018-06725RGPIN-201705080)+2 种基金the Discovery Accelerator Supplement Grant program(RGPAS-2018-522651)by the New Frontiers in Research Fund-Exploration program(NFRFE-2019-00488)support from the University of Alberta and Future Energy Systems(FES)。
文摘Highly active and durable electrocatalysts towards oxygen reduction reaction(ORR)are imperative for the commercialization application of proton exchange membrane fuel cells.By manipulating ligand effect,structural control,and strain effect,we report here the precise preparation of Mo-doped Pt_(3)Co alloy nanowires(Pt_(3)Co-Mo NWs)as the efficient catalyst towards ORR with high specific activity(0.596 mA cm^(−2))and mass activity(MA,0.84 A mg^(−1)_(Pt)),much higher than those of undoped counterparts.Besides activity,Pt_(3)Co-Mo NWs also demonstrate excellent structural stability and cyclic durability even after 50,000 cycles,again surpassing control samples without Mo dopants.According to the strain maps and DFT calculations,Mo dopants could modify the electronic structure of both Pt and Co to achieve not only optimized oxygen-intermediate binding energy on the interface but also increased the vacancy formation energy of Co,together leading to enhanced activity and durability.This work provides not only a facile methodology but also an in-depth investigation of the relationship between structure and properties to provide general guidance for future design and optimization.
