Intrinsic magnetic topological insulators have been reported to exhibit novel physical phenomena such as the quantum anomalous Hall effect and axion insulator states,demonstrating potential for applications in spintro...Intrinsic magnetic topological insulators have been reported to exhibit novel physical phenomena such as the quantum anomalous Hall effect and axion insulator states,demonstrating potential for applications in spintronics and topological quantum computing.Here we perform low-temperature scanning tunneling microscopy(STM)investigations of the antiferromagnetic ground state of MnSb_(2)Te_(4),a predicted magnetic topological insulator isostructural with MnBi_(2)Te_(4).We visualize the hexagonal Te-terminated surface of MnSb_(2)Te_(4)and identify two distinct defects originating from different antisite substitutions.Notably,we identify an in-gap state above the Fermi energy where the tunneling spectrum exhibits a negative differential conductance behavior.This electronic state can be modulated by external electric and magnetic fields,suggesting effective pathways for electronic state manipulation.Spin-resolved STM measurements further reveal additional magnetic resonance peaks associated with Mn antisite defects.Our results provide novel insights into the investigation of magnetic topological insulators and demonstrate a promising approach to modulate the localized electronic states.展开更多
A simple modified analytic EAM model for bcc Fe and fcc Al was used to calculate the lattice constant and elastic constants of B2 FeAl and DO3 Fe3Al alloys. The formation energies of ...A simple modified analytic EAM model for bcc Fe and fcc Al was used to calculate the lattice constant and elastic constants of B2 FeAl and DO3 Fe3Al alloys. The formation energies of vacancy and antisite were also calculated. The present calculations are in agreement with the experimental data and the theoretical results obtained by other authors.展开更多
From the UV?Vis absorption spectra,the FT-IR absorption spectra and the Raman spectra,it is deduced that Co ionsprimarily occupy the tetrahedral(A)site,with a minor number of them entering into the octahedral(B)site i...From the UV?Vis absorption spectra,the FT-IR absorption spectra and the Raman spectra,it is deduced that Co ionsprimarily occupy the tetrahedral(A)site,with a minor number of them entering into the octahedral(B)site in the Ni1?xCoxCr2O4compounds.The origin of the position disorder of the Co ions is consistent with the similar ionic radii of the Co ion(0.65?)and theCr ion(0.62?)at B site.The FT-IR peak at about510cm?1shifts towards high frequency side with the increasing cobalt content.Itis resulted from the reduction of the cation?oxygen distance in the octahedron by the replacement of the Ni2+with the Co2+ions.Themagnetic measurement shows that Curie temperatures(TC)are75and90K for the compounds with x=0.2and0.8,respectively.展开更多
Developing transition metal oxides(TMOs)with high energy,power,and long cycle lifetime for elec-tric energy storage devices remains a critical challenge to date.Herein,we demonstrate a facile method that enables in-si...Developing transition metal oxides(TMOs)with high energy,power,and long cycle lifetime for elec-tric energy storage devices remains a critical challenge to date.Herein,we demonstrate a facile method that enables in-situ transformation of nickel cobalt oxide nanowire arrays(NiCoO NWA)into hierarchical nanowire-nanosheet arrays(ac-NiCoO NWSA)for enhanced energy storage properties.More specifically,the method leads to formation of atomically thin nanosheets(only 2.0 nm)and creates abundant an-tisite defects and oxygen vacancies.Owing to these merits,the as-prepared ac-NiCoO NWSA electrode exhibits over five-fold higher specific capacity,superior rate capability(up to 100 A/g),and excellent cy-cling stability of 10,000 cycles at 50 A/g in alkaline electrolyte compared to pristine NiCoO NWA.Density functional theory(DFT)simulations elucidate the electrochemical activity enhancement mechanism of the TMOs.Moreover,our method triggers similar structural reconstruction phenomenon on other TMOs including ZnCo-,CoMn-and ZnNiCo-oxides,proving the universality of the method.Our findings provide a general method towards simultaneously manipulating the micro-morphologies and defects of TMOs for advanced energy storage devices.展开更多
The ferromagnetic semiconductor La2NiMnO6 （LNMO） has recently received much attention due to its high Curie temperature （Tc 280 K）, which is close to room temperature. We prepared single-phase LNMO polycrystaUine...The ferromagnetic semiconductor La2NiMnO6 （LNMO） has recently received much attention due to its high Curie temperature （Tc 280 K）, which is close to room temperature. We prepared single-phase LNMO polycrystaUine samples and investigated the temperature- and field-dependent magnetic behaviors of bulk LNMO. Between Tc and T＊ = 300 K, we observed upward and downward deviations from the Curie-Weiss law for high and low magnetic fields, respectively. From the electron spin resonance results, we can exclude the existence of the Griffiths phase. On the contrary, our results indicate that the abnormal magnetic behaviors might be induced by antisite phase boundaries with antiferromagnetic interaction.展开更多
A half-metallic full-Heusler Mn_(2)VAl alloy is a potential p-type thermoelectric material that can directly generate electricity from waste heat via the Seebeck effect.For practical use,the Seebeck coefficient S of M...A half-metallic full-Heusler Mn_(2)VAl alloy is a potential p-type thermoelectric material that can directly generate electricity from waste heat via the Seebeck effect.For practical use,the Seebeck coefficient S of Mn_(2)VAl should be increased while maintaining a high electrical conductivity s from its half-metallic character.Herein,we achieved this objective through antisite defect engineering.Theoretically,it was predicted that the S was maximized by regulating partial density of states of majority-spin sp-electrons through the control of the fraction of antisite defect,f_(AD),between V and Al atoms in Mn_(2)VAl.Experi-mentally,a significant increase in S and a slight decrease in s were observed for an Mn_(2)VAl sample with an optimal fAD=33%,enhancing the thermoelectric power factor PF by 2.7 times from an Mn_(2)VAl sample with fAD=14%.Furthermore,we combined the antisite defect engineering with a partial substitution method.An Mn_(2)V(Al_(0.96)Si_(0.04))sample with fAD=33%exhibited the highest PF=4.5×10^(-4)W·m^(-1)·K^(-2)at 767 K among the samples.The maximum dimensionless figure-of-merit zT of the Mn_(2)V(Al_(0.96)Si_(0.04))sample with f_(AD)=33%was measured to be 3.4×10^(-2)at 767 K,which is the highest among the p-type half-metallic full-Heusler alloys.展开更多
The rapid advancement of metal halide perovskites can be attributed to their exceptional optoelectronic properties and facile solution processing technique.Noteworthy strides have been achieved in the realm of perovsk...The rapid advancement of metal halide perovskites can be attributed to their exceptional optoelectronic properties and facile solution processing technique.Noteworthy strides have been achieved in the realm of perovskite solar cells(PSCs),with a certified power conversion efficiency(PCE)escalating to 26.7%over the course of a decade,positioning them as promising contenders for next-generation photovoltaic technologies[1].However,the formation of crystal defects,including anion/cation vacancies,Pb–I antisite defects,and uncoordinated Pb^(2+),along the surface and grain boundaries(GBs)of perovskite layers during the solution processing stage poses a significant challenge,compromising the photoelectric performance and stability of PSCs.展开更多
The temporal evolution feature of a microscopic phase field model is utilized to study the antisite defects of L1 2-Ni 3 Al;this is quite different from other physicist’ interests.There are mainly two points in brief...The temporal evolution feature of a microscopic phase field model is utilized to study the antisite defects of L1 2-Ni 3 Al;this is quite different from other physicist’ interests.There are mainly two points in brief.Firstly,antisite defects Ni Al and Al Ni ,which are caused by the deviation from the stoichiometric Ni 3 Al,coexist in the Ni 3 Al phase.The surplus Ni atom in the Ni-rich side is prone to substitute Al thus producing the antisite defect Ni Al that maintains the stability of the L1 2 structure.In other case,the surplus Al atom in the Al-rich side is accommodated by a Ni sublattice consequently giving rise to antisite defect Al Ni .The calculated equilibrium occupancy probability of Ni Al is much higher than that of Al Ni .This point is generally in line with other theoretical and experimental works.Additionally,both Ni Al and Al Ni have a strong negative correlation to time step during the disorder-order transformation.Since the initial value of Ni Al and Al Ni on each site of the matrix is right at the concentration that we set,we can observe the decrease process of Ni Al and Al Ni from the initial disordered high anti-structure state to their respective equilibrium state,i.e.to the result of the ordering process further coarsening.展开更多
As an ion conductor, the Al-doped Li1+xAlxGe2-x(PO4)3(LAGP) demonstrates the superionic Li diffusion behavior, however,without the convinced verifications. In this context, the density functional theory(DFT) calculati...As an ion conductor, the Al-doped Li1+xAlxGe2-x(PO4)3(LAGP) demonstrates the superionic Li diffusion behavior, however,without the convinced verifications. In this context, the density functional theory(DFT) calculations are employed to clarify the structural origin of the fast Li ion migration kinetics in LAGP solid electrolytes. The calculated results show that doping of Al leads to an emerging high-energy 36 f Li site, which plays an important role in promoting the Li diffusion and can largely lower the Li ion diffusion energy barrier. Moreover, the Li/Al antisite defect is investigated firstly, with which the Li ions are excited to occupy a relatively high energy site in LAGP. The obvious local structural distortion by Li/Al antisite results in the coordination change upon Li diffusion(lattice field distortion), which facilitates the Li diffusion significantly and is probably the main reason to account for the superionic diffusion phenomenon. Therefore, the occupation of Li at high-energy sites should be an effective method to establish the fast Li diffusion, which implies a rewarding avenue to build better Li-ion batteries.展开更多
Microscopic phase field simulation is performed to study antisite defect type and temporal evolution characteristic of D022-Ni3V structure in Ni75AlxV25-x ternary system.The result demonstrates that two types of antis...Microscopic phase field simulation is performed to study antisite defect type and temporal evolution characteristic of D022-Ni3V structure in Ni75AlxV25-x ternary system.The result demonstrates that two types of antisite defect VNi and NiV coexist in D022 structure;however,the amount of NiV is far greater than VNi;when precipitates transform from D022 singe phase to two phases mixture of D022 and L12 with enhanced Al:V ratio,the amount of VNi has no evident response to the secondary L12 phase,while NiV exhibits a definitely contrary variation tendency:NiV rises without L12 structure precipitating from matrix but declines with it;temporal evolution characteristic and temperature dependent antisite defect VNi,NiV are also studied in this paper:The concentrations of the both defects decline from high antistructure state to equilibrium level with elapsed time but rise with elevated temperature;the ternary alloying element aluminium atom occupies both α and β sublattices of D022 structure with a strong site preference of substituting α site.展开更多
Benefited from its high process feasibility and controllable costs,binary-metal layered structured LiNi_(0.8)Mn_(0.2)O_(2)(NM)can effectively alleviate the cobalt supply crisis under the surge of global electric vehic...Benefited from its high process feasibility and controllable costs,binary-metal layered structured LiNi_(0.8)Mn_(0.2)O_(2)(NM)can effectively alleviate the cobalt supply crisis under the surge of global electric vehicles(EVs)sales,which is considered as the most promising nextgeneration cathode material for lithium-ion batteries(LIBs).However,the lack of deep understanding on the failure mechanism of NM has seriously hindered its application,especially under the harsh condition of high-voltage without sacrifices of reversible capacity.Herein,singlecrystal LiNi_(0.8)Mn_(0.2)O_(2) is selected and compared with traditional LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2)(NCM),mainly focusing on the failure mechanism of Cofree cathode and illuminating the significant effect of Co element on the Li/Ni antisite defect and dynamic characteristic.Specifically,the presence of high Li/Ni antisite defect in NM cathode easily results in the extremely dramatic H2/H3 phase transition,which exacerbates the distortion of the lattice,mechanical strain changes and exhibits poor electrochemical performance,especially under the high cutoff voltage.Furthermore,the reaction kinetic of NM is impaired due to the absence of Co element,especially at the single-crystal architecture.Whereas,the negative influence of Li/Ni antisite defect is controllable at low current densities,owing to the attenuated polarization.Notably,Co-free NM can exhibit better safety performance than that of NCM cathode.These findings are beneficial for understanding the fundamental reaction mechanism of single-crystal Ni-rich Co-free cathode materials,providing new insights and great encouragements to design and develop the next generation of LIBs with low-cost and high-safety performances.展开更多
We describe a novel mechanism for the synthesis of a stable high-entropy alloy powder from an otherwise immiscible Mg-Ti rich metallic mixture by employing high-energy mechanical milling.The presented methodology expe...We describe a novel mechanism for the synthesis of a stable high-entropy alloy powder from an otherwise immiscible Mg-Ti rich metallic mixture by employing high-energy mechanical milling.The presented methodology expedites the synthesis of amorphous alloy powder by strategically injecting entropic disorder through the inclusion of multi-principal elements in the alloy composition.Predictions from first principles and materials theory corroborate the results from microscopic characterizations that reveal a transition of the amorphous phase from a precursor intermetallic structure.This transformation,characterized by the emergence of antisite disorder,lattice expansion,and the presence of nanograin boundaries,signifies a departure from the precursor intermetallic structure.Additionally,this phase transformation is accelerated by the presence of multiple principal elements that induce severe lattice distortion and a higher configurational entropy.The atomic size mismatch of the dissimilar elements present in the alloy produces a stable amorphous phase that resists reverting to an ordered lattice even on annealing.展开更多
Combining the first-principles calculations and structural enumeration with recognition,the delithiation process of LiNiO_(2)is investigated,where various supercell shapes are considered in order to obtain the formati...Combining the first-principles calculations and structural enumeration with recognition,the delithiation process of LiNiO_(2)is investigated,where various supercell shapes are considered in order to obtain the formation energy of Li_(x)NiO_(2).Meanwhile,the voltage profile is simulated and the ordered phases of lithium vacancies corresponding to concentrations of 1/4,2/5,3/7,1/2,2/3,3/4,5/6,and 6/7 are predicted.To understand the capacity decay in the experiment during the charge/discharge cycles,deoxygenation and Li/Ni antisite defects are calculated,revealing that the chains of oxygen vacancies will be energetically preferrable.It can be inferred that in the absence of oxygen atom in high delithiate state,the diffusion of Ni atoms is facilitated and the formation of Li/Ni antisite is induced.展开更多
We investigate the evolution of magnetic properties as well as the content and distribution of Mn for Mn(Sb_(1-x)Bi_(x))_(2)Te_(4) single crystals grown by large-temperature-gradient chemical vapor transport method.It...We investigate the evolution of magnetic properties as well as the content and distribution of Mn for Mn(Sb_(1-x)Bi_(x))_(2)Te_(4) single crystals grown by large-temperature-gradient chemical vapor transport method.It is found that the ferromagnetic MnSb_(2)Te_(4) changes to antiferromagnetism with Bi doping when x≥0.25.Further analysis implies that the occupations of Mn ions at Sb/Bi site Mn_(Sb/Bi) and Mn site Mn_(Mn) have a strong influence on the magnetic ground states of these systems.With the decrease of Mn_(Mn) increase of Mn_(Sb/Bi),the system will favor the ferromagnetic ground state.In addition,the rapid decrease of T_(C/N) with increasing Bi content when x ≤0.25 and the insensitivity of T_(N) to x when x> 0.25 suggest that the main magnetic interaction may change from the Ruderman-Kittel-Kasuya-Yosida type at low Bi doping region to the van-Vleck type in high Bi doped samples.展开更多
Based on the microscopic phase-field model, the correlation between site occupation evolution of alloying elements in Ni3V-DO22 phase and growth of Ni3Al-L12 phase was studied during the phase transformation of Ni75Al...Based on the microscopic phase-field model, the correlation between site occupation evolution of alloying elements in Ni3V-DO22 phase and growth of Ni3Al-L12 phase was studied during the phase transformation of Ni75Al4.2V20.8. The results demonstrate that the growth of L12 phase can be divided into two stages： at the early stage, the composition of alloying elements in DO22 phase almost remains unchanged; at the late stage, the compositions of Ni and Al decrease while V increases in DO22 phase. Part of alloying elements for L12 phase growth are supplied from the site occupation evolution of alloying elements on three kinds of sublattices in DO22 phase. Ni is mainly supplied from V sublattice, and part of Al is supplied from NiⅠ and V sites at the centre of DO22 phase. The excessive V from the decreasing DO22 phase migrates into the centre of DO22 phase and mainly occupies V and NiII sites. It is the site occupation evolution of antisite atoms and ternary additions in DO22 phase that controls the growth rate of L12 phase at the late stage.展开更多
Correlation between site occupation evolution of alloying elements in L12 phase and growth of DO22 phase in Ni75Al7.5V17.5 was studied using microscopic phase field model. The results demonstrate that the growing proc...Correlation between site occupation evolution of alloying elements in L12 phase and growth of DO22 phase in Ni75Al7.5V17.5 was studied using microscopic phase field model. The results demonstrate that the growing process of DO22 phase can be divided into two stages. At the early stage, composition in the centre part of L12 phase almost remains unchanged, and the nucleation and growth of DO22 phase is controlled by the decrease of interface between L12 phases. At the late stage, part of V for growth of DO22 phase is supplied from the centre part of L12 phase and mainly comes from Al sublattice, the excess Ni spared from the decreasing L12 phase migrates into the centre part of L12 phase and occupies the Ni sublattices exclusively, while the excess Al mainly occupies the Al sublattice. At the late stage, the growth of DO22 phase is controlled by the evolution of antisite atoms and ternary additions in the centre part of L12 phase.展开更多
Magnesium aluminate spinel(MgAl2O4)is widely used in steel metallurgy industry.Thermal conductivity at high temperature signifcantly infuences the cooling process of blast furnace and the heat preservation of steel co...Magnesium aluminate spinel(MgAl2O4)is widely used in steel metallurgy industry.Thermal conductivity at high temperature signifcantly infuences the cooling process of blast furnace and the heat preservation of steel converter.The efect of external(temperature)and internal(antisite defect and grain boundary)factors on the thermal conductivity of MgAl2O4 was studied with non-equilibrium molecular dynamics.The main factors afecting the thermal conductivity of MgAl2O4 were summarized.In the temperature range of 100-2000 K,the results showed that the thermal conductivity of MgAl2O4 changed from 11.54 to 4.95 W/(m K)with the increase in temperature and was relatively stable at the temperature above 1000 K.The thermal conductivity of MgAl2O4 declined frst and then rose with the increase in the antisite defects,and the minimum value was 6.95 W/(m K)at the inversion parameter i=0.35.In addition,grain boundaries reduced the thermal conductivity of MgAl2O4 by 20%-30%at temperature below 1000 K comparing with the non-grain boundary system.The grain boundary rotation angle at temperature above 1000 K had less efect on the thermal conductivity than that below 1000 K.Present simulation scheme for thermal conductivity of MgAl2O4 can also be applied to the study of other nonmetallic ceramics.展开更多
The nonstoichiometric β-SIC powders were synthesized via combustion reaction of Si and C system in a 0.1 MPa nitrogen atmosphere, using Teflon as the chemical activator. The prepared powders were invistigated by XRD ...The nonstoichiometric β-SIC powders were synthesized via combustion reaction of Si and C system in a 0.1 MPa nitrogen atmosphere, using Teflon as the chemical activator. The prepared powders were invistigated by XRD and Raman spectra. The results indicates that the cell parameters of all the prepared β-SIC powder are smaller than the standard value of β-SIC because of generation of CSi defects. The complex permittivity of prepared products was carried out in the frequency range of 8.2-12.4 GHz. It shows that the dielectric property of prepared β-SiC powder decrease with increasing PTFE content. The effect of CSi defects on dielectric property of β-SiC powder has been discussed.展开更多
Equilibrium equation of point defects in Ll_2 type intermetallic compounds was established to calculate the relations of the concentration of antisite defects and vacancies and bulk composi- tion in Ni_3Al.The examina...Equilibrium equation of point defects in Ll_2 type intermetallic compounds was established to calculate the relations of the concentration of antisite defects and vacancies and bulk composi- tion in Ni_3Al.The examination of temperature effects on the point defects cleared up the mis. understanding of the properties of the“constitutional point defects”in Ni_3Al.展开更多
Strongly ordered B2 compounds exist in many alloy systems. This paper presented an overview of their mechanical properties, which depend strongly on the concentrations of constitutional defects, that is, on the consti...Strongly ordered B2 compounds exist in many alloy systems. This paper presented an overview of their mechanical properties, which depend strongly on the concentrations of constitutional defects, that is, on the constitutional vacancies and antisite atoms, and, hence, on composition.展开更多
基金Project supported by the National Key R&D Program of China(Grant Nos.2022YFA1403800 and 2023YFA1406500)the National Natural Science Foundation of China(Grant No.12274459)。
文摘Intrinsic magnetic topological insulators have been reported to exhibit novel physical phenomena such as the quantum anomalous Hall effect and axion insulator states,demonstrating potential for applications in spintronics and topological quantum computing.Here we perform low-temperature scanning tunneling microscopy(STM)investigations of the antiferromagnetic ground state of MnSb_(2)Te_(4),a predicted magnetic topological insulator isostructural with MnBi_(2)Te_(4).We visualize the hexagonal Te-terminated surface of MnSb_(2)Te_(4)and identify two distinct defects originating from different antisite substitutions.Notably,we identify an in-gap state above the Fermi energy where the tunneling spectrum exhibits a negative differential conductance behavior.This electronic state can be modulated by external electric and magnetic fields,suggesting effective pathways for electronic state manipulation.Spin-resolved STM measurements further reveal additional magnetic resonance peaks associated with Mn antisite defects.Our results provide novel insights into the investigation of magnetic topological insulators and demonstrate a promising approach to modulate the localized electronic states.
文摘A simple modified analytic EAM model for bcc Fe and fcc Al was used to calculate the lattice constant and elastic constants of B2 FeAl and DO3 Fe3Al alloys. The formation energies of vacancy and antisite were also calculated. The present calculations are in agreement with the experimental data and the theoretical results obtained by other authors.
基金Project(11264024)supported by the National Natural Science Foundation of ChinaProjects(2015MS0102,2015MS0524)supported by Natural Science Foundation of Inner Mongolia,China
文摘From the UV?Vis absorption spectra,the FT-IR absorption spectra and the Raman spectra,it is deduced that Co ionsprimarily occupy the tetrahedral(A)site,with a minor number of them entering into the octahedral(B)site in the Ni1?xCoxCr2O4compounds.The origin of the position disorder of the Co ions is consistent with the similar ionic radii of the Co ion(0.65?)and theCr ion(0.62?)at B site.The FT-IR peak at about510cm?1shifts towards high frequency side with the increasing cobalt content.Itis resulted from the reduction of the cation?oxygen distance in the octahedron by the replacement of the Ni2+with the Co2+ions.Themagnetic measurement shows that Curie temperatures(TC)are75and90K for the compounds with x=0.2and0.8,respectively.
基金supported by National Natural Science Foundation of China (Nos. 21905229, 22071195 and 21805227)China Postdoctoral Science Foundation (No. 2020M683557)+2 种基金Fundamental Research Funds for the Central Universities (No. 3102017jc01001)the postgraduate research scholarship at Queensland University of Technology (QUT-PRA scholarship)the Youth Innovation Team of Shaanxi Universities
文摘Developing transition metal oxides(TMOs)with high energy,power,and long cycle lifetime for elec-tric energy storage devices remains a critical challenge to date.Herein,we demonstrate a facile method that enables in-situ transformation of nickel cobalt oxide nanowire arrays(NiCoO NWA)into hierarchical nanowire-nanosheet arrays(ac-NiCoO NWSA)for enhanced energy storage properties.More specifically,the method leads to formation of atomically thin nanosheets(only 2.0 nm)and creates abundant an-tisite defects and oxygen vacancies.Owing to these merits,the as-prepared ac-NiCoO NWSA electrode exhibits over five-fold higher specific capacity,superior rate capability(up to 100 A/g),and excellent cy-cling stability of 10,000 cycles at 50 A/g in alkaline electrolyte compared to pristine NiCoO NWA.Density functional theory(DFT)simulations elucidate the electrochemical activity enhancement mechanism of the TMOs.Moreover,our method triggers similar structural reconstruction phenomenon on other TMOs including ZnCo-,CoMn-and ZnNiCo-oxides,proving the universality of the method.Our findings provide a general method towards simultaneously manipulating the micro-morphologies and defects of TMOs for advanced energy storage devices.
基金supported by the National Key Basic Research Program of China(Grant No.2011CB921801)the National Natural Science Foundation of China(Grant Nos.11074293 and 51021061)
文摘The ferromagnetic semiconductor La2NiMnO6 （LNMO） has recently received much attention due to its high Curie temperature （Tc 280 K）, which is close to room temperature. We prepared single-phase LNMO polycrystaUine samples and investigated the temperature- and field-dependent magnetic behaviors of bulk LNMO. Between Tc and T＊ = 300 K, we observed upward and downward deviations from the Curie-Weiss law for high and low magnetic fields, respectively. From the electron spin resonance results, we can exclude the existence of the Griffiths phase. On the contrary, our results indicate that the abnormal magnetic behaviors might be induced by antisite phase boundaries with antiferromagnetic interaction.
基金supported by Grant-in-Aid for JSPS Fellows(no.20J11073)from the Japan Society for the Promotion of Science and by the Tsinghua-Tohoku Collaborative Research Fund from Tsinghua University and Tohoku Universitysupported by the Grant-in-Aid for Scientific Research(B)(nos.20H01841,22H02161)from the Japan Society for the Promotion of Science.
文摘A half-metallic full-Heusler Mn_(2)VAl alloy is a potential p-type thermoelectric material that can directly generate electricity from waste heat via the Seebeck effect.For practical use,the Seebeck coefficient S of Mn_(2)VAl should be increased while maintaining a high electrical conductivity s from its half-metallic character.Herein,we achieved this objective through antisite defect engineering.Theoretically,it was predicted that the S was maximized by regulating partial density of states of majority-spin sp-electrons through the control of the fraction of antisite defect,f_(AD),between V and Al atoms in Mn_(2)VAl.Experi-mentally,a significant increase in S and a slight decrease in s were observed for an Mn_(2)VAl sample with an optimal fAD=33%,enhancing the thermoelectric power factor PF by 2.7 times from an Mn_(2)VAl sample with fAD=14%.Furthermore,we combined the antisite defect engineering with a partial substitution method.An Mn_(2)V(Al_(0.96)Si_(0.04))sample with fAD=33%exhibited the highest PF=4.5×10^(-4)W·m^(-1)·K^(-2)at 767 K among the samples.The maximum dimensionless figure-of-merit zT of the Mn_(2)V(Al_(0.96)Si_(0.04))sample with f_(AD)=33%was measured to be 3.4×10^(-2)at 767 K,which is the highest among the p-type half-metallic full-Heusler alloys.
基金supported by the Science,Technology,Innovation Commission of Shenzhen Municipality(GJHZ20220913143204008)Postdoctoral Research Project Funding in Shaanxi Province.
文摘The rapid advancement of metal halide perovskites can be attributed to their exceptional optoelectronic properties and facile solution processing technique.Noteworthy strides have been achieved in the realm of perovskite solar cells(PSCs),with a certified power conversion efficiency(PCE)escalating to 26.7%over the course of a decade,positioning them as promising contenders for next-generation photovoltaic technologies[1].However,the formation of crystal defects,including anion/cation vacancies,Pb–I antisite defects,and uncoordinated Pb^(2+),along the surface and grain boundaries(GBs)of perovskite layers during the solution processing stage poses a significant challenge,compromising the photoelectric performance and stability of PSCs.
基金financially supported by the National Natural Science Foundation of China (Grant Nos.50875217,10902086,and 50941020)the Doctorate Foundation of Northwestern Polytechnical University of China (Grant No.CX200806)the Natural Science Foundation of Shaanxi Province (Grant Nos.SJ08-ZT05 and SJ08-B14)
文摘The temporal evolution feature of a microscopic phase field model is utilized to study the antisite defects of L1 2-Ni 3 Al;this is quite different from other physicist’ interests.There are mainly two points in brief.Firstly,antisite defects Ni Al and Al Ni ,which are caused by the deviation from the stoichiometric Ni 3 Al,coexist in the Ni 3 Al phase.The surplus Ni atom in the Ni-rich side is prone to substitute Al thus producing the antisite defect Ni Al that maintains the stability of the L1 2 structure.In other case,the surplus Al atom in the Al-rich side is accommodated by a Ni sublattice consequently giving rise to antisite defect Al Ni .The calculated equilibrium occupancy probability of Ni Al is much higher than that of Al Ni .This point is generally in line with other theoretical and experimental works.Additionally,both Ni Al and Al Ni have a strong negative correlation to time step during the disorder-order transformation.Since the initial value of Ni Al and Al Ni on each site of the matrix is right at the concentration that we set,we can observe the decrease process of Ni Al and Al Ni from the initial disordered high anti-structure state to their respective equilibrium state,i.e.to the result of the ordering process further coarsening.
基金supported by the National Key Research and Development Program of China (Grant No. 2019YFA0705700)National Natural Science Foundation of China (Grant No. 11704019)+1 种基金the Hundreds of Talents Program of Sun Yat-sen Universitythe Fundamental Research Funds for the Central Universities。
文摘As an ion conductor, the Al-doped Li1+xAlxGe2-x(PO4)3(LAGP) demonstrates the superionic Li diffusion behavior, however,without the convinced verifications. In this context, the density functional theory(DFT) calculations are employed to clarify the structural origin of the fast Li ion migration kinetics in LAGP solid electrolytes. The calculated results show that doping of Al leads to an emerging high-energy 36 f Li site, which plays an important role in promoting the Li diffusion and can largely lower the Li ion diffusion energy barrier. Moreover, the Li/Al antisite defect is investigated firstly, with which the Li ions are excited to occupy a relatively high energy site in LAGP. The obvious local structural distortion by Li/Al antisite results in the coordination change upon Li diffusion(lattice field distortion), which facilitates the Li diffusion significantly and is probably the main reason to account for the superionic diffusion phenomenon. Therefore, the occupation of Li at high-energy sites should be an effective method to establish the fast Li diffusion, which implies a rewarding avenue to build better Li-ion batteries.
基金Supported by the National Natural Science Foundation of China (Grant Nos. 50671084 and 50875217)the Doctorate Foundation of Northwestern Polytechnical University of China (Grant No. CX200806)+1 种基金the China Postdoctoral Science Founda-tion Funded Project (Grant No. 20070420218)the Natural Science Foundation of Shaanxi Province of China
文摘Microscopic phase field simulation is performed to study antisite defect type and temporal evolution characteristic of D022-Ni3V structure in Ni75AlxV25-x ternary system.The result demonstrates that two types of antisite defect VNi and NiV coexist in D022 structure;however,the amount of NiV is far greater than VNi;when precipitates transform from D022 singe phase to two phases mixture of D022 and L12 with enhanced Al:V ratio,the amount of VNi has no evident response to the secondary L12 phase,while NiV exhibits a definitely contrary variation tendency:NiV rises without L12 structure precipitating from matrix but declines with it;temporal evolution characteristic and temperature dependent antisite defect VNi,NiV are also studied in this paper:The concentrations of the both defects decline from high antistructure state to equilibrium level with elapsed time but rise with elevated temperature;the ternary alloying element aluminium atom occupies both α and β sublattices of D022 structure with a strong site preference of substituting α site.
基金the National Natural Science Foundation of China(52070194,52073309,51902347,51908555)Natural Science Foundation of Hunan Province(2022JJ20069,2020JJ5741).
文摘Benefited from its high process feasibility and controllable costs,binary-metal layered structured LiNi_(0.8)Mn_(0.2)O_(2)(NM)can effectively alleviate the cobalt supply crisis under the surge of global electric vehicles(EVs)sales,which is considered as the most promising nextgeneration cathode material for lithium-ion batteries(LIBs).However,the lack of deep understanding on the failure mechanism of NM has seriously hindered its application,especially under the harsh condition of high-voltage without sacrifices of reversible capacity.Herein,singlecrystal LiNi_(0.8)Mn_(0.2)O_(2) is selected and compared with traditional LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2)(NCM),mainly focusing on the failure mechanism of Cofree cathode and illuminating the significant effect of Co element on the Li/Ni antisite defect and dynamic characteristic.Specifically,the presence of high Li/Ni antisite defect in NM cathode easily results in the extremely dramatic H2/H3 phase transition,which exacerbates the distortion of the lattice,mechanical strain changes and exhibits poor electrochemical performance,especially under the high cutoff voltage.Furthermore,the reaction kinetic of NM is impaired due to the absence of Co element,especially at the single-crystal architecture.Whereas,the negative influence of Li/Ni antisite defect is controllable at low current densities,owing to the attenuated polarization.Notably,Co-free NM can exhibit better safety performance than that of NCM cathode.These findings are beneficial for understanding the fundamental reaction mechanism of single-crystal Ni-rich Co-free cathode materials,providing new insights and great encouragements to design and develop the next generation of LIBs with low-cost and high-safety performances.
基金supported in part by the National Science Foundation(NSF)award#CMMI-1944040。
文摘We describe a novel mechanism for the synthesis of a stable high-entropy alloy powder from an otherwise immiscible Mg-Ti rich metallic mixture by employing high-energy mechanical milling.The presented methodology expedites the synthesis of amorphous alloy powder by strategically injecting entropic disorder through the inclusion of multi-principal elements in the alloy composition.Predictions from first principles and materials theory corroborate the results from microscopic characterizations that reveal a transition of the amorphous phase from a precursor intermetallic structure.This transformation,characterized by the emergence of antisite disorder,lattice expansion,and the presence of nanograin boundaries,signifies a departure from the precursor intermetallic structure.Additionally,this phase transformation is accelerated by the presence of multiple principal elements that induce severe lattice distortion and a higher configurational entropy.The atomic size mismatch of the dissimilar elements present in the alloy produces a stable amorphous phase that resists reverting to an ordered lattice even on annealing.
基金Project supported by the Science Fund of the Guangdong Major Project of Basic and Applied Basic Research,China(Grant No.2019B030302011)the Fund of the Science and Technology Program of Guangzhou,China(Grant No.202201010090)。
文摘Combining the first-principles calculations and structural enumeration with recognition,the delithiation process of LiNiO_(2)is investigated,where various supercell shapes are considered in order to obtain the formation energy of Li_(x)NiO_(2).Meanwhile,the voltage profile is simulated and the ordered phases of lithium vacancies corresponding to concentrations of 1/4,2/5,3/7,1/2,2/3,3/4,5/6,and 6/7 are predicted.To understand the capacity decay in the experiment during the charge/discharge cycles,deoxygenation and Li/Ni antisite defects are calculated,revealing that the chains of oxygen vacancies will be energetically preferrable.It can be inferred that in the absence of oxygen atom in high delithiate state,the diffusion of Ni atoms is facilitated and the formation of Li/Ni antisite is induced.
基金Project supported by the Beijing Natural Science Foundation (Grant No. Z200005)the National Key R&D Program of China (Grant Nos. 2022YFA1403800 and 2023YFA1406500)+1 种基金the National Natural Science Foundation of China (Grant No. 12274459)Collaborative Research Project of Laboratory for Materials and Structures, Institute of Innovative Research, Tokyo Institute of Technology。
文摘We investigate the evolution of magnetic properties as well as the content and distribution of Mn for Mn(Sb_(1-x)Bi_(x))_(2)Te_(4) single crystals grown by large-temperature-gradient chemical vapor transport method.It is found that the ferromagnetic MnSb_(2)Te_(4) changes to antiferromagnetism with Bi doping when x≥0.25.Further analysis implies that the occupations of Mn ions at Sb/Bi site Mn_(Sb/Bi) and Mn site Mn_(Mn) have a strong influence on the magnetic ground states of these systems.With the decrease of Mn_(Mn) increase of Mn_(Sb/Bi),the system will favor the ferromagnetic ground state.In addition,the rapid decrease of T_(C/N) with increasing Bi content when x ≤0.25 and the insensitivity of T_(N) to x when x> 0.25 suggest that the main magnetic interaction may change from the Ruderman-Kittel-Kasuya-Yosida type at low Bi doping region to the van-Vleck type in high Bi doped samples.
基金Projects(51174168,51274167)supported by the National Natural Science Foundation of ChinaProject(2013M532082)supported by Postdoctoral Science Foundation of ChinaProjects(13R21421700,13R21421800)supported by the Postdoctoral Science Foundation of Shanghai,China
文摘Based on the microscopic phase-field model, the correlation between site occupation evolution of alloying elements in Ni3V-DO22 phase and growth of Ni3Al-L12 phase was studied during the phase transformation of Ni75Al4.2V20.8. The results demonstrate that the growth of L12 phase can be divided into two stages： at the early stage, the composition of alloying elements in DO22 phase almost remains unchanged; at the late stage, the compositions of Ni and Al decrease while V increases in DO22 phase. Part of alloying elements for L12 phase growth are supplied from the site occupation evolution of alloying elements on three kinds of sublattices in DO22 phase. Ni is mainly supplied from V sublattice, and part of Al is supplied from NiⅠ and V sites at the centre of DO22 phase. The excessive V from the decreasing DO22 phase migrates into the centre of DO22 phase and mainly occupies V and NiII sites. It is the site occupation evolution of antisite atoms and ternary additions in DO22 phase that controls the growth rate of L12 phase at the late stage.
基金Projects (50941020, 10902086, 50875217, 20903075) supported by the National Natural Science Foundation of ChinaProjects (SJ08-ZT05, SJ08-B14) supported by the Natural Science Foundation of Shaanxi Province, China
文摘Correlation between site occupation evolution of alloying elements in L12 phase and growth of DO22 phase in Ni75Al7.5V17.5 was studied using microscopic phase field model. The results demonstrate that the growing process of DO22 phase can be divided into two stages. At the early stage, composition in the centre part of L12 phase almost remains unchanged, and the nucleation and growth of DO22 phase is controlled by the decrease of interface between L12 phases. At the late stage, part of V for growth of DO22 phase is supplied from the centre part of L12 phase and mainly comes from Al sublattice, the excess Ni spared from the decreasing L12 phase migrates into the centre part of L12 phase and occupies the Ni sublattices exclusively, while the excess Al mainly occupies the Al sublattice. At the late stage, the growth of DO22 phase is controlled by the evolution of antisite atoms and ternary additions in the centre part of L12 phase.
基金This work is sponsored by the National Natural Science Foundation of China(Grant Nos.21233010 and 51474047).
文摘Magnesium aluminate spinel(MgAl2O4)is widely used in steel metallurgy industry.Thermal conductivity at high temperature signifcantly infuences the cooling process of blast furnace and the heat preservation of steel converter.The efect of external(temperature)and internal(antisite defect and grain boundary)factors on the thermal conductivity of MgAl2O4 was studied with non-equilibrium molecular dynamics.The main factors afecting the thermal conductivity of MgAl2O4 were summarized.In the temperature range of 100-2000 K,the results showed that the thermal conductivity of MgAl2O4 changed from 11.54 to 4.95 W/(m K)with the increase in temperature and was relatively stable at the temperature above 1000 K.The thermal conductivity of MgAl2O4 declined frst and then rose with the increase in the antisite defects,and the minimum value was 6.95 W/(m K)at the inversion parameter i=0.35.In addition,grain boundaries reduced the thermal conductivity of MgAl2O4 by 20%-30%at temperature below 1000 K comparing with the non-grain boundary system.The grain boundary rotation angle at temperature above 1000 K had less efect on the thermal conductivity than that below 1000 K.Present simulation scheme for thermal conductivity of MgAl2O4 can also be applied to the study of other nonmetallic ceramics.
基金supported by the National Natural Science Foundation of China under grant No. 50572090the fund of the Slate Key Laboratory of Solidification Processing in NWPU, No. KP200901
文摘The nonstoichiometric β-SIC powders were synthesized via combustion reaction of Si and C system in a 0.1 MPa nitrogen atmosphere, using Teflon as the chemical activator. The prepared powders were invistigated by XRD and Raman spectra. The results indicates that the cell parameters of all the prepared β-SIC powder are smaller than the standard value of β-SIC because of generation of CSi defects. The complex permittivity of prepared products was carried out in the frequency range of 8.2-12.4 GHz. It shows that the dielectric property of prepared β-SiC powder decrease with increasing PTFE content. The effect of CSi defects on dielectric property of β-SiC powder has been discussed.
文摘Equilibrium equation of point defects in Ll_2 type intermetallic compounds was established to calculate the relations of the concentration of antisite defects and vacancies and bulk composi- tion in Ni_3Al.The examination of temperature effects on the point defects cleared up the mis. understanding of the properties of the“constitutional point defects”in Ni_3Al.
文摘Strongly ordered B2 compounds exist in many alloy systems. This paper presented an overview of their mechanical properties, which depend strongly on the concentrations of constitutional defects, that is, on the constitutional vacancies and antisite atoms, and, hence, on composition.
