Controlled disordering of substitutional and interstitial site occupation at high pressure can lead to important changes in the structural and physical properties of iron–nickel nitrides.Despite important progress th...Controlled disordering of substitutional and interstitial site occupation at high pressure can lead to important changes in the structural and physical properties of iron–nickel nitrides.Despite important progress that has been achieved,structural characterization of ternary Fe–Ni–N compounds remains an open problem owing to the considerable technical challenges faced by current synthetic and structural approaches for fabrication of bulk ternary nitrides.Here,iron–nickel nitride samples are synthesized as spherical-like bulk materials through a novel highpressure solid-state metathesis reaction.By employing a wide array of techniques,namely,neutron powder diffraction,Rietveld refinement methods combined with synchrotron radiation angle-dispersive x-ray diffraction,scanning electron microscopy/energy dispersive x-ray spectroscopy,and transmission electron microscopy,we demonstrate that high-temperature and high-pressure confinement conditions favor substitutional and interstitial site disordering in ternary iron–nickel nitrides.In addition,the effects of interstitial nitrogen atoms and disorderly substituted nickel atoms on the elastic properties of the materials are discussed.展开更多
Mn-based intermetallic compounds have attracted much attention due to their fascinating structural and physical properties,especially their interesting hard magnetic properties.In this paper,we have summarized the mag...Mn-based intermetallic compounds have attracted much attention due to their fascinating structural and physical properties,especially their interesting hard magnetic properties.In this paper,we have summarized the magnetic and structural properties of Mn-based intermetallic compounds(Mn X,where X=Al,Bi,and Ga).Various methods for synthesizing single phases of MnAl,MnBi,and Mnx Ga were developed in our lab.A very high saturation magnetization of 125 emu/g,coercivity of 5 kOe,and maximum energy product(BH)_(max)of 3.1 MG·Oe were achieved at room temperature for the pureτ-Mn–Al magnetic phase without carbon doping and the extrusion process.Low temperature phase(LTP)MnBi with a purity above 95 wt.%can be synthesized.An abnormal temperature coefficient of the coercivity was observed for the LTP MnBi magnet.Its coercivity increased with temperature from 100 K to 540 K,reached a maximum of 2.5 T at about540 K,and then decreased slowly to 1.8 T at 610 K.The positive temperature coefficient of the coercivity is related to the evolution of the structure and magnetocrystalline anisotropy field of the LTP MnBi phase with temperature.The LTP MnBi bonded magnets show maximum energy products(BH)_(max)of 8.9 MG·Oe(70 kJ/m^(3))and 5.0 MG·Oe(40 k J/m^(3))at room temperature and 400 K,respectively.Ferrimagnetic Mn_(x)Ga phases with L10 structures(x〈2.0)and D0_(22)structures(x〉2.0)were obtained.All of the above structures can be described by a D0_(22)supercell model in which 2 a-Ga and 2 b-Mn are simultaneously substituted.The tetragonal D0_(22)phases of the Mn_(x)Ga show high coercivities ranging from 7.2 kOe for low Mn content x=1.8 to 18.2 kOe for high Mn content x=3 at room temperature.The Mn_(1.2)Ga sample exhibits a room temperature magnetization value of 80 emu/g.The hard magnetic properties of coercivityiH_(c)=3.5 kOe,remanence M_(r)=43.6 emu/g,and(BH)_(max)=2.5 MG·Oe were obtained at room temperature.Based on the above studies,we believe that Mn-based magnetic materials could be promising candidates for rare earth free permanent magnets exhibiting a high Curie temperature,high magnetocrystalline anisotropy,and very high coercivity.展开更多
A series of deuterated ammonium dihydrogen phosphate(DADP) crystals were grown and their structures were investigated by using powder neutron diffraction method. In the entire composition range, the deuterated level i...A series of deuterated ammonium dihydrogen phosphate(DADP) crystals were grown and their structures were investigated by using powder neutron diffraction method. In the entire composition range, the deuterated level in the crystals is lower compared with the aqueous growth solution. The deuterium segregation coefficient in the crystals decreases with increasing deuterium content of the solution. The deuterium content in the NH_4^+ group is higher than that in H_2PO_4^- group.In addition, the variations of lattice parameters are shown here.展开更多
In the context of the gradual popularity of electric vehicles(EVs),the development of lithium battery systems with high energy density and power density is regarded as the foremost way to improve the range of EVs.LiNi...In the context of the gradual popularity of electric vehicles(EVs),the development of lithium battery systems with high energy density and power density is regarded as the foremost way to improve the range of EVs.LiNi_(1-x-y)Co_(x)Mn_(y)O_(2)(NCM)cathodes have been the focus of researchers due to their high energy density,excellent power performance,and low-temperature resistance.However,the elaboration of the decay mechanism of NCM cathode based on lithium metal batteries(LMBs)is still being restricted to the primary level.In the past decades,the development and application of advanced in-situ characterization tools have facilitated researchers'understanding of the internal operation mechanism of batteries during charging and discharging.In this minireview,the latest progress of in-situ observation of the NCM cathode by X-ray diffraction(XRD),fourier transform infrared(FT-IR)spectroscopy,Raman spectroscopy,atomic force microscopy(AFM),transmission electron microscope(TEM),optical microscope,and other characterization tools is summarized.The mechanisms of structural degradation,cathode-electrolyte interfaces(CEIs)composition,and dynamic changes of NCM,electrolyte breakdown,and gas production are elaborated.Finally,based on the existing research progress,the opportunities and challenges for future in-situ characterization technology in the study of the mechanism of LMBs are discussed in depth.Therefore,the purpose of this minireview is to summarize recent work that focuses on the outstanding application of in-situ characterization techniques in the mechanistic study of LMBs,and pointing the way to the future development of high energy density and power density LMBs systems.展开更多
Magnetic materials with non-collinear spin orderings provide an outstanding platform to probe spin-tronic phenomena owing to their strong spin-orbit coupling(SOC)and unique Berry phase.It is thus important to obtain a...Magnetic materials with non-collinear spin orderings provide an outstanding platform to probe spin-tronic phenomena owing to their strong spin-orbit coupling(SOC)and unique Berry phase.It is thus important to obtain a non-collinear antiferromagnetic(AFM)phase at room temperature(RT).Signifi-cantly,the discovery of novel materials with nearly zero thermal expansion(ZTE)property near RT is required and pursued for avoiding thermal stress and fracture in spintronic devices.Herein,the doping of Sn(Ge)at the Ag site in the triangular lattice Mn_(3)Ag_(1-x)Sn(Ge)_(x)N compounds increases effectively the Neel point and makes the interesting non-collinearГ^(5g)AFM phase exist above RT.The magnetic phase diagrams withГ^(5g)phase up to 498 K were built by the combined analysis of neutron powder diffraction(NPD),magnetic measurements,electronic transport,and differential scanning calorimetry(DSC).The thermal expansion behaviors of Mn_(3)Ag_(1-x)Sn(Ge)_(x)N were modulated,and the nearly ZTE above RT was achieved in Mn_(3)Ag_(0.5)Ge_(0.5)N withinГ^(5g)AFM ordering.Our findings offer an effective way to tailor the non-collinear AFM ordering and correlated thermal expansion behavior for potential use in the emerging field of thermal stress-free magnetic chip materials.展开更多
The barium ferrite BaTi_(x)Fe_(12−x)O_(19)(x=0.2,0.4,0.6,0.8)(BFTO-x)ceramics doped by Ti4+were synthesized by a modified sol–gel method.The crystal structure and magnetic structure of the samples were determined by ...The barium ferrite BaTi_(x)Fe_(12−x)O_(19)(x=0.2,0.4,0.6,0.8)(BFTO-x)ceramics doped by Ti4+were synthesized by a modified sol–gel method.The crystal structure and magnetic structure of the samples were determined by neutron diffraction,and confirm that the BFTO-x ceramics were high quality single phase with sheet microstructure.With x increasing from 0.2 to 0.8,the saturation magnetization(M_(s))decreases gradually but the change trend of coercivity(H_(c))is complex under the synergy of the changed grain size and the magnetic crystal anisotropy field.Relying on the high valence of Ti^(4+),double resonance peaks are obtained in the curves of the imaginary part of magnetic conductivity(μ′′)and the resonance peaks could move toward the low frequency with the increase of x,which facilitate the samples perform an excellent wideband modulation microwave absorption property.In the x=0.2 sample,the maximum reflection loss(RL)can reach−44.9 dB at the thickness of only 1.8 mm,and the bandwidth could reach 5.28 GHz at 2 mm when RL is less than−10 dB.All the BFTO-x ceramics show excellent frequency modulation ability varying from 18(x=0.8)to 4 GHz(x=0.4),which covers 81%of the investigated frequency in microwave absorption field.This work not only implements the tunable of electromagnetic parameters but also broadens the application of high-performance microwave absorption devices.展开更多
Off-stoichiometry of perovskite structural Bi0.5Na0.5TiO3(BNT)ferroelectrics can give rise to considerable oxide-ion conductivity.The inherent structural characteristics are urgent to be resolved due to its particular...Off-stoichiometry of perovskite structural Bi0.5Na0.5TiO3(BNT)ferroelectrics can give rise to considerable oxide-ion conductivity.The inherent structural characteristics are urgent to be resolved due to its particular sensitivity of the conduction mechanism to the nominal composition and synthesis process.Herein,a thorough study of the temperature-dependent neutron,X-ray diffraction and Raman spectrum is carried out on a series of equivalently substituted A-site deficient non-stoichiometric and pristine BNT.Phase transition and defect association are systemically investigated in these dominated rhombohedral phases at room temperature,associated with well saturated ferroelectric states.Significant structural evolution identified by Rietveld refinements and the origin of the electrical performance are clarified at elevated temperatures,focusing on the subtle distortions of ionic displacements,oxygen octahedral tilts and local chemical environments for oxygen vacancies.The ion migration ability mediated by oxygen vacancies that are not energetically favorable in BNT mainly depends on the external substitutional disorder,and is strongly affected by the dopant concentration.Together with the lone pair substitution concept,superior oxide ionic conductivity is achieved,and an alternative strategy is provided in designing BNT based oxide ion conductors.展开更多
The phase equilibria and thermodynamic properties of the U-Nb system were investigated through experiments and thermodynamic modeling.In the experiments,a series of samples with different content of Nb were prepared b...The phase equilibria and thermodynamic properties of the U-Nb system were investigated through experiments and thermodynamic modeling.In the experiments,a series of samples with different content of Nb were prepared by arc melting.The Nb content covers the entire composition range of the U-Nb binary system.After solidification,the samples were annealed and then analyzed by X-ray diffraction,scanning electron microscopy,energy dispersive X-ray spectroscopy,differential scanning calorimeter and neutron diffraction.The equilibrium phases,including γ1(U-rich bcc),αU,and γ2(U-depleted bcc),were determined in detail from the experimental characterization.The occurrence of the invariant reaction γ1→αU+γ2 was confirmed,and the reaction temperature and composition were accurately identified.Moreover,the experimental findings clarify the dispute between the Dwight and Terekhov theories regarding the phase region(i.e.,whether the phase region is αU+γ1 or βU+γ2).Furthermore,the U-Nb phase diagram was reassessed by incorporating the present experimental data and previously published reliable experimental data from the literature.A set of self-consistent thermodynamic parameters were developed using CALPHAD(Calculation of phase diagrams),and the calculations reasonably agree with the experimental observations.展开更多
基金support by the National Natural Science Foundation of China(Grant Nos.U2030107 and 11774247)the Joint Usage/Research Center PRIUS,Ehime University,Japan.
文摘Controlled disordering of substitutional and interstitial site occupation at high pressure can lead to important changes in the structural and physical properties of iron–nickel nitrides.Despite important progress that has been achieved,structural characterization of ternary Fe–Ni–N compounds remains an open problem owing to the considerable technical challenges faced by current synthetic and structural approaches for fabrication of bulk ternary nitrides.Here,iron–nickel nitride samples are synthesized as spherical-like bulk materials through a novel highpressure solid-state metathesis reaction.By employing a wide array of techniques,namely,neutron powder diffraction,Rietveld refinement methods combined with synchrotron radiation angle-dispersive x-ray diffraction,scanning electron microscopy/energy dispersive x-ray spectroscopy,and transmission electron microscopy,we demonstrate that high-temperature and high-pressure confinement conditions favor substitutional and interstitial site disordering in ternary iron–nickel nitrides.In addition,the effects of interstitial nitrogen atoms and disorderly substituted nickel atoms on the elastic properties of the materials are discussed.
基金Project supported by the National Natural Science Foundation of China(Grant Nos.51731001,11805006,51371009,11504348,and 11675006)National Key Research and Development Program of China(Grant Nos.2016YFB0700901,2017YFA0401502,and 2017YFA0206303)
文摘Mn-based intermetallic compounds have attracted much attention due to their fascinating structural and physical properties,especially their interesting hard magnetic properties.In this paper,we have summarized the magnetic and structural properties of Mn-based intermetallic compounds(Mn X,where X=Al,Bi,and Ga).Various methods for synthesizing single phases of MnAl,MnBi,and Mnx Ga were developed in our lab.A very high saturation magnetization of 125 emu/g,coercivity of 5 kOe,and maximum energy product(BH)_(max)of 3.1 MG·Oe were achieved at room temperature for the pureτ-Mn–Al magnetic phase without carbon doping and the extrusion process.Low temperature phase(LTP)MnBi with a purity above 95 wt.%can be synthesized.An abnormal temperature coefficient of the coercivity was observed for the LTP MnBi magnet.Its coercivity increased with temperature from 100 K to 540 K,reached a maximum of 2.5 T at about540 K,and then decreased slowly to 1.8 T at 610 K.The positive temperature coefficient of the coercivity is related to the evolution of the structure and magnetocrystalline anisotropy field of the LTP MnBi phase with temperature.The LTP MnBi bonded magnets show maximum energy products(BH)_(max)of 8.9 MG·Oe(70 kJ/m^(3))and 5.0 MG·Oe(40 k J/m^(3))at room temperature and 400 K,respectively.Ferrimagnetic Mn_(x)Ga phases with L10 structures(x〈2.0)and D0_(22)structures(x〉2.0)were obtained.All of the above structures can be described by a D0_(22)supercell model in which 2 a-Ga and 2 b-Mn are simultaneously substituted.The tetragonal D0_(22)phases of the Mn_(x)Ga show high coercivities ranging from 7.2 kOe for low Mn content x=1.8 to 18.2 kOe for high Mn content x=3 at room temperature.The Mn_(1.2)Ga sample exhibits a room temperature magnetization value of 80 emu/g.The hard magnetic properties of coercivityiH_(c)=3.5 kOe,remanence M_(r)=43.6 emu/g,and(BH)_(max)=2.5 MG·Oe were obtained at room temperature.Based on the above studies,we believe that Mn-based magnetic materials could be promising candidates for rare earth free permanent magnets exhibiting a high Curie temperature,high magnetocrystalline anisotropy,and very high coercivity.
基金Project supported by the National Natural Science Foundation of China(Grant No.51402173)Shandong Provincial Natural Science Joint Foundation with Universities and Scientific Research Institution,China(Grant No.ZR2017LEM006)+1 种基金the Neutron Physics Laboratory,China Academy of Engineering Physics(Grant No.2014BB07)the Fundamental Research Funds for Central Universities,China(Grant No.FRF-TP-15-099A1)
文摘A series of deuterated ammonium dihydrogen phosphate(DADP) crystals were grown and their structures were investigated by using powder neutron diffraction method. In the entire composition range, the deuterated level in the crystals is lower compared with the aqueous growth solution. The deuterium segregation coefficient in the crystals decreases with increasing deuterium content of the solution. The deuterium content in the NH_4^+ group is higher than that in H_2PO_4^- group.In addition, the variations of lattice parameters are shown here.
基金supports by the National Natural Science Foundation of China(Nos.U20A2072,52072352,and 21875226)the Foundation for the Youth S&T Innovation Team of Sichuan Province(No.2020JDTD0035)Tianfu Rencai Plan.
文摘In the context of the gradual popularity of electric vehicles(EVs),the development of lithium battery systems with high energy density and power density is regarded as the foremost way to improve the range of EVs.LiNi_(1-x-y)Co_(x)Mn_(y)O_(2)(NCM)cathodes have been the focus of researchers due to their high energy density,excellent power performance,and low-temperature resistance.However,the elaboration of the decay mechanism of NCM cathode based on lithium metal batteries(LMBs)is still being restricted to the primary level.In the past decades,the development and application of advanced in-situ characterization tools have facilitated researchers'understanding of the internal operation mechanism of batteries during charging and discharging.In this minireview,the latest progress of in-situ observation of the NCM cathode by X-ray diffraction(XRD),fourier transform infrared(FT-IR)spectroscopy,Raman spectroscopy,atomic force microscopy(AFM),transmission electron microscope(TEM),optical microscope,and other characterization tools is summarized.The mechanisms of structural degradation,cathode-electrolyte interfaces(CEIs)composition,and dynamic changes of NCM,electrolyte breakdown,and gas production are elaborated.Finally,based on the existing research progress,the opportunities and challenges for future in-situ characterization technology in the study of the mechanism of LMBs are discussed in depth.Therefore,the purpose of this minireview is to summarize recent work that focuses on the outstanding application of in-situ characterization techniques in the mechanistic study of LMBs,and pointing the way to the future development of high energy density and power density LMBs systems.
基金supported by the financial support of National Key R&D Program of China(2022YFA1402600)National Natural Science Foundation of China(NSFC)(52272264)+1 种基金Sino-German Mobility Programme Project(M-0273)the Guangdong Basic and Applied Basic Research Foundation(2022A1515140117).
文摘Magnetic materials with non-collinear spin orderings provide an outstanding platform to probe spin-tronic phenomena owing to their strong spin-orbit coupling(SOC)and unique Berry phase.It is thus important to obtain a non-collinear antiferromagnetic(AFM)phase at room temperature(RT).Signifi-cantly,the discovery of novel materials with nearly zero thermal expansion(ZTE)property near RT is required and pursued for avoiding thermal stress and fracture in spintronic devices.Herein,the doping of Sn(Ge)at the Ag site in the triangular lattice Mn_(3)Ag_(1-x)Sn(Ge)_(x)N compounds increases effectively the Neel point and makes the interesting non-collinearГ^(5g)AFM phase exist above RT.The magnetic phase diagrams withГ^(5g)phase up to 498 K were built by the combined analysis of neutron powder diffraction(NPD),magnetic measurements,electronic transport,and differential scanning calorimetry(DSC).The thermal expansion behaviors of Mn_(3)Ag_(1-x)Sn(Ge)_(x)N were modulated,and the nearly ZTE above RT was achieved in Mn_(3)Ag_(0.5)Ge_(0.5)N withinГ^(5g)AFM ordering.Our findings offer an effective way to tailor the non-collinear AFM ordering and correlated thermal expansion behavior for potential use in the emerging field of thermal stress-free magnetic chip materials.
基金This work was supported by the National Natural Science Foundation of China(U2130110 and 51502054).
文摘The barium ferrite BaTi_(x)Fe_(12−x)O_(19)(x=0.2,0.4,0.6,0.8)(BFTO-x)ceramics doped by Ti4+were synthesized by a modified sol–gel method.The crystal structure and magnetic structure of the samples were determined by neutron diffraction,and confirm that the BFTO-x ceramics were high quality single phase with sheet microstructure.With x increasing from 0.2 to 0.8,the saturation magnetization(M_(s))decreases gradually but the change trend of coercivity(H_(c))is complex under the synergy of the changed grain size and the magnetic crystal anisotropy field.Relying on the high valence of Ti^(4+),double resonance peaks are obtained in the curves of the imaginary part of magnetic conductivity(μ′′)and the resonance peaks could move toward the low frequency with the increase of x,which facilitate the samples perform an excellent wideband modulation microwave absorption property.In the x=0.2 sample,the maximum reflection loss(RL)can reach−44.9 dB at the thickness of only 1.8 mm,and the bandwidth could reach 5.28 GHz at 2 mm when RL is less than−10 dB.All the BFTO-x ceramics show excellent frequency modulation ability varying from 18(x=0.8)to 4 GHz(x=0.4),which covers 81%of the investigated frequency in microwave absorption field.This work not only implements the tunable of electromagnetic parameters but also broadens the application of high-performance microwave absorption devices.
基金This work was supported by the National Natural Science Foundation(51702249,51602252,51761135118,U1732117)the China Postdoctoral Science Foundation(2017M613065)+2 种基金the Shaanxi Province Science Foundation(2020JQ-751)the Outstanding Youth Science Fund of XUST(2018YQ2-11)The authors thank Shiyanjia Lab for the XPS measurement.
文摘Off-stoichiometry of perovskite structural Bi0.5Na0.5TiO3(BNT)ferroelectrics can give rise to considerable oxide-ion conductivity.The inherent structural characteristics are urgent to be resolved due to its particular sensitivity of the conduction mechanism to the nominal composition and synthesis process.Herein,a thorough study of the temperature-dependent neutron,X-ray diffraction and Raman spectrum is carried out on a series of equivalently substituted A-site deficient non-stoichiometric and pristine BNT.Phase transition and defect association are systemically investigated in these dominated rhombohedral phases at room temperature,associated with well saturated ferroelectric states.Significant structural evolution identified by Rietveld refinements and the origin of the electrical performance are clarified at elevated temperatures,focusing on the subtle distortions of ionic displacements,oxygen octahedral tilts and local chemical environments for oxygen vacancies.The ion migration ability mediated by oxygen vacancies that are not energetically favorable in BNT mainly depends on the external substitutional disorder,and is strongly affected by the dopant concentration.Together with the lone pair substitution concept,superior oxide ionic conductivity is achieved,and an alternative strategy is provided in designing BNT based oxide ion conductors.
基金This work was financially supported by the Science Challenge Project of China(No.TZ2016004)the National Natural Science Foundation of China(No.51701193)the National Key Research and Development Program(No.2016YFB0700404)。
文摘The phase equilibria and thermodynamic properties of the U-Nb system were investigated through experiments and thermodynamic modeling.In the experiments,a series of samples with different content of Nb were prepared by arc melting.The Nb content covers the entire composition range of the U-Nb binary system.After solidification,the samples were annealed and then analyzed by X-ray diffraction,scanning electron microscopy,energy dispersive X-ray spectroscopy,differential scanning calorimeter and neutron diffraction.The equilibrium phases,including γ1(U-rich bcc),αU,and γ2(U-depleted bcc),were determined in detail from the experimental characterization.The occurrence of the invariant reaction γ1→αU+γ2 was confirmed,and the reaction temperature and composition were accurately identified.Moreover,the experimental findings clarify the dispute between the Dwight and Terekhov theories regarding the phase region(i.e.,whether the phase region is αU+γ1 or βU+γ2).Furthermore,the U-Nb phase diagram was reassessed by incorporating the present experimental data and previously published reliable experimental data from the literature.A set of self-consistent thermodynamic parameters were developed using CALPHAD(Calculation of phase diagrams),and the calculations reasonably agree with the experimental observations.
