P2型层状过渡金属氧化物(P2-Na_(x)TMO_(2))因其优异的循环稳定性和倍率性能,成为钠离子电池正极材料的有力候选者。然而,其在高电压下的不可逆相变和固有低理论容量问题,阻碍了实际应用。本研究工作提出高熵策略与双相结构的协同设计...P2型层状过渡金属氧化物(P2-Na_(x)TMO_(2))因其优异的循环稳定性和倍率性能,成为钠离子电池正极材料的有力候选者。然而,其在高电压下的不可逆相变和固有低理论容量问题,阻碍了实际应用。本研究工作提出高熵策略与双相结构的协同设计来克服这些挑战。通过在P2相高熵基体中引入O3相,构建新型P2/O3双相高熵层状氧化物Na_(0.70)Ni_(0.25)Mn_(0.35)Co_(0.15)Fe_(0.05)Ti_(0.20)O_(2)(简称Na_(0.70)NMCFT)。其中,高熵设计通过构型熵稳定效应有效抑制P2相的不可逆相变,而O3相则通过协同作用弥补容量不足并提升循环稳定性。此外,双相组分之间的相互作用进一步促进P2-O3与P2-P3相变的高度可逆性。Na_(0.70)NMCFT在1C倍率下的初始放电容量为102.08 mAhg^(-1),200次循环后容量保持率达88.15%,表明具有优异的循环稳定性。更重要的是,即使在10C的高倍率下,Na_(0.70)NMCFT仍能提供85.67 mAh g^(-1)的初始放电比容量,并在1000次循环后容量保持率达70%。本工作证实双相高熵设计在提升钠离子电池正极性能中的关键作用,为开发先进钠离子电池正极材料提供了新思路。展开更多
Supercritical fluids play a crucial role in material transport within Earth's deep interior.Investigating the pressure-dependent atomic structures and transport properties of such fluids is essential for understan...Supercritical fluids play a crucial role in material transport within Earth's deep interior.Investigating the pressure-dependent atomic structures and transport properties of such fluids is essential for understanding their petrological,chemical,and geophysical behaviors.In this study,we employed first-principles molecular dynamics simulations to explore the structures,self-diffusion coefficients(D),and viscosities(η)of supercritical NaAlSi_(3)O_(8)-H_(2)O fluids under conditions of 2000 K and 3-10 GPa,with water contents of 30 wt% and 50 wt%.Our calculations indicate that at a water content of 30 wt%,Q^(2) and Q^(3) exhibit a certain degree of positive and negative pressure dependence,respectively,while other Q^(n) species(n represents the number of bridging oxygens connected to Si/Al)show minimal changes.At a water content of 50 wt%,Q^(2) and Q^(0) exhibit a certain degree of positive and negative pressure dependence,respectively,while other Q^(n) species show minimal changes.At both water contents,Si-O-H and molecular water in the system exhibit negative pressure dependence,suggesting that the migration of supercritical fluids from deep to shallow regions is accompanied by the release of water.The self-diffusion coefficients in the supercritical NaAlSi_(3)O_(8)-H_(2)O fluid follow the order D_(Na)≈D_(H)>D_(O)>D_(Al)≈D_(Si),with an overall weak negative pressure dependence.By comparing the viscosities of anhydrous and hydrous silicate melts from previous studies,we found that the addition of water caused a transition from negative to positive pressure dependence of viscosity,corresponding to a structural change from polymerization to depolymerization.Additionally,we calculated the fluid mobility Δp/η of supercritical NaAlSi_(3)O_(8)-H_(2)O fluids and found that their mobility is several orders of magnitude higher than that of basalt melt and is also significantly greater than that of carbonate melt.As supercritical fluids ascend from deeper to shallower regions,their mobility is further enhanced,significantly contributing to the transport of elements from subducting slabs to the overlying mantle wedge.展开更多
A graphite carbon nitride(g-C3N4)modified Bi4O5I2 composite was successfully prepared insitu via the thermal treatment of a g-C3N4/Bi OI precursor at 400°C for 3 hr.The as-prepared g-C3N4/Bi4O5I2 showed high phot...A graphite carbon nitride(g-C3N4)modified Bi4O5I2 composite was successfully prepared insitu via the thermal treatment of a g-C3N4/Bi OI precursor at 400°C for 3 hr.The as-prepared g-C3N4/Bi4O5I2 showed high photocatalytic performance in Methyl Orange(MO)degradation under visible light.The best sample presented a degradation rate of 0.164 min^-1,which is 3.2 and 82 times as high as that of Bi4O5I2 and g-C3N4,respectively.The g-C3N4/Bi4O5I2 was characterized by X-ray powder diffractometer(XRD),scanning electron microscopy(SEM),transmission electron microscopy(TEM),Raman,X-ray photoelectron spectroscopy(XPS),ultraviolet-visible diffuse reflectance spectra(DRS),electrochemical impedance spectroscopy(EIS)and transient photocurrent response in order to explain the enhanced photoactivity.Results indicated that the decoration with a small amount of g-C3N4 influenced the specific surface area only slightly.Nevertheless,the capability for absorbing visible light was improved measurably,which was beneficial to the MO degradation.On top of that,a strong interaction between g-C3N4 and Bi4O5I2 was detected.This interplay promoted the formation of a favorable heterojunction structure and thereby enhanced the charge separation.Thus,the g-C3N4/Bi4O5I2 composite presented greater charge separation efficiency and much better photocatalytic performance than Bi4O5I2.Additionally,g-C3N4/Bi4O5I2 also presented high stability.·O2^- and holes were verified to be the main reactive species.展开更多
Sc^3＋-doped lithium manganese oxides were synthesized by solid-state reaction. The influences of doping element on structure, mean valence of manganese, and electrochemical performances were studied by X-ray diffract...Sc^3＋-doped lithium manganese oxides were synthesized by solid-state reaction. The influences of doping element on structure, mean valence of manganese, and electrochemical performances were studied by X-ray diffraction （XRD）, galvanostatic charge-discharge and cyclic voltammetric tests, and also electrochemical impedance spectroscopy （EIS）. XRD tests showed that doped lithium manganese oxides were pure spinel structure without other phases. Redox titration and visible spectrophotometry tests indicated that the mean valence of manganese in doped lithium manganese oxides was higher than that of pure one. LiSc0.02Mn1.9804 remained 92.9% of the initial specific discharge capacity after 50th cycle at a constant current of 50 m/g, and the reversibility of LiSc0.02Mn1.98O4 was improved in comparison with pure LiMn2O4 at 50 ℃. EIS indicated that film deposition on spinel particles was suppressed because of Sc^3＋ doping, and the charge transfer between the surface film and spinel particles with increasing temperature for Sc^3＋-doped materials became easier as compared with undoped one.展开更多
This study evaluated the mechanical properties and thermal properties of Al-12 vol%B4 C composite at elevated temperature strengthened with in situ Al2 O3 network.The composite was fabricated using powder metallurgy(P...This study evaluated the mechanical properties and thermal properties of Al-12 vol%B4 C composite at elevated temperature strengthened with in situ Al2 O3 network.The composite was fabricated using powder metallurgy(PM)with raw materials of fine atomized aluminum powders,and the associated microstructures were observed.At 350℃,the composite had ultimate tensile strength of UTS=137 MPa,yield strength of YS0.2=118 MPa,and elongation ofε=4%.Besides,the mechanical properties of the composite remained unchanged at 350℃after the long holding periods up to 1000 h.The excellent mechanical properties and thermal stability at 350℃were secured by in situ am-Al2O3 network that strengthened the grain boundaries.The interfacial debonding and brittle cracking of B4 C particles were the main fracture mechanisms of the composite.In addition,the influence of sintering temperature and rolling deformation on the microstructures and mechanical properties was studied.展开更多
文摘P2型层状过渡金属氧化物(P2-Na_(x)TMO_(2))因其优异的循环稳定性和倍率性能,成为钠离子电池正极材料的有力候选者。然而,其在高电压下的不可逆相变和固有低理论容量问题,阻碍了实际应用。本研究工作提出高熵策略与双相结构的协同设计来克服这些挑战。通过在P2相高熵基体中引入O3相,构建新型P2/O3双相高熵层状氧化物Na_(0.70)Ni_(0.25)Mn_(0.35)Co_(0.15)Fe_(0.05)Ti_(0.20)O_(2)(简称Na_(0.70)NMCFT)。其中,高熵设计通过构型熵稳定效应有效抑制P2相的不可逆相变,而O3相则通过协同作用弥补容量不足并提升循环稳定性。此外,双相组分之间的相互作用进一步促进P2-O3与P2-P3相变的高度可逆性。Na_(0.70)NMCFT在1C倍率下的初始放电容量为102.08 mAhg^(-1),200次循环后容量保持率达88.15%,表明具有优异的循环稳定性。更重要的是,即使在10C的高倍率下,Na_(0.70)NMCFT仍能提供85.67 mAh g^(-1)的初始放电比容量,并在1000次循环后容量保持率达70%。本工作证实双相高熵设计在提升钠离子电池正极性能中的关键作用,为开发先进钠离子电池正极材料提供了新思路。
基金funded by National Natural Science Foundation of China(42373033,Yicheng Sun)Fundamental Research Funds for the Central Universities(B240201111,Yicheng Sun)。
文摘Supercritical fluids play a crucial role in material transport within Earth's deep interior.Investigating the pressure-dependent atomic structures and transport properties of such fluids is essential for understanding their petrological,chemical,and geophysical behaviors.In this study,we employed first-principles molecular dynamics simulations to explore the structures,self-diffusion coefficients(D),and viscosities(η)of supercritical NaAlSi_(3)O_(8)-H_(2)O fluids under conditions of 2000 K and 3-10 GPa,with water contents of 30 wt% and 50 wt%.Our calculations indicate that at a water content of 30 wt%,Q^(2) and Q^(3) exhibit a certain degree of positive and negative pressure dependence,respectively,while other Q^(n) species(n represents the number of bridging oxygens connected to Si/Al)show minimal changes.At a water content of 50 wt%,Q^(2) and Q^(0) exhibit a certain degree of positive and negative pressure dependence,respectively,while other Q^(n) species show minimal changes.At both water contents,Si-O-H and molecular water in the system exhibit negative pressure dependence,suggesting that the migration of supercritical fluids from deep to shallow regions is accompanied by the release of water.The self-diffusion coefficients in the supercritical NaAlSi_(3)O_(8)-H_(2)O fluid follow the order D_(Na)≈D_(H)>D_(O)>D_(Al)≈D_(Si),with an overall weak negative pressure dependence.By comparing the viscosities of anhydrous and hydrous silicate melts from previous studies,we found that the addition of water caused a transition from negative to positive pressure dependence of viscosity,corresponding to a structural change from polymerization to depolymerization.Additionally,we calculated the fluid mobility Δp/η of supercritical NaAlSi_(3)O_(8)-H_(2)O fluids and found that their mobility is several orders of magnitude higher than that of basalt melt and is also significantly greater than that of carbonate melt.As supercritical fluids ascend from deeper to shallower regions,their mobility is further enhanced,significantly contributing to the transport of elements from subducting slabs to the overlying mantle wedge.
基金financially supported by National Undergraduate Training Program for Innovation and Entrepreneurship(Nos.201810345012 and 201810345051)
文摘A graphite carbon nitride(g-C3N4)modified Bi4O5I2 composite was successfully prepared insitu via the thermal treatment of a g-C3N4/Bi OI precursor at 400°C for 3 hr.The as-prepared g-C3N4/Bi4O5I2 showed high photocatalytic performance in Methyl Orange(MO)degradation under visible light.The best sample presented a degradation rate of 0.164 min^-1,which is 3.2 and 82 times as high as that of Bi4O5I2 and g-C3N4,respectively.The g-C3N4/Bi4O5I2 was characterized by X-ray powder diffractometer(XRD),scanning electron microscopy(SEM),transmission electron microscopy(TEM),Raman,X-ray photoelectron spectroscopy(XPS),ultraviolet-visible diffuse reflectance spectra(DRS),electrochemical impedance spectroscopy(EIS)and transient photocurrent response in order to explain the enhanced photoactivity.Results indicated that the decoration with a small amount of g-C3N4 influenced the specific surface area only slightly.Nevertheless,the capability for absorbing visible light was improved measurably,which was beneficial to the MO degradation.On top of that,a strong interaction between g-C3N4 and Bi4O5I2 was detected.This interplay promoted the formation of a favorable heterojunction structure and thereby enhanced the charge separation.Thus,the g-C3N4/Bi4O5I2 composite presented greater charge separation efficiency and much better photocatalytic performance than Bi4O5I2.Additionally,g-C3N4/Bi4O5I2 also presented high stability.·O2^- and holes were verified to be the main reactive species.
文摘Sc^3＋-doped lithium manganese oxides were synthesized by solid-state reaction. The influences of doping element on structure, mean valence of manganese, and electrochemical performances were studied by X-ray diffraction （XRD）, galvanostatic charge-discharge and cyclic voltammetric tests, and also electrochemical impedance spectroscopy （EIS）. XRD tests showed that doped lithium manganese oxides were pure spinel structure without other phases. Redox titration and visible spectrophotometry tests indicated that the mean valence of manganese in doped lithium manganese oxides was higher than that of pure one. LiSc0.02Mn1.9804 remained 92.9% of the initial specific discharge capacity after 50th cycle at a constant current of 50 m/g, and the reversibility of LiSc0.02Mn1.98O4 was improved in comparison with pure LiMn2O4 at 50 ℃. EIS indicated that film deposition on spinel particles was suppressed because of Sc^3＋ doping, and the charge transfer between the surface film and spinel particles with increasing temperature for Sc^3＋-doped materials became easier as compared with undoped one.
基金financially supported by Shenzhen Engineering Laboratory of Nuclear Materials and Service Safety。
文摘This study evaluated the mechanical properties and thermal properties of Al-12 vol%B4 C composite at elevated temperature strengthened with in situ Al2 O3 network.The composite was fabricated using powder metallurgy(PM)with raw materials of fine atomized aluminum powders,and the associated microstructures were observed.At 350℃,the composite had ultimate tensile strength of UTS=137 MPa,yield strength of YS0.2=118 MPa,and elongation ofε=4%.Besides,the mechanical properties of the composite remained unchanged at 350℃after the long holding periods up to 1000 h.The excellent mechanical properties and thermal stability at 350℃were secured by in situ am-Al2O3 network that strengthened the grain boundaries.The interfacial debonding and brittle cracking of B4 C particles were the main fracture mechanisms of the composite.In addition,the influence of sintering temperature and rolling deformation on the microstructures and mechanical properties was studied.
