Iron‐based pyrophosphates are attractive cathodes for sodium‐ion batteries due to their large framework,cost‐effectiveness,and high energy density.However,the understanding of the crystal structure is scarce and on...Iron‐based pyrophosphates are attractive cathodes for sodium‐ion batteries due to their large framework,cost‐effectiveness,and high energy density.However,the understanding of the crystal structure is scarce and only a limited candidates have been reported so far.In this work,we found for the first time that a continuous solid solution,Na_(4−α)Fe_(2+α)_(2)(P_(2)O_(7))_(2)(0≤α≤1,could be obtained by mutual substitution of cations at center‐symmetric Na3 and Na4 sites while keeping the crystal building blocks of anionic P_(2)O_(7) unchanged.In particular,a novel off‐stoichiometric Na_(3)Fe(2.5)(P_(2)O_(7))_(2)is thus proposed,and its structure,energy storage mechanism,and electrochemical performance are extensively investigated to unveil the structure–function relationship.The as‐prepared off‐stoichiometric electrode delivers appealing performance with a reversible discharge capacity of 83 mAh g^(−1),a working voltage of 2.9 V(vs.Na^(+)/Na),the retention of 89.2%of the initial capacity after 500 cycles,and enhanced rate capability of 51 mAh g^(−1)at a current density of 1600 mA g^(−1).This research shows that sodium ferric pyrophosphate could form extended solid solution composition and promising phase is concealed in the range of Na_(4−α)Fe_(2+α)_(2)(P_(2)O_(7))_(2),offering more chances for exploration of new cathode materials for the construction of high‐performance SIBs.展开更多
Ion mobility in solid solutions of the fluorite structure 50Pb2–30BiF3–20KF (I) and 50Pb2–30BiF3–20NaF (II) was studied by NMR method. Analysis of 19F, 23Na NMR spectra made it possible to reveal the character of ...Ion mobility in solid solutions of the fluorite structure 50Pb2–30BiF3–20KF (I) and 50Pb2–30BiF3–20NaF (II) was studied by NMR method. Analysis of 19F, 23Na NMR spectra made it possible to reveal the character of ion motions in the fluoride and sodium sublattices with temperature variation, to determine the types and temperature ranges in which they took place. It was found that the dominant form of ionic mobility in the samples I and II above 380 K was the diffusion of fluoride and sodium ions. According to preliminary results of electro-physical studies, the conductivity reached values of ~ 2×10–2 – 10–3 S/cm above 500 K. The solid solutions I and II can be recommended as a basis for use in the development of new functional materials.展开更多
Ultrafine particles prepared by evaporating pure Fe in CH4 atmosphere using arc-dischargeheating method, were found to consist of Fe-C solid solution, γ-Fe and Fe3C phases. EfFect of annealing temperature on phase tr...Ultrafine particles prepared by evaporating pure Fe in CH4 atmosphere using arc-dischargeheating method, were found to consist of Fe-C solid solution, γ-Fe and Fe3C phases. EfFect of annealing temperature on phase transformation and hyperfine interactions has been investigated by Mossbauer spectroscopy, X-ray diffraction (XRD), differential thermal analysis and thermogravimetry (DTA-TG), transmission electron microscopy (TEM), oxygen determination and vibrating sample magnetometer (VSM) measurements. It was observed that phase transformation of γ-Fe to α-Fe occurs during annealing in vacuum. The mechanism causing the change of hyperfine interactions with annealing temperature differs for Fe-C solution and interstitial compounds. DifFerence of hyperfine interactions of Fe-C solid solution in the starting sample and its annealed samples is ascribed to the improvement of activation of interstitial carbon atoms. Stress-relieving in structure of annealed Fe3C particle can result in a weak influence on hyperfine interactions. Parameters fitted to the Mossbauer spectra show the existence of superparamagnetism in all the samples. Absorbed and combined oxygen on particle surface of the starting sample were determined.展开更多
Nominal composition of Ca1-xZnxTiO3 ： 0. 002Pr^3 ＋ （x = 0. 000 - 0. 200） phosphors were prepared by conventional solid reaction route. XRD and PL measurements were used to investigate the solid-solution structure ...Nominal composition of Ca1-xZnxTiO3 ： 0. 002Pr^3 ＋ （x = 0. 000 - 0. 200） phosphors were prepared by conventional solid reaction route. XRD and PL measurements were used to investigate the solid-solution structure and luminescence properties of Zn-doped Ca1-xZnxTiO3：0.002Pr^3＋ phosphors. The effect of solid-solution structure formed by substitution between Ca^2 ＋ and Zn^2＋ ions on the luminescent properties was analyzed. The results reveal that, with the increase of Zn substitution content below 0.010, lattice parameters and the intensity of excitation peak at both 260 and 330 nm as well as the corresponding 610 nm emission intensity are monotonously decreased quickly in a similar tendency. Also, the evolution of luminescence intensity and crystal cell parameters against Zn doping concentration are in good agreement. Above results are closely related with the structure change within Ca1- xZnxTiO3：0.002Pr^3＋ solid-solution phase formed by the Zn ions substitution for the Ca sites. Present study reveals that the solid-solution structure formed by substitution between Ca^2＋ and Zn^2＋ ions has significant effect on the luminescence properties of single phase Ca1-xZnxTiO3：0.002Pr^3＋ phosphors.展开更多
To understand the effect of the doping amount of Cu^2+ on the structure and reactivity of SnO2 in NOx-SCR with NH3, a series of Sn-Cu-O binary oxide catalysts with different Sn/Cu ratios have been prepared and thoroug...To understand the effect of the doping amount of Cu^2+ on the structure and reactivity of SnO2 in NOx-SCR with NH3, a series of Sn-Cu-O binary oxide catalysts with different Sn/Cu ratios have been prepared and thoroughly characterized. Using the XRD extrapolation method, the SnO2 lattice capacity for Cu^2+ cations is determined at 0.10 g Cu O per g of SnO2, equaling a Sn/Cu molar ratio of 84/16. Therefore, in a tetragonal rutile SnO2 lattice, only a maximum of 16% of the Sn4+ cations can be replaced by Cu^2+ to form a stable solid solution structure. If the Cu content is higher, Cu O will form on the catalyst surface, which has a negative effect on the reaction performance. For samples in a pure solid solution phase, the number of surface defects increase with increasing Cu content until it reaches the lattice capacity, as confirmed by Raman spectroscopy. As a result, the amounts of both active oxygen species and acidic sites on the surface, which critically determine the reaction performance, also increase and reach the maximum level for the catalyst with a Cu content close to the lattice capacity. A distinct lattice capacity threshold effect on the structure and reactivity of Sn-Cu binary oxide catalysts has been observed. A Sn-Cu catalyst with the best reaction performance can be obtained by doping the SnO2 matrix with the lattice capacity amount of Cu^2+.展开更多
By X-ray powder diffraction technique and oxygen content analysis, a solid solution Sm1+xBa2-xCu3Oy has been determined in the range 0≤x≤0.4. When x<0.25. the Sm1+xBa2-xCu3Oy presents orthorhombic symmetry, and ...By X-ray powder diffraction technique and oxygen content analysis, a solid solution Sm1+xBa2-xCu3Oy has been determined in the range 0≤x≤0.4. When x<0.25. the Sm1+xBa2-xCu3Oy presents orthorhombic symmetry, and the orthorhombic-tetragonaJ transition ocCurs at x = 0.25. With the increase of x, TC decreases and finally breaks. The correlation between ox ygen content and phase structure at different quench temperatures related to Sm Ba2Cu3Oy has been investigated as well展开更多
For the pursuit of high energy supercapacitors,the development of high performance pseudocapacitance or battery-type negative electrode material is urgently needed to make up for the capacity shortage of commercial el...For the pursuit of high energy supercapacitors,the development of high performance pseudocapacitance or battery-type negative electrode material is urgently needed to make up for the capacity shortage of commercial electric double layer capacitor(EDLC)type materials.Herein,a porous and defect-rich Fe_(x)Bi_(2-x)S_(3) solid solution structure is firstly constructed by employing Fe-doped Bi_(2)O_(2)CO_(3) porous nanosheets as a precursor,which presents dramatically increased energy storage performance than Bi_(2)S_(3) and FeS_(2) phase.For the optimized Fe_(x)Bi_(2-x)S_(3) solid solution(FeBiS-60%),the Fe solute is free and random dispersed in Bi_(2)S_(3) framework,which can effectively modulate the electronic structure of Bi element and introduce rich-defect due to the existence of Fe(II).Meanwhile,the FeBiS-60%,constructed by pore nanosheets that are assembled by self-supported basic nanorod units,presents rich mesoporous channels for fast mass transfer and abundant active sites for promoting capacity performance.Therefore,a high capacitance of 832.8 F·g^(-1) at a current density of 1 A·g^(-1) is achieved by the FeBiS-60%electrode.Furthermore,a fabricated Ni3S_(2)@Co_(3)S_(4)(NCS)//FeBiS-60%hybrid supercapacitor device delivers an outstanding energy density of 85.33 Wh·kg^(-1) at the power density of 0.799 kW·kg^(-1),and ultra-long lifespan of remaining 86.7%initial capacitance after 8700 cycles.展开更多
Changing the N content in the Ti_(3)AlC_(2−y)N_(y) MAX phase solid solutions allows for the fine-tuning of their properties.However,systematic studies on the synthesis and properties of Ti_(3)AlC_(2−y)N_(y) solid solu...Changing the N content in the Ti_(3)AlC_(2−y)N_(y) MAX phase solid solutions allows for the fine-tuning of their properties.However,systematic studies on the synthesis and properties of Ti_(3)AlC_(2−y)N_(y) solid solution bulks have not been reported thus far.Here,previously reported Ti_(3)AlC_(2−y)N_(y) solid solution bulks(y=0.3,0.5,0.8,and 1.0)were synthesized via hot pressing of their powder counterparts under optimized conditions.The prepared Ti_(3)AlC_(2−y)N_(y) bulks are dense and have a fine microstructure with grain sizes of 6–8μm.The influence of the N content on the mechanical properties,electrical conductivities,and coefficients of thermal expansion(CTEs)of the prepared Ti_(3)AlC_(2−y)N_(y) bulk materials was clarified.The flexural strength and Vickers hardness values increased with increasing N content,suggesting that solid solution strengthening effectively improved the mechanical properties of Ti_(3)AlC_(2−y)N_(y).Ti_(3)AlCN(y=1)had the highest Vickers hardness and flexural strength among the studied samples,reaching 5.54 GPa and 550 MPa,respectively.However,the electrical conductivity and CTEs of the Ti_(3)AlC_(2−y)N_(y) solid solutions decreased with increasing N content,from 8.93×10^(−6) to 7.69×10^(−6) K^(−1) and from 1.33×10^(6) to 0.95×10^(6) S/m,respectively.This work demonstrated the tunable properties of Ti_(3)AlC_(2−y)N_(y) solid solutions with varying N contents and widened the MAX phase family for fundamental studies and applications.展开更多
Ca2-xSrxZn4Ti15O36∶Pr red long decay phosphor was synthesized by high temperature solid state reaction. Photoluminescence property and crystalline and unit cell parameters of the orthorhombic were investigated by flu...Ca2-xSrxZn4Ti15O36∶Pr red long decay phosphor was synthesized by high temperature solid state reaction. Photoluminescence property and crystalline and unit cell parameters of the orthorhombic were investigated by fluorescence spectrophotometer and by powder X-ray diffraction, respectively. The emission intensity at 618 nm changes sharply when the concentration of Sr2+ （x） is less than 0.1 and the emission intensity reaches the maximum when x is equal to 0.007. There is an obviously broad excitation band at 270 nm when x is equal to 0.003 and it disappears gradually when x is over 0.01. The unit cell a parameter of Ca2-xSrxZn4Ti15O36∶Pr decreases while c parameter increases with the increases of the concentration of the doped Sr2+. When x is over 0.1 the value of the unit cell parameters a and c become stable. TL peaks of Ca2Zn4Ti15O36∶Pr, Ca1.993Sr0.007Zn4Ti15O36∶0.002Pr3+, 0.002Na+, are located at 62 ℃, 88 ℃, respectively, which indicates that there are deeper traps in Ca1.993Sr0.007Zn4 Ti15O36∶0.002Pr3+, 0.002Na+.展开更多
基金National Natural Science Foundation of China,Grant/Award Numbers:21972108,U20A20249,U22A20438Changzhou Science and Technology Bureau,Grant/Award Number:CM20223017Innovation and Technology Commission(ITC)of Hong Kong,The Innovation&Technology Fund(ITF)with Project No.ITS/126/21。
文摘Iron‐based pyrophosphates are attractive cathodes for sodium‐ion batteries due to their large framework,cost‐effectiveness,and high energy density.However,the understanding of the crystal structure is scarce and only a limited candidates have been reported so far.In this work,we found for the first time that a continuous solid solution,Na_(4−α)Fe_(2+α)_(2)(P_(2)O_(7))_(2)(0≤α≤1,could be obtained by mutual substitution of cations at center‐symmetric Na3 and Na4 sites while keeping the crystal building blocks of anionic P_(2)O_(7) unchanged.In particular,a novel off‐stoichiometric Na_(3)Fe(2.5)(P_(2)O_(7))_(2)is thus proposed,and its structure,energy storage mechanism,and electrochemical performance are extensively investigated to unveil the structure–function relationship.The as‐prepared off‐stoichiometric electrode delivers appealing performance with a reversible discharge capacity of 83 mAh g^(−1),a working voltage of 2.9 V(vs.Na^(+)/Na),the retention of 89.2%of the initial capacity after 500 cycles,and enhanced rate capability of 51 mAh g^(−1)at a current density of 1600 mA g^(−1).This research shows that sodium ferric pyrophosphate could form extended solid solution composition and promising phase is concealed in the range of Na_(4−α)Fe_(2+α)_(2)(P_(2)O_(7))_(2),offering more chances for exploration of new cathode materials for the construction of high‐performance SIBs.
文摘Ion mobility in solid solutions of the fluorite structure 50Pb2–30BiF3–20KF (I) and 50Pb2–30BiF3–20NaF (II) was studied by NMR method. Analysis of 19F, 23Na NMR spectra made it possible to reveal the character of ion motions in the fluoride and sodium sublattices with temperature variation, to determine the types and temperature ranges in which they took place. It was found that the dominant form of ionic mobility in the samples I and II above 380 K was the diffusion of fluoride and sodium ions. According to preliminary results of electro-physical studies, the conductivity reached values of ~ 2×10–2 – 10–3 S/cm above 500 K. The solid solutions I and II can be recommended as a basis for use in the development of new functional materials.
文摘Ultrafine particles prepared by evaporating pure Fe in CH4 atmosphere using arc-dischargeheating method, were found to consist of Fe-C solid solution, γ-Fe and Fe3C phases. EfFect of annealing temperature on phase transformation and hyperfine interactions has been investigated by Mossbauer spectroscopy, X-ray diffraction (XRD), differential thermal analysis and thermogravimetry (DTA-TG), transmission electron microscopy (TEM), oxygen determination and vibrating sample magnetometer (VSM) measurements. It was observed that phase transformation of γ-Fe to α-Fe occurs during annealing in vacuum. The mechanism causing the change of hyperfine interactions with annealing temperature differs for Fe-C solution and interstitial compounds. DifFerence of hyperfine interactions of Fe-C solid solution in the starting sample and its annealed samples is ascribed to the improvement of activation of interstitial carbon atoms. Stress-relieving in structure of annealed Fe3C particle can result in a weak influence on hyperfine interactions. Parameters fitted to the Mossbauer spectra show the existence of superparamagnetism in all the samples. Absorbed and combined oxygen on particle surface of the starting sample were determined.
文摘Nominal composition of Ca1-xZnxTiO3 ： 0. 002Pr^3 ＋ （x = 0. 000 - 0. 200） phosphors were prepared by conventional solid reaction route. XRD and PL measurements were used to investigate the solid-solution structure and luminescence properties of Zn-doped Ca1-xZnxTiO3：0.002Pr^3＋ phosphors. The effect of solid-solution structure formed by substitution between Ca^2 ＋ and Zn^2＋ ions on the luminescent properties was analyzed. The results reveal that, with the increase of Zn substitution content below 0.010, lattice parameters and the intensity of excitation peak at both 260 and 330 nm as well as the corresponding 610 nm emission intensity are monotonously decreased quickly in a similar tendency. Also, the evolution of luminescence intensity and crystal cell parameters against Zn doping concentration are in good agreement. Above results are closely related with the structure change within Ca1- xZnxTiO3：0.002Pr^3＋ solid-solution phase formed by the Zn ions substitution for the Ca sites. Present study reveals that the solid-solution structure formed by substitution between Ca^2＋ and Zn^2＋ ions has significant effect on the luminescence properties of single phase Ca1-xZnxTiO3：0.002Pr^3＋ phosphors.
文摘To understand the effect of the doping amount of Cu^2+ on the structure and reactivity of SnO2 in NOx-SCR with NH3, a series of Sn-Cu-O binary oxide catalysts with different Sn/Cu ratios have been prepared and thoroughly characterized. Using the XRD extrapolation method, the SnO2 lattice capacity for Cu^2+ cations is determined at 0.10 g Cu O per g of SnO2, equaling a Sn/Cu molar ratio of 84/16. Therefore, in a tetragonal rutile SnO2 lattice, only a maximum of 16% of the Sn4+ cations can be replaced by Cu^2+ to form a stable solid solution structure. If the Cu content is higher, Cu O will form on the catalyst surface, which has a negative effect on the reaction performance. For samples in a pure solid solution phase, the number of surface defects increase with increasing Cu content until it reaches the lattice capacity, as confirmed by Raman spectroscopy. As a result, the amounts of both active oxygen species and acidic sites on the surface, which critically determine the reaction performance, also increase and reach the maximum level for the catalyst with a Cu content close to the lattice capacity. A distinct lattice capacity threshold effect on the structure and reactivity of Sn-Cu binary oxide catalysts has been observed. A Sn-Cu catalyst with the best reaction performance can be obtained by doping the SnO2 matrix with the lattice capacity amount of Cu^2+.
文摘By X-ray powder diffraction technique and oxygen content analysis, a solid solution Sm1+xBa2-xCu3Oy has been determined in the range 0≤x≤0.4. When x<0.25. the Sm1+xBa2-xCu3Oy presents orthorhombic symmetry, and the orthorhombic-tetragonaJ transition ocCurs at x = 0.25. With the increase of x, TC decreases and finally breaks. The correlation between ox ygen content and phase structure at different quench temperatures related to Sm Ba2Cu3Oy has been investigated as well
基金support from the National Natural Science Foundation of China(Nos.52272222,52072197)Outstanding Youth Foundation of Shandong Province,China(No.ZR2019JQ14)+4 种基金University Youth Innovation Team of Shandong Province(Nos.2019KJC004,202201010318)the Natural Science Foundation of Shandong Province,China(No.ZR2021MB061)Major Scientific and Technological Innovation Project(No.2019JZZY020405)Taishan Scholar Young Talent Program(No.tsqn201909114)Major Basic Research Program of Natural Science Foundation of Shandong Province under Grant(No.ZR2020ZD09).
文摘For the pursuit of high energy supercapacitors,the development of high performance pseudocapacitance or battery-type negative electrode material is urgently needed to make up for the capacity shortage of commercial electric double layer capacitor(EDLC)type materials.Herein,a porous and defect-rich Fe_(x)Bi_(2-x)S_(3) solid solution structure is firstly constructed by employing Fe-doped Bi_(2)O_(2)CO_(3) porous nanosheets as a precursor,which presents dramatically increased energy storage performance than Bi_(2)S_(3) and FeS_(2) phase.For the optimized Fe_(x)Bi_(2-x)S_(3) solid solution(FeBiS-60%),the Fe solute is free and random dispersed in Bi_(2)S_(3) framework,which can effectively modulate the electronic structure of Bi element and introduce rich-defect due to the existence of Fe(II).Meanwhile,the FeBiS-60%,constructed by pore nanosheets that are assembled by self-supported basic nanorod units,presents rich mesoporous channels for fast mass transfer and abundant active sites for promoting capacity performance.Therefore,a high capacitance of 832.8 F·g^(-1) at a current density of 1 A·g^(-1) is achieved by the FeBiS-60%electrode.Furthermore,a fabricated Ni3S_(2)@Co_(3)S_(4)(NCS)//FeBiS-60%hybrid supercapacitor device delivers an outstanding energy density of 85.33 Wh·kg^(-1) at the power density of 0.799 kW·kg^(-1),and ultra-long lifespan of remaining 86.7%initial capacitance after 8700 cycles.
基金supported by the Fundamental Research Funds for the Central Universities(Nos.2023YJS061 and 2023JBZY019).
文摘Changing the N content in the Ti_(3)AlC_(2−y)N_(y) MAX phase solid solutions allows for the fine-tuning of their properties.However,systematic studies on the synthesis and properties of Ti_(3)AlC_(2−y)N_(y) solid solution bulks have not been reported thus far.Here,previously reported Ti_(3)AlC_(2−y)N_(y) solid solution bulks(y=0.3,0.5,0.8,and 1.0)were synthesized via hot pressing of their powder counterparts under optimized conditions.The prepared Ti_(3)AlC_(2−y)N_(y) bulks are dense and have a fine microstructure with grain sizes of 6–8μm.The influence of the N content on the mechanical properties,electrical conductivities,and coefficients of thermal expansion(CTEs)of the prepared Ti_(3)AlC_(2−y)N_(y) bulk materials was clarified.The flexural strength and Vickers hardness values increased with increasing N content,suggesting that solid solution strengthening effectively improved the mechanical properties of Ti_(3)AlC_(2−y)N_(y).Ti_(3)AlCN(y=1)had the highest Vickers hardness and flexural strength among the studied samples,reaching 5.54 GPa and 550 MPa,respectively.However,the electrical conductivity and CTEs of the Ti_(3)AlC_(2−y)N_(y) solid solutions decreased with increasing N content,from 8.93×10^(−6) to 7.69×10^(−6) K^(−1) and from 1.33×10^(6) to 0.95×10^(6) S/m,respectively.This work demonstrated the tunable properties of Ti_(3)AlC_(2−y)N_(y) solid solutions with varying N contents and widened the MAX phase family for fundamental studies and applications.
文摘Ca2-xSrxZn4Ti15O36∶Pr red long decay phosphor was synthesized by high temperature solid state reaction. Photoluminescence property and crystalline and unit cell parameters of the orthorhombic were investigated by fluorescence spectrophotometer and by powder X-ray diffraction, respectively. The emission intensity at 618 nm changes sharply when the concentration of Sr2+ （x） is less than 0.1 and the emission intensity reaches the maximum when x is equal to 0.007. There is an obviously broad excitation band at 270 nm when x is equal to 0.003 and it disappears gradually when x is over 0.01. The unit cell a parameter of Ca2-xSrxZn4Ti15O36∶Pr decreases while c parameter increases with the increases of the concentration of the doped Sr2+. When x is over 0.1 the value of the unit cell parameters a and c become stable. TL peaks of Ca2Zn4Ti15O36∶Pr, Ca1.993Sr0.007Zn4Ti15O36∶0.002Pr3+, 0.002Na+, are located at 62 ℃, 88 ℃, respectively, which indicates that there are deeper traps in Ca1.993Sr0.007Zn4 Ti15O36∶0.002Pr3+, 0.002Na+.
