NASICON (sodium (Na) superionic conductor) compounds have attracted considerable attention as promising solid electrolyte materials for advanced Na-based batteries. In this study, we investigated the improvement in io...NASICON (sodium (Na) superionic conductor) compounds have attracted considerable attention as promising solid electrolyte materials for advanced Na-based batteries. In this study, we investigated the improvement in ionic conductivities of von-Alpen-type NASICON (vA-NASICON) ceramic electrolytes by introducing a magnesium ion (Mg^(2+)) as a heterogeneous element. The optimal Mg-doped vA-NASICON exhibited a high ionic conductivity of 3.64×10^(−3) S·cm^(−1), which was almost 80% higher than that of un-doped vA-NASICON. The changes in physicochemical properties of the vA-NASICONs through the Mg introduction were systematically analyzed, and their effects on the ionic conductivities of the vA-NASICON were studied in detail. When the optimal ratio of Mg^(2+) was used in a synthetic process, the relative density (96.6%) and grain boundary ionic conductivity (σgb) were maximized, which improved the total ionic conductivity (σt) of the vA-NASICON. However, when Mg^(2+) was introduced in excess, the ionic conductivity decreased because of the formation of an undesired sodium magnesium phosphate (NaxMgyPO_(4)) secondary phase. The results of this study are expected to be effectively applied in the development of advanced sodium-based solid electrolytes with high ionic conductivities.展开更多
Silicon suboxide(SiO_(x),x≈1)is promising in serving as an anode material for lithium-ion batteries with high capacity,but it has a low initial Coulombic efficiency(ICE)due to the irreversible formation of lithium si...Silicon suboxide(SiO_(x),x≈1)is promising in serving as an anode material for lithium-ion batteries with high capacity,but it has a low initial Coulombic efficiency(ICE)due to the irreversible formation of lithium silicates during the first cycle.In this work,we modify SiO_(x) by solid-phase Mg doping reaction using low-cost Mg powder as a reducing agent.We show that Mg reduces SiO_(2) in SiO_(x) to Si and forms MgSiO_(3) or Mg_(2)SiO_(4).The MgSiO_(3) or Mg_(2)SiO_(4) are mainly distributed on the surface of SiO_(x),which suppresses the irreversible lithium-ion loss and enhances the ICE of SiO_(x).However,the formation of MgSiO_(3) or Mg_(2)SiO_(4) also sacrifices the capacity of SiO_(x).Therefore,by controlling the reaction process between Mg and SiO_(x),we can tune the phase composition,proportion,and morphology of the Mg-doped SiO_(x) and manipulate the performance.We obtain samples with a capacity of 1226 mAh g^(–1) and an ICE of 84.12%,which show significant improvement over carbon-coated SiO_(x) without Mg doping.By the synergistical modification of both Mg doping and prelithiation,the capacity of SiO_(x) is further increased to 1477 mAh g^(–1) with a minimal compromise in the ICE(83.77%).展开更多
Calcium magnesium chlorosilicate doped by europium, Ca8Mg(SiO4)4Cl2: Eu^2+, was prepared by the solid state reaction at high temperature. The compound obtained is pure Ca8Mg(SiO4)4Cl2 phase with cubic structure....Calcium magnesium chlorosilicate doped by europium, Ca8Mg(SiO4)4Cl2: Eu^2+, was prepared by the solid state reaction at high temperature. The compound obtained is pure Ca8Mg(SiO4)4Cl2 phase with cubic structure. Its average particle size is 5 μm, and it has good dispersity and morphological form. The excitation spectrum of Ca8Mg(SiO4)4Cl2: Eu^2+ is a wide band, which covers from 270 to 480 nm. The emission spectrum is also a wide band peaked at 510 nm. The luminescent intensity reaches to the maximum when the concentration of Eu^2 + is 2%. The wavelength of emission and excitation of the phosphor with various Eu^2 + contents keeps constant. This spectrum range matches violet and blue LED chips very well, and its strong luminescence intensity is suitable for a green phosphor of tricolor phosphor of white light LED.展开更多
基金supported by Korea Institute of Energy Technology Evaluation and Planning(KETEP)grant funded by the Korea government(MOTIE)(20215610100040,Development of 20 Wh seawater secondary battery unit cell).
文摘NASICON (sodium (Na) superionic conductor) compounds have attracted considerable attention as promising solid electrolyte materials for advanced Na-based batteries. In this study, we investigated the improvement in ionic conductivities of von-Alpen-type NASICON (vA-NASICON) ceramic electrolytes by introducing a magnesium ion (Mg^(2+)) as a heterogeneous element. The optimal Mg-doped vA-NASICON exhibited a high ionic conductivity of 3.64×10^(−3) S·cm^(−1), which was almost 80% higher than that of un-doped vA-NASICON. The changes in physicochemical properties of the vA-NASICONs through the Mg introduction were systematically analyzed, and their effects on the ionic conductivities of the vA-NASICON were studied in detail. When the optimal ratio of Mg^(2+) was used in a synthetic process, the relative density (96.6%) and grain boundary ionic conductivity (σgb) were maximized, which improved the total ionic conductivity (σt) of the vA-NASICON. However, when Mg^(2+) was introduced in excess, the ionic conductivity decreased because of the formation of an undesired sodium magnesium phosphate (NaxMgyPO_(4)) secondary phase. The results of this study are expected to be effectively applied in the development of advanced sodium-based solid electrolytes with high ionic conductivities.
基金supported by the National Natural Science Foundation(52232009)the National Natural Science Foundation for Distinguished Young Scholar(52125404)+1 种基金the National Youth Talent Support Program,“131”First Level Innovative Talents Training Project in Tianjinthe Tianjin Natural Science Foundation for Distinguished Young Scholar(18JCJQJC46500).
文摘Silicon suboxide(SiO_(x),x≈1)is promising in serving as an anode material for lithium-ion batteries with high capacity,but it has a low initial Coulombic efficiency(ICE)due to the irreversible formation of lithium silicates during the first cycle.In this work,we modify SiO_(x) by solid-phase Mg doping reaction using low-cost Mg powder as a reducing agent.We show that Mg reduces SiO_(2) in SiO_(x) to Si and forms MgSiO_(3) or Mg_(2)SiO_(4).The MgSiO_(3) or Mg_(2)SiO_(4) are mainly distributed on the surface of SiO_(x),which suppresses the irreversible lithium-ion loss and enhances the ICE of SiO_(x).However,the formation of MgSiO_(3) or Mg_(2)SiO_(4) also sacrifices the capacity of SiO_(x).Therefore,by controlling the reaction process between Mg and SiO_(x),we can tune the phase composition,proportion,and morphology of the Mg-doped SiO_(x) and manipulate the performance.We obtain samples with a capacity of 1226 mAh g^(–1) and an ICE of 84.12%,which show significant improvement over carbon-coated SiO_(x) without Mg doping.By the synergistical modification of both Mg doping and prelithiation,the capacity of SiO_(x) is further increased to 1477 mAh g^(–1) with a minimal compromise in the ICE(83.77%).
文摘Calcium magnesium chlorosilicate doped by europium, Ca8Mg(SiO4)4Cl2: Eu^2+, was prepared by the solid state reaction at high temperature. The compound obtained is pure Ca8Mg(SiO4)4Cl2 phase with cubic structure. Its average particle size is 5 μm, and it has good dispersity and morphological form. The excitation spectrum of Ca8Mg(SiO4)4Cl2: Eu^2+ is a wide band, which covers from 270 to 480 nm. The emission spectrum is also a wide band peaked at 510 nm. The luminescent intensity reaches to the maximum when the concentration of Eu^2 + is 2%. The wavelength of emission and excitation of the phosphor with various Eu^2 + contents keeps constant. This spectrum range matches violet and blue LED chips very well, and its strong luminescence intensity is suitable for a green phosphor of tricolor phosphor of white light LED.