A solid state reaction method was used to prepare the perovskite-structured compounds BaZrl-xYxO3-a （x=0, 0.05, 0.1, 0.15, 0.2, 0.25, 0.3）. The X-ray diffraction （XRD） pattern indicated that the target perovsldte ...A solid state reaction method was used to prepare the perovskite-structured compounds BaZrl-xYxO3-a （x=0, 0.05, 0.1, 0.15, 0.2, 0.25, 0.3）. The X-ray diffraction （XRD） pattern indicated that the target perovsldte phases were obtained. With increasing Y con- centration the unit cell parameters of BaZrl-xYxO3-a samples were expanded, and Y doping became more difficult. However, high synthesis temperature is helpful to promote Y doping. The SEM results showed that the samples exhibited poor sinterability with in- creasing Y-doping content. Thermal gravimetric （TG） curves analysis showed the more mass decreasing of BaZrl-xYxO3-a （0≤x≤0.3） samples at high temperature with more Y doping and more proton introducing. The electrochemical impedance spectra （EIS） of specimens showed that conductivities of BaZrl_xYxO3（0≤x≤0.3） increased with increasing temperature from 300 to 900 ℃ in wet air. At 900 ℃, the conductivity of BaZrl-xYxO3-a （0≤x≤0.3） first increased with increasing doped amount of Y, and reached the high- est value of 1.07x 104 S/cm when x was 0.2, then decreased gradually with further increasing Y content. At 600 ℃, BaZr0.75Y0.2503-a displayed the highest conductivity, while the conductivity of BaZro.rYo.303-a was the highest at 300 ℃. The results indicated that there should be an optimum Y doping concentration yielding the highest conductivity at a constant temperature, and the optimum Y doping concentration should increase in the humidity atmosphere as the temperature decreases. So increasing the Y-doping concen- tration is helpful to improve the conductivities of BaZrl-xYxO3-a materials at low temperature.展开更多
It is of great significance to develop high-temperature anhydrous proton conducting materials.Herein,we report a new strategy to significantly enhance the proton conductivity of covalent organic frameworks(COFs)throug...It is of great significance to develop high-temperature anhydrous proton conducting materials.Herein,we report a new strategy to significantly enhance the proton conductivity of covalent organic frameworks(COFs)through expanding the dimensionality of proton conduction.Three COF-based composites,COF-1@PA,COF-2@PA,and COF-3@PA(PA:phosphoric acid),are prepared by PA doping of three COFs with similar pore sizes but different amounts of hydrophilic groups.With the increase of hydrophilic groups,COFs can load more PA because of the enhanced hydrogen–bonding interactions between PA and the frameworks.powder X-ray diffraction(PXRD),scanning electron microscopy(SEM),and two-dimensional(2D)solid-state nuclear magnetic resonance(NMR)analyses show that PA can not only enter the channels of COF-3,but also insert into its 2D interlayers.This expands the proton conduction pathways from one-dimensional(1D)to three-dimensional(3D),which greatly improves the proton conductivity of COF-3.Meanwhile,the confinement effect of 1D channels and 2D layers of COF-3 also makes the hydrogen-bonded networks more orderly in COF-3@PA-30(30μL of PA loaded on COF-3).At 150℃,COF-3@PA-30 exhibits an ultrahigh anhydrous proton conductivity of 1.4 S·cm−1,which is a record of anhydrous proton conductivity reported to date.This work develops a new strategy for increasing the proton conductivity of 2D COF materials.展开更多
Energy storage devices with high volumetric and gravimetric capacitance are in urgent demand due to the booming market of portable and wearable electronics.Using redox-active molecules as electrolytes is a strategy to...Energy storage devices with high volumetric and gravimetric capacitance are in urgent demand due to the booming market of portable and wearable electronics.Using redox-active molecules as electrolytes is a strategy to improve the capacitance and energy density of solid-state supercapacitors(SCs).In this study,polyoxometalates(POMs)are applied as proton conductors and redox mediators in polyvinyl alcohol(PVA)electrolytes,which increase the capacitance of obtained SCs with polyaniline(PANI).H_(3)PMo_(12)O_(40)-loaded PANI electrodes provide pseudocapacitance with an eight-electron Faraday reaction in a charge–discharge cycle.This has rarely been reported in SCs before.The largest capacitance of SCs with H_(3)PMo_(12)O_(40)and H_(3)PW_(12)O_(40)as electrolytes is 7.69 F/cm^(2)(3840 F/g)based on a single electrode at 0.5 mA/cm^(2).In addition,POM electrolytes exhibit excellent self-healing ability,which is attributed to the rich hydrogen-bonding network between POMs and PVA.This study demonstrates that the capacitance of solid-state SCs is improved by using molecular redox-active electrolytes and showcases the potential of applying this strategy to other energy storage devices in the future.展开更多
基金Project supported by National Natural Science Foundation of China （51074038, 51274057） and National High Technology Research and Development Program of China （2013AA030902）
文摘A solid state reaction method was used to prepare the perovskite-structured compounds BaZrl-xYxO3-a （x=0, 0.05, 0.1, 0.15, 0.2, 0.25, 0.3）. The X-ray diffraction （XRD） pattern indicated that the target perovsldte phases were obtained. With increasing Y con- centration the unit cell parameters of BaZrl-xYxO3-a samples were expanded, and Y doping became more difficult. However, high synthesis temperature is helpful to promote Y doping. The SEM results showed that the samples exhibited poor sinterability with in- creasing Y-doping content. Thermal gravimetric （TG） curves analysis showed the more mass decreasing of BaZrl-xYxO3-a （0≤x≤0.3） samples at high temperature with more Y doping and more proton introducing. The electrochemical impedance spectra （EIS） of specimens showed that conductivities of BaZrl_xYxO3（0≤x≤0.3） increased with increasing temperature from 300 to 900 ℃ in wet air. At 900 ℃, the conductivity of BaZrl-xYxO3-a （0≤x≤0.3） first increased with increasing doped amount of Y, and reached the high- est value of 1.07x 104 S/cm when x was 0.2, then decreased gradually with further increasing Y content. At 600 ℃, BaZr0.75Y0.2503-a displayed the highest conductivity, while the conductivity of BaZro.rYo.303-a was the highest at 300 ℃. The results indicated that there should be an optimum Y doping concentration yielding the highest conductivity at a constant temperature, and the optimum Y doping concentration should increase in the humidity atmosphere as the temperature decreases. So increasing the Y-doping concen- tration is helpful to improve the conductivities of BaZrl-xYxO3-a materials at low temperature.
基金We are grateful for financial support from the National Natural Science Foundation of China(Nos.21771193 and 22275210)Key Research and Development Projects of Shandong Province(No.2019JZZY010331).
文摘It is of great significance to develop high-temperature anhydrous proton conducting materials.Herein,we report a new strategy to significantly enhance the proton conductivity of covalent organic frameworks(COFs)through expanding the dimensionality of proton conduction.Three COF-based composites,COF-1@PA,COF-2@PA,and COF-3@PA(PA:phosphoric acid),are prepared by PA doping of three COFs with similar pore sizes but different amounts of hydrophilic groups.With the increase of hydrophilic groups,COFs can load more PA because of the enhanced hydrogen–bonding interactions between PA and the frameworks.powder X-ray diffraction(PXRD),scanning electron microscopy(SEM),and two-dimensional(2D)solid-state nuclear magnetic resonance(NMR)analyses show that PA can not only enter the channels of COF-3,but also insert into its 2D interlayers.This expands the proton conduction pathways from one-dimensional(1D)to three-dimensional(3D),which greatly improves the proton conductivity of COF-3.Meanwhile,the confinement effect of 1D channels and 2D layers of COF-3 also makes the hydrogen-bonded networks more orderly in COF-3@PA-30(30μL of PA loaded on COF-3).At 150℃,COF-3@PA-30 exhibits an ultrahigh anhydrous proton conductivity of 1.4 S·cm−1,which is a record of anhydrous proton conductivity reported to date.This work develops a new strategy for increasing the proton conductivity of 2D COF materials.
基金support from the National Natural Science Foundation of China(nos.21871042,21471028,and 21673098)。
文摘Energy storage devices with high volumetric and gravimetric capacitance are in urgent demand due to the booming market of portable and wearable electronics.Using redox-active molecules as electrolytes is a strategy to improve the capacitance and energy density of solid-state supercapacitors(SCs).In this study,polyoxometalates(POMs)are applied as proton conductors and redox mediators in polyvinyl alcohol(PVA)electrolytes,which increase the capacitance of obtained SCs with polyaniline(PANI).H_(3)PMo_(12)O_(40)-loaded PANI electrodes provide pseudocapacitance with an eight-electron Faraday reaction in a charge–discharge cycle.This has rarely been reported in SCs before.The largest capacitance of SCs with H_(3)PMo_(12)O_(40)and H_(3)PW_(12)O_(40)as electrolytes is 7.69 F/cm^(2)(3840 F/g)based on a single electrode at 0.5 mA/cm^(2).In addition,POM electrolytes exhibit excellent self-healing ability,which is attributed to the rich hydrogen-bonding network between POMs and PVA.This study demonstrates that the capacitance of solid-state SCs is improved by using molecular redox-active electrolytes and showcases the potential of applying this strategy to other energy storage devices in the future.
