针对光固化Al2O3陶瓷在脱脂烧结后易形成孔洞、力学性能差的问题,系统研究了石墨烯添加对陶瓷浆料流变性、沉降性、固化行为及烧结体力学性能的影响。采用γ-缩水甘油醚氧丙基三甲氧基硅烷(KH560)对Al2O3粉体进行表面改性,并加入不同含...针对光固化Al2O3陶瓷在脱脂烧结后易形成孔洞、力学性能差的问题,系统研究了石墨烯添加对陶瓷浆料流变性、沉降性、固化行为及烧结体力学性能的影响。采用γ-缩水甘油醚氧丙基三甲氧基硅烷(KH560)对Al2O3粉体进行表面改性,并加入不同含量的石墨烯,制备高固相、低粘度的光固化浆料。通过傅里叶红外光谱、旋转流变仪、沉降试验及Beer-Lambert模型分析,优化了浆料配方与光固化工艺参数。结果表明:当KH560含量为2.5wt%、石墨烯含量为0.01wt%时,浆料粘度最低、沉降分层最少;在曝光时间4 s条件下,添加0.01wt%石墨烯的浆料透射深度为382μm,临界曝光能量为44.3 m J/cm2。经1750℃烧结后,陶瓷零件致密度达99.7%,弯曲强度为27.61 MPa,维氏硬度为13.45GPa。石墨烯通过位阻效应及裂纹偏转机制有效促进了烧结致密化并改善了力学性能。本研究为光固化增材制造高致密、高性能氧化铝陶瓷提供了试验依据。展开更多
The ineluctable introduction of lithium salt to polymer solid-state electrolytes incurs a compromise between strength,ionic conductivity,and thickness.Here,we propose Al2O3-coated polyimide(AO/PI)porous film as ...The ineluctable introduction of lithium salt to polymer solid-state electrolytes incurs a compromise between strength,ionic conductivity,and thickness.Here,we propose Al2O3-coated polyimide(AO/PI)porous film as a high-strength substrate to support fast-ion-conducting polymer-in-salt(PIS)solid-state electrolytes,aiming to suppress lithium dendrite growth and improve full-cell performance.The Al2O3coating layer not only refines the wettability of polyimide porous film to PIS,but also performs as a high modulus protective layer to suppress the growth of lithium dendrites.The resulting PI/AO@PIS exhibits a small thickness of only 35μm with an outstanding tensile strength of 11.3 MPa and Young's modulus of 537.6 MPa.In addition,the PI/AO@PIS delivers a high ionic conductivity of 0.1 m S/cm at 25°C.As a result,the PI/AO@PIS enables symmetric Li cells to achieve exceptional cyclability for over 1000 h at 0.1 m A/cm2without noticeable lithium dendrite formation.Moreover,the PI/AO@PIS-based LiFePO4||Li full cells demonstrate outstanding rate performance(125.7 m Ah/g at 5 C)and impressive cycling stability(96.1%capacity retention at 1 C after 200 cycles).This work highlights the efficacy of enhancing the mechanical properties of polymer matrices and extending cell performance through the incorporation of a dense inorganic interface layer.展开更多
Electrolytic reduction is a crucial process during the pyroprocessing of oxide spent fuel.This paper investigates the effects of different concentrations of Li2O on the properties of the LiCl-UCl3-Li2O mol...Electrolytic reduction is a crucial process during the pyroprocessing of oxide spent fuel.This paper investigates the effects of different concentrations of Li2O on the properties of the LiCl-UCl3-Li2O molten salt system during electrolytic reduction using first-principles molecular dynamics simulations.The study reveals that increasing Li2O concentration lowers the ion diffusion coefficients of Li+,Cl-,and O2-in the electrolyte,which has negative effect on the transport property of the system.A thorough analysis of the ligand structures formed by various components in the molten salt was conducted,including radial distribution functions and angular distribution functions.The analysis reveals that oxygen ions compete with chloride ions for coordination with cations.This competitive interaction has a significant impact on the coordination between Li-Cl and U-Cl elements,thereby influencing the microstructure.The analysis of electronic structures shows that the addition of Li2O affects the charge transfer among lithium,uranium,and chlorine,impacting the bond strength between anions and cations.Finally,the calculation of redox potential shows that an appropriate concentration of Li2O is beneficial to the electrochemical reduction process.The research results provide a theoretical basis for the design of molten salts in the electrolytic reduction process.展开更多
A S 2O 2- 8/ZrO 2 Al 2O 3 type solid superacid catalyst was prepared from ZrOCl 2·8H 2O, AlCl 3· 6H 2O and (NH 4) 2S 2O 8 by coprecipitation, maceration and calcination processes. Their crystal structures an...A S 2O 2- 8/ZrO 2 Al 2O 3 type solid superacid catalyst was prepared from ZrOCl 2·8H 2O, AlCl 3· 6H 2O and (NH 4) 2S 2O 8 by coprecipitation, maceration and calcination processes. Their crystal structures and acidities were determined by XRD and Hammett method, respectively. The activity of the catalyst was studied as function of Al 2O 3 content, calcination temperature and time in the esterification of acetic acid with butanol, and a conversion of 96 5% was obtained. The catalyst gave also higher yields in syntheses of ketals and acetals: cyclohexanone ethylene ketal(86 2%), acetophenone ethylene ketal(78 5%), acetylacetic ester ketal(88 5%), benzaldehyde glycol acetal(76 3%). The chemical structures of the products were confirmed by IR spectra.展开更多
摘要针对光固化Al2O3陶瓷在脱脂烧结后易形成孔洞、力学性能差的问题,系统研究了石墨烯添加对陶瓷浆料流变性、沉降性、固化行为及烧结体力学性能的影响。采用γ-缩水甘油醚氧丙基三甲氧基硅烷(KH560)对Al2O3粉体进行表面改性,并加入不同含量的石墨烯,制备高固相、低粘度的光固化浆料。通过傅里叶红外光谱、旋转流变仪、沉降试验及Beer-Lambert模型分析,优化了浆料配方与光固化工艺参数。结果表明:当KH560含量为2.5wt%、石墨烯含量为0.01wt%时,浆料粘度最低、沉降分层最少;在曝光时间4 s条件下,添加0.01wt%石墨烯的浆料透射深度为382μm,临界曝光能量为44.3 m J/cm2。经1750℃烧结后,陶瓷零件致密度达99.7%,弯曲强度为27.61 MPa,维氏硬度为13.45GPa。石墨烯通过位阻效应及裂纹偏转机制有效促进了烧结致密化并改善了力学性能。本研究为光固化增材制造高致密、高性能氧化铝陶瓷提供了试验依据。
基金the financial support from the 261Project of MIIT and Natural Science Foundation of Jiangsu Province(No.BK20240179)。
摘要The ineluctable introduction of lithium salt to polymer solid-state electrolytes incurs a compromise between strength,ionic conductivity,and thickness.Here,we propose Al2O3-coated polyimide(AO/PI)porous film as a high-strength substrate to support fast-ion-conducting polymer-in-salt(PIS)solid-state electrolytes,aiming to suppress lithium dendrite growth and improve full-cell performance.The Al2O3coating layer not only refines the wettability of polyimide porous film to PIS,but also performs as a high modulus protective layer to suppress the growth of lithium dendrites.The resulting PI/AO@PIS exhibits a small thickness of only 35μm with an outstanding tensile strength of 11.3 MPa and Young's modulus of 537.6 MPa.In addition,the PI/AO@PIS delivers a high ionic conductivity of 0.1 m S/cm at 25°C.As a result,the PI/AO@PIS enables symmetric Li cells to achieve exceptional cyclability for over 1000 h at 0.1 m A/cm2without noticeable lithium dendrite formation.Moreover,the PI/AO@PIS-based LiFePO4||Li full cells demonstrate outstanding rate performance(125.7 m Ah/g at 5 C)and impressive cycling stability(96.1%capacity retention at 1 C after 200 cycles).This work highlights the efficacy of enhancing the mechanical properties of polymer matrices and extending cell performance through the incorporation of a dense inorganic interface layer.
基金financial support provided by the National Natural Science Foundation of China(22476130 and 12205190)。
摘要Electrolytic reduction is a crucial process during the pyroprocessing of oxide spent fuel.This paper investigates the effects of different concentrations of Li2O on the properties of the LiCl-UCl3-Li2O molten salt system during electrolytic reduction using first-principles molecular dynamics simulations.The study reveals that increasing Li2O concentration lowers the ion diffusion coefficients of Li+,Cl-,and O2-in the electrolyte,which has negative effect on the transport property of the system.A thorough analysis of the ligand structures formed by various components in the molten salt was conducted,including radial distribution functions and angular distribution functions.The analysis reveals that oxygen ions compete with chloride ions for coordination with cations.This competitive interaction has a significant impact on the coordination between Li-Cl and U-Cl elements,thereby influencing the microstructure.The analysis of electronic structures shows that the addition of Li2O affects the charge transfer among lithium,uranium,and chlorine,impacting the bond strength between anions and cations.Finally,the calculation of redox potential shows that an appropriate concentration of Li2O is beneficial to the electrochemical reduction process.The research results provide a theoretical basis for the design of molten salts in the electrolytic reduction process.
摘要A S 2O 2- 8/ZrO 2 Al 2O 3 type solid superacid catalyst was prepared from ZrOCl 2·8H 2O, AlCl 3· 6H 2O and (NH 4) 2S 2O 8 by coprecipitation, maceration and calcination processes. Their crystal structures and acidities were determined by XRD and Hammett method, respectively. The activity of the catalyst was studied as function of Al 2O 3 content, calcination temperature and time in the esterification of acetic acid with butanol, and a conversion of 96 5% was obtained. The catalyst gave also higher yields in syntheses of ketals and acetals: cyclohexanone ethylene ketal(86 2%), acetophenone ethylene ketal(78 5%), acetylacetic ester ketal(88 5%), benzaldehyde glycol acetal(76 3%). The chemical structures of the products were confirmed by IR spectra.