A first-principles study was reported based on density functional theory of hydrogen vacancy,metal dopants,metal dopant-vacancy complex in LiBH4,a promising material for hydrogen storage.The formation of H vacancy and...A first-principles study was reported based on density functional theory of hydrogen vacancy,metal dopants,metal dopant-vacancy complex in LiBH4,a promising material for hydrogen storage.The formation of H vacancy and metal doping in LiBH4 is difficult,and their concentrations are low.The presence of one kind of defect is helpful to the formation of other kind of defect.Based on the analysis of electronic structure,the improvement of the dehydrogenating kinetics of LiBH4 by metal catalysts is due to the weaker bonding of B—H and the new metal-like system,which makes H atom diffuse easily;H vacancy accounts for a trace amount of BH3 release during the decomposing process of LiBH4;metal dopant weakens the strength of B—H bonds,which reduces the dehydriding temperature of LiBH4.The roles of metal and vacancy in the metal dopant-vacancy complex can be added in LiBH4 system.展开更多
The development of a high-performing pseudocapacitor requires a comprehensive understanding of electrode materials from the aspects of electron transfer and electrolyte ion adsorption and diffusion.Herein,these factor...The development of a high-performing pseudocapacitor requires a comprehensive understanding of electrode materials from the aspects of electron transfer and electrolyte ion adsorption and diffusion.Herein,these factors are considered over the prototype TiO_(2),and a high pseudocapacitance is achieved via the introduction of various defects,i.e.,oxygen defect(V_(O))and co-doped defect(V_(O)+N_(O)).The study is based on joint explorations of first-principle calculations and the transfer matrix method.Relative to pristine TiO_(2)(300 F g^(-1)),defective TiO_(2) produces pseudocapacitance as high as 1700 F g^(-1).Moreover,defects induce small barriers for electron transmission caused by surface band bending.The climbing image nudged elastic band diffusion of H ions displays a much higher barrier in TiO_(2)-V_(O) than in TiO_(2)-V_(O)+N_(O).Such a result indicates easy H diffusion in the co-doped system.This work provides insights into the adsorption and diffusion of electrolyte ions and the influence of defects on electron transfer.The results are also significant for the design and optimization of electrode materials for the next generation of supercapacitors.展开更多
He defect properties in Sc, Y, Gd, Tb, Dy, Ho, Er and Lu were studied using first-principles calculations based on density functional theory. The results indicate that the formation energy of an interstitial He atom i...He defect properties in Sc, Y, Gd, Tb, Dy, Ho, Er and Lu were studied using first-principles calculations based on density functional theory. The results indicate that the formation energy of an interstitial He atom is smaller than that of a substitutional He atom in all hcp rare-earth metals considered. Furthermore, the tetrahedral interstitial position is more favorable than an octahedral position for He defects. The results are compared with those from bcc and fcc metals.展开更多
基金Project (2009AA05Z105) supported by the High-tech Research and Development Program of ChinaProject (20102173) supported by the Natural Science Foundation of Liaoning Province,China
文摘A first-principles study was reported based on density functional theory of hydrogen vacancy,metal dopants,metal dopant-vacancy complex in LiBH4,a promising material for hydrogen storage.The formation of H vacancy and metal doping in LiBH4 is difficult,and their concentrations are low.The presence of one kind of defect is helpful to the formation of other kind of defect.Based on the analysis of electronic structure,the improvement of the dehydrogenating kinetics of LiBH4 by metal catalysts is due to the weaker bonding of B—H and the new metal-like system,which makes H atom diffuse easily;H vacancy accounts for a trace amount of BH3 release during the decomposing process of LiBH4;metal dopant weakens the strength of B—H bonds,which reduces the dehydriding temperature of LiBH4.The roles of metal and vacancy in the metal dopant-vacancy complex can be added in LiBH4 system.
基金financially supported by the National Key Research and Development Program(2016YFB0901600)Tianjin City Distinguished Young Scholar Fund(17JCJQJC45100)+3 种基金the National Natural Science Foundation of China(21975136 and 21573117)Tianjin Key Research and Development Program(18ZXSZSF00060)the Open Funds from the National Engineering Lab for Mobile Source Emission Control Technology(NELMS2018A01)the project of Shenzhen Science,Technology and Innovation Committee(JCYJ20190808151603654)。
文摘The development of a high-performing pseudocapacitor requires a comprehensive understanding of electrode materials from the aspects of electron transfer and electrolyte ion adsorption and diffusion.Herein,these factors are considered over the prototype TiO_(2),and a high pseudocapacitance is achieved via the introduction of various defects,i.e.,oxygen defect(V_(O))and co-doped defect(V_(O)+N_(O)).The study is based on joint explorations of first-principle calculations and the transfer matrix method.Relative to pristine TiO_(2)(300 F g^(-1)),defective TiO_(2) produces pseudocapacitance as high as 1700 F g^(-1).Moreover,defects induce small barriers for electron transmission caused by surface band bending.The climbing image nudged elastic band diffusion of H ions displays a much higher barrier in TiO_(2)-V_(O) than in TiO_(2)-V_(O)+N_(O).Such a result indicates easy H diffusion in the co-doped system.This work provides insights into the adsorption and diffusion of electrolyte ions and the influence of defects on electron transfer.The results are also significant for the design and optimization of electrode materials for the next generation of supercapacitors.
基金supported by the National Natural Science Foundation of China (Grant No. 10976007)the Fundamental Research Funds for the Central Universities (Grant No. ZYGX2009J040)+1 种基金the Science and Tech-nology Foundation of China Academy of Engineering Physics (Grant No. 2009A0301015)the US Department of Energy, Office of Fusion En-ergy Science (Grant No. DE-AC06-76RLO 1830)
文摘He defect properties in Sc, Y, Gd, Tb, Dy, Ho, Er and Lu were studied using first-principles calculations based on density functional theory. The results indicate that the formation energy of an interstitial He atom is smaller than that of a substitutional He atom in all hcp rare-earth metals considered. Furthermore, the tetrahedral interstitial position is more favorable than an octahedral position for He defects. The results are compared with those from bcc and fcc metals.