利用对氧缺陷的TiO_2-B材料进行密度泛函理论的计算,阐述了氧空穴对于TiO_2-B材料的电化学性质的影响。计算研究主要聚焦于缺陷材料的锂离子迁移和电子导电性等基本问题。计算结果表明在低锂离子浓度下(x(Li/Ti)≤0.25),相比于无缺陷的T...利用对氧缺陷的TiO_2-B材料进行密度泛函理论的计算,阐述了氧空穴对于TiO_2-B材料的电化学性质的影响。计算研究主要聚焦于缺陷材料的锂离子迁移和电子导电性等基本问题。计算结果表明在低锂离子浓度下(x(Li/Ti)≤0.25),相比于无缺陷的TiO_2-B,氧缺陷TiO_2-B有着更高的插入电压和更低的b轴方向迁移活化能,意味着锂离子的嵌入也更容易,这对于可充电电池的充电过程是有利的。而在高浓度下(x(Li/Ti)=1),锂饱和的氧缺陷TiO_2-B相较于无缺陷的TiO_2-B有着较低的插入电压,更有利于锂离子的脱嵌过程,这对于可充电电池的放电过程也是有利的。电子结构计算表明缺陷材料的禁带宽度在1.0-2.0 e V之间,低于无缺陷的材料的3.0 e V。主要态密度贡献者是Ti-Ov-3d,并且随着氧空穴的增加它的强度也变得更强。这就表明氧缺陷TiO_2-B有更好的电子导电性。展开更多
Mesoporous TiO_2-B/anatase microparticles have been in-situ synthesized from K_2Ti_2O_5 without template.The TiO_2-B phase around the particle surface accelerates the diffusion of charges through the interface,while t...Mesoporous TiO_2-B/anatase microparticles have been in-situ synthesized from K_2Ti_2O_5 without template.The TiO_2-B phase around the particle surface accelerates the diffusion of charges through the interface,while the anatase phase in the core maintains the capacity stability.The heterojunction interface between the main polymorph of anatase and the trace of TiO_2-B exhibits promising lithium ion battery performance.This trace of 5%(by mass) TiO_2-B determined by Raman spectra brings the first discharge capacity of this material to 247 mA · h ·g^(-1),giving 20%improvement compared to the anatase counterpart Stability testing at 1 C reveals that the capacity maintains at 171 mA·h·^(-1),which is better than 162 mA·h·g^(-1) for single phase anatase or 159 mA·h·g^(-1) for TiO_2-B.The mesoporous TiO_2-B/anatase rnicroparticles also show superior rate performance with 100 mA·h·g^(-1) at 40 C,increased by nearly 25%as compared to pure anatase.This opens a possibility of a general design route,which can be applied to other metal oxide electrode materials for rechargeable batteries and supercapacitors.展开更多
TiO2-B was synthesized by solid-state reaction. The structures, surface morphologies and electrochemical performances of TiO2-B were characterized by X-ray diffractometry （XRD）, scanning electron microscopy （SEM） ...TiO2-B was synthesized by solid-state reaction. The structures, surface morphologies and electrochemical performances of TiO2-B were characterized by X-ray diffractometry （XRD）, scanning electron microscopy （SEM） and electrochemical measurement, respectively. The effects of calcining temperature, molar ratio of K2O to TiO2 and calcining time on the characteristics of TiO2-B were investigated. The results show that the calcining time exerts a significant influence on the electrochemical performances of TiO2-B. The TiO2-B is obtained with good crystal structure and suitable size by using K2Ti4O9, which is prepared at 950 ℃for 24 h under the condition of x（K2O）/x（TiO2）=1：3.5. The TiO2-B delivers all initial discharge capacity of 231.6 mA.h/g. And the rate caoacitv is 73.2 mA-h/g at 1 675 mA/g, which suggests that TiO2-B is a promising anode material for the lithium ion batteries.展开更多
This paper reports a simple yet efficient method for the synthesis of hierarchical TiO2-B nanowire@α-Fe2O3 nanothorn core-branch arrays based on a stepwise hydrothermal approach. The as-fabricated hybrid arrays show ...This paper reports a simple yet efficient method for the synthesis of hierarchical TiO2-B nanowire@α-Fe2O3 nanothorn core-branch arrays based on a stepwise hydrothermal approach. The as-fabricated hybrid arrays show impressive performance as a high-capacity anode for lithium-ion batteries. The key design in this study is a core-branch hybrid architecture, which not only provides large surface active sites for lithium ion insertion/extraction, but also enables fast charge transport owing to the reduced diffusion paths for both electrons and lithium ions. The peculiar combination of attributes of TiO2 （good structural stability） and Fe2O3 （large specific capacity） provides the hybrid array electrodes with several desirable electrochemical features： large reversible capacity （-800 mA.h.g^-1 for specific mass capacity and -750 μA.h-cm^-2 for specific areal＂ capacity）, good cycling stability, and high rate capability. The impressive electrochemical performance, together with the facile synthesis procedure, may provide an efficient platform to integrate the TiO2 nanowire@Fe2O3 nanothorn core-branch arrays as a three-dimensional thin film electrode for lithium-ion microbatteries.展开更多
基金supported by the State Key Program of Natural Science Foundation of Tianjin,China(13JCZDJC26800)Foundation of State Key Laboratory of Coal Conversion,China(J15-16-908)Natural Science Foundation of Shanxi Province,China(2013011012-8)~~
文摘利用对氧缺陷的TiO_2-B材料进行密度泛函理论的计算,阐述了氧空穴对于TiO_2-B材料的电化学性质的影响。计算研究主要聚焦于缺陷材料的锂离子迁移和电子导电性等基本问题。计算结果表明在低锂离子浓度下(x(Li/Ti)≤0.25),相比于无缺陷的TiO_2-B,氧缺陷TiO_2-B有着更高的插入电压和更低的b轴方向迁移活化能,意味着锂离子的嵌入也更容易,这对于可充电电池的充电过程是有利的。而在高浓度下(x(Li/Ti)=1),锂饱和的氧缺陷TiO_2-B相较于无缺陷的TiO_2-B有着较低的插入电压,更有利于锂离子的脱嵌过程,这对于可充电电池的放电过程也是有利的。电子结构计算表明缺陷材料的禁带宽度在1.0-2.0 e V之间,低于无缺陷的材料的3.0 e V。主要态密度贡献者是Ti-Ov-3d,并且随着氧空穴的增加它的强度也变得更强。这就表明氧缺陷TiO_2-B有更好的电子导电性。
基金Supported by the Program for Changjiang Scholars and Innovative Research Team in University(PCSIRT 0732)the National Natural Science Foundation of China(21136004,20736002,21176113,20876073)+2 种基金NSFC-RGC(20731160614)China Postdoctoral Science Foundation(20110491407)the National Basic Research Program of China(2009CB623407,2009CB219902 and 2009CB226103)
文摘Mesoporous TiO_2-B/anatase microparticles have been in-situ synthesized from K_2Ti_2O_5 without template.The TiO_2-B phase around the particle surface accelerates the diffusion of charges through the interface,while the anatase phase in the core maintains the capacity stability.The heterojunction interface between the main polymorph of anatase and the trace of TiO_2-B exhibits promising lithium ion battery performance.This trace of 5%(by mass) TiO_2-B determined by Raman spectra brings the first discharge capacity of this material to 247 mA · h ·g^(-1),giving 20%improvement compared to the anatase counterpart Stability testing at 1 C reveals that the capacity maintains at 171 mA·h·^(-1),which is better than 162 mA·h·g^(-1) for single phase anatase or 159 mA·h·g^(-1) for TiO_2-B.The mesoporous TiO_2-B/anatase rnicroparticles also show superior rate performance with 100 mA·h·g^(-1) at 40 C,increased by nearly 25%as compared to pure anatase.This opens a possibility of a general design route,which can be applied to other metal oxide electrode materials for rechargeable batteries and supercapacitors.
基金Project(2007BAE12B01) supported by the National Key Technology R&D Program of China
文摘TiO2-B was synthesized by solid-state reaction. The structures, surface morphologies and electrochemical performances of TiO2-B were characterized by X-ray diffractometry （XRD）, scanning electron microscopy （SEM） and electrochemical measurement, respectively. The effects of calcining temperature, molar ratio of K2O to TiO2 and calcining time on the characteristics of TiO2-B were investigated. The results show that the calcining time exerts a significant influence on the electrochemical performances of TiO2-B. The TiO2-B is obtained with good crystal structure and suitable size by using K2Ti4O9, which is prepared at 950 ℃for 24 h under the condition of x（K2O）/x（TiO2）=1：3.5. The TiO2-B delivers all initial discharge capacity of 231.6 mA.h/g. And the rate caoacitv is 73.2 mA-h/g at 1 675 mA/g, which suggests that TiO2-B is a promising anode material for the lithium ion batteries.
基金This work was supported by the National Natural Science Foundation of China （No. 51102134）, the Natural Science Foundation of Jiangsu Province （No. BK20131349）, the China Postdoctoral Science Foundation （No. 2013M530258）, and the Jiangsu Planned Projects for Postdoctoral Research Funds （No. 1202001B）.
文摘This paper reports a simple yet efficient method for the synthesis of hierarchical TiO2-B nanowire@α-Fe2O3 nanothorn core-branch arrays based on a stepwise hydrothermal approach. The as-fabricated hybrid arrays show impressive performance as a high-capacity anode for lithium-ion batteries. The key design in this study is a core-branch hybrid architecture, which not only provides large surface active sites for lithium ion insertion/extraction, but also enables fast charge transport owing to the reduced diffusion paths for both electrons and lithium ions. The peculiar combination of attributes of TiO2 （good structural stability） and Fe2O3 （large specific capacity） provides the hybrid array electrodes with several desirable electrochemical features： large reversible capacity （-800 mA.h.g^-1 for specific mass capacity and -750 μA.h-cm^-2 for specific areal＂ capacity）, good cycling stability, and high rate capability. The impressive electrochemical performance, together with the facile synthesis procedure, may provide an efficient platform to integrate the TiO2 nanowire@Fe2O3 nanothorn core-branch arrays as a three-dimensional thin film electrode for lithium-ion microbatteries.
