Na_(2)Ti_(3)O_(7)and Na_(2)Ti_(6)O_(13)are two typical titanate-based sodium-storage materials,featuring the high theoretical capacity and favorable structure stability,respectively.Regulating the ratio of them in the...Na_(2)Ti_(3)O_(7)and Na_(2)Ti_(6)O_(13)are two typical titanate-based sodium-storage materials,featuring the high theoretical capacity and favorable structure stability,respectively.Regulating the ratio of them in the composite material is the key to strengthen its electrochemical characteristics.Herein,based on the high specific surface area and abundant surface functional groups of carbon dots(CDs),sodium titanate precursors containing CDs were in situ prepared by one-step hydrothermal method.After the thermal conversion of the precursors,a composite material(NNTO/C)of Na_(2)Ti_(3)O_(7)and Na_(2)Ti_(6)O_(13)was obtained,containing conductive carbon derived from CDs.The introduc⁃tion of conductive carbon not only adjusts the composition ratio of the mixed phases,but also provides a small charge transfer impedance(Rct,7.48Ω)and a big specific surface area(100.8 m^(2)/g).As a result,NNTO/C composites exhibit better sodium storage behavior while playing the synergistic interaction of mixed phases.When employed as the anode,after 200 cycles at 0.05 A/g,NNTO/C still maintains a specific capacity of 143.8 mA‧h/g.After 400 cycles at 1.00 A/g,the specific capacity remains as high as 108 mA‧h/g.This study suggests an innovative thinking for designing two-phase structures of electrode materials and the greater use of CDs in electrochemical energy storage.展开更多
The microwave absorption properties of Ti_(2)O_(3)were systematically investigated.Experimental results indicate that Ti_(2)O_(3)has microwave absorption performance with a minimum reflection loss value of-37.6 d B at...The microwave absorption properties of Ti_(2)O_(3)were systematically investigated.Experimental results indicate that Ti_(2)O_(3)has microwave absorption performance with a minimum reflection loss value of-37.6 d B at 18.6 GHz and an effective absorption bandwidth(RL<-10 d B)of 2 GHz.Further,vacancy defects were introduced into Ti_(2)O_(3)by carbothermal reduction.Interestingly,the effective absorption bandwidth of Ti_(2)O_(3)with vacancy defects reach 3.2 GHz.First-principles calculations provide evidence that vacancy defects result in the changes of electric dipole state,leading to a wider effective absorption bandwidth.These results have significance in understanding the origin of electromagnetic phenomena and developing electromagnetic wave absorption materials.展开更多
The low O^(2-)diffusion rate in the electro-deoxidation of titanium containing compounds by either the OS process or the FFC process leads to a low reaction speed and a low current efficiency.In this study,Ca_(3)Ti_(2...The low O^(2-)diffusion rate in the electro-deoxidation of titanium containing compounds by either the OS process or the FFC process leads to a low reaction speed and a low current efficiency.In this study,Ca_(3)Ti_(2)O_(7) was used as a precursor to improve the reduction speed of titanium.Because of the greater number of"diffusion channels"created in cathode as Ca^(2+) liberates from Ca_(3)Ti_(2)O_(7) precursor in the electrodeoxidation process,the O^(2-)diffusion rate was improved significantly by using Ca_(3)Ti_(2)O_(7) instead of CaTiO3 as precursor.Parallel constant voltage electrolysis(3.2 V)confirms that Ca_(3)Ti_(2)O_(7) and CaTiO3 are reduced simultaneously because of their similar crystal structures.However,the reduction area of Ca_(3)Ti_(2)O_(7) spreads much faster than that of CaTiO3,indicating a difference in the O^(2-) diffusion rate.Constant voltage cyclic voltammetry(CV)and theoretical analysis of the crystal structure were also conducted to compare the differences between Ca_(3)Ti_(2)O_(7) and CaTiO3.The results indicate that using a precursor with a greater number of soluble cations,titanium reduction speed can be greatly improved in the electro-deoxidation process.Finally,a new electrolysis method for converting and recycling excess CaO from the Ca_(3)Ti_(2)O_(7) precursor was proposed.展开更多
Na2Ti3O7 has attracted much attention in the field of anode materials for Na-ion batteries thanks to its non-toxicity and very low working potential of 0.3 V vs Na0/Na+.Building a clearer picture of its formation from...Na2Ti3O7 has attracted much attention in the field of anode materials for Na-ion batteries thanks to its non-toxicity and very low working potential of 0.3 V vs Na0/Na+.Building a clearer picture of its formation from cheap Na_(2)CO_(3) and TiO_(2) starting materials is therefore of obvious interest.Here,we report new insights from an in-situ high temperature X-ray diffraction study conducted from room temperature to 800°C,complemented by ex-situ characterizations.We were thereby able to position the previously reported Na_(4)Ti_(5)O_(12) and Na_(2)Ti_(6)O_(13) intermediate phases in a reaction scheme involving three successive steps and temperature ranges.Shifts and/or broadening of a subset of the Na_(2)Ti_(6)O_(13) reflections suggested a combination of intra-layer disorder with the well-established ordering of successive layers.This in-situ study was carried out on reproducible mixtures of Na_(2)CO_(3) and TiO_(2) in 1:3 molar ratio prepared by spraydrying of mixed aqueous suspensions.Single-phase Na_(2)Ti_(3)O_(7) was obtained after only 8 h at 800°C in air,instead of a minimum of 20 h for a conventional solid-state route using the same precursors.Microstructure analysis revealed~15 mm diameter granules made up from rectangular rods of a fewmm length presenting electrochemical properties in line with expectations.In the absence of grinding or formation of intimate composites with conductive carbon,the specific capacity of 137 m Ah/g at C/5 decreased at higher rates.展开更多
The thermodynamic properties of Fe_(2)Ti_(3)O_(9) and Fe_(2)TiO_(5) were measured by means of the following solid state electrolyte cells:Pt,Fe+"FeO"||ZrO_(2)(CaO)||FeTiO_(3)+Fe_(2)Ti_(3)O_(9)+Fe_(2)O_(3),Pt...The thermodynamic properties of Fe_(2)Ti_(3)O_(9) and Fe_(2)TiO_(5) were measured by means of the following solid state electrolyte cells:Pt,Fe+"FeO"||ZrO_(2)(CaO)||FeTiO_(3)+Fe_(2)Ti_(3)O_(9)+Fe_(2)O_(3),Pt Pt,Fe+"FeOM"||ZrO_(2)(CaO)||FeTiO_(3)+Fe_(2)TiO_(5)+TiO_(2),Pt From the experimental data,the Gibbs energies of formation of Fe_(2)Ti_(3)O_(9) and Fe_(2)TiO_(5) were obtained:△G^(0)_(pr)(kJ·mol^(-1))=3459.7-0.847T,(1053K<T<1153K) △G^(0)_(pb)(kJ·mol^(-1))=-1700.2-0.465T,(1173K<T<1273K) Experimental results fit approximately to those of estimation.展开更多
In this work,flexible photothermal PVA/Ti_(2)O_(3) composite films with different amount(0 wt%,5 wt%,10 wt%,15 wt%)of Ti_(2)O_(3) particles modified by steric acid were prepared by a simple solution casting method.The...In this work,flexible photothermal PVA/Ti_(2)O_(3) composite films with different amount(0 wt%,5 wt%,10 wt%,15 wt%)of Ti_(2)O_(3) particles modified by steric acid were prepared by a simple solution casting method.The microstructures,XRD patterns,FTIR spectra,UV-Vis-NIR spectra thermo-conductivity,thermo-stability and photothermal effects of these composite films were all characterized.These results indicated that Ti_(2)O_(3) particles were well dispersed throughout the polyvinyl alcohol(PVA)matrix in the PVA/Ti_(2)O_(3) composite films.And Ti_(2)O_(3) particles could also effectively improve the photothermal properties of the composite films which exhibited high light absorption and generated a high temperature(about 57.4℃for film with 15 wt%Ti_(2)O_(3) amount)on the surface when it was irradiated by a simulated sunlight source(1 kW/m^(2)).展开更多
Zn_(2)Ti_(3)O_(8),as a new type of anode material for lithium-ion batteries,is attracting enormous attention because of its low cost and excellent safety.Though decent capacities have been reported,the electrochemical...Zn_(2)Ti_(3)O_(8),as a new type of anode material for lithium-ion batteries,is attracting enormous attention because of its low cost and excellent safety.Though decent capacities have been reported,the electrochemical reaction mechanism of Zn_(2)Ti_(3)O_(8)has rarely been studied.In this work,a porous Zn_(2)Ti_(3)O_(8)anode with considerably high capacity(421 mAh/g at 100 mA/g and 209 mAh/g at 5000 mA/g after 1500 cycles)was reported,which is even higher than ever reported titanium-based anodes materials including Li_(4)Ti_(5)O_(12),TiO_(2)and Li_(2)ZnTi_(3)O_(8).Here,for the first time,the accurate theoretical capacity of Zn_(2)Ti_(3)O_(8)was confirmed to be 266.4 mAh/g.It was also found that both intercalation reaction and pseudocapacitance contribute to the actual capacity of Zn_(2)Ti_(3)O_(8),making it possibly higher than the theoretical value.Most importantly,the porous structure of Zn_(2)Ti_(3)O_(8)not only promotes the intercalation reaction,but also induces high pseudocapacitance capacity(225.4 mAh/g),which boosts the reversible capacity.Therefore,it is the outstanding pseudocapacitance capacity of porous Zn_(2)Ti_(3)O_(8)that accounts for high actual capacity exceeding the theoretical one.This work elucidates the superiorities of porous structure and provides an example in designing high-performance electrodes for lithium-ion batteries.展开更多
文摘Na_(2)Ti_(3)O_(7)and Na_(2)Ti_(6)O_(13)are two typical titanate-based sodium-storage materials,featuring the high theoretical capacity and favorable structure stability,respectively.Regulating the ratio of them in the composite material is the key to strengthen its electrochemical characteristics.Herein,based on the high specific surface area and abundant surface functional groups of carbon dots(CDs),sodium titanate precursors containing CDs were in situ prepared by one-step hydrothermal method.After the thermal conversion of the precursors,a composite material(NNTO/C)of Na_(2)Ti_(3)O_(7)and Na_(2)Ti_(6)O_(13)was obtained,containing conductive carbon derived from CDs.The introduc⁃tion of conductive carbon not only adjusts the composition ratio of the mixed phases,but also provides a small charge transfer impedance(Rct,7.48Ω)and a big specific surface area(100.8 m^(2)/g).As a result,NNTO/C composites exhibit better sodium storage behavior while playing the synergistic interaction of mixed phases.When employed as the anode,after 200 cycles at 0.05 A/g,NNTO/C still maintains a specific capacity of 143.8 mA‧h/g.After 400 cycles at 1.00 A/g,the specific capacity remains as high as 108 mA‧h/g.This study suggests an innovative thinking for designing two-phase structures of electrode materials and the greater use of CDs in electrochemical energy storage.
基金the National Natural Science Foundation of China(Nos.52071071,51431005,51571056,51771048 and 51601033)the Liao Ning Revitalization Talents Program(No.XLYC1802023)the Fundamental Research Funds for the Central Universities of China(Nos.N180204011 and N180204013)。
文摘The microwave absorption properties of Ti_(2)O_(3)were systematically investigated.Experimental results indicate that Ti_(2)O_(3)has microwave absorption performance with a minimum reflection loss value of-37.6 d B at 18.6 GHz and an effective absorption bandwidth(RL<-10 d B)of 2 GHz.Further,vacancy defects were introduced into Ti_(2)O_(3)by carbothermal reduction.Interestingly,the effective absorption bandwidth of Ti_(2)O_(3)with vacancy defects reach 3.2 GHz.First-principles calculations provide evidence that vacancy defects result in the changes of electric dipole state,leading to a wider effective absorption bandwidth.These results have significance in understanding the origin of electromagnetic phenomena and developing electromagnetic wave absorption materials.
基金the National Natural Science Foundation of China(Nos.51604255 and U1702251)。
文摘The low O^(2-)diffusion rate in the electro-deoxidation of titanium containing compounds by either the OS process or the FFC process leads to a low reaction speed and a low current efficiency.In this study,Ca_(3)Ti_(2)O_(7) was used as a precursor to improve the reduction speed of titanium.Because of the greater number of"diffusion channels"created in cathode as Ca^(2+) liberates from Ca_(3)Ti_(2)O_(7) precursor in the electrodeoxidation process,the O^(2-)diffusion rate was improved significantly by using Ca_(3)Ti_(2)O_(7) instead of CaTiO3 as precursor.Parallel constant voltage electrolysis(3.2 V)confirms that Ca_(3)Ti_(2)O_(7) and CaTiO3 are reduced simultaneously because of their similar crystal structures.However,the reduction area of Ca_(3)Ti_(2)O_(7) spreads much faster than that of CaTiO3,indicating a difference in the O^(2-) diffusion rate.Constant voltage cyclic voltammetry(CV)and theoretical analysis of the crystal structure were also conducted to compare the differences between Ca_(3)Ti_(2)O_(7) and CaTiO3.The results indicate that using a precursor with a greater number of soluble cations,titanium reduction speed can be greatly improved in the electro-deoxidation process.Finally,a new electrolysis method for converting and recycling excess CaO from the Ca_(3)Ti_(2)O_(7) precursor was proposed.
基金supported by the Walloon Region under the “PE PlanMarshall2.vert”program(BATWAL–1318146)。
文摘Na2Ti3O7 has attracted much attention in the field of anode materials for Na-ion batteries thanks to its non-toxicity and very low working potential of 0.3 V vs Na0/Na+.Building a clearer picture of its formation from cheap Na_(2)CO_(3) and TiO_(2) starting materials is therefore of obvious interest.Here,we report new insights from an in-situ high temperature X-ray diffraction study conducted from room temperature to 800°C,complemented by ex-situ characterizations.We were thereby able to position the previously reported Na_(4)Ti_(5)O_(12) and Na_(2)Ti_(6)O_(13) intermediate phases in a reaction scheme involving three successive steps and temperature ranges.Shifts and/or broadening of a subset of the Na_(2)Ti_(6)O_(13) reflections suggested a combination of intra-layer disorder with the well-established ordering of successive layers.This in-situ study was carried out on reproducible mixtures of Na_(2)CO_(3) and TiO_(2) in 1:3 molar ratio prepared by spraydrying of mixed aqueous suspensions.Single-phase Na_(2)Ti_(3)O_(7) was obtained after only 8 h at 800°C in air,instead of a minimum of 20 h for a conventional solid-state route using the same precursors.Microstructure analysis revealed~15 mm diameter granules made up from rectangular rods of a fewmm length presenting electrochemical properties in line with expectations.In the absence of grinding or formation of intimate composites with conductive carbon,the specific capacity of 137 m Ah/g at C/5 decreased at higher rates.
基金Supported by the National Natural Science Foundation of Chinathe Committee of Science and Technology of Liaoning Province and the State Education Committee of China。
文摘The thermodynamic properties of Fe_(2)Ti_(3)O_(9) and Fe_(2)TiO_(5) were measured by means of the following solid state electrolyte cells:Pt,Fe+"FeO"||ZrO_(2)(CaO)||FeTiO_(3)+Fe_(2)Ti_(3)O_(9)+Fe_(2)O_(3),Pt Pt,Fe+"FeOM"||ZrO_(2)(CaO)||FeTiO_(3)+Fe_(2)TiO_(5)+TiO_(2),Pt From the experimental data,the Gibbs energies of formation of Fe_(2)Ti_(3)O_(9) and Fe_(2)TiO_(5) were obtained:△G^(0)_(pr)(kJ·mol^(-1))=3459.7-0.847T,(1053K<T<1153K) △G^(0)_(pb)(kJ·mol^(-1))=-1700.2-0.465T,(1173K<T<1273K) Experimental results fit approximately to those of estimation.
基金Funded by the Youth Backbone Teacher Training Plan in University of Henan Province(No.21220028)Science and Technology Research Project of Henan Province(No.242102321066)+2 种基金Natural Science Foundation of Henan Province(No.232300420312)Henan University of Technology Young Backbone Teacher Training Plan(No.21421260)the Innovation Training Program for College Students in Henan Province(No.202310463046)。
文摘In this work,flexible photothermal PVA/Ti_(2)O_(3) composite films with different amount(0 wt%,5 wt%,10 wt%,15 wt%)of Ti_(2)O_(3) particles modified by steric acid were prepared by a simple solution casting method.The microstructures,XRD patterns,FTIR spectra,UV-Vis-NIR spectra thermo-conductivity,thermo-stability and photothermal effects of these composite films were all characterized.These results indicated that Ti_(2)O_(3) particles were well dispersed throughout the polyvinyl alcohol(PVA)matrix in the PVA/Ti_(2)O_(3) composite films.And Ti_(2)O_(3) particles could also effectively improve the photothermal properties of the composite films which exhibited high light absorption and generated a high temperature(about 57.4℃for film with 15 wt%Ti_(2)O_(3) amount)on the surface when it was irradiated by a simulated sunlight source(1 kW/m^(2)).
基金the support of Project Supported by Keypoint Research and Invention in Shaanxi Province of China(No.2020GY-270)Service local special plan project of Education Department of Shaanxi Province(No.19JC009)。
文摘Zn_(2)Ti_(3)O_(8),as a new type of anode material for lithium-ion batteries,is attracting enormous attention because of its low cost and excellent safety.Though decent capacities have been reported,the electrochemical reaction mechanism of Zn_(2)Ti_(3)O_(8)has rarely been studied.In this work,a porous Zn_(2)Ti_(3)O_(8)anode with considerably high capacity(421 mAh/g at 100 mA/g and 209 mAh/g at 5000 mA/g after 1500 cycles)was reported,which is even higher than ever reported titanium-based anodes materials including Li_(4)Ti_(5)O_(12),TiO_(2)and Li_(2)ZnTi_(3)O_(8).Here,for the first time,the accurate theoretical capacity of Zn_(2)Ti_(3)O_(8)was confirmed to be 266.4 mAh/g.It was also found that both intercalation reaction and pseudocapacitance contribute to the actual capacity of Zn_(2)Ti_(3)O_(8),making it possibly higher than the theoretical value.Most importantly,the porous structure of Zn_(2)Ti_(3)O_(8)not only promotes the intercalation reaction,but also induces high pseudocapacitance capacity(225.4 mAh/g),which boosts the reversible capacity.Therefore,it is the outstanding pseudocapacitance capacity of porous Zn_(2)Ti_(3)O_(8)that accounts for high actual capacity exceeding the theoretical one.This work elucidates the superiorities of porous structure and provides an example in designing high-performance electrodes for lithium-ion batteries.
