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
We present an efficient strategy,that is the co-substitution of Fe^(3+)and Ta^(5+)ions with large radius for Ti^(4+)ion,to enhance energy storage performance of Ba_(2)Bi_(4)Ti_(5)O_(18) film.For the films co-doped wit...We present an efficient strategy,that is the co-substitution of Fe^(3+)and Ta^(5+)ions with large radius for Ti^(4+)ion,to enhance energy storage performance of Ba_(2)Bi_(4)Ti_(5)O_(18) film.For the films co-doped with Fe^(3+)and Ta^(5+)ions,the maximum polarization under the same external electric field is improved because the radius of Fe^(3+)and Ta^(5+)ions is larger than that of Ti^(4+)ion.Moreover,due to the composition and chemical disorder,the relaxor properties are also slightly improved,which can not be achieved by the film doped with Fe^(3+)ions only.What is more,for the films doped with Fe^(3+)ion only,the leakage current density increases greatly due to the charge imbalance,resulting in a significant decrease in breakdown strength.It is worth mentioning that the breakdown strength of Fe^(3+)and Ta^(5+)ions co-doped film does not decrease due to the charge balance.Another important point is the recoverable energy storage density of the films co-doped with Fe^(3+)and Ta^(5+)ions has been greatly improved based on the fact that the maximum external electric field does not decrease and the maximum polarization under the same external electric field increases.On top of that,the hysteresis of the polarization has also been improved.Finally,the co-doped films with Fe^(3+)and Ta^(5+)ions have good frequency and temperature stability.展开更多
Aqueous zinc ion batteries(ZIBs)show great potential in large-scale energy storage systems for their advantages of high safety,low cost,high capacity,and environmental friendliness.However,the poor performance of Zn m...Aqueous zinc ion batteries(ZIBs)show great potential in large-scale energy storage systems for their advantages of high safety,low cost,high capacity,and environmental friendliness.However,the poor performance of Zn metal anode seriously hinders the application of ZIBs.Herein,we use the zinc-ion intercalatable V_(2)O_(5)nH_(2)O(VO)as the interface modification material,for the first time,to on-site build a Zn^(2+)-conductive ZnxV_(2)O_(5)nH_(2)O(ZnVO)interfacial layer via the spontaneous short-circuit reaction between the pre-fabricated VO film and Zn metal foil.Compared with the bare Zn,the ZnVO-coated Zn anode exhibits better electrochemical performances with dendrite-free Zn deposits,lower polarization,higher coulombic efficiency over 99%after long cycles and 10 times higher cycle life,which is confirmed by constructing Zn symmetrical cell and Zn|ZnSO_(4)+Li_(2)SO_(4)|LiFePO_(4) full cell.展开更多
As a type of titanate,the pseudobrookite(MTi_(2)O_(5)/M_(2)TiO_(5))exhibits a low thermal expansion coefficient and thermal conductivity,as well as excellent dielectric and solar spectrum absorption properties.However...As a type of titanate,the pseudobrookite(MTi_(2)O_(5)/M_(2)TiO_(5))exhibits a low thermal expansion coefficient and thermal conductivity,as well as excellent dielectric and solar spectrum absorption properties.However,the pseudobrookite is unstable and prone to decomposing below 1200℃,which limits the practical application of the pseudobrookite.In this paper,the high-entropy pseudobrookite ceramic is synthesized for the first time.The pure high-entropy(Mg,Co,Ni,Zn)Ti_(2)O_(5) with the pseudobrookite structure and the biphasic high-entropy ceramic composed of the highentropy pseudobrookite(Cr,Mn,Fe,Al,Ga)_(2)TiO_(5) and the high-entropy spinel(Cr,Mn,Fe,Al,Ga,Ti)_(3)O_(4) are successfully prepared by the in-situ solid-phase reaction method.The comparison between the theoretical crystal structure of the pseudobrookite and the aberration-corrected scanning transmission electron microscopy(AC-STEM)images of high-entropy(Mg,Co,Ni,Zn)Ti_(2)O_(5) shows that the metal ions(M and Ti ions)are disorderly distributed at the A site and the B site in high-entropy(Mg,Co,Ni,Zn)Ti_(2)O_(5),leading to an unprecedentedly high configurational entropy of high-entropy(Mg,Co,Ni,Zn)Ti_(2)O_(5).The bulk high-entropy(Mg,Co,Ni,Zn)Ti_(2)O_(5) ceramics exhibit a low thermal expansion coefficient of 6.35×10^(−6) K^(−1) in the temperature range of 25-1400℃ and thermal conductivity of 1.840 W·m^(−1)·K^(−1) at room temperature,as well as the excellent thermal stability at 200,600,and 1400℃.Owing to these outstanding properties,high-entropy(Mg,Co,Ni,Zn)Ti_(2)O_(5) is expected to be the promising candidate for high-temperature thermal insulation.This work has further extended the family of different crystal structures of high-entropy ceramics reported to date.展开更多
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This work was financially supported by the National Natural Science Foundation of China(Grant Nos.12074204,11864028,and 11904054)the Natural Science Foundation of Inner Mongolia,China(Grant No.2022ZD06).
文摘We present an efficient strategy,that is the co-substitution of Fe^(3+)and Ta^(5+)ions with large radius for Ti^(4+)ion,to enhance energy storage performance of Ba_(2)Bi_(4)Ti_(5)O_(18) film.For the films co-doped with Fe^(3+)and Ta^(5+)ions,the maximum polarization under the same external electric field is improved because the radius of Fe^(3+)and Ta^(5+)ions is larger than that of Ti^(4+)ion.Moreover,due to the composition and chemical disorder,the relaxor properties are also slightly improved,which can not be achieved by the film doped with Fe^(3+)ions only.What is more,for the films doped with Fe^(3+)ion only,the leakage current density increases greatly due to the charge imbalance,resulting in a significant decrease in breakdown strength.It is worth mentioning that the breakdown strength of Fe^(3+)and Ta^(5+)ions co-doped film does not decrease due to the charge balance.Another important point is the recoverable energy storage density of the films co-doped with Fe^(3+)and Ta^(5+)ions has been greatly improved based on the fact that the maximum external electric field does not decrease and the maximum polarization under the same external electric field increases.On top of that,the hysteresis of the polarization has also been improved.Finally,the co-doped films with Fe^(3+)and Ta^(5+)ions have good frequency and temperature stability.
基金supported by the National Natural Science Foundation(51772115)the National Key Research and Development Program of China(2018YFE0206900)the Hubei Provincial Natural Science Foundation(2019CFA002)。
文摘Aqueous zinc ion batteries(ZIBs)show great potential in large-scale energy storage systems for their advantages of high safety,low cost,high capacity,and environmental friendliness.However,the poor performance of Zn metal anode seriously hinders the application of ZIBs.Herein,we use the zinc-ion intercalatable V_(2)O_(5)nH_(2)O(VO)as the interface modification material,for the first time,to on-site build a Zn^(2+)-conductive ZnxV_(2)O_(5)nH_(2)O(ZnVO)interfacial layer via the spontaneous short-circuit reaction between the pre-fabricated VO film and Zn metal foil.Compared with the bare Zn,the ZnVO-coated Zn anode exhibits better electrochemical performances with dendrite-free Zn deposits,lower polarization,higher coulombic efficiency over 99%after long cycles and 10 times higher cycle life,which is confirmed by constructing Zn symmetrical cell and Zn|ZnSO_(4)+Li_(2)SO_(4)|LiFePO_(4) full cell.
基金the National Natural Science Foundation of China(No.52172072).
文摘As a type of titanate,the pseudobrookite(MTi_(2)O_(5)/M_(2)TiO_(5))exhibits a low thermal expansion coefficient and thermal conductivity,as well as excellent dielectric and solar spectrum absorption properties.However,the pseudobrookite is unstable and prone to decomposing below 1200℃,which limits the practical application of the pseudobrookite.In this paper,the high-entropy pseudobrookite ceramic is synthesized for the first time.The pure high-entropy(Mg,Co,Ni,Zn)Ti_(2)O_(5) with the pseudobrookite structure and the biphasic high-entropy ceramic composed of the highentropy pseudobrookite(Cr,Mn,Fe,Al,Ga)_(2)TiO_(5) and the high-entropy spinel(Cr,Mn,Fe,Al,Ga,Ti)_(3)O_(4) are successfully prepared by the in-situ solid-phase reaction method.The comparison between the theoretical crystal structure of the pseudobrookite and the aberration-corrected scanning transmission electron microscopy(AC-STEM)images of high-entropy(Mg,Co,Ni,Zn)Ti_(2)O_(5) shows that the metal ions(M and Ti ions)are disorderly distributed at the A site and the B site in high-entropy(Mg,Co,Ni,Zn)Ti_(2)O_(5),leading to an unprecedentedly high configurational entropy of high-entropy(Mg,Co,Ni,Zn)Ti_(2)O_(5).The bulk high-entropy(Mg,Co,Ni,Zn)Ti_(2)O_(5) ceramics exhibit a low thermal expansion coefficient of 6.35×10^(−6) K^(−1) in the temperature range of 25-1400℃ and thermal conductivity of 1.840 W·m^(−1)·K^(−1) at room temperature,as well as the excellent thermal stability at 200,600,and 1400℃.Owing to these outstanding properties,high-entropy(Mg,Co,Ni,Zn)Ti_(2)O_(5) is expected to be the promising candidate for high-temperature thermal insulation.This work has further extended the family of different crystal structures of high-entropy ceramics reported to date.
