The orthorhombic CuNb_(2)O_(6)(O-CNO)is established as a competitive anode for lithium-ion capacitors(LICs)owing to its attractive compositional/structural merits.However,the high-temperature synthesis(>900℃)and c...The orthorhombic CuNb_(2)O_(6)(O-CNO)is established as a competitive anode for lithium-ion capacitors(LICs)owing to its attractive compositional/structural merits.However,the high-temperature synthesis(>900℃)and controversial charge-storage mechanism always limit its applications.Herein,we develop a low-temperature strategy to fabricate a nano-blocks-constructed hierarchical accordional O-CNO framework by employing multilayered Nb_(2)CT_(x)as the niobium source.The intrinsic stress-induced formation/transformation mechanism of the monoclinic CuNb_(2)O_(6)to O-CNO is tentatively put forward.Furthermore,the integrated phase conversion and solid solution lithium-storage mechanism is reasonably unveiled with comprehensive in(ex)situ characterizations.Thanks to its unique structural merits and lithium-storage process,the resulted O-CNO anode is endowed with a large capacity of 150.3 mAh g^(-1)at 2.0 A g^(-1),along with long-duration cycling behaviors.Furthermore,the constructed O-CNO-based LICs exhibit a high energy(138.9 Wh kg^(-1))and power(4.0 kW kg^(-1))densities with a modest cycling stability(15.8%capacity degradation after 3000 consecutive cycles).More meaningfully,the in-depth insights into the formation and charge-storage process here can promote the extensive development of binary metal Nb-based oxides for advanced LICs.展开更多
As a promising anode material for magnesium ion rechargeable batteries,magnesium metavanadate(MgV_(2)O_(6))has attracted considerable research interest in recent years.A MgV_(2)O_(6)sample was synthesized via a facile...As a promising anode material for magnesium ion rechargeable batteries,magnesium metavanadate(MgV_(2)O_(6))has attracted considerable research interest in recent years.A MgV_(2)O_(6)sample was synthesized via a facile solid-state reaction by multistep-firing stoichiometric mixtures of MgO and V2O5 powder under an air atmosphere.The solid-state phase transition fromα-MgV_(2)O_(6)toβ-MgV_(2)O_(6)occurred at 841 K and the enthalpy change was 4.37±0.04 kJ/mol.The endothermic effect at 1014 K and the enthalpy change was 26.54±0.26 kJ/mol,which is related to the incongruent melting ofβ-MgV_(2)O_(6).In situ XRD was performed to investigate phase transition of the as-prepared MgV_(2)O_(6)at high temperatures.The cell parameters obtained by Rietveld refinement indicated that it crystallizes in a monoclinic system with the C2/m space group,and the lattice parameters of a=9.280 A°,b=3.501 A°,c=6.731 A°,β=111.76°.The solid-state phase transition fromα-MgV_(2)O_(6)toβ-MgV_(2)O_(6)was further studied by thermal kinetics,indicating that this process is controlled first by a fibril-like mechanism and then by a spherulitic-type mechanism with an increasing heating rate.Additionally,the enthalpy change of MgV_(2)O_(6)at high temperatures was measured utilizing the drop calorimetry,heat capacity was calculated and given as:Cp=208.3+0.03583T-4809000T^(−2)(298-923 K)(J mol^(−1)K^(−1)),the high-temperature heat capacity can be used to calculate Gibbs free energy of MgV_(2)O_(6)at high temperatures.展开更多
A glass frit containing Li_(2)O-MgO-ZnO-B_(2)O_(3)-SiO_(2)component was used to explore the low-temperature sintering behaviors and microwave dielectric characteristics of tri-rutile MgTa_(2)O_(6)ceramics in this stud...A glass frit containing Li_(2)O-MgO-ZnO-B_(2)O_(3)-SiO_(2)component was used to explore the low-temperature sintering behaviors and microwave dielectric characteristics of tri-rutile MgTa_(2)O_(6)ceramics in this study.The good low-firing effects are presented due to the high matching relevance between Li_(2)O-MgO-ZnO-B_(2)O_(3)-SiO_(2)glass and MgTa_(2)O_(6)ceramics.The pure tri-rutile MgTa_(2)O_(6)structure remains unchanged,and high sintering compactness can also be achieved at 1150℃.We found that the Li_(2)O-MgO-ZnO-B_(2)O_(3)-SiO_(2)glass not only greatly improves the low-temperature sintering characteristics of MgTa_(2)O_(6)ceramics but also maintains a high(quality factor(Q)×resonance frequency(f))value while still improving the temperature stability.Typically,great microwave dielectric characteristics when added with 2wt%Li_(2)O-MgO-ZnO-B_(2)O_(3)-SiO_(2)glass can be achieved at 1150℃:dielectric constant,ε_(r)=26.1;Q×f=34267 GHz;temperature coefficient of resonance frequency,τ_(f)=-8.7×10^(-6)/℃.展开更多
基金financially supported by the National Natural Science Foundation of China(No.52072151,52171211,52102253,52271218,and U22A20145)Taishan Scholars(No.ts201712050)+1 种基金Jinan Independent Innovative Team(2020GXRC015)Major Program of Shandong Province Natural Science Foundation(ZR2021ZD05)
文摘The orthorhombic CuNb_(2)O_(6)(O-CNO)is established as a competitive anode for lithium-ion capacitors(LICs)owing to its attractive compositional/structural merits.However,the high-temperature synthesis(>900℃)and controversial charge-storage mechanism always limit its applications.Herein,we develop a low-temperature strategy to fabricate a nano-blocks-constructed hierarchical accordional O-CNO framework by employing multilayered Nb_(2)CT_(x)as the niobium source.The intrinsic stress-induced formation/transformation mechanism of the monoclinic CuNb_(2)O_(6)to O-CNO is tentatively put forward.Furthermore,the integrated phase conversion and solid solution lithium-storage mechanism is reasonably unveiled with comprehensive in(ex)situ characterizations.Thanks to its unique structural merits and lithium-storage process,the resulted O-CNO anode is endowed with a large capacity of 150.3 mAh g^(-1)at 2.0 A g^(-1),along with long-duration cycling behaviors.Furthermore,the constructed O-CNO-based LICs exhibit a high energy(138.9 Wh kg^(-1))and power(4.0 kW kg^(-1))densities with a modest cycling stability(15.8%capacity degradation after 3000 consecutive cycles).More meaningfully,the in-depth insights into the formation and charge-storage process here can promote the extensive development of binary metal Nb-based oxides for advanced LICs.
基金supported by the National Key R&D Program of China(2018YFC1900500)the Graduate Scientific Research and Innovation Foundation of Chongqing,China(Grant No.CYB20002).
文摘As a promising anode material for magnesium ion rechargeable batteries,magnesium metavanadate(MgV_(2)O_(6))has attracted considerable research interest in recent years.A MgV_(2)O_(6)sample was synthesized via a facile solid-state reaction by multistep-firing stoichiometric mixtures of MgO and V2O5 powder under an air atmosphere.The solid-state phase transition fromα-MgV_(2)O_(6)toβ-MgV_(2)O_(6)occurred at 841 K and the enthalpy change was 4.37±0.04 kJ/mol.The endothermic effect at 1014 K and the enthalpy change was 26.54±0.26 kJ/mol,which is related to the incongruent melting ofβ-MgV_(2)O_(6).In situ XRD was performed to investigate phase transition of the as-prepared MgV_(2)O_(6)at high temperatures.The cell parameters obtained by Rietveld refinement indicated that it crystallizes in a monoclinic system with the C2/m space group,and the lattice parameters of a=9.280 A°,b=3.501 A°,c=6.731 A°,β=111.76°.The solid-state phase transition fromα-MgV_(2)O_(6)toβ-MgV_(2)O_(6)was further studied by thermal kinetics,indicating that this process is controlled first by a fibril-like mechanism and then by a spherulitic-type mechanism with an increasing heating rate.Additionally,the enthalpy change of MgV_(2)O_(6)at high temperatures was measured utilizing the drop calorimetry,heat capacity was calculated and given as:Cp=208.3+0.03583T-4809000T^(−2)(298-923 K)(J mol^(−1)K^(−1)),the high-temperature heat capacity can be used to calculate Gibbs free energy of MgV_(2)O_(6)at high temperatures.
基金This study is supported by the National Key Research and Development Program of China(No.2022YFB2807405)the Qinchuangyuan Citing High-level Innovation and Entrepreneurship Talent Projects(No.QCYRCXM-2022-40)+2 种基金the National Natural Science Foundation of China(Nos.U2341263 and 62371366)Open project of Yunnan Precious Metals Laboratory Co.,Ltd(No.YPML-2023050246)Innovation Capability Support Program of Shaanxi,China(Nos.2023-CX-PT-30 and 2022TD-28).
文摘A glass frit containing Li_(2)O-MgO-ZnO-B_(2)O_(3)-SiO_(2)component was used to explore the low-temperature sintering behaviors and microwave dielectric characteristics of tri-rutile MgTa_(2)O_(6)ceramics in this study.The good low-firing effects are presented due to the high matching relevance between Li_(2)O-MgO-ZnO-B_(2)O_(3)-SiO_(2)glass and MgTa_(2)O_(6)ceramics.The pure tri-rutile MgTa_(2)O_(6)structure remains unchanged,and high sintering compactness can also be achieved at 1150℃.We found that the Li_(2)O-MgO-ZnO-B_(2)O_(3)-SiO_(2)glass not only greatly improves the low-temperature sintering characteristics of MgTa_(2)O_(6)ceramics but also maintains a high(quality factor(Q)×resonance frequency(f))value while still improving the temperature stability.Typically,great microwave dielectric characteristics when added with 2wt%Li_(2)O-MgO-ZnO-B_(2)O_(3)-SiO_(2)glass can be achieved at 1150℃:dielectric constant,ε_(r)=26.1;Q×f=34267 GHz;temperature coefficient of resonance frequency,τ_(f)=-8.7×10^(-6)/℃.
