Vanadium oxide cathode materials with stable crystal structure and fast Zn^(2+) storage capabilities are extremely important to achieving outstanding electrochemical performance in aqueous zinc‐ion batteries.In this ...Vanadium oxide cathode materials with stable crystal structure and fast Zn^(2+) storage capabilities are extremely important to achieving outstanding electrochemical performance in aqueous zinc‐ion batteries.In this work,a one‐step hydrothermal method was used to manipulate the bimetallic ion intercalation into the interlayer of vanadium oxide.The pre‐intercalated Cu ions act as pillars to pin the vanadium oxide(V‐O)layers,establishing stabilized two‐dimensional channels for fast Zn^(2+) diffusion.The occupation of Mn ions between V‐O interlayer further expands the layer spacing and increases the concentration of oxygen defects(Od),which boosts the Zn^(2+) diffusion kinetics.As a result,as‐prepared Cu_(0.17)Mn_(0.03)V_(2)O_(5−□)·2.16H_(2)O cathode shows outstanding Zn‐storage capabilities under room‐and lowtemperature environments(e.g.,440.3 mAh g^(−1) at room temperature and 294.3 mAh g^(−1)at−60°C).Importantly,it shows a long cycling life and high capacity retention of 93.4%over 2500 cycles at 2 A g^(−1) at−60°C.Furthermore,the reversible intercalation chemistry mechanisms during discharging/charging processes were revealed via operando X‐ray powder diffraction and ex situ Raman characterizations.The strategy of a couple of 3d transition metal doping provides a solution for the development of superior room‐/lowtemperature vanadium‐based cathode materials.展开更多
V_(3)O_(7)·H_(2)O(VO)is a high capacity cathode material in the field of aqueous zinc ion batteries(AZIBs),but it is limited by slow ion migration and low electrical conductivity.In this paper,polypyridine(PPyd)i...V_(3)O_(7)·H_(2)O(VO)is a high capacity cathode material in the field of aqueous zinc ion batteries(AZIBs),but it is limited by slow ion migration and low electrical conductivity.In this paper,polypyridine(PPyd)intercalated VO with nanoribbon structure was prepared by a simple in-situ pre-intercalation,which is noted VO-PPyd.The total density of states(TDOS)shows that after the pre-intercalation of PPyd,an intermediate energy level appears between the valence band and conduction band,which provides a step that can effectively reduce the band gap and enhance the electron conductivity.Furthermore,the density functional theory(DFT)results found that Zn^(2+)is more easily de-intercalated from the V-O skeleton,which proves that the embeddedness of PPyd improves the diffusion kinetics of Zn^(2+).Electrochemical studies have shown that VO-PPyd cathode materials exhibit excellent rate performance(high specific capacity of 465 and 192 mA h g^(-1)at 0.2 and 10 A g^(-1),respectively)and long-term cycling performance(92.7%capacity retention rate after 5300 cycles),due to their advantages in structure and composition.More importantly,the energy density of VO-PPyd//Zn at 581 and 5806 W kg^(-1)is 375 and 247 W h kg^(-1),respectively.VO-PPyd exhibits excellent electrochemical properties compared to previously reported vanadium based cathodes,which makes it highly competitive in the field of high-performance cathode materials of AZIBs.展开更多
How to effectively improve Zn^(2+)-storage properties is now becoming an urgent issue in the development of high-energy-density aqueous zinc-ion batteries.Here,a new method is proposed to massively increase the electr...How to effectively improve Zn^(2+)-storage properties is now becoming an urgent issue in the development of high-energy-density aqueous zinc-ion batteries.Here,a new method is proposed to massively increase the electrochemical capacity of aqueous Zn/V_(5)O_(12)·6H_(2)Obatteries.By adding a small amount of platinum(Pt,1.5 wt.%)and keeping other factors constant,the V_(5)O_(12)·6H_(2)O-Pt electrodes deliver a much higher specific capacity(440 m Ah g^(-1)at 500 m A g^(-1))than do V_(5)O_(12)·6H_(2)Oelectrodes(270 m Ah g^(-1)at500 m A g^(-1)).The structural and morphological evolution of V_(5)O_(12)·6H_(2)Oduring cycling results in Zn^(2+)ion insertion/extraction and the formation/disappearance of the zinc hydroxyl complex(Zn_(4)SO_(4)(OH)_(6)·5H_(2)O,ZHS),where the latter is closely related to the surface redox reaction,promoting Zn^(2+)ion stripping/plating on the Zn anode and consequently leading to extra electron transfer.Electrochemical tests in the absence of oxygen reveal that the Pt additive has no contribution and is even counterproductive to electric conductivity but favors remarkable enhancement of the pseudocapacitance.Accordingly,it is apparent that a strong causal relationship exists between Pt and the ZHS.In consideration of the catalytic application for oxygen reduction,Pt is expected to play a vital role in enhancing the electrochemical capacity through the pseudo-Zn-air reaction.This finding introduces a new strategy for achieving high-performance aqueous zinc-ion batteries.展开更多
Developing suitable anode materials for potassium-ion batteries(PIBs)remains a great challenge owing to the limited theoretical capacity of active materials and large radius of K+ion(1.38?).To solve these obstacles,by...Developing suitable anode materials for potassium-ion batteries(PIBs)remains a great challenge owing to the limited theoretical capacity of active materials and large radius of K+ion(1.38?).To solve these obstacles,by integrating the principles of multielectron transfer and rational porous crystal framework,we creatively propose the monoclinic Cu_(3)(OH)_(2)V_(2)O_(7)·2H_(2)O(CVO)as a novel anode for PIBs.Furthermore,inspired by the metastable nature of CVO under high temperature/pressure,we skillfully design a facile hydrothermal recrystallization strategy without the phase change and surfactants addition.Thus,for the first time,the porous composite of Cu_(3)(OH)_(2)V_(2)O_(7)·2H_(2)O nanobelts covered in situ by reduced graphene oxide(CVO NBs/r GO)was assembled,greatly improving the deficiencies of CVO.When used as a novel anode for PIBs,CVO NBs/r GO delivers large specific capacity(up to 551.4 m Ah g^(-1)at 50 m A g^(-1)),high-rate capability(215.3 m Ah g^(-1)at 2.5 A g^(-1))and super durability(203.6 m Ah g^(-1)at 500 m A g^(-1)even after 1000 cycles).The outstanding performance can be ascribed to the synergistic merits of desirable structural features of monoclinic CVO nanobelts and the highly conductive graphene 3D network,thus promoting the composite material stability and electrical/ionic conductivity.This work reveals a novel metal vanadate-based anode material for PIBs,would further motivate the subsequent batteries research on M_(3)(OH)_(2)V_(2)O_(7)-n H_(2)O(M;Co,Ni,Cu,Zn),and ultimately expands valuable fundamental understanding on designing other high-performance electrode materials,including the combined strategies of multielectron transfer with rational porous crystal framework,and the composite fabrication of 1D electrode nanostructure with conductive carbon matrix.展开更多
Vanadium oxides,par-ticularly hydrated forms like V_(2)O_(5)·nH_(2)O(VOH),stand out as promising cathode candidates for aqueous zinc ion batteries due to their adjustable layered structure,unique electronic chara...Vanadium oxides,par-ticularly hydrated forms like V_(2)O_(5)·nH_(2)O(VOH),stand out as promising cathode candidates for aqueous zinc ion batteries due to their adjustable layered structure,unique electronic characteristics,and high theoretical capacities.However,challenges such as vanadium dissolution,sluggish Zn^(2+)diffusion kinetics,and low operating voltage still hinder their direct application.In this study,we present a novel vanadium oxide([C_(6)H_(6)N(CH_(3))_(3)]_(1.08)V_(8)O_(20)·0.06H_(2)O,TMPA-VOH),developed by pre-inserting trimethylphenylammonium(TMPA+)cations into VOH.The incorporation of weakly polarized organic cations capitalizes on both ionic pre-intercalation and molecular pre-intercalation effects,resulting in a phase and morphology transition,an expansion of the interlayer distance,extrusion of weakly bonded interlayer water,and a substantial increase in V^(4+)content.These modifications synergistically reduce the electrostatic interactions between Zn^(2+)and the V-O lattice,enhancing structural stability and reaction kinetics during cycling.As a result,TMPA-VOH achieves an elevated open circuit voltage and operation voltage,exhibits a large specific capacity(451 mAh g^(-1)at 0.1 A g^(-1))coupled with high energy efficiency(89%),the significantly-reduced battery polarization,and outstanding rate capability and cycling stability.The concept introduced in this study holds great promise for the development of high-performance oxide-based energy storage materials.展开更多
The magnetic properties of Fe_(72.5)Cu_1Nb_2V_2Si_(13.5)B_9 alloy are investigated from an amorphous to a nanocrystalline and complete crystalline state. The sample annealed at 550℃ for 0.5 h shows a homogeneous nano...The magnetic properties of Fe_(72.5)Cu_1Nb_2V_2Si_(13.5)B_9 alloy are investigated from an amorphous to a nanocrystalline and complete crystalline state. The sample annealed at 550℃ for 0.5 h shows a homogeneous nanocrystalline structure and presents excellent soft magnetic properties. When the specimens were annealed at a temperature above 600℃, the magnetic properties are obviously deteriorated because the grain size grows up, exceeding the exchange length.展开更多
Driven by safety issues,environmental concerns,and high costs,rechargeable aqueous zinc-ion batteries(ZIBs)have received increasing attention in recent years owing to their unique advantages.However,the sluggish kinet...Driven by safety issues,environmental concerns,and high costs,rechargeable aqueous zinc-ion batteries(ZIBs)have received increasing attention in recent years owing to their unique advantages.However,the sluggish kinetics of divalent charge Zn^(2+)in the cathode materials caused by the strong electrostatic interaction and their unsatisfactory cycle life hinder the development of ZIBs.Herein,organic cations and Zn^(2+)ions co-pre-inserted vanadium oxide([N(CH_(3))_(4)]_(0.77),Zn_(0.23))V_(8)O_(20)·3.8H_(2)O are reported as the cathode for ultra-stable aqueous ZIBs,in which the weaker electrostatic interactions between Zn^(2+)and organic ion-pinned vanadium oxide can induce the high reversibility of Zn^(2+)insertion and extraction,thereby improving the cycle life.It is demonstrated that([N(CH_(3))_(4)]_(0.77),Zn_(0.23))V_(8)O_(20)·3.8H_(2)O cathodes deliver a discharge capacity of 181 mA h g^(-1)at8 A g^(-1)and ultra-long life span(99.5%capacity retention after 2000 cycles).A reversible Zn^(2+)/H^(+)ions(de)intercalation storage process and pseudocapacitive charge storage are characterized.The weaker interactions between organic ion and Zn^(2+)open a novel avenue for the design of highly reversible cathode materials with long-term cycling stability.展开更多
基金National Natural Science Foundation of China,Grant/Award Numbers:52372188,51902090,51922008,520721142023 Introduction of studying abroad talent program,the China Postdoctoral Science Foundation,Grant/Award Number:2019 M652546+3 种基金Xinxiang Major Science and Technology Projects,Grant/Award Number:21ZD001Henan Province Postdoctoral Start‐Up Foundation,Grant/Award Number:1901017Henan Center for Outstanding Overseas Scientists,Grant/Award Number:GZS2018003Overseas Expertise Introduction Project for Discipline Innovation,Grant/Award Number:D17007。
文摘Vanadium oxide cathode materials with stable crystal structure and fast Zn^(2+) storage capabilities are extremely important to achieving outstanding electrochemical performance in aqueous zinc‐ion batteries.In this work,a one‐step hydrothermal method was used to manipulate the bimetallic ion intercalation into the interlayer of vanadium oxide.The pre‐intercalated Cu ions act as pillars to pin the vanadium oxide(V‐O)layers,establishing stabilized two‐dimensional channels for fast Zn^(2+) diffusion.The occupation of Mn ions between V‐O interlayer further expands the layer spacing and increases the concentration of oxygen defects(Od),which boosts the Zn^(2+) diffusion kinetics.As a result,as‐prepared Cu_(0.17)Mn_(0.03)V_(2)O_(5−□)·2.16H_(2)O cathode shows outstanding Zn‐storage capabilities under room‐and lowtemperature environments(e.g.,440.3 mAh g^(−1) at room temperature and 294.3 mAh g^(−1)at−60°C).Importantly,it shows a long cycling life and high capacity retention of 93.4%over 2500 cycles at 2 A g^(−1) at−60°C.Furthermore,the reversible intercalation chemistry mechanisms during discharging/charging processes were revealed via operando X‐ray powder diffraction and ex situ Raman characterizations.The strategy of a couple of 3d transition metal doping provides a solution for the development of superior room‐/lowtemperature vanadium‐based cathode materials.
基金supported by the National Natural Science Foundation of China (21676036)the Natural Science Foundation of Chongqing (CSTB2023NSCQ-MSX0580)the Graduate Research and Innovation Foundation of Chongqing (CYB22043 and CYS22073)。
文摘V_(3)O_(7)·H_(2)O(VO)is a high capacity cathode material in the field of aqueous zinc ion batteries(AZIBs),but it is limited by slow ion migration and low electrical conductivity.In this paper,polypyridine(PPyd)intercalated VO with nanoribbon structure was prepared by a simple in-situ pre-intercalation,which is noted VO-PPyd.The total density of states(TDOS)shows that after the pre-intercalation of PPyd,an intermediate energy level appears between the valence band and conduction band,which provides a step that can effectively reduce the band gap and enhance the electron conductivity.Furthermore,the density functional theory(DFT)results found that Zn^(2+)is more easily de-intercalated from the V-O skeleton,which proves that the embeddedness of PPyd improves the diffusion kinetics of Zn^(2+).Electrochemical studies have shown that VO-PPyd cathode materials exhibit excellent rate performance(high specific capacity of 465 and 192 mA h g^(-1)at 0.2 and 10 A g^(-1),respectively)and long-term cycling performance(92.7%capacity retention rate after 5300 cycles),due to their advantages in structure and composition.More importantly,the energy density of VO-PPyd//Zn at 581 and 5806 W kg^(-1)is 375 and 247 W h kg^(-1),respectively.VO-PPyd exhibits excellent electrochemical properties compared to previously reported vanadium based cathodes,which makes it highly competitive in the field of high-performance cathode materials of AZIBs.
基金supported by the National Natural Science Foundation of China(91963210,U1801255,and 51872340)the Basic Scientific Research Fund of Sun Yat-Sen University(grant no.18lgpy06)
文摘How to effectively improve Zn^(2+)-storage properties is now becoming an urgent issue in the development of high-energy-density aqueous zinc-ion batteries.Here,a new method is proposed to massively increase the electrochemical capacity of aqueous Zn/V_(5)O_(12)·6H_(2)Obatteries.By adding a small amount of platinum(Pt,1.5 wt.%)and keeping other factors constant,the V_(5)O_(12)·6H_(2)O-Pt electrodes deliver a much higher specific capacity(440 m Ah g^(-1)at 500 m A g^(-1))than do V_(5)O_(12)·6H_(2)Oelectrodes(270 m Ah g^(-1)at500 m A g^(-1)).The structural and morphological evolution of V_(5)O_(12)·6H_(2)Oduring cycling results in Zn^(2+)ion insertion/extraction and the formation/disappearance of the zinc hydroxyl complex(Zn_(4)SO_(4)(OH)_(6)·5H_(2)O,ZHS),where the latter is closely related to the surface redox reaction,promoting Zn^(2+)ion stripping/plating on the Zn anode and consequently leading to extra electron transfer.Electrochemical tests in the absence of oxygen reveal that the Pt additive has no contribution and is even counterproductive to electric conductivity but favors remarkable enhancement of the pseudocapacitance.Accordingly,it is apparent that a strong causal relationship exists between Pt and the ZHS.In consideration of the catalytic application for oxygen reduction,Pt is expected to play a vital role in enhancing the electrochemical capacity through the pseudo-Zn-air reaction.This finding introduces a new strategy for achieving high-performance aqueous zinc-ion batteries.
基金supported by the National Natural Science Foundation of China(52072118,51772089)the Youth 1000 Talent Program of China+3 种基金the Research and Development Plan of Key Areas in Hunan Province(2019GK2235)the Key Research and Development Program of Ningxia(2020BDE03007)the China Postdoctoral Science Foundation(2019M653649)the Guangdong Basic and Applied Basic Research Fund(2019A1515110518,2019A1515111188,2020B0909030004)。
文摘Developing suitable anode materials for potassium-ion batteries(PIBs)remains a great challenge owing to the limited theoretical capacity of active materials and large radius of K+ion(1.38?).To solve these obstacles,by integrating the principles of multielectron transfer and rational porous crystal framework,we creatively propose the monoclinic Cu_(3)(OH)_(2)V_(2)O_(7)·2H_(2)O(CVO)as a novel anode for PIBs.Furthermore,inspired by the metastable nature of CVO under high temperature/pressure,we skillfully design a facile hydrothermal recrystallization strategy without the phase change and surfactants addition.Thus,for the first time,the porous composite of Cu_(3)(OH)_(2)V_(2)O_(7)·2H_(2)O nanobelts covered in situ by reduced graphene oxide(CVO NBs/r GO)was assembled,greatly improving the deficiencies of CVO.When used as a novel anode for PIBs,CVO NBs/r GO delivers large specific capacity(up to 551.4 m Ah g^(-1)at 50 m A g^(-1)),high-rate capability(215.3 m Ah g^(-1)at 2.5 A g^(-1))and super durability(203.6 m Ah g^(-1)at 500 m A g^(-1)even after 1000 cycles).The outstanding performance can be ascribed to the synergistic merits of desirable structural features of monoclinic CVO nanobelts and the highly conductive graphene 3D network,thus promoting the composite material stability and electrical/ionic conductivity.This work reveals a novel metal vanadate-based anode material for PIBs,would further motivate the subsequent batteries research on M_(3)(OH)_(2)V_(2)O_(7)-n H_(2)O(M;Co,Ni,Cu,Zn),and ultimately expands valuable fundamental understanding on designing other high-performance electrode materials,including the combined strategies of multielectron transfer with rational porous crystal framework,and the composite fabrication of 1D electrode nanostructure with conductive carbon matrix.
基金This work was supported by the National Science Foundation(CBET-1803256)Dr.C.Liu acknowledges the support from National Natural Science Foundation of China(52102277)the Fundamental Research Funds for the Central Universities,conducted by Tongji University.
文摘Vanadium oxides,par-ticularly hydrated forms like V_(2)O_(5)·nH_(2)O(VOH),stand out as promising cathode candidates for aqueous zinc ion batteries due to their adjustable layered structure,unique electronic characteristics,and high theoretical capacities.However,challenges such as vanadium dissolution,sluggish Zn^(2+)diffusion kinetics,and low operating voltage still hinder their direct application.In this study,we present a novel vanadium oxide([C_(6)H_(6)N(CH_(3))_(3)]_(1.08)V_(8)O_(20)·0.06H_(2)O,TMPA-VOH),developed by pre-inserting trimethylphenylammonium(TMPA+)cations into VOH.The incorporation of weakly polarized organic cations capitalizes on both ionic pre-intercalation and molecular pre-intercalation effects,resulting in a phase and morphology transition,an expansion of the interlayer distance,extrusion of weakly bonded interlayer water,and a substantial increase in V^(4+)content.These modifications synergistically reduce the electrostatic interactions between Zn^(2+)and the V-O lattice,enhancing structural stability and reaction kinetics during cycling.As a result,TMPA-VOH achieves an elevated open circuit voltage and operation voltage,exhibits a large specific capacity(451 mAh g^(-1)at 0.1 A g^(-1))coupled with high energy efficiency(89%),the significantly-reduced battery polarization,and outstanding rate capability and cycling stability.The concept introduced in this study holds great promise for the development of high-performance oxide-based energy storage materials.
基金This work is supported by the National Natural Science Foundation of China(No.59671020).
文摘The magnetic properties of Fe_(72.5)Cu_1Nb_2V_2Si_(13.5)B_9 alloy are investigated from an amorphous to a nanocrystalline and complete crystalline state. The sample annealed at 550℃ for 0.5 h shows a homogeneous nanocrystalline structure and presents excellent soft magnetic properties. When the specimens were annealed at a temperature above 600℃, the magnetic properties are obviously deteriorated because the grain size grows up, exceeding the exchange length.
基金supported by the funding from the National Natural Science Foundation of China(grant nos.51902187,52072224,and 51732007)the Natural Science Foundation of Shandong Province(ZR2018BEM010)+3 种基金the Science Fund for Distinguished Young Scholars of Shandong Province(ZR2019JQ16)the Fundamental Research Funds of Shandong UniversityYoung Elite Scientist Sponsorship Program by CAST(YESS)the support from Collaborative Innovation Center of Technology and Equipment for Biological Diagnosis and Therapy in Universities of Shandong
文摘Driven by safety issues,environmental concerns,and high costs,rechargeable aqueous zinc-ion batteries(ZIBs)have received increasing attention in recent years owing to their unique advantages.However,the sluggish kinetics of divalent charge Zn^(2+)in the cathode materials caused by the strong electrostatic interaction and their unsatisfactory cycle life hinder the development of ZIBs.Herein,organic cations and Zn^(2+)ions co-pre-inserted vanadium oxide([N(CH_(3))_(4)]_(0.77),Zn_(0.23))V_(8)O_(20)·3.8H_(2)O are reported as the cathode for ultra-stable aqueous ZIBs,in which the weaker electrostatic interactions between Zn^(2+)and organic ion-pinned vanadium oxide can induce the high reversibility of Zn^(2+)insertion and extraction,thereby improving the cycle life.It is demonstrated that([N(CH_(3))_(4)]_(0.77),Zn_(0.23))V_(8)O_(20)·3.8H_(2)O cathodes deliver a discharge capacity of 181 mA h g^(-1)at8 A g^(-1)and ultra-long life span(99.5%capacity retention after 2000 cycles).A reversible Zn^(2+)/H^(+)ions(de)intercalation storage process and pseudocapacitive charge storage are characterized.The weaker interactions between organic ion and Zn^(2+)open a novel avenue for the design of highly reversible cathode materials with long-term cycling stability.
