Layered V_(2)O_(5) cathode holds the merits of high theoretical specific capacity(589 mA h g^(-1))in aqueous zinc-ion batteries(AZIBs),yet it still suffers from inferior bulk conductivity and structure degradation not...Layered V_(2)O_(5) cathode holds the merits of high theoretical specific capacity(589 mA h g^(-1))in aqueous zinc-ion batteries(AZIBs),yet it still suffers from inferior bulk conductivity and structure degradation notably during prolonged cycling.Herein,we ingeniously design cations(Na^(+)/Co^(2+)/Al^(3+))and anion(F^(-))synergistic-doped hydrated V_(2)O_(5)·0.48H_(2)O cathode(VNACOF)to enhance the electronic and spatial effects in the bulk.A range of in-situ,ex-situ characterizations,and DFT calculations profoundly clarify the strengthened ionic/electronic conductivities,structural stability,and Zn^(2+)diffusion kinetics.As a result,the VNACOF displays a superior discharge capacity(529 mA h g^(-1)@0.1 C),rate capabilities(488 mA h g^(-1)@0.5 C,437 mA h g^(-1)@1C),and cycling stability(301 mA h g^(-1)@10 C@5000 cycles@93%)with sufficient energy density(393 W h kg^(-1)),Furthermore,the pouch-cells with high-load(60 mg)also deliver superior cyclic(2 C@178 mA h g^(-1)@1000 cycles@90%)and rate performance(132 mA h g^(-1)@5 C),revealing great application potential for high-energy-density and high-stability AZIBs.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
利用水热合成法合成了分子组成为(C6H11NH3)5H(P2Mo5O23)4H2O的杂多化合物, 用单晶X-ray衍射方法测定了它的结构,该晶体属于单斜晶系,空间群P21/c, a = 12.830(3), b = 14.848(3), c = 25.258(5) ? b = 92.95(3), Mr = 1483.62, V = 48...利用水热合成法合成了分子组成为(C6H11NH3)5H(P2Mo5O23)4H2O的杂多化合物, 用单晶X-ray衍射方法测定了它的结构,该晶体属于单斜晶系,空间群P21/c, a = 12.830(3), b = 14.848(3), c = 25.258(5) ? b = 92.95(3), Mr = 1483.62, V = 4805.1(17) 3, Z = 4, Dc = 2.051 g/cm3, m = 1.431 mm-1, F(000) = 3000, I >2s(I) 的可观察衍射点4426个, 最终结构偏差因子R = 0.0464, wR = 0.0801, S = 0.731。在[P2Mo5O23]6-杂多阴离子中5个MoO6八面体通过共边和共角相连, 形成1个近似的五角平面骨架, 2个PO4四面体加在五角平面的两侧。热性质研究表明杂多阴离子骨架在547.4 ℃左右分解。展开更多
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
基金financially supported by the National Key Research and Development Program of China(2022YFA1505700,2019YFA0210403)the National Natural Science Foundation of China(52102216)+4 种基金the Natural Science Foundation of Fujian Province(2022J01625,2022-S-002)the Anhui Key Laboratory of Nanomaterials and Nanotechnology,the Major Science and Technology Projects in Anhui Province(202305a12020006)the Open Project of State Key Laboratory of Inorganic Synthesis and Preparative Chemistry(2025-22)the Innovation Training Program for College Students(cxxl-2024131,cxxl-2024136)support by Transmission Electron Microscope Platform and High-performance Computing Platform of Fujian Science&Technology Innovation Laboratory for Optoelectronic Information of China。
文摘Layered V_(2)O_(5) cathode holds the merits of high theoretical specific capacity(589 mA h g^(-1))in aqueous zinc-ion batteries(AZIBs),yet it still suffers from inferior bulk conductivity and structure degradation notably during prolonged cycling.Herein,we ingeniously design cations(Na^(+)/Co^(2+)/Al^(3+))and anion(F^(-))synergistic-doped hydrated V_(2)O_(5)·0.48H_(2)O cathode(VNACOF)to enhance the electronic and spatial effects in the bulk.A range of in-situ,ex-situ characterizations,and DFT calculations profoundly clarify the strengthened ionic/electronic conductivities,structural stability,and Zn^(2+)diffusion kinetics.As a result,the VNACOF displays a superior discharge capacity(529 mA h g^(-1)@0.1 C),rate capabilities(488 mA h g^(-1)@0.5 C,437 mA h g^(-1)@1C),and cycling stability(301 mA h g^(-1)@10 C@5000 cycles@93%)with sufficient energy density(393 W h kg^(-1)),Furthermore,the pouch-cells with high-load(60 mg)also deliver superior cyclic(2 C@178 mA h g^(-1)@1000 cycles@90%)and rate performance(132 mA h g^(-1)@5 C),revealing great application potential for high-energy-density and high-stability AZIBs.
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.
