Polypyride intercalation boosting the kinetics and stability of V_(3)O_(7)·H_(2)O cathodes for aqueous zinc-ion batteries

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.

棒状V_(3)O_(7)•H_(2)O电极材料的制备及印刷超级电容器

以V2O5为原料,利用溶剂热法一步制备了V_(3)O_(7)•H_(2)O纳米棒,采用SEM、XRD、EDS、XPS和FTIR对样品进行了测试。以V_(3)O_(7)•H_(2)O纳米棒为电极材料,探究了丝网印刷工艺对电极电化学性能的影响,将此电极组装超级电容器并评价了其电化学性能。结果表明,丝网印刷电极比电容可达268.0 F/g(电流密度为0.3 A/g),经过5000次循环后电容保持率为85.9%,优于涂抹电极的比电容(246.0 F/g)和电容保持率(68.0%),这得益于丝网印刷的油墨规则排列的结构。组装的纽扣超级电容器也表现出优异的电化学性能,比电容和电容保持率为134.2 F/g(0.5 A/g电流密度)和91.2%(5000次充放电循环),且当能量密度为22.0 W·h/kg时,功率密度最高可达4125.0 W/kg。

Monoclinic Cu_(3)(OH)_(2)V_(2)O_(7)·2H_(2)O nanobelts/reduced graphene oxide:A novel high-capacity and long-life composite for potassium-ion battery anodes

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.

Three-dimensional Co_(2)V_(2)O_(7)·nH_(2)O superstructures assembled by nanosheets for electrochemical energy storage

Hierarchical superstructures assembled by nanosheets can effectively prevent aggregation of nanosheets and improve performance in energy storage.Therefore,we proposed a facile hydrothermal method to obtain three-dimensional(3D)superstructure assembled by nanosheets.We found that the ratio of Co^(2+)/HMTA affected the morphology of the samples,and the 3D hierarchical structures of are obtained while the ratio of Co^(2+)/HMTA is 12:25.The hierarchical structures with sufficient interior space preserves the original sheet-like dimensional components and results in sufficient active sites and efficient mass diffusion.Hence,the 3D Co_(2)V_(2)O_(7)·nH_(2)O hierarchical structure exhibits good rate capability and high stability while as electrode materials.Meanwhile,when power density is 745.13 W/kg,the assembled CVO-2//AC shows an energy density of 47.7 Wh/kg.The work displays a facile method for fabrication of 3D superstructure assembled by 2D nanosheets that can be applied in energy storage.

Weakly Polarized Organic Cation-Modified Hydrated Vanadium Oxides for High-Energy Efficiency Aqueous Zinc-Ion Batteries

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.

PVA-assisted hydrated vanadium pentoxide/reduced graphene oxide films for excellent Li^(+)and Zn^(2+)storage properties

Low-cost,high safety and environment-friendly aqueous energy storage systems(ESSs)are huge potential for grid-level energy storage,but the(de)intercalation of metal ions in the electrode materials(e.g.vanadium oxides)to obtain superior long-term cycling stability is a significant challenge.Herein,we demonstrate that polyvinyl alcohol(PVA)-assisted hydrated vanadium pentoxide/reduced graphene oxide(V_(2)O_(5)·n H_(2)O/r GO/PVA,denoted as the VGP)films enable long cycle stability and high capacity for the Li^(+)and Zn^(2+)storages in both the VGP//Li Cl(aq)//VGP and the VGP//Zn SO4(aq)//Zn cells.The binderfree VGP films are synthesized by a one-step hydrothermal method combination with the filtration.The extensive hydrogen bonds are formed among PVA,GO and H_(2)O,and they act as structural pillars and connect the adjacent layers as glue,which contributes to the ultrahigh specific capacitance and ultralong cyclic performance of Li^(+)and Zn^(2+)storage properties.As for Li^(+)storage,the binder-free VGP4 film(4mg PVA)electrode achieves the highest specific capacitance up to 1381 F g^(-1)at 1.0 A g^(-1)in the three-electrode system and 962 F g^(-1)at 1.0 A g^(-1)in the symmetric two-electrode system.It also behaves the outstanding cyclic performance with the capacitance retention of 96.5%after 15000 cycles in the three-electrode system and 99.7%after 25000 cycles in the symmetric two-electrode system.As for Zn^(2+)storage,the binder-free VGP4 film electrode exhibits the high specific capacity of 184 m A h g^(-1)at 0.5A g^(-1)in the VGP4//Zn SO4(aq)//Zn cell and the superb cycle performance of 98.5%after 25000 cycles.This work not only provides a new strategy for the construction of vanadium oxides composites and demonstrates the potential application of PVA-assisted binder-free film with excellent electrochemical properties,but also extends to construct other potential electrode materials for metal ion storage cells.

片状焦钒酸锌的制备及光催化性能

以六水合硝酸锌和偏钒酸铵为无机源,十六烷基三甲基溴化铵为表面活性剂,采用水热法合成纳米焦钒酸锌。考察了表面活性剂的浓度对纳米焦钒酸锌结构和性能的影响,通过XRD、SEM等对合成产物进行表征,以亚甲基蓝为目标降解物进行光催化实验,并对光催化机理进行了自由基捕获测试。其中制备的片状结构Zn_(3)(OH)_(2)V_(2)O_(7)·2H_(2)O具有最佳的光催化性能,在光照射140 min后对MB的降解率达到98%左右。