Pre-intercalation is the mainstream approach to inhibit the unpredicted structural degradation and the sluggish kinetics of Zn-ions migrating in vanadium oxide cathode of aqueous zinc-ion batteries(AZIBs),which has be...Pre-intercalation is the mainstream approach to inhibit the unpredicted structural degradation and the sluggish kinetics of Zn-ions migrating in vanadium oxide cathode of aqueous zinc-ion batteries(AZIBs),which has been extensively explored over the past 5 years.The functional principles behind the improvement are widely discussed but have been limited to the enlargement of interspace between VO layers.As the different types of ions could change the properties of vanadium oxides in various ways,the review starts with a comprehensive overview of pre-intercalated vanadium oxide cathode with different types of molecules and ions,such as metal ions,water molecules,and non-metallic cations,along with their functional principles and resulting performance.Furthermore,the pre-intercalated vanadium cathodes reported so far are summarized,comparing their interlayer space,capacity,cycling rate,and capacity retention after long cycling.A discussion of the relationship between the interspace and the performance is provided.The widest interspaces could result in the decay of the cycling stability.Based on the data,the optimal interspace is likely to be around 12?indicating that precise control of the interspace is a useful method.However,more consideration is required regarding the other impacts of pre-intercalated ions on vanadium oxide.It is hoped that this review can inspire further understanding of pre-intercalated vanadium oxide cathodes,paving a new pathway to the development of advanced vanadium oxide cathodes with better cycling stability and larger energy density.展开更多
Zinc-ion batteries(ZIBs)possess great advantages in terms of high safety and low cost,and are regarded as promising alternatives to lithium-ion batteries(LIBs).However,limited by the electrochemical kinetics and struc...Zinc-ion batteries(ZIBs)possess great advantages in terms of high safety and low cost,and are regarded as promising alternatives to lithium-ion batteries(LIBs).However,limited by the electrochemical kinetics and structural stability of the typical cathode materials,it is still difficult to simultaneously achieve high rates and high cycling stability for ZIBs.Herein,we present a manganese oxide(Sn_(x)Mn O_(2)/Sn O_(2))material that is dual-modified by Sn O_(2)/Mn O_(2)heterostructures and pre-intercalated Sn;cations as the cathode material for ZIBs.Such modification provides sufficient hetero-interfaces and expanded interlayer spacing in the material,which greatly facilitates the insertion/extraction of Zn^(2+).Meanwhile,the“structural pillars”of Sn^(4+) cations and the“pinning effect”of SnO_(2)also structurally stabilizes the Mn O_(2)species during the repeated Zn^(2+) insertion/extraction,leading to ultra-high cycling stability.Due to these merits,the Sn_(x)MnO_(2)/SnO_(2)cathode exhibits a high reversible capacity of 316.1 m Ah g^(-1) at 0.3 A g^(-1),superior rate capability of 179.4 m Ah g^(-1) at 2 A g^(-1),and 92.4%capacity retention after 2000 cycles.Consequently,this work would provide a promising yet efficient strategy by combining heterostructures and cations preintercalation to obtain high-performance cathodes for ZIBs.展开更多
Aqueous aluminum ion batteries(AAIBs)have garnered extensive attention due to their environmental friendliness,high theoretical capacity,and low cost.However,the sluggish reaction kinetics and severe structural collap...Aqueous aluminum ion batteries(AAIBs)have garnered extensive attention due to their environmental friendliness,high theoretical capacity,and low cost.However,the sluggish reaction kinetics and severe structural collapse of the cathode material,especially manganese oxide,during the cycling process have hindered its further application.Herein,Cu^(2+)pre-interca la ted layeredδ-MnO_(2)was synthesized via a hydrothermal method.The pre-intercalated Cu^(2+)ions not only improve the conductivity of MnO_(2)cathode but also stabilize the structure to enhance stability.X-ray absorption fine structure(XAFS)combined with density functional theory(DFT)calculations confirm the formation of the covalent bond between Cu and O,increasing the electronegativity of O atoms and enhancing the H^(+)adsorption energy.Moreover,ex-situ measurements not only elucidate the Al^(3+)/H^(+)co-insertion energy storage mechanism but also demonstrate the high reversibility of the Cu-MnO_(2)cathode during cycling.This work provides a promising modification approach for the application of manganese oxides in AAIBs.展开更多
Layered manganese dioxide(δ-MnO_(2))is a promising cathode material for aqueous zinc-ion batteries(AZIBs)due to its high theoretical capacity,high operating voltage,and low cost.However,its practical application face...Layered manganese dioxide(δ-MnO_(2))is a promising cathode material for aqueous zinc-ion batteries(AZIBs)due to its high theoretical capacity,high operating voltage,and low cost.However,its practical application faces challenges,such as low electronic conductivity,sluggish diffusion kinetics,and severe dissolution of Mn^(2+).In this study,we developed a δ-MnO_(2) coated with a 2-methylimidazole(δ-MnO_(2)@2-ML)hybrid cathode.Density functional theory(DFT)calculations indicate that 2-ML can be integrated into δ-MnO_(2) through both pre-intercalation and surface coating,with thermodynamically favorable outcomes.This modification expands the interlayer spacing of δ-MnO_(2) and generates Mn-N bonds on the surface,enhancing Zn^(2+)accommodation and diffusion kinetics as well as stabilizing surface Mn sites.The experimentally prepared δ-MnO_(2)@2-ML cathode,as predicted by DFT,features both 2-ML pre-intercalation and surface coating,providing more zinc-ion insertion sites and improved structural stability.Furthermore,X-ray diffraction shows the expanded interlayer spacing,which effectively buffers local electrostatic interactions,leading to an enhanced Zn^(2+)diffusion rate.Consequently,the optimized cathode(δ-MnO_(2)@2-ML)presents improved electrochemical performance and stability,and the fabricated AZIBs exhibit a high specific capacity(309.5mAh/g at 0.1 A/g),superior multiplicative performance(137.6mAh/g at 1 A/g),and impressive capacity retention(80%after 1350 cycles at 1 A/g).These results surpass the performance of most manganese-based and vanadium-based cathode materials reported to date.This dual-modulation strategy,combining interlayer engineering and interface optimization,offers a straightforward and scalable approach,potentially advancing the commercial viability of low-cost,high-performance AZIBs.展开更多
Large anions exhibit slow diffusion kinetics in graphite cathode of dual-ion batteries(DIBs);particularly at high current density,it suffers severely from the largely-reduced interlayer utilization of graphite cathode...Large anions exhibit slow diffusion kinetics in graphite cathode of dual-ion batteries(DIBs);particularly at high current density,it suffers severely from the largely-reduced interlayer utilization of graphite cathode,which as a bottleneck limits the fast charge application of DIBs.To maximize interlayer utilization and achieve faster anion diffusion kinetics,a fast and uncrowded anion transport channel must be established.Herein,Li^(+)was pre-intercalated into the graphite paper(GP)cathode to increase the interlayer spacing,and then hosted for the PF_(6)^(-)anion storage.Combined with theoretical calculation,it shows that the local interlayer spacing enlargement and the residual Li^(+)reduce the anion intercalation energy and diffusion barrier,leading to better rate stability.The obtained GP with Li^(+)pre-intercalation(GP-Li)electrode exhibits a discharge capacity of 23.1 m Ah g^(-1) at a high current of 1300 m A g^(-1).This work provides a facile method to efficiently improve the interlayer utilization of graphite cathode at large currents.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
Cathode materials with excellent performance are a key to exploiting aqueous zinc ion batteries.In this study,we developed a cathode material for aqueous zinc ion batteries using an in situ anion–cation pre-intercala...Cathode materials with excellent performance are a key to exploiting aqueous zinc ion batteries.In this study,we developed a cathode material for aqueous zinc ion batteries using an in situ anion–cation pre-intercalation strategy with a metal–organic framework.In situ doping of S and Zn in a vanadium-based metal–organic framework structure forms a Zn–S pre-intercalated vanadium oxide((Zn,S)VO)composite.The combination of the additional Zn^(2+)storage sites with pseudocapacitive behavior on the amorphous surface of the enriched oxygen defects and the enhancement of the structural toughness by strong ionic bonding together the unique nanostructure of the nanochains by the process of‘‘oriented attachment’’led to the preparation of the high-performance(Zn,S)VO composite.The results show that the(Zn,S)VO electrode has a capacity of 602.40 mAh·g^(-1)at 0.1 A·g^(-1),an initial discharge capacity of 300.60 mAh·g^(-1)at 10.0 A·g^(-1),and a capacity retention rate of 99.93%after 3,500 cycles.Using the gel electrolyte,the capacity of(Zn,S)VO electrode is 233.15 and 650.93 mAh·g^(-1)at 0.2 A·g^(-1)in-20 and 60°C environments,respectively.Meanwhile,the(Zn,S)VO flexible batteries perform well in harsh environments.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
Exploring suitable high-capacity V_(2)O_(5)-based cathode materials is essential for the rapid advancement of aqueous zinc ion batteries(ZIBs).However,the typical problem of slow Zn^(2+)diffusion kinetics has severely...Exploring suitable high-capacity V_(2)O_(5)-based cathode materials is essential for the rapid advancement of aqueous zinc ion batteries(ZIBs).However,the typical problem of slow Zn^(2+)diffusion kinetics has severely limited the feasibility of such materials.In this work,unique hydrated vanadates(CaVO,BaVO)were obtained by intercalation of Ca^(2+)or Ba^(2+)into hydrated vanadium pentoxide.In the CaVO//Zn and BaVO//Zn batteries systems,the former delivered up to a 489.8 mAh g^(-1)discharge specific capacity at 0.1 A g^(-1).Moreover,the remarkable energy density of 370.07 Wh kg^(-1)and favorable cycling stability yard outperform BaVO,pure V_(2)O_(5),and many reported cathodes of similar ionic intercalation compounds.In addition,pseudocapacitance analysis,galvanostatic intermittent titration(GITT)tests,and Trasatti analysis revealed the high capacitance contribution and Zn^(2+)diffusion coefficient of CaVO,while an in-depth investigation based on EIS elucidated the reasons for the better electrochemical performance of CaVO.Notably,ex-situ XRD,XPS,and TEM tests further demonstrated the Zn^(2+)insertion/extraction and Zn-storage mechanism that occurred during the cycle in the CaVO//Zn battery system.This work provides new insights into the intercalation of similar divalent cations in vanadium oxides and offers new solutions for designing cathodes for high-capacity aqueous ZIBs.展开更多
Aqueous Zn-ion batteries(AZIBs)are recognized as a promising energy storage system with intrinsic safety and low cost,but its applications still rely on the design of high-capacity and stable-cycling cathode materials...Aqueous Zn-ion batteries(AZIBs)are recognized as a promising energy storage system with intrinsic safety and low cost,but its applications still rely on the design of high-capacity and stable-cycling cathode materials.In this work,we present an intercalation mechanism-based cathode materials for AZIB,i.e.the vanadium oxide with pre-intercalated manganese ions and lattice water(noted as MVOH).The synergistic effect between Mn^(2+)and lattice H_(2)O not only expands the interlayer spacing,but also significantly enhances the structural stability.Systematic in-situ and ex-situ characterizations clarify the Zn^(2+)/H^(+)co–(de)intercalation mechanism of MVOH in aqueous electrolyte.The demonstrated remarkable structure stability,excellent kinetic behaviors and ion-storage mechanism together enable the MVOH to demonstrate satisfactory specific capacity of 450 mA h g^(−1)at 0.2 A g^(−1),excellent rate performance of 288.8 mA h g^(−1)at 10 A g^(−1)and long cycle life over 20,000 cycles at 5 A g^(−1).This work provides a practical cathode material,and contributes to the understanding of the ion-intercalation mechanism and structural evolution of the vanadium-based cathode for AZIBs.展开更多
Pre-intercalation of metal ions into vanadium oxide is an effective strategy for optimizing the performance of rechargeable zinc-ion battery(ZIB)cathodes.However,the battery long-lifespan achievement and high-capacity...Pre-intercalation of metal ions into vanadium oxide is an effective strategy for optimizing the performance of rechargeable zinc-ion battery(ZIB)cathodes.However,the battery long-lifespan achievement and high-capacity retention remain a challenge.Increasing the electronic conductivity while simultaneously prompting the cathode diffusion kinetics can improve ZIB electrochemical performance.Herein,N-doped vanadium oxide(N-(Zn,en)VO)via defect engineering is reported as cathode for aqueous ZIBs.Positron annihilation and electron paramagnetic resonance clearly indicate oxygen vacancies in the material.Density functional theory(DFT)calculations show that N-doping and oxygen vacancies concurrently increase the electronic conductivity and accelerate the diffusion kinetics of zinc ions.Moreover,the presence of oxygen vacancies substantially increases the storage sites of zinc ions.Therefore,N-(Zn,en)VO exhibits excellent electrochemical performance,including a peak capacity of 420.5 mA h g^(-1)at 0.05 A g^(-1),a high power density of more than 10000 W kg^(-1)at 65.3 Wh kg^(-1),and a long cycle life at 5 A g^(-1)(4500 cycles without capacity decay).The methodology adopted in our study can be applied to other cathodic materials to improve their performance and extend their practical applications.展开更多
Silver vanadate(Ag_(0.33)V_(2)O_(5))nanorods were successfully synthesized by the pre-intercalation of Ag+into the interlayer of V_(2)O_(5)through a sol-gel method,which presented a favorable electrochemical performan...Silver vanadate(Ag_(0.33)V_(2)O_(5))nanorods were successfully synthesized by the pre-intercalation of Ag+into the interlayer of V_(2)O_(5)through a sol-gel method,which presented a favorable electrochemical performance of high capacity,rate capacity,and cycle stability.Specific ally,Ag_(0.33)V_(2)O_(5)electrode presented a high capacity of about 311 mAh·g^(-1)at the current density of0.1 A·g^(-1).It also delivered long-term cycling stability(144 mAh·g^(-1)after 500 cycles at 2 A·g^(-1)).The reasons for the superior electrochemical performance were the preintercalation Ag^+extended interlayer distance,and the introduction of elemental silver improved conductivity during charge/discharge.Additionally,the Zn^(2+)storage mechanism was revealed by various characteristic measurements.The prepared Ag_(0.33)V_(2)O_(5)nanorods from the sol-gel method were demonstrated as a promising cathode material for aqueous Zn^(2+)batteries.展开更多
Aqueous rechargeable zinc-ion batteries(ARZIBs)have a bright future for energy storage due to their high energy density and safety.However,for traditional ARZIBs,cathode materials always suffer from the limited space ...Aqueous rechargeable zinc-ion batteries(ARZIBs)have a bright future for energy storage due to their high energy density and safety.However,for traditional ARZIBs,cathode materials always suffer from the limited space for large-sized zinc ions storage and transport,leading to low Coulombic efficiency and inferior cycling performance.To build a reliable host with large tunnel,1-butyl-1-methylpyrrolidinium ion(PY14^(+))pre-intercalated TiS_(2)(PY14^(+)-TiS_(2))is designed as an alternative intercalation-type electrode.As the insertion organic vip widens the interlayer space of TiS_(2)and buffers the lattice stress generated during the electrochemical cycles,the structural reversibility,cycling stability and kinetics properties of PY14^(+)-TiS_(2) are enhanced greatly.A specific capacity of 130.9 mAh g^(−1) with 84.3%capacity retention over 500 cycles can be achieved at 0.1 A g^(−1).Therefore,this study paves the way for enhancing the aqueous Zn ions storage capability by organic interlayer engineering.展开更多
With the rise of aqueous multivalent rechargeable batteries,inorganic-organic hybrid cathodes have attracted more and more attention due to the complement of each other’s advantages.Herein,a strategy of designing hyb...With the rise of aqueous multivalent rechargeable batteries,inorganic-organic hybrid cathodes have attracted more and more attention due to the complement of each other’s advantages.Herein,a strategy of designing hybrid cathode is adopted for high efficient aqueous zinc-ion batteries(AZIBs).Methylene blue(MB)intercalated vanadium oxide(HVO-MB)was synthesized through sol-gel and ion exchange method.Compared with other organic-inorganic intercalation cathode,not only can the MB intercalation enlarge the HVO interlayer spacing to improve ion mobility,but also provide coordination reactions with the Zn^(2+)to enhance the intrinsic electrochemical reaction kinetics of the hybrid electrode.As a key component for the cathode of AZIBs,HVO-MB contributes a specific capacity of 418 mA h g^(-1) at 0.1 A g^(-1),high rate capability(243 mA h g^(-1) at 5 A g^(-1))and extraordinary stability(88%of capacity retention after 2000cycles at a high current density of 5 A g^(-1))in 3 M Zn(CF_(3)SO_(3))_(2) aqueous electrolyte.The electrochemical kinetics reveals HVO-MB characterized with large pseudocapacitance charge storage behavior due to the fast ion migration provided by the coordination reaction and expanded interlayer distance.Furthermore,a mixed energy storage mechanism involving Zn^(2+)insertion and coordination reaction is confirmed by various ex-situ characterization.Thus,this work opens up a new path for constructing the high performance cathode of AZIBs through organic-inorganic hybridization.展开更多
In aqueous zinc-ion batteries(AZIB),layered manganese dioxide(δ-MnO_(2))is considered to be a suitable cathode material due to its high theoretical capacity,suitable operating voltage and Zn^(2+)/H^(+)cointercalation...In aqueous zinc-ion batteries(AZIB),layered manganese dioxide(δ-MnO_(2))is considered to be a suitable cathode material due to its high theoretical capacity,suitable operating voltage and Zn^(2+)/H^(+)cointercalation mechanism.However,the strong coulomb interaction between Zn^(2+)andδ-MnO_(2)results in the slow diffusion dynamics of Zn^(2+)in the electrochemical process,which affects the structural stability of the cathode.Herein,we report a structural design that stabilizes theδ-MnO_(2)-layered structure by preintercalation of Cu^(2+)to expand the layer spacing,and thus improve H^(+)-transfer kinetics.Compared with the bulkδ-MnO_(2),the modified cathode showed excellent electrochemical performances,including a highly reversible capacity of 280 mA h g^(-1)at 1 A g^(-1)and 62.5%capacity retention after 1500 cycles at 5 A g^(-1).The results shown above confirmed the possibility of increasing the capacity contribution of H^(+)through structural design,and provides a novel idea for the development of high-performance cathode materials.展开更多
Rechargeable aqueous zinc-ion batteries(ZIBs)are regarded as the next promising large scale energy storage systems owing to their low cost,high safety and environmental friendliness.Vanadium-based materials are one of...Rechargeable aqueous zinc-ion batteries(ZIBs)are regarded as the next promising large scale energy storage systems owing to their low cost,high safety and environmental friendliness.Vanadium-based materials are one of the most important cathodes of ZIBs due to their high abundance and multielectron transfer of various oxidations of vanadium.Nevertheless,the strong electrostatic interaction between Zn^(2+)and cathodes,intrinsic poor electronic conductivity and solubility of vanadium-based cathodes in electrolytes bring about inferior electrochemical performance.In this work,we introduce aliovalent Cr^(3+)into the interlayer of hydrated vanadium oxide(Cr-VOH)as pillar to significantly increase the structural stability and electrochemical reversibility.The pre-intercalation of Cr^(3+)also provides an enhanced electronic conductivity and fast Zn^(2+)diffusion dynamics,enabling superior Zn2+storage performance of the Cr-VOH cathode.As a result,the Cr-VOH cathode exhibits a high reversible discharge capacity of~380 mAh g^(−1)at 50 mA g^(−1),excellent rate capacity of 166 mAh g^(−1)at 8 A g^(−1)and prolonged cycling stability over 500 cycles.Furthermore,it displays a high energy density of 273.6 W h kg^(−1)at 0.05 A g^(−1)and the power density of 4960 W kg^(−1)at 8 A g^(−1),contributing to the practical application potential of aqueous ZIBs.展开更多
Vanadium bronzes have been well-demonstrated as promising cathode materials for aqueous zinc-ion batteries. However, conventional single-ion pre-intercalated V_(4)O_(9)nearly reached its energy/power ceiling due to th...Vanadium bronzes have been well-demonstrated as promising cathode materials for aqueous zinc-ion batteries. However, conventional single-ion pre-intercalated V_(4)O_(9)nearly reached its energy/power ceiling due to the nature of micro/electronic structures and unfavourable phase transition during Zn;storage processes. Here, a simple and universal in-situ anodic oxidation method of quasi-layered Ca V_(4)O_(9)in a tailored electrolyte was developed to introduce dual ions(Ca^(2+) and Zn^(2+)) into bilayer δ-V_(4)O_(9)frameworks forming crystallographic ultra-thin vanadium bronzes,Ca^(2+)Zn^(2+)V_(4)O_(9)·n H;O. The materials deliver transcendental maximum energy and power densities of 366 W h kg-1(478 m A h g^(-1)@ 0.2 A g^(-1)) and 6627 W kg-1(245 m A h g^(-1)@10 A g^(-1)), respectively, and the long cycling stability with a high specific capacity up to 205 m A h g^(-1)after 3000 cycles at10 A g^(-1). The synergistic contributions of dual ions and Ca^(2+) electrolyte additives on battery performances were systematically investigated by multiple in-/ex-situ characterisations to reveal reversible structural/chemical evolutions and enhanced electrochemical kinetics, highlighting the significance of electrolyte-governed conversion reaction process. Through the computational approach, reinforced “pillar” effects,charge screening effects and regulated electronic structures derived from pre-intercalated dual ions were elucidated for contributing to boosted charge storage properties.展开更多
The rechargeable magnesium batteries(RMBs)are getting more and more attention because of their high-energy density,high-security and low-cost.Nevertheless,the high charge density of Mg^2+makes the diffusion of Mg2+in ...The rechargeable magnesium batteries(RMBs)are getting more and more attention because of their high-energy density,high-security and low-cost.Nevertheless,the high charge density of Mg^2+makes the diffusion of Mg2+in the conventional cathodes very slow,resulting in a lack of appropriate electrode materials for RMBs.In this work,we enlarge the layer spacing of V2Os by introducing Na^2+in the crystal structure to promote the diffusion kinetics of Mg^2+.The NaVeO15(NVO)synthesized by a facile method is studied as a cathode material for RMBs with the anhydrous pure Mg^2+electrolyte.As a result,the NVO not only exhibits high discharge capacity(119.2 mAh:g^-1 after 100 cycles at the current density of 20 mA:g^-1)and working voltage(above 1.6 V vs.Mg^2+/Mg),but also expresses good rate capability.Besides,the eX-situ characterizations results reveal that the Mg^2+storage mechanism in NVO is based on the intercalation and deintercalation.The density functional theory(DFT)calculation results further indicate that Mg^2+tends to occupy the semi-occupied sites of Na^+in the NVO.Moreover,the galvanostatic intermittent titration technique(GITT)demonstrates that NVO electrode has the fast diffusion kinetics of Mg^2+during discharge process ranging from 7.55×10^-13 to2.41×10^-11 cm^2·s^-1.Our work proves that the NVO is a potential cathode material for RMBs.展开更多
Rechargeable aqueous zinc ion batteries (ZIBs),with the easy operation,cost effectiveness,and high safety,are emerging candidates for high-energy wearable/portable energy storage systems.Unfortunately,the unsatisfacto...Rechargeable aqueous zinc ion batteries (ZIBs),with the easy operation,cost effectiveness,and high safety,are emerging candidates for high-energy wearable/portable energy storage systems.Unfortunately,the unsatisfactory energy density and undesired long-term cycling performance of the cathode hinder the development of ZIBs.Here,we report the chemical preintercalation of a small amount of calcium ions into V2O5 as the cathode material.The cathode of Ca0.04V2O5·1.74H2O (CVO)was demonstrated to have a high specific capacity of 400 mA h g^-1at the current density of 0.05 A g^-1and 187 mA h g^-1at 10 A g^-1,along with impressive capacity retention (100%capacity retention at 10 A g^-1 for 3,000 cycles).Meanwhile,the CVO//Zn battery exhibits a high energy density of 308 Wh kg^-1and a power density of 467 W kg^-1at 0.5 A g^-1.The superior performance originates from the pinning effect of the calcium ions and the lubricating effect of the structural water.The energy storage mechanism of the CVO cathode was also investigated in detail.The new phase (Zn3(OH)2V2O7·2H2O) generated upon cycling participates in the electrochemical reaction and thus contributes to the excellent electrochemical performance.The small amount of Ca^2+ pre-inserted into the interlayer of V2O5 sheds light on constructing cathodes with high energy density for ZIBs.展开更多
Intercalation of ions between the adjacent MXene layers can change the interlayer environment and influence the electrochemical ion storage capacity.In order to understand the effect of multi-ions confined by the MXen...Intercalation of ions between the adjacent MXene layers can change the interlayer environment and influence the electrochemical ion storage capacity.In order to understand the effect of multi-ions confined by the MXene layers on the performance of electrochemical energy storage,Co^(2+),Mn^(2+)and Ni^(2+)intercalated into Ti_(3)C_(2)T_(x)MXene which already pre-intercalated Al3+are obtained by spontaneous static action.Based on the monitor of(002)crystal orientation,intercalated multi-ions can regulate and control the interlayer environment of MXenes via stress,which induces lattice shrinkage occurring in the c axis.Limited by ion storage mechanism-performance,the multi-ion occupies the interspace of MXene and affects the electrochemical performance.This work would offer guidance to understand the relationship among the multi-ion and MXene by two-dimensional(2D)layered materials.展开更多
基金funded by the Startup fund at Hubei University of Technology(Grant Nos.00709)a High-level Talent grant(Grant No.GCC2024012)from Hubei province.
文摘Pre-intercalation is the mainstream approach to inhibit the unpredicted structural degradation and the sluggish kinetics of Zn-ions migrating in vanadium oxide cathode of aqueous zinc-ion batteries(AZIBs),which has been extensively explored over the past 5 years.The functional principles behind the improvement are widely discussed but have been limited to the enlargement of interspace between VO layers.As the different types of ions could change the properties of vanadium oxides in various ways,the review starts with a comprehensive overview of pre-intercalated vanadium oxide cathode with different types of molecules and ions,such as metal ions,water molecules,and non-metallic cations,along with their functional principles and resulting performance.Furthermore,the pre-intercalated vanadium cathodes reported so far are summarized,comparing their interlayer space,capacity,cycling rate,and capacity retention after long cycling.A discussion of the relationship between the interspace and the performance is provided.The widest interspaces could result in the decay of the cycling stability.Based on the data,the optimal interspace is likely to be around 12?indicating that precise control of the interspace is a useful method.However,more consideration is required regarding the other impacts of pre-intercalated ions on vanadium oxide.It is hoped that this review can inspire further understanding of pre-intercalated vanadium oxide cathodes,paving a new pathway to the development of advanced vanadium oxide cathodes with better cycling stability and larger energy density.
基金supported by the National Natural Science Foundation of China(21905202 and 22002107)。
文摘Zinc-ion batteries(ZIBs)possess great advantages in terms of high safety and low cost,and are regarded as promising alternatives to lithium-ion batteries(LIBs).However,limited by the electrochemical kinetics and structural stability of the typical cathode materials,it is still difficult to simultaneously achieve high rates and high cycling stability for ZIBs.Herein,we present a manganese oxide(Sn_(x)Mn O_(2)/Sn O_(2))material that is dual-modified by Sn O_(2)/Mn O_(2)heterostructures and pre-intercalated Sn;cations as the cathode material for ZIBs.Such modification provides sufficient hetero-interfaces and expanded interlayer spacing in the material,which greatly facilitates the insertion/extraction of Zn^(2+).Meanwhile,the“structural pillars”of Sn^(4+) cations and the“pinning effect”of SnO_(2)also structurally stabilizes the Mn O_(2)species during the repeated Zn^(2+) insertion/extraction,leading to ultra-high cycling stability.Due to these merits,the Sn_(x)MnO_(2)/SnO_(2)cathode exhibits a high reversible capacity of 316.1 m Ah g^(-1) at 0.3 A g^(-1),superior rate capability of 179.4 m Ah g^(-1) at 2 A g^(-1),and 92.4%capacity retention after 2000 cycles.Consequently,this work would provide a promising yet efficient strategy by combining heterostructures and cations preintercalation to obtain high-performance cathodes for ZIBs.
基金financially supported by the National Natural Science Foundation of China(52102233)Science and Technology Project of Hebei Education Department(QN2023019)。
文摘Aqueous aluminum ion batteries(AAIBs)have garnered extensive attention due to their environmental friendliness,high theoretical capacity,and low cost.However,the sluggish reaction kinetics and severe structural collapse of the cathode material,especially manganese oxide,during the cycling process have hindered its further application.Herein,Cu^(2+)pre-interca la ted layeredδ-MnO_(2)was synthesized via a hydrothermal method.The pre-intercalated Cu^(2+)ions not only improve the conductivity of MnO_(2)cathode but also stabilize the structure to enhance stability.X-ray absorption fine structure(XAFS)combined with density functional theory(DFT)calculations confirm the formation of the covalent bond between Cu and O,increasing the electronegativity of O atoms and enhancing the H^(+)adsorption energy.Moreover,ex-situ measurements not only elucidate the Al^(3+)/H^(+)co-insertion energy storage mechanism but also demonstrate the high reversibility of the Cu-MnO_(2)cathode during cycling.This work provides a promising modification approach for the application of manganese oxides in AAIBs.
基金supported by the the National Natural Science Foundation of China(52203303)the Shenzhen Science and Technology Program(SGDX20211123151002003 and GJHZ20220913142812025)+1 种基金the International Partnership Program of the Chinese Academy of Sciences(321GJHZ2023189FN)the SIAT International Joint Lab(E5G108).
文摘Layered manganese dioxide(δ-MnO_(2))is a promising cathode material for aqueous zinc-ion batteries(AZIBs)due to its high theoretical capacity,high operating voltage,and low cost.However,its practical application faces challenges,such as low electronic conductivity,sluggish diffusion kinetics,and severe dissolution of Mn^(2+).In this study,we developed a δ-MnO_(2) coated with a 2-methylimidazole(δ-MnO_(2)@2-ML)hybrid cathode.Density functional theory(DFT)calculations indicate that 2-ML can be integrated into δ-MnO_(2) through both pre-intercalation and surface coating,with thermodynamically favorable outcomes.This modification expands the interlayer spacing of δ-MnO_(2) and generates Mn-N bonds on the surface,enhancing Zn^(2+)accommodation and diffusion kinetics as well as stabilizing surface Mn sites.The experimentally prepared δ-MnO_(2)@2-ML cathode,as predicted by DFT,features both 2-ML pre-intercalation and surface coating,providing more zinc-ion insertion sites and improved structural stability.Furthermore,X-ray diffraction shows the expanded interlayer spacing,which effectively buffers local electrostatic interactions,leading to an enhanced Zn^(2+)diffusion rate.Consequently,the optimized cathode(δ-MnO_(2)@2-ML)presents improved electrochemical performance and stability,and the fabricated AZIBs exhibit a high specific capacity(309.5mAh/g at 0.1 A/g),superior multiplicative performance(137.6mAh/g at 1 A/g),and impressive capacity retention(80%after 1350 cycles at 1 A/g).These results surpass the performance of most manganese-based and vanadium-based cathode materials reported to date.This dual-modulation strategy,combining interlayer engineering and interface optimization,offers a straightforward and scalable approach,potentially advancing the commercial viability of low-cost,high-performance AZIBs.
基金financially supported by the National Natural Science Foundation of China(51932003,51872115)the 2020 International Cooperation Project of the Department of Science and Technology of Jilin Province(20200801001GH)the Project supported by State Key Laboratory of Luminescence and Applications(KLA-2020-05)。
文摘Large anions exhibit slow diffusion kinetics in graphite cathode of dual-ion batteries(DIBs);particularly at high current density,it suffers severely from the largely-reduced interlayer utilization of graphite cathode,which as a bottleneck limits the fast charge application of DIBs.To maximize interlayer utilization and achieve faster anion diffusion kinetics,a fast and uncrowded anion transport channel must be established.Herein,Li^(+)was pre-intercalated into the graphite paper(GP)cathode to increase the interlayer spacing,and then hosted for the PF_(6)^(-)anion storage.Combined with theoretical calculation,it shows that the local interlayer spacing enlargement and the residual Li^(+)reduce the anion intercalation energy and diffusion barrier,leading to better rate stability.The obtained GP with Li^(+)pre-intercalation(GP-Li)electrode exhibits a discharge capacity of 23.1 m Ah g^(-1) at a high current of 1300 m A g^(-1).This work provides a facile method to efficiently improve the interlayer utilization of graphite cathode at large currents.
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.
基金supported by the Natural Science Research Project of the Education Department of Guizhou Province(No.QJJ[2022]001)。
文摘Cathode materials with excellent performance are a key to exploiting aqueous zinc ion batteries.In this study,we developed a cathode material for aqueous zinc ion batteries using an in situ anion–cation pre-intercalation strategy with a metal–organic framework.In situ doping of S and Zn in a vanadium-based metal–organic framework structure forms a Zn–S pre-intercalated vanadium oxide((Zn,S)VO)composite.The combination of the additional Zn^(2+)storage sites with pseudocapacitive behavior on the amorphous surface of the enriched oxygen defects and the enhancement of the structural toughness by strong ionic bonding together the unique nanostructure of the nanochains by the process of‘‘oriented attachment’’led to the preparation of the high-performance(Zn,S)VO composite.The results show that the(Zn,S)VO electrode has a capacity of 602.40 mAh·g^(-1)at 0.1 A·g^(-1),an initial discharge capacity of 300.60 mAh·g^(-1)at 10.0 A·g^(-1),and a capacity retention rate of 99.93%after 3,500 cycles.Using the gel electrolyte,the capacity of(Zn,S)VO electrode is 233.15 and 650.93 mAh·g^(-1)at 0.2 A·g^(-1)in-20 and 60°C environments,respectively.Meanwhile,the(Zn,S)VO flexible batteries perform well in harsh environments.
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the financial support from the National Key Research and Development Program of China(2022YFA1207503)the Giga Force Electronics Interdisciplinary Funding(JJHXM002208-2023)。
文摘Exploring suitable high-capacity V_(2)O_(5)-based cathode materials is essential for the rapid advancement of aqueous zinc ion batteries(ZIBs).However,the typical problem of slow Zn^(2+)diffusion kinetics has severely limited the feasibility of such materials.In this work,unique hydrated vanadates(CaVO,BaVO)were obtained by intercalation of Ca^(2+)or Ba^(2+)into hydrated vanadium pentoxide.In the CaVO//Zn and BaVO//Zn batteries systems,the former delivered up to a 489.8 mAh g^(-1)discharge specific capacity at 0.1 A g^(-1).Moreover,the remarkable energy density of 370.07 Wh kg^(-1)and favorable cycling stability yard outperform BaVO,pure V_(2)O_(5),and many reported cathodes of similar ionic intercalation compounds.In addition,pseudocapacitance analysis,galvanostatic intermittent titration(GITT)tests,and Trasatti analysis revealed the high capacitance contribution and Zn^(2+)diffusion coefficient of CaVO,while an in-depth investigation based on EIS elucidated the reasons for the better electrochemical performance of CaVO.Notably,ex-situ XRD,XPS,and TEM tests further demonstrated the Zn^(2+)insertion/extraction and Zn-storage mechanism that occurred during the cycle in the CaVO//Zn battery system.This work provides new insights into the intercalation of similar divalent cations in vanadium oxides and offers new solutions for designing cathodes for high-capacity aqueous ZIBs.
基金supported by the grants from the Chinese Academy of Sciences(124GJHZ2023031MI)the National Natural Science Foundation of China(52173274)+1 种基金the National Key R&D Project from the Ministry of Science and Technology(2021YFA1201603)the Fundamental Research Funds for the Central Universities.
文摘Aqueous Zn-ion batteries(AZIBs)are recognized as a promising energy storage system with intrinsic safety and low cost,but its applications still rely on the design of high-capacity and stable-cycling cathode materials.In this work,we present an intercalation mechanism-based cathode materials for AZIB,i.e.the vanadium oxide with pre-intercalated manganese ions and lattice water(noted as MVOH).The synergistic effect between Mn^(2+)and lattice H_(2)O not only expands the interlayer spacing,but also significantly enhances the structural stability.Systematic in-situ and ex-situ characterizations clarify the Zn^(2+)/H^(+)co–(de)intercalation mechanism of MVOH in aqueous electrolyte.The demonstrated remarkable structure stability,excellent kinetic behaviors and ion-storage mechanism together enable the MVOH to demonstrate satisfactory specific capacity of 450 mA h g^(−1)at 0.2 A g^(−1),excellent rate performance of 288.8 mA h g^(−1)at 10 A g^(−1)and long cycle life over 20,000 cycles at 5 A g^(−1).This work provides a practical cathode material,and contributes to the understanding of the ion-intercalation mechanism and structural evolution of the vanadium-based cathode for AZIBs.
基金National Natural Science Foundation of China,Grant/Award Numbers:51732007,51902187,52072224Natural Science Foundation of Shandong Province,Grant/Award Numbers:ZR2018BEM010,ZR2020YQ35+1 种基金Collaborative Innovation Center of Technology and Equipment for Biological Diagnosis and Therapy in Universities of ShandongYoung Elite Scientists Sponsorship Program,Grant/Award Number:2019QNRC001。
文摘Pre-intercalation of metal ions into vanadium oxide is an effective strategy for optimizing the performance of rechargeable zinc-ion battery(ZIB)cathodes.However,the battery long-lifespan achievement and high-capacity retention remain a challenge.Increasing the electronic conductivity while simultaneously prompting the cathode diffusion kinetics can improve ZIB electrochemical performance.Herein,N-doped vanadium oxide(N-(Zn,en)VO)via defect engineering is reported as cathode for aqueous ZIBs.Positron annihilation and electron paramagnetic resonance clearly indicate oxygen vacancies in the material.Density functional theory(DFT)calculations show that N-doping and oxygen vacancies concurrently increase the electronic conductivity and accelerate the diffusion kinetics of zinc ions.Moreover,the presence of oxygen vacancies substantially increases the storage sites of zinc ions.Therefore,N-(Zn,en)VO exhibits excellent electrochemical performance,including a peak capacity of 420.5 mA h g^(-1)at 0.05 A g^(-1),a high power density of more than 10000 W kg^(-1)at 65.3 Wh kg^(-1),and a long cycle life at 5 A g^(-1)(4500 cycles without capacity decay).The methodology adopted in our study can be applied to other cathodic materials to improve their performance and extend their practical applications.
基金financially supported by the National Natural Science Foundation of China (No.52101243)the Natural Science Foundation of Guangdong Province (No. 2020A1515010886)the Science and Technology Planning Project of Guangzhou (No.202102010373)
文摘Silver vanadate(Ag_(0.33)V_(2)O_(5))nanorods were successfully synthesized by the pre-intercalation of Ag+into the interlayer of V_(2)O_(5)through a sol-gel method,which presented a favorable electrochemical performance of high capacity,rate capacity,and cycle stability.Specific ally,Ag_(0.33)V_(2)O_(5)electrode presented a high capacity of about 311 mAh·g^(-1)at the current density of0.1 A·g^(-1).It also delivered long-term cycling stability(144 mAh·g^(-1)after 500 cycles at 2 A·g^(-1)).The reasons for the superior electrochemical performance were the preintercalation Ag^+extended interlayer distance,and the introduction of elemental silver improved conductivity during charge/discharge.Additionally,the Zn^(2+)storage mechanism was revealed by various characteristic measurements.The prepared Ag_(0.33)V_(2)O_(5)nanorods from the sol-gel method were demonstrated as a promising cathode material for aqueous Zn^(2+)batteries.
基金supported by the NSAF joint Fund(No.U1830106)the National Natural Science Foundation of China(No.U1632114).
文摘Aqueous rechargeable zinc-ion batteries(ARZIBs)have a bright future for energy storage due to their high energy density and safety.However,for traditional ARZIBs,cathode materials always suffer from the limited space for large-sized zinc ions storage and transport,leading to low Coulombic efficiency and inferior cycling performance.To build a reliable host with large tunnel,1-butyl-1-methylpyrrolidinium ion(PY14^(+))pre-intercalated TiS_(2)(PY14^(+)-TiS_(2))is designed as an alternative intercalation-type electrode.As the insertion organic vip widens the interlayer space of TiS_(2)and buffers the lattice stress generated during the electrochemical cycles,the structural reversibility,cycling stability and kinetics properties of PY14^(+)-TiS_(2) are enhanced greatly.A specific capacity of 130.9 mAh g^(−1) with 84.3%capacity retention over 500 cycles can be achieved at 0.1 A g^(−1).Therefore,this study paves the way for enhancing the aqueous Zn ions storage capability by organic interlayer engineering.
基金supported by the National Natural Science Foundation of China(21965027 and 22065030)the Natural Science Foundation of Ningxia Province(2022AAC03109)the National First-rate Discipline Construction Project of Ningxia:Chemical Engineering and Technology(NXY-LXK2017A04)。
文摘With the rise of aqueous multivalent rechargeable batteries,inorganic-organic hybrid cathodes have attracted more and more attention due to the complement of each other’s advantages.Herein,a strategy of designing hybrid cathode is adopted for high efficient aqueous zinc-ion batteries(AZIBs).Methylene blue(MB)intercalated vanadium oxide(HVO-MB)was synthesized through sol-gel and ion exchange method.Compared with other organic-inorganic intercalation cathode,not only can the MB intercalation enlarge the HVO interlayer spacing to improve ion mobility,but also provide coordination reactions with the Zn^(2+)to enhance the intrinsic electrochemical reaction kinetics of the hybrid electrode.As a key component for the cathode of AZIBs,HVO-MB contributes a specific capacity of 418 mA h g^(-1) at 0.1 A g^(-1),high rate capability(243 mA h g^(-1) at 5 A g^(-1))and extraordinary stability(88%of capacity retention after 2000cycles at a high current density of 5 A g^(-1))in 3 M Zn(CF_(3)SO_(3))_(2) aqueous electrolyte.The electrochemical kinetics reveals HVO-MB characterized with large pseudocapacitance charge storage behavior due to the fast ion migration provided by the coordination reaction and expanded interlayer distance.Furthermore,a mixed energy storage mechanism involving Zn^(2+)insertion and coordination reaction is confirmed by various ex-situ characterization.Thus,this work opens up a new path for constructing the high performance cathode of AZIBs through organic-inorganic hybridization.
基金supported by the National Natural Science Foundation of China(52225204,52173233,52002059 and 52202085)Innovation Program of Shanghai Municipal Education Commission(2021-01-07-00-03-E00109)+3 种基金Natural Science Foundation of Shanghai(23ZR1479200)“Shuguang Program”supported by the Shanghai Education Development Foundation and Shanghai Municipal Education Commission(20SG33)DHU Distinguished Young Professor Program(LZA2022001 and LZB2023002)the Fundamental Research Funds for Central Universities(2232023G-07,2232024Y-01).
文摘In aqueous zinc-ion batteries(AZIB),layered manganese dioxide(δ-MnO_(2))is considered to be a suitable cathode material due to its high theoretical capacity,suitable operating voltage and Zn^(2+)/H^(+)cointercalation mechanism.However,the strong coulomb interaction between Zn^(2+)andδ-MnO_(2)results in the slow diffusion dynamics of Zn^(2+)in the electrochemical process,which affects the structural stability of the cathode.Herein,we report a structural design that stabilizes theδ-MnO_(2)-layered structure by preintercalation of Cu^(2+)to expand the layer spacing,and thus improve H^(+)-transfer kinetics.Compared with the bulkδ-MnO_(2),the modified cathode showed excellent electrochemical performances,including a highly reversible capacity of 280 mA h g^(-1)at 1 A g^(-1)and 62.5%capacity retention after 1500 cycles at 5 A g^(-1).The results shown above confirmed the possibility of increasing the capacity contribution of H^(+)through structural design,and provides a novel idea for the development of high-performance cathode materials.
基金This work was supported by the National Key Research and Development Program of China(2019YFE0118800)National Natural Science Foundation of China(22005215)+1 种基金Tianjin Science and Technology Project(19YFSLQY00070)Hebei Province Innovation Ability Promotion Project(20544401D,20312201D).
文摘Rechargeable aqueous zinc-ion batteries(ZIBs)are regarded as the next promising large scale energy storage systems owing to their low cost,high safety and environmental friendliness.Vanadium-based materials are one of the most important cathodes of ZIBs due to their high abundance and multielectron transfer of various oxidations of vanadium.Nevertheless,the strong electrostatic interaction between Zn^(2+)and cathodes,intrinsic poor electronic conductivity and solubility of vanadium-based cathodes in electrolytes bring about inferior electrochemical performance.In this work,we introduce aliovalent Cr^(3+)into the interlayer of hydrated vanadium oxide(Cr-VOH)as pillar to significantly increase the structural stability and electrochemical reversibility.The pre-intercalation of Cr^(3+)also provides an enhanced electronic conductivity and fast Zn^(2+)diffusion dynamics,enabling superior Zn2+storage performance of the Cr-VOH cathode.As a result,the Cr-VOH cathode exhibits a high reversible discharge capacity of~380 mAh g^(−1)at 50 mA g^(−1),excellent rate capacity of 166 mAh g^(−1)at 8 A g^(−1)and prolonged cycling stability over 500 cycles.Furthermore,it displays a high energy density of 273.6 W h kg^(−1)at 0.05 A g^(−1)and the power density of 4960 W kg^(−1)at 8 A g^(−1),contributing to the practical application potential of aqueous ZIBs.
基金supported by the Engineering and Physical Sciences Research Council (EPSRC, EP/V027433/1) of UKthe National Key Research and Development Program of China (2018YFA0704502 and 2017YFA0700103)+2 种基金the National Natural Science Foundation of China (21703248)the Strategic Priority Research Program of the Chinese Academy of Sciences (XDB20000000)the Royal Society (RGSR1211080, IESR2212115) of UK。
文摘Vanadium bronzes have been well-demonstrated as promising cathode materials for aqueous zinc-ion batteries. However, conventional single-ion pre-intercalated V_(4)O_(9)nearly reached its energy/power ceiling due to the nature of micro/electronic structures and unfavourable phase transition during Zn;storage processes. Here, a simple and universal in-situ anodic oxidation method of quasi-layered Ca V_(4)O_(9)in a tailored electrolyte was developed to introduce dual ions(Ca^(2+) and Zn^(2+)) into bilayer δ-V_(4)O_(9)frameworks forming crystallographic ultra-thin vanadium bronzes,Ca^(2+)Zn^(2+)V_(4)O_(9)·n H;O. The materials deliver transcendental maximum energy and power densities of 366 W h kg-1(478 m A h g^(-1)@ 0.2 A g^(-1)) and 6627 W kg-1(245 m A h g^(-1)@10 A g^(-1)), respectively, and the long cycling stability with a high specific capacity up to 205 m A h g^(-1)after 3000 cycles at10 A g^(-1). The synergistic contributions of dual ions and Ca^(2+) electrolyte additives on battery performances were systematically investigated by multiple in-/ex-situ characterisations to reveal reversible structural/chemical evolutions and enhanced electrochemical kinetics, highlighting the significance of electrolyte-governed conversion reaction process. Through the computational approach, reinforced “pillar” effects,charge screening effects and regulated electronic structures derived from pre-intercalated dual ions were elucidated for contributing to boosted charge storage properties.
基金We gratefully acknowledge the financial support from the National Natural Science Foundation of China(Nos.21875198 and 21621091).
文摘The rechargeable magnesium batteries(RMBs)are getting more and more attention because of their high-energy density,high-security and low-cost.Nevertheless,the high charge density of Mg^2+makes the diffusion of Mg2+in the conventional cathodes very slow,resulting in a lack of appropriate electrode materials for RMBs.In this work,we enlarge the layer spacing of V2Os by introducing Na^2+in the crystal structure to promote the diffusion kinetics of Mg^2+.The NaVeO15(NVO)synthesized by a facile method is studied as a cathode material for RMBs with the anhydrous pure Mg^2+electrolyte.As a result,the NVO not only exhibits high discharge capacity(119.2 mAh:g^-1 after 100 cycles at the current density of 20 mA:g^-1)and working voltage(above 1.6 V vs.Mg^2+/Mg),but also expresses good rate capability.Besides,the eX-situ characterizations results reveal that the Mg^2+storage mechanism in NVO is based on the intercalation and deintercalation.The density functional theory(DFT)calculation results further indicate that Mg^2+tends to occupy the semi-occupied sites of Na^+in the NVO.Moreover,the galvanostatic intermittent titration technique(GITT)demonstrates that NVO electrode has the fast diffusion kinetics of Mg^2+during discharge process ranging from 7.55×10^-13 to2.41×10^-11 cm^2·s^-1.Our work proves that the NVO is a potential cathode material for RMBs.
基金This work was supported by the National Natural Science Foundation of China(51902187,52072224,51732007)the Natural Science Foundation of Shandong Province(ZR2018BEM010)+2 种基金the Science Fund for Distinguished Young Scholars of Shandong Province(ZR2019JQ16)the Fundamental Research Funds of Shandong University,Young Elite Scientist Sponsorship Program by CAST(YESS)the Collaborative Innovation Center of Technology and Equipment for Biological Diagnosis and Therapy in Universities of Shandong.
文摘Rechargeable aqueous zinc ion batteries (ZIBs),with the easy operation,cost effectiveness,and high safety,are emerging candidates for high-energy wearable/portable energy storage systems.Unfortunately,the unsatisfactory energy density and undesired long-term cycling performance of the cathode hinder the development of ZIBs.Here,we report the chemical preintercalation of a small amount of calcium ions into V2O5 as the cathode material.The cathode of Ca0.04V2O5·1.74H2O (CVO)was demonstrated to have a high specific capacity of 400 mA h g^-1at the current density of 0.05 A g^-1and 187 mA h g^-1at 10 A g^-1,along with impressive capacity retention (100%capacity retention at 10 A g^-1 for 3,000 cycles).Meanwhile,the CVO//Zn battery exhibits a high energy density of 308 Wh kg^-1and a power density of 467 W kg^-1at 0.5 A g^-1.The superior performance originates from the pinning effect of the calcium ions and the lubricating effect of the structural water.The energy storage mechanism of the CVO cathode was also investigated in detail.The new phase (Zn3(OH)2V2O7·2H2O) generated upon cycling participates in the electrochemical reaction and thus contributes to the excellent electrochemical performance.The small amount of Ca^2+ pre-inserted into the interlayer of V2O5 sheds light on constructing cathodes with high energy density for ZIBs.
基金supports by the Science and Tech-nology Research Project of Education Department of jilin Province(JKH20210453KJ,JJKH20210449KJ)the Development Plan of Sci-ence and Technology of jilin Province(YDZJ202101ZYTS187).
文摘Intercalation of ions between the adjacent MXene layers can change the interlayer environment and influence the electrochemical ion storage capacity.In order to understand the effect of multi-ions confined by the MXene layers on the performance of electrochemical energy storage,Co^(2+),Mn^(2+)and Ni^(2+)intercalated into Ti_(3)C_(2)T_(x)MXene which already pre-intercalated Al3+are obtained by spontaneous static action.Based on the monitor of(002)crystal orientation,intercalated multi-ions can regulate and control the interlayer environment of MXenes via stress,which induces lattice shrinkage occurring in the c axis.Limited by ion storage mechanism-performance,the multi-ion occupies the interspace of MXene and affects the electrochemical performance.This work would offer guidance to understand the relationship among the multi-ion and MXene by two-dimensional(2D)layered materials.
