Zinc ion hybrid capacitors(ZIHCs), which integrate the features of the high power of supercapacitors and the high energy of zinc ion batteries, are promising competitors in future electrochemical energy storage applic...Zinc ion hybrid capacitors(ZIHCs), which integrate the features of the high power of supercapacitors and the high energy of zinc ion batteries, are promising competitors in future electrochemical energy storage applications. Carbon-based materials are deemed the competitive candidates for cathodes of ZIHC due to their cost-effectiveness, high electronic conductivity, chemical inertness, controllable surface states, and tunable pore architectures. In recent years, great research efforts have been devoted to further improving the energy density and cycling stability of ZIHCs. Reasonable modification and optimization of carbon-based materials offer a remedy for these challenges. In this review, the structural design, and electrochemical properties of carbon-based cathode materials with different dimensions, as well as the selection of compatible, robust current collectors and separators for ZIHCs are discussed. The challenges and prospects of ZIHCs are showcased to guide the innovative development of carbon-based cathode materials and the development of novel ZIHCs.展开更多
High-performance and low-cost sodium-ion capacitors(SICs)show tremendous potential applications in public transport and grid energy storage.However,conventional SICs are limited by the low specific capacity,poor rate ...High-performance and low-cost sodium-ion capacitors(SICs)show tremendous potential applications in public transport and grid energy storage.However,conventional SICs are limited by the low specific capacity,poor rate capability,and low initial coulombic efficiency(ICE)of anode materials.Herein,we report layered iron vanadate(Fe5V15O39(OH)9·9H2O)ultrathin nanosheets with a thickness of~2.2 nm(FeVO UNSs)as a novel anode for rapid and reversible sodium-ion storage.According to in situ synchrotron X-ray diffractions and electrochemical analysis,the storage mechanism of FeVO UNSs anode is Na+intercalation pseudocapacitance under a safe potential window.The FeVO UNSs anode delivers high ICE(93.86%),high reversible capacity(292 mAh g^−1),excellent cycling stability,and remarkable rate capability.Furthermore,a pseudocapacitor–battery hybrid SIC(PBH-SIC)consisting of pseudocapacitor-type FeVO UNSs anode and battery-type Na3(VO)2(PO4)2F cathode is assembled with the elimination of presodiation treatments.The PBH-SIC involves faradaic reaction on both cathode and anode materials,delivering a high energy density of 126 Wh kg^−1 at 91 W kg^−1,a high power density of 7.6 kW kg^−1 with an energy density of 43 Wh kg−1,and 9000 stable cycles.The tunable vanadate materials with high-performance Na+intercalation pseudocapacitance provide a direction for developing next-generation highenergy capacitors.展开更多
Potassium-ion hybrid capacitors(PIHCs)reconcile the advantages of batteries and supercapacitors,exhibiting both good energy density and high-power density.However,the low-rate performance and poor cycle stability of b...Potassium-ion hybrid capacitors(PIHCs)reconcile the advantages of batteries and supercapacitors,exhibiting both good energy density and high-power density.However,the low-rate performance and poor cycle stability of battery-type anodes hinder their practical application.Herein,phosphorus/nitrogen co-doped hollow carbon fibers(P-HCNFs)are prepared by a facile template method.The stable grape-like structure with continuous and interconnected cavity structure is an ideal scaffold for shortening the ion transport and relieving volume expansion,while the introduction of P atoms and intrinsic N atoms can create abundant extrinsic/intrinsic defects and additional active sites,reducing the K+diffusion barrier and improving the capacitive-controlled capacity.The P-HCNFs delivers a high specific capacity of 310 mAh·g^(-1)at 0.1 A·g^(-1)with remarkable ultra-high-rate performance(140 mAh·g^(-1)at 50 A·g^(-1))and retains an impressive capacity retention of 87%after 10,000 cycles at 10 A·g^(-1).As expected,the as-assembled PIHCs present a high energy density(115.8 Wh·kg^(-1)at 378.0 W·kg^(-1))and excellent capacity retention of 91%after 20,000 cycles.This work not only shows great potential for utilizing heteroatom-doping and structural design strategies to boost potassium storage,but also paves the way for advancing the practicality of high-energy PIHCs devices.展开更多
Several emerging energy storage technologies and systems have been demonstrated that feature low cost,high rate capability,and durability for potential use in large-scale grid and high-power applications.Owing to its ...Several emerging energy storage technologies and systems have been demonstrated that feature low cost,high rate capability,and durability for potential use in large-scale grid and high-power applications.Owing to its outstanding ion conductivity,ultrafast Na-ion insertion kinetics,excellent structural stability,and large theoretical capacity,the sodium superionic conductor(NASICON)-structured insertion material NaTi2(PO4)3(NTP)has attracted considerable attention as the optimal electrode material for sodium-ion batteries(SIBs)and Na-ion hybrid capacitors(NHCs).On the basis of recent studies,NaTi2(PO4)3 has raised the rate capabilities,cycling stability,and mass loading of rechargeable SIBs and NHCs to commercially acceptable levels.In this comprehensive review,starting with the structures and electrochemical properties of NTP,we present recent progress in the application of NTP to SIBs,including non-aqueous batteries,aqueous batteries,aqueous batteries with desalination,and sodium-ion hybrid capacitors.After a thorough discussion of the unique NASICON structure of NTP,various strategies for improving the performance of NTP electrode have been presented and summarized in detail.Further,the major challenges and perspectives regarding the prospects for the use of NTP-based electrodes in energy storage systems have also been summarized to offer a guideline for further improving the performance of NTP-based electrodes.展开更多
Carbon nanofibers films are typical flexible electrode in the field of energy storage,but their application in Zinc-ion hybrid capacitors(ZIHCs)is limited by the low energy density due to the lack of active adsorption...Carbon nanofibers films are typical flexible electrode in the field of energy storage,but their application in Zinc-ion hybrid capacitors(ZIHCs)is limited by the low energy density due to the lack of active adsorption sites.In this work,an in-situ exfoliation strategy is reported to modulate the chemisorption sites of carbon nanofibers by high pyridine/pyrrole nitrogen doping and carbonyl functionalization.The experimental results and theoretical calculations indicate that the highly electronegative pyridine/pyrrole nitrogen dopants can not only greatly reduce the binding energy between carbonyl group and Z n2+by inducing charge delocalization of the carbonyl group,but also promote the adsorption of Zn2+by bonding with the carbonyl group to form N–Zn–O bond.Benefit from the multiple highly active chemisorption sites generated by the synergy between carbonyl groups and pyridine/pyrrole nitrogen atoms,the resulting carbon nanofibers film cathode displays a high energy density,an ultralong-term lifespan,and excellent capacity reservation under commercial mass loading(14.45 mg cm-2).Particularly,the cathodes can also operate stably in flexible or quasi-solid devices,indicating its application potential in flexible electronic products.This work established a universal method to solve the bottleneck problem of insufficient active adsorption sites of carbon-based ZIHCs.Imoproved should be changed into Improved.展开更多
Lithium-ion hybrid capacitors(LIHCs)have drawn extensive attention in fleld of energy storage.However,the absence of appropriate electrode materials with rapid kinetics restricted the overall performance of the capaci...Lithium-ion hybrid capacitors(LIHCs)have drawn extensive attention in fleld of energy storage.However,the absence of appropriate electrode materials with rapid kinetics restricted the overall performance of the capacitors.Herein,hierarchical N,P-codoped hollow car-bon nanospheres coupling with WS_(2) nanosheets(N,P-codoped HCNS/WS_(2)NSs)were fabricated for boosting lithium storage materials.Specially,the WS_(2) nanosheets with several layers embedded in the N,P-codoped hollow carbon nanospheres could not only enhance the conduc-tivity of composites,but also provide abundant channels for the rapid transfer of ions.As a result,as-prepared N,P-codoped HCNS/WS_(2) NSs demonstrated superior rate performance and long-term cycling stability.The reversible discharge capacity of 725.2 mAh·g^(-1) could be preserved after 1000 cycles at a current density of 1.0 A·g^(-1).Fur-thermore,LIHCs devices were assembled by using N,P-codoped HCNS/WS_(2) NSs and activated carbon(AC)as the cathode and anode,which exhibited high energy density of 166.7 Wh·kg^(-1) and power density of 5312.4 W·kg^(-1).Last but not least,the capacity almost had no obvious deterioration after 6000 cycles at a high current density of 10.0 A·g^(-1).展开更多
The design and development of energy storage device with high energy/power density has become a research hotspot.Zinc-ion hybrid capacitors(ZHCs)are considered as one of the most promising candidates.However,the appli...The design and development of energy storage device with high energy/power density has become a research hotspot.Zinc-ion hybrid capacitors(ZHCs)are considered as one of the most promising candidates.However,the application of ZHCs is hindered by their low energy density at high power density due to the unsatisfactory cathode material.In this study,a novel 3D phosphorus-doped carbon nanotube/reduced graphene oxide(P-CNT/rGO)aerogel cathode is synthesized through a synergistic modification strategy of CNT insertion and P doping modification combined with 3D porous design.The as-obtained P-CNT/rGO aerogel cathode manifests significantly increased surface aera,expanded interlayer spacing,and enhanced pseudocapacitance behavior,thus leading to significantly enhanced specific capacitance and superb ions transport performance.The as-assembled ZHC based on P-CNT/rGO cathode delivers a superior energy density of 42.2 Wh/kg at an extreme-high power density of 80 kW/kg and excellent cycle life.In-depth kinetic analyses are undertaken to prove the enhanced pseudocapacitance behavior and exceptional power output capability of ZHCs.Furthermore,the reaction mechanism of physical and chemical adsorption/desorption of electrolyte ions on the P-CNT/rGO cathode is revealed by systematic ex-situ characterizations.This work can provide a valuable reference for developing advanced graphene-based cathode for high energy/power density ZHCs.展开更多
Potassium ion hybrid capacitors(PIHC)have promising applications in medium and large-scale energy storage systems due to their high energy/power density,abundant potassium resource and low cost.However,the slow kineti...Potassium ion hybrid capacitors(PIHC)have promising applications in medium and large-scale energy storage systems due to their high energy/power density,abundant potassium resource and low cost.However,the slow kinetics of battery-type anodes originating from the large-size K+results in a mismatch between the two electrodes,rendering the modest energy density of PIHC.Herein,we first develop an electrospinning strategy to successfully synthesize fibrous precursor by using the HNO_(3)pre-oxidized low-softening-point coal pitch as the low-cost raw material.With further carbonization or KOH activation,the two types of carbon nanofibers(CNF)are fabricated as anode and cathode materials,respectively,towards the dual-carbon PIHC devices.Thanks to its threedimensional interconnected porous conducting network and large layer spacing,the resulted CNF anode material is endowed with high reversible capacities,excellent rate and long cycle stability.Meanwhile,the activated CNF cathode with a large surface area of 2169 m^(2)·g^(-1)exhibits excellent capacitive performance.A PIHC constructed with the two fibrous electrodes delivers an energy density of110.0 Wh·kg^(-1)at 200.0 W kg^(-1),along with a capacitance retention of 83.5%after 10,000 cycles at 1.0 A·g^(-1).The contribution here provides a cost-efficiency avenue and platform for advanced dual-carbon PIHC.展开更多
Although aqueous zinc ion hybrid capacitors have advantageous integration of batteries and supercapacitors,they still suffer from the inherent problems of dendrite growth and interfacial side reactions on Zn anodes.He...Although aqueous zinc ion hybrid capacitors have advantageous integration of batteries and supercapacitors,they still suffer from the inherent problems of dendrite growth and interfacial side reactions on Zn anodes.Herein,a universal fast zinc-ion diffusion layer on a three-dimensional(3 D)mesh structure model is demonstrated to effectively improve Zn plating/stripping reversibility.The fast ion diffusion alloy layer accelerates the Zn^(2+)migration in an orderly manner to homogenize Zn^(2+)flux and overcomes the defects of the commercial mesh substrate,effectively avoiding dendrite growth and side reactions.Consequently,the proof-of-concept silver-zinc alloy modified stainless steel mesh delivers superb reversibility with the high coulombic efficiency over 99.4%at 4 mA cm^(-2)after 1600 cycles and excellent reliability of over 830 h at 1 mA cm^(-2),Its feasibility is also evidenced in commercial zinc ion hybrid capacitors with activated carbon as the cathode.This work enriches the fundamental comprehension of fast zinc-ion diffusion layer combined with a 3 D substrate on the Zn deposition and opens a universal approach to design advanced host for Zn electrodes in zinc ion hybrid capacitors.展开更多
The widespread implementation of supercapacitors is hindered by the limited energy density and the pricey porous carbon electrode materials.The cost of porous carbon is a significant factor in the overall cost of supe...The widespread implementation of supercapacitors is hindered by the limited energy density and the pricey porous carbon electrode materials.The cost of porous carbon is a significant factor in the overall cost of supercapacitors,therefore a high carbon yield could effectively mitigate the production cost of porous carbon.This study proposes a method to produce porous carbon spheres through a spray drying technique combined with a carbonization process,utilizing renewable enzymatic hydrolysis lignin as the carbon source and KOH as the activation agent.The purpose of this study is to examine the relationship between the quantity of activation agent and the development of morphology,pore structure,and specific surface area of the obtained porous carbon materials.We demonstrate that this approach significantly enhances the carbon yield of porous carbon,achieving a yield of 22%in contrast to the conventional carbonization-activation method(9%).The samples acquired through this method were found to contain a substantial amount of mesopores,with an average pore size of 1.59 to 1.85 nm and a mesopore ratio of 25.6%.Additionally,these samples showed high specific surface areas,ranging from 1051 to 1831 m2·g^(−1).Zinc ion hybrid capacitors with lignin-derived porous carbon cathode exhibited a high capacitance of 279 F·g^(−1) at 0.1 A·g^(−1) and an energy density of 99.1 Wh·kg^(−1) when the power density was 80 kW·kg^(−1).This research presents a novel approach for producing porous carbons with high yield through the utilization of a spray drying approach.展开更多
To satisfy the requirements for various electric systems and energy storage devices with both high energy density and power density as well as long lifespan, sodium-ion capacitors(SICs) consisting of battery anode and...To satisfy the requirements for various electric systems and energy storage devices with both high energy density and power density as well as long lifespan, sodium-ion capacitors(SICs) consisting of battery anode and supercapacitor cathode, have attracted much attention due to the abundant resources and low cost of sodium source. SICs bridge the gap between the batteries and the supercapacitors,which can be used as competitive candidates for large-scale energy storage. In this review, the battery-type anode materials and the capacitor-type cathode materials are classified and introduced in detail. The advantages of various electrolytes including organic electrolytes, aqueous electrolytes and ion liquid electrolytes are also discussed sequentially. In addition, from the perspective of practical value, the presentations of the SICs at the current situation and the potential application in urban rail are displayed. Finally, the challenge,future research and prospects towards the SICs are put forward.展开更多
Bismuth(Bi),as an alloy-based anode material,has attracted much atte ntion in the developme nt of sodiumion hybrid capacitors(SIHCs)due to its high theoretical capacity.However,the volume expansion of the Bi-based ano...Bismuth(Bi),as an alloy-based anode material,has attracted much atte ntion in the developme nt of sodiumion hybrid capacitors(SIHCs)due to its high theoretical capacity.However,the volume expansion of the Bi-based anode during the sodiation/desodiation process results in limited rate capability.In the present work,a porous Bi-based composite was constructed by a one-step hydrothermal method,and Bi was encapsulated in ligninderived nitrogen-doped porous carbon(Bi@LNPC)after carbonization.The obtained Bi nanoparticles could effectively adapt to the strain and shorten the diffusion distance of Na^(+).In addition,porous carbon skeleton provides a rigid conductive network for electronic transportation.Therefore,the assembled sodium-ion half-cell with Bi@LNPC anode shows ultra-high-rate capability.When the current density was enhanced from 0.1 to 50 A·g^(-1),the specific capacity decreased slightly from 351.5 to 342.8 mAh·g^(-1).Even at an extremely high current density of 200 A·g^(-1),it retains 81.3%capacity retention when compared to a current density of 1 A·g^(-1).The SIHCs assembled by Bi@LNPC show a high energy density of 63 Wh·kg^(-1).This work provides an effective method for developing high-rate Bi anode materials for sodium-ion hybrid capacitors(SIHCs)and sodium-ion batteries(SIBs).展开更多
Aqueous hybrid supercapacitors are attracting increasing attention due to their potential low cost,high safety and eco-friendliness.However,the narrow operating potential window of aqueous electrolyte and the lack of ...Aqueous hybrid supercapacitors are attracting increasing attention due to their potential low cost,high safety and eco-friendliness.However,the narrow operating potential window of aqueous electrolyte and the lack of suitable negative electrode materials seriously hinder its future applications.Here,we explore high concentrated lithium acetate with high ionic conductivity of 65.5 mS cm−1 as a green“water-in-salt”electrolyte,providing wide voltage window up to 2.8 V.It facilitates the reversible function of niobium tungsten oxide,Nb18W16O93,that otherwise only operations in organic electrolytes previously.The Nb18W16O93 with lithium-ion intercalation pseudocapacitive behavior exhibits excellent rate performance,high areal capacity,and ultra-long cycling stability.An aqueous lithium-ion hybrid capacitor is developed by using Nb18W16O93 as negative electrode combined with graphene as positive electrode in lithium acetate-based“water-in-salt”electrolyte,delivering a high energy density of 41.9 W kg−1,high power density of 20,000 W kg−1 and unexceptionable stability of 50,000 cycles.展开更多
As prospective energy storage devices,zinc-ion hybrid capacitors(ZHCs)still suffer from unsatisfactory cathode materials.Herein,the three dimensional(3D)N,B dual-doped carbon quantum dots/reduced graphene oxide(N,B-CQ...As prospective energy storage devices,zinc-ion hybrid capacitors(ZHCs)still suffer from unsatisfactory cathode materials.Herein,the three dimensional(3D)N,B dual-doped carbon quantum dots/reduced graphene oxide(N,B-CQDs/rGO)composite aerogel is prepared via a onepot hydrothermal method.Thanks to the synergism of CQDs modification and N,B dual-doping,the resultant N,B-CQDs/rGO composite aerogel delivers superior electrochemical properties.Furthermore,the as-obtained N,B-CQDs/rGO composite aerogel is served as a cathode for aqueous and flexible quasi-solid-state ZHCs for the first time.Impressively,the aqueous N,B-CQDs/rGO//Zn ZHC manifests a large energy density of 96.2 Wh·kg^(-1)at80 W·kg^(-1)and still remains a high energy density of 54.7Wh·kg^(-1)at a superb power density of 80 kW·kg^(-1).Meanwhile,kinetic analyses are employed to elucidate the prominent power performance,and various ex situ tests are undertaken to explore the energy storage mechanism of aqueous ZHC.More notably,the flexible quasi-solid-state N,B-CQDs/rGO//Zn ZHC displays a desirable energy density(89.1μWh·cm^(-2)),a superior power density(96,000μW·cm^(-2))and exceptional flexible performance.The present study offers a valuable reference for designing and developing advanced cathode materials for aqueous and flexible quasi-solid-state ZHCs.展开更多
Zinc-ion hybrid super-capacitors are regarded as promising safe energy storage systems,However,the relatively low volumetric energy density has become the main bottlenecks in practical applications of portable electro...Zinc-ion hybrid super-capacitors are regarded as promising safe energy storage systems,However,the relatively low volumetric energy density has become the main bottlenecks in practical applications of portable electronic devices,In this work,the zinc-ion hybrid super-capacitor with high volumetric energy density and superb cycle stability had been constructed which employing the high-density threedimensional graphene hydrogel as cathode and Zn foil used as anode in 1 mol/L ZnSO4 electrolyte.Benefiting from the abundant ion transport paths and the abundant active sites for graphene hydrogel with high density and porous structure,the zinc-ion hybrid super-capacitor exhibited an extremely high volumetric energy density of 118.42 Wh/L and a superb power density of 24.00 kW/L,as well as an excellent long cycle life(80% retention after 30,000 cycles at 10 A/g),which was superior to the volumetric energy density of the reported zinc-ion hybrid super-capacitors.This device,based on the fast ion adsorption/deso rption on the capacitor-type graphene cathode and reversible Zn^(2+) plating/stripping on the battery-type Zn anode,which will inspire the development of zinc-ion hybrid super-capacitor in miniaturized devices.展开更多
Sodium-based storage devices based on conversion-type metal sulfide anodes have attracted great atten-tion due to their multivalent ion redox reaction ability.However,they also suffer from sodium polysul-fides(NaPSs)s...Sodium-based storage devices based on conversion-type metal sulfide anodes have attracted great atten-tion due to their multivalent ion redox reaction ability.However,they also suffer from sodium polysul-fides(NaPSs)shuttling problems during the sluggish Na^(+) redox process,leading to"voltage failure"and rapid capacity decay.Herein,a metal cobalt-doping vanadium disulfide(Co-VS_(2))is proposed to simulta-neously accelerate the electrochemical reaction of VS_(2) and enhance the bidirectional redox of soluble NaPSs.It is found that the strong adsorption of NaPSs by V-Co alloy nanoparticles formed in situ during the conversion reaction of Co-VS_(2) can effectively inhibit the dissolution and shuttle of NaPSs,and ther-modynamically reduce the formation energy barrier of the reaction path to effectively drive the complete conversion reaction,while the metal transition of Co elements enhances reconversion kinetics to achieve high reversibility.Moreover,Co-VS_(2) also produce abundant sulfur vacancies and unsaturated sulfur edge defects,significantly improve ionic/electron diffusion kinetics.Therefore,the Co-VS_(2) anode exhibits ultrahigh rate capability(562 mA h g^(-1) at 5 A g^(-1)),high initial coulombic efficiency(~90%)and 12,000 ultralong cycle life with capacity retention of 90%in sodium-ion batteries(SIBs),as well as impressive energy/power density(118 Wh kg^(-1)/31,250 W kg^(-1))and over 10.000 stable cycles in sodium-ion hybrid capacitors(SIHCs).Moreover,the pouch cell-type SIHC displays a high-energy density of 102 Wh kg^(-1) and exceed 600 stable cycles.This work deepens the understanding of the electrochemical reaction mechanism of conversion-type metal sulfide anodes and provides a valuable solution to the shuttlingofNaPSs inSIBsandSIHCs.展开更多
The aqueous ammonium ion(NH_(4)^(+))is a promising charge carrier in virtue of its safety,environmental friendliness,abundant resources and small hydrated ionic size.The exploration of NH_(4)^(+)host electrodes with g...The aqueous ammonium ion(NH_(4)^(+))is a promising charge carrier in virtue of its safety,environmental friendliness,abundant resources and small hydrated ionic size.The exploration of NH_(4)^(+)host electrodes with good reversibility and large storage capacity to construct high-performance ammonium-ion hybrid capacitors(AIHCs),however,is still in its infancy.Herein,a facile etching technique is put forward to produce oxygen-deficient MnO_(2)(O_(d)-MnO_(2))as the electrode material for NH_(4)^(+)storage.According to the experimental and theoretical calculation results,the etching process not only creates more porosity,offering abundant active sites,but also generates abundant oxygen vacancies,which modify the structure of pristine MnO_(2),enhance charge storage capacity and boost ion diffusion kinetics.Consequently,Od-MnO_(2)can deliver a specific capacity of 155 mAh·g^(-1)at 0.5 A·g^(-1)and a good long-term cycling stability with86.8%capacity maintained after 10,000 cycles at5.0 A·g^(-1).Additionally,the NH_(4)^(+)storage mechanism was evidenced by several ex-situ characterization analyses.To examine the actual implementation of O_d-MnO_(2)as a positive electrode for NH_(4)^(+)full device,AIHCs are assembled with activated carbon functionalized with Fe_3O_(4)nanoparticles(Fe_(3)O_(4)@AC)as a negative electrode.A high specific capacitance of 184 F·g^(-1)at 0.5 A·g^(-1),satisfactory energy density of 102 Wh·kg^(-1)at 500 W·kg^(-1),a low self-discharge rate and good cycling durability after 10,000 cycles are attained.The electrochemical performance of these AIHCs is comparable to or surpass those of traditional supercapacitors with metal ions as charge carriers,highlighting the advantages of structural modification in enhancing the NH_(4)^(+)storage performance.展开更多
Aqueous zinc ion hybrid capacitors(ZIHCs)hold great potential for large-scale energy storage applications owing to their high safety and low cost,but suffer from low capacity and energy density.Herein,pyridinic nitrog...Aqueous zinc ion hybrid capacitors(ZIHCs)hold great potential for large-scale energy storage applications owing to their high safety and low cost,but suffer from low capacity and energy density.Herein,pyridinic nitrogen enriched porous carbon(nPC)was successfully synthesized via the growth,subsequent annealing and acid etching of bimetal organic frameworks for high capacity and safe ZIHCs with exceptional rate capability.Benefiting from the mesopores for easy ion diffusion,high electrical conductivity enabled by in-situ grown carbon nanotubes matrix and residual metal Co nanoparticles for fast electron transfer,sufficient micropores and high N content(8.9 at%)with dominated pyridinic N(54%)for enhanced zinc ion storage,the resulting nPC cathodes for ZIHCs achieved high capacities of 302 and137 m Ah g^(-1) at 1 and 18 A g^(-1),outperforming most reported carbon based cathodes.Theoretical results further disclosed that pyridinic N possessed larger binding energy of-4.99 eV to chemically coordinate with Zn2+than other N species.Moreover,quasi-solid-state ZIHCs with gelatin based gel electrolytes exhibited high energy density of 157.6 Wh kg^(-1) at 0.69 kW kg^(-1),high safety and mechanical flexibility to withstand mechanical deformation and drilling.This strategy of developing pyridinic nitrogen enriched porous carbon will pave a new avenue to construct safe ZIHCs with high energy densities.展开更多
基金the financial support from the National Natural Science Foundation of China (22108044)the 111 Project (B20088)+3 种基金the Fundamental Research Funds for the Central Universities (2572022DJ02)the Research and Development Program in Key Fields of Guangdong Province (2020B1111380002)the Basic Research and Applicable Basic Research in Guangzhou City (202201010290)the Guangdong Provincial Key Laboratory of Plant Resources Biorefinery (2021GDKLPRB07)。
文摘Zinc ion hybrid capacitors(ZIHCs), which integrate the features of the high power of supercapacitors and the high energy of zinc ion batteries, are promising competitors in future electrochemical energy storage applications. Carbon-based materials are deemed the competitive candidates for cathodes of ZIHC due to their cost-effectiveness, high electronic conductivity, chemical inertness, controllable surface states, and tunable pore architectures. In recent years, great research efforts have been devoted to further improving the energy density and cycling stability of ZIHCs. Reasonable modification and optimization of carbon-based materials offer a remedy for these challenges. In this review, the structural design, and electrochemical properties of carbon-based cathode materials with different dimensions, as well as the selection of compatible, robust current collectors and separators for ZIHCs are discussed. The challenges and prospects of ZIHCs are showcased to guide the innovative development of carbon-based cathode materials and the development of novel ZIHCs.
基金This work was financially supported by the National Natural Science Foundation of China(No.22005256)the National Key R&D Program of China(Grant No.2016YFA0202600)the Natural Science Foundation of Fujian Province of China(No.2020J01034).
文摘High-performance and low-cost sodium-ion capacitors(SICs)show tremendous potential applications in public transport and grid energy storage.However,conventional SICs are limited by the low specific capacity,poor rate capability,and low initial coulombic efficiency(ICE)of anode materials.Herein,we report layered iron vanadate(Fe5V15O39(OH)9·9H2O)ultrathin nanosheets with a thickness of~2.2 nm(FeVO UNSs)as a novel anode for rapid and reversible sodium-ion storage.According to in situ synchrotron X-ray diffractions and electrochemical analysis,the storage mechanism of FeVO UNSs anode is Na+intercalation pseudocapacitance under a safe potential window.The FeVO UNSs anode delivers high ICE(93.86%),high reversible capacity(292 mAh g^−1),excellent cycling stability,and remarkable rate capability.Furthermore,a pseudocapacitor–battery hybrid SIC(PBH-SIC)consisting of pseudocapacitor-type FeVO UNSs anode and battery-type Na3(VO)2(PO4)2F cathode is assembled with the elimination of presodiation treatments.The PBH-SIC involves faradaic reaction on both cathode and anode materials,delivering a high energy density of 126 Wh kg^−1 at 91 W kg^−1,a high power density of 7.6 kW kg^−1 with an energy density of 43 Wh kg−1,and 9000 stable cycles.The tunable vanadate materials with high-performance Na+intercalation pseudocapacitance provide a direction for developing next-generation highenergy capacitors.
基金financially supported by the Youth Innovation Team of Colleges and Universities in Shandong Province(No.2022KJ223)the National Natural Science Foundation of China(Nos.22078179 and 52007110)+1 种基金the Natural Science Foundation of Shandong Province(Nos.ZR2022JQ10 and ZR2021MA026)Taishan S cholar Foundation(No.tsqn201812063)。
文摘Potassium-ion hybrid capacitors(PIHCs)reconcile the advantages of batteries and supercapacitors,exhibiting both good energy density and high-power density.However,the low-rate performance and poor cycle stability of battery-type anodes hinder their practical application.Herein,phosphorus/nitrogen co-doped hollow carbon fibers(P-HCNFs)are prepared by a facile template method.The stable grape-like structure with continuous and interconnected cavity structure is an ideal scaffold for shortening the ion transport and relieving volume expansion,while the introduction of P atoms and intrinsic N atoms can create abundant extrinsic/intrinsic defects and additional active sites,reducing the K+diffusion barrier and improving the capacitive-controlled capacity.The P-HCNFs delivers a high specific capacity of 310 mAh·g^(-1)at 0.1 A·g^(-1)with remarkable ultra-high-rate performance(140 mAh·g^(-1)at 50 A·g^(-1))and retains an impressive capacity retention of 87%after 10,000 cycles at 10 A·g^(-1).As expected,the as-assembled PIHCs present a high energy density(115.8 Wh·kg^(-1)at 378.0 W·kg^(-1))and excellent capacity retention of 91%after 20,000 cycles.This work not only shows great potential for utilizing heteroatom-doping and structural design strategies to boost potassium storage,but also paves the way for advancing the practicality of high-energy PIHCs devices.
基金supported by the National Natural Science Foundation of China (No. 51302079)the Natural Science Foundation of Hunan Province (No. 2017JJ1008)the Key Research and Development Program of Hunan Province of China under Grant 2018GK2031
文摘Several emerging energy storage technologies and systems have been demonstrated that feature low cost,high rate capability,and durability for potential use in large-scale grid and high-power applications.Owing to its outstanding ion conductivity,ultrafast Na-ion insertion kinetics,excellent structural stability,and large theoretical capacity,the sodium superionic conductor(NASICON)-structured insertion material NaTi2(PO4)3(NTP)has attracted considerable attention as the optimal electrode material for sodium-ion batteries(SIBs)and Na-ion hybrid capacitors(NHCs).On the basis of recent studies,NaTi2(PO4)3 has raised the rate capabilities,cycling stability,and mass loading of rechargeable SIBs and NHCs to commercially acceptable levels.In this comprehensive review,starting with the structures and electrochemical properties of NTP,we present recent progress in the application of NTP to SIBs,including non-aqueous batteries,aqueous batteries,aqueous batteries with desalination,and sodium-ion hybrid capacitors.After a thorough discussion of the unique NASICON structure of NTP,various strategies for improving the performance of NTP electrode have been presented and summarized in detail.Further,the major challenges and perspectives regarding the prospects for the use of NTP-based electrodes in energy storage systems have also been summarized to offer a guideline for further improving the performance of NTP-based electrodes.
基金funds from the National Natural Science Foundation of China(51772082,51804106,and 51574117)the Natural Science Foundation of Hunan Province(2019JJ30002,2019JJ50061 and 2020CB1007)Natural Science Foundation of Guangdong Providence(2018A030310571)。
文摘Carbon nanofibers films are typical flexible electrode in the field of energy storage,but their application in Zinc-ion hybrid capacitors(ZIHCs)is limited by the low energy density due to the lack of active adsorption sites.In this work,an in-situ exfoliation strategy is reported to modulate the chemisorption sites of carbon nanofibers by high pyridine/pyrrole nitrogen doping and carbonyl functionalization.The experimental results and theoretical calculations indicate that the highly electronegative pyridine/pyrrole nitrogen dopants can not only greatly reduce the binding energy between carbonyl group and Z n2+by inducing charge delocalization of the carbonyl group,but also promote the adsorption of Zn2+by bonding with the carbonyl group to form N–Zn–O bond.Benefit from the multiple highly active chemisorption sites generated by the synergy between carbonyl groups and pyridine/pyrrole nitrogen atoms,the resulting carbon nanofibers film cathode displays a high energy density,an ultralong-term lifespan,and excellent capacity reservation under commercial mass loading(14.45 mg cm-2).Particularly,the cathodes can also operate stably in flexible or quasi-solid devices,indicating its application potential in flexible electronic products.This work established a universal method to solve the bottleneck problem of insufficient active adsorption sites of carbon-based ZIHCs.Imoproved should be changed into Improved.
基金the National Natural Science Foundation of China(Nos.51902266 and 22002003)the Innovation Foundation for Doctor Dissertation of Northwestern Poly technical University(No.CX2021009)+1 种基金the Key Research and Development Projects of Shaanxi Province(No.2020GXLH-Z-032)the Research Fund of the State Key Laboratory of Solidification Processing(NPU),China(No.G8QT0461G),and the Research Fund of the State Key Laboratory of Solidification Processing(NPU),China(No.SKLSP202004)。
文摘Lithium-ion hybrid capacitors(LIHCs)have drawn extensive attention in fleld of energy storage.However,the absence of appropriate electrode materials with rapid kinetics restricted the overall performance of the capacitors.Herein,hierarchical N,P-codoped hollow car-bon nanospheres coupling with WS_(2) nanosheets(N,P-codoped HCNS/WS_(2)NSs)were fabricated for boosting lithium storage materials.Specially,the WS_(2) nanosheets with several layers embedded in the N,P-codoped hollow carbon nanospheres could not only enhance the conduc-tivity of composites,but also provide abundant channels for the rapid transfer of ions.As a result,as-prepared N,P-codoped HCNS/WS_(2) NSs demonstrated superior rate performance and long-term cycling stability.The reversible discharge capacity of 725.2 mAh·g^(-1) could be preserved after 1000 cycles at a current density of 1.0 A·g^(-1).Fur-thermore,LIHCs devices were assembled by using N,P-codoped HCNS/WS_(2) NSs and activated carbon(AC)as the cathode and anode,which exhibited high energy density of 166.7 Wh·kg^(-1) and power density of 5312.4 W·kg^(-1).Last but not least,the capacity almost had no obvious deterioration after 6000 cycles at a high current density of 10.0 A·g^(-1).
基金financially supported by Distinguished Young Scientists of Hunan Province(No.2022JJ10024)National Natural Science Foundation of China(No.21601057)+1 种基金Natural Science Foundation of Hunan Province(No.2021JJ30216)Key Projects of Hunan Provincial Education Department(No.22A0412).
文摘The design and development of energy storage device with high energy/power density has become a research hotspot.Zinc-ion hybrid capacitors(ZHCs)are considered as one of the most promising candidates.However,the application of ZHCs is hindered by their low energy density at high power density due to the unsatisfactory cathode material.In this study,a novel 3D phosphorus-doped carbon nanotube/reduced graphene oxide(P-CNT/rGO)aerogel cathode is synthesized through a synergistic modification strategy of CNT insertion and P doping modification combined with 3D porous design.The as-obtained P-CNT/rGO aerogel cathode manifests significantly increased surface aera,expanded interlayer spacing,and enhanced pseudocapacitance behavior,thus leading to significantly enhanced specific capacitance and superb ions transport performance.The as-assembled ZHC based on P-CNT/rGO cathode delivers a superior energy density of 42.2 Wh/kg at an extreme-high power density of 80 kW/kg and excellent cycle life.In-depth kinetic analyses are undertaken to prove the enhanced pseudocapacitance behavior and exceptional power output capability of ZHCs.Furthermore,the reaction mechanism of physical and chemical adsorption/desorption of electrolyte ions on the P-CNT/rGO cathode is revealed by systematic ex-situ characterizations.This work can provide a valuable reference for developing advanced graphene-based cathode for high energy/power density ZHCs.
基金financially supported by the National Natural Science Foundation of China(Nos.52072151 and 52171211)Taishan Scholars(No.ts201712050)+2 种基金Jinan Independent Innovative Team(No.2020GXRC015)the Natural Science Doctoral Foundation of Shandong Province(No.ZR2019BB057)the Major Program of Shandong Province Natural Science Foundation(No.ZR2021ZD05)。
文摘Potassium ion hybrid capacitors(PIHC)have promising applications in medium and large-scale energy storage systems due to their high energy/power density,abundant potassium resource and low cost.However,the slow kinetics of battery-type anodes originating from the large-size K+results in a mismatch between the two electrodes,rendering the modest energy density of PIHC.Herein,we first develop an electrospinning strategy to successfully synthesize fibrous precursor by using the HNO_(3)pre-oxidized low-softening-point coal pitch as the low-cost raw material.With further carbonization or KOH activation,the two types of carbon nanofibers(CNF)are fabricated as anode and cathode materials,respectively,towards the dual-carbon PIHC devices.Thanks to its threedimensional interconnected porous conducting network and large layer spacing,the resulted CNF anode material is endowed with high reversible capacities,excellent rate and long cycle stability.Meanwhile,the activated CNF cathode with a large surface area of 2169 m^(2)·g^(-1)exhibits excellent capacitive performance.A PIHC constructed with the two fibrous electrodes delivers an energy density of110.0 Wh·kg^(-1)at 200.0 W kg^(-1),along with a capacitance retention of 83.5%after 10,000 cycles at 1.0 A·g^(-1).The contribution here provides a cost-efficiency avenue and platform for advanced dual-carbon PIHC.
基金financially supported by the National Natural Science Foundation of China(51901249,U1904216)。
文摘Although aqueous zinc ion hybrid capacitors have advantageous integration of batteries and supercapacitors,they still suffer from the inherent problems of dendrite growth and interfacial side reactions on Zn anodes.Herein,a universal fast zinc-ion diffusion layer on a three-dimensional(3 D)mesh structure model is demonstrated to effectively improve Zn plating/stripping reversibility.The fast ion diffusion alloy layer accelerates the Zn^(2+)migration in an orderly manner to homogenize Zn^(2+)flux and overcomes the defects of the commercial mesh substrate,effectively avoiding dendrite growth and side reactions.Consequently,the proof-of-concept silver-zinc alloy modified stainless steel mesh delivers superb reversibility with the high coulombic efficiency over 99.4%at 4 mA cm^(-2)after 1600 cycles and excellent reliability of over 830 h at 1 mA cm^(-2),Its feasibility is also evidenced in commercial zinc ion hybrid capacitors with activated carbon as the cathode.This work enriches the fundamental comprehension of fast zinc-ion diffusion layer combined with a 3 D substrate on the Zn deposition and opens a universal approach to design advanced host for Zn electrodes in zinc ion hybrid capacitors.
基金support from the National Natural Science Foundation of China(Grant No.22108044)the Research and Development Program in Key Fields of Guangdong Province(Grant No.2020B1111380002)the Basic Research and Applicable Basic Research in Guangzhou City(Grant No.202201010290).
文摘The widespread implementation of supercapacitors is hindered by the limited energy density and the pricey porous carbon electrode materials.The cost of porous carbon is a significant factor in the overall cost of supercapacitors,therefore a high carbon yield could effectively mitigate the production cost of porous carbon.This study proposes a method to produce porous carbon spheres through a spray drying technique combined with a carbonization process,utilizing renewable enzymatic hydrolysis lignin as the carbon source and KOH as the activation agent.The purpose of this study is to examine the relationship between the quantity of activation agent and the development of morphology,pore structure,and specific surface area of the obtained porous carbon materials.We demonstrate that this approach significantly enhances the carbon yield of porous carbon,achieving a yield of 22%in contrast to the conventional carbonization-activation method(9%).The samples acquired through this method were found to contain a substantial amount of mesopores,with an average pore size of 1.59 to 1.85 nm and a mesopore ratio of 25.6%.Additionally,these samples showed high specific surface areas,ranging from 1051 to 1831 m2·g^(−1).Zinc ion hybrid capacitors with lignin-derived porous carbon cathode exhibited a high capacitance of 279 F·g^(−1) at 0.1 A·g^(−1) and an energy density of 99.1 Wh·kg^(−1) when the power density was 80 kW·kg^(−1).This research presents a novel approach for producing porous carbons with high yield through the utilization of a spray drying approach.
基金financially supported by the National Natural Science Foundation of China (51672308, 51972025 and 61888102)
文摘To satisfy the requirements for various electric systems and energy storage devices with both high energy density and power density as well as long lifespan, sodium-ion capacitors(SICs) consisting of battery anode and supercapacitor cathode, have attracted much attention due to the abundant resources and low cost of sodium source. SICs bridge the gap between the batteries and the supercapacitors,which can be used as competitive candidates for large-scale energy storage. In this review, the battery-type anode materials and the capacitor-type cathode materials are classified and introduced in detail. The advantages of various electrolytes including organic electrolytes, aqueous electrolytes and ion liquid electrolytes are also discussed sequentially. In addition, from the perspective of practical value, the presentations of the SICs at the current situation and the potential application in urban rail are displayed. Finally, the challenge,future research and prospects towards the SICs are put forward.
基金financially supported by the National Natural Science Foundation of China(No.22108044)the Research and Development Program in Key Fields of Guangdong Province(No.2020B1111380002)+1 种基金the Basic Research and Applicable Basic Research in Guangzhou City(No.202201010290)the financial support from the Guangdong Provincial Key Laboratory of Plant Resources Biorefinery(No.2021GDKLPRB07)。
文摘Bismuth(Bi),as an alloy-based anode material,has attracted much atte ntion in the developme nt of sodiumion hybrid capacitors(SIHCs)due to its high theoretical capacity.However,the volume expansion of the Bi-based anode during the sodiation/desodiation process results in limited rate capability.In the present work,a porous Bi-based composite was constructed by a one-step hydrothermal method,and Bi was encapsulated in ligninderived nitrogen-doped porous carbon(Bi@LNPC)after carbonization.The obtained Bi nanoparticles could effectively adapt to the strain and shorten the diffusion distance of Na^(+).In addition,porous carbon skeleton provides a rigid conductive network for electronic transportation.Therefore,the assembled sodium-ion half-cell with Bi@LNPC anode shows ultra-high-rate capability.When the current density was enhanced from 0.1 to 50 A·g^(-1),the specific capacity decreased slightly from 351.5 to 342.8 mAh·g^(-1).Even at an extremely high current density of 200 A·g^(-1),it retains 81.3%capacity retention when compared to a current density of 1 A·g^(-1).The SIHCs assembled by Bi@LNPC show a high energy density of 63 Wh·kg^(-1).This work provides an effective method for developing high-rate Bi anode materials for sodium-ion hybrid capacitors(SIHCs)and sodium-ion batteries(SIBs).
基金Shengyang Dong and Yi Wang contributed equally to this work.This work was supported by the National Natural Science Foundation of China(Nos.U1802256,51672128,51802154)the Key Research and Development Program in Jiangsu Province(BE2018122)+1 种基金Jiangsu Specially-Appointed Professors Program,the Fundamental Research Funds for the Central Universities(NE2016005)the Startup Foundation for Introducing Talent of NUIST(1441622001004).
文摘Aqueous hybrid supercapacitors are attracting increasing attention due to their potential low cost,high safety and eco-friendliness.However,the narrow operating potential window of aqueous electrolyte and the lack of suitable negative electrode materials seriously hinder its future applications.Here,we explore high concentrated lithium acetate with high ionic conductivity of 65.5 mS cm−1 as a green“water-in-salt”electrolyte,providing wide voltage window up to 2.8 V.It facilitates the reversible function of niobium tungsten oxide,Nb18W16O93,that otherwise only operations in organic electrolytes previously.The Nb18W16O93 with lithium-ion intercalation pseudocapacitive behavior exhibits excellent rate performance,high areal capacity,and ultra-long cycling stability.An aqueous lithium-ion hybrid capacitor is developed by using Nb18W16O93 as negative electrode combined with graphene as positive electrode in lithium acetate-based“water-in-salt”electrolyte,delivering a high energy density of 41.9 W kg−1,high power density of 20,000 W kg−1 and unexceptionable stability of 50,000 cycles.
基金financially supported by the Distinguished Young Scientists of Hunan Province(No.2022JJ10024)the National Natural Science Foundation of China(No.21601057)+1 种基金the Natural Science Foundation of Hunan Province(No.2021JJ30216)Key Projects of Hunan Provincial Education Department(No.22A0412)。
文摘As prospective energy storage devices,zinc-ion hybrid capacitors(ZHCs)still suffer from unsatisfactory cathode materials.Herein,the three dimensional(3D)N,B dual-doped carbon quantum dots/reduced graphene oxide(N,B-CQDs/rGO)composite aerogel is prepared via a onepot hydrothermal method.Thanks to the synergism of CQDs modification and N,B dual-doping,the resultant N,B-CQDs/rGO composite aerogel delivers superior electrochemical properties.Furthermore,the as-obtained N,B-CQDs/rGO composite aerogel is served as a cathode for aqueous and flexible quasi-solid-state ZHCs for the first time.Impressively,the aqueous N,B-CQDs/rGO//Zn ZHC manifests a large energy density of 96.2 Wh·kg^(-1)at80 W·kg^(-1)and still remains a high energy density of 54.7Wh·kg^(-1)at a superb power density of 80 kW·kg^(-1).Meanwhile,kinetic analyses are employed to elucidate the prominent power performance,and various ex situ tests are undertaken to explore the energy storage mechanism of aqueous ZHC.More notably,the flexible quasi-solid-state N,B-CQDs/rGO//Zn ZHC displays a desirable energy density(89.1μWh·cm^(-2)),a superior power density(96,000μW·cm^(-2))and exceptional flexible performance.The present study offers a valuable reference for designing and developing advanced cathode materials for aqueous and flexible quasi-solid-state ZHCs.
基金supported by the National Nature Science Foundations of China (No.21965019)the China Postdoctoral Science Foundation (No.2017M613248)+1 种基金the Natural Science Foundation of Gansu Province (No.1506 RJZA091)the Scientific Research Foundation of the Higher Education Institutions of Gansu Province (No.2015A-037)。
文摘Zinc-ion hybrid super-capacitors are regarded as promising safe energy storage systems,However,the relatively low volumetric energy density has become the main bottlenecks in practical applications of portable electronic devices,In this work,the zinc-ion hybrid super-capacitor with high volumetric energy density and superb cycle stability had been constructed which employing the high-density threedimensional graphene hydrogel as cathode and Zn foil used as anode in 1 mol/L ZnSO4 electrolyte.Benefiting from the abundant ion transport paths and the abundant active sites for graphene hydrogel with high density and porous structure,the zinc-ion hybrid super-capacitor exhibited an extremely high volumetric energy density of 118.42 Wh/L and a superb power density of 24.00 kW/L,as well as an excellent long cycle life(80% retention after 30,000 cycles at 10 A/g),which was superior to the volumetric energy density of the reported zinc-ion hybrid super-capacitors.This device,based on the fast ion adsorption/deso rption on the capacitor-type graphene cathode and reversible Zn^(2+) plating/stripping on the battery-type Zn anode,which will inspire the development of zinc-ion hybrid super-capacitor in miniaturized devices.
基金supported by the National Natural Science Foundation of China(Grant Nos.52072322,22209137,51604250)the Department of Science and Technology of Sichuan Province(CN)(GrantNos.2022YFG0294,23GJHZ0147,23ZDYF0262)Production-Education Integration Demonstration Project of Sichuan Province"Photovoltaic Industry Production-Education Integration Comprehensive Demonstration Base of Sichuan Province"(Sichuan Financial Education[2022]No.106.n)。
文摘Sodium-based storage devices based on conversion-type metal sulfide anodes have attracted great atten-tion due to their multivalent ion redox reaction ability.However,they also suffer from sodium polysul-fides(NaPSs)shuttling problems during the sluggish Na^(+) redox process,leading to"voltage failure"and rapid capacity decay.Herein,a metal cobalt-doping vanadium disulfide(Co-VS_(2))is proposed to simulta-neously accelerate the electrochemical reaction of VS_(2) and enhance the bidirectional redox of soluble NaPSs.It is found that the strong adsorption of NaPSs by V-Co alloy nanoparticles formed in situ during the conversion reaction of Co-VS_(2) can effectively inhibit the dissolution and shuttle of NaPSs,and ther-modynamically reduce the formation energy barrier of the reaction path to effectively drive the complete conversion reaction,while the metal transition of Co elements enhances reconversion kinetics to achieve high reversibility.Moreover,Co-VS_(2) also produce abundant sulfur vacancies and unsaturated sulfur edge defects,significantly improve ionic/electron diffusion kinetics.Therefore,the Co-VS_(2) anode exhibits ultrahigh rate capability(562 mA h g^(-1) at 5 A g^(-1)),high initial coulombic efficiency(~90%)and 12,000 ultralong cycle life with capacity retention of 90%in sodium-ion batteries(SIBs),as well as impressive energy/power density(118 Wh kg^(-1)/31,250 W kg^(-1))and over 10.000 stable cycles in sodium-ion hybrid capacitors(SIHCs).Moreover,the pouch cell-type SIHC displays a high-energy density of 102 Wh kg^(-1) and exceed 600 stable cycles.This work deepens the understanding of the electrochemical reaction mechanism of conversion-type metal sulfide anodes and provides a valuable solution to the shuttlingofNaPSs inSIBsandSIHCs.
基金financially supported by the National Natural Science Foundation of China(No.22365001)。
文摘The aqueous ammonium ion(NH_(4)^(+))is a promising charge carrier in virtue of its safety,environmental friendliness,abundant resources and small hydrated ionic size.The exploration of NH_(4)^(+)host electrodes with good reversibility and large storage capacity to construct high-performance ammonium-ion hybrid capacitors(AIHCs),however,is still in its infancy.Herein,a facile etching technique is put forward to produce oxygen-deficient MnO_(2)(O_(d)-MnO_(2))as the electrode material for NH_(4)^(+)storage.According to the experimental and theoretical calculation results,the etching process not only creates more porosity,offering abundant active sites,but also generates abundant oxygen vacancies,which modify the structure of pristine MnO_(2),enhance charge storage capacity and boost ion diffusion kinetics.Consequently,Od-MnO_(2)can deliver a specific capacity of 155 mAh·g^(-1)at 0.5 A·g^(-1)and a good long-term cycling stability with86.8%capacity maintained after 10,000 cycles at5.0 A·g^(-1).Additionally,the NH_(4)^(+)storage mechanism was evidenced by several ex-situ characterization analyses.To examine the actual implementation of O_d-MnO_(2)as a positive electrode for NH_(4)^(+)full device,AIHCs are assembled with activated carbon functionalized with Fe_3O_(4)nanoparticles(Fe_(3)O_(4)@AC)as a negative electrode.A high specific capacitance of 184 F·g^(-1)at 0.5 A·g^(-1),satisfactory energy density of 102 Wh·kg^(-1)at 500 W·kg^(-1),a low self-discharge rate and good cycling durability after 10,000 cycles are attained.The electrochemical performance of these AIHCs is comparable to or surpass those of traditional supercapacitors with metal ions as charge carriers,highlighting the advantages of structural modification in enhancing the NH_(4)^(+)storage performance.
基金financially supported by the National Key R@D Program of China(Grants 2016YBF0100100 and 2016YFA0200200)National Natural Science Foundation of China(Grants 51872283,and 21805273)+8 种基金Liaoning BaiQianWan Talents Program,LiaoNing Revitalization Talents Program(Grant XLYC1807153)Natural Science Foundation of Liaoning Province(2020-MS-095)Joint Research Fund Liaoning-Shenyang National Laboratory for Materials Science(Grants 20180510038)DICP(DICP ZZBS201708,DICP ZZBS201802,and DICP I202032)DICP&QIBEBT(Grant No.DICP&QIBEBT UN201702)Dalian National Laboratory For Clean Energy(DNL),CAS,DNL Cooperation Fund,CAS(DNL180310,DNL180308,DNL201912,and DNL201915)the Fundamental Research Funds for the Central Universities of China(N180503012)the State Key Laboratory of Fine Chemicals(KF1911)the CAS Key Laboratory of Carbon Materials(KLCMKFJJ2004)。
文摘Aqueous zinc ion hybrid capacitors(ZIHCs)hold great potential for large-scale energy storage applications owing to their high safety and low cost,but suffer from low capacity and energy density.Herein,pyridinic nitrogen enriched porous carbon(nPC)was successfully synthesized via the growth,subsequent annealing and acid etching of bimetal organic frameworks for high capacity and safe ZIHCs with exceptional rate capability.Benefiting from the mesopores for easy ion diffusion,high electrical conductivity enabled by in-situ grown carbon nanotubes matrix and residual metal Co nanoparticles for fast electron transfer,sufficient micropores and high N content(8.9 at%)with dominated pyridinic N(54%)for enhanced zinc ion storage,the resulting nPC cathodes for ZIHCs achieved high capacities of 302 and137 m Ah g^(-1) at 1 and 18 A g^(-1),outperforming most reported carbon based cathodes.Theoretical results further disclosed that pyridinic N possessed larger binding energy of-4.99 eV to chemically coordinate with Zn2+than other N species.Moreover,quasi-solid-state ZIHCs with gelatin based gel electrolytes exhibited high energy density of 157.6 Wh kg^(-1) at 0.69 kW kg^(-1),high safety and mechanical flexibility to withstand mechanical deformation and drilling.This strategy of developing pyridinic nitrogen enriched porous carbon will pave a new avenue to construct safe ZIHCs with high energy densities.
