Aqueous proton batteries(APBs)embody a compelling alternative in the realm of economical and reliable energy technologies by virtue of their distinctive“Grotthuss mechanism”.Sustainable production and adjustable mol...Aqueous proton batteries(APBs)embody a compelling alternative in the realm of economical and reliable energy technologies by virtue of their distinctive“Grotthuss mechanism”.Sustainable production and adjustable molecular structure make organic polymers a promising choice for APB electrodes.However,inadequate proton-storage redox capability currently hinders their practical implementation.To address this issue,we introduce a pioneering phenazine-conjugated polymer(PPZ),synthesized through a straightforward polymerization process,marking its debut in APB applications.The inclusion of N-heteroaromatic fused-ring in the extendedπ-conjugated framework not only prevents the dissolution of redox-active units but also refines the energy bandgap and electronic properties,endowing the PPZ polymer with both structural integrity and enhanced redox activity.Consequently,the PPZ polymer as an electrode material achieves a remarkable proton-storage capacity of 211.5 mAh/g,maintaining a notable capacity of 158.3 mAh/g even under a high rate of 8 A/g with a minimal capacity fade of merely 0.00226%per cycle.The rapid,stable and impressive redox behavior is further elucidated through in-situ techniques and theoretical calculations.Ultimately,we fabricate an APB device featuring satisfactory electrochemical attributes with an extraordinary longevity over 10,000 cycles,thereby affirming its auspicious potential for eminent applications.展开更多
Supercapacitor diode is a novel ion device that performs both supercapacitor energy storage and ion diode rectification functions.However,previously reported devices are limited by their large size and complex process...Supercapacitor diode is a novel ion device that performs both supercapacitor energy storage and ion diode rectification functions.However,previously reported devices are limited by their large size and complex processes.In this work,we demonstrate a screen-printed micro supercapacitor diode(MCAPode)that based on the insertion of a finger mode with spinel ZnCo_(2)O_(4) as cathode and activated carbon as anode for the first time,and featuring an excellent area specific capacitance(1.21 mF cm^(-2)at 10 mV s^(-1))and high rectification characteristics(rectification ratioⅠof 11.99 at 40 mV s^(-1)).Taking advantage of the ionic gel electrolyte,which provides excellent stability during repeated flexing and at high temperatures.In addition,MCAPode exhibits excellent electrochemical performance and rectification capability in"AND"and"OR"logic gates.These findings provide practical solutions for future expansion of micro supercapacitor diode applications.展开更多
With the increasing demand for high energy density energy storage device,Li metal has received intensive attention for its ultrahigh capacity and the lowest redox potential.LiNO_(3)is widely used as electrolyte additi...With the increasing demand for high energy density energy storage device,Li metal has received intensive attention for its ultrahigh capacity and the lowest redox potential.LiNO_(3)is widely used as electrolyte additive for ether electrolyte,which can improve the cycle performance of Li metal anode.Compared to ethers,carbonates are more suitable for Li metal batteries with high voltage cathode because they have a wider electrochemical window.However,LiNO_(3)performs poor solubility in carbonate electrolyte,restricting its application in high voltage Li battery.Herein,we presented a facile method to introduce abundant LiNO_(3)additive to carbonate electrolyte system by introducing LiNO_(3)-PAN es as the interlayer of the cell.LiNO_(3)-PAN es is in sufficient contact with the electrolyte so that it can continuously releases LiNO_(3)to assist the formation of Li_(2)N_(2)O_(2)-rich single nitrogenous component SEI layer on Li surface.With the help of LiNO_(3)-PAN es,Li metal anode shows excellent cycle stability even at a high current density of 4mA/cm^(2),so that the cycle performance of the full cells was significantly improved,whether in the anode-free Cu||LFP cell or the Li||NCM622 cell.展开更多
Polyethylene oxide(PEO)-based solid-state polymer electrolytes(SPEs)are limited by their poor cyclic stability and inferior ionic conductivity for applicating in high-safety,long-cycling and high-energy-density lithiu...Polyethylene oxide(PEO)-based solid-state polymer electrolytes(SPEs)are limited by their poor cyclic stability and inferior ionic conductivity for applicating in high-safety,long-cycling and high-energy-density lithium metal batteries.Herein,porous boron nitride nanofibers(BNNFs)are filled into PEO-based SPE,which significantly suppresses Li dendrites growth and enhances the electrochemical performance of Li metal battery.BNNFs with high porosity have more active sites to connect with PEO,which can effectively reduce the crystallinity of the PEO matrix and enhance its ionic conductivity.Moreover,owing to the hardness and good stability of BNNFs,BNNFs/PEO/Li TFSI electrolyte exhibits a wider electrochemical window,better mechanical property and higher thermal stability compared with PEO/Li TFSI electrolyte.Consequently,the Li symmetric cell composed of 1%BNNFs/PEO/Li TFSI performs good cyclic stability(>1800 h),and the Li||1%BNNFs/PEO/Li TFSI||LFP full battery shows obviously improved performances in charge-discharge polarization voltage,discharge specific capacity,rate performance and cyclic stability than the Li||PEO/Li TFSI||LFP battery.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
Although Ti3 C2 MXene sheets have attracted extensive attention in lithium-ion storage techniques,their restacking makes against and even hinders the Li ions diffusion within them,thereby decreasing the capacity as we...Although Ti3 C2 MXene sheets have attracted extensive attention in lithium-ion storage techniques,their restacking makes against and even hinders the Li ions diffusion within them,thereby decreasing the capacity as well as rate performance of conventional MXene anode.Here,for the first time,we roll up the Ti3 C2 Tx sheets into scrolls with unclosed topological structure and the interlayer galleries to alleviate the restacking problem.Thus,Ti3 C2 Tx scrolls as anode materials in lithium-ion batteries(LIBs)have higher capacity and better rate performance than Ti3 C2 Tx sheets.On the bases of these,high-capacity silicon nanoparticles are added during the rolling process to in-situ produce Ti3 C2 Tx/Si composite scrolls.The addition of 10%silicon nanoparticles shows the best overall improvement among capacity,rate capability and cyclic stability for Ti3 C2 Tx scrolls.展开更多
Aqueous supercapacitors(SCs)have received considerable attention owing to the utilization of low-cost,non-flammable,and low-toxicity aqueous electrolytes thus could eliminate the safety and cost concerns,but their wid...Aqueous supercapacitors(SCs)have received considerable attention owing to the utilization of low-cost,non-flammable,and low-toxicity aqueous electrolytes thus could eliminate the safety and cost concerns,but their wide temperature range applications have generally suffered from frozen of electrolyte and insufficient ionic conductivity at low temperatures.Herein,we demonstrate the feasibility of using an unconventional Deep Eutectic Solvent(DES)based on H2O-Mg(ClO4)2·6 H2O binary system as electrolyte to construct all-climate aqueous carbon-based SC.This unconventional class DES completely base on inorganic substances and achieving simply mix inexpensive salts and water together at the right proportions.Attributed to the attractive feature of extremely low freeze temperature of-69℃,this electrolyte can enable the 1.8 V carbon-based SC to fully work at-40℃with outstanding cycling stability.This DES electrolyte comprising of a single salt and a single solvent without any additive will open up an avenue for developing simple and green electrolytes to construct all-climate SC.展开更多
Stable solid electrolyte interphase(SEI)has been well established to be critical for the reversible operation of Li(ion)batteries,yet our understanding of its mechanical properties currently remains incomplete.Here,we...Stable solid electrolyte interphase(SEI)has been well established to be critical for the reversible operation of Li(ion)batteries,yet our understanding of its mechanical properties currently remains incomplete.Here,we used an electrochemical quartz crystal microbalance combined with dissipation monitoring(EQCM-D)to investigate SEI formation.By quantitatively estimating in-situ,the change in mass,shear modulus,and viscosity of the SEI,we show that the SEI formation in propylene carbonate(PC)-and ethylene carbonate/diethyl carbonate(EC/DEC)-based electrolytes involves the growth of a rigid laye r followed by a viscoelastic layer,whereas a distinct"one-layer"rigid model is applicable to the SEI formulated in tetraethylene glycol dimethyl ether(TEGDME)-based electrolyte.With the continuous formation of the SEI,its shear modulus decreases accompanied by an increase in viscosity.In TEGDME,the lightest/thinnest SEI(mass lower than in PC by a factor of nine)yet having the greatest stiffness(more than five times that in PC)is obtained.We attribute this behavior to differences in the chemical composition of the SEIs,which have been revealed by tracking the mass-change-per-mole-of-electrontransferred using EQCM-D and further confirmed by X-ray photoelectron spectroscopy.展开更多
Zinc-based electrochemistry ene rgy sto rage with high safety and high theoretical capacity is considered to be a competitive candidate to replace lithium-ion batteries.In electrochemical energy storage,multimetal oxi...Zinc-based electrochemistry ene rgy sto rage with high safety and high theoretical capacity is considered to be a competitive candidate to replace lithium-ion batteries.In electrochemical energy storage,multimetal oxide cathode materials can generally provide a wider electrochemical stability window and a higher capacity compared with single metal oxides cathode.Here,a new type of cathode material,MnFe2Co3O8 nanodots/functional graphene sheets,is designed and used for aqueous hybrid Zn-based energy storage.Coupling with a hybrid electrolyte based on zinc sulfate and potassium hydroxide,the asfabricated battery was able to work with a wide electrochemical window of 0.1~1.8 V,showed a high specific capacity of 660 mAh/g,delivered an ultra high energy density of 1135 Wh/kg and a scalable power density of 5754 W/kg(calculated based on the cathode),and displayed a long cycling life of 1000 cycles.These are mainly attributed to the valence charge density distribution in MnFe2Co3O8 nanodots,the good structural strengthening as well as high conductivity of the cathode,and the right electrolyte.Such cathode material also exhibited high electrocatalytic activity for oxygen evolution reaction and thus could be used for constructing a Zn-air battery with an ultrahigh reversible capacity of 9556 mAh/g.展开更多
Sodium ion hybrid capacitors are of great concern in large-scale and cost-effective electrical energy storage owing to their high energy and power densities,as well as natural abundance and wide distribution of sodium...Sodium ion hybrid capacitors are of great concern in large-scale and cost-effective electrical energy storage owing to their high energy and power densities,as well as natural abundance and wide distribution of sodium.However,it is difficult to find a well-pleasing anode material that matches the high-performance cathode materials to achieve good energy and power output for sodium ion hybrid capacitors.In this paper,nitrogen and sulfur co-doped nanotube-like carbon prepared by a simple carbonization process of high sulfur-loaded polyaniline nanotubes is introduced as the anode.The assembled sodium ion half cell based on the optimal nanotube-like carbon delivers a high reversible capacity of ~304.8 mAh/g at 0.2 A/g and an excellent rate performance of ~124.8 mAh/g at 10 A/g in a voltage window of 0.01-2.5 V(versus sodium/sodium ion).For the hybrid capacitors assembled using the optimal nanotube-like carbon as the anode and high-capacity activated carbon as the cathode,high energy densities of ~100.2 Wh/kg at 250 W/kg and ~50.69 Wh/kg at 12,500 W/kg are achieved.展开更多
Pseudocapacitive materials that store charges via reversible surface or near-surface faradaic reactions are capable of overcoming the capacity limitations of electrical double-layer capacitors.Revealing the structure...Pseudocapacitive materials that store charges via reversible surface or near-surface faradaic reactions are capable of overcoming the capacity limitations of electrical double-layer capacitors.Revealing the structure–activity relationship between the microstructural features of pseudocapacitive materials and their electrochemical performance on the atomic scale is the key to build high-performance capacitor-type devices containing ideal pseudocapacitance effect.Currently,the high brightness(flux),and spectral and coherent nature of synchrotron X-ray analytical techniques make it a powerful tool for probing the structure–property relationship of pseudocapacitive materials.Herein,we report a comprehensive and systematic review of four typical characterization techniques(synchrotron X-ray diffraction,pair distribution function[PDF]analysis,soft X-ray absorption spectroscopy,and hard X-ray absorption spectroscopy)for the study of pseudocapacitance mechanisms.In addition,we offered significant insights for understanding and identifying pseudocapacitance mechanisms(surface redox pseudocapacitance,intercalation pseudocapacitance,and the extrinsic pseudocapacitance phenomenon in battery materials)by combining in situ hard XAS and electrochemical analyses.Finally,a perspective for further depth of understanding into the pseudocapacitance mechanism using synchrotron X-ray analytical techniques is proposed.展开更多
The rapid development of next-generation flexible electronics stimulates the growing demand for flexible and wearable power sources with high energy density.Li metal capacitor(LMC),combining with a Li metal anode and ...The rapid development of next-generation flexible electronics stimulates the growing demand for flexible and wearable power sources with high energy density.Li metal capacitor(LMC),combining with a Li metal anode and an activated carbon cathode,exhibits extremely high energy density and high power density due to the unique energy storage mechanism,thus showing great potential for powering wearable electronic devices.Herein,a flexible LMC based on an in situ prepared PETEA-based gel polymer electrolyte(GPE)was reported for the first time.Owing to the high ionic conductivity of PETEA-based GPE(5.75×10^(−3)S/cm at 20℃),the assembled flexible LMC delivers a high capacitance of 210 F/g at 0.1 A/g within the voltage range from 1.5 V to 4.3 V vs.Li/Li^(+),a high energy density of 474 Wh/kg at 0.1 A/g and a high power density of 29 kW/kg at 10 A/g.More importantly,PETEA-based GPE endows the LMC with excellent flexibility and safety,which could work normally under abuse tests,such as bending,nail penetration and cutting.The in situ prepared PETEA-based GPE simplifies the fabrication process,avoids the risk of leakage and inhibits the growth of Li dendrite,making LMC a promising flexible energy storage device for the flexible electronic field.展开更多
Similar to lithium-ion batteries(LIBs),during the first charge/discharge process of lithium-ion capacitors(LICs),lithium-intercalated anodes(e.g.,silicon,graphite,and hard carbon)also exhibit irreversible lithium inte...Similar to lithium-ion batteries(LIBs),during the first charge/discharge process of lithium-ion capacitors(LICs),lithium-intercalated anodes(e.g.,silicon,graphite,and hard carbon)also exhibit irreversible lithium intercalation behaviors,such as the formation of a solid electrolyte interface(SEI),which will consume Li^(+)in the electrolyte and significantly reduce the electrochemical performance of the system.Therefore,pre-lithiation is an indispensable procedure for LICs.At present,commercial LICs mostly use lithium metal as the lithium source to compensate for the irreversible capacity loss,which has the demerits of operational complexity and danger.However,the pre-lithiation strategy based on cathode sacrificial lithium salts(CSLSs)has been proposed,which has the advantages of low cost,simple operation,environmental protection,and safety.Therefore,there is an urgent need for a timely and comprehensive summary of the application of CSLSs to LICs.In this review,the important roles of pre-lithiation in LICs are detailed,and different pre-lithiation methods are reviewed and compared systematically and comprehensively.After that,we systematically discuss the pre-lithiation strategies based on CSLSs and mainly introduce the lithium extraction mechanism of CSLSs and the influence of intrinsic characteristics and doping amount of CSLSs on LICs performance.In addition,a summary and outlook are conducted,aiming to provide the essential basic knowledge and guidance for developing a new pre-lithiation technology.展开更多
Three-dimensional （3D） carbonaceous materials derived from bacterial cellulose （BC） has been introduced as electrode for supercapacitors in recent. Here, we report a simple strategy for the synthesis of functional...Three-dimensional （3D） carbonaceous materials derived from bacterial cellulose （BC） has been introduced as electrode for supercapacitors in recent. Here, we report a simple strategy for the synthesis of functional carbon frameworks through 2,2,6,6-tetramethylpilperidine l-oxyl radical （TEMPO） mediated oxidation of bacterial cellulose （BC） followed by carbonization. TEMPO-mediated oxidation can efficiently convert the hydroxyls on the surface of BC to carboxylate groups to improve electrochemical activity. Because of its high porosity, good hydrophilicity, rich oxygen groups, and continuous ion transport in-between sheet-like porous network, the TEMPO-oxidized BC delivers a much higher gravimetric capacitance （137.3 Fig） at low annealing temperature of 500℃ than that of pyrolysis BC （31 F/g） at the same annealing temperature. The pyrolysis modified BC obtained at 900℃ shows specific capacitance （160.2Fig）, large current stability and long-term stability （84.2% of its initial capacitance retention after 10,000 cycles）.展开更多
Lithium-ion hybrid supercapacitors （LIHSs）, also called Li-ion capacitors, are electrochemical energy stor- age devices that combining the advantages of high power density of supercapacitor and high energy density o...Lithium-ion hybrid supercapacitors （LIHSs）, also called Li-ion capacitors, are electrochemical energy stor- age devices that combining the advantages of high power density of supercapacitor and high energy density of Li-ion battery. However, high power density and long cycle life are still challenges for the cul~ rent LIHSs due to the imbalance of charge-storage capacity and electrode kinetics between capacitor-type cathode and battery-type anode. Therefore, great efforts have been made on designing novel cathode materials with high storage capacity and anode material with enhanced kinetic behavior for LIHSs. With unique two-dimensional form and numerous appealing properties, for the past several years, the rational designed graphene and its composites materials exhibit greatly improved electrochemical performance as cathode or anode for LIHSs. Here, we summarized and discussed the latest advances of the state- of-art graphene-based materials for LIHSs applications. The major roles of graphene are highlighted as （1） a superior active material, （2） ultrathin 2D flexible support to remedy the sluggish reaction of the metal compound anode, and （3） good 2D building blocks for constructing macroscopic 3D pOFOUS car- bonjgraphene hybrids. In addition, some high performance aqueous LIHSs using graphene as electrode were also summarized. Finally, the perspectives and challenges are also proposed for further develop- ment of more advanced graphene-based LIHSs.展开更多
The perovskite oxides were known as an oxygen anion intercalation electrode material for pseudocapacitance in 2014[1].Although this new energy storage mechanism is defined as oxygen anion intercalation,it differs fund...The perovskite oxides were known as an oxygen anion intercalation electrode material for pseudocapacitance in 2014[1].Although this new energy storage mechanism is defined as oxygen anion intercalation,it differs fundamentally from ion intercalation in batteries.As shown in Fig.1a,b,energy storage and release are mainly achieved through bulk redox reactions in the electrodes for batteries,controlled by bulk diffusion,demonstrating high energy and low power density[2].For pseudocapacitors,a type of supercapacitor,their electrochemical characteristics differ from those of double-layer capacitors,which only undergo physical reactions,and also differ from batteries,which undergo Faraday redox reactions in the bulk phase.Pseudocapacitance primarily relies on surface Faradaic reactions caused by charge transfer at or near the surface,without bulk diffusion control,enabling them to maintain impressive energy density while also exhibiting extremely fast reaction kinetics[3].Oxygen anion intercalation is a typical pseudocapacitive behavior.展开更多
Lithium-air capacitor-battery(LACB)is a novel electrochemical energy storage device that integrates the fast charging-anddischarging function of a supercapacitor into a conventional lithium-air battery(LAB),thereby ga...Lithium-air capacitor-battery(LACB)is a novel electrochemical energy storage device that integrates the fast charging-anddischarging function of a supercapacitor into a conventional lithium-air battery(LAB),thereby gaining a substantial increase in power density compared to the lithium-air battery.However,its development is severely limited by the complex dual-electrolyte and dual-atmosphere construction used in the reported devices.Herein,we present a prototype lithium-air capacitor-battery with an exceptionally simplified single electrolyte and double-cathode(an air electrode and a capacitor electrode)structure under one gas atmosphere.In particular,the ingenious introduction of an oxygen-barrier film between the two cathodes allows the device to exhibit reliable and rapid conversion between high energy and high power by controlling current density.Thus obtained cathode delivers a large full capacity of 16.9 m Ah cm^(-2)and it also exhibits excellent cycle stability for stable operation up to 5,500 laps at a fixed capacity of 0.1 m Ah cm^(-2)at the current density of 2 m A cm^(-2).In addition,the LACB has a self-charging capability.This work puts forward a new construction strategy for LACB systems,which is conducive to their rapid development.展开更多
Hard carbon(HC)is currently recognized as the leading anode material for commercial sodium-ion batteries(SIBs).However,its low initial Coulombic efficiency(ICE)severely limits its broader application.Herein,we propose...Hard carbon(HC)is currently recognized as the leading anode material for commercial sodium-ion batteries(SIBs).However,its low initial Coulombic efficiency(ICE)severely limits its broader application.Herein,we propose a microstructure regulation strategy for resin-derived HC through a synergistic approach involving a controllable precursor polymerization assisted by melamine and a subsequent crosslinking reaction with succinic anhydride.Structural characterizations reveal that the optimized HC(MPFS)exhibits an expanded interlayer spacing(0.38 nm),a reduced specific surface area(2.61 m^(2)g^(-1)),and abundant closed pores within the material,contrasting with the original resin-derived HC.These structural advantages enable the MPFS anode to achieve a remarkable ICE of 92.2%coupled with a high reversible capacity of 324.4 m A h g^(-1),which is superior to commercial HC(81.7%,276.6 mA h g^(-1))and the original resin-derived HC(87.0%,297.0 mA h g^(-1)).This study establishes an effective methodology for enhancing the ICE of HC without sacrificing the reversible capacity through rational microstructure design,providing critical insights for advancing the development of SIBs.展开更多
The electrochemical stability window(ESW)is crucial for determining the energy density of electric double-layer capacitors(EDLCs).However,current ESW testing protocols of EDLCs are strongly affected by artificial fact...The electrochemical stability window(ESW)is crucial for determining the energy density of electric double-layer capacitors(EDLCs).However,current ESW testing protocols of EDLCs are strongly affected by artificial factors,thereby leading to unreliable result.To solve this problem,we first identify the key shortcomings of the traditional protocols by analyzing their test principles.Subsequently,taking an aqueous carbon-based EDLC as an example,we design a side reaction descriptor to represent the response difference in the charging capacitance to side reactions between the cyclic voltammetry and galvanostatic chargedischarge methods.With the aid of this descriptor,we propose a new ESW testing protocol,which is not only able to completely avoid the adverse influence of subjective factors but also fully consider the operating condition limitations.The protocol can be extended from the single electrode to the full device.This work proposes a more rigorous definition of ESW and provides a reliable protocol for evaluating the ESW of EDLCs.展开更多
基金supported by the National Natural Science Foundation of China(No.52002157)the China Postdoctoral Science Foundation(No.2023M741471).
文摘Aqueous proton batteries(APBs)embody a compelling alternative in the realm of economical and reliable energy technologies by virtue of their distinctive“Grotthuss mechanism”.Sustainable production and adjustable molecular structure make organic polymers a promising choice for APB electrodes.However,inadequate proton-storage redox capability currently hinders their practical implementation.To address this issue,we introduce a pioneering phenazine-conjugated polymer(PPZ),synthesized through a straightforward polymerization process,marking its debut in APB applications.The inclusion of N-heteroaromatic fused-ring in the extendedπ-conjugated framework not only prevents the dissolution of redox-active units but also refines the energy bandgap and electronic properties,endowing the PPZ polymer with both structural integrity and enhanced redox activity.Consequently,the PPZ polymer as an electrode material achieves a remarkable proton-storage capacity of 211.5 mAh/g,maintaining a notable capacity of 158.3 mAh/g even under a high rate of 8 A/g with a minimal capacity fade of merely 0.00226%per cycle.The rapid,stable and impressive redox behavior is further elucidated through in-situ techniques and theoretical calculations.Ultimately,we fabricate an APB device featuring satisfactory electrochemical attributes with an extraordinary longevity over 10,000 cycles,thereby affirming its auspicious potential for eminent applications.
基金the financial support from the Key Project of National Natural Science Foundation of China(12131010)the National Natural Science Foundation of China(22279166)+2 种基金the Special Project for Marine Economy Development of Guangdong Province(GDNRC[2023]26)the International Cooperation Base of Infrared Reflection Liquid Crystal Polymers and Device(2015B050501010)the Guangdong Basic and Applied Basic Research Foundation(2022B1515120019)。
文摘Supercapacitor diode is a novel ion device that performs both supercapacitor energy storage and ion diode rectification functions.However,previously reported devices are limited by their large size and complex processes.In this work,we demonstrate a screen-printed micro supercapacitor diode(MCAPode)that based on the insertion of a finger mode with spinel ZnCo_(2)O_(4) as cathode and activated carbon as anode for the first time,and featuring an excellent area specific capacitance(1.21 mF cm^(-2)at 10 mV s^(-1))and high rectification characteristics(rectification ratioⅠof 11.99 at 40 mV s^(-1)).Taking advantage of the ionic gel electrolyte,which provides excellent stability during repeated flexing and at high temperatures.In addition,MCAPode exhibits excellent electrochemical performance and rectification capability in"AND"and"OR"logic gates.These findings provide practical solutions for future expansion of micro supercapacitor diode applications.
基金supported by the National Key R&D Program of China(No.2022YFB2402600)National Natural Science Foundation of China(No.22279166)+1 种基金Basic and Applied Basic Research Foundation of Guangdong Province-Regional joint fund project(No.2022B1515120019)the Fundamental Research Funds for the Central Universities,Sun Yat-Sen University(Nos.22qntd0101 and 22dfx01).
文摘With the increasing demand for high energy density energy storage device,Li metal has received intensive attention for its ultrahigh capacity and the lowest redox potential.LiNO_(3)is widely used as electrolyte additive for ether electrolyte,which can improve the cycle performance of Li metal anode.Compared to ethers,carbonates are more suitable for Li metal batteries with high voltage cathode because they have a wider electrochemical window.However,LiNO_(3)performs poor solubility in carbonate electrolyte,restricting its application in high voltage Li battery.Herein,we presented a facile method to introduce abundant LiNO_(3)additive to carbonate electrolyte system by introducing LiNO_(3)-PAN es as the interlayer of the cell.LiNO_(3)-PAN es is in sufficient contact with the electrolyte so that it can continuously releases LiNO_(3)to assist the formation of Li_(2)N_(2)O_(2)-rich single nitrogenous component SEI layer on Li surface.With the help of LiNO_(3)-PAN es,Li metal anode shows excellent cycle stability even at a high current density of 4mA/cm^(2),so that the cycle performance of the full cells was significantly improved,whether in the anode-free Cu||LFP cell or the Li||NCM622 cell.
基金financially supported by the National Key R&D Program of China(No.2022YFB2402600)National Natural Science Foundation of China(Nos.22279166,52203346)+4 种基金Basic and Applied Basic Research Foundation of Guangdong Province(Nos.2021A1515110168,2022B1515120019)Basic and Applied Basic Research Foundation of Guangzhou(No.202201011322)Fundamental Research Funds for the Central UniversitiesSun Yat-Sen University(Nos.22qntd0101 and 22dfx01)Special Fund of Science and Technology Innovation Cultivation for College Students in Guangdong Province(No.pdjh2021b0022)。
文摘Polyethylene oxide(PEO)-based solid-state polymer electrolytes(SPEs)are limited by their poor cyclic stability and inferior ionic conductivity for applicating in high-safety,long-cycling and high-energy-density lithium metal batteries.Herein,porous boron nitride nanofibers(BNNFs)are filled into PEO-based SPE,which significantly suppresses Li dendrites growth and enhances the electrochemical performance of Li metal battery.BNNFs with high porosity have more active sites to connect with PEO,which can effectively reduce the crystallinity of the PEO matrix and enhance its ionic conductivity.Moreover,owing to the hardness and good stability of BNNFs,BNNFs/PEO/Li TFSI electrolyte exhibits a wider electrochemical window,better mechanical property and higher thermal stability compared with PEO/Li TFSI electrolyte.Consequently,the Li symmetric cell composed of 1%BNNFs/PEO/Li TFSI performs good cyclic stability(>1800 h),and the Li||1%BNNFs/PEO/Li TFSI||LFP full battery shows obviously improved performances in charge-discharge polarization voltage,discharge specific capacity,rate performance and cyclic stability than the Li||PEO/Li TFSI||LFP battery.
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 No.21573265,21673263,and 21805291)One-Three-Five Strategic Planning of Chinese Academy of Sciences and the DNL Cooperation Fund,CAS(DNL180307)。
文摘Although Ti3 C2 MXene sheets have attracted extensive attention in lithium-ion storage techniques,their restacking makes against and even hinders the Li ions diffusion within them,thereby decreasing the capacity as well as rate performance of conventional MXene anode.Here,for the first time,we roll up the Ti3 C2 Tx sheets into scrolls with unclosed topological structure and the interlayer galleries to alleviate the restacking problem.Thus,Ti3 C2 Tx scrolls as anode materials in lithium-ion batteries(LIBs)have higher capacity and better rate performance than Ti3 C2 Tx sheets.On the bases of these,high-capacity silicon nanoparticles are added during the rolling process to in-situ produce Ti3 C2 Tx/Si composite scrolls.The addition of 10%silicon nanoparticles shows the best overall improvement among capacity,rate capability and cyclic stability for Ti3 C2 Tx scrolls.
基金financially supported by the DNL Cooperation Fund,Chinese Academy of Sciences(DNL180307)Natural Science Foundation of Gansu Province(18JR3RA159)。
文摘Aqueous supercapacitors(SCs)have received considerable attention owing to the utilization of low-cost,non-flammable,and low-toxicity aqueous electrolytes thus could eliminate the safety and cost concerns,but their wide temperature range applications have generally suffered from frozen of electrolyte and insufficient ionic conductivity at low temperatures.Herein,we demonstrate the feasibility of using an unconventional Deep Eutectic Solvent(DES)based on H2O-Mg(ClO4)2·6 H2O binary system as electrolyte to construct all-climate aqueous carbon-based SC.This unconventional class DES completely base on inorganic substances and achieving simply mix inexpensive salts and water together at the right proportions.Attributed to the attractive feature of extremely low freeze temperature of-69℃,this electrolyte can enable the 1.8 V carbon-based SC to fully work at-40℃with outstanding cycling stability.This DES electrolyte comprising of a single salt and a single solvent without any additive will open up an avenue for developing simple and green electrolytes to construct all-climate SC.
基金funding from the Natural Science Foundation of China(Nos.51761145046,21975243 and 51672262)support from the 100 Talents Program of the Chinese Academy of Sciencesthe National Program for Support of Top-notch Young Professionals,and iChEM。
文摘Stable solid electrolyte interphase(SEI)has been well established to be critical for the reversible operation of Li(ion)batteries,yet our understanding of its mechanical properties currently remains incomplete.Here,we used an electrochemical quartz crystal microbalance combined with dissipation monitoring(EQCM-D)to investigate SEI formation.By quantitatively estimating in-situ,the change in mass,shear modulus,and viscosity of the SEI,we show that the SEI formation in propylene carbonate(PC)-and ethylene carbonate/diethyl carbonate(EC/DEC)-based electrolytes involves the growth of a rigid laye r followed by a viscoelastic layer,whereas a distinct"one-layer"rigid model is applicable to the SEI formulated in tetraethylene glycol dimethyl ether(TEGDME)-based electrolyte.With the continuous formation of the SEI,its shear modulus decreases accompanied by an increase in viscosity.In TEGDME,the lightest/thinnest SEI(mass lower than in PC by a factor of nine)yet having the greatest stiffness(more than five times that in PC)is obtained.We attribute this behavior to differences in the chemical composition of the SEIs,which have been revealed by tracking the mass-change-per-mole-of-electrontransferred using EQCM-D and further confirmed by X-ray photoelectron spectroscopy.
基金supported by the National Nature Science Foundations of China(Nos.21673263 and 21805292)One-Three-Five Strategic Planning of Chinese Academy of Sciences(CAS)the DNL Cooperation Fund,CAS(No.DNL180307)。
文摘Zinc-based electrochemistry ene rgy sto rage with high safety and high theoretical capacity is considered to be a competitive candidate to replace lithium-ion batteries.In electrochemical energy storage,multimetal oxide cathode materials can generally provide a wider electrochemical stability window and a higher capacity compared with single metal oxides cathode.Here,a new type of cathode material,MnFe2Co3O8 nanodots/functional graphene sheets,is designed and used for aqueous hybrid Zn-based energy storage.Coupling with a hybrid electrolyte based on zinc sulfate and potassium hydroxide,the asfabricated battery was able to work with a wide electrochemical window of 0.1~1.8 V,showed a high specific capacity of 660 mAh/g,delivered an ultra high energy density of 1135 Wh/kg and a scalable power density of 5754 W/kg(calculated based on the cathode),and displayed a long cycling life of 1000 cycles.These are mainly attributed to the valence charge density distribution in MnFe2Co3O8 nanodots,the good structural strengthening as well as high conductivity of the cathode,and the right electrolyte.Such cathode material also exhibited high electrocatalytic activity for oxygen evolution reaction and thus could be used for constructing a Zn-air battery with an ultrahigh reversible capacity of 9556 mAh/g.
基金financially supported from the National Natural Science Foundation of China(Nos.61376068,11304132 and 11304133)the Fundamental Research Funds for the Central Universities(Nos.lzujbky-2017-178 and lzujbky-2017-181)。
文摘Sodium ion hybrid capacitors are of great concern in large-scale and cost-effective electrical energy storage owing to their high energy and power densities,as well as natural abundance and wide distribution of sodium.However,it is difficult to find a well-pleasing anode material that matches the high-performance cathode materials to achieve good energy and power output for sodium ion hybrid capacitors.In this paper,nitrogen and sulfur co-doped nanotube-like carbon prepared by a simple carbonization process of high sulfur-loaded polyaniline nanotubes is introduced as the anode.The assembled sodium ion half cell based on the optimal nanotube-like carbon delivers a high reversible capacity of ~304.8 mAh/g at 0.2 A/g and an excellent rate performance of ~124.8 mAh/g at 10 A/g in a voltage window of 0.01-2.5 V(versus sodium/sodium ion).For the hybrid capacitors assembled using the optimal nanotube-like carbon as the anode and high-capacity activated carbon as the cathode,high energy densities of ~100.2 Wh/kg at 250 W/kg and ~50.69 Wh/kg at 12,500 W/kg are achieved.
基金financialy supported by National Key R&D Program of China(2022YFB2402600)the National Natural Science Foundation of China(22279166)+1 种基金the Research Start-up Funds from Sun Yat-Sen University(200306)the Fundamental Research Funds for the Central Universities,Sun Yat-Sen University(22qntd0101 and 22dfx01)
文摘Pseudocapacitive materials that store charges via reversible surface or near-surface faradaic reactions are capable of overcoming the capacity limitations of electrical double-layer capacitors.Revealing the structure–activity relationship between the microstructural features of pseudocapacitive materials and their electrochemical performance on the atomic scale is the key to build high-performance capacitor-type devices containing ideal pseudocapacitance effect.Currently,the high brightness(flux),and spectral and coherent nature of synchrotron X-ray analytical techniques make it a powerful tool for probing the structure–property relationship of pseudocapacitive materials.Herein,we report a comprehensive and systematic review of four typical characterization techniques(synchrotron X-ray diffraction,pair distribution function[PDF]analysis,soft X-ray absorption spectroscopy,and hard X-ray absorption spectroscopy)for the study of pseudocapacitance mechanisms.In addition,we offered significant insights for understanding and identifying pseudocapacitance mechanisms(surface redox pseudocapacitance,intercalation pseudocapacitance,and the extrinsic pseudocapacitance phenomenon in battery materials)by combining in situ hard XAS and electrochemical analyses.Finally,a perspective for further depth of understanding into the pseudocapacitance mechanism using synchrotron X-ray analytical techniques is proposed.
基金the financial support from the Natural Science Foundation of Gansu(No.20JR10RA611)the Fundamental Research Funds for the Central Universities(Nos.Lzujbky-2017-178 and lzujbky-2017-181).
文摘The rapid development of next-generation flexible electronics stimulates the growing demand for flexible and wearable power sources with high energy density.Li metal capacitor(LMC),combining with a Li metal anode and an activated carbon cathode,exhibits extremely high energy density and high power density due to the unique energy storage mechanism,thus showing great potential for powering wearable electronic devices.Herein,a flexible LMC based on an in situ prepared PETEA-based gel polymer electrolyte(GPE)was reported for the first time.Owing to the high ionic conductivity of PETEA-based GPE(5.75×10^(−3)S/cm at 20℃),the assembled flexible LMC delivers a high capacitance of 210 F/g at 0.1 A/g within the voltage range from 1.5 V to 4.3 V vs.Li/Li^(+),a high energy density of 474 Wh/kg at 0.1 A/g and a high power density of 29 kW/kg at 10 A/g.More importantly,PETEA-based GPE endows the LMC with excellent flexibility and safety,which could work normally under abuse tests,such as bending,nail penetration and cutting.The in situ prepared PETEA-based GPE simplifies the fabrication process,avoids the risk of leakage and inhibits the growth of Li dendrite,making LMC a promising flexible energy storage device for the flexible electronic field.
基金supported by the National Natural Science Foundation of China[grant number 22005318,22075303]the Western Young Scholars Foundations of Chinese Academy of Sciences,the Science Fund of Shandong Laboratory of Yantai Advanced Materials and Green Manufacturing(AMGM2022A02)the Provincial Youth Science and Technology Fund Program of Gansu Province[Project No.21JR7RA092].
文摘Similar to lithium-ion batteries(LIBs),during the first charge/discharge process of lithium-ion capacitors(LICs),lithium-intercalated anodes(e.g.,silicon,graphite,and hard carbon)also exhibit irreversible lithium intercalation behaviors,such as the formation of a solid electrolyte interface(SEI),which will consume Li^(+)in the electrolyte and significantly reduce the electrochemical performance of the system.Therefore,pre-lithiation is an indispensable procedure for LICs.At present,commercial LICs mostly use lithium metal as the lithium source to compensate for the irreversible capacity loss,which has the demerits of operational complexity and danger.However,the pre-lithiation strategy based on cathode sacrificial lithium salts(CSLSs)has been proposed,which has the advantages of low cost,simple operation,environmental protection,and safety.Therefore,there is an urgent need for a timely and comprehensive summary of the application of CSLSs to LICs.In this review,the important roles of pre-lithiation in LICs are detailed,and different pre-lithiation methods are reviewed and compared systematically and comprehensively.After that,we systematically discuss the pre-lithiation strategies based on CSLSs and mainly introduce the lithium extraction mechanism of CSLSs and the influence of intrinsic characteristics and doping amount of CSLSs on LICs performance.In addition,a summary and outlook are conducted,aiming to provide the essential basic knowledge and guidance for developing a new pre-lithiation technology.
基金supported by the National Nature Science Foundations of China (Nos.21573265 and 21673263)the Independent Innovation Plan Foundations of Qingdao City of China (No.16-5-1-42-jch)the plan of Youth Science foundations of Gansu Province (No.1610RJYA019)
文摘Three-dimensional （3D） carbonaceous materials derived from bacterial cellulose （BC） has been introduced as electrode for supercapacitors in recent. Here, we report a simple strategy for the synthesis of functional carbon frameworks through 2,2,6,6-tetramethylpilperidine l-oxyl radical （TEMPO） mediated oxidation of bacterial cellulose （BC） followed by carbonization. TEMPO-mediated oxidation can efficiently convert the hydroxyls on the surface of BC to carboxylate groups to improve electrochemical activity. Because of its high porosity, good hydrophilicity, rich oxygen groups, and continuous ion transport in-between sheet-like porous network, the TEMPO-oxidized BC delivers a much higher gravimetric capacitance （137.3 Fig） at low annealing temperature of 500℃ than that of pyrolysis BC （31 F/g） at the same annealing temperature. The pyrolysis modified BC obtained at 900℃ shows specific capacitance （160.2Fig）, large current stability and long-term stability （84.2% of its initial capacitance retention after 10,000 cycles）.
基金supported by the National Nature Science Foundations of China(Grant No.21673263,21573265)the Independent Innovation Plan Foundations of Qingdao City of China(Grant No.16-5-1-42-jch)the western Young Scholars Foundations of Chinese Academy of Sciences
文摘Lithium-ion hybrid supercapacitors （LIHSs）, also called Li-ion capacitors, are electrochemical energy stor- age devices that combining the advantages of high power density of supercapacitor and high energy density of Li-ion battery. However, high power density and long cycle life are still challenges for the cul~ rent LIHSs due to the imbalance of charge-storage capacity and electrode kinetics between capacitor-type cathode and battery-type anode. Therefore, great efforts have been made on designing novel cathode materials with high storage capacity and anode material with enhanced kinetic behavior for LIHSs. With unique two-dimensional form and numerous appealing properties, for the past several years, the rational designed graphene and its composites materials exhibit greatly improved electrochemical performance as cathode or anode for LIHSs. Here, we summarized and discussed the latest advances of the state- of-art graphene-based materials for LIHSs applications. The major roles of graphene are highlighted as （1） a superior active material, （2） ultrathin 2D flexible support to remedy the sluggish reaction of the metal compound anode, and （3） good 2D building blocks for constructing macroscopic 3D pOFOUS car- bonjgraphene hybrids. In addition, some high performance aqueous LIHSs using graphene as electrode were also summarized. Finally, the perspectives and challenges are also proposed for further develop- ment of more advanced graphene-based LIHSs.
基金financially supported by the Guangdong Basic and Applied Basic Research Foundation(2022B1515120019)the Science and Technology Development Project of Guangdong Academy of Sciences(2022GDASZH-2022010109,2023GDASZH-2023030601)。
文摘The perovskite oxides were known as an oxygen anion intercalation electrode material for pseudocapacitance in 2014[1].Although this new energy storage mechanism is defined as oxygen anion intercalation,it differs fundamentally from ion intercalation in batteries.As shown in Fig.1a,b,energy storage and release are mainly achieved through bulk redox reactions in the electrodes for batteries,controlled by bulk diffusion,demonstrating high energy and low power density[2].For pseudocapacitors,a type of supercapacitor,their electrochemical characteristics differ from those of double-layer capacitors,which only undergo physical reactions,and also differ from batteries,which undergo Faraday redox reactions in the bulk phase.Pseudocapacitance primarily relies on surface Faradaic reactions caused by charge transfer at or near the surface,without bulk diffusion control,enabling them to maintain impressive energy density while also exhibiting extremely fast reaction kinetics[3].Oxygen anion intercalation is a typical pseudocapacitive behavior.
基金supported by the Guangdong Basic and Applied Basic Research Foundation(2022B1515120019)the National Natural Science Foundation of China(22279166,52203346)the National Key R&D Program of China(2022YFB2402600)。
文摘Lithium-air capacitor-battery(LACB)is a novel electrochemical energy storage device that integrates the fast charging-anddischarging function of a supercapacitor into a conventional lithium-air battery(LAB),thereby gaining a substantial increase in power density compared to the lithium-air battery.However,its development is severely limited by the complex dual-electrolyte and dual-atmosphere construction used in the reported devices.Herein,we present a prototype lithium-air capacitor-battery with an exceptionally simplified single electrolyte and double-cathode(an air electrode and a capacitor electrode)structure under one gas atmosphere.In particular,the ingenious introduction of an oxygen-barrier film between the two cathodes allows the device to exhibit reliable and rapid conversion between high energy and high power by controlling current density.Thus obtained cathode delivers a large full capacity of 16.9 m Ah cm^(-2)and it also exhibits excellent cycle stability for stable operation up to 5,500 laps at a fixed capacity of 0.1 m Ah cm^(-2)at the current density of 2 m A cm^(-2).In addition,the LACB has a self-charging capability.This work puts forward a new construction strategy for LACB systems,which is conducive to their rapid development.
基金supported by the National Key R&D Program of China(2022YFB2402600)the National Natural Science Foundation of China(22279166,52203346)the Guangdong Basic and Applied Basic Research Foundation(2022B1515120019)。
文摘Hard carbon(HC)is currently recognized as the leading anode material for commercial sodium-ion batteries(SIBs).However,its low initial Coulombic efficiency(ICE)severely limits its broader application.Herein,we propose a microstructure regulation strategy for resin-derived HC through a synergistic approach involving a controllable precursor polymerization assisted by melamine and a subsequent crosslinking reaction with succinic anhydride.Structural characterizations reveal that the optimized HC(MPFS)exhibits an expanded interlayer spacing(0.38 nm),a reduced specific surface area(2.61 m^(2)g^(-1)),and abundant closed pores within the material,contrasting with the original resin-derived HC.These structural advantages enable the MPFS anode to achieve a remarkable ICE of 92.2%coupled with a high reversible capacity of 324.4 m A h g^(-1),which is superior to commercial HC(81.7%,276.6 mA h g^(-1))and the original resin-derived HC(87.0%,297.0 mA h g^(-1)).This study establishes an effective methodology for enhancing the ICE of HC without sacrificing the reversible capacity through rational microstructure design,providing critical insights for advancing the development of SIBs.
基金supported by the National Key R&D Program of China(2022YFB2402600)the National Natural Science Foundation of China(22279166)the Guangdong Basic and Applied Basic Research Foundation(2022B1515120019)。
文摘The electrochemical stability window(ESW)is crucial for determining the energy density of electric double-layer capacitors(EDLCs).However,current ESW testing protocols of EDLCs are strongly affected by artificial factors,thereby leading to unreliable result.To solve this problem,we first identify the key shortcomings of the traditional protocols by analyzing their test principles.Subsequently,taking an aqueous carbon-based EDLC as an example,we design a side reaction descriptor to represent the response difference in the charging capacitance to side reactions between the cyclic voltammetry and galvanostatic chargedischarge methods.With the aid of this descriptor,we propose a new ESW testing protocol,which is not only able to completely avoid the adverse influence of subjective factors but also fully consider the operating condition limitations.The protocol can be extended from the single electrode to the full device.This work proposes a more rigorous definition of ESW and provides a reliable protocol for evaluating the ESW of EDLCs.
