The key challenges and future opportunities of electrochemical capacitors

Electrochemical capacitors(ECs)with unique merits of fast charge/discharge rate and long cyclability are one of the representative electrochemical energy storage systems,possessing wide applications in power electronics and automotive transportation,etc.[1,2].Furthermore.

Pseudo-capacitance of ruthenium oxide/carbon black composites for electrochemical capacitors

Hydrous ruthenium oxide was formed by a new process. The precursor was obtained by mixing the aqueous solutions of RuCl3xH2O and NaHCO3. The addition of NaHCO3 led to the formation of an oxide with extremely fine RuO2 particles forming a porous network structure in the oxide electrode. Polyethylene glycol was added as a controller to partly inhibit the sol-gel reaction. The rate capacitance of 530 F·g^-1 was measured for the powder formed at an optimal annealing temperature of 210℃. Several details concerning this new material, including crystal structure, particle size as a function of temperature, and electrochemical properties, were also reported. In addition, the rate capacitance of the composite electrode reached 800 F·g^-1 after carbon black was added. By using the modified electrode of a RuO2/carbon black composite electrode, the electrochemical capacitor exhibits high energy density and stable power characteristics. The values of specific energy and maximum specific power of 24 Wh·kg^-1 and 4 kW·kg^-1, respectively, are demonstrated for a cell voltage between 0 and 1 V.

Chemically Modified Ordered Mesoporous Carbon/Polyaniline Composites for Electrochemical Capacitors

Chemically modified ordered mesoporous carbon CMK-3 materials were prepared by means of an easy wet-oxidative method in 2 mol/L nitric acid aqueous solution. A large amount of oxygen-containing functional groups were introduced onto the CMK-3 surface. Modified CMK-3（m-CMK-3） and aniline monomer were polymerized via an in situ chemical oxidative polymerization method. Morphological characterizations of m-CMK-3/PANI （polyaniline） composites were carried out via field emission scanning electron microscopy（SEM）. Their electrochemical properties were investigated with cyclic voltammetry, galvanostatic charge-discharge, and electrochemical impedance spectroscopy. The m-CMK-3/PANI composites have excellent properties in capacitance, and the highest specific capacitance（SC） value was up to 489 F/g, suggesting their potential application in the electrode material for electrochemical capacitors.

AC Line Filter Electrochemical Capacitors:Materials,Morphology,and Configuration

Recently,more and more supercapacitors(SCs)have been developed as AC line filter capacitors,which are generally named AC line filter electrochemical capacitors(FECs).Compared to traditional bulky aluminum electrolytic capacitors(AECs),FECs have higher capacity and lower space occupancy,which makes them a strong competitor.However,different from the common SCs for energy storage,it is necessary to consider the frequency response of the SCs for AC line filtering,where the contradiction between frequency response and specific capacitance is a challenge.The researchers have proposed different solutions from the perspective of materials,morphology,and configuration for this challenge.Based on the above background,in this review,we briefly introduce the principle and parameters of AC line filter electrochemical capacitors.We systematically summarize the state-of-the-art progresses of FECs and discuss their possible application and development in the future.The development of FECs can greatly promote the planarization,integration,and miniaturization of filter capacitors,and provide a new solution for the utilization of green and unstable energy.

Biomass-derived activated carbon materials with plentiful heteroatoms for high-performance electrochemical capacitor electrodes

Activated carbons for electrochemical capacitor electrodes are prepared from soyabean using chemical activation with KOH. The pore size is easily controllable by changing the mass ratio between KOH and carbonized product. The as-prepared materials possess a large specific surface area, unique structure, well- developed hierarchical porosity and plentiful heteroatoms（mainly O and N）. Thus resulted in its high specific capacitance,good rate capacity and cycling stability. Moreover, attributing to worldwide availability, renewable nature and low-cost, activated carbon prepared from soyabean has a good potential in energy conversion and storage devices.

Nanosized Nickel Oxides Derived from the Citrate Gel Process and Performances for Electrochemical Capacitors

Nanosized nickel oxide powders were prepared by thermal decomposition of the nickel citrate gel precursors. The thermal decomposition and powder materials derived from calcination of these gel precursors with various ratios of citric acid （CA） to nickel at different temperatures and times were characterized by thermal analysis （TG/DTA）, scanning electron microscopy （SEM）, x-ray diffraction （XRD）, and measurement of specific surface area （BET） with porosity analyses. The optimized processing conditions of calcination temperature 400℃ for 1 hour with the CA/Ni ratio of 1.2, were determined to produce the nanosized nickel oxide pow- ders with a high specific surface area of 181 m^2/g, nanometer particle sizes of 15-25 nm, micro-pore diameter distribution between 4-10 nm. The capacitance characteristics of the nanosized nickel oxide electrode in various concentrations of KOH solutions were studied by the cyclic voltammetry （CV） exhibiting both a double-layer capacitance and a faradaic pseudocapacitance. The nanosized nickel oxide electrode shows a high cyclic stability and is promising for high performance electrochemical capacitors.

Intedrcalation in Two-Dimensional Transition Metal Carbides and Nitrides(MXenes) toward Electrochemical Capacitor and Beyond

Since its discovery in 2011,the emerging family of two-dimensional(2D)transition metal carbides,nitrides,and carbonitrides(denoted as MXenes)has shown tremendous promise in the field of energy storages,especially electrochemical capacitors(ECs).The intercalation of foreign species,including but not limited to proton,cations,organic ions,and solvents,is demonstrated as one of the dominant facts during the energy storage process of MXenes,through which interlayer spacing of MXenes can be reversibly tuned,followed with reversible redox reactions on the surface of MXenes.Such a mechanism provides MXenes extremely high capacitance up to 1500 F cm-3,in aqueous acidic electrolyte.In addition,because of the versatile terminations on their surface,the intercalation of ions into MXenes can simultaneously induce the reversible transformation of their electronic structure to trigger some other phenomenon,for example,electrochromic effect,which has great potential on electrochromic smart window—an extended application of ECs.Accordingly,regulating and facilitating the intercalation in MXenes is of great significance for MXene-based ECs.In this review,we summarize the recent progress on the intercalation in MXenes towards ECs,discussing on the intercalated species,working mechanisms,and methods to promote the intercalation.Furthermore,we prospect the future research directions of intercalation of MXenes in ECs,such as the combination of simulation and experiment on finding the best intercalation species,precisely controlling the interlayer spacing and beyond,to boost the electrochemical performance of MXene toward practical applications and multi-functional devices.

A review of neutral pH polymer electrolytes for electrochemical capacitors:Transitioning from liquid to solid devices

The development of neutral pH polymer electrolytes has enabled high-performance solid-state,thin,and flexible electrochemical capacitors(ECs)to provide power for future consumer electronics and Internet-of-Thing devices.Notwithstanding their promising prospect,there is still some lack of understandings or disconnections from fundamental science to practical applications of these electrolytes.In this review,we provide an overview of stateof-the-art studies on ECs with neutral pH electrolytes in both liquid and solid configurations.Starting from the fundamental studies on the voltage window and ion conduction of salt species in liquid solution to polymer electrolytes,key considerations in developing neutral pH polymer electrolytes are discussed.The performance of the polymer electrolytes along with their enabled solid symmetric and asymmetric EC devices,as well as some enhanced functionalities are presented.The future directions for research on neutral pH polymer electrolytes are proposed,expected to provide reference for further enriching the fundamental knowledge and improving the device performances.

Alternatingly stacked thin film electrodes-based compact aqueous hybrid electrochemical capacitors for hundred-volts AC line filtering

Filtering capacitor with compact configuration and a wide range of operating voltage has been attracting increasing attention for the smooth conversion of the electric signal in modern circuits.Lossless integration of capacitor units can be regarded as one of the efficient ways to achieve a wider voltage range,which has not yet been fully conquered due to the lack of rational designs of the electrode structure and integration technology.This study presents an alternatingly stacked assemble technology to conveniently fabricate compact aqueous hybrid integrated filtering capacitors on a large scale,in which a unit consists of rGO/MXene composite film as a negative electrode and PEDOT:PSS based film as a positive electrode.Benefiting from the synergistic effect of rGO and MXene components,and morphological characteristics of PEDOT:PSS,the capacitor unit exhibits outstanding AC line filtering with a large areal specific energy density of 1,015 μF V^(2)cm^(-2)(0.28 μW h cm^(-2)) at 120 Hz.After rational integration,the assembled capacitors present compact/lightweight configuration and lossless frequency response,as reflected by almost constant resistor-capacitor time constant of 0.2 ms and dissipation factor of 15% at120 Hz,identical to those of the single capacitor unit.Apart from standing alone steadily on a flower,a small volume(only 8.1 cm^(3)) of the integrated capacitor with 70 units connected in series achieves hundred-volts alternating current line filtering,which is superior to most reported filtering capacitors with sandwich configuration.This study provides insight into the fabrication and application of compact/ultralight filtering capacitors with lossless frequency response,and a wide range of operating voltage.

Nanosized Ni-Mn Oxides Prepared by the Citrate Gel Process and Performances for Electrochemical Capacitors

Nanosized Ni-Mn oxide powders have been successfully citrate gel precursors. The powder materials derived from prepared by thermal decomposition of the Ni-Mn calcination of the gel precursors with various molar ratios of nickel and manganese at different temperatures and time were characterized using thermal analysis （TG-DSC）, scanning electron microscopy （SEM）, X-ray diffraction （XRD） and Brunauer-Emmet-Teller （BET）. The optimized processing conditions of calcination at 400℃ for 1 h with Ni/Mn molar ratio 6 were proved to produce the nanosized Ni-Mn oxide powders with a high specific surface area of 109.62 m^2/g and nanometer particle sizes of 15-30 nm. The capacitance characteristics of the nanosized Ni-Mn oxide electrode in various concentrations of KOH solutions were studied by the cyclic voltammetry （CV） and exhibited both a doublelayer capacitance and a Faradaic capacitance which could be attributed to the electrode consisting of Ni-Mn oxides and residual carbons from the organic gel thermal decomposition. A specific capacitance of 194.8 F/g was obtained for the electrode at the sweep rate of 10 mV/s in 4 mol/L KOH electrolyte and the capacitor showed quite high cyclic stability and is promising for advanced electrochemical capacitors.

Renewable biomass-derived carbons for electrochemical capacitor applications

Biomass is rich,renewable,sustainable,and green resources,thereby excellent raw material for the fabrication of carbon materials.The diversity in structure and morphology of biomass are relevant in obtaining carbon materials with dif-ferent structures and performances.The inherent ordered porous structure of biomass also benefits the activation process to yield porous carbons with ultra-high specific surface area and pore volume.Besides,obtained biomass-derived carbons(BDCs)are hard carbon with porous morphology,stable structure,supe-rior hardness/strength,and good cycling performances when used in electro-chemical capacitors(ECs).The inherent N,S,P,and O elements in biomass yield naturally self-doped N,S,P,and O BDCs with unique intrinsic structures.In this paper,the synthesis approaches and applications of BDCs in ECs are reviewed.It shows that BDCs electrochemical performances are highly determined by their pore structures,specific surface areas,heteroatoms doping,graphitization degree,defects,and morphologies.The electrochemical performances of BDCs can further be improved by compositing with other materials,such as graphene,carbon nanofibers/nanotubes,transition metal oxides or hydroxides,and con-ducting polymers.The future challenges and outlooks of BDCs are also provided.

Self-assembly of nanoparticles at solid-liquid interface for electrochemical capacitors

Self-assembly of nanoparticles at solid-liquid interface could be promising to realize the assembled functions for various applications,such as rechargeable batteries,supercapacitors,and electrocatalysis.This review summarizes the self-assembly of the nanoparticles at solid-liquid interface according to the different driving forces of assembly,including hydrophilic-hydrophobic interactions,solvophobic and electrostatic interaction.To be specific,the self-assembly can be divided into the following two types:surfactant-assisted self-assembly and direct self-assembly of Janus particles(inorganic and amphiphilic copolymer-inorganic Janus nanoparticles).Using the emulsion stabilized by nanoparticles as the template,the self-assembly constructed by the interaction of the nanostructure unit(including metal,metal oxide,and semiconductor,etc.)not only possesses the characteristic of nanostructure unit,but also exhibits the excellent assembly performance in electrochemistry aspect.The application of these assemblies in the area of electrochemical capacitors is presented.Finally,the current research progress and perspectives toward the self-assembly of nanoparticles at stabilized solid-liquid interface are proposed.

In situ Chemical Deposition of Polyaniline on Activated Carbon for Electrochemical Capacitors

Polyaniline （PA） film was chemically deposited onto the surface of activated carbon （AC） uniformly. Chemical deposition was carried out in 0.1 mol/L aniline plus 0.5 mol/L H2SO4 solution adopting V2O5·nH2O coated on the surface of activated carbon as oxidant. The surface morphologies and structures of the composite materials were characterized by scanning electron microscopy and FT-IR spectra. The electrochemical properties of the composite material electrodes were studied by cyclic voltammetry and constant current charge/discharge tests in 1 molFL H2SO4 solutions. The specific capacitance of composite materials was exhibited as high as 237.5 F/g at a current density of 1.0 A/g compared with a value of 120 F/g for pure carbon electrode. Good power characteristic and good stability of composite electrodes were also demonstrated.

Electrochemical capacitors based on the composite of graphene and nickel foam

An improved Hummers method was developed for the simple and efficient production of high-quality graphene oxide （GO）, and the composite of GO and nickel foam （NF） （GO/NF） was fabricated by ultrasonication-vacuum-assisted deposition of an aqueous solution of GO on NF. After chemical or thermal reduction, the composite of reduced GO and nickel foam （rGO/NF） was obtained. The electrochemical capacitance performance of rGO/NF was investigated using cyclic voltammetry and gal- vanostatic charge/discharge measurements. The chemically reduced rGO/NF composite （C-rGO/NF） exhibited high specific capacitance of 379 F/g at 1.0 A/g and 266.5 F/g at 10 A/g. We also prepared thermally reduced graphene oxide at 473 K in or- der to illuminate the difference in effect between the chemical and low-temperature thermal reduction methods on electro- chemical properties. The cycling performance of thermally reduced rGO/NF composite （T-rGO/NF） and C-rGO/NF had ~91% and ~95% capacitance retention after 2000 cycles in a 6 mol/L KOH electrolyte, respectively. Electrochemical experiments in- dicated that the obtained rGO/NF has very good capacitive performance and could be used as a potential application of elec- trochemical capacitors. Our work revealed high electrochemical capacitor performance of rGO/NF composite and provided a facile method of rGO/NF preparation.

The effect of calcination temperature on the capacitive properties of WO3-based electrochemical capacitors synthesized via a sol-gel method

Electrochemical capacitor （EC） is a promising energy storage device which can be hybridized with other energy conversion or energy storage devices. One type of ECs is pseudocapacitor made of metal oxides. WO3 is an inexpensive semiconductor metal oxide which has many applications. However the application of WO3 as an EC material was rarely reported. Therefore in this research EC was prepared from WO3 nanomaterial synthesized by a sol-gel process. The WO3 gel was spin-coated on graphite substrates and calcined at various temperatures of 300~C, 400℃, 500℃ and 600℃ for 1 h. Cyclic voltammetry （CV） measurements were used to observe the capacitive property of the WO3 samples. SEM, XRD, FTIR and Brunauer-Emmett-Teller （BET） analyses were used to characterize the material structures. WO3 calcined at 400~C was proved to have the highest capacitance of 233.63 Fo g^-1 （1869 mFo cm-2） at a scan rate of 2 mVo s-1 in 1 mol/L H2SO4 between potentials -0.4 and 0.4 V vs. SCE. Moreover it also showed the most symmetric CV curves as the indication of a good EC. Hence WO3 calcined at 400℃ is a potential candidate for EC material of pseudocapacitor type.

Preparation and Application of Nano-composite Poly(vinyl alcohol) Gel Electrolyte in Electrochemical Capacitor

A nano-composite polymer gel electrolyte was prepared using titanium oxide nanowire,poly(vinyl alcohol)(PVA),lithium salt and organic solvent N-methyl-2-pyrrolidone(NMP).The obtained electrolyte has the potential for application in electrochemical capacitor,the PVA in it is in an amorphous state.The ionic conductivities of electrolytes increased after addition of the nanowire,and the electrolyte with 3%(ω) of nanowire exhibited the highest ionic conductivity of 3.2 mS/cm at 20℃,as measured by electrochemical impedance spectroscopy.The temperature dependence of the conductivity was found to be in agreement with the Arrhenius equation.Functioning as separator and electrolyte,this nano-composite PVA gel electrolyte was used to assemble the electrochemical capacitor with active carbon film as electrodes.The compositing of nanowire may extend the life of electrochemical capacitors as they keep more than 90% of their capacitance after 5000 cycles of charging and discharging.

LaSr_2Mn_2O_7 Ruddlesden-Popper manganites for oxygen reduction and electrochemical capacitors

LaSr2 Mn2 O7,a Ruddlesden-Popper type bilayered perovskite,was investigated as oxygen catalyst for oxygen reduction reaction(ORR) and active electrode material for electrochemical capacitors in KOH solutions.XPS results show that Mn takes a mixed Mn2+,Mn3+and Mn4+valence state with an average valence of 3.4.As catalyst towards ORR,LaSr2 Mn2 O7 and LaSr2 Mn2 O7/acetylene black composite favor four electron pathways for ORR.LaSr2 Mn2 O7/C composite shows a comparable onset potential for ORR to that of Pt/C electrode.The improved ORR activity of LaSr2 Mn2 O7/acetylene black composite is attributed to the synergy between catalytic LaSr2 Mn2 O7 and conductive acetylene black.As electrode material for electrochemical capacitors,LaSr2 Mn2 O7 exhibits a maximum specific capacitance of 167.2 F/g with 62%faradic contribution at a scan rate of 1 mV/s in cyclic voltammetry test.

Fabrication and Electrochemical Properties of Carbon Nanotube-based Composite Electrodes for Electrochemical Capacitor Applications

1 Results Electrochemical capacitors (ECs) are expected to be used in hybrid electric vehicles in combination with batteries or fuel cells because of their higher power density than batteries. ECs using electrical double layer capacitance of carbon based materials and pseudocapacitance of transition metal oxides are called electrochemical double layer capacitors (EDLC) and supercapacitors (or pseudocapacitor), respectively. Transition metal oxides are considered the best candidates for high energy dens...

Chemical Treatment of Carbon Nanotubes as Electrodes in Electrochemical Double-Layer Capacitors

Multi-walled carbon nanombes with homogeneous diameters （40 - 60 nm）, produced by chemical vapor deposition of hydrocarbon gas, are purified by nitric acids. Infrared and Raman studies indicate that oxygen containing surface groups, which are predominately carboxylic, phenolic and lactonic groups, are introduced into purified carbon nanotubes. Then three kinds of block-form porous tablets of carbon nanotubes are fabricated as electrodes in electrochemical double-layer capacitors. Using mounded mixture comprising carbon nanotubes and binder powders provides these tablets. Comparison of the effect of different processing on the structural performance of the capacitors is specifically investigated. Using chemically treated electrodes, electrochemical double-layer capacitors with a specific capacitance of about 33 F/g are obtained with 38 wt % H2SO4 as the electrolyte.

Structural and Electrochemical Performances of α-MnO2 Doped with Tin for Supercapacitors

To improve the electrochemical performances of α-MnO2 as electrode materials for supercapacitors, Sn-doped α-MnO2 in the presence of the doping amount of 1%-4% was successfully synthesized by hydrothermal method. As-prepared α-MnO2 presents nanorod shape and no other impurities exist. By ultraviolet-visible absorption spectroscopy, it is convinced that the band gaps of α-MnO2 decrease with increasing Sn-doping amount. Cyclic voltammetry investigation indicates that undoped and doped α-MnO2 all have regular capacitive response. As the scan rate enlarged, the profiles of curves gradually deviate from rectangle. Compared with undoped α-MnO2, doped α-MnO2 has larger specific capacitance. The specific capacitance of 3% doped α-MnO2 reaches 241.0 F/g while undoped α-MnO2 only has 173.0 F/g under 50 m A/g current density in galvanostatical charge-discharge measurement. Enhanced conductivity by Sn-doping is considered to account for doped sample＇s enhanced electrochemical specific capacitance.