New design of electric double layer capacitors with aqueous LiOH electrolyte as alternative to capacitor with KOH solution

Activated carbon (AC) fiber cloths and a hydrophobic microporous polypropylene (PP) membrane, both modified with lithiated acetone oligomers, were used as electrodes and a separator in electric double layer capacitors (EDLCs) with aqueous lithium hydroxide (LiOH) as the electrolyte. Electrochemical characteristics of EDLCs were investigated by cyclic voltammetry (CV), galvanostatic charge-discharge cycle tests and impedance spectroscopy (EIS), compared with a case of the capacitor with aqueous potassium hydroxide (KOH) as an electrolyte. As a result, the capacitor with LiOH aqueous solution and a modified separator and electrodes was found to exhibit higher specific capacitance, maximum energy stored and maximum power than that with KOH aqueous solution.     

Impedance analysis on electric double layer capacitor with transmission line model

A new electrode model involving the fractal structure of activated carbon used as electrode material was proposed for an electric double layer capacitor (EDLC). The fractal structure of activate carbon was simulated by branch pore structure of three sizes of cylindrical pores. Three sizes of cylindrical pores were related to macro, meso, and micro pore, since the pore size of activated carbon has wide distribution with a few modes of nm order. The impedance spectrum of EDLC describes the locus of blocking electrode in low frequency range, and the curve at an angle of almost 45° to real axis in high frequency range on the Nyquist plane. The low and high frequency ranges of the impedance spectrum were defined as a lumped constant-type and a distributed constant-type, respectively. Computer simulation of electrochemical impedance with the present electrode model was carried out to understand the relation between the impedance and the electrode structure. The contributions of five parameters to impedance spectrum were discussed, i.e., depth of pore, diameter of pore, specific resistance, the interfacial impedance at electrode/solution, and branch number. The specific resistance p influenced on the shape of impedance spectrum in distributed constant-type range significantly. On other hand, the interfacial impedance at electrode/solution interface controlled the shape of the impedance spectrum in lumped constant-type range. In the course of the curve-fitting to impedance spectrum of EDLC, the separated impedance spectra related to macro, meso, and micro pores were obtained, and the roles of these pores on electric capacity were discussed.     

The effects of temperature on the performance of electrochemical double layer capacitors

An electrochemical double layer capacitor test cell containing activated carbon xerogel electrodes and ionic liquid electrolyte was tested at 15, 25 and 40 °C to examine the effect of temperature on electrolyte resistance (R_S) and equivalent series resistance (ESR) measured using impedance spectroscopy and capacitance using charge/discharge cycling. A commercial 10 F capacitor was used as a comparison. Viscosity, ionic self-diffusion coefficients and differential scanning calorimetry measurements were used to provide an insight into the behaviour of the 1,2-dimethyl-3-propylimdazolium electrolyte. Both R_S and ESR decreased with increasing temperature for both capacitors. Increasing the temperature also increased the capacitance for both the test cell and the commercial capacitor but proportionally more for the test cell. An increase in temperature decreased the ionic liquid electrolyte viscosity and increased the self-diffusion coefficients of both the anion and the cation indicating an increase in dissociation and increase in ionic mobility.     

Significantly enhanced charge conduction in electric double layer capacitors using carbon nanotube-grafted activated carbon electrodes

Carbon nanotube (CNT)-grafting by chemical vapor deposition was conducted to reduce the resistance of activated carbon fiber serving as an electrode for electric double layer capacitors. Sputtering deposition of Ni catalyst particles led to a uniform growth of CNTs on the carbon fiber surface through the tip-growth mechanism. Because sputtering deposition ensures little pore blockage (in comparison with wet-impregnation), the surface area decrease of the carbon fiber due to Ni loading was minimized. By using H₂SO₄ aqueous solution as the electrolyte, a capacitor cell assembled with the CNT-grafted fiber showed higher electron and electrolyte-ion conductivities relative to a cell assembled with the bare fiber. By increasing the discharging current density from 1 to 150 mA cm⁻², the bare fiber exhibited a capacitance loss of 17% while the CNT-grafted fiber showed a mitigated capacitance loss of only 7%. This developed CNT-grafting technique renders activated carbon fiber a promising electrode material for a variety of electrochemical applications.     

A thin layer including a carbon material improves the rate capability of an electric double layer capacitor

We present a new method to improve the rate capability of an electric double layer capacitor (EDLC) using a thin polymer layer having a high concentration of carbon material on a current collector (CLC). A novel thermocuring coating composed of a glycol-chitosan, a pyromellitic acid and a conductive carbon powder can form stable CLC on a metal foil current collector simply by spreading and curing at 160 °C for a couple of minutes. We compared the performance of some demonstration EDLC cells using three kinds of current collector: a conventional aluminum oxide foil for EDLC, an aluminum foil and an aluminum foil with CLC. The cell with the CLC had a much higher rate capability than the cell without CLC. Only the CLC cell was able to discharge at a current density of 500C. This cell shows a slight deterioration in capacity in a high temperature, continuous charging, life test, and the CLC has a suppressing effect on the internal resistance increase of EDLCs. The use of a CLC film current collector is one of the most effective and simple methods for the improvement of EDLC rate performance. In particular, a current collector consisting of aluminum foil coupled with a CLC promises to be a low cost alternative to the aluminum oxide foil commonly used in EDLCs.     

Electrochemical cell studies based on non-aqueous magnesium electrolyte for electric double layer capacitor applications

Performances of electric double layer capacitors (EDLCs) based on an activated carbon electrode with acetonitrile (ACN), propylene carbonate (PC), or a ternary electrolyte, i.e., PC:ethylene carbonate (EC):diethyl carbonate (DEC), at 1 mol dm⁻³ of magnesium perchlorate [Mg(ClO₄)₂] salt have been investigated. The electrochemical responses were studied by impedance spectroscopy, cyclic voltammetry, and galvanostatic charge-discharge experiments at 25 °C in a three-electrode configuration. For a comparative evaluation, lithium perchlorate (LiClO₄) salt-based systems were also evaluated. All the observed results showed typical EDLC characteristics within the potential range between 0 and 1 V vs. an Ag/Ag⁺ reference electrode. The Mg-based systems exhibited similar or rather better performances than the corresponding Li-based electrolytes; in particular, the rate capability of Mg-based ACN and PC electrolytes was much better than the corresponding Li-based electrolytes, indicating the high accessibility and utility of activated carbon pores by solvated Mg ions.     

Mesoporous activated carbon fiber as electrode material for high-performance electrochemical double layer capacitors with ionic liquid electrolyte

Activated carbon fibers (ACFs) with super high surface area and well-developed small mesopores have been prepared by pyrolyzing polyacrylonitrile fibers and NaOH activation. Their capacitive performances at room and elevated temperatures are evaluated in electrochemical double layer capacitors (EDLCs) using ionic liquid (IL) electrolyte composed of lithium bis(trifluoromethane sulfone)imide (LiN(SO₂CF₃)₂) and 2-oxazolidinone (C₃H₅NO₂). The surface area of the ACF is as high as 3291 m² g⁻¹. The pore volume of the carbon reaches 2.162 cm³ g⁻¹, of which 66.7% is the contribution of the small mesopores of 2-5 nm. The unique microstructures enable the ACFs to have good compatibility with the IL electrolyte. The specific capacitance reaches 187 F g⁻¹ at room temperature with good cycling and self-discharge performances. As the temperature increases to 60 °C, the capacitance increases to 196 F g⁻¹, and the rate capability is dramatically improved. Therefore, the ACF can be a promising electrode material for high-performance EDLCs.     

Solid state double layer capacitor based on a polyether polymer electrolyte blend and nanostructured carbon black electrode composites

An all solid double layer capacitor was assembled by using poly(ethylene oxide)/poly(propylene glycol)-b-poly(ethylene glycol)-b-poly(propylene glycol)-bis(2-aminopropyl ether) blend (PEO-NPPP) and LiClO₄ as polymer electrolyte layer and PEO-NPPP–carbon black (CB) as electrode film. High molecular weight PEO and the block copolymer NPPP with molecular mass of 2000 Da were employed, which means that the design is safe from the point of view of solvent or plasticizer leakage and thus, a separator is not necessary. Highly conductive with large surface area nanostructured carbon black was dispersed in the polymer blend to produce the electrode composite. The electrolyte and electrode multilayers prepared by spray were studied by differential scanning calorimetry, atomic force microscopy (AFM) and impedance spectroscopy. The ionic conductivity as a function of temperature was fitted with the Williams–Landel–Ferry equation, which indicates a conductivity mechanism typical of solid polymer electrolyte. AFM images of the nanocomposite electrode showed carbon black particles of approximately 60 nm in size well distributed in a semicrystalline and porous polymer blend coating. The solid double layer capacitor with 10 wt.% CB was designed with final thickness of approximately 130 μm and delivered a capacitance of 17 F g⁻¹ with a cyclability of more than 1000 cycles. These characteristics make possible the construction of a miniature device in complete solid state which will avoid electrolyte leakage and present a performance superior to other similar electric double layer capacitors (EDLCs) presented in literature, as assessed in specific capacitance by total carbon mass.     

Performance and stability of electrochemical capacitor based on anthraquinone modified activated carbon

A series of high surface area activated carbon powders modified with various loadings of electroactive anthraquinone groups was obtained by the spontaneous reduction of the corresponding in situ generated diazonium derivative on activated carbon. The diazotation and grafting reactions are fast and efficient and by varying the stoichiometry of these reactions the grafting amount can be controlled. With appropriate reaction conditions, the attachment of anthraquinone groups allows to double the capacitance of the modified carbonaceous material (195 F g⁻¹) compared to the unmodified carbon (100 F g⁻¹) due to the contribution of the redox reaction of grafted anthraquinone molecules. Long time galvanostatic charge-discharge cycling experiments were performed for composite electrodes prepared using modified carbons having two different AQ loadings (e.g. 6.7 and 11.1 wt.%). Following 10 000 charge/discharge cycles, only a 17% loss of the faradaic capacitance was observed for these two carbons. Thus, this hybrid bifunctional material appears to be an excellent candidate for application as active electrode in electrochemical capacitors.     

Improvement of capacitance value as the electrode of an electrochemical capacitor by mixing starch with guanidine phosphate

Starch or starch mixed with phosphoric acid, guanidine carbonate, or guanidine phosphate is heat-treated for use as an electrode in an electrochemical capacitor. In the case of starch, the capacitance value is low (31.2 F g⁻¹ at 50 mA g⁻¹). However, the capacitance value significantly increases with the addition of guanidine phosphate, which can act as a flame-retardant (124.1F g⁻¹ at 50 mA g⁻¹). The method used in this study, which involves mixing with a flame-retardant by immersion, should be a promising candidate for improving of the capacitance value of starch-derived carbon.     

Asymmetric capacitor based on superior porous Ni-Zn-Co oxide/hydroxide and carbon electrodes

Hierarchical porous multi-phase Ni-Zn-Co oxide/hydroxide is synthesized by using metal-organic framework-5 (MOF-5) as the template. Hierarchical porous carbon is obtained by the facile direct decomposition of the MOF-5 framework with phenolic resin. The structures and textures are characterized by X-ray diffraction, high-resolution transmission electron microscopy, scanning electron microscopy, and nitrogen sorption at 77 K. An asymmetric capacitor incorporating the Ni-Zn-Co oxide/hydroxide as the positive electrode and the porous carbon as the negative electrode is fabricated. A maximum energy density of 41.65 Wh kg⁻¹ is obtained, which outperforms many other available asymmetric capacitors. The asymmetric capacitor also shows a good high-rate performance, possessing an energy density of 16.62 Wh kg⁻¹ at the power density of about 2900 W kg⁻¹.     

Performance of nitrogen- and sulfur-containing carbon material derived from thiourea and formaldehyde as electrochemical capacitor

In order to investigate the performance of an electrochemical capacitor consisting of a nitrogen- and sulfur-containing carbon material, the carbon material derived from thiourea and urea was synthesized by a polymerization process of the urea resin. No solid appeared after the polymerization process. When the dried sample after the polymerization process was heated in flowing N2 gas, we obtained carbon material. However, there was no product when only thiourea was heated under the same conditions. The percentages of nitrogen and sulfur in all the samples synthesized from thiourea were roughly 5-20 wt.% and 3-8 wt.% even after washing with hot water, respectively. No specific peak derived from the redox reaction appeared in the CV graphs for the samples. The capacitance value of T-urea800W, which was synthesized by the heat treatment at 800 °C and then wash with hot water, was 138.8 F g⁻¹ at the current density of 50 mA g⁻¹ in a 1 M H₂SO₄ water solution whereas that value of a commercial activated carbon was 107.1 F g⁻¹ under the same conditions. It was presumed from the XPS measurements that the status of the nitrogen and sulfur in the materials are a pyridine-like nitrogen at the edge part of the graphitic structure, a quaternary nitrogen in the graphitic-layered structure, and S⁰, S⁴⁺, and S²⁻, respectively.     

Investigation of the life process of the electric double layer capacitor during float charging

The electric double layer capacitor (EDLC) should have an almost indefinite life, because the EDLC is charged and discharged by the electrostatic adsorption and desorption of ions on electrodes whose processing involves mass transfers without a chemical reaction. However, the actual life of an EDLC is finite, such that its performance begins to slowly degrade and is significantly deteriorated at some point. We have investigated this phenomenon in detail by analyzing changes in the species of the EDLC during its life. We found that reactions on the positive and negative electrode occurred in phase with the consumption of oxygen, carbon in the electrode materials, and anions in the electrolyte during EDLC charging to change the electrode potentials and the abundance of ions on the electrodes. A product and/or disappearance by the side reactions deteriorated the performance of the active materials. Here we suggest a life process during the float charge of the EDLC and a directional concept for extending its life while comparing experimental data with theoretical models of EDLC charging.     

Enhanced electrochemical performance in microbial fuel cell with carbon nanotube/NiCoAl-layered double hydroxide nanosheets as air-cathode

The ternary component NiCoAl-layered double hydroxide (NiCoAl-LDH) and carbon nanotube (CNT) nano-composite (CNT/NiCoAl-LDH) were successfully prepared by a simple hydrothermal method. The NiCoAl-LDH nanosheets were effectively and uniformly grown on CNTs, forming a cross-linked conductive network structure, and stainless steel (SS) mesh was used as the base to load CNT/NiCoAl-LDH for microbial fuel cell (MFC) cathode. X-ray diffraction (XRD) results presented that the CNT/NiCoAl-LDH hybrid exhibited the (003), (006), (012), (015), (018), (110) and (113) crystal planes of hydrotalcite reflection. The surface functional groups C-O, C=O, C-H, C-N and M-O of the hybrid were confirmed. The cross-linked network structure of the hybrid was observed and the content and proportion of each element of the hybrid were found. CNT/NiCoAl-LDH showed excellent catalytic oxygen reduction reaction (ORR) ability by cyclic voltammetry (CV) and linear voltammetry (LSV) due to its abundant electrochemical active sites and excellent conductivity. The maximum output voltage of CNT/NiCoAl-LDH catalyst as MFC cathode was 450 mV, the maximum power density was 433.5 ± 14.8 mW/m², and the maximum voltage stabilization time was 7–8 d. The results indicated that the CNT/NiCoAl-LDH hybrid was full potential as a high-performance, low-cost MFC cathode catalyst in future.     

Effects of addition of different carbon materials on the electrochemical performance of nickel hydroxide electrode

Nickel hydroxide is used as an active material in positive electrodes of rechargeable alkaline batteries. The capacity of nickel-metal hydride (Ni-MH) batteries depends on the specific capacity of the positive electrode and utilization of the active material because of the Ni(OH)₂/NiOOH electrode capacity limitation. The practical capacity of the positive nickel electrode depends on the efficiency of the conductive network connecting the Ni(OH)₂ particle with the current collector. As β-Ni(OH)₂ is a kind of semiconductor, the additives are necessary to improve the conductivity between the active material and the current collector. In this study the effect of adding different carbon materials (flake graphite, multi-walled carbon nanotubes (MWNT)) on the electrochemical performance of pasted nickel-foam electrode was established. A method of production of MWNT special type of catalysts had an influence on the performance of the nickel electrodes. The electrochemical tests showed that the electrode with added MWNT (110-170 nm diameter) exhibited better electrochemical properties in the chargeability, specific discharge capacity, active material utilization, discharge voltage and cycling stability. The nickel electrodes with MWNT addition (110-170 nm diameter) have exhibited a specific capacity close to 280 mAh g⁻¹ of Ni(OH)₂, and the degree of active material utilization was ∼96%.     

Electrospun nickel oxide/polymer fibrous electrodes for electrochemical capacitors and effect of heat treatment process on their performance

Electrospinning is a versatile method for preparation of submicron-size fibers under ambient temperature. We demonstrate a new approach based on this method for preparing an electrode which consists of the fibers coated with nickel oxide (NiO) and acetylene black (AB) on their surfaces. The NiO/polymer fibrous electrodes show the electrochemical responses based on the electrochemical reaction of Ni(OH)₂ which is produced from NiO in alkaline aqueous solution. The capacitance of the test half cell with the as-prepared NiO/polymer fibrous electrode in 1 mol l⁻¹ KOH aqueous solution is 5.8 F g⁻¹ (per gram of NiO). Heat treatment (at 150 °C for 1 h in the air) of the NiO/polymer fibrous electrode increases the capacitance of the NiO/polymer fibrous electrode. The capacitance of the cell with the heat treated (HT) NiO/polymer fibrous electrode is 163 F g⁻¹ (per gram of NiO). SEM observation of the heat treated electrode suggests that partial melt of the fibers on the current collector forms the conducting passes and networks between the NiO particles and the collector and increases the specific capacity of the fibrous electrode.     

Analysis on the effect of operating conditions on electrochemical conversion of carbon dioxide to formic acid

Electrochemical reduction of CO₂ to HCOOH was performed on a Sn electrode using a proton exchange membrane-embedded electrolysis cell. The effects of reaction conditions such as catholyte and anolyte types, reduction potential, catholyte pH, and reaction temperature on the amount of HCOOH and its faradaic efficiency were investigated. Four different electrolytes (KOH, KHCO₃, KCl, KHSO₄) were chosen as the candidate catholyte and anolyte; the most suitable electrolyte was chosen by monitoring the amount of HCOOH and faradaic efficiency. The effect of the pH of the selected catholyte on the conversion of CO₂ to HCOOH was also investigated. In addition, the reaction temperature was varied and its effect was studied. From the observations made, we determined the optimal reaction conditions for the production of HCOOH via the electrochemical reduction of CO₂ by a systematic approach.     

Study on the in situ sulfidation and electrochemical performance of spherical nickel hydroxide

In this paper, atmospheric reflux in water is used to directly form a nickel sulfide layer in-situ with excellent conductivity sulfide on the surface of spherical nickel hydroxide particles, significantly improving the conductivity of nickel hydroxide particles. The experimental results show that the spherical Ni(OH)₂@NiS material synthesized by the in situ sulfurization method. As the cathode active material of nickel-iron batteries exhibits excellent electrochemical performance, especially high-rate discharge and cycle performance, which are better than nickel hydroxide electrodes with cobalt oxide. The atmospheric reflux method in water has a simple process and equipment and has no pollution to the environment. Spherical Ni(OH)₂@NiS materials synthesized by in situ vulcanization can completely replace nickel hydroxide material with cobalt, and they have great commercial application value and market competitiveness as cathode active materials for alkaline nickel-based batteries.     

Effects of the cationic structures of fluorohydrogenate ionic liquid electrolytes on the electric double layer capacitance

Electric double layer capacitance of an activated carbon electrode has been measured for fluorohydrogenate ionic liquids (FHILs) based on five different cations (1,3-dimethylimidazolium (DMIm⁺), 1-ethyl-3-methylimidazolium (EMIm⁺), 1-butyl-3-methylimidazolium (BMIm⁺), 1-ethyl-1-methylpyrrolidinium (EMPyr⁺), and 1-methoxymethyl-1-methylpyrrolidinium (MOMMPyr⁺)) at 25 °C. For all the FHILs, the capacitance increases with increase in charging voltage, and exhibits the maximum value around 2.7 V. The capacitances for FHILs are higher than those for EMImBF₄ or 1 M tetraethylammonium tetrafluoroborate in propylene carbonate (TEABF₄/PC) in the measured range (1.0 < V < 3.2). For the three imidazolium-based FHILs, the maximum capacitance decreases with increase in the size of the cation in the order, DMIm(FH)_2.3F (178 F g⁻¹) > EMIm(FH)_2.3F (162 F g⁻¹) > BMIm(FH)_2.3F (135 F g⁻¹). On the other hand, the maximum capacitance observed for MOMMPyr(FH)_2.3F (152 F g⁻¹) is larger than that for EMPyr(FH)_2.3F (134 F g⁻¹) in spite of the larger size of MOMMPyr⁺ than EMPyr⁺, which is derived from introduction of the methoxy group. Some FHILs with low melting points exhibit a sufficient capacitance even at −40 °C (64 F g⁻¹ for EMIm(FH)_2.3F).     

Ageing behaviour of electrochemical double layer capacitors: Part I. Experimental study and ageing model

Different types of commercially available electrochemical double layer capacitors (EDLCs) were analysed in accelerated ageing tests by impedance spectroscopy. From these measurements the parameters of an impedance model were determined. The characteristic change of the impedance parameters is discussed and an ageing model for EDLCs is developed.