Capacitive matching of pore size and ion size in the negative and positive electrodes for supercapacitors

The capacitive behavior of activated carbons with different pore structures in two kinds of electrolytes, Bu₄NBF₄ and Et₄NBF₄ in propylene carbonate (PC) was studied using three kinds of cell configuration. The correlations between adsorbed ion size and pore size on the positive and negative electrodes were investigated. The matching of pore size and cation size was more predominant in the capacitor unit, especially for the electrode materials with less developed porosity. The asymmetric capacitance distribution of 7 F g⁻¹ in the negative electrode and 113 F g⁻¹ in the positive electrode occurred for electrode materials with less developed porosity. This could be ascribed to the surface saturation of the negative electrode by electrolyte ions, limiting the overall capacitance and working voltage of device. However, very developed porosity could not profit from the sufficient unitization of surface area, due to a weakened interaction between ions and pores wall. The specific area capacitance experienced a significant decrease from 11.3 to 6.7 μF cm⁻² with the pore volume increasing. Since the different pore sizes were required for different electrolytes ion on the negative and positive electrodes, the optimal matching between pores size and ions dimension with respect to each electrode should be considered for the maximum capacitance value of the capacitor unit.     

Improvement of the structural and chemical properties of a commercial activated carbon for its application in electrochemical capacitors

The present paper shows that the performance of an inexpensive activated carbon used in electrochemical capacitors can be significantly enhanced by a simple treatment with KOH at 850 °C. The changes in the specific surface area, as well as in the surface chemistry, lead to high capacitance values, which provide a noticeable energy density.The KOH-treatment of a commercial activated carbon leads to highly pure carbons with effective surface areas in the range of 1300-1500 m² g⁻¹ and gravimetric capacitances as high as three times that of the raw carbon.For re-activated carbons, one obtains at low current density (50 mA g⁻¹) values of 200 F g⁻¹ in aqueous electrolytes (1M H₂SO₄ and 6M KOH) and around 150 F g⁻¹ in 1M (C₂H₅)₄NBF₄ in acetonitrile. Furthermore, the resulting carbons present an enhanced and stable performance for high charge/discharge load in organic and aqueous media.This work confirms the possibilities offered by immersion calorimetry on its own for the prediction of the specific capacitance of carbons in (C₂H₅)₄NBF₄/acetonitrile. On the other hand, it also shows the limitations of this technique to assess, with a good accuracy, the suitability of a carbon to be used as capacitor electrodes operating in aqueous electrolytes (H₂SO₄ and KOH).     

Morphology and organic EDLC applications of chemically activated AR-resin-based carbons

A morphological characterization of activated AR-resin was carried out. The time and temperature effect of the EDLC (electric double layer capacitor) properties of AR-resin were investigated. In order to clarify the relation between the electric double layer capacitance and the ion mobility in the organic solvent, a computer simulation was used to calculate the possible solvation size of Et₄NBF₄ in propylene carbonate. The sample (HTT 700) activated at a heat treatment temperature (HTT) of 700 °C for 2 h has a specific capacitance as high as 35.27 F g⁻¹ (equivalent to 141.08 F g⁻¹ for a single electrode), when it is charged to 2.5 V and discharged at 1 mA cm⁻². The capacitance increase by using a longer activation time at each HTT was as follows: 2.3 times at HTT 600, 1.6 times at HTT 700, 1.3 times at HTT 800 and 1.2 times at HTT 900. This variation could be forecast from image analysis using a TEM photograph. Furthermore, a possible ion size of electrolyte (Et₄NBF₄) in a solvent was calculated and it is related to the mobility of charge carriers in a micropore.     

Highly mesoporous carbonaceous material of activated carbon beads for electric double layer capacitor

The activated carbon beads (ACB) are prepared by a new preparation method, which is proposed by mixing the coal tar pitch and fumed silica powder at a certain weight ratio and activation by KOH at different weight ratios and different temperatures. The BET surface area, pore volume and average pore size are obtained based on the nitrogen adsorption isotherms at 77 K by using ASAP 2010 apparatus. The results show that our samples have much high specific surface area (SSA) of 3537 m² g⁻¹and high pore volume value of 3.05 cm³ g⁻¹. The percentage of mesopore volume increases with the weight ratio of KOH/ACB ranging from 4% to 72%. The electrochemical double layer capacitors (EDLCs) are assembled with resultant carbon electrode and electrolyte of 1 mol L⁻¹ Et₄NBF₄/PC. The specific capacitance of the ACB sample could be as high as 191.7 F g⁻¹ by constant current charge/discharge technique, indicating that the ACB presents good characteristics prepared by the method proposed in this work. The investigation of influence of carbon porosity structure on capacitance indicates that the SSA plays an important role on the capacitance and all the pore sizes of less than 1 nm, from 1 to 2 nm and larger than 2 nm contribute to the capacitance. Mesopore structure is beneficial for the performance at high current density.     

EDLC performance of carbide-derived carbons in aprotic and acidic electrolytes

This study shows that carbide-derived carbons (CDCs) with average pore size distributions around 0.9-1 nm and effective surface areas of 1300-1400 m² g⁻¹ provide electrochemical double-layer capacitors with high performances in both aqueous (2M H₂SO₄) and aprotic (1M (C₂H₅)₄NBF₄ in acetonitrile) electrolytes.In the acidic electrolytic solution, the gravimetric capacitance at low current density (1 mA cm⁻²) can exceed 200 F g⁻¹, whereas the volumetric capacitance reaches 90 F cm⁻³. In the aprotic electrolyte they reach 150 F g⁻¹ and 60 F cm⁻³.A detailed comparison of the capacitive behaviour of CDCs at high current density (up to 100 mA cm⁻²) with other microporous and mesoporous carbons indicates better rate capabilities for the present materials in both electrolytes. This is due to the high surface area, the accessible porosity and the relatively low oxygen content.It also appears that the surface-related capacitances of the present CDCs in the aprotic electrolyte are in line with other carbons and show no anomalous behaviour.     

Performance of templated mesoporous carbons in supercapacitors

By analogy with other types of carbons, templated mesoporous carbons (TMCs) can be used as supercapacitors. Their contribution arises essentially from the double layer capacity formed on their surface, which corresponds to 0.14 F m⁻² in aqueous electrolytes such as H₂SO₄ and KOH and 0.06 F m⁻² for the aprotic medium (C₂H₅)₄NBF₄ in CH₃CN. In the case of a series of 27 TMCs, it appears that the effective surface area determined by independent techniques can be as high as 1500-1600 m² g⁻¹, and therefore exceeds the value obtained for many activated carbons (typically 900-1300 m² g⁻¹). On the other hand, the relatively low amount of surface oxygen in the present TMCs, as opposed to activated carbons, reduces the contribution of pseudo-capacitance effects and limits the gravimetric capacitance to 200-220 F g⁻¹ for aqueous electrolytes. In the case of non-aqueous electrolyte, it rarely exceeds 100 F g⁻¹.It is also shown that the average mesopore diameter of these TMCs does not improve significantly the ionic mobility compared with typical activated carbons of pore-widths above 1.0-1.3 nm.This study suggests that activated carbons remain the more promising candidates for supercapacitors with high performances.     

Polyfurfuryl alcohol derived activated carbons for high power electrical double layer capacitors

Polyfurfuryl alcohol (PFA) derived activated carbons were prepared by the acid catalysed polymerization of furfuryl alcohol, followed by potassium hydroxide activation. Activated carbons with apparent BET surface areas ranging from 1070 to 2600 m² g⁻¹, and corresponding average micropore sizes between 0.6 and 1.6 nm were obtained. The porosity of these carbons can be carefully controlled during activation and their performance as electrode materials in electric double layer capacitors (EDLCs) in a non-aqueous electrolyte (1 M Et₄NBF₄/ACN) is investigated.Carbon materials with a low average pore size (<∼0.6 nm) exhibited electrolyte accessibility issues and an associated decrease in capacitance at high charging rates. PFA carbons with larger average pore sizes exhibited greatly improved performance, with specific electrode capacitances of 150 F g⁻¹ at an operating voltage window of 0-2.5 V; which corresponds to 32 Wh kg⁻¹ and 38 kW kg⁻¹ on an active material basis. These carbons also displayed an outstanding performance at high current densities delivering up to 100 F g⁻¹ at current densities as high as 250 A g⁻¹. The exceptionally high capacitance and power of this electrode material is attributed to its good electronic conductivity and a highly effective combination of micro- and fine mesoporosity.     

Ethylene carbonate-based organic electrolytes for electric double layer capacitors

A new electrolytic solution based on a mixed solvent of ethylene carbonate (EC) with sulfolane (SL) or -butyrolactone (-BL) has been examined as an electric double layer capacitor. Fundamental properties, such as electrolytic conductivity, viscosity, and thermal stability, were measured for solutions containing quaternary alkylammonium salts as the supporting electrolyte. Maximum conductivities were obtained for the solutions with mixed solvent of 20–40 mol % EC in the EC+-BL system: 1.2–1.3×10^–2S cm^–1 for EC+-BL dissolving 0.5 M Et₄ NBF₄ (Et=C₂H₅). The electrochemical and the thermal stabilities of the solution were dependent on the electrolytic salt as well as the solvent composition. A stable discharge capacitance and a high coulombic efficiency were obtained in a model capacitor using carbon fibre electrodes and the organic electrolyte of EC+-BL/Et₄NBF₄ (or EC+-BL/Et₄NPF₆).     

Effect of mesoporosity on specific capacitance of carbons

The study compares the structural and electrochemical properties of 12 porous carbons based on phenolic resins, using both aqueous (H₂SO₄) and aprotic ((C₂H₅)₄NBF₄ in acetonitrile) electrolytes. It appears that they fit into the general pattern observed for other carbons. The present carbons have micropore volumes varying between 0.29 and 0.66 cm³ g⁻¹ and average pore widths L_o between 0.62 and 1.23 nm. Five samples are exclusively microporous, whereas seven also display a relatively important mesoporosity. This allows a direct comparison between pairs of carbons with similar micropore systems, with and without mesopores, in order to assess the role of mesoporosity in the electrochemical properties. It appears that mesopores have only a limited influence on the decrease in capacitance at high current density as opposed to earlier assumptions.     

Characterisation of activated nanoporous carbon for supercapacitor electrode materials

Commercial nanoporous carbon RP-20 was activated with water vapor in the temperature range from 950 °C to 1150 °C. The XRD analysis was carried out on nanoporous carbon powder samples to investigate the structural changes (graphitisation) in modified carbon that occurred at activation temperatures T ? 1150 °C. The first-order Raman spectra showed the absorption peak at 1582 cm⁻¹ and the disorder (D) peak at 1350 cm⁻¹. The low-temperature N₂ adsorption experiments were performed at −196 °C and a specific surface area up to 2240 m²g⁻¹ for carbon activated at T = 1050 °C was measured. The cell capacitance for two electrode activated nanoporous carbon system advanced up to 60 F g⁻¹ giving the specific capacitance ∼240 F g⁻¹ to one electrode nanoporous carbon ∣1.2 M (C₂H₅)₃CH₃NBF₄ + acetonitrile solution interface. A very wide region of ideal polarisability for two electrode system (∼3.2 V) was achieved. The low frequency limiting specific capacitance very weakly increases with the rise of specific area explained by the mass transfer limitations in the nanoporous carbon electrodes. The electrochemical characteristics obtained show that some of these materials under discussion can be used for compilation of high energy density and power density non-aqueous electrolyte supercapacitors with higher power densities than aqueous supercapacitors.     

1-Alkyl-2,3-dimethylimidazolium bis(trifluoromethanesulfonyl)imide ionic liquids as highly safe electrolyte for Li/LiFePO4 battery

Several 1-alkyl-2,3-dimethylimidazolium bis(trifluoromethanesulfonyl)imide ionic liquids (alkyl-DMimTFSI) were prepared by changing carbon chain lengths and configuration of the alkyl group, and their electrochemical properties and compatibility with Li/LiFePO₄ battery electrodes were investigated in detail. Experiments indicated the type of ionic liquid has a wide electrochemical window (−0.16 to 5.2 V vs. Li⁺/Li) and are theoretically feasible as an electrolyte for batteries with metallic lithium as anode. Addition of vinylene carbonate (VC) improves the compatibility of alkyl-DMimTFSI-based electrolytes towards lithium anode and LiFePO₄ cathode, and enhanced the formation of solid electrolyte interface to protect lithium anodes from corrosion. The electrochemical properties of the ionic liquids obviously depend on carbon chain length and configuration of the alkyl, including ionic conductivity, viscosity, and charge/discharge capacity etc. Among five alkyl-DMimTFSI-LiTFSI-VC electrolytes, Li/LiFePO₄ battery with the electrolyte-based on amyl-DMimTFSI shows best charge/discharge capacity and reversibility due to relatively high conductivity and low viscosity, its initial discharge capacity is about 152.6 mAh g⁻¹, which the value is near to theoretical specific capacity (170 mAh g⁻¹). Although the battery with electrolyte-based isooctyl-DMimTFSI has lowest initial discharge capacity (8.1 mAh g⁻¹) due to relatively poor conductivity and high viscosity, the value will be dramatically added to 129.6 mAh g⁻¹ when 10% propylene carbonate was introduced into the ternary electrolyte as diluent. These results clearly indicates this type of ionic liquids have fine application prospect for lithium batteries as highly safety electrolytes in the future.     

Easy synthesis of mesoporous carbon using nano-CaCO3 as template

Mesoporous carbon has been synthesized using nano-CaCO₃ as a template and sucrose as carbon precursor. It is shown that the CaCO₃/sucrose weight ratio has a marked effect on the porosity of the carbon. At a weight ratio of CaCO₃/sucrose of 1:1, the surface area of the carbon reaches 892 m² g⁻¹ and the pore size is around 45 nm. The carbon shows a capacitance of 155 F/g with excellent rate capability in 6 mol L⁻¹ KOH aqueous electrolytes.     

Synthesis and electrochemical characterization of bis(3,4-ethylene-dioxythiophene)-(4,4′-dinonyl-2,2′-bithiazole) comonomer

The synthesis and characterization of a novel donor acceptor donor type bis(3,4-ethylene-dioxythiophene)-(4,4′-dinonyl-2,2′-bithiazole) comonomer and its electrochemically prepared polymer on carbon fiber, Pt button and ITO plate is reported in this paper. Cyclic voltammetry of the polymer in 0.1 M Et₄NBF₄/CH₂Cl₂ exhibits a very well defined and reversible redox processes and this co-monomer can be either p-doped or n-doped. The half-wave oxidation potentials of the polymer (E_1/2) were observed at 0.303 and 0.814 V versus Ag/AgCl. The polymer is electrochromic; the onset for the π-π^* transition (E_g) of 1.75 eV with a λ_max at 2.15 eV and the homogeneous and high quality film of the polymer is stable of its optical properties offering fast switching time which is less than 0.25 s. The morphological studies reveal that the polymer was deposited as a continuous and very well adhering film to surface of the carbon fiber microelectrode. All these properties make this polymer favorable for use in electronic devices.     

Iodide/triiodide electrochemistry in ionic liquids: Effect of viscosity on mass transport, voltammetry and scanning electrochemical microscopy

The electrochemistry of I⁻/I₃⁻ was studied in ionic liquids using a combination of cyclic voltammetry, chronoamperometry and scanning electrochemical microscopy (SECM). The electrolytes were 1-alkyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide [C_nC₁Im][Tf₂N], ionic liquids (where n = 2, 4 and 8) and I⁻ was typically added at a concentration of approximately 11 mM. During cyclic voltammetry, two sets of peaks were observed in each ionic liquid due to oxidation and reduction of the I⁻/I₃⁻ redox couple and oxidation/reduction of the I₃⁻/I₂ redox couple. The diffusion coefficients of I⁻ and I₃⁻, as determined using chronoamperometry, increased with increasing temperature and decreased with increasing ionic liquid viscosity. The effect of ionic liquid viscosity on ultramicroelectrode (UME) voltammetry was also determined using the I⁻/I₃⁻ redox couple. Steady-state behaviour was observed at 1.3 μm UMEs at slow voltammetric scan rates and steady-state SECM feedback approach curves were also obtained at a 1.3 μm Pt SECM tips, provided that the tip approach speed was sufficiently low.     

Gill inspired hierarchical wrinkles of reduced graphene oxide encapsulated carbon nanotubes with significantly boosted supercapacitor performance

It has long been pursued in the energy storage community that 3D carbon materials can be constructed with 1D carbon nanotubes and 2D graphene in a proper manner that fully develops their appealing synergistic effects of high conductivity and large surface area. However, the present hybrid nanostructures suffer from either weak bonding strength or heavy dependence on high cost processing techniques. Here we report a gill-inspired hierarchical structure created by a simple annealing strategy, where carbon nanotubes are encapsulated in the wrinkles made of reduced graphene oxide, in resemblance to the vessels embedded in the wrinkle-like gill lamellae. The wrinkled structure enables enriched micropore structures and improved specific surface area, while the embedded carbon nanotubes guarantee the enhanced electrical conductivity. Thus, rGO@CNTs@AC (1000) achieved a 75% increase in the specific capacity @ 1 A g⁻¹ (200 F g⁻¹ vs. 120 F g⁻¹) when compared to a commericial AC in 1 M Et₄NBF₄/PC. In addition, the encapsulation strategy improved the supercapacitor stability by preventing the electrode materials from falling apart during the cycling. After 1000 cycles @ 1 A g⁻¹, the capacity retention rate of rGO@CNTs@AC (1000) remained above 90% while that of AC only maintained around 60%. More importantly, the proposed strategy should be applicable to general electrode materials for further improvement as supercapacitors. This work offers a novel bio-inspired strategy to effectively improve the supercapacitor performance by rationally designed hierarchical nanostructures.     

All solid electric double layer capacitors based on Nafion ionomer

The aim of the present work is to demonstrate that an efficient all solid electric double layer capacitor (EDLC) may be realised with electrolyte membrane and carbon based electrodes prepared by using a Nafion ionomer solution. Polymer membrane was prepared by a casting method. Electrodes were prepared with two overlapped layers formed of a carbon-Nafion layer and a carbon paper substrate. Three different electrolyte separators in capacitor configuration have been tested and compared: (1) a commercial Nafion 115 membrane (N115), (2) a membrane prepared by casting the Nafion 1100 solution (NRG50) and (3) a porous glass fibre matrix impregnated with a 1 M H₂SO₄ solution (FVH2SO4). The membrane and electrodes assemblies (MEA) had thickness of 0.6-0.8 mm and geometric area of 4 cm². The EDLCs characteristics have been studied by conductivity, cyclic voltammetry and DC charge-discharge methods. Proton conductivities of 5.7×10⁻² and 3.1×10⁻² S cm⁻¹ have been measured at room temperature for the N115 and the NRG50, respectively. Specific capacity of 13.2 F g⁻¹ has been obtained by capacitor utilising the cast Nafion membrane. This value is 70% of specific capacity obtained from the capacitor using sulphuric acid and about 140% of that using Nafion 115.     

Effect of surface modified porous inorganic-organic hybrid polyphosphazene nanotubes on the properties of polyethylene oxide based solid polymer electrolytes

2-(2-methyloxyethoxy)ethanol modified poly (cyclotriphosphazene-co-4,4′-sufonyldiphenol) (PZS) nanotubes were synthesized and solid composite polymer electrolytes based on the surface modified polyphosphazene nanotubes added to PEO/LiClO₄ model system were prepared. Differential Scanning Calorimetry (DSC) and Scanning Electron Microscopy (SEM) were used to investigate the characteristics of the composite polymer electrolytes (CPE). The ionic conductivity, lithium ion transference number and electrochemical stability window can be enhanced after the addition of surface modified PZS nanotubes. The electrochemical investigation shows that the solid composite polymer electrolytes incorporated with PZS nanotubes have higher ionic conductivity and lithium ion transference number than the filler SiO₂. Maximum ionic conductivity values of 4.95 × 10⁻⁵ S cm⁻¹ at ambient temperature and 1.64 × 10⁻³ S cm⁻¹ at 80 °C with 10 wt % content of surface modified PZS nanotubes were obtained and the lithium ion transference number was 0.41. The good chemical properties of the solid state composite polymer electrolytes suggested that the inorganic-organic hybrid polyphosphazene nanotubes had a promising use as fillers in solid composite polymer electrolytes and the PEO₁₀-LiClO₄-PZS nanotubes solid composite polymer electrolyte can be used as a candidate material for lithium polymer batteries.     

A dilatometric and small-angle X-ray scattering study of the electrochemical activation of mesophase pitch-derived carbon in non-aqueous electrolyte solution

The electrochemical activation of certain pitch-derived carbons has been proposed as a promising route towards obtaining high-capacitance electrodes for electrochemical double-layer capacitors. In the present work, the mechanism of electrochemical activation of a graphitizable carbon after calcination and KOH-activation was studied by nitrogen adsorption, electrochemical dilatometry and in situ small-angle X-ray scattering (SAXS). During electrochemical activation, a large capacitance gain from 1 to 121 F/g (at 0 V in a 1 mol/L solution of Et₄NBF₄ in propylene carbonate) was accompanied by a significant irreversible swelling of the electrode by 24% (6%) for activation in the negative (positive) potential range, respectively. In situ SAXS provided clear evidence for the insertion of ions into the latent microporosity of the carbon during electrochemical activation. Thus, the mechanism of electrochemical activation of weakly activated graphitizable carbon is not strictly due to ion intercalation between parallel graphene sheets.     

Core–shell Ni0.5TiOPO4/C composites as anode materials in Li ion batteries

Pristine Ni_0.5TiOPO₄ was prepared via a traditional solid-state reaction, and then Ni_0.5TiOPO₄/C composites with core–shell nanostructures were synthesized by hydrothermally treating Ni_0.5TiOPO₄ in glucose solution. X-ray diffraction patterns indicate that Ni_0.5TiOPO₄/C crystallizes in monoclinic P2₁/c space group. Scanning electron microscopy and transmission electron microscopy show that the small particles with different sizes are coated with uniform carbon film of ∼3 nm in thickness. Raman spectroscopy also confirms the presence of carbon in the composites. Ni_0.5TiOPO₄/C composites presented a capacity of 276 mAh g⁻¹ after 30 cycles at the current density of 42.7 mA g⁻¹, much higher than that of pristine Ni_0.5TiOPO₄ (155 mAh g⁻¹). The improved electrochemical performances can be attributed to the existence of carbon shell.     

Polymer electrolytes based on a ternary miscible blend of poly(ethylene oxide), poly(bisphenol A-co-epichlorohydrin) and poly(vinyl ethyl ether)

Ternary blends of poly(ethylene oxide) (PEO), poly(bisphenol A-co-epichlorohydrin) (PBE) and poly(vinyl ethyl ether) (PVEE) were obtained as films and characterized by differential scanning calorimetry (DSC) and vibrational spectroscopy (FTIR). From the DSC results, phase diagrams for the ternary blends were determined, where the variation of the viscoelastic phase extent as a function of the polymers composition was determined. The DSC results also indicated miscibility of the system, exhibiting only one glass transition temperature (T_g) and decrease in the crystallinity of the system, as well as decrease in the crystallinity of PEO present in the blends. Vibrational spectroscopy (FTIR) provided information on the intermolecular interactions between the pairs PBE/PEO and PBE/PVEE, via hydrogen bond interaction. From the FTIR analyses, molecular model systems of equilibrium among the interacting structures were proposed as a molecular basis for the miscibility of the system.Polymer electrolytes based on the ternary blend containing 60/25/15 (PEO/PBE/PVEE) mass percent and lithium perchlorate (LiClO₄) were obtained and characterized by DSC, FTIR, optical microscopy and electrochemical impedance spectroscopy (EIS). Solid electrolytes containing up to 10 wt% LiClO₄ exhibited a single-phase behavior, evidenced by the DSC results. For these electrolytes, FTIR spectra indicated the formation of polymer-ion complexes, in which the cation (Li⁺) acts favoring the polymer-polymer miscibility. Electrolytes containing LiClO₄ higher than 10 wt% exhibit a multiple phase behavior, in which a PEO-rich, salt-containing phase is present in equilibrium with PBE or PVEE-rich phases. Maximum ionic conductivity at room temperature, for the electrolyte containing 20 wt% LiClO₄, reached 4.23 × 10⁻³ Ω⁻¹ cm⁻¹, while all samples exhibited conductivity of approximately 10⁻¹ Ω⁻¹ cm⁻¹ at 80 °C.