Synthesis and electrochemical capacitance of binderless nanocomposite electrodes formed by dispersion of carbon nanotubes and carbon aerogels

Novel nanocomposite carbon aerogel (CAG)-multi-walled carbon nanotubes (MWNT) materials have been synthesized and studied in 5 M KOH for electrochemical capacitor applications. The amount of MWNT in the nanocomposite was varied from 3 to 10 wt%. High specific surface areas ranging between 670 and 710 m² g⁻¹ were obtained as measured by nitrogen gas adsorption method, whereas the average pore diameter ranged between 1 and 4 nm.     

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.     

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.     

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.     

Electrochemical properties of manganese oxide coated onto carbon nanotubes for energy-storage applications

Birnessite-type manganese dioxide (MnO₂) is coated uniformly on carbon nanotubes (CNTs) by employing a spontaneous direct redox reaction between the CNTs and permanganate ions (MnO₄⁻). The initial specific capacitance of the MnO₂/CNT nanocomposite in an organic electrolyte at a large current density of 1 A g⁻¹ is 250 F g⁻¹. This is equivalent to 139 mAh g⁻¹ based on the total weight of the electrode material that includes the electroactive material, conducting agent and binder. The specific capacitance of the MnO₂ in the MnO₂/CNT nanocomposite is as high as 580 F g⁻¹ (320 mAh g⁻¹), indicating excellent electrochemical utilization of the MnO₂. The addition of CNTs as a conducting agent improves the high-rate capability of the MnO₂/CNT nanocomposite considerably. The in situ X-ray absorption near-edge structure (XANES) shows improvement in the structural and electrochemical reversibility of the MnO₂/CNT nanocomposite after heat-treatment.     

Long-term cycling behavior of asymmetric activated carbon/MnO2 aqueous electrochemical supercapacitor

Activated carbon–MnO₂ hybrid electrochemical supercapacitor cells have been assembled and characterized in K₂SO₄ aqueous media. A laboratory cell achieved 195,000 cycles with stable performance. The maximal cell voltage was 2 V associated with 21 ± 2 F g⁻¹ of total composite electrode materials (including activated carbon and MnO₂, binder and conductive additive) and an equivalent serie resistance (ESR) below 1.3 Ω cm². Long-life cycling was achieved by removing dissolved oxygen from the electrolyte, which limits the corrosion of current collectors. Scaling up has been realized by assembling several electrodes in parallel to build a prismatic cell. A stable capacity of 380 F and a cell voltage of 2 V were maintained over 600 cycles. These encouraging results show the interest of developing such devices, including non-toxic and safer components as compared to the current organic-based devices.     

Electrochemical hydrogen storage properties of ball-milled multi-wall carbon nanotubes

The structure changes of multi-wall carbon nanotubes (MWNTs) processed by mechanical ball milling and the influence on their electrochemical hydrogen storage capacities were studied. TEM micrographs show that MWNTs are shortened and open-ended after ball milling. The effects of different MWNT type and ball milling time on the discharging capacity were investigated. Among all the samples examined, the sample of short MWNTs with diameter of 5 nm and ball milling time of 12 h has the largest discharge capacity (741.1 mAh/g). According to the analysis of Raman spectra and nitrogen adsorption experiments, it can be inferred that the micropore volume, specific surface area and appropriate defects are crucial to the storage capacity. In the cyclic voltammograms, the hydrogen desorption peak appears prior to hydrogen oxidation peak, which is attributed to the slow reaction of hydrogen oxidation at MWNTs. The results also suggest the possible existence of the strong chemisorption of hydrogen.     

Electrochemical micro-capacitors of patterned electrodes loaded with manganese oxide and carbon nanotubes

MnO₂ and carbon nanotubes (CNT) composite electrodes have been built on the interdigital stack layers of Fe-Al/SiO₂ and Fe-Al/Au/Ti/SiO₂ for the electrochemical micro-capacitors, using photolithography and thin-film technologies. The electrode properties and the performance of micro-cells are measured and analyzed with cyclic voltammetry (CV), impedance spectroscopy, and galvanostatic charge/discharge test in 0.1 M Na₂SO₄ electrolyte. The vertically aligned CNT, grown on Fe-Al/SiO₂, is more suitable for supporting the pseudocapacitive MnO₂ than the random CNT on Fe-Al/Au/Ti/SiO₂, but ohmic resistance of the former electrode is higher. We have prepared three cells on each stack layer with different electrode materials. The Ragone plot shows systematic variations in power and energy performance, reflecting their differences in electrode structure and polarization loss. The asymmetric cell of a pseudocapacitive positive electrode, loaded with MnO₂ and CNT, exhibits a small IR drop and a high specific energy during discharge. Built on Fe-Al/SiO₂, this asymmetric cell discharges at specific power 0.96 kW kg⁻¹ with specific energy 10.3 Wh kg⁻¹; while on Fe-Al/Au/Ti/SiO₂, the asymmetric cell discharges at power 1.16 kW kg⁻¹ with energy 5.71 Wh kg⁻¹.     

Electrochemically activated carbon micro-electrode arrays for electrochemical micro-capacitors

Interdigitated carbon micro-electrode arrays for micro-capacitors are fabricated through the carbon microelectromechanical systems (C-MEMS) technique which is based on the carbonization of patterned photoresist. To improve the capacitive behavior, electrochemical activation is performed on carbon micro-electrode arrays. Cyclic voltammetry (CV) and galvanostatic charge-discharge results demonstrate that the electrochemical activation effectively increases the capacitance of the micro-electrode arrays by three orders of magnitude. Although the charge-discharge experiments show the non-ideal behavior of micro-capacitors, the specific geometric capacitance reaches as high as 75 mF cm⁻² at a scan rate of 5 mV s⁻¹ after electrochemical activation for 30 min. The capacitance loss is less than 13% after 1000 CV cycles. These results indicate that electrochemically activated C-MEMS micro-electrode arrays are promising candidates for on-chip electrochemical micro-capacitor application.     

Hydrogen storage in coiled carbon nanotubes

We report a density functional calculation of the adsorption of molecular hydrogen on the external surface of coiled carbon nanotube (CCNT). Binding energies of single molecule have been studied as a function of three different orientations and at three different sites like hexagon, pentagon and heptagon. The binding energy values are larger than linear (5,5) armchair nanotube, which has approximately same diameter as that of coiled carbon nanotube. The curvature and topology of CCNT are responsible for this considerable enhancement. The system with full coverage is also studied. When the nanotube surface is fully covered with one molecule per graphitic hexagon, pentagon and heptagon gives the 6.8 wt% storage capacity. The binding energy per molecule decreases due to repulsive interactions between neighbor molecules. It gives good storage medium for hydrogen. Almost it meets the DOE target.     

Permeability,thermal and wetting properties of aligned composite nanofiber membranes containing carbon nanotubes

In this paper, aligned single wall carbon nanotubes/Polyacrylonitrile (SWNTs/PAN) nanofiber membranes were fabricated by a modified parallel electrode method (MPEM), in which a positively charged copper ring was placed between the needle and the parallel electrode collector. The permeability, thermal and wetting properties of aligned SWNTs/PAN membranes obtained by MPEM were investigated. And the experimental results showed that the addition of the SDBS-modified SWNTs could enhance hydrophilicity of PAN nanofiber membranes, and the alignment of composite membranes could improve the permeability and wetting properties. In addition, an illustration of wetting property was given through the geometric potential. The illustration was in good agreement with the experimental data, and showed the MPEM could make hydrophobic materials more hydrophobic and make hydrophilic materials more hydrophilic.     

Nitrogen doped carbon fibers derived from carbonization of electrospun polyacrylonitrile as efficient metal-free HER electrocatalyst

Development of durable and efficient electrocatalyst for hydrogen evolution reaction (HER) is significantly important for forwarding the commercialization of water splitting technology. In this work, we report a facile synthesis of nitrogen doped carbon fibers derived from the carbonization of the electron-spun polyacrylonitrile (PAN) membrane at 800 °C (NCFs-800) as efficient and stable metal-free electrocatalyst for HER catalysis in both acidic and alkaline mediums. Ascribing to the homogenous nitrogen dopants in electrocatalyst, NCFs-800 requires only 114.3 mV and 198.6 mV vs. RHE to achieve current density of 10 mA cm⁻² in 0.5 M H₂SO₄ and 1 M KOH electrolytes, respectively. Moreover, the HER activity is well maintained after 2000 potential cycles indicating that NCFs-800 possesses high durability in both acidic and alkaline conditions due to the fibrous structure with high corrosion resistance. Our study offers new strategy to synthesize stable and efficient metal-free electrocatalyst, which could be extended to other heteroatom doped carbon electrocatalyst.     

Modification of single wall carbon nanotubes (SWNT) for hydrogen storage

Due to unique structural, mechanical and electrical properties of single wall carbon nanotubes, SWNTs, they have been proposed as promising hydrogen storage materials especially in automotive industries. This research deals with investing of CNT’s and some activated carbons hydrogen storage capacity. The CNT’s were prepared through natural gas decomposition at a temperature of 900?C over cobalt-molybdenum nanoparticles supported by nanoporous magnesium oxide (Co–Mo/MgO) during a chemical vapor deposition (CVD) process. The effects of purity of CNT (80–95%wt.) on hydrogen storage were investigated here. The results showed an improvement in the hydrogen adsorption capacity with increasing the purity of CNT’s. Maximum adsorption capacity was 0.8%wt. in case of CNT’s with 95% purity and it may be raised up with some purification to 1%wt. which was far less than the target specified by DOE (6.5%wt.). Also some activated carbons were manufactured and the results compared to CNTs. There were no considerable H₂-storage for carbon nanotubes and activated carbons at room-temperature due to insufficient binding between H₂ molecules carbon nanostructures. Therefore, hydrogen must be adsorbed via interaction of atomic hydrogen with the storage environment in order to achieve DOE target, because the H atoms have a very stronger interaction with carbon nanostructures.     

Oxygen-doped activated carbon fiber cloth as electrode material for electrochemical capacitor

Novel oxygen-doped activated carbon fiber cloths (OACFC), with different compositions of surface oxygen functionalities, have been prepared by direct electrooxidative/reductive methods in an undivided electrolytic cell filled with high purity water without a supporting electrolyte under high voltage conditions. The morphology and surface chemical composition of the materials have been investigated by SEM, Raman and XPS spectroscopies. They revealed an electrochemical erosion of the CF surface upon activation, concomitant with a strong change of the D/G ratio of characteristic Raman bands and the surface O/C atomic ratio, respectively. Thus pretreated material was tested as electrodes for an electrochemical capacitor by cyclic voltammetry, galvanostatic charge/discharge, and electrochemical impedance spectroscopy measurements in 3.75 M H₂SO₄. The performance of the electrochemical capacitor based on modified carbon electrodes was compared to that of an analogous device with unmodified carbon. The measurements revealed altered electrochemical behavior of the OACFC in terms of the determined capacitances. The proposed activation method is also superior to other electrochemical activation procedures, since it uses much less energy per CF surface or mass.     

Nickel hydroxide/activated carbon composite electrodes for electrochemical capacitors

In this paper, a nickel hydroxide/activated carbon (AC) composite electrode for use in an electrochemical capacitor was prepared by a simple chemical precipitation method. The structure and morphology of nickel hydroxide/AC were characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM). The results showed that nano-sized nickel hydroxide was loading on the surface of activated carbon. Electrochemical performance of the composite electrodes with different loading amount was studied by cyclic voltammetry and galvanostatic charge/discharge measurements. It was demonstrated that the introduction of a small amount of nickel hydroxide to activated carbon could promote the specific capacitance of a composite electrode. The composite electrodes have good electrochemical performance and high charge–discharge properties. Moreover, when the loading amount of nickel hydroxide was 6 wt.%, the composite electrode showed a high specific capacitance of 314.5 F g⁻¹, which is 23.3% higher than pure activated carbon (255.1 F g⁻¹). Also, the composite electrochemical capacitor exhibits a stable cyclic life in the potential range of 0–1.0 V.     

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.     

The porous structures of activated carbon aerogels and their effects on electrochemical performance

The pore structures of carbon aerogels were designed and controlled by changing conditions for both the microemulsion-templated sol–gel polymerization and the KOH activation processes. The resulting pore structures were characterized by means of N₂ adsorption and SEM. A new pore model is proposed and the relationship between the pore structures of the activated carbon aerogels (ACAs) and their electrochemical performance is discussed. The experimental results show that the ACAs which were prepared contain four types of pores: (A) micropores with diameters below 2 nm; (B) small mesopores with diameters from 2 to 5 nm; (C) large mesopores with diameters from 5 to 40 nm; and (D) large pores and channels with diameters over 40 nm. Appropriate activation with KOH can increase the numbers of micropores and small mesopores as well as the BET areas, resulting in an increase in the specific capacitance (C_s) of the ACA samples. The type D pores and channels play an important role in the enhancement of the electrochemical capacitance under high charge–discharge current conditions. Though ACAs with different porous models show a linear relation between C_s and BET area separately, the surface areas of micropores of the ACAs with appropriate type D pores and channels have a higher accessibility and efficiency in the storage of energy than those with closed type C pores.     

Pd nanoparticles assembled on Ni- and N-doped carbon nanotubes towards superior electrochemical activity

Metal-based catalysts within single-atom to 1–2 nm size range are attracting considerable attention recent years. Carbon-based materials with their excellent electro- and photo-chemical properties are ideal candidates as supporting substrate for constructing of metal catalyst. Here we report a palladium (less than 5 nm in average diameter) deposited Ni carbon nanotubes (CNTs) with Ni metal nanoparticles (NPs) to be around single atom to 1–2 nm on average. Mono-dispersed Pd NPs are homogeneously immobilized on both synthesized Ni- and N-doped CNTs and N-doped commercial made CNTs using poly(diallyldimethyl ammonium) chloride (PDDA) as the key bonding components. Enhanced electrocatalytic activity is observed in measurements including hydrogen evolution reaction (HER), oxygen reduction reaction (ORR), oxygen evolution reaction (OER) and methanol oxidation reaction (MOR), with some of the samples having higher HER (under acidic condition) and OER (under basic condition) activity comparing with the commercial Pd/C (40 wt%) sample. The result provides a forward-looking strategy for fabricating efficient and low-cost catalysts.     

Investigation of hydrogen storage capacity of various carbon materials

Hydrogen storage capacity of various carbon materials, including activated carbon (AC), single-walled carbon nanohorn, single-walled carbon nanotubes, and graphitic carbon nanofibers, was investigated at 303 and 77 K, respectively. The results showed that hydrogen storage capacity of carbon materials was less than 1 wt% at 303 K, and a super activated carbon, Maxsorb, had the highest capacity (0.67 wt%). By lowering adsorption temperature to 77 K, hydrogen storage capacity of carbon materials increased significantly and Maxsorb could store a large amount of hydrogen (5.7 wt%) at a relatively low pressure of 3 MPa. Hydrogen storage capacity of carbon materials was proportional to their specific surface area and the volume of micropores, and the narrow micropores was preferred to adsorption of hydrogen, indicating that all carbon materials adsorbed hydrogen gas through physical adsorption on the surface.