Investigation of thin sputtered Mn films for electrochemical capacitors

Pseudocapacitive manganese oxide films have been synthesized by anodic oxidation of metallic films deposited by sputtering. Results are presented from an electrochemical investigation into properties of these thin sputtered manganese films. Mn films with thickness ranging from 20 to 200 nm have been sputtered onto Pt coated Si wafers in an Argon atmosphere. Electrochemical oxidation converts the metal film into a porous, dendritic structure which displays significant pseudocapacitance. We have observed a specific capacitance (C_s) of 700 F/g when cycled very slowly at a constant current density of 160 μA/cm². The same films probed by cyclic voltammetry (CV) at a rate of 5 mV/s yielded a lower specific capacitance of 400-450 F/g. Post-oxidation material loading was measured to be in the range of 25-75 μg/cm².     

Aligned carbon nanotube thin films for DNA electrochemical sensing

Carbon nanotubes are interesting materials for DNA electrochemical sensing due to their unique electric properties: high surface area, fast heterogeneous electron transfer, and electrochemical stability. In this work aligned Carbon NanoTube (CNT) thin films were designed and tested as candidate platforms for DNA immobilization and for the development of an electrochemical genosensor.The films were prepared by Chemical Vapor Deposition (CVD) using acetylene and ammonia as precursor gases and nickel particles as catalyst. A preliminary electrochemical characterization was performed using cyclic voltammetry since, so far, these films have been used only for gas sensing. The surfaces were then covalently functionalized with a DNA oligonucleotide probe, complementary to the sequence of the most common inserts in the GMOs: the Promoter 35S. The genosensor format involved the immobilization of the probe onto the sensor surface, the hybridization with the target-sequence and the electrochemical detection of the duplex formation. Careful attention was paid to the probe immobilization conditions in order to minimize the signal due to non-specifically adsorbed sequences. For the detection of the hybridization event both label-free and enzyme-labelled methods were investigated. In case of the enzyme-labelled method a target concentration at nanomolar level can be easily detected, with a linear response from 50 nM to 200 nM, whereas the label-free method showed a linear response between 0.5 μM and 10 μM. The reproducibility was 11% and 20% with the enzyme-labelled method and the label-free method, respectively. The batch-to-batch reproducibility of the different sensors was also evaluated.     

Preparation and characterization of the electrodeposited Ni-Co oxide thin films for electrochemical capacitors

Nickel-cobalt (Ni-Co) oxide thin films were electrodeposited onto copper substrates in an electrolyte containing cobalt chloride and nickel chloride, and the electrochemical capacitor behaviors of these films were investigated. The XRD pattern revealed that the electrodeposited Ni-Co oxide thin film was comprised of NiCo₂O₄. In the SEM image, the electrodeposited Ni-Co oxide film was covered with hexagonal and cubical shaped particles. The electrodeposited Ni-Co oxide electrode exhibited a specific capacitance of 148 F/g at a scan rate of 20 mV, and the current density was fairly stable over 200 cycles. The charge-discharge test confirmed that capacitance of the electrodeposited Ni-Co oxide electrode resulted from the electric double layer capacitance and pseudocapacitance.     

Polystyrene-based carbon spheres as electrode for electrochemical capacitors

A series of carbon spheres with various porous texture parameters were prepared from polystyrene-based macroreticular resin spheres by carbonization and activation. The as-prepared carbon spheres had a maximum specific surface area of 996 m² g^?1, total pore volume of 1.34 cm³ g^?1 and average pore size of 5.39 nm. Moreover, these carbon spheres showed a mesopore size distributed mainly in about 40 nm. A high specific capacitance of 153 F g^?1 for carbon sphere by carbonization, 164 F g^?1 for carbon sphere by activation for 1 h and 182 F g^?1 for carbon sphere by activation for 2 h can be obtained. Moreover, a specific energy between 2.3 and 5.1 Wh kg^?1 for these carbon spheres can be obtained in 6 mol L^?1 KOH electrolyte.     

Polypyrrole/carbon composite electrode for high-power electrochemical capacitors

Nano-thin polypyrrole (PPy) layers with thickness from ∼5 nm to several 10s nm were deposited on vapor grown carbon fibers (VGCF) by an in situ chemical polymerization. Using different concentrations of the pyrrole could control the thicknesses of deposited PPy layers. Surface morphology and thickness of the deposited PPy layers were confirmed by means of scanning electron microscopy and scanning transmission emission microscopy. Pseudo-capacitive behavior of the deposited PPy layers on VGCF investigated by means of cyclic voltammetry. Then, the PPy/VGCF composites were mixed with activated carbons (AC) at various mixing ratios. For the PPy/VGCF/AC composite electrodes, characteristics of specific capacitance and power capability were examined by half-cell tests. As results of this study, it was investigated that nano-thin PPy layer below ∼10 nm deposited on VGCF had high pseudo-capacitance and fast reversibility. Its specific capacitance per averaged weight of active material (PPy) was obtained as ∼588 F g⁻¹ at 30 mV s⁻¹ and maintained as ∼550 F g⁻¹ at 200 mV s⁻¹ of scan rate. Also, from the mixing 60 wt.% of the PPy/VGCF with 25 wt.% of AC, the PPy/VGCF/AC composite electrode exhibited higher power capability maintaining the specific capacitance per active materials of PPy and AC as ∼300 F g⁻¹ at 200 mV s⁻¹ in 6 M KOH.     

Investigations of multilayer polyoxometalates-modified carbon nanotubes for electrochemical capacitors

A simple and effective method to improve over previous approaches to add pseudocapacitance to carbon substrates through deposition of polyoxometalates (POMs) was demonstrated on multi-walled carbon nanotubes (MWCNTs). By superimposing layers of different pseudocapacitive polyoxometalates, SiMo₁₂O₄₀⁻⁴ (SiMo₁₂) and PMo₁₂O₄₀⁻³ (PMo₁₂), the POMs exhibited continuous overlapped oxidation/reduction reactions and achieved an up to fourfold increase in area specific capacitance when compared with the double layer capacitance of bare MWCNTs. The superimposed SiMo₁₂ and PMo₁₂ layers were studied by Scanning Electron Microscopy (SEM) and X-ray Photoelectron Spectroscopy (XPS). Analyses of the potential/pH relationship provided important insights into the deposition mechanism and suggested that the layer closest to the electrode substrate was dominating in terms of chemistry and kinetics of the coated MWCNT.     

On the electrochemical activation of alkali-treated soft carbon for advanced electrochemical capacitors

The electrochemical activation process of the so-called “alkali-treated soft carbon” (ASC) has been examined in organic electrolyte solutions. SEM observation demonstrated that the edge plane of graphene structure of the ASC particle becomes rough after the activation, and XRD measurements indicated that the average lattice constant of graphene stacking in ASC increases after the activation process. Ex-situ ⁷Li NMR measurements proved that the insertion of cation (Li⁺) into the pore structure of ASC is associated with the activation process in the electrolyte dissolving Li salt. The pore-size distribution determined from N₂-gas adsorption for ASC electrodes before and after the electrochemical activation indicates that the pore structure becomes developed after the electrochemical polarization, especially in the pore-diameter range of 2–10 nm. A schematic model of the activation process has been presented, which includes electrochemical insertion of ions into the inside of the ASC.     

Disordered carbon negative electrode for electrochemical capacitors and high-rate batteries

In order to understand the properties of high-rate capability and cycleability for a disordered carbon negative electrode in LiPF₆/PC based electrolyte solution, the cell performance tests with various rates and depth of discharges (DODs) has been studied by spectroscopic and electrochemical analyses. From the charge-discharge measurements, a surface carbon-edge redox reaction occurring between a carbonyl (C_edgeO) and a lithium alkoxide (C_edge-OLi) that delivers a large capacity was found fast and high cycleability at only shallow DOD (2.0-0.4 V). The limited or shallow charge-discharge cycling utilizing such facile and reversible action of the C_edgeO/C_edge-OLi of the disordered carbon is suited to an application for an negative electrode of asymmetric hybrid capacitors. A deep DOD discharge (2.0-0.0 V) revealed the existence of some complex processes involving a lithium cluster deposition at pores or microvoids as well as a lithium ion intercalation at graphene layers. The cluster deposition at pores was found to be relatively fast and reproducible. The lithium ion intercalation at graphenes and the subsequent cluster deposition at microvoids were found to be slow and degrade the cycleability after 100 cycles because of the accumulation of a thick and low-ion-conductive solid electrolyte interface (SEI) film on surface.     

Manganese oxide precipitated into activated carbon electrodes for electrochemical capacitors

Manganese oxide was prepared at different pH and temperatures and then precipitated into activated carbon by the chemical impregnation method. Size distributions of manganese oxide sol were also measured by light scattering. The electrodes were annealed in nitrogen gas at different temperatures. In addition, electrochemical characterization was carried out using cyclic voltammetry (CV) at a scan rate of 25 mV s⁻¹ and chronopotentiometry (CP) with constant-current (10 mA cm⁻²). Maximum capacitance of 461.3 F g⁻¹ was obtained in a 0.1 M Na₂SO₄ solution for manganese oxide prepared under optimum conditions (pH = 13.11 and T = 25 oC) and annealed at a temperature of 195 oC. The manganese oxide particle size decreased with annealing. This probably leads to increased specific capacitance. Using X-ray photoelectron spectroscopy (XPS) the results reveal that manganese oxide species are transformed from hydroxide to oxide after annealing.     

Bottom electrode crystallization of PZT thin films for ferroelectric capacitors

The bottom electrode crystallization (BEC) method was applied to the crystallization of PZT thin films deposited by laser ablation over Si/SiO₂/Ti(Zr)/Pt structures, with the platinum films being deposited at two different temperatures. The results were compared with those obtained by rapid annealing with halogen lamps and furnace annealing. PZT films crystallized over Pt made at lower temperature with Ti adhesion layers tend to have a (1 1 1) preferential orientation, while those deposited on platinum made at higher temperature tend to have a (1 0 0)/(1 1 1) mixed orientation. When Zr adhesion layers are used, the PZT films crystallized over Pt have a preferential (1 0 0) orientation, except for films deposited over Pt made at 500 °C and crystallized with a high heating rate. The ferroelectric properties of the films crystallized with the BEC method are good, being similar to those obtained with the other crystallization methods using the same parameters.     

Sulfur-incorporated,porous graphene films for high performance flexible electrochemical capacitors

Graphene and its derivatives are considered potential electrode materials for flexible electrochemical capacitors (f-ECs), but their capacitive performances have to be improved for practical applications. Herein, we demonstrate fabrication of flexible sulfur (S)-incorporated reduced graphene oxide (SRGO) electrodes obtained by pyrolyzing free-standing film consisting of benzyl disulfide-functionalized graphene oxides at 900 °C. The effect of S incorporation on morphology and chemical structure of SRGO were investigated by various microscopic and spectroscopic methods. Incorporation of S and the crumpled and porous morphology of SRGO electrodes improve capacitive performance of f-ECs; SRGO f-ECs show a specific capacitance of 140.8 F/g at 1 A/g, rate capability of 91.5% retention, and cyclic performance of 93.4% after 1000 charge/discharge cycles at 4 A/g. Impressively, SRGO f-ECs exhibit excellent electrochemical and mechanical durability after 1000 charge/discharge cycles at a bending angle of 120° with values that greatly exceed those of conventional RGO-based f-ECs. This study provides a fundamental foundation of the correlation between S composition of carbon nanomaterials and their electrochemical (or surface) properties.     

Mesoporous N-containing carbon nanosheets towards high-performance electrochemical capacitors

We developed a direct carbonization strategy to efficiently fabricate mesoporous N-containing carbon nanosheets (N-CNSs) by using polyaniline nanosheets as a carbon precursor. Physicochemical characterizations revealed that the as-synthesized N-CNSs with 5.9 wt.% N species possessed a well-developed mesoporous architecture with large specific surface area of 352 m² g⁻¹, high mesoporous volume of 0.32 cm³ g⁻¹, and average pore size of ∼5.2 nm. When further utilized as an electrode for electrochemical capacitors, the mesoporous N-CNSs delivered a large specific capacitance of 239 F g⁻¹ at 0.5 A g⁻¹, and even 197 F g⁻¹ at a high current load of 8 A g⁻¹, indicating its good rate behavior. Furthermore, the capacitance degradation of ∼4% over continuous 5000 charge–discharge cycles at 6 A g⁻¹ further verified its good electrochemical stability at high rates for long-term electrochemical capacitors application.     

Activation of ultra‐thin activated carbon fibers as electrodes for high performance electrochemical double layer capacitors

Activated carbon fibers (ACFs) contain pores with a weak resistance to electrolyte migration but with high electrical resistance between the fibers. The ACFs used herein were prepared from ultra‐thin polyacrylonitrile (PAN) fibers, to be used as electrodes in electrochemical double layer capacitors (EDLCs), by varying the activation temperatures and the holding times during steam activation. As the activation temperature and holding time were increased, the specific surface area increased along with the specific capacitance (F g^?1). A maximum specific capacitance as high as 283 F g^?1 can be obtained using the ultra‐thin ACFs fabricated at 1000°C for 10 min with a specific surface area of 1408 m² g^?1. This investigation demonstrates that the surface area, pore structure, and surface functional groups of ACFs were all significant factors in determining the capacitive characteristics of ACFs. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Activated porous carbon nanofibers using Sn segregation for high-performance electrochemical capacitors

Activated porous carbon nanofibers (CNFs) with three different types of porous structures, which were controlled to contain 1, 4, and 8 wt% of Sn–poly(vinylpyrrolidone) (PVP) precursors in the core region and 7 wt% polyaniline (PAN)–PVP precursors in the shell region during electrospinning, were synthesized using a co-electrospinning technique with H₂-reduction. The formation mechanisms of activated porous CNF electrodes with the three different types of samples were demonstrated. The activated porous CNFs, for use as electrodes in high-performance electrochemical capacitors, have excellent capacitances (289.0 F/g at 10 mV/s), superior cycling stability, and high energy densities; these values are much better than those of the conventional CNFs. The improved capacitances of the activated porous CNFs are explained by the synergistic effect of the improved porous structures in the CNF electrodes and the formation of activated states on the CNF surfaces.     

RF oxygen plasma treatment of activated carbon electrodes for electrochemical capacitors

Activated carbon modified by Radio Frequency (RF) plasma at different power levels, times and volume flow rates of oxygen was prepared for activated carbon electrodes. Electrochemical characterization of different activated carbon electrodes was carried out using cyclic voltammetry (CV) with different electrolytes at a concentration of 0.1 M. A maximum capacitance of 38.9 F g⁻¹ was obtained in a 0.1 M H₂SO₄ solution for the activated carbon (precursor material: coconut shell made in Japan) with plasma treatment conditions: power = 300 W, time = 3 min, and volume flow rates of oxygen = 45 sccm (standard cubic centimeter per minute). In addition, specific surface areas/pore-size distributions, functional groups, and surface morphologies of activated carbon with/without plasma treatment were examined by gas adsorption meter, Fourier transform infrared spectroscopy (FTIR), and scanning electron microscope (SEM), respectively.     

Preparation and electrochemical properties of gold nanoparticles containing carbon nanotubes-polyelectrolyte multilayer thin films

Multi-walled carbon nanotubes (MWCNT)/polyelectrolyte (PE) hybrid thin films were fabricated by alternatively depositing negatively charged MWCNT and positively charged (diallyldimethylammonium chloride) (PDDA) via layer-by-layer (LbL) assembly technique. The stepwise growth of the multilayer films of MWCNT and PDDA was characterized by UV–vis spectroscopy. Scanning electron microscopy (SEM) images indicated that the MWCNT were uniformly embedded in the film to form a network and the coverage density of MWCNT increased with layer number. Au nanoparticles (NPs) could be further adsorbed onto the film to form PE/MWCNT/Au NPs composite films. The electron transfer behaviour of multilayer films with different compositions were studied by cyclic voltammetry using [Fe(CN)₆]^3−/4− as an electrochemical probe. The results indicated that the incorporation of MWCNT and Au NPs not only greatly improved the electronic conductivity of pure polyelectrolyte films, but also provided excellent electrocatalytic activity towards the oxidation of nitric oxide (NO).