Microstructural controls of titanate nanosheet composites using carbon fibers and high-rate electrode properties for lithium ion secondary batteries

Composite electrodes of reassembled titanate and two kinds of carbon fibers were prepared and their high-rate electrode properties were examined. Multi-walled carbon nanotubes (MWNT) and vapor-grown carbon fibers (VGCF) were used for preparing the composites. The electronic conductivity of the MWNT composites increased with increasing contents of MWNT and exhibited a typical insulator-conductor transition. The MWNT composite with a MWNT content of 50 wt.% showed a capacity of 150 ± 5 mAh (g titanate)⁻¹ at a discharge rate of 0.67 C, and did not show a good high-rate capability due to the large content of hydrated water. The effect of the porous structure of the electrodes was revealed in the high-rate electrode properties of the microstructurally controlled composites with both MWNT and VGCF. The composites with 50 wt.% VGCF and 10 wt.% MWNT showed a reversible capacity of approximately 160 mAh (g titanate)⁻¹ at a discharge rate of 0.63 C and almost no capacity fading at relatively large discharge rate up to 19 C. A composite electrode with excellent high-rate capability was obtained by the microstructural control with carbon fibers.     

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.     

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%.     

Hydrogen generation by water electrolysis using carbon nanotube anode

Anode made of multiwalled carbon nanotubes (MWNT) results in enhancement of exchange current density compared to graphite anode in a conventional alkaline water electrolysis cell. The hydrogen production rate with the nanotubes was measured to be ∼375 lh⁻¹ m⁻² at pH ∼ 14 which was nearly double of that obtained from traditional graphitic carbon electrodes at the same overpotential. This effect appears to be caused by defects on the nanotubes which reduces the energy barrier for the dissociation of OH⁻ into oxygen at the anode.     

Preparation and properties of carbon nanotube/polypropylene nanocomposite bipolar plates for polymer electrolyte membrane fuel cells

This study aims at the fabrication of lightweight and high performance nanocomposite bipolar plates for the application in polymer electrode membrane fuel cells (PEMFCs). The thin nanocomposite bipolar plates (the thickness <1.2 mm) consisting of multiwalled carbon nanotubes (MWCNTs), graphite powder and PP were fabricated by means of compression molding. Three types of polypropylene (PP) with different crystallinities including high crystallinity PP (HC-PP), medium crystallinity PP (MC-PP), low crystallinity PP (LC-PP) were prepared to investigate the influence of crystallinity on the dispersion of MWCNTs in PP matrix. The optimum composition of original composite bipolar plates was determined at 80 wt.% graphite content and 20 wt.% PP content based on the measurements of electrical and mechanical properties with various graphite contents. Results also indicate that MWCNTs was dispersed better in LC-PP than other PP owing to enough dispersed regions in nanocomposite bipolar plates. This good MWCNT dispersion of LC-PP would cause better bulk electrical conductivity, mechanical properties and thermal stability of MWCNTs/PP nanocomposite bipolar plates. In the MWCNTs/LC-PP system, the bulk electrical conductivities with various MWCNT contents all exceed 100 S cm⁻¹. The flexural strength of the MWCNTs/LC-PP nanocomposite bipolar plate with 8 phr of MWCNTs was approximately 37% higher than that of the original nanocomposite bipolar plate and the unnotched Izod impact strength of MWCNTs/LC-PP nanocomposite bipolar plates was also increased from 68.32 J m⁻¹ (0 phr) to 81.40 J m⁻¹ (8 phr), increasing 19%. In addition, the coefficient of thermal expansion of MWCNTs/LC-PP nanocomposite bipolar plate was decreased from 32.91 μm m⁻¹ °C⁻¹ (0 phr) to 25.79 μm m⁻¹ °C⁻¹ (8 phr) with the increasing of MWCNT content. The polarization curve of MWCNTs/LC-PP nanocomposite bipolar plate compared with graphite bipolar plate was also evaluated. These results confirm that the addition of MWCNTs in LC-PP leads to a significant improvement on the cell performance of the nanocomposite bipolar plate.     

Facile synthesis of hierarchically structured Fe3O4/carbon micro-flowers and their application to lithium-ion battery anodes

A flower-like Fe₃O₄/carbon nanocomposite with nano/micro hierarchical structure is prepared by controlled thermal decomposition of the iron alkoxide precursor, which is obtained via an ethylene glycol-mediated solvothermal reaction of FeCl₃ and hexamethylenetetramine (HMT) in the absence of any surfactant. The nanocomposite is characterized by the assembly of porous nanoflakes consisting of Fe₃O₄ nanoparticles and amorphous carbon that is in situ generated from the organic components of alkoxide precursor. When used as the anode materials for the lithium-ion batteries, the resultant nanocomposite shows high capacity and good cycle stability (1030 m Ah g⁻¹ at a current density of 0.2 C up to 150 cycles), as well as enhanced rate capability. The excellent electrochemical performance can be attributed to the high structural stability and high rate of ionic/electronic conduction arising from the synergetic effect of the unique nano/micro hierarchical structure and conductive carbon coating.     

Effect of carbon black concentration in carbon fiber paper on the performance of low-temperature proton exchange membrane fuel cells

This study uses fuel cell gas diffusion layers (GDLs) made from carbon fiber paper containing carbon black in proton exchange membrane fuel cells (PEMFCs) in order to determine the relationship between carbon black content and fuel cell performance. The connection between fuel cell performance and the carbon black content of the carbon fiber paper is discussed, and the effects of carbon black on the carbon fiber paper's thickness, density, and surface resistivity are investigated. When a carbon fiber paper GDL contains 10 wt% phenolic resin and 2% carbon black, and reaction area was 25 cm² and operating temperature 40 °C, tests show that a carbon electrode fuel cell could achieve 1026.4 mA cm⁻² and maximum power of 612.8 mW cm⁻² under a 0.5 V load.     

Growth of polyaniline nanowhiskers on mesoporous carbon for supercapacitor application

Vertically aligned polyaniline nanowhiskers (PANI-NWs) doped with (1R)-(−)-10-Camphorsulfonic acid (L-CSA) have been successfully synthesized on the external surface of ordered mesoporous carbon (CMK-3) by chemical oxidative polymerization. The specific surface area of the PANI-NWs/CMK-3 nanocomposite remains as high as 497 m² g⁻¹ by removing mesoporous silica template after the polymerization of aniline. Structural and morphological characterizations of the nanocomposite were further investigated by XRD, FTIR and FE-SEM measurements. The result shows that the nanocomposite with 40 wt% PANI applying in supercapacitor devices possesses a large specific capacitance of 470 F g⁻¹ and good capacitance retention of 90.4% is achieved after 1000 cycles at a current density of 1.0 A g⁻¹. The synergistic effect of small PANI nanowhisker arrays and well-ordered mesoporous carbon endows the composite with high electrochemical capacitance and good cycling stability.     

Au–MnO2/MWNT and Au–ZnO/MWNT as oxygen reduction reaction electrocatalyst for polymer electrolyte membrane fuel cell

Bi-functional catalysts based on Au supported on oxide based nanomaterials for use in fuel cells were evaluated by electrochemical methods for oxygen reduction reaction (ORR) in Polymer Electrolyte Membrane Fuel Cell (PEMFC). Metal oxide coated multi walled carbon nanotubes (MWNTs) (MnO₂/MWNT and ZnO/MWNT) were prepared by reduction of potassium permanganate and oxidation of Zn powder on MWNT surface respectively. Au–MnO₂/MWNT and Au–ZnO/MWNT were prepared by chemical reduction of chloroauric acid on MnO₂/MWNT and ZnO/MWNT. The samples were characterized and linear sweep voltammetric studies were performed in N₂ saturated, O₂ saturated and methanol containing 1 M KOH solution and the results have been discussed. A single fuel cell was also constructed using Au–MnO₂/MWNT and Au–ZnO/MWNT as ORR electrocatalysts. A maximum power density of 45 mW/cm² and 56 mW/cm² was obtained with Au–MnO₂/MWNT and Au–ZnO/MWNT respectively. Additionally, the methanol tolerance of these electrocatalysts has been investigated and results have been discussed.     

Effect of carbon fiber cloth with different structure on the performance of low temperature proton exchange membrane fuel cells

This study uses fuel cell gas diffusion layers (GDLs) fabricated in the laboratory from carbon fiber cloth with different structure in proton exchange membrane fuel cells (PEMFCs), and investigates the relationship between the structure of the carbon fiber cloth and fuel cell performance.The paper discusses the relationship between fuel cell performance and structure of the carbon fiber cloth, and also examines the effect of the carbon fiber cloth’s thickness, air permeability, surface resistivity, XRD and elemental analysis. Carbon fiber cloth is carbonized at rates of 190, 220, 250, 280, and 310 °C min⁻¹ respectively, and the resulting carbon fiber cloth is tested in cells. When the test piece area is 25 cm², the test temperature 40 °C, the gasket thickness 0.36 mm, and the carbonization rate 280 °C min⁻¹, a fuel cell using the carbon fiber cloth achieves a current density of 1968 mA cm⁻² and a maximum power density of 633 mW cm⁻² at 0.3 V.     

Structure and electrochemical properties of activated polyacrylonitrile based carbon fibers containing carbon nanotubes

Solution spun polyacrylonitrile (PAN), PAN/multi-wall carbon nanotube (MWCNT), and PAN/single-wall carbon nanotube (SWCNT) fibers containing 5 wt.% carbon nanotubes were stabilized in air and activated using CO₂ and KOH. The surface area as determined by nitrogen gas adsorption was an order of magnitude higher for KOH activated fibers as compared to the CO₂ activated fibers. The specific capacitance of KOH activated PAN/SWCNT samples was as high as 250 F g⁻¹ in 6 M KOH electrolyte. Under the comparable KOH activation conditions, PAN and PAN/SWCNT fibers had comparable surface areas (BET surface area about 2200 m² g⁻¹) with pore size predominantly in the range of 1–5 nm, while surface area of PAN/MWCNT samples was significantly lower (BET surface area 970 m² g⁻¹). The highest capacitance and energy density was obtained for PAN/SWCNT samples, suggesting SWCNT advantage in charge storage. The capacitance behavior of these electrodes has also been tested in ionic liquids, and the energy density in ionic liquid is about twice the value obtained using KOH electrolyte.     

Corrosion of carbon support for PEM fuel cells by electrochemical quartz crystal microbalance

During the voltammetry of carbon supports for proton exchange membrane fuel cells (PEMFCs), including commercial carbon blacks, graphitized carbon black and multi-wall carbon nanotubes (MWNTs), in deaerated 0.5 M H₂SO₄ solution results in mass changes as observed by using in situ electrochemical quartz crystal microbalance (EQCM). The mass change and corrosion onset potential during electrochemical carbon corrosion indicate that oxides are formed and accumulated on the carbon surface, leading to an increase in mass. A decrease in the mass is associated with carbon loss from the gasification of carbon surface oxides into carbon dioxide. High BET surface area carbon blacks ECP600 and ECP 300 have a carbon loss of 0.0245 ng cm⁻² s⁻¹ and 0.0144 ng cm⁻² s⁻¹ and as compared to 0.0115 ng cm⁻² s⁻¹ for low surface area support XC-72 and so they are less resistant to corrosion. Graphitized XC-72 and MWNTs, with higher graphitization have higher carbon corrosion onset potential at 1.65 V and 1.62 V and appear to be more intrinsically resistant to corrosion.     

Effect of carbon fiber paper made from carbon felt with different yard weights on the performance of low temperature proton exchange membrane fuel cells

This study employed fuel cell gas diffusion layers (GDLs) consisting of carbon fiber paper made from carbon fiber felt with different yard weights in proton exchange membrane fuel cells (PEMFCs), and investigated the relationship between the yard weight of the carbon fiber paper and the fuel cell performance and thickness of the gasket. In this paper we discuss the relationship between carbon fiber felt with different yard weights and fuel cell performance and also explore the effect of carbon fiber paper thickness, air permeability, surface resistivity, and structural study. We focused on the material used for the gas diffusion layer in this study. Carbon fiber paper made in-house in this study contained 10 wt% (all percentages are by weight unless otherwise noted) phenolic resin. When the tested area was 25 cm², the test temperature was 40 °C, the gasket thickness was 0.06 mm, and the yard weight 70 g m⁻², fuel cell current density was 1968 mA cm⁻² at a load 0.3 V. When the gasket thickness was 0.36 mm and yard weight was 190 g m⁻², fuel current density was 1710 mA cm⁻² at a load of 0.3 V.     

Sea urchin-like mesoporous carbon material grown with carbon nanotubes as a cathode catalyst support for fuel cells

A sea urchin-like carbon (UC) material with high surface area (416 m² g⁻¹), adequate electrical conductivity (59.6 S cm⁻¹) and good chemical stability was prepared by growing carbon nanotubes onto mesoporous carbon hollow spheres. A uniform dispersion of Pt nanoparticles was then anchored on the UC, where the Pt nanoparticles were prepared using benzylamine as the stabilizer. For this Pt loaded carbon, cyclic voltammogram measurements showed an exceptionally high electrochemically active surface area (EAS) (114.8 m² g⁻¹) compared to the commonly used commercial E-TEK catalyst (65.2 m² g⁻¹). The durability test demonstrates that the carbon used as a support exhibited minor loss in EAS of Pt. Compared to the E-TEK (20 wt%) cathode catalyst, this Pt loaded UC catalyst has greatly enhanced catalytic activity toward the oxygen reduction reaction, less cathode flooding and considerably improved performance, resulting in an enhancement of ca. 37% in power density compared with that of E-TEK. Based on the results obtained, the UC is an excellent support for Pt nanoparticles used as cathode catalysts in proton exchange membrane fuel cells.     

Platinum-sputtered electrode based on blend of carbon nanotubes and carbon black for polymer electrolyte fuel cell

A novel Pt-sputtered electrode based on a blend layer of carbon black (CB) and carbon nanotubes (CNTs) is developed for polymer electrolyte fuel cells. The Pt is sputtered on the surface of the blend to form a catalyst layer. The CNTs generate a pore in the blend layer, and the CB provides a high surface roughness for the blend layer. At a CNT content of 50 wt.%, the maximum value (20.6 m² g⁻¹) for the electrochemical area of the Pt is obtained, which indicates that the surface area of the blend layer exposed for Pt deposition is the largest. The power density of a membrane-electrode assembly (MEA) employing the Pt-sputtered electrodes shows a linear increase with electrochemical area. The mass activity of the optimized Pt-sputtered electrode with a Pt loading of 0.05 mg cm⁻² is 8.1 times that of an electrode with a Pt loading of 0.5 mg cm⁻² prepared using a conventional screen-printing technique. Excellent mass transfer is obtained with the Pt-sputtered electrode.     

Effective debundling of carbon nanotubes and simultaneous synthesis of Pt nanoparticles by Nafion induced emulsions

Carbon nanostructures and, in particular, Single Wall Carbon Nanotubes (SWNT) or Multi Wall Carbon Nanotubes (MWNT) provide unique properties, notably outstanding chemical stability and electronic conductivity. Therefore they can be seen as a potential replacement for carbon black, which is frequently used as support material for polymer electrolyte membrane fuel cell (PEMFC) catalysts. This paper describes a new synthesis method to deposit platinum nanoparticles on carbon by using MWNT/Nafion^® emulsions in the reduction reaction of hexachloroplatinate with ethylene glycol and butyl acetate. In contrast to other syntheses described in the literature, the formation of an emulsion allows effective debundling and a good dispersion of MWNTs in the solvent. This strategy helps to maintain a narrow Pt particle size distribution of 3 nm ± 0.5 nm and a homogeneous dispersion of the nanoparticles on the support even at loadings of up to 50 wt%. It furthermore reduces agglomeration of the MWNTs during electrode manufacturing, so that an airbrush technique can be used, and enhances the ionic conductivity of the electrode layer. Catalyst morphology and distribution are investigated by transmission electron microscopy, X-ray diffraction and scanning electron microscopy. Electrodes are produced by a conventional airbrush technique on Nafion^® membranes (Nafion^® 117 and Nafion^® NRE 212) and tested in a fuel cell test bench.     

Morphology and electrical properties of conductive carbon coatings for cathode materials

Many interesting cathode materials, such as LiFePO₄, LiMnPO₄, LiFeBO₃ or the recently discovered Li₂FeSiO₄ and Li₂MnSiO₄, exhibit extremely low electronic conductivity (<10⁻⁹ S cm⁻¹). A very efficient way for improving the electronic transport in such materials is supposed to be the preparation of carbon coatings around individual active particles. Despite the increasing number of reports on preparation of various carbon coatings, neither the formation mechanism nor the detailed coating properties have been explained satisfactorily. The present paper is an attempt to find a clear correlation between the synthesis parameters, the resulting coating morphology and, finally, its electrical properties. As a substrate material for deposition of coatings, more or less monodisperse TiO₂ particles in various sizes were used. As a carbon precursor, citrate was used because it had given excellent results in our previous investigation of the LiFePO₄ system. It is shown that citrate precursor delivers pretty good conductivity (ca. 30 S cm⁻¹) after a 10 h heat treatment at 700 °C or higher. The conductivity percolation threshold can be reached already at 1.5 vol.% of carbon, while the plateau conductivity of the whole composite is about 0.1 S cm⁻¹. At that level, the carbon phase is supposed to form a well-distributed 3D electrical network within the composite.     

Electrochemical double layer capacitor and lithium-ion capacitor based on carbon black

In this paper we report the physical investigation and the electrochemical performance of the carbon black SC3 from Cabot Corporation. The SC3 carbon black was investigated in terms of BET surface area, pore size distribution, resistivity and morphology. Composite electrodes containing SC3 as active material were prepared and used for the realization of electrochemical double layer capacitor (EDLC) and lithium-ion capacitor (LIC). In EDLC, at 5 mA cm⁻² charge-discharge currents, the carbon black displays a specific capacity of 40 mAh g⁻¹ and a specific capacitance of 115 F g⁻¹. It also displays a very good cycling stability for over 50,000 cycles and excellent performance retention at currents up to 50 mA cm⁻². The performance retention at high currents outstandingly differentiates this carbon black from a few commercially available EDLC-grade activated carbons. Because of the high specific capacity of SC3, the carbon black electrodes were also used in combination with LiFePO₄ electrodes in LIC. The results of this study indicate that SC3 carbon black is an interesting carbonaceous candidate for the realization of LIC.     

Reversible high capacity nanocomposite anodes of Si/C/SWNTs for rechargeable Li-ion batteries

Nanocomposites comprising silicon (Si), graphite (C) and single-walled carbon nanotubes (SWNTs), denoted as Si/C/SWNTs, have been synthesized by dispersing SWNTs via high power ultrasonication into a pre-milled Si/C composite mixture, followed by subsequent thermal treatment. The Si/C composite powder was prepared by high-energy mechanical milling (HEMM) of elemental Si and graphite using polymethacrylonitrile (PMAN) as a diffusion barrier suppressing the possible mechanochemical reaction between silicon and graphite to form SiC, and further prevent the amorphization of graphite during extended milling. A nanocomposite with nominal composition of Si-35 wt.% SWNTs-37 wt.% exhibits a reversible discharge capacity of ∼900 mAh g⁻¹ with an excellent capacity retention of capacity loss of 0.3% per cycle up to 30 cycles. Functionalization of the SWNTs with LiOH significantly improves the cyclability of the nanocomposite containing Si-45 wt.% SWNTs-28 wt.% exhibiting a reversible capacity of 1066 mAh g⁻¹ and displaying almost no fade in capacity up to 30 cycles. The improved electrochemical performance is hypothesized to be attributed to the formation of a nanoscale conductive network by the dispersed SWNTs which leads to successful maintenance of good electrical contact between the electrochemically active particles during cycling.     

Textural and electrochemical characterization of porous carbon nanofibers as electrodes for supercapacitors

Porous carbon nanofibers (CNFs) enriched with the graphitic structure were synthesized by thermal decomposition from a mixture containing polyethylene glycol and nickel chloride (catalyst). The textural and electrochemical properties of porous CNFs were systematically compared with those of commercially available multi-walled carbon nanotubes (MWCNTs). The high ratio of mesopores and large amount of open edges of porous CNFs with a higher specific surface area, very different from that of MWCNTs, are favorable for the penetration of electrolytes meanwhile the graphene layers of porous CNFs serve as a good electronic conductive medium of electrons. The electrochemical properties of porous CNFs and MWCNTs were characterized for the application of supercapacitors using cyclic voltammetry, galvanostatic charge–discharge method, and electrochemical impedance spectroscopic analyses. The porous CNFs show better capacitive performances (C_S = 98.4 F g⁻¹ at 25 mV s⁻¹ and an onset frequency of behaving as a capacitor at 1.31 kHz) than that of MWCNTs (C_S = 17.8 F g⁻¹ and an onset frequency at 1.01 kHz). This work demonstrates the promising capacitive properties of porous CNFs for the application of electrochemical supercapacitors.