High-performance supercapacitor electrode materials from cellulose-derived carbon nanofibers

Nitrogen-functionalized carbon nanofibers (N-CNFs) were prepared by carbonizing polypyrrole (PPy)-coated cellulose NFs, which were obtained by electrospinning, deacetylation of electrospun cellulose acetate NFs, and PPy polymerization. Supercapacitor electrodes prepared from N-CNFs and a mixture of N-CNFs and Ni(OH)2 showed specific capacitances of ∼236 and ∼1045 F g(-1), respectively. An asymmetric supercapacitor was further fabricated using N-CNFs/Ni(OH)2 and N-CNFs as positive and negative electrodes. The supercapacitor device had a working voltage of 1.6 V in aqueous KOH solution (6.0 M) with an energy density as high as ∼51 (W h) kg(-1) and a maximum power density of ∼117 kW kg(-1). The device had excellent cycle lifetime, which retained ∼84% specific capacitance after 5000 cycles of cyclic voltammetry scans. N-CNFs derived from electrospun cellulose may be useful as an electrode material for development of high-performance supercapacitors and other energy storage devices.

High-performance supercapacitor electrode from cellulose-derived, inter-bonded carbon nanofibers

Carbon nanofibers with inter-bonded fibrous structure show high supercapacitor performance when being used as electrode materials. Their preparation is highly desirable from cellulose through a pyrolysis technique, because cellulose is an abundant, low cost natural material and its carbonization does not emit toxic substance. However, interconnected carbon nanofibers prepared from electrospun cellulose nanofibers and their capacitive behaviors have not been reported in the research literature. Here we report a facile one-step strategy to prepare inter-bonded carbon nanofibers from partially hydrolyzed cellulose acetate nanofibers, for making high-performance supercapacitors as electrode materials. The inter-fiber connection shows considerable improvement in electrode electrochemical performances. The supercapacitor electrode has a specific capacitance of ∼241.4 F g-1 at 1 A g-1 current density. It maintains high cycling stability (negligible 0.1% capacitance reduction after 10,000 cycles) with a maximum power density of ∼84.1 kW kg-1. They may find applications in the development of efficient supercapacitor electrodes for energy storage applications.

Cycling performance of lithium metal polymer cells assembled with ionic liquid and poly(3-methyl thiophene)/carbon nanotube composite cathode

A poly(3-methylthiophene) (PMT)/multi-walled carbon nanotube (CNT) composite is synthesized by in situ chemical polymerization. The PMT/CNT composite is used as an active cathode material in lithium metal polymer cells assembled with ionic liquid (IL) electrolytes. The IL electrolyte consists of 1-ethyl-3-methylimidazolium tetrafluoroborate (EMIBF4) and LiBF4. A small amount of vinylene carbonate is added to the IL electrolyte to prevent the reductive decomposition of the imidazolium cation in EMIBF4. A porous poly(vinylidene fluoride-co-hexafluoropropylene) (P(VdF-co-HFP)) film is used as a polymer membrane for assembling the cells. Electrochemical properties of the PMT/CNT composite electrode in the IL electrolyte are evaluated and the effect of vinylene carbonate on the cycling performance of the lithium metal polymer cells is investigated. The cells assembled with a non-flammable IL electrolyte and a PMT/CNT composite cathode are promising candidates for high-voltage–power sources with enhanced safety.

High rates of oxygen reduction over a vapor phase-polymerized PEDOT electrode

The air electrode, which reduces oxygen (O₂), is a critical component in energy generation and storage applications such as fuel cells and metal/air batteries. The highest current densities are achieved with platinum (Pt), but in addition to its cost and scarcity, Pt particles in composite electrodes tend to be inactivated by contact with carbon monoxide (CO) or by agglomeration. We describe an air electrode based on a porous material coated with poly(3,4-ethylenedioxythiophene) (PEDOT), which acts as an O₂ reduction catalyst. Continuous operation for 1500 hours was demonstrated without material degradation or deterioration in performance. O₂ conversion rates were comparable with those of Pt-catalyzed electrodes of the same geometry, and the electrode was not sensitive to CO. Operation was demonstrated as an air electrode and as a dissolved O₂ electrode in aqueous solution.

Evidence for the direct interaction between methylene blue and guanine bases using DNA-modified carbon paste electrodes

It is explored that methylene blue interacts with the guanine bases specifically, rather than the bases of ss-DNA in general. This interaction can be used as a method of quantifying the amount of oligonucleotide that is immobilized onto an electrode surface.

Protein electrochemistry using aligned carbon nanotube arrays

The remarkable electrocatalytic properties and small size of carbon nanotubes make them ideal for achieving direct electron transfer to proteins, important in understanding their redox properties and in the development of biosensors. Here, we report shortened SWNTs can be aligned normal to an electrode by self-assembly and act as molecular wires to allow electrical communication between the underlying electrode and redox proteins covalently attached to the ends of the SWNTs, in this case, microperoxidase MP-11. The efficiency of the electron transfer through the SWNTs is demonstrated by electrodes modified with tubes cut to different lengths having the same electron-transfer rate constant.

MoO3 nanoparticles dispersed uniformly in carbon matrix : a high capacity composite anode for Li-ion batteries

A MoO₃-carbon nanocomposite was synthesized from a mixture of MoO₃ and graphite by a controlled ball milling procedure. The as-prepared product consists of nanosized MoO₃ particles (2-180 nm) homogeneously distributed in carbon matrix. The nanocomposite acts as a high capacity anode material for lithium-ion batteries and exhibits good cyclic behavior. Its initial capacity exceeds the theoretical capacity of 745 mA h g^-1 in a mixture of MoO₃ and graphite (1:1 by weight), and the stable capacity of 700 mA h g^-1 (94% of the theoretical capacity) is still retained after 120 cycles. The electrode performance is linked with the unique nanoarchitecture of the composite and is compared with the performance of MoO₃-based anode materials reported in the literature previously (nanoparticles, ball milled powders, and carbon-coated nanobelts). The high value of capacity and good cyclic stability of MoO₃-carbon nanocomposite are attractive in respect to those of the reported MoO₃ electrodes.

Substrate-induced coagulation (SIC) of nano-disperse carbon black in non-aqueous media : a method of manufacturing highly conductive cathode materials for Li-ion batteries by self-assembly

Substrate-induced coagulation (SIC) is a coating process based on self-assembly for coating different surfaces with fine particulate materials. The particles are dispersed in a suitable solvent and the stability of the dispersion is adjusted by additives. When a surface, pre-treated with a flocculant e.g. a polyelectrolyte, is dipped into the dispersion, it induces coagulation resulting in the deposition of the particles on the surface. A non-aqueous SIC process for carbon coating is presented, which can be performed in polar, aprotic solvents such as N-Methyl-2- pyrrolidinone (NMP). Polyvinylalcohol (PVA) is used to condition the surface of substrates such as mica, copperfoil, silicon-wafers and lithiumcobalt oxide powder, a cathode material used for Li-ion batteries. The subsequent SIC carbon coating produces uniform layers on the substrates and causes the conductivity of lithiumcobalt oxide to increase drastically, while retaining a high percentage of active battery material.

Harvesting waste thermal energy using a carbon-nanotube-based thermo-electrochemical cell

Low efficiencies and costly electrode materials have limited harvesting of thermal energy as electrical energy using thermo-electrochemical cells (or “thermocells”). We demonstrate thermocells, in practical configurations (from coin cells to cells that can be wrapped around exhaust pipes), that harvest low-grade thermal energy using relatively inexpensive carbon multiwalled nanotube (MWNT) electrodes. These electrodes provide high electrochemically accessible surface areas and fast redox-mediated electron transfer, which significantly enhances thermocell current generation capacity and overall efficiency. Thermocell efficiency is further improved by directly synthesizing MWNTs as vertical forests that reduce electrical and thermal resistance at electrode/substrate junctions. The efficiency of thermocells with MWNT electrodes is shown to be as high as 1.4% of Carnot efficiency, which is 3-fold higher than for previously demonstrated thermocells. With the cost of MWNTs decreasing, MWNT-based thermocells may become commercially viable for harvesting low-grade thermal energy.

Oxygen reduction reaction activity of La-based perovskite oxides in alkaline medium : a thin-film rotating ring-disk electrode study

In this work, LaMO₃ and LaNi_0.5M_0.5O₃ (M = Ni, Co, Fe, Mn and Cr) perovskite oxide electrocatalysts were synthesized by a combined ethylenediaminetetraacetic acid-citrate complexation technique and subsequent calcinations at 1000 °C in air. Their powder X-ray diffraction patterns demonstrate the formation of a specific crystalline structure for each composition. The catalytic property of these materials toward the oxygen reduction reaction (ORR) was studied in alkaline potassium hydroxide solution using the rotating disk and rotating ring-disk electrode techniques. Carbon is considered to be a crucial additive component because its addition into perovskite oxide leads to optimized ORR current density. For LaMO₃ (M = Ni, Co, Fe, Mn and Cr)), in terms of the ORR current densities, the performance is enhanced in the order of LaCrO₃, LaFeO₃, LaNiO₃, LaMnO₃, and LaCoO3. For LaNi_0.5M_0.5O₃, the ORR current performance is enhanced in the order of LaNi_0.5Fe_0.5O₃, LaNi_0.5Co_0.5O₃, LaNi_0.5Cr_0.5O₃, and LaNi_0.5Mn_0.5O₃. Overall, LaCoO₃ demonstrates the best performance. Most notably, substituting half of the nickel with cobalt, iron, manganese, or chromium translates the ORR to a more positive onset potential, suggesting the beneficial catalytic effect of two transition metal cations with Mn as the most promising candidate. Koutecky–Levich analysis on the ORR current densities of all compositions indicates that the four-electron pathway is favored on these oxides, which are consistent with hydroperoxide ion formation of <2%.