RESUMO
The ultimate goal of Li ion battery design should consist of fully accessible metallic current collectors, possibly of nanoscale dimensions, intimately in contact with high capacity stable electrode materials. Here we engineer three-dimensional porous nickel based current collector coated conformally with layers of silicon, which typically suffers from poor cycle life, to form high-capacity electrodes. These binder/conductive additive free silicon electrodes show excellent electrode adhesion resulting in superior cyclic stability and rate capability. The nickel current collector design also allows for an increase in silicon loading per unit area leading to high areal discharge capacities of up to 0.8 mAh/cm(2) without significant loss in rate capability. An excellent electrode utilization (â¼85%) and improved cyclic stability for the metal/silicon system is attributed to reduced internal stresses/fracture upon electrode expansion during cycling and shorter ionic/electronic diffusion pathways that help in improving the rate capability of thicker silicon layers.
RESUMO
Non-aqueous Li-air or Li-O(2) cells show considerable promise as a very high energy density battery couple. Such cells, however, show sudden death at capacities far below their theoretical capacity and this, among other problems, limits their practicality. In this paper, we show that this sudden death arises from limited charge transport through the growing Li(2)O(2) film to the Li(2)O(2)-electrolyte interface, and this limitation defines a critical film thickness, above which it is not possible to support electrochemistry at the Li(2)O(2)-electrolyte interface. We report both electrochemical experiments using a reversible internal redox couple and a first principles metal-insulator-metal charge transport model to probe the electrical conductivity through Li(2)O(2) films produced during Li-O(2) discharge. Both experiment and theory show a "sudden death" in charge transport when film thickness is ~5 to 10 nm. The theoretical model shows that this occurs when the tunneling current through the film can no longer support the electrochemical current. Thus, engineering charge transport through Li(2)O(2) is a serious challenge if Li-O(2) batteries are ever to reach their potential.
RESUMO
Among the many important challenges facing the development of Li-air batteries, understanding the electrolyte's role in producing the appropriate reversible electrochemistry (i.e., 2Li(+) + O2 + 2e(-) â Li2O2) is critical. Quantitative differential electrochemical mass spectrometry (DEMS), coupled with isotopic labeling of oxygen gas, was used to study Li-O2 electrochemistry in various solvents, including carbonates (typical Li ion battery solvents) and dimethoxyethane (DME). In conjunction with the gas-phase DEMS analysis, electrodeposits formed during discharge on Li-O2 cell cathodes were characterized using ex situ analytical techniques, such as X-ray diffraction and Raman spectroscopy. Carbonate-based solvents were found to irreversibly decompose upon cell discharge. DME-based cells, however, produced mainly lithium peroxide on discharge. Upon cell charge, the lithium peroxide both decomposed to evolve oxygen and oxidized DME at high potentials. Our results lead to two conclusions; (1) coulometry has to be coupled with quantitative gas consumption and evolution data to properly characterize the rechargeability of Li-air batteries, and (2) chemical and electrochemical electrolyte stability in the presence of lithium peroxide and its intermediates is essential to produce a truly reversible Li-O2 electrochemistry.
RESUMO
Single-wall and multiwall carbon nanotubes are employed as carbon supports in direct methanol fuel cells (DMFC). The morphology and electrochemical activity of single-wall and multiwall carbon nanotubes obtained from different sources have been examined to probe the influence of carbon support on the overall performance of DMFC. The improved activity of the Pt-Ru catalyst dispersed on carbon nanotubes toward methanol oxidation is reflected as a shift in the onset potential and a lower charge transfer resistance at the electrode/electrolyte interface. The evaluation of carbon supports in a passive air breathing DMFC indicates that the observed power density depends on the nature and source of carbon nanostructures. The intrinsic property of the nanotubes, dispersion of the electrocatalyst and the electrochemically active surface area collectively influence the performance of the membrane electrode assembly (MEA). As compared to the commercial carbon black support, single wall carbon nanotubes when employed as the support for anchoring the electrocatalyst particles in the anode and cathode sides of MEA exhibited a approximately 30% enhancement in the power density of a single stack DMFC operating at 70 degrees C.
Assuntos
Metanol/química , Nanotubos de Carbono/química , Fontes de Energia Elétrica , Eletroquímica , Eletrodos , Oxirredução , Tamanho da Partícula , Propriedades de SuperfícieRESUMO
Significant enhancement in the electrocatalytic activity of Pt particles toward oxygen reduction reaction (ORR) has been achieved by depositing them on a single wall carbon nanotubes (SWCNT) support. Compared to a commercial Pt/carbon black catalyst, Pt/SWCNT films cast on a rotating disk electrode exhibit a lower onset potential and a higher electron-transfer rate constant for oxygen reduction. Improved stability of the SWCNT support is also confirmed from the minimal change in the oxygen reduction current during repeated cycling over a period of 36 h. These studies open up ways to utilize SWCNT/Pt electrocatalyst as a cathode in the proton-exchange-membrane-based hydrogen and methanol fuel cells.
RESUMO
A membrane electrode assembly (MEA) for hydrogen fuel cells has been fabricated using single-walled carbon nanotubes (SWCNTs) support and platinum catalyst. Films of SWCNTs and commercial platinum (Pt) black were sequentially cast on a carbon fiber electrode (CFE) using a simple electrophoretic deposition procedure. Scanning electron microscopy and Raman spectroscopy showed that the nanotubes and the platinum retained their nanostructure morphology on the carbon fiber surface. Electrochemical impedance spectroscopy (EIS) revealed that the carbon nanotube-based electrodes exhibited an order of magnitude lower charge-transfer reaction resistance (R(ct)) for the hydrogen evolution reaction (HER) than did the commercial carbon black (CB)-based electrodes. The proton exchange membrane (PEM) assembly fabricated using the CFE/SWCNT/Pt electrodes was evaluated using a fuel cell testing unit operating with H(2) and O(2) as input fuels at 25 and 60 degrees C. The maximum power density obtained using CFE/SWCNT/Pt electrodes as both the anode and the cathode was approximately 20% better than that using the CFE/CB/Pt electrodes.
Assuntos
Hidrogênio/química , Nanotubos de Carbono/química , Eletroquímica , Eletrodos , Microscopia Eletrônica de Varredura , Oxigênio/química , Análise Espectral RamanRESUMO
A hybrid carbon fiber electrode (CFE) consisting of TiO2 semiconductor photocatalyst and Pt-Ru catalyst has been developed to boost the performance of direct methanol fuel cells (DMFC). These two catalyst nanoparticles are deposited on opposite sides of the carbon fiber paper such that methanol oxidation is carried out catalytically on Pt-Ru and photocatalytically on TiO2 under UV-light irradiation. Since both catalysts carry out methanol oxidation independently, we observe an additive effect in the current generation. The carbon support fibers provide a large network to collect the electrons from both of these catalytic processes and thus assist in efficient current generation. In addition, TiO2 improves the performance of the Pt-Ru catalyst in dark, indicating possible surface area improvement or diminished poisoning effects. The concept of incorporating a photocatalyst provides new ways to minimize precious metal content and enhance the performance of DMFCs. At low catalyst loadings (0.15 mg/cm2) at 295 K, a 25% enhancement in the peak power density is observed upon illumination with light.
RESUMO
A one-step process of solubilization of single wall carbon nanotubes (SWCNT) in an organic solvent has enabled us to polarize them asymmetrically in a dc electric field. Quaternary ammonium ion-capped SWCNTs readily suspend in organic solvents; under the influence of a dc electric field, they assemble as stretched bundles anchored on the positive electrode. At low dc applied field (approximately 40 V), all of the SWCNTs from the suspension are deposited on the electrode, thus providing a simple methodology to design robust SWCNT films. At higher applied voltages (>100 V), the SWCNT bundles stretch out into the solution and orient themselves perpendicular to the electrode surface. The alignment of these bundles is responsive to the ON-OFF cycles of the applied electric field. The possibility of modulating the alignment of SWCNT in an electric field opens new ways to achieve electrical contacts in nano- to micro-devices.