Deactivation of carbon electrode for elimination of carbon dioxide evolution from rechargeable lithium-oxygen cells

Carbon has unfaired advantages in material properties to be used as electrodes. It offers a low cost, light weight cathode that minimizes the loss in specific energy of lithium-oxygen batteries as well. To date, however, carbon dioxide evolution has been an unavoidable event during the operation of non-aqueous lithium-oxygen batteries with carbon electrodes, due to the reactivity of carbon against self-decomposition and catalytic decomposition of electrolyte. Here we report a simple but potent approach to eliminate carbon dioxide evolution by using an ionic solvate of dimethoxyethane and lithium nitrate. We show that the solvate leads to deactivation of the carbon against parasitic reactions by electrochemical doping of nitrogen into carbon. This work demonstrates that one could take full advantage of carbon by mitigating the undesired activity. © 2014 Macmillan Publishers Limited. All rights reserved.open8

Synergistic effect of quinary molten salts and Ruthenium catalyst for high-power-density Lithium-carbon dioxide cell

With a recent increase in interest in metal-gas batteries, the lithium-carbon dioxide cell has attracted considerable attention because of its extraordinary carbon dioxide-capture ability during the discharge process and its potential application as a power source for Mars exploration. However, owing to the stable lithium carbonate discharge product, the cell enables operation only at low current densities, which significantly limits the application of lithium-carbon dioxide batteries and effective carbon dioxide-capture cells. Here, we investigate a high-performance lithium-carbon dioxide cell using a quinary molten salt electrolyte and ruthenium nanoparticles on the carbon cathode. The nitrate-based molten salt electrolyte allows us to observe the enhanced carbon dioxide-capture rate and the reduced discharge-charge over-potential gap with that of conventional lithium-carbon dioxide cells. Furthermore, owing to the ruthernium catalyst, the cell sustains its performance over more than 300 cycles at a current density of 10.0Ag(-1) and exhibits a peak power density of 33.4mWcm(-2). Lithium-carbon dioxide cells are challenging due to the sluggish electron transfer in the Lithium carbonate in aprotic electrolyte. Here, the authors report synergistic effect of molten salt electrolyte and Ruthenium catalyst to enhance the electrochemical performance of Lithium-carbon dioxide batterie

Platinum particles supported on titanium nitride: an efficient electrode material for the oxidation of methanol in alkaline media

In the present study, titanium nitride which shows exceptional stability, extreme corrosion resistance, good electronic conductivity and adhesion behaviour is used to support platinum particles and then used for methanol oxidation in an alkaline medium. The catalyst shows very good CO tolerance for the electrochemical oxidation of methanol. In situ infrared spectroelectrochemical data show the remarkable ability of TiN to decompose water at low over potentials leading to -OH type functional groups on its surface which in turn help in alleviating the carbon monoxide poisoning associated with methanol oxidation. TiN supported catalysts are found to be very good in terms of long term stability, exchange current density and stable currents at low over voltages. Supporting evidence from X-ray photoelectron spectroscopic data and cyclic voltammetry clearly demonstrates the usefulness of TiN supported Pt catalysts for efficient methanol oxidation in alkaline media

Pd Supported on Titanium Nitride for Efficient Ethanol Oxidation

The excellent metal support interaction between palladium (Pd) and titanium nitride (TiN) is exploited in designing an efficient anode material. Pd-TN, that could be useful for direct ethanol fuel cell in alkaline media. The physicochemical and electrochemical characterization of the Pd-TiN/electrolyte interface reveals an efficient oxidation of ethanol coupled with excellent stability of the catalyst under electrochemical conditions. Characterization of the interface using in situ Fourier transform infrared spectroscopy (in situ FITR) shows the production CO2 at low overvoltages revealing an efficient cleaving of the C-C bond. The performance comparison of Pd supported on TiN (Pd-TiN) with that supported on carbon (Pd-C) clearly demonstrates the advantages of TiN support over carbon. A positive chemical shift of Pd (3d) binding energy confirms the existence of metal support interaction between pd and TiN, which in turn helps weaken the Pd-CO synergetic bonding interaction. The remarkable ability of TiN to accumulate -OH species on its surface coupled with the strong adhesion of Pd makes TiN an active support material for electrocatalysts

Ruthenium nanocrystal decorated vertical graphene nanosheets@Ni foam as highly efficient cathode catalysts for lithium-oxygen batteries

The electrochemical performance of lithium-oxygen (Li-O2) batteries can be markedly improved through designing the architecture of cathode electrodes with sufficient spaces to facilitate the diffusion of oxygen and accommodate the discharge products, and optimizing the cathode catalyst to promote the oxygen reduction reaction and oxygen evolution reaction (OER). Herein, we report the synthesis of ruthenium (Ru) nanocrystal-decorated vertically aligned graphene nanosheets (VGNS) grown on nickel (Ni) foam. As an effective binder-free cathode catalyst for Li-O2 batteries, the Ru-decorated VGNS@Ni foam can significantly reduce the charge overpotential via the effects on the OER and achieve high specific capacity, leading to an enhanced electrochemical performance. The Ru-decorated VGNS@Ni foam electrode has demonstrated low charge overpotential of ~0.45 V and high reversible capacity of 23 864 mAh g−1 at the current density of 200 mA g−1, which can be maintained for 50 cycles under full charge and discharge testing condition in the voltage range of 2.0-4.2 V. Furthermore, Ru nanocrystal decorated VGNS@Ni foam can be cycled for more than 200 cycles with a low overpotential of 0.23 V under the capacity curtained to be 1000 mAh g−1 at a current density of 200 mA g−1. Ru-decorated VGNS@Ni foam electrodes have also achieved excellent high rate and long cyclability performance. This superior electrochemical performance should be ascribed to the unique three-dimensional porous nanoarchitecture of the VGNS@Ni foam electrodes, which provide sufficient pores for the diffusion of oxygen and storage of the discharge product (Li2O2), and the effective catalytic effect of Ru nanocrystals on the OER, respectively. Ex situ field emission scanning electron microscopy, X-ray diffraction, Raman and Fourier transform infrared measurements revealed that Ru-decorated VGNS@Ni foam can effectively decompose the discharge product Li2O2, facilitate the OER and lead to a high round-trip efficiency. Therefore, Ru-decorated VGNS@Ni foam is a promising cathode catalyst for rechargeable Li-O2 batteries with low charge overpotential, long cycle life and high specific capacity