Anders Lundblad

Influence of the composition on the structure and electrochemical characteristics of the PEFC cathode

The influence the composition of the cathode has on its structure and electrochemical performance was investigated for a Nafion content spanning from 10 to 70 wt.%. The cathodes were formed on a Na ...

Investigation of Mass-Transport Limitations in the Solid Polymer Fuel Cell Cathode II. Experimental

In this work, we investigated the kinetics and mass-transport limitations of the oxygen reduction reaction in the solid polymer fuel cell. The information obtained from electrochemical experiments ...

Synthesis of LiCoO2 starting from carbonate precursors I. The reaction mechanisms

Abstract The reaction mechanisms during calcination of a Li 2CO 3/Co 3O 4 mixture in air and CO 2 were monitored by thermogravimetry, differential thermal analysis and complementary calcinations at 300 and 500 °C. It was determined how weight reduction, specific surface area and the formation of phases develop. Below 400 °C the main process is the decomposition of CoCO 3. Formation of LiCoO 2 starts above 400 °C but at high O 2 partial pressures some Li 2CO 3 seems to react already at 300 °C.

Synthesis and Performance of LiCoO2 Cathodes for the Molten Carbonate Fuel Cell

A method for fabricating LiCoO2 electrodes has been developed. LiCoO2 powder was synthesized from Li2CO3 and CoCO3 powder by calcining in air at 650-degrees-C. Electrodes were tape cast in a nona ...

Gas Diffusion Electrodes and Membrane Electrode Assemblies Based on a Sulfonated Polysulfone for High-Temperature PEMFC

Membrane electrode assemblies MEAs with a sulfonated polysulfone sPSU as the proton-conducting phase were fuel cellevaluated at varying temperatures in over-humidified conditions. The sPSU was prep ...

In situ micro-Raman on the membrane in a working PEM cell

An electrochemical cell has been designed for in situ micro-Raman measurements on the polymer membrane in an operating polymer electrolyte cell (PEM). The method is applicable to studies of both th ...

Effect of sintering procedures in development of LiCoO2-cathodes for the molten carbonate fuel cell

Abstract LiCoO 2 -powder was synthesized from carbonate precursors by calcination in air. Greentapes were tape-cast using a non-aqueous slurry and 10 μm plastic spheres as pore formers. Sintering was carried out in air at 850–950°C and in argon/air at 500/750°C. The two sintering procedures led to very different sub-micron morphologies, with the primary particles being much smaller in the latter case. The electrochemical performance at 650°C, in terms of overpotential at 160 mA/cm 2 , for the air- and argon/air-sintered electrodes was 57 and 81 mV, respectively. The potential drop due to contact resistance between electrode and current collector was estimated to be 100 and 70 mV, respectively. The electrode materials were characterized by scanning electron microscopy (SEM), Hg-porosimetry, the BET-method (N 2 -adsorption), X-ray diffractometry (XRD), flame atomic absorption spectrometry (F-AAS), carbon analysis and a van der Pauw conductivity measurement set-up.

Effects of Pore Surface Oxidation on Electrochemical and Mass-Transport Properties of Nanoporous Carbon

In this doctoral project, a relatively new form of carbon material, with unique narrow pore size distribution around 7 A and with uniform structure, has been electrochemically characterised using the single particle microelectrode technique. The carbon has been used as electrode material for supercapacitors. This type of capacitors is used as high power energy buffers in hybrid vehicles and for stationary power backup. The principle for the microelectrode technique consists of connecting a carbon particle with a carbon fibre by means of a micromanipulator. The single particle and carbon fibre together form a microelectrode. Combination of this technique with electroanalytical methods such as cyclic voltammetry and potential step measurements allows for the survey of electrochemical phenomena and for the determination of ion transport parameters inside the nanopores. A mathematical model based on Fick’s second law, for diffusion of ions inside the nanopores at non steady state, was used for the determination of effective diffusion coefficients (Deff). The coefficients were calculated from an asymptotic solution of Fick’s equation, applied for a thin layer adjacent to the external surface of the carbon particles and valid for the current response in a short time region. Another asymptotic solution was obtained, using spherical geometry and valid for the current response in a long time region. In this doctoral work, the carbon particles have been exposed to potential cycling, which mimics that of large electrodes during operation of a double layer capacitor. The potential-current response, E-I, for the nanoporous carbon, shows a pure capacitive behaviour between –0.5 V and 0.1 V vs. the Hg|HgO reference electrode. The detection of the faradaic processes beyond these potentials was possible by lowering of the voltammometric sweep rate. The electrochemical processes occurring at positive and at negative potential were investigated separately. Cyclic voltammometric measurements showed that the chemisorption of hydroxyl groups, occurring between 0.1 and 0.3 V, leads to a mild oxidation of the carbon structure, resulting in surface groups containing an oxygen atom at a specific carbon site (e.g., phenolic or quinine type). These oxygen-containing surface groups caused an increase of the specific capacitance, which remained constant throughout a number of voltammometric cycles. The Deff decreased on the other hand with the number of cycles. The Deff decreases also with the positive potential. The evaluation of Deff indicates adsorption of hydroxyl groups and an increase of the effective tortuosity of the pore system. The oxidation of the carbon particles, between 0 and 0.5 V, leads to more extensive oxidation and to surface groups containing two oxygen atoms at a single carbon site, followed by formation of carbonate ions. The oxygen-containing surface groups and carbonate ions formed at these potentials do not contribute to the specific capacitance and drastically retard or obstruct the ion transport inside the nanopores. At negative potentials the carbon particles show a dominantly capacitive behaviour. The faradaic processes taking place below –0.5 V vs. Hg|HgO reference electrode are generation and adsorption of hydrogen. These processes do not perturb significantly the electrochemical and ion transport properties of the nanoporous carbon particles. It was found that hydrogen generation occurs at –0.5 V vs. Hg|HgO and that two hydrogen oxidation processes take place at positive potentials. The results indicate that the weakly adsorbed hydrogen undergoes oxidation between 0 and 0.1 V and that the strongly adsorbed hydrogen is oxidised at more positive potentials. The single particle technique was adapted for the determination of diffusion coefficients of an organic electrolyte. The different size of the anions and cations caused different transport characteristics at negative and positive potentials. Slow cycling was found important for ion penetration inside the nanopores and for the evaluation of the effective diffusion coefficients. The effective diffusion coefficients for the nanoporous carbon using aqueous 6M KOH and 0.1M TEABF4 in acetonitrile were estimated to 1.4 (±0.8).10-9 cm2 s-1 and 1.3 (±0.4) 10-8 cm2 s-1, respectively.

Synthesis of LiCoO2 starting from carbonate precursors II. Influence of calcination conditions and leaching

Abstract The effect of initial Li:Co ratio, calcination atmosphere, temperature, leaching in H 2 O or acetic acid solution on reaction completeness, final Li:Co ratio, primary particle size, conductivity and its sensitivity to different atmospheres has been investigated. The calcination gas composition was found to be very important. A powder with a primary particle size of 100–300 nm and with less than 3 wt.% of unreacted Li 2 CO 3 was obtained.

Determination of the effective diffusion coefficient of nanoporous carbon by means of a single particle microelectrode technique

In this doctoral project, a relatively new form of carbon material, with unique narrow pore size distribution around 7 A and with uniform structure, has been electrochemically characterised using the single particle microelectrode technique. The carbon has been used as electrode material for supercapacitors. This type of capacitors is used as high power energy buffers in hybrid vehicles and for stationary power backup. The principle for the microelectrode technique consists of connecting a carbon particle with a carbon fibre by means of a micromanipulator. The single particle and carbon fibre together form a microelectrode. Combination of this technique with electroanalytical methods such as cyclic voltammetry and potential step measurements allows for the survey of electrochemical phenomena and for the determination of ion transport parameters inside the nanopores. A mathematical model based on Fick’s second law, for diffusion of ions inside the nanopores at non steady state, was used for the determination of effective diffusion coefficients (Deff). The coefficients were calculated from an asymptotic solution of Fick’s equation, applied for a thin layer adjacent to the external surface of the carbon particles and valid for the current response in a short time region. Another asymptotic solution was obtained, using spherical geometry and valid for the current response in a long time region. In this doctoral work, the carbon particles have been exposed to potential cycling, which mimics that of large electrodes during operation of a double layer capacitor. The potential-current response, E-I, for the nanoporous carbon, shows a pure capacitive behaviour between –0.5 V and 0.1 V vs. the Hg|HgO reference electrode. The detection of the faradaic processes beyond these potentials was possible by lowering of the voltammometric sweep rate. The electrochemical processes occurring at positive and at negative potential were investigated separately. Cyclic voltammometric measurements showed that the chemisorption of hydroxyl groups, occurring between 0.1 and 0.3 V, leads to a mild oxidation of the carbon structure, resulting in surface groups containing an oxygen atom at a specific carbon site (e.g., phenolic or quinine type). These oxygen-containing surface groups caused an increase of the specific capacitance, which remained constant throughout a number of voltammometric cycles. The Deff decreased on the other hand with the number of cycles. The Deff decreases also with the positive potential. The evaluation of Deff indicates adsorption of hydroxyl groups and an increase of the effective tortuosity of the pore system. The oxidation of the carbon particles, between 0 and 0.5 V, leads to more extensive oxidation and to surface groups containing two oxygen atoms at a single carbon site, followed by formation of carbonate ions. The oxygen-containing surface groups and carbonate ions formed at these potentials do not contribute to the specific capacitance and drastically retard or obstruct the ion transport inside the nanopores. At negative potentials the carbon particles show a dominantly capacitive behaviour. The faradaic processes taking place below –0.5 V vs. Hg|HgO reference electrode are generation and adsorption of hydrogen. These processes do not perturb significantly the electrochemical and ion transport properties of the nanoporous carbon particles. It was found that hydrogen generation occurs at –0.5 V vs. Hg|HgO and that two hydrogen oxidation processes take place at positive potentials. The results indicate that the weakly adsorbed hydrogen undergoes oxidation between 0 and 0.1 V and that the strongly adsorbed hydrogen is oxidised at more positive potentials. The single particle technique was adapted for the determination of diffusion coefficients of an organic electrolyte. The different size of the anions and cations caused different transport characteristics at negative and positive potentials. Slow cycling was found important for ion penetration inside the nanopores and for the evaluation of the effective diffusion coefficients. The effective diffusion coefficients for the nanoporous carbon using aqueous 6M KOH and 0.1M TEABF4 in acetonitrile were estimated to 1.4 (±0.8).10-9 cm2 s-1 and 1.3 (±0.4) 10-8 cm2 s-1, respectively.