Polymer electrolyte films based on poly(trimethylene carbonate) (PTMC) mixed with LiTFSI salt in different compositions were synthesized and investigated as electrolytes for lithium ion batteries, where the ionic conductivity is the most interesting material property. Electrochemical impedance spectroscopy (EIS) and DSC were used to measure the ionic conductivity and thermal properties, respectively. Additionally, FTIR and Raman spectroscopy were used to examine ion coordination in the material. Additives of nanosized TiO2 and powders of superionically conducting Li1.3Al0.3Ti1.7(PO4)3 were investigated as enhancers of ionic conductivity, but no positive effect could be shown. The most conductive composition was found at a [Li+]:[carbonate] ratio of 1, corresponding to a salt concentration of 74 percent by weight, which showed an ionic conductivity of 2.0 × 10–6 S cm–1 at 25 °C and 2.2 × 10–5 S cm–1 at 60 °C, whereas for even larger salt concentrations, the mechanical durability of the polymeric material was dramatically reduced, preventing use as a solid electrolyte material. Macroscopic salt crystallization was also observed for these concentrations. Ion coordination to carbonyls on the polymer chain was examined for high salt content compositions with FTIR spectroscopy, where it was found to be relatively similar between the samples, possibly indicating saturation. Moveover, with FTIR, the ion-pairing was found to increase with salt concentration. The ionic conductivity was found to be markedly lower after 7 weeks of aging of the materials with highest salt concentrations.

The polymer electrolyte membrane fuel cell (PEMFC) converts the chemical energy of hydrogen and oxygen (air) into usable electrical energy. At the cathode (the positive electrode), a considerable amount of platinum is generally required to catalyse the sluggish oxygen reduction reaction (ORR). This has implications regarding the cost in high-power applications, and for making a broad commercialisation of the PEMFC technology possible, it would be desirable to lower the amount of Pt used to catalyse the ORR. In this thesis a number of techniques are described that have been developed in order to investigate catalytic activity at the cathode of the PEMFC. These methodologies resemble traditional three-electrode research in liquid electrolytes, including cyclic voltammetry in inert gas, but with the advantage of performing the experiments in the true PEMFC environment. From the porous electrode studies it was seen that it is possible to reach mass activities close to 0.2 gPt/kW at potentials above 0.65 V at 60 ◦C, but that the mass activities may become considerably lower when raising the temperature to 80 ◦C and changing the measurement methodology regarding potential cycling limits and electrode manufacturing. The model electrode studies rendered some interesting results regarding the ORR at the Pt/Nafion interface. Using a novel measurement setup for measuring on catalysed planar glassy carbon disks, it was seen that humidity has a considerable effect on the ORR kinetics of Pt. The Tafel slopes become steeper and the activity decreases when the humidity level of the inlet gases decreases. Since no change in the the electrochemical area of the Pt/Nafion interface could be seen, these kinetic phenomena were ascribed to a lowered Pt oxide coverage at the lower humidity level, in combination with a lower proton activity. Using bi-layered nm-thick model electrodes deposited directly on Nafion membranes, the behaviour of TiO2 and other metal oxides in combination with Pt in the PEMFC environment was investigated. Kinetically, no intrinsic effect could be seen for the model electrodes when adding a metal oxide, but compared to porous electrodes, the surface (specific) activity of a 3 nm film of Pt deposited on Nafion seems to be higher than for a porous electrode using ∼4 nm Pt grains deposited on a carbon support. Comparing the cyclic voltammograms in N2, this higher activity could be ascribed to less Pt oxide formation, possibly due to a particle size effect. For these bi-layered films it was also seen that TiO2 may operate as a proton-conducting electrolyte in the PEMFC. / I polymerelektrolytbränslecellen (PEMFC) omvandlas den kemiska energin hos vätgas och syrgas (luft) direkt till användbar elektrisk energi. På katoden (den positiva elektroden) krävs betydande mängder platina för att katalysera den tröga syrereduktionsreaktionen (ORR). Detta inverkar på kostnaden för högeffektsapplikationer, och för att göra en bred kommersialisering av PEMFC-teknologin möjlig skulle det vara önskvärt att minska den Pt-mängd som används för att katalysera ORR. I denna avhandling beskrivs ett antal tekniker som utvecklats för att undersöka katalytisk aktivitet på katoden i PEMFC. Metodiken liknar traditionella treelektrodexperiment i vätskeformig elektrolyt, med cyklisk voltammetri i inert gas, men med fördelen att försöken utförs i den riktiga PEMFC-miljön. I försök med porösa elektroder visades att det är möjligt att nå massaktiviteter nära 0.2 gPt/kW för potentialer över 0.65 V vid 60 ◦C, men massaktiviteterna kan bli betydligt lägre om temperaturen höjs till 80 ◦C, och om potentialsvepgränser och elektrodentillverkningsmetod ändras. Försök med modellelektroder resulterade i intressanta resultat rörande ORR i gränsskiktet Pt/Nafion. Genom att använda en ny metodik för att mäta på katalyserade plana elektroder av vitröst kol (glassy carbon), var det möjligt att se att gasernas fuktighet har en betydande inverkan på ORR-kinetiken hos Pt. Tafellutningarna blir brantare och aktiviteten minskar när inloppsgasernas fuktighetsgrad minskar. Eftersom den elektrokemiska arean hos Pt/Nafion-gränsskiktet inte ändrades, ansågs dessa kinetiska effekter bero på en lägre täckningsgrad av Ptoxider vid lägre fuktigheter, i kombination med lägre protonaktivitet. Genom att använda Nafionmembran belagda med nm-tjocka tvåskiktsmodellelektroder undersöktes hur Pt i kombination med TiO2 och andra metalloxider verkar i PEMFC-miljön. Kinetiskt sett hade tillsatsen av metalloxider ingen inre påverkan på aktiviteten, men vid jämförelse med porösa elektroder tycks den specifika ytaktiviteten vara högre hos en 3 nm film av Pt på Nafion än för en porös elektrod baserad på ∼4 nm Pt-korn belagda på ett kolbärarmaterial. Jämför man de cykliska voltammogrammen i N2, kan den högre aktiviteten tillskrivas en lägre grad av Pt-oxidbildning, vilket i sin tur kan bero på en storlekseffekt hos Pt-partiklarna. Försöken med dessa tvåskiktselektroder visade också att TiO2 kan verka som protonledande elektrolyt i PEMFC. / QC 20100706