Rechargeable lithium-ion batteries have both the power and energy capabilities to be utilized in hybrid electric vehicles and other power demanding applications. However, there are obstacles primarily related to reliability in safety and lifetime. Additionally, there is still room for improvement in the battery performance. In this work, physics-based mathematical models have been successfully set-up and numerically solved to investigate performance, safety, and aging in lithium-ion battery systems. This modeling approach enabled a detailed analysis of the electrochemical processes related to these issues. As the models included many parameters and spatial resolution of several variables with time or frequency, strategies for investigation needed to be developed for most of the work. The accuracy of the investigation was consolidated by the utilization of parameters characterized from experimental work. The performance expressed in terms of polarization was determined for a power-optimized battery cell undergoing various operating conditions. A methodology that separated and quantified the contribution of each process to the polarization was set up, allowing the study of the contributions as a snapshot in time and as an average over a cycle. Mass transport in electrolyte was shown to be a crucial feature to improve especially if the battery is expected to undergo high current-loads for long periods of time. Safety-concerns when a battery cell is short-circuited were investigated for three types of short-circuit scenarios. All scenarios raised the temperature to the point where exothermic side reactions were initiated. The similarities between the scenarios in temperature increase were a result of the limiting current being reached. The differences, however small, were related to the placement of the short-circuit. Especially when the current collectors were not directly connected by the short circuit, an increased electronic resistance was observed which lowered both the generated current and heat. The aging of a battery cell was investigated by model analysis of electrodes harvested from fresh and aged cells. A methodology was used where a frequency-dependent model was fitted to three-electrode impedance experiments by tuning parameters associated to electrode degradation. For cycled cells, electrolyte decomposition products inhibiting the mass transport in the electrolyte and particle cracking in the positive electrode increased the impedance. A similar model was also set up for investigation of the lithium intercalation processes in PAN-based carbon fibers, showing it to have both good mass transport and kinetic capabilities. / Laddningsbara litiumjonbatterier har både ur energi- och effektsynpunkt möjligheten att kunna användas i elhybridfordon och inom andra effektkrävande tillämpningsområden. Batteriets säkerhet och livslängd är dock inte helt tillförlitliga. Dessutom finns det fortfarande utrymme för förbättringar av litiumjonbatteriets prestanda. I det här arbetet har matematiska modeller baserade på fysikaliska egenskaper framgångsrikt ställts upp och lösts numeriskt för att studera prestandan, säkerheten samt åldrandet hos litiumjonbatterisystem. Denna typ av modellering gjorde det möjligt att detaljerat analysera hur de elektrokemiska processerna bidrar. Eftersom modellerna omfattade ett stort antal parametrar och har variabler som förändras i åtminstone en dimension med tid eller frekvens, krävdes det att tydliga strategier för arbetet ställdes upp. Modelleringsstudiens noggrannhet stärktes av att flertalet av de använda parametrarna hade bestämts experimentellt. Polarisationen som ett mått på prestanda bestämdes för ett effektoptimerat batteri under olika laster. En metodik som separerar och beräknar hur mycket varje process bidrar till polarisationen skapades och användes för att studera bidragen över tid eller över en hel lastcykel. Resultaten visade att masstransporten i elektrolyten påverkar till stor del och bör förbättras om batteriet förväntas belastas med hög ström under lång tid. Säkerheten i samband med kortslutning av en battericell undersöktes för tre olika fall av kortslutningar. Alla fall uppvisade en temperaturökning som skulle kunna bidra till att exoterma reaktioner startas och termisk rusning uppstår. Temperaturökningen var liknande i samtliga kortslutningsfall och berodde på att gränsströmmen nåddes inom cellen. Skillnaderna mellan kortslutningsfallen var inte så betydande men kunde härledas till kortslutningens placering. Framförallt fallet då strömtilledarna inte kontakterades av kortslutningen observerades en ökad elektronisk resistans som sänkte både strömmen och värmeproduktionen. Åldringen i en battericell undersöktes genom modellanalys av elektroder som tagits från nya eller åldrade celler. Som metod användes en frekvensberoende modell som anpassades till tre-elektrod-impedansmätningar genom förändring av parametrar som beskriver elektrodnedbrytning. Då cellerna cyklats, visade förändringen av dessa parametrar att impedansen ökar på grund av nedbrytningsprodukter från elektrolyten som hindrar masstransporten och att det aktiva materialet i positiva elektroden spricker. En liknande modell användes också till att undersöka PAN-baserade kolfibrers förmåga att interkalera litium och resultaten visade på att den har mycket goda elektrokemiska egenskaper. / <p>QC 20130520</p>

Organic electronics is a hot and modern topic which holds great promise for present and future applications. One such application is the light-emitting electrochemical cell (LEC). It can be fully solution processed and driven at low voltage providing light emission from a large surface. Inkjet printers available today can print a variety of inks, both solutions and dispersions. The technique is scalable and a quick and easy way to accurately deposit small quantities of material in user definable patterns onto a substrate. This is desirable to make low cost and efficient optical devices like displays. In this thesis it has been shown that solid electrolytes, after being dissolved in a liquid solvent, can be inkjet printed into a set of well separated distinct drops with an average maximum thickness of 150 nm. The electrolytes are commonly used in LECs and comprised by poly(ethylene glycol) with molar masses ranging from 1 – 35 kg/mol, and potassium trifluoromethanesulfonate (KCF3 SO3 )—together dissolved incyclohexanone to form an ink. The smallest achieved edge to edge distance between the printed drops was 40 μm. Together with a drop diameter of 50 μm it yields a coverage of 24% at a resolution of 280 dpi. Profiles of dried deposited drops of electrolyte were examined with a profilometer, which showed adistinct coffee ring effect on each drop. In particular, the ridges of the coffee rings were broken into pillar like shapes, together forming a structure akin to a scandinavian ancient remnant called stone ship. Different drop diameters were measured in and between the indium tin oxide samples. The drops’ speeds and sizes atejection from the nozzles seemed unchanged, and wettability is most probably the physical phenomena tolook into in order to understand what generates the differences. Local changes in surface roughness and/or surface energy, possibly originating from the cleaning process of the samples, is most likely the cause. No indications towards large differences in surface tension between the printable inks were seen, however their viscoelastic properties were not measured. As part of the thesis work a LEC characterization set-up was built. It drives a LEC at constant currentand measures the driving voltage, -current, and luminance over time. The set-up is controlled by a Labview virtual instrument and the data exported to a text-file for later analysis. The precision of the luminance measurements is ±0.1 cd/m2 for readings &lt; 50 cd/m2 , but the accuracy is uncertain. The conclusion of this thesis is that it is indeed possible to print solid electrolytes dissolved in cyclo-hexanone with an inkjet printer. However, in order to fully understand the spreading and drying of thedrops, studies of the inks’ viscoelastic properties, together with surface roughness and -energy density ofthe substrates, are needed. The largest molar mass of nicely printable poly(ethylene glycol), at an ink concentration of 10 mg/ml, was 35 kg/mol. This is comparable to the molar mass of an active light-emittingmaterial, “SuperYellow”, often used in LECs. Even though their respective molecular structures are very different, this indicates that inkjet printing of complete LEC-inks, containing both the active material and solid electrolyte, is feasible. Most probably it would require substantial tuning of the printing parameters. This thesis provides further hope for future fully inkjet printed LECs.