Sammanfattning på svenska: I nutiden, forskning och innovationer båda från akademi och industri försätter för att minska effekterna från klimatförändring. Ett av många viktiga område där utvecklingen fortsätter är litiumjonbatterier (LIB). På grund av den ökade energiförbrukningen i många områden (främst transporter) har ökat fossila bränsleförbrukningar och orsakat behovet av energi att lagras mer. Samhället kan inte bara fokusera på global miljövänlig batteriproduktion för att lösa detta problem. Samtidigt är det nödvändigt att koncentrera på hur man utvärderas begagnade batterierna som vi redan har. Återvinning av litiumjonbatterier har därför börjat få en ökad betydelse. Utmaningar för batteri återvinning är energi kravet för steg på processen och andra processer kan orsaka att skadliga ämnen släpps ut i naturen. Därför är det mycket viktigt att veta hur ett batteri påverkas av interna och externa förändringar från första till sista steget i återvinning och hur detta kommer att påverka de andra stegen. Detta examensarbete fokuserar på lösningsbaserade urladdningssteget i LIB-återvinning och syftar till att hitta den optimal temperatur genom att utforska möjliga förändringar som observerats på katodmaterialet. Inom ramen för projektet planerades temperaturoptimeringsstudien att göras genom att kombinera kemiska förändringar både inom och utanför batteriet i lösningsurladdningen. Detta är med en diskussion om särskilt fokus på att uppnå en hållbar återhämtning och kvaliteten på katodmaterialet. / In today's world, where global warming is felt in every sense, Research & Development (R&D) studies are continuing rapidly both in companies and in research networks to minimize its effects. One of the most important areas where developments continue is on lithium-ion batteries (LIBs). The increased energy consumption in many areas (mainly transportation), has increased fossil fuel consumption and caused the need for energy to be stored more. In this sense, focusing on only global-environmentally friendly battery production is insufficient to solve this problem. At the same time, it is necessary to concentrate on how to evaluate the used batteries that we already have. Therefore, lithium-ion battery recycling has begun to gain importance. Challenges for battery recycling are that some of the processes require energy inputs and others can generate harmful substances that require containment. Therefore, it is very important to know how a battery is affected by internal and external changes from the first to the last stage of recycling and how this will affect the other stages. This master thesis focuses on the solution discharge step in LIB recycling and aims to find the optimum temperature range for the discharge step of LIB recycling by exploration of the possible changes observed on the cathode material. In the scope of the project, the temperature optimization study was done by combining the chemical changes both inside and outside of the battery in the solution discharge. This is with a discussion of a particular focus on achieving a sustainable recovery and the quality of cathode material.

Målet med projektet var att undersöka samt implementera en fysikbaserad DFN modell för att simulera kalender samt cyklingåldrande av litiumbatterier som används i elbilar. Den fysikbaserade modellen var konstruerad baserad på ett Python biblioteket vid namn PyBaMM, vilket till skillnad från datadrivna modeller ger essentiell information om de kemiska processerna inuti batteriet. Den första delen av projektet täcker konceptet av kalenderåldring, vilket inkluderar en jämförelse mellan tre olika tre olika hastighetsbegränsande SEI modeller. Parametrar som påverkar det erhållna resultatet från modellen är identifierade, estimerade, och till slut validerade för att säkerhetsställa att modellen och parametrarna är identifierbara gentemot experimentella data. Resultatet av jämförelsen gav att SEI tillväxt begränsad av litium interstitiell diffusion är den mest optimala modellen att applicera när kalenderåldring för litiumbatterier ska modelleras. Resultaten visade också att endast en parameter, inre SEI litium interstitiell diffusivitet ska justeras för att erhålla optimal anpassning mot experimentella data. Andra delen av projektet använde resultatet från den första delen och litium plätering implementerades som en andraåldringsmekanism som undersöktes under tre olika laddningsprotokoll. Modellen var optimerad och anpassad gentemot experimentella data, där parametervärdet för kinetisk hasighetskonstanten för plätering var estimerad. Den optimerade modellen användes därefter för att erhålla mer information om elektrokemiska variabler för att kunna analysera samt beskriva åldringsprocessen utan att behöva genomföra praktiska laborationer. Resultaten visade att mängden pläterat litium på den negativa elektroden ökade för celler som var exponerade till högre ström under laddningsprocessen, samt när cellerna var laddade vid höga SoC nivåer. Sammanfattningsvis, visade modellen hög potential att representera och evaluera experimentella data, samt tillhandahålla en inblick i elektrokemiska processer och kapacitetsförluster länkade till SEI tillväxt och litium plätering. Däremot, för att erhålla en högre grad noggrannhet av elektrokemiska åldringsmekanismer i litiumbatterier, fler ytterligare mekanismer måste implementeras såsom mekanisk stress av både negativ och positiv elektrod. / The aim of this study was to investigate and apply a physics-based DFN model to simulate the calendar and cycling ageing of lithium-ion batteries manufactured for EV applications. The physics-based cell ageing model was constructed based on the open-source software Python library PyBaMM, which in comparison to data-driven models provides more essential information about the chemical process within the battery cell. The first part of the project covers the concept of calendar ageing which includes comparisons between three different rate-limiting SEI growth models. Parameters that affect the output from the physics-based model are isolated, estimated with numerical methods, and lastly validated to ensure that the model and the parameters rep- resent the physics behind the experimental data. It was found that the SEI growth limited by lithium interstitial diffusion is the most optimal model to apply for a physics-based model when modeling calendar ageing. It was also found that the only parameter that should be tuned against experimental data is the inner SEI lithium interstitial diffusivity. The second part of the project utilizes the results from the first part and introduces lithium plating as a second cell ageing mechanism under three different charging protocols. The model was optimized and fitted against experimental data by sweeping the lithium plating kinetic rate constant parameter. The optimized model was thereafter used to generate outputs that more thoroughly can explain the degradation effects of the cell without constructing real-world experiments. Where increased rate of plated lithium could be observed for the cell subjected to higher charging C-rate, and when the cells were charged at high SoC levels. To summarize, the model showed great potential in representing and evaluating the experimental data and providing the project with insight into the electrochemical processes and cell capacity losses of SEI growth and lithium plating. However, in order to achieve a higher accuracy of cell ageing model in relation to the lithium-ion cells used in customer vehicles, several additional cell degradation mechanisms have to be introduced, such as mechanical degradation of the two electrodes.

Doped ZnO nanoparticles were synthesized by three different methods – electrochemical deposition under oxidizing conditions (EDOC) , combustion method and wet chemical synthesis – for investigating the oxygen gas sensing response. Ga-doped ZnO was mostly synthesized but also In-doped ZnO was made. The samples were analyzed by XRD, SEM, EDX and TEM. Gas response curves are given alongside with Langmuir fitted curves and data for pure ZnO and Ga-doped ZnO. DFT quantum chemical investigation of cluster models ZnO nanoparticles were performed to evaluate defect effects and oxygen and nitrogen dioxide reactions with the ZnO surface. Defects were investigated by DOS and HOMO-LUMO plots , and are oxygen vacancy, zinc vacancy, zinc interstitial and gallium doping by replacing zinc with gallium. Oxygen and nitrogen dioxide reactions were investigated by computing Mulliken charges, bond lengths, DOS spectra and HOMO-LUMO plots.

The aim of the project was to develop a method to measure and studythe degree of activation of the negative electrode (MH) in a NiMH battery.This was done by characterization of the gases produced during charge of a battery – O2 and H2 – using a Gas Chromatograph. The current applied in the very first charge of the battery was varied in order to examine how this affects the gas evolution. In the developed method, batteries were charged to 8Ah with 9A, after which a gas sample was taken and analyzed with Gas Chromatography. An additional goal was to use the method to examine the difference in activation between virgin and recycled negative electrode material. A module charged stepwise with 0.07C followed by 0.2C had the lowest share of H2 after two cycles, indicated best activation. However, a higher amount of H2 in the beginning of the activation process could possibly enhance the degree of activation during the following cycles. The method indicated that the module with recycled MH was better activated than the virgin MH. To improve the technique, repeated measurements to get better statistics should be done. Gas samples should be taken at dV/dt=0 in order to take samples at same SoC. The charge current should be adjusted so that the same C rate is always used. This would make the results easier to interpret.

Electrochemical systems, which rely on coupled phenomena of the chemical change and electricity, have been utilized for development an interface between biological systems and conventional electronics.  The development and detailed understanding of the operation mechanism of such interfaces have a great importance to many fields within life science and conventional electronics. Conducting polymer materials are extensively used as a building block in various applications due to their ability to transduce chemical signal to electrical one and vice versa. The mechanism of the coupling between the mass and charge transfer in electrochemical systems, and particularly in conductive polymer based system, is highly complex and depends on various physical and chemical properties of the materials composing the system of interest. The aims of this thesis have been to study electrochemical systems including conductive polymer based systems and provide knowledge for future development of the devices, which can operate with both chemical and electrical signals. Within the thesis, we studied the operation mechanism of ion bipolar junction transistor (IBJT), which have been previously utilized to modulate delivery of charged molecules. We analysed the different operation modes of IBJT and transition between them on the basis of detailed concentration and potential profiles provided by the model. We also performed investigation of capacitive charging in conductive PEDOT:PSS polymer electrode. We demonstrated that capacitive charging of PEDOT:PSS electrode at the cyclic voltammetry, can be understood within a modified Nernst-Planck-Poisson formalism for two phase system in terms of the coupled ion-electron diffusion and migration without invoking the assumption of any redox reactions. Further, we studied electronic structure and optical properties of a self-doped p-type conducting polymer, which can polymerize itself along the stem of the plants. We performed ab initio calculations for this system in undoped, polaron and bipolaron electronic states. Comparison with experimental data confirmed the formation of undoped or bipolaron states in polymer film depending on applied biases. Finally, we performed simulation of the reduction-oxidation reaction at microband array electrodes. We showed that faradaic current density at microband array electrodes increases due to non-linear mass transport on the microscale compared to the corresponding macroscale systems.  The studied microband array electrode was used for developing a laccase-based microband biosensor. The biosensor revealed improved analytical performance, and was utilized for in situ phenol detection.

Perovskite based materials have great potentials for various energy applications and the search for new materials for uses in SOFCs has largely been concentrated to this class of compounds. In this search, we have studied perovskite phases in the system La2Co1+z(Ti1-xMgx)1-zO6, with 0  x 0.9 and z = 0.0, 0.2, 0.4, 0.6. Crystal structures were characterized by XRD and, for selected compositions, also by NPD and SAED. They exhibit with increasing x, as well as increasing z, a progressive increase in symmetry from monoclinic to orthorhombic to rhombohedral. The main focus in this work has been on the investigation of structure-property relations for compositions with 0.0 x 0.5 and z = 0. The nominal oxidation state of Co increases for these with increasing x, from Co2+ for x = 0 to Co3+ for x = 0.5. Magnetic measurements and XANES studies showed that the average spin state of Co changes linearly with increasing x, up to x = 0.5, in accordance with varying proportions of Co with two fixed oxidation states, i.e. Co2+ and Co3+. The data suggests that the Co3+ ions have an IS spin state or a mixture of LS and HS spin states for all compositions with nominally only Co2+ and Co3+ ions, possibly with the exception of the composition with x = 0.1, 0.2 and z = 0, for which the data indicate that the spin state might be HS. The XANES data indicate furthermore that for the perovskite phases with z = 0 and x > 0.5, which in the absence of O atom vacancies contain formally Co4+, the highest oxidation state of Co is Co3+, implying that the substitution of Ti4+ by Mg2+ for x ³ 0.5 effects an oxidation of O2- ions rather than an oxidation of Co3+ ions. The thermal expansion was found to increase nearly linearly with increasing oxidation state of Co. This agrees well with findings in previous studies and is attributable to an increase in the ionic radius of Co3+ ions with increasing temperature, due to a thermal excitation from a LS to IS or LS/HS spin states. High temperature electronic conductivity measurements indicate that the electronic conductivity increases with an increase of both relative and absolute amount of Co3+. The latter can be attributed to an increase in the number of Co-O-Co connections. Additional high temperature magnetic measurements for selected samples, whose susceptibilities did not follow a Curie law behaviour up to room temperature, showed effective magnetic moments that did approach plateaus even at high temperatures (900 K). Interpretations of these data are, however, hindered by the samples losing oxygen during the applied heating-cooling cycle. The present study has shown that the investigated system is suitable for further studies, of more fundamental character, which could provide further insight of the structure-property relationships that depend on the oxidation state of Co. / Studies of cobalt based perovskites for cathode materials in solid oxide fuel cells.

The promising role resistive random-access memory (RRAM) plays in the imminent reality of wearable electronics calls for a new, updated physical model of their operating mechanism. Their high applicability as the next-generation flexible non-volatile memory (NVM) devices has promoted the recent emergence of a novel ultra-thin (< 5nm) organic/inorganic hybrid dielectric RRAM. A deep understanding of their resistive switching (RS) behavior is required to unlock their suitability in future electronics applications. However, the extremely reduced thicknesses bring about new challenges in terms of material characterization sample processing, while the RS observations through electrical characterization techniques lack uniformity in the key switching parameters, thus hindering the identification of any clear trends.  This work studies the RS mechanism in ultra-thin Al/Hf-hybrid/Ni RRAM devices through uniformity-improved electrical observations. First, the focus is to implement a ramped-pulse train method during the reset process to reduce the dispersion of the voltage and resistance fluctuations at different starting voltage amplitudes and pulse widths. After finding the optimal electrical programming conditions for reduced parameter dispersions, a temperature test was performed to study the contributions of the metal ions and oxygen vacancies (V2+) in the switching layer. Finally, a physical model describing the operating mechanism in flexible RRAM is proposed after the close observation and study of the processed devices. The model is based on the coexistence of a hetero-metallic portion composed of Al and Hf3Al2, and a V2+ portion connected to form the hybrid conducting filament (CF) and turning the device on. The CF forming processes emphasize the strong presence of these vacancies partaking in RS, as the temperature dependence results suggest the majority of their concentration to be generated during this step. Also, the different electrical potential, temperature, and concentration gradients influencing the V2+ migration during RS may explain some of the failure mechanisms in the rupture and the re-forming of the filament. Additionally, the possible presence of a thin Al-oxide layer in the Al/Hf-hybrid interface may give a reason for leaky on-states. A detailed physical model of the RS mechanism in next-generation flexible RRAMs is key to learn to unlock a range of emerging technologies fitted to today’s needs. / Den senaste introduktionen av ultratunn (<5 nm) organisk-oorganisk hybrid dielektrisk RRAM som nästa generations icke-flyktiga minnesenheter kräver en djup förståelse för hybridskiktresistiv växling (RS). Den extremt reducerade tjockleken hindrar emellertid deras bearbetbarhet för materialkarakteriseringstekniker. Dessutom hindrar den dåliga enhetligheten i viktiga omkopplingsparametrar fortfarande i RRAM att alla trender kan definieras tydligt genom elektrisk karakterisering. Detta arbete använder elektrisk manipulation genom en RPS-metod (ramped-pulse series) för att förbättra spännings- och motståndsfluktuationerna i återställningsprocessen för ultratunna Al/Hf-hybrid/Ni-enheter vid olika spänningsamplitud, pulsbredd och temperaturförhållanden. Från de erhållna RPS-optimerade resultaten föreslås en ny och detaljerad fysisk modell som beskriver driftsmekanismen. Samexistensen i den ledande filamenten (CF) av en hybridmetalldel, sammansatt av Al och Hf3Al2, och en syrevakansdel bekräftas. Vår modell betonar vakansbidraget i RS, där majoriteten genereras under CF-formningsprocessen och deltar i olika grad i filamentbrottet för RPS och ingen RPS-bearbetade enheter via Joule-uppvärmning, drift och Fick-krafter. Dessutom förklaras kopplingsfelhändelser baserat på närvaron av ett Al2O3-lager i Al/Hf-hybridgränssnittet.

A fairly new technology used to produce metallic components is powder metallurgy (PM). Among the advantages with this technique are decreased cost of production for complex-shaped parts, new alloys are made possible, reduced end processing, less material loss, and vibrational damping effects. The downside is the number of pores created which can alter the tribological properties of the material. The focus of this report is to investigate how lean PM steel behaves under tribological contacts.  Friction and wear will be investigated using a pin-on-disc setup to mimic the sliding part of a gear tooth mesh. Previous studies show that the amount of wear, and if the wear increases or decreases with increased density is dependent on the degree of porosity and the pore size. This means that the wear might be minimized by optimizing the number of pores in the material and their shape and size. The result of this study shows that the friction coefficient decreases with increasing density. The wear coefficient show signs of the same correlations but further tests are needed. The main wear comes from adhesive wear, with signs of abrasive wear. The amount of abrasive wear seems to increase with an increase in density, supporting previous studies claiming that pores can trap wear debris and decrease the number of abrasive particles in the contact.

The direct variable costs for heat and electricity production based on solid biomass fuel combustion is approximately 3-5 times lower than the costs in a fossil fuel-oil based boiler in Sweden. In addition waste derived biomass fuels are typically much cheaper than biomass not classified as waste. The introduction of the waste derived fuels; wastewater treatment sludge, demolition wood, and animal waste in a 50MWth circulating fluidized bed (CFB) biomass boiler located in Perstorp, Sweden, led to rapid deposit buildup in superheaters, heavy ash accumulation in economizers and failing boiler tubes and vortex finders that forced frequent boiler shutdowns. This in turn increased the use of expensive oil (fossil fuel) in backup boilers and the CO2 footprint of the on-site energy conversion system. This work aims to increase the general mechanistic understanding of combustion systems using complex fuels, and includes: A mapping of the boiler failure and preventive maintenance statistics; elemental composition analysis of ash, deposits and fuel fractions; flue-gas composition measurements; chemical speciation analysis; an attempt to describe the overall ash transformation reactions and mass balance throughout the combustion process. Scanning electron microscope (SEM) equipped with energy dispersive X-ray spectroscopy (EDS) was used to analyze the elemental composition of ash and deposits. The SEM-EDS results were used together with data from X-ray powder diffraction (XRD) analysis, thermodynamic phase data, and equilibrium calculations in an attempt to quantify the crystalline phases and the overall ash transformation of the process. Based on the findings concerning ash transformation and the failure statistics, it has been possible to identify generic key parameters regarding boiler design and process parameters, enabling major improvements of the CFB boiler availability, a lower overall energy conversion cost and a reduced CO2 footprint. / Den direkta rörliga kostnaden för värme-och elproduktion baserad på fast biobränsle är ungefär 3-5 gånger lägre än kostnaden för fossiloljebaserad produktion. Avfallsklassade fasta biobränslen är vidare oftast betydligt billigare än fasta biobränslen som inte är klassade som avfall. Införandet av de avfallsklassade bränslena; reningsslam, rivningsvirke, och animaliskt avfall i en 50MWth cirkulerande fluidiserad bädd (CFB) -panna, ledde till kraftig beläggningstillväxt i överhettare och ackumulering av aska i ekonomisers, samt haveri av panntuber och centrumrör i cyklonerna, som tvingade fram frekventa pannstopp. Detta ökade i sin tur användningen aveldningsolja (fossilt bränsle) i reservkrafts-pannor vilket resulterade i ett större CO2 utsläpp och en högre kostnad för energiomvandlingen på siten. Detta arbete syftar till att öka den allmänna mekanistiska förståelsen av förbränningssystem som använder komplexa bränslen, och omfattar; haveri- och underhållsstatistik, elementarsammansättningsanalys av aska, beläggningar och bränslefraktioner, rökgasens sammansättning, kemisk specificering av askor och beläggningar, ett försök att beskriva de övergripande askomvandlingsreaktionerna, samt en massbalans för förbränningsprocessen. Svepelektronmikroskop (SEM) utrustat med energidispersiv röntgenspektroskopi (EDS) användes för att analysera den elementära sammansättningen av aska och beläggningar. SEM-EDS-resultaten användes tillsammans med pulverröntgendiffraktionsanalys (XRD), termodynamiska fasdata, och jämviktsberäkningar i ett försök att kvantifiera de kristallina faserna och de övergripande askomvandlingsreaktionerna i processen. Baserat på resultaten rörande askomvandling och haveristatistik, har det varit möjligt att identifiera generiska nyckelparametrar gällande panndesign och processparametrar, som möjliggjort stora förbättringar av CFB pannans tillgänglighet, en lägre totalkostnad för energiomvandlingen på siten samt ett minskat CO2-utsläpp.

Over the past decades, evidence show that the anthropogenetic greenhouse gases (GHG) emissions of carbon dioxide (CO₂) and methane (CH₄) are the main drivers behind global warming and are becoming stronger. Globally, hydropower is among the main sources of renewable energy and the popular notion that hydropower electricity is carbon neutral has been under debate as evidence from measurements in different regions of the globe show significant and highly variable carbon emissions from hydropower reservoirs. But these global estimates are still highly uncertain since they are restricted to a few locations in the south of Europe, North America, and South America, and lack both the temporal and spatial variability in addition to some of the flux pathways (often downstream emission and degassing). This study assesses the CH4 and CO₂ emissions from reservoirs associated to three small hydropower stations in the south of Sweden and aims to understand potential spatial and temporal variability in the temperate region. The study performed flux measurements of CH4 and CO₂, an analysis of CH4 and DIC concentration in the water, and a depth profile of temperature, DO, CH4 and DIC at the hydropower station’s reservoirs. In summation this study finds significant CH4 and DIC concentrations, as well as CH4 and CO₂emissions from the studied reservoirs. The findings of this study underline the notion that hydropower might be a `blind spot` in the Swedish GHG budget report, and if so, the carbon emissions from hydropower electricity need to be re-evaluated.