De par sa capacité spécifique théorique dix fois plus élevée que celle du graphite actuellement utilisé comme matériau actif d'anode pour les batteries Li-ion, le silicium peut jouer un rôle important dans l'augmentation de la densité d'énergie de ces systèmes. La réaction d'alliage mise en place lors de sa lithiation se traduit cependant par une forte expansion volumique du silicium (~300 % contre seulement ~10 % pour le graphite), conduisant à la dégradation structurale de l'électrode, affectant notablement sa tenue au cyclage. Comprendre en détail ces phénomènes de dégradation et développer des stratégies pour limiter leur impact sur le fonctionnement de l'électrode présentent un intérêt indéniable pour la communauté scientifique du domaine. L'objectif de ces travaux de thèse était en premier lieu de développer une technique de caractérisation adaptée à l'observation de ces phénomènes de dégradation et d'en tirer les informations nécessaires pour optimiser la formulation des anodes à base de silicium. Dans ce contexte, nous avons utilisé la tomographie aux rayons X qui présente l'avantage d'être une technique analytique non-destructive permettant le suivi in situ et en 3D des variations morphologiques s'opérant au sein de l'électrode lors de son fonctionnement. Cette technique a pu être adaptée à l'étude de cas du silicium en ajustant les volumes d'électrodes analysés, la résolution spatiale et la résolution temporelle aux phénomènes à observer. Des procédures de traitement d'images adéquates ont été appliquées afin d'extraire de ces analyses tomographiques un maximum d'informations qualitatives et quantitatives pertinentes sur leur variation morphologique. De plus, cette technique a pu être couplée à la diffraction des rayons X afin de compléter la compréhension de ces phénomènes. Nous avons ainsi montré que l'utilisation d'un collecteur de courant 3D structurant en papier carbone permet d'atténuer les déformations morphologiques d'une anode de Si et d'augmenter leur réversibilité en comparaison avec un collecteur de courant conventionnel de géométrie plane en cuivre. Nous avons aussi montré que l'utilisation de nanoplaquettes de graphène comme additif conducteur en remplacement du noir de carbone permet de former un réseau conducteur plus à même de supporter les variations volumiques importantes du silicium. Enfin, la tomographie RX a permis d'étudier de façon dynamique et quantitative la fissuration et la délamination d'une électrode de Si déposée sur un collecteur de cuivre. Nous avons ainsi mis en évidence l'impact notable d'un procédé de "maturation" de l'électrode pour minimiser ces phénomènes délétères de fissuration-délamination de l'électrode. / Because of its theoretical specific capacity ten times higher than that of graphite currently used as active anode material for Li-ion batteries, silicon can play an important role in increasing the energy density of these systems. However, the alloying reaction set up during its lithiation results in a high volume expansion of silicon (~300% compared with only ~10% for graphite) leading to the structural degradation of the electrode, which is significantly affecting its cycling behavior. Understanding in detail these phenomena of degradation and developing strategies to limit their impact on the functioning of the electrode are of undeniable interest for the scientific community of the field. The objective of this thesis work was first to develop a characterization technique adapted to the observation of these degradation phenomena and to draw the necessary information to optimize the formulation of silicon-based anodes. In this context, we have used X-ray tomography which has the advantage of being a non-destructive analytical technique allowing in situ and 3D monitoring of the morphological variations occurring within the electrode during its operation. This technique has been adapted to the case study of silicon by adjusting the analyzed electrode volumes, the spatial resolution and the temporal resolution to the phenomena to be observed. Appropriate image processing procedures were applied to extract from these tomographic analyzes as much qualitative and quantitative information as possible on their morphological variation. In addition, this technique could be coupled to X-ray diffraction to complete the understanding of these phenomena. We have shown that the use of a carbon paper structuring 3D current collector makes it possible to attenuate the morphological deformations of an Si anode and to increase their reversibility in comparison with a conventional copper current collector of plane geometry. We have also shown that the use of graphene nanoplatelets as a conductive additive to replace carbon black can form a conductive network more able to withstand the large volume variations of silicon. Finally, the X-ray tomography allowed studying dynamically and quantitatively the cracking and delamination of an Si electrode deposited on a copper collector. We have thus demonstrated the significant impact of a process of "maturation" of the electrode to minimize these deleterious phenomena of cracking-delamination of the electrode.

Le développement des énergies renouvelables, telles que le solaire photovoltaïque ou l’éolien, est fortement conditionné par la nature intermittente de ces sources d’énergie. Cette intermittence se traduit par un décalage entre pics de production et de consommation. Le stockage de l’énergie électrique revêt donc un caractère primordial dans la gestion de ce décalage. Pour accomplir cette tâche, la technologie lithium-ion est une bonne candidate parmi les technologies de stockage électrochimique de l’énergie. Mais les applications visées exigent des durées de vie bien supérieures à celles requises pour l’électronique portable ou pour les véhicules électriques. En effet les performances des batteries, notamment en termes de capacité, doivent être préservées pendant des durées de 15 à 20 ans. Cette thèse a alors pour but l’étude des mécanismes de vieillissement à long terme d’accumulateurs Li-ion composés d’oxydes lamellaires Li(NixMnyCo1 x y)O2 à l’électrode positive et de graphite à l’électrode négative, en se focalisant sur les interfaces électrode/électrolyte qui sont le lieu privilégié des mécanismes de vieillissement. Ce travail a été réalisé à l'aide de la spectroscopie photoélectronique à rayonnement X (XPS) et de la spectroscopie d’impédance électrochimique (EIS), deux techniques complémentaires particulièrement bien adaptées à l’étude des interfaces, l'une permettant de sonder les environnements chimiques en extrême surface, l'autre donnant la réponse d’un système à une sollicitation électrique sinusoïdale de fréquence variable. La contrainte importante induite par les durées de vie visées (20 ans) ont conduit à simuler le vieillissement à long terme des batteries en leur faisant subir des sollicitations électrochimiques beaucoup plus importantes que lors d’une utilisation normale Les caractérisations par XPS et EIS ont été systématiquement mises en relation avec l’évolution des performances électrochimiques des batteries considérées. Cette étude a permis d'apporter des améliorations aux batteries pour apporter une meilleure réponse à ces phénomènes de vieillissement en termes de maintien des performances: modification de la formulation des électrodes, des électrolytes, de la nature des matériaux actifs, etc. / Development of renewable energy sources such as photovoltaic or wind energy is limited by the intermittent nature of these energy sources. This intermittent nature results in the mismatch between production and consumption peaks. As a result, the storage of electrical energy plays an essential role to manage this mismatch. To this aim, lithium-ion technology appears as a good candidate among other ways of electrochemical storage of energy. However the targeted applications require much greater life span than those commonly admitted for portable electronics or electric vehicles. Battery performances, e.g. rechargeable capacity, should be preserved over 15 or 20 years. This PhD thesis aims at studying the long-term aging mechanisms of Li-ion batteries made up of lamellar oxides Li(NixMnyCo1 x y)O2 at the positive electrode and graphite at the negative electrode. We focused on the electrode/electrolyte interfaces which are the major place of aging processes. The work has been performed by X-ray photoelectron spectroscopy (XPS) and electrochemical impedance spectroscopy (EIS), two complementary techniques especially adapted to the study of interfaces, the former giving access to the chemical environments of atoms at the surface, the latter giving the answer of a system to a sinusoidal electric current with various frequencies. An important technical constraint was the difference between the targeted life span for the application (20 years) and the duration of the thesis (3 years). In order to simulate long-term aging the batteries were submitted to electrochemical stress in much harder conditions than in normal use. XPS and EIS characterizations were constantly related to evolution of electrochemical performances of batteries. This study allowed us during the duration of the project to bring improvements to batteries in order to obtain a better response to aging mechanisms regarding retention of electrochemical performances: e.g. change of electrodes or electrolyte formulation, change of active materials composition, etc.

Indiana University-Purdue University Indianapolis (IUPUI) / Heat generation is a major safety concern in the design and development of Li ion batteries (LIBs) for large scale applications, such as electric vehicles. The total heat generation in LIBs includes entropic heat, enthalpy, reaction heat, and heat of mixing. The main objective of this study is to investigate the influence of heat of mixing on the LIBs and to understand whether it is necessary to consider the heat of mixing during the design and development of LIBs. In the previous research, Thomas and Newman derived methods to compute heat of mixing in LIB cells. Their results show that the heat of mixing cannot be neglected in comparison with the other heat sources at 2 C rate. In this study, the heat of mixing in different materials, porosity, particle sizes, and charging/discharging rate was investigated. A COMSOL mathematical model was built to simulate the heat generation of LIBs. The LIB model was based on Newman’s model. LiMn2O4 and LiCoO2 were applied as the cathode materials, and LiC6 was applied as the anode material. The results of heat of mixing were compared with the other heat sources to investigate the weight of heat of mixing in the total heat generation. The heat of mixing in cathode is smaller than the heat of mixing in anode, because of the diffusivity of LiCoO2 is 1 ×10-13 m2/s, which is larger than LiC6's diffusivity 2.52 × 10-14 m2/s. In the comparison, the heat of mixing is not as much as the irreversible heat and reversible heat, but it still cannot be neglected. Finally, a special situation will be discussed, which is the heat of mixing under the relaxation status. For instance, after the drivers turn off their vehicles, the entropy, ix enthalpy and reaction heat in LIBs will stop generating, but the heat will still be generated due to the release of heat of mixing. Therefore, it is meaningful to investigate to see if this process has significant influence on the safety and cycle life of LIBs.

The germylenes, germanium(II) 2-(oxidomethyl)phenolate (1), germanium(II) 4-methyl-2-(oxidomethyl)phenolate (2) and germanium(II) 4-bromo-2-(oxidomethyl)phenolate (3) were synthesized and their thermally induced twin polymerization to give organic–inorganic hybrid materials was studied. The compounds 1–3 form oligomers including dimers, trimers and tetramers as a result of intermolecular coordination of the benzylic oxygen atom to germanium. The structural motifs were studied by single crystal X-ray diffraction analysis and DFT-D calculations. Thermally induced twin polymerization of these germylenes gave hybrid materials based on germanium-containing phenolic resins. Carbonization of these resins under reductive conditions resulted in porous materials that are composed of germanium and carbon (Ge@C materials), while oxidation with air provided non-porous germanium dioxide. The porous Ge@C materials were tested as potential anode materials for rechargeable Li-ion batteries. Reversible capacities of 540 mA h g−1 were obtained at a current density of 346 mA g−1 without apparent fading for 100 cycles, which demonstrates that germanium is well accessible in the hybrid material. / Dieser Beitrag ist aufgrund einer (DFG-geförderten) Allianz- bzw. Nationallizenz frei zugänglich.

Li-ion batteries have demonstrated to be a very flexible source with energystorage capability. Due to their scalability and wide range of power and energydensities, they are suitable for several applications. Li-ion storage cantherefore provide different services, the remuneration of which depends onthe electricity market of the country. In this work, two different case studiesof combination of Li-ion batteries with large-scale renewable power plantshave been investigated: batteries with solar PV in India and with wind powerin Sweden. Simulation models have been developed to assess the operationand profitability potential of different services in these two case studies. Themodels have been built using control algorithms, linear optimization (LP) andstochastic programming techniques. The results show that the use of batteriesfor solar power output smoothing under a power purchase agreement canbe a profitable business case in India. Moreover, batteries providing primaryfrequency regulation (FCR-N) in Sweden show to have a positive economicvalue. System breakeven costs to make the stacking of wind power productionimbalance compensation and FCR-N services profitable have been found,which based on conservative price expectations should be achieved by 2022. / Li-ion batterier har visat sig vara en mycket effektiv källa för lagring av energi.Tack vare deras skalbarhet och det breda utbudet av kraft och energidensiteterhar de flera användningsområden. Li-ion batterier kan därför användas föratt tillhandahålla olika typer av tjänster vars ekonomiska ersättning beror avlandets elmarknad. Detta arbete undersöker två fallstudier av Li-ion batterieri kombination med storskaliga kraftverk som drivs av förnybara energikällor:batterier i kombination med solkraft i Indien och vindkraft i Sverige. Simuleringsmodellerhar utvecklats för att undersöka driften och lönsamhetspotentialenför olika tjänster i de två fallstudierna. Modellerna baserar sig påkontrollalgoritmer, linjär optimering och stokastisk programmeringsteknik.Resultaten visar att användningen av batterier för utjämning av solenergi enligtett kraftköpavtal kan vara lönsamma i Indien. Dessutom har användningenav batterier för primärreglering (FCR-N) visat sig ha ett positivt ekonomisktvärde i Sverige. Breakeven kostnaderna för att göra kombinationen av vindkraftsproduktionensbalanskompensering och FCR-N tjänster lönsamma harhittats, vilket ska uppnås senast år 2022 baserat på en konservativ prisprognos.

The purpose of this study is to compare the life-cycle cost and environmental impact of the existing fuel-based propulsion system, on public commuter ferries in Stockholm, with a battery based propulsion system. The study is divided into multiple layers. First, the operating characteristics of the route Line 80 within Stockholm’s waterborne public transportation (WPT) are collected, such as fuel consumption, propulsion power output, speed, voyage time and propulsion system configuration. Second, based on the energy demand of the route, important parameters related to the existing fuel-based propulsion system and the battery-based propulsion system are accounted for and modeled. Third, Life Cycle Assessment (LCA) and the cost assessment methods are applied to examine the effectiveness of the electrification of commuter ferries on a financial and environmental scale. With the help of the software GaBi 2020, GREET 2020, and other literature studies, the environmental impacts at the construction, use and end-of-life (EOL) phase are evaluated. There are in total 8 scenarios considered, 4 for the fuel-based and 4 for the battery-based propulsion system. The environmental performance of these 8 scenarios are discussed in terms of Globalwarmingpotential(GWP), Acidificationpotential(AP), Eutrophicationpotential(EP) and Photo-chemical ozone creation potential (POCP). Themostpollutingphaseistheusephase for all scenarios. Propulsion system powered by diesel (scenario 1) is considered as a reference for comparative analysis of 7 other scenarios. The best performing system is the one powered by batteries with the assumption of an electricity mix based on hydro, wind and nuclear power, which is scenario 7 and 8 with a net reduction of GWP by more than 98%, AP by 90%, EP by 96%, and the POCP by 96%. If we consider the current Swedish electricity mix (scenario 5 and 6), the decrease in GWP, AP, EP and POCP are 90%, 80%, 82% and 91% respectively. Alternative fuels also present promising results for GWP in comparison to diesel (with the origin of the feed-stock creating mostly negative impacts) but the contribution to other impact categories is significantly higher. With inputs from the industry and the environmental evaluation, the cost assessment compares the costs related to fuel-based and battery-based propulsion systems with different energy sources. For the battery-based system, 3 scenarios are modeled for two different types of Li-ion batteries. The vessels in the developed scenarios are charged more frequently than the existing electric vessel and the number of charging stations is varied. The costs that are included in the assessment are the initial capital cost, the cost for fuel/electricity, maintenance cost, end-of-life cost and emissions cost. When concerning all the cost categories, the battery-based system is more cost-efficient than a fuel-based system, if run on the Swedish electricity mix, due to the lower cost for electricity and emissions. The reduction of cost is more than 68% when comparing traditional diesel with battery-based systems, but the source of the electricity is very important. / Syftet med denna studie är att jämföra livscykelkostnaden och miljöpåverkan av de befintliga framdrivningssystemen på pendelbåtarna inom Stockholms kollektivtrafik, med batteridrivna system på motsvarande båtar. De befintliga framdrivningssystemen drivs av olika typer av diesel. Studien är uppdelad i flera steg. Först samlas driftsegenskaperna in, såsom bränsleförbrukning, framdrivningseffekt, hastighet, färdtidochframdrivningssystemetsuppbyggnad, etc, på linje 80, som är en del av Stockholms vattenburna kollektivtrafik. För det andra undersöks det befintliga framdrivningssystemet som drivs av diesel eller alternativa bränslen som RME eller HVO och fullt batteridrivna system utifrån energibehovet. För det tredje tillämpas metoderna för kostnadsanalys och livscykelanalys (LCA) för att undersöka hur elektrifieringen av pendelbåtar påverkar ekonomin och miljön. Med hjälp av programmet GaBi 2020, GREET 2020 och andra litteraturstudier utvärderas miljöpåverkan av faserna tillverkning, användning och avfallshantering. Det är totalt 8 scenarier som övervägs, 4 för bränslebaserade och 4 för batteri baserade framdrivningssystem. Hur bra dessa 8 scenarier presterar miljömässigt diskuteras i termer av växthuseffekt (GWP), försurning (AP), övergödning (EP) och marknära ozon (POCP). Den fasen med mest utsläpp, för alla scenarier, är användningsfasen. Framdrivningssystemet som drivs av diesel (scenario 1) används som referens att jämföra de övriga 7 scenarierna mot. Det system som presterar bästa är det som drivs av batterier, med antagandet att elmixen är baserad på vatten-, vind-och kärnkraft, detta motsvarar scenario 7 och 8 med en reduktion av GWP på mer än 98%, AP med 90%, EP med 96% och POCP med 96%. Om vi tittar på den aktuella svenska elmixen (scenario 5 och 6) så är minskningen av GWP, AP, EP och POCP 90%, 80%, 82% respektive 91%. Alternativa bränslen ger också lovande resultat för GWP jämfört med diesel (där råvarans ursprung skapar mest negativa effekter) men bidraget till andra påverkanskategorier är betydligt högre. Med input från företag och miljöutvärderingen kan kostnadsanalysen jämföra kostnaderna för bränslebaserade och batteri baserade framdrivningssystem med olika energikällor. Det batteri baserade systemet modelleras även på 3 utvecklade scenarier för 2 olika typer av batterier. Fartygen i de utvecklade scenarierna laddas oftare än det befintliga batteridrivna fartyget och antalet laddstationer varierar mellan scenarierna. De kostnader som inkluderas i analysen är de initiala kapitalkostnaderna, kostnaden för bränsle/el, underhållskostnader, avfallshanteringskostnader ochutsläppskostnader. Medallakostnaderinkluderadeiberäkningarna är batteri baserade system mer kostnadseffektiva än bränslebaserade system om de körs på svensk elmix, tack vare de lägre kostnaderna för el och utsläpp. Minskningen av den totala kostnaden är mer än 68% när man jämför traditionell diesel med batterisystem, men elens ursprung är mycket viktig.

Detta examensarbete utreder den tekniska och ekonomiska passbarheten av batterilagringssystem (BESS) inom den svenska el infrastrukturen. Syftet är att konstruera tre olika affärsfall för att representera den tekniska och den ekonomiska passbarheten av BESS inom den svenska el infrastrukturen, specifikt med uppkoppling mot distributionsnätverket på den regionala nivån, 6 kilovolt till 132 kilovolt (kV). Affärsfallen adresserar dem tekniska funktioner och kunder inom infrastrukturen som utifrån en litteraturstudie anses vara dem mest attraktiva att bygga ett affärsfall utifrån. Litteraturstudien utreder den svenska el infrastrukturens struktur samt dess existerande och uppkommande utmaningar. Studien utforskar även hela spektrumet energilagringssystem (ESS) för att rättfärdiga valet av litium-jon BESS. Litium-jon BESS är närmare undersökt, där systemets operativa parametrar samt komponenter är kartlagda. Vidare undersöks dem tekniska funktionernas tekniska krav och ekonomiska incitament i en marknadsanalys. Slutligen utforskas regler och lagar omkring BESS implementering i den svenska el infrastrukturen samt placeringen och de kostnader för att bygga en BESS anläggning. De tre affärfallen som är konstruerade i denna studie är: Kombinationen av frekvensrelaterade nätverksstödtjänster för en fristående BESS-tillgångsoperatör. Avbrottsfri strömtillförsel för ett datacenter. Skala effekttoppar och kombination av frekvensrelaterade nätverksstöddtjänster för en industri. Litium-jon BESS anses vara den mest tillämpliga tekniken på grund av dess snabba responstid, höga effekt- och energidensitet samt skalbarheten för att passa majoriteten av de tekniska funktioner som undersökts inom studien. Affärsfallens ekonomiska passbarhet utvärderas efter två ekonomiska indikatorer, nuvärdesberäkning (NPV) samt återbetalningstiden. Affärsfall nummer tvås tekniska funktion erbjuder ingen möjlighet att generera en inkomst vilket gör att den kommer bli utvärderad efter kostnad för service, där utgifterna är uppdelade utöver projektets livstid genom linjär amortering. Vidare används linjär amortering för att räkna ut kostnaden per kilo sparat CO2 utöver livstiden på projektet. Både affärsfall 1 (NPV= 231,0 MSEK, återbetalningstid= 7,8 år) samt affärsfall 3 (NPV= 17,3 MSEK, återbetalningstid= 8,8 år) visar en lönsamhet där affärsfall 2 ger en kostnad för service mellan 5,4 och 5,8 MSEK/år och där kostnaden per sparat kilo CO2 mellan 20,9 och 22,7 SEK/kg CO2. Denna studie fokuserar på de tre största distributionsnätverksoperatorerna (DNO) inom distributionsnätverket på en regional nivå: Vattenfall, Eon och Ellevio. Lönsamheten av de undersökta affärsfallen är starkt kopplade till placeringsområde inom nätverket, spänningsnivån och typ av DNO. Möjlighet att koppla upp BESS till en existerande transformatorstation på anläggningen för affärsfall två och tre minskar investeringskostnaden samt driftkostnaderna vilket vidare förbättrar dess lönsamhet. Affärsfall ett behöver gå igenom en noggrann bedömning för att försäkra sig om lönsamheten. NPV samt återbetalningstiden kan påverkas i affärsfall ett och tre på grund av den ständigt förändrande frekvensregleringsmarknaden där priserna är volatila på grund av nya marknadsinitiativ. Att konstruera ett BESS affärsfall medför att flertalet osäkerheter bör räknas in, såsom de ekonomiska incitamenten som inte visar någon garanti på att vara fortsatt lönsamt. Det höga priset på litium-jon batterier saktar ner attraktiviteten av affärsfallen och måste vidare sjunka för att främja ett lönsamt affärsfall. Andra ESS som flödesbatterier och vätgaslagringssystem visar god passbarhet att bli implementerad i den svenska el infrastrukturen men måste vidare utveckla sin tekniska och kommersiella mognadsgrad innan dem kan vara konkurrenskraftiga med litium-jon BESS.  Examensarbetet är utfört i samarbete med Omexom Infratek Sverige AB med målet att bidra till en större förståelse av BESS roll i den svenska el infrastrukturen och vidare bidra till att konstruera ett tekniskt erbjudande för Omexom Infratek Sverige AB. / This master thesis investigates the technical and economic feasibility of battery energy storage systems (BESS) in the Swedish electrical infrastructure. The aim is to construct three business cases to represent the technical and economic feasibility of BESS implementation in the Swedish electrical infrastructure in the distribution network on the regional level, 6 kilovolts to 132 kilovolts (kV). The business cases address the technical functions and customers within the infrastructure that is recognized through a literature study to build the most attractive and incentivized business cases from. The literature study investigates the Swedish electrical infrastructure’s structure and its existing and upcoming challenges. It investigates the spectrum of energy storage systems (ESS) to justify the choice of the lithium-ion (Li-ion) BESS. The Li-ion BESS is closer examined, where the systems operational parameters and components are mapped out. Furthermore, the technical functions technical requirements and economic incentives are investigated in a market analysis. Lastly, considerations regarding regulations and permits, the placement of BESS within the infrastructure and its surrounding costs is evaluated. The three business cases that are constructed within the thesis are:  Combination of frequency related grid support services for a standalone BESS asset operator. Uninterruptable power supply for a data center. Peak shaving and a combination of frequency related grid support services for an industrial plant.  The, Li-ion BESS is considered to most applicable technology due its fast response time, high power and energy density and scalability to suit the majority of technical functions investigated in the thesis. The business cases economic feasibility is evaluated after two economic indicators, the net present value (NPV) and the payback period. Business case two’s technical function offers no possible revenues and is evaluated as a cost for service where the expenses is divided throughout the project lifetime through linear amortization and the cost per saved kg CO2 is calculated over the lifetime of the BESS. Both business case 1 (NPV= 231.0 MSEK, payback period= 7.8 years) and case 3 (NPV=17.3 MSEK, payback period= 8.8 years) show profitability where business case 2 gives a cost per service between 5.4 and 5.8 MSEK/year and cost per saved kg CO2 between 20.9 and 22.7 SEK/kg CO2.  This thesis focuses on the three largest distribution network operators (DNO) in the distribution network on a regional level: Vattenfall, Eon, and Ellevio. The profitability of the business cases investigated are strongly connected to the location in the network, the voltage connection level, and the type of DNO. Being able to connect to an existing substation on site as for business cases 2 and 3 will lower the capital and operational costs and further improve the profitability. Business case 1 needs a thorough assessment of placement in the electrical infrastructure in Sweden to assure profitability. The NPV and payback period in business cases 1 and 3 could conflict with the interchanging frequency regulation market where prices are rather volatile due to new market initiatives. Therefore, looking forward, building a BESS business case to be implemented comes with lots of uncertainties as the economic incentives shows no guarantee to continuously be profitable. The high price of Li-ion batteries is slowing down the attractiveness of the business cases and need to further decrease to promote profitable business cases. Other ESS technologies as flow batteries and hydrogen storage systems show good applicability to be implemented in the Swedish electrical infrastructure but needs to develop its technical and commercial maturity until it can become competitive with Li-ion BESS.  The master thesis is performed in conjunction with Omexom Infratek Sverige AB with the aim to contribute to a broader understanding of the role of BESS in the Swedish electrical infrastructure and to help building BESS technical offers for Omexom Infratek Sverige AB.

All solid state Li-ion batteries (thin film micro batteries) have become inevitable for miniaturized devices and sensors as power sources. Fabrication of electrode materials for batteries in thin film form has been carried out with the existing technologies used in semiconductor industry. In the present thesis, radio frequency (RF) sputtering has been chosen for deposition of cathode material (ceramic oxides) thin films because of several advantages such as precise thickness control and deposition of compound thin films with equivalent composition. Conventional sputtering involves fabrication of thin film using custom made pellet according to the specification of sputter gun. However several issues such as target breaking are inevitable with the pellet sputtering. To forfend the issues, powder sputtering has been implemented for the deposition of various thin film cathodes in an economically feasible approach. Optimization of various process parameters during film deposition of cathode materials LiCoO2, Li2MnO3, LiNixMnyO4, mixed oxide cathodes of LiMn2O4, LiCoO2 and TiO2 etc., have been executed successfully by the present approach to achieve optimum electrochemical performance. Thereafter the optimized process parameters would be useful for selection of cathode layers for micro battery fabrication. Chapter 1 gives a brief introduction to the Li ion and thin film solid state batteries. It also highlights the advantages of powder sputtering compared to conventional pellet sputtering. In Chapter 2, the materials used and methods employed for the fabrication of thin film electrodes and analytical characterizations have been discussed. In chapter 3, implementation of powder sputtering for the deposition of LiCoO2 thin films has been discussed. X-Ray diffraction (XRD), X-Ray photoelectron spectroscopy (XPS) and electrochemical investigations have been carried out and promising results have been achieved. Charge discharge studies delivered a discharge capacity of 64 µAh µm-1 cm-2 in the first cycle in the potential range 3.0-4.2 V vs. Li/Li+. The possible causes for the moderate cycle life performance have been discussed. Systematic investigations for RF power optimization for the deposition of Li2-xMnO3-y thin films have been carried out. Galvanostatic charge discharge studies delivered a highest discharge capacity of 139 µAh µm-1cm-2 in the potential window 2.0-3.5 V. Thereafter, effect of LMO film thickness on electrochemical performance has been studied in the thickness range 70 nm to 300 nm. Films of lower thickness delivered higher discharge capacity with good cycle life than the thicker films. These details are discussed in chapter 4. In Chapter 5, fabrication and electrochemical performance of LiNixMnyO4 thin films are presented. LMO thin films have been deposited on nickel coated stainless steel substrates. The as deposited films were annealed at 500 °C in ambient conditions. Nickel diffuses in to LMO film and results in LiNixMnyO4 (LMNO) film. These films were further characterized. Electrochemical studies were conducted up to higher potential 4.4 V resulted in discharge capacities of the order of 55 µAh µm-1cm-2. In chapter 6, electrochemical investigations of mixed oxide thin films of LiCoO2 and LiMn2O4 have been carried out. Electrochemical investigations have been carried out in the potential window 2.0–4.3 V and a discharge capacity of 24 µAh µm-1cm-2 has been achieved. In continuation, TiO2 powder was added to the former composition and the deposited films were characterized for electrochemical performance. The potential window as well as the discharge capacity enhanced after TiO2 doping. Electrochemical characterization has been carried out in the potential window 1.4–4.5 V, and a discharge capacity of 135 µAh µm-1cm-2 has been achieved. Finally chapter 7 gives overall conclusions and future directions to the continuation of the work.

Lithium-ion battery is attractive for various applications because of its high energy density. The performance of Li-ion battery is influenced by several properties of the electrode materials such as particle size, surface area, ionic and electronic conductivity, etc. Porosity is another important property of the electrode material, which influences the performance. Pores can allow the electrolyte to creep inside the particles and also facilitate volume expansion/contraction arising from intercalation/deintercalation of Li+ ions. Additionally, the rate capability and cycle-life can be enhanced. The following porous electrode materials are investigated. Poorly crystalline porous -MnO2 is synthesized by hydrothermal route from a neutral aqueous solution of KMnO4 at 180 oC and the reaction time of 24 h. On heating, there is a decrease in BET surface area and also a change in morphology from nanopetals to clusters of nanorods. As prepared MnO2 delivers a high discharge specific capacity of 275 mAh g-1 at a specific current of 40 mA g-1 (C/5 rate). Lithium rich manganese oxide (Li2MnO3) is prepared by reverse microemulsion method employing Pluronic acid (P123) as a soft template. It has a well crystalline structure with a broadly distributed mesoporosity but low surface area. However, the sample gains surface area with narrowly distributed mesoporosity and also electrochemical activity after treating in 4 M H2SO4. A discharge capacity of about 160 mAh g-1 is obtained at a discharge current of 30 mA g-1. When the acid-treated sample is heated at 300 °C, the resulting porous sample with a large surface area and dual porosity provides a discharge capacity of 240 mAh g-1 at a discharge current density of 30 mA g-1. Solid solutions of Li2MnO3 and LiMO2 (M=Mn, Ni, Co, Fe and their composites) are more attractive positive electrode materials because of its high capacity >200 mAh g-1.The solid solutions are prepared by microemulsion and polymer template route, which results in porous products. All the solid solution samples exhibit high discharge capacities with high rate capability. Porous flower-like α-Fe2O3 nanostructures is synthesized by ethylene glycol mediated iron alkoxide as an intermediate and heated at different temperatures from 300 to 700 oC. The α-Fe2O3 samples possess porosity with high surface area and deliver discharge capacity values of 1063, 1168, 1183, 1152 and 968 mAh g-1 at a specific current of 50 mA g-1 when prepared at 300, 400, 500, 600 and 700 oC, respectively. Partially exfoliated and reduced graphene oxide (PE-RGO) is prepared by thermal exfoliation of graphite oxide (GO) under normal air atmosphere at 200-500 oC. Discharge capacity values of 771, 832, 1074 and 823 mAh g -1 are obtained with current density of 30 mA g-1 at 1st cycle for PE-RGO samples prepared at 200, 300, 400 and 500 oC, respectively. The electrochemical performance improves on increasing of exfoliation temperature, which is attributed to an increase in surface area. The high rate capability is attributed to porous nature of the material. Results of these studies are presented and discussed in the thesis.

A prototype 3-dimensional (3D) anode, based on multiwall carbon nanotubes (MWCNTs), for Li-ion batteries (LIBs), with potential use in Electric Vehicles (EVs) was investigated. The unique 3D design of the anode allowed much higher areal mass density of MWCNTs as active materials, resulting in more amount of Li+ ion intake, compared to that of a conventional 2D counterpart. Furthermore, 3D amorphous Si/MWCNTs hybrid structure offered enhancement in electrochemical response (specific capacity 549 mAhg-1). Also, an anode stack was fabricated to further increase the areal or volumetric mass density of MWCNTs. An areal mass density of the anode stack 34.9 mg/cm2 was attained, which is 1,342% higher than the value for a single layer 2.6 mg/cm2. Furthermore, the binder-assisted and hot-pressed anode stack yielded the average reversible, stable gravimetric and volumetric specific capacities of 213 mAhg-1 and 265 mAh/cm3, respectively (at 0.5C). Moreover, a large-scale patterned novel flexible 3D MWCNTs-graphene-polyethylene terephthalate (PET) anode structure was prepared. It generated a reversible specific capacity of 153 mAhg-1 at 0.17C and cycling stability of 130 mAhg-1 up to 50 cycles at 1.7C.