There are today clear indications that the Li-ion battery of the type currently used worldwide in mobile-phones and lap-tops is also destined to soon become the battery of choice in more energy-demanding concepts such as electric and electric hybrid vehicles (EVs and EHVs). Since the currently used cathode materials (typically of the Li(Ni,Co)O2-type) are too expensive in large-scale applications, these new batteries will have to exploit some much cheaper transition-metal. Ideally, this should be the very cheapest - iron(Fe) - in combination with a graphite(C)-based anode. In this context, the obvious Fe-based active cathode of choice appears to be LiFePO4. A second and in some ways even more attractive material - Li2FeSiO4 - has emerged during the course of this work. An effort has here been made to understand the Li extraction/insertion mechanism on electrochemical cycling of Li2FeSiO4. A fascinating picture has emerged (following a complex combination of Mössbauer, X-ray diffraction and electrochemical studies) in which the material is seen to cycle between Li2FeSiO4 and LiFeSiO4, but with the structure of the original Li2FeSiO4 transforming from a metastable short-range ordered solid-solution into a more stable long-range ordered structure during the first cycle. Density Functional Theory calculations on Li2FeSiO4 and the delithiated on LiFeSiO4 structure provide an interesting insight into the experimental result. Photoelectron spectroscopy was used to study the surface chemistry of both carbon-treated LiFePO4 and Li2FeSiO4 after electrochemical cycling. The surface-layer on both materials was concluded to be very thin and with incomplete coverage, giving the promise of good long-term cycling. LiFePO4 and Li2FeSiO4 should both be seen as highly promising candidates as positive-electrode materials for large-scale Li-ion battery applications.

Les métaux lourds et les radionucléides sont présents dans différents écosystèmes du monde à cause de contaminations naturelles ou des activités anthropiques. L’utilisation de micro-organismes pour restaurer ces écosystèmes pollués, processus connu sous le nom de bioremédiation, suscite beaucoup d’intérêt, spécialement aux pH proches de la neutralité. Les minéraux de fer qui encroûtent les bactéries neutrophiles du fer, notamment les Oxydes de Fer Biogéniques (BIOS en anglais), ont une structure très faiblement cristalline, qui en plus de leur grande surface et réactivité font d’eux d’excellents supports pour le piégeage de polluants inorganiques. Dans cette thèse nous avons étudié les différents mécanismes de piégeage de l’uranium uranium par la bactérie neutrophile Sphaerotilus natans, choisie comme modèle bactérien de micro-organismes du fer capables de filamenter en formant des gaines. S. natans peut croître sous forme de cellules individuelles ou formant des filaments. Ces derniers ont été utilisés pour étudier la biosorption d’U(VI) et sa sorption sur les BIOS. De plus, la sorption d’U(VI) sur les analogues abiotiques de ces minéraux de fer a été testée. Afin d’utiliser les filaments de S. natans pour piéger l’U(VI), il était nécessaire d’identifier les facteurs induisant la filamentation de S. natans. L’influence de l’oxygène a été établie en utilisant des techniques de biologie moléculaire et nos résultats ont démontré que tandis qu’en condition d’oxygène saturé elle croît sous forme de cellules individuelles, une diminution modérée d’oxygène à ~ 3 mg O2.L-1 la fait croître sous la forme désirée, des filaments de S. natans.Les BIOS attachés aux filaments de S. natans ainsi que ses analogues abiotiques ont été analysés pas XAS au seuil K du Fe. Les deux matériaux identifiés sont des phosphates de fer(III) amorphes avec une faible proportion de fer(II), qui présentent une réactivité élevée pour le piégeage de polluants inorganiques. L’EXAFS au seuil LIII de l’U a montré la même structure pour les couches O, tandis que celles P, Fe et C étaient différentes en fonction des sorbants. Une étude intégrée qui combine des techniques expérimentales avec des calculs de spéciation a permis de décrire les isothermes d’adsorption de l’U(VI) en utilisant un modèle de complexation de surface. Ces résultats suggèrent que les groupes phosphoryles et carboxyles sont les groupes fonctionnels principaux pour la biosorption d’U(VI) par des filaments de S. natans. Les résultats de cette thèse vont aider à comprendre les processus contrôlant l’immobilisation de l’U(VI), soit par la biosorption sur S. natans, la sorption sur les BIOS ou la sorption sur les phosphates de fer, et en conséquence le devenir de l’U en conditions neutres / Heavy metals and radionuclides are present in some ecosystems worldwide due to natural contaminations or anthropogenic activities. The use of microorganisms to restore those polluted ecosystems, a process known as bioremediation, is of increasing interest, especially under near-neutral pH conditions. Iron minerals encrusting neutrophilic iron-related bacteria, especially Bacteriogenic Iron Oxides (BIOS), have a poorly crystalline structure, which in addition to their large surface area and reactivity make them excellent scavengers for inorganic pollutants. In this PhD work we studied the different mechanisms of uranium scavenging by the neutrophilic bacterium Sphaerotilus natans, chosen as a model bacterium for iron-related sheath-forming filamentous microorganisms. S. natans can grow as single cells and filaments. The latter were used to investigate U(VI) biosorption and U(VI) sorption onto BIOS. In addition, uranium sorption onto the abiotic analogues of such iron minerals was assessed. In order to use S. natans filaments for U(VI) scavenging, it was necessary to identify factors inducing S. natans filamentation. The influence of oxygen was ascertained by using molecular biology techniques and our results revealed that while saturated oxygen conditions resulted in single cell growth, a moderate oxygen depletion to ~ 3 mg O2.L-1 led to the desired filamentous growth of S. natans. BIOS attached to S. natans filaments as well as the abiotic analogues were analysed by XAS at Fe K-edge. Both materials were identified as amorphous iron(III) phosphates with a small component of Fe(II), with a high reactivity towards scavenging of inorganic pollutants. In addition, EXAFS at the U LIII-edge revealed a common structure for the O shells, while those for P, Fe and C were different for each sorbent. An integrated approach combining experimental techniques and speciation calculations made it possible to describe U(VI) adsorption isotherms by using a surface complexation model. These results suggested the role of phosphoryl and carboxyl groups as the main functional groups involved in the U(VI) biosorption by S. natans. The results of this PhD work will help to better understand the processes governing U(VI) immobilization, either by S. natans biosorption, sorption onto BIOS or sorption onto iron phosphates, an thus the fate of uranium in near-neutral pH environments

Die vorliegende Dissertation beschäftigt sich mit der Synthese, den Li+-Transporteigenschaften und der Thermodynamik von Olivin-Typ LiFePO4. Es werden verschiedene Solvothermalsynthesen untersucht. Neben der Einstellung von Partikelgröße und Partikelmorphologie steht die Analyse der Hydrothermalsynthese aus Li3PO4 und Vivianit durch in situ Messung der elektrolytischen Leitfähigkeit im Vordergrund. Die Untersuchung des Li+-Transportes geschieht auf Basis von Redoxreaktionen. Die formalkinetische Auswertung von Lithiierungs- und Delithiierungsreaktionen und eine Nukleationsanalyse wird durch ein Modell zur Auswirkung von antisite-Defekten auf die Kapazität des Elektrodenmaterials ergänzt. Die Ramanspektroskopie wird in Verbindung mit Lösungsenthalpien zur Identifizierung reaktiver Spezies herangezogen. Schwerpunkt der thermodynamischen Charakterisierung ist die experimentelle Ermittlung der Wärmekapazität. Diese wurde unter Berücksichtigung einer magnetischen Phasenumwandlung im Bereich von 2 K bis 773 K ermittelt. Die Daten erlauben die Berechnung wichtiger thermodynamischer Funktionen.

Journal articles are the formal medium for the communication of results among scientists, and often contain valuable data. However, manually collecting article data from a large field like lithium-ion battery chemistry is tedious and time consuming, which is an obstacle when searching for statistical trends and correlations to inform research decisions. To address this a platform for the automatic retrieval and analysis of large numbers of articles is created and applied to the field of lithium-ion battery chemistry. Example data produced by the platform is presented and evaluated and sources of error limiting this type of platform are identified, with problems related to text extraction and pattern matching being especially significant. Some solutions to these problems are presented and potential future improvements are proposed.

Магистерская диссертация посвящена синтезу и исследованию структуры положительного электродного материала на основе железофосфата лития. В работе проведена работа по поиску и систематизации информации по интересующей теме, описаны методики синтеза, изучению методом спектроскопии комбинационного рассеивания света и результаты измерения структуры, как железофосфата лития, так и композитов на его основе. Изучена зависимость спектра КРС от мощности лазерного излучения. Сделано предположение о модификации поверхностного слоя частиц железофосфата лития после воздействия лазерного излучения. / The master's thesis is devoted to the synthesis and study of the structure of the positive electrode material based on lithium iron phosphate. The work was carried out to search for and systematize information on a topic of interest, describes synthesis methods, studies of Raman spectroscopy and the results of measuring the structure of both lithium iron phosphate and composites based on it. The dependence of the Raman spectrum on the power of laser radiation was studied. An assumption was made about the modification of the surface layer of lithium iron phosphate particles after exposure to laser irradiation.

Elanvändningen i Sverige förväntas fördubblas till 2045 på grund av ökad elektrifiering av det svenska samhället. För att ställa om till ett elsystem som är beroende av mer förnyelsebara elproduktionsslag föreslår Svenska kraftnät (2021) att Sverige kommer att behöva öka sin flexibilitet i elnätet. Ett sätt att göra detta på är genom ellagring, där batterisystem är ett alternativ. Någon konkret plan för hur och när detta skulle genomföras har inte gjorts av Svenska kraftnät. Därför syftade detta projekt till att ta reda på om ett litiumjärnfosfat (LFP) batterienergilagringssystem skulle vara en lönsam investering att använda för energiomställning i det svenska elmarknadsområdet SE3. Detta mål uppnåddes genom att modellera ett batterilager över ett år och extrapolera dessa resultat till en investeringskalkyl genom annuitetsmetoden. Sammanfattat så konstaterades det att det inte är en lönsam investering. Men det fullständiga svaret är mer komplicerat än så. Batteriets storlek och livslängd påverkar batteriets investeringskostnad, som vidare påverkar batteriets lönsamhet. Batteriets livslängd är beroende av egenskaper som batteriets upp och urladdningstid (s.k. C-rate) samt i vilken utsträckning batteriet laddas och laddas ur (s.k. state of charge), som i sin tur influerar totala antalet laddningscykler batteriet kan genomföra. Exakt hur mycket dessa egenskaper påverkar livslängden för LFP:erna är oklart eftersom resultaten från tidigare studier av LFP-batteriers prestanda skiljer sig något. Till exempel är det känt att state of charge för ett batteri påverkar livslängden för ett LFP-batteri, men mer exakt hur mycket varierar beroende på studie, vilket visas i detta examensarbete. Det som gör detta ännu mer komplicerat är det faktum att investeringskostnaden kommer att förändras beroende på till exempel vilken state of charge som används. Dessutom varierar uppskattningar av investeringskostnaden för LFP-batterier i olika källor. Allt detta leder till flera typer av osäkerheter för att bestämma den exakta investeringskalkylen. Det huvudsakliga bidraget denna studie kan ge är dock att den kan ge en första inblick i hur ett batterilagringssystem för kortvarig energilagring (energy shifting) skulle fungera i Sverige. Med fler studier liknande detta projekt skulle en mer konkret plan kunna göras för genomförandet av det statliga klimatmålet om netto noll utsläpp av växthusgaser till år 2045 (Naturvårdsverket, 2023). / The electricity use in Sweden is expected to double before 2045 due to increased electrification of the Swedish society. In order to transition into an electrical system that is dependent of more sustainable renewable energy sources, Svenska kraftnät (2021) is suggesting that Sweden will need to increase their flexibility in the power grid. One of the main ideas on how to do that is through energy storages, where battery systems could play an important part. However, a concrete plan of how and when this would happen was not made clear by Svenska kraftnät. Therefore, this project aimed at finding out whether a Lithium iron phosphate (LFP) battery energy storage system would be a worthwhile investment to use for energy shifting in the Swedish SE3 electricity market area. This aim was reached through modelling a battery storage over a year and extrapolating these results into an investment calculation using the annuity method. In short, it was found that it is not a profitable investment. But the full answer was found to be more complicated than that. The battery’s size and lifetime affect the battery’s investment cost, which further affects the battery’s profitability. The battery’s lifetime is dependent on battery characteristics such as the charge/discharge time of the battery (C-rate) and the extent to which the battery is charged and discharged (state of charge), which in turn influences the total amount of charge cycles a battery can perform. Further, how significant these characteristics affect cost and lifetime of the LFP’s is unclear as the results from previous studies on LFP batteries differ somewhat. For example, it is known that the state of charge range of a battery affects the lifetime of an LFP battery, but by exactly how much varies with different studies, which is explained in this master thesis. What makes this even more complicated is the fact that depending on the state of charge used, the investment cost will change. Additionally, the assessed investment cost also changes depending on the source used. Therefore, the exact cost is difficult to determine. However, the main contribution this study has is that it can give a first insight into how a battery storage system for energy shifting would work. With more case-like studies similar to this project, a more concrete plan could be made about how to realise the Swedish governmental climate goal of net zero greenhouse gas emissions by the year 2045 (Naturvårdsverket, 2023).

No description available.

Power outages, electric-grid deficiencies and renewable energies are all examples where stationary energy storages are useful. In this master thesis, two types of stationary electrochemical energy storages are examined; vent-regulated lead-acid batteries (VRLA) and lithium iron phosphate batteries (LFP), to find out the more beneficial one in stationary uses. The techniques are examined for a large range of electric-grid services in a techno-economical investigation. The cost per delivered kWh of the energy storage is the basis of comparison which is calculated using battery degradation data with respect to C-rate, SoC, DoD, temperature, storage time and cycle frequency to estimate calendar and cyclic aging. Modelling presents neither alternative as superior although LFP is the more versatile alternative. VRLA-batteries can be a more cost-beneficial alternative for applications demanding less than 1 cycle/day, at temperatures lower than 30C, short project lifetimes and when utilizing storages beyond 80% EoL. The investment cost is lower for VRLA at equal C-rates. Cost items neglected will decrease the chances of VRLA being the cheapest technique. From a sustainability point of view, LFP is under almost all circumstances the less energy and CO2-intense technology, however recyclability is in clear favor for VRLA. / Strömavbrott, underdimensionerade elnät och förnybar energi är tre exempel där ett stationärt energilager kan tillämpas. I den här masteruppsatsen undersöks två typer av stationära elektrokemiska energilager; ventilreglerade bly-syra-batterier och litium-järnfosfat-batterier (LFP), för att finna det mer fördelaktiga alternativet i stationära applikationer. De två teknikerna analyseras i ett stort antal elnätsapplikationer i en tekno-ekonomisk studie. Kostnaden per levererad kWh av energilagret används som jämförelsebas vilken beräknas utifrån batteridegraderingsdata med avseende på C-rate, SoC, DoD, temperatur, lagringstid och cykelfrekvens för att estimera kalender- och cyklisk åldring. Modellering visar att inget av batterialternativen är överlägset i alla situationer men LFP är det mångsidigare alternativet. Bly-syra-batterier kan vara mer kostnadseffektiva för applikationer som kräver mindre än 1 (full-ekvivalent) cykel/dag vid temperaturer lägre än 30C, korta projektlivstider samt när batterilagren används bortom 80% EoL. Investeringskostnaden är lägre för bly-syra-batterier när likadan C-rate appliceras. Negligerade kostnadsposter kommer minska chanserna att bly-syra-batterier är det billigaste alternativet. Från ett hållbarhetsperspektiv är LFP nästan uteslutande den mindre energikrävande och mindre CO2-intensiva tekniken. Bly-syra-batterier har dock en klar fördel när det kommer till återvinningsbarhet.

Dans cette thèse nous démontrons le travail fait sur deux matériaux de cathodes pour les piles lithium-ion. Dans la première partie, nous avons préparé du phosphate de fer lithié (LiFePO4) par deux méthodes de lithiation présentées dans la littérature qui utilisent du phosphate de fer (FePO4) amorphe comme précurseur. Pour les deux méthodes, le produit obtenu à chaque étape de la synthèse a été analysé par la spectroscopie Mössbauer ainsi que par diffraction des rayons X (DRX) pour mieux comprendre le mécanisme de la réaction. Les résultats de ces analyses ont été publiés dans Journal of Power Sources. Le deuxième matériau de cathode qui a été étudié est le silicate de fer lithié (Li2FeSiO4). Une nouvelle méthode de synthèse a été développée pour obtenir le silicate de fer lithié en utilisant des produits chimiques peu couteux ainsi que de l’équipement de laboratoire de base. Le matériau a été obtenu par une synthèse à l’état solide. Les performances électrochimiques ont été obtenues après une étape de broyage et un dépôt d’une couche de carbone. Un essai a été fait pour synthétiser une version substituée du silicate de fer lithié dans le but d’augmenter les performances électrochimiques de ce matériau. / In this thesis, we demonstrate work on two different cathode materials for lithium-ion batteries. First, the synthesis of lithium iron phosphate (LiFePO4) is reproduced from literature using two lithiation methods starting with amorphous iron phosphate (FePO4). For both reactions, the product at each step of the synthesis was analyzed using Mössbauer Spectroscopy and X-ray diffraction in order to gain further insight of the reaction mechanism. The results of this work were published in Journal of Power Sources. The second cathode material of interest was lithium iron silicate (Li2FeSiO4). A novel synthetic method was developed to produce lithium iron silicate cost effectively starting with low cost precursors and basic laboratory equipment. The material was synthesized using a solid- state synthesis after milling and carbon coating, electrochemical performance was evaluated. An attempt was made to synthesize off-stoichiometric lithium iron silicate in order to increase the electrochemical performance of the material.

Nous avons mis au point une approche novatrice pour la synthèse d’un matériau de cathode pour les piles lithium-ion basée sur la décomposition thermique de l’urée. Les hydroxydes de métal mixte (NixMnxCo(1-2x)(OH)2) ont été préparés (x = 0.00 à 0.50) et subséquemment utilisés comme précurseurs à la préparation de l’oxyde de métal mixte (LiNixMnxCo(1-2x)O2). Ces matériaux, ainsi que le phosphate de fer lithié (LiFePO4), sont pressentis comme matériaux de cathode commerciaux pour la prochaine génération de piles lithium-ion. Nous avons également développé un nouveau traitement post-synthèse afin d’améliorer la morphologie des hydroxydes. L’originalité de l’approche basée sur la décomposition thermique de l’urée réside dans l’utilisation inédite des hydroxydes comme précurseurs à la préparation d’oxydes de lithium mixtes par l’intermédiaire d’une technique de précipitation uniforme. De plus, nous proposons de nouvelles techniques de traitement s’adressant aux méthodes de synthèses traditionnelles. Les résultats obtenus par ces deux méthodes sont résumés dans deux articles soumis à des revues scientifiques. Tous les matériaux produits lors de cette recherche ont été analysés par diffraction des rayons X (DRX), microscope électronique à balayage (MEB), analyse thermique gravimétrique (ATG) et ont été caractérisés électrochimiquement. La performance électrochimique (nombre de cycles vs capacité) des matériaux de cathode a été conduite en mode galvanostatique. / We have developed a novel approach to the synthesis of cathode materials for lithium-ion batteries, based on the thermal decomposition of urea. Mixed metal hydroxides (NixMnxCo(1-2x)(OH)2), x = 0.00 to 0.50, were prepared and subsequently used as precursor for lithiated mixed metal oxide (LiNixMnxCo(1-2x)O2). These materials along with lithium iron phosphate (LiFePO4) are being considered as cathode materials for the next generation of lithium-ion batteries. We have also developed new post-synthetic treatments on the hydroxides in order to enhance the morphology, which would result in improved electrode properties. The novelty of this thesis is that for the first time mixed metal hydroxides for use as precursors for lithium mixed oxides have been prepared via a uniform precipitation technique from solution. In addition, we have proposed new treatments techniques towards the more traditional synthesis method for mixed metal hydroxides. The results obtained from these two methods are summarized within two articles that were recently submitted to peer-reviewed journals. Within this thesis, all materials were analyzed with X-ray diffraction (XRD), scanning electron microscopy (SEM), thermal gravimetric analysis (TGA) and electrochemical measurements. The electrochemical performance (capacity vs cycle number) of the cathode materials were tested galvanostatically.