A new preparation concept of a partially porous solid-state bilayer electrolyte (BE) for high-temperature sodium-ion batteries has been developed. The porous layer provides mechanical strength and is infiltrated with liquid and highly conductive NaAlCl4 salt, while the dense layer prevents short circuits. Both layers consist, at least partially, of Na-β-alumina. The BEs are synthesized by a three-step procedure, including a sol-gel synthesis, the preparation of porous, calcined bulk material, and spin coating to deposit a dense layer. A detailed study is carried out to investigate the effect of polyethylene oxide (PEO) concentration on pore size and crystallization of the bulk material. The microstructure and crystallographic composition are verified for all steps via mercury intrusion, X-ray diffraction, and scanning electron microscopy. The porous bulk material exhibits an unprecedented open porosity for a NaxAlOy bilayer-system of ≤57% with a pore size of ≈200–300 nm and pore volume of ≤0.3 cm3∙g−1. It contains high shares of crystalline α-Al2O3 and Na-β-alumina. The BEs are characterized by impedance spectroscopy, which proved an increase of ionic conductivity with increasing porosity and increasing Na-β-alumina phase content in the bulk material. Ion conductivity of up to 0.10 S∙cm−1 at 300 °C is achieved.

Because of the changing energy supply landscape, with the transition towards renewable energy, an emerging demand for energy storage systems (ESS) is expected in the near future. Battery energy storage is promising to contribute to mitigate the greenhouse gas emissions, but face issues considering resource use (IEA, 2023; IRENA, 2022). Sodium-ion batteries are a promising technology for the ESS-market, expected to take up 21 % of new installations by 2030. This means an anticipated demand of about 50 GWh of sodium-ion cells required in 2030. Key drivers for the expected entrance of sodium-ion storage are the low price, high abundance of cell materials and expectations of a more safe and sustainable battery. Lithium-ion technology is currently dominating the energy storage market, but have concerns with ethical resource supply and rising mineral prices combined with the growing demand. (BloombergNEF, 2023; IEA, 2023) There is a scarcity of information considering sodium-ion environmental reporting (Liu et al., 2021; Peters et al., 2021). Therefore, the purpose of this study is to evaluate the environmental aspect of sodium-ion storage technology. Thereby, with this study a life cycle assessment (LCA) is performed on a specific sodium-ion cell. The specific scope for the thesis is to look at 1 kWh of produced battery energy storage, in a cradle-to-gate perspective. The results are to be presented with a decomposition of the emissions across the value chain including materials, transport, and energy influence. As well a division of the cell materials impacts are demonstrated. For the assessed cell, it is assumed to be intended for a giga scale production (>1 GWh annual cell storage produced). Hypothetically this is to be placed in Europe, with both a global and a local supply chain presented. In order with European initiatives, there is a guideline called PEFCR, that recommends how to access the environmental footprint of different products. Among these guidelines, there is a certain standard for battery environmental assessment, which was pursued to be followed. According to these recommendations, the methodology of this assessment will include 16 environmental perspectives, called EF2.0. The EF2.0 emission categories presented as main result are Climate Change (total), Acidification, Resource Use (fossils), Resource Use (minerals & metals), and Particulate Matter, since these are considered relevant for batteries by PEFCR. (European Commission and ReCharge, 2018) Furthermore, it was chosen for this study to have its core in analysing the EF2.0 Climate Change impact, with the aim to identify measures on how to reduce the carbon footprint caused by the cell’s life cycle. With the perspective of the 16 environmental effects, a sodium-ion current state scenario was put in focus. On top of this, a decarbonized scenario is presented for the EF2.0 Climate Change impact. For the current state scenario, a comparison is made with a lithium-ion cell from industry, produced from fossil-free energy. This is framing the sodium-ion environmental results in the perspective of how a decarbonized lithium-ion cell performs environmentally. Both the sodium and lithium cells included in the comparison, have the aim to be used for energy storage system applications (ESS). Regarding the results for the 16 environmental categories, overall, the cathode is the main driver for emissions, followed by electrolyte and anode. Furthermore, in the decarbonized scenario, it is illustrated that implementing certain measures within the value chain could reduce the sodium-cell carbon emissions with potentially more than half of what is estimated today. Altogether, the sodium-ion value chain is in an emerging expansion phase (Rho motion, 2023), with a young supply chain starting to form. It is discussed that in the near future, with higher energy density on sodium cells commercialized (Peters et al., 2021), the environmental footprint for sodium-ion could significantly improve. Anyhow, the strongest indication from this study, is that the resource use from minerals and metals drastically would reduce with a technology switch from lithium to sodium. Among the 16 environmental impacts as a whole, the main trend is that sodium-ion cells induce less harm on the environment compared to lithium technologies. Certainly, in the future sodium-ion cells could be a low cost and sustainable option available for energy storage systems. / I och med dagens förändrade energiförsörjningslandskap, med en pågående trend mot mer förnybar energi, förväntas en ökad efterfrågan på storskaliga energilagringssystem (ESS) inom en snar framtid. Däribland är batterilagring lovande för att bidra till att minska utsläppen av växthusgaser, men försörjningen av batterier står samtidigt inför utmaningar vad gäller resursutarmning (IEA, 2023; IRENA, 2022). Natriumjonbatterier är en lovande teknik för ESS-marknaden, som förväntas uppta 21 % av försäljningsmarknaden till 2030. Vilket skulle motsvara en efterfrågan på cirka 50 GWh natriumjonceller till 2030. De viktigaste drivkrafterna för en förmodad ökning av natriumbatterilagring är låga kostnader, överflödig tillgång på cellmaterial och förväntningar om att det ska vara ett säkrare och mer hållbart batteri. Litiumbatterier dominerar för närvarande energilagringsmarknaden, men har problem med etisk resursförsörjning och stigande mineralpriser, samtidigt som det finns en växande efterfrågan av energilagring. (BloombergNEF, 2023; IEA, 2023) Eftersom det finns sparsamt med information kring miljökonsekvenser av natriumbatteriproduktion (Liu et al., 2021; Peters et al., 2021) är syftet med den här studien att utvärdera miljöavtrycket av natriumjonbatterilagring. I studien utförs därför en livscykelanalys (LCA) på en bestämd natriumjoncell. Mer specifikt omfattar det att analysera det ekologiska avtrycket av 1 kWh producerad batterikapacitet, i ett cradle-to-gate-perspektiv. Resultaten presenteras dels som en fördelning av utsläppen över hela värdekedjan, inklusive material, transport och produktionspåverkan. Därtill visas en differentiering av cellmaterialets miljöpåverkan. Det berörda batteriet antas vara tillverkad i en giga scale produktion (>1 GWh årlig celltillverkning). Hypotetiskt antas tillverkningen placeras i Europa, men både en global och en lokal leveranskedja bedöms. I enlighet med europeiska initiativ finns det riktlinjer kallade PEFCR, som rekommenderar hur bedömningar av produkters miljöavtryck bör utföras. Det finns en specifik standard för miljöbedömning av batterier, vilken har eftersträvats i den här studien. I enlighet med rekommendationerna, innefattar den här studiens metod att utvärdera 16 miljöperspektiv, kallade EF2.0. De utsläppskategorier (EF2.0) som presenteras som huvudresultat är Climate Change (total), Acidification, Resource Use (fossils), Resource Use (minerals & metals), och Particulate Matter, eftersom dessa enligt PEFCR anses vara relevanta för just batterier. (European Commission and ReCharge, 2018) Det bör understrykas att den här studie har sitt huvudfokus på att analysera EF2.0 Climate Change (total), med målet att identifiera åtgärder för hur koldioxidavtrycket orsakat av batteriets livscykel kan minskas. För de 16 miljökategorierna, har ett natriumbatteris nuvarande läge ”current state scenario” satts i fokus. Utöver det presenteras ett ”decarbonized scenario” för EF2.0 Climate Change (total). För ”current state”-scenariot görs en jämförelse med ett litiumbatteri från industrin, vilket produceras med fossilfri energi. Därmed skapas förståelse för hur natriumbatteriets miljöpåverkan skiljer sig från det lågfossilintensiva litiumjoncellen. Både natrium- och litiumcellerna som ingår i jämförelsen har som avsikt att användas för energilagringssystem (ESS). Gällande resultatet av de 16 miljökategorierna är det tydligt att katoden är den främsta källan för utsläpp, följt av elektrolyten och anoden. I ”decarbonized scenario” illustreras därtill att om vissa specifika åtgärder implementeras i värdekedjan, skulle det kunna minska natriumbatteriers koldioxidutsläpp med potentiellt mer än hälften av vad som uppskattats idag. I nuläget pågår en utveckling och expansion av leveranskedjan för natriumbatteriproduktion (Rho motion, 2023), med en materialproduktion som börjar ta form. Samtidigt kan det i en snart framtid förväntas levereras natriumbatterier med högre energidensitet (Peters et al., 2021) och då skulle miljöpåverkan från natriumceller kunna sjunka avsevärt. Det centrala medskicket från den här studien är att resursanvändningen av mineraler och metaller drastiskt skulle minska i och med ett teknikskifte från litium- till natriumbatterier. Med de 16 miljöperspektiven i åtanke, är det övergripande resultatet att natriumceller orsakar mindre miljöskada jämfört med litiumteknik. Högst troligt, kan natriumceller i framtiden vara ett billigt och hållbart alternativ för energilagringssystem.

La demande urgente d'innovations dans le domaine du stockage de l'énergie est liée au développement récent de la production d'énergie renouvelable ainsi qu'à la diversification des produits électroniques portables qui consomment de plus en plus d'énergie. Il existe plusieurs technologies pour le stockage et la conversion électrochimique de l'énergie, les plus notables étant les batteries aux ions lithium, les piles à combustible et les supercondensateurs. Ces systèmes sont utilisés de façon complémentaire des uns aux autres dans des applications différentes. Par exemple, les batteries sont plus facilement transportables que les piles à combustible et ont de bonne densité d'énergie alors que les supercondensateurs ont des densités de puissance plus élevés et une meilleure durée de vie. L'objectif principal de ces travaux est d'étudier les performances électrochimiques d'une nouvelle famille de matériaux bidimensionnel appelée MXène, en vue de proposer de nouvelles solutions pour le stockage de l'énergie. Pour y arriver, plusieurs directions ont été explorées. Dans un premier temps, la thèse se concentre sur les supercondensateurs dans des électrolytes aqueux et aux effets des groupes de surface. La seconde partie se concentre sur les systèmes de batterie et de capacités à ions sodium. Une cellule complète comportant une anode en carbone et une cathode de MXène a été développées. La dernière partie de la thèse présente l'étude des MXènes pour les supercondensateur en milieu organique. Une attention particulière est apportée à l'étude du mécanisme d'intercalation des ions entre les feuillets de MXène. Différentes techniques de caractérisations ont été utilisées, en particulier la voltampérométrie cyclique, le cyclage galvanostatique, la spectroscopie d'impédance, la microscopie électronique et la diffraction des rayons X. / An increase in energy and power densities is needed to match the growing energy storage demands linked with the development of renewable energy production and portable electronics. Several energy storage technologies exist including lithium ion batteries, sodium ion batteries, fuel cells and electrochemical capacitors. These systems are complementary to each other. For example, electrochemical capacitors (ECs) can deliver high power densities whereas batteries are used for high energy densities applications. The first objective of this work is to investigate the electrochemical performances of a new family of 2-D material called MXene and propose new solutions to tackle the energy storage concern. To achieve this goal, several directions have been explored. The first part of the research focuses on MXene behavior as electrode material for electrochemical capacitors in aqueous electrolytes. The next part starts with sodium-ion batteries, and a new hybrid system of sodium ion capacitor is proposed. The last part is the study of MXene electrodes for supercapacitors is organic electrolytes. The energy storage mechanisms are thoroughly investigated. Different characterization techniques were used in this work, such as cyclic voltammetry, galvanostatic charge-discharge, electrochemical impedance spectroscopy, scanning electron microscopy and X-ray diffraction.

Na-ion batteries (NIBs) are expected to revolutionise the battery sector by promising an affordable technology while capitalising on sustainable development. To compete with Li-ion batteries, however, electrode materials with higher capacities need to be developed. Transition metal nitroprussides (TM-NPs), NaxM[Fe(CN)5NO]1-y ·zH2O, is a material class derived from one of the most popular positive electrode materials for NIBs, Prussian blue analogues (PBAs), where one of the cyano ligands have been replaced by an electroactive nitrosyl (NO) ligand. Thus, in theory TM-NPs should be able to reach higher capacities than PBAs and therefore be attractive candidates for high-capacity electrodes. However, if the nitrosyl is redox active in NIBs and how the cycling behaviour may be affected by the M cation is unknown. The focus in this thesis is therefore to explore the charge-discharge behaviour of four different TM-NPs (M=Fe, Ni, Mn, and Cu) in Na-ion half-cell batteries to gain an initial understanding of their electrochemical behaviour and to set up research questions to be pursued in the future. Based on our observations and previous studies, we propose that the nitrosyl is electrochemically active in all four TM-NPs, and that it contributes with a considerable amount of capacity, although with a large voltage hysteresis. It is further concluded that all M cations apart from Ni were redox active, but to varying degrees on charging and discharging. We argue that both the redox and the voltage hysteresis is caused by anisotropic charge transfer within the materials, and that it needs to be understood before commercialisation of TM-NPs can be realised. Though there are challenges to overcome, the many interesting attributes of TM-NPs, including anionic redox, anisotropic charge transfer and structural diversity, makes them promising as a new type of cheap and sustainable electrode material for NIBs.

Emerging markets in electrochemical energy storage, such as stationary grid storage, coupled with future concerns over the availability of lithium, places sodium-ion battery (SIB) technologies at a unique position to enter the market as a commercially viable alternative. Current shortcomings in the performance of cathode materials in SIBs would necessarily need to be addressed if this technology is to compete with existing commercial lithium-ion battery counterparts. Prussian White (PW), a promising cathode material currently being produced by Altris AB in Uppsala, Sweden, has been shown in many regards to be a promising candidate as a cathode material. In efforts to improve the lifetime, thermal stability, and rate capability of the material, both zinc oxide (ZnO) and polyaniline (PANI) coatings were applied to the active material powder.  Scanning electron microscopy (SEM) images of the ZnO coated PW showed that the ZnO was concentrated to certain regions, resulting in a rough and compromised coating. Furthermore, the notable presence of iron 2p orbital peaks in XPS spectra for ZnO and PANI coated samples, together with the SEM images, suggests that no method resulted in a conformal coating. Crystallographic information obtained using a capillary X-ray diffractometer showed that the PANI coating process had caused the PW to transition from a monoclinic to a cubic structure. This phase transition, based on subsequent thermogravimetric analysis, is attributed to an increase in both interstitial and lattice water content.  A comparative analysis of particle size and morphology, before and after slurry homogenization, showed that the ball milling technique used resulted in a reduction in size. Moreover, the ball milling process affected the uncoated PW more than the ZnO coated PW.  Findings, based on galvanostatic cycling of both full and half cells, indicate that the ZnO coating method on average results in a 12 mAh g1 loss in discharge capacity. The PANI coated PW showed a drop in capacity of approximately half that of the uncoated reference samples. No significant differences were observed in capacity retention, coulombic efficiency, and thermal stability between ZnO coated and uncoated PW. The better rate capability of the uncoated PW is suggested to be a result of the smaller particle size. Explanations for the observed similarities in electrochemical performance include (i) the breaking up of particles and agglomerates during the ball milling process (exposing uncoated faces), and (ii) the compromised coating. / Framväxande marknader inom elektrokemisk energilagring, såsom stationär nätlagring, i kombination med framtida oro över tillgängligheten av litium, placerar natriumjonbatteriteknik (SIB) i en unik position för att komma in på marknaden som ett kommersiellt lönsamt alternativ. Nuvarande brister i prestanda av katodmaterial i SIB måste nödvändigtvis åtgärdas om denna teknik ska konkurrera med befintliga kommersiella litiumjonbatterier. Prussian White (PW), ett lovande katodmaterial som produceras av Altris AB i Uppsala, Sverige, har i många avseenden visat sig vara en lovande kandidat som katodmaterial. I försök att förbättra materialets livslängd, termiska stabilitet och cyklingshastighetsförmåga applicerades både zinkoxid (ZnO) och polyanilin (PANI) -beläggningar på PW.  Svepelektronmikroskopi (SEM) -bilder av den ZnO-belagda PW visade att ZnO koncentrerades till vissa regioner, vilket resulterade i en grov och komprimerad beläggning. Vidare antyder närvaron av järn 2p orbitaltoppar i XPS-spektra för ZnO- och PANI-belagda prover, tillsammans med SEM-bilderna, att ingen metod resulterade i en lyckad beläggning. Kristallografisk information erhållen med användning av en kapillär röntgendiffraktometer visade att PANI-beläggningsprocessen hade orsakat en fasomvandling från en monoklinisk till en kubisk struktur. Denna fasomvandling, baserad på efterföljande termogravimetrisk analys, tillskrivs en ökning av både interstitiellt och gittervatteninnehåll.  En jämförande analys av partikelstorlek och morfologi före och efter homogenisering visade att den använda kulkvarnstekniken resulterade i en minskning i storlek. Dessutom påverkade kulkvarnsprocessen den obelagda PW mer än den ZnO-belagda PW.  Resultat, baserade på galvanostatisk cykling av både hel- och halvceller, indikerar att ZnO-beläggningsmetoden i genomsnitt resulterar i en 12 mAh g-1-förlust i urladdningskapacitet. Den PANI-belagda PW uppvisade en minskning i kapacitet på ungefär hälften av de obelagda referensproverna. Inga signifikanta skillnader observerades i kapacitetsretention, coulombisk effektivitet och termisk stabilitet mellan ZnO-belagd och obelagd PW. Den bättre hastighetsförmågan hos obelagd PW föreslås vara ett resultat av den mindre partikelstorleken. Förklaringar för de observerade likheterna i elektrokemisk prestanda innefattar (i) uppbrytning av partiklar och agglomerat under kulfräsningsprocessen (exponering av obelagda ytor) och (ii) ofullständig beläggning.

<p>Sodium (Na)-ion battery displays many properties similar to Lithium (Li)-ion battery, such as operating principles and capacity, which noticeably compressed the Na-ion battery cathode exploration period. Having said that, anode materials of Na-ion battery is still underperforming as commercial graphite is inadequate in storing bulky Na ions. In the search for anode materials, both alloy-type and Na metal anode materials have gained popularity as these materials can absorb more charges and have higher storage capacity. It is essential to remember that such materials exhibit massive volume expansion upon sodiation and hence experience considerable mechanical stress upon cycling, leading to fractures and pulverization of the electrodes. In addition to electrode stability, ionic motions between the electrode and electrolyte are pivotal in determining the battery response. The decomposition of the electrolyte cocktails forms a passivation layer on the electrode surface, known as solid electrolyte interphase (SEI), which can rupture and regenerate in unstable cycles. Rickety SEI can cause the consumption of active Na and the formation of local hotspots for notorious dendrite growth, leading to short battery durability.</p> <p><br></p> <p>In the first part of the thesis, Tin (Sn) has been selected as an exemplar system to study the dynamic changes in a Na-ion battery. Higher ion-uptake capabilities of Sn electrode come with a price of large structural and morphological changes and can be controlled by careful charting of non-active phases such as binder and suitable electrolyte solution. This work comprehensively studies the technical challenges associated with Sn with different binder domains and in different liquid electrolyte environments. Parallelly, the sensitivity of the Na-Sn system towards the operating potential window and the crosstalk between the working electrode (alloying and de-alloying) and the counter electrode (plating and stripping) has been untied. Also, a fundamental understanding of the materials-transport-interface interactions during thermal abuse tests and their implication on the safety aspects of Na-ion batteries has been addressed. </p> <p><br></p> <p>Following that, the morphological stability of the Na metal anode is investigated based on the distinct electrochemical reactions arising from the composition of different liquid electrolytes. The role heterogeneity in the SEI layer of Na metal for the growth of dendritic patterns has been discussed. A unified framework incorporating a detailed electrochemical study of various electrolyte formulations, cognizant of the reactions and kinetics at the electrode-electrolyte interface, has been developed. To mechanistically counter the heterogeneity implications and synergistically leverage the electrolyte-additive-driven improvement in ionic transport, a flux-homogenizing separator has been introduced to extend the battery cycling. Based on this synergistic approach, the complex interplay between the homogeneity in SEI composition, electrodeposition/dissolution morphology, and cell performance in Na-metal-based batteries has been identified.</p> <p><br></p> <p>This work tried to offer fresh insights on fundamental mechanisms governing the evolution of the electrode-electrolyte interphases and their role in determining electro-chemo-mechano-thermal stability for future research endeavors in the Na-ion battery field. </p>

The need for highly efficient energy storage devices has been steadily increasing due to growing energy demands. Research in electrochemical energy storage in the form of batteries has consequently become crucial. Currently, the most commercialized battery technology is the lithium ion battery (LIB). Concerns over the relatively limited global lithium supply, however, have led to the development of sodium ion batteries (SIBs). Solid-state nuclear magnetic resonance (ssNMR) spectroscopy is an ideal technique for analyzing battery materials as it can potentially distinguish between different ions within the material. The most typical cathode for commercial LIBs are the family of NMC layered oxides with the general form Li[NixMnyCo1-x-y]O2, which consist of Li layers between sheets of transition metals (TMs). The pj-MATPASS NMR technique, in conjunction with Monte Carlo simulations, was applied to investigate the ionic arrangement within TM layers of NMC622 (Li[Ni0.6Mn0.2Co0.2]O2), which revealed the presence of ion clustering in the pristine form of this material. This thesis also investigated the promising SIB cathode, Na3V2(PO4)2F3 (NVPF). NVPF has the capability to produce energy densities comparable to those of LIBs and is well understood from a structural standpoint, however ion dynamics within the material are still undetermined. A series of materials have, therefore, been synthesized with the general form, Na3V2-xGax(PO4)2F3 (where x = 0, 1, and 2), where diamagnetic Ga3+ was introduced into the structure to enable the establishment of a structural correlation with observed Na-ion dynamics. It, therefore, became possible to explore ionic site exchange using 23Na ssNMR. Density functional theory (DFT) calculations have also been performed alongside ssNMR to confirm chemical shift assignments and provide structural insight. Additionally, electron paramagnetic resonance (EPR) spectroscopy was also used to investigate the paramagnetic nature of NVPF and its variants. Insights into the ionic arrangement and very fast Na-ion dynamics within these materials were revealed. / Thesis / Master of Science (MSc) / The need for highly efficient energy storage devices, especially in the form of batteries, has been steadily increasing due to growing energy demands. Presently, the most commercialized types of batteries are lithium ion batteries (LIBs). Concerns over the relatively limited global lithium supply, however, have led to the development of sodium ion battery (SIB) alternatives. Various solid-state nuclear magnetic resonance (ssNMR) techniques have been employed in this thesis to investigate both LIB and SIB cathode materials. The LIB cathode Li[Ni0.6Mn0.2Co0.2]O2 was examined with a combination of ssNMR and Monte Carlo simulations, and it was found that ion clustering occurs in the pristine form of these materials. The promising family of SIB cathodes, Na3V2-xGax(PO4)2F3, was studied by a combination of ssNMR, ab initio calculations, and EPR, which allowed for a correlation to be established between the crystal structure and the fast ion dynamics within these materials.

In dieser Arbeit wurden zwei Messaufbauten für die online Gasanalyse von elektrochemischen Reaktionen entwickelt und im Hinblick auf ihre Unterschiede und Gemeinsamkeiten sowie auf den Designprozess im Allgemeinen verglichen: Differenzielle elektrochemische Massenspektrometrie (DEMS) zur Untersuchung von Nebenreaktionen in Natriumionenbatterien (SIBs). Verschiedene Designansätze aus der Literatur wurden verglichen, um den für die Anwendung in SIBs am besten geeigneten zu finden. Danach wurde ein selbst entwickeltes Design implementiert und validiert. Für die Datenauswertung wird ein neuartiger Ansatz für DEMS in Alkaliionenbatterien vorgestellt, der eine interne Validierung der Ergebnisse ermöglicht. Eine Zusammenfassung der Literatur über bekannte Reaktionen, die zur Gasbildung in Alkali-Ionen-Batterien führen, wird als Referenz die Gasentwicklung in den in dieser Arbeit untersuchten Materialien herangezogen. Das System wird zur Messung der Gasentwicklung verschiedener Elektrodenmaterialien in Halbzellenkonfiguration und zur Bewertung des Zusammenspiels einiger Elektroden in Vollzellenkonfiguration verwendet. Bei den untersuchten Materialien handelt es sich um: Natrium-Mangan-Nickeloxid (NaMNO), Natrium-Vanadium-Phosphat (NVP), Preußisch Weiß (PW), Graphit und Hartkohlenstoff. Als Elektrolyte wurden überwiegend 1M NaPF6 in Diglyme (2G), bzw. Propylencarbonat (PC) verwendet. Das zweite System ist eine rotierende Scheibenelektrode in Verbindung mit Gaschromatographie (RDE-GC). Es wurde entwickelt, um kinetische Effekte bei der elektrokatalytischen CO2-Reduktion an Kupferelektroden zu untersuchen. Die Korrelation von Massentransporteigenschaften und der Gasproduktanalyse kann Aufschluss über die Massentransportabhängigkeit von Selektivität und Aktivität der Reaktion geben. Hier wird die Gasanalyse genutzt, um die elektrochemischen Daten in Teilstromdichten zu dekonvolutieren, die unter definierten Stofftransportbedingungen zur Bildung verschiedener Produkte führen. / In this thesis two independent measurement setups for online gas analysis, in electrochemical reactions are developed and compared in terms of their differences and similarities and on the design: Differential electrochemical mass spectrometry (DEMS) for the investigation of side reactions in sodium-ion batteries (SIBs). Different design approaches from literature are evaluated to find the most suitable for the application in SIBs. After that a custom design is implemented and validated. A novel approach to DEMS in alkali-ion batteries for the data evaluation is presented, that enables internal verification of the results. Known reactions that lead to gas formation in alkali-ion batteries are reviewed form the literature, as a reference to discuss the gas evolution found in materials investigated. The system is used to measure the gas evolution of different electrode materials in half-cell configuration, and to evaluate the interplay of some of the electrodes in full-cell configuration. Materials that are studied are: sodium manganese nickel oxide (NaMNO), sodium vanadium phosphate (NVP), prussian white (PW), graphite and hard carbon. To do that two model electrolytes were selected 1M NaPF6 in diglyme (2G) and propylene carbonate (PC). The second system is a rotating disc electrode coupled with gas chromatography (RDE-GC). It is designed to study kinetic effects on the electrocatalytic CO2 reduction (CO2RR) on copper electrodes. The correlation of defined mass transport properties and gas product analysis can give insight into the mass transport dependencies on the selectivity and activity of the reaction. Here the gas analysis is used to deconvolute the electrochemical data into partial current densities, that lead to the formation of different products, under defined mass transport conditions. While some challenges remain, preliminary data that underlines the capability of such system as well as the findings on how to design such a system are presented.

An urgent transformation from fossil fuels to cleaner energy sources to combat climate change has led to the utilization of renewable energies like solar, wind, and tidal power. However, the intermittency of these sources hinders their wider implementation. To address this, large-scale electrical energy storage (EES) systems are needed. These systems store excess energy during periods of surplus and release it during peak demand, enhancing grid reliability. Secondary batteries have been developed as promising EES solutions due to their reliability, independence from weather, and ease of maintenance. While lithium-ion batteries (LIBs) are popular as secondary batteries, their limited lithium supply, and rising costs demand for cost-effective alternatives. This study focuses on developing sodium iron fluorophosphate (Na2FePO4F) as a promising cathode material for SIBs. Because of its iron-based composition, which is generated from sustainable sources, Na2FePO4F offers a potential solution to the cost and supply difficulties related with LIBs. However, challenges exist, including low electronic conductivity and inferior electrochemical performance. To address these challenges, this research explores mechanochemically assisted solid-state synthesis routes as a low-cost and environmentally friendly approach. The characterization and performance evaluation of Na2FePO4F (NFPF) and NFPF/C positive electrode materials for sodium-ion batteries (SIBs) were systematically investigated through a range of analytical techniques, including XRD, TGA, SEM-EDS, FT-IR, and Raman analyses. A single-step solid-state synthesis demonstrates effectiveness in producing NFPF and NFPF/C-positive electrode materials. Moreover, Fe2O3 nanoparticles serve as the primary iron source in the solid-state synthesis of iron-based fluorophosphate Na2FePO4F/C, successfully producing both NFPF pristine phase and NFPF carbon-coated active materials. Finally, a comparison between the two synthesis pathways reveals that the active material from single-step solid-state synthesis exhibits a superior initial discharge specific capacity of 74.24 mAh⋅g−1 at 0.005 C, outperforming the double-step solid-state synthesis. These findings can contribute to the development of affordable and sustainable energy storage solutions, offering alternatives to traditional LIBs. / En akut omvandling från fossila bränslen till renare energikällor för att bekämpa klimatförändringarna har lett till ett utnyttjande av förnybar energi som sol-, vind- och tidvattenkraft. Emellertid hindrar dessa källors intermittenser deras bredare genomförande. För att komma till rätta med detta behövs storskaliga system för lagring av elektrisk energi (EES). Dessa system lagrar överskottsenergi under perioder med överskott och släpper ut den under toppbelastning, vilket förbättrar nätets tillförlitlighet. Sekundära batterier har utvecklats som lovande EES-lösningar på grund av deras tillförlitlighet, väderberoende och enkla underhåll. Medan litiumjonbatterier (LIB) är populära som sekundära batterier, kräver deras begränsade litiumtillgång och stigande kostnader kostnadseffektiva alternativ. Denna studie fokuserar på att utveckla natriumjärnfluorfosfat (Na2FePO4F) som ett lovande katodmaterial för SIB. På grund av sin järnbaserade sammansättning, som genereras från hållbara källor, erbjuder Na2FePO4F en potentiell lösning på kostnads- och försörjningssvårigheter relaterade till LIB. Men det finns utmaningar, inklusive låg elektronisk konduktivitet och sämre elektrokemisk prestanda. För att möta dessa utmaningar undersöker denna forskning mekanokemiskt assisterade syntesvägar i fast tillstånd som ett billigt och miljövänligt tillvägagångssätt. Karakteriseringen och prestandautvärderingen av Na2FePO4F (NFPF) och NFPF/C positiva elektrodmaterial för natriumjonbatterier (SIB) undersöktes systematiskt genom en rad analytiska tekniker, inklusive XRD, TGA, SEM-EDS, FT-IR och Raman analyser. En enstegs solid state-syntes visar effektivitet vid framställning av NFPF och NFPF/C-positiva elektrodmaterial. Dessutom tjänar Fe2O3-nanopartiklar som den primära järnkällan i solid state-syntesen av järnbaserat fluorfosfat Na2FePO4F/C, vilket framgångsrikt producerar både NFPF orörd fas och NFPF kolbelagda aktiva material. Slutligen avslöjar en jämförelse mellan de två syntesvägarna att det aktiva materialet från enstegs-solid-state-syntes uppvisar en överlägsen initial urladdningsspecifik kapacitet på 74,24 mAh⋅g−1 vid 0,005 C, vilket överträffar dubbelstegs-solid-state-syntesen. Dessa resultat kan bidra till utvecklingen av prisvärda och hållbara energilagringslösningar, som erbjuder alternativ till traditionella LIB.

The environmental concerns over the use of fossil fuels, and their resource constraints, as well as energy security concerns, have spurred great interest in generating electric energy from renewable sources. Solar and wind energy are abundant and potentially readily available. However, the generation of sustainable energies is generally intermittent and these energies have geographical limits which are relative to current large-scale energy generation facilities. To smooth out the intermittency of renewable energy production, low-cost electrical energy storage (EES) devices are becoming highly necessary. Among these EES technologies, lithium ion batteries are one of the most promising EES devices in terms of the characteristics of high gravimetric, volumetric energy density and environmentally friendly compared to lead-acid batteries and Ni-Cd batteries. Other advantages of Li-ion batteries are the ability of being recharged hundreds of times and high stability. Moreover, the dramatically growing market share of hybrid electrical and electrical vehicles in automobiles has motivated the development of high energy and power density LIBs with high mass loading. However, there are still several remaining challenges in LIBs for their further application in grid-scale ESSs. One of the global issues to date is the high costs including the cost of raw materials such as lithium and cobalt, production, machining, and transportation, etc. In addition, the increasing energy demand thereby leads to the pressures on the resource supply chains and thus increasing the cost of LIBs. Therefore, it is urgent to find a complementary or alternative EES device in a short term to satisfy the growing energy demand. Under the background of fast development of LIBs technology as well as the establishment of Li chemistry fundamentals in the last 40 years, rechargeable battery systems utilizing Na element have been extensively studied to develop less expensive and more sustainable ESSs. The sodium resource is abundantly existed in the planet. According to the periodic table, sodium is the most possible alternative to lithium, because it has the similar chemical and physical properties towards to lithium. As a consequence, the established fundamentals in LIBs can be reasonably analogized to SIBs. Moreover, Sodium is readily available from various sources-foods that contain sodium naturally, foods containing salt and other sodium-containing ingredients. Therefore, The study of SIBs technology and sodium chemistry are gaining increasing interests and attentions both in the scientific researchers and battery industry. However, theoretically speaking, the energy density of SIBs is lower than that of LIBs by using same electrode materials because sodium is more than 3 times heavier than Li as well as the standard electrode potential of Na (-2.71 V) is higher than Li (-3.04 V). Therefore, SIBs are not thought as an ideal candidate to substitute LIBs in the fields of small or middle-size portable devices, but are more favorable in a large grid support where the operation cost is the primary choice. Negative electrode is important component in a single cell. Exploring negative electrode materials with high electrochemical performance in LIBs and SIBs is indeed required for fulfilling the spreading energy demand. Among various negative electrode materials, layered transition metal sulfides (MSs) are reckoned as a promising class with high theoretical specific capacity and power capability due to their intrinsically layered structure which is beneficial to the diffusion of Li+ and Na+ . However, layered transition metal sulfides are suffering from intrinsically poor electrical conductivity, volume changes, high irreversibility and sluggish kinetics during Li+ /Na+ storage process. To address these issues, numerous strategies are applied to explore high performance LIBs and SIBs negative electrode materials in this PHD thesis. / Die ökologischen Bedenken hinsichtlich der Nutzung fossiler Brennstoffe und deren Ressourcenbeschränkungen sowie Bedenken hinsichtlich der Energiesicherheit haben großes Interesse an der Erzeugung elektrischer Energie aus erneuerbaren Quellen geweckt. Sonnen- und Windenergie sind im Überfluss vorhanden und potenziell leicht verfügbar. Die Erzeugung nachhaltiger Energien ist jedoch in der Regel intermittierend, und diese Energien haben geographische Grenzen, die im Vergleich zu den derzeitigen großen Energieerzeugungsanlagen relativ begrenzt sind. Um die Unterbrechungen in der Produktion erneuerbarer Energien auszugleichen, werden kostengünstige elektrische Energiespeicher (EES) dringend notwendig. Unter diesen EES-Technologien sind Lithium-Ionen-Batterien eines der vielversprechendsten EES-Geräte hinsichtlich der Eigenschaften einer hohen gravimetrischen, volumetrischen Energiedichte und umweltfreundlich im Vergleich zu Blei-Säure-Batterien und Ni-Cd-Batterien. Weitere Vorteile von Lithium-Ionen-Batterien sind die Fähigkeit, hunderte Male wieder aufgeladen werden zu können, und die hohe Stabilität. Darüber hinaus hat der dramatisch wachsende Marktanteil von Hybrid- und Elektrofahrzeugen in Automobilen die Entwicklung von LIBs mit hoher Energie- und Leistungsdichte und hoher Massenbelastung motiviert. Es gibt jedoch noch einige Herausforderungen in den LIBs, die für die weitere Anwendung in den ESSs im Rastermaßstab erforderlich sind. Eine der bisherigen globalen Fragen sind die Gesamtkosten einschließlich der Kosten für Rohstoffe wie Lithium und Kobalt, Produktion, Bearbeitung und Transport usw. Darüber hinaus führt die steigende Energienachfrage dadurch zu einem Druck auf die Ressourcenversorgungsketten und damit zu einer Verteuerung der LIBs. Daher ist es dringend erforderlich, kurzfristig eine ergänzende und alternative EES-Technologie zu finden, um den wachsenden Energiebedarf zu decken. Vor dem Hintergrund der schnellen Entwicklung der LIBs-Technologie sowie der Etablierung der Grundlagen der Li-Chemie in den letzten 40 Jahren wurden wiederaufladbare Batteriesysteme, die das Na-Element verwenden, umfassend untersucht, um kostengünstigere und nachhaltigere ESSs zu entwickeln. Die Natriumressource ist auf der Erde im Überfluss vorhanden. Nach dem Periodensystem ist Natrium die möglichste Alternative, da es die ähnlichen chemischen und physikalischen Eigenschaften von Lithium hat. Folglich lassen sich die etablierten Grundlagen der LIBs in vernünftiger Weise mit denen der SIBs vergleichen. Darüber hinaus ist Natrium aus verschiedenen Quellen leicht erhältlich - aus Lebensmitteln, die von Natur aus Natrium enthalten, aus Lebensmitteln, die Salz und andere natriumhaltige Zutaten enthalten. Daher gewinnt das Studium der SIBs-Technologie und Natriumchemie sowohl in der wissenschaftlichen Forschung als auch in der Batterieindustrie zunehmend an Interesse und Aufmerksamkeit. Theoretisch gesehen ist jedoch die Energiedichte von SIBs bei Verwendung der gleichen Elektrodenmaterialien niedriger als die von LIBs, da Natrium mehr als dreimal schwerer als Li ist und das Standardelektrodenpotential von Na (-2,71 V) höher als Li (-3,04 V) ist. Daher werden SIBs nicht als idealer Kandidat für den Ersatz von LIBs im Bereich kleiner oder mittelgroßer tragbarer Geräte angesehen, sondern sie sind günstiger bei einer großen Netzunterstützung, bei der die Betriebskosten die primäre Wahl sind. Die negative Elektrode ist ein notwendiger und wichtiger Teil in einer einzelnen Zelle. In der Tat ist es zur Erfüllung des sich ausbreitenden Energiebedarfs erforderlich, negative Elektroden-Materialien mit hoher elektrochemischer Leistung in LIBs und SIBs zu untersuchen. Unter den verschiedenen Materialien für negative Elektroden gelten geschichtete Übergangsmetallsulfide (MS) als eine vielversprechende Klasse mit hoher theoretischer spezifischer Kapazität und Leistungskapazität aufgrund ihrer intrinsisch geschichteten Struktur, die der Diffusion von Li+ und Na+ förderlich ist. Allerdings leiden schichtförmige Übergangsmetallsulfide unter inhärent schlechter elektrischer Leitfähigkeit, Volumenänderungen, hoher Irreversibilität und träger Kinetik während des Li+ /Na+ -Speicherprozesses. Um diese Probleme anzugehen, werden in dieser Doktorarbeit zahlreiche Strategien zur Untersuchung von Hochleistungs-LIBs und SIBs für negative Elektrodenmaterialien angewandt.