This diploma thesis deals with the description of individual types of batteries. The first part is focused to primary and secondary batteries, materials for their positive and negative electrodes with a focus on lithium-ion batteries and their changes over time. The next section focuses on a more detailed description of sodium-ion batteries, used electrode materials and to their problems. Practical part is focesed to preparing of electrode materials and to completing of measuring electrochemical cell and to discribing of measuring methodes and to evaluation of measured data.

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most popular positive electrode materials for NIBs, Prussian blue analogues (PBAs), where one of the cyano ligands have been replaced by an electroactive nitrosyl (NO) ligand.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>

Opioid analgesics have been a major contribution to pain therapy with opioids being used as an effective treatment for various recalcitrant pain conditions. The drug class has come under increased scrutiny due to the raising concerns about the public health crisis of opioid misuse and addiction, thereby increasing the need for alternative and safer analgesics. The exploration of alternative pharmacotherapy for pain management has led to an increasing paradigm shift towards the development of a single-drug-multiple-target approach that takes inspiration from numerous naturally occurring drugs. The mu-opioid receptor has been the primary target for the management of pain; however, the voltage-gated sodium channel Nav1.7 is gaining attention as a putative antinociceptive target based on human genetic evidence. The proposed research aims to develop multi-target directed ligands (MTDL) that modulates two key targets for pain perception, the MOR, and Nav1.7 to generate analgesics with reduced side effects and enhanced analgesia. This will be achieved by exploiting polypharmacology to develop hybrid analgesia in two ways: (i) performing structure-activity relationship (SAR) studies to design a single drug with two pharmacophores that specifically interacts with both the targets (ii) exploiting in silico techniques by performing structure-based virtual ligand screening (VLS) of a chemical library. In our work, we report that through SAR studies and molecular docking studies that the designed compounds having in combination the pharmacophore of PZM21 and aryl sulfonamide demonstrate significant interactions between the active compounds and both the MOR and Nav1.7 proteins. This study also reports the first ever bifunctional virtual ligand screening where a library consisting of over a million compounds was screened for bifunctional activity at the MOR and the Nav1.7 ion channel. We also report the development of a novel mechanism-specific membrane potential assay to that can be used to screen for subtype selective Nav1.7 inhibitors. The research performed in this thesis will serve as a platform to explore the possibility of MTDL as potential therapeutic solutions to diseases of complex etiologies such as chronic pain. It will also serve as a starting point to exploring bifunctional VLS as a way to screen large chemical libraries for MTDLs.

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 this thesis, a Sb/C composite electrode for sodium-ion batteries isprepared by a simple high energy ball milling and calenderingmethod. The prepared Sb/C composite electrode was assembled in ahalf-cell and symmetrical cell setups in order to perform avariety of electrochemical measurements.The composite electrode showed a reversible specific capacity of595 mAh/g, at a discharge/charge current rate of 15 mA/g. Theelectrode also showed a relatively good performance (compared toprevious studies) of 95% capacity retention after more than 100cycles, at a higher discharge/charge current rate of 60 mA/g. Theelectrode furthermore showed excellent self-dischargecharacteristics, in pause tests implemented over 200 hours (overeight days), which underlined the electrode materials good shelflife properties. A series of Sb/C symmetrical cells assembledthrough-out the project, furthermore, highlighted the stability ofthe solid electrolyte interface (SEI) layer formed on the Sb/Ccomposite electrode during cycling. Scanning electron microscopy(SEM) and Energy-dispersive X-ray spectroscopy (EDS) were used tocharacterize the surface morphology and composition of the Sb/Celectrode, respectively.A non-milled and milled (12 hours) graphite electrodes were alsoprepared for reference and comparison. The milled graphite matrixelectrode provided a reversible capacity of 95 mAhg-1 and acoulombic efficiency (CE) of 99% in over 250 cycles, at a currentrate of 30 mA/g. Milled and non-milled graphite were characterizedwith SEM and Raman spectroscopy, to help have a fundamentalunderstanding of the particle size and material phase,respectively.

This work focuses on sodium-ion batteries. It describes the basic principles of accumulators, focusing more on secondary cells, their electrodes, especially negative electrodes. The work is lightly based on the basics of lithium-ion batteries. The practical part of the work is the production of negative electrodes Na2Ti3O7, which are further measured at three different temperatures. These measurements are then evaluated.

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.