Li-ion battery technology is currently the most efficient form of electrochemical energy storage. The commercialization of Li-ion batteries in the early 1990’s revolutionized the portable electronics market, but further improvements are necessary for applications in electric vehicles and load levelling of the electric grid. In this thesis, three new iron based electrode materials for positive electrodes in Li-ion batteries were investigated. Utilizing the redox activity of iron is beneficial over other transition metals due to its abundance in the Earth’s crust. The condensed phosphate Li2FeP2O7 together with two different LiFeSO4F crystal structures that were studied herein each have their own advantageous, challenges, and scientific questions, and the combined insights gained from the different materials expand the current understanding of Li-ion battery electrodes. The surface reaction kinetics of all three compounds was evaluated by coating them with a conductive polymer layer consisting of poly(3,4-ethylenedioxythiophene), PEDOT. Both LiFeSO4F polymorphs showed reduced polarization and increased charge storage capacity upon PEDOT coating, showing the importance of controlling the surface kinetics for this class of compounds. In contrast, the electrochemical performance of PEDOT coated Li2FeP2O7 was at best unchanged. The differences highlight that different rate limiting steps prevail for different Li-ion insertion materials. In addition to the electrochemical properties of the new iron based energy storage materials, also their underlying material properties were investigated. For tavorite LiFeSO4F, different reaction pathways were identified by in operando XRD evaluation during charge and discharge. Furthermore, ligand involvement in the redox process was evaluated, and although most of the charge compensation was centered on the iron sites, the sulfate group also played a role in the oxidation of tavorite LiFeSO4F. In triplite LiFeSO4F and Li2FeP2O7, a redistribution of lithium and iron atoms was observed in the crystal structure during electrochemical cycling. For Li2FeP2O7, and increased randomization of metal ions occurred, which is similar to what has been reported for other iron phosphates and silicates. In contrast, triplite LiFeSO4F showed an increased ordering of lithium and iron atoms. An electrochemically induced ordering has previously not been reported upon electrochemical cycling for iron based Li-ion insertion materials, and was beneficial for the charge storage capacity of the material.

The aim of this master thesis was to establish if sodium is trapped in aluminium current collectors, which in turn could affect the capacity fade in sodium-ion battery systems. In the case of lithium-ion batteries, previous studies have shown that a trapping mechanism, where lithium diffuses through the active material and current collectors, can explain the capacity fade observed for several systems. However, no such reports have been published in the sodium case, motivating this pioneering investigation. Contact samples of sodium and aluminium current collector material confirmed the uptake of sodium as shown by ICP-AES analyses. The uptake of sodium in the aluminium was equivalent to a charge of 0.4 µAh after 70 days of contact at 55°C. The main characterisation method was galvanostatic plating and stripping of sodium on aluminium in a pouch-cell configuration. When using a bare aluminium working electrode with a metallic sodium counter electrode in a 1 M NaPF6/diglyme electrolyte, the galvanostatic cycling showed coulombic efficiency instabilities. It was concluded that a more stable, high efficient plating-stripping would be needed to quantify the effects of sodium trapping with the employed electrochemical methods. Coulombic efficiency values that exceeded 100 % were attributed to the oxidation of disconnected (detached) sodium from previous plating cycles. On consecutive cycles some of the disconnected sodium got reconnected, resulting in coulombic efficiency values well over 100 %.

<p>This thesis is based on a study of five distinct intermetallic systems with the aim of expanding the general knowledge of aperiodically modulated crystal structures. Families of compounds that contain a variety of superstructures together with incommensurately modulated structures have been investigated mainly by means of single crystal X-ray diffraction and higher dimensional structure models.</p><p>A uniform (3+1)-dimensional structure for Bi-Se phases was developed with the composition as a single variable. The structure description is based on a cubic NaCl type structure with homoatomic layer stackings. It is shown by computational modelling that the formation energies of bismuth selenides with more than 40 at. % Bi are close to zero, a result that supports the idea of a continuous series of stackings corresponding to an ordered solid solution of Bi in Bi₂Se₃.</p><p>The Nowotny chimney-ladder structures are described with a (3+1)-dimensional composite structure, valid for all such compounds regardless of the included elements, the composition or the valence electron concentration. A new member is added to this family by the ZrBi_1.62 compound. The modulation is believed to arise as a secondary effect of the criteria of a fixed electron count.</p><p>A symmetry analysis is presented for the <i>RE</i>_1+ε(MB)₄ (<i>RE</i> = rare earth elements, M = iron metal elements) family of compounds and a uniform (3+1)-dimensional composite structure description has been developed. The modulation may be due to the presence of unusually short contacts between the <i>RE</i> channel atoms, giving rise to a rotational modulation of the (MB)₄ tetraederstern chains.</p><p>A (3+1)-dimensional incommensurate structure has been determined for the novel δ₁ – CoZn compound. The structure displays a unique assembly of fused icosahedra and the modulation is induced by geometric strain.</p><p>The structure of the K(PtSi)₄ compound was re-determined. Despite a close kinship with the <i>RE</i>_1+ε(MB)₄ compounds, this structure is not modulated.</p>

<p>Nano-powders of BaTiO₃, SrTiO₃, Ba_0.6Sr_0.4TiO₃, a mixture of the composition (BaTiO₃)_0.6(SrTiO₃)_0.4 with particle sizes in the range of 60 to 80 nm, and Bi₄Ti₃O₁₂ with an average particle size of 100 nm were consolidated by spark plasma sintering (SPS). The kinetics of reaction, densification and grain growth were studied. An experimental procedure is outlined that allows the determination of a “kinetic window” within which dense nano-sized compacts can be prepared. It is shown that the sintering behaviour of the five powders varies somewhat, but is generally speaking fairly similar. However, the types of grain growth behaviour of these powders are quite different, exemplified by the observation that the kinetic window for the (BaTiO₃)_0.6(SrTiO₃)_0.4 mixture is 125 ^oC, ~75 ^oC for Bi₄Ti₃O₁₂, ~25^oC for BaTiO₃ and SrTiO₃, while it is hard to observe an apparent kinetic window for obtaining nano-sized compacts of Ba_0.6Sr_0.4TiO₃. During the densification of the (BaTiO₃)_0.6(SrTiO₃)_0.4 mixture the reaction 0.6BaTiO₃+0.4SrTiO₃ → Ba_0.6Sr_0.4TiO₃ takes place, and this reaction is suggested to have a self-pinning effect on the grain growth, which in turn explains why this powder has a large kinetic window. Notably, SPS offers a unique opportunity to more preciously investigate and monitor the sintering kinetics of nano-powders, and it allows preparation of ceramics with tailored microstructures.</p><p>The dielectric properties of selected samples of (Ba, Sr)TiO₃ ceramics have been studied. The results are correlated with the microstructural features of these samples, <i>e.g.</i> to the grain sizes present in the compacts. The ceramic with nano-sized microstructure exhibits a diffuse transition in permittivity and reduced dielectric losses in the vicinity of the Curie temperature, whereas the more coarse-grained compacts exhibit normal dielectric properties in the ferroelectric region.</p><p>The morphology evolution, with increasing sintering temperature, of bismuth layer-structured ferroelectric ceramics such as Bi₄Ti₃O₁₂ (BIT) and CaBi₂Nb₂O₉ (CBNO) was investigated. The subsequent isothermal sintering experiments revealed that the nano-sized particles of the BIT precursor powder grew into elongated plate-like grains within a few minutes, via a dynamic ripening mechanism.</p><p>A new processing strategy for obtaining highly textured ceramics is described. It is based on a<i> directional dynamic ripening mechanism</i> <i>induced by superplastic deformation</i>. The new strategy makes it possible to produce a <i>textured</i> microstructure within minutes, and it allows production of textured ferroelectric ceramics with tailored morphology and improved physical properties.</p><p>The ferroelectric, dielectric, and piezoelectric properties of the textured bismuth layer-structured ferroelectric ceramics have been studied, and it was revealed that all textured samples exhibited anisotropic properties and improved performance. The highly textured Bi₄Ti₃O₁₂ ceramic exhibited ferroelectric properties equal to or better than those of corresponding single crystals, and much better than those previously reported for grain-orientated Bi₄Ti₃O₁₂ ceramics. Textured CaBi₂Nb₂O₉ ceramics exhibited a very high Curie temperature, <i>d</i><i>33</i>-values nearly three times larger than those of conventionally sintered materials, and a high thermal depoling temperature indicating that it is a very promising material for high-temperature piezoelectric applications.</p>

<p>Complex transition metals oxyhalides containing a lone pair element, such as tellurium (IV), form an attractive research field because there is a high probability of finding new low-dimensionally arranged compounds and, particularly, a low-dimensionally arranged transition metals substructures, leading to interesting physical properties. Tellurium (IV) can drive the formation of many unusual structures because of its stereochemically active lone pair electrons, E. It commonly takes a coordination of three or four oxygen atoms to form either a TeO3E square pyramid or a TeO3+1E trigonal bipyramid. These lone pairs are very important players involved in lowering the dimensionality of crystal structures. Previous studies in transition metal tellurium (IV) oxohalide quarternary systems revealed a family of compounds, many of which exhibit interesting properties e.g. magnetic frustration. The unique point of this thesis is to employ alkaline earth elements (AE) to augment this ability of lone pair elements to lower the dimensionality of the transition metal arrangements. By this double usage of “chemical scissors” (a lone pair element used in conjunction with alkaline earth elements) we obtained new types of low-dimensionally arranged compounds.</p><p>This thesis is focused on the syntheses and characterization of a series of compounds in the pentanary (five components) system AE-TeIV-TM-O-X (AE=alkaline earth metal, TM=transition metal and X=halogen), in which nine new compounds were found. The crystal structures of each of these compounds were determined by the single crystal X-ray diffraction data.</p>

<p>There is a strong driving force to increase the competitiveness of the pulping industry by finding new business opportunities. In this context full utilisation of the wood raw material used in conventional pulping mills is of vital importance. One focus area is to increase the utilisation areas of lignin. LignoBoost is a new method to obtain kraft lignin of high purity.</p><p>The aim of the project was to investigate and increase the ability of LignoBoost kraft lignins to bind metals in aqueous solutions.</p><p>The metal binding property of kraft lignins was evaluated using copper (II) ions. The metal binding capacities were 1.76 mg Cu²⁺/g LignoBoost softwood kraft lignin, 0.96 mg Cu²⁺/g LignoBoost hardwood kraft lignin and 1.12 mg Cu²⁺/g condensed softwood kraft lignin. The metal binding capacities of the softwood and hardwood kraft lignins from LignoBoost were lower than expected, when compared to the metal binding capacities of other lignins found in literature. The highest copper binding capacity of a kraft lignin found in literature was almost 50 times greater than that of the LignoBoost softwood kraft lignin.</p><p> </p><p>The Mannich reaction was used to increase the nitrogen content in softwood lignin, and thereby increase its electron-donating capacity. An increase in electron-donating capacity should promote its metal binding capacity.</p><p> </p><p>The Mannich reaction occurs in the vacant ortho position of the phenolic groups of lignin, introducing an aminomethyl group at that position. The only vacant ortho position in the phenol unit for reaction is in the guaicyl unit. Softwood lignin underwent a Mannich reaction, since softwood contains a greater number of guaiacyl units than hardwoods.</p><p> </p><p>A screening of the products from this Mannich reaction on LignoBoost softwood kraft lignin was performed to optimise the reaction conditions. The reaction time, temperature, amount of formaldehyde and dimethylamine were varied. The Mannich products were evaluated by elemental analysis. The conditions giving the highest nitrogen content in the product were used further in a Mannich reaction of condensed softwood kraft lignin. The condensed softwood kraft lignin (7 g) was treated with dimethylamine (0.35 mol) and formaldehyde (0.35 mol) at 80°C for 24 hours.</p><p> </p><p>The metal binding experiment could not be carried out with Mannich-modified condensed softwood kraft lignin since the lignin dissolved in the copper solution.</p><p> </p><p>When introducing nitrogen functionalities into lignin the electron-donating capacity should increase. An increase in donor groups should promote the metal binding capacity of the lignin. A problem that occurred when introducing aminomethyl groups was an increase in solubility of the lignin. Water solubility of the lignin derivative is undesirable in the envisaged utilization area, metal binding in, for example mine deposits, from where contaminated water may be a concentrated source of heavy metals.</p>

<p>In discussions of heterogeneous catalysis and other surface-related phenomena, the dynamical properties of the catalytic material are often neglected, even at elevated temperatures. An example is the three-way catalyst (TWC), used for treatment of exhaust gases from combustion engines operating at several hundred degrees Celsius. In the TWC, reduced ceria (CeO_2-x) is one of the key components, where it functions as an oxygen buffer, storing and releasing oxygen to provide optimal conditions for the catalytic conversion of the pollutants. In this process it is evident that dynamics plays a crucial role, not only ionic vibrations, but also oxygen diffusion.</p><p>In this thesis, the structure and dynamics of several ionic crystalline compounds and their surfaces have been studied by means of Molecular dynamics (MD) simulations and Lattice dynamics (LD) calculations. The main focus lies on CeO_2-x, but also CeO₂, MgO and CaF₂ have been investigated.</p><p>The presence of oxygen vacancies in ceria is found to lead to significant distortions of the oxygen framework around the defect (but not of the cerium framework). As a consequence, a new O-O distance emerges, as well as a significantly broadened Ce-O distance distribution.</p><p>The presence of oxygen vacancies in ceria also leads to increased dynamics. The oxygen self-diffusion in reduced ceria was calculated from MD simulations in the temperature range 800-2000 K, and was found to follow an Arrhenius behaviour with a vacancy mechanism along the crystallographic <100> directions only.</p><p>The cation and anion vibrational surface dynamics were investigated for MgO (001) using DFT-LD and for CaF₂ (111) in a combined LEED and MD study. Specific surface modes were found for MgO and increased surface dynamics was found both experimentally and theoretically for CaF₂, which is isostructural with CeO₂.</p><p>Many methodological aspects of modeling dynamics in ionic solids are also covered in this thesis. In many cases, the representation of the model system (slab thickness, simulation box-size and the choice of ensemble) was found to have a significant influence on the results.</p>

<p>Electrochemical deposition finds applications in the electronics- and protective coating industries. The technique is a versatile tool for the synthesis of alloys and thin films. Knowledge of the fundamental aspects of the electrode processes enables the design of nanostructured materials. In this thesis, electrodeposition processes in solutions containing metal ion complexes were studied and new methods for the preparation of metal/metal-oxide coatings were developed and evaluated. </p><p>Metal/metal oxide coatings were electrodeposited from aqueous solutions containing metal complexes of hydroxycarboxylic acids under reducing conditions. The mass changes of the working electrode were monitored <i>in-situ</i> with the electrochemical quartz crystal microbalance (EQCM) technique and ellipsometry was used to detect the formation of Cu₂O. The coatings were further characterized with XRD, XPS, SEM, TEM, and Raman spectroscopy. Electrochemical methods, including reduction of Sb/Sb₂O₃ in an organic electrolyte, were also used to study the properties of the deposited materials. </p><p>Nanostructured coatings of Cu/Cu₂O were obtained during spontaneous potential or current oscillations in alkaline Cu(II)-citrate solutions. The oscillations were due to local pH variations induced by a subsequent chemical step and comproportionation between Cu and Cu²⁺. Well-defined layers of Cu and Cu₂O could be prepared by a galvanostatic pulsing technique, allowing independently controlled thickness of several hundred nanometers. Coatings, containing Sb and co-deposited, nanograins of Sb₂O_3, with a thickness of up to 200 nm were prepared from poorly buffered Sb(III)-tartrate solutions. Galvanostatic cycling showed that the latter material could be reversibly charged and discharged in a Li-ion battery for more than 50 cycles with a capacity of 660 mAh/g. </p><p>The results show that precipitations of metal oxides can occur due to local pH increases during electrochemical deposition from metal complexes with ligands containing hydroxyl groups. The ability to deposit metal oxides using cathodic deposition relies on a sufficiently slow reduction of the oxide. </p>

<p>Diamond and cubic boron nitride surfaces have extreme properties that can be exploited in novel tribological, electrochemical and electronic applications. Normally insulating diamond surfaces can exhibit high surface conductivities due to hydrogen termination and the nature of the surrounding atmosphere. Successful growth of cubic boron nitride thin films is hindered when harsh synthesis methods are used.</p><p>Three significant surface-related properties are addressed in this thesis using computational methods: (1) the structure, energy stability and reactivity of clean and differently terminated diamond surfaces, (2) the high surface conductivity of diamond, and (3) the adsorption-induced stability, reactivity and reconstruction of the cubic boron nitride (100) surface. Density Functional Theory (DFT) has been used at the GGA level under periodic boundary conditions to simulate the diamond and cubic boron nitride surfaces. </p><p>The diamond surface structures are shown to be insensitive to hydrogen desorption. Oxygen atoms bind in different positions and with different bond strengths. Hydroxyl groups experience both attractive hydrogen bonding and steric repulsions within the adsorbed species. The reconstruction of diamond (111)-1x1 is strongly dependent on the species adsorbed onto the surface. Electron transfer was observed from a diamond surface into a water-based adlayer, yielding a p-type doped surface, depending on the nature of the surface and the adlayer. The cubic boron nitride (100)-1x1 surface was shown to reconstruct into a 2x1 configuration on both the boron- and nitrogen-rich side through the formation of B-B bonds, as well as N–N dimer-induced surface relaxation. Hydrogen stabilized the (100)-1x1 surface, but the partial removal of hydrogen yielded non-reactive dimer formation on the surface. </p>

A whisker is a common name of single crystalline inorganic fibre of small dimensions, typically 0.5-1 μm in diameter and 20-50 μm in length. Whiskers are mainly used as reinforcement of ceramics. This work describes the synthesis and characterisation of new whisker types. Ti0.33Ta0.33Nb0.33CxN1-x, TiB2, B4C, and LaxCe1-xB6 have been prepared by carbothermal vapour–liquid–solid (CTR-VLS) growth mechanisms in the temperature range 900-1800°C, in argon or nitrogen. Generally, carbon and different suitable oxides were used as whisker precursors. The oxides reacted via a carbothermal reduction process. A halogenide salt was added to form gaseous metal halogenides or oxohalogenides and small amount of a transition metal was added to catalyse the whisker growth. In this mechanism, the whisker constituents are dissolved into the catalyst, in liquid phase, which becomes supersaturated. Then a whisker could nucleate and grow out under continuous feed of constituents. The syntheses of TiC, TiB2, and B4C were followed at ordinary synthesis conditions by means of mass spectrometry (MS), thermogravimetry (TG), differential thermal analysis (DTA) and quenching. The main reaction starting temperatures and reaction time for the different mixtures was revealed, and it was found that the temperature inside the crucible during the reactions was up to 100°C below the furnace set-point, due to endothermic nature of the reactions. Quench experiments showed that whiskers were formed already when reaching the temperature plateau, but the yield increased fast with the holding time and reached a maximum after about 20-30 minutes. Growth models for whisker formation have been proposed. Alumina based composites reinforced by (2-5 vol.%) TiCnano and TiNnano and 25 vol.% of carbide, and boride phases (whiskers and particulates of TiC, TiN, TaC, NbC, (Ti,Ta)C, (Ti,Ta,Nb)C, SiC, TiB2 and B4C) have been prepared by a developed aqueous colloidal processing route followed by hot pressing for 90 min at 1700°C, 28 MPa or SPS sintering for 5 minutes at 1200-1600°C and 75 MPa. Vickers indentation measurements showed that the lowest possible sintering temperature is to prefer from mechanical properties point of view. In the TiNnano composites the fracture mode was typically intergranular, while it was transgranular in the SiCnano composites. The whisker and particulate composites have been compared in terms of e.g. microstructure and mechanical properties. Generally, additions of whiskers yielded higher fracture toughness compared to particulates. Composites of commercially available SiC whiskers showed best mechanical properties with a low spread but all the other whisker phases, especially TiB2, exhibited a great potential as reinforcement materials.