Sodium dithionite (Na2S2O4) is a powerful reducing agent. It has therefore been suggested to be used as an additive in kraft pulping to improve the yield. However, sodium dithionite easily decomposes and it is thus important to determine the effect of different conditions. The aim of this thesis has been to investigate the thermal stability of sodium dithionite under anaerobic conditions using ATR-FTIR spectroscopy under different conditions, such as heating temperature, concentration of the solution, heating time and pH. The stability of sodium dithionite was found to decrease with increasing heating temperature, concentration of sodium dithionite, heating time and pH. Sodium dithionite was found to be relatively stable at moderate alkaline pH:s 11.5 and 12.5, while a rapid decrease in stability with time was noted at higher heating temperatures and concentrations of sodium dithionite. Based on this study on the thermal stability of sodium dithionite, the following conditions are suggested as the most promising, when adding sodium dithionite to the kraft cooking as an additive; pH 12.5, with 0.4 M concentration of the solution, at a heating temperature of 100 °C.

Den svenska vård-och omsorgsmarknaden har sedan dess avreglering för ca 20 år sedan utvecklats. Från att ha varit ett offentligt monopol har vi nu istället en starkt konkurrensutsatt marknad. Konkurrensfördelar som tillväxtstrategi kan nu vara avgörande för ett bolags framgång. Genom en närmast unik möjlighet att ta del av bolagsdata från ett av Sveriges största vård- och omsorgskoncerner har denna studie undersökt huruvida organiska eller oorganiska tillväxtstrategier lämpar sig bäst för vård- och omsorgsbolag som ämnar öka sin omsättning på ett kapitalmässigt effektivt sätt. Datat som tillhandahölls sträckte sig över fem år och innefattade 56 bolag. Studien genomfördes i form av två analyser. En kvantitativ regressionsanalys för att ta fram ett jämförelsetal motsvarande omsättning per krona spenderad i organiska investeringar och en delvis kvantitativ analys för att ta fram ett jämförelsetal motsvarande omsättning per krona spenderad i oorganiska investeringar. Analyserna visade sammanlagt att oorganiska tillväxtstrategier enligt datat är mer kapitalmässigt effektiva med avseende till omsättningstillväxt än organiska tillväxtstrategier. Studien tog dock bland annat inte hänsyn till potentiella synergieffekter från förvärv eller riskprofilen förknippad med de olika strategierna. Det framgick även från datat att investeringar i personal är positivt korrelerad med omsättningstillväxt, medan det inte gick att påvisa en korrelation mellan omsättningstillväxt och investeringar i IT eller generella investeringar. / The Swedish welfare industry has since its deregulation 20 years ago evolved. What was previously a publicly owned monopoly is now a competitive market. Competitive advantages such as growth strategies is now a key for a company’s success. Through an almost unique opportunity to use data from one of Sweden’s largest welfare groups this study has investigated whether organic or inorganic growth strategies is best suited for welfare companies looking to increase their total revenue in an, in terms of capital, effective way. The data provided spanned over five years and included data from 56 companies. The study was conducted as two separate analyses. A quantitative regression analysis was made to calculate a comparison number corresponding to revenue per SEK spent on organic investments. The second, in part quantitative analysis aimed to create a corresponding number for inorganic investments. The conclusion from the analyses was that according to the data, the inorganic growth strategies outperformed the organic growth strategies. The study did however not consider the potential synergy effects from acquisitions or the risk profile associated with the strategies. The study also revealed that according to the data investments in staff is positively correlated with revenue growth, but a correlation between revenue growth and both investments in IT and general investments could not be proven.

With an increasing demand for sustainable transport solutions, there is a demand for electrified vehicles. One way to store energy on board an electrified vehicle is to use a lithium-ion battery (LIB). This battery technology has many advantages, such as being rechargeable and enabling reasonably high power output and capacity. To ensure reliable operation of LIB:s, the battery management system (BMS) must be designed with regards to the electrochemical dynamics of the battery. However, since the battery ages over time, the dynamics changes as well. It is possible to predict ageing, but some ageing mechanisms can occur randomly, e.g. due to variations of circumstances during manufacturing, and variations of battery user choices. Hence, by monitoring ageing mechanisms in situ, the BMS can adapt accordingly, similar to a closed loop control system. One ageing mechanism in LIB:s is lithium plating. This mechanism signifies when Li ions are electrochemically deposited as metal onto the negative electrode of the LIB during charging, and can induce other ageing mechanisms, such as gassing or electrolyte reduction. The present project has investigated a method for detecting Li plating in situ after its occurrence by both analysing the voltage change over time during open-circuit voltage (OCV) periods after charging and monitoring battery swelling forces. Results show a correlation between a high probability of Li plating and the appearance of a swelling force peak and an OCV plateau. However, results also show a possible correlation between the onset of Li plating and the onset of the swelling force peak, while also showing a greater detectability of the force signal compared to the electrochemical signal. Furthermore, the present results show that the magnitudes of both signals are probably related to the amount of plated Li. The amount of irreversibly lost Li from plating is shown to have a possible correlation with accumulation of swelling pressure. However, to further validate the feasibility of these two signals, more advanced analysis is required, which was not available during this project. / Med en ökande efterfråga på hållbara transportlösningar så finns det ett behov av elektrifierade fordon. Ett sätt att lagra energi ombord ett elektrifierat fordon är att använda et litium-jon-batteri. Denna batteriteknologi har många fördelar: t.ex. är dessa batterier återladdningsbara, och de kan leverera höga uteffekter samtidigt som de kan ha ett stort energiinnehåll. för att säkerställa en säker drift av litium-jon-batterier måste batteriets styrsystem vara designat med hänsyn till den elektrokemiska dynamiken inuti batteriet. Dock åldras batteriet med tiden, vilket innebär att denna dynamik ändras med tiden, vilket innebär att styrningen av batteriet måste anpassa sig till denna föråldring. Det är möjligt att förutspå åldring av batterier, men vissa åldringsmekanismer kan ske slumpartat, t.ex. via slumpmässiga förändringar i tillverkningsprocessen av batteriet, eller variationer i användningen av batteriet. Genom att därmed bevaka dessa åldringsmekanismer in situ så kan styrsystemets algoritm anpassa sig utmed batteriåldringen, trots dessa slumpartade effekter. En åldringmekanism hos litium-jon-batterier är s.k. litiumplätering. Denna mekanism innebär att litium-joner elektrokemiskt pläteras i form av metalliskt litium på ytan av litium-jon-batteriets negativa elektrod. Mekanismen kan också inducera andra åldringsmekanismer, t.ex. gasutveckling eller elektrolytreduktion. Detta projekt har undersökt en metod för att detektera litiumplätering in situ efter att plätering har skett, genom att både analysera öppencellspänningens (OCV) förändring med tiden direkt efter uppladdning samt analysera de svällande krafterna som uppstår under uppladdning av batteriet. Resultaten visar på en korrelation mellan en hög sannolikhet för litiumplätering och observationen av en topp i svällningskraft och en platå i OCV-kurvan. resultaten visar också en möjlig korrelation mellan påbörjandet av litium-plätering och påbörjandet av toppen i svällningskraft. Vidare visar även resultaten ett troligt samband mellan signalernas magnitud och mängden pläterat litium. Slutligen visar resultaten också ett möjligt samband mellan irreversibelt pläterat litium och ett svällningstryck som ackumuleras med varje uppladdningscykel. Dock krävs det en validering med mer avancerade analysmetoder för att säkerställa användningsbarheten av dessa två signaler, vilket ej var möjligt inom detta projekt.

Gasformig koldioxid kan absorberas i en ammoniaklösning och bilda salt. De möjliga produkterna är ammoniumvätekarbonat (NH4HCO3), ammoniumkarbamat (NH2COONH4) och ammoniumkarbonat ((NH4)2CO3). Ammoniak är gasformigt i rumstemperatur. För att förhindra avdunstning av ammoniak undersöktes det i den här rapporten om nedkylning av reaktionslösningen eller ett oljelager ovanför skulle kunna förhindra detta och därmed tillåta saltbildning i lösningen. Dessutom skulle absorptionen genomföras utan både oljelager och nedkylt förhållande för att bestämma vad som var mest effektivt för att ge ett så högt utbyte som möjligt. För bestämning av de bildade salternas sammansättning användes XRD som analysmetod.  Resultatet från experimentet visade att salterna bildades i gasfasen och inget salt erhölls från vätskefasen. Orsaken till det är inte fastslagen, men tros bero på parametrar som salternas löslighet, lösningens pH, flödeshastighet på koldioxiden som gynnar ammoniakens avdunstning samt temperaturen. Utbytet från de olika försöksuppställningarna blev lågt i samtliga experiment, som högst erhölls relativt utbyte på 1,5%. Experimentet som gav högst relativt utbyte var försök vid 15% ammoniakkoncentration och koldioxidflöde på 181 ml CO2/min. Vid detta försök gjordes inga åtgärder för att förhindra ammoniakavdunstning från lösningen. Av de proverna som analyserades med XRD erhölls endast den önskade produkten med säkerhet i ett av proverna (isbad, 15 % NH3, 181 ml CO2/min). För att bestämma optimala reaktionsbetingelser krävs vidare studier.

In this thesis H-bonded systems (natural gas hydrates, water clusters, and crystal ice) are studied by density functional theory (DFT) computations. Natural gas hydrates (NGHs) play an important role in energy and environmental fields: NGHs are considered as a promising backup energy resource in the near-future due to their tremendous carbon content; improper exploration of NGHs could induce geological disasters and aggravate the greenhouse effect. In addition, many technologies based on gas hydrates are being applied and developed. The thermodynamic stabilities of various water cavities in different clathrate crystalline phases occupied by hydrocarbon gas molecules are studied by dispersion-corrected hybrid functionals. The Raman spectra of C-C and C-H stretching vibrations of hydrocarbon molecules in various water cavities in the solid state are derived. The trends of C-H stretching vibrational frequencies are found to follow the prediction by the “loose cage ─| tight cage” model. In addition, the trends and origins of 13C NMR chemical shifts of hydrocarbon molecules in various NGHs are presented. These theoretical results will enlarge the database of C-C and C-H stretching vibrational frequencies and 13C NMR parameters of hydrocarbon molecules in NGHs, and provide valuable information to help identify the types of clathrate phases and varieties of guest molecules included in NGHs samples taken from natural sites. The behavior of water clusters may help to understand the properties of its liquid and solid states. The thermodynamic stabilities and IR spectra of a small-, medium-, and large-sized water cluster are studied in this work. After full optimization of (H2O)20,54,100 using the hybrid functional B3LYP, the electronic energies, zero-point energies, internal energies, enthalpies, entropies, and Gibbs free energies of the water clusters are computed. The OH stretching vibrational IR spectra of (H2O)20,54,100 are also presented and split into sub-spectra for different H-bond types based on the specific contributions from each group. It is found that the OH stretching vibrational frequencies of water are sensitive to the conformations of the H-bonds and the vibrations of the H-bonds belonging to different types are located in separated regions in the IR spectra. Thus, the spectroscopic fingerprints will reflect the H-bond topology of the water molecules in a water cluster. Ice XI has been suggested to be involved in the process of planetary formation as a considerable electric field might be formed from the ferroelectric ice XI in space. IR and Raman spectroscopic technology can be directly used to identify the occurrence of ferroelectric ice XI in laboratory or extraterrestrial settings. Due to the difficulty for DFT to describe non-covalent systems, the performance of 16 different DFT methods applied on the ice Ih, VIII, IX, and XI crystal phases are assessed. Based on the computational accuracy and cost, the IR and Raman spectra of ice Ih and XI are derived and compared. The librational vibrations are found to be the identifier which can be used to distinguish ice Ih and ice XI in the universe. In addition, the existence only one kind of H-bond in ice Ih is demonstrated from the overlapping sub-spectra for different types of H-bonded pair configurations in 16 isomers of ice Ih. The region of water under negative pressure is an exotic land in lack of exploitation. Guest free clathrate hydrate (clathrate ice) of sII type has been recently confirmed experimentally at negative pressure. Does any other clathrate ice phase exist at negative pressure region? Since clathrate hydrate are isostructural with silica clathrate minerals and semiconductor clathrates, and crystal structure prediction by analogy with known structures and first-principles computations is an effective way to find new crystalline phases of solid materials, we are motived to look for new clathrate ice phases from silica or semiconductor clathrate materials based on first-principles computations. Borrowing the idea new clathrate frameworks of ZnO and SiC can be constructed by connecting their bubble clusters in different ways, new clathrate ice phases (sL, sL_I, sL_II, and sL_III) are generated by connecting the water bubble clusters according to different rules. Using the non-local dispersion-corrected vdW-DF2 functional, clathrate ice sL with ultralow density (0.6 g/cm3) is predicted by first-principles phase diagram computations to be stable under larger negative pressures than the sII phase. The phase diagram of water is thus extended into the lower negative pressure region.

CVD (Chemical Vapour Deposition) is an advanced technique for depositing a coating on a substrate. CVD implies that a solid phase is deposited on a normally heated substrate surface using a reactive, gaseous mixture. The reaction gas mixture must be carefully chosen to prevent homogeneous nucleation in the gas phase. As the solid phase is formed, gaseous by-products are formed and they must be removed from the CVD system. The thermally activated CVD process requires a deposition system which can regulate the total pressure and mass flows of the separate gas components as well as maintain a sufficiently high temperature to initiate a chemical reaction on the substrate surface. In this thesis a new CVD system was constructed to meet these challenges. Initially it will be used to deposit hard, wear resistant coatings but by changing the gases, it is possible to explore other chemical systems. The CVD system functions well up to a deposition temperature of 1100 ºC as long as the CVD processes are thermally activated. Apart from manual operation, a LabView control interface was implemented that can automate process steps by reading recipe files as csv (comma-separated variables). In this way complex coating architectures can be deposited. The aim of this thesis is to give a detailed description of the hardware set-up and of the software developed for it. Provided in this work are also a few examples of W and WN (tungsten nitride) coatings, including a multi-layered structure to show the potential of complex structures. Since the system also contains a titanium precursor, a TiN (titanium nitride) coating is presented to conceptually show the flexibility of the equipment. / CVD är en avancerad teknik för att lägga en tunn film runt ett substrat. CVD innebär att en fast fas bildas på den normalt uppvärmda substratytan från en reaktiv gasblandning. Gasblandningen är väl vald att inte förorsaka homogen kärnbildning i gasfasen. När den fasta fasen bildas så bildas också gasformiga biprodukter som måste pumpas ut ur systemet. Den termiskt aktiverade CVD processen kräver ett system som kan styra total trycket och massflödet av de individuella gaskomponenterna samt hålla en tillräcklig temperatur för att initiera kemiska reaktioner på substratytan. I denna avhandling presenteras ett CVD-system byggt för att möta dessa utmaningar. Initialt kommer systemet att deponera hårda, slittåliga skikt men genom gasbyte byte av gas kan andra materialsystem utforskas. CVD-systemet kan deponera andra typer av filmer upp till en deponeringstemperatur på 1100°C så länge som CVD-processerna är termiskt aktiverade. Utöver manuell styrning har ett styrprogram i LabView implementerats för att medge automatisering av processtegen genom att läsa av receptfiler i csv-format. På det här sättet kan mer komplicerade skiktarkitekturer deponeras. Målet med detta arbete är att ge en detaljerad beskrivning av uppställningen samt mjukvaran som framställts. Ett antal exempel på W- (volfram) och WN-skikt (volframnitrid) presenteras tillsammans med en multiskiktslösning för att visa potentialen för komplicerade strukturer. Eftersom systemet även har tillgång till en titankälla presenteras ett TiN-skikt (titannitrid) för att konceptuellt demonstrera utrustningens flexibilitet.

Thermoelectrics is the reversible process which transforms a temperature gradient across a material into an external voltage through a phenomenon known as the Seebeck effect. This has resulted in niche applications such as solid-state cooling for electronic and optoelectronic devices which exclude the need for a coolant or any moving parts and long-lasting, maintenance-free radioisotope thermoelectric generators used for deep-space exploration. However, the high price and low efficiency of thermoelectric generators have prompted scientists to search for new materials and/or methods to improve the efficiency of the already existing ones. Thermoelectric efficiency is governed by the dimensionless figure of merit 𝑧𝑇, which depends on the electrical conductivity, thermal conductivity and Seebeck coefficient value of the material and has rarely surpassed unity. In order to address these issues, research conducted on early transition metal nitrides spearheaded by cubic scandium nitride (ScN) thin films showed promising results with high power factors close to 3000 μWm−1K−2 at 500 °C. In this thesis, rock-salt cubic chromium nitride (CrN) deposited in the form of thin films by reactive magnetron sputtering was chosen for its large Seebeck coefficient of approximately -200 μV/K and low thermal conductivity between 2 and 4 Wm−1K−1. The results show that CrN in single crystal form has a low electrical resistivity below 1 mΩcm, a Seebeck coefficient value of -230 μV/K and a power factor close to 5000 μWm−1K−2 at room temperature. These promising results could lead to CrN based thermoelectric modules which are cheaper and more stable compared to traditional thermoelectric material such as bismuth telluride (Bi2Te3) and lead telluride (PbTe). In addition, the project resulting this thesis was prompted to investigate prospective ternary nitrides equivalent to ScN with (hopefully) better thermoelectric properties. Scandium nitride has a relatively high thermal conductivity value (close to 10 Wm−1K−1), resulting in a low 𝑧𝑇. A hypothetical ternary equivalent to ScN may have a similar electronic band structure and large power factor, but with a lower thermal conductivity value leading to better thermoelectric properties. Thus the elements magnesium, titanium, zirconium and hafnium were chosen for this purpose. DFT calculations were used to simulate TiMgN2, ZrMgN2 and HfMgN2. The results show the MeMgN2 stoichiometry to be stable, with two rivaling crystal structures: trigonal NaCrS2 and monoclinic LiUN2. / <p>The series name <em>Linköping Studies in Science and Technology Licentiate Thesis</em> is incorrect. The correct series name is <em>Linköping Studies in Science and Technology Thesis</em>.</p>

<p>Fosfaters reaktioner i energiomvandlingsprocesser är kritisk för den generella processen som helhet, för askrelaterade problem, emissioner liksom för en effektiv och hållbar användning av askan.</p><p>Denna avhandling är en sammanställning och diskussion med utgångspunkt i åtta artiklar som behandlar strukturella och termodynamiska studier på faser i CaO-K₂O-P₂O₅-systemet, vilka är av relevans inom förbränning av biomassa. Målsättningen med denna avhandling var: i) att sammanställa och granska tillgängliga strukturella och termodynamiska data i CaO-K₂O-P₂O₅-systemet samt att identifiera avsaknad av data, ii) att fylla i dessa luckor med grundläggande termodynamiska, strukturella och fasstabilitets studier samt iii) att visa på användning samt fördelarna med dessa nya data vid praktisk tillämpning.</p><p>En initial litteraturundersökning i CaO-K₂O-P₂O₅-systemet visade att det saknades både strukturella och termodynamiska data. När det gällde tillgängliga termodynamiska data var situationen särskilt otillfredsställande. Det fanns endast data för några kalcium– och kaliumfosfater med varierande tillförlitlighet. Situationen beträffande pulverröntgen för fasidentifiering var bättre, fast fördunklad av det faktum att strukturellt liknande fasövergångar ofta förekommer i det undersökta systemet. Däremot fattades det tillfredställande enkristallstrukturdata för ternära faser i det undersökta systemet.</p><p>Enkristallröntgendiffraktion användes för att bestämma strukturerna för CaK₂P₂O₇, CaKP₃O₉, Ca₁₀K(PO₄)₇ och CaKPO₄. Faserna CaK₂P₂O₇ and CaKPO₄ tillsammans med Ca₃(PO₄)₂, KPO₃ och K₄P₂O₇ studerades med pulverröntgendiffraktion och termiska analysmetoder för att klargöra fasmodifikationer och övergångstemperaturer. Gibbs bildningsenergi bestämdes för Ca(PO₃)₂, Ca₂P₂O₇, Ca₃(PO₄)₂, Ca₁₀K(PO₄)₇, CaK₂P₂O₇, CaKPO₄ och CaK₄(PO₄)₂ med ems-metodik och yttriastabiliserad zirkonia som fast elektrolyt och Ni/Ni₃P som hjälpsystem. Både de strukturella och termodynamiska data användes sedan vid analyser i ett förbrännningexperiment av olika sädesslag. Framtagna data användes både vid identifiering och även vid kvantifiering av bildade faser i biomassaresterna.</p> / <p>The behaviour of phosphates in thermochemical biomass conversion processes are critical for the general process chemistry, for ash related problems, for emissions as well as for an efficient, sustainable and beneficial use of the ash residues.</p><p>This thesis is a summary and a discussion of eight papers dealing with structural and thermodynamical studies of phases in the CaO-K₂O-P₂O₅ system, with relevance for biomass combustion. The objectives were: i) to compile and review the available structural and thermodynamical data of phases in the CaO-K₂O-P₂O₅ system as well as to identify existing gaps in the field of these data, ii) to fill in as many as possible of the gaps by fundamental thermodynamic, structural and phase stability studies and iii) to demonstrate the uses and the benefits of the new data in practical applications.</p><p>An initial review of the CaO-K₂O-P₂O₅ system showed that both structural information and thermodynamic data were lacking. The situation regarding the available thermodynamic data was especially unsatisfactory, data could only be found for some few calcium phosphates and a few potassium phosphates with varying reliability. Concerning powder X-ray diffraction patterns for phase identification the situation was better, though obscured by the fact that structurally close related phase transitions often occur in the studied system. However, adequate single crystal structural data of ternary phases in the system was completely missing.</p><p>Crystal structures of CaK₂P₂O₇, CaKP₃O₉, Ca₁₀K(PO₄)₇ and CaKPO₄ were determined by single-crystal X-ray diffraction. The phases CaK₂P₂O₇ and CaKPO₄ were together with Ca₃(PO₄)₂, KPO₃ and K₄P₂O₇, investigated by powder X-ray diffraction and thermal analysis to elucidate phase modifications and transitions temperatures. Gibbs standard energy of formation was determined for Ca(PO₃)₂, Ca₂P₂O₇, Ca₃(PO₄)₂, Ca₁₀K(PO₄)₇, CaK₂P₂O₇, CaKPO₄ and CaK₄(PO₄)₂ by solid state emf measurements with yttria stabilised zirconia as solid electrolyte and Ni/Ni₃P as auxiliary solid couple. Both the structural and thermodynamical data were subsequently utilised in analysis of a combustion experiment of cereal grains. The data were also used to both identify and quantify the phases formed in biomass combustion residues.</p>

<p>ZnO nanoparticles in the size range 2.5–7 nm have been synthesised by a wet chemical method where ZnO particles were grown in basic zinc acetate solution. The optical band gap increases when the size of the particles decreases. An empirical relation between the optical band gap given from absorption measurements, and particle size given from XRD measurements has been developed and compared to other similar relations found in the literature.</p><p>   Time resolved UV-Vis spectroscopy has been used to follow the growth of particles in situ in solution. The data show that the growth mechanism not can be described by a simple Oswald ripening approach and nor by an exclusive agglomeration of smaller clusters into larger particles. The growth mechanism is more likely a combination of the proposed reaction themes. The data also reveal that particle formation do not demand a heating step for formation of the commonly assumed initial cluster Zn₄O(CH₃COO)₆.</p><p>   Steady state fluorescence has been studied as a function of particle size during growth in solution. These measurements confirm what is found in the literature in that the visible fluorescence is shifted to longer wavelengths and loses in intensity as the particles grow. Some picosecond spectroscopy has also been done where the UV fluorescence has been investigated. From these measurements it is apparent that the lifetime of the fluorescence increases with particle size.</p><p>    The phonon spectrum of ZnO has been studied with Raman spectroscopy for a number of different particle sizes. From these measurements it is clear that there is a strong quenching of the phonons due to confinement for the small particles, and the only clearly observed vibration is one at 436 cm^-1 which intensity strongly increases with particle size.   </p>

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