In-plane micro-supercapacitors (MSCs), as promising power candidates for micro-devices, typically exhibit high power densities, large charge/discharge rates, and long cycling lifetimes. The high areal/volumetric capacitances, high energy/power densities, high rate capability, as well as flexibility are the main scientific pursue in recent years. Among diverse electrode materials for MSCs, coordination polymer frameworks are emerging due to the designable porous structure and tunable functionality. However, the unsatisfied electrochemical performance still hinders their practical applications. In this work, we demonstrate the first time an efficient in-situ growth approach to precisely modify the vacancy of Prussian-blue nano-thin films with pyridine by coordination reaction for high energy-density MSCs. Confirmed by the experimental results and density functional theory calculation, the vacancy modification within Prussian-blue network improved the film-forming property, hydrophilicity, and electrochemical activity of the thin films. The resultant MSCs based on pyridine-modified Prussian-blue exhibited an ultrahigh energy density of up to 12.1 mWh cm⁻³ and an ultra-low time constant (t₀) of 0.038 ms, which are the best values among the state-of-the-art in-plane MSCs. This work provides an attractive solution for structural engineering of promising active materials on molecule level toward high-performance micro-energy devices.

Batteries are increasingly seen as an indispensable element in the rapid progress of the energy transition. With forecasts for global demand set to reach 2 TWh by 2030 and increasing policy support for battery manufacturers, many questions arise on whether the current rapid expansion of battery manufacturing industry is sustainable. Issues regarding the stability of the supply chain and rising energy security concerns has led to an expanded focus on alternate battery technologies. Sodium ion cells are commonly cited as a potential solution to many of the current issues facing the lithium-ion battery industry. With sodium ion cells reaching commercialization, this thesis would like to explore the viability of commercial sodium ion cells through a bottom-up manufacturing and regional cost analysis of Sodium Prussian Blue Analogues and Sodium Layered Oxides. To account for the more qualitative aspects of regional battery manufacturing, the current policy framework and supply chain are briefly explored. To study the current commercial sodium ion cells, the report considers Na0.9[Cu0.22Fe0.30Mn0.48] O2 (Na Oxide) and Na2MnFe(CN)6 (Na PBA) cathode chemistries which are similar to the cells manufactured by HiNa and Novasis Energies respectively. These cells are compared to two of the most common Lithium chemistries on the market, LiFePO4 (LFP) and LiNi0.3Mn0.3Co0.3 (Li NMC111). Various manufacturing scales of the model plant are explored for each chemistry, and the changes in manufacturing costs for the US, China, India, Sweden and Chile are explored. Considering a baseline plant of 1500 MWh/yr, the base case results show that from the cost perspective the sodium ion cells are not too different from that of the lithium-ion cells. The cost of the lithium ion cells NMC111 and LFP (2019 US$) are at 126 $/kWh and 113$/kWh while the Na Oxide and Na PBA cell costs are at 125 $/kWh and 148 $/kWh. While the costs are comparable, the volumetric energy density of the sodium cells is almost half that of their lithium counterparts, which hampers the overall cost advantage from the cheaper materials. Compared to the lithium cells where the cathode and anode are on average the most expensive components, the separator and the hard carbon anode become the most expensive cost components in the sodium ion cells studied. In the regional analysis, China and Chile have the cheapest cell costs for both sodium and lithium, while the US and India are the most expensive within the countries studied with the maximum cost difference in the range of 15 $/kWh. While most countries have differing approaches in terms of policy support, the trend towards domestic sourcing of supplies can clearly be seen in most of the countries studied. The past three years has seen interest in battery manufacturing escalate significantly, with slow policy support in the 2010s from most countries. Chile is a notable exception with a lack of strong policy support. For the manufacturing scale, it was found that the minimum effective scale was 1500 MWh annually. The capital costs for the sodium ion cell plants were 16% more expensive than the lithium cell plants due to increased production rates to meet the same annual production. With cathode thickness, it was found that the Na PBA cell benefited the most with the increase in thickness, as it had the highest CAM capacity. The cost advantages of the sodium ion cells start to materialise when considering the increase in price of materials in 2022. When considering increased metal costs in 2022, the price of the Li NMC and LFP cells increase to around 186 $/kWh, while sodium ion cells don’t display an appreciable change in cost. Furthermore, when considering a higher power rate of 5C, the lithium cells perform poorly with Li NMC increasing to 188 $/kWh and LFP to 148 $/kWh while the sodium cells remain close to their 0.2C costs at 148$/kWh for Na PBA and 127 $/kWh for Na Oxide. / Batterier betraktas i allt högre grad som en oumbärlig komponent i den snabba utvecklingen av energiomställningen. Med prognoser som visar att den globala efterfrågan kommer att nå 2 TWh år 2030, och med ökat stöd från myndigheter till batteritillverkare, uppstår många frågor om huruvida den nuvarande snabba expansionen av batteritillverkningsindustrin är hållbar. Frågor om stabiliteten i leveranskedjan och ökad oro för energisäkerheten har lett till ett ökat fokus på alternativa batteriteknologier. Natriumjonceller nämns ofta som en potentiell lösning på många av de aktuella problemen som litiumjonbatteriindustrin står inför. Denna avhandling syftar till att undersöka livsdugligheten hos kommersiella natriumjonceller genom en bottom-up-tillverkning och regional kostnadsanalys av natriumpreussiska blåanaloger och natriumskiktade oxider. För att belysa de mer kvalitativa aspekterna av regional batteritillverkning undersöks även den nuvarande politiska ramen och leveranskedjan kortfattat. För att studera de nuvarande kommersiella natriumjoncellerna överväger rapporten katodkemin Na0.9[Cu0.22Fe0.30Mn0.48]O2 (Na Oxide) och Na2MnFe(CN)6 (Na PBA), som liknar celler som tillverkas av HiNa respektive Novasis Energies. Dessa celler jämförs med två av de vanligaste litiumkemikalierna på marknaden, LiFePO4 (LFP) och LiNi0.3Mn0.3Co0.3 (Li NMC111). Olika tillverkningsskalor i modellfabriker undersöks för varje kemikalie, och förändringarna i tillverkningskostnaderna i USA, Kina, Indien, Sverige och Chile analyseras. Med en baslinjeanläggning på 1500 MWh/år visar basfallsresultaten att natriumjoncellerna inte skiljer sig alltför mycket kostnadsmässigt från litiumjoncellerna. Kostnaden för litiumjoncellerna NMC111 och LFP är 126 $/kWh respektive 113 $/kWh, medan kostnaderna för Na Oxide och Na PBA-celler ligger på 125 $/kWh respektive 148 $/kWh. Trots att kostnaderna är jämförbara är natriumcellernas volymetriska energitäthet nästan hälften så stor som deras litiumequivalenter, vilket minskar den totala kostnadsfördelen av de billigare materialen. Jämfört med litiumcellerna, där katoden och anoden i genomsnitt utgör de dyraste komponenterna, är separatorn och hårdkolanoden de dyraste kostnadskomponenterna i de undersökta natriumjoncellerna. I den regionala analysen har Kina och Chile de lägsta cellkostnaderna för både natrium och litium, medan USA och Indien är dyrast bland de undersökta länderna med en maximal kostnadsskillnad på 15 $/kWh. Även om de flesta länder har olika tillvägagångssätt när det gäller politiskt stöd, kan trenden mot inhemska inköp av material tydligt ses i de flesta av de undersökta länderna. Under de senaste tre åren har intresset för batteritillverkning ökat betydligt, efter ett långsamt politiskt stöd under 2010-talet från de flesta länder. Chile utgör ett anmärkningsvärt undantag med brist på starkt politiskt stöd. Vid tillverkningsskalan fann man att den lägsta effektiva skalan var 1500 MWh årligen. Kapitalkostnaderna för natriumjoncellsanläggningar var 16 % dyrare än för litiumjoncellsanläggningar på grund av ökade produktionshastigheter för att uppnå samma årsproduktion. När det gäller katoddjocklek så gynnades Na PBA-cellen mest av en ökning i tjocklek, eftersom den hade den högsta CAM-kapaciteten. Fördelarna med natriumjonceller börjar realiseras när man beaktar prisökningen på material år 2022. Vid en ökning av metallkostnaderna 2022 ökar priset på Li NMC- och LFP-cellerna till cirka 186 $/kWh, medan kostnaden för natriumjoncellerna inte uppvisar någon märkbar förändring. Dessutom, vid en högre effekt på 5C, presterar litiumcellerna dåligt med en kostnad på 188 $/kWh för Li NMC och 148 $/kWh för LFP, medan kostnaden för natriumcellerna förblir nära deras kostnader vid 0,2C, nämligen 148 $/kWh för Na PBA och 127 $/kWh för Na Oxide.

No description available.

Nach der nationalsozialistischen Machtübernahme im Jahre 1933 wurde schon bald klar, dass es an der 1810 gegründeten Friedrich – Wilhelm – Universität zu Berlin, der größten deutschen Universität, zu einem Umbruch in der finanziellen und materiellen Ausstattung kommen würde. Bereits für das Rechnungsjahr 1934 wurde der Universität durch Erlass des Preußischen Ministers für Wissenschaft das Recht zur Aufstellung des jährlichen Haushaltsplanes entzogen. Damit war die Übernahme ihrer Einnahmen auf den Preußischen Staatshaushalt verbunden. Die Ausgabemittel für die Universität wurden nun im Staatshaushalt bereitgestellt. An die Stelle des Universitätshaushaltsplanes traten Kassenanschläge der Wissenschaftsverwaltung, in welchen den Fakultäten und Instituten die jährlichen Etatmittel zugewiesen wurden. Der staatliche Verwaltungsdirektor/Kurator überwachte deren Ausführung; denn ihm oblag die Aufsicht über das Haushalts- und Kassenwesen der Universität. Die Gründung der fünften und sechsten Fakultät sowie die Errichtung neuer (NS-) Institute wurde allein durch das Wissenschaftsministerium – weitgehend ohne Beteiligung der Universitätsleitung - entschieden. In der Folge stiegen die Etatmittel für das wissenschaftliche Personal exorbitant. - Die Betriebsmittel- und Geschäftsbedürfnisfonds der wissenschaftlichen Anstalten stagnierten auf dem Niveau der Jahre 1933/34. Investitionen in das Universitätsvermögen mussten hinter anderen für kriegswichtig erachteten Ausgaben des Deutschen Reiches zurückstehen. Selbst für die Behebung der Luftkriegsschäden an den Universitätsgebäuden standen Geldmittel nur in eingeschränktem Umfang zur Verfügung. Zudem verhinderte der eklatante Rohstoffmangel den Wiederaufbau. Bei Kriegsende 1945 war die Friedrich – Wilhelm – Universität zu Berlin in Trümmer gefallen. / After the national socialists came into power in 1933 it soon became clear, that financial and material changes were supposed to happen to the 1810 founded Friedrich-Wilhelms-University of Berlin, Germany´s largest university by that time. Already for the financial year of 1934 the Prussian Ministry of Science revoked the right of the university, to put together the annual financial budget. Thus, its earnings were now being taken over by the Prussian state budget and its expenses allocated by the state budget. Instead of a university budget the state administration allocates a certain amount of money for the faculties and institutions. The State Director of Administration / Curator supervised their execution; because he was the one responsible for overseeing the budget and cash management of the university. The foundation of the fifth and sixth faculty as well as the construction of new National Socialists („NS“) Institutes was decided solely by the Ministry of Science – largely without the participation of the management of the university. As a consequence, the budget funds for scientific personnel increased exorbitantly. Operating funds and funds for business needs of the scientific institutions stagnated at the level of 1933 / 1934. Investments into the assets of the university had to stay back behind war expenditures that were deemed essential of the German Reich. Even for the elimination of the air warfare damages at the buildungs of the university funds were allocated only to a very limited extent. In addition, the glaring lack of raw materials made the reconstruction almost impossible. When the war ended in 1945 only ruins were left of the Friedrich – Wilhelms – University of Berlin.

In this work, an electrochemical method based on a cyt c biosensor has been developed, for the detection of selected arsenic and cyanide compounds. Boron Doped Diamond (BDD) electrode was used as a transducer, onto which cyt c was immobilised and used for direct determination of Prussian blue, potassium cyanide and arsenic trioxide by inhibition mechanism. The sensitivity as calculated from cyclic voltammetry (CV) and square wave voltammetry (SWV), for each analyte in phosphate buffer (pH= 7) was found to be (1.087- 4.488 ×10-9 M) and the detection limits ranging from 0.0043- 9.1 μM. These values represent a big improvement over the current Environmental Protection Agency (EPA) and World Health Organisation (WHO) guidelines.

Miniaturization has become a driving force in different areas of technology including microelectronics, sensoric- and bio-technologies and in fundamental science. Because of the well-known limitations of conventional lithographic methods, newly emerging bottom-up approach, utilizing self-assembly of various nanoobjects including single polymer molecules and carbon nanotubes constitutes a very promising alternative for fabrication of ultimately small devices. Carbon nanotubes are attractive materials for nanotechnology and hold much promise to revolutionize fundamental science in a investigation of phenomena, associated with the nanometer–sized objects.It was found in this work that grafted chains of poly(2-vinylpyridine) form a shell covering the carbon nanotubes that makes them dispersible in organic solvents and in acidic water (CNTs-g-P2VP).The positively charged poly(2-vinylpyridine) shell is responsible for the selective deposition of carbon nanotubes onto oppositely charged surfaces. It was established that the deposition CNTs-g-P2VP from aqueous dispersions at low pH is an effective method to prepare ultra-thin films with a tunable density of carbon nanotubes.It was shown that poly(2-vinylpyridine) grafted to carbon nanotubes is a universal support for the immobilization of various nanoclusters at the carbon nanotube's surface. Prussian Blue nanoparticles were selectively attached to the surface of CNTs-g-P2VP.Conducting polymer nanowires are another very promising kind of nanomaterials that could be also suitable for applications in nanodevices and nanosensors. In this work was developed a simple method to control the conformation and orientation of single adsorbed polyelectrolyte molecules by co-deposition with octylamine. A simple chemical route to conductive polypyrrole nanowires by the grafting of polypyrrole from molecules of polystyrensulfonic acid was developed. The dc conductivity of individual polypyrrole nanowires approaches the conductivity of polypyrole in bulk.The conductivity can be described using variable-range hopping model.

In this work, an electrochemical method based on a cyt c biosensor has been developed, for the detection of selected arsenic and cyanide compounds. Boron Doped Diamond (BDD) electrode was used as a transducer, onto which cyt c was immobilised and used for direct determination of Prussian blue, potassium cyanide and arsenic trioxide by inhibition mechanism. The sensitivity as calculated from cyclic voltammetry (CV) and square wave voltammetry (SWV), for each analyte in phosphate buffer (pH= 7) was found to be (1.087- 4.488 ×10-9 M) and the detection limits ranging from 0.0043- 9.1 μM. These values represent a big improvement over the current Environmental Protection Agency (EPA) and World Health Organisation (WHO) guidelines.

Magister Scientiae - MSc / In this work, an electrochemical method based on a cyt c biosensor has been developed, for the detection of selected arsenic and cyanide compounds. Boron Doped Diamond (BDD) electrode was used as a transducer, onto which cyt c was immobilised and used for direct determination of Prussian blue, potassium cyanide and arsenic trioxide by inhibition mechanism. The sensitivity as calculated from cyclic voltammetry (CV) and square wave voltammetry (SWV), for each analyte in phosphate buffer (pH= 7) was found to be (1.087- 4.488 ×10-9 M) and the detection limits ranging from 0.0043- 9.1 μM. These values represent a big improvement over the current Environmental Protection Agency (EPA) and World Health Organisation (WHO) guidelines. / South Africa

L'Electrogravimetria AC empra una microbalança de quars electroquímica (EQCM) en règim dinàmic. En l'EQCM un dels elèctrodes d'or depositats sobre el cristall és recobert amb una fina pelolícula d'un polímer electroactiv i és emprat com a elèctrode de treball (WE) dins d'una celola electroquímica. Les variacions de la freqüència de ressonància de la microbalança de quars (QCM) permeten obtindre la resposta massa associada amb la transferència de càrrega que es dóna en la interfície polímer-electròlit. L'Electrogravimetria AC va ser proposta a fi de caracteritzar i separadament identificar el moviment dels ions i el solvent en la interfície polímer-electròlit. En esta tècnica s'analitza en el domine de la freqüència la resposta de massa davant de xicotetes pertorbacions de voltatge gràcies a l'ocupació de la microbalança de quars en règim dinàmic. Per a este propòsit s'aplica una xicoteta pertorbació sinusoidal superposada a una tensió contínua, entre l'elèctrode de referència i l'elèctrode de treball de la celola. Posteriorment, es pot dibuixar la funció de transferència electrogravimètrica (EGTF), definida esta com la raó (?m/?E) entre l'amplitud dels canvis de massa induïts (?m) i l'amplitud de la pertorbació sinusoïdal aplicada (?E). Esta funció de transferència se dibuixa en un pla complex per a cada una de les freqüències de la senyal de pertorbació. Les distintes espècies iònicas involucrades són identificades en el pla complex per mitjà de bucles característics sempre que els bucles no se superposen. Per mitjà d'esta tesi doctoral es proposa un nou sistema de conversió de freqüència-tensió basat en un doble ajust de freqüència implementat amb un PLL mesclant elements analògics i digitals (AD PLL). Els resultats trobats tant en la caracterització electrònica del dispositiu com en la fase experimental proven la fiabilitat del sistema per als mesuraments realitzats en la tècnica d'Electrogravimetria AC. / Torres Villa, RA. (2007). Instrumental techniques for improving the measurements based on Quartz Crystal Microbalances (Técnicas instrumentales para mejorar las mediciones con microbalanzas de cuarzo) [Tesis doctoral no publicada]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/17323 / Palancia

Miniaturization has become a driving force in different areas of technology including microelectronics, sensoric- and bio-technologies and in fundamental science. Because of the well-known limitations of conventional lithographic methods, newly emerging bottom-up approach, utilizing self-assembly of various nanoobjects including single polymer molecules and carbon nanotubes constitutes a very promising alternative for fabrication of ultimately small devices. Carbon nanotubes are attractive materials for nanotechnology and hold much promise to revolutionize fundamental science in a investigation of phenomena, associated with the nanometer–sized objects.It was found in this work that grafted chains of poly(2-vinylpyridine) form a shell covering the carbon nanotubes that makes them dispersible in organic solvents and in acidic water (CNTs-g-P2VP).The positively charged poly(2-vinylpyridine) shell is responsible for the selective deposition of carbon nanotubes onto oppositely charged surfaces. It was established that the deposition CNTs-g-P2VP from aqueous dispersions at low pH is an effective method to prepare ultra-thin films with a tunable density of carbon nanotubes.It was shown that poly(2-vinylpyridine) grafted to carbon nanotubes is a universal support for the immobilization of various nanoclusters at the carbon nanotube's surface. Prussian Blue nanoparticles were selectively attached to the surface of CNTs-g-P2VP.Conducting polymer nanowires are another very promising kind of nanomaterials that could be also suitable for applications in nanodevices and nanosensors. In this work was developed a simple method to control the conformation and orientation of single adsorbed polyelectrolyte molecules by co-deposition with octylamine. A simple chemical route to conductive polypyrrole nanowires by the grafting of polypyrrole from molecules of polystyrensulfonic acid was developed. The dc conductivity of individual polypyrrole nanowires approaches the conductivity of polypyrole in bulk.The conductivity can be described using variable-range hopping model.