No description available.

In this research, gel-state and quasi-solid state dye-sensitized solar cells (DSSCs) were fabricated with polydimethylbenzimidazole(PDMBI) as the polymer electrolyte. These devices are stable under room light in air, even without encapsulation. The energy conversion efficiency of gel-state cells was drastically increased around 200% after the device worked. We propose that appropriately aggregated PDMBI in electrolyte layer could provide pathways which would facilitate the diffusion of ion through the electrolyte. Moreover, this arrangement induces it an ion exchange reaction which could lead to the promotion of the diffusion rate between iodide species. An optimized device performs well with a power conversion efficiency of 4.98% under air-mass 1.5 global (AM 1.5G) illumination. For the fabrication of quasi-solid state dye-sensitized solar cells, we immersed a few liquid electrolyte to improve electrical contact between TiO2 porous layer and PDMBI layer. The quasi-solid state cell efficiency fabricated with PDMBI as electrolyte was 2.26%. Furthermore, our device architecture is performing well because of the good band alignment among TiO2, dye, and PDMBI. In this research, we have successfully demonstrated gel-state and quasi-solid state dye-sensitized solar cells comprising PDMBI as electrolyte.

<p dir="ltr">The thesis goal was to design a quasi-solid-state battery electrolyte, which was optimized to function at ambient as well as low temperatures. In the first project, an array of quasi-solid-state electrolytes were developed and compared. A series of electrochemical, spectroscopic, and thermal experiments in addition to imaging techniques determined a top performer as well as elucidated possible mechanistic explanations. This systematic study attempted to validate literature conclusions about the failure mechanisms governing batteries (solid-state batteries) at ultralow temperatures, while also offering hypothesis driven additional insight. The optimized electrolyte, which will be deemed as CSPE@2MMeTHF, performed well for several key reasons, traced to the co-solvent used (Me-THF), the salt concentration, and its formation of a stable and suitable cathode-electrolyte interphase. It was able to perform well at 25 °C, and down to -25 °C. The second part of the work, focused on further optimizing the electrolyte by removing a ‘polymer wetting/soaking’ step, removing a ceramic component, and pairing it with a recently discovered anodic electrode material. Given that narrowing the research gap for low temperatures requires both electrolyte and electrode design, it was important to consider this aspect of the problem as well. The cathodic electrode used for the first project, traditionally performs poorly at low temperatures, allowing for a suitable experimental control for the electrolyte. However, the new anodic electrode had two ways of storing lithium ions, as opposed to just one in the former, making it an attractive option for the stated goal of a low-temperature solid-state battery. This second project is akin to a ‘proof-of-concept’ work and there is much more room for further study, especially in preparing a full cell with the aforementioned electrodes cathode (LFP) and anode (NbWO) with the second SPE@51DMMeT electrolyte. In summary, this thesis shows method design to prepare solid-state electrolytes with portion of liquid, two successfully developed electrolyte systems for low temperatures, and a rigorous discussion of factors that affect electrochemical performance. Demonstrated research activities are of great value to defense as the current lithium-ion batteries does not perform well at subzero temperatures.</p>

京都大学 / 新制・課程博士 / 博士(エネルギー科学) / 甲第24002号 / エネ博第438号 / 新制||エネ||83(附属図書館) / 京都大学大学院エネルギー科学研究科エネルギー基礎科学専攻 / (主査)准教授 高井 茂臣, 教授 萩原 理加, 教授 佐川 尚 / 学位規則第4条第1項該当 / Doctor of Energy Science / Kyoto University / DFAM

NASCION-type lithium-aluminum-germanium-phosphate (LAGP) glass-ceramic is one of the most promising solid electrolyte (SEs) material for the next generation Li-ion battery. Based on the crystallization of glass-ceramic material, the two-step heat treatment was designed to control the crystallization of Li-ion conducting crystal in the glass matrix. The results show that the LAGP crystal is preferred to internally crystalize, Tg + 60%∆T is the nucleation temperature that provides the highest ion conductivity. The compositional investigation also found that, pure LAGP crystal phase can be synthesized by lowering the amount of GeO2. To fill gap of atomic structure in LAGP glass-ceramic, molecular dynamic (MD) simulation was used to build the crystal, glass, and interfacial structure LAGP. The aliovalent ion substitution induced an simultaneously redistribution of Li to the 36f interstitial site, and the rapid cooperative motion between the Li-ions at 36f can drop the activation energy of LAGP crystal by decreasing the relaxation energy; furthermore, an energy model was built based on the time-based analysis of Li-ion diffusion to articulate the behavior. The glass and interfacial structure show and accumulation of AlO4, GeO4 and Li at the interface, which explains the Li-trapping on the intergranular glass phase. An in-situ synchrotron X-ray study found that, by using two-step heat treatment, the nucleation of Li-ion conducting crystal in the glass-matrix induced large strain from interfacial tension, which can also promote the incorporation of aliovalent ion substitution in the NASICON crystal and enhances the ion conductivity.

Für den Einsatz in Autobatterien gibt es besondere Anforderungen an den Elektrolyten im Bereich der Energie- und Leistungsdichten, um beispielsweise thermische Verluste gering zu halten. Hochleitfähige Elektrolyte mit Leitfähigkeiten im Millisiemensbereich sind hier ebenso notwendig wie auch sichere, d.h. möglichst nicht brennbare und einen niedrigen Dampfdruck besitzende Materialien. Um diese Vorgaben zu erreichen, ist es notwendig, einen polymeren Separator zu entwickeln, welcher auf brennbare organische Lösungsmittel verzichtet und damit eine drastische Steigerung der Sicherheit gewährleistet. Gleichzeitig müssen hierbei die Leistungsvorgaben bezüglich der Leitfähigkeit erfüllt werden. Zu diesem Zweck wurde ein Konzept basierend auf der Kombination von einer polymeren sauerstoffreichen Matrix und einer ionischen Flüssigkeit entwickelt und verifiziert. Dabei wurden folgende Erkenntnisse gewonnen: 1. Es wurden neuartige diacrylierte sauerstoffreiche Matrixkomponenten mit vielen Carbonylfunktionen, für eine gute Lithiumleitfähigkeit, synthetisiert. 2. Es wurden mehrere neue ionische Flüssigkeiten sowohl auf Imidazolbasis als auch auf Ammoniumbasis synthetisiert und charakterisiert. 3. Die Einflüsse der Kationenstruktur und der Einfluss der Gegenionen im Bezug auf Schmelzpunkte und Leitfähigkeiten wurden untersucht. 4. Aus den entwickelten Materialien wurden Blendsysteme hergestellt und mittels Impedanzspektrometrie untersucht: Leitfähigkeiten von 10-4S/cm bei Raumtemperatur sind realisierbar. 5. Die Blendsysteme wurden auf ihre thermische Stabilität hin untersucht: Stabilitäten bis 250°C sind erreichbar. Dabei wird keine kristalline Struktur beobachtet. / Within the field of energy storage and charge transfer, the lithium polymer batteries are one of the leading technologies, due to their low manufacture cost and their possible variety of packaging shapes. Despite their good thermal stability and very good weight to energy ratio, lithium ion batteries use as a electrolyte system a mixture of ethylene carbonate and diethyl carbonate as solvent which have a high risk of deflagration when they come in contact with water. Thus the developement of new materials for lithium-ion-batteries are necessary. For the electrolyte there are special requirements in terms of energy- and power density e.g. in order to minimize thermal loss. High conductivity electrolytes with conductivities in the range of milisiemens are as essential as safe materials, like non flammable non-volatile materials. To fulfill these requirements it is important to develop a polymeric lithium ion conductor, which is free of flammable organic solvents in order to ensure safety. Simultaneously it is also ,mandatory to achieve high performances in terms of ion-conductivity. Therefore a concept based on a combination of an oxygen rich polymeric matrix and ionic liquids was developed and verified. Following results were achieved . 1. Synthesis of new diacryalted oxygen rich matrix components with many carbonylfunctions for a good lithium ion transport. 2. Synthesis and characterization of new ionic liquids based on imidazol or ammonium compounds. 3. Investigation of the influences of the cation structure and counter ions for melting points and ion conductivity. 4. Creation of Blendsystems with the developed materials 5. Thermal investigations of these solid-state-electrolytes with DSC and TGA measurements, resulting in thermal stabilities up to 250°C.No crystallization were observed. 6. investigation of these solid-state-electrolytes via AC-impedance spectrometry, resulting in conductivities of 10-4S/cm at room temperature.

Τα συστατικά μιας ευαισθητοποιημένης φωτοηλεκτροχημικής ηλιακής κυψελίδας μελετήθηκαν ξεχωριστά: ημιαγωγός, χρωστική και ηλεκτρολύτης. Παρασκευάστηκε και χαρακτηρίστηκε ένας στερεός ηλεκτρολύτης με βάση το υψηλού μοριακού βάρους πολυαιθυλενοξείδιο και νανοδομημένη τιτάνια. Ο ηλεκτρολύτης αυτός έφτασε σε ολικές αποδόσεις μετατροπής της ηλιακής ενέργειας σε ηλεκτρική της τάξεως του 4,55%, μία από τις μεγαλύτερες τιμές στη βιβλιογραφία. Χρήση άλλων ημιαγωγών πέρα του διοξειδίου του τιτανίου, όπως το οξείδιο του κασσιτέρου, δεν επέφερε αύξηση της παραπάνω απόδοσης. Νέα σύμπλοκα δισθενούς ρουθηνίου με διαφορετικούς πυριδινικούς υποκαταστάτες χρησιμοποιήθηκαν επίσης ως χρωστικές με αποδόσεις που έφτασαν μόλις το 1.74%. Επίσης, έγινε χρήση της φασματοσκοπίας micro-Raman για να θεμελιωθούν αρχικά συνθήκες συντονισμού και να μελετηθεί η χημειορρόφηση της χρωστικής στον ημιαγωγό. Τέλος μελετήθηκαν οι αλληλεπιδράσεις του οξειδοαναγωγικού ζεύγους με τη χρωστική κατά τη λειτουργία της κυψελίδας. / Τhe components of a dye-sensitized solar cell were thoroughly studied:semiconductor, dye and electrolyte. A novel electrolyte based on high molecular weight polyethylene oxide polymer filled with titania nanoparticles was prepared and characterized. The use of this electrolyte led to significantly high overall efficiencies (solar to electrical power) up to 4.55%, a value that is still one of the highest in literature. The use of different than titania conducting substrates, like tin oxide, did not improve the above efficiencies. Novel ruthenium(II) complexes with diver pyridine ligands were used leading to efficiencies up to only 1.74%. Micro-Raman spectrocopy was also used in order to establish resonance conditions to detect the dye chemisorption on the semiconductor substrate. Finally, the redox couple-dye interactions were thorouglh studied during the cell operation.

No description available.

Non-stoichiometric strontium iron oxide is described by an abbreviated formula SrFeOx (2.5 ≤ x ≤ 3.0) exhibits a variety of interesting physical and chemical properties over a broad range of temperatures and in different gaseous environments. The oxide contains a mixture of iron in the trivalent and the rare tetravalent state. The material at elevated temperature is a mixed oxygen conductor and it, or its derivatives,can have practical applications in oxygen conducting devices such as pressure driven oxygen generators, partial oxidation reactors in electrodes for solid oxide fuel cells (SOFC). ¶ This thesis examines the behaviour of the material at ambient and elevated temperatures using a broad spectrum of solid state experimental techniques such as: x-ray and neutron powder diffraction,thermogravimetric and calorimetric methods,scanning electron microscopy and Mossbauer spectroscopy. Changes in the oxide were induced using conventional thermal treatment in various atmospheres as well as mechanical energy (ball milling). The first experimental chapter examines the formation of the ferrite from a mixture of reactants.It describes the chemical reactions and phase transitions that lead to the formation of the oxide. Ball milling of the reactants prior to annealing was found to eliminate transient phases from the reaction route and to increase the kinetics of the reaction at lower temperatures. Examination of the thermodynamics of iron oxide (hematite) used for the reactions led to a new route of synthesis of the ferrite frommagnetite and strontium carbonate.This chapter also explores the possibility of synthesis of the material at room temperature using ball milling. ¶ The ferrite strongly interacts with the gas phase so its behaviour was studied under different pressures of oxygen and in carbon dioxide.The changes in ferrite composition have an equilibrium character and depend on temperature and oxygen concentration in the atmosphere. Variations of the oxygen content x were described as a function of temperature and oxygen partial pressure, the results were used to plot an equilibrium composition diagram. The heat of oxidation was also measured as a function of temperature and oxygen partial pressure. ¶ Interaction of the ferrite with carbon dioxide below a critical temperature causes decomposition of the material to strontium carbonate and SrFe12O19 . The critical temperature depends on the partial pressure of CO2 and above the critical temperature the carbonate and SrFe12O19 are converted back into the ferrite.The resulting SrFe12O19 is very resistant towards carbonation and the thermal carbonation reaction does not lead to a complete decomposition of SrFeOx to hematite and strontium carbonate. ¶ The thermally induced oxidation and carbonation reactions cease at room temperature due to sluggish kinetics however,they can be carried out at ambient temperature using ball milling.The reaction routes for these processes are different from the thermal routes.The mechanical oxidation induces two or more concurrent reactions which lead to samples containing two or more phases. The mechanical carbonation on the other hand produces an unknown metastable iron carbonate and leads a complete decomposition of the ferrite to strontiumcarbonate and hematite. ¶ Thermally and mechanically oxidized samples were studied using Mossbauer spectroscopy. The author proposes a new interpretation of the Sr4Fe4O11 (x=2.75) and Sr8Fe8O23 (x=2.875)spectra.The interpretation is based on the chemistry of the compounds and provides a simpler explanation of the observed absorption lines.The Mossbauer results froma range of compositions revealed the roomtemperature phase behaviour of the ferrite also examined using x-ray diffraction. ¶ The high-temperature crystal structure of the ferrite was examined using neutron powder diffraction.The measurements were done at temperatures up to 1273K in argon and air atmospheres.The former atmosphere protects Sr2Fe2O5 (x=2.5) against oxidation and the measurements in air allowed variation of the composition of the oxide in the range 2.56 ≤ x ≤ 2.81. Sr2Fe2O5 is an antiferromagnet and undergoes phase transitions to the paramagnetic state at 692K and from the orthorhombic to the cubic structure around 1140K.The oxidized formof the ferrite also undergoes a transition to the high-temperature cubic form.The author proposes a new structural model for the cubic phase based on a unit cell with the Fm3c symmetry. The new model allows a description of the high-temperature cubic form of the ferrite as a solid solution of the composition end members.The results were used to draw a phase diagramfor the SrFeOx system. ¶ The last chapter summarizes the findings and suggests directions for further research.