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No description available.

Polycondensation reaction was carried out for synthesizing rigid-rod polymer hPBI. Various molar ratios (50:1, 25:1, and 15:1) of 2-hydroterephthalic acid and 5-hydroisophthalic acid were also introduced in the synthesis for articulated rigid-rod polymer a-hPBI. The polymers were further derivatized with 1,3-propanesulton for pendants of lithium ionomer to become water soluble polyelectrolytes hPBI-PS(Li+) and a-hPBI-PS(Li+), respectively. Lithium salt doped cast film of the rigid-rod polyelectrolyte hPBI-PS(Li+) showed a room-temperature DC conductivity parallel to film surface as high as 4.02¡Ñ10-3 S/cm. Molecular weight of the rigid-rod polyelectrolyte was low indicating a small molecular aspect ratio. In cast film, the molecules were randomly distributed and highly isotropic facilitated Li cations mobility for a high film conductivity. The conductivity was also insensitive to the anion of lithium salt. No apparent layered structure was revealed by scanning electron microscope suggesting that the cast films had near three-dimensionally isotropic structure and conductivity.

Poly(p-phenylenebenzobisimidazole), PBI, is a rigid-rod polymer with a fully conjugated backbone having superior mechanical properties, thermo-oxi- dative and solvent stabilities. The stabilities cause processing difficulties and in terms limit its applications in critical technologies, such as conducting polymers, nonlinear optics, and solid polyelectrolytes. In this study, a chemical derivative of PBI, poly[1,7-dihydrobenzo[1,2- d:4,5-d¡¦]diimidazo-2,6-diyl[2-(2-sulfo)-p-phenylene]], sPBI, was synthesized by polycondensation reaction of 1,2,4,5-tetraaminobenzene tetrahydrochloride with 2-sulfoterephthalic acid in poly(phosphoric acid). Isolated sPBI was measured in 30oC methanesulfonic acid for an intrinsic viscosity as high as 10.5 dL/g. sPBI polymer was then reacted with 1,3-propanesultone in dimethylsulfoxide containing sodium hydride for water-soluble rigid-rod polyelectrolyte, poly[1,7- dipropylsulfobenzo-[1,2-d:4,5-d¡¦]diimidazo-2,6-diyl-[2,(2-sulfo)-p-phenylene]], sPBI-PS(Na+). sPBI-PS(Na+) was further converted to sPBI-PS(Li+) with hydrochloride and followed with lithium hydroxide. Various analyses were applied to ascertain chemical structure, purities and thermal properties of synthesized monomers and polymers. sPBI-PS(Li+) aqueous solutions were doped individually with lithium salts of LiI, LiBF4, and LiCF3SO3 at concentrations up to 1.7¡Ñ10-5 wt./wt., which were cast into freestanding films of 10-25 £gm in thickness. Direct-current conductivity measured at room- temperature parallel to the film surface was as large as 9.74¡Ñ10-5 S/cm. The ionic nature of the conductivity was revealed by constant-voltage depletion measurements. X-ray scattering results suggested that the cast film was in-plane isotropic but out-of-the plane anisotropic with the rigid-rod backbone lying in the plane of the film.

Kyoto University (京都大学) / 0048 / 新制・課程博士 / 博士(工学) / 甲第18983号 / 工博第4025号 / 新制||工||1620 / 31934 / 京都大学大学院工学研究科材料工学専攻 / (主査)教授 田中 功, 教授 宇田 哲也, 教授 白井 泰治 / 学位規則第4条第1項該当

Saving energy in buildings is of great importance because about 30 to 40 % of the energy in the world is used in buildings. An electrochromic window (ECW), which makes it possible to regulate the inflow of visible light and solar energy into buildings, is a promising technology providing a reduction in energy consumption in buildings along with indoor comfort. A polymer electrolyte is positioned at the center of multi-layer structure of an ECW and plays a significant role in the working of the ECW. In this study, polyethyleneimine: lithium (bis(trifluoromethane)sulfonimide (PEI:LiTFSI)-based polymer electrolytes were characterized by using dielectric/impedance spectroscopy, differential scanning calorimetry, viscosity recording, optical spectroscopy, and electrochromic measurements. In the first part of the study, PEI:LiTFSI electrolytes were characterized at various salt concentrations and temperatures. Temperature dependence of viscosity and ionic conductivity of the electrolytes followed Arrhenius behavior. The viscosity was modeled by the Bingham plastic equation. Molar conductivity, glass transition temperature, viscosity, Walden product, and iso-viscosity conductivity analysis showed effects of segmental flexibility, ion pairs, and mobility on the conductivity. A connection between ionic conductivity and ion-pair relaxation was seen by means of (i) the Barton-Nakajima-Namikawa relation, (ii) activation energies of the bulk relaxation, and ionic conduction and (iii) comparing two equivalent circuit models, containing different types of Havriliak-Negami elements, for the bulk response. In the second part, nanocomposite PEI:LiTFSI electrolytes with SiO2, In2O3, and In2O3:Sn (ITO) were examined. Adding SiO2 to the PEI:LiTFSI enhanced the ionic conductivity by an order of magnitude without any degradation of the optical properties. The effect of segmental flexibility and free ion concentration on the conduction in the presence of SiO2 is discussed. The PEI:LiTFSI:ITO electrolytes had high haze-free luminous transmittance and strong near-infrared absorption without diminished ionic conductivity. Ionic conductivity and optical clarity did not deteriorate for the PEI:LiTFSI:In2O3 and the PEI:LiTFSI:SiO2:ITO electrolytes. Finally, propylene carbonate (PC) and ethylene carbonate (EC) were added to PEI:LiTFSI in order to perform electrochromic measurements. ITO and SiO2 were added to the PEI:LiTFSI:PC:EC and to a proprietary electrolyte. The nanocomposite electrolytes were tested for ECWs with the configuration of the ECWs being plastic/ITO/WO3/polymer electrolyte/NiO (or IrO2)/ITO/plastic. It was seen that adding nanoparticles to polymer electrolytes can improve the coloring/bleaching dynamics of the ECWs. From this study, we show that nanocomposite polymer electrolytes can add new functionalities as well as enhancement in ECW applications.

Disertacijoje yra nagrinėjama, kokią įtaką ličio katijonų ir deguonies vakansijų (Vo) kietųjų elektrolitų elektrinėms savybėms daro jų struktūra ir elementinė sudėtis. Darbe yra aprašomos technologinės superjoninių junginių (SJ) keramikų ir sluoksnių gamybos sąlygos, lemiančios jų mikrostruktūrą, bei pateikiami SJ paviršių, temperatūrinio stabilumo ir elektrinių savybių tyrimo rezultatai. Li+ SJ priklauso monoklininei, ortorombinei arba romboedrinei singonijoms. Keramikų mikrostruktūra labiausiai priklauso nuo jų kepinimo temperatūros. LiCe2/3PO4 keramiką paveikus elektriniu lauku, XPS buvo parodyta, kad šioje medžiagoje vyksta Li+ jonų pernaša. Kompleksinės varžos spektroskopijos tyrimai parodė, kad sistemose Li1+xScxZr2-x(PO4)3, Li1+xZr2-2xAlxTix(PO4)3 ir Li1+xGe2-2xAlxTix(PO4)3 (čia x = 0,1, 0,2, 0,3), didinant x, didėja kristalitiniai keramikų laidžiai, o jų aktyvacijos energijos mažėja. Li3Sc2–xBx(PO4)3 junginiuose vykstančio superjoninio fazinio virsmo temperatūra priklauso nuo x. Li3-xSc2-x-yYyZrx(PO4)3 sistemoje kai x = 0,1, y = 0, 0,1 temperatūrinėse kristalitinio laidžio prieklausose yra stebimos anomalijos, susijusios su superjoniniais faziniais virsmais šiose medžiagose, o kai x = 0,2 tirtame temperatūrų intervale faziniai virsmai nevyksta. Magnetroninio dulkinimo metodu suformuotų YSZ storųjų sluoksnių joninis laidis ir šio laidžio aktyvacijos energija priklauso nuo jų paruošimo technologinių sąlygų. Didinant NiO-CGO sluoksnių, suformuotų purškimo pirolizės... [toliau žr. visą tekstą] / The influence of the structure and elemental composition of lithium ions’ and oxygen vacancies’ (Vo) solid electrolytes (SE) on their electrical properties are investigated in the dissertation. The technological conditions of SE ceramics’ and films’ fabrication, which influence their microstructure, are described. The results of the investigation of the surfaces, temperature stability, and electrical properties are presented. Li+ SE belong to monoclinic, orthorhombic, or rhombohedral symmetries. The microstructure of the ceramics is mainly influenced by the temperature of their sintering. It has been shown by XPS that LiCe2/3PO4 ceramic is Li+-ion conductor. Complex impedance spectroscopy investigation showed that the increase of x in the systems Li1+xScxZr2-x(PO4)3, Li1+xZr2-2xAlxTix(PO4)3, and Li1+xGe2-2xAlxTix(PO4)3 (where x = 0.1, 0.2, 0.3) leads to the increase of bulk ionic conductivity of the ceramics and to the decrease of its activation energy. Phase transition temperature in Li3Sc2–xBx(PO4)3 compounds depends on x. The anomalies of temperature dependencies of bulk conductivity of Li3-xSc2-x-yYyZrx(PO4)3 system were observed when x = 0.1, y = 0, 0.1. The anomalies are related to superionic phase transitions in the materials, but no phase transitions have been detected for x = 0.2 compound in the studied temperature range. Ionic conductivity and its activation energy of YSZ thick films prepared by magnetron sputtering depend on their preparation’s technological... [to full text]

The influence of the structure and elemental composition of lithium ions’ and oxygen vacancies’ (Vo) solid electrolytes (SE) on their electrical properties are investigated in the dissertation. The technological conditions of SE ceramics’ and films’ fabrication, which influence their microstructure, are described. The results of the investigation of the surfaces, temperature stability, and electrical properties are presented. Li+ SE belong to monoclinic, orthorhombic, or rhombohedral symmetries. The microstructure of the ceramics is mainly influenced by the temperature of their sintering. It has been shown by XPS that LiCe2/3PO4 ceramic is Li+-ion conductor. Complex impedance spectroscopy investigation showed that the increase of x in the systems Li1+xScxZr2-x(PO4)3, Li1+xZr2-2xAlxTix(PO4)3, and Li1+xGe2-2xAlxTix(PO4)3 (where x = 0.1, 0.2, 0.3) leads to the increase of bulk ionic conductivity of the ceramics and to the decrease of its activation energy. Phase transition temperature in Li3Sc2–xBx(PO4)3 compounds depends on x. The anomalies of temperature dependencies of bulk conductivity of Li3-xSc2-x-yYyZrx(PO4)3 system were observed when x = 0.1, y = 0, 0.1. The anomalies are related to superionic phase transitions in the materials, but no phase transitions have been detected for x = 0.2 compound in the studied temperature range. Ionic conductivity and its activation energy of YSZ thick films prepared by magnetron sputtering depend on their preparation’s technological... [to full text] / Disertacijoje yra nagrinėjama, kokią įtaką ličio katijonų ir deguonies vakansijų (Vo) kietųjų elektrolitų elektrinėms savybėms daro jų struktūra ir elementinė sudėtis. Darbe yra aprašomos technologinės superjoninių junginių (SJ) keramikų ir sluoksnių gamybos sąlygos, lemiančios jų mikrostruktūrą, bei pateikiami SJ paviršių, temperatūrinio stabilumo ir elektrinių savybių tyrimo rezultatai. Li+ SJ priklauso monoklininei, ortorombinei arba romboedrinei singonijoms. Keramikų mikrostruktūra labiausiai priklauso nuo jų kepinimo temperatūros. LiCe2/3PO4 keramiką paveikus elektriniu lauku, XPS buvo parodyta, kad šioje medžiagoje vyksta Li+ jonų pernaša. Kompleksinės varžos spektroskopijos tyrimai parodė, kad sistemose Li1+xScxZr2-x(PO4)3, Li1+xZr2-2xAlxTix(PO4)3 ir Li1+xGe2-2xAlxTix(PO4)3 (čia x = 0,1, 0,2, 0,3), didinant x, didėja kristalitiniai keramikų laidžiai, o jų aktyvacijos energijos mažėja. Li3Sc2–xBx(PO4)3 junginiuose vykstančio superjoninio fazinio virsmo temperatūra priklauso nuo x. Li3-xSc2-x-yYyZrx(PO4)3 sistemoje kai x = 0,1, y = 0, 0,1 temperatūrinėse kristalitinio laidžio prieklausose yra stebimos anomalijos, susijusios su superjoniniais faziniais virsmais šiose medžiagose, o kai x = 0,2 tirtame temperatūrų intervale faziniai virsmai nevyksta. Magnetroninio dulkinimo metodu suformuotų YSZ storųjų sluoksnių joninis laidis ir šio laidžio aktyvacijos energija priklauso nuo jų paruošimo technologinių sąlygų. Didinant NiO-CGO sluoksnių, suformuotų purškimo pirolizės... [toliau žr. visą tekstą]

The ionic conductivity of the lithium ionic conductor, Li5La3Ta2O12, is studied in an attempt to better understand the intrinsic bulk ionic conductivity and extrinsic sample dependent contributions to the ionic conductivity, such as grain boundary effects and the electrode-electrolyte interface. To characterize the material, traditional AC impedance spectroscopy studies were performed as well novel in-situ nanoscale transport measurements. To perform the nanoscale measurements, higher quality samples were required and new synthesis techniques developed. The results of these new synthesis techniques was samples with higher densities, up to 96% of theoretical, and slightly higher room temperature ionic conductivity, 2x10^−5 S/cm. By combining the AC impedance spectroscopy results and in-situ nanoscale transport measurements from this study and prior reported results, as well as introducing models traditionally used to analyze supercapacitor systems, a new interpretation of the features seen in the AC impedance spectroscopy studies is presented. This new interpretation challenges the presence of Warburg Diffusion at low frequencies and the offers a new interpretation for the features that have been traditionally associated with grain boundary effects.

This thesis primarily focuses on the systematic understanding of structure – reactivity relationships in two representative systems: bixbyite and related structures as well as indium doped CeO2. Topotactic reaction routes have gained significant attention over the past two decades due to their potential to access kinetically controlled metastable materials. This has contributed substantially to the understanding of solid state reaction pathways and provided first insights into mechanisms. Contrary to the widely used ex-situ methods, in – situ techniques including powder x-ray diffraction and thermogravimetric – differential thermal analysis have been employed extensively throughout this work in order to follow the reaction pathways in real time. Detailed analysis of the AVO3 (A = In, Sc) bixbyite reactivity under oxidative conditions has been carried out and a variety of novel metastable oxygen defect phases have been identified and characterized. The novel metastable materials have oxygen deficient fluorite structures and consequently are potential ion conductors. Structural aspects of the topotactic vs. reconstructive transformations are illustrated with this model system. The structure – reactivity study of AVO3 phases was extended to AVO3 perovskite family. Based on the research methodologies and results from AVO3 bixbyite reactivity studies a generalized mechanistic oxidation pathway has been established with a non-vanadium phase, ScTiO3 bixbyite. However, there is stark contrast in terms of structural stability and features beyond this stability limit during AVO3 and ScTiO3 bixbyite reaction pathways. A series of complex reaction sequences including phase separation and phase transitions were identified during the investigation of ScTiO3 reactivity. The two-step formation pathway for the fluorite – type oxide ion conductor Ce1-xInxO2-δ (0 ≤ x ≤ 0.3) is being reported. The formation of the BaCe1-xInxO3-δ perovskites and the subsequent CO2-capture reaction with the formation of Ce1-xInxO2-δ (0 ≤ x ≤ 0.3) has been investigated in detail. The two-step formation pathway is contrasted with the unsuccessful direct method. The stability and the extent of In – doping for the CeO2 fluorite phases that can be achieved through this CO2 – capture method are reported. The necessity and strategies for the selection of appropriate intermediate precursors for the preparation of doped CeO2 are also reported.