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Title: Dielectric materials for high power energy storage
Author: Yu, Chuying
ISNI:       0000 0004 7652 7159
Awarding Body: Queen Mary University of London
Current Institution: Queen Mary, University of London
Date of Award: 2017
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Energy storage is currently gaining considerable attention due to the current energy crisis and severe air pollution. The development of new and clean forms of energy and related storing devices is in high demanded. Dielectric capacitors, exhibiting high power density, long life and cycling life, are potential candidates for portable devices, transport vehicles and stationary energy resources applications. However, the energy density of dielectric capacitors is relatively low compared to that of traditional batteries, which inhibits their future development. In the current work, three types of dielectrics, namely antiferroelectric samarium-doped BiFeO3 (Bi1-xSmxFeO3), linear dielectric (potential antiferroelectric) BiNbO4 and incipient ferroelectric TiO2, have been investigated to develop their potential as energy storage capacitors. For the samarium-doped BiFeO3 (Bi1-xSmxFeO3) system, the effect of samarium content in the A-site (x=0.15, 0.16, 0.165 and 0.18) on the structural phase transitions and electrical properties across the Morphotropic Phase Boundary (MPB) were studied. A complex coexistence of rhombohedral R3c, orthorhombic Pbam and orthorhombic Pnma was found in the selected compositions. The R3c phase is the structure of pure BiFeO3, the Pbam phase has a PbZrO3-like antiferroelectric structure and the Pnma phase has a SmFeO3-like paraelectric structure. The presence of the PbZrO3-like antiferroelectric structure was confirmed by the observation of the 14{110}, 14{001}, 12{011} and 12{111} superlattice reflections in the transmission electron microscopy diffraction patterns. The weight fractions of the three phases varied with different calcination conditions and Sm substitution level. By increasing the calcination temperature, the weight fractions of the Pbam increased, while that of the R3c decreased. The fraction of the Pnma phase is mainly derived by the Sm concentration and is barely affected by the calcination temperature. The increase of Sm concentration, determined an increase of the weight fraction of the Pnma phase and a decrease of the Pbam and the R3c phases. Temperature dependent dielectric measurements and high temperature XRD of Bi0.85Sm0.15FeO3 revealed several phase transitions. The drastic weight fraction change between the Pbam and the Pnma phase around 200 °C is assumed as the Curie transition of the antiferroelectric Pbam phase. The transition at 575 °C is related to the diminishing of the R3c phase and is suggested as the Curie transition of the ferroelectric R3c phase. The Curie point of the antiferroelectric Pbam phase and the ferroelectric R3c phase in the Bi1-xSmxFeO3 ceramics shifted towards lower temperature with an increase of the Sm concentration. Current peaks were obtained in current-electric field loops in Bi0.85Sm0.15FeO3, which are correlated to domain switching in the R3c phase. The ferroelectric behavior was suppressed in Bi1-xSmxFeO3 (x=0.16, 0.165, 0.18), which is due to the gradually diminished contribution from the R3c phase. The system Bi0.82Sm0.18FeO3 showed the highest energy density of 0.64 J cm-3 (error bar ±0.02). For the BiNbO4 system, single phase α-BiNbO4 (space group Pnna) and β-BiNbO4 (space group P-1) powder and ceramics were produced. The longstanding issue related to the sequence of the temperature-induced phase transitions has been clarified. It is demonstrated that the β phase powder could be converted back to the  phase when annealed in the temperature range 800 °C -1000 °C with certain incubation time. The β to  phase transition is a slow kinetic process because sufficient temperature and time are required for the transition. In bulk ceramics with β phase, this transformation is impeded by inner stress, while it is favored by graphite-induced reducing atmosphere. A high temperature  phase has been revealed and the structure has been resolved. The structure of the  phase is monoclinic with a space group of P21/c. The lattice parameters are: a = 7.7951(1) Å, b = 5.64993(9) Å, c = 7.9048(1) Å,  = 104.691(2) Z=4. The volume is 336.76 (2) Å3. The calculated density is 7.217 g cm-3. The phase relationships among ,  and  phases have been clarified. It was found that the  phase (for both powder and ceramic) transforms into the  phase at 1040 °C on heating, and that the  phase always transforms into the  phase at 1000 °C on cooling. Meanwhile, a reversible first-order  to  phase transition is observed at ca. 1000 °C for both powder and ceramic if no incubation is processed on heating. The electric properties of both α- and - BiNbO4 have been investigated. The breakdown field of both ceramics were too low to observe any possible field-induced transition. As a result, linear P-E loops were obtained in each phase. The energy densities of α- and - BiNbO4 ceramics are 0.03 and 0.04 J cm-3 (error bar ±0.001), respectively. For the TiO2 system, ceramics were produced by conventional sintering and spark plasma sintering (SPS). Compared to conventional sintering, SPS technique produced dense ceramics without using sintering aids and avoided abnormal grain growth. Relaxation behavior related to the oxygen hopping among vacant sites is observed in the temperature range of 200 to 600 °C. TiO2 exhibits ultra-low loss at terahertz frequencies due to the reduced contribution of oxygen vacancies relaxation. TiO2 has a high breakdown field, but still has low polarization. The highest energy density obtained inTiO2 ceramics is 0.3 J cm-3 (error bar ±0.01).
Supervisor: Not available Sponsor: China Scholarship Council
Qualification Name: Thesis (Ph.D.) Qualification Level: Doctoral
EThOS ID:  DOI: Not available
Keywords: Engineering and Materials Science ; Dielectric Materials ; High Power Energy Storage