Thermoelectric n-Type Oxide Materials for Energy Generation

  • Samuel Jackson

Student thesis: Phd


The thermoelectric properties of lanthanum-doped strontium titanate (LSTO) were investigated for high temperature applications. Ceramics with the formulation La(2x/3)Sr(1-x)TiO(3-delta) (x = 0.1, 0.3, 0.5, 0.7, 0.9) were produced using the conventional mixed oxide route. After 18 hours of milling the powders were calcined at 1373 K for 4 hours and sintered at 1733 K (± 180 K/hour) for 4 hours in air. SEM, XRD, and TEM techniques were employed to characterise the microstructure of the ceramics as well as density measurements. Subsequently the electrical conductivity, Seebeck coefficient, and thermal conductivity in order to determine the thermoelectric figure of merit of the ceramics. Key thermal conductivity results were further investigated using a computational approach. This production method resulted in high quality, high density (> 97 %) ceramics that were mostly single phase determined by XRD with a Pm3m space group, with the exception of the x = 0.9 ceramic that had a Cmmm space group. SEM imaging confirmed this finding and revealed a core-shell structure in x = 0.1 and x = 0.3 ceramics whereby the core was La-rich/Sr-deficient. Thermal conductivity of the ceramics decreased with increasing La content. This was investigated further computationally employing the Green-Kubo method. It was established that the decrease in thermal conductivity was due to phonon-scattering from A-site vacancies, and not from the stabilisation of oxygen vacancies as suggested elsewhere.The electrical properties were dramatically improved through sintering the LSTO ceramics in a 5 % H2 95 % Ar atmosphere. This led to a reduction of Ti4+ to Ti3+. The maximum electrical conductivity increased to 789 resulting in a power factor of 0.0013 W.m-1 K-2 at 477 K for x = 0.3. A zT of 0.27 at 870 K for x = 0.5 was obtained due to a lower thermal conductivity.The ceramic LSTO x50H was subsequently doped with excess lanthanum; A maximum of 3 % excess was able to be fully incorporated into the lattice. This resulted in a further increase of the electrical conductivity to 875 at 377 K. A decrease in the lattice thermal conductivity of ∼ 1 W.m-1 K-1 was also achieved due to the oxygen vacancies that were introduced as a result of the reducing sintering conditions. Overall a zT 0.27 at 1016 K was obtained for 3 % excess lanthanum. The ceramic LSTO x50H was also doped with niobium and vanadium. Reduction in the lattice parameter from the La substitution inhibited the niobium from fullyincorporating into the matrix. This was not the case for vanadium that resulted in an electrical conductivity of 144 , Seebeck coefficient of -106 µV.K-1 , and thermal conductivity of 2.08 W.m-1 K-1 at 308 K, resulting in an overall maximum zT of 0.08 at 1070 K.
Date of Award1 Aug 2016
Original languageEnglish
Awarding Institution
  • The University of Manchester
SupervisorRobert Freer (Supervisor)


  • Strontium Titanate
  • Ceramic
  • Thermoelectric

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