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A series of compact La/O-vacant La(1-x)CoO(3-y) compounds were prepared by a cold high-pressure procedure, and their thermoelectric (TE) properties were investigated. Compared with the ion-substituted hole-type LaCoO(3) systems (e.g., La(1-x)Sr(x)CoO(3)), the thermal conduction of La(1-x)CoO(3-y) is noticeably reduced by the La/O vacancies, whereas the electric transport is less influenced, which results in an efficient ZT enhancement. We demonstrate that the large thermal conductivity reduction originates from the strong point-defect scattering, and La(1-x)CoO(3-y) can be rationalized as a partially filled solid solution: La(1-x)square(x)CoO(3-y)square(y), where square denotes a vacancy. Such intrinsic thermal conductivity suppression provides an effective pathway for the design of better TE materials.

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