A complete thiospinel solid solution CuCoxTi2-xS4 (0 ≤ x < 1) has been synthesized by conventional sealed tube synthesis followed by Spark Plasma Sintering, whereas, for x = 1, the presence of secondary phases is observed. The compounds exhibit a semi-metallic behavior in the whole composition range in spite of the existence of two subdomains characterized by different major redox species: (I) involving Cu+, Ti3+, Ti4+, Co2+ for 0 ≤ x ≤ 0.5 and (II) involving Cu+, Cu2+, Ti4+, Co2+for 0.5 < x ≤ 1. The thermoelectric properties show that, in the compositional range x = 0.3–0.8, the figure of merit does not depend significantly on x, ZT ranging from 0.13 to 0.18 at 675 K, whereas for the limit x = 0, it drops down to 0.04. This behavior is interpreted in terms of the predominant influence of the redox couple Ti3+/Ti4+ on the transport properties, as long as Cu+ is present, according to the equilibrium Cu+ + Ti4+⇌ Cu2+ + Ti3+. The thiospinel CuCo0.6Ti1.4S4, which exhibits the higher ZT of 0.18 at 675 K, opens the route to the research of new “Ti4+-Cu+” based thermoelectric sulfides with different structures.
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