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This work investigated the enhanced sintering and electrical properties of (Ba 0.95 Ca 0.05 )(Ti 0.90 Sn 0.10 )O 3 - x Li 2 O (BCTSLi x , x = 0, 1, 2, 3, 4, 5 and 6 mol%) lead-free piezoelectric ceramics benefiting from the Li 2 O addition. Highly dense BCTS ceramics with good piezoelectric properties were fabricated at reduced sintering temperatures by adding a small amount of Li 2 O. It was found that the sintering densification is promoted mainly by reaction liquid phase at the early sintering stage and the formation of oxygen vacancies should be considered as an additional factor. The coexistence of R and T phases was confirmed by the Raman spectrum at a temperature range from−50 °C to 40 °C as x = 2 and at room temperature for all other Li 2 O added samples, while their specific ratio of R to T phase decreases with increasing Li 2 O addition. Better properties with d 33 = 457 pC/N, k p = 25.18% and Q m = 491 were obtained when adding 4 mol% Li 2 O, which are attributed dominantly to the appropriate specific ratio of R to T phase because of the similar grain size and density for samples at 3 ≤ x ≤ 6. [ABSTRACT FROM AUTHOR]