Piezoelectric energy harvesters (PEHs) fabricated using piezoceramics could convert directly the mechanical vibration energy in the environment into electrical energy. The high piezoelectric charge coefficient (d33) and large piezoelectric voltage coefficient (g33) are key factors for the high-performance PEHs. However, high d33 and large g33 are difficult to simultaneously achieve with respect to g33 = d33/(ε0εr) and d33 = 2Qε0εrPr. Herein, the energy harvesting performance is optimized by tailoring the CaZrO3 content in (0.964−x)(K0.52Na0.48)(Nb0.96Sb0.04)O3 −0.036(Bi0.5Na0.5)ZrO3−xCaZrO3 ceramics. First, the doping CaZrO3 could enhance the dielectric relaxation due to the compositional fluctuation and structural disordering, and thus reduce the domain size to ∼30 nm for x = 0.006 sample. The nanodomains switch easily to external electric field, resulting in large polarization. Second, the rhombohedral–orthorhombic–tetragonal phases coexist in x = 0.006 sample, which reduces the polarization anisotropy and thus improves the piezoelectric properties. The multiphase coexistence structures and miniaturized domains contribute to the excellent piezoelectric properties of d33 (354 pC/N). Furthermore, the dielectric relative permittivity (εr) reduces monotonously as the CaZrO3 content increases due to the relatively low ion polarizability of Ca2+ and Zr4+. As a result, the optimized energy conversion coefficient (d33 × g33, 5508 × 10−15 m2/N) is achieved for x = 0.006 sample. Most importantly, the assembled PEH with the optimal specimen shows the excellent output power (∼48 µW) and lights up 45 red commercial light-emitting diodes (LEDs). This work demonstrates that tailoring ferroelectric/relaxor behavior in (K,Na)NbO3-based piezoelectric ceramics could effectively enhance the electrical output of PEHs.
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