Composite-based piezoelectric devices are extensively studied to develop sustainable power supply and selfpowered devices owing to their excellent mechanical durability and output performance. In this study, we design a leadfree piezoelectric nanocomposite utilizing (Ba0.85Ca0.15)(Ti0.9Zr0.1)O3 (BCTZ) nanomaterials for realizing highly flexible energy harvesters. To improve the output performance of the devices, we incorporate porous BCTZ nanowires (NWs) into the nanoparticle (NP)-based piezoelectric nanocomposite. BCTZ NPs and NWs are synthesized through the solidstate reaction and sol-gel-based electrospinning, respectively; subsequently, they are dispersed inside a polyimide matrix. The output performance of the energy harvesters is measured using an optimized measurement system during repetitive mechanical deformation by varying the composition of the NPs and NWs. A nanocomposite-based energy harvester with 4:1 weight ratio generates the maximum open-circuit voltage and short-circuit current of 0.83 V and 0.28 A, respectively. In this study, self-powered devices are constructed with enhanced output performance by using piezoelectric energy harvesting for application in flexible and wearable devices.

BNKT Ceramics, one of the representative Pb free based piezoelectric ceramics, constitutes a perovskite(ABO3) structure. At this time, the perovskite structure (ABO3) is in the form where the corners of the octahedrons are connected, and in the unit cell, two ions, A and B, are cations, A ion is located at the body center, B ion is located at each corner, and an anion O is located at the center of each side. Since Bi, Na, and K sources constituting the A site are highly volatile at a sintering temperature of 1100℃ or higher, it is difficult to maintain uniformity of the composition. In order to solve this problem, there should be suppression of volatilization of the A site material or additional compensation of the volatilized. In this study, the basic composition of BNKT Ceramics was set to Bi0.5(Na0.78K0.22)0.5TiO3 (= BNKT), and volatile site (Bi, Na, and K sources) were coated in the form of a shell to compensate additionally for the A site ions. In addition, the physical and electrical properties of BNKT and its coated with shell additives(= @BNK) were compared and analyzed, respectively. As a result of analyzing the crystal structure through XRD, both BNKT(Core) and @BNK(Shell) had perovskite phases, and the crystallinity was almost similar. Although the Curie temperature of the two sintered bodies was almost the same (TC = 290 ~ 300 ℃), it was confirmed that the d33 (piezoelectric coefficient) and Pr (residual polarization) values were different. The experimental results indicated that the additional compensation for a shell additive causes the coarsening, resulting in a decrease in sintering density and Pr(remanent polarization). However, coating shell additives to compensate for A site ion is an effective way to suppress volatilization. Based on these experimental results, it would be the biggest advantage to develop an eco-friendly material (Lead-free) that replaced lead (Pb), which is harmful to the human body. This lead-free piezoelectric material can be applied to a biomedical device or products(ex. earphones (hearing aids), heart rate monitors, ultrasonic vibrators, etc.) and skin beauty improvement products (mask packs for whitening and wrinkle improvement).

NKN [(Na,K)NbO3] is a candidate lead-free piezoelectric material to replace PZT [Pb(Zr,Ti)O3]. A single crystal has excellent piezoelectric-properties and its properties are dependent of the crystal orientation direction. However, it is hard to fabricate a single crystal with stoichiometrically stable composition due to volatilization of sodium during the growth process. To solve this problem, a solid solution composition is designed (Na,K)NbO3-Ba(Cu,Nb)O3 and solid state grain growth is studied for a sizable single crystal. Ceramic powders of (Na,K)NbO3-M(Cu,Nb)O3 (M = Ca, Sr, Ba) are synthesized and grain growth behavior is investigated for different temperatures and times. Average normal grain sizes of individual specimens, which are heat-treated at 1,125 oC for 10 h, are 6.9, 2.8, and 1.6 m for M = Ca, Sr, and Ba, respectively. Depending on M, the distortion of NKN structure can be altered. XRD results show that (NKN-CaCuN: shrunken orthorhombic; NKN-SrCuN: orthorhombic; NKN-BaCuN: cubic). For the sample heat-treated at 1,125 oC for 10 h, the maximum grain sizes of individual specimens are measured as 40, 5, and 4,000 m for M = Ca, Sr, and Ba, respectively. This abnormal grain size is related to the partial melting temperature (NKN-CaCuN: 960 oC; NKN-SrCuN: 971 oC; NKN-BaCuN: 945 oC).

Pb(Zr,Ti)O3 (PZT) is used for the various piezoelectric devices owing to its high piezoelectric properties. However, lead (Pb), which is contained in PZT, causes various environment contaminations. (K,Na)NbO3 (NKN) is the most well-known candidate for a lead-free composition to replace PZT. A single crystal has excellent piezoelectric-properties and its properties can be changed by changing the orientation direction. It is hard to fabricate a NKN single crystal due to the sodium and potassium. Thus, (Na,K)NbO3-Ba(Cu,Nb)O3 (NKN-BCuN) is chosen to fabricate the single crystal with relative ease. NKNBCuN pellets consist of two parts, yellow single crystals and gray poly-crystals that contain copper. The area that has a large amount of copper particles may melt at low temperature but not the other areas. The liquid phase may be responsible for the abnormal grain growth in NKN-BCuN ceramics. The dielectric constant and tan δ are measured to be 684 and 0.036 at 1 kHz in NKN-BCuN, respectively. The coercive field and remnant polarization are 14 kV/cm and 20 μC/cm2.

This work focuses on the electrical conduction mechanism in a lead free (Na0.5K0.5NbO3 ; NKN) ceramics system with LiNbO3 content of approximately critical concentration x ≥ 0.2. Lead free (1-x)(Na0.5K0.5)NbO3 - x(LiNbO3), NKN-LNx (x = 0.1, 0.2) ceramics were synthesized by solid-state reaction method. Crystal structures are confirmed by X-ray diffraction. The electric-mechanical bond coefficient k p decreases and the phase transition temperature T c increases with increasing x content, as determined by dielectric and piezoelectric measurements. The value of the real dielectric constants ε' and kBTε'' showed anomalies around T c (462 oC in the NKN-LN0.1 and 500 oC in the NKN-LN0.2). For the ionic conduction of mobile ions, the activation energies are obtained as EI = 1.76 eV (NKN-LN0.1) and EI = 1.55 eV (NKN-LN0.2), above T c, and EII = 0.78 (NKNLN0.1) and EII = 0.81 (NKN-LN0.2) below T c. It is believed that the conduction mechanisms of NKN-LNx ceramics are related to ionic hopping conduction, which may arise mainly due to the jumping of Li+ ions.

New lead-free piezoelectric ceramics 0.96[{Bi0.5 (Na0.84 K0.16)0.5}1-xLax(Ti1-y Nby)O3]-0.04SrTiO3 (BNKT-ST-LN, where x = y = 0.00 ≤ (x = y) ≤ 0.015) were synthesized using the conventional solid-state reaction method. Their crystal structure, microstructure, and electrical properties were investigated as a function of the La and Nb (LN) content. The X-ray diffraction patterns revealed the formation of a single-phase perovskite structure for all the LN-modified BNKT-ST ceramics in this study. The temperature dependence of the dielectric curves showed that the maximum dielectric constant temperature (Tm) shifted towards lower temperatures and the curves became more diffuse with an increasing LN content. At the optimum composition (LN 0.005), a maximum value of remnant polarization (33 C/cm2) with a relatively low coercive field (22 kV/cm) and high piezoelectric constant (215 pC/N) was observed. These results indicate that the LN co-modified BNKT-ST ceramic system is a promising candidate for lead-free piezoelectric materials.

Studies on lead-free piezoelectrics have been attractive as means of meeting environmental requirements. We synthesized lead-free piezoelectric (Bi1/2Na1/2)TiO3-Ba(Cu1/3Nb2/3)O3 (BNT-BCN) ceramics, and their dielectric, piezoelectric, and strain behavior were characterized. As BCN with a tetragonal phase was incorporated into the rhombohedral BNT lattice, the lattice constant increased. A small amount of BCN increased the density and dielectric constant forming the complete solid solution with BNT. However, BCN above 10 mol% was precipitated into a separate phase, and which was detected with XRD. In addition, EDX measurement revealed that Cu in BCN was not distributed homogeneously but was accumulated in a certain area. A lower density with a large amount of BCN was attributed to the nonsinterable property of BCN with large tetragonaliy. The dielectric constant vs the temperature change and the strain vs the electric field indicated that the ferroelectric property of BNT was diminished and paraelectric behavior was enhanced with the BCN addition. BNT-7.5BCN showed a 0.11% unimorph strain with a 9.0 kV/mm electric field with little hysteresis.