Because collagen is inherently piezoelectric, research is being actively conducted to utilize it to harvest energy. In this study, a collagen solution was prepared using edible low-molecular-weight peptide collagen powder, and collagen films were fabricated using a dip coating method. The collagen films prepared by dip coating showed a smooth surface without defects such as pinholes or cracks. Dehydrothermal treatment of the collagen films was performed to induce a stable molecular structure through cross-linking. The collagen film subjected to dehydrothermal treatment at 110 °C for 24 h showed a thickness reduction rate of 19 %. Analysis of the collagen films showed that the crystallinity of the collagen film improved by about 7.9 % after dehydrothermal treatment. A collagen film-based piezoelectric nanogenerator showed output characteristics of approximately 13.7 V and 1.4 μA in a pressure test of 120 N. The generator showed a maximum power density of about 2.91 mW/m2 and an output voltage of about 8~19 V during various human body movements such as finger tapping. The collagen film-based piezoelectric generator showed improved output performance with improved crystallinity and piezoelectricity after dehydrothermal treatment.

In this study, we investigated the microstructure and piezoelectric properties of 0.96(K0.456Na0.536)Nb0.95Sb0.05-0.04 Bi0.5(Na0.82K0.18)0.5ZrO3 (KNNS-BNKZ) ceramics based on one-step and two-step sintering processes. One-step sintering led to significant abnormal grain (AG) growth at temperatures above 1,085 °C. With increasing sintering temperature, piezoelectric and dielectric properties were enhanced, resulting in a high d33 = 506 pC/N for one-step specimen sintered at 1,100 °C (one-step 1,100 °C specimen). However, for one-step 1,115 °C specimen, a slight decrease in d33 was observed, emphasizing the importance of a high tetragonal (T) phase fraction for superior piezoelectric properties. Achieving a relative density above 84 % for samples sintered by the one-step sintering process was challenging. Conversely, two-step sintering significantly improved the relative density of KNNS-BNKZ ceramics up to 96 %, attributed to the control of AG nucleation in the first step and grain growth rate control in the second step. The quantity of AG nucleation was affected by the duration of the first step, determining the final microstructure. Despite having a lower T phase fraction than that of the one-step 1,100 °C specimen, the two-step specimen exhibited higher piezoelectric coefficients (d33 = 574 pC/N and kp = 0.5) than those of the one-step 1,100 °C specimen due to its higher relative density. Performance evaluation of magnetoelectric composite devices composed of one-step and twostep specimens showed that despite having a higher g33, the magnetoelectric composite with the one-step 1,100 °C specimen exhibited the lowest magnetoelectric voltage coefficient, due to its lowest kp. This study highlights the essential role of phase fraction and relative density in enhancing the performance of piezoelectric materials and devices, showcasing the effectiveness of the two-step sintering process for controlling the microstructure of ceramic materials containing volatile elements.

BaTiO3-Poly vinylidene fluoride (PVDF) solution was prepared by adding 0~25 wt% BaTiO3 nanopowder and 10 wt% PVDF powder in solvent. BaTiO3-PVDF film was fabricated by spreading the solution on a glass with a doctor blade. The output performance increased with increasing BaTiO3 concentration. When the BaTiO3 concentration was 20 wt%, the output voltage and current were 4.98 V and 1.03 μA at an applied force of 100 N. However, they decreased when the over 20 wt% BaTiO3 powder was added, due to the aggregation of particles. To enhance the output performance, the generator was poled with an electric field of 150~250 kV/cm at 100 °C for 12 h. The output performance increased with increasing electric field. The output voltage and current were 7.87 V and 2.5 μA when poled with a 200 kV/cm electric field. This result seems likely to be caused by the c-axis alignment of the BaTiO3 after poling treatment. XRD patterns of the poled BaTiO3-PVDF films showed that the intensity of the (002) peak increased under high electric field. However, when the generator was poled with 250 kV/cm, the output performance of the generator degraded due to breakdown of the BaTiO3-PVDF film. When the generator was matched with 800 Ω resistance, the power density of the generator reached 1.74 mW/m2. The generator was able to charge a 10 μF capacitor up to 1.11 V and turn on 10 red LEDs.

리튬 금속 기반 전극의 높은 용량에도 불구하고, 제어가 어려운 덴드라이트 성장은 낮은 쿨롱 효율, 안전 문제를 야기해, 리튬금속 배터리의 상용화를 제한한다. 본 연구에서는 압전 복합체인 BaTiO3/PVDF (BTO@PVDF) 기반 보호층을 리튬금속에 코팅, 덴드라이트에 의한 부피팽창으로 발생한 변형을 분극을 이용하여, 리튬 금속 전극의 안정성 및 성능을 향상 하고자 한다. 이를 통해, 균일한 리튬이온의 증착이 가능해졌으며, BTO@PVDF 전극은 100 사이클 동안 약 98.1% 이상의 쿨 롱 효율을 나타내었다. 또한, CV를 통해 향상된 리튬이온의 확산계수(DLi+) 증가를 보였으며, 본 연구에서 제시된 전략은 리 튬 금속 전극의 성능 향상에 새로운 길을 나타내준다.

K0.5Bi0.5TiO3 (KBT) thin films were prepared by sol-gel processing for future use in piezoelectric generators. It is believed that the annealing temperature of films plays an important role in the output performance of piezoelectric generators. KBT films prepared on Ni substrates were annealed at 500 ~ 700 oC. Tetragonal KBT films were formed after annealing process. As the annealing temperature increased, the grain size of KBT films increased. KBT thin films show piezoelectric constant (d33) from 23 to 41 pC/N. The increase of grain size in KBT films brought about output voltage and current in the KBT generators. Also, the increase in the displacement of specimens during bending test resulted in increases in output voltage and current. Although KBT generators showed lower output power than those of generators prepared using NBT films, as reported previously, the KBT films prepared by sol-gel method show applicability as piezoelectric thin films for lead-free nanogenerators, along with NBT films.

(Bi1/2Na1/2)TiO3 (BNT)-based ceramics are considered promising candidates for actuator application owing to their excellent electromechanical strain properties However, to obtain large strain properties, there remain several issues such as thermal stability and high operating fields. Therefore, this study investigates a reduction of operating field in (0.98-x)Bi1/2Na1/ 2TiO3-0.02 BiAlO3-xSrTiO3 (BNT-2BA-100xST, x = 0.20, 0.21, 0.22, 0.23, and 0.24) via analyses of the microstructure, crystal structure, dielectric, polarization, ferroelectric and electromechanical strain properties. The average grain size of BNT-2BA- 100xST ceramics decreases with increasing ST content. Results of polarization and electromechanical strain properties indicate that a ferroelectric to relaxor state transition is induced by ST modification. As a consequence, a large electromechanical strain of 592 pm/V is obtained at a relatively low electric field of 4 kV/mm in 22 mol% ST-modified BNT-2BA ceramics. We believe that the materials synthesized in this study are promising candidates for actuator applications.

Piezoelectric ceramic specimens with the Pb(Mg1/3Nb2/3)0.65Ti0.35O3 (PMN-PT) composition are prepared by the solid state reaction method known as the “columbite precursor” method. Moreover, the effects of the Li2O-Bi2O3 additive on the microstructure, crystal structure, and piezoelectric properties of sintered PMN-PT ceramic samples are investigated. The addition of Li2O-Bi2O3 lowers the sintering temperature from 1,200oC to 950oC. Moreover, with the addition of >5 wt.% additive, the crystal structure changes from tetragonal to rhombohedral. Notably, the sample with 3 wt.% additive exhibits excellent piezoelectric properties (d33 = 596 pC/N and Kp = 57%) and a sintered density of 7.92 g/cm3 after sintering at 950oC. In addition, the sample exhibits a curie temperature of 138.6oC at 1 kHz. Finally, the compatibility of the sample with a Cu electrode is examined, because the energy-dispersive X-ray spectroscopy data indicate the absence of interdiffusion between Cu and the ceramic material.

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.

The impact of different mixing methods and sintering temperatures on the microstructure and piezoelectric properties of PZNN-PZT ceramics is investigated. To improve the sinterability and piezoelectric properties of these ceramics, the composition of 0.13Pb((Zn0.8Ni0.2)1/3Nb2/3)O3-0.87Pb(Zr0.5Ti0.5)O3 (PZNN-PZT) containing a Pb-based relaxor component is selected. Two methods are used to create the powder for the PZNN-PZT ceramics. The first involves blending all source powders at once, followed by calcination. The second involves the preferential creation of columbite as a precursor, by reacting NiO with Nb2O5 powder. Subsequently, PZNN-PZT powder can be prepared by mixing the columbite powder, PbO, and other components, followed by an additional calcination step. All the PZNNPZT powder samples in this study show a nearly-pure perovskite phase. High-density PZNN-PZT ceramics can be fabricated using powders prepared by a two-step calcination process, with the addition of 0.3 wt% MnO2 at even relatively low sintering temperatures from 800℃ to 1000℃. The grain size of the ceramics at sintering temperatures above 900℃ is increased to approximately 3 μm. The optimized PZNN-PZT piezoelectric ceramics show a piezoelectric constant (d33) of 360 pC/N, an electromechanical coupling factor (kp) of 0.61, and a quality factor (Qm) of 275.

The effects of an excess of Bi on the piezoelectric and dielectric properties of 0.60Bi1+xFeO3-0.40BaTiO3 (x = 0, 0.01, 0.03, 0.05, 0.07) were investigated. The ceramics were processed through a conventional solid state reaction method and then quenched after sintering at different temperatures in the range of 980~1070 oC. A single perovskite structure without any secondary phase was confirmed for all compositions and temperatures. It was found that excess Bi reduced the sintering temperatures, acted as a sintering aid and enhanced the properties in combination with quenching. Curie temperature (TC) was found to slightly increase due to the presence of excess Bi; electrical properties were also improved by quenching. At x = 0.03 and 1030 oC, remnant polarization (2Pr) was as high as 45.4 μC/cm2 and strain at 40 kV/cm was up to 0.176 %.

Presently, the most promising family of lead-free piezoelectric ceramics is based on K0.5Na0.5NbO3(KNN). Lithium, silver and antimony co-doped KNN ceramics show high piezoelectric properties at room temperature, but often suffer from abnormal grain growth. In the present work, the (Ba0.85Ca0.15)(Ti0.88Zr0.12)O3 component, which has relaxor ferroelectric characteristics, was doped to suppress the abnormal grain growth. To investigate this effect, Lead-Free 0.95(K0.5Na0.5)0.95Li0.05NbO3-(0.05-x)AgSbO3-x(Ba0.85Ca0.15)(Ti0.88Zr0.12)O3[KNLN-AS-xBCTZ] piezoelectric ceramics were synthesized by ball mill and nanosized-milling processes in lead-Free 0.95(K0.5Na0.5)0.95Li0.05NbO3-(0.05-x)AgSbO3 in order to suppress the abnormal grain growth. The nanosized milling process of calcined powders enhanced the sintering density. The phase structure, microstructure, and ferroelectric and piezoelectric properties of the KNLN-AS ceramics were systematically investigated. XRD patterns for the doped and undoped samples showed perovskite phase while tetragonality was increased with increasing BCZT content, which increase was closely related to the decrease of TO-T. Dense and uniform microstructures were observed for all of the doped BCZT ceramics. After the addition of BCTZ, the tetragonal-cubic and orthorhombic-tetragonal phase transitions shifted to lower temperatures compared to those for the pure KNNL-AS. A coexistence of the orthorhombic and tetragonal phases was hence formed in the ceramics with x = 0.02 mol at room temperature, leading to a significant enhancement of the piezoelectric properties. For the composition with x = 0.02 mol, the piezoelectric properties showed optimum values of: d33 = 185 pC/N, kp = 41%, Tc=325˚C, TO-T=-4˚C.

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.

For use in ultrasonic actuators, we investigated the structural and piezoelectric properties of (1 - x)Pb(Zr0.515Ti0.485)O3 - xPb(Sb1/2Nb1/2)O3 + 0.5 wt% MnO2 [(1 - x)PZT - xPSN + MnO2] ceramics with a variation of x (x = 0.02, 0.04, 0.06, 0.08). All the ceramics, which were sintered at 1250˚C for 2 h, showed a typical perovskite structure, implying that they were well synthesized. A homogeneous micro structure was also developed for the specimens, and their average grain size was slightly decreased to 1.3μm by increasing x to 0.8. Moreover, a second phase with a pyrochlore structure appeared when x was above 0.06, which resulted in the deterioration of their piezoelectric properties. However, the 0.96PZT-0.04PSN+MnO2 ceramics, which corresponds with a morphotropic phase boundary (MPB) composition in the (1 - x)PZT - xPSN + MnO2 system, exhibited good piezoelectric properties: a piezoelectric constant (d33) of 325 pC/N, an electromechanical coupling factor (kp) of 70.8%, and a mechanical quality factor (Qm) of 1779. The specimens with a relatively high curie temperature (Tc) of 305˚C also showed a significantly high dielectric constant (εr) value of 1109. Therefore, the 0.96PZT - 0.04PSN + MnO2 ceramics are suitable for use in ultrasonic vibrators.

Piezoelectric energy harvesting from our surrounding vibration has been studied for driving the wireless sensor node. To change the vibration energy into the electric-energy efficiently, the natural frequency of cantilever needs to be adjusted to that of a vibration source. When adding 6.80g mass on the end of the fabricated cantilever, a natural frequency shifts from 136 Hz into 49.5 Hz. In addition, electro-mechanical coupling factor increased from 10.20% to 11.90% and resulted in the 1.18 times increase of maximum output power.