• 한국분말재료학회지
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• 제30권6호
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• pp.509-515
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• 2023

Lead-free perovskite ceramics, which have excellent energy storage capabilities, are attracting attention owing to their high power density and rapid charge-discharge speed. Given that the energy-storage properties of perovskite ceramic capacitors are significantly improved by doping with various elements, modifying their chemical compositions is a fundamental strategy. This study investigated the effect of Zn doping on the microstructure and energy storage performance of potassium sodium niobate (KNN)-based ceramics. Two types of powders and their corresponding ceramics with compositions of (1-x)(K,Na)NbO₃-xBi(Ni_2/3Ta_1/3)O₃ (KNN-BNT) and (1-x)(K,Na)NbO₃-xBi(Ni_1/3Zn_1/3Ta_1/3)O₃ (KNN-BNZT) were prepared via solid-state reactions. The results indicate that Zn doping retards grain growth, resulting in smaller grain sizes in Zn-doped KNN-BNZT than in KNN-BNT ceramics. Moreover, the Zn-doped KNN-BNZT ceramics exhibited superior energy storage density and efficiency across all x values. Notably, 0.9KNN-0.1BNZT ceramics demonstrate an energy storage density and efficiency of 0.24 J/cm³ and 96%, respectively. These ceramics also exhibited excellent temperature and frequency stability. This study provides valuable insights into the design of KNN-based ceramic capacitors with enhanced energy storage capabilities through doping strategies.

• 센서학회지
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• 제30권6호
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• pp.408-414
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• 2021

This study analyzes the phase transition behavior and electrical properties of lead-free (1-x)K_0.5Na_0.5NbO₃-xBaZrO₃ (KNN-100xBZ) piezoelectric ceramics. The stabilized crystal structures in BaZrO₃-modified KNN ceramics is clarified to be pseudocubic. The polymorphic phase transition from the orthorhombic to pseudocubic phases can be observed with KNN-6BZ ceramics considering the optimized piezoelectric constant (d₃₃). Electromechanical strain behaviors are discussed. Accordingly, the enhancement of strain value at x = 0.08 (composition) may originate from the coexistence of ferroelectric domains and polar nanoregions. A schematic of domains for KNN, KNN-8BZ, and KNN-15BZ ceramics has been proposed to describe the relationship between the stabilized relaxor and changes in electrical properties.

• 한국재료학회지
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• 제33권4호
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• pp.135-141
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• 2023

The volatilization of alkali ions in (K,Na)NbO₃ (KNN) ceramics was inhibited by doping them with alkaline earth metal ions. In addition, the grain growth behavior changed significantly as the sintering duration (t_s) increased. At 1,100 ℃, the volatilization of alkali ions in KNN ceramics was more suppressed when doped with alkaline earth metal ions with smaller ionic size. A Ca²⁺-doped KNN specimen with the least alkali ion volatilization exhibited a microstructure in which grain growth was completely suppressed, even under long-term sintering for t_s = 30 h. The grain growth in Sr²⁺-doped and Ba²⁺-doped KNN specimens was suppressed until t_s = 10 h. However, at t_s = 30 h, a heterogeneous microstructure with abnormal grains and small-sized matrix grains was observed. The size and number of abnormal grains and size distribution of matrix grains were considerably different between the Sr²⁺-doped and Ba²⁺-doped specimens. This microstructural diversity in KNN ceramics could be explained in terms of the crystal growth driving force required for two-dimensional nucleation, which was directly related to the number of vacancies in the material.

• 한국전기전자재료학회:학술대회논문집
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• 한국전기전자재료학회 2010년도 하계학술대회 논문집
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• pp.302-302
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• 2010

The lead-free piezoelectric ceramics must have high piezoelectric properties and electrical properties for the applications of piezoelectric devices. Therefore, KNN ceramics were investigated as a function of the variation of Nb. The density was increased with the increase of Nb. The density was saturated above 0.8895 mol Nb. The maximum value of electromechanical coupling coefficient(kp) was obtained 0.428 at 0.8895mol Nb. This result can be attributed to the well sintered of specimens. Also, The maximum value of mechanical quality factor(Qm) showed 1554 at 0.8895mol Nb. Therefore, this composition can be used for application of piezoelectric device such as piezoelectric transformer and piezoelectric actuator.

• 한국분말재료학회지
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• 제17권5호
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• pp.399-403
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• 2010

The effects of $MnO_2$ doping on the crystal structure, ferroelectric, and piezoelectric properties of (K,Na)$NbO_3$ (KNN) ceramics have been investigated. $MnO_2$ was found to be effective in enhancing the densification and grain growth during sintering. X-ray diffraction analysis indicated that Mn ions substituted B-site Nb ions up to 2 mol%, however, further doping induced unwanted secondary phases. In comparison with undoped KNN ceramics, the well developed microstructure and the substitution to B-sites in 2 mol% Mn-doped KNN ceramics resulted in significant improvements in both piezoelectric coupling coefficient and electromechanical quality factor.

• Advances in materials Research
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• 제5권2호
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• pp.93-105
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• 2016

KNN-based ceramics modified with small amounts of $Bi_4Zr_3O_{12}$ (BiZ) has been synthesized using high-throughput experimentation (HTE). The results from X-ray diffraction show that for samples with base composition $(K_{0.5}Na_{0.5})NbO_3$ (KNN), the phase present changes from orthorhombic to pseudo-cubic with more than 0.2 mol% BiZ addition; for samples with base composition $(K_{0.48}Na_{0.48}Li_{0.04})(Nb_{0.9}Ta_{0.1})O_3$ (KNNLT), the phase present changes from a mixture of orthorhombic and tetragonal symmetry to pseudo-cubic with more than 0.4 mol % while for samples with base composition $(K_{0.48}Na_{0.48}Li_{0.04})(Nb_{0.86}Ta_{0.1}Sb_{0.04})O_3$ (KNNLST), the phase present is tetragonal with <0.3 mol% BiZ addition and transforms to pseudo-cubic with more dopant addition. The microstructures of the samples show that addition of BiZ decreases the average grain size and increases the volume of pores at the grain boundaries. The values of dielectric constant for KNN and KNNLT compositions increase slightly with BiZ addition while that for KNNLST decreases gradually with BiZ addition. The dielectric loss values are between 0.02 and 0.04 for KNNLT and KNNLST compositions while they are ~ 0.05 for KNN samples. The resistivity values increases with BiZ addition and values in the range of $10^{10}{\Omega}cm$ and $10^{12}{\Omega}cm$ are obtained. The piezoelectric charge coefficient ($d{^*}_{33}$) is highest for KNNLST samples and decreases gradually from ~400 pm/V to ~100 pm/V with BiZ addition.

• 한국전기전자재료학회논문지
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• 제21권11호
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• pp.1000-1004
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• 2008

In this paper, the influences of poling electric field on piezoelectric properties of $0.95(K_{0.5}Na_{0.5})NbO_3$-$0.05Li(Sb_{0.8}Nb_{0.2})O_3$ (abbreviated as KNN-LSN) ceramics were investigated. The specimens was sintered at sintering temperature of $1050^{\circ}C$. They showed orthorhombic phase structure without secondary phase. Electromechanical coupling factor (kp), dielectric and piezoelectric constant($d_{33}$) increased with poling electric field. However, mechanical quality factor (Qm) decreased. Take into account of poling conditions and piezoelectric properties of KNN-LSN ceramics, the optimum poling condition for KNN-LSN ceramics was poling electric field of 4.5 kV/mm. At the time, kp of 0.458, Qm of 43.97, $d_{33}$ of 278 pC/N, and dielectric constant of 1079 were shown, respectively.

• 한국전기전자재료학회논문지
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• 제36권5호
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• pp.513-519
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• 2023

It was reported that a tetragonal phase can be stabilized with maintaining good piezoelectric properties when Na_0.5K_0.5NbO₃ (KNN) is modified with 0.06 mol SrTiO₃. However, such a high amount of SrTiO₃ leads not only to poor sinterability but low Curie temperature (T_C). To maintain high TC with good piezoelectric properties in KNN-based lead-free piezoelectric ceramics, this study investigates the effect of Li-doping on the dielectric and piezoelectric properties of 0.96Na_0.5K_0.5NbO₃-0.04SrTiO₃ (KNN-4ST) ceramics. As a result, the orthorhombic-tetragonal phase transition was observed at 2 mol% Li₂CO₃ modified KNN-4ST ceramics, whose T_C, d₃₃ and k_p values are 328℃, 165pC/N and 0.33, respectively.

• 한국전기전자재료학회논문지
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• 제24권7호
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• pp.563-567
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• 2011

The most widely used piezoelectric ceramics are lead oxide based ferroelectrics (PZT). However, the toxicity of lead oxide and its high vapor pressure during processing have led to a demand for alternative lead-free piezoelectric materials. We synthesized Lead-free piezoelectric ceramics of $0.96(K_{0.5}Na_{0.5})NbO_3-0.04SrZrO_3+x$ mol% $ZrO_2$ [KNN-SZ+$xZrO_2$; x= 0~0.10] doped with 0.1 wt% $MnO_2$ by a conventional solid state method. We investigated the piezoelectric properties and microstructures of these disk samples sintered in reduced atmosphere in order to evaluate the possibility of the multilayered piezoelectric ceramics having the base metal such as Ni as a internal electrode. All of these KNN-SZ samples sintered in 3%$H_2-97%N_2$ atmosphere at $1,140^{\circ}C$ exhibit pure perovskite structure irrespective of the content of $ZrO_2$. Meanwhile, the sintering denisty and piezoelectric properties such as $K_p$, $Q_m$ and $d_{33}$ of KNN-SZ samples as a function of $ZrO_2$ content show the maxima ($k_p$=28.07%, $Q_m$= 101.34, $d_{33}$= 156 pC/N) at x= 0.04 and it is likely that there is some morphotropic phase boundary(MPB) in this KNN-SZ+$xZrO_2$ composition system. These results indicate that the ceramic composition is a promising candidate material for applications in lead free multilayer piezoelectric ceramics.

• 한국재료학회지
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• 제22권1호
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• pp.35-41
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• 2012

Presently, the most promising family of lead-free piezoelectric ceramics is based on $K_{0.5}Na_{0.5}NbO_3$(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 $(Ba_{0.85}Ca_{0.15})(Ti_{0.88}Zr_{0.12})O_3$ component, which has relaxor ferroelectric characteristics, was doped to suppress the abnormal grain growth. To investigate this effect, Lead-Free $0.95(K_{0.5}Na_{0.5})_{0.95}Li_{0.05}NbO_3-(0.05-x)AgSbO_3-x(Ba_{0.85}Ca_{0.15})(Ti_{0.88}Zr_{0.12})O_3$[KNLN-AS-xBCTZ] piezoelectric ceramics were synthesized by ball mill and nanosized-milling processes in lead-Free $0.95(K_{0.5}Na_{0.5})_{0.95}Li_{0.05}NbO_3-(0.05-x)AgSbO_3$ 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: $d_{33}$ = 185 pC/N, $k_P$ = 41%, $T_C=325^{\circ}C$, $T_{O-T}=-4^{\circ}C$.