High strain (0.4%) Bi(Mg2/3Nb1/3)O3‐BaTiO3‐BiFeO3 lead‐free piezoelectric ceramics and multilayers

The relationship between the piezoelectric properties and the structure/microstructure for 0.05Bi(Mg_2/3Nb_1/3)O₃‐(0.95‐x)BaTiO₃‐xBiFeO₃ (BBFT, x = 0.55, 0.60, 0.63, 0.65, 0.70, and 0.75) ceramics has been investigated. Scanning electron microscopy revealed a homogeneous microstructure for x < 0.75 but there was evidence of a core‐shell cation distribution for x = 0.75 which could be suppressed in part through quenching from the sintering temperature. X‐ray diffraction (XRD) suggested a gradual structural transition from pseudocubic to rhombohedral for 0.63 < x < 0.70, characterized by the coexistence of phases. The temperature dependence of relative permittivity, polarization‐electric field hysteresis loops, bipolar strain‐electric field curves revealed that BBFT transformed from relaxor‐like to ferroelectric behavior with an increase in x, consistent with changes in the phase assemblage and domain structure. The largest strain was 0.41% for x = 0.63 at 10 kV/mm. The largest effective piezoelectric coefficient (d₃₃^*) was 544 pm/V for x = 0.63 at 5 kV/mm but the largest Berlincourt d₃₃ (148 pC/N) was obtained for x = 0.70. We propose that d₃₃^* is optimized at the point of crossover from relaxor to ferroelectric which facilitates a macroscopic field induced transition to a ferroelectric state but that d₃₃ is optimized in the ferroelectric, rhombohedral phase. Unipolar strain was measured as a function of temperature for x = 0.63 with strains of 0.30% achieved at 175°C, accompanied by a significant decrease in hysteresis with respect to room temperature measurements. The potential for BBFT compositions to be used as high strain actuators is demonstrated by the fabrication of a prototype multilayer which achieved 3 μm displacement at 150°C.     

New Lead‐Free (1 − x)(K0.5Na0.5)NbO3–x(Bi0.5Na0.5)ZrO3 Ceramics with High Piezoelectricity

For enhancing the piezoelectric properties of ceramics (Bi_0.5Na_0.5)ZrO₃ (BNZ) was used to partially substitute (K_0.5Na_0.5)NbO₃ (KNN). The addition of BNZ changes the symmetry of KNN ceramics from orthorhombic to tetragonal, and finally to rhombohedral phase. A new phase boundary with both rhombohedral–orthorhombic and orthorhombic–tetragonal phase transitions near room temperature is identified for KNN–0.050BNZ ceramics, where optimum electrical properties were obtained: d₃₃ = 360 pC/N, k_p = 32.1%, ε_r = 1429, tanδ = 3.5%, and T_C = 329°C. The results indicated a new method for designing high‐performance lead‐free piezoelectric materials.     

The Composition and Temperature‐Dependent Structure Evolution and Large Strain Response in (1−x)(Bi0.5Na0.5)TiO3−xBa(Al0.5Ta0.5)O3 Ceramics

The (1?x) (Bi_0.5Na_0.5)TiO₃?xBa(Al_0.5Ta_0.5)O₃((1?x)BNT‐xBAT) lead‐free piezoceramics was fabricated using a conventional solid‐state reaction method. The temperature and composition‐dependent strain behavior, dielectric, ferroelectric (FE), piezoelectric, and pyroelectric properties have been systematically investigated to develop lead‐free piezoelectric materials with large strain response for actuator application. As the BAT content increased, the FE order is disrupted resulting in a degradation of the remanent polarization, coercive field, and the depolarization temperature (T_d). A large strain of 0.36% with normalized strain d₃₃* = 448pm/V was obtained for the optimum composition x = 0.045 at room temperature. The bipolar and unipolar strains for the compositions x = 0.035 and x = 0.04 reach almost identical maximum values when the temperature is in the vicinity of their respective depolarization temperature (T_d). The Raman‐spectra analysis, macroscopic properties, thermal depolarization results, and temperature‐dependent relationships of both polarization and strain demonstrated that the origin of the large strain response for this investigated system is attributed to a field‐induced relaxor to FE phase transformation.     

Temperature‐insensitive strain behavior in 0.99[(1−x)Bi0.5(Na0.80K0.20)0.5TiO3−xBiFeO3]–0.01Ta lead‐free piezoelectric ceramics

Lead‐free 0.99[(1?x)Bi_0.5(Na_0.80K_0.20)_0.5TiO₃?xBiFeO₃]–0.01Ta (BNKT20–100xBF–1Ta) lead‐free piezoelectric ceramics were fabricated through conventional solid state sintering method. Results showed that change of BF content in the BNKT20–100xBF–1Ta induced a phase transition from ferroelectric to ergodic relaxor phase with a significant disruption of the long‐range ferroelectric order. A large electric‐field‐induced strain of 0.36% (at 80 kV/cm driving field, corresponding to a large signal of ~450 pm/V) which is derived from a reversible field‐induced ergodic relaxor to ferroelectric phase transformation, was obtained in the composition with x=0.01 near the ferroelectric‐ergodic relaxor phase boundary. Moreover, an attractive property for application in nonlinear actuators demanding enhanced thermal stability was obtained in this material, which showed a temperature‐insensitive strain characteristic in the temperature range from room temperature to 100°C.     

Structural and Piezoelectric Properties of (1−x)Pb(Zr1−yTiy)O3–xPb(Zn0.4Ni0.6)1/3Nb2/3O3 Ceramics Near Triple Point

The crystal structure and piezoelectric properties of (1?x)Pb(Zr_1?yTi_y)O₃‐xPb(Zn_0.4Ni_0.6)_1/3Nb_2/3O₃ [(1?x)PZ_1?yT_y‐xPZNN] ceramics were investigated. The 0.665PZ_0.45T_0.55‐0.335PZNN ceramic has the triple point composition, where the rhombohedral, pseudocubic, and tetragonal structures coexist. Maximum d₃₃ and k_p values of 770 pC/N and 0.69, respectively, were observed from this specimen; it also exhibited a large ε^T₃₃/ε_o value of 3250. Although the maximum d₃₃ value was obtained from the triple point composition specimen, its g₃₃ and d₃₃ × g₃₃ values were relatively small because of its large ε^T₃₃/ε_o value. However, the 0.665PZ_0.46T_0.54‐0.335PZNN ceramic, which has a rhombohedral structure, exhibited a large g₃₃ value of 43 × 10^?3 Vm/N and a d₃₃ × g₃₃ value of 27 000 × 10^?15 m²/N. Therefore, this ceramic is a good candidate for multilayer actuators and piezoelectric energy harvesters.     

Piezoelectric properties of (Na0.5K0.5)(Nb1‐xSbx)O3‐SrTiO3 ceramics with tetragonal‐pseudocubic PPB structure

CuO‐added 0.96(Na_0.5K_0.5)(Nb_1‐xSb_x)O₃‐0.04SrTiO₃ ceramics sintered at the low temperature of 960°C for 10 hours showed dense microstructures and high relative densities. The specimens with 0.0 ≤  x ≤ 0.04 had orthorhombic‐tetragonal polymorphic phase boundary (PPB) structure. Tetragonal‐pseudocubic PPB structure was observed in specimens with 0.05 ≤  x ≤ 0.07, while the specimen with x = 0.08 has a pseudocubic structure. The structural variation in the specimens is explained by the decreases in the orthorhombic‐tetragonal transition temperature and Curie temperature with the addition of Sb⁵⁺ ions. The specimens with 0.05 ≤  x ≤ 0.07, which have tetragonal‐pseudocubic PPB structure, had large electric field‐induced strains of 0.14%‐0.016%. Moreover, these specimens also showed increased d₃₃ values between 280 pC/N and 358 pC/N. In particular, the specimen with x = 0.055 showed particularly enhanced piezoelectric properties: d₃₃ of 358 pC/N, k_p of 0.45, and the electric field‐induced strain of 0.16% at 4.5 kV/mm.     

High permittivity (1−x)Bi1/2Na1/2TiO3‐xPbMg1/3Nb2/3O3 ceramics for high‐temperature‐stable capacitors

(1?x)Bi_1/2Na_1/2TiO₃‐xPbMg_1/3Nb_2/3O₃[(1?x)BNT‐xPMN] ceramics have been fabricated via a conventional solid‐state method for compositions x ≤ 0.3. The microstructure, phase structure, ferroelectric, and dielectric properties of ceramics were systematically studied as high‐temperature capacitor materials. XRD pattern certified perovskite phase with no secondary phase in all compositions. As PMN concentration increased, the phase of (1?x)BNT‐xPMN ceramics transformed from ferroelectric to relaxor gradually at room temperature, with prominent enhancement of dielectric temperature stability. For the composition x = 0.2, the temperature coefficient of capacitance (TCC) was <15% in a wide temperature range from 56 to 350°C with high relative permittivity (>3300) and low dielectric loss (<0.02) at 150°C, which indicated promising future for (1?x)BNT‐xPMN system as high‐temperature stable capacitor materials.     

Properties and structures of nonstoichiometric (K,Na)NbO3‐based lead‐free ceramics

The 0.968[(K_0.48Na_0.52)]Nb_0.95+xSb_0.05O₃–0.032(Bi_0.5Na_0.5)ZrO₃ [KNN_xS–BNZ] lead‐free ceramics with nonstoichiometric niobium ion were fabricated via conventional solid‐state sintering technique and their piezoelectric, dielectric and ferroelectric properties were investigated. When x = 0.010, enhanced piezoelectric properties (d₃₃ ≈ 421 pC/N and k_p ≈ 0.47) were obtained due to the construction of rhombohendral—tetragonal phase boundary near room temperature. The KNN_xS–BNZ ceramics possesses enhanced Curie temperature (T_c) with improved piezoelectric constant. A large d₃₃ of ~421 pC/N and a high T_c ~256°C can be simultaneously induced in the ceramics with x = 0.010. Especially, good thermal stability was observed in a broad temperature range. The results indicated that our work could benefit development of KNN‐based ceramics and widen their application range.     

Phase Diagram and Properties of High TC/TR−T Pb(In1/2Nb1/2) O3–Pb(Zn1/3Nb2/3)O3–PbTiO3 Ferroelectric Ceramics

A ternary ferroelectric ceramic system, (1?x?y)Pb(In_1/2Nb_1/2)O₃–xPb(Zn_1/3Nb_2/3)O₃–yPbTiO₃ (PIN–PZN–PT, x = 0.21, 0.27, 0.36, 0.42), was prepared using a two‐step precursor method. The phase structure, dielectric, piezoelectric, and ferroelectric properties of the ternary ceramics were systematically investigated. A morphotropic phase boundary (MPB) was identified by X‐ray diffraction. The optimum piezoelectric and electromechanical properties were achieved for a composition close to MPB (0.5PIN–0.21PZN–0.29PT), where the piezoelectric coefficient d₃₃, planar electromechanical coupling factor k_p, and remnant polarization P_r are 660 pC/N,72%, and 45 μC/cm², respectively. The Curie temperature T_C and rhombohedral to tetragonal phase transition temperature T_R?T were also derived by temperature dependence of dielectric measurements. The strongly “bended” MPB in the PIN–PT system was found to be “flattened” after addition of PZN in the PIN–PT–PZN system. The results demonstrate a possibility of growing ferroelectric single crystals with high electromechanical properties and expanded range of application temperature.     

Structure and electrical properties of perovskite layer (1−x)Sr2Nb2O7‐x(Na0.5Bi0.5)TiO3 high‐temperature piezoceramics

The structure and electrical properties of perovskite layer structured (PLS) (1?x)Sr₂Nb₂O₇‐x(Na_0.5Bi_0.5)TiO₃ (SNO‐NBT) prepared by solid‐state reaction method are investigated. The addition of NBT is beneficial to speed up mass transfer and particle rearrangement during sintering, leading to better sinterability and higher bulk density up to 96.8%. The solid solution limit x in the SNO‐NBT system is below 0.03, over which Ti⁴⁺ is preferable to aggregate and results in the generation of secondary phase. After the modification by NBT, all SNO‐NBT ceramics have a Curie temperature T_c up to over 1300°C and piezoelectric constant d₃₃ about 1.0 pC/N. The breakthrough of piezoelectricity can mainly be attributed to rotation and distortion of oxygen octahedron as well as higher poling electric field resulting from the improved bulk density. This study not only demonstrates how to improve piezoelectricity by NBT addition, but also opens up a new direction to design PLS piezoceramics by introducing appropriate second phase.     

Composition‐ and Temperature‐Dependent Large Strain in (1−x)(0.8Bi0.5Na0.5TiO3–0.2Bi0.5K0.5TiO3)– xNaNbO3 Ceramics

Ternary solid solutions of (1 ? x)(0.8Bi_0.5Na_0.5TiO₃–0.2Bi_0.5K_0.5TiO₃)– xNaNbO₃ (BNKT–xNN) lead‐free piezoceramics were fabricated using a conventional solid‐state reaction method. Pure BNKT composition exhibited an electric‐field‐induced irreversible structural transition from pseudocubic to ferroelectric rhombohedral phase at room temperature. Accompanied with the ferroelectric‐to‐relaxor temperature T_F‐R shifted down below room temperature as the substitution of NN, a compositionally induced nonergodic‐to‐ergodic relaxor transition was presented, which featured the pinched‐shape polarization and sprout‐shape strain hysteresis loops. A strain value of ~0.445% (under a driving field of 55 kV/cm) with large normalized strain of ~810 pm/V was obtained for the composition of BNKT–0.04NN, and the large strain was attributed to the reversible electric‐field‐induced transition between ergodic relaxor and ferroelectric phase.     

High Na‐ion conducting Na1+x[SnxGe2−x(PO4)3] glass‐ceramic electrolytes: Structural and electrochemical impedance studies

Na‐ion conducting Na_1+x[Sn_xGe_2?x(PO₄)₃] (x = 0, 0.25, 0.5, and 0.75 mol%) glass samples with NASICON‐type phase were synthesized by the melt quenching method and glass‐ceramics were formed by heat treating the precursor glasses at their crystallization temperatures. XRD traces exhibit formation of most stable crystalline phase NaGe₂(PO₄)₃ (ICSD‐164019) with trigonal structure. Structural illustration of sodium germanium phosphate [NaGe₂(PO₄)₃] displays that each germanium is surrounded by 6 oxygen atom showing octahedral symmetry (GeO₆) and phosphorous with 4 oxygen atoms showing tetrahedral symmetry (PO₄). The highest bulk Na⁺ ion conductivities and lowest activation energy for conduction were achieved to be 8.39 × 10^?05 S/cm and 0.52 eV for the optimum substitution levels (x = 0.5 mol%, Na_1.5[Sn_0.5Ge_1.5(PO₄)₃]) of tetrahedral Ge⁴⁺ ions by Sn⁴⁺ on Na–Ge–P network. CV studies of the best conducting Na_1.5[Sn_0.5Ge_1.5(PO₄)₃] glass‐ceramic electrolyte possesses a wide electrochemical window of 6 V. The structural and EIS studies of these glass‐ceramic electrolyte samples were monitored in light of the substitution of Ge by its larger homologue Sn.     

Phase‐Composition‐Dependent Piezoelectric and Electromechanical Strain Properties in (Bi1/2Na1/2)TiO3–Ba(Ni1/2Nb1/2)O3 Lead‐Free Ceramics

New lead‐free perovskite solid solution ceramics of (1 ? x)(Bi_1/2Na_1/2)TiO₃–xBa(Ni_1/2Nb_1/2)O₃[(1?x)BNT–xBNN,x = 0.02–0.06) were prepared and their dielectric, ferroelectric, piezoelectric, and electromechanical properties were investigated as a function of the BNN content. The X‐ray diffraction results indicated that the addition of BNN has induced a morphotropic phase transformation from rhombohedral to pseudocubic symmetry approximately at x = 0.045, accompanying an evolution of dielectric relaxor behavior as characterized by enhanced dielectric diffuseness and frequency dispersion. In the proximity of the ferroelectric rhombohedral and pseudocubic phase coexistence zone, the x = 0.045 ceramics exhibited optimal piezoelectric and electromechanical coupling properties of d₃₃~121 pC/N and k_p~0.27 owing to decreased energy barriers for polarization switching. However, further addition of BNN could cause a decrease in freezing temperatures of polar nanoregions till the coexistence of nonergodic and ergodic relaxor phases occurred near room temperature, especially for the x = 0.05 sample which has negligible negative strains and thus show the maximum electrostrain of 0.3% under an external electric field of 7 kV/mm, but almost vanished piezoelectric properties. This was attributed to the fact that the induced long‐range ferroelectric order could reversibly switch back to its original ergodic state upon removal of external electric fields.     

Normal‐Relaxor‐Diffuse Ferroelectric Phase Transition and Electrical Properties of Bi(Mg1/2Ti1/2)3–PbZrO3–PbTiO3 Solid Solution Ceramics Near the Morphotropic Phase Boundary

Perovskite‐type xBi(Mg_1/2Ti_1/2)O₃–(0.56 ? x)PbZrO₃–0.44PbTiO₃ (xBMT–PZ–PT) ternary solid solution ceramics were synthesized via a conventional solid‐state reaction method. The phase transition behaviors, dielectric, ferroelectric, and piezoelectric properties were investigated as a function of the BMT content. The X‐ray diffraction analysis showed that the tetragonality of xBMT–PZ–PT was enhanced with increasing the BMT content, and a morphotropic phase boundary (MPB) between rhombohedral and tetragonal phases was identified approximately in the composition of x = 0.08. In addition, the dielectric diffuseness and frequency dispersion behavior were induced with the addition of BMT and a normal‐relaxor‐diffuse ferroelectric transformation was observed from the PZ‐rich side to the BMT‐rich side. The electrical properties of xBMT–PZ–PT ceramics exhibit obviously compositional dependence. The x = 0.08 composition not only possessed the optimum properties with ε^T₃₃/ε₀ = 1450, Q_m = 69, d₃₃ = 390 pC/N, k_p = 0.46, P_r = 30 μC/cm², E_c = 1.4 kV/mm, T_c = 325°C, and a strain of 0.174% (d₃₃^* = 436 pm/V) under an electric field of 4 kV/mm as a result of the coexistence of two ferroelectric phases near the MPB, but also owned a good thermal‐depolarization behavior with a d₃₃ value of >315 pC/N up to 290°C and a frequency‐insensitive strain behavior.     

Large Strain Response in 0.99(Bi0.5Na0.4K0.1)TiO3–0.01(KxNa1−x)NbO3 Lead‐Free Ceramics Induced by the Change of K/Na Ratio in (KxNa1−x)NbO3

Influence of K/Na ratio in (K_xNa_1?x)NbO₃ on the ferroelectric stability and consequent changes in the electrical properties of 0.99(Bi_0.5Na_0.4K_0.1)TiO₃–0.01(K_xNa_1?x)NbO₃ (BNKT–K_xNN) ceramics were investigated. Results showed that change of K/Na ratio in KNN induces a phase transition from ferroelectric to ergodic relaxor phase with a significant disruption of the long‐range ferroelectric order, and correspondingly adjusts the ferroelectric–relaxor transition point T_F?R to room temperature. Accordingly, giant strain of ~0.46% (corresponding to a large signal d₃₃* of ~575 pm/V) which is comparable to that of Pb‐based antiferroelectrics is obtained at a K/Na ratio of ~1, and the emergence of large strain response induced by the change of K/Na ratio of KNN can be well explained by the correlation between the position of ferroelectric–ergodic relaxor phase boundary in the BNKT–K_xNN system and the tolerance factor t of the end number (K_xNN). In situ high‐energy X‐ray scattering experiments with external field reveals that the large strain response in the studied system is likely related to the electric field‐induced distortion from the pseudocubic structure.     

Semiconductivity in Acceptor‐Doped BaTi1−xHoxO3−x/2−δ/2

Acceptor‐doped BaTiO₃ powders of formula: BaTi_1?xHo_xO_3?x/2?δ/2: x = 0.0001, 0.001, 0.01, 0.03, and 0.07, were prepared by sol‐gel synthesis, fired at 800°C–1500°C and either quenched or slow‐cooled to room temperature. Electrical properties of ceramics depended on firing conditions, Ho content, and cooling rate. Pellets of all x values fired at 800°C–1000°C were insulating and, from the presence of OH bands in the IR spectra, charge balance appeared to involve co‐doping of Ho³⁺ and H⁺ ions without necessity for oxygen vacancy creation. At higher firing temperatures, OH bands were absent. Pellets fired at 1400°C in air and slow cooled were insulating for both low x (0.0001) and high x (0.07) but at intermediate x (0.001 and 0.01) passed through a resistivity minimum of 20–30 Ω cm at room temperature, attributed to the presence of Ti³⁺ ions; it is suggested that, for these dilute Ho contents, each oxygen vacancy is charge compensated by one Ho³⁺ and one Ti³⁺ ion. At higher x, charge compensation is by Ho³⁺ ions and samples are insulating. A second, more general mechanism to generate Ti³⁺ ions, and a modest level of semiconductivity, involves reversible oxygen loss at high temperatures.     

Large electric‐field‐induced strain and enhanced piezoelectric constant in CuO‐modified BiFeO3‐BaTiO3 ceramics

In this work, we fabricated the (1‐x)BiFeO₃‐xBaTiO₃+y‰ mol CuO ceramics by the modified thermal quenching technique. The pure perovskite phase was formed and a morphotropic phase boundary (MPB) was observed in the ceramics with x = 0.30‐0.33. The addition of CuO can significantly enhance the density of the BiFeO₃‐BaTiO₃ material. Importantly, an enhanced piezoelectric constant (d₃₃=165 pC/N), a large electric‐field‐induced strain (?S = 0.54%: peak to peak strain) and a large piezoelectric actuator constant (d₃₃*=449 pm/V) together with a high Curie temperature (T_C) of 503°C were observed in the ceramics with x = 0.30 and y = 5. As a result, the enhanced piezoelectricity and large electric‐field‐induced strain could significantly stimulate further researches in BFO‐based ceramics.     

Temperature‐ and Frequency‐Dependent Properties of the 0.75Bi1/2Na1/2TiO3–0.25SrTiO3 Lead‐Free Incipient Piezoceramic

The dielectric and electromechanical properties of 0.75Bi_1/2Na_1/2TiO₃–0.25 SrTiO₃ (25ST) as a function of temperature and frequency were studied. It is shown that the 25ST is a relaxor ferroelectric as evidenced by the temperature‐dependent dielectric relaxations with an incipient piezoelectricity featured by the presence of a reversible electric‐field‐induced phase transformation at room temperature. The transition occurs on a broad electric field strength range depending on field amplitude and frequency. It is also accompanied by a huge strain that is attributed to repetitive poling and depoling originating due to the reversibility of the phase transition. The 25ST makes an attractive lead‐free candidate for stack actuators as it presents a high normalized d₃₃* of ~600 pm/V at a low electric field of 4 kV/mm for frequencies ranging from 0.1 up to 100 Hz.     

Structure and microwave dielectric properties of the Li2/3(1−x)Sn1/3(1−x)MgxO systems (x = 0‐4/7)

In this paper, the Li_2/3(1?x)Sn_1/3(1?x)Mg_xO (LSMxO) ceramic systems were prepared by solid‐state reaction using novel atmosphere‐controlled sintering (x = 0‐4/7). Pure Li₂SnO₃ was observed for x = 0, the Li₂Mg₃SnO₆ and Li₂SnO₃ coexisted for x = 1/7, and the coexistence of three kinds of phases was detected for x = 1/5 and 1/4, including Li₄MgSn₂O₇ impurity phase. Pure Li₂Mg₃SnO₆‐like phase with cubic rock salt structure in Fm‐3m space group was obtained in the range of 1/3‐4/7. All samples showed well‐dense and smooth microstructures. The microwave dielectric properties highly depended on the phase composition, bond valence, FWHM of Raman spectrum, Raman shift, average grain sizes, and octahedral distortion. The LSMxO ceramics sintered at 1250°C for 5 hours possessed excellent comprehensive properties of ε_r = 15.43, Q×f = 80 902 GHz and τ_f = +5.61 ppm/°C for x = 1/7. Typically, the LSMxO ceramics sintered at 1350°C for 5 hours showed a maximum Q × f of 168 330 GHz for x = 1/2.     

Piezoelectric properties of (Na1−xKx)NbO3‐based lead‐free piezoelectric ceramics and their application in knocking sensor

Piezoelectric knocking sensors with a dense microstructure were fabricated at 960°C for 2 hours using various CuO‐added (Na_0.5K_0.5)NbO₃ (NKN)‐based piezoelectric ceramics. The practical sensitivity (S_P) of the knocking sensor, which is the ability to detect the knocking of a car engine, was influenced by the g₃₃ × k_p value of the piezoelectric ceramics, indicating that the g₃₃ × k_p can be considered a figure of merit of the piezoelectric ceramics used in the knocking sensor. The knocking sensor synthesized using the CuO‐added 0.95(Na_0.5K_0.5)(Nb_0.95Sb_0.05)O₃–0.05CaTiO₃ (CNKNS–CT) ceramic, which showed a g₃₃ of 25.7 Vm/N and k_p of 0.46, exhibited a high S_P of 119 mV/g at the resonance frequency. The S_P of the commercial knocking sensor, which was synthesized using the Pb(Zr,Ti)O₃ (PZT)‐based ceramic, was 112 mV/g at the resonance frequency. Hence, the knocking sensor fabricated using the CNKNS–CT piezoelectric ceramic can be used to replace the commercial PZT‐based knocking sensor.