WO2017006984A1 - Piezoelectric ceramic electronic component, and method for manufacturing piezoelectric ceramic electronic component - Google Patents

Abstract

In a piezoelectric ceramic electronic component, internal electrodes 3 are embedded in a piezoelectric ceramic element assembly 1. The piezoelectric ceramic element assembly 1 contains Zr, a lead-free perovskite compound including at least Li and Nb, and a composite oxide including a bivalent metallic element. The molar content of Li and the bivalent metallic element, and the combined molar content thereof are 0.025-0.080 part by mole, 0.045-0.086 part by mole, and 0.076-0.166 part by mole, respectively, with respect to 1 part by mole of Nb. The internal electrodes 3 contain Ni. The piezoelectric ceramic element assembly 1 is obtained by performing calcining synthesis of the perovskite compound, then adding a metallic element compound and a Zr compound thereto and performing calcining synthesis again, and then firing the product. By adjusting the blending ratio of the lead-free piezoelectric ceramic composition, a lead-free piezoelectric ceramic electronic component and a method for manufacturing the same are obtained whereby piezoelectric characteristics can be further enhanced relative to the prior art even when firing is performed together with Ni.

Description

Piezoelectric ceramic electronic component and method for manufacturing piezoelectric ceramic electronic component

The present invention relates to a piezoelectric ceramic electronic component and a method for manufacturing the piezoelectric ceramic electronic component, and more particularly to a piezoelectric ceramic electronic component such as a laminated piezoelectric actuator using a lead-free piezoelectric ceramic composition and a method for manufacturing the same.

In recent years, there has been an increasing demand for multilayer piezoelectric ceramic electronic components such as multilayer piezoelectric actuators that can acquire a large amount of displacement even with a small voltage.

This type of piezoelectric ceramic electronic component is generally manufactured by alternately laminating ceramic green sheets serving as piezoelectric ceramic layers and conductive films serving as internal electrodes and co-firing.

As the internal electrode material, Ag-based materials such as Ag and Ag—Pd alloy have been widely used conventionally. However, Ag-based materials are prone to migration, so that the occurrence of migration can be effectively suppressed. It is also desirable to use Ni that is readily available at a relatively low price.

Since this Ni is easily oxidized when fired in an air atmosphere, it is necessary to fire in a reducing atmosphere, and a piezoelectric material that can be co-fired in a reducing atmosphere is required.

However, with a zirconate titanate-based material or lead titanate-based material containing Pb, the environmental load is large, and Pb is reduced when firing in a reducing atmosphere, and desired stable piezoelectric characteristics are obtained. I can't.

Therefore, in recent years, various lead-free piezoelectric ceramic compositions mainly composed of alkali niobate materials have been developed.

For example, in Patent Document 1, the main component is represented by the general formula {(1-x) (K _1-ab Na _a Li _b ) (Nb _1-c Ta _c ) O ₃ -xM2M4O ₃ } (where M2 is Ca , Ba, and Sr, M4 is at least one of Zr, Sn, and Hf, and x, a, b, and c are 0.005 ≦ x ≦ 0.1, respectively. 0 ≦ a ≦ 0.9, 0 ≦ b ≦ 0.1, 0 ≦ a + b ≦ 0.9, and 0 ≦ c ≦ 0.3), and Mn is 100 mol of the main component. Piezoelectric ceramic compositions containing 2 to 15 mol and M4 in the range of 0.1 to 5.0 mol with respect to 100 mol of the main component have been proposed.

In Patent Document 1, a predetermined amount of Mn is contained in the piezoelectric ceramic composition, and Zr is contained in excess of the stoichiometric composition, thereby enabling firing in a reducing atmosphere in which Ni is not oxidized. . In Example 1, when Yb as a rare earth element was further contained, the content of Li and Ca relative to 1 mol part of Nb was set to 0.02 mol part and 0.04 mol part, respectively. Piezoelectric characteristics with a point Tc of 150 to 290 ° C., a piezoelectric constant d ₃₃ of 85 to 143 pC / N, and an electromechanical coupling coefficient kp of 16.8 to 30.5% are obtained.

International Publication No. 2008/152851 (Claim 1, Tables 1 to 6)

However, in Example 1 of Patent Document 1 described above, the piezoelectric constant d ₃₃ is not 143pC / N obtained only at most, further improvement in piezoelectric characteristics has been demanded.

The present invention has been made in view of such circumstances, and by adjusting the blending ratio of the piezoelectric ceramic composition, lead-free lead can be further improved in piezoelectric characteristics compared to the conventional case even when co-fired with Ni. It is an object of the present invention to provide a piezoelectric ceramic electronic component and a method for manufacturing the piezoelectric ceramic electronic component.

In order to achieve the above object, a piezoelectric ceramic electronic component according to the present invention is a piezoelectric ceramic electronic component comprising a piezoelectric ceramic body and an internal electrode embedded in the piezoelectric ceramic body, The ceramic body contains a lead-free perovskite compound containing at least Li and Nb, a composite oxide containing Zr, and a divalent metal element, and the molar content of Li is based on 1 mol part of Nb. 0.025 mol part or more and 0.080 mol part or less, and the content molar amount of the divalent metal element is 0.045 mol part or more and 0.086 mol part or less with respect to the Nb1 mol part, and The total content of the Li and the divalent metal element is 0.076 mol part or more and 0.166 mol part or less relative to the Nb1 mol part, and the internal electrode contains Ni. It is characterized in that.

The piezoelectric ceramic electronic component according to the present invention is a piezoelectric ceramic electronic component comprising a piezoelectric ceramic body and an external electrode formed on the surface of the piezoelectric ceramic body, wherein the piezoelectric ceramic body is The lead-containing perovskite compound containing at least Li and Nb, Zr, and a complex oxide containing a divalent metal element are contained, and the molar content of Li is 0.025 mole part relative to 1 mole part of Nb. It is 0.080 mol part or less, and the content molar amount of the divalent metal element is 0.045 mol part or more and 0.086 mol part or less with respect to the Nb1 mol part, and the Li and the 2 The total content of valent metal elements is 0.076 mol part or more and 0.166 mol part or less with respect to 1 mol part of Nb, and the external electrode contains Ni. It is.

In the piezoelectric ceramic electronic component of the present invention, it is preferable that the molar content of Zr is equal to or greater than the molar content of the divalent metal element.

Since Zr contributes to the improvement of piezoelectric characteristics, even better piezoelectric characteristics can be obtained by setting the molar content of Zr to be equal to or greater than the molar content of the divalent metal element.

In the piezoelectric ceramic electronic component of the present invention, it is preferable that the perovskite compound contains at least one element of K and Na.

In the piezoelectric ceramic electronic component of the present invention, the divalent metal element is preferably Ba, and in this case, the piezoelectric ceramic body preferably contains Mn.

In addition, the present inventors conducted extensive research on a production method suitable for the production of the piezoelectric ceramic electronic component. First, the perovskite compound was calcined and synthesized, and then the calcined powder was mixed with a metal element compound. It was found that the desired piezoelectric ceramic electronic component described above can be obtained by using the piezoelectric ceramic composition thus prepared by adding sinter and Zr compound and calcining again.

That is, the method for manufacturing a piezoelectric ceramic electronic component according to the present invention is a method for manufacturing a piezoelectric ceramic electronic component that forms a piezoelectric ceramic body containing at least Nb, Li, Zr, and a divalent metal element, At least the Nb compound and the Li compound are mixed and calcined so that the Li content is 0.025 mol part or more and 0.080 mol part or less with respect to 1 mol part of the Nb, and the first calcined powder is obtained. The step of producing, and the molar content of the divalent metal element is 0.045 mol part or more and 0.086 mol part or less relative to the Nb1 mol part, and the divalent metal element and the Li content mol The metal element compound, the Zr compound, and the first calcined powder are mixed and calcined so that the total amount is 0.076 mol part or more and 0.166 mol part or less with respect to the Nb1 mol part, First It is characterized in that it comprises a step of preparing a calcined powder.

In addition, the method for manufacturing a piezoelectric ceramic electronic component according to the present invention includes a step of integrally forming the second calcined powder and an electrode material containing Ni to produce a formed body, and the forming body in a reducing atmosphere. And a step of baking below.

Thus, a piezoelectric ceramic electronic component having good piezoelectric characteristics can be obtained with high efficiency even if it is co-sintered with Ni.

Furthermore, in the method for manufacturing a piezoelectric ceramic electronic component according to the present invention, the metal element compound is preferably a Ba compound.

According to the piezoelectric ceramic electronic component of the present invention, the piezoelectric ceramic body contains a complex oxide containing a lead-free perovskite compound containing at least Li and Nb, Zr, and a divalent metal element, and Nb, Since the respective molar amounts of Li and divalent metal elements are in the above-mentioned ranges, it is only necessary to adjust the blending ratio of the ceramic material forming the piezoelectric ceramic body without adding other additives. Thus, it is possible to obtain a lead-free piezoelectric ceramic electronic component having much better piezoelectric characteristics than conventional ones.

In addition, according to the method for manufacturing a piezoelectric ceramic electronic component of the present invention, after preliminarily synthesizing a perovskite compound having a predetermined composition, a predetermined amount of a metal element compound and a Zr compound are added and calcined again. Thus, a piezoelectric ceramic electronic component having high piezoelectric characteristics can be efficiently produced.

1 is a cross-sectional view showing an embodiment of a piezoelectric ceramic electronic component according to the present invention. It is a perspective view of the ceramic green sheet obtained in the manufacture process of the said multilayer piezoelectric actuator. It is a perspective view of the laminated piezoelectric actuator. It is sectional drawing which shows other embodiment of the piezoelectric ceramic electronic component which concerns on this invention. It is a figure which shows the mapping analysis of Ba element in the sample number 41. FIG. It is a figure which shows the mapping analysis of Ba element in sample number 41 '.

Next, an embodiment of the present invention will be described in detail.

FIG. 1 is a cross-sectional view showing an embodiment of a laminated piezoelectric actuator as a piezoelectric ceramic electronic component according to the present invention. The laminated piezoelectric actuator has a conductive material such as Ag at both ends of a piezoelectric ceramic body 1. The external electrode 2 (2a, 2b) is formed, and the piezoelectric ceramic body 1 is embedded with internal electrodes 3 (3a to 3g).

In the laminated piezoelectric actuator, one end of the internal electrodes 3a, 3c, 3e, and 3g is electrically connected to one external electrode 2a, and one end of the internal electrodes 3b, 3d, and 3f is electrically connected to the other external electrode 2b. Has been. In the laminated piezoelectric actuator, when a voltage is applied between the external electrode 2a and the external electrode 2b, the laminated piezoelectric actuator is displaced in the laminating direction indicated by the arrow X by the piezoelectric longitudinal effect.

The internal electrode 2 is formed of a conductive material containing Ni as a main component (for example, 30 wt% or more).

The piezoelectric ceramic body 1 is formed of a piezoelectric ceramic composition, and the piezoelectric ceramic composition includes an alkali niobate-based complex oxide whose main component is a lead-free perovskite compound, Zr, and divalent It is formed of a complex oxide containing the metal element.

Specifically, the main component of the piezoelectric ceramic composition can be represented by the general formula (A).

{(K _a Na _b ) _1-x Li _x } NbO ₃ + yMO + zZrO ₂ (A)
Here, M is a divalent metal element such as Ca, Ba, or Sr.

That is, this piezoelectric ceramic composition contains x mol part of Li, y mol part of divalent metal element M, and z mol part of Zr with respect to 1 mol part of Nb.

In the present invention, the main component is an alkali niobate-based composite oxide represented by the general formula (A), a solid solution of a composite oxide containing Zr, and a divalent metal element has an abundance ratio of 80% or more. It means having. In this case, the abundance ratio of the main component can be examined by a powder X-ray diffraction method (hereinafter referred to as “powder XRD method”). When analyzed by the powder XRD method, if a compound different from the above-mentioned solid solution is present, an X-ray diffraction peak is detected at a position different from that of the solid solution. Therefore, a known amount of a compound different from the solid solution is mixed with the solid solution in advance, and the peak intensity of this mixture is measured. If the relationship between the amount of the compound different from the solid solution and the peak intensity is obtained as a calibration curve, the abundance ratio can be detected from the peak intensity of X-ray diffraction.

Further, the solid solution means a state in which at least divalent metal elements M and Zr exist in the crystal or crystal grains of the alkali niobate complex oxide. The component composition of this solid solution was determined by analyzing the crystals or crystal grains of the fired alkali niobate complex oxide with a transmission electron microscope (TEM), and using an energy dispersive X-ray analyzer (EDS). It can be identified by analyzing the ratio.

Here, x and y satisfy the formulas (1) to (3).

0.025 ≦ x ≦ 0.080 (1)
0.045 ≦ y ≦ 0.086 (2)
0.076 ≦ x + y ≦ 0.166 (3)
In general formula (A), (yMO + zZrO ₂ ) is usually a complex oxide form of MZrO ₃ , which is a composite of MO and ZrO _2, and is an alkali niobate complex oxide {(K _a Na _b ) It is dissolved in _1-x Li _x } NbO ₃ .

Then, the piezoelectric ceramic composition represented by the general formula (A) satisfies only the formulas (1) to (3), and only the mixing ratio of the main component is adjusted without adding other additives. Thus, it is possible to obtain a lead-free multilayer piezoelectric actuator having much better piezoelectric characteristics than conventional ones.

The inventors of the present invention have increased the Li content molar amount relative to Nb1 mol part from 0.016 mol part, while the Curie point Tc is increased while the second phase transition point T _2nd is decreased. It was found that the piezoelectric constant d ₃₃ tends to be high.

When both of the divalent metal elements M and Li are increased from 0.04 mol part and 0.016 mol part with respect to 1 mol part of Nb, respectively, the Curie point Tc and the second phase transition point T _2nd fluctuate greatly. It was found that the piezoelectric characteristics can be further improved only by adjusting the main component composition, without making it.

That is, in the piezoelectric ceramic composition represented by the general formula (A), by adjusting and optimizing the blending ratio of Li and the divalent metal element M, a lead-free type having even better piezoelectric characteristics. A piezoelectric ceramic composition can be obtained.

Next, the reason why x and y are limited as in equations (1) to (3) will be described.

(1) Mol part x of Li with respect to Nb1 mol part
It is possible to improve the piezoelectric constant d ₃₃ by a molar portion x 0.016 mole part or more of Li to Nb1 molar portion piezoelectric ceramic composition. However, only by adjusting the main component composition, for example, the piezoelectric constant d ₃₃ is 170 pC / N or more and the displacement characteristic value Smax / Emax value (hereinafter referred to as “Smax / Emax value”) is 120 pm / V or more. In order to obtain piezoelectric characteristics, the Li content is 0.025 mol or more with respect to 1 mol of Nb even if the content of the divalent metal element M satisfies the formula (2). There is a need to. On the other hand, if the molar amount of Li exceeds 0.080 mole part with respect to 1 mole part of Nb, the insulation properties may be lowered, and the desired piezoelectricity may not be obtained.

Therefore, in the present embodiment, the molar part x of Li with respect to Nb1 mol part is set to 0.025 mol part or more and 0.080 mol part or less.

(2) Y part of divalent metal element M with respect to 1 part by mole of Nb
The molar content of the divalent metal element M with respect Nb1 molar parts can be improved piezoelectric constant d ₃₃ by 0.04 mol or more parts. However, only by adjusting the main component composition, for example, in order to obtain good piezoelectric characteristics with a piezoelectric constant d ₃₃ of 170 pC / N or more and an Smax / Emax value of 120 pm / V or more, the divalent metal element M Even if the content molar amount of Li satisfies Formula (1), the content molar amount needs to be 0.045 mol part or more with respect to 1 mol part of Nb. On the other hand, when the content of the divalent metal element M exceeds 0.086 mol part with respect to 1 mol part of Nb, the content of the divalent metal element M becomes excessive, and the Curie point Tc is significantly lowered. It is not preferable.

Therefore, in the present embodiment, the molar part y of the divalent metal element M relative to 1 part by mole of Nb is set to 0.045 mole part or more and 0.086 mole part or less.

(3) Sum of mole parts of divalent metal elements M and Li with respect to 1 mole part of Nb (x + y)
Even if the molar part x of Li relative to the molar part of Nb and the molar part y of the divalent metal element M satisfy the formulas (1) and (2), Li and the divalent metal element M relative to the molar part of Nb When the total (x + y) of each mole part is 0.076 mole part or less, the Smax / Emax value becomes less than 120 pm / V, and it may not be possible to obtain desired piezoelectric characteristics. On the other hand, if the total (x + y) of each mole part of Li and the divalent metal element M with respect to 1 part by mole of Nb exceeds 0.166 mole part, the electromechanical coupling coefficient kp decreases, the Curie point Tc and Smax / Emax. There is a risk of deterioration of various characteristics such as a decrease in value.

Therefore, in the present embodiment, the total (x + y) of the molar part of Li and the divalent metal element M with respect to 1 mol part of Nb is set to 0.076 mol part or more and 0.166 mol part or less.

As described above, in the present embodiment, since the blending ratio of the piezoelectric ceramic composition is adjusted so that the general formula (A) satisfies the mathematical formulas (1) to (3), the reducing property is such that Ni is not oxidized. Even when fired in an atmosphere, a piezoelectric ceramic electronic component having even better piezoelectric characteristics than before can be obtained. In other words, even if Ni is used as the internal electrode material, it is possible to perform co-firing, thereby obtaining a lead-free multilayer piezoelectric actuator having even better piezoelectric characteristics than conventional ones at a stable and low cost. be able to.

In addition, as a manufacturing method of the piezoelectric ceramic electronic component, as described later, first, an alkali niobate composite oxide is calcined and then an oxide containing a divalent metal element M and Zr is added. By again calcining synthesis, the divalent metal elements M and Li can be successfully solid-solved in the crystal grains, thereby efficiently obtaining the piezoelectric ceramic electronic component having a desired solid solution as a main component. be able to.

The molar content of Zr is not particularly limited, but Zr is present in the form of MZrO ₃ in combination with the divalent metal element M in the piezoelectric ceramic composition, and Zr is piezoelectric. Since it contributes to the improvement of the characteristics, it is possible to further improve the piezoelectric characteristics such as the piezoelectric constant d ₃₃ by containing the same or more than the stoichiometric composition represented by MZrO ₃ . That is, it is preferable that the molar part z with respect to the Nb1 molar part of Zr is equal to or more than the molar part y of the divalent metal element M with respect to the Nb1 molar part, and specifically satisfies the formula (4). preferable.

y ≦ z (4)
In addition, the content molar amount of K and Na after firing in the general formula (A) is not particularly limited, and is arbitrary in the range of 0.02 ≦ a ≦ 1.00 and 0 ≦ b ≦ 0.98, for example. Value can be set.

In the present invention, the main component only needs to satisfy the general formula (A), and it is also preferable to add various additives as necessary. For example, it is also preferable to contain Mn as a subcomponent with respect to the main component, which can improve piezoelectric characteristics such as an electromechanical coupling coefficient and a piezoelectric constant.

For example, when the divalent metal element M is formed of Ba, Ba may be segregated in the piezoelectric ceramic composition if Mn is not contained in the piezoelectric ceramic composition. If Ba segregates in the piezoelectric ceramic composition in this way, such segregated portions may hinder the expression of characteristics, and the piezoelectric characteristics may not be sufficiently improved.

In contrast, when Mn is contained in the piezoelectric ceramic composition when the divalent metal element M is formed from Ba, Ba is suppressed from segregating in the piezoelectric ceramic composition, and uniform or substantially uniform. Distributed. Thus, by distributing Ba uniformly or substantially uniformly in the piezoelectric ceramic composition, it is possible to improve piezoelectric characteristics such as an electromechanical coupling coefficient and a piezoelectric constant.

In this case, the piezoelectric ceramic composition can be represented by the general formula (B).

{(K _a Na _b ) _1-x Li _x } NbO ₃ + yBaO + zZrO ₂ + wMnO (B)
In addition, when Mn is contained in the piezoelectric ceramic composition as described above, the following effects can be obtained.

That is, when a piezoelectric material whose main component contains an alkali niobate-based composite oxide is fired in a reducing atmosphere, oxygen vacancies are easily formed, and therefore, the entire charge is easily evaporated so as to maintain neutrality. Alkali metal elements (K, Na, Li) are easily detached from the crystal lattice.

However, when Mn is contained as a subcomponent, Mn is solid-solved as an acceptor at the Nb site, and it is possible to compensate to some extent the charge of oxygen vacancies formed during firing in a reducing atmosphere. In addition, when Zr is added in excess of the stoichiometric composition (y <z), as with Mn, it becomes a solid solution at the Nb site as an acceptor, and the charge of oxygen vacancies formed during firing in a reducing atmosphere is effective. Therefore, it is possible to stably obtain a laminated piezoelectric actuator capable of further improving the piezoelectric characteristics, and to improve the reliability.

And this invention is also preferable to contain additives, such as Ni, like Example 3 of patent document 1, and this demonstrates the synergistic effect with optimization of the compounding ratio of a main component composition, and is better Realization of a laminated piezoelectric actuator having excellent piezoelectric characteristics is expected.

Next, a method for manufacturing the multilayer piezoelectric actuator will be described in detail.

First, Li-containing Li compound and Nb-containing Nb compound are prepared as ceramic raw materials, and K-containing K compound and Na-containing Na compound are prepared as necessary. The form of the ceramic raw material compound may be any of oxide, carbonate, hydroxide, fluoride, and chloride.

Next, the ceramic raw material is adjusted so that the content of Li in the fired piezoelectric ceramic composition (piezoelectric ceramic body) is 0.032 mole part or more and 0.075 mole part or less with respect to 1 mole part of Nb. Then, these weighed materials are put into a ball mill containing a grinding medium such as partially stabilized zirconia (hereinafter referred to as “PSZ”) balls, and sufficiently wet-ground in a solvent such as ethanol to obtain a mixture. obtain.

Then, after drying the mixture, the mixture is calcined at a predetermined temperature (for example, 850 to 1000 ° C.) for a predetermined time to synthesize, pulverize, and thereby the first calcined composed of the alkali niobate complex oxide. A powder is obtained (first calcination treatment).

Next, an M compound containing a divalent metal element M and a Zr compound containing Zr are prepared. The form of the M compound and the Zr compound may be any of oxide, carbonate, hydroxide, and chloride.

Next, the content molar amount of the divalent metal element M in the fired piezoelectric ceramic composition is 0.045 mol part or more and 0.086 mol part or less with respect to 1 mol part of Nb, and the divalent metal element M is And the total content of Li is 0.075 mol part or more and 0.166 mol part or less with respect to 1 mol part of Nb, and the Zr content mol amount is preferably equal to the divalent metal element M content mol amount. As described above, the first calcined powder, the M compound, and the Zr compound are weighed, and these weighed products are put into a ball mill containing a grinding medium such as a PSZ ball, and sufficiently in a solvent such as ethanol. To obtain a mixture.

The mixture is dried and then calcined at a predetermined temperature (for example, 850 to 1000 ° C.) for a predetermined time to synthesize and pulverize to obtain a second calcined powder as a main component powder (second Calcination treatment).

Thereby, the piezoelectric ceramic composition in which both Li and the divalent metal element M are solid-solved in the crystal grains can be obtained.

That is, for example, all of the ceramic raw materials that contribute to the formation of the main component are weighed at the same time, and both Li and the divalent metal element M are contained in the crystal particles even if synthesized by one calcination treatment. It is difficult to form a solid solution, and it is impossible to form a solid solution that can exhibit the effects of the present invention. When synthesized by a single calcining treatment, the synthesis reaction and the synthesis rate differ depending on the additive element, so that a heterogeneous phase having no perovskite structure is generated, and the synthesis of the main component may be partially inhibited.

Also, after calcining and synthesizing an alkali niobate-based composite oxide, a solid solution capable of exhibiting the effects of the present invention is formed even when a divalent metal element compound and a Zr compound are added and fired. I can't. This is because once the alkali niobate complex oxide is synthesized, the divalent metal element compound or Zr compound cannot be dissolved in the alkali niobate complex oxide.

Furthermore, after preparing a composite of a metal element compound and a Zr compound, even if these are mixed with an alkali metal compound and the main component is calcined, it is added in the same manner as when synthesized by a single calcining treatment. Since the synthesis reaction and the speed of synthesis differ depending on the element, there is a possibility that impurities that affect the characteristics are synthesized.

On the other hand, as described above, when the calcination process is performed in two steps of the first calcination process and the second calcination process, {(K _a Na _b ) _1-x Li _x } NbO A desired piezoelectric ceramic composition mainly composed of a solid solution of ₃ and MZrO ₃ can be obtained. That is, a part of alkali metal such as Li is volatilized in the first calcining treatment, but the alkali metal that has not volatilized is coordinated to the crystal lattice of the perovskite structure and is solidly dissolved in the crystal grains. Thus, a first calcined powder made of an alkali niobate-based composite oxide having a desired composition can be produced. Then, by calcining a mixture of the first calcined powder, M compound, and Zr compound in the subsequent second calcining treatment, the first calcined powder maintains its composition and the M compound and Zr. It is considered that a piezoelectric ceramic composition in which a desired solid solution is formed by solid solution with a complex oxide containing a compound can be obtained.

Next, various additives such as MnCO ₃ are added to the second calcined powder thus obtained, if necessary, and then an organic binder and a dispersant are added. Wet mix in to obtain a ceramic slurry. And after that, a ceramic green sheet is produced by carrying out a shaping | molding process using a doctor blade method etc.

Next, a conductive paste for internal electrodes containing Ni as a main component is used, and a conductive layer 5 (5a-5g) having a predetermined shape is formed on the ceramic green sheets 4 (4a-4g) by screen printing as shown in FIG. Form.

Next, the ceramic green sheets 4a to 4g on which the conductive layers 5a to 5g are formed are stacked, and then sandwiched between the ceramic green sheets 6a and 6b on which the conductive layers 5a to 5g are not formed, followed by pressure bonding. Thereby, a ceramic laminate in which the conductive layers 5a to 5g and the ceramic green sheets 4a to 4g are alternately laminated is manufactured. Next, the ceramic laminate is cut into a predetermined size and accommodated in an alumina pod (sheath), subjected to a binder removal treatment at a predetermined temperature (for example, 250 to 500 ° C.), and then a predetermined temperature ( For example, the piezoelectric ceramic body 1 in which the internal electrodes 3a to 3g are embedded is formed by firing at 1000 to 1160 ° C.).

Next, an external electrode conductive paste made of Ag or the like is applied to both ends of the piezoelectric ceramic body 1 and subjected to a baking process at a predetermined temperature (for example, 750 ° C. to 850 ° C.), as shown in FIG. 2a and 2b are formed. Thereafter, a predetermined polarization process is performed, whereby a laminated piezoelectric actuator is manufactured. The external electrodes 2a and 2b may be formed by a thin film forming method such as a sputtering method or a vacuum vapor deposition method as long as the adhesion is good.

As described above, in this embodiment, a first calcined powder having a desired composition made of an alkali niobate-based composite oxide is produced, and then the metal element compound and the Zr compound are mixed with the first calcined powder and again. Since the second calcined powder is calcined, the volatilization of alkali metal such as Li is suppressed in the second calcining process and the divalent metal elements M and Zr are easily contained in the crystal grains. Thus, it is possible to obtain a laminated piezoelectric actuator having a good piezoelectric characteristic composed mainly of a solid solution having a desired composition.

In the multilayer piezoelectric actuator, the ceramic green sheet 4 is formed of the piezoelectric ceramic composition, and the internal electrode is mainly composed of Ni, not a noble metal material such as Ag. Therefore, the multilayer piezoelectric actuator has good piezoelectric characteristics at low cost. Thus, it is possible to obtain a piezoelectric ceramic electronic component with excellent practicality that is effective in suppressing the occurrence of migration.

FIG. 4 is a sectional view showing another embodiment of a single plate type piezoelectric actuator as another embodiment of the piezoelectric ceramic electronic component according to the present invention.

That is, in this piezoelectric actuator, external electrodes 12 a and 12 b made of a conductive material such as Ni are formed on the surface of the piezoelectric ceramic body 11. In the piezoelectric actuator, when a voltage is applied between the external electrode 12a and the external electrode 12b, the piezoelectric actuator is displaced in the arrow Y direction by the piezoelectric longitudinal effect.

In this piezoelectric actuator, after forming a molded body having the above-described component composition by using a sheet method or press working, a conductive paste for external electrodes mainly composed of Ni is applied to both surfaces of the molded body. Can be easily produced by co-firing in a reducing atmosphere.

The present invention is not limited to the above embodiment. In the above embodiment, the multilayer piezoelectric actuator and the single plate type piezoelectric actuator are exemplified as the piezoelectric ceramic electronic component, but it goes without saying that the piezoelectric ceramic electronic component can be applied to various piezoelectric components.

Further, representative examples of the divalent metal element M include Ca, Sr, and Ba, but other divalent metal elements such as Mg may be included. Mg may be dissolved in Ca, Sr, or Ba and exist in the crystal grains, but does not affect the characteristics.

Next, specific examples of the present invention will be described.

Table 1 shows the composition components at the time of preparation of the samples of sample numbers 1 to 24.

That is, first, K ₂ CO ₃ , Na ₂ CO ₃ , Li ₂ CO ₃ , and Nb ₂ O ₅ were prepared as ceramic raw materials. Then, in the general formula: [{(K _a Na _b ) _1-x Li _x } NbO ₃ ], the ceramic raw materials were weighed so that the charged amounts of a, b, and x were as shown in Table 1. Next, these weighed materials were put into a ball mill containing PSZ balls having a diameter of 2 mm, and thoroughly wet mixed using ethanol as a solvent. And after drying the obtained mixture, it calcined for 2 hours in air | atmosphere at the temperature of 850 degreeC, and was crushed by this, and obtained the 1st calcined powder.

Next, in addition to the first calcined powder, BaCO ₃ and ZrO ₂ are prepared. In the general formula: [{(K _a Na _b ) _1-x Li _x } NbO ₃ + yBaO + zZrO ₂ ], charging y and z The first calcined powder, BaCO ₃ , and ZrO ₂ were weighed so that the amounts were as shown in Table 1. Next, these weighed materials were put into a ball mill containing PSZ balls as described above, and sufficiently wet mixed using ethanol as a solvent. And after drying the obtained mixture, it calcined in air | atmosphere for 2 hours at the temperature of 850 degreeC, and obtained the 2nd calcined powder by this.

It was confirmed whether this powder has a perovskite structure using the powder XRD method. The presence of the perovskite structure can be confirmed by whether or not an X-ray diffraction peak appears at a specific position of the X-ray diffraction pattern obtained by the X-ray diffraction method. For example, Non-Patent Document 1 describes powder X-ray diffraction data of (Na _0.35 K _0.65 ) NbO ₃ .

Next, this second calcined powder and MnCO ₃ were prepared. In the general formula: [{(K _a Na _b ) _1-x Li _x } NbO ₃ + yBaO + zZrO ₂ + wMnO], the amount of w charged was as shown in Table 1. Weigh it so that it becomes, put it into a ball mill containing PSZ balls together with an organic binder, dispersant, and pure water, mix thoroughly by wet, and then perform molding using the doctor blade method, thickness A ceramic green sheet having a thickness of 120 μm was obtained.

Next, this ceramic green sheet is punched out into a circular shape with a diameter of 10 mm after firing, and thereafter, 11 ceramic green sheets punched into this circular shape are stacked and applied at a pressure of about 2.45 × 10 ⁷ Pa. To obtain a ceramic molded body.

Next, the ceramic molded body is fired at a temperature of about 1100 ° C. for 2 hours in a reducing atmosphere adjusted so that the metal Ni and NiO are on the reduction side 0.5 digit from the equilibrium oxygen partial pressure at which the metal Ni and NiO are in an equilibrium state. Thus, a piezoelectric ceramic body was obtained. Then, sputtering is performed on both main surfaces of this piezoelectric ceramic body to form an external electrode made of Ag, and then an electric field of 3 kV / mm is applied in silicone oil at 80 ° C. for 30 minutes. ~ 24 samples were obtained.

Next, the piezoelectric constant d ₃₃ , the Smax / Emax value, the Curie point Tc, the second phase transition point T _2nd , and the electromechanical coupling coefficient kp of the radial resonance vibration were measured for each of the sample numbers 1 to 24.

The piezoelectric constant d ₃₃ was obtained from the amount of generated charges at the measurement frequency of 110 Hz with a force of 0.25 N _rms loaded using a d ₃₃ meter.

The Smax / Emax value was determined as follows.

That is, an electric field E of 0.5 to 11 kV / mm is applied at a measurement frequency of 1 kHz, the amount of radial displacement of each sample is measured with a laser Doppler vibrometer, and this measured value is divided by the diameter (= 10 mm). The strain S was determined, and then the strain S was divided by the electric field E to calculate the displacement characteristic value S / E. The maximum value of the displacement characteristic value S / E was defined as the Smax / Emax value.

Curie point Tc was measured by measuring the temperature characteristic of relative permittivity εr at a measurement frequency of 1 kHz with an impedance analyzer, and calculating the maximum temperature of relative permittivity εr, which was taken as Curie point Tc.

Similarly, the second phase transition point T _2nd, than the Curie point Tc to calculate the maximum temperature of the relative dielectric constant of the low temperature side, which was used as a second phase transition point T _2nd.

For each of the piezoelectric ceramic bodies of sample numbers 1 to 24, the powder XRD method was used, the temperature was changed, and the crystal system of the main component with respect to the temperature was analyzed. In general, it is known that the crystal system changes at the Curie point Tc and the second phase transition point T _2nd . Therefore, from the analysis of such a crystal system, it is found that the temperature at the boundary between the tetragonal crystal and the cubic crystal is the Curie point Tc, and the temperature at the boundary between the orthorhombic or rhombohedral crystal and the tetragonal crystal is the second phase transition point T _2nd. confirmed.

The electromechanical coupling coefficient kp was obtained by a resonance-antiresonance method using an impedance analyzer. That is, Formula (1) is established between the electromechanical coupling coefficient kp, the resonance frequency Fr, and the antiresonance frequency Fa.

Then, using the impedance analyzer, the resonance frequency Fr and anti-resonance frequency Fa of the spreading vibration of the disk were measured, and the measurement result was substituted into Equation (1) to calculate the electromechanical coupling coefficient kp.

The method for calculating the electromechanical coupling coefficient kp is based on Non-Patent Document 2.
Published by Japan Electronics and Information Technology Industries Association, "JEITA EM-4501 Electrical Testing Method for Piezoelectric Ceramic Vibrators", September 2010

Further, each of the samples Nos. 1 to 24 was subjected to composition analysis using inductively coupled plasma-emission spectroscopy (Inductively-Coupled-Plasma-Atomic-Emission-Spectroscopy; hereinafter referred to as "ICP-AES"), and Nb1 mol. Each molar part of K, Na, Li, Ba, (Li + Ba), Zr, and Mn after firing on the part was determined.

Table 2 shows the measurement results of the component compositions after firing of sample numbers 1 to 24, the piezoelectric constant d ₃₃ , the Smax / Emax value, the Curie point Tc, the second phase transition point T _2nd , and the electromechanical coupling coefficient kp. .

The piezoelectric constant d ₃₃ is 170 pC / N or more, the Smax / Emax value is 120 pm / V or more, the Curie point Tc is 160 ° C. or more, the second phase transition point T _2nd is 100 ° C. or less, and the electromechanical coupling coefficient kp is 31%. The above was judged as a good product.

Sample No. 1 does not contain Li in the piezoelectric ceramic composition, so that the piezoelectric constant d ₃₃ is 133 pC / N and the Smax / Emax value is low at 86 pm / V, indicating that the piezoelectric characteristics are inferior. It was.

In Sample Nos. 2 to 6, the total (x + y) of the mole parts of Li and Ba relative to 1 mole part of Nb is 0.051 to 0.074 mole part, and is less than 0.076 mole part. Therefore, the piezoelectric constant d ₃₃ Was 146 to 165 pC / N, and Smax / Emax values were low, 109 to 118 pm / V, indicating that the piezoelectric properties were inferior.

Sample No. 8,20, molar portion y of the Ba is less 0.035 parts by mole with respect Nb1 moles unit, Thus the piezoelectric constant d ₃₃ is 167 ~ 168pC / N, Smax / Emax value is as low as 114 ~ 118pm / V The piezoelectric characteristics could not be sufficiently improved.

Sample No. 15 has a small molar portion y is 0.034 mole of Ba with respect Nb1 molar parts, although the piezoelectric constant d ₃₃ of the order 190pC / N was obtained, Smax / Emax values as low as 115pm / V It was.

In any case, it was found from Sample Nos. 8, 15, and 20 that when the mole part y of Ba with respect to 1 part by mole of Nb is less than 0.045, it is difficult to achieve both the piezoelectric constant d ₃₃ and the Smax / Emax value. .

In Sample Nos. 14, 19, and 23, the Cury point Tc was lowered to 100 to 120 ° C. because the molar part y of Ba was excessively 0.100 to 0.101 mole part relative to 1 mole part of Nb. In particular, in sample No. 23, the total (x + y) of the molar part of Li and Ba with respect to 1 part by mole of Nb is also excessive at 0.172 part by mole, so that the piezoelectric constant d ₃₃ and Smax / Emax value are also reduced, and the piezoelectric characteristics are reduced. It has also been found that this leads to deterioration.

In Sample No. 24, since the molar part x of Li with respect to 1 mol part of Nb is excessive as 0.081 mol part, the insulating property is lowered and the polarization treatment cannot be performed, and the piezoelectric characteristics cannot be measured. It was.

In contrast, Sample Nos. 7, 9 to 13, 16 to 18, 21, and 22 have a molar part x of Li and a molar part y of Ba of 0.025 to 0.080 mole part, and Nb1 mole part, respectively. Since the total amount (x + y) of the molar parts of Li and Ba is 0.076 to 0.166 mole part within the range of the present invention, the piezoelectric constant d ₃₃ is 170. 246 pC / N, Smax / Emax values are as large as 122 to 187 pm / V, Curie point Tc is as high as 160 to 310 ° C., second phase transition point T _2nd is as low as 30 to 100 ° C., and Curie point Tc is It was found that the difference from the phase transition point T _2nd was sufficient, and the electromechanical coupling coefficient kp was 31.2 to 38.3%, and good piezoelectric characteristics were obtained.

In this Example 2, samples were prepared by different manufacturing methods, and the characteristics were evaluated.

[Production process (1)]
Sample No. 12 produced in Example 1 was prepared and used as a sample for the production process (1).

[Production process (2)]
As ceramic raw materials, K ₂ CO ₃ , Na ₂ CO ₃ , Li ₂ CO ₃ , Nb ₂ O ₅ , BaCO ₃ , ZrO ₂ , and MnCO ₃ were prepared. Then, in the general formula: [{(K _a Na _b ) _1−x Li _x } NbO ₃ + yBaO + zZrO ₂ + wMnO], preparation amounts of a, b, x, y, z, and w are as shown in Table 3 (2 ) Was weighed so that the composition shown in FIG.

Next, these weighed materials were put into a ball mill containing PSZ balls having a diameter of 2 mm, and thoroughly wet mixed using ethanol as a solvent. And after drying the obtained mixture, it calcined in air | atmosphere for 2 hours at the temperature of 850 degreeC, and was crushed by this, and calcined powder was obtained.

Next, this calcined powder is put into a ball mill containing PSZ balls together with an organic binder, a dispersant, and pure water and mixed sufficiently wet, and then subjected to a molding process using a doctor blade method, A ceramic green sheet having a thickness of 120 μm was obtained.

Thereafter, a molding process and a firing process were performed by the same method and procedure as in Example 1 to prepare samples Nos. 31 to 33.

[Production process (3)]
As ceramic raw materials, K ₂ CO ₃ , Na ₂ CO ₃ , Li ₂ CO ₃ , and Nb ₂ O ₅ were prepared. And, in the general formula: [{(K _a Na _b ) _1-x Li _x } NbO ₃ ], the a, b, x are charged so as to have the composition shown in the production process (3) in Table 3. The ceramic raw material was weighed. Next, these weighed materials were put into a ball mill containing PSZ balls having a diameter of 2 mm, and thoroughly wet mixed using ethanol as a solvent. And after drying the obtained mixture, it calcined in the air | atmosphere for 2 hours at the temperature of 850 degreeC, and thereby calcined powder was obtained.

Then, in addition to this calcined powder, BaCO ₃ , ZrO ₂ , and MnCO ₃ are prepared. In the general formula: [{(K _a Na _b ) _1-x Li _x } NbO ₃ + yBaO + zZrO ₂ + wMnO], y, z The calcined powder, BaCO ₃ , ZrO ₂ , and MnCO ₃ were weighed so that the charged amounts of w and w had the composition shown in the production process (3) of Table 3. Next, these weighed materials are put into a ball mill containing PSZ balls together with an organic binder, a dispersant, and pure water and mixed sufficiently wet, and then subjected to a molding process using a doctor blade method. A 120 μm ceramic green sheet was obtained.

Thereafter, a molding process, a firing process, and the like were performed by the same method and procedure as in Example 1 to prepare a sample of Sample No. 34.

[Production process (4)]
BaCO ₃ and ZrO ₂ were prepared, and BaCO ₃ and ZrO ₂ were weighed to form BaZrO ₃ . Next, these weighed materials were put into a ball mill containing PSZ balls having a diameter of 2 mm, and thoroughly wet mixed using ethanol as a solvent. And after drying the obtained mixture, it calcined in air | atmosphere at the temperature of 1000 degreeC for 2 hours, and, thereby, the 1st calcined powder was obtained.

Next, in addition to the first calcined powder, K ₂ CO ₃ , Na ₂ CO ₃ , Li ₂ CO ₃ , Nb ₂ O ₅ , and ZrO ₂ were prepared. In the general formula [{(K _a Na _b ) _1−x Li _x } NbO ₃ + yBaO + zZrO ₂ ], the preparation amounts of a, b, x, y, and z are the compositions shown in the production process (4) in Table 3. Weighed so that

Next, these weighed materials were put into a ball mill containing PSZ balls having a diameter of 2 mm, and thoroughly wet mixed using ethanol as a solvent. And after drying the obtained mixture, it calcined in air | atmosphere for 2 hours at the temperature of 850 degreeC, and obtained the 2nd calcined powder by this.

Next, this second calcined powder and MnCO ₃ are prepared. In the general formula: [{(K _a Na _b ) _1-x Li _x } NbO ₃ + yBaO + zZrO ₂ + wMnO], the amount of w charged is as shown in Table 3. The composition was weighed so as to have the composition shown in the production process (4).

Next, these weighed materials are put into a ball mill containing PSZ balls together with an organic binder, a dispersant, and pure water and mixed sufficiently wet, and then subjected to a molding process using a doctor blade method to obtain a thickness. A ceramic green sheet having a thickness of 120 μm was obtained.

Thereafter, a molding process, a firing process, and the like were performed by the same method and procedure as in Example 1 to prepare a sample of Sample No. 35.

Table 3 shows the composition of the components of Sample No. 12 and Sample Nos. 31 to 35 when charged.

Next, for each sample Nos. 31 to 35, composition analysis was performed using ICP-AES in the same manner and procedure as in Example 1, and K, Na, Li, Ba, Each molar part of (Li + Ba), Zr, and Mn was determined, and the piezoelectric constant d ₃₃ and Smax / Emax value were measured.

Table 4 shows the composition components after firing of the sample numbers 31 to 35, the piezoelectric constant d ₃₃ and the Smax / Emax values. In Table 4, the measurement result of sample number 12 is shown again.

In Sample Nos. 31 to 33, each ceramic raw material contributing to the formation of the main component is weighed and calcined at the same time. Therefore, the piezoelectric constant d ₃₃ is 105 to 143 pC / N, and the Smax / Emax value is 75 to 111 pm / V, which is lower than that of Sample No. 12.

In Sample No. 31, the molar parts x and y of Li and Ba with respect to Nb1 mol part are outside the scope of the present invention, and in Sample No. 32, the molar part y of Ba with respect to Nb1 mol part is out of the scope of the present invention. In any case, it is considered difficult to obtain a solid solution having a crystal structure that satisfies the requirements of the present invention if the ceramic raw materials are weighed and calcined at the same time.

In sample No. 34, only the alkali niobate complex oxide was calcined and then the other components (BaCO ₃ , ZrO ₂ , and MnCO ₃ ) were added and fired, so the piezoelectric constant d ₃₃ was 141 pC. / N and Smax / Emax values were 102 pm / V, which was also lower than that of Sample No. 12.

In Sample No. 35, BaZrO ₃ was calcined and synthesized, and each alkali metal compound and ZrO ₂ were mixed with the BaZrO ₃ and calcined. Therefore, the piezoelectric constant d ₃₃ was 94 pC / N, and the Smax / Emax value was 56 pm / V, which is also lower than that of sample number 12.

On the other hand, sample No. 12 was calcined and synthesized after the alkali niobate-based composite oxide was calcined, and BaCO ₃ , ZrO ₂ , and MnCO ₃ were added and calcined again. Therefore, the piezoelectric constant d ₃₃ was 230 pC / The N and Smax / Emax values were 179 pm / V, and good results were obtained.

Thus, it was found that different piezoelectric characteristics can be obtained due to the difference in the manufacturing process. As a result of analyzing each sample having reduced piezoelectricity by the powder XRD method, many heterogeneous phases having a perovskite structure as the main component were detected, and the synthesis of the main component was partially inhibited. Then, after preparing a first calcined powder by calcining an alkali niobate complex oxide as in the production process (1), BaCO ₃ , ZrO ₂ , and It was found that a piezoelectric ceramic composition having desired piezoelectric characteristics can be obtained by adding MnCO ₃ and calcining again, followed by firing.

First, as ceramic base materials _were prepared _{K 2 CO 3, Na 2 CO} 3, Li 2 CO 3, Nb 2 O 5. Then, in the general formula: [{(K _a Na _b ) _1-x Li _x } NbO ₃ ], the ceramic raw materials were weighed so that the charged amounts of a, b, and x were as shown in Table 5. Next, these weighed materials were put into a ball mill containing PSZ balls having a diameter of 2 mm, and thoroughly wet mixed using ethanol as a solvent. And after drying the obtained mixture, it calcined for 2 hours in air | atmosphere at the temperature of 850 degreeC, and was crushed by this, and obtained the 1st calcined powder.

Thereafter, samples Nos. 41 and 42 were prepared by the same method and procedure as in Example 1.

And about each sample of sample numbers 41 and 42, composition analysis was performed using ICP-AES in the same manner and procedure as in Example 1, and K, Na, Li, Ba, (Li + Ba), The molar parts of Zr and Mn were determined, and the piezoelectric constant d ₃₃ and Smax / Emax values were measured.

Table 5 shows the component composition at the time of preparation of sample numbers 41 and 42, and Table 6 shows the component composition after firing, the piezoelectric constant d ₃₃ and the Smax / Emax value. In Tables 5 and 6, sample number 12 is shown again for comparison.

As is apparent from Tables 5 and 6, if the molar parts x and y of Li and Ba and the total of these molar parts (x + y) are within the scope of the present invention relative to 1 molar part of Nb, the molar content of K and Na It was found that a piezoelectric ceramic composition having desired good piezoelectric characteristics can be obtained even if the amount is varied.

A sample No. 41 ′ having the same composition as Sample No. 41 was prepared except that Mn was not added.

Then, for each of the samples Nos. 41 and 41 ′, a Ba element mapping analysis was performed using a WDX (wavelength dispersive X-ray spectrometer).

FIG. 5 is a diagram showing a mapping analysis of sample number 41, and FIG. 6 is a diagram showing a mapping analysis of sample number 41 ′.

Sample No. 41 ′ not containing Mn shows that Ba is segregated in the piezoelectric ceramic composition as shown in FIG. 6 (indicated by S in the figure).

On the other hand, as shown in FIG. 5, it was confirmed that the sample number 41 containing no Mn was uniformly or substantially uniformly distributed with the segregation in the Ba piezoelectric ceramic composition suppressed.

And, it is considered that improvement of piezoelectric characteristics such as an electromechanical coupling coefficient and a piezoelectric constant can be achieved by uniformly and substantially uniformly distributing Ba in the piezoelectric ceramic composition.

By adjusting the blending ratio of the piezoelectric ceramic composition, a lead-free piezoelectric ceramic electronic component capable of further improving the piezoelectric characteristics compared with the conventional one even when co-fired with Ni is realized.

1 Piezoelectric Ceramic Element 2a, 2b External Electrode 3a-3g Internal Electrode 11 Piezoelectric Ceramic Element 12a, 12b External Electrode

Claims (9)

1. A piezoelectric ceramic electronic component comprising a piezoelectric ceramic body and an internal electrode embedded in the piezoelectric ceramic body,
   The piezoelectric ceramic body contains a complex oxide containing a lead-free perovskite compound containing at least Li and Nb, Zr, and a divalent metal element, and the molar content of Li is the Nb1 mole part. 0.025 mol part or more and 0.080 mol part or less, and the content molar amount of the divalent metal element is 0.045 mol part or more and 0.086 mol part or less with respect to the Nb1 mol part, And the total of the content molar amount of the Li and the divalent metal element is 0.076 mol part or more and 0.166 mol part or less with respect to the Nb1 mol part,
   The piezoelectric ceramic electronic component, wherein the internal electrode contains Ni.
2. A piezoelectric ceramic electronic component comprising a piezoelectric ceramic body and external electrodes formed on the surface of the piezoelectric ceramic body,
   The piezoelectric ceramic body contains a complex oxide containing a lead-free perovskite compound containing at least Li and Nb, Zr, and a divalent metal element, and the molar content of Li is the Nb1 mole part. 0.025 mol part or more and 0.080 mol part or less, and the content molar amount of the divalent metal element is 0.045 mol part or more and 0.086 mol part or less with respect to the Nb1 mol part, And the total of the content molar amount of the Li and the divalent metal element is 0.076 mol part or more and 0.166 mol part or less with respect to the Nb1 mol part,
   The piezoelectric ceramic electronic component, wherein the external electrode contains Ni.
3. 3. The piezoelectric ceramic electronic component according to claim 1, wherein the molar amount of Zr is equal to or greater than the molar amount of the divalent metal element.
4. The piezoelectric ceramic electronic component according to any one of claims 1 to 3, wherein the perovskite compound contains at least one element of K and Na.
5. The piezoelectric ceramic electronic component according to any one of claims 1 to 4, wherein the divalent metal element is Ba.
6. The piezoelectric ceramic electronic component according to claim 5, wherein the piezoelectric ceramic body contains Mn.
7. A method of manufacturing a piezoelectric ceramic electronic component for forming a piezoelectric ceramic body containing at least Nb, Li, Zr, and a divalent metal element,
   First calcined powder is obtained by mixing and calcining at least a Nb compound and a Li compound so that the content of Li is 0.025 mol part or more and 0.080 mol part or less with respect to 1 mol part of Nb. A step of producing
   The content molar amount of the divalent metal element is 0.045 mol part or more and 0.086 mol part or less with respect to the Nb1 mol part, and the total of the content mol amounts of the divalent metal element and Li is the above. The metal element compound, the Zr compound, and the first calcined powder are mixed and calcined so as to be 0.076 mol part or more and 0.166 mol part or less with respect to 1 mol of Nb, and the second calcined And a method of manufacturing a piezoelectric ceramic electronic component.
8. The method includes: a step of integrally molding the second calcined powder and an electrode material containing Ni to produce a molded body; and a step of firing the molded body in a reducing atmosphere. Item 8. A method for manufacturing a piezoelectric ceramic electronic component according to Item 7.
9. 9. The method of manufacturing a piezoelectric ceramic electronic component according to claim 7, wherein the metal element compound is a Ba compound.

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