CN115490514A - Piezoelectric ceramic and preparation method and application thereof - Google Patents

Piezoelectric ceramic and preparation method and application thereof Download PDF

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CN115490514A
CN115490514A CN202110726568.1A CN202110726568A CN115490514A CN 115490514 A CN115490514 A CN 115490514A CN 202110726568 A CN202110726568 A CN 202110726568A CN 115490514 A CN115490514 A CN 115490514A
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piezoelectric
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piezoelectric ceramic
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CN115490514B (en
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郭益平
皇甫庚
李毅
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Shanghai Jiaotong University
Fuxin Dare Automotive Parts Co Ltd
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Fuxin Dare Automotive Parts Co Ltd
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Abstract

The invention discloses a piezoelectric ceramic and a preparation method and application thereof. The general formula of the piezoelectric ceramic is (1-x) (Na) y K z Li 1‑y‑z )NbO 3 ‑xSr(Nb 1‑m Ni m )O 3 Wherein x is more than or equal to 0.01 and less than or equal to 0.10, y is more than or equal to 0.45 and less than or equal to 0.55, z is more than or equal to 0.45 and less than or equal to 0.55, and m is more than or equal to 0 and less than or equal to 0.4. The piezoelectric ceramic has excellent electrostrictive strain performance, has the advantages of large electrostrictive strain, low driving electric field, good fatigue resistance, wide use temperature range and the like, and can be used for piezoelectric drivers or piezoelectric sensors.

Description

Piezoelectric ceramic and preparation method and application thereof
The present application claims priority of Chinese patent application with application number 202110681012.5, entitled "piezoelectric ceramic and its preparation method and application", filed in China patent office at 18/6/2021, the entire contents of which are incorporated herein by reference.
Technical Field
The invention relates to the technical field of piezoelectric materials, in particular to piezoelectric ceramic and a preparation method and application thereof.
Background
The inorganic perovskite type oxide ferroelectric material is a typical ferroelectric piezoelectric material, has a large piezoelectric coefficient and large electrostriction, is often applied to the fields of sensing, driving and the like, and plays an important role in industrial production and daily life of people. The current commercial piezoelectric ceramics are mainly based on lead zirconate titanate (PZT), but due to the harm of lead element to human health and natural environment, western countries have already made regulations and will gradually eliminate lead-containing piezoelectric ceramics. Potassium sodium niobate (KNN), which is a representative of lead-free piezoelectric ceramics, is a lead-free piezoelectric system that has been most widely studied at present, and has exhibited properties not inferior to PZT in terms of piezoelectric coefficient, electrostriction, temperature stability, and the like, and is therefore considered to be the most promising lead-free piezoelectric ceramic system for replacing PZT.
For a piezoelectric actuator, a piezoelectric material is required to have the characteristics of large electric strain, low driving voltage, small strain hysteresis, fatigue resistance, wide use temperature range and the like. At present, sodium bismuth titanate (NBT) based lead-free piezoelectric ceramics have the largest electrostriction (0.5-0.74%). However, the NBT-based ceramic has the characteristic of large coercive field, which results in high driving voltage and large strain hysteresis, and is not suitable for application in piezoelectric drivers. For example, (1-x) (0.8 Bi) 0.5 Na 0.5 TiO 3 -0.2Bi 0.5 K 0.5 TiO 3 )-xSr 0.8 Bi 0.1 Ti 0.8 Zr 0.2 O 2.95 The ceramic can reach a maximum strain of 0.72%, however, a strong electric current of 110kV/cmThe strain obtained under the field under the drive of a conventional electric field of 50kV/cm is less than 0.5%, indicating that the large strain of the NBT-based ceramic requires a large drive voltage. Large strain hysteresis is also a common problem for NBT based ceramics. Typical NBT-based ceramic 0.85 (Na) 0.5- x La x Bi 0.5 )(Ti 1-x Nb x )O 3 -0.11K 0.5 Bi 0.5 TiO 3 -0.04BaTiO 3 The strain-electric field curve of (2) shows that the strain hysteresis reaches about 60%, so that the driving precision is low, and the application of the driving aspect is hindered. Another NBT-based ceramic ((Bi) 1/2 (Na 0.84 K 0.16 ) 1/2 ) 0.96 Sr 0.04 )(Ti 1-x Nb x )O 3 Although large strains of 0.7% can be achieved at an electric field of 50kV/cm, the large strains are derived from the electric field-induced phase transition from the nano-domain relaxation phase to the ferroelectric three-dimensional phase, which also causes the electric strain to show a significant decay after 100 cycles, making the ceramic unsuitable for piezoelectric drives.
Compared with NBT-based materials, the KNN-based ceramic has more proper driving voltage and strain hysteresis, and also has good fatigue resistance and a using temperature range, but the research on the KNN-based ceramic mainly focuses on the improvement of a positive piezoelectric coefficient, and the research on large-strain ceramic is less. At present, most KNN-based ceramics can only realize 0.1% -0.2% of strain under an electric field of 40kV/cm, and cannot meet the requirements of a piezoelectric driver. Recently reported Fe 2+ Or Cu + The KNN-doped ceramic can obtain large strain of 0.4% or 0.5%, but needs to be sintered in a high-purity argon atmosphere, so that the production cost is high. In addition, the difficult sintering, the nonuniform performance and the poor repeatability of the high-performance KNN-based ceramic are also generally recognized by academia. Therefore, the KNN-based ceramic which is simple in component, easy to sinter and large in electrostriction is developed and researched, and has important significance for promoting the application of the KNN-based ceramic to a driver and promoting the lead-free piezoelectric element.
Disclosure of Invention
The invention provides a piezoelectric ceramic and a preparation method and application thereof, which are used for solving the problem of small electrostriction of potassium-sodium niobate-based piezoelectric ceramic in the prior art.
In a first aspect, embodiments of the present invention provide a piezoelectric ceramic having a general formula of (1-x) (Na) y K z Li 1-y-z )NbO 3 -xSr(Nb 1-m Ni m )O 3 Wherein x is more than or equal to 0.01 and less than or equal to 0.10, y is more than or equal to 0.45 and less than or equal to 0.55, z is more than or equal to 0.45 and less than or equal to 0.55, and m is more than or equal to 0 and less than or equal to 0.4.
Optionally, in some embodiments, 0.02 ≦ x ≦ 0.06.
Optionally, in some embodiments, y = z =0.5 and/or m =1/3.
In a second aspect, an embodiment of the present invention further provides a method for preparing a piezoelectric ceramic, including the following steps:
s1, mixing powders respectively containing Na, K, nb, sr, ni and Li according to the formula (1-x) (Na) y K z Li 1-y-z )NbO 3 -xSr(Nb 1- m Ni m )O 3 Proportioning according to the stoichiometric ratio, wherein x is more than or equal to 0.01 and less than or equal to 0.10, y is more than or equal to 0.45 and less than or equal to 0.55, z is more than or equal to 0.45 and less than or equal to 0.55, m is more than or equal to 0 and less than or equal to 0.4, and performing ball milling treatment on the proportioned powder;
s2, calcining the powder subjected to ball milling treatment to obtain pretreated powder;
s3, carrying out secondary ball milling treatment on the pretreated powder;
s4, molding the powder subjected to the secondary ball milling treatment to obtain a blank; and
s5, sintering the blank.
Optionally, in some embodiments, in step S1, the powder containing Na includes Na 2 CO 3 The powder containing K comprises K 2 CO 3 The Nb-containing powder comprises Nb 2 O 5 The Sr-containing powder comprises SrCO 3 The Ni-containing powder includes NiO and/or the Li-containing powder includes Li 2 CO 3 。
Optionally, in some embodiments, in step S2, the temperature of the calcination is 700 to 900 degrees celsius; and/or in the step S5, the sintering temperature is 1140-1200 ℃.
In a third aspect, the present invention also provides a piezoelectric element, including:
a first electrode;
a second electrode; and
a piezoelectric layer provided between the first electrode and the second electrode and comprising any of the above piezoelectric ceramics or comprising a piezoelectric ceramic produced by any of the above production methods.
In a fourth aspect, the present invention also provides a multilayer piezoelectric element comprising:
a multilayer piezoelectric layer; and
a plurality of internal electrode layers;
wherein the piezoelectric layers and the internal electrode layers are alternately stacked, and at least one layer of the piezoelectric layers comprises any one of the piezoelectric ceramics or the piezoelectric ceramics prepared by any one of the preparation methods.
In a fifth aspect, an embodiment of the present invention further provides a method for preparing a multilayer piezoelectric ceramic, including the following steps:
s10, providing a plurality of piezoelectric diaphragms and a plurality of internal electrodes, wherein at least one layer of piezoelectric diaphragm comprises piezoelectric ceramics with the following general formula: (1-x) (Na) y K z Li 1-y-z )NbO 3 -xSr(Nb 1-m Ni m )O 3 Wherein x is more than or equal to 0.01 and less than or equal to 0.10, y is more than or equal to 0.45 and less than or equal to 0.55, z is more than or equal to 0.45 and less than or equal to 0.55, and m is more than or equal to 0 and less than or equal to 0.4, or at least one layer of the piezoelectric membrane is prepared according to any one of the preparation methods;
s20, alternately stacking a plurality of piezoelectric diaphragms and a plurality of inner electrodes to form a stack; and
and S30, sintering the laminated layer.
In a sixth aspect, the present invention further provides a use of any one of the above piezoelectric ceramics or the piezoelectric ceramics obtained by any one of the above methods, or the above piezoelectric element or the above multilayer piezoelectric element, or the multilayer piezoelectric element obtained by any one of the above methods, in a piezoelectric actuator or a piezoelectric sensor.
The piezoelectric ceramic has excellent electrostrictive strain performance, large electrostrictive strain, low driving electric field, good fatigue resistance and wide application temperature range. The piezoelectric ceramic is suitable for piezoelectric ceramic drivers or piezoelectric sensors.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the drawings needed to be used in the description of the embodiments will be briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without creative efforts.
Fig. 1 is a flowchart of a method for manufacturing a piezoelectric ceramic according to an embodiment of the present invention.
Fig. 2 is a schematic structural diagram of a piezoelectric element according to an embodiment of the present invention.
Fig. 3 is a schematic structural diagram of a multilayer piezoelectric element according to an embodiment of the present invention.
Fig. 4 is a flowchart of a method for manufacturing a multilayer piezoelectric element according to an embodiment of the present invention.
FIG. 5 is (1-x) (Na) prepared in examples 1 to 5 of the present invention 0.5 K 0.5 )NbO 3 -xSr(Nb 2/3 Ni 1/3 )O 3 (X =0.02 to 0.09) an X-ray diffraction pattern of the piezoelectric ceramic.
FIG. 6 is (1-x) (Na) prepared in examples 1-5 of the present invention 0.5 K 0.5 )NbO 3 -xSr(Nb 2/3 Ni 1/3 )O 3 (x =0.02 to 0.09) a polarization-electric field curve of the piezoelectric ceramic.
FIGS. 7a and 7b are (1-x) (Na) prepared by examples 1-5 of the present invention 0.5 K 0.5 )NbO 3 -xSr(Nb 2/3 Ni 1/3 )O 3 (x =0.02 to 0.09) a bipolar strain-electric field curve of the piezoelectric ceramic.
FIGS. 7c and 7d are (1-x) (Na) prepared in examples 1-5 of the present invention 0.5 K 0.5 )NbO 3 -xSr(Nb 2/3 Ni 1/3 )O 3 (x =0.02 to 0.09) a unipolar strain-electric field curve of the piezoelectric ceramic.
FIG. 8aAnd FIG. 8b are each 0.97 (Na) prepared in example 2 of the present invention 0.5 K 0.5 )NbO 3 -0.03Sr(Nb 2/3 Ni 1/3 )O 3 The result of the bipolar strain-electric field curve fatigue performance test of the piezoelectric ceramics at room temperature and 160 ℃.
FIGS. 9a and 9b the present invention is 0.97 (Na), respectively, prepared in example 2 0.5 K 0.5 )NbO 3 -0.03Sr(Nb 2/3 Ni 1/3 )O 3 Bipolar and unipolar strain curves of the piezoelectric ceramic at a temperature range of 25 ℃ to 200 ℃.
FIG. 10 shows (1-x) (Na) prepared in examples 3 to 5 of the present invention 0.5 K 0.5 )NbO 3 -xSr(Nb 2/3 Ni 1/3 )O 3 (x =0.04 to 0.09) the light transmittance of the piezoelectric ceramic is 380nm to 1500 nm.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. The scope of the invention is not limited to the specific embodiments described below. Test methods in which specific conditions are not noted in the following examples are generally performed under conventional conditions or conditions recommended by each manufacturer.
The embodiment of the invention provides piezoelectric ceramic and a preparation method and application thereof. The following are detailed below. It should be noted that the following description of the embodiments is not intended to limit the preferred order of the embodiments. In addition, in the description of the present invention, the term "includes" means "including but not limited to". Various embodiments of the invention may exist in a range of forms; it should be understood that the description in range format is merely for convenience and brevity and should not be construed as an inflexible limitation on the scope of the invention; accordingly, the described range descriptions should be considered to have specifically disclosed all the possible sub-ranges as well as individual numerical values within that range. For example, it is contemplated that the description of a range from 1 to 6 has specifically disclosed sub-ranges such as, for example, from 1 to 3, from 1 to 4, from 1 to 5, from 2 to 4, from 2 to 6, from 3 to 6, etc., as well as individual numbers within a range such as, for example, 1, 2, 3, 4, 5, and 6, as applicable regardless of the range. In addition, whenever a numerical range is stated herein, it is understood that both endpoints of each numerical range, and any number (fraction or integer) between the two endpoints, are optional unless the invention otherwise specified. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In addition to the specific methods, devices, and materials used in the examples, any methods, devices, and materials similar or equivalent to those described in the examples may be used in the practice of the invention in addition to the specific methods, devices, and materials used in the examples, in keeping with the knowledge of one skilled in the art and with the description of the invention.
The embodiment of the invention provides piezoelectric ceramic, and the general formula of the piezoelectric ceramic is (1-x) (Na) y K z Li 1-y-z )NbO 3 -xSr(Nb 1-m Ni m )O 3 (ii) a Wherein x is more than or equal to 0.01 and less than or equal to 0.10, y is more than or equal to 0.45 and less than or equal to 0.55, z is more than or equal to 0.45 and less than or equal to 0.55, and m is more than or equal to 0 and less than or equal to 0.4.
It is understood that x represents Sr (Nb) 1-m Ni m )O 3 Y, z and m respectively represent the atom number of the corresponding element in each component, namely the atom percentage. x may be any value within the range of 0.01 to 0.10, for example 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 0.10, etc. y and z may each take any value within the range of 0.45 to 0.55, such as 0.45, 0.46, 0.47, 0.48, 0.49, 0.50, 0.51, 0.52, 0.53, 0.54, 0.55, and the like. m can be any value within the range of 0 to 0.4, such as 0, 0.1, 0.2, 0.3, 0.33, 0.35, 0.37, 0.4, and the like.
The piezoelectric ceramic provided by the embodiment of the invention introduces Sr (Nb) on the basis of potassium sodium niobate base 1-m Ni m )O 3 And m is more than or equal to 0 and less than or equal to 0.4, so that the piezoelectric ceramic has excellent electrostrictive strain performance and a large electrostrictive strain value, and the problem that the potassium-sodium niobate-based piezoelectric ceramic in the prior art cannot meet the requirement of a piezoelectric driver due to insufficient strain and can not be applied to the piezoelectric driver is solved. And is provided withThe piezoelectric ceramic also has the advantages of low driving electric field, good fatigue resistance and wide use temperature range. In addition, the piezoelectric ceramic disclosed by the embodiment is simple in component and easy to sinter, and solves the problems of complex component, high production cost and difficulty in sintering of the conventional piezoelectric ceramic. The piezoelectric ceramic of the embodiment can also be prepared into multilayer co-fired ceramic by component modification, sintering aid addition and/or glass equivalent methods, and further applied to the fields of multilayer ceramic drivers and the like.
In some embodiments, 0.02 ≦ x ≦ 0.06. The embodiment can enable the piezoelectric ceramic to have excellent electrostrictive performance. In other embodiments, 0.02 ≦ x ≦ 0.04. The embodiment can enable the piezoelectric ceramic to have excellent electrostrictive strain performance and large electrostrictive strain value.
In other embodiments, 0.04 ≦ x ≦ 0.09. The piezoelectric material can have high visible and near infrared region transmittance, and has light transmittance of not less than 45% for 600nm, light transmittance of not less than 65% for 900nm and light transmittance of not less than 70% for 1500 nm.
In some embodiments, the piezoelectric ceramic has a chemical composition as one of:
0.98(Na 0.5 K 0.5 )NbO 3 -0.02Sr(Nb 2/3 Ni 1/3 )O 3 ；
0.97(Na 0.5 K 0.5 )NbO 3 -0.03Sr(Nb 2/3 Ni 1/3 )O 3 ；
0.96(Na 0.5 K 0.5 )NbO 3 -0.04Sr(Nb 2/3 Ni 1/3 )O 3 ；
0.94(Na 0.5 K 0.5 )NbO 3 -0.06Sr(Nb 2/3 Ni 1/3 )O 3 (ii) a And
0.91(Na 0.5 K 0.5 )NbO 3 -0.09Sr(Nb 2/3 Ni 1/3 )O 3 。
the crystal structure of the piezoelectric ceramic of the present embodiment is a single perovskite structure.
In some embodiments, y and z may be unequal. For example: y is 0.5, z is 0.45, and Li is 0.05. In other embodiments, y and z may be equal. For example, y is 0.48, z is 0.48, then Li is 0.04, as another example: y is 0.5, z may be 0.5, li is 0.
In some embodiments, y is 0.5 and z is 0.5.
In some embodiments, 0 < m ≦ 0.4. It is understood that m can be any value in the range of 0 to 0.4, such as 0.01, 0.1, 0.2, 0.3, 0.33, 0.35, 0.37, 0.4, etc. In other embodiments, 0.3. Ltoreq. M.ltoreq.0.4. It is understood that m can be any value in the range of 0.3 to 0.4, such as 0.3, 0.33, 0.35, 0.37, 0.4, etc.
In some embodiments, m is 1/3. This embodiment can make Sr (Nb) 1-m Ni m )O 3 The electrovalence of (2) is balanced, and oxygen vacancies are reduced to reduce dielectric loss.
In some embodiments, m is 1/3, y is 0.5, and z is 0.5.
Referring to fig. 1, an embodiment of the present invention further provides a method for preparing a piezoelectric ceramic, including the following steps:
s1, mixing powders respectively containing Na, K, nb, sr, ni and Li according to the formula (1-x) (Na) y K z Li 1-y-z )NbO 3 -xSr(Nb 1- m Ni m )O 3 Proportioning according to the stoichiometric ratio, wherein x is more than or equal to 0.01 and less than or equal to 0.10, y is more than or equal to 0.45 and less than or equal to 0.55, z is more than or equal to 0.45 and less than or equal to 0.55, and m is more than or equal to 0 and less than or equal to 0.4, and performing ball milling treatment on the proportioned powder;
s2, calcining the powder subjected to ball milling treatment to obtain pretreated powder;
s3, performing secondary ball milling treatment on the pretreated powder;
s4, performing molding treatment on the powder subjected to the secondary ball milling treatment to obtain a blank; and
s5, sintering the blank.
It is understood that "powder" in the embodiments of the present application is simply referred to as "powder raw material". In step S1, the powder containing Na, K, nb, sr, ni, and Li means that Na, K, and Nb are contained in the powderSr element, ni element and Li element. The proportion of each element is determined according to the general formula (1-x) (Na) of the piezoelectric ceramic to be prepared y K z Li 1-y-z )NbO 3 -xSr(Nb 1-m Ni m )O 3 (x is more than or equal to 0.01 and less than or equal to 0.10, y is more than or equal to 0.45 and less than or equal to 0.55, z is more than or equal to 0.45 and less than or equal to 0.55, and m is more than or equal to 0 and less than or equal to 0.4). The powder is, for example, of high purity (purity not less than 98%).
In step S1, the powder containing Na includes Na 2 CO 3 The powder containing K comprises K 2 CO 3 The Nb-containing powder comprises Nb 2 O 5 The Sr-containing powder comprises SrCO 3 The Ni-containing powder comprises NiO and/or the Li-containing powder comprises Li 2 CO 3 . The Na-containing powder may include other Na-containing powder, the K-containing powder may include other K-containing powder, the Nb-containing powder may include other Nb-containing powder, the Sr-containing powder may include other Sr-containing powder, the Ni-containing powder may include other Ni-containing powder, and the Li-containing powder may include other Li-containing powder. In some embodiments, in step S1, the powder containing Na is Na 2 CO 3 The powder is K 2 CO 3 The powder is Nb 2 O 5 The powder containing Sr is SrCO 3 The powder, the Ni-containing powder is NiO powder and/or the Li-containing powder is Li 2 CO 3 And (3) powder.
In some embodiments, in step S1, the meal comprises Na 2 CO 3 、K 2 CO 3 、Nb 2 O 5 、SrCO 3 And a powder mixture of NiO. In other embodiments, in step S1, the powder material is Na-containing 2 CO 3 、K 2 CO 3 、Nb 2 O 5 、SrCO 3 NiO and Li 2 CO 3 The powder mixture of (1).
In step S1, the ball milling process may be dry ball milling or wet ball milling. In one embodiment, wet ball milling is used, comprising: and performing ball milling treatment on the prepared powder in a liquid medium, and drying after the ball milling treatment. The liquid medium is, for example, an absolute ethanol medium or a deionized water medium. The time of the ball milling treatment is, for example, 2 to 48 hours (h). The powder with uniform and refined components can be obtained through ball milling treatment, and further the comprehensive performance of the piezoelectric ceramic can be improved.
In step S2, the temperature of calcination is, for example, 700 to 900 degrees celsius (° c). The calcination time is, for example, 2 to 10 hours. The calcination may be carried out, for example, in air. It is understood that the temperature of calcination can be anywhere from 700 ℃ to 900 ℃, such as 700 ℃, 750 ℃, 800 ℃, 850 ℃,900 ℃ and the like. The calcining time can be any value in the range of 2h to 10h, such as 2h, 4h, 6h, 8h, 10h and the like. The purpose of the calcination is to cause the respective raw materials to undergo a solid-phase reaction at a high temperature, so that carbon elements and a part of oxygen elements in carbides and oxides are ablated, so as to synthesize a piezoelectric ceramic having the above-mentioned chemical composition.
In step S3, the secondary ball milling process may be dry ball milling or wet ball milling. In one embodiment, the secondary ball milling treatment is wet ball milling comprising: and (3) carrying out secondary ball milling treatment on the pretreated powder in a liquid medium, and drying after the secondary ball milling treatment. The liquid medium is, for example, an anhydrous ethanol medium or a deionized water medium. The time of the ball milling treatment is, for example, 2 to 48 hours (h). The calcined powder can be finely vibrated, uniformly mixed and ground through secondary ball milling treatment, and a foundation is laid for the ceramic forming uniformity of the piezoelectric ceramics.
In step S4, the molding process may employ, for example, cold press molding. Cold press forming is carried out, for example, at a pressure of 50 MPa. The powder can be compacted into a preform of pre-formed size and shape by forming.
In step S5, the temperature of sintering is, for example, 1140 ℃ to 1200 ℃. The sintering time is, for example, 4 to 8 hours. The sintering is carried out, for example, in air. It is understood that the sintering temperature can be anywhere from 1140 deg.C to 1200 deg.C, such as 1140 deg.C, 1160 deg.C, 1180 deg.C, 1200 deg.C, etc. The dense piezoelectric ceramics having the above chemical composition can be obtained by sintering.
The details of the present embodiment that are not described in detail refer to the description of the above embodiments.
Referring to fig. 2, an embodiment of the invention further provides a piezoelectric element, which includes a first electrode 10, a second electrode 30, and a piezoelectric layer 20.
A piezoelectric layer 20 is arranged between said first electrode 10 and said second electrode 30. The piezoelectric layer 20 comprises any of the piezoelectric ceramics described above or a piezoelectric ceramic produced by any of the preparation methods described above. It is understood that the piezoelectric layer 20 can include other components, such as a sintering aid (e.g., copper oxide, bismuth oxide, etc.), as desired, in addition to any of the piezoelectric ceramics described above. The shape of the piezoelectric layer 20 is not limited and it may be configured in a desired pattern. In one embodiment, the piezoelectric layer 20 comprises only piezoelectric ceramics.
The material of the first electrode 10 may be, for example, at least one of silver, aluminum, copper, titanium, nickel, and thallium. The first electrode 10 is formed, for example, by means of sputtering or vapor deposition. The shape of the first electrode 10 is not limited, and it may be configured in a desired pattern. The material of the second electrode 30 may be, for example, at least one of silver, aluminum, copper, titanium, nickel, and thallium. The second electrode 30 is formed by means of sputtering or vapor deposition, for example. The shape of the second electrode 30 is not limited, and it may be configured in a desired pattern.
The details of the present embodiment that are not described in detail refer to the description of the above embodiments.
Referring to fig. 3, an embodiment of the invention further provides a multi-layer piezoelectric device, which includes a plurality of piezoelectric layers 100 and a plurality of internal electrode layers 200. The piezoelectric layers 100 and the internal electrode layers 200 are alternately stacked to form a stacked structure. At least one of the piezoelectric layers 100 comprises the piezoelectric ceramic described above or the piezoelectric ceramic prepared by the preparation method described above.
It is understood that each of the piezoelectric layers 100 may include any of the piezoelectric ceramics described above, or may be prepared according to any of the methods for preparing the piezoelectric ceramics described above. The shapes of the multilayer piezoelectric layers 100 and the multilayer internal electrode layers 200 are not limited, and they may be configured in a desired pattern. When the piezoelectric ceramic is produced by any of the above production methods, it can be formed into a desired shape, for example, a diaphragm. The piezoelectric layer 100 may include other components, such as a component including a sintering aid (e.g., copper oxide, bismuth oxide, etc.), as needed, in addition to any of the piezoelectric ceramics described above. In one embodiment, the piezoelectric layer 100 comprises only piezoelectric ceramics.
The piezoelectric element may further include an outer electrode. For example, a first external electrode and a second external electrode. The first external electrode is disposed at the left side of the stacked structure (i.e., at the left side of the stacked structure in fig. 3, not shown in fig. 3), and is connected to a portion of the internal electrode layer 200; the second external electrode is disposed at the right side of the stacked structure (i.e., at the right side of the stacked structure in fig. 3, not shown in fig. 3), and is connected to another portion of the internal electrode layer 200.
The details of the present embodiment that are not described in detail refer to the description of the above embodiments.
Referring to fig. 4, an embodiment of the present application further provides a method for manufacturing a multi-layer piezoelectric device, which includes the following steps:
s10, providing a plurality of piezoelectric diaphragms and a plurality of internal electrodes, wherein at least one layer of piezoelectric diaphragm comprises piezoelectric ceramics with the following general formula: (1-x) (Na) y K z Li 1-y-z )NbO 3 -xSr(Nb 1-m Ni m )O 3 Wherein x is more than or equal to 0.01 and less than or equal to 0.10, y is more than or equal to 0.45 and less than or equal to 0.55, z is more than or equal to 0.45 and less than or equal to 0.55, and m is more than or equal to 0 and less than or equal to 0.4, or at least one layer of the piezoelectric membrane is prepared according to any one of the preparation methods;
s20, alternately stacking a plurality of piezoelectric diaphragms and a plurality of inner electrodes to form a stack; and
and S30, sintering the laminated layer.
The details of the present embodiment that are not described in detail refer to the description of the above embodiments.
The invention also provides application of any one of the piezoelectric ceramics in a piezoelectric driver or a piezoelectric sensor. In particular, the followingThe piezoelectric ceramic has a general formula: (1-x) (Na) y K z Li 1-y-z )NbO 3 -xSr(Nb 1- m Ni m )O 3 Wherein x is more than or equal to 0.01 and less than or equal to 0.10, y is more than or equal to 0.45 and less than or equal to 0.55, z is more than or equal to 0.45 and less than or equal to 0.55, and m is more than or equal to 0 and less than or equal to 0.4. The piezoelectric actuator includes a piezoelectric motor, a piezoelectric vibration device, a piezoelectric ejection device, and a piezoelectric precision actuator. The piezoelectric ejection device may include a piezoelectric inkjet printhead, a piezoelectric fuel jet, or the like. The piezoelectric ceramic is used, for example, as a piezoelectric layer in a piezoelectric actuator or a piezoelectric sensor.
The invention also provides application of the piezoelectric ceramic prepared by the preparation method of any one of the piezoelectric ceramics in a piezoelectric driver or a piezoelectric sensor.
The invention also provides an application of any one of the piezoelectric elements in a piezoelectric driver or a piezoelectric sensor.
The invention also provides an application of any one of the multilayer piezoelectric elements in a piezoelectric driver or a piezoelectric sensor.
The invention also provides application of the multilayer piezoelectric element prepared by the preparation method of any one of the multilayer piezoelectric elements in a piezoelectric driver or a piezoelectric sensor.
Illustratively, the piezoelectric actuator includes, but is not limited to, a piezoelectric motor, a piezoelectric vibration device, a piezoelectric ejection device, a piezoelectric precision actuator, and the like. Including but not limited to piezoelectric ink jet printheads, piezoelectric fuel jets, and the like.
The following is a further detailed description of the embodiments.
Example 1
Preparation with a composition of 0.98 (Na) 0.5 K 0.5 )NbO 3 -0.02Sr(Nb 2/3 Ni 1/3 )O 3 (abbreviated as KNN-2 SNN) and tested for electrical properties. The preparation method comprises the following steps:
the first step is as follows: according to the general formula 0.98 (Na) 0.5 K 0.5 )NbO 3 -0.02Sr(Nb 2/3 Ni 1/3 )O 3 Weighing high-purity (purity not less than 98%) Na 2 CO 3 、K 2 CO 3 、Nb 2 O 5 、SrCO 3 Ball milling NiO powder raw materials in an absolute ethyl alcohol medium for 24 hours;
the second step is that: drying the dispersion liquid obtained in the first step, and calcining the obtained powder in the air at 700 ℃ for 5 hours;
the third step: ball-milling the powder obtained in the second step in an absolute ethyl alcohol medium for 24 hours;
the fourth step: and drying the dispersion liquid obtained in the third step, carrying out cold press molding on the obtained powder, and sintering for 6 hours at 1170 ℃ in the air.
Example 2
Preparation content of 0.97 (Na) 0.5 K 0.5 )NbO 3 -0.03Sr(Nb 2/3 Ni 1/3 )O 3 (abbreviated as KNN-3 SNN) potassium-sodium niobate-strontium niobate piezoelectric ceramics. The preparation method in this example is substantially the same as in example 1, except that 0.97 (Na) is used in the first step 0.5 K 0.5 )NbO 3 -0.03Sr(Nb 2/3 Ni 1/3 )O 3 Weighing raw materials according to the chemical general formula.
Example 3
Preparation of 0.96 (Na) 0.5 K 0.5 )NbO 3 -0.04Sr(Nb 2/3 Ni 1/3 )O 3 (abbreviated as KNN-4 SNN) potassium-sodium niobate-strontium niobate piezoelectric ceramics. The preparation process in this example is approximately the same as in example 1, except that 0.96 (Na) is used in the first step 0.5 K 0.5 )NbO 3 -0.04Sr(Nb 2/3 Ni 1/3 )O 3 Weighing raw materials according to the chemical general formula.
Example 4
Preparation with a composition of 0.94 (Na) 0.5 K 0.5 )NbO 3 -0.06Sr(Nb 2/3 Ni 1/3 )O 3 (abbreviated as KNN-6 SNN) potassium-sodium niobate-strontium niobate piezoelectric ceramics. The preparation method in this example is substantially the same as that in example 1, except that 0.94 (Na) is used in the first step 0.5 K 0.5 )NbO 3 -0.06Sr(Nb 2/3 Ni 1/3 )O 3 Weighing raw materials according to the chemical general formula.
Example 5
Preparation content of 0.91 (Na) 0.5 K 0.5 )NbO 3 -0.09Sr(Nb 2/3 Ni 1/3 )O 3 (abbreviated as KNN-9 SNN) potassium-sodium niobate-strontium niobate piezoelectric ceramics. The preparation process in this example is approximately the same as in example 1, except that 0.91 (Na) is used in the first step 0.5 K 0.5 )NbO 3 -0.09Sr(Nb 2/3 Ni 1/3 )O 3 Weighing raw materials according to the chemical general formula.
The effects that can be obtained by the above embodiments will be described in detail below with reference to specific experiments.
1. X-ray diffraction pattern
FIG. 5 shows (1-x) (Na) prepared in examples 1 to 5 of the present invention 0.5 K 0.5 )NbO 3 -xSr(Nb 2/3 Ni 1/3 )O 3 (X =0.02 to 0.09) an X-ray diffraction pattern of the piezoelectric ceramic. The spectrum shows that the piezoelectric ceramics with different components prepared in the technical scheme of the invention are all perovskite structures at room temperature, and when x =0.02 or 0.03, the XRD spectrum of the KNN-xSNN piezoelectric ceramics is very similar to the KNN standard spectrum of an orthorhombic Amm2 space group, which shows that the KNN-2SNN and KNN-3SNN piezoelectric ceramics are in orthorhombic structures at room temperature. As x is gradually increased, each diffraction peak is gradually more symmetrical, and the peak separation phenomenon is not obvious, which indicates that the phase structure of the piezoelectric ceramic is gradually changed from an orthogonal structure to a pseudo-cubic structure.
2. Electrical Performance testing
The test method comprises the following steps: grinding the piezoelectric ceramic plate prepared in the embodiment 1-5 to be about 0.5mm thin, and polarizing the two surfaces of the piezoelectric ceramic plate by silver under an electric field of 40kV/cm for 10 minutes; the samples were aged for 12 days after polarization and tested again. The polarization intensity-electric field (P-E) curve and the strain-electric field (S-E) curve of the piezoelectric ceramic are tested by adopting an aixACCT TF1000 ferroelectric property tester under the excitation of 50kV/cm electric field intensity and 10Hz bipolar or unipolar triangular waves. The samples were immersed in silicone oil for testing.
FIG. 6 is (1-x) (Na) prepared in examples 1 to 5 of the present invention 0.5 K 0.5 )NbO 3 -xSr(Nb 2/3 Ni 1/3 )O 3 (x =0.02 to 0.09) polarization-electric field (P-E) curve of the piezoelectric ceramic. As can be seen from the P-E curve, as x increases, the remanent polarization and the maximum polarization of the piezoelectric ceramic gradually decrease, and the coercive field also gradually decreases. Along with the gradual transformation of the piezoelectric ceramic structure to the pseudo-cubic structure, the ferroelectricity of the material is gradually reduced.
FIGS. 7a and 7b are (1-x) (Na) 0.5 K 0.5 )NbO 3 -xSr(Nb 2/3 Ni 1/3 )O 3 (x =0.02 to 0.09) strain-electric field (S-E) curve of the piezoelectric ceramic under excitation of a bipolar triangular wave of 10hz, 50kv/cm. As can be seen from the graph, the maximum strain of the piezoelectric ceramic increases and then decreases with increasing x, reaching a maximum value of about 0.8% at x = 0.03. At the same time, the asymmetry of the S-E curve also reaches a maximum at x =0.03, and then gradually approaches the "butterfly curve" common to common piezoelectric ceramics.
FIGS. 7c and 7d are (1-x) (Na) 0.5 K 0.5 )NbO 3 -xSr(Nb 2/3 Ni 1/3 )O 3 (x =0.02 to 0.09) S-E curve of the piezoelectric ceramic under excitation of a monopole triangular wave at 10Hz and 50kV/cm. The KNN-xSNN piezoceramic unipolar strain has the same tendency as the bipolar strain, with the strain reaching a maximum value of about 0.71% at x = 0.03.
The specific test results for each example are as follows:
the electrical properties of the piezoelectric ceramic prepared in example 1 were: in the P-E curve, the remanent polarization is about 17 μ C/cm 2 The coercive field is about 15kV/cm. The strain at zero field in the S-E curve was determined to be 0, and the maximum strain at 50kV/cm bipolar excitation voltage was measured to be about 0.69%, and the maximum strain at unipolar excitation to be about 0.40%. Quotient S of maximum strain and maximum electric field strength max /E max For evaluation of the electrostrictive properties, this was about 1380pm/V under bipolar excitation and about 880pm/V under monopolar excitation.
The electrical properties of the piezoelectric ceramic prepared in example 2 were: in the P-E curve, the remanent polarization is about 15 μ C/cm 2 The coercive field is about 16kV/cm. The strain value at zero field in the S-E curve is determined to be 0,the maximum strain was measured to be about 0.80% under bipolar excitation at 50kV/cm and about 0.71% under monopolar excitation. S max /E max About 1590pm/V under bipolar excitation and about 1410pm/V under monopolar excitation.
The electrical properties of the piezoelectric ceramic prepared in example 3 were: in the P-E curve, the remanent polarization is about 11 μ C/cm 2 The coercive field is about 14kV/cm. The strain at zero field in the S-E curve was determined to be 0, and the maximum strain at 50kV/cm bipolar excitation voltage was about 0.33%, and the maximum strain at unipolar excitation was about 0.26%. S max /E max At bipolar excitation, approximately 760pm/V and at unipolar excitation, approximately 540pm/V.
The electrical properties of the piezoelectric ceramic prepared in example 4 were: in the P-E curve, the remanent polarization is about 7. Mu.C/cm 2 The coercive field is about 10kV/cm. The strain at zero field in the S-E curve was determined to be 0, and the maximum strain at 50kV/cm bipolar excitation voltage was about 0.22%, and the maximum strain at unipolar excitation was about 0.18%. S max /E max At bipolar excitation, approximately 440pm/V, and at monopolar excitation, approximately 350pm/V.
The electrical properties of the piezoelectric ceramic prepared in example 5 were: in the P-E curve, the remanent polarization is about 4 μ C/cm 2 The coercive field is about 7kV/cm. The strain at zero field in the S-E curve was determined to be 0, and the maximum strain at 50kV/cm bipolar excitation voltage was about 0.09%, and the maximum strain at unipolar excitation was about 0.09%. S. the max /E max At bipolar excitation, about 190pm/V, and at unipolar excitation, about 180pm/V.
3. Fatigue test and temperature change test
Using the piezoelectric ceramic prepared in example 2 as an example, an electrostrictive strain test was performed at a temperature ranging from room temperature to 200 ℃ and a cycle 10 was performed under 30kV/cm bipolar triangular wave excitation 5 Secondary fatigue test. In the temperature change test, the temperature is tested at the temperature points of 25 ℃, 40 ℃, 60 ℃, 80 ℃, 100 ℃, 120 ℃, 140 ℃, 160 ℃, 180 ℃ and 200 ℃ for one time, and the temperature overshoot is avoided during the test.
FIG. 8a is 0.97 (Na) 0.5 K 0.5 )NbO 3 -0.03Sr(Nb 2/3 Ni 1/3 )O 3 And (3) testing the S-E curve fatigue of the piezoelectric ceramic at room temperature. In the fatigue test, 10 runs 4 Maximum strain at 50kV/cm bipolar excitation voltage after the secondary cycle is about 0.76%; through 10 5 After the secondary cycle, the maximum strain under a bipolar excitation voltage of 50kV/cm is about 0.70%, and the maximum strain attenuation is 88.6% of the fatigue initial state.
FIG. 8b is 0.97 (Na) 0.5 K 0.5 )NbO 3 -0.03Sr(Nb 2/3 Ni 1/3 )O 3 And (3) testing the S-E curve fatigue of the piezoelectric ceramic at 160 ℃. Fatigue test at 160 ℃ of 10 5 After the secondary cycle, the maximum strain under a bipolar excitation voltage of 50kV/cm is about 1.36%, and the maximum strain attenuation is 89.6% of the fatigue initial state.
FIG. 9a and FIG. 9b are each 0.97 (Na) 0.5 K 0.5 )NbO 3 -0.03Sr(Nb 2/3 Ni 1/3 )O 3 The test result of the temperature-changing bipolar strain and the unipolar strain of the piezoelectric ceramic at the temperature of 25-200 ℃. In the temperature change test, the electrical strain performance of the KNN-3SNN gradually increases and then decreases with increasing temperature, and reaches a maximum value at 160 ℃, the maximum strain is about 1.52 percent under a bipolar excitation voltage of 50kV/cm, and the maximum strain is about 1.18 percent under a unipolar excitation.
4. Optical Performance testing
The test method comprises the following steps: the ceramic sheets prepared in examples 3-5 were thinned to about 300 μm and polished on both sides. The PerkinElmer LAMBDA 750s visible-near infrared spectrophotometer is adopted to place the ceramic chip on quartz glass to test the light transmittance of 380-1500 nm. Samples were removed before testing and blank lines were collected as background subtraction.
FIG. 10 is (1-x) (Na) 0.5 K 0.5 )NbO 3 -xSr(Nb 2/3 Ni 1/3 )O 3 (x =0.04 to 0.09) the light transmittance of the piezoelectric ceramic in the range of 380nm to 1500 nm. The light transmittance of 600nm is not less than 45%, the light transmittance of 900nm is not less than 65%, and the light transmittance of 1500nm is not less than 70%, which shows that the KNN-xSNN (x = 0.04-0.09) piezoelectric ceramic has higher visible and near infrared band transmittance.
The optical test results for each example are as follows:
the optical properties of the piezoelectric ceramic prepared in example 3 were: the transmittance generally gradually increases as the wavelength of light increases, but absorption occurs at two places around 700nm and 1150nm, which shows a certain decrease in transmittance. The transmittance of the KNN-4SNN piezoelectric ceramic rises to about 50% at 600nm and about 43% at 700nm, and then rises continuously. The transmittance at 900nm is about 68%, decreases to about 59% at 1150nm, and then continues to increase, with a transmittance at 1500nm of about 75%.
The optical properties of the piezoelectric ceramic prepared in example 4 were: the transmittance gradually increases as the wavelength of light increases as a whole, but absorption occurs at two points around 700nm and 1150nm, which indicates a certain decrease in transmittance. The transmittance of the KNN-6SNN piezoelectric ceramic rises to about 54% at 600nm and about 50% at 700nm, and then rises continuously. The transmittance at 900nm is about 73%, and at 1150nm it decreases to about 68%, and then continues to increase, and at 1500nm it is about 78%.
The optical properties of the piezoelectric ceramic prepared in example 5 were: the transmittance generally gradually increases as the wavelength of light increases, but absorption occurs at two places around 700nm and 1150nm, which shows a certain decrease in transmittance. The transmittance of the KNN-9SNN piezoelectric ceramic rises to about 56% at 600nm and about 48% at 700nm, and then rises continuously. The transmittance at 900nm is about 72%, decreases to about 61% at 1150nm, then continues to increase, and the transmittance at 1500nm is about 78%.
Therefore, it can be seen from the above experiments that the piezoelectric ceramic provided by the embodiment of the present invention includes the following characteristics:
(1) Under 10Hz dipole triangular wave excitation, the strain-electric field curve is asymmetric. The electric field has a large strain in one direction and exhibits a cut-off or small strain in the other direction;
(2) The asymmetry of the strain-electric field curve is strongest at x = 0.02-0.03. As the material composition gradually moves away from this critical point, the shape of the strain-electric field curve gradually approaches the "butterfly curve" of most piezoelectric ceramics;
(3) The value of the electrostriction strain reaches the maximum at the position where x =0.03, and the maximum electrostriction strain can reach 0.80 percent under the excitation electric field of 50 kV/cm;
(4) Has a general formula of 0.97 (Na) 0.5 K 0.5 )NbO 3 -0.03Sr(Nb 2/3 Ni 1/3 )O 3 The piezoelectric ceramic of (1), passing through a 10-inch cylinder at a room temperature under an electric field strength of 30kV/cm 5 After secondary fatigue test, the electrostriction is attenuated by 11.4%;
(5) Has the general formula 0.97 (Na) 0.5 K 0.5 )NbO 3 -0.03Sr(Nb 2/3 Ni 1/3 )O 3 The electrostrictive strain of the piezoelectric ceramic is gradually increased and then decreased along with the temperature increase, the maximum electrostrictive strain is reached at 160 ℃, and the maximum electrostrictive strain can reach 1.52 percent under the excitation electric field of 50 kV/cm;
(6) Has a general formula of 0.97 (Na) 0.5 K 0.5 )NbO 3 -0.03Sr(Nb 2/3 Ni 1/3 )O 3 The piezoelectric ceramic of (1) is passed through a chamber at 160 ℃ under an electric field strength of 30kV/cm 5 After the secondary fatigue test, the electrostrictive strain decayed by 10.4%.
In conclusion, the piezoelectric ceramic has excellent electrostrictive strain performance, and not only has large electrostrictive strain, but also has low driving electric field, good fatigue resistance and wide use temperature range. The piezoelectric ceramic can be used for processing a single-layer ceramic driver, and can also be applied to the fields of piezoelectric ceramic elements (such as multilayer co-fired ceramics), piezoelectric ceramic devices, piezoelectric drivers (such as multilayer co-fired ceramic drivers and piezoelectric precision drivers), piezoelectric sensors, piezoelectric motors, piezoelectric vibration devices or piezoelectric ejection devices and the like.
The above detailed description is provided for the piezoelectric ceramic and the preparation method and application thereof provided by the embodiments of the present invention, and the specific examples are applied herein to explain the principle and the embodiments of the present invention, and the description of the above embodiments is only used to help understanding the method and the core idea of the present invention; meanwhile, for those skilled in the art, according to the idea of the present invention, the specific embodiments and the application range may be changed, and in summary, the content of the present specification should not be construed as limiting the present invention.

Claims (10)

1. AA piezoelectric ceramic characterized in that the general formula of the piezoelectric ceramic is (1-x) (Na) y K z Li 1-y-z )NbO 3 -xSr(Nb 1-m Ni m )O 3 Wherein x is more than or equal to 0.01 and less than or equal to 0.10, y is more than or equal to 0.45 and less than or equal to 0.55, z is more than or equal to 0.45 and less than or equal to 0.55, and m is more than or equal to 0 and less than or equal to 0.4.
2. The piezoelectric ceramic according to claim 1, wherein x is 0.02. Ltoreq. X.ltoreq.0.06.
3. The piezoelectric ceramic of claim 1, wherein y = z =0.5 and/or m =1/3.
4. A preparation method of piezoelectric ceramics is characterized by comprising the following steps:
s1, mixing powders respectively containing Na, K, nb, sr, ni and Li according to the proportion of (1-x) (Na) y K z Li 1-y-z )NbO 3 -xSr(Nb 1-m Ni m )O 3 Proportioning according to the stoichiometric ratio, wherein x is more than or equal to 0.01 and less than or equal to 0.10, y is more than or equal to 0.45 and less than or equal to 0.55, z is more than or equal to 0.45 and less than or equal to 0.55, m is more than or equal to 0 and less than or equal to 0.4, and performing ball milling treatment on the proportioned powder;
s2, calcining the powder subjected to ball milling treatment to obtain pretreated powder;
s3, performing secondary ball milling treatment on the pretreated powder;
s4, molding the powder subjected to the secondary ball milling treatment to obtain a blank; and
s5, sintering the blank.
5. The method of manufacturing a piezoelectric ceramic according to claim 4, wherein in step S1, the Na-containing powder includes Na 2 CO 3 The powder containing K comprises K 2 CO 3 The Nb-containing powder comprises Nb 2 O 5 The Sr-containing powder comprises SrCO 3 The Ni-containing powder comprises NiO and/or the Li-containing powder comprises Li 2 CO 3 。
6. The method for producing a piezoelectric ceramic according to claim 4,
in step S2, the temperature of the calcination is 700 to 900 ℃; and/or the presence of a gas in the gas,
in step S5, the sintering temperature is 1140 to 1200 ℃.
7. A piezoelectric element, comprising:
a first electrode;
a second electrode; and
a piezoelectric layer provided between the first electrode and the second electrode and comprising the piezoelectric ceramic according to any one of claims 1 to 3 or the piezoelectric ceramic produced by the production method according to any one of claims 4 to 6.
8. A multilayer piezoelectric element, characterized by comprising:
a plurality of piezoelectric layers; and
a plurality of internal electrode layers;
wherein the piezoelectric layers and the internal electrode layers are alternately stacked, and at least one of the piezoelectric layers comprises the piezoelectric ceramic according to any one of claims 1 to 3 or the piezoelectric ceramic produced by the production method according to any one of claims 4 to 6.
9. A method for manufacturing a multilayer piezoelectric element, comprising the steps of:
s10, providing a plurality of piezoelectric diaphragms and a plurality of internal electrodes, wherein at least one layer of piezoelectric diaphragm comprises piezoelectric ceramics with the following general formula: (1-x) (Na) y K z Li 1-y-z )NbO 3 -xSr(Nb 1-m Ni m )O 3 Wherein x is 0.01-0.10, y is 0.45-0.55, z is 0.45-0.55, m is 0-0.4, or at least one layer of the piezoelectric membrane is prepared according to the preparation method of any one of claims 4 to 6;
s20, alternately stacking a plurality of piezoelectric diaphragms and a plurality of inner electrodes to form a stack; and
and S30, sintering the laminated layer.
10. Use of the piezoelectric ceramic according to any one of claims 1 to 3 or the piezoelectric ceramic produced by the production method according to any one of claims 4 to 6 or the piezoelectric element according to claim 7 or the multilayer piezoelectric element according to claim 8 or the multilayer piezoelectric element produced by the production method according to claim 9 in a piezoelectric actuator or a piezoelectric sensor.
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