CN114436653B - Anti-reduction potassium-sodium niobate based lead-free piezoelectric ceramic with fatigue resistance, high inverse voltage resistance and high stability and preparation method thereof - Google Patents

Anti-reduction potassium-sodium niobate based lead-free piezoelectric ceramic with fatigue resistance, high inverse voltage resistance and high stability and preparation method thereof Download PDF

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CN114436653B
CN114436653B CN202011228094.XA CN202011228094A CN114436653B CN 114436653 B CN114436653 B CN 114436653B CN 202011228094 A CN202011228094 A CN 202011228094A CN 114436653 B CN114436653 B CN 114436653B
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王晓慧
岑侦勇
李龙土
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Tsinghua University
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Abstract

The invention discloses a reduction-resistant potassium sodium niobate-based leadless piezoelectric ceramic with fatigue resistance, high inverse voltage and high stability and a preparation method thereof. The potassium-sodium niobate-based leadless piezoelectric ceramic has the following chemical formula: (1-x) Na1‑yKyNb1‑zTazO3‑xBa1+hZrO3+ t% M + k% N; wherein x, y, z, h, t and k represent mole fractions, x is more than or equal to 0.04 and less than or equal to 0.07, y is more than or equal to 0.46 and less than or equal to 0.55, z is more than or equal to 0 and less than or equal to 0.08, h is more than or equal to 0.1 and less than or equal to 0.1, t is more than or equal to 4 and less than or equal to 10, and k is more than or equal to 0.5 and less than or equal to 8; m represents a manganese compound and N represents ZrO2Or HfO2. The preparation method comprises the following steps: (1) Mixing Na2CO3、K2CO3、Nb2O5、ZrO2、HfO2、BaCO3、Ta2O5Mixing the manganese compound and the potassium sodium niobate base lead-free piezoelectric ceramic according to the stoichiometric ratio in the chemical formula of the reduction-resistant potassium sodium niobate base lead-free piezoelectric ceramic, and then carrying out ball milling, drying and calcining in sequence to obtain a porcelain; (2) The porcelain is sequentially subjected to ball milling, granulation, compression molding, binder removal and sintering to obtain the reduction-resistant potassium sodium niobate-based lead-free piezoelectric ceramic; the sintering is performed in a reducing atmosphere. The product of the invention has high inverse piezoelectric coefficient, good reduction resistance, high fatigue resistance and high inverse piezoelectric coefficient d* 33Temperature stability of (3).

Description

Anti-reduction potassium sodium niobate based leadless piezoelectric ceramic with fatigue resistance, high inverse voltage and high stability and preparation method thereof
Technical Field
The invention relates to a reduction-resistant potassium sodium niobate-based lead-free piezoelectric ceramic with fatigue resistance, high inverse voltage resistance and high stability and a preparation method thereof, belonging to the technical field of lead-free piezoelectric ceramic materials.
Background
The inverse piezoelectric performance of piezoelectric ceramics is an important index of piezoelectric actuators. In the current domestic piezoelectric actuator market, lead-based piezoelectric actuator materials, such as PZT-based piezoelectric ceramics, hold a significant market share. However, lead-based materials present a very toxic hazard to humans and the environment during production and disposal, and thus, many countries and regions have long legislated restrictions that prohibit the use of lead-based materials, including lead-based piezoelectric driven devices. Based on the current situation, it is urgent to develop lead-free piezoelectric materials that can replace lead-based piezoelectric actuators.
The air-sintered potassium sodium niobate-based piezoelectric ceramic has been developed for many years, and part of the piezoelectric properties (positive piezoelectric coefficient d)33650pC/N and inverse piezoelectric coefficient d* 33750 pm/V) have been able to compete with lead-based piezoelectric materials (Tao, h; wu, h.; liu, y.; zhang, y.; wu, j.; li, F.; lyu, x.; zhao, c.; xiao, d.; zhu, j.; pennyook, S.J. journal of the American Chemical Society 2019,141, 13987.). However, many potassium sodium niobate-based piezoelectric materials have insufficient temperature stability of piezoelectric performance, which is a problem that limits practical use of the materials. In the aspect of piezoelectric actuator application, the main performance is as follows: insufficient piezoelectric displacement and poor temperature stability.
For piezoelectric actuator materials, the application demands that a lower driving voltage be designed and a larger displacement be driven at this voltage. Will K0.5Na0.5NbO3The multilayering of the base material is the best way to solve the problem of insufficient strain of the material, namely, the total displacement of the piezoelectric material can be improved through the design of a multilayer structure. When the same piezoelectric is applied to the lead-free piezoelectric material with the same thickness, the displacement of the piezoelectric material with the multilayer structure design can be nearly doubled, namely
Total displacement SGeneral assemblyNumber of layers (N). Times.monolayer (S)Sheet)。
With the development of advanced science and technology, high precision, miniaturization, functionalization, low cost and high stability are becoming the standards of lead-free piezoelectric actuators. However, the sintering temperature of current multilayer devices is substantially above 1100 ℃. The inner electrode of the lead-based system or the lead-free system is usually a silver palladium electrode, and the price of the electrode is high, so that the cost of the device is not reduced. Therefore, the use of base metal materials as the internal electrodes is the best solution. Taking a nickel electrode as an example, the nickel electrode has the following advantages as an inner electrode: 1. the nickel electrode has low cost which is only about 5 percent of the conventional Pd30-Ag70 electrode; 2. the electromigration speed of nickel atoms is lower than that of Ag or Pd-Ag, so that the nickel atoms have good electrochemical stability and can improve the reliability of the multilayer piezoelectric ceramic; 3. the nickel electrode has good corrosion resistance and heat resistance to the solder and good process stability; 4. the oxidation resistance of the Ni electrode is better than that of the Ag electrode; 5. the Ni electrode has a high melting point which can reach more than 1400 ℃, which determines that the Ni electrode slurry has a wide application range.
However, nickel metal electrodes are subject to oxidation reactions when heated to 330 ℃ or higher in air, and therefore, the conditions for sintering must be reducing atmosphere conditions (oxygen partial pressure less than 10X 10)-11MPa). This also puts new demands on the co-fired multilayer ceramic material, namely, to have good anti-reduction property; moreover, the reliability requirements of the device application are high, namely the fatigue characteristics of the piezoelectric actuator material are high. Therefore, it is highly desirable to develop a K compound having both good anti-reduction properties and excellent fatigue properties0.5Na0.5NbO3A lead-free piezoelectric ceramic.
Disclosure of Invention
The invention aims to provide an anti-reduction potassium sodium niobate based lead-free piezoelectric ceramic and a preparation method and application thereof. The potassium-sodium niobate-based leadless piezoelectric ceramic has high inverse piezoelectric coefficient, good anti-reduction characteristic and high inverse piezoelectric coefficient d* 33Temperature stability (Te); the preparation method is used for sintering in a reducing atmosphere to obtain the potassium-sodium niobate-based lead-free piezoelectric ceramic, the sintering temperature is the lowest, and the electric energy is saved; the Bi-free ceramic material reduces the volatilization of Bi in the ceramic sintering process, reduces the vacancy in the material and is beneficial to improving the reliability of the material.
The invention provides potassium-sodium niobate based leadless piezoelectric ceramics, which has the following chemical formula:
(1-x)Na1-yKyNb1-zTazO3-xBa1+h ZrO3+t％M+k％N；
wherein x, y, z, h, t and k represent mole fractions, x is more than or equal to 0.04 and less than or equal to 0.07, y is more than or equal to 0.46 and less than or equal to 0.55, z is more than or equal to 0 and less than or equal to 0.08, h is more than or equal to 0.1 and less than or equal to 0.1, t is more than or equal to 4 and less than or equal to 10, and k is more than or equal to 0.5 and less than or equal to 8; m represents a manganese compound, wherein the manganese compound is MnO or Mn2O3、MnCO3Or MnO2N represents ZrO2Or HfO2。
The anti-reduction potassium sodium niobate based leadless piezoelectric ceramic provided by the invention can be any one of the following 1) -8):
1) The chemical formula is as follows:
(1-x)Na1-yKyNb1-zTazO3-xBa1+h ZrO3+t％M+k％N；
wherein x, y, z, h, t and k represent mole fractions, x is more than or equal to 0.04 and less than or equal to 0.06, y is more than or equal to 0.47 and less than or equal to 0.55, z is more than or equal to 0.03 and less than or equal to 0.08, h is more than or equal to 0.1 and less than or equal to 0.1, t is more than or equal to 4 and less than or equal to 9, and k is more than or equal to 1 and less than or equal to 8; m represents a manganese compound, wherein the manganese compound is MnO or Mn2O3、MnCO3Or MnO2N represents ZrO2Or HfO2；
In a specific example, x =0.055, y =0.48, z =0.04, h =0, t =5, k =1.5, m represents MnO, and N represents HfO2(ii) a The chemical formula is as follows:
0.945Na0.52K0.48Nb0.96Ta0.04O3-0.055BaZrO3+5mol％MnO+1.5mol％HfO2；
2) The chemical formula is as follows:
(1-x)Na1-yKyNb1-zTazO3-xBa1+h ZrO3+t％M+k％N；
wherein x, y, z, h, t and k represent mole fractions, x is more than or equal to 0.05 and less than or equal to 0.06, y is more than or equal to 0.46 and less than or equal to 0.52, z is more than or equal to 0.02 and less than or equal to 0.06, h is more than or equal to 0 and less than or equal to 0.05, t is more than or equal to 4 and less than or equal to 6, and k is more than or equal to 1 and less than or equal to 7; m represents a manganese compound, wherein the manganese compound is MnO or Mn2O3、MnCO3Or MnO2N represents ZrO2Or HfO2；
In a specific example, x =0.06, y =0.5,z =0.06, h =0, t =5, k =2, M represents MnO2N represents HfO2(ii) a The chemical formula is as follows:
0.94Na0.5K0.5Nb0.94Ta0.06O3-0.06BaZrO3+5mol％MnO2+2mol％ZrO2；
3) The chemical formula is as follows:
(1-x)Na1-yKyNb1-zTazO3-xBa1+h ZrO3+t％M+k％N；
wherein x, y, z, h, t and k represent mole fractions, x is more than or equal to 0.05 and less than or equal to 0.06, y is more than or equal to 0.48 and less than or equal to 0.50, z is more than or equal to 0.01 and less than or equal to 0.045, h is more than or equal to 0.01 and less than or equal to 0.06, t is more than or equal to 4 and less than or equal to 6, and k is more than or equal to 3 and less than or equal to 7; m represents a manganese compound, wherein the manganese compound is MnO or Mn2O3、MnCO3Or MnO2N represents ZrO2Or HfO2；
In a specific example, x =0.05, y =0.5, z =0.02, h =0.01, t =4, k =3, and m represents MnO2N represents HfO2(ii) a The chemical formula is as follows:
0.96Na0.5K0.5Nb0.98Ta0.02O3-0.05Ba1.01ZrO3+4mol％MnO2+3mol％HfO2
4) The chemical formula is as follows:
(1-x)Na1-yKyNb1-zTazO3-xBa1+hZrO3+t％M+k％N；
wherein x, y, z, h, t and k represent mole fractions, x is more than or equal to 0.045 and less than or equal to 0.06, y is more than or equal to 0.48 and less than or equal to 0.52, z is more than or equal to 0.01 and less than or equal to 0.04, h is more than or equal to 0.08 and less than or equal to 0.06, t is more than or equal to 4 and less than or equal to 6, and k is more than or equal to 3 and less than or equal to 4; m represents a manganese compound, wherein the manganese compound is MnO or Mn2O3、MnCO3Or MnO2N represents ZrO2Or HfO2；
In a specific example, x =0.06, y =0.52, z =0.01, h =0, t =4, k =3, and m represents Mn2O3N represents ZrO2(ii) a The chemical formula is as follows:
0.94Na0.48K0.52Nb0.99Ta0.01O3-0.06BaZrO3+4mol％Mn2O3+3mol％ZrO2；
5) The chemical formula is as follows:
(1-x)Na1-yKyNb1-zTazO3-xBa1+h ZrO3+t％M+k％N；
wherein x, y, z, t and k represent mole fractions, x is more than or equal to 0.05 and less than or equal to 0.07, y is more than or equal to 0.46 and less than or equal to 0.50, z is more than or equal to 0.03 and less than or equal to 0.05, h is more than or equal to 0 and less than or equal to 0.04, t is more than or equal to 4 and less than or equal to 6, and k is more than or equal to 2 and less than or equal to 5; m represents a manganese compound, wherein the manganese compound is MnO or Mn2O3、MnCO3Or MnO2N represents ZrO2Or HfO2；
In a specific example, x =0.07, y =0.49, z =0.03, h =0, t =5, k =3, m represents MnCO3N represents ZrO2(ii) a The chemical formula is as follows:
0.93Na0.51K0.49Nb0.97Ta0.03O3-0.07BaZrO3+5mol％MnCO3+3mol％ZrO2；
6) The chemical formula is as follows:
(1-x)Na1-yKyNb1-zTazO3-xBa1+h ZrO3+t％M+k％N；
wherein x, y, z, t and k represent mole fractions, x is more than or equal to 0.045 and less than or equal to 0.06, y is more than or equal to 0.50 and less than or equal to 0.55, z is more than or equal to 0.05 and less than or equal to 0.07, h is more than or equal to 0 and less than or equal to 0.02, t is more than or equal to 4 and less than or equal to 5, and k is more than or equal to 1 and less than or equal to 2; m represents a manganese compound, wherein the manganese compound is MnO or Mn2O3、MnCO3Or MnO2N represents ZrO2Or HfO2；
In a specific example, x =0.055, y =0.5, z =0.07, h =0.01, t =4, k =1.5, and m represents Mn3O4N represents ZrO2(ii) a The chemical formula is as follows:
0.955Na0.5K0.5Nb0.93Ta0.07O3-0.055Ba1.01ZrO3+4mol％Mn3O4+1.5mol％ZrO2；
7) The chemical formula is as follows:
(1-x)Na1-yKyNb1-zTazO3-xBa1+h ZrO3+t％M+k％N；
wherein x, y, z, t and k represent mole fractions, x is more than or equal to 0.05 and less than or equal to 0.06, y is more than or equal to 0.50 and less than or equal to 0.54, z is more than or equal to 0.03 and less than or equal to 0.06, h is more than or equal to 0 and less than or equal to 0.03, t is more than or equal to 5 and less than or equal to 8, and k is more than or equal to 2 and less than or equal to 5; m represents a manganese compound, wherein the manganese compound is MnO or Mn2O3、MnCO3Or MnO2N represents ZrO2Or HfO2；
8) The chemical formula is as follows:
(1-x)Na1-yKyNb1-zTazO3-xBa1+h ZrO3+t％M+k％N；
wherein x, y, z, t and k represent mole fractions, x is more than or equal to 0.045 and less than or equal to 0.06, y is more than or equal to 0.48 and less than or equal to 0.52, z is more than or equal to 0.02 and less than or equal to 0.05, h is more than or equal to 0.01 and less than or equal to 0.02, t is more than or equal to 5 and less than or equal to 9, and k is more than or equal to 5.5 and less than or equal to 8; m represents a manganese compound, wherein the manganese compound is MnO or Mn2O3、MnCO3Or MnO2N represents ZrO2Or HfO2。
The invention also provides a preparation method of the anti-reduction potassium sodium niobate based lead-free piezoelectric ceramic, which comprises the following steps:
(1) Mixing Na2CO3、K2CO3、Nb2O5、ZrO2、HfO2、BaCO3、Ta2O5Mixing the manganese compound and the anti-reduction potassium sodium niobate-based lead-free piezoelectric ceramic according to the stoichiometric ratio in the chemical formula of the anti-reduction potassium sodium niobate-based lead-free piezoelectric ceramic, and then performing ball milling, drying and calcining in sequence to obtain a porcelain material;
(2) The porcelain is subjected to ball milling, granulation, compression molding and glue discharge in sequence, and then sintering and reoxidation are carried out to obtain the reduction-resistant potassium sodium niobate-based lead-free piezoelectric ceramic;
the sintering is performed in a reducing atmosphere.
In the step (1) of the preparation method, the ball mill uses absolute ethyl alcohol as a medium, and the mass of the medium is 10 to 20 times of the total mass of the raw materials, specifically 15 times, 10 to 15 times, 15 to 20 times or 12 to 18 times;
the raw material is the Na2CO3K to2CO3The Nb2O5The ZrO2The HfO2The BaCO3Ta2O5And the manganese compound.
In the step (1) of the preparation method, the rotation speed of the ball mill may be 300 to 400 rpm, specifically 300 rpm, and the time may be 20 to 30 hours, specifically 24 hours.
In the step (1) of the preparation method, the drying temperature can be 60-80 ℃, specifically 60 ℃, 60-70 ℃ or 60-75 ℃, and the drying time can be 1-3 hours, specifically 1 hour, 1-2 hours or 1-2.5 hours; the drying mode is carried out by adopting a reduced pressure distillation mode.
In the step (1) of the preparation method, the calcination temperature may be 800-950 ℃, specifically 930 ℃, 800-930 ℃, 930-950 ℃ or 850-950 ℃, and the calcination time may be 2-6 hours, specifically 2 hours, 2-3 hours, 2-4 hours or 2-5 hours.
In the step (2) of the preparation method, the ball mill uses absolute ethyl alcohol as a medium, and the mass of the medium is 10 to 20 times of the total mass of the porcelain, specifically 15 times, 10 to 15 times, 15 to 20 times or 12 to 17.5 times;
the rotation speed of the ball milling can be 250-350 r/min, specifically 300 r/min, and the ball milling time can be 20-30 h, specifically 24h.
In the step (2) of the preparation method, the adhesive used for granulation is polyvinyl butyral;
the mass of the adhesive can be 5-7% of the total mass of the porcelain, and specifically can be 5%.
In the step (2) of the preparation method, the conditions of the compression molding are as follows: applying 100-150 MPa, specifically 100MPa or 100-120 MPa;
the rubber discharging steps are as follows: firstly, heating to 500-600 ℃ in air at a heating rate of 180-200 ℃/h, and preserving heat for 1-2 h, specifically heating to 600 ℃ at a heating rate of 200 ℃/h, discharging glue, and preserving heat for 2h.
In the step (2) of the preparation method, the sintering conditions are as follows: the temperature is raised to 1050-1080 ℃ at the heating rate of 240-360 ℃/h, specifically to 1050-1080 ℃ at the heating rate of 300 ℃/h, and the time can be 2-4 h, specifically 2h or 2-3 h.
In the step (2) of the preparation method, the reducing atmosphere is composed of N with a volume fraction of 98-99.5%2And 0.5-2% by volume of H2Composition, specifically may be volume fraction 99%2/1％H2；
Oxygen partial pressure Po of the reducing atmosphere in the sintering2Can be 1 × 10-10～1×10-13atm, in particular 10-10～10-12atm。
In the step (2) of the preparation method, the reoxidation oxidation process is as follows: after the sintering heat preservation is finished, the temperature is reduced to 800-900 ℃ at a rate of 240-420 ℃/h (specifically, the temperature is increased to the sintering temperature at 300 ℃/h and reduced to 850 ℃), and N is adjusted2And H2Ratio of oxygen partial pressure of the reducing atmosphere to 10-6～10-9atm (specifically 10)-6～10-7atm), keeping the temperature for 7-10 h (specifically 9 h), and keeping the atmosphere to be cooled to room temperature after finishing.
In the present invention, the room temperature is a common knowledge in the art, and may be specifically 10 to 30 ℃.
In the step (2) of the preparation method, the method further comprises the steps of gold-coated electrode and polarization which are sequentially carried out after the sintering step;
the gold-coated electrode adopts a magnetron sputtering method;
the polarization is carried out in silicone oil;
the polarization conditions were as follows: the polarization temperature can be 80-130 deg.C, specifically 80 deg.C, the polarization electric field can be 3-4 kV/mm, specifically 3kV/mm, and the polarization time can be 20-30 min, specifically 30min.
The invention also provides a multilayer piezoelectric ceramic driver which is prepared by co-firing the anti-reduction potassium sodium niobate-based lead-free piezoelectric ceramic and a Ni electrode.
The reduction-resistant potassium sodium niobate-based lead-free piezoelectric ceramic is applied to the preparation of a multilayer piezoelectric ceramic driver.
The invention has the following advantages:
the reduction-resistant potassium-sodium niobate-based lead-free piezoelectric ceramic provided by the invention has excellent piezoelectric performance and comprehensive performance. By selecting proper x, y, z, h, t and k values and process parameters, the inverse piezoelectric coefficient d capable of being driven to be high under a lower electric field is obtained* 33The material of (1). Its inverse piezoelectric constant d* 33To 480pm/V (E =20 kV/cm). And under the electric field, the inverse piezoelectric coefficient d increases along with the increase of the test temperature* 33Before the range of less than-10%, the effective temperature can reach Te =155 ℃. Meanwhile, the strain of the material is weakened by less than 10% after 100 ten thousand unipolar cycles of applying an electric field of 20 kV/cm.
Drawings
FIG. 1 is a graph showing the relationship between the unipolar strain and the electric field of the potassium-sodium niobate-based lead-free piezoelectric ceramic prepared in example 1 of the present invention; the monopole strain data is shown in the graph with the electric field intensity decreasing from 40kV/cm to 10kV/cm in the direction of the arrow.
FIG. 2 shows the inverse piezoelectric coefficient d of the potassium sodium niobate-based lead-free piezoelectric ceramic prepared in example 1 of the present invention* 33And the relationship between the electric field.
FIG. 3 shows the inverse piezoelectric coefficient d of the potassium sodium niobate-based lead-free piezoelectric ceramic prepared in example 4 of the present invention* 33Graph with temperature.
Fig. 4 shows the room temperature fatigue properties of the potassium sodium niobate-based lead-free piezoelectric ceramic prepared in example 6 of the present invention.
Detailed Description
The experimental procedures used in the following examples are all conventional procedures unless otherwise specified.
Materials, reagents and the like used in the following examples are commercially available unless otherwise specified.
Example 1 preparation of Potassium sodium niobate-based lead-free piezoelectric ceramics
The composition expression of the potassium-sodium niobate based lead-free piezoelectric ceramic in the embodiment is as follows:
0.945Na0.52K0.48Nb0.96Ta0.04O3-0.055BaZrO3+5mol％MnO+1.5mol％HfO2；
the preparation method comprises the following steps:
(1) Wet milling, drying and firing:
take 600mL ball mill pot as an example, for analytically pure Na2CO3、K2CO3、Nb2O5、ZrO2、HfO2、BaCO3、Ta2O5And MnO as raw materials, preparing materials according to the chemical formula, carrying out planetary ball milling for 24 hours (the rotating speed is 300 r/min) by taking absolute ethyl alcohol (about 350mL, and the mass ratio of the medium to the porcelain is specifically 15 times) as a medium, drying the powder by rotary evaporation (the temperature is 60 ℃, the time is 1 hour), and then carrying out heat preservation at 930 ℃ for 2 hours for calcination;
(2) Secondary ball milling, granulation, compression molding, binder removal and sintering:
and (2) performing planetary ball milling on the porcelain obtained in the step (1) for 24 hours (the rotating speed is 300 r/min) by taking absolute ethyl alcohol (about 350mL, and the mass ratio of the medium to the porcelain is specifically 15 times) as a medium, adding a PVB (polyvinyl butyral) binder accounting for 5% of the mass of the porcelain, granulating, and performing compression molding at 100 MPa. Firstly, heating the ceramic green body to 600 ℃ at the heating rate of 200 ℃/h for binder removal, and preserving heat for 2h. Then taking out and moving the mixture to an atmosphere furnace, heating the mixture to 1050-1080 ℃ at the heating rate of 300 ℃/h for sintering, and keeping the temperature for 2h, wherein N is introduced in the process2/H2(volume fraction about: 99% by weight N2/1％H2) Controlling the oxygen partial pressure at 10-10～10-12In the atm range, the temperature can be reduced to 850 ℃ at the cooling rate of 300 ℃/h, and N is adjusted2And H2Ratio, oxygen partial pressure of reducing atmosphere controlled to 10-6～10-7atm, carrying out reoxidationAfter 9h, the reducing atmosphere was maintained and the furnace was cooled to room temperature (25 ℃).
(3) Polishing, gold coating and polarization in silicone oil:
and (3) subjecting the two surfaces of the ceramic wafer obtained after sintering in the step (2) to simple grinding treatment, then coating gold on the two surfaces, coating a gold electrode with the thickness of 3 mu m by adopting a magnetron sputtering method, and polarizing the gold electrode in silicone oil at 100 ℃, wherein the polarizing electric field is 3kV/mm, and the polarizing time is 30min, so that the potassium-sodium niobate-based lead-free piezoelectric ceramic with high inverse piezoelectric coefficient, good anti-reduction characteristic and high inverse piezoelectric coefficient temperature stability can be obtained.
And (3) placing the prepared potassium sodium niobate-based lead-free piezoelectric ceramic sample at room temperature for 24 hours to test the performance. The results of the experiment are shown in table 1. The relationship between the unipolar strain and the electric field is shown in fig. 1. FIG. 2 shows the inverse piezoelectric coefficient d in example 1 of the present invention* 33And the electric field. The potassium sodium niobate based leadless piezoelectric ceramic sample system generates a corresponding electric field with the maximum inverse piezoelectric coefficient as low as 20kV/cm, has the advantage of low driving electric field, and can provide materials for the design of future micro devices. Meanwhile, the temperature stability is good, namely the Te value is high (155 ℃), and the application range is wide; inverse piezoelectric coefficient d33 *Excellent and high temperature stability, and simultaneously, the driving electric field is as low as 20kV/cm, which is beneficial to being used as a base material of a micro-voltage driving electric device.
TABLE 1 EXAMPLE 1 Potassium sodium niobate-based lead-free piezoelectric ceramics Properties
Figure BDA0002764252040000071
Example 2 preparation of Potassium sodium niobate-based lead-free piezoelectric ceramics
The composition expression of the potassium-sodium niobate based lead-free piezoelectric ceramic in the embodiment is as follows: 0.94Na0.5K0.5Nb0.94Ta0.06O3-0.06BaZrO3+5mol％MnO2+2mol％ZrO2；
The preparation method comprises the following steps:
to analyze pure Na2CO3、K2CO3、Nb2O5、ZrO2、BaCO3、Ta2O5And MnO2The raw materials are mixed according to the expression, and the rest steps are the same as the example 1.
The experimental results are shown in table 2, and the results in table 1 show that the performance of the potassium sodium niobate-based lead-free piezoelectric ceramic of the present invention has better system temperature stability than that reported in the prior art that the potassium sodium niobate-based ceramic is sintered in a reducing atmosphere.
TABLE 2 EXAMPLE 2 Potassium sodium niobate-based leadless piezoelectric ceramics Properties
Figure BDA0002764252040000072
Example 3 preparation of Potassium sodium niobate-based lead-free piezoelectric ceramics
The composition expression of the potassium-sodium niobate-based lead-free piezoelectric ceramic in the embodiment is as follows: 0.96Na0.5K0.5Nb0.98Ta0.02O3-0.05Ba1.01ZrO3+4mol％MnO2+3mol％HfO2；
The preparation method comprises the following steps:
to analyze pure Na2CO3、K2CO3、Nb2O5、ZrO2、HfO2、BaCO3、Ta2O5And MnO2The raw materials are mixed according to the expression, and the rest steps are the same as the example 1.
The results of the experiment are shown in table 3. As can be seen from Table 3, the sample material of this example has high resistivity, good anti-reduction properties, and superior temperature stability to the other examples.
TABLE 3 EXAMPLE 3 Potassium sodium niobate-based leadless piezoelectric ceramics Properties
Figure BDA0002764252040000081
Example 4 preparation of Potassium sodium niobate-based lead-free piezoelectric ceramics
The composition expression of the potassium-sodium niobate-based lead-free piezoelectric ceramic in the embodiment is as follows: 0.94Na0.48K0.52Nb0.99Ta0.01O3-0.06BaZrO3+4mol％Mn2O3+3mol％ZrO2The preparation method comprises the following steps:
to analyze pure Na2CO3、K2CO3、Nb2O5、ZrO2、BaCO3、Ta2O5And Mn2O3The raw materials are mixed according to the expression, and the rest steps are the same as the example 1. The relationship between the dielectric constant and the temperature of the potassium-sodium niobate-based lead-free piezoelectric ceramic is shown in fig. 3.
The results of the experiment are shown in table 4. As can be seen from Table 4, the resistivity of this example is high, the temperature stability is good, d* 33High value and good comprehensive performance.
TABLE 4 EXAMPLE 4 Potassium sodium niobate-based leadless piezoelectric ceramics Properties
Figure BDA0002764252040000082
Example 5 preparation of Potassium sodium niobate-based lead-free piezoelectric ceramics
The composition expression of the potassium-sodium niobate based lead-free piezoelectric ceramic in the embodiment is as follows: 0.93Na0.51K0.49Nb0.97Ta0.03O3-0.07BaZrO3+5mol％MnCO3+3mol％ZrO2；
The preparation method comprises the following steps:
to analyze pure Na2CO3、K2CO3、Nb2O5、ZrO2、BaCO3、Ta2O5And MnCO3The raw materials are mixed according to the expression, and the rest steps are the same as the example 1.
The results of the experiment are shown in Table 5. As can be seen from the data in Table 5, the sample of this example has very high temperature stability, which is superior to the data reported in the prior art; and the driving electric field is as low as 2kV/mm, and the resistivity is excellent.
TABLE 5 EXAMPLE 5 Potassium sodium niobate-based lead-free piezoelectric ceramics Properties
Figure BDA0002764252040000091
Example 6 preparation of Potassium sodium niobate-based lead-free piezoelectric ceramics
The composition expression of the potassium-sodium niobate-based lead-free piezoelectric ceramic in the embodiment is as follows: 0.955Na0.5K0.5Nb0.93Ta0.07O3-0.055Ba1.01ZrO3+4mol％Mn3O4+1.5mol％ZrO2(ii) a The preparation method comprises the following steps:
to analyze pure Na2CO3、K2CO3、Nb2O5、ZrO2、BaCO3、Ta2O5And Mn3O4The raw materials are mixed according to the expression, and the rest steps are the same as the example 1.
The room-temperature fatigue properties of the potassium-sodium niobate-based lead-free piezoelectric ceramics prepared in example 6 of the present invention are shown in fig. 4, and the results of the performance test of the potassium-sodium niobate-based lead-free piezoelectric ceramics are shown in table 6. The potassium sodium niobate-based lead-free piezoelectric ceramic prepared by the embodiment has high resistivity, d* 33Also has excellent temperature stability and outstanding comprehensive performance.
TABLE 6 EXAMPLE 6 Potassium sodium niobate-based lead-free piezoelectric ceramics Properties
Figure BDA0002764252040000092

Claims (10)

1. The reduction-resistant potassium-sodium niobate-based leadless piezoelectric ceramic has the following chemical formula:
(1-x)Na1-yKyNb1-zTazO3-xBa1+hZrO3+t %M+k %N；
wherein x, y, z, h, t and k represent mole fractions, and are not less than 0.04x≤0.07，0.46≤y≤0.55，0≤z≤0.08，-0.1≤h≤0.1，4≤t≤10，0.5≤kLess than or equal to 8; m represents a manganese compound, wherein the manganese compound is MnO or Mn2O3、MnCO3Or MnO2N represents ZrO2Or HfO2。
2. The method for preparing the reduction-resistant potassium sodium niobate-based lead-free piezoelectric ceramic as claimed in claim 1, comprising the steps of:
(1) Na is mixed with2CO3、K2CO3、Nb2O5、ZrO2、HfO2、BaCO3、Ta2O5Mixing the manganese compound and the anti-reduction potassium sodium niobate-based lead-free piezoelectric ceramic according to the stoichiometric ratio in the chemical formula of the anti-reduction potassium sodium niobate-based lead-free piezoelectric ceramic, and then performing ball milling, drying and calcining in sequence to obtain a porcelain;
(2) Sequentially carrying out ball milling, granulation, press forming and glue discharging on the porcelain, and then sintering and reoxidizing to obtain the reduction-resistant potassium sodium niobate-based lead-free piezoelectric ceramic;
the sintering is performed in a reducing atmosphere.
3. The production method according to claim 2, characterized in that: in the step (1), absolute ethyl alcohol is used as a medium for ball milling, and the mass of the medium is 10 to 20 times of the total mass of the raw materials;
the raw material is the Na2CO3K to2CO3The Nb2O5The ZrO2The HfO2The BaCO3Ta2O5And the manganese compound;
the rotation speed of the ball mill is 300-400 r/min, and the time is 20-30h; and/or the presence of a gas in the atmosphere,
the drying temperature is 60 to 80 ℃, and the drying time is 1 to 3h; the drying mode is carried out by adopting a reduced pressure distillation mode; and/or the presence of a gas in the gas,
the calcining temperature is 800 to 950 ℃, and the time is 2 to 6h.
4. The production method according to claim 2 or 3, characterized in that: in the step (2), the ball milling takes absolute ethyl alcohol as a medium, and the mass of the medium is 10 to 20 times of the total mass of the porcelain;
the rotation speed of the ball milling is 250 to 350 r/min, and the ball milling time is 20 to 30h; and/or the presence of a gas in the gas,
the adhesive used for granulation is polyvinyl butyral;
the mass of the adhesive is 5% -7% of the total mass of the porcelain.
5. The production method according to claim 2 or 3, characterized in that: in the step (2), the conditions of the compression molding are as follows: 100 to 150 MPa;
the rubber discharging steps are as follows: firstly, the temperature is controlled to be 180 to 200 ℃ in the airoHeating to 500-600 ℃ at a temperature rise rate of C/hoC, and keeping the temperature for 1 to 2h.
6. The production method according to claim 2 or 3, characterized in that: in the step (2), the sintering conditions are as follows: the heating rate is 240 to 360oC/h heating to the sintering temperature of 1050 to 1080 ℃ for 2 to 4h;
the reducing atmosphere is composed of 98 to 99.5 volume percent of N2And H with the volume fraction of 0.5 to 2 percent2Forming;
oxygen partial pressure of reducing atmosphere in the sinteringPo2Is 1 × 10-10~1×10-13atm。
7. The production method according to claim 2 or 3, characterized in that: in the step (2), the reoxidation oxidation process is as follows: after the sintering is finished and the heat preservation is finished, the temperature is controlled to be 240 to 420 DEGoThe C/h cooling rate is reduced to 800 to 900oC, and by adjusting N2And H2The oxygen partial pressure of the reducing atmosphere is controlled to be 10-6~10-9and (5) keeping the temperature of the atm for 7 to 10h, and then keeping the atmospheric condition to be cooled to the room temperature.
8. The production method according to claim 2 or 3, characterized in that: in the step (2), the method further comprises the steps of gold electrode and polarization which are sequentially carried out after the sintering step;
the gold-coated electrode adopts a magnetron sputtering method;
the poling is carried out in silicone oil;
the polarization conditions were as follows: the polarization temperature is 80 to 130 ℃, the polarization electric field is 3 to 4kV/mm, and the polarization time is 20 to 30min.
9. A multilayer piezoelectric ceramic actuator obtained by cofiring the reduction-resistant potassium sodium niobate-based lead-free piezoelectric ceramic of claim 1 with a Ni electrode.
10. Use of the anti-reducing potassium sodium niobate-based lead-free piezoelectric ceramic of claim 1 in the preparation of a multilayer piezoelectric ceramic actuator.
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