CN111087242A - High-polarization ferroelectric ceramic and preparation method thereof - Google Patents
High-polarization ferroelectric ceramic and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a high-polarization ferroelectric ceramic with a stoichiometric formula of (1-x）NaNbO3‑xLiTaO3. The invention also discloses a preparation method of the ceramic material, namely LiTaO3Added to NaNbO3In the preparation method, (1-x）NaNbO3‑xLiTaO3Ceramic samples. The highly polarized (1-x）NaNbO3‑xLiTaO3The preparation process of the ceramic material is simple, the material cost is low, and the ferroelectric ceramic matrix with high polarization is provided.
Description
Technical Field
The invention relates to the field of high-polarization dielectric ceramic capacitors, in particular to (1-x）NaNbO3-xLiTaO3Ferroelectric ceramic material and a method for preparing the same.
Background
With the miniaturization, light weight and integration of power electronic equipment, it becomes a challenge for researchers and a matter with social and economic benefits to improve the energy density and power density of energy storage devices. The dielectric material applied to the energy storage capacitor can be divided into linear dielectric and cis-dielectricElectric, ferroelectric, relaxor ferroelectric, and antiferroelectric. The unique antiparallel polarization structure of antiferroelectric is considered as the best candidate material for pulse energy storage materials. However, most antiferroelectric materials contain lead and a noble metal element, such as PbZrO3And AgNbO3And the like. For cost and environmental considerations, the development of lead-free antiferroelectric for pulsed energy storage applications has become very urgent. In recent years, sodium niobate NaNbO3Ceramics have received much attention from researchers as an antiferroelectric material. However, it is difficult to obtain dense NaNbO due to the volatility of the alkali metal Na element3A ceramic. NaNbO obtained by traditional solid phase method3Ceramic particles are coarse and vacancies have been created by sodium, which has prevented intensive research into their intrinsic physical properties.
Disclosure of Invention
The present invention is directed to a ferroelectric ceramic material with high polarization and a method for preparing the same, which overcome the above-mentioned problems. The ceramic obtained by the method has the characteristics of high polarization, strong ferroelectricity, simple preparation process, low material cost and environmental friendliness.
In order to achieve the purpose, the invention adopts the following technical scheme:
a lead-free, highly polarized ferroelectric ceramic material having the stoichiometric formula: (1-x）NaNbO3-xLiTaO3，x=0~0.2。
And the preparation method of the high-polarization ferroelectric ceramic material comprises the following steps:
the method comprises the following steps: respectively weighing Li with corresponding mass according to molar ratio2CO3、Ta2O5、Na2CO3And Nb2O5Synthesis of NaNbO3Powder and LiTaO3Powder and then according to the stoichiometric formula (1-x）NaNbO3-xLiTaO3，xTaking NaNbO for 0-0.23Powder and LiTaO3Uniformly mixing the powder to form a complete ingredient;
step two: mixing the complete ingredients with zirconia ball stone and deionized water, and then performing ball milling, drying and sieving to form a sieved material;
step three: and pressing the screened material into a sample by cold isostatic pressing under the pressure of 200-220 MPa, and performing microwave sintering on the prepared sample to obtain a sintered sample.
Further, in step one, LiTaO3The preparation method of the powder comprises the following steps: firstly, weighing Li according to a molar ratio of 1:12CO3And Ta2O5Mixing to form a mixture A; then mixing the mixture A, zircon and deionized water according to the mass ratio of 1:5:1, ball-milling, drying and briquetting in sequence, and finally preserving heat at 1200-1250 ℃ for 4 hours to obtain pure-phase LiTaO3And (3) powder.
Further, in step one, NaNbO3The preparation method of the powder comprises the following steps: firstly, weighing Na according to the molar ratio of 1:12CO3And Nb2O5Mixing to form a mixture B; then mixing the mixture B, zircon and deionized water according to the mass ratio of 1:5:1, ball-milling, drying, calcining at 820-840 ℃ for 3-4 hours to obtain powder C, and ball-milling, drying and calcining the powder C again under the conditions to obtain pure-phase NaNbO3And (3) powder.
Further, in the second step, the complete ingredients, zirconia ball stones and deionized water are mixed according to the mass ratio of 1:5:1 and then ball-milled.
Further, the ball milling time in the second step is 36 h.
Furthermore, the mesh number of the screen during sieving in the second step is 150 meshes.
Further, in the third step of compression molding, the pressure is maintained at 200MPa for 3 minutes, at last at 190MPa for 5 minutes, and at last the pressure is released at 40 MPa/min.
Further, the sintering is carried out in a box-type furnace in the third step, and the process specifically comprises the following steps: firstly, heating to 500 ℃ in 100min, then heating to 900 ℃ in 100min, and preserving heat for 120 min; then the temperature is reduced to 500 ℃ within 100min, and finally the temperature is cooled to room temperature along with the furnace.
And a method for preparing a high-polarization ferroelectric ceramic material by using the ceramic material, which comprises the following specific steps: polishing and cleaning the sintered sampleUniformly coating silver electrode slurry on the front and back surfaces of the polished and cleaned sintered sample, and sintering the sample coated with the silver electrode to obtain (1-x）NaNbO3-xLiTaO3A ferroelectric ceramic material with high polarization of ceramic base.
Further, the (1-x）NaNbO3-xLiTaO3The sintering conditions of the ceramic-based high-polarization ferroelectric ceramic material are as follows: sintering at 580-600 ℃ for 10-20 min.
And (1-x）NaNbO3-xLiTaO3A ferroelectric ceramic material with high polarization of ceramic base.
Compared with the prior art, the invention has the following beneficial technical effects:
(1) prepared by the method of the inventionx）NaNbO3-xLiTaO3The ceramic material not only has high polarization, but also has simple preparation process, low material cost and environmental protection, and becomes an important candidate material of a novel piezoelectric transformer.
Drawings
FIG. 1 is (1-x）NaNbO3-xLiTaO3A picture of the micro-morphology of the ceramic material;
FIG. 2 shows (1-x）NaNbO3-xLiTaO3An XRD pattern of the ceramic material;
FIG. 3 is (1-x）NaNbO3-xLiTaO3Hysteresis loop of ceramic material under critical polarization electric field.
Detailed Description
Embodiments of the invention are described in further detail below:
a high-polarization ferroelectric ceramic material with the stoichiometric formula of (1-x）NaNbO3-xLiTaO3Whereinx=0~0.2。
High polarization ferroelectric (1-x）NaNbO3-xLiTaO3The preparation method of the ceramic material comprises the following steps:
the method comprises the following steps: preparation of pure-phase NaNbO3With pure phase LiTaO3And (5) standby. Weighing Li according to a molar ratio of 1:12CO3And Ta2O5Mixing to form a mixture A; weighing Na according to the molar ratio of 1:12CO3And Nb2O5Mixing to form a mixture B; li2CO3、Ta2O5、Na2CO3、Nb2O5The purity of (A) is 99.0% or more.
Step two: mixing A, B mixture with zircon and deionized water according to the mass ratio of 1:5 (0.8-1) to 1:5 (1-1.2), ball milling for 18-24 h by using a planetary ball mill, drying for 20-24 h at 85-100 ℃, briquetting, placing in a box furnace, and respectively preserving heat of A, B at 1150-1200 ℃ for 2.5-3 h and 820-840 ℃ for 3-4 h to form LiTaO3Powder and NaNbO3Powder for later use;
step three: according to the chemical formula (1-x）NaNbO3-xLiTaO3，xTaking NaNbO for 0-0.23Powder and LiTaO3Uniformly mixing the powder to form a complete ingredient, mixing the complete ingredient with zirconia ball stone and deionized water according to the mass ratio of 1 (4.8-5.2) to (0.8-1.2), ball-milling for 18-24 h, and drying to obtain a dried material;
step four: grinding the dried material and sieving the ground material with a 120-mesh sieve to form a sieved material;
step five: pressing the screened material obtained in the fourth step into a sample by cold isostatic pressing under the pressure of 200-220 MPa, placing the prepared sample into an alumina sagger taking zirconia as a base plate, and then placing the alumina sagger into a box-type furnace, wherein the process specifically comprises the following steps: firstly, heating to 500 ℃ in 100min, then heating to 900 ℃ in 100min, and preserving heat for 120 min; then the temperature is reduced to 500 ℃ within 100min, and finally the temperature is cooled to room temperature along with the furnace.
Step six: polishing and cleaning the sintered sample obtained in the fifth step, uniformly coating silver electrode slurry on the front surface and the back surface of the polished and cleaned sintered sample, placing the sample coated with the silver electrode in an alumina sagger taking zirconia as a backing plate, then placing the alumina sagger in a box-type furnace, and sintering at the temperature of 580-600 ℃ for 10-20 min to obtain (1-x）NaNbO3-xLiTaO3A ceramic.
The invention will now be described in further detail with reference to the following examples, but it should be understood that the following detailed description is only illustrative of the invention and is not intended to limit the invention:
example 1
The preparation method of the high polarization ferroelectric ceramic comprises the following formula (1-x）NaNbO3-xLiTaO3Whereinx=0.00。
The method comprises the following steps: preparation of pure-phase NaNbO3Weighing Na according to the molar ratio of 1:1 for later use2CO3And Nb2O5Mixing to form a mixture A; na (Na)2CO3、Nb2O5The purity of (A) is 99.0% or more.
Step two: mixing the mixture A, zircon and deionized water according to the mass ratio of 1:5:1, ball-milling for 24 hours by using a planetary ball mill, drying for 24 hours at 80 ℃, briquetting, and placing the mixture A in a box furnace to respectively keep the temperature at 820 ℃ for 4 hours to form NaNbO3Powder for later use;
step three: taking NaNbO3Mixing the powder with zirconia ball stone and deionized water according to the mass ratio of 1:5:1, ball-milling for 24h, and drying to obtain a dried material;
step four: grinding the dried material and sieving the ground material with a 120-mesh sieve to form a sieved material;
step five: pressing the screened material obtained in the fourth step into a sample by cold isostatic pressing under the pressure of 200MPa, placing the prepared sample into an alumina sagger taking zirconia as a backing plate, and then placing the alumina sagger into a box-type furnace, wherein the process specifically comprises the following steps: firstly, heating to 500 ℃ in 100min, then heating to 900 ℃ in 100min, and preserving heat for 120 min; then the temperature is reduced to 500 ℃ within 100min, and finally the temperature is cooled to room temperature along with the furnace.
Step six: polishing and cleaning the sintered sample obtained in the fifth step, uniformly coating silver electrode slurry on the front surface and the back surface of the polished and cleaned sintered sample, placing the sample coated with the silver electrode in an alumina sagger taking zirconia as a backing plate, and then placing the alumina saggerPlacing the pot in a box furnace, and sintering at 600 ℃ for 20min to obtain NaNbO3The system is ceramic.
Example 2
The preparation method of the high polarization ferroelectric ceramic material comprises the following formula (1-x）NaNbO3-xLiTaO3Whereinx=0.05。
The method comprises the following steps: pure phase LiTaO3 was prepared for use with pure phase NaNbO 3. Weighing Li according to a molar ratio of 1:12CO3And Ta2O5Mixing to form a mixture A; weighing Na according to the molar ratio of 1:12CO3And Nb2O5Mixing to form a mixture B; li2CO3、Ta2O5、Na2CO3、Nb2O5The purity of (A) is 99.0% or more.
Step two: mixing the mixture A, B with zircon and deionized water respectively according to the mass ratio of 1:5:1 and 1:5:1, ball milling for 24h by using a planetary ball mill, drying for 24h at 80 ℃, briquetting, placing A, B in a box furnace respectively, preserving heat for 3 h at 1200 ℃ and preserving heat for 4h at 820 ℃ to form LiTaO respectively3Powder and NaNbO3Powder for later use;
step three: according to the chemical formula (1-x）NaNbO3-xLiTaO3，x=0.05, take LiTaO3Powder and NaNbO3Uniformly mixing the powder to form a complete ingredient, mixing the complete ingredient with zirconia ball stone and deionized water according to the mass ratio of 1:5:1, ball-milling for 24 hours, and drying to obtain a dried material;
step four: grinding the dried material and sieving the ground material with a 120-mesh sieve to form a sieved material;
step five: pressing the screened material obtained in the fourth step into a sample by cold isostatic pressing under the pressure of 200MPa, placing the prepared sample into an alumina sagger taking zirconia as a backing plate, and then placing the alumina sagger into a box-type furnace, wherein the process specifically comprises the following steps: firstly, heating to 500 ℃ in 100min, then heating to 900 ℃ in 100min, and preserving heat for 120 min; then the temperature is reduced to 500 ℃ within 100min, and finally the temperature is cooled to room temperature along with the furnace.
Step six: polishing and cleaning the sintered sample obtained in the fifth step, uniformly coating silver electrode slurry on the front surface and the back surface of the polished and cleaned sintered sample, placing the sample coated with the silver electrode into an alumina sagger taking zirconia as a backing plate, then placing the alumina sagger into a box furnace, and sintering at the temperature of 600 ℃ for 20min to obtain 0.95NaNbO3-0.05LiTaO3The system is ceramic.
Example 3
The preparation method of the high-polarization ferroelectric ceramic material comprises the following formula (1-x）NaNbO3-xLiTaO3Whereinx=0.10。
The method comprises the following steps: preparation of pure phase LiTaO3 and pure phase NaNbO3And (5) standby. Weighing Li according to a molar ratio of 1:12CO3And Ta2O5Mixing to form a mixture A; weighing Na according to the molar ratio of 1:12CO3And Nb2O5Mixing to form a mixture B; li2CO3、Ta2O5、Na2CO3、Nb2O5The purity of (A) is 99.0% or more.
Step two: mixing the mixture A, B with zircon and deionized water respectively according to the mass ratio of 1:5:1 and 1:5:1, ball milling for 24h by using a planetary ball mill, drying for 24h at 80 ℃, briquetting, placing A, B in a box furnace respectively, preserving heat for 3 h at 1200 ℃ and preserving heat for 4h at 820 ℃ to form LiTaO respectively3Powder and NaNbO3Powder for later use;
step three: according to the chemical formula (1-x）NaNbO3-xLiTaO3，x=0.10, take LiTaO3Powder and NaNbO3Uniformly mixing the powder to form a complete ingredient, mixing the complete ingredient with zirconia ball stone and deionized water according to the mass ratio of 1:5:1, ball-milling for 24 hours, and drying to obtain a dried material;
step four: grinding the dried material and sieving the ground material with a 120-mesh sieve to form a sieved material;
step five: pressing the screened material obtained in the fourth step into a sample by cold isostatic pressing under the pressure of 200MPa, placing the prepared sample into an alumina sagger taking zirconia as a backing plate, and then placing the alumina sagger into a box-type furnace, wherein the process specifically comprises the following steps: firstly, heating to 500 ℃ in 100min, then heating to 900 ℃ in 100min, and preserving heat for 120 min; then the temperature is reduced to 500 ℃ within 100min, and finally the temperature is cooled to room temperature along with the furnace.
Step six: polishing and cleaning the sintered sample obtained in the fifth step, uniformly coating silver electrode slurry on the front surface and the back surface of the polished and cleaned sintered sample, placing the sample coated with the silver electrode into an alumina sagger taking zirconia as a backing plate, then placing the alumina sagger into a box furnace, and sintering at the temperature of 600 ℃ for 20min to obtain 0.90NaNbO3-0.10LiTaO3The system is ceramic.
Example 4
The preparation method of the high polarization ferroelectric ceramic material comprises the following formula (1-x）NaNbO3-xLiTaO3Whereinx=0.15。
The method comprises the following steps: preparation of pure phase LiTaO3With pure phase NaNbO3And (5) standby. Weighing Li according to a molar ratio of 1:12CO3And Ta2O5Mixing to form a mixture A; weighing Na according to the molar ratio of 1:12CO3And Nb2O5Mixing to form a mixture B; li2CO3、Ta2O5、Na2CO3、Nb2O5The purity of (A) is 99.0% or more.
Step two: mixing the mixture A, B with zircon and deionized water respectively according to the mass ratio of 1:5:1 and 1:5:1, ball milling for 24h by using a planetary ball mill, drying for 24h at 80 ℃, briquetting, placing A, B in a box furnace respectively, preserving heat for 3 h at 1200 ℃ and preserving heat for 4h at 820 ℃ to form LiTaO respectively3Powder and NaNbO3Powder for later use;
step three: according to the chemical formula (1-x）NaNbO3-xLiTaO3，x=0.15, take LiTaO3Powder and NaNbO3Uniformly mixing the powder to form a complete ingredient, mixing the complete ingredient with zirconia ball stone and deionized water according to the mass ratio of 1:5:1, and then carrying outBall-milling for 24h, and drying to obtain a dried material;
step four: grinding the dried material and sieving the ground material with a 120-mesh sieve to form a sieved material;
step five: pressing the screened material obtained in the fourth step into a sample by cold isostatic pressing under the pressure of 200MPa, placing the prepared sample into an alumina sagger taking zirconia as a backing plate, and then placing the alumina sagger into a box-type furnace, wherein the process specifically comprises the following steps: firstly, heating to 500 ℃ in 100min, preserving heat for 3 min, and then, preserving heat for 120min when heating to 900 ℃ in 100 min; then the temperature is reduced to 500 ℃ within 100min, and finally the temperature is cooled to room temperature along with the furnace.
Step six: polishing and cleaning the sintered sample obtained in the fifth step, uniformly coating silver electrode slurry on the front surface and the back surface of the polished and cleaned sintered sample, placing the sample coated with the silver electrode into an alumina sagger taking zirconia as a backing plate, then placing the alumina sagger into a box furnace, and sintering at the temperature of 600 ℃ for 20min to obtain 0.85NaNbO3-0.15LiTaO3The system is ceramic.
Example 5
The preparation method of the high polarization ferroelectric ceramic material comprises the following formula (1-x）NaNbO3-xLiTaO3Whereinx=0.20。
The method comprises the following steps: preparation of pure phase LiTaO3With pure phase NaNbO3And (5) standby. Weighing Li according to a molar ratio of 1:12CO3And Ta2O5Mixing to form a mixture A; weighing Na according to the molar ratio of 1:12CO3And Nb2O5Mixing to form a mixture B; li2CO3、Ta2O5、Na2CO3、Nb2O5The purity of (A) is 99.0% or more.
Step two: mixing the mixture A, B with zircon and deionized water respectively according to the mass ratio of 1:5:1 and 1:5:1, ball milling for 24h by using a planetary ball mill, drying for 24h at 80 ℃, briquetting, placing A, B in a box furnace respectively, preserving heat for 3 h at 1200 ℃ and preserving heat for 4h at 820 ℃ to form LiTaO respectively3Powder and NaNbO3Powder for later use;
step three: according to the chemical formula (1-x）NaNbO3-xLiTaO3，x=0.20, take LiTaO3Powder and NaNbO3Uniformly mixing the powder to form a complete ingredient, mixing the complete ingredient with zirconia ball stone and deionized water according to the mass ratio of 1:5:1, ball-milling for 24 hours, and drying to obtain a dried material;
step four: grinding the dried material and sieving the ground material with a 120-mesh sieve to form a sieved material;
step five: pressing the screened material obtained in the fourth step into a sample by cold isostatic pressing under the pressure of 200MPa, placing the prepared sample into an alumina sagger taking zirconia as a backing plate, and then placing the alumina sagger into a box-type furnace, wherein the process specifically comprises the following steps: firstly, heating to 500 ℃ in 100min, preserving heat for 3 min, and then, preserving heat for 120min when heating to 900 ℃ in 100 min; then the temperature is reduced to 500 ℃ within 100min, and finally the temperature is cooled to room temperature along with the furnace.
Step six: polishing and cleaning the sintered sample obtained in the fifth step, uniformly coating silver electrode slurry on the front surface and the back surface of the polished and cleaned sintered sample, placing the sample coated with the silver electrode into an alumina sagger taking zirconia as a backing plate, then placing the alumina sagger into a box furnace, and sintering at the temperature of 600 ℃ for 20min to obtain 0.80NaNbO3-0.20LiTaO3The system is ceramic.
Example 5
The microstructure analysis of the samples prepared in examples 1-5 was performed to obtain the results shown in FIG. 1, wherein FIG. 1 is (1-x）NaNbO3-xLiTaO3And (3) a microscopic morphology picture of the system ceramic. From FIG. 1 it can be seen that addition of LiTaO3Thereafter, the grains are significantly finer and the sample is dense with a grain size from about 60
m is reduced to 3-4
m（x= 0.15). Li is used to replace high-temperature volatile Na, so increasing the compactness of ceramic, and Li and Ta have sintering aidActing to reduce the grain size when LiTaO3Is added in an amount ofxIf the solubility exceeds 0.20, a small amount of LiTaO is present3Occurs because the presence of the second phase results in non-uniform grain size.
XRD testing was performed on the samples prepared in examples 1-5 to obtain the results shown in FIG. 2, in which FIG. 2 is (1-x）NaNbO3-xLiTaO3XRD pattern of system ceramic. As can be seen from fig. 2, all samples exhibited perovskite crystal structures. With increasing doping, a small amount of second phase is formed.
The samples of examples 1-5 were tested for P-E loops at different electric fields, and the results of FIG. 3 were obtained. FIG. 3 is (1-x）NaNbO3-xLiTaO3The addition of LiTaO can be found in the P-E loops of the system ceramics under the critical polarization electric field3Then, the polarization of the hysteresis loop is increased and then decreased atxMax is reached when = 0.15. The sodium niobate ceramic prepared by the present invention exhibits superior polarization strength compared to the current study: (>45
C/cm2). The possibility is provided for achieving high piezoelectric performance.
Claims (8)
1. The lithium tantalate is used for improving the compactness of the sodium niobate ceramic material or improving the polarization strength of the sodium niobate ceramic material.
2. Use according to claim 1, characterized in that it comprises the following steps:
mixing NaNbO3With LiTaO3And ball milling after uniform mixing, pressing into a green body, and sintering to obtain the sintered ceramic.
3. The use of claim 2, wherein the lithium tantalate and the sodium niobate satisfy the following metering relationship: (1-x）NaNbO3-xLiTaO3，x≤0.2。
4. Use according to claim 2, wherein the green body is pressed by cold isostatic pressing at a pressure of 200 to 220 MPa.
5. Use according to claim 2, wherein the sintering conditions are: in a box furnace, firstly, heating to 500 ℃ in 100 min; then heating to 900 ℃ for 100min, and preserving heat for 120 min; then the temperature is reduced to 500 ℃ within 100min, and finally the temperature is cooled to room temperature along with the furnace.
6. The use according to claim 2, wherein the NaNbO is milled in a ball mill3With LiTaO3Mixing uniformly to form a complete ingredient, mixing the complete ingredient with zirconia ball stone and deionized water according to the mass ratio of 1:5:1, and fully ball-milling.
7. The use according to claim 2, comprising the steps of:
the method comprises the following steps: mixing NaNbO3Powder and LiTaO3The powder is according to the stoichiometric formula (1-x）NaNbO3-xLiTaO3，xLess than or equal to 0.2, and mixing uniformly to form a complete ingredient;
step two: ball-milling the whole ingredients, drying and sieving to form a sieved material;
step three: pressing the screened material into a green body, and sintering the prepared green body to obtain the sintered ceramic.
8. A ferroelectric ceramic material with high polarization, which is characterized in that the stoichiometric formula is (1-x）NaNbO3-xLiTaO3，x=0.15。
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