CN107311656B - Antiferroelectric ceramic material with giant negative electric-card effect, preparation method and application thereof - Google Patents

Antiferroelectric ceramic material with giant negative electric-card effect, preparation method and application thereof Download PDF

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CN107311656B
CN107311656B CN201710537751.0A CN201710537751A CN107311656B CN 107311656 B CN107311656 B CN 107311656B CN 201710537751 A CN201710537751 A CN 201710537751A CN 107311656 B CN107311656 B CN 107311656B
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antiferroelectric ceramic
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CN107311656A (en
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李彼
唐新桂
刘秋香
蒋艳平
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Guangdong University of Technology
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Abstract

The invention provides an antiferroelectric ceramic material with a giant negative electric card effect, which comprises the following chemical components: (Pb)1‑3x/2Lax)(Zr0.95Ti0.05)O3(ii) a X is 0.02-0.1; the antiferroelectric ceramic material has a giant negative electrocaloric effect. Compared with the prior art, the antiferroelectric ceramic material electric card effect refrigeration provided by the invention has the characteristics of large refrigeration coefficient, higher energy conversion rate and easiness in realizing integration.

Description

Antiferroelectric ceramic material with giant negative electric-card effect, preparation method and application thereof
Technical Field
The invention belongs to the technical field of refrigeration, and particularly relates to an antiferroelectric ceramic material with a giant negative electric-card effect, and a preparation method and application thereof.
Background
In recent years, environmental and energy problems have been highlighted, and it is necessary to significantly improve the conventional refrigeration technology. Taking an air conditioner as an example, the air conditioner used in large-scale households at present takes freon as a refrigerant, but the freon can damage an ozone layer, and the energy conversion efficiency of an air compression technology is low. With the development of economic technology, the demand of people on refrigeration technology is rapidly increased, and the development of new technology also requires diversification on refrigeration, so the importance of high-efficiency, energy-saving and environment-friendly refrigeration technology is highlighted. According to the new refrigeration physical effect, new materials are searched, and new and environment-friendly refrigerators such as thermoelectric refrigeration, magnetic refrigeration, ferroelectric refrigeration and the like are developed to be paid more and more attention by researchers.
In particular, the electric card effect has advantages in that a large electric field for obtaining a large temperature change is more easily obtained than a large magnetic field and the cost is lower, compared with the magnetic card effect; although thermoelectric refrigeration also has the advantages of environmental protection, fast reaction and controllability, the efficiency is too low and the cost is relatively high; the refrigerator prepared by using the ferroelectric material does not need an additional compressor, is extremely beneficial to miniaturization, and can meet most of refrigeration requirements under new potential, so the development of ferroelectric refrigeration has positive significance.
Disclosure of Invention
In view of the above, the technical problem to be solved by the present invention is to provide an antiferroelectric ceramic material with a giant negative electrical-card effect, a preparation method thereof, and a use thereof.
The invention provides an antiferroelectric ceramic material with a giant negative electric card effect, which comprises the following chemical components:
(Pb1-3x/2Lax)(Zr0.95Ti0.05)O3；
x is 0.02-0.1;
the antiferroelectric ceramic material has a giant negative electrocaloric effect.
Preferably, x is 0.02, 0.04, 0.06, 0.08 or 0.1.
Preferably, the negative electric clamping effect of the antiferroelectric ceramic material is-0.26K to-3.25K under the field strength of 55 kV/cm.
The invention also provides a preparation method of the antiferroelectric ceramic material, which comprises the following steps:
s1) mixing a lead source, a titanium source, a zirconium source and a lanthanum source, performing ball milling, and calcining to obtain a first intermediate;
s2) carrying out secondary ball milling on the first intermediate, and after molding, sequentially carrying out glue removal treatment and high-temperature sintering to obtain the antiferroelectric ceramic material.
Preferably, the dispersing agent for ball milling in the step S1) is an alcohol solvent; the ball milling time is 20-30 h; the dispersing agent for the secondary ball milling in the step S2) is an alcohol solvent; the time of the secondary ball milling is 20-30 h.
Preferably, the calcining temperature is 700-900 ℃; and the calcining time is 3-8 h.
Preferably, the temperature of the rubber discharge treatment is 550-700 ℃; the heating rate of the glue discharging treatment is 1-5 ℃/min.
Preferably, the high-temperature sintering temperature is 1000-1500 ℃; the high-temperature sintering time is 3-8 h; the heating rate of the high-temperature sintering is 1-5 ℃/min.
The invention also provides an application of the antiferroelectric ceramic material as a refrigeration material.
The invention also provides a refrigeration device which comprises the antiferroelectric ceramic material.
The invention provides an antiferroelectric ceramic material with a giant negative electric card effect, which comprises the following chemical components: (Pb)1-3x/2Lax)(Zr0.95Ti0.05)O3(ii) a X is 0.02-0.1; the antiferroelectric ceramic material has a giant negative electrocaloric effect. Compared with the prior art, the antiferroelectric ceramic material electric card effect refrigeration provided by the invention has the characteristics of large refrigeration coefficient, higher energy conversion rate and easiness in realizing integration.
Drawings
FIG. 1 is a dielectric thermogram of an antiferroelectric ceramic material prepared in example 1 of the present invention;
FIG. 2 is a DSC chart and a hysteresis chart of the antiferroelectric ceramic material prepared in example 1 of the present invention;
FIG. 3 is a graph of polarization intensity at different temperatures and pyroelectric coefficients at different temperatures of an antiferroelectric ceramic material prepared in example 1 of the present invention;
fig. 4 is a graph showing the giant negative electrical clamping effect Δ S and the giant negative electrical clamping effect Δ T of the antiferroelectric ceramic material prepared in example 1 of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to 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. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides an antiferroelectric ceramic material with a giant negative electric card effect, which comprises the following chemical components:
(Pb1-3x/2Lax)(Zr0.95Ti0.05)O3；
the x is 0.02-0.1, preferably 0.02-0.08, more preferably 0.02, 0.04, 0.06, 0.08 or 0.1.
The antiferroelectric ceramic material has a giant negative charge-clamping effect, and the negative charge-clamping effect is-0.26K to-3.25K under the field intensity of 55kV/cm of electric field.
The antiferroelectric ceramic material provided by the invention has the characteristics of large refrigeration coefficient, higher energy conversion rate and easiness in realizing integration.
The invention also provides a preparation method of the antiferroelectric ceramic material, which comprises the following steps: s1) mixing a lead source, a titanium source, a zirconium source and a lanthanum source, performing ball milling, and calcining to obtain a first intermediate; s2) carrying out secondary ball milling on the first intermediate, and after molding, sequentially carrying out glue removal treatment and high-temperature sintering to obtain the antiferroelectric ceramic material.
Mixing a lead source, a titanium source, a zirconium source and a lanthanum source, and carrying out ball milling; wherein, the lead source is known to those skilled in the art, and is not particularly limited, the present invention is preferably lead oxide, and more preferably one or more of lead oxide tetraoxide, lead dioxide and lead sesquioxide; the titanium source is not particularly limited as long as it is known to those skilled in the art, and in the present invention, titanium dioxide is preferable; the zirconium source is not particularly limited as long as it is a zirconium source known to those skilled in the art, and in the present invention, zirconium dioxide is preferable; the lanthanum source is a lanthanum source known to those skilled in the art, and is not particularly limited, and lanthanum oxide is preferred in the present invention; mixing the lead source, the titanium source, the zirconium source and the lanthanum source according to the stoichiometric requirement of the composition, wherein the lead source is preferably in excess of 2-10 percent, more preferably in excess of 3-8 percent, still more preferably in excess of 4-6 percent, and most preferably in excess of 5 percent; the ball milling is a ball milling method well known to those skilled in the art, and is not particularly limited, and wet ball milling is preferred in the present invention; the dispersing agent for ball milling is preferably an alcohol solvent, more preferably ethanol, and still more preferably absolute ethanol; the ball milling time is preferably 20-30 h, more preferably 22-28 h, and further preferably 24-26 h.
After ball milling, preferably drying and then calcining to obtain a first intermediate; the calcination is preferably carried out in an alumina crucible; the calcination temperature is preferably 700-900 ℃, more preferably 800-900 ℃, and further preferably 850 ℃; the calcination time is preferably 3-8 h, more preferably 4-7 h, and still more preferably 5-6 h.
Carrying out secondary ball milling on the first intermediate; the method of the secondary ball milling is a method well known to those skilled in the art, and is not particularly limited, and wet ball milling is preferred in the present invention; the dispersing agent for the secondary ball milling is preferably an alcohol solvent, more preferably ethanol, and still more preferably absolute ethanol; the time of the secondary ball milling is preferably 20-30 h, more preferably 22-28 h, and further preferably 24-26 h.
After ball milling, preferably drying and then molding; the molding method is not particularly limited as long as it is a method known to those skilled in the art, and in the present invention, it is preferable to mix the dried raw material with a binder and press-mold it; the binder is not particularly limited as long as it is well known to those skilled in the art, and in the present invention, polyvinyl alcohol PVA or polyvinyl propanol PVB is preferable; the mass of the binder is preferably 2 to 10%, more preferably 3 to 8%, even more preferably 5 to 7%, and most preferably 5% of the mass of the dried raw material; the dried raw materials and the binder are preferably ground and mixed; the press forming is preferably carried out by a hydraulic press. After the press molding, it is preferable to further perform isostatic pressing; the isostatic pressing treatment is preferably carried out by using a cold isostatic press; the isostatic pressing treatment is preferably performed under vacuum conditions.
After molding, sequentially carrying out glue discharging treatment and high-temperature sintering; the heating rate of the rubber discharge treatment is preferably 1-5 ℃/min, more preferably 2-4 ℃/min, and further preferably 2-3 ℃/min; the temperature of the rubber discharge treatment is preferably 550-700 ℃, more preferably 600-700 ℃, and further preferably 600-650 ℃; after the glue discharging treatment, continuously heating for high-temperature sintering to obtain an antiferroelectric ceramic material; the heating rate of the high-temperature sintering is preferably 1-5 ℃/min, more preferably 2-4 ℃/min, and further preferably 2-3 ℃/min; the high-temperature sintering temperature is preferably 1000-1500 ℃, more preferably 1100-1400 ℃, still more preferably 1200-1300 ℃, and most preferably 1250 ℃; the high-temperature sintering time is preferably 3-8 h, more preferably 4-7 h, and further preferably 5-6 h.
The invention adopts a high-temperature solid phase method to prepare the antiferroelectric ceramic material, and the preparation method is simple.
The performance of the obtained antiferroelectric ceramic material is tested, the obtained antiferroelectric ceramic material is polished into a ceramic wafer with the thickness of 0.6-0.8 mm, a silver electrode is plated after polishing, the electrode is sintered at the temperature of 600 ℃, a ceramic sample can be obtained, and the test of the change of the dielectric constant and the loss along with the temperature is carried out; and then testing the antiferroelectric ceramic material at the field intensity of 30-55 kV/cm at every 10 ℃, increasing the temperature from room temperature to 200 ℃, and performing fitting operation on the obtained saturated polarization value to obtain a refrigerating indirect test result, wherein the negative charge-up effect of the obtained antiferroelectric ceramic material is-0.26K-3.25K under the field intensity of 55 kV/cm.
The invention also provides application of the obtained antiferroelectric ceramic material as a refrigeration material.
The invention also provides a refrigeration device comprising the obtained antiferroelectric ceramic material.
In order to further illustrate the present invention, the following examples are provided to describe in detail an antiferroelectric ceramic material with giant negative electrocaloric effect, and its preparation method and use.
The reagents used in the following examples are all commercially available.
Example 1
The chemical composition of the ceramic a is as follows: (Pb)0.97La0.02)(Zr0.95Ti0.05)O3(PLZT2/95/5) method for producing ceramic. The preparation of the ceramic adopts a high-temperature solid-phase reaction method to prepare PLZT2/95/5 antiferroelectric ceramic, and specifically comprises the following steps:
1.1 use of oxides of high purity components according to the formula (Pb)0.97La0.02)(Zr0.95Ti0.05)O3The stoichiometric requirements of (1) are mixed, all at 99% Pb3O4，TiO2，ZrO2And La2O3As raw material, with Pb3O4An excess of 5% by weight.
1.2 putting the weighed raw materials into a ball milling tank, adding 80-100 mL of absolute ethyl alcohol as a dispersing agent, carrying out ball milling for 24h, drying the slurry after ball milling, and calcining for 5h at 850 ℃ by using an alumina crucible to obtain a first intermediate.
And (3) adding 80-100 mL of absolute ethyl alcohol serving as a dispersing agent into the mixture of the first intermediate and the second intermediate, performing secondary ball milling for 24 hours, and drying the slurry after ball milling.
1.4 using 5 wt% PVA as a binder, thoroughly mixing 1g of fine powder with 15 drops of PVA, grinding in an agate bowl, and pressing into cylindrical pellets with a diameter of 12mm and a thickness of 1-2 mm by a hydraulic press.
1.5 the sample is placed in a vacuum bag for vacuum pumping and sealing, and then isostatic pressing is carried out by an LDJ100/320 and 300 type cold isostatic pressing machine.
1.6 heating up in a muffle furnace at the heating rate of 2 ℃/min, discharging the glue of the sample in a covered alumina crucible at the temperature of 650 ℃, and sintering at the temperature of 1250 ℃ for 5h to obtain the antiferroelectric ceramic material.
And (3) sample testing: polishing the antiferroelectric ceramic material obtained in the embodiment 1 into a ceramic sheet with the thickness of 0.6-0.8 mm, plating a silver electrode after polishing, firing the electrode at 600 ℃ to obtain a ceramic sample, and testing the change of dielectric constant and loss along with the temperature; and then testing the temperature of the sample at every 10 ℃ under the field intensity (30-55 kV/cm) by using a ferroelectric instrument, raising the temperature from room temperature to 200 ℃, and performing fitting operation on the obtained saturated polarization value to obtain a refrigerating indirect test result, wherein the negative charge-blocking effect of the sample is-3.25K under the field intensity of 55kV/cm of an electric field.
The obtained dielectric temperature spectrum is shown in figure 1, the measurement of the functional relation between the dielectric constant and the dielectric loss is an important content and means for researching the dielectricity and the structure of the antiferroelectric material, and two different phase transitions can be observed, wherein the first peak represents the transition from the antiferroelectric phase to the ferroelectric phase (T)o) The second peak represents the transition from the ferroelectric phase to the paraelectric phase (T)C)。
The DSC curve is shown in FIG. 2(a), and the hysteresis loop is shown in FIG. 2 (b); from (a) the DSC analysis results showed that latent heat associated with the phase change was detected in PLZT2/95/5 ceramic, indicating the presence of a region of macroscopic phase change within it. The DSC plot shows two anomalous peaks, consistent with the representation of the dielectric constant spectrum, and the presence of two distinct phase transitions is observed, the first of which represents the transition from the antiferroelectric phase to the ferroelectric phase (T)o) The second peak represents ironTransition of electric phase to paraelectric phase (T)C) (ii) a It can also be seen from the graph (b) that a typical antiferroelectric hysteresis loop appears with the change of temperature.
Obtaining a polarization intensity diagram at different temperatures as shown in (a) in fig. 3 and a pyroelectric coefficient diagram at different temperatures as shown in (b) in fig. 3; as can be seen from the graph (a), for the ceramic sample, under the same electric field, the polarization intensity gradually increases with the increase of the temperature; at the same temperature, the polarization strength of the ceramic sample is increased along with the increase of an external electric field, because the application of the external electric field enables the spontaneous polarization direction of electric dipoles in the material to tend to the direction of the electric field, and the higher the electric field is, the higher the polarization strength is; the polarization strength P of the crystal at different temperatures is obtained from the hysteresis loop, and then the slope is obtained from the curve of P to T, so as to obtain the pyroelectric coefficient
Figure BDA0001341047880000061
Graph (b), the larger the abrupt change in the polarization intensity, i.e., the larger the electrocaloric coefficient, the larger the electrocaloric effect of the ceramic.
Obtaining a giant negative electrical card effect delta S diagram as shown in (a) in fig. 4 and a giant negative electrical card effect delta T diagram as shown in (b) in fig. 4; in the dielectric material, the polarization state of the dipole is changed due to the action of an external electric field, so that isothermal entropy change deltaS or the change deltaT of a thermometer of the dielectric material is generated, and the phenomenon is called electrocaloric effect; the electrocaloric effect (ECE) is generally characterized by a relatively intuitive isothermal entropy change Δ S and a reversible adiabatic temperature Δ T, and is measured indirectly by the following formula:
Figure BDA0001341047880000071
Figure BDA0001341047880000072
as can be seen in FIG. 4, the PLZT2/95/5 ceramic exhibits a good negative electrocaloric effect. As seen in fig. 4, the isothermal entropy change (Δ S) and adiabatic temperature change (Δ T) exhibited similar variation trends with temperature. | Δ S | andthe value of Δ T varies with temperature and Δ E; at the same temperature, | Δ S | and | Δ T | values increase with increasing Δ E; with increasing temperature, | Δ S | and | Δ T | increase and then decrease, then increase to a maximum value, and then gradually decrease, at a Curie temperature TCA maximum value is reached in the vicinity. As can be seen from plot (a), Δ S reached a minimum at 428K and 498K at an electric field of 55kV/cm, corresponding to a and b of-0.32J kg-1K-1and-1.56J kg-1K-1(ii) a As seen in FIG. (b), the corresponding Δ T reaches a minimum at 428K and 498K, where a 'and b' are-0.66K and-3.25K, respectively; the maximum electric clamping value delta T is-3.25K, which corresponds to the electric clamping effect refrigeration action generated in the phase transition process of AFE-FE and FE-PE of antiferroelectric ceramic field. As the electric field increases, the temperature change of the dipole and the corresponding entropy change will increase from one increment to the next until saturation. When the dipole is completely rotated to the direction of the applied electric field, the corresponding entropy change and temperature change of the dipole are saturated. So far, the reports about the positive electrocaloric effect are more, while the reports about the negative electrocaloric effect are less, and the reports are found in the antiferroelectric material PLZT2/95/5 ceramic. The electric clamping effect of the block material is improved, and the requirements of large and medium-sized refrigeration equipment can be met.
Example 2
The chemical composition of the ceramic b is as follows: (Pb)0.94La0.04)(Zr0.95Ti0.05)O3(PLZT4/95/5) preparation method of ceramic the preparation of the ceramic adopts a high-temperature solid-phase reaction method to prepare PLZT4/95/5 antiferroelectric ceramic, and the preparation method specifically comprises the following steps:
2.1 use of oxides of high purity as a constituent of the formula (Pb)0.94La0.04)(Zr0.95Ti0.05)O3The stoichiometric requirements of (1) are mixed, all at 99% Pb3O4，TiO2，ZrO2And La2O3As raw material, with Pb3O4An excess of 5% by weight.
2.2 putting the weighed raw materials into a ball milling tank, adding 80-100 mL of absolute ethyl alcohol as a dispersing agent, carrying out ball milling for 24h, drying the slurry after ball milling, and calcining for 5h at 850 ℃ by using an alumina crucible to obtain a first intermediate.
And 2.3, adding 80-100 mL of absolute ethyl alcohol serving as a dispersing agent to perform secondary ball milling with the first intermediate, performing ball milling for 24 hours, and drying the ball-milled slurry.
2.4 use 5 wt% PVA as binder, 1g fine powder and 15 drops of PVA thoroughly mixed, grinding in agate bowl, pressing into cylindrical pellets of 12mm diameter and 1-2 mm thickness with hydraulic press.
2.5 the sample is placed in a vacuum bag for vacuum sealing, and then isostatic pressing is carried out by using an LDJ100/320 and 300 type cold isostatic pressing machine.
6) And then heating in a muffle furnace at the heating rate of 2 ℃/min, removing glue from a sample in a covered alumina crucible at the temperature of 650 ℃, and sintering at the temperature of 1250 ℃ for 5 hours to obtain the antiferroelectric ceramic material.
And (3) sample testing: and (3) polishing the obtained antiferroelectric ceramic material into a ceramic wafer with the thickness of 0.6-0.8 mm, plating a silver electrode on the polished sample, sintering the silver electrode at 600 ℃ to obtain a ceramic sample, and testing the change of dielectric constant and loss along with the temperature. And then testing the temperature of the sample at every 10 ℃ under the field intensity (30-55 kV/cm) by using a ferroelectric instrument, raising the temperature from room temperature to 200 ℃, and performing fitting operation on the obtained saturated polarization value to obtain a refrigerating indirect test result, wherein the negative charge-up effect of the sample is-0.64K under the field intensity of 55kV/cm of an electric field.
Example 3
The ceramic c comprises the following chemical components: (Pb)0.91La0.06)(Zr0.95Ti0.05)O3(PLZT6/95/5) preparation method of ceramic the preparation of the ceramic adopts a high-temperature solid-phase reaction method to prepare PLZT6/95/5 antiferroelectric ceramic, and the preparation method specifically comprises the following steps:
3.1 use of oxides of high purity components according to the formula (Pb)0.91La0.06)(Zr0.95Ti0.05)O3(the stoichiometry of each is 99% Pb3O4，TiO2，ZrO2And La2O3As raw material, with Pb3O4An excess of 5% by weight.
3.2 putting the weighed raw materials into a ball milling tank, adding 80-100 mL of absolute ethyl alcohol as a dispersing agent, carrying out ball milling for 24h, drying the slurry after ball milling, and calcining for 5h at 850 ℃ by using an alumina crucible to obtain a first intermediate.
And 3.3, adding 80-100 mL of absolute ethyl alcohol serving as a dispersing agent to perform secondary ball milling with the first intermediate, performing ball milling for 24 hours, and drying the ball-milled slurry.
3.4 use 5 weight% PVA as the binder, 1g of fine powder and 15 drops of PVA thoroughly mixed, grinding in an agate bowl, pressing into cylindrical pellets with a diameter of 12mm and a thickness of 1-2 mm by a hydraulic press.
3.5 the sample is placed in a vacuum bag for vacuum pumping and sealing, and then isostatic pressing is carried out by using an LDJ100/320 and 300 type cold isostatic pressing machine.
3.6 heating up in a muffle furnace at the heating rate of 2 ℃/min, discharging the glue of the sample in a covered alumina crucible at the temperature of 650 ℃, and sintering at the temperature of 1250 ℃ for 5h to obtain the antiferroelectric ceramic material.
And (3) sample testing: and (3) polishing the obtained antiferroelectric ceramic material into a ceramic wafer with the thickness of 0.6-0.8 mm, plating a silver electrode after polishing the sample, and sintering the electrode at 600 ℃ to obtain the ceramic sample. Measurements of dielectric constant and loss as a function of temperature were performed. And then testing the temperature of the sample at every 10 ℃ under the field intensity (30-55 kV/cm) by using a ferroelectric instrument, raising the temperature from room temperature to 200 ℃, and performing fitting operation on the obtained saturated polarization value to obtain a refrigerating indirect test result, wherein the negative charge-up effect of the sample is-0.27K under the field intensity of 55kV/cm of an electric field.
Example 4
The chemical composition of the ceramic d is as follows: (Pb)0.88La0.08)(Zr0.95Ti0.05)O3(PLZT8/95/5) preparation method of ceramic the preparation of the ceramic adopts a high-temperature solid-phase reaction method to prepare PLZT8/95/5 antiferroelectric ceramic, and the preparation method specifically comprises the following steps:
4.1 use of oxides of high purity components according to the formula (Pb)0.88La0.08)(Zr0.95Ti0.05)O3(the stoichiometry of each is 99% Pb3O4，TiO2，ZrO2And La2O3As raw material, with Pb3O4An excess of 5% by weight.
4.2 putting the weighed raw materials into a ball milling tank, adding 80-100 mL of absolute ethyl alcohol as a dispersing agent, carrying out ball milling for 24h, drying the slurry after ball milling, and calcining for 5h at 850 ℃ by using an alumina crucible to obtain a first intermediate.
And 4.3, adding 80-100 mL of absolute ethyl alcohol serving as a dispersing agent to perform secondary ball milling with the first intermediate, performing ball milling for 24 hours, and drying the ball-milled slurry.
4.4 use 5 weight% PVA as the binder, 1g of fine powder and 15 drops of PVA thoroughly mixed, grinding in an agate bowl, pressing into cylindrical pellets with a diameter of 12mm and a thickness of 1-2 mm with a hydraulic press.
4.5 the sample is placed in a vacuum bag for vacuum sealing, and then isostatic pressing is carried out by using an LDJ100/320 and 300 type cold isostatic pressing machine.
4.6 heating up in a muffle furnace at the heating rate of 2 ℃/min, discharging the glue of the sample in a covered alumina crucible at the temperature of 650 ℃, and sintering at the temperature of 1250 ℃ for 5h to obtain the antiferroelectric ceramic material.
And (3) sample testing: and (3) polishing the obtained antiferroelectric ceramic material into a ceramic wafer with the thickness of 0.6-0.8 mm, plating a silver electrode after polishing the sample, and sintering the electrode at 600 ℃ to obtain the ceramic sample. Measurements of dielectric constant and loss as a function of temperature were performed. And then testing the temperature of the sample at every 10 ℃ under the field intensity (30-55 kV/cm) by using a ferroelectric instrument, raising the temperature from room temperature to 200 ℃, and performing fitting operation on the obtained saturated polarization value to obtain a refrigerating indirect test result, wherein the negative charge-up effect of the sample is-0.26K under the field intensity of 55kV/cm of an electric field.
The antiferroelectric ceramic provided by the invention shows the good giant negative electricity card effect of PLZT2/95/5 antiferroelectric ceramic, and due to the unique refrigeration characteristic of the electricity card effect, the PLZT2/95/5 antiferroelectric ceramic has the application prospect of negative electricity card effect application refrigeration devices which cannot be underestimated.

Claims (8)

1. An antiferroelectric ceramic material with giant negative electric-card effect, characterized in that the chemical composition of the antiferroelectric ceramic material is as follows:
(Pb1-3x/2Lax)(Zr0.95Ti0.05)O3；
the antiferroelectric ceramic material has a giant negative electric card effect;
x is 0.02, 0.04, 0.06, 0.08 or 0.1;
the negative electricity clamping effect of the antiferroelectric ceramic material is-0.26K to-3.25K under the field intensity of 55 kV/cm.
2. A method of preparing an antiferroelectric ceramic material according to claim 1, comprising the steps of:
s1) mixing a lead source, a titanium source, a zirconium source and a lanthanum source, performing ball milling, and calcining to obtain a first intermediate;
s2) carrying out secondary ball milling on the first intermediate, and after molding, sequentially carrying out glue removal treatment and high-temperature sintering to obtain the antiferroelectric ceramic material.
3. The preparation method according to claim 2, wherein the dispersant for ball milling in the step S1) is an alcohol solvent; the ball milling time is 20-30 h; the dispersing agent for the secondary ball milling in the step S2) is an alcohol solvent; the time of the secondary ball milling is 20-30 h.
4. The method of claim 2, wherein the temperature of the calcination is 700 ℃ to 900 ℃; and the calcining time is 3-8 h.
5. The preparation method according to claim 2, wherein the temperature of the degumming treatment is 550-700 ℃; the heating rate of the glue discharging treatment is 1-5 ℃/min.
6. The preparation method according to claim 2, wherein the temperature of the high-temperature sintering is 1000 ℃ to 1500 ℃; the high-temperature sintering time is 3-8 h; the heating rate of the high-temperature sintering is 1-5 ℃/min.
7. Use of the antiferroelectric ceramic material of claim 1 or the antiferroelectric ceramic material prepared according to any one of claims 2 to 6 as a refrigeration material.
8. A refrigeration device comprising the antiferroelectric ceramic material of claim 1 or the antiferroelectric ceramic material prepared according to any one of claims 2 to 6.
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