CN114907123B - A-site disubstituted silver niobate-based perovskite antiferroelectric ceramic material and preparation method thereof - Google Patents
A-site disubstituted silver niobate-based perovskite antiferroelectric ceramic material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses an A-site disubstituted silver niobate based perovskite antiferroelectric ceramic material and a preparation method thereof, which are prepared by a conventional solid phase reaction methodSynthesizing solid solution, and specifically operating the steps of: ag with 2 O，Nb 2 O 5 ，K 2 CO 3 And Sm 2 O 3 The silver niobate-based antiferroelectric ceramic material is prepared by weighing the raw materials in proportion, mixing, ball milling, drying, grinding, sieving, presintering, granulating, press forming and sintering. Under the applied electric field of 330kV/cm, the silver niobate-based perovskite antiferroelectric ceramic material has the density of 3.96J/cm 3 The energy storage density and the energy storage efficiency of 73.56 percent, and provides a new idea for improving the energy storage performance of the silver niobate-based material.
Description
Technical Field
The invention belongs to the technical field of lead-free dielectric energy storage materials, and particularly relates to an A-site disubstituted silver niobate-based perovskite antiferroelectric ceramic material and a preparation method thereof.
Background
With the rapid development of the electronic industry, there is an increasing demand for power storage devices. The current energy storage devices mainly have the following three types: batteries, supercapacitors, and dielectric capacitors. Compared with the first two energy storage devices, the electric energy stored by the dielectric capacitor can be rapidly released in an ultra-short time, so that the requirement of a pulse power system is met, and the device is expected to be applied to the fields of industry, medical treatment, military and the like. In the dielectric material, the antiferroelectric body has higher P m Smaller P r Certain advantages are presented in the energy storage field, and extensive research is caused.
However, antiferroelectric materials with excellent energy storage properties reported so far almost all contain a large amount of lead element. It is known that lead element can cause great harm to human body and environment during the manufacturing and using process, so that the searching of a novel lead-free antiferroelectric material has great significance.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides an A-site disubstituted silver niobate-based perovskite antiferroelectric ceramic material and a preparation method thereof, which reduce the hysteresis of silver niobate AFE-FE phase transition, thereby showing higher maximum polarization and smaller residual polarization and improving the energy storage performance.
The invention adopts the following technical scheme:
an A-site disubstituted silver niobate based perovskite antiferroelectric ceramic material comprises the following chemical compositions: (Ag) 1-x-3y K x Sm y )NbO 3 Wherein x, y is mole percent and 0.01<x＝y≤0.07。
Specifically, the thickness of the A-site disubstituted silver niobate based perovskite antiferroelectric ceramic material is 0.1-0.15 mm, and the energy storage density is 1.1-3.96J/cm 3 The energy storage efficiency is 42.1% -73.56%.
The invention also provides a method for preparing an A-site disubstituted silver niobate-based perovskite antiferroelectric ceramic material, which comprises the following steps:
s1, according to chemical composition (Ag) 1-x-3y K x Sm y )NbO 3 The calculated mass of the metering ratio x=y=0.01, 0.03, 0.05 and 0.07 in the formula is respectively weighed Ag 2 O，Nb 2 O 5 ，K 2 CO 3 And Sm 2 O 3 Powder;
s2, weighing Ag in the step S1 2 O，Nb 2 O 5 ，K 2 CO 3 And Sm 2 O 3 Mixing the powder, performing first ball milling treatment, and then sequentially performing drying, grinding and sieving treatment;
s3, presintering the mixed powder after the sieving treatment in the step S2, performing secondary ball milling treatment after natural cooling, taking out the powder, and drying to obtain a presintered powder;
s4, grinding the prefabricated powder obtained in the step S3, sieving to obtain screening powder, adding PVA solution with the mass concentration of 5% -6% into the screening powder, uniformly mixing to obtain granulating powder, and pressing the granulating powder into a blank;
s5, sintering the blank obtained in the step S4, and naturally cooling to obtain a sintered ceramic sheet;
and S6, polishing the sintered ceramic sheet obtained in the step S5, and naturally airing to obtain the A-site disubstituted silver niobate-based antiferroelectric ceramic material.
Specifically, in the step S2, the rotation speed of the first ball milling is 400-450 r/min, the time is more than or equal to 8 hours, the drying temperature is 65-70 ℃, and the 80-100 mesh screen is used for sieving treatment after grinding.
Specifically, in the step S3, the temperature of the presintering treatment is 950-1000 ℃, the time is 4-5 hours, the atmosphere is pure oxygen, the rotating speed of the second ball milling is 400-450 rpm, the time is 4-5 hours, and the drying temperature is 65-70 ℃.
Further, in the first ball milling and the second ball milling, raw materials to be ball milled: solvent: the mass ratio of the ball milling medium is 1 (1-1.25): (1.65-1.85).
Further, the solvent is absolute ethyl alcohol or water, and the ball milling medium is zirconia balls or alumina balls.
Specifically, in the step S4, a 60-100 mesh screen is used for sieving, the adding amount of PVA solution is 6-10% of the mass of the sieving powder, and the pressing pressure is 20-25 MPa.
Further, the mass concentration of the PVA solution is 5% -6%.
Specifically, in step S5, the sintering process is specifically:
heating to 600-650 ℃ at a speed of 5-6 ℃/min, preserving heat for 2-3 hours, continuously heating to 1140-1160 ℃ and preserving heat for 6-7 hours, cooling to 400-500 ℃, and naturally cooling to room temperature along with a furnace to obtain the sintered ceramic sheet.
Compared with the prior art, the invention has at least the following beneficial effects:
the invention relates to an A-site disubstituted silver niobate-based perovskite antiferroelectric ceramic material, which has the chemical general formula: (Ag) 1-x-3y K x Sm y )NbO 3 Wherein x, y is mole percent and 0.01<x=y is less than or equal to 0.07. Silver niobate is a typical perovskite structure, and Sm with smaller ionic radius is selected according to the principle of tolerance factor t 3+ Ion substituted Ag + Ions can stabilize antiferroelectric property and K with larger ion radius is selected + Ion substituted Ag + The ion can stabilize the ferroelectricity, a small amount of the two ions are combined to replace the A position together, and an 'slender' type electric hysteresis loop can be displayed, so that the energy storage performance of the ion is obviously improved, and when K is + And Sm 3+ At a content of more than 0.07, it is not completely solid-dissolved in the silver niobate substrate, so that 0.01 is set<x＝y≤0.07。
Furthermore, the thickness of the A-site disubstituted silver niobate-based perovskite antiferroelectric ceramic material is 0.1-0.15 mm, and a higher electric field can be applied by polishing the thickness to 0.1-0.15 mm, so that better energy storage performance is obtained.
Method for preparing A-site disubstituted silver niobate-based perovskite antiferroelectric ceramic material by weighing Ag 2 O，Nb 2 O 5 ，K 2 CO 3 And Sm 2 O 3 After powder is mixed, performing ball milling treatment for the first time to fully and uniformly mix and refine raw materials, and then sequentially performing drying, grinding and sieving treatment to ensure uniform granularity of the powder; presintering the mixed powder after sieving, performing secondary ball milling after natural cooling, taking out the powder and drying to obtain a pre-powder body, preliminarily synthesizing pure-phase pre-powder body by presintering the mixed powder body, obtaining a denser ceramic sample in the subsequent sintering process, and further refining the pre-powder body by performing secondary ball milling; grinding the pre-prepared powder, sieving to ensure uniform particle size of the powder to obtain screened powder, adding PVA solution with mass concentration of 5% -6% into the screened powder, uniformly mixing to obtain granulated powder, pressing the granulated powder into a blank, wherein PVA is used as an adhesive, and the PVA can increase the cohesiveness among the powder, so that the molding is easy; sintering the blank body to obtain a sintered ceramic sheet; polishing the sintered ceramic sheet to make it apply higher electric field, naturally airing to obtain A-site double substitutionSilver niobate-based antiferroelectric ceramic material of (a).
Further, the rotational speed of the first ball milling is 400-450 rpm, the time is more than or equal to 8 hours, if the rotational speed of the ball milling is less than 400 rpm, the powder is unevenly mixed at too small rotational speed, and the rotational speed is more than 450 rpm, the interior of the ball milling tank is possibly damaged, so the rotational speed of the ball milling is set to 400-450 rpm. The ball milling for the first time is to fully and uniformly mix the raw materials, so that the ball milling time is more than or equal to 8 hours to ensure the full mixing; the drying temperature is 65-70 ℃, the ignition point of absolute ethyl alcohol is 75 ℃, and if the temperature is higher than the ignition point, the sample burns, so that the drying is carried out at 65-70 ℃; after grinding, a 80-100 mesh screen is used for sieving, so that the raw material size can be ensured to be uniform and the raw material cannot be oversized.
Further, the presintering treatment is carried out at 950-1000 ℃ for 4-5 hours under pure oxygen atmosphere, so that Ag can be promoted under the oxygen atmosphere 2 O and Nb 2 O 5 Inhibit the generation of Ag simple substance, and is favorable for synthesizing high-quality single-phase AgNbO 3 And (3) a base ceramic sample. The presintering temperature is 950-1000 ℃, and the heat preservation time is 4-5 hours, so that the pure-phase prefabricated powder can be obtained. The rotation speed of the second ball milling is 400-450 rpm, the time is 4-5 hours, if the rotation speed of the ball milling is less than 400 rpm, the powder is mixed unevenly under the too small rotation speed, and if the rotation speed is more than 450 rpm, the damage in the ball milling tank can be possibly caused, so the rotation speed of the ball milling is 400-450 rpm, the size of the powder after presintering is reduced by the second ball milling, and the ball milling time is shorter than 4-5 hours. The drying temperature is set to 65-70 ℃, the ignition point of the absolute ethyl alcohol is 75 ℃, and if the temperature is higher than the ignition point, the sample burns, so that the drying at 65-70 ℃ is selected.
Further, in the first ball milling and the second ball milling, raw materials to be ball milled: solvent: the mass ratio of the ball milling medium is 1 (1-1.25) (1.65-1.85), and the raw materials to be ball milled are: the mass ratio of the solvent is 1 (1-1.25), so that the solvent can completely submerge the raw materials to be ball-milled, the grinding balls are difficult to move due to the fact that the adding amount is too small, and the adhesion of powder to the grinding balls is weakened due to the fact that the adding amount is too large; ball milling raw materials: the mass ratio of the ball milling media is 1 (1.65-1.85), the powder cannot be further refined due to too little ball milling media, and the grinding balls can be mutually pressed and overlapped due to too much ball milling media, so that the breaking capacity of each grinding ball cannot be fully exerted.
Furthermore, the solvent is absolute ethyl alcohol or water, the ball milling medium is zirconia balls or alumina balls, the absolute ethyl alcohol (or water) is used as the solvent because the absolute ethyl alcohol (or water) cannot react with the raw materials, and the zirconia balls (or alumina balls) are used as the ball milling medium because the absolute ethyl alcohol (or water) has high hardness and good toughness, and cannot pollute the raw materials. .
Further, the size uniformity of the granulated powder can be ensured by sieving with a 60-100-mesh screen, the addition amount of PVA solution is 6-10% of the mass of the sieved powder, so that the powder is fully and uniformly mixed with PVA, and the green embryo can be better molded under the pressing pressure of 20-25 Mpa.
Further, the PVA solution has a mass concentration of 5% -6%, the PVA solution is thinner when the concentration is less than 5%, the adhesion between the powder is poor, the PVA solution is sticky when the concentration is more than 6%, and the powder is easy to agglomerate in the granulating process.
Further, the temperature is raised to 600 to 650 ℃ at the speed of 5 to 6 ℃/min, the heat is preserved for 2 to 3 hours, the temperature is continuously raised to 1140 to 1160 ℃ and the heat is preserved for 6 to 7 hours, the temperature is cooled to 400 to 500 ℃, and the sintered ceramic sheet is obtained after natural cooling to room temperature along with a furnace. The temperature is kept for 2 to 3 hours at 600 to 650 ℃ to fully discharge PVA in the green body, sintering is carried out at 1140 to 1160 ℃ and the temperature is kept for 6 to 7 hours to reach the sintering condition of ceramic, the ceramic is cooled to 400 to 500 ℃ and then cooled to room temperature along with a furnace, the relative porosity can be reduced, and the better shrinkage of the ceramic is ensured.
In conclusion, the invention adopts the equivalent price K + Ions and alien Sm 3+ Ions replace the A site in the silver niobate-based antiferroelectric ceramic material together, and a solid solution is formed by a solid phase reaction method, so that the preparation process is simple and the repeatability is good; the releasable energy density of the obtained silver niobate based antiferroelectric material can reach 3.96J/cm 3 The energy storage efficiency reaches 73.56 percent, and the energy storage performance of the silver niobate-based ceramic material is improved.
The technical scheme of the invention is further described in detail through the drawings and the embodiments.
Drawings
FIG. 1 is a graph showing total energy storage density, effective energy storage density and energy effectiveness of an AKSN ceramic sample according to the invention under a maximum electric field with increased Sm content along with doped K;
fig. 2 is a schematic diagram of the effective energy storage density and energy effectiveness of the same component of the AKSN ceramic sample of the present invention at x=y=0.01;
fig. 3 is a schematic diagram of the effective energy storage density and energy effectiveness of the same component of the AKSN ceramic sample of the present invention at x=y=0.03;
fig. 4 is a schematic diagram of the effective energy storage density and energy effectiveness of the same component of the AKSN ceramic sample of the present invention at x=y=0.05;
fig. 5 is a schematic diagram of the effective energy storage density and energy effectiveness of the same component of the AKSN ceramic sample of the present invention at x=y=0.07.
Detailed Description
The following description of the present invention will be made clearly and fully, and it is apparent that the embodiments described are some, but not all, of the embodiments of the present invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
In the present invention, all embodiments and preferred methods of implementation mentioned herein may be combined with each other to form new solutions, unless otherwise specified.
In the present invention, all technical features mentioned herein and preferred features may be combined with each other to form new technical solutions, unless otherwise specified.
In the present invention, the percentage (%) or parts refer to weight percentage or parts by weight relative to the composition unless otherwise specified.
In the present invention, the components or preferred components thereof may be combined with each other to form a new technical solution, unless otherwise specified.
In the present invention, unless otherwise indicated, the numerical ranges "a-b" represent shorthand representations of any combination of real numbers between a and b, where a and b are both real numbers. For example, the numerical range "6-22" means that all real numbers between "6-22" have been listed throughout, and "6-22" is only a shorthand representation of a combination of these values.
The "range" disclosed herein may take the form of a lower limit and an upper limit, which may be one or more lower limits and one or more upper limits, respectively.
In the present invention, the term "and/or" as used herein refers to any and all possible combinations of one or more of the associated listed items, and includes such combinations.
In the present invention, each reaction or operation step may be performed sequentially or sequentially unless otherwise indicated. Preferably, the reaction processes herein are performed sequentially.
Unless otherwise defined, the technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. In addition, any method or material similar or equivalent to those described may be used in the present invention.
Silver niobate is a novel lead-free antiferroelectric material, exhibits unique double-hysteresis loop, and has phase-change electric field of high (120 kV/cm) and high polarization intensity (52 muC/cm) 2 ) Is considered to be the most potential antiferroelectric energy storage material. Based on microstructure design, the aim of optimizing the energy storage performance of the silver niobate based antiferroelectric material can be achieved through an A-site disubstituted chemical composition strategy, so that the silver niobate based antiferroelectric material with excellent energy storage performance is obtained.
The invention provides an A-site disubstituted silver niobate-based perovskite antiferroelectric ceramic material and a preparation method thereof, wherein a solid solution is synthesized by a conventional solid phase reaction method, and the specific operation steps are as follows: ag with 2 O，Nb 2 O 5 ，K 2 CO 3 And Sm 2 O 3 The silver niobate-based antiferroelectric ceramic material is prepared by weighing the raw materials in proportion, mixing, ball milling, drying, grinding, sieving, presintering, granulating, press forming and sintering. Under the additional electric field of 330kV/cm, the material has higher energy storageDensity (3.96J/cm) 3 ) And higher energy storage efficiency (73.56%), and provides a new idea for improving the energy storage performance of the silver niobate-based material.
The invention relates to an A-site disubstituted silver niobate-based perovskite antiferroelectric ceramic material, which comprises the following chemical components: (Ag) 1-x- 3y K x Sm y )NbO 3 Wherein x, y are mole percent and 0<x＝y≤0.07。
The invention relates to a preparation method of an A-site disubstituted silver niobate-based perovskite antiferroelectric ceramic material, which comprises the following steps:
s1, according to chemical composition (Ag) 1-x-3y K x Sm y )NbO 3 The calculated mass at the metering ratios x=y=0.01, 0.03, 0.05 and 0.07 of the formula (i) respectively weigh Ag 2 O，Nb 2 O 5 ，K 2 CO 3 And Sm 2 O 3 Powder;
s2, mixing the powder weighed in the step S1, placing the mixture in a ball milling tank for the first time, performing ball milling treatment, wherein a solvent used in the ball milling treatment is absolute ethyl alcohol (or water), a ball milling medium is zirconia balls (or alumina balls), the mass ratio of raw materials to be ball milled, the solvent and the ball milling medium is 1 (1-1.25) (1.65-1.85), the ball milling rotating speed is 400-450 r/min, the ball milling time is more than or equal to 8 hours, then drying the obtained mixed powder in an oven at 65-70 ℃, and sieving the powder with a 80-100-mesh screen after grinding;
s3, placing the mixed powder obtained in the step S2 into a tube furnace, introducing flowing oxygen, presintering for 4-5 hours at 950-1000 ℃, performing secondary ball milling treatment after natural cooling, taking out the powder after ball milling for 4-5 hours, and drying in a drying oven at 65-70 ℃ to obtain a pre-powder;
s4, grinding the prefabricated powder obtained in the step S3, passing through a 60-100-mesh screen to obtain screening powder, adding PVA solution with the mass concentration of 5-6% into the screening powder, uniformly mixing to obtain granulated powder, drying the granulated powder, weighing 0.5-0.55 g, placing into a metal mold with the diameter of 10-12 mm, and pressing into a blank under the uniaxial pressure of 20-25 MPa;
s5, placing the embryo obtained in the step S4 in Al 2 O 3 Placing the ceramic boat into a tube furnace to perform sintering treatment under pure oxygen, heating to 600-650 ℃ at a speed of 5-6 ℃/min, preserving heat for 2-3 hours, continuously heating to 1140-1160 ℃ and preserving heat for 6-7 hours, cooling to 400-500 ℃, naturally cooling to room temperature along with the furnace, and naturally cooling to obtain a sintered ceramic sheet;
and S6, polishing the sintered ceramic sheet obtained in the step S5 to a thickness of 0.1-0.15 mm, and naturally airing to obtain the A-site disubstituted silver niobate-based antiferroelectric ceramic material with high energy storage density.
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments of the present invention. The components of the embodiments of the present invention generally described and illustrated in the figures herein may be arranged and designed in a wide variety of different configurations. Thus, the following detailed description of the embodiments of the invention, as presented in the figures, is not intended to limit the scope of the invention, as claimed, but is merely representative of selected embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
A silver niobate-based antiferroelectric ceramic material with A-site disubstituted and high energy storage density has a chemical composition formula expressed by the following formula: (Ag) 0.96 K 0.01 Sm 0.01 )NbO 3 。
A preparation method of an A-site disubstituted silver niobate-based antiferroelectric ceramic material with high energy storage density comprises the following steps:
s1, calculating the mass of each composition according to the chemical composition, and respectively weighing Ag according to the corresponding mass 2 O，Nb 2 O 5 ，K 2 CO 3 And Sm 2 O 3 Powder;
s2, mixing the powder weighed in the step S1, placing the mixture in a ball milling tank for first ball milling treatment, wherein a solvent used in the ball milling treatment is absolute ethyl alcohol (or water), a ball milling medium is zirconia balls (or alumina balls), the mass ratio of raw materials to be ball milled, the solvent and the ball milling medium is 1:1:1.65, the ball milling rotating speed is 400 rpm, the ball milling time is 8 hours, drying the mixed powder in a drying oven at 65 ℃, and sieving the powder by using a 80-mesh sieve after grinding;
s3, placing the mixed powder after the sieving treatment in the step S2 into a tube furnace, introducing flowing oxygen, presintering for 4 hours at 950 ℃, performing secondary ball milling treatment after natural cooling, taking out the powder after ball milling for 4 hours, and drying in a drying oven at 65 ℃ to obtain a pre-powder;
s4, grinding the prefabricated powder obtained in the step S3, passing through a 60-mesh screen to obtain screening powder, adding PVA solution with the mass concentration of 5% into the screening powder, uniformly mixing to obtain granulated powder, drying the granulated powder, weighing 0.5g, placing the granulated powder into a metal mold with the diameter of 10mm, and pressing into a blank under the uniaxial pressure of 20 MPa;
s5, placing the embryo obtained in the step S4 in Al 2 O 3 Placing the ceramic boat into a tube furnace to perform sintering treatment under pure oxygen condition, heating to 600 ℃ at the speed of 5 ℃/min, keeping the temperature for 2 hours, continuously heating to 1140 ℃ and keeping the temperature for 6 hours, cooling to 400 ℃, naturally cooling to room temperature along with the furnace, and naturally cooling to obtain a sintered ceramic sheet;
and S6, polishing the sintered ceramic sheet obtained in the step S5 to a thickness of 0.15mm, and naturally airing to obtain the A-site disubstituted silver niobate-based antiferroelectric ceramic material with high energy storage density.
The effective energy storage density and energy storage efficiency of the ceramic material obtained in this example were calculated, and the result is shown in FIG. 2, and the energy storage density of the obtained ceramic material under an electric field of 140kV/cm was 1.1J/cm 3 The energy storage efficiency is 42.1%.
Example 2
A silver niobate-based antiferroelectric ceramic material with A-site disubstituted and high energy storage density has a chemical composition formula expressed by the following formula: (Ag) 0.88 K 0.03 Sm 0.03 )NbO 3 。
A preparation method of an A-site disubstituted silver niobate-based antiferroelectric ceramic material with high energy storage density comprises the following steps:
s1, calculating the mass of each composition according to the chemical composition, and respectively weighing Ag according to the corresponding mass 2 O，Nb 2 O 5 ，K 2 CO 3 And Sm 2 O 3 Powder;
s2, mixing the powder weighed in the step S1, placing the mixture in a ball milling tank for first ball milling treatment, wherein a solvent used in the ball milling treatment is absolute ethyl alcohol (or water), a ball milling medium is zirconia balls (or alumina balls), the mass ratio of raw materials to be ball milled, the solvent and the ball milling medium is 1:1.2:1.75, the ball milling rotating speed is 425 rpm, the ball milling time is 8 hours, drying the mixed powder in a drying oven at 65 ℃, and sieving the powder with a 80-mesh sieve after grinding;
s3, placing the mixed powder obtained in the step S2 into a tube furnace, introducing flowing oxygen, presintering for 4.5 hours at 950 ℃, performing secondary ball milling treatment after natural cooling, taking out the powder after ball milling for 4.5 hours, and drying in a drying oven at 65 ℃ to obtain a pre-powder;
s4, grinding the prefabricated powder obtained in the step S3, passing through a 80-mesh screen to obtain screening powder, adding PVA solution with the mass concentration of 5% into the screening powder, uniformly mixing to obtain granulated powder, drying the granulated powder, weighing 0.5g, placing the granulated powder into a metal mold with the diameter of 10mm, and pressing into a blank under the uniaxial pressure of 20 MPa;
s5, placing the embryo obtained in the step S4 in Al 2 O 3 Placing the ceramic boat into a tubular furnace to perform sintering treatment under pure oxygen, heating to 600 ℃ at the speed of 6 ℃/min, preserving heat for 2.5 hours, continuously heating to 1140 ℃ and preserving heat for 6 hours, cooling to 400 ℃, naturally cooling to room temperature along with the furnace, and naturally cooling to obtain a sintered ceramic sheet;
and S6, polishing the sintered ceramic sheet obtained in the step S5 to a thickness of 0.12mm, and naturally airing to obtain the A-site disubstituted silver niobate-based antiferroelectric ceramic material with high energy storage density.
The effective energy storage density and energy storage efficiency of the ceramic material obtained in this example were calculated, and the result is shown in FIG. 3, and the energy storage density of the obtained ceramic material under an electric field of 205kV/cm was 2.06J/cm 3 The energy storage efficiency is 52.65%.
Example 3
A silver niobate-based antiferroelectric ceramic material with A-site disubstituted and high energy storage density has a chemical composition formula expressed by the following formula: (Ag) 0.8 K 0.05 Sm 0.05 )NbO 3 。
A preparation method of an A-site disubstituted silver niobate-based antiferroelectric ceramic material with high energy storage density comprises the following steps:
s1, calculating the mass of each composition according to the chemical composition, and respectively weighing Ag according to the corresponding mass 2 O，Nb 2 O 5 ，K 2 CO 3 And Sm 2 O 3 Powder;
s2, mixing the powder weighed in the step S1, performing ball milling treatment for the first time in a ball milling tank, wherein a solvent used in the ball milling treatment is absolute ethyl alcohol (or water), a ball milling medium is zirconia balls (or alumina balls), the mass ratio of raw materials to be ball milled, the solvent and the ball milling medium is 1:1.25:1.85, the ball milling rotating speed is 425 rpm, the ball milling time is 8 hours, drying the mixed powder obtained in the step S2 in a 70 ℃ oven, and sieving the powder by using a 90-mesh sieve after grinding;
s3, placing the mixed powder obtained in the step 2 into a tube furnace, introducing flowing oxygen, presintering for 5 hours at 1000 ℃, performing secondary ball milling treatment after natural cooling, taking out the powder after ball milling for 5 hours, and drying in a drying oven at 70 ℃ to obtain a pre-powder;
s4, grinding the pre-prepared powder, passing through a 80-mesh screen to obtain screening powder, adding PVA solution with the mass concentration of 6% into the screening powder, uniformly mixing to obtain granulated powder, drying the obtained granulated powder, weighing 0.55g, placing the obtained granulated powder into a metal mold with the diameter of 12mm, and pressing into a blank under the uniaxial pressure of 25 MPa;
s5, placing the embryo obtained in the step S4 in Al 2 O 3 Putting into a porcelain boatSintering in a furnace under pure oxygen condition, heating to 650 ℃ at a speed of 6 ℃/min, preserving heat for 3 hours, continuously heating to 1140 ℃ and preserving heat for 6.5 hours, cooling to 500 ℃, naturally cooling to room temperature along with the furnace, and naturally cooling to obtain a sintered ceramic sheet;
and S6, polishing the sintered ceramic sheet obtained in the step S5 to a thickness of 0.1mm, and naturally airing to obtain the A-site disubstituted silver niobate-based antiferroelectric ceramic material with high energy storage density.
The effective energy storage density and energy storage efficiency of the ceramic material obtained in this example were calculated, and the result is shown in FIG. 4, and the energy storage density of the obtained ceramic material under an electric field of 350kV/cm was 3.53J/cm 3 The energy storage efficiency is 59.5%.
Example 4
A silver niobate-based antiferroelectric ceramic material with A-site disubstituted and high energy storage density has a chemical composition formula expressed by the following formula: (Ag) 0.72 K 0.07 Sm 0.07 )NbO 3 。
A preparation method of an A-site disubstituted silver niobate-based antiferroelectric ceramic material with high energy storage density comprises the following steps:
s1, calculating the mass of each composition according to the chemical composition, and respectively weighing Ag according to the corresponding mass 2 O，Nb 2 O 5 ，K 2 CO 3 And Sm 2 O 3 Powder;
s2, mixing the powder weighed in the step S1, performing ball milling treatment for the first time in a ball milling tank, wherein a solvent used in the ball milling treatment is absolute ethyl alcohol (or water), a ball milling medium is zirconia balls (or alumina balls), the mass ratio of raw materials to be ball milled, the solvent and the ball milling medium is 1:1.25:1.85, the ball milling rotating speed is 450 r/min, the ball milling time is 8.5 hours, drying the mixed powder obtained in the step S2 in a 70 ℃ oven, and sieving the powder with a 100-mesh sieve after grinding;
s3, placing the mixed powder obtained in the step S3 into a tube furnace, introducing flowing oxygen, presintering for 5 hours at 1000 ℃, performing secondary ball milling treatment after natural cooling, taking out the powder after ball milling for 5 hours, and drying in a drying oven at 70 ℃ to obtain a pre-powder;
s4, grinding the prefabricated powder obtained in the step S3, passing through a 100-mesh screen to obtain screening powder, adding PVA solution with the mass concentration of 6% into the screening powder, uniformly mixing to obtain granulated powder, drying the granulated powder, weighing 0.55g, placing the granulated powder into a metal mold with the diameter of 12mm, and pressing into a blank under the uniaxial pressure of 25 MPa;
s5, placing the embryo obtained in the step S4 in Al 2 O 3 Placing the ceramic boat into a tubular furnace to perform sintering treatment under pure oxygen condition, heating to 650 ℃ at the speed of 6 ℃/min, keeping the temperature for 3 hours, continuously heating to 1160 ℃ and keeping the temperature for 7 hours, cooling to 500 ℃, naturally cooling to room temperature along with the furnace, and naturally cooling to obtain a sintered ceramic sheet;
and S6, polishing the sintered ceramic sheet obtained in the step S5 to a thickness of 0.1mm, and naturally airing to obtain the A-site disubstituted silver niobate-based antiferroelectric ceramic material with high energy storage density.
The effective energy storage density and energy storage efficiency of the ceramic material obtained in this example were calculated, and the result is shown in fig. 5. The energy storage density of the obtained ceramic material is 3.96J/cm under the electric field of 330kV/cm 3 The energy storage efficiency is 73.56%.
The samples obtained in the above examples were tested for their polarization strength as a function of electric field, and their energy storage densities W were calculated by the formulas (1), (2) and (3), respectively store Effective energy storage density W rec And energy efficiency η.
Wherein W is store Is the total energy storage density; w (W) rec Is the effective energy storage density; e is the electric field strength; p is the polarization intensity; p (P) max Is the maximum polarization intensity; p (P) r Is the remnant polarization.
As can be seen from FIG. 1, with K + Ions and Sm 3+ The increase in ion doping content increases the releasable energy storage density and energy storage efficiency of the ceramic sample, and when x=y=0.05, the ceramic sample has a maximum total energy storage density of 5.94J/cm 3 . When x=y=0.07, the ceramic sample achieved 3.96J/cm 3 Is a high releasable energy density of 73.56%.
In conclusion, the A-site disubstituted silver niobate-based perovskite antiferroelectric ceramic material and the preparation method thereof adopt the same-valence K + Ions and alien Sm 3+ Ions replace the A site in the silver niobate-based antiferroelectric ceramic material together, and a solid solution is formed by a solid phase reaction method, so that the preparation process is simple and the repeatability is good. The hysteresis of silver niobate AFE-FE phase transition is reduced, thereby showing higher maximum polarization and smaller residual polarization, and improving the energy storage density and the energy storage efficiency.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and not for limiting the same; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the invention.
Claims (5)
1. A method for preparing A-site disubstituted silver niobate based perovskite antiferroelectric ceramic material comprises the following chemical compositions: (Ag) 1-x-3y K x Sm y )NbO 3 Wherein x, y is mole percent and 0.01<x=y is less than or equal to 0.07, the thickness of the A-site disubstituted silver niobate-based perovskite antiferroelectric ceramic material is 0.1-0.15 mm, and the energy storage density is highIs 1.1 to 3.96J/cm 3 The energy storage efficiency is 42.1% -73.56%; the method comprises the following steps:
s1, according to chemical composition (Ag) 1-x-3y K x Sm y )NbO 3 The metering ratio in the method is respectively weighing Ag 2 O，Nb 2 O 5 ，K 2 CO 3 And Sm 2 O 3 Powder;
s2, weighing Ag in the step S1 2 O，Nb 2 O 5 ，K 2 CO 3 And Sm 2 O 3 Mixing the powder, performing first ball milling treatment, and then sequentially performing drying, grinding and sieving treatment;
s3, presintering the mixed powder after sieving in the step S2, performing secondary ball milling after natural cooling, taking out the powder and drying to obtain a presintered powder, wherein in the primary ball milling and the secondary ball milling, raw materials to be ball milled are: solvent: the mass ratio of the ball milling medium is 1 (1-1.25): (1.65-1.85), wherein the solvent is absolute ethyl alcohol or water, and the ball milling medium is zirconia balls or alumina balls;
s4, grinding the prefabricated powder obtained in the step S3, sieving to obtain screening powder, adding PVA solution with the mass concentration of 5% -6% into the screening powder, uniformly mixing to obtain granulating powder, and pressing the granulating powder into a blank;
s5, sintering the blank obtained in the step S4, and naturally cooling to obtain a sintered ceramic sheet;
and S6, polishing the sintered ceramic sheet obtained in the step S5, and naturally airing to obtain the A-site disubstituted silver niobate-based antiferroelectric ceramic material.
2. The preparation method of the A-site disubstituted silver niobate-based perovskite antiferroelectric ceramic material according to claim 1, wherein in the step S2, the rotation speed of the first ball milling is 400-450 rpm, the time is more than or equal to 8 hours, the drying temperature is 65-70 ℃, and the 80-100 mesh screen mesh is used for sieving after grinding.
3. The preparation method of the A-site disubstituted silver niobate-based perovskite antiferroelectric ceramic material according to claim 1, wherein in the step S3, the presintering treatment is performed at 950-1000 ℃ for 4-5 hours, the atmosphere is pure oxygen, the rotation speed of the second ball milling is 400-450 rpm, the time is 4-5 hours, and the drying temperature is 65-70 ℃.
4. The preparation method of the A-site disubstituted silver niobate-based perovskite antiferroelectric ceramic material is characterized in that in the step S4, a 60-100-mesh screen is used for sieving, the addition amount of PVA solution is 6% -10% of the mass of the sieving powder, and the pressing pressure is 20-25 MPa.
5. The method for preparing a-site disubstituted silver niobate based perovskite antiferroelectric ceramic material according to claim 1, wherein in step S5, the sintering treatment is specifically:
heating to 600-650 ℃ at a speed of 5-6 ℃/min, preserving heat for 2-3 hours, continuously heating to 1140-1160 ℃ and preserving heat for 6-7 hours, cooling to 400-500 ℃, and naturally cooling to room temperature along with a furnace to obtain the sintered ceramic sheet.
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