CN114907123A - 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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- 229910010293 ceramic material Inorganic materials 0.000 title claims abstract description 58
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 238000004146 energy storage Methods 0.000 claims abstract description 67
- 238000002156 mixing Methods 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 19
- 239000002994 raw material Substances 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000000843 powder Substances 0.000 claims description 113
- 238000000498 ball milling Methods 0.000 claims description 95
- 239000000919 ceramic Substances 0.000 claims description 37
- 238000001816 cooling Methods 0.000 claims description 33
- 238000001035 drying Methods 0.000 claims description 29
- 239000000203 mixture Substances 0.000 claims description 23
- 238000000227 grinding Methods 0.000 claims description 22
- 238000007873 sieving Methods 0.000 claims description 21
- 239000002904 solvent Substances 0.000 claims description 19
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical group O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 18
- 238000005245 sintering Methods 0.000 claims description 18
- 239000000126 substance Substances 0.000 claims description 17
- 238000010438 heat treatment Methods 0.000 claims description 16
- 239000011812 mixed powder Substances 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 13
- 238000003825 pressing Methods 0.000 claims description 11
- 238000005303 weighing Methods 0.000 claims description 11
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 9
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 8
- 238000005498 polishing Methods 0.000 claims description 7
- 238000003860 storage Methods 0.000 claims description 2
- 150000003378 silver Chemical class 0.000 abstract description 30
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 abstract description 15
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- 239000004332 silver Substances 0.000 abstract description 15
- 230000005684 electric field Effects 0.000 abstract description 12
- 239000000463 material Substances 0.000 abstract description 10
- 238000003746 solid phase reaction Methods 0.000 abstract description 4
- 239000006104 solid solution Substances 0.000 abstract description 4
- 239000000243 solution Substances 0.000 description 23
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- 150000002500 ions Chemical group 0.000 description 8
- 229910052760 oxygen Inorganic materials 0.000 description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 239000012071 phase Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 229910001414 potassium ion Inorganic materials 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
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- 238000005469 granulation Methods 0.000 description 2
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- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000003989 dielectric material Substances 0.000 description 1
- 230000005621 ferroelectricity Effects 0.000 description 1
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Abstract
The invention discloses 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 preparation method comprises the following specific operation steps: mixing Ag with water 2 O，Nb 2 O 5 ，K 2 CO 3 And Sm 2 O 3 And the raw materials are weighed according to a certain proportion, mixed and ball-milled, dried, ground, screened, presintered, granulated, pressed, molded and sintered to obtain the silver niobate-based antiferroelectric ceramic material. Under an external electric field of 330kV/cm, the silver niobate-based perovskite antiferroelectric ceramic material has the thickness of 3.96J/cm 3 The energy storage density and the energy storage efficiency of 73.56 percent provide 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, the demand of people for power storage devices is increasing. The current energy storage devices mainly have three types: batteries, supercapacitors and dielectric capacitors. Compared with the former two energy storage devices, the electric energy stored by the dielectric capacitor can be quickly released in an ultrashort time, 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. Among dielectric materials, antiferroelectric has a higher P m And smaller P r Has certain advantages in the field of energy storage, and has led to extensive research.
However, the antiferroelectric materials with excellent energy storage performance reported at present almost contain a large amount of lead element. As is known to all, lead element can generate great harm to human bodies and the environment in the manufacturing and using processes, so that the finding of a novel lead-free antiferroelectric material has very important significance.
Disclosure of Invention
The technical problem to be solved by the present invention is to provide an a-site disubstituted silver niobate-based perovskite antiferroelectric ceramic material and a preparation method thereof, which reduce the phase transition lag of silver niobate AFE-FE, thereby showing higher maximum polarization and smaller remnant polarization, and improving the energy storage performance thereof.
The invention adopts the following technical scheme:
an A-site disubstituted silver niobate-based perovskite antiferroelectric ceramic material comprises the following chemical components: (Ag) 1-x-3y K x Sm y )NbO 3 Wherein x and y are mole percentages 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 the A-site disubstituted silver niobate-based perovskite antiferroelectric ceramic material, which comprises the following steps:
s1, chemical composition (Ag) 1-x-3y K x Sm y )NbO 3 The mass calculated from the above stoichiometric ratio of x to y of 0.01, 0.03, 0.05 and 0.07 was measured for each of 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, pre-burning the mixed powder sieved in the step S2, naturally cooling, performing secondary ball milling, taking out the powder and drying to obtain prefabricated powder;
s4, grinding the prefabricated powder obtained in the step S3, sieving to obtain screened powder, adding a PVA solution with the mass concentration of 5% -6% into the screened powder, mixing uniformly to obtain granulated powder, and pressing the granulated powder into a blank;
s5, sintering the blank obtained in the step S4, and naturally cooling to obtain a sintered ceramic wafer;
and S6, polishing the sintered ceramic wafer obtained in the step S5, and naturally airing to obtain the A-site disubstituted silver niobate-based antiferroelectric ceramic material.
Specifically, in step S2, the rotation speed of the first ball milling is 400-450 rpm, the time is greater than or equal to 8 hours, the drying temperature is 65-70 ℃, and the first ball milling is performed by sieving with a 80-100 mesh sieve.
Specifically, in step S3, the temperature of the pre-sintering treatment is 950 to 1000 ℃, the time is 4 to 5 hours, the atmosphere is pure oxygen, the rotation speed of the second ball milling is 400 to 450 rpm, the time is 4 to 5 hours, and the drying temperature is 65 to 70 ℃.
Further, in the first ball milling and the second ball milling, the ball milling raw materials: solvent: the mass ratio of the ball milling medium is 1 (1-1.25): (1.65-1.85).
Furthermore, the solvent is absolute ethyl alcohol or water, and the ball milling medium is zirconia balls or alumina balls.
Specifically, in step S4, a screen mesh of 60-100 meshes is used for sieving, the adding amount of the PVA solution is 6-10% of the mass of the sieved 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 specifically includes:
heating to 600-650 ℃ at the speed of 5-6 ℃/min, preserving heat for 2-3 hours, continuously heating to 1140-1160 ℃, preserving heat for 6-7 hours, cooling to 400-500 ℃, and naturally cooling to room temperature along with the furnace to obtain the sintered ceramic plate.
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 and y are mole percentages and 0.01<x is equal to or less than 0.07. Silver niobate is a typical perovskite structure, and Sm with a smaller ionic radius is selected according to the principle of tolerance factor t 3+ Ion substituted Ag + Ions, which can stabilize antiferroelectric properties, and a larger ionic radius of K + Ion substituted Ag + Ions can stabilize the ferroelectricity of the composite material, and a small amount of the two ions jointly replace the A site to show a slender electric hysteresis loop, so that the energy storage performance of the composite material is obviously improved, and when K is used + And Sm 3+ When the content is more than 0.07, it cannot be completely dissolved in the silver niobate matrix, 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 when the thickness of the A-site disubstituted silver niobate-based perovskite antiferroelectric ceramic material is polished to be 0.1-0.15 mm, so that the good energy storage performance is obtained.
A method for preparing A-site disubstituted silver niobate-based perovskite antiferroelectric ceramic material is calledTaking Ag 2 O，Nb 2 O 5 ，K 2 CO 3 And Sm 2 O 3 After the powder is mixed, carrying out first ball milling treatment to fully and uniformly mix and refine the raw materials, and then sequentially carrying out drying, grinding and sieving treatment to ensure that the particle size of the powder is uniform; pre-burning the mixed powder after sieving, naturally cooling, performing secondary ball milling, taking out the powder, drying to obtain a prefabricated powder, pre-burning the mixed powder to preliminarily synthesize a pure-phase prefabricated powder, obtaining a compact ceramic sample in the subsequent sintering process, and further refining the prefabricated powder by performing secondary ball milling; grinding the prefabricated powder, sieving to ensure uniform powder granularity to obtain screened powder, then adding a PVA solution with the mass concentration of 5-6% into the screened powder, uniformly mixing to obtain granulated powder, pressing the granulated powder into a blank, wherein the PVA is an adhesive and can increase the cohesiveness among the powder by adding the PVA so as to be easy to form; sintering the blank to obtain a sintered ceramic sheet; and (3) polishing the sintered ceramic sheet to enable the sintered ceramic sheet to apply a higher electric field, and naturally airing to obtain the A-site disubstituted silver niobate-based antiferroelectric ceramic material.
Furthermore, the rotation speed of the first ball milling is 400-450 rpm, the time is more than or equal to 8 hours, if the rotation speed of the ball milling is less than 400 rpm, the powder with too low rotation speed is not uniformly mixed, and the rotation speed is more than 450 rpm, the internal damage of the ball milling tank can be caused, so the rotation speed of the ball milling is set to be 400-450 rpm. The first ball milling aims at fully and uniformly mixing 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 the absolute ethyl alcohol is 75 ℃, if the temperature is higher than the ignition point, the sample is burnt, and therefore, the drying is carried out at 65-70 ℃; after grinding, a sieve with 80-100 meshes is used for sieving, so that the raw materials are uniform in size and cannot be overlarge.
Further, the temperature of the pre-sintering treatment is 950-1000 ℃, the time is 4-5 hours, the atmosphere is pure oxygen, and Ag can be promoted in the oxygen atmosphere 2 O and Nb 2 O 5 The reaction of (2) inhibits the generation of Ag simple substance, and is beneficial to synthesizing high qualitySingle phase AgNbO 3 A base ceramic sample. And the pre-sintering temperature is 950-1000 ℃, and the heat preservation time is 4-5 hours, so that 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 not uniformly mixed when the rotation speed is too low, and the rotation speed is more than 450 rpm, the internal damage of the ball milling tank can be caused, so the rotation speed of the ball milling is set to be 400-450 rpm, the size of the powder after presintering is reduced by the second ball milling, and the ball milling time is 4-5 hours. The drying temperature is set to be 65-70 ℃, the ignition point of the absolute ethyl alcohol is 75 ℃, if the temperature is higher than the ignition point, the sample is burnt, and therefore, the drying is carried out at 65-70 ℃.
Further, in the first ball milling and the second ball milling, the ball milling raw materials: solvent: the mass ratio of the ball milling medium is 1 (1-1.25) to 1.65-1.85, and the ball milling raw materials: 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 too small addition amount, and the adhesion of powder to the grinding balls is weakened due to too large addition amount; and (3) ball-milling raw materials: the mass ratio of the ball milling media is 1 (1.65-1.85), the powder cannot be further refined when the ball milling media are too small, the grinding balls can be mutually pressed and stacked when the ball milling media are too large, and the crushing 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) does not 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 does not pollute the raw materials. .
Furthermore, the powder after granulation can be ensured to be uniform in size by sieving with a 60-100-mesh sieve, the PVA solution is added in an amount which is 6-10% of the mass of the sieved powder, so that the powder can be fully and uniformly mixed with PVA, and the green blank can be well molded under the pressing pressure of 20-25 Mpa.
Furthermore, the mass concentration of the PVA solution is 5% -6%, the PVA solution is thinner due to the concentration being less than 5%, the powder has poor adhesion, the PVA solution is viscous due to the concentration being more than 6%, and the powder is easy to agglomerate in the granulation process.
Further, heating to 600-650 ℃ at a speed of 5-6 ℃/min, preserving heat for 2-3 hours, continuously heating to 1140-1160 ℃, preserving heat for 6-7 hours, cooling to 400-500 ℃, and naturally cooling to room temperature along with the furnace to obtain the sintered ceramic wafer. And (3) preserving heat for 2-3 hours at 600-650 ℃ to fully discharge the PVA in the blank, sintering at 1140-1160 ℃ and preserving heat for 6-7 hours to achieve the sintering condition of the ceramic, cooling to 400-500 ℃, and slowly cooling to room temperature along with the furnace to reduce the relative porosity and ensure the better shrinkage rate of the ceramic.
In summary, the present invention employs the same price K + Ions and aliovalents Sm 3+ The ions jointly replace the A site in the silver niobate-based antiferroelectric ceramic material, and the solid solution is formed by a solid-phase reaction method, so that the preparation process is simple and the repeatability is good; the obtained silver niobate-based antiferroelectric material has the releasable energy density of 3.96J/cm 3 The energy storage efficiency reaches 73.56%, and the energy storage performance of the silver niobate-based ceramic material is improved.
The technical solution of the present invention is further described in detail by the accompanying drawings and embodiments.
Drawings
FIG. 1 is a schematic diagram of the total energy storage density, the effective energy storage density and the energy efficiency of AKSN ceramic samples according to the invention under the maximum electric field with increasing content of K, Sm doped;
fig. 2 is a schematic diagram of the effective energy storage density and energy efficiency of the same component of AKSN ceramic sample at x ═ y ═ 0.01;
fig. 3 is a schematic diagram of the effective energy storage density and energy efficiency of the same composition of AKSN ceramic sample at x ═ y ═ 0.03;
fig. 4 is a schematic diagram of the effective energy storage density and energy efficiency of the same composition of AKSN ceramic sample at x ═ y ═ 0.05;
fig. 5 is a schematic diagram of the effective energy storage density and energy efficiency of the same composition at x-y-0.07 for AKSN ceramic samples of the present invention.
Detailed Description
The technical solutions of the present invention will be described clearly and completely below, and it should be apparent that the described embodiments are some, but not all, embodiments of the present invention. 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.
In the present invention, all the embodiments and preferred methods mentioned herein can be combined with each other to form a new technical solution, if not specifically stated.
In the present invention, all the technical features mentioned herein and preferred features may be combined with each other to form a new technical solution, if not specifically stated.
In the present invention, the percentage (%) or parts means the weight percentage or parts by weight with respect to the composition, if not otherwise specified.
In the present invention, the components referred to or the preferred components thereof may be combined with each other to form a novel embodiment, if not specifically stated.
In the present invention, unless otherwise stated, the numerical range "a-b" represents a shorthand representation of any combination of real numbers between a and b, where a and b are both real numbers. For example, a numerical range of "6 to 22" means that all real numbers between "6 to 22" have been listed herein, and "6 to 22" is simply a shorthand representation of the combination of these values.
A "range" disclosed herein can be in the form of one or more lower limits and one or more upper limits, respectively, in terms of lower limits and upper limits.
As used herein, the term "and/or" refers to any and all possible combinations of one or more of the associated listed items and includes such combinations.
In the present invention, unless otherwise specified, the individual reactions or operation steps may be performed sequentially or may be performed in sequence. Preferably, the reaction processes herein are carried out sequentially.
Unless otherwise defined, technical and scientific terms used herein have the same meaning as is familiar to those skilled in the art. In addition, any methods or materials similar or equivalent to those described herein can also be used in the present invention.
Silver niobate is a novel lead-free antiferroelectric material, shows unique double hysteresis loop, and has high phase-change electric field (120 kV/cm) and large polarization intensity (52 mu C/cm) 2 ) Is considered as the most potential antiferroelectric energy storage material. Based on microstructure design, the purpose of optimizing the energy storage performance of the 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 preparation method comprises the following specific operation steps: mixing Ag with water 2 O，Nb 2 O 5 ，K 2 CO 3 And Sm 2 O 3 The silver niobate-based antiferroelectric ceramic material is obtained by mixing, ball milling, drying, grinding, sieving, presintering, granulating, press-forming and sintering the raw materials which are weighed in proportion. Under an external electric field of 330kV/cm, the material has higher energy storage density (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 and 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, chemical composition (Ag) 1-x-3y K x Sm y )NbO 3 The amounts of Ag in (1) and (2) were measured in terms of the mass ratios x to y of 0.01, 0.03, 0.05 and 0.07, respectively 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 the solvent used in the ball milling treatment is absolute ethyl alcohol (or water), the ball milling medium is zirconia balls (or alumina balls), the ball milling raw materials, the solvent and the ball milling medium are mixed according to the mass ratio of 1 (1-1.25) (1.65-1.85), the ball milling rotation speed is 400-450 r/m, the ball milling time is more than or equal to 8 hours, drying the obtained mixed powder in an oven at 65-70 ℃, and screening the powder by using a screen mesh of 80-100 meshes after grinding;
s3, placing the mixed powder obtained in the step S2 in a tube furnace, introducing flowing oxygen, pre-burning for 4-5 hours at 950-1000 ℃, naturally cooling, performing secondary ball milling treatment, taking out the powder after ball milling for 4-5 hours, and drying in an oven at 65-70 ℃ to obtain prefabricated powder;
s4, grinding the prefabricated powder obtained in the step S3, sieving the ground prefabricated powder with a sieve of 60-100 meshes to obtain screened powder, adding a PVA solution with the mass concentration of 5-6% into the screened powder, uniformly mixing to obtain granulated powder, drying the granulated powder, weighing 0.5-0.55 g of the granulated powder, placing the weighed granulated powder into a metal mold with the diameter of 10-12 mm, and pressing the granulated powder into a blank under the uniaxial pressure of 20-25 MPa;
s5, placing the blank obtained in the step S4 in Al 2 O 3 Putting the ceramic boat into a tube furnace, sintering under the condition of pure oxygen, heating to 600-650 ℃ at the speed of 5-6 ℃/min, preserving heat for 2-3 hours, continuing heating to 1140-1160 ℃, 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 wafer;
and S6, polishing the sintered ceramic plate 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.
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are some, 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 present invention, 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 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.
Example 1
An A-site disubstituted silver niobate-based antiferroelectric ceramic material with high energy storage density, the chemical composition formula of which is 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 component 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 ball milling raw material, the solvent and the ball milling medium are mixed according to the mass ratio of 1:1:1.65, the ball milling rotation speed is 400 r/min, the ball milling time is 8 hours, drying the mixed powder in an oven at 65 ℃, and sieving the powder by using a 80-mesh sieve after grinding;
s3, placing the mixed powder sieved in the step S2 in a tube furnace, introducing flowing oxygen, pre-burning for 4 hours at 950 ℃, naturally cooling, performing secondary ball milling for 4 hours, taking out the powder after ball milling, and drying in an oven at 65 ℃ to obtain prefabricated powder;
s4, grinding the prefabricated powder obtained in the step S3, sieving the ground prefabricated powder with a 60-mesh sieve to obtain screened powder, adding a PVA solution with the mass concentration of 5% into the screened powder, uniformly mixing to obtain granulated powder, drying the granulated powder, weighing 0.5g of the granulated powder, placing the weighed granulated powder into a metal die with the diameter of 10mm, and pressing the granulated powder into a blank under the uniaxial pressure of 20 MPa;
s5, placing the blank obtained in the step S4 in Al 2 O 3 Putting the ceramic boat into a tube furnace, sintering under the condition of pure oxygen, heating to 600 ℃ at the speed of 5 ℃/min, keeping the temperature for 2 hours, continuing 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 wafer;
s6, polishing the sintered ceramic plate obtained in the step S5 to the 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 the energy storage efficiency of the ceramic material obtained in the embodiment are calculated, the result is shown in FIG. 2, and the energy storage density of the obtained ceramic material is 1.1J/cm under an electric field of 140kV/cm 3 The energy storage efficiency was 42.1%.
Example 2
An A-site disubstituted silver niobate-based antiferroelectric ceramic material with high energy storage density, the chemical composition formula of which is 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 component 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 ball milling raw material, the solvent and the ball milling medium are mixed according to the mass ratio of 1:1.2:1.75, the ball milling rotating speed is 425 revolutions per minute, the ball milling time is 8 hours, drying the mixed powder in an oven at 65 ℃, and sieving the powder by using a 80-mesh sieve after grinding;
s3, placing the mixed powder obtained in the step S2 in a tube furnace, introducing flowing oxygen, pre-burning for 4.5 hours at 950 ℃, naturally cooling, performing secondary ball milling treatment, taking out the powder after ball milling for 4.5 hours, and drying in a drying oven at 65 ℃ to obtain prefabricated powder;
s4, grinding the prefabricated powder obtained in the step S3, sieving the ground prefabricated powder with a 80-mesh sieve to obtain screened powder, adding a PVA solution with the mass concentration of 5% into the screened powder, uniformly mixing to obtain granulated powder, drying the granulated powder, weighing 0.5g of the granulated powder, placing the weighed granulated powder into a metal die with the diameter of 10mm, and pressing the granulated powder into a blank under the uniaxial pressure of 20 MPa;
s5, placing the blank obtained in the step S4 in Al 2 O 3 Putting the ceramic boat into a tube furnace, sintering under the condition of pure oxygen, heating to 600 ℃ at the speed of 6 ℃/min, keeping the temperature for 2.5 hours, continuing heating to 1140 ℃, 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 wafer;
s6, grinding the sintered ceramic plate obtained in the step S5 to the 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 the energy storage efficiency of the ceramic material obtained in the embodiment are calculated, the result is shown in FIG. 3, and the energy storage density of the obtained ceramic material is 2.06J/cm under an electric field of 205kV/cm 3 The energy storage efficiency was 52.65%.
Example 3
An A-site disubstituted silver niobate-based antiferroelectric ceramic material with high energy storage density, the chemical composition formula of which is 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 component 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 ball milling time is 8 hours when the mass ratio of a ball milling raw material, the solvent and the ball milling medium is 1:1.25:1.85, the ball milling rotating speed is 425 revolutions per minute, and the mixed powder obtained in the step S2 is dried in an oven at 70 ℃, and the powder is sieved by a 90-mesh screen after being ground;
s3, placing the mixed powder obtained in the step 2 in a tube furnace, introducing flowing oxygen, pre-burning for 5 hours at 1000 ℃, naturally cooling, performing secondary ball milling treatment, taking out the powder after ball milling for 5 hours, and drying in an oven at 70 ℃ to obtain prefabricated powder;
s4, grinding the prefabricated powder, sieving the ground prefabricated powder by a 80-mesh sieve to obtain screened powder, adding a PVA solution with the mass concentration of 6% into the screened powder, uniformly mixing to obtain granulated powder, drying the obtained granulated powder, weighing 0.55g of the granulated powder, placing the weighed granulated powder into a metal die with the diameter of 12mm, and pressing the granulated powder into a blank under the uniaxial pressure of 25 MPa;
s5, placing the blank obtained in the step S4 in Al 2 O 3 Putting the ceramic boat into a tube furnace, sintering under the condition of pure oxygen, heating to 650 ℃ at the speed of 6 ℃/min, keeping the temperature for 3 hours, continuing heating to 1140 ℃ and keeping the temperature for 6.5 hours, cooling to 500 ℃, naturally cooling to room temperature along with the furnace, and naturally cooling to obtain a sintered ceramic wafer;
s6, polishing the sintered ceramic plate obtained in the step S5 to the 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 the energy storage efficiency of the ceramic material obtained in the embodiment are calculated, the result is shown in figure 4, and the energy storage density of the obtained ceramic material is 3.53J/cm under an electric field of 350kV/cm 3 The energy storage efficiency was 59.5%.
Example 4
An A-site disubstituted silver niobate-based antiferroelectric ceramic material with high energy storage density, the chemical composition formula of which is 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 component 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 ball milling time is 8.5 hours when the mass ratio of a ball milling raw material, the solvent and the ball milling medium is 1:1.25:1.85, the ball milling rotating speed is 450 revolutions per minute, and the mixed powder obtained in the step S2 is dried in an oven at 70 ℃, and the powder is sieved by a 100-mesh screen after being ground;
s3, placing the mixed powder obtained in the step S3 in a tube furnace, introducing flowing oxygen, pre-burning for 5 hours at 1000 ℃, naturally cooling, performing secondary ball milling treatment, taking out the powder after ball milling for 5 hours, and drying in an oven at 70 ℃ to obtain prefabricated powder;
s4, grinding the prefabricated powder obtained in the step S3, sieving the ground prefabricated powder with a 100-mesh sieve to obtain screened powder, adding a PVA solution with the mass concentration of 6% into the screened powder, uniformly mixing to obtain granulated powder, drying the granulated powder, weighing 0.55g of the granulated powder, placing the weighed granulated powder into a metal die with the diameter of 12mm, and pressing the granulated powder into a blank under the uniaxial pressure of 25 MPa;
s5, placing the blank obtained in the step S4 in Al 2 O 3 Putting the ceramic boat into a tube furnace, sintering under the condition of pure oxygen, heating to 650 ℃ at the speed of 6 ℃/min, keeping the temperature for 3 hours, continuing 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 wafer;
s6, polishing the sintered ceramic plate obtained in the step S5 to the thickness of 0.1mm, and naturally airing to obtain the A-site disubstituted silver niobate-based antiferroelectric ceramic material with high energy storage density.
Effective energy storage Density of the ceramic Material obtained in this exampleThe energy storage efficiency was calculated and the results are shown in fig. 5. The energy storage density of the obtained ceramic material is 3.96J/cm under an electric field of 330kV/cm 3 The energy storage efficiency was 73.56%.
The polarization intensity of the sample obtained in the above embodiment was tested for the performance varying with the electric field, and then the energy storage density W was calculated by the formulas (1), (2) and (3) respectively store Effective energy storage density W rec And an energy efficiency η.
Wherein, W store The total energy storage density; w rec Is the effective energy storage density; e is the electric field strength; p is the polarization; p max Is the maximum polarization intensity; p r The remanent polarization.
As can be seen from FIG. 1, with K + Ions and Sm 3+ The releasable energy storage density and the energy storage efficiency of the ceramic sample are increased along with the increase of the ion doping content, and when x is equal to y and is equal to 0.05, the maximum total energy storage density of the ceramic sample is 5.94J/cm 3 . When x-y-0.07, the ceramic sample achieved 3.96J/cm 3 High releasable energy density and high energy storage efficiency of 73.56%.
In conclusion, the A-site disubstituted silver niobate-based perovskite antiferroelectric ceramic material and the preparation method thereof adopt the K with the same valence + Ions and aliovalents Sm 3+ The ions jointly replace the A site in the silver niobate-based antiferroelectric ceramic material, and the solid solution is formed by a solid-phase reaction method, so that the preparation process is simple and the repeatability is good. Reduces the phase change lag of silver niobate AFE-FE, thereby showing higher maximum polarization and higher polarizationAnd the small residual polarization improves the energy storage density and the energy storage efficiency.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (10)
1. An A-site disubstituted silver niobate-based perovskite antiferroelectric ceramic material is characterized in that the A-site disubstituted silver niobate-based perovskite antiferroelectric ceramic material has the chemical composition: (Ag) 1-x-3y K x Sm y )NbO 3 Wherein x and y are mole percentages and 0.01<x＝y≤0.07。
2. The A-site disubstituted silver niobate-based perovskite antiferroelectric ceramic material according to claim 1, wherein the A-site disubstituted silver niobate-based perovskite antiferroelectric ceramic material has a thickness of 0.1 to 0.15mm and a storage energy density of 1.1 to 3.96J/cm 3 The energy storage efficiency is 42.1% -73.56%.
3. A method for preparing an a-site disubstituted silver niobate-based perovskite antiferroelectric ceramic material of claim 1 or 2, comprising the steps of:
s1, chemical composition (Ag) 1-x-3y K x Sm y )NbO 3 The mass calculated from the above stoichiometric ratio of x to y of 0.01, 0.03, 0.05 and 0.07 was measured for each of 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 of powdersThen carrying out first ball milling treatment, and then sequentially carrying out drying, grinding and sieving treatment;
s3, pre-burning the mixed powder sieved in the step S2, naturally cooling, performing secondary ball milling, taking out the powder and drying to obtain prefabricated powder;
s4, grinding the prefabricated powder obtained in the step S3, sieving to obtain screened powder, adding a PVA solution with the mass concentration of 5% -6% into the screened powder, mixing uniformly to obtain granulated powder, and pressing the granulated powder into a blank;
s5, sintering the blank obtained in the step S4, and naturally cooling to obtain a sintered ceramic wafer;
and S6, polishing the sintered ceramic wafer obtained in the step S5, and naturally airing to obtain the A-site disubstituted silver niobate-based antiferroelectric ceramic material.
4. The method for preparing the A-site disubstituted silver niobate-based perovskite antiferroelectric ceramic material according to claim 3, wherein in step S2, the rotation speed of the first ball milling is 400-450 rpm, the time is not less than 8 hours, the drying temperature is 65-70 ℃, and the grinding is carried out by sieving with a sieve of 80-100 meshes.
5. The method for preparing an A-site disubstituted silver niobate-based perovskite antiferroelectric ceramic material according to claim 3, wherein in step S3, the pre-sintering treatment is performed at 950 to 1000 ℃ for 4 to 5 hours in pure oxygen atmosphere, the rotation speed of the second ball milling is 400 to 450 rpm for 4 to 5 hours, and the drying temperature is 65 to 70 ℃.
6. The preparation method of the A-site disubstituted silver niobate-based perovskite antiferroelectric ceramic material according to claim 4 or 5, wherein in the first ball milling and the second ball milling, the raw materials to be ball milled: solvent: the mass ratio of the ball milling medium is 1 (1-1.25): (1.65-1.85).
7. The method for preparing the A-site disubstituted silver niobate-based perovskite antiferroelectric ceramic material according to claim 6, wherein the solvent is absolute ethanol or water, and the ball milling medium is zirconia balls or alumina balls.
8. The method for preparing the A-site disubstituted silver niobate-based perovskite antiferroelectric ceramic material according to claim 3, wherein in step S4, a sieve of 60-100 meshes is used for sieving, the PVA solution is added in an amount of 6-10% of the mass of the sieved powder, and the pressing pressure is 20-25 MPa.
9. The method for preparing the A-site disubstituted silver niobate-based perovskite antiferroelectric ceramic material according to claim 8, wherein the mass concentration of the PVA solution is 5-6%.
10. The method for preparing an a-site disubstituted silver niobate-based perovskite antiferroelectric ceramic material according to claim 3, wherein in step S5, the sintering treatment specifically comprises:
heating to 600-650 ℃ at the speed of 5-6 ℃/min, preserving heat for 2-3 hours, continuously heating to 1140-1160 ℃, preserving heat for 6-7 hours, cooling to 400-500 ℃, and naturally cooling to room temperature along with the furnace to obtain the sintered ceramic plate.
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