CN109180178B - Barium strontium titanate-based lead-free relaxation ferroelectric ceramic with high energy storage density and preparation method thereof - Google Patents
Barium strontium titanate-based lead-free relaxation ferroelectric ceramic with high energy storage density and preparation method thereof Download PDFInfo
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Abstract
The invention relates to aThe barium strontium titanate based lead-free relaxation ferroelectric ceramic with high energy storage density comprises the following chemical components: (1-x) (Ba0.55Sr0.45)TiO3‑xBi(Mg2/3Nb1/3)O3Wherein x is more than 0 and less than or equal to 0.15.
Description
Technical Field
The invention relates to a lead-free energy storage ceramic material, in particular to a barium strontium titanate-based lead-free relaxation ferroelectric ceramic with high energy storage density and a preparation method thereof, belonging to the field of functional ceramics.
Background
With the continuous development of scientific technology, the application field of the pulse power technology is wider and wider. Pulsed power technology stores energy at a relatively slow rate by means of a low power source and then compresses the energy into high power pulses by a pulsed power system, which can then be discharged to a specific load in a very short time (up to nanoseconds). As pulsed power technology has been constrained by energy storage technology, electrical energy storage materials have received increasing attention in recent years. The energy storage material has a wide range of coverage, including fuel cells, lithium ion batteries, electrochemical supercapacitors, electrostatic capacitors, and the like. Although various batteries have high energy storage density, the output power is low due to the fact that the batteries are limited by charge carriers with slow migration speed; the dielectric capacitor stores energy by means of polarization response under an external electric field, and can realize that the electric energy is directly stored in the two polar plates in the form of static charge, and the process does not involve the diffusion of substances, so that the dielectric capacitor has extremely high charge and discharge speed and high output power density.
Currently, dielectrics used in energy storage capacitors can be largely classified into two categories, ceramics and polymers. The polymer has high energy storage density due to high dielectric breakdown strength, but the polymer has low melting point and reduced dielectric property at high temperature; the ceramic has unique mechanical and chemical stability, and can be suitable for extreme environments such as high temperature and high pressure. Ceramic dielectrics are classified into four categories according to different polarization response mechanisms under an electric field: linear media, ferroelectric media, relaxor ferroelectric media, and antiferroelectric media. The polarization strength of the linear dielectric increases linearly with the external electric field, the dielectric constant is basically kept unchanged, and the linear dielectric generally has high dielectric breakdown strength and low dielectric loss, but the polarization strength is small, so that the linear dielectric is not beneficial to energy storage; ferroelectric media have large spontaneous polarization and moderate dielectric breakdown strength, but their energy storage density and efficiency are low due to excessive remanent polarization; the antiferroelectric medium has larger spontaneous polarization intensity and smaller remanent polarization intensity, thereby having larger energy storage density, but because the antiferroelectric-ferroelectric phase change exists under the action of an electric field and is accompanied with larger strain, the antiferroelectric medium is easy to have dielectric breakdown under a turning electric field. Unlike ferroelectric media with long-range ordered electric domain structures and high remanent polarization, relaxor ferroelectric media with polar nano micro-regions exhibit small remanent polarization, high saturation polarization and low coercive field. These properties of the relaxor ferroelectric medium are very advantageous for achieving high energy storage density and energy storage efficiency, but most of these materials are lead-containing systems. Since 2002, the european union, the united states and japan have enacted strict environmental laws (WEEE/RoHS) that restrict or prohibit the use of various toxic substances including Pb in electronic devices. On the other hand, the energy storage density of the conventional dielectric capacitor is low, so that the volume of an energy storage device is large and occupies 40-60% of the volume of the whole equipment. Therefore, it is an important trend of development of dielectric ceramics to increase energy storage density and achieve lead-free.
Barium strontium titanate ((Ba)xSr1-x)TiO3BST for short) is barium titanate (BaTiO)3) And strontium titanate (SrTiO)3) The dielectric constant of the material is high, the dielectric loss is low, and the dielectric property of the material can be adjusted in a wide temperature range by changing the Ba/Sr ratio. H.B.Yang et al (J.Eur.Ceram.Soc.38, 1367-containing 1373(2018)) in Ba0.4Sr0.6TiO3In which Bi is added2O3-B2O3-SiO2The maximum energy storage density of the glass frit is 1.98J/cm under 279kV/cm3The efficiency was 90.57%. J.Y.Wu et al (N)ano Energy,50, 723-732(2018)) by doping Sr and Li into BNT to construct a relaxor ferroelectric ceramic with a polar nano micro-region (PNRs) structure, the maximum Energy storage density is 1.7J/cm3The energy storage efficiency was 87.2%.
Disclosure of Invention
The invention aims to provide a barium strontium titanate-based lead-free relaxation ferroelectric ceramic with high energy storage density and a preparation method thereof, namely (1-x) (Ba)0.55Sr0.45)TiO3-xBi(Mg2/3Nb1/3)O3The effective energy storage density of the ferroelectric ceramic at room temperature can reach 4.55J/cm3。
In one aspect, the present invention provides a barium strontium titanate-based lead-free relaxor ferroelectric ceramic material, which has a chemical composition of: (1-x) (Ba0.55Sr0.45)TiO3-xBi(Mg2/3Nb1/3)O3Wherein x is more than 0 and less than or equal to 0.15.
The invention is based on that barium strontium titanate is in a cubic paraelectric phase structure when the Sr content is more than 0.4 at room temperature, and Bi is considered at the same time3+And O2-Can increase the spontaneous polarization intensity, Mg2+And Nb5+Destroying the ferroelectric long-range ordered structure, constructing a polar nano micro-area, and designing the following components: (1-x) (Ba0.55Sr0.45)TiO3-xBi(Mg2/3Nb1/3)O3High energy storage density and energy storage efficiency can be simultaneously realized, and lead-free is realized. The ceramic material is in a pseudo-cubic phase at room temperature, the polar nano micro-regions can be coupled into a long-range ordered electric domain structure with orientation tending to the direction of an electric field under the action of the electric field, and the polar nano micro-regions with random orientation can be recovered under the action of thermal motion after the electric field is removed.
Preferably, the barium strontium titanate-based lead-free relaxor ferroelectric ceramic material has an energy storage density (effective energy storage density) of 3.0J/cm3The above.
The effective energy storage density of the barium strontium titanate-based lead-free relaxation ferroelectric ceramic material at room temperature can reach 4.55J/cm3The energy storage efficiency may be 80% or more.
On the other hand, the invention also provides a preparation method of the barium strontium titanate-based lead-free relaxor ferroelectric ceramic material, which comprises the following steps:
according to (Ba)0.55Sr0.45)TiO3Mixing a Ba source, a Sr source and a Ti source according to the stoichiometric ratio, drying, briquetting, and carrying out first synthesis at 1100-1200 ℃ to obtain BST ceramic powder;
the Bi source, the Mg source, the Nb source and the BST ceramic powder are mixed according to the proportion of (1-x) (Ba)0.55Sr0.45)TiO3-xBi(Mg2/ 3Nb1/3)O3Mixing the raw materials according to the stoichiometric ratio, drying, briquetting, and carrying out secondary synthesis at 900-1000 ℃ to obtain BST-BMN ceramic powder;
adding a binder into the BST-BMN ceramic powder, granulating, aging, pressing and forming, and removing plastic to obtain a green body; and sintering the green body to obtain the barium strontium titanate-based lead-free relaxor ferroelectric ceramic material.
The invention prepares BST ceramic powder by a solid phase method, mixes the BST ceramic powder with a Bi source, an Mg source and an Nb source to synthesize BST-BMN ceramic powder, and prepares the barium strontium titanate-based lead-free relaxation ferroelectric ceramic material by molding, plastic removal and sintering. The volatilization of Bi is reduced and the synthesis is more sufficient by regulating and optimizing the components, and the lead-free BST-BMN ferroelectric ceramic with high energy storage density and high energy storage efficiency is prepared. The ceramic prepared by the invention has the characteristics of high dielectric breakdown strength, large effective energy storage density and high energy storage efficiency, and the effective energy storage density can reach 4.55J/cm at room temperature3The energy storage efficiency can be more than 80 percent, and the prepared (Ba) is prepared under the same conditions0.55Sr0.45)TiO3Compared with ceramics, the effective energy storage density is improved by 2.85J/cm3The amplitude is improved by 167.6 percent, and the energy storage efficiency is improved by 25.1 percent. The lead-free relaxation ferroelectric ceramic material is expected to be applied to the technical field of high-power pulse. Moreover, the method has simple process, low requirement on equipment and low production cost.
The Ba source may be BaTiO3、BaCO3、Ba(NO3)2、(CH3COO)2At least one of Ba. The above-mentionedThe Sr source can be SrTiO3、SrCO3、Sr(NO3)2、(CH3COO)2Sr. The Ti source may be BaTiO3、SrTiO3、TiO2At least one of (1).
The BST ceramic powder can be BaTiO3、SrTiO3Powder, or BaCO3、SrCO3And TiO2And (3) powder.
The time for the first synthesis can be 2-6 hours.
The source of Bi can be Bi2O3、Bi(NO3)3、C6H9BiO6At least one of (1). The Mg source may be MgO, MgCO3、CH4Mg2O6At least one of (1). The Nb source may be Nb2O5、Nb(OH)5At least one of (1).
The time of the second synthesis can be 2-6 hours.
The temperature of plastic removal can be 600-700 ℃, and the time can be 2-6 hours.
The sintering temperature can be 1250-1350 ℃, and the sintering time can be 2-6 hours.
Preferably, the green body is covered with the BST-BMN ceramic powder and sintered. By covering the green compact with ceramic powder having the same composition, volatilization of the Bi component can be prevented.
In yet another aspect, the present invention also provides a ferroelectric ceramic element made of any one of the barium strontium titanate-based lead-free relaxor ferroelectric ceramic materials described above.
The ferroelectric ceramic element can be obtained by processing any barium strontium titanate-based lead-free relaxation ferroelectric ceramic material into a required size, cleaning, printing silver, drying and burning silver.
Drawings
FIG. 1 shows the conventional solid phase method for preparing Ba0.55Sr0.45TiO3And (1-x) (Ba0.55Sr0.45)TiO3-xBi(Mg2/ 3Nb1/3)O3(X ═ 0.05, 0.07, 0.10) of the ceramic material at room temperature X-ray diffraction pattern (left panel (a)) and its partial enlarged view (right panel (b));
fig. 2(a) -2 (d) are graphs showing the variation of dielectric constant and dielectric loss with temperature at different frequencies of barium strontium titanate-based ceramic samples; wherein FIG. 2(a) shows Ba0.55Sr0.45TiO3(comparative example 1); FIG. 2(b) shows 0.95 (Ba)0.55Sr0.45)TiO3-0.05Bi(Mg2/3Nb1/3)O3(example 1); FIG. 2(c) shows 0.93 (Ba)0.55Sr0.45)TiO3-0.07Bi(Mg2/3Nb1/3)O3(example 2); FIG. 2(d) shows 0.90 (Ba)0.55Sr0.45)TiO3-0.10Bi(Mg2/3Nb1/3)O3(example 3);
FIG. 3 is a hysteresis loop at the highest electric field strength at room temperature of 1Hz for the barium strontium titanate-based ceramic samples of the examples and the comparative ceramic samples;
fig. 4 is a graph showing the change of the energy storage characteristics with the electric field in example 2.
Detailed Description
The present invention is further described below in conjunction with the following embodiments, which are intended to illustrate and not to limit the present invention.
The invention relates to a barium strontium titanate-based lead-free relaxation ferroelectric ceramic with high energy storage density and a preparation method thereof. The ceramic material comprises the following components: (1-x) (Ba0.55Sr0.45)TiO3-xBi(Mg2/3Nb1/3)O3Wherein x is more than 0 and less than or equal to 0.15, and x is mole percent. The preparation method of the ceramic material comprises the following steps: a Ba source, a Sr source and a Ti source (e.g., BaTiO)3And SrTiO3Or BaCO3、SrCO3And TiO2) Push (Ba)0.55Sr0.45)TiO3Proportioning materials according to a stoichiometric ratio, drying, briquetting, and synthesizing at 1100-1200 ℃ for 2-6 hours to obtain BST ceramic powder; a Bi source, a Mg source, a Nb source (e.g. Bi)2O3、MgO、Nb2O5) And BST ceramic powder according to (1-x) (Ba)0.55Sr0.45)TiO3-xBi(Mg2/3Nb1/3)O3(x is more than 0 and less than or equal to 0.15), mixing according to a stoichiometric ratio, drying, briquetting, synthesizing for 2-6 hours at 900-1000 ℃ to obtain BST-BMN ceramic powder, adding a binder for granulation, molding, and removing plastic to obtain a green body: and sintering the green body at 1250-1350 ℃ to prepare the barium strontium titanate-based lead-free relaxation ferroelectric ceramic with high energy storage density. The ceramic prepared by the invention has the characteristics of high breakdown strength, large effective energy storage density and high energy storage efficiency, and the effective energy storage density can reach 4.55J/cm at room temperature3The energy storage efficiency can be more than 80 percent compared with that of (Ba) prepared under the same conditions0.55Sr0.45)TiO3Compared with ceramics, the effective energy storage density is improved by 2.85J/cm3The amplitude is improved by 167.6 percent, and the energy storage efficiency is improved by 25.1 percent. Here. "effective energy storage density" refers to the energy density that can be released after charging. The lead-free relaxation ferroelectric ceramic material is expected to be applied to the technical field of high-power pulse.
The invention is based on that barium strontium titanate is in a cubic paraelectric phase structure when the Sr content is more than 0.4 at room temperature, and Bi is considered at the same time3+And O2-Can increase the spontaneous polarization intensity, Mg2+And Nb5+Destroying ferroelectric long-range ordered structure, constructing polar nano micro region, and designing (1-x) (Ba)0.55Sr0.45)TiO3-xBi(Mg2/3Nb1/3)O3Wherein x is more than 0 and less than or equal to 0.15, preferably 0.05 and less than or equal to 0.1, can simultaneously realize high energy storage density and energy storage efficiency and realize lead-free. When x is more than 0 and less than or equal to 0.15, the composite material has the advantages of high solid solution degree and large dielectric constant.
Hereinafter, a method for preparing a barium strontium titanate-based lead-free relaxor ferroelectric ceramic according to the present invention is schematically illustrated.
First, according to (Ba)0.55Sr0.45)TiO3Mixing Ba source, Sr source and Ti source according to the stoichiometric ratio to obtain powder A to be synthesized. BaTiO can be used as Ba source3(barium titanate), BaCO3(barium carbonate), Ba (NO)3)2(barium nitrate), (CH)3COO)2Ba (barium acetate), and the like. SrTiO can be used as Sr source3Strontium titanate (SrCO)3(strontium carbonate), Sr (NO)3)2(strontium nitrate), (CH)3COO)2Sr (strontium acetate), and the like. As the Ti source, BaTiO can be used3、SrTiO3、TiO2(titanium dioxide), and the like. In one example, BaTiO may be used3、SrTiO3Powder, or BaCO3、SrCO3And TiO2Powder as raw material (Ba)0.55Sr0.45)TiO3Proportioning corresponding to the stoichiometric ratio of the elements. The mixing method may be, for example, wet ball milling. In this case, the raw materials may be mixed for 24 to 48 hours in a mass ratio of 1 (4.5 to 5.2) to 1.5 to 1.7, wherein the ball-milling medium may be zirconium balls or agate balls. The raw material mixture may be dried and sieved (e.g., 40-120 mesh sieve) after mixing.
And then, briquetting the powder A to be synthesized, carrying out first synthesis, and cooling to room temperature along with the furnace to obtain BST ceramic powder. The pressure of the pressing block can be 4-6 MPa. The temperature of the first synthesis can be 1100-1200 ℃, the time can be 2-6 hours, and the heating rate can be less than or equal to 2 ℃/min.
Or the sample can be crushed (ground) after the first synthesis and sieved (for example, sieved by a 40-120 mesh sieve) to obtain powder with the particle size of 1-5 microns.
Next, the Bi source, the Mg source, the Nb source and the BST ceramic powder are mixed in accordance with (1-x) (Ba)0.55Sr0.45)TiO3-xBi(Mg2/ 3Nb1/3)O3And (x is more than 0 and less than or equal to 0.15) to obtain powder B to be synthesized. Bi can be used as the Bi source2O3(bismuth trioxide) and Bi (NO)3)3(bismuth nitrate) and C6H9BiO6(bismuth acetate), and the like. As the Mg source, MgO (magnesium oxide) or MgCO can be used3(magnesium carbonate), CH4Mg2O6(basic magnesium carbonate), and the like. Nb source may be Nb2O5(niobium oxide), Nb (OH)5(niobium hydroxide), and the like. The mixing method may be, for example, wet ball milling.In this case, the raw materials may be mixed for 24 to 48 hours in a mass ratio of 1 (4.5 to 5.2) to 1.5 to 1.7, wherein the ball-milling medium may be zirconium balls or agate balls. The raw material mixture may be dried and sieved (e.g., 40-120 mesh sieve) after mixing.
And then, briquetting the powder B to be synthesized, and carrying out secondary synthesis to obtain BST-BMN ceramic powder. The pressure of the pressing block can be 4-6 MPa. The conditions for the second synthesis may be: heating to 900-1000 ℃ at a heating rate of not higher than 2 ℃/min, preserving heat for 2-6 hours, and cooling to room temperature along with the furnace. The powder B to be synthesized can also be synthesized in a closed environment (such as a closed alumina crucible) so as to inhibit the volatilization of Bi.
The sample may also be reground (ground) and sieved (e.g., 40 mesh) after the second synthesis.
And then, adding a binder into the BST-BMN ceramic powder, granulating, aging, pressing and forming, and performing plastic discharging to obtain a green body (ceramic biscuit). The binder can be polyvinyl alcohol (PVA), polyvinyl butyral (PVB) and the like, the concentration of the binder is 7%, and the adding amount of the binder can be 5-7% of the weight of the ceramic powder. The aging time can be 21-25 hours. It may also be sieved after aging (e.g., 40 mesh sieve). In one example, the molding process may be, for example: the obtained powder was dry-pressed to obtain a green compact having a diameter of 13mm, but the size is not limited to this size and can be set as required. The pressure of the pressing forming can be 1.3-2.0 MPa.
Or the BST-BMN ceramic powder is finely ground and dried by a ball milling method before the binder is added, so that powder with the grain size of 0.5-1.5 mu m is obtained. In one example, the wet ball milling method is to finely mill the ceramic powder for 24 to 48 hours according to the mass ratio of (5.0 to 5.6) to (1.4 to 1.6) of the ceramic powder, the ball and the deionized water, wherein the ball milling medium can be zirconium balls or agate balls.
The plastic removing conditions can be as follows: heating to 600-700 ℃ at a heating rate of not higher than 2 ℃/min, preserving heat for 2-6 hours, and cooling to room temperature along with the furnace. The organic binder can be removed through plastic removal, and the blank has certain mechanical strength.
Subsequently, the green body is sintered. The sintering temperature (for example, the sintering is carried out by adopting a high-temperature furnace) can be 1250-1350 ℃, the time can be 2-6 hours, and the heating rate can be less than or equal to 2 ℃/min. The green body may be sintered by covering it with a BST-BMN ceramic powder. By covering the green compact with ceramic powder having the same composition, volatilization of the Bi component can be prevented. The green body may also be sintered in a closed environment.
Cooling to room temperature along with the furnace to obtain the barium strontium titanate-based lead-free relaxor ferroelectric ceramic material. The barium strontium titanate-based lead-free relaxation ferroelectric ceramic material is in a pseudo cubic phase at room temperature, polar nano micro regions can be coupled into a long-range ordered electric domain structure with orientation tending to the direction of an electric field under the action of the electric field, and the polar nano micro regions with random orientation can be recovered under the action of thermal motion after the electric field is removed.
The lead-free relaxation ferroelectric ceramic material is expected to be applied to the technical field of high-power pulse. In one example, the sintered ceramic may be processed to a desired size, cleaned, silver printed, dried, and silver fired to obtain the ferroelectric ceramic element.
The silver firing conditions can be as follows: heating to 700-800 ℃ at a heating rate of not higher than 2 ℃/min, and preserving heat for 10-30 minutes. The ferroelectric ceramic element prepared by the barium strontium titanate-based lead-free relaxation ferroelectric ceramic material has the advantages of high dielectric breakdown strength, large effective energy storage density and high energy storage efficiency.
The invention has the advantages that:
the barium strontium titanate-based lead-free relaxation ferroelectric ceramic material has the characteristics of high dielectric breakdown strength, large effective energy storage density and high energy storage efficiency, and the effective energy storage density reaches 4.55J/cm at room temperature3Energy storage efficiency of more than 80%, and prepared under the same conditions (Ba)0.55Sr0.45)TiO3Compared with ceramics, the effective energy storage density is improved by 2.85J/cm3The amplitude is improved by 167.6 percent, and the energy storage efficiency is improved by 25.1 percent.
The present invention will be described in detail by way of examples. It is also to be understood that the following examples are illustrative of the present invention and are not to be construed as limiting the scope of the invention, and that certain insubstantial modifications and adaptations of the invention by those skilled in the art may be made in light of the above teachings. The specific process parameters and the like of the following examples are also only one example of suitable ranges, i.e., those skilled in the art can select the appropriate ranges through the description herein, and are not limited to the specific values exemplified below.
Example 1:
the composition of the material is
0.95(Ba0.55Sr0.45)TiO3-0.05Bi(Mg2/3Nb1/3)O3
(1) With BaTiO3、SrTiO3Powder as raw material according to (Ba)0.55Sr0.45)TiO3Preparing stoichiometric ratio, mixing by wet ball milling method, ball milling and mixing for 24 hours according to the mass ratio of ball to deionized water of 1:4.5:1.7, drying, sieving with 40 mesh sieve, pressing into blocks under the pressure of 5MPa, raising the temperature to 1150 ℃ at the rate of 2 ℃/min, preserving the temperature for 4 hours, and synthesizing (Ba)0.55Sr0.45)TiO3Powder;
(2) grinding the powder prepared in the step (1), sieving with a 40-mesh sieve, and mixing with Bi2O3、MgO、Nb2O5The raw materials are mixed according to the proportion of 0.95 (Ba)0.55Sr0.45)TiO3-0.05Bi(Mg2/3Nb1/3)O3The preparation method comprises the steps of preparing according to the stoichiometric ratio, mixing the raw materials according to the mass ratio of 1:5:1.55 of balls to deionized water for 24 hours, drying, sieving by a 40-mesh sieve, pressing into large blocks under the pressure of 5MPa, raising the temperature to 1000 ℃ at the heating rate of 2 ℃/min, preserving the temperature for 2 hours, and synthesizing 0.95 (Ba)0.55Sr0.45)TiO3-0.05Bi(Mg2/3Nb1/3)O3Powder;
(3) and (3) grinding the powder prepared in the step (2), sieving the powder by a 40-mesh sieve, finely grinding the powder by a wet ball grinding method for 24 hours according to the mass ratio of the raw materials, namely balls and deionized water of 1:5:1.5, and drying the finely ground powder. Then adding 5 wt.% of PVA binder, granulating, briquetting, aging for 24 hours, sieving with a 40-mesh sieve, pressing into a green body with the diameter of 13mm under the pressure of 1.6MPa, then heating to 600 ℃, preserving heat for 4 hours, and removing plastic to obtain a ceramic biscuit;
(4) putting the ceramic biscuit into an alumina crucible, covering ceramic powder with the same composition on the ceramic biscuit in order to prevent volatilization of a Bi component, covering an alumina cover plate with a ground opening, heating to 1325 ℃ at the heating rate of 2 ℃/min, preserving heat for 2 hours, and cooling to room temperature along with a furnace to obtain a ceramic material;
(5) processing the sintered ceramic sample into a thickness of 0.2mm, cleaning, drying, printing silver paste, drying again, raising the temperature to 750 ℃ at the heating rate of 2 ℃/min, and preserving the temperature for 30 minutes to obtain a ceramic element;
(6) an X-ray diffraction analyzer (XRD) was used to determine the crystal structure and phase structure of the synthesized powder and sintered ceramic samples. Dielectric properties were tested with a Novocontrol broadband dielectric impedance spectrometer. Testing a ceramic electric hysteresis loop by adopting a TF-2000 ferroelectric analyzer;
(7) the ceramic element prepared in this example 1 was subjected to the unipolar hysteresis loop test at the highest electric field strength at room temperature, and the results are shown in fig. 3, and the maximum effective energy storage density, dielectric breakdown strength, and energy storage efficiency are shown in table 1.
Example 2:
the composition of the material is
0.93(Ba0.55Sr0.45)TiO3-0.07Bi(Mg2/3Nb1/3)O3
(1) With BaTiO3、SrTiO3Powder as raw material according to (Ba)0.55Sr0.45)TiO3Preparing stoichiometric ratio, mixing by wet ball milling method, ball milling and mixing for 24 hours according to the mass ratio of ball to deionized water of 1:4.5:1.7, drying, sieving with 40 mesh sieve, pressing into blocks under the pressure of 5MPa, raising the temperature to 1150 ℃ at the rate of 2 ℃/min, preserving the temperature for 4 hours, and synthesizing (Ba)0.55Sr0.45)TiO3Powder;
(2) grinding the powder prepared in the step (1), sieving with a 40-mesh sieve, and mixing with Bi2O3、MgO、Nb2O5Raw materials were as follows 0.93 (Ba)0.55Sr0.45)TiO3-0.07Bi(Mg2/3Nb1/3)O3The raw materials are mixed for 24 hours according to the mass ratio of 1:5:1.55 of the ball to the deionized water, the mixture is dried and sieved by a 40-mesh sieve, the mixture is pressed into large blocks under the pressure of 5MPa, the temperature is increased to 1000 ℃ at the heating rate of 2 ℃/min, the temperature is kept for 2 hours, and 0.93 (Ba) is synthesized0.55Sr0.45)TiO3-0.07Bi(Mg2/3Nb1/3)O3Powder;
(3) and (3) grinding the powder prepared in the step (2), sieving the powder by a 40-mesh sieve, finely grinding the powder by a wet ball grinding method for 24 hours according to the mass ratio of the raw materials, namely balls and deionized water of 1:5:1.5, and drying the finely ground powder. Then adding 5 wt.% of PVA binder, granulating, briquetting, aging for 24 hours, sieving with a 40-mesh sieve, pressing into a green body with the diameter of 13mm under the pressure of 1.6MPa, then heating to 600 ℃, preserving heat for 4 hours, and removing plastic to obtain a ceramic biscuit;
(4) putting the ceramic biscuit into an alumina crucible, covering ceramic powder with the same composition on the ceramic biscuit in order to prevent volatilization of a Bi component, covering an alumina cover plate with a ground opening, heating to 1300 ℃ at the heating rate of 2 ℃/min, preserving heat for 2 hours, and cooling to room temperature along with a furnace to obtain a ceramic material;
(5) processing the sintered ceramic sample into a thickness of 0.2mm, cleaning, drying, printing silver paste, drying again, raising the temperature to 750 ℃ at the heating rate of 2 ℃/min, and preserving the temperature for 30 minutes to obtain a ceramic element;
(6) an X-ray diffraction analyzer (XRD) was used to determine the crystal structure and phase structure of the synthesized powder and sintered ceramic samples. Dielectric properties were tested with a Novocontrol broadband dielectric impedance spectrometer. Testing a ceramic electric hysteresis loop by adopting a TF-2000 ferroelectric analyzer;
(7) the ceramic element prepared in this example 2 was subjected to the unipolar hysteresis loop test at the highest electric field strength at room temperature, and the results are shown in fig. 3, and the maximum effective energy storage density, dielectric breakdown strength, and energy storage efficiency are shown in table 1.
Example 3:
the composition of the material is
0.90(Ba0.55Sr0.45)TiO3-0.10Bi(Mg2/3Nb1/3)O3
(1) With BaTiO3、SrTiO3Powder as raw material according to (Ba)0.55Sr0.45)TiO3Preparing stoichiometric ratio, mixing by wet ball milling method, ball milling and mixing for 24 hours according to the mass ratio of ball to deionized water of 1:4.5:1.7, drying, sieving with 40 mesh sieve, pressing into blocks under the pressure of 5MPa, raising the temperature to 1150 ℃ at the rate of 2 ℃/min, preserving the temperature for 4 hours, and synthesizing (Ba)0.55Sr0.45)TiO3Powder;
(2) grinding the powder prepared in the step (1), sieving with a 40-mesh sieve, and mixing with Bi2O3、MgO、Nb2O5The raw materials are mixed according to the proportion of 0.90 (Ba)0.55Sr0.45)TiO3-0.10Bi(Mg2/3Nb1/3)O3The preparation method comprises the steps of preparing according to the stoichiometric ratio, mixing the raw materials according to the mass ratio of 1:5:1.55 of balls to deionized water for 24 hours, drying, sieving by a 40-mesh sieve, pressing into large blocks under the pressure of 5MPa, raising the temperature to 1000 ℃ at the heating rate of 2 ℃/min, preserving the temperature for 2 hours, and synthesizing 0.90 (Ba)0.55Sr0.45)TiO3-0.10Bi(Mg2/3Nb1/3)O3Powder;
(3) and (3) grinding the powder prepared in the step (2), sieving the powder by a 40-mesh sieve, finely grinding the powder by a wet ball grinding method for 24 hours according to the mass ratio of the raw materials, namely balls and deionized water of 1:5:1.5, and drying the finely ground powder. Then adding 5 wt.% of PVA binder, granulating, briquetting, aging for 24 hours, sieving with a 40-mesh sieve, pressing into a green body with the diameter of 13mm under the pressure of 1.6MPa, then heating to 600 ℃, preserving heat for 4 hours, and removing plastic to obtain a ceramic biscuit;
(4) putting the ceramic biscuit into an alumina crucible, covering ceramic powder with the same composition on the ceramic biscuit in order to prevent volatilization of a Bi component, covering an alumina cover plate with a ground opening, heating to 1275 ℃ at a heating rate of 2 ℃/min, preserving heat for 2 hours, and cooling to room temperature along with a furnace to obtain a ceramic material;
(5) processing the sintered ceramic sample into a thickness of 0.2mm, cleaning, drying, printing silver paste, drying again, raising the temperature to 750 ℃ at the heating rate of 2 ℃/min, and preserving the temperature for 30 minutes to obtain a ceramic element;
(6) an X-ray diffraction analyzer (XRD) was used to determine the crystal structure and phase structure of the synthesized powder and sintered ceramic samples. Dielectric properties were tested with a Novocontrol broadband dielectric impedance spectrometer. Testing a ceramic electric hysteresis loop by adopting a TF-2000 ferroelectric analyzer;
(7) the ceramic element prepared in this example 3 was subjected to the unipolar hysteresis loop test at the highest electric field strength at room temperature, and the results are shown in fig. 3, and the maximum effective energy storage density, dielectric breakdown strength, and energy storage efficiency are shown in table 1.
Comparative example 1:
the composition of the material is
(Ba0.55Sr0.45)TiO3
(1) With BaTiO3、SrTiO3Powder as raw material according to (Ba)0.55Sr0.45)TiO3Preparing stoichiometric ratio, mixing by wet ball milling method, ball milling and mixing for 24 hours according to the mass ratio of ball to alcohol of 1:4.5:1.7, drying, sieving with 40 mesh sieve, pressing into blocks under the pressure of 5MPa, raising the temperature to 1150 ℃ at the rate of 2 ℃/min, preserving the temperature for 4 hours, and synthesizing (Ba)0.55Sr0.45)TiO3Powder;
(2) grinding the powder prepared in the step (1), sieving the powder with a 40-mesh sieve, finely grinding the powder by a wet ball grinding method for 24 hours according to the mass ratio of the raw materials, namely balls and deionized water of 1:5:1.6, and drying the finely ground powder. Then adding 5 wt.% of PVA binder, granulating, briquetting, aging for 24 hours, sieving with a 40-mesh sieve, and pressing under the pressure of 1.5MPa to obtain a green body with the diameter of 13mm to obtain a ceramic green body;
(3) heating the green sheet to 600 ℃ at the heating rate of 1 ℃/min, and preserving heat for 2 hours; then the temperature is raised to 1200 ℃ at the speed of 2 ℃/min, and the temperature is kept for 2 hours; finally, heating to 1350 ℃ at the heating rate of 3 ℃/min and preserving heat for 4 h;
(4) processing the sintered ceramic sample into a thickness of 0.2mm, cleaning, drying, printing silver paste, drying again, raising the temperature to 750 ℃ at a heating rate of 2 ℃, and preserving the temperature for 30 minutes to obtain a ceramic element;
(5) the ceramic element prepared in comparative example 1 was subjected to a unipolar hysteresis loop test at the highest electric field strength at room temperature, and the results are shown in fig. 3, and the maximum effective energy storage density, dielectric breakdown strength and energy storage efficiency are shown in table 1.
Table 1: dielectric breakdown strength, effective energy storage density and energy storage efficiency of each example and comparative example
| Sample (I) | Dielectric breakdown Strength (kV/cm) | Effective energy storage Density (J/cm)3) | Energy storage efficiency (%) |
| Example 1 | 420 | 3.92 | 72.5 |
| Example 2 | 450 | 4.55 | 81.8 |
| Example 3 | 380 | 3.56 | 86.2 |
| Comparative example 1 | 240 | 1.70 | 56.7 |
Table 1 shows (Ba) prepared in examples 1 to 3 and comparative example 1 of the present invention0.55Sr0.45)TiO3And (1-x) (Ba0.55Sr0.45)TiO3-xBi(Mg2/3Nb1/3)O3Dielectric breakdown strength, maximum effective energy storage density and energy storage efficiency of the ceramic at room temperature at 1 Hz. As can be seen from Table 1, the high energy storage density barium strontium titanate based lead-free relaxor ferroelectric ceramic prepared by the invention has an energy storage density of 3.56-4.55J/cm at room temperature3The energy storage efficiency is 72.5-86.2%, and the pure (Ba) prepared under the same conditions0.55Sr0.45)TiO3The energy storage density of the ceramic at room temperature is 1.7J/cm3The energy storage efficiency is only 56.7%.
FIG. 1 is a conventional solid phase method for preparing Ba0.55Sr0.45TiO3And (1-x) (Ba0.55Sr0.45)TiO3-xBi(Mg2/3Nb1/3)O3(X ═ 0.05, 0.07, 0.10) ceramic materials in the X-ray diffraction pattern at room temperature. As shown in FIG. 1 (a), Bi (Mg) is introduced2/3Nb1/3)O3After that, the ceramic was still a single perovskite phase, and no second phase appeared, indicating that Bi (Mg)2/3Nb1/3)O3Has been fully incorporated into the host lattice; FIG. 1 (b) is a partial enlarged view of the (200) peak, and it can be seen that the ceramic has a pseudo-cubic structure and is accompanied by Bi (Mg)2/3Nb1/3)O3Increasing the content the diffraction peaks shifted to lower angles, indicating an increase in the lattice constant.
Fig. 2(a) -2 (d) are graphs showing the dielectric constant and dielectric loss of the barium strontium titanate-based ceramic samples of each example and comparative example as a function of temperature at different frequencies. As can be seen from fig. 2(a) -2 (d), with the incorporation of BMN, the sharp curie peak gradually flattens and a frequency dispersion phenomenon, which is a characteristic feature of the relaxor ferroelectric, appears. FIG. 3 is a hysteresis loop at the highest electric field strength at 1Hz in the sample temperature of the barium strontium titanate-based ceramics of each example and comparative example. As can be seen from fig. 3, with the BMN being doped, the highest electric field strength that the ceramic sample can endure is increased and then decreased, and the hysteresis loop becomes more and more slender, but the maximum polarization intensity gradually decreases. Fig. 4 is a graph showing the change of the energy storage characteristics with the electric field in example 2. As can be seen from fig. 4, the effective energy storage density is gradually increased by gradually increasing the electric field strength, and the energy storage efficiency is slightly decreased.
Claims (4)
1. A preparation method of a barium strontium titanate based lead-free relaxor ferroelectric ceramic material is characterized in that the chemical composition of the barium strontium titanate based lead-free relaxor ferroelectric ceramic material is as follows: (1-x) (Ba0.55Sr0.45)TiO3-xBi(Mg2/3Nb1/3)O3Wherein x is more than 0 and less than or equal to 0.15; the preparation method comprises the following steps:
according to (Ba)0.55Sr0.45)TiO3Mixing a Ba source, a Sr source and a Ti source according to the stoichiometric ratio, drying, briquetting, and carrying out first synthesis at 1100-1200 ℃ to obtain BST ceramic powder; the time for the first synthesis is 2-6 hours;
the Bi source, the Mg source, the Nb source and the BST ceramic powder are mixed according to the proportion of (1-x) (Ba)0.55Sr0.45)TiO3-xBi(Mg2/3Nb1/3)O3Mixing the raw materials according to the stoichiometric ratio, drying, briquetting, and carrying out secondary synthesis at 900-1000 ℃ to obtain BST-BMN ceramic powder; the time for the second synthesis is 2-6 hours;
adding a binder into the BST-BMN ceramic powder, granulating, aging, pressing and forming, and removing plastic to obtain a green body; the temperature of the plastic discharging is 600-700 ℃, and the time is 2-6 hours; and
sintering the green body to obtain a barium strontium titanate-based lead-free relaxor ferroelectric ceramic material; the sintering temperature is 1250-1350 ℃, and the sintering time is 2-6 hours.
2. The method according to claim 1, wherein the Ba source is BaTiO3、BaCO3、Ba(NO3)2、(CH3COO)2At least one of Ba; the Sr source is SrTiO3、SrCO3、Sr(NO3)2、(CH3COO)2Sr; the Ti source is BaTiO3、SrTiO3、TiO2At least one of (1).
3. The method according to claim 1, wherein the Bi source is Bi2O3、Bi(NO3)3、C6H9BiO6At least one of; the Mg source is MgO and MgCO3、CH4Mg2O6At least one of; the Nb source is Nb2O5、Nb(OH)5At least one of (1).
4. The method of claim 1, wherein the green body is sintered by covering the BST-BMN ceramic powder.
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| CN117153562A (en) * | 2023-09-19 | 2023-12-01 | 江苏飞特尔通信有限公司 | Bismuth-based adjustable MLCC capacitor for LTCC and preparation method |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005097704A1 (en) * | 2004-04-07 | 2005-10-20 | Techpowder S.A. | Production of barium titanate compounds |
| CN101941832A (en) * | 2009-07-06 | 2011-01-12 | 株式会社电装 | Stupalith and electron device |
| CN101977845A (en) * | 2008-03-19 | 2011-02-16 | 日本化学工业株式会社 | Manufacturing method for barium titanate |
| CN104086172A (en) * | 2014-07-16 | 2014-10-08 | 武汉理工大学 | Ultra-wide-temperature high-stability lead-free capacitor ceramic dielectric material and preparation method thereof |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4767732A (en) * | 1986-08-28 | 1988-08-30 | Kabushiki Kaisha Toshiba | High dielectric constant ceramic material and method of manufacturing the same |
| WO2010038914A1 (en) * | 2008-10-02 | 2010-04-08 | Inova Inc. | Radio frequency identification tag using a relaxor ferroelectric substrate having a micro polar region and method for manufacturing the same |
| KR101123722B1 (en) * | 2009-07-17 | 2012-03-15 | 한국세라믹기술원 | Pb-free PIEZOELECTRIC CERAMICS AND METHOD OF MANUFACTURING THE SAME |
| CN103208365B (en) * | 2013-01-25 | 2016-01-06 | 湖北大学 | Heterogeneous laminated dielectric ceramic capacitor of a kind of temperature-stable and preparation method thereof |
| CN103993286B (en) * | 2014-05-30 | 2016-06-15 | 天津大学 | A kind of preparation method of the voltage-controlled varactor of BST/BMN laminated film |
| CN104051709A (en) * | 2014-06-10 | 2014-09-17 | 奇瑞汽车股份有限公司 | Preparation method of lithium ion battery positive electrode material |
| CN104072127A (en) * | 2014-07-09 | 2014-10-01 | 武汉理工大学 | Dielectric material for multi-layer ceramic capacitor and preparation method thereof |
| CN106631021A (en) * | 2017-01-11 | 2017-05-10 | 中国人民解放军空军工程大学 | Ceramic material high in energy storage density and energy storage efficiency and preparation method of ceramic material |
-
2018
- 2018-10-10 CN CN201811179291.XA patent/CN109180178B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005097704A1 (en) * | 2004-04-07 | 2005-10-20 | Techpowder S.A. | Production of barium titanate compounds |
| CN101977845A (en) * | 2008-03-19 | 2011-02-16 | 日本化学工业株式会社 | Manufacturing method for barium titanate |
| CN101941832A (en) * | 2009-07-06 | 2011-01-12 | 株式会社电装 | Stupalith and electron device |
| CN104086172A (en) * | 2014-07-16 | 2014-10-08 | 武汉理工大学 | Ultra-wide-temperature high-stability lead-free capacitor ceramic dielectric material and preparation method thereof |
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