CN115504784A - Lead-free relaxor ferroelectric high-energy-density ceramic material and preparation method thereof - Google Patents
Lead-free relaxor ferroelectric high-energy-density ceramic material and preparation method thereof Download PDFInfo
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Abstract
The invention provides a lead-free relaxor ferroelectric high energy storage density ceramic material and a preparation method thereof, belonging to the technical field of functional ceramic materials, wherein the chemical general formula of the lead-free relaxor ferroelectric high energy storage density ceramic material is [ (1-x) NaNbO 3 ‑xBa(Fe 0.5 Nb 0.5 )O 3 ]+yMnO 2 ，0.1<x≤0.2，0<y is less than or equal to 0.05. By adding an appropriate amount of Ba (Fe 0) .5 Nb 0.5 )O 3 And Mn doped into NaNbO 3 In the matrix, naNbO 3 The ceramic is converted from (anti) ferroelectric into relaxor ferroelectric, and the crystal grains are refined, so that the residual polarization of the prepared lead-free relaxor ferroelectric high energy storage density ceramic material is greatly reduced, the breakdown field intensity is greatly improved, and the ceramic material with high energy storage density and high energy storage efficiency is obtained.
Description
Technical Field
The invention belongs to the technical field of functional ceramic materials, and particularly relates to a lead-free relaxor ferroelectric high-energy-density ceramic material and a preparation method thereof
Background
With the comprehensive development of social modernization, the conflict between the increasing energy demand and the shortage of non-renewable energy sources such as petroleum and the like is aggravated, so that people face a huge energy crisis in the future. Therefore, how to efficiently utilize energy and develop new energy becomes more and more important, and becomes a focus of common attention of all countries in the world. Based on the effective utilization of renewable energy, the development and utilization of electrical energy storage has become an important way to alleviate the current energy crisis, and it is extremely necessary to find new materials and new processes for electrical energy storage. The dielectric capacitors have the advantages of high charging and discharging speed, long service life and the like, so that the dielectric capacitors can meet the application requirements in different aspects. With the continuous development of scientific technology, new requirements are put on energy storage materials in certain specific applications such as pulse power supply systems and the like, namely ultra-fast charge and discharge rates and ultra-high power density. The modification of capacitors and their materials to obtain materials with both high energy and power density has become the main direction and focus of current research. Currently, the research on high energy storage density dielectric materials for the preparation of capacitors is mainly focused on three main categories, polymer-ceramic composite materials and ceramics. Among them, the dielectric ceramic material is widely used in energy storage devices due to its advantages of high dielectric constant, good adjustability, good thermal stability, high energy storage density, low energy loss, etc.
The dielectric materials of the energy storage ceramic are mainly divided into three categories of linear ceramics, ferroelectric ceramics and antiferroelectric ceramics. The three types of ceramic media have different advantages and disadvantages of energy storage characteristics. Constructing a relaxor ferroelectric or a relaxor antiferroelectric is currently an effective way to achieve high energy storage density and high energy storage efficiency. The relaxor ferroelectric ceramic dielectric material has the potential of obtaining excellent energy storage characteristics due to the fact that relaxation characteristics are constructed, so that the relaxor ferroelectric ceramic dielectric material has high saturation polarization strength and low polarization hysteresis. However, most of the current (anti-) ferroelectric ceramic materials are lead-based materials, and their compositions often contain a large amount of Pb elements harmful to the environment and human body, such as lead-based complex perovskite type relaxor ferroelectrics: pb (Zr) x Ti 1-x )O 3 Doping with Pb (Mg) 1/3 Nb 2/3 )O 3 (PMN) and Pb (Zn) of Pb-Zn-Nb system 1/3 Nb 2/3 )O 3 (PZN). Therefore, in combination with current sustainable development and energy conservation and emission reduction strategies, the development of environment-friendly lead-free dielectric energy storage materials becomes of great importance. (K, na) NbO 3 (KNN) is the most promising lead-free dielectric system to replace lead-based materials due to its excellent ferroelectric properties. However, the system has high temperature volatilization of K element and K 2 CO 3 The raw materials are easy to deliquesce and the like, a second phase is easy to generate in the sintering process, and the KNN material is inevitably difficult to sinter on the ground, poor in process stability and the like, so that most of the fired dielectric ceramics have large dielectric loss (which means poor electric field breakdown strength) and are contrary to excellent dielectric energy storage characteristics.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a lead-free relaxor ferroelectric high energy storage density ceramic material and a preparation method thereof, wherein a proper amount of Ba (Fe 0) .5 Nb 0.5 )O 3 Doping into NaNbO 3 In a matrix so that NaNbO 3 The structural distortion of the ceramic is weakened, so that the ferroelectricity of the ceramic is increased and the grain size is greatly reduced, more importantly, with the increase of the doping amount, the long-range ordered structure of a macroscopic ferroelectric domain of the ceramic is destroyed, a relaxor ferroelectric with a polar nanometer micro-region at room temperature is formed, a proper amount of Mn element is added, the sintering of the ceramic is promoted on the premise of ensuring that the phase structure of the sintered ceramic is not destroyed, and the sintering temperature region, the sintering rate and the quality (including compactness, shrinkage rate, ceramic forming state and the like) of the ceramic are greatly improved. Under the comprehensive action, the remanent polarization of the prepared lead-free relaxor ferroelectric high energy storage density ceramic material is greatly reduced, the breakdown field intensity is greatly improved, and the ceramic material with high energy storage density and high energy storage efficiency is obtained.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
in one aspect, the present invention provides a lead-free relaxor ferroelectric high energy storage density ceramic material, which is characterized in that the chemical formula of the lead-free relaxor ferroelectric high energy storage density ceramic material is [ (1-x)NaNbO 3 -xBa(Fe 0.5 Nb 0.5 )O 3 ]+yMnO 2 ，0.1<x≤0.2，0<y≤0.05。
Further, x is more than or equal to 0.15 and less than or equal to 0.2, and y is less than or equal to 0.02.
On the other hand, the invention discloses a preparation method of the lead-free relaxor ferroelectric high energy storage density ceramic material, which comprises the following steps: weighing chemically pure or analytically pure raw materials according to the stoichiometric ratio of the chemical general formula, and blending to obtain an initial mixture; carrying out primary ball milling on the initial mixture in a protective medium, and drying to obtain mixed powder; preserving the temperature of the mixed powder at 800-950 ℃ for at least 2h in an air atmosphere to obtain pre-synthesized powder; grinding and crushing the pre-synthesized powder, performing secondary ball milling in a protective medium, drying, and performing dry pressing to form a ceramic blank with a certain shape; and sintering the ceramic blank in an air atmosphere to obtain the lead-free relaxor ferroelectric high energy storage density ceramic material.
Further, the raw material includes Na 2 CO 3 、BaCO 3 、Nb 2 O 5 、FeNbO 4 And MnO 2 。
Further, the FeNbO 4 The preparation method comprises the following steps: according to FeNbO 4 Weighing chemically pure or analytically pure Nb in stoichiometric ratio of chemical general formula 2 O 5 And Fe 2 O 3 Preparing raw materials of oxides; performing primary ball milling on the raw materials in a protective medium, mixing the raw materials by ball milling for not less than 8 hours, and drying to obtain mixed powder; preserving the mixed powder at 1000-1200 ℃ for at least 4h in an air atmosphere to complete high-temperature presynthesizing of a precursor to obtain precursor synthetic powder; grinding and crushing the precursor synthetic powder, performing secondary ball milling in a protective medium, mixing materials by ball milling for not less than 24 hours, drying and sieving with a 100-150-mesh sieve to obtain FeNbO 4 Raw materials.
Further, the protective medium is absolute ethyl alcohol or water.
Further, the grinding and mixing time of the primary and secondary ball milling is not less than 8h.
Further, after the secondary ball milling is finished, drying, sieving by a 100-150 mesh sieve, and pressing under the pressure of 50-200MPa to prepare a ceramic blank with a certain shape.
Further, the ceramic green body is sintered in the air under normal pressure by adopting a powder embedding method and is placed in an inverted double crucible, the sintering temperature is 1100-1250 ℃, the sintering time is 1-4 hours, and the heating rate is 1-5 ℃/min.
The lead-free relaxor ferroelectric high energy storage density ceramic material obtained by the preparation method or the lead-free relaxor ferroelectric high energy storage density ceramic material is applied as a capacitor.
Compared with the prior art, the technical scheme provided by the invention has the following beneficial effects: the invention is realized by adding proper amount of Ba (Fe 0) .5 Nb 0.5 )O 3 Doped into NaNbO 3 In the matrix, ba (Fe) 0.5 Nb 0.5 )O 3 Compared with the larger tolerance factor of NN, the Ba ion with larger radius is used as a substitute element to substitute the A site, the Fe ion is used to substitute the B site, and the substituted NaNbO 3 The structural distortion of the ceramic is weakened, so that the ferroelectricity of the ceramic is increased and the grain size of the ceramic is greatly reduced, more importantly, along with the increase of the doping amount, the long-range ordered structure of a macroscopic ferroelectric domain of the ceramic is destroyed, a relaxation ferroelectric with a polar nanometer micro-region at room temperature is formed, and a proper amount of Mn element is added, so that the sintering of the ceramic is promoted on the premise of ensuring that the phase structure of the sintered ceramic is not destroyed, and the sintering temperature region, the sintering rate and the quality (including the compactness, the shrinkage rate, the ceramic forming state and the like) of the ceramic are greatly improved. Under the comprehensive action, the remanent polarization of the prepared lead-free relaxor ferroelectric high energy storage density ceramic material is greatly reduced, the breakdown field intensity is greatly improved, and the ceramic material with high energy storage density and high energy storage efficiency is obtained. Compared with the existing lead-free potential ferroelectric material (K, na) NbO 3 (KNN) although it possesses excellent ferroelectric properties, the system has high temperature volatilization of K element and K 2 CO 3 The raw materials are easy to deliquesce and the like, a second phase is easy to generate in the sintering process, and the KNN material is inevitably difficult to sinter on the ground and has poor process stability and the like, so that the sintered product is obtainedMost of the dielectric ceramics have large dielectric loss (which means poor electric field breakdown strength) contrary to excellent dielectric energy storage characteristics.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the drawings needed to be used in the description of the embodiments will be briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without creative efforts.
FIG. 1 is an XRD pattern of a lead-free relaxor ferroelectric high energy storage density ceramic material according to example 1 of the present invention;
FIG. 2 is an SEM image of a lead-free relaxor ferroelectric high energy density ceramic material of example 1 of the present invention;
FIG. 3 is a dielectric temperature spectrum of a lead-free relaxor ferroelectric high energy storage density ceramic material in example 1 of the present invention;
FIG. 4 is a ferroelectric hysteresis loop of the lead-free relaxor ferroelectric high energy storage density ceramic material of example 1 of this invention;
FIG. 5 is a ferroelectric hysteresis loop of the lead-free relaxor ferroelectric high energy storage density ceramic material of comparative example 1 of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be further described in detail with reference to the accompanying drawings and specific embodiments. The embodiments of the present invention are not limited to the specific embodiments set forth herein, and those skilled in the art can make similar modifications without departing from the spirit of the present invention, and therefore the present invention is not limited to the disclosed specific embodiments.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
The invention provides a lead-free relaxor ferroelectric high energy storage density ceramic materialThe general chemical formula of the porcelain material is [ (1-x) NaNbO 3 -xBa(Fe0 .5 Nb 0.5 )O 3 ]+yMnO 2 ，0.1<x≤0.2，0<y≤0.05。
It is to be noted that, in the above formula, x and y represent the molar ratio of each substance in the material components.
The invention is realized by adding proper amount of Ba (Fe 0) .5 Nb 0.5 )O 3 Doping into NaNbO 3 In the matrix, ba (Fe) 0.5 Nb 0.5 )O 3 Compared with the larger tolerance factor of NN, the Ba ion with larger radius is used as a substitute element to substitute the A site, the Fe ion is used to substitute the B site, and the substituted NaNbO 3 The structural distortion of the ceramic is weakened, so that the ferroelectricity of the ceramic is increased and the grain size of the ceramic is greatly reduced, more importantly, along with the increase of the doping amount, the long-range ordered structure of a macroscopic ferroelectric domain of the ceramic is destroyed, a relaxation ferroelectric with a polar nanometer micro-region at room temperature is formed, and a proper amount of Mn element is added, so that the sintering of the ceramic is promoted on the premise of ensuring that the phase structure of the sintered ceramic is not destroyed, and the sintering temperature region, the sintering rate and the quality (including the compactness, the shrinkage rate, the ceramic forming state and the like) of the ceramic are greatly improved. Under the comprehensive action, the remanent polarization of the prepared lead-free relaxor ferroelectric high energy storage density ceramic material is greatly reduced, the breakdown field intensity is greatly improved, and the ceramic material with high energy storage density and high energy storage efficiency is obtained. Compared with the existing lead-free potential ferroelectric material (K, na) NbO 3 (KNN) which has excellent ferroelectric properties, but in which K element is volatilized at high temperature and K is present 2 CO 3 The KNN material is inevitably difficult to sinter on the ground, has poor process stability and the like, so that most of sintered dielectric ceramics have larger dielectric loss (which means poorer electric field breakdown strength) and are contradictory to excellent dielectric energy storage characteristics.
In particular, when x is more than or equal to 0.15 and less than or equal to 0.2, and y is more than or equal to 0 and less than or equal to 0.02, the lead-free relaxor ferroelectric high energy storage density ceramic material has better performance.
In order to obtain the lead-free relaxor ferroelectric high energy storage density ceramic material, the lead-free relaxor ferroelectric high energy storage density ceramic material is prepared by the following method comprising the following steps of:
s1, weighing chemically pure or analytically pure raw materials according to the stoichiometric ratio of the chemical general formula, and blending to obtain the initial mixture.
The raw material comprises Na 2 CO 3 、BaCO 3 、Nb 2 O 5 、FeNbO 4 And MnO 2 . By using FeNbO 4 Precursor replacing oxide Fe 2 O 3 And Nb 2 O 5 As raw material powder for subsequent ceramic preparation, making cation Fe 3+ And Nb 5+ The pre-reaction can obviously reduce the sintering temperature of the ceramic, improve the compactness and the distribution uniformity of the doping elements in the ceramic, and finally lead Ba (Fe) 0.5 Nb 0.5 )O 3 The prepared ceramic can effectively reduce dielectric loss.
The FeNbO 4 The preparation method comprises the following steps:
according to FeNbO 4 Weighing chemically pure or analytically pure Nb in stoichiometric ratio of chemical general formula 2 O 5 And Fe 2 O 3 Preparing raw materials of oxides;
performing primary ball milling on the raw materials in a protective medium, mixing the raw materials by ball milling for not less than 8 hours, and drying to obtain mixed powder;
preserving the mixed powder at 1000-1200 ℃ for at least 4h in an air atmosphere to complete high-temperature presynthesizing of a precursor to obtain precursor synthetic powder;
grinding and crushing the precursor synthetic powder, performing secondary ball milling in a protective medium, mixing materials by ball milling for not less than 24 hours, drying and sieving with a 100-150-mesh sieve to obtain FeNbO 4 Raw materials.
S2, performing primary ball milling on the initial mixture in a protective medium, and drying to obtain mixed powder; and the grinding and mixing time of the primary ball milling is not less than 8h.
S3, preserving the heat of the mixed powder at 800-950 ℃ for at least 2h in an air atmosphere to obtain the pre-synthesized powder. The mixed powder is placed in an alumina crucible and calcined and synthesized in the air atmosphere.
And S4, grinding and crushing the pre-synthesized powder, performing secondary ball milling in a protective medium, drying, and performing dry pressing to form a ceramic blank body in a certain shape, wherein the grinding and mixing time of the secondary ball milling is not less than 8h, after the secondary ball milling is finished, drying, sieving with a 100-150-mesh sieve, and pressing under the pressure of 50-200MPa to form the ceramic blank body in the certain shape. The shape of the ceramic blank in the embodiment of the invention is preferably a circular disc with the diameter of 8mm and the thickness of 0.5-1mm so as to improve the stress distribution uniformity of the blank.
In the embodiment of the invention, the ceramic blank is preferably prepared by a dry pressing method, and the blank prepared by the dry pressing method has the advantages of high density, accurate size, small shrinkage, high mechanical strength and good electrical property.
S5, sintering the ceramic blank in an air atmosphere to obtain the lead-free relaxor ferroelectric high energy storage density ceramic material.
Specifically, the ceramic green body is sintered in air under normal pressure by a powder embedding method and is placed in an inverted double crucible, the sintering temperature is 1100-1250 ℃, the sintering time is 1-4 hours, and the heating rate is 1-5 ℃/min.
The rotation speed of the primary ball milling and the secondary ball milling is preferably 300-500rpm. The grinding balls are preferably graded zirconium balls; the graded zirconium balls comprise large zirconium balls and small zirconium balls; the diameter of the large zirconium balls is preferably 8-10mm, and the diameter of the small zirconium balls is preferably 3-5mm; the diameter ratio of the large zirconium balls to the small zirconium balls is preferably 1.8:1.
subsequently, the structure and the electrical property of the lead-free relaxor ferroelectric high energy storage density ceramic material are measured, and an Aix ACCT-TF1000 type ferroelectric parameter tester is adopted to carry out ferroelectric property test in the embodiment of the invention; after polishing the lead-free relaxor ferroelectric high energy storage density ceramic material, respectively coating silver electrodes with the thickness of 0.015-0.02mm on the upper surface and the lower surface of the ceramic, placing the ceramic in a resistance furnace, keeping the temperature at 550 ℃ for 30 minutes, naturally cooling the ceramic to room temperature, and testing the change relation between the dielectric constant and the loss of the material with the temperature under different frequencies by adopting Agilent E4980 type dielectric Wen Puyi; XRD measurements were performed using a Rigaku Smartlab type diffractometer (Co target).
The lead-free relaxor ferroelectric high energy storage density ceramic material provided by the invention or the lead-free relaxor ferroelectric high energy storage density ceramic material prepared by adopting the preparation method can be applied as a capacitor.
Example 1
In this embodiment, the lead-free relaxor ferroelectric high energy storage density ceramic material has a chemical formula:
[0.82NaNbO 3 -0.18Ba(Fe 0.5 Nb 0.5 )O 3 ]-0.005MnO 2 。
the preparation method of the lead-free relaxor ferroelectric high energy storage density ceramic material comprises the following steps:
s11 is according to the formula [0.82NaNbO 3 -0.18Ba(Fe 0.5 Nb 0.5 )O 3 ]-0.005MnO 2 In stoichiometric ratio of (A) chemically pure or analytically pure Na is weighed 2 CO 3 、BaCO 3 、Nb 2 O 5 、FeNbO 4 And MnO 2 And (4) batching to obtain the initial mixture.
S12, carrying out primary ball milling on the initial mixture in absolute ethyl alcohol, mixing materials through ball milling for 8 hours, and drying to obtain mixed powder.
S13, preserving the heat of the mixed powder for 4 hours at 850 ℃ in an air atmosphere to obtain pre-synthesized powder.
S14, grinding and crushing the pre-synthesized powder, performing secondary ball milling in absolute ethyl alcohol, mixing materials through ball milling for 12 hours, sieving the dried powder with a 120-mesh sieve, and then performing dry pressing under the pressure of 100MPa to form a wafer with the diameter of 8mm and the thickness of 0.8mm to obtain a ceramic blank.
S15, sintering the ceramic blank in the air under normal pressure by adopting a powder embedding method, placing the ceramic blank in an inverted double crucible, sintering at 1140 ℃, sintering for 2h, and sintering at a temperature rise rate of 5 ℃/min to obtain the lead-free relaxor ferroelectric high energy storage density ceramic material.
As shown in FIG. 1, the ceramic material prepared by the embodiment of the present invention has a pure perovskite structure.
As shown in FIG. 2, the ceramic material prepared by the embodiment of the present invention has a small grain size, and the average grain size is 0.9. Mu.m.
As shown in FIG. 3, the ceramic material prepared according to the example of the present invention has a dielectric constant of about 1300 at room temperature (25 ℃ C.) and a dielectric loss of about 0.004. Compared with the prior art, the dielectric constant is greatly increased, and the dielectric loss is sharply reduced.
As shown in FIG. 4, P of the ceramic material prepared by the embodiment of the present invention max (maximum polarization) of 22.6. Eta.C/cm 2 ，P r (residual polarization intensity) of 3.3. Eta.C/cm 2 The breakdown field strength is as high as 44kV/mm. The energy storage performance W calculated by the electric hysteresis loop is 4J/cm 3 The energy storage efficiency was 75%.
Example 2
In this embodiment, the chemical formula of the lead-free relaxor ferroelectric high energy storage density ceramic material is [0.85NaNbO ] 3 -0.15Ba(Fe 0.5 Nb 0.5 )O 3 ]-0.02MnO 2 。
The preparation method of the lead-free relaxor ferroelectric high energy storage density ceramic material comprises the following steps:
s21 is according to the chemical formula [0.85NaNbO 3 -0.15Ba(Fe 0.5 Nb 0.5 )O 3 ]-0.02MnO 2 In stoichiometric ratio of (A) chemically pure or analytically pure Na is weighed 2 CO 3 、BaCO 3 、Nb 2 O 5 、FeNbO 4 And MnO 2 And (4) batching to obtain the initial mixture.
S22, carrying out primary ball milling on the initial mixture in absolute ethyl alcohol, mixing materials through ball milling for 8 hours, and drying to obtain mixed powder.
S23, preserving the heat of the mixed powder for 4 hours at 900 ℃ in an air atmosphere to obtain pre-synthesized powder.
S24, grinding and crushing the pre-synthesized powder, performing secondary ball milling in absolute ethyl alcohol, mixing materials through ball milling for 24 hours, sieving the dried powder with a 120-mesh sieve, and then performing dry pressing under the pressure of 100MPa to form a wafer with the diameter of 8mm and the thickness of 0.8mm to obtain a ceramic blank.
S25, sintering the ceramic blank in the air under normal pressure by adopting a powder embedding method, placing the ceramic blank in an inverted double crucible, wherein the sintering temperature is 1200 ℃, the sintering time is 2h, and the heating rate is 3 ℃/min, and sintering to obtain the lead-free relaxor ferroelectric high energy storage density ceramic material.
The ceramic material prepared by the embodiment has a pure perovskite structure; at room temperature, the dielectric constant is about 2000, and the dielectric loss is about 0.009; p max Is 23.2 eta.C/cm 2 ，P r Is 4 eta C/cm 2 The breakdown field strength is as high as 44kV/mm; the energy storage performance W calculated by the electric hysteresis loop is 3.4J/cm 3 The energy storage efficiency was 71%.
Example 3
In this embodiment, the chemical formula of the lead-free relaxor ferroelectric high energy storage density ceramic material is [0.8NaNbO ] 3 -0.2Ba(Fe 0.5 Nb 0.5 )O 3 ]-0.02MnO 2 。
The preparation method of the lead-free relaxor ferroelectric high energy storage density ceramic material comprises the following steps:
s31 is according to the chemical formula [0.8NaNbO 3 -0.2Ba(Fe 0.5 Nb 0.5 )O 3 ]-0.02MnO 2 In stoichiometric ratio of (A) chemically pure or analytically pure Na is weighed 2 CO 3 、BaCO 3 、Nb 2 O 5 、FeNbO 4 And MnO 2 And (4) batching to obtain the initial mixture.
S32, carrying out primary ball milling on the initial mixture in absolute ethyl alcohol, mixing materials through ball milling for 8 hours, and drying to obtain mixed powder.
S33, preserving the temperature of the mixed powder for 4 hours at 830 ℃ in an air atmosphere to obtain the pre-synthesized powder.
S34, grinding and crushing the pre-synthesized powder, performing secondary ball milling in absolute ethyl alcohol, mixing materials by ball milling for 24 hours, sieving the dried powder with a 120-mesh sieve, and performing dry pressing under the pressure of 100MPa to form a wafer with the diameter of 8mm and the thickness of 0.8mm to obtain a ceramic blank.
S35, sintering the ceramic blank in the air under normal pressure by adopting a powder embedding method, placing the ceramic blank in an inverted double crucible, wherein the sintering temperature is 1120 ℃, the sintering time is 2h, and the heating rate is 5 ℃/min, and sintering to obtain the lead-free relaxor ferroelectric high energy storage density ceramic material.
The ceramic material prepared by the embodiment has a pure perovskite structure; at room temperature, the dielectric constant is about 1000, and the dielectric loss is about 0.004; p max Is 19.1 eta.C/cm 2 ，P r Is 2.43 eta.C/cm 2 The breakdown field strength reaches 31kV/mm; the energy storage performance W calculated by the electric hysteresis loop is 2.6J/cm 3 The energy storage efficiency was 79.1%.
Example 4
In this embodiment, the chemical formula of the lead-free relaxor ferroelectric high energy storage density ceramic material is [0.875NaNbO ] 3 -0.125Ba(Fe 0.5 Nb 0.5 )O 3 ]-0.05MnO 2 。
The preparation method of the lead-free relaxor ferroelectric high energy storage density ceramic material comprises the following steps:
s41 is according to the chemical formula [0.875NaNbO 3 -0.125Ba(Fe 0.5 Nb 0.5 )O 3 ]-0.05MnO 2 In stoichiometric ratio of (A) to (B) in the presence of Na 2 CO 3 、BaCO 3 、Nb 2 O 5 、FeNbO 4 And MnO 2 And (4) batching to obtain the initial mixture.
S42, carrying out primary ball milling on the initial mixture in absolute ethyl alcohol, carrying out ball milling mixing for 8 hours, and drying to obtain mixed powder.
S43, preserving the temperature of the mixed powder at 900 ℃ for 2h in an air atmosphere to obtain the pre-synthesized powder.
S44, grinding and crushing the pre-synthesized powder, performing secondary ball milling in absolute ethyl alcohol, mixing materials through ball milling for 8 hours, sieving the dried powder with a 100-mesh sieve, and then performing dry pressing under the pressure of 200MPa to form a wafer with the diameter of 8mm and the thickness of 0.8mm to obtain a ceramic blank.
S45, sintering the ceramic blank in the air under normal pressure by adopting a powder embedding method, placing the ceramic blank in an inverted double crucible, sintering at the temperature of 1220 ℃, the sintering time of 3h and the heating rate of 3 ℃/min, and sintering to obtain the lead-free relaxor ferroelectric high energy storage density ceramic material.
The ceramic material prepared by the embodiment has a pure perovskite structure; at room temperature, the dielectric constant is about 2800, and the dielectric loss is about 0.016; p max Is 17.3 eta.C/cm 2 ，P r Is 2.05 eta C/cm 2 The breakdown field strength reaches 23kV/mm; the energy storage performance W calculated by the electric hysteresis loop is 1.2J/cm 3 The energy storage efficiency was 78.9%.
Example 5
In this embodiment, the chemical formula of the lead-free relaxor ferroelectric high energy storage density ceramic material is [0.87NaNbO ] 3 -0.13Ba(Fe 0.5 Nb 0.5 )O 3 ]-0.01MnO 2 。
The preparation method of the lead-free relaxor ferroelectric high energy storage density ceramic material comprises the following steps:
s51 according to the chemical formula [0.87NaNbO 3 -0.13Ba(Fe 0.5 Nb 0.5 )O 3 ]-0.01MnO 2 In stoichiometric ratio of (A) chemically pure or analytically pure Na is weighed 2 CO 3 、BaCO 3 、Nb 2 O 5 、FeNbO 4 And MnO 2 And (4) batching to obtain the initial mixture.
S52, carrying out primary ball milling on the initial mixture in absolute ethyl alcohol, carrying out ball milling mixing for 8 hours, and drying to obtain mixed powder.
S53, preserving the heat of the mixed powder for 3 hours at 900 ℃ in an air atmosphere to obtain the pre-synthesized powder.
S54, grinding and crushing the pre-synthesized powder, performing secondary ball milling in absolute ethyl alcohol, mixing materials through ball milling for 8 hours, sieving the dried powder with a 120-mesh sieve, and then performing dry pressing under the pressure of 200MPa to form a wafer with the diameter of 8mm and the thickness of 0.8mm to obtain a ceramic blank.
S55, sintering the ceramic blank in the air under normal pressure by adopting a powder embedding method, placing the ceramic blank in an inverted double crucible, wherein the sintering temperature is 1180 ℃, the sintering time is 1.5h, and the heating rate is 3 ℃/min, and sintering to obtain the lead-free relaxor ferroelectric high energy storage density ceramic material.
The ceramic material prepared in this example is pure calciumA titanium ore structure; at room temperature, the dielectric constant is 2600, and the dielectric loss is about 0.015; p is max Is 24.7 eta.C/cm 2 ，P r Is 4.4 eta.C/cm 2 (ii) a The breakdown field strength reaches 29kV/mm; the energy storage performance W calculated by the electric hysteresis loop is 2.2J/cm 3 The energy storage efficiency was 78.8%.
Example 6
In this embodiment, the chemical formula of the lead-free relaxor ferroelectric high energy storage density ceramic material is [0.89NaNbO ] 3 -0.11Ba(Fe 0.5 Nb 0.5 )O 3 ]-0.02MnO 2 。
The preparation method of the lead-free relaxor ferroelectric high energy storage density ceramic material comprises the following steps:
s61 according to the formula [0.89NaNbO 3 -0.11Ba(Fe 0.5 Nb 0.5 )O 3 ]-0.02MnO 2 In stoichiometric ratio of (A) to (B) in the presence of Na 2 CO 3 、BaCO 3 、Nb 2 O 5 、FeNbO 4 And MnO 2 And (4) batching to obtain the initial mixture.
S62, carrying out primary ball milling on the initial mixture in absolute ethyl alcohol, mixing materials through ball milling for 8 hours, and drying to obtain mixed powder.
S63, preserving the temperature of the mixed powder at 920 ℃ for 2h in an air atmosphere to obtain the pre-synthesized powder.
S64, grinding and crushing the pre-synthesized powder, performing secondary ball milling in absolute ethyl alcohol, mixing materials through ball milling for 9 hours, sieving the dried powder with a 150-mesh sieve, and then, dry-pressing the powder into a wafer with the diameter of 8mm and the thickness of 0.8mm under the pressure of 150MPa to obtain a ceramic blank.
S65, sintering the ceramic blank in the air under normal pressure by adopting a powder embedding method, placing the ceramic blank in an inverted double crucible, wherein the sintering temperature is 1240 ℃, the sintering time is 2h, and the heating rate is 4 ℃/min, and sintering to obtain the lead-free relaxor ferroelectric high energy storage density ceramic material.
The ceramic material prepared by the embodiment has a pure perovskite structure; at room temperature, the dielectric constant is about 3000, and the dielectric loss is about 0.022; p is max Is 25.4 eta.C/cm 2 ，P r Is 3.1 eta.C/cm 2 (ii) a The breakdown field strength reaches 26kV/mm. The energy storage performance W calculated by the electric hysteresis loop is 1.01J/cm 3 The energy storage efficiency was 82.4%.
Comparative example 1
The ceramic material prepared by the comparative example has the same chemical formula as that of example 1, and is [0.82NaNbO 3 -0.18Ba(Fe 0.5 Nb 0.5 )O 3 ]-0.005MnO 2 . The difference is that the chemically pure or analytically pure Na is weighed according to the stoichiometric ratio 2 CO 3 、BaCO 3 、Nb 2 O 5 、Fe 2 O 3 、Nb 2 O 5 And MnO 2 The materials are mixed and the ceramic material is prepared by the same process.
The ceramic material prepared by the comparative example is of a pure perovskite structure; at room temperature, the dielectric constant is about 1400, and the dielectric loss is about 0.025; the hysteresis loop is shown in FIG. 5, P max Is 19.2 eta.C/cm 2 ，P r Is 3.7 eta.C/cm 2 (ii) a The breakdown field strength reaches 33kV/mm; the energy storage performance W calculated by the electric hysteresis loop is 2.8J/cm 3 The energy storage efficiency was 66.7%. It can be seen that although comparative example 1 is the same ceramic material as example 1, the difference in properties is large due to the difference in the raw material preparation process.
Comparative example 2
Different from example 1, the ceramic material prepared in this comparative example has a chemical formula of [0.82 (K) 0.5 Na 0.5 )NbO 3 -0.18Ba(Fe 0.5 Nb 0.5 )O 3 ]-0.005MnO 2 . Weighing chemically pure or analytically pure Na according to stoichiometric ratio 2 CO 3 、BaCO 3 、K 2 CO 3 、Nb 2 O 5 、FeNbO 4 And MnO 2 The materials are mixed and the ceramic material is prepared by the same process.
The ceramic material prepared by the comparative example is of an impure phase structure; and the sintered ceramic has poor quality, large dielectric loss and poor energy storage performance.
Comparative example 3
Unlike example 1, the ceramic material prepared in this comparative example has a chemical formula of [0.82NaNbO 3 -0.18Ba(Ni 0.5 Nb 0.5 )O 3 ]-0.005MnO 2 Weighing chemically pure or analytically pure Na according to stoichiometric ratio 2 CO 3 、BaCO 3 、Nb 2 O 5 NiO and MnO 2 The materials are mixed and the ceramic material is prepared by the same process.
The ceramic material prepared by the comparative example has a non-pure perovskite structure and has impurity phases; the energy storage performance W under the 18kV/mm electric field is calculated to be 0.97J/cm through the electric hysteresis loop 3 The energy storage efficiency was 55.8%.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (10)
1. The lead-free relaxor ferroelectric high energy storage density ceramic material is characterized in that the chemical general formula of the lead-free relaxor ferroelectric high energy storage density ceramic material is [ (1-x) NaNbO 3 -xBa(Fe 0.5 Nb 0.5 )O 3 ]+yMnO 2 ，0.1<x≤0.2，0<y≤0.05。
2. The lead-free relaxor ferroelectric high energy storage density ceramic material of claim 1, wherein 0.15 ≦ x ≦ 0.2,0 ≦ y ≦ 0.02.
3. The method for preparing a lead-free relaxor ferroelectric high energy storage density ceramic material according to any of claims 1 or 2, comprising:
weighing chemically pure or analytically pure raw materials according to the stoichiometric ratio of the chemical general formula, and blending to obtain an initial mixture;
carrying out primary ball milling on the initial mixture in a protective medium, and drying to obtain mixed powder;
preserving the temperature of the mixed powder at 800-950 ℃ for at least 2h in an air atmosphere to obtain pre-synthesized powder;
grinding and crushing the pre-synthesized powder, performing secondary ball milling in a protective medium, drying, and performing dry pressing to form a ceramic blank with a certain shape;
and sintering the ceramic blank in an air atmosphere to obtain the lead-free relaxor ferroelectric high energy storage density ceramic material.
4. The method of claim 3, wherein the starting material comprises Na 2 CO 3 、BaCO 3 、Nb 2 O 5 、FeNbO 4 And MnO 2 。
5. The method of claim 4, wherein the FeNbO is 4 The preparation method comprises the following steps:
according to FeNbO 4 Weighing chemically pure or analytically pure Nb in stoichiometric ratio of chemical general formula 2 O 5 And Fe 2 O 3 Preparing raw materials of oxides;
performing primary ball milling on the raw materials in a protective medium, performing ball milling mixing for not less than 8 hours, and drying to obtain mixed powder;
preserving the mixed powder at 1000-1200 ℃ for at least 4h in air atmosphere to complete high-temperature presynthesizing of a precursor, thereby obtaining precursor synthetic powder;
grinding and crushing the precursor synthetic powder, performing secondary ball milling in a protective medium, mixing materials by ball milling for not less than 24 hours, drying and sieving with a 100-150-mesh sieve to obtain FeNbO 4 Raw materials.
6. The method according to any one of claims 3 to 5, wherein the protective medium is absolute ethanol or water.
7. The preparation method according to claim 3, characterized in that the milling mixing time of the primary and secondary ball milling is not less than 8h.
8. The preparation method of claim 3, wherein after the secondary ball milling is completed, the ceramic blank is dried, sieved by a 100-150 mesh sieve and pressed into a ceramic blank with a certain shape under the pressure of 50-200 MPa.
9. The method according to claim 3, wherein the ceramic body is sintered by a powder burying method in air under normal pressure and is placed in an inverted double crucible, the sintering temperature is 1100-1250 ℃, the sintering time is 1-4 hours, and the heating rate is 1-5 ℃/min.
10. Use of the lead-free relaxor ferroelectric high energy storage density ceramic material according to any of claims 1 to 2 or the lead-free relaxor ferroelectric high energy storage density ceramic material obtained by the preparation method according to any of claims 3 to 9 as a capacitor.
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