CN115504784B - Leadless relaxation ferroelectric high energy storage density ceramic material and preparation method thereof - Google Patents
Leadless relaxation ferroelectric high energy storage 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 lead-free relaxor ferroelectric high-energy-storage-density ceramic material has a chemical general formula of [ (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 mixing a proper amount of Ba (Fe 0) .5 Nb 0.5 )O 3 And Mn doping into NaNbO 3 NaNbO in matrix 3 The ceramic is converted from (anti) ferroelectric into relaxor ferroelectric, and grains are thinned, so that the remnant polarization of the prepared lead-free relaxor ferroelectric ceramic material with high energy storage density 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 in particular relates to a lead-free relaxor ferroelectric ceramic material with high energy storage density and a preparation method thereof
Background
With the comprehensive development of society modernization, the conflict of increasing energy demand and shortage of fossil fuel non-renewable energy such as petroleum is aggravated, so that people will face a huge energy crisis in the future. Therefore, how to efficiently utilize energy and develop new energy has become more and more important, and has become a focus of attention in countries around the world. Based on the efficient use of renewable energy sources, the development and utilization of electrical energy storage has become an important approach to alleviate the current energy crisis, and the search for new materials and new technologies for electrical energy storage is necessary. Dielectric capacitors can meet application requirements in different aspects due to the advantages of high charge and discharge speed, long service life and the like. With the continuous development of science and technology, new demands are being placed on energy storage materials in certain specific applications, such as pulse power systems, that is, ultra-fast charge and discharge rates and ultra-high power densities. The achievement of materials with both high energy and power density through modification of capacitors and their materials has become a major direction and hotspot of current research. Currently, research for preparing high energy storage density dielectric materials for capacitors is mainly focused on three major categories, polymer-ceramic composite materials and ceramics. The dielectric ceramic material is widely applied to energy storage devices because of the advantages of high dielectric constant, good adjustability, good thermal stability, high energy storage density, low energy loss and the like.
The energy storage ceramic dielectric materials are mainly divided into three major categories of linear ceramics, ferroelectric ceramics and antiferroelectric ceramics. All three types of ceramic media have the advantages and disadvantages of different energy storage characteristics. The construction of relaxor ferroelectrics or relaxor antiferroelectrics is currently an effective way to achieve high energy storage densities and high energy storage efficiencies. The relaxation ferroelectric ceramic dielectric material has excellent energy storage property potential due to the fact that relaxation property is built, so that the relaxation ferroelectric ceramic dielectric material has high saturation polarization intensity and low polarization hysteresis. However, most (anti) ferroelectric ceramic materials are currently lead-based materials, the composition of which often contains a large amount of Pb elements harmful to the environment and the human body, such as lead-based composite perovskite relaxor ferroelectrics: pb (Zr) x Ti 1-x )O 3 Pb (Mg) doped 1/3 Nb 2/3 )O 3 (PMN) and Pb (Zn) of lead-zinc-niobium series 1/3 Nb 2/3 )O 3 (PZN). Therefore, in combination with current sustainable development and energy conservation and emission reduction strategies, it is becoming particularly important to develop environmentally friendly lead-free dielectric energy storage materials. (K, na) NbO 3 (KNN) is a lead-free dielectric system that is most promising as a replacement for lead-based materials because of its excellent ferroelectric properties. However, the system has high-temperature volatilization of K element and K 2 CO 3 The raw materials are deliquescent and the like, and the sintering process is easy to generate a second phase, so that the KNN material inevitably faces the problems of difficult sintering, poor process stability and the like, and the sintered dielectric ceramics mostly have larger dielectric loss (which means poor electric field breakdown strength) and are contrary to the excellent dielectric energy storage property.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention provides a lead-free relaxor ferroelectric ceramic material with high energy storage density and a preparation method thereof, which is prepared by mixing a proper amount of Ba (Fe 0) .5 Nb 0.5 )O 3 Doped into NaNbO 3 In the matrix, naNbO is formed 3 The structural distortion of the ceramic is weakened, so that the ferroelectricity is increased, the grain size is greatly reduced, more importantly, along with the increase of the doping amount, the long-range ordered structure of the 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 compactness, shrinkage, porcelain forming state and the like) of the ceramic are greatly improved. Under the comprehensive action, the residual polarization of the prepared lead-free relaxation ferroelectric ceramic material with high energy storage density 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 above purpose, the technical scheme adopted by the invention is as follows:
on one hand, the invention provides a lead-free relaxor ferroelectric high-energy-storage-density ceramic material, which is characterized in that the lead-free relaxor ferroelectric high-energy-storage-density ceramic material has a chemical general formula of [ (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 more than or equal to 0 and less than or equal to 0.02.
On the other hand, the invention discloses a preparation method of the lead-free relaxor ferroelectric ceramic material with high energy storage density, which comprises the following steps: weighing chemically pure or analytically pure raw materials according to the stoichiometric ratio of the chemical general formula, and proportioning to obtain an initial mixture; ball milling is carried out on the initial mixture in a protective medium for one time, and the mixture is dried to obtain mixed powder; the mixed powder is kept at the temperature of 800-950 ℃ for at least 2 hours under the 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 ceramic material with high energy storage density.
Further toThe raw materials include Na 2 CO 3 、BaCO 3 、Nb 2 O 5 、FeNbO 4 And MnO 2 。
Further, the FeNbO 4 The preparation method of (2) is as follows: according to FeNbO 4 Stoichiometric ratio of chemical formula to analytically pure Nb 2 O 5 And Fe (Fe) 2 O 3 Preparing an oxide raw material; ball milling is carried out on the raw materials in a protective medium for one time, and mixed materials are dried after ball milling for no less than 8 hours to obtain mixed powder; the mixed powder is subjected to heat preservation for at least 4 hours at the temperature of 1000-1200 ℃ in an air atmosphere, and the high-temperature pre-synthesis of the precursor is completed, so that precursor synthesized powder is obtained; grinding and crushing the precursor synthesized powder, performing secondary ball milling in a protective medium, performing ball milling and mixing for not less than 24 hours, and 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 8 hours.
Further, after the secondary ball milling is finished, the ceramic blank is dried and then is sieved by a 100-150 mesh sieve, and is pressed into a ceramic blank body with a certain shape under the pressure of 50-200 MPa.
Further, sintering the ceramic body in air under normal pressure by adopting a powder burying method, and placing the ceramic body in a double crucible which is placed upside down, wherein 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 lead-free relaxor ferroelectric high-energy-storage-density ceramic material or the preparation method is applied to a capacitor.
Compared with the prior art, the technical scheme provided by the invention has the following beneficial effects: the invention is characterized in that a 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 NN, the tolerance factor is larger, the A position is replaced by taking Ba ion with larger radius as a replacing element, and Fe ion is adoptedB-site is replaced, and the replaced NaNbO is prepared 3 The structural distortion of the ceramic is weakened, so that the ferroelectricity is increased, the grain size is greatly reduced, more importantly, along with the increase of the doping amount, the long-range order structure of the 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 compactness, shrinkage, porcelain forming state and the like) of the ceramic are greatly improved. Under the comprehensive action, the residual polarization of the prepared lead-free relaxation ferroelectric ceramic material with high energy storage density 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 addition, compared with the prior lead-free potential ferroelectric material (K, na) NbO 3 (KNN), although possessing excellent ferroelectric properties, the system has high-temperature volatilization of K element and K 2 CO 3 The raw materials are deliquescent and the like, and the sintering process is easy to generate a second phase, so that the KNN material inevitably faces the problems of difficult sintering, poor process stability and the like, and most of sintered dielectric ceramics have larger dielectric loss (which means poor electric field breakdown strength) and are contrary to the excellent dielectric energy storage property.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings required for the description of the embodiments will be briefly described below, and it is apparent that the drawings in the following description are only some embodiments of the present invention, and other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is an XRD pattern for a lead-free relaxed ferroelectric high storage density ceramic material of example 1 of the present invention;
FIG. 2 is an SEM image of a lead-free relaxed ferroelectric high energy storage density ceramic material of example 1 of the present invention;
FIG. 3 is a graph of the dielectric temperature of the lead-free relaxor ferroelectric high storage density ceramic material of example 1 of the present invention;
FIG. 4 is a hysteresis loop of the lead-free relaxed ferroelectric high storage density ceramic material of example 1 of the present invention;
fig. 5 is a hysteresis loop of the lead-free relaxed ferroelectric high storage density ceramic material of comparative example 1 of the present invention.
Detailed Description
The present invention will be further described in detail with reference to the drawings and the specific embodiments thereof in order to make the objects, technical solutions and advantages of the present invention more apparent. The detailed description of the invention is not limited to the specific embodiments disclosed herein, but is intended to cover modifications and other modifications of the invention as fall within the spirit and scope of the invention.
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 material, which has a chemical general formula of [ (1-x) NaNbO 3 -xBa(Fe0 .5 Nb 0.5 )O 3 ]+yMnO 2 ，0.1<x≤0.2，0<y≤0.05。
It should be noted that in the above formula x and y represent the molar ratio of the respective substances in the material component.
The invention is characterized in that a 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 NN, the tolerance factor is larger, the A site is replaced by taking Ba ion with larger radius as a replacing element, the B site is replaced by adopting Fe ion, and the replaced NaNbO is prepared 3 The structural distortion of the ceramic is weakened, so that the ferroelectricity is increased and the grain size is greatly reduced, more importantly, along with the increase of doping amount, the long-range order structure of the macroscopic ferroelectric domain of the ceramic is destroyed, a relaxation ferroelectric with polar nanometer micro-regions at room temperature is formed, and proper amount of Mn element is added, so that the self-destruction of the sintered ceramic is avoidedOn the premise of the phase structure of the ceramic, the sintering of the ceramic is promoted, and the sintering temperature area, the sintering rate and the quality (including the density, the shrinkage, the porcelain forming state and the like) of the ceramic are greatly improved. Under the comprehensive action, the residual polarization of the prepared lead-free relaxation ferroelectric ceramic material with high energy storage density 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 addition, compared with the prior lead-free potential ferroelectric material (K, na) NbO 3 (KNN), although possessing excellent ferroelectric properties, the system has high-temperature volatilization of K element and K 2 CO 3 The raw materials are deliquescent and the like, and the sintering process is easy to generate a second phase, so that the KNN material inevitably faces the problems of difficult sintering, poor process stability and the like, and most of sintered dielectric ceramics have larger dielectric loss (which means poor electric field breakdown strength) and are contrary to the excellent dielectric energy storage property.
Specifically, when x is more than or equal to 0.15 and less than or equal to 0.2, 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 preparation method comprises the following steps:
s1, weighing chemically pure or analytically pure raw materials according to the stoichiometric ratio of the chemical general formula, and proportioning to obtain the initial mixture.
The raw materials comprise Na 2 CO 3 、BaCO 3 、Nb 2 O 5 、FeNbO 4 And MnO 2 . By FeNbO 4 Precursor instead of oxide Fe 2 O 3 And Nb (Nb) 2 O 5 As raw material powder for the subsequent ceramic preparation, the cationic Fe is prepared 3+ And Nb (Nb) 5+ The pre-reaction can obviously reduce the sintering temperature of the ceramic, improve the density and the uniformity of the distribution of doping elements in the ceramic, and finally lead the Ba (Fe) 0.5 Nb 0.5 )O 3 The prepared ceramic can effectively reduce dielectric loss.
The FeNbO 4 The preparation method of (2) is as follows:
according to FeNbO 4 Of the general chemical formulaStoichiometric ratio of chemically or analytically pure Nb 2 O 5 And Fe (Fe) 2 O 3 Preparing an oxide raw material;
ball milling is carried out on the raw materials in a protective medium for one time, and mixed materials are dried after ball milling for no less than 8 hours to obtain mixed powder;
the mixed powder is subjected to heat preservation for at least 4 hours at the temperature of 1000-1200 ℃ in an air atmosphere, and the high-temperature pre-synthesis of the precursor is completed, so that precursor synthesized powder is obtained;
grinding and crushing the precursor synthesized powder, performing secondary ball milling in a protective medium, performing ball milling and mixing for not less than 24 hours, and drying and sieving with a 100-150 mesh sieve to obtain FeNbO 4 Raw materials.
S2, performing ball milling on the initial mixture in a protective medium for one time, and drying to obtain mixed powder; the grinding and mixing time of the primary ball milling is not less than 8 hours.
S3, preserving the temperature of the mixed powder for at least 2 hours at 800-950 ℃ in the air atmosphere to obtain the pre-synthesized powder. In the invention, the mixed powder is placed in an alumina crucible and calcined and synthesized in an 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 with a certain shape, wherein the grinding and mixing time of the secondary ball milling is not less than 8 hours, and after the secondary ball milling is finished, drying and sieving with a 100-150 mesh sieve, and pressing into the ceramic blank body with a certain shape under the pressure of 50-200 MPa. The ceramic blank in the embodiment of the invention is preferably a circular sheet with the diameter of 8mm and the thickness of 0.5-1mm so as to improve the uniformity of stress distribution 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 body is sintered by adopting a powder burying method in air under normal pressure, and is placed in a double crucible which is placed upside down, wherein the sintering temperature is 1100-1250 ℃, the sintering time is 1-4 hours, and the heating rate is 1-5 ℃/min.
The rotational speed of the primary and 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.
the structure and the electrical property of the lead-free relaxor ferroelectric high-energy-storage density ceramic material are measured subsequently, and the embodiment of the invention adopts an Aix ACCT-TF1000 type ferroelectric parameter tester to test the ferroelectric property; 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 and lower surfaces of the ceramic, placing the ceramic in a resistance furnace, preserving heat at 550 ℃ for 30 minutes, naturally cooling to room temperature, and testing the change relation between the dielectric constants and the loss of the material with the temperature under different frequencies by adopting Agilent E4980 type dielectric Wen Puyi; XRD testing was 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 prepared by the preparation method can be used as a capacitor.
Example 1
The chemical formula of the lead-free relaxor ferroelectric high-energy-storage-density ceramic material is as follows:
[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 chemical formula [0.82NaNbO ] 3 -0.18Ba(Fe 0.5 Nb 0.5 )O 3 ]-0.005MnO 2 Is to weigh chemically or analytically pure Na 2 CO 3 、BaCO 3 、Nb 2 O 5 、FeNbO 4 And MnO 2 Proceeding withBatching to obtain the initial mixture.
S12, ball milling is carried out on the initial mixture in absolute ethyl alcohol for one time, ball milling and mixing are carried out for 8 hours, and mixed powder is obtained after drying.
S13, preserving the temperature of the mixed powder for 4 hours at 850 ℃ in an air atmosphere to obtain the pre-synthesized powder.
S14, grinding and crushing the pre-synthesized powder, performing secondary ball milling in absolute ethyl alcohol, performing ball milling and mixing for 12 hours, sieving the dried powder with a 120-mesh sieve, and performing dry pressing on the powder under 100MPa to obtain a wafer with the diameter of 8mm and the thickness of 0.8mm, thereby obtaining a ceramic blank.
S15, sintering the ceramic blank by adopting a powder burying method in air at normal pressure, and placing the ceramic blank in a reverse double crucible, wherein the sintering temperature is 1140 ℃, the sintering time is 2 hours, the heating rate is 5 ℃/min, and the lead-free relaxor ferroelectric ceramic material with high energy storage density is obtained by sintering.
As shown in fig. 1, the ceramic material prepared by the embodiment of the invention has a pure perovskite structure.
As shown in FIG. 2, the ceramic material prepared in the example 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 dielectric constant of the ceramic material prepared by the embodiment of the invention is about 1300 at room temperature (25 ℃), and the dielectric loss is about 0.004. Compared with the prior art, the dielectric constant is greatly increased, and the dielectric loss is drastically reduced.
As shown in FIG. 4, the ceramic material prepared according to the embodiment of the invention has P max (maximum polarization) of 22.6. Eta.C/cm 2 ，P r (remnant polarization Strength) was 3.3. Eta.C/cm 2 The breakdown field strength is as high as 44kV/mm. The energy storage property W calculated by the hysteresis loop is 4J/cm 3 The energy storage efficiency is 75%.
Example 2
The lead-free relaxor ferroelectric high-energy-storage-density ceramic material provided by the embodiment has a chemical formula of [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 Is to weigh chemically or analytically pure Na 2 CO 3 、BaCO 3 、Nb 2 O 5 、FeNbO 4 And MnO 2 And (5) batching to obtain the initial mixture.
S22, ball milling is carried out on the initial mixture in absolute ethyl alcohol for one time, ball milling and mixing are carried out for 8 hours, and mixed powder is obtained after drying.
S23, preserving the temperature of the mixed powder for 4 hours at 900 ℃ under the air atmosphere to obtain the pre-synthesized powder.
S24, grinding and crushing the pre-synthesized powder, performing secondary ball milling in absolute ethyl alcohol, performing ball milling and mixing for 24 hours, sieving the dried powder with a 120-mesh sieve, and performing dry pressing on the powder under 100MPa to obtain a wafer with the diameter of 8mm and the thickness of 0.8mm, thereby obtaining a ceramic blank.
S25, sintering the ceramic blank by adopting a powder burying method in air at normal pressure, placing the ceramic blank in a reverse double crucible, wherein the sintering temperature is 1200 ℃, the sintering time is 2h, 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 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 (P) max 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 property W calculated by the hysteresis loop is 3.4J/cm 3 The energy storage efficiency was 71%.
Example 3
The lead-free relaxor ferroelectric high-energy-storage-density ceramic material provided by the embodiment has a chemical formula of [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 Is to weigh chemically or analytically pure Na 2 CO 3 、BaCO 3 、Nb 2 O 5 、FeNbO 4 And MnO 2 And (5) batching to obtain the initial mixture.
S32, ball milling is carried out on the initial mixture in absolute ethyl alcohol for one time, ball milling and mixing are carried out for 8 hours, and mixed powder is obtained after drying.
S33, preserving the temperature of the mixed powder for 4 hours at the temperature of 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, performing ball milling and mixing for 24 hours, sieving the dried powder with a 120-mesh sieve, and performing dry pressing on the powder under 100MPa to obtain a wafer with the diameter of 8mm and the thickness of 0.8mm, thereby obtaining a ceramic blank.
S35, sintering the ceramic blank by adopting a powder burying method in air at normal pressure, and placing the ceramic blank in a reverse double crucible, wherein the sintering temperature is 1120 ℃, the sintering time is 2h, the heating rate is 5 ℃/min, and the lead-free relaxor ferroelectric ceramic material with high energy storage density is obtained by sintering.
The ceramic material prepared in 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 (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 property W calculated by the hysteresis loop is 2.6J/cm 3 The energy storage efficiency is 79.1%.
Example 4
The lead-free relaxor ferroelectric high-energy-storage-density ceramic material provided by the embodiment has a chemical formula of [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 Is to weigh chemically or analytically pure Na 2 CO 3 、BaCO 3 、Nb 2 O 5 、FeNbO 4 And MnO 2 And (5) batching to obtain the initial mixture.
S42, ball milling is carried out on the initial mixture in absolute ethyl alcohol for one time, ball milling and mixing are carried out for 8 hours, and mixed powder is obtained after drying.
S43, preserving the temperature of the mixed powder for 2 hours at 900 ℃ under the air atmosphere to obtain the pre-synthesized powder.
S44, grinding and crushing the pre-synthesized powder, performing secondary ball milling in absolute ethyl alcohol, performing ball milling and mixing for 8 hours, sieving the dried powder with a 100-mesh sieve, and performing dry pressing under the pressure of 200MPa to obtain a wafer with the diameter of 8mm and the thickness of 0.8mm, thereby obtaining a ceramic blank.
S45, sintering the ceramic blank by adopting a powder burying method in air at normal pressure, placing the ceramic blank in a reverse double crucible, wherein the sintering temperature is 1220 ℃, the sintering time is 3h, 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 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 (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 property W calculated by the hysteresis loop is 1.2J/cm 3 The energy storage efficiency is 78.9%.
Example 5
The lead-free relaxor ferroelectric high-energy-storage-density ceramic material provided by the embodiment has a chemical formula of [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 is according to the chemical formula [0.87NaNbO ] 3 -0.13Ba(Fe 0.5 Nb 0.5 )O 3 ]-0.01MnO 2 Is to weigh a chemical or analytical purityNa 2 CO 3 、BaCO 3 、Nb 2 O 5 、FeNbO 4 And MnO 2 And (5) batching to obtain the initial mixture.
S52, performing ball milling on the initial mixture in absolute ethyl alcohol for one time, performing ball milling and mixing for 8 hours, and drying to obtain mixed powder.
And S53, preserving the temperature 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, performing ball milling and mixing for 8 hours, sieving the dried powder with a 120-mesh sieve, and performing dry pressing under the pressure of 200MPa to obtain a wafer with the diameter of 8mm and the thickness of 0.8mm, thereby obtaining a ceramic blank.
S55, sintering the ceramic blank by adopting a powder burying method in air at normal pressure, placing the ceramic blank in a reverse double crucible, wherein the sintering temperature is 1180 ℃, the sintering time is 1.5h, 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 the embodiment has a pure perovskite structure; at room temperature, the dielectric constant is 2600, and the dielectric loss is about 0.015; p (P) max 24.7 eta C/cm 2 ，P r 4.4 eta C/cm 2 The method comprises the steps of carrying out a first treatment on the surface of the The breakdown field strength reaches 29kV/mm; the energy storage property W calculated by the hysteresis loop is 2.2J/cm 3 The energy storage efficiency is 78.8%.
Example 6
The lead-free relaxor ferroelectric high-energy-storage-density ceramic material provided by the embodiment has a chemical formula of [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 is according to the chemical formula [0.89NaNbO ] 3 -0.11Ba(Fe 0.5 Nb 0.5 )O 3 ]-0.02MnO 2 Is to weigh chemically or analytically pure Na 2 CO 3 、BaCO 3 、Nb 2 O 5 、FeNbO 4 And MnO 2 And (5) batching to obtain the initial mixture.
S62, performing ball milling on the initial mixture in absolute ethyl alcohol for one time, performing ball milling and mixing for 8 hours, and drying to obtain mixed powder.
S63, preserving the temperature of the mixed powder for 2 hours at the temperature of 920 ℃ in the air atmosphere to obtain the pre-synthesized powder.
S64, grinding and crushing the pre-synthesized powder, performing secondary ball milling in absolute ethyl alcohol, performing ball milling and mixing for 9 hours, sieving the dried powder with a 150-mesh sieve, and performing dry pressing under 150MPa to obtain a wafer with the diameter of 8mm and the thickness of 0.8mm, thereby obtaining a ceramic blank.
S65, sintering the ceramic blank by adopting a powder burying method in air at normal pressure, placing the ceramic blank in a reverse double crucible, wherein the sintering temperature is 1240 ℃, the sintering time is 2h, 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 in 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 (P) max 25.4 eta C/cm 2 ，P r Is 3.1 eta C/cm 2 The method comprises the steps of carrying out a first treatment on the surface of the The breakdown field strength reaches 26kV/mm. The energy storage property W calculated by the hysteresis loop is 1.01J/cm 3 The energy storage efficiency is 82.4%.
Comparative example 1
The ceramic materials prepared in this comparative example had the same chemical formula as in example 1, and were all [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 And (3) preparing materials and adopting the same process to prepare the ceramic material.
The ceramic material prepared in this comparative example has a pure perovskite structure; a dielectric constant of about 1400 and a dielectric loss of about 0.025 at room temperature; 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 The method comprises the steps of carrying out a first treatment on the surface of the The breakdown field strength reaches 33kV/mm; the energy storage property W calculated by the hysteresis loop is 2.8J/cm 3 The energy storage efficiency is 66.7%. It can be seen that although comparative example 1 is the same ceramic material as example 1, the difference in performance is large due to the difference in the raw material preparation process.
Comparative example 2
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 or analytically pure Na according to a stoichiometric ratio 2 CO 3 、BaCO 3 、K 2 CO 3 、Nb 2 O 5 、FeNbO 4 And MnO 2 And (3) preparing materials and adopting the same process to prepare the ceramic material.
The ceramic material prepared in this comparative example is of a non-pure perovskite structure, and has a hetero-phase; and the ceramic obtained by sintering 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 had a chemical formula of [0.82NaNbO 3 -0.18Ba(Ni 0.5 Nb 0.5 )O 3 ]-0.005MnO 2 Weighing chemically or analytically pure Na according to stoichiometric ratio 2 CO 3 、BaCO 3 、Nb 2 O 5 NiO and MnO 2 And (3) preparing materials and adopting the same process to prepare the ceramic material.
The ceramic material prepared in this comparative example is of a non-pure perovskite structure, and has a hetero-phase; the energy storage performance W of the electric field of 18kV/mm is calculated to be 0.97J/cm through a hysteresis loop 3 The energy storage efficiency is 55.8%.
The foregoing description of the preferred embodiments of the invention is not intended to limit the invention to the precise form disclosed, and any such modifications, equivalents, and alternatives falling within the spirit and scope of the invention are intended to be included within the scope of the invention.
Claims (10)
1. A leadless relaxor ferroelectric high energy storage density ceramic material is characterized in that the leadless relaxor ferroelectric high energy storage density ceramic material has a chemical general formula of [ (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 storage density ceramic material as claimed in claim 1, wherein x is 0.15.ltoreq.0.2 and y is 0.02.
3. A method of preparing a lead-free relaxor ferroelectric high storage density ceramic material as claimed in any one 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 proportioning to obtain an initial mixture;
ball milling is carried out on the initial mixture in a protective medium for one time, and the mixture is dried to obtain mixed powder;
the mixed powder is kept at the temperature of 800-950 ℃ for at least 2 hours under the 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 ceramic material with high energy storage density.
4. A method according to 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 according to claim 4, wherein the FeNbO is 4 The preparation method of (2) is as follows:
according to FeNbO 4 Stoichiometry of the general chemical formulaWeighing chemically or analytically pure Nb 2 O 5 And Fe (Fe) 2 O 3 Preparing an oxide raw material;
ball milling is carried out on the raw materials in a protective medium for one time, and mixed materials are dried after ball milling for no less than 8 hours to obtain mixed powder;
the mixed powder is subjected to heat preservation for at least 4 hours at the temperature of 1000-1200 ℃ in an air atmosphere, and the high-temperature pre-synthesis of the precursor is completed, so that precursor synthesized powder is obtained;
grinding and crushing the precursor synthesized powder, performing secondary ball milling in a protective medium, performing ball milling and mixing for not less than 24 hours, and 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. A method of preparing according to claim 3, wherein the primary and secondary ball milling is performed for a period of not less than 8 hours.
8. The method according to claim 3, wherein after the secondary ball milling is completed, the ceramic body is dried and sieved by a 100-150 mesh sieve and pressed into a ceramic body 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 at normal pressure and placed in a double crucible placed upside down, the sintering temperature is 1100-1250 ℃, the sintering time is 1-4 hours, and the heating rate is 1-5 ℃/min.
10. Use of a lead-free relaxor ferroelectric high storage density ceramic material according to any one of claims 1-2 or obtained by the method of preparation according to any one of claims 3-9 as a capacitor.
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| CN104725042A (en) * | 2014-12-30 | 2015-06-24 | 中国科学院声学研究所 | Multielement composite pyroelectric ceramic material and preparation method thereof |
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