CN115180944B - Full-filled tungsten bronze structure high-entropy ferroelectric ceramic material and preparation method thereof - Google Patents
Full-filled tungsten bronze structure high-entropy ferroelectric ceramic material and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a full-filled tungsten bronze structure high-entropy ferroelectric ceramic material and a preparation method thereof, wherein the material has a chemical formula as follows: a. The 3 B 5 O 15 The content of the six elements at the A position is equal molar ratio. The invention introduces the high-entropy design concept into the tungsten bronze structure material for the first time, designs and successfully prepares the high-entropy ferroelectric ceramic with the tungsten bronze structure, and obtains 6.048J/cm 3 The invention adopts a solid phase method for preparation, has simple process flow and belongs to a lead-free bismuth-free material. The invention is expected to be practically applied to the capacitor and provides a new idea for the research and development of novel dielectric ceramic materials.
Description
Technical Field
The invention belongs to the technical field of functional ceramics, and relates to a full-filling type tungsten bronze structure high-entropy ferroelectric ceramic and a preparation method thereof.
Background
The dielectric ceramic capacitor is distinguished in polymers, chemical batteries and other energy storage devices by the advantages of ultra-fast charge and discharge speed, high power density, excellent temperature/mechanical stability and the like, and is widely concerned and applied in the fields of electromagnetic weapons, medical treatment, communication and the like. Among dielectric ceramic materials, relaxor ferroelectric ceramics show good saturation polarization characteristics and slender ferroelectric hysteresis loops, can obtain higher energy storage density, and also have the advantages of good cycle stability, thermal stability, high power density, rapid charge and discharge rate and the like, thereby being an energy storage material with great prospect. Lead-based and bismuth-based relaxor ferroelectric ceramics play an important role in the research field of relaxor ferroelectric ceramics, but lead-based compounds are not friendly to the natural environment and human health, and bismuth-based materials are easy to react with electrodes. Therefore, the research and development of the lead-free and bismuth-free dielectric ceramic material with high energy storage characteristics have important significance.
The high-entropy material is composed of five or more elements, which are mixed in a ratio of approximately equimolar amounts to give the maximum configurational entropy (. DELTA.S) config Not less than 1.61R, R = 8.314J/mol.K) to formA stable single-phase structure. Because of more element types and different atomic radii, some peculiar effects appear in the high-entropy material: firstly, the Gibbs free energy of the system is effectively reduced by high mixed entropy according to a Gibbs free energy formula, and thermodynamic stability is achieved, so that a stable single phase is formed; secondly, the lattice distortion effect is caused by the random distribution of various elements and the difference of the radius and valence state of atoms of each element; thirdly, the delayed diffusion effect, due to the complex element composition, the internal potential energy environment is highly disordered to cause slow atom movement, and simultaneously, the internal stress generated by lattice distortion also hinders the diffusion of atoms; and fourthly, the cocktail effect, the influence of different elements on the structure and the performance shows different effects, and the mutual coupling effect among the elements shows not only single superposition but also the synergistic effect of multiple elements. The appearance of the high-entropy material provides a new concept and path for developing a non-metal material with excellent performance, and the high-entropy ceramic is a new ceramic material system which is gradually developed on the basis of high-entropy alloy in recent years.
At present, the research on the high-entropy ferroelectric ceramics mostly focuses on perovskite structures and perovskite layered structures, and the obtained high-entropy relaxation ferroelectric ceramics obtain good energy storage characteristics. Such as perovskite structural component (Bi) 0.2 Na 0.2 K 0.2 La 0.2 Sr 0.2 )TiO 3 (Journal of the American Ceramic Society,2021,105 (2): 1083-1094), having a storage density W rec ＝0.959J/cm 3 Energy storage efficiency η =90%; (Na) 0.2 Bi 0.2 Ba 0.2 Sr 0.2 Ca 0.2 )TiO 3 (Applied Physics Letters,2019,115 (22): 223901) gave higher energy storage densities (W) rec ＝1.02J/cm 3 ). Perovskite layered structure component (Ca) 0.25 Sr 0.25 Ba 0.25 Pb 0.25 )Bi 2 Nb 2 O 9 And (Ca) 0.2 Sr 0.2 Ba 0.2 Pb 0.2 Nd 0.1 Na 0.1 )Bi 2 Nb 2 O 9 Also exhibit relaxation properties.
Tungsten bronze structureThe second largest class of lead-free dielectric material structure, second only to perovskite structure, is a Tetragonal Tungsten Bronze (TTB) structure compound, which is a typical ferroelectric material, receiving a great deal of attention due to its complex structure and abundant properties. The structural general formula of the tetragonal tungsten bronze is (A1) 2 (A2) 4 (C) 4 (B1) 2 (B2) 8 O 30 The unit cell is composed of 10 oxygen octahedrons BO 6 The crystal lattice network formed by connecting the common vertexes forms three gaps with different sizes A1, A2 and C (A1 is a square gap, the coordination number is 12, A2 is a pentagonal gap, and 15 coordinates; C is a triangular gap), and the three types can be divided into a filling type (the three gaps are completely filled), a filling type (A1 and A2 are completely filled, and C is empty) and a non-filling type (A1 and A2 are partially filled, and C is empty) according to the ion filling degree. In this view, tungsten bronze has a higher specific perovskite type oxide (ABO) 3 ) The structure is more complex, and the gaps at A position, B position and C position which are not equivalent on the crystal structure can be occupied by ions with different ionic radiuses and valence states, so that the tungsten bronze structure has flexibility of component design and freedom degree of structure regulation to a great extent. At present, most of research and development on high-entropy ceramics are concentrated on a perovskite system, tungsten bronze structure high-entropy ceramics are not reported, the concept of high-entropy design is introduced into the tungsten bronze structure, and a new thought is provided for design and research and development of dielectric ceramic materials.
Disclosure of Invention
Based on the analysis, the concept of the high-entropy ceramic is combined with the tungsten bronze structure, and the invention aims to provide the high-entropy ferroelectric ceramic with the filled tungsten bronze structure and the preparation method thereof.
In a first aspect, the invention provides a full-filled tungsten bronze structure high-entropy ferroelectric ceramic material, and the chemical formula of the full-filled tungsten bronze structure high-entropy ferroelectric ceramic material is A 3 B 5 O 15 Wherein the A site is full, six elements with equal molar ratio content are contained, and (Sr) is preferred 0.5 Ba 0.5 K 0.5 La 0.5 Ag 0.5 Na 0.5 )Nb 5 O 15 。
In the invention, the tungsten bronze structureThe A site of (A) is designed to be Sr in an equimolar ratio 2+ 、Ba 2+ 、Ag + 、K + 、La 3+ 、Na + Six kinds of metal ions are used to obtain the full-filled tungsten bronze structure high-entropy ferroelectric ceramic material.
On the structure of the ferroelectric ceramic material with the tungsten bronze structure, the A position occupies 6 positions (full), and the ferroelectric ceramic material is a full-filling type tungsten bronze structure.
The ferroelectric ceramic material with the tungsten bronze structure has configuration entropy Delta S mix Not less than 1.61R, which is a high entropy system.
In a second aspect, the invention provides a preparation method of a filled tungsten bronze structure high-entropy ferroelectric ceramic material, which comprises the following steps:
selecting strontium carbonate powder, barium carbonate powder, potassium carbonate powder, lanthanum oxide powder, silver oxide, sodium carbonate powder and niobium pentoxide powder as raw materials according to a chemical formula (Sr) 0.5 Ba 0.5 K 0.5 La 0.5 Ag 0.5 Na 0.5 )Nb 5 O 15 Weighing and mixing, and then calcining and finely grinding to obtain ceramic powder;
mixing the obtained ceramic powder with a binder, and then granulating, sieving and forming to obtain a ceramic green body;
and (3) performing plastic removal and sintering on the obtained ceramic green body to obtain the high-entropy ferroelectric ceramic material with the full-filling type tungsten bronze structure.
Preferably, in the step (1), the mixing mode is ball milling mixing; absolute ethyl alcohol is used as ball milling medium, the rotating speed is 200-220 r/min, and the time is 6-24 hours.
Preferably, in the step (1), the calcination temperature is about 1200 ℃ and the calcination time is 3 to 4 hours.
Preferably, in the step (2), the binder is a polyvinyl alcohol aqueous solution with a concentration of 6 to 7wt.%; the addition amount of the binder is 6-7 wt.% of the mass of the ceramic powder; the screened screen mesh is 40 meshes.
Preferably, in the step (3), the temperature for plastic removal is 600 ℃ and the time is 2 hours.
Preferably, in the step (3), the sintering temperature is 1160-1220 ℃, the time is 3-4 hours, and the sintering temperature rise rate is 2 ℃/min.
In another aspect, the invention provides a tungsten bronze structure ferroelectric ceramic, which comprises the filled type tungsten bronze structure high-entropy ferroelectric ceramic material.
The invention combines the high-entropy concept with the tungsten bronze structure, the obtained high-entropy ferroelectric ceramic material with the full-filling type tungsten bronze structure has a stable single-phase structure, the A-site complex atom arrangement configuration enhances the relaxation property of a material system, the high-entropy ferroelectric ceramic can obtain the energy storage density of 6.048J/cm < 3 > and the energy storage efficiency of 82.1% under 560kV/cm, and has potential application in pulse power capacitors. The technical scheme of the invention provides a new idea for designing a novel dielectric material, and the preparation process is simple.
Drawings
Other features, objects and advantages of the present invention will become more apparent upon reading of the following detailed description of non-limiting embodiments thereof, with reference to the accompanying drawings.
FIG. 1 is an X-ray diffraction pattern of a filled tungsten bronze structured high entropy ferroelectric ceramic material of example 1;
FIG. 2 is a surface micro-topography of the filled tungsten bronze structured high-entropy ferroelectric ceramic material of example 1;
FIG. 3 is a dielectric thermogram of the filled tungsten bronze structure high entropy ferroelectric ceramic material of example 1;
FIG. 4 is a unipolar hysteresis loop diagram of the filled tungsten bronze structured high entropy ferroelectric ceramic material of example 1.
Detailed Description
The present invention is further illustrated by the following examples, which are to be construed as merely illustrative, and not a limitation of the present invention.
In the invention, the chemical formula of the filled tungsten bronze structure high-entropy ferroelectric ceramic material is A 3 B 5 O 15 Preferably is (Sr) 0.5 Ba 0.5 K 0.5 La 0.5 Ag 0.5 Na 0.5 )Nb 5 O 15 。
The invention adopts a solid phase method to prepare the high-entropy ferroelectric ceramic material with the full-filling type tungsten bronze structure, and the process flow is simple. The preparation method of the filled tungsten bronze structure high-entropy ferroelectric ceramic material provided by the invention is exemplarily described as follows.
In the present invention, according to the formula (Sr) 0.5 Ba 0.5 K 0.5 La 0.5 Ag 0.5 Na 0.5 )Nb 5 O 15 Performing material calculation, wherein the used raw materials comprise strontium carbonate powder, barium carbonate powder, potassium carbonate powder, lanthanum oxide powder, silver oxide powder, sodium carbonate powder and niobium pentoxide powder; and weighing by using an electronic balance until the weighing is accurate to 0.001g. Wherein, the purity of strontium carbonate is 99.99 percent, the purity of barium carbonate is 99.5 percent, the purity of potassium carbonate is 99.0 percent, the purity of lanthanum oxide is 99.95 percent, the purity of silver oxide is 99.7 percent, the purity of sodium carbonate is 99.8 percent, and the purity of niobium pentoxide is 99.99 percent.
And mixing the weighed raw material powder, putting the mixture into a ball mill, carrying out ball milling mixing by taking a zirconia column, zirconia balls and absolute ethyl alcohol as media, and finally drying and calcining to obtain the ceramic powder. Wherein the calcining temperature can be 1200 ℃ and the calcining time can be 3-4 hours. The zirconia balls used for ball milling and mixing have the particle size of 6mm, the zirconia columns have the size of 10mm in diameter multiplied by 10mm in height, and the number of the zirconia columns respectively accounts for half.
The ceramic powder is put into a stirring mill, and is milled by taking zirconia balls with small particle size (for example, the particle size of the zirconia balls is 1 mm) and absolute ethyl alcohol as media, and dried to obtain mixed powder.
And uniformly mixing the mixed powder with a binder, grinding, granulating, sieving and carrying out compression molding to obtain the ceramic green body. The adhesive is preferably polyvinyl alcohol aqueous solution, the concentration is 6-7 wt.%, and the addition amount is 5-7% of the mass of the ceramic powder. The screening mesh is preferably 40 mesh.
And performing plastic removal and sintering on the ceramic green body to obtain the full-filled tungsten bronze structure high-entropy ferroelectric ceramic material. Wherein the temperature for plastic discharge can be 600 ℃ and the time can be 2 hours. The sintering temperature is preferably 1200 ℃ and the sintering time is preferably 4 hours.
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 insubstantial modifications and adaptations of the invention by those skilled in the art based on the foregoing description are intended to be included within the scope of the invention. The specific process parameters and the like of the following examples are also merely 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
(1) (Sr) according to the formula of the invention 0.5 Ba 0.5 K 0.5 La 0.5 Ag 0.5 Na 0.5 )Nb 5 O 15 And (6) carrying out ingredient calculation.
The raw materials used include: the purity of the strontium carbonate is 99.99 percent, molecular weight is 147.630; the purity of barium carbonate is 99.5%, and the molecular weight is 197.336; the purity of the potassium carbonate is 99.00 percent, and the molecular weight is 138.250; the purity of lanthanum oxide is 99.95 percent, and the molecular weight is 325.809; the purity of the silver oxide is 99.70 percent, and the molecular weight is 231.736; the purity of the sodium carbonate is 99.8 percent, and the molecular weight is 105.990; the purity of niobium pentoxide was 99.99%, and the molecular weight was 265.810. Weighing by using an electronic balance, wherein the weighing is accurate to 0.001g;
(2) Mixing the weighed raw materials, putting the raw materials into a nylon tank, adding absolute ethyl alcohol with the height not higher than 2/3 of the height of the tank body into the tank, and putting the nylon tank on a planetary ball mill for mixing for 6 hours by taking zirconia balls and zirconia columns as media (the grain diameter of the zirconia balls is 6mm, the size of the zirconia columns is 10mm in diameter and 10mm in height, and the number of the zirconia balls is half respectively); then pouring out the powder to be dried in a baking oven, sieving the powder by using a 40-mesh nylon sieve, and pressing the sieved mixed powder into a cylinder with the diameter of 15mm multiplied by 2mm in height on a press machine; synthesizing for 3 hours at 1200 ℃ in an oxygen atmosphere, and then crushing and screening by a 40-mesh screen to obtain ceramic powder;
(3) Putting the obtained ceramic powder into a stirring mill, grinding the ceramic powder for 6 hours by taking zirconia balls with the diameter of 1mm and absolute ethyl alcohol as media, and drying the ceramic powder in a baking oven to obtain ceramic powder;
(4) Adding a polyvinyl alcohol aqueous solution with the concentration of 7wt.% into the mixed powder, wherein the adding amount of the polyvinyl alcohol aqueous solution is 6.5% of the mass of the ceramic powder. Then evenly granulating, sieving with a 40-mesh sieve, carrying out compression molding to obtain small cylinders with the diameter of 13mm multiplied by 1mm, and carrying out plastic discharge;
(5) And sintering the obtained blank after plastic removal in an alumina crucible at the sintering temperature of 1200 ℃ for 4 hours, naturally cooling to room temperature, and taking out the sample to obtain the full-filled tungsten bronze structure high-entropy ferroelectric ceramic material.
The prepared filled tungsten bronze structure high-entropy ferroelectric ceramic material is subjected to an X-ray diffraction test, and an X-ray diffraction pattern of example 1 is shown in attached figure 1.
A surface topography was taken after the ceramic surface was treated and figure 2 shows the surface topography of example 1.
Grinding and polishing two sides of the ceramic, plating silver on the electrodes, testing electrical properties, and showing a dielectric temperature spectrum of the embodiment 1 in an attached figure 3; figure 4 shows the unipolar hysteresis loop of example 1.
FIG. 1 shows the X-ray diffraction pattern of example 1, and it can be seen from the figure that the obtained ceramic of example 1 has no impurity phase, is basically consistent with standard card PDF #38-1236, and has a space group P4bm, and belongs to a tetragonal tungsten bronze crystal system.
FIG. 2 shows the surface topography of example 1, from which it can be seen that the ceramic surface is dense and the grains are uniformly distributed.
Fig. 3 shows the dielectric temperature spectrum of example 1, from which it can be seen that the maximum dielectric constant gradually decreases as the frequency increases and the dielectric peak moves toward a high temperature direction, showing the characteristics of a typical relaxor ferroelectric; the material loss is kept at a low level within the temperature range of-50 to 200 ℃.
FIG. 4 shows the unipolar hysteresis loop of example 1, from which it is apparent that the ceramic breakdown field strength is 560kV/cm and the maximum polarization is 35.64. Mu.C/cm 2 The energy storage density is 6.048J/cm 3 The energy storage efficiency was 82.1%.
In conclusion, the preparation process of the embodiment of the invention is simple, and the prepared full-filling type tungsten bronze structure high-entropy ferroelectric ceramic material has potential application in pulse power capacitors in energy storage density and energy storage efficiency.
The foregoing is a more detailed description of the invention in connection with specific preferred embodiments and it is not intended that the invention be limited to these specific details. For those skilled in the art to which the invention pertains, several simple deductions or substitutions can be made without departing from the spirit of the invention, and all shall be considered as belonging to the protection scope of the invention.
Claims (9)
1. A filled tungsten bronze structure high-entropy ferroelectric ceramic material is characterized in that the structural formula of the ceramic material is as follows: a. The 3 B 5 O 15 Wherein, the A site is full and contains six elements with equal molar ratio, the structural formula of the ceramic material is as follows: (Sr) 0.5 Ba 0.5 K 0.5 La 0.5 Ag 0.5 Na 0.5 )Nb 5 O 15 。
2. A filled tungsten bronze structure high-entropy ferroelectric ceramic material according to claim 1, characterized in that the ceramic material has a configuration entropy Δ S mix ≥1.61R。
3. A method for preparing a high-entropy ferroelectric ceramic material with a filled tungsten bronze structure according to claim 1, comprising:
selecting strontium carbonate powder, barium carbonate powder, potassium carbonate powder, lanthanum oxide powder, silver oxide powder, sodium carbonate powder and niobium pentoxide powder as raw materials according to a chemical formula (Sr) 0.5 Ba 0.5 K 0.5 La 0.5 Ag 0.5 Na 0.5 )Nb 5 O 15 Weighing and mixing, and then calcining and finely grinding to obtain ceramic powder;
step (2), mixing the obtained ceramic powder with a binder, and then granulating, sieving and forming to obtain a ceramic green body;
and (3) performing plastic removal and sintering on the obtained ceramic green body to obtain the high-entropy ferroelectric ceramic material with the full-filling type tungsten bronze structure.
4. The method according to claim 3, wherein in the step (1), the mixing is performed by ball milling; the absolute ethyl alcohol is used as a ball milling medium, the rotating speed is 200-220 r/min, and the time is 6-24 hours.
5. The method according to claim 3, wherein in the step (1), the calcination is carried out at 1200 ℃ for 3 to 4 hours.
6. The method according to claim 3, wherein in the step (2), the binder is an aqueous polyvinyl alcohol solution having a concentration of 6 to 7wt.%; the addition amount of the binder is 6-7 wt.% of the mass of the ceramic powder; the screened screen mesh is 40 meshes.
7. The method according to claim 3, wherein in the step (3), the temperature of the plastic discharge is 600 ℃ and the time is 2 hours.
8. The method according to claim 3, wherein in the step (3), the sintering temperature is 1160-1220 ℃ for 3-4 hours, and the sintering temperature rise rate is 2 ℃/min.
9. A tungsten bronze structure ferroelectric ceramic comprising the filled tungsten bronze structure high entropy ferroelectric ceramic material of any one of claims 1-2.
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| CN107253859B (en) * | 2017-07-14 | 2019-12-03 | 陕西师范大学 | Luminous ferroelectric ceramic material of the Eu-Bi codope tungsten bronze structure of high-incidence photo and thermal stability and preparation method thereof |
| CN111875389B (en) * | 2020-08-13 | 2022-10-28 | 西安科技大学 | Method for regulating and controlling performance of lead-free piezoelectric ceramic |
| WO2022132883A1 (en) * | 2020-12-15 | 2022-06-23 | University Of Maryland, College Park | Multi-element compound nanoparticles, and systems and methods of making and use thereof |
| CN112876247B (en) * | 2021-01-26 | 2022-08-02 | 杭州电子科技大学 | Wide-temperature-stability high-energy-storage-density strontium sodium niobate-based tungsten bronze ceramic and preparation method thereof |
| CN113024250B (en) * | 2021-03-30 | 2022-09-06 | 陕西师范大学 | Sb with high energy storage density and energy storage efficiency 5+ Strontium sodium silver tungsten bronze doped ferroelectric ceramic material and preparation method thereof |
| CN114621004B (en) * | 2022-01-26 | 2023-07-07 | 杭州电子科技大学 | High-entropy ceramic material with high energy storage density and preparation method thereof |
| CN114685165B (en) * | 2022-04-08 | 2022-11-22 | 桂林理工大学 | High-entropy oxide ceramic with ten-component brown yttrium niobium ore structure and preparation method thereof |
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