CN110451807B - Bismuth barium sodium niobate-based glass ceramic material with high energy storage density and preparation and application thereof - Google Patents
Bismuth barium sodium niobate-based glass ceramic material with high energy storage density and preparation and application thereof Download PDFInfo
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- 238000004146 energy storage Methods 0.000 title claims abstract description 70
- 239000006112 glass ceramic composition Substances 0.000 title claims abstract description 34
- KOJWXHDDSAMYEG-UHFFFAOYSA-N [Na].[Ba].[Bi] Chemical compound [Na].[Ba].[Bi] KOJWXHDDSAMYEG-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000011521 glass Substances 0.000 claims abstract description 40
- 238000002425 crystallisation Methods 0.000 claims abstract description 26
- 230000008025 crystallization Effects 0.000 claims abstract description 26
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 claims abstract description 22
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 21
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Chemical compound O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 claims abstract description 21
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(iii) oxide Chemical compound O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 11
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 11
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910000029 sodium carbonate Inorganic materials 0.000 claims abstract description 11
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 11
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 11
- 238000002844 melting Methods 0.000 claims abstract description 7
- 230000008018 melting Effects 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 6
- 239000000463 material Substances 0.000 claims description 41
- 239000003990 capacitor Substances 0.000 claims description 17
- 239000002002 slurry Substances 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 5
- 238000000465 moulding Methods 0.000 claims description 3
- 239000002241 glass-ceramic Substances 0.000 abstract description 23
- 230000015556 catabolic process Effects 0.000 abstract description 15
- 239000011232 storage material Substances 0.000 abstract description 13
- 239000002994 raw material Substances 0.000 abstract description 9
- 238000000137 annealing Methods 0.000 abstract description 8
- 239000000126 substance Substances 0.000 abstract description 8
- 238000005520 cutting process Methods 0.000 abstract description 7
- 230000008901 benefit Effects 0.000 abstract description 4
- 238000001035 drying Methods 0.000 abstract description 2
- 239000000156 glass melt Substances 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 description 15
- 238000000498 ball milling Methods 0.000 description 12
- 239000000203 mixture Substances 0.000 description 12
- 230000004913 activation Effects 0.000 description 10
- 239000000919 ceramic Substances 0.000 description 9
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 229910003378 NaNbO3 Inorganic materials 0.000 description 6
- 230000010287 polarization Effects 0.000 description 6
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 5
- 229910052700 potassium Inorganic materials 0.000 description 5
- 239000011591 potassium Substances 0.000 description 5
- 239000003989 dielectric material Substances 0.000 description 4
- 238000000113 differential scanning calorimetry Methods 0.000 description 4
- 238000001453 impedance spectrum Methods 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- 230000008859 change Effects 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 229910000906 Bronze Inorganic materials 0.000 description 2
- 239000010974 bronze Substances 0.000 description 2
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 239000010937 tungsten Substances 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910003334 KNbO3 Inorganic materials 0.000 description 1
- RMIBFJWHAHLICA-UHFFFAOYSA-N [K].[Ba] Chemical compound [K].[Ba] RMIBFJWHAHLICA-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000006121 base glass Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000005621 ferroelectricity Effects 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- MUPJWXCPTRQOKY-UHFFFAOYSA-N sodium;niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Na+].[Nb+5] MUPJWXCPTRQOKY-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B19/00—Other methods of shaping glass
- C03B19/02—Other methods of shaping glass by casting molten glass, e.g. injection moulding
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B32/00—Thermal after-treatment of glass products not provided for in groups C03B19/00, C03B25/00 - C03B31/00 or C03B37/00, e.g. crystallisation, eliminating gas inclusions or other impurities; Hot-pressing vitrified, non-porous, shaped glass products
- C03B32/02—Thermal crystallisation, e.g. for crystallising glass bodies into glass-ceramic articles
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C1/00—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C10/00—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G4/00—Fixed capacitors; Processes of their manufacture
- H01G4/002—Details
- H01G4/018—Dielectrics
- H01G4/06—Solid dielectrics
- H01G4/08—Inorganic dielectrics
- H01G4/12—Ceramic dielectrics
- H01G4/129—Ceramic dielectrics containing a glassy phase, e.g. glass ceramic
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Abstract
The invention relates to a bismuth barium sodium niobate based glass ceramic material with high energy storage density, and preparation and application thereof, wherein the chemical components of the glass ceramic material conform to the chemical general formula of 21.6BaCO3‑2.4Bi2O3‑6Na2CO3‑30Nb2O5‑40SiO2With BaCO3、Bi2O3、Na2CO3、Nb2O5、SiO2The glass melt is prepared by uniformly mixing raw materials, drying, and then melting at high temperature; quickly pouring the high-temperature melt into a preheated mold, removing residual stress in a glass body through annealing treatment, and then cutting the glass block into glass sheets with equal size and thickness; and performing controlled crystallization on the glass sheet to obtain the glass ceramic energy storage material. Compared with the prior art, the glass ceramic energy storage material prepared by the invention has the advantages of high dielectric constant (118), high breakdown field strength (1878.75 kV/cm) and high energy storage density (18.4J/cm)3) Low loss (about 0.025), and good temperature stability.
Description
Technical Field
The invention belongs to the field of dielectric energy storage materials, and particularly relates to a bismuth barium sodium niobate-based glass ceramic material with high energy storage density, and a preparation method and application thereof.
Background
With the development of social industry, energy demand is increasing, and in the face of energy crisis, the problems of improving the utilization efficiency of traditional energy and developing new energy are increasingly prominent, in order to meet the application demand in the energy field, energy storage devices are developing towards miniaturization and light weight, and in order to reduce the device volume, the energy storage density in the unit volume of the device must be improved, and therefore, research and development and application of high energy storage density dielectric are concerned. In order to meet the requirements of high energy storage density, high charging and discharging speed, high utilization efficiency and the like of an energy storage capacitor, the preparation of a dielectric material with high dielectric constant and high breakdown field strength is a main target of the current energy storage dielectric research. At present, with the development of light weight and integration of pulse power systems, it becomes more and more important to further improve the energy storage density of energy storage elements in pulse power equipment. However, the energy storage density of the existing capacitor element is generally low. In order to increase the energy storage density of the capacitor, various capacitors using ferroelectric ceramics, antiferroelectric ceramics, and high polymers as dielectrics have been developed. However, the disadvantages of these materials are also evident, limiting their application in practical scenarios. For ferroelectric ceramics, the dielectric constant is high, but pores often exist in ceramic materials, so that breakdown-resistant field strength of the materials can be reduced, meanwhile, the density of the materials is reduced due to the pores, internal consumption of a capacitor is large, and heat is easily generated in the capacitor to damage electronic components. For antiferroelectric materials, microcracks are easily caused during repeated charge and discharge due to the ferroelectric-antiferroelectric phase transition to damage the capacitor. High polymer energy storage materials, which have the advantage of high breakdown field resistance, have very low dielectric constant, usually less than 10, resulting in low energy storage density, and poor thermal stability, and can easily damage capacitors if electronic components generate too high heat.
The glass ceramic is also called as microcrystalline glass, and is a dielectric material which realizes uniform coexistence of microcrystalline phase and glass phase by melting raw materials with designed components into base glass and then separating out required specific microcrystalline phase in a glass matrix through controlling crystallization. The crystal grain appearance and the size of the glass ceramic material can be controlled through a crystallization process, the precipitated crystal phase is uniform, the size is usually from nanometer to micron, the crystallization process is directly carried out in a compact glass matrix, the compactness is very high, so the glass ceramic material usually has higher breakdown-resistant field intensity, and meanwhile, the improvement of the dielectric constant can be realized through controlling the precipitation of the ferroelectric phase, so that the high dielectric constant and the high breakdown field intensity are realized simultaneously, the energy storage density is greatly improved, the discharge speed is high, and the glass ceramic material has great potential in pulse power application. In addition, the glass ceramic material has very large component adjustability and very high flexibility, both the glass phase and the ceramic phase can be adjusted and controlled, and because the grain size is small, the ferroelectricity of the ceramic phase is not shown, and the glass ceramic material is generally linear, namely, the charging and discharging efficiency is high. However, glass ceramic materials also suffer from the same problems as polymer-ceramic composite dielectrics, in that a considerable interfacial polarization occurs due to the large difference in dielectric constant between the glass phase and the ceramic phase. The influence of interface polarization on the energy storage performance is mainly to cause the energy stored in the material to be not fully released, and to have adverse effect on the charge and discharge performance in practical application.
Chen J. et al by reaction on BaO-SrO-TiO2-Al2O3-SiO2System glass ceramic adding AlF3And MnO2The microstructure and the dielectric property of the ceramic are optimized, and the addition of a proper amount of AlF is found3The dielectric constant can be improved, and the crystal form can be changed; and MnO is added2The dielectric loss can be reduced, and the resistivity can be increased. Chen J. et al studied the effect of Ba/Ti ratio on dielectric properties and microstructure of barium strontium titanate-based glass ceramics, and found that the increase of Ba content, the increase of dielectric constant of glass ceramics, the decrease of breakdown resistance, and the presence of dendrites observed in microstructure. 2011, Zhang Y. et al in BaO-SrO-TiO2-Al2O3-SiO2-BaF2The corresponding research on the system glass ceramic shows that when the crystallization temperature is increased from 780 ℃ to 830 ℃, the dielectric constant is obviously increased, which is considered to be caused by that when the crystallization temperature is increased, the surface crystallization of the glass is transformed into the whole crystallization, so that a great amount of ferroelectric phase crystals are precipitated. Xiu S. et al report on SrO-BaO-Nb2O5-SiO2-Al2O3The microstructure of the material can be optimized by changing the Al/Si ratio in the system, and when the Al/Si ratio is 0.29, the energy storage density of the materialCan reach 4.8J/cm3。
Chinese patent with application number 201610051694.0 discloses a barium potassium niobate-based glass ceramic energy storage material and a preparation method thereof, wherein the chemical components conform to the chemical general formula: 32xBaO-32(1-x)K2O-32Nb2O5-36SiO2Wherein, in the step (A),xthe value range of (A) is 0.5-0.9. Firstly, weighing BaCO3、K2CO3、Nb2O5And SiO2Uniformly mixing, and melting at high temperature to obtain a high-temperature melt; and then quickly pouring the high-temperature melt into a preheated metal mold, preserving the heat for several hours at a certain temperature, performing stress relief annealing to prepare transparent glass, slicing to obtain a glass sheet, and finally performing controlled crystallization on the glass sheet to prepare the glass ceramic sample. Although the method is simple, the glass ceramic material prepared by the patent contains more KNbO3And KNb3O8Phase, materials are easily deliquesced by moisture absorption; meanwhile, the dielectric constant of the capacitor is lower than 70 under the test conditions of room temperature and 100kHz, which is not beneficial to improving the capacitance of the capacitor.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide the composition, preparation and application of the bismuth barium sodium niobate-based glass ceramic material with high energy storage density.
The purpose of the invention can be realized by the following technical scheme:
the bismuth barium sodium niobate based glass ceramic material with high energy storage density has ceramic particle component mainly comprising NaNbO of perovskite phase3And Ba of tungsten bronze phase2NaNb5O15The chemical composition of the glass ceramic material conforms to the chemical general formula of 21.6BaCO3-2.4Bi2O3-6Na2CO3-30Nb2O5-40SiO2。
The preparation method of the bismuth barium sodium niobate-based glass ceramic material with high energy storage density comprises the following steps:
(1) with BaCO3、Bi2O3、Na2CO3、Nb2O5、SiO2Is prepared from 21.6BaCO by mol3-2.4Bi2O3-6Na2CO3-30Nb2O5-40SiO2Burdening, uniformly mixing, and melting at high temperature to prepare high-temperature molten slurry;
(2) pouring the high-temperature molten slurry prepared in the step (1) into a preheated mold for molding, keeping the preheating temperature for several hours to remove residual stress in the glass, preparing transparent uniform glass, and slicing to obtain glass sheets;
(3) and (4) performing controlled crystallization on the glass sheet prepared in the step (3) to obtain the niobate-based glass ceramic energy storage material.
In the step (1), the high-temperature melting is controlled at 1450-1550 ℃ for 1-2 h.
As a preferred embodiment, the temperature is 1550 ℃.
In the step (2), the preheating temperature of the die is 600-650 ℃, and the stress removing time of the high-temperature molten slurry in the die is 5-6 h.
In a preferred embodiment, the preheating temperature is 650 ℃ and the stress relief time is 6 h.
And (3) controlling the temperature rise rate to be 3 ℃/min during controlled crystallization in the step (3), controlling the crystallization temperature to be 850-1000 ℃, and controlling the temperature for 3-5 h.
In a preferred embodiment, the crystallization temperature is 950 ℃ and the temperature is controlled for 3 h.
The bismuth barium sodium niobate based glass ceramic material with high energy storage density can be used as an energy storage capacitor material due to high dielectric constant and energy storage density and wide temperature range of controlled crystallization.
Compared with the existing potassium-containing energy storage capacitor material, if the potassium-containing material is directly and simply replaced by sodium, uniform glass cannot be obtained, so that the stable performance of the subsequent treatment of the material cannot be ensured, the dielectric constant of the general potassium-containing material is lower than 70, and if the potassium-containing material is not treated under the conditions of the designed mixture ratio and the corresponding heat treatment process, the dielectric constant of the obtained product at room temperature cannot be 100, so that the product obtained by the treatment of the invention is superior to the potassium-containing material.
Further, the present application requires strict control of Na2CO3The addition amount of (A) is firstly considered to be capable of obtaining a homogeneous glass sample under the condition of the mixture ratio to ensure the stability after subsequent treatment, and secondly, the high-dielectric constant phase NaNbO is obtained by crystallization under the mixture ratio3（ɛrAnd = 500-600), the energy storage density of the glass ceramic sample is effectively improved. The temperature of crystallization, preheating destressing temperature and time were obtained based on the results of Differential Scanning Calorimetry (DSC), as shown in FIG. 7, and the glass transition temperature (T) of the present invention according to the DSC profileg) At 660-680 ℃, so that the stress removal temperature is not higher than Tg(ii) a The spectrum shows that exothermic peaks appear at 740-770 ℃ and 870-900 ℃, and phase change can occur in the two temperature ranges, so the temperature range disclosed by the application is selected.
Compared with the prior art, the dielectric constant and the energy storage density of the glass ceramic are remarkably improved by adjusting the crystallization temperature, and the prepared glass ceramic energy storage material has the advantages of high dielectric constant (118), high breakdown field strength (1878.75 kV/cm) and high energy storage density (18.4J/cm)3) Low loss (-0.025), good temperature stability and the like. Particularly, when the crystallization temperature is 950 ℃, the dielectric constant reaches 118, the breakdown field strength reaches 1878.75kV/cm, and the theoretical energy storage density reaches the optimal value of 18.4J/cm3. This is because Bi is added2O3Ba with high dielectric constant is precipitated after heat treatment at 950 DEG C2NaNb5O15And NaNbO3(ii) a Meanwhile, the crystal phases are uniformly distributed in the glass matrix and have lower activation energy, so that the material has higher breakdown-resistant field strength. Moreover, the invention also has the following advantages:
(1) from the dielectric temperature spectrum, the glass ceramic sample subjected to crystallization treatment at 850-1000 ℃ can keep a relatively stable dielectric constant when the environmental temperature range is-70-110 ℃, and the change of the dielectric constant is less than 5%. Thus having good temperature stability.
(2) Na in the raw Material2CO3Mostly with Ba2NaNb5O15And NaNbO3The phase is separated out, and the material is not easy to absorb moisture and age.
(3) The preparation method is simple, does not need complex post-treatment steps, and is economical and practical.
Drawings
FIG. 1 shows 21.6BaCO at different crystallization temperatures3-2.4Bi2O3-6Na2CO3-30Nb2O5-40SiO2Dielectric constant of (mol%) base glass-ceramic, change curve of dielectric loss with temperature;
FIG. 2 shows the crystallization temperature of 21.6BaCO3-2.4Bi2O3-6Na2CO3-30Nb2O5-40SiO2(mol%) Weibull distribution curve of breakdown-resistant field strength of the glass ceramic energy storage material;
FIG. 3 shows the crystallization temperature of 21.6BaCO3-2.4Bi2O3-6Na2CO3-30Nb2O5-40SiO2(mol%) theoretical energy storage density curve of the glass ceramic energy storage material;
FIG. 4 shows the crystallization temperature of 21.6BaCO3-2.4Bi2O3-6Na2CO3-30Nb2O5-40SiO2(mol%) complex impedance curve of glass ceramic energy storage material;
FIG. 5 shows 21.6BaCO3-2.4Bi2O3-6Na2CO3-30Nb2O5-40SiO2(mol%) relation curve of activation energy, breakdown strength and crystallization temperature of the glass ceramic energy storage material;
FIG. 6 shows 21.6BaCO at different crystallization temperatures3-2.4Bi2O3-6Na2CO3-30Nb2O5-40SiO2(mol%) XRD spectrogram of the glass ceramic energy storage material;
FIG. 7 shows 21.6BaCO at different heating rates3-2.4Bi2O3-6Na2CO3-30Nb2O5-40SiO2Differential scanning calorimetry of parent phase glassAnalysis (DSC) of the spectrum.
Detailed Description
The present invention will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way. It should be noted that variations and modifications can be made by persons skilled in the art without departing from the spirit of the invention. All falling within the scope of the present invention.
The bismuth barium sodium niobate based glass ceramic material with high energy storage density has ceramic particle component mainly comprising NaNbO of perovskite phase3And Ba of tungsten bronze phase2NaNb5O15The chemical composition of the glass ceramic material conforms to the chemical general formula of 21.6BaCO3-2.4Bi2O3-6Na2CO3-30Nb2O5-40SiO2。
The preparation method of the bismuth barium sodium niobate-based glass ceramic material with high energy storage density comprises the following steps:
(1) with BaCO3、Bi2O3、Na2CO3、Nb2O5、SiO2Is prepared from 21.6BaCO by mol3-2.4Bi2O3-6Na2CO3-30Nb2O5-40SiO2Burdening, uniformly mixing, and controlling the temperature to be 1450-1550 ℃ for high-temperature melting for 1-2 h to prepare high-temperature molten slurry;
(2) pouring the high-temperature molten slurry prepared in the step (1) into a preheated mold at 600-650 ℃ for molding, keeping the preheating temperature for 5-6 h to remove residual stress in glass, preparing transparent uniform glass, and slicing to obtain glass sheets;
(3) and (4) performing controlled crystallization on the glass sheet prepared in the step (3), wherein the temperature rise rate is controlled to be 3 ℃/min during the controlled crystallization, the crystallization temperature is 850-1000 ℃, and the temperature control time is 3-5 h, so that the niobate-based glass ceramic energy storage material is prepared.
The following are more detailed embodiments, and the technical solutions and the technical effects obtained by the present invention will be further described by the following embodiments.
Example 1
The preparation method of the bismuth barium sodium niobate-based glass ceramic material with high energy storage density comprises the following steps:
(1) with a purity of more than 99 wt.% of BaCO3、Bi2O3、Na2CO3、Nb2O5、SiO2The raw materials are mixed according to the mol percentage of 21.6%, 2.4%, 6%, 30% and 40%, and the mixture is subjected to ball milling for 24 hours, dried at 100 ℃ for 6 hours and then melted at 1550 ℃ for 2 hours, (the ball milling takes absolute ethyl alcohol as a medium, and the ball-to-material ratio is 1.5: 1).
(2) Pouring the high-temperature melt obtained in the step (1) into a square metal mold, performing stress relief annealing at 650 ℃ for 6 hours, and then cutting to obtain a glass sheet with the thickness of 1.0-1.5 mm;
(3) and (3) putting an equal number of the glass sheets prepared in the step (2) into a crucible, heating to 850 ℃ at a heating speed of 3 ℃/min, and preserving heat for 3h to obtain the glass ceramic.
The dielectric properties of the sample prepared in this example are shown in fig. 1, the dielectric constant is 102 at room temperature, and the loss is 0.029; the withstand voltage performance is 1444.46kV/cm as shown in figure 2, the energy storage density is shown in figure 3, and the theoretical energy storage density is 9.4J/cm at most3The material can be applied to energy storage capacitor materials; the impedance spectrum is shown in FIG. 4, and the activation energy is shown in FIG. 5 and is 1.02 eV; XRD is shown in figure 6.
In this example, there is Ba2NaNb5O15And NaNbO3And the material is precipitated, so that the dielectric constant of the material is greatly improved compared with that of glass. The activation energy of the material is smaller, which indicates that the degree of interfacial polarization is lower, so that the breakdown field strength is higher.
Example 2
The preparation method of the bismuth barium sodium niobate-based glass ceramic material with high energy storage density comprises the following steps:
(1) with a purity of more than 99 wt.% of BaCO3、Bi2O3、Na2CO3、Nb2O5、SiO2The raw materials are mixed according to the mol percentage of 21.6%, 2.4%, 6%, 30% and 40%, and the mixture is subjected to ball milling for 24 hours, dried at 100 ℃ for 6 hours and then melted at 1550 ℃ for 2 hours, (the ball milling takes absolute ethyl alcohol as a medium, and the ball-to-material ratio is 1.5: 1).
(2) Pouring the high-temperature melt obtained in the step (1) into a square metal mold, performing stress relief annealing at 650 ℃ for 6 hours, and then cutting to obtain a glass sheet with the thickness of 1.0-1.5 mm;
(3) and (3) putting an equal number of the glass sheets prepared in the step (2) into a crucible, heating to 900 ℃ at a heating rate of 3 ℃/min, and then preserving heat for 3h to obtain the glass ceramic.
The dielectric properties of the sample prepared in this example are shown in fig. 1, the dielectric constant is 105 at room temperature, and the loss is 0.017; the withstand voltage is 1238.97kV/cm as shown in FIG. 2, the energy storage density is 7.1J/cm at most as shown in FIG. 33The material can be applied to energy storage capacitor materials; the impedance spectrum is shown in FIG. 4, and the activation energy is shown in FIG. 5 and is 1.45 eV; XRD is shown in figure 6.
In this example, there is Ba2NaNb5O15And NaNbO3The precipitation amount is increased, so that the dielectric constant of the material is improved. The activation energy of the material increases, indicating an increase in the degree of interfacial polarization and thus a decrease in the breakdown field strength.
Example 3
The preparation method of the bismuth barium sodium niobate-based glass ceramic material with high energy storage density comprises the following steps:
(1) with a purity of more than 99 wt.% of BaCO3、Bi2O3、Na2CO3、Nb2O5、SiO2The raw materials are mixed according to the mol percentage of 21.6%, 2.4%, 6%, 30% and 40%, and the mixture is subjected to ball milling for 24 hours, dried at 100 ℃ for 6 hours and then melted at 1550 ℃ for 2 hours, (the ball milling takes absolute ethyl alcohol as a medium, and the ball-to-material ratio is 1.5: 1).
(2) Pouring the high-temperature melt obtained in the step (1) into a square metal mold, performing stress relief annealing at 650 ℃ for 6 hours, and then cutting to obtain a glass sheet with the thickness of 1.0-1.5 mm;
(3) and (3) putting an equal number of the glass sheets prepared in the step (2) into a crucible, heating to 950 ℃ at a heating rate of 3 ℃/min, and then preserving heat for 3h to obtain the glass ceramic.
The dielectric properties of the sample prepared in this example are shown in fig. 1, the dielectric constant is 118 at room temperature, and the loss is 0.025; the withstand voltage performance is 1878.75kV/cm as shown in figure 2, the energy storage density is shown in figure 3, and the theoretical energy storage density is 18.4J/cm at most3The material can be applied to energy storage capacitor materials; the impedance spectrum is shown in FIG. 4, and the activation energy is shown in FIG. 5 and is 1.40 eV; XRD is shown in figure 6.
In this example, there is Ba2NaNb5O15And NaNbO3The precipitation amount is further increased, so that the dielectric constant of the material is further improved. The activation energy of the material is reduced, which indicates that the degree of interfacial polarization is reduced, and thus the breakdown field strength is improved.
Example 4
The preparation method of the bismuth barium sodium niobate-based glass ceramic material with high energy storage density comprises the following steps:
(1) with a purity of more than 99 wt.% of BaCO3、Bi2O3、Na2CO3、Nb2O5、SiO2The raw materials are mixed according to the mol percentage of 21.6%, 2.4%, 6%, 30% and 40%, and the mixture is subjected to ball milling for 24 hours, dried at 100 ℃ for 6 hours and then melted at 1550 ℃ for 2 hours, (the ball milling takes absolute ethyl alcohol as a medium, and the ball-to-material ratio is 1.5: 1).
(2) Pouring the high-temperature melt obtained in the step (1) into a square metal mold, performing stress relief annealing at 650 ℃ for 6 hours, and then cutting to obtain a glass sheet with the thickness of 1.0-1.5 mm;
(3) and (3) putting an equal number of the glass sheets prepared in the step (2) into a crucible, heating to 1000 ℃ at a heating speed of 3 ℃/min, and then preserving heat for 3h to obtain the glass ceramic.
The dielectric properties of the sample prepared in this example are shown in FIG. 1, the dielectric constant is 123 at room temperature, and the loss is 0.026; the withstand voltage performance is 1505.73kV/cm as shown in figure 2, the energy storage density is as shown in figure 3, and the theoretical energy storage density is 12.3J/cm at most3The material can be applied to energy storage capacitor materials; the impedance spectrum is shown in FIG. 4, and the activation energy is shown in FIG. 5 and is 1.42 eV; XRD is shown in figure 6.
In this example, there is Ba2NaNb5O15And NaNbO3The amount of precipitation increases, so that the dielectric constant of the material increases. The activation energy of the material increases, indicating an increase in the degree of interfacial polarization, and thus the breakdown field strength begins to decrease again.
In the description herein, references to the description of "one embodiment," "an example," "a specific example" or the like are intended to mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
Example 5
The preparation method of the bismuth barium sodium niobate-based glass ceramic material with high energy storage density comprises the following steps:
(1) with a purity of more than 99 wt.% of BaCO3、Bi2O3、Na2CO3、Nb2O5、SiO2The raw materials are mixed according to the mol percentage of 21.6%, 2.4%, 6%, 30% and 40%, and are subjected to ball milling and mixing for 24 hours, after drying for 6 hours at 100 ℃, the mixture is melted for 1 hour at 1450 ℃, and the ball milling takes absolute ethyl alcohol as a medium, and the ball-to-material ratio is 1.5: 1.
(2) Pouring the high-temperature melt obtained in the step (1) into a square metal mold, performing stress relief annealing at the temperature of 600 ℃ for 5 hours, and then cutting to obtain a glass sheet with the thickness of 1.0 mm;
(3) and (3) putting an equal number of the glass sheets prepared in the step (2) into a crucible, heating to 850 ℃ at a heating speed of 3 ℃/min, and preserving heat for 5 hours to obtain the glass ceramic.
Example 6
The preparation method of the bismuth barium sodium niobate-based glass ceramic material with high energy storage density comprises the following steps:
(1) with a purity of more than 99 wt.% of BaCO3、Bi2O3、Na2CO3、Nb2O5、SiO2The raw materials are mixed according to the mol percentage of 21.6%, 2.4%, 6%, 30% and 40%, and the mixture is subjected to ball milling for 24 hours, dried at 100 ℃ for 6 hours and then melted at 1500 ℃ for 1 hour, (the ball milling takes absolute ethyl alcohol as a medium, and the ball-to-material ratio is 1.5: 1).
(2) Pouring the high-temperature melt obtained in the step (1) into a square metal mold, performing stress relief annealing at the temperature of 600 ℃ for 6 hours, and then cutting to obtain a glass sheet with the thickness of 1.0-1.5 mm;
(3) and (3) putting an equal number of the glass sheets prepared in the step (2) into a crucible, heating to 950 ℃ at a heating rate of 3 ℃/min, and preserving heat for 4h to obtain the glass ceramic.
The embodiments described above are intended to facilitate the understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.
Claims (7)
1. A preparation method of a bismuth barium sodium niobate-based glass ceramic material with high energy storage density is characterized by comprising the following steps:
(1) with BaCO3、Bi2O3、Na2CO3、Nb2O5、SiO2Is prepared from 21.6BaCO by mol3-2.4Bi2O3-6Na2CO3-30Nb2O5-40SiO2Proportioning, mixing, and high-temp fusingMelting to prepare high-temperature molten slurry;
(2) pouring the high-temperature molten slurry prepared in the step (1) into a preheated mold for molding, keeping the preheating temperature for hours, removing residual stress in the glass, and preparing uniform glass and then slicing;
(3) and (3) performing controlled crystallization on the glass sheet prepared in the step (2) at 850 ℃ or 950-1000 ℃ to prepare the bismuth barium sodium niobate-based glass ceramic material.
2. The preparation method of the bismuth barium sodium niobate-based glass ceramic material with high energy storage density as claimed in claim 1, wherein the high temperature melting at 1450-1550 ℃ in the step (1) is controlled for 1-2 h.
3. The preparation method of the high energy storage density bismuth barium sodium niobate-based glass ceramic material according to claim 1, wherein the preheating temperature of the mold in the step (2) is 600-650 ℃.
4. The preparation method of the high energy storage density bismuth barium sodium niobate-based glass ceramic material according to claim 1, wherein the stress relief time of the high temperature molten slurry in the step (2) in a mold is 5-6 h.
5. The preparation method of the high energy storage density bismuth barium sodium niobate-based glass ceramic material according to claim 1, wherein the temperature rise rate is controlled to be 3 ℃/min during controlled crystallization in the step (3), and the temperature control time is 3-5 h.
6. A bismuth barium sodium niobate-based glass ceramic material with high energy storage density, which is prepared by the method of any one of claims 1 to 5.
7. The use of the high energy storage density bismuth barium sodium niobate-based glass ceramic material of claim 6 as an energy storage capacitor material.
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