CN108395106B - Barium niobate lead sodium based glass ceramic material with high energy storage density and preparation method thereof - Google Patents
Barium niobate lead sodium based glass ceramic material with high energy storage density and preparation method thereof Download PDFInfo
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- CN108395106B CN108395106B CN201810366442.6A CN201810366442A CN108395106B CN 108395106 B CN108395106 B CN 108395106B CN 201810366442 A CN201810366442 A CN 201810366442A CN 108395106 B CN108395106 B CN 108395106B
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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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- 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
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- 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
Abstract
The invention relates to a barium niobate lead-sodium based glass ceramic material with high energy storage density and a preparation method thereof, wherein the ceramic particle component mainly comprises NaNbO of perovskite phase3And Ba of tungsten bronze phase2NaNb5O15. The chemical components of the glass ceramic energy storage material conform to a chemical general formula of 6.4Na2CO3‑23.04BaCO3‑2.56PbO‑32Nb2O5‑36SiO2With Na2CO3、BaCO3、PbO、Nb2O5、SiO2The glass melt is prepared by the steps of grinding and mixing materials by a roller, drying the materials, and then melting the materials at high temperature; quickly pouring the high-temperature melt onto a preheated mold, preserving heat in a constant-temperature furnace body for several hours to remove residual stress in glass under rapid cooling, and then cutting a 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, wherein the barium sodium niobate-based glass ceramic energy storage material is used as an energy storage capacitor material. Compared with the prior art, the glass ceramic energy storage material prepared by the invention has the advantages of high dielectric constant and energy storage density, wide heat treatment temperature range and the like.
Description
Technical Field
The invention belongs to the field of dielectric energy storage materials, relates to a dielectric energy storage material and a preparation method thereof, and particularly relates to a barium niobate lead sodium based glass ceramic material with high energy storage density and a preparation method thereof.
Background
The traditional fossil energy is inevitably polluted in the using process, and the like, and is a non-renewable energy source which is gradually exhausted. Environmental pollution and energy crisis caused by fossil energy have driven people to continuously explore new energy sources which are environment-friendly and renewable. Meanwhile, in order to improve the energy utilization rate, various energy storage technologies and energy storage materials are developed, wherein a high energy storage density capacitor is an important energy storage element. Materials currently used as energy storage dielectrics for capacitors include conventional ferroelectric ceramics, antiferroelectric ceramics and polymer composites, but the disadvantages of these materials themselves limit their applications. 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. The high polymer energy storage material has the advantages of high breakdown electric field resistance (such as PVDF-3 MV/cm), but the dielectric constant of the high polymer is extremely low (<10), so that the energy storage density is not high, and in addition, the thermal stability of the high polymer energy storage material is poor, and a capacitor is easy to damage if an electronic element generates too high heat.
As an energy storage material, namely a glass ceramic energy storage material, which is researched in a recent hot spot, a high-temperature melting method is adopted, and glass and ceramic components are firstly melted to prepare glass melt slurry. Then, forming and destressing the bulk glass; finally, the glass-ceramic which is composed of large proportion of submicron and nanometer crystals and residual glass phase and has no pores is prepared by a controllable crystallization method, and in the controllable crystallization process, the effective control of the grain size and the content of the crystal phase of the junction phase can be realized by adjusting the relative proportion of metal oxide generating the ceramic phase and a glass phase network former, so that the performance of the glass ceramic material is optimized to a great extent. The glass ceramic prepared by high-temperature melting and controllable crystallization has the characteristics of high dielectric constant, high density and high breakdown resistance. Thereby achieving high energy storage density. Compared with the traditional barium strontium titanate-based glass ceramic, the barium sodium niobate-based glass ceramic phase can be obtained by controllable crystallization in a glass matrix (the crystallization temperature is low), so that the barium sodium niobate-based glass ceramic is superior to the dielectric constant of the barium strontium titanate-based glass ceramic; in the high-temperature crystallization process of barium strontium titanate-based glass ceramic, dendritic crystals appear in the glass ceramic due to excessive barium elements, so that the breakdown resistance electric field of the glass ceramic is extremely unfavorable, and the barium sodium niobate-based glass ceramic has no intrinsic factor of the concern. In the description, the barium sodium niobate-based glass ceramic composite material with high dielectric constant and high breakdown-resistant electric field is obtained at low heat treatment temperature by using the barium sodium niobate with high dielectric constant as a ceramic phase and silicate as a glass phase, which has important significance for the practical application of the dielectric energy storage material.
In recent years, niobate glass ceramics are another high-energy-storage glass ceramic material which is a hot research at home and abroad. The niobate microcrystalline glass is a composite material mainly composed of niobate crystals with tungsten bronze type structures and perovskite structures and a glass phase. In a niobate glass ceramic system, some scholars perform corresponding optimization and doping modification researches on the niobate glass ceramic system. M.P.Graca et al investigated the heat treatment on SiO2-Na2O-Nb2O5The influence of the electrical and dielectric properties of the glass-ceramic. The composition is found to be 60SiO2-30Na2O-10Nb2O5(mol%) the glass of the system is heat-treated for 4h at 650 ℃, the dielectric constant of the material is up to 48.19, and the dielectric loss is 1.07 at the lowest. The barium strontium niobate-based glass ceramic is prepared by Shyu and the like through an integral crystallization method, the SBN phase content is increased along with the increase of the sintering temperature, the calculated crystallization phase content is up to 40 percent, and the dielectric constant is up to 180 at most; (SrO, BaO) -Nb subsequently investigated2O5When the crystallization temperature of the system glass ceramic is lower than 1000 ℃, the dielectric constant of a sample is up to 351, the breakdown strength is up to 4.5kV/cm, and the residual polarization strength is 0.15 mu C/cm2. Subsequently, Zeng et al studied BaF2Additive pair SrO-BaO-Nb2O5-B2O3The influence of the crystallization kinetics and the dielectric property of the glass, and the dielectric constant of the microcrystalline glass of the system is found to be dependent on BaF2The increase in the amount of addition shows a change of increasing first and then decreasing, and the breakdown resistance tends to increase. When 5 mol% of BaF is added2Then, the microcrystalline glass ceramic with the optimal performance of dielectric constant of 337 and breakdown resistance of 527kV/cm is obtained. Jun Luo et al are based on Na2O-PbO-Nb2O5-SiO2The glass ceramic system can successfully prepare the capacitor with a multilayer structure and excellent performance, and the energy storage density reaches 8J/cm3. Wang et al investigated the dielectric properties of Ba/K-vs. (BaO, K2O) -Nb2O5-SiO2 systems in different ratiosAccording to research, when the Ba/K is 4, after the sample is insulated for 3 hours at 900 ℃, the breakdown field strength of the sample can reach 1973kV/cm, and the energy storage density is 12.06J/cm 3. Han, etc. apply casting fast cooling and controllable crystallization technology to prepare 3 kinds of glass ceramic nano composite dielectric materials, including lead-free strontium sodium niobate and barium sodium niobate systems. When the Sr/Na ratio and the Ba/Na ratio are 1:1, the dielectric constant of the material is increased along with the rise of the heat treatment temperature, after the material is subjected to heat treatment at 900 ℃ for 180min, the dielectric constant of the (BaO, Na2O) -Nb2O5-SiO2 system can reach 300, and the dielectric constant of the (SrO, Na2O) -Nb2O5-SiO2 system can reach 370. The method has important significance for improving the energy storage density of the glass ceramic by adjusting the composition of the ceramic phase, optimizing and changing the crystallization temperature to a certain extent.
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: 32x BaO-32(1-x) K2O–32Nb2O5–36SiO2Wherein the value range of x 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 pouring the high-temperature melt into a preheated metal mold, performing stress relief annealing to obtain transparent glass, slicing to obtain a glass sheet, and finally performing controlled crystallization on the glass sheet to obtain the target product. Although the method is simple, the glass ceramic material prepared by the patent contains more KNbO3And KNb3O8Phase, the material is susceptible to aging due to moisture absorption; meanwhile, the dielectric constant of the capacitor is lower than 70 under the test conditions of 25 ℃ 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 barium niobate lead sodium-based glass-ceramic material with high energy storage density.
The purpose of the invention can be realized by the following technical scheme:
the barium niobate lead sodium based glass ceramic material with high energy storage density has ceramic particle component mainly comprising perovskite phaseNaNbO3And Ba of tungsten bronze phase2NaNb5O15The chemical composition of the glass ceramic material conforms to the chemical general formula 6.4Na2CO3-23.04BaCO3-2.56PbO-32Nb2O5-36SiO2。
The content of PbO in the raw material components can be 10-15 wt% in excess.
The preparation method of the barium niobate lead sodium based glass ceramic material with high energy storage density comprises the following steps:
(1) with Na2CO3、BaCO3、PbO、Nb2O5、SiO2Is prepared from raw materials with a molar ratio of 6.4Na2CO3-23.04BaCO3-2.56PbO-32Nb2O5-36SiO2Burdening, 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 to prepare transparent uniform glass without stones, 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.
Melting at 1500 deg.C for 20-40min in step (1).
In the step (2), the preheating temperature of the die is 600 ℃, and the high-temperature molten slurry is preheated in the die for 6 hours.
And (3) controlling the temperature rise rate to be 5 ℃/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 900 ℃ and the temperature is controlled for 5 h.
The barium niobate lead sodium 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 prior art, the dielectric constant and the energy storage density of the glass ceramic are obviously improved by adjusting the crystallization temperature. Particularly, when the crystallization temperature is 900 ℃,the theoretical energy storage density reaches the optimal value of 20.3J/cm3(ii) a When the crystallization temperature is 950 ℃, the dielectric constant reaches the optimal value, the dielectric constant is 150 at 100kHz room temperature, and the theoretical energy storage density is 16.5J/cm3. This is because the material is more prone to precipitate Ba with high dielectric constant after adding PbO, heat treatment at 900 ℃ and 950 ℃2NaNb5O15，Pb0.3Ba0.7Nb2O6And NaNbO3The content of impure phases is less; meanwhile, the crystalline phases are uniformly distributed in the glass matrix, and the microscopic appearance is uniform and compact, so that the material has higher breakdown field strength. Moreover, the invention also has the following advantages:
(1) by optimizing the crystallization temperature, the ferroelectric phase Ba can be effectively improved2NaNb5O15And Pb0.3Ba0.7Nb2O6Thereby increasing the dielectric constant of the glass-ceramic; under the heat treatment temperature of 850 ℃ to 950 ℃, the microscopic appearance of the glass ceramic is always uniform and compact, and the breakdown-resistant field strength is kept at a higher level. For glass ceramic materials, the energy storage density is equal to 0.5 epsilon0εrE2Thereby obviously improving the theoretical density.
(2) From the DSC curve, Tp at a temperature rise rate of 10 ℃/min1＝775℃，Tp2906 ℃ and the difference between the two is 131 ℃, and the main crystal phase precipitated in the temperature interval is Ba by combining XRD analysis2NaNb5O15、Pb0.3Ba0.7Nb2O6And NaNbO3And (4) phase(s). Therefore, the temperature range of controlled crystallization of the material is wide.
(3) Na in the raw Material2CO3Mostly with Ba2NaNb5O15And NaNbO3The phase is separated out, and the material is not easy to absorb moisture and age.
(4) The preparation method is simple, does not need complex post-treatment steps, and is economical and practical.
Drawings
FIG. 1 shows 6.4Na2CO3-23.04BaCO3-2.56PbO-32Nb2O5-36SiO2(mol%) DSC curve of base glass at a temperature rise rate of 10 deg.C/min;
FIG. 2 shows 6.4Na at different crystallization temperatures2CO3-23.04BaCO3-2.56PbO-32Nb2O5-36SiO2(mol%) curve of energy storage density of glass ceramic energy storage material and electric field;
FIG. 3 shows 6.4Na at different crystallization temperatures2CO3-23.04BaCO3-2.56PbO-32Nb2O5-36SiO2(mol%) dielectric constant and loss of glass ceramic energy storage material;
FIG. 4 shows 6.4Na at different crystallization temperatures2CO3-23.04BaCO3-2.56PbO-32Nb2O5-36SiO2(mol%) Weibull distribution curve of breakdown-resistant field strength of the glass ceramic energy storage material;
FIG. 5 shows 6.4Na at different crystallization temperatures2CO3-23.04BaCO3-2.56PbO-32Nb2O5-36SiO2(mol%) XRD spectrogram of the glass ceramic energy storage material;
FIG. 6 shows 6.4Na at different crystallization temperatures2CO3-23.04BaCO3-2.56PbO-32Nb2O5-36SiO2SEM image of (mol%) glass ceramic energy storage material.
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.
Example 1
The preparation method of the barium niobate lead sodium based glass ceramic energy storage material with high energy storage density comprises the following steps:
(1) in the form of Na with a purity of more than 99 wt%2CO3、BaCO3、PbO、Nb2O5、SiO2The raw materials are proportioned, the mole percentages of the components are 6.4%, 23.04%, 2.56%, 32% and 36%, the materials are mixed for 24 hours by ball milling, dried for 6 hours at 120 ℃, and then melted for 30 minutes at 1500 ℃; (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 copper 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 square crucible, heating to 850 ℃ at a heating speed of 5 ℃/min, and preserving heat for 5h to obtain the glass ceramic.
The energy storage density of the sample prepared in this example is shown in FIG. 2, and the maximum energy storage density is 19.7J/cm3The material can be applied to energy storage capacitor materials. The dielectric properties are shown in FIG. 3, 124; the withstand voltage performance test is shown in FIG. 4, which is 1893 kV/cm; XRD is shown in FIG. 5, and SEM is shown in FIG. 6.
In this embodiment, the main crystal phase of the ceramic phase is Ba2NaNb5O15With NaNbO3And Pb0.3Ba0.7Nb2O6And (4) precipitating to enable the material to have a higher dielectric constant. The microscopic appearance of the glass ceramic is found to be very compact by SEM, and after crystallization, the ceramic phase and the glass phase are distributed more uniformly, so that the glass ceramic has higher breakdown field strength.
Example 2
The preparation method of the barium niobate lead sodium based glass ceramic energy storage material with high energy storage density comprises the following steps:
(1) in the form of Na with a purity of more than 99 wt%2CO3、BaCO3、PbO、Nb2O5、SiO2The raw materials are proportioned, the mole percentages of the components are 6.4%, 23.04%, 2.56%, 32% and 36%, the materials are mixed for 24 hours by ball milling, dried for 6 hours at 120 ℃, and then melted for 30 minutes at 1500 ℃; (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 copper 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 the glass sheets prepared in the step (2) into a square crucible in equal quantity, heating to 900 ℃ at a heating speed of 5 ℃/min, and then preserving heat for 5h to obtain the glass ceramic.
The energy storage density of the sample prepared in this example is shown in FIG. 2, and the maximum energy storage density is 20.3J/cm3The material can be applied to energy storage capacitor materials. The dielectric properties are shown in FIG. 3, which is 134; the withstand voltage performance test is 1848kV/cm as shown in FIG. 4; XRD is shown in FIG. 5, and SEM is shown in FIG. 6.
In this embodiment, the main crystal phase of the ceramic phase is Ba2NaNb5O15With NaNbO3And Pb0.3Ba0.7Nb2O6And (4) precipitating to enable the material to have a higher dielectric constant. The microscopic appearance of the glass ceramic is found to be very compact by SEM, and after crystallization, the ceramic phase and the glass phase are distributed more uniformly, so that the glass ceramic has higher breakdown field strength.
Example 3
The preparation method of the barium niobate lead sodium based glass ceramic energy storage material with high energy storage density comprises the following steps:
(1) in the form of Na with a purity of more than 99 wt%2CO3、BaCO3、PbO、Nb2O5、SiO2The raw materials are proportioned, the mole percentages of the components are 6.4%, 23.04%, 2.56%, 32% and 36%, the materials are mixed for 24 hours by ball milling, dried for 6 hours at 120 ℃, and then melted for 30 minutes at 1500 ℃; (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 copper 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 the glass sheets prepared in the step (2) into a square crucible in equal quantity, heating to 950 ℃ at a heating rate of 5 ℃/min, and then preserving heat for 5h to obtain the glass ceramic.
The energy storage density of the sample prepared in this example is shown in FIG. 2The maximum degree is 16.5J/cm3The material can be applied to energy storage capacitor materials. The dielectric properties are shown in FIG. 3, which is 150; the withstand voltage performance test is 1575kV/cm as shown in FIG. 4; XRD is shown in FIG. 5, and SEM is shown in FIG. 6.
In this embodiment, the main crystal phase of the ceramic phase is Ba2NaNb5O15With NaNbO3And Pb0.3Ba0.7Nb2O6Precipitation of a low dielectric ceramic phase BaAl was performed in comparison with examples 1 and 22Si2O8And AlNbO4So that the breakdown field strength decreases. The microscopic appearance of the glass ceramic is found to be compact by SEM, but after crystallization, the distribution uniformity of the ceramic phase and the glass phase is poor, so that the breakdown field intensity is reduced.
Example 4
The preparation method of the barium niobate lead sodium based glass ceramic energy storage material with high energy storage density comprises the following steps:
(1) in the form of Na with a purity of more than 99 wt%2CO3、BaCO3、PbO、Nb2O5、SiO2The raw materials are proportioned, the mole percentages of the components are 6.4%, 23.04%, 2.56%, 32% and 36%, the materials are mixed for 24 hours by ball milling, dried for 6 hours at 120 ℃, and then melted for 30 minutes at 1500 ℃; (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 copper 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 the glass sheets prepared in the step (2) into a square crucible in equal quantity, heating to 1000 ℃ at a heating speed of 5 ℃/min, and preserving heat for 5h to obtain the glass ceramic.
The energy storage density of the sample prepared in this example is shown in FIG. 2, and the maximum energy storage density is 12.6J/cm. The dielectric properties are shown in FIG. 3, 138; the withstand voltage performance test is 1437kV/cm as shown in FIG. 4; XRD is shown in FIG. 5, and SEM is shown in FIG. 6.
In this embodiment, the main crystal phase of the ceramic phase is Ba2NaNb5O15With NaNbO3And Pb0.3Ba0.7Nb2O6Precipitation of a low dielectric ceramic phase BaAl was performed in comparison with examples 1 and 22Si2O8And AlNbO4So that the breakdown field strength decreases. SEM shows that the glass ceramic has more pores in the microscopic morphology, and the ceramic phase and the glass phase have poor distribution uniformity, so that the breakdown field intensity is reduced.
Example 5
The barium niobate lead sodium 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 6.4Na2CO3-23.04BaCO3-2.56PbO-32Nb2O5-36SiO2. The material is prepared by the following method:
(1) with Na2CO3、BaCO3、PbO、Nb2O5、SiO2Preparing raw materials according to the molar ratio of the raw materials, uniformly mixing, and melting at 1500 ℃ for 20min to prepare high-temperature molten slurry;
(2) pouring the high-temperature molten slurry prepared in the step (1) into a mold preheated to 600 ℃ for molding, keeping the preheating temperature for 6 hours to remove residual stress in glass, preparing transparent uniform glass without stones, 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 5 ℃/min, the crystallization temperature is 850 ℃, and the temperature control time is 5h during the controlled crystallization, so that the niobic acid-based glass ceramic energy storage material is prepared, and the prepared material can be used as an energy storage capacitor material due to high dielectric constant and energy storage density and wide temperature range of the controlled crystallization.
Example 6
The barium niobate lead sodium based glass ceramic material with high energy storage density has ceramic particle component mainly comprising NaNbO of perovskite phase3And Ba of tungsten bronze phase2NaNb5O15Chemical composition of the glass-ceramic materialCorresponds to the chemical general formula 6.4Na2CO3-23.04BaCO3-2.56PbO-32Nb2O5-36SiO2In this example, the PbO content in the raw material composition may also be 10 wt.% excess. The material is prepared by the following method:
(1) with Na2CO3、BaCO3、PbO、Nb2O5、SiO2Preparing raw materials according to the molar ratio of the raw materials, uniformly mixing, and melting at 1500 ℃ for 30min to prepare high-temperature molten slurry;
(2) pouring the high-temperature molten slurry prepared in the step (1) into a mold preheated to 600 ℃ for molding, keeping the preheating temperature for 6 hours to remove residual stress in glass, preparing transparent uniform glass without stones, 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 5 ℃/min, the crystallization temperature is 950 ℃, and the temperature control time is 4h during the controlled crystallization, so that the niobic acid-based glass ceramic energy storage material is prepared, and the prepared material can be used as an energy storage capacitor material due to high dielectric constant and energy storage density and wide temperature range of the controlled crystallization.
Example 7
The barium niobate lead sodium 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 6.4Na2CO3-23.04BaCO3-2.56PbO-32Nb2O5-36SiO2In this example, the PbO content in the raw material composition may also be 15 wt.% excess. The material is prepared by the following method:
(1) with Na2CO3、BaCO3、PbO、Nb2O5、SiO2Preparing raw materials according to the molar ratio of the raw materials, uniformly mixing, and melting at 1500 ℃ for 40min to prepare high-temperature molten slurry;
(2) pouring the high-temperature molten slurry prepared in the step (1) into a mold preheated to 600 ℃ for molding, keeping the preheating temperature for 6 hours to remove residual stress in glass, preparing transparent uniform glass without stones, 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 5 ℃/min, the crystallization temperature is 1000 ℃, and the temperature control time is 3h during the controlled crystallization, so that the niobic acid-based glass ceramic energy storage material is prepared, and the prepared material can be used as an energy storage capacitor material due to high dielectric constant and energy storage density and wide temperature range of the controlled crystallization.
FIG. 1 is a graph (DSC curve) of the heat flow rate with temperature change at a temperature rise rate of 10 ℃/min of a mother glass of a barium lead sodium niobate-based glass ceramic having a high energy storage density. The chemical composition of the glass conforms to the chemical general formula 6.4Na2CO3-23.04BaCO3-2.56PbO-32Nb2O5-36SiO2. It can be seen that the glass has a softening temperature Tg of 706 deg.C and two exothermic peaks, Tp respectively1775 ℃ and Tp2906 ℃. When the XRD spectrum of FIG. 5 is combined, Tp is observed1And Tp2The main crystal phase precipitated from the sample is basically unchanged, and the main crystal phase is NaNbO of a perovskite phase3And Ba of tungsten bronze phase2NaNb5O15And Pb0.3Ba0.7Nb2O6. Referring to FIG. 6, it is shown that a uniform and dense glass-ceramic material can be obtained after controlled devitrification of the glass at 850 ℃ to 950 ℃. The temperature range for controlled crystallization of the material is wide.
The foregoing description of specific embodiments of the present invention has been presented. It is to be understood that the present invention is not limited to the specific embodiments described above, and that various changes and modifications may be made by one skilled in the art within the scope of the appended claims without departing from the spirit of the invention.
Claims (8)
1. The barium niobate lead sodium based glass ceramic material with high energy storage density is characterized in that the chemical composition of the material conforms to the chemical general formula of 6.4Na2CO3-23.04BaCO3-2.56PbO-32Nb2O5-36SiO2Of the materialThe component mainly comprises NaNbO of a perovskite phase3And Ba of tungsten bronze phase2NaNb5O15；
The material is prepared by the following steps:
(1) with Na2CO3、BaCO3、PbO、Nb2O5、SiO2Is prepared from raw materials with a molar ratio of 6.4Na2CO3-23.04BaCO3-2.56PbO-32Nb2O5-36SiO2Burdening, 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 to prepare transparent uniform glass without stones, and slicing to obtain glass sheets;
(3) performing controlled crystallization on the glass sheet prepared in the step (2) to obtain the niobate-based glass ceramic energy storage material;
and (3) controlling the temperature rise rate to be 5 ℃/min during controlled crystallization in the step (3), controlling the crystallization temperature to be 850-1000 ℃ and controlling the temperature for 3-5 h.
2. The barium lead sodium niobate-based glass ceramic material with high energy storage density as claimed in claim 1, wherein the excess content of PbO in the raw material components is 10-15 wt%.
3. The method for preparing the barium lead sodium niobate-based glass ceramic material with high energy storage density according to claim 1, which comprises the following steps:
(1) with Na2CO3、BaCO3、PbO、Nb2O5、SiO2Is prepared from raw materials with a molar ratio of 6.4Na2CO3-23.04BaCO3-2.56PbO-32Nb2O5-36SiO2Burdening, 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 to prepare transparent uniform glass without stones, and slicing to obtain glass sheets;
(3) performing controlled crystallization on the glass sheet prepared in the step (2) to obtain the niobate-based glass ceramic energy storage material;
and (3) controlling the temperature rise rate to be 5 ℃/min during controlled crystallization in the step (3), controlling the crystallization temperature to be 850-1000 ℃ and controlling the temperature for 3-5 h.
4. The preparation method of the barium lead sodium niobate-based glass ceramic material with high energy storage density as claimed in claim 3, wherein the melting in step (1) is carried out at 1500 ℃ for 20-40 min.
5. The method for preparing the barium lead sodium niobate-based glass ceramic material with high energy storage density as claimed in claim 3, wherein the preheating temperature of the mold in the step (2) is 600 ℃.
6. The method for preparing the barium lead sodium niobate-based glass ceramic material with high energy storage density as claimed in claim 3, wherein the stress relief time of the high-temperature molten slurry in the step (2) in the mold is 6 h.
7. The preparation method of the barium lead sodium niobate-based glass ceramic material with high energy storage density as claimed in claim 3, wherein the crystallization temperature in the step (3) is 900 ℃, and the temperature is controlled for 5 h.
8. The use of the barium lead sodium niobate-based glass ceramic material with high energy storage density of claim 1 as an energy storage capacitor material.
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| CN109467313A (en) * | 2018-12-13 | 2019-03-15 | 同济大学 | High energy storage density barium sodium niobate (BNN) base glass ceramics energy storage material and its preparation and application |
| CN110240409B (en) * | 2019-05-30 | 2021-10-08 | 同济大学 | Barium niobate lead sodium based glass ceramic material with high energy storage density and preparation method thereof |
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| CN112159223B (en) * | 2020-09-25 | 2022-06-07 | 陕西科技大学 | High-temperature-stability high-dielectric-constant low-loss dielectric ceramic material, and preparation method and application thereof |
| CN112209713B (en) * | 2020-10-12 | 2022-05-10 | 桂林理工大学 | High-energy-storage and high-efficiency sodium niobate-based ceramic material and preparation method thereof |
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