CN113233770A - Containing Na0.9K0.1NbO3Crystalline phase high dielectric borate glass ceramics, preparation and application thereof - Google Patents
Containing Na0.9K0.1NbO3Crystalline phase high dielectric borate glass ceramics, preparation and application thereof Download PDFInfo
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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
- C03C10/0054—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 containing PbO, SnO2, B2O3
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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
Containing Na0.9K0.1NbO3The crystalline phase high dielectric borate glass ceramic material is prepared by the following steps: at first adopt K2CO3、Na2CO3、Nb2O5And H3BO3As a raw material, according to the chemical formula 0.9((1-x)K2O‑xNa2O)‑2Nb2O5‑0.1B2O3（0.00≤xNot more than 0.50), uniformly mixing the powder by mechanical ball milling, and annealing; melting, cooling, forming and annealing to obtain glass block, and processing at 800oAnd C, preserving heat for 2 hours, and performing crystallization treatment to obtain the glass ceramic material. The invention has simple preparation process, low raw material price and low manufacturing cost, can obtain a linear electric hysteresis loop at room temperature, and has the highest energy storage density of 1.68J/cm3Low dielectric lossAt 0.04, at 120oAnd C, ensuring the energy storage efficiency to be more than 96% at high temperature.
Description
Technical Field
The invention relates to the field of glass ceramic materials and a preparation method thereof, in particular to a method for obtaining Na-containing glass ceramic material0.9K0.1NbO3Crystalline phase high dielectric borate glass ceramic material and preparation method and application thereof.
Background
In recent years, the rapid development of pulse technology in the fields of hybrid vehicles, aerospace, oil drilling and the like has made demands for energy storage dielectric capacitors of high temperature, high energy density and high reliability. Glass-ceramics consisting of a crystalline phase and a dense glass phase are favored by researchers in the field of energy-storing dielectric materials, depending on the high breakdown field strength of their internal dense glass phase and the good dielectric properties of their ferroelectric crystalline phase.
Formula for calculating energy storage density according to linear dielectric medium
The energy storage density of the available energy storage element and the relative dielectric constant of the available energy storage element are related to the breakdown field strength. In order to achieve higher energy storage densities in glass-ceramic materials, there is work on adding Pb to the matrix glass system4+To improve various performances thereof. In order to realize lead-free materials, researchers have begun to study perovskite and tungsten bronze ferroelectric materials. At present, niobate glass ceramics are a hotspot study of energy storage glass ceramics, and most studies are carried out around strontium barium niobate glass powder or ceramics, but the raw materials used in the preparation process of the strontium barium niobate glass ceramics are complex, and the defect of low utilization of the raw materials exists; but the research on the potassium-sodium niobate glass ceramic material is very little. Potassium sodium niobate (i.e., (K, Na) NbO)3) Belonging to a typical perovskite crystal structure. ABO3The perovskite crystal structure is a stable and widely applied crystal form which is a typical ferroelectric, and has more researches on ferroelectricity, piezoelectricity and pyroelectricity, and has more novel research attention on photocatalysis and energy storage.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide a Na-containing material0.9K0.1NbO3The method has the advantages of highly uniform reaction of raw materials, high utilization rate and good dielectric property of the prepared glass ceramic material, and the main crystal phase of the prepared glass ceramic material is Na with good dielectric property0.9K0.1NbO3Crystalline phase, and has high dielectric strength, high dielectric constant and low dielectric loss.
The invention introduces sodium oxide to promote Na with a perovskite structure0.9K0.1NbO3The crystal phase is separated out and becomes the main crystal phase to obtain high dielectric constant, and meanwhile, the borate glass network structure is optimized, and the migration of carriers is inhibited to improve the breakdown strength. 0.9((1-x)K2O-xNa2O)-2Nb2O5-0.1B2O3The dielectric and voltage-resisting properties of the glass network structure and the matrix are further modified by introducing sodium oxide into the system glass ceramic material.
On one hand, the invention selects the glass phase as boron oxide, the boron oxide can effectively reduce the viscosity of the glass, accelerate the diffusion and mass transfer to promote the precipitation of the crystal phase, and the introduction of sodium oxide promotes Na with the perovskite structure0.9K0.1NbO3Crystal phase precipitation and reduction of non-ferroelectric phase K2B4O7Thereby obtaining a high dielectric constant. On the other hand, the free oxygen provided by the alkali metal oxide makes the framework [ BO ] in the borate glass network3]The boron-oxygen triangle body is broken, so that the glass network structure is loose. The capacity of the sodium oxide for providing free oxygen is weaker than that of the potassium oxide, so that the capacity of providing free oxygen is integrally reduced along with the introduction of the sodium oxide, the fracture degree of a glass network framework is reduced, and a compact glass network structure is obtained, so that the obtaining of high pressure resistance is facilitated.
In order to realize the purpose, the technical scheme adopted by the glass ceramic is as follows:
containing Na0.9K0.1NbO3The chemical formula of the crystalline phase high dielectric borate glass ceramic material is 0.9((1-x)K2O-xNa2O)-2Nb2O5-0.1B2O3WhereinxIs Na2The substitution amount of O is less than or equal to 0.00xLess than or equal to 0.50, whereinxExpressed as mole percent. The glass ceramic material is prepared by mixing, melting, molding, annealing and crystallizing according to a formula.
The preparation method of the glass ceramic material adopts the technical scheme that the preparation method comprises the following steps:
1) according to 0.9 ((1-)x)K2O-xNa2O)-2Nb2O5-0.1B2O3(0.00≤xLess than or equal to 0.50) is weighed2CO3、Na2CO3、Nb2O5And H3BO3Uniformly mixing by mechanical ball milling, drying and sieving;
2) placing the mixture obtained in the step 1) in a quartz crucible and heating until a uniformly mixed melt is formed; pouring the melt into a preheated mold for molding, and then carrying out annealing treatment to obtain a glass sample;
3) the glass sample after annealing treatment is crystallized to obtain 0.9((1-x)K2O-xNa2O)-2Nb2O5-0.1B2O3Glass-ceramic materials.
The ball milling time in the step (1) is 2-4 hours.
And (2) mixing the mixed oxide with zircon and alcohol in the step (1), ball-milling and drying to form a mixture.
The heating temperature in the step 2) is 1300-1350%oC。
The preheating temperature of the grinding tool in the step 2) is 400-500 DEG CoC
The annealing treatment in the step 2) is 500-550oAnd C, preserving the heat for 2-4 h.
The crystallization treatment system in the step 3) is 2oC/min heating to 200oC is further increased by 3oC/min heating to 500oC, finally 5 againoC/min heating to 800oAnd C, preserving heat for 2 hours.
Compared with the prior art, the invention has the beneficial effects that:
the potassium-sodium niobate borate glass ceramic material prepared by the invention has good compactness, extremely small porosity and uniform grain size. Meanwhile, as three parts of a network former, a network exosome and a network intermediate are needed for forming glass, the raw material of the target product of the sodium potassium niobate to be prepared has the alkali metal oxide K2O、Na2O exists as a network exosome in the glass system, thereby simplifying the glass formula, not only reducing the cost, but also fundamentally reducing the types of precipitated impurities. The invention selects the glass phase as boron oxide, the boron oxide can effectively reduce the viscosity of the glass, accelerate the separation of the diffusion and mass transfer promotion crystalline phase, and the introduction of sodium oxide promotes Na with the perovskite structure0.9K0.1NbO3Crystal phase precipitation and reduction of non-ferroelectric phase K2B4O7The obtained high dielectric constant reaches 150, and the dielectric loss can be reduced to 0.04; in addition, the free oxygen provided by the alkali metal oxide contributes to the framework [ BO ] in the borate glass network3]The boron-oxygen triangle body is broken, so that the glass network structure is loose. The capacity of sodium oxide for providing free oxygen is weaker than that of potassium oxide, so that the capacity of providing free oxygen is integrally reduced along with the introduction of sodium oxide, the fracture degree of a glass network framework is reduced, a compact glass network structure is obtained, the obtaining of high voltage resistance is facilitated, the breakdown field strength can reach 505 kV/cm, and the obtained energy storage density is 1.68J/cm3. At 120oAnd C, under a high-temperature working environment, a linear electric hysteresis loop is still maintained, the energy storage efficiency is over 96 percent, and the material is suitable for being applied to energy storage materials at high temperature.
In addition, with the enhancement of environmental awareness of people, the production of materials avoids the influence on the environment, and the raw materials adopted by the invention are environment-friendly because the raw materials do not contain heavy metal elements such as lead and the like, so the preparation process cannot damage the environment. The invention selects the glass phase as boron oxide, and compared with silicon oxide, the boron oxide can effectively lower the melting temperature and reduce the energy consumption. The preparation method of the invention only needs to carry out mixing melting, molding, annealing and crystallization treatment on the raw materials to obtain the potassium-sodium niobate borate glass ceramic material. The invention adopts a melting method, the raw materials are highly uniformly reacted, the experimental operation is simple, the forming methods are more, the internal stress can be effectively eliminated after annealing, and meanwhile, the segmented heat preservation is adopted during the crystallization treatment, so that the crystal phase growth is more complete, the crystallization is more thorough, and the glass ceramic with finer internal crystal grains, higher homogenization degree and higher energy storage density can be obtained.
Drawings
FIG. 1 is an X-ray diffraction (XRD) pattern of borate glass-ceramic materials prepared according to examples 1, 2, 3, 4 and 5 of the present invention;
FIG. 2 is a graph of dielectric constant versus dielectric loss for borate glass-ceramic materials prepared in accordance with the present invention;
FIG. 3 is a Weibull distribution diagram of the potassium sodium niobate-based borate glass ceramic material prepared by the present invention.
Detailed Description
The method comprises the following specific steps:
1) according to 0.9 ((1-)x)K2O-xNa2O)-2Nb2O5-0.1B2O3（0.00≤xLess than or equal to 0.50) is weighed2CO3、Na2CO3、Nb2O5And H3BO3Uniformly mixing by mechanical ball milling, drying and sieving;
2) heating a quartz crucible to 1000-1100 ℃ from room temperature along with a furnaceoC, starting to add the mixture, and then continuously heating to 1300-1350oC, preserving heat for 50-60 min to enable the mixture to be fully melted and bubble-free, and finally obtaining a mixed molten material; molding the mixed molten material on a preheated copper plate mold at room temperature, and quickly putting the molded mixed molten material into an annealing furnace at 500-550 DEG CoC, annealing for 1-2 hours to eliminate internal stress and obtain a glass sample;
the glass sample is processed at 800oC, preserving heat, performing crystallization treatment for 2 hours, and then cooling to room temperature along with the furnace to obtain 0.9((1-x)K2O-xNa2O)-2Nb2O5-0.1B2O3Glass-ceramic materials.
The present invention is further illustrated in detail below with reference to specific examples:
example 1:
crystallization treatment of the glass sample in this example: at 800oAnd C, preserving the heat for 2 h.
The preparation method of the glass ceramic material comprises the following steps:
1) the glass ceramic material of the embodiment is prepared from (1-x)：x（x= 0.00), take K2CO3，Na2CO3，Nb2O5And H and3BO3uniformly mixing by ball milling, drying and sieving to obtain a mixture;
2) heating the quartz crucible with the furnace from room temperature to 1100oC, the mixture is initially added, and heating is continued to 1350oC, and is in 1350oC, keeping the temperature for 50min to enable the mixture to be melted uniformly to obtain a mixed molten material; mixing the molten materials at 450oC forming the preheated copper plate, and rapidly placing the copper plate into a furnace at 500 DEG CoC, annealing for 1h to obtain an annealed glass substrate;
3) at 800oC, preserving the heat for 2 hours, and then cooling to room temperature along with the furnace to obtain 0.9 (K)2O-2Nb2O5-0.1B2O3The system is made of glass ceramic material.
Cutting the potassium-sodium niobate glass ceramic obtained in the embodiment into a sheet with the thickness of 0.1-0.2 mm by using a cutting machine, polishing and cleaning the sheet, uniformly coating silver electrode slurry on the front surface and the back surface of the sheet, and performing 600 DEG CoAnd C, preserving the temperature for 20 minutes to obtain the glass ceramic sample to be detected.
Example 2:
the formula of the glass sample in this example is (1-x)：x（x= 0.125) and at 1350oThe C charge was melted and held for 50min, otherwise the conditions were the same as in example 1.
Example 3:
the formula of the glass sample in this example is (1-x)：x（x= 0.25), the other conditions are the same as those of the caseExample 2.
Example 4:
the formula of the glass sample in this example is (1-x)：x（x= 0.375), other conditions are the same as example 2.
Example 5:
the formula of the glass sample in this example is (1-x)：x（x= 0.50), the other conditions were the same as in example 2.
FIG. 1 is an X-ray diffraction analysis of the above five examples, showing the effect of different experimental formulations on their degree of crystallinity and phase. The X-ray diffraction result shows that when the content of sodium oxide is low, the separated main crystal phase is non-ferroelectric phase K2B4O7It has a limiting effect on the achievement of excellent dielectric properties. Na with perovskite structure is gradually precipitated along with the increase of the content of sodium oxide0.9K0.1NbO3Crystal phase, while precipitating a partially filled tetragonal tungsten bronze structure of K6Nb10.8O30And (4) phase(s). FIG. 1 (b) shows the crystallinity of each crystal phase, and the glass ceramic obtained in example 5 has a main crystal phase of Na having a perovskite structure0.9K0.1NbO3A crystalline phase and very little non-ferroelectric phase K is precipitated2B4O7And K of tungsten bronze type structure6Nb10.8O30And (4) phase(s).
FIG. 2 is a graph of dielectric constant versus dielectric loss as a function of frequency and temperature for the glass-ceramic materials prepared in the above five examples. Fig. 2 (a) shows that the glass-ceramics prepared by the five examples all have appropriate dielectric constants and remain unchanged, which shows good frequency stability. The glass ceramic obtained in example 5 had the largest dielectric constant, since the main crystal phase of the glass ceramic was Na having a perovskite structure0.9K0.1NbO3A crystalline phase and very little non-ferroelectric phase K is precipitated2B4O7And K of tungsten bronze type structure6Nb10.8O30And (4) phase(s). The dielectric loss of the glass ceramic materials prepared by the five embodiments is kept to be low below 0.04, which is beneficial to practical application. In FIG. 2(b)The temperature dependence of the electrical properties shows that the dielectric constant and the dielectric loss change with the sodium oxide content in the same manner as before. From room temperature to 200oC, the curve changes with temperature almost negligibly, which shows that the glass ceramic material prepared by the above five examples has excellent temperature stability.
FIG. 3 is a Weibull distribution plot of the glass-ceramic materials obtained in the above five examples, and the glass-ceramic material obtained in example 4 has a higher breakdown strength due to the framework BO in the borate glass network caused by free oxygen provided by the boron alkali metal oxide3]The boron-oxygen triangle body is broken, so that the glass network structure is loose. The sodium oxide has a weaker ability to provide free oxygen than potassium oxide, and thus, with the introduction of sodium oxide, the ability to provide free oxygen is reduced as a whole, and the degree of fracture of the glass network skeleton is reduced, so that a compact glass network structure is obtained. The compact glass network structure can effectively block the carrier migration and reduce the conductivity. The breakdown strength is closely related to the electrical conductivity and the compactness of the glass network structure. Both the low conductivity and the compact glass network structure are advantageous for obtaining a high breakdown strength (505 kV/cm). According to the energy storage formula:
the glass ceramic material prepared in example 3 has a high energy storage density of 1.68J/cm3。
The invention selects the glass phase as boron oxide, the boron oxide can effectively reduce the viscosity of the glass, accelerate the diffusion and mass transfer to promote the precipitation of crystal phase, the obtained high dielectric constant reaches 175, and the dielectric loss can be reduced to 0.04; the content of the alkali metal oxide and the content of the glass phase are regulated and controlled, the content of free oxygen provided by the alkali metal oxide is reduced, and the borate glass network structure realizes the transformation from the boron-oxygen triangle with a laminated structure to the boron-oxygen tetrahedron with a frame structure. The middle layers of the boron-oxygen triangle body with the layered structure are connected through Van der Waals force, and obviously, the frame structure of the boron-oxygen tetrahedron enables the glass network structure to be compact, thereby being beneficial to obtaining high breakdown performance. The ferroelectric glass ceramic with high dielectric constant, high breakdown field strength and low dielectric loss is obtained. And the sample is prepared by adopting a melting method, the process is simple and convenient, the forming method is more, the breakdown strength is high, and the method is an important method for preparing the material with high energy storage density. The borate glass ceramic material with low dielectric loss and high energy storage density and compact structure prepared by the invention becomes one of important candidate materials.
The above description is only one embodiment of the present invention, and not all or only one embodiment, and any equivalent alterations to the technical solutions of the present invention, which are made by those skilled in the art through reading the present specification, are covered by the claims of the present invention.
Claims (10)
1.Na2O and/or Na2CO3The application of the glass network structure in improving the high pressure resistance or energy storage density of the potassium-sodium niobate borate glass ceramic or optimizing the system or improving the energy storage performance.
2. The use according to claim 1, characterized by Na in potassium sodium niobate borate glass ceramics2O to K2Increased amount of substitution with O and Na having perovskite structure0.9K0.1NbO3Increased precipitation of crystalline phase, non-ferroelectric phase K2B4O7The precipitation is reduced.
3. The use according to claim 1, characterized by Na in potassium sodium niobate borate glass ceramics2O to K2The improvement of O substitution amount, the reduction of free oxygen supply capacity of potassium-sodium niobate borate glass ceramic system, and the framework [ BO ] in borate glass network3]The fracture degree of the boron-oxygen triangle is reduced.
4. The use as claimed in claim 1, wherein the potassium-sodium niobate borate glass ceramic has a chemical formula of 0.9 ((1-)x)K2O-xNa2O)-2Nb2O5-0.1B2O3，0<x≤0.50。
5. Containing Na0.9K0.1NbO3Of a crystalline phaseThe high dielectric borate glass ceramic material is characterized in that the chemical formula is 0.9 ((1-)x)K2O-xNa2O)-2Nb2O5-0.1B2O3，0<x≤0.50。
6. A method for preparing the material of claim 5, comprising the steps of:
according to the chemical formula 0.9((1-x)K2O-xNa2O)-2Nb2O5-0.1B2O3Weighing Na from Na, K, Nb and B2CO3、K2CO3、Nb2O5And H3BO3And mixed therein, wherein 0<xLess than or equal to 0.50; through ball milling, heating to melt the mixture, forming, annealing to eliminate internal stress and crystallizing heat treatment, Na-containing material is obtained0.9K0.1NbO3Crystalline phase high dielectric borate glass-ceramic materials.
7. The method of claim 6, comprising the steps of:
1) according to 0.9 ((1-)x)K2O-xNa2O)-2Nb2O5-0.1B2O3Weighing Na in mole percentage of Na, K, Nb and B2CO3、K2CO3、Nb2O5And H3BO3Uniformly mixing by mechanical ball milling, drying and sieving;
2) heating the mixture in step 1) until a uniformly mixed melt is formed; pouring the melt into a preheated mold for molding to obtain a glass sample, and then annealing the glass sample;
3) the glass sample after annealing treatment is crystallized according to the crystallization system of 800oC, keeping the temperature for 2 hours to obtain 0.9((1-x)K2O-xNa2O)-2Nb2O5-0.1B2O3Glass-ceramic materials.
8. The method of claim 6, wherein step 1) comprises: and mixing the mixture with zircon and alcohol, ball-milling for 2-4 hours, and drying to form a mixture.
9. The method of claim 6, wherein step 2) comprises: heating the mixture to 1300-1350%oC forming a melt, adding 400-500 parts of the meltoC, forming in a preheated die to obtain a glass sample, and then carrying out 500-550 treatment on the glass sampleoAnd C, preserving heat for 2-4 h for annealing treatment.
10. The method of claim 6, wherein step 3) comprises: crystallizing the annealed glass sample to obtain 2oC/min heating to 200oC is further increased by 3oC/min heating to 500oC, finally 5 againoC/min heating to 800oAnd C, preserving heat for 2 hours.
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