CN111410426A - High-energy-density rare earth-doped niobate-based glass ceramic material and preparation method and application thereof - Google Patents

High-energy-density rare earth-doped niobate-based glass ceramic material and preparation method and application thereof Download PDF

Info

Publication number
CN111410426A
CN111410426A CN202010260194.4A CN202010260194A CN111410426A CN 111410426 A CN111410426 A CN 111410426A CN 202010260194 A CN202010260194 A CN 202010260194A CN 111410426 A CN111410426 A CN 111410426A
Authority
CN
China
Prior art keywords
energy storage
temperature
glass ceramic
ceramic material
rare earth
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN202010260194.4A
Other languages
Chinese (zh)
Inventor
沈波
陈开开
翟继卫
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Tongji University
Original Assignee
Tongji University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Tongji University filed Critical Tongji University
Priority to CN202010260194.4A priority Critical patent/CN111410426A/en
Publication of CN111410426A publication Critical patent/CN111410426A/en
Pending legal-status Critical Current

Links

Images

Classifications

    • 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
    • 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Ceramic Engineering (AREA)
  • Organic Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Inorganic Insulating Materials (AREA)
  • Glass Compositions (AREA)

Abstract

The invention relates to a high energy storage density rare earth doped niobate base glass ceramic material and a preparation method and application thereof, wherein the material is 21.6BaCO3‑2.4Bi2O3‑6Na2CO3‑30Nb2O5‑40SiO2‑xR2O3‑yMnO2(ii) a The preparation method comprises the steps of uniformly mixing the raw materials, and sequentially carrying out high-temperature melting, slicing and controlled crystallization to obtain the niobate-based glass ceramic material; the prepared material can be used as a material of an energy storage capacitor. Compared with the prior art, the glass ceramic energy storage material prepared by the invention has the advantages of high dielectric constant (107), high breakdown field strength (2158.14 kV/cm) and high energy storage density (22.06J/cm)3) Low loss (0.003), good temperature stability and the like.

Description

High-energy-density rare earth-doped niobate-based glass ceramic material and preparation method and application thereof
Technical Field
The invention belongs to the technical field of dielectric energy storage materials, and relates to a high-energy-density rare earth-doped niobate-based glass ceramic material 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 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 micro-morphology 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 material can reach 4.8J/cm3。
Chinese patent Z L201310185574.6 discloses preparation and application of barium strontium titanate-based glass ceramic energy storage material with high energy density, wherein the chemical components of the calcium glass ceramic energy storage material accord with the chemical general formula of 100 wt% (Ba)xSr1-xTiO3-aAl2O3-bSiO2)+ywt％(BaxSr1-x)TiO3Wherein x is 0.4-0.6, (a + b)/(2+ a + b) is 0.3-0.35, a/b is 0.5-1.0, y is 0-200; firstly, BaCO is added3、SrCO3、TiO2、SiO2、Al2O3Ball-milling the raw materials, mixing, drying, melting at high temperature, and directly pouring into deionized water to obtain BaxSr1-xAl2O3-bSiO2Powder and (Ba)xSr1-x)TiO3Mixing the powder, uniformly stirring, granulating and pressing into ceramic green sheets; and (3) performing viscosity removing treatment on the ceramic green sheet, sintering and preserving heat to obtain the ceramic green sheet. Although the preparation method of the patent is simple, the prepared energy storage material has relatively low energy storage density.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a rare earth doped niobate-based glass ceramic material with high dielectric constant, high energy storage density and wide controlled crystallization temperature range, and a preparation method and application thereof.
The purpose of the invention can be realized by the following technical scheme:
a high-energy-density rare-earth doped niobate-base glass ceramic material contains the ceramic particles (NaNbO) as perovskite phase3And Ba of tungsten bronze phase2NaNb5O15And the chemical composition of the glass ceramic material conforms to the chemical general formula of 21.6BaCO3-2.4Bi2O3-6Na2CO3-30Nb2O5-40SiO2-xR2O3-yMnO2Wherein x and y represent the molar ratio of each component, and satisfy 0-1, and x and y are not all zero, and R is one of L a, Gd and Yb.
Since Bi2O3Is volatile at high temperature, so Bi in the raw material components in the patent2O3The content can be 5-10 wt% in excess.
A preparation method of a rare earth doped niobate-based glass ceramic material with high energy storage density comprises the following steps:
1) with BaCO3、Bi2O3、Na2CO3、Nb2O5、SiO2、R2O3And MnO2As raw material, according to 21.6BaCO3-2.4Bi2O3-6Na2CO3-30Nb2O5-40SiO2-xR2O3-yMnO2The components are mixed according to the molar ratio and are uniformly mixed, and then high-temperature melting slurry is prepared after high-temperature melting; wherein x is more than or equal to 0 and less than or equal to 1, y is more than or equal to 0 and less than or equal to 1, and x and y are not all zero, R2O3Is L a2O3、Gd2O3Or Yb2O3One of (1);
2) pouring the high-temperature molten slurry prepared in the step 1) into a mold for molding, removing residual stress in glass through a constant temperature process to obtain uniform glass, and then slicing the glass to obtain glass sheets;
3) and (3) performing controlled crystallization on the glass sheet prepared in the step 2) to obtain the niobate-based glass ceramic material.
Further, in the step 1), the melting temperature in the high-temperature melting is 1450-.
As a preferable technical scheme, the melting temperature is 1550 ℃.
Further, in the step 2), the mold is a preheating mold, and the preheating temperature is 600-650 ℃.
As a preferred technical scheme, the preheating temperature is 650 ℃.
Further, in the step 2), in the constant temperature process, the constant temperature is 600-650 ℃, and the constant temperature time is 5-6 h.
As a preferable technical scheme, the constant temperature is 650 ℃, and the constant temperature time is 6 h.
Further, in the step 3), in the controlled crystallization process, the temperature rise rate is 1-5 ℃/min, the crystallization temperature is 850-.
Further, the crystallization temperature is 950 ℃, and the crystallization time is 5 hours.
The invention prepares the glass ceramic material by a high-temperature melting and controllable crystallization method: firstly, the raw material powder after ball milling is melted and rapidly cooled to obtain a glass block, then the glass block is cut into glass slices, and the glass ceramic is prepared by a controllable crystallization technology. The high energy storage density rare earth doped niobate-based glass ceramic material can be used as an energy storage capacitor material for preparing an energy storage capacitor due to the advantages of high dielectric constant and energy storage density and wide controlled crystallization temperature range.
Compared with the prior art, the invention has the following characteristics:
1) the dielectric glass ceramic composite material with niobate nano ferroelectric particles uniformly distributed in a non-porous glass matrix is prepared by preparing glass and then performing controllable crystallization, so that the glass ceramic composite material has high dielectric constant (105), high breakdown strength (1800 kV/cm) and low dielectric loss (0.006);
2) 21.6BaCO in the invention3-2.4Bi2O3-6Na2CO3-30Nb2O5-40SiO2-0.2Yb2O3-0.5MnO2The material is subjected to crystallization treatment at 950 ℃, the dielectric constant of the glass ceramic at room temperature reaches 107, the breakdown strength reaches 2158.14kV/cm, the loss tangent value reaches 0.003, and the theoretical energy storage density reaches 22.06J/cm3；
3) By optimizing the crystallization temperature, the ferroelectric phase Ba can be effectively improved2NaNb5O15And NaNbO3The dielectric constant of the glass ceramic is improved, the microscopic appearance of the glass ceramic is uniform and compact at the crystallization temperature of 950 ℃, and the breakdown-resistant field strength is kept at a higher level;
4) na in the raw Material2CO3Mostly with Ba2NaNb5O15And NaNbO3The phase is separated out, and the material is not easy to absorb moisture and age;
5) the preparation method is simple, does not need complex post-treatment steps, and is economical and practical;
6) the present invention utilizes rare earth metal oxide L a2O3、Gd2O3Or Yb2O3And MnO2The energy storage density is greatly improved (by 18.4J/cm)3Increased to 22.06J/cm3) The rare earth metal oxide can inhibit the precipitation of dendritic crystals, greatly improves the microstructure of the glass ceramic, thereby improving the breakdown resistance of the glass ceramic, and the inhibiting effect is more obvious as the radius of the rare earth ions is smaller; and MnO2So that Mn is Mn3+、Mn4+Into the B1/B2 position of the tungsten bronze structure to form a defect complex
Figure BDA0002438993560000041
And
Figure BDA0002438993560000042
the defect concentration is reduced, thereby reducing the loss of the glass ceramic.
Drawings
FIG. 1 shows 21.6BaCO3-2.4Bi2O3-6Na2CO3-30Nb2O5-40SiO2-xR2O3-yMnO2(the molar ratio is more than or equal to 0 and less than or equal to 1, y is 0, and R is L a) the change curve of the dielectric constant and the dielectric loss of the glass ceramic material along with the temperature;
FIG. 2 shows 21.6BaCO3-2.4Bi2O3-6Na2CO3-30Nb2O5-40SiO2-xR2O3-yMnO2(the molar ratio is more than or equal to 0 and less than or equal to 1, y is 0, and R is L a) the Weibull distribution curve of the breakdown-resistant field strength of the glass ceramic material;
FIG. 3 shows 21.6BaCO3-2.4Bi2O3-6Na2CO3-30Nb2O5-40SiO2-xR2O3-yMnO2(molar ratio, x is 0.2, y is 0, and R is L a, Gd, Yb) change curve of dielectric constant and dielectric loss with temperature;
FIG. 4 shows 21.6BaCO3-2.4Bi2O3-6Na2CO3-30Nb2O5-40SiO2-xR2O3-yMnO2(molar ratio, x is 0.2, y is 0, and R is L a, Gd, Yb) Weibull profile of breakdown field strength of glass-ceramic material;
FIG. 5 shows 21.6BaCO3-2.4Bi2O3-6Na2CO3-30Nb2O5-40SiO2-xR2O3-yMnO2(molar ratio, x is 0.2, y is 0, and R is L a, Gd, Yb) XRD spectrum of glass ceramic material;
FIG. 6 shows 21.6BaCO3-2.4Bi2O3-6Na2CO3-30Nb2O5-40SiO2-xR2O3-yMnO2(the molar ratio x is 0.2, y is more than or equal to 0 and less than or equal to 1, and R is Yb) the change curve of the dielectric constant and the dielectric loss of the glass ceramic material along with the temperature;
FIG. 7 shows 21.6BaCO3-2.4Bi2O3-6Na2CO3-30Nb2O5-40SiO2-xR2O3-yMnO2(the molar ratio x is 0.2, y is more than or equal to 0 and less than or equal to 1, and R is Yb) is the Weibull distribution curve of the breakdown-resistant field intensity of the glass ceramic material;
FIG. 8 shows 21.6BaCO3-2.4Bi2O3-6Na2CO3-30Nb2O5-40SiO2-xR2O3-yMnO2(the mol ratio of x is 0.2, y is more than or equal to 0 and less than or equal to 1, and R is Yb) of the glass ceramic material.
Detailed Description
The invention is described in detail below with reference to the figures and specific embodiments. The present embodiment is implemented on the premise of the technical solution of the present invention, and a detailed implementation manner and a specific operation process are given, but the scope of the present invention is not limited to the following embodiments.
The high energy storage density rare earth doped niobate base glass ceramic material has ceramic grain component comprising mainly NaNbO in perovskite phase3And Ba of tungsten bronze phase2NaNb5O15Chemical composition of the glass ceramic materialGeneral chemical formula 21.6BaCO3-2.4Bi2O3-6Na2CO3-30Nb2O5-40SiO2-xR2O3-yMnO2Wherein x and y represent the molar ratio of each component, and respectively satisfy x is more than or equal to 0 and less than or equal to 1, y is more than or equal to 0 and less than or equal to 1, x and y are not all zero, and R is one of L a, Gd and Yb.
The preparation method of the high energy storage density rare earth doped niobate-based glass ceramic material comprises the following steps:
1) with BaCO3、Bi2O3、Na2CO3、Nb2O5、SiO2、R2O3、MnO2Is prepared from 21.6BaCO by mol3-2.4Bi2O3-6Na2CO3-30Nb2O5-40SiO2-xR2O3-yMnO2Mixing materials, wherein x and y represent the molar ratio of each component, x is more than or equal to 0 and less than or equal to 1, y is more than or equal to 0 and less than or equal to 1, R is one of L a, Gd and Yb, uniformly mixing, and controlling the temperature to melt at 1450-;
2) pouring the high-temperature molten slurry prepared in the step 1) into a preheated mold at the temperature of 600-650 ℃ for molding, keeping the preheating temperature for 5-6h to remove residual stress in the glass, preparing transparent uniform glass, and slicing to obtain glass sheets;
3) and (3) performing controlled crystallization on the glass sheet prepared in the step 3), wherein the temperature rise rate is controlled to be 3 ℃/min, the crystallization temperature is 850-1000 ℃, and the temperature control time is 3-5h during the controlled crystallization, 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:
a high energy storage density rare earth doped niobate base glass ceramic material is prepared by the following steps:
1) with a purity of more than 99 wt.% of BaCO3、Bi2O3、Na2CO3、Nb2O5、SiO2、La2O3The raw materials are mixed according to a molar ratio of 21.6:2.4:6:30:40: x, and the mixture is subjected to ball milling for 24 hours, then dried at 100 ℃ for 6 hours, and then melted at 1550 ℃ for 2 hours to obtain high-temperature molten slurry; wherein x is 0, 0.1, 0.2, 0.5 and 1, absolute ethyl alcohol is used as a medium in the ball milling process, and the ball-to-material ratio is 1.5: 1;
2) pouring the high-temperature molten slurry prepared in the step 1) into a square metal mold, performing stress annealing at 650 ℃ for 6 hours, and then cutting to obtain a glass sheet with the thickness of 1.0-1.5 mm;
3) putting equal amount of glass sheets prepared in the step 2) into a crucible, heating to 950 ℃ at a heating rate of 3 ℃/min, and keeping the temperature for 5h to obtain the niobate-based glass ceramic material.
The dielectric properties of the sample prepared in this example are shown in fig. 1, the dielectric breakdown strength is shown in fig. 2, and when x is 0.2, the dielectric constant is 116 and the loss is 0.012 at room temperature; the pressure resistance is 1924.4kV/cm, and the theoretical energy storage density is 19.0J/cm3The material can be applied to energy storage capacitor materials; the XRD pattern is shown in figure 5.
Example 2:
a high energy storage density rare earth doped niobate base glass ceramic material is prepared by the following steps:
1) with a purity of more than 99 wt.% of BaCO3、Bi2O3、Na2CO3、Nb2O5、SiO2、Gd2O3The raw materials are mixed according to a molar ratio of 21.6:2.4:6:30:40:0.2, the mixture is subjected to ball milling for 24 hours, then dried at 100 ℃ for 6 hours, and then melted at 1550 ℃ for 2 hours to obtain high-temperature molten slurry; wherein, the ball milling process takes absolute ethyl alcohol as a medium, and the ball-to-material ratio is 1.5: 1;
2) pouring the high-temperature molten slurry prepared in the step 1) into a square metal mold, performing stress annealing at 650 ℃ for 6 hours, and then cutting to obtain a glass sheet with the thickness of 1.0-1.5 mm;
3) putting equal amount of glass sheets prepared in the step 2) into a crucible, heating to 950 ℃ at a heating rate of 3 ℃/min, and keeping the temperature for 5h to obtain the niobate-based glass ceramic material.
The dielectric properties of the sample prepared in this example are shown in fig. 3, the dielectric constant is 119 at room temperature, and the loss is 0.016; the withstand voltage performance is 1981.9kV/cm and the theoretical energy storage density is 20.7J/cm as shown in figure 43The material can be applied to energy storage capacitor materials; the XRD pattern is shown in figure 5.
Example 3:
a high energy storage density rare earth doped niobate base glass ceramic material is prepared by the following steps:
1) with a purity of more than 99 wt.% of BaCO3、Bi2O3、Na2CO3、Nb2O5、SiO2、Yb2O3The raw materials are mixed according to a molar ratio of 21.6:2.4:6:30:40:0.2, the mixture is subjected to ball milling for 24 hours, then dried at 100 ℃ for 6 hours, and then melted at 1550 ℃ for 2 hours to obtain high-temperature molten slurry; wherein, the ball milling process takes absolute ethyl alcohol as a medium, and the ball-to-material ratio is 1.5: 1;
2) pouring the high-temperature molten slurry prepared in the step 1) into a square metal mold, performing stress annealing at 650 ℃ for 6 hours, and then cutting to obtain a glass sheet with the thickness of 1.0-1.5 mm;
3) putting equal amount of glass sheets prepared in the step 2) into a crucible, heating to 950 ℃ at a heating rate of 3 ℃/min, and keeping the temperature for 5h to obtain the niobate-based glass ceramic material.
The dielectric properties of the sample prepared in this example are shown in fig. 3, the dielectric constant is 121 at room temperature, and the loss is 0.015; the withstand voltage performance is 2046.5kV/cm and the theoretical energy storage density is 22.4J/cm as shown in figure 43The material can be applied to energy storage capacitor materials; the XRD pattern is shown in figure 5.
Example 4:
a high energy storage density rare earth doped niobate base glass ceramic material is prepared by the following steps:
1) with a purity of more than 99 wt.% of BaCO3、Bi2O3、Na2CO3、Nb2O5、SiO2、Yb2O3、MnO2The raw materials are mixed according to a molar ratio of 21.6:2.4:6:30:40:0.2: y, and the mixture is subjected to ball milling for 24 hours, then dried at 100 ℃ for 6 hours, and then melted at 1550 ℃ for 2 hours to obtain high-temperature molten slurry; wherein y is 0, 0.1, 0.2, 0.5 and 1, and absolute ethyl alcohol is used as a medium in the ball milling process, and the ball-to-material ratio is 1.5: 1;
2) pouring the high-temperature molten slurry prepared in the step 1) into a square metal mold, performing stress annealing at 650 ℃ for 6 hours, and then cutting to obtain a glass sheet with the thickness of 1.0-1.5 mm;
3) putting equal amount of glass sheets prepared in the step 2) into a crucible, heating to 950 ℃ at a heating rate of 3 ℃/min, and keeping the temperature for 5h to obtain the niobate-based glass ceramic material.
The dielectric properties of the sample prepared in this example are shown in fig. 6, the dielectric breakdown voltage is shown in fig. 7, and when y is 0.2, the dielectric constant is 107 at room temperature, and the loss is 0.003; 2158.1kV/cm and the theoretical energy storage density of the material is 22.06J/cm3The material can be applied to energy storage capacitor materials; the XRD spectrum is shown in figure 8.
Example 5:
a high energy storage density rare earth doped niobate base glass ceramic material can be used as an energy storage capacitor material, and the preparation method comprises the following steps:
1) with a purity of more than 99 wt.% of BaCO3、Bi2O3、Na2CO3、Nb2O5、SiO2、Gd2O3、MnO2The raw materials are proportioned, wherein the molar ratio of the components is 21.6:2.4:6:30:40:0.5:0.8, and the materials are ball-milled and mixed for 24 hours and then melted at the high temperature of 1450 ℃ for 2 hours to prepare high-temperature molten slurry; wherein, the ball milling process takes absolute ethyl alcohol as a medium, and the ball-to-material ratio is 1.5: 1;
2) pouring the high-temperature molten slurry prepared in the step 1) into a preheated square metal mold at 600 ℃ for molding, keeping the temperature at 600 ℃ for 6 hours to remove residual stress in glass to obtain uniform glass, and then cutting the glass to obtain glass sheets with the thickness of 1.0-1.5 mm;
3) putting equal amount of glass sheets prepared in the step 2) into a crucible for controlled crystallization, namely heating to 850 ℃ at the heating rate of 3 ℃/min and then preserving heat for 5h to prepare the niobate-based glass ceramic material.
Example 6:
a high energy storage density rare earth doped niobate base glass ceramic material can be used as an energy storage capacitor material, and the preparation method comprises the following steps:
1) with a purity of more than 99 wt.% of BaCO3、Bi2O3、Na2CO3、Nb2O5、SiO2、Yb2O3、MnO2The raw materials are proportioned, wherein the molar ratio of the components is 21.6:2.4:6:30:40:0.6:1, and the high-temperature molten slurry is prepared after ball milling and mixing for 24 hours and then high-temperature melting for 1 hour at 1550 ℃; wherein, the ball milling process takes absolute ethyl alcohol as a medium, and the ball-to-material ratio is 1.5: 1;
2) pouring the high-temperature molten slurry prepared in the step 1) into a preheated square metal mold at 650 ℃ for molding, keeping the temperature at 650 ℃ for 5 hours to remove residual stress in glass to obtain uniform glass, and then cutting the glass to obtain glass sheets with the thickness of 1.0-1.5 mm;
3) putting equal amount of glass sheets prepared in the step 2) into a crucible for controlled crystallization, namely heating to 1000 ℃ at a heating rate of 3 ℃/min and then preserving heat for 3h to prepare the niobate-based glass ceramic material.
Example 7:
a high energy storage density rare earth doped niobate base glass ceramic material can be used as an energy storage capacitor material, and the preparation method comprises the following steps:
1) with a purity of more than 99 wt.% of BaCO3、Bi2O3、Na2CO3、Nb2O5、SiO2、La2O3、MnO2The raw materials are proportioned, wherein the molar ratio of the components is 21.6:2.4:6:30:40:1:0.8, and the high-temperature melt slurry is prepared after ball milling and mixing for 24 hours and then high-temperature melting for 1.5 hours at 1500 ℃; wherein the above ball milling processAbsolute ethyl alcohol is used as a medium, and the ball material ratio is 1.5: 1;
2) pouring the high-temperature molten slurry prepared in the step 1) into a preheated square metal mold at 630 ℃ for molding, keeping the temperature at 630 ℃ for 5.5 hours to remove residual stress in the glass to obtain uniform glass, and then cutting the glass to obtain glass sheets with the thickness of 1.0-1.5 mm;
3) putting equal amount of glass sheets prepared in the step 2) into a crucible for controlled crystallization, namely heating to 950 ℃ at a heating rate of 3 ℃/min and then preserving heat for 4h to prepare the niobate-based glass ceramic material.
The embodiments described above are described to facilitate an 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 (8)

1. The high energy storage density rare earth doped niobate base glass ceramic material is characterized in that the chemical general formula of the material is 21.6BaCO3-2.4Bi2O3-6Na2CO3-30Nb2O5-40SiO2-xR2O3-yMnO2Wherein x is more than or equal to 0 and less than or equal to 1, y is more than or equal to 0 and less than or equal to 1, and R is one of L a, Gd and Yb.
2. The method of claim 1 for preparing a high energy storage density rare earth doped niobate-based glass ceramic material, comprising the steps of:
1) mixing BaCO3、Bi2O3、Na2CO3、Nb2O5、SiO2、R2O3And MnO2Uniformly mixing, and melting at high temperature to obtain high-temperature molten slurry;
2) pouring the high-temperature molten slurry prepared in the step 1) into a mold for molding, removing residual stress through a constant temperature process, and slicing to obtain a glass sheet;
3) and (3) performing controlled crystallization on the glass sheet prepared in the step 2) to obtain the niobate-based glass ceramic material.
3. The method as claimed in claim 2, wherein the melting temperature in step 1) is 1450-.
4. The method as claimed in claim 2, wherein the step 2) is carried out at a temperature of 600-650 ℃.
5. The method as claimed in claim 2, wherein in the step 2), the constant temperature is 600-650 ℃ and the constant temperature time is 5-6 h.
6. The method as claimed in claim 2, wherein in the step 3), the temperature-raising rate is 1-5 ℃/min, the crystallization temperature is 850 ℃ and 1000 ℃, and the crystallization time is 3-5 h.
7. The method for preparing a rare earth doped niobate-based glass ceramic material with high energy storage density as claimed in claim 6, wherein the crystallization temperature is 950 ℃ and the crystallization time is 3-5 h.
8. Use of a high energy storage density rare earth doped niobate-based glass ceramic material according to claim 1, for the preparation of an energy storage capacitor.
CN202010260194.4A 2020-04-03 2020-04-03 High-energy-density rare earth-doped niobate-based glass ceramic material and preparation method and application thereof Pending CN111410426A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202010260194.4A CN111410426A (en) 2020-04-03 2020-04-03 High-energy-density rare earth-doped niobate-based glass ceramic material and preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202010260194.4A CN111410426A (en) 2020-04-03 2020-04-03 High-energy-density rare earth-doped niobate-based glass ceramic material and preparation method and application thereof

Publications (1)

Publication Number Publication Date
CN111410426A true CN111410426A (en) 2020-07-14

Family

ID=71487978

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202010260194.4A Pending CN111410426A (en) 2020-04-03 2020-04-03 High-energy-density rare earth-doped niobate-based glass ceramic material and preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN111410426A (en)

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104803605A (en) * 2015-03-26 2015-07-29 同济大学 Rare-earth-doped barium-strontium-titanate-based glass ceramic energy storage material and preparation method thereof
JP2018111634A (en) * 2017-01-12 2018-07-19 株式会社オハラ Glass, and glass ceramics
CN110451807A (en) * 2019-07-29 2019-11-15 同济大学 The bismuth niobate barium sodium base glass ceramic material of high energy storage density and its preparation and application

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104803605A (en) * 2015-03-26 2015-07-29 同济大学 Rare-earth-doped barium-strontium-titanate-based glass ceramic energy storage material and preparation method thereof
JP2018111634A (en) * 2017-01-12 2018-07-19 株式会社オハラ Glass, and glass ceramics
CN110451807A (en) * 2019-07-29 2019-11-15 同济大学 The bismuth niobate barium sodium base glass ceramic material of high energy storage density and its preparation and application

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
SHAOMEI XIU ETAL.: "The effects of MnO2 addition on the structure and dielectric properties of the strontium barium niobate glass-ceramics", 《MATERIALS RESEARCH BULLETIN》 *

Similar Documents

Publication Publication Date Title
CN108395106B (en) Barium niobate lead sodium based glass ceramic material with high energy storage density and preparation method thereof
CN111763082B (en) Barium strontium titanate-based dielectric ceramic material and preparation method and application thereof
CN102260044B (en) Energy storage niobate microcrystalline glass dielectric material and preparation method thereof
CN113582683B (en) BaTiO for X8R MLCC 3 Preparation method of base ceramic material
CN110451807B (en) Bismuth barium sodium niobate-based glass ceramic material with high energy storage density and preparation and application thereof
CN110240409B (en) Barium niobate lead sodium based glass ceramic material with high energy storage density and preparation method thereof
CN101531461B (en) Dielectric material of glass-ceramics with high energy storage density and preparation method
CN111995391A (en) Low-sintering antiferroelectric ceramic material for high-energy-storage-density capacitor and preparation method thereof
CN111978082A (en) Strontium magnesium niobate doped modified sodium bismuth titanate based energy storage ceramic material and preparation method thereof
CN114716248A (en) High-energy-storage-property rare earth-doped tungsten bronze structure ceramic material and preparation method thereof
CN105271761A (en) High-energy-density niobate-based glass ceramic energy storage material and preparation and application thereof
CN114031396B (en) Preparation method for effectively reducing sintering temperature of antiferroelectric ceramic material
CN105712634B (en) Lanthanum oxide doping strontium barium niobate base glass ceramics energy storage material and preparation method thereof
CN108585515B (en) Bismuth niobate-based glass ceramic material with high energy storage density and preparation method and application thereof
CN113213923A (en) Lead hafnate titanate-based antiferroelectric ceramic material and preparation method thereof
CN105731806A (en) High energy storage density strontium potassium niobate based glass ceramic energy storage material and preparation and application thereof
CN105399405A (en) Low dielectric microwave ferroelectric ceramics and preparation method thereof
KR20030090978A (en) Dielectric Composition For Multilayer Ceramic Condenser And Multilayer Ceramic Condenser Using The Same
CN116425543A (en) B-bit high-entropy ceramic with high energy storage and charge-discharge performance as dielectric material and preparation method thereof
CN111410426A (en) High-energy-density rare earth-doped niobate-based glass ceramic material and preparation method and application thereof
CN115947598B (en) Antiferroelectric material capable of being co-fired with base metal inner electrode and preparation method thereof
CN109293353B (en) Lead-free BiFeO with high energy storage density and high energy storage efficiency3Ferroelectric ceramic material and its preparation method
CN115611627A (en) Lead zirconate stannate-based antiferroelectric ceramic material and preparation method and application thereof
CN112960981B (en) Preparation method of lanthanum-tin doped lead zirconate titanate ceramic material
CN115368132A (en) Barium titanate-based ceramic material and preparation method thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
RJ01 Rejection of invention patent application after publication
RJ01 Rejection of invention patent application after publication

Application publication date: 20200714