CN106186704B - A kind of strontium barium niobate potassium base glass ceramics energy storage material and the preparation method and application thereof - Google Patents
A kind of strontium barium niobate potassium base glass ceramics energy storage material and the preparation method and application thereof Download PDFInfo
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- CN106186704B CN106186704B CN201610578443.8A CN201610578443A CN106186704B CN 106186704 B CN106186704 B CN 106186704B CN 201610578443 A CN201610578443 A CN 201610578443A CN 106186704 B CN106186704 B CN 106186704B
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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
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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
- C03C1/00—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels
Abstract
The present invention relates to a kind of strontium barium niobate potassium base glass ceramics energy storage materials and the preparation method and application thereof, and the preparation method is specifically includes the following steps: with SrCO3、BaCO3、K2CO3、Nb2O5、SiO2For raw material, 25.6mol% [xSrCO in molar ratio3+(1‑x)BaCO3] -6.4mol%K2CO3- 32mol%Nb2O5- 36mol%SiO2Ingredient is carried out, wherein x value range is 0.2-1；By ingredient after ball mill mixing, drying, and high temperature melting is carried out, high-temperature fusant is made；High-temperature fusant is poured into the metal die of preheating, stress relief annealing, transparent glass is made, and the transparent glass is cut into glass flake；Glass flake is subjected to Controlled Crystallization, obtains the strontium barium niobate potassium base glass ceramics energy storage material, which is applied to energy-storage capacitor material.Compared with prior art, the present invention in niobic acid barium potassium system by adding the glass ceramics energy storage material not only energy storage density (17.28J/cm with higher of strontium preparation3), the microstructure of more uniform densification, and the tangent value (0.006) with lower dielectric loss angle.
Description
Technical field
The invention belongs to dielectric energy storage material technical fields, are related to a kind of strontium barium niobate potassium base glass ceramics energy storage material
And the preparation method and application thereof.
Background technique
With the development of industry, energy demand is continuously increased, and faces energy crisis, is improved energy utilization rate and is developed new energy
Source becomes the major issue of scientific research.In order to improve energy utilization rate, various energy storage technologies and energy storage material come into being,
Middle high energy-storage capacitor is quite important, it is common circuit components.For energy-storage capacitor, it have energy storage density it is high,
The key properties such as charge/discharge speed is fast, utilization rate is high, performance is stable.In recent years, Pulse Power Techniques are widely used to electronics
The national defence such as computer, communication, radar, all-electric warship, electromagnetic railgun weapon, hybrid vehicle, controlled laser nuclear fusion
And modern industrial technology field.Obviously breaking through does not occur also in the energy storage density of current material, and the volume of energy storage device is entire
Occupy in pulser greatly, this also constrains pulser to miniaturization, the development of lightness significantly.Therefore, mesh
The preceding requirement in order to meet the miniaturization and high energy storage density of pulse power system, various countries material worker just try to explore to study
With high dielectric constant, the low dielectric material for connecing electrical loss and high withstand voltage intensity.
Glass ceramics is to prepare glass matrix using high-temperature fusion-method for quick cooling, is prepared using controllable crystallization method
At glass ceramics.Strontium barium niobate potassium base glass ceramics has some apparent advantages compared with traditional ceramics material, for example, preparation
Uncomplicated, resistance to disruptive field intensity is high, dielectric adjustable is strong, dielectric loss is low, possess wide application in dielectric material field before
Scape.Strontium barium niobate potash glass ceramics can form the co-melting body of strontium barium niobate and strontium potassium niobate, realize that the high dielectric of potassium niobate is normal
The features such as number, the resistance to disruptive field intensity of height of niobic acid barium and low-dielectric loss.Result of study shows that strontium barium niobate potassium base glass ceramics is stored up
It can material energy storage density with higher.
Currently, the energy storage density of the energy storage material for capacitor, pulse technique etc. is also smaller, however it remains greatly
Development space.In order to improve the energy storage density of material, many scholars are to titanate and niobates glass ceramics dielectric properties and storage
Energy characteristic conducts extensive research.Wherein, D.F.Han et al. is by changing strontium lead ratio to niobates glass ceramics energy-storage property
It is optimized, the study found that dielectric constant first increases and then decreases, resistance to disruptive field intensity reduces always, phase as strontium lead ratio increases
The energy storage density first increases and then decreases for the glass ceramic material answered, when strontium lead ratio reach suitably than when, energy storage density reaches most
Greatly 2.27J/cm3(Ceramics International, 2012,38:6903-6906).The niobic acid of Jun Du et al. research
The energy storage density of barium sodium base glass ceramics is 1.87J/cm3(J.Phys.:Conf.Ser., 2009,152:0212061).And
Shuangxi Xue et al. has studied the influence that barium sodium compares barium sodium niobate (BNN) base glass ceramic material energy-storage property, studies have shown that
When barium sodium ratio reaches proper ratio, energy storage density reaches maximum 5.12J/cm3(Shuangxi Xue,et al.Ceramics
International, 2014,40:7495-7499), and influence of the addition rare earth to barium sodium niobate (BNN) base glass ceramics performance,
Wherein energy storage density maximum value reaches 8.4J/cm3(Shuangxi Xue, et al.Ceramics International,
2015,41:S441-S446).The energy storage density that Guohua Chen et al. has studied barium strontium niobate Na20-B203-Si02 glass is 4J/cm3
(Journal of electronceramics,2011,27:78-82).Shi Xiao has studied strontium potassium niobate aluminosilicate glass pottery
The crystallization behavior and dielectric properties of ceramic material, they have found, as the temperature increases, resistance to disruptive field intensity reduces system, and dielectric
Constant first increases and reduces afterwards, and corresponding energy storage density first increases to be reduced afterwards, and maximum energy storage density is 4.41J/cm3.So far,
Although people conduct extensive research dielectric energy storage material, the energy storage for the glass ceramics energy storage material reported is close
Degree is not also sufficiently large, and dielectric loss is not sufficiently low.
Application No. is the Chinese invention patents of 201610006156.X to disclose a kind of strontium barium niobate potassium of high energy storage density
Base glass ceramics energy storage material and the preparation method and application thereof, the strontium barium niobate potassium base glass ceramics energy storage material include SrO,
Na2O、Nb2O5、SiO2Four kinds of ingredients, and the molar ratio of four kinds of substances is SrO:Na2O:Nb2O5: SiO2=42x:42 (1-x): 28:
30, it is made by following steps: weighing raw material, after ball mill mixing, drying, and high temperature melting is carried out, high-temperature fusant is made；So
It is poured into the metal die of preheating afterwards, stress relief annealing, transparent glass is made, is cut into a thickness of 0.9~1.2mm's
Glass flake carries out Controlled Crystallization, obtains product, which can be applied to energy-storage capacitor material.Compared with above-mentioned patent,
The present invention has following difference: 1) raw material and proportion are different；2) the more uniform densification of microstructure；3) in high energy storage density
In the case of, dielectric constant improves nearly 2 times, and dielectric loss substantially reduces.
Summary of the invention
It is an object of the present invention to overcome the above-mentioned drawbacks of the prior art and provide a kind of energy storage density is higher,
Dielectric loss is low, strontium barium niobate potassium base glass ceramics energy storage material of dense micro-structure and the preparation method and application thereof.
The purpose of the present invention can be achieved through the following technical solutions:
A kind of preparation method of strontium barium niobate potassium base glass ceramics energy storage material, this method specifically includes the following steps:
(1) with SrCO3、BaCO3、K2CO3、Nb2O5、SiO2For raw material, 25.6mol% [xSrCO in molar ratio3+(1-x)
BaCO3] -6.4mol%K2CO3- 32mol%Nb2O5- 36mol%SiO2Ingredient is carried out, wherein x value range is 0.2-1；
(2) by the ingredient of step (1) after ball mill mixing, drying, and high temperature melting is carried out, high-temperature fusant is made；
(3) high-temperature fusant made from step (2) is poured into the metal die of preheating, stress relief annealing is made transparent
Glass, and the transparent glass is cut into glass flake；
(4) glass flake made from step (3) is subjected to Controlled Crystallization, obtains the strontium barium niobate potassium base glass pottery
Porcelain energy storage material.
The value of x is 0.2,0.4,0.6,0.8 or 1 in step (1).
SrCO described in step (1)3、BaCO3、K2CO3、Nb2O5And SiO2Purity be greater than 99wt%.
The time of ball mill mixing described in step (2) is 10-20h, and the temperature of the high temperature melting is 1500-1650
DEG C, the time of high temperature melting is 1.5-4h.
The time of ball mill mixing described in step (2) is 12-16h, the high temperature melting as a preferred technical solution,
Temperature be 1500-1600 DEG C, time of high temperature melting is 2-3h.
The temperature of stress relief annealing described in step (3) is 600-700 DEG C, and the time of the stress relief annealing is 4-
7h。
The temperature of stress relief annealing described in step (3) is 600-680 DEG C as a preferred technical solution, and described goes
The time of stress annealing is 5h.
Glass flake described in step (3) with a thickness of 1.4-1.6mm.
The temperature of Controlled Crystallization described in step (4) is 650-1100 DEG C, soaking time 2-5h.
The temperature of Controlled Crystallization described in step (4) is 900-1100 DEG C as a preferred technical solution, and soaking time is
2-4h。
The strontium barium niobate potassium base glass ceramics energy storage material being prepared using the above method.
The application of strontium barium niobate potassium base glass ceramics energy storage material, the strontium barium niobate potassium base glass ceramics energy storage material
Applied to energy-storage capacitor material.
In the present invention, the glass ceramics energy storage material is mainly by amorphous glass phase and ceramic phase composition, ceramic phase master
It to be blue copper phase SrNb2O6, Sr0.5Ba0.5Nb2O6, SrBaKNb5O15Deng 25.6mol% [xSrCO in molar ratio3+(1-x)
BaCO3] -6.4mol%K2CO3- 32mol%Nb2O5- 36mol%SiO2Ingredient is carried out, wherein x=0.2~1.Through ball mill mixing,
Drying, then high temperature melting reaction is carried out, and high-temperature fusant Quick pouring is formed into metal die, subsequent stress relief annealing,
It is cut into glass flake, then Controlled Crystallization, obtains the strontium barium niobate potassium base glass ceramics energy storage material.
The present invention is based on 25.6mol% [xSrCO3+(1-x)BaCO3] -6.4mol%K2CO3- 32mol%Nb2O5-
36mol%SiO2Ingredient, wherein x=0.2~1；By adjusting SrCO3And BaCO3After mole when different heat treatment temperature
Glass ceramics, phase structure improved, and resistance to disruptive field intensity significantly improves, and as x=0.4, crystallization temperature is 900 DEG C, resistance to
Disruptive field intensity is optimal value 1883kV/cm, and theoretical energy storage density reaches 17.28J/cm3, dielectric loss at room temperature is reduced to
0.6%.
Compared with prior art, the invention has the characteristics that:
1) it is matched by changing ceramic composition, improves resistance to disruptive field intensity, so its energy storage density is made to be improved significantly,
Dielectric loss is substantially reduced；
2) system is simple, and preparation method is simple, economical and practical without complicated post-processing step, (Sr/Ba, K) obtained
NbO3Base glass ceramics energy storage material has superior dielectric performance, and the energy storage characteristic of material is significantly improved.
Detailed description of the invention
Fig. 1 is the X-ray diffraction analysis figure (XRD) of embodiment 1-5 strontium barium niobate potassium base glass ceramic material；
Fig. 2 is the X-ray diffraction analysis figure (XRD) of embodiment 6-8 strontium barium niobate potassium base glass ceramic material；
Fig. 3 is the dielectric temperature spectrum and dielectric loss figure of embodiment 1-5 strontium barium niobate potassium base glass ceramic material；
Fig. 4 is the dielectric temperature spectrum and dielectric loss figure of embodiment 6-8 strontium barium niobate potassium base glass ceramic material；
Fig. 5 is the Weibull distribution map of the resistance to disruptive field intensity of embodiment 1-5 strontium barium niobate potassium base glass ceramic material；
Fig. 6 is the Weibull distribution map of the resistance to disruptive field intensity of embodiment 6-8 strontium barium niobate potassium base glass ceramic material；
Fig. 7-1 is the scanning electron microscope diagram spectrum of 1 strontium barium niobate potassium base glass ceramic material of embodiment；
Fig. 7-2 is the scanning electron microscope diagram spectrum of 2 strontium barium niobate potassium base glass ceramic material of embodiment；
Fig. 7-3 is the scanning electron microscope diagram spectrum of 3 strontium barium niobate potassium base glass ceramic material of embodiment；
Fig. 7-4 is the scanning electron microscope diagram spectrum of 4 strontium barium niobate potassium base glass ceramic material of embodiment；
Fig. 7-5 is the scanning electron microscope diagram spectrum of 5 strontium barium niobate potassium base glass ceramic material of embodiment；
Fig. 7-6 is the scanning electron microscope diagram spectrum of 6 strontium barium niobate potassium base glass ceramic material of embodiment；
Fig. 7-7 is the scanning electron microscope diagram spectrum of 7 strontium barium niobate potassium base glass ceramic material of embodiment；
Fig. 7-8 is the scanning electron microscope diagram spectrum of 8 strontium barium niobate potassium base glass ceramic material of embodiment；
Wherein, in Fig. 5 and Fig. 6, εrFor dielectric constant, tan δ is dielectric loss, EiFor the resistance to breakdown of i-th of test sample
Field strength, n are the summation of resistance to breakdown field intensity values, EbFor the resistance to disruptive field intensity being distributed by Weibull.
Specific embodiment
The present invention is described in detail with specific embodiment below in conjunction with the accompanying drawings.
Abbreviation used in throughout the specification has following meanings, unless clearly indicating otherwise in text: DEG C=Celsius
Degree, kV=kilovolt, cm=centimetres；Mol=moles, h=hours；Min=minutes, mol%=molar percentage.Various raw materials
It is purchased from commercial supplier with reagent, without being further purified, unless otherwise indicated.The raw materials and reagents of moisture-sensitive are deposited in
It in hermetically sealed bottle, and directly uses, without specially treated.
Embodiment 1:
(1) it is greater than the SrCO of 99wt% with purity3、BaCO3、K2CO3、Nb2O5And SiO2For feed proportioning, above-mentioned each component
Molar percentage be 5.12%, 20.48%, 6.4%, 32% and 36%, after ball mill mixing 16h, drying, in 1500 DEG C of height
Temperature fusing 2h；
(2) high-temperature fusant that step (1) obtains is poured into metal die, in 600 DEG C of temperature stress relief annealing 6h, so
The glass flake with a thickness of 0.9~1.5mm is obtained by cutting；
(3) glass flake made from step (2) is subjected to Controlled Crystallization in 900 DEG C of heat preservation 3h, obtains glass ceramics.
The XRD of sample obtained by the present embodiment as shown in Figure 1, dielectric properties as shown in figure 3, pressure-resistant performance test as schemed
Shown in 5, for microscopic appearance as shown in Fig. 7-1, energy storage density is as shown in table 1.
Embodiment 2:
(1) it is greater than the SrCO of 99wt% with purity3、BaCO3、K2CO3、Nb2O5And SiO2For feed proportioning, above-mentioned each component
Molar percentage be 10.24%, 15.36%, 6.4%, 32% and 36%, after ball mill mixing 16h, drying, at 1500 DEG C
High temperature melting 2h；
(2) high-temperature fusant that step (1) obtains is poured into metal die, in 600 DEG C of temperature stress relief annealing 6h, so
The glass flake with a thickness of 0.9~1.5mm is obtained by cutting；
(3) glass flake made from step (2) is subjected to Controlled Crystallization in 900 DEG C of heat preservation 3h, obtains glass ceramics.
The XRD of sample obtained by the present embodiment as shown in Figure 1, dielectric properties as shown in figure 3, pressure-resistant performance test as schemed
Shown in 5, for microscopic appearance as shown in Fig. 7-2, energy storage density is as shown in table 1, value 17.28J/cm3, can be used as energy-storage capacitor
Material.
Embodiment 3:
(1) it is greater than the SrCO of 99wt% with purity3、BaCO3、K2CO3、Nb2O5And SiO2For feed proportioning, above-mentioned each component
Molar percentage be 15.36%, 10.24%, 6.4%, 32% and 36%, after ball mill mixing 16h, drying, at 1500 DEG C
High temperature melting 2h；
(2) high-temperature fusant that step (1) obtains is poured into metal die, in 600 DEG C of temperature stress relief annealing 6h, so
The glass flake with a thickness of 0.9~1.5mm is obtained by cutting；
(3) glass flake made from step (2) is subjected to Controlled Crystallization in 900 DEG C of heat preservation 3h, obtains glass ceramics.
The XRD of sample obtained by the present embodiment as shown in Figure 1, dielectric properties as shown in figure 3, pressure-resistant performance test as schemed
Shown in 5, for microscopic appearance as shown in Fig. 7-3, energy storage density is as shown in table 1, value 15.99J/cm3, can be used as energy-storage capacitor
Material.
Embodiment 4:
(1) it is greater than the SrCO of 99wt% with purity3、BaCO3、K2CO3、Nb2O5And SiO2For feed proportioning, above-mentioned each component
Molar percentage be 20.48%, 5.12%, 6.4%, 32% and 36%, after ball mill mixing 16h, drying, in 1500 DEG C of height
Temperature fusing 2h；
(2) high-temperature fusant that step 1) obtains is poured into metal die, in 600 DEG C of temperature stress relief annealing 6h, so
The glass flake with a thickness of 0.9~1.5mm is obtained by cutting；
(3) glass flake made from step (2) is subjected to Controlled Crystallization in 900 DEG C of heat preservation 3h, obtains glass ceramics.
The XRD of sample obtained by the present embodiment as shown in Figure 1, dielectric properties as shown in figure 3, pressure-resistant performance test as schemed
Shown in 5, for microscopic appearance as shown in Fig. 7-4, energy storage density is as shown in table 1.
Embodiment 5:
(1) it is greater than the SrCO of 99wt% with purity3、BaCO3、K2CO3、Nb2O5And SiO2For feed proportioning, above-mentioned each component
Molar percentage be 25.6%, 6.4%, 32% and 36%, after ball mill mixing 16h, drying, in 1500 DEG C of high temperature meltings
2h；
(2) high-temperature fusant that step 1) obtains is poured into metal die, in 600 DEG C of temperature stress relief annealing 6h, so
The glass flake with a thickness of 0.9~1.5mm is obtained by cutting；
(3) glass flake made from step (2) is subjected to Controlled Crystallization in 900 DEG C of heat preservation 3h, obtains glass ceramics.
The XRD of sample obtained by the present embodiment as shown in Figure 1, dielectric properties as shown in figure 3, pressure-resistant performance test as schemed
Shown in 5, for microscopic appearance as shown in Fig. 7-5, energy storage density is as shown in table 1.
Embodiment 6:
It is identical as 2 step of embodiment (1) and (2), the difference is that step (3) Controlled Crystallization temperature is 800 DEG C.
The XRD of sample obtained by the present embodiment as shown in Fig. 2, dielectric properties as shown in figure 4, pressure-resistant performance test as schemed
Shown in 6, for microscopic appearance as shown in Fig. 7-6, energy storage density is as shown in table 1.
Embodiment 7:
It is identical as 2 step of embodiment, the process is repeated here just to compare.Sample obtained by the present embodiment
The XRD of product as shown in Fig. 2, dielectric properties as shown in figure 4, pressure-resistant performance test as shown in fig. 6, microscopic appearance as shown in Fig. 7-7,
Energy storage density is as shown in table 1
Embodiment 8:
It is identical as 2 step of embodiment (1) and (2), the difference is that step (3) Controlled Crystallization temperature is 1000 DEG C.
The XRD of sample obtained by the present embodiment as shown in Fig. 2, dielectric properties as shown in figure 4, pressure-resistant performance test as schemed
Shown in 6, microscopic appearance is as Figure 7-8, and energy storage density is as shown in table 1.
Table 1
From case study on implementation above, the present invention has prepared the strontium barium niobate potassium base glass ceramics energy storage material of high energy storage density
Material, energy storage density is compared with and dielectric loss is lower, and therefore, the material of the system is used as energy-storage capacitor material.
Embodiment 9:
The preparation method of the present embodiment strontium barium niobate potassium base glass ceramics energy storage material, specifically includes the following steps:
(1) with SrCO3、BaCO3、K2CO3、Nb2O5、SiO2For raw material, 25.6mol% [0.3SrCO in molar ratio3+
0.7BaCO3] -6.4mol%K2CO3- 32mol%Nb2O5- 36mol%SiO2Carry out ingredient；
(2) by the ingredient of step (1) after ball mill mixing, drying, and high temperature melting is carried out, high-temperature fusant is made；
(3) high-temperature fusant made from step (2) is poured into the metal die of preheating, stress relief annealing is made transparent
Glass, and the transparent glass is cut into the glass flake with a thickness of 1.4mm；
(4) glass flake made from step (3) is subjected to Controlled Crystallization, obtains the strontium barium niobate potassium base glass pottery
Porcelain energy storage material.
SrCO described in step (1)3、BaCO3、K2CO3、Nb2O5And SiO2Purity be greater than 99wt%.
In step (2), time of ball mill mixing is 10h, and the temperature of high temperature melting is 1500 DEG C, and the time of high temperature melting is
4h。
In step (3), the temperature of stress relief annealing is 600 DEG C, and the time of stress relief annealing is 7h.
In step (4), the temperature of Controlled Crystallization is 650 DEG C, soaking time 5h.
Strontium barium niobate potassium base glass ceramics energy storage material made from the present embodiment is applied to energy-storage capacitor material.
Embodiment 10:
The preparation method of the present embodiment strontium barium niobate potassium base glass ceramics energy storage material, specifically includes the following steps:
(1) with SrCO3、BaCO3、K2CO3、Nb2O5、SiO2For raw material, 25.6mol% [0.2SrCO in molar ratio3+
0.8BaCO3] -6.4mol%K2CO3- 32mol%Nb2O5- 36mol%SiO2Carry out ingredient；
(2) by the ingredient of step (1) after ball mill mixing, drying, and high temperature melting is carried out, high-temperature fusant is made；
(3) high-temperature fusant made from step (2) is poured into the metal die of preheating, stress relief annealing is made transparent
Glass, and the transparent glass is cut into the glass flake with a thickness of 1.5mm；
(4) glass flake made from step (3) is subjected to Controlled Crystallization, obtains the strontium barium niobate potassium base glass pottery
Porcelain energy storage material.
SrCO described in step (1)3、BaCO3、K2CO3、Nb2O5And SiO2Purity be greater than 99wt%.
In step (2), time of ball mill mixing is 12h, and the temperature of high temperature melting is 1600 DEG C, and the time of high temperature melting is
3h。
In step (3), the temperature of stress relief annealing is 680 DEG C, and the time of stress relief annealing is 5h.
In step (4), the temperature of Controlled Crystallization is 900 DEG C, soaking time 4h.
Strontium barium niobate potassium base glass ceramics energy storage material made from the present embodiment is applied to energy-storage capacitor material.
Embodiment 11:
The preparation method of the present embodiment strontium barium niobate potassium base glass ceramics energy storage material, specifically includes the following steps:
(1) with SrCO3、BaCO3、K2CO3、Nb2O5、SiO2For raw material, 25.6mol% [0.4SrCO in molar ratio3+
0.6BaCO3] -6.4mol%K2CO3- 32mol%Nb2O5- 36mol%SiO2Carry out ingredient；
(2) by the ingredient of step (1) after ball mill mixing, drying, and high temperature melting is carried out, high-temperature fusant is made；
(3) high-temperature fusant made from step (2) is poured into the metal die of preheating, stress relief annealing is made transparent
Glass, and the transparent glass is cut into the glass flake with a thickness of 1.6mm；
(4) glass flake made from step (3) is subjected to Controlled Crystallization, obtains the strontium barium niobate potassium base glass pottery
Porcelain energy storage material.
SrCO described in step (1)3、BaCO3、K2CO3、Nb2O5And SiO2Purity be greater than 99wt%.
In step (2), time of ball mill mixing is 16h, and the temperature of high temperature melting is 1580 DEG C, and the time of high temperature melting is
2.5h。
In step (3), the temperature of stress relief annealing is 640 DEG C, and the time of stress relief annealing is 5h.
In step (4), the temperature of Controlled Crystallization is 1000 DEG C, soaking time 3h.
Strontium barium niobate potassium base glass ceramics energy storage material made from the present embodiment is applied to energy-storage capacitor material.
Embodiment 12:
The preparation method of the present embodiment strontium barium niobate potassium base glass ceramics energy storage material, specifically includes the following steps:
(1) with SrCO3、BaCO3、K2CO3、Nb2O5、SiO2For raw material, 25.6mol% [0.6SrCO in molar ratio3+
0.4BaCO3] -6.4mol%K2CO3- 32mol%Nb2O5- 36mol%SiO2Carry out ingredient；
(2) by the ingredient of step (1) after ball mill mixing, drying, and high temperature melting is carried out, high-temperature fusant is made；
(3) high-temperature fusant made from step (2) is poured into the metal die of preheating, stress relief annealing is made transparent
Glass, and the transparent glass is cut into the glass flake with a thickness of 1.5mm；
(4) glass flake made from step (3) is subjected to Controlled Crystallization, obtains the strontium barium niobate potassium base glass pottery
Porcelain energy storage material.
SrCO described in step (1)3、BaCO3、K2CO3、Nb2O5And SiO2Purity be greater than 99wt%.
In step (2), time of ball mill mixing is 20h, and the temperature of high temperature melting is 1650 DEG C, and the time of high temperature melting is
1.5h。
In step (3), the temperature of stress relief annealing is 700 DEG C, and the time of stress relief annealing is 4h.
In step (4), the temperature of Controlled Crystallization is 1100 DEG C, soaking time 2h.
Strontium barium niobate potassium base glass ceramics energy storage material made from the present embodiment is applied to energy-storage capacitor material.
Embodiment 13:
The preparation method of the present embodiment strontium barium niobate potassium base glass ceramics energy storage material, specifically includes the following steps:
(1) with SrCO3、BaCO3、K2CO3、Nb2O5、SiO2For raw material, 25.6mol% [0.8SrCO in molar ratio3+
0.2BaCO3] -6.4mol%K2CO3- 32mol%Nb2O5- 36mol%SiO2Carry out ingredient；
(2) by the ingredient of step (1) after ball mill mixing, drying, and high temperature melting is carried out, high-temperature fusant is made；
(3) high-temperature fusant made from step (2) is poured into the metal die of preheating, stress relief annealing is made transparent
Glass, and the transparent glass is cut into the glass flake with a thickness of 1.5mm；
(4) glass flake made from step (3) is subjected to Controlled Crystallization, obtains the strontium barium niobate potassium base glass pottery
Porcelain energy storage material.
SrCO described in step (1)3、BaCO3、K2CO3、Nb2O5And SiO2Purity be greater than 99wt%.
In step (2), time of ball mill mixing is 10h, and the temperature of high temperature melting is 1620 DEG C, and the time of high temperature melting is
2h。
In step (3), the temperature of stress relief annealing is 690 DEG C, and the time of stress relief annealing is 6h.
In step (4), the temperature of Controlled Crystallization is 800 DEG C, soaking time 5h.
Strontium barium niobate potassium base glass ceramics energy storage material made from the present embodiment is applied to energy-storage capacitor material.
Embodiment 14:
The preparation method of the present embodiment strontium barium niobate potassium base glass ceramics energy storage material, specifically includes the following steps:
(1) with SrCO3、BaCO3、K2CO3、Nb2O5、SiO2For raw material, 25.6mol%SrCO in molar ratio3- 6.4mol%
K2CO3- 32mol%Nb2O5- 36mol%SiO2Carry out ingredient；
(2) by the ingredient of step (1) after ball mill mixing, drying, and high temperature melting is carried out, high-temperature fusant is made；
(3) high-temperature fusant made from step (2) is poured into the metal die of preheating, stress relief annealing is made transparent
Glass, and the transparent glass is cut into the glass flake with a thickness of 1.5mm；
(4) glass flake made from step (3) is subjected to Controlled Crystallization, obtains the strontium barium niobate potassium base glass pottery
Porcelain energy storage material.
SrCO described in step (1)3、BaCO3、K2CO3、Nb2O5And SiO2Purity be greater than 99wt%.
In step (2), time of ball mill mixing is 18h, and the temperature of high temperature melting is 1500 DEG C, and the time of high temperature melting is
4h。
In step (3), the temperature of stress relief annealing is 600 DEG C, and the time of stress relief annealing is 7h.
In step (4), the temperature of Controlled Crystallization is 960 DEG C, soaking time 4h.
Strontium barium niobate potassium base glass ceramics energy storage material made from the present embodiment is applied to energy-storage capacitor material.
The above description of the embodiments is intended to facilitate ordinary skill in the art to understand and use the invention.
Person skilled in the art obviously easily can make various modifications to these embodiments, and described herein general
Principle is applied in other embodiments without having to go through creative labor.Therefore, the present invention is not limited to the above embodiments, ability
Field technique personnel announcement according to the present invention, improvement and modification made without departing from the scope of the present invention all should be of the invention
Within protection scope.
Claims (8)
1. a kind of preparation method of strontium barium niobate potassium base glass ceramics energy storage material, which is characterized in that this method specifically include with
Lower step:
(1) with SrCO3、BaCO3、K2CO3、Nb2O5、SiO2For raw material, 25.6mol% [xSrCO in molar ratio3+(1-x)
BaCO3] -6.4mol%K2CO3- 32mol%Nb2O5- 36mol%SiO2Ingredient is carried out, wherein x value range is 0.2-0.8；
(2) by the ingredient of step (1) after ball mill mixing, drying, and high temperature melting is carried out, high-temperature fusant is made；
(3) high-temperature fusant made from step (2) is poured into the metal die of preheating, stress relief annealing, transparent glass is made,
And the transparent glass is cut into glass flake；
(4) glass flake made from step (3) is subjected to Controlled Crystallization, obtains the strontium barium niobate potassium base glass ceramics storage
It can material；
The glass ceramics energy storage material includes blue copper phase SrNb2O6、Sr0.5Ba0.5Nb2O6、SrBaKNb5O15。
2. a kind of preparation method of strontium barium niobate potassium base glass ceramics energy storage material according to claim 1, feature exist
In the value of x is 0.2,0.4,0.6 or 0.8 in step (1).
3. a kind of preparation method of strontium barium niobate potassium base glass ceramics energy storage material according to claim 1, feature exist
In SrCO described in step (1)3、BaCO3、K2CO3、Nb2O5And SiO2Purity be greater than 99wt%.
4. a kind of preparation method of strontium barium niobate potassium base glass ceramics energy storage material according to claim 1, feature exist
In the time of ball mill mixing described in step (2) is 10-20h, and the temperature of the high temperature melting is 1500-1650 DEG C, high temperature
The time of fusing is 1.5-4h.
5. a kind of preparation method of strontium barium niobate potassium base glass ceramics energy storage material according to claim 1, feature exist
In the temperature of stress relief annealing described in step (3) is 600-700 DEG C, and the time of the stress relief annealing is 4-7h.
6. a kind of preparation method of strontium barium niobate potassium base glass ceramics energy storage material according to claim 1, feature exist
In the temperature of Controlled Crystallization described in step (4) is 650-1100 DEG C, soaking time 2-5h.
7. the strontium barium niobate potassium base glass ceramics energy storage material being prepared using method as claimed in any one of claims 1 to 6.
8. the application of strontium barium niobate potassium base glass ceramics energy storage material as claimed in claim 7, which is characterized in that the niobium
Sour strontium barium potassium base glass ceramics energy storage material is applied to energy-storage capacitor material.
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