CN106186704A - A kind of strontium barium niobate potassio glass ceramics energy storage material and preparation method and application - Google Patents

A kind of strontium barium niobate potassio glass ceramics energy storage material and preparation method and application Download PDF

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CN106186704A
CN106186704A CN201610578443.8A CN201610578443A CN106186704A CN 106186704 A CN106186704 A CN 106186704A CN 201610578443 A CN201610578443 A CN 201610578443A CN 106186704 A CN106186704 A CN 106186704A
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energy storage
potassio
glass
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strontium barium
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CN106186704B (en
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王海涛
翟继卫
刘金花
沈波
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Tongji University
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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
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B19/00—Other methods of shaping glass
    • C03B19/02—Other methods of shaping glass by casting molten glass, e.g. injection moulding
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B32/00—Thermal after-treatment of glass products not provided for in groups C03B19/00, C03B25/00 - C03B31/00 or C03B37/00, e.g. crystallisation, eliminating gas inclusions or other impurities; Hot-pressing vitrified, non-porous, shaped glass products
    • C03B32/02—Thermal crystallisation, e.g. for crystallising glass bodies into glass-ceramic articles
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C1/00—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels

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Abstract

The present invention relates to a kind of strontium barium niobate potassio glass ceramics energy storage material and preparation method and application, described preparation method specifically includes following steps: with SrCO3、BaCO3、K2CO3、Nb2O5、SiO2For raw material, in molar ratio 25.6mol% [xSrCO3+(1‑x)BaCO3] 6.4mol%K2CO332mol%Nb2O536mol%SiO2Carrying out dispensing, wherein x span is 0.2 1；By dispensing after ball mill mixing, dry, and carry out high temperature melting, prepare high-temperature fusant；High-temperature fusant is poured in the metal die of preheating, stress relief annealing, prepares clear glass, and this clear glass is cut into glass flake；Glass flake carrying out Controlled Crystallization, i.e. prepares described strontium barium niobate potassio glass ceramics energy storage material, this strontium barium niobate potassio glass ceramics energy storage material is applied to energy-storage capacitor material.Compared with prior art, the glass ceramics energy storage material that the present invention is prepared by adding strontium in niobic acid barium potassium system not only has higher energy storage density (17.28J/cm3), the microstructure of more uniform densification, and there is the tangent value (0.006) of relatively low dielectric loss angle.

Description

A kind of strontium barium niobate potassio glass ceramics energy storage material and preparation method and application
Technical field
The invention belongs to dielectric energy storage material technical field, relate to a kind of strontium barium niobate potassio glass ceramics energy storage material And preparation method and application.
Background technology
Along with industrial expansion, energy demand is continuously increased, and in the face of energy crisis, improves energy utilization rate and develops 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 arise at the historic moment, its Middle high energy-storage capacitor is the most important, and it is conventional circuit components.For energy-storage capacitor, it have energy storage density high, The key properties such as charge/discharge rates is fast, utilization rate is high, stable performance.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.The energy storage density of current material, does not also occur substantially breaking through, and the volume of energy storage device is whole Occupying in pulser greatly, this constrains pulser the most significantly to miniaturization, the development of lightness.Therefore, mesh The requirement of front miniaturization and high energy storage density in order to meet pulse power system, various countries material supplier author is just trying to explore research There is high-k, the low dielectric material connecing electrical loss and high compressive resistance.
Glass ceramics is to use high-temperature fusion-method for quick cooling to prepare glass basis, then prepares through controlled crystallize method Become glass ceramics.Strontium barium niobate potassio glass ceramics has some obvious advantages, such as, preparation compared with traditional ceramics material Disruptive field intensity uncomplicated, resistance to is high, dielectric adjustable is strong, dielectric loss is low, in dielectric material field, have wide application before Scape.Strontium barium niobate potash glass pottery can form the co-melting body of strontium barium niobate and strontium potassium niobate, it is achieved 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, strontium barium niobate potassio glass ceramics is stored up Can have higher energy storage density by material.
The energy storage density of the energy storage material being presently used for capacitor, pulse technique etc. is 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 Can characteristic conduct extensive research.Wherein, D.F.Han et al. is by changing strontium lead ratio to niobates glass ceramics energy-storage property Being optimized, research finds, along with strontium lead ratio increases, dielectric constant first increases and then decreases, resistance to disruptive field intensity reduces always, phase The energy storage density first increases and then decreases of the glass ceramic material answered, when strontium lead ratio reach suitably than time, energy storage density reaches 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 sodio glass ceramics is 1.87J/cm3(J.Phys.:Conf.Ser., 2009,152:0212061).And Shuangxi Xue et al. have studied the impact of barium sodium comparison barium sodium niobate (BNN) base glass ceramic material energy-storage property, and research shows, When barium sodium ratio reaches proper ratio, energy storage density reaches maximum 5.12J/cm3(Shuangxi Xue,et Al.CeramicsInternational, 2014,40:7495-7499), and add rare earth to barium sodium niobate (BNN) base glass ceramics The impact of performance, wherein energy storage density maximum reaches 8.4J/cm3(Shuangxi Xue,et Al.CeramicsInternational, 2015,41:S441-S446).Guohua Chen et al. have studied barium strontium niobate sodium boron The energy storage density of silica glass is 4J/cm3(Journal of electronceramics,2011,27:78-82)。Shi Xiao Have studied crystallization behavior and the dielectric properties of strontium potassium niobate aluminosilicate glass ceramic material, they find, system is along with the increasing of temperature Adding, resistance to disruptive field intensity reduces, and dielectric constant first increases and reduces afterwards, and corresponding energy storage density first increases and reduces afterwards, maximum energy storage Density is 4.41J/cm3.So far, although dielectric energy storage material is conducted extensive research by people, but reported The energy storage density of glass ceramics energy storage material be also insufficient to greatly, and dielectric loss is insufficient to low.
The Chinese invention patent of Application No. 201610006156.X discloses the strontium barium niobate potassium of a kind of high energy storage density Base glass ceramics energy storage material and preparation method and application, this strontium barium niobate potassio glass ceramics energy storage material include SrO, Na2O、Nb2O5、SiO2Four kinds of compositions, and the mol ratio of four kinds of materials is SrO:Na2O:Nb2O5: SiO2=42x:42 (1-x): 28: 30, prepared by following steps: weigh raw material, after ball mill mixing, dry, and carry out high temperature melting, prepare high-temperature fusant；So After be poured in the metal die of preheating, stress relief annealing, prepare clear glass, cutting into thickness is 0.9～1.2mm Glass flake, carries out Controlled Crystallization, i.e. prepares product, and this product can be applicable to energy-storage capacitor material.Compared with above-mentioned patent, The present invention has a following difference: 1) raw material and proportioning are different；2) microstructure more even compact；3) at high energy storage density In the case of, dielectric constant improves nearly 2 times, and dielectric loss is substantially reduced.
Summary of the invention
Defect that the purpose of the present invention is contemplated to overcome above-mentioned prior art to exist and provide a kind of energy storage density higher, Dielectric loss is low, strontium barium niobate potassio glass ceramics energy storage material of dense micro-structure and preparation method and application.
The purpose of the present invention can be achieved through the following technical solutions:
A kind of preparation method of strontium barium niobate potassio glass ceramics energy storage material, the method specifically includes following steps:
(1) with SrCO3、BaCO3、K2CO3、Nb2O5、SiO2For raw material, in molar ratio 25.6mol% [xSrCO3+(1-x) BaCO3]-6.4mol%K2CO3-32mol%Nb2O5-36mol%SiO2Carrying out dispensing, wherein x span is 0.2-1；
(2) by the dispensing of step (1) after ball mill mixing, dry, and carry out high temperature melting, prepare high-temperature fusant；
(3) high-temperature fusant that step (2) prepares is poured in the metal die of preheating, stress relief annealing, prepares transparent Glass, and this clear glass is cut into glass flake；
(4) glass flake that step (3) prepares is carried out Controlled Crystallization, i.e. prepare described strontium barium niobate potassio glass pottery Porcelain energy storage material.
In step (1), the value of x is 0.2,0.4,0.6,0.8 or 1.
SrCO described in step (1)3、BaCO3、K2CO3、Nb2O5And SiO2Purity more than 99wt%.
The time of the ball mill mixing described in step (2) is 10-20h, and the temperature of described high temperature melting is 1500-1650 DEG C, the time of high temperature melting is 1.5-4h.
As preferred technical scheme, the time of the ball mill mixing described in step (2) is 12-16h, described high temperature melting Temperature be 1500-1600 DEG C, the time of high temperature melting is 2-3h.
The temperature of the stress relief annealing described in step (3) is 600-700 DEG C, and the time of described stress relief annealing is 4- 7h。
As preferred technical scheme, the temperature of the stress relief annealing described in step (3) is 600-680 DEG C, and described goes The time of stress annealing is 5h.
The thickness of the glass flake described in step (3) is 1.4-1.6mm.
The temperature of the Controlled Crystallization described in step (4) is 650-1100 DEG C, and temperature retention time is 2-5h.
As preferred technical scheme, the temperature of the Controlled Crystallization described in step (4) is 900-1100 DEG C, and temperature retention time is 2-4h。
Use the strontium barium niobate potassio glass ceramics energy storage material that said method is prepared from.
The application of strontium barium niobate potassio glass ceramics energy storage material, described strontium barium niobate potassio glass ceramics energy storage material It is applied to energy-storage capacitor material.
In the present invention, described glass ceramics energy storage material is mainly made up of amorphous glass phase and ceramic phase, ceramic phase master Blue copper phase SrNbO to be6, Sr0.5Ba0.5Nb6, SrBaKNb5O15Deng, 25.6mol% [xSrCO in molar ratio3+(1-x) BaCO3]-6.4mol%K2CO3-32mol%Nb2O5-36mol%SiO2Carry out dispensing, wherein x=0.2～1.Through ball mill mixing, Dry, then carry out high temperature melting reaction, and by molding in high-temperature fusant Quick pouring to metal die, stress relief annealing subsequently, Cut into glass flake, then Controlled Crystallization, i.e. prepare described strontium barium niobate potassio glass ceramics energy storage material.
The present invention is based on 25.6mol% [xSrCO3+(1-x)BaCO3]-6.4mol%K2CO3-32mol%Nb2O5- 36mol%SiO2Dispensing, wherein x=0.2～1；By adjusting SrCO3And BaCO3After mole the most different heat treatment temperature Glass ceramics, phase structure is improved, and resistance to disruptive field intensity significantly improves, and as x=0.4, recrystallization temperature is 900 DEG C, resistance to Disruptive field intensity reaches optimal value 1883kV/cm, and theoretical energy storage density reaches 17.28J/cm3, the dielectric loss under room temperature is reduced to 0.6%.
Compared with prior art, the invention have the characteristics that:
1) by changing ceramic component proportioning, improve resistance to disruptive field intensity, institute so that its energy storage density is improved significantly, Dielectric loss substantially reduces；
2) system is simple, and preparation method is simple, it is not necessary to complicated post-processing step, economical and practical, (Sr/Ba, the K) prepared NbO3Base glass ceramics energy storage material has superior dielectric performance, and the energy storage characteristic of material is significantly improved.
Accompanying drawing explanation
Fig. 1 is the X-ray diffraction analysis figure (XRD) of embodiment 1-5 strontium barium niobate potassio glass ceramic material；
Fig. 2 is the X-ray diffraction analysis figure (XRD) of embodiment 6-8 strontium barium niobate potassio glass ceramic material；
Fig. 3 is dielectric temperature spectrum and the dielectric loss figure of embodiment 1-5 strontium barium niobate potassio glass ceramic material；
Fig. 4 is dielectric temperature spectrum and the dielectric loss figure of embodiment 6-8 strontium barium niobate potassio glass ceramic material；
Fig. 5 is the Weibull scattergram of the resistance to disruptive field intensity of embodiment 1-5 strontium barium niobate potassio glass ceramic material；
Fig. 6 is the Weibull scattergram of the resistance to disruptive field intensity of embodiment 6-8 strontium barium niobate potassio glass ceramic material；
Fig. 7-1 is the scanning electron microscope diagram spectrum of embodiment 1 strontium barium niobate potassio glass ceramic material；
Fig. 7-2 is the scanning electron microscope diagram spectrum of embodiment 2 strontium barium niobate potassio glass ceramic material；
Fig. 7-3 is the scanning electron microscope diagram spectrum of embodiment 3 strontium barium niobate potassio glass ceramic material；
Fig. 7-4 is the scanning electron microscope diagram spectrum of embodiment 4 strontium barium niobate potassio glass ceramic material；
Fig. 7-5 is the scanning electron microscope diagram spectrum of embodiment 5 strontium barium niobate potassio glass ceramic material；
Fig. 7-6 is the scanning electron microscope diagram spectrum of embodiment 6 strontium barium niobate potassio glass ceramic material；
Fig. 7-7 is the scanning electron microscope diagram spectrum of embodiment 7 strontium barium niobate potassio glass ceramic material；
Fig. 7-8 is the scanning electron microscope diagram spectrum of embodiment 8 strontium barium niobate potassio glass ceramic material；
Wherein, in Fig. 5 and Fig. 6, εrFor dielectric constant, tan δ is dielectric loss, EiResistance to for i-th test sample punctures Field intensity, n is the summation of resistance to breakdown field intensity values, EbFor being distributed the resistance to disruptive field intensity obtained by Weibull.
Detailed description of the invention
The present invention is described in detail with specific embodiment below in conjunction with the accompanying drawings.
The abbreviation used throughout the specification has following implication, unless clearly indicated otherwise in literary composition: DEG C=Celsius Degree, kV=kilovolt, cm=centimetre；Mol=mole, h=hour；Min=minute, mol%=molar percentage.Various raw materials It is purchased from commercial supplier, without being further purified, except as otherwise noted with reagent.Raw material and the reagent of moisture-sensitive are all deposited in In hermetically sealed bottle, and directly use, all without special handling.
Embodiment 1:
(1) SrCO of 99wt% it is more than 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, dry, high at 1500 DEG C Temperature fusing 2h；
(2) high-temperature fusant that step (1) obtains is poured in metal die, 600 DEG C of temperature stress relief annealings 6h, so The glass flake that thickness is 0.9～1.5mm is obtained by cutting；
(3) glass flake step (2) prepared carries out Controlled Crystallization at 900 DEG C of insulation 3h, obtains glass ceramics.
The XRD of the sample obtained by the present embodiment is as it is shown in figure 1, dielectric properties are as it is shown on figure 3, pressure performance test is as schemed Shown in 5, microscopic appearance is as shown in Fig. 7-1, and energy storage density is as shown in table 1.
Embodiment 2:
(1) SrCO of 99wt% it is more than 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, dry, at 1500 DEG C High temperature melting 2h；
(2) high-temperature fusant that step (1) obtains is poured in metal die, 600 DEG C of temperature stress relief annealings 6h, so The glass flake that thickness is 0.9～1.5mm is obtained by cutting；
(3) glass flake step (2) prepared carries out Controlled Crystallization at 900 DEG C of insulation 3h, obtains glass ceramics.
The XRD of the sample obtained by the present embodiment is as it is shown in figure 1, dielectric properties are as it is shown on figure 3, pressure performance test is as schemed Shown in 5, microscopic appearance is as shown in Fig. 7-2, and energy storage density is as shown in table 1, and its value is 17.28J/cm3, can be as energy-storage capacitor Material.
Embodiment 3:
(1) SrCO of 99wt% it is more than 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, dry, at 1500 DEG C High temperature melting 2h；
(2) high-temperature fusant that step (1) obtains is poured in metal die, 600 DEG C of temperature stress relief annealings 6h, so The glass flake that thickness is 0.9～1.5mm is obtained by cutting；
(3) glass flake step (2) prepared carries out Controlled Crystallization at 900 DEG C of insulation 3h, obtains glass ceramics.
The XRD of the sample obtained by the present embodiment is as it is shown in figure 1, dielectric properties are as it is shown on figure 3, pressure performance test is as schemed Shown in 5, microscopic appearance is as shown in Fig. 7-3, and energy storage density is as shown in table 1, and its value is 15.99J/cm3, can be used as energy-storage capacitor Material.
Embodiment 4:
(1) SrCO of 99wt% it is more than 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, dry, high at 1500 DEG C Temperature fusing 2h；
(2) by step 1) high-temperature fusant that obtains is poured in metal die, 600 DEG C of temperature stress relief annealings 6h, so The glass flake that thickness is 0.9～1.5mm is obtained by cutting；
(3) glass flake step (2) prepared carries out Controlled Crystallization at 900 DEG C of insulation 3h, obtains glass ceramics.
The XRD of the sample obtained by the present embodiment is as it is shown in figure 1, dielectric properties are as it is shown on figure 3, pressure performance test is as schemed Shown in 5, microscopic appearance is as shown in Fig. 7-4, and energy storage density is as shown in table 1.
Embodiment 5:
(1) SrCO of 99wt% it is more than 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, dry, 1500 DEG C of high temperature melting 2h；
(2) by step 1) high-temperature fusant that obtains is poured in metal die, 600 DEG C of temperature stress relief annealings 6h, so The glass flake that thickness is 0.9～1.5mm is obtained by cutting；
(3) glass flake step (2) prepared carries out Controlled Crystallization at 900 DEG C of insulation 3h, obtains glass ceramics.
The XRD of the sample obtained by the present embodiment is as it is shown in figure 1, dielectric properties are as it is shown on figure 3, pressure performance test is as schemed Shown in 5, microscopic appearance is as shown in Fig. 7-5, and energy storage density is as shown in table 1.
Embodiment 6:
Identical with embodiment 2 step (1) and (2), except for the difference that step (3) Controlled Crystallization temperature is 800 DEG C.
The XRD of the sample obtained by the present embodiment as in figure 2 it is shown, dielectric properties as shown in Figure 4, pressure performance test such as figure Shown in 6, microscopic appearance is as shown in Fig. 7-6, and energy storage density is as shown in table 1.
Embodiment 7:
Identical with embodiment 2 step, repeat this process just to carrying out contrasting here.Sample obtained by the present embodiment The XRD of product as in figure 2 it is shown, dielectric properties as shown in Figure 4, pressure performance test as shown in Figure 6, microscopic appearance as shown in Fig. 7-7, Energy storage density is as shown in table 1
Embodiment 8:
Identical with embodiment 2 step (1) and (2), except for the difference that step (3) Controlled Crystallization temperature is 1000 DEG C.
The XRD of the sample obtained by the present embodiment as in figure 2 it is shown, dielectric properties as shown in Figure 4, pressure performance test such as figure Shown in 6, as Figure 7-8, energy storage density is as shown in table 1 for microscopic appearance.
Table 1
From case study on implementation above, the present invention has prepared the strontium barium niobate potassio glass ceramics energy storage material of high energy storage density Material, relatively, and dielectric loss is relatively low for its energy storage density, and therefore, the material of this system is used as energy-storage capacitor material.
Embodiment 9:
The preparation method of the present embodiment strontium barium niobate potassio glass ceramics energy storage material, specifically includes following steps:
(1) with SrCO3、BaCO3、K2CO3、Nb2O5、SiO2For raw material, in molar ratio 25.6mol% [0.3SrCO3+ 0.7BaCO3]-6.4mol%K2CO3-32mol%Nb2O5-36mol%SiO2Carry out dispensing；
(2) by the dispensing of step (1) after ball mill mixing, dry, and carry out high temperature melting, prepare high-temperature fusant；
(3) high-temperature fusant that step (2) prepares is poured in the metal die of preheating, stress relief annealing, prepares transparent Glass, and this clear glass is cut into the glass flake that thickness is 1.4mm；
(4) glass flake that step (3) prepares is carried out Controlled Crystallization, i.e. prepare described strontium barium niobate potassio glass pottery Porcelain energy storage material.
SrCO described in step (1)3、BaCO3、K2CO3、Nb2O5And SiO2Purity more than 99wt%.
In step (2), the 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, and temperature retention time is 5h.
The strontium barium niobate potassio glass ceramics energy storage material that the present embodiment prepares is applied to energy-storage capacitor material.
Embodiment 10:
The preparation method of the present embodiment strontium barium niobate potassio glass ceramics energy storage material, specifically includes following steps:
(1) with SrCO3、BaCO3、K2CO3、Nb2O5、SiO2For raw material, in molar ratio 25.6mol% [0.2SrCO3+ 0.8BaCO3]-6.4mol%K2CO3-32mol%Nb2O5-36mol%SiO2Carry out dispensing；
(2) by the dispensing of step (1) after ball mill mixing, dry, and carry out high temperature melting, prepare high-temperature fusant；
(3) high-temperature fusant that step (2) prepares is poured in the metal die of preheating, stress relief annealing, prepares transparent Glass, and this clear glass is cut into the glass flake that thickness is 1.5mm；
(4) glass flake that step (3) prepares is carried out Controlled Crystallization, i.e. prepare described strontium barium niobate potassio glass pottery Porcelain energy storage material.
SrCO described in step (1)3、BaCO3、K2CO3、Nb2O5And SiO2Purity more than 99wt%.
In step (2), the 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, and temperature retention time is 4h.
The strontium barium niobate potassio glass ceramics energy storage material that the present embodiment prepares is applied to energy-storage capacitor material.
Embodiment 11:
The preparation method of the present embodiment strontium barium niobate potassio glass ceramics energy storage material, specifically includes following steps:
(1) with SrCO3、BaCO3、K2CO3、Nb2O5、SiO2For raw material, in molar ratio 25.6mol% [0.4SrCO3+ 0.6BaCO3]-6.4mol%K2CO3-32mol%Nb2O5-36mol%SiO2Carry out dispensing；
(2) by the dispensing of step (1) after ball mill mixing, dry, and carry out high temperature melting, prepare high-temperature fusant；
(3) high-temperature fusant that step (2) prepares is poured in the metal die of preheating, stress relief annealing, prepares transparent Glass, and this clear glass is cut into the glass flake that thickness is 1.6mm；
(4) glass flake that step (3) prepares is carried out Controlled Crystallization, i.e. prepare described strontium barium niobate potassio glass pottery Porcelain energy storage material.
SrCO described in step (1)3、BaCO3、K2CO3、Nb2O5And SiO2Purity more than 99wt%.
In step (2), the 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, and temperature retention time is 3h.
The strontium barium niobate potassio glass ceramics energy storage material that the present embodiment prepares is applied to energy-storage capacitor material.
Embodiment 12:
The preparation method of the present embodiment strontium barium niobate potassio glass ceramics energy storage material, specifically includes following steps:
(1) with SrCO3、BaCO3、K2CO3、Nb2O5、SiO2For raw material, in molar ratio 25.6mol% [0.6SrCO3+ 0.4BaCO3]-6.4mol%K2CO3-32mol%Nb2O5-36mol%SiO2Carry out dispensing；
(2) by the dispensing of step (1) after ball mill mixing, dry, and carry out high temperature melting, prepare high-temperature fusant；
(3) high-temperature fusant that step (2) prepares is poured in the metal die of preheating, stress relief annealing, prepares transparent Glass, and this clear glass is cut into the glass flake that thickness is 1.5mm；
(4) glass flake that step (3) prepares is carried out Controlled Crystallization, i.e. prepare described strontium barium niobate potassio glass pottery Porcelain energy storage material.
SrCO described in step (1)3、BaCO3、K2CO3、Nb2O5And SiO2Purity more than 99wt%.
In step (2), the 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, and temperature retention time is 2h.
The strontium barium niobate potassio glass ceramics energy storage material that the present embodiment prepares is applied to energy-storage capacitor material.
Embodiment 13:
The preparation method of the present embodiment strontium barium niobate potassio glass ceramics energy storage material, specifically includes following steps:
(1) with SrCO3、BaCO3、K2CO3、Nb2O5、SiO2For raw material, in molar ratio 25.6mol% [0.8SrCO3+ 0.2BaCO3]-6.4mol%K2CO3-32mol%Nb2O5-36mol%SiO2Carry out dispensing；
(2) by the dispensing of step (1) after ball mill mixing, dry, and carry out high temperature melting, prepare high-temperature fusant；
(3) high-temperature fusant that step (2) prepares is poured in the metal die of preheating, stress relief annealing, prepares transparent Glass, and this clear glass is cut into the glass flake that thickness is 1.5mm；
(4) glass flake that step (3) prepares is carried out Controlled Crystallization, i.e. prepare described strontium barium niobate potassio glass pottery Porcelain energy storage material.
SrCO described in step (1)3、BaCO3、K2CO3、Nb2O5And SiO2Purity more than 99wt%.
In step (2), the 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, and temperature retention time is 5h.
The strontium barium niobate potassio glass ceramics energy storage material that the present embodiment prepares is applied to energy-storage capacitor material.
Embodiment 14:
The preparation method of the present embodiment strontium barium niobate potassio glass ceramics energy storage material, specifically includes following steps:
(1) with SrCO3、BaCO3、K2CO3、Nb2O5、SiO2For raw material, in molar ratio 25.6mol%SrCO3-6.4mol% K2CO3-32mol%Nb2O5-36mol%SiO2Carry out dispensing；
(2) by the dispensing of step (1) after ball mill mixing, dry, and carry out high temperature melting, prepare high-temperature fusant；
(3) high-temperature fusant that step (2) prepares is poured in the metal die of preheating, stress relief annealing, prepares transparent Glass, and this clear glass is cut into the glass flake that thickness is 1.5mm；
(4) glass flake that step (3) prepares is carried out Controlled Crystallization, i.e. prepare described strontium barium niobate potassio glass pottery Porcelain energy storage material.
SrCO described in step (1)3、BaCO3、K2CO3、Nb2O5And SiO2Purity more than 99wt%.
In step (2), the 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, and temperature retention time is 4h.
The strontium barium niobate potassio glass ceramics energy storage material that the present embodiment prepares is applied to energy-storage capacitor material.
The above-mentioned description to embodiment is to be understood that for ease of those skilled in the art and use invention. These embodiments obviously easily can be made various amendment by person skilled in the art, and described herein typically Principle is applied in other embodiments without through performing creative labour.Therefore, the invention is not restricted to above-described embodiment, ability Field technique personnel should be the present invention's according to the announcement of the present invention, the improvement made without departing from scope and amendment Within protection domain.

Claims (8)

1. the preparation method of a strontium barium niobate potassio glass ceramics energy storage material, it is characterised in that the method specifically include with Lower step:
(1) with SrCO3、BaCO3、K2CO3、Nb2O5、SiO2For raw material, in molar ratio 25.6mol% [xSrCO3+(1-x) BaCO3]-6.4mol%K2CO3-32mol%Nb2O5-36mol%SiO2Carrying out dispensing, wherein x span is 0.2-1；
(2) by the dispensing of step (1) after ball mill mixing, dry, and carry out high temperature melting, prepare high-temperature fusant；
(3) high-temperature fusant that step (2) prepares is poured in the metal die of preheating, stress relief annealing, prepares clear glass, And this clear glass is cut into glass flake；
(4) glass flake that step (3) prepares is carried out Controlled Crystallization, i.e. prepare described strontium barium niobate potassio glass ceramics storage Can material.
The preparation method of a kind of strontium barium niobate potassio glass ceramics energy storage material the most according to claim 1, its feature exists In, in step (1), the value of x is 0.2,0.4,0.6,0.8 or 1.
The preparation method of a kind of strontium barium niobate potassio glass ceramics energy storage material the most according to claim 1, its feature exists In, the SrCO described in step (1)3、BaCO3、K2CO3、Nb2O5And SiO2Purity more than 99wt%.
The preparation method of a kind of strontium barium niobate potassio glass ceramics energy storage material the most according to claim 1, its feature exists In, the time of the ball mill mixing described in step (2) is 10-20h, and the temperature of described high temperature melting is 1500-1650 DEG C, high temperature The time of fusing is 1.5-4h.
The preparation method of a kind of strontium barium niobate potassio glass ceramics energy storage material the most according to claim 1, its feature exists In, the temperature of the stress relief annealing described in step (3) is 600-700 DEG C, and the time of described stress relief annealing is 4-7h.
The preparation method of a kind of strontium barium niobate potassio glass ceramics energy storage material the most according to claim 1, its feature exists In, the temperature of the Controlled Crystallization described in step (4) is 650-1100 DEG C, and temperature retention time is 2-5h.
7. use the strontium barium niobate potassio glass ceramics energy storage material that the method described in any one of claim 1 to 6 is prepared from.
8. the application of strontium barium niobate potassio glass ceramics energy storage material as claimed in claim 7, it is characterised in that described niobium Acid strontium barium potassio glass ceramics energy storage material is applied to energy-storage capacitor material.
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CN105753472A (en) * 2016-01-26 2016-07-13 同济大学 High-energy-storage-density barium potassium niobate based glass ceramic energy storage material and preparation as well as application

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CN105753472A (en) * 2016-01-26 2016-07-13 同济大学 High-energy-storage-density barium potassium niobate based glass ceramic energy storage material and preparation as well as application

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CN112390535A (en) * 2020-11-18 2021-02-23 同济大学 Ta with low dielectric loss2O5Niobate-doped glass ceramic material and preparation method and application thereof
CN112390535B (en) * 2020-11-18 2021-12-31 同济大学 Ta with low dielectric loss2O5Niobate-doped glass ceramic material and preparation method and application thereof

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