CN105541115B - A kind of metatitanic acid niobic acid composite glass-ceramic and its preparation method and application - Google Patents
A kind of metatitanic acid niobic acid composite glass-ceramic and its preparation method and application Download PDFInfo
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- C—CHEMISTRY; METALLURGY
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- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C10/00—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition
- C03C10/0036—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition containing SiO2, Al2O3 and a divalent metal oxide as main constituents
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- 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
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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
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- C03C3/062—Glass compositions containing silica with less than 40% silica by weight
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Abstract
The present invention relates to a kind of metatitanic acid niobic acid composite glass-ceramic and its preparation method and application, which is Sr0.5Ba0.5Nb2O6、Ba0.27Sr0.75Nb2O5.7And Sr6Ti2Nb4O20, glass phase SiO2, chemical formula 8Al2O3·32SiO2·20BaO·20SrO·xTiO2·(20‑x)Nb2O5, wherein x=5~15；Preparation process uses two step crystallizations, which can apply in terms of energy-storage capacitor material.Compared with prior art, metatitanic acid niobic acid composite glass-ceramic of the invention has many advantages, such as that resistance to breakdown field intensity values are big, energy storage density is big.
Description
Technical field
The invention belongs to field of dielectric energy storage material, and in particular to a kind of metatitanic acid niobic acid composite glass-ceramic and its preparation
Methods and applications.
Background technique
Glass ceramics, is called devitrified glass, and the characteristic of devitrified glass zero air void rate has glass ceramics much higher than sintering
The dielectric breakdown strength of ceramics, so glass ceramics will show better adaptability when applying under high direct voltage.Therefore,
Glass ceramics has not only assembled the high breakdown fields powerful feature of glass, is also provided with the high dielectric constant performance of dielectric ceramic system,
The advantages of in view of the two aspects, glass ceramics has also obtained the concern of more and more people, therefore, also becomes high storage in recent years
Hot spot (Science, 2006,313 (5785): 334-336 of energy investigation of materials；Physica B, 2007,396 (1-2): 62-
69).The high-compactness of the material, zero porosity make devitrified glass become current people's research high energy storage density ceramic condenser
The preferred material of device and High pulse power technology.
The energy storage density of glass ceramic material and the dielectric coefficient of medium are directly proportional, with the resistance to disruptive field intensity of highest of medium
It is square directly proportional.Therefore, the energy storage density of capacitor is improved, can be started with from the resistance to disruptive field intensity for improving dielectric coefficient and material.
Currently, there is no the media for being provided simultaneously with high-dielectric coefficient and Gao Nai disruptive field intensity in various dielectric substances, it can only be from this
A more appropriate compromise is chosen in the two, it is also contemplated that material is compound.
Currently, the glass ceramics of people's research mainly has metatitanic acid alkali glass ceramics and niobate glass ceramics.Wherein,
Herczog of Corning Incorporated et al. (Trans.on Parts Hybrids Package, Vol.9, No.14, pp.247-
256,1973；Journal of the American Ceramic Society,vol.67,no.7,pp.484–490,1984)
It is successfully prepared for the devitrified glass using barium titanate as principal crystalline phase earliest.The glass ceramics of metatitanic acid alkali is the earliest dielectric of research
Glass ceramics.The ceramic phase being precipitated in metatitanic acid alkali is relatively simple for structure, is a kind of ferroelectric most widely used at present.Titanate
Glass ceramics since the offset meeting of Ti ion is so that spontaneous polarization can occur for such material, such material is with higher
Dielectric constant, while metatitanic acid alkali glass ceramics has a fatal weakness, Ti vacancy easy to form when being exactly melting annealing, this is very
It is easy to cause leakage current larger (Assemblies&Materials Association, 1997,255-260), therefore, improves glass
The energy storage density of glass ceramic material, improving dielectric constant is only one of the necessary condition for realizing raising system energy storage density, is mentioned
The resistance to disruptive field intensity of high glass ceramic material is also the necessary condition of a raising system energy storage density.Consider linear medium material
Material, energy storage density is directly proportional to dielectric constant, and square directly proportional to resistance to disruptive field intensity, this means that the resistance to of raising system hits
The energy storage density that field strength is more advantageous to raising system is worn, therefore, during selecting raising system energy storage density, can preferentially be examined
Consider the resistance to disruptive field intensity for improving glass ceramic material.For barium strontium titanate niobate composite glass-ceramic system, differential thermal analysis curve is shown
Barium strontium titanate niobate composite glass-ceramic system has apparent nucleation temperature, in order to enable uniformly analysing in the glass idiosome of preparation
Ceramic crystal phase out, then just needs accurately to determine the best nucleation temperature of the glass ceramics system, about nucleation temperature
Research before determination is seldom (devitrified glass, P.W. William McMillan, p115).
Chinese patent CN101531461B discloses a kind of dielectric material of glass-ceramics with high energy storage density and its preparation side
Method.The main component of dielectric material of glass-ceramics is BaO, SrO, TiO2、SiO2And Al2O3, composition doping AlF3And MnO2,
Adulterate AlF3Molal quantity account for the 2~8% of component total mole number, adulterate MnO2Molal quantity account for component total mole number 0.1~
1%.By igneous fusion after raw material ball milling, glass flake is prepared, carries out Controlled Crystallization, obtained ferroelectric glass-ceramic dielectric applies
Silver paste is covered, sintering curing forms metal silver electrode, and glass-ceramics with high energy storage density dielectric is made.The glass provided in the patent
Nb is not included in glass ceramic material2O5, contain only TiO2, Ti ion is readily formed the vacancy Ti when forming crystal phase, leads to glass
Ceramic material leakage electrical conduction current easy to form under high field intensity.
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 resistance to breakdown field intensity values
Greatly, the big metatitanic acid niobic acid composite glass-ceramic of energy storage density and two step crystallization methods of use prepare the method and the glass of the glass ceramics
Application of the glass ceramics in terms of energy-storage capacitor material.
The purpose of the present invention can be achieved through the following technical solutions:
A kind of metatitanic acid niobic acid composite glass-ceramic, the glass ceramics principal crystalline phase are Sr0.5Ba0.5Nb2O6、
Ba0.27Sr0.75Nb2O5.7And Sr6Ti2Nb4O20, glass phase SiO2, chemical formula 8Al2O3·32SiO2·20BaO·
20SrO·xTiO2·(20-x)Nb2O5, wherein x=5~15.
The x=10.
A kind of preparation method of metatitanic acid niobic acid composite glass-ceramic, method includes the following steps:
(1) Al is weighed2O3、SiO2、BaCO3、SrCO3、TiO2And Nb2O5According to molar ratio Al2O3:SiO2:BaCO3:
SrCO3:TiO2:Nb2O5=8:32:20:20:x:(20-x) it carries out ingredient and is uniformly mixed, high-temperature fusion is made in high temperature melting
Body；
(2) high temperature melting melt body is poured into the metal die of preheating, and carries out stress relief annealing, transparent glass is made,
And it is cut into glass flake；
(3) glass flake is first kept the temperature into 1~3h under 770~830 DEG C of nucleation temperature, then with the liter of 1~3 DEG C/min
Warm rate is warming up to 930~970 DEG C of crystallization temperature, and keeps the temperature 2~4h and carry out Controlled Crystallization to get metatitanic acid niobic acid compound glass is arrived
Glass ceramics.
The Al2O3、SiO2、BaCO3、SrCO3、TiO2And Nb2O5Purity be all larger than 99%.
Mixing in step (1) is used the method through ball mill mixing and drying after ingredient addition alcohol, ball mill mixing
Time is 10~20h；The temperature of high temperature melt is 1500~1650 DEG C, and the high temperature melt time is 2~4h；
Preferably, the time of the ball mill mixing in step (1) is 12~16h, and the temperature of high temperature melt is 1500~1600
DEG C, the high temperature melt time is 2~3h.
Stress relief annealing temperature in step (2) is 550~700 DEG C, and the stress relief annealing time is 4~7h；Glass flake
With a thickness of 0.9~1.2mm.
Stress relief annealing temperature in step (2) is 600~680 DEG C, and the stress relief annealing time is 5h.
In step (3) by glass flake first 800 DEG C at a temperature of keep the temperature 2h, protected at a temperature of then heating to 950 DEG C
Warm 3h carries out Controlled Crystallization.
Heating rate in the step (3) is 2 DEG C/min.Heating rate is too fast to be will lead in temperature-rise period on sample
There are the temperature difference, cause in sample Crystallization Process that uneven heating is even to be caused to be broken；On the contrary, will lead to if heating rate is excessively slow
Nucleus through being formed, which will appear, non-uniform grow up or the miscellaneous of some undesirable appearance occurs.
A kind of application of metatitanic acid niobic acid composite glass-ceramic in terms of energy-storage capacitor material.
The present invention is by Al2O3、SiO2、BaCO3、SrCO3、TiO2And Nb2O5According to molar ratio 8:32:20:20:x:(20-x)
Ingredient is carried out, using two step crystallization methods (crystallization under present nucleation temperature, then in crystallization after determining optimal nucleation temperature
At a temperature of crystallization) to metatitanic acid niobic acid composite glass-ceramic system carry out Controlled Crystallization, the heat treatment method can for improve glass pottery
The pressure voltage of ceramic material provides a kind of effective scheme.Different nucleation temperatures (770 DEG C, 800 are selected with differential thermal analysis curve
DEG C, 830 DEG C) optimize, different nucleation temperatures choose crystallization temperature be 950 DEG C, when T=800 DEG C of crystallization of nucleation temperature
At T=950 DEG C of temperature, resistance to disruptive field intensity is optimal value 1817kV/cm, is obtained under a step crystallization (not considering nucleation temperature)
1.88 times of resistance to breakdown field intensity values 963kV/cm of glass ceramic material, the energy storage density for the glass ceramics that two step crystallizations obtain
Value is 2.9 times of the glass ceramic material that a step crystallization obtains.
The addition of Nb2O5 can significantly improve the resistance to disruptive field intensity of glass ceramic material in the present invention, increase glass ceramics
The compactness of microstructure, and Nb2O5Addition can substantially improve leakage electrical conduction current generation.
One step crystallization method is not consider nucleation temperature, is directly warming up to crystallization temperature, which does not account for being nucleated
Temperature is not just warming up to crystallization temperature to the enough nucleation times of sample, and the nucleus quantity that will lead to generation in this way is few, and meeting
It is uneven to there is nucleus size, it is uneven that the crystal after crystallization just will appear grain size, seriously affects glass ceramic material
Resistance to disruptive field intensity.
The first step is nucleation in two step crystallization methods, and second step is crystallization, keeps the temperature 2h under nucleation temperature, it can be ensured that glass
Ceramic material can grow enough fine and compact nucleus, then, be warming up to crystallization temperature heat preservation 3h, can make
These nucleus can grow up to the crystal grain of even compact.Therefore, two step crystallizations can greatly improve the energy storage of glass ceramic material
Density.
Compared with prior art, the invention has the following advantages that
(1) nucleation temperature is first determined by differential thermal analysis curve, carries out two steps further according to the specific value of nucleation temperature
Crystallization, the method for determination of nucleation temperature is as follows here: first, best crystallization temperature is read, we are according on differential thermal curve here
(950 DEG C) of the corresponding temperature of highest exothermic peak are used as crystallization temperature.Second, different nucleation temperatures is chosen respectively (to be distinguished here
Choose 770 DEG C, 800 DEG C, 830 DEG C), identical crystallization temperature (950 DEG C) study their energy storage density value respectively.As a result table
Bright, nucleation temperature is 800 DEG C, and crystallization temperature is 950 DEG C of energy storage density highest, therefore, select 800 DEG C as nucleation temperature.
By comparing, the resistance to disruptive field intensity for the glass ceramic material that two step crystallization methods obtain is the glass ceramic material that a step crystallization obtains
1.88 times.Its energy storage density is 2.9 times of the glass ceramic material that a step crystallization method obtains；
(2) this method can simply, accurately determine the nucleation temperature of metatitanic acid niobic acid composite glass-ceramic energy storage material, into
And improve the glass ceramics system Controlled Crystallization degree.
Detailed description of the invention
Fig. 1 is that chemical formula is 8Al2O3·32SiO2·20BaO·20SrO·10TiO2·10Nb2O5Metatitanic acid niobic acid it is multiple
Close the differential thermal analysis curve of glass ceramics；
Fig. 2 is the Controlled Crystallization figure of the metatitanic acid niobic acid composite glass-ceramic of embodiment 2；
Fig. 3 is the dielectric temperature spectrum and dielectric loss figure of the metatitanic acid niobic acid composite glass-ceramic of Examples 1 to 3 and comparative example 1；
Fig. 4 is Weibull points of the resistance to disruptive field intensity of the metatitanic acid niobic acid composite glass-ceramic of Examples 1 to 3 and comparative example 1
Butut；
In figure, εrFor dielectric constant, tan δ is dielectric loss, EiFor the resistance to disruptive field intensity of i-th of test sample, n is resistance to hits
Wear the summation of field intensity value, EbFor the resistance to disruptive field intensity being distributed by Weibull, exdhermic is heat release,
Endothermic heat absorption.
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.
The preparation of the metatitanic acid niobic acid composite glass-ceramic of Examples 1 to 3 and comparative example 1 is taken from purity greater than 99wt%
BaCO3、SrCO3、Nb2O5、TiO2、SiO2And Al2O3For feed proportioning, the molar percentage of above-mentioned each component is respectively 20%,
20%, 10%, 10%, 32% and 8%, after ball mill mixing 16h, drying forms high-temperature fusion in 1500 DEG C of high temperature melting 2h
Body, in 600 DEG C of temperature stress relief annealing 6h, then obtains then melt cast into copper mold through cutting with a thickness of 0.9
Then the glass flake of~1.2mm carries out the preparation of the metatitanic acid niobic acid composite glass-ceramic of Examples 1 to 3 and comparative example 1.
Embodiment 1
Prior glass flake obtained is kept into constant temperature 2h in 770 DEG C of Crystallization Furnace, then with the heating speed of 2 DEG C/min
Rate is warming up to 950 DEG C, and carries out Controlled Crystallization in 950 DEG C of heat preservation 3h, obtains the 8Al of the present embodiment2O3·32SiO2·
20BaO·20SrO·10TiO2·10Nb2O5Metatitanic acid niobic acid composite glass-ceramic.
The selection of the present embodiment nucleation temperature and crystallization temperature is chosen all in accordance with Fig. 1.The dielectric properties of obtained sample
As shown in Fig. 3 (embodiment 1), shown in pressure-resistant performance test such as Fig. 4 (embodiment 1), resistance to disruptive field intensity and theoretical energy storage density
Value is as shown in table 1.
Embodiment 2
Prior glass flake obtained is kept constant temperature 2 hours in 800 DEG C of Crystallization Furnace, then with the liter of 2 DEG C/min
Warm rate is warming up to 950 DEG C, and carries out Controlled Crystallization in 950 DEG C of heat preservation 3h, obtains the 8Al of the present embodiment2O3·32SiO2·
20BaO·20SrO·10TiO2·10Nb2O5Metatitanic acid niobic acid composite glass-ceramic.
The selection of the present embodiment nucleation temperature and crystallization temperature is chosen all in accordance with Fig. 1.The dielectric properties of obtained sample
As shown in Fig. 3 (embodiment 2), shown in pressure-resistant performance test such as Fig. 4 (embodiment 2), resistance to disruptive field intensity and theoretical energy storage density
Value is as shown in table 1.
Embodiment 3
Prior glass flake obtained is kept constant temperature 2 hours in 830 DEG C of Crystallization Furnace, then with the liter of 2 DEG C/min
Warm rate is warming up to 950 DEG C, and carries out Controlled Crystallization in 950 DEG C of heat preservation 3h, obtains the 8Al of the present embodiment2O3·32SiO2·
20BaO·20SrO·10TiO2·10Nb2O5Metatitanic acid niobic acid composite glass-ceramic.
The selection of the present embodiment nucleation temperature and crystallization temperature is chosen all in accordance with Fig. 1.The dielectric properties of obtained sample
As shown in Fig. 3 (embodiment 3), shown in pressure-resistant performance test such as Fig. 4 (embodiment 3), resistance to disruptive field intensity and theoretical energy storage density
Value is as shown in table 1.
Comparative example 1
In advance glass flake obtained Controlled Crystallization directly will be carried out in 950 DEG C of heat preservation 3h, will be obtained without nucleation temperature
The 8Al of one step crystallization2O3·32SiO2·20BaO·20SrO·10TiO2·10Nb2O5Metatitanic acid niobic acid composite glass-ceramic material
Material.
Shown in the dielectric properties of sample obtained by the present embodiment such as Fig. 3 (comparative example 1), pressure-resistant performance test such as Fig. 4 is (right
Ratio 1) shown in, the value of resistance to disruptive field intensity and theoretical energy storage density is as shown in table 1.
Table 1
From case study on implementation above, we illustrate the methods of the pressure voltage of a raising glass ceramics, while can also have
The surface topography of the improvement glass ceramic material of effect.Resistance to breakdown field intensity values not only can be improved in this two steps Crystallization method can be with
Substantially improve the microscopic appearance of glass ceramic material.In Fig. 3 Examples 1 to 3 be set forth 770 DEG C, 800 DEG C of nucleation temperature and
830 DEG C and 950 DEG C of crystallization temperature of dielectric constant and dielectric loss value, as seen from Figure 3 different nucleation temperature, phase
The dielectric constant values that same crystallization temperature obtains are not much different (about 57), and dielectric loss is also not much different (less than 2%)；In Fig. 3,
What comparative example 1 provided is the value (about 65) of the dielectric constant of a step crystallization method, and dielectric loss is compared with two step crystallizations without obvious
Change (less than 2%).770 DEG C of nucleation temperature, 800 DEG C, 830 DEG C is set forth in Fig. 4 embodiment 1-3,950 DEG C of crystallization temperature
Resistance to disruptive field intensity.The value difference of resistance to disruptive field intensity of different nucleation temperatures, identical crystallization temperature material is not larger, wherein i.e. real
The resistance to disruptive field intensity highest that example 2 (nucleation temperature is 800 DEG C, crystallization temperature is 950 DEG C) provides is applied, 1817KV/cm is reached；Fig. 4
In, that comparative example provides is the resistance to breakdown field intensity values 962KV/cm that a step crystallization method obtains, the glass pottery that two step crystallization methods obtain
The resistance to disruptive field intensity of ceramic material is 1.88 times of the glass ceramic material that a step crystallization obtains.
Embodiment 4
The BaCO that purity is greater than 99wt% is chosen in the preparation of the metatitanic acid niobic acid composite glass-ceramic of the present embodiment3、SrCO3、
Nb2O5、TiO2、SiO2And Al2O3For feed proportioning, the molar percentage of above-mentioned each component is respectively 20%, 20%, 5%,
15%, 32% and 8%, preparation method is substantially the same manner as Example 1, finally obtains the 8Al of the present embodiment2O3·32SiO2·
20BaO·20SrO·15TiO2·5Nb2O5Metatitanic acid niobic acid composite glass-ceramic, resistance to breakdown field intensity values are big, energy storage density is big, energy
It enough applies in terms of energy-storage capacitor material.
Embodiment 5
The BaCO that purity is greater than 99wt% is chosen in the preparation of the metatitanic acid niobic acid composite glass-ceramic of the present embodiment3、SrCO3、
Nb2O5、TiO2、SiO2And Al2O3For feed proportioning, the molar percentage of above-mentioned each component is respectively 20%, 20%, 15%,
5%, 32% and 8%, preparation method is substantially the same manner as Example 1, finally obtains the 8Al of the present embodiment2O3·32SiO2·
20BaO·20SrO·5TiO2·15Nb2O5Metatitanic acid niobic acid composite glass-ceramic, resistance to breakdown field intensity values are big, energy storage density is big, energy
It enough applies in terms of energy-storage capacitor material.
Embodiment 6
The present embodiment is substantially the same manner as Example 1, the difference is that, the present embodiment metatitanic acid niobic acid composite glass-ceramic
Controlled Crystallization process is warming up to the heating rate of crystallization temperature from nucleation temperature as 1 DEG C/min in preparation process.
Embodiment 7
The present embodiment is substantially the same manner as Example 1, the difference is that, the present embodiment metatitanic acid niobic acid composite glass-ceramic
Controlled Crystallization process is warming up to the heating rate of crystallization temperature from nucleation temperature as 3 DEG C/min in preparation process.
Embodiment 8
The process of raw material proportioning and two step crystallizations that the present embodiment uses is same as Example 1, the difference is that, this reality
It applies through ball mill mixing and drying after adding alcohol after the feed proportioning of example, the ball mill mixing time is 10h, then in 1650 DEG C of temperature
Lower high temperature melt 2h is spent, high temperature melting melt body is obtained, then molten mass is poured into copper mold, in 550 DEG C of temperature destressings
Anneal 7h, then obtains the glass flake with a thickness of 0.9~1.2mm through cutting, then carries out niobium titanate by two step crystallization methods
The preparation of sour composite glass-ceramic.
Embodiment 8
The process of raw material proportioning and two step crystallizations that the present embodiment uses is same as Example 1, the difference is that, this reality
It applies through ball mill mixing and drying after adding alcohol after the feed proportioning of example, the ball mill mixing time is 20h, then in 1600 DEG C of temperature
Lower high temperature melt 2h is spent, high temperature melting melt body is obtained, then molten mass is poured into copper mold, in 700 DEG C of temperature destressings
Anneal 4h, then obtains the glass flake with a thickness of 0.9~1.2mm through cutting, then carries out niobium titanate by two step crystallization methods
The preparation of sour composite glass-ceramic.
Claims (11)
1. a kind of metatitanic acid niobic acid composite glass-ceramic, which is characterized in that the glass ceramics principal crystalline phase is Sr0.5Ba0.5Nb2O6、
Ba0.27Sr0.75Nb2O5.7And Sr6Ti2Nb4O20, glass phase SiO2, chemical formula 8Al2O3·32SiO2·20BaO·
20SrO·xTiO2·(20-x)Nb2O5, wherein x=5~15；
The preparation method of the metatitanic acid niobic acid composite glass-ceramic the following steps are included:
(1) Al is weighed2O3、SiO2、BaCO3、SrCO3、TiO2And Nb2O5According to molar ratio Al2O3:SiO2:BaCO3:SrCO3:
TiO2:Nb2O5=8:32:20:20:x:(20-x) it carries out ingredient and is uniformly mixed, high temperature melting melt body is made in high temperature melting；
(2) high temperature melting melt body is poured into the metal die of preheating, and carries out stress relief annealing, transparent glass is made, and cut
It is cut into glass flake；
(3) glass flake is first kept the temperature into 1~3h under 800 DEG C of nucleation temperature, then with the heating rate liter of 1~3 DEG C/min
The crystallization temperature of temperature to 950 DEG C, and keep the temperature 2~4h and carry out Controlled Crystallization to get metatitanic acid niobic acid composite glass-ceramic is arrived；
Wherein, the determination of the nucleation temperature in step (3) uses following methods:
(a) according to the corresponding temperature of highest exothermic peak on differential thermal curve as crystallization temperature；
(b) the metatitanic acid niobic acid compound glass pottery that two step crystallizations obtain is carried out under more different nucleation temperatures, identical crystallization temperature
The energy storage density value of porcelain selects the corresponding nucleation temperature of highest energy storage density value as nucleation temperature.
2. a kind of metatitanic acid niobic acid composite glass-ceramic according to claim 1, which is characterized in that the x=10.
3. a kind of preparation method of metatitanic acid niobic acid composite glass-ceramic as described in claim 1, which is characterized in that this method packet
Include following steps:
(1) Al is weighed2O3、SiO2、BaCO3、SrCO3、TiO2And Nb2O5According to molar ratio Al2O3:SiO2:BaCO3:SrCO3:
TiO2:Nb2O5=8:32:20:20:x:(20-x) it carries out ingredient and is uniformly mixed, high temperature melting melt body is made in high temperature melting；
(2) high temperature melting melt body is poured into the metal die of preheating, and carries out stress relief annealing, transparent glass is made, and cut
It is cut into glass flake；
(3) glass flake is first kept the temperature into 1~3h under 800 DEG C of nucleation temperature, then with the heating rate liter of 1~3 DEG C/min
The crystallization temperature of temperature to 950 DEG C, and keep the temperature 2~4h and carry out Controlled Crystallization to get metatitanic acid niobic acid composite glass-ceramic is arrived.
4. a kind of preparation method of metatitanic acid niobic acid composite glass-ceramic according to claim 3, which is characterized in that described
Al2O3、SiO2、BaCO3、SrCO3、TiO2And Nb2O5Purity be all larger than 99%.
5. a kind of preparation method of metatitanic acid niobic acid composite glass-ceramic according to claim 3, which is characterized in that
Mixing in step (1) was used the method through ball mill mixing and drying, the time of ball mill mixing after ingredient addition alcohol
For 10~20h；The temperature of high temperature melt is 1500~1650 DEG C, and the high temperature melt time is 2~4h.
6. a kind of preparation method of metatitanic acid niobic acid composite glass-ceramic according to claim 5, which is characterized in that step
(1) time of the ball mill mixing in is 12~16h, and the temperature of high temperature melt is 1500~1600 DEG C, the high temperature melt time is 2~
3h。
7. a kind of preparation method of metatitanic acid niobic acid composite glass-ceramic according to claim 3, which is characterized in that step
(2) the stress relief annealing temperature in is 550~700 DEG C, and the stress relief annealing time is 4~7h；Glass flake with a thickness of 0.9~
1.2mm。
8. a kind of preparation method of metatitanic acid niobic acid composite glass-ceramic according to claim 7, which is characterized in that step
(2) the stress relief annealing temperature in is 600~680 DEG C, and the stress relief annealing time is 5h.
9. a kind of preparation method of metatitanic acid niobic acid composite glass-ceramic according to claim 3, which is characterized in that step
(3) in by glass flake first 800 DEG C at a temperature of keep the temperature 2h, at a temperature of then heating to 950 DEG C keep the temperature 3h carry out it is controlled
Crystallization.
10. a kind of preparation method of metatitanic acid niobic acid composite glass-ceramic according to claim 3, which is characterized in that described
The step of (3) in heating rate be 2 DEG C/min.
11. a kind of application of the metatitanic acid niobic acid composite glass-ceramic as described in claim 1 in terms of energy-storage capacitor material.
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