CN106630642B - A kind of barium strontium niobate sodium base glass ceramics energy storage material and the preparation method and application thereof - Google Patents
A kind of barium strontium niobate sodium base glass ceramics energy storage material and the preparation method and application thereof Download PDFInfo
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- CN106630642B CN106630642B CN201610843365.XA CN201610843365A CN106630642B CN 106630642 B CN106630642 B CN 106630642B CN 201610843365 A CN201610843365 A CN 201610843365A CN 106630642 B CN106630642 B CN 106630642B
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- 238000004146 energy storage Methods 0.000 title claims abstract description 70
- 239000011734 sodium Substances 0.000 title claims abstract description 49
- 239000006121 base glass Substances 0.000 title claims abstract description 48
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 title claims abstract description 45
- 229910052708 sodium Inorganic materials 0.000 title claims abstract description 45
- DKDQMLPMKQLBHQ-UHFFFAOYSA-N strontium;barium(2+);oxido(dioxo)niobium Chemical compound [Sr+2].[Ba+2].[O-][Nb](=O)=O.[O-][Nb](=O)=O.[O-][Nb](=O)=O.[O-][Nb](=O)=O DKDQMLPMKQLBHQ-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 239000000919 ceramic Substances 0.000 title claims abstract description 33
- 239000011232 storage material Substances 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000011521 glass Substances 0.000 claims abstract description 32
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Inorganic materials O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 claims abstract description 25
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 24
- 238000002425 crystallisation Methods 0.000 claims abstract description 20
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 20
- 230000008025 crystallization Effects 0.000 claims abstract description 19
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 18
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 18
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 18
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 18
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 18
- 229910000018 strontium carbonate Inorganic materials 0.000 claims abstract description 17
- 238000000137 annealing Methods 0.000 claims abstract description 16
- LEDMRZGFZIAGGB-UHFFFAOYSA-L strontium carbonate Chemical compound [Sr+2].[O-]C([O-])=O LEDMRZGFZIAGGB-UHFFFAOYSA-L 0.000 claims abstract description 16
- 239000000463 material Substances 0.000 claims abstract description 15
- 238000002156 mixing Methods 0.000 claims abstract description 13
- 238000002844 melting Methods 0.000 claims abstract description 12
- 230000008018 melting Effects 0.000 claims abstract description 12
- 229910000029 sodium carbonate Inorganic materials 0.000 claims abstract description 12
- 238000001035 drying Methods 0.000 claims abstract description 11
- 229910052751 metal Inorganic materials 0.000 claims abstract description 11
- 239000002184 metal Substances 0.000 claims abstract description 11
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 claims abstract description 9
- 239000004615 ingredient Substances 0.000 claims abstract description 9
- 239000002994 raw material Substances 0.000 claims abstract description 6
- 239000003990 capacitor Substances 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- 238000002791 soaking Methods 0.000 claims description 3
- 239000010955 niobium Substances 0.000 claims 2
- DZSGQDBQANIYQT-UHFFFAOYSA-N [Na].[Ba].[Sr] Chemical compound [Na].[Ba].[Sr] DZSGQDBQANIYQT-UHFFFAOYSA-N 0.000 claims 1
- 229910052758 niobium Inorganic materials 0.000 claims 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims 1
- 239000002241 glass-ceramic Substances 0.000 abstract description 16
- 238000012805 post-processing Methods 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract description 2
- 229910010293 ceramic material Inorganic materials 0.000 description 20
- 238000002441 X-ray diffraction Methods 0.000 description 13
- 238000001228 spectrum Methods 0.000 description 11
- 238000010586 diagram Methods 0.000 description 9
- 238000011056 performance test Methods 0.000 description 9
- 238000005520 cutting process Methods 0.000 description 6
- 238000004321 preservation Methods 0.000 description 6
- PILOURHZNVHRME-UHFFFAOYSA-N [Na].[Ba] Chemical compound [Na].[Ba] PILOURHZNVHRME-UHFFFAOYSA-N 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- KHKWDWDCSNXIBH-UHFFFAOYSA-N [Sr].[Pb] Chemical compound [Sr].[Pb] KHKWDWDCSNXIBH-UHFFFAOYSA-N 0.000 description 3
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229910052788 barium Inorganic materials 0.000 description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000003989 dielectric material Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910052573 porcelain Inorganic materials 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- PWYYWQHXAPXYMF-UHFFFAOYSA-N strontium(2+) Chemical compound [Sr+2] PWYYWQHXAPXYMF-UHFFFAOYSA-N 0.000 description 2
- 241000530268 Lycaena heteronea Species 0.000 description 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
- 229910003576 Sr0.5Ba0.5 Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- MSJIBCNUPFPONA-UHFFFAOYSA-N [K].[Sr] Chemical compound [K].[Sr] MSJIBCNUPFPONA-UHFFFAOYSA-N 0.000 description 1
- WOIHABYNKOEWFG-UHFFFAOYSA-N [Sr].[Ba] Chemical compound [Sr].[Ba] WOIHABYNKOEWFG-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 229910001422 barium ion Inorganic materials 0.000 description 1
- ZADPBFCGQRWHPN-UHFFFAOYSA-N boronic acid Chemical compound OBO ZADPBFCGQRWHPN-UHFFFAOYSA-N 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000003181 co-melting Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 239000006112 glass ceramic composition Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000007500 overflow downdraw method Methods 0.000 description 1
- 229940072033 potash Drugs 0.000 description 1
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 1
- 235000015320 potassium carbonate Nutrition 0.000 description 1
- UKDIAJWKFXFVFG-UHFFFAOYSA-N potassium;oxido(dioxo)niobium Chemical compound [K+].[O-][Nb](=O)=O UKDIAJWKFXFVFG-UHFFFAOYSA-N 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- 229910001427 strontium ion Inorganic materials 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C10/00—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B32/00—Thermal after-treatment of glass products not provided for in groups C03B19/00, C03B25/00 - C03B31/00 or C03B37/00, e.g. crystallisation, eliminating gas inclusions or other impurities; Hot-pressing vitrified, non-porous, shaped glass products
- C03B32/02—Thermal crystallisation, e.g. for crystallising glass bodies into glass-ceramic articles
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G4/00—Fixed capacitors; Processes of their manufacture
- H01G4/002—Details
- H01G4/018—Dielectrics
- H01G4/06—Solid dielectrics
- H01G4/08—Inorganic dielectrics
- H01G4/12—Ceramic dielectrics
- H01G4/1209—Ceramic dielectrics characterised by the ceramic dielectric material
- H01G4/1254—Ceramic dielectrics characterised by the ceramic dielectric material based on niobium or tungsteen, tantalum oxides or niobates, tantalates
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Geochemistry & Mineralogy (AREA)
- Crystallography & Structural Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Power Engineering (AREA)
- Dispersion Chemistry (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Compositions Of Oxide Ceramics (AREA)
- Inorganic Insulating Materials (AREA)
- Glass Compositions (AREA)
Abstract
The present invention relates to a kind of barium strontium niobate sodium base glass ceramics energy storage materials and the preparation method and application thereof, and the barium strontium niobate sodium base glass ceramics energy storage material is mainly by BaCO3、SrCO3、Na2CO3、Nb2O5And SiO2Raw material is prepared, and the molar ratio of five kinds of substances is BaCO3: SrCO3: Na2CO3: Nb2O5: SiO2=33.6x:33.6 (1-x): 8.4:28:30 carries out ingredient, and wherein x value range is 0-0.8；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 barium strontium niobate sodium base glass ceramics energy storage material.Compared with prior art, system of the present invention is simple, and preparation method is simple, economical and practical without complicated post-processing step, and glass ceramics energy storage material obtained has superior dielectric performance, and the energy storage characteristic of material is significantly improved.
Description
Technical field
The invention belongs to dielectric energy storage material technical fields, are related to a kind of barium strontium niobate sodium base glass ceramics energy storage material
And preparation method thereof with answer.
Background technique
In recent years, Pulse Power Techniques are widely used to electronic computer, communication, radar, all-electric warship, electromagnetism rail
The national defence such as road big gun weapon, hybrid vehicle, controlled laser nuclear fusion and modern industrial technology field.The energy storage of current material is close
Obviously breaking through, does not occur also in degree, and the volume of energy storage device is occupied greatly in entire pulser, this also makes significantly
About pulser is to miniaturization, the development of lightness.Therefore, currently in order to meeting the miniaturization and high storage of pulse power system
Can density requirement, various countries material worker, which just tries to explore research, to be had high dielectric constant, low connects electrical loss and high voltage is strong
The dielectric material of degree.
Glass ceramics is to prepare glass matrix using high-temperature fusion-method for quick cooling, is prepared using controllable crystallization method
At glass ceramics.Compared with traditional ceramics material, barium strontium niobate sodium base glass ceramics has some apparent advantages, for example, system
Standby uncomplicated, resistance to disruptive field intensity height, dielectric adjustable is strong, dielectric loss is low, possesses wide application in dielectric material field
Prospect.Strontium barium niobate potash glass ceramics can form the co-melting body of strontium barium niobate and strontium potassium niobate, realize the high dielectric of potassium niobate
The features such as constant, the resistance to disruptive field intensity of height of niobic acid barium and low-dielectric loss.Result of study shows barium strontium niobate sodium base glass ceramics
Energy storage 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 phosphoric acid to boronate glass ceramics performance, wherein
Energy storage density maximum value reaches 9.1J/cm3(Guohua Chen et al.Mater.Lett., 2016,176:46-53).At present
Until, although people conduct extensive research dielectric energy storage material, the glass ceramics energy storage material reported
Energy storage density 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 SrNb2 O6 sodium base of high energy storage density
Glass ceramics energy storage material and the preparation method and application thereof, which includes 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；Then
It is poured into the metal die of preheating, stress relief annealing, transparent glass is made, is cut into the glass with a thickness of 0.9~1.2mm
Glass thin slice carries out Controlled Crystallization, obtains product, which can be applied to energy-storage capacitor material.Compared with above-mentioned patent, this
Invention has following difference: 1) part strontium ion is substituted by barium ions；2) the more uniform densification of microstructure；3) it is stored up in height
Under energy density case, dielectric constant improves nearly 1~4 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, barium strontium niobate sodium 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 barium strontium niobate sodium base glass ceramics energy storage material, this method specifically includes the following steps:
(1) with BaCO3、SrCO3、Na2CO3、Nb2O5、SiO2For raw material, 33.6mol% [x BaCO in molar ratio3+(1-x)
SrCO3] -8.4mol%Na2CO3- 28mol%Nb2O5- 30mol%SiO2Ingredient is carried out, wherein x value range is 0-0.8；
(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 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 barium strontium niobate sodium base glass pottery
Porcelain energy storage material.
The value of x is 0,0.2,0.33,0.5 or 0.8 in step (1).
BaCO described in step (1)3、SrCO3、Na2CO3、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 600-700 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 0.9-1.5mm.
The temperature of Controlled Crystallization described in step (4) is 750-1100 DEG C, soaking time 2-5h.
The temperature of Controlled Crystallization described in step (4) is 750-950 DEG C as a preferred technical solution, and soaking time is
2-4h。
The barium strontium niobate sodium base glass ceramics energy storage material being prepared using the above method.
The application of barium strontium niobate sodium base glass ceramics energy storage material, the barium strontium niobate sodium 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 Sr6Nb10O30、Sr0.5Ba0.5Nb6、SrBaNaNb5O15Deng 33.6mol% [x BaCO in molar ratio3+(1-
x)SrCO3] -8.4mol%Na2CO3- 28mol%Nb2O5- 30mol%SiO2Ingredient is carried out, wherein x=0~0.8.It is mixed through ball milling
Material, drying, then high temperature melting reaction is carried out, and high-temperature fusant Quick pouring is formed into metal die, subsequent destressing is moved back
Fire is cut into glass flake, then Controlled Crystallization, obtains the barium strontium niobate sodium base glass ceramics energy storage material.The present invention
Based on 33.6mol% [xBaCO3+(1-x)SrCO3] -8.4mol%Na2CO3- 28mol%Nb2O5- 30mol%SiO2Ingredient,
Middle x value range is 0~0.8；By adjusting BaCO3And SrCO3Glass pottery after mole when different heat treatment temperature
Porcelain, phase structure are improved, and resistance to disruptive field intensity significantly improves, and as x=0.2, crystallization temperature is 750 DEG C, resistance to disruptive field intensity
It is optimal value 2287kV/cm, theoretical energy storage density reaches 18.06J/cm3, dielectric loss at room temperature is reduced to 0.0077.
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 barium strontium niobate sodium base glass ceramic material；
Fig. 2 is the X-ray diffraction analysis figure (XRD) of embodiment 6-8 barium strontium niobate sodium base glass ceramic material；
Fig. 3 is the dielectric temperature spectrum and dielectric loss figure of embodiment 1-5 barium strontium niobate sodium base glass ceramic material；
Fig. 4 is the dielectric temperature spectrum and dielectric loss figure of embodiment 6-8 barium strontium niobate sodium base glass ceramic material；
Fig. 5 is the Weibull distribution map of the resistance to disruptive field intensity of embodiment 1-5 barium strontium niobate sodium base glass ceramic material；
Fig. 6 is the Weibull distribution map of the resistance to disruptive field intensity of embodiment 6-8 barium strontium niobate sodium base glass ceramic material；
Fig. 7-1 is the scanning electron microscope diagram spectrum of 1 barium strontium niobate sodium base glass ceramic material of embodiment；
Fig. 7-2 is the scanning electron microscope diagram spectrum of 2 barium strontium niobate sodium base glass ceramic material of embodiment；
Fig. 7-3 is the scanning electron microscope diagram spectrum of 3 barium strontium niobate sodium base glass ceramic material of embodiment；
Fig. 7-4 is the scanning electron microscope diagram spectrum of 4 barium strontium niobate sodium base glass ceramic material of embodiment；
Fig. 7-5 is the scanning electron microscope diagram spectrum of 5 barium strontium niobate sodium base glass ceramic material of embodiment；
Fig. 7-6 is the scanning electron microscope diagram spectrum of 6 barium strontium niobate sodium base glass ceramic material of embodiment；
Fig. 7-7 is the scanning electron microscope diagram spectrum of 7 barium strontium niobate sodium base glass ceramic material of embodiment；
Fig. 7-8 is the scanning electron microscope diagram spectrum of 8 barium strontium niobate sodium base glass ceramic material of embodiment；
Fig. 7-9 is the scanning electron microscope diagram spectrum of 9 barium strontium niobate sodium 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 BaCO of 99wt% with purity3、SrCO3、Na2CO3、Nb2O5、SiO2For feed proportioning, above-mentioned each component
Molar percentage be 0,33.6%, 8.4%, 28% and 30%, after ball mill mixing 16h, drying, in 1520 DEG C of high temperature meltings
3h；
(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 800 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 BaCO of 99wt% with purity3、SrCO3、Na2CO3、Nb2O5、SiO2For feed proportioning, above-mentioned each component
Molar percentage be 6.72%, 26.88%, 8.4%, 28% and 30%, after ball mill mixing 16h, drying, in 1520 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 800 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 14.87J/cm3, can be used as energy-storage capacitor
Material.
Embodiment 3:
(1) it is greater than the BaCO of 99wt% with purity3、SrCO3、Na2CO3、Nb2O5、SiO2For feed proportioning, above-mentioned each component
Molar percentage be 11.2%, 22.4%, 8.4%, 28% and 30%, after ball mill mixing 16h, drying, in 1520 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 800 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 12.83J/cm3, can be used as energy-storage capacitor
Material.
Embodiment 4:
(1) it is greater than the BaCO of 99wt% with purity3、SrCO3、Na2CO3、Nb2O5、SiO2For feed proportioning, above-mentioned each component
Molar percentage be 16.8%, 16.8%, 8.4%, 28% and 30%, after ball mill mixing 16h, drying, in 1520 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 800 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 BaCO of 99wt% with purity3、SrCO3、Na2CO3、Nb2O5、SiO2For feed proportioning, above-mentioned each component
Molar percentage be 26.88%, 6.72%, 8.4%, 28% and 30%, after ball mill mixing 16h, drying, in 1520 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 800 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:
In the preparation method of the present embodiment barium strontium niobate sodium base glass ceramic material, Controlled Crystallization temperature is 750 DEG C, remaining
With embodiment 2.
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, value 18.06J/cm3, can be used as energy-storage capacitor
Material.
Embodiment 7:
In the preparation method of the present embodiment barium strontium niobate sodium base glass ceramic material, Controlled Crystallization temperature is 900 DEG C, remaining
With embodiment 2.
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. 7-7, energy storage density is as shown in table 1.
Embodiment 8:
In the preparation method of the present embodiment barium strontium niobate sodium base glass ceramic material, Controlled Crystallization temperature is 1000 DEG C,
Remaining same embodiment 2.
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.
Embodiment 9:
In the preparation method of the present embodiment barium strontium niobate sodium base glass ceramic material, Controlled Crystallization temperature is 1100 DEG C,
Remaining same embodiment 2.
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 7-9, and energy storage density is as shown in table 1.
1 barium strontium niobate sodium base glass ceramics energy storage material performance characterization of table
Based on the above embodiment, the present invention has prepared the barium strontium niobate sodium base glass ceramics energy storage material of high energy storage density
Material, energy storage density maximum may be up to 18.06J/cm3, and dielectric loss is relatively low, and therefore, barium strontium niobate produced by the present invention
Sodium base glass ceramics energy storage material is used as energy-storage capacitor material.
Embodiment 10:
(1) it is greater than the BaCO of 99wt% with purity3、SrCO3、Na2CO3、Nb2O5、SiO2For feed proportioning, above-mentioned each component
Molar percentage be 11.09%, 22.51%, 8.4%, 28% and 30%, after ball mill mixing 12h, drying, at 1580 DEG C
High temperature melting 2.5h；
(2) high-temperature fusant that step (1) obtains is poured into metal die, in 640 DEG C of temperature stress relief annealing 5h, so
The glass flake with a thickness of 0.9mm is obtained by cutting；
(3) glass flake made from step (2) is subjected to Controlled Crystallization in 800 DEG C of heat preservation 3h, obtains glass ceramics.
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 (6)
1. a kind of preparation method of barium strontium niobate sodium base glass ceramics energy storage material, which is characterized in that this method specifically include with
Lower step:
(1) with BaCO3、SrCO3、Na2CO3、Nb2O5、SiO2For raw material, 33.6mol% [xBaCO in molar ratio3+(1-x)
SrCO3] -8.4mol%Na2CO3- 28mol%Nb2O5- 30mol%SiO2Ingredient is carried out, wherein x value is 0.2；
(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, crystallization temperature is 750 DEG C, soaking time 3h makes
Obtain the barium strontium niobate sodium base glass ceramics energy storage material.
2. a kind of preparation method of barium strontium niobate sodium base glass ceramics energy storage material according to claim 1, feature exist
In BaCO described in step (1)3、SrCO3、Na2CO3、Nb2O5And SiO2Purity be greater than 99wt%.
3. a kind of preparation method of barium strontium niobate sodium 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.
4. a kind of preparation method of barium strontium niobate sodium 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.
5. the barium strontium niobate sodium base glass ceramics energy storage material being prepared using the described in any item methods of Claims 1-4.
6. the application of barium strontium niobate sodium base glass ceramics energy storage material as claimed in claim 5, which is characterized in that the niobium
Sour barium strontium sodium base glass ceramics energy storage material is applied to energy-storage capacitor material.
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| CN105645772A (en) * | 2016-01-06 | 2016-06-08 | 同济大学 | High-energy-storage-density strontium-sodium-niobate-base glass ceramic energy storage material, and preparation and application thereof |
| 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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| CN105645772A (en) * | 2016-01-06 | 2016-06-08 | 同济大学 | High-energy-storage-density strontium-sodium-niobate-base glass ceramic energy storage material, and preparation and application thereof |
| 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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