CN108395106A - Lead bariun niobate sodium base glass ceramic material of high energy storage density and preparation method thereof - Google Patents
Lead bariun niobate sodium base glass ceramic material of high energy storage density and preparation method thereof Download PDFInfo
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- CN108395106A CN108395106A CN201810366442.6A CN201810366442A CN108395106A CN 108395106 A CN108395106 A CN 108395106A CN 201810366442 A CN201810366442 A CN 201810366442A CN 108395106 A CN108395106 A CN 108395106A
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C10/00—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B19/00—Other methods of shaping glass
- C03B19/02—Other methods of shaping glass by casting molten glass, e.g. injection moulding
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B32/00—Thermal after-treatment of glass products not provided for in groups C03B19/00, C03B25/00 - C03B31/00 or C03B37/00, e.g. crystallisation, eliminating gas inclusions or other impurities; Hot-pressing vitrified, non-porous, shaped glass products
- C03B32/02—Thermal crystallisation, e.g. for crystallising glass bodies into glass-ceramic articles
Abstract
The present invention relates to lead bariun niobate sodium base glass ceramic materials of high energy storage density and preparation method thereof, and ceramic particle component mainly includes the NaNbO of Perovskite Phase3And the Ba of tungsten bronze2NaNb5O15.The chemical composition of the glass ceramics energy storage material meets chemical general formula 6.4Na2CO3‑23.04BaCO3‑2.56PbO‑32Nb2O5‑36SiO2, with Na2CO3、BaCO3、PbO、Nb2O5、SiO2For raw material, dried after roller grinds batch mixing, then high temperature melting, obtains glass melt；High-temperature fusant is quickly poured on the mold of preheating, in constant temperature oven internal insulation a few hours to remove the residual stress under chilling in glass, glass block such as is then cut into at big few and thickness glass flake；Glass flake is subjected to Controlled Crystallization to get to the glass ceramics energy storage material of the present invention, barium sodium niobate (BNN) base glass ceramics energy storage material is for energy-storage capacitor material.Compared with prior art, the glass ceramics energy storage material that prepared by the present invention has many advantages, such as that dielectric constant and energy storage density are high, and heat-treatment temperature range is wide.
Description
Technical field
The invention belongs to field of dielectric energy storage material, it is related to a kind of dielectric energy storage material and preparation method thereof, especially
It is to be related to a kind of lead bariun niobate sodium base glass ceramic material of high energy storage density and preparation method thereof.
Background technology
Traditional fossil energy can inevitably cause the problems such as environmental pollution in use, and fossil energy
It is non-renewable energy resources, it can increasingly depleted.Environmental pollution caused by fossil energy and energy crisis push people constantly to go to visit
Grommet is protected and reproducible new energy.Meanwhile in order to improve energy utilization rate, various energy storage technologies and energy storage material are also met the tendency of
And give birth to, wherein high density capacitors are a kind of highly important energy storage original papers.Currently used as the energy storage dielectric of capacitor
Material include traditional ferroelectric ceramics, antiferroelectric ceramics and high polymer composite material, but limited the shortcomings that these materials itself
Their application is made.For ferroelectric ceramics, with higher dielectric constant, but often deposited in ceramic material itself
In stomata, the resistance to disruptive field intensity of material can be reduced, while stomata can make the consistency of material reduce and lead to the interior of capacitor
Consumption is big, is easy to damage electronic component in capacitor internal heat production.For antiferroelectric materials, due to the antiferroelectric phase transformation of ferroelectricity-
Presence, easily cause micro-crack in charge and discharge process repeatedly and damage capacitor.High polymer energy storage material, advantage exist
In high resistance to breakdown electric field (such as PVDF~3MV/cm), but the dielectric constant of high polymer it is extremely extremely low (<10) it, is stored up so as to cause it
Energy density is not also high, and in addition the thermal stability of high polymer energy storage material is poor, if electronic component heat production is excessively high to be easily damaged capacitor.
As energy storage material-glass ceramics energy storage material of nearest hot research, using the method for high temperature-melting, head will
Glass molten slurry is prepared in glass and ceramic composition fusing.Then, the molding and destressing of both bulk glasses；Finally, by controllably analysing
Brilliant method prepare the sub-micron of large scale, the crystal of nano-scale and remnants glass phase composition and be imporous glass
Glass-ceramics, in controllable Crystallization Process, by adjusting the phase for the metal oxide and glass phase Network former for generating ceramic phase
Effective control to junction phase crystal grain grain ruler and content may be implemented in comparative example, so that the performance of glass ceramic material is very big
Optimized in degree.It is this that there is high-k, high cause by the high-temperature fusion glass ceramics that controllable crystallization is prepared again
The characteristics of density, high resistance to breakdown.To reach high energy storage density.Compared with traditional barium-strontium titanate-based glass ceramics, niobic acid
Barium sodium base ceramic phase more can obtain (recrystallization temperature is low) in its glass matrix by controllable crystallization, to make barium sodium niobate (BNN) base glass
Glass ceramics are better than the dielectric constant of barium-strontium titanate-based glass ceramics；In barium-strontium titanate-based glass ceramics high temperature Crystallization Process, mistake
More barium elements can lead to occur Dendritic TiC in glass ceramics, totally unfavorable to its resistance to breakdown electric field, and barium sodium niobate (BNN) base glass
Internal factor of the ceramics without such worry.Using the barium sodium niobate (BNN) of high dielectric constant as ceramic phase in this explanation, with silicate
For the composition of glass phase the barium sodium niobate (BNN) base glass of high-k, high resistance to breakdown electric field is obtained under low heat treatment temperature
Glass ceramic composite, this is of great significance to the practical application of medium energy storage material.
In recent years, niobates glass pottery is the another kind of high energy storage glass ceramic material of domestic and international hot research.Niobates
Devitrified glass is mainly by the composite material of niobate crystal and glass phase composition with tungsten bronze type structure and perovskite structure.
In niobates glass ceramics system, some scholars optimize it accordingly, doping vario-property is studied.M.P.Graca etc. is ground
Heat treatment has been studied carefully to SiO2-Na2O-Nb2O5The influence of the electricity and dielectric properties of series vitro-ceramic.The study found that group becomes
60SiO2-30Na2O-10Nb2O5(mol%) glass of system is heat-treated 4h at 650 DEG C, and material dielectric constant is up to 48.19,
Dielectric loss minimum 1.07.Shyu etc. prepares strontium barium niobate base glass ceramics by whole crystallization method, with sintering temperature liter
Height, SBN phase contents increase, and calculate analysis crystal content and are up to 40%, dielectric constant is up to 180；Then study again (SrO,
BaO)-Nb2O5System glass ceramics, it is found that when recrystallization temperature is less than 1000 DEG C, the dielectric constant of sample is up to 351, breakdown strength
Up to 4.5kV/cm, 0.15 μ C/cm of remanent polarization2.Then, Zeng et al. studies BaF2Additive is to SrO-BaO-
Nb2O5-B2O3The precipitation behaviour of glass and the influence of dielectric properties find the dielectric constant of the system devitrified glass with BaF2Add
The variation of reduction after first increase is presented in the increase of dosage, and the trend to become larger always occurs in resistance to breakdown.As addition 5mol%BaF2
When, obtain dielectric constant~337, the devitrified glass ceramics of resistance to breakdown~527kV/cm optimal performances.Jun Luo etc. are based on
Na2O-PbO-Nb2O5-SiO2Glass ceramics system, successfully prepares the multilayered structure capacitor of function admirable, and energy storage density reaches
8J/cm3.The dielectric properties that Wang et al. compares (BaO, K2O)-Nb2O5-SiO2 systems by studying the Ba/K of different proportion are ground
Study carefully, find when Ba/K is 4, after 900 DEG C of heat preservation 3h, up to 1973kV/cm, energy storage density is the disruptive field intensity of sample
12.06J/cm3.The application such as Han casting rapid cooling and controllable crystallization technique prepare 3 kinds of nano combined dielectric materials of glass ceramics,
Include unleaded SrNb2 O6 sodium and barium sodium niobate (BNN) system.When Sr/Na ratios and Ba/Na ratios are 1:When 1, the dielectric constant of material with
Heat treatment temperature increases and rises, after 900 DEG C of heat treatment 180min, the dielectric constant of (BaO, Na2O)-Nb2O5-SiO2 systems
300 are can reach, and (SrO, Na2O)-Nb2O5-SiO2 system dielectric constants are up to 370.Pass through the group of certain adjusting ceramic phase
At, optimization, change recrystallization temperature to improve glass ceramics energy storage density have great importance.
Application No. is 201610051694.0 Chinese patents to disclose a kind of niobic acid barium potassium base glass ceramics energy storage material
And preparation method thereof, each chemical composition meets chemical general formula：32x BaO-32(1-x)K2O–32Nb2O5–36SiO2, wherein, x's
Value range is 0.5~0.9；First, BaCO is weighed3、K2CO3、Nb2O5And SiO2It is uniformly mixed, high temperature melting, high temperature melting is made
Body；Then high-temperature fusant is poured into the metal die after preheating, stress relief annealing, transparent glass is made, slice obtains glass
Glass flake is finally carried out Controlled Crystallization, obtains purpose product by glass thin slice.Although the data method is simple, this is specially
Contain more KNbO in glass ceramic material prepared by profit3And KNb3O8Phase, material are easy the aging due to moisture absorption；Meanwhile
Dielectric constant is below 70 under 25 DEG C, the test condition of 100kHz, is unfavorable for the raising of condenser capacity.
Invention content
It is an object of the present invention to overcome the above-mentioned drawbacks of the prior art and provide a kind of high energy storage densities
The composition of lead bariun niobate sodium base glass-ceramic material and its preparation and application.
The purpose of the present invention can be achieved through the following technical solutions：
The lead bariun niobate sodium base glass ceramic material of high energy storage density, ceramic particle component include mainly Perovskite Phase
NaNbO3And the Ba of tungsten bronze2NaNb5O15, the chemical composition of the glass ceramic material meets chemical general formula 6.4Na2CO3-
23.04BaCO3-2.56PbO-32Nb2O5-36SiO2。
PbO contents can excessive 10~15wt.% in material composition.
The preparation method of the lead bariun niobate sodium base glass ceramic material of high energy storage density, using following steps：
(1) with Na2CO3、BaCO3、PbO、Nb2O5、SiO2It is 6.4Na by mol ratio for raw material2CO3-23.04BaCO3-
2.56PbO-32Nb2O5-36SiO2Dispensing, after mixing, high-temperature molten slurry is made in high temperature melting；
(2) high-temperature molten slurry prepared by step (1) is poured into the die for molding of preheating and is kept for preheating temperature a few hours
The uniform glass of transparent no calculus is prepared with the residual stress removed in glass, slice obtains glass flake；
(3) glass flake made from step (3) is subjected to Controlled Crystallization, obtains the niobic acid base glass ceramics energy storage
Material.
In step (1) at 1500 DEG C high temperature melting 20-40min.
The preheating temperature of mold is 600 DEG C in step (2), and high-temperature molten slurry preheats 6h in a mold.
It is 5 DEG C/min to control heating rate in step (3) when Controlled Crystallization, and recrystallization temperature is 850 DEG C~1000 DEG C, temperature control
Time is 3~5h.
As preferred embodiment, recrystallization temperature is 900 DEG C, temperature control 5h.
The lead bariun niobate sodium base glass ceramic material of high energy storage density is since dielectric constant and energy storage density are high, Controlled Crystallization
Temperature range it is wide, energy-storage capacitor material can be used as.
Compared with prior art, for the present invention by adjusting the glass ceramics after recrystallization temperature, dielectric constant and energy storage are close
Degree significantly improves.Particularly, when recrystallization temperature is 900 DEG C, theoretical energy storage density reaches optimal value 20.3J/cm3；When crystallization temperature
When degree is 950 DEG C, dielectric constant is optimal value, and 100kHz is 150 at room temperature, and theoretical energy storage density is to 16.5J/cm3.This
It is because PbO is added, after 900 DEG C and 950 DEG C heat treatments, material is more easy to be precipitated with high-k
Ba2NaNb5O15, Pb0.3Ba0.7Nb2O6And NaNbO3, dephasign content is less；These crystalline phases are evenly distributed on glass matrix simultaneously
In, microscopic appearance is uniform and fine and close, therefore the material has higher resistance to disruptive field intensity.Also, the present invention also has following excellent
Point：
(1) by optimizing recrystallization temperature, ferroelectric phase Ba can be effectively improved2NaNb5O15And Pb0.3Ba0.7Nb2O6Content,
To improve the dielectric constant of glass ceramics；Under 850 DEG C to 950 DEG C heat treatment temperatures, the microscopic appearance of glass ceramics is always
Uniform compact, resistance to disruptive field intensity are maintained at a higher level.For glass ceramic material, energy storage density meets J=0.5
ε0εrE2, to make its theoretical density be improved significantly.
(2) from DSC curve, when heating rate is 10 DEG C/min, Tp1=775 DEG C, Tp2=906 DEG C, between the two
131 DEG C of difference, the principal crystalline phase being precipitated in this temperature range known to the XRD analysis are Ba2NaNb5O15、
Pb0.3Ba0.7Nb2O6And NaNbO3Phase.Therefore the temperature range of the material Controlled Crystallization is wide.
(3) Na in raw material2CO3Major part is with Ba2NaNb5O15And NaNbO3It is mutually precipitated, material is not easy moisture absorption aging.
(4) preparation method is simple, economical and practical without complicated post-processing step.
Description of the drawings
Fig. 1 is 6.4Na2CO3-23.04BaCO3-2.56PbO-32Nb2O5-36SiO2(mole %) parent glass 10 DEG C/
DSC curve under the heating rate of min；
Fig. 2 is 6.4Na under different recrystallization temperatures2CO3-23.04BaCO3-2.56PbO-32Nb2O5-36SiO2(mole %)
The energy storage density of glass ceramics energy storage material and the relation curve of electric field；
Fig. 3 is 6.4Na under different recrystallization temperatures2CO3-23.04BaCO3-2.56PbO-32Nb2O5-36SiO2(mole %)
The dielectric constant of glass ceramics energy storage material and loss；
Fig. 4 is 6.4Na under different recrystallization temperatures2CO3-23.04BaCO3-2.56PbO-32Nb2O5-36SiO2(mole %)
The Weibull profile curves of the resistance to disruptive field intensity of glass ceramics energy storage material；
Fig. 5 is 6.4Na under different recrystallization temperatures2CO3-23.04BaCO3-2.56PbO-32Nb2O5-36SiO2(mole %)
The XRD spectra of glass ceramics energy storage material；
Fig. 6 is 6.4Na under different recrystallization temperatures2CO3-23.04BaCO3-2.56PbO-32Nb2O5-36SiO2(mole %)
The SEM image of glass ceramics energy storage material.
Specific implementation mode
With reference to specific embodiment, the present invention is described in detail.Following embodiment will be helpful to the technology of this field
Personnel further understand the present invention, but the invention is not limited in any way.It should be pointed out that the ordinary skill of this field
For personnel, without departing from the inventive concept of the premise, various modifications and improvements can be made.These belong to the present invention
Protection domain.
Embodiment 1
The preparation method of the lead bariun niobate sodium base glass ceramics energy storage material of high energy storage density, includes the following steps：
(1) it is more than the Na of 99wt% with purity2CO3、BaCO3、PbO、Nb2O5、SiO2For feed proportioning, each component rubs
Your percentage is 6.4%, 23.04%, 2.56%, 32%, 36%, for 24 hours through ball mill mixing, after being dried 6 hours at 120 DEG C,
In 1500 DEG C of high temperature melting 30min；(above-mentioned ball milling using absolute ethyl alcohol as medium, ratio of grinding media to material 1.5：1).
(2) high-temperature fusant that step (1) obtains is poured into rectangular copper mould, in 600 DEG C of temperature stress relief annealing 6h,
Then the glass flake that thickness is 1.0~1.5mm is obtained after cutting；
(3) quantity such as take to be put into rectangular crucible glass flake made from step (2), with the heating rate of 5 DEG C/min
To after 850 DEG C, heat preservation 5h obtains glass ceramics.
The energy storage density of sample obtained by the present embodiment is as shown in Fig. 2, its energy storage density is up to 19.7J/cm3, can
Applied to energy-storage capacitor material.Dielectric properties are as shown in figure 3, be 124；Pressure-resistant performance test is as shown in figure 4, be 1893kV/
cm；XRD is as shown in figure 5, SEM is as shown in Figure 6.
In the present embodiment, the principal crystalline phase of ceramic phase is Ba2NaNb5O15, while having NaNbO3And Pb0.3Ba0.7Nb2O6It is precipitated,
So that material has higher dielectric constant.Find that glass ceramics microscopic appearance is very fine and close by SEM, and after crystallization, ceramics
Mutually and glass distributed mutually is relatively uniform, makes it have higher disruptive field intensity.
Embodiment 2
The preparation method of the lead bariun niobate sodium base glass ceramics energy storage material of high energy storage density, includes the following steps：
(1) it is more than the Na of 99wt% with purity2CO3、BaCO3、PbO、Nb2O5、SiO2For feed proportioning, each component rubs
Your percentage is 6.4%, 23.04%, 2.56%, 32%, 36%, for 24 hours through ball mill mixing, after being dried 6 hours at 120 DEG C,
In 1500 DEG C of high temperature melting 30min；(above-mentioned ball milling using absolute ethyl alcohol as medium, ratio of grinding media to material 1.5：1).
(2) high-temperature fusant that step (1) obtains is poured into rectangular copper mould, in 600 DEG C of temperature stress relief annealing 6h,
Then the glass flake that thickness is 1.0~1.5mm is obtained after cutting；
(3) quantity such as take to be put into rectangular crucible glass flake made from step (2), with the heating rate of 5 DEG C/min
To after 900 DEG C, heat preservation 5h obtains glass ceramics.
The energy storage density of sample obtained by the present embodiment is as shown in Fig. 2, its energy storage density is up to 20.3J/cm3, can
Applied to energy-storage capacitor material.Dielectric properties are as shown in figure 3, be 134；Pressure-resistant performance test is as shown in figure 4, be 1848kV/
cm；XRD is as shown in figure 5, SEM is as shown in Figure 6.
In the present embodiment, the principal crystalline phase of ceramic phase is Ba2NaNb5O15, while having NaNbO3And Pb0.3Ba0.7Nb2O6It is precipitated,
So that material has higher dielectric constant.Find that glass ceramics microscopic appearance is very fine and close by SEM, and after crystallization, ceramics
Mutually and glass distributed mutually is relatively uniform, makes it have higher disruptive field intensity.
Embodiment 3
The preparation method of the lead bariun niobate sodium base glass ceramics energy storage material of high energy storage density, includes the following steps：
(1) it is more than the Na of 99wt% with purity2CO3、BaCO3、PbO、Nb2O5、SiO2For feed proportioning, each component rubs
Your percentage is 6.4%, 23.04%, 2.56%, 32%, 36%, for 24 hours through ball mill mixing, after being dried 6 hours at 120 DEG C,
In 1500 DEG C of high temperature melting 30min；(above-mentioned ball milling using absolute ethyl alcohol as medium, ratio of grinding media to material 1.5：1).
(2) high-temperature fusant that step (1) obtains is poured into rectangular copper mould, in 600 DEG C of temperature stress relief annealing 6h,
Then the glass flake that thickness is 1.0~1.5mm is obtained after cutting；
(3) quantity such as take to be put into rectangular crucible glass flake made from step (2), with the heating rate of 5 DEG C/min
To after 950 DEG C, heat preservation 5h obtains glass ceramics.
The energy storage density of sample obtained by the present embodiment is as shown in Fig. 2, its energy storage density is up to 16.5J/cm3, can
Applied to energy-storage capacitor material.Dielectric properties are as shown in figure 3, be 150；Pressure-resistant performance test is as shown in figure 4, be 1575kV/
cm；XRD is as shown in figure 5, SEM is as shown in Figure 6.
In the present embodiment, the principal crystalline phase of ceramic phase is Ba2NaNb5O15, while having NaNbO3And Pb0.3Ba0.7Nb2O6It is precipitated,
Compared to embodiment 1 and embodiment 2, low dielectric constant ceramic phase BaAl has been precipitated2Si2O8And AlNbO4So that disruptive field intensity declines.
Find that glass ceramics microscopic appearance is comparatively dense by SEM, but after crystallization, ceramic phase and glass distributed mutually uniformity are poor, make it
Disruptive field intensity declines.
Embodiment 4
The preparation method of the lead bariun niobate sodium base glass ceramics energy storage material of high energy storage density, includes the following steps：
(1) it is more than the Na of 99wt% with purity2CO3、BaCO3、PbO、Nb2O5、SiO2For feed proportioning, each component rubs
Your percentage is 6.4%, 23.04%, 2.56%, 32%, 36%, for 24 hours through ball mill mixing, after being dried 6 hours at 120 DEG C,
In 1500 DEG C of high temperature melting 30min；(above-mentioned ball milling using absolute ethyl alcohol as medium, ratio of grinding media to material 1.5：1).
(2) high-temperature fusant that step (1) obtains is poured into rectangular copper mould, in 600 DEG C of temperature stress relief annealing 6h,
Then the glass flake that thickness is 1.0~1.5mm is obtained after cutting；
(3) quantity such as take to be put into rectangular crucible glass flake made from step (2), with the heating rate of 5 DEG C/min
To after 1000 DEG C, heat preservation 5h obtains glass ceramics.
The energy storage density of sample obtained by the present embodiment is as shown in Fig. 2, its energy storage density is up to 12.6J/cm.Dielectric
Performance is as shown in figure 3, be 138；Pressure-resistant performance test is as shown in figure 4, be 1437kV/cm；XRD is as shown in figure 5, SEM such as Fig. 6 institutes
Show.
In the present embodiment, the principal crystalline phase of ceramic phase is Ba2NaNb5O15, while having NaNbO3And Pb0.3Ba0.7Nb2O6It is precipitated,
Compared to embodiment 1 and embodiment 2, low dielectric constant ceramic phase BaAl has been precipitated2Si2O8And AlNbO4So that disruptive field intensity declines.
Finding glass ceramics microscopic appearance by SEM, there are increased number of stomata, and ceramic phase and glass distributed mutually uniformity are poor, make its breakdown field
It is strong to decline.
Embodiment 5
The lead bariun niobate sodium base glass ceramic material of high energy storage density, ceramic particle component include mainly Perovskite Phase
NaNbO3And the Ba of tungsten bronze2NaNb5O15, the chemical composition of the glass ceramic material meets chemical general formula 6.4Na2CO3-
23.04BaCO3-2.56PbO-32Nb2O5-36SiO2.This kind of material is prepared using following methods：
(1) with Na2CO3、BaCO3、PbO、Nb2O5、SiO2It is uniformly mixed by above-mentioned raw materials mol ratio dispensing for raw material
Afterwards, high-temperature molten slurry is made in high temperature melting 20min at 1500 DEG C；
(2) high-temperature molten slurry prepared by step (1) is poured into the die for molding of 600 DEG C of preheating and keeps the preheating temperature control
The uniform glass of transparent no calculus is prepared with the residual stress removed in glass by warm 6h, and slice obtains glass flake；
(3) glass flake made from step (3) is subjected to Controlled Crystallization, when Controlled Crystallization control heating rate be 5 DEG C/
Min, recrystallization temperature are 850 DEG C, and the temperature control time is 5h, obtains the niobic acid base glass ceramics energy storage material, is prepared
Material due to dielectric constant and energy storage density it is high, the temperature range of Controlled Crystallization is wide, can be used as energy-storage capacitor material.
Embodiment 6
The lead bariun niobate sodium base glass ceramic material of high energy storage density, ceramic particle component include mainly Perovskite Phase
NaNbO3And the Ba of tungsten bronze2NaNb5O15, the chemical composition of the glass ceramic material meets chemical general formula 6.4Na2CO3-
23.04BaCO3-2.56PbO-32Nb2O5-36SiO2, in the present embodiment, PbO contents can also be excessive in material composition
10wt.%.This kind of material is prepared using following methods：
(1) with Na2CO3、BaCO3、PbO、Nb2O5、SiO2It is uniformly mixed by above-mentioned raw materials mol ratio dispensing for raw material
Afterwards, high-temperature molten slurry is made in high temperature melting 30min at 1500 DEG C；
(2) high-temperature molten slurry prepared by step (1) is poured into the die for molding of 600 DEG C of preheating and keeps the preheating temperature control
The uniform glass of transparent no calculus is prepared with the residual stress removed in glass by warm 6h, and slice obtains glass flake；
(3) glass flake made from step (3) is subjected to Controlled Crystallization, when Controlled Crystallization control heating rate be 5 DEG C/
Min, recrystallization temperature are 950 DEG C, and the temperature control time is 4h, obtains the niobic acid base glass ceramics energy storage material, is prepared
Material due to dielectric constant and energy storage density it is high, the temperature range of Controlled Crystallization is wide, can be used as energy-storage capacitor material.
Embodiment 7
The lead bariun niobate sodium base glass ceramic material of high energy storage density, ceramic particle component include mainly Perovskite Phase
NaNbO3And the Ba of tungsten bronze2NaNb5O15, the chemical composition of the glass ceramic material meets chemical general formula 6.4Na2CO3-
23.04BaCO3-2.56PbO-32Nb2O5-36SiO2, in the present embodiment, PbO contents can also be excessive in material composition
15wt.%.This kind of material is prepared using following methods：
(1) with Na2CO3、BaCO3、PbO、Nb2O5、SiO2It is uniformly mixed by above-mentioned raw materials mol ratio dispensing for raw material
Afterwards, high-temperature molten slurry is made in high temperature melting 40min at 1500 DEG C；
(2) high-temperature molten slurry prepared by step (1) is poured into the die for molding of 600 DEG C of preheating and keeps the preheating temperature control
The uniform glass of transparent no calculus is prepared with the residual stress removed in glass by warm 6h, and slice obtains glass flake；
(3) glass flake made from step (3) is subjected to Controlled Crystallization, when Controlled Crystallization control heating rate be 5 DEG C/
Min, recrystallization temperature are 1000 DEG C, and the temperature control time is 3h, obtains the niobic acid base glass ceramics energy storage material, is prepared
Material due to dielectric constant and energy storage density it is high, the temperature range of Controlled Crystallization is wide, can be used as energy-storage capacitor material.
Fig. 1 is that female glass of the lead bariun niobate sodium base glass ceramics of high energy storage density is warm under the heating rate of 10 DEG C/min
The curve (DSC curve) that flow rate varies with temperature.The chemical composition of the glass meets chemical general formula 6.4Na2CO3-
23.04BaCO3-2.56PbO-32Nb2O5-36SiO2.It can be seen that Tg=706 DEG C of the softening temperature of the glass, there are two heat releases
Peak, respectively Tp1=775 DEG C and Tp2=906 DEG C.In conjunction with Fig. 5 XRD spectrum it is found that in Tp1And Tp2Between, what sample was precipitated
Principal crystalline phase does not change substantially, is all the NaNbO of Perovskite Phase3And the Ba of tungsten bronze2NaNb5O15With
Pb0.3Ba0.7Nb2O6.In conjunction with Fig. 6, it is known that after the glass carries out Controlled Crystallization between 850 DEG C to 950 DEG C, can access
One fine and close glass ceramic material.So the temperature range of the material Controlled Crystallization is wide.
Specific embodiments of the present invention are described above.It is to be appreciated that the invention is not limited in above-mentioned
Particular implementation, those skilled in the art can make various deformations or amendments within the scope of the claims, this not shadow
Ring the substantive content of the present invention.
Claims (9)
1. the lead bariun niobate sodium base glass ceramic material of high energy storage density, which is characterized in that the meeting of chemical composition of the material
Learn general formula 6.4Na2CO3-23.04BaCO3-2.56PbO-32Nb2O5-36SiO2。
2. the lead bariun niobate sodium base glass ceramic material of high energy storage density according to claim 1, which is characterized in that raw material
PbO contents can excessive 10~15wt% in ingredient.
3. the preparation method of the lead bariun niobate sodium base glass ceramic material of high energy storage density as described in claim 1, feature
It is, this method uses following steps：
(1) with Na2CO3、BaCO3、PbO、Nb2O5、SiO2It is 6.4Na by mol ratio for raw material2CO3-23.04BaCO3-
2.56PbO-32Nb2O5-36SiO2Dispensing, after mixing, high-temperature molten slurry is made in high temperature melting；
(2) high-temperature molten slurry prepared by step (1) is poured into the die for molding of preheating and is kept for preheating temperature a few hours to go
Except the uniform glass of transparent no calculus is prepared in the residual stress in glass, slice obtains glass flake；
(3) glass flake made from step (3) is subjected to Controlled Crystallization, obtains the niobic acid base glass ceramics energy storage material
Material.
4. the preparation method of the lead bariun niobate sodium base glass ceramic material of high energy storage density according to claim 3, special
Sign is, in step (1) at 1500 DEG C high temperature melting 20-40min.
5. the preparation method of the lead bariun niobate sodium base glass ceramic material of high energy storage density according to claim 3, special
Sign is that the preheating temperature of mold is 600 DEG C in step (2).
6. the preparation method of the lead bariun niobate sodium base glass ceramic material of high energy storage density according to claim 3, special
Sign is that the destressing time is 6h to the high-temperature molten slurry described in step (2) in a mold.
7. the preparation method of the lead bariun niobate sodium base glass ceramic material of high energy storage density according to claim 3, special
Sign is that it is 5 DEG C/min to control heating rate when Controlled Crystallization in step (3), and recrystallization temperature is 850 DEG C~1000 DEG C, temperature control
Time is 3~5h.
8. the preparation method of the lead bariun niobate sodium base glass ceramic material of high energy storage density according to claim 7, special
Sign is that recrystallization temperature is 900 DEG C in step (3), temperature control 5h.
9. the lead bariun niobate sodium base glass ceramic material of high energy storage density as described in claim 1 is as energy-storage capacitor material
Application.
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