CN109467313A - High energy storage density barium sodium niobate (BNN) base glass ceramics energy storage material and its preparation and application - Google Patents
High energy storage density barium sodium niobate (BNN) base glass ceramics energy storage material and its preparation and application Download PDFInfo
- Publication number
- CN109467313A CN109467313A CN201811528685.1A CN201811528685A CN109467313A CN 109467313 A CN109467313 A CN 109467313A CN 201811528685 A CN201811528685 A CN 201811528685A CN 109467313 A CN109467313 A CN 109467313A
- Authority
- CN
- China
- Prior art keywords
- energy storage
- glass ceramics
- bnn
- storage material
- sodium niobate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
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
- C03C10/16—Halogen containing crystalline phase
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B19/00—Other methods of shaping glass
- C03B19/02—Other methods of shaping glass by casting molten glass, e.g. injection moulding
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B32/00—Thermal after-treatment of glass products not provided for in groups C03B19/00, C03B25/00 - C03B31/00 or C03B37/00, e.g. crystallisation, eliminating gas inclusions or other impurities; Hot-pressing vitrified, non-porous, shaped glass products
- C03B32/02—Thermal crystallisation, e.g. for crystallising glass bodies into glass-ceramic articles
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B5/00—Melting in furnaces; Furnaces so far as specially adapted for glass manufacture
- C03B5/16—Special features of the melting process; Auxiliary means specially adapted for glass-melting furnaces
Abstract
The present invention relates to high energy storage density barium sodium niobate (BNN) base glass ceramics energy storage materials and its preparation and application, the chemical component of the energy storage material to meet chemical general formula 6.8Na2CO3‑27.2BaCO3‑34Nb2O5‑32SiO2‑mCaF2, wherein m=0-4, with Na2CO3、BaCO3、Nb2O5、SiO2、CaF2For raw material, dried after roller is ground；Then high-temperature fusion obtains glass melt, and melt is quickly poured on preheating copper mold, in constant temperature oven internal insulation a few hours to remove the residual stress under chilling in glass, obtains the fast body of glass；Then glass block such as is cut at big few and thickness glass flake；Glass flake is finally subjected to Controlled Crystallization to get glass ceramics energy storage material of the invention is arrived.Compared with prior art, the advantages that glass ceramics energy storage material prepared by the present invention has dielectric constant high, and pressure resistance is functional, and discharge energy density and energy density are high, and the velocity of discharge is fast, and temperature, electric field have good stability.
Description
Technical field
The present invention relates to a kind of energy storage materials, more particularly, to a kind of high energy storage density barium sodium niobate (BNN) base glass ceramics energy storage
Material and its preparation and application.
Background technique
With the progress of science and technology and the raising of industrial requirement, the miniaturization and lightweight of energy-storage capacitor has become industry
The direction of boundary's long-run development causes the demand to the novel energy-storing dielectric material of high energy storage density very urgent.The study found that storage
Energy density and the dielectric constant and breakdown strength of energy-accumulating medium itself are closely related.For general dielectric material, dielectric constant increases
Breakdown strength can decrease while adding.Such as traditional ceramic material, dielectric constant is very big (~4000), but due to internal gas
The presence in hole causes its breakdown strength lower (~100kV/cm)；Although polymer material have high breakdown strength (such as PVDF~
3MV/cm), but dielectric constant is very low (< 10)；Although antiferroelectric have higher dielectric constant and disruptive field intensity, due to
The presence of the antiferroelectric phase transformation of ferroelectricity-, practical application repeated charge process very in easily cause micro-crack and damage capacitor
Device.Therefore, a kind of high dielectric constant, the High-energy-storage density dielectric material of high breakdown strength are found, while can guarantee that it has again
Good cyclical stability is the severe challenge currently faced.Glass ceramics (devitrified glass) combines the high dielectric constant of ceramics
And the high breakdown field strength of glass, and there is longer discharge life and extremely short discharge time, it is expected to become a kind of reason
The high energy storage density dielectric material thought.
Glass ceramics (also known as devitrified glass) is manufactured with the glass control crystallization or induction crystallization suitably formed.This
Class material is the non-porous complex as composed by a large amount of tiny crystal and a small amount of residual glass phase.It has concentrated glass and ceramics
The advantages of, its internal crystallization construction carefully much than the crystal in many ceramic materials, and more uniform densification, almost without
Stomata.By high-temperature fusion, the glass ceramics that controllable crystallization is prepared has the characteristics that high dielectric constant, high resistance to breakdown, thus
Reach high energy storage density.The every field such as national defence sophisticated technology, industry, building and biological medicine are applied to, are become
One of new material and the hot spot of new industrial research.
Glass ceramics is broadly divided into metatitanic acid alkali glass ceramics and niobate glass ceramics, metatitanic acid alkali glass ceramics,
Its higher crystallization temperature, which will lead to, there is Dendritic TiC in glass ceramics, so that its pressure-resistant performance is decreased, it is close to limit energy storage
The promotion of degree.So studying at present more for niobate glass ceramics, many scholars carry out niobate glass ceramics
Corresponding optimization, doping vario-property research.Du etc. has studied Na2O-PbO-Nb2O5-SiO2The crystallization behavior of series vitro-ceramic.Hair
Now there are high dielectric constant (> 600) by the sample that 3h at 850 DEG C is handled, at this time with NaNbO3For principal crystalline phase, it is precipitated simultaneously
PbNb2O6Crystal.A nanometer NaNbO is dispersed in sample3And PbNb2O6Particle is the main original that material has high dielectric constant
Cause.Zhang Wenjun etc. has studied Na2O content is to SrO-BaO-Nb2O5-SiO2-B2O3The shadow of system glass ceramics structure and performance
It rings, finds with Na2The addition of O, crystal phase is by being not added with Na2Ba when O0.5Sr0.5Nb2O6It is changed into Ba0.25Sr0.75Nb2O6, and
NaSr is then also precipitated1.2Ba0.8Nb5O15And Na2Ba2Si2O7Phase, dielectric constant change in " N " font, and disruptive field intensity reduces.Not
Add Na2The breakdown strength of sample is 1500kV/cm when O, and energy storage density reaches 3J/cm3.Chen etc. has studied on this basis
Containing 5% (molar fraction) Na2The electrical property of the system of O, its dielectric is normal when discovery heat treating regime is 800 DEG C of 3h+950 DEG C of 3h
Number about 50, breakdown strength is up to 1400kV/cm, energy storage density 4J/cm3。
Zhou etc. has studied different content Gd2O3To 17.08BaO-17.08Na2O-34.09Nb2O5-31.75SiO2Dielectric
The influence of performance and pressure-resistant performance.Research finds 1%Gd2O3Glass ceramics under 900 DEG C of crystallization temperature, dielectric constant is high
Up to 349, but its breakdown strength only has 561.6kJ/cm3.Wang etc. has studied crystallization temperature to 25.6BaCO3-6.4K2CO3-
32Nb2O5-36SiO2The influence of glass ceramics pressure resistance performance and energy-storage property.It was found that pressure-resistant performance is up to when 750 DEG C of crystallizations
2418.7kJ/cm3, but in the charge and discharge process of practical application, due to the discharge time being exceedingly fast, high frequency causes
The breakdown performance and energy-storage property of material are declined, therefore discharge energy density is high.Application No. is
201610051694.0 Chinese patent discloses a kind of niobic acid barium potassium base glass ceramics energy storage material and preparation method thereof, eachization
It studies and point meets chemical general formula: 32xBaO-32 (1-x) K2O-32Nb2O5-36SiO2, wherein the value range of x is 0.5~0.9,
Although the dielectric constant and energy storage density of the simple but prepared glass ceramic material of the patent method are relatively low.
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 high dielectric constants, height
Resistance to breakdown high field, the barium sodium niobate (BNN) base glass ceramics energy storage material of high discharge energy density and energy density and preparation and application.
The purpose of the present invention can be achieved through the following technical solutions:
High energy storage density barium sodium niobate (BNN) base glass ceramics energy storage material, the chemical component of the energy storage material meet chemical general formula
6.8Na2CO3-27.2BaCO3-34Nb2O5-32SiO2-mCaF2, wherein m=0-4, but be not 0.
Preferably, m=0.5,1,2,3 or 4, as most preferred technical solution, m 3.By adding different content
CaF2, dielectric constant significantly improves, and pressure-resistant performance also has a certain upgrade.Particularly, work as CaF2When content is 3%, theoretical energy storage
Density is optimal value.Discharge energy density reaches 46.26MW/cm3 at this time, and discharge energy density reaches 0.551J/cm3。
The preparation method of high energy storage density barium sodium niobate (BNN) base glass ceramics energy storage material, using following steps:
(1) with Na2CO3、BaCO3、CaF2、Nb2O5、SiO2For raw material, by the formula ingredient of chemical general formula, roller mill uniformly after
High-temperature molten slurry is made in drying, high temperature melting；
(2) high temperature molten slurry is poured into the copper mould of preheating and forms and the remnants in preheating temperature removal glass is kept to answer
Power prepares transparent glass；
(3) it is sliced transparent glass made from step (2) to obtain glass flake；
(4) glass flake made from step (3) is subjected to Controlled Crystallization, sodium niobate base glass ceramics energy storage material is prepared
Material.
Controlled at high temperature melting 2-3h at 1500-1550 DEG C in step (1).
Copper mould preheating temperature described in step (2) is 600-650 DEG C, and high temperature molten slurry keeps 5-6h in copper mould.
It is 5 DEG C/min that step (4), which carries out control heating rate when Controlled Crystallization, is warming up to 850 DEG C of isothermal holding 5h.
The barium sodium niobate (BNN) base glass ceramics energy storage material dielectric constant and energy storage density for the high energy storage density being prepared are high,
Discharge energy density and energy density are high, and temperature stability is good, and resistance to sparking can be high, are used as energy-storage capacitor material.
Compared with prior art, the invention has the characteristics that:
(1) by addition nucleating agent, the dielectric constant of glass ceramics, while the resistance to breakdown of glass ceramics can effectively be improved
Field strength is also promoted, so that its theoretical density be made to be improved significantly.
(2) preparation method is simple, economical and practical.
(3) discharge energy density and discharge energy density of the component optimized are attained by a high value.
Detailed description of the invention
Fig. 1 is 6.8Na2CO3-27.2BaCO3-34Nb2O5-32SiO2-3CaF2(mole %) glass ceramics energy storage material
The relation curve and discharge energy density and the relationship of time of discharge energy density and electric field；
Fig. 2 is 6.8Na under different temperatures2CO3-27.2BaCO3-34Nb2O5-32SiO2-3CaF2(mole %) glass ceramics
The discharge current of energy storage material and the relation curve of time；
Fig. 3 is 6.8Na2CO3-27.2BaCO3-34Nb2O5-32SiO2-mCaF2(m=0,0.5,1,2,3,4) it (rubs
You are %), different content CaF2The dielectric constant and loss variation with temperature relation curve of doped-glass ceramics energy storage material；
Fig. 4 is 6.8Na2CO3-27.2BaCO3-34Nb2O5-32SiO2-mCaF2(m=0,0.5,1,2,3,4) it (rubs
You are %), different content CaF2The Weibull profile curve of the resistance to disruptive field intensity of doped-glass ceramics energy storage material；
Fig. 5 is 6.8Na2CO3-27.2BaCO3-34Nb2O5-32SiO2-mCaF2(m=0,0.5,1,2,3,4) it (rubs
You are %), different content CaF2The XRD spectra of doped-glass ceramics energy storage material；
Fig. 6 is 6.8Na2CO3-27.2BaCO3-34Nb2O5-32SiO2-mCaF2(m=0,0.5,1,2,3,4) it (rubs
You are %), different content CaF2The SEM image of doped-glass ceramics energy storage material.
Specific embodiment
The present invention is described in detail combined with specific embodiments below.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 scope.
Comparative example
The preparation method of the barium sodium niobate (BNN) base glass ceramics energy storage material of high energy storage density, comprising the following steps:
(1) it is greater than the Na of 99wt% with purity2CO3、BaCO3、Nb2O5、SiO2For feed proportioning, moles the hundred of each component
Divide than being 6.8%, 27.2%, 34%, 32%, for 24 hours through ball mill mixing, after drying 8h at 110 DEG C, in 1550 DEG C of high temperature meltings
2h；(above-mentioned ball milling is using dehydrated 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 650 DEG C of temperature stress relief annealing 6h,
Then the glass flake with a thickness of 1.0~1.5mm is obtained through 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 dielectric properties of sample obtained by the present embodiment are as shown in figure 3, be 100；Pressure-resistant performance test as shown in figure 4,
For 1424.83kV/cm；Higher dielectric constant and pressure-resistant performance can bring higher energy storage density to glass ceramic material, count
The theoretical energy storage density of calculation is 8.99J/cm3；XRD as shown in figure 5, high dielectric constant Ba2NaNb5O15, NaNbO3And BaNbO3
The precipitation of phase, so that the dielectric constant of material reaches a high value；SEM is as shown in fig. 6, have found ceramic phase and glass by SEM
Phase distributing homogeneity is poor, keeps its disruptive field intensity not high.
Embodiment 1
The preparation method of the barium sodium niobate (BNN) base glass ceramics energy storage material of high energy storage density, comprising the following steps:
(1) it is greater than the Na of 99wt% with purity2CO3、BaCO3、Nb2O5、SiO2、CaF2For feed proportioning, each component
Molar percentage is 6.8%, 27.2%, 34%, 32%, 0.5%, for 24 hours through ball mill mixing, after drying 8h at 110 DEG C,
1550 DEG C of high temperature melting 2h；(above-mentioned ball milling is using dehydrated 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 650 DEG C of temperature stress relief annealing 6h,
Then the glass flake with a thickness of 1.0~1.5mm is obtained through 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 dielectric properties of sample obtained by the present embodiment are as shown in Fig. 2, be 111；Pressure-resistant performance test as shown in figure 3,
For 1463.74kV/cm；Higher dielectric constant and pressure-resistant performance can bring higher energy storage density to glass ceramic material, count
The theoretical energy storage density of calculation is 10.5J/cm3；XRD as shown in figure 5, high dielectric constant Ba2NaNb5O15, NaNbO3And BaNbO3
The precipitation of phase, so that the dielectric constant of material reaches a high value；SEM is as shown in fig. 6, have found ceramic phase and glass by SEM
Phase distributing homogeneity makes moderate progress, its disruptive field intensity is made to increase.
Embodiment 2
The preparation method of the barium sodium niobate (BNN) base glass ceramics energy storage material of high energy storage density, comprising the following steps:
(1) it is greater than the Na of 99wt% with purity2CO3、BaCO3、Nb2O5、SiO2、CaF2For feed proportioning, each component
Molar percentage is 6.8%, 27.2%, 34%, 32%, 1%, for 24 hours through ball mill mixing, after drying 8h at 110 DEG C, 1550
DEG C high temperature melting 2h；(above-mentioned ball milling is using dehydrated 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 650 DEG C of temperature stress relief annealing 6h,
Then the glass flake with a thickness of 1.0~1.5mm is obtained through 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 dielectric properties of sample obtained by the present embodiment are as shown in figure 3, be 115；Pressure-resistant performance test as shown in figure 4,
For 1494.95kV/cm；Higher dielectric constant and pressure-resistant performance can bring higher energy storage density to glass ceramic material, count
The theoretical energy storage density of calculation is 11.4J/cm3；XRD as shown in figure 5, high dielectric constant Ba2NaNb5O15, NaNbO3And BaNbO3
The precipitation of phase, so that the dielectric constant of material reaches a high value；SEM is as shown in fig. 6, have found ceramic phase and glass by SEM
Phase distributing homogeneity makes moderate progress, its disruptive field intensity is made to increase.
Embodiment 3
The preparation method of the barium sodium niobate (BNN) base glass ceramics energy storage material of high energy storage density, comprising the following steps:
(1) it is greater than the Na of 99wt% with purity2CO3、BaCO3、Nb2O5、SiO2、CaF2For feed proportioning, each component
Molar percentage is 6.8%, 27.2%, 34%, 32%, 2%, for 24 hours through ball mill mixing, after drying 8h at 110 DEG C, 1550
DEG C high temperature melting 2h；(above-mentioned ball milling is using dehydrated 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 650 DEG C of temperature stress relief annealing 6h,
Then the glass flake with a thickness of 1.0~1.5mm is obtained through 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 dielectric properties of sample obtained by the present embodiment are as shown in figure 3, be 122；Pressure-resistant performance test as shown in figure 4,
For 1515.38kV/cm；Higher dielectric constant and pressure-resistant performance can bring higher energy storage density to glass ceramic material, count
The theoretical energy storage density of calculation is 12.4J/cm3；XRD as shown in figure 5, high dielectric constant Ba2NaNb5O15And NaNbO3The analysis of phase
Out, so that the dielectric constant of material reaches a high value；SEM is as shown in fig. 6, have found that ceramic phase and glass phase are distributed by SEM
Uniformity makes moderate progress, and further increases its disruptive field intensity.
Embodiment 4
The preparation method of the barium sodium niobate (BNN) base glass ceramics energy storage material of high energy storage density, comprising the following steps:
(1) it is greater than the Na of 99wt% with purity2CO3、BaCO3、Nb2O5、SiO2、CaF2For feed proportioning, each component
Molar percentage is 6.8%, 27.2%, 34%, 32%, 3%, for 24 hours through ball mill mixing, after drying 8h at 110 DEG C, 1550
DEG C high temperature melting 2h；(above-mentioned ball milling is using dehydrated 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 650 DEG C of temperature stress relief annealing 6h,
Then the glass flake with a thickness of 1.0~1.5mm is obtained through 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.
Fig. 1 is the discharge energy density for the glass ceramics energy storage material that the present embodiment is prepared and the relationship song of electric field
The relationship of line and discharge energy density and time, when the electric field of application is 500kV/cm, discharge energy density reaches
46.26MW/cm3, discharge energy density reached 0.551J/cm3；Glass ceramics energy storage material puts obtained by the present embodiment
Electro-temperature stability is as shown in Fig. 2, the current time under different temperatures hardly changes, it can be seen that its good temperature is stablized
Property；The dielectric properties of sample obtained by the present embodiment are 134 as shown in figure 3, dielectric constant has reached a high value；It is resistance to
Performance test is pressed as shown in figure 4, being 1551.04kV/cm, reaches peak；Due to high dielectric properties and pressure-resistant performance, reason
Therefore also reach a high value by energy storage density, is 14.3J/cm3；XRD as shown in figure 5, high dielectric constant Ba2NaNb5O15
And NaNbO3The precipitation of phase, so that the dielectric constant of material reaches a high value；SEM is as shown in fig. 6, have found glass by SEM
Ceramic microstructures pattern is very fine and close, and after crystallization, and ceramic phase and glass phase distribution are relatively uniform, makes it have higher breakdown
Field strength.
Embodiment 5
The preparation method of the barium sodium niobate (BNN) base glass ceramics energy storage material of high energy storage density, comprising the following steps:
(1) it is greater than the Na of 99wt% with purity2CO3、BaCO3、Nb2O5、SiO2、CaF2For feed proportioning, each component
Molar percentage is 6.8%, 27.2%, 34%, 32%, 4%, for 24 hours through ball mill mixing, after drying 8h at 110 DEG C, 1550
DEG C high temperature melting 2h；(above-mentioned ball milling is using dehydrated 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 650 DEG C of temperature stress relief annealing 6h,
Then the glass flake with a thickness of 1.0~1.5mm is obtained through 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 dielectric properties of sample obtained by the present embodiment are as shown in figure 3, be 141；Pressure-resistant performance test as shown in figure 4,
For 1320.10kV/cm；Higher dielectric constant and pressure-resistant performance can bring higher energy storage density to glass ceramic material, count
The theoretical energy storage density of calculation is 10.9J/cm3；XRD as shown in figure 5, high dielectric constant Ba2NaNb5O15And BaNbO3The analysis of phase
Out, so that the dielectric constant of material reaches a high value；SEM is as shown in fig. 6, SEM discovery glass ceramics microscopic appearance exists
Increased number of stomata, ceramic phase and glass phase distributing homogeneity are poor, decline its disruptive field intensity.
Embodiment 6
High energy storage density barium sodium niobate (BNN) base glass ceramics energy storage material, the chemical component of the energy storage material meet chemical general formula
6.8Na2CO3-27.2BaCO3-34Nb2O5-32SiO2-2.5CaF2。
The preparation method of high energy storage density barium sodium niobate (BNN) base glass ceramics energy storage material, using following steps:
(1) with Na2CO3、BaCO3、CaF2、Nb2O5、SiO2For raw material, by the formula ingredient of above-mentioned chemical general formula, roller mill is equal
Drying after even, controlled at 1500 DEG C, high-temperature molten slurry is made in high temperature melting 3hization；
(2) high temperature molten slurry is poured into the copper mould of 600 DEG C of preheating and is formed, kept in preheating temperature 6h removal glass
Residual stress prepares transparent glass；
(3) it is sliced transparent glass made from step (2) to obtain glass flake；
(4) glass flake made from step (3) is subjected to Controlled Crystallization, control heating rate is 5 DEG C/min, is warming up to
Sodium niobate base glass ceramics energy storage material is prepared in 850 DEG C of isothermal holding 5h.
The barium sodium niobate (BNN) base glass ceramics energy storage material dielectric constant and energy storage density for the high energy storage density being prepared are high,
Discharge energy density and energy density are high, and temperature stability is good, and resistance to sparking can be high, are used as energy-storage capacitor material.
Embodiment 7
High energy storage density barium sodium niobate (BNN) base glass ceramics energy storage material, the chemical component of the energy storage material meet chemical general formula
6.8Na2CO3-27.2BaCO3-34Nb2O5-32SiO2-0.8CaF2。
The preparation method of high energy storage density barium sodium niobate (BNN) base glass ceramics energy storage material, using following steps:
(1) with Na2CO3、BaCO3、CaF2、Nb2O5、SiO2For raw material, by the formula ingredient of above-mentioned chemical general formula, roller mill is equal
Drying after even, controlled at 1520 DEG C, high-temperature molten slurry is made in high temperature melting 2hization；
(2) high temperature molten slurry is poured into the copper mould of 650 DEG C of preheating and is formed, kept in preheating temperature 5h removal glass
Residual stress prepares transparent glass；
(3) it is sliced transparent glass made from step (2) to obtain glass flake；
(4) glass flake made from step (3) is subjected to Controlled Crystallization, control heating rate is 5 DEG C/min, is warming up to
Sodium niobate base glass ceramics energy storage material is prepared in 850 DEG C of isothermal holding 5h.
By hair can be understood and used the above description of the embodiments is intended to facilitate those skilled in the art
It is bright.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,
Those skilled in the art's announcement according to the present invention, improvement and modification made without departing from the scope of the present invention all should be in this hairs
Within bright protection scope.
Claims (9)
1. high energy storage density barium sodium niobate (BNN) base glass ceramics energy storage material, which is characterized in that the chemical component of the energy storage material accords with
Close chemical general formula 6.8Na2CO3-27.2BaCO3-34Nb2O5-32SiO2-mCaF2, wherein m=0-4, but be not 0.
2. high energy storage density barium sodium niobate (BNN) base glass ceramics energy storage material according to claim 1, which is characterized in that wherein
M=0.5,1,2,3 or 4.
3. high energy storage density barium sodium niobate (BNN) base glass ceramics energy storage material according to claim 1, which is characterized in that wherein
M is preferably 3.
4. the preparation method of high energy storage density barium sodium niobate (BNN) base glass ceramics energy storage material as described in claim 1, feature
It is, this method uses following steps:
(1) with Na2CO3、BaCO3、CaF2、Nb2O5、SiO2For raw material, by the formula ingredient of chemical general formula, roller mill is uniformly rear to be dried,
High-temperature molten slurry is made in high temperature melting；
(2) high temperature molten slurry is poured into the copper mould of preheating to the residual stress system for forming and keeping in preheating temperature removal glass
For glass transparent out；
(3) it is sliced transparent glass made from step (2) to obtain glass flake；
(4) glass flake made from step (3) is subjected to Controlled Crystallization, sodium niobate base glass ceramics energy storage material is prepared.
5. the preparation method of high energy storage density barium sodium niobate (BNN) base glass ceramics energy storage material according to claim 4, special
Sign is, controlled at high temperature melting 2-3h at 1500-1550 DEG C in step (1).
6. the preparation method of high energy storage density barium sodium niobate (BNN) base glass ceramics energy storage material according to claim 4, special
Sign is that copper mould preheating temperature described in step (2) is 600-650 DEG C.
7. the preparation method of high energy storage density barium sodium niobate (BNN) base glass ceramics energy storage material according to claim 4, special
Sign is that high temperature molten slurry described in step (2) keeps 5-6h in copper mould.
8. the preparation method of high energy storage density barium sodium niobate (BNN) base glass ceramics energy storage material according to claim 4, special
Sign is that it is 5 DEG C/min that step (4), which carries out control heating rate when Controlled Crystallization, is warming up to 850 DEG C of isothermal holding 5h.
9. the application of high energy storage density barium sodium niobate (BNN) base glass ceramics energy storage material as described in claim 1, which is characterized in that
The barium sodium niobate (BNN) base glass ceramics energy storage material dielectric constant and energy storage density for the high energy storage density being prepared are high, discharge power
Density and energy density are high, and temperature stability is good, and resistance to sparking can be high, are used as energy-storage capacitor material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811528685.1A CN109467313A (en) | 2018-12-13 | 2018-12-13 | High energy storage density barium sodium niobate (BNN) base glass ceramics energy storage material and its preparation and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811528685.1A CN109467313A (en) | 2018-12-13 | 2018-12-13 | High energy storage density barium sodium niobate (BNN) base glass ceramics energy storage material and its preparation and application |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109467313A true CN109467313A (en) | 2019-03-15 |
Family
ID=65675145
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811528685.1A Pending CN109467313A (en) | 2018-12-13 | 2018-12-13 | High energy storage density barium sodium niobate (BNN) base glass ceramics energy storage material and its preparation and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109467313A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114685050A (en) * | 2022-04-28 | 2022-07-01 | 电子科技大学 | High-energy-storage-efficiency silicon niobate microcrystalline glass material and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6130178A (en) * | 1998-04-16 | 2000-10-10 | Corning Incorporated | Strong miserite glass-ceramics |
| CN102046551A (en) * | 2008-05-27 | 2011-05-04 | 默克专利股份有限公司 | Glass-ceramic discs for use in pigments |
| CN103723925A (en) * | 2012-10-10 | 2014-04-16 | 株式会社小原 | Crystallized glass and method for manufacturing same |
| CN106865989A (en) * | 2017-01-06 | 2017-06-20 | 陕西科技大学 | The KNN base energy storage microcrystal glass materials and preparation method of a kind of ultralow dielectric loss |
| CN108395106A (en) * | 2018-04-23 | 2018-08-14 | 同济大学 | Lead bariun niobate sodium base glass ceramic material of high energy storage density and preparation method thereof |
-
2018
- 2018-12-13 CN CN201811528685.1A patent/CN109467313A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6130178A (en) * | 1998-04-16 | 2000-10-10 | Corning Incorporated | Strong miserite glass-ceramics |
| CN102046551A (en) * | 2008-05-27 | 2011-05-04 | 默克专利股份有限公司 | Glass-ceramic discs for use in pigments |
| CN103723925A (en) * | 2012-10-10 | 2014-04-16 | 株式会社小原 | Crystallized glass and method for manufacturing same |
| CN106865989A (en) * | 2017-01-06 | 2017-06-20 | 陕西科技大学 | The KNN base energy storage microcrystal glass materials and preparation method of a kind of ultralow dielectric loss |
| CN108395106A (en) * | 2018-04-23 | 2018-08-14 | 同济大学 | Lead bariun niobate sodium base glass ceramic material of high energy storage density and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| SHUANGXI XUE ER AL.: "Effect of the Ba/Na ratio on the microstructure and dielectric properties of (BaO, Na2O)–Nb2O5–SiO2 glass–ceramics", 《CERAMICS INTERNATIONAL》 * |
| WANG,SHUJIAN ET AL.: "Crystallization kinetics behavior and dielectric energy storage properties of strontium potassium niobate glass-ceramics with different nucleating agents", 《CERAMICS INTERNATIONAL》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114685050A (en) * | 2022-04-28 | 2022-07-01 | 电子科技大学 | High-energy-storage-efficiency silicon niobate microcrystalline glass material and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108395106B (en) | Barium niobate lead sodium based glass ceramic material with high energy storage density and preparation method thereof | |
| CN102260044B (en) | Energy storage niobate microcrystalline glass dielectric material and preparation method thereof | |
| WO2018010633A1 (en) | Cbs-class ltcc material and manufacturing method thereof | |
| CN103342466A (en) | strontium barium niobate based glass-ceramic dielectric material and preparation method thereof | |
| CN105271761A (en) | High-energy-density niobate-based glass ceramic energy storage material and preparation and application thereof | |
| CN110451807A (en) | The bismuth niobate barium sodium base glass ceramic material of high energy storage density and its preparation and application | |
| CN107963890B (en) | Preparation method of titanium nitride porous conductive ceramic | |
| CN105418068A (en) | Novel niobate-base glass ceramic energy-storing material and preparation method and application thereof | |
| CN110240409A (en) | Lead bariun niobate sodium base glass ceramic material of high energy storage density and preparation method thereof | |
| CN109321979A (en) | Barium strontium titanate monocrystalline and preparation method | |
| CN105948737A (en) | Novel CaTiO3-based linear energy-storage-medium ceramic material and preparation method thereof | |
| CN109467313A (en) | High energy storage density barium sodium niobate (BNN) base glass ceramics energy storage material and its preparation and application | |
| CN111153694A (en) | Microwave dielectric ceramic material and preparation method thereof | |
| CN110407579B (en) | Microwave dielectric material with ultrahigh Q value and preparation method thereof | |
| CN108585515B (en) | Bismuth niobate-based glass ceramic material with high energy storage density and preparation method and application thereof | |
| CN109305811A (en) | A kind of microwave-assisted zinc oxide ceramics sintering method | |
| CN105800939B (en) | Devitrified glass of nearly zero-temperature coefficient and preparation method thereof | |
| CN105399333A (en) | Strontium barium niobate-based glass ceramic energy storage material and preparation method thereof | |
| CN100551824C (en) | The preparation method of modified Nano boron oxide | |
| CN104788094A (en) | Preparation method for bismuth titanate ceramic material | |
| CN112079631B (en) | Low-dielectric LTCC material with near-zero temperature coefficient and preparation method thereof | |
| Wang et al. | A new strategy to realize phase structure and morphology of BaTiO3 nanowires controlled in ZnO-B2O3-SiO2 glass | |
| CN106495171A (en) | A kind of LaxBa2‑xTiSi2O8Amorphous and preparation method thereof | |
| Wang et al. | Synthesis and microwave dielectric properties of CaO–MgO–SiO2 submicron powders doped with Li2O–Bi2O3 by sol–gel method | |
| Han et al. | Crystallization kinetics and the dielectric properties of SrO-BaO-Nb 2 O 5-B 2 O 3 glass-ceramics |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20190315 |