CN108585515A - Niobic acid bismuthino glass ceramic material of high energy storage density and its preparation method and application - Google Patents
Niobic acid bismuthino glass ceramic material of high energy storage density and its preparation method and application Download PDFInfo
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- CN108585515A CN108585515A CN201810437270.7A CN201810437270A CN108585515A CN 108585515 A CN108585515 A CN 108585515A CN 201810437270 A CN201810437270 A CN 201810437270A CN 108585515 A CN108585515 A CN 108585515A
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- 238000004146 energy storage Methods 0.000 title claims abstract description 72
- 239000002253 acid Substances 0.000 title claims abstract description 27
- -1 bismuthino Chemical group 0.000 title claims abstract description 25
- 239000006112 glass ceramic composition Substances 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 238000002425 crystallisation Methods 0.000 claims abstract description 23
- 230000004927 fusion Effects 0.000 claims abstract description 12
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 11
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical group [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000000203 mixture Substances 0.000 claims abstract description 7
- 239000000126 substance Substances 0.000 claims abstract description 7
- 239000011521 glass Substances 0.000 claims description 57
- 230000008025 crystallization Effects 0.000 claims description 20
- 238000010438 heat treatment Methods 0.000 claims description 16
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Inorganic materials O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 claims description 16
- 239000000463 material Substances 0.000 claims description 14
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 11
- 229910052681 coesite Inorganic materials 0.000 claims description 11
- 229910052802 copper Inorganic materials 0.000 claims description 11
- 239000010949 copper Substances 0.000 claims description 11
- 229910052906 cristobalite Inorganic materials 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
- 239000000377 silicon dioxide Substances 0.000 claims description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 11
- 239000002002 slurry Substances 0.000 claims description 11
- 229910052682 stishovite Inorganic materials 0.000 claims description 11
- 229910052905 tridymite Inorganic materials 0.000 claims description 11
- 239000003990 capacitor Substances 0.000 claims description 10
- 238000010792 warming Methods 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 8
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(iii) oxide Chemical compound O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 claims description 6
- 238000004321 preservation Methods 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 5
- 239000002241 glass-ceramic Substances 0.000 description 38
- 239000011232 storage material Substances 0.000 description 14
- 239000000919 ceramic Substances 0.000 description 8
- 238000001953 recrystallisation Methods 0.000 description 8
- 238000002844 melting Methods 0.000 description 6
- 230000008018 melting Effects 0.000 description 6
- 239000010955 niobium Substances 0.000 description 6
- 238000011160 research Methods 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 238000000137 annealing Methods 0.000 description 5
- 238000000498 ball milling Methods 0.000 description 5
- 230000015556 catabolic process Effects 0.000 description 5
- 238000000227 grinding Methods 0.000 description 5
- 238000011056 performance test Methods 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- 229910001632 barium fluoride Inorganic materials 0.000 description 3
- 239000006121 base glass Substances 0.000 description 3
- 229910010293 ceramic material Inorganic materials 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- WOIHABYNKOEWFG-UHFFFAOYSA-N [Sr].[Ba] Chemical compound [Sr].[Ba] WOIHABYNKOEWFG-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive 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
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000011835 investigation Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229910052573 porcelain Inorganic materials 0.000 description 2
- 229910000906 Bronze Inorganic materials 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 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 description 1
- 229910019695 Nb2O6 Inorganic materials 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229910010252 TiO3 Inorganic materials 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052454 barium strontium titanate Inorganic materials 0.000 description 1
- 229910002113 barium titanate Inorganic materials 0.000 description 1
- 239000010974 bronze Substances 0.000 description 1
- 239000002419 bulk glass Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- CMIHHWBVHJVIGI-UHFFFAOYSA-N gadolinium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Gd+3].[Gd+3] CMIHHWBVHJVIGI-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- UYLYBEXRJGPQSH-UHFFFAOYSA-N sodium;oxido(dioxo)niobium Chemical compound [Na+].[O-][Nb](=O)=O UYLYBEXRJGPQSH-UHFFFAOYSA-N 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 229910000018 strontium carbonate Inorganic materials 0.000 description 1
- LEDMRZGFZIAGGB-UHFFFAOYSA-L strontium carbonate Chemical compound [Sr+2].[O-]C([O-])=O LEDMRZGFZIAGGB-UHFFFAOYSA-L 0.000 description 1
- 230000005619 thermoelectricity Effects 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 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
- C03C10/0009—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition containing silica as main constituent
-
- 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
-
- 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
- H01G4/10—Metal-oxide dielectrics
- H01G4/105—Glass dielectric
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Ceramic Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Power Engineering (AREA)
- Thermal Sciences (AREA)
- Dispersion Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Glass Compositions (AREA)
Abstract
The present invention relates to niobic acid bismuthino glass ceramic materials of a kind of high energy storage density and its preparation method and application, and the chemical composition of niobic acid bismuthino glass ceramic material meets general formula 25Bi2O3‑25Nb2O5‑50SiO2, principal crystalline phase is bismuth niobate；Preparation method is prepared using high-temperature fusion Controlled Crystallization method.Compared with prior art, the advantages that present invention has energy storage density higher, and temperature stability is preferable, and preparation method is simple, feature at low cost, follow-up study application potential is larger.
Description
Technical field
The present invention relates to field of dielectric energy storage material, make pottery more particularly, to a kind of niobic acid bi-based glass of high energy storage density
Ceramic material and preparation method thereof.
Background technology
In recent years, step-by-step counting has been widely used for electrometer as the important component in various electronic systems
Calculate it is mechanical, electrical depending on, communicate, radar, remote control observing and controlling, automatically control, the fields such as radionavigation and measuring technique.Pulse technique refers to
More than hundred megawatts (MW), short time energy of the pulse width less than 1s discharges power.Pulse power device can be reduced to, first
The electric energy of low-power is stored in energy storage device, such as capacitor, when the energy of storage is reached with designated value, passes through charge and discharge
Electric circuit conversion quickly releases the energy of storage, within the extremely short time to achieve the purpose that high current, high-power output.
The quality of pulse power system is evaluated mainly there are two parameter, when the size of its reservoir energy, second is that its charge/discharge rates
Speed.Since current practical energy storage material energy storage density is relatively low so that pulse power system volume is excessively huge, the day of one's doom
The application of this technology is made.Therefore, the energy storage material for finding the stabilization with high energy storage density is that scientific research personnel is total to instantly
Know.
Glass ceramics energy storage material, using the method for high-temperature fusion, the melting sources of specific proportioning will be prepared glass by head
Then obtained molten slurry chilling is obtained the unformed both bulk glasses of uniform component by glass molten slurry, finally, pass through the side of controllable crystallization
Method prepares the imporous glass-ceramic of the crystalline phase particle and remaining glass phase composition of sub-micron or nano-scale.Can
Control Crystallization Process in, by adjusting generate ceramic phase metal oxide and glass phase Network former relative scale and after
The control of continuous crystallization treatment process, may be implemented to crystalline phase particle size, effective control of form and content ensures that glass
The performance of glass ceramic material has larger adjustability.It is this to have by the high-temperature fusion glass ceramics that controllable crystallization is prepared again
There is the characteristics of high-compactness, high resistance to breakdown and high energy storage density.In recent years, niobates glass pottery is to study high energy storage both at home and abroad
The thermoelectricity of glass ceramic material.Niobate microcrystalline glass is mainly brilliant by the niobates with tungsten bronze type structure and perovskite structure
The composite material of body and glass phase composition.In niobates glass ceramics system, some scholars optimize it, are mixed accordingly
Miscellaneous study on the modification.The Na of Guo-hua Chen et al. reports2O-BaO-SrO-Nb2O5-B2O3-SiO2Glass ceramics reaches
4.0J/cm3Energy storage density.Yi Zhou et al. BaO-Na2O-Nb2O5-SiO2Component on the basis of be added to Gd2O3, as a result show
Show, is added to the Gd of 1% mole2O3Significantly improve the dielectric property of glass ceramics, resistance to disruptive field intensity and dielectric constant point
349 and 56.16kV/mm.Jun Song etc. are not reached with BaCO3, SrCO3, Nb2O5, H3BO3For raw material, different Sr/ are had studied
Ba compares the influence of glass ceramics dielectric properties.M.P.Graca etc. has studied heat treatment to SiO2-Na2O-Nb2O5It is glass pottery
The influence of the electricity and dielectric properties of porcelain, the study found that group becomes 60SiO2-30Na2O-10Nb2O5The glass of system is 650
DEG C heat treatment 4h, material dielectric constant is up to 48.19.Shyu etc. prepares strontium barium niobate base glass pottery by whole crystallization method
Porcelain is increased with sintering temperature, and SBN phase contents increase, and is calculated analysis crystal content and is up to 40%, dielectric constant is up to 180.Then
(SrO, the BaO)-Nb studied again2O5System glass ceramics, it is found that when recrystallization temperature is less than 1000 DEG C, the dielectric constant of sample is high
Up to 351, breakdown strength is up to 4.5kV/cm, 0.15 μ C/cm of remanent polarization2.Then, Zeng et al. studies BaF2Additive
To SrO-BaO-Nb2O5-B2O3The precipitation behaviour of glass and the influence of dielectric properties, find the dielectric of the system devitrified glass
Constant is with BaF2The variation of reduction after first increase is presented in the increase of additive amount, and the trend to become larger always occurs in resistance to breakdown.When adding
Add 5mol%BaF2When, it is 337 to obtain dielectric constant, and resistance to disruptive field intensity is the devitrified glass ceramics of 527kV/cm optimal performances.
Jun Luo et al. are based on Na2O-PbO-Nb2O5-SiO2Glass ceramics system successfully prepares the multilayered structure electricity of function admirable
Container, energy storage density reach 8J/cm3。
In previous research, for glass phase in glass ceramics raw material mainly using such as barium, potassium, sodium, strontium etc.
The oxide or hydrocarbon of element, finally obtained glass ceramics crystalline phase is mostly made of these elements and niobium, oxygen, such as metatitanic acid
Barium (BaTiO3), strontium barium niobate (SrxBa1-xNb2O6), barium strontium titanate (SrxBa1-xTiO3), sodium niobate (NaNbO3) etc., through excessive
Year research, the development of energy storage density is already close to bottleneck stage, in this context, attempt exploitation it is new have high energy storage close
The material system of degree seems particularly necessary.
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
Niobic acid bismuthino glass ceramic material and its preparation method and application.
The purpose of the present invention can be achieved through the following technical solutions：
A kind of niobic acid bismuthino glass ceramic material of high energy storage density, chemical composition meet general formula 25Bi2O3-
25Nb2O5-50SiO2, principal crystalline phase is bismuth niobate.
The preparation method of the niobic acid bismuthino glass ceramic material of the high energy storage density, includes the following steps：
(1) with Bi2O3、Nb2O5And SiO2For raw material, according to 25Bi2O3-25Nb2O5-50SiO2Mole chemical ratio dispensing,
After mixing, high-temperature fusion obtains high temp glass molten slurry for barreling；
(2) high temp glass molten slurry prepared by step (1) is poured into the copper mould of preheating and is molded and keeps the preheating temperature
To remove the residual stress in glass, the glass of the amorphous state of uniform component is prepared, glass flake is obtained after slice；
(3) glass flake made from step (2) is subjected to Controlled Crystallization, obtains the bismuth niobate of the high energy storage density
Base glass ceramic material.
Preferably, the process conditions of step (1) high-temperature fusion are：1~3h is kept the temperature at 1500~1600 DEG C.
Preferably, the process conditions of step (1) high-temperature fusion are：2h is kept the temperature at 1550 DEG C.
Preferably, in step (2), high temp glass molten slurry prepared by step (1) is poured into and is preheated in 600 DEG C of copper mould
It is molded and keeps preheating temperature 6h to remove the residual stress in glass.
Preferably, the condition of Controlled Crystallization is in step (3)：With the heating rate of 2~4 DEG C/min be warming up to 700 DEG C~
900 DEG C, keep the temperature 4~8h.
Preferably, the condition of Controlled Crystallization is in step (3)：700~900 DEG C are warming up to the heating rate of 3 DEG C/min,
Keep the temperature 6h.
Preferably, the condition of best Controlled Crystallization is in step (3)：800 DEG C are warming up to the heating rate of 3 DEG C/min,
Keep the temperature 6h.
The application of the niobic acid bismuthino glass ceramic material of the high energy storage density, can be used as energy-storage capacitor material.
The present invention is based on 25Bi2O3-25Nb2O5-50SiO2(mole %) dispensing, by adjusting the glass after recrystallization temperature
Ceramics, dielectric constant are kept at a higher level with resistance to disruptive field intensity.Particularly, when recrystallization temperature is 800 DEG C, storage
Energy density reaches maximum value, and theoretical energy storage density reaches 17.16J/cm3。
Compared with prior art, the present invention has the following advantages：
(1) the present invention relates to a kind of bismuth-containing, molar composition ratio 25Bi2O3-25Nb2O5-50SiO2Component, comparison
The research about glass ceramics before is clearly distinguishable from common glass as the glass ceramics of glass ceramics principal crystalline phase using bismuth niobate
Glass ceramics crystalline phase, and energy storage density value is larger, can be used for making high density capacitors, can subsequently continue on this basis
Expansion is to using bismuth niobate as the research of the glass ceramics of principal crystalline phase, there is larger further investigation value to anticipate with practical application
Justice.
(2) preparation method is simple, and temperature stability is good, and processability is good, and crystalline range is wide.
The present invention is based on 25Bi2O3-25Nb2O5-50SiO2(mole %) dispensing, has successfully been precipitated using bismuth niobate as principal crystalline phase
Glass ceramics, and energy storage density is big, can be used for making high density capacitors, can subsequently continue to be unfolded on this basis
To using bismuth niobate as the research of the glass ceramics of principal crystalline phase, there is larger further investigation value and practical application meaning.
Description of the drawings
Fig. 1 is 25Bi under different recrystallization temperatures2O3-25Nb2O5-50SiO2The energy storage of (mole %) glass ceramics energy storage material
Density；
Fig. 2 is 25Bi under different recrystallization temperatures2O3-25Nb2O5-50SiO2The dielectric of (mole %) glass ceramics energy storage material
Constant；
Fig. 3 is 25Bi under different recrystallization temperatures2O3-25Nb2O5-50SiO2(mole %) the resistance to of glass ceramics energy storage material hits
Wear the Weibull profile curves of field strength；
Fig. 4 is 25Bi under different recrystallization temperatures2O3-25Nb2O5-50SiO2The XRD of (mole %) glass ceramics energy storage material
Spectrogram；
Fig. 5 (a)~(e) is 25Bi under Examples 1 to 5 difference recrystallization temperature2O3-25Nb2O5-50SiO2(mole %) glass
The SEM image of ceramic energy storage material.
Specific implementation mode
A kind of niobic acid bismuthino glass ceramic material of high energy storage density, chemical composition meet general formula 25Bi2O3-
25Nb2O5-50SiO2, principal crystalline phase is bismuth niobate.
The preparation method of the niobic acid bismuthino glass ceramic material of above-mentioned high energy storage density, includes the following steps：
(1) with Bi2O3、Nb2O5And SiO2For raw material, according to 25Bi2O3-25Nb2O5-50SiO2Mole chemical ratio dispensing,
After mixing, high-temperature fusion obtains high temp glass molten slurry for barreling；
(2) high temp glass molten slurry prepared by step (1) is poured into the copper mould of preheating and is molded and keeps the preheating temperature
To remove the residual stress in glass, the glass of the amorphous state of uniform component is prepared, glass flake is obtained after slice；
(3) glass flake made from step (2) is subjected to Controlled Crystallization, obtains the bismuth niobate of the high energy storage density
Base glass ceramic material.
The process conditions of preferred steps (1) high-temperature fusion are：1~3h is kept the temperature at 1500~1600 DEG C.Further preferably
The process conditions of step (1) high-temperature fusion are：2h is kept the temperature at 1550 DEG C.
Preferably, in step (2), high temp glass molten slurry prepared by step (1) is poured into and is preheated in 600 DEG C of copper mould
It is molded and keeps preheating temperature 6h to remove the residual stress in glass.
The condition of Controlled Crystallization is in preferred steps (3)：It is warming up to 700 DEG C~900 with the heating rate of 2~4 DEG C/min
DEG C, keep the temperature 4~8h.The condition of Controlled Crystallization is in further preferred step (3)：It is warming up to 700 with the heating rate of 3 DEG C/min
~900 DEG C, keep the temperature 6h.The condition of best Controlled Crystallization is still more preferably in step (3)：With the heating rate of 3 DEG C/min
800 DEG C are warming up to, 6h is kept the temperature.
The present invention is described in detail with specific embodiment below in conjunction with the accompanying drawings.
Embodiment 1
The preparation method of the niobic acid bismuthino glass ceramics energy storage material of high energy storage density, includes the following steps：
(1) it is more than the Bi of 99wt% with purity2O3, Nb2O5, SiO2Molar percentage for feed proportioning, each component is
25%, 25%, 50% through ball mill mixing for 24 hours, after being dried 6 hours at 120 DEG C, in 1550 DEG C of high temperature melting 2h；(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 3 DEG C/min
To after 700 DEG C, heat preservation 6h obtains glass ceramics.
The energy storage density of sample obtained by the present embodiment is as shown in Figure 1, its energy storage density is 13.41J/cm3, can apply
In energy-storage capacitor material.Dielectric properties are as shown in Fig. 2, be 67；Pressure-resistant performance test is as shown in figure 3, be 2126kV/cm；XRD
As shown in figure 4, the crystalline phase being wherein precipitated is α ﹣ BiNbO4, shown in SEM such as Fig. 5 (a).Glass ceramics microscopic appearance is found by SEM
It is very fine and close, and after crystallization, ceramic phase and residual glass phase form void-free structure, make it have higher breakdown field
By force.
Embodiment 2
The preparation method of the niobic acid bismuthino glass ceramics energy storage material of high energy storage density, includes the following steps
(1) it is more than the Bi of 99wt% with purity2O3, Nb2O5, SiO2Molar percentage for feed proportioning, each component is
25%, 25%, 50% through ball mill mixing for 24 hours, after being dried 6 hours at 120 DEG C, in 1550 DEG C of high temperature melting 2h；(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 3 DEG C/min
To after 750 DEG C, heat preservation 6h obtains glass ceramics.
The energy storage density of sample obtained by the present embodiment is as shown in Figure 1, its energy storage density is 15.13J/cm3, can apply
In energy-storage capacitor material.Dielectric properties are as shown in Fig. 2, be 84；Pressure-resistant performance test is as shown in figure 3, be 2017kV/cm；XRD
As shown in Figure 4, wherein the crystalline phase being precipitated is α ﹣ BiNbO4, shown in SEM such as Fig. 5 (b).Glass ceramics microscopic appearance is found by SEM
It is very fine and close, and after crystallization, ceramic phase mutually forms void-free structure with glass, makes it have higher disruptive field intensity.
Embodiment 3
The preparation method of the niobic acid bismuthino glass ceramics energy storage material of high energy storage density, includes the following steps：
(1) it is more than the Bi of 99wt% with purity2O3, Nb2O5, SiO2Molar percentage for feed proportioning, each component is
25%, 25%, 50% through ball mill mixing for 24 hours, after being dried 6 hours at 120 DEG C, in 1550 DEG C of high temperature melting 2h；(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 3 DEG C/min
To after 800 DEG C, heat preservation 6h obtains glass ceramics.
The energy storage density of sample obtained by the present embodiment is as shown in Figure 1, its energy storage density is 17.16J/cm3, can apply
In energy-storage capacitor material.Dielectric properties are as shown in Fig. 2, be 121；Pressure-resistant performance test is as shown in figure 3, be 1790kV/cm；
XRD is as shown in Figure 4, wherein the crystalline phase being precipitated is β ﹣ BiNbO4, shown in SEM such as Fig. 5 (c).The microcosmic shape of glass ceramics is found by SEM
Looks are very fine and close, and after crystallization, and ceramic phase mutually forms void-free structure with glass, make it have higher breakdown field
By force.
Embodiment 4
The preparation method of the niobic acid bismuthino glass ceramics energy storage material of high energy storage density, includes the following steps：
(1) it is more than the Bi of 99wt% with purity2O3, Nb2O5, SiO2Molar percentage for feed proportioning, each component is
25%, 25%, 50% through ball mill mixing for 24 hours, after being dried 6 hours at 120 DEG C, in 1550 DEG C of high temperature melting 2h；(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 3 DEG C/min
To after 850 DEG C, heat preservation 6h obtains glass ceramics.
The energy storage density of sample obtained by the present embodiment is as shown in Figure 1, its energy storage density is 9.54J/cm3, can apply
In energy-storage capacitor material.Dielectric properties are as shown in Fig. 2, be 89；Pressure-resistant performance test is as shown in figure 3, be 1556kV/cm；XRD
As shown in Figure 4, wherein the crystalline phase being precipitated is β ﹣ BiNbO4, shown in SEM such as Fig. 5 (d).Glass ceramics microscopic appearance is found by SEM
It is very fine and close, and after crystallization, ceramic phase mutually forms void-free structure with glass, makes it have higher disruptive field intensity.
Embodiment 5
The preparation method of the niobic acid bismuthino glass ceramics energy storage material of high energy storage density, includes the following steps：
(1) it is more than the Bi of 99wt% with purity2O3, Nb2O5, SiO2Molar percentage for feed proportioning, each component is
25%, 25%, 50% through ball mill mixing for 24 hours, after being dried 6 hours at 120 DEG C, in 1550 DEG C of high temperature melting 2h；(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 3 DEG C/min
To after 900 DEG C, heat preservation 6h obtains glass ceramics.
The energy storage density of sample obtained by the present embodiment is as shown in Figure 1, its energy storage density is 3.62J/cm3, can apply
In energy-storage capacitor material.Dielectric properties are as shown in Fig. 2, be 45；Pressure-resistant performance test is as shown in figure 3, be 1348kV/cm；XRD
As shown in Figure 4, wherein the crystalline phase being precipitated is β ﹣ BiNbO4, shown in SEM such as Fig. 5 (e).Glass ceramics microscopic appearance is found by SEM
It is very fine and close, and after crystallization, ceramic phase mutually forms void-free structure with glass, makes it have higher disruptive field intensity.
The above-mentioned description to embodiment is for ease of ordinary skill in the art to understand and use the invention.It is ripe
The personnel for knowing art technology obviously easily can make various modifications to these embodiments, and general original described herein
It ought to use in other embodiment without having to go through creative labor.Therefore, the present invention is not limited to the above embodiments, this field
Technical staff's announcement according to the present invention, improvement and modification made without departing from the scope of the present invention all should be in the guarantors of the present invention
Within the scope of shield.
Claims (9)
1. a kind of niobic acid bismuthino glass ceramic material of high energy storage density, which is characterized in that its chemical composition meets general formula
25Bi2O3-25Nb2O5-50SiO2, principal crystalline phase is bismuth niobate.
2. the preparation method of the niobic acid bismuthino glass ceramic material of high energy storage density as described in claim 1, which is characterized in that
Include the following steps：
(1) with Bi2O3、Nb2O5And SiO2For raw material, according to 25Bi2O3-25Nb2O5-50SiO2Mole chemical ratio dispensing, barreling
After mixing, high-temperature fusion obtains high temp glass molten slurry；
(2) high temp glass molten slurry prepared by step (1) is poured into the copper mould of preheating and is molded and keeps the preheating temperature to go
Except the residual stress in glass, the glass of the amorphous state of uniform component is prepared, glass flake is obtained after slice；
(3) glass flake made from step (2) is subjected to Controlled Crystallization, obtains the niobic acid bismuthino glass of the high energy storage density
Glass ceramic material.
3. the preparation method of the niobic acid bismuthino glass ceramic material of high energy storage density according to claim 2, feature exist
In the process conditions of step (1) high-temperature fusion are：1~3h is kept the temperature at 1500~1600 DEG C.
4. the preparation method of the niobic acid bismuthino glass ceramic material of high energy storage density according to claim 3, feature exist
In the process conditions of step (1) high-temperature fusion are：2h is kept the temperature at 1550 DEG C.
5. the preparation method of the niobic acid bismuthino glass ceramic material of high energy storage density according to claim 2, feature exist
In in step (2), high temp glass molten slurry prepared by step (1) is poured into be preheated to being molded in 600 DEG C of copper mould and keep this
Preheating temperature 6h is to remove the residual stress in glass.
6. the preparation method of the niobic acid bismuthino glass ceramic material of high energy storage density according to claim 2, feature exist
In the condition of Controlled Crystallization is in step (3)：It is warming up to 700 DEG C~900 DEG C with the heating rate of 2~4 DEG C/min, heat preservation 4~
8h。
7. the preparation method of the niobic acid bismuthino glass ceramic material of high energy storage density according to claim 6, feature exist
In the condition of Controlled Crystallization is in step (3)：700~900 DEG C are warming up to the heating rate of 3 DEG C/min, keeps the temperature 6h.
8. the preparation method of the niobic acid bismuthino glass ceramic material of high energy storage density according to claim 7, feature exist
In the condition of Controlled Crystallization is in step (3)：800 DEG C are warming up to the heating rate of 3 DEG C/min, keeps the temperature 6h.
9. the application of the niobic acid bismuthino glass ceramic material of high energy storage density as described in claim 1, which is characterized in that by it
As energy-storage capacitor material.
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| CN112159110A (en) * | 2020-10-10 | 2021-01-01 | 陕西科技大学 | Energy storage glass ceramic capable of adjusting ferroelectricity by controlling crystallization power, preparation method and application |
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| CN110451807A (en) * | 2019-07-29 | 2019-11-15 | 同济大学 | The bismuth niobate barium sodium base glass ceramic material of high energy storage density and its preparation and application |
| CN110451807B (en) * | 2019-07-29 | 2022-04-05 | 同济大学 | Bismuth barium sodium niobate-based glass ceramic material with high energy storage density and preparation and application thereof |
| CN112159110A (en) * | 2020-10-10 | 2021-01-01 | 陕西科技大学 | Energy storage glass ceramic capable of adjusting ferroelectricity by controlling crystallization power, preparation method and application |
| CN112159110B (en) * | 2020-10-10 | 2022-12-06 | 陕西科技大学 | Energy storage glass ceramic capable of adjusting ferroelectricity by controlling crystallization power, preparation method and application |
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