CN116253516A - Microcrystalline glass material with high energy storage and high optical transmittance and preparation method thereof - Google Patents
Microcrystalline glass material with high energy storage and high optical transmittance and preparation method thereof Download PDFInfo
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- CN116253516A CN116253516A CN202310057777.0A CN202310057777A CN116253516A CN 116253516 A CN116253516 A CN 116253516A CN 202310057777 A CN202310057777 A CN 202310057777A CN 116253516 A CN116253516 A CN 116253516A
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- 239000011521 glass Substances 0.000 title claims abstract description 90
- 239000000463 material Substances 0.000 title claims abstract description 38
- 230000003287 optical effect Effects 0.000 title claims abstract description 20
- 238000002834 transmittance Methods 0.000 title claims abstract description 19
- 238000004146 energy storage Methods 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title abstract description 8
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims abstract description 27
- 229910004298 SiO 2 Inorganic materials 0.000 claims abstract description 27
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 15
- 239000010937 tungsten Substances 0.000 claims abstract description 15
- 229910052709 silver Inorganic materials 0.000 claims abstract description 12
- 229910006404 SnO 2 Inorganic materials 0.000 claims abstract description 10
- 229910010413 TiO 2 Inorganic materials 0.000 claims abstract description 10
- 229910000906 Bronze Inorganic materials 0.000 claims abstract description 8
- 239000010974 bronze Substances 0.000 claims abstract description 8
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 claims abstract description 8
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 3
- 229910052718 tin Inorganic materials 0.000 claims abstract description 3
- 239000007788 liquid Substances 0.000 claims description 19
- 239000013078 crystal Substances 0.000 claims description 18
- 238000000137 annealing Methods 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 16
- 239000002994 raw material Substances 0.000 claims description 13
- 229910052751 metal Inorganic materials 0.000 claims description 12
- 239000002184 metal Substances 0.000 claims description 12
- 238000002425 crystallisation Methods 0.000 claims description 9
- 230000008025 crystallization Effects 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- 238000000465 moulding Methods 0.000 claims description 8
- 238000005498 polishing Methods 0.000 claims description 8
- 238000012545 processing Methods 0.000 claims description 8
- 239000006112 glass ceramic composition Substances 0.000 claims description 5
- 238000004321 preservation Methods 0.000 claims description 4
- 230000010287 polarization Effects 0.000 abstract description 7
- 230000005684 electric field Effects 0.000 abstract description 2
- 238000012360 testing method Methods 0.000 description 20
- 239000003989 dielectric material Substances 0.000 description 16
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 8
- 239000004332 silver Substances 0.000 description 8
- 239000002241 glass-ceramic Substances 0.000 description 7
- 239000000203 mixture Substances 0.000 description 5
- 238000000498 ball milling Methods 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 238000013461 design Methods 0.000 description 4
- 229910052697 platinum Inorganic materials 0.000 description 4
- 238000007650 screen-printing Methods 0.000 description 4
- 238000005245 sintering Methods 0.000 description 4
- 239000000919 ceramic Substances 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000005621 ferroelectricity Effects 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 239000003990 capacitor Substances 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
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Classifications
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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
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P40/00—Technologies relating to the processing of minerals
- Y02P40/50—Glass production, e.g. reusing waste heat during processing or shaping
- Y02P40/57—Improving the yield, e-g- reduction of reject rates
Abstract
The invention discloses a microcrystalline glass material with high energy storage and high optical transmittance and a preparation method thereof, wherein the microcrystalline glass material has a tetragonal tungsten bronze crystalline phase structure or a tetragonal perovskite crystalline phase structure, and the microcrystalline glass material comprises the following components: a is that 2 O‑A′O‑B 2 O 5 ‑B′O 2 ‑Al 2 O 3 ‑SiO 2 And BaO-TiO 2 ‑SnO 2 ‑Al 2 O 3 ‑SiO 2 Wherein A represents K, na or Ag element, A 'represents Ba or Sr element, B represents Nb, ta or P element, and B' represents Ti or Sn element. The invention maintains a lower residual polarization value and an ultra-short discharge time while having a higher electric polarization value under a higher external electric field<20 ns) to realize high power discharge in the glass ceramicsThe rate density and the high stored energy, and has good temperature stability and high optical transmittance.
Description
Technical Field
The invention relates to the technical field of dielectric materials, in particular to a microcrystalline glass material with high energy storage and high optical transmittance and a preparation method thereof.
Background
Among inorganic dielectric materials, dielectric ceramics and glass ceramics are two candidate materials that are primarily used in dielectric energy storage applications. For dielectric ceramic materials, the main advantage is the high polarization value caused by strong ferroelectricity, but the ferroelectric domain inversion can lead to larger remnant polarization and longer discharge time (> 1 [ mu ] s). In addition, its higher porosity and larger grain size result in lower breakdown field strengths, typically less than 400 kV/cm, and thus, it is difficult to achieve both high stored energy and high power density. The microcrystalline glass consists of a high dielectric ceramic phase and a low dielectric glass phase with nanometer and sub-nanometer dimensions, and has good bulk density, proper dielectric constant and high breakdown strength. In addition, due to the existence of the glass phase, the microcrystalline glass has shorter discharge time than ceramic, so that the microcrystalline glass dielectric capacitor is expected to realize higher power density, and has better application prospect in a high-voltage high-power pulse system.
As a medium, glass ceramics generally have a high dielectric constant, which means that ferroelectricity is enhanced, and accordingly, a remnant polarization value is increased, so that stored energy is reduced, and therefore, development of a glass ceramics dielectric material with higher power density and stored energy is important. In addition, the miniaturization development trend of the device requires that the device has multifunctional application prospect, and further, the main body material forming the device has requirements for multiple physical properties. The microcrystalline glass material has extremely high band gap width, which is generally more than 3.0 and eV, so that the microcrystalline glass material not only has good dielectric energy storage property, but also has the characteristic of high optical transmittance, and has great application potential in the aspect of optical device application.
Disclosure of Invention
The invention provides a microcrystalline glass dielectric material with super-cis-electricity characteristics, which has higher electric polarization value and simultaneously keeps lower residual polarization value under higher external electric field, and the discharge time is super-short (< 20 ns), so that high discharge power density and high energy storage energy are realized in microcrystalline glass at the same time, and the microcrystalline glass dielectric material has good temperature stability and high optical transmittance. The invention also provides a preparation method of the microcrystalline glass dielectric material.
The microcrystalline glass material medium material provided by the invention has a tetragonal tungsten bronze crystal phase structure or a tetragonal perovskite crystal phase structure, and the microcrystalline glass material with the tetragonal tungsten bronze crystal phase structure comprises the following components: a is that 2 O-A′O-B 2 O 5 -B′O 2 -Al 2 O 3 -SiO 2 Ratio of each oxide: 0 to 10mol% of A 2 O,15 to 35mol% of A' O,0 to 35mol% of B 2 O 5 0 to 30mol% of B' O 2 5 to 25mol% of Al 2 O 3 0 to 25mol% of SiO 2 The method comprises the steps of carrying out a first treatment on the surface of the Wherein: a represents K, na or Ag element, A 'represents Ba or Sr element, B represents Nb, ta or P element, and B' represents Ti or Sn element. The microcrystalline glass material with the tetragonal perovskite crystal phase structure comprises the following components: baO-TiO 2 -SnO 2 -Al 2 O 3 -SiO 2 Ratio of each oxide: 15-35 mol% of BaO and 0-30 mol% of TiO 2 0 to 30mol% of SnO 2 5 to 25mol% of Al 2 O 3 0 to 25mol% of SiO 2 。
The invention also provides a preparation method of the microcrystalline glass material dielectric material.
The preparation method of the microcrystalline glass material with the tetragonal tungsten bronze crystal phase structure comprises the following steps:
(1) In K 2 CO3、Na 2 CO 3 、Ag 2 O、BaCO 3 、SrCO 3 、Nb 2 O 5 、P 2 O 5 、Ta 2 O 5 、Al 2 O 3 And SiO 2 Raw materials are proportioned according to the proportion of each oxide, then the raw materials are ball-milled for 24 hours in a ball mill by a wet method, dried and placed in a crucible for heat preservation for 2+/-0.5 hours at 1450-1500 ℃ to prepare uniform glass liquid.
(2) And (3) rapidly pouring the obtained glass liquid into a preheated metal mould for molding, annealing in an annealing furnace at 550-570 ℃, and cutting into glass sheets with set areas after stress relief.
(3) And heating the glass sheet at a heating rate of 5 ℃/min, and preserving the temperature for 2+/-0.5 h at 750-830 ℃ to perform crystallization.
(4) And processing the obtained microcrystalline glass material sheet, and polishing the microcrystalline glass material sheet into a sheet with a set thickness.
The preparation method of the microcrystalline glass material with the tetragonal perovskite crystal phase structure comprises the following steps:
(1) In BaCO 3 、TiO 2 、SnO 2 、Al 2 O 3 And SiO 2 Raw materials are proportioned according to the proportion of each oxide, then the raw materials are ball-milled in a ball mill by a wet method, dried and placed in a crucible to be melted into uniform glass liquid after heat preservation for 2+/-0.5 h at 1450-1500 ℃;
(2) Rapidly pouring the obtained glass liquid into a preheated metal mold for molding, annealing in an annealing furnace at 550-650 ℃, and cutting into glass sheets with set areas after stress relief;
(3) Heating the glass sheet at a heating rate of 5 ℃/min, and preserving the temperature for 2+/-0.5 h at 850-950 ℃ for crystallization;
(4) And processing the obtained microcrystalline glass material sheet, and polishing the microcrystalline glass material sheet into a sheet with a set thickness.
The invention has the technical characteristics and effects that:
the invention has a tetragonal tungsten bronze crystal phase structure or a tetragonal perovskite crystal phase structure, and the composition of the tetragonal tungsten bronze crystal phase structure is A 2 O-A′O-B 2 O 5 -B′O 2 -Al 2 O 3 -SiO 2 Is prepared by a high-temperature melting-controllable crystallization method. Wherein A is 2 O and A' O provide corresponding ions for A-site substitution modulation of microcrystalline glass, B 2 O 5 B' O 2 Providing corresponding ions for B-site substitution modulation of microcrystalline glass. The super-cis electric phase composite structure is realized by separating out microcrystalline glass with a tetragonal tungsten bronze structure or a perovskite structure and by the occupied modulation of different A/B ions, and finally the high-power (more than 500 MW/cm) is obtained 3 ) High storage energy density (> 3.0J/cm) 3 ) High temperature stability (25-120)The super-cis electric structure microcrystalline glass dielectric material with the energy storage density reduced by less than 15 percent and high optical transmittance (the optical transmittance is more than 50 percent in the visible light range) can be applied to a high-voltage high-power pulse power supply system in a multi-temperature environment. In addition, the microcrystalline glass does not contain lead, so that the aim of environmental protection is fulfilled.
Description of the drawings:
FIG. 1 is a graph showing measured discharge energy density and power density of example 1;
FIG. 2 shows the measured discharge energy density temperature stability of example 1;
FIG. 3 depicts the optical transmittance of example 1;
FIG. 4 is a graph showing measured discharge energy density and power density of example 2;
FIG. 5 depicts the optical transmittance of example 2;
FIG. 6 is a graph showing measured discharge energy density and power density of example 3;
FIG. 7 depicts the optical transmittance of example 3;
FIG. 8 is the measured discharge energy density and power density of example 4;
FIG. 9 is a graph showing measured discharge energy density temperature stability of example 4;
fig. 10 depicts the optical transmittance of example 4.
Detailed Description
The following examples are given to illustrate the practice of the invention and the benefits obtained.
Example 1:
the composition design of the product of this example is K 2 O-BaO-SrO-Nb 2 O 5 -Ta 2 O 5 -Al 2 O 3 -SiO 2 The precipitated crystal phase is a tetragonal phase tungsten bronze structure.
(1) To analytically pure K 2 CO 3 、BaCO 3 、SrCO 3 、Nb 2 O 5 、Ta 2 O 5 、Al 2 O 3 And SiO 2 As a starting material, according to 10mol% K 2 CO 3 -7mol%BaCO 3 -16mol%SrCO 3 -34mol%Nb 2 O 5 -4mol%Ta 2 O 5 -15mol%Al 2 O 3 -14mol%SiO 2 The raw materials are subjected to wet ball milling for 24 hours in a ball mill, dried and placed in a crucible for 2.0 hours at 1450 ℃ to be melted into uniform glass liquid.
(2) Rapidly pouring the glass liquid obtained in the step 1 into a metal mold for molding, then annealing 6 h in an annealing furnace at 550 ℃ to eliminate stress, and then cutting into the glass liquid with the area of 1-2 cm 2 Is provided.
(3) Heating the glass sheet prepared in the step 2 at a heating rate of 5 ℃/min, and crystallizing at a crystallization temperature of 830 ℃ for 2 hours to obtain a tungsten bronze structure (KBASrNb 5 O 15 ) Is a glass ceramic dielectric material.
(4) And (3) processing the microcrystalline glass material sheet obtained in the step (3) and polishing the microcrystalline glass material sheet into a sheet with the thickness of 0.05-1 mm.
(5) And (3) carrying out screen printing or manual coating on the microcrystalline glass sheet obtained in the step (4) to obtain medium-temperature silver paste (noble lapping platinum industry), and sintering and curing at 600 ℃ to form a metal silver electrode, thus obtaining the super-cis-electric microcrystalline glass dielectric material capable of carrying out electrical test.
Through test, the measured discharge energy storage density of the obtained microcrystalline glass material can reach 5.46J/cm 3 At 1300, kV/cm, the peak power density can reach 665 MW/cm 3 The energy storage density is reduced by about 14% in the temperature range of 25-120 ℃, and the optical transmittance is more than 55% in the visible light wave band. Test conditions: the charge and discharge test system (voltage 10 kV, load 200 omega, test temperature 25-120 ℃).
Example 2:
the composition design of the product of this example is K 2 O-BaO-SrO-Nb 2 O 5 -Ag 2 O-Al 2 O 3 -SiO 2 The precipitated crystal phase is a tetragonal phase tungsten bronze structure.
(1) To analytically pure K 2 CO 3 、BaCO 3 、SrCO 3 、Nb 2 O 5 、Ag 2 O、Al 2 O 3 And SiO 2 As a starting material, according to 10mol% K 2 CO 3 -11mol%BaCO 3 -11mol%SrCO 3 -34mol%Nb 2 O 5 -1mol%Ag 2 O-15mol%Al 2 O 3 -14mol%SiO 2 The raw materials are subjected to wet ball milling for 24 hours in a ball mill, dried and placed in a crucible for 2.0 hours at 1450 ℃ to be melted into uniform glass liquid.
(2) Rapidly pouring the glass liquid obtained in the step 1 into a metal mold for molding, then annealing 6 h in an annealing furnace at 550 ℃ to eliminate stress, and then cutting into the glass liquid with the area of 1-2 cm 2 Is provided.
(3) Heating the glass sheet prepared in the step 2 at a heating rate of 5 ℃/min, and crystallizing at a crystallization temperature of 750 ℃ for 2 hours to obtain a glass sheet with a main crystal phase of a tungsten bronze structure (KBASrNb 5 O 15 ) Is a glass ceramic dielectric material.
(4) And (3) processing the microcrystalline glass material sheet obtained in the step (3) and polishing the microcrystalline glass material sheet into a sheet with the thickness of 0.08-1 mm.
(5) And (3) carrying out screen printing or manual coating on the microcrystalline glass sheet obtained in the step (4) to obtain medium-temperature silver paste (noble lapping platinum industry), and sintering and curing at 600 ℃ to form a metal silver electrode, thus obtaining the super-cis-electric microcrystalline glass dielectric material capable of carrying out electrical test.
Through test, the room temperature dielectric constant of the obtained microcrystalline glass material reaches 258, and the measured discharge energy storage density can reach 3.62J/cm 3 @800 kV/cm, a peak power density of up to 532MW/cm 3 The optical transmittance of the light source is more than 60% in the visible light wave band. Test conditions: charge and discharge test system (voltage 10 kV, load 200 Ω, test temperature 25 ℃).
Example 3:
the composition design of the product of this example is K 2 O-BaO-Nb 2 O 5 -P 2 O 5 -Al 2 O 3 -SiO 2 The precipitated crystal phase is a tetragonal phase tungsten bronze structure.
(1) To analytically pure K 2 CO 3 、BaCO 3 、Nb 2 O 5 、P 2 O 5 、Al 2 O 3 And SiO 2 As a starting material, according to 12mol% K 2 CO 3 -15mol%BaCO 3 -33mol%Nb 2 O 5 -12molP 2 O 5 -8mol%Al 2 O 3 -20mol%SiO 2 The raw materials are subjected to wet ball milling for 24 hours in a ball mill, dried and placed in a crucible to be melted into uniform glass liquid at 1500 ℃ for 2.0 hours.
(2) Rapidly pouring the glass liquid obtained in the step 1 into a metal mold for molding, then annealing 6 h in an annealing furnace at 560 ℃ to eliminate stress, and then cutting into 1-2 cm in area 2 Is provided.
(3) Heating the glass sheet prepared in the step 2 at a heating rate of 5 ℃/min, and crystallizing at a crystallization temperature of 860 ℃ for 2 hours to obtain a tungsten bronze structure (KBASrNb 5 O 15 ) Is a glass ceramic dielectric material.
(4) And (3) processing the microcrystalline glass material sheet obtained in the step (3) and polishing the microcrystalline glass material sheet into a sheet with the thickness of 0.08-1 mm.
(5) And (3) carrying out screen printing or manual coating on the microcrystalline glass sheet obtained in the step (4) to obtain medium-temperature silver paste (noble lapping platinum industry), and sintering and curing at 600 ℃ to form a metal silver electrode, thus obtaining the super-cis-electric microcrystalline glass dielectric material capable of carrying out electrical test.
Through test, the room temperature dielectric constant of the obtained glass ceramic material reaches 176, and the measured discharge energy storage density can reach 4.45J/cm 3 @800 kV/cm, peak power densities of up to 795 MW/cm 3 The optical transmittance of the light source is more than 50% in the visible light wave band. Test conditions: charge and discharge test system (voltage 10 kV, load 200 Ω, test temperature 25 ℃).
Example 4:
the composition design of the product of this example was BaO-TiO 2 -SnO 2 -Al 2 O 3 -SiO 2 The precipitated crystal phase is a tetragonal perovskite structure.
(1) In analytical pure BaCO (purity not less than 99%) 3 、TiO 2 、SnO 2 、Al 2 O 3 And SiO 2 As a raw material, according to 30mol% BaCO 3 -25mol%TiO 2 -5mol%SnO 2 -18mol%Al 2 O 3 -22mol%SiO 2 The raw materials are subjected to wet ball milling for 24 hours in a ball mill, dried and placed in a crucible to be melted into uniform glass liquid at 1500 ℃ for 2.0 hours.
(2) Rapidly pouring the glass liquid obtained in the step 1 into a metal mold for molding, then annealing 6 h in an annealing furnace at 600 ℃ to eliminate stress, and then cutting into the glass liquid with the area of 1-2 cm 2 Is provided.
(3) Heating the glass sheet prepared in the step 2 at a heating rate of 5 ℃/min, and crystallizing at a crystallization temperature of 900 ℃ for 2 hours to obtain a perovskite structure (BaTiO) as a main crystal phase 3 ) Is a glass ceramic dielectric material.
(4) And (3) processing the microcrystalline glass material sheet obtained in the step (3) and polishing the microcrystalline glass material sheet into a sheet with the thickness of 0.05-1 mm.
(5) And (3) carrying out screen printing or manual coating on the microcrystalline glass sheet obtained in the step (4) to obtain medium-temperature silver paste (noble lapping platinum industry), and sintering and curing at 600 ℃ to form a metal silver electrode, thus obtaining the super-cis-electric microcrystalline glass dielectric material capable of carrying out electrical test.
Through test, the measured discharge energy storage density of the obtained microcrystalline glass material can reach 9.06J/cm 3 At 1500 kV/cm, the power density can reach 1038 MW/cm 3 The energy storage density is reduced by about 8% in the temperature range of 25-120 ℃, and the optical transmittance is more than 60% in the visible light wave band. Test conditions: the charge and discharge test system (voltage 10 kV, load 200 omega, test temperature 25-120 ℃).
Claims (4)
1. The microcrystalline glass material with high energy storage and high optical transmittance is characterized by having a tetragonal tungsten bronze crystalline phase structure, and comprises the following components: a is that 2 O-A′O-B 2 O 5 -B′O 2 -Al 2 O 3 -SiO 2 ,
Ratio of each oxide: 0 to 10mol% of A 2 O,15 to 35mol% of A' O,0 to 35mol% of B 2 O 5 0 to 30mol% of B' O 2 ,525mol% of Al 2 O 3 0 to 25mol% of SiO 2 The method comprises the steps of carrying out a first treatment on the surface of the Wherein: a represents K, na or Ag element, A 'represents Ba or Sr element, B represents Nb, ta or P element, and B' represents Ti or Sn element.
2. The glass-ceramic material according to claim 1, wherein the glass-ceramic material having a tetragonal tungsten bronze crystal phase structure is prepared by a method comprising the steps of:
(1) In K 2 CO3、Na 2 CO 3 、Ag 2 O、BaCO 3 、SrCO 3 、Nb 2 O 5 、P 2 O 5 、Ta 2 O 5 、Al 2 O 3 And SiO 2 Raw materials are proportioned according to the proportion of each oxide, then the raw materials are ball-milled for 24 hours in a ball mill by a wet method, dried and placed in a crucible for heat preservation for 2+/-0.5 hours at 1450-1500 ℃ to prepare uniform glass liquid;
(2) Rapidly pouring the obtained glass liquid into a preheated metal mold for molding, annealing in an annealing furnace at 550-570 ℃, and cutting into glass sheets with set areas after stress relief;
(3) Heating the glass sheet at a heating rate of 5 ℃/min, and preserving heat for 2+/-0.5 h at 750-830 ℃ for crystallization;
(4) And processing the obtained microcrystalline glass material sheet, and polishing the microcrystalline glass material sheet into a sheet with a set thickness.
3. The microcrystalline glass material with high energy storage and high optical transmittance is characterized by having a tetragonal perovskite crystal phase structure, and comprises the following components: baO-TiO 2 -SnO 2 -Al 2 O 3 -SiO 2 Ratio of each oxide: 15-35 mol% of BaO and 0-30 mol% of TiO 2 0 to 30mol% of SnO 2 5 to 25mol% of Al 2 O 3 0 to 25mol% of SiO 2 。
4. A glass-ceramic material according to claim 3, wherein the glass-ceramic material having a tetragonal perovskite crystal phase structure is prepared by a method comprising the steps of:
(1) In BaCO 3 、TiO 2 、SnO 2 、Al 2 O 3 And SiO 2 Raw materials are proportioned according to the proportion of each oxide, then the raw materials are ball-milled in a ball mill by a wet method, dried and placed in a crucible to be melted into uniform glass liquid after heat preservation for 2+/-0.5 h at 1450-1500 ℃;
(2) Rapidly pouring the obtained glass liquid into a preheated metal mold for molding, annealing in an annealing furnace at 550-650 ℃, and cutting into glass sheets with set areas after stress relief;
(3) Heating the glass sheet at a heating rate of 5 ℃/min, and preserving the temperature for 2+/-0.5 h at 850-950 ℃ for crystallization;
(4) And processing the obtained microcrystalline glass material sheet, and polishing the microcrystalline glass material sheet into a sheet with a set thickness.
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