CN114890676A - High-dielectric high-energy-storage microcrystalline glass dielectric material and preparation method thereof - Google Patents

High-dielectric high-energy-storage microcrystalline glass dielectric material and preparation method thereof Download PDF

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CN114890676A
CN114890676A CN202110685704.7A CN202110685704A CN114890676A CN 114890676 A CN114890676 A CN 114890676A CN 202110685704 A CN202110685704 A CN 202110685704A CN 114890676 A CN114890676 A CN 114890676A
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dielectric material
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CN114890676B (en
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尚飞
陈国华
许积文
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Guilin University of Electronic Technology
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    • 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
    • C03C10/0072—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 having a ferro-electric crystal phase
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    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
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    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B32/00—Thermal after-treatment of glass products not provided for in groups C03B19/00, C03B25/00 - C03B31/00 or C03B37/00, e.g. crystallisation, eliminating gas inclusions or other impurities; Hot-pressing vitrified, non-porous, shaped glass products
    • C03B32/02—Thermal crystallisation, e.g. for crystallising glass bodies into glass-ceramic articles
    • 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
    • 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
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/001—General methods for coating; Devices therefor
    • C03C17/002—General methods for coating; Devices therefor for flat glass, e.g. float glass
    • 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
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/06—Surface treatment of glass, not in the form of fibres or filaments, by coating with metals
    • C03C17/10—Surface treatment of glass, not in the form of fibres or filaments, by coating with metals by deposition from the liquid phase
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    • 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
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    • C03C4/16—Compositions for glass with special properties for dielectric glass
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    • C03C2217/00—Coatings on glass
    • C03C2217/20—Materials for coating a single layer on glass
    • C03C2217/25—Metals
    • C03C2217/251—Al, Cu, Mg or noble metals
    • C03C2217/254—Noble metals
    • C03C2217/256—Ag
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    • 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
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    • C03C2218/11—Deposition methods from solutions or suspensions
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    • 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
    • C03C2218/00—Methods for coating glass
    • C03C2218/10—Deposition methods
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    • C03C2218/119—Deposition methods from solutions or suspensions by printing
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    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P40/00—Technologies relating to the processing of minerals
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Abstract

The invention relates to a dielectric energy storage material, in particular to a high-dielectric high-energy storage microcrystalline glass dielectric material and a preparation method thereof, wherein the chemical components of the prepared microcrystalline glass dielectric material are as follows: x (AXO) 3 )‑y(aSiO 2 ‑bB 2 O 3 ‑cAl 2 O 3 )‑zM m O n (ii) a The dielectric constant can be adjusted within the range of 200-1500, the direct current breakdown strength range is 0.9-2.0MV/cm, and the highest theoretical energy storage density reaches 71.6J/cm3, can be used for preparing various high energy storage density and ultra-high voltage capacitors; meanwhile, the glass composition is lead-free, so that the purpose of environmental protection is achieved.

Description

High-dielectric high-energy-storage microcrystalline glass dielectric material and preparation method thereof
Technical Field
The invention relates to a dielectric energy storage material, in particular to a high-dielectric high-energy storage glass ceramic dielectric material and a preparation method thereof.
Background
The pulse power technology has wide application in national defense important military scientific research (such as fully electric ships and warfare vehicles, laser nuclear fusion, high-power energy generators and the like) and civil (such as pulse lasers, medical CT, renewable clean energy application and the like). Meanwhile, along with the rapid development of the electronic industry, higher requirements are put on the light weight and miniaturization of electronic equipment, namely, the equipment is required to be light and tiny as much as possible while more energy is stored. This puts higher demands on the performance of the capacitor as an important energy storage element, and the quality of the energy storage characteristics of the dielectric material as a key component of the capacitor device obviously directly restricts the overall energy storage performance of the capacitor.
Although the dielectric constant of the conventional ceramic dielectric material is higher than that of other dielectric materials, the conventional ceramic dielectric material has the disadvantages that pores are easily generated in the preparation process, so that the breakdown strength is low, and the increase of the energy storage density is limited. Compared with ceramic materials, the polymer materials have the advantages of high compactness and flexibility, but the dielectric constant is generally low, the increase of the energy storage density is also limited, and in addition, the polymer materials are not suitable for being used in high-temperature extreme environments. Compared with the two dielectric materials, the microcrystalline glass belongs to one of the composite materials, and crystals are precipitated from a glass matrix by melting powder with certain components into glass and then carrying out controllable crystallization heat treatment, so that the composite material with coexistence of a ceramic phase and a glass phase is obtained, and therefore, the microcrystalline glass has obvious advantages: on one hand, the dielectric constant can be regulated and controlled through composition design and a controllable crystallization heat treatment process; on the other hand, because the matrix is made of glass, the porosity is low, the breakdown strength is high, and the promotion space of the energy storage density is large. Therefore, the microcrystalline glass has better application prospect and development potential as a dielectric energy storage material in a pulse power technology.
Glass-ceramic dielectric materials can be broadly classified from their polarization behavior into linear glass-ceramics and ferroelectric glass-ceramics. The former has higher breakdown field strength but relatively lower dielectric constant, and the latter can obtain higher dielectric constant but lower breakdown field strength. Therefore, a 'double-high' glass ceramic dielectric energy storage material which has a 'giant dielectric constant' (the dielectric constant is more than or equal to 200) and a high breakdown field strength (the breakdown field strength is more than or equal to 1.0MV/cm) needs to be searched, so as to meet the application requirements of the glass ceramic dielectric energy storage material in the pulse power technology.
Disclosure of Invention
In order to solve the above problems, the first aspect of the present invention provides a high dielectric high energy storage density microcrystalline glass dielectric material, comprising a main crystal phase, a glass phase and a transition metal oxide phase, wherein the main crystal phase is precipitated from the glass phase, and a relaxation ferroelectric crystal of a polycrystalline nano domain is precipitated in the glass phase; the main crystal phase includes a ferroelectric phase material or a multiferroic phase material of a perovskite structure.
As a preferred technical scheme, the chemical formula of the main crystal phase is AXO 3 The chemical formula of the glassy phase is aSiO 2 -bB 2 O 3 -cAl 2 O 3 The transition metal oxide phase has the formula M m O n (ii) a Wherein, the element A is selected from at least one of Pb, K, Na, Ba, Sr and Bi; the X element is at least one of Ti, Nb and Fe; m element is selected from at least one of Sc, Y, Hf, V, Ta, Mn, Zn and Sn; a, b and c are SiO in glass phase respectively 2 、B 2 O 3 、Al 2 O 3 The mole percentage of a is more than or equal to 60 percent and less than or equal to 80 percent, b is more than or equal to 6 percent and less than or equal to 20 percent, and c is more than or equal to 0 percent and less than or equal to 34 percent.
As a preferable technical scheme, the chemical components of the microcrystalline glass dielectric material are as follows: x (AXO) 3 )-y(aSiO 2 -bB 2 O 3 -cAl 2 O 3 )-zM m O n (ii) a Wherein x, y and z are respectively the mole percentages of a main crystal phase, a glass phase and a transition metal oxide phase in the microcrystalline glass dielectric material, x is more than or equal to 60 and less than or equal to 80 percent, y is more than or equal to 10 and less than or equal to 40 percent, and z is more than or equal to 0 and less than or equal to 10 percent.
As a preferred embodiment, a: b: c is 10:2: 1.
As a preferred embodiment, x: y: z ═ 19:5: 1.
The second aspect of the invention provides a preparation method of a microcrystalline glass dielectric material, which comprises the following steps:
s1, according to x (AXO) 3 )-y(aSiO 2 -bB 2 O 3 -cAl 2 O 3 )-zM m O n The materials are proportioned, ball-milled for 24 hours, dried and then placed in a crucible for heat preservation for 0.5-2 hours at the melting temperature of 1400-1600 ℃ to be melted into uniform glass liquid;
s2, pouring the molten glass of the step S1 into a metal mold for molding, annealing in an annealing furnace at 600-680 ℃ for 4-10h to eliminate stress, and cutting into pieces with an area of 1-2 cm 2 A rectangular glass sheet of (a);
s3, heating the glass sheet prepared in the step S2 at a heating rate of 3 ℃/min, and carrying out crystallization at 800-1100 ℃ for 1-6h to obtain the microcrystalline glass dielectric material.
As a preferable technical scheme, the melting temperature in the step S1 is 1550 ℃, and the holding time is 1.5 h.
As a preferable technical solution, the annealing temperature in the step S2 is 640 ℃, and the annealing time is 6 h.
As a preferable technical solution, in the step S3, the crystallization temperature is 1050 ℃, and the crystallization time is 3 hours.
The third aspect of the invention provides a method for preparing a microcrystalline glass dielectric material capable of being electrically tested, which comprises the following steps:
s1, according to x (AXO) 3 )-y(aSiO 2 -bB 2 O 3 -cAl 2 O 3 )-zM m O n The materials are proportioned, ball-milled for 24 hours, dried and then placed in a crucible for heat preservation for 0.5-2 hours at the melting temperature of 1400-1600 ℃ to be melted into uniform glass liquid;
s2, pouring the molten glass of the step S1 into a metal mold for molding, annealing in an annealing furnace at 600-680 ℃ for 4-10h to eliminate stress, and cutting into pieces with an area of 1-2 cm 2 A rectangular glass sheet of (a);
s3, heating the glass sheet prepared in the step S2 at a heating rate of 3 ℃/min, and carrying out crystallization at 800-1100 ℃ for 1-6h to obtain a microcrystalline glass dielectric material;
s4, polishing the microcrystalline glass dielectric material obtained in the step S3 into a sheet with the thickness of 0.05-1 mm; and (3) screen printing or manually coating medium-temperature silver paste on the sheet, and sintering and curing at 600 ℃ to form the metal silver electrode.
Has the advantages that:
the invention adjusts the basic components of the glass and M m O n The kind and content of transition metal oxide can obtain a high dielectric high energy storage density relaxation ferroelectric glass ceramics medium material. The dielectric constant of the obtained relaxation ferroelectric glass ceramics material can be adjusted within the range of 200-1500, the direct current breakdown strength range is 0.9-2.0MV/cm, the highest theoretical energy storage density reaches 71.6J/cm3, and the relaxation ferroelectric glass ceramics material can be used for preparing various high energy storage density and ultrahigh voltage capacitors; meanwhile, the glass composition is lead-free, so that the purpose of environmental protection is achieved.
Drawings
Fig. 1 is an XRD spectrum of a sample of the microcrystalline glass dielectric material prepared in examples 1 and 2.
Fig. 2 is SEM photographs of samples of the microcrystalline glass dielectric material prepared in examples 1 (fig. 2(a)) and 2 (fig. 2 (b)).
Fig. 3 is a ferroelectric hysteresis loop of a sample of the microcrystalline glass dielectric material prepared in examples 1 and 2.
Fig. 4 is a graph of the distribution interval of the dielectric constant of the samples of the microcrystalline glass dielectric materials prepared in examples 1 and 2.
Fig. 5 is a weber distribution diagram of breakdown field strength of samples of the microcrystalline glass dielectric materials prepared in examples 1 and 2.
Detailed Description
The technical solutions of the present invention are described in detail below with reference to the accompanying drawings and specific embodiments, but the scope of the present invention is not limited to the embodiments.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. To the extent that a definition of a particular term disclosed in the prior art is inconsistent with any definition provided in the present disclosure, the definition of the term provided in the present disclosure controls.
As used herein, a feature that does not define a singular or plural form is also intended to include a plural form of the feature unless the context clearly indicates otherwise. It will be further understood that the term "prepared from …," as used herein, is synonymous with "comprising," including, "comprising," "having," "including," and/or "containing," when used in this specification means that the recited composition, step, method, article, or device is present, but does not preclude the presence or addition of one or more other compositions, steps, methods, articles, or devices. Furthermore, the use of "preferred," "preferably," "more preferred," etc., when describing embodiments of the present invention, is meant to refer to embodiments of the invention that may provide certain benefits, under certain circumstances. However, other embodiments may be preferred, under the same or other circumstances. In addition, the recitation of one or more preferred embodiments does not imply that other embodiments are not useful, nor is it intended to exclude other embodiments from the scope of the invention.
In order to solve the above problems, the first aspect of the present invention provides a high dielectric high energy storage density microcrystalline glass dielectric material, comprising a main crystal phase, a glass phase and a transition metal oxide phase, wherein the main crystal phase is precipitated from the glass phase, and a relaxation ferroelectric crystal of a polycrystalline nano domain is precipitated in the glass phase; the main crystal phase includes a ferroelectric phase material or a multiferroic phase material of a perovskite structure.
The design idea of the composition is as follows: based on the nano domain engineering regulation and control technology, the precipitation of the relaxation ferroelectric crystal with the polycrystalline nano domain is realized in the glass crystallization process, and finally the relaxation ferroelectric microcrystalline glass dielectric material with the giant dielectric constant and high breakdown-resistant field strength is obtained.
In some preferred embodiments, the main crystalline phase has the formula AXO 3 The chemical formula of the glass phase is aSiO 2 -bB 2 O 3 -cAl 2 O 3 The transition metal oxide phase has the formula M m O n (ii) a Wherein, the element A is selected from at least one of Pb, K, Na, Ba, Sr and Bi; the X element is at least one of Ti, Nb and Fe; m m O n The M element is selected from at least one of Sc, Y, Hf, V, Ta, Mn, Zn and Sn; a, b and c are SiO in glass phase respectively 2 、B 2 O 3 、Al 2 O 3 The mole percentage of a is more than or equal to 60 percent and less than or equal to 80 percent, b is more than or equal to 6 percent and less than or equal to 20 percent, and c is more than or equal to 0 percent and less than or equal to 34 percent.
In some preferred embodiments, the chemical composition of the microcrystalline glass dielectric material is: x (AXO) 3 )-y(aSiO 2 -bB 2 O 3 -cAl 2 O 3 )-zM m O n (ii) a Wherein x, y and z are respectively the mole percentages of a main crystal phase, a glass phase and a transition metal oxide phase in the microcrystalline glass dielectric material, x is more than or equal to 60 and less than or equal to 80 percent, y is more than or equal to 10 and less than or equal to 40 percent, and z is more than or equal to 0 and less than or equal to 10 percent.
In some preferred embodiments, a: b: c ═ 10:2: 1.
In some preferred embodiments, x: y: z ═ 19:5: 1.
In some preferred embodiments, the perovskite structure material is BaTiO 3 。
For the above-mentioned main crystal phase, glass phase material, by adding M m O n Transition metal oxide, and high temperature melting and subsequent heat treatment controllable crystallization process to prepare high dielectric and high energy storing density relaxed ferroelectric glass ceramic material m O n Under the regulation and control action of the transition metal oxide, the main crystal phase crystals are precipitated from the glass phase matrix, so that the composite material with coexistence of the ceramic phase and the glass phase is obtained, and on one hand, the dielectric constant can be regulated and controlled through composition design and a controllable crystallization heat treatment process; on the other hand, because the matrix is made of glass, the porosity is low, the breakdown strength is high, and the promotion space of the energy storage density is large.
The second aspect of the invention provides a preparation method of a microcrystalline glass dielectric material, which comprises the following steps:
s1, according to x (AXO) 3 )-y(aSiO 2 -bB 2 O 3 -cAl 2 O 3 )-zM m O n The materials are proportioned, ball-milled for 24 hours, dried and then placed in a crucible for heat preservation for 0.5-2 hours at the melting temperature of 1400-1600 ℃ to be melted into uniform glass liquid; preferably, the melting temperature is 1550 ℃, and the temperature is kept for 1.5 h;
s2, pouring the molten glass of the step S1 into a metal mold for molding, annealing in an annealing furnace at 600-680 ℃ for 4-10h to eliminate stress, and cutting into pieces with an area of 1-2 cm 2 A rectangular glass sheet of (a); preferably, the annealing temperature is 640 ℃, and the annealing is carried out for 6 hours;
s3, heating the glass sheet prepared in the step S2 at a heating rate of 3 ℃/min, and carrying out heat preservation at 800-1100 ℃ for 1-6h for crystallization to obtain the microcrystalline glass dielectric material, wherein the preferable crystallization temperature is 1050 ℃, and the heat preservation time is 3 h.
In some preferred embodiments, a method for preparing a microcrystalline glass dielectric material comprises the following steps:
s1, analytically pure (purity is more than or equal to 99 percent) BaCO 3 、TiO 2 、H 3 BO 3 、Al 2 O 3 、SiO 2 And high purity (99.9%) M m O n As starting material, according to x (AXO) 3 )-y(aSiO 2 -bB 2 O 3 -cAl 2 O 3 )-zM m O n The mixture is prepared according to the proportion of (1), wherein x is 76%; y is 20; z is 4; a is 77%; b is 15%; and c is 8 percent. Then, the raw materials are ball-milled for 24 hours in a wet method in a ball mill, dried and then placed in a crucible to be insulated for 0.5 to 2 hours at the melting temperature of 1400 ℃ and 1600 ℃, preferably the melting temperature of 1550 ℃ and the insulation time of 1.5 hours, and then melted into uniform glass liquid;
s2 pouring the molten glass of step S1 into a metal mold for molding, annealing in an annealing furnace at 600-680 ℃ for 4-10h to eliminate stress, and cutting into pieces with an area of 1-2 cm 2 The annealing temperature of the rectangular glass sheet is 640 ℃, and the annealing time is 6 hours;
s3, heating the glass sheet prepared in the step S2 at a heating rate of 3 ℃/min, and carrying out heat preservation at 1100 ℃ of 800 ℃ for 1-6h for crystallization, preferably 1050 ℃ for 3h to obtain a main crystal phase of barium titanate (BaTiO) 3 ) The relaxed ferroelectric glass-ceramic dielectric material of (1).
In some preferred embodiments, the grinding balls for ball milling in S1 are yttria-stabilized zirconia balls, and the ball milling medium is absolute ethanol or deionized water.
In some preferred embodiments, the metal mold in S2 is made of copper and has a rectangular or circular shape.
The third aspect of the invention provides a method for preparing a microcrystalline glass dielectric material capable of being electrically tested, wherein the microcrystalline glass dielectric material obtained in the step S3 is polished into a thin sheet with the thickness of 0.05-1 mm; and (3) screen printing or manually coating medium-temperature silver paste on the sheet, and sintering and curing at 600 ℃ to form the metal silver electrode.
The present invention will be specifically described below by way of examples. It should be noted that the following examples are only for illustrating the present invention and should not be construed as limiting the scope of the present invention, and that the insubstantial modifications and adaptations of the present invention by those skilled in the art based on the above disclosure are still within the scope of the present invention.
In addition, the starting materials used are all commercially available, unless otherwise specified.
Examples
Example 1：
Example 1 provides a high dielectric high energy storage relaxed ferroelectric microcrystalline glass dielectric material with a chemical composition of x (BaTiO) 3 )-y(aSiO 2 -bB 2 O 3 -cAl 2 O 3 )-zSnO 2 ；x＝76％；y＝20％；z＝4％；a＝77％；b＝15％；c＝8％。
Wherein x, y and z are respectively the main crystal phase BaTiO in the microcrystalline glass dielectric material 3 Glass phase (aSiO) 2 -bB 2 O 3 -cAl 2 O 3 ) Transition metal oxide phase SnO 2 Mole percent of (c); a, b and c are respectively glass phase (aSiO) 2 -bB 2 O 3 -cAl 2 O 3 ) SiO 2 2 、B 2 O 3 、Al 2 O 3 Mole percent of (c).
Example 1 also provides a method for its preparation, comprising the steps of:
s1, analytically pure (purity is more than or equal to 99 percent) BaCO 3 、TiO 2 、H 3 BO 3 、Al 2 O 3 、SiO 2 And high purity (99.9%) SnO 2 Mixing the raw materials according to the proportion of the chemical components, performing wet ball milling on the raw materials in a ball mill for 24 hours, drying, placing the raw materials in a crucible, and performing heat preservation at 1550 ℃ for 1.5 hours to prepare uniform glass liquid;
s2, pouring the molten glass of the step S1 into a metal mold for molding, then annealing for 6 hours in an annealing furnace at 640 ℃ to relieve stress, and then cutting into pieces with the area of 2cm 2 A rectangular glass sheet of (a);
s3, heating the glass sheet prepared in the step S2 at a heating rate of 3 ℃/min, and crystallizing at a crystallization temperature of 1050 ℃ for 3h to obtain a main crystal phase of barium titanate (BaTiO) 3 ) The dielectric material of the relaxed ferroelectric glass-ceramic of (1), as shown in the attached figure;
s4, processing the microcrystalline glass material sheet obtained in the step S3, and polishing the microcrystalline glass material sheet into a sheet with the thickness of 1 mm;
and S5, screen printing or manually coating medium-temperature silver paste (purchased from noble platinum industry) on the microcrystalline glass sheet obtained in the step S4, and sintering and curing at 600 ℃ to form a metallic silver electrode, so that the relaxor ferroelectric microcrystalline glass dielectric material capable of being subjected to electrical testing is prepared.
Tests show that the electric hysteresis curve of the obtained microcrystalline glass material has obvious polarization behavior of a relaxation ferroelectric, the micro-morphology is a nano sheet structure (shown in figure 2), the median value of the dielectric constant is 1169 (shown in figure 4), the dielectric loss is 0.06, the breakdown field strength is 1.176MV/cm (shown in figure 5), and the theoretical energy storage density is 71.6J/cm 3 (as shown in figure 3). And (3) testing conditions are as follows: the hysteresis loop is tested by a radial ferroelectric tester in the United states, the dielectric constant and the dielectric loss are 1kHz, the test equipment is tested by an Agilent 4294A precision impedance tester, and the test temperature is room temperature; the breakdown strength is measured at room temperature by taking silicone oil as a medium, the test equipment is domestic equipment, and the high-voltage source is an east high-voltage power supply.
Example 2：
Example 2 provides a high dielectric high energy storage relaxation ferroelectric microcrystalline glass dielectric material with a chemical composition of x (BaTiO) 3 )-y(aSiO 2 -bB 2 O 3 -cAl 2 O 3 )-z HfO 2 。
Wherein x, y and z are respectively the main crystal phase BaTiO in the microcrystalline glass dielectric material 3 Glass phase (aSiO) 2 -bB 2 O 3 -cAl 2 O 3 ) Transition metal oxide phase HfO 2 Mole percent of (c); a, b and c are respectively glass phase (aSiO) 2 -bB 2 O 3 -cAl 2 O 3 ) SiO 2 2 、B 2 O 3 、Al 2 O 3 Mole percent of (c).
Example 2 also provides a method for its preparation, comprising the steps of:
s1, analytically pure (purity is more than or equal to 99 percent) BaCO 3 、TiO 2 、H 3 BO 3 、Al 2 O 3 、SiO 2 And high purity (99.9%) HfO 2 Mixing the raw materials according to the proportion of the chemical components, performing wet ball milling on the raw materials in a ball mill for 24 hours, drying, placing the raw materials in a crucible, and performing heat preservation at 1550 ℃ for 1.5 hours to prepare uniform glass liquid;
s2, pouring the molten glass of the step S1 into a metal mold for molding, then annealing for 6 hours in an annealing furnace at 640 ℃ to relieve stress, and then cutting into pieces with the area of 2cm 2 A rectangular glass sheet of (a);
s3, heating the glass sheet prepared in the step S2 at a heating rate of 3 ℃/min, and crystallizing at a crystallization temperature of 1025 ℃ for 2h to obtain a main crystal phase of barium titanate (BaTiO) 3 ) The relaxed ferroelectric glass-ceramic dielectric material of (a);
s4, processing the microcrystalline glass material sheet obtained in the step S3, and polishing the microcrystalline glass material sheet into a sheet with the thickness of 1 mm;
and S5, screen printing or manually coating medium-temperature silver paste (purchased from noble platinum industry) on the microcrystalline glass sheet obtained in the step S4, and sintering and curing at 600 ℃ to form a metallic silver electrode, so that the relaxor ferroelectric microcrystalline glass dielectric material capable of being subjected to electrical testing is prepared.
Tests show that the electric hysteresis curve of the obtained microcrystalline glass material has obvious polarization behavior of relaxation ferroelectric and microscopic shapeThe appearance is a nano spherical structure (as shown in figure 2), the mean value of the dielectric constant is 288, the dielectric loss is 0.011, the breakdown field strength is 1.254MV/cm, and the theoretical energy storage density is 20.0J/cm 3 . And (3) testing conditions: the electric hysteresis loop, the dielectric constant and the dielectric loss are 1kHz, and the temperature is room temperature; the breakdown strength is measured at room temperature by taking silicone oil as a medium.
Example 3：
Example 3 provides a high dielectric high energy storage relaxed ferroelectric microcrystalline glass dielectric material with a chemical composition of x (BaTiO) 3 )-y(aSiO 2 -bB 2 O 3 -cAl 2 O 3 )-zSnO 2 Wherein x is 30%; y is 60; z is 10; a is 77; b is 15; and c is 8.
Wherein x, y and z are respectively the main crystal phase BaTiO in the microcrystalline glass dielectric material 3 Glass phase (aSiO) 2 -bB 2 O 3 -cAl 2 O 3 ) Transition metal oxide phase SnO 2 Mole percent of (c); a, b and c are respectively glass phase (aSiO) 2 -bB 2 O 3 -cAl 2 O 3 ) SiO 2 2 、B 2 O 3 、Al 2 O 3 Mole percent of (c).
Example 3 also provides a method for its preparation, comprising the steps of:
s1, analytically pure (purity is more than or equal to 99 percent) BaCO 3 、TiO 2 、H 3 BO 3 、Al 2 O 3 、SiO 2 And high purity (99.9%) SnO 2 Mixing the raw materials according to the proportion of the chemical components, performing wet ball milling on the raw materials in a ball mill for 24 hours, drying, placing the raw materials in a crucible, and performing heat preservation at 1550 ℃ for 1.5 hours to prepare uniform glass liquid;
s2, pouring the molten glass of the step S1 into a metal mold for molding, then annealing for 6 hours in an annealing furnace at 640 ℃ to relieve stress, and then cutting into pieces with the area of 2cm 2 A rectangular glass sheet of (a);
s3, heating the glass sheet prepared in the step S2 at a heating rate of 3 ℃/min, and crystallizing at a crystallization temperature of 1050 ℃ for 3h to obtain a main crystal phase of barium titanate ()BaTiO 3 ) The relaxed ferroelectric glass-ceramic dielectric material of (a);
s4, processing the microcrystalline glass material sheet obtained in the step S3, and polishing the microcrystalline glass material sheet into a sheet with the thickness of 1 mm;
and S5, screen printing or manually coating medium-temperature silver paste (purchased from noble platinum industry) on the microcrystalline glass sheet obtained in the step S4, and sintering and curing at 600 ℃ to form a metallic silver electrode, so that the relaxor ferroelectric microcrystalline glass dielectric material capable of being subjected to electrical testing is prepared.
Tests show that the electric hysteresis curve of the obtained microcrystalline glass material has obvious polarization behavior of relaxation ferroelectric, the micro-morphology of the microcrystalline glass material is a nano spherical structure, the microcrystalline glass material is similar to the microcrystalline glass material in example 1, the mean value of the dielectric constant is 110, the dielectric loss is 0.023, the breakdown field strength is 0.9MV/cm, and the theoretical energy storage density is 3.94J/cm 3 。
Example 4：
Example 4 provides a high dielectric high energy storage relaxed ferroelectric microcrystalline glass dielectric material with a chemical composition of x (BaTiO) 3 )-y(aSiO 2 -bB 2 O 3 -cAl 2 O 3 )-zSnO 2 Wherein x is 76%; y is 20%; z is 4%; a is 77%; b is 15%; and c is 8 percent.
Wherein x, y and z are respectively the main crystal phase BaTiO in the microcrystalline glass dielectric material 3 Glass phase (aSiO) 2 -bB 2 O 3 -cAl 2 O 3 ) Transition metal oxide phase SnO 2 The mole percentage of (c); a, b and c are respectively glass phase (aSiO) 2 -bB 2 O 3 -cAl 2 O 3 ) SiO 2 2 、B 2 O 3 、Al 2 O 3 Mole percent of (c).
Example 4 also provides a method for its preparation, comprising the steps of:
s1, analytically pure (purity is more than or equal to 99 percent) BaCO 3 、TiO 2 、H 3 BO 3 、Al 2 O 3 、SiO 2 And high purity (99.9%) SnO 2 Mixing the raw materials according to the proportion of the chemical components, and wet-grinding the raw materials in a ball millBall-milling for 24h, drying, placing in a crucible, keeping the temperature at 1550 ℃ for 1.5h, and melting into uniform glass liquid;
s2, pouring the molten glass of the step S1 into a metal mold for molding, then annealing for 6 hours in an annealing furnace at 640 ℃ to relieve stress, and then cutting into pieces with the area of 2cm 2 A rectangular glass sheet of (a);
s3, heating the glass sheet prepared in the step S2 at a heating rate of 3 ℃/min, and crystallizing at a crystallization temperature of 1150 ℃ for 6h to obtain a main crystal phase of barium titanate (BaTiO) 3 ) The relaxed ferroelectric glass-ceramic dielectric material of (a);
s4, processing the microcrystalline glass material sheet obtained in the step S3, and polishing the microcrystalline glass material sheet into a sheet with the thickness of 1 mm;
and S5, screen printing or manually coating medium-temperature silver paste (purchased from noble platinum industry) on the microcrystalline glass sheet obtained in the step S4, and sintering and curing at 600 ℃ to form a metallic silver electrode, so that the relaxor ferroelectric microcrystalline glass dielectric material capable of being subjected to electrical testing is prepared.
Tests prove that the electric hysteresis curve of the obtained microcrystalline glass material has obvious polarization behavior of the relaxation ferroelectric, the micro-morphology is a nano sheet structure, the micro-morphology is similar to that of the microcrystalline glass material in the embodiment 1, the mean value of the dielectric constant is 875, the dielectric loss is 0.05, the breakdown field strength is 0.4MV/cm, and the theoretical energy storage density is 6.20J/cm 3 。
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.

Claims (10)

1. A high-dielectric high-energy storage microcrystalline glass dielectric material is characterized in that: the ferroelectric phase-change material comprises a main crystal phase, a glass phase and a transition metal oxide phase, wherein the main crystal phase is precipitated from the glass phase, and a relaxation ferroelectric crystal of a polycrystalline nano domain is precipitated in the glass phase; the main crystal phase includes a ferroelectric phase material or a multiferroic phase material of a perovskite structure.
2. A microcrystalline glass dielectric material as claimed in claim 1, wherein: the main crystal phase has a chemical formula of AXO 3 The chemical formula of the glassy phase is aSiO 2 -bB 2 O 3 -cAl 2 O 3 The transition metal oxide phase has the formula M m O n (ii) a Wherein, the element A is selected from at least one of Pb, K, Na, Ba, Sr and Bi; the X element is at least one of Ti, Nb and Fe; m element is selected from at least one of Sc, Y, Hf, V, Ta, Mn, Zn and Sn; a, b and c are SiO in glass phase respectively 2 、B 2 O 3 、Al 2 O 3 The mole percentage of a is more than or equal to 60 percent and less than or equal to 80 percent, b is more than or equal to 6 percent and less than or equal to 20 percent, and c is more than or equal to 0 percent and less than or equal to 34 percent.
3. A microcrystalline glass dielectric material as claimed in claim 2, wherein: the chemical components of the microcrystalline glass dielectric material are as follows: x (AXO) 3 )-y(aSiO 2 -bB 2 O 3 -cAl 2 O 3 )-zM m O n (ii) a Wherein x, y and z are respectively the mole percentages of a main crystal phase, a glass phase and a transition metal oxide phase in the microcrystalline glass dielectric material, x is more than or equal to 60 and less than or equal to 80 percent, y is more than or equal to 10 and less than or equal to 40 percent, and z is more than or equal to 0 and less than or equal to 10 percent.
4. A microcrystalline glass dielectric material as claimed in claim 3, wherein: a, b and c are 10:2: 1.
5. A microcrystalline glass dielectric material as claimed in claim 4, wherein: x, y, z-19: 5: 1.
6. A method for preparing a microcrystalline glass dielectric material as claimed in any of claims 1-5, which comprises the following steps:
s1, according to x (AXO) 3 )-y(aSiO 2 -bB 2 O 3 -cAl 2 O 3 )-zM m O n The materials are proportioned, ball-milled for 24 hours, dried and then placed in a crucible for heat preservation for 0.5-2 hours at the melting temperature of 1400-1600 ℃ to be melted into uniform glass liquid;
s2, pouring the molten glass of the step S1 into a metal mold for molding, annealing in an annealing furnace at 600-680 ℃ for 4-10h to eliminate stress, and cutting into pieces with an area of 1-2 cm 2 A rectangular glass sheet of (a);
s3, heating the glass sheet prepared in the step S2 at a heating rate of 3 ℃/min, and carrying out crystallization at 800-1100 ℃ for 1-6h to obtain the microcrystalline glass dielectric material.
7. The method for preparing the microcrystalline glass dielectric material as claimed in claim 6, wherein: the melting temperature in the step S1 is 1550 ℃, and the heat preservation time is 1.5 h.
8. The method for preparing the microcrystalline glass dielectric material as claimed in claim 6, wherein: the annealing temperature in the step S2 is 640 ℃, and the annealing time is 6 h.
9. The method for preparing the microcrystalline glass dielectric material as claimed in claim 6, wherein: in the step S3, the crystallization temperature is 1050 ℃, and the crystallization time is 3 h.
10. A method for preparing a microcrystalline glass dielectric material capable of being electrically tested is characterized by comprising the following steps:
s1, according to x (AXO) 3 )-y(aSiO 2 -bB 2 O 3 -cAl 2 O 3 )-zM m O n The materials are proportioned, ball-milled for 24 hours, dried and then placed in a crucible for heat preservation for 0.5-2 hours at the melting temperature of 1400-1600 ℃ to be melted into uniform glass liquid;
s2, pouring the molten glass of the step S1 into a metal mold for molding, annealing in an annealing furnace at 600-680 ℃ for 4-10h to eliminate stress, and cutting into pieces with an area of 1-2 cm 2 A rectangular glass sheet of (a);
s3, heating the glass sheet prepared in the step S2 at a heating rate of 3 ℃/min, and carrying out crystallization at 800-1100 ℃ for 1-6h to obtain a microcrystalline glass dielectric material;
s4, polishing the microcrystalline glass dielectric material obtained in the step S3 into a sheet with the thickness of 0.05-1 mm; and (3) screen printing or manually coating medium-temperature silver paste on the sheet, and sintering and curing at 600 ℃ to form the metal silver electrode.
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