CN115536390B - Transparent dielectric energy storage ceramic material and preparation method and application thereof - Google Patents

Transparent dielectric energy storage ceramic material and preparation method and application thereof Download PDF

Info

Publication number
CN115536390B
CN115536390B CN202211250523.2A CN202211250523A CN115536390B CN 115536390 B CN115536390 B CN 115536390B CN 202211250523 A CN202211250523 A CN 202211250523A CN 115536390 B CN115536390 B CN 115536390B
Authority
CN
China
Prior art keywords
raw material
energy storage
niobate
magnesium niobate
drying
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN202211250523.2A
Other languages
Chinese (zh)
Other versions
CN115536390A (en
Inventor
李卓
王子煊
张家勇
杨强斌
张丹丹
王卓
耿九光
牛艳辉
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Changan University
Original Assignee
Changan University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Changan University filed Critical Changan University
Priority to CN202211250523.2A priority Critical patent/CN115536390B/en
Publication of CN115536390A publication Critical patent/CN115536390A/en
Application granted granted Critical
Publication of CN115536390B publication Critical patent/CN115536390B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/495—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on vanadium, niobium, tantalum, molybdenum or tungsten oxides or solid solutions thereof with other oxides, e.g. vanadates, niobates, tantalates, molybdates or tungstates
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/009—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone characterised by the material treated
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
    • C04B41/50—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
    • C04B41/51—Metallising, e.g. infiltration of sintered ceramic preforms with molten metal
    • C04B41/5116—Ag or Au
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
    • C04B41/81—Coating or impregnation
    • C04B41/85—Coating or impregnation with inorganic materials
    • C04B41/88—Metals
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3201—Alkali metal oxides or oxide-forming salts thereof
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3205—Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
    • C04B2235/3206—Magnesium oxides or oxide-forming salts thereof
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3205—Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
    • C04B2235/3213—Strontium oxides or oxide-forming salts thereof
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3205—Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
    • C04B2235/3215—Barium oxides or oxide-forming salts thereof
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
    • C04B2235/3232—Titanium oxides or titanates, e.g. rutile or anatase
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3298—Bismuth oxides, bismuthates or oxide forming salts thereof, e.g. zinc bismuthate
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
    • C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
    • C04B2235/6562—Heating rate
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
    • C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
    • C04B2235/6567—Treatment time
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
    • C04B2235/9646—Optical properties
    • C04B2235/9653—Translucent or transparent ceramics other than alumina
    • 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
    • Y02P40/60—Production of ceramic materials or ceramic elements, e.g. substitution of clay or shale by alternative raw materials, e.g. ashes

Abstract

The invention provides a sodium niobate-bismuth magnesium niobate-barium magnesium niobate-strontium titanate transparent medium energy storage ceramic material, which has the composition formula: 0.95[ 2 ], [0.90NaNbO ] 3 ‑0.10((1‑x)Bi(Mg 2/3 Nb 1/3 )O 3 ‑xBa(Mg 1/3 Nb 2/3 )O 3 )]‑0.05SrTiO 3 X is mole percentage, x is more than or equal to 0.10 and less than or equal to 0.25. Also provides a preparation method, which is to dry Na 2 CO 3 Raw material, bi 2 O 3 Raw material, baCO 3 Raw material SrCO 3 Raw Material, nb 2 O 5 Raw Material, tiO 2 The raw materials and MgO raw materials are weighed and mixed, and then are subjected to ball milling, presintering, secondary ball milling, tabletting and sintering, and then are subjected to polishing and surface metallization to prepare the magnesium-based alloy material. The preparation method is simple, good in repeatability and high in yield, and has excellent energy storage performance and a certain light transmittance. The practicality is strong, and easily conventional batch production, and can compromise energy storage performance and optical property, is the unleaded transparent energy storage pottery of a superior performance, is hopeful to be used for aspects such as transparent pulse capacitor.

Description

Transparent dielectric energy storage ceramic material and preparation method and application thereof
Technical Field
The invention belongs to the technical field of ceramic materials, in particular to a sodium niobate-bismuth magnesium niobate-barium magnesium niobate-strontium titanate transparent medium energy storage ceramic material and a preparation method and application thereof.
Background
The dielectric capacitor is widely applied to the fields of pulse power systems, electric automobiles, aerospace, defense technologies and the like as an extremely key electronic component. In recent years, with the development of miniaturization, light weight, safety and diversification of application fields of electronic components, inorganic electronic information materials advance toward high efficiency, high reliability, intellectualization and function integration, and further, higher requirements are provided for innovation of design and preparation technology of new materials, and multiple functional responses are realized in the same dielectric material, so that the inorganic electronic information materials become one of research hotspots of novel intelligent materials.
Sodium niobate ceramic is an important system of dielectric capacitor materials, and is considered as the material with the most commercial application potential due to the wide band gap (large breakdown electric field), no volatile K element (easy preparation) and low volume density (light weight), thereby causing wide attention of wide scientific and technological workers and enterprises. At present, regarding the research of sodium niobate-based ceramics, most researchers mainly focus on the aspects of improving and optimizing energy storage performance, on one hand, the large delta P (Pmax-Pr) is obtained by destroying the long-range order of ferroelectrics and enhancing the relaxation characteristic thereof through the local random field formed by doping A/B site ions and solid solution of two-phase and multi-phase components; on the other hand, the crystal grains with uniform distribution and fine size are obtained through the optimization of the preparation process, so that the breakdown field intensity (Eb) of the material is improved, and the energy storage characteristic of the material is improved.
Considering the development of high intelligence and high integration of materials and the development and application of transparent pulse capacitors, the design and preparation of new materials combining energy storage performance and optical transparency conform to the current material design concept, and especially play an extremely important role in the development of new-generation transparent pulse capacitors.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a sodium niobate-bismuth magnesium niobate-barium magnesium niobate-strontium titanate transparent medium energy storage ceramic material, a preparation method and application thereof aiming at the defects of the prior art, wherein the preparation method is simple, good in repeatability, high in yield, and excellent in energy storage performance and certain in light transmittance. The material has strong practicability, is easy for routine batch production, can give consideration to energy storage performance and optical performance, is lead-free transparent energy storage ceramic with excellent performance, and is expected to be used in the aspects of transparent pulse capacitors and the like.
In order to solve the technical problems, the invention adopts the technical scheme that: a sodium niobate-bismuth magnesium niobate-barium magnesium niobate-strontium titanate transparent medium energy storage ceramic material has a composition formula as follows: 0.95[ 2 ], [0.90NaNbO ] 3 -0.10((1-x)Bi(Mg 2/3 Nb 1/3 )O 3 -xBa(Mg 1/3 Nb 2/3 )O 3 )]-0.05SrTiO 3 Wherein x is mole percentage, and x is more than or equal to 0.10 and less than or equal to 0.25.
The invention also provides a method for preparing the sodium niobate-bismuth magnesium niobate-barium magnesium niobate-strontium titanate transparent medium energy storage ceramic material, which comprises the following steps:
s1, drying materials: respectively adding Na 2 CO 3 Raw material, bi 2 O 3 Raw material, baCO 3 Raw material and SrCO 3 Drying the raw materials for 6h at 300 ℃ respectively;
mixing Nb with 2 O 5 Raw material, tiO 2 Respectively drying the raw material and the MgO raw material for 4 hours in strips at the temperature of 900 ℃;
the Na is 2 CO 3 The purity of the raw material is 99.8 percent, and the Bi is 2 O 3 The purity of the raw material is 99.8 percent, and the BaCO 3 The purity of the raw material is 99 percent, and the SrCO 3 The purity of the raw material is 99 percent, and the Nb is 2 O 5 The purity of the MgO raw material is 99.5 percent, and the purity of the MgO raw material is 98.5 percent;
s2, preparing materials: drying the dried Na in the S1 2 CO 3 Raw material, bi 2 O 3 Raw material, baCO 3 Raw material SrCO 3 Raw material, nb 2 O 5 Raw material, tiO 2 The raw material and MgO raw material were adjusted to 0.95[ 2.90 ] NaNbO 3 -0.10((1-x)Bi(Mg 2/3 Nb 1/3 )O 3 -x Ba(Mg 1/ 3 Nb 2/3 )O 3 )]-0.05SrTiO 3 Respectively weighing the above stoichiometric ratio, uniformly mixing to obtain a premix, adding agate balls and absolute ethyl alcohol, ball-milling for 6-10 h, separating the agate balls, drying at 80-100 ℃ for 12-24 h, and sieving with a 120-mesh sieve to obtain a raw material mixture;
s3, pre-burning: pre-burning the raw material mixture obtained in the step S2 for 2 to 4 hours at the temperature of 850 to 950 ℃, naturally cooling to room temperature, and grinding to obtain pre-burnt powder;
s4, secondary ball milling: adding agate balls and absolute ethyl alcohol into the pre-sintered powder obtained in the S3, performing ball milling for 6-10 h, separating the agate balls, drying at the temperature of 80-100 ℃ for 12-24 h, and sieving through a 180-mesh sieve after grinding to obtain the pre-sintered powder after ball milling;
s5, tabletting, namely adding 6 percent of polyvinyl alcohol aqueous solution into the pre-sintered powder after the grinding balls obtained in the S4, granulating, sieving by a 40-mesh sieve to obtain spherical powder substances, and maintaining the pressure for 20-60S under the condition of the unidirectional pressure of 150-200 MPa to obtain a disk-shaped ceramic blank;
s6, sintering: sintering the disk-shaped ceramic blank obtained in the step S5 to obtain a sintered ceramic blank; the sintering conditions are as follows: firstly heating from room temperature to 550 ℃ at the heating rate of 3 ℃/min, preserving heat for 3h, then heating to 1230-1300 ℃ at the heating rate of 3-5 ℃/min, sintering for 2-4 h, and then cooling to room temperature at the cooling rate of 5 ℃/min;
s7, polishing: polishing the upper surface and the lower surface of the sintered ceramic blank obtained in the step S6 by using 600-mesh abrasive paper, polishing the upper surface and the lower surface by using 2000-mesh abrasive paper and carborundum until the thickness is 0.3-0.5 mm, putting the polished ceramic blank into deionized water, ultrasonically cleaning and drying the polished ceramic blank to obtain a polished ceramic blank;
s8, surface metallization: and (4) uniformly coating silver pastes with the thickness of 0.01-0.03 mm on the upper surface and the lower surface of the polished ceramic blank obtained in the step (S7), preserving the heat for 10min at the temperature of 850 ℃, and naturally cooling to room temperature to obtain the sodium niobate-bismuth magnesium niobate-barium magnesium niobate-strontium titanate transparent medium energy storage ceramic material.
The invention selects Na 2 CO 3 Raw material, bi 2 O 3 Raw material, baCO 3 、SrCO 3 Raw material, nb 2 O 5 Raw material, tiO 2 The raw materials and MgO are directly synthesized to prepare a quaternary solid solution system of sodium niobate, bismuth magnesium niobate, barium magnesium niobate and strontium titanate, and the synthesized components have a pseudo-cubic phase structure with higher symmetry, so that the birefringence phenomenon of incident light between adjacent crystal grains is effectively avoided, the light scattering loss is reduced, and the light transmittance of the ceramic material is improved; the ball milling is carried out twice in the preparation process, on one hand, the uniform mixing and the full reaction of the initial raw materials are facilitated to form a uniform single-phase structure, and on the other hand, the ball milling is carried out for two timesOn one hand, the powder particles are refined, the size and the air holes of the ceramic crystal particles are reduced, the density of the ceramic crystal particles is improved, incident light easily passes through the crystal, meanwhile, the light scattering of a crystal boundary is reduced, and the transparency of the ceramic is improved.
Preferably, the dosage ratio of the premix, the agate balls and the absolute ethyl alcohol in the S2 is 0.35g: 0.52mL.
Preferably, the dosage ratio of the agate balls to the absolute ethyl alcohol added into the pre-sintering powder of S4 is 0.30g: 0.40mL.
Preferably, the mass ratio of the 6% polyvinyl alcohol aqueous solution to the pre-sintered powder after ball grinding in the S5 is (25% -35%): 1.
the invention also provides application of the prepared sodium niobate-bismuth magnesium niobate-barium magnesium niobate-strontium titanate transparent medium energy storage ceramic material, which is characterized in that the sodium niobate-bismuth magnesium niobate-barium magnesium niobate-strontium titanate transparent medium energy storage ceramic material has light transmission and is used for preparing transparent pulse capacitors.
Compared with the prior art, the invention has the following advantages:
the ceramic material prepared by the invention has simple preparation method, good repeatability and high yield, and the obtained 0.95[0.90NaNbO ] 3 -0.10((1-x)Bi(Mg 2/3 Nb 1/3 )O 3 -xBa(Mg 1/3 Nb 2/3 )O 3 )]-0.05SrTiO 3 The transparent dielectric energy storage ceramic material has excellent energy storage performance and certain light transmittance. The practicality is strong, and easily conventional batch production, and can compromise energy storage performance and optical property, is the unleaded transparent energy storage pottery of a superior performance, is hopeful to be used for aspects such as transparent pulse capacitor.
The present invention will be described in further detail with reference to the accompanying drawings and examples.
Drawings
FIG. 1 is an XRD pattern of ceramic samples prepared in examples 1-4 of the present invention.
FIG. 2 is an electron microscope photograph of ceramic samples prepared in examples 1 to 4 of the present invention.
FIG. 3 is a graph of breakdown field strength for ceramic samples made in examples 1-4 of the present invention.
FIG. 4 is a P-E curve of ceramic samples made in examples 1-4 of the present invention.
FIG. 5 is the value of 0.95[0.90NaNbO ] prepared in example 3 of the present invention 3 -0.10(0.80Bi(Mg 2/3 Nb 1/3 )O 3 -0.20Ba(Mg 1/3 Nb 2/3 )O 3 )]-0.05SrTiO 3 Temperature stability picture of energy storage performance of ceramic sample.
FIG. 6 is a photograph of 0.95[ 2 ], [0.90NaNbO ] obtained in example 3 of the present invention 3 -0.10(0.80Bi(Mg 2/3 Nb 1/3 )O 3 -0.20Ba(Mg 1/3 Nb 2/3 )O 3 )]-0.05SrTiO 3 Frequency stability picture of energy storage performance of ceramic sample.
FIG. 7 is 0.95[ 2 ], [0.90NaNbO ] prepared in example 3 of the present invention 3 -0.10(0.80Bi(Mg 2/3 Nb 1/3 )O 3 -0.20Ba(Mg 1/3 Nb 2/3 )O 3 )]-0.05SrTiO 3 And (5) testing the light transmittance of the ceramic sample.
Detailed Description
Example 1
The sodium niobate-bismuth magnesium niobate-barium magnesium niobate-strontium titanate transparent medium energy storage ceramic material of the embodiment has a composition formula as follows: 0.95[ 2 ], [0.90NaNbO ] 3 -0.10(0.90Bi(Mg 2/3 Nb 1/3 )O 3 -0.10Ba(Mg 1/3 Nb 2/3 )O 3 )]-0.05SrTiO 3 。
The embodiment also provides a method for preparing the sodium niobate-bismuth magnesium niobate-barium magnesium niobate-strontium titanate transparent medium energy storage ceramic material, which comprises the following steps:
s1, drying materials: respectively adding Na 2 CO 3 Raw material, bi 2 O 3 Raw material, baCO 3 Raw material and SrCO 3 Drying the raw materials for 6h at 300 ℃ respectively;
mixing Nb with 2 O 5 Raw material, tiO 2 Respectively drying the raw material and the MgO raw material for 4 hours in strips at the temperature of 900 ℃;
the Na is 2 CO 3 The purity of the raw material is 99.8 percent, and the Bi is 2 O 3 The purity of the raw material is 99.8 percent, and the BaCO 3 The purity of the raw material is 99 percent, and the SrCO 3 The purity of the raw material is 99 percent, and the Nb is 2 O 5 The purity of the MgO raw material is 99.5 percent, the purity of the MgO raw material is 98.5 percent, and the MgO raw material is purchased from chemical reagents of national medicine group, inc.;
s2, preparing materials: drying the Na in the S1 2 CO 3 Raw material, bi 2 O 3 Raw material, baCO 3 Raw material SrCO 3 Raw material, nb 2 O 5 Raw material, tiO 2 The raw material and MgO raw material are in accordance with 0.95[ 2 ], [0.90NaNbO ] 3 -0.10(0.90Bi(Mg 2/3 Nb 1/3 )O 3 -0.10Ba(Mg 1/ 3 Nb 2/3 )O 3 )]-0.05SrTiO 3 The stoichiometric ratio of (A) is respectively weighed, namely the dried Na is weighed 2 CO 3 Raw materials 5.1089g, bi 2 O 3 2.2642g of raw material, baCO 3 0.2131g of raw material, srCO 3 0.8391g of raw materials, nb 2 O 5 13.3748g of raw material, tiO 2 0.4586g of raw material and 0.2770g of MgO raw material are uniformly mixed to obtain a premix, agate balls and absolute ethyl alcohol are added, ball milling is carried out at the speed of 300r/min for 8 hours, after the agate balls are separated, drying is carried out at the temperature of 90 ℃ for 12 hours, and after grinding, the mixture is sieved by a 120-mesh sieve to obtain a raw material mixture; the dosage ratio of the premix, the agate balls and the absolute ethyl alcohol is 0.35g: 0.52mL;
s3, pre-burning: pre-burning the raw material mixture obtained in the step S2 at 900 ℃ for 3h, naturally cooling to room temperature, and grinding to obtain pre-burnt powder;
s4, secondary ball milling: adding agate balls and absolute ethyl alcohol into the pre-sintering powder obtained in the step S3, carrying out ball milling for 8 hours, separating the agate balls, drying at the temperature of 90 ℃ for 20 hours, and sieving through a 180-mesh sieve after grinding to obtain the pre-sintering powder after ball milling; the dosage ratio of the agate balls to the absolute ethyl alcohol added into the pre-sintering powder is 0.30g: 0.40mL;
s5, tabletting, namely adding 6% polyvinyl alcohol aqueous solution in percentage by mass into the pre-sintered powder after the grinding balls obtained in the S4, granulating, sieving by a 40-mesh sieve to obtain spherical powder substances, and maintaining the pressure for 40S under the condition of the unidirectional pressure of 180MPa to obtain a wafer-shaped ceramic blank; the mass ratio of the 6% polyvinyl alcohol aqueous solution to the pre-sintered powder after ball grinding is 30%:1;
s6, sintering: sintering the disk-shaped ceramic blank obtained in the step S5 to obtain a sintered ceramic blank; the sintering conditions are as follows: firstly, heating from room temperature to 550 ℃ at the heating rate of 3 ℃/min, preserving heat for 3h, then heating to 1250 ℃ at the heating rate of 4 ℃/min, sintering for 3h, and then cooling to room temperature at the cooling rate of 5 ℃/min;
s7, polishing: grinding the upper surface and the lower surface of the sintered ceramic blank obtained in the step S6 by using 600-mesh abrasive paper, polishing the upper surface and the lower surface by using 2000-mesh abrasive paper and carborundum until the thickness of the sintered ceramic blank is 0.3mm, putting the polished ceramic blank into deionized water, ultrasonically cleaning and drying the polished ceramic blank to obtain a polished ceramic blank;
s8, surface metallization: and (4) uniformly coating silver pastes with the thickness of 0.03mm on the upper surface and the lower surface of the polished ceramic blank obtained in the step (S7), preserving the heat for 10min at the temperature of 850 ℃, and naturally cooling to room temperature to obtain the sodium niobate-bismuth magnesium niobate-barium magnesium niobate-strontium titanate transparent medium energy storage ceramic material.
Example 2
The sodium niobate-bismuth magnesium niobate-barium magnesium niobate-strontium titanate transparent medium energy storage ceramic material of the embodiment has a composition formula as follows: 0.95[ 2 ], [0.90NaNbO ] 3 -0.10(0.85Bi(Mg 2/3 Nb 1/3 )O 3 -0.15Ba(Mg 1/3 Nb 2/3 )O 3 )]-0.05SrTiO 3 。
The embodiment also provides a method for preparing the sodium niobate-bismuth magnesium niobate-barium magnesium niobate-strontium titanate transparent medium energy storage ceramic material, which comprises the following steps:
s1, drying materials: respectively adding Na 2 CO 3 Raw material, bi 2 O 3 Raw material, baCO 3 Raw material and SrCO 3 Drying the raw materials for 6h at 300 ℃ respectively;
nb to 2 O 5 Raw material, tiO 2 Respectively drying the raw material and the MgO raw material for 4 hours in strips at the temperature of 900 ℃;
the Na is 2 CO 3 The purity of the raw material is 99.8 percent, and the Bi is 2 O 3 The purity of the raw material is 99.8 percent, and the BaCO is 3 The purity of the raw material is 99 percent, and the SrCO 3 The purity of the raw material is 99 percent, and the Nb is 2 O 5 The purity of (2) is 99.5%, the purity of the MgO raw material is 98.5%, and the MgO raw material is purchased from national medicine group chemical reagent limited company;
s2, preparing materials: drying the Na in the S1 2 CO 3 Raw material, bi 2 O 3 Raw material, baCO 3 Raw material SrCO 3 Raw material, nb 2 O 5 Raw Material, tiO 2 The raw material and MgO raw material are in accordance with 0.95[ 2 ], [0.90NaNbO ] 3 -0.10(0.85Bi(Mg 2/3 Nb 1/3 )O 3 -0.15Ba(Mg 1/ 3 Nb 2/3 )O 3 )]-0.05SrTiO 3 The stoichiometric ratio of (A) is respectively weighed, namely the dried Na is weighed 2 CO 3 5.1156g of raw material and Bi 2 O 3 2.1412g of raw material, baCO 3 Raw material 0.3200g, srCO 3 Raw materials 0.8401g, nb 2 O 5 13.4161g of raw Material, tiO 2 0.4592g of raw material and 0.2701g of MgO raw material are uniformly mixed to obtain premix, agate balls and absolute ethyl alcohol are added, ball milling is carried out for 10h at the speed of 300r/min, after the agate balls are separated, drying is carried out for 24h at the temperature of 80 ℃, and after grinding, sieving is carried out by a 120-mesh sieve to obtain a raw material mixture; the dosage ratio of the premix, the agate balls and the absolute ethyl alcohol is 0.35g: 0.52mL;
s3, pre-burning: pre-burning the raw material mixture obtained in the step S2 for 4 hours at the temperature of 850 ℃, naturally cooling to room temperature, and grinding to obtain pre-burnt powder;
s4, secondary ball milling: adding agate balls and absolute ethyl alcohol into the pre-sintering powder obtained in the step S3, carrying out ball milling for 6 hours, separating the agate balls, drying at the temperature of 80 ℃ for 24 hours, and sieving through a 180-mesh sieve after grinding to obtain the pre-sintering powder after ball milling; the dosage ratio of the agate balls to the absolute ethyl alcohol added into the pre-sintering powder is 0.30g: 0.40mL;
s5, tabletting, namely adding 6% polyvinyl alcohol aqueous solution in percentage by mass into the pre-sintered powder after the grinding balls obtained in the S4, granulating, sieving by a 40-mesh sieve to obtain spherical powder substances, and maintaining the pressure for 60S under the condition of 150MPa of one-way pressure to obtain a wafer-shaped ceramic blank; the mass ratio of the 6% polyvinyl alcohol aqueous solution to the pre-sintered powder after ball grinding is 25%:1;
s6, sintering: sintering the disk-shaped ceramic blank obtained in the step S5 to obtain a sintered ceramic blank; the sintering conditions are as follows: firstly, heating from room temperature to 550 ℃ at the heating rate of 3 ℃/min, keeping the temperature for 3h, then heating to 1230 ℃ at the heating rate of 3 ℃/min, sintering for 4h, and then cooling to room temperature at the cooling rate of 5 ℃/min;
s7, polishing: polishing the upper surface and the lower surface of the sintered ceramic blank obtained in the step S6 by using 600-mesh abrasive paper, polishing the upper surface and the lower surface by using 2000-mesh abrasive paper and carborundum until the thickness is 0.5mm, putting the ceramic blank into deionized water, ultrasonically cleaning and drying the ceramic blank to obtain a polished ceramic blank;
s8, surface metallization: and (4) uniformly coating silver pastes with the thickness of 0.01mm on the upper surface and the lower surface of the polished ceramic blank obtained in the step (S7), preserving the heat for 10min at the temperature of 850 ℃, and naturally cooling to room temperature to obtain the sodium niobate-bismuth magnesium niobate-barium magnesium niobate-strontium titanate transparent medium energy storage ceramic material.
Example 3
The sodium niobate-bismuth magnesium niobate-barium magnesium niobate-strontium titanate transparent medium energy storage ceramic material of the embodiment has a composition formula as follows: 0.95[ 2 ], [0.90NaNbO ] 3 -0.10(0.80Bi(Mg 2/3 Nb 1/3 )O 3 -0.20Ba(Mg 1/3 Nb 2/3 )O 3 )]-0.05SrTiO 3 。
The embodiment also provides a method for preparing the sodium niobate-bismuth magnesium niobate-barium magnesium niobate-strontium titanate transparent medium energy storage ceramic material, which comprises the following steps:
s1, drying materials: respectively adding Na 2 CO 3 Raw material, bi 2 O 3 Raw material, baCO 3 Raw material and SrCO 3 Drying the raw materials respectively at 300 ℃ for 6h;
nb to 2 O 5 Raw material, tiO 2 Respectively drying the raw material and the MgO raw material for 4 hours in strips at the temperature of 900 ℃;
the Na is 2 CO 3 The purity of the raw material is 99.8 percent, and the Bi is 2 O 3 The purity of the raw material is 99.8 percent, and the BaCO is 3 The purity of the raw material is 99 percent, and the SrCO 3 The purity of the raw material is 99 percent, and the Nb is 2 O 5 The purity of (2) is 99.5%, the purity of the MgO raw material is 98.5%, and the MgO raw material is purchased from national medicine group chemical reagent limited company;
s2, preparing materials: drying the dried Na in the S1 2 CO 3 Raw material, bi 2 O 3 Raw material, baCO 3 Raw material SrCO 3 Raw Material, nb 2 O 5 Raw material, tiO 2 The raw material and MgO raw material are in accordance with 0.95[ 2 ], [0.90NaNbO ] 3 -0.10(0.8Bi(Mg 2/3 Nb 1/3 )O 3 -0.2Ba(Mg 1/3 Nb 2/3 )O 3 )]-0.05SrTiO 3 The stoichiometric ratio of (A) is respectively weighed, namely the dried Na is weighed 2 CO 3 5.1223g of raw Material, bi 2 O 3 2.0179g of raw material, baCO 3 0.4273g of raw material and SrCO 3 0.8412g of raw materials, nb 2 O 5 Raw materials 13.4575g, tiO 2 0.4598g of raw material and 0.2631g of MgO raw material are uniformly mixed to obtain premix, agate balls and absolute ethyl alcohol are added, ball milling is carried out for 6h at the speed of 300r/min, after the agate balls are separated, drying is carried out for 12h at the temperature of 100 ℃, and after grinding, sieving is carried out by a 120-mesh sieve to obtain a raw material mixture; the dosage ratio of the premix, the agate balls and the absolute ethyl alcohol is 0.35g: 0.52mL;
s3, pre-burning: pre-burning the raw material mixture obtained in the step S2 for 2 hours at the temperature of 950 ℃, naturally cooling to room temperature, and grinding to obtain pre-burnt powder;
s4, secondary ball milling: adding agate balls and absolute ethyl alcohol into the pre-sintering powder obtained in the step S3, carrying out ball milling for 10 hours, separating the agate balls, drying at the temperature of 100 ℃ for 12 hours, and sieving through a 180-mesh sieve after grinding to obtain the pre-sintering powder after ball milling; the dosage ratio of the agate balls to the absolute ethyl alcohol added into the pre-sintering powder is 0.30g: 0.40mL;
s5, tabletting, namely adding 6% polyvinyl alcohol aqueous solution in percentage by mass into the pre-sintered powder after the grinding balls obtained in the S4, granulating, sieving by a 40-mesh sieve to obtain spherical powder substances, and maintaining the pressure for 20S under the condition of the one-way pressure of 200MPa to obtain a wafer-shaped ceramic blank; the mass ratio of the 6% polyvinyl alcohol aqueous solution to the pre-sintered powder after ball grinding is 35%:1;
s6, sintering: sintering the disk-shaped ceramic blank obtained in the step S5 to obtain a sintered ceramic blank; the sintering conditions are as follows: firstly heating from room temperature to 550 ℃ at the heating rate of 3 ℃/min, preserving heat for 3h, then heating to 1300 ℃ at the heating rate of 5 ℃/min, sintering for 2h, and then cooling to room temperature at the cooling rate of 5 ℃/min;
s7, polishing: grinding the upper surface and the lower surface of the sintered ceramic blank obtained in the step S6 by using 600-mesh abrasive paper, polishing the upper surface and the lower surface by using 2000-mesh abrasive paper and carborundum until the thickness is 0.5mm, putting the ceramic blank into deionized water, ultrasonically cleaning and drying the ceramic blank to obtain a polished ceramic blank;
s8, surface metallization: and (4) uniformly coating silver paste with the thickness of 0.03mm on the upper surface and the lower surface of the polished ceramic blank obtained in the step (S7), preserving the heat for 10min at the temperature of 850 ℃, and naturally cooling to room temperature to obtain the sodium niobate-bismuth magnesium niobate-barium magnesium niobate-strontium titanate transparent medium energy storage ceramic material.
Example 4
The sodium niobate-bismuth magnesium niobate-barium magnesium niobate-strontium titanate transparent medium energy storage ceramic material of the embodiment has a composition formula as follows: 0.95[ 2 ], [0.90NaNbO ] 3 -0.10(0.75Bi(Mg 2/3 Nb 1/3 )O 3 -0.25Ba(Mg 1/3 Nb 2/3 )O 3 )]-0.05SrTiO 3 。
The embodiment also provides a method for preparing the sodium niobate-bismuth magnesium niobate-barium magnesium niobate-strontium titanate transparent medium energy storage ceramic material, which comprises the following steps:
s1, drying materials: respectively adding Na 2 CO 3 Raw material, bi 2 O 3 Raw Material, baCO 3 Raw material and SrCO 3 Drying the raw materials for 6h at 300 ℃ respectively;
nb to 2 O 5 Raw material, tiO 2 The raw material and MgO raw material are respectively heated at 900 deg.CDrying the strips at the temperature of 4 hours;
the Na is 2 CO 3 The purity of the raw material is 99.8 percent, and the Bi is 2 O 3 The purity of the raw material is 99.8 percent, and the BaCO 3 The purity of the raw material is 99 percent, and the SrCO 3 The purity of the raw material is 99 percent, and the Nb is 2 O 5 The purity of the MgO raw material is 99.5 percent, the purity of the MgO raw material is 98.5 percent, and the MgO raw material is purchased from chemical reagents of national medicine group, inc.;
s2, preparing materials: drying the dried Na in the S1 2 CO 3 Raw material, bi 2 O 3 Raw material, baCO 3 Raw material SrCO 3 Raw Material, nb 2 O 5 Raw material, tiO 2 The raw material and MgO raw material are in accordance with 0.95[ 2 ], [0.90NaNbO ] 3 -0.10(0.75Bi(Mg 2/3 Nb 1/3 )O 3 -0.25Ba(Mg 1/ 3 Nb 2/3 )O 3 )]-0.05SrTiO 3 The stoichiometric ratio of (A) is respectively weighed, namely the dried Na is weighed 2 CO 3 5.1290g of raw material and Bi 2 O 3 Raw material 1.8942g, baCO 3 0.5348g of raw material, srCO 3 Raw materials 0.8423g, nb 2 O 5 13.4990g of raw material, tiO 2 0.4604g of raw material and 0.2562g of MgO raw material are uniformly mixed to obtain a premix, agate balls and absolute ethyl alcohol are added, ball milling is carried out for 7 hours at the speed of 300r/min, after the agate balls are separated, drying is carried out for 15 hours at the temperature of 90 ℃, and after grinding, the mixture is sieved by a 120-mesh sieve to obtain a raw material mixture; the dosage ratio of the premix, the agate balls and the absolute ethyl alcohol is 0.35g: 0.52mL;
s3, pre-burning: pre-burning the raw material mixture obtained in the step S2 for 2 hours at the temperature of 880 ℃, naturally cooling to room temperature, and grinding to obtain pre-burnt powder;
s4, secondary ball milling: adding agate balls and absolute ethyl alcohol into the pre-sintering powder obtained in the step S3, carrying out ball milling for 9 hours, separating the agate balls, drying at the temperature of 95 ℃ for 15 hours, and sieving with a 180-mesh sieve after grinding to obtain the pre-sintering powder after ball milling; the dosage ratio of the agate balls to the absolute ethyl alcohol added into the pre-sintering powder is 0.30g: 0.40mL;
s5, tabletting, namely adding 6% polyvinyl alcohol aqueous solution in percentage by mass into the pre-sintered powder after the grinding balls obtained in the S4, granulating, sieving by a 40-mesh sieve to obtain spherical powder substances, and maintaining the pressure for 30S under the condition of the unidirectional pressure of 180MPa to obtain a wafer-shaped ceramic blank; the mass ratio of the 6% polyvinyl alcohol aqueous solution to the pre-sintered powder after ball grinding is 25%:1;
s6, sintering: sintering the disk-shaped ceramic blank obtained in the step S5 to obtain a sintered ceramic blank; the sintering conditions are as follows: firstly, heating from room temperature to 550 ℃ at the heating rate of 3 ℃/min, preserving heat for 3h, then heating to 1280 ℃ at the heating rate of 3 ℃/min, sintering for 3h, and then cooling to room temperature at the cooling rate of 5 ℃/min;
s7, polishing: polishing the upper surface and the lower surface of the sintered ceramic blank obtained in the step S6 by using 600-mesh abrasive paper, polishing the upper surface and the lower surface by using 2000-mesh abrasive paper and carborundum until the thickness is 0.4mm, putting the ceramic blank into deionized water, ultrasonically cleaning and drying the ceramic blank to obtain a polished ceramic blank;
s8, surface metallization: and (4) uniformly coating silver pastes with the thickness of 0.02mm on the upper surface and the lower surface of the polished ceramic blank obtained in the step (S7), preserving the heat for 10min at the temperature of 850 ℃, and naturally cooling to room temperature to obtain the sodium niobate-bismuth magnesium niobate-barium magnesium niobate-strontium titanate transparent medium energy storage ceramic material.
As can be seen from FIG. 1, the ceramic materials prepared in examples 1 to 4 are all pure perovskite structures. As can be seen from FIG. 2, the ceramic materials prepared in examples 1 to 4 have uniform grain size and dense particle distribution. As can be seen from FIGS. 3 and 4, the breakdown field strengths of the ceramic materials prepared in examples 1 to 4 reached 326Kv/cm,347Kv/cm,424Kv/cm and 372Kv/cm, respectively, where 0.95[0.90NaNbO ] prepared in example 3 3 -0.10(0.80Bi(Mg 2/3 Nb 1/3 )O 3 -0.20Ba(Mg 1/3 Nb 2/3 )O 3 )]-0.05SrTiO 3 The ceramic material has the best energy storage performance, and the maximum polarization intensity (Pmax) is 27.56 mu C/cm 2 The residual polarization intensity (Pr) was 0.92. Mu.C/cm 2 Energy storage Density (W) rec ) Reaches 4.49J/cm 3 The energy storage efficiency (eta) reaches 87 percent. As can be seen from FIGS. 5 and 6, 0.95[ 2 ] 0.90NaNbO prepared in example 3 3 -0.10(0.80Bi(Mg 2/3 Nb 1/3 )O 3 -0.20Ba(Mg 1/3 Nb 2/3 )O 3 )]-0.05SrTiO 3 The ceramic material has excellent energy storage performance, temperature stability and frequency stability, and the change value of the energy storage density Wrec in the temperature range of 25-175 DEG C<17% of the total weight of the composition, and the variation value is in the range of 1-300Hz<2 percent. As can be seen from fig. 7, the ceramic material prepared in example 3 exhibits a certain light transmittance, which can reach 50.60% in the near infrared region.
Meanwhile, the light transmittance of the ceramic materials prepared in example 1, example 2 and example 4 in the near infrared region was measured to be 48.90%, 47.80% and 49.80%, respectively
Therefore, the sodium niobate-bismuth magnesium niobate-barium magnesium niobate-strontium titanate transparent dielectric energy storage ceramic material prepared in the embodiments 1 to 4 has light transmittance, and can be used for preparing a transparent pulse capacitor, compared with the common methods of hot-pressing sintering, hot isostatic pressing sintering, vacuum sintering, microwave sintering and the like in the conventional transparent ceramic preparation, the preparation method adopts common normal-pressure sintering, no sintering aid is required to be added, the production process is simple, the cost is low, economy and energy conservation are realized, the purity of the obtained ceramic material is high, the capacitor prepared by the material overcomes the defect that the conventional pulse capacitor can not simultaneously meet the requirements of high light transmittance and high energy storage density, and the material has huge application potential and economic benefit in the fields of transparent electronic equipment, such as electronic readers, smart phones, touch screens and the like.
The above description is only for the preferred embodiment of the present invention, and is not intended to limit the present invention in any way. Any simple modification, change and equivalent changes of the above embodiments according to the technical essence of the invention are still within the protection scope of the technical solution of the invention.

Claims (6)

1. The sodium niobate-bismuth magnesium niobate-barium magnesium niobate-strontium titanate transparent medium energy storage ceramic material is characterized by comprising the following components in percentage by weight: 0.95[ 2 ], [0.90NaNbO ] 3 -0.10((1-x)Bi(Mg 2/3 Nb 1/3 )O 3 -xBa(Mg 1/3 Nb 2/3 )O 3 )]-0.05SrTiO 3 Wherein x is mole percentage, and x is more than or equal to 0.10 and less than or equal to 0.25.
2. A method for preparing the sodium niobate-bismuth magnesium niobate-barium magnesium niobate-strontium titanate transparent medium energy storage ceramic material of claim 1, which comprises the following steps:
s1, drying materials: respectively adding Na 2 CO 3 Raw material, bi 2 O 3 Raw Material, baCO 3 Raw material and SrCO 3 Drying the raw materials respectively at 300 ℃ for 6h;
mixing Nb with 2 O 5 Raw material, tiO 2 Respectively drying the raw material and the MgO raw material for 4 hours at the temperature of 900 ℃;
the Na is 2 CO 3 The purity of the raw material is 99.8 percent, and the Bi is 2 O 3 The purity of the raw material is 99.8 percent, and the BaCO is 3 The purity of the raw material is 99 percent, and the SrCO 3 The purity of the raw material is 99 percent, and the Nb is 2 O 5 The purity of the MgO raw material is 99.5 percent, and the purity of the MgO raw material is 98.5 percent;
s2, preparing materials: drying the dried Na in the S1 2 CO 3 Raw material, bi 2 O 3 Raw material, baCO 3 Raw material SrCO 3 Raw material, nb 2 O 5 Raw material, tiO 2 The raw material and MgO raw material are in accordance with 0.95[ 2 ], [0.90NaNbO ] 3 -0.10((1-x)Bi(Mg 2/3 Nb 1/3 )O 3 -xBa(Mg 1/3 Nb 2/3 )O 3 )]-0.05SrTiO 3 Respectively weighing the above stoichiometric ratio, uniformly mixing to obtain a premix, adding agate balls and absolute ethyl alcohol, ball-milling for 6-10 h, separating the agate balls, drying at 80-100 ℃ for 12-24 h, and sieving with a 120-mesh sieve to obtain a raw material mixture;
s3, pre-burning: pre-burning the raw material mixture obtained in the step S2 at 850-950 ℃ for 2-4 h, naturally cooling to room temperature, and grinding to obtain pre-burned powder;
s4, secondary ball milling: adding agate balls and absolute ethyl alcohol into the pre-sintered powder obtained in the S3, performing ball milling for 6-10 h, separating the agate balls, drying at the temperature of 80-100 ℃ for 12-24 h, and sieving through a 180-mesh sieve after grinding to obtain the pre-sintered powder after ball milling;
s5, tabletting, namely adding 6 percent of polyvinyl alcohol aqueous solution into the pre-sintered powder after the grinding balls obtained in the S4, granulating, sieving by a 40-mesh sieve to obtain spherical powder substances, and maintaining the pressure for 20-60S under the condition of the unidirectional pressure of 150-200 MPa to obtain a disk-shaped ceramic blank;
s6, sintering: sintering the disk-shaped ceramic blank obtained in the step S5 to obtain a sintered ceramic blank; the sintering conditions are as follows: firstly, heating up to 550 ℃ from room temperature at a heating rate of 3 ℃/min, keeping the temperature for 3h, then heating up to 1230-1300 ℃ at a heating rate of 3-5 ℃/min, sintering for 2-4 h, and then cooling to room temperature at a cooling rate of 5 ℃/min;
s7, polishing: polishing the upper surface and the lower surface of the sintered ceramic blank obtained in the step S6 by using 600-mesh abrasive paper, polishing the upper surface and the lower surface by using 2000-mesh abrasive paper and carborundum until the thickness is 0.3-0.5 mm, putting the polished ceramic blank into deionized water, ultrasonically cleaning and drying the polished ceramic blank to obtain a polished ceramic blank;
s8, surface metallization: and (4) uniformly coating silver pastes with the thickness of 0.01-0.03 mm on the upper surface and the lower surface of the polished ceramic blank obtained in the step (S7), preserving the heat for 10min at the temperature of 850 ℃, and naturally cooling to room temperature to obtain the sodium niobate-bismuth magnesium niobate-barium magnesium niobate-strontium titanate transparent medium energy storage ceramic material.
3. The method according to claim 2, wherein the premix, the agate balls and the absolute ethyl alcohol in the S2 are used in a ratio of 0.35g: 0.52mL.
4. The method according to claim 2, characterized in that the amount ratio of the agate balls to the absolute ethyl alcohol added to the pre-sintering powder of S4 is 0.30g: 0.40mL.
5. The method according to claim 2, wherein the mass ratio of the 6% polyvinyl alcohol aqueous solution to the pre-sintered powder after ball milling in S5 is (25-35%): 1.
6. the application of the sodium niobate-bismuth magnesium niobate-barium magnesium niobate-strontium titanate transparent medium energy storage ceramic material prepared by the method as claimed in any one of claims 2 to 5, wherein the sodium niobate-bismuth magnesium niobate-barium magnesium niobate-strontium titanate transparent medium energy storage ceramic material has light transmittance and is used for preparing transparent pulse capacitors.
CN202211250523.2A 2022-10-12 2022-10-12 Transparent dielectric energy storage ceramic material and preparation method and application thereof Active CN115536390B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202211250523.2A CN115536390B (en) 2022-10-12 2022-10-12 Transparent dielectric energy storage ceramic material and preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202211250523.2A CN115536390B (en) 2022-10-12 2022-10-12 Transparent dielectric energy storage ceramic material and preparation method and application thereof

Publications (2)

Publication Number Publication Date
CN115536390A CN115536390A (en) 2022-12-30
CN115536390B true CN115536390B (en) 2023-04-18

Family

ID=84732878

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202211250523.2A Active CN115536390B (en) 2022-10-12 2022-10-12 Transparent dielectric energy storage ceramic material and preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN115536390B (en)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116063074B (en) * 2023-01-19 2023-09-26 同济大学 Ceramic material with high energy storage density and preparation method and application thereof
CN116854469A (en) * 2023-06-28 2023-10-10 长安大学 Sodium bismuth titanate-based high-entropy medium energy storage ceramic material and preparation method and application thereof

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2342259A1 (en) * 1976-02-26 1977-09-23 Morin Denise Transparent, ceramic, ferroelectric, lead free niobate - made by sintering fine precurson powder and used for optical commutators
JP2008056549A (en) * 2006-09-04 2008-03-13 National Institute Of Advanced Industrial & Technology Unleaded piezoelectric porcelain composition
CN110342933B (en) * 2019-06-19 2021-05-28 西安交通大学 Method for regulating curie temperature of sodium niobate ceramic
CN111704463B (en) * 2020-07-18 2022-04-12 桂林理工大学 Dielectric ceramic material and preparation method thereof
CN112919907B (en) * 2021-02-09 2022-09-20 杭州电子科技大学 Lead-free ferroelectric ceramic material with enhanced energy storage efficiency and high energy storage capacity and preparation method thereof

Also Published As

Publication number Publication date
CN115536390A (en) 2022-12-30

Similar Documents

Publication Publication Date Title
CN115536390B (en) Transparent dielectric energy storage ceramic material and preparation method and application thereof
CN109354492B (en) Bismuth-based lead-free high-energy-density ceramic material and preparation method thereof
CN109574656A (en) A kind of high energy storage bismuth-sodium titanate-strontium titanate base dielectric material and preparation method thereof
CN109180181B (en) Lead-free relaxation antiferroelectric ceramic energy storage material and preparation method thereof
CN106587997A (en) SrTiO&lt;3&gt;-based lead-free high-energy-density ceramic material and preparation method thereof
CN102826847A (en) Composite high dielectric constant microwave dielectric ceramic material and preparation method thereof
CN102674832A (en) Barium-titanate-base lead-free bismuth-containing relaxation ferroelectric ceramic material and preparation method thereof
CN110981479B (en) High-breakdown ferroelectric ceramic and preparation method thereof
CN112876247A (en) Wide-temperature-stability high-energy-storage-density strontium sodium niobate-based tungsten bronze ceramic and preparation method thereof
CN111004030B (en) MgTiO (magnesium-titanium-oxide) powder3Microwave-based dielectric ceramic and preparation method thereof
CN110357624B (en) High-dielectric-constant glass frit modified strontium zirconate doped potassium-sodium niobate lead-free transparent ceramic material and preparation method thereof
CN102976748A (en) High-density barium strontium titanate ceramic and preparation method thereof
CN100584796C (en) Y2O3-TiO2 series microwave dielectric ceramic and preparation method thereof
CN114085079A (en) High-energy-storage non-equimolar-ratio high-entropy perovskite oxide ceramic material and preparation method thereof
CN113511893B (en) BNT-based high-energy-density ceramic with three-layer structure and preparation method thereof
CN114436643A (en) Giant dielectric constant and low dielectric loss ceramic and preparation method thereof
CN113929458A (en) High-efficiency high-energy-storage sodium niobate-based ceramic material and preparation method thereof
CN116986902A (en) High-entropy perovskite ceramic material with submicron fine grain structure and preparation method thereof
CN112645709A (en) PZT-based piezoelectric ceramic and preparation method thereof
CN111217604A (en) Sodium bismuth titanate-based electronic ceramic with high energy storage density and high efficiency and preparation method thereof
CN105884352A (en) Novel ceramic capacitor material Ba4RFe0.5Nb9.5O30(R=La, Eu, Gd) and preparation method thereof
CN111153698B (en) Transparent ferroelectric ceramic material and preparation method and application thereof
CN113800904A (en) High-energy low-loss BNT-SBT-xSMN ceramic material and preparation method thereof
CN114560695B (en) Preparation method of composite ceramic material with high energy storage density and high energy storage efficiency
CN109851357A (en) A kind of unleaded high-dielectric and low-loss X9R temperature-stable ceramic composite and preparation method thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant