CN107473732B - Strontium titanate-based ceramic material with high energy storage density and low dielectric loss and preparation method thereof - Google Patents

Strontium titanate-based ceramic material with high energy storage density and low dielectric loss and preparation method thereof Download PDF

Info

Publication number
CN107473732B
CN107473732B CN201710771033.XA CN201710771033A CN107473732B CN 107473732 B CN107473732 B CN 107473732B CN 201710771033 A CN201710771033 A CN 201710771033A CN 107473732 B CN107473732 B CN 107473732B
Authority
CN
China
Prior art keywords
energy storage
ceramic material
dielectric loss
storage density
low dielectric
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
CN201710771033.XA
Other languages
Chinese (zh)
Other versions
CN107473732A (en
Inventor
杨海波
闫非
林营
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.)
Shaanxi University of Science and Technology
Original Assignee
Shaanxi University of Science and Technology
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 Shaanxi University of Science and Technology filed Critical Shaanxi University of Science and Technology
Priority to CN201710771033.XA priority Critical patent/CN107473732B/en
Publication of CN107473732A publication Critical patent/CN107473732A/en
Application granted granted Critical
Publication of CN107473732B publication Critical patent/CN107473732B/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
    • C04B35/46—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 titanium oxides or titanates
    • C04B35/462—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 titanium oxides or titanates based on titanates
    • C04B35/465—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 titanium oxides or titanates based on titanates based on alkaline earth metal titanates
    • C04B35/47—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 titanium oxides or titanates based on titanates based on alkaline earth metal titanates based on strontium titanates
    • 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
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • 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
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • C04B35/62605—Treating the starting powders individually or as mixtures
    • 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
    • C04B2235/3201—Alkali metal oxides or oxide-forming salts thereof
    • C04B2235/3203—Lithium oxide 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
    • C04B2235/3224—Rare earth oxide or oxide forming salts thereof, e.g. scandium oxide
    • C04B2235/3227—Lanthanum oxide 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
    • C04B2235/3234—Titanates, not containing zirconia
    • 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
    • C04B2235/3244—Zirconium oxides, zirconates, hafnium oxides, hafnates, 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
    • C04B2235/3298—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
    • C04B2235/60—Aspects relating to the preparation, properties or mechanical treatment of green bodies or pre-forms
    • C04B2235/602—Making the green bodies or pre-forms by moulding
    • C04B2235/6025—Tape casting, e.g. with a doctor blade
    • 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
    • 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
    • C04B2235/74—Physical characteristics
    • C04B2235/76—Crystal structural characteristics, e.g. symmetry
    • C04B2235/768—Perovskite structure ABO3
    • 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
    • C04B2235/74—Physical characteristics
    • C04B2235/78—Grain sizes and shapes, product microstructures, e.g. acicular grains, equiaxed grains, platelet-structures
    • C04B2235/782—Grain size distributions
    • 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
    • C04B2235/74—Physical characteristics
    • C04B2235/78—Grain sizes and shapes, product microstructures, e.g. acicular grains, equiaxed grains, platelet-structures
    • C04B2235/786—Micrometer sized grains, i.e. from 1 to 100 micron

Abstract

A strontium titanate-based ceramic material with high energy storage density and low dielectric loss and a preparation method thereof, according to the chemical formula (1-x) SrTiO3‑xBi0.48La0.02Na0.48Li0.02Ti0.98Zr0.02O3The preparation method comprises the steps of burdening and uniformly mixing to obtain raw material powder, uniformly mixing an organic solvent and an emulsifier, then adding the raw material powder, a binder, a dispersant and a plasticizer, uniformly mixing, carrying out tape casting, then cutting and stacking, and then carrying out pressurization, binder removal and sintering to obtain the strontium titanate-based ceramic material with high energy storage density and low dielectric loss. The ceramic material disclosed by the invention is simple in preparation process, mature in technology, suitable for industrial production, and based on the calculation of the hysteresis loop, the energy storage density is 1.98-2.59J/cm3The energy storage efficiency is 69-87%, and the electric field intensity is more than 200 kV/cm. It has excellent energy storage property and low dielectric loss.

Description

Strontium titanate-based ceramic material with high energy storage density and low dielectric loss and preparation method thereof
Technical Field
The invention belongs to the field of energy storage ceramics, and particularly relates to a strontium titanate-based ceramic material with high energy storage density and low dielectric loss and a preparation method thereof.
Background
Miniaturization and integration of pulsed power systems require energy storage dielectric materials with high energy storage density and low dielectric loss. The energy storage ceramic capacitor has the advantages of high charging and discharging speed, cyclic aging resistance, good mechanical property and suitability for extreme environments such as high temperature and high pressure, and the like, and further improves the energy storage density of the energy storage ceramic material while keeping lower dielectric loss is the key for developing and realizing the miniaturization of pulse components. In general, the energy storage density of the energy storage ceramic material can be calculated by a hysteresis loop (P-E curve). Its releasable energy density (W)rec) A closed region formed by a discharge curve and a Y axis in the electric hysteresis loop, and a total energy density (W) is a closed region formed by a charge curve and a Y axis in the electric hysteresis looprecThe ratio to W represents the energy storage efficiency (. eta.), WrecAnd η may be represented by the following formula:
Figure BDA0001395026970000011
Figure BDA0001395026970000012
as can be seen from the above formulas (1) and (2), in order to obtain a higher energy storage density, the prepared ceramic material must have a high electric field strength (E) and a large maximum polarization strength (P)max) And small remanent polarization (P)r). Meanwhile, the energy storage efficiency must be high in practical application. Since if the energy storage efficiency is too low, most of the stored energy will be released as heat during the energy release process, the released heat will reduce the life and other properties of the material. In addition, low dielectric losses are necessary over a range of operating frequencies and operating temperatures. The dielectric loss not only consumes the stored energy, but also causes the temperature of the device to rapidly increase along with the increase of the service time due to the dielectric loss, thereby affecting the normal use of the device.
SrTiO3Belong to ABO3The perovskite crystal is a typical quantum paraelectric body, has a cubic structure at room temperature, is paraelectric, has higher dielectric constant and higher compressive strength, has low dielectric loss and good frequency stability, and is one of the lead-free energy storage dielectric ceramic systems which are the most widely researched and most attractive at present. But SrTiO3The saturation polarization of the ceramic is low, and the energy storage density is low, so that the application of the ceramic in practical production is limited.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provides a strontium titanate-based ceramic material with high energy storage density and low dielectric loss and a preparation method thereof, the ceramic material has low dielectric loss and excellent energy storage density and energy storage efficiency, and the energy storage density can reach 2.59J/cm3The energy storage efficiency can reach more than 85%, the electric field intensity can reach 323kV/cm, the tape casting technology adopted in the preparation process is mature, and the used raw materials are low in price and have the characteristics of environmental friendliness, good practicability and the like.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a strontium titanate-based ceramic material with high energy storage density and low dielectric loss comprises the following steps:
(1) SrTiO according to the formula (1-x)3-xBi0.48La0.02Na0.48Li0.02Ti0.98Zr0.02O3Mixing the materials and uniformly mixing to obtain raw material powder, wherein x represents Bi0.48La0.02Na0.48Li0.02Ti0.98Zr0.02O3The mole fraction of x is more than or equal to 0.1 and less than or equal to 0.4;
(2) preparation of casting slurry: uniformly mixing an organic solvent and an emulsifier, adding the raw material powder obtained in the step (1), a binder, a dispersant and a plasticizer, and uniformly mixing to obtain casting slurry;
(3) preparation of a green body: carrying out tape casting on the tape casting slurry in a tape casting mode, then cutting and superposing the tape casting slurry as required, and pressurizing the tape casting slurry under the pressure of 150-200 MPa to obtain a ceramic material green body;
(4) and (4) carrying out glue discharging treatment on the ceramic material green body prepared in the step (3), and sintering the sample subjected to glue discharging treatment into ceramic to obtain the strontium titanate-based ceramic material with high energy storage density and low dielectric loss.
In a further development of the invention, the SrTiO3The powder was prepared by the following procedure: according to the formula SrTiO3Analytically pure SrCO3And TiO2Burdening and uniformly mixing, then sieving, briquetting, presintering at 1150-1200 ℃ for 3-5 hours to obtain blocky solid, then crushing the blocky solid and sieving by a 120-mesh sieve to obtain SrTiO3And (3) powder.
In a further development of the invention, Bi0.48La0.02Na0.48Li0.02Ti0.98Zr0.02O3The powder was prepared by the following procedure: according to the formula Bi0.48La0.02Na0.48Li0.02Ti0.98Zr0.02O3Adding Bi2O3、La2O3、Na2CO3、Li2CO3、TiO2And ZrO2Mixing, sieving,Briquetting, presintering for 3-4 hours at 800-850 ℃ to obtain blocky solid, crushing the blocky solid, and sieving with a 120-mesh sieve to obtain Bi0.48La0.02Na0.48Li0.02Ti0.98Zr0.02O3And (3) powder.
The further improvement of the invention is that the process of uniformly mixing in the step (1) is carried out by ball milling with absolute ethyl alcohol as a medium for 12-16 hours, and drying is carried out at 100 ℃ after ball milling.
The further improvement of the invention is that the process of uniformly mixing in the step (2) is carried out by ball milling, and the ball milling time is 4-6 hours.
The invention has the further improvement that in the step (2), the organic solvent is a mixture of absolute ethyl alcohol and butanone; the emulsifier is triolein; the binder is polyvinyl butyral; the dispersant is polyethylene glycol; the plasticizer is dibutyl phthalate.
The invention has the further improvement that the addition amount of the absolute ethyl alcohol in the step (2) is 50-55% of the mass of the raw material powder; the addition amount of butanone is the same as the mass of the raw material powder; the adding amount of the triolein is 3-4% of the mass of the raw material powder; the addition amount of the polyvinyl butyral is 9.5-10.5% of the mass of the raw material powder; the adding amount of the polyethylene glycol is 3-4% of the mass of the raw material powder; the adding amount of the dibutyl phthalate is 3-4% of the mass of the raw material powder.
The invention has the further improvement that the glue discharging treatment in the step (4) is specifically carried out by keeping the temperature at 500-600 ℃ for 10-15 hours.
The invention is further improved in that the sintering temperature in the step (4) is 1300-1350 ℃, and the time is 2-3 hours.
A strontium titanate-based ceramic material with high energy storage density and low dielectric loss has a chemical formula as follows: (1-x) SrTiO3-xBi0.48La0.02Na0.48Li0.02Ti0.98Zr0.02O3Wherein x represents Bi0.48La0.02Na0.48Li0.02Ti0.98Zr0.02O3The mole fraction of x is more than or equal to 0.1 and less than or equal to 0.4.
The further improvement of the invention is that the electric field intensity of the ceramic material is 209 to 323kV/cm, and the energy storage density is 1.98 to 2.59J/cm3And the energy storage efficiency reaches 87%.
Compared with the prior art, the invention has the following beneficial effects: the invention separately mixes SrTiO3Powder and Bi0.48La0.0 2Na0.48Li0.02Ti0.98Zr0.02O3The powder is uniformly mixed by a ball milling process according to the stoichiometric ratio, then tape casting is carried out, then binder removal treatment is carried out, and sintering is carried out, thus obtaining the strontium titanate-based ceramic material with high energy storage density and low dielectric loss. The strontium titanate-based ceramic material with high energy storage density and low dielectric loss has the advantages of low dielectric loss, simple preparation process, good stability, high density, no lead and no pollution, can meet the requirements of different applications, has cheap related raw materials and mature technical process, and is suitable for industrial production; according to the invention, high energy storage density and high energy storage efficiency can be obtained at the same time, wherein the high energy storage efficiency can effectively prevent the stored energy from being released in a thermal form, and the service life of the material is prolonged.
Furthermore, the organic solvent in the tape-casting slurry is composed of absolute ethyl alcohol and butanone, the mass ratio of the absolute ethyl alcohol to the butanone is 0.5-0.55, and due to the difference of volatilization speeds of the absolute ethyl alcohol and the butanone, the selection of the absolute ethyl alcohol and the butanone in a specific ratio can ensure that the solvent is volatilized and has residues at the same time, so that surface cracking caused by too fast volatilization is effectively avoided. Meanwhile, the casting slurry obtained by the invention has good stability and rheological property and high solid content, can be dried quickly and efficiently, shortens the drying time and is beneficial to industrial mass production.
The strontium titanate-based ceramic material with high energy storage density and low dielectric loss has uniform grain size distribution and high density, so that the material has higher breakdown electric field, can effectively improve the energy storage density, has excellent energy storage characteristic, and can reach the energy storage density of 2.59J/cm calculated based on the hysteresis loop3Efficiency of energy storageThe rate can reach more than 85 percent, and the electric field intensity is more than 200 kV/cm. Meanwhile, the energy storage ceramic dielectric material has low dielectric loss, and the dielectric loss under 1kHz is less than 0.007. The Curie temperature of the material under 1kHz is adjustable within the range of-130 to-10 ℃, and the dielectric property mutation caused by ferroelectric-paraelectric phase change can be effectively avoided according to the requirement of practical application, so that the material has better stability.
Drawings
Fig. 1 is an XRD spectrum of the strontium titanate-based high energy storage density and low dielectric loss ceramic material prepared in example 1;
fig. 2 is an XRD spectrum of the strontium titanate-based high energy storage density and low dielectric loss ceramic material prepared in example 2;
fig. 3 is an XRD spectrum of the strontium titanate-based high energy storage density and low dielectric loss ceramic material prepared in example 3;
fig. 4 is an XRD spectrum of the strontium titanate-based high energy storage density and low dielectric loss ceramic material prepared in example 4;
fig. 5 is an SEM image of the strontium titanate-based high energy storage density and low dielectric loss ceramic material prepared in example 1;
fig. 6 is an SEM image of the strontium titanate-based high energy storage density and low dielectric loss ceramic material prepared in example 2;
fig. 7 is an SEM image of the strontium titanate-based high energy storage density and low dielectric loss ceramic material prepared in example 3;
fig. 8 is an SEM image of the strontium titanate-based high energy storage density and low dielectric loss ceramic material prepared in example 4;
FIG. 9 is a hysteresis loop plot at a test frequency of 10Hz for the strontium titanate-based high energy storage density and low dielectric loss ceramic material prepared in example 1;
FIG. 10 is a hysteresis loop plot at 10Hz test frequency for the strontium titanate-based high energy storage density and low dielectric loss ceramic material prepared in example 2;
FIG. 11 is a hysteresis loop plot at 10Hz test frequency for the strontium titanate-based high energy storage density and low dielectric loss ceramic material prepared in example 3;
FIG. 12 is a plot of the hysteresis loop of the strontium titanate-based high energy storage density and low dielectric loss ceramic material prepared in example 4 at a test frequency of 10 Hz;
fig. 13 is a dielectric spectrum of the strontium titanate-based high energy storage density and low dielectric loss ceramic material prepared in example 1 at room temperature;
fig. 14 is a dielectric spectrum of the strontium titanate-based ceramic material with high energy storage density and low dielectric loss prepared in example 2 at room temperature;
fig. 15 is a dielectric spectrum of the strontium titanate-based high energy storage density and low dielectric loss ceramic material prepared in example 3 at room temperature;
fig. 16 is a dielectric spectrum of the strontium titanate-based ceramic material with high energy storage density and low dielectric loss prepared in example 4 at room temperature;
fig. 17 is a dielectric temperature spectrum of the strontium titanate-based ceramic material with high energy storage density and low dielectric loss prepared in example 1 at different testing frequencies;
fig. 18 is a dielectric temperature spectrum of the strontium titanate-based ceramic material with high energy storage density and low dielectric loss prepared in example 2 at different testing frequencies;
fig. 19 is a dielectric temperature spectrum of the strontium titanate-based high energy storage density and low dielectric loss ceramic material prepared in example 3 at different testing frequencies;
fig. 20 is a dielectric temperature spectrum of the strontium titanate-based ceramic material with high energy storage density and low dielectric loss prepared in example 4 at different testing frequencies.
Detailed Description
The present invention will be described in further detail with reference to the accompanying drawings and specific embodiments.
A strontium titanate-based ceramic material with high energy storage density and low dielectric loss has a chemical formula as follows: (1-x) SrTiO3-xBi0.48La0.02Na0.48Li0.02Ti0.98Zr0.02O3Wherein x represents Bi0.48La0.02Na0.48Li0.02Ti0.98Zr0.02O3The mole fraction of x is more than or equal to 0.1 and less than or equal to 0.4.
(1-x) of the present invention)SrTiO3-xBi0.48La0.02Na0.48Li0.02Ti0.98Zr0.02O3The preparation method comprises the following steps:
(1) according to the formula SrTiO3Analytically pure SrCO3And TiO2Preparing materials and uniformly mixing, then drying at 100 ℃, sieving with a 120-mesh sieve, briquetting, presintering for 3-5 hours at 1150-1200 ℃ to obtain blocky solid, then crushing the blocky solid and sieving with a 120-mesh sieve to obtain SrTiO3Powder;
(2) according to the formula Bi0.48La0.02Na0.48Li0.02Ti0.98Zr0.02O3Adding Bi2O3、La2O3、Na2CO3、Li2CO3、TiO2And ZrO2Burdening and uniformly mixing, then sieving, briquetting, presintering for 3-4 hours at 800-850 ℃ to obtain blocky solid, then crushing the blocky solid and sieving by a 120-mesh sieve to obtain Bi0.48La0.02Na0.48Li0.02Ti0.98Zr0.02O3Powder;
(3) SrTiO of step (1)3Powder and Bi in step (2)0.48La0.02Na0.48Li0.02Ti0.98Zr0.02O3The powder is SrTiO according to the chemical formula (1-x)3-xBi0.48La0.02Na0.48Li0.02Ti0.98Zr0.02O3Mixing materials, uniformly mixing, and sieving with a 120-mesh sieve to obtain raw material powder, wherein x represents Bi0.48La0.02Na0.48Li0.02Ti0.98Zr0.02O3The mole fraction of x is more than or equal to 0.1 and less than or equal to 0.4;
(4) preparation of casting slurry:
weighing an organic solvent (absolute ethyl alcohol and butanone) and an emulsifier (glyceryl trioleate) according to a ratio, ball-milling for 4-6 hours, and uniformly mixing;
and secondly, adding the raw material powder obtained in the step (3), a binder (polyvinyl butyral), a dispersant (polyethylene glycol) and a plasticizer (dibutyl phthalate) into the slurry uniformly mixed in the step (I), and performing ball milling for 4-6 hours to uniformly mix. Wherein the addition amount of the absolute ethyl alcohol is 50-55% of the mass of the raw material powder; the addition amount of butanone is the same as the mass of the raw material powder; the adding amount of the triolein is 3-4% of the mass of the raw material powder; the addition amount of the polyvinyl butyral is 9.5-10.5% of the mass of the raw material powder; the adding amount of the polyethylene glycol is 3-4% of the mass of the raw material powder; the adding amount of dibutyl phthalate is 3-4% of the mass of the raw material powder;
(5) carrying out tape casting on the slurry obtained in the step (4) by adopting a tape casting mode, then cutting and superposing the slurry according to the requirement, and pressurizing the slurry under the pressure of 150-200 MPa to obtain a strontium titanate-based ceramic material green body with high energy storage density and low dielectric loss;
(6) performing heat preservation on the strontium titanate-based ceramic material green body with high energy storage density and low dielectric loss obtained in the step (5) at 500-600 ℃ for 10-15 hours for glue removal treatment, and then performing heat preservation at 1300-1350 ℃ for 2-3 hours to sinter the strontium titanate-based ceramic material into ceramic to obtain the strontium titanate-based ceramic material with high energy storage density and low dielectric loss;
(6) carrying out X-ray diffraction test on the prepared strontium titanate-based ceramic material with high energy storage density and low dielectric loss;
(7) processing the sintered sample into a sheet with two smooth surfaces and a thickness of about 0.2mm, plating an electrode with gold, testing the ferroelectric property of the sample at the frequency of 10Hz at room temperature, and calculating the energy storage characteristic;
the step (1), the step (2) and the step (3) are uniformly mixed by using absolute ethyl alcohol as a medium and performing ball milling for 12-16 hours, and drying the mixture at 100 ℃ after ball milling.
The contents of the present invention will be further clarified by the following examples, which are not intended to limit the present invention.
Example 1
The chemical formula of the ceramic material is as follows: (1-x) SrTiO3-xBi0.48La0.02Na0.48Li0.02Ti0.98Zr0.02O3Wherein x represents Bi0.48La0.02Na0.48Li0.02Ti0.98Zr0.02O3Mole fraction, and x is 0.1.
The preparation method of the strontium titanate-based ceramic material with high energy storage density and low dielectric loss comprises the following steps:
(1) according to the formula SrTiO3Analytically pure SrCO3And TiO2After burdening, using absolute ethyl alcohol as a medium, ball-milling for 12 hours, uniformly mixing, drying at 100 ℃, sieving with a 120-mesh sieve, briquetting, presintering for 5 hours at 1150 ℃ to obtain a blocky solid, crushing the blocky solid, and sieving with the 120-mesh sieve to obtain SrTiO3Powder;
(2) according to the formula Bi0.48La0.02Na0.48Li0.02Ti0.98Zr0.02O3Adding Bi2O3，La2O3，Na2CO3，Li2CO3，TiO2And ZrO2Burdening, using absolute ethyl alcohol as a medium, ball-milling for 12 hours, uniformly mixing, drying at 100 ℃, then sieving with a 120-mesh sieve, briquetting, presintering at 800 ℃ for 4 hours to obtain blocky solids, crushing the blocky solids, and sieving with the 120-mesh sieve to obtain Bi0.48La0.02Na0.48Li0.02Ti0.98Zr0.02O3Powder;
(3) SrTiO of step (1)3Powder and Bi in step (2)0.48La0.02Na0.48Li0.02Ti0.98Zr0.02O3The powder is SrTiO according to the chemical formula (1-x)3-xBi0.48La0.02Na0.48Li0.02Ti0.98Zr0.02O3The materials are mixed, absolute ethyl alcohol is used as a medium, the materials are uniformly mixed through ball milling for 12 hours, then the materials are dried at the temperature of 100 ℃, and the materials are sieved by a 120-mesh sieve to obtain raw material powder. Wherein x represents Bi0.48La0.02Na0.48Li0.02Ti0.98Zr0.02O3Mole fraction, and x is 0.1;
(4) preparation of casting slurry: weighing organic solvent (absolute ethyl alcohol and butanone) and emulsifier (triolein) according to a ratio, ball-milling for 4 hours, and uniformly mixing; and secondly, adding the raw material powder obtained in the step (3), a binder (polyvinyl butyral), a dispersant (polyethylene glycol) and a plasticizer (dibutyl phthalate) into the slurry uniformly mixed in the step (I), and performing ball milling for 4 hours to uniformly mix the raw material powder, the binder (polyvinyl butyral), the dispersant (polyethylene glycol) and the plasticizer (dibutyl phthalate). Wherein the addition amount of the absolute ethyl alcohol is 50 percent of the mass of the raw material powder; the addition amount of butanone is the same as the mass of the raw material powder; the adding amount of the triolein is 3 percent of the mass of the raw material powder; the adding amount of the polyvinyl butyral is 9.5 percent of the mass of the raw material powder; the adding amount of the polyethylene glycol is 3 percent of the mass of the raw material powder; the adding amount of dibutyl phthalate is 3 percent of the mass of the raw material powder;
(5) carrying out tape casting on the slurry obtained in the step (4) by adopting a tape casting mode, then cutting and superposing the slurry according to the requirement, and pressurizing the slurry under the pressure of 150MPa to obtain a strontium titanate-based ceramic material green body with high energy storage density and low dielectric loss;
(6) performing heat preservation on the strontium titanate-based ceramic material green body with high energy storage density and low dielectric loss obtained in the step (5) at 500 ℃ for 15 hours for glue removal treatment, and then performing heat preservation at 1350 ℃ for 2 hours to sinter the strontium titanate-based ceramic material with high energy storage density and low dielectric loss into ceramic;
(7) and carrying out X-ray diffraction test on the prepared energy storage medium ceramic. Referring to fig. 1, it can be seen from the XRD spectrum that the ceramic material prepared in this example has a pure perovskite structure. FIG. 5 is an SEM image of the dielectric ceramic material prepared in the present example, which shows that the ceramic material has a compact structure and uniform grain size distribution, and the average grain size is 1.4 μm;
(8) processing the sintered sample into a sheet with two smooth surfaces and a thickness of about 0.2mm, plating a gold electrode, and then testing the ferroelectric property at room temperature under the frequency of 10Hz, as shown in FIG. 9, the ferroelectric property is shown in the hysteresis loop of the ceramic material of the embodiment, the hysteresis loop is relatively thin and long, the breakdown strength is 323kV/cm, and the energy storage density of the lead-free energy storage dielectric ceramic of the embodiment is calculated by performing energy storage characteristic calculation, and is 2.59J/ioncm3The energy storage efficiency is 85%. As shown in fig. 13, which is a dielectric frequency diagram measured at room temperature for the ceramic material of this embodiment, it can be seen that the dielectric constant of the prepared strontium titanate-based ceramic material with high energy storage density and low dielectric loss is about 940, and the strontium titanate-based ceramic material is substantially invariant with frequency increase, has good frequency stability, and has a dielectric loss of about 0.0009 at 1 kHz. Table 1 shows the dielectric and energy storage characteristics of the lead-free energy storage dielectric ceramic material of this embodiment. The dielectric temperature spectra of the energy storage ceramic material under different test frequencies are shown in FIG. 17, the Curie peak of a sample under 1kHz is about-130 ℃, and the dielectric loss of the sample is small in the range of-180-150 ℃.
Example 2
The chemical formula of the ceramic material is as follows: (1-x) SrTiO3-xBi0.48La0.02Na0.48Li0.02Ti0.98Zr0.02O3Wherein x represents Bi0.48La0.02Na0.48Li0.02Ti0.98Zr0.02O3Mole fraction, and x is 0.2.
The preparation method of the strontium titanate-based ceramic material with high energy storage density and low dielectric loss comprises the following steps:
(1) according to the formula SrTiO3Analytically pure SrCO3And TiO2After burdening, using absolute ethyl alcohol as a medium, ball-milling for 14 hours, uniformly mixing, drying at 100 ℃, sieving with a 120-mesh sieve, briquetting, presintering at 1180 ℃ for 4 hours to obtain a blocky solid, crushing the blocky solid, and sieving with the 120-mesh sieve to obtain SrTiO3Powder;
(2) according to the formula Bi0.48La0.02Na0.48Li0.02Ti0.98Zr0.02O3Adding Bi2O3、La2O3、Na2CO3、Li2CO3、TiO2And ZrO2Mixing materials, ball milling with anhydrous alcohol as medium for 14 hr, drying at 100 deg.C, sieving with 120 mesh sieve, briquetting, presintering at 850 deg.C for 3 hr to obtain block solid, and mixing with the above solidCrushing the blocky solid and sieving the blocky solid by a 120-mesh sieve to obtain Bi0.48La0.02Na0.48Li0.02Ti0.98Zr0.02O3Powder;
(3) SrTiO of step (1)3Powder and Bi in step (2)0.48La0.02Na0.48Li0.02Ti0.98Zr0.02O3The powder is SrTiO according to the chemical formula (1-x)3-xBi0.48La0.02Na0.48Li0.02Ti0.98Zr0.02O3The materials are mixed, absolute ethyl alcohol is used as a medium, the materials are uniformly mixed by ball milling for 14 hours, then the materials are dried at the temperature of 100 ℃, and the materials are sieved by a 120-mesh sieve to obtain raw material powder. Wherein x represents Bi0.48La0.02Na0.48Li0.02Ti0.98Zr0.02O3Mole fraction, and x is 0.2;
(4) preparation of casting slurry: weighing organic solvent (absolute ethyl alcohol and butanone) and emulsifier (triolein) according to a ratio, ball-milling for 6 hours, and uniformly mixing; and secondly, adding the raw material powder obtained in the step (3), a binder (polyvinyl butyral), a dispersant (polyethylene glycol) and a plasticizer (dibutyl phthalate) into the slurry uniformly mixed in the step (I), and performing ball milling for 4 hours to uniformly mix the raw material powder, the binder (polyvinyl butyral), the dispersant (polyethylene glycol) and the plasticizer (dibutyl phthalate). Wherein the addition amount of the absolute ethyl alcohol is 55 percent of the mass of the raw material powder; the addition amount of butanone is the same as the mass of the raw material powder; the addition amount of the triolein is 4 percent of the mass of the raw material powder; the adding amount of the polyvinyl butyral is 10.5 percent of the mass of the raw material powder; the addition of the polyethylene glycol is 4 percent of the mass of the raw material powder; the adding amount of dibutyl phthalate is 4 percent of the mass of the raw material powder;
(5) carrying out tape casting on the slurry obtained in the step (4) by adopting a tape casting mode, then cutting and superposing the slurry according to the requirement, and pressurizing the slurry under the pressure of 200MPa to obtain a strontium titanate-based ceramic material green body with high energy storage density and low dielectric loss;
(6) performing heat preservation on the strontium titanate-based ceramic material green body with high energy storage density and low dielectric loss obtained in the step (5) at 600 ℃ for 10 hours for glue removal treatment, and then performing heat preservation at 1325 ℃ for 3 hours to sinter the strontium titanate-based ceramic material with high energy storage density and low dielectric loss into ceramic;
(7) and carrying out X-ray diffraction test on the prepared energy storage medium ceramic. As shown in fig. 2, the XRD spectrum shows that the ceramic material prepared in this example has a pure perovskite structure. FIG. 6 is an SEM image of the dielectric ceramic material prepared in the present example, which shows that the ceramic material has a compact structure and uniform grain size distribution, and the average grain size is 1.7 μm;
(8) processing the sintered sample into a sheet with two smooth surfaces and a thickness of about 0.2mm, plating a gold electrode, and then testing the ferroelectric property at room temperature at a frequency of 10Hz, as shown in FIG. 10, the ferroelectric property is the hysteresis loop of the ceramic material of the embodiment, the hysteresis loop is relatively thin and long, the breakdown strength is 264kV/cm, and the energy storage density of the lead-free energy storage dielectric ceramic of the embodiment is calculated by performing the energy storage characteristic calculation, and is 2.14J/cm3The energy storage efficiency was 87%. As shown in fig. 14, which is a dielectric frequency diagram measured at room temperature for the ceramic material of this embodiment, it can be seen that the dielectric constant of the prepared strontium titanate-based ceramic material with high energy storage density and low dielectric loss is about 1524, and the strontium titanate-based ceramic material is substantially invariant with the increase of frequency, has good frequency stability, and has a dielectric loss of about 0.0012 at 1 kHz. Table 1 shows the dielectric and energy storage characteristics of the lead-free energy storage dielectric ceramic material of this embodiment. The dielectric temperature spectra of the energy storage ceramic material under different test frequencies are shown in FIG. 18, the Curie peak of a sample under 1kHz is about-83 ℃, and the dielectric loss of the sample is small in the range of-180-150 ℃.
Example 3
The chemical formula of the ceramic material is as follows: (1-x) SrTiO3-xBi0.48La0.02Na0.48Li0.02Ti0.98Zr0.02O3Wherein x represents Bi0.48La0.02Na0.48Li0.02Ti0.98Zr0.02O3Mole fraction, and x is 0.3.
The preparation method of the strontium titanate-based ceramic material with high energy storage density and low dielectric loss comprises the following steps:
(1) according to the formula SrTiO3Analytically pure SrCO3And TiO2After burdening, using absolute ethyl alcohol as a medium, ball-milling for 16 hours, uniformly mixing, drying at 100 ℃, sieving with a 120-mesh sieve, briquetting, presintering at 1200 ℃ for 3 hours to obtain a blocky solid, crushing the blocky solid, and sieving with the 120-mesh sieve to obtain SrTiO3Powder;
(2) according to the formula Bi0.48La0.02Na0.48Li0.02Ti0.98Zr0.02O3Adding Bi2O3，La2O3，Na2CO3，Li2CO3，TiO2And ZrO2Burdening, using absolute ethyl alcohol as a medium, ball-milling for 16 hours, uniformly mixing, drying at 100 ℃, sieving with a 120-mesh sieve, briquetting, presintering at 830 ℃ for 3.5 hours to obtain blocky solids, crushing the blocky solids, and sieving with the 120-mesh sieve to obtain Bi0.48La0.02Na0.48Li0.02Ti0.98Zr0.02O3Powder;
(3) SrTiO of step (1)3Powder and Bi in step (2)0.48La0.02Na0.48Li0.02Ti0.98Zr0.02O3The powder is SrTiO according to the chemical formula (1-x)3-xBi0.48La0.02Na0.48Li0.02Ti0.98Zr0.02O3The materials are mixed, absolute ethyl alcohol is used as a medium, the materials are uniformly mixed by ball milling for 16 hours, then the materials are dried at the temperature of 100 ℃, and the materials are sieved by a 120-mesh sieve to obtain raw material powder. Wherein x represents Bi0.48La0.02Na0.48Li0.02Ti0.98Zr0.02O3Mole fraction, and x is 0.3;
(4) preparation of casting slurry: weighing organic solvent (absolute ethyl alcohol and butanone) and emulsifier (triolein) according to a ratio, ball-milling for 5 hours, and uniformly mixing; and secondly, adding the raw material powder obtained in the step (3), a binder (polyvinyl butyral), a dispersant (polyethylene glycol) and a plasticizer (dibutyl phthalate) into the slurry uniformly mixed in the step (I), and performing ball milling for 5 hours to uniformly mix the raw material powder, the binder (polyvinyl butyral), the dispersant (polyethylene glycol) and the plasticizer (dibutyl phthalate). Wherein the addition amount of the absolute ethyl alcohol is 53 percent of the mass of the raw material powder; the addition amount of butanone is the same as the mass of the raw material powder; the adding amount of the triolein is 3.4 percent of the mass of the raw material powder; the adding amount of the polyvinyl butyral is 10 percent of the mass of the raw material powder; the adding amount of the polyethylene glycol is 3.4 percent of the mass of the raw material powder; the adding amount of the dibutyl phthalate is 3.4 percent of the mass of the raw material powder;
(5) carrying out tape casting on the slurry obtained in the step (4) by adopting a tape casting mode, then cutting and superposing the slurry according to the requirement, and pressurizing the slurry under the pressure of 180MPa to obtain a strontium titanate-based ceramic material green body with high energy storage density and low dielectric loss;
(6) performing heat preservation on the strontium titanate-based ceramic material green body with high energy storage density and low dielectric loss obtained in the step (5) at 550 ℃ for 12 hours for glue removal treatment, and then performing heat preservation at 1325 ℃ for 2 hours to sinter the strontium titanate-based ceramic material with high energy storage density and low dielectric loss into ceramic;
(7) and carrying out X-ray diffraction test on the prepared energy storage medium ceramic. As shown in fig. 3, the XRD spectrum shows that the ceramic material prepared in this example has a pure perovskite structure. FIG. 7 is an SEM image of the dielectric ceramic material prepared in the present example, which shows that the ceramic material has a compact structure and uniform grain size distribution, and the average grain size is 1.9 μm;
(8) processing the sintered sample into a sheet with two smooth surfaces and a thickness of about 0.2mm, plating a gold electrode, and then testing the ferroelectric property at room temperature under a frequency of 10Hz, as shown in FIG. 11, the ferroelectric property is the hysteresis loop of the ceramic material of the embodiment, the hysteresis loop is relatively thin and long, the breakdown strength is 230kV/cm, and the energy storage characteristic calculation is performed, so that the energy storage density of the lead-free energy storage dielectric ceramic of the embodiment is 2.22J/cm3The energy storage efficiency is 82%. As shown in fig. 15, which is a dielectric frequency diagram measured at room temperature for the ceramic material of this embodiment, it can be seen that the dielectric constant of the prepared strontium titanate-based ceramic material with high energy storage density and low dielectric loss is about 2238, and the strontium titanate-based ceramic material is substantially invariant with frequency increase, has good frequency stability, and has a dielectric loss of about 0.0061 at 1 kHz. TABLE 1 showsThe lead-free energy storage dielectric ceramic material has dielectric and energy storage characteristics. The dielectric temperature spectra of the energy storage ceramic material under different test frequencies are shown in figure 19, the Curie peak of a sample under 1kHz is about-41 ℃, and the dielectric loss of the sample is small in the range of-180-150 ℃.
Example 4
The chemical formula of the ceramic material is as follows: (1-x) SrTiO3-xBi0.48La0.02Na0.48Li0.02Ti0.98Zr0.02O3Wherein x represents Bi0.48La0.02Na0.48Li0.02Ti0.98Zr0.02O3Mole fraction, and x is 0.4.
The preparation method of the strontium titanate-based ceramic material with high energy storage density and low dielectric loss comprises the following steps:
(1) according to the formula SrTiO3Analytically pure SrCO3And TiO2After burdening, using absolute ethyl alcohol as a medium, ball-milling for 12 hours, uniformly mixing, drying at 100 ℃, sieving with a 120-mesh sieve, briquetting, presintering for 4 hours at 1160 ℃ to obtain a blocky solid, crushing the blocky solid, and sieving with the 120-mesh sieve to obtain SrTiO3Powder;
(2) according to the formula Bi0.48La0.02Na0.48Li0.02Ti0.98Zr0.02O3Adding Bi2O3，La2O3，Na2CO3，Li2CO3，TiO2And ZrO2Burdening, using absolute ethyl alcohol as a medium, ball-milling for 12 hours, uniformly mixing, drying at 100 ℃, then sieving with a 120-mesh sieve, briquetting, presintering at 820 ℃ for 4 hours to obtain blocky solids, crushing the blocky solids, and sieving with the 120-mesh sieve to obtain Bi0.48La0.02Na0.48Li0.02Ti0.98Zr0.02O3Powder;
(3 mixing the SrTiO of the step (1)3Powder and Bi in step (2)0.48La0.02Na0.48Li0.02Ti0.98Zr0.02O3The powder is SrTiO according to the chemical formula (1-x)3-xBi0.48La0.02Na0.48Li0.02Ti0.98Zr0.02O3The materials are mixed, absolute ethyl alcohol is used as a medium, the materials are uniformly mixed through ball milling for 12 hours, then the materials are dried at the temperature of 100 ℃, and the materials are sieved by a 120-mesh sieve to obtain raw material powder. Wherein x represents Bi0.48La0.02Na0.48Li0.02Ti0.98Zr0.02O3Mole fraction, and x is 0.4;
(4) preparation of casting slurry: weighing organic solvent (absolute ethyl alcohol and butanone) and emulsifier (triolein) according to a ratio, ball-milling for 4 hours, and uniformly mixing; and secondly, adding the raw material powder obtained in the step (3), a binder (polyvinyl butyral), a dispersant (polyethylene glycol) and a plasticizer (dibutyl phthalate) into the slurry uniformly mixed in the step (I), and performing ball milling for 4 hours to uniformly mix the raw material powder, the binder (polyvinyl butyral), the dispersant (polyethylene glycol) and the plasticizer (dibutyl phthalate). Wherein the addition amount of the absolute ethyl alcohol is 52 percent of the mass of the raw material powder; the addition amount of butanone is the same as the mass of the raw material powder; the adding amount of the triolein is 3.6 percent of the mass of the raw material powder; the adding amount of the polyvinyl butyral is 10 percent of the mass of the raw material powder; the adding amount of the polyethylene glycol is 3.6 percent of the mass of the raw material powder; the adding amount of the dibutyl phthalate is 3.6 percent of the mass of the raw material powder;
(5) carrying out tape casting on the slurry obtained in the step (4) by adopting a tape casting mode, then cutting and superposing the slurry according to the requirement, and pressurizing the slurry under the pressure of 160MPa to obtain a strontium titanate-based ceramic material green body with high energy storage density and low dielectric loss;
(6) performing heat preservation on the strontium titanate-based ceramic material green body with high energy storage density and low dielectric loss obtained in the step (5) at 580 ℃ for 14 hours for glue removal treatment, and then performing heat preservation at 1300 ℃ for 2 hours to sinter the ceramic material into a strontium titanate-based ceramic material with high energy storage density and low dielectric loss;
(7) and carrying out X-ray diffraction test on the prepared energy storage medium ceramic. As shown in fig. 4, the XRD spectrum shows that the ceramic material prepared in this example has a pure perovskite structure. FIG. 8 is an SEM image of the dielectric ceramic material prepared in the present example, which shows that the ceramic material has a compact structure and uniform grain size distribution, and the average grain size is 2.6 μm;
(8) processing the sintered sample into a sheet with two smooth surfaces and a thickness of about 0.2mm, plating a gold electrode, and then testing the ferroelectric property at the room temperature under the frequency of 10Hz, as shown in FIG. 12, the ferroelectric property is the hysteresis loop of the ceramic material of the embodiment, the hysteresis loop is relatively thin and long, the breakdown strength is 209kV/cm, and the energy storage characteristic calculation is performed, so that the energy storage density of the lead-free energy storage dielectric ceramic of the embodiment is 1.98J/cm3The energy storage efficiency was 69%. As shown in fig. 16, which is a dielectric frequency diagram measured at room temperature for the ceramic material of this embodiment, it can be seen that the dielectric constant of the prepared strontium titanate-based ceramic material with high energy storage density and low dielectric loss is about 3293, and the strontium titanate-based ceramic material is substantially invariant with the increase of frequency, has good frequency stability, and has a dielectric loss of about 0.0066 at 1 kHz. Table 1 shows the dielectric and energy storage characteristics of the lead-free energy storage dielectric ceramic material of this embodiment. The dielectric temperature spectra of the energy storage ceramic material under different test frequencies are shown in figure 20, the Curie peak of a sample under 1kHz is about-10 ℃, and the dielectric loss of the sample is small in the range of-180-150 ℃.
TABLE 1 ferroelectric and energy storage characteristics of the lead-free energy storage ceramic materials of the examples
Figure BDA0001395026970000151
As is clear from Table 1, (1-x) SrTiO of the present invention3-xBi0.48La0.02Na0.48Li0.02Ti0.98Zr0.02O3The energy storage ceramic material has high energy storage density, high energy storage efficiency and low dielectric loss. The energy storage density of the invention is 1.98-2.59J/cm3And the energy storage efficiency is 69-87%. The dielectric loss at 1kHz is less than about 0.007. Meanwhile, the energy storage ceramic dielectric material has higher breakdown strength>200kV/cm), the bias range during use can be widened. In addition, the Curie temperature of the invention is adjustable within the range of-130 to-10 ℃, which can effectively avoid ironThe dielectric property mutation caused by the electric paraelectric phase change enables the material to have better dielectric temperature stability.
The ceramic material has the advantages of simple preparation process, mature technology, suitability for industrial production, excellent energy storage property and low dielectric loss. The energy storage density calculated based on the electric hysteresis loop is 1.98-2.59J/cm3The energy storage efficiency is 69-87%, and the electric field intensity is more than 200 kV/cm.
The contents of the present invention will be further clearly understood from the examples given above, but are not intended to limit the present invention.

Claims (7)

1. A preparation method of a strontium titanate-based ceramic material with high energy storage density and low dielectric loss is characterized by comprising the following steps:
(1) SrTiO according to the formula (1-x)3-xBi0.48La0.02Na0.48Li0.02Ti0.98Zr0.02O3Mixing the materials and uniformly mixing to obtain raw material powder, wherein x represents Bi0.48La0.02Na0.48Li0.02Ti0.98Zr0.02O3The mole fraction of x is more than or equal to 0.1 and less than or equal to 0.4; wherein, Bi0.48La0.02Na0.48Li0.02Ti0.98Zr0.02O3The powder was prepared by the following procedure: according to the formula Bi0.48La0.0 2Na0.48Li0.02Ti0.98Zr0.02O3Adding Bi2O3、La2O3、Na2CO3、Li2CO3、TiO2And ZrO2Burdening and uniformly mixing, then sieving, briquetting, presintering for 3-4 hours at 800-850 ℃ to obtain blocky solid, then crushing the blocky solid and sieving by a 120-mesh sieve to obtain Bi0.48La0.02Na0.48Li0.02Ti0.98Zr0.02O3Powder;
(2) preparation of casting slurry: uniformly mixing an organic solvent and an emulsifier, adding the raw material powder obtained in the step (1), a binder, a dispersant and a plasticizer, and uniformly mixing to obtain casting slurry; wherein the organic solvent is a mixture of absolute ethyl alcohol and butanone; the emulsifier is triolein; the binder is polyvinyl butyral; the dispersant is polyethylene glycol; the plasticizer is dibutyl phthalate; wherein the mass ratio of the absolute ethyl alcohol to the butanone is 0.5-0.55;
(3) preparation of a green body: carrying out tape casting on the tape casting slurry in a tape casting mode, then cutting and superposing the tape casting slurry as required, and pressurizing the tape casting slurry under the pressure of 150-200 MPa to obtain a ceramic material green body;
(4) and (4) carrying out glue discharging treatment on the ceramic material green body prepared in the step (3), and sintering the sample subjected to glue discharging treatment into ceramic to obtain the strontium titanate-based ceramic material with high energy storage density and low dielectric loss.
2. The method for preparing strontium titanate-based ceramic material with high energy storage density and low dielectric loss according to claim 1, wherein SrTiO is used as the material3The powder was prepared by the following procedure: according to the formula SrTiO3Analytically pure SrCO3And TiO2Burdening and uniformly mixing, then sieving, briquetting, presintering at 1150-1200 ℃ for 3-5 hours to obtain blocky solid, then crushing the blocky solid and sieving by a 120-mesh sieve to obtain SrTiO3And (3) powder.
3. The preparation method of the strontium titanate-based ceramic material with high energy storage density and low dielectric loss according to claim 1, wherein the step (1) of uniformly mixing is performed by ball milling with absolute ethyl alcohol as a medium, the ball milling time is 12-16 hours, and the ball milling is performed at 100 ℃ and then dried.
4. The preparation method of the strontium titanate-based ceramic material with high energy storage density and low dielectric loss according to claim 1, wherein the addition amount of the absolute ethyl alcohol in the step (2) is 50-55% of the mass of the raw material powder; the addition amount of butanone is the same as the mass of the raw material powder; the adding amount of the triolein is 3-4% of the mass of the raw material powder; the addition amount of the polyvinyl butyral is 9.5-10.5% of the mass of the raw material powder; the adding amount of the polyethylene glycol is 3-4% of the mass of the raw material powder; the adding amount of the dibutyl phthalate is 3-4% of the mass of the raw material powder.
5. The preparation method of the strontium titanate-based ceramic material with high energy storage density and low dielectric loss according to claim 1, wherein the step (4) of glue removal treatment is specifically to preserve heat at 500-600 ℃ for 10-15 hours.
6. The method for preparing a strontium titanate-based ceramic material with high energy storage density and low dielectric loss according to claim 1, wherein the sintering temperature in the step (4) is 1300-1350 ℃ and the sintering time is 2-3 hours.
7. A strontium titanate-based ceramic material with high energy storage density and low dielectric loss prepared by the method of any one of claims 1 to 6, wherein the ceramic material has a chemical formula: (1-x) SrTiO3-xBi0.48La0.02Na0.48Li0.02Ti0.98Zr0.02O3Wherein x represents Bi0.48La0.02Na0.48Li0.02Ti0.98Zr0.02O3The mole fraction of x is more than or equal to 0.1 and less than or equal to 0.4;
the electric field intensity of the ceramic material is 209-323 kV/cm, and the energy storage density is 1.98-2.59J/cm3And the energy storage efficiency reaches 69-87%.
CN201710771033.XA 2017-08-31 2017-08-31 Strontium titanate-based ceramic material with high energy storage density and low dielectric loss and preparation method thereof Active CN107473732B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201710771033.XA CN107473732B (en) 2017-08-31 2017-08-31 Strontium titanate-based ceramic material with high energy storage density and low dielectric loss and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201710771033.XA CN107473732B (en) 2017-08-31 2017-08-31 Strontium titanate-based ceramic material with high energy storage density and low dielectric loss and preparation method thereof

Publications (2)

Publication Number Publication Date
CN107473732A CN107473732A (en) 2017-12-15
CN107473732B true CN107473732B (en) 2020-10-27

Family

ID=60604355

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201710771033.XA Active CN107473732B (en) 2017-08-31 2017-08-31 Strontium titanate-based ceramic material with high energy storage density and low dielectric loss and preparation method thereof

Country Status (1)

Country Link
CN (1) CN107473732B (en)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108640675B (en) * 2018-06-13 2019-11-05 陕西科技大学 A kind of unleaded multilayer high energy storage density ceramic material and preparation method thereof
CN108623301B (en) * 2018-06-13 2019-10-11 陕西科技大学 A kind of unleaded low-dielectric loss and high energy storage density ceramics and preparation method thereof with sandwich structure
CN110967637B (en) * 2019-06-24 2020-12-29 宁德时代新能源科技股份有限公司 Method, device, system and storage medium for estimating allowable power of battery
CN110967638B (en) * 2019-06-24 2021-03-23 宁德时代新能源科技股份有限公司 Method, device, system and storage medium for estimating remaining usable energy of battery

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106699170A (en) * 2017-02-21 2017-05-24 陕西科技大学 Strontium titanate-based lead-free high-energy storage density and high-energy storage efficiency ceramic material and preparation method thereof

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106699170A (en) * 2017-02-21 2017-05-24 陕西科技大学 Strontium titanate-based lead-free high-energy storage density and high-energy storage efficiency ceramic material and preparation method thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
《High energy storage density over a broad temperature range in sodium bismuth titanate-based lead-free ceramics》;Haibo Yang等;《Scientific Reports》;20170818;第7卷(第8726期);DOI:10.1038/s41598-017-06966-7 *

Also Published As

Publication number Publication date
CN107473732A (en) 2017-12-15

Similar Documents

Publication Publication Date Title
CN107473732B (en) Strontium titanate-based ceramic material with high energy storage density and low dielectric loss and preparation method thereof
CN108929112B (en) Tin-doped lead lanthanum zirconate titanate thick film ceramic and preparation and application thereof
CN106699170B (en) Strontium titanate-based lead-free ceramic material with high energy storage density and high energy storage efficiency and preparation method thereof
CN107602115B (en) Lead-free high-energy-storage-density wide-temperature-range stable ceramic material and preparation method thereof
CN101805185B (en) Method for preparing leadmagnesio-niobate lead titanate relaxation ferroelectric ceramics
CN111978082B (en) Strontium magnesium niobate doped modified sodium bismuth titanate based energy storage ceramic material and preparation method thereof
CN106915960B (en) Lead-free ceramic material with high energy storage density and energy storage efficiency and preparation method thereof
CN106587986B (en) The multi-functional lead-free ceramics and preparation method for having energy storage, strain and wide dielectric warm area
CN107140974A (en) A kind of unleaded high energy storage density ST NBT ceramic materials of microwave sintering and preparation method thereof
CN113213929A (en) Potassium sodium niobate based ferroelectric ceramic material with high energy storage efficiency and density and preparation method thereof
CN109180181A (en) A kind of unleaded relaxation antiferroelectric ceramics energy storage material and preparation method thereof
CN111484325A (en) Barium strontium titanate-based ceramic material and preparation method and application thereof
CN111004030B (en) MgTiO (magnesium-titanium-oxide) powder3Microwave-based dielectric ceramic and preparation method thereof
CN107445616B (en) Strontium titanate-based lead-free high-pressure-resistant energy storage ceramic material and preparation method thereof
CN112209711A (en) Zirconium-titanium-tin lead niobate thick film ceramic and preparation method and application thereof
CN109650875B (en) Giant dielectric calcium copper titanate composite ceramic material and preparation method and application thereof
CN107814569A (en) A kind of lead-free anti-ferroelectric body ceramics and preparation method thereof
CN107445611B (en) Lead-free low-loss high-energy-storage-density ceramic material and preparation method thereof
CN108623301B (en) A kind of unleaded low-dielectric loss and high energy storage density ceramics and preparation method thereof with sandwich structure
CN106915964B (en) Lead-free high-energy-storage-density ceramic material and preparation method thereof
CN112521145A (en) Barium strontium titanate-based ceramic with high energy storage density and power density and preparation method thereof
CN116063074B (en) Ceramic material with high energy storage density and preparation method and application thereof
CN109456055A (en) A kind of high breakdown high polarization bismuth-sodium titanate ceramic material, preparation method and application
CN114478006A (en) KNNS-BNZ + CuO piezoceramic material and preparation method and application thereof
CN114591080A (en) Preparation method and application of dielectric ceramic material with high energy storage density

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