CN114220659B - Oxide reinforced inorganic dielectric amorphous composite film with high energy storage density and high breakdown strength and preparation method thereof - Google Patents
Oxide reinforced inorganic dielectric amorphous composite film with high energy storage density and high breakdown strength and preparation method thereof Download PDFInfo
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- 238000004146 energy storage Methods 0.000 title claims abstract description 67
- 239000002131 composite material Substances 0.000 title claims abstract description 66
- 230000015556 catabolic process Effects 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 238000004528 spin coating Methods 0.000 claims abstract description 34
- 238000000034 method Methods 0.000 claims abstract description 22
- 239000002243 precursor Substances 0.000 claims abstract description 21
- 229910052755 nonmetal Inorganic materials 0.000 claims abstract description 18
- 239000000758 substrate Substances 0.000 claims abstract description 16
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 15
- 238000000137 annealing Methods 0.000 claims abstract description 14
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 14
- 238000000197 pyrolysis Methods 0.000 claims abstract description 13
- 239000000203 mixture Substances 0.000 claims abstract description 10
- 239000000126 substance Substances 0.000 claims abstract description 10
- 239000011159 matrix material Substances 0.000 claims abstract description 6
- 229910052751 metal Inorganic materials 0.000 claims abstract description 6
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 6
- 150000003624 transition metals Chemical group 0.000 claims abstract description 6
- 239000002184 metal Substances 0.000 claims abstract description 3
- 239000012744 reinforcing agent Substances 0.000 claims abstract description 3
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 24
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 21
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims description 14
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 13
- 230000007062 hydrolysis Effects 0.000 claims description 13
- 238000006460 hydrolysis reaction Methods 0.000 claims description 13
- ITHZDDVSAWDQPZ-UHFFFAOYSA-L barium acetate Chemical compound [Ba+2].CC([O-])=O.CC([O-])=O ITHZDDVSAWDQPZ-UHFFFAOYSA-L 0.000 claims description 10
- 239000011259 mixed solution Substances 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims description 7
- 238000006068 polycondensation reaction Methods 0.000 claims description 7
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 6
- 150000004703 alkoxides Chemical class 0.000 claims description 5
- 239000012702 metal oxide precursor Substances 0.000 claims description 5
- 238000013329 compounding Methods 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000010408 film Substances 0.000 abstract description 97
- 239000010409 thin film Substances 0.000 abstract description 8
- 238000010438 heat treatment Methods 0.000 abstract description 7
- 239000002994 raw material Substances 0.000 abstract description 3
- 229910021423 nanocrystalline silicon Inorganic materials 0.000 abstract 1
- 230000010287 polarization Effects 0.000 description 13
- 239000000463 material Substances 0.000 description 11
- 238000002441 X-ray diffraction Methods 0.000 description 9
- 238000012360 testing method Methods 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 238000001755 magnetron sputter deposition Methods 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 3
- 229910002113 barium titanate Inorganic materials 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 239000003990 capacitor Substances 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 229910010293 ceramic material Inorganic materials 0.000 description 2
- 238000002003 electron diffraction Methods 0.000 description 2
- 239000006104 solid solution Substances 0.000 description 2
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 239000011365 complex material Substances 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 239000003989 dielectric material Substances 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003623 enhancer Substances 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- PVFSDGKDKFSOTB-UHFFFAOYSA-K iron(3+);triacetate Chemical compound [Fe+3].CC([O-])=O.CC([O-])=O.CC([O-])=O PVFSDGKDKFSOTB-UHFFFAOYSA-K 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
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- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229940078494 nickel acetate Drugs 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- LGQXXHMEBUOXRP-UHFFFAOYSA-N tributyl borate Chemical compound CCCCOB(OCCCC)OCCCC LGQXXHMEBUOXRP-UHFFFAOYSA-N 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G4/00—Fixed capacitors; Processes of their manufacture
- H01G4/33—Thin- or thick-film capacitors
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D1/00—Processes for applying liquids or other fluent materials
- B05D1/002—Processes for applying liquids or other fluent materials the substrate being rotated
- B05D1/005—Spin coating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
- B05D3/02—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by baking
- B05D3/0209—Multistage baking
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
- B05D3/02—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by baking
- B05D3/0254—After-treatment
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
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- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Manufacturing & Machinery (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Inorganic Insulating Materials (AREA)
Abstract
The invention discloses an oxide reinforced inorganic dielectric amorphous composite film with high energy storage density and high breakdown strength and a preparation method thereof. The amorphous composite film takes an amorphous BaTiO 3 film as a matrix and takes metal oxide or nonmetal oxide as a reinforcing agent, the chemical composition expression of the amorphous composite film is (1-x) BaTiO 3 -xMeO, x=0.01-0.2, wherein MeO is metal oxide or nonmetal oxide; the metal in the metal oxide is transition metal or Al; the nonmetal in the nonmetal oxide is B or Si. Preparing a precursor solution, standing to form sol, preparing a film on a substrate by adopting a sol-gel spin coating method, performing pyrolysis, and finally annealing to obtain the nano-crystalline silicon thin film. The film has the advantages of high energy storage density, high breakdown strength, good temperature stability, excellent dielectric property, simple preparation method, low heat treatment temperature, short time, low-cost and easily-obtained raw materials and wide industrial application prospect.
Description
Technical Field
The invention belongs to the technical field of dielectric ceramic film energy storage materials, and particularly relates to an oxide reinforced inorganic dielectric amorphous composite film with high energy storage density and high breakdown strength and a preparation method thereof.
Background
The dielectric capacitor is widely applied to the fields of advanced pulse power systems, hybrid electric vehicles and the like because of the characteristics of high power density, long service life and the like. Currently, widely studied dielectric ceramic materials can be divided into thin films (thickness <1 mm) and bulk (thickness >100 mm). The dielectric ceramic material with large volume has low breakdown strength, cannot obtain large energy storage density, and cannot meet the requirements of miniaturization and integration of advanced electronic equipment. Generally, the main factors for evaluating the energy storage capacity of a dielectric capacitor are energy storage density, energy storage efficiency, stability and the like. While factors affecting energy storage density and energy storage efficiency are mainly maximum polarization (P max), breakdown strength (BDS), and remnant polarization (P r). Films generally exhibit higher breakdown strength and higher polarization due to low defect concentrations. Therefore, further development of ceramic thin film dielectrics with high energy storage density and high breakdown strength is a current trend.
Barium titanate (BaTiO 3) is widely used in the field of energy storage capacitors due to its high P max, but its low breakdown strength and high P r limit its application in energy storage. In recent years, in order to increase the energy storage density of BT-based thin film materials, researchers have proposed relaxor ferroelectrics that allow for a significant reduction in remnant polarization while retaining a greater polarization. However, researchers often focus on achieving larger Δp, and lower E b limits their intended use. Researchers can obtain a thin film material with an amorphous structure by compounding BT with BiMeO 3 (Me is Mg, zn, zr and the like) and controlling a preparation process through the low melting point of Bi, and the method can improve the breakdown strength of the material, but can reduce the polarization of the material at the same time, so that the method is unfavorable for realizing high energy storage density. In order to obtain higher energy storage density of the BT-based material, the proposal adopted at present mostly needs a complex material system and preparation technology to realize, which is unfavorable for the concept of green preparation and the wide application of the material. Therefore, how to achieve a high energy storage density of BT-based materials by a simple method is urgent.
Disclosure of Invention
The invention aims to provide an oxide reinforced inorganic dielectric amorphous composite film with high energy storage density and high breakdown strength and a preparation method thereof, wherein the film has the advantages of high energy storage density, high breakdown strength, good temperature stability and excellent dielectric property, and the preparation method is simple, low in heat treatment temperature, short in time, low in cost and easy in acquisition of raw materials, and has wide industrial application prospects.
In order to solve the technical problems, the invention provides the following technical scheme:
An oxide reinforced inorganic dielectric amorphous composite film with high energy storage density and high breakdown strength is provided, wherein the amorphous composite film takes an amorphous BaTiO 3 film as a matrix, takes metal oxide or nonmetal oxide as a reinforcing agent, and has a chemical composition expression of (1-x) BaTiO 3 -xMeO, x=0.01-0.2, wherein MeO is metal oxide or nonmetal oxide; the metal in the metal oxide is transition metal or Al; the nonmetal in the nonmetal oxide is B or Si.
According to the scheme, x=0.01-0.1.
According to the scheme, the transition metal is Cr, mn, fe, co, ni, cu or Zn.
According to the scheme, the discharge energy storage density of the amorphous composite film is 60-150J cm -3, the breakdown strength is 6-10MV cm -1, and the energy storage efficiency is kept above 80%.
According to the scheme, the thickness of the amorphous composite film is 100-200nm.
The preparation method of the oxide reinforced inorganic dielectric amorphous composite film with high energy storage density and high breakdown strength is provided, and the preparation method is prepared by a sol-gel spin coating method and comprises the following steps:
1) Compounding according to the stoichiometric ratio of metal elements in the chemical composition expression (1-x) BaTiO 3 -xMeO, and preparing a precursor solution containing barium acetate, metal oxide or non-metal oxide precursor alkoxide and tetrabutyl titanate;
2) Standing the precursor solution obtained in the step 1) in air, and forming clear and stable sol through full hydrolysis and polycondensation;
3) Preparing a film on a substrate by adopting the sol obtained in the step 2) through a sol-gel spin coating method, and performing pyrolysis to obtain a xerogel film;
4) Repeating the step 3) for 4-8 times, and annealing the obtained xerogel film to obtain the oxide reinforced inorganic dielectric amorphous composite film with high energy storage density and high breakdown strength.
According to the scheme, in the step 1), the concentration of the precursor solution is 0.05-0.3mol L -1.
According to the scheme, the precursor solution is prepared by the following steps: dissolving barium acetate and metal oxide or non-metal oxide precursor alkoxide in acetic acid to obtain a mixed solution A, dissolving tetrabutyl titanate in ethylene glycol methyl ether, and adding acetylacetone to inhibit hydrolysis to obtain a mixed solution B; mixing the mixed solution A and the mixed solution B, and stirring in a water bath to obtain a precursor solution.
Preferably, the volume ratio of the ethylene glycol methyl ether, the acetic acid and the acetylacetone is 60-70:20-30:1-4.
Preferably, the water bath stirring conditions are: stirring in water bath at 40-70deg.C for 12-48 hr.
According to the scheme, in the step 2), standing is carried out for 12-48h in the air.
According to the above scheme, in the step 3), the sol-gel spin coating process is as follows: spin-coating for 10-30s at the rotation speed of 600-1000rmp, and spin-coating for 30-90s at the rotation speed of 3000-5000rmp to perform secondary spin-coating; the pyrolysis conditions are as follows: pyrolysis is carried out for three times according to the temperature from low to high within the temperature range of 200-500 ℃, the temperature difference between two adjacent times is 100-150 ℃, and the pyrolysis time is 4-6 minutes each time.
According to the above scheme, in the step 3), the substrate is a Pt/Ti/SiO 2/Si substrate.
According to the scheme, in the step 4), the annealing temperature is 450-600 ℃, and the annealing time is 90-120s.
The working mechanism of the invention is as follows:
The invention takes the amorphous film as a matrix, and realizes high breakdown strength through the amorphous disordered state. Meanwhile, oxide is introduced as an enhancer, so that the breakdown strength of the film can be further improved due to the high breakdown strength of the oxide; on the other hand, the cations of the oxide may form solid solutions with BaTiO 3 of the matrix, and these solid solutions may form defective dipoles with oxygen vacancies, which may be bound in an amorphous network, and increase polarization of the thin film under an applied electric field, thereby achieving high energy storage density. The polarization of the material can be improved by the synergistic effect of the oxide and the amorphous structure on the premise of realizing high breakdown strength, so that high energy storage density is realized. In addition, due to the amorphous structure and the nature of the oxide itself, the material more closely approximates a linear dielectric, so that the film can maintain dielectric and energy storage stability over a wide temperature range.
The beneficial effects of the invention are as follows:
1. The invention provides an oxide reinforced inorganic dielectric amorphous composite film, which can adjust the insulativity of the film and strengthen the breakdown strength of the film by adding high-insulation transition metal (or Al) oxide or non-metal oxide B 2O3,SiO2 and the like into a barium titanate film, and meanwhile, the amorphous film can control the formation of micro-stages in the film, so that the voltage resistance is improved, the leakage current is reduced, the energy storage efficiency is improved, and in addition, the oxide and the amorphous BaTiO 3 matrix cooperate to improve the polarization of the film and realize high energy storage density; the amorphous composite film has ultrahigh pressure resistance, ensures that the film obtains excellent energy storage performance under ultrahigh voltage, has discharge energy storage density in the range of 60-150J cm -1, has breakdown strength in the range of 6-10MV cm -1, and keeps energy storage efficiency above 80%.
2. The amorphous composite film provided by the invention has good dielectric property, shows excellent frequency stability in the range of 1k-1MHz, has dielectric constant variation less than 14% respectively, and is beneficial to the application of materials in the field of dielectric energy storage; meanwhile, in the range of 20-200 ℃, the dielectric constant and dielectric loss have good temperature stability, and no obvious dielectric peak appears; the variation of dielectric constant is less than 5%, and the dielectric loss is less than 0.06 in the temperature range of 20-200 ℃.
3. The amorphous composite film provided by the invention also has good temperature stability, the change rate of energy storage efficiency is less than 11% and the delta W rec/Wrec20℃ is less than 2.2% in the range of 20-200 ℃, the excellent temperature stability is shown, and the amorphous composite film has high application potential under different working conditions.
4. The invention adopts sol-gel spin coating method to prepare amorphous composite film, and has simple process and short experimental period; the heat treatment temperature is low, the time is short, and the energy is saved; the raw materials do not contain rare earth elements and noble metal elements, and the cost is low; the amorphous composite film overcomes the low withstand voltage characteristic of the traditional dielectric film material, realizes high energy storage density, dielectric property and energy storage stability, and is beneficial to realizing industrialization and green manufacturing due to simple process.
Drawings
FIG. 1 is an XRD pattern of the amorphous composite thin film prepared in examples 1 to 4 of the present invention;
FIG. 2 is a high resolution transmission electron microscope (left image) and a Selective Area Electron Diffraction (SAED) image (right image) of the amorphous composite film prepared in example 2 of the present invention.
FIG. 3 is a graph showing the variation of dielectric constant and dielectric loss with frequency in the frequency range of 1k-1MHz of the amorphous composite films prepared in examples 1-4 of the present invention.
FIG. 4 is a graph showing the dielectric constant and dielectric loss of the amorphous composite film prepared in example 2 according to the present invention over the temperature range of 20 to 200 ℃.
FIG. 5 is a graph showing the hysteresis loop of the amorphous composite films prepared in examples 1 to 4 according to the present invention under the breakdown strength.
FIG. 6 is a graph showing the change rate of energy storage density and the change efficiency with temperature in the range of 20-200 ℃ for the amorphous composite film prepared in example 2 of the present invention.
Detailed Description
In order that the skilled person may better understand the invention, the following will further illustrate the invention with reference to examples and figures.
Example 1
An oxide reinforced inorganic amorphous dielectric composite film is provided, the chemical composition expression of which is (1-x) BaTiO 3 -xNiO (x=0.03), and the preparation method specifically comprises the following steps:
(1) Barium acetate, nickel acetate and tetrabutyl titanate were weighed according to the molar ratio, dissolved in 30ml of acetic acid, tetrabutyl titanate was dissolved in 67.8ml of ethylene glycol methyl ether, and added with 2.2ml of acetylacetone to inhibit hydrolysis. Finally, all the solutions are mixed and stirred for 12 hours under the water bath condition of 40 ℃ to obtain a stable precursor solution.
(2) And (3) standing the precursor solution obtained in the step (1) in air for 24 hours, and forming clear and stable sol through full hydrolysis and polycondensation.
(3) Dripping the sol obtained in the step (2) on a Pt/Ti/SiO 2/Si substrate by using a sol-gel spin coating method, carrying out low-speed spin coating for 10s at a rotating speed of 1000rmp, and carrying out high-speed spin coating for 30s at a rotating speed of 5000 rmp; and (3) placing the substrate subjected to spin coating on a heating table, and respectively pyrolyzing at 200 ℃, 350 ℃ and 450 ℃ for 5 minutes to obtain a xerogel film.
(4) And (3) repeating the step (3) for 6 times, and then placing the obtained xerogel film in a rapid annealing furnace, and annealing for 90s at 550 ℃ to obtain the inorganic dielectric composite film with high energy storage density and high breakdown strength, wherein the thickness of the inorganic dielectric composite film is about 120 nm.
The amorphous composite film prepared in example 1 was subjected to analysis of the crystal structure of the film by X-ray diffraction test (XRD), and the spectrum is shown in fig. 1, and no distinct perovskite characteristic peak was found in the sample, and a dispersed broad peak appeared between 20 ° and 30 °, indicating that the film exists in an amorphous form.
The amorphous composite film prepared in example 1 was prepared into a top electrode by magnetron sputtering, and the energy storage performance and the dielectric property were tested. As shown in fig. 3, the dielectric constant of the film was 121.4 and the electrical loss was 0.044 at a frequency of 10 kHz.
The amorphous composite film prepared in example 1 was tested for breakdown field strength and hysteresis loop through a ferroelectric workstation. As shown in FIG. 5, the breakdown strength is 8.073MV cm -1, the maximum polarization strength is 40.32 mu C cm -2, and the discharge energy storage density of the film is calculated to be 144.4J cm -3, and the energy storage efficiency is calculated to be 80.6%.
Example 2
An oxide reinforced inorganic amorphous dielectric composite film is provided, the chemical composition expression of which is (1-x) BaTiO 3 -xFeO (x=0.05), the preparation method comprises the following steps:
(1) Barium acetate, iron acetate and tetrabutyl titanate were weighed according to the molar ratio, dissolved in 30ml of acetic acid, tetrabutyl titanate was dissolved in 67.8ml of ethylene glycol methyl ether, and added with 2.2ml of acetylacetone to inhibit hydrolysis. Finally, all the solutions are mixed and stirred for 12 hours under the water bath condition of 40 ℃ to obtain a stable precursor solution.
(2) And (3) standing the precursor solution obtained in the step (1) in air for 24 hours, and forming clear and stable sol through full hydrolysis and polycondensation.
(3) Dripping the sol obtained in the step (2) on a Pt/Ti/SiO 2/Si substrate by using a sol-gel spin coating method, spin-coating for 10s at a low speed at a rotating speed of 1000rmp, and then telling the spin-coating for 30s at a rotating speed of 5000 rmp; and (3) placing the substrate subjected to spin coating on a heating table, and respectively pyrolyzing at 200 ℃, 350 ℃ and 450 ℃ for 5 minutes to obtain a xerogel film.
(4) And (3) repeating the step (3) for 6 times, and then placing the obtained xerogel film in a rapid annealing furnace, and annealing for 90s at 550 ℃ to obtain the inorganic dielectric composite film with high energy storage density and high breakdown strength, wherein the thickness of the inorganic dielectric composite film is about 120 nm.
The amorphous composite film prepared in example 2 was subjected to analysis of the crystal structure of the film by X-ray diffraction test (XRD), and the spectrum is shown in fig. 1, and no distinct perovskite characteristic peak was found in the sample, exhibiting characteristics of amorphous structure.
The amorphous composite film prepared in example 2 was subjected to high resolution transmission electron microscopy and selective electron diffraction (SAED) testing. As shown in fig. 2, the thin film exists in an amorphous form, in which the existing portion presents a nano-region with a certain polarity of lattice fringes.
The amorphous composite film prepared in example 2 was prepared into a top electrode by magnetron sputtering, and the energy storage performance and the dielectric property were tested. As shown in fig. 3, the dielectric constant of the film was 82.4 and the electrical loss was 0.037 at a frequency of 10 kHz.
The amorphous composite film prepared in example 2 was tested for temperature stability of dielectric properties in the range of 20-200 ℃. As shown in fig. 4, no significant dielectric peak appears, the variation of dielectric constant is <5%, and the dielectric loss is <0.06.
The amorphous composite film prepared in example 2 was tested for breakdown field strength and hysteresis loop through a ferroelectric workstation. As shown in FIG. 5, the breakdown strength is 8.076MV cm -1, the maximum polarization strength is 25.68 mu C cm -2, and the discharge energy storage density of the film is 104.7J cm -3 and the energy storage efficiency is 88.3 percent.
The amorphous composite film prepared in example 2 was tested for temperature stability of energy storage performance in the range of 20-200 ℃. As shown in FIG. 6, the energy storage efficiency is reduced from 95.7% to 85.0% in the range of 20-200 ℃, the discharge energy storage density is basically unchanged, and the DeltaW rec/Wrec20℃ is less than 2.2%, so that the temperature stability is very good.
Example 3
An oxide reinforced inorganic amorphous dielectric composite film is provided, the chemical composition expression of which is (1-x) BaTiO 3-xSiO2 (x=0.05), and the preparation method specifically comprises the following steps:
(1) Barium acetate, tetraethyl orthosilicate and tetrabutyl titanate were weighed according to the molar ratio, dissolved in 30ml of acetic acid, tetrabutyl titanate was dissolved in 67.8ml of ethylene glycol methyl ether, and added with 2.2ml of acetylacetone to inhibit hydrolysis. Finally, all the solutions are mixed and stirred for 12 hours under the water bath condition of 40 ℃ to obtain a stable precursor solution.
(2) And (3) standing the precursor solution obtained in the step (1) in air for 24 hours, and forming clear and stable sol through full hydrolysis and polycondensation.
(3) Dripping the sol obtained in the step (2) on a Pt/Ti/SiO 2/Si substrate by using a sol-gel spin coating method, spin-coating for 10s at a low speed at a rotating speed of 1000rmp, and then telling the spin-coating for 30s at a rotating speed of 5000 rmp; and (3) placing the substrate subjected to spin coating on a heating table, and respectively pyrolyzing at 200 ℃, 350 ℃ and 450 ℃ for 5 minutes to obtain a xerogel film.
(4) And (3) repeating the step (3) for 6 times, and then placing the obtained xerogel film in a rapid annealing furnace, and annealing for 90s at 550 ℃ to obtain the inorganic dielectric composite film with high energy storage density and high breakdown strength, wherein the thickness of the inorganic dielectric composite film is about 120 nm.
The amorphous composite film prepared in example 3 was subjected to analysis of the crystal structure of the film by X-ray diffraction test (XRD), the spectrum is shown in fig. 1, and the sample shows a dispersed broad peak, indicating that the film exists in an amorphous form.
The amorphous composite film prepared in example 3 was prepared into a top electrode by magnetron sputtering, and the energy storage property and the dielectric property were tested. As shown in FIG. 3, at a frequency of 10kHz, the dielectric constant of the film was 31.4, and the electrical loss was 0.041.
The amorphous composite film prepared in example 3 was tested for breakdown field strength and hysteresis loop through a ferroelectric workstation. As shown in FIG. 5, the breakdown strength was 8.07MV cm -1, the maximum polarization strength was 23.94 μC cm -2, and the discharge energy storage density of the film was 94.3J cm -3, and the energy storage efficiency was 82.6%.
Example 4
An oxide reinforced inorganic amorphous dielectric composite film is provided, the chemical composition expression of which is (1-x) BaTiO 3-xB2O3 (x=0.07), the preparation method comprises the following steps:
(1) Barium acetate, tributyl borate and tetrabutyl titanate were weighed according to the molar ratio, barium acetate and tetraethyl orthosilicate were dissolved in 30ml of acetic acid, tetrabutyl titanate was dissolved in 67.8ml of ethylene glycol methyl ether and 2.2ml of acetylacetone was added to inhibit hydrolysis. Finally, all the solutions are mixed and stirred for 12 hours under the water bath condition of 40 ℃ to obtain a stable precursor solution.
(2) And (3) standing the precursor solution obtained in the step (1) in air for 24 hours, and forming clear and stable sol through full hydrolysis and polycondensation.
(3) Dripping the sol obtained in the step (2) on a Pt/Ti/SiO 2/Si substrate by using a sol-gel spin coating method, spin-coating for 10s at a low speed at a rotating speed of 1000rmp, and then telling the spin-coating for 30s at a rotating speed of 5000 rmp; and (3) placing the substrate subjected to spin coating on a heating table, and respectively pyrolyzing at 200 ℃, 350 ℃ and 450 ℃ for 5 minutes to obtain a xerogel film.
(4) And (3) repeating the step (3) for 6 times, and then placing the obtained xerogel film in a rapid annealing furnace, and annealing for 90s at 550 ℃ to obtain the inorganic dielectric composite film with high energy storage density and high breakdown strength, wherein the thickness of the inorganic dielectric composite film is about 120 nm.
The amorphous composite film prepared in example 4 was subjected to analysis of the crystal structure of the film by X-ray diffraction test (XRD), the spectrum is shown in fig. 1, and the sample shows a dispersed broad peak, indicating that the film exists in an amorphous form.
The amorphous composite film prepared in example 4 was prepared into a top electrode by magnetron sputtering, and the energy storage property and the dielectric property were tested. As shown in fig. 3, the dielectric constant of the film was 22.6 and the electrical loss was 0.051 at a frequency of 10 kHz.
The amorphous composite film prepared in example 4 was tested for breakdown field strength and hysteresis loop through a ferroelectric workstation. As shown in FIG. 5, the breakdown strength was 7.05MV cm -1, the maximum polarization strength was 20.42 μC cm -2, and the discharge energy storage density of the film was calculated to be 68.5J cm -3, and the energy storage efficiency was 85.4%.
In summary, in combination with the above detailed description of the embodiments of the present invention, the oxide reinforced inorganic amorphous dielectric composite film with high energy storage density and high breakdown strength and the preparation method thereof provided by the present invention solve the problems of high breakdown strength and low application temperature of the conventional barium titanate-based film P r and the conventional composite material, and the prepared (1-x) BaTiO 3 -xMeO (x=0.01-0.2) has high breakdown field strength, high energy storage density and high energy storage efficiency, and has stable electrical properties in a wide temperature range.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, alternatives, and improvements that fall within the spirit and scope of the invention.
Claims (8)
1. The oxide reinforced inorganic dielectric amorphous composite film with high energy storage density and high breakdown strength is characterized in that the amorphous composite film takes an amorphous BaTiO 3 film as a matrix, takes metal oxide or nonmetal oxide as a reinforcing agent, and has a chemical composition expression of (1-x) BaTiO 3 -xMeO and x=0.01-0.2, wherein MeO is metal oxide or nonmetal oxide; the metal in the metal oxide is transition metal; the nonmetal in the nonmetal oxide is B or Si; wherein:
the preparation of the amorphous composite film comprises the following steps:
1) Compounding according to the stoichiometric ratio of metal elements in the chemical composition expression (1-x) BaTiO 3 -xMeO, and preparing a precursor solution containing barium acetate, metal oxide or non-metal oxide precursor alkoxide and tetrabutyl titanate;
2) Standing the precursor solution obtained in the step 1) in air, and forming clear and stable sol through full hydrolysis and polycondensation;
3) Preparing a film on a substrate by adopting the sol obtained in the step 2) through a sol-gel spin coating method, and carrying out pyrolysis to obtain a xerogel film; the method comprises the following specific steps: spin-coating for 10-30s at 600-1000rpm for primary spin-coating, and spin-coating for 30-90s at 3000-5000rpm for secondary spin-coating; the pyrolysis conditions are as follows: pyrolysis is carried out for three times according to the temperature from low to high in the temperature range of 200-500 ℃, the temperature difference between two adjacent times is 100-150 ℃, and the pyrolysis time is 4-6 minutes each time;
4) Repeating the step 3) for 4-8 times, and annealing the obtained xerogel film at 450-600 ℃ for 90-120s to obtain the oxide reinforced inorganic dielectric amorphous composite film with high energy storage density and high breakdown strength.
2. The amorphous composite film according to claim 1, wherein the transition metal is Cr, mn, fe, co, ni, cu or Zn.
3. The amorphous composite film according to claim 1, wherein the amorphous composite film has a discharge energy storage density of 60-150J cm -3, a breakdown strength of 6-10MV cm -1, and an energy storage efficiency maintained at 80% or more.
4. The amorphous composite film according to claim 1, wherein the amorphous composite film has a thickness of 100 to 200nm.
5. A method for preparing the oxide-reinforced inorganic dielectric amorphous composite film with high energy storage density and high breakdown strength according to any one of claims 1 to 4, comprising the following steps:
1) Compounding according to the stoichiometric ratio of metal elements in the chemical composition expression (1-x) BaTiO 3 -xMeO, and preparing a precursor solution containing barium acetate, metal oxide or non-metal oxide precursor alkoxide and tetrabutyl titanate;
2) Standing the precursor solution obtained in the step 1) in air, and forming clear and stable sol through full hydrolysis and polycondensation;
3) Preparing a film on a substrate by adopting the sol obtained in the step 2) through a sol-gel spin coating method, and carrying out pyrolysis to obtain a xerogel film; the method comprises the following specific steps: spin-coating for 10-30s at 600-1000rpm for primary spin-coating, and spin-coating for 30-90s at 3000-5000rpm for secondary spin-coating; the pyrolysis conditions are as follows: pyrolysis is carried out for three times according to the temperature from low to high in the temperature range of 200-500 ℃, the temperature difference between two adjacent times is 100-150 ℃, and the pyrolysis time is 4-6 minutes each time;
4) Repeating the step 3) for 4-8 times, and annealing the obtained xerogel film at 450-600 ℃ for 90-120s to obtain the oxide reinforced inorganic dielectric amorphous composite film with high energy storage density and high breakdown strength.
6. The method according to claim 5, wherein in the step 1), the precursor solution concentration is 0.05 to 0.3mol L -1; in the step 2), standing is carried out in air for 12-48h.
7. The method of claim 5, wherein the precursor solution is prepared by: dissolving barium acetate and metal oxide or non-metal oxide precursor alkoxide in acetic acid to obtain a mixed solution A, dissolving tetrabutyl titanate in ethylene glycol methyl ether, and adding acetylacetone to inhibit hydrolysis to obtain a mixed solution B; mixing the mixed solution A and the mixed solution B, and stirring in a water bath at 40-70 ℃ for 12-48h to obtain a precursor solution.
8. The method according to claim 5, wherein in the step 3), the substrate is a Pt/Ti/SiO 2/Si substrate.
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