CN115341201A - Chromium and cadmium doped calcium copper titanate film with high energy storage density and preparation method thereof - Google Patents
Chromium and cadmium doped calcium copper titanate film with high energy storage density and preparation method thereof Download PDFInfo
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- HAUBPZADNMBYMB-UHFFFAOYSA-N calcium copper Chemical compound [Ca].[Cu] HAUBPZADNMBYMB-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 239000011651 chromium Substances 0.000 title claims abstract description 52
- 238000004146 energy storage Methods 0.000 title claims abstract description 40
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 229910052793 cadmium Inorganic materials 0.000 title claims abstract description 35
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 title claims abstract description 35
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 229910052804 chromium Inorganic materials 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 59
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims abstract description 36
- 238000000034 method Methods 0.000 claims abstract description 32
- 239000002904 solvent Substances 0.000 claims abstract description 29
- 239000000758 substrate Substances 0.000 claims abstract description 26
- 239000010949 copper Substances 0.000 claims abstract description 22
- 238000010438 heat treatment Methods 0.000 claims abstract description 22
- 235000019260 propionic acid Nutrition 0.000 claims abstract description 18
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims abstract description 18
- 239000008139 complexing agent Substances 0.000 claims abstract description 16
- 239000011575 calcium Substances 0.000 claims abstract description 15
- 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 abstract description 14
- 108010025899 gelatin film Proteins 0.000 claims abstract description 12
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims abstract description 11
- 229910004298 SiO 2 Inorganic materials 0.000 claims abstract description 10
- VSGNNIFQASZAOI-UHFFFAOYSA-L calcium acetate Chemical compound [Ca+2].CC([O-])=O.CC([O-])=O VSGNNIFQASZAOI-UHFFFAOYSA-L 0.000 claims abstract description 8
- 239000001639 calcium acetate Substances 0.000 claims abstract description 8
- 235000011092 calcium acetate Nutrition 0.000 claims abstract description 8
- 229960005147 calcium acetate Drugs 0.000 claims abstract description 8
- LHQLJMJLROMYRN-UHFFFAOYSA-L cadmium acetate Chemical compound [Cd+2].CC([O-])=O.CC([O-])=O LHQLJMJLROMYRN-UHFFFAOYSA-L 0.000 claims abstract description 7
- WYYQVWLEPYFFLP-UHFFFAOYSA-K chromium(3+);triacetate Chemical compound [Cr+3].CC([O-])=O.CC([O-])=O.CC([O-])=O WYYQVWLEPYFFLP-UHFFFAOYSA-K 0.000 claims abstract description 7
- 239000010408 film Substances 0.000 claims description 76
- 239000010936 titanium Substances 0.000 claims description 32
- 238000003756 stirring Methods 0.000 claims description 19
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 18
- 239000010409 thin film Substances 0.000 claims description 14
- 239000012298 atmosphere Substances 0.000 claims description 13
- 239000003153 chemical reaction reagent Substances 0.000 claims description 13
- 229960000583 acetic acid Drugs 0.000 claims description 9
- 239000012362 glacial acetic acid Substances 0.000 claims description 9
- 229910021645 metal ion Inorganic materials 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- 229910052791 calcium Inorganic materials 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- 230000032683 aging Effects 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 238000009423 ventilation Methods 0.000 claims description 3
- 238000003980 solgel method Methods 0.000 claims description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims 4
- 229910052802 copper Inorganic materials 0.000 claims 4
- 239000002243 precursor Substances 0.000 claims 4
- 229910052719 titanium Inorganic materials 0.000 claims 4
- OPOYZAITYWRTKF-UHFFFAOYSA-N [Ca].[Cr].[Cd] Chemical compound [Ca].[Cr].[Cd] OPOYZAITYWRTKF-UHFFFAOYSA-N 0.000 claims 2
- 238000003618 dip coating Methods 0.000 claims 1
- 230000002194 synthesizing effect Effects 0.000 claims 1
- 230000008569 process Effects 0.000 abstract description 7
- 239000000463 material Substances 0.000 abstract description 3
- 230000009022 nonlinear effect Effects 0.000 abstract description 3
- 239000007858 starting material Substances 0.000 abstract description 2
- 230000015556 catabolic process Effects 0.000 description 28
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 15
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 10
- 238000005516 engineering process Methods 0.000 description 8
- 239000003990 capacitor Substances 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 6
- 239000003989 dielectric material Substances 0.000 description 6
- 229910052710 silicon Inorganic materials 0.000 description 6
- 239000010703 silicon Substances 0.000 description 6
- 239000004408 titanium dioxide Substances 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 4
- 229910052697 platinum Inorganic materials 0.000 description 4
- 238000004544 sputter deposition Methods 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- 239000003985 ceramic capacitor Substances 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
- 238000007747 plating Methods 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- 238000002791 soaking Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 230000010355 oscillation Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 238000005273 aeration Methods 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- -1 batteries Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- AOWKSNWVBZGMTJ-UHFFFAOYSA-N calcium titanate Chemical compound [Ca+2].[O-][Ti]([O-])=O AOWKSNWVBZGMTJ-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
- C23C18/1204—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material inorganic material, e.g. non-oxide and non-metallic such as sulfides, nitrides based compounds
- C23C18/1208—Oxides, e.g. ceramics
- C23C18/1216—Metal oxides
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
- C23C18/125—Process of deposition of the inorganic material
- C23C18/1254—Sol or sol-gel processing
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- Physics & Mathematics (AREA)
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- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
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- Compositions Of Oxide Ceramics (AREA)
Abstract
The invention discloses a high energy storage density cadmium and chromium doped calcium copper titanate film and a preparation method thereof, wherein the film material is Ca 0.5‑x Cr x Cd 0.5 Cu 3 Ti 4 O 12 The value of x is 0 to 0.2. Preparing sol by using calcium acetate, chromium acetate, cadmium acetate, copper acetate and tetrabutyl titanate as starting materials, propionic acid as a complexing agent and ethanol as a solvent, and carrying out a pulling method on Pt/Ti/SiO 2 Preparing a gel film on a Si substrate, and carrying out heat treatment to obtain the cadmium and chromium doped calcium copper titanate film. The film prepared by the invention has the advantages of simple process, low cost, good repeatability, excellent dielectric and nonlinear properties, and energy storage density of 5.8 to 10.4J/cm 3 And the application prospect is wide.
Description
Technical Field
The invention discloses a chromium and cadmium doped calcium copper titanate film with high energy storage density and a preparation method thereof, which can be used for a high energy storage film capacitor.
Background
With the global consensus of reducing carbon emissions, global energy transformation is imminent, and since renewable energy is an intermittent resource, energy storage is becoming a key part of the energy revolution under the wave of new energy in the world. Electric energy storage is the most widely used energy storage technology, and in recent years, many countries around the world are dedicated to the exploration of the energy storage industry. There is a pressing need to develop advanced technologies to solve the storage and conversion problems of electrical energy. The film capacitor is used as a physical energy storage device and has important application in many fields, such as high-voltage direct current transmission, flexible direct current transmission engineering and the like developed in recent years. In addition, the pulse power technology, the electromagnetic ejection technology, the electric automobile technology, the national major scientific plan large-scale device and the like all put urgent demands on the high energy storage thin film capacitor.
Currently, research in energy storage technology is mainly focused on dielectric capacitors, electrochemical capacitors, batteries, and solid oxide fuel cells. The ceramic capacitor is used as a passive device, has high power density (GW/kg), high charging and discharging speed (mus, even ns), and long fatigue life (more than or equal to 10) 6 Sub-cycle), high temperature stability, plays a very important role in solid state power storage. The national basic research and development plan and the important scientific research plan in 2015 use the inorganic dielectric material with high energy storage density as an important support direction. However, the energy density of physical power ceramic capacitors based on dipole orientation is lower than that of lithium ion batteries and solid oxide fuel cells. Therefore, increasing the energy density of ceramic capacitors is a key to expanding their practical applications.
The energy storage density of a linear dielectric can be expressed as:
(0.0≤E≤E b ) In which epsilon 0 、ε r 、E b Are respectively trueDielectric constant in air, relative dielectric constant and breakdown field strength. The polarizability of linear dielectrics is linear with the electric field, while their relatively low dielectric constant (. Epsilon.) r ) Making it difficult to achieve higher energy densities. Thereby increasing the dielectric constant ε r And breakdown field strength E b The two methods are effective two methods for improving the energy storage density, and the two parameters are difficult to simultaneously improve for the dielectric material;
in recent years, lead-free giant dielectric constant copper calcium titanate (CaCu) 3 Ti 4 O 12 CCTO) material is widely noticed, and the dielectric constant of its film reaches 10 as a linear dielectric material 3 And at low frequencies: (<10 6 Hz) has better stability from 100K to 600K, and is expected to be widely applied to high-density information storage, thin film devices (such as MEMS and GB-DRAM) and high-dielectric capacitors. However, the breakdown field strength of CCTO materials is small, which limits its commercial applications; researchers usually adopt polymer composite CCTO powder to improve the breakdown field strength, which can cause the condition that the addition amount of the powder is limited due to agglomeration, and the dielectric constant of the composite is greatly reduced, and the preparation process is complex. Therefore, the development of thin film dielectric materials with high dielectric constant and high breakdown field strength is urgently needed to meet the application requirements.
Disclosure of Invention
The invention aims to prepare a chromium and cadmium doped calcium copper titanate film with high energy storage density by using a sol-gel method, and the method simultaneously improves the dielectric constant and breakdown field strength of the film so as to improve the energy storage density of the film.
The principle of the method is that cadmium is used for replacing half of calcium in copper calcium titanate, so that the dielectric constant and breakdown field strength of the film are improved; and the chromium is used for partially replacing the remaining half of calcium, so that the breakdown field intensity of the film is further improved while the high dielectric constant of the film is kept, and the dielectric constant and the breakdown field intensity of the calcium copper titanate film are greatly improved, so that the energy storage density of the calcium copper titanate film is improved.
In order to achieve the purpose, the invention adopts the following technical scheme:
a chromium and cadmium doped calcium copper titanate film with high energy storage density and a preparation method thereof are characterized in thatIs characterized in that: the chemical formula of the film is Ca 0.5-x Cr x Cd 0.5 Cu 3 Ti 4 O 12 0.0. Ltoreq. X.ltoreq.0.2, preferably 0.05. Ltoreq. X.ltoreq.0.15.
Preferably, at room temperature, when x =0.1, the breakdown field strength of the film is 160kV/mm, the dielectric constant at 1kHz is 9160, and the energy storage density is 10.4J/cm 3 。
Preferably, at room temperature, the dielectric constant of the calcium copper titanate film is 8120-9310, the breakdown field strength is 125-160 kV/mm, and the energy storage density is 5.8-10.4J/cm 3 。
The preparation method of the chromium and cadmium doped calcium copper titanate film comprises the following steps:
the method comprises the following steps: preparation of the Sol
In a glove box with the humidity of less than 20%, adding a propionic acid complexing agent into the reagent A, then adding an ethanol solvent, and stirring and dissolving to obtain a solution A; the reagent A is: propionic acid: the molar ratio of the ethanol solvent is 1: (2-3): (5-10), wherein the reagent A is a mixture of calcium acetate, cadmium acetate and chromium acetate according to the stoichiometric ratio.
In a glove box with the humidity less than 20%, adding a propionic acid complexing agent into copper acetate, adding an ethanol solvent, and stirring under the heating condition of 40-70 ℃ to obtain a solution B; the copper acetate: propionic acid: the molar ratio of the ethanol solvent is 1: (7-10): (5-10).
In a glove box with the humidity less than 20%, adding complexing agent glacial acetic acid into tetrabutyl titanate, stirring, then adding an ethanol solvent, and continuously stirring to obtain a solution C; the reagent tetrabutyl titanate: glacial acetic acid: the molar ratio of the alcohol solvent is 1: (0.5-1): (5-10).
Mixing the solutions, stirring uniformly, and aging to obtain chromium and cadmium doped copper calcium titanate sol; the molar ratio of metal ions in the solution is controlled to be (Ca) 2+ +Cd 2+ +Cr 3+ )：Cu 2+ ：Ti 4+ 4, controlling the total concentration of metal ions in the solution to be 1.5-2 mol/L;
step two: preparation of gel films
Pt/Ti/SiO 2 Si substrateThe preparation process comprises the following steps: firstly, respectively soaking a silicon substrate in dilute hydrochloric acid and acetone to remove surface stains; then washing with deionized water, respectively carrying out ultrasonic oscillation cleaning in ethanol, and drying for later use; depositing a tetrabutyl titanate gel film on a silicon substrate by a Czochralski method, and then sintering for 1.5 hours in the air at the temperature of 600 ℃ to obtain a titanium dioxide film; plating a platinum electrode on the surface of the titanium dioxide film by using a small-sized ion sputtering instrument to obtain Pt/Ti/SiO 2 a/Si substrate.
Slowly immersing the substrate into the chromium-and cadmium-doped calcium copper titanate sol prepared in the first step through a drawing machine, standing for 30-40 s, wherein the drawing speed is 8-10 cm/min, drawing the substrate out of the surface of the sol at a constant speed, respectively preserving heat for 10-15 min in drying ovens at 100-150 ℃ and 200-250 ℃ to obtain a gel film, and repeating the steps for 4-6 times.
Step three: heat treatment process of film
(1) Heating to 500-600 ℃ from room temperature at a speed of 2 ℃/min, and preserving heat for 1-2 hours in air atmosphere;
(2) heating from 500 deg.c to 800-820 deg.c in 1 deg.c/min, maintaining in oxygen atmosphere for 2-3 hr, stopping ventilation and cooling to room temperature.
In the first step, the reagent A: propionic acid: the molar ratio of the ethanol solvent is 1:2.5:8.
copper acetate is preferred in the first step: propionic acid: the molar ratio of the ethanol solvent is 1:8: the heating temperature is preferably 40 to 45 ℃.
Tetrabutyl titanate is preferred in the first step: glacial acetic acid: the molar ratio of the alcohol solvent is 1:0.75:3.
in the second step, the substrate is preferably kept stand in the sol for 35s, the pulling rate is 8 cm/min, the temperature of the oven is 120 ℃ and 230 ℃, and the temperature is kept for 12 minutes.
In the second step, the above step is preferably repeated 5 times.
Heat treatment process for optimizing film in the third step
(1) Raising the temperature from room temperature to 550 ℃ at the speed of 2 ℃/min, and preserving the heat for 1.5 hours in the air atmosphere;
(2) the temperature is raised from 500 ℃ to 810 ℃ at a rate of 1 ℃/min, and the temperature is kept in an oxygen atmosphere for 2.5 hours.
The method takes calcium acetate, chromium acetate, cadmium acetate, copper acetate and tetrabutyl titanate as starting raw materials, propionic acid as a complexing agent and ethanol as a solvent to prepare sol; czochralski method at Pt/Ti/SiO 2 Preparing a gel film on a Si substrate, and obtaining the cadmium and chromium doped calcium copper titanate film with high energy storage density after heat treatment in a certain temperature and atmosphere.
Compared with the prior art, the invention has the advantages that: the preparation method is simple, the cost is low, the repeatability is good, the dielectric property and the nonlinear property of the obtained film are excellent, and the energy storage density can reach 5.8 to 10.4J/cm 3 . The method has very important application value in the fields of pulse power supplies, medical equipment, electromagnetic energy weapons, particle accelerators and the like.
Drawings
FIG. 1 is an XRD pattern of chromium and cadmium doped calcium copper titanate films prepared according to comparative example 1 and examples 1-5 of the present invention;
FIG. 2 is a graph showing the change of dielectric constant with frequency for chromium and cadmium doped calcium copper titanate films prepared in comparative example 1 and examples 1-5 in accordance with the present invention;
FIG. 3 is an impedance plot of chromium and cadmium doped calcium copper titanate films prepared in comparative example 1 and examples 1-5 of the present invention;
FIG. 4 is a graph of current density versus field strength for chromium and cadmium doped calcium copper titanate thin films prepared in comparative example 1 and examples 1-5 of the present invention;
FIG. 5 is a graph showing the change in the nonlinear coefficient, breakdown field strength, and energy storage density of chromium-and cadmium-doped calcium copper titanate thin films prepared in comparative example 1 and examples 1 to 5 in accordance with the present invention;
Detailed Description
The following further details embodiments of the invention:
a high energy storage density chromium and cadmium doped calcium copper titanate film and a preparation method thereof are characterized in that: the chemical general formula of the copper calcium titanate film is Ca 0.5-x Cr x Cd 0.5 Cu 3 Ti 4 O 12 ，0.0<x.ltoreq.0.2, preferably 0.05. Ltoreq. X.ltoreq.0.15.
The invention is realized by the copolymerization of cadmium and chromiumThe calcium is simultaneously replaced, so that the dielectric constant of the chromium and cadmium doped calcium copper titanate film is improved to 8120 to 9310, the breakdown field strength is 125 to 160kV/mm, and the energy storage density is 5.8 to 10.4J/cm 3 。
The preparation method of the copper calcium titanate film comprises the following steps:
the method comprises the following steps: preparation of the Sol
In a glove box with the humidity less than 20%, adding a propionic acid complexing agent into a mixture of calcium acetate, cadmium acetate and chromium acetate, adding an ethanol solvent, and stirring for dissolving to obtain a solution A; the reagents (calcium acetate, cadmium acetate and chromium acetate): propionic acid: the molar ratio of the ethanol solvent is 1: (2-3): (5-10).
In a glove box with the humidity less than 20%, adding a propionic acid complexing agent into copper acetate, then adding an ethanol solvent, and stirring under the heating condition of 40-70 ℃ to obtain a solution B; the reagent is copper acetate: propionic acid: the molar ratio of the ethanol solvent is 1: (7-10): (5-10).
In a glove box with the humidity less than 20%, adding complexing agent glacial acetic acid into tetrabutyl titanate, stirring, adding an ethanol solvent, and continuously stirring to obtain a solution C; the reagent tetrabutyl titanate: glacial acetic acid: the molar ratio of the alcohol solvent is 1: (0.5-1): (2-4).
Mixing the solutions, stirring uniformly, and aging to obtain chromium and cadmium doped copper calcium titanate sol; the molar ratio of metal ions in the solution is controlled to be (Ca) 2+ +Cd 2+ +Cr 3+ )：Cu 2+ ：Ti 4+ 4, controlling the total concentration of metal ions in the solution to be 1.5-2 mol/L;
step two: preparation of gel films
Pt/Ti/SiO 2 The preparation flow of the/Si substrate is as follows: firstly, respectively soaking a silicon substrate in dilute hydrochloric acid and acetone to remove surface stains; then washing with deionized water, respectively carrying out ultrasonic oscillation cleaning in ethanol, and drying for later use; depositing a tetrabutyl titanate gel film on a silicon substrate by a pulling method, and then sintering for 1.5 hours in the air at 600 ℃ to obtain a titanium dioxide film; plating platinum electrode on the surface of the titanium dioxide film by using a small ion sputtering instrument to obtain Pt/Ti/SiO 2 a/Si substrate.
Slowly immersing the substrate into the chromium-and cadmium-doped calcium copper titanate sol prepared in the first step through a drawing machine, standing for 30-40 s, wherein the drawing speed is 8-10 cm/min, drawing the substrate out of the surface of the sol at a constant speed, respectively preserving heat for 10-15 min in drying ovens at 100-150 ℃ and 200-250 ℃ to obtain a gel film, and repeating the steps for 4-6 times.
Step three: heat treatment process of film
(1) Heating from room temperature to 500-600 deg.c at 2 deg.c/min, and maintaining in air atmosphere for 1-2 hr;
(2) heating from 500 deg.c to 800-820 deg.c in 1 deg.c/min, maintaining in oxygen atmosphere for 2-3 hr, stopping ventilation and cooling to room temperature.
The present invention will be described in further detail with reference to examples. It is also to be understood that the following examples are illustrative of the present invention and are not to be construed as limiting the scope of the invention, and that insubstantial modifications and adaptations of the invention by those skilled in the art based on the foregoing description are intended to be included within the scope of the invention. The specific process parameters and the like of the following examples are also only one example of suitable ranges, i.e., those skilled in the art can select the appropriate ranges through the description herein, and are not limited to the specific values exemplified below.
Example 1:
the copper calcium titanate film comprises the following components: : ca 0.48 Cr 0.02 Cd 0.5 Cu 3 Ti 4 O 12 (x = 0.02), and the amounts of substances of the respective components in the starting materials were calculated in accordance with the above-described chemical formula compositions.
The method comprises the following steps: preparation of the Sol
In a glove box with the humidity less than 20%, firstly adding a propionic acid complexing agent into calcium acetate, then adding an ethanol solvent, and stirring and dissolving to obtain a solution A; the reagents (calcium acetate, chromium acetate and cadmium acetate): propionic acid: the molar ratio of the ethanol solvent is 1:2.5:8.
in a glove box with the humidity less than 20%, adding a propionic acid complexing agent into copper acetate, adding an ethanol solvent, and stirring under the heating condition of 42 ℃ to obtain a solution B; the copper acetate: propionic acid: the molar ratio of the ethanol solvent is 1:8:6.
in a glove box with the humidity less than 20%, adding complexing agent glacial acetic acid into tetrabutyl titanate, stirring, then adding an ethanol solvent, and continuously stirring to obtain a solution C; the reagent tetrabutyl titanate: glacial acetic acid: the molar ratio of the alcohol solvent is 1:0.75:3.
mixing the solutions, stirring uniformly, and aging to obtain chromium and cadmium doped calcium copper titanate sol; controlling the molar ratio of metal ions in the solution to be (Ca) 2+ +Cd 2+ +Cr 3+ )：Cu 2+ ：Ti 4+ 4, controlling the total concentration of metal ions in the solution to be 1.8mol/L;
step two: preparation of gel films
Pt/Ti/SiO 2 The preparation flow of the/Si substrate is as follows: firstly, respectively soaking a silicon substrate in dilute hydrochloric acid and acetone to remove surface stains; then washing with deionized water, respectively ultrasonically oscillating and cleaning in ethanol, and drying for later use; depositing a tetrabutyl titanate gel film on a silicon substrate by a pulling method, and then sintering for 1.5 hours in the air at 600 ℃ to obtain a titanium dioxide film; plating platinum electrode on the surface of the titanium dioxide film by using a small ion sputtering instrument to obtain Pt/Ti/SiO 2 a/Si substrate.
Slowly immersing the substrate into the chromium-cadmium-doped calcium copper titanate sol prepared in the first step through a drawing machine, standing for 35s, drawing the substrate out of the sol liquid level at a constant speed, keeping the temperature in ovens at 120 ℃ and 230 ℃ for 12 minutes respectively to obtain a gel film, and repeating the steps for 5 times.
Step three: heat treatment process of film
(1) Raising the temperature from room temperature to 550 ℃ at the speed of 2 ℃/min, and preserving the heat for 1.5 hours in the air atmosphere;
(2) heating from 500 deg.C to 810 deg.C at 1 deg.C/min, maintaining in oxygen atmosphere for 2.5 hr, stopping aeration, and cooling to room temperature.
The obtained film has a dielectric constant of 8430 at 1kHz, a breakdown field strength of 125kV/mm, and an energy density of 5.8J/cm 3 。
Example 2:
the copper calcium titanate film comprises the following components: ca 0.45 Cr 0.05 Cd 0.5 Cu 3 Ti 4 O 12 (x = 0.05), and the other steps are the same as in example 1. The obtained film has a dielectric constant of 9310 at 1kHz, a breakdown field strength of 141kV/mm, and an energy density of 8.2J/cm 3 。
Example 3:
the copper calcium titanate film comprises the following components: ca 0.4 Cr 0.1 Cd 0.5 Cu 3 Ti 4 O 12 (x = 0.1), and the other steps are the same as in example 1. The obtained film has dielectric constant of 9160 at 1kHz, breakdown field strength of 160kV/mm, and energy density of 10.4J/cm 3 。
Example 4:
the copper calcium titanate film comprises the following components: ca 0.35 Cr 0.15 Cd 0.5 Cu 3 Ti 4 O 12 (x = 0.15), and the other steps are the same as in example 1. The obtained film has dielectric constant of 8830, breakdown field strength of 148kV/mm, and energy density of 8.6J/cm at 1kHz 3 。
Example 5:
the copper calcium titanate film comprises the following components: ca 0.3 Cr 0.2 Cd 0.5 Cu 3 Ti 4 O 12 (x = 0.2), and the other steps are the same as in example 1. The obtained film has dielectric constant of 8120 at 1kHz, breakdown field strength of 132kV/mm, and energy density of 6.2J/cm 3 。
Example 6:
the copper calcium titanate film comprises the following components: ca 0.3 Cr 0.2 Cd 0.5 Cu 3 Ti 4 O 12 (x = 0.08), and the other steps are the same as in example 1. The obtained film has a dielectric constant of 9355 at 1kHz, a breakdown field strength of 149kV/mm, and an energy density of 9.2J/cm 3 。
Example 7:
the copper calcium titanate film comprises the following components: ca 0.3 Cr 0.2 Cd 0.5 Cu 3 Ti 4 O 12 (x = 0.12), and the other steps are the same as in example 1. The obtained film has dielectric constant of 8930 at 1kHz, breakdown field strength of 152kV/mm, and energy density of 9.1J/cm 3 。
Example 8:
the copper calcium titanate film comprises the following components: ca 0.3 Cr 0.2 Cd 0.5 Cu 3 Ti 4 O 12 (x = 0.18), and the other steps are the same as in example 1. The obtained film has dielectric constant of 8300, breakdown field strength of 136kV/mm, and energy density of 6.8J/cm at 1kHz 3 。
Comparative example 1:
the copper calcium titanate film comprises the following components: caCu 3 Ti 4 O 12 (x = 0), and the other steps are the same as in example 1. The obtained film has a dielectric constant of 2100, a breakdown field strength of 32kV/mm, and an energy density of 0.25J/cm at 1kHz 3 。
Platinum electrodes were prepared on the surfaces of the films prepared in examples 1 to 5 and comparative example 1 above using a small ion sputtering apparatus to conduct electrical property tests. The inventor adopts a JSM-7001F field emission electron microscope manufactured by Japan, a SmartLab SE type ray diffractometer manufactured by Japan science and technology, a 4294A type precision impedance analyzer manufactured by Agilent technologies and a United states Gishili KEITHLEY 4200 test system to perform characterization tests on the thickness, the structure and the electrical property of the film, and calculates related performance parameters by using the following formula.
Dielectric constant: epsilon r ＝Cd/ε 0 A and C are capacitors, d is the thickness of the film, epsilon 0 Is a vacuum dielectric constant (8.85 × 10) - 12 F/m), A is the area of the electrode.
Nonlinear coefficient:
U 1 ，U 2 are respectively I 1 ＝0.1mA，I 2 Voltage corresponding to 1 mA.
Energy storage density: the energy storage density of the linear dielectric material is determined by the dielectric constant and the breakdown field strength
Wherein epsilon 0 、ε r Respectively, the dielectric constant in vacuum (8.85X 10) -12 F/m) and relative dielectric constant;
for breakdown field strength, U 2 Is I 1 Voltage at 1mA, and d is the film thickness.
As can be seen from fig. 1, the calcium copper titanate thin films prepared in comparative example 1 and examples 1 to 5 both have a single perovskite structure, and no significant second phase is generated. As can be seen from FIG. 2, the dielectric constant of the calcium copper titanate film is significantly improved after the chromium and cadmium are doped, and the frequency is 100-10 5 Good stability is maintained in the Hz range. As can be seen from FIG. 3, the doping significantly enhances the grain boundary resistance of the thin film, which is beneficial to the improvement of the breakdown field strength. This is confirmed by the current density versus field strength variation of FIG. 4, i.e., the breakdown field strength is higher with higher grain boundary resistance, and FIG. 4 also shows a good nonlinear relationship for the thin film; the nonlinear coefficients, breakdown field strengths, and energy storage densities obtained for comparative example and examples 1-5 are shown in FIG. 5. From the results, the chromium and cadmium doping improves the dielectric constant of the film and improves the nonlinear properties such as nonlinear coefficient, breakdown field strength and the like, so that the energy storage density of the film is obviously improved. Comparative example 1 the storage density of the undoped calcium copper titanate thin film was only 0.25J/cm 3 (ii) a And the energy density of the embodiments 1 to 5 after the chromium and the cadmium are doped is 5.8 to 10.4J/cm 3 In particular example 3,Ca 0.4 Cr 0.1 Cd 0.5 Cu 3 Ti 4 O 12 The energy density of the film reaches 10.4J/cm 3 . Therefore, the energy storage density of the copper calcium titanate film obtained by the invention is obviously improved, the method has simple process, low cost and good repeatability, and the obtained product has very important application prospect in the fields of pulse power supplies, medical equipment, electromagnetic energy weapons, particle accelerators and the like。
Claims (10)
1. A chromium and cadmium doped calcium copper titanate film with high energy storage density is characterized in that: the chemical general formula of the chromium and cadmium doped calcium copper titanate film is Ca 0.5-x Cr x Cd 0.5 Cu 3 Ti 4 O 12 ，0.0<x≤0.2。
2. The high energy storage density chromium and cadmium doped copper calcium titanate film of claim 1, wherein: the chemical general formula of the chromium and cadmium doped calcium copper titanate film is Ca 0.5-x Cr x Cd 0.5 Cu 3 Ti 4 O 12 ，0.05≤x≤0.15。
3. The method of claim 2, wherein the method comprises the steps of: firstly, preparing a solution of calcium, cadmium, chromium, copper and titanium by using a sol-gel method, and synthesizing sol; second, in Pt/Ti/SiO 2 Preparing a gel film on a/Si substrate by using a dip-coating method; finally, heat treatment is carried out at a certain temperature and in a certain atmosphere to obtain the film.
4. The method of claim 3, wherein the method comprises the steps of:
(1) Preparing sol: respectively preparing a calcium-chromium-cadmium solution, a copper solution and a titanium solution, uniformly mixing the solutions, and then aging to obtain a precursor sol;
(2) Preparation of gel film: precursor sol is dipped and pulled in Pt/Ti/SiO 2 Preparing a gel film on a Si substrate, then putting the gel film into an oven for drying, and repeating the steps for 4-6 times;
(3) And (3) heat treatment of the film: carrying out heat treatment on the film obtained in the step (2) at a certain temperature and in a certain atmosphere to obtain Ca 0.5-x Cr x Cd 0.5 Cu 3 Ti 4 O 12 A film.
5. The method for preparing the chromium and cadmium doped calcium copper titanate thin film with high energy storage density as claimed in claim 2, wherein the preparation steps of the calcium cadmium chromium solution in the step (1) are as follows: in a glove box with the humidity of less than 30%, adding a propionic acid complexing agent into the reagent A, then adding an ethanol solvent, stirring and dissolving to obtain a solution A, wherein the ratio of the reagent A in the solution is as follows: complexing agent: the molar ratio of the alcohol solvent is 1: (2-4): (10-40), wherein the reagent A is a mixture of calcium acetate, cadmium acetate and chromium acetate according to the stoichiometric ratio.
6. The method for preparing the chromium and cadmium doped calcium copper titanate thin film with high energy storage density as claimed in claim 2, wherein the preparation step of the copper solution in the step (1) is as follows: in a glove box with the humidity less than 30%, adding a propionic acid complexing agent into copper acetate, adding an ethanol solvent, and stirring under the heating condition of 40-50 ℃ to obtain a solution B; copper acetate in solution: complexing agent: the molar ratio of the ethanol solvent is 1: (3-10): (10 to 40).
7. The method for preparing chromium and cadmium doped calcium copper titanate thin film with high energy storage density as claimed in claim 2, wherein the titanium solution in step (1) is prepared by the following steps: in a glove box with the humidity less than 30%, adding complexing agent glacial acetic acid into tetrabutyl titanate, stirring, then adding an ethanol solvent, and continuously stirring to obtain a solution C, wherein tetrabutyl titanate in the solution: glacial acetic acid: the molar ratio of the ethanol solvent is 1:2: (10 to 30).
8. The method for preparing the chromium and cadmium doped calcium copper titanate thin film with high energy storage density according to any one of claims 4 to 7, wherein the molar ratio of calcium, cadmium, chromium, copper and titanium metal ions in the precursor sol in the step (1) is 1.
9. The method for preparing a chromium and cadmium doped calcium copper titanate film with high energy storage density as claimed in claim 8, wherein in the step (2), the cleaned and dried substrate is slowly immersed into the prepared precursor sol by a drawing machine, the substrate is kept stand for 30-40 s at a drawing speed of 8-10 cm/min, the substrate is uniformly drawn out of the surface of the sol, and then the substrate is respectively kept at 100-150 ℃ and 200-250 ℃ for 10-15 min.
10. The method for preparing the chromium and cadmium doped calcium copper titanate thin film with high energy storage density as claimed in claim 8, wherein the heat treatment in the step (3) comprises the following steps:
(1) heating to 500-600 ℃ from room temperature at a speed of 2 ℃/min, and preserving heat for 1-2 hours in air atmosphere;
(2) heating from 500 deg.c to 800-820 deg.c in 1 deg.c/min, maintaining in oxygen atmosphere for 2-3 hr, stopping ventilation and cooling to room temperature.
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