CN107188559B - A kind of high breakdown field strength and the silica-doped copper titanate cadmium giant dielectric ceramic material of energy storage density and preparation method - Google Patents
A kind of high breakdown field strength and the silica-doped copper titanate cadmium giant dielectric ceramic material of energy storage density and preparation method Download PDFInfo
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- 229910010293 ceramic material Inorganic materials 0.000 title claims abstract description 34
- 238000004146 energy storage Methods 0.000 title claims abstract description 25
- 239000010949 copper Substances 0.000 title claims abstract description 15
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 14
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 14
- 229910052793 cadmium Inorganic materials 0.000 title claims abstract description 14
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 title claims abstract description 14
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 14
- 230000015556 catabolic process Effects 0.000 title claims abstract description 13
- 238000002360 preparation method Methods 0.000 title abstract description 14
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 21
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000000843 powder Substances 0.000 claims abstract description 17
- 239000000919 ceramic Substances 0.000 claims abstract description 16
- 229960000583 acetic acid Drugs 0.000 claims abstract description 10
- 239000000463 material Substances 0.000 claims abstract description 10
- 239000012362 glacial acetic acid Substances 0.000 claims abstract description 9
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 9
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 8
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 8
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 8
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 8
- 238000000498 ball milling Methods 0.000 claims abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 6
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 5
- 239000012046 mixed solvent Substances 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 2
- 238000000034 method Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 239000002243 precursor Substances 0.000 abstract description 4
- 238000005469 granulation Methods 0.000 abstract description 3
- 230000003179 granulation Effects 0.000 abstract description 3
- 229910003068 Ti(C4H9O)4 Inorganic materials 0.000 abstract description 2
- 239000002738 chelating agent Substances 0.000 abstract description 2
- 230000000694 effects Effects 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 238000005245 sintering Methods 0.000 abstract description 2
- 238000003980 solgel method Methods 0.000 abstract description 2
- 239000010936 titanium Substances 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 9
- 239000003990 capacitor Substances 0.000 description 8
- PLZFHNWCKKPCMI-UHFFFAOYSA-N cadmium copper Chemical compound [Cu].[Cd] PLZFHNWCKKPCMI-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 description 4
- 238000000227 grinding Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 241000790917 Dioxys <bee> Species 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229910003978 SiClx Inorganic materials 0.000 description 2
- 239000003989 dielectric material Substances 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 238000001069 Raman spectroscopy Methods 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000003985 ceramic capacitor Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 229960004756 ethanol Drugs 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- VDGJOQCBCPGFFD-UHFFFAOYSA-N oxygen(2-) silicon(4+) titanium(4+) Chemical compound [Si+4].[O-2].[O-2].[Ti+4] VDGJOQCBCPGFFD-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
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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
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Abstract
The invention discloses a kind of high breakdown field strength and the silica-doped copper titanate cadmium giant dielectric ceramic material of energy storage density and preparation methods, and the ceramic material is by CdCu3Ti4O12- x wt%SiO2The material of expression forms, and it is with Cd (NO that wherein the value of x, which is 1.0~4.0,3)2·4H2O、Cu(NO3)2·3H2O、Ti(C4H9O)4For raw material, glacial acetic acid is chelating agent, first prepares precursor powder using sol-gel method, and precursor powder is calcined at a lower temperature, obtains the CdCu that can be mixed on a molecular scale and uniformity is preferable, activity is high3Ti4O12Then silicon dioxide powder is added in ceramic powder into ceramic powder, be prepared through ball milling, granulation, tabletting, dumping, sintering.The preparation method of ceramic material of the present invention is simple, reaction temperature is lower, reproducible, high yield rate, and the dielectric properties of ceramic material are excellent, and disruptive field intensity may be up to 895~2352V/cm, 0.712~1.77mJ/cm of energy storage density3, it is with a wide range of applications.
Description
Technical field
The invention belongs to electron ceramic material technical fields, and in particular to arrive a kind of high breakdown field strength and energy storage density dioxy
SiClx doped titanic acid copper cadmium giant dielectric ceramic material and preparation method.
Background technique
Energy and environment are one of the greatest problem that the world today faces and challenge, therefore, how effectively to store energy, subtract
Few energy loss mitigates the hot spot that environmental pressure is scientists study during the last ten years.Energy storage material and its technology are a kind of new
The energy saving means of type increasingly play an important role in daily life and industrial production.However, most of renewable energy
It must be first converted into electric energy, although electric energy can be by cable long distance delivery to the place needed, not due to demand
Together, it is still desirable to develop effective electric energy storage technology.
A few days ago, common electric energy storing device mainly has: chemical cell, supercapacitor and dielectric capacitor.Wherein,
Chemical cell power density is lower, and environmental pollution is larger；Supercapacitor structures are complicated, operation voltage is low, leakage electrical conduction current
Greatly, cycle period is short, it has not been convenient to use；And dielectric capacitor combines the advantages of traditional capacitor and battery, avoids electricity
The defect of chemical supercapacitor is a kind of solid state power supply having a extensive future.But its energy storage density is lower, how to improve electricity
Dielectric capacitor energy storage density is research hotspot and forward position in current solid-state super capacitor field.For linear dielectric
Say that its energy storage density (γ) depends on permittivity ε and dielectric strength Eb, γ=ε0εEb 2/ 2, from formula as can be seen that obtaining height
Dielectric constant and high dielectric strength (height breakdown electric-field strength) are the preconditions for obtaining high energy storage density.Therefore, the high breakdown of exploitation
Field strength and energy storage density dielectric material be there is an urgent need to.
Summary of the invention
Technical problem to be solved by the present invention lies in provide a kind of dioxy with high breakdown field strength and high energy storage density
SiClx doped titanic acid copper cadmium giant dielectric ceramic material, and a kind of preparation method is provided for it.
Ceramic material used by above-mentioned technical problem is solved by CdCu3Ti4O12- x wt%SiO2The material of expression forms,
Wherein the value of x is 1.0~4.0.
The preparation method of inventive silica doped titanic acid copper cadmium giant dielectric ceramic material is made of following step:
1, according to CdCu3Ti4O12Stoichiometric ratio, by Cd (NO3)2·4H2O、Cu(NO3)2·3H2O is added to anhydrous
The in the mixed solvent of ethyl alcohol and deionized water is configured to solution A, by Ti (C4H9O)4It is added in dehydrated alcohol and is configured to solution B；
Solution A and solution B are mixed, and glacial acetic acid is added, the concentration of butyl titanate is 0.3~0.7mol/L, ice in gained mixed liquor
The volume fraction of acetic acid is 2.5%~10%, the volume fraction of deionized water is 5%~15%, is heated simultaneously at 30~75 DEG C
It stirs evenly, obtains colloidal sol, continue stirring until colloidal sol becomes gel, drying, obtains xerogel after gel is aged；It will be dry solidifying
After glue grinding, is calcined 8~10 hours at 600~700 DEG C, obtain CdCu3Ti4O12Ceramic powder.
2, to CdCu3Ti4O12The silicon dioxide powder of its quality 1.0%~4.0% is added in ceramic powder, through ball milling, dries
After dry, granulation, tabletting, dumping, it is sintered 10~15 hours at 960~1000 DEG C, obtains silica-doped huge Jie of copper titanate cadmium
Electroceramics material.
In above-mentioned steps 1, the concentration of butyl titanate is the volume fraction of 0.5mol/L, glacial acetic acid preferably in gained mixed liquor
Volume fraction for 5%, deionized water is 10%.
In above-mentioned steps 1, further preferably heats and stir evenly at 40~50 DEG C, obtain colloidal sol.
In above-mentioned steps 1, after more preferably grinding xerogel, calcined 10 hours at 650 DEG C.
In above-mentioned steps 2, it is sintered 15 hours preferably at 980 DEG C.
The present invention is with Cd (NO3)2·4H2O、Cu(NO3)2·3H2O、Ti(C4H9O)4For raw material, glacial acetic acid is chelating agent, first
Precursor powder is prepared using sol-gel method, and precursor powder is calcined at a lower temperature, obtains mixing on a molecular scale
Conjunction and the CdCu that uniformity is preferable, activity is high3Ti4O12Ceramic powder, then into ceramic powder be added silicon dioxide powder ball milling,
Silica-doped huge Jie of copper titanate cadmium of high breakdown field strength and high energy storage density can be obtained in granulation, tabletting, dumping, sintering
Electroceramics material.
The preparation method of ceramic material of the present invention is simple, reaction temperature is lower, reproducible, high yield rate, and ceramic material
The dielectric properties of material are excellent, and disruptive field intensity may be up to 895~2352V/cm, 0.712~1.77mJ/cm of energy storage density3, practical
Property is strong, can be used for preparing the dielectric material of dynamic RAM capacitor to store information, is also expected to be used for high-voltage capacitor etc.
Aspect.
Detailed description of the invention
Fig. 1 is the XRD diagram of the ceramic material of comparative example 1 and Examples 1 to 3 preparation.
Fig. 2 is the dielectric constant of the ceramic material of comparative example 1 and Examples 1 to 3 preparation with the variation relation of test frequency
Figure.
Fig. 3 be comparative example 1 and Examples 1 to 3 preparation ceramic material current density with work field strength variation relation figure.
The disruptive field intensity and energy storage density that Fig. 4 is the ceramics sample of comparative example 1 and Examples 1 to 3 preparation are with SiO2Doping
The variation relation figure of amount.
Specific embodiment
The present invention is described in more detail with reference to the accompanying drawings and examples, but protection scope of the present invention is not limited only to
These embodiments.
Embodiment 1
1, according to CdCu3Ti4O12Stoichiometric ratio, by 3.1159g Cd (NO3)2·4H2O、7.3212g Cu
(NO3)2·3H2O is added to 10mL dehydrated alcohol and the in the mixed solvent of deionized water is configured to solution A, by 13.8mL Ti
(C4H9O)4It is added in 52.2mL dehydrated alcohol and is configured to solution B；Solution A and solution B are mixed, and 4mL glacial acetic acid is added,
The concentration of butyl titanate is 0.5mol/L in gained mixed liquor, the volume fraction of glacial acetic acid is 5.0%, the volume of deionized water point
Number be 10%, heat and stir evenly at 45 DEG C, obtain colloidal sol, continue stirring until colloidal sol become gel, gel is aged
It is 48 hours dry at 100 DEG C after 12 hours, obtain the loose shape xerogel of brown blue；After xerogel is ground, at 650 DEG C
Calcining 10 hours, obtains CdCu3Ti4O12Ceramic powder.
2, to CdCu3Ti4O12The silicon dioxide powder of its quality 1.0% is added in ceramic powder, using dehydrated alcohol as medium,
It after agate ball ball milling 10 hours of 5~6mm, is dried at 80 DEG C, the polyvinyl alcohol water that mass fraction is 5% is then added
Solution, grinding are granulated, and after crossing 120 meshes, are pressed into 11.5mm cylinder blank under 6MPa pressure with powder compressing machine, will be justified
Column blank is placed on zirconium oxide plate, was warming up to 500 DEG C with 380 minutes, 2 hours is kept the temperature, then with 2 DEG C/min of heating
Rate is warming up to 980 DEG C, Isothermal sinter 15 hours, cools to room temperature with the furnace, obtains high breakdown field strength and energy storage density titanium dioxide
Silicon doped titanic acid copper cadmium giant dielectric ceramic material.
Embodiment 2
In the present embodiment, to CdCu3Ti4O12The silicon dioxide powder of its quality 2.0% is added in ceramic powder, other steps
It is same as Example 1, obtain high breakdown field strength and the silica-doped copper titanate cadmium giant dielectric ceramic material of energy storage density.
Embodiment 3
In the present embodiment, to CdCu3Ti4O12The silicon dioxide powder of its quality 4.0% is added in ceramic powder, other steps
It is same as Example 1, obtain high breakdown field strength and the silica-doped copper titanate cadmium giant dielectric ceramic material of energy storage density.
Comparative example 1
Silicon dioxide powder is not added, other steps are same as Example 1, obtain copper titanate cadmium giant dielectric ceramic material.
Ceramic material surfaces prepared by above-described embodiment 1~3 and comparative example 1 are polished, polishing, ultrasound, are wiped over clean, In
Silver paste is respectively coated in its upper and lower surface, is placed in Muffle furnace and keeps the temperature 30 minutes for 840 DEG C, cooled to room temperature.Inventor uses
D/max-2200X type x ray diffractometer x, the 4294A type of Anjelen Sci. & Tech. Inc's production of Rigaku company production are accurate
The iron of impedance analyzer, the micro confocal laser Raman spectrometer of Reinshaw company, Britain production and U.S. Radiant production
Electric tester carries out characterization test to its structure and performance, and passes through the various calculating correlation performance parameters of following formula:
Permittivity εr: εr=4Ct/ (π ε0d)
γ: γ=1/2 ε of energy storage density0εrEb 2
In formula, C is capacitor, and t is the thickness of potsherd, ε0For permittivity of vacuum (8.85 × 10-12F/m), d is ceramics
The diameter of piece, EbFor disruptive field intensity.The result is shown in Figure 1~4.
As seen from Figure 1, the ceramic material that prepared by comparative example 1 is pure perovskite-like structure, the ceramic material of Examples 1 to 3
Occurs SiO in material2Second phase, while with SiO2The increase of doping, SiO2Second phase phase diffraction maximum quantity intensity gradually increases
Add.From Figure 2 it can be seen that good giant dielectric is presented in comparative example 1 and the ceramic material of Examples 1 to 3 preparation, arrived in 40Hz
Very high dielectric constant (> 10 is all kept within the scope of 100kHz3).By Fig. 3 and Fig. 4 as it can be seen that ceramic material prepared by comparative example 1
Disruptive field intensity is about 257V/cm, doped SiO2It is afterwards the ceramic material disruptive field intensity and energy storage density of Examples 1 to 3 preparation
It is significantly improved, disruptive field intensity is about 895~2352V/cm, 0.712~1.77mJ/cm of energy storage density3, especially work as SiO2
When doping is 4.0%, ceramic material keeps good giant dielectric (under 1kHz, relative dielectric constant 5635), while its
Disruptive field intensity may be up to 2352V/cm, and energy storage density is up to 1.77mJ/cm at this time3.It can be seen that ceramic material of the present invention has
There are high dielectric constant, high breakdown field strength, high energy storage density, it is practical, it is expected to dynamic random storage (DRAM) and chip multilayer
The application of the electronic markets such as ceramic capacitor (MLCC).
Claims (5)
1. a kind of high breakdown field strength and the silica-doped copper titanate cadmium giant dielectric ceramic material of energy storage density, it is characterised in that:
The ceramic material is by CdCu3Ti4O12-x wt% SiO2The material of expression forms, whereinxValue be 1.0~4.0；The ceramics material
Material is prepared by the following method to obtain:
(1) according to CdCu3Ti4O12Stoichiometric ratio, by Cd (NO3)2•4H2O、Cu(NO3)2•3H2O be added to dehydrated alcohol with
The in the mixed solvent of deionized water is configured to solution A, by Ti (C4H9O)4It is added in dehydrated alcohol and is configured to solution B；By solution
A and solution B mixing, and are added glacial acetic acid, in gained mixed liquor the concentration of butyl titanate be 0.3~0.7mol/L, glacial acetic acid
Volume fraction is 2.5%~10%, the volume fraction of deionized water is 5%~15%, heats and stirs evenly at 30~75 DEG C, obtains
To colloidal sol, continue stirring until colloidal sol becomes gel, drying, obtains xerogel after gel is aged；After xerogel is ground, In
It is calcined 8~10 hours at 600~700 DEG C, obtains CdCu3Ti4O12Ceramic powder；
(2) to CdCu3Ti4O12The silicon dioxide powder of its quality 1.0%~4.0% is added in ceramic powder, through ball milling, dries, make
It after grain, tabletting, dumping, is sintered 10~15 hours at 960~1000 DEG C, obtains silica-doped copper titanate cadmium giant dielectric ceramics
Material.
2. silica-doped copper titanate cadmium giant dielectric ceramic material according to claim 1, it is characterised in that: step
(1) in, the concentration of butyl titanate is 0.5mol/L in gained mixed liquor, the volume fraction of glacial acetic acid is 5%, the body of deionized water
Fraction is 10%.
3. silica-doped copper titanate cadmium giant dielectric ceramic material according to claim 1, it is characterised in that: step
(1) it in, heats and stirs evenly at 40~50 DEG C, obtain colloidal sol.
4. silica-doped copper titanate cadmium giant dielectric ceramic material according to claim 1, it is characterised in that: step
(1) it in, after xerogel is ground, is calcined 10 hours at 650 DEG C.
5. silica-doped copper titanate cadmium giant dielectric ceramic material according to claim 1, it is characterised in that: step
(2) it in, is sintered 15 hours at 980 DEG C.
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| CN103253933A (en) * | 2013-05-09 | 2013-08-21 | 陕西师范大学 | Lithium replaced copper cadmium titanate gigantic dielectric ceramic material and preparation method thereof |
| CN106882963A (en) * | 2017-03-31 | 2017-06-23 | 天津大学 | A kind of method that CaCu 3 Ti 4 O is prepared based on sol-gal process |
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| CN103253933A (en) * | 2013-05-09 | 2013-08-21 | 陕西师范大学 | Lithium replaced copper cadmium titanate gigantic dielectric ceramic material and preparation method thereof |
| CN106882963A (en) * | 2017-03-31 | 2017-06-23 | 天津大学 | A kind of method that CaCu 3 Ti 4 O is prepared based on sol-gal process |
Non-Patent Citations (3)
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| Improved Dielectric and Nonlinear Electrical Properties of Fine-Grained CaCu3Ti4O12 Ceramics Prepared by a Glycine-Nitrate Process;Prasit Thongbai;《J. Am. Ceram. Soc.》;20141231;第1785–1790页 * |
| Observation of giant dielectric constant in CdCu3Ti4O12 ceramics;Rongqing Zuo et al.;《Solid State Communications》;20061231;第91–94页 * |
| SiO2 添加物对CaCu3 Ti4 O12 陶瓷的微观结构与介电性能的影响;李 旺等;《人工晶体学报》;20091231;第1365-1369页 * |
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