CN202796464U - High-dielectric-material porous structure capacitor - Google Patents

High-dielectric-material porous structure capacitor Download PDF

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CN202796464U
CN202796464U CN 201220161667 CN201220161667U CN202796464U CN 202796464 U CN202796464 U CN 202796464U CN 201220161667 CN201220161667 CN 201220161667 CN 201220161667 U CN201220161667 U CN 201220161667U CN 202796464 U CN202796464 U CN 202796464U
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porous
high dielectric
dielectric material
dielectric
capacitor
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符建
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    • Y02E60/13—Energy storage using capacitors

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Abstract

The utility model discloses a high-dielectric-material porous structure capacitor. The capacitor comprises a porous-metal high-dielectric-material composite substrate, a metal medium with a low melting point, a sealing container, a positive electrode and a negative electrode. The porous-metal high-dielectric-material composite substrate is a porous material which is formed through depositing one layer or multilayer high dielectric materials on a foam metal skeleton surface. The porous-metal high-dielectric-material composite substrate is infiltrated in the metal medium with the low melting point and is packaged in the sealing container. The porous-metal high-dielectric-material composite substrate is connected with the positive electrode. A conductive liquid medium is connected with the negative electrode. A super capacitor which stores electric energy is formed. According to the utility model, a porous electrode is used because of possessing a great surface area; a BaTiO3 or CaCu3Ti4O12 high dielectric coefficient can realize a high-capacity capacitor. By using the current super capacitor, a working voltage is low. By using the capacitor of the utility model, the above problem is solved and the capacitor acquires a high energy accumulation density.

Description

A kind of high dielectric material loose structure electric capacity
Technical field
The utility model relates to the electric capacity for storing electrical energy, relates in particular to a kind of high dielectric material loose structure electric capacity.
Background technology
The electric power storage technology mainly contains two kinds at present, and a kind of is lithium ion battery: utilize lithium (Li +) the chemical reaction realization charge and discharge process of ion between anode and negative electrode, another kind is super capacitor: utilize porous electrode huge surface area and minimum spacing to form the huge double layer capacity structure of capacity, realize discharging and recharging by physical process.
These two kinds of technology respectively have pluses and minuses on electric power storage is used: lithium ion battery has the advantages such as energy storage density is large, and leakage current is little, recycles the shortcomings such as number of times is few, the life-span is short, the charging interval is long, power density is little, poor stability but exist; It is short that super capacitor has the charging interval, and power density is large and recycle often and the advantage such as the life-span is long, but the energy storage density of super capacitor only has about 1/10th of battery at present, is difficult to replace battery to realize that extensive electric power storage uses.
Present super capacitor utilizes the double layer capacity structure mostly, utilizes the great surface area of activated carbon loose structure and water-based or polyelectrolyte at the as thin as a wafer sheath that these surfaces form, and has realized very large capacitance.Common this electric capacity can reach thousands of farads.But because electrolytical disassociation voltage is very low, so the operating voltage of these electric capacity only has several volts.Because square being directly proportional of electric capacity energy accumulation and voltage, so the super capacitor energy density of this principle is smaller.
Recently, United States Patent (USP) (US7466536) proposes a kind of patent of utilizing high-k material to realize large electric capacity electric power storage, by put into one deck BaTiO as thin as a wafer between two electrodes 3Then high-k material realizes enough large capacity by a lot of capacitive stacks.United States Patent (USP) (US20070121274) proposes a kind of CaCu 3Ti 4O 12Plural layers are realized large bulk capacitance.This bi-material has very high dielectric constant, and these two patents prepare the high-k material rete by methods such as plated film or nano-encapsulated.Can bear very high withstand voltagely on this capacitance principle, so energy density can increase substantially.But these two kinds of methods will realize that high capacitance needs very many laminated construction, and preparation is got up very difficultly on the one hand, and this planar structure surface area that can provide is very limited on the other hand.
In order to solve this difficulty, we use for reference the principle that existing super capacitor utilizes the porous electrode huge surface area, propose a kind of preferred plan in conjunction with two kinds of methods: high dielectric material loose structure super capacitor.Can solve on the one hand the existing low problem of super capacitor operating voltage, greatly increase on the other hand surface area and increased capacitance.
Summary of the invention
The purpose of this utility model is to overcome the deficiencies in the prior art, and a kind of high dielectric material loose structure electric capacity is provided.
High dielectric material loose structure electric capacity comprises porous metals high dielectric material composite base plate, low-melting-point metal medium, airtight container, positive electrode, negative electrode; Porous metals high dielectric material composite base plate is the porous material that forms at foam metal skeleton surface one or more layers high dielectric material of deposition, porous metals high dielectric material composite base plate infiltrates in the low-melting-point metal medium, and be encapsulated in the airtight container, porous metals high dielectric material composite base plate links to each other with positive electrode, conductive fluid medium links to each other with negative electrode, forms the capacitor of accumulating electric energy.
Described high dielectric material is BaTiO 3Or CaCu 3Ti 4O 12High-k material, perhaps bi-material alternately is formed by stacking.
The material of described foam metal skeleton is copper, nickel, titanium or the aluminium of porous foam attitude.
The BaTiO of described porous metals high dielectric material composite base plate 3The step of sol gel sintered method is:
4.1) be that two kinds of solution of A, B of 1:1 mix with mol ratio, in the water-bath of 40 ℃～80 ℃ of temperature, carry out chemical reaction, the reaction time is 10 minutes～1 hour, obtains the colloidal sol that solution concentration is 0.3～0.5mol/L; A solution is comprised of according to mol ratio 1:1 barium acetate and acetic acid solution; B solution is by butyl titanate and the solution composition of mol ratio 1:1 Ethanol-Acetic Acid; The acetic acid that adds mol ratio 1:1 reduces pH value inhibition butyl titanate and is hydrolyzed in solution;
4.2) the foam metal skeleton is put into the colloidal sol complete wetting, then ageing 4～8 hours in air vacuumizes more than 10 minutes again;
4.3) in 100 ℃～160 ℃ baking ovens, dry, obtain being attached with the foam metal skeleton of xerogel;
4.4) sintering temperature is 900 ℃～1150 ℃ in Muffle furnace, is incubated 1～4 hour, obtains BaTiO 3Porous metals high dielectric material composite base plate.
The CaCu of described porous metals high dielectric material composite base plate 3Ti 4O 12The step of sol gel sintered method is:
5.1) be that two kinds of solution of C, D of 1:4 mix with mol ratio, fully stir and obtained the colloidal sol that solution concentration is 0.3～0.5mol/L in 1 hour; C solution is mixed then fully to stir with mol ratio 1:1 ethanolic solution by 3:1 by copper nitrate, calcium acetate and forms; D solution is comprised of butyl titanate adding mol ratio 1:1 ethanol, glacial acetic acid solution; Adding mol ratio 1:1 acetic acid reduction pH value inhibition butyl titanate is hydrolyzed in solution;
5.2) the foam metal skeleton is put into the colloidal sol complete wetting, then ageing 4～6 hours in air vacuumized more than 10 minutes;
5.3) in 70 ℃ of baking ovens, dry, obtain being attached with the foam metal skeleton of xerogel;
5.4) the foam metal bone that is attached with xerogel is sintering in 700 ℃～1150 ℃ Muffle furnaces in temperature, is incubated 6～10 hours, obtains CaCu 3Ti 4O 12Porous metals high dielectric material composite base plate.
Described low-melting-point metal medium be gallium, indium, zinc, tin, magnesium, copper or gold one or more.
Described impregnation process is to allow first the low-melting-point metal medium melt fully, then porous metals high dielectric material composite base plate is immersed in the low-melting-point metal medium, allows the low-melting-point metal medium penetrate into fully in the hole of porous metals high dielectric material composite base plate.
The utility model not only utilizes porous electrode to have great surface area, and utilizes sol-gel method to realize BaTiO 3System or CaCu 3Ti 4O 12Be that high-k material is for comprehensive covering on porous electrode surface, utilize simultaneously low-melting-point metal to penetrate into fully in the hole of porous metals high dielectric material composite base plate, realize the little gap of trying one's best between two electrodes of electric capacity, thereby greatly increased capacitance.This method not only can solve the existing low problem of super capacitor operating voltage, and because huge surface area is accumulated density so that electric capacity has obtained high energy.
Description of drawings
Fig. 1 is high dielectric material loose structure super capacitor schematic diagram;
Fig. 2 is foam metal skeleton micrograph;
Fig. 3 has deposited the thin high dielectric material foam metal skeleton micrograph of one deck;
Fig. 4 is the electric power storage principle schematic.
Among the figure: porous metals high dielectric material composite base plate 1, low-melting-point metal medium 2, airtight container 3, positive electrode 4, negative electrode 5, foam metal skeleton 6, high dielectric material 7.
Embodiment
As shown in Figure 1, high dielectric material loose structure electric capacity comprises porous metals high dielectric material composite base plate 1, low-melting-point metal medium 2, airtight container 3, positive electrode 4, negative electrode 5; Porous metals high dielectric material composite base plate 1 is the porous material that forms at one or more layers high dielectric material 7 of foam metal skeleton 6 surfaces deposition, porous metals high dielectric material composite base plate 1 infiltrates in low-melting-point metal medium 2, and be encapsulated in 3 li of airtight containers, porous metals high dielectric material composite base plate 1 links to each other with positive electrode 4, conductive fluid medium 2 links to each other with negative electrode 5, forms the capacitor of accumulating electric energy.
Described high dielectric material 7 is BaTiO 3Or CaCu 3Ti 4O 12High-k material, perhaps bi-material alternately is formed by stacking.
The material of described foam metal skeleton 6 is copper, nickel, titanium or the aluminium of porous foam attitude.
The BaTiO of described porous metals high dielectric material composite base plate 1 3The step of sol gel sintered method is:
4.1) be that two kinds of solution of A, B of 1:1 mix with mol ratio, in the water-bath of 40 ℃～80 ℃ of temperature, carry out chemical reaction, the reaction time is 10 minutes～1 hour, obtains the colloidal sol that solution concentration is 0.3～0.5mol/L; A solution is comprised of according to mol ratio 1:1 barium acetate and acetic acid solution; B solution is by butyl titanate and the solution composition of mol ratio 1:1 Ethanol-Acetic Acid; The acetic acid that adds mol ratio 1:1 reduces pH value inhibition butyl titanate and is hydrolyzed in solution;
4.2) foam metal skeleton 6 is put into the colloidal sol complete wetting, then ageing 4～8 hours in air vacuumizes more than 10 minutes again;
4.3) in 100 ℃～160 ℃ baking ovens, dry, obtain being attached with the foam metal skeleton 6 of xerogel;
4.4) sintering temperature is 900 ℃～1150 ℃ in Muffle furnace, is incubated 1～4 hour, obtains BaTiO 3Porous metals high dielectric material composite base plate 1.
The CaCu of described porous metals high dielectric material composite base plate 1 3Ti 4O 12The step of sol gel sintered method is:
5.1) be that two kinds of solution of C, D of 1:4 mix with mol ratio, fully stir and obtained the colloidal sol that solution concentration is 0.3～0.5mol/L in 1 hour; C solution is mixed then fully to stir with mol ratio 1:1 ethanolic solution by 3:1 by copper nitrate, calcium acetate and forms; D solution is comprised of butyl titanate adding mol ratio 1:1 ethanol, glacial acetic acid solution; Adding mol ratio 1:1 acetic acid reduction pH value inhibition butyl titanate is hydrolyzed in solution;
5.2) foam metal skeleton 6 is put into the colloidal sol complete wetting, then ageing 4～6 hours in air vacuumized more than 10 minutes;
5.3) in 70 ℃ of baking ovens, dry, obtain being attached with the foam metal skeleton of xerogel;
5.4) the foam metal bone that is attached with xerogel is sintering in 700 ℃～1150 ℃ Muffle furnaces in temperature, is incubated 6～10 hours, obtains CaCu 3Ti 4O 12Porous metals high dielectric material composite base plate 1.
Described low-melting-point metal medium 2 be gallium, indium, zinc, tin, magnesium, copper or gold one or more.
Described impregnation process is to allow first low-melting-point metal medium 2 melt fully, then porous metals high dielectric material composite base plate 1 is immersed in the low-melting-point metal medium 2, allow low-melting-point metal medium 2 penetrate into fully in the hole of porous metals high dielectric material composite base plate 1.
Fig. 2 is foam metal skeleton 6 micrographs, the foam metal skeleton is to be made of porous foam metal, porous foam metal is a kind of metal material that contains the hole of some, certain size aperture, certain porosity in metallic matrix, such as nickel foam, foam copper, foamed aluminium etc.This porous foam metal has through hole type sponge attitude foaming structure, and porosity can be up to 98%, and specific area can be up to 9000cm 2/ cm 3More than.Because porous foam metal has through-hole structure, in the time of in being immersed in collosol and gel, ageing by the long period and the measure such as vacuumize, inner each micropore can both be infiltrated by collosol and gel fully, but can form very thin very firmly high dielectric material layer 7 at the porous foam metal inner surface by these collosol and gels of high-temperature baking.
Fig. 3 has deposited the thin high dielectric material foam metal skeleton micrograph of one deck, can find out because high dielectric material layer 7 is thinner from displaing micro picture, therefore can not stop up internal capillary.It is contemplated that this material is immersed in the low-melting-point metal medium 2 of thawing, low-melting-point metal medium 2 all will be penetrated into each micropore fully, thereby and form capacitance structure between the foam metal skeleton.
Fig. 4 is the electric power storage principle schematic, when foam metal skeleton 6 links to each other with positive electrode 4, low-melting-point metal 2 links to each other with negative electrode 5, because there is one deck high dielectric material layer 7 on foam metal skeleton 6 surfaces, so forms an electric capacity between foam metal skeleton 6 and the low-melting-point metal 2.Between electrode, add appropriate voltage, high dielectric material layer 7 produces polarity effect, store a large amount of positive charges at the interface that links to each other with foam metal skeleton 6, and store a large amount of negative electrical charges at the interface that links to each other with low-melting-point metal 2, can accumulate a large amount of electric energy thus.According to capacitance equation C=ε as can be known rε 0S/d as can be known, surface area more high capacitance is larger, simultaneously more high capacitance is also larger for material dielectric constant.By the analysis of front as can be known, the foam metal skeleton provides great surface area, has therefore greatly increased capacitance.From pertinent literature as can be known, because BaTiO 3And CaCu 3Ti 4O 12Grain boundary effect cause these materials can produce huge dielectric constant, for example: BaTiO 3Relative dielectric constant ε rUnder the KHz frequency, can reach more than 19818, and CaCu 3Ti 4O 12Can up to 194735, therefore adopt this bi-material can realize high capacitance.Accumulated the formula E=CU of electric energy by electric capacity 2/ 2 as can be known, and square being directly proportional of electric capacity charge capacity and voltage improves the withstand voltage of dielectric materials layer, can larger raising electric capacity charge capacity.Because high dielectric material layer 7 is solid matters, has very high withstand voltage, for example: BaTiO 3Withstand voltagely can reach 500MV/m, CaCu 3Ti 4O 12Withstand voltagely can reach 250MV/m.Even therefore dielectric materials layer only has micron order, the electric capacity operating voltage also can reach hundreds of volts, and this electric capacity can obtain high energy and accumulate density.

Claims (2)

1. a high dielectric material loose structure electric capacity is characterized in that comprising porous metals high dielectric material composite base plate (1), low-melting-point metal medium (2), airtight container (3), positive electrode (4), negative electrode (5); Porous metals high dielectric material composite base plate (1) is the porous material that forms at foam metal skeleton (6) surface one or more layers high dielectric material of deposition (7), porous metals high dielectric material composite base plate (1) infiltrates in low-melting-point metal medium (2), and it is inner to be encapsulated in airtight container (3), porous metals high dielectric material composite base plate (1) links to each other with positive electrode (4), conductive fluid medium (2) links to each other with negative electrode (5), forms the capacitor of accumulating electric energy; Described high dielectric material (7) is BaTiO 3Or CaCu 3Ti 4O 12High-k material, perhaps bi-material alternately is formed by stacking; Described low-melting-point metal medium (2) be gallium, indium, zinc, tin, magnesium, copper or gold one or more.
2. a kind of high dielectric material loose structure electric capacity as claimed in claim 1, the material that it is characterized in that described foam metal skeleton (6) is copper, nickel, titanium or the aluminium of porous foam attitude.
CN 201220161667 2012-04-17 2012-04-17 High-dielectric-material porous structure capacitor Expired - Fee Related CN202796464U (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103956274A (en) * 2014-04-22 2014-07-30 上海大学 Super capacitor combined electrode preparing method
WO2017121201A1 (en) * 2016-01-11 2017-07-20 苏州大学张家港工业技术研究院 Barium titanate foam ceramic and preparation method therefor
US20240079183A1 (en) * 2022-08-23 2024-03-07 U.S. Army DEVCOM, Army Research Laboratory Dielectric capacitor formed of a dielectric-coated electrically conductive porous scaffold filled with metal

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103956274A (en) * 2014-04-22 2014-07-30 上海大学 Super capacitor combined electrode preparing method
WO2017121201A1 (en) * 2016-01-11 2017-07-20 苏州大学张家港工业技术研究院 Barium titanate foam ceramic and preparation method therefor
US20240079183A1 (en) * 2022-08-23 2024-03-07 U.S. Army DEVCOM, Army Research Laboratory Dielectric capacitor formed of a dielectric-coated electrically conductive porous scaffold filled with metal

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