CN103065807A - High-energy density super capacitor based on nanometer dielectric material layer - Google Patents

High-energy density super capacitor based on nanometer dielectric material layer Download PDF

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CN103065807A
CN103065807A CN2013100108098A CN201310010809A CN103065807A CN 103065807 A CN103065807 A CN 103065807A CN 2013100108098 A CN2013100108098 A CN 2013100108098A CN 201310010809 A CN201310010809 A CN 201310010809A CN 103065807 A CN103065807 A CN 103065807A
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dielectric layer
nanometer dielectric
carbon nano
electrode
nanometer
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姜训勇
刘慧敏
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Tianjin University of Technology
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Tianjin University of Technology
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/13—Energy storage using capacitors

Abstract

A high-energy density super capacitor based on a nanometer dielectric material layer is composed of a positive electrode, a negative electrode, a nanometer dielectric layer, electrolyte and a capacitor external connection wire. The positive electrode and the negative electrode which serve as electric conduction electrodes are provided with high specific surface areas. The nanometer dielectric layer is coated on the surfaces of the positive electrode and the negative electrode. The positive electrode and the negative electrode coated by the nanometer dielectric layer are immersed in the electrolyte. The positive electrode and the negative electrode are combination electrodes of nickel, aluminum and copper sheet and carbon nano tube or foamed aluminum, foamed nickel and foamed copper and the carbon nano tube or are foamed aluminium anodic oxidation treatment electrodes. The nanometer dielectric layer is Al 2 O 3 or Ta 2 O 5 and the thickness of the nanometer dielectric layer is 10-500 nm. The electrolyte is KCL water solution with concentration of 0.1-50 w or KOH water solution with concentration of 0.1-50 w. The high-energy density super capacitor based on the nanometer dielectric material layer has the advantages that a pressurization layer made of dielectric materials and with high breakdown voltage resistance is coated on the surface of electrode material of a traditional capacitor, working voltage of the super capacitor is improved, and energy density of the super capacitor is improved.

Description

A kind of high-energy-density ultracapacitor based on the nanometer dielectric materials layer
[technical field]
The present invention relates to the electrode material of ultracapacitor, particularly a kind of high-energy-density ultracapacitor based on the nanometer dielectric materials layer.
[background technology]
The energy density of electric capacity is the energy that unit volume or quality electric capacity can provide, and it is relevant with the energy that electric capacity can provide.Improve the method for the energy density of electric capacity, a kind of is the capacity that significantly improves electric capacity, and another kind is the operating voltage that improves electric capacity, referring to: 1) Winter, M.; J.Brodd, R.Chem.Rew.2004,104,25; 2) Ma, L.P.and Y. Yang, Applied Physic Letters87 (12), 2005:3; 3) Zhang Zhian, Yang Bangchao, Deng Meigen, Hu Yongda, Journal of Inorganic Materials, Vol20, No.3,2005:p529; 4) Liu Yexiang, battery, Vol35, No.3,2005:p196; 5) B.E.Conway work, Chen Ai etc. translate, electric chemical super capacitor-the principles of science and technology are used, Chemical Industry Press, 2005 years 1 edition.
Ultracapacitor (Supercapacitors) mainly is to utilize the electric double layer capacitance that is present on electrode material and the electrolyte interface to come store electrical energy, its electrode material adopts usually has high surface area nano-porous material, referring to 1) Yong-gang Wang, Yong-yao Xia, Journal of the electrochemical society, Vol153 (2), 2006:pA450; 2) Kenneth H.Reimen, Karen M.Brace, toby J.Gordon-smith, etal, Electrochemistry Commuciations, Vol.8,2006:p517; 3) Sang-Bok Ma, Kyung-Wan Nam, etal, Journal of Power Sources, 128,2008:p483; 4) M.Lazzari, F.Soavi, M.Mastragotino, Journal of Power Source, 178,2008:p490; 5) Frackowiak, E.; Beguin, F.Carbon2002,40, (10), 1775-1787; 6) Ma, S.B.; Nam, K.W.; Yoon, W.S.; Yang, X.Q.; Ahn, K.Y.; Oh, K.H.; Kim, K.B.Electrochemistry Communications2007,9, (12), 2807-2811.Ultracapacitor is because its electrode material (such as nano material) has high specific area, and electric double layer thickness is nanometer scale, thereby its capacitance will exceed much than the capacity of traditional capacitance.
The capacitance of ultracapacitor can reach more than the 1300F g-1 at present, referring to: Patrice Simon, YurY GoGotSi, Nature Materials, 2007,7,845-854.But the shortcoming of ultracapacitor is its operating voltage to be compared much lower with traditional electric capacity.Energy and the capacitance of electric capacity are linear, are quadratic relationship with the operating voltage of electric capacity.Although ultracapacitor has higher capacitance, because its low operating voltage causes its energy density very low.Want to improve the energy of electric capacity, except obtaining the high degree of electrical capacity, must improve the operating voltage of electric capacity.Under the characteristics that keep the ultracapacitor high-capacitance, further improve simultaneously its operating voltage, be the effective way that obtains high energy density capacitor.
The operating voltage of ultracapacitor depends on the decomposition voltage of electrolyte, referring to: Baughman, R.H.e.a.Science2002,297,787-792.For the symmetry electrode electric capacity that adopts water electrolysis liquid, the operating voltage of ultracapacitor can not surpass 1V, referring to: Frackowiak, E.; Beguin, F.Carbon2002,40, (10), 1775-1787.If adopt the asymmetric electrode design, the operating voltage of water electrolysis liquid system electric capacity can reach 2V, referring to: Ma, S.B.; Nam, K.W.; Yoon, W.S.; Yang, X.Q.; Ahn, K.Y.; Oh, K.H.; Kim, K.B.Electrochemistry Communications2007,9, (12), 2807-2811.Even if water electrolysis liquid is replaced with nonaqueous electrolytic solution, such as organic electrolyte or ionic liquid, the operating voltage of electric capacity is also just about 4V, referring to Lazzari, M.; Soavi, F.; Mastragostino, M.Journal of Power Sources2008,178, (1), 490-496.Because the restriction of the decomposition voltage of electrolyte, the operating voltage that further improves ultracapacitor under present ultracapacitor technical system is very difficult.
[summary of the invention]
The present invention is directed to the shortcoming of present ultracapacitor low-work voltage, a kind of high-energy-density ultracapacitor based on the nanometer dielectric materials layer is provided, this ultracapacitor adopts the dielectric materials layer with high voltage endurance capability to cover the electrode material for super capacitor surface, significantly improve the ultracapacitor operating voltage thereby reach, improve the purpose of super capacitor energy density.
Technical scheme of the present invention:
A kind of high-energy-density ultracapacitor based on the nanometer dielectric materials layer, by positive pole, negative pole, the nanometer dielectric layer, electrolyte and electric capacity external lead wire consist of, positive pole and negative pole as conductive electrode have high-specific surface area, the nanometer dielectric layer is coated on the surface of anodal and negative pole, the positive pole and the negative pole that are coated with the nanometer dielectric layer are immersed in the electrolyte, and described positive pole and negative pole are nickel-carbon nano-tube combination electrode, aluminium-carbon nano-tube combination electrode, copper-carbon nano-tube combination electrode or or nickel foam-carbon nano-tube combination electrode, foamed aluminium-carbon nano-tube combination electrode, foam copper-carbon nano-tube combination electrode or foamed aluminium anodized electrode; The nanometer dielectric layer is Al 2O 3Or Ta 2O 5, thickness is 10-500nm; Electrolyte is that mass percent concentration is the KCl aqueous solution or the KOH aqueous solution of 0.1-50%.
The method that described nanometer dielectric layer is coated on the surface of anodal and negative pole is electrophoresis, physical vaporous deposition or chemical vapour deposition technique.
Working mechanism of the present invention:
This ultracapacitor conductive electrode surface coverage one deck forms Withstand voltage layer by the nanometer dielectric layer material with high breakdown voltage resistant ability, capacitance voltage falls mainly to be born by the nanometer dielectric materials layer, and conductive electrode does not directly contact with electrolyte, thereby the high-capacitance that can keep electric capacity, the breakdown voltage resistant of electric capacity can have been compared significantly raising by force rate tradition ultracapacitor simultaneously, cause this ultracapacitor more working under the high voltage, its energy density is compared with traditional ultracapacitor and is improved a lot.
Advantage of the present invention is:
This ultracapacitor adopts the Withstand voltage layer that is comprised of dielectric material that has high breakdown voltage resistant ability in traditional electrode material for super capacitor surface coverage, can significantly improve the operating voltage of ultracapacitor, thus the energy density of raising ultracapacitor.
[description of drawings]
Accompanying drawing is this supercapacitor structures schematic diagram.
Among the figure: 1. anodal 2. negative poles, 3. electrolyte, 4. nanometer dielectric layers, 5. electric capacity external lead wires
[embodiment]
Tell about by the following examples detailed process of the present invention, it is convenience in order to understand that embodiment is provided, and never is restriction the present invention.
Embodiment 1:
A kind of high-energy-density ultracapacitor based on the nanometer dielectric materials layer, as shown in drawings, consisted of by positive pole 1, negative pole 2, nanometer dielectric layer 3, electrolyte 4 and electric capacity external lead wire 5, positive pole and negative pole as conductive electrode have high-specific surface area, the nanometer dielectric layer is coated on the surface of anodal and negative pole, the positive pole and the negative pole that are coated with the nanometer dielectric layer are immersed in the electrolyte, and described positive pole and negative pole are nickel foam-carbon nano-tube combination electrode, and the nanometer dielectric layer is Al 2O 3, thickness is 20nm, electrolyte is that mass percent concentration is 1% the KCl aqueous solution; Its preparation methods steps is as follows:
1) multi-walled carbon nano-tubes is dispersed in the ethanol, the adding mass percent is 0.5% MgNO 3, fully mix.
2) with porous nickel mesh as negative pole, adopt electrophoresis that multi-walled carbon nano-tubes is deposited on the porous nickel mesh;
3) with granularity be the Al of 20-40nm 2O 3Be dispersed in the alcohol, the adding mass percent is 0.5%MgNO 3, mix;
4) take the nickel electrode that deposits carbon nano-tube as substrate, adopt electrophoresis depositing Al on electrode 2O 3, at carbon nano tube surface clad nano dielectric layer;
5) can make the high-energy-density ultracapacitor after positive pole, negative pole, electrolyte and the assembling of electric capacity external lead wire with the clad nano dielectric layer.
Test result shows: the operating voltage of this ultracapacitor is not less than 10V, and energy density is not less than 500Wh/kg.
Embodiment 2:
A kind of high-energy-density ultracapacitor based on the nanometer dielectric materials layer, anodal and negative pole is foam copper-carbon nano-tube combination electrode, the nanometer dielectric layer is Ta 2O 5, thickness is 20nm, electrolyte is that mass percent concentration is 10% the KCl aqueous solution, its preparation methods steps is as follows:
1) multi-walled carbon nano-tubes is dispersed in the ethanol, the adding mass percent is 0.5% MgNO 3, fully mix.
2) with the foam copper coin as negative pole, adopt electrophoresis that multi-walled carbon nano-tubes is deposited on the foam copper coin;
3) with granularity be the Ta of 20-40nm 2O 5Be dispersed in the alcohol, the adding mass percent is 0.5%MgNO 3, mix;
4) take the copper electrode that deposits carbon nano-tube as substrate, adopt electrophoresis to deposit Ta at electrode 2O 5, at carbon nano tube surface clad nano dielectric layer;
5) can make the high-energy-density ultracapacitor after positive pole, negative pole, electrolyte and the assembling of electric capacity external lead wire with the clad nano dielectric layer.
Test result shows: the operating voltage of this ultracapacitor is not less than 10V, and energy density is not less than 500Wh/kg.
Embodiment 3:
A kind of high-energy-density ultracapacitor based on the nanometer dielectric materials layer, anodal and negative pole is foamed aluminium-carbon nano-tube combination electrode, the nanometer dielectric layer is Al 2O 3, thickness is 20nm, electrolyte is that mass percent concentration is 5% the KOH aqueous solution, its preparation methods steps is as follows:
1) multi-walled carbon nano-tubes is dispersed in the ethanol, the adding mass percent is 0.5% MgNO 3, fully mix.
2) with foamed aluminium board as negative pole, adopt electrophoresis that multi-walled carbon nano-tubes is deposited on the foamed aluminium board;
3) with granularity be the Al of 20-40nm 2O 3Be dispersed in the alcohol, the adding mass percent is 0.5%MgNO 3, mix;
4) take the aluminium electrode that deposits carbon nano-tube as substrate, adopt electrophoresis depositing Al on electrode 2O 3, at carbon nano tube surface clad nano dielectric layer;
5) can make the high-energy-density ultracapacitor after positive pole, negative pole, electrolyte and the assembling of electric capacity external lead wire with the clad nano dielectric layer.
Test result shows: the operating voltage of this ultracapacitor is not less than 10V, and energy density is not less than 500Wh/kg.
Embodiment 4:
A kind of high-energy-density ultracapacitor based on the nanometer dielectric materials layer, anodal and negative pole is the nickel carbon nano-tube combination electrode, the nanometer dielectric layer is Ta 2O 5, thickness is 20nm, electrolyte is that mass percent concentration is 10% the KOH aqueous solution, its preparation methods steps is as follows:
1) multi-walled carbon nano-tubes is dispersed in the ethanol, the adding mass percent is 0.5% MgNO 3, fully mix.
2) the metallic nickel sheet take thickness as 0.5mm adopts electrophoresis that multi-walled carbon nano-tubes is deposited on the nickel sheet as negative pole;
3) with granularity be the Ta of 20-40nm 2O 5Be dispersed in the alcohol, the adding mass percent is 0.5%MgNO 3, mix;
4) take the nickel electrode that deposits carbon nano-tube as substrate, adopt electrophoresis to deposit Ta at electrode 2O 5, at carbon nano tube surface clad nano dielectric layer;
5) can make the high-energy-density ultracapacitor after positive pole, negative pole, electrolyte and the assembling of electric capacity external lead wire with the clad nano dielectric layer.
Test result shows: the operating voltage of this ultracapacitor is not less than 10V, and energy density is not less than 500Wh/kg.
Embodiment 5:
A kind of high-energy-density ultracapacitor based on the nanometer dielectric materials layer, anodal and negative pole is aluminium-carbon nano-tube combination electrode, the nanometer dielectric layer is Al 2O 3, thickness is 20nm, electrolyte is that mass percent concentration is 10% the KCl aqueous solution, its preparation methods steps is as follows:
1) multi-walled carbon nano-tubes is dispersed in the ethanol, the adding mass percent is 0.5% MgNO 3, fully mix.
2) the metal aluminium flake take thickness as 0.5mm adopts electrophoresis that multi-walled carbon nano-tubes is deposited on the aluminium flake as negative pole;
3) with granularity be the Al of 20-40nm 2O 3Be dispersed in the alcohol, the adding mass percent is 0.5%MgNO 3, mix;
4) take the aluminium electrode that deposits carbon nano-tube as substrate, adopt electrophoresis depositing Al on electrode 2O 3, at carbon nano tube surface clad nano dielectric layer;
5) can make the high-energy-density ultracapacitor after positive pole, negative pole, electrolyte and the assembling of electric capacity external lead wire with the clad nano dielectric layer.
Test result shows: the operating voltage of this ultracapacitor is not less than 10V, and energy density is not less than 500Wh/kg.
Embodiment 6:
A kind of high-energy-density ultracapacitor based on the nanometer dielectric materials layer, anodal and negative pole is the copper carbon nano-tube combination electrode, the nanometer dielectric layer is Ta 2O 5, thickness is 20nm, electrolyte is that mass percent concentration is 5% the KOH aqueous solution, its preparation methods steps is as follows:
1) multi-walled carbon nano-tubes is dispersed in the ethanol, the adding mass percent is 0.5% MgNO 3, fully mix.
2) the metal copper sheet take thickness as 0.5mm adopts electrophoresis that multi-walled carbon nano-tubes is deposited on the copper sheet as negative pole;
3) with granularity be the Ta of 20-40nm 2O 5Be dispersed in the alcohol, the adding mass percent is 0.5%MgNO 3, mix;
4) take the copper electrode that deposits carbon nano-tube as substrate, adopt electrophoresis to deposit Ta at electrode 2O 5, at carbon nano tube surface clad nano dielectric layer;
5) can make the high-energy-density ultracapacitor after positive pole, negative pole, electrolyte and the assembling of electric capacity external lead wire with the clad nano dielectric layer.
Test result shows: the operating voltage of this ultracapacitor can reach 30V, and energy density is not less than 400Wh/kg.
Embodiment 7:
A kind of high-energy-density ultracapacitor based on the nanometer dielectric materials layer, anodal and negative pole is foamed aluminium anodized electrode, the nanometer dielectric layer is Al 2O 3, Al 2O thickness is 15nm, and electrolyte is that mass percent concentration is 10% the KCl aqueous solution, and its preparation methods steps is as follows:
1) with foamed aluminium in 10% boric acid aqueous solution, under the 300V direct voltage, carry out anodized with aluminium as anode, obtaining thickness is the nanometer Al of 15nm 2O 3Dielectric layer.
2) with the foamed aluminium after the anodic oxidation as electrode of super capacitor, adopting the 10%KCl aqueous solution is electrolyte, makes ultracapacitor.
Test result shows: the operating voltage of this ultracapacitor can reach 30V, and energy density is not less than 400Wh/kg.

Claims (2)

1. high-energy-density ultracapacitor based on the nanometer dielectric materials layer, it is characterized in that: by positive pole, negative pole, the nanometer dielectric layer, electrolyte and electric capacity external lead wire consist of, positive pole and negative pole as conductive electrode have high-specific surface area, the nanometer dielectric layer is coated on the surface of anodal and negative pole, the positive pole and the negative pole that are coated with the nanometer dielectric layer are immersed in the electrolyte, and described positive pole and negative pole are nickel-carbon nano-tube combination electrode, aluminium-carbon nano-tube combination electrode, copper-carbon nano-tube combination electrode or or nickel foam-carbon nano-tube combination electrode, foamed aluminium-carbon nano-tube combination electrode, foam copper-carbon nano-tube combination electrode or foamed aluminium anodized electrode; The nanometer dielectric layer is Al 2O 3Or Ta 2O 5, thickness is 10-500nm; Electrolyte is that mass percent concentration is the KCl aqueous solution or the KOH aqueous solution of 0.1-50%.
2. described high-energy-density ultracapacitor based on the nanometer dielectric materials layer according to claim 1 is characterized in that the method that described nanometer dielectric layer is coated on the surface of anodal and negative pole is electrophoresis, physical vaporous deposition or chemical vapour deposition technique.
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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105448378A (en) * 2014-09-04 2016-03-30 詹承镇 Foam body
CN110010365A (en) * 2019-03-20 2019-07-12 华东师范大学 A kind of capacitor based on copolyesters preparation with flexibility with compression property
CN110957143A (en) * 2019-12-03 2020-04-03 西安交通大学 Electrode for supercapacitor and preparation method and application thereof
CN111210998A (en) * 2020-02-25 2020-05-29 济南大学 3D multifunctional flexible material and application thereof

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CN101625930A (en) * 2009-06-19 2010-01-13 东南大学 Ordered nano-tube array structure electrode material, preparation method and stored energy application
US20110272288A1 (en) * 2010-05-05 2011-11-10 Lin Chuen-Chang Method for fabricating carbon nanotube aluminum foil electrode
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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105448378A (en) * 2014-09-04 2016-03-30 詹承镇 Foam body
CN110010365A (en) * 2019-03-20 2019-07-12 华东师范大学 A kind of capacitor based on copolyesters preparation with flexibility with compression property
CN110957143A (en) * 2019-12-03 2020-04-03 西安交通大学 Electrode for supercapacitor and preparation method and application thereof
CN111210998A (en) * 2020-02-25 2020-05-29 济南大学 3D multifunctional flexible material and application thereof
CN111210998B (en) * 2020-02-25 2022-02-11 济南大学 3D multifunctional flexible material and application thereof

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Application publication date: 20130424