CN103560010A - Electrochemical capacitor - Google Patents

Electrochemical capacitor Download PDF

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Publication number
CN103560010A
CN103560010A CN201310495372.1A CN201310495372A CN103560010A CN 103560010 A CN103560010 A CN 103560010A CN 201310495372 A CN201310495372 A CN 201310495372A CN 103560010 A CN103560010 A CN 103560010A
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China
Prior art keywords
electrochemical capacitor
pole piece
carbon materials
capacitor according
porous carbon
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Pending
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CN201310495372.1A
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Chinese (zh)
Inventor
关成善
宗继月
王勇
张敬捧
辛军委
李蜜蜜
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Shandong Goldencell Electronics Technology Co Ltd
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Shandong Goldencell Electronics Technology Co Ltd
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Priority to CN201310495372.1A priority Critical patent/CN103560010A/en
Publication of CN103560010A publication Critical patent/CN103560010A/en
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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

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  • Electric Double-Layer Capacitors Or The Like (AREA)

Abstract

The invention discloses an electrochemical capacitor which comprises an outer shell, a positive pole piece, a negative pole piece, a membrane and an organic electrolyte. The positive pole piece and the negative pole piece are packaged inside a shell body. The membrane is arranged between the positive pole piece and the negative pole piece. The organic electrolyte is filled into a positive pole, a negative pole and a gap in the membrane. The positive pole piece is composed of LiNi0.5Mn1.5O4, porous carbon materials, conductive black, a binding agent and an aluminum foil. The negative pole piece is made of Li4Ti5012, porous carbon materials, conductive black, a binding agent and a copper foil. The porous carbon materials are at least one of porous activated carbon or graphene or carbon nano tubes. The organic electrolyte is composed of electrolyte salts and mixed liquor of an organic solvent, wherein the electrolyte salts contain a quaternary ammonium salt and Lithium-ions. The electrochemical capacitor is manufactured by utilizing the advantageous structures of a lithium ion battery and a super capacitor, and has the advantages of being long in cycling life and good in safety.

Description

Electrochemical capacitor
Technical field
The invention belongs to electrochemical capacitor technical field, be specifically related to a kind of model electrochemical capacitor.
Background technology
It is a kind of Novel energy storage apparatus between traditional capacitor and secondary cell occurring in recent years that electrochemical capacitor is again ultracapacitor, it is when retaining the feature that traditional capacitor power density is large, have and can reach the even static capacity of up to ten thousand farads of farad level, so it has the advantages that energy density is higher.Electrochemical capacitor generally can be divided into three kinds: a kind of is the double electric layer electrochemical capacitors (EDLC) that utilizes the electric double layer principle stored charge of electrode and electrolyte interface, a kind of is to utilize electrode material that the fake capacitance device that surperficial Quick Oxidation reduction reaction principle stores electric charge occurs, also having a kind of is the hybrid electrochemical capacitor in device inside combination by double electric layer electrochemical capacitors and lithium ion battery, and the present invention just belongs to this class electrochemical capacitor.
Because hybrid electrochemical capacitor has higher energy density, also there is higher power density simultaneously, therefore become the focus that electrochemical capacitor industry is paid close attention to.The lithium-ion capacitor of the application for a patent for invention of publication No. CN102543460A, its positive electrode is LiFePO4, because the electrochemical potentials of LiFePO4 is lower, so the electrochemical window of lithium ion super capacitor is lower, energy density is restricted; Its negative pole adopts the material with carbon element doped with lithium ion to be directed at cycle life shortening.
Summary of the invention
The object of this invention is to provide a kind of low cost, high electrochemical window, more high-energy-density, electrochemical capacitor that cycle life is longer.
For solving the problems of the technologies described above, the present invention adopts following technical scheme:
, comprise shell, be packaged in the positive plate in housing, negative plate, the barrier film between positive/negative plate and be filled in both positive and negative polarity and barrier film space in organic electrolyte, it is characterized in that,
Described positive plate is by LiNi 0.5mn 1.5o 4, porous carbon materials, conductive black, binding agent and aluminium foil form;
Described negative plate adopts Li 4ti 50 12, porous carbon materials, conductive black, binding agent and Copper Foil;
Wherein said organic electrolyte is that the mixed liquor of quaternary ammonium salt and the electrolytic salt that contains lithium ion and organic solvent forms,
Described porous carbon materials is at least one in porous activated carbon, Graphene or carbon nano-tube.
Electrochemical capacitor according to described, is characterized in that, in positive plate, the weight content of each material is LiNi 0.5mn 1.5o 440% ~ 95%, porous carbon materials 0.5% ~ 55%, conductive carbon black 1% ~ 15%, binding agent 3% ~ 10%; Aluminium foil 10 μ m ~ 30 μ m.
Electrochemical capacitor according to described, is characterized in that, described aluminium foil can or be light face aluminium foil for corrosive aluminum foil.
Electrochemical capacitor according to described, is characterized in that, in described negative plate, the weight content of each material is Li 4ti 50 1250% ~ 95%, porous carbon materials is 0.5% ~ 45%, conductive carbon black 1% ~ 15%, binding agent 3% ~ 10%; Copper Foil 8 μ m ~ 20 μ m.
Electrochemical capacitor according to described, is characterized in that, the electrolytic salt in described organic electrolyte is by doped quaternary ammonium salt Et 4nBF 4, MeEt 3nBF 4in a kind of and electrolytic salt LiPF6, the LiClO4, LiBOB, the LiBF that contain lithium ion 4in a kind of mixing.
Electrochemical capacitor according to described, is characterized in that, in described electrolytic salt, quaternary ammonium salt is 0.2 ~ 9:1 with the weight ratio containing lithium electrolyte salt.
Electrochemical capacitor according to described, is characterized in that, in described organic electrolyte, electrolytical concentration is 0.5mol/L ~ 5 mol/L.
Electrochemical capacitor of the present invention compared with prior art, because positive active material adopts LiNi 0.5mn 1.5o 4so product has higher electrochemical window, corresponding energy density has also obtained large increase; Especially because negative pole adopts Li 4ti 50 12as active material, make product there is better cycle life and security performance.
specific implementation method
, comprise shell, be packaged in the positive plate in housing, negative plate, the barrier film between positive/negative plate and be filled in both positive and negative polarity and barrier film space in organic electrolyte, it is characterized in that,
Described positive plate is by LiNi 0.5mn 1.5o 4, porous carbon materials, conductive black, binding agent and aluminium foil form;
Described negative plate adopts Li 4ti 50 12, porous carbon materials, conductive black, binding agent and Copper Foil;
Wherein said organic electrolyte is that the mixed liquor of quaternary ammonium salt and the electrolytic salt that contains lithium ion and organic solvent forms,
Described porous carbon materials is at least one in porous activated carbon, Graphene or carbon nano-tube.
Electrochemical capacitor according to described, is characterized in that, in positive plate, the weight content of each material is LiNi 0.5mn 1.5o 440% ~ 95%, porous carbon materials 0.5% ~ 55%, conductive carbon black 1% ~ 15%, binding agent 3% ~ 10%; Aluminium foil 10 μ m ~ 30 μ m.
Electrochemical capacitor according to described, is characterized in that, described aluminium foil can or be light face aluminium foil for corrosive aluminum foil.
Electrochemical capacitor according to described, is characterized in that, in described negative plate, the weight content of each material is Li 4ti 50 1250% ~ 95%, porous carbon materials is 0.5% ~ 45%, conductive carbon black 1% ~ 15%, binding agent 3% ~ 10%; Copper Foil 8 μ m ~ 20 μ m.
Electrochemical capacitor according to described, is characterized in that, the electrolytic salt in described organic electrolyte is by doped quaternary ammonium salt Et 4nBF 4, MeEt 3nBF 4in a kind of and electrolytic salt LiPF6, the LiClO4, LiBOB, the LiBF that contain lithium ion 4in a kind of mixing.
Electrochemical capacitor according to described, is characterized in that, in described electrolytic salt, quaternary ammonium salt is 0.2 ~ 9:1 with the weight ratio containing lithium electrolyte salt.
Electrochemical capacitor according to described, is characterized in that, in described organic electrolyte, electrolytical concentration is 0.5mol/L ~ 5 mol/L.
Electrochemical capacitor of the present invention can be made into column type, square and coin shape.Can adopt stainless steel case, plastic housing, aluminum hull and aluminum plastic film encapsulation.
With regard to specific embodiment of the invention, describe:
Embodiment 1,
The Kynoar that takes 4 mass parts incorporates in the 1-METHYLPYRROLIDONE of 150 mass parts, adds the conductive black Super-P Li of 5 mass parts, and 26 mass parts specific areas are 1800m 2the LiNi of the active carbon of/g and 60 mass parts 0.5mn 1.5o 4, in planetary de-airing mixer, stir more than 8 hours, with coating machine, the slurry preparing is coated on light face aluminium foil, roll extrusion after drying, cut and make anode pole piece.
The Kynoar that takes 5 mass parts dissolves in the 1-METHYLPYRROLIDONE of 200 mass parts, adds the Li of 80 mass parts 4ti 50 12, 10 mass parts specific areas are 1800m 2the conductive black Super-P Li of the active carbon of/g and 5 mass parts stirs more than 10 hours in planetary de-airing mixer, with coating machine, the slurry preparing is coated on Copper Foil, roll extrusion after drying, cuts and makes cathode pole piece.
LiNi in the anode pole piece of preparation 0.5mn 1.5o 4quality is Li in cathode pole piece 4ti 50 124/5 of quality, anode pole piece and cathode pole piece be through tab welding, and reel after adding barrier film between both positive and negative polarity pole piece, packs housing into, injects the Et that contains of 2mol/L 4nBF 4and LiPF 6two kinds of electrolyte solutions, make hybrid electrochemical capacitor after sealing.After seasoned with 1C carry out capacity after charge and discharge cycles 2000 times not yet initial capacity 92%, the energy density of 1C electric discharge reaches 115Wh/Kg.
Embodiment 2,
The Kynoar that takes 5 mass parts incorporates in the 1-METHYLPYRROLIDONE of 250 mass parts, adds the Ketjen black ECP-600JD of 2 mass parts, and 13 mass parts specific areas are 1800m 2the LiNi of the active carbon of/g and 80 mass parts 0.5mn 1.5o 4, in planetary de-airing mixer, stir more than 6 hours, with coating machine, the slurry preparing is coated on light face aluminium foil, roll extrusion after drying, cut and make anode pole piece.
The Kynoar that takes 4 mass parts dissolves in the 1-METHYLPYRROLIDONE of 200 mass parts, adds the Li of 80 mass parts 4ti 50 12, 14 mass parts specific areas are 1800m 2the Ketjen black ECP-600JD of the active carbon of/g and 2 mass parts stirs more than 10 hours in planetary de-airing mixer, with coating machine, the slurry preparing is coated on Copper Foil, roll extrusion after drying, cuts and makes cathode pole piece.
LiNi in the anode pole piece of preparation 0.5mn 1.5o 4quality is Li in cathode pole piece 4ti 50 127/8 of quality, anode pole piece and cathode pole piece be through tab welding, and reel after adding barrier film between both positive and negative polarity pole piece, packs housing into, injects the MeEt that contains of 2.5mol/L 3nBF 4and LiPF 6two kinds of electrolyte solutions, make hybrid electrochemical capacitor after sealing.After seasoned with 1C carry out capacity after charge and discharge cycles 2000 times not yet initial capacity 91.5%, the energy density of 1C electric discharge reaches 145Wh/Kg.
Embodiment 3,
The Kynoar that takes 10 mass parts incorporates in the 1-METHYLPYRROLIDONE of 450 mass parts, adds the Ketjen black ECP-600JD of 4 mass parts, and 26 mass parts specific areas are 1600m 2the LiNi of the active carbon of/g and 60 mass parts 0.5mn 1.5o 4, in planetary de-airing mixer, stir more than 10 hours, with coating machine, the slurry preparing is coated on light face aluminium foil, roll extrusion after drying, cut and make anode pole piece.
The Kynoar that takes 6 mass parts dissolves in the 1-METHYLPYRROLIDONE of 300 mass parts, adds the Li of 70 mass parts 4ti 50 12, 18 mass parts specific areas are 1800m 2the Ketjen black ECP-600JD of the active carbon of/g and 6 mass parts stirs more than 7 hours in planetary de-airing mixer, with coating machine, the slurry preparing is coated on Copper Foil, roll extrusion after drying, cuts and makes cathode pole piece.
LiNi in the anode pole piece of preparation 0.5mn 1.5o 4li in quality and cathode pole piece 4ti 50 12mass ratio is 1:1, and anode pole piece and cathode pole piece be through tab welding, and reels after adding barrier film between both positive and negative polarity pole piece, packs housing into, injects the MeEt that contains of 1.5mol/L 3nBF 4and LiPF 6two kinds of electrolyte solutions, make hybrid electrochemical capacitor after sealing.After seasoned with 1C carry out capacity after charge and discharge cycles 2000 times not yet initial capacity 93.1%, the energy density of 1C electric discharge reaches 125Wh/Kg.
Embodiment 4,
The Kynoar that takes 7 mass parts incorporates in the 1-METHYLPYRROLIDONE of 400 mass parts, adds the carbon nano-tube of 2 mass parts, and 31 mass parts specific areas are 2100m 2the LiNi of the active carbon of/g and 60 mass parts 0.5mn 1.5o 4, in planetary de-airing mixer, stir more than 10 hours, with coating machine, the slurry preparing is coated on light face aluminium foil, roll extrusion after drying, cut and make anode pole piece.
The Kynoar that takes 4 mass parts dissolves in the 1-METHYLPYRROLIDONE of 300 mass parts, adds the Li of 70 mass parts 4ti 50 12, 23 mass parts specific areas are 1800m 2the carbon nano-tube of the active carbon of/g and 3 mass parts stirs more than 7 hours in planetary de-airing mixer, with coating machine, the slurry preparing is coated on Copper Foil, roll extrusion after drying, cuts and makes cathode pole piece.
LiNi in the anode pole piece of preparation 0.5mn 1.5o 4li in quality and cathode pole piece 4ti 50 12mass ratio is 1:1, and anode pole piece and cathode pole piece be through tab welding, and reels after adding barrier film between both positive and negative polarity pole piece, packs housing into, injects the MeEt that contains of 1.8mol/L 3nBF 4and LiPF 6two kinds of electrolyte solutions, make hybrid electrochemical capacitor after sealing.After seasoned with 1C carry out capacity after charge and discharge cycles 2000 times not yet initial capacity 92.7%, the energy density of 1C electric discharge reaches 131Wh/Kg.
Embodiment recited above is described the preferred embodiment of the present invention; not design of the present invention and protection range are limited; do not departing under the prerequisite of design concept of the present invention; various modification and improvement that in this area, common engineers and technicians make technical scheme of the present invention, all should fall into protection scope of the present invention.

Claims (7)

1. an electrochemical capacitor, comprises shell, is packaged in the positive plate in housing, negative plate, the barrier film between positive/negative plate and be filled in both positive and negative polarity and barrier film space in organic electrolyte, it is characterized in that,
Described positive plate is by LiNi 0.5mn 1.5o 4, porous carbon materials, conductive black, binding agent and aluminium foil form;
Described negative plate adopts Li 4ti 50 12, porous carbon materials, conductive black, binding agent and Copper Foil;
Wherein said organic electrolyte is that the mixed liquor of quaternary ammonium salt and the electrolytic salt that contains lithium ion and organic solvent forms,
Described porous carbon materials is at least one in porous activated carbon, Graphene or carbon nano-tube.
2. electrochemical capacitor according to claim 1, is characterized in that, in positive plate, the weight content of each material is LiNi 0.5mn 1.5o 440% ~ 95%, porous carbon materials 0.5% ~ 55%, conductive carbon black 1% ~ 15%, binding agent 3% ~ 10%; Aluminium foil 10 μ m ~ 30 μ m.
3. electrochemical capacitor according to claim 2, is characterized in that, described aluminium foil can or be light face aluminium foil for corrosive aluminum foil.
4. electrochemical capacitor according to claim 1, is characterized in that, in described negative plate, the weight content of each material is Li 4ti 50 1250% ~ 95%, porous carbon materials is 0.5% ~ 45%, conductive carbon black 1% ~ 15%, binding agent 3% ~ 10%; Copper Foil 8 μ m ~ 20 μ m.
5. electrochemical capacitor according to claim 1, is characterized in that, the electrolytic salt in described organic electrolyte is by doped quaternary ammonium salt Et 4nBF 4, MeEt 3nBF 4in a kind of and electrolytic salt LiPF6, the LiClO4, LiBOB, the LiBF that contain lithium ion 4in a kind of mixing.
6. electrochemical capacitor according to claim 5, is characterized in that, in described electrolytic salt, quaternary ammonium salt is 0.2 ~ 9:1 with the weight ratio containing lithium electrolyte salt.
7. electrochemical capacitor according to claim 1, is characterized in that, in described organic electrolyte, electrolytical concentration is 0.5mol/L ~ 5 mol/L.
CN201310495372.1A 2013-10-22 2013-10-22 Electrochemical capacitor Pending CN103560010A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104795249A (en) * 2015-01-06 2015-07-22 宁波南车新能源科技有限公司 Novel battery capacitor based on composite positive and negative electrode materials
CN104952629A (en) * 2015-06-08 2015-09-30 深圳博磊达新能源科技有限公司 Aluminum capacitor battery and preparation method thereof
CN105405678A (en) * 2015-12-21 2016-03-16 山东精工电子科技有限公司 Preparation method of graphene-containing supercapacitor slurry

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101847516A (en) * 2010-02-26 2010-09-29 上海奥威科技开发有限公司 Capacitor battery of high-specific-energy organic system
CN102543460A (en) * 2010-10-21 2012-07-04 三星电机株式会社 Lithium ion capacitor
CN102789907A (en) * 2011-05-20 2012-11-21 三星电机株式会社 Hybrid capacitor
WO2013012391A1 (en) * 2011-07-21 2013-01-24 National University Of Singapore A redox flow battery system
CN103050676A (en) * 2013-01-11 2013-04-17 山东同大新能源有限公司 Lithium-ion power battery and quick charging electric automobile with same

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101847516A (en) * 2010-02-26 2010-09-29 上海奥威科技开发有限公司 Capacitor battery of high-specific-energy organic system
CN102543460A (en) * 2010-10-21 2012-07-04 三星电机株式会社 Lithium ion capacitor
CN102789907A (en) * 2011-05-20 2012-11-21 三星电机株式会社 Hybrid capacitor
WO2013012391A1 (en) * 2011-07-21 2013-01-24 National University Of Singapore A redox flow battery system
CN103050676A (en) * 2013-01-11 2013-04-17 山东同大新能源有限公司 Lithium-ion power battery and quick charging electric automobile with same

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104795249A (en) * 2015-01-06 2015-07-22 宁波南车新能源科技有限公司 Novel battery capacitor based on composite positive and negative electrode materials
CN104795249B (en) * 2015-01-06 2018-11-06 宁波中车新能源科技有限公司 A kind of novel battery capacitance based on compound positive and negative electrode material
CN104952629A (en) * 2015-06-08 2015-09-30 深圳博磊达新能源科技有限公司 Aluminum capacitor battery and preparation method thereof
CN105405678A (en) * 2015-12-21 2016-03-16 山东精工电子科技有限公司 Preparation method of graphene-containing supercapacitor slurry
CN105405678B (en) * 2015-12-21 2018-03-30 山东精工电子科技有限公司 A kind of method for preparing super capacitor slurry containing graphene

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Application publication date: 20140205