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WO2001027947A1 - Condensateur electrochimique - Google Patents

Condensateur electrochimique Download PDF

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Publication number
WO2001027947A1
WO2001027947A1 PCT/DE2000/003446 DE0003446W WO0127947A1 WO 2001027947 A1 WO2001027947 A1 WO 2001027947A1 DE 0003446 W DE0003446 W DE 0003446W WO 0127947 A1 WO0127947 A1 WO 0127947A1
Authority
WO
WIPO (PCT)
Prior art keywords
electrochemical capacitor
capacitor according
electrodes
nanostructured elements
nanostructured
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/DE2000/003446
Other languages
German (de)
English (en)
Inventor
Werner Scherber
Mathias BÖHMISCH
Cornelius Haas
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Dornier GmbH
Original Assignee
Dornier GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Dornier GmbH filed Critical Dornier GmbH
Publication of WO2001027947A1 publication Critical patent/WO2001027947A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/26—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/26—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features
    • H01G11/28—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features arranged or disposed on a current collector; Layers or phases between electrodes and current collectors, e.g. adhesives
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • 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

Definitions

  • the invention relates to an electrochemical capacitor according to the preamble of patent claim 1.
  • the material concepts based on active carbon have become established, which, in combination with organic electrolytes, are currently considered to have the greatest market potential in terms of performance data and costs.
  • there are a large number of concepts for producing these activated carbon supercapacitors or their electrodes for example EP 0 712 143 A2, DE 197 24 712 A1.
  • a maximum of 50 to 100 farads capacity per gram of the active electrode material can be achieved here.
  • approx. 25 percent by mass is currently accounted for by the actual electrodes and approx.
  • the ratio of useful energy and storage weight is often still too small to be used as a peak load storage for these elements to use real applications economically sensible.
  • the performance data can therefore be optimized both via the stack design (several individual cells connected in series stacked one above the other) and via the actual capacitor electrodes (surface structures and materials).
  • the typically rather sponge-like geometry of activated carbon materials also has a disadvantageous effect on the frequency behavior of the capacitance. Because for the electrolyte it is synonymous with relatively long and narrow paths and therefore inevitably linked to a relatively high ohmic internal resistance. Due to the high capacities connected in series, this leads to a reduction in the cutoff frequency of the overall component, i.e. Even at moderate frequencies (typically around 1 Hz), only a fraction of the electrode capacity available with DC voltage can be used. This further limits the practical use of supercapacitors with such electrodes.
  • the relatively high ohmic resistance also causes dissipative losses, which are possible due to the associated thermal load on the component restrict even further or, with appropriate design measures (cooling plates, etc.), drastically reduce the usable mass and volume-related energy storage density.
  • the present invention is therefore based on the object of creating a supercapacitor with improved performance data compared to the known capacitors, the electrode geometry and electrode material of which simultaneously allow a significantly improved stack design.
  • the electrodes are formed from an electrically conductive or semiconducting, nanostructured film, in which nanostructured discrete, needle-shaped elements are anchored in an electrically conductive manner on a surface.
  • Nanostructured element in the sense of the present invention refers to a material structure with dimensions of at least one structural dimension in the nanometer range ( ⁇ 1 ⁇ m).
  • the electrodes according to the invention produce a large effective surface for forming the Helmholtz storage layer.
  • Their size on a flat metallic surface is typically about 40 ⁇ F / cm 2 in the aqueous electrolyte.
  • the areal density of the nanostructured elements is preferably in the range of 1-500 per ⁇ m 2 , the diameter of which is preferably in the range of 15-500 nm, B. the necessary material stability is guaranteed for metallic structures.
  • the aspect ratio (ratio between height and average diameter) of the nanostructured needle-shaped elements is greater than 20.
  • the discrete - preferably regular - arrangement of the nanostructures according to the invention elements moreover, a faster and complete formation of the Helmholtz layers on the existing surface and thus a significant improvement in the performance characteristics.
  • the electrode structure according to the invention in the form of laterally arranged nanostructured elements reduces the thermal losses during charging and discharging processes, and thus the range of use of the supercapacitors is also expanded for higher-frequency applications (> 1 Hz).
  • the effective surface area of a single electrode can be determined directly. It has been shown that in the manufacture of the electrode by electrochemical growth by means of a suitable choice of the concentration, elements with additional inner sponge-like porosity and hollow cylindrical elements (tubes) can also be formed. A further increase in the effective surface area by at least a factor of two and thus an increase in the Helmholtz capacity can thereby be achieved.
  • Some metal oxides e.g. Ru0 2
  • conductive polymers allow energy storage in suitable electrolytes through surface redox reactions.
  • the recharging of such redox systems on the electrode surface leads to the formation of the Helmholtz double layer and an additional electrode capacity (pseudo capacity).
  • This property can be achieved in the electrodes of the present invention either by a thin ( ⁇ 10 nm) coating with a corresponding redox system (for example Ru0 2 ) or by direct formation of the nanostructured elements from precisely this material.
  • the nanostructured electrode film can be produced from any semiconducting or conductive materials such as metals, noble metals, galvanometals (electrodepositable metals), in particular nickel or conductive polymers, using suitable manufacturing processes.
  • the production of the carrier film and then the growth of the nanostructured elements can be carried out in one work step when using electrochemical deposition.
  • the thickness of the carrier film is advantageously set between 1 and 20 ⁇ m. This guarantees the electrical conductivity, contactability and also the mechanical stability for the construction of a supercapacitor single cell or stack.
  • 1 a supercapacitor electrode according to the invention
  • 2 SEM image of a supercapacitor electrode according to the invention
  • 3 a supercapacitor according to the invention, consisting of a single cell
  • 4 a supercapacitor according to the invention, consisting of a stack of several individual cells
  • 5 Frequency behavior of the specific Helmholtz capacitances of a supercapacitor electrode according to the invention according to FIG. 2 in 1 molar KOH.
  • FIG. 1 shows a supercapacitor electrode according to the invention made of a self-supporting film 2 and nanostructured, discrete elements 1 anchored thereon, which are needle-shaped.
  • Discrete in the sense of the present invention means that the elements are separate from one another, each with its own structure, that is to say not elements that are connected to one another, as is the case, for example, with a sponge-like structure.
  • FIG. 2 shows the SEM image of a supercapacitor electrode according to the invention made of a self-supporting nickel foil 4 and nanostructured elements 3 made of nickel anchored thereon.
  • the nanostructured needle-shaped elements 3 are oriented essentially perpendicular to the surface of the film 4 in this embodiment and are evenly distributed over the surface of the film 4.
  • FIG. 3 shows a supercapacitor according to the invention.
  • it consists of a single cell which comprises the electrodes 8, 9, a spacer 5 and a liquid electrolyte 6 which wets the electrodes and the spacer.
  • the electrodes are designed in the form of nanostructured thin-film electrodes.
  • the spacer 5 prevents mechanical contact between the electrodes 8, 9 and is permeable to the electrolyte. For this purpose it is e.g. porous.
  • Reference number 7 designates the external contacting of the supercapacitor. If a solid electrolyte is used instead of a liquid electrolyte, the spacer 5 is omitted.
  • two electrodes 8, 9 according to the invention are pressed onto the porous spacer 5, the nanostructured sides of the two electrodes 8, 9 facing each other.
  • the electrodes are contacted on their unstructured side, the entire system is filled with the electrolyte 6 and enclosed in a suitable housing and sealed.
  • the individual cells are stacked on top of one another and pressed. This creates a series connection of individual capacitor elements via the conductive electrode films without additional contacting steps.
  • the contacting of the stack, the filling with electrolyte and the encapsulation in a housing is carried out analogously to the single cell.
  • 5 shows a diagram of the frequency behavior of the specific Helmholtz capacitances (dashed line: per mass; solid line: per volume) of a supercapacitor electrode according to the invention. KOH was used as the electrolyte.
  • the capacitance decreases only slowly when the frequency is applied compared to the DC voltage value (0 Hz) and also remains at higher frequencies, e.g. 100 Hz largely preserved.
  • the electrodes according to the invention advantageously have a DC voltage value of the specific Helmholtz capacitance of more than 10F / g or more than 10F / cm 3 , particularly advantageously more than 50F / g or more than 50F / cm 3 .
  • the electrodes according to the invention advantageously have a value of the specific Helmholtz capacitance of more than 1 F / g or more than 1 F / cm 3 , particularly advantageously more than 5F / g or more than 5F / cm 3 on.
  • the anodic oxidation of an aluminum substrate creates a nanoporous oxide film with parallel, continuously cylindrical pores aligned perpendicular to the substrate surface.
  • the pore diameter can be set in the range of 15-500 nm, the surface density of the pores from approx. 1 to 500 per ⁇ m 2 , and the pore length up to 100 ⁇ m.
  • the oxide film is detached from the aluminum substrate, so that a ceramic nanoporous filter membrane is created. This membrane is vapor-coated on one side with a metallic film as a contact electrode. The film thickness is selected so that the oxide pores are closed.
  • the vapor-deposited is used to produce nanostructured nickel elements on a nickel film Contacted membrane and placed in a galvanic nickel bath.
  • the oxide pores are filled with the desired nanostructured elements from the vapor-deposited base electrode, and on the other hand the base electrode is thickened to a metallic film in the micrometer range.
  • the oxide ceramic can then be selectively pickled using wet chemistry, so that the desired electrode film with conductively bonded nanostructured nickel elements is produced.

Landscapes

  • Engineering & Computer Science (AREA)
  • Power Engineering (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Electric Double-Layer Capacitors Or The Like (AREA)

Abstract

L'invention concerne un condensateur électrochimique constitué d'une cellule individuelle ou d'une pile de cellules individuelles, chaque cellule individuelle comportant une électrode (8), une contre-électrode (9) ainsi qu'un électrolyte (6) mouillant les électrodes. Selon l'invention, les électrodes (8, 9) sont constituées d'un film électroconducteur ou semi-conducteur, nanostructuré, dans lequel des éléments (1, 3) en forme d'aiguilles, nanostructurés, discrets, sont ancrés, de façon électroconductrice, sur une surface.
PCT/DE2000/003446 1999-10-09 2000-09-30 Condensateur electrochimique Ceased WO2001027947A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19948742.1 1999-10-09
DE1999148742 DE19948742C1 (de) 1999-10-09 1999-10-09 Elektrochemischer Kondensator, insb. Doppelschichtkondensator oder Superkondensator

Publications (1)

Publication Number Publication Date
WO2001027947A1 true WO2001027947A1 (fr) 2001-04-19

Family

ID=7925111

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/DE2000/003446 Ceased WO2001027947A1 (fr) 1999-10-09 2000-09-30 Condensateur electrochimique

Country Status (2)

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DE (1) DE19948742C1 (fr)
WO (1) WO2001027947A1 (fr)

Families Citing this family (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU2001250957A1 (en) 2000-03-24 2001-10-08 Cymbet Corporation Integrated capacitor-like battery and associated method
US7294209B2 (en) 2003-01-02 2007-11-13 Cymbet Corporation Apparatus and method for depositing material onto a substrate using a roll-to-roll mask
US7603144B2 (en) 2003-01-02 2009-10-13 Cymbet Corporation Active wireless tagging system on peel and stick substrate
US6906436B2 (en) 2003-01-02 2005-06-14 Cymbet Corporation Solid state activity-activated battery device and method
US7211351B2 (en) 2003-10-16 2007-05-01 Cymbet Corporation Lithium/air batteries with LiPON as separator and protective barrier and method
WO2007011899A2 (fr) 2005-07-15 2007-01-25 Cymbet Corporation Batteries a films minces presentant des couches electrolytiques polymeriques ou lipon, et procede
US7776478B2 (en) 2005-07-15 2010-08-17 Cymbet Corporation Thin-film batteries with polymer and LiPON electrolyte layers and method
US10658705B2 (en) 2018-03-07 2020-05-19 Space Charge, LLC Thin-film solid-state energy storage devices
US11996517B2 (en) 2011-06-29 2024-05-28 Space Charge, LLC Electrochemical energy storage devices
US9853325B2 (en) 2011-06-29 2017-12-26 Space Charge, LLC Rugged, gel-free, lithium-free, high energy density solid-state electrochemical energy storage devices
US10601074B2 (en) 2011-06-29 2020-03-24 Space Charge, LLC Rugged, gel-free, lithium-free, high energy density solid-state electrochemical energy storage devices
US11527774B2 (en) 2011-06-29 2022-12-13 Space Charge, LLC Electrochemical energy storage devices
AT514443B1 (de) 2013-06-17 2015-03-15 Univ Wien Tech Halbleiter-Bauteil

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5062025A (en) * 1990-05-25 1991-10-29 Iowa State University Research Foundation Electrolytic capacitor and large surface area electrode element therefor
EP0712143A2 (fr) * 1994-11-02 1996-05-15 Japan Gore-Tex, Inc. Condensateur électrique à double couche et méthode de fabrication d'une électrode pour celui-ci
WO1996041745A1 (fr) * 1995-06-09 1996-12-27 Zvi Horovitz Fibres de carbone paralleles, a masse volumique apparente elevee
US5680292A (en) * 1994-12-12 1997-10-21 T/J Technologies, Inc. High surface area nitride, carbide and boride electrodes and methods of fabrication thereof

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5862035A (en) * 1994-10-07 1999-01-19 Maxwell Energy Products, Inc. Multi-electrode double layer capacitor having single electrolyte seal and aluminum-impregnated carbon cloth electrodes
DE19724712A1 (de) * 1997-06-11 1998-12-17 Siemens Ag Doppelschichtkondensator

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5062025A (en) * 1990-05-25 1991-10-29 Iowa State University Research Foundation Electrolytic capacitor and large surface area electrode element therefor
EP0712143A2 (fr) * 1994-11-02 1996-05-15 Japan Gore-Tex, Inc. Condensateur électrique à double couche et méthode de fabrication d'une électrode pour celui-ci
US5680292A (en) * 1994-12-12 1997-10-21 T/J Technologies, Inc. High surface area nitride, carbide and boride electrodes and methods of fabrication thereof
WO1996041745A1 (fr) * 1995-06-09 1996-12-27 Zvi Horovitz Fibres de carbone paralleles, a masse volumique apparente elevee

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
SHUI X ET AL: "Electrochemical behavior of hairy carbons", CARBON,US,ELSEVIER SCIENCE PUBLISHING, NEW YORK, NY, vol. 35, no. 10-11, 1997, pages 1439 - 1455, XP004098165, ISSN: 0008-6223 *

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