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WO2000002215A1 - Condensateur hybride - Google Patents

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Publication number
WO2000002215A1
WO2000002215A1 PCT/EP1999/002109 EP9902109W WO0002215A1 WO 2000002215 A1 WO2000002215 A1 WO 2000002215A1 EP 9902109 W EP9902109 W EP 9902109W WO 0002215 A1 WO0002215 A1 WO 0002215A1
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Prior art keywords
electrode
porous
carbon
metal
hybrid capacitor
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Ceased
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PCT/EP1999/002109
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English (en)
Inventor
Anders Olof Lundblad
Viktor Petrovitj Kuznetsov
Roustam Aminovich Mirzoev
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Alfar International Ltd
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Alfar International Ltd
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Priority to AU39263/99A priority Critical patent/AU3926399A/en
Publication of WO2000002215A1 publication Critical patent/WO2000002215A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • 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
    • H01G11/04—Hybrid capacitors
    • 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
    • H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
    • 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
    • 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
    • H01G11/32—Carbon-based
    • H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
    • 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

  • This invention relates to an electrochemical capacitor.
  • Double layer capacitors, pseudo capacitors and hybrid capacitors represent a new group of energy storage devices which are often called supercapacitors.
  • One important application for supercapacitors is pulse power.
  • Efforts in today's development of supercapacitor technology are, for electrode materials and electrolytes, mainly directed towards increasing energy and power of the devices.
  • Double layer capacitors are characterised by the charges being stored in the electrochemical double-layer of the solid/liquid interface of the electrodes.
  • a pseudo capacitor the charges are stored through a reversible electrochemical reduction/oxidation reaction (redox).
  • redox electrochemical reduction/oxidation reaction
  • activated carbon fiber cloths The most commonly used material for double layer capacitor electrodes are activated carbon fiber cloths. Such materials has high specific surface areas, thus, providing a large interface to the electrolyte.
  • the drawbacks of activated carbon fiber cloths are that they, due to their open woven structure, have a high porosity and thereby not so high specific capacitance per volume, and that the pore size distribution is generally rather wide and thereby not optimised for any electrolyte used.
  • WO 97/20333 discloses a double layer capacitor comprising at least two electrodes made from a nanoporous skeleton carbon.
  • the nanoporous carbon described in this patent has an even higher specific surface area per volume (1200 m 2 /cm 3 ) than carbon fiber cloth, with a very narrow pore size distribution around 8 A. This feature gives the capacitors, using this material, a specific capacitance per volume which is one of the
  • hybrid capacitor is dependent on the performance of both the negative double-layer electrode and the positive redox electrode. Typically, however, the charge/discharge performance is higher of the redox electrode. This is due to the fact that the density of the storable charges is usually higher in a redox electrode than in double-layer electrodes. This enables the redox electrode to be made thinner than the carbon double-layer electrode and thereby the ionic mass transport resistance of the redox electrode becomes smaller.
  • the design of state-of-the-art hybrid capacitor is such that the capacitance of the positive redox electrode is much higher than that of the negative double-layer electrode. The consequence is usually that both the energy and power capability of the device are limited by the negative carbon electrode. Thus, further development of hybrid capacitors are mainly dependent on finding better carbon materials.
  • the object of the present invention is to obtain a supercapacitor having a high energy storage density and a high extractable power.
  • a hybrid capacitor including a positive and a negative electrode, separated by a separator, the electrodes and the separator being saturated by an aqueous electrolyte, characterized by a negative electrode made of nanoporous carbon, essentially made from carbide precursor, the majority of nanopores having a size less than 5 nm, preferably 2 nm. It has surprisingly been found that the ionic mass transport resistance of a nanoporous carbon decreases with decreasing starting potential which makes the use of electrodes of nanoporous carbon as negative electrodes advantageous.
  • the carbon content in the negative electrode exceeds 95 %wt and the nanoporous carbon is a nanoporous skeleton carbon.
  • the amount of transport pores in the negative electrode can be varied between 10-55 % of the total volume of the electrode and the amount of nanopores can be varied between 15-55 %.
  • the nanopores in the negative electrode can be of the same or different types, each type having a narrow size distribution.
  • the positive electrode is a porous Ni electrode made by thermochemical treatment of a TiNi-alloy.
  • the positive electrode can also be a porous metal made by chemical and electrochemical treatment of a metal or metal-alloy, for example Ni, Co, Pb.
  • the positive electrode can be a porous Ni electrode made by chemical and electrochemical treatment of a NiAl-alloy.
  • FIG. 1 is a schematic sectional view of a hybrid capacitor
  • FIG. 2 is a principal drawing of an experimental microelectrode set-up
  • FIG. 3 gives the initial currents vs. starting potential obtained in the potential step microelectrode experiments
  • FIG. 4 shows a charge-discharge curve of an electrochemical cell having a porous nickel cathode and an anode made of nanoporous carbon made according to an ⁇ , . embodiment of the invention.
  • a hybrid capacitor is a supercapacitor where the positive electrode is using a red-ox reaction for charge storage (e.g. porous Ni electrodes), and the negative electrode stores charges in the electrochemical double layer.
  • a red-ox reaction for charge storage e.g. porous Ni electrodes
  • Nanoporosity - system of nanopores Nanoporosity - system of nanopores.
  • nanoporous carbons is meant, in this text, a carbon electrode material, essentially made from carbide precursor, containing nanopores in more than 15 % of the total pore volume, preferably more than 30 % (e.g. a carbon material essentially produced by chemically extracting the non-carbon material out of a carbide material, such as SiC, TiC, etc).
  • a nanoporous carbon may for instance be a nanoporous skeleton carbon.
  • nanoporous skeleton carbon is meant, in this text, a rigid skeleton network of carbon particles stemming from carbides, which are bound together only by carbon.
  • Internal resistance is in this patent defined in a wide sense, including not only the electrical resistance of the solid phases and the liquid phases, and the contact resistance but also the resistance related to ionic mass transport hindrance in the electrolyte phase (in the pore system of the electrodes etc).
  • Specific capacitance, power density and energy density are in this patent calculated or estimated on the basis of the active materials of the capacitor (e.g. specific capacitance
  • the present invention relates to a mass-transport phenomenon which has been observed on small nanoporous carbon particles (size: 35-290 ⁇ m) by means of a microelectrode technique.
  • the microelectrode measurements were made using a potential step technique and measuring the generated initial current maximum created by exposing the particles to a potential step.
  • the measurements have suprisingly shown that the initial current obtained (which also is the maximum current), when exposing a nanoporous carbon particle to a potential step of 100 mV, depends on the starting potential of the particle (i.e. its state-of-charge). If for example, the particle is charged to a starting potential of- 500 mV then the initial current is more than 5 times higher than when the starting potential is +500 mV.
  • the effect is believed to be related to the transport of ions, diffusion and migration, in the nanometer sized channels of the nanoporous carbons.
  • One possible explanation for this phenomena is that there is chemisorption of hydroxide ions reacting with active sites at more positive potentials. In this way hydroxyl groups are fixed on the nanopore wall and they are partially blocking the pores for further diffusion. At more negative potentials the pores will become less blocked.
  • nanoporous carbons work better as negative double-layer electrodes in aqueous basic solutions, more specifically potassium hydroxide solutions.
  • a negatively charged nanoporous carbon electrode has a higher effective diffusion coefficient and can thereby support/provide higher charge/discharge currents than a positively charged nanoporous carbon electrode,
  • the charge/discharge rate difference between the positive and the negative electrode is expected to increase with smaller nanopore size.
  • the effect should, thus, be greater when using a carbon essentially made from SiC or TiC which results in the majority of the nanopore volume pores being smaller than 2 nm, than when using a carbon essentially made from other carbides which results in the majority of the nanppore volume pores being greater than 2 nm. For nanopores having a size larger than 5 nm, the effect is no longer significant.
  • the essence of the present invention is a hybrid electrochemical capacitor, schematically shown in Figure 1, with a combined mechanism of charge storage, comprising at least two electrodes 2, 5 separated by an ion conducting separator 3. These elements are covered by a two-piece metal cap 7, the two pieces being sealed by sealing insulator 4. Current collector layers 6 are extended between the electrodes and the respective inner wall of the metal cap 7.
  • the negative electrode 5 performs the charge storage in the electrochemical double layer at the solid/liquid interface and is made of a nanoporous carbon material.
  • the positive electrode 2 realising the charge storage mechanism through a reversible electrochemical redox reaction taking place in the mono- or poly-molecular layers of products resulting from interaction of electrode material with electrolyte, is made out of a porous material, comprising at least a metal from the following group: nickel (Ni), cobalt (Co), lead (Pb).
  • Said porous metal can be made in several different ways.
  • One preferable way being the thermochemical treatment of a NiTi alloy in chlorine gas at elevated temperatures.
  • Another preferable way being the electrochemical treatment of a mckel aluminium alloy (formed by annealing of a bi- or tri-metal foil) in a basic solution of potassium hydroxide.
  • Yet another preferable way being firstly an oxidation of a metal or metal-alloy substrate providing a porous surface oxide layer and secondly, reducing the porous surface -oxide layer to a porous metal layer.
  • the working voltage of the device can be increased compared to a double-layer capacitor
  • a capacitor device By designing a hybrid capacitor with the capacitance of the positive electrode being much higher than that of the negative double-layer electrode, a capacitor device can be obtained which has a energy storage density more than 4 times higher and a maximum extractable power density which is more than 2 times higher than a what is obtained from a similar double-layer device made of two similar nanoporous carbon electrodes.
  • a preferred way of producing said nanoporous skeleton carbon is by:
  • particles of chosen carbide or carbide powders are formed into an intermediate body with a porosity in the range of 30-70% by any known method, e.g. by pressing with or without a temporary binder, slip casting, tape casting.
  • the size and distribution of the transport pores can be controlled by selecting appropriate particle sizes and particle distribution.
  • the degree of packing due to the forming process will of course also influence the porosity of the work-piece.
  • the subsequent step of forming which results in the production of a work-piece with high mechanical strength and a desired transport porosity, can be treating of the intermediate body in a medium of gaseous hydrocarbon or hydrocarbon mixtures at a temperature above their decomposition temperature.
  • natural gas and/or at least a hydrocarbon selected from the group comprising acetylene, methane, ethane, propane, pentane, hexane, benzene and their derivates.
  • Duration of treatment in said medium is controlled by measuring the mass of the article. When the mass has changed by at least 3%, the strength is already sufficient for use of the article as a capacitor electrode.
  • Another way of forming the work piece when using SiC as a starting material is by infiltrating the pyrocarbon deposited intermediate body with liquid silicon at 1500 - 1700 °C, thus, converting also the pyrocarbon into SiC.
  • Nanoporosity is formed at removal of volatile chlorides of carbide-forming elements in accordance with reaction:
  • a finished electrode produced by the described method has a predetermined shape and size, and its structure is a porous carbon skeleton with a transport porosity of 10-55% obtained in the step of forming of the work-piece and a nanoporosity of 15-55%.
  • the electrode comprises one or several types of nanopores and each type is being characterised with narrow distribution by size.
  • the type of nanopore depends on the type of carbide used for the particles forming the workpiece.
  • the carbon content in the electrode is more than 95%wt, preferably 99%wt, i.e., the obtained article consists practically of pure carbon and has considerable strength and high electrical conductivity allowing to increase its life-time and also to decrease the amount of leakage currents occurring in the capacitor due to electrode impurities.
  • Such a way of producing a nanoporous skeleton carbon is known from WO 97/20233, WO 98/54111 and US 5,876,787.
  • nanoporous carbon can of course be used but the above mentioned method is preferred due to that it yields a nanoporous skeleton carbon with high purity and high electrical conductivity.
  • the positive electrode is a porous nickel electrode made by thermochemical treatment in halogen gas of a nickel alloy.
  • the production steps are:
  • an intermediate body of nickel and modifier As modifier, elements from III, rv, or V group of the Mendeleyev's Periodic System of Elements, and more preferably Ti, B, Si and P are used.
  • An intermediate body is produced by metallurgical, chemical and physico-chemical methods (alloying, chemical interaction, spraying, diffusion processes, etc.) Shaping of the intermediate body can be made by methods of rolling, deformation, etc. 2.
  • the duration of the process depends on the type of modifier and also on the goal. For example, when the process is short in time it is possible to produce a porous nickel material only on the surface of an intermediate body and the content of the intermediate body in the centre of the sample practically remains the same. Thus, a material containing both porous and nonporous parts is produced. A similar material also can be produced if a layer of nickel-modifier alloy is deposited on the surface of nickel. In this case, porosity will be formed only in those parts of the intermediate body, which contain modifier.
  • a step of heat treatment in a reducing (air) or inert (argon, etc.) medium or in vacuum can be used.
  • the produced porous metallic body has good physico-chemical properties, in particular high electrical capacitance in electrolyte solutions, and hence such bodies can be effectively used as electrodes for charge accumulation and storage.
  • Foils prepared from Ni-modifier alloys Ni foil with sprayed Ni-modifier alloys
  • Ni foil + introduced Si (or B, etc.) to produce NiSi (or NiB., etc.) film on the surface Ni-modifier compound films produced by electrochemical deposition
  • the carbon electrode and the nickel electrode can be exposed to thermochemical treatment in a halogen gas, such as chlorine, at the same time.
  • the positive electrode is a porous nickel (Ni) or c bajt (Co) electrode made in accordance with the Russian patent application (appl. No. 9811373).
  • the electrode consists of a backing layer made of a material chemically and electrochemically inactive in the electrolyte and an electrochemically active layer being obtained by means of chemical and/or electrochemical treatment in solutions of acids, salts or alkalis of a Ni-alloy being deposited or formed on the backing layer.
  • Said alloy can be formed on one or both sides of said backing layer. Said alloy satisfying the formula:
  • Mi - loosening metal from the group: aluminium (Al), zinc (Zn), tin (Sn), alkali and alkali-earth metals, or their combinations,
  • M2 - a metal from the group: nickel (Ni), cobalt (Co) or their alloys, or an alloy of at least one metal out of this group with one or several additional alloying elements from the group: silver (Ag), lanthanum (La) or lanthanides, molybdenum (Mo), tungsten (W), manganese (Mn), vanadium (V), titanium (Ti), bismuth (Bi), antimony (Sb), iron (Fe).
  • the backing layer of said positive electrode should be within 5 to 150 ⁇ m, more preferably from 10 to 50 ⁇ m, and the thickness of the electrochemically active layer should preferably be within 5 to 100 ⁇ m.
  • Said backing and alloy layer can preferably be formed by annealing a bi- or tri-metal foil in an inert gas at elevated temperatures.
  • said positive electrode is obtained by means of chemical and/or electrochemical treatment of said backing and alloy layer in aqueous solutions of sulphuric or phosphoric acids of 1 to 30% mass, or by means of aqueous solution of potassium, sodium or ammonium salts of chemical and/or electrochemical treatment of said backing and alloy layer in aqueous solutions of potassium, sodium or ammonium salts of both organic and inorganic acids, or by means of chemical and/or electrochemical treatment of said backing and alloy layer in aqueous or mixed aqueous-organic solutions of alkalis of 1 to 70% mass.
  • the treatment leads to that the loosening metal is completely or partially removed.
  • the positive redox electrode is obtained by a method of forming a porous metal layer of open porosity from an electrically conducting substrate, consisting in that on the electrically conducting substrate first a surface layer of intermediate oxides is formed, which then is converted to a layer of the final composition in the form of a porous metal layer of open porosity. Formation of the porous intermediate oxide surface layer on the electrically conducting substrate is made by porous oxidation (producing pores) of the substrate initial surface layer material, the initial surface layer being a dense or porous metal or metal-alloy. Finally, the porous intermediate oxide surface layer obtained on the substrate is being reduced to metal at temperature which is below the sintering temperature for the pore structure of the porous layer.
  • the porous oxidation of the substrate initial surface layer material is carried out electrochemically in electrolyte solution, plasma-elecfrochemically in electrolyte solution, electrochemically in a molten electrolyte, as well as chemically in the solution.
  • the thereby received intermediate surface layer of a porous oxide is then being reduced to metal chemically in a solution, containing a reducing agent in its composition, chemically in gas medium containing a reducing gas, electrochemically cathodically in a electrolyte solution, as well as electrochemically cathodically in a molten electrolyte.
  • the substrate materials it is possible to use metals from the following group: zinc (Zn), lead (Pb), copper (Cu), silver (Ag), iron (Fe), nickel (Ni), cobalt (Co), cadmium (Cd), bismuth (Bi), antimony (Sb), tin (Sn), titanium (Ti) and their alloys.
  • the surface layer of a porous oxide contains in its composition one or several metals out of group : zinc (Zn), lead (Pb), copper (Cu), silver (Ag), iron (Fe), nickel (Ni), cobalt (Co), cadmium (Cd), bismuth (Bi), antimony (Sb), tin (Sn), titanium (Ti).
  • the porous oxidation procedure is carried out, for example, by dipping the substrate in electrolyte (solution or melt) of appropriate composition at a defined temperature and connecting it to the positive pole of power source, to the negative pole of which the auxiliary electrode - cathode is connected (an example of electrochemical oxidation). It is possible to carry out that porous oxidation using alternating current or current of complex form, as well as without current at all (an example of chemical oxidation).
  • the second operation - the operation of conversion of a porous oxide layer into a porous metal layer - presents in itself a technological operation of reducing the porous oxide to metal which is carried out chemically or electrochemically.
  • the operation of electrochemical conversion of a porous oxide layer to porous metal layer is carried out, for example, by means of electrochemical cathodic reduction of porous oxide in an electrolyte solution or melt.
  • Electrochemical cathodic reduction of porous oxide in electrolyte solution is carried out, for example, by dipping the oxidised substrate into an aqueous electrolyte solution at a defined temperature and connecting it to a negative pole of the power source. The positive pole of the power source is connected to the auxiliary electrode - anode.
  • the electrochemical cathodic reduction of porous oxide in electrolyte melt is carried out.
  • Chemical reduction is carried out by simply exposing the oxidised substrate to a solution, a melt, a gas medium containing an appropriate reducing agent, which is capable to reduce the oxide to metallic state. It is essential that the temperature during the reduction is below the temperature of sintering the oxide and metal in order that during the reduction, no sintering of the oxide microstructure take place and , correspondingly, of porous metal.
  • nanoporous carbon as a negative electrode has been demonstrated by a microelectrode experiment.
  • the nanoporous carbon particles used in this experiment were made from SiC powder (producer: Norton-Lillesand AS, Norway) that had been chlorine treated by a process described in WO 97/20333 to become carbon. This carbon has a very narrow pore size distribution of about 8A.
  • FIG. 2 shows a principal drawing of an experimental microelectrode set up, where 8 is a microscope, 9 is the particle, 10 the separator, 11 the carbon fibre, 12 is the counter electrode, 13 the micro manipulator, and 14 is the reference electrode.
  • the experimental cell was surrounded by a sealed plastic cover and a slight overpressure of a protection gas (N2) was applied.
  • the counter electrode 12 was a piece of activated carbon fibre cloth.
  • the potential of the counter electrode 12 was between 0 and -200 mV (normally around -100 mV) versus the reference electrode 14 (Hg/HgO in 6M KOH). Before an experiment was started the potential of the counter electrode 12 was allowed to equilibrate for at least 24 hours.
  • the counter electrode 12 served as a reference during the experiments.
  • the charging/discharging of the nanoporous carbon particle 9 did not have any significant influence on the potential of the counter electrode 12.
  • the electrolyte was 6M KOH and the experiments were all conducted at room temperature.
  • Both the current and the potential of the particle 9 were probed through the carbon fibre 11 contact.
  • the current was determined as a potential drop over a 1 k ⁇ resistor (R ⁇ ).
  • the current source was a standard 1,5 V R20 battery.
  • the data was collected by a digital multimeter (PREMA 5017) connected with a PC. The resolution of the multimeter was 10 nV at a minimum sampling time of 2 seconds.
  • the resistance of the carbon fibre 11 (0,5-3 k ⁇ ) was measured ex-situ, before starting each experiment.
  • the experimental set-up can be regarded as a double layer capacitor with the nanoporous carbon particle 9 being much smaller than the carbon fibre counter electrode 12.
  • the cell was used to conduct potential step experiments where the potential is instantaneously changed and the current response is monitored.
  • the potential step experiments were conducted by opening for charging or closing for discharging the contact (Ci). Before recording the nanoporous carbon particle 9 was cycled and allowed to equilibrate at least twice.
  • the multimeter was first set to a sampling time of 2 s, but for the negative side the experiments were repeated with a sampling time of 0.2 s, the particle being charged: -500 to -600 mV, discharged: -600 to -500 mV, charged: 0 to -100 mV, discharged -100 to 0 mV.
  • the whole set of experiments were conducted within 4h (see Fig. 3).
  • Fig. 3. shows how the initial current, i 0 , increases as the starting potential decreases. It can be concluded that a more than 5 times higher current can be obtained by a 100 mV potential step at a potential of -500 mV compared to at +500 mV.
  • a sample of porous nickel is produced according a method described in patent application PCT/EP98/06106.
  • the intermediate body is produced by cold rolling of NiTi alloy containing 45 %wt Ti and 55 %wt Ni.
  • a foil of thickness 200 microns and size 25 x 20 mm were prepared by the described way. The foil was chlorinated in a chlorine flow (0.3 1 min). Heat treatment in chlorine was carried out at temperature of
  • the produced sample was used as a cathode of 020mm (positive electrode) of a hybrid capacitor cell.
  • Electrolyte in the cell was 25 % aqueous solution of KOH.
  • the cell was charged by DC 10 mA and then discharged through external resistor 100 Ohm.
  • the obtained charging- discharging curve is presented in Fig. 4.
  • the exhibited electrical capacitance of the cell is 21 F, while a capacitance of the same cell with carbon cathode produced according to US 5,876,787 is 10 F.
  • Ni-electrode consists of a dense backing layer (-0.03 mm) and a porous active layer (-0.05 mm).
  • the produced sample was used as a cathode of 020mm (positive electrode) of a hybrid capacitor cell.
  • the double-layer capacitor and the hybrid capacitor were charged and discharged between 0.4-0.8 V and 0.7-1.4 V, respectively, the charging capacitances are presented in Table 1.
  • Example 2 and Example 3 were electrochemically tested using a Russian test equipment named IEK-5.
  • the IEK-5 instrument is designed, for measurement of capacitance at charging with constant current at any part of the charging curve.
  • a porous nickel foil was prepared according to example 3. Two circular electrodes of 3 cm 2 area were cut from the nickel foil.
  • a nanoporous carbon electrode was prepared from a SiC precursor powder of about 1 ⁇ m particle size, pressed to a work-piece tablet of 1.4 mm thickness. Pyrocarbon was deposited on the work-piece using natural gas at 820°C for 5h. Chlorination was conducted at 1000°C for 3h. The pyrocarbon content of the final electrode was about 25%wt, the total porosity was about 65% and the nanoporosity was about 30%.
  • An electrode of activated carbon fiber cloth was cut out from a commercial carbon fiber cloth (Institute of Sci. & Tech., Electrostal of Moscow, type: TSA) of 0.5 mm thickness.
  • Two hybrid capacitor cells of 3 cm 2 were made using the one nickel foil as positive electrode and the two different carbons as negative electrodes in each cell.
  • the carbon electrodes were coated with nickel (up to 7 ⁇ m thick layer) on one side to decrease the contact resistance.
  • the separator was 0.1 mm thick.
  • the capacitors were tested at 10 mA.
  • the capacitances and other characteristics of the capacitors are given in Table 1.
  • the higher specific capacitance of the hybrid using a nanoporous carbon is due to the higher specific capacitance of the nanoporous electrode.
  • Examples 5-7 presents different redox electrodes suitable as positive electrodes in the present invention.
  • the roughness coefficient C R of the obtained porous metal layers is defined by means of correlation of cyclic voltammagrams obtained of these layers, with voltammagrams obtained on a smooth (mechanically or electromechanically polished) sample of metal which is of the same composition, as that of the porous layers.
  • the electrolyte and the range of cycling potentials for each metal were selected in such way, that the reversible redox reactions of formation by reduction of the thin, surface mono or polymolecular oxide(hydrooxide), layers took place in the selected potential range. Oxidation and reduction current of these layers depends on the rate of potential scanning and on the value of true surface of a sample.
  • a 0,5 mm thick foil of a cobalt alloy (87% mass) with tungsten (13% mass) was electrochemically oxidated in a molten mixture of alkalies: KOH - NaOH (ratio 1 : 1 mol.) at temperature 250 °C during 60 min at voltage of 1,2 V.
  • the cathode is a plate out of steel X18H10T.
  • Current density was decreasing from 10 mA/cm 2 to 3 mA/cm 2 during 20 min, further it stayed approximately constant, equal to (2,5 - 3) mA/cm 2 .
  • As a result of the oxidation 25 - 27 ⁇ m thick porous oxide layers were formed on both sides of the foil.
  • the cathode reduction of porous oxide was carried out in 3% aqueous KOH solution at temperature of 450°C and current density of 5 mA/cm 2 .
  • a porous metal layer of 25 ⁇ m thickness was received, having the following composition: Co - 95%, W - 4,5%, O - 0,4%, H - 0,1% mass.
  • Cathode is a plate out of steel X18H10T. Current density was maintained constant at 25 mA/cm until reaching a voltage of 1.6 V. The oxidation time was 200 min. In these conditions the nickel foil was not oxidated and the layer of the above mentioned alloy turned into a layer of porous oxide of 60 ⁇ m thickness.
  • V A porous lead electrode, obtained by sintering a powder of particles with sizes (100 -

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Abstract

La présente invention concerne un condensateur hybride comprenant une électrode positive (2) et une électrode négative (5) séparées par un séparateur (3), les électrodes et le séparateur étant saturés par un électrolyte aqueux. Dans le procédé selon l'invention, l'électrode négative (5) est formée de carbone nanoporeux, essentiellement formé à partir d'un précurseur de carbure, la plupart des nanopores présentant une taille inférieure à 5 nm et de préférence à 2 nm.
PCT/EP1999/002109 1998-07-03 1999-03-26 Condensateur hybride Ceased WO2000002215A1 (fr)

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AU39263/99A AU3926399A (en) 1998-07-03 1999-03-26 A hybrid capacitor

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RU98113174/09A RU2145132C1 (ru) 1998-07-03 1998-07-03 Электрохимический конденсатор с комбинированным механизмом накопления заряда
RU98113174 1998-07-03

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WO2002039468A3 (fr) * 2000-11-09 2003-03-06 Ultratec Ltd Supercondensateur et son procede de fabrication
WO2006111079A1 (fr) * 2005-04-21 2006-10-26 Fudan University Dispositif de stockage d'energie aqueux hybride
WO2007016077A1 (fr) * 2005-07-30 2007-02-08 Corning Incorporated Condensateurs hybrides cellulaires en nid d’abeille avec une géométrie de cellule non uniforme
GB2443221A (en) * 2006-10-25 2008-04-30 Nanotecture Ltd Hybrid supercapacitor comprising double layer electrode and redox electrode
US9773620B2 (en) 2013-04-24 2017-09-26 Commissariat à l'énergie atomique et aux énergies alternatives Electrochemical supercapacitor device made from an electrolyte comprising, as a conductive salt, at least one salt made from an alkali element other than lithium
RU2644398C2 (ru) * 2013-12-20 2018-02-12 Интел Корпорейшн Гибридный электрохимический конденсатор

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RU2170468C1 (ru) * 2000-04-10 2001-07-10 Мирзоев Рустам Аминович Электрохимический накопитель энергии высокой удельной мощности и электрод для него
RU2338286C2 (ru) * 2002-03-26 2008-11-10 Сергей Николаевич Разумов Электрохимический конденсатор
CN101657941B (zh) * 2007-02-16 2013-07-31 通用超级电容器公司 电化学超级电容器/铅酸电池混合电能储能装置

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EP0763509A1 (fr) * 1995-03-30 1997-03-19 Nippon Sanso Corporation Matiere carbonee poreuse, procede de production de ladite matiere et utilisation de cette derniere
WO1997020333A1 (fr) * 1995-11-30 1997-06-05 Alfar International Ltd. Condensateur electrique double-couche, des electrodes poreuses en carbone et procede pour realiser ces electrodes

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Publication number Priority date Publication date Assignee Title
WO2002039468A3 (fr) * 2000-11-09 2003-03-06 Ultratec Ltd Supercondensateur et son procede de fabrication
US6602742B2 (en) 2000-11-09 2003-08-05 Foc Frankenburg Oil Company Est. Supercapacitor and a method of manufacturing such a supercapacitor
US6697249B2 (en) 2000-11-09 2004-02-24 Foc Frankenburg Oil Company Supercapacitor and a method of manufacturing such a supercapacitor
WO2006111079A1 (fr) * 2005-04-21 2006-10-26 Fudan University Dispositif de stockage d'energie aqueux hybride
WO2007016077A1 (fr) * 2005-07-30 2007-02-08 Corning Incorporated Condensateurs hybrides cellulaires en nid d’abeille avec une géométrie de cellule non uniforme
GB2443221A (en) * 2006-10-25 2008-04-30 Nanotecture Ltd Hybrid supercapacitor comprising double layer electrode and redox electrode
WO2008050120A3 (fr) * 2006-10-25 2008-10-02 Nanotecture Ltd Electrodes pour des piles électrochimiques
US9773620B2 (en) 2013-04-24 2017-09-26 Commissariat à l'énergie atomique et aux énergies alternatives Electrochemical supercapacitor device made from an electrolyte comprising, as a conductive salt, at least one salt made from an alkali element other than lithium
RU2644398C2 (ru) * 2013-12-20 2018-02-12 Интел Корпорейшн Гибридный электрохимический конденсатор

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RU2145132C1 (ru) 2000-01-27

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