WO2015069853A1 - Perfectionnements apportés à des condensateurs utilisant du charbon traité en tant qu'électrodes - Google Patents

Perfectionnements apportés à des condensateurs utilisant du charbon traité en tant qu'électrodes Download PDF

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WO2015069853A1
WO2015069853A1 PCT/US2014/064275 US2014064275W WO2015069853A1 WO 2015069853 A1 WO2015069853 A1 WO 2015069853A1 US 2014064275 W US2014064275 W US 2014064275W WO 2015069853 A1 WO2015069853 A1 WO 2015069853A1
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och
carbonate
electrochemical device
methyl
solvent system
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PCT/US2014/064275
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English (en)
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W. Novis Smith
Joel R. Mccloskey
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Retriev Technologies Incorporated
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Priority claimed from US14/073,302 external-priority patent/US9034517B1/en
Priority claimed from US14/073,401 external-priority patent/US8785057B1/en
Application filed by Retriev Technologies Incorporated filed Critical Retriev Technologies Incorporated
Publication of WO2015069853A1 publication Critical patent/WO2015069853A1/fr

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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
    • H01G11/54—Electrolytes
    • H01G11/58—Liquid electrolytes
    • H01G11/60—Liquid electrolytes characterised by the solvent
    • 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
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0568—Liquid materials characterised by the solutes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0569—Liquid materials characterised by the solvents
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • 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
    • H01G11/54—Electrolytes
    • H01G11/58—Liquid electrolytes
    • H01G11/62—Liquid electrolytes characterised by the solute, e.g. salts, anions or cations therein
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0025—Organic electrolyte
    • H01M2300/0028—Organic electrolyte characterised by the solvent
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0025—Organic electrolyte
    • H01M2300/0028—Organic electrolyte characterised by the solvent
    • H01M2300/0037—Mixture of solvents
    • 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
    • Y02E60/10—Energy storage using batteries
    • 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 present invention relates to novel electrolyte solutions for electrochemical devices such as capacitors and having carbon electrodes with conditioned carbon elements. More particularly, there is a synergism found with the use of the electrolyte solutions with the conditioned carbon cathodes which improves the energy density with a conductive salt such as a lithium salt or quaternary ammonium salt.
  • a conductive salt such as a lithium salt or quaternary ammonium salt.
  • blends of organic carbonates have been used along with the addition of ethers and low molecular weight esters to achieve low temperature (-60°C) freezing points of the mixed solvents containing lithium hexafluorophosphate for low temperature lithium-ion battery performance.
  • the use of mixtures of ethylmethyl carbonate with dimethyl carbonate and small quantities of ethylene carbonate have allowed performance down to -20°C and even -30°C in some cases for lithium battery electrolytes.
  • the use of tetrahydrofuran (THF) and methyl formate and methyl acetate and dimethyl ethylene glycol (glyme) or dimethoxy ethane (DME) has allowed some battery electrolytes to achieve -40°C or even -50°C performance.
  • Propylene carbonate has been used in mixtures with other organic carbonates for capacitor electrolytes but this solvent also limits cell voltage to about 3 V and the solubility of the tetrafluoroborate salt decreases rapidly on cooling and results in low conductivity of the electrolyte at temperatures below -20°C.
  • the use of ethylene carbonate (mp 35°C) with cyclic organic carbonate mixtures containing organic quaternary tetrafluoroborate salts for capacitor use gives higher operating cell voltage in ultra capacitors, but these electrolytes freeze before - 20°C is reached.
  • Low temperature cycling performance non-freezing
  • the temperature desired is down to -40°C.
  • these applications desire high temperature performance (>70°C) with low vapor pressure. This means that volatile solvents which are used for low temperature performance cause problems at the high end of the desired performance range.
  • Activated carbon is the preferred material for use in preparing electrodes for carbon electrode capacitors.
  • This activated carbon is prepared from a number of different sources such as coconut shells, wood, sugar, cellulosics and phenolic resins. After converting these materials to carbon under steam controlled conditions, the carbons are "activated” in a second step using steam or catalyzed with KOH, NaOH and/or carbon dioxide and KOH to increase the surface area to very high surface areas such as 1000 to 2400 m /g.
  • These activated carbons usually contain about 2% oxygen after they have been thoroughly dried and traces of inorganic salts. This oxygen is probably present as quinones, hydroquinones, esters, phenols, carboxylic acids, furans and possibly ketones etc. with some nitrogen compounds present— all of which under high voltage conditions greater than 3 V. will undergo electrochemical
  • Electrolytic capacitors and electrochemical double layer capacitors also have an electrolyte.
  • the electrodes are provided by an oxide or carbon layer formed on metal foil and are separated by a porous non-conducting membrane such as paper, porous polymer, etc.
  • the liquid electrolyte provides electrical contact to the opposite electrode through the separator.
  • the inherently high resistance of electrolytic capacitors is generally mitigated by rolling a large sheet of the electrode material into a roll to give high surface area.
  • the dielectric is provided by the electrolyte.
  • the resistance of the electrolyte is a significant factor in the total device resistance.
  • the temperature has a major influence on the electrolyte in the performance of the capacitor since the conductivity of the electrolyte decreases with temperature.
  • Electrochemical double layer capacitors including super capacitors typically comprise electrodes, electrical contacts to a power supply, separators for electrodes and/or cells, and electrolyte and environmental seals.
  • electrolyte typically comprises a combination of a conductive salt and a solvent.
  • Desirable electrolytes are typically liquid with low viscosity, low density, and high conductivity over a range of ambient temperature conditions. They should also be commercially inexpensive, chemically and electrochemically stable, and compatible with carbon.
  • Aqueous electrolyte systems have been used extensively and provide voltage restricted below 1.8 V. For example, ultra capacitors in Japan are not permitted to use acetonitrile for the electrolyte.
  • U.S. Patent No. 6,743,947 to Xu, et al. discloses an electrolyte system comprising a mixture of ethylene carbonate and dimethyl carbonate at a concentration of the electrolyte salt at 0.5 -2.5 M which has poor conductivity at low temperatures.
  • U.S. Patent No. 7,924,549 to Smith, et al discloses conditioned carbon electrodes for capacitors and lithium batteries having conditioned carbon electrodes that have also been heat treated and used in an electrolyte comprising a quaternary ammonium tetrafluorobotrate salt in an aprotic solvent.
  • U.S. Patent Application Publication No. 20070002522 discloses capacitors having electrodes with alkali-activated carbon electrodes in electrolytic solutions comprising a quaternary ammonium salt and a solvent containing a carboxylic ester.
  • Electrochemical double layer capacitors capable of high energy density have been assembled from a variety of materials.
  • super-capacitors have been constructed from a variety of materials.
  • This type of super-capacitor incorporates electrodes based on carbon that may be prepared from organic gels.
  • ammonium salt of hydrogen fluoride with an imidazolium compound in a nitrile solvent which operate at temperatures between -60 and 150 degrees C.
  • the tetrafluoroborate salt can be used in the present invention with the present electrolyte solutions.
  • lithium ion batteries and capacitors containing carbon electrodes an electrolyte solution which comprises a conductive salt such as a lithium salt or a quaternary ammonium salt and a solvent system comprised of at least 20% by weight (i.e., 25 to 75% by weight) of one or more symmetrical and/or unsymmetrical (asymmetrical) carbonates of the formula:
  • R is selected from the group consisting of methyl, ethyl, propyl, isopropyl,
  • R 1 is selected from the group consisting of CH 3 OCH 2 CH 2 -, CH 3 OCH 2 CH 2 OCH 2 CH 2 -, CH 3 OCH 2 CH 2 OCH 2 CH 2 OCH 2 CH 2 -,
  • an electrochemical device e.g., a lithium battery or a capacitor, such as an ultra capacitor or an electrochemical double layer capacitor
  • an electrochemical device comprising the combination of a conditioned and heat treated carbon electrode having reduced chemically bound oxygen, nitrogen and sulfur and an electrolyte solution, the electrolyte solution comprising a non-aqueous solvent system comprising 20 to 100% by weight of one or more symmetrical and/or asymmetrical carbonates of the general formula:
  • R is selected from the group consisting of methyl, ethyl, isopropyl, propyl,
  • R 1 is selected from the group consisting of CH 3 OCH 2 CH 2 -, CH 3 OCH 2 CH 2 OCH 2 CH 2 -, CH 3 OCH 2 CH 2 OCH 2 CH 2 OCH 2 CH 2 -,
  • R" is methyl, ethyl, propyl or isopropyl, and a conductive salt (e.g., a lithium salt or a quaternary ammonium tetrafluoroborate or triflate) at a concentration of from 0.6 to 3 mol/1.
  • a conductive salt e.g., a lithium salt or a quaternary ammonium tetrafluoroborate or triflate
  • the novel carbonates of the invention can be mixed with each other or with other organic cyclic or linear carbonates, ethers and carboxylic esters such that they comprise at least 20% by weight of the solvent systems.
  • the solvents are utilized in combination with capacitors having carbon electrodes which have been "activated” or post-treated to reduce or remove all chemically bound oxygen, nitrogen and sulfur and preferably heat treated after acid washing at temperatures of 1100-1500°C under an inert atmosphere.
  • the surface area of the carbon present in the carbon electrode is >1200 m 2 /g.
  • the internal resistance of an ultra capacitor cell is reduced or minimized by lowering the functional Equivalent Series Resistance (ESR) as measured on the RCL meter (Resistance Capacitance and Inductance) which measures the capacitor's impedance in a circuit.
  • ESR Equivalent Series Resistance
  • the ESR limits the power at which the device can operate from a direct or alternating current.
  • capacitor refers to all capacitors which are provided with at least one activated carbon electrode and includes Electric Double Layer Capacitors (EDLC) and Ultra Capacitors (UC).
  • EDLC Electric Double Layer Capacitors
  • UC Ultra Capacitors
  • a yet still further aspect of the invention provides an ultra capacitor having a stable operating cell voltage of about 4V when containing, as part of an electrolyte solution, about 2M of a quaternary ammonium tetrafluoroborate salt at room temperature.
  • Also provided by the present invention is a method of making an electrochemical device, comprising the step of combining a carbon electrode with an electrolyte solution comprising a non-aqueous solvent system comprising 20 to 100% by weight of one or more symmetrical and/or asymmetrical carbonates of the general formula:
  • R is selected from the group consisting of methyl, ethyl, isopropyl, propyl,
  • R 1 is selected from the group consisting of CH 3 OCH 2 CH 2 -, CH 3 OCH 2 CH 2 OCH 2 CH 2 -, CH 3 OCH 2 CH 2 OCH 2 CH 2 OCH 2 CH 2 -,
  • capacitors having the synergistic combination of at least one activated carbon electrode in an electrolyte solution comprising a conductive salt (e.g., a lithium salt or a quaternary ammonium salt) in a concentration of 0.6 to 3 M wherein the solvent system used for the electrolyte solution is acetonitrile-free and comprises 20 to 100% by weight, preferably 25 to 75%> by weight, of one or more symmetrical and/or unsymmetrical carbonates of the formula:
  • a conductive salt e.g., a lithium salt or a quaternary ammonium salt
  • R is selected from the group consisting of methyl, ethyl, isopropyl, propyl,
  • R 1 is selected from the group consisting of CH 3 OCH 2 CH 2 -, CH 3 OCH 2 CH 2 OCH 2 CH 2 -, CH 3 OCH 2 CH 2 OCH 2 CH 2 OCH 2 CH 2 -,
  • the carbonate solvents of the invention may be a mixture of themselves or with other linear or cyclic carbonates, esters and/or ethers, preferably ethylene carbonate.
  • the solvent system comprises, consists essentially of, or consists of ethylene carbonate (EC) and methyl- (2-methoxyethyl)-carbonate (MMC).
  • An amount of MMC may be present in combination with EC which is effective to provide a solvent system having a freezing point of -20°C or lower, - 30°C or lower, -40°C or lower, or even -50°C or lower.
  • An EC/MMC solvent system may contain, for example, 10 to 80% by weight EC, with the balance being MMC.
  • such a solvent system may contain up to 5% by weight of one or more solvents other than EC and MMC, such as a cyclic or linear carbonate.
  • Cyclic carbonates include ethylene carbonate (hereafter designated as EC) and propylene carbonate (PC).
  • Linear carbonates include dimethyl carbonate (DMC), diethyl carbonate (DEC), ethylmethyl carbonate (EMC), etc.
  • the carboxylic ester optionally used herein preferably has three or more carbon atoms and one or more carboxylic ester bonds.
  • the upper limit of the number of carbon atoms in the carboxylic ester is not particularly limited.
  • the carboxylic ester preferably has ten or less carbon atoms and more preferably eight or less carbon atoms.
  • the number of carboxylic ester bonds in the carboxylic ester is one or more as described above. Since an increase in the number of carboxylic ester bonds generally leads to an increase in the viscosity of the carboxylic ester, the number of carboxylic ester bonds is preferably one or two.
  • carboxylic esters examples include dimethyl succinate, ethyl methyl succinate, diethyl succinate, dimethyl 2-methylsuccinate, ethyl methyl 2-methylsuccinate, dimethyl glutarate, ethyl methyl glutarate, diethyl glutarate, dimethyl 2-methylglutarate, ethyl methyl 2-methylglutarate, diethyl 2-methylglutarate, dimethyl adipate, ethyl methyl adipate, diethyl adipate, 1,2-diacetoxyethane, 1 ,2-diacetoxypropane, 1 ,4-diacetoxybutane, glycerin triacetate, methyl 4-acetoxybutyrate, gamma butyrolactone, and methyl 2-acetoxyisobutyrate, ethyl acetate and methyl acetate.
  • the electrolyte solutions of the present invention for capacitors comprise the solvent systems of the invention and at least one conductive salt dissolved as an electrolyte.
  • the conductive salt may be any that is capable of being used in electrical storage devices, such as lithium secondary cells, lithium ion secondary cells and electrical double-layer capacitors.
  • Conductive salts that may be used include alkali metal salts and quaternary ammonium salts. Combinations and mixtures of different conductive salts may be utilized.
  • Preferred alkali metal salts are lithium salts, sodium salts and potassium salts. Specific examples include: (1) lithium salts such as lithium tetrafluoroborate, lithium
  • lithium perchlorate lithium trifluoromethanesulfonate, sulfonyl imide lithium salts, sulfonyl methide lithium salts, lithium acetate, lithium trifluoroacetate, lithium benzoate, lithium p-toluenesulfonate, lithium nitrate, lithium bromide, lithium iodide and lithium tetraphenylborate;
  • sodium salts such as sodium perchlorate, sodium iodide, sodium tetrafluoroborate, sodium hexafluorophosphate, sodium trifluoromethanesulfonate and sodium bromide
  • potassium salts such as potassium iodide, potassium tetrafluoroborate, potassium hexafluorophosphate and potassium trifluoromethanesulfonate.
  • quaternary ammonium salt useful in the present invention include, but are not limited to, quaternary ammonium tetrafluoroborates and quaternary ammonium triflates such as triethylmethylammonium tetrafluoroborate, diethyldimethylammonium tetrafluoroborate, ethyltrimethylammonium tetrafluoroborate, dimethylpyrrolidinium tetrafluoroborate, diethylpyrrolidinium tetrafluoroborate,
  • quaternary ammonium tetrafluoroborate salts preferably have a molecular weight in the range of 178-240.
  • tetrafluoroborate and the like are particularly preferable.
  • the concentration of the conductive salt in the electrolyte solution of the present invention is preferably from 0.6 to 3 mol/1, particularly preferably from 1 M to 2 M of the electrolytic solution.
  • the concentration of the conductive salt is less than 0.6 mol/1, the conductivity may be insufficient; if more than 3 mol/1, the low temperature performance and economical efficiency may be impaired.
  • the electrolyte solution should remain liquid with high salt concentrations of salt, e.g., from >1 M up to 2 M.
  • the organic carbonates of the invention meet all of these requirements.
  • the liquidus range of this solvent is about -65°C to 170°C, providing outstanding low temperature and high temperature performance while dissolving a high level of conductive salt.
  • This solvent has a stable operating cell voltage of about 4 V in ultra capacitor performance when containing 2 M diethyldimethyl ammonium tetrafluoroborate at room temperature.
  • Other quaternary alkylammonium tetrafluoroborates can also be used for this same stable high operating voltage in this solvent and related solvents.
  • the catalyst can be neutralized with an acid or acid salt and the reaction mixture distilled to remove the alcohols and obtain pure organic carbonate components or a useful mixture of organic carbonates.
  • Using an excess of the DMC in this case favors more of the desired MMC (asymmetrical component) as opposed to the symmetrical component bis-2-methoxyethyl carbonate (BMC).
  • BMC bis-2-methoxyethyl carbonate
  • Mixtures of both with the starting material can be used as long as the alcohols are removed.
  • the MMC is a preferred solvent of these series of organic carbonates. MMC may be isolated in pure form by distillation.
  • the preferred carbon electrodes of the invention can be prepared following the procedure disclosed in U.S. Patent No. 7,924,549 of Smith, et al., incorporated herein by reference in its entirety for all purposes.
  • Electrodes may be made of 90% treated carbon and 10% Kynar® binder in an acetone slurry.
  • a 1-mil thick sheet of aluminum foil pre-treated with a conductive carbon layer may be trimmed to size and prepared for coating.
  • a draw knife may be used to deliver the proper thickness of slurry coating onto the foil.
  • the acetone evaporates and then the other side of the aluminum foil may be coated.
  • proper sized rectangles may be cut from the aluminum sheet with small plain aluminum tabs still attached to one end. Once cut, the electrodes may be baked under vacuum to remove any residual moisture.
  • the ESR of cells was reduced as follows:
  • the higher temperature (above 1 100°C) chemically eliminates most (if not all) chemically bound oxygen and nitrogen, which are susceptible to electrochemical oxidation reduction at cell voltages above approximately 3.4 V in the ultra capacitor. Their presence contributes to leakage current (electrochemical oxidation currents on charging the UC and accelerate self discharge) which degrades UC performance, especially at operating voltages above 3.4V.
  • conditioning the carbon electrodes according to the present preferred process optimizes the performance of the ultra capacitor when used with the electrolyte solutions of the invention
  • the prior art carbon electrodes, for example, which have been alkali conditioned will also be synergistically improved with the electrolyte solutions of the invention.
  • the distillate was continuously collected and checked by GC for the presence of products (MMC and bis(2-methoxy ethyl)- carbonate (BMC)). This was continued until the reaction flask reached a temperature of 100°C and the distillation temperature reached 72°C. At this point, the reaction flask contents contained only a small percentage of DMC and no methanol.
  • the reaction mixture was allowed to cool to room temperature.
  • the reaction mixture was then filtered to remove the sodium methoxide catalyst.
  • the slightly yellow filtrate was treated with NaH ⁇ PC ⁇ , mixed, and re-filtered. This step was then repeated and the filtrate checked to assure that no catalyst remained.
  • the filtrate was then transferred to a 500 mL 3-necked flask and stirred. This was then vacuum-distilled slowly.
  • the first fraction started at a distillation temperature of 28°C and a reaction flask temperature of 35°C. These fractions were mostly DMC.
  • the MMC laden fractions were collected under vacuum (24 mm Hg) at a distillation temperature of 43 °C and a reaction flask temperature of 55°C.
  • the GC analysis showed a 91% yield of MMC in the final fraction of MMC product collected.
  • the remainder of the mix was composed of 6% BMC and 3% 2-methoxy ethanol.

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Abstract

L'invention concerne un perfectionnement apporté à des condensateurs comprenant des électrodes en charbon actif, par l'utilisation d'une solution électrolytique contenant un carbonate de formule RO(C=O)OR1 et un sel conducteur tel qu'un sel de lithium ou un sel d'ammonium quaternaire selon une concentration allant de 0,6 à 3 moles/l.
PCT/US2014/064275 2013-11-06 2014-11-06 Perfectionnements apportés à des condensateurs utilisant du charbon traité en tant qu'électrodes WO2015069853A1 (fr)

Applications Claiming Priority (4)

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US14/073,401 2013-11-06
US14/073,302 US9034517B1 (en) 2013-11-06 2013-11-06 Capacitors having conditioned carbon for electrodes
US14/073,302 2013-11-06
US14/073,401 US8785057B1 (en) 2013-11-06 2013-11-06 Electrolyte solution for capacitors and batteries

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JP2000228216A (ja) * 1999-02-08 2000-08-15 Denso Corp 非水電解液および非水電解液二次電池
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US7924549B1 (en) * 2008-10-14 2011-04-12 Lithdyne, LLC Carbon electrodes and electrochemical capacitors

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