WO2014175756A1 - Électrode en carbone et procédé de fabrication d'électrode en carbone - Google Patents

Électrode en carbone et procédé de fabrication d'électrode en carbone Download PDF

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Publication number
WO2014175756A1
WO2014175756A1 PCT/RU2013/000341 RU2013000341W WO2014175756A1 WO 2014175756 A1 WO2014175756 A1 WO 2014175756A1 RU 2013000341 W RU2013000341 W RU 2013000341W WO 2014175756 A1 WO2014175756 A1 WO 2014175756A1
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Prior art keywords
pieces
carbon
electrode
range
strip
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PCT/RU2013/000341
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English (en)
Inventor
Sergey Gennadyevich ULYAKHIN
Viktor Andreyevich NIKITIN
Gleb Sergeyevich KURKIN
Anton Valeryevich GLOTOV
Vyacheslav Ivanovich SHUMOVSKII
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Zakrytoye Aktsionernoye Obshchestvo "Elton"
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Priority to PCT/RU2013/000341 priority Critical patent/WO2014175756A1/fr
Publication of WO2014175756A1 publication Critical patent/WO2014175756A1/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
    • H01G11/22—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
    • H01G11/24—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
    • H01G11/32—Carbon-based
    • 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
    • H01G11/38—Carbon pastes or blends; Binders or additives therein
    • 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
    • H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
    • H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
    • 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
    • H01M4/04—Processes of manufacture in general
    • H01M4/0402—Methods of deposition of the material
    • H01M4/0411—Methods of deposition of the material by extrusion
    • 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
    • H01M4/04—Processes of manufacture in general
    • H01M4/043—Processes of manufacture in general involving compressing or compaction
    • H01M4/0435—Rolling or calendering
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1393—Processes of manufacture of 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621—Binders
    • H01M4/622—Binders being polymers
    • H01M4/623—Binders being polymers fluorinated polymers
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • 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
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • 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

Definitions

  • the present group of inventions relates to electronics, particularly, to the field of porous carbon electrodes manufacturing.
  • the carbon electrodes obtained with the use of the method disclosed can accumulate electric charge due to the electric double layer formation on its surface and can be used in the energy storage devices of different types.
  • the energy generation and consumption are the constituents of human progress. There is a great number of different methods of electric energy generation, and significant number of different types of consumers. Depending on the method of energy generation, its transmission is possible by means of electric circuit (electrons and ions movement), physical movement of energy resources, etc. But except generation, transmission and consumption of electric energy, its storing is also required.
  • Electric energy storage devices are well known.
  • One of the first electric energy storage devices is considered to be Voltaic cell.
  • This device was invented back in 1800 and had two plates made of Cu and Zn, which were immersed in a jar containing acid. Thus, a so called «galvanic cell» has been developed. The most successful were the galvanic cells made on the base of lead acid system. These devices have been developed more than 100 years ago and up to now are the most widely spread electrochemical energy storage devices.
  • Electrostatic capacitors as electric charge (and, relatively, electrical energy) storage devices have been developed even earlier. First records about the devices similar by their operation principle with the state of the art electrostatic capacitors were dated 1745 when the so-called «Leyden jar» has been invented.
  • Capacitance values of the modern electrostatic capacitors can be as high as several farads.
  • the carbon electrodes are porous carbon powders, produced from plants or mineral raw materials by the activation method.
  • the main advantage of such materials is their high specific surface area, reaching several thousand m 2 /g, as well as relatively low cost.
  • the electrodes are made from porous powders together with binding material and further formation of sheets or films of a certain thickness, having direct electrical contact with current collector.
  • the latter comprise the material with high conductivity - usually more than 10 3 Sm/cm and more than 0,1 Sm/cm 2 .
  • the contact between the active electrode material and current collector is often provided by means of electrically conductive adhesive or by another material, which demonstrates the characteristics of high adhesion both to the current collector and to the porous active material.
  • electrically conductive adhesive instead of electrically conductive adhesive, electric contact is provided by means of mechanic pressure between the current collector and the active material.
  • binder must, on the one hand, provide mechanical (and, relatively, electrical) contact between the particles of the active material. Frequently it requires using the relatively large amount of binder. Moreover, binder is often selected from a number of thermoplastic polymers (for example, polyethylene, polypropylene, etc.), which don't possess intrinsic porosity and, therefore, the space, occupied by this binder, is unavailable for the ions of electrolyte. It is also evident that adding the binder into composite material decreases the amount of porous material contained in the electrode. This fact directly influences the capacitance and efficiency of electrochemical capacitors.
  • the cold flow capable polymeric materials are used. They can form fibrillar matrix under the influence of the shear forces applied to the composite having such binder. Therefore, the electrodes of majority of commercial supercapacitors are produced with the use of polytetrafluorethylene (further referred to as - PTFE) as a binder.
  • - PTFE polytetrafluorethylene
  • Another advantage of PTFE is its exclusive chemical and electrochemical resistance. In addition, PTFE is more or less cheaper and commercially available material. PTFE is used in a form of powders or dispersions, which are further mixed homogeneously with powders or dispersions of porous carbon materials.
  • Such additives generally include carbon black, graphite, nanotubes, nano-graphene, metal powders and shavings, insertion of the conductive grid into the active material, etc.
  • porous carbon electrodes manufacturing One of the wide spread among the well known methods of the porous carbon electrodes manufacturing is the method of the strips rolling from granules. This method is often used in production of double-layer capacitors of a jelly roll structure: two electrodes in a form of thin layers on the surface of current collector divided by a separator are coiled into a roll (see. patent RU 2427052 CI, published on 20.08.2011). When using this structure, the thickness of porous carbon layer usually lies in the range of 0,05 to 0,5 mm (see. patent US6713034 published on 30.03.2004).
  • the method of electrode strip manufacturing in such case implies the usage of a mixture of the dry carbon powders and a process liquid with subsequent stepped rolling in one direction by means of multiple-roll calender with rolls diameter ranging from 40 to 350 mm until a necessary thickness is achieved.
  • Manufacturing techniques are fully described by the authors of US patents #6778379 B2, published 02.09.2004 and US patent #7160615 B2, published 03.06.2004.
  • the US patent #4153661 published on 08.05.1979 describes the method of the composite sheets manufacturing on the base of different powders and PTFE as a binder.
  • composite material formation is provided by means of preliminary mixing the PTFE dispersion with the filler in powder state and followed by a biaxial rolling of the obtained pasty mass through a calender several times with half-and-half product folding or decreasing calendar rolls gap between the stages of rolling.
  • This method enables to produce composites of high homogeneity and mechanical strength.
  • One of the main drawbacks of such process is its low productivity specified by use of a number of the repeating operations. It makes scaling of this process in commercial production quite complicated.
  • any additional substances required for the implementation of a certain technology are considered as pollutants and require further removal, for instance, by means of heat treatment or washing that in its turn makes production process more complicated and expensive. Also, according to the description this technology allows to produce carbon electrode materials with thickness from 30 to 250 microns.
  • Dry active mass of carbon electrodes contained carbon black and fluoroplastic binder in the amount of 8-10%.
  • carbon electrode manufacturing by a single-stage rolling becomes unacceptable in the case of necessity to produce carbon electrodes with thickness more than 1000 microns.
  • the requirements to a large diameter of rolls are critical during formation of electrode material because the characteristics of the carbon electrodes of specific thickness are directly dependent on the rolls diameter.
  • this method has one more significant drawback. As there is only one direction calendering, the mechanical and electrical characteristics in the machine and transverse directions may differ. It is explained by the internal processes, occurring in the material structure during rolling.
  • the binder During such material passing through the calender rolls, the binder generates the internal connections (fibrills, strands, fibres], basically, in the calendering direction. Therefore, in order to provide isotropy of the carbon electrode's mechanical and electrical properties, it is necessary to ensure rolling in all directions, which is impossible by using of the existing methods. Anisotropy of the electrode properties has an impact on the specific capacitance and specific energy parameters of the electrodes. In particular, electrodes manufactured by a single-pass rolling possess anisotropy of electrical resistance, which may lead to effectiveness decreasing of electric energy storage devices made with use of such electrodes.
  • the objective of the invention is improving the manufacturing methods of carbon electrode, having thickness more than 1000 microns. By using this method it is possible to produce the active material of carbon electrodes used in the electrochemical capacitors and hybrid energy storage devices.
  • the manufacturing method of carbon electrode has been developed, composed of, but not limited to, porous carbon material, conductive additive and polymeric binder, wherein:
  • a. porous carbon material, conductive additive, polymer binder and a process liquid are homogeneously mixed together to form a pasty substance.
  • Homogenizing the mixture containing porous carbon and conductive additive can be carried out by a mill.
  • Blending and homogenizing the mixture containing the porous carbon, conductive additive, polymer binder and a process liquid can be carried out by a twin-screw extruder or a continuous mixer with co-rotating screws.
  • the length and screws diameter (L:D) ratio may vary from 10:1 to 40:1;
  • the temperature of, at least, a part of a material cylinder of extruder or a continuous mixer in the process of operation may be selected from the range 20 - 100 °C;
  • Distilled or deionized water may be used as a process liquid.
  • Organic solvent may be used as process liquid.
  • the amount of process liquid in relation to the dry components may be selected from the range of 1,5:1 - 3:1.
  • Process liquid may be added on the stage of mixing in an extruder or a continuous mixer. Process liquid may be added before the stage of mixing in an extruder or a continuous mixer.
  • the material granules may be 1-5 mm in size
  • Strip may be cut into parallelogram-shaped pieces
  • At least one of the parallelogram vertices angle may be equal to 45 - 90°.
  • Pressing the parallelogram-shaped pieces may be executed by means of the caterpillar press.
  • Caterpillar press may contain two continuous conveyor belts, arranged one above the other.
  • the gap between the conveyor belts may depend on the size of the pieces being pressed.
  • the gap between the conveyor belts may depend on a number of pieces, arranged one above the other in a string before rolling through a caterpillar press.
  • the gap between the conveyor belts at the caterpillar press output may be, at least, not higher than the total thickness of the string of pieces, fed into the caterpillar press.
  • Pressing the parallelogram-shaped pieces may be executed by means of the multiple-roll press.
  • Rolls may be arranged in pairs.
  • the gap between the rolls arranged in pairs may be set, based on the thickness of the semi-products string, fed into the multiple-roll press.
  • the gaps between the rolls arranged in pairs may be set, based on the quantity of the finished products, arranged one above the other.
  • Number of rolls in the multiple-roll press may be selected from a range of 4-
  • Maximum distance between the rolls, relating to different pairs, may not exceed maximum dimensions of the semi-finished products, feeding to the multiple-roll press.
  • the strip cutting into pieces, their subsequent stacking, compaction and calendering may be repeated several times.
  • Drying may be carried out at the atmospheric pressure and the temperature of 20 - 300 °C .
  • Carbon strip drying duration may be chosen from the range 1 - 10 hours.
  • Drying may be carried out at the low pressure.
  • Pressure may be chosen from the range 0.1 - 0.5 bar.
  • Drying period at low pressure may last from 10 to 120 minutes.
  • Calender rolls diameter may be selected from the range 90 - 1000 mm.
  • Temperature of calender rolls can be selected from the range 20 - 100 °C.
  • the carbon electrode has been developed based on the above described method, actually presenting a sheet composed of porous carbon material, containing conductive additive and polymer binder, characterized by a thickness lying in the range of 1-3 mm, electrical resistance uniformity along the carbon electrode area not higher than 10%, density lying in the range 0.6 - 0.7 g/cm 3 , tensile strength not less than 0,1 MPa, specific electrical capacitance in the sulphuric acid electrolyte equal to 1200 - 1600 F/g, capacitance density in sulphuric acid electrolyte is equal to 750-900 F/cm 3 .
  • Porous carbon material may comprise the powder with particles 0,5-10 microns in size.
  • Porous carbon material may be characterized by a specific surface area value equal to 500 - 3000 m 2 /g.
  • Content of porous carbon material in carbon electrode may be selected from the range 80-99%.
  • Carbon black, graphite powder, carbon nanotubes, graphene nanosheets or their mixture may be used as a conductive additive.
  • Content of conductive additive in carbon electrode may be selected from the range 0-15%.
  • PTFE may be used as a polymer binder.
  • Content of polymer binder may be selected from a range of 1-10%.
  • Electric energy storage device has also been developed, containing, as a minimum, one carbon electrode, manufactured by the method being suggested, together with current collector, minimum one counter electrode, electrolyte, a separator and a body with terminals where the indicated components are placed.
  • Stationary energy storage system has been additionally developed using suggested electric energy storage device.
  • the essence of the present invention concerns to the development of a new continuous manufacturing method of the carbon electrode material for the chemical current source device which demonstrates characteristics of high specific capacitance and energy.
  • the method implies initial mixing the carbon electrode components, partial fibrillation of the binder, granulating the obtained mass, forming a strip by means of a roll mill or a calender, cutting the strip into pieces, their imposition one above the other and further mutual pressing at some angle to the initial rolling direction.
  • Fig.2 Active mass granulation and carbon strip formation process.
  • Fig.5 Vehicle made with the use of energy storage device containing carbon electrode.
  • Fig.6 Stationary energy storage system, using energy storage device, containing carbon electrode.
  • the invention embodiment is using the mechanism of the semi-finished products stacking and rolling at different angles for continuous manufacturing of carbon electrode with thickness not less than 1000 microns having isotropic mechanical and electrical characteristics.
  • the mechanism of the products rolling at different angles has been developed according to the present invention.
  • the process flowchart of carbon electrodes manufacturing is shown in Fig.l.
  • the porous carbon powder is used (1) with high porosity and specific area.
  • the conductive additive such as nonporous carbon powder (2).
  • preliminary blending or grinding (5) of the fine-dispersed nonporous carbon powders together with porous carbon powders for the purpose of their homogenization may be applied.
  • the conditions and duration of the materials dispersion depend on the initial and final parameters of particles distribution pursuant to their sizes.
  • One of the most effective methods of homogeneous blending of active carbon material with conductive additive is their mutual grinding in a ball mill or a vibration mill. Grinding bodies made of sturdy materials which do not contain or isolate hazardous chemical elements are often used during operation process.
  • the process liquid (3) and the polymer binder (4) are added to the indicated carbon-carbon mixture, afterwards additional blending of the indicated components and homogenization of obtained mixture is carried out (6), as a result the carbon-polymeric composition containing process liquid is obtained.
  • Duration and conditions of homogenization depend on electrode material parameters, characteristics of binders and used materials.
  • the obtained carbon-polymeric substance represents the initial material for the carbon electrode formation.
  • the required properties of carbon electrodes manufactured by the method described are achieved by means of further mechanical interaction of the components at certain conditions. As a result of such interaction, polymer binder network composed of fibrils is formed under the active shear deformations inside the material containing such a binder.
  • the substance containing porous carbon powder, conductive additive, process liquid and partially fibrillated binder is fed to the device allowing making granules with specific size distribution (7).
  • the composition of the substance is to be selected such that the granules obtained do not stick to each other during their handling.
  • the produced granules are fed to the hopper located directly over the rolls of a roll-mill. After passing through the roll-mill, the granules are formed in a continuous carbon strip [8) with a certain thickness. It should be noted that the mechanical and electrical characteristics of a carbon strip obtained at this step will differ in parallel and perpendicular directions towards rolling direction. To be noted as well, that the carbon strip manufactured at this process usually has multiple defects such as holes and cracks.
  • the obtained semi-finished product in a form of a strip is cut into substantially equal pieces of a specific predetermined shape [9], which are then laid on the conveyor belt where they are subsequently stacked in a continuous string of multiple layers (10).
  • the continuous string of pieces is delivered to the caterpillar press or multiple-roll calender, where pressing (11) of the obtained multi-layer structure is carried out till the layers are physically connected into a single strip.
  • the next stage is the calendering (12) of the strip obtained to provide high thickness uniformity.
  • the homogenous semi-finished product in a form of a carbon strip and, substantially, having no defects and with high mechanical strength as compared to the initial material is manufactured.
  • the operations (9) - (12) can be repeated several times.
  • the next stage is drying procedure (13). Drying process has a substantial impact on the characteristics of the manufactured carbon strip. This process can be carried out (but not limited) by using the infrared heaters, by means of hot air or in a vacuum.
  • the purpose of drying is removal of, at least, a part of a process liquid.
  • the manufactured carbon strips consist of, significantly, porous carbon materials
  • the considerable part of a process liquid is contained in the pores of a carbon material.
  • Liquid is usually slowly removed from the porous material, therefore the drying duration should be in the range of 1 - 10 hours, depending on the pore sizes of the carbon powder, temperature of thermal drying and a process liquid volatility. Drying temperature is selected thus not to lead to irreversible changes of parameters of carbon powders (1, 2), binders (3) and a process liquid (4). This procedure is also affective at a lower pressure.
  • the semi-finished carbon strip is formed and dried its calendering is carried out (14).
  • This process may be performed by means of a two- or multiple- roll calender with rolls of specific diameter, heated up to the required temperature. Calendering process provides high density and certain thickness to the manufactured carbon electrode.
  • This invention allows to produce electrode active material of super capacitor with thickness not less than 1000 microns, allowing to increase specific electrical, energy and performance parameters of supercapacitors and hybrid energy storage devices and is characterized by a resistance of not higher than 1 Om*cm, resistance uniformity along the surface not higher than 10% and a tensile strength in all directions not less than 0.1 MPa.
  • the produced electrodes are applicable for the manufacture of electric energy storage devices with high specific capacitance. They can be used both in stationary electric energy storage systems and vehicles. Exemplary embodiments: Example 1
  • the original powders of the activated carbon powder with size of 7 microns (D50) and carbon black were mutually grinded in a vibrating ball mill MB-001 in proportion 10 parts of porous carbon powder to 1 part of acetylene black.
  • PTFE suspension of 6% mass concentration in relation to dry components was used as a binder.
  • the obtained pasty substance was transported to the mechanical grater with holes of 2 mm in diameter.
  • the strip obtained as a result of previous stage was cut into separate pieces of rhomb shape with one of the angles at the vertex of 60°. Each side of rhombs were 0,25 m in length.
  • the strip obtained at the previous step was exposed to recurrent cutting into separate pieces of rhomb shape with one of the vertex angles of 60°. Each side of rhombs were 0,25 m in length. 10.
  • the pieces obtained at the previous step were continuously laid one above the other in direction parallel to one of the rhombs sides in 5 layers with 50 mm horizontal displacement between them and rolled through a caterpillar press with initial gap of 6 mm and final gap of 4 mm between the belts. As a result, a 4- mm strip has been obtained.
  • the strip obtained at the previous step was put on a smooth horizontal surface and exposed to drying in the drying chamber at the temperature of 130°C during 4 hours.
  • the dried strip was fed into a calender with heated rolls having diameter 250 mm with a gap of 2 mm between them.
  • An asymmetrical electrochemical capacitor was assembled, containing 20 carbon electrode sheets, 11 current collectors, 10 lead-oxide electrodes, a separator, electrolyte in a form of 35% aqueous solution of sulfuric acid and a box containing the indicated components.
  • Maximum capacity of the device was equal to 260 Ah, and specific energy - 0,17 MJ/kg.
  • the electric energy storage devices in the amount of 6 pieces were connected in series and mutually with control charge-discharge equipment and a power inverter installed on a transportation device containing internal combustion engine. As a result, energy saving due to the braking energy recuperation reached 40%. 16.
  • the electric energy storage devices in the amount of 6 pieces were connected in series and mutually with control charge-discharge equipment and a power inverter were used as uninterruptible power supply. As a result, a continuous load of 500 W was kept operating during 4 h 45 m.
  • a colloidal dispersion of carbon black was mixed with porous carbon powder in 1:10 proportion during 3 minutes using a planetary mixer.
  • PTFE dispersion in the amount of 6% mass concentration in relation to dry components was used as a binder.
  • Carbon materials dispersions were mixed with PTFE binder solution within 3 minutes using a planetary mixer.
  • the obtained pasty mass was transported to the mechanical grater with holes of 2 mm in diameter.
  • the strip obtained at the previous stage was cut into separate pieces of rhomb shape with one of the angles at the vertices of 60°. Each side of rhombs were 0,25 m in length.
  • the dried strip was fed into a calender with heated rolls having diameter 250 mm with a gap of 2 mm between them.
  • An asymmetrical electrochemical capacitor was assembled, containing 20 carbon electrode sheets, 11 current collectors, 10 lead-oxide electrodes, a separator, electrolyte in a form of 35% aqueous solution of sulfuric acid and a box containing all the indicated components.
  • Maximum capacity of the device was equal to 260 Ah and specific energy - 0,17 MJ/kg.
  • the electric energy storage devices in the amount of 6 pieces were connected in series and mutually with control charge-discharge equipment and a power inverter were installed on a transportation device containing internal combustion engine. As a result, energy saving due to the braking energy recuperation reached 40%.
  • the obtained pasty substance was then transported to the mechanical grater with holes of 2 mm in diameter.
  • the strip obtained at the previous stage was cut into separate pieces of rhomb shape with one of the angles at the vertices of 60°. Each side of rhombs were 0,25 m in length.
  • the strip obtained at the previous step was fed into a calender with heated rolls having diameter 250 mm with a gap of 2 mm between them. 10.
  • the strip obtained at the previous step was exposed to recurrent cutting into separate pieces of rhomb shape with one of the vertex angles of 60°. Each side of rhombs were 0,25 m in length.
  • the pieces obtained at the previous step were continuously put one above the other in direction parallel to one of the rhombs sides in 5 layers with 50 mm horizontal displacement between them and rolled through a caterpillar press with initial gap of 10 mm and final gap of 8 mm between the belts. As a result, a 8- mm strip has been obtained.
  • the strip obtained at the previous step was fed into a calender with heated rolls having diameter 250 mm with a gap of 4 mm between them.
  • the strip obtained at the previous step was put on a smooth horizontal surface and exposed to drying in the drying chamber at the temperature of 130°C during 5 hours.
  • the dried strip was fed into a calender with heated rolls having diameter 250 mm with a gap of 2 mm between them.
  • An asymmetrical electrochemical capacitor was assembled, containing 20 carbon electrode sheets, 11 current collectors, 10 lead-oxide electrodes, a separator, electrolyte in a form of 35% aqueous solution of sulfuric acid and a box containing all the indicated components.
  • Maximum capacity of the device was 250 Ah and specific energy - 0,16 MJ/kg.
  • the electric energy storage devices in the amount of 6 pieces were connected in series and mutually with control charge-discharge equipment and a power inverter were installed on a transportation device containing internal combustion engine. As a result, energy saving due to the braking energy recuperation reached 40%.
  • the electric energy storage devices in the amount of 6 pieces were connected in series and mutually with control charge-discharge equipment and a power inverter were used as uninterruptible power supply. As a result, a continuous load of 500 W was kept operating during 4 h 20 m.
  • a carbon pasty substance obtained at the previous step was fed to the lab extruder with screws diameter of 35 mm, L:D - 40:1. Rotation speed - 64 rpm, temperature of material cylinder - 25°C.
  • the obtained pasty substance was transported to the mechanical grater with holes of 2 mm in diameter. 6. 1-3 mm sized granules were supplied to hopper, located above the horizontal rolls with diameter of 240 mm and a gap of 1 mm between them.
  • the strip obtained at the previous stage was cut into separate pieces of rhomb shape with one of the angles at the vertices of 60°. Each side of rhombs were 0,25 m in length.
  • the strip obtained at the previous step was fed into a calender with heated rolls having diameter 250 mm with a gap of 2 mm between them.
  • the strip obtained at the previous step was exposed to recurrent cutting into separate pieces of rhomb shape with one of the vertex angles of 60°. Each side of rhombs were 0,25 m in length.
  • the strip obtained at the previous step was fed into a calender with heated rolls having diameter 250 mm with a gap of 2 mm between them.
  • the strip obtained at the previous step was put on a smooth horizontal surface and exposed to drying in the drying chamber at the temperature of 130°C during 5 hours.
  • An asymmetrical electrochemical capacitor was assembled, containing 20 carbon electrode sheets, 11 current collectors, 10 lead-oxide electrodes, a separator, electrolyte in a form of 35% aqueous solution of sulfuric acid and a box containing all the indicated components.
  • Maximum capacity of the device was 220 Ah and specific energy - 0,14 MJ/kg.
  • the electric energy storage devices in the amount of 6 pieces were connected in series and mutually with control charge-discharge equipment and a power inverter were installed on a transportation device containing internal combustion engine. As a result, energy saving due to the braking energy recuperation reached 35%.
  • the electric energy storage devices in the amount of 6 pieces were connected in series and mutually with control charge-discharge equipment and a power inverter were used as uninterruptible power supply. As a result, a continuous load of 500 W was kept operating during 4 h 00 m.

Landscapes

  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Power Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Manufacturing & Machinery (AREA)
  • Electric Double-Layer Capacitors Or The Like (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

L'invention porte sur le champ technique de l'ingénierie électrique, en particulier le champ technique des techniques de fabrication d'électrodes en carbone poreuses. Un mode de réalisation du procédé de fabrication d'électrode en carbone consiste : à mélanger et homogénéiser un matériau de carbone poreux à un additif conducteur, un liant polymère et un liquide de traitement, à homogénéiser le mélange obtenu, à obtenir les granules du mélange, à rouler les granules à travers un laminoir pour obtenir un produit semi-fini en forme de bande, à couper la bande en pièces de forme spécifique, à empiler les pièces les unes sur les autres dans une chaîne à couches multiples continue à chevauchement partiel sur la base de la supposition que l'aire de contact entre les pièces adjacentes est sensiblement constante et de valeur préétablie, à presser la chaîne de pièces jusqu'à ce qu'un semi-produit sous forme d'une bande de carbone soit formé, à sécher le semi-produit obtenu et enfin à calandrer le semi-produit pour obtenir l'électrode en carbone ayant les paramètres requis.
PCT/RU2013/000341 2013-04-22 2013-04-22 Électrode en carbone et procédé de fabrication d'électrode en carbone WO2014175756A1 (fr)

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PCT/RU2013/000341 WO2014175756A1 (fr) 2013-04-22 2013-04-22 Électrode en carbone et procédé de fabrication d'électrode en carbone

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CN108470648A (zh) * 2018-06-20 2018-08-31 深圳清华大学研究院 多孔电极片及其制备方法和电容器
DE102018211189A1 (de) * 2018-07-06 2020-01-09 Robert Bosch Gmbh Verfahren und Vorrichtung zur Herstellung eines Elektrodenmaterialbandes
CN110692150A (zh) * 2017-09-29 2020-01-14 株式会社Lg化学 电极混合物制造方法和电极混合物
CN114039024A (zh) * 2021-11-08 2022-02-11 上海联净电子科技有限公司 水系电池石墨电极材料的生产方法以及装置
CN114207864A (zh) * 2019-01-16 2022-03-18 麦斯韦尔技术股份有限公司 用于制造干电极的系统和方法
DE102020216546A1 (de) 2020-12-23 2022-06-23 Volkswagen Aktiengesellschaft Verfahren zur Herstellung einer Elektrodenpulvermischung einer Batteriezelle
CN114830374A (zh) * 2019-12-27 2022-07-29 日本瑞翁株式会社 电化学装置用构件的制造或再利用方法、电化学装置的制造方法、电化学装置用构件、以及电化学装置

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RU2098879C1 (ru) * 1994-03-11 1997-12-10 Наталия Корнеевна Товстюк Конденсатор большой мощности на двойном электрическом слое
US20100119699A1 (en) * 2003-07-09 2010-05-13 Maxwell Technologies, Inc. Particle based electrodes and methods of making same
RU2427052C1 (ru) * 2010-04-19 2011-08-20 Открытое акционерное общество Воронежское специальное конструкторское бюро "Рикон" (ОАО ВСКБ "Рикон") Электродный материал для конденсатора электрического, способ его изготовления и суперконденсатор электрический

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110692150A (zh) * 2017-09-29 2020-01-14 株式会社Lg化学 电极混合物制造方法和电极混合物
CN108470648A (zh) * 2018-06-20 2018-08-31 深圳清华大学研究院 多孔电极片及其制备方法和电容器
CN108470648B (zh) * 2018-06-20 2020-07-28 深圳清华大学研究院 多孔电极片及其制备方法和电容器
DE102018211189A1 (de) * 2018-07-06 2020-01-09 Robert Bosch Gmbh Verfahren und Vorrichtung zur Herstellung eines Elektrodenmaterialbandes
CN114207864A (zh) * 2019-01-16 2022-03-18 麦斯韦尔技术股份有限公司 用于制造干电极的系统和方法
CN114830374A (zh) * 2019-12-27 2022-07-29 日本瑞翁株式会社 电化学装置用构件的制造或再利用方法、电化学装置的制造方法、电化学装置用构件、以及电化学装置
DE102020216546A1 (de) 2020-12-23 2022-06-23 Volkswagen Aktiengesellschaft Verfahren zur Herstellung einer Elektrodenpulvermischung einer Batteriezelle
EP4020615A1 (fr) * 2020-12-23 2022-06-29 Volkswagen Ag Procédé de production d'un mélange pulvérulent d'électrode d'un élément de batterie
CN114039024A (zh) * 2021-11-08 2022-02-11 上海联净电子科技有限公司 水系电池石墨电极材料的生产方法以及装置

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