TW201322287A - A multi-element electrochemical capacitor and a method for manufacturing the same - Google Patents

Abstract

The invention relates to electrical engineering, in particular, to the manufacture of electrochemical capacitors having a combined charge storage mechanism or other similar rechargeable energy storages. A multi-element electrochemical capacitor consisting of at least one layer of insulating film and alternating opposite-polarity electrode sheets placed thereon in succession and interspaced by a porous ion-permeable separator, all coiled into a roll and impregnated with electrolyte, each electrode sheet being a substrate made of nonwoven polymer material of a high pore ratio, with at least one electrode secured to one side or both sides thereof, or embedded within the same, the electrodes of the opposite-polarity electrode sheets consisting of nano-structured carbon materials of different types, one of said materials having the largest possible specific surface area and a relatively low conductance, and the other material having a relatively large specific surface area and a relatively high conductance. The electrodes further comprising nano-sized particles of a metal or compounds thereof, or redox polymers. In the proposed invention is increased specific characteristics of an electrochemical energy storage, stability of its specific characteristics, and longer service life.

Description

Multi-element electrochemical capacitor and method of manufacturing same

This invention relates to electrical engineering, in particular, to the fabrication of electrochemical capacitors having a combined charge storage mechanism or other similar rechargeable energy storage.

The closest related prior art to the present invention is disclosed in the application No. WO 2009103661 (Applicant BATSCAP, France et al.), published on Aug. 27, 2009, which is directed to the design of a multi-component capacitor and its method of manufacture. The capacitor comprises at least two adjacent composite electrodes spaced apart by a distance d and at least one composite electrode shared by the two electrodes and held apart from each other by a porous separator that is crimped into a spiral generating reel.

A drawback of this prior art invention is that its multi-element capacitor design uses individual components in the form of spaced apart electrodes and is therefore difficult to manufacture from multiple components, particularly in a continuous reel assembly process. The drawback is also that it uses a multilayer composite structure, ie the electrodes are applied to the surface of the metal collector. This design leads to unavoidable problems when providing reliable low resistance contact between the electrodes and the current collector. Furthermore, the discontinuous electrode material may be responsible for the improper reaction between the electrolyte and the current collector material and the operating voltage of the capacitor is reduced due to the electrochemical decomposition potential of the current collector. The lack of insulation between adjacent capacitor electrodes is another significant drawback of prior art designs that reduces the voltage and thus the specific energy of the capacitor. Therefore, when the capacitor segments are connected in series, the potential difference of the electrodes may be on the order of twice the operating voltage of the capacitor elements. This in turn may trigger an electrochemical electrode reaction, thereby limiting the useful life of the capacitor.

It is an object of the present invention to develop a segmented multi-element electrochemical reel type capacitor that does not have the drawbacks closest to the related prior art and that has specific performance characteristics acceptable in electrical engineering, and that particular performance characteristics make it an engineering A reasonable and economical choice of use.

The technical result of the present invention is the specific characteristics of the improved electrochemical energy storage, the stability of its particular features, and the long service life.

The technical result is achieved in a multi-element electrochemical capacitor consisting of at least one insulating film and alternating opposite polarity electrode sheets disposed thereon and separated by a porous ion permeable separator, all of which are wound into a roll and Impregnated with an electrolyte, each electrode sheet is a substrate made of a high porosity non-woven polymer material, and has at least one electrode fastened to one side or both sides or embedded therein, and electrodes of opposite polarity electrode sheets are Different types of nanostructured carbon materials, one of which has the largest possible specific surface area and relatively low electrical conductivity, while the other material has a relatively large specific surface area and a relatively high electrical conductivity, the electrodes Further comprising nanoparticles of a metal or a compound thereof or a redox polymer.

The substrate is made of a material that is chemically inert and electrochemically inert in the electrolyte and is electron impermeable and ion impermeable. The electrode is composed of a carbon nanomaterial such as activated carbon, activated carbon black, metal impregnated carbon mixed with several layers of thick carbon nanotubes, a nano carbon material based on carbides of metals such as boron, titanium and niobium, and natural flakes. A composition in which graphite or acetylene black is mixed. The nanostructured carbon material consists of several layers of thick carbon nanotubes. The electrochemically active layer of the electrode sheet disposed in contact with the electrically insulating film faces the electrically insulating film, and the next electrode sheet is disposed to be displaced to half the width of the electrochemically active layer thereof, and the electrochemically active layers of the electrode sheets face each other And separated by a porous ion permeability separator. The electrode is continuously fastened to the substrate.

The technical structure is also achieved in a method of fabricating a multi-element electrochemical capacitor, the method comprising preparing an electrode mixture composed of different types of nanostructured carbon materials, one of the materials having a maximum possible specific surface area and a relatively low electrical conductivity, And another material has a relatively large specific surface area and a relatively high electrical conductivity; a metal-sized or a compound thereof or a nano-sized particle of a redox polymer is added to the electrode mixture; by fastening the electrode mixture to each One or both sides of a substrate made of a high porosity non-woven polymer material of an electrode sheet or embedded therein to produce opposite polarity electrode sheets; opposite polarity electrode sheets spaced apart by a porous ion permeability separator Continuously covering at least one layer of electrically insulating film; crimping the layers to form a roll; and impregnating the roll with an electrolyte.

A multilayered carbon nanotube obtained by pyrolysis of a mixture of a gaseous hydrocarbon and hydrogen and having a size of 5 to 50 nm, a specific surface area of 500 to 1,000 m ² /g, and a specific conductivity of 10 to 100 Sm/cm As a nanostructured carbon material, activated carbon obtained from a carbide material and a nanoporous carbon material are used as another nanostructured carbon material. Pyrolysis of a mixture of gaseous hydrocarbons and hydrogen is carried out on a catalyst such as a cobalt- and molybdenum-based compound at a temperature maintained in the range of 650 ° C to 900 ° C and a pressure in the range of 0.1 to 1.0 MPa, and using natural gas or propane or Butane or ethylene is used as a gaseous hydrocarbon. The carbon nanotubes are produced by pyrolyzing a mixture of an aromatic hydrocarbon and an alcohol. Pyrolysis of a mixture of an aromatic hydrocarbon and an alcohol is carried out on a catalyst such as a compound based on iron, nickel and magnesium oxide at a temperature maintained in the range of 650 ° C to 900 ° C and a pressure in the range of 0.1 to 1.0 MPa, and is used Benzene and toluene are used as aromatic hydrocarbons, and ethanol is used as the alcohol. After the carbon nanotubes are produced, they are treated with oxidizing agents, ultrasonic waves and water under supercritical conditions to increase their specific surface area. Activated carbon is produced by forming a synthetic monomer in a fluid, followed by carbonization and high temperature vapor activation at a temperature of 600 ° C to 1,100 ° C. The nanoporous carbon material is produced from carbides of boron, titanium and niobium, and then subjected to high temperature thermochemical treatment with chlorine gas at a temperature between 600 ° C and 1,200 ° C. To prepare the electrode mixture, the thin carbon nanotubes are mixed with activated carbon in a ratio of 1:3 to 3:1 and ground to a particle size of 10 to 100 nm in a ball mill, sieved at 100 nm mesh, and super The sonication is performed to prepare an electrode mixture that is as homogeneous as possible. The positive electrode is composed of a metal such as magnesium, mercury, silver, and nickel, and a nanosized particle such as a metal compound of magnesium oxide, magnesium hydroxide, oxidized mercury, silver oxide, lead oxide, lead sulfate, nickel hydroxide, and lithium cobalt oxide. Manufacturing. The negative electrode is made of a nano-sized particle such as a metal of zinc, lead, cadmium, iron, and lithium, and a metal compound such as zinc hydroxide, zinc chloride, lead sulfate, cadmium hydroxide, and iron hydroxide. The electrode sheet is produced by coating the electrode mixture on the porous polymer sheet in the form of an electrode suspension containing the electrode mixture dispersed in an organic solvent by ultrasonic waves. Isopropanol or ethanol is used as an organic solvent for preparing an electrode suspension. The electrode mixture is applied to the porous polymer sheet by electrostatic force in the form of a powder. After coating the electrode mixture, the electrode sheet is placed on a contact electrode such as a graphite foil, which is then heated to a temperature between 120 ° C and 150 ° C and subjected to a pressure of 0.5 to 1.0 MPa. A porous separator having a thickness of one to four layers may be made of a polymer film having a thickness of 3 to 5 μm, a porosity of 20% to 40%, and a pore size of 0.05 to 0.1 μm, or a thickness of 10 μm and a density of 15 a sheet of a non-woven polymer material such as propylene up to 40 mg/cm ² , or an ion-permeable polymer made of polybenzimidazole having a thickness of 10 to 15 μm, impregnated with an electrolyte and containing 3 to 10 parts by mass of an electrolyte Membrane obtained. The electrode reel is fabricated from a length of the electrode sheet at an opposite end of the electrically insulating film contacting the contact electrode, one end of the contact electrode is connected to the center electrode, and the double layer electrode sheet is wound around the center electrode so as to be in contact with the second electrode sheet The second length of the electrode sheet forms the outer surface of the roll; and the outer surface of the roll is connected to the outer peripheral electrode. The center electrode and the peripheral electrode are made of a metal tube such as aluminum or an alloy thereof, and a cap of an electrically insulating material (for example, plastic) is interposed between the center electrode and the peripheral electrode at both ends of the electrode roll, and the cap of the electrically insulating material is attached thereto. The reel has been inserted after being impregnated with electrolyte. The electrolyte used for impregnating the electrode reel is an organic electrolyte, that is, containing an ammonium or imidazole-based cation and including tetrafluoroborate, hexafluorophosphate or trifluoromethanesulfonimide or bistrifluoromethanesulfonimide or An organic salt solution of an anion of hexafluoroethyltrifluorophosphate in acetonitrile or propylene carbonate or formamide, or a mixed electrolyte, that is, a solution of zinc chloride in acetonitrile or an inorganic electrolyte , that is, an aqueous solution of potassium base. The electrode reel is impregnated with electrolyte in a vacuum chamber, for example at a residual pressure of 10 Pa. In accordance with the method of the present invention, a plurality of parallel electrode sheets are wound into a roll and placed in a parallelepiped or cylindrically shaped outer casing.

As shown in FIGS. 1 to 7, it is a multi-element electrochemical capacitor of the present invention and a method of manufacturing the same . The multi-element electrochemical capacitor (Figs. 1 to 3) comprises at least one electrically insulating film 40; an electrode sheet 10 which is a substrate 11 having electrodes 1 continuously fastened thereon; and an electrode sheet 20 having electrodes 2 The substrate 11 is continuously fastened thereto, and the electrode sheets are spaced apart by the porous separator 30. Each of the layers of the electrically insulating film, the electrode sheets 10 and 20, and the porous separator are wound into a roll and impregnated with an ion permeable electrolyte.

The electrodes 1 and 2 are made of a carbon nanomaterial such as activated carbon, activated carbon black, metal-impregnated carbon, or a metal based on, for example, Ti, B or Si, mixed with a carbon nanotube (for example, a plurality of thick carbon nanotubes). The carbide (CDC) nanocarbon material is made of a combination of natural flake graphite or thermally expanded graphite or acetylene black. The type, ratio and distribution of the composition components in the electrode area depend on the polarity of the working portion of the electrode, the type of electrolyte and the applied voltage. For example, when ethyl tetramethylborate tetrafluoroborate (EMIM BF4) is used, it is preferred to use a specific absorption surface area in the range of 1,500 to 1,800 cm ² /g according to the BAT method, preferably having a size according to the size. Peak pore distribution, and pore size in the range of 0.6 to 0.8 nm, submicropore size in the range of 1.1 to 1.5 nm and specific pore volume of 0.7 to 0.9 cm ³ /g, volume ratio of 1:2 to 2:1 Activated carbon or boron carbide based CDC. Even if the activated carbon and CDC having the above parameters do not exhibit high specific conductivity, they can provide a high charge surface density. To enhance the local conductivity, a carbon nanotube is added to the composition, preferably having a thin wall and a diameter in the range of 7 to 12 nm and a ratio in the range of 700 to 900 cm ² /g according to the BAT method. A carbon nanotube that absorbs surface area. The ratio of the nanocarbon material to the added carbon nanotubes is preferably in the range of 1:3 to 3:1.

By adding 10% by mass to 20% by mass of a highly conductive carbon material such as natural flake graphite or thermally expanded graphite or acetylene black, the integrated volume conductivity of the composition can be increased and a lower electrode resistance can be achieved.

The porous separator 30 may be, for example, a track film having a thickness of 3 to 5 μm, a porosity of 20% to 40%, and a pore size of 0.05 to 0.1 μm made of a polymer film such as PVDF, or a thickness of 10 μm and a density of 15 Sheet of non-woven polymer material (polypropylene) up to 40 mg/cm ² , or ion permeation of 10 to 15 μm thick, electrolyte impregnated and containing 3 to 10 parts by mass of electrolyte obtained from PBI (polybenzimidazole) A polymer film is provided.

The substrate 11 of the electrode sheets 10 and 20 of the electrochemical capacitor of the present invention is made of a material which is chemically inert and electrochemically inert in the working electrolyte, such as polypropylene (PP) produced by, for example, extrusion, or borrowed. The PVDF obtained by, for example, extrusion, or electrospun polytetrafluoroethylene (PTFE) or carbon fiber produced by, for example, extrusion. The thickness and specific porosity of the substrate are selected in consideration of ease of assembly and specific parameters, such as a thickness of 10 to 100 μm and a density in the range of 15 to 45 mg/cm ² .

If the pair of electrodes are connected in series, the length of the electrode sheets 10 and 20 is set such that the displacement is equal to one half of the width of the electrode, and the electrochemically active layers thereof face each other to produce alternating pairs of opposite polarity electrodes. The composition of the opposite portions of the electrodes of the two sheets is selected in consideration of the predetermined polarity of the charge generated on the inner surface of the electrochemically active material of the respective electrode portions, or depending on the type of material used and the requirements of the multi-element electrochemical capacitor. The parameters are the same. The two halves of the peripheral electrode of the electrode sheet serve as a current collector common to all of the basic capacitors produced by the alternating electrodes and connected in series. In order to maintain reliable electrical contact with the external switching line and to seal the internal space of the multi-element capacitor, the peripheral electrode is brought into contact with the contact electrode 12 made of a conductive carbon material such as a graphite foil.

Electrochemically active surface material of the positively charged working portion of electrodes 1 and 2 of the electrochemical capacitor of the present invention by using a metal such as magnesium or nickel, a metal compound such as magnesium oxide or nickel hydroxide, or a redox polymer The nano-sized particles are added to a composite electrode mixture comprising, for example, a thin-walled carbon nanotube and activated carbon black to be chemically and/or electrochemically produced.

The electrochemically active surface material of the negatively charged working portion of the electrodes 1 and 2 of the electrochemical capacitor of the present invention is oxidized by a metal such as zinc or iron, a metal compound such as magnesium hydroxide or iron hydroxide. The nanosized particles of the reduced polymer are added to the composite electrode mixture comprising, for example, a thin-walled carbon nanotube and activated carbon black to be chemically and/or electrochemically produced.

The foregoing chemical and/or electrochemical treatment of the electrochemically active material in a particular embodiment of the electrochemical capacitor of the present invention can be carried out in a sulfuric acid or phosphoric acid aqueous solution having a concentration of from 1% by mass to 30% by mass in the organic acid and potassium salt of the inorganic acid. An aqueous or non-aqueous solution of a salt, a sodium salt or an ammonium salt such as an alkali metal or ammonium or a composite compound of a sulfate, a chloride, a fluoride, a phosphate, a diphosphate, an acetate, a tartrate and a formate. It is carried out or in an aqueous solution or a water-organic solution having a concentration of 1% by mass to 70% by mass of a base.

The metal or its compound or the redox polymer additive changes the structure and composition of the positively charged and negatively charged working portion of the electrodes 1 and 2, and can improve the operational characteristics of the electrode and the capacitor as a whole, such as by reversible oxidation The energy output growth caused by the reduction reaction, the working voltage is high, and the mechanical properties of the coating are improved.

Electrode 1 and 2 are chemically and/or electrochemically coated with an electrode material and an electrolyte in a range of 1:1 to 1:2 by ultrasonic dispersion with or without a solvent added to the polymer frame of the electrode sheet. The mass is obtained by dispersing a dispersion of the electrode mixture prepared in an organic electrolyte (ionic liquid), followed by treating the dispersion prepared as above in a vacuum.

The organic electrolyte is added by applying an aerosol dispersion of a solvent or a solvent-free organic electrolyte to the electrode sheet before winding, or by impregnating the composite electrode material and the porous separator during the winding process, or The composite electrode material is pre-impregnated under critical CO ₂ conditions, or a multi-component capacitor wound into a roll is placed in an electrolyte bath, or a composite electrode material and a porous separator wound into a multi-element capacitor are immersed under supercritical CO ₂ conditions.

In a particular embodiment of the electrochemical capacitor of the present invention, the thickness of the substrate 11 can vary from 5 to 150 μm, preferably between 10 and 50 μm, and the thickness of the electrochemically active layer of electrodes 1 and 2 is between 100 and In the range of 500 μm, preferably between 300 and 400 μm.

The electrode sheets 10 and 20 as provided above and spaced apart by the porous separator 30 are disposed on the electric insulating film 40 and subjected to heat treatment (lamination) under pressure to seal the electrode sheets of the divided electrodes, and then the electrode sheets and the porous separator And the electrically insulating film is wound together into a roll 50, the roll 50 comprising an electrically insulating film supported thereon to be disposed opposite to each other with a displacement equal to one half of the width of the electrodes 1 and 2 and separated by a porous separator The length of the electrode sheet.

To produce an electrode roll, the electrode sheet protrudes beyond the peripheral electrode of the last opposite electrode at the opposite end of the electrically insulating film to the conductive current collector; one of the peripheral electrodes is connected to the central current collector 13; and the double electrode sheet is wound around the center The current collector is crimped to form a peripheral current collector 12 on the outer surface of the drum, the peripheral current collector 12 being coupled to the second electrode. The center and peripheral current collectors are made of a metal tube such as aluminum and its alloy, and a cap 60 of electrically insulating material (e.g., plastic) is inserted between the center and the peripheral current collector at both ends of the electrode roll. Typically, the cap of electrically insulating material is inserted after the electrode reel has been impregnated with the electrolyte. The point of contact between the cap and the end edge of the coiled electrode roll is sealed by known methods, such as by an epoxy based composition.

The electrolyte used to impregnate the electrode reel is an organic electrolyte, that is, a solution based on, for example, an organic salt of tetraalkylammonium tetrafluoroborate or dialkylimidazolium tetrafluoroborate in an organic solvent such as acetonitrile, or contains, for example, chlorination. The inorganic salt of zinc is a mixed electrolyte in an organic solvent such as acetonitrile, or an inorganic electrolyte such as an aqueous solution of potassium base. The electrode reel is impregnated with electrolyte in a vacuum chamber, for example at a residual pressure of 10 Pa.

The electrochemical capacitor may comprise an electrode sheet or a plurality of parallel electrode sheets wound into a roll and impregnated with an electrolyte. One electrode sheet or a plurality of electrode sheets impregnated with the electrolyte may be disposed in a parallelepiped-shaped outer casing.

The electrochemical capacitor assembled as described above is ready for immediate use. To improve the energy characteristics of the electrochemical capacitor, it should be operated at a high temperature in the range of 30 ° C to 65 ° C, preferably at 60 ° C. The electrochemical capacitor is charged at a relatively high current with constant current conditions. The individual electrochemical capacitors are connected in a parallel and series circuit to a battery pack that delivers the optimal energy and power output of the charge stored by the capacitor.

Moreover, unlike the closest prior art, the electrochemical capacitor is substantially equal to a conventional electrochemical capacitor having a carbon electrode and using a two-layer charge storage mechanism or a chemical current source using a reversible redox chemical reaction. Cost improves specific characteristics (specific energy output, energy density, current density, specific power, specific charge and voltage). This contributes to the achievement of the object of the invention for the development of electrochemical capacitors having specific characteristics, with particular features making it a technically suitable and economical choice of use.

The multilayer electrochemical capacitor produced by the method of the present invention operates at a temperature in the range of 30 ° C to 60 ° C. The electrochemical capacitor is charged under constant current conditions and its parameters (discharge current and voltage) are controlled during its discharge.

The feasibility of the multi-element electrochemical capacitor of the present invention is illustrated by the following examples:

Example 1

Assemble a three-element capacitor. An electrode having a size of 80×45 mm ² and an active FAS carbon having a total weight of 0.14 g and a ratio of 1:1:1 and a carbon nanotube obtained by pyrolysis of benzene on a ferrocene-containing catalyst and A mixture of ASCG silicone added thereto is prepared. The ball mill was ground for 20 minutes and the solution of the carbon material in ethanol was initially treated with a 10 W ultrasonic source for 10 minutes, and then applied to the GF-D graphite foil as an aerosol dispersion. Adjacent electrodes are spaced 5 mm apart. The electrodes were separated by a separator consisting of a four-layer track film having a porosity of 11.7% and a thickness of 23 μm. The electrodes and membranes were impregnated with an EMIM BF4 (Merck) ionic fluid. Figure 5 shows a cyclic voltage-current plot at a charge-discharge rate of 50 mV/sec. The specific parameters calculated based on the CVA data are as follows: charging voltage dU=9V, C=0.4°F; E _charging = 47.7 W.hr per kilogram of active electrode material, and E _discharge = 32.2 W.hr per kilogram of active electrode material, And the efficiency is equal to 67.6%. Figure 5 illustrates an example of a cyclic voltage-current diagram of a three-element capacitor fabricated by the method of the present invention and comprising two electrode sheets each having two fastenings thereon and made of a PVDF track film a composite carbon material electrode separated by a porous separator, the porous separator being impregnated with an ionic fluid of 1-butyl-3-methyl-imidazole tetrafluoroborate;

Example 2

Assemble a 60-element capacitor. Electrode measuring 200×85 mm ² by activated carbon (coco substrate) with a ratio of 2:2:1 and carbon nanotubes obtained by toluene pyrolysis on a catalyst containing ferrocene and adding Made of carbon black to it. The ball mill was ground for 20 minutes and the carbon material in ethanol was preliminarily treated with a 10 W ultrasonic source for 10 minutes, and then coated with an aerosol dispersion on a GF-D graphite foil to a thickness of 140 μm. The electrode material weighed 46.8 g. Adjacent electrodes are spaced 5 mm apart. The electrodes were spaced apart by a porous separator consisting of a four-layer track film having a porosity of 11.7% and a thickness of 23 μm. The electrode and membrane were impregnated with an electrolyte 1 M KOH solution. When a specific parameter is calculated based on voltage and current over time, the stored energy is 2.7 W.hr per kilogram of active electrode mass. As a result of Example 2, an exemplary charge-discharge cycle (charge current 0.4 A) of one of the 60-element capacitors having a 1 M KOH electrolyte is illustrated in FIG.

Example 3

Assemble a 15-component capacitor. An electrode measuring 40×85 mm2 is made up of a ratio of 5:1 activated carbon black PFT-O and a carbon nanotube obtained by pyrolysis of methane on a catalyst containing cobalt and molybdenum and 20 added thereto. % made of GSM-2 graphite. The ball mill was ground for 20 minutes and the carbon material in ethanol was initially treated with a 10 W ultrasonic source for 10 minutes, and then coated as an aerosol dispersion on a non-woven polypropylene sheet to a layer having a thickness of 90 μm. The electrode material coated on the length of the GF-D graphite foil weighed 1.1 g. Adjacent electrodes are spaced 5 mm apart. The electrodes were spaced apart by a porous separator consisting of two layers of track membranes having a porosity of 11.7% and a thickness of 23 μm. The electrode and membrane were impregnated with an electrolyte EMIM BF4 (Merck) ionic fluid. When a specific parameter is calculated based on the voltage and current data over time, the stored discharge energy is 41 W.hr per kilogram of active electrode mass at a charging voltage of 45 V and 107 W per kilogram of active electrode mass at a charging voltage of 60 V electrode. .hr. The specific power at discharge was 13.5 kW per kilogram of active electrode at a charging voltage of 45 V and 14.3 kW per kilogram of active electrode at a charging voltage of 65 V. Figure 7. The ordinate is the charge-discharge energy (Joules) and the abscissa is the time (seconds).

In the upper graph, the yellow curve shows the charge-discharge energy dependence with time when the charge voltage is 45 volts; the blue curve shows the charge-discharge energy dependence with time when the discharge voltage is 45 volts.

In the lower graph, the yellow curve illustrates the charge-discharge energy dependence with time when the charge voltage is 60 volts; the blue curve illustrates the charge-discharge energy dependence with time when the discharge voltage is 60 volts.

1. . . electrode

2. . . electrode

10. . . Electrode sheet

11. . . Substrate

12. . . Contact electrode

13. . . Current collector

20. . . Electrode sheet

30. . . Porous separator

40. . . Electrical insulating film

50. . . reel

60. . . Cap

Figure 1 is a diagram of a multi-element electrochemical capacitor;

2 is a diagram showing the structure of a multi-element electrochemical capacitor, showing a stack of an electrically insulating film and an electrode sheet, and a porous separator disposed therebetween;

Figure 3 is a diagram showing the structure of a multi-element electrochemical capacitor showing the position of the electrode of the electrode sheet wound into a reel;

4 is a view of an electrode made of a composite nanostructured carbon material composed of active FAS carbon and carbon nanotubes;

Figure 5 illustrates an example of a cyclic voltage-current diagram of a three-element capacitor fabricated by the method of the present invention and comprising two electrode sheets each having two fastenings thereon and made of a PVDF track film a composite carbon material electrode separated by a porous separator, the porous separator being impregnated with an ionic fluid of 1-butyl-3-methyl-imidazole tetrafluoroborate;

Figure 6 illustrates an exemplary charge-discharge cycle (charge current 0.4 A) of one of a 60-element capacitor having a 1 M KOH electrolyte;

Figure 7 illustrates an example of calculation of charge-discharge energy of a 15-element capacitor containing an EMIM BF4 organic electrolyte.

10. . . Electrode sheet

20. . . Electrode sheet

30. . . Porous separator

40. . . Electrical insulating film

50. . . reel

Claims (26)

A multi-element electrochemical capacitor comprising at least one electrically insulating film and alternating opposite polarity electrode sheets disposed thereon and spaced apart by a porous ion permeable separator, the electrode sheets and the porous separator being wound into a roll, Each of the electrode sheets is a substrate of a non-woven polymer material having a high porosity and having at least one electrode fastened to one or both sides or embedded therein The electrodes of the opposite polarity electrode sheets are made of different types of nanostructured carbon materials, one of the nanostructured carbon materials having the largest possible specific surface area and a relatively low electrical conductivity, and the second nanometer The structural material has a relatively large specific surface area and a relatively high electrical conductivity, and the electrodes further contain nanoparticles of a metal or a compound thereof or a redox polymer. The multi-component electrochemical capacitor of claim 1, wherein the substrate is made of an electron impermeable and ion-impermeable material that is chemically inert and electrochemically inert in the electrolyte. The multi-component electrochemical capacitor of claim 1, wherein the electrodes are made of a carbon material such as activated carbon, activated carbon black, metal impregnated carbon mixed with a plurality of layers of carbon nanotubes. A form of a composition in which a nanocarbon material based on a carbide of a metal such as boron, titanium, and niobium is mixed with natural flake graphite or thermally expanded graphite or acetylene black. The multi-component electrochemical capacitor of claim 1, wherein the nanostructured carbon material is composed of several layers of thick carbon nanotubes. The multi-element electrochemical capacitor according to claim 1, wherein the electrode sheet in contact with the electrically insulating film is disposed such that an electrochemically active layer faces the electrically insulating film, and the next electrode sheet is displaced to the electrochemical Half of the width of the active layer, the electrochemically active layers of the electrode sheets face each other and are separated by a porous ion permeable separator. The multi-element electrochemical capacitor of claim 1, wherein the electrodes are continuously fastened to the substrate. A method of fabricating a multi-element electrochemical capacitor, the method comprising preparing an electrode mixture comprising carbon materials of different types of nanostructures, one of the nanostructured carbon materials having a maximum possible specific surface area and a relatively low electrical conductivity, and a nanostructured carbon material having a relatively large specific surface area and a relatively high electrical conductivity, wherein the electrode mixture is added with a metal or a compound thereof or a nanosized particle of a redox polymer; by coating the electrode mixture One or both sides of the substrate of the non-woven polymer material covering each electrode sheet or embedded therein to produce opposite polarity electrode sheets, the non-woven polymer material having high porosity; to be made of porous ion permeability separator The oppositely-polarized electrode sheets are continuously disposed on at least one of the electrically insulating films; the layers disposed as above are wound into a roll; and the roll is impregnated with an electrolyte. The method of manufacturing a multi-element electrochemical capacitor according to claim 7, wherein a plurality of layers of carbon nanotubes are used as a nanostructured carbon material, and the carbon nanotubes are pyrolyzed by a gaseous hydrocarbon and a hydrogen gas. The mixture is produced and has a size of 5 to 50 nm, a specific surface area of 500 to 1,000 m ² /g, and a specific conductivity of 10 to 100 Sm/cm, and an activated carbon obtained from a carbide material and a nanoporous carbon material are used as the mixture. Another nanostructured carbon material. The method of manufacturing a multi-element electrochemical capacitor according to claim 8 wherein the mixture of the pyrolyzed gaseous hydrocarbon and the hydrogen is carried out at a temperature maintained in the range of 650 ° C to 900 ° C and a pressure in the range of 0.1 to 1.0 MPa. And a compound based on cobalt and molybdenum is used as a catalyst, and natural gas or propane or butane or ethylene is used as the gaseous hydrocarbon. The method of manufacturing a multi-element electrochemical capacitor according to claim 8, wherein the plurality of layers of carbon nanotubes are produced by pyrolyzing a mixture of an aromatic hydrocarbon and an alcohol. The method of manufacturing a multi-element electrochemical capacitor according to claim 10, wherein the mixture of the pyrolyzed aromatic hydrocarbon and the alcohol is maintained at a temperature in the range of 650 ° C to 900 ° C and a pressure in the range of 0.1 to 1.0 MPa. The following was carried out, and a compound based on iron, nickel and magnesium oxide was used as a catalyst, benzene and toluene were used as an aromatic hydrocarbon, and ethanol was used as an alcohol. The method of manufacturing a multi-element electrochemical capacitor according to claim 8 or 10, wherein the plurality of layers of carbon nanotubes are subjected to oxidant, ultrasonic wave and water further under supercritical conditions after they are produced. deal with. The method of manufacturing a multi-element electrochemical capacitor according to claim 8, wherein the activated carbon is formed by wet forming a synthetic monomer, followed by carbonization and high-temperature vapor activation at a temperature ranging from 600 ° C to 1,000 ° C. . The method for manufacturing a multi-element electrochemical capacitor according to the invention of claim 8, wherein the nanoporous carbon material is obtained from boron, titanium and lanthanum carbide and further heated at a temperature of 600 ° C to 1,200 ° C with chlorine gas. Thermochemical treatment. The method of manufacturing a multi-element electrochemical capacitor according to claim 7, wherein the electrode mixture is prepared by mixing a plurality of layers of carbon nanotubes and activated carbon in a ratio of 1:3 to 3:1 in a ball mill. Grains having a size of about 10 to 100 nm are produced, sieved on a screen having a typical mesh size of 100 nm, and ultrasonically treated to maximize the uniformity of the electrode mixture. The method of manufacturing a multi-element electrochemical capacitor according to claim 7, wherein the positive electrode is made of a metal such as magnesium, surface, silver, and nickel, and such as magnesium oxide, magnesium hydroxide, oxidation meter, silver oxide, lead oxide, sulfuric acid. A nano-sized particle of a metal compound of lead, nickel hydroxide, and lithium cobalt oxide, and the negative electrode is made of a metal such as zinc, lead, cadmium, iron, and lithium, and such as zinc hydroxide, zinc chloride, lead sulfate, or hydroxide Manufacture of nanosized particles of metal compounds of cadmium and iron hydroxide. The method of manufacturing a multi-element electrochemical capacitor according to claim 7, wherein the electrode sheet is fabricated by coating the electrode mixture as an electrode suspension on a substrate, the electrode suspension being dispersed by ultrasonic waves. An electrode mixture in an organic solvent. A method of manufacturing a multi-element electrochemical capacitor according to the invention of claim 17, wherein isopropanol or ethanol is used as the organic solvent for preparing the electrode suspension. The method of producing a multi-element electrochemical capacitor according to claim 7, wherein the electrode mixture is fastened to the substrate in the form of a powder under electrostatic force. The method of producing a multi-element electrochemical capacitor according to claim 7, wherein the obtained electrode sheet is placed on a contact electrode such as a graphite foil after the electrode mixture has been applied thereto and then heated to 120. The temperature between ° C and 150 ° C and withstand a pressure of 0.5 to 1.0 MPa. The method of manufacturing a multi-element electrochemical capacitor according to claim 7, wherein the porous separator composed of one to four layers is made of a polymer film having a thickness of 3 to 5 μm and a porosity of 20% to 40. a track film having a pore size of 0.05 to 0.1 μm, or a sheet of a non-woven polymer material such as polypropylene having a thickness of 10 μm and a density of 15 to 40 mg/cm ² , or a polybenzimidazole An ion permeable polymer film having a thickness of 10 to 15 μm, impregnated with an electrolyte, and containing 3 to 10 parts by mass of an electrolyte. The method of manufacturing a multi-element electrochemical capacitor according to claim 7, wherein the electrode reel is provided by bringing a length of the electrode foil at an opposite end of the electrically insulating film into contact with the contact electrode; One end of the electrode is connected to the center electrode; the double-layer electrode sheet is wound around the center electrode such that a second length of the electrode sheet contacting the second electrode sheet forms an outer surface of the roll; and the outer surface of the roll Connect to the peripheral electrode. The method of manufacturing a multi-element electrochemical capacitor according to claim 22, wherein the center electrode and the peripheral electrode are made of a metal pipe such as aluminum or an alloy thereof, and a cap of an electrically insulating material such as plastic is Both ends of the electrode reel are inserted between the center electrode and the peripheral electrode, and the caps of the electrically insulating material are inserted after the reel has been impregnated with the electrolyte. The method of manufacturing a multi-element electrochemical capacitor according to claim 7, wherein the electrolyte for impregnating the reel is an organic electrolyte, that is, containing an ammonium or imidazole-based cation, including tetrafluoroborate, and a sixth An organic salt of an anion of fluorophosphate or trifluoromethanesulfonimide or bistrifluoromethanesulfonimide or hexafluoroethyltrifluorophosphate in acetonitrile or propylene carbonate or formamide The solution, or a mixed electrolyte, that is, a solution of zinc chloride in acetonitrile, or an inorganic electrolyte such as an aqueous solution of potassium base. A method of manufacturing a multi-element electrochemical capacitor according to claim 7 or claim 24, wherein the reel is immersed in the electrolyte in a vacuum chamber at a residual pressure of 10 Pa. A method of manufacturing a multi-element electrochemical capacitor according to claim 7 wherein a plurality of parallel electrode sheets are wound into a roll and disposed in a housing in the form of a parallelepiped or cylinder.