WO2023176989A1 - Séparateur pour condensateur et condensateur au graphène le comprenant - Google Patents

Séparateur pour condensateur et condensateur au graphène le comprenant Download PDF

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WO2023176989A1
WO2023176989A1 PCT/KR2022/003575 KR2022003575W WO2023176989A1 WO 2023176989 A1 WO2023176989 A1 WO 2023176989A1 KR 2022003575 W KR2022003575 W KR 2022003575W WO 2023176989 A1 WO2023176989 A1 WO 2023176989A1
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capacitor
separator
graphene
ceramic layer
layer
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PCT/KR2022/003575
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English (en)
Korean (ko)
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지용주
김익휘
이광제
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주식회사 동평기술
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Publication of WO2023176989A1 publication Critical patent/WO2023176989A1/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
    • 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
    • H01G11/52—Separators
    • 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
    • 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
    • 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 a separator for a capacitor and a graphene capacitor including the same. More specifically, the present invention provides a graphene-coated separator for a capacitor that has improved durability, can activate the electrolyte and anode of the capacitor, and can extend the life of the capacitor, a graphene capacitor containing the same, and a method of manufacturing the same. It's about.
  • Supercapacitors have the advantage of providing high power density and long cycle life with fast and stable charge/discharge capabilities through the formation of an electric double layer (EDL), but have the disadvantage of low energy density.
  • EDL electric double layer
  • These supercapacitors can be broadly divided into electric double layer supercapacitors, pseudo supercapacitors, and hybrid supercapacitors.
  • Hybrid supercapacitor refers to a supercapacitor that uses different energy storage methods on both electrodes.
  • a hybrid supercapacitor is a hybrid energy storage device that uses a cathode material that stores energy through oxidation/reduction reactions like a battery and an anode material that collects charges in an electric double layer like a storage battery (electric double layer capacitor).
  • Lithium-ion hybrid supercapacitor (LIHS) is a combination of lithium ion insertion/extraction reaction of LIB type anode electrode and PF 6- adsorption/desorption of EDL type cathode electrode.
  • a supercapacitor typically includes an anode and a cathode, and the two electrodes are separated by a porous separator.
  • a porous separator between the electrodes allows the flow of ionic charge but prevents electrical contact between the electrodes.
  • the variables that have the greatest impact on the power density of a supercapacitor are electrodes, electrolyte, and It is the resistance of the separator.
  • electrodes electrolyte
  • It is the resistance of the separator.
  • water-soluble and organic liquid electrolytes and porous polyolefin separators were used, or polyacrylic acid (PAA) and polyvinyl alcohol (PVA)-based polymer gel electrolytes containing KOH (potassium hydroxide) aqueous solution were used as electrolytes and separators. It has been used.
  • the porous polyolefin-based separator used in conventional technology has the advantage of having sufficient mechanical strength, but its porosity is usually 40-80%, which is significantly lower than that of non-woven fabrics, and the interfacial energy of the surface is lower than that of the electrolyte solvent, so its wettability in the electrolyte is greatly reduced.
  • the separator electrolyte with high ionic conductivity.
  • the electrode and the separator are not integrated, which increases the interfacial resistance and causes leakage due to the use of a liquid electrolyte.
  • the polymer gel electrolyte separator improves leakage and safety, but still has low ionic conductivity and does not use a separate separator reinforcement, so its mechanical properties are low, making it difficult to manufacture ultra-high capacity capacitors and improve their characteristics.
  • the purpose of the present invention is to provide a separator for a capacitor that improves the durability of the separator, activates the electrolyte and anode of the capacitor, and maintains the optimal condition of the capacitor to extend its lifespan.
  • Another object of the present invention is to efficiently manufacture a separator for a capacitor through a simple process, which can improve the durability of the separator, activate the electrolyte and anode of the capacitor, and extend the lifespan by maintaining the optimal capacitor condition. It provides a way to do it.
  • Another object of the present invention is to provide a graphene capacitor with improved durability, activated electrolyte and anode, and extended lifespan by maintaining an optimal capacitor condition.
  • the object of the present invention is not limited to the objects mentioned above, and other objects not mentioned can be clearly understood from the detailed description.
  • a substrate a ceramic layer formed on at least one side of the substrate;
  • a separator for a capacitor is provided, including a graphene layer formed on the ceramic layer.
  • the ceramic layer and the graphene layer may be formed on both sides of the substrate.
  • the ceramic layer may include spherical alumina particles.
  • the ceramic layer and the graphene layer may further include one or more types of organic and inorganic binders.
  • the graphene layer may have a thickness of 0.2 to 5 nm per cm2 per unit area.
  • the separator for the capacitor may have a thickness of 5 to 25 ⁇ m or less.
  • a separator for a capacitor including.
  • a ceramic material in step ii) may include forming a ceramic layer using a dry dispenser supplied with a ceramic layer material including one or more of organic and inorganic binders.
  • step iii) may include forming a graphene layer using a dry dispenser supplied with a graphene layer material containing graphene particles.
  • steps ii) and step iii) may include forming the ceramic layer and the graphene layer on both sides of the substrate.
  • the ceramic layer and the graphene layer may include continuously forming the graphene layer after forming the ceramic layer while moving the substrate in a certain direction.
  • the method of manufacturing a separator for a capacitor of the present application may further include iv) a heat treatment step of heating the separator.
  • a graphene capacitor including a is provided.
  • the capacitor may be a pseudo supercapacitor, an electric double layer (EDLC) supercapacitor, or a hybrid supercapacitor.
  • EDLC electric double layer
  • the graphene coating separator for a capacitor of the present application forms a graphene layer on a ceramic layer, thereby improving the durability of the separator, activating the electrolyte and anode agent of the capacitor, and maintaining the optimal state of the capacitor. You can extend the life of the capacitor by maintaining it.
  • the method of manufacturing a separator for a capacitor of the present application includes a continuous process including a dry dispensing step, so that the durability of the separator is improved, the electrolyte and anode of the capacitor can be activated, and the optimal capacitor is produced.
  • a graphene-coated separator for a capacitor that can maintain its condition and extend the life of the capacitor can be efficiently manufactured through a simple process.
  • the durability of a graphene capacitor including the graphene coating separator for a capacitor of the present application can be improved, the electrolyte and anode agent are activated, and the optimal capacitor condition is maintained, thereby extending the lifespan.
  • FIG. 1 is a cross-sectional view schematically showing a separator for a capacitor according to an embodiment of the present invention.
  • Figure 2 is a flow chart schematically showing a method of manufacturing a separator for a capacitor according to an embodiment of the present invention.
  • Figure 3 is a schematic diagram schematically showing a method of manufacturing a separator for a capacitor according to an embodiment of the present invention.
  • Figure 4 is a diagram schematically showing a supercapacitor according to an embodiment of the present invention.
  • a component such as a layer, part, or substrate
  • it is directly “on,” or “on” the other component. It may be “connected” or “coupled,” and may have one or more other components interposed between the two components.
  • a component is described as being “directly on,” “directly connected to,” or “directly coupled to” another component, there cannot be any intervening components between the two components. .
  • FIG. 1 is a cross-sectional view schematically showing a separator for a capacitor according to an embodiment of the present invention.
  • a separator 1 for a capacitor of the present invention includes a substrate 100; A ceramic layer 200 formed on at least one side of the substrate 100; and a graphene layer 300 formed on the ceramic layer 200.
  • the separator 1 provided between the cathode and anode of the capacitor allows the flow of ionic charges, but serves to prevent electrical contact between the electrodes.
  • the substrate 100 of the separator 1 is an insulating porous material and is a bare separator.
  • the substrate 100 includes polypropylene (PP), polyethylene (PE), polyimide (PI), polyolefin, polyester, polyacrylonitrile, polyvinylidene fluoride-hexafluoropropylene, etc.
  • a fibrous non-woven fabric or porous glass filter that may include one or more of polymer, cellulose acetate, cellulose acetate butylate, cellulose acetate propionate, polyvinyl butyral, polyvinyl alcohol, polyvinylpyrrolidone, and polyamideimide. It can be.
  • the substrate 100 of the separator is polyethylene nonwoven fabric, polypropylene nonwoven fabric, polyester nonwoven fabric, polyacrylonitrile porous separator, poly(vinylidene fluoride) hexafluoropropane copolymer porous separator, cellulose porous separator, kraft paper, or rayon.
  • separator material commonly used in the battery and capacitor fields, such as fiber.
  • the thickness of the substrate 100 is 1 to 20 ⁇ m, which ensures a smooth flow of ionic charges and has excellent strength and electrical insulation among the physical properties to improve the capacity and lifespan of the capacitor. It may be suitable.
  • the ceramic layer 200 serves to reinforce electrical properties and mechanical strength between electrodes. Additionally, the ceramic layer 200 can suppress side reactions on the surface of the metal electrode and also suppress the generation of dendrites.
  • the ceramic layer 200 may be composed of inorganic particles that are various ceramic materials. Although not limited thereto, the ceramic layer 200 may contain metal fluoride, metal oxide, metal nitride, metal carbide, or a combination thereof. At this time, the metals contained in the inorganic particles are Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, Rb, Sr, Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Cd, In, Sn, Sb, Cs, Ba, La, Hf, Ta, W, Re, Os, Ir, Pt, Au, Hg, Tl, Pb, Bi, Po, Fr, Ra, Ac, It may be Si, P, As, Se or Te.
  • the inorganic particles may be nano-inorganic particles with a diameter of nanometers. As an example, the inorganic particles may be a metal oxide that exhibits insulating properties, such as aluminum oxide.
  • the ceramic layer 200 is composed of spherical alumina particles, which can be stably fused to the substrate 100 compared to plate-shaped alumina particles, and provides smooth charge transfer and stable coating of the graphene layer 300. It may be suitable for.
  • the ceramic layer 200 has a thickness of 10 to 200 nm so that it can be stably fused to the substrate 100 and is suitable for smooth ion movement and stable coating of the graphene layer 300, and has a thickness of 20 to 170 nm. It may be more suitable.
  • the ceramic layer 200 may further include a binder that binds the inorganic particles together with the inorganic particles.
  • the binder in the ceramic layer 200 is polyacrylic acid (PAA), polyvinylidene fluoride (PVDF), polyvinylidene fluoride-co-hexafluoropropylene (PVDF-co-HFP), chitosan, polyethylene glycol, and xanthan. It may include gum, gum arabic, polyacrylonitrile (PAN), poly(3,4-ethylenedioxythiophene) (PEDOT), polystyrene sulfonate (PSS), PEDOT:PSS, or mixtures thereof.
  • the binder may be located only in the area between the inorganic particles and serve to bind them together. Specifically, the weight ratio of the inorganic particles and binder in the ceramic layer 200 may be within the range of 2:1 to 8:1.
  • the ceramic layer 200 may have multiple nanometer-sized pores.
  • the pore size of the substrate 100 may be 0.01 to 5 ⁇ m. According to the above configuration, the flow of ions can be facilitated while maintaining electrical insulation.
  • the graphene layer 300 includes graphene particles.
  • Graphene is a thin film with a thickness of only 0.2 nm per atom, in which carbon atoms are arranged in a honeycomb shape in which hexagons are laid out tightly.
  • Graphene has the same bonding structure as it has the thickness of one atom layer, but is composed of multiple layers. It is a material that exhibits significantly different characteristics from existing graphite and surpasses carbon nanotubes with excellent properties.
  • both materials have excellent electrical and mechanical properties, but CNT shows conductor and semiconductor characteristics, while graphene shows conductor characteristics.
  • graphene which has a flat structure, is advantageous for large areas and applications in electronic processes. Using these characteristics of graphene, it can be usefully applied to energy storage devices.
  • the graphene layer 300 can improve the electrical conductivity of the electrode and also reduce current density. As a result, in addition to improving the electrochemical reaction efficiency of the electrode active material, it is possible to prevent destruction of the electrode active material or subsequent performance degradation.
  • the average thickness per cm2 per unit area of the graphene particles in the graphene layer 300 may be 0.2 to 20 nm, specifically 0.2 to 10 nm, more specifically 0.2 to 5 nm, and more specifically 0.35 to 5 nm. there is. Additionally, the average width of the graphene particles may be 0.1 to 20 ⁇ m, specifically 1 to 15 ⁇ m, and more specifically 7 to 13 ⁇ m. In addition, the graphene particle may have one or several atomic layers, and as an example, about 1 to 100 atomic layers, more specifically 1 to 50 atomic layers, more specifically 1 to 25 atomic layers, More specifically, it may have 1 to 10 atomic layers, more specifically 1 to 5 atomic layers, and more specifically 1 to 3 atomic layers.
  • Inorganic particles such as silicon particles included in the conventional ceramic layer 200 may crack due to large volume expansion and contraction during charging and discharging, which may have the disadvantage of greatly reducing electrical continuity.
  • an electrolyte layer is created on the surface of the damaged particle, and as charging and discharging continues, the layer becomes thicker, which can be a problem in that capacitor capacity and lifespan are greatly reduced.
  • we attempted to solve this problem by forming a graphene layer 300 on the surface of the ceramic layer 200.
  • the separator 1 including the graphene layer 300 can maintain a charge/discharge speed superior to that of an existing hybrid capacitor and distribute charges evenly due to the electrical characteristics of the graphene mesh. Therefore, it is possible to prevent activation of the electrolyte and positive electrode agent from being inhibited by uneven temperature distribution and uneven electrode distribution due to conventional uneven charge distribution.
  • the problems caused by the conventional ceramic layer 200 described above can be solved, the durability of the separator 1 can be further improved, the electrolyte and anode of the capacitor can be activated, and optimal By maintaining the condition of the capacitor, the lifespan of the capacitor can be extended.
  • the graphene layer 300 may further include one or more types of carbon particles such as carbon nanotubes, acetylene black, Super-P, Ketjen black, activated carbon, etc.
  • the graphene layer 300 may further include a binder.
  • the binder in the graphene layer 300 is polyacrylic acid (PAA), polyvinylidene fluoride (PVDF), polyvinylidene fluoride-co-hexafluoropropylene (PVDF-co-HFP), chitosan, polyethylene glycol, and xanthan. It may include gum, gum arabic, polyacrylonitrile (PAN), poly(3,4-ethylenedioxythiophene) (PEDOT), polystyrene sulfonate (PSS), PEDOT:PSS, or mixtures thereof.
  • the binder in the graphene layer 300 may be PVDF.
  • the binder in the graphene layer 300 may further include, for example, graphite powder, which is a conductive adhesive. It may be appropriate to include 1 to 50 parts by weight of the graphite powder per 100 parts by weight of the binder.
  • the graphene layer 300 is stably fused to the ceramic layer 200, the durability of the separator 1 can be further improved, the electrolyte and anode of the capacitor can be activated, and the optimal By maintaining the condition of the capacitor, the lifespan of the capacitor can be extended.
  • the graphite powder may be Everyohm 30CE (Nippon Graphite Industries, Ltd.).
  • the ceramic layer 200 and the graphene layer 300 may be formed on both sides of the substrate 100. According to the above configuration, the problems caused by the conventional ceramic layer described above can be solved, the durability of the separator 1 can be further improved, the electrolyte and anode agent of the capacitor can be activated, and the optimal state of the capacitor can be maintained. This can further help extend the life of the capacitor.
  • the separator 1 for a capacitor may have a thickness of 1 to 25 ⁇ m, specifically 5 to 25 ⁇ m, and more specifically 10 to 25 ⁇ m. According to the above configuration, the capacity and lifespan of the capacitor can be improved while optimizing the function of the separator.
  • Figure 2 is a flow chart schematically showing a method of manufacturing a separator for a capacitor according to an embodiment of the present invention.
  • Figure 3 is a schematic diagram schematically showing a method of manufacturing a separator for a capacitor according to an embodiment of the present invention.
  • a method of manufacturing a separator for a capacitor includes the steps of i) preparing a substrate 100 (S10); ii) forming a ceramic layer 200 on at least one side of the substrate 100 (S20); and iii) forming a graphene layer 300 on the ceramic layer 200 (S30).
  • Step i) is a step (S10) of preparing the substrate 100, which is a bare separator.
  • the substrate 100 may be prepared as an insulating porous material.
  • the substrate 100 may be formed to have a thickness of 1 to 20 ⁇ m. According to the above configuration, smooth movement of charges can be ensured and the capacity and lifespan of the capacitor can be improved.
  • Step ii) is a step (S20) of forming a ceramic layer 200 on at least one side of the substrate 100.
  • the ceramic layer 200 may be formed by various known methods, such as blade coating or spray coating. Although it is not limited to this, it may be appropriate for the ceramic layer 200 to be formed using dry dispensing in terms of improving process efficiency. i.e. ceramic material in step ii);
  • the ceramic layer 200 may be formed using the dry first dispenser 400 supplied with a ceramic layer 200 material containing at least one type of organic and inorganic binder. At this time, the ceramic layer 200 may be formed on the substrate 100 due to electrostatic attraction.
  • Inorganic particles which are the material of the ceramic layer 200, and at least one type of organic and inorganic binder that binds the inorganic particles and helps fusion to the substrate 100 are mixed in a certain ratio, and the first dispenser 400 ) can be supplied to.
  • the ceramic layer 200 material is stably fused to the substrate 100 by the dry first dispenser 400 supplied with the ceramic layer 200 material containing at least one type of organic and inorganic binder. It can be done, and the continuous process can be simple and efficient compared to the wet process using slurry.
  • the ceramic layer 200 is composed of spherical alumina particles, fluidity can be secured during internal movement and spraying in the first dispenser 400 compared to plate-shaped alumina particles, and the substrate 100 It can be stably fused to and can be suitable for smooth charge transfer and stable coating of the graphene layer 300.
  • the ceramic layer 200 formed to a thickness of 10 to 200 nm can be stably fused to the substrate 100 and is suitable for smooth charge transfer and stable coating of the graphene layer 300. and 20 to 170 nm may be more suitable.
  • Step iii) is a step (S30) of forming a graphene layer 300 on the ceramic layer 200.
  • Step iii) may include forming the graphene layer 300 using a dry second dispenser 500 supplied with a graphene layer 300 material including graphene particles and a binder.
  • Graphene particles which are the material of the graphene layer 300, and at least one type of organic and inorganic binder that binds the graphene particles and helps fusion to the ceramic layer 200 are mixed in a certain ratio, and the second dispenser Supplied to (500).
  • the graphene layer 300 material containing at least one type of organic and inorganic binder can be stably fused to the ceramic layer 200 by the dry second dispenser 500 supplied, and can be stably fused to the ceramic layer 200 using a slurry.
  • continuous processes can be simple and efficient.
  • Step ii) and step iii) may include forming the ceramic layer 200 and the graphene layer 300 on both sides of the substrate 100.
  • the ceramic layer 200 and the graphene layer 300 are formed by moving the substrate 100 in a certain direction and forming the ceramic layer 200. It may include continuously forming the fin layer 300. According to the above configuration, the separator 1 for a capacitor can be efficiently manufactured through a batch continuous process.
  • the method of manufacturing a separator for a capacitor of the present application may further include iv) a heat treatment step of heating the separator.
  • the heat treatment may be performed at a temperature of 50 to 130° C. for 1 to 10 hours. According to the heat treatment under the above conditions, the ceramic layer 200 and the graphene layer 300 can be stably fixed by the binder, and the mechanical and electrical properties of the separator can be excellent.
  • Figure 4 is a diagram schematically showing a capacitor including a separator according to an embodiment of the present invention.
  • a graphene capacitor 1000 includes a cathode 1100; anode (1200); A separator 1 for a capacitor described herein provided between the cathode 1100 and the anode 1200; and an electrolyte solution (not shown) in contact with the cathode 1100, the anode 1200, and the separator 1.
  • the graphene capacitor 1000 of the present application refers to a capacitor in which a graphene layer 300, which is a graphene coating layer, is formed on a separator 1.
  • the capacitor may be a pseudo supercapacitor, an electric double layer (EDLC) supercapacitor, or a hybrid supercapacitor.
  • EDLC electric double layer
  • the supercapacitor may be a coin-type, cylindrical, or square-type supercapacitor.
  • Supercapacitors are energy storage devices that can be used as auxiliary batteries or as replacements for batteries due to their excellent output characteristics, long lifespan, low maintenance costs, rapid output response characteristics, and excellent stability.
  • the hybrid capacitor may be a lithium ion capacitor.
  • Supercapacitors can use an asymmetric electrode structure.
  • the cathode 1100 may be a carbon-based electrode with high energy density
  • the anode 1200 may be a lithium or sodium transition metal oxide-based electrode with high output and long lifespan.
  • the negative electrode 1100 may be formed by mixing a negative electrode active material, a binder, a conductive material, and a dispersion medium into various forms.
  • the negative electrode material may be appropriate to add the negative electrode material in an amount of 2 to 20 parts by weight of the conductive material and 2 to 10 parts by weight of the binder based on 100 parts by weight of activated carbon.
  • the content of the dispersion medium is not particularly limited, but may be added in an amount of 200 to 300 parts by weight based on 100 parts by weight of activated carbon.
  • the negative electrode active material may be a mixture of one or more of activated carbon, soft carbon, hard carbon, and graphite.
  • the activated carbon is not particularly limited, and activated carbon used in general electrode production can be used.
  • coconut shell-based carbonized activated carbon, phenol resin-based carbonized activated carbon, etc. can be used, and this includes partially crystalline activated carbon.
  • the specific surface area of the activated carbon powder used is preferably 300 to 2500 m2/g. It may be appropriate for the activated carbon powder to have a particle size in the range of 0.9 to 20 ⁇ m to facilitate electrode forming and dispersion.
  • the conductive material is not particularly limited as long as it is an electronically conductive material that does not cause chemical changes. Examples include natural graphite, artificial graphite, carbon black, acetylene black, Ketjen black, Super-P, Denka black, carbon fiber, and copper. , metal powders such as nickel, aluminum, and silver, or metal fibers, etc. are possible.
  • the binder is polytetrafluoroethylene (PTFE), polyvinylidenefloride (PVdF), carboxymethylcellulose (CMC), polyvinyl alcohol (PVA), and polyvinyl butyral.
  • PTFE polytetrafluoroethylene
  • PVdF polyvinylidenefloride
  • CMC carboxymethylcellulose
  • PVA polyvinyl alcohol
  • polyvinyl butyral polyvinyl butyral
  • PVB poly-N-vinylpyrrolidone
  • SBR styrene butadiene rubber
  • polyamide-imide polyimide
  • One type or two or more types selected from the like may be used in combination.
  • the dispersion medium may be an organic solvent such as ethanol (EtOH), acetone, isopropyl alcohol, methyl pyrrolidone (NMP), propylene glycol, or water.
  • EtOH ethanol
  • NMP methyl pyrrolidone
  • propylene glycol or water.
  • the positive electrode 1200 may be formed in various forms by mixing a positive electrode active material containing lithium or sodium transition metal oxide and activated carbon, a binder, a conductive material, and a dispersion medium.
  • the cathode material includes 100 parts by weight of the cathode active material, 2 to 15 parts by weight of a conductive material per 100 parts by weight of the cathode active material, and 2 to 10 parts by weight of a binder per 100 parts by weight of the cathode active material, and the dispersion medium is 100 parts by weight of the cathode active material. It may be appropriate to manufacture it at 200 to 300 parts by weight.
  • the lithium transition metal oxide may be a composite metal oxide having a layered structure, spinel structure, or olivine structure containing lithium and a transition metal.
  • the transition metal may be at least one metal selected from the group consisting of titanium (Ti), vanadium (V), manganese (Mn), iron (Fe), cobalt (Co), aluminum (Al), and nickel (Ni). .
  • These lithium transition metal oxides include LiMn 2 0 4 , LiCoO 2 , LiNi1/3Co1/3Mn1/3O 2 , Examples include LiNixCoxAlxO 2 and the like.
  • the specific surface area of the lithium transition metal oxide may be suitably in the range of 0.1 to 100 m2/g.
  • the positive electrode develops capacity through a mechanism using chemical reactions, resulting in output asymmetry with the negative electrode.
  • a chemical reaction occurs in the anode using lithium transition metal oxide and a physical reaction occurs in the cathode using activated carbon, resulting in output asymmetry between the anode and the cathode. Therefore, the voltage shock is relatively applied to the carbon electrode, which is the cathode, which limits the use of the hybrid ion capacitor at high output and high voltage, and may cause reliability problems.
  • activated carbon is used as a positive electrode active material along with lithium transition metal oxide.
  • Activated carbon powder used as a positive electrode active material may be coconut shell-based activated carbon, phenol resin-based activated carbon, coke-based activated carbon, or a mixture thereof, and it may be appropriate to use activated carbon powder having a specific surface area of 1,000 to 2,500 m2/g.
  • the activated carbon powder used as a positive electrode active material may be appropriately contained in an amount of 1 to 30 parts by weight based on 100 parts by weight of the positive electrode active material. If the content of activated carbon powder used as a cathode active material is less than 1 part by weight, the effect of suppressing output asymmetry is weak, and if it exceeds 30 parts by weight, the effect of suppressing output asymmetry can no longer be expected, and the energy density of activated carbon is low due to lithium transfer. Because it is insufficient compared to metal oxide, a significant portion of the efficiency of the hybrid system is lost due to capacity reduction. Therefore, the weight ratio of lithium transition metal oxide and activated carbon powder (lithium transition metal oxide: activated carbon powder) in the positive electrode active material is preferably in the range of 99:1 to 70:30.
  • the cathode active material can contain sodium, which is abundant in resources but inexpensive.
  • the conductive material is not particularly limited as long as it is an electronically conductive material that does not cause chemical changes. Examples include natural graphite, artificial graphite, carbon black, acetylene black, Ketjen black, Super-P, Denka black, carbon fiber, and copper. , metal powders such as nickel, aluminum, and silver, or metal fibers, etc. are possible.
  • the binder is polytetrafluoroethylene (PTFE), polyvinylidenefloride (PVdF), carboxymethylcellulose (CMC), polyvinyl alcohol (PVA), and polyvinyl butyral (polyvinyl butyral). From vinyl butyral (PVB), poly-N-vinylpyrrolidone (PVP), styrene butadiene rubber (SBR), polyamide-imide, polyimide, etc. One selected type or a mixture of two or more types can be used.
  • the dispersion medium may be an organic solvent such as ethanol (EtOH), acetone, isopropyl alcohol, methyl pyrrolidone (NMP), propylene glycol (PG), or water.
  • EtOH ethanol
  • NMP methyl pyrrolidone
  • PG propylene glycol
  • the electrolyte solution may include an organic solvent and lithium salt.
  • the above organic solvent and lithium salt can be used as conventional solvents.
  • a hybrid supercapacitor cell can be formed by injecting an electrolyte solution containing a dissolved lithium salt to impregnate the electrode structure and sealing it.
  • the lithium salt is a lithium salt commonly used in capacitors and is not particularly limited, for example, LiPF 6 , LiBF 4 , LiClO 4 , Li(CF 3 SO 2 ) 2 , LiCF 3 SO 3 , LiSbF 6 or LiAsF 6 etc. can be used.
  • the solvent constituting the electrolyte solution is not particularly limited, but cyclic carbonate-based solvents, linear carbonate-based solvents, ester-based solvents, ether-based solvents, nitrile-based solvents, amide-based solvents, etc. can be used.
  • Ethylene carbonate, propylene carbonate, butylene carbonate, vinylene carbonate, etc. can be used as the cyclic carbonate-based solvent, and dimethyl carbonate, methyl ethyl carbonate, diethyl carbonate, etc. can be used as the linear carbonate-based solvent.
  • Ester-based solvents include methyl acetate, ethyl acetate, propyl acetate, methyl propionate, ethyl propionate, and ⁇ -butyrolactone
  • ether-based solvents include 1,2-dimethoxyethane and 1,2-diethane. Toxyethane, tetrahydrofuran, 1,2-dioxane, 2-methyltetrahydrofuran, etc. can be used.
  • the nitrile-based solvent can be used such as acetonitrile
  • the amide-based solvent can be used such as dimethylformamide. can be used.
  • Carbon materials are used as electrode materials for supercapacitors.
  • Graphene is a nanocarbon material that has a high specific surface area and excellent electrical conductivity, making it a very suitable material for application in supercapacitors as it has excellent compatibility with existing carbon-based electrode materials. can do.
  • a porous membrane substrate of polypropylene was prepared.
  • spherical Al 2 O 3 nanopowder As a ceramic layer material, 45 mg of spherical Al 2 O 3 nanopowder (Aldrich, USA) and 11.3 mg of polyvinylidene fluoride (PVDF, Arkema) (mass ratio approximately 4:1) were added to 15 ml of acetone and sonicated for 2 hours. Al 2 O 3 slurry was obtained by mixing through mixing, which was then powdered and supplied to the first dispenser.
  • PVDF polyvinylidene fluoride
  • graphene layer material As a graphene layer material, 45 mg of graphene (thickness 1.6 nm) and 11.3 mg of polyvinylidene fluoride (PVDF, Arkema) (mass ratio approximately 4:1) were added to 15 ml of acetone and mixed through sonication for 2 hours to form graphene. After obtaining the slurry, it was powdered and supplied to the second dispenser.
  • PVDF polyvinylidene fluoride
  • a ceramic layer material was sprayed through the spray nozzles of the first dispenser provided on both sides of the substrate to form a ceramic layer on the surface of the substrate.
  • a separator for a capacitor was manufactured by spraying a graphene layer material on the surface on which the ceramic layer was formed through the spray nozzles of a second dispenser located on both sides of the substrate and behind the first dispenser to form a graphene layer on the surface of the ceramic layer. .

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

Abstract

La présente invention concerne un séparateur pour un condensateur et un condensateur au graphène le comprenant. Plus spécifiquement, la présente invention concerne : un séparateur revêtu de graphène pour un condensateur, le séparateur ayant une durabilité améliorée, et étant apte à activer l'électrolyte et le matériau d'électrode positive d'un condensateur et à prolonger la durée de vie d'un condensateur ; un condensateur au graphène le comprenant ; et son procédé de production.
PCT/KR2022/003575 2022-03-14 2022-03-15 Séparateur pour condensateur et condensateur au graphène le comprenant WO2023176989A1 (fr)

Applications Claiming Priority (2)

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KR10-2022-0031303 2022-03-14
KR1020220031303A KR102640431B1 (ko) 2022-03-14 2022-03-14 커패시터용 분리막 및 이를 포함하는 그래핀 커패시터

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WO2023176989A1 true WO2023176989A1 (fr) 2023-09-21

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20130244119A1 (en) * 2012-03-16 2013-09-19 Li-Tec Battery Gmbh Graphene-containing separator for lithium ion batteries
KR20200091563A (ko) * 2019-01-23 2020-07-31 현대자동차주식회사 이중 코팅 분리막 및 이를 포함하는 리튬 이차전지
KR20200119579A (ko) * 2019-04-10 2020-10-20 한국전력공사 슈퍼커패시터용 분리막, 이의 제조방법 및 이를 포함하는 슈퍼커패시터
KR20210021729A (ko) * 2019-08-19 2021-03-02 주식회사 제라브리드 그래핀을 포함하는 2차원소재 코팅 조성물과 이를 이용한 이차전지 분리막 및 그 제조방법
JP2021180097A (ja) * 2020-05-13 2021-11-18 株式会社ダイセル 二次電池用セパレータ、セパレータの製造方法、及びセパレータを備えた二次電池

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20130244119A1 (en) * 2012-03-16 2013-09-19 Li-Tec Battery Gmbh Graphene-containing separator for lithium ion batteries
KR20200091563A (ko) * 2019-01-23 2020-07-31 현대자동차주식회사 이중 코팅 분리막 및 이를 포함하는 리튬 이차전지
KR20200119579A (ko) * 2019-04-10 2020-10-20 한국전력공사 슈퍼커패시터용 분리막, 이의 제조방법 및 이를 포함하는 슈퍼커패시터
KR20210021729A (ko) * 2019-08-19 2021-03-02 주식회사 제라브리드 그래핀을 포함하는 2차원소재 코팅 조성물과 이를 이용한 이차전지 분리막 및 그 제조방법
JP2021180097A (ja) * 2020-05-13 2021-11-18 株式会社ダイセル 二次電池用セパレータ、セパレータの製造方法、及びセパレータを備えた二次電池

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