WO2006015518A1 - Procédé de fabrication d’un dispositif de stockage d’énergie ayant une efficacité de fabrication et une fiabilité du produit accrues - Google Patents

Procédé de fabrication d’un dispositif de stockage d’énergie ayant une efficacité de fabrication et une fiabilité du produit accrues Download PDF

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Publication number
WO2006015518A1
WO2006015518A1 PCT/CN2004/000946 CN2004000946W WO2006015518A1 WO 2006015518 A1 WO2006015518 A1 WO 2006015518A1 CN 2004000946 W CN2004000946 W CN 2004000946W WO 2006015518 A1 WO2006015518 A1 WO 2006015518A1
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WIPO (PCT)
Prior art keywords
energy storage
storage device
electrode
manufacturing
rubber
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Ceased
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PCT/CN2004/000946
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English (en)
Chinese (zh)
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Minxing SUN
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Individual
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Priority to PCT/CN2004/000946 priority Critical patent/WO2006015518A1/fr
Priority to CNA2004800437982A priority patent/CN101023501A/zh
Publication of WO2006015518A1 publication Critical patent/WO2006015518A1/fr
Anticipated expiration legal-status Critical
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Classifications

    • 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
    • H01G11/10—Multiple hybrid or EDL capacitors, e.g. arrays or modules
    • H01G11/12—Stacked hybrid or EDL capacitors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/78—Cases; Housings; Encapsulations; Mountings
    • 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
    • H01G11/78—Cases; Housings; Encapsulations; Mountings
    • H01G11/80—Gaskets; Sealings
    • 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

Definitions

  • the invention relates to a method for manufacturing an energy storage device which improves manufacturing efficiency and product reliability, in particular for a bipolar structure of an ultra high capacity capacitor, and the most critical problem of the energy storage device is side leakage sealing and storage.
  • the electric unit is equalized, and the invention can completely solve the bottleneck of mass production and construct a high reliability and high efficiency energy storage component. Background technique
  • a battery such as a lithium battery of a secondary battery, a nickel-metal hydride battery, or a dry battery in a primary battery
  • a capacitor aluminum electrolytic capacitor, a ceramic capacitor, or a tantalum capacitor
  • a battery is an energy storage device for electrical energy that has high storage energy characteristics but only low output power.
  • the capacitor is just the opposite. It is a power storage device with high output power but poor energy storage characteristics.
  • Ultracapacitor is an electronic component between a battery and a conventional capacitor. It has the advantages of battery and capacitor, and can make up for its shortcomings. It has small size, light weight, high power, high capacitance and long life cycle. It is a new energy storage tool with high power and high energy density.
  • Ultra-high-capacity capacitors basically contain two forms of storage: one is to store static electricity in a double layer mechanism; the other is to remove redox layers to store redox.
  • the energy density is about 5 to 10 times that of the electric double layer mechanism.
  • Electrode materials for supercapacitors can be roughly classified into three types, carbon materials, metal oxides, and conductive polymers.
  • Carbon supercapacitor is the representative of electric double layer mechanism energy storage. It is generally composed of active carbon, glass cabon or activated carbon fiber cloth. The energy storage mechanism is due to the electrode and electrolyte interface. The electric double layer generated by the charge separation.
  • electrode materials commonly used for pseudo-capacitors (1) metal oxides such as Ru ⁇ 2 , Ir ⁇ 2 , Co 3 ⁇ 4 , Mo ⁇ 3 , WC and molybdenum nitride; (2) Conductive Polymeric films such as polyaniline, polypyrrole, and polythiophene.
  • the first one is a wound type, and many of the carbon ultra-capacitors are wound.
  • the biggest advantage is that it can provide large-area winding, but the characteristics such as series connection, bulk density and electrode connection between the ultra-capacitor units are poor.
  • the second type is a stacked type assembly, which has the advantages of easy series connection between cells and high bulk density.
  • the third type is bipolar stacking.
  • the electrodes are used as positive and negative electrodes on both sides of the electrode. It is easy to obtain high working voltage components.
  • the unit assembly is more efficient, and the size of the components is easily reduced, which can reduce the manufacturing cost. This method requires independent isolation and operation of the electrolyte of the unit, and the technical difficulty is high.
  • the basic unit 10 of the ultracapacitor is composed of two electrode plates of the substrate 11 to which the electrode 12 is applied, and is insulated by an insulating object, and the electrolyte is further impregnated with the separator 14 to seal the adhesive 13 .
  • the operating voltage of the unit varies from IV (aqueous electrolyte) to 3V (organic solution electrolyte).
  • the basic unit can increase the working voltage and capacitance by series and parallel connection.
  • the IV, 1F basic unit can be connected in series by 100 to increase the working voltage to 100V, but the capacitance is only 1/100. In parallel, 100, the capacitance can reach .100F, but the working voltage is still only IV.
  • the ultracapacitor unit can be operated with a high operating voltage via a circuit, adhesive and bipolar configuration.
  • Circuit series is the easiest way to connect an infinite number of supercapacitors via a circuit.
  • the circuit series requires a large number of circuit systems.
  • a balancing circuit must be added to ensure the reliability of the overall supercapacitor.
  • Ultracapacitors that make high operating voltages are not only disadvantageous in terms of size, weight, price, and manufacturing.
  • the supercapacitor unit is a more efficient method of bonding the supercapacitor unit in series through the adhesion of silver or conductive paste.
  • Taiwan Patent No. 472271 in which an electrolyte is filled and sealed between a pair of electrode sheets to form a single electricity storage unit. Then, a plurality of power storage units formed in the same manner are adhered to each other.
  • Figure 2 shows the power storage unit
  • Figure 3 shows the stacked power storage unit.
  • the power storage units are glued with silver glue or conductive glue, just like the series connection of the power storage units.
  • the container is provided to stack the stacked power storage cells up and down with the conductive elastic body against the top plate and the bottom plate to form a high working voltage ultracapacitor device.
  • this method is superior to the circuit series, the deterioration of charge and discharge of silver glue or conductive glue makes the super capacitor challenged in reliability.
  • the use of the electrode sheets is far less efficient than a bipolar package.
  • the bipolar package is the most efficient series configuration, with the positive and negative roles acting on both sides of each electrode.
  • Each unit can be connected in series.
  • the electrode is only used in half the thickness of the series. For example, a 100V operating voltage supercapacitor requires 200 IV unit electrode pads, and a bipolar configuration requires only 101 pieces.
  • the feature of the method is that the electrical storage units are uniform in electrical and physical properties, and the electrolytes of the respective units are isolated independently.
  • FIG. 4 it is a conventional ultra high capacity capacitor structure 20.
  • the top and bottom of the capacitor have an upper conductive sheet 211 and a lower conductive sheet 212.
  • the electrode 22 of a certain number of layers is directly stacked into a dry preparation unit.
  • a cord 23 is used which results in a sealed port 24 reserved by the dry preparation unit.
  • a gasket is sandwiched between each of the electrode sheets, and finally the sealing port is filled with an electrolyte to complete the fabrication of the ultra-high capacity capacitor structure 20.
  • the above bipolar structure has serious flaws in reliability and process efficiency.
  • reliability Firstly, the hole 3D is connected to the hole, causing leakage on the side. Secondly, the distance between the electrodes is different, resulting in different heights of the storage unit. When the supercapacitor is charged and discharged, the unit cannot share the voltage evenly, causing expansion or bursting problems.
  • process efficiency Due to the setting of the gasket (gasket), the placement and extraction of the bar and the sealing and sealing of the sealing port, the mass production efficiency is slow.
  • the high capacitance characteristics of the ultracapacitor mainly come from the high surface area of the holes of the electrode sheets, and the holes can exist in 2D or 3D structure or independent holes, as shown in Fig. 5.
  • the pores can be divided into micropores of less than 10 ⁇ m, pores larger than 50 m, and mesopores in between.
  • the micropore is ineffective, and the mesoporous size is most suitable. Since the hole 3D is connected, the leakage of the capacitor component will be caused.
  • the hole A of the electrode surface is easily blocked by the sealant, but the inner hole of the electrode edge and the side is difficult to seal.
  • Taiwan Patent No. 472271 Even if a rubber wall is applied around the electrode, the low-viscosity colloid is immersed in the hole, as in Taiwan Patent No. 472271. This method still does not prevent side leakage, because the holes around the electrodes are not completely connected to the bottom by the vertical direction. In the electrode layer, some of the holes do not communicate with the surface of the electrode, but are connected to the upper side or the lower side, and the electrolyte leaks from the side of these channels.
  • each supercapacitor unit shares the same voltage.
  • the capacitor begins to expand, leak and rupture.
  • each unit composition should be the same.
  • the distance between the electrode sheets is a very important parameter, and the distance is controlled by a rubber wall or a gasket between the electrode sheets.
  • Taiwan Patent No. 472271 uses a glue wall to dispense or screen print on a holed electrode sheet as an isolating electrode and control the height of the supercapacitor unit.
  • 284921 are the heights of the control unit using a gasket, which is first immersed in the electrode hole with a low viscosity sealant, and then The height of the unit is controlled by a washer, but it is also difficult to control the thickness due to the glue in the hole, which also causes the gasket to lose accuracy. Causes the height of the unit to be different, affecting the distance between the units.
  • the present invention utilizes a special design to develop an energy storage device manufacturing method that improves manufacturing efficiency and product reliability.
  • the energy storage electrode sheets according to the required working voltage are stacked to form a prefabricated energy storage unit, and the capacitor leakage and the unit voltage equalization problem are solved by three sealing glues, and then the electrolyte is injected and sealed to complete the energy storage device. It will make the supercapacitor easier to manufacture, with higher efficiency and lower manufacturing cost.
  • an object of the present invention to provide an energy storage device that improves manufacturing efficiency and product reliability.
  • Process method suitable for mass production processes. Solve the current leakage reliability and low-efficiency commercial mass production problems, increase product yield, improve component energy storage operation life, and reduce production costs.
  • the electrodes and the separator are stacked into a pre-constructed energy storage unit according to the electrical requirements of the design.
  • the electrolyte is injected again, and the filling holes are finally sealed, thereby completing the manufacture of the ultra high capacity capacitor.
  • the method of constructing the invention comprises the following steps:
  • Pre-assembly unit stacking The holes are reserved for the electrode sheets, and the spacers are placed therebetween to stack the pre-formed units.
  • Reflow wall Heat the first, second and third rubber walls of the reflow, and completely seal the energy storage prefabricated unit except for the reserved filling holes. Remove the pressure and complete the energy storage prefabricated unit manufacturing.
  • B. Filling the electrolyte Filling the pores, filling the electrolyte to fill the energy storage prefabricated unit
  • the metal substrate can be titanium, tantalum, niobium, zirconium, iron, copper, lead, tin, nickel, zinc or a mixture thereof.
  • the coated metal oxide has a thickness of about 0.1 to 200 ⁇ m, and can be selected from tin, lead, vanadium, titanium, niobium, tantalum, niobium, tantalum, niobium, iron, cobalt, nickel, copper, molybdenum, niobium, chromium, magnesium, lanthanum. Or lanthanide metals or alloys or mixed metal oxides with each other, and it is possible to add a few percent of the additive to increase the conductivity.
  • the metal oxide coating method on the metal substrate is (1) solution method (including sol gel) (2) electrochemical deposition method (3) chemical vapor deposition method.
  • solution method including sol gel
  • electrochemical deposition method (3) chemical vapor deposition method.
  • the solution method is the most common, and can be divided into 1. Dip plating 2. Spray plating 3. Pressure plating 4. Rotating plating 5. Scraper method.
  • the rubber wall is made of electrically insulating polymer glue, which has good adhesion to the electrode sheets and is resistant to acid (alkali).
  • a thermal plastic polymer can be heated, remelted, and then cured.
  • the first rubber wall is a low-viscosity polymer glue that penetrates the porous metal oxide electrode and enters the hole on the surface of the electrode.
  • the coating area is about 10% of the electrode.
  • the first rubber wall can be made by immersion plating. You can use a dispenser or screen printer for dispensing or screen printing.
  • the material of the second rubber wall is the same as that of the first rubber wall.
  • the glue or screen printing rubber wall or the same material gasket can be used to construct a rubber wall of 10 ⁇ 100 ⁇ higher than the first rubber wall.
  • the rubber wall can fix and control the distance of the electric level plate, which has a considerable influence on the voltage equalization of the unit, and the too thin plastic wall will cause a large leakage current.
  • the third rubber wall is responsible for the side leakage prevention function, and the thickness is about 10 ⁇ 100 ⁇ .
  • the hot air, infrared, ultrasonic or high-frequency hot-melt sealant can be used to make it more sealed and complete the pre-constructed energy storage unit.
  • the separator between the two electrodes needs to be porous, acid-resistant (alkali), thin, etc., and can be glass fiber, polymer film (polyolefin plastic: polyethylene, polypropylene, PTFE, etc.), its shape size and uncoated
  • the electrodes of the rubber wall are the same.
  • the filled electrolyte contains an aqueous solution of an aqueous solution (aqueous solution of sulfuric acid or potassium hydroxide) or an organic solution, which is vacuum-injected into the filling holes of the energy storage prefabrication unit.
  • an aqueous solution aqueous solution of sulfuric acid or potassium hydroxide
  • an organic solution which is vacuum-injected into the filling holes of the energy storage prefabrication unit.
  • the sealing of the filling hole of the energy storage prefabrication unit can be the same as that of the rubber wall, coated or poured into the filling hole by a glue gun or a brush, and finally filled with an insulating resin (such as epoxy resin or acrylic). Resin) Forming.
  • an insulating resin such as epoxy resin or acrylic. Resin
  • Figure 1 is the supercapacitor basic unit
  • FIG. 2 shows the power storage unit
  • FIG. 3 shows the stacked storage units
  • Figure 4 is a conventional bipolar package supercapacitor structure diagram
  • FIG. 5 is a porous electrode diagram
  • Figure 6 is a diagram showing the electrode of the ultra high capacity capacitor of the present invention.
  • Figure 7 is an electrode scraping diagram of the ultra high capacity capacitor of the present invention.
  • Figure 9 is a second rubber wall coating diagram of the ultra high capacity capacitor of the present invention.
  • Figure 10 is a cutaway view of the electrode sheet of the ultra high capacity capacitor of the present invention.
  • Figure 11 is a stack diagram of the electrode sheets of the ultra high capacity capacitor of the present invention.
  • Figure 13 is a diagram showing the filling hole sealing of the ultra high capacity capacitor prefabrication unit of the present invention
  • Figure 14 is a schematic illustration of the pre-assembly unit diagram component of the ultra high capacity capacitor of the present invention
  • the packaging process of a high reliability and high efficiency energy storage device according to the present invention is as follows: First, as shown in FIG. 6, an electrode sheet 30 is provided, and the electrode 32 is uniformly coated on the metal substrate 31, and the electrode The thickness of 32 is about several ⁇ m to several tens of ⁇ m, and there are holes of different sizes on the surface.
  • the two sides of the electrode sheet 30 covered with the electrode 32 are scraped off into a square shape with a circular arc (not limited to a square shape, which can be various patterns), and a flat metal substrate (titanium) 31 is exposed.
  • the first rubber wall 33 of the isolation electrode is constructed, and a 1 ⁇ 10% low viscosity sealant, such as Kraton (Shell) sealant, is applied in the toluene/acetone solvent along the edge of the electrode. Dip the glue into the electrode. The thickness is slightly higher than the electrode height (about tens of ⁇ ⁇ ) and the width is between 0.1 and 2 mm. Because the edge electrode holes are different in depth, it is difficult to grasp the height after the glue is applied. Therefore, the first rubber wall 33 does not control the height, but seals the edge of the electrode to avoid most leakage.
  • a 1 ⁇ 10% low viscosity sealant such as Kraton (Shell) sealant
  • a second rubber wall 34 is coated on the surface of the flat substrate.
  • the width of the gap is between 0.1 and 2 mm and the height is about 50 100 ⁇ m.
  • the height of the second rubber wall 34 can be measured by an optical flatness meter, so that the height of the second rubber wall is the same on all sides (the error is less than 5%).
  • the second rubber wall 33 is the key to controlling the thickness of the electric storage unit and uniformly dividing the ultra-capacitance. As shown in Figure 9, a substrate circular area 35 is left under the electrodes. It is also possible to leave two or more circular areas on the electrodes.
  • the large electrode sheet is cut into small electrode sheets, and a hole is reserved in the circular area of the substrate reserved for the electrode.
  • the aperture 36 has an area smaller than the circular area of the substrate.
  • Cutting methods are available for wire cutting (WDM), stamping and laser cutting.
  • the electrode sheets 30 are stacked according to the required operating voltage.
  • a separator 40 having a shape such as an electrode 31 is placed between each of the two electrode sheets.
  • the outermost electrode sheet has an electrode extension piece 41 or a connecting piece on the splicing joint for connection to an external electric device.
  • the electrode sheets are in contact with the second rubber wall 34, and the thickness of the separator 40 is smaller than the height of the two second rubber walls 34 between the electrode sheets.
  • the separator may be a glass fiber, a high molecular weight film (polyolefin plastic: polyethylene, polypropylene, PTFE, etc.) having the same shape as that of the uncoated rubber wall.
  • the thickness is about 15 ⁇ 150 ⁇ m, and it is necessary to impregnate the electrolyte in addition to the characteristics of porosity, acid resistance (alkali) and thin thickness. Too thin a thickness will cause a large leakage current, while too thick will increase the equivalent series resistance (ESR).
  • ESR equivalent series resistance
  • the electrode sheets pressed under pressure are pressed using the press jig 50.
  • the electrode sheets will be shortened to a minimum.
  • a third rubber wall 51 is constructed by coating.
  • the first, second and third rubber walls of the soft melt are heated to fuse them together to improve the sealing property. Heating reflow methods include hot air, infrared, ultrasonic or high frequency thermal soft sealants.
  • the pressure is relieved to form a prefabricated energy storage unit 60.
  • the electrolyte is then poured into the vacuum to fill the pre-configured energy storage unit 60.
  • the filling hole 62 the only thing that communicates with the outside is the filling hole 62.
  • the sealant is applied to the edge of the filling hole 62 by using the coating 61, and the surface of the flat substrate and the edge of the porous electrode are contacted to ensure the sealing effect.
  • the filling holes are filled with a potting sealant or filled with other encapsulating materials such as epoxy.
  • the pre-constructed energy storage unit 60 injects a sealing resin such as epoxy resin as an outer casing for protecting the energy storage component, that is, completing the energy storage assembly 70.

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  • Engineering & Computer Science (AREA)
  • Power Engineering (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Manufacturing & Machinery (AREA)
  • Electric Double-Layer Capacitors Or The Like (AREA)

Abstract

La présente invention concerne un procédé de fabrication d’un dispositif de stockage d’énergie pouvant accroître l’efficacité de la fabrication et la fiabilité du produit. Des feuilles électrodes de stockage d’énergie en fonction du voltage de travail sont empilées pour constituer des unités de stockage d’énergie préformées. Les plus grandes difficultés concernant l’assemblage des condensateurs, la fuite de solutions et la pression moyenne des unités sont résolues par trois lignes de colle d’étanchéité, puis une solution électrolyte est injectée sous vide, renfermant les unités, et il est ainsi obtenu un dispositif de stockage d’énergie. Chacune des électrodes poreuses du dispositif possède deux surfaces servant simultanément d’électrode positive et d’électrode négative. Les feuilles électrodes sont empilées en polarité trempée, comme le dispositif de stockage d’énergie en série, pour le dispositif de stockage d’énergie, cela réduit la taille et le poids ainsi que les coûts de fabrication. Ainsi, les unités de stockage d’énergie peuvent en outre correspondre aux besoins des clients et les spécifications peuvent être réglées par différentes quantités de couches et zones d’électrodes, ceci étant favorable pour la fabrication industrielle en ligne.
PCT/CN2004/000946 2004-08-13 2004-08-13 Procédé de fabrication d’un dispositif de stockage d’énergie ayant une efficacité de fabrication et une fiabilité du produit accrues Ceased WO2006015518A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
PCT/CN2004/000946 WO2006015518A1 (fr) 2004-08-13 2004-08-13 Procédé de fabrication d’un dispositif de stockage d’énergie ayant une efficacité de fabrication et une fiabilité du produit accrues
CNA2004800437982A CN101023501A (zh) 2004-08-13 2004-08-13 提高制造效率及产品可靠度的储能装置制程方法

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/CN2004/000946 WO2006015518A1 (fr) 2004-08-13 2004-08-13 Procédé de fabrication d’un dispositif de stockage d’énergie ayant une efficacité de fabrication et une fiabilité du produit accrues

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WO2006015518A1 true WO2006015518A1 (fr) 2006-02-16

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WO (1) WO2006015518A1 (fr)

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1096611A (zh) * 1992-09-18 1994-12-21 宾纳科尔研究院 能量存储装置及其制造方法
CN1368745A (zh) * 2001-02-06 2002-09-11 国际超能源高科技股份有限公司 超电容能量储存装置的蓄电单元的封装方法

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1096611A (zh) * 1992-09-18 1994-12-21 宾纳科尔研究院 能量存储装置及其制造方法
CN1368745A (zh) * 2001-02-06 2002-09-11 国际超能源高科技股份有限公司 超电容能量储存装置的蓄电单元的封装方法

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