WO2015098052A1 - Séparateur pour dispositif de stockage d'énergie à électrolyte aqueux, son procédé de production et dispositif de stockage d'énergie à électrolyte aqueux l'utilisant - Google Patents

Séparateur pour dispositif de stockage d'énergie à électrolyte aqueux, son procédé de production et dispositif de stockage d'énergie à électrolyte aqueux l'utilisant Download PDF

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WO2015098052A1
WO2015098052A1 PCT/JP2014/006312 JP2014006312W WO2015098052A1 WO 2015098052 A1 WO2015098052 A1 WO 2015098052A1 JP 2014006312 W JP2014006312 W JP 2014006312W WO 2015098052 A1 WO2015098052 A1 WO 2015098052A1
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Prior art keywords
epoxy resin
separator
storage device
aqueous electrolyte
power storage
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PCT/JP2014/006312
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English (en)
Japanese (ja)
Inventor
伊藤　聡
俊祐 能見
矢野　雅也
洋佑 山田
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日東電工株式会社
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Publication of WO2015098052A1 publication Critical patent/WO2015098052A1/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
    • H01G11/52—Separators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/411—Organic material
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/403—Manufacturing processes of separators, membranes or diaphragms
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2220/00—Batteries for particular applications
    • H01M2220/10—Batteries in stationary systems, e.g. emergency power source in plant
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2220/00—Batteries for particular applications
    • H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to a separator for an aqueous electrolyte electricity storage device and an aqueous electrolyte electricity storage device, and more particularly to a separator suitable for an aqueous electrolyte electricity storage device represented by an electric double layer capacitor using an aqueous electrolyte and this kind of electricity storage device.
  • Known separators for water-based electrolyte electricity storage devices include, for example, fiber sheets made of inorganic fibers (for example, Patent Document 1) and porous membranes using a polyolefin-based resin (for example, Patent Document 2).
  • the separator for the aqueous electrolyte storage device is required to have high affinity with the aqueous electrolyte.
  • the present invention A separator for an aqueous electrolyte electricity storage device, A three-dimensional network skeleton composed of epoxy resin; Pores communicating so that ions can move between the front and back surfaces of the separator; The separator for water-system electrolyte electrical storage devices provided with this.
  • the present invention provides: Preparing an epoxy resin composition comprising an epoxy resin, a curing agent and a porogen; A step of molding the cured product of the epoxy resin composition into a sheet shape or curing the sheet-shaped molded product of the epoxy resin composition so as to obtain an epoxy resin sheet; Removing the porogen from the epoxy resin sheet; The manufacturing method of the separator for water-system electrolyte electrical storage devices containing this is provided.
  • the present invention provides: A positive electrode; A negative electrode, The separator of the present invention disposed between the positive electrode and the negative electrode; An aqueous electrolyte impregnated in the separator; A water-based electrolyte electricity storage device is provided.
  • Epoxy resin has a high affinity with aqueous electrolytes and is suitable for forming a microporous structure in which short-circuiting between electrodes is unlikely to occur.
  • ADVANTAGE OF THE INVENTION According to this invention, the separator for aqueous
  • FIG. 1 is a schematic cross-sectional view of an aqueous electrolyte electricity storage device according to an embodiment of the present invention. Schematic diagram of the cutting process
  • the water-based electrolyte power storage device refers to a power storage device using an aqueous electrolyte solution (aqueous electrolyte solution).
  • the water-based electrolyte electricity storage device 100 is a water-based electric double layer capacitor including a positive electrode 2, a negative electrode 3, and a separator 4.
  • the separator 4 is disposed between the positive electrode 2 and the negative electrode 3.
  • the positive electrode 2, the negative electrode 3, and the separator 4 are integrally wound to constitute the element body 10.
  • the positive electrode 2 and the negative electrode 3 are each configured by laminating a polarizable electrode, a collector electrode, and a polarizable electrode in this order.
  • the separator 4 includes a three-dimensional network skeleton made of an epoxy resin and holes that communicate with each other so that ions can move between the front surface and the back surface of the separator.
  • the element body 10 is accommodated in the cylindrical case 6. That is, the water-based electrolyte electricity storage device 100 has a cylindrical shape. However, the shape of the water-based electrolyte electricity storage device 100 is not particularly limited. The water-based electrolyte electricity storage device 100 may have a flat square shape, for example. The element body 10 does not necessarily have a winding structure. A plate-shaped element body may be formed by simply laminating the positive electrode 2, the separator 4, and the negative electrode 3.
  • the case 6 is made of a metal such as stainless steel or aluminum.
  • the water-based electrolyte electricity storage device 100 further includes a positive electrode terminal 2a and a negative electrode terminal 3a.
  • the positive electrode terminal 2 a and the negative electrode terminal 3 a protrude upward from the upper surface of the case 6.
  • the element body 10 is impregnated with an aqueous electrolyte.
  • the positive electrode 2, the negative electrode 3, and other members constituting the water-based electrolyte electricity storage device 100 those conventionally known can be used without particular limitation.
  • the water-based electric double layer capacitor is taken as an example, but the present invention is not limited to this, and can be applied to a water-based electrolyte electricity storage device using a water-based electrolyte and a separator.
  • the separator 4 is composed of a porous epoxy resin film having a three-dimensional network skeleton and pores. Adjacent holes may be in communication with each other so that ions can move between the front surface and the back surface of the separator 4, that is, ions can move between the positive electrode 2 and the negative electrode 3.
  • the separator 4 has a thickness in the range of 5 to 50 ⁇ m, for example. If the separator 4 is too thick, it becomes difficult to move ions between the positive electrode 2 and the negative electrode 3. Although it is not impossible to manufacture the separator 4 having a thickness of less than 5 ⁇ m, in order to ensure the reliability of the water-based electrolyte electricity storage device 100, a thickness of 5 ⁇ m or more, particularly 10 ⁇ m or more is preferable.
  • the separator 4 has, for example, a porosity of 20 to 80%, preferably 20 to 60%, and an average pore diameter of 0.02 to 1 ⁇ m. When the porosity and average pore diameter are adjusted to such ranges, the separator 4 can sufficiently exhibit the required functions.
  • the average pore diameter can be obtained by observing the cross section of the separator 4 with a scanning electron microscope. Specifically, image processing is performed for each of the holes existing in a range of a field width of 60 ⁇ m and a predetermined depth from the surface (for example, 1/5 to 1/100 of the thickness of the separator 4). Thus, the pore diameter can be obtained, and the average value thereof can be obtained as the average pore diameter.
  • Image processing can be performed using, for example, free software “Image J” or “Photoshop” manufactured by Adobe.
  • the separator 4 may have an air permeability (Gurley value) in the range of 1 to 1000 seconds / 100 cm 3 . Since the separator 4 has air permeability in such a range, ions can easily move inside the separator 4.
  • the air permeability can be measured according to a method defined in Japanese Industrial Standard (JIS) P8117.
  • the separator for an aqueous electrolyte electricity storage device (separator 4) of this embodiment includes an epoxy resin porous film having a microporous structure, and short-circuiting between electrodes is less likely to occur. Even when the film thickness is small, short-circuiting is unlikely to occur, so this separator is suitable for increasing the capacity of the aqueous electrolyte electricity storage device.
  • the separator for an aqueous electrolyte electricity storage device of this embodiment does not contain a filler. For this reason, it is suitable for weight reduction and thickness reduction of an electrical storage device.
  • the separator for an aqueous electrolyte electricity storage device of the present embodiment is easy for the electrolyte to penetrate.
  • the internal resistance in the electricity storage device can be suppressed, and the characteristics of the aqueous electrolyte electricity storage device can be improved.
  • the time until the separator is filled with the aqueous electrolytic solution can be shortened, so that the productivity of the aqueous electrolyte electrical storage device can be improved.
  • the epoxy resin porous membrane can be produced, for example, by any of the following methods (a), (b), and (c).
  • the methods (a) and (b) are common in that the curing step is performed after the epoxy resin composition is formed into a sheet.
  • the method (c) is characterized in that an epoxy resin block-shaped cured body is formed and the cured body is formed into a sheet shape.
  • Method (a) An epoxy resin composition containing an epoxy resin, a curing agent and a porogen is applied onto a substrate so that a sheet-like molded body of the epoxy resin composition is obtained. Thereafter, the sheet-like molded body of the epoxy resin composition is heated to three-dimensionally crosslink the epoxy resin. At that time, a co-continuous structure is formed by phase separation of the crosslinked epoxy resin and the porogen. Thereafter, the porogen is removed by washing from the obtained epoxy resin sheet and dried to obtain an epoxy resin porous film having pores communicating with the three-dimensional network skeleton.
  • substrate is not specifically limited, A plastic substrate, a glass substrate, a metal plate, etc. can be used as a board
  • Method (b) An epoxy resin composition containing an epoxy resin, a curing agent and a porogen is applied on the substrate. Thereafter, another substrate is placed on the applied epoxy resin composition to produce a sandwich structure. Note that spacers (for example, double-sided tape) may be provided at the four corners of the substrate in order to ensure a certain distance between the substrates. Next, the sandwich structure is heated to cross-link the epoxy resin three-dimensionally. At that time, a co-continuous structure is formed by phase separation of the crosslinked epoxy resin and the porogen. Thereafter, the obtained epoxy resin sheet is taken out, the porogen is removed by washing, and dried to obtain an epoxy resin porous membrane having pores communicating with the three-dimensional network skeleton.
  • substrate is not restrict
  • Method (c) An epoxy resin composition containing an epoxy resin, a curing agent and a porogen is filled into a mold having a predetermined shape. Thereafter, a cured product of the cylindrical or columnar epoxy resin composition is produced by three-dimensionally crosslinking the epoxy resin. At that time, a co-continuous structure is formed by phase separation of the crosslinked epoxy resin and the porogen. Then, while rotating the hardening body of an epoxy resin composition centering on a cylinder axis
  • the method for producing the porous epoxy resin membrane will be described in more detail while taking the method (c) as an example.
  • the process of preparing an epoxy resin composition, the process of hardening an epoxy resin, the process of removing a porogen, etc. are common to each method.
  • the material which can be used is common to each method.
  • the epoxy resin porous membrane can be manufactured through the following main steps.
  • An epoxy resin composition is prepared.
  • a cured product of the epoxy resin composition is formed into a sheet.
  • the porogen is removed from the epoxy resin sheet.
  • an epoxy resin composition containing an epoxy resin, a curing agent and a porogen is prepared. Specifically, an epoxy resin and a curing agent are dissolved in a porogen to prepare a uniform solution.
  • an aromatic epoxy resin either an aromatic epoxy resin or a non-aromatic epoxy resin can be used.
  • the aromatic epoxy resin include a polyphenyl-based epoxy resin, an epoxy resin containing a fluorene ring, an epoxy resin containing triglycidyl isocyanurate, an epoxy resin containing a heteroaromatic ring (for example, a triazine ring), and the like.
  • Polyphenyl-based epoxy resins include bisphenol A type epoxy resins, brominated bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol AD type epoxy resins, stilbene type epoxy resins, biphenyl type epoxy resins, and bisphenol A novolak type epoxy resins.
  • Non-aromatic epoxy resins include aliphatic glycidyl ether type epoxy resins, aliphatic glycidyl ester type epoxy resins, alicyclic glycidyl ether type epoxy resins, alicyclic glycidyl amine type epoxy resins, and alicyclic glycidyl ester type epoxy resins. Etc. These may be used alone or in combination of two or more.
  • bisphenol A type epoxy resin brominated bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AD type epoxy resin, aromatic glycidylamine type epoxy resin, epoxy resin containing fluorene ring, triglycidyl isocyanurate
  • Preferred is at least one selected from the group consisting of an epoxy resin, an alicyclic glycidyl ether type epoxy resin, an alicyclic glycidyl amine type epoxy resin, and an alicyclic glycidyl ester type epoxy resin. What has an equivalent can be used conveniently.
  • these epoxy resins are used, a uniform three-dimensional network skeleton and uniform pores can be formed, and excellent chemical resistance and high strength can be imparted to the epoxy resin porous film.
  • the epoxy resin composition includes a glycidylamine type epoxy resin, such as a glycidylamine type epoxy resin and a bisphenol A type epoxy resin, a brominated bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a bisphenol.
  • AD type epoxy resin epoxy resin containing fluorene ring, epoxy resin containing triglycidyl isocyanurate, alicyclic glycidyl ether type epoxy resin, and at least one epoxy resin selected from the group consisting of alicyclic glycidyl ester type epoxy resins Including.
  • the glycidyl amine type epoxy resin is an epoxy resin having a structure in which the hydrogen atom of the amino group of the amine compound is substituted with a glycidyl group, and the glycidyl amine type epoxy resin has two or more diglycidyl from the viewpoint of particularly high crosslinkability. It preferably has an amino group.
  • a specific example of such a glycidylamine type epoxy resin is 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane (commercially available from Mitsubishi Gas Chemical Company under the trade name “TETRAD®-C”).
  • N, N, N ′, N′-tetraglycidyl-m-xylenediamine (commercially available from Mitsubishi Gas Chemical Co., Ltd. under the trade name “TETRAD (registered trademark) -X”)
  • an epoxy resin having a diglycidylamino group (commercially available from Mitsubishi Gas Chemical Co., Ltd. under the trade name “TETRAD (registered trademark) -X”)
  • an epoxy resin having a diglycidylamino group When using glycidylamine type epoxy resin, uniform three-dimensional network skeleton and uniform pores can be formed, crosslink density after curing is improved, and epoxy resin porous film has high strength, heat resistance and chemical resistance. Can be granted.
  • a glycidylamine type epoxy resin may be used independently and may use 2 or more types together.
  • Aromatic curing agents include aromatic amines (eg, metaphenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, benzyldimethylamine, dimethylaminomethylbenzene), aromatic acid anhydrides (eg, phthalic anhydride, trimellitic anhydride) , Pyromellitic anhydride), phenol resins, phenol novolac resins, amines containing heteroaromatic rings (for example, amines containing triazine rings), and the like.
  • Non-aromatic curing agents include aliphatic amines (eg, ethylenediamine, 1,4-butylenediamine, 1,5-pentanediamine, 1,6-hexanediamine, 1,7-heptanediamine, 1,8-octane.
  • aliphatic amines eg, ethylenediamine, 1,4-butylenediamine, 1,5-pentanediamine, 1,6-hexanediamine, 1,7-heptanediamine, 1,8-octane.
  • Alicyclic amines eg, isophoronediamine, menthanediamine, N-aminoethylpiperazine, 3,9-bis (3-aminopropyl) 2,4,8,10-tetraoxaspiro (5,5) undecane adduct, Bis (4-amino-3-methyl Kurohekishiru) methane, bis (4-aminocyclohexyl) methane, these modified products
  • aliphatic polyamide amines containing a polyamine and a dimer acid may be used alone or in combination of two or more.
  • a curing agent having two or more primary amines in the molecule can be suitably used.
  • 1,6-hexanediamine is preferred because of the high crosslink density of the resulting epoxy resin porous membrane, higher chemical stability, and ease of availability and handling.
  • a combination of an epoxy resin and a curing agent a combination of an aromatic epoxy resin and an aliphatic amine curing agent, a combination of an aromatic epoxy resin and an alicyclic amine curing agent, or an alicyclic epoxy resin and an aromatic amine A combination with a curing agent is preferred.
  • excellent heat resistance can be imparted to the porous epoxy resin membrane.
  • the porogen may be a solvent that can dissolve the epoxy resin and the curing agent. Porogens are also used as solvents that can cause reaction-induced phase separation after the epoxy resin and curing agent are polymerized. Specifically, cellosolves such as methyl cellosolve and ethyl cellosolve, esters such as ethylene glycol monomethyl ether acetate and propylene glycol monomethyl ether acetate, glycols such as polyethylene glycol and polypropylene glycol, polyoxyethylene monomethyl ether and polyoxyethylene Ethers such as dimethyl ether can be used as the porogen. These may be used alone or in combination of two or more.
  • at least one selected from the group consisting of polyethylene glycol having a molecular weight of 200 or less, polypropylene glycol having a molecular weight of 500 or less, polyoxyethylene monomethyl ether, and propylene glycol monomethyl ether acetate can be preferably used.
  • these porogens are used, a uniform three-dimensional network skeleton and uniform pores can be formed. These may be used alone or in combination of two or more.
  • a solvent in which a reaction product of the epoxy resin and the curing agent is soluble can be used as a porogen.
  • porogen include brominated bisphenol A type epoxy resin (“Epicoat 5058” manufactured by Japan Epoxy Resin Co., Ltd.).
  • the porosity, average pore size, and pore size distribution of the epoxy resin porous membrane vary depending on the type of raw material, the mixing ratio of the raw material, and the reaction conditions (for example, heating temperature and heating time during reaction-induced phase separation). Therefore, it is preferable to select optimum conditions in order to obtain the target porosity, average pore diameter, and pore diameter distribution.
  • the reaction conditions for example, heating temperature and heating time during reaction-induced phase separation. Therefore, it is preferable to select optimum conditions in order to obtain the target porosity, average pore diameter, and pore diameter distribution.
  • the co-continuous structure of the crosslinked epoxy resin and porogen is fixed in a specific state and stable. A porous structure can be obtained.
  • the blending ratio of the curing agent to the epoxy resin is, for example, 0.6 to 1.5 in terms of the curing agent equivalent to 1 equivalent of epoxy group.
  • Appropriate curing agent equivalent contributes to improvement of properties such as heat resistance, chemical durability and mechanical properties of the epoxy resin porous membrane.
  • a curing accelerator may be added to the solution in order to obtain the desired porous structure.
  • the curing accelerator include tertiary amines such as triethylamine and tributylamine, and imidazoles such as 2-phenol-4-methylimidazole, 2-ethyl-4-methylimidazole, and 2-phenol-4,5-dihydroxyimidazole. It is done.
  • porogen 40 to 80% by weight of porogen can be used with respect to the total weight of epoxy resin, curing agent and porogen.
  • an epoxy resin porous film having a desired porosity, average pore diameter, and air permeability can be formed.
  • the average pore diameter of the epoxy resin porous membrane As one method for adjusting the average pore diameter of the epoxy resin porous membrane to a desired range, there is a method of using a mixture of two or more epoxy resins having different epoxy equivalents.
  • the difference in epoxy equivalent is preferably 100 or more, and there are cases where an epoxy resin that is liquid at normal temperature and an epoxy resin that is solid at normal temperature are mixed and used.
  • a cured product of the epoxy resin composition is prepared from a solution containing an epoxy resin, a curing agent and a porogen. Specifically, the solution is filled in a mold and heated as necessary. A cured body having a predetermined shape is obtained by three-dimensionally crosslinking the epoxy resin. In that case, a co-continuous structure is formed by phase-separation of a crosslinked epoxy resin and a porogen.
  • the shape of the cured body is not particularly limited. If a columnar or cylindrical mold is used, a cured body having a cylindrical or columnar shape can be obtained. When the cured body has a cylindrical or columnar shape, it is easy to carry out a cutting step (see FIG. 2) described later.
  • the temperature and time required for curing the epoxy resin composition are not particularly limited because they vary depending on the type of epoxy resin and curing agent.
  • a curing treatment can be performed at room temperature.
  • the temperature is about 20 to 40 ° C., and the time is about 3 to 100 hours, preferably about 20 to 50 hours.
  • the temperature is about 40 to 120 ° C., preferably about 60 to 100 ° C., and the time is about 10 to 300 minutes, preferably about 30 to 180 minutes.
  • post-cure post-treatment
  • post-curing conditions are not particularly limited, but the temperature is room temperature or about 50 to 160 ° C., and the time is about 2 to 48 hours.
  • the dimensions of the cured body are not particularly limited.
  • the diameter of the cured body is, for example, 20 cm or more, preferably 30 to 150 cm, from the viewpoint of manufacturing efficiency of the epoxy resin porous film.
  • the length (axial direction) of the cured body can also be appropriately set in consideration of the dimensions of the epoxy resin porous film to be obtained.
  • the length of the cured body is, for example, 20 to 200 cm, preferably 20 to 150 cm, and more preferably 20 to 120 cm from the viewpoint of ease of handling.
  • the cured body is formed into a sheet.
  • the cured body having a cylindrical or columnar shape can be formed into a sheet shape by the following method. Specifically, the cured body 12 is attached to the shaft 14 as shown in FIG.
  • the surface layer portion of the cured body 12 is cut (sliced) at a predetermined thickness using a cutting blade 18 (slicer) so that an epoxy resin sheet 16 having a long shape is obtained.
  • the surface layer portion of the cured body 12 is cut while rotating the cured body 12 relative to the cutting blade 18 around the cylindrical axis O (or columnar axis) of the cured body 12. According to this method, the epoxy resin sheet 16 can be produced efficiently.
  • the line speed when cutting the cured body 12 is in the range of 2 to 70 m / min, for example.
  • the thickness of the epoxy resin sheet 16 is determined according to the target thickness (10 to 50 ⁇ m) of the epoxy resin porous film. Since the thickness slightly decreases when the porogen is removed and dried, the epoxy resin sheet 16 is usually slightly thicker than the target thickness of the epoxy resin porous film.
  • the length of the epoxy resin sheet 16 is not specifically limited, From a viewpoint of the production efficiency of the epoxy resin sheet 16, it is 100 m or more, for example, Preferably it is 1000 m or more.
  • the porogen is extracted from the epoxy resin sheet 16 and removed.
  • the porogen can be removed from the epoxy resin sheet 16 by immersing the epoxy resin sheet 16 in a solvent.
  • the solvent is preferably a halogen-free solvent that does not have a large environmental load.
  • the halogen-free solvent for removing the porogen from the epoxy resin sheet 16 at least one selected from the group consisting of water, DMF (N, N-dimethylformamide), DMSO (dimethyl sulfoxide), and THF (tetrahydrofuran) is used as the porogen. It can be used depending on the type. Also, supercritical fluids such as water and carbon dioxide can be used as a solvent for removing porogen. In order to positively remove the porogen from the epoxy resin sheet 16, ultrasonic cleaning may be performed, or the solvent may be heated and used.
  • the cleaning device for removing the porogen is not particularly limited, and a known cleaning device can be used.
  • a multistage cleaning apparatus having a plurality of cleaning tanks can be suitably used.
  • the number of cleaning stages is more preferably 3 or more.
  • the temperature of the solvent may be changed or the type of the solvent may be changed in the cleaning of each stage.
  • the epoxy resin porous film is dried.
  • the drying conditions are not particularly limited, and the temperature is usually about 40 to 120 ° C., preferably about 50 to 100 ° C., and the drying time is about 10 seconds to 5 minutes.
  • a drying apparatus employing a known sheet drying method such as a tenter method, a floating method, a roll method, or a belt method can be used. A plurality of drying methods may be combined.
  • an epoxy resin porous film having a microporous structure that can be used as the separator 4 can be manufactured very easily. Since the process required at the time of manufacture of a polyolefin porous membrane, for example, an extending process, can be omitted, an epoxy resin porous membrane can be manufactured with high productivity.
  • the separator 4 may be comprised only by the epoxy resin porous film, and may be comprised by the laminated body of an epoxy resin porous film and another porous material.
  • porous materials include polyolefin porous films such as polyethylene porous films and polypropylene porous films, cellulose porous films, and fluororesin porous films.
  • Other porous materials may be provided only on one side of the epoxy resin porous membrane, or may be provided on both sides.
  • the separator 4 may be composed of a laminate of an epoxy resin porous film and a reinforcing material.
  • the reinforcing material include woven fabric and non-woven fabric.
  • the reinforcing material may be provided only on one side of the epoxy resin porous membrane, or may be provided on both sides.
  • RO water means pure water obtained by processing using a reverse osmosis membrane.
  • the short circuit rate was measured by the following method. An aluminum foil having a thickness of 20 ⁇ m was cut into a 30 mm square. Next, the separator was cut into a 40 mm square. This separator was immersed in a 0.5 mol / L sulfuric acid aqueous solution as an electrolytic solution, and then sandwiched between the aluminum foils to prepare an electrode group. Next, a square aluminum plate having a thickness of 5 mm and a 35 mm square, and an electrode group was sandwiched from both sides using an aluminum plate having a terminal connection portion prepared on the end face.
  • interposed this electrode group was inserted
  • the test electrode group obtained as described above was placed in a pressure device.
  • An AC resistance measuring machine manufactured by Hioki Electric Co., Ltd.
  • Pressure was applied until a surface pressure of 0.2 MPa was applied to the test electrode group, and the resistance value was measured. When the resistance value decreased, it was determined that a short circuit occurred. This measurement was carried out 10 times in total for each example, and the short circuit rate was X / 10 (of 10 measurements, the number of short circuits was X times).
  • Example 1 In a 3 L cylindrical plastic container, jER (registered trademark) 828 (bisphenol A type epoxy resin, manufactured by Mitsubishi Chemical Corporation, epoxy equivalent of 184 to 194 g / eq.) And TETRAD (registered trademark) -C (glycidylamine) Type epoxy resin, Mitsubishi Gas Chemical Co., Ltd., epoxy equivalent 95-110 g / eq.) 25.0 parts by weight is dissolved in polypropylene glycol (ADEKA Co., Ltd., Adeka Polyether P-400) 211.9 parts by weight, An epoxy resin / polypropylene glycol solution was prepared.
  • the polypropylene glycol was removed by immersion in water for 12 hours. Then, it dried for 2 hours in 80 degreeC atmosphere, and obtained the epoxy resin porous membrane (separator) which has a thickness of 48 micrometers.
  • Example 2 The same procedure as in Example 1 was carried out except that a continuous lathe was sliced with a thickness of 22 ⁇ m using a cutting lathe device to obtain an epoxy resin porous film (separator) having a thickness of 21 ⁇ m.
  • Table 1 shows the evaluation results for the examples.
  • Example 1 As shown in Table 1, in Example 1, no short circuit between the electrodes occurred. Also in Example 2 in which the film thickness was made thinner than Example 1, no short circuit occurred between the electrodes. Moreover, these epoxy resin porous membranes (separator) showed favorable liquid absorptivity, and it turned out that it has high affinity with the sulfuric acid aqueous solution which is aqueous electrolyte solution.
  • the separator provided by the present invention can be suitably used for water-based electrolyte electricity storage devices such as electric double layer capacitors, and is particularly required for vehicles, motorcycles, ships, construction machinery, industrial machinery, residential electricity storage systems, and the like. It can be suitably used for a capacitor having a capacity.

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  • Power Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Cell Separators (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
  • Electric Double-Layer Capacitors Or The Like (AREA)

Abstract

L'invention concerne un séparateur pour un dispositif de stockage d'énergie à électrolyte aqueux. Le séparateur est hautement compatible avec une batterie à électrolyte aqueux et il est approprié pour prévenir des courts-circuits entre les électrodes. L'invention concerne un séparateur pour un dispositif de stockage d'énergie à électrolyte aqueux, le séparateur étant pourvu d'une structure de réseau tridimensionnel qui est constitué d'une résine époxy et de pores qui communiquent de façon à permettre aux ions de se mouvoir entre les surfaces avant et arrière du séparateur. L'épaisseur du séparateur est compris dans la plage de 5 µm à 50 μm, par exemple. Ce séparateur peut être produit, par exemple, en retirant les agents porogènes d'une feuille de résine époxy.
PCT/JP2014/006312 2013-12-25 2014-12-17 Séparateur pour dispositif de stockage d'énergie à électrolyte aqueux, son procédé de production et dispositif de stockage d'énergie à électrolyte aqueux l'utilisant WO2015098052A1 (fr)

Applications Claiming Priority (2)

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JP2013267882A JP2015126029A (ja) 2013-12-25 2013-12-25 水系電解質蓄電デバイス用セパレータとその製造方法、及びそれを用いた水系電解質蓄電デバイス
JP2013-267882 2013-12-25

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WO2015098052A1 true WO2015098052A1 (fr) 2015-07-02

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008013672A (ja) * 2006-07-06 2008-01-24 Kyoto Institute Of Technology エポキシ樹脂硬化物多孔体と繊維を含んでなる複合材料
JP2010077358A (ja) * 2008-09-29 2010-04-08 Nitto Denko Corp エポキシ樹脂多孔質膜及びその製造方法
WO2010047383A1 (fr) * 2008-10-23 2010-04-29 日東電工株式会社 Procédé de production d’une feuille poreuse en résine thermodurcissable, feuille poreuse en résine thermodurcissable, et membrane composite semi-perméable utilisant celle-ci
JP2011103430A (ja) * 2009-11-11 2011-05-26 Taiwan Textile Research Inst 電気二重層キャパシタの水系電解質および当該水系電解質を用いた電気二重層キャパシタ
JP2013004210A (ja) * 2011-06-13 2013-01-07 Nitto Denko Corp 非水電解質蓄電デバイス用セパレータ、非水電解質蓄電デバイス及びそれらの製造方法

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008013672A (ja) * 2006-07-06 2008-01-24 Kyoto Institute Of Technology エポキシ樹脂硬化物多孔体と繊維を含んでなる複合材料
JP2010077358A (ja) * 2008-09-29 2010-04-08 Nitto Denko Corp エポキシ樹脂多孔質膜及びその製造方法
WO2010047383A1 (fr) * 2008-10-23 2010-04-29 日東電工株式会社 Procédé de production d’une feuille poreuse en résine thermodurcissable, feuille poreuse en résine thermodurcissable, et membrane composite semi-perméable utilisant celle-ci
JP2011103430A (ja) * 2009-11-11 2011-05-26 Taiwan Textile Research Inst 電気二重層キャパシタの水系電解質および当該水系電解質を用いた電気二重層キャパシタ
JP2013004210A (ja) * 2011-06-13 2013-01-07 Nitto Denko Corp 非水電解質蓄電デバイス用セパレータ、非水電解質蓄電デバイス及びそれらの製造方法

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