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WO1992016977A1 - Separateur pour batterie au plomb du type ferme - Google Patents

Separateur pour batterie au plomb du type ferme Download PDF

Info

Publication number
WO1992016977A1
WO1992016977A1 PCT/JP1992/000306 JP9200306W WO9216977A1 WO 1992016977 A1 WO1992016977 A1 WO 1992016977A1 JP 9200306 W JP9200306 W JP 9200306W WO 9216977 A1 WO9216977 A1 WO 9216977A1
Authority
WO
WIPO (PCT)
Prior art keywords
separator
weight
synthetic pulp
acid battery
polyolefin
Prior art date
Application number
PCT/JP1992/000306
Other languages
English (en)
Japanese (ja)
Inventor
Koji Horimoto
Motofumi Nakamura
Motoyuki Esaki
Yoshitaka Tanaka
Original Assignee
Mitsui Petrochemical Industries, Ltd.
Gs Kasei Kogyo K.K.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from JP4045219A external-priority patent/JPH05283053A/ja
Application filed by Mitsui Petrochemical Industries, Ltd., Gs Kasei Kogyo K.K. filed Critical Mitsui Petrochemical Industries, Ltd.
Publication of WO1992016977A1 publication Critical patent/WO1992016977A1/fr

Links

Classifications

    • 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
    • H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
    • H01M50/417—Polyolefins
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0002—Aqueous electrolytes
    • H01M2300/0005—Acid electrolytes
    • 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 a sealed lead-acid battery comprising a porous mat, and more particularly, to a porous pine obtained by dry-making a material mainly composed of a polyolefin synthetic pulp.
  • the present invention relates to a separator for a sealed lead-acid battery, which is composed of a battery.
  • Eve's sealed lead-acid battery in which oxygen gas generated from the positive electrode is absorbed by the negative electrode while the battery is being charged, comes in two types: retainer type and gel type.
  • retainer type a mat-like separator with liquid retention properties is inserted between the positive and negative plates to maintain the electrolytic properties necessary for battery discharge and to separate the electrodes, thereby eliminating maintenance.
  • it has been used as a backup power supply for portable devices, computers in an emergency (power failure), or a power supply for automobiles, etc., taking advantage of its characteristics such as liquid leakage and position-free.
  • a closed type lead-acid battery of the retainer type uses a mat made of ultra-fine glass fiber (hereinafter referred to as a glass separator) (see, for example, Japanese Patent Application Laid-Open No. 60-110118). No. 61, Japanese Patent Application Laid-Open No. 59-73842), and a separator composed of a polyolefin-based wet nonwoven fabric has also been proposed (Japanese Patent Application Laid-Open No. 62-268890). No. Refer to the gazette).
  • separators using extra-fine crow fibers glass fibers are very expensive and are not considered to be industrially suitable materials.
  • separators made of polyolefin-based wet nonwoven fabric Must be bulky in order to have sufficient liquid retention, as a means of mixing glass fibers, etc., which is inevitably disadvantageous in terms of cost.
  • batteries that are used for many purposes are generally required to be lighter and have higher capacities.
  • An object of the present invention is to provide a separator for a sealed type lead-acid battery which is reduced in cost, improves low-temperature high-rate discharge capacity, is excellent in battery discharge characteristics, and is lightweight.
  • the present invention has been proposed to achieve the above object, and uses a mat made of a material mainly composed of a polyolefin-based synthetic valve made porous by a special method as a separator. It is characterized by the following.
  • a separator for a sealed lead-acid battery characterized by comprising a porous mat obtained by the above method.
  • Closed hermetic lead storage comprising porous mat obtained by dry-papermaking 98 to 50% by weight and a binder having a melting point lower than that of the synthetic pulp, 2 to 50% by weight.
  • a battery separator will be provided.
  • a sealed lead-acid battery having further excellent characteristics as described above is obtained by using the polyolefin synthetic pulp having a specific surface area of 1 m 2 or more as measured by a BET adsorption method. Separate evenings will be provided.
  • FIG. 1 is a schematic view of an apparatus for measuring the maximum pore diameter of a separator in an embodiment of the present invention.
  • the polyolefin-based synthetic pulp is subjected to a hydrophilic treatment, particularly a hydrophilic treatment using an aqueous solution of a surfactant, so that a separator for a sealed lead-acid battery having more excellent respective physical properties can be obtained.
  • a hydrophilic treatment particularly a hydrophilic treatment using an aqueous solution of a surfactant
  • a separator for a sealed lead-acid battery having more excellent respective physical properties can be obtained.
  • Suitable for sealed lead-acid batteries by blending various synthetic fibers, natural pulp, and acid-resistant inorganic powder in the following ranges
  • a separator can be provided.
  • the separator obtained by the present invention is manufactured by dry paper-making in particular, there is a feature that a bulky material can be easily obtained without shrinkage due to surface tension of water during drying.
  • the synthetic pulp used as a main material a polyolefin-based synthetic pulp is used, and in particular, a solution or a solution obtained by flash spinning emulsion is preferably used.
  • Polyolefin-based synthetic pulp is known per se, and those manufactured by various methods as described below can be used.
  • those produced by emulsion flash method using polyvinyl alcohol (PVA) as a hydrophilizing agent are preferably used.
  • the PVA content is preferably 0.01 to 10% by weight.
  • these polyolefin synthetic pulp have a specific surface area of 1 m 2 Zg or more as measured by the BET adsorption method.
  • it is
  • polystyrene resin examples include homopolymers of olefins such as polyethylene and polyethylene, copolymers of ethylene and propylene, copolymers of ethylene and 1-butene, and copolymers of ethylene and 1-methylpentene. Copolymers of ethylene and another ⁇ -olefin are preferred, and among them, crystalline polyolefin is preferably used in terms of mechanical strength.
  • the polyolefin-based synthetic pulp thus obtained has a fiber length of 0.1 to 10 and can be easily dry-processed thereafter. It has excellent discharge characteristics and is lightweight and inexpensive. '
  • polyolefin-based synthetic pulp is itself hydrophobic, it is possible to use a hydrophilic-treated synthetic pulp in order to improve the water retention of the obtained separator.
  • polyester acrylic, polypropylene, polyethylene, polystyrene, methyl meth acrylate, acrylonitrile
  • synthetic fibers such as vinylidene chloride resin, natural fibers, glass fibers, silica fibers, alumina silicate fibers, inorganic fibers such as slag fibers, and acid-resistant inorganic powders such as silica powder and diatomaceous earth are required. Mix according to be able to.
  • Dry papermaking is a method in which the above-mentioned synthetic pulp is made into a sheet in a dried state mainly using a card or the like.
  • a binder having a lower melting point than the polyolefin-based synthetic pulp is added to the above-mentioned synthetic pulp.
  • the method called fiber bonding, in which the two are mixed and thermally fused at the melting temperature of the binder, is the shortest, simple and economical.
  • a hot air penetration type method in which the above-mentioned raw material sprayed on a running mesh-shaped support is heated from above while vacuuming from below, and the formed web is A method in which a low-melting binder mixed with a hot roll is melted to fix a polyolefin-based synthetic pulp; a method in which the formed web is melt-bonded to the binder in a heat oven; an infrared heater; or A method of melting the binder using ultrasonic energy and bonding the webs may be used, but a hot air penetration method is preferably used in terms of heat treatment temperature and imparting bulkiness of the product.
  • the binder used for the polyolefin-based synthetic pulp, the polyolefin-based fiber, and the core have a melting point higher than the melting point of the synthetic pulp, and the sheath part has a melting point higher than the melting point of the synthetic pulp.
  • has a low melting point so-called Composite fiber of sheath-core type, polyolefin resin powder, low melting point polyester powder, butyl chloride resin powder, evoxy resin powder, or emulsion thereof, natural or synthetic rubber latex, and acrylic emulsion
  • At least one kind of pulp carried from the group is exemplified. Among them, it is preferable to use polyolefin synthetic pulp.
  • This binder must have a melting point lower than the melting point of the polyolefin synthetic pulp as the main raw material, preferably 5 or lower.
  • the mixing ratio of the polyolefin-based synthetic pulp and the binder is such that the polyolefin-based synthetic pulp is 100 to 50% by weight, preferably 98 to 50% by weight, the binder is 0 to 50% by weight, Preferably, it is 2 to 50% by weight.
  • the air laid method described in ⁇ for example, a method of randomly arranging binders having melting points in an air stream and bonding them by heat is exemplified.
  • the product obtained by dry papermaking can obtain a porous mat having high bulk (low density), that is, a high void ratio and excellent water retention, as compared with wet papermaking, which is an object of the present invention. It can be used very suitably as a separator for a sealed lead-acid battery.
  • the water retention of the mat can be further improved by subjecting the mat obtained as described above to a hydrophilization treatment.
  • This hydrophilization treatment is performed, for example, by immersing the mat in an aqueous solution of a surfactant, or by spray-spraying the mat, followed by drying.
  • a surfactant an anionic surfactant is preferable.
  • the degree of the hydrophilization treatment is preferably such that the amount of the surfactant attached is in the range of 0.05 to 5.0% by weight, more preferably 0.2 to 2.0% by weight.
  • Such a hydrophilization treatment is effective when synthetic pulp that has not been subjected to a hydrophilization treatment is used.
  • the lead-acid battery separator made of the mat thus obtained has a low density of 0.05 to 0.30 gZee, is excellent in water retention, and is a sealed lead-acid battery using this. Is also excellent in low temperature and high rate discharge capacity.
  • the water retention and the maximum pore size are related to the following characteristics of the lead storage battery.
  • the capacity of a lead-acid battery is determined by the amount of active material on the plates and the amount of electrolyte.
  • the electrolyte is limited to that contained in the retainer mat and that contained in the electrode plates. Therefore, when the electrodes are the same, the battery capacity, especially under low temperature and high rate discharge, Since the capacity to be removed depends on the amount of the electrolyte contained in the retainer mat, the retainer mat preferably contains a larger amount of the electrolyte, that is, has better water retention.
  • the separator (or retainer mat in the case of a closed lead-acid battery of the retainer type) is inserted between the positive electrode and the single electrode, and serves to prevent contact short-circuit between the two electrodes.
  • the separator should be as small as possible, since lead precipitated by repeated charge and discharge and lead powder released from the electrode plate will short-circuit both electrode plates through the pores of the separator and shorten the battery life. Is good. That is, since the life performance of the battery is affected by the size of the maximum pore diameter of the separator, the smaller the maximum pore diameter of the separator is, the better.
  • synthetic pulp mainly composed of polyolefin since synthetic pulp mainly composed of polyolefin is used as a material, it has excellent water retention and a small maximum hole diameter as compared with synthetic fiber using synthetic fibers. This is because synthetic fibers made by melt-spinning and the like have a columnar structure, whereas polyolefin-based synthetic pulp is highly branched and has many coatings on its surface. It is considered that performance is exhibited. Further, according to the present invention, by dry-synthesizing the synthetic pulp, it is possible to provide a low-density and low-cost separator with excellent acid resistance.
  • the sealed lead-acid battery used is characterized by excellent low-temperature high-rate discharge capacity. mmrn
  • A-75% by weight, B-15% by weight, and C 10% by weight were mixed and dry-processed by an air laid method to obtain a 2.0 mm thick mat.
  • hydrophilization treatment is performed with an anionic surfactant (aqueous solution of sodium dialkyl sulfosuccinate).
  • Table 1 shows the physical properties of the obtained mat.
  • a mat was obtained in the same manner as in Example 1 except that the above conditions were satisfied.
  • Table 1 shows the separator characteristics of the obtained mat.
  • a mat was obtained in the same manner as in Example 1 except that Table 1 shows the physical properties of the obtained mat.
  • Example 1 With the same raw materials and proportions as in Example 1, wet papermaking was performed to obtain a 2.0 mm thick mat.
  • the pine Bok having conducted a heat treatment by through 1 2 0 seconds hot air 1 3 2 e C.
  • a hydrophilic treatment was performed with an anionic surfactant (aqueous sodium dialkyl sulfosuccinate) to obtain a mat having a surfactant adhesion of 0.8% by weight.
  • Table 1 shows the physical properties of the obtained mat.
  • a mat was prepared in the same manner as in Example 1, except that the following material was used as the material A.
  • melt blown spun fiber mat (melt blown nonwoven fabric) of polypropylene was compared as a comparison.
  • a mat was prepared in the same manner as in Example 1, except that the following material was used as the material of A.
  • the weight percentage of the water contained in the separation evening relative to the weight of the separation evening when the sample is immersed in water and fully hydrated, and left (suspended) for 1 minute in a vertical state in the air.
  • test piece 2 5 0 was immersed in a methanol solution, the apparatus shown Hosoananai in Figure 1 was replaced with methanol, gradually applying pressure gradually, from the surface of the test piece bubbles (N 2 gas) Read the differential pressure at the time of appearance, and determine the maximum pore diameter of the sample from the surface tension of methanol ( ⁇ 1 ⁇ 2 23).
  • the calculation formula is
  • the 5-hour rate discharge capacity was measured as the time from the start of discharge until the terminal voltage of the battery reached 1.70 V, and the time was defined as the discharge capacity.
  • the low-temperature high-rate discharge capacity was measured by measuring the time from the start of discharge until the terminal voltage of the battery reached 1.00 V, and that time was defined as the discharge capacity.
  • the voltage at the 5th second is the terminal voltage of the battery 5 seconds after the start of discharging when measuring the low-temperature high-rate discharge capacity.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Cell Separators (AREA)

Abstract

Un séparateur pour une batterie au plomb du type fermé comprend un matelas poreux que l'on produit en mélangeant, en tant que composant principal, une pâte synthétique de polyoléfine avec un liant dont le point de fusion est inférieur à celui de ladite pâte synthétique, en transformant le mélange obtenu en papier, puis en traitant thermiquement le papier à une température inférieure à celle du point de fusion de la pâte synthétique et supérieure au point de fusion du liant. Le séparateur est bon marché étant donné que l'on n'utilise pas de fibre de verre, il présente des propriétés excellentes de rétention d'eau et une grande résistance à l'acide, et sa masse volumique est faible. Les batteries au plomb du type fermé comprenant un tel séparateur ont une grande capacité de décharge à haute intensité, à basse température.
PCT/JP1992/000306 1991-03-13 1992-03-13 Separateur pour batterie au plomb du type ferme WO1992016977A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP4800291 1991-03-13
JP3/48002 1991-03-13
JP4/45219 1992-03-03
JP4045219A JPH05283053A (ja) 1991-03-13 1992-03-03 密閉型鉛蓄電池用セパレータ

Publications (1)

Publication Number Publication Date
WO1992016977A1 true WO1992016977A1 (fr) 1992-10-01

Family

ID=26385194

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP1992/000306 WO1992016977A1 (fr) 1991-03-13 1992-03-13 Separateur pour batterie au plomb du type ferme

Country Status (1)

Country Link
WO (1) WO1992016977A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0616379A1 (fr) * 1993-03-19 1994-09-21 Mitsui Petrochemical Industries, Ltd. Feuille bouffante en pâte synthétique, utilisable comme séparateur de batteries au plomb étanches, et son procédé de fabrication
US10907284B2 (en) 2015-03-16 2021-02-02 Toray Fine Chemicals Co., Ltd. Nonwoven fabric and method of manufacturing same

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5398401A (en) * 1977-02-04 1978-08-28 Fuji Photo Film Co Ltd Porous sheet
JPS5755062A (en) * 1980-09-18 1982-04-01 Nippon Muki Kk Battery separator
JPS6151754A (ja) * 1984-08-20 1986-03-14 Matsushita Electric Ind Co Ltd 密閉型鉛蓄電池

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5398401A (en) * 1977-02-04 1978-08-28 Fuji Photo Film Co Ltd Porous sheet
JPS5755062A (en) * 1980-09-18 1982-04-01 Nippon Muki Kk Battery separator
JPS6151754A (ja) * 1984-08-20 1986-03-14 Matsushita Electric Ind Co Ltd 密閉型鉛蓄電池

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0616379A1 (fr) * 1993-03-19 1994-09-21 Mitsui Petrochemical Industries, Ltd. Feuille bouffante en pâte synthétique, utilisable comme séparateur de batteries au plomb étanches, et son procédé de fabrication
US10907284B2 (en) 2015-03-16 2021-02-02 Toray Fine Chemicals Co., Ltd. Nonwoven fabric and method of manufacturing same

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