WO2017150279A1 - 鉛蓄電池用不織布セパレータ、及びこれを用いた鉛蓄電池 - Google Patents
鉛蓄電池用不織布セパレータ、及びこれを用いた鉛蓄電池 Download PDFInfo
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- WO2017150279A1 WO2017150279A1 PCT/JP2017/006395 JP2017006395W WO2017150279A1 WO 2017150279 A1 WO2017150279 A1 WO 2017150279A1 JP 2017006395 W JP2017006395 W JP 2017006395W WO 2017150279 A1 WO2017150279 A1 WO 2017150279A1
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/06—Lead-acid accumulators
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- H—ELECTRICITY
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- 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
- H01M50/44—Fibrous material
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- H—ELECTRICITY
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- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/06—Lead-acid accumulators
- H01M10/08—Selection of materials as electrolytes
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- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/06—Lead-acid accumulators
- H01M10/12—Construction or manufacture
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/06—Lead-acid accumulators
- H01M10/12—Construction or manufacture
- H01M10/121—Valve regulated lead acid batteries [VRLA]
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- H—ELECTRICITY
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- 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
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- H—ELECTRICITY
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- 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
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- 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
- H01M50/429—Natural polymers
- H01M50/4295—Natural cotton, cellulose or wood
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- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/431—Inorganic material
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- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
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- 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
- H01M50/443—Particulate material
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- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/446—Composite material consisting of a mixture of organic and inorganic materials
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- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
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- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
- H01M50/457—Separators, membranes or diaphragms characterised by the material having a layered structure comprising three or more layers
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- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/46—Separators, membranes or diaphragms characterised by their combination with electrodes
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- H—ELECTRICITY
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- 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
- H01M50/463—Separators, membranes or diaphragms characterised by their shape
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- 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
- H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
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- H—ELECTRICITY
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- 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
- H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
- H01M50/491—Porosity
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- 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
- H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
- H01M50/494—Tensile strength
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- 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
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- 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
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- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Definitions
- the present invention relates to a non-woven fabric separator for lead-acid batteries and a lead-acid battery using the same.
- the stratification phenomenon can be cited as a factor that reduces the battery performance when used for a long time.
- Stratification means that the concentration of sulfuric acid, which is the electrolyte in the battery cell, varies between the upper and lower layers. Usually, high-concentration sulfate ions generated by electrode reaction are precipitated. In conventional lead-acid batteries used for starting automobile engines, etc., gas is generated from the electrode surface due to electrode reaction in an overcharged state, so the bubbling effect expands sales of the electrolyte and eliminates the stratification phenomenon. It did not become a problem. On the other hand, in an idling stop application or a DC application that is required to be used in a partially charged state, there is no reaction in an overcharged state, so that the electrolyte solution by gas is not expanded and the concentration difference between the upper and lower layers is not eliminated. In the vicinity of the lower electrode having a high sulfuric acid concentration, lead sulfate is deposited, and the life performance is lowered.
- Patent Documents 1 and 2 As a means for eliminating stratification, a control valve type lead storage battery including a fiber-containing separator is known (Patent Documents 1 and 2).
- Patent Document 1 discloses a control valve type lead-acid battery using a separator composed of glass fibers, acid-resistant organic fibers such as acrylic and polyolefin, and silica. The same document reports that stratification is suppressed by the adsorption effect of sulfate ions by silica, but does not show a clear effect of organic fibers, and does not mention a specific separator structure. . Moreover, since the glass fiber is contained in the separator described in the literature, the flexibility of the separator is poor, and there is a drawback that it is vulnerable to impact.
- Patent Document 2 discloses a control valve type lead-acid battery using a first separator made of an ultrafine glass mat and a second separator made of a synthetic fiber nonwoven fabric. According to the control valve type lead storage battery described in the same document, it has been reported that the cycle life characteristics are improved, but the detailed structure and material of the synthetic fiber are not disclosed.
- valve-regulated lead-acid batteries described in Patent Documents 1 and 2 still have room for improvement from the viewpoint of extending cycle life while ensuring high capacity, high output, and low resistance.
- the problem to be solved by the present invention is to provide a lead-acid battery nonwoven fabric separator and a lead-acid battery that have a high capacity, a high output, a low resistance, and a long cycle life.
- the present invention is as follows.
- the relationship between the average pore diameter (D) and the number of holes (N) of the nonwoven fabric separator is the following formula: 1.0 ⁇ 10 2 ⁇ D * N ⁇ 1.0 ⁇ 10 4
- [5] The separator according to any one of [1] to [4], wherein the nonwoven fabric separator has a porosity of 30% to 95%.
- the nonwoven fabric separator is composed of at least two layers including a nonwoven fabric layer (I layer) composed of the ultrafine fibers and a nonwoven fabric layer (II layer) composed of fibers having a fiber diameter of 5 ⁇ m to 30 ⁇ m.
- separator [10] The separator according to [9], wherein the nonwoven fabric separator is composed of three layers in which the I layer is disposed as an intermediate layer between the II layer and the II layer. [11] The separator according to any one of [1] to [10], wherein the nonwoven fabric separator is composed of the synthetic fiber. [12] The separator according to any one of [1] to [11], wherein the nonwoven fabric separator is composed of polyester fibers. [13] The separator according to any one of [1] to [12], wherein the nonwoven fabric separator is composed of polyolefin fibers. [14] The separator according to any one of [1] to [13], wherein the nonwoven fabric separator is composed of cellulose fibers.
- the nonwoven fabric separator contains an inorganic oxide.
- the nonwoven fabric separator includes a nonwoven fabric substrate having a void structure, and inorganic particles present on the surface portion of the nonwoven fabric substrate or the fiber surface inside the nonwoven fabric substrate.
- the separator according to item 1. [22] The separator according to [21], wherein the inorganic particles include a silicon component.
- the nonwoven fabric separator obtained by the present invention has an optimal material and a highly controlled structure, it has excellent ion permeability, liquid retention, electrical insulation, and chemical stability.
- the lead storage battery of the present invention is excellent in processing suitability as a battery, and has a non-woven mat used in the embodiment of the present invention, so that it is a stable production process, has a good yield, and is produced at a low cost. it can.
- the lead acid battery of the present invention has a high output, low resistance, and a very long cycle life.
- the nonwoven fabric separator of the present embodiment is composed of a recycled fiber manufactured using natural fiber (natural polymer) as a raw material, or a synthetic fiber purely synthetically manufacturing an organic polymer compound.
- examples of the regenerated fiber include rayon, cupra, polynosic, cellulose nanofiber, cellulose-based acetate, and protein-based promix.
- Synthetic fibers include, but are not limited to, polyester resins, polyolefin resins, polyamide resins, polyphenylene sulfide resins, polyvinyl chloride, polyimide, ethylene / vinyl acetate copolymer, polyacrylonitrile, polycarbonate, polystyrene. , Ionomers, and mixtures thereof.
- polyester resin examples include polyethylene terephthalate (PET), polybutylene terephthalate, and polyethylene naphthalate.
- polyolefin resins include homopolymers or copolymers of ⁇ -olefins such as ethylene, propylene, 1-butene, 1-hexene, 4-methyl-1-pentene and 1-octene; high-pressure low-density polyethylene, wire Low density polyethylene (LLDPE), high density polyethylene, polypropylene (propylene homopolymer), polypropylene random copolymer, poly 1-butene, poly 4-methyl-1-pentene, ethylene / propylene random copolymer, ethylene Examples thereof include 1-butene random copolymer and propylene / 1-butene random copolymer.
- ⁇ -olefins such as ethylene, propylene, 1-butene, 1-hexene, 4-methyl-1-pentene and 1-octene
- high-pressure low-density polyethylene wire Low density polyethylene (LLDPE), high density polyethylene, polypropylene (propylene homopolymer), polypropylene
- polyamide-based resin examples include nylon-6 (Ny), nylon-66, polymetaxylene adipamide, and the like.
- a nonwoven fabric composed of glass fibers is used as a nonwoven fabric separator for lead-acid batteries.
- the nonwoven fabric containing this glass fiber is weak against penetration or bone bending from the viewpoint of mechanical strength (such as puncture strength), causes a short circuit, increases process defects, and has low cycle characteristics.
- a nonwoven fabric mat composed of recycled fibers or synthetic fibers has an excellent mechanical strength and is excellent in processability into bags and the like, and is optimal.
- a nonwoven fabric separator made of synthetic fibers is preferred. Since the synthetic fiber is stable when wet with the electrolytic solution, the porous structure of the separator can be maintained.
- Non-woven fabric with highly controlled pore size physically inhibits sedimentation due to the specific gravity of sulfate ions, and by making the sulfate ions in the lower layer uniform throughout the layer through the nonwoven fabric, the effect of suppressing stratification is more pronounced become.
- the nonwoven fabric separator of this embodiment is preferably composed of polyester fibers.
- Polyester fibers are easier to be stretched and oriented than other materials, and high single yarn strength can be found. Therefore, the polyester fiber is very suitable for use in a lead-acid battery separator used in a bag shape, a cylindrical shape, or the like.
- the polyester fiber is chemically stable with respect to the sulfuric acid electrolyte solution having very high acidity, and the wettability is not bad. Therefore, a separator including a nonwoven fabric composed of polyester fibers can maintain a high ionic conductivity while maintaining a porous structure unique to the nonwoven fabric for a long period of time. Is possible. In that sense, the polyester fiber is more preferably a fiber formed of polyethylene terephthalate.
- the nonwoven fabric separator of the present embodiment is also preferably composed of polyolefin fibers.
- Polyolefin fibers have higher acid resistance at each stage than other materials, and very high chemical stability in sulfuric acid. Therefore, even when a separator made of polyolefin fibers is used at a relatively high temperature, such as an in-vehicle lead storage battery, the decomposition reaction is hardly promoted and the strength of the nonwoven fabric is not deteriorated at all. In that respect, as a lead-acid battery, the separator structure can be maintained for a long time, so that the life can be extended. In that sense, polypropylene and polyethylene are more preferable as the polyolefin fiber.
- the nonwoven fabric separator of the present embodiment is also preferably composed of cellulose fibers.
- Cellulose fibers that are excellent in water absorption have good affinity with the electrolytic solution, and are excellent in the retention of sulfate ions at the electrode interface. Therefore, in a battery including a separator made of cellulose fiber, it is possible to suppress sulfate ions from precipitating due to specific gravity due to chemical adsorption, and the concentration in the system is kept uniform, and stratification proceeds. It is difficult to extend the service life.
- the separator comprised from the cellulose fiber is excellent also in ion permeability, and can find a high capacity
- the nonwoven fabric separator of this embodiment is preferably composed of a nonwoven fabric having a fiber diameter of 0.1 to 30 ⁇ m. If the fiber diameter is 0.1 ⁇ m or more, the nonwoven fabric separator has a low resistance and a high capacity without impairing ionic conductivity. By setting the fiber diameter to 30 ⁇ m or less, the fiber diameter is not too large, and the fiber itself, which is a resin lump, has low resistance without hindering ionic conductivity by the separator between the electrodes. In addition, when there is a nonwoven fabric layer having a fiber diameter of 30 ⁇ m or less on the surface in contact with the electrode, the electrode reaction is not inhibited.
- the nonwoven fabric separator of the present embodiment is particularly preferably composed of a nonwoven fabric containing ultrafine fibers having a fiber diameter of 0.1 to 5 ⁇ m. Thereby, stratification can be suppressed and a low-resistance separator can be obtained. If the fiber diameter is 5 ⁇ m or less, the fiber gap does not become too large, and sulfate ions can be effectively retained, the sulfuric acid precipitation phenomenon can be suppressed, and stratification can be suppressed. In that sense, the fiber diameter of the ultrafine fiber is more preferably 0.2 ⁇ m to 4.0 ⁇ m, and still more preferably 0.3 ⁇ m to 3.0 ⁇ m.
- the nonwoven fabric separator of this embodiment includes a nonwoven fabric layer (I layer) composed of ultrafine fibers having a fiber diameter of 0.1 to 5 ⁇ m and a nonwoven fabric layer (II layer) composed of fibers having a fiber diameter of 5 to 30 ⁇ m. It is preferable that it is comprised by the at least 2 layer containing these.
- the nonwoven fabric layer (I layer) composed of ultrafine fibers having a fiber diameter of 0.1 to 5 ⁇ m is a functional layer
- the nonwoven fabric layer (II layer) composed of fibers having a fiber diameter of 5 to 30 ⁇ m is a strength layer.
- a role As a role.
- a two-layer laminated nonwoven fabric combining a nonwoven fabric layer (I layer) and a nonwoven fabric layer (II layer) can form a denser network-like nonwoven fabric structure.
- the nonwoven fabric layer (I layer) is arranged in the fiber gaps constituting the nonwoven fabric layer (II layer), the fibers are arranged more uniformly.
- the separator having at least two layers described above has a strength layer, the separator strength is high, and not only is post-processing easy, but also the productivity of the nonwoven fabric is very high.
- I layer-II layer two layer structure, I layer-II layer-I layer three layer structure, II layer-I layer-II layer three layer structure (that is, as an intermediate layer of two II layers) A three-layer structure in which an I layer is disposed) and a four-layer structure of I layer-II layer-I layer-I layer are preferable.
- each nonwoven fabric layer used in the embodiment of the present invention is not limited.
- the production method of the nonwoven fabric layer (II layer) is preferably a spunbond method, a dry method, a wet method or the like.
- the fibers for the nonwoven fabric layer (II layer) may be thermoplastic resin fibers or the like.
- the method for producing the non-woven fabric layer (I layer) composed of ultrafine fibers is preferably a dry method using ultrafine fibers, a wet method or the like, or an electrospinning method, a melt-blown method, force spinning. Etc. can be used.
- the nonwoven fabric layer (I layer) is particularly preferably formed by a melt blown method from the viewpoint that a nonwoven fabric layer composed of ultrafine fibers can be easily and densely formed. Further, the fiber may be used for producing a nonwoven fabric after realizing splitting or fibrillation by beating, partial dissolution or the like.
- thermal bonding For example, a method of jetting a high-speed water stream and three-dimensional entanglement, and a method of integrating with a particulate or fibrous adhesive.
- thermal bonding a method of jetting a high-speed water stream and three-dimensional entanglement, and a method of integrating with a particulate or fibrous adhesive.
- thermal bonding a method of jetting a high-speed water stream and three-dimensional entanglement, and a method of integrating with a particulate or fibrous adhesive.
- thermal bonding examples include integration by hot embossing (hot embossing roll method) and integration by high-temperature hot air (air-through method). Integration by thermal bonding is preferable from the viewpoint of maintaining the tensile strength and bending flexibility of the nonwoven fabric and maintaining heat resistance stability.
- Integration by thermal bonding is also preferable in that a laminated nonwoven fabric having a plurality of nonwoven fabric layers can be formed without using a binder.
- a binder is used when fibers are integrated to form a laminated nonwoven fabric, the binder is eluted into the electrolyte. There is no problem if the binder does not affect the battery performance without participating in the electrode reaction. However, depending on the binder, the electrode reaction is affected, and a desired capacity or voltage may not be obtained, which is a problem. Moreover, if the pore structure peculiar to the nonwoven fabric of the binder is blocked, the effect of retaining sulfuric acid cannot be obtained and stratification proceeds, which is not preferable.
- a nonwoven fabric that is integrated only by heat and does not use a binder is preferable. Furthermore, also from the viewpoint of the rationality of the process of forming the laminated nonwoven fabric, integration by heat alone is preferable because the cost can be further reduced.
- thermal bonding can be realized by thermally bonding two or more nonwoven fabric layers.
- the thermal bonding step can be performed, for example, by bonding using a flat roll at a temperature lower by 50 to 120 ° C. than the melting point of the synthetic resin and at a linear pressure of 100 to 1000 N / cm. If the linear pressure in the thermal bonding step is less than 100 N / cm, it may be difficult to obtain sufficient adhesion and to develop sufficient strength. On the other hand, when the linear pressure exceeds 1000 N / cm, the deformation of the fiber increases, the apparent density increases, the porosity decreases, and the effects of the present invention may not be obtained.
- the most preferable method for forming the laminated nonwoven fabric according to the present embodiment is to sequentially produce a spunbond nonwoven fabric layer, a meltblown nonwoven fabric layer and / or a spunbond nonwoven fabric layer, and laminate these to form an embossing roll or a hot press roll. It is the method of crimping with. This method is preferable for the purpose of obtaining a uniform nonwoven fabric with a low basis weight because it can form a laminated nonwoven fabric with the same material and can be produced on a continuous integrated production line. Specifically, one or more spunbond nonwoven fabric layers are spun on a conveyor using a thermoplastic resin, and then an ultrafine fiber having a fiber diameter of 0.1 to 5 ⁇ m is melt blown using the thermoplastic resin. Spray one or more non-woven fabric layers, then laminate one or more non-woven fabrics composed of thermoplastic resin fibers using a thermoplastic resin, and then crimp these layers using an embossing roll or flat roll. The method of integrating by is preferable.
- an ultrafine fiber nonwoven fabric layer (I layer) by a melt blown method is directly sprayed on a nonwoven fabric layer (II layer) composed of thermoplastic resin fibers.
- a nonwoven fabric layer (I layer) can be penetrated into a nonwoven fabric layer (II layer) comprised of thermoplastic resin fibers.
- the voids in the nonwoven fabric layer (II layer) composed of thermoplastic resin fibers can be made uniform by the ultrafine fiber layer. This facilitates the formation of a laminated nonwoven fabric having an appropriate interfiber distance and an appropriate pore size distribution. That is, according to the above-described method, in the laminated nonwoven fabric, a part of the I layer can be retained in the II layer while maintaining a continuous I layer. Smooth exchange of ions, including supply to the surface.
- the manufacturing method of the nonwoven fabric separator including the process of forming I layer by the melt blown method using the ultrafine fiber demonstrated above is also 1 aspect of this invention.
- the method for manufacturing the nonwoven fabric separator may include a step of integrating the I layer and the II layer by the method described above after the formation of the I layer.
- the crystallinity of fibers formed by the meltblown method can be adjusted to a range of 5 to 40% under general meltblown spinning conditions.
- the crystallinity can be evaluated by, for example, a method using differential scanning calorimetry (DSC). Specifically, the polymer forming the laminated nonwoven fabric was measured using a viscosity tube in a constant temperature water bath having a concentration of 0.01 g / mL and a temperature of 35 ° C. when o-chlorophenol (OCP) was used as a solvent.
- DSC differential scanning calorimetry
- the melt-blown fiber is constituted using a resin selected from PET resin and polyphenylene sulfide (PPS) resin,
- the solution viscosity ( ⁇ sp / c) of these resins is preferably 0.2 to 0.8.
- the crystallinity of the meltblown fiber is more preferably 10 to 40%.
- the laminated nonwoven fabric is preferably calendered.
- a more uniform structure can be given to the laminated nonwoven fabric.
- the calendering treatment is performed at a temperature that is 10 ° C. or more higher than the thermal bonding temperature and 10 to 100 ° C. lower than the melting point of the thermoplastic resin fibers.
- the calendering is performed at a linear pressure of 100 to 1000 N / cm.
- the calendering treatment temperature is lower than the melting point of the thermoplastic resin fiber and the difference is less than 10 ° C., the apparent density tends to be too high, and the difference is lower than the melting point of the thermoplastic resin fiber.
- the temperature exceeds 100 ° C., it is difficult to obtain sufficient strength, and fluffing occurs on the surface, the surface smoothness is impaired, and there is a tendency that the capacitor element does not have a uniform structure.
- the nonwoven fabric separator of this embodiment is preferably composed of continuous long fibers.
- the continuous long fiber refers to a fiber defined by JIS-L0222.
- a nonwoven fabric composed of short fibers has low strength because each fiber is not continuous and has low single yarn strength. Moreover, since the fibers fall off during the processing step such as slitting, it becomes a cause of defects.
- continuous long-fiber non-woven fabrics are very strong and are retained in the electrolyte solution, and are therefore optimal as lead-acid battery separators that wrap electrodes in a bag shape or cylindrical shape.
- the average pore diameter of the nonwoven fabric separator of this embodiment is preferably 0.1 to 50 ⁇ m. If the average pore diameter is larger than 50 ⁇ m, a sulfate ion precipitation phenomenon occurs, the sulfuric acid concentration gradient increases, and not only stratification occurs, but also an internal short circuit occurs, and the battery characteristics are lost. On the other hand, when the average pore diameter is smaller than 0.1 ⁇ m, the ionic conductivity between the electrodes is lowered, and the resistance as a separator is increased. In that sense, the average pore diameter of the nonwoven fabric separator is more preferably 0.3 to 40 ⁇ m, and further preferably 0.5 ⁇ m to 30 ⁇ m.
- the product of the average pore diameter (D) and the number of pores (N) of the nonwoven fabric separator of this embodiment is preferably 1.0 ⁇ 10 2 to 1.0 ⁇ 10 4 .
- the relationship between the size of the space formed by the inter-fiber structure and the average pore diameter and the number of pores, which represents the number, correlates with the ability to retain sulfate ions.
- sulfate ions generated in the vicinity of the electrode interface have a heavy specific gravity, so that the stratification phenomenon that settles to the lower part of the system is caused by a nonwoven fabric with controlled average pore diameter (D) and number of pores (N) at the electrode interface.
- D ⁇ N is more preferably in the range of 2.5 ⁇ 10 2 to 7.5 ⁇ 10 3 , and further preferably in the range of 5.0 ⁇ 10 2 to 5.0 ⁇ 10 3 .
- the nonwoven fabric separator of this embodiment preferably has a thickness of 30 to 1000 ⁇ m and a basis weight of 5 to 300 g / m 2 .
- the thickness exceeds 1000 ⁇ m, the distance between the electrodes increases and the resistance increases.
- the thickness exceeds 1000 ⁇ m, the thickness per cell increases, and as a result, the number of cells that can be mounted on the entire battery decreases and the capacity decreases. If the thickness is less than 30 ⁇ m, the active material movement during the electrode reaction cannot be endured, and a short circuit occurs. In that sense, the thickness is more preferably 40 to 900 ⁇ m, and further preferably 50 to 800 ⁇ m.
- the basis weight is 300 g / m 2 or less, it is easy to set the thickness of the entire nonwoven fabric within a preferable range. On the other hand, if the basis weight is 5 g / m 2 or more, it is possible to have the strength to hold the electrode in a bag shape by the nonwoven fabric. In that sense, the basis weight is more preferably 10 to 280 g / m 2 , and further preferably 20 to 250 g / m 2 .
- the porosity of the nonwoven fabric separator of this embodiment is preferably 30 to 95%. When the porosity of the nonwoven fabric is within this range, it is preferable from the viewpoints of electrolyte permeability, ion permeability, liquid retention, cycle life, and short circuit prevention.
- the porosity of the nonwoven fabric can be, for example, 40 to 90%, 45 to 85%, or 50 to 80%.
- the air permeability of the nonwoven fabric separator of this embodiment is preferably 0.01 to 10 sec / 100 cc (0.01 to 10 sec / 100 cm 3 ). If the air permeability is 10 sec / 100 cc or less, it is possible to maintain a low resistance without inhibiting the ionic conductivity. If the air permeability is 0.01 sec / 100 cc or more, the sulfuric acid precipitation effect can be suppressed.
- the nonwoven fabric separator of the present embodiment preferably has a nonwoven fabric tensile strength of 15 to 300 N / 15 mm from the viewpoint of handling properties, reduction of defective rate, and the like. If the tensile strength is 300 N or less, the handling is good and the bag can be processed. If the tensile strength is 15 N or more, even if an electrode is inserted, it can be held as a bag without breaking.
- the specific surface area of the nonwoven fabric separator of this embodiment is preferably 0.1 to 50 m 2 / g.
- Sulfate ions generated from the electrode surface control the electrolyte concentration inside the battery by sucking up sulfate ions once settled in the system at the continuous interface (fiber surface, particles, etc.) existing inside the separator. It is possible. Furthermore, ion mobility in the thickness direction can be improved, and stratification can be suppressed while maintaining a battery design with low electrical resistance and high capacity.
- the specific surface area is more preferably from 0.15 to 48 m 2 / g, and further preferably from 0.2 to 45 m 2 / g.
- the nonwoven fabric separator of the present embodiment is preferably a hydrophilic nonwoven fabric.
- a non-woven fabric subjected to hydrophilic processing can provide a lead storage battery separator excellent in ion permeability and electrolyte retention, and is preferable.
- Hydrophilic processing methods include physical processing methods such as hydrophilization by corona treatment or plasma treatment; chemical processing methods such as introduction of surface functional groups such as oxidation treatment, sulfonic acid groups, carboxylic acids, etc. Introducing a group or the like; a water-soluble polymer such as polyvinyl alcohol (PVA), polystyrene sulfonic acid or polyglutamic acid, and / or a surfactant such as a nonionic surfactant, an anionic surfactant, Processing with a treating agent such as a cationic surfactant or an amphoteric surfactant can be employed.
- PVA polyvinyl alcohol
- styrene sulfonic acid or polyglutamic acid and / or a surfactant such as a nonionic surfactant, an anionic surfactant
- Processing with a treating agent such as a cationic surfactant or an amphoteric surfactant can be employed.
- a person skilled in the art can select an
- the nonwoven fabric separator of this embodiment is a nonwoven fabric integrated by thermal bonding.
- a nonwoven fabric can be satisfactorily formed by thermally bonding fibers in the nonwoven fabric layer by calendering.
- the calendering include a method in which the nonwoven fabric layer is pressure-bonded with a hot roll. This method can be carried out in a continuous integrated production line, and is therefore suitable for the purpose of obtaining a uniform nonwoven fabric with a low basis weight.
- the heat bonding step can be performed, for example, at a temperature lower by 50 ° C. to 120 ° C. with respect to the melting point of the thermoplastic resin and at a linear pressure of 100 to 1000 N / cm.
- the heat roll used in calendering may be a roll with unevenness on the surface, such as embossing or satin pattern, or a smooth flat roll.
- the surface pattern of the roll having irregularities on the surface is not limited as long as the fibers can be bonded together by heat, such as an embossed pattern, a satin pattern, a rectangular pattern, and a line pattern.
- the nonwoven fabric separator of this embodiment contains an inorganic oxide. Since the nonwoven fabric containing the inorganic oxide has a large specific surface area, there are many interfaces capable of holding sulfate ions, and the effect of adsorption is exhibited. Therefore, it becomes possible to suppress the sedimentation phenomenon and stratification of sulfuric acid.
- Preferred inorganic oxides are silicon dioxide, titanium dioxide, and zirconium dioxide. A more preferred inorganic oxide is silicon dioxide.
- the method for disposing the inorganic oxide in the nonwoven fabric structure is not limited.
- the inorganic oxide can be filled in the separator by impregnating the nonwoven fabric separator with a coating liquid (including inorganic oxide, solvent, binder, etc.) by post-processing.
- the solvent may be any solvent that can uniformly disperse inorganic fine particles, heat-meltable fine particles and the like, and can dissolve or disperse the binder uniformly.
- aromatic hydrocarbon such as toluene; methyl ethyl ketone, methyl isobutyl Organic solvents such as ketones such as ketones may be used.
- ketones such as ketones may be used.
- water may be used as a solvent.
- alcohols, propylene oxide glycol ethers, and the like may be added to these solvents to control the interfacial tension.
- the nonwoven fabric separator of this embodiment can be heat sealed. Adopting a heat-sealable non-woven fabric when processing the separator in the form of a bag makes it possible to have good adhesion and very high sealing performance.
- the method for imparting heat sealability is not limited. For example, it is possible to provide sealing performance by disposing a two-component sheath core yarn on the surface of the nonwoven fabric and making the fiber surface a low melting point material.
- the coated nonwoven fabric separator of this embodiment contains the nonwoven fabric base material which has a void structure, and the inorganic particle which exists in the surface part of the base material, or the fiber surface inside a base material.
- the inorganic particles are formed as a layer in which inorganic particles are continuously present on the outer surface of the nonwoven fabric, the surface portion of the base material, or the fiber surface inside the base material, or form a discontinuous bulk. You may do it.
- the coated nonwoven fabric separator of this embodiment can be produced by using, for example, the following inorganic particle-dispersed slurry as one type of raw material.
- the inorganic particle dispersed slurry includes inorganic particles, a dispersion medium, and a binder.
- the inorganic particles dispersed in the slurry are not particularly limited, but are preferably non-conductive, and more preferably chemically and electrochemically stable with respect to the material constituting the electrochemical element.
- any of synthetic products and natural products can be used without particular limitation.
- inorganic particles for example, alumina such as gibbsite, bayerite, boehmite, corundum, silicic force, titania, zirconia, magnesia, ceria, yttria, zinc oxide and iron oxide and other oxide ceramics, silicon nitride, nitride Nitride-based ceramics such as titanium and boron nitride, silicon carbide, calcium carbonate, aluminum sulfate, aluminum hydroxide, magnesium hydroxide, potassium titanate, talc, synthetic force orinite, force orinlay, force orinite, flybonite, stevensite, Day force, Nacrite, Haguchi iteite, Pai mouth philite, Audinite, Montmori mouth night, Baydelite, Non-Mouth mouth night, Volcon Kosoy ⁇ , Saponite, Hectorite, Fluorine hectorite, Sauconite,
- inorganic particles are used alone or in combination of two or more.
- an action of suppressing the precipitation of sulfate ions discharged on the electrode surface by the battery reaction by a separator in contact with the electrode surface or a diffusion action through the separator is required. Therefore, it is preferable to use inorganic oxides such as alumina and silica for the purpose of adsorbing and retaining sulfate ions at the interface of the inorganic particles present on the nonwoven fabric substrate.
- non-woven fabric substrate is hydrophilized with the same inorganic particles, a diffusion action of sulfate ions can be expected.
- silica is preferable from the viewpoint that it is possible to subdivide the particle size and to expect more excellent sedimentation suppressing action and diffusing action using innumerable interfaces.
- the average particle size of the inorganic particles is preferably 1 to 5000 nm.
- the average particle size of the inorganic particles in the slurry is preferably 1 to 5000 nm.
- the particle size of the inorganic particles in the slurry is 1 nm or more, in the layer coated on the substrate, the interface of the inorganic particles appears on the surface (of the coating layer) in the composite with the binder, and the interface is more effective.
- an action of adsorbing or diffusing sulfate ions can be obtained.
- the average particle diameter is more preferably 2 to 3000 nm, and still more preferably 5 to 1000 nm.
- the content ratio of the inorganic particles in the slurry is preferably 1 to 80% by mass, more preferably 5 to 70% by mass from the viewpoint of slurry viscosity, coatability, and shortening of the drying process of the slurry. .
- the specific surface area of the inorganic particles is preferably 0.1 to 1000 m 2 / g.
- the specific surface area of the inorganic particles is preferably 0.1 to 1000 m 2 / g.
- the dispersion medium of the inorganic particles those capable of uniformly and stably dispersing the inorganic particles are preferable.
- N-methylpipridone, N, N-dimethylformamide, N, N-dimethylacetamide, water, ethanol, toluene, heat Xylene, methylene chloride and hexane are mentioned.
- water is preferable from the viewpoint of environmental protection.
- the inorganic particle-dispersed slurry of the present embodiment can contain a binder for the purpose of binding the inorganic particles or fixing the inorganic particles to the nonwoven fabric substrate.
- a binder for the purpose of binding the inorganic particles or fixing the inorganic particles to the nonwoven fabric substrate.
- a resin binder is preferable.
- Specific examples include, for example, polyolefin resins such as polyethylene and polypyrene, polybutene and copolymers thereof, and modified polyolefin resins obtained by acid-modifying polyolefin resins; polyvinylidene fluoride and polytetrafluoroethylene.
- Fluorine-containing resins such as vinylidene fluoride-hexafluorine-mouth-pyrene-tetrafluorine-mouthed ethylene copolymer and ethylene-tetrafluorinated-mouthed ethylene copolymer; (meth) acrylic acid-styrene-butadiene copolymer And its hydride acrylic nitrile butadiene copolymer and its hydride, acrylic nitrile butadiene-styrene copolymer and its hydride, methacrylic acid ester-acrylic acid ester copolymer, styrene-acrylic acid ester Copolymer, Acryguchi Ryl-acrylic acid ester copolymers, rubbers such as ethylene propylene rubber, polyvinyl alcohol and polyvinyl acetate; cellulose derivatives such as ethyl cellulose, methyl cellulose, hydroxyethyl cellulose and ruboxymethyl cellulose; polyphenylene
- resin binders are used singly or in combination of two or more.
- an acrylic binder is more preferable as a resin binder from the viewpoint of adhesiveness with a base material and inorganic particles. It is not limited to the above, and a plurality of types of binders may be used in combination.
- the binder content in the inorganic particle-dispersed slurry is preferably 1 part by mass or more, preferably 4 parts by mass or more with respect to 100 parts by mass of the inorganic particles, from the viewpoint of more effectively exerting the binding and fixing action by the binder. It is more preferable that it is 6 parts by mass or more.
- the inclusion of a binder is preferably 500 parts by mass or less and more preferably 300 parts by mass or less with respect to 100 parts by mass of the inorganic particles.
- the slurry contains a dispersant such as a surfactant; a thickener; a wetting agent; an antifoaming agent; an antiseptic and a bactericidal agent; an acid and an alkali in order to stabilize the dispersion of inorganic particles and improve coating properties.
- a dispersant such as a surfactant; a thickener; a wetting agent; an antifoaming agent; an antiseptic and a bactericidal agent; an acid and an alkali in order to stabilize the dispersion of inorganic particles and improve coating properties.
- Various additives such as a pH adjusting agent may be added. These additives are preferably those that can be removed when the solvent is removed. However, the additive may remain in the separator as long as it is electrochemically stable in the range of use of the electrochemical element and does not inhibit the battery reaction.
- dispersant such as a surfactant
- anionic surfactants such as sulfate ester type, phosphate ester type, strong rubonic acid type, and sulfonic acid type
- quaternary ammonium salt types and force thiones such as amidoamine type.
- amphoteric surfactants such as alkyl betaine type, amide betaine type, amine oxide type, nonionic surfactants such as ether type, fatty acid ester type, alkyl glucooxide, polyacrylic acid, polyacrylate,
- Various surfactants can be used such as polysulfonic acid salts, polynaphthalene sulfonates, polyalkylene polyamine alkylene oxides, polyalkylene polyimine alkylene oxides, polyvinyl pipridone, and cellulose type polymer surfactants. These are used alone or in combination of two or more for the purpose of preventing aggregation of fillers.
- the dispersant is not limited to these as long as the same effects as those described above can be obtained.
- an alcohol such as methyl alcohol, ethyl alcohol, isopyl pill alcohol, ethylene glycol or propylene glycol, or ether such as monomethyl acetate can be added to the slurry. These are used singly or in combination of two or more.
- the additive for controlling the interfacial tension is not limited to these as long as the same effect can be obtained.
- the thickener examples include polyethylene glycol, urethane-modified polyether, polyacrylic acid, polyvinyl alcohol, vinyl methyl ether-maleic anhydride copolymer, and other synthetic polymers, strong rubomethoxycellulose, hydroxoxyethylcellulose, hydride.
- examples thereof include cellulose derivatives such as mouth-kiff mouth pill cellulose, natural polysaccharides such as xanthan gum, dieutan gum, welan gum, gellan gum, guar gum, and power raginan gum, and starches such as dexamerine and pregelatinized starch.
- the thickener is appropriately selected from the viewpoint of the viscosity of the slurry, pot life and particle size distribution. These may be used alone or in combination of two or more.
- the thickener is not limited to those as long as the same effects as those described above can be obtained.
- a wetting agent is added to the slurry for the purpose of improving the wettability with the nonwoven fabric fibers (for example, synthetic fibers) and suppressing pinholes. be able to.
- the wetting agent include sulfosuccinic acid type surfactants, aliphatic polyether type nonionic surfactants, polyoxyalkylene type nonionic surfactants, modified silicones, modified polyethers, dimethyl cyclohexane polyoxyalkylene copolymer. Coalescence can be used. These are used singly or in combination of two or more.
- the wetting agent is not limited to these as long as the same effects as those described above can be obtained.
- antifoaming agent for example, various defoaming agents of mineral oil type, silicone type, acrylic type and polyether type can be used. These are used singly or in combination of two or more.
- the antifoaming agent is not limited to these as long as the same effects as those described above can be obtained.
- a slurry can be prepared by dispersing inorganic particles in a solvent which is a dispersion medium.
- the method of dissolving or dispersing the inorganic particles and the binder in the solvent of the slurry is not particularly limited as long as the dissolution text of the slurry required when applying the slurry to the substrate or the like can realize the dispersion characteristics. .
- Examples of the dissolving or dispersing method include a ball mill, a bead mill, a planetary ball mill, a vibrating ball mill, a sand mill, a colloid mill, an attritor, a roll mill, a high-speed impeller dispersion, a disperser, a homogenizer, an ultrasonic homogenizer, a pressure homogenizer, and an ultrahigh pressure homogenizer.
- the coated nonwoven fabric separator of this embodiment includes a nonwoven fabric substrate having an infinite number of void structures.
- the nonwoven fabric substrate is a substrate having spaces (pores or voids) therein.
- the nonwoven fabric substrate is preferably composed of organic fibers.
- the organic fiber include natural fiber, regenerated fiber produced using the same as a raw material, or synthetic fiber produced purely for producing an organic polymer compound.
- Natural fibers include, but are not limited to, vegetable fibers; cotton, hemp, Manila asa, palm, rush, animal fibers; wool, wool, silk, and the like.
- Recycled fibers are not particularly limited, and examples include rayon, cupra, polynosic, cellulose nanofibers, cellulose-based acetates, and protein-based promixes.
- the synthetic fiber is not particularly limited, but polyester resin, polyolefin resin, polyamide resin, polyphenylene sulfide resin, polyvinyl chloride, polyimide, ethylene / vinyl acetate copolymer, polyacrylonitrile, polycarbonate, Polystyrene, ionomer, and mixtures thereof.
- polyester-based resin include polyethylene terephthalate (PET), polybutylene terephthalate, and polyethylene naphthalate.
- polyolefin resins include homopolymers or copolymers of ⁇ -olefins such as ethylene, propylene, 1-butene, 1-hexene, 4-methyl-1-pentene and 1-octene; high-pressure low-density polyethylene, wire Low density polyethylene (LLDPE), high density polyethylene, polypropylene (propylene homopolymer), polypropylene random copolymer, poly 1-butene, poly 4-methyl-1-pentene, ethylene / propylene random copolymer, ethylene Examples thereof include 1-butene random copolymer and propylene / 1-butene random copolymer.
- ⁇ -olefins such as ethylene, propylene, 1-butene, 1-hexene, 4-methyl-1-pentene and 1-octene
- high-pressure low-density polyethylene wire Low density polyethylene (LLDPE), high density polyethylene, polypropylene (propylene homopolymer), polypropylene
- polyamide-based resin examples include nylon-6 (Ny), nylon-66, polymetaxylene adipamide, and the like.
- a single material (for example, polyester) using these resins may be used, or a blend resin in which two or more kinds of resins are mixed may be used.
- a nonwoven fabric composed of glass fiber is used as a lead-acid battery separator.
- the nonwoven fabric containing this glass fiber is weak against penetration or bone bending from the viewpoint of mechanical strength (such as piercing strength), causes a short circuit, increases process defects, and lowers cycle characteristics.
- a nonwoven fabric composed of organic fibers has an excellent mechanical strength and is excellent in processability and flexibility into bags and the like, and is optimal.
- a nonwoven fabric substrate composed of synthetic fibers is preferable. Synthetic fibers have little behavior such as swelling, and are stable when wet with an electrolyte solution. Therefore, it is possible to maintain a unique porous structure of a nonwoven fabric. Therefore, since the nonwoven fabric base material itself which becomes the base of the inorganic particles has shape stability, it has shape stability on the electrolyte as a separator, and it is possible to maintain a continuous interface with the continuous inorganic particles.
- the nonwoven fabric substrate is preferably composed of polyester fibers.
- Polyester fibers are easier to be stretched and oriented than other materials, and high single yarn strength can be found. Therefore, the polyester fiber is very suitable for use in a lead-acid battery separator used in a bag shape, a cylindrical shape, or the like.
- the polyester fiber is chemically stable with respect to the sulfuric acid electrolyte solution having very high acidity, and the wettability is not bad. Therefore, a separator including a nonwoven fabric composed of polyester fibers can maintain a high ionic conductivity while maintaining a porous structure unique to the nonwoven fabric for a long period of time. Is possible.
- the coating property of the slurry in which inorganic particles are dispersed is good, and a separator that is easily and highly controlled can be produced.
- the polyester fiber is more preferably a fiber formed of polyethylene terephthalate.
- the nonwoven fabric substrate is also preferably composed of polyolefin fibers.
- Polyolefin fibers have higher acid resistance at each stage than other materials, and very high chemical stability in sulfuric acid. Therefore, even when a separator made of polyolefin fibers is used at a relatively high temperature, such as an in-vehicle lead storage battery, the decomposition reaction is hardly promoted and the strength of the nonwoven fabric is not deteriorated at all. In that respect, as a lead-acid battery, the separator structure can be maintained for a long time, so that the life can be extended. In that sense, polypropylene and polyethylene are more preferable as the polyolefin fiber.
- the nonwoven fabric substrate is also preferably composed of cellulose fibers.
- Cellulose fibers that are excellent in water absorption have good affinity with the electrolytic solution, and are excellent in the retention of sulfate ions at the electrode interface. Therefore, in a battery including a separator made of cellulose fiber, it is possible to suppress sulfate ions from precipitating due to specific gravity due to chemical adsorption, and the concentration in the system is kept uniform, and stratification proceeds. It is difficult to extend the service life.
- the separator comprised from the cellulose fiber is excellent also in ion permeability, and can find a high capacity
- the nonwoven fabric substrate is preferably composed of continuous long fibers.
- the continuous long fiber refers to a fiber defined by JIS-L0222. Since the nonwoven fabric base material comprised by the continuous long fiber has connected the fiber continuously, when arranging the interface of the continuous inorganic particle on the surface, it is very effective. This affects the diffusibility of sulfate ions, and the more the continuous inorganic particles are arranged, the higher the sulfuric acid uniformity effect. Furthermore, the strength of the nonwoven fabric is high, it can withstand tension even in the coating process, and is optimal as a lead-acid battery separator that wraps the electrode in a bag or cylinder. On the other hand, non-woven fabrics composed of short fibers are not strong because the individual fibers are not continuous and the single yarn strength is low, and the strength is weak. It becomes.
- the porosity of the nonwoven fabric substrate is preferably 35 to 95%.
- the porosity of the nonwoven fabric is within this range, it is preferable from the viewpoints of electrolyte permeability, ion permeability, liquid retention, cycle life, and short circuit prevention.
- the particles can be sufficiently filled in the voids.
- a more preferable range of the porosity of the nonwoven fabric is 40 to 90%, and more preferably 45 to 85%.
- the average pore size of the nonwoven fabric substrate is preferably 0.1 to 200 ⁇ m. If the average pore diameter is larger than 200 ⁇ m, large pores (holes formed by fiber-fiber gaps) exist, so that even if inorganic particles are applied, they cannot be filled, resulting in pinholes. As a deadly short circuit is induced. In addition, when coating inorganic particles, the strike-through is significant, and the separator cannot be manufactured stably during continuous production. On the other hand, when the average pore diameter is smaller than 0.1 ⁇ m, the ionic conductivity between the electrodes is lowered, and the resistance as a separator is increased. In that sense, the average pore diameter of the nonwoven fabric separator is more preferably 0.2 to 150 ⁇ m, and further preferably 0.5 ⁇ m to 100 ⁇ m.
- the nonwoven fabric substrate preferably has a thickness of 10 to 5000 ⁇ m and a basis weight of 5 to 500 g / m 2 .
- thickness exceeds 5000 micrometers, the distance between electrodes will become large and resistance will become high.
- the thickness per cell increases, the number of cells that can be mounted on the entire battery is reduced, resulting in a reduction in capacity. If the thickness is less than 10 ⁇ m, the active material movement during the electrode reaction cannot be endured, and a short circuit occurs.
- the basis weight is 500 g / m 2 or less, it is easy to set the thickness of the entire nonwoven fabric within a preferable range.
- the basis weight is 5 g / m 2 or more, it is possible to have the strength to hold the electrode in a bag shape by the nonwoven fabric.
- the basis weight is more preferably 7 to 480 g / m 2 , and further preferably 10 to 450 g / m 2 .
- the nonwoven fabric substrate is preferably composed of a nonwoven fabric containing ultrafine fibers having a fiber diameter of 0.1 to 5 ⁇ m. If the fiber diameter is 5 ⁇ m or less, the fiber gap does not become too large, and a short circuit can be suppressed. Moreover, since the fiber surface area is secured to a certain level or more, when inorganic particles are formed thereon, the number of interfaces can be remarkably increased. Furthermore, when the number of interfaces is constant, the basis weight of the nonwoven fabric substrate can be reduced as compared with the case where the fiber diameter is large, and the separator can be made thinner. In terms of battery design, many cells can be incorporated, and high capacity and high output can be achieved.
- the fiber diameter of the ultrafine fiber is more preferably 0.15 ⁇ m to 4.0 ⁇ m, and still more preferably 0.2 ⁇ m to 3.0 ⁇ m.
- the nonwoven fabric substrate is composed of a nonwoven fabric layer (I layer) composed of ultrafine fibers having a fiber diameter of 0.1 to 5 ⁇ m and fibers having a fiber diameter of 5 to 30 ⁇ m. It is preferable that it is composed of at least two layers including a non-woven fabric layer (II layer).
- the nonwoven fabric layer (I layer) composed of ultrafine fibers having a fiber diameter of 0.1 to 5 ⁇ m is a functional layer
- the nonwoven fabric layer (II layer) composed of fibers having a fiber diameter of 5 to 30 ⁇ m is a strength layer.
- a two-layer laminated nonwoven fabric combining a nonwoven fabric layer (I layer) and a nonwoven fabric layer (II layer) can form a denser, network-like nonwoven fabric structure,
- sulfate ions diffuse at the interface, so that the diffusion action works more uniformly and quickly, and as a result, uniform sulfuric acid concentration can always be achieved.
- the nonwoven fabric layer (II layer) has many void volumes and numbers in the separator, a large number of sulfate ion adsorption spaces can exist, which also leads to the effect of suppressing stratification.
- the separator having at least two layers described above has a strength layer, the separator strength is high, and not only is post-processing easy, but also the productivity of the nonwoven fabric is very high.
- a two-layer structure of I layer-II layer, a three-layer structure of I layer-II layer-I layer, and a three-layer structure of II layer-I layer-II layer (that is, as an intermediate layer of two II layers) A three-layer structure in which an I layer is disposed) and a four-layer structure of I layer-II layer-I layer-I layer are preferable.
- the method for producing each nonwoven fabric layer is not limited.
- the production method of the nonwoven fabric layer (II layer) is preferably a spunbond method, a dry method, a wet method or the like.
- the fibers for the nonwoven fabric layer (II layer) may be thermoplastic resin fibers or the like.
- the method for producing the non-woven fabric layer (I layer) composed of ultrafine fibers is preferably a dry method using ultrafine fibers, a wet method or the like, or an electrospinning method, a melt-blown method, force spinning. Etc. can be used.
- the nonwoven fabric layer (I layer) is particularly preferably formed by a melt blown method from the viewpoint that a nonwoven fabric layer composed of ultrafine fibers can be easily and densely formed. Further, the fiber may be used for producing a nonwoven fabric after realizing splitting or fibrillation by beating, partial dissolution or the like.
- thermal bonding For example, a method of jetting a high-speed water stream and three-dimensional entanglement, and a method of integrating with a particulate or fibrous adhesive.
- thermal bonding a method of jetting a high-speed water stream and three-dimensional entanglement, and a method of integrating with a particulate or fibrous adhesive.
- thermal bonding a method of jetting a high-speed water stream and three-dimensional entanglement, and a method of integrating with a particulate or fibrous adhesive.
- thermal bonding examples include integration by hot embossing (hot embossing roll method) and integration by high-temperature hot air (air-through method). Integration by thermal bonding is preferable from the viewpoint of maintaining the tensile strength and bending flexibility of the nonwoven fabric and maintaining heat resistance stability.
- Integration by thermal bonding is also preferable in that a laminated nonwoven fabric having a plurality of nonwoven fabric layers can be formed without using a binder. If a binder is used when fibers are integrated to form a laminated nonwoven fabric, the binder is eluted into the electrolyte. There is no problem if the binder does not affect the battery performance without participating in the electrode reaction. However, depending on the binder, the electrode reaction is affected, and a desired capacity or voltage may not be obtained, which is a problem.
- thermal bonding can be realized by thermally bonding two or more nonwoven fabric layers.
- the thermal bonding step can be performed, for example, by bonding using a flat roll at a temperature lower by 50 to 120 ° C. than the melting point of the synthetic resin and at a linear pressure of 100 to 1000 N / cm. If the linear pressure in the thermal bonding step is less than 100 N / cm, it may be difficult to obtain sufficient adhesion and to develop sufficient strength. On the other hand, when the linear pressure exceeds 1000 N / cm, the deformation of the fiber increases, the apparent density increases, the porosity decreases, and the effects of the present invention may not be obtained.
- the most preferable method for forming the nonwoven fabric substrate is to sequentially produce a spunbond nonwoven fabric layer, a meltblown nonwoven fabric layer and / or a spunbond nonwoven fabric layer, and laminate these layers.
- This is a method of pressure bonding with an embossing roll or a hot press roll.
- This method is preferable for the purpose of obtaining a uniform nonwoven fabric with a low basis weight because it can form a laminated nonwoven fabric with the same material and can be produced on a continuous integrated production line.
- one or more spunbond nonwoven fabric layers are spun on a conveyor using a thermoplastic resin, and then an ultrafine fiber having a fiber diameter of 0.1 to 5 ⁇ m is melt blown using the thermoplastic resin.
- Spray one or more non-woven fabric layers then laminate one or more non-woven fabrics composed of thermoplastic resin fibers using a thermoplastic resin, and then crimp these layers using an embossing roll or flat roll.
- the method of integrating by is preferable.
- an ultrafine fiber nonwoven fabric layer (I layer) by a melt blown method is directly sprayed on a nonwoven fabric layer (II layer) composed of thermoplastic resin fibers.
- a nonwoven fabric layer (I layer) can be penetrated into a nonwoven fabric layer (II layer) comprised of thermoplastic resin fibers.
- the voids in the nonwoven fabric layer (II layer) composed of thermoplastic resin fibers can be made uniform by the ultrafine fiber layer. This facilitates the formation of a laminated nonwoven fabric having an appropriate interfiber distance and an appropriate pore size distribution. That is, according to the above-described method, in the laminated nonwoven fabric, a part of the I layer can be retained in the II layer while maintaining a continuous I layer. Smooth exchange of ions, including supply to the surface.
- the manufacturing method of the nonwoven fabric separator including the process of forming I layer by the melt blown method using the ultrafine fiber demonstrated above is also 1 aspect of this invention.
- the method for manufacturing the nonwoven fabric separator may include a step of integrating the I layer and the II layer by the method described above after the formation of the I layer.
- the crystallinity of fibers formed by the meltblown method can be adjusted to a range of 5 to 40% under general meltblown spinning conditions.
- the crystallinity can be evaluated by, for example, a method using differential scanning calorimetry (DSC). Specifically, the polymer forming the laminated nonwoven fabric was measured using a viscosity tube in a constant temperature water bath having a concentration of 0.01 g / mL and a temperature of 35 ° C. when o-chlorophenol (OCP) was used as a solvent.
- DSC differential scanning calorimetry
- the melt-blown fiber is constituted using a resin selected from PET resin and polyphenylene sulfide (PPS) resin,
- the solution viscosity ( ⁇ sp / c) of these resins is preferably 0.2 to 0.8.
- the crystallinity of the meltblown fiber is more preferably 10 to 40%.
- the laminated nonwoven fabric that is the nonwoven fabric substrate is calendered.
- a more uniform structure can be given to the laminated nonwoven fabric.
- the calendering treatment is performed at a temperature that is 10 ° C. or more higher than the thermal bonding temperature and 10 to 100 ° C. lower than the melting point of the thermoplastic resin fibers.
- the calendering is performed at a linear pressure of 100 to 1000 N / cm.
- the calendering treatment temperature is lower than the melting point of the thermoplastic resin fiber and the difference is less than 10 ° C., the apparent density tends to be too high, and the difference is lower than the melting point of the thermoplastic resin fiber.
- the temperature exceeds 100 ° C., it is difficult to obtain sufficient strength, and fluffing occurs on the surface, the surface smoothness is impaired, and there is a tendency that the capacitor element does not have a uniform structure.
- the nonwoven fabric substrate is preferably a hydrophilic processed nonwoven fabric.
- a hydrophilic treatment sulfuric acid as an electrolyte is easily retained in the voids of the nonwoven fabric, so that the sulfuric acid sedimentation phenomenon can be suppressed.
- a non-woven fabric subjected to hydrophilic processing can provide a lead storage battery separator excellent in ion permeability and electrolyte retention, and is preferable.
- Hydrophilic processing methods include physical processing methods such as hydrophilization by corona treatment or plasma treatment; chemical processing methods such as introduction of surface functional groups such as oxidation treatment, sulfonic acid groups, carboxylic acids, etc. Introducing a group or the like; a water-soluble polymer such as polyvinyl alcohol (PVA), polystyrene sulfonic acid or polyglutamic acid, and / or a surfactant such as a nonionic surfactant, an anionic surfactant, Processing with a treating agent such as a cationic surfactant or an amphoteric surfactant can be employed.
- PVA polyvinyl alcohol
- styrene sulfonic acid or polyglutamic acid and / or a surfactant such as a nonionic surfactant, an anionic surfactant
- Processing with a treating agent such as a cationic surfactant or an amphoteric surfactant can be employed.
- a person skilled in the art can select an
- the nonwoven fabric base material is preferably a nonwoven fabric integrated by thermal bonding.
- a nonwoven fabric can be satisfactorily formed by thermally bonding fibers in the nonwoven fabric layer by calendering.
- the calendering include a method in which the nonwoven fabric layer is pressure-bonded with a hot roll. This method can be carried out in a continuous integrated production line, and is therefore suitable for the purpose of obtaining a uniform nonwoven fabric with a low basis weight.
- the heat bonding step can be performed, for example, at a temperature lower by 50 ° C. to 120 ° C. with respect to the melting point of the thermoplastic resin and at a linear pressure of 100 to 1000 N / cm.
- the heat roll used in calendering may be a roll with unevenness on the surface, such as embossing or satin pattern, or a smooth flat roll.
- the surface pattern of the roll having irregularities on the surface is not limited as long as the fibers can be bonded together by heat, such as an embossed pattern, a satin pattern, a rectangular pattern, and a line pattern.
- the nonwoven fabric separator of the present embodiment may be used alone as a separator, or may be used by being laminated with another nonwoven fabric or a microporous membrane.
- the lamination method is not particularly limited. In particular, it is preferable to use a nonwoven fabric separator and a microporous membrane or a nonwoven fabric separator and a glass fiber nonwoven fabric laminated.
- a microporous membrane having extremely high density and pore size uniformity is arranged between electrodes compared to a single nonwoven fabric, and short-circuiting is unlikely to occur.
- the fiber is arranged at the electrode interface, so the concentration of sulfuric acid is made uniform, the stratification phenomenon is suppressed, and the life can be extended. It becomes.
- the glass fiber nonwoven fabric is rich in compression elasticity, making it possible to follow the electrode foil that repeatedly swells and shrinks, effectively uniforming the sulfuric acid concentration by the nonwoven fabric Is obtained.
- the lead storage battery of this embodiment is composed of a lead electrode-separator-lead electrode, and uses sulfuric acid as an electrolyte.
- a particularly preferable battery type is a liquid type or a control valve type.
- the lead storage battery includes a positive electrode and a negative electrode, an electrode plate group including a nonwoven fabric separator disposed therebetween, and sulfuric acid as an electrolytic solution.
- the length direction of the nonwoven fabric is the MD direction (machine direction), and the width direction is a direction perpendicular to the length direction.
- Weight per unit area (g / m 2 ) According to the method specified in JIS L-1906, test specimens measuring 20 cm in length x 25 cm in width were sampled at 3 locations per 1 m in the width direction and 3 locations per 1 m in the length direction, for a total of 9 locations per 1 m ⁇ 1 m. The basis weight was determined by converting the average value into mass per unit area.
- Thickness ( ⁇ m) According to the method specified in JIS L-1906, the thickness of 10 locations per 1 m width of the test piece was measured, and the average value was obtained. The thickness was measured under a load of 9.8 kPa.
- the nonwoven fabric was cut into 10 cm ⁇ 10 cm and pressed on an iron plate at 60 ° C. at a pressure of 0.30 MPa for 90 seconds, and then the nonwoven fabric was vapor-deposited with platinum. Using a SEM apparatus (JSM-6510, manufactured by JEOL Ltd.), the deposited nonwoven fabric was photographed under conditions of an acceleration voltage of 15 kV and a working distance of 21 mm. The photographing magnification was 10,000 times for yarns having an average fiber diameter of less than 0.5 ⁇ m, 6000 times for yarns having an average fiber diameter of 0.5 ⁇ m or more and less than 1.5 ⁇ m, and 4000 times for yarns having an average fiber diameter of 1.5 ⁇ m or more.
- the field of view at each magnification was 12.7 ⁇ m ⁇ 9.3 ⁇ m at 10,000 ⁇ , 21.1 ⁇ m ⁇ 15.9 ⁇ m at 6000 ⁇ , and 31.7 ⁇ m ⁇ 23.9 ⁇ m at 4000 ⁇ .
- 100 or more fibers were randomly photographed and all fiber diameters were measured. However, the fibers fused in the yarn length direction were excluded from the measurement target.
- the weight average fiber diameter (Dw) obtained by the above was defined as the average fiber diameter ( ⁇ m).
- d C ⁇ r / P (Where d (unit: ⁇ m) is the pore size of the filter, r (unit: N / m) is the surface tension of the liquid, P (unit: Pa) is the pressure at which the liquid film of that pore size is broken, and C is It is a constant.) From the above formula, the flow rate (wetting flow rate) when the pressure P applied to the filter immersed in the liquid is continuously changed from low pressure to high pressure is measured. At the initial pressure, the flow rate is zero because the liquid film with the largest pores is not broken. As the pressure is increased, the liquid film with the largest pores is destroyed and a flow rate is generated (bubble point). As the pressure is further increased, the flow rate increases with each pressure.
- the flow rate at the pressure when the liquid film with the smallest pore is broken matches the dry flow rate (dry flow rate).
- dry flow rate dry flow rate
- the value obtained by dividing the wetting flow rate at a certain pressure by the dry flow rate at the same pressure is called a cumulative filter flow rate (unit:%).
- the pore size of the liquid film that is broken at a pressure at which the cumulative filter flow rate is 50% is referred to as the average flow pore size.
- This average flow pore size was defined as the average pore size (D) of the present invention.
- the number of pores obtained at that time was defined as the number of pores (N).
- the maximum pore diameter of the present invention is determined by measuring the nonwoven fabric as the filter sample, and the cumulative filter flow rate is in the range of -2 ⁇ where the cumulative filter flow rate is 50%. did. Three points were measured for each sample by the above measurement method, and the average flow pore size, the minimum pore size, and the maximum pore size were calculated as average values.
- Air permeability (sec / 100cc) The air permeability was measured based on JIS-P8117 (Gurley tester method).
- Puncture strength Except for 10 cm of each end portion of the sample (nonwoven fabric), five test pieces having a width of 1.5 cm and a length of 20 cm were cut out per 1 m width. A load was applied to the test piece at a compression of 100 kg cell at 50 m / min, and the load until the jig was penetrated was defined as the piercing strength.
- general-purpose PET as a thermo
- a PET solution solution viscosity measured at a temperature of 35 ° C. using OCP as
- Example 3 The web was laminated directly on the continuous long-fiber nonwoven fabric produced by the spunbond method by the same melt blown method as described above to obtain a PET-SM structure. Furthermore, while integrating with a calender roll, the nonwoven fabric separator was obtained by adjusting thickness and apparent density so that it might become desired thickness.
- Examples 4 and 5 to 13 The web is laminated by the same melt blown method as described above directly on the continuous long fiber nonwoven fabric produced by the spunbond method, and the continuous long fiber nonwoven fabric (fiber diameter 15 ⁇ m) produced by the spunbond method is further laminated thereon, A PET-SMS structure was adopted. Furthermore, while integrating with a calender roll, thickness and apparent density were adjusted so that it might become desired thickness, and each nonwoven fabric separator was obtained.
- Example 14 The web was laminated directly on the continuous long-fiber nonwoven fabric produced by the spunbond method by the same melt blown method as described above to obtain a PET-SM structure. Further, a web was laminated thereon by a melt blown method or a spun bond method to obtain a PET-SMMS structure. Finally, a nonwoven fabric separator was obtained by integrating with a calender roll and adjusting the thickness and the apparent density so as to obtain a desired thickness.
- a nonwoven fabric separator was obtained in the same manner as in [Example 4] using polyethylene (PE) resin.
- Example 16 A cupra nonwoven fabric “Benlyse (registered trademark)” manufactured by Asahi Kasei Fibers Co., Ltd. was used as a nonwoven fabric separator. This nonwoven fabric was composed of cellulose (Cel) fibers.
- Example 17 In the same manner as in [Example 1], 3 g / m 2 of polyester microfiber (fiber diameter 0.01 ⁇ m) obtained by electrospinning (ELSP) is laminated on the nonwoven fabric obtained by the spunbond method, and then calendered. The laminated nonwoven fabric was obtained by integrating with a roll.
- ELSP electrospinning
- Example 18 A co-PET / PET sheath core with a fiber diameter of 16 ⁇ m is collected on the net by a spunbond method so that it becomes 20 g / m 2, and after dehydration and drying, it is pressure-bonded with a flat roll so that the fibers do not dissipate. A short fiber web was obtained. Next, as in [Example 4], an melt-blown fiber to be a non-woven fabric layer (I layer) is sprayed thereon to form an intermediate layer thereon, and a non-woven fabric layer (II layer) is further formed thereon as [implementation]. A thermoplastic long fiber web having the same structure as in Example 4] was laminated. The obtained laminated web was thermally bonded with a flat roll and a calender roll to obtain a laminated nonwoven fabric.
- Example 20 and 45 A glass fiber nonwoven fabric was further arranged outside the nonwoven fabric separator obtained in [Example 4] and [Example 31].
- colloidal silica average particle size: 20 nm
- binder acrylic styrene
- Examples 27 and 28 The web is laminated by the same melt blown method as described above directly on the continuous long fiber nonwoven fabric produced by the spunbond method, and the continuous long fiber nonwoven fabric (fiber diameter 15 ⁇ m) produced by the spunbond method is further laminated thereon, A PET-SMS structure was adopted.
- the basis weight and the fiber diameter were appropriately adjusted from the viewpoint of controlling the pore diameter.
- the thickness and the apparent density were adjusted so as to obtain a desired thickness, and each nonwoven fabric separator was obtained.
- spinning temperature 300 ° C.
- heated air Under the condition of 1000 Nm3 / hr / m
- the resin melting temperature, spinning gas temperature, single-hole discharge amount of the molten resin, and the like were appropriately selected, and the thermoplastic resin was pulled and thinned.
- Various conditions regarding discharge, cooling, and collection were set from the viewpoint of suppressing fusion.
- the fiber diameter and the degree of crystallinity were adjusted by adjusting the amount of heated air to obtain a nonwoven fabric separator composed of a nonwoven fabric layer (I layer) composed of ultrafine fibers.
- Example 30 The web was laminated directly on the continuous long-fiber nonwoven fabric produced by the spunbond method by the same melt blown method as described above to obtain a PET-SM structure.
- the melting temperature of the meltblown resin, the spinning gas temperature, the single-hole discharge amount of the molten resin, and various conditions relating to discharge, cooling, and collection were set from the viewpoint of suppressing fusion.
- the nonwoven fabric separator was obtained by adjusting thickness and apparent density so that it might become desired thickness.
- Examples 31 to 40 The web is laminated by the same melt blown method as described above directly on the continuous long fiber nonwoven fabric produced by the spunbond method, and the continuous long fiber nonwoven fabric (fiber diameter 15 ⁇ m) produced by the spunbond method is further laminated thereon, A PET-SMS structure was adopted.
- the melting temperature of the meltblown resin, the spinning gas temperature, the single-hole discharge amount of the molten resin, and various conditions relating to discharge, cooling, and collection were set from the viewpoint of suppressing fusion.
- thickness and apparent density were adjusted so that it might become desired thickness, and each nonwoven fabric separator was obtained.
- Example 41 The web was laminated directly on the continuous long-fiber nonwoven fabric produced by the spunbond method by the same melt blown method as described above to obtain a PET-SM structure. Further, a web was laminated thereon by a melt blown method or a spun bond method to obtain a PET-SMMS structure. However, the melting temperature of the meltblown resin, the spinning gas temperature, the single-hole discharge amount of the molten resin, and various conditions relating to discharge, cooling, and collection were set from the viewpoint of suppressing fusion. Finally, a nonwoven fabric separator was obtained by integrating with a calender roll and adjusting the thickness and the apparent density so as to obtain a desired thickness.
- Example 42 A nonwoven fabric separator was obtained in the same manner as in [Example 31] using polypropylene (PP) resin.
- Example 43 A co-PET / PET sheath core with a fiber diameter of 16 ⁇ m is collected on the net by a spunbond method so that it becomes 20 g / m 2, and after dehydration and drying, it is pressure-bonded with a flat roll so that the fibers do not dissipate. A short fiber web was obtained.
- an intermediate layer is formed by spraying melt-blown fibers to be a non-woven fabric layer (I layer), and further, a non-woven fabric layer (II layer) is formed thereon.
- a thermoplastic long fiber web having the same structure as in Example 4] was laminated. The obtained laminated web was thermally bonded with a flat roll and a calender roll to obtain a laminated nonwoven fabric.
- OCP o-chlorophenol
- the distance from the meltblown nozzle to the thermoplastic resin long fiber web was set to 100 mm
- the suction force on the collecting surface immediately below the meltblown nozzle was set to 0.2 kPa
- the wind speed was set to 7 m / sec.
- the fiber diameter and the degree of crystallinity are adjusted by adjusting the amount of heated air.
- a nonwoven fabric having an SM structure comprising a nonwoven fabric layer (I layer) composed of ultrafine fibers Obtained.
- the web was further laminated on the obtained web by the same spunbond method as described above, and finally a nonwoven fabric having an SMS structure was produced.
- the nonwoven fabric base material was obtained by adjusting thickness and apparent density so that it might become desired thickness.
- the inorganic particle slurry was obtained by the following method. Colloidal silica (common name: silica / average particle size 12 nm) 10 parts by mass, 1 part by mass of ruboxymethylcellulose, 2.2 parts by mass of acrylic styrene binder (solids concentration 45%), sulfosuccinic acid surfactant (solids concentration) 50%) 1 part by mass and 85.8 parts by mass of water are accommodated in a container of NBK-1 (trade name, manufactured by Nippon Seiki Seisakusho Co., Ltd.) which is a non-bubbling kneader, and has a rotation speed of 1500 rpm and a dispersion treatment time of 5 Dispersion treatment was performed under conditions of minutes to obtain a uniform slurry.
- NBK-1 trade name, manufactured by Nippon Seiki Seisakusho Co., Ltd.
- the slurry was apply
- Example 57 Aluminum hydroxide (common name: alumina) was used for the inorganic particles in the applied slurry.
- Example 64 As the nonwoven fabric substrate, a pulp-based short fiber nonwoven fabric obtained by a papermaking method was used.
- Example 65 Using a polypropylene (PP) resin, a nonwoven fabric separator was obtained in the same manner as in [Example 48].
- PP polypropylene
- general-purpose PET as a thermoplastic resin
- OCP o-chlorophenol
- a PET solution solution viscosity measured at a temperature of 35 ° C. using O
- Example 73 The web was laminated directly on the continuous long-fiber nonwoven fabric produced by the spunbond method by the same melt blown method as described above to obtain a PET-SM structure. Finally, while integrating with a calender roll, the nonwoven fabric base material was obtained by adjusting thickness and apparent density so that it might become desired thickness.
- Example 74 A cupra nonwoven fabric “Benlyse (registered trademark)” manufactured by Asahi Kasei Fibers Co., Ltd. was used as a nonwoven fabric substrate. This nonwoven fabric was composed of cellulose (Cel) fibers.
- Example 75 A co-PET / PET sheath core with a fiber diameter of 16 ⁇ m is collected on the net by a spunbond method so that it becomes 20 g / m 2, and after dehydration and drying, it is pressure-bonded with a flat roll so that the fibers do not dissipate. A short fiber web was obtained. Next, as in [Example 4], an melt-blown fiber to be a non-woven fabric layer (I layer) is sprayed thereon to form an intermediate layer thereon, and a non-woven fabric layer (II layer) is further formed thereon as [implementation]. A thermoplastic long fiber web having the same structure as in Example 51] was laminated. The obtained laminated web was thermally bonded with a flat roll and a calender roll to obtain a nonwoven fabric substrate.
- Example 76 A polyethylene microporous membrane separator was further arranged outside the separator obtained in [Example 48].
- Example 77 A glass fiber nonwoven fabric was further arranged outside the separator obtained in [Example 48].
- Example 78 The separator obtained in [Example 72] was mounted on a control valve type lead-acid battery.
- the nonwoven fabric separator obtained by the present invention has an optimal material and a highly controlled structure, it has excellent ion permeability, liquid retention, electrical insulation, and chemical stability.
- the processing suitability as a battery is excellent, and the lead storage battery of the present invention can be produced at a low cost with a stable production process, a good yield, by having the nonwoven fabric mat of the present invention.
- the cycle life is very long with high output and low resistance. Therefore, the lead acid battery of this invention is utilized suitably.
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Abstract
Description
[1]
再生繊維又は合成繊維で構成された不織布を含む、鉛蓄電池用不織布セパレータ。
[2]
該不織布セパレータの平均孔径が、0.1μm~50μmである、[1]に記載のセパレータ。
[3]
該不織布セパレータの平均孔径(D)と孔数(N)の関係が、下記式:
1.0×102< D*N <1.0×104
を満たす、[1]又は[2]に記載のセパレータ。
[4]
該不織布セパレータの厚みが、30μm~1000μmであり、かつ目付が5g/m2~300g/m2である、[1]~[3]のいずれか1項に記載のセパレータ。
[5]
該不織布セパレータの空隙率が、30%~95%である、[1]~[4]のいずれか1項に記載のセパレータ。
[6]
該不織布が長繊維で構成されている、[1]~[5]のいずれか1項に記載のセパレータ。
[7]
該不織布の繊維径が、0.1μm~30μmである、[1]~[6]のいずれか1項に記載のセパレータ。
[8]
該不織布が、繊維径0.1μm~5μmを有する極細繊維を含む、[1]~[7]のいずれか1項に記載のセパレータ。
[9]
該不織布セパレータが、該極細繊維で構成される不織布層(I層)と、繊維径5μm~30μmを有する繊維で構成されている不織布層(II層)とを含む少なくとも2層で構成されている、[8]に記載のセパレータ。
[10]
該不織布セパレータが、該II層と該II層の中間層として該I層を配置した3層で構成されている、[9]に記載のセパレータ。
[11]
該不織布セパレータが、該合成繊維から構成されている、[1]~[10]のいずれか1項に記載のセパレータ。
[12]
該不織布セパレータが、ポリエステル繊維から構成されている、[1]~[11]のいずれか1項に記載のセパレータ。
[13]
該不織布セパレータが、ポリオレフィン繊維から構成されている、[1]~[12]のいずれか1項に記載のセパレータ。
[14]
該不織布セパレータが、セルロース繊維から構成されている、[1]~[13]のいずれか1項に記載のセパレータ。
[15]
該不織布セパレータの透気度が、0.01秒/100cc~10秒/100ccである、[1]~[14]のいずれか1項に記載のセパレータ。
[16]
該不織布セパレータの引張強度が、15N/15mm~300N/15mmである、[1]~[15]のいずれか1項に記載のセパレータ。
[17]
該不織布セパレータの比表面積が、0.1m2/g~50m2/gである、[1]~[16]のいずれか1項に記載のセパレータ。
[18]
該不織布セパレータが、親水加工された不織布である、[1]~[17]のいずれか1項に記載のセパレータ。
[19]
該不織布セパレータが、熱的結合により一体化された不織布である、[1]~[18]のいずれか1項に記載のセパレータ。
[20]
該不織布セパレータが、無機酸化物を含む、[1]~[19]のいずれか1項に記載のセパレータ。
[21]
該不織布セパレータが、空隙構造を有する不織布基材と、該不織布基材の表面部分又は該不織布基材の内部の繊維表面に存在する無機粒子とを含む、[1]~[20]のいずれか1項に記載のセパレータ。
[22]
該無機粒子が、ケイ素成分を含む、[21]に記載のセパレータ。
[23]
該無機粒子の平均粒径が、1nm~5000nmである、[21]又は[22]に記載のセパレータ。
[24]
該無機粒子の比表面積が、0.1m2/g~1000m2/gである、[21]~[23]のいずれか1項に記載のセパレータ。
[25]
該不織布セパレータが、該不織布基材の内部に存在するバインダーを、該無機粒子100質量部に対して1~500質量部含む、[21]~[24]のいずれか1項に記載のセパレータ。
[26]
該不織布セパレータが、熱シール可能である、[1]~[25]のいずれか1項に記載のセパレータ。
[27]
該不織布セパレータと微多孔膜を積層させた、[1]~[26]のいずれか1項に記載のセパレータ。
[28]
該不織布セパレータとガラス繊維から成る不織布とを積層させた、[1]~[27]のいずれか1項に記載のセパレータ。
[29]
該極細繊維を用いてメルトブロウン法で該I層を形成する工程を含む、[9]に記載のセパレータの製造方法。
[30]
正極及び負極、並びにそれらの間に配置された[1]~[28]のいずれか1項に記載の不織布セパレータを含む極板群と、電解液とを含む液式鉛蓄電池。
[31]
[1]~[28]のいずれか1項に記載の不織布セパレータを搭載した制御弁式鉛蓄電池。
本実施形態の不織布セパレータは、天然繊維(天然高分子)を原料にして製造される再生繊維、又は純合成的に有機高分子化合物を製造する合成繊維で構成されている。
本実施形態の塗工不織布セパレータは、空隙構造を有する不織布基材と、その基材の表面部分、又は基材内部の繊維表面に存在する無機粒子と、を含むことが好ましい。無機粒子は、不織布の外表面、あるいは基材の表面部分、あるいは基材内部の繊維表面に連続的に無機粒子が存在する層として形成しているか、または非連続的なバルク(塊)を形成していてもよい。
JIS L-1906に規定の方法に従い、縦20cm×横25cmの試験片を、試料の幅方向1m当たり3箇所、長さ方向1m当たり3箇所の、計1m×1m当たり9箇所採取して質量を測定し、その平均値を単位面積当たりの質量に換算して目付けを求めた。
JIS L-1906に規定の方法に従い、試験片の幅1m当たり10箇所の厚みを測定し、その平均値を求めた。荷重9.8kPaの条件下で厚みの測定を行った。
上記(1)にて測定した目付け(g/m2)、及び上記(2)にて測定した厚み(mm)を用い、単位を調整して以下の式:
見掛け密度=(目付け)/(厚み)
により見掛け密度を算出した。
上記(3)にて計算した見掛け密度(g/cm3)を用いて、以下の式:
空隙率={1-(見掛け密度)/(樹脂密度)}/100
より空隙率を算出した。
不織布を10cm×10cmにカットし、上下60℃の鉄板に0.30MPaの圧力で90秒間プレスした後、不織布を白金にて蒸着した。SEM装置(JSM-6510 日本電子株式会社製)を用いて、加速電圧15kV、ワーキングディスタンス21mmの条件で、蒸着された不織布を撮影した。撮影倍率は、平均繊維径が0.5μm未満の糸は10000倍、平均繊維径が0.5μm以上1.5μm未満の糸は6000倍、1.5μm以上の糸は4000倍とした。それぞれの撮影倍率での撮影視野は、10000倍では12.7μm×9.3μm、6000倍では21.1μm×15.9μm、4000倍では31.7μm×23.9μmとした。ランダムに繊維100本以上を撮影し、全ての繊維径を測長した。ただし、糸長方向で融着している繊維同士は測定対象から除いた。以下の式:
Dw=ΣWi・Di=Σ(Ni・Di2)/(Ni・Di)
{式中、Wi=繊維径Diの重量分率=Ni・Di/ΣNi・Diである。}
により求められる重量平均繊維径(Dw)を、平均繊維径(μm)とした。
PMI社のパームポロメーター(型式:CFP-1200AEX)を用いた。測定には浸液にPMI社製のシルウィックを用い、試料を浸液に浸して充分に脱気した後、測定を行なった。
本測定装置は、フィルターを試料として、予め表面張力が既知の液体にフィルターを浸し、フィルターの全ての細孔を液体の膜で覆った状態からフィルターに圧力を掛け、液膜の破壊される圧力と液体の表面張力とから計算された細孔の孔径を測定する。計算には下記の数式を用いる。
d=C・r/P
(式中、d(単位:μm)はフィルターの孔径、r(単位:N/m)は液体の表面張力、P(単位:Pa)はその孔径の液膜が破壊される圧力、かつCは定数である。)
上記の数式より、液体に浸したフィルターに掛ける圧力Pを低圧から高圧に連続的に変化させた場合の流量(濡れ流量)を測定する。初期の圧力では、最も大きな細孔の液膜でも破壊されないので流量は0である。圧力を上げていくと、最も大きな細孔の液膜が破壊され、流量が発生する(バブルポイント)。さらに圧力を上げていくと、各圧力に応じて流量は増加する。最も小さな細孔の液膜が破壊されたときの圧力における流量が、乾いた状態の流量(乾き流量)と一致する。
本測定装置による測定方法では、或る圧力における濡れ流量を、同圧力での乾き流量で除した値を累積フィルター流量(単位:%)と呼ぶ。累積フィルター流量が50%となる圧力で破壊される液膜の孔径を、平均流量孔径と呼ぶ。この平均流量孔径を、本発明の平均孔径(D)とした。またその際得られる細孔数を孔数(N)とした。
本発明の最大孔径は、不織布を上記フィルター試料として測定し、累積フィルター流量が50%の-2σの範囲、すなわち、累積フィルター流量が2.3%となる圧力で破壊される液膜の孔径とした。上記測定方法にて、各サンプルについて3点測定を行い、その平均値として平均流量孔径、及び最少孔径と最大孔径とを計算した。
JIS-P8117(ガーレー試験機法)に基づき、透気度を測定した。
試料(不織布)の各端部10cmを除き、幅3cm×長さ20cmの試験片を、1m幅につき5箇所切り取った。試験片が破断するまで荷重を加え、MD方向の試験片の最大荷重時の強さの平均値を求めた。
試料(不織布)の各端部10cmを除き、幅1.5cm×長さ20cmの試験片を、1m幅につき5箇所切り取った。試験片に圧縮100kgセル、50m/minにて荷重を加え、冶具が貫通されるまでの荷重を突き刺し強度とした。
装置型式:Gemini2360 株式会社島津製作所製を用いた。
不織布を円筒状に丸め比表面積測定用セルに詰めた。この際に投入するサンプル重量は0.20~0.60g程度が好ましい。サンプルを投入したセルを60℃の条件下で30分間乾燥した後に、10分間冷却を行った。その後、上記の比表面積測定装置にセルをセットし、サンプル表面への窒素ガス吸着により、下記BETの下記式:
P/(V(P0-P))=1/(Vm×C)+((C-1)/(Vm×C))(P/P0)
{式中、P0:飽和水蒸気圧(Pa)、Vm:単分子層吸着量(mg/g)、C:吸着熱などに関するパラメーター(-)<0であり、本関係式は、特にP/P0=0.05~0.35の範囲で良く成り立つ。}を適用し、比表面積値を求めた。BET式とは、一定温度で吸着平衡状態である時、吸着平衡圧Pと、その圧力での吸着量Vの関係を表した式である。
測定装置として、HIOKI製Dital Super Megohmmeter、及びHIOKI製平板試料用電極SME-8311を使用した。100mm×100mmの試験片(不織布)を準備し、電圧10V、及び測定時間60秒の測定条件下で、体積抵抗値(Ω/□)を測定した。
電解液とした硫酸40%水溶液に、直径40mmにサンプリングした不織布を浸漬させた後、減圧下で1時間脱気を行う。脱気後のサンプルを鉛電極(鉛、及び酸化鉛を直径20mmの円板形状にした鉛にペーストしたもの)の間に挿入し、12cNの荷重を電極間にかけ電極及び不織布を固定した。次にこの挿入に伴う増加した電極間の電気抵抗を不織布の電気抵抗とし、20℃、100kHzの周波数でLCRメータを用いて測定した(単位はΩ)。
不織布の試験片(150mm×150mm)を用意し、その乾燥質量(Wa)を測定した。硫酸(比重1.28g/cm3)中に試験片を広げて浸し、1時間後に水溶液から引き上げ、相対湿度65%の無風室内に10分間放置した後の試験片質量(Wb)を測定し、電解液保液率(%)を下記式:
電解液保液率(%)=(Wa-Wb)/Wa×100
により算出した。
(14)加工適性
正極板をセパレータに内包する際に、セパレータが目視で分かる程度に膨らんだ状態に歪んで変形したり、シールが上手くできていなかったりするものを不良品として、1000枚加工したときの不良品率を測定し、0.5%未満をA、0.5~1%未満をB、1%~5%をC、それ以上をDとして、加工適性の指標とした。
正極板(酸化鉛)1枚の両側にセパレータを介して負極板(鉛)を電槽内に配置した後、電解液(比重1.28の希硫酸)を注いで、液式鉛蓄電池を作製した。作製した鉛蓄電池を、下記放電条件、充電条件にて充放電を繰り返し行った。
放電条件:10A(0.5CA)、下限電圧10.5V
充電条件(定電圧法):最大充電電流10A、最大充電圧14.7V
最大充電時間12時間
25℃の雰囲気下で電池に振動を加え、放電から充電までのサイクルを1サイクルとし、電極反応を開始した。その際、初期容量を測定し、短絡の有無を確認した。また、初期容量80%を下回った時点のサイクル数をサイクル特性とした。
電槽内上部、下部から溶液を10mLずつ採取し、これらのサンプルの比重を測定し、上部と下部の比重の差を比重差とした。
熱可塑性樹脂繊維で構成される不織布層(II層)を形成した。具体的には、汎用的なPET(熱可塑性樹脂として)の溶液(o-クロロフェノール(OCP)を溶媒として用い、温度35℃で測定した溶液粘度:ηsp/c=0.67を有する)(溶液粘度は温度35℃の恒温水槽中の粘度管で測定した。以下同じ。)を用い、スパンボンド法により、紡糸温度300℃で、フィラメント群を、移動する捕集ネット面に向けて押し出し、紡糸速度4500m/分で紡糸した。次いで、コロナ帯電で3μC/g程度帯電させてフィラメント群を十分に開繊させ、熱可塑性樹脂長繊維ウェブを捕集ネット上に形成した。繊維径の調整は、牽引条件を変えることにより行い、不織布セパレータを得た。
極細繊維不織布層(I層)として、PETの溶液(OCPを溶媒として用い、温度35℃で測定した溶液粘度:ηsp/c=0.50を有するもの)を用い、紡糸温度300℃、加熱空気1000Nm3/hr/mの条件下で、メルトブロウン法により紡糸して、上記の熱可塑性樹脂長繊維ウェブ上に吹きつけた。この際、メルトブロウンノズルから熱可塑性樹脂長繊維ウェブまでの距離を100mmとし、メルトブロウンノズル直下の捕集面における吸引力を0.2kPa、風速を7m/secに設定した。繊維径及び結晶化度の調整は、加熱空気量を調整することにより行い、極細繊維で構成される不織布層(I層)から成る不織布セパレータを得た。
スパンボンド法で作製した連続長繊維不織布上に直接、上記と同じメルトブロウン法によりウェブを積層させ、PET-SM構造とした。さらに、カレンダーロールにて一体化するとともに、所望の厚みとなるように厚み及び見掛け密度を調整することで、不織布セパレータを得た。
スパンボンド法で作製した連続長繊維不織布上に直接、上記と同じメルトブロウン法によりウェブを積層させ、さらにその上にスパンボンド法で作製した連続長繊維不織布(繊維径15μm)を積層して、PET-SMS構造とした。さらに、カレンダーロールにて一体化するとともに、所望の厚みとなるように厚み及び見掛け密度を調整し、各不織布セパレータを得た。
スパンボンド法で作製した連続長繊維不織布上に直接、上記と同じメルトブロウン法によりウェブを積層させ、PET-SM構造とした。さらにその上に、メルトブロウン法、スパンボンド法により、ウェブを積層させていき、PET―SMMS構造とした。最終的に、カレンダーロールにて一体化するとともに、所望の厚みとなるように厚み及び見掛け密度を調整することで、不織布セパレータを得た。
ポリプロピレン(PP)樹脂を使用して、[実施例4]と同様の方法で不織布セパレータを得た。
ポリエチレン(PE)樹脂を使用して、[実施例4]と同様の方法で不織布セパレータを得た。
旭化成せんい株式会社製のキュプラ不織布「ベンリーゼ(登録商標)」を不織布セパレータとして用いた。この不織布は、セルロース(Cel)繊維から構成されていた。
[実施例1]と同様にスパンボンド法により得られた不織布の上に、静電紡糸(ELSP)により得られたポリエステル極細繊維(繊維径0.01μm)を3g/m2積層させ、その後カレンダーロールにて一体化させ、積層不織布を得た。
繊維径16μmのco-PET/PET鞘芯をスパンボンド法にてネット上に20g/m2となるように捕集し、脱水乾燥後、繊維が散逸しない程度に、フラットロールにて圧着して短繊維ウェブを得た。次いで、その上に中間層として、[実施例4]と同様に、不織布層(I層)となるメルトブロウン繊維を吹きつけて形成し、さらに、その上に不織布層(II層)として[実施例4]と同じ構成の熱可塑性樹脂長繊維ウェブを積層した。得られた積層ウェブを、フラットロール及びカレンダーロールにて熱接着し、積層不織布を得た。
[実施例4]、[実施例31]でそれぞれ得られた不織布セパレータの外側にさらにポリエチレン微多孔膜セパレータを配置させた。
[実施例4]、[実施例31]でそれぞれ得られた不織布セパレータの外側にさらにガラス繊維不織布を配置させた。
[実施例4]、[実施例31]でそれぞれ得られた不織布セパレータにコロイダルシリカ(平均粒径:20nm)とバインダー(アクリルスチレン系)を含んだ水溶液(コロイダルシリカ:バインダー:水=40%:10%:50%)をデイッピング方式により塗工させた。
[実施例2]、[実施例29]で得られた不織布セパレータを制御弁式鉛蓄電池に搭載した。
スパンボンド法で作製した連続長繊維不織布上に直接、上記と同じメルトブロウン法によりウェブを積層させ、さらにその上にスパンボンド法で作製した連続長繊維不織布(繊維径15μm)を積層して、PET-SMS構造とした。メルトブロウン層には、孔径を制御する観点で、目付量及び繊維径を適宜調整した。さらに孔数を制御する観点で、適切な硬度を有するカレンダーロールにて一体化するとともに、所望の厚みとなるように厚み及び見掛け密度を調整し、各不織布セパレータを得た。
極細繊維不織布層(I層)として、PETの溶液(OCPを溶媒として用い、温度35℃で測定した溶液粘度:ηsp/c=0.50を有するもの)を用い、紡糸温度300℃、加熱空気1000Nm3/hr/mの条件下で、メルトブロウン法により紡糸して、上記の熱可塑性樹脂長繊維ウェブ上に吹きつけた。この際、メルトブロウンノズルから熱可塑性樹脂長繊維ウェブまでの距離を100mmとし、メルトブロウンノズル直下の捕集面における吸引力を0.2kPa、風速を7m/secに設定した。樹脂の溶融温度、紡糸ガス温度、溶融樹脂の単孔吐出量などを適宜選択し、熱可塑性樹脂を牽引細化させた。吐出、冷却、及び捕集に関する各種条件は融着を抑制させる観点でそれぞれ設定した。繊維径及び結晶化度の調整は、加熱空気量を調整することにより行い、極細繊維で構成される不織布層(I層)から成る不織布セパレータを得た。
スパンボンド法で作製した連続長繊維不織布上に直接、上記と同じメルトブロウン法によりウェブを積層させ、PET-SM構造とした。ただし、メルトブロウンの樹脂の溶融温度、紡糸ガス温度、及び溶融樹脂の単孔吐出量、並びに吐出、冷却及び捕集に関する各種条件は、融着を抑制させる観点でそれぞれ設定した。さらに、カレンダーロールにて一体化するとともに、所望の厚みとなるように厚み及び見掛け密度を調整することで、不織布セパレータを得た。
スパンボンド法で作製した連続長繊維不織布上に直接、上記と同じメルトブロウン法によりウェブを積層させ、さらにその上にスパンボンド法で作製した連続長繊維不織布(繊維径15μm)を積層して、PET-SMS構造とした。ただし、メルトブロウンの樹脂の溶融温度、紡糸ガス温度、及び溶融樹脂の単孔吐出量、並びに吐出、冷却及び捕集に関する各種条件は、融着を抑制させる観点でそれぞれ設定した。さらに、カレンダーロールにて一体化するとともに、所望の厚みとなるように厚み及び見掛け密度を調整し、各不織布セパレータを得た。
スパンボンド法で作製した連続長繊維不織布上に直接、上記と同じメルトブロウン法によりウェブを積層させ、PET-SM構造とした。さらにその上に、メルトブロウン法、スパンボンド法により、ウェブを積層させていき、PET―SMMS構造とした。ただし、メルトブロウンの樹脂の溶融温度、紡糸ガス温度、及び溶融樹脂の単孔吐出量、並びに吐出、冷却及び捕集に関する各種条件は、融着を抑制させる観点でそれぞれ設定した。最終的に、カレンダーロールにて一体化するとともに、所望の厚みとなるように厚み及び見掛け密度を調整することで、不織布セパレータを得た。
ポリプロピレン(PP)樹脂を使用して、[実施例31]と同様の方法で不織布セパレータを得た。
繊維径16μmのco-PET/PET鞘芯をスパンボンド法にてネット上に20g/m2となるように捕集し、脱水乾燥後、繊維が散逸しない程度に、フラットロールにて圧着して短繊維ウェブを得た。次いで、その上に中間層として、[実施例31]と同様に、不織布層(I層)となるメルトブロウン繊維を吹きつけて形成し、さらに、その上に不織布層(II層)として[実施例4]と同じ構成の熱可塑性樹脂長繊維ウェブを積層した。得られた積層ウェブを、フラットロール及びカレンダーロールにて熱接着し、積層不織布を得た。
熱可塑性樹脂繊維で構成される不織布層(II層)を形成した。具体的には、汎用的なPET(熱可塑性樹脂として)の溶液(o-クロロフェノール(OCP)を溶媒として用い、温度35℃で測定した溶液粘度:ηsp/c=0.67を有する)(溶液粘度は温度35℃の恒温水槽中の粘度管で測定した。以下同じ。)を用い、スパンボンド法により、紡糸温度300℃で、フィラメント群を、移動する捕集ネット面に向けて押し出し、紡糸速度4500m/分で紡糸した。次いで、コロナ帯電で3μC/g程度帯電させてフィラメント群を十分に開繊させ、熱可塑性樹脂長繊維ウェブを捕集ネット上に形成した。捕集したウェブ上に、極細繊維不織布層(I層)を積層させた。具体的には、PETの溶液(OCPを溶媒として用い、温度35℃で測定した溶液粘度:ηsp/c=0.50を有するもの)を用い、紡糸温度300℃、加熱空気1000Nm3/hr/mの条件下で、メルトブロウン法により紡糸して、上記の熱可塑性樹脂長繊維ウェブ上に吹きつけた。この際、メルトブロウンノズルから熱可塑性樹脂長繊維ウェブまでの距離を100mmとし、メルトブロウンノズル直下の捕集面における吸引力を0.2kPa、風速を7m/secに設定した。繊維径及び結晶化度の調整は、加熱空気量を調整することにより行い、不織布層(II層)の上に、極細繊維で構成される不織布層(I層)から成るSM構造からなる不織布を得た。その後、得られたウェブ上に、さらに上記と同様のスパンボンド法により、ウェブを積層させ、最終的にSMS構造からなる不織布を作製した。最終的には、カレンダーロールにて一体化するとともに、所望の厚みとなるように厚み及び見掛け密度を調整することで、不織布基材を得た。
無機粒子スラリーは、以下の方法により得た。コロイダルシリカ(通称:シリカ/平均粒径12nm)10質量部、力ルボキシメチルセルロース1質量部、アクリルスチレンバインダー(固形分濃度45%)2.2質量部、スルホコハク酸系界面活性剤(固形分濃度50%)1質量部、及び水85.8質量部を、ノンバブリングニーダーであるNBK-1((株)日本精機製作所製商品名)の容器内に収容し、回転数1500rpm、分散処理時間5分間の条件にて、分散処理を施して、均一なスラリーを得た。
そして、得られた不織布基材の上にスラリーを、コンマコート方式(ライン速度:10m/min、ギャップ10μm)により塗布した。更に、80℃のオーブンで乾燥して溶媒を除去して、セパレータを得た。塗工量は適宜、シリカ含有量にて調製した。
塗布したスラリー中の無機粒子には、水酸化アルミニウム(通称:アルミナ)を使用した。
不織布基材には、抄造法により得られたパルプ系短繊維不織布を使用した。
ポリプロピレン(PP)樹脂を使用して、[実施例48]と同様の方法で不織布セパレータを得た。
熱可塑性樹脂繊維で構成される不織布層(II層)を形成した。具体的には、汎用的なPET(熱可塑性樹脂として)の溶液(o-クロロフェノール(OCP)を溶媒として用い、温度35℃で測定した溶液粘度:ηsp/c=0.67を有する)(溶液粘度は温度35℃の恒温水槽中の粘度管で測定した。以下同じ。)を用い、スパンボンド法により、紡糸温度300℃で、フィラメント群を、移動する捕集ネット面に向けて押し出し、紡糸速度4500m/分で紡糸した。次いで、コロナ帯電で3μC/g程度帯電させてフィラメント群を十分に開繊させ、熱可塑性樹脂長繊維ウェブを捕集ネット上に形成し、不織布基材を得た。
極細繊維不織布層(I層)として、PETの溶液(OCPを溶媒として用い、温度35℃で測定した溶液粘度:ηsp/c=0.50を有するもの)を用い、紡糸温度300℃、加熱空気1000Nm3/hr/mの条件下で、メルトブロウン法により紡糸して、上記の熱可塑性樹脂長繊維ウェブ上に吹きつけた。この際、メルトブロウンノズルから熱可塑性樹脂長繊維ウェブまでの距離を100mmとし、メルトブロウンノズル直下の捕集面における吸引力を0.2kPa、風速を7m/secに設定した。繊維径及び結晶化度の調整は、加熱空気量を調整することにより行い、極細繊維で構成される不織布層(I層)から成る不織布基材を得た。
スパンボンド法で作製した連続長繊維不織布上に直接、上記と同じメルトブロウン法によりウェブを積層させ、PET-SM構造とした。最終的に、カレンダーロールにて一体化するとともに、所望の厚みとなるように厚み及び見掛け密度を調整することで、不織布基材を得た。
旭化成せんい株式会社製のキュプラ不織布「ベンリーゼ(登録商標)」を不織布基材として用いた。この不織布は、セルロース(Cel)繊維から構成されていた。
繊維径16μmのco-PET/PET鞘芯をスパンボンド法にてネット上に20g/m2となるように捕集し、脱水乾燥後、繊維が散逸しない程度に、フラットロールにて圧着して短繊維ウェブを得た。次いで、その上に中間層として、[実施例4]と同様に、不織布層(I層)となるメルトブロウン繊維を吹きつけて形成し、さらに、その上に不織布層(II層)として[実施例51]と同じ構成の熱可塑性樹脂長繊維ウェブを積層した。得られた積層ウェブを、フラットロール及びカレンダーロールにて熱接着し、不織布基材を得た。
[実施例48]で得られたセパレータの外側にさらにポリエチレン微多孔膜セパレータを配置させた。
[実施例48]で得られたセパレータの外側にさらにガラス繊維不織布を配置させた。
[実施例72]で得られたセパレータを制御弁式鉛蓄電池に搭載した。
セパレータとして、鉛蓄電池用に市販されているポリエチレン製微多孔膜を使用した。
セパレータとして、鉛蓄電池用に市販されているポリエチレン製微多孔膜にガラスマット(GM)を貼り合わせて使用した。
セパレータとして、鉛蓄電池用に市販されているAGM(Absorbed Glass Mat)セパレータを制御式鉛蓄電池に搭載した。
セパレータとして、市販されているポリエステル製織物を使用した。
Claims (31)
- 再生繊維又は合成繊維で構成された不織布を含む、鉛蓄電池用不織布セパレータ。
- 該不織布セパレータの平均孔径が、0.1μm~50μmである、請求項1に記載のセパレータ。
- 該不織布セパレータの平均孔径(D)と孔数(N)の関係が、下記式:
1.0×102< D*N <1.0×104
を満たす、請求項1又は2に記載のセパレータ。 - 該不織布セパレータの厚みが、30μm~1000μmであり、かつ目付が5g/m2~300g/m2である、請求項1~3のいずれか1項に記載のセパレータ。
- 該不織布セパレータの空隙率が、30%~95%である、請求項1~4のいずれか1項に記載のセパレータ。
- 該不織布が長繊維で構成されている、請求項1~5のいずれか1項に記載のセパレータ。
- 該不織布の繊維径が、0.1μm~30μmである、請求項1~6のいずれか1項に記載のセパレータ。
- 該不織布が、繊維径0.1μm~5μmを有する極細繊維を含む、請求項1~7のいずれか1項に記載のセパレータ。
- 該不織布セパレータが、該極細繊維で構成される不織布層(I層)と、繊維径5μm~30μmを有する繊維で構成されている不織布層(II層)とを含む少なくとも2層で構成されている、請求項8に記載のセパレータ。
- 該不織布セパレータが、該II層と該II層の中間層として該I層を配置した3層で構成されている、請求項9に記載のセパレータ。
- 該不織布セパレータが、該合成繊維から構成されている、請求項1~10のいずれか1項に記載のセパレータ。
- 該不織布セパレータが、ポリエステル繊維から構成されている、請求項1~11のいずれか1項に記載のセパレータ。
- 該不織布セパレータが、ポリオレフィン繊維から構成されている、請求項1~12のいずれか1項に記載のセパレータ。
- 該不織布セパレータが、セルロース繊維から構成されている、請求項1~13のいずれか1項に記載のセパレータ。
- 該不織布セパレータの透気度が、0.01秒/100cc~10秒/100ccである、請求項1~14のいずれか1項に記載のセパレータ。
- 該不織布セパレータの引張強度が、15N/15mm~300N/15mmである、請求項1~15のいずれか1項に記載のセパレータ。
- 該不織布セパレータの比表面積が、0.1m2/g~50m2/gである、請求項1~16のいずれか1項に記載のセパレータ。
- 該不織布セパレータが、親水加工された不織布である、請求項1~17のいずれか1項に記載のセパレータ。
- 該不織布セパレータが、熱的結合により一体化された不織布である、請求項1~18のいずれか1項に記載のセパレータ。
- 該不織布セパレータが、無機酸化物を含む、請求項1~19のいずれか1項に記載のセパレータ。
- 該不織布セパレータが、空隙構造を有する不織布基材と、該不織布基材の表面部分又は該不織布基材の内部の繊維表面に存在する無機粒子とを含む、請求項1~20のいずれか1項に記載のセパレータ。
- 該無機粒子が、ケイ素成分を含む、請求項21に記載のセパレータ。
- 該無機粒子の平均粒径が、1nm~5000nmである、請求項21又は22に記載のセパレータ。
- 該無機粒子の比表面積が、0.1m2/g~1000m2/gである、請求項21~23のいずれか1項に記載のセパレータ。
- 該不織布セパレータが、該不織布基材の内部に存在するバインダーを、該無機粒子100質量部に対して1~500質量部含む、請求項21~24のいずれか1項に記載のセパレータ。
- 該不織布セパレータが、熱シール可能である、請求項1~25のいずれか1項に記載のセパレータ。
- 該不織布セパレータと微多孔膜を積層させた、請求項1~26のいずれか1項に記載のセパレータ。
- 該不織布セパレータとガラス繊維から成る不織布とを積層させた、請求項1~27のいずれか1項に記載のセパレータ。
- 該極細繊維を用いてメルトブロウン法で該I層を形成する工程を含む、請求項9に記載のセパレータの製造方法。
- 正極及び負極、並びにそれらの間に配置された請求項1~28のいずれか1項に記載の不織布セパレータを含む極板群と、電解液とを含む液式鉛蓄電池。
- 請求項1~28のいずれか1項に記載の不織布セパレータを搭載した制御弁式鉛蓄電池。
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Cited By (4)
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JP2019145418A (ja) * | 2018-02-22 | 2019-08-29 | 宇部興産株式会社 | 鉛電池用硫酸イオン沈降抑制部材及びそれを用いる鉛電池 |
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US20210376304A1 (en) * | 2020-05-29 | 2021-12-02 | Johns Manville | Multilayer non-woven mat for lead acid batteries and applications therefor |
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US20220336925A1 (en) * | 2021-04-15 | 2022-10-20 | Hollingsworth & Vose Company | Dual-layer separator for batteries |
KR102523085B1 (ko) * | 2021-04-28 | 2023-04-18 | 한국앤컴퍼니 주식회사 | 다공성 폴리에스터 부직포를 적용하여 이온 이동성을 향상시키는 납축전지용 극판 제조방법 |
KR102617644B1 (ko) * | 2021-08-13 | 2023-12-27 | 한국앤컴퍼니 주식회사 | 강도 개선을 위하여 스프링 구조의 유기 섬유를 적용한 납축전지용 격리판 제조 방법 |
Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5795071A (en) * | 1980-12-04 | 1982-06-12 | Fujikura Ltd | Manufacture of separator for acid battery |
JPS61281454A (ja) * | 1985-06-06 | 1986-12-11 | Asahi Chem Ind Co Ltd | 電池用セパレ−タ |
JPS6264055A (ja) * | 1985-09-13 | 1987-03-20 | Matsushita Electric Ind Co Ltd | 鉛蓄電池 |
JPH06236752A (ja) * | 1992-12-17 | 1994-08-23 | Nippon Muki Co Ltd | 鉛蓄電池用セパレータ並びにその製造法 |
WO2001048065A1 (en) * | 1999-12-28 | 2001-07-05 | Hitoshi Kanazawa | Method of modifying polymeric material and use thereof |
JP2002260714A (ja) | 2001-03-01 | 2002-09-13 | Matsushita Electric Ind Co Ltd | 制御弁式鉛蓄電池 |
JP2011070904A (ja) * | 2009-09-25 | 2011-04-07 | Shin Kobe Electric Mach Co Ltd | 鉛蓄電池用セパレータ及びそれを用いた鉛蓄電池 |
JP2014160588A (ja) | 2013-02-20 | 2014-09-04 | Panasonic Corp | 制御弁式鉛蓄電池 |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS6264056A (ja) * | 1985-09-17 | 1987-03-20 | Matsushita Electric Ind Co Ltd | 鉛蓄電池の製造法 |
KR101417539B1 (ko) | 2009-08-19 | 2014-07-08 | 아사히 가세이 셍이 가부시키가이샤 | 세퍼레이터 및 고체 전해 콘덴서 |
WO2013008454A1 (ja) | 2011-07-11 | 2013-01-17 | パナソニック株式会社 | 鉛蓄電池 |
TWI618279B (zh) | 2012-04-04 | 2018-03-11 | Asahi Kasei Fibers Corp | 分隔件材料 |
-
2017
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- 2017-02-21 CN CN201780013831.4A patent/CN108701795B/zh active Active
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Patent Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5795071A (en) * | 1980-12-04 | 1982-06-12 | Fujikura Ltd | Manufacture of separator for acid battery |
JPS61281454A (ja) * | 1985-06-06 | 1986-12-11 | Asahi Chem Ind Co Ltd | 電池用セパレ−タ |
JPS6264055A (ja) * | 1985-09-13 | 1987-03-20 | Matsushita Electric Ind Co Ltd | 鉛蓄電池 |
JPH06236752A (ja) * | 1992-12-17 | 1994-08-23 | Nippon Muki Co Ltd | 鉛蓄電池用セパレータ並びにその製造法 |
WO2001048065A1 (en) * | 1999-12-28 | 2001-07-05 | Hitoshi Kanazawa | Method of modifying polymeric material and use thereof |
JP2002260714A (ja) | 2001-03-01 | 2002-09-13 | Matsushita Electric Ind Co Ltd | 制御弁式鉛蓄電池 |
JP2011070904A (ja) * | 2009-09-25 | 2011-04-07 | Shin Kobe Electric Mach Co Ltd | 鉛蓄電池用セパレータ及びそれを用いた鉛蓄電池 |
JP2014160588A (ja) | 2013-02-20 | 2014-09-04 | Panasonic Corp | 制御弁式鉛蓄電池 |
Non-Patent Citations (1)
Title |
---|
See also references of EP3425697A4 |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2019102282A (ja) * | 2017-12-04 | 2019-06-24 | 日立化成株式会社 | 鉛蓄電池 |
JP7152831B2 (ja) | 2017-12-04 | 2022-10-13 | 昭和電工マテリアルズ株式会社 | 鉛蓄電池 |
CN111433941A (zh) * | 2017-12-05 | 2020-07-17 | 日立化成株式会社 | 铅蓄电池用隔膜和铅蓄电池 |
JP2019145418A (ja) * | 2018-02-22 | 2019-08-29 | 宇部興産株式会社 | 鉛電池用硫酸イオン沈降抑制部材及びそれを用いる鉛電池 |
JP7040110B2 (ja) | 2018-02-22 | 2022-03-23 | 宇部興産株式会社 | 鉛電池用硫酸イオン沈降抑制部材及びそれを用いる鉛電池 |
WO2022014543A1 (ja) * | 2020-07-14 | 2022-01-20 | 旭化成株式会社 | 不織布セパレータ |
JPWO2022014543A1 (ja) * | 2020-07-14 | 2022-01-20 |
Also Published As
Publication number | Publication date |
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US10700325B2 (en) | 2020-06-30 |
KR20180089526A (ko) | 2018-08-08 |
EP3425697B1 (en) | 2020-09-16 |
CN108701795B (zh) | 2021-10-01 |
KR102130432B1 (ko) | 2020-07-07 |
TW201737531A (zh) | 2017-10-16 |
JP6735811B2 (ja) | 2020-08-05 |
TWI636604B (zh) | 2018-09-21 |
US20190051878A1 (en) | 2019-02-14 |
EP3425697A1 (en) | 2019-01-09 |
CN108701795A (zh) | 2018-10-23 |
EP3425697A4 (en) | 2019-01-09 |
ES2824780T3 (es) | 2021-05-13 |
JPWO2017150279A1 (ja) | 2018-09-06 |
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