JP2018006258A - Lead-acid battery separator and lead-acid battery using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide: a non-woven fabric separator for a lead-acid battery suppressing the stratification of a battery, the lead-acid battery being high in output, high in durability and low in resistance and further extending cycle life; and a lead-acid battery.SOLUTION: There are provided a separator having excellent ion permeability, liquid retaining properties, electrical insulating properties, and chemical stability, and a lead-acid battery which includes the separator and which is high in output, high in durability and low in resistance and further extends cycle life. There is also provided a method of manufacturing a separator, which is excellent in processing suitability as a battery, and which is stable, high in yield, and low in cost since the separator comprises a non-woven fabric mat.SELECTED DRAWING: None

Description

  The present invention relates to a lead-acid battery separator and a lead-acid battery using the same.

  Currently, the world's most produced lead-acid battery among secondary batteries is in-vehicle applications including automobiles such as engine starting, golf carts, ships, aircraft, and other special vehicles, as well as forklifts and farming It is widely used in industrial applications that are used for powering machines, railways, submarines, etc., and for stationary equipment such as uninterruptible power supplies (UPS) and communication equipment.

  In recent years, along with diversification of market needs, lead-acid batteries having high functions such as high output, high durability, and long life have been developed.

  In particular, extending the battery performance is required for idling stop applications that repeatedly charge and discharge in a partially charged state (PSOC: Partial State of Charge), or DC (Deep Cycle) applications that involve extremely deep charging depths. .

  In relation to the extension of the battery performance, a 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. If this state continues, the reaction on the electrode surface is biased during charge / discharge behavior, and lead sulfate Dense crystals can be formed. This increases the surface resistance, hinders the electrode reaction itself, and leads to deterioration of battery performance. Usually, high-concentration sulfate ions with large specific gravity generated by electrode reaction are discharged from the electrode surface and then settled, resulting in stratification. However, in conventional lead-acid batteries used for starting automobile engines, etc. Gas was generated from the electrode surface due to the electrode reaction at, so that the electrolytic solution was diffused by the bubbling effect, and the stratification phenomenon was eliminated, which was not an important problem. On the other hand, in an idling stop application or a DC application that requires use in a partially charged state, a reaction in an overcharged state is not involved, so that the electrolyte solution due to gas is not diffused, 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.

  Various separators have been devised as means for eliminating stratification.

  In Patent Document 1, a non-woven fabric composed of fibers of at least one material selected from a material group consisting of glass, pulp and polyolefin, preferably a mixed non-woven fabric mainly composed of glass fibers, pulp and inorganic oxide powder is used as a separator. By using as a liquid lead-acid battery in which discharge to a load is performed in a partially charged state, the battery is not fully charged under PSOC, so it is difficult to stir the electrolyte due to gas generation Even in this case, it has been reported that the stratification of the electrolyte is suppressed and the life performance is improved. However, since glass fibers are used, blade wear is severe in the slitting process due to the difference in material hardness compared to conventionally used polyolefins, and stable production cannot be achieved. In addition, in mixed nonwoven fabrics mainly composed of glass fiber, pulp and inorganic oxide powder, each material that floats uniformly on the dispersion liquid forms a web at once, so that it is like a continuous organic fiber layer and inorganic particle layer. A highly advanced layer structure cannot be obtained. Further, since the voids in the separator are all filled with silica, which is an inorganic particle, ion permeability is hindered, the electrical resistance between the separators is increased, and a high output battery design cannot be performed.

  In patent document 2, it produces at the time of charge of a lead storage battery by using the separator comprised by the hydrophobic resin which is a base material, and the porous hydrophilic coating layer provided in the surface of the said hydrophobic resin. It has been reported that stratification is suppressed, battery performance is maintained, and lead-acid battery manufacturing is facilitated. However, a woven fabric or a polyolefin substrate having a fiber diameter of 10 to 20 μm is used, and the nonwoven fabric structure having the same fiber diameter is several tens of nanometers even if the hydrophilic coating layer is applied in a fibrous form. Therefore, the most important short circuit as a separator occurs, and the original performance of the battery cannot be satisfied. Moreover, the porosity is also set to 90 to 98%, and when the coating agent is applied on the nonwoven fabric base material, the agent is broken through and stable production cannot be performed.

  In Patent Document 3, short-circuit suppression is achieved while maintaining discharge capacity at a high rate by using a non-woven fabric base material with a specified porosity and average flow pore size and a separator containing inorganic particles whose particle size is highly controlled. It is reported that a lithium ion secondary battery that is possible and exhibits stable charge / discharge behavior is obtained. However, the role of the inorganic particles is to suppress short-circuiting, and there is no description of the effect of diffusion / retention of sulfate ions that is effective for suppressing stratification of lead-acid batteries, which is required for this separator.

International Publication No. 2012/157311 JP 2014-194911 A International Publication No. 2014/046094

  In view of the above-described problems, the problem to be solved by the present invention is to suppress the stratification of the battery, to have a high output, a high durability, a low resistance, and a long cycle life. It is to provide a storage battery.

As a result of intensive studies and experiments, the present inventors have unexpectedly found that the above problem can be solved by the following configuration, and have completed the present invention. That is, the present invention is as follows.
[1] A separator comprising a nonwoven fabric base material having a void structure and inorganic particles present on the surface portion of the base material or on the fiber surface inside the base material, wherein the base material is composed of organic fibers. Separator.
[2] The separator according to [1], wherein the separator has an air permeability of 0.01 to 20 seconds.
[3] The separator according to [1] or [2], wherein the separator has an average pore diameter of 0.1 to 100 μm.
[4] The separator according to any one of [1] to [3], wherein a contact angle of the separator is 0 to 100 degrees.
[5] The separator according to any one of [1] to [4], wherein the separator has a thickness of 10 to 5000 μm.
[6] The separator according to any one of [1] to [5], wherein the separator has a tensile strength of 5 to 300 N / 15 mm.
[7] The separator according to any one of [1] to [6], wherein the inorganic particles contained in the separator include a silicon component.
[8] The separator according to any one of [1] to [7], wherein an average particle size of the inorganic particles contained in the separator is 1 nm to 5000 nm.
[9] The separator according to any one of [1] to [8], wherein the specific surface area of the inorganic particles contained in the separator is 0.1 to 1000 m ² / g.
[10] The separator according to any one of [1] to [9], wherein the separator includes 1 to 500 parts by mass of a binder present inside the nonwoven fabric substrate with respect to 100 parts by mass of the inorganic particles. Separator.
[11] The separator according to any one of [1] to [10], wherein the nonwoven fabric substrate of the separator is composed of continuous long fibers.
[12] The separator according to any one of [1] to [11], wherein the nonwoven fabric base material of the separator is composed of polyester fibers.
[13] The separator according to any one of [1] to [11], wherein the nonwoven fabric substrate of the separator is composed of polyolefin fibers.
[14] The separator according to any one of [1] to [13], wherein the nonwoven fabric substrate has a porosity of 35 to 95%.
[15] The separator according to any one of [1] to [14], wherein the nonwoven fabric base material of the separator has an average pore diameter of 0.1 to 200 μm.
[16] The separator according to [1] to [15], wherein the nonwoven fabric base material of the separator includes ultrafine fibers having a fiber diameter of 0.1 to 5 μm.
[17] The nonwoven fabric substrate of the separator includes at least 2 nonwoven fabric layers (I layer) composed of the ultrafine fibers and nonwoven fabric layers (II layer) composed of fibers having a fiber diameter of 5 μm to 30 μm. The separator according to any one of [1] to [16], comprising a layer.
[18] The separator according to [1] to [17], wherein the nonwoven fabric base material of the 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.
[19] The separator according to any one of [1] to [18], wherein the nonwoven fabric substrate of the separator is a nonwoven fabric integrated by thermal bonding.
[20] The separator according to any one of [1] to [19], wherein the separator can be heat-sealed.
[21] A method for producing a separator according to any one of [1] to [20], wherein a step of preparing a slurry by dispersing inorganic particles in a dispersion medium, and applying the slurry to a substrate The method comprising: a step of impregnating to produce a slurry-containing substrate; and a step of drying the slurry-containing substrate.
[22] The method for producing a separator according to [16], including a step of forming the I layer by a melt blown method using the ultrafine fibers.
[23] The separator obtained by laminating the separator according to any one of [1] to [20] and a microporous film.
[24] The separator, wherein the separator according to any one of [1] to [20] and a nonwoven fabric made of glass fiber are laminated.
[25] A positive electrode and a negative electrode, and an electrode plate group including the separator according to any one of [1] to [20], [23] and [24] disposed therebetween, an electrolyte solution, Liquid lead-acid battery containing
[26] A positive electrode and a negative electrode, and an electrode plate group including the separator according to any one of [1] to [20], [23], and [24], and an electrolyte And a control valve type lead acid battery.

  Since the 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. In addition, 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. Furthermore, the lead acid battery of the present invention has high output, high durability, and low resistance, and further extends the cycle life. The above description does not disclose all embodiments of the present invention and all advantages related to the present invention.

Hereinafter, the present invention will be described in more detail for the purpose of illustrating representative embodiments of the present invention, but the present invention is not limited to these embodiments.
(Separator)

  The 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 may be 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 even if a non-continuous bulk is formed. Good.

  The air permeability of the separator of the present embodiment is preferably 0.01 to 20 sec / 100 cc. When the air permeability is 20 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, a fatal short circuit as a separator can be suppressed. In that sense, the air permeability of the separator is more preferably in the range of 0.05 to 18 sec / 100 cc, and still more preferably in the range of 0.1 to 15 sec / 100 cc.

  The average pore diameter of the separator of this embodiment is preferably 0.1 to 100 μm. If the average pore diameter is larger than 0.1 μm, the electrodes can be isolated without hindering ionic conductivity between the electrodes. On the other hand, if the average pore diameter is smaller than 100 μm, an internal short circuit occurs and the characteristics as a battery are lost. In that sense, the average pore diameter of the separator is more preferably 0.3 to 90 μm, and further preferably 0.5 μm to 80 μm.

  The separator contact angle of this embodiment is preferably 0 to 100 degrees. When the contact angle is 0 to 100 degrees, the ion permeability between the electrodes is not hindered and the internal resistance can be maintained low. In addition, the sulfate ions in the separator are easily diffused, and the sulfuric acid concentration that is the electrolytic solution can be made uniform.

  It is preferable that the thickness of the separator of this embodiment is 10-5000 micrometers. When thickness exceeds 5000 micrometers, the distance between electrodes will become large and the internal resistance of a battery will become high. Further, when the thickness exceeds 5000 μm, the thickness per cell increases, and as a result, the number of cells that can be mounted on the entire battery decreases, and the battery capacity decreases. If the thickness is less than 10 μm, the active material movement during the electrode reaction cannot be endured, and a short circuit occurs. In that sense, the thickness of the separator is more preferably 15 to 4500 μm, and further preferably 20 to 4000 μm.

The tensile strength of the separator according to the present embodiment is preferably 5 to 300 N / 15 mm from the viewpoints 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 5N or more, even if an electrode is inserted, it can be held as a bag without breaking.
(Inorganic particles)

  The 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 contains 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 preferably chemically and electrochemically stable with respect to the material constituting the electrochemical element.

  As such inorganic particles, any of synthetic products and natural products can be used without particular limitation. As 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 卜, Saponite, Hectorite, Fluorine hectorite, Sauconite, Swin Rudai, Vermiculite, Fluorine Vermiculite, Burcherin, Sericite, Amesite, Kelly Eye, Freponite, Prindri Eye, Ben Agate Night, Zeolite, Biotite, Phlogopite, Fluorophlogopite, Iron Mica, Ysmite Night, Teniolite, side phyllite tetraferri iron mica, scale mica, fluorotetrasilicon mica, polyriccionite, muscovite, celadon stone, iron ceradon stone, iron alumino ceradon stone, alumino ceradon stone, tobe mica, soda mica, clinnite , Kinoshita, bite mica, ananda stone, pearl mica, klinok mouth a, chamosite, pennite, nimite, bailik mouth a, dombasite, kukke sight, sudoh eyelid, hydrotalcite, calcium silicate, magnesium silicate, silica Aluminum oxide, diatomaceous earth and ke Such as sand, and ceramics. These inorganic particles are used alone or in combination of two or more. In order to suppress the stratification of the battery, it is necessary to make the sulfate ions in the electrolyte uniform. In order to make the sulfate ions uniform, it is necessary to act to suppress the precipitation of sulfate ions discharged on the electrode surface by the battery reaction by the separator in contact with the electrode surface, or to diffuse through the separator. In order to make it so, it is preferable to use inorganic oxides, such as an alumina and a silica, in order to adsorb | suck and hold | maintain a sulfate ion in the interface of the inorganic particle which exists on a nonwoven fabric base material. Moreover, since the non-woven fabric substrate is hydrophilized with the same inorganic particles, a diffusion action of sulfate ions can be expected. Furthermore, silica is preferable for the purpose of being able to subdivide the particle size and expecting a more excellent sedimentation-inhibiting action and diffusing action using a myriad of interfaces.

  The average particle size of the inorganic particles is preferably 1 to 5000 nm. By setting the particle size of the inorganic particles in the slurry to 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. In particular, it effectively acts to adsorb or diffuse sulfate ions. Further, when the particle size is 5000 nm or less, the number and area of the interfaces where silica is exposed on the fiber surface are maintained at a certain level or more, and an effect of homogenizing sulfuric acid can be expected. In that sense, 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 the viscosity of the slurry, coating properties, and shortening of the drying step of the slurry. .

The specific surface area of the inorganic particles is preferably 0.1 to 1000 m ² / g. By making the specific surface area of the inorganic particles 0.1 m ² / g, it becomes possible to effectively utilize the particle interface protruding from the surface of the nonwoven fabric substrate, and to effectively adsorb or diffuse sulfate ions. it can. In addition, by setting the specific surface area to 1000 m ² / g, it is possible to balance the adsorption and desorption of sulfate ions, and it is possible to both suppress sedimentation and supply to the electrode surface.

  As the dispersion medium of the inorganic particles, those capable of dispersing the inorganic particles more uniformly and stably are preferable. For example, N-methylpiridone, N, N-dimethylformamide, N, N-dimethylacetamide, water, ethanol, toluene , Hot xylene, methylene chloride and hexane. Among these, water is preferable from the viewpoint of environmental protection.

  Moreover, the inorganic particle-dispersed slurry of the present embodiment can contain a binder for the purpose of binding inorganic particles to each other or fixing the inorganic particles to a nonwoven fabric substrate. There is no particular limitation on the type of the binder, but it is preferable to use a material that is stable with respect to sulfuric acid as an electrolytic solution and electrochemically stable. For example, 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: Fluorine-containing rubbers such as vinylidene fluoride-hexafluorine-mouth-pyrene-tetrafluorine-mouthed ethylene copolymer and ethylene-tetrafluorine-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, acrylic mouth 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 ether, polysulfone, Examples thereof include resins having a melting point and / or glass transition temperature of 18 ° C. or higher, such as polyethersulfone, polyphenylene sulfide, polyetherimide, polyamideimide, polyamide and polyester. These resin binders are used singly or in combination of two or more. Among these, 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 content ratio of the binder in the inorganic particle-dispersed slurry is preferably 1 part 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. More preferably, it is more preferably 6 parts by mass or more. In addition, the content ratio of the binder from the viewpoint of surfaceizing the minute interface of the inorganic particles, effective adsorption and diffusion of sulfate ions, and maintaining the ion permeability by utilizing the voids unique to the nonwoven fabric substrate 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. 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.

  Examples of the dispersant such as a surfactant include anionic surfactants such as sulfate ester type, phosphate ester type, strong rubonic acid type, and sulfonic acid type, and quaternary ammonium salt types and force thiones such as amidoamine type. Surfactants, 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.

  Furthermore, for the purpose of controlling the interfacial tension, 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.

  Examples of the thickener 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, diane tan gum, welan gum, gellan gum, guar gum, and power raginan gum, and starches such as dexamerine and alpha-unified 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, even if two or more sentences are combined. The thickener is not limited to those as long as the same effects as those described above can be obtained.

  When the substrate is a non-woven fabric, a wetting agent can be added to the slurry for the purpose of improving the wettability of the non-woven fabric with fibers (for example, synthetic fibers) and suppressing pinholes. Examples of 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.

  As the antifoaming agent, for example, various types of 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.

In this embodiment, a slurry can be prepared by dispersing inorganic particles in a solvent that 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, a disperser, a homogenizer, an ultrasonic homogenizer, and a pressure homogenizer. And high-speed homogenizer, high-speed homogenizer high-speed impact mill, thin-film swirl-type high-speed mixer, ultrasonic dispersion and mechanical stirring by stirring blades.
(Nonwoven fabric substrate)

  The 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 base material of this embodiment is comprised with the organic fiber. Examples of 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.

  Although it does not specifically limit as natural fiber, Plant fiber; Cotton, hemp, Manila Asa, palm, rush, animal fiber; Wool, wool, silk, etc. are mentioned.

  The regenerated fiber is not particularly limited, and examples include rayon, cupra, polynosic, cellulose nanofiber, cellulose-based acetate, and protein-based promix.

  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. Examples of the polyester-based resin include polyethylene terephthalate (PET), polybutylene terephthalate, and polyethylene naphthalate. Examples of polyolefin resins include homopolymers or copolymers of α-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. Examples of the polyamide-based resin 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.

  Generally, the nonwoven fabric comprised with glass fiber is used as a 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 piercing strength), causes a short circuit, increases process defects, and lowers cycle characteristics. On the other hand, 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. In particular, from the viewpoint of electrolytic solution stability, 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.

  It is preferable that the nonwoven fabric base material of this embodiment is comprised from the polyester fiber. 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. Moreover, 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. Moreover, 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. In that sense, the polyester fiber is more preferably a fiber formed of polyethylene terephthalate.

  It is also preferable that the nonwoven fabric base material of this embodiment is comprised from polyolefin fiber. 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.

  It is also preferable that the nonwoven fabric base material of this embodiment is comprised from a cellulose fiber. 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. Moreover, the separator comprised from the cellulose fiber is excellent also in ion permeability, and can find a high capacity | capacitance battery performance. In that sense, as the cellulose fiber, cupra, rayon, acetate, and cellulose nanofiber are more preferable.

  It is preferable that the nonwoven fabric base material of this embodiment is comprised from the continuous long fiber. In the present specification, 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.

  It is preferable that the porosity of the nonwoven fabric base material of this embodiment is 35 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. When inorganic particles are applied, the particles can be sufficiently filled in the voids. A more preferable range of the porosity of the nonwoven fabric is 40 to 90%, more preferably 45 to 85%.

  It is preferable that the average pore diameter of the nonwoven fabric base material of this embodiment is 0.1-200 micrometers. If the average pore diameter is larger than 200 μm, 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 μm, 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 μm, and further preferably 0.5 μm to 100 μm.

It is preferable that the nonwoven fabric base material of this embodiment has a thickness of 10 to 5000 μm and a basis weight of 5 to 500 g / m ² . When thickness exceeds 5000 micrometers, the distance between electrodes will become large and resistance will become high. In addition, since 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 μm, the active material movement during the electrode reaction cannot be endured, and a short circuit occurs. Moreover, if 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. 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 this sense, the basis weight is more preferably 7~480g / ^{m 2,} further preferably 10~450g / ^{m 2.}

  It is preferable that the nonwoven fabric base material of this embodiment is comprised with the nonwoven fabric containing the ultrafine fiber which has a fiber diameter of 0.1-5 micrometers. If the fiber diameter is 5 μm or less, the fiber gap does not become too large, and 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. Furthermore, it is possible to increase the number of interfaces without filling the voids in the nonwoven fabric substrate with a small amount of inorganic particles applied, and the electrical resistance as a separator is greatly reduced, resulting in overall separator manufacturing costs. Can also be suppressed. If the fiber diameter is 0.1 μm or more, the fiber gap does not become too small, and it is possible to suppress an increase in the electrical resistance of the separator. In that sense, the fiber diameter of the ultrafine fiber is more preferably 0.15 μm to 4.0 μm, and still more preferably 0.2 μm to 3.0 μm.

  The nonwoven fabric base material of this embodiment includes a nonwoven fabric layer (I layer) composed of ultrafine fibers having a fiber diameter of 0.1 to 5 μm, and a nonwoven fabric layer (II layer) composed of fibers having a fiber diameter of 5 to 30 μm. And at least two layers. In this case, the nonwoven fabric layer (I layer) composed of ultrafine fibers having a fiber diameter of 0.1 to 5 μm is a functional layer, and the nonwoven fabric layer (II layer) composed of fibers having a fiber diameter of 5 to 30 μm is a strength layer. As a role. Compared with the case where each layer is used alone as a separator, 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, In the separator coated with particles, 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. In addition, since 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. Furthermore, since 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. In that sense, 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 the I layer is disposed) and a four-layer structure of I layer-II layer-II layer-I layer are preferable.

  The manufacturing method of each nonwoven fabric layer used in this invention form is not limited. However, 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. Moreover, the manufacturing method of the nonwoven fabric layer (I layer) comprised by the ultrafine fiber, Preferably the manufacturing method, such as the dry method and wet method using an ultrafine fiber, or the electrospinning method, the melt-blown (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.

  As a method for forming a laminated nonwoven fabric by laminating a plurality of layers having a nonwoven fabric layer (I layer) composed of ultrafine fibers and a nonwoven fabric layer (II layer) composed of thermoplastic resin fibers, for example, 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. Especially, it is preferable to form a laminated nonwoven fabric by integration by thermal bonding. Examples of the integration method by thermal bonding 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. Moreover, if the pore structure peculiar to the nonwoven fabric of the binder is blocked, the reduction of the surface area where the inorganic particles are arranged becomes remarkable, and the ideal effect of adsorption and diffusion of sulfate ions cannot be obtained, and stratification proceeds. Therefore, it is not preferable. For the above reasons, 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.

  Integration by 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 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 an ultrafine fiber having a fiber diameter of 0.1 to 5 μm is melt blown using a thermoplastic resin thereon. 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.

  When the above manufacturing method is used, 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. Thus, not only the strength of the laminated nonwoven fabric structure itself is improved by intruding and fixing the ultrafine fibers by the melt-blown method into the nonwoven fabric layer (II layer) composed of thermoplastic resin fibers. Since movement due to external force of the ultrafine fiber nonwoven fabric layer (I layer) is less likely to occur, 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 the fiber formed by the meltblown method (that is, meltblown fiber) can be adjusted to a range of 5 to 40% under general meltblown spinning conditions. Note that 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. The crystallinity can be achieved by using a resin having a solution viscosity (ηsp / c) of preferably 0.2 to 0.8, more preferably 0.2 to 0.6. In the nonwoven fabric used in the present embodiment, from the viewpoint of preferably high dimensional stability when wet, the melt-blown fiber is constituted using a resin selected from PET resin and polyphenylene sulfide (PPS) resin, The solution viscosity (ηsp / c) of these resins is preferably 0.2 to 0.8. The crystallinity of the meltblown fiber is more preferably 10 to 40%.

  In the present embodiment, the laminated nonwoven fabric is preferably calendered. In this case, a more uniform structure can be given to the laminated nonwoven fabric. Specifically, after joining the fibers using the above-described thermal bonding step, as a calendering treatment, 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 fiber. And calendering at a linear pressure of 100 to 1000 N / cm. By the calendering as described above, the laminated nonwoven fabric has good strength, and the apparent density can be in a particularly preferable range (for example, within the range described in the examples of the present specification).

  When 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. When 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.

  When the linear pressure in the calendar processing is less than 100 N / cm, it is difficult to obtain sufficient adhesion, and sufficient strength tends not to be exhibited. On the other hand, if it exceeds 1000 N / cm, the deformation of the fiber becomes large, the apparent density becomes high, and it may be difficult to obtain the effect of the present invention.

  The nonwoven fabric separator of the present embodiment is preferably a hydrophilic processed nonwoven fabric. When the nonwoven fabric is subjected to 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. A person skilled in the art can select an appropriate hydrophilization processing method and conditions, for example, the amount of treatment agent used, the amount of functional groups introduced, and the like in consideration of the affinity with the electrolytic solution.

It is preferable that 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. Examples of 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. and a linear pressure of 100 to 1000 N / cm based on the melting point of the thermoplastic resin. When the linear pressure in the calendering is within the above range, it is preferable from the viewpoint of the strength of the nonwoven fabric, the reduction of fiber deformation, the reduction of the apparent density, etc., and the highly controlled pore distribution in the nonwoven fabric mat for lead storage battery of the present embodiment Is easier to achieve. 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.
(Other)

  It is preferable that the 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.

  It does not specifically limit as a manufacturing method of the separator of this embodiment. Specific examples include a dip method, a gravure method, a kiss method, a comma method, a die method, and a knife method. Specifically, after the separator or the nonwoven fabric substrate is immersed in the dispersion and pulled up, the excess dispersion is pressurized and removed with a roller or the like, and then thermally cured. Alternatively, there is a method of absorbing excess dispersion liquid on thick paper or the like. However, in consideration of mass production, a roller method capable of immediately removing excess dispersion is suitable.

  The separator of the present embodiment may be used alone as a separator, or may be used in combination with another nonwoven fabric or a microporous membrane. The lamination method is not particularly limited. In particular, when used in a superposed manner, the separator and the microporous membrane, or the separator and a glass fiber nonwoven fabric are preferably laminated and used.

  When the separator and the microporous membrane of this embodiment are laminated, the microporous membrane having a very high density and uniform pore size is arranged between the electrodes compared to a single nonwoven fabric, and a short circuit occurs. Not likely to occur. In addition, since the nonwoven fabric separator and the microporous membrane are laminated, the interface of the countless inorganic particles applied to the nonwoven fabric substrate is arranged at the electrode interface. As a result, the concentration is made uniform, the stratification phenomenon is suppressed, and the life can be extended.

  In addition, when the separator of this embodiment and the glass fiber nonwoven fabric are laminated, the glass fiber nonwoven fabric is rich in compression elasticity, so that it is possible to follow the electrode foil that repeatedly swells and shrinks. A sulfuric acid concentration homogenizing effect is obtained.

  The lead storage battery of this embodiment is comprised by the lead electrode-separator-lead electrode, and uses a sulfuric acid as electrolyte solution. A particularly preferable battery type is a liquid type or a control valve type. Specifically, the lead acid battery includes a positive electrode and a negative electrode, an electrode plate group including the separator of the present embodiment disposed between them, and sulfuric acid as an electrolytic solution.

  EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated further more concretely, this invention is not limited to these Examples at all. Hereinafter, unless otherwise specified, 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.

(1) Weight per unit area (g / m ² )
In accordance with the method specified in JIS L-1906, 9 test pieces of 20cm in length x 25cm in width were sampled at 3 places per 1m in the width direction of the sample and 3 places per 1m in the length direction. The basis weight was determined by converting the average value into mass per unit area.

(2) Thickness (mm)
According to the method prescribed 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.

(3) Apparent density (g / cm ³ )
Using the basis weight (g / m ² ) measured in (1) above and the thickness (mm) measured in (2) above, the unit is adjusted and the following formula:
Apparent density = (weight per unit area) / (thickness)
Was used to calculate the apparent density.

(4) Porosity (%)
Using the apparent density (g / cm ³ ) calculated in (3) above, the following formula:
Porosity = {1- (apparent density) / (resin density)} / 100
From this, the porosity was calculated.

(5) Fiber diameter (μm)
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 device (JSM-6510, manufactured by JEOL Ltd.), the deposited nonwoven fabric was photographed under the 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 μm, 6000 times for yarns having an average fiber diameter of 0.5 μm or more and less than 1.5 μm, and 4000 times for yarns having an average fiber diameter of 1.5 μm or more. The field of view at each magnification was 12.7 μm × 9.3 μm at 10,000 ×, 21.1 μm × 15.9 μm at 6000 ×, and 31.7 μm × 23.9 μm 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 following formula:
Dw = ΣWi · Di = Σ (Ni · Di ² ) / (Ni · Di)
{In the formula, Wi = weight fraction of fiber diameter Di = Ni · Di / ΣNi · Di. }
The weight average fiber diameter (Dw) obtained by the above was defined as the average fiber diameter (μm).

(6) Hole diameter distribution (average flow hole diameter and maximum hole diameter)
PMI palm porometer (model: CFP-1200AEX) was used. For the measurement, a PMI Sylwick was used as the immersion liquid, and the sample was immersed in the immersion liquid and sufficiently deaerated before measurement.
This measurement device uses a filter as a sample, immerses the filter in a liquid with a known surface tension in advance, applies pressure to the filter from a state in which all pores of the filter are covered with a liquid film, and the pressure at which the liquid film is destroyed And the pore diameter calculated from the surface tension of the liquid. The following formula is used for the calculation.
d = C · r / P
(Where d (unit: μm) 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).
In the measurement method using this measuring apparatus, 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 taken as the average pore size of the laminated nonwoven fabric of the present invention.
The maximum pore size of the laminated nonwoven fabric of the present invention is measured by using the nonwoven fabric as the above filter sample, and the liquid film is destroyed at a pressure where the cumulative filter flow rate is −2σ, ie, the cumulative filter flow rate is 2.3%. Of the pore diameter. 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.

(7) Air permeability (sec / 100cc)
The air permeability was measured based on JIS-P8117 (Gurley tester method).

(8) Tensile strength (N / 15mm)
Except for 10 cm of each end portion of the sample (nonwoven fabric), 5 test pieces each having a width of 3 cm and a length of 20 cm were cut out per 1 m width. A load was applied until the test piece broke, and an average value of the strength at the maximum load of the test piece in the MD direction was determined.

(9) Average particle diameter of inorganic particles The average particle diameter of inorganic particles in the slurry is determined as follows. That is, after adding distilled water to the prepared slurry and squeezing to adjust the concentration of inorganic particles to 0.01% by mass, using a laser set particle size distribution measuring device (SALD-2100 manufactured by Shimadzu Corporation). The particle size distribution based on the measured volume was obtained, and the average particle size was obtained from the cumulative frequency.
(10) Specific surface area of inorganic particles Device type: Gemini 2360 Shimadzu Corporation was used. The inorganic particles were dried at 60 ° C. for 30 minutes and then cooled for 10 minutes. Thereafter, a cell is set in the above specific surface area measuring apparatus, and nitrogen gas adsorption on the sample surface results in the following formula of the following BET:
P / (V (P0−P)) = 1 / (Vm × C) + ((C−1) / (Vm × C)) (P / P0)
{In the formula, P0: saturated water vapor pressure (Pa), Vm: adsorption amount of monomolecular layer (mg / g), C: parameter (−) <0 related to heat of adsorption, etc., and this relational expression is particularly P / P0 = It is well established in the range of 0.05 to 0.35. } Was applied to determine the specific surface area value. The BET formula is a formula that represents the relationship between the adsorption equilibrium pressure P and the adsorption amount V at that pressure when the adsorption equilibrium state is maintained at a constant temperature.
(11) Puncture strength (N)
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.

(12) Measurement of Volume Resistance (Ω / □) As a measuring device, HIOKI Digital Super Megameter and HIOKI flat plate sample electrode SME-8311 were used. A 100 mm × 100 mm test piece (nonwoven fabric) was prepared, and the volume resistance value (Ω / □) was measured under measurement conditions of a voltage of 10 V and a measurement time of 60 seconds.

(13) Impedance measurement A non-woven fabric sampled to a diameter of 40 mm is immersed in a 40% sulfuric acid aqueous solution as an electrolytic solution, and then deaerated under reduced pressure for 1 hour. The sample after deaeration was inserted between lead electrodes (lead and lead oxide pasted into a 20 mm-diameter disk-shaped lead), and a load of 12 cN was applied between the electrodes to fix the electrodes and the nonwoven fabric. Next, the increased electrical resistance between the electrodes due to this insertion was taken as the electrical resistance of the nonwoven fabric, and was measured using an LCR meter at a frequency of 20 ° C. and 100 kHz (unit: Ω).

<Measurement method of battery performance>
(14) Processing suitability When the positive electrode plate was encapsulated in the separator, 1000 sheets were processed as defective products that were distorted and deformed into a state where the separator swelled to the extent that it could be visually confirmed, or the seal was not well formed. The defective product rate was measured, and A was less than 0.5%, B was less than 0.5 to 1%, C was 1% to 5%, and D was more than that.

(15) Initial characteristics and cycle characteristics After placing a negative electrode plate (lead) in a battery case via a separator on both sides of one positive electrode plate (lead oxide), pour an electrolyte (diluted sulfuric acid with a specific gravity of 1.28) Thus, a liquid lead-acid battery was produced. The produced lead storage battery was repeatedly charged and discharged under the following discharge conditions and charge conditions.
Discharge conditions: 10A (0.5CA), lower limit voltage 10.5V
Charging conditions (constant voltage method): maximum charging current 10A, maximum charging pressure 14.7V
Maximum charging time 12 hours Vibration was applied to the battery in an atmosphere of 25 ° C., and the cycle from discharging to charging was set to 1 cycle, and the electrode reaction was started. At that time, the initial capacity was measured to confirm the presence or absence of a short circuit. The cycle number when the initial capacity was less than 80% was defined as cycle characteristics.

(16) Difference in specific gravity of sulfuric acid 10 mL of the solution was collected from the upper and lower portions of the battery case, the specific gravity of these samples was measured, and the difference in specific gravity between the upper and lower portions was defined as the specific gravity difference.

[Examples 1-9, 11-16, 19-23]
A non-woven fabric layer (II layer) composed of thermoplastic resin fibers was formed. Specifically, a general-purpose PET (as a thermoplastic resin) solution (having solution viscosity: ηsp / c = 0.67 measured using o-chlorophenol (OCP) as a solvent at a temperature of 35 ° C.) ( The solution viscosity was measured with a viscosity tube in a constant temperature water bath at a temperature of 35 ° C. The same applies hereinafter.), And the filament group was extruded toward the moving collection net surface at a spinning temperature of 300 ° C. by the spunbond method. Spinning was performed at a spinning speed of 4500 m / min. Next, the filament group was sufficiently opened by charging about 3 μC / g by corona charging, and a thermoplastic resin long fiber web was formed on the collection net. An ultrafine fiber nonwoven fabric layer (I layer) was laminated on the collected web. Specifically, a solution of PET (having a viscosity of solution measured at a temperature of 35 ° C. using OCP as a solvent: ηsp / c = 0.50), a spinning temperature of 300 ° C., and heated air of 1000 Nm ³ / hr / Under the condition of m, spinning was performed by the melt blown method and sprayed onto the above-mentioned thermoplastic resin long fiber web. At this time, 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, and 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. On the nonwoven fabric layer (II layer), a nonwoven fabric having an SM structure composed of a nonwoven fabric layer (I layer) composed of ultrafine fibers is applied. Obtained. Thereafter, 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. 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.
The inorganic particle slurry was obtained by the following method. Colloidal silica (common name: silica / average particle size 12 nm) 10 parts by mass, strong rubymethylcellulose 1 part by mass, acrylic styrene binder (solids concentration 45%) 2.2 parts by mass, 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 binder, and has a rotational speed of 1500 rpm and dispersion treatment. Dispersion treatment was performed under conditions of 5 minutes to obtain a uniform slurry.
And the slurry was apply | coated on the obtained nonwoven fabric base material by the comma coating system (line speed: 10 m / min, gap 10 micrometers). Furthermore, it dried in 80 degreeC oven and the solvent was removed, and the separator was obtained. The coating amount was appropriately adjusted with the silica content.

[Example 10]
Aluminum hydroxide (common name: alumina) was used for the inorganic particles in the applied slurry.

[Example 17]
As the nonwoven fabric substrate, a pulp-based short fiber nonwoven fabric obtained by a papermaking method was used.

[Example 18]
A nonwoven fabric separator was obtained in the same manner as in [Example 1] using polypropylene (PP) resin.

[Example 24]
A non-woven fabric layer (II layer) composed of thermoplastic resin fibers was formed. Specifically, a general-purpose PET (as a thermoplastic resin) solution (having solution viscosity: ηsp / c = 0.67 measured using o-chlorophenol (OCP) as a solvent at a temperature of 35 ° C.) ( The solution viscosity was measured with a viscosity tube in a constant temperature water bath at a temperature of 35 ° C. The same applies hereinafter.), And the filament group was extruded toward the moving collection net surface at a spinning temperature of 300 ° C. by the spunbond method. Spinning was performed at a spinning speed of 4500 m / min. Next, the filament group was sufficiently opened by charging about 3 μC / g by corona charging, and a thermoplastic long fiber web was formed on the collection net to obtain a nonwoven fabric substrate.

[Example 25]
As the ultrafine fiber nonwoven fabric layer (I layer), a PET solution (solution viscosity measured at a temperature of 35 ° C. using OCP as a solvent: ηsp / c = 0.50), spinning temperature of 300 ° C., heated air Under the condition of 1000 Nm3 / hr / m, spinning was performed by the melt blown method and sprayed onto the above-mentioned thermoplastic resin long fiber web. At this time, 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, and the wind speed was set to 7 m / sec. The adjustment of the fiber diameter and the degree of crystallinity was performed by adjusting the amount of heated air to obtain a nonwoven fabric substrate composed of a nonwoven fabric layer (I layer) composed of ultrafine fibers.

[Example 26]
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 27]
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 28]
A co-PET / PET sheath core with a fiber diameter of 16 μm is collected on the net so as to be 20 g / m ² by the spunbond method, 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 nonwoven fabric substrate.

[Example 29]
A polyethylene microporous membrane separator was further disposed outside the separator obtained in [Example 1].

[Example 30]
A glass fiber nonwoven fabric was further arranged outside the separator obtained in [Example 1].

[Example 31]
The separator obtained in [Example 1] was mounted on a control valve type lead-acid battery.

[Comparative Example 1]
The nonwoven fabric substrate obtained in [Example 1] was used as a separator as it was.

[Comparative Example 2]
As the separator, a polyethylene microporous film commercially available for lead-acid batteries was used.

[Comparative Example 3]
As a separator, a glass mat (GM) was bonded to a polyethylene microporous film commercially available for lead storage batteries.

[Comparative Example 4]
As the separator, an AGM (Absorbed Glass Mat) separator, which is commercially available for lead-acid batteries, was mounted on a control-type lead-acid battery.

[Comparative Example 5]
A commercially available polyester fabric was used as the separator.

  The properties and evaluation results of the separators of Examples 1 to 31 and Comparative Examples 1 to 5 are shown in Table 1 below.

  Since the 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. In addition, 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. Furthermore, the cycle life is very long with high output and low resistance. Therefore, the lead acid battery of this invention is utilized suitably.

Claims (26)

  A separator comprising a nonwoven fabric base material having a void structure and inorganic particles present on the surface portion of the base material or on the fiber surface inside the base material, wherein the base material is composed of organic fibers .   The separator according to claim 1 whose air permeability of said separator is 0.01-20 seconds.   The separator according to claim 1 or 2, wherein the separator has an average pore diameter of 0.1 to 100 µm.   The separator according to any one of claims 1 to 3, wherein a contact angle of the separator is 0 to 100 degrees.   The separator as described in any one of Claims 1-4 whose thickness of the said separator is 10-5000 micrometers.   The separator as described in any one of Claims 1-5 whose tensile strength of the said separator is 5-300 N / 15mm.   The separator as described in any one of Claims 1-6 in which the inorganic particle contained in the said separator contains a silicon component.   The separator as described in any one of Claims 1-7 whose average particle diameter of the inorganic particle contained in the said separator is 1 nm-5000 nm. The separator as described in any one of Claims 1-8 whose specific surface area of the inorganic particle contained in the said separator is 0.1-1000 m < ² > / g.   The separator as described in any one of Claims 1-9 in which the said separator contains 1-500 mass parts with respect to 100 mass parts of said inorganic particles of the binder which exists in the inside of the said nonwoven fabric base material.   The separator as described in any one of Claims 1-10 in which the nonwoven fabric base material of the said separator is comprised from the continuous long fiber.   The separator as described in any one of Claims 1-11 in which the nonwoven fabric base material of the said separator is comprised from the polyester fiber.   The separator as described in any one of Claims 1-11 in which the nonwoven fabric base material of the said separator is comprised from the polyolefin fiber.   The separator as described in any one of Claims 1-13 whose porosity of the nonwoven fabric base material of the said separator is 35-95%.   The separator as described in any one of Claims 1-14 whose average pore diameter of the nonwoven fabric base material of the said separator is 0.1-200 micrometers.   The separator as described in any one of Claims 1-15 in which the nonwoven fabric base material of the said separator contains the ultrafine fiber which has a fiber diameter of 0.1-5 micrometers.   The nonwoven fabric substrate of the 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 μm to 30 μm. The separator as described in any one of Claims 1-16 which is made.   The separator as described in any one of Claims 1-17 by which the nonwoven fabric base material of the said separator is comprised by 3 layers which have arrange | positioned the said I layer as an intermediate | middle layer of the said II layer and the said II layer.   The separator according to any one of claims 1 to 18, wherein the nonwoven fabric substrate of the separator is a nonwoven fabric integrated by thermal bonding.   The said separator formed by heat-sealing the separator as described in any one of Claims 1-19.   It is a manufacturing method of the separator as described in any one of Claims 1-20, Comprising: The process which prepares a slurry by disperse | distributing an inorganic particle to a dispersion medium, The coating sentence impregnates the said slurry to a base material. The said method including the process of producing a slurry containing base material, and the process of drying the said slurry containing base material.   The manufacturing method of the separator of Claim 16 including the process of forming the said I layer by the melt blown method using the said ultrafine fiber.   The said separator which laminated | stacked the separator and microporous film as described in any one of Claims 1-20.   The said separator which laminated | stacked the separator and the nonwoven fabric which consist of glass fibers as described in any one of Claims 1-20.   The liquid lead acid battery containing the positive electrode, the negative electrode, the electrode group containing the separator as described in any one of Claims 1-20, 23, and 24 arrange | positioned among them, and electrolyte solution.   A control valve-type lead-acid battery comprising a positive electrode and a negative electrode, and an electrode plate group including the separator according to any one of claims 1 to 20, 23, and 24, and an electrolyte.