WO2017170977A1 - Séparateur destiné à un accumulateur au plomb du type liquide - Google Patents

Séparateur destiné à un accumulateur au plomb du type liquide Download PDF

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Publication number
WO2017170977A1
WO2017170977A1 PCT/JP2017/013500 JP2017013500W WO2017170977A1 WO 2017170977 A1 WO2017170977 A1 WO 2017170977A1 JP 2017013500 W JP2017013500 W JP 2017013500W WO 2017170977 A1 WO2017170977 A1 WO 2017170977A1
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WIPO (PCT)
Prior art keywords
separator
microporous film
sheet
weight
lead
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Ceased
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PCT/JP2017/013500
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English (en)
Japanese (ja)
Inventor
蔀　貴史
和田　忠正
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Nippon Sheet Glass Co Ltd
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Nippon Sheet Glass Co Ltd
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Application filed by Nippon Sheet Glass Co Ltd filed Critical Nippon Sheet Glass Co Ltd
Priority to JP2018509493A priority Critical patent/JP7248425B2/ja
Priority to CN201780020347.4A priority patent/CN108886124B/zh
Publication of WO2017170977A1 publication Critical patent/WO2017170977A1/fr
Anticipated expiration legal-status Critical
Priority to JP2022072931A priority patent/JP7444920B2/ja
Ceased legal-status Critical Current

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Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/489—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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention is not a so-called sealed lead-acid battery (also referred to as a control valve-type lead-acid battery) in which the electrolyte is made non-fluidized to be maintenance-free, but is a so-called liquid having a fluid electrolyte that is a conventional method.
  • the present invention relates to a liquid lead-acid battery separator used for a type lead-acid battery (also called a vent-type lead-acid battery or an open-type lead-acid battery).
  • a separator for a liquid lead-acid battery called a polyethylene separator
  • a polyolefin resin having a weight average molecular weight of 500,000 or more (usually ultra-high molecular weight polyethylene) and a specific surface area of 50 m 2 / g or more.
  • inorganic powder usually silica fine powder
  • plasticizer usually mineral oil
  • surfactant solid content
  • separator made of a microporous film comprising 0 to 5% by weight of an agent (antioxidant, weathering agent, etc.).
  • the separator made of the microporous film is usually a raw material composition obtained by mixing the polyolefin resin, the inorganic powder, the plasticizer (mixed more than the separator composition), the surfactant, and the additive.
  • the base thickness is about 0.1 to 0.3 mm obtained by extruding into a sheet while heating and melting and kneading, roll rolling to a predetermined thickness, and extracting and removing all or part of the plasticizer.
  • the sheet has an average pore diameter (mercury intrusion method) of about 0.01 to 0.5 ⁇ m and a porosity (mercury intrusion method) of about 50 to 90% by volume.
  • the role of the inorganic powder is to adsorb and carry a plasticizer when the raw material composition is heated and melted and kneaded, and to create a microporous structure (dense and complex pore structure and high porosity) of the microporous film.
  • a plasticizer when the raw material composition is heated and melted and kneaded, and to create a microporous structure (dense and complex pore structure and high porosity) of the microporous film.
  • it can withstand sheet shrinkage that occurs when the plasticizer is removed during the manufacturing process of the microporous film to maintain dimensional stability, and the drying process (moisture removal process) that is performed before using the microporous film in a battery.
  • silica fine powder is usually used as the inorganic powder, and in particular, from the viewpoints of a large specific surface area, a large oil absorption, a large amount of hydrophilic groups (silanol groups), etc.
  • synthetic amorphous silica produced by a wet precipitation method is used.
  • the synthetic amorphous silica produced by the precipitation method is a method in which an amorphous silica is precipitated by reacting an aqueous solution of alkali silicate (sodium silicate) and mineral acid (sulfuric acid) under neutral or alkaline conditions.
  • alkali silicate sodium silicate
  • mineral acid sulfuric acid
  • the produced amorphous silica contains salts such as sodium sulfate as a by-product, and a process of removing salts by a filtration and washing process (a process of increasing purity) is performed in a subsequent process. It has been broken.
  • the produced amorphous silica usually contains a small amount of by-product sodium sulfate. Therefore, the microporous film manufactured using such silica fine powder also contains a small amount of sodium sulfate, and when used as a lead-acid battery separator, as the battery usage proceeds, the electrolyte solution If Na ions are eluted and the amount of elution is large, it may be a factor that hinders improvement in charge acceptability.
  • the water used for washing may contain Cl as a halogen.
  • tap water containing residual chlorine
  • groundwater containing salt sodium chloride
  • the present invention provides a separator for a liquid lead-acid battery comprising a microporous membrane manufactured using silica fine powder that is a synthetic amorphous silica manufactured by a precipitation method as a main raw material. Therefore, even when the battery is used with a battery using this, the amount of alkali metal ions and halogen ions eluted from the separator into the electrolyte can be reduced, and the improvement in charge acceptability can be hardly hindered.
  • An object of the present invention is to provide a separator that can hardly cause a decrease in battery life performance.
  • the separator for a liquid lead-acid battery according to the present invention comprises, as described in claim 1, reacting an alkali silicate aqueous solution with a mineral acid to synthesize amorphous silica by precipitation, followed by filtration and washing with water.
  • a separator for a liquid type lead-acid battery comprising a microporous membrane containing 40% by weight or more of silica fine powder, which is a synthetic amorphous silica produced by a precipitation method for adjusting the purity by the above-described microporous membrane (10 cm Concentration of alkali metals (Li, Na, K, Rb, Cs) when immersed in 126 g of sulfuric acid with a specific gravity of 1.26 at a temperature of 50 ° C.
  • ICP emission spectroscopic analysis Is not more than 5 mg / 100 cm 2 / sheet (however, the base thickness of the microporous membrane is converted to 0.2 mm) and the concentration of halogen (F, Cl, Br, I) (ICP emission spectroscopic analysis) is 0. 4mg / 100cm 2 / Sheet or less (however, the base thickness of the microporous membrane is converted to 0.2 mm).
  • the separator for liquid lead-acid batteries according to claim 2 is the separator for liquid lead-acid batteries according to claim 1, wherein the filtration / washing does not include ion-exchanged water or salt (sodium chloride). It is characterized by using groundwater.
  • the liquid lead-acid battery separator according to claim 3 is the liquid lead-acid battery separator according to claim 1 or 2, wherein the microporous film is mainly composed of the silica fine powder and a polyolefin resin. It is a microporous film.
  • the separator for a liquid lead-acid battery according to claim 4 is the separator for a liquid lead-acid battery according to claim 3, wherein the microporous film has a base thickness of 0.1 to 0.3 mm, an average It is a microporous film having a pore diameter (mercury intrusion method) of 0.01 to 0.5 ⁇ m and a porosity (mercury intrusion method) of 50 to 90% by volume.
  • a lead-acid battery separator comprising a microporous membrane manufactured using silica fine powder, which is a synthetic amorphous silica manufactured by a precipitation method, as a main raw material. Even when usage progresses, the amount of alkali metal ions and halogen ions eluted from the separator into the electrolyte can be reduced, and it is difficult to prevent improvement in charge acceptability, and it is difficult to cause deterioration in battery life performance.
  • a separator can be provided.
  • the separator for a liquid lead-acid battery according to the present invention reacts with an alkali silicate aqueous solution and a mineral acid, synthesizes amorphous silica by precipitation, and then adjusts the purity by filtration and washing with water (removing by-product salts and removing amorphous substances).
  • a microporous membrane containing 40% by weight or more of silica fine powder (hereinafter sometimes simply referred to as “silica fine powder”), which is a synthetic amorphous silica produced by a sedimentation method that increases the purity of porous silica)
  • silica fine powder which is a synthetic amorphous silica produced by a sedimentation method that increases the purity of porous silica
  • the alkali metal content (Li, Na, K, Rb, Cs) concentration (ICP emission spectroscopic analysis) is 5 mg / 100 cm 2 / sheet or less (however, the base thickness of the microporous film is 0.2 mm equivalent), and the halogen content (F, Cl, Br, I) Concentration (ICP emission spectroscopic analysis) is .4mg / 100cm 2 / sheet or less (based thickness 0.2mm converted value of the microporous membrane) with the proviso that a.
  • the alkali metal content (Li, Na, K, Rb, Cs) when the microporous membrane (10 cm ⁇ 10 cm ⁇ 2 sheets) was left immersed in 126 g of sulfuric acid having a specific gravity of 1.26 at a temperature of 50 ° C. for 24 hours.
  • the alkali eluted from the separator into the electrolyte by adjusting the concentration (ICP emission spectroscopic analysis) to 5 mg / 100 cm 2 / sheet or less. Since the amount of metal ions can be suppressed, it is difficult to hinder improvement in charge acceptance.
  • the concentration of alkali metal is 4 mg. / 100 cm 2 / sheet or less is more preferable.
  • ICP Concentration of halogen content (F, Cl, Br, I) when the microporous membrane (10 cm ⁇ 10 cm ⁇ 2 sheets) was immersed in 126 g of sulfuric acid having a specific gravity of 1.26 at a temperature of 50 ° C. for 24 hours.
  • the halogen ions eluted from the separator into the electrolyte solution by setting the emission spectroscopic analysis to 0.4 mg / 100 cm 2 / sheet or less. Since the amount can be suppressed, it is difficult to cause a decrease in battery life performance by accelerating corrosion of the electrode plate lattice and the pole column.
  • the concentration of halogen content is 0. 2 mg / 100 cm, more preferably 2 / sheet or less, 0.1 mg / 100 cm 2 / sheet or less is more preferable.
  • the microporous film is preferably a microporous film mainly composed of the silica fine powder and a polyolefin resin, and the microporous film has a base thickness of 0.1 to 0.3 mm and an average value.
  • a microporous film having a pore diameter (mercury intrusion method) of 0.01 to 0.5 ⁇ m and a porosity (mercury intrusion method) of 50 to 90% by volume is preferable.
  • the base thickness is, for example, a term used to distinguish the total thickness including rib-shaped protrusions when the microporous film has rib-shaped protrusions, and excludes the height of the rib-shaped protrusions (ribs This is the film thickness (when no projection is provided).
  • the silica fine powder has a plasticizer adsorbed and supported when the raw material composition is heated, melted and kneaded, and has a microporous structure (dense and complex pore structure and high porosity). That can withstand sheet shrinkage that occurs when the plasticizer is removed during the manufacturing process of microporous film, and that maintains dimensional stability.
  • salts such as sodium are contained and the salt is removed by filtration and washing in the subsequent process, the salt removal treatment is not complete, and tap water (residual chlorine And groundwater containing salt (sodium chloride) can be used, and therefore contains trace amounts of Na and Cl which can adversely affect battery performance.
  • the silica fine powder it is a synthetic amorphous silica produced by a wet precipitation method, and an alkali metal component (Li, Na, K, Rb, Cs) or a halogen component (F, Cl, The content of Br, I) is the alkali metal when the finally obtained microporous membrane (10 cm ⁇ 10 cm ⁇ 2) is immersed in 126 g of sulfuric acid having a specific gravity of 1.26 at a temperature of 50 ° C. for 24 hours.
  • an alkali metal component Li, Na, K, Rb, Cs
  • a halogen component F, Cl, The content of Br, I
  • the amorphous silica of the present invention is prepared using ion-exchanged water or groundwater not containing salt (sodium chloride). Is preferred.
  • the groundwater which does not contain salt (sodium chloride) refers to the groundwater whose salt (sodium chloride) density
  • concentration is 300 ppm or less.
  • the base thickness of the microporous film is preferably 0.1 to 0.3 mm. However, if it exceeds 0.3 mm, the electrical resistance deteriorates, and if it is less than 0.1 mm, good short-circuit resistance is achieved.
  • Short-circuit here refers to permeation short circuit called dendritic short, weak part of local substrate, high pressure from the convex part of the electrode plate, impact and piercing, oxidative wear due to oxidizing power from the electrode plate, etc. It is difficult to maintain a normal short circuit caused by a hole opening or cracking.
  • the porosity of the microporous film is preferably 50% by volume or more, but by being 50% by volume or more, the internal resistance (electrical resistance) as a liquid lead-acid battery separator is low. This contributes to higher performance of liquid lead-acid batteries. Therefore, the porosity of the microporous film (mercury intrusion method) is preferably 60 to 90% by volume, more preferably 70 to 90% by volume.
  • the method for obtaining the microporous film is preferably by melt-kneading a raw material composition mainly composed of a polyolefin resin, the silica fine powder, and a plasticizer to remove part or all of the plasticizer after film formation. .
  • a raw material composition mainly composed of a polyolefin resin, the silica fine powder, and a plasticizer to remove part or all of the plasticizer after film formation.
  • membrane is obtained.
  • An example of a specific manufacturing method is shown below. First, a raw material in which various additives (surfactant, antioxidant, weathering agent, etc.) are added to a predetermined amount of polyolefin-based resin, silica fine powder, and plasticizer as necessary is a Henschel mixer or a Ladige mixer.
  • the mixture is stirred and mixed to obtain a raw material mixture.
  • this mixture is put into a twin-screw extruder having a T-die attached to the tip, extruded into a sheet shape while being heated and melted and kneaded, and passed between a pair of forming rolls having a predetermined groove formed in one roll.
  • a film-like product is obtained in which a rib having a predetermined shape is integrally formed on one side of the flat sheet.
  • this film-like material is immersed in a suitable solvent (for example, n-hexane), and a predetermined amount of mineral oil is extracted and removed, followed by drying, and the desired microporous film is obtained.
  • a suitable solvent for example, n-hexane
  • the raw material composition refers to a composition composed of all raw materials brought into the melt-kneading step, and means “all raw materials (compositions)”, and specifically, a raw material mixture. It does not mean that it is a melt-kneaded product.
  • the total content of the polyolefin resin, the silica fine powder and the plasticizer is 90% by weight or more, the content of the polyolefin resin is 20 to 60% by weight, and the content of the silica fine powder is 40 to 80%.
  • the content of the plasticizer is 0 to 30% by weight, and the content of the surfactant is 0 to 8% by weight.
  • the content of the polyolefin resin exceeds 60% by weight or the content of the silica fine powder is less than 40% by weight, it is difficult to secure a large porosity and a fine and complicated pore structure of the microporous film. Therefore, the good electrical resistance characteristics of the microporous film separator cannot be maintained.
  • polystyrene resin homopolymers or copolymers such as polyethylene, polypropylene, polybutene, polymethylpentene, and mixtures thereof can be used.
  • polyethylene is the main component in terms of moldability and economy.
  • Polyethylene has a melt molding temperature lower than that of polypropylene, has good productivity, and can suppress production costs.
  • the polyolefin resin has a weight average molecular weight of 500,000 or more, the mechanical strength of the membrane can be ensured even in a microporous film containing a large amount of silica fine powder.
  • the polyolefin resin preferably has a weight average molecular weight of 1,000,000 or more, more preferably 1,500,000 or more.
  • Polyolefin-based resin has good mixability with silica fine powder, is in a microporous film, maintains strength while bonding the skeleton of silica fine powder as an adhesive functional material, and is chemically stable and highly safe .
  • silica fine powder those having a fine particle size and having a pore structure inside or on the surface can be used.
  • silica has a wide selection range of various powder properties such as particle diameter and specific surface area, is relatively inexpensive and easily available, and has few impurities.
  • the silica fine powder has a specific surface area of 100 m 2 / g or more, the pore structure of the microporous film is made finer (densified) and complicated to improve short-circuit resistance, and the microporous film has an electrolyte solution retained. It is preferable to enhance the hydrophilicity of the microporous film by increasing the force and providing a large number of hydrophilic groups (—OH) on the powder surface.
  • —OH hydrophilic groups
  • the specific surface area of the silica fine powder is 150 m 2 / g or more. Moreover, it is preferable that the specific surface area of the said silica fine powder is 400 m ⁇ 2 > / g or less. When the specific surface area of the silica fine powder exceeds 400 m 2 / g, the surface activity of the particles is high and the cohesive force becomes strong, so that the silica fine powder is not easily dispersed uniformly in the microporous film, which is not preferable.
  • the plasticizer it is preferable to select a material that can be a plasticizer of a polyolefin resin, and various organic liquids that are compatible with the polyolefin resin and can be easily extracted with various solvents can be used.
  • Can be used mineral oils such as industrial lubricating oils composed of saturated hydrocarbons (paraffins), higher alcohols such as stearyl alcohol, ester plasticizers such as dioctyl phthalate, and the like. Among these, mineral oil is preferable because it can be easily reused.
  • the plasticizer is preferably blended in an amount of 30 to 70% by weight in the raw material composition mainly composed of polyolefin resin, silica fine powder, and plasticizer.
  • the plasticizer is melted and kneaded with a raw material composition mainly composed of a polyolefin-based resin, silica fine powder, and a plasticizer to be formed into a film-like product having a predetermined shape, and then removed to make a porous material.
  • the content of the plasticizer in the microporous film separator may be zero.
  • an appropriate amount of a plasticizer such as mineral oil can be contained to contribute to an improvement in oxidation resistance.
  • the content of the plasticizer in the separator is preferably 5 to 30% by weight.
  • the content of the plasticizer is 20 More preferably, it is less than or equal to weight percent.
  • saturated hydrocarbon organic solvents such as hexane, heptane, octane, nonane and decane can be used.
  • a surfactant hydrophilizing agent
  • an antioxidant an antioxidant
  • an ultraviolet absorber e.g., sodium bicarbonate
  • a weathering agent e.g., sodium bicarbonate
  • a lubricant e.g., sodium bicarbonate
  • an antibacterial agent e.g., sodium bicarbonate
  • an antifungal agent e.g., sodium bicarbonate
  • a pigment e.g., sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate
  • the microporous film contains a large amount of the silica fine powder having a large specific surface area and high hydrophilicity, which alone has hydrophilicity, wettability with respect to sulfuric acid electrolyte of a liquid lead acid battery that is an aqueous solution, Sulfuric acid electrolyte has permeability (penetration), but when the sulfuric acid electrolyte is injected into the laminate in which the electrode plate and separator are closely integrated in the battery case, In order to quickly absorb the electrolyte and replace the voids of the separator with the electrolyte, the microporous film may contain 0.2 to 8% by weight of a surfactant (solid content). preferable.
  • a surfactant solid content
  • Examples of the method for adding the surfactant to the microporous film include a method in which the surfactant is added in a dispersed state in the raw material composition before film formation (internal addition method), Although there is a method (external addition method) for post-processing (attachment treatment) to the porous film, the manufacturing process can be simplified and the surfactant can hardly be oozed out of the microporous film of the present invention.
  • a method of adding in advance to the raw material composition is preferred.
  • the content (required amount) of the surfactant (solid content) is 0.2 to 8% by weight in the microporous film.
  • the content of the surfactant (solid content) is increased beyond this range, the effect of improving the hydrophilicity of the microporous film does not greatly increase, and conversely, the porosity of the microporous film is decreased.
  • the internal resistance electrical resistance
  • the content of the surfactant (solid content) is more preferably 0.2 to 5% by weight in the microporous film.
  • the surfactant may be any material that can improve the hydrophilicity of the microporous film, and any of a nonionic surfactant, a cationic surfactant, and an anionic surfactant can be used.
  • a nonionic surfactant polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyoxyethylene alkyl allyl ethers, fatty acid monoglycerides, sorbitan fatty acid esters and the like can be used.
  • As the cationic surfactant aliphatic amine salts, quaternary ammonium salts, polyoxyethylene alkylamines, alkylamine oxides and the like can be used.
  • alkyl sulfonate, alkyl benzene sulfonate, alkyl naphthalene sulfonate, alkyl sulfosuccinate, dodecyl benzene sulfonate and the like can be used.
  • a high hydrophilicity can be imparted with a small amount of addition to the polyolefin-based resin, and a surfactant is added to the raw material composition in advance because it has a relatively high heat resistance.
  • Alkyl benzene sulfonate, alkyl sulfosuccinate, and dodecyl benzene sulfonate are preferred because they can be produced (manufactured by hot melt molding).
  • Example 1 1000 parts by weight of ultrahigh molecular weight polyethylene resin powder (melting point: about 135 ° C.) having a weight average molecular weight of 1.5 million as a polyolefin-based resin, and a specific surface area by a BET method, which is a synthetic amorphous silica produced by a precipitation method, is 200 m 2.
  • silica fine powder (however, the content of salts such as sodium sulfate produced as a by-product in the production process is reduced by increasing the flow rate of water for washing water more than before, and more than the Cl content than before)
  • the final microporous membrane (10 cm x 10 cm x 2 sheets) is immersed in 126 g of sulfuric acid with a specific gravity of 1.26 at a temperature of 50 ° C for 24 hours.
  • alkali metal component (Li, Na, K, Rb , Cs) concentration (ICP emission spectral analysis) 5 mg / 100 cm 2 / sheet or less
  • a halogen component (F, Cl, Br, Concentration of) (ICP emission spectrometry) are those to be 0.4 mg / 100 cm 2 / sheet or less) 2590 parts by weight, and 5380 parts by weight of a paraffinic mineral oil as a plasticizer, an alkyl sulfosuccinate as a surfactant 109 parts by weight of salt (solid content) is mixed with a Laedige mixer, and this raw material composition is extruded into a sheet while heating and kneading using a twin screw extruder with a T die attached to the tip, and one roll Is passed through a pair of forming rolls with predetermined grooves for electrode plate contact main ribs, and the electrode plate contact main ribs having a predetermined shape are integrally formed on one surface of the flat sheet.
  • a film was obtained. Next, this film-like product is immersed in n-hexane, a predetermined amount of paraffinic mineral oil is extracted and removed, and dried to obtain 22.9% by weight of polyethylene resin, 59.3% by weight of fine silica powder, paraffin. Composed of 16.0% by weight of mineral oil and 1.8% by weight of surfactant (solid content), base thickness is 0.20mm, porosity by mercury intrusion method is 62% by volume, by mercury intrusion method A ribbed microporous film having an average pore size of 0.09 ⁇ m and a maximum pore size of 0.65 ⁇ m by mercury porosimetry was obtained. This was used as the liquid lead-acid battery separator of Example 1.
  • Example 2 1000 parts by weight of ultrahigh molecular weight polyethylene resin powder (melting point: about 135 ° C.) having a weight average molecular weight of 1.5 million as a polyolefin-based resin, and a specific surface area by a BET method, which is a synthetic amorphous silica produced by a precipitation method, is 200 m 2.
  • silica fine powder (however, the content of salts such as sodium sulfate produced as a by-product in the production process is further reduced by increasing the flow rate of water for washing treatment from Example 1 and By using water that has been washed with water with low Cl content, mixing of Cl content is reduced, and the final microporous membrane (10 cm x 10 cm x 2 sheets) is placed in 126 g of sulfuric acid with a specific gravity of 1.26 at a temperature of 50 ° C.
  • a film-like product obtained by molding was obtained.
  • this film-like product is immersed in n-hexane, a predetermined amount of paraffinic mineral oil is extracted and removed, and dried to obtain 22.9% by weight of polyethylene resin, 59.3% by weight of fine silica powder, paraffin.
  • Example 3 1000 parts by weight of ultrahigh molecular weight polyethylene resin powder (melting point: about 135 ° C.) having a weight average molecular weight of 1.5 million as a polyolefin-based resin, and a specific surface area by a BET method, which is a synthetic amorphous silica produced by a precipitation method, is 200 m 2.
  • / G of silica fine powder (however, the content of salts such as sodium sulfate produced as a by-product in the production process is reduced by increasing the flow rate of the washing water as compared with the prior art, and Cl is higher than in Example 1.
  • microporous membrane (10 cm ⁇ 10 cm ⁇ 2 sheets) in 126 g of sulfuric acid having a specific gravity of 1.26 at a temperature of 50 ° C.
  • a film-like product obtained by molding was obtained.
  • this film-like product is immersed in n-hexane, a predetermined amount of paraffinic mineral oil is extracted and removed, and dried to obtain 22.9% by weight of polyethylene resin, 59.3% by weight of fine silica powder, paraffin.
  • Comparative Example 1 1000 parts by weight of ultrahigh molecular weight polyethylene resin powder (melting point: about 135 ° C.) having a weight average molecular weight of 1.5 million as a polyolefin-based resin, and a specific surface area by a BET method, which is a synthetic amorphous silica produced by a precipitation method, is 200 m 2. / G of silica fine powder (however, the content of salts such as sodium sulfate produced as a by-product in the manufacturing process is the same as before, and the Cl content is reduced when the conventional water is used for water washing.
  • the final concentration of the microporous membrane (10 cm ⁇ 10 cm ⁇ 2) was immersed in 126 g of sulfuric acid having a specific gravity of 1.26 at a temperature of 50 ° C. for 24 hours and left standing (ICP emission).
  • Spectral analysis exceeds 5 mg / 100 cm 2 / sheet
  • concentration of halogen exceeds 0.4 mg / 100 cm 2 / sheet
  • 2590 weight Parts 5380 parts by weight of a paraffinic mineral oil as a plasticizer, and 109 parts by weight of an alkylsulfosuccinate (solid content) as a surfactant are mixed with a Ladige mixer.
  • the alkali metal concentration is 5 mg / 100 cm 2 / sheet or less.
  • the base thickness is 0.20 mm
  • mercury intrusion is composed of 5% by weight, silica fine powder 59.3% by weight, paraffinic mineral oil 16.0% by weight, and surfactant (solid content) 1.8% by weight.
  • a ribbed microporous film having a porosity of 62 vol% by the method, an average pore diameter of 0.09 ⁇ m by the mercury intrusion method, and a maximum pore diameter of 0.65 ⁇ m by the mercury intrusion method was obtained. This was used as the liquid lead-acid battery separator of Comparative Example 3.
  • MD means the production direction of the sheet to be produced
  • CD means a direction orthogonal to the MD direction.
  • ⁇ Base thickness> Using a dial gauge (Peacock G-6 manufactured by Ozaki Seisakusho Co., Ltd.), arbitrary points and several points of a microporous film (a portion not including rib-like projections when rib-like projections are included) were measured.
  • ⁇ Tensile strength, elongation> A test piece is cut from the microporous film into a rectangular size of 10 mm ⁇ 70 mm in the MD and CD directions.
  • the interval (a) between the grips of the tester is about 50 mm
  • a test piece is attached, and a tensile test is performed at a pulling speed of 200 mm per minute.
  • the tensile strength is calculated by dividing the tensile load (b) by the cross-sectional area of the test piece.
  • the elongation is calculated by dividing the distance (c) by the interval (a) between the grips of the tester.
  • ⁇ Porosity Vp / ((1 / ⁇ ) + Vp) Where Vp: pore volume (cm 3 / g), ⁇ : true density (g / cm 3 ) ⁇ Average pore diameter> The pore size distribution was calculated from the pressure and mercury volume at the time of mercury intrusion. The pore diameter at the time when mercury having a volume of 50% of the total pore volume was injected was defined as the average pore diameter (median diameter).
  • a positive electrode and a negative electrode made of a square lead plate of 50 mm ⁇ 50 mm are laminated with a microporous film separator cut into a 70 mm ⁇ 70 mm square shape, concentrically and in a square orientation, and laminated. After applying a pressure of 19.6 kPa to the electrode group consisting of the positive electrode (one piece), the separator (one piece), and the negative electrode (one piece) in the battery case, it was diluted with a specific gravity of 1.300 (20 ° C.).
  • the center of the three squares coincide with each other and the sides of the three squares are parallel to each other so that they are placed horizontally in the battery case, and a 5 kg weight is placed on them (at the center of the square).
  • a saturated lead sulfate aqueous solution is injected.
  • a current of 3.2 mA is applied to the lead electrode plate, and the voltage change is continuously recorded.
  • the voltage increases slightly after the start of energization and then gradually decreases. Time is measured until the voltage drops to 70% of the maximum voltage at this time.
  • Table 1 shows the relative values when the value of Comparative Example 1 is 100.
  • the obtained value is converted from ppm to mg / 100 cm 2 / sheet (weight per microporous film having an area of 100 cm 2 ) (provided that the base thickness is 0.1 per microporous film). If the base thickness is different from this, the value is converted and corrected so that the base thickness is about 0.2 mm).
  • Battery test charge acceptance, battery life
  • the charge acceptance is based on JIS D 5301 (2006), and measures the charge current after the start of charging when discharged at a 5-hour rate current for 2.5 hours.
  • the battery life is a light load life test method based on JIS D 5301 (2006), and a charge / discharge cycle test is performed, and the number of cycles when the voltage at 30 seconds becomes 7.2 V or less is measured.
  • the charge acceptability and battery life in Table 1 are displayed as relative values (relative results) when the value of Comparative Example 1 is 100.
  • the separator of Example 1 of the present invention has an alkali metal concentration (ICP emission spectroscopic analysis) of 5 mg / 100 cm 2 / sheet or less, so that the charge acceptance is improved and the halogen content is high. By setting the (ICP emission spectroscopic analysis) to 0.4 mg / 100 cm 2 / sheet or less, corrosion of the electrode plate lattice and the pole column was hindered, and the battery life was improved.
  • the separator of Example 2 of the present invention has a charge-accepting property by further reducing the concentration of alkali metal (ICP emission spectroscopic analysis) to 4 mg / 100 cm 2 / sheet or less with respect to the separator of Example 1. Improved further.
  • the separator of Example 3 of the present invention has a battery life that is less than that of the separator of Example 1 with a halogen content (ICP emission spectroscopic analysis) of 0.1 mg / 100 cm 2 / sheet or less. Improved further. (4) Therefore, if the separators of Examples 1 to 3 of the present invention are applied to a lead acid battery for automobiles, it is considered that it contributes to the improvement in charge acceptance and battery life required for an idling stop vehicle.
  • the separator of Comparative Example 1 Since the separator of Comparative Example 1 has an alkali metal concentration (ICP emission spectroscopic analysis) of more than 5 mg / 100 cm 2 / sheet, the charge acceptability is not improved to 100%, and halogen Since the concentration of the minute (ICP emission spectroscopic analysis) exceeds 0.4 mg / 100 cm 2 / sheet, corrosion of the electrode plate lattice and pole column was promoted, and the battery life was not improved to 100%. (6) The separator of Comparative Example 2 has a halogen content (ICP emission spectroscopic analysis) of 0.4 mg / 100 cm 2 / sheet or less, thereby preventing corrosion of the electrode plate lattice and the pole column, thereby reducing battery life.
  • ICP emission spectroscopic analysis alkali metal concentration

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

Abstract

L'invention concerne un séparateur destiné à un accumulateur au plomb du type liquide, comprenant une membrane microporeuse comportant au moins 40 % en poids de poudre de silice fine, qui est une silice amorphe synthétique fabriquée au moyen d'un procédé de précipitation dans lequel de la silice amorphe est synthétisée par provocation d'une réaction d'une solution aqueuse de silicate alcalin avec un acide minéral puis précipitation, après quoi sa pureté est ajustée par filtration et lavage à l'eau, caractérisé en ce que, lorsque la membrane microporeuse (10 cm × 10 cm × 2 feuilles) a été immergée dans 126 g d'acide sulfurique présentant une densité de 1,26 à une température de 50 °C et laissée reposer pendant 24 heures, la concentration (analyse par spectroscopie d'émission ICP) de composants métalliques alcalins (Li, Na, K, Rb, Cs) est inférieure ou égale à 5 mg/100 cm2/feuille (après conversion pour une épaisseur de base de 0,2 mm de la membrane microporeuse), et la concentration (analyse de spectroscopie d'émission ICP) de composants halogènes (F, Cl, Br, I) est inférieure ou égale à 0,4 mg/100 cm2/feuille (après conversion pour une épaisseur de base de 0,2 mm de la membrane microporeuse).
PCT/JP2017/013500 2016-03-31 2017-03-31 Séparateur destiné à un accumulateur au plomb du type liquide Ceased WO2017170977A1 (fr)

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JP2018509493A JP7248425B2 (ja) 2016-03-31 2017-03-31 液式鉛蓄電池用セパレータ
CN201780020347.4A CN108886124B (zh) 2016-03-31 2017-03-31 液体式铅蓄电池用分隔体
JP2022072931A JP7444920B2 (ja) 2016-03-31 2022-04-27 液式鉛蓄電池用セパレータ

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JPWO2017170977A1 (ja) 2019-02-07
CN108886124A (zh) 2018-11-23

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