CN108886124A - Liquid-type lead storage battery spacer body - Google Patents
Liquid-type lead storage battery spacer body Download PDFInfo
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- CN108886124A CN108886124A CN201780020347.4A CN201780020347A CN108886124A CN 108886124 A CN108886124 A CN 108886124A CN 201780020347 A CN201780020347 A CN 201780020347A CN 108886124 A CN108886124 A CN 108886124A
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- spacer body
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- 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
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- 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
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- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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Abstract
Liquid-type lead storage battery spacer body, microporous membrane of the liquid-type lead storage battery with spacer body comprising the fine silica powder containing 40 weight % or more, the fine silica powder are the synthesis amorphous silicas manufactured using following sedimentation：Make alkali silicate aqueous solution and inorganic acid reaction, after synthesizing amorphous silica by Precipitation, by the adjustment for filtering and washing progress purity；It is characterized in that, being 5mg/100cm by the concentration (ICP ICP Atomic Emission Spectrophotometer) that above-mentioned microporous membrane (10cm × 10cm × 2) impregnates the alkali metal component (Li, Na, K, Rb, Cs) when placed for 24 hours in the sulfuric acid 126g of the specific gravity 1.26 of temperature 50 C2/ or less the concentration (ICP ICP Atomic Emission Spectrophotometer) of (scaled value of the base thickness 0.2mm of microporous membrane) and halogenic ingredient (F, Cl, Br, I) be 0.4mg/100cm2/ or less (the base thickness 0.2mm scaled value of microporous membrane).
Description
Technical field
The present invention relates to be not to make electrolyte non-currentization and non-maintaining so-called hermetic type lead storage battery (is also referred to as controlled
Valve type lead storage battery processed) in but previous mode be include the so-called liquid-type lead storage battery with the electrolyte of mobility
Liquid-type lead storage battery used in (also referred to as exhaust lead storage battery, opening lead storage battery) is with spacer body (partition).
Background technique
In the past, as liquid-type lead storage battery spacer body, micro- porous membrane system of referred to as sub-polyethylene spacer separates
Body generally comprises the polyolefin-based resins (usually ultra-high molecular weight polyethylene) 20~60 that weight average molecular weight is 500,000 or more
Weight %, specific surface area 50m240~80 weight % of inorganic particle (usually fine silica powder) of/g or more, as opening
0~30 weight % of plasticizer (usually mineral oil), 0~10 weight % of surfactant (solid component) and the additive of hole agent
(antioxidant, weather resisting agent etc.) 0~5 weight %.
Above-mentioned micro- porous membrane spacer body generally by obtain as follows, base thickness be 0.1~0.3mm or so,
Average fine pore (mercury penetration method) is 0.01~0.5 μm or so, voidage (mercury penetration method) is 50~90 volume % or so
Sheet material：For said polyolefins system resin, above-mentioned inorganic particle, above-mentioned plasticizer is (much than above-mentioned spacer body composition
Cooperation), the feedstock composition that mixes of above-mentioned surfactant and above-mentioned additive, be extruded as piece when heating melting is kneaded
Material shape, roll-forming is after specific thickness, all or part of by above-mentioned plasticizer extracts removing.
The effect of above-mentioned inorganic particle is：Absorption carriage plasticizer when feedstock composition heating melting is kneaded；It produces
The microporous structure (fine and close and complicated pore structure and high voidage) of micro- porous membrane；It is resistant to the manufacture in micro- porous membrane
The sheet material generated when removing plasticizer in journey is shunk, remaining dimensionally-stable property；Make when micro- porous membrane is in battery assembly
Sheet material is also resistant to when heat treatment such with the drying process (moisture removal step) preceding carried out to shrink, and is remained dimensionally-stable
Property；Improve the electrolyte absorbability of micro- porous membrane；Improve the electrolyte wetability of micro- porous membrane；Improve micro- porous membrane
Electrolyte retentivity etc..
Therefore, usually as above-mentioned inorganic particle, using fine silica powder, especially from large specific surface area, oil absorption
Greatly, hydrophilic group (silanol group) viewpoints such as mostly are set out, and use the sedimentation legal system of wet process in the manufacturing method by dry or wet
The synthesis amorphous silica made.
On the other hand, lead storage battery it is vehicle-mounted on the way, for being equipped on the lead storage battery of idling flameout vehicle, by
It is more in electric discharge quantitative change, therefore gradually require charge acceptance height.It is known the charge acceptance of lead storage battery to be improved the case where
Under, if largely there is alkali metal (Li, Na, K, Rb, Cs) ion in the electrolytic solution, interfere the raising (patent of charge acceptance
Document 1).
In addition, it is also known that in lead storage battery, if the impurity of halogen (F, Cl, Br, I) is mixed into large quantities, corroding lead or
Electrode plate grid, the pole of metal can become the principal element (patent document 2) for reducing life performance.
The synthesis amorphous silica manufactured by above-mentioned sedimentation obtains with the following method：In neutral or alkali
Alkali silicate (sodium metasilicate) aqueous solution is reacted with inorganic acid (sulfuric acid) under property, makes amorphous silica Precipitation；In life
At amorphous silica in contain the salts such as sodium sulphate as by-product, carried out in rear process through filtering washing
Handle the processing (improving the processing of purity) for removing salt.
Existing technical literature
Patent document
Patent document 1：International Publication No. 2014/128803
Patent document 2：Japanese Unexamined Patent Publication 2005-251394 bulletin
Summary of the invention
Subject to be solved by the invention
But the removing of the salt in the manufacturing process of above-mentioned amorphous silica processing is not exclusively, therefore, in general,
The above-mentioned amorphous silica of manufacture contains the sodium sulphate of micro by-product.Therefore, micro- using such silica
Also contain micro sodium sulphate in above-mentioned micro- porous membrane of powder manufacture, the case where being used as lead storage battery with spacer body
Under, the progress used with battery dissolves out Na ion in the electrolytic solution, in the case where more than the amount of dissolution, can become and interfere fill
The principal element of the Receptive raising of electricity.
In addition, when the removing of the salt in the manufacturing process for carrying out above-mentioned amorphous silica by washing is handled,
Water used in washing can also cause the case where being mixed into the Cl ingredient as halogen.That is, existing using tap water (containing residual
Chlorine) situation, use the situation of underground water etc. of (sodium chloride) of containing salt.Therefore, water is being carried out using with such water
It washes in above-mentioned micro- porous membrane of the fine silica powder manufacture of processing also containing micro Cl ingredient, is used as lead storage battery
In the case where spacer body use, the progress used with battery dissolves out Cl ion in the electrolytic solution, in the situation more than the amount of dissolution
Under, promote the corrosion of electrode plate grid, pole, the principal element for reducing life performance can be become.
Therefore, the present invention is in view of the above existing problems, and it is an object of the present invention to provide spacer body, is the liquid for including microporous membrane
Body formula lead storage battery spacer body, the microporous membrane use fine silica powder to manufacture as main material, the fine silica powder
Be by sedimentation manufacture synthesis amorphous silica, in the battery for having used the spacer body with battery use into
In the case where row, it can also reduce from spacer body and dissolve out alkali metal ion amount, halide ion amount into electrolyte, enable to
It is not easy to interfere the raising of charge acceptance, enables to the reduction for being not easy to incur life performance.
Means for solving the problems
To achieve the goals above, as being recorded in technical solution 1, liquid-type lead storage battery spacer body of the invention
It is the liquid-type lead storage battery spacer body of the microporous membrane comprising the fine silica powder containing 40 weight % or more, the dioxy
SiClx micro mist is the synthesis amorphous silica manufactured by following sedimentation：Make alkali silicate aqueous solution and inorganic acid
After synthesizing amorphous silica by Precipitation, the adjustment for carrying out purity is washed by filtering for reaction；Its feature exists
In impregnating above-mentioned microporous membrane (10cm × 10cm × 2) in the sulfuric acid 126g of the specific gravity 1.26 of temperature 50 C placed
The concentration (ICP ICP Atomic Emission Spectrophotometer) of alkali metal component (Li, Na, K, Rb, Cs) when for 24 hours is 5mg/100cm2/ or less it is (micro-
The base thickness 0.2mm scaled value of perforated membrane) and the concentration (ICP ICP Atomic Emission Spectrophotometer) of halogenic ingredient (F, Cl, Br, I) be
0.4mg/100cm2/ or less (the base thickness 0.2mm scaled value of microporous membrane).
In addition, the liquid-type lead storage battery recorded in technical solution 2 is the liquid-type recorded in technical solution 1 with spacer body
Lead storage battery spacer body, which is characterized in that using ion exchange water or the progress of the underground water without salinity (sodium chloride) is above-mentioned
Filtering washing.
In addition, the liquid-type lead storage battery recorded in technical solution 3 is the liquid recorded in technical solution 1 or 2 with spacer body
Body formula lead storage battery spacer body, which is characterized in that above-mentioned microporous membrane is with above-mentioned fine silica powder and polyolefin tree
Micro- porous membrane made of based on rouge.
In addition, the liquid-type lead storage battery recorded in technical solution 4 is the liquid-type recorded in technical solution 3 with spacer body
Lead storage battery spacer body, which is characterized in that above-mentioned micro- porous membrane is that base thickness is 0.1~0.3mm, average fine pore
Micro- porous membrane that (mercury penetration method) is 0.01~0.5 μm, voidage (mercury penetration method) is 50~90 volume %.
Invention effect
It is the lead storage battery spacer body for including microporous membrane in accordance with the invention it is possible to provide spacer body, this is micro- porous
Film uses fine silica powder to manufacture as main material, which is the synthesis noncrystalline two manufactured by sedimentation
Silica in the case where the progress used in the battery for having used the spacer body with battery, can also be reduced from spacer body
Alkali metal ion amount, the halide ion amount in electrolyte are dissolved out, the raising for being not easy to interfere charge acceptance is enabled to, it can
So that being not easy to incur the reduction of life performance.
Specific embodiment
Liquid-type lead storage battery of the invention uses spacer body using following the description as condition：By microporous membrane (10cm ×
10cm × 2) in the sulfuric acid 126g of the specific gravity 1.26 of temperature 50 C dipping when placed for 24 hours alkali metal component (Li, Na,
K, Rb, Cs) concentration (ICP ICP Atomic Emission Spectrophotometer) be 5mg/100cm2/ or less (the base thickness 0.2mm of microporous membrane is changed
Calculation value) and halogenic ingredient (F, Cl, Br, I) concentration (ICP ICP Atomic Emission Spectrophotometer) be 0.4mg/100cm2/ or less it is (micro- more
The base thickness 0.2mm scaled value of pore membrane), above-mentioned microporous membrane includes that the fine silica powder of 40 weight % or more (has below
When be referred to as " above-mentioned fine silica powder "), above-mentioned fine silica powder is the synthesis amorphous manufactured using following sedimentation
Matter silica：Make alkali silicate aqueous solution and inorganic acid reaction, after synthesizing amorphous silica by Precipitation, passes through
Filtering washing carries out the adjustment (removing the salt as by-product, improve the purity of amorphous silica) of purity.
By make by above-mentioned microporous membrane (10cm × 10cm × 2) the specific gravity 1.26 of temperature 50 C sulfuric acid 126g
The concentration (ICP ICP Atomic Emission Spectrophotometer) of alkali metal component (Li, Na, K, Rb, Cs) when middle dipping is placed for 24 hours is 5mg/
100cm2/ hereinafter, in the liquid-type lead storage battery for having used liquid-type lead storage battery spacer body of the invention, energy
It is enough to inhibit to dissolve out the alkali metal ion amount into electrolyte from spacer body, therefore become the raising for being not easy to interfere charge acceptance.
Therefore, above-mentioned microporous membrane (10cm × 10cm × 2) is impregnated to placement in the sulfuric acid 126g of the specific gravity 1.26 of temperature 50 C
Concentration (ICP ICP Atomic Emission Spectrophotometer) more preferable 4mg/100cm of alkali metal component when for 24 hours2/ or less.
By making above-mentioned microporous membrane (10cm × 10cm × 2) in the sulfuric acid 126g of the specific gravity 1.26 of temperature 50 C
The concentration (ICP ICP Atomic Emission Spectrophotometer) of halogenic ingredient (F, Cl, Br, I) when dipping placed for 24 hours is 0.4mg/100cm2/
Hereinafter, in the liquid-type lead storage battery for having used liquid-type lead storage battery spacer body of the invention, be able to suppress from
Spacer body dissolves out the halide ion amount into electrolyte, therefore becomes to be not easy to incur that the corrosion of electrode plate grid, pole is promoted to be drawn
The reduction of the life performance risen.Therefore, by above-mentioned microporous membrane (10cm × 10cm × 2) temperature 50 C specific gravity
Concentration (ICP ICP Atomic Emission Spectrophotometer) more preferable 0.2mg/ of halogenic ingredient when dipping placed for 24 hours in 1.26 sulfuric acid 126g
100cm2/ open hereinafter, further preferred 0.1mg/100cm2/ or less.
Above-mentioned microporous membrane is preferably using above-mentioned fine silica powder and polyolefin-based resins as micro- more made of main body
Hole film, in addition, it is that 0.1~0.3mm, average fine pore (mercury penetration method) are that micro- porous membrane, which is preferably base thickness,
0.01~0.5 μm, voidage (mercury penetration method) be 50~90 volume % micro- porous membrane.It should be noted that so-called basis is thick
Degree (base thickness) be for example micro- porous membrane have rib in the case where in order to comprising rib
Overall thickness distinguishes and the term that uses, refers to (when not set rib) film thickness except the height by rib.
As described above, above-mentioned fine silica powder has：Absorption carriage is plasticized when feedstock composition heating melting is kneaded
Agent；Produce the microporous structure (fine and close and complicated pore structure and high voidage) of micro- porous membrane；Tolerance is micro- porous thin
The sheet material generated when removing plasticizer in the manufacturing process of film is shunk, remaining dimensionally-stable property；In micro- porous membrane in battery
Sheet material contraction is also resistant to as drying process (moisture removal step) when assembled using preceding progress when heat treatment, is kept
Dimensional stability；Improve the electrolyte absorbability of micro- porous membrane；Improve the electrolyte wetability of micro- porous membrane；Improve micro- more
The effects of electrolyte retentivity of hole film, therefore, from large specific surface area, oil absorption is big, hydrophilic group (silanol group) mostly etc.
Viewpoint is set out, and needs to be the synthesis noncrystalline titanium dioxide by the sedimentation manufacture of wet process in the manufacturing method of dry or wet
Silicon, however contain the salt such as sodium sulphate as by-product in the synthesis amorphous silica that the sedimentation by wet process manufactures
Class, although having carried out the processing for removing salt by the processing of filtering washing in rear process, the removing processing of salt
Not exclusively, in addition, can be used that tap water (containing residual chlorine), contain salt the underground water of (sodium chloride) in washing process, because
This, which contains, micro can generate dysgenic Na ingredient, Cl ingredient to battery performance.Therefore, in the present invention, as titanium dioxide
Silicon powder has used following fine silica powders, is the synthesis amorphous silica manufactured by the sedimentation of wet process,
The content of alkali metal component (Li, Na, K, Rb, Cs), halogenic ingredient (F, Cl, Br, I) is reduced to following level：It is obtained final
To microporous membrane (10cm × 10cm × 2) impregnated in the sulfuric acid 126g of the specific gravity 1.26 of temperature 50 C placed for 24 hours when
Alkali metal component concentration (ICP ICP Atomic Emission Spectrophotometer) become 5mg/100cm2/ or less and halogenic ingredient concentration
(ICP ICP Atomic Emission Spectrophotometer) becomes 0.4mg/100cm2/ or less.In addition, the system of above-mentioned amorphous silica of the invention
The washing process (processing for removing the salt of by-product) in process is made it is preferable to use ion exchange water or without salinity (chlorination
Sodium) underground water carry out.It should be noted that in the application, the so-called underground water without salinity (sodium chloride) refers to salinity (chlorination
Sodium) concentration be 300ppm underground water below.
The base thickness of above-mentioned micro- porous membrane is preferably 0.1~0.3mm, if it exceeds 0.3mm, then resistive penalties, such as
Fruit then becomes difficult to be able to maintain that (short circuit mentioned here refers to referred to as dendrite short circuit to good resistance to short-circuit less than 0.1mm
The short circuit penetration and the vulnerable area due to local substrate of (dendrite short), the protrusion from pole plate high compressing,
Impact, puncture, oxidation loss caused by the oxidizing force from pole plate etc. and so that hole is opened or generate caused common of rupture
It is both short-circuit).
The voidage (mercury penetration method) of above-mentioned micro- porous membrane is preferably 50 volume % or more, by for 50 volume % with
On, can internal resistance (resistance) be inhibited low as liquid-type lead storage battery spacer body, facilitate liquid-type lead electric power storage
The high performance in pond.Therefore, the voidage (mercury penetration method) of micro- porous membrane is more preferably 60~90 volume %, further excellent
It is selected as 70~90 volume %.
Obtain the method for above-mentioned micro- porous membrane preferably with the following method：To with polyolefin-based resins, above-mentioned titanium dioxide
Feedstock composition based on silicon powder and plasticizer carries out melting mixing, removes part or all of plasticizer after film
It goes.It obtains foring the countless connections with pahtfinder hard that is uniform and fine and intricately tangling in entire film as a result,
The film in hole.An example of specific manufacturing method described below.Firstly, for polyolefin-based resins, the above-mentioned dioxy in specified amount
It joined the former material of various additives (surfactant, antioxidant, weather resisting agent etc.) in SiClx micro mist, plasticizer as needed
Material, is stirred mixing using mixing machines such as Henschel mixer Huo レ ー デ ィ ゲ mixing machines, obtains raw mixture.It connects
Get off, which is dropped in the biaxial extruder that front end is mounted with T die head, is extruded into sheet material when heating melting is kneaded
Shape is carved from one roller and is passed through between a pair of of the forming roller for being equipped with regulation slot, to obtain the single side one in tabular sheet material
Form to body the tympan of the rib of regulation shape.Next, by the tympan at solvent appropriate (such as n-hexane)
The mineral oil extract of specified amount is removed and is dried, then obtains micro- porous membrane of target by middle dipping.It should be noted that former
Feed composition refers to the composition being made of the whole raw material fed in melting mixing process, and meaning refers to " complete eventually
The raw material (composition) in portion ", not refer in particular to the meaning of raw mixture, melting mixing object.
Total content of above-mentioned micro- porous membrane preferred polyolefm system resin, above-mentioned fine silica powder and plasticizer is 90
Weight % or more, the content of polyolefin-based resins are 20~60 weight %, and the content of above-mentioned fine silica powder is 40~80 weights
% is measured, the content of plasticizer is 0~30 weight %, and the content of surfactant is 0~8 weight %.If polyolefin-based resins
Content less than the content of 20 weight % or above-mentioned fine silica powder be more than 80 weight %, then polyolefin-based resins generate
For the mechanical strength of micro- porous membrane, inoxidizability, leakproofness ensure it is insufficient, if the content of polyolefin-based resins
More than the content of 60 weight % or above-mentioned fine silica powder less than 40 weight %, then become difficult to ensure micro- porous membrane
Big voidage, fine and complicated pore structure cannot maintain the good resistance characteristic of micro- porous membrane spacer body.
As said polyolefins system resin, it is able to use the homopolymerization of polyethylene, polypropylene, polybutene, polymethylpentene etc.
Object or copolymer and their mixture.Wherein, in terms of mouldability, economy, preferably using polyethylene as main body.
The melt molding temperature of polyethylene is lower than polypropylene, and productivity is good, and manufacturing cost is inhibited.With regard to polyolefin-based resins
Speech, by making weight average molecular weight become 500,000 or more, even micro- porous membrane largely containing fine silica powder, also can
Ensure the mechanical strength of film.Therefore, the weight average molecular weight of polyolefin-based resins is more preferably 1,000,000 or more, further preferably
1500000 or more.The Combination of polyolefin-based resins and fine silica powder is also good, and side is as bonding function in micro- porous membrane
Energy material makes the skeleton combination side of fine silica powder maintain intensity, while chemically stable, highly-safe.
As above-mentioned fine silica powder, it is able to use partial size carefully and there is the silica of pore structure on internal, surface
Micro mist.In inorganic particle, the range of choice of the various powder characteristics such as partial size, specific surface area of silica is wide, is easy to compare
It obtains cheaply, impurity is few.If the specific surface area of above-mentioned fine silica powder is 100m2/ g or more then makes micro- porous membrane
Pore structure further miniaturize (densification) and complicate and improve resistance to short-circuit, improve micro- porous membrane electrolyte keep
Power, in the hydrophily that there is powder surface a large amount of hydrophilic group (- OH) thus to improve micro- porous membrane, therefore preferably.Therefore, on
The specific surface area for stating fine silica powder is more preferably 150m2/ g or more.In addition, the specific surface area of above-mentioned fine silica powder is excellent
It is selected as 400m2/ g or less.It is more than 400m in the specific surface area of above-mentioned fine silica powder2In the case where/g, the surface-active of particle
Degree is high, aggregation force enhancing, thus become difficult in micro- porous membrane above-mentioned fine silica powder is evenly dispersed, therefore it is unexcellent
Choosing.
As above-mentioned plasticizer, the material that can become the plasticizer of polyolefin-based resins, usable and polyene are preferably selected
Hydrocarbon system resin has compatibility, the various organic liquids that can easily be extracted with various solvents etc., specifically, is able to use and includes
The plasticising of the esters systems such as higher alcohols, the dioctyl phthalates such as mineral oil, the stearyl alcohols such as the Industrial Oil of saturated hydrocarbons (paraffin)
Agent etc..Wherein, it is easy for for recycling this respect, preferably mineral oil.With polyolefin-based resins, fine silica powder, increasing
Agent is moulded as in the feedstock composition of main body, preferably cooperates the plasticizer of 30~70 weight %.
As described above, by the raw material group using polyolefin-based resins, fine silica powder and plasticizer as main body
It closes object to carry out melting mixing and remove above-mentioned plasticizer after being shaped to the tympan of regulation shape, so that porous, micro- more
The content of plasticizer in the film spacer body of hole can be zero.But in liquid-type lead storage battery spacer body, by containing
There is plasticizer as suitable mineral oil, can aid in antioxidative raising.Under such circumstances, preferably make spacer body
In plasticizer content be 5~30 weight %.But, if increasing the content of plasticizer, the gap of micro- porous membrane
Rate reduces, the resistive penalties of micro- porous membrane spacer body, therefore from such a viewpoint, the content of plasticizer is more preferably
20 weight % or less.
As for extracting the solvent for removing above-mentioned plasticizer, the saturation such as hexane, heptane, octane, nonane, decane can be used
The organic solvent of hydrocarbon system.
In addition, in above-mentioned raw materials composition or above-mentioned micro- porous membrane mesh of the invention can not damaged as needed
And add (cooperation) in the range of effect or contain surfactant (hydrophilic agent), antioxidant, ultraviolet absorbing agent, resistance to
Wait the additives such as agent, lubricant, antibacterial agent, mould inhibitor, pigment, dyestuff, colorant, antifoggant, delustering agent.
Above-mentioned micro- porous membrane is in large quantities containing large specific surface area and the high above-mentioned fine silica powder of hydrophily, even if such as
This has the sulfuric acid electrolyte of wetability, sulfuric acid to(for) the liquid-type lead storage battery as aqueous solution although having hydrophily
The permeability (dipped type) of electrolyte, but the injection sulphur of the laminated body in battery case is closely being assembled by pole plate and spacer body
When acid electrolyte, in order to promptly in the gap of spacer body Electolyte-absorptive, promptly the gap of spacer body is replaced into electricity
Liquid is solved, the surfactant (solid component) in micro- porous membrane containing 0.2~8 weight % is preferably made.
As the method for containing above-mentioned surfactant in micro- porous membrane is made, have pre- in the feedstock composition before film
First post-processed in the method (internal addition method) of dispersity addition, for film and by micro- porous membrane that plasticizer removes
The method (external addition method) of (attachment processing) manufacturing process's this respect and can be such that surfactant is difficult to from of the invention from that can simplify
Micro- porous membrane exudation this respect consideration, the pre-added method (internal addition method) preferably in feedstock composition.Surfactant
The content (necessary amounts) of (solid component) is 0.2~8 weight % in micro- porous membrane.Even if by surfactant (solid at
Point) content increase to the range or more, the hydrophilic effect for improving micro- porous membrane is not also significantly increased, on the contrary,
Making the voidage of micro- porous membrane reduces, and incurs the increase of internal resistance (resistance) as liquid-type lead storage battery spacer body,
Or incur the increase of self discharge as liquid-type lead storage battery spacer body.Therefore, surfactant (solid component) contains
Amount is 0.2~5 weight % more preferably in micro- porous membrane.
As above-mentioned surfactant, as long as can be improved the hydrophilic material of micro- porous membrane, nonionic
It is that surfactant, cationic system surfactant, anionic surfactant are able to use.As nonionic system surface
Polyoxyethylene alkyl ether class, polyoxyethylene alkyl phenyl ether class, polyoxyethylene alkylallyl base ethers, sweet can be used in activating agent
Oily mono fatty acid ester, sorbitan fatty acid ester class etc..As cationic system surfactant, aliphatic amine salt can be used
Class, quaternary ammonium salt, polyoxyethylene alkyl amine, alkyl amine oxide etc..As anionic surfactant, alkyl sulfonic acid can be used
Salt, alkylbenzene sulfonate, alkylnaphthalene sulfonate, alkyl sulfo succinate, dodecyl benzene sulfonate etc..Wherein, from for
Polyolefin-based resins lead to too small amount of addition can assign high-hydrophilic, by with relatively high heat resistance so as to by surface
Activating agent adds to carry out manufacture of micro- porous membrane (using the molding manufacture of heating melting) etc. in advance in feedstock composition
It sets out, optimizing alkyl benzene sulfonate, alkyl sulfo succinate, dodecyl benzene sulfonate.
Embodiment
Next, being explained in detail together with comparative example for the embodiment of the present invention.
(embodiment 1)
Polyvinyl resin with super-high molecular weight powder (the fusing point for being 1,500,000 by the weight average molecular weight as polyolefin-based resins
About 135 DEG C) 1000 parts by weight, as the ratio of the synthesis amorphous silica manufactured by sedimentation obtained using BET method
Surface area is 200m2The fine silica powder body of/g is (wherein, by making the flow-rate ratio of washing process water is in the past more making to reduce
The content of the salts such as the sodium sulphate generated during making as by-product, and the washing process using Cl ingredient less than in the past
Water, so that being mixed into for Cl ingredient is reduced, so that by finally obtained microporous membrane (10cm × 10cm × 2) in temperature 50 C
(ICP's concentration of alkali metal component (Li, Na, K, Rb, Cs) when dipping placed for 24 hours in the sulfuric acid 126g of specific gravity 1.26 shines
Spectrum analysis) become 5mg/100cm2/ or less and halogenic ingredient (F, Cl, Br, I) concentration (ICP ICP Atomic Emission Spectrophotometer)
As 0.4mg/100cm2/ or less) 2590 parts by weight, as 5380 parts by weight of paraffin mineral oil of plasticizer and as table
The 109 parts by weight Yong レ ー デ ィ ゲ mixing machine of alkyl sulfo succinate (solid component) of face activating agent mixes, using in front end
It is mounted with the biaxial extruder of T die head, which is extruded into sheet when heating melting is kneaded, from one roller
Middle carve passes through between a pair of of the forming roller for being equipped with the regulation slot for being used for pole plate abutting main rib, obtains the one side in tabular sheet material
The tympan of the integrally formed pole plate abutting main rib for being machined with regulation shape.Next, the tympan is impregnated in
In n-hexane, the specified amount of paraffin mineral oil is extracted and is removed, makes it dry, has obtained being weighed by polyvinyl resin 22.9
Measure %, 59.3 weight % of fine silica powder body, 16.0 weight % of paraffin mineral oil, surfactant (solid component) 1.8
Weight % constitute, base thickness 0.20mm, the voidage for using mercury penetration method to obtain for 62 volume %, using mercury pressure
Enter the average fine pore that method obtains be 0.09 μm, the maximum diameter of hole that uses mercury penetration method to obtain it is micro- with rib for 0.65 μm
Porous membrane.As the liquid-type lead storage battery spacer body of embodiment 1.
(embodiment 2)
Polyvinyl resin with super-high molecular weight powder (the fusing point for being 1,500,000 by the weight average molecular weight as polyolefin-based resins
About 135 DEG C) 1000 parts by weight, as the ratio of the synthesis amorphous silica manufactured by sedimentation obtained using BET method
Surface area is 200m2The fine silica powder body of/g is (wherein, by making the flow-rate ratio embodiment more than 1 of washing process water come into one
Step reduces the content of the salts such as sodium sulphate generated in the fabrication process as by-product, and use Cl ingredient is less than in the past
Washing process water, so that being mixed into for Cl ingredient is reduced, so that by finally obtained microporous membrane (10cm × 10cm × 2) in temperature
The concentration of alkali metal component (Li, Na, K, Rb, Cs) when dipping placed for 24 hours in the sulfuric acid 126g of the specific gravity 1.26 of 50 DEG C of degree
(ICP ICP Atomic Emission Spectrophotometer) becomes 4mg/100cm2/ or less and halogenic ingredient (F, Cl, Br, I) concentration (ICP shine point
Light analysis) become 0.4mg/100cm2/ or less) 2590 parts by weight, 5380 parts by weight of paraffin mineral oil as plasticizer
109 parts by weight Yong レ ー デ ィ ゲ mixing machine of alkyl sulfo succinate (solid component) mixing with as surfactant, makes
It is mounted with the biaxial extruder of T die head used in front end, which is extruded into sheet when heating melting is kneaded, from
Pass through carving to be equipped between a pair of of forming roller for the regulation slot of pole plate abutting main rib in one roller, obtains in tabular piece
The tympan of the integrally formed pole plate abutting main rib for being machined with regulation shape of the one side of material.Next, by the film-form
Object is impregnated in n-hexane, and the specified amount of paraffin mineral oil is extracted and is removed, makes it dry, has obtained by polyvinyl resin
22.9 weight %, 59.3 weight % of fine silica powder body, 16.0 weight % of paraffin mineral oil, surfactant (solid at
Point) 1.8 weight % constitute, base thickness 0.20mm, use mercury penetration method to obtain voidage for 62 volume %, use
The average fine pore that mercury penetration method obtains is 0.09 μm, mercury penetration method is used to obtain maximum diameter of hole has for 0.65 μm
Micro- porous membrane of rib.As the liquid-type lead storage battery spacer body of embodiment 2.
(embodiment 3)
Polyvinyl resin with super-high molecular weight powder (the fusing point for being 1,500,000 by the weight average molecular weight as polyolefin-based resins
About 135 DEG C) 1000 parts by weight, as the ratio of the synthesis amorphous silica manufactured by sedimentation obtained using BET method
Surface area is 200m2The fine silica powder body of/g is (wherein, by making the flow-rate ratio of washing process water is in the past more making to reduce
The content of the salts such as the sodium sulphate generated during making as by-product, and at the washing for using Cl ingredient fewer than embodiment 1
Water is managed, so that being mixed into for Cl ingredient is further reduced, so that by finally obtained microporous membrane (10cm × 10cm × 2) in temperature
The concentration of alkali metal component (Li, Na, K, Rb, Cs) when dipping placed for 24 hours in the sulfuric acid 126g of the specific gravity 1.26 of 50 DEG C of degree
(ICP ICP Atomic Emission Spectrophotometer) becomes 5mg/100cm2/ or less and halogenic ingredient (F, Cl, Br, I) concentration (ICP shine point
Light analysis) become 0.1mg/100cm2/ or less) 2590 parts by weight, 5380 parts by weight of paraffin mineral oil as plasticizer
109 parts by weight Yong レ ー デ ィ ゲ mixing machine of alkyl sulfo succinate (solid component) mixing with as surfactant, makes
It is mounted with the biaxial extruder of T die head used in front end, which is extruded into sheet when heating melting is kneaded, from
Pass through carving to be equipped between a pair of of forming roller for the regulation slot of pole plate abutting main rib in one roller, obtains in tabular piece
The tympan of the integrally formed pole plate abutting main rib for being machined with regulation shape of the one side of material.Next, by the film-form
Object is impregnated in n-hexane, and the specified amount of paraffin mineral oil is extracted and is removed, makes it dry, has obtained by polyvinyl resin
22.9 weight %, 59.3 weight % of fine silica powder body, 16.0 weight % of paraffin mineral oil, surfactant (solid at
Point) 1.8 weight % constitute, base thickness 0.20mm, use mercury penetration method to obtain voidage for 62 volume %, use
The average fine pore that mercury penetration method obtains is 0.09 μm, mercury penetration method is used to obtain maximum diameter of hole has for 0.65 μm
Micro- porous membrane of rib.As the liquid-type lead storage battery spacer body of embodiment 3.
(comparative example 1)
Polyvinyl resin with super-high molecular weight powder (the fusing point for being 1,500,000 by the weight average molecular weight as polyolefin-based resins
About 135 DEG C) 1000 parts by weight, as the ratio of the synthesis amorphous silica manufactured by sedimentation obtained using BET method
Surface area is 200m2Fine silica powder body (the salts such as sodium sulphate wherein, generated in the fabrication process as by-product of/g
Content as in the past and in the case where using Cl ingredient washing process water as in the past, do not reduce the mixed of Cl ingredient
Enter, so that by finally obtained microporous membrane (10cm × 10cm × 2) in the sulfuric acid 126g of the specific gravity 1.26 of temperature 50 C
The concentration (ICP ICP Atomic Emission Spectrophotometer) of alkali metal component when dipping placed for 24 hours is more than 5mg/100cm2/ and halogen at
The concentration (ICP ICP Atomic Emission Spectrophotometer) divided is more than 0.4mg/100cm2/) 2590 parts by weight, the paraffin series mine as plasticizer
Object 5380 parts by weight of oil and the 109 parts by weight Yong レ ー デ ィ of alkyl sulfo succinate (solid component) as surfactant
ゲ mixing machine mixing, using the biaxial extruder for being mounted with T die head in front end, by the raw mixture when heating melting is kneaded
It is extruded into sheet, carves to be equipped between a pair of of forming roller for the regulation slot of pole plate abutting main rib from one roller and lead to
It crosses, obtains the tympan in the integrally formed pole plate abutting main rib for being machined with regulation shape of the one side of tabular sheet material.
Next, the tympan is impregnated in n-hexane, the specified amount of paraffin mineral oil is extracted and is removed, makes it dry, obtains
It has arrived by 22.9 weight % of polyvinyl resin, 59.3 weight % of fine silica powder body, 16.0 weight % of paraffin mineral oil, table
That 1.8 weight % of face activating agent (solid component) is constituted, base thickness 0.20mm, the voidage obtained using mercury penetration method
It is 62 volume %, the average fine pore for using mercury penetration method to obtain for 0.09 μm, the largest hole that is obtained using mercury penetration method
Micro- porous membrane with rib that diameter is 0.65 μm.As the liquid-type lead storage battery spacer body of comparative example 1.
(comparative example 2)
The use as the synthesis amorphous silica manufactured by sedimentation has been used as fine silica powder body
The specific surface area that BET method obtains is 200m2The fine silica powder body of/g (wherein, is generated as by-product in the fabrication process
The salts such as sodium sulphate content as in the past, but the washing process water using Cl ingredient less than in the past, thus reduce Cl at
Point be mixed into so that by finally obtained microporous membrane (10cm × 10cm × 2) the specific gravity 1.26 of temperature 50 C sulfuric acid
The concentration (ICP ICP Atomic Emission Spectrophotometer) of alkali metal component when dipping placed for 24 hours in 126g is more than 5mg/100cm2/ and
The concentration (ICP ICP Atomic Emission Spectrophotometer) of halogenic ingredient becomes 0.4mg/100cm2/ or less), it is in addition to this, same with comparative example 1
Sample, it has obtained by 22.9 weight % of polyvinyl resin, 59.3 weight % of fine silica powder body, 16.0 weight of paraffin mineral oil
Amount %, 1.8 weight % of surfactant (solid component) are constituted, base thickness 0.20mm, it is obtained using mercury penetration method
Voidage be 62 volume %, the average fine pore that uses mercury penetration method to obtain is obtained for 0.09 μm, using mercury penetration method
Maximum diameter of hole be 0.65 μm of micro- porous membrane with rib.Separate as the liquid-type lead storage battery of comparative example 2
Body.
(comparative example 3)
The use as the synthesis amorphous silica manufactured by sedimentation has been used as fine silica powder body
The specific surface area that BET method obtains is 200m2The fine silica powder body of/g (wherein, keeps the flow-rate ratio of washing process water previous
It is reduce the content of the salts such as the sodium sulphate generated in the fabrication process as by-product more, but used Cl ingredient as in the past that
In the case where the washing process water of sample, do not reduce being mixed into for Cl ingredient so that by finally obtained microporous membrane (10cm ×
10cm × 2) concentration of alkali metal component of dipping when placed for 24 hours in the sulfuric acid 126g of the specific gravity 1.26 of temperature 50 C
(ICP ICP Atomic Emission Spectrophotometer) is 5mg/100cm2/ or less and the concentration (ICP ICP Atomic Emission Spectrophotometer) of halogenic ingredient be more than
0.4mg/100cm2/), in addition to this, in the same manner as comparative example 1, obtain by 22.9 weight % of polyvinyl resin, titanium dioxide
59.3 weight % of silicon micropowder, 16.0 weight % of paraffin mineral oil, 1.8 weight % of surfactant (solid component) are constituted
, base thickness 0.20mm, the voidage for using mercury penetration method to obtain obtained for 62 volume %, using mercury penetration method
0.65 μm of micro- porous membrane with rib is in the maximum diameter of hole that average fine pore is 0.09 μm, mercury penetration method is used to obtain.
As the liquid-type lead storage battery spacer body of comparative example 3.
Next, for each spacer body of Examples 1 to 3 obtained above, comparative example 1~3, using the following method into
Various characteristics evaluation is gone.It shows the result in table 1.It should be noted that MD (direction MD) refers to the manufacturer of manufactured sheet material
To CD (direction CD) refers to the direction orthogonal with the direction MD.
< base thickness >
It is (prominent with rib shape to micro- porous membrane using amesdial (the rugged production institute Co. Ltd. system ピ ー U ッ Network G-6 of tail)
The position of rib is free of in the case where rising) arbitrary point, several positions are determined.
< tensile strength, elongation >
The rectangle size for cutting out 10mm × 70mm from micro- porous membrane on the direction MD and CD, as coupons.
Using capacity 294N Shopper formula below or according to its cupping machine, making the clamping interval (a) of testing machine is about
50mm installs coupons, carries out tension test with the tensile speed of 200mm per minute, and stretching when reading coupons fracture carries
Lotus (b), distance (c).Tensile strength by with tensile load (b) divided by coupons sectional area and calculate.Elongation passes through use
Distance (c) is calculated divided by the clamping interval (a) of testing machine.
< voidage >
By the pore volume (mercury penetration method) and real density (infusion process) of micro- porous membrane, calculate according to the following formula.
Voidage=Vp/ ((1/ ρ)+Vp)
Wherein, Vp：Pore volume (cm3/g),ρ：Real density (g/cm3)
< average fine pore >
Pressure and mercury capacity when being pressed by mercury have calculated fine pore distribution.By 50% appearance of whole pore volumes
Fine pore at the time of long-pending mercury is pressed into is defined as average fine pore (meso-position radius).
The maximum diameter of hole < >
By average fine pore test in fine pore distribution curve, the aperture for having started the indentation of mercury is defined as maximum
Aperture.
< permeability >
Micro- porous membrane is cut into specific gravity 1.20 of the coupons of the square dimensions of 70mm × 70mm at 20 DEG C of temperature
Sulfuric acid liquid level floating after, sulfuric acid infiltration in the surface of coupons, measurement until a part discoloration of coupons time, rule
It is set to permeability (second).
< resistance >
The square dimensions that micro- porous membrane is cut into 70mm × 70mm, are made coupons, using according to SBA S
0402 experimental rig is measured.
< resistance to oxidation service life >
The anode and cathode for making the stereotype of the square of 50mm × 50mm are to clamp the pros for cutting into 70mm × 70mm
Micro- porous membrane spacer body of shape, concentrically and make square direction be consistently laminated, for the anode (1 by being laminated
), spacer body (1), (1), cathode composition electrode group apply the pressurization of 19.6kPa, after being assembled into battery case, injection
The dilute sulfuric acid electrolyte of the specific gravity 1.300 (20 DEG C) of 1000ml flows through the permanent electricity of direct current of 5.0A at 50 ± 2 DEG C of fluid temperature
Stream, conduction time at the time of measurement terminal voltage becomes 2.6V or less or voltage difference becomes 0.2V or more is, it is specified that be resistance to
Oxidization time (h).It should be noted that indicating the relative value when value of comparative example 1 is set as 100 in table 1.
< dendrite short circuit characteristic >
Micro- porous membrane square Plante-type plate of 2 50mm × 50mm of the square of 70mm × 70mm will be cut into
(pure lead system, thickness 3mm) clamping, so that micro- porous membrane is consistent with this 3 square centers of 2 Plante-type plates and 3 pros
Each side of shape is parallel to each other, and is arranged to horizontality in battery case, places 5kg's (in the center of square) on it
After weight (weight り), injection saturation lead sulfate aqueous solution.Thereafter, for the electric current of Plante-type plate energization 3.2mA, continuously record is electric
The variation of pressure.Voltage slightly rises after energization starts, and slowly declines thereafter.Metering is until voltage drops to maximum at this time
70% time of voltage.It should be noted that indicating the relative value when value of comparative example 1 is set as 100 in table 1.
< ICP ICP Atomic Emission Spectrophotometer >
The micro- porous membrane 2 for being cut into the square of 100mm × 100mm is opened and is put into the sulfuric acid 126g equipped with specific gravity 1.26
Beaker in.It puts it into and is held in 50 DEG C of thermostatic water bath, stand 24 hours.After 24 hours stand, from sulfuric acid (extracting solution)
It is middle to take out micro- porous membrane.Sulfuric acid (extracting solution) is diluted to 1/10, using ICP emission spectrophotometer in dilution
Alkali metal component (Li, Na, K, Rb, Cs) and halogenic ingredient (F, Cl, Br, I) carry out quantitative analysis.By obtained value from ppm
It is scaled mg/100cm2/ (every 1 area be 100cm2Micro- porous membrane weight) it is (wherein, so-called every 1 micro- porous thin
Film, it is specified that be every 0.2mm base thickness, in the case where base thickness is different from, converted, corrected to value so that at
For the base thickness of every 0.2mm).
< battery testing (charge acceptance, battery life) >
For charge acceptance, it is based on JIS D 5301 (2006), measurement has been discharged 2.5 hours with 5 hour rate currents
When, charging start after charging current.For battery life, using the light-loaded lifetime for being based on JIS D 5301 (2006)
The method of test, carries out charge and discharge cycles test, and the 30th second voltage of measurement becomes recurring number when 7.2V or less.It should say
Bright, the charge acceptance of table 1, battery life indicate the relative value (relative result) when the value of comparative example 1 to be set as to 100.
[table 1]
Content below as shown in Table 1.
(1) for the spacer body of the embodiment of the present invention 1, by concentration (the ICP luminescence spectrometer point for making alkali metal component
Analysis) become 5mg/100cm2/ hereinafter, to charge acceptance improve, while by make halogenic ingredient concentration (ICP shine
Spectrum analysis) become 0.4mg/100cm2/ corrosion hereinafter, to prevent electrode plate grid, pole is opened, battery life improves.
(2) for the spacer body of the embodiment of the present invention 2, relative to the spacer body of embodiment 1, by further making alkali
The concentration (ICP ICP Atomic Emission Spectrophotometer) of metal component becomes 4mg/100cm2/ open hereinafter, to which charge acceptance further changes
It is kind.
(3) for the spacer body of the embodiment of the present invention 3, relative to the spacer body of embodiment 1, by further making halogen
The concentration (ICP ICP Atomic Emission Spectrophotometer) of plain ingredient becomes 0.1mg/100cm2/ open hereinafter, to which battery life further improves.
(4) it is therefore contemplated that having if the spacer body of the embodiment of the present invention 1~3 is applied to automotive lead-acid battery
Help the raising of charge acceptance required for idling flameout vehicle and battery life.
(5) for the spacer body of comparative example 1, since the concentration (ICP ICP Atomic Emission Spectrophotometer) of alkali metal component is more than
5mg/100cm2/, therefore charge acceptance is 100%, improvement is not seen, in addition, due to the concentration (ICP of halogenic ingredient
ICP Atomic Emission Spectrophotometer) more than 0.4mg/100cm2/, therefore the corrosion of electrode plate grid, pole is promoted, battery life is
100%, do not see improvement.
(6) for the spacer body of comparative example 2, although by make the concentration (ICP ICP Atomic Emission Spectrophotometer) of halogenic ingredient at
For 0.4mg/100cm2/ hereinafter, battery life improves to prevent the corrosion of electrode plate grid, pole, but due to alkali metal at
The concentration (ICP ICP Atomic Emission Spectrophotometer) divided is more than 5mg/100cm2/, therefore charge acceptance is 100%, does not see and changing
It is kind.
(7) for the spacer body of comparative example 3, although the concentration (ICP ICP Atomic Emission Spectrophotometer) by making alkali metal component
As 5mg/100cm2/ hereinafter, to which charge acceptance improves, but due to the concentration of halogenic ingredient (ICP luminescence spectrometer point
Analysis) more than 0.4mg/100cm2/, therefore the corrosion of electrode plate grid, pole is promoted, battery life 100% is not seen
Improve.
Claims (4)
1. liquid-type lead storage battery spacer body, liquid-type lead storage battery spacer body includes two containing 40 weight % or more
The microporous membrane of ultrafine silica powder, the fine silica powder are the synthesis noncrystalline titanium dioxides manufactured by following sedimentation
Silicon：Make alkali silicate aqueous solution and inorganic acid reaction, after synthesizing amorphous silica by Precipitation, passes through filtering
Washing carries out the adjustment of purity；It is characterized in that, by above-mentioned microporous membrane (10cm × 10cm × 2) temperature 50 C specific gravity
Concentration (the ICP luminescence spectrometer of alkali metal component (Li, Na, K, Rb, Cs) when dipping placed for 24 hours in 1.26 sulfuric acid 126g
Analysis) it is 5mg/100cm2/ or less (the base thickness 0.2mm scaled value of microporous membrane) and halogenic ingredient (F, Cl, Br,
I concentration (ICP ICP Atomic Emission Spectrophotometer)) is 0.4mg/100cm2/ or less (the base thickness 0.2mm of microporous membrane converts
Value).
2. liquid-type lead storage battery spacer body described in claim 1, which is characterized in that use ion exchange water or not saliferous
The underground water of (sodium chloride) is divided to carry out above-mentioned filtering washing.
3. liquid-type lead storage battery spacer body of any of claims 1 or 2, which is characterized in that above-mentioned microporous membrane is above
Micro- porous membrane made of stating based on fine silica powder and polyolefin-based resins.
4. liquid-type lead storage battery spacer body as claimed in claim 3, which is characterized in that above-mentioned micro- porous membrane is basic thick
Degree is 0.1~0.3mm, average fine pore (mercury penetration method) is 0.01~0.5 μm, voidage (mercury penetration method) is 50~90
Micro- porous membrane of volume %.
Applications Claiming Priority (3)
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| JP2016072387 | 2016-03-31 | ||
| JP2016-072387 | 2016-03-31 | ||
| PCT/JP2017/013500 WO2017170977A1 (en) | 2016-03-31 | 2017-03-31 | Separator for liquid-type lead storage battery |
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| CN108886124A true CN108886124A (en) | 2018-11-23 |
| CN108886124B CN108886124B (en) | 2021-06-04 |
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| JP (2) | JP7248425B2 (en) |
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| Publication number | Publication date |
|---|---|
| JP2022100369A (en) | 2022-07-05 |
| JPWO2017170977A1 (en) | 2019-02-07 |
| WO2017170977A1 (en) | 2017-10-05 |
| JP7248425B2 (en) | 2023-03-29 |
| CN108886124B (en) | 2021-06-04 |
| JP7444920B2 (en) | 2024-03-06 |
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