CN1265166A - Non-woven fabric laminate - Google Patents

Non-woven fabric laminate Download PDF

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Publication number
CN1265166A
CN1265166A CN98807673A CN98807673A CN1265166A CN 1265166 A CN1265166 A CN 1265166A CN 98807673 A CN98807673 A CN 98807673A CN 98807673 A CN98807673 A CN 98807673A CN 1265166 A CN1265166 A CN 1265166A
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CN
China
Prior art keywords
fabric
laminate
arbitrary described
fiber
fibre
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN98807673A
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Chinese (zh)
Inventor
乔瓦尼·金蒂尔科尔
伊恩·M·兰开斯特
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Scimat Ltd
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Scimat Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
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Publication of CN1265166A publication Critical patent/CN1265166A/en
Pending legal-status Critical Current

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/22—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed
    • B32B5/24—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer
    • B32B5/28—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer impregnated with or embedded in a plastic substance
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/22—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed
    • B32B5/24—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer
    • B32B5/26—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer another layer next to it also being fibrous or filamentary
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B38/00—Ancillary operations in connection with laminating processes
    • B32B38/08—Impregnating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
    • B32B5/022—Non-woven fabric
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H13/00—Other non-woven fabrics
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H5/00—Non woven fabrics formed of mixtures of relatively short fibres and yarns or like filamentary material of substantial length
    • D04H5/04—Non woven fabrics formed of mixtures of relatively short fibres and yarns or like filamentary material of substantial length strengthened or consolidated by applying or incorporating chemical or thermo-activatable bonding agents in solid or liquid form
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/411—Organic material
    • H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
    • H01M50/417—Polyolefins
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/44—Fibrous material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
    • H01M50/457—Separators, membranes or diaphragms characterised by the material having a layered structure comprising three or more layers
    • 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
    • H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
    • H01M50/494—Tensile strength
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
    • B32B2260/02—Composition of the impregnated, bonded or embedded layer
    • B32B2260/021—Fibrous or filamentary layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/02—Synthetic macromolecular fibres
    • B32B2262/0253—Polyolefin fibres
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/718—Weight, e.g. weight per square meter
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/73—Hydrophobic
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2309/00—Parameters for the laminating or treatment process; Apparatus details
    • B32B2309/08—Dimensions, e.g. volume
    • B32B2309/10—Dimensions, e.g. volume linear, e.g. length, distance, width
    • B32B2309/105—Thickness
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2310/00—Treatment by energy or chemical effects
    • B32B2310/08—Treatment by energy or chemical effects by wave energy or particle radiation
    • B32B2310/0806—Treatment by energy or chemical effects by wave energy or particle radiation using electromagnetic radiation
    • B32B2310/0831—Treatment by energy or chemical effects by wave energy or particle radiation using electromagnetic radiation using UV radiation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00—Electrical equipment
    • B32B2457/10—Batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/34—Gastight accumulators
    • H01M10/345—Gastight metal hydride accumulators
    • 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Electrochemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Cell Separators (AREA)
  • Secondary Cells (AREA)
  • Nonwoven Fabrics (AREA)
  • Laminated Bodies (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)

Abstract

A laminate suitable for use as an electrode separator in an electrochemical device is formed from first and second non-woven fabrics which each comprise fibres of a hydrophobic polymeric material. The first fabric is formed from spun fibres and the second fabric is a melt-blown fabric. The fibres of the fabrics have undergone a copolymerisation reaction with a vinyl monomer which is capable of reacting with an acid or a base to form a salt directly or indirectly such as acrylic acid. The reaction involves exposure of the laminate to ultraviolet radiation while impregnated with a solution of the vinyl monomer, and results in grafting of the vinyl monomer to the surfaces of the fibres.

Description

Non-woven fabric laminate
The present invention relates to a kind of laminate and the method for handling non-woven fabric laminate by the bondedfibre fabric preparation.This laminate can be used as the dividing plate in the electrochemical apparatus.
The process of bondedfibre fabric manufacturing comprises that a. melts and sprays b. spinning c. wet method or dry-laying.The fiber of the fabric that obtains by spinning and wet method or dry-laying requires bonded to each other, makes fabric have globality, thereby has the required mechanical performance of effect that reaches satisfied.When fabric made by spinning, its fiber was bonded together by heating and pressurized, thereby made the structure of fabric keep stable.When fabric was made by wet method or dry-laying by polypropylene fibre, polyethylene was melted in the fabric, or as the fiber of only forming by polyethylene, or as two component fibres of forming by polypropylene nuclear and polyethylene sheath.When fabric was heated to above the temperature of the softening point of polyethylene, the result made the polyethylene in the fabric that the bonding of necessity can be provided.
Bondedfibre fabric can be used as the separators in the electrochemical apparatus.The example of this device comprises nickel chromium triangle and nickel metal colloidal metal cell.Dividing plate should be an inertia for its material that contacts in battery, and this material is particularly including alkaline electrolyte and electrode material.Dividing plate also should have a kind of like this physical property, makes in assembly equipment and use thereof, can sustain the processing that is stood.For example, it can bear the stress that is run into when occurring in cell device spiral pitch of the laps; It also can stop the growth of dendrite between electrode between charge period.
The fabric (" spun-bonded type " fabric) that makes from the textile fabric that is bonded together shortcoming be that thus the hole of blocking fabric effectively makes the bonding effective surface area that has reduced the fabric that is used for ion-exchange.The uneven CURRENT DISTRIBUTION that causes owing to this uneven pore size distribution can cause the generation of dendrite in the charging of battery, finally cause battery short circuit.Therefore, should reach a kind of balance between owing to interfibrous bonding mechanical strength that strengthens and the chemical property that weakens that causes by it for this fabric.
In addition, use the fabric that makes by textile fabric (bonded to each other or not bonding), particularly mounting equipment and as before the fabric of dividing plate and among, can cause comprising the distortion in relatively move (in the interval that bonding is arranged) of fabric fibre.This moving comprises that for example separating of fiber twines.It causes the opening of fabric construction.Add fabric as separators in, usually owing to shortened electrode and show and to have reduced fabric as the effect of barrier thing and increased the possibility that equipment breaks down.
The structure of meltblown fabric is stable when placing stress following time.Another advantage of meltblown fabric be little fiber size (it is usually less than about 5 microns, and often low about 1 micron or lower), thereby this fabric can be carried the dividing plate that arch has good barrier effect.Yet the fine size of fabric fibre means that this fabric can only bear the purposes of the strain of little stress and little degree.Big stress or high strain can cause breaking of fabric.
Has gratifying mechanical performance by the wet method of fiber or the fabric of dry-laying formation.Yet when particularly using two component fibres, it is undesirably big that fiber size becomes, often greater than 15 microns.Just another deficiency with bicomponent fiber is its cost height.
The invention provides a kind of laminate that melts and sprays with textile fiber, the fiber of this laminate is handled with vinyl monomer such as acrylic acid graft copolymerization.
Therefore, the invention provides a kind of laminate that forms by first and second bondedfibre fabrics on the one hand, each contains fibre of a hydrophobic polymeric material this bondedfibre fabric, first fabric is prepared by textile fabric, and second thing is prepared by meltblown fibers, copolyreaction has taken place with the vinyl monomer that can be directly or indirectly forms salt with acid or alkali reaction in the fiber of fabric, this reaction comprises when laminated product is immersed in vinyl monomer, laminated product is carried out ultraviolet radiation treatment, make vinyl monomer-grafted arrive the surface of fiber.
When the advantage of laminate of the present invention is to bear it and is used, for example assembling wherein this laminate as before the electrochemical apparatus of separators and among the stress that applied.Particularly, it is stable that the structure of this laminate still keeps under moderate duty, and when fabric be the trend that does not have opening when forming by textile fabric.In addition, than meltblown fibers, the structure of this laminate is when placing the following time of loading to reduce the possibility of breaking.
Another advantage of laminate of the present invention is: when its during as the separators of electrochemical apparatus, can show the good barrier performance that can obtain by melt-blown nonwoven fabric.This is because cause the little effective aperture that occurs in the laminate.The effective aperture in the hole that is limited by fabric fibre can be fixed by Coulter apertometer side.The effective aperture of preferred this laminate is more preferably less than about 20 microns, for example less than about 15 microns less than about 30 microns.The advantage of small-bore has been to increase the ability that dividing plate stops electrode material such as dendrite to pass.Laminate of the present invention can stand the processing of press polish step during fabrication.
When the processing fiber made it possess hydrophilic property, the small-bore also can increase the ability that fabric absorbs and keep electrolyte.The advantage of high electrolyte absorbability is to reduce and adopts laminate as the internal resistance in the equipment of separators, and prolongs the life-span of equipment.
When it was used as the separators of electrochemical apparatus, another advantage of laminate of the present invention resulted from the fine structure that meltblown fabric provides.This laminate can combine above-mentioned good physical property with the ability of absorb polluted matter.Can and use these pollutants that comprise ammonia and metal ion of in electrochemical apparatus, being found behind some electrode materials such as nickel hydroxide and the metal hydride cell in preparation.Adsorbed contaminants has the advantage that suppresses the self discharge reaction in equipment.Therefore, than the equipment that uses known dividing plate, can improve and use the life-span of laminate of the present invention as the equipment of dividing plate.
In the ammonia that the nitrate ion pollutant that can produce by reason nickel hydroxide electrode also form, found except with standard method as the ion-exchange capacity of measuring with the film of potassium hydroxide Titrable acid form, the ion-exchange capacity of remnants in addition.Believe that this remaining ion-exchange capacity can make ammonia in the electrochemical apparatus and other pollutant by absorption.Remaining ion-exchange can be represented with the milliequivalent of every gram laminate, and be measured as follows.Preferred its is at least about 0.15meq.g -1, preferably at least about 0.25meq.g -1, more preferably at least about 0.3meq.g -1, for example about 0.35meq.g -1
Compare the product based on bicomponent fiber such as polyethylene and polypropylene bicomponent fiber, being also advantageous in that of laminate of the present invention reduced cost.
Before forming laminate, the fiber of first fabric can be bonded to each other, as passing through the local joint (weld) between fabric.Then, but the fabric of the first fabric spun bonded.
The fiber of first fabric can right and wrong be bonding each other basically, wherein do not form this fabric by the bonding forming step of using heat and pressurization.Has weak active force between the fiber of these fabrics.For example in middle gentleness, depress, fabric is carried out press polish can cause weak active force, thereby cause the local deformation of fibrous material, especially in place that fiber contacts with each other.Yet these active forces can overcome when fabric tension is placed.This just may draw a clear line of demarcation between the fiber of fabric, makes not have any tight mixing that forms the fibrous material that produces because of joint.The performance of handling by the fabric of non-binder fiber preparation be disclosed in UK patent application 9712690.8 be priority, be entitled as in " bondedfibre fabric processing " patent application (proxy number is P10599), that in basis, please submit to.The theme that is disclosed in this patent is incorporated herein by reference.
Preferably bonding between first and second fabrics of this laminate.For example, can form bonding by local heat and pressurization.Can be laminate by heating between the hot-rolling with suitable profile surface and pressurizeing.This processing can cause forming between fabric local joint.These joints also can form bonding (this may be bonded to each other before lamination) between the fiber of first fabric.Preferably, the ratio that forms bonding zone in the laminate is less than about 20%, be more preferably less than about 15%, particularly less than about 10%, for example about 8%.
Preferably the average thickness (can measure by average diameter, especially when fiber has circular cross-section) by the fiber of first fabric of bondedfibre fabric preparation is not more than about 30 microns, more preferably no more than about 20 microns.The average thickness of the fiber of first fabric is often at least about 5 microns, for example about 10 microns.
Preferably the average thickness (can measure by average diameter, especially when fiber has circular cross-section) by the fiber of second fabric of bondedfibre fabric preparation is not more than about 8 microns, more preferably no more than about 5 microns.The average thickness of the fiber of second fabric is often at least about 0.5 micron.
The ratio of the fibre weight in the fibre weight of second fabric and the whole laminate is at least about 0.1, more preferably at least about 0.2, particularly at least about 0.4, for example at least about 0.5.
Use has different structure or different fiber or not only has different structure but also have asymmetric performance for the fabric of different fibers can make laminate.This can cause laminate one side to opposite side copolyreaction in various degree.When laminate was used as the dividing plate of some electrochemical apparatus, the surface that the laminate lower relatively than other surface hydrophobic occur was useful.Water-wetted surface is easier to be wetting by aqueous electrolyte institute, and this aqueous electrolyte can be useful in the positive electrode zone.When battery recharge, this can suppress hydrogen and flow to positive electrode from negative electrode.The relatively poor surface of hydrophily makes that (between the oxygen that electrode surface, electrolyte and this electrode produce) has produced three-phase boundary on the surface of negative electrode, owing to produced oxygen, the interior pressure when this can help to control charging in the battery.
Except first and second fabrics, laminate of the present invention also can comprise one or more fabrics.For example, laminate of the present invention can comprise the first and second above-mentioned fabrics, also has the 3rd and may also have the 4th fabric.The 3rd fabric can be prepared by textile fabric.The 3rd fabric can have identical structure with first fabric.The textile fabric of the 3rd fabric can be bonded to each other before forming laminate, promptly as spun-bonded fibre.Yet,, form bonding between the fabric of laminate by it usually by local heat with to add the fiber of pressure handle the 3rd fabric bonded to each other.First fabric and can be arranged in the reverse side of second fabric by the 3rd fabric that textile fabric forms.
According to following method of testing with meqg -1Measure the ion-exchange capacity of polymerization matter, measure the fibrous material and the graft copolymerization of vinyl monomer extent of reaction.Preferably, it is about 0.25 that ion-exchange capacity is at least, and preferably is at least approximately 0.4, especially preferably is at least approximately 0.6, and the preferred ion exchange capacity is no more than 2.0, more preferably no more than 1.6, especially preferably is no more than 1.4, for example is no more than 1.2.Have been found that the bondedfibre fabric grafting degree that particularly improvement of the physical property when being formed by polypropylene fibre can be lower reaches, the grafting degree is corresponding to the numerical value of ion-exchange capacity.
The gel fraction of textile material is measured according to ASTM D2765-84, thereby has measured the crosslinking degree of fabric.It is about 10% that preferred gel fraction is at least, and more preferably is at least approximately 20%, especially preferably is at least about 30%.
The thickness of fabric is about to 2.0 kilograms of weights with 2.0mms preferably by the DIN53105 test determines -1It is 2.0cm that speed is put into area 2Knit the layer sample strip on.This thickness is preferably greater than about 80 microns, more preferably greater than about 100 microns.Preferred this thickness is more preferably less than about 250 microns less than about 400 microns.The preparation method of laminate comprises fabric carried out press polish so that its thickness is reduced in the above-mentioned scope, and it is about 5% that the minimizing degree is at least, and preferably is at least about 15%, more preferably be at least about 25%, and, preferably, be more preferably less than about 40% less than about 45% less than about 60%.The advantage of press polish is to reduce effective size in fabric aperture, improves its screen-wall performance.The press polish step can be carried out before or after laminate and glycerol polymerization solution reaction.Have been found that before graft polymerization reaction laminate being carried out the press polish processing can increase reaction rate.Behind graft polymerization reaction, laminate is carried out press polish handle the electrolyte absorbability that can be enhanced.The laminate that press polish was handled behind the graft reaction has the ability of improved absorption impurity, particularly the ammonia that may exist in the Electolyte-absorptive system.In addition, carry out press polish and handle behind graft polymerization reaction, the fiber of laminate will be difficult for by physical damage.
Can directly form salt with the vinyl monomer of the polypropylene generation graft copolymerization of fiber surface, or, can form salt indirectly through after the suitable processing (may comprise for example hydrolysis or sulfonation) with acid or alkali reaction.Preferred vinyl monomer comprises ethylenically unsaturated carboxylic acids and ester thereof, as acrylic acid, methacrylic acid, methyl acrylate and methyl methacrylate.Spendable other vinyl monomer comprises acrylamide, vinylpyridine, vinyl pyrrolidone and styrene sulfonic acid.
Preferably, for example contain in the surfacing of at least some fibers, preferably at least about 60 weight %, more preferably at least about the polypropylene of 80 weight % at least about 40 weight %.At least 40 weight % are polypropylene in the material of the fiber of preferred first kind of fabric or second kind of fabric or these two kinds of fabrics, more preferably at least about 60 weight %, especially preferably at least about 80 weight %.
Preferably, in the fibrous material of the one-level of formation or secondary fabric (or each fabric) at least some, for example at least about 40 weight %, preferably at least about about 60 weight %, more preferably the material of at least 80 weight % mainly is homogeneous phase in whole fiber thickness.The material of preferred most fibers is mainly equal phase time in its thickness range, it can be suitable for multiple application, so these fibers can only be made by polypropylene or other suitable material (if required, can add proper additive).
On the other hand, the invention provides a kind of method of handling laminate, this laminate is formed by first and second bondedfibre fabrics that each contains polymer fiber, and wherein first fabric is made of textile fabric, second fabric is made of meltblown fibers, and this method comprises:
A. laminate is impregnated into and can be directly or indirectly forms in the vinyl monomer of salt with acid or alkali, solvent wherein is a kind of at the solvent that subsequently fabric is carried out can not volatilizing in a large number in the step of radiation treatment, and
B. when laminate and oxygen are isolated, the fabric behind the dipping is carried out ultraviolet radiation treatment, make monomer and fibrous material generation copolymerization.
The polymerisation that ultra-violet radiation causes can be carried out soon astoundingly, as long as the fabric after for example will flooding carried out radiation treatment about 15 seconds, even as long as 5 or 10 seconds.Have been found that and contain a large amount of grafted monomers in the reacted fabric, thereby make fabric be enough to reach wettable the aqueous solution in some electrochemical apparatus.This with graft reaction wherein with as the technology of beam bombardment (fabric of dipping or be exposed to fabric before the monomer solution) initiation opposite, many minutes reaction time of this reaction needed is to reach tangible grafting degree, and after both having made such reaction time, the degree of graft reaction is too low and can not be used for many purposes.These technologies can make the vinyl monomer homopolymerization or make textile material or vinyl monomer or textile material and vinyl monomer degraded.Therefore, it can not be processed continuously in mode of the present invention.
Be included in after the radiation detail that makes the hydrophilic method of the polymer fiber of bondedfibre fabric with the vinyl monomer dipping, be disclosed in WO-A-93/01622.Be disclosed in the document theme and introduce the application as a reference.
In radiation, stop dipping back laminate to contact with oxygen, for example the ultra-violet radiation step is carried out under inert atmosphere, for example in argon gas or nitrogen, fabric after maybe will flooding is sealed between the oxygen impermeable material layer, but this material should be saturating for the ultra-violet radiation of the suitable wavelength that causes copolyreaction.
Preferably, dipping solution comprises initiators for polymerization, and the initator of preferred initiation reaction is by atom is captured out from a kind of reaction raw materials, for example captures a hydrogen atom to generate a polymerization free radical from the polypropylene of fabric fibre.Capture after, polymerization free radical contacts with monomer in the solution, thus the generation of initiation grafting side chain.After an atom captured from the polypropylene of fabric fibre, the polypropylene molecule of activation can with another polypropylene molecule reaction, make the polypropylene in the fabric crosslinked, perhaps can with vinyl monomer generation copolyreaction.A kind of example of suitable initator is a benzophenone.It is about 50 that the mol ratio of vinyl monomer and initator preferably is at least, and more preferably is at least approximately 100, especially preferably is at least about 175; And this ratio is preferably less than about 1500, be more preferably less than about 1000, especially preferably less than about 500, more especially preferably less than about 350, according to appointment 200.
But dipping solution can comprise the component of ethene suppressing base monomer homopolymerization.Suitable inhibitor comprises iron (II) salt and copper (II) salt that dissolves in reaction medium.Preferred aqueous medium material is ferric sulfate (II).Yet find, selects the solvent of suitable graft polymerization reaction, speed by its restriction homopolymerization and degree just do not need inhibitor as the ability as radiator.This reduces the amount of polluting in the laminate in expectation is an advantage.
Dipping solution can comprise extra component with the optimization reaction condition, as contains surfactant to guarantee solution thorough impregnation bondedfibre fabric, contains the uniformity of the mixture of appropriate solvent with assurance solution, or the like.
The physical property (the strong rate that particularly stretches, aqueous solution wettable, or the two together) that an advantage of the present invention is to handle the back fabric can keep stablizing being in alkaline solution for a long time.Fabric with stable physical property is particularly suitable for as the dividing plate in the electrochemical apparatus, and wherein electrolyte comprises alkaline solution.The method that test is in the alkaline solution stability comprises fabric sample under 71 ℃, stores 21 days in the solution that contains 30 weight % potassium hydroxide, and relatively this is in the selected performance of fabric behind the alkaline solution with not being in fabric in the alkaline solution then.
On the other hand, the invention provides a kind of electrochemical apparatus, the electrode separator that comprises anode, negative electrode, a certain amount of electrolyte, makes by above-mentioned fabrics.Negative electrode in the preferred equipment comprises nickel hydroxide (II).The examples of material of making anode in this equipment comprises cadmium.In addition, also metal hydride cell of anode.Other electrochemical apparatus that can use dividing plate of the present invention comprises battery such as lead-acid battery.
The measuring method of ion-exchange capacity
With the bondedfibre fabric sample of heavily about 0.5 gram, changed into acid (H in 2 hours by being immersed in 60 ℃ the 1.0M hydrochloric acid +) formula.Sample with distilled water wash until the pH of the water that washes out value in 6～7 scopes.Then sample is dried to constant weight at 70 ℃.
Dried sample is put into 100 milliliters of polyethylene bottles, and wherein this bottle has accurately added the potassium hydroxide solution of 10 milliliters of about 0.1M.Add distilled water again with complete submergence sample.Add 10 milliliters of potassium hydroxide solutions in second polyethylene bottle, add distilled water (amount that contains in the sample is identical with joining) simultaneously, two bottles were deposited 2 hours at 60 ℃ at least.
After the cooling, the item transfer in each bottle in the glass conical flask, with 0.1M standard salt acid solution, is made indicator with phenolphthalein, the amount of potassium hydroxide in each bottle of titration.
Film is at dry acid (H +) during form, ion-exchange capacity is by equation IEC=(t 2-t 1)/10w calculates, and unit is milliequivalent/gram, wherein t 1Be to contain the value of salt acidometric titration in the bottle of sample, t 2Be not have the value of salt acidometric titration in the bottle of sample, w is with acid (H +) weight of the dry film that exists of form.
The measuring method of remaining absorbability
With the non-woven fabric laminate sample of having weighed, changed into the sylvite pattern in 1 hour by being immersed among 70 ℃ the 0.1M KOH.Sample is removed excessive KOH with distilled water wash.Remove excessive water with paper handkerchief.
Prepare ammonia spirit by mixing 120ml distilled water and 5ml 0.3M NH3.Immerse sample in this solution and put into 40 ℃ baking oven 2 hours.Then sample is cooled off.
Then, use the 0.1M hydrochloric acid solution, make indicator with methyl red, the 100ml sample solution is to neutral in the titration flask.Never the ammonia of laminate sample obtains contrasting reading in the solution of distilled water.
List the example of the separators that preparation forms by the on-woven polypropylene fibre below.
Comparative Examples 1:
Is thickness 316 microns, and the about 15-20 micron of fiber size, basis weights are 60gm -2Spunbond nonwoven polypropylene fabric be compacted after being heated to 125 ℃ smooth roll by one group.Thickness after its compacting is 170 microns.
By the roller of the chamber of fabric by being arranged in blanket of nitrogen, make fabric pass through acrylic acid solution, thereby use the acrylic acid solution impregnate fabric.Press following prescription (percetage by weight) obtain solution:
Composition weight %
Acrylic acid 30.0
Benzophenone 0.25 surfactant (Lutensol ON70 TM) 0.5
Water 69.25
Fabric behind the dipping is remained on N 2In the atmosphere, through the radiation chamber of a quartz glass wall.Medium pressure mercury lamp is put in quartz glass wall mistress's both sides parallel to each other.The power output of mercury lamp is 120wcm -1, and being positioned at fabric 16 centimeters, every lamp provides 10 centimetres wide parallel ultraviolet bundle.The whole time that fabric is in radiation was about for 6 seconds.
Spend the deionised water fabric then removing unreacted component, and in baking oven about 70 ℃ dry down.
The performance of handling the back fabric is listed in the table below, and compares with the respective performances of polypropylene fabric raw material.
Not after the grafting grafting
Ion-exchange capacity (meqg -1) 0 0.72
Gel content (%)
(ASTM?D2765-84)???????????????????????0????????????53.3
TENSILE STRENGTH (Nm on the machine direction -1)
(ASTM?D882)???????????????????????????2800?????????3100
Percentage elongation on the machine direction (%)
(ASTM?D882)???????????????????????????＞70?????????45
60 seconds 600 seconds 60 seconds 600 seconds (30% w/w KOH) (DIN 53924-78) (millimeters) 00 45 80 of electrolyte wicking rate (time)
Electrolyte trap (%)
(AD 447301 US Air Force Manual) are not wettable a2905
The survivor ion exchange capacity
(meq.q -1)????????????????????????0???????????????0.28
Comparative Examples 2
Is thickness 200 microns, and the about 3-5 micron of fiber size, basis weights are 46gm -2The melt-blown nonwoven polypropylene fabric as described in the Comparative Examples 1 with acrylic acid solution dipping and radiation.
The performance of handling the back fabric is listed in the table below, and compares with the respective performances of polypropylene fabric raw material.
Not after the grafting grafting
Ion-exchange capacity (meqg -1) 0 0.75
Gel content (%)
(ASTM?D2765-84)???????????????????????0????????????43
TENSILE STRENGTH (Nm on the machine direction -1)
(ASTM?D882)???????????????????????????0.8??????????1.077
Percentage elongation on the machine direction (%)
(ASTM?D882)???????????????????????????11???????????8
Electrolyte wicking rate (time) 60 seconds 600 seconds 60 seconds 600 seconds (30% w/w KOH) is (millimeter) 00 39 132 (DIN53924-78)
Electrolyte trap (%)
(AD 447301 US Air Force Manual) are not wettable a550
The survivor ion exchange capacity
(meq.q -1)????????????????????????0?????0.48
Embodiment 1:
Constitute laminate by fusion-jetting polypropylene fabric and textile fiber.The basic weight of meltblown fabric is 14gm -2, the about 3-5 micron of fiber size.The basic weight of spun-bonded fibre is 36gm -2, the about 15-20 micron of fiber size.By local heat with add to be pressed between the fabric fibre and form local joint and prepare this laminate.The thickness of this laminate is 294 microns.Be compacted after being heated to 125 ℃ smooth roll by one group.Thickness after its compacting is 170 microns.
As described in Comparative Examples 1, flood and this laminate of radiation with acrylic acid solution.
The performance of handling the back fabric is listed in the table below, and compares with the respective performances of polypropylene fabric raw material.
Not after the grafting grafting
Ion-exchange capacity (meqg -1) 0 0.4
TENSILE STRENGTH (Nm on the machine direction -1)
(ASTM?D882)????????????????????????????1770?????????2400
Percentage elongation on the machine direction (%)
(ASTM?D882)????????????????????????????41???????????19
60 seconds 600 seconds 60 seconds 600 seconds (30% w/w KOH) (DIN 53924-78) (millimeters) 00 50 110 of electrolyte wicking rate (time)
Electrolyte trap (%)
(AD 447301 US Air Force Manual) are not wettable a240
The survivor ion exchange capacity
(meq.q -1)?????????????????????????????0????????????0.4
Embodiment 2:
Be arranged in a kind of laminate of textile that the textile fabric of the reverse side of this meltblown fabric constitutes by fusion-jetting polypropylene fabric and two.The basic weight of meltblown fabric is 12gm -2, the about 3-5 micron of fiber size.The basic weight of spun-bonded fibre is 19gm -2, the about 15-20 micron of fiber size.By local heat with add to be pressed between the fabric fibre and form local joint and prepare this laminate.The thickness of this laminate is 229 microns.
As described in embodiment 1, flood and this laminate of radiation with acrylic acid solution.
Behind radiation and the washing step, this laminate by being heated to 97 ℃ smooth roll, with further its thickness to 151 of reduction micron.
The performance of handling the back fabric is listed in the table below, and compares with the respective performances of polypropylene fabric raw material.
Not after the grafting grafting
Ion-exchange capacity (meqg -1) 0 0.75
Gel content (%)
(ASTM?D2765-84)????????????????????????0????????????52.7
TENSILE STRENGTH (Nm on the machine direction -1)
(ASTM?D882)????????????????????????????2070?????????2600
Percentage elongation on the machine direction (%)
(ASTM?D882)????????????????????????????74???????????55
60 seconds 600 seconds 60 seconds 600 seconds (30% w/w KOH) (DIN 5 3924-78) of electrolyte wicking rate (time) (millimeter) 00 22 70
Electrolyte trap (%)
(AD 447301 US Air Force Manual) are not wettable a335
The survivor ion exchange capacity
(meq.q -1)?????????????????????????????0????????????0.37
Application in the battery
Remove a kind of AA type alkalescence screw type colloidal state nickel clipped wire (Misch metal electrode) photoelectric tube, its electrode area has reduced about 30%.Its dividing plate replaces with the foregoing description 2 preparations.KOH electrolyte with 30% re-assemblies battery.The charging under 350 milliamperes continuously of this battery is discharged under 10 ohm load, find this battery can be when disconnecting discharge for 1.0 volts 600 milliamperes/hour of outputs.
Strain rate and elongation at break
The deformation performance of the laminate of Comparative Examples 1 and 2 fabric and embodiment 2 relatively.Test with LloydInstrument tensilometer (model 10030).Write down elongation at break under the differently strained speed (%) and power (N).Laterally cutting sample and record width on width of fabric is 50mm, the long 200mm of being.
Strain rate (mm. branch -1) To example 1 ratio To example 2 ratios Embodiment 2
Elongation Power Elongation Power Elongation Power
????50 ????58 ????183 ????22 ????52 ????60 ????153
????250 ????56 ????194 a ????18 ????54 ????53 ????162 a
????500 ????52 ????205 ????16 ????59 ????44 ????154
????1000 ????46 ????186 ????10 ????68 ????36 ????140
( a--yield force)
These results show: under high strain rate as when twine the assembled battery element, meltblown fabric is because stretch-proof power of its difference and inapplicable.Textile fabric and laminate have bigger stretch-proof power.Strain rate and percentage elongation
Analysis is used for assessing the test material therefor of the strain rate of predetermined elongation to the influence of tensile property, measures its influence to the fabric maximum diameter of hole.The aperture is measured with Coulter pore instrument, represents with micron.
Strain rate (mm. branch -1) Percentage elongation (%) Maximum diameter of hole (micron)
Comparative Examples 1 Comparative Examples 2 Embodiment 2
0 ????0 ????76.72 ????20.04 ????14.43
1000 ????5 ????90.14 ????20.85 ????15.29
1000 ????7 ????90.14 ????2085 ????20.85
1000 ????10 ????109.2 Can't test ????19.73
These results show: the meltblown fabric of comparative example 2 can keep its structure under high strain rate, but only arrives limited elongation degree.Therefore, it is unwell to by winding and joins in the electrochemical apparatus.
The textile fiber of Comparative Examples 1 can bear big distortion under high strain rate.Yet destroyed the aperture thus.
The pore structure of the laminate structure of embodiment 2 is kept under height distortion and high strain rate.

Claims (16)

1. laminate that forms by first and second bondedfibre fabrics, each contains fibre of a hydrophobic polymeric material this bondedfibre fabric, first fabric is prepared by textile fabric, and second thing is prepared by meltblown fibers, copolyreaction has taken place with the vinyl monomer that can be directly or indirectly forms salt with acid or alkali reaction in the fiber of fabric, this reaction comprises textile impregnation carries out ultraviolet radiation treatment to fabric in vinyl monomer, make vinyl monomer-grafted arrive the surface of fiber.
2. laminate as claimed in claim 1 wherein exists bonding between first and second fabrics of this laminate.
3. laminate as claimed in claim 2, wherein together bonded to each other fabric by local joint.
4. as the arbitrary described laminate of claim 1-3, wherein the thickness of first fabric fibre is not worked energetically about 30 microns.
5. as the arbitrary described laminate of claim 1-4, wherein the thickness of first fabric fibre is at least about 5 microns.
6. as the arbitrary described laminate of claim 1-5, wherein the thickness of second fabric fibre is not more than about 8 microns.
7. as the arbitrary described laminate of claim 1-6, therein ethylene base monomer comprises ethylenically unsaturated carboxylic acids or its ester.
8. as the arbitrary described laminate of claim 1-7, wherein the ratio of the fibre weight in the fibre weight of second fabric and the whole laminate is at least about 0.1.
9. as the arbitrary described laminate of claim 1-8, it also comprises the 3rd fabric.
10. laminate as claimed in claim 9, wherein the 3rd fabric is prepared by textile fabric.
11. as claim 9 or 10 described laminates, wherein the first and the 3rd fabric is arranged in the reverse side of second fabric.
12. as the arbitrary described laminate of claim 1-11, its thickness is less than about 400 microns.
13. as the arbitrary described laminate of claim 1-12, wherein the fibrous material of at least a fabric comprises polypropylene.
14. laminate as claimed in claim 14, wherein the fibrous material of every kind of fabric comprises polypropylene.
15. a method of handling laminate, this laminate is formed by first and second bondedfibre fabrics that each contains polymer fiber, and wherein first fabric is made of textile fabric, and second fabric is made of meltblown fibers, and this method comprises:
A. laminate is impregnated into and can be directly or indirectly forms in the vinyl monomer of salt with acid or alkali, solvent wherein is a kind of at the solvent that subsequently fabric is carried out can not volatilizing in a large number in the step of radiation treatment, and
B. when laminate and oxygen are isolated, the fabric behind the dipping is carried out ultraviolet radiation treatment, make monomer and fibrous material generation copolymerization.
16. an electrochemical apparatus comprises anode, negative electrode, a certain amount of electrolyte and the electrode separator of being made by the arbitrary described laminate of claim 1-14.
CN98807673A 1997-06-18 1998-06-08 Non-woven fabric laminate Pending CN1265166A (en)

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EP0991804A1 (en) 2000-04-12

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