CN104521029A - Separator for lithium ion cell - Google Patents

Separator for lithium ion cell Download PDF

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Publication number
CN104521029A
CN104521029A CN201380030474.4A CN201380030474A CN104521029A CN 104521029 A CN104521029 A CN 104521029A CN 201380030474 A CN201380030474 A CN 201380030474A CN 104521029 A CN104521029 A CN 104521029A
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China
Prior art keywords
porous body
dividing plate
inorganic particulate
nonwoven substrate
lithium ion
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CN201380030474.4A
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Chinese (zh)
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CN104521029B (en
Inventor
渡边宏明
加藤真
加藤隆久
增田敬生
高滨信子
落合贵仁
加藤加寿美
笠井誉子
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Mitsubishi Paper Mills Ltd
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Mitsubishi Paper Mills Ltd
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Priority to CN201711214163.XA priority Critical patent/CN107834009B/en
Publication of CN104521029A publication Critical patent/CN104521029A/en
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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
    • 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
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/058—Construction or manufacture
    • 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
    • H01M50/431—Inorganic material
    • H01M50/434—Ceramics
    • 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
    • H01M50/443—Particulate material
    • 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

Abstract

A separator for a lithium ion cell, the separator comprising at least a porous body principally made of inorganic particles, wherein the separator is characterized in that the organic particles are of amorphous configuration. The performance of the separator for a lithium ion cell is such that internal resistance is low, pinholing and flaking is minimal, and current leakage is small.

Description

Lithium ion battery dividing plate
Technical field
The present invention relates to lithium ion battery dividing plate (below can referred to as " dividing plate ").
Background technology
Lithium ion battery as one of electrochemical element is the secondary cell with the high feature of energy density.As the power supply extensive use of the portable electric appts such as portable phone, portable music player, notebook PC.In addition, in the main equipments such as electric bicycle, car with mixed energy source, electric automobile, utilize the trend of lithium ion battery increasingly extensive.Therefore, people require the performances such as the charge-discharge characteristic under high capacity, big current to lithium ion battery.But known lithium ion battery is nonaqueous battery, the danger of therefore compared with water system battery, smoldering, catching fire, breaking etc. is high, also requires the raising of fail safe.
In lithium ion battery, the danger that the temperature rising, overcharge, internal short-circuit, external short circuit etc. that cause due to outside heat and making is smoldered etc. increases.The protection that they can be undertaken to a certain degree by outer protection circuit.In addition, as perforated membrane melting near 120 DEG C of the polyolefin resin that lithium ion battery uses with dividing plate, hole is inaccessible, thus blocks the flowing of electric current, ion, and the temperature of battery can be suppressed thus to raise.This is called as closedown (shut down) function.But when external heat causes temperature to raise, or temperature rising causes when inside battery generation chemical reaction, even if closing function plays a role, battery temperature also can raise further.Then, if battery temperature reaches more than 150 DEG C, then perforated membrane shrinks, and causes internal short-circuit, may cause and catch fire.
As mentioned above, the closing function of dividing plate is difficult to suppress catching fire of battery.In addition, along with the high capacity of battery, big current during discharge and recharge is developed, and in order to suppress the Joule heat now produced, the resistance value of the dividing plate being impregnated with electrolyte itself also must be made to reduce.Therefore, for following purpose, be developed and use the dividing plate of metal oxide particle: at the height making heat shrink temperature than the perforated membrane of polyolefin resin, make internal short-circuit be difficult to occur thus, thus while suppressing the catching fire of battery, reduce resistance value.In this dividing plate, control micropore diameter by metal oxide particle, can internal short-circuit be suppressed, improve thermal endurance, reduce resistance value.
Such as someone proposes the dividing plate with micro-porous pseudobochmite layer, described micro-porous pseudobochmite layer is mixed with binding agent by the pseudobochmite of inorganic particulate, be coated on the film for preparing separately, then dry and stripping, thus with (such as with reference to patent documentation 1) that the form of perforated membrane obtains.But, although the heat shrink temperature of this dividing plate improves, easily there is dry linting, cracking, be therefore difficult to take out separately with the form of the dividing plate of curling shape, the problem of operability difference when there is battery manufacture.
Somebody proposes has the dividing plate of porous inorganic covering on the nonwoven fabric with in non-weaving cloth, and wherein this inorganic covering has the oxide particle (such as with reference to patent documentation 2 and 3) for the aluminium (Al) of inorganic particulate, silicon (Si) and/or zirconium (Zr).This dividing plate is owing to utilizing non-weaving cloth as base material, and therefore operability improves.But, because the silicon oxide particle generated by sol-gal process causes clogging other inorganic particulate, therefore easily occur because impacting or being out of shape the dry linting, the cracking that cause, this causes the generation of pin hole, become the reason of the leakage current coming from small internal short-circuit, thus be difficult to be called useful dividing plate.
Somebody proposes a kind of dividing plate, wherein arranges the porous body (such as with reference to patent documentation 4 and 5) containing inorganic particulate and organic binder bond on the nonwoven fabric with in non-weaving cloth.Propose inorganic particulate in patent documentation 4 and adopt flat boehmite particle.But when using flat boehmite particle, although suppress the effect of leakage current to improve, flat inorganic particulate can block the micropore of dividing plate, therefore hinders passing through of lithium ion, has the problem that internal resistance raises.
In addition, propose in patent documentation 5 there is the secondary particle structure that primary particle is connected boehmite particle as inorganic particulate.In lithium ion battery, in order to store more energy in less battery volume, preferably generating to be tried one's best slimming without the component such as dividing plate of directly contribution.But, in such dividing plate be coated on by inorganic particulate on base material, according to dispersity or the coating method of this inorganic particulate, pin hole may be produced, being difficult to when making dividing plate thinning fully guarantee the insulation between positive electrode and negative material, leakage current may be made to increase.
In addition, on the nonwoven fabric be provided with in the dividing plate of the porous body containing inorganic particulate and organic binder bond in non-weaving cloth, when the administered dose of porous body (below can referred to as " coating weight ") is few, existence cannot obtain the problem of the little battery of leakage current, when coating weight is many, there is the problem that cannot obtain the dividing plate that thickness is thin, internal resistance is low.In order to solve this problem, there has been proposed different for micropore diameter 2 dividing plates that coating is laminated (such as with reference to patent documentation 6), but do not reach leakage current and internal resistance yet with high level and the product deposited.
Prior art document
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Application Publication 2001-527274 publication
Patent documentation 2: Japanese Unexamined Patent Application Publication 2005-536658 publication
Patent documentation 3: Japanese Unexamined Patent Application Publication 2009-507353 publication
Patent documentation 4: Japanese Unexamined Patent Publication 2007-157723 publication
Patent documentation 5: International Publication No. 2008/114727 pamphlet
Patent documentation 6: Japanese Unexamined Patent Application Publication 2006-507635 publication.
Summary of the invention
Invent problem to be solved
Problem of the present invention is to provide a kind of lithium ion battery dividing plate, and it is at least high containing the thermal endurance of inorganic particulate lithium ion battery dividing plate, performances such as wherein, having low internal resistance concurrently, be difficult to occur pin hole or dry linting, leakage current is few.
Solve the scheme of problem
The present inventor conducts in-depth research for solving described problem, found that following invention.
(1) the lithium ion battery dividing plate containing the porous body at least based on inorganic particulate, it is characterized in that, the shape of this inorganic particulate is amorphous.
(2) the lithium ion battery dividing plate described in (1), wherein, inorganic particulate has the shape having depression.
(3) (1) or the lithium ion battery dividing plate described in (2), wherein, inorganic particulate is hydrated alumina.
(4) the lithium ion battery dividing plate containing the porous body at least based on inorganic particulate, it is characterized in that, inorganic particulate is following hydrated alumina: the pH of its 20 quality % water dispersion is less than more than 7.0 8.3, and the viscosity of this water dispersion is more than 50mPas below 2000mPas.
(5) the lithium ion battery dividing plate according to any one of (1)-(4), this lithium ion battery dividing plate contains nonwoven substrate.
(6) the lithium ion battery dividing plate described in (5), wherein, has the fiber of nonwoven substrate to expose at least one side.
(7) lithium ion battery dividing plate, it is characterized in that: the 1st porous body and the 2nd porous body are laminated on nonwoven substrate successively, a face of nonwoven substrate is covered by the 2nd porous body in fact, has the fiber of nonwoven substrate to expose on opposite sides; Wherein, described 1st porous body disperses particle diameter to be more than 1.0 μm less than 3.0 μm, has the inorganic particulate of agglutinate structure for main body, the 2nd porous body be based on shape be amorphous, for have the shape of depression, dispersion particle diameter lower than 1.0 μm, not there is the inorganic particulate of agglutinate structure.
Invention effect
In the present invention, can provide a kind of lithium ion battery dividing plate, it is at least high containing the thermal endurance of inorganic particulate lithium ion battery dividing plate, performances such as having low internal resistance concurrently, be difficult to occur pin hole or dry linting, leakage current is few.
Lithium ion battery dividing plate containing the porous body at least based on inorganic particulate, is characterized in that: the shape of this inorganic particulate is amorphous; By this lithium ion battery dividing plate, pin hole and the few effect of dry linting can be realized.
In addition, inorganic particulate has the shape having depression, thus, even if by under inorganic particle filled state, easily form space due to depression, therefore can realize the few and effect that internal resistance is low of leakage current.
Inorganic particulate is hydrated alumina, and the thermal endurance that can realize dividing plate thus improves and uses the effect that the battery life of this dividing plate also extends.
Lithium ion battery dividing plate containing the porous body at least based on inorganic particulate, is characterized in that: inorganic particulate is that the pH of its 20 quality % water dispersion is less than more than 7.0 8.3, the viscosity of this water dispersion is the hydrated alumina of more than 50mPas below 2000Pas; By this lithium ion battery dividing plate, the effect that pin hole is few can be realized.
In addition, containing in the lithium ion battery dividing plate of porous body at least based on inorganic particulate, by further containing nonwoven substrate, can realize obtaining the homogeneous and effect of the dividing plate that hot strength is high of operability excellence, performance.
In addition, at least one face of the dividing plate containing nonwoven substrate, the fiber of nonwoven substrate exposes, and can realize the little effect of leakage current thus.
In addition, by having the lithium ion battery dividing plate of following characteristics, can realize that leakage current is little, thickness is thin and the effect that internal resistance is low: the 1st porous body and the 2nd porous body are laminated on nonwoven substrate successively, a face of nonwoven substrate is covered by the 2nd porous body in fact, has the fiber of nonwoven substrate to expose on opposite sides; Wherein, described 1st porous body to disperse particle diameter to be more than 1.0 μm less than 3.0 μm, there is the inorganic particulate of agglutinate structure, the 2nd porous body based on shape be amorphous, for have the shape of depression, dispersion particle diameter lower than 1.0 μm, not there is the inorganic particulate of agglutinate structure.
Accompanying drawing explanation
[Fig. 1] shape is sweep electron microscope (SEM) photo of unbodied inorganic particulate.
[Fig. 2] has the SEM photo of the inorganic particulate of rhombus column.
[Fig. 3] has the SEM photo of the inorganic particulate of cubic.
[Fig. 4] has the SEM photo of the inorganic particulate of the shape having depression.
[Fig. 5] has the SEM photo of flat inorganic particulate.
[Fig. 6] has the SEM photo of columned inorganic particulate.
[Fig. 7] represents the concept map of the cross section structure of the lithium ion battery dividing plate containing nonwoven substrate and the porous body at least based on inorganic particulate.
[Fig. 8] represents the concept map of the cross section structure of the lithium ion battery dividing plate containing nonwoven substrate and the porous body at least based on inorganic particulate.
[Fig. 9] represents the concept map of the cross section structure of the lithium ion battery dividing plate containing nonwoven substrate and the porous body at least based on inorganic particulate.
[Figure 10] represents the concept map of the cross section structure of the lithium ion battery dividing plate containing nonwoven substrate and the porous body at least based on inorganic particulate.
[Figure 11] represents the concept map of the cross section structure of the lithium ion battery dividing plate containing nonwoven substrate and the porous body at least based on inorganic particulate.
Embodiment
Dividing plate of the present invention is the lithium ion battery dividing plate containing the porous body at least based on inorganic particulate.Porous body forms to the multiple set of major general's inorganic particulate.Such as can enumerate: only by the porous body of multiple for inorganic particulate set, by the porous body etc. of inorganic particulate multiple set together with at least one being selected from inorganic binder, organic binder bond etc.In the present invention, " porous body at least based on inorganic particulate " refers to " porous body that 70 more than volume % of the part beyond space are made up of inorganic particulate ".
The feature of dividing plate of the present invention (1) is: the shape of inorganic particulate is amorphous.The SEM photo of Fig. 1 to be shape be unbodied inorganic particulate.Fig. 2 and Fig. 3 is the SEM photo of the inorganic particulate of setting.Fig. 2 is the inorganic particulate of rhombus column, and Fig. 3 is the inorganic particulate of cubic.Fig. 1 is flat particle, but the shape of each particle is uneven, for amorphous.The shape of inorganic particulate is amorphous, and in porous body, inorganic particulate is disorganized form thus, can closely fill, complex configurations, therefore can prevent dry linting, suppresses pin hole.And, can low current leakage be realized.
The method making amorphous inorganic particulate is not particularly limited.Such as can enumerate: make the stage of inorganic particulate crystal growth, make unbodied method by operation growth conditions; The method that inorganic particulate fragmentation is formed.
As dividing plate of the present invention (2), preferable shape is that unbodied inorganic particulate has the shape having depression.Fig. 4 is the SEM photo of the inorganic particulate with the shape having depression.Fig. 2, Fig. 3, Fig. 5 and Fig. 6 are the SEM photos of the inorganic particulate with nonpitting shape.Fig. 5 is unbodied tabular inorganic particulate.Fig. 6 is the cylindric inorganic particulate of setting.Fig. 2 is the rhombus column inorganic particulate of setting.Fig. 3 is the cubic inorganic particulate of setting.Fig. 4 and Fig. 5 is same, be unbodied tabular inorganic particulate, but a part for its outer rim has depression (white arrow part).By the existence of this depression, even if inorganic particulate still forms space when closely filling in porous body.By closely filling and leakage current can being suppressed, and internal resistance can be reduced by the formation in the space caused of caving in.
The method that inorganic particulate forms depression is not particularly limited.Such as can enumerate: in the stage of crystal growth making inorganic particulate, be formed the method for depression by operation growth conditions; The method etc. that inorganic particulate fragmentation is formed.
In the present invention, inorganic particulate can be enumerated: the aluminium oxide such as Alpha-alumina, beta-alumina, gama-alumina; The hydrated aluminas such as boehmite; The oxide of the alkaline-earth metal such as magnesium oxide, calcium oxide; Silicon dioxide; The alkaline earth metals carbonate such as calcium carbonate, magnesium carbonate; The composite oxides etc. such as alumina silicate.Particularly, from the viewpoint of stability, preferably use aluminium oxide or hydrated alumina.In addition, as dividing plate of the present invention (3), more preferably inorganic particulate is hydrated alumina.Hydrated alumina can be enumerated: the hydrated alumina of the various crystal formations of gibbsite type, boehmite-type, pseudobohemite type, bayerite type, diaspore type.In the present invention, consider from the angle obtaining the battery that thermal endurance is high, cycle life is good, preferably synthesize boehmite.
The feature of dividing plate of the present invention (4) is, inorganic particulate is following hydrated alumina: the pH of its 20 quality % water dispersion is less than more than 7.0 8.3, and the viscosity of this water dispersion is more than 50mPas below 2000mPas.Viscosity more preferably more than 100mPas below the 500mPas of this water dispersion.
The pH of 20 quality % water dispersions of inorganic particulate is: use conductivity be the ion exchange water of 0.5 below μ S/cm be prepared as the hydrated alumina particle of 20 quality % water dispersion at 25 DEG C by pH that glass electrode pH meter measures.
The viscosity of 20 quality % water dispersions of inorganic particulate is expressed as: according to JIS-Z8803, adopt Brookfield viscometer (Brookfield viscometer), use conductivity to be the measured value of water dispersion at 25 DEG C that the ion exchange water of 0.5 below μ S/cm is prepared as the hydrated alumina particle of 20 quality %.
In dividing plate of the present invention (4), hydrated alumina can be enumerated: the hydrated alumina of the various crystal formations of gibbsite type, boehmite-type, pseudobohemite type, bayerite type, diaspore type.In the present invention, consider from the angle that can obtain the battery that thermal endurance is high, cycle life is good, preferably synthesize boehmite.Shape for the particle of hydrated alumina is not particularly limited, and can be the granular of approximate sphericity, American football shape, cubic etc., also can be flakey or needle-like, tabular etc.Primary particle can also be used to be aggregated into the material of offspring, or non-agglutination particle.But the shape of preferred particle is amorphous, more preferably has the shape having depression.
In the present invention, in order to make inorganic particulate bonding, binding agent can be contained in porous body.As long as binding agent electrochemical stability and to nonaqueous electrolytic solution stablize, be not particularly limited, can inorganic binder be used, also can use organic binder bond.
As inorganic binder, such as, usually also referred to as silane coupler, the 3-glycidyl oxygen base trimethoxy silane, methacryloxypropyl trimethoxy silane, APTES etc. that make inorganic oxide be combined with chemistry of organic compound via dehydration or dealcoholization etc., there is the silicon compound of organo-functional group and the mixture of the inorganic oxide sol such as silicon dioxide, zirconia, due to its bonding strength, excellent heat resistance, therefore preferred, but be not limited to this.
As organic binder bond, such as, can enumerate: the nonaqueous binders of the resins such as vinyl-vinyl acetate copolymer (EVA), acrylate copolymer, fluorine class rubber, styrene butadiene ribber (SBR), acrylate copolymer, polyurethane etc.Also the binding agent imported for preventing the cross-linked structure be dissolved in nonaqueous electrolytic solution can be used in a part for these resins.Polyvinyl alcohol, PVP etc. can also be used to synthesize macromolecule; The cellulose derivative of the salt, CMC etc. of carboxymethyl cellulose; The water-soluble binder of the natural polymers such as starch, gelatin and their modifier, casein, albumin, alginic acid and salt thereof etc.These binding agents can be used alone a kind, also may be two kinds or more.Wherein particularly preferably SBR, acrylate copolymer, polyvinyl alcohol, PVP etc. synthesize macromolecule; The cellulose derivative such as salt, CMC of carboxymethyl cellulose.
From the viewpoint of maintenance dividing plate necessary ion permeability, the addition of binding agent must lower than 30 volume % of the porous body volume outside removal space, preferably lower than 20 volume %.In addition, from the viewpoint of the dry linting reduced from porous body, preferably 3 more than volume %.
Dividing plate of the present invention can make dividing plate separately by porous body, but from the viewpoint of the necessary intensity of maintenance dividing plate, the base material preferably containing perforated membrane, woven cloths, non-weaving cloth, braid etc.Specifically, the dividing plate on perforated membrane with porous body can be enumerated, on the base material formed by fibrous materials such as woven cloths, non-weaving cloth, braids or there is in the emptying aperture of base material inside the dividing plate etc. of porous body.
Form the method for porous body such as can enumerate: the coating fluid of coating containing inorganic particulate on the film etc. with stripping performance is also dry, then peels off, thus forms the method for porous body; On the negative or positive electrode of lithium ion battery, the coating fluid of coating containing inorganic particulate is also dry, thus forms the method for porous body; On the base material of woven cloths, non-weaving cloth, braid, perforated membrane etc., the coating fluid of coating containing inorganic particulate is also dry, thus forms the method etc. of porous body.
As long as the constituent material electrochemical stability of the base materials such as woven cloths, non-weaving cloth, braid, perforated membrane and to nonaqueous electrolytic solution stablize, be not particularly limited.Such as can enumerate: the polyester such as PETG, polybutylene terephthalate (PBT) and their derivative, aromatic polyester, full-aromatic polyester; Polyolefin; Acrylic polymer, polyacetals; Merlon; The polyketone such as aliphatic polyketones, aromatic polyketone; The polyamide such as aliphatic polyamide, aromatic polyamides, Wholly aromatic polyamide, partially aromatic polyamide; Polyimides; Polyamidoimide; Polyphenylene sulfide; Polybenzimidazoles; Polyether-ether-ketone; Polyether sulfone; Poly-(to phenylene benzo double thiazole); Poly-(to phenylene-2,6-benzo-dioxazole); The fluororesin such as Kynoar, polytetrafluoroethylene; Polyvinyl alcohol; Polyurethane; Polyvinyl chloride etc.From these constituent materials, two or more can also be combinationally used.Wherein, polyester or aromatic polyamides because fusing point is high, simultaneously high and preferred to the patience of the electrolyte used in battery.
The method of the coating fluid of coated inorganic particle is not particularly limited, such as, can enumerate: the method using Kohler coater, blade coating machine, knife, bar coater, extrusion coating machine, dip coater, gravure coater, kiss roll coater, die applicator, inverse roller coating cloth machine, delivery roll coating machine, flush coater, rotor wetting (rotor dampening) etc.
In the present invention, method dry after coating is not particularly limited, and particularly, blow the method for hot blast, irradiate ultrared method etc. and carry out dry method by heating, their productivity is good, preferably uses.
In the above-mentioned methods, in order to manufacture evenly porous body, can suitably use thickener, defoamer, wetting agent, anticorrisive agent etc. as required.
In the present invention, the basic weight of dividing plate is 10.0-40.0g/m 2, more preferably 15.0-37.5 g/m 2.The preferred 10.0-40.0 μm of thickness of dividing plate, more preferably 15.0-35.0 μm.The preferred 0.4-1.2g/cm of density of dividing plate 3, more preferably 0.6-1.0g/cm 3.
In the present invention, the amount of porous body is preferably 1.0-20.0g/m in dry solid content composition 2, be further preferably 4.0-17.5g/m 2.If the amount of porous body is lower than 1.0g/m 2, then micropore diameter increases, and can be short-circuited, and possibly cannot show good battery behavior.On the other hand, if the amount of porous body is more than 20.0g/m 2, then the filming of dividing plate may become difficulty.
In the present invention, in order to realize the planarization of porous bodies or control thickness, the surface smoothing of dividing plate can be made by press polish process or hot calendered process.
When dividing plate of the present invention contains the base materials such as perforated membrane, woven cloths, non-weaving cloth, braid, excellent for operability, easily obtain the homogeneous dividing plate of performance, can the reasons such as hot strength be improved, be more preferably the dividing plate (5) containing nonwoven substrate.
Nonwoven substrate such as can use by spun-bond process, meltblown, other dry process; Damp process; The nonwoven substrate that the methods such as method of electrostatic spinning manufacture.
In the present invention, in order to realize the planarization on nonwoven substrate surface or control thickness, nonwoven substrate smoothing can be made by press polish process or hot calendered process.
The nonwoven substrate preferred unit area weight used in lithium ion battery dividing plate of the present invention is 5.0-20.0g/m 2.If weight per unit area is more than 20.0g/m 2, then only nonwoven substrate just occupies the more than half of dividing plate, may be difficult to the effect that acquisition porous body brings.If lower than 5.0g/m 2, then may be difficult to obtain the homogeneity as nonwoven substrate.More preferably the weight per unit area of nonwoven substrate is 7.0-20.0g/m 2.It should be noted that, weight per unit area refers to the basic weight of the method according to JIS P8124 (paper and paperboard-basic weight determination method) defined.
When dividing plate of the present invention contains nonwoven substrate, porous body independently can be present in the surface of nonwoven substrate, also can penetrate into nonwoven substrate inside, with nonwoven substrate one integrated mass exist.Can also be the inside that the part of porous body penetrates into nonwoven substrate, the remainder of porous body be independently present in the surface of nonwoven substrate.
When dividing plate of the present invention contains nonwoven substrate, be preferably and at least one face have the fiber of nonwoven substrate to be exposed to the dividing plate (6) on surface." fiber of nonwoven substrate exposes " refers to that, when by scanning electron-microscopic observation, less than 80% of viewing area area is covered by porous body.When the two sides of nonwoven substrate is covered by porous body, may be difficult to reduce leakage current.The reason of this phenomenon is not yet clear and definite, is that the micropore diameter near relative face increases relatively because the micropore diameter near the face covered by porous body reduces relatively by inference, can produce some effects to suppression leakage current.In addition, be exposed in the dividing plate on the surface on two sides by inference at the fiber of nonwoven substrate, the degree of exposing on two sides produces difference under many circumstances, and the micropore diameter missionary society on consequent two sides produces some effects to suppression leakage current.
Fig. 7-Figure 11 is the concept map of the cross section structure of the dividing plate (5) represented containing nonwoven substrate.In (A) of Fig. 7, porous body 3 penetrates into the inside of nonwoven substrate 1, and nonwoven substrate 1 exists with porous body 3 one integrated mass ground.The fiber of nonwoven substrate 1 is had to expose on the two sides of nonwoven substrate 1.
(B), in, on a face of nonwoven substrate 1, porous body 3 is independent to be existed.(C) in, a part for porous body 3 penetrates into the inside of nonwoven substrate 1, and the remainder of porous body 3 is independently present on a face of nonwoven substrate 1.(B) and in (C), in the face relative with self-existent of porous body 3, the fiber of nonwoven substrate 1 exposes.
In (D) of Fig. 8, a part for porous body 3 penetrates in the inside entirety of nonwoven substrate 1, and the remainder of porous body 3 is independently present on a face of nonwoven substrate 1.(D), in, the fiber of nonwoven substrate 1 does not expose.
In (E) of Fig. 9, a part for porous body 3 penetrates into the inside entirety of nonwoven substrate 1, and the remainder of porous body 3 is independently present in the two sides of nonwoven substrate 1.(F), in, porous body 3 is independently present in the two sides of nonwoven substrate 1.(G) in, a part for porous body 3 penetrates into the inside of nonwoven substrate 1, and the remainder of porous body 3 is independently present in the two sides of nonwoven substrate 1.There is the region that porous body 3 does not permeate in the cross section central portion of nonwoven substrate 1.
(H)-(M) of Figure 10-Figure 11 is the dividing plate also containing other porous body 2 except porous body 3, nonwoven substrate 1.Other porous body 2 (below can referred to as " porous body 2 ") is based on the porous body of the inorganic particulate different from the inorganic particulate in dividing plate (1)-(4).
(H), in, porous body 2 permeates the inside in nonwoven substrate 1, with nonwoven substrate 1 one integrated mass exist.A part for porous body 3 penetrates into the inside of nonwoven substrate 1, and the remainder of porous body 3 is independently present on a face of nonwoven substrate 1.(I), in, both porous body 2 and porous body 3 are independently present on a face of nonwoven substrate 1 successively.(J) in, a part for porous body 2 penetrates into the inside of nonwoven substrate 1, and the remainder of porous body 2 is independently present on a face of nonwoven substrate 1.Porous body 3 is independently present on porous body 2 on a face of nonwoven substrate 1.(H), in-(J), be independently present on relative face, the face of most surface with porous body 3, the fiber of nonwoven substrate 1 exposes.
(K), in, porous body 3 penetrates into the inside of nonwoven substrate 1, with nonwoven substrate 1 one integrated mass exist.A part for porous body 2 penetrates into the inside of nonwoven substrate 1, and the remainder of porous body 2 is independently present on a face of nonwoven substrate 1.(L), in, porous body 3 and both porous bodies 2 are independently present on a face of nonwoven substrate 1 successively.(M) in, a part for porous body 3 penetrates into the inside of nonwoven substrate 1, and the remainder of porous body 3 is independently present on a face of nonwoven substrate 1.Porous body 2 is independently present on porous body 3 on a face of nonwoven substrate 1.(K), in-(M), be independently present on relative face, the face of most surface with porous body 2, the fiber of nonwoven substrate 1 exposes.
Also containing in the dividing plate of other porous body 2 except porous body 3, nonwoven substrate 1, for preferred scheme---dividing plate of the present invention (7) is described in detail.
In dividing plate (7), be more than 1.0 μm less than 3.0 μm to disperse particle diameter, have the 1st porous body of the inorganic particulate of agglutinate structure and based on shape be amorphous, for have the shape of depression, dispersion particle diameter lower than 1.0 μm, the 2nd porous body of the inorganic particulate without agglutinate structure is laminated on nonwoven substrate successively, a face of nonwoven substrate is covered by the 2nd porous body in fact, has the fiber of nonwoven substrate to expose on opposite sides.By dividing plate (7), can realize that leakage current is little, thickness is thin and the effect that internal resistance is low." the 1st porous body " is equivalent to " other porous body 2 ", and " the 2nd porous body " is equivalent to " porous body 3 ".
" face of nonwoven substrate is covered by the 2nd porous body in fact " refers to when by scanning electron-microscopic observation, and more than 95% of viewing area area is covered by the 2nd porous body." fiber of nonwoven substrate exposes " refers to when by scanning electron-microscopic observation, viewing area area less than 80% by arbitrary covering of the 1st porous body and the 2nd porous body.
" the dispersion particle diameter " of inorganic particulate represents: measure with laser diffraction formula particles distribution instrument the coating fluid that porous body forms middle use, its 50% value.
The dispersion particle diameter of the inorganic particulate in the 2nd porous body is preferably lower than 0.80 μm.In addition, if micropore diameter is too small, then possibly cannot obtain low internal resistance, therefore be preferably more than 0.10 μm.
Whether agglutinate structure is had about inorganic particulate, when by the inorganic particulate diagonal pitch of scanning electron-microscopic observation from intermediate value lower than above-mentioned dispersion particle diameter 1/2 time, then be judged as " having agglutinate structure ", be then judged as " without agglutinate structure " when being more than 1/2.Fig. 3 is the cubic inorganic particulate of setting, and dispersion particle diameter is 2.3 μm, is the inorganic particulate of " having agglutinate structure ".Fig. 4 is unbodied tabular inorganic particulate, and dispersion particle diameter is 0.4 μm, is the inorganic particulate of " without agglutinate structure ".
In order to obtain the effect realized by dividing plate (7), must successively laminated disperseing particle diameter to be more than 1.0 μm less than 3.0 μm, have the 1st porous body of the inorganic particulate of agglutinate structure and based on shape be amorphous, for have the shape of depression, dispersion particle diameter lower than 1.0 μm, not there is the 2nd porous body of the inorganic particulate of agglutinate structure.When being used alone the 1st porous body and the 2nd porous body arbitrary, when 1st porous body and the 2nd porous body arbitrary is differently composed, when laminated order is different, when a face of nonwoven substrate is not covered in fact by the 2nd porous body, when opposite face does not have the fiber of nonwoven substrate to expose etc. in situation, be difficult to the effect that acquisition can be realized by dividing plate (7).Below this point is described in detail.
Nonwoven substrate is only arranged disperse particle diameter to be more than 1.0 μm less than 3.0 μm, when there is the 1st porous body of the inorganic particulate of agglutinate structure, in order to reduce leakage current, necessary 1st porous body of thickness setting more than 10 μm.Therefore be difficult to manufacture the thin dividing plate of thickness.And nonwoven substrate is only arranged based on shape be amorphous, for have the shape of depression, dispersion particle diameter lower than 1.0 μm, not there is the 2nd porous body of inorganic particulate of agglutinate structure time, 2nd porous body easily produces pin hole, therefore in order to manufacture the little dividing plate of leakage current, must select such as to pass through containing fine fiber, increase thickness etc. as nonwoven substrate thus being difficult to produce the nonwoven substrate of pin hole.Therefore, except being difficult to generate except pin hole, angularly considering from cost, intensity, selecting best nonwoven substrate to become difficult.
On nonwoven substrate successively laminated based on disperse particle diameter lower than 1.0 μm, have the inorganic particulate of agglutinate structure the 1st porous body and based on shape be amorphous, for have the shape of depression, dispersion particle diameter lower than 1.0 μm, not there is the 2nd porous body of inorganic particulate of agglutinate structure time, be difficult to manufacture the low dividing plate of internal resistance.
On nonwoven substrate successively laminated based on the 1st porous body of the inorganic particulate without agglutinate structure and based on shape be amorphous, for have the shape of depression, dispersion particle diameter lower than 1.0 μm, not there is the 2nd porous body of inorganic particulate of agglutinate structure time, easily pin hole is produced in 1st porous body, except being difficult to generate except pin hole, angularly consider from cost, intensity, select best nonwoven substrate to become difficult.
At the interface of the 1st porous body and the 2nd porous body, the inorganic particulate of the 2nd porous body may enter the interparticle space of the 1st porous body.On nonwoven substrate successively laminated disperseing particle diameter more than 3.0 μm, have the 1st porous body of the inorganic particulate of agglutinate structure and based on shape be amorphous, for have the shape of depression, dispersion particle diameter lower than 1.0 μm, not there is the 2nd porous body of inorganic particulate of agglutinate structure time, the amount entering the inorganic particulate of the 2nd porous body in interparticle space too much blocks, and manufactures the low dividing plate of internal resistance and becomes difficult.
On nonwoven substrate successively laminated disperseing particle diameter to be more than 1.0 μm less than 3.0 μm, there is the 1st porous body of the inorganic particulate of agglutinate structure and to disperse particle diameter to be the 2nd porous body of the inorganic particulate of more than 1.0 μm time, in order to realize little leakage current, possible coating weight must be over 10.0g/m 2, manufacture the thin dividing plate of thickness and become difficult.Non-laminated disperseing particle diameter to be more than 1.0 μm less than 3.0 μm, when there is the 1st porous body of the inorganic particulate of agglutinate structure and the 2nd porous body based on the inorganic particulate with agglutinate structure successively on woven cloths base material, equally, in order to realize little leakage current, possible coating weight must be over 10.0g/m 2, manufacture the thin dividing plate of thickness and become difficult.
For on nonwoven substrate successively laminated based on shape be amorphous, for have the shape of depression, dispersion particle diameter lower than 1.0 μm, not there is the 1st porous body of the inorganic particulate of agglutinate structure, with to disperse particle diameter to be more than 1.0 μm less than 3.0 μm, there is the dividing plate of the 2nd porous body of the inorganic particulate of agglutinate structure, easily in the 1st porous body, produce pin hole, in order to this pin hole inaccessible, reduce leakage current, coating weight must be set more than 10.0g/m 2the 2nd porous body, the dividing plate therefore manufacturing thinner thickness becomes difficult.
In the dividing plate that the dividing plate do not covered in fact by the 2nd porous body in a face of nonwoven substrate or opposite face do not have the fiber of nonwoven substrate to expose, be difficult to reduce leakage current.The reason of this phenomenon is still not clear, and is that the micropore diameter near the face owing to substantially being covered by the 2nd porous body is relatively little by inference, and the micropore diameter near opposite face is relatively large, and this has some to affect for suppression leakage current.
Dividing plate (7) is manufactured by the following: be coated with successively to disperse particle diameter to be more than 1.0 μm less than 3.0 μm, there is the inorganic particulate of agglutinate structure on nonwoven substrate the coating fluid of the 1st porous body being main body and based on shape be amorphous, for have the shape of depression, dispersion particle diameter lower than 1.0 μm, not there is the coating fluid of the 2nd porous body of the inorganic particulate of agglutinate structure.After the coating fluid of coating the 1st porous body, the coating fluid of the 1st porous body can be made dry, then after the coating fluid of coating the 2nd porous body, makes the drying of the coating fluid of the 2nd porous body.Can also be after the coating fluid of coating the 1st porous body, do not make the coating fluid of the 1st porous body dry and be coated with the coating fluid of the 2nd porous body, and making the coating fluid of the 1st porous body dry together with the coating fluid of the 2nd porous body.When the coating fluid of the 1st porous body mixes before it is dried with the coating fluid of the 2nd porous body, 1st porous body can block, and internal resistance may raise, therefore, preferably drying removes the volatile ingredient of the 1st porous body coating fluid at least partly, is then coated with the coating fluid of the 2nd porous body.
In dividing plate (7), the method that nonwoven substrate is coated with the coating fluid of the 1st porous body and the 2nd porous body can adopt the coating process of above-mentioned inorganic particulate coating fluid.Preferred method is the method using gravure coater, die applicator, blade coating machine, bar coater, roll coater etc.Particularly the coating of the 1st porous body coating fluid preferably adopts the method for gravure coater, die applicator.This is because these two kinds of coating methods are difficult to produce the dynamic pressure made in coating fluid infiltration nonwoven substrate, is difficult to produce pin hole on the 1st porous body.
In dividing plate (7), the coating weight of the 1st porous body is preferably 3.0g/m according to dry solid content composition meter 2above 10.0g/m 2below, more preferably 4.0g/m 2above 8.0g/m 2below.When the coating weight of the 1st porous body is very few, may produce pin hole, leakage current increases.In addition, when the coating weight of the 1st porous body is too much, the thickness of dividing plate is thickening, and internal resistance also may raise.
In dividing plate (7), the coating weight of the 2nd porous body is preferably 2.0g/m according to dry solid content composition meter 2above 8.0g/m 2below, more preferably 3.0g/m 2above 6.0g/m 2below.When the coating weight of the 2nd porous body is very few, leakage current may increase.In addition, when the coating weight of the 2nd porous body is too much, the thickness of dividing plate is thickening, and internal resistance also may raise.
The thickness of dividing plate (7) preferably lower than 30 μm, more preferably less than 25 μm.For the dividing plate thicker than this, even if be not the formation as dividing plate (7), the selection of nonwoven substrate also can not be significantly restricted, can manufacture the dividing plate that leakage current is little.
The nonwoven substrate used in dividing plate (7) its diameter preferably containing more than 50 quality % is the fiber of less than 3.5 μm.Thus, can more positively prevent from producing pin hole in porous body.In addition, the thickness preferably more than 10 μm of the nonwoven substrate used in dividing plate (7), more preferably more than 15 μm.Can more positively prevent from thus producing pin hole in porous body.On the other hand, when the thickness of the nonwoven substrate used in dividing plate (7) is blocked up, the thickness of dividing plate can become blocked up, therefore the thickness of nonwoven substrate preferably less than 30 μm, more preferably less than 25 μm.
Embodiment
Below embodiments of the invention are shown.In embodiment, as being not particularly limited, percentage (%) and part are quality criteria.When representing number in (), it is the number of the nonvolatile component (solid content composition) in express liquid.Coating weight is drying coated amount.
" the first experiment "
The making > of < nonwoven substrate 1
Be 0.06dtex (fiber diameter 2.4 μm) by 45 parts of fiber numbers, fibre length is oriented crystalline PETG (PET) the class short fiber of 3mm, 15 parts of fiber numbers are 0.1dtex (fiber diameter 3.0 μm), the oriented crystalline PET class short fiber of fibre length 3mm, be 0.2dtex (fiber diameter 4.3 μm) with 40 parts of fiber numbers, the single component type binding agent PET class short fiber (softening point 120 DEG C of fibre length 3mm, fusing point 230 DEG C) be mixed together, dissociated in water by pulp machine, the use slurry of manufacturing paper with pulp uniformly that concentration is 1% is prepared by the stirring of blender.Use cylinder paper machine, by the damp process system of copying, this is manufactured paper with pulp with slurry, then by the drying of 120 DEG C, binding agent PET class short fiber is bonded, and performance non-weaving cloth intensity, makes weight per unit area 12.2g/m 2non-weaving cloth.Further use comprises single nip hot pressing ray machine of metallic roll-metallic roll, implements heat treated, make the nonwoven substrate 1 of thickness 21 μm with roller temperature 185 DEG C, line pressure 740N/cm, transfer rate 20m/ minute to this non-weaving cloth.
(embodiment 1)
Be unbodied inorganic particulate (Fig. 1 by be scaled solid content composition be the shape of 90 parts, hydrated alumina), be scaled sanlose (1% aqueous solution B viscosity 200mPas that solid content composition is 0.2 part, degree of etherification falling 0.65) mix with refiner, stir, then mixing is scaled sanlose (1% aqueous solution B viscosity 7000 mPas that solid content composition is 0.2 part, degree of etherification falling 0.7) and stir, then mixing is scaled latex that solid content composition is the styrene butadiene ribber of 6 parts and stirs, add ion exchange water further, make the coating fluid that solid content constituent concentration is the porous body of 20%.By on the nonwoven substrate 1 of gravure coater after above-mentioned hot calendered process, to make dry solid content composition for 10.2g/m 2mode, this coating fluid of even spread on a face of nonwoven substrate 1 is also dry, obtains the dividing plate that thickness is 25.2 μm.
(comparative example 1)
Use the rhombus column inorganic particulate (Fig. 2, hydrated alumina) of setting as inorganic particulate, in addition similarly to Example 1, prepare coating fluid, carry out being coated with, dry, the dry solid content composition obtaining porous body is 10.6g/m 2, thickness is the dividing plate of 25.8 μm.
(comparative example 2)
Use the cubic inorganic particulate (Fig. 3, hydrated alumina) of setting as inorganic particulate, in addition similarly to Example 1, prepare coating fluid, carry out being coated with, dry, the dry solid content composition obtaining porous body is 10.1g/m 2, thickness is the dividing plate of 25.2 μm.
< evaluates >
Dividing plate for embodiment and comparative example gained carries out following evaluation, and result is as shown in table 1.
[table 1]
Dry linting Pin hole
Embodiment 1 ○ ○
Comparative example 1 × ×
Comparative example 2 × ×
[dry linting evaluation]
For the dividing plate made, be cut into 50mm wide × strip of 200mm, fixed by upper end adhesive tape, slipped over thereon by the black cloth being loaded with 50g counterweight, visual confirmation black cloth now and dividing plate, evaluate according to following degree.
Zero: have no porous body peeling off the attachment of black cloth and porous body
×: black cloth surface is with porous body, and visible porous body peels off.
[pin hole evaluation]
For the dividing plate made, use transmitted light, in visual confirmation 10cm × 10cm dividing plate, the generation situation of pin hole, evaluates by following degree.
Zero: do not observe transmitted light completely, have no the generation of pin hole
×: the generation or uneven of visible pin hole.
In embodiment 1, in the dividing plate containing the porous body at least based on inorganic particulate, the shape of this inorganic particulate is amorphous, therefore in pin hole evaluation and dry linting evaluation, all obtains good result.In comparative example 1 and 2, inorganic particulate is not unbodied, is therefore bad result in pin hole evaluation or dry linting are evaluated.
" the second experiment "
(embodiment 2)
Shape is used to be inorganic particulate (Fig. 4 that unbodied tabular has depression, hydrated alumina) as inorganic particulate, in addition prepare coating fluid similarly to Example 1, carry out being coated with, dry, the dry solid content composition obtaining porous body is 10.2g/m 2, thickness 25.2 μm dividing plate.
(embodiment 3)
Shape is used to be inorganic particulate (Fig. 5 that unbodied tabular does not cave in, hydrated alumina) as inorganic particulate, in addition prepare coating fluid similarly to Example 1, carry out being coated with, dry, the dry solid content composition obtaining porous body is 10.5g/m 2, thickness 26.0 μm dividing plate.
(comparative example 3)
Use the columned inorganic particulate (Fig. 6, hydrated alumina) of setting as inorganic particulate, in addition to prepare coating fluid similarly to Example 1, carry out being coated with, dry, the dry solid content composition obtaining porous body is 10.2g/m 2, thickness 25.4 μm dividing plate.
< evaluates >
Dividing plate for embodiment and comparative example gained carries out following evaluation, and result is as shown in table 2.
[making of lithium rechargeable battery]
Use LiMn2O4 as positive active material, Delanium as negative electrode active material, lithium hexafluoro phosphate (LiPF 6) ethylene carbonate/diethyl carbonate/dimethyl carbonate mixed solvent (volume ratio 1/1/1) solution (1mol/L) as electrolyte, use each dividing plate of above-mentioned making as dividing plate, the painting face of dividing plate is made to be negative electrode active material side, bag (pouch) the formula lithium ion battery of assembling design capacity 30mAh.
[leakage current evaluation]
Use each lithium rechargeable battery of above-mentioned making, measure charging capacity when to carry out the charging of constant current constant voltage (1/10C cut-out) under 1C, 4.2V, calculate the ratio with design capacity, evaluate according to following degree.
Zero: lower than 125% of design capacity
△: be less than more than 125% 150% of design capacity
×: than more than 150% of design capacity.
[internal resistance evaluation]
Use each lithium rechargeable battery of above-mentioned making, aging (the activation (Inertia ら of 3 circulations is carried out with 1C, break-in) discharge and recharge), then constant current constant voltage charging (1/10C cut-out) is carried out with 1C, 4.2V, then discharge with 0.2C and 1C, calculate internal resistance value (Ω) by following formula (1).
Formula (1) internal resistance value (Ω)=(A-B)/C
A=discharges with 0.2C, reaches the voltage of 9 one-tenth capacity of the discharge capacity under 1C
B=discharges with 1C, reaches the voltage of 9 one-tenth capacity of the discharge capacity under 1C
C=(current value of 0.2C)-(current value of 1C).
[table 2]
Leakage current Internal resistance value (Ω)
Embodiment 2 ○ 4.1
Embodiment 3 ○ 5.1
Comparative example 1 × 4.9
Comparative example 2 × 4.1
Comparative example 3 × 4.7
The dividing plate of embodiment 2 contains the porous body at least based on inorganic particulate, and this inorganic particulate is unbodiedly have the shape having depression, and therefore the evaluation of leakage current and internal resistance value all obtains good result.
Shape is adopted to be amorphous but nonpitting inorganic particulate in the dividing plate of embodiment 3, therefore compared with the dividing plate of embodiment 2, the tendency that visible internal resistance raises, but in the evaluation of leakage current, obtain good result.In comparative example 1-3, inorganic particulate is the shape not having to cave in of setting, and be therefore deteriorated as seen tendency in the evaluation of leakage current.In addition, in the evaluation of internal resistance, comparative example 1 with 3 dividing plate compared with the dividing plate of embodiment 2, internal resistance value is high.
" the 3rd experiment "
The making > of < nonwoven substrate 2
Be 0.06dtex (fiber diameter 2.4 μm) by 45 parts of fiber numbers, fibre length is the oriented crystalline PET class short fiber of 3mm, 15 parts of fiber numbers are 0.1dtex (fiber diameter 3.0 μm), the oriented crystalline PET class short fiber of fibre length 3mm, be 0.2dtex (fiber diameter 4.3 μm) with 40 parts of fiber numbers, the single component type binding agent PET class short fiber (softening point 120 DEG C of fibre length 3mm, fusing point 230 DEG C) be mixed together, dissociated in water by pulp machine, the use slurry of manufacturing paper with pulp uniformly that concentration is 1% is prepared by the stirring of blender.Use cylinder paper machine, by the damp process system of copying, this is manufactured paper with pulp with slurry, then makes binding agent PET class short fiber bonding by the drying of 120 DEG C, and performance non-weaving cloth intensity, makes weight per unit area 15.2g/m 2non-weaving cloth.Further use comprises single nip hot pressing ray machine of metallic roll-metallic roll, implements heat treated, make the nonwoven substrate 2 of thickness 27 μm with roller temperature 185 DEG C, line pressure 740N/cm, transfer rate 20m/ minute to this non-weaving cloth.
(embodiment 4)
The pH7.8 that solid content composition is 90 parts will be scaled as inorganic particulate, hydrated alumina (the boehmite of viscosity 348mPas, Nabaltec company manufactures, trade name: APYRAL (registered trade mark)-AOH100XP), be scaled sanlose (1% aqueous solution B viscosity 200mPas that solid content composition is 0.2 part, degree of etherification falling 0.65) mix with refiner, stir, then, mixing is scaled sanlose (1% aqueous solution B viscosity 7000mPas that solid content composition is 0.2 part, degree of etherification falling 0.7) and stir, then mixing is scaled latex that solid content composition is the styrene butadiene ribber of 9 parts and stirs, add ion exchange water further, making solid content constituent concentration is the coating fluid of 20%.With gravure coater, this coating fluid of even spread on a face of the nonwoven substrate 2 after above-mentioned hot calendered process is also dry, and the dry solid content composition making porous body is 10.2g/m 2, obtain the dividing plate that thickness is 30.2 μm.
(comparative example 4)
Hydrated alumina (the boehmite that use pH8.4, viscosity are 2750mPas, Nabaltec company manufactures, trade name: ACTILOX (registered trade mark)-200SM) as inorganic particulate, in addition coating fluid is prepared similarly to Example 4, carry out being coated with, dry, the dry solid content composition obtaining porous body is 10.7g/m 2, thickness 31.2 μm dividing plate.
(comparative example 5)
Hydrated alumina (the boehmite that use pH7.9, viscosity are 6mPas, Nabaltec company manufactures, trade name: APYRAL (registered trade mark)-AOH60) as inorganic particulate, in addition coating fluid is prepared similarly to Example 4, carry out being coated with, dry, the dry solid content composition obtaining porous body is 10.5g/m 2, thickness 31.0 μm dividing plate.
(comparative example 6)
Hydrated alumina (the boehmite that use pH8.4, viscosity are 47mPas, great Ming chemical industry society manufactures, trade name: C20) as inorganic particulate, in addition coating fluid is prepared similarly to Example 4, carry out being coated with, dry, the dry solid content composition obtaining porous body is 10.1g/m 2, thickness 30.7 μm dividing plate.
(comparative example 7)
Hydrated alumina (the boehmite that use pH9.3, viscosity are 1720mPas, great Ming chemical industry society manufactures, trade name: C06) as inorganic particulate, in addition coating fluid is prepared similarly to Example 4, carry out being coated with, dry, the dry solid content composition obtaining porous body 2 is 10.4g/m 2, thickness 31.0 μm dividing plate.
(comparative example 8)
Hydrated alumina (the boehmite that use pH4.0, viscosity are 9mPas, SASOL company manufactures, trade name: DISPERAL (registered trade mark)-8F4) as inorganic particulate, in addition coating fluid is prepared similarly to Example 4, carry out being coated with, dry, the dry solid content composition obtaining porous body is 10.7g/m 2, thickness 31.2 μm dividing plate.
< evaluates >
Carry out following evaluation for the dividing plate made in embodiment and comparative example, result is as shown in table 3.
[table 3]
Pin hole
Embodiment 4 ○
Comparative example 4 △
Comparative example 5 △
Comparative example 6 △
Comparative example 7 ×
Comparative example 8 ×
[pin hole evaluation]
For the state of the pin hole of made dividing plate, use transmitted light, a slice dividing plate for A4 size carries out visual confirmation, evaluates by following degree.
Zero: the generation having no pin hole under visual
△: there is the part indistinctly observing transmitted light
×: observe a large amount of significantly transmitted light.
In the dividing plate of embodiment 4, inorganic particulate is following hydrated alumina: the pH of its 20 quality % water dispersion is less than more than 7.0 8.3, viscosity is more than 50mPas below 2000mPas, therefore obtains the good result that pin hole is few.
At the pH of water dispersion more than 8.3, viscosity also more than in the dividing plate of the comparative example 4 of 2000mPas and the dividing plate of viscosity lower than the comparative example 5 and 6 of 50mPas, pin hole is more than the dividing plate of embodiment 4.In addition, at the dividing plate of the comparative example 7 of pH significantly more than 8.3 and pH significantly lower than 7.0, in the dividing plate of viscosity also lower than the comparative example 8 of 50mPas, pin hole significantly increases.
" the 4th experiment "
The making > of < nonwoven substrate 3
Be 0.1dtex (fiber diameter 3.0 μm) by 60 parts of fiber numbers, fibre length is the single component type binding agent PET class short fiber (softening point 120 DEG C that the oriented crystalline PET short fiber of 3mm and 40 parts of fiber numbers are 0.2dtex (fiber diameter 4.3 μm), fibre length is 3mm, fusing point 230 DEG C) be scattered in water by pulp machine, preparation concentration is the use slurry of manufacturing paper with pulp uniformly of 1%.This is manufactured paper with pulp and copies system with slurry cylinder type paper machine by damp process, by the dryings of 135 DEG C make the crosspoint between binding agent PET class short fiber and binding agent PET class short fiber bonding with the crosspoint of oriented crystalline PET class short fiber, performance non-weaving cloth intensity, obtains weight per unit area 11g/m 2non-weaving cloth.Further use comprises single nip formula hot pressing ray machine of induction heating roller (metal hot-rolling) and resilient roller, with the condition of heat roller temperature 200 DEG C, line pressure 100kN/m, processing speed 30m/ minute, this non-weaving cloth is carried out hot calendered process, make the nonwoven substrate 3 of thickness 15 μm.
The preparation > of the coating fluid (the 1st coating fluid) of < the 1st porous body
By 100 parts of dispersion particle diameters be 2.3 μm, specific area is 3m 2the hydrated alumina of/g is as inorganic particulate, and 0.3% aqueous solution (0.4 part) being the sanlose of 200mPas with the viscosity of 1% aqueous solution at 25 DEG C mixes and fully stirs.Then, at mixing 25 DEG C, the viscosity of 1% aqueous solution is 0.5% aqueous solution (0.3 part) of the sanlose of 7000mPas and is-18 DEG C as the glass transition temperature of binding agent, disperses particle diameter be acrylate resin emulsion (solid content constituent concentration 50%) (6 parts) of 0.2 μm and stir, and makes the coating fluid of the 1st porous body.
Fig. 3 is the sweep electron microscope photo of used hydrated alumina.By the diagonal pitch of the inorganic particulate of this scanning electron-microscopic observation from intermediate value obviously less than 1/2 of above-mentioned dispersion particle diameter, this hydrated alumina is judged as " having agglutinate structure ".In table 4, when inorganic particulate is for " having agglutinate structure ", be designated as " aggegation ".
The preparation > of the coating fluid (the 2nd coating fluid) of < the 2nd porous body
By 100 parts of shapes be unbodied there is depression, dispersion particle diameter is 0.4 μm, specific area is 11m 2the hydrated alumina of/g is as inorganic particulate, and 0.3% aqueous solution (0.4 part) being the sanlose of 200mPas with the viscosity of 1% aqueous solution at 25 DEG C mixes and fully stirs.Then, at mixing 25 DEG C the viscosity of 1% aqueous solution be the sanlose of 7000mPas 0.5% aqueous solution (0.3 part) and as the glass transition temperature of binding agent be-18 DEG C, nonvolatile component concentration is 50%, dispersion particle diameter is the acrylate resin emulsion (6 parts) of 0.2 μm and stirs, and makes the coating fluid of the 2nd porous body.
Fig. 4 is the sweep electron microscope photo of used hydrated alumina.By the inorganic particulate diagonal pitch of this scanning electron-microscopic observation from intermediate value obviously larger than 1/2 of above-mentioned dispersion particle diameter, this hydrated alumina is judged as " not having agglutinate structure ".In table 4, when inorganic particulate is not for " having agglutinate structure ", be designated as " non-agglutination ".
(embodiment 5)
Use reverse kiss to be coated with the gravure coater of (kiss reverse) mode, described nonwoven substrate 3 is coated with the 1st coating fluid, makes coating weight be 6.0g/m 2, and dry with air drier, form the 1st porous body.Then use the gravure coater of reverse kiss painting mode, at the surface of the 1st porous body coating the 2nd coating fluid, make coating weight be 4.0g/m 2, and dry with air drier, make the dividing plate that thickness (measuring with micrometer) is 22 μm.
(embodiment 6-9, comparative example 9-18)
The coating weight of the agglutinate structure of the inorganic particulate of the 1st coating fluid and the 2nd coating fluid, dispersion particle diameter, each porous body is changed to shown in table 1, in addition similarly to Example 5, makes dividing plate.Table 4 also illustrates the thickness of each dividing plate.
(comparative example 19)
Use extrusion coating machine to replace gravure coater to carry out the coating of the 1st coating fluid, the 2nd coating fluid, in addition similarly to Example 5, make the dividing plate that thickness is 20 μm.
(comparative example 20)
On the opposite face being coated with the face of the 2nd coating fluid of the dividing plate of embodiment 5, then be coated with order 2 coating fluids, make coating weight be 6.0g/m 2, thus form the 3rd porous body, in addition similarly to Example 5, make the dividing plate that thickness is 32 μm.
(comparative example 21)
On the opposite face being coated with the face of the 2nd coating fluid of the dividing plate of embodiment 5, then be coated with order 1 coating fluid, make coating weight be 6.0g/m 2, thus form the 3rd porous body, in addition similarly to Example 5, make the dividing plate that thickness is 32 μm.
< evaluates >
[microscopic examination]
With the surface of each dividing plate made by scanning electron-microscopic observation, as a result, for the dividing plate of embodiment 5-9, comparative example 9-18, a face of nonwoven substrate is covered by the 2nd porous body, has the fiber of nonwoven substrate to expose at opposite face.For the dividing plate of comparative example 19, the fiber of nonwoven substrate is all had to expose in each face.For the dividing plate of comparative example 20, a face is covered by the 2nd porous body, and opposite face is covered by the 3rd porous body (using the 2nd coating fluid of embodiment 5), and each face does not all have exposing of nonwoven substrate fiber.For the dividing plate of comparative example 21, a face is covered by the 2nd porous body, and opposite face is covered by the 3rd porous body (using the 1st coating fluid of embodiment 5), and each face does not all have exposing of nonwoven substrate fiber.
[table 4]
[making of evaluation electricity pool]
Positive active material uses LiMn2O4, and negative electrode active material uses mesocarbon microbeads, and electrolyte uses lithium hexafluoro phosphate (LiPF 6) the mixed solvent solution of 1mol/L diethyl carbonate/ethylene carbonate (volume ratio 7/3), using each dividing plate of above-mentioned making as dividing plate, make the 2nd porous body relative with negative pole, make the pocket type lithium ion battery that design capacity is 30mAh.
[evaluation of leakage current]
For each evaluation electricity pool, carry out primary charging according to the order of " 30mA constant current charge → 4.2V constant voltage charging (stopping electric current 3mA) ", measure charging capacity now.Each dividing plate is divided into following 3 levels according to charging capacity.If charging capacity significantly exceedes design capacity 30mAh, then represent that inside battery produces leakage current.
Zero: primary charging capacity is lower than 35mAh
△: primary charging capacity is more than 35mAh but lower than 40mAh
×: primary charging capacity is more than 40mAh.
[evaluation of internal resistance]
Each evaluation electricity pool after evaluating for leakage current, carries out according to the order of " 30mA constant current charge → 4.2V constant voltage charging (1 hour) → 30mA constant current discharge (final voltage 2.8V) " aging (the activation discharge and recharge) of 2 circulations.Then with " 30mA constant current charge → 4.2V constant voltage charging (1 hour) " charging, then constant current discharge is carried out with 90mA.According to the following formula (2), by electric discharge, after 480 seconds, the voltage E of (the residual charge rate calculated is 60%) obtains internal resistance.
Formula (2) internal resistance=(3.88V-E)/90mA
The open circuit voltage of 3.88V is the residual charge rate of this evaluation electricity pool when being 50% battery, has nothing to do with dividing plate, is confirmed to be constant value.
Zero: internal resistance is lower than 4.0 Ω
△: internal resistance is that 4.0 more than Ω are lower than 5.0 Ω
×: internal resistance is 5.0 more than Ω.
As shown in table 4, the leakage current of the dividing plate of embodiment 5-9 is little, and thickness is thin, and internal resistance is low.In these dividing plates, be more than 1.0 μm less than 3.0 μm to disperse particle diameter, have the 1st porous body of the inorganic particulate of agglutinate structure and based on shape be amorphous, for have the shape of depression, dispersion particle diameter lower than 1.0 μm, the 2nd porous body of the inorganic particulate without agglutinate structure is laminated on nonwoven substrate successively, a face of nonwoven substrate is covered by the 2nd porous body in fact, opposite face has the fiber of nonwoven substrate expose.
On the other hand, only laminated based on disperse particle diameter more than 1.0 μm less than 3.0 μm, there is the comparative example 9 of the porous body of the inorganic particulate of agglutinate structure the leakage current of dividing plate large.In addition, by disperseing particle diameter to be more than 1.0 μm less than 3.0 μm, there is the porous body of the inorganic particulate of agglutinate structure to thicken and in the dividing plate of laminated comparative example 10, although inhibit leakage current, thickness is thick, and internal resistance is also high.Only laminated based on shape be amorphous, for have the shape of depression, dispersion particle diameter lower than 1.0 μm, the leakage current of the dividing plate without the comparative example 11 of the porous body of the inorganic particulate of agglutinate structure is large.
1st porous body is also large based on the leakage current of the dividing plate without the comparative example 12 of the inorganic particulate of agglutinate structure.1st porous body based on disperse particle diameter lower than 1.0 μm, the internal resistance of the dividing plate with the comparative example 13 of the inorganic particulate of agglutinate structure is high.1st porous body is also high with the internal resistance of the dividing plate disperseing particle diameter more than 3.0 μm, have the comparative example 14 that the inorganic particulate of agglutinate structure is main body.
2nd porous body is large based on the leakage current of the dividing plate with the comparative example 15 of the inorganic particulate of agglutinate structure.The dividing plate of the comparative example 16 thickened by the 2nd porous body of the inorganic particulate to have agglutinate structure can suppress leakage current, but thickness is thick, and internal resistance is also high.
1st porous body based on shape be amorphous, for have the shape of depression, dispersion particle diameter lower than 1.0 μm, not there is the inorganic particulate of agglutinate structure, the 2nd porous body is large based on the leakage current of the dividing plate disperseing particle diameter to be more than 1.0 μm less than 3.0 μm, have the comparative example 17 of the inorganic particulate of agglutinate structure.1st porous body based on shape be amorphous, for have the shape of depression, dispersion particle diameter lower than 1.0 μm, not there is the inorganic particulate of agglutinate structure, 2nd porous body is to disperse particle diameter to be more than 1.0 μm less than 3.0 μm, to have the inorganic particulate of agglutinate structure, and the dividing plate of the comparative example 18 making each porous body thicken can suppress leakage current, but thickness is thick, internal resistance is also high.
Be more than 1.0 μm less than 3.0 μm to disperse particle diameter, have the 1st porous body of the inorganic particulate of agglutinate structure and based on shape be amorphous, for have the shape of depression, dispersion particle diameter lower than 1.0 μm, the 2nd porous body of the inorganic particulate without agglutinate structure is laminated successively, but the dividing plate of the comparative example 19 that nonwoven substrate face is not covered by the 2nd porous body in fact, two faces of dividing plate all have fiber to expose, and in the dividing plate 20 and 21 that the two sides of dividing plate is all covered by porous body, the fiber of nonwoven substrate does not expose, leakage current is large.
Industrial applicability
Lithium ion battery dividing plate of the present invention is used for lithium ion battery purposes, in addition also can be used in manganese dry cell, alkaline manganese battery, silver oxide cell, lithium primary battery, lead accumulator, nickel-cadmium accumulator, nickel-hydrogen dattery, nickel-zinc battery, oxidation silver zinc storage battery, lithium polymer battery, various gel electrolyte battery, zinc-air accumulator, iron-air accumulator, aluminium-air accumulator, fuel cell, solar cell, sodium-sulphur battery, Polybenzol Batlery, electrolytic capacitor, double electric layer capacitor, lithium-ion capacitor etc.
Symbol description
1 nonwoven substrate
2 other porous bodies
3 porous bodies.

Claims (7)

1. the lithium ion battery dividing plate containing the porous body at least based on inorganic particulate, it is characterized in that, the shape of this inorganic particulate is amorphous.
2. lithium ion battery dividing plate according to claim 1, wherein, inorganic particulate has the shape having depression.
3. the lithium ion battery dividing plate described in claim 1 or 2, wherein, inorganic particulate is hydrated alumina.
4. the lithium ion battery dividing plate containing the porous body at least based on inorganic particulate, it is characterized in that, inorganic particulate is following hydrated alumina: the pH of its 20 quality % water dispersion is less than more than 7.0 8.3, and the viscosity of this water dispersion is more than 50mPas below 2000mPas.
5. the lithium ion battery dividing plate according to any one of claim 1-4, this lithium ion battery dividing plate contains nonwoven substrate.
6. lithium ion battery dividing plate according to claim 5, wherein, has the fiber of nonwoven substrate to expose at least one side.
7. lithium ion battery dividing plate, is characterized in that: the 1st porous body and the 2nd porous body are laminated on nonwoven substrate successively, and a face of nonwoven substrate is covered by the 2nd porous body in fact, has the fiber of nonwoven substrate to expose on opposite sides; Wherein, described 1st porous body disperses particle diameter to be more than 1.0 μm less than 3.0 μm, has the inorganic particulate of agglutinate structure for main body, the 2nd porous body be based on shape be amorphous, for have the shape of depression, dispersion particle diameter lower than 1.0 μm, not there is the inorganic particulate of agglutinate structure.
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