CN101180751B - Separator for lithium ion secondary battery and lithium ion secondary battery - Google Patents

Separator for lithium ion secondary battery and lithium ion secondary battery Download PDF

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Publication number
CN101180751B
CN101180751B CN200680017331XA CN200680017331A CN101180751B CN 101180751 B CN101180751 B CN 101180751B CN 200680017331X A CN200680017331X A CN 200680017331XA CN 200680017331 A CN200680017331 A CN 200680017331A CN 101180751 B CN101180751 B CN 101180751B
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dividing plate
rechargeable battery
lithium rechargeable
nonwoven fabrics
aromatic polyamide
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CN101180751A (en
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西川聪
本元博行
大道高弘
佐野弘树
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Teijin Ltd
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Teijin Ltd
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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
    • 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
    • H01M50/423—Polyamide resins
    • 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
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • 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
    • H01M50/403—Manufacturing processes of separators, membranes or diaphragms
    • 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
    • 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
    • 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
    • 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
    • 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
    • H01M50/454—Separators, membranes or diaphragms characterised by the material having a layered structure comprising a non-fibrous layer and a fibrous layer superimposed on one another
    • 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
    • H01M50/463—Separators, membranes or diaphragms characterised by their shape
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
    • H01M50/491—Porosity
    • 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
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • 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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Ceramic Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Cell Separators (AREA)
  • Secondary Cells (AREA)

Abstract

Disclosed is a membrane as a separator for lithium ion secondary batteries wherein a porous layer mainly composed of an aromatic polyamide is formed on both sides of a nonwoven fabric. This separator has sufficiently high heat resistance and good handling properties, and is an effective measure against overcharging. Safety of a lithium ion secondary battery can be improved by using such a separator.

Description

Lithium rechargeable battery is with dividing plate and lithium rechargeable battery
Technical field
The dividing plate that the present invention relates to use in the lithium rechargeable battery.Be particularly related to the dividing plate technology that rises to purpose with the fail safe of lithium rechargeable battery.
Background technology
Therefore embedding by lithium ion and take off the lithium rechargeable battery that embedding obtains electromotive force and have the feature of high-energy-density, is extensively popularized as the battery of portable electric appts such as mobile phone, notebook computer.In addition, also begin to be applied to improve the power supply purposes of the electric tool etc. of power.
In recent years, owing to making, the earth environment problem increases for the concern of hybrid electric vehicle (HEV), present situation is generally to use Ni-MH battery as battery, but comparing with Ni-MH battery, lithium rechargeable battery do not have memory effect therefore to use easily, in addition, therefore advantage that can miniaturization owing to have high-energy, high output density etc. is studied with battery as HEV.When being considered as HEV and using battery, be different with the requirement of portable electric appts certainly.For example, battery is exposed to the possibility height under the high temperature among the HEV, therefore guarantees that the fail safe under the hot environment is a very important characteristic.As mentioned above, the desired characteristic of battery is different in portable electric appts and HEV, so the desired characteristic of the component parts of battery is also different certainly.
In the present lithium rechargeable battery, the micro-porous film that the use polyethylene is made is as dividing plate.This dividing plate has closing function, helps to guarantee the fail safe of battery.This closing function is to have utilized the micro-porous film heat fusing to make the inaccessible this point in hole, is characterized by thermal cut temperature (Hot ヒ ユ one ズ temperature) and short circuit temperature.The thermal cut temperature is because the hole obturation temperature that causes dividing plate resistance to begin to rise, and the short circuit temperature is partition ruptures and temperature that dividing plate resistance sharply descends.Between this thermal cut temperature and the short circuit temperature, dividing plate resistance is very high, can block electric current.It is said this function guarantees it is effective for the fail safe of external short circuit etc.
Under the situation of HEV, be assumed to from the outside the actively situation of heating.When considering closing function in such purposes, thermal cut may be exposed to high temperature decreased performance of following time relation arranged, rupture of membranes may on firely have a relation with internal short-circuit anodal and negative pole cause.Therefore, the dividing plate that has closing function at present in HEV may not be effective, thinks that having abundant stable on heating dividing plate is fit to.
Structure about the high dividing plate of thermal endurance has proposed several schemes.For example, the nonwoven fabric sheet that constitutes by such as the high fiber of thermal endurances such as aromatic polyamide fibre has been proposed in No. 3142693 grade of Japan Patent.The such form mesh of nonwoven fabrics is big, with prevent the both positive and negative polarity short circuit and keep the relevant characteristic of the such dividing plate of electrolyte essence insufficient, in order to reduce mesh, can use fine fibre, but in the present technical merit, it is very difficult with the dividing plate of dividing plate to obtain being suitable as lithium rechargeable battery, does not have practicability.
In addition, the perforated membrane that constitutes by such as the high polymer of thermal endurances such as aromatic polyamide has been proposed in WO01/019906 specification etc.This system is from because the viewpoint of the short circuit that causes of rupture of membranes considers that thermal endurance is sufficient.But owing to inner overcharging and causing energetically under the situation of heating, battery might be on fire because of runaway reaction, under such situation fail safe guarantee insufficiently, have other Security Countermeasures complicated problems that becomes.In addition, the perforated membrane that is made of aromatic polyamide considers also to exist the low problem of productivity ratio from the viewpoint of intensity.
The technology of giving closing function on the perforated membrane that is made of the high polymer of aforesaid thermal endurance has also been proposed.For example, the technology that is coated with the porous layer that is made of the high-fire resistance resin on the perforated membrane of closing function having is disclosed in the TOHKEMY 2001-23602 communique.But the resistance of the resistance after the thermal cut before with respect to thermal cut only rises to about 10 times, and sufficient closing function aspect the fail safe of guaranteeing battery therefore is difficult to say so.In addition, in Japanese kokai publication hei 10-6453 communique, proposed in the perforated membrane that constitutes by heat-resistant resin to mix constituting of the particulate that constitutes by polyethylene.This system can not obtain sufficient closing function equally.
Constituting of porous layer that coating is made of the polyvinylidene fluoride alkene copolymer proposed in the WO01/067536 specification on the nonwoven fabrics that the fiber high by thermal endurance constitutes.Having put down in writing in this specification can realize overcharging by the form of suitably controlling dividing plate prevents the technology essential factor of function.In addition, the suitable manufacture method relevant with this morphology Control disclosed in the TOHKEMY 2003-171495 communique.But, the thermal endurance of the polyvinylidene fluoride alkene copolymer that expands in electrolyte is high anything but, at high temperature produce fusion, therefore think that the thermal endurance of this system is guaranteed by nonwoven fabrics, prevent that the both positive and negative polarity short circuit lacks the such problem of reliability but similarly exist by nonwoven fabrics with the discussion of No. the 3142693rd, Japan Patent.
In Japanese kokai publication hei 10-324758 communique, disclose with the contraposition aromatic polyamide polymer of porous and covered the surface of the base material that constitutes by fiber or paper pulp and space and the dividing plate that forms.Japan Patent is for No. 3175730 the system of disperseing pottery on the basis of the system of Japanese kokai publication hei 10-324758 communique in porous layer.The method for making of the dividing plate of putting down in writing in these patent documentations is: by nonwoven fabrics being placed on the carrier board and beginning to be coated with contraposition aromatic polyamide polymer coating from the top, the method that contraposition aromatic polyamide polymer is separated out obtains perforated membrane.This method in fact can not be at the contraposition aromatic polyamide polymer of the two sided coatings porous of nonwoven fabrics, obviously just single face coating.In addition, speed of separating out also is different in the table, and therefore the form of porous layer becomes very asymmetric in the table.Dividing plate with difference in so remarkable table is difficult to form suitable electrode/dividing plate interface, has problems on the battery performance, and is impracticable.In addition, therefore there is the problem of serviceability difference owing to curl.In addition, contraposition aromatic polyamide polymer also exists coating to regulate or the such problem of difficulty that is shaped.Particularly, the hole is difficult to form continuously, and can only form very little hole, therefore can not obtain sufficient ion permeability.In addition, also there is the manufacture method complicated problems in this technology.
Summary of the invention
As previously mentioned, the high dividing plate of thermal endurance of heat-resistant resins such as application aromatic polyamide has been proposed, but also not have at present to find with this thermal endurance is the formation of the good dividing plate of fail safe, the productivity ratio of characteristic remarkable ground raising lithium rechargeable battery, does not reach practicability as yet.The inventor thinks, from the viewpoint of the fail safe of guaranteeing lithium rechargeable battery, it is the countermeasure of overcharging that is caused runaway reaction by own heating of inside that the dividing plate that thermal endurance is fully high lacks.Therefore, the object of the present invention is to provide a kind of thermal endurance fully high, for overcharging countermeasure also effectively and the good dividing plate of operating characteristics.
The inventor has carried out extensive and deep research to above-mentioned problem, found that, in the table of nonwoven fabrics two sided coatings mainly comprise the porous layer of aromatic polyamide and the dividing plate that obtains, be effectively in the fail safe of guaranteeing lithium rechargeable battery, finally finished the present invention.That is, the invention provides a kind of lithium rechargeable battery dividing plate, wherein, the two sides has formed the porous layer that mainly comprises meta-aromatic polyamide in the table of nonwoven fabrics.In addition, the invention provides following invention.
1. the lithium rechargeable battery dividing plate of foregoing invention, wherein, the thickness of this dividing plate is that 15 to 40 μ m, Gurley value (JIS P8117) they are 10 to 50 seconds/100cc;
2. each described lithium rechargeable battery dividing plate among foregoing invention or the 1st, wherein, be attached with surfactant on the described porous layer, described surfactant comprises and is selected from least a in the group that is made of cationic surfactant, anion surfactant, amphoteric surfactant and non-ionic surface active agent;
3. above-mentioned the 2nd described lithium rechargeable battery dividing plate, wherein, the adhesion amount of described surfactant is 0.005 to 0.750g/m 2
4. each described lithium rechargeable battery dividing plate among foregoing invention or the 1st to 3, wherein, described nonwoven fabrics is for mainly comprising the nonwoven fabrics of PETG;
5. above-mentioned the 4th described lithium rechargeable battery dividing plate, wherein, the weight that mainly comprises the described porous layer of meta-aromatic polyamide is 4 to 10g/m 2
6. each described lithium rechargeable battery dividing plate among foregoing invention or the 1st to 3, wherein, described nonwoven fabrics is for mainly comprising the nonwoven fabrics of meta-aromatic polyamide;
7. each described lithium rechargeable battery dividing plate among foregoing invention or the 1st to 3, wherein, described nonwoven fabrics comprises meta-aromatic polyamide short fiber and contraposition aromatic polyamide pulp;
8. each described lithium rechargeable battery dividing plate among foregoing invention or the 1st to 5, wherein, described meta-aromatic polyamide is a poly;
9. each described lithium rechargeable battery dividing plate among foregoing invention or the 1st to 8 wherein, contains the ceramic particle of average grain diameter 0.05 to 2 μ m in the described porous layer, is 30 to 80 weight % with respect to the weight ceramic particle of porous layer;
10. a lithium rechargeable battery is with the manufacture method of dividing plate, wherein, to be the polymer solution of the solvent of good solvent with meta-aromatic polyamide with to this meta-aromatic polyamide as principal component, coat two sides in the table of nonwoven fabrics, making the nonwoven fabrics after the coating then is to solidify in the solvent of poor solvent and the mixed liquor for the solvent of good solvent mainly comprising this meta-aromatic polyamide, then washing, drying;
11. a lithium rechargeable battery has positive pole, negative pole, nonaqueous electrolytic solution and dividing plate, the embedding by lithium ion and take off embedding and obtain electromotive force, and wherein, dividing plate is that the two sides has formed the porous layer that mainly comprises meta-aromatic polyamide in the table of nonwoven fabrics;
12. above-mentioned the 11st described lithium rechargeable battery, wherein, the thickness of described dividing plate is that 15 to 40 μ m, Gurley value (JIS P8117) are 10 to 50 seconds/100cc;
13. the lithium rechargeable battery described in above-mentioned the 11st or 12, wherein, be attached with surfactant on the described porous layer, described surfactant comprises and is selected from least a in the group that is made of cationic surfactant, anion surfactant, amphoteric surfactant and non-ionic surface active agent;
14. above-mentioned the 13rd described lithium rechargeable battery dividing plate, wherein, the adhesion amount of described surfactant is 0.005 to 0.750g/m 2
15. each described lithium rechargeable battery in above-mentioned the 11st to 14, wherein, described nonwoven fabrics is for mainly comprising the nonwoven fabrics of PETG;
16. above-mentioned the 15th described lithium rechargeable battery, wherein, the weight that mainly comprises the described porous layer of meta-aromatic polyamide is 4 to 10g/m 2
17. above-mentioned the 15th described lithium rechargeable battery, wherein, the electrolyte of electrolyte is with LiPF 6Be main body,, contain vinylene carbonate or the vinyl acetate of 0.5 to 5 weight % with respect to the solvent total weight;
18. each described lithium rechargeable battery in above-mentioned the 11st to 14, wherein, described nonwoven fabrics is for mainly comprising the nonwoven fabrics of meta-aromatic polyamide;
19. each described lithium rechargeable battery in above-mentioned the 11st to 18, wherein, described meta-aromatic polyamide is a poly.
Description of drawings
Fig. 1 is the result of overcharge test.
Embodiment
Below, mode of the present invention is described.
[dividing plate]
Lithium rechargeable battery dividing plate of the present invention is characterized in that, the two sides has formed the porous layer that mainly comprises meta-aromatic polyamide in the table of nonwoven fabrics.By using nonwoven fabrics can improve porous film strength and the dimensional stability that comprises aromatic polyamide, improve operating characteristics and productivity ratio.
At this, the two sides forms the porous layer that mainly comprises meta-aromatic polyamide in the table of nonwoven fabrics, when being meant in the table of observing dividing plate, is all covered by the porous layer that comprises aromatic polyamide in the table, cannot see the fiber that constitutes nonwoven fabrics.This can be observed at an easy rate by ESEM (SEM).Table and in constitute the dividing plate that the fiber of nonwoven fabrics exposes among either party or two sides, the joint interface of electrode and dividing plate is inhomogeneous, battery performance generation fault.Its main cause is that the electrolyte retentivity in electrode/dividing plate interface is insufficient, and along with the electrolyte exhaustion of circulation through existing in electrode/dividing plate interface, the flash-over characteristic of cycle characteristics or circulation process is bad.
In the dividing plate of the present invention, the layer that forms in nonwoven surface is the porous layer that comprises meta-aromatic polyamide.Need to form continuously the hole in the porous layer, the structure of this porous layer can be an index with Gurley value (JIS P8117).The Gurley value of dividing plate of the present invention is suitably 10 to 50 seconds/100cc.When the Gurley value was lower than 10 seconds/100cc, nonwoven fabrics formed fiber and exposes or exist pin hole, and the probability height that such defect part exists is therefore not preferred.In addition, ion permeability is insufficient during greater than 50 seconds/100cc, and multiplying power property (レ one ト characteristic) descends, and is therefore not preferred.In addition, be difficult to obtain well overcharging of WO01/067536 specification record and prevent function, the viewpoint of the fail safe when guaranteeing to overcharge is considered not preferred.
In the dividing plate of the present invention, thickness is suitably 15 to 40 μ m.Thickness during less than 15 μ m the original short circuit of dividing plate prevent that function is insufficient.In addition, follow the resistance of ionic conduction to uprise when surpassing 40 μ m, it is insufficient to produce multiplying power property, and perhaps the problem that do not raise of the energy density of battery is therefore not preferred.
In order to realize above-mentioned block board thickness, preferred nonwoven thickness is about 10 to about 39 μ m, comprises in the porous layer thickness table of meta-aromatic polyamide to add up to about 1 to about 10 μ m.The actual strength of dividing plate of the present invention determined by nonwoven fabrics, but nonwoven thickness is difficult to guarantee as the abundant intensity of lithium ion battery with dividing plate during less than 10 μ m.In addition, when surpassing 39 μ m, making block board thickness is to be actually the comparison difficulty below the 40 μ m.In addition, when adding up in this porous layer thickness table, in fact be difficult to all cover nonwoven fabrics table the inside less than 1 μ m, therefore not preferred.This porous layer is probably being controlled the ionic conduction resistance of dividing plate, when surpassing 10 μ m, considers it is not preferred from the viewpoint of guaranteeing discharge property.
The preferred mesh of the nonwoven fabrics that uses in the dividing plate of the present invention is tiny as far as possible, in order to obtain so tiny nonwoven fabrics of nonwoven fabrics optimum fiber diameter.From the viewpoint, the fibre diameter that constitutes the fiber of nonwoven fabrics is suitably below the 10 μ m, further below the preferred 5 μ m.
When nonwoven fabrics is shaped, need be used for binder with principal fiber and principal fiber combination.Be used for binder optimum fiber or pulp that this nonwoven fabrics is shaped.
The manufacture method of this nonwoven fabrics can application of known method.Particularly, can enumerate: dry process, water acupuncture manipulation, wet type are copied paper method, spun-bond process, meltblown, electrical spinning method etc.When considering thin paperization with the mesh uniformity, preferred especially wet type is copied the paper method.
If constitute that the material of this nonwoven fabrics has sufficient thermal endurance and to the patience of electrolyte, then be not particularly limited, can enumerate particularly: be polyester, aromatic polyamide, polysulfones, polyether sulfone, polyphenylene sulfide, polyimides of representative etc. with PETG (PET).Consider preferred especially PET from fiber and the high viewpoint of thermal endurance that easy formation is thinner.In addition, consider from the viewpoint of high strength and high-fire resistance, the preferred fragrance polyamide, preferred especially meta-aromatic polyamide considers that from the viewpoint of formability poly is particularly suitable.In not influencing the stable on heating scope of nonwoven fabrics, also can be in this nonwoven fabrics the TPO fiber of mix polyethylene, polypropylene etc., when sneaking into these materials on a small quantity, the situation that exists fail safe to improve.The addition of the polyolefine fiber of this moment is preferably below the 30 weight % with respect to the weight of this nonwoven fabrics.
Consider that from film and high-intensity viewpoint use comprises the short fiber of meta-aromatic polyamide and the nonwoven fabrics of contraposition aromatic polyamide pulp is particularly suitable for.This nonwoven fabrics and the affinity height that is used to form the meta-aromatic polyamide of porous layer can obtain high strength by compoundization.In addition, the nonwoven fabrics of said structure becomes film easily.
In the dividing plate of the present invention, it is more suitable that the material of formation porous layer is mainly meta-aromatic polyamide.Aromatic polyamide is for being the contraposition aromatic polyamide of representative with the PPTA and being the meta-aromatic polyamide of representative with the poly, preferred meta-aromatic polyamide in the dividing plate of the present invention, preferred especially poly.The dissolubility of contraposition aromatic polyamide in solvent is low, even also have very high viscosity under the low concentration, therefore is very difficult to form intensity, ion permeability this porous layer fully.Particularly, only form aperture, and these holes are discontinuous, so ion permeability is insufficient.Relative therewith, meta-aromatic polyamide is fully dissolving in solvent, from the suitable polymer solution of the easy preparation of the viewpoint of concentration and viscosity.In addition, aperture control is also easy, can guarantee sufficient ion permeability.For show the WO01/067536 specification overcharge and prevent function, need suitably control the aperture of this porous layer especially, consider that from additional such functional point of view meta-aromatic polyamide is more suitable than contraposition aromatic polyamide.
Form the main preferred meta-aromatic polyamide of material of this porous layer, in the feature that does not influence meta-aromatic polyamide is the scope of structure control of thermal endurance and porous layer, also can mix other material.Specifically can enumerate: contraposition aromatic polyamide, polysulfones, polyether sulfone, Kynoar, polyvinylidene fluoride alkene copolymer, polyacrylonitrile, polymethyl methacrylate, poly(ethylene oxide), PPOX, PVP etc., these compositions are to be fit to below the 30 weight % with respect to the meta-aromatic polyamide that is used to form porous layer.
PET is used under the situation of nonwoven fabrics, the weight that forms the meta-aromatic polyamide of this porous layer is 4 to 10g/m 2Be suitable.When PET is used for lithium rechargeable battery and uses separator material, the durability existing problems under the particular surroundings, but by can significantly improving durability with meta-aromatic polyamide is compound.The weight of meta-aromatic polyamide is less than 4g/m 2The time, durability is improved insufficient, and is therefore not preferred.Weight surpasses 10g/m 2The time, the problem of generation ion permeability variation.
Meta-aromatic polyamide among the present invention is dissolved under the situation in the N-N-methyl-2-2-pyrrolidone N-, is 0.8 to 2.5dl/g with the logarithmic viscosity number of following formula (1) expression preferably, the polymer of preferred 1.0 to 2.2dl/g scopes.Logarithmic viscosity number can not get sufficient mechanical during less than 0.8dl/g, and logarithmic viscosity number is difficult to obtain stable polymer solution when surpassing 2.5dl/g, and is therefore not preferred in order to form uniform porous layer.
Logarithmic viscosity number (unit: dl/g)=ln (T/T0)/C (1)
T: meta-aromatic polyamide 0.5g is dissolved in the solution that forms among the N-N-methyl-2-2-pyrrolidone N-100mL flowing time at 30 ℃ of following capillary viscometers
The T0:N-N-methyl-2-2-pyrrolidone N-is at the flowing time of 30 ℃ of following capillary viscometers
C: the polymer concentration in the polymer solution (g/dl).
In the dividing plate of the present invention, consider that from anlistatig viewpoint the attaching surface activating agent also is fit on this porous layer.This surfactant is not particularly limited, and for example can use the surfactant of cationic, anionic species, zwitterionic classes, nonionic class.As the cationic surfactant, can enumerate higher amines halogen acid salt, halogenated alkyl pyridine, quaternary ammonium salt etc.As the anionic species surfactant, can enumerate higher fatty acids alkali salt, polyoxyethylene alkyl ether sulphonic acid ester salt, polyoxyethylene alkyl ether phosphonate, alkyl sulfate, alkylsulfonate, alkylaryl sulfonates, sulfosuccinate ester salt etc.As the zwitterionic classes surfactant, can enumerate alkyl betaine compounds, imidazolines, alkyl amine oxide, dioxy borate (bisoxyborate) compounds etc.As non-ionic surface active agent, can enumerate polyoxyethylene alkyl ether class, polyoxyethylene alkyl phenyl ether class, polyxyethylated allyl ether series, fatty acid glyceride, polyoxyethylene sorbitan fatty acid ester, fatty acid esters of sorbitan etc.
Particularly the antistatic effect of cationic surfactant, anionic species surfactant, zwitterionic classes surfactant is strong, can reduce use amount, therefore preferred the use.In addition,, also can improve the affinity of aromatic polyamide and surfactant, improve antistatic effect by these are mixed.
The expectation of the adhesion amount of surfactant is 0.005 to 0.750g/m 2, when being lower than 0.005g/m 2The time, can not get sufficient antistatic effect, and when surpassing 0.750g/m 2The time, battery performance is had a negative impact.Can by measure by after the coating surface activating agent in 10 hours battery separator of 90 ℃ of vacuumize, with the solvent that impregnated in the solubilized surfactant in back of poor quality in 10 hours battery separator of 90 ℃ of vacuumize, the extraction composition that obtains after perhaps will solution dry solidification with the solvent extraction of solubilized surfactant, carry out methods such as assay determination quality by H-NMR or gas chromatography etc., thereby can obtain the adhesion amount of surfactant.
As the method for estimating static, can use the frictional electrification voltage determination method of JIS L 1084.The half-life of the static of measuring by frictional electrification voltage determination method is to be suitable below 30 seconds.Half-life is more than 30 seconds the time, and the decay of static is slow, so antistatic effect is insufficient.
[autofrettage of dividing plate]
Lithium rechargeable battery of the present invention can be by the whole bag of tricks manufacturing, for autofrettage without limits with dividing plate.For example, can enumerate by making the method for its crimping in the face of the processing of pressurizeing of meta-aromatic polyamide perforated membrane at two of nonwoven fabrics; Comprise the polymer solution of meta-aromatic polyamide in the two sided coatings of nonwoven fabrics, make the method for this coating layer generation microphase-separated etc. by any method in dry process, dry-and wet-type method and the damp process.
Especially, to be that the solvent of good solvent is that the polymer solution of main component is coated on two sides in the table of nonwoven fabrics with meta-aromatic polyamide with to it, making the nonwoven fabrics after the coating then is to solidify in the solvent of poor solvent and the mixed liquor (solidification liquid) for the solvent of good solvent mainly comprising meta-aromatic polyamide, washing, drying then, this autofrettage (wet type microphase-separated method) is what relatively to be fit to.By adopting this manufacture method, the honeycomb sandwich control of meta-aromatic polyamide porous layer becomes easy.In addition,, can not make nonwoven fabrics constitute fiber because of the dipping of polymer solution is bad and expose by being coated with on two cloth in the table, can the high dividing plate of workmanship.
Can use patent documentation 6 described manufacturing installation or notions particularly about above-mentioned autofrettage.Specifically can enumerate: as the coating method that polymer solution is coated on two sides in the nonwoven fabrics table, supply with excessive polymer solution from the two sides of nonwoven fabrics, nonwoven fabrics is passed through between opposed a pair of silk rod (マ イ ヤ one バ one) or the mould, in this mode of measuring.The nonwoven fabrics that further will be coated with polymer solution impregnated in and makes in the solidification liquid that the two sides contacts with solidification liquid in the table, can form the porous layer that solidifies in the two sides in the table of nonwoven fabrics thus.
In this autofrettage, this good solvent is that amide solvent is more suitable, for example, and preferred dimethylacetylamide, N-N-methyl-2-2-pyrrolidone N-etc.In addition, this poor solvent specifically can be enumerated alcohols, water etc., and water is particularly suitable for.
Polymer concentration as this polymer solution, depend on kind, the degree of polymerization of employed meta-aromatic polyamide greatly, therefore can not generally determine, still, when for example using poly, the scope of 5 to 20 weight % is most suitable.
When polymer concentration hangs down, can obtain the good especially dividing plate of ion permeability, but because the viscosity of polymer solution is low, the viewpoint from pin hole etc. when coating nonwoven fabrics considers that productivity ratio is insufficient.Reduce the polymer concentration of polymer solution, when obtaining the good especially dividing plate of ion permeability, the method for adding ceramic particle in this polymer solution is very suitable.By adding ceramic particle, the viscosity of this polymer solution increases, and also can easily coat nonwoven fabrics even polymer concentration is low.
As this ceramic particle, can enumerate particularly: silicon dioxide, aluminium oxide, zirconia, magnesium oxide, titanium oxide, barium titanate, aluminium nitride, calcium oxide, calcium carbonate, lithium fluoride, lithia etc.Particularly suitable is aluminium oxide, zirconia, magnesium oxide.
The average grain diameter of this ceramic particle is suitably 0.05 to 2 μ m, the scope of preferred especially 0.1 to 1 μ m.Ceramic particle is 0.05 μ m when following, considers from the viewpoint of aggegation etc., is difficult to operate.In addition, be 2 μ m when above, it is therefore not preferred to be easy to generate a mouthful mould striped (ダ イ muscle) when coating.At this, average grain diameter can be measured by the determination of laser diffraction method, the median particle diameter (D50) in the expression volume particle size distribution.In addition, the average grain diameter among the present invention is meant the average grain diameter of primary particle.
The addition of this ceramic particle is suitably determined by the polymer concentration of taking into account polymer solution, generally speaking, be preferably 30 to 80 weight % with respect to the meta-aromatic polyamide that forms this porous (in it is also contained in when containing other organic polymer) and the weight of ceramic particle.The amount of ceramic particle can not get sufficient thickening effect during less than 30 weight %, and effect is insufficient.In addition, when the amount of ceramic particle surpasses 80 weight %, produce problems such as powder when being configured as dividing plate, therefore not preferred.
The additive effect of the ceramic particle on this autofrettage when the polymer concentration in this polymer solution be that 10 weight % are particularly suitable for when following.
In addition, the additive effect of ceramic particle not only has the effect in the above-mentioned autofrettage, and has the feature on the formation of the following stated.The general thermal endurance of ceramic particle is than meta-aromatic polyamide height, even when battery temperature rises near 400 ℃ of meta-aromatic polyamide thermal decomposition, because the formation of having added ceramic particle also works as dividing plate.In addition, ceramic particle also works as lubricant, and the operating characteristics when helping antistatic effect or producing static improves.
In order to control loose structure, can in this polymer solution, add phase separation agent.Phase separation agent is if be poor solvent with respect to meta-aromatic polyamide, and compatible in solidification liquid, just can use.Particularly, water or alcohols are fit to, and especially preferably contain propylene glycol, ethylene glycol, diethylene glycol, the tripropylene glycol, 1 of polymer, 3-butanediol, 1, polyalcohols such as 4-butanediol, polyethyleneglycol ether, methyl alcohol, ethanol, glycerine etc.The concentration of the phase separation agent in this polymer solution is with respect to the scope that is fit to select 0 to 40 weight % in the mixed liquor of this good solvent and phase separation agent.
This solidification liquid is preferably the mixed liquor of aforementioned good solvent and poor solvent.At this, when using phase separation agent in polymer solution, mixing this phase separation agent with suitable ratio in solidification liquid is preferred in process management.Particularly, the ratio of this good solvent in this polymer solution and phase separation agent and the ratio in the solidification liquid is consistent is fit to.
The ratio of this poor solvent in this solidification liquid is answered in this poor solvent under the situation of water, and the scope of suitable from 10 to 80 weight % is selected.
Next the nonwoven fabrics that has formed the porous layer that solidifies moves to washing step, then in drying process with the water drying, can obtain dividing plate of the present invention thus.At this, drying process is fit to selection and contacts the dry mode of carrying out with warm-up mill.
In the autofrettage of dividing plate of the present invention, when surfactant is adhered to, its method has no particular limits, and can enumerate: with surfactant dissolves in solvent, to perforated membrane spraying and make its dry method or make the perforated membrane dipping and make its dry method etc.
[lithium rechargeable battery]
Usually, lithium rechargeable battery is to flood electrolyte by clipping at anodal and negative pole in the cell device that the dividing plate relative bonding forms, and is encapsulated into then to constitute in the external packing.Lithium rechargeable battery of the present invention is characterized in that using aforementioned dividing plate of the present invention, and other inscape can the application of known technology, does not have in essence restriction for other inscape.
The general use of negative pole will be coated on the current-collector and the negative pole that forms by the layer that negative electrode active material, adhesive and conductive auxiliary agent form.Thereby mediate and make slurry by in negative electrode active material, adhesive and conductive auxiliary agent, adding solvent, this slurry is coated on the current-collector, carry out drying, compacting then, make negative pole thus.The total weight of negative electrode active material, adhesive and conductive auxiliary agent was made as 100% o'clock, and the weight of negative electrode active material is 80 to 98 weight %, and adhesive is 2 to 20 weight %, and conductive auxiliary agent is that the scope of 0 to 10 weight % suits.Can enumerate as negative electrode active material: material with carbon element, silicon, tin etc.Can enumerate as material with carbon element: with the material with carbon element that obtains as precursor such as easy graphited pitches such as carbonaceous mesophase spherules or little carbon fiber etc.; To be difficult to material with carbon element that graphited material obtains as precursor etc. such as phenolic resins etc.Can enumerate as adhesive: Kynoar or carboxymethyl cellulose etc.Suitable powdered graphite, acetylene black, Ketjen black (ケ Star チ エ Application Block ラ Star Network), the gas-phase growth of carbon fibre etc. of using of conductive auxiliary agent.Suitable Copper Foil, the stainless steel etc. of using of current-collector.
Positive pole is also same with negative pole, and general use will be by layer coating on the current-collector and the positive pole that obtains that positive active material, adhesive and conductive auxiliary agent form.Thereby mediate and make slurry by in positive active material, adhesive and conductive auxiliary agent, adding solvent, this slurry is coated on the current-collector, carry out drying, compacting then, make anodal thus.The total weight of positive active material, adhesive and conductive auxiliary agent was made as 100% o'clock, and the weight of positive active material is 80 to 98 weight %, and adhesive is 2 to 20 weight %, and conductive auxiliary agent is that the scope of 0 to 10 weight % suits.Can enumerate as positive active material: LiCoO 2, LiNiO 2, spinel-type LiMn 2O 4, olivine-type LiFePO 4Deng and in these materials, make element solid solution not of the same race and the material that forms, these materials also can mix use.As the adhesive Kynoar that can suit to use.Suitable powdered graphite, acetylene black, Ketjen black (ケ Star チ エ Application Block ラ Star Network), the gas-phase growth of carbon fibre etc. of using of conductive auxiliary agent.Suitable Copper Foil, the stainless steel etc. of using of current-collector.
Electrolyte uses lithium salts is dissolved in the nonaqueous solvents and the nonaqueous electrolytic solution that obtains.As lithium salts, the suitable LiPF that uses 6, LiBF 4, LiClO 4Deng.Nonaqueous solvents can be enumerated: propylene carbonate (PC), ethylene carbonate (EC), dimethyl carbonate (DMC), diethyl carbonate (DEC), methyl ethyl carbonate (EMC) etc.These lithium salts and nonaqueous solvents can use separately also can mix use two or more.The concentration of lithium salts suits in 0.5 to 2.0M scope.In addition, adding vinylene carbonate (VC), vinyl acetate (VA) in electrolyte considers to be fit to from the viewpoint of durability.
In the lithium rechargeable battery of the present invention, the cell device that will comprise above-mentioned positive pole, negative pole and dividing plate is reeled and is made cylindric or flat, perhaps makes laminar structure, is encapsulated in the external packing again.Prevent the functional point of view consideration from showing well to overcharge, preferably have warp architecture, especially preferably reel and make the structure of flat.
External packing can be implemented with any form of metal shell, aluminium lamination press mold housing etc.
Embodiment
Below, by embodiment in detail the present invention is described in detail.But, the invention is not restricted to following examples.
[embodiment 1]
PET short fiber and the PET short fiber of fineness 0.33dtex (the about 5.5 μ m of fiber diameter) and the adhesive PET short fiber of fineness 0.22dtex (the about 4.5 μ m of fiber diameter) with fineness 0.11dtex (the about 3.2 μ m of fiber diameter), weight ratio with 3/2/5 is carried out blending, copies the paper method with basic weight 12.6g/m by wet type 2The system film carries out press polish at 140 ℃, obtains the PET nonwoven fabrics of thickness 18 μ m.
With poly (Supreme Being people テ Network ノ プ ロ ダ Network Star Co., Ltd. system, trade name " コ one ネ Star Network ス ") be dissolved in dimethylacetylamide: making concentration in the mixed solvent of tripropylene glycol=85: 15 (weight ratio) is 9 weight %, has prepared polymer solution.This polymer solution is coated the two sides of this PET nonwoven fabrics, and will be coated with thing with dimethylacetylamide: dipping obtained solidifying film in 60 seconds in 30 ℃ of coagulating baths that water=55: 45 (weight ratio) is formed.This is solidified film in 50 ℃ water-bath, washed 10 minutes, dry then, obtain lithium rechargeable battery dividing plate of the present invention.This dividing plate note is made dividing plate 1 of the present invention.The thickness of dividing plate 1 of the present invention is that 21 μ m, basic weight are 14.7g/m 2, Gurley value (JIS P8117) is 23 seconds/100cc.
Utilize ESEM (SEM) to observe two sides in the table of this sample, the result does not observe the fiber that constitutes nonwoven fabrics and exposes.
[embodiment 2]
Use the poly short fiber of fineness 0.9dtex (the about 10 μ m of fiber diameter), by dry process with basic weight 15.0g/m 2The system film carries out press polish at 320 ℃, obtains the nonwoven fabrics of thickness 30 μ m.
Use this nonwoven fabrics, use polymer solution similarly to Example 1, obtain lithium rechargeable battery dividing plate of the present invention after the same method.This dividing plate note is made dividing plate 2 of the present invention.The thickness of dividing plate 2 of the present invention is that 34 μ m, basic weight are 18.1g/m 2, Gurley value (JIS P8117) is 35 seconds/100cc.
[comparative example 1]
Nonwoven fabrics similarly to Example 1 is fixed on the PET film, is coated with the polymer solution that uses among the embodiment 1 thereon.Impregnated in and obtain solidifying film in the solidification liquid similarly to Example 1.This is solidified film in 50 ℃ water-bath, washed 10 minutes, dry then.Afterwards, peel off the PET film, obtain comparison dividing plate 1.Relatively the thickness of dividing plate 1 is that 20 μ m, basic weight are 13.9g/m 2, Gurley value (JIS P8117) is 15 seconds/100cc.
Utilize ESEM (SEM) to observe two sides in the table of this sample, the result obviously observes the fiber that constitutes nonwoven fabrics and exposes on a face that contacts with the PET film.
[comparative example 2]
Use the PET short fiber of fineness 0.33dtex (fiber diameter 5.5 μ m) and the adhesive PET fiber of fineness 0.22dtex (fiber diameter 4.5 μ m), the weight ratio blending with 6/4 is copied the paper method with basic weight 12.0g/m by wet type 2The system film carries out press polish at 200 ℃, obtains the PET nonwoven fabrics of thickness 18 μ m.
With vinylidene: hexafluoropropylene: the polyvinylidene fluoride alkene copolymer of chlorotrifluoroethylene=95.5: 2.3: 2.2 (weight ratio) is dissolved in dimethylacetylamide: making its concentration in the mixed solvent of tripropylene glycol=70: 30 (weight ratio) is 12 weight %, has prepared polymer solution.
This polymer solution is coated on the two sides of this PET nonwoven fabrics, and will be coated with thing with dimethylacetylamide: dipping obtained solidifying film in 60 seconds in 30 ℃ of coagulating baths that water=55: 45 (weight ratio) is formed.This is solidified film in 50 ℃ water-bath, washed 10 minutes, dry then, obtain comparison dividing plate 2.Relatively the thickness of dividing plate 2 is that 24 μ m, basic weight are 17.3g/m 2, Gurley value (JISP8117) is 12 seconds/100cc.
[thermal endurance estimates 1]
With the invention described above dividing plate 1 and 2, relatively dividing plate 1 and 2 and commercially available lithium rechargeable battery cut out 10cm * 10cm respectively with dividing plate polypropylene microporous film (セ Le ガ one De corporate system, trade name: " セ Le ガ one De #2400 ").Electrolyte is got in the 70cc sample bottle.At this, electrolyte uses 1M LiBF 4PC/EC (1/1 weight ratio).Put into this sample bottle with cutting the dividing plate that, handled 2 hours at 150 ℃.Then, from sample bottle, take out dividing plate and observe dividing plate.The result is as shown in table 1.
[thermal endurance estimates 2]
With the invention described above dividing plate 1 and 2, relatively dividing plate 1 and 2 and commercially available lithium rechargeable battery cut out 10cm * 10cm respectively with dividing plate polypropylene microporous film (セ Le ガ one De corporate system, trade name: " セ Le ガ one De #2400 ").Being fixed in can 4 on the fixing frame of direction, 200 ℃ of heat treatments 30 minutes.Form and size after the mensuration heat treatment.The result is as shown in table 1.
[embodiment 3]
Use N-N-methyl-2-2-pyrrolidone N-solvent with cobalt acid lithium (LiCoO 2Japan chemical industrial company system) powder 89.5 weight portions, acetylene black 4.5 weight portions and Kynoar 6 weight portions are mediated, and have made slurry.The slurry that obtains is coated on the aluminium foil of thickness 20 μ m, suppressed after the drying, obtain the positive pole of 100 μ m.
(MCMB: Osaka gas chemical company system) powder 87 weight portions, acetylene black 3 weight portions and Kynoar 10 weight portions are mediated, and have made slurry with carbonaceous mesophase spherules to use N-N-methyl-2-2-pyrrolidone N-solvent.The slurry that obtains is coated on the Copper Foil of thickness 18 μ m, suppressed after the drying, obtain the negative pole of 90 μ m.
It is opposed to make above-mentioned positive pole and negative pole clip the dividing plate of the present invention 1 that embodiment 1 makes.Flood electrolyte therein, and be encapsulated in the external packing that constitutes by the aluminium lamination press mold, made lithium rechargeable battery of the present invention.At this, electrolyte uses 1M LiPF 6EC/EMC (3/7 weight ratio).This battery note is made battery 1 of the present invention.
[comparative example 3]
Use and compare dividing plate 1, made lithium rechargeable battery by method similarly to Example 1 as dividing plate.This lithium rechargeable battery is remembered the battery 1 of making comparisons.
[comparative example 4]
Use commercially available lithium rechargeable battery as dividing plate, to make lithium rechargeable battery by method similarly to Example 1 with dividing plate polypropylene microporous film (セ Le ガ one De corporate system, trade name: " セ Le ガ one De #2400 ").This lithium rechargeable battery is remembered the battery 2 of making comparisons.
[cyclic test]
For battery 1 of the present invention and battery 1 and 2 relatively, the constant-current discharge 100 times of 1C, 4,2V, 2 hours constant-current constant-voltage charging and 1C, 2.75V is carried out in circulation.Obtain (capacity sustainment rate)=(discharge capacity of the 100th circulation)/(discharge capacity of the 1st circulation) for each battery.Its result is as shown in table 2.Only used the comparative example 1 of observing the comparison dividing plate 1 that nonwoven fabrics exposes, the cycle characteristics significance difference uses the battery of the present invention 1 of the dividing plate of the present invention 1 that has applied coating on the two sides to have equal characteristic with commercially available dividing plate.
[overcharge test]
For battery 1 of the present invention and comparison battery 2, under 1C, carry out 10 hours constant current charge (carrying out overcharge test) with respect to 10 times of chargings of original charging.But, stop charging by force if voltage reaches 6V.The situation that arrives voltage 6V, stops charging by force before through 10 hours is insufficient as the characteristic of overcharging, and the situation conduct that will be different from this characteristic of overcharging is abundant.The result of overcharge test uses the characteristic of overcharging of battery of the present invention 1 of dividing plate of the present invention abundant, and uses the comparison battery 2 of commercially available dividing plate insufficient as shown in Figure 1.
[embodiment 4]
With エ マ Le ゲ Application 120 (flower king system: nonionic class surfactant) be dissolved in the methyl alcohol, made the solution of 1 weight %.The dividing plate of the present invention 1 that embodiment 1 is made impregnated in this surfactant methanol solution and drying, and surfactant is adhered to, and obtains dividing plate 3 of the present invention.At this, the amount of surfactant of adhering on the dividing plate 3 of the present invention is 0.15g/m 2
[embodiment 5]
With エ レ Network ト ロ ス ト リ Star パ-AC (flower king system: the zwitterionic classes surfactant) be dissolved in the methyl alcohol, made the solution of 1 weight %.The dividing plate of the present invention 1 that embodiment 1 is made impregnated in this surfactant methanol solution and drying, and surfactant is adhered to, and obtains dividing plate 4 of the present invention.At this, the amount of surfactant of adhering on the dividing plate 4 of the present invention is 0.02g/m 2
[embodiment 6]
With コ one タ ミ Application 60W (flower king system: the cationic surfactant) be dissolved in the methyl alcohol, made the solution of 1 weight %.The dividing plate of the present invention 1 that embodiment 1 is made impregnated in this surfactant methanol solution and drying, and surfactant is adhered to, and obtains dividing plate 5 of the present invention.At this, the amount of surfactant of adhering on the dividing plate 5 of the present invention is 0.04g/m 2
[embodiment 7]
With エ レ Network ト ロ ス ト リ Star パ-F (flower king system: the anionic species surfactant) be dissolved in the methyl alcohol, made the solution of 1 weight %.The dividing plate of the present invention 1 that embodiment 1 is made impregnated in this surfactant methanol solution and drying, and surfactant is adhered to, and obtains dividing plate 6 of the present invention.At this, the amount of surfactant of adhering on the dividing plate 6 of the present invention is 0.10g/m 2
[electrostatic pressure mensuration]
Use ス タ テ イ Star Network オ ネ ス ト メ one タ H-0110 (シ シ De static gas system) to measure the electrostatic pressure half-life of dividing plate 1,3 to 6 of the present invention.The result is as shown in table 3.As known from Table 3, the attaching surface activating agent for antistatic be effective.
[embodiment 8]
With fineness 0.9dtex (the about 10 μ m of fiber diameter) poly short fiber as principal fiber, the pulp that will comprise para-aramid is as binder, they are mixed with principal fiber/adhesive=1/1 (weight ratio), copy the paper method with basic weight 29.9g/m by wet type 2The system film, and carry out press polish, obtain the aramid nonwoven fabric (aramid paper) of thickness 30 μ m.
With poly (Supreme Being people テ Network ノ プ ロ ダ Network Star Co., Ltd. system, trade name " コ one ネ Star Network ス ") be dissolved in dimethylacetylamide: making concentration in the mixed solvent of tripropylene glycol=85: 15 (weight ratio) is 9 weight %, has prepared polymer solution.This polymer solution is coated the two sides of this aramid nonwoven fabric, and will be coated with thing at dimethylacetylamide: dipping obtained solidifying film in 60 seconds in 40 ℃ of coagulating baths that water=60: 40 (weight ratio) is formed.This is solidified film in 30 ℃ water-bath, washed 10 minutes, dry then, obtain lithium rechargeable battery dividing plate of the present invention.This dividing plate note is made dividing plate 7 of the present invention.The thickness of dividing plate 7 of the present invention is that 39 μ m, basic weight are 34.5g/m 2, Gurley value (JIS P8117) is 40 seconds/100cc.In addition, the weight that comprises the porous layer of poly is 4.6g/m 2
[embodiment 9]
PET short fiber and the PET short fiber of fineness 0.33dtex (the about 5.5 μ m of fiber diameter) and the adhesive PET short fiber of fineness 0.22dtex (the about 4.5 μ m of fiber diameter) with fineness 0.11dtex (the about 3.2 μ m of fiber diameter), weight ratio with 3/2/5 is carried out blending, copies the paper method with basic weight 13.0g/m by wet type 2The system film, and carry out press polish, obtain the PET nonwoven fabrics of thickness 18 μ m.
Use this nonwoven fabrics, the method by similarly to Example 8 obtains lithium rechargeable battery dividing plate of the present invention.This dividing plate note is made dividing plate 8 of the present invention.The thickness of dividing plate 8 of the present invention is that 29 μ m, basic weight are 18.3g/m 2, Gurley value (JIS P8117) is 28 seconds/100cc.In addition, the weight that comprises the porous layer of poly is 5.3g/m 2
[embodiment 10]
By method similarly to Example 9, change coating clearance, obtaining thickness is that 37 μ m, basic weight are 22.1g/m 2, Gurley value (JIS P8117) is the dividing plate of the present invention 9 of 32 seconds/100cc.In addition, the weight that comprises the porous layer of poly is 9.1g/m 2
[embodiment 11]
By method similarly to Example 9, change coating clearance, obtaining thickness is that 22 μ m, basic weight are 16.3g/m 2, Gurley value (JIS P8117) is the dividing plate of the present invention 10 of 32 seconds/100cc.In addition, the weight that comprises the porous layer of poly is 3.3g/m 2
[embodiment 12]
By method similarly to Example 9, change coating clearance, obtaining thickness is that 24 μ m, basic weight are 17.3g/m 2, Gurley value (JIS P8117) is the dividing plate of the present invention 11 of 32 seconds/100cc.In addition, the weight that comprises the porous layer of poly is 4.3g/m 2
[puncture strength detection]
To the puncture mensuration of intensity of dividing plate 2,7 to 11 of the present invention.Puncture intensity is by dividing plate being installed on the fixed frame of 11.3mm φ, plugs the pin of a tip of a root end diameter 0.5mm on the central vertical ground of dividing plate, measures with the constant speed insertion pin of 2mm/ second.With pin move 5mm apart from the peak load that is applied on the median septum as the puncture intensity.The results are shown in the table 4.When the material of nonwoven fabrics was used the aromatic polyamides material, the recruitment of puncture intensity was big before and after the coating.Comprise the nonwoven fabrics of aromatic polyamides material and the affinity height of the poly that forms porous layer,, therefore consider it is effective from the viewpoint that obtains the high strength dividing plate owing to obtain higher reinforced effects.
[embodiment 13 to 16]
The dividing plate of the present invention 8 to 11 that uses embodiment 9 to 12 to obtain has obtained battery 2 to 5 of the present invention similarly to Example 3.
[embodiment 17 to 20]
The dividing plate of the present invention 8 to 11 that uses embodiment 9 to 12 to obtain, electrolyte uses 1MLiPF 6EC/EMC/VC (29/70/1 weight ratio) obtains battery 6 to 9 of the present invention in addition similarly to Example 3.
[embodiment 21 to 24]
The dividing plate of the present invention 8 to 11 that uses embodiment 9 to 12 to obtain, electrolyte uses 1MLiPF 6EC/EMC/VA (29/70/1 weight ratio) obtains battery 10 to 13 of the present invention in addition similarly to Example 3.
[comparative example 5]
Except that the PET nonwoven fabrics that uses embodiment 9 to make as the dividing plate, make battery with method similarly to Example 3.This battery is remembered the battery 3 of making comparisons.
[cell durability evaluation]
The battery of the present invention 2 to 13 that embodiment 13 to 24 is made and relatively battery 3 charge to 4.2V, preserved 4 days down at 80 ℃.Then, battery is disassembled, the dividing plate that takes out is wherein observed.The result is as shown in table 5.As can be seen from Table 5, the effect that has abundant inhibition PET deterioration under the situation that the coating weight of poly is suitable.In addition, as can be seen, in order to prevent this PET deterioration, interpolation VC or VA also are effective in electrolyte.
[embodiment 25]
PET short fiber and the PET short fiber of fineness 0.33dtex (the about 5.5 μ m of fiber diameter) and the adhesive PET short fiber of fineness 0.22dtex (the about 4.5 μ m of fiber diameter) with fineness 0.11dtex (the about 3.2 μ m of fiber diameter), weight ratio with 3/2/5 is carried out blending, copies the paper method with basic weight 12.6g/m by wet type 2The system film carries out press polish at 140 ℃, obtains the PET nonwoven fabrics of thickness 18 μ m.
With poly (Supreme Being people テ Network ノ プ ロ ダ Network Star Co., Ltd. system, trade name " コ one ネ Star Network ス ") be dissolved in dimethylacetylamide: making concentration in the mixed solvent of tripropylene glycol=60: 30 (weight ratio) is 6 weight %, has prepared polymer solution.Make alpha-alumina fine particle (rock paddy chemical industrial company system with the average grain diameter 0.8 μ m of poly identical weight part; SA-1) be dispersed in this polymer solution, made the coating slurry.This coating is coated the two sides of this PET nonwoven fabrics with slurry, and will be coated with thing at dimethylacetylamide: dipping obtained solidifying film in 60 seconds in 40 ℃ of coagulating baths that water=50: 50 (weight ratio) is formed.This is solidified film in 50 ℃ water-bath, washed 10 minutes, dry then, obtain lithium rechargeable battery dividing plate of the present invention.This dividing plate note is made dividing plate 12 of the present invention.The thickness of dividing plate 1 of the present invention is that 23 μ m, basic weight are 16.6g/m 2, Gurley value (JIS P8117) is 20 seconds/100cc.In addition, visual observations dividing plate 12 of the present invention, the result does not observe pin hole.
[reference example 1]
With poly (Supreme Being people テ Network ノ プ ロ ダ Network Star Co., Ltd. system, trade name " コ one ネ Star Network ス ") be dissolved in dimethylacetylamide: making concentration in the mixed solvent of tripropylene glycol=60: 30 (weight ratio) is 6 weight %, has prepared polymer solution.
This polymer solution is coated the two sides of the PET nonwoven fabrics that embodiment 25 obtains, and will be coated with thing at dimethylacetylamide: dipping obtained solidifying film in 60 seconds in 40 ℃ of coagulating baths that water=50: 50 (weight ratio) is formed.This is solidified film in 50 ℃ water-bath, washed 10 minutes, dry then, obtain dividing plate of the present invention, but a large amount of pin hole that produces does not obtain satisfied dividing plate.
[reference example 2]
Except the amount with alpha-alumina fine particle is set at respect to poly is 10%, makes dividing plate of the present invention similarly to Example 25, but a large amount of pin holes that produce can not obtain satisfied dividing plate.
[reference example 3]
Except the amount with alpha-alumina fine particle is set at respect to poly is 900%, make dividing plate of the present invention similarly to Example 25, but, solidify with washing step in alpha-alumina fine particle drop, can not obtain the satisfied dividing plate of operating characteristics.
[film resistance mensuration]
Electrolyte be impregnated in the dividing plate, the gained dividing plate is used the pair of electrodes (size: 2cm * 1.4cm=2.8cm that constitutes by aluminium foil 2) clamp, and be encapsulated in the aluminium lamination press mold, made to measure and used battery.At this, electrolyte uses 1M LiBF 4PC/EC (1/1 weight ratio).In this battery, separately resistance when to measure dividing plate be 1,2 and 3 by AC impedence method, the slope by this resistance during with respect to the sheet number mapping of dividing plate is obtained the resistance of 1 dividing plate.AC impedance is measured and is undertaken by 4 terminal methods, and amplitude is 10mV, frequency 100kHZ.In addition, measure temperature and be set at 20 ℃.
Dividing plate 1 of the present invention and 12 is carried out above-mentioned film resistance measure, film resistance is respectively 6.026ohmcm as a result 2And 5.211ohmcm 2
From the measurement result of above-mentioned film resistance as can be known, the concentration that reduces the poly in the polymer solution is effective.But when using such polymer solution to be coated with, shown in reference example 1 and 2, viscosity is low excessively to cause a large amount of generation pin holes, thereby is difficult to obtain satisfied dividing plate.Shown in embodiment 25, can address this problem by suitably adding ceramic particle.But, shown in reference example 3, when ceramic particle excessively adds, produce the powder problem, thereby be difficult to obtain satisfied filming.
Table 1
Dividing plate Thermal endurance estimates 1 Thermal endurance estimates 2 Evaluation
Dividing plate 1 of the present invention No change No change ○
Dividing plate 2 of the present invention No change No change ○
Compare dividing plate 1 No change No change ○
Compare dividing plate 2 The dissolving of polyvinylidene fluoride alkene copolymer, only nonwoven fabrics is residual Size does not change, but the dissolving of polyvinylidene fluoride alkene copolymer ×
The polypropylene microporous film Extremely shrink, can not keep original shape Rupture of membranes ×
Table 2
The capacity sustainment rate
Battery 1 of the present invention 90.6％
Compare battery 1 63.5％
Compare battery 2 90.7％
Table 3
Dividing plate Second half-life
Dividing plate 1 of the present invention 1600
Dividing plate 3 of the present invention 12
Dividing plate 4 of the present invention 15
Dividing plate 5 of the present invention 8
Dividing plate 6 of the present invention 20
Table 4
Figure G200680017331XD00261
Table 5
Battery Dividing plate Aromatic polyamides porous layer weight g/m 2 Electrolyte The dividing plate degradation
Battery 2 of the present invention Dividing plate 8 of the present invention 5.3 Electrolyte A No deterioration
Battery
3 of the present invention Dividing plate 9 of the present invention 9.1 Electrolyte A No deterioration
Battery 4 of the present invention Dividing plate 10 of the present invention 3.3 Electrolyte A In the Copper Foil part PET nonwoven fabrics deterioration relative with dividing plate
Battery
5 of the present invention Dividing plate 11 of the present invention 4.3 Electrolyte A No deterioration
Battery
6 of the present invention Dividing plate 8 of the present invention 5.3 Electrolyte B No deterioration
Battery 7 of the present invention Dividing plate 9 of the present invention 9.1 Electrolyte B No deterioration
Battery 8 of the present invention Dividing plate 10 of the present invention 3.3 Electrolyte B No deterioration
Battery 9 of the present invention Dividing plate 11 of the present invention 4.3 Electrolyte B No deterioration
Battery Dividing plate Aromatic polyamides porous layer weight g/m 2 Electrolyte The dividing plate degradation
Battery 10 of the present invention Dividing plate 8 of the present invention 5.3 Electrolyte C No deterioration
Battery 11 of the present invention Dividing plate 9 of the present invention 9.1 Electrolyte C No deterioration
Battery 12 of the present invention Dividing plate 10 of the present invention 3.3 Electrolyte C No deterioration
Battery 13 of the present invention Dividing plate 11 of the present invention 4.3 Electrolyte C No deterioration
Compare battery 3 The PET nonwoven fabrics - Electrolyte A The part PET nonwoven fabrics deterioration that Copper Foil is relative with dividing plate
Electrolyte A:1M LiPF 6EC/EMC (30/70 weight ratio)
Electrolyte B:1M LiPF 6EC/EMC/VC (29/70/1 weight ratio)
Electrolyte C:1M LiPF 6EC/EMC/VA (29/70/1 weight ratio)
Industrial applicability
Separator for lithium ion secondary battery heat resistance of the present invention is high, and is also effective for the countermeasure of overcharging, and therefore can improve the security of the lithium rechargeable battery that uses this dividing plate. Use the lithium rechargeable battery of the present invention of dividing plate of the present invention, be suitable for requirement and guarantee security under the high temperature and the HEV purposes of performance.

Claims (18)

1. lithium rechargeable battery dividing plate, wherein, the two sides has formed the porous layer that mainly comprises meta-aromatic polyamide in the table of nonwoven fabrics, and the thickness of this dividing plate is 15 to 40 μ m, be 10 to 50 seconds/100cc according to the Gurley value of JIS P8117.
2. the described lithium rechargeable battery dividing plate of claim 1, wherein, be attached with surfactant on the described porous layer, described surfactant comprises and is selected from least a in the group that is made of cationic surfactant, anion surfactant, amphoteric surfactant and non-ionic surface active agent.
3. the described lithium rechargeable battery dividing plate of claim 2, wherein, the adhesion amount of described surfactant is 0.005 to 0.750g/m 2
4. each described lithium rechargeable battery dividing plate in the claim 1 to 3, wherein, described nonwoven fabrics is the nonwoven fabrics that mainly comprises PETG.
5. the described lithium rechargeable battery dividing plate of claim 4, wherein, the weight that mainly comprises the described porous layer of meta-aromatic polyamide is 4 to 10g/m 2
6. each described lithium rechargeable battery dividing plate in the claim 1 to 3, wherein, described nonwoven fabrics is for mainly comprising the nonwoven fabrics of meta-aromatic polyamide.
7. each described lithium rechargeable battery dividing plate in the claim 1 to 3, wherein, described nonwoven fabrics comprises meta-aromatic polyamide short fiber and contraposition aromatic polyamide pulp.
8. each described lithium rechargeable battery dividing plate in the claim 1 to 5, wherein, described meta-aromatic polyamide is a poly.
9. each described lithium rechargeable battery dividing plate in the claim 1 to 8 wherein, contains the ceramic particle of average grain diameter 0.05 to 2 μ m in the described porous layer, is 30 to 80 weight % with respect to the weight ceramic particle of porous layer.
10. a lithium rechargeable battery is with the manufacture method of dividing plate, wherein, to be that the solvent of good solvent is coated two sides in the table of nonwoven fabrics as the polymer solution of principal component with meta-aromatic polyamide with to this meta-aromatic polyamide, making the nonwoven fabrics after the coating then is to solidify in the solvent of poor solvent and the mixed liquor for the solvent of good solvent mainly comprising this meta-aromatic polyamide, then washing, drying.
11. lithium rechargeable battery, have positive pole, negative pole, nonaqueous electrolytic solution and dividing plate, embedding by lithium ion and take off embedding and obtain electromotive force, wherein, dividing plate two sides in the table of nonwoven fabrics forms the porous layer that mainly comprises meta-aromatic polyamide, and the thickness of described dividing plate is 15 to 40 μ m, be 10 to 50 seconds/100cc according to the Gurley value of JIS P8117.
12. the described lithium rechargeable battery of claim 11, wherein, be attached with surfactant on the described porous layer, described surfactant comprises and is selected from least a in the group that is made of cationic surfactant, anion surfactant, amphoteric surfactant and non-ionic surface active agent.
13. the described lithium rechargeable battery dividing plate of claim 12, wherein, the adhesion amount of described surfactant is 0.005 to 0.750g/m 2
14. each described lithium rechargeable battery in the claim 11 to 13, wherein, described nonwoven fabrics is the nonwoven fabrics that mainly comprises PETG.
15. the described lithium rechargeable battery of claim 14, wherein, the weight that mainly comprises the described porous layer of meta-aromatic polyamide is 4 to 10g/m 2
16. the described lithium rechargeable battery of claim 14, wherein, described nonaqueous electrolyte is made of electrolyte and this electrolytical solvent of dissolving, and this electrolyte is with LiPF 6Be main body, this solvent contains vinylene carbonate or the vinyl acetate of 0.5 to 5 weight % with respect to the solvent total weight.
17. each described lithium rechargeable battery in the claim 11 to 13, wherein, described nonwoven fabrics is for mainly comprising the nonwoven fabrics of meta-aromatic polyamide.
18. each described lithium rechargeable battery in the claim 11 to 17, wherein, described meta-aromatic polyamide is a poly.
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