CN104137301A - Separators for electrochemical cells containing polymer particles - Google Patents

Separators for electrochemical cells containing polymer particles Download PDF

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Publication number
CN104137301A
CN104137301A CN201380011292.2A CN201380011292A CN104137301A CN 104137301 A CN104137301 A CN 104137301A CN 201380011292 A CN201380011292 A CN 201380011292A CN 104137301 A CN104137301 A CN 104137301A
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China
Prior art keywords
partition
particle
cross
present
layer
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Pending
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CN201380011292.2A
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Chinese (zh)
Inventor
O·格龙瓦尔德
K·莱特纳
N·詹森
C·J·韦伯
M·罗特
G·豪贝尔
S·法卢西
S·盖格尔
M·贝格
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BASF SE
Carl Freudenberg KG
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BASF SE
Carl Freudenberg KG
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Publication of CN104137301A publication Critical patent/CN104137301A/en
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/14—Dynamic membranes
    • B01D69/141—Heterogeneous membranes, e.g. containing dispersed material; Mixed matrix membranes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/14—Dynamic membranes
    • B01D69/141—Heterogeneous membranes, e.g. containing dispersed material; Mixed matrix membranes
    • B01D69/1411—Heterogeneous membranes, e.g. containing dispersed material; Mixed matrix membranes containing dispersed material in a continuous matrix
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/44—Polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, not provided for in a single one of groups B01D71/26-B01D71/42
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/44—Polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, not provided for in a single one of groups B01D71/26-B01D71/42
    • B01D71/441—Polyvinylpyrrolidone
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/52—Separators
    • 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/386—Silicon or alloys based on silicon
    • 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/387—Tin or alloys based on tin
    • 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • 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
    • H01M50/44—Fibrous material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/02—Details
    • H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
    • H01M8/023—Porous and characterised by the material
    • H01M8/0239—Organic resins; Organic polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2323/00—Details relating to membrane preparation
    • B01D2323/30—Cross-linking
    • 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
    • H01M2200/00—Safety devices for primary or secondary batteries
    • H01M2200/20—Pressure-sensitive devices
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2220/00—Batteries for particular applications
    • H01M2220/10—Batteries in stationary systems, e.g. emergency power source in plant
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2220/00—Batteries for particular applications
    • H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
    • 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
    • H01M50/491—Porosity
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • 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
    • Y02E60/13—Energy storage using capacitors
    • 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
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Abstract

The present invention relates to separators for electrochemical cells, comprising (A) at least one layer, containing (a) crosslinked polyvinylpyrrolidone in the form of particles, (b) at least one binder, and (c) possibly a base body, wherein the mass ratio of the crosslinked polyvinylpyrrolidone in the form of particles (a) to the sum of the mass of the binders (b) in the layer (A) has a value in the range of from 99.0:0.1 to 50:50. Furthermore, the present invention relates to the use of separators according to the invention and apparatuses, in particular electrochemical cells, containing separators according to the invention.

Description

The electrochemical cell partition that contains polymer beads
The present invention relates to electrochemical cell partition, comprise
(A) at least one layer that comprises following component:
(a) cross-linking polyethylene pyrrolidone of particle form,
(b) at least one adhesive, and
(c) optional basal body structure,
Wherein the cross-linking polyethylene pyrrolidone of particle form (a) is 99.9:0.1-50:50 with the mass ratio of the quality summation of the middle adhesive (b) of layer (A).
The device that the invention further relates to the purposes of partition of the present invention and comprise partition of the present invention, especially electrochemical cell.
For a long time, the storage of energy has become the theme that continues to receive publicity.Electrochemical cell, for example battery pack or storage battery can be used for store electrical energy.Recently, so-called lithium ion battery group has received special concern.It is better than conventional batteries group at several technical elements.For example, it can be used for producing the voltage that cannot be obtained by the battery pack based on aqueous electrolyte.
In electrochemical cell, positively charged and electronegative electrod composition are by the non-conductive layer machinery separation mutually that is known as partition, to avoid internal discharge.Due to its loose structure, these partitions allow the conveying of ionic charge to continue the basic premise of outflow as electric current in the operating process of this battery pack.Partition must satisfied basic demand be to the two chemistry and electrochemical stability of active electrode composition and electrolyte.In addition, must guarantee the high mechanical properties with regard to the tension force with regard to occurring in battery production technology process.On structure level, must exist high porosity to guarantee high ion-conductivity for electrolytical absorption.Meanwhile, the hole dimension in duct and structure must effectively suppress the growth of Metal tree dendrite, to avoid short circuit, as Journal Power Sources 2007,164, described in 351-364.
Partition as microporous layers is made up of polymer film or non-woven fabric conventionally.
Current conventionally will be based on polyethylene and polyacrylic polymer film as the partition in electrochemical cell, but these films have not enough stability at the rising temperature of 130-150 DEG C.
The substitute of normally used polyolefin partition is the partition based on non-woven fabric, this non-woven fabric is filled with ceramic particle and additionally fixes with the inorganic bond of the oxide of containing element silicon, aluminium and/or zirconium, as DE10255122A1, DE10238941A1, DE10208280A1, described in DE10208277 A1 and WO 2005/038959A1.But, the weight (basis weight) that is filled with the non-woven fabric of ceramic particle per unit area compared with filling non woven thing not increase and thickness larger.
WO 2009/033627 discloses a kind of layer that can use as lithium ion battery group partition.It comprises non-woven fabric and embeds in this non-woven fabric and by organic polymer and part inorganic material forms if possible particle.The short circuit allegedly being caused by Metal tree dendrite is avoided by such partition.But WO 2009/033627 does not disclose long-term cyclic test.
WO 2009/103537 discloses a kind of layer with basal body structure with holes, and this layer further comprises crosslinked adhesive.In preferred embodiments, at least part of filler particles of this basal body structure.Disclosed layer can be used as partition in battery pack.But, in WO 2009/103537, there is no to produce or detect the electrochemical cell with described layer.
WO 2010/118822 discloses a kind of have different cathode side aspect respective material consistency and the asymmetrical cell group partition of anode-side.
By the known partition of the document with regard to one or more in the required performance of partition, for example thickness is little, good mechanical stability in lightweight, the course of processing of per unit area is as high-flexibility or low abrasion, or with regard to Metal tree dendritic growth, good thermal stability, low-shrinkage characteristic, high porosity, good ionic conductivity and good electrolyte wetability, still has defect in the operation of battery pack.Some defects of partition finally cause the life-span reduction of the electrochemical cell that comprises them.In addition partition not only mechanically stable but also target material, anode material and electrolyte chemically stable in principle.
Therefore, the object of the invention is to provide a kind of for the cheap partition of long-life electrochemical cell, it has advantage with regard to one or more performances of known partition, especially except thickness is little, also show high porosity, low-shrinkage and high thermal stability and can be in wide temperature range with high security requirement for thering is the partition of electrochemical cell of high power and energy density.
This object realizes by starting defined electrochemical cell partition, and this partition comprises:
(A) at least one layer that comprises following component:
(a) cross-linking polyethylene pyrrolidone of particle form,
(b) at least one adhesive, and
(c) optional basal body structure,
Wherein the cross-linking polyethylene pyrrolidone of particle form (a) is 99.9:0.1-50:50 with the mass ratio of the quality summation of the middle adhesive (b) of layer (A).
Be applicable to electrochemical cell, especially the partition of rechargeable electrochemical cell comprises at least one layer, also referred to as layer (A), the cross-linking polyethylene pyrrolidone that this layer comprises (a) particle form, also referred to as cross-linking polyethylene pyrrolidone particle (a) or particle (a), (b) at least one adhesive, also referred to as adhesive (b), and (c) optional basal body structure, also referred to as basal body structure (c), wherein the cross-linking polyethylene pyrrolidone of particle form (a) is 99.9:0.1-50:50 with the mass ratio of the quality summation of the middle adhesive (b) of layer (A), preferably 99:1-80:20, more preferably 98:2-90:10, especially 97:3-93:7.
The cross-linking polyethylene pyrrolidone of particle form is known in principle.Water-insoluble but the vinyl pyrrolidone polymer of water-swellable also referred to as the cross-linking polyethylene pyrrolidone of Crospovidone, it for example can be to be for example described in US 3,933,766 or WO 2007/071580 walk to the 5th page of the 33rd popped rice polymerization in row preparation for the 2nd page the 21st.Cross-linking polyethylene pyrrolidone by being greater than 80 % by weight, is preferably greater than 90 % by weight conventionally, and the monomer vinyl pyrrolidones that is especially greater than 96 % by weight forms.By preparation method itself or by the pulverizing of the polymer beads obtaining and suitable method for sieving, can produce the cross-linking polyethylene pyrrolidone powder with the various particle mean sizes in wide region in cross-linking polyethylene pyrrolidone preparation.For medicinal application, for example, as tablet disintegrant, the product type with the particle mean size of different range can be commercial, for example with productName is commercial by BASF SE.The particle mean size that the cross-linking polyethylene pyrrolidone (a) of particle form preferably has in layer (A) is 0.01-50 μ m, preferably 0.01-10 μ m, especially 0.1-5 μ m.
In a preferred embodiment of the invention, with in partition, be present in cross-linking polyethylene pyrrolidone (a) in layer (A) and have the particle mean size of 0.1-5 μ m at electrochemical cell of the present invention with particle form.
Particle size distribution is used from Malvern Instruments GmbH according to DIN ISO 13320-1 with powder type by laser diffraction technology, and the Mastersizer of German Herrenberg measures.The key value of particle mean size is so-called d90 value.The d90 value that volume weighting distributes refers in particle that the granularity of 90% particle volume is less than or equal to d90 value.
Cross-linking polyethylene pyrrolidone particle (a) can have difformity according to production method.In principle, can expect the particle of regular shape, for example spheric granules, or erose particle.Erose cross-linking polyethylene pyrrolidone particle for example can obtain by above-mentioned popped rice polymerization.Preferably have erose particle is polyhedron in the context of the invention, and it not only has bandy outer surface composition but also have aduncate outer surface composition.For the outward appearance with erose cross-linking polyethylene pyrrolidone particle (a) is described, with reference to V.Buehler, " Polyvinylpyrrolidone Excipients for Pharmaceuticals ", the 130th page, Springer Verlag Berlin Heidelberg, 2005 accompanying drawing.
In another embodiment of the present invention, at electrochemical cell of the present invention, with in partition, the cross-linking polyethylene pyrrolidone particle (a) being present in layer (A) has irregularly shaped.
In particularly preferred embodiment of the present invention,, be present in particle form particle mean size and the particle that cross-linking polyethylene pyrrolidone (a) in layer (A) has 0.1-5 μ m and have irregularly shaped with in partition at electrochemical cell of the present invention.
The part by weight of the cross-linking polyethylene pyrrolidone (a) of particle form in the gross mass of layer (A) can be at most 99.9 % by weight.The part by weight of the cross-linking polyethylene pyrrolidone (a) of particle form in the gross mass of layer (C) is preferably at least 5 % by weight, more preferably 20-80 % by weight, especially 30-60 % by weight.
Electrochemical cell of the present invention comprises at least one adhesive (b), for example one or more organic polymers with the layer (A) of partition.Suitable adhesive is for example organic (being total to) polymer, for example, describe in detail as WO 2009/033627 walks to the 12nd page of the 11st row for the 8th page the 7th.Use the adhesive being formed by organic polymer to allow to produce the partition with enough mechanical flexibility.
Suitable (being total to) polymer, be that homopolymers or copolymer for example can be selected from (being total to) polymer that can obtain by anion, catalysis or free radical (being total to) polymerization, especially be selected from the copolymer that polyethylene, polyacrylonitrile, polybutadiene, polystyrene and at least two kinds are selected from following comonomer: ethene, propylene, styrene, (methyl) acrylonitrile and 1,3-butadiene, especially Styrene-Butadiene.Polypropylene is also suitable.Extra suitable is polyisoprene and polyacrylate.Particularly preferably polyacrylonitrile.
Polyacrylonitrile is interpreted as not only referring to polyacrylonitrile homopolymers, and refers to acrylonitrile and 1,3-butadiene or cinnamic copolymer in the context of the invention.Optimization polypropylene nitrile homopolymers.
In the context of the invention, polyethylene is interpreted as not only referring to ceridust, and refer to comprise at least 50mol% ethene and at the most at least one other comonomer of 50mol% with copolymerized form, for example alpha-olefin is as propylene, butylene (1-butylene), 1-hexene, 1-octene, 1-decene, 1-dodecylene, 1-amylene and also have isobutene, vinyl-arene, for example styrene, also has (methyl) acrylic acid, vinyl acetate, propionate, (methyl) acrylic acid C 1-C 10arrcostab, especially methyl acrylate, methyl methacrylate, ethyl acrylate, EMA, n-butyl acrylate, 2-ethylhexyl acrylate, n-BMA, methacrylic acid 2-ethylhexyl, the in addition ethylene copolymer of maleic acid, maleic anhydride and itaconic anhydride.Polyethylene can be HDPE or LDPE.
In the context of the invention, polypropylene is interpreted as not only referring to the homopolymers of propylene, and refer to comprise at least 50mol% propylene and at the most at least one other comonomer of 50mol% with copolymerized form, for example ethene and alpha-olefin are as the propylene copolymer of butylene, 1-hexene, 1-octene, 1-decene, 1-dodecylene and 1-amylene.Polypropylene is preferably isotaxy or basic isotactic polypropylene.
In the context of the invention, polystyrene is interpreted as not only referring to styrene homopolymers, and refers to and acrylonitrile, 1,3-butadiene, (methyl) acrylic acid, (methyl) acrylic acid C 1-C 10arrcostab, divinylbenzene, especially 1,3-divinylbenzene, the copolymer of 1,2-diphenylethlene and AMS.
Another preferred adhesive is polybutadiene.
Other suitable adhesives are selected from polyethylene glycol oxide (PEO), cellulose, carboxymethyl cellulose, PVP, polyimides and polyvinyl alcohol.
In one embodiment of the invention, adhesive is selected from mean molecule quantity M wbe 50 000-1 000 000g/mol, preferably those (being total to) polymer of 50 000-500 000g/mol.
Adhesive can be crosslinked or uncrosslinked (being total to) polymer.
In a preferred embodiment of the invention, adhesive is selected from halo (being total to) polymer, especially fluoro (being total to) polymer.Halo or fluoro (being total to) polymer is interpreted as referring to that comprising at least one per molecule with copolymerized form has at least one halogen atom or at least one fluorine atom, and preferably per molecule has those (being total to) polymer of (copolymerization) monomer of at least two halogen atoms or at least two fluorine atoms.
Example is polyvinyl chloride, polyvinylidene chloride, polytetrafluoroethylene, polyvinylidene fluoride (PVdF), tetrafluoraoethylene-hexafluoropropylene copolymer, vinylidene difluoride-hexafluoropropylene copolymer (PVdF-HFP), vinylidene fluoride-TFE copolymer, perfluoroalkyl vinyl ether copolymer, ethylene-tetrafluoroethylene copolymer, vinylidene fluoride-mono-chlorotrifluoroethylcopolymer copolymer and ethene-chlorine fluoride copolymers.
Suitable adhesive is polyvinyl alcohol, water-soluble polyethylene base pyrrolidones, styrene butadiene rubbers, polyacrylonitrile, carboxymethyl cellulose and fluoro (being total to) polymer, especially styrene butadiene rubbers especially.
In another embodiment of the present invention, use in partition at electrochemical cell of the present invention, the adhesive (b) being present in layer (A) is selected from following polymer: polyvinyl alcohol, water-soluble polyethylene base pyrrolidones, styrene butadiene rubbers, polyacrylonitrile, carboxymethyl cellulose and fluoro (being total to) polymer, especially water-soluble polyethylene base pyrrolidones and styrene butadiene rubbers.
Another feature that layer (A) has is that the cross-linking polyethylene pyrrolidone (a) of particle form is 99.9:0.1-50:50 with the mass ratio of the quality summation of the middle adhesive (b) of layer (A), preferably 99:1-80:20, more preferably 98:2-90:10, especially 97:3-93:7.
Layer (A) can comprise matrix as another component except the cross-linking polyethylene pyrrolidone (a) of particle form and at least one adhesive (b), the basal body structure (c) for example being formed by fiber, as yarn fabric, felt, non-woven fabric, paper or pad, especially non-woven fabric, basal body structure (c) is guaranteed to improve the stability of layer (A) and is not damaged its necessary porosity and ion permeability.Alternatively or extraly, can also comprise at least one porous polymer layer, for example polyolefin film, especially polyethylene or polypropylene screen as the layer (A) of basal body structure.Polyolefin film can be formed by one or more layers again.Porous polyolefin membrane or non-woven fabric itself can meet the function of independent partition as explained in beginning.In principle, layer (A) can also additionally comprise the inorganic particle as described in for example as capable in the 8th page of 4-8 of WO 2009/033627.The gross mass of partition of the present invention based on partition preferably comprises and is less than 5 % by weight, is especially less than the inorganic particle of 1 % by weight.In addition, layer (A) can also comprise the particle that for example walks to the 17th page of the 18th other organic polymers as described in row as WO 2009/033627 for the 12nd page the 23rd in principle.Partition of the present invention preferably also comprises and is less than 50 % by weight based on the particle gross mass of existence in layer (A) except cross-linking polyethylene pyrrolidone particle (a), be more preferably less than 20 % by weight, even be more preferably less than 5 % by weight, be especially less than other organic polymer particles of 1 % by weight.
In another embodiment of the present invention, use in partition at electrochemical cell of the present invention, layer (A) further comprises the basal body structure (c) being made up of fiber, and layer (A) more specifically further comprises the basal body structure (c) being made up of non-woven fabric.
The basal body structure (c) being made up of non-woven fabric can be by inorganic or organic material, preferred organic manufacture of materials.
The example of organic non-woven fabric is polyester nonwoven thing, especially PETG non-woven fabric (PET non-woven fabric), polybutylene terephthalate (PBT) non-woven fabric (PBT non-woven fabric), polyimides non-woven fabric, polyethylene and polypropylene nonwoven, PVdF non-woven fabric and PTFE non-woven fabric.
The example of inorganic non-woven fabric is glass fibre non-woven fabric and ceramic fibre non-woven fabric.
In another embodiment of the present invention, use in partition at electrochemical cell of the present invention, basal body structure (c) is made up of fiber and has by fibroplastic the first hole, basal body structure (c) is crosslinked at least partly PVP particle (a) filling and cross-linking polyethylene pyrrolidone particle (a) is filled at least partly the first hole and formed the region that is filled with cross-linking polyethylene pyrrolidone particle (a), cross-linking polyethylene pyrrolidone particle (a) forms the second hole in fill area, the average diameter of cross-linking polyethylene pyrrolidone particle (a) is greater than the average cell size in most of the second hole.
WO 2009/033514 walks to the 6th page of the 12nd row for the 5th page the 16th and has provided being described in more detail of the layer structure that comprise non-woven fabric and particle, especially spheric granules.Having erose cross-linking polyethylene pyrrolidone particle (a) can fill the hole in the basal body structure (c) being made up of non-woven fabric and form high porosity and can produce the labyrinth-like pore structure that does not allow to form harmful Metal tree dendrite and effectively prevent battery pack short circuit simultaneously.
Depend on production method, cross-linking polyethylene pyrrolidone particle (a) can be applied to or introduce in basal body structure (c) equably or with difference amount.Preferably particulate application (a) so that they be evenly distributed on the whole region of basal body structure (c).The advantage of this arrangement is explained in more detail in the 7th page of 4-12 of WO 2009/033514 is capable.
In another embodiment of the present invention, at electrochemical cell of the present invention, with in partition, the cross-linking polyethylene pyrrolidone particle (a) being present in layer (A) is evenly distributed on the whole region of matrix (c).
Basal body structure (c) can also have the coating that comprises particle (a).Coating equally advantageously suppresses the short circuit in electrochemical cell.Interface zone between coatings and substrate structure (c) is inevitably filled with particle at least partly.
In another embodiment of the present invention, at electrochemical cell of the present invention, with in partition, at least a portion fill area is the coating form of cross-linking polyethylene pyrrolidone particle (a) on basal body structure (c).
In the present invention, preferably use the basal body structure (c) being formed by non-woven fabric, now produce the fiber of non-woven fabric preferably by least one organic polymer, the organic polymer that is especially selected from polybutylene terephthalate (PBT), PETG, polyacrylonitrile, polyvinylidene fluoride, polyether-ether-ketone, PEN, polysulfones, polyimides, polyester, polypropylene, polyformaldehyde, polyamide and PVP is produced.
Especially preferably its fiber, by being greater than 90 % by weight, more preferably greater than 95 % by weight, is especially greater than the non-woven fabric that 98 % by weight PETGs form.
In another embodiment of the present invention, at electrochemical cell of the present invention, with in partition, basal body structure (c) is selected from by least one the non-woven fabric that the organic polymer of polybutylene terephthalate (PBT), PETG, polyacrylonitrile, polyvinylidene fluoride, polyether-ether-ketone, PEN, polysulfones, polyimides, polyester, polypropylene, polyformaldehyde, polyamide and polyvinylpyrrolidone forms for its fiber.Particularly preferably by polyester as PETG or polybutylene terephthalate (PBT), especially PETG form non-woven fabric.
The average length of the fiber of non-woven fabric can at least double its average diameter, preferably times over its average diameter.This special tectonic allows to manufacture tear-resistant especially non-woven fabric, because fiber loops mutually.
In non-woven fabric, at least 90% fiber can have the average diameter of 12 μ m at the most.This special tectonic allows structure to have the layer in the first hole of lower cell size.Even thinner porosity can have the average diameter of 8 μ m at the most by least 40% fiber in non-woven fabric to be realized.
Layer (A) and especially partition totally preferably have the thickness of 100 μ m at the most.Have the layer of this thickness or partition can without any problem reel and allow very battery pack operation reliably.This thickness can be more preferably 25 μ m at the most.Layer or the partition with this thickness allow structure very compact battery pack or capacitor.In other embodiments, this thickness is at least 3,5 or 10 μ m, more preferably 5-100 or 10-60 μ m, especially 9-50 μ m.
In another embodiment of the present invention, at electrochemical cell of the present invention, with in partition, layer (A) has the average thickness of 9-50 μ m.
Partition of the present invention, the partition that especially comprises the basal body structure (c) being made up of non-woven fabric can have at least 25% porosity.The partition with this porosity suppresses the formation of short circuit especially effectively due to its density of material.This partition can preferably have at least 35 porosity.The partition with this porosity allows to produce the battery pack with high power density.The partition that comprises non-woven fabric described herein has high porosity but demonstrates the second very little hole, thereby can not form dendrite growth from a side of this partition to opposite side.For this background, can expect that the second hole forms the labyrinth-like structure that wherein can not form dendrite growth from a side of this partition to opposite side.In another embodiment, porosity is 25-70%, especially 35-60%.
Partition of the present invention, the partition that especially comprises the basal body structure (c) being made up of non-woven fabric can have the cell size of 3 μ m at the most.The selection that has been found that this cell size is advantageous particularly for preventing short circuit.Cell size can be more preferably 1 μ m at the most.This partition particularly advantageously prevents due to Metal tree dendritic growth, in the time pressurizeing, directly contacts from the abrasion of electrode particle the short circuit causing with electrode.
Partition of the present invention, the partition that especially comprises the basal body structure (c) being made up of non-woven fabric can have the maximum tension of at least 15 newton/5cm in the vertical.The partition with this intensity can be wound up on the electrode of battery pack and not tear in particularly no problem mode.
The weight of the per unit area of partition of the present invention can be 10-60g/m 2, especially 15-50g/m 2.
Production partition of the present invention, the method that especially comprises the partition of the basal body structure (c) being made up of non-woven fabric is for example described in more detail in WO 2009/033627 and walks to for the 21st page the 20th in the 23rd page of the 12nd row.In situation of the present invention, the unspecified particles in other aspects (3) by cross-linking polyethylene pyrrolidone particle as above (a) substitute, and other components can as described in use.Coating and post-processing approach, the calendering process of especially emphasizing in WO 2009/033627 can carry out as described therein.Calendering can strengthen partition of the present invention by machinery.Calendering causes that surface roughness reduces.Be present in the lip-deep particle of non-woven fabric (a) and demonstrate smooth spot after calendering.
Partition of the present invention is particularly suitable for constructing the long-life electrochemical cell with high power density and energy density.In conjunction with the weight of little thickness and low per unit area, it demonstrates good mechanical performance and has high porosity and good ionic conductivity.
Above-mentioned electrochemical cell of the present invention can be in battery pack with partition, especially in rechargeable battery, or for capacitor, effectively to prevent short circuit especially therein.
Partition of the present invention can also be used for fuel cell as gas diffusion layers or film, because it demonstrates good wettability and can fluid transfer.
Therefore, the present invention also further provides the invention described above partition purposes as partition in fuel cell, battery pack or capacitor, or as gas diffusion layers or as the purposes of film.
The present invention equally also provides a kind of fuel cell, battery pack or capacitor, and it comprises at least one partition of the present invention as above.
Particularly preferably a kind of electrochemical cell that comprises following component:
At least one partition of the present invention as above, and
(B) at least one negative electrode, and
(C) at least one anode.
Electrochemical cell of the present invention, especially rechargeable electrochemical cell, be preferably wherein main those that are completed by lithium cation of the transmission of the electric charge in battery.
For suitable cathode material, suitable anode material, suitable electrolyte and possible setting, with reference to related art, for example corresponding separate edition and reference works: such as Wakihara etc. (editor): Lithium Ion Batteries, the 1st edition, Wiley VCH, Weinheim, 1998; David Linden:Handbook of Batteries (McGraw-Hill Handbooks), the 3rd edition, McGraw-Hill Professional, New York 2008; J.O.Besenhard:Handbook of Battery Materials, Wiley-VCH, 1998.
Useful negative electrode (B) especially comprises that wherein cathode material comprises lithium-transition metal oxide, for example lithium-cobalt/cobalt oxide, lithium-nickel oxide, lithium-cobalt-nickel oxide, lithium-Mn oxide (spinelle), lithium-nickel-cobalt-aluminum oxide, lithium, nickel, cobalt, manganese oxide or lithium-barium oxide, or lithium-transition metal phosphate, those negative electrodes as phosphatic in lithium-iron.But, if the cathode material that is intended to use is to comprise those of the polymer that comprises sulphur or polysulfide bridge, must guarantee that anode loaded Li before this electrochemical cell can discharge and recharge 0.
Partition of the present invention is particularly suitable for wherein negative electrode (B) and comprises at least one transistion metal compound containing lithium ion, for example transistion metal compound LiCoO 2, LiFePO 4or those electrochemical cells of lithium-galaxite, these compounds are that the skilled person of lithium ion battery technical group field is known.
Negative electrode (B) preferably comprise contain manganese as transition metal containing the transition metal oxide of lithium ion as the transistion metal compound containing lithium ion.
Contain manganese as transition metal in the context of the invention, be interpreted as not only referring to have with cationic form those oxides of at least one transition metal containing the transition metal oxide of lithium ion, and refer to there are those of at least two kinds of transition metal oxides with cationic form.In addition,, in the context of the invention, term " containing the transition metal oxide of lithium ion " also comprises except lithium and also comprises at least one nontransition metal with cationic form, those compounds of for example aluminium or calcium.
In preferred embodiments, manganese can be present in negative electrode (B) with+4 form oxidation state (formal oxidation state).Manganese in negative electrode (B) more preferably exists with+3.5 to+4 form oxidation state.
Many elements are ubiquitous.For example, sodium, potassium and chloride ion are substantially can detecting with a certain very little ratio in institute's organic and/or inorganic materials.In the context of the invention, not consideration ratio is less than cation or the anion of 0.1 % by weight.Therefore, comprise and be less than being considered not containing sodium containing the hybrid transition metal oxide of lithium ion of 0.1 % by weight sodium in the context of the invention.Correspondingly, comprise be less than 0.1 % by weight sulfate ion in the context of the invention, be considered not containing sulfate radicals containing the hybrid transition metal oxide of lithium ion.
In one embodiment of the invention, be the hybrid transition metal oxide that not only comprises manganese but also comprise at least one other transition metal containing the transition metal oxide of lithium ion.
In one embodiment of the invention, transistion metal compound containing lithium ion is selected from the lithium iron phosphate containing manganese, preferably, containing the spinelle and the transition metal oxide containing manganese with layer structure of manganese, especially there is the hybrid transition metal oxide containing manganese of layer structure.
In one embodiment of the invention, be selected from those compounds of the lithium with hyperstoichiometry ratio containing the transistion metal compound of lithium ion.
In one embodiment of the invention, be selected from those of general formula (I) containing the spinelle of manganese:
Li aM 1 bMn 3-a-bO 4-d (I)
Wherein variable separately following institute define:
0.9≤a≤1.3, preferably 0.95≤a≤1.15,
0≤b≤0.6, for example 0.0 or 0.5,
The M that wherein ought choose 1during for Ni, preferably 0.4≤b≤0.55,
-0.1≤d≤0.4, preferably 0≤d≤0.1.
M 1be selected from the element that one or more are selected from the transition metal in the 1st cycle of Al, Mg, Ca, Na, B, Mo, W and the periodic table of elements.M 1be preferably selected from Ni, Co, Cr, Zn, Al, M 1most preferably be Ni.
In one embodiment of the invention, be selected from formula LiNi containing the spinelle of manganese 0.5mn 1.5o 4-dand LiMn 2o 4those.
In another embodiment of the present invention, the transition metal oxide containing manganese with layer structure is selected from those of formula (II):
Li 1+tM 2 1-tO 2
Wherein variable separately following institute define:
0≤t≤0.3, and
M 2be selected from Al, Mg, B, Mo, W, Na, Ca and the periodic table of elements transition metal in the 1st cycle, this transition metal or at least one transition metal are manganese.
In one embodiment of the invention, based on M 2total content, at least 30mol%, the preferably M of 35mol% at least 2be selected from manganese.
In one embodiment of the invention, M 2be selected from the combination of Ni, Co and Mn, do not comprise any other element with significant quantity.
In another embodiment, M 2be selected from the composition of Ni, Co and Mn, comprise at least one other element, for example 1-10mol%Al, Ca or Na with significant quantity.
What in one embodiment of the invention, have a layer structure is selected from wherein M containing the transition metal oxide of manganese 2be selected from Ni 0.33co 0.33mn 0.33, Ni 0.5co 0.2mn 0.3, Ni 0.4co 0.3mn 0.4, Ni 0.4co 0.2mn 0.4and Ni 0.45co 0.10mn 0.45those.
In one embodiment, transition metal oxide containing lithium is the primary granule form that agglomerates into spherical secondary granule, and the average grain diameter (D50) of primary granule is that the average grain diameter (D50) of 50nm to 2 μ m and secondary granule is 2-50 μ m.
Negative electrode (B) can comprise one or other compositions.For example, negative electrode (B) can comprise and be the polymorphic carbon of conduction, for example, be selected from graphite, carbon black, carbon nano-tube, Graphene or above-mentioned substance the mixture of at least two kinds.
In addition, negative electrode (B) can comprise one or more adhesives, for example one or more organic polymers.Suitable adhesive is for example selected from just those adhesives described in adhesive (b) partition for of the present invention.
Be particularly suitable for especially polyvinyl alcohol and halo (being total to) polymer of adhesive of negative electrode (B), for example polyvinyl chloride or polyvinylidene chloride, especially fluoro (being total to) polymer is as polyvinyl fluoride and especially polyvinylidene fluoride and polytetrafluoroethylene.
In addition, negative electrode (B) can have this other compositions as routine, for example output conductor, and it can be configured to the form of metal wire, metal grill, metallic sieve, expanding metal, sheet metal or metal forming.Suitable metal forming is especially aluminium foil.
In one embodiment of the invention, the thickness of negative electrode (B) is 25-200 μ m, is preferably 30-100 μ m, based on the thickness that does not comprise output conductor.
Electrochemical cell of the present invention also comprises at least one anode (C) except partition of the present invention and negative electrode (B).
In one embodiment of the invention, the anode that anode (C) can select free carbon to form, the anode that comprises Sn or Si and contained Li 4+xti 5o 12the anode of lithium titanate, the numerical value that wherein x is >0 to 3.The anode being made up of carbon is for example selected from hard carbon, soft carbon, Graphene, graphite, especially the mixture of two or more in the graphite of graphite, intercalation and above-mentioned carbon.The anode that comprises Sn or Si for example can be selected from Nanoparticulate Si or Sn powder, Si or Sn fiber, carbon-Si or carbon-Sn composite material and Si-metal or Sn-metal alloy.
In another embodiment of the present invention, in electrochemical cell of the present invention, anode, the anode that comprises Sn or Si and contained Li that anode (C) selects free carbon to form 4+xti 5o 12the anode of lithium titanate, the numerical value that wherein x is >0 to 3.
Anode (C) can comprise one or more adhesives.Selected adhesive can be one or more in above-mentioned adhesive (b) described with regard to the explanation of partition of the present invention.
In addition, anode (C) can have other conventional composition itself, for example can be with metal wire, metal grill, metallic sieve, expanding metal, or the output conductor of metal forming or sheet metal formal construction.Especially Copper Foil of suitable metal forming.
In one embodiment of the invention, the thickness of the thickness of anode (C) based on there is no output conductor is 15-200 μ m, preferably 30-100 μ m.
Electrochemical cell of the present invention can also have conventional composition itself, for example conducting salt, nonaqueous solvents and also have cable connectors and shell.
In one embodiment of the invention, it can be at room temperature liquid or solid that electrochemical cell of the present invention comprises at least one, is at room temperature preferably liquid and the nonaqueous solvents that is preferably selected from polymer, ring-type or non-annularity ether, ring-type or non-annularity acetal, ring-type or non-annularity organic carbonate and ionic liquid.
Especially PAG of the example of suitable polymers, preferably poly--C 1-C 4aklylene glycol, especially polyethylene glycol.Polyethylene glycol can comprise one or more C of 20mol% at the most with copolymerized form 1-C 4aklylene glycol.PAG is preferably the PAG of methyl or the two end-blockings of ethyl.
The molecular weight M of suitable polyalkylene glycol and especially suitable polyethylene glycol wcan be 400g/mol at least.
The molecular weight M of suitable polyalkylene glycol and especially suitable polyethylene glycol wcan be 5 000 000g/mol at the most, preferably 2 000 000g/mol at the most.
The example of suitable non-annularity ether is for example diisopropyl ether, di-n-butyl ether, 1,2-dimethoxy-ethane, 1,2-diethoxyethane, preferably 1,2-dimethoxy-ethane.
The example of suitable cyclic ether is oxolane and Isosorbide-5-Nitrae-bis- alkane.
Suitable non-annularity acetal is for example dimethoxymethane, diethoxymethane, 1,1-dimethoxy-ethane and 1,1-diethoxyethane.
The example of suitable cyclic acetal is 1,3-bis- alkane and especially DOX.
The example of suitable non-annularity organic carbonate is dimethyl carbonate, ethylmethyl carbonate and diethyl carbonate.
The example of suitable cyclic organic carbonates is general formula (X) and compound (XI):
Wherein R 1, R 2and R 3can be selected from identical or different and separately hydrogen and C 1-C 4alkyl, for example methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl group, sec-butyl and the tert-butyl group, wherein R 2and R 3when preferred difference, it is the tert-butyl group.
In particularly preferred embodiments, R 1for methyl and R 2and R 3hydrogen or R respectively do for oneself 1, R 2and R 3the hydrogen of respectively doing for oneself.
Another preferred cyclic organic carbonates is the carbonic acid ethenylidene ester of formula (XII):
Preferably use the solvent that is anhydrous state, water content is 1ppm to 0.1 % by weight, and this for example can pass through Karl Fischer titration determination.
Electrochemical cell of the present invention further comprises at least one conducting salt.Suitable conducting salt is especially lithium salts.The example of suitable lithium salts is LiPF 6, LiBF 4, LiClO 4, LiAsF 6, LiCF 3sO 3, LiC (C nf 2n+1sO 2) 3, imino group lithium is as LiN (C nf 2n+1sO 2) 2, the integer that wherein n is 1-20, LiN (SO 2f) 2, Li 2siF 6, LiSbF 6, LiAlCl 4and general formula (C nf 2n+1sO 2) mthe salt of XLi, wherein m is defined as follows:
In the time that X is selected from oxygen and sulphur, m=1;
In the time that X is selected from nitrogen and phosphorus, m=2; And
In the time that X is selected from carbon and silicon, m=3.
Preferred conducting salt is selected from LiC (CF 3sO 2) 3, LiN (CF 3sO 2) 2, LiPF 6, LiBF 4, LiClO 4, be particularly preferably LiPF 6and LiN (CF 3sO 2) 2.
Electrochemical cell of the present invention further comprises shell, and it can be any shape, for example cube or cylindrical shape.In another embodiment, electrochemical cell of the present invention has prismatic shape.In a modification, shell used is the metal-plastic composite membrane as bag processing.
Electrochemical cell of the present invention provides the high voltage of about 4.8V at the most, and significantly part is high-energy-density and good stability.More particularly, the remarkable part of electrochemical cell of the present invention is during iterative cycles, only to have minimum capacitance loss.
The present invention further provides the purposes of electrochemical cell of the present invention in lithium ion battery group.The present invention further provides the lithium ion battery group that comprises at least one electrochemical cell of the present invention.Electrochemical cell of the present invention can be in lithium ion battery group of the present invention combination with one another, for example serial or parallel connection.Preferably series connection.
The present invention further provides the purposes of the invention described above electrochemical cell in automobile, bicycle, aircraft, boats and ships or fixed energies storage by electrical motor driven.
Therefore, the present invention also further provides lithium ion battery group of the present invention at equipment, the especially purposes in mobile device.The example of mobile device is the vehicles, for example automobile, bicycle, aircraft, or marine communication means is as ship or ship.Other examples of mobile device be portable those, for example computer, especially notebook computer, telephone set or electric tool, the screwdriver of the electric tool of for example building field, especially rig, battery driven or the tacker of battery driven.
The use of the lithium ion battery group of the present invention that comprises partition of the present invention in equipment obtained following advantage: in during the running time extending before charging again and the running time extending, less capacitance loss and the self-discharge of battery being caused by short circuit and risk of damage reduce.Obtain identical running time if be intended to having compared with the electrochemical cell of low energy densities, must accept higher electrochemical cell weight.
Set forth the present invention by embodiment below, but these embodiment do not limit the present invention.
The numerical value representing with % is separately based on % by weight, unless otherwise expressly noted.
Method of testing:
In work embodiment, use following method of testing:
Particle size distribution is used from Malvern Instruments GmbH with powder type by laser diffraction technology, and the Mastersizer of German Herrenberg measures.
Average cell size is measured according to ASTM E 1294 (Standard Test Method for Pore Size Characteristics of Membrane Filters Using Automated Liquid Porosimeter).
In order to measure the weight of per unit area, respectively the do for oneself sample of 100 × 100mm of 3 sizes of punching press, the sample measured value is multiplied by 100 of weighing.
Thickness is measured with the accurate calibrator of 2000U/Elektrik.Measurement area is 2cm 2, gaging pressure is 1000cN/cm 2.
Porosity is by thickness, weight and the density calculation of material therefor.
In order to measure shrinkage, punching press is of a size of the sample of 100 × 100mm and it is stored to 10 minutes in the drier of Mathis laboratory at 160 DEG C.Then the shrinkage of working sample.
Through-plane (through-plane) air penetration of battery pack partition is measured by Gurley method (ISO 5636/5).
I. produce cross-linking polyethylene pyrrolidone particle
To be cross-linked and micronizing PVP particle (from BASF SE's cL-M) being sieved into granularity with the AFG wind screening device with deflecting wheel is less than 5 μ m (× 90=4.94 μ m) for × 10=1.23 μ m, × 50=2.57 μ m.
II. produce partition
II.1 production partition of the present invention (S.1)
To 180 parts from example I. the aqueous dispersion of 30% cross-linked pvp particle (D 90=4.94 μ adds 70 part of 0.5% PVP aqueous solution (from the Luvitec K90 of BASF SE) in m) and this mixture is stirred 30 minutes.Then in stirring, add 5 part of 50% styrene butadiene rubbers dispersion (particle mean size: 190nm equally; Glass transition temperature :-10 DEG C).This dispersion is stirred 2 hours and measuring stability at least 24 hours.Dispersions obtained viscosity is that 70cP and pH are 7.4.
Coating
By rolling method by the PET non-woven fabric of wide 15cm (thickness: 20 μ m, the weight of per unit area: 10.6g/m 2) continuously with above-mentioned dispersion coating dry at 120 DEG C.
The weight that obtains per unit area is 18.6g/m 2and thickness is the impregnated nonwoven (S.1) of 31 μ m.Gurley value: 26 seconds/50ml air.
S.1 present following shrinkage:
At 160 DEG C 1 hour: 1.32%
II.2 produces non-partition of the present invention (C-S.2)
In constant agitation, in 200 parts of 60%PTFE dispersions (Dyneon TF 5032R, from 3M, particle mean size 160nm), add 50 parts of 1%CMC (carboxymethyl cellulose) solution.Then in stirring, add 13.3 parts of 50%SBR (styrene butadiene rubbers) dispersions and 50 parts of deionized waters equally.This dispersion is stirred 2 hours and measuring stability at least 24 hours.Dispersions obtained viscosity is that 200cP and pH are 9.5.
Coating
By rolling method by PET non-woven fabric (thickness: 19 μ m, the weight of per unit area: 11g/m 2) continuously with above-mentioned dispersion coating, moving freely low suspension dry with infrared radiator.
The weight that obtains per unit area is 59g/m 2and thickness is the impregnated nonwoven of 42 μ m.The porosity of calculating is 35%.
II.3 produces non-partition of the present invention (C-S.3)
In 322 parts of 1%CMC (carboxymethyl cellulose) solution, add 1470 part of 65% aluminium oxid-dispersion (Al 2o 3) (particle mean size 0.59 μ m) and by this mixture stirs 30 minutes.Then (particle mean size 0.2 μ m) in stirring, to add 100 parts of 50%NBR dispersions equally.This dispersion is stirred 2 hours and measuring stability at least 24 hours.Dispersions obtained viscosity is that 110cP and pH are 9.6.Coating
By rolling method by the PET non-woven fabric of wide 15cm (thickness: 19 μ m, the weight of per unit area: 11g/m 2) continuously with above-mentioned dispersion coating dry at 120 DEG C.
The weight that obtains per unit area is 32.6g/m 2and thickness is the impregnated nonwoven of 29 μ m.Average cell size is that the porosity of 0.22 μ m and calculating is 60%.
Partition of the present invention is compared with the specific conductivity of non-partition of the present invention.Specific conductivity L is calculated by following formula:
L=(d/A*R), the resistance [Ω] that wherein R is individual layer, gross thickness [cm] and A that d is film are electrode area [cm 2].
Other performance compilations of partition of the present invention and non-partition of the present invention
Partition S.1 C-S.2 C-S.3
Thickness/[μ m] 31 42 29
Weight/[the g/m of per unit area 2] 19 59 33
Average cell size/[μ m] 0.2 0.4 0.2
Maximum cell size/[μ m] - - -
Theoretical porosity/[%] 45 Approximately 35 Approximately 60
Gurley/[s/50cm 3] 26 165 380
Maximum tension/[N/5cm] 30 36 38
Shrinkage at 160 DEG C, 1h/[%] 1.3 2 <1
Abrasion no no no
Nail thorn test/[N] 720 540 730
III. in electrochemical cell, test partition
For electrochemical Characterization is in example II. the partition of middle production S.1 and C-S.2, structure electrochemical cell, it is called the bag-shaped battery of individual layer.Bag-shaped battery is known to those skilled in the art electrochemical cell.Combination, described combination and the metal-polymer laminated film lamination of the positive and negative electrode that their each self-contained partitions being soaked by electrolyte are separated.For this reason, except the partition of producing, use in each case the negative electrode that is of a size of 5 × 5cm and the anode that is of a size of 5.6 × 5.6cm in II., they are made up of following component:
Anode: graphite-based anode (the capacity 1.7mAh/cm on Copper Foil conductor 2).
In order to produce electrode, first produce the black suspension in N-ethyl pyrrolidone of 91 % by weight powdered graphites, 6 % by weight PVDF adhesives and 3 % by weight conduction and by planetary-type mixer blend.With Labcoater (from Erichsen), this suspension is applied to copper and carries on the back on paper tinsel, then at 120 DEG C, drying under reduced pressure spends the night.
Negative electrode: nickel aluminate cobalt negative electrode (the capacity 1.4mAh/cm on aluminium conductor 2, LiNi 0.80co 0.15al 0.05o 2).
In order to produce electrode, first produce 88 % by weight LiNi 0.80co 0.15al 0.05o 2the suspension of the black and 3 % by weight graphite of powder, 6 % by weight PVDF adhesives, 3 % by weight conductions in N-ethyl pyrrolidone by planetary-type mixer blend.With Labcoater (from Erichsen), this suspension is applied to copper and carries on the back on paper tinsel, then at 120 DEG C, drying under reduced pressure spends the night.
Electrolyte: be dissolved in mass ratio and be the 1M LiPF in ethylene carbonate and the ethylmethyl carbonate of 1:1 6.
Partition of the present invention, S.1 for the production of electrochemical cell EC.1 of the present invention, will be contrasted to partition C-S.2 for the production of contrast electrochemical cell C-EC.2.
Electrochemical cell EC.1 of the present invention is characterised in that the more high power capacity (table 1) that is in a ratio of 177mAh/g under 0.5C with 159mAh/g compared with contrast electrochemical cell C-EC.2.In addition at least 1.4 times of height compared with the cell resistance of C-EC.2 and the cell resistance of EC.1.In addition, battery EC.1 of the present invention has much better C speed stability (rate stability) (table 1).Under the load of 2C, compared with the 141mAh/g of EC.1, the capacity of C-EC.2 falls after rise to 9mAh/g.Under 4C, EC.1 still demonstrates 95mAh/g, and C-EC.2 no longer discharges any electric current at all.
The C speed stability of table 1:EC.1 and C-EC.2
Capacity 0.5C 1.0C 2.0C 4.0C
EC.1 177mAh/g 159mAh/g 141mAh/g 95mAh/g
C-EC.2 159mAh/g 124mAh/g 9mAh/g ---

Claims (17)

1. an electrochemical cell partition, comprises
(A) at least one layer that comprises following component:
(a) cross-linking polyethylene pyrrolidone of particle form,
(b) at least one adhesive, and
(c) optional basal body structure,
Wherein the cross-linking polyethylene pyrrolidone of particle form (a) is 99.9:0.1-50:50 with the mass ratio of the quality summation of the middle adhesive (b) of layer (A).
2. according to the partition of claim 1, be wherein present in described cross-linking polyethylene pyrrolidone (a) in layer (A) and have the particle mean size of 0.1-5 μ m with particle form.
3. according to the partition of claim 1 or 2, the cross-linking polyethylene pyrrolidone particle (a) being wherein present in layer (A) has irregularly shaped.
4. according to the partition of any one in claim 1-3, the adhesive (b) being wherein present in layer (A) is selected from following polymer: polyvinyl alcohol, water-soluble polyethylene base pyrrolidones, styrene butadiene rubbers, polyacrylonitrile, carboxymethyl cellulose and fluoro (being total to) polymer.
5. according to the partition of any one in claim 1-4, its middle level (A) further comprises the basal body structure (c) being made up of non-woven fabric.
6. according to the partition of any one in claim 1-5, wherein basal body structure (c) is made up of fiber and has by fibroplastic the first hole, basal body structure (c) is crosslinked at least partly PVP particle (a) filling and cross-linking polyethylene pyrrolidone particle (a) is filled at least partly the first hole and formed the region that is filled with cross-linking polyethylene pyrrolidone particle (a), cross-linking polyethylene pyrrolidone particle (a) forms the second hole in fill area, the average diameter of cross-linking polyethylene pyrrolidone particle (a) is greater than the average cell size in most of the second hole.
7. according to the partition of any one in claim 1-6, the cross-linking polyethylene pyrrolidone particle (a) being wherein present in layer (A) is evenly distributed on the Zone Full of basal body structure (c).
8. according to the partition of claim 6 or 7, wherein at least a portion fill area is the coating form of the basal body structure (c) with cross-linking polyethylene pyrrolidone particle (a).
9. according to the partition of any one in claim 1-8, wherein basal body structure (c) is selected from by least one the non-woven fabric that the organic polymer of polybutylene terephthalate (PBT), PETG, polyacrylonitrile, polyvinylidene fluoride, polyether-ether-ketone, PEN, polysulfones, polyimides, polyester, polypropylene, polyformaldehyde, polyamide and PVP is produced for its fiber.
10. according to the partition of any one in claim 1-9, its middle level (A) has the average thickness of 9-50 μ m.
11. according to the partition of any one in claim 1-10 in fuel cell, battery pack or capacitor as partition or as the purposes of gas diffusion layers or film.
12. 1 kinds of fuel cells, battery pack or capacitors, comprise at least one according to the partition of any one in claim 1-10.
13. 1 kinds of electrochemical cells, comprise at least one according to the partition of any one in claim 1-10 and
(B) at least one negative electrode, and
(C) at least one anode.
14. according to the electrochemical cell of claim 13, the anode that its Anodic (C) selects free carbon to form, the anode that comprises Sn or Si and contained Li 4+xti 5o 12the anode of lithium titanate, the numerical value that wherein x is >0 to 3.
15. according to the electrochemical cell of claim 13 or 14 purposes in lithium ion battery group.
16. 1 kinds of lithium ion battery groups, comprise at least one according to the electrochemical cell of claim 13 or 14.
17. according to the electrochemical cell of claim 13 or 14 purposes in automobile, bicycle, aircraft, boats and ships or fixed energies storage by electrical motor driven.
CN201380011292.2A 2012-02-27 2013-02-25 Separators for electrochemical cells containing polymer particles Pending CN104137301A (en)

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