JP2001520439A - Composite materials suitable for electrochemical cells - Google Patents

Abstract

  (57) [Summary] Aa) a) 1 to 95% by weight of solid III, preferably basic solid III, having a primary particle size of 5 nm to 20 μm, and b) 5 to 99% by weight of b1) 5 based on composition IV. At least one compound VI capable of reacting with from 100 to 100% by weight of α) a carboxylic acid or a sulfonic acid or a derivative thereof or a mixture thereof, and β) at least one mole of at least one compound per mole of compound VI. A condensation product V of a carboxylic acid or sulfonic acid VII containing two free-radically polymerizable functional groups, or a derivative thereof or a mixture thereof, and b2) 0 to 95% by weight, based on the composition IV Having an average molecular weight (number average) of at least 5,000 and having a polyether in its main or side chain. At least one first layer comprising a mixture Ia comprising a mixture IIa consisting of a polymer composition IV obtainable by polymerizing a further compound VIII having a mixture segment VIII having a mass fraction of 1% in the mixture Ia And 100% by weight), wherein the first layer does not include an electroconductive electrochemically active compound, and B) at least one first layer including an electroconductive electrochemically active compound. A composite material comprising two layers, wherein one or more of the first layers and one or more of the second layers are combined in two ways V1 or V2: V1) by the action of heat or pressure or by the action of heat and pressure. Laminating one or more of the first layers with one or more of the second layers, or V2) one or more of the first layers, one or more of the second layers Alternatively, the corona treatment of one or more of the first layer and the one or more of the second layers, and the subsequent corona-treated one or more first layers and one or more corona-treated or untreated second layers A composite material which is joined to one another by one of the methods of integration with a layer.

Description

DETAILED DESCRIPTION OF THE INVENTION

TECHNICAL FIELD The present invention relates, inter alia, to composites suitable for electrochemical cells having an electrolyte containing lithium ions; for example, the use of the composites in electrodes; electrodes, sensors, electros, and the like comprising such composites. Chromic windows, displays, capacitors and ion-conducting films; and electrochemical cells comprising such moldings;
About.

BACKGROUND OF THE INVENTION Electrochemical cells, particularly rechargeable electrochemical cells, are generally known. (See, for example, "Ullmann's Encyclopedia of Industry."
real Chemistry "5th edition, volume A3, VCH Verlagsg
esellschaft mbH, Weinheim, 1985, 343-39.
See page 7).

[0003] Among these batteries, a special position is occupied by lithium batteries and lithium ion batteries, especially as secondary batteries, because of their high specific energy storage density.

As described, for example, in the above-cited “Ullmann” reference, the cathode of such a cell may be LiMn ₂ O ₄ , LiCoO ₂ , LiV ₂ O ₅ or stoichiometrically simple. Includes mixed oxides of lithium and manganese, cobalt, vanadium or nickel, which can be described as LiNiO ₂ .

[0005] These mixed oxides react reversibly with compounds capable of incorporating lithium ions into their lattice, such as graphite, for example, where lithium ions are extracted from the crystal lattice and manganese, cobalt present in the latter are present. Alternatively, metal ions such as nickel ions are oxidized. In the electrochemical cell, the lithium ions migrate from the mixed oxide to the anode material inside the electrochemical cell between the compound that takes in the lithium ions as the anode material and the lithium-containing mixed oxide as the cathode material (in the charging operation). Cases) are used to store electrical energy by being separated by an electrolyte.

[0006] Compounds suitable for reversible storage of lithium ions are usually fixed to the collector electrode by a binder.

[0007] When charging a battery, electrons flow through an external power source and lithium cations travel through an electrolyte toward an anode material. When using a battery, lithium cations flow through the electrolyte, while electrons flow from the anode material through the load to the cathode material.

To avoid short circuits in electrochemical cells, an electrically insulating but lithium cation permeable layer is located between the two electrolytes. This layer may be a solid electrolyte or a normal separator.

In the manufacture of many electrochemical cells, for example, lithium ion cells in the form of round cells, the required battery films, cathode, anode and separator film, are combined using a rolling device to obtain a battery roll. In a conventional lithium-ion battery, the cathode and anode film (s) are joined to a collector electrode, for example, of foil or aluminum. Such a metal foil ensures sufficient mechanical stability.

[0010] In contrast, separator films must themselves be resistant to mechanical stress, which is a problem in the case of conventional separator films having a normal thickness, for example based on polyolefins. Do not present. In order to further improve the mechanical stability of such a conventional separator film, JP 09-134 7
30 and JP 09-161 815 propose to bond these separator films to anode and / or cathode films by means of a tie layer.

[0011] In contrast to conventional separator films, the mechanical stability of solid-filled separator films is generally not sufficient to ensure trouble-free film rolling.

It is an object of the present invention to provide a composite material having at least one layer filled with a solid, suitable for use in an electrochemical cell, for example, capable of withstanding mechanical stress in the manufacture of the cell. .

[0013] The inventors have found that this object is achieved by the composite of the present invention.

The composite includes at least one first layer (eg, a separator layer) filled with a solid, and at least one second layer, which can be a cathode or anode layer. Accordingly, the composites of the present invention include a separator layer / anode layer combination or a separator layer / cathode layer combination or a cathode layer / separator layer / anode layer combination, and, of course, the support materials and / or additional Layers can also be present.

Embodiments Accordingly, the present invention provides, in a first embodiment, a process comprising the steps of: Aa) a) 1 to 95% by weight of a solid III having a primary particle size of 5 nm to 20 μm, preferably a basic solid III, And b) 5 to 99% by weight, b1) 5 to 100% by weight, based on composition IV, α) a carboxylic acid or sulfonic acid or a derivative thereof or at least one capable of reacting with a mixture thereof. One compound VI and β) a carboxylic acid or sulfonic acid VII containing at least one mole of at least one free-radical polymerizable functional group per mole of compound VI, or a derivative thereof or a mixture of two or more thereof B) 0 to 95% by weight, based on composition IV, of less than A mixture comprising a mixture IIa consisting of a polymer composition IV having an average molecular weight (number average) of both 5,000 and obtainable by polymerizing a further compound VIII having a polyether segment in its main or side chain At least one first layer containing the material Ia (where the mass proportion of the mixture IIa in the mixture Ia is 1 to 100% by weight), wherein the first layer does not contain an electroconductive electrochemically active compound. A composite comprising: one layer; and B) at least one second layer comprising an electrically conductive electrochemically active compound. One or more of the first layers and one or more of the second layers are formed in two ways V1 or V2: V1) One or more of the first layer and the singular by the action of heat or pressure or by the action of heat and pressure. Or V2) one or more of the first layers, one or more of the second layers, or one or more of the first layers and one or more of the second layers. Joined to one another by one of two layers of corona treatment followed by integration of the corona-treated one or more first layers and the corona-treated or untreated one or more second layers .

The first layer or the first layers preferably comprise: a) 1 to 95% by weight of a solid III having a primary particle size of 5 nm to 20 μm, preferably a basic solid III, and b) 5 to 5% by weight. B) 5 to 100% by weight, based on polymer composition IV, of α) polyhydric alcohol VI containing carbon and oxygen atoms in its main chain, and β) per mole of polyhydric alcohol VI. At least 1 mol of a condensation product V of an α, β-unsaturated carboxylic acid VII, and b2) from 0 to 95% by weight, based on composition IV, having an average molecular weight (number average) of at least 5,000. And a polymer composition I obtainable by polymerizing a further compound VIII having a polyether segment in its main or side chain A mixed material Ia containing a mixture IIa consisting of V 2 is contained. Here, the mass ratio of the mixture IIa in the mixture material Ia is 1 to 100% by mass.

In another aspect, the present invention provides a method comprising: a) 1) to 95% by weight of a solid III having a primary particle size of 5 nm to 20 μm, preferably a basic solid, and b) 5 to 99% by weight. B1) from 5 to 75% by weight, based on polymer IX, of compound X which is free-radically polymerizable and which is different from carboxylic acid or sulfonic acid VII, or a derivative thereof or a mixture of two or more thereof, and b2 ) 25-95% by weight, based on polymer IX, of at least 5,000
At least one first material containing a mixture Ib comprising a mixture IIb consisting of a polymer IX obtained by the polymerization of a further compound VIII having an average molecular weight (number average) of B) the first layer, which is free of electroconductive electrochemically active compounds, wherein the first layer does not contain an electroconductive electrochemically active compound; and A composite comprising at least one second layer comprising a non-electrochemically active compound.

Here, the one or more first layers and the one or more second layers are formed in two ways V1 or V2: V1) one or more by the action of heat or pressure or by the action of heat and pressure. Laminating the first layer with one or more second layers, or V2) one or more first layers, one or more second layers, or one or more first layers and Bonding to one another by one of corona treatment of the one or more second layers and subsequent integration of the corona-treated one or more first layers and the corona-treated one or more second layers Is done.

The present invention further provides at least one first layer Aa, or at least one first layer Ab, or at least one first layer Aa and at least one first layer Ab; C) at least one tie layer.

The components present in each layer of the composite of the present invention are described in more detail below. First layer A The solids III used in this layer are, first of all, the I, II, II
Oxides, mixed oxides, silicates of the I and main IV and IV transition elements,
Inorganic solids, preferably inorganic basic solids, selected from the group consisting of sulfates, carbonates, phosphates, nitrides, amides, imides and carbides; polyethylene, polypropylene, polystyrene, polytetrafluoroethylene, polyvinylidene fluoride, A polymer selected from the group consisting of polyamides and polyimides; solid dispersions containing such polymers; and mixtures of two or more thereof.

Examples are, in particular, calcium oxide, silicon dioxide, aluminum oxide, magnesium oxide or titanium dioxide, for example silicon, calcium, aluminum,
Oxides such as mixed oxides of elements such as magnesium and titanium; ladder, chain, plate and skeletal silicates (preferably wollastonite, especially hydrophobic wollastonite); alkali metals and alkaline earths Sulfates such as metal sulfates; carbonates such as alkali metal and alkaline earth metal carbonates (eg calcium carbonate, magnesium carbonate or barium carbonate or lithium carbonate, potassium carbonate or sodium carbonate; phosphoric acid such as apatite) Amides; carbides; polymers such as polyethylene, polypropylene, polystyrene, polytetrafluoroethylene and polyvinylidene fluoride; polyamides; polyimides; or other thermoplastics, thermosets and microgels, solid dispersions (Especially the polymer described above) Dressings), and mixtures of two or more of the solid and the like.

Furthermore, an inorganic solid that conducts Li ions, preferably an inorganic basic solid that conducts Li ions, can be used according to the invention as solid III.

Examples are Li ₄ B ₆ O ₁₁ * xH ₂ O, Li ₃ (BO ₂ ) ₃ , Li ₂ B ₄ O ₇ * xH ₂ O
, LiBO ₂ (where x can be 0 to 20); aluminates such as Li ₂ O * Al ₂ O ₃ * H ₂ O, Li ₂ Al ₂ O ₄ , LiAlO ₂ Lithium; lithium-containing zeolites, feldspars, feldspars, phyllosilicates and inosilicates, and especially LiAlSi ₂ O ₆ (spodumene), LiAlSi ₄ O ₁₀ (petulite), LiAlSiO ₄ (eucryptide), K [Li _{, Al] 3 [AlSi] 4} O 10 (F-OH) 2 / K [Li, Al, Fe] 3 [AlSi] 4 O 10 (F-OH) 2 ( mica) aluminosilicate lithium like; lithium zeolite (Especially those of fibrous, plate-like or cubic shape, in particular of the formula Li _{2 / z} O * Al ₂ O ₃ * xSiO ₂ * yH ₂ O (where z is related to valency and x is 1.8 to about 1 In it, y is 0 to about 8) ones); Li ₂ C _2, carbide Lithium such as _{Li 4 C; Li 3 N;} LiAlO 2, Li 2 MnO 3, Li 2 O, Li 2 O ₂ , Li ₂ Mn
Lithium oxides and mixed oxides such as O ₄ , Li ₂ TiO ₃ ; Li ₂ NH; Li
NH ₂ ; Li ₃ PO ₄ , LiPO ₃ , LiAlFPO ₄ , LiAl (OH) PO ₄ , L
Lithium phosphates such as iFePO ₄ , LiMnPO ₄ ; ladder, chain, plate and skeleton shaped lithium silicates (eg Li ₂ SiO ₃ , Li ₂ SiO ₄ and Li ₆ Si ₂ ); Li ₂ SO ₄ , LiHSO _4, lithium sulfate as LiKSO _4; Li compound shown when addressing the cathode de layer (in the case of using these as a solid III, of conductive carbon black contained is excluded from the mixture); Li-
Mixtures of two or more of the above solids that conduct ions.

Particularly suitable solids III are basic solids. As far as the present invention is concerned, basic solids are those in which a mixture of a diluent and a solid containing water and water, which itself has a pH of approximately 7, has a higher pH than this diluent.

The solid is significantly insoluble in the liquid used as the electrolyte,
Preferably, it is electrochemically inert in the battery medium.

Particularly suitable solids are 5 nm to 20 μm, preferably 0.01 to 10 μm
m, particularly preferably having a primary particle size of 0.1 to 5 μm,
The specific particle size is determined by an electron microscope. The melting point of the solid is preferably above the normal operating temperature of the electrochemical cell, and has proved to be particularly useful when it has a melting point above 120 ° C, especially above 150 ° C.

With regard to its external shape, the solid has a symmetrical shape, ie, a height: width: length aspect ratio of about 1, a sphere, a fine grain, a substantially round structure, or a cuboid, tetrahedron May be any polyhedral shape, such as a hexahedron, octahedron or bipyramid,
Alternatively, a distorted or asymmetric shape, i.e., a needle: asymmetric tetrahedron, asymmetric bipyramid, asymmetric hexahedron or octahedron, where the aspect ratio of height: width: length is not equal to 1, It may be in the form of a small flat plate, a disk or a fiber. If the solid is in the form of asymmetric particles, the above upper limits for primary particle size refer to the smallest axis in each case.

Carboxylic acid or sulfonic acid VII, or a derivative or a derivative thereof
As compound VI capable of reacting with the above mixture, in principle, all compounds satisfying this criterion can be used.

Compound VI is selected from the group consisting of a monohydric or polyhydric alcohol having only carbon atoms in its main chain; oxygen, phosphorus and nitrogen in addition to at least 2 carbons in its main chain. Mono- or polyhydric alcohols having at least one atom; silicon-containing compounds; amines having at least one primary amino group; amines having at least one secondary amino group; amino alcohols; Preferred are compounds selected from the group consisting of thiols; compounds having at least one thiol group and at least one hydroxyl group; and mixtures of two or more thereof.

Of these, compounds VI having two or more functional groups capable of reacting with carboxylic acids or sulfonic acids are preferred.

When a compound VI containing an amino group as a functional group is used, a secondary amino group is added after condensation / crosslinking so that the mixed material Ia has no or only a small amount of free NH groups. It is preferable to use those having

Specific examples of preferred compounds include those having only carbon atoms in the main chain thereof and having 1 to 20 alcoholic OH groups (preferably 2 to 20 alcoholic O
Monohydric or polyhydric alcohols having an H group, particularly preferably 2 to 10 alcoholic OH groups), particularly preferably ethylene glycol, 1,2- or 1,1
3-propanediol, 1,2- or 1,3-butanediol, 1,4-butanediol, 1,4-butynediol, 1,6-hexanediol, neopentyl glycol, 1,2-dodecanediol, glycerol And dihydric, trihydric and tetrahydric alcohols having 2 to 20 carbon atoms, such as trimethylolpropane, pentaerythritol, sugar alcohols, hydroquinone, novolak and bisphenol A. As is clear from the above, monohydric alcohols such as methanol, ethanol, propanol, n-, sec- or tert-butanol can also be used. It is also possible to use a polyhydroxy olefin having two terminal hydroxyl groups, preferably α, ω-dihydroxybutadiene. For example, Ulmmans Encyclop
For example, polyester polyols obtained by reacting a dihydric alcohol with a polybasic, preferably dibasic polycarboxylic acid, as in adie der technischen Chemie, 4th edition, Vol. 19, pp. 62-65. Can also be used. Further, a monohydric or polyhydric alcohol containing at least one oxygen atom in addition to two or more carbon atoms in its main chain, preferably an alkylene epoxide (for example, isobutylene oxide, propylene oxide, ethylene oxide, 1,2- Epoxy butane, 1,2-epoxy pentane, 1,2-
Polyester alcohols such as the polymerization products of epoxy hexane, tetrahydrofuran and styrene oxide) can also be used. Also, polyether alcohols modified with end groups, for example, polyether alcohols modified with NH ₂ end groups, can be used. These alcohols preferably have a molecular weight (number average) of 100 to 5,000, more preferably 200 to 1,000, particularly preferably 300 to 800. Such compounds are known per se and are, for example, registered under the trademark Plurio or Pluronic (BA
It is available on the market under the name SF Aktiengesellschaft). It is also possible to use the above alcohols in which some or all of the carbon atoms have been replaced by silicon. Compounds of this type that can be used include:
In particular there are, for example, polysiloxanes or alkylene oxide-siloxane copolymers or mixtures of polyether alcohols and polysiloxanes, as described for example in EP-B 581 296 and EP-A 525 728, with regard to the molecular weight of these alcohols. What is stated applies. Also, the above-mentioned alcohols in which some or all of the oxygen atoms have been replaced by sulfur atoms, particularly polyether alcohols, can be used. As regards the molecular weight of these alcohols, the same already applies. Further, a monohydric or polyhydric alcohol containing at least one phosphorus atom or at least one nitrogen atom in addition to at least two carbon atoms in its main chain (eg, diethanolamine and triethanolamine), wherein z is 1 lactones (eg, .epsilon.-caprolactone, beta-propiolactone, .gamma.-butyrolactone or methyl -ε- caprolactone) which to be derived from a compound of formula HO- (CH _{2) z} -COOH 20 can be used. Further silicon-containing compounds such as dichlorosilane or trichlorosilane, phenyltrichlorosilane, diphenyldichlorosilane, dimethylvinylchlorosilane; silanols such as trimethylsilanol;
Amines having at least one primary and / or secondary amino group, such as 2-ethylhexylamine, ethylenediamine, hexamethylenediamine, diethylenetriamine, tetraethylenepentamine, pentaethylenehexamine, aniline, phenylenediamine; 4, 7-dioxydecane-1,10-diamine,
Polyether diamines such as 4,11-dioxytetradecane-1,14-diamine; for example, methanethiol, ethanethiol, cyclohexanethiol,
Aliphatic thiols such as dodecanethiol; and, for example, thiophenol, 4
Mono- or polyvalent thiols such as aromatic thiols such as chlorothiophenol, 2-mercaptoaniline; at least one thiol group such as 4-hydroxythiophenol and monothio derivatives of the above-mentioned polyhydric alcohols and at least one A compound having one hydroxyl group; ethanolamine, N-methylethanolamine, N-ethylethanolamine, N-butylethanolamine,
2-amino-1-propanol, 2-amino-1-phenylethanol, and monoamino or polyaminopolyols having two or more aliphatically linked hydroxy groups (e.g., tris (hydroxymethyl) -methylamine, glucamine, N,
Amino alcohols such as N'-bis (2-hydroxymethyl) ethylenediamine) can be used.

It is also possible to use mixtures of two or more of the abovementioned compounds VI.

According to the invention, the compound VI described above is condensed with a carboxylic acid or sulfonic acid VII having at least one free-radically polymerizable functional group, or a derivative thereof or a mixture of two or more thereof, In the condensation reaction, compound VI
At least one, and preferably all, of the condensable free radicals present in compound VI
Condensed with I.

The carboxylic or sulphonic acids VII which can be used for the purposes of the invention are in principle all carboxylic or sulphonic acids having at least one free-radical polymerizable functional group, or derivatives thereof. is there. Used here
The term "derivative" is derived from a carboxylic or sulfonic acid, an ester,
Compounds in which acid functional groups such as acid halides and acid anhydrides are modified, and compounds derived from carboxylic acids or sulfonic acids and in which the carbon skeleton of carboxylic acids or sulfonic acids such as halocarboxylic acids and halosulfonic acids are modified , Including both.

Examples of compounds VII include, in particular, α, β-unsaturated carboxylic acids or β, γ-
Unsaturated carboxylic acids.

Particularly suitable α, β-unsaturated carboxylic acids have the formula:

[0038]

Embedded image Wherein R ¹ , R ² and R ³ are hydrogen or a C ₁ -C ₄ -alkyl group, of which acrylic acid and methacrylic acid are particularly preferred, among which other suitable compounds Is cinnamic, maleic, fumaric, itaconic or p
-Vinylbenzoic acid and acid anhydrides such as maleic anhydride or itaconic acid; halides (especially chlorides such as acryloyl chloride or methacryloyl chloride; for example, methyl, ethyl, propyl, butyl, hexyl, 2-ethylhexyl) (Cyclo) alkyl (α-methyl) acrylates having up to 20 carbon atoms in an alkyl group such as, stearyl, lauryl, cyclohexyl, benzyl, trifluoromethyl, hexafluoropropyl, tetrafluoropropyl (
α-methyl) acrylate, propylene glycol mono (α-methyl) acrylate, polyethylene glycol mono (α-methyl) acrylate, for example, glyceryl di (α-methyl) acrylate, trimethylolpropane di (α-methyl) acrylate, pentaerythritol diacrylate Or poly (α-methyl) acrylates of polyhydric alcohols such as tri (α-methyl) acrylate, diethylene glycol bis (mono (2-acryloxy-ethyl) carbonate), for example (α-
Methyl) acrylic acid and alcohols such as esters of vinyl and / or allyl alcohol which themselves have groups capable of free radical polymerization
Esters such as -methyl) acrylate; for example, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl hexanoate, vinyl octanoate, vinyl decanoate,
Vinyl esters of other aliphatic or aromatic carboxylic acids such as vinyl stearate, vinyl palmitate, vinyl crotonate, divinyl adipate, vinyl sebacate, vinyl 2-ethylhexanoate, vinyl trifluoroacetate; Allyl, allyl propionate, allyl butyrate, allyl hexanoate, allyl crotonate, allyl decanoate, allyl stearate, allyl palmitate, allyl crotonate, allyl salicylate, allyl lactate, diallyl oxalate, diallyl malate,
Allyl and diallyl succinate, diallyl glutarate, diallyl adipate, diallyl pimerate, diallyl cinnamate, diallyl maleate, diallyl phthalate,
Allyl esters of other aliphatic or aromatic carboxylic acids such as diallyl isophthalate, triallyl benzene-1,3,5-tricarboxylate, diallyl cinnatricarboxylate, allyl trifluoroacetate, allyl perfluorobutyrate, allyl perfluorooctanoate; For example, β, γ-unsaturated carboxylic acids such as vinyl acetic acid, 2-methylvinyl lactic acid, isobutyl 3-butenoate, allyl 3-butenoate, allyl 2-hydroxy-3-butenoate, diketone or derivatives thereof; Sulfonic acids and their esters and halides, such as vinylsulfonic acid, allyl- and methylylsulfonic acid, and derivatives such as vinyl benzenesulfonate and 4-vinylbenzenesulfonamide.

Also, a mixture of two or more of the above carboxylic acids and / or sulfonic acids can be used.

Specific examples of compounds X capable of free radical polymerization and which can be used to synthesize polymer IX are: ethylene, propylene, butylene, isobutylene, hexene or higher homologues and olefins such as vinylcyclohexane (Α-methyl) acrylonitrile; vinylidene fluoride, vinylidene chloride, vinyl fluoride, vinyl chloride, hexafluoropropene, trifluoropropene, 1,2-dichloroethylene, 1,2-difluoroethylene and tetrafluoroethylene Halogen-containing olefinic compounds such as; vinyl alcohol, vinyl acetate, N-vinylpyrrolidone, N-vinylimidazole, vinylformamide; phosphonitrile chloride such as hexachloro (triphosphazene), and alkoxy; Derivatives thereof partially or completely substituted by enoxy, amino and fluoroalkoxy groups (ie compounds capable of polymerizing to give polyphosphazenes); aromatic olefinic compounds such as styrene, α-methylstyrene Vinyl ethers such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, hexyl, octyl, decyl, dodecyl, 2-ethylhexyl, cyclohexyl, benzyl, trifluoromethyl, hexafluoropropyl and tetrafluoropropyl vinyl ether.

Of course, it is also possible to use mixtures of the compounds X, which, depending on the preparation process, result in copolymers in which the monomers are distributed randomly or arranged in blocks.

Both compound X and condensation product V can be prepared by methods well known to those skilled in the art (
Preferably by free radical polymerization); with regard to molecular weight, the following applies in relation to compound VIII.

A suitable compound VIII is firstly at least 5,000, preferably 5
20,000 to 20,000,000, particularly preferably 100,000 to 6
It is a compound having an average molecular weight (number average) of 9,000,000, capable of solvating lithium cation, and functioning as a binder. Examples of suitable compounds VIII are
At least 30% by weight, based on the total weight of compound VIII, of the following structural units:

[0044]

Embedded image (Wherein R ¹ , R ² , R ³ and R ⁴ are an aryl group or an alkyl group (preferably a methyl group) or hydrogen, which may be the same or different, and include oxygen, nitrogen,
(Which may contain heteroatoms such as sulfur and silicon).

Such compounds are described, for example, in M. B. Armand et. al. , Fas
t Ion Transport in Solids, Elsevier, N
ew York, 1979, 131-136 and FR-A 7832976.

Compound VIII can also consist of a mixture of two or more such compounds.

The above-described polymer composition IV or polymer IX may be in the form of a foam, in which case the solid III is dispersed therein.

According to the invention, the mixture IIa comprises 1 to 95% by weight, preferably 25 to 90% by weight, particularly preferably 30 to 70% by weight of solid III and 5 to 99% by weight, preferably 10 to 75% by weight And particularly preferably 30 to 70
% By weight of the polymer composition IV, wherein the compound VIII in the polymer composition IV
Is from 5,000 to 100,000,000, preferably from 50,000 to 8
It is desirable to have an average molecular weight (number average) of 3,000,000. Polymer composition IV is 5 to 100% by weight, preferably 3% by weight, based on polymer composition IV.
It can be obtained by reacting 0 to 70% by weight of compound V with 0 to 95% by weight, particularly preferably 30 to 70% by weight, based on polymer composition IV, of compound VIII.

According to the invention, mixture IIb comprises 1 to 95% by weight, preferably 25 to 90% by weight, particularly preferably 30 to 70% by weight of solid III and 5 to 99% by weight, preferably 10 to 75% by weight %, Particularly preferably 30 to 7
0% by weight of polymer IX, wherein compound VIII in polymer IX
0 to 100,000,000, preferably 50,000 to 8,000,000
It is desirable to have an average molecular weight (number average) of 000. The polymer IX is obtained by reacting 5 to 75% by weight, preferably 30 to 70% by weight, of the compound X based on the polymer IX with 25 to 95% by weight, in particular 30 to 70% by weight, of the compound VIII based on the polymer IX. Can be obtained by

In the following, the admixtures Ia and Ib used in the present invention and the mixtures IIa and IIb used in the present invention will be discussed together and will be referred to as “the admixture used in the present invention” and “
The mixture used in the present invention ".

The admixture used according to the invention, which contains the mixture according to the invention in an amount of 1 to 100% by weight, preferably 35 to 100% by weight, particularly preferably 30 to 70% by weight, based on the admixture used according to the invention. To synthesize, solid III, condensation product V and
If necessary, a mixture of compound VIII or a mixture of solid III, compound X, compound VIII and a plasticizer (preferably a plasticizer including polyethylene oxide or polypropylene oxide) is prepared.

Second layer B The polymer binders used in this second layer B include, in particular, the following polymers: 1) homopolymers obtainable by polymerization of the mixtures Ia or Ib,
Copolymer or block copolymer IVa (polymer IVa), 2) polycarbonates such as polyethylene carbonate, polypropylene carbonate, polybutadiene carbonate, polyvinylidene carbonate, 3) a) ethylene, propylene, butylene, isobutylene, propene, hexene or higher homologs Olefinic hydrocarbons, such as butadiene, cyclopentene, cyclohexene, norbornene, vinylcyclohexane, b) aromatic hydrocarbons, such as styrene and methylstyrene, c) esters of acrylic or methacrylic acid, for example, methyl, ethyl, propyl , Isopropyl, butyl, isobutyl, hexyl, octyl, decyl, dodecyl, 2-ethylhexyl, cyclohexyl, benzyl, trifluoro Lomethyl,
Hexafluoropropyl or tetrafluoropropyl acrylate or methacrylate, d) acrylonitrile, methacrylonitrile, N-methylpyrrolidone, N-vinylimidazole, vinyl acetate, e) methyl, ethyl, propyl, isopropyl, butyl, isobutyl, hexyl, octyl, Decyl, dodecyl, 2-ethylhexyl, cyclohexyl, benzyl, vinyl ether such as trifluoromethyl, hexafluoropropyl or tetrafluoropropyl vinyl ether; f) vinyl chloride, vinyl fluoride, vinylidene fluoride, vinylidene chloride, hexafluoropropene, tri From halogen-containing olefinic compounds such as fluoropropene, 1,2-dichloroethene, 1,2-difluoroethene, tetrafluoroethene; Homopolymers, copolymers or block copolymers to be synthesized 4) a) organic diisocyanates having 6 to 30 carbon atoms (for example, aliphatic acyclics such as hexamethylene 1,5-diisocyanate and hexamethylene 1,6-diisocyanate) Aliphatic cyclic diisocyanates such as diisocyanate, cyclohexylene 1,4-diisocyanate, dicyclohexylmethane diisocyanate and isophorone diisocyanate, or toluene 2,4-
Aromatic diisocyanates such as diisocyanate, toluene 2,6-diisocyanate, m-tetramethylxylene diisocyanate, p-tetramethylxylene diisocyanate, tetrahydronaphthalene 1,5-diisocyanate and diphenylmethane 4,4'-diisocyanate) or such compounds B) polyurethanes which can be obtained by reacting a mixture of the above with b) polyhydric alcohols such as polyesterols, polyesterols and diols.

The polyesterol is preferably a linear polymer having mainly terminal OH groups (preferably 2 or 3, particularly preferably 2 OH terminal groups). The acid value of the polyesterol is less than 10, preferably less than 3. Polyesterols esterify aliphatic or aromatic dicarboxylic acids having 4 to 15 carbon atoms (preferably 4 to 6 carbon atoms) with glycols (preferably glycols having 2 to 25 carbon atoms). Or a simple method such as a method of polymerizing a lactone having 3 to 20 carbon atoms. Examples of dicarboxylic acids which can be used are glutaric acid, pimelic acid, suberic acid, sebacic acid, dodecanoic acid and preferably adibic acid and succinic acid.
Suitable aromatic dicarboxylic acids are terephthalic acid, isophthalic acid, phthalic acid, or mixtures of these dicarboxylic acids with other dicarboxylic acids such as diphenic acid, sebacic acid, succinic acid and adipic acid. The dicarboxylic acids can be used individually or as a mixture. To synthesize polyesterol, it is preferable to use a carboxylic anhydride or a carboxylic acid chloride instead of the dicarboxylic acid. Examples of suitable glycols are diethylene glycol, 1,5-pentanediol, 1,10-decanediol and 2,2,4-trimethylpentane-1,
5-diol. 1,2-ethanediol, 1,3-propanediol, 2
-Methylpropane-1,3-diol, 1,4-butanediol, 1,6-hexanediol, 2,2-dimethylpropane-1,3-diol, 1,4-dimethylolcyclohexane, 1,4-diethanol It is a product obtained by ethoxylating or propoxylating cyclohexane and 2,2-bis (4-hydroxyphenyl) propane (bisphenol A). Depending on the desired properties of the polyurethane,
The polyols can be used alone or as mixtures of various mixing ratios. Suitable lactones for producing polyesterols are, for example, α, α-
Dimethyl-β-propiolactone, γ-butyrolactone and preferably ε-caprolactone.

Polyetherol is a substantially linear substance having a terminal hydroxyl group and containing an ether bond. Suitable polyetherols can be obtained by polymerization of a cyclic ether such as tetrahydrofuran or by adding 2 to 4 alkylene groups.
It can be readily synthesized by reacting one or more alkylene oxides having two carbon atoms with an initiator molecule containing two active hydrogen atoms in the form of a bond in the alkylene group. Suitable alkylene oxides are ethylene oxide, 1,2-propylene oxide, epichlorohydrin, 1,2-butylene oxide and 2,3-butylene oxide. The alkylene oxides can be used individually, sequentially or as a mixture. Suitable initiator molecules are, for example, water, glycols such as ethylene glycol, propylene glycol, 1,4-butanediol and 1,6-hexanediol, ethylenediamine, hexamethylenediamine and 4,4'-diaminodiphenylmethane. Amines and amino alcohols such as ethanolamine. For suitable polyesterols and polyetherols and their synthesis, see, for example, EP
-B 416 386; suitable polycarbonate diols are
Preferably they are based on 1,6-hexonediol, their synthesis being described, for example, in US Pat. No. 4,131,731.

Preferably, up to 30% by weight, based on the total weight of the alcohol, of 2 to 20%
Aliphatic diols having from 2, preferably 2 to 10 carbon atoms, such as 1
, 2-ethanediol, 1,3-propanediol, 1,4-butanediol,
1,6-hexanediol, 1,5-pentanediol, 1,10-decanediol, 2-methylpropane-1,3-diol, 2,2-dimethylpropane-1
, 3-diol, 2-methyl-2-butylpropane-1,3-diol, 2,2
-Dimethylbutane-1,4-diol, 1,4-dimethylolcyclohexane,
Neopentyl glycol hydroxypivalate, diethylene glycol, triethylene glycol and methyldiethanolamine, or an aromatic-aliphatic or aromatic having 8 to 30 carbon atoms, wherein the possible aromatic structure is a heterocyclic or preferably isocyclic system -Cycloaliphatic diols such as naphthalene or especially bisphonol A, symmetrically diethoxylated bisphenol A, symmetrically dipropoxylated bisphenol A, higher ethoxylated or propoxylated bisphenol A derivatives or bisphenol F Benzene derivatives, such as derivatives), and mixtures of such compounds.

Up to 5% by weight, based on the total weight of the alcohol, of aliphatic triols having 3 to 15, preferably 3 to 10 carbon atoms (for example trimethylolpropane or glycerol), such compounds and Echilen oxide and / or
Alternatively, reaction products with propylene oxide and mixtures of such compounds can be used.

Polyhydric alcohols are functional groups, for example neutral groups such as siloxane groups, in particular basic groups such as tertiary amino groups or acidic groups or their salts or groups which are easily converted to acidic groups. Can carry. These groups are introduced via a polyhydric alcohol. Diol compounds bearing such groups (eg, N-methyldiethanolamine, diethyl N, N-bis (hydroxyethyl) aminomethylphosphonate or 3-sulfopropyl N, N-bis (hydroxyethyl) -2-aminoacetate), Preference is given to dicarboxylic acids bearing such groups which can be used for the synthesis of polyesterols, for example 5-sulfoisophthalic acid.

Acid groups are, in particular, phosphoric, phosphonic, sulfuric, sulfonic, carboxyl or ammonium groups.

Groups which are easily converted to acidic groups are, for example, ester groups or preferably salts of alkali metals such as lithium, sodium or potassium. 5) It should be noted that the polyesterols themselves; it should be ensured that a molecular weight in the range of 10,000 to 2,000,000, preferably 50,000 to 1,000,000 is obtained. 6) Polyamines, polysiloxanes and polyphosphazenes, especially polymer IV
Those already discussed in the description of b. 7) Polyetherols, such as those mentioned in the discussion of polymer IVa as compound IX or in the discussion of polyurethane.

If layer B is a cathode layer, the layer is preferably lithium ion
Electric conductivity commonly used as a cathode (cathode compound) that can release
It contains an electrochemically active compound (preferably a lithium compound). To mention
Specific examples that can be made are: LiCoO_Two, LiNiO_Two, LiN_xCo_yO_Two, LiNi_xCO_yAl_zO_Two, (Where 0 <x, y, z "1), Li_xMnO_Two(0 <x ”1), Li_xMn_TwoO_Four(0 <x) 2), Li_xMoO_Two(0 <x) 2), Li_xMnO_Three(0 <x ”1), Li_x MnO_Two(0 <x) 2), Li_xMn_TwoO_Four(0 <x) 2), Li_xV_TwoO_Four(0 <x) 2
. 5), Li_xV_TwoO_Three(0 <x) 3.5), Li_xVO_Two(0 <x ”1), Li_xWO _Two (0 <x ”1), Li_xWO_Three(0 <x ”1), Li_xTiO_Two(0 <x ”1), Li _x Ti_TwoO_Four(0 <x) 2), Li_xRuO_Two(0 <x ”1), Li_xFe_TwoO_Three(0 <x
2), Li_xFe_ThreeO_Four(0 <x) 2), Li_xCr_TwoO_Three(0 <x) 3), Li_xCr _Three O_Four(0 <x) 3.8), Li_xV_ThreeS_Five(0 <x) 1.8), Li_xTa_TwoS_Two(0 <
x "1), Li_xFeS (0 <x ”1), Li_xFeS_Two(0 <x ”1), Li_xNb S_Two(0 <x) 2.4), Li_xMoS_Two(0 <x) 3), Li_xTiS_Two(0 <x) 2
), Li_xZrS_Two(0 <x) 2), Li_xNbSe_Two(0 <x) 3), Li_xVSe_Two (0 <x ”1), Li_xNiPS_Two(0 <x ”1.5), Li_xFePS_Two(0 <x) 1.5.

If layer B is an anode layer, the layer comprises a conventional, electrically conductive, electrochemically active compound (anode compound) known in the prior art, capable of taking up lithium ions upon charging; Specific examples that may be mentioned are: lithium, lithium-containing metal alloys, micronized carbon black, natural and synthetic graphite, synthetically graphitized carbon powders and fibers, titanium dioxide, zinc oxide, tin oxide, molybdenum oxide and Oxides such as tungsten oxide, and carbonates such as titanium carbonate, molybdenum carbonate and zinc carbonate.

If layer B is used as an anode layer, the layer may further comprise up to 20% by weight of a conductive black, based on the total weight of the material present (polymer binder + anode compound) and, if necessary, Contains additives. If layer B is used as or for producing a cathode, it further comprises 0.1 to 20% by weight of conductive black, based on the total weight of the material present (polymer binder + cathode compound). contains.

Bonding layer C As the bonding layer C, in principle, all materials capable of bonding the above-mentioned single or plural first layers and the above-mentioned single or plural second layers can be used. it can.

The tie layer generally comprises one or more first layers or one or more second layers, especially if the layers in question are joined by hot lamination.
Alternatively, it is a material having a melting point lower than the melting point of one or more first layers and one or more second layers, preferably 20 to 50 ° C. The melting points of these materials are generally between 25 and 250 ° C., preferably between 50 and 200 ° C.
Especially 70 to 180 ° C.

The tie layer can also include solid III. The amount of the solid substantially corresponds to the amount specified for layers A and B, each based on the material forming the tie layer.

As such a material forming the tie layer, all materials commonly used as adhesives can be used. Of course, by conventional methods of layer formation (eg, printing, casting, spraying, extrusion, doctor blade coating, etc.)
These materials can be applied to layers A and / or B.

The use of a polymer compound as a material forming the tie layer is preferred.

The following may be mentioned: melt-type adhesives, which are generally based on ethylene-vinyl acetate copolymers further mixed with a resin and / or wax or paraffin so as to change their melt flow index, Molecular weight (co)
Melt adhesives based on polyethylene, atactic (co) polypropylene, ethylene-acrylic ester copolymers and styrene-butadiene and styrene-isoprene block copolymers, polyisobutylene and poly (meth) acrylate, and also their melt flow index Polyesters, such as polyethylene terephthalate, each of which can be mixed with a plasticizer (especially those listed here) to alter it; a mixture of finely divided polyvinyl chloride dispersed in a plasticizer and reacted by the action of heat to combine Adhesive plastisol (eg, epoxy resin compound, phenolic resin, etc.) substantially mixed with a low molecular weight substance acting as an agent; vinyl chloride or vinylidyl chloride which can also be mixed with other polymers or resins Down, copolymers of vinyl acetate, polymethacrylic esters, thermal bonding adhesives based on polyurethane and polyester;
Contact adhesives such as those based on natural rubber, synthetic rubber mixed with resins and solutions of high molecular weight polyurethane elastomers (where the rubber component used is mostly polychloroprene, nitrile or SBR rubber, The resins used are primarily phenolic, rosin and hydrocarbon resins); synthetic and natural rubbers, poly (methacrylic) esters, polyvinyl ethers and polyethers, respectively, also combined with modified natural resins, phenol-formaldehyde resins or hydrocarbon resins. Pressure sensitive adhesives, such as those based on isobutylene; poly (α
Pressure-sensitive dispersion adhesives based on -methyl) acrylic acid; cold-curing, hot-curing (about 80 to about 100 ° C.) and heat-curing (about 100 to about 250 ° C.) such as one- or two-component polymerized adhesives ) Reactive adhesive (The polymer used in the two-component polymerized adhesive is
In particular, accelerators such as amine-based accelerators and synthetic rubbers such as polychloroprene, styrene-butadiene rubber, butyl rubber, polystyrene, polymethacrylate containing, for example, benzoyl peroxide as a curing agent, one-component polymerization Examples of adhesives are based on cyanoacrylate); epoxy adhesives such as adhesives based on the condensation products of polychlorophenols such as epichlorohydrin and bisphenol A; aminoplastisols; phenols Resin adhesives; reactive polyurethane adhesives; polymethylol compounds; silicone adhesives; and polyimides and polyimidazoles such as polyaminamide and polybenzimidazole.

Particular examples are: polyethylene oxide; poly (vinyl methyl ether), poly (vinyl ethyl ether), poly (vinyl propyl ether), poly (vinyl butyl ether)
(Co) polyacrylates and (co) polymethacrylates, preferably polybutyl (meth) acrylate or polyhexyl (meth) acrylate with relatively long alkyl chains; polyvinylpyrrolidone; Polyurethanes (the above polyurethanes can be used as well); waxy (co) polyolefins such as polyethylene, polypropylene and polyisoprene wax; rubbery materials; polyisobutylene; and mixtures of two or more thereof.

Further details about the materials that can be used in the present invention in the tie layer can be found in
An article entitled "Kleben und Klebestoffe" (Che
Mie in unser Zeit, number 4 (1980),
And Ullmann, Encyclopedia technisc
hen Chemie, 4th edition (1977), volume1
4, 227-268 and the references cited therein),
The content of the adhesive material is incorporated herein by reference.

Layer A and / or B and / or C further comprise a plasticizer.

Plasticizers that can be used are those that solvate aprotic solvents, preferably Li ions (eg, dimethyl carbonate, diethyl carbonate, dipropyl carbonate, diisopropyl carbonate, dibutyl carbonate, ethylene carbonate and propylene carbonate); Dibutyl ether, di-tert
-Butyl ether, dipentyl ether, dihexyl ether, diheptyl ether, dioctyl ether, dinonyl ether, didecyl ether, didodecyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, 1-tert-butoxy-2-methoxyethane, 1- tert-butoxy-2-ethoxyethane, 1,2-dimethoxypropane, 2-methoxyethyl ether, 2-ethoxyethyl ether, diethylene glycol dibutyl ether, dimethylene glycol tert-butyl methyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether Oligoalkylene oxides such as, γ-butyrolactone, dimethylformamide;
nH2n + 2 (where 7 <n <50) hydrocarbons; organic phosphorus compounds, especially trimethyl phosphate, triethyl phosphate, tripropyl phosphate, tributyl phosphate, triisobutyl phosphate, tripentyl phosphate, phosphorus Trihexyl acid, trioctyl phosphate, tris (2-ethylhexyl) phosphate, tridecyl phosphate, diethyl n-butyl phosphate, tris (butoxyethyl) phosphate, tris (2-methoxyethyl) phosphate, tris (tetrahydrochloride) Frill), tris phosphate (1H, 1H, 5
H-octafluoropentyl), tris (1H, 1H-trifluoroethyl) phosphate, tris (2- (diethylamino) ethyl) phosphate, diethyl ethylphosphonate, dipropyl propylphosphonate, dibutyl butylphosphonate, hexylphosphonic acid Dihexyl, dioctyl octyl phosphonate, ethyl dimethyl phosphonoacetate, methyl diethyl phosphonoacetate, triethyl phosphonoacetate, dimethyl (2-oxopropyl) phosphonate, diethyl (2-oxopropyl) phosphonate, (
Phosphates and phosphonates such as dipropyl 2-oxo) phosphonate, ethyl diethoxyphosphinylformate, trimethyl phosphonoacetate, triethyl phosphonoacetate, tripropyl phosphonoacetate, tributyl phosphonoacetate; sulfates, sulfonates, sulfoxides, sulfones and sulfites Organic sulfur compounds such as dimethyl sulfite, diethyl sulfite, glycol sulfite, dimethyl sulfone, diethyl sulfone, diethyl propyl sulfone, dibutyl sulfone, tetramethylene sulfone, methyl sulfolane, dimethyl sulfoxide, diethyl sulfoxide, dipropyl sulfoxide , Dibutylsulfoxide, tetramethylenesulfoxide, ethylmethanesulfonate, 1
, 4-butanediol bis (methanesulfonate), diethyl sulfate, dipropyl sulfates, dibutyl sulfates, dihexyl sulfate, dioctyl sulfate, SO ₂ C _l F; nitriles such as acrylonitrile; dispersing (especially surfactant And a mixture thereof.

Further, at least one ester of the following formulas (E1) to (E5) can be used as a plasticizer.

[0074]

Embedded image

Embedded image

Embedded image

Embedded image

Embedded image In the formula, R ¹ , R ² , R ³ , and R ⁴ may be the same or different, and each is independently a linear or branched C ₁ -C ₄ alkyl group, (− CH ₂ —CH ₂ —O) _n —CH ₃ (where n is 1 to 3), a C ₃ —C ₆ -cycloalkyl group, an aromatic hydrocarbon (which may be substituted, provided that R ^1, R ^2, R ³ or at least one of R ⁴ is _{(-CH 2 -CH 2 -O) n} -CH 3 ( here, n represents from 1 3)).

[0075] Among the esters of the above formulas (E1) to (E5), it is preferable to use a phosphoric ester of the formula (E3).

Examples of groups R 1 and R 2 and, if present, R 3 and / or R 4 include:
Methyl, ethyl, n-propyl, isopropyl, n- and tert-butyl,
Cyclopentyl, cyclohexyl and benzyl and, (-CH ₂ -CH ₂ -
O) _n -CH ₃ where n is 1 to 3, however, as already mentioned, at least one of the radicals R ¹ , R ² , R ³ or R ⁴ is (-CH _2- CH ₂ —O
) _N -CH ₃ (here, n represents 1 to 3 should preferably be noted that it is 1 or 2).

Further, R ¹ , R ² and, if present, R ³ and / or R ⁴ are the same and are —CH ₂ —CH ₂ O—CH ₃ or (—CH ₂ —CH ₂ —O) Preference is given to using esters of the formulas (E1) to (E5) which are _2- CH ₃ , with the corresponding phosphoric esters being particularly preferred.

Examples of particularly preferred compounds are those of the formulas (E1a) to (E5a):

[0079]

Embedded image

Embedded image Is a compound of

Due to their properties, the esters used here are very suitable as plasticizers for the layer in question, generally at room temperature “10 mPas, preferably” 5 mPas,
Particularly preferably, it has a viscosity of 3 mPas. They generally each have a boiling point, measured at atmospheric pressure, of at least about 200 ° C., preferably at least about 250 ° C., particularly preferably at least about 300 ° C., at the temperature at which they are used (ie at about -50 ° C.). (Temperature of about 150 ° C. to about 150 ° C.) with a sufficiently low vapor pressure of about 10 ^{−5 to} about 100 mbar. As a result of their boiling points, they can be distilled and thus be produced in high purity. Furthermore, these esters are liquids over a wide temperature range at atmospheric pressure,
It is generally still liquid down to temperatures as low as -30C, preferably down to about -40C. The esters described herein can be used as a plasticizer and as a solvent in electrolyte systems for Li-ion batteries at at least about 80 ° C, preferably at least about 120 ° C, more preferably at least about 150 ° C.

Of course, the ester used in the present invention can also be used as a mixture with the above plasticizer.

It has a sufficiently low viscosity, can strongly solvate the ions of the conductive salt, is liquid over a wide temperature range, is sufficiently electrochemically and chemically stable, and is resistant to hydrolysis. Are preferred.

The esters used according to the invention are described, for example, in Chem. High Pol
ymers (Japan), 7, 188-193 (1950). Mu
by Ra Kami and Organoboron Chemistry
Chapter 5, J. Am. Wiley & Sons, N.W. Y. H in 1964
. Synthesized by conventional methods as described by Steinberg. In these syntheses, acids, acid anhydrides or acid chlorides, such as boric acid, C (O) Cl ₂ , POCl ₃ , SO ₂ Cl ₂ and SiCl ₄ , are used as starting materials, with suitable monovalent or polyhydric acids. Reaction with a dihydric alcohol or etherol by a known method.

The plasticizer content of each layer is from 0 to 200% by weight, preferably from 0 to 100% by weight, more preferably from 0 to 200% by weight, based on the mixture present therein or the material making up the layer (polymer binder + cathode or anode material). Is from 0 to 70% by mass.

The starting materials used in each layer can be dissolved or dispersed in an inorganic or, preferably, organic liquid diluent, wherein the resulting solution is from 100 to 50,000 m
It is desirable to have a viscosity of Pas, followed by, for example, spray coating, casting, dipping, spin coating, roller coating or relief printing, gravure, planography or screen printing, or by known methods such as extrusion. Can be applied to the support material if desired. That is, a film-like structure can be formed by giving a shape. Further processing can be performed in a conventional manner, for example, by removing the diluent and curing the material.

Suitable organic diluents include aliphatic ethers (especially tetrahydrofuran and dioxane), hydrocarbons (especially mixtures of hydrocarbons such as petroleum spirit, toluene and xylene), aliphatic esters (especially ethyl acetate and butyl acetate) ), Ketones (especially acetone, ethyl methyl ketone) and cyclohexanone. Also, combinations of such diluents can be used.

Suitable support materials are the substances conventionally used in electrodes, and are preferably metals such as aluminum and copper. In addition, a coated glass substrate (in particular, I
A temporary intermediate support such as a TO-coated glass substrate) or a film (especially a polymer film such as a polyethylene terephthalate film) can be used. Such a film is preferably provided with a release layer of polysiloxane.

Similarly, the manufacture of the individual films, which then form the layers in the composite of the invention, comprises:
For example, if necessary, further calendering can be performed, and thermoplastic processing can be performed by injection molding, melt casting, pressing, kneading or extrusion.

After film formation, volatile components such as solvents or plasticizers can be removed.

If crosslinking of the layers is necessary, this can be done in a manner known per se,
It can be carried out in a manner such as, for example, ion or ionizing radiation, irradiation with an electron beam (preferably an accelerating voltage of 20 to 2000 kV and a radiation dose of 5 to 50 Mrad), irradiation with UV or visible light, where conventional It is preferred to add an initiator such as benzyldimethyl ketal or 1,3,5-trimethylbenzoyl-triphenylphosphine oxide in an amount of at most 1% by weight, based on the components to be crosslinked, in the starting material. Is generally
Preferably, it is performed within 0.5 to 15 minutes under an inert gas such as nitrogen or argon. It can also be carried out by thermal free-radical polymerization, preferably at a temperature above 60 ° C., wherein at the most based on the components to be crosslinked in the starting materials, it is generally at most 5% by weight, preferably from 0.05 to 5% by weight. It is desirable to add an initiator such as azobisisobutyronitrile in an amount of 1% by weight. It can also be carried out by electrochemically induced polymerization or by ionic polymerization (
For example, it can be carried out by acid-catalyzed cationic polymerization). The suitable catalysts here are, first of all, acids, preferably Lewis acids such as BF _{3, in} particular LiBF ₄ or LiPF ₆ . Lithium - ion-containing catalysts, for example, LiBF ₄ or LiPF ₆ can advantageously previously played as conductive salt in the solid electrolyte or separator in.

The layers described herein also contain a dissociable compound containing a lithium cation (eg, a conductive salt) and, if necessary, especially additives such as organic solvents (eg, electrolytes). be able to.

Some or all of these materials can be added to the mixture during the production of the layer, or can be introduced into the layer after the latter.

The conductive salts which can be used are, for example, the generally known conductive salts as described in EP-A 0 096 629. According to the present invention, the conductive salt used is _{preferably, LiPF 6, LiBF 4, LiClO} 4, LiAs F 6, LiCF 3 SO 3, LiC (CF 3 SO 2) 3, LiN (CF 3 SO 2) _{2, Li n (SO 2 C} n F 2n + 1) 2, LiC [(C n F 2n + 1) SO 2] 3, Li (C n F 2n + 1) SO 3 ( here, n is the In this case, 2 to 20), LiN (SO ₂ F) ₂ , LiAlCl ₄ , LiSiF ₆ , LiSbF ₆ or a mixture of two or more thereof, and the use of LiBF ₄ or LiPF ₆ as a conductive salt is preferred.

These conductive salts are in each case 0.1 to 5 based on the material forming each layer.
It is used in an amount of 0% by weight, preferably 0.1 to 20% by weight, particularly preferably 1 to 10% by weight.

The films / layers forming the composites of the present invention are generally from 5 to 500 μm,
Preferably it has a thickness of 10 to 500 μm, more preferably 10 to 200 μm. Preferably, the composite in the form of a film generally comprises 15 to 15
It has a total thickness of 00 μm, in particular a total thickness of 50 to 500 μm.

Furthermore, the present invention provides a method of laminating under the action of heat or pressure or heat and pressure, preferably by hot lamination, by means of one or more first or plural first laminations.
There is provided a method of making a composite, characterized in that layer A and one or more second layers B and, if present, one or more tie layers are joined to one another. Depending on the material used in the tie layer, it should be ensured that the joining can always take place at room temperature or at temperatures up to 50 ° C. or by hot lamination.

In hot or cold lamination, all conventional techniques such as roller melt, simple pressing and extrusion lamination can be used.

For hot lamination, the temperature used is generally from about 50 ° C. to about 250 ° C., preferably from about 70 ° C. to about 200 ° C., more preferably about 100 ° C.
To about 180 ° C.

One or more first layers, or one or more second layers, or one or more first layers and one or more second layers, are subjected to corona treatment,
Also provided is a method of making a composite comprising joining one or more first corona-treated layers to one or more second corona-treated or untreated layers, preferably by hot lamination.

The corona treatment is a method widely used in surface treatment for roughening / functionalizing the surface. In this way, roughening / functionalization is achieved by electrical charging of the surface. The generator produces an AC voltage of about 10 to about 20 KV at a frequency of about 20 to about 40 KHz, and the generated energy is applied via the electrode system to the surface of the substrate to be treated, here the layer or layers mentioned above. The discharge results in a functionalized / roughened surface of the layer. According to the invention, both layers are preferably corona treated on the surface to which they are joined.

For further details on the instruments required for corona treatment and techniques for performing such treatment, see "Flexible Anpassung der effect."
Papier + Kuns titled "even Kontaktflache"
tsofferverbeitung, number 8 (1980) and "Oberflachenbehandlungsmethoden zur.
Papier + Kunst titled "Hafteverbesserung"
stoffverarbeitung, number 7 (1981) and the references cited therein.

The invention further applies at least one tie layer to one or more first layers, one or more second layers, or one or more first layers and one or more second layers. And, subsequently, there is provided a method of making a composite, comprising joining the first layer or layers to the second layer or layers via the bonding layer or layers, preferably by hot lamination.

Further, the present invention provides a method of using the above-described composite to manufacture an electrochemical cell in a sensor, an electrochromic window, a display, a capacitor or an ion-conducting film.

In addition, there is provided an electrochemical cell comprising the composite of the present invention or a combination of two or more thereof.

Suitable organic electrolytes for this purpose are the compounds discussed above under “Plasticizers”, customary organic electrolytes, preferably such as ethylene carbonate, propylene carbonate, dimethyl carbonate and diethyl carbonate. Preference is given to using esters or mixtures of such compounds.

As can be seen from the above, the first electrode layer (eg, cathode) /
If desired, a composite consisting of a tie layer / separator layer / second electrode layer (eg, anode) can be easily manufactured. Of course, here, the tie layer can also have the function of a separator so that the separator can be omitted.

The technique is, for example, as follows.

Anode materials such as graphite, conductive black and PVDF copolymers
Mixed with each other, the resulting mixture is cast on Cu foil and subsequently dried
(Layer 1). Subsequently, a cathode material such as LiMn_TwoO_FourOr LiCoO _Two The conductive black and PVDF copolymer are mixed with one another, cast on aluminum foil and dried (layer 2). By hot lamination, two above
Layer and separator layer and, if necessary, at least one tie layer together.
Bonded and combined with any solid and / or liquid electrolyte,
Obtain a composite material that can be used as a battery.

The filling of the composite material with the electrolyte and the conductive salt can be carried out even before the layers are joined, but after joining, if desired, a suitable collector electrode (for example, a metal foil)
Is preferably provided, and even after the composite material has been introduced into the battery housing. When using the admixture of the present invention, the special pore structure of the layers, especially as a result of the presence of the solids in each layer, incorporates electrolytes and conductive salts,
It allows replacement of air in the holes. Filling can be performed at 0 ° C. to about 100 ° C., depending on the electrolyte used.

The electrochemical cell according to the invention can be used in particular in automotive cells, electric equipment cells, flat cells or polymer cells.

EXAMPLES Preparation of Anode Foil 400 g of MCMB (Osaka Gas), 35 g of Kynar2®
801 (Elf Atochem), 35.6 g of ethylene carbonate and 35.6 g of dimethyl carbonate were added to 460 g of THF. This mixture was ground for several days and subsequently applied to copper foil pre-printed with anchor coat.
After drying, this foil was used as the anode foil for the following examples.

Example 1 75 g wollastonite (Tremin 800 EST, Quarzwerke Freche having an average particle size of 3 μm and hydrophobized with epoxysilane)
n) was dispersed in 300 g of toluene with a high-speed stirrer. Then 12.5 g of polyethylene oxide (Polyox®, Union Carbide®) having an average molecular weight of Mw = 2,000,000, 12.5 g
A methacrylic diester of a propylene oxide ethylene oxide block copolymer (registered trademark Plurio PE600, manufactured by BASF AG);
02 g of UV photoinitiator (registered trademark Lucirin BDK, manufactured by BASF AG)
Was added to the mixture. The mixture was then applied to the siliconized polyethylene terephthalate at 60 ° C. by a doctor blade with a 300 μm casting slit, the toluene was removed for 5 minutes, and the dried coating was peeled off, leaving a film about 30 μm thick. Obtained (separator film) Example 2 Anode foil is coated with a powder of Kynar 2811 (copolymer of vinylidene fluoride and hexafluoropropane from Elf Atochem) powder and subsequently at 160 ° C. using a model IL12HR laminator from Ibico. It was closely bonded to the separator film.

Example 3 One side of a separator film was coated with Kynar 2811 powder and the side with the powder was placed on an anode foil. The two sheets were subsequently intimately joined together at 160 ° C. using the laminator described in Example 2.

Example 4 Aqueous polyethylene dispersion (Polygen WII®, solids content 35)
%, From BASF) was applied to the untreated polyethylene film by a doctor blade. The polyethylene layer applied in this way had a thickness of 2 μm. Subsequently, the dispersion described in Example 1 was treated with P
Cast on ET film. After drying, the formed separator film was peeled off from the PET film. The polyethylene coated side of the separator was placed on the anode foil. The two sheets were subsequently intimately joined together at 160 ° C. using a laminator.

Example 5 The procedure of Example 4 was repeated, except that 5% based on the dispersion Aerosil R812 (from Degussa) was added to the polyethylene dispersion.

Example 6 The procedure of Example 4 was repeated, except that 5% of titanium dioxide T805 (from Degussa) based on the dispersion was added to the polyethylene dispersion.

Example 7 5% Wollastonite® Tremin 939 (Quarzwe based on dispersion)
rke) was added to the polyethylene dispersion, but the procedure of Example 4 was repeated.

Example 8 A solution of polyethylene oxide in THF was applied to silicone-treated polyethylene terephthalate by a doctor blade. The polyethylene oxide layer applied in this way had a thickness of 2 μm. Subsequently, the dispersion described in Example 1 was cast on a PET film thus pretreated.
After drying, the parator film was peeled off from the PET film. The polyethylene oxide coated side of the separator was placed on the anode foil. The two sheets were subsequently bonded intimately to each other at 160 ° C. using the laminator described in Example 2.

Example 9 5% Proprietary Aerosil R812 (from Degussa) based on solution
Example 8 was repeated except that was added to the polyethylene oxide solution.

Example 10 The procedure of Example 8 was repeated, except that 5% of titanium dioxide T805 (from Degussa) based on the solution was added to the polyethylene oxide solution.

Example 11 5% Wollastonite ® Tremin 939 (Quarzwer based on solution)
The procedure of Example 8 was repeated except that ke) was added to the polyethylene oxide solution.

Example 12 The procedure of Example 8 was repeated except that 3% propylene carbonate based on the solution was added to the polyethylene oxide solution.

Example 13 The procedure of Example 8 was repeated, except that 3% of tris (2-ethylhexyl) phosphate based on the solution was added to the polyethylene oxide solution.

Example 14 5% Wollastonite® Tremin 939 (Quarzwer based on solution)
Example 8 was repeated except that ke) and 3% tris (2-ethylhexyl) phosphate were added to the polyethylene oxide solution.

Example 15 A solution of Acronal 102 (a toluene solution of polybutyl acrylate, manufactured by BASF) was applied to a polyethylene terephthalate film siliconized by a doctor blade. The polybutyl acrylate layer applied in this way had a thickness of 2 μm.

Subsequently, the dispersion described in Example 1 was mixed with the thus-treated PE
Cast to T-film. After drying, the separator film was peeled off from the PET film. The polybutyl acrylate coated side of the separator was placed on the anode foil. The two sheets were subsequently intimately joined together at 160 ° C. using a laminator.

Example 16 5% Aerosil® 812 (from Degussa) based on solution
Example 14 was repeated except that was added to the polybutyl acrylate solution.

Example 17 The procedure of Example 14 was repeated, except that 5% titanium dioxide T805 (from Degussa) based on the solution was added to the polybutyl acrylate solution.

Example 18 5% Wollastonite ® Tremin 939 (Quarzwer based on solution)
ke) was added to the polybutyl acrylate solution, but the procedure of Example 14 was repeated.

Example 19 A solution of Oppanol B200® (from BASF, polyisobutylene n
-Hexane solution) was applied to a polyethylene terephthalate film siliconized by a doctor blade. The polyisobutylene layer applied in this way had a thickness of 3 μm. Subsequently, the dispersion described in Example 1 was cast on a PET film thus pretreated. After drying, the separator film was peeled off from the PET film. The polyisobutylene-coated side of the separator was placed on the anode foil. The two sheets were subsequently intimately joined together at 160 ° C. using a laminator.

Example 20 5% Trademark Aerosil® 812 (from Degussa) based on solution
Example 18 was repeated except that was added to the polyisobutylene solution.

Example 21 The procedure of Example 18 was repeated, except that 5% of titanium dioxide T805 (from Degussa) based on the solution was added to the polyisobutylene solution.

Example 22 5% Wollastonite ® Tremin 939 (Quarzwer based on solution)
ke 18) was added to the polyisobutylene solution, except that the procedure of Example 18 was repeated.

The following table shows the qualitative results when the compositions described in Examples 1 to 22 were tested.

[0135]

[Table 1]

[Table 2]

[Procedural Amendment] Submission of translation of Article 34 Amendment of the Patent Cooperation Treaty

[Submission date] April 10, 2000 (2000.4.10)

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] Claims

[Correction method] Change

[Correction contents]

[Claims]

──────────────────────────────────────────────────続 き Continuation of front page (81) Designated country EP (AT, BE, CH, CY, DE, DK, ES, FI, FR, GB, GR, IE, IT, LU, MC, NL, PT, SE ), EA (AM, AZ, BY, KG, KZ, MD, RU, TJ, TM), AL, AU, BG, BR, BY, CA, CN, CZ, GE, HU, ID, IL, JP, KR , KZ, LT, LV, MX, NO, NZ, PL, RO, RU, SG, SI, SK, TR, UA, US (72) Inventor Bronstert, Bernd Germany, D-67166, Otterstadt, Tsunder Strasse, 35 (72) Inventor Mewald, Helmut Germany, D-76855, Annweiler, Marquardt Uttrath, 16 (72) Inventor Stephan, Oscar Germany, D-68766, Hockenheim, Kolpingstrasse, 1 (72) Inventor, Hisashi Tsukamoto 1F Term Reference) 5G307 GA02 GC02 5H029 AJ11 AK03 AK05 AL01 AL02 AL06 AL07 AL08 AL12 AM02 AM03 AM04 AM05 AM07 AM11 AM16 EJ12 EJ14

Claims (12)

[Claims] 1. Aa) a) 1 to 95% by weight of a solid III, preferably basic solid III, having a primary particle size of 5 nm to 20 μm, and b) 5 to 99% by weight of a b1) composition Α) at least one compound VI capable of reacting with 5 to 100% by weight, based on IV) of a) a carboxylic acid or a sulfonic acid or a derivative thereof or a mixture thereof, and β) at least one mole of compound VI. 1 mol of a condensation product V of a carboxylic acid or sulfonic acid VII containing at least one free-radical polymerizable functional group, or a derivative thereof or a mixture of two or more thereof, and b2) based on composition IV 0 to 95% by weight, having an average molecular weight (number average) of at least 5,000, Or at least one first layer comprising a mixture Ia comprising a mixture IIa consisting of a polymer composition IV 1 obtainable by polymerizing a further compound VIII having a polyether segment in the side chain (mixture in mixture Ia IIa is from 1 to 100% by weight), wherein the first layer does not contain an electroconductive electrochemically active compound, and B) an electroconductive electrochemically active compound. A composite comprising at least one second layer comprising: one or more of the first layers and one or more of the second layers in two methods V1
Or V2: V1) lamination of one or more first layers and one or more second layers by the action of heat or pressure or the action of heat and pressure; or V2) one or more of the first layers Corona treatment of layer, one or more of said second layers, or one or more of said first layer and one or more of said second layers, and subsequent corona-treated one or more first layers and corona treatment A composite material characterized in that it is joined together by one of the following methods: integrated with unprocessed or untreated second layer or layers. 2. Ab) a) 1 to 95% by weight of a solid III having a primary particle size of 5 nm to 20 μm, preferably a basic solid, and b) 5 to 99% of b1) based on polymer IX 5 to 75% by weight of a compound X which is free-radically polymerizable and which is different from carboxylic acid or sulfonic acid VII, or a derivative thereof or a mixture of two or more thereof, and b2) 25 based on polymer IX At least 5,000 to 95% by weight
At least one first layer comprising a mixture Ib comprising a mixture IIb comprising a polymer IX obtained by polymerization of a further compound VIII having a polyether segment in the main or side chain, having an average molecular weight (number average) of (A mass ratio of the mixture IIb in the mixture material Ib is from 1 to 100% by mass), wherein the first layer does not contain an electroconductive electrochemically active compound, and B) A composite comprising at least one second layer comprising an electrochemically active compound, the composite comprising one or more first layers and one or more second layers comprising two methods V1
Or V2: V1) lamination of one or more first layers and one or more second layers by the action of heat or pressure or the action of heat and pressure; or V2) one or more of the first layers Corona treatment of layer, one or more of said second layers, or one or more of said first layers and one or more of said second layers, followed by corona-treated one or more first layers and corona treatment A composite material, wherein the composite material is bonded to one another by one of the methods described above. 3. At least one first layer Aa according to claim 1 or 2.
Or at least one first layer Ab, or at least one first layer Aa and at least one first layer Ab, at least one second layer B, and C) at least one tie layer. 4. The method according to claim 1, wherein the bonding layer or layers C has a melting point of one or more of the first layer, one or more of the second layers, or one or more of the first and one or more of the second layers. The composite of claim 3 having a low melting point. 5. The method according to claim 1, wherein the one or more tie layers C are polyethylene oxide, polyvinyl ether, polyacrylate, polymethacrylate, polyvinylpyrrolidone, polyurethane, waxy (co) polyolefin, rubbery material, polyisobutylene or two or more thereof. The composite according to claim 3 or 4, which is a mixture. 6. The method according to claim 1, wherein the bonding layer (s) C is a solid III, a plasticizer or
The composite according to any one of claims 3 to 5, comprising a combination of the above. 7. The method according to claim 1, comprising bonding the first layer or layers and the second layer or layers and, if present, the bonding layer or layers to each other by hot lamination. 7. The method for producing a composite material according to any one of 6. 8. The corona treatment of one or more first layers, one or more second layers or one or more first layers and one or more second layers, followed by one or more corona treatments. The method of claim 1 or 2, comprising joining the treated first layer to one or more corona treated or untreated second layers. 9. Applying at least one tie layer to one or more first layers, one or more second layers or one or more first and second layers, followed by one or more The method for producing a composite material according to any one of claims 3 to 6, further comprising joining one or more first layers to one or more second layers via the bonding layer. 10. A method of using a composite according to any one of claims 1 to 6 for producing an electrochemical cell in a sensor, an electrochromic window, a display, a capacitor or an ionically conductive film. 11. The composite material or 2 according to any one of claims 1 to 6,
An electrochemical cell comprising a combination of the above. 12. A method of using the electrochemical cell according to claim 11, as an automobile battery, an appliance battery, a planar battery or a polymer battery.