MXPA01009980A - Composite body suitable for utilization as a lithium ion battery - Google Patents

Abstract

The invention relates to a composite body having:Aa) at least one separator layer (Aa) comprising a mixture (Ia) containing a mix (IIa) consisting of a) 1 to 95 percent by weight of a solid (III), preferably a basic solid (III), with a primary particle size ranging from 5 nm to 20&mgr;m and b) 5 to 99 percent by weight of a polymeric material (IV) obtained by polymerization of b1) 5 to 100 percent by weight, in relation to the material (IV), of a condensation product (V) consisting of (&agr;) at least one compound (VI) capable of reacting with a carboxylic acid or a sulphonic acid or a derivative or a mixture of two or more thereof and (&bgr;) at least one mole per mole of the compound (VI) consisting of a carboxylic acid or sulphonic acid (VII) having at least one radically polymerizable functional group or a derivative thereof or a mixture of two or more thereof, b2) 0 to 95 percent by weight, in relation to the material (IV), of an additional compound (VIII) having a mean molecular weight (numerical average) of at least 5000 with polyether segments in the main or side chain, wherein the percentage by weight of the mix (Iia) contained in the mixture (Ia) ranges between 1 and 100 percent by weight of a conductive electrochemically active compound;B) at least one cathode layer (B) containing an electron conductive, electrochemically active compound capable of releasing lithium ions during charging;C) at least one anode layer (C) containing an electron conductive, electrochemical compound capable of receiving lithium ions during charging.

Description

COMPOSITE BODY SUITABLE FOR USE LIKE A LITHIUM ION BATTERY The present invention relates to compounds that are suitable, inter alia, electrochemical cells having electrolytes containing lithium ions; its use as, for example, lithium-ion batteries, batteries, sensors, electrochromic windows, displays, capacitors and films that conduct ions comprising such a compound. Electrochemical cells, in particular rechargeable cells, are generally known, for example from "Ullmann's Encyclopedia of Industrial Chemistry", 5th Ed., Vol. A3, VCH Verlagsgesellschaft mbH, Weinheim, 1985, pages 343-397. Among these cells, a special position is occupied by lithium batteries and lithium ion batteries, in particular as secondary cells, due to their high density of specific energy storage. As described, for example, in the above citation from "Ullmann", the cathode of such cells comprises lithiated manganese, cobalt, vanadium or mixed nickel oxides which in the stoichiometrically simplest case can be described, such as LiMn204, LiCo02, LiV205 or LiNi02. These mixed oxides react reversibly with compounds that can incorporate lithium ions into their lattice, for example graphite, with the lithium ions removed from the crystalline lattice and the metal ions such as manganese, cobalt or nickel ions present in the later part being removed. oxidizes This reaction can be used in an electrochemical cell to store electrical energy by separating the compound that collects lithium ions, ie the anodic material, and the mixed oxide containing lithium, ie the cathode material, by means of an electrolyte through the which lithium ions migrate from the mixed oxide within the anodic material (loading operation). Suitable compounds for the reversible storage of lithium ions are usually fixed on collecting electrodes by means of a binder. When the cell is charged, the electrons flow through an external voltage source and the lithium cations flow through the electrolyte to the anodic material. When the cell is used, the lithium cations flow through the electrolyte while the electrons flow through a charge from the anodic material to the cathode material. To avoid a short circuit inside the electrochemical cell, a layer that is electrically insulating but permeable to the lithium cations is situated between the two electrodes. This layer can be a solid electrolyte or a conventional separator.

In the production of many electrochemical cells, for example a lithium ion battery in the form of a round cell, the necessary battery films, ie the cathode, anode and separator films, are combined using a winding apparatus to produce a drum roller. In conventional lithium-ion batteries, the cathodic and anodic films are joined to collecting electrodes in the form of, for example, a thin sheet of aluminum or copper. Such thin metal sheets ensure sufficient mechanical stability. In contrast, the separating film has to withstand the mechanical stresses by itself, which is not a problem in the case of conventional separating films based on, for example, polyolefins and having the conventional thickness. To further improve the mechanical stability of such conventional separator films, JP 09-134 730 and JP 09-161 815 propose to join these separator films to the anode and / or cathode film by means of a tie layer. In contrast to conventional separator films, the mechanical stability of the separate films filled with a solid is not generally sufficient to ensure problem-free curl of the films. A compound that is able to withstand the mechanical stresses that occur in the manufacture of, for example, battery, is described in WO 99/19917 by the applicant. The compound claimed therein comprises at least one layer which is filled with a solid, for example, a separating layer, and at least one second layer which may be a cathodic layer or an anodic layer. It is an object of the present invention to develop the compound claimed in WO 99/19917 further and to provide a compound that can be used directly as an electrochemical cell, in particular as a lithium ion battery and can therefore be introduced directly into a housing appropriate for such a cell or such a battery. The present invention accordingly provides, in one embodiment, a compound comprising Aa) at least one spacer layer Aa comprising a mixture comprising a mixture a) consisting of a) from 1 to 95% by weight of a solid III , preferably a basic solid III, having a primary particle size of 5 nm to 20 μm and b) from 5 to 99% by weight of a polymeric composition IV obtainable by the polymerization of b) from 5 to 100% by weight based on the composition IV, of a condensation product V of a) at least one compound VI which is capable of reacting with a carboxylic acid or a sulfonic acid or a derivative or a mixture of the two or more thereof, and ß) to the minus 1 mole per mole of compound VI of a carboxylic acid or sulfonic acid VII containing at least one free radically polymerizable functional group, or a derivative thereof or a mixture of two or more thereof, and b2) from 0 to 95% by weight based on the composition ion IV, of an additional compound VIII having an average molecular weight (number average) of at least 5000 and polyether segments in the main chain or a secondary chain, wherein the weight ratio of the mixture in the mixture is 1 at 100% by weight, and the layer is free of an electron-conducting electrochemically active compound, YB) at least one cathodic layer B comprising an electron-conducting electrochemically active compound which is capable of releasing lithium ions upon loading, ) At least one anodic layer C comprising an electron-conducting electrochemical compound that is capable of collecting lithium ions upon charging. The separating layer or layers Aa preferably comprises or comprises a mixture comprising a mixture a) consisting of a) from 1 to 95% by weight of a solid III, preferably a basic solid III having a main particle size of 5 mM to 20 μm and b) from 5 to 99% by weight of a polymeric composition IV obtainable by the polymerization of b) from 5 to 100% by weight, based on the composition IV of a condensation product V of a) a polyhydric alcohol VI having carbon and oxygen atoms in the main chain, and ß) at least 1 mole per mole of the polyhydric alcohol VI of an unsaturated α, ß-carboxylic acid VII, and b2) from 0 to 95% by weight based on in composition IV of an additional compound VIII having a mean molecular weight (number average) of at least 5000 and polyether segments in the main chain or a secondary chain, wherein the weight ratio of the mixture in the mixture is from 1 to 100% by weight. In a further embodiment, the present invention provides a compound comprising. Ab) at least a first separating layer Ab comprising a mixture Ib comprising a mixture IIb consisting of a) from 1 to 95% by weight of a solid III, preferably a basic solid, having a main particle size of 5. nm at 20 μm and b) from 5 to 99% by weight of a polymer IX obtainable by the polymerization of b) from 5 to 75% by weight based on polymer IX of a free radical polymerizable compound X which is different from the carboxylic acid or the sulfonic acid VII or a derivative thereof, or a mixture of two or more thereof, and b2) from 25 to 95% by weight, based on the polymer IX, of an additional compound VIII having a mean molecular weight (number average) of at least 5000 and polyether segments in the main chain or a side chain, wherein the weight ratio of the mixture Ilb in the mixture Ib is 1 at 100% by weight and the layer is free of an electron-conducting electrochemically active compound, and at least one cathodic layer B and at least one anodic layer C, each as defined above. The present invention further provides a compound comprising al. minus a separating layer Aa or at least one separating layer Ab or at least one separating layer Aa and at least one separating layer Ab, at least one cathodic layer B, at least one anodic layer C, each defined above, and D) at less a tie layer D. The respective layers of the compound of the present invention, which are preferably in the form of a film, are described in greater detail in the following.

Separating Layer Aa / Ab The term "Solid III" covers all compounds that are solid under normal conditions and, during battery operation, can not collect or release electrons under the conditions prevailing during battery charging, in particular Lithium-ion batteries. Such solids are distinguished for the purposes of the present invention from the "electrochemically active electron-conducting" compounds in the anodic or cathodic layer. The solid III used in this layer is first and foremost an inorganic solid, preferably an inorganic basic solid, selected from the group consisting of oxides, mixed oxides, silicates, sulfates, carbonates, phosphates, nitrides, amides, imides , and carbides of the elements of the main groups I, II, III and IV and the transition group IV of the Periodic Table; a polymer selected from the group consisting of polyethylene, polypropylene, polystyrene, polytetrafluoroethylene, polyvinylidene fluoride, polyamides, polyimides; a dispersion of solids comprising such a polymer; and a mixture of 2 or more thereof. Examples which may be mentioned are, in particular: oxides such as calcium oxide, silicon dioxide, aluminum oxide, magnesium oxide or titanium dioxide, mixed oxides, for example of the elements silicon, calcium, aluminum, magnesium, titanium; silicates such as ladder, chain, sheet and structure silicates, preferably wollastonite, in particular hydrophobicized wollastonite, sulfates such as alkali metal and alkaline earth metal sulfates; carbonates such as alkali metal and alkaline earth metal carbonates; for example calcium, magnesium or barium carbonate or lithium, potassium or sodium carbonate; phosphates such as apatites; nitrides; amides, imides, carbides, polymers such as polyethylene, polypropylene, polystyrene, polytetrafluoroethylene, polyvinylidene fluoride, polyamides, polyimides or other thermoplastic, thermosetting dispersions, microgels, solid, in particular those comprising the aforementioned polymers, and also mixtures of two or more of the aforementioned solids.

In addition, the inorganic solids which conduct Li ions, preferably an inorganic basic solid which conducts Li ions, can be used according to the invention as solid III. Examples are: lithium borates such as LYLBTOH * xH20, Li3 (B02) 3, Li2B407 * xH20, LiB02, where x can be from 0 to 20; lithium aluminates such as Li20 * Al203 * H20, Li2Al20, LiA102; lithium aluminosilicates such as lithium containing zeolites, feldspars, feldspar substitutes, phyllosilicates and inosilicates, and, in particular, LiAlSi206 (spodumene), LiAlSi4O? 0 (petulite), LiAlSi04 (eucryptite), mica such as K [Li, Al] 3 [AlSi] 0? o (F-OH) 2, / K [Li, Al, Fe] 3 [Al Si] 4O10 (F-OH) 2; lithium zeolites, in particular those in the form of fiber, foil or cube, in particular those having the formula Li2 zO * A1203 * xSi02 * and H20, where z corresponds to the valence, x is from 1.8 to about 12 and y is 0 up to about 8; lithium carbides such as Li2C2, Li4C; Li3N; lithium oxides and mixed oxides such as LiA102, Li2Mn03, Li20, Li202, Li2Mn04, Li2Ti03; Li2NH; LiNH2; lithium phosphates such as Li3P04, LiP03, LIAIFPO4, LiAl (OH) P04, LiFeP04, LiMnP04; Li2C03; lithium silicates in the form of a ladder, chain, sheet and structure, for example Li2Si03, Li2Si04 and Li6Si2; lithium sulfates such as Li2S04, LiHS04, LiKS04; the Li compounds mentioned in the discussion of the cathodic layer, with the presence of conductive black being excluded when used as the solid III; and also mixtures of two or more of the aforementioned solids that conduct Li ions. Particularly suitable solids III are basic solids. For the purposes of the present invention, basic solids are those whose mixing with a liquid, diluent containing water which itself has a pH of at most 7, has a higher pH than this diluent. The solids are preferably very largely insoluble in the liquid used as electrolyte and electrochemically inert in the middle of the battery. Particularly suitable solids are those having a main particle size of 5 nm to 20 μm, preferably 0.01 to 10 u and in particular 0.1 to 5 μm, where the specified particle sizes are determined by electron microscopy. The melting point of the solid is preferably above the customary operating temperature for the electrochemical cell; Melting points above 120 ° C, particularly above 0 ° C, have been found to be particularly useful. In terms of their external shape, the solids can be symmetrical, that is they have an aspect ratio of height: width: length of about 1 and are in the form of spheres, granules, roughly round structures, but also in the form of any polyhedra such as cuboids, tetrahedra, hexahedra, octahedra or dipyramids, or they can be distorted or asymmetric, that is they have an aspect ratio of height: width: length different from 1 and are in the form of needles, asymmetric tetrahedrons, asymmetric dipyramids, hexahedrons or asymmetric octahedrons, platelets, discs or as fibers. If the solids are in the form of asymmetric particles, the aforementioned upper limit for the primary particle size refers in each case to the smallest axis. As compound VI which is capable of reacting with a carboxylic acid or a sulfonic acid (VII) or a derivative or a mixture of two or more thereof, it is possible in principle to use all the compounds that fulfill this criterion. Compound VI is preferably selected from the group consisting of monohydric or polyhydric alcohols having only carbon atoms in the main chain; monohydric or polyhydric alcohols whose main chain comprises at least 2 carbon atoms plus at least one atom selected from the group consisting of oxygen, phosphorus and nitrogen; compounds containing silica; amines having at least one primary amino group; amines having at least one secondary amino group; aminoalcohols; monohydric or polyhydric thiols; compounds containing at least one thiol group and at least one hydroxyl group; and mixtures of two or more thereof. Among these, preference is given to compounds VI that contain two or more functional groups that can react with the carboxylic acid or sulfonic acid. When VI compounds containing amino groups are used as a functional group, preference is given to using those having groups to inosecundarios so that after condensation / reticuted there are absolutely no free NH groups or only small amounts thereof present in the mix the Specific examples of the preferred compounds are: Monohydric or polyhydric alcohols having only carbon atoms in the main chain and having from 1 to 20, preferably from 2 to 20 and in particular from 2 to 10, alcoholic OH groups, in particular alcohols dihydric, trihydric and tetrahydric, preferably having from 2 to 20 carbon atoms, for example ethylene glycol, 1,2- or 1,3-propanediol, 1,2- or 1,3-butanediol, 1,4-b? tendiol or 1,4-b-tindiol, 1,6-hexanediol, neopentyl glycol, 1,2-dodecanediol, glycerol, trimethylolpropane, pentaerythritol or sugar alcohols, hydroquinone, novolac, bisphenol A; it is also possible, as can be seen from the above definition, to use monohydric alcohols such as methanol, ethanol, propanol, n-, sec- or tert-butyl, etc .; it is also possible to use polyhydroxylene glycols, preferably those having 2 terminal hydroxyl groups, for example α, β-dihydroxybutadiene; polyester polyols as are known, for example, from Ulmanns Encycl opadie der tech ni schen Chemi e, 4-edition, Volume 19, pp 62-65 and are obtained, for example, by the reaction of dihydric alcohols with polycarboxylic acids , polybasic, preferably dibasic; Monohydric or polyhydric alcohols whose main chain comprises at least two carbon atoms plus at least one oxygen atom, preferably polyether alcohols such as polymerization products of alkylene epoxides, for example isobutylene oxide, propylene oxide, ethylene oxide 1 , 2-epoxybutane, 1,2-eooxypentane, 1,2-epoxyhexane, tetrahydrofuran, styrene oxide; it is also possible to use polyether alcohols which are modified in the final groups, for example polyether alcohols modified in the terminal groups, for example polyether alcohols modified by terminal groups NH2; these alcohols preferably have a molecular weight (average number) from 100 to 5000, more preferably from 200 to 1000 and in particular from 300 to 800; such compounds are known to be and to eat the iiieplement, for example, under the trade names Pluriol * or Pluronic0 (BASF Ak! i engesel 1 sena í ~ L); alcohols as defined above in which some or all of the carbon atoms are replaced by silicon; compounds of this type that can be used are, in pa r i. i?! a r, pol isiloxapos O flake! Examples of alkylene-siloxane oxides or mixtures of polyether alcohols and polyalloxanes as disclosed, for example, FP-R 581 296 and EP-A 525 728, with respect to molecular weight these aleonóles, Lamnién api i ca i ue i ho anler crínenle;?. alcohols as defined above, in pa ri, ic the alcohols pol ELER, in ome or sludges oxygen atoms which reepiplazan by Sulfur atoms, with H.sup.s to the molecular ufi.o of these alcohols, what has been said above applies equally, iiionohmr Ios or polyhydric alcohols whose main chain comprises at least two carbon atoms plus at least pn ALOMO of rósforo or at least one of nii.rógeno ALOMO, for example dietanolami ay trietanola ina; laclonas that an der i pari go compueslos (] (- > the formula HO- (CH2) 2-C00H where z is from 1 to 20, by PTPT ?? I n F-ranrnifltr'trina. R-nrnninlsrrnns. v-hnrirnisrfnna r. methyl-e-caprolactone; pue compuesLos coniJenen sil i Lal tio is eating) I r uJ tio iano or L r i cl r osyl year, f n i 1 L r Id ocosilano, di phenyldichlorosilane, dimethylvinylchlorosilane.; silanols lal s as L r iipel i 1 if 1 anol; amines having at least one primary secondary amino group and / or, for example butylamine, 2-etilhexiiamina, ethylenediamine, hexamethylenediamine, diethylenetriamine, L lrael J ienpe ldtii na, penlael i 1 xaitü na, aniline, phenylenediamine, polyetherdiamine, such as 4,7-dioxysercan-1, 10-d Lamina, 4,11 -d? xi le Ir adec no-1, 14-dJ aai Lna; monohydric or polyhydric thiols, for example They are made as they are nickel !, IOJ, elanLLol, cyclohexanthiol, dodecantiol; aromatic thiols such as Liofenoj, 4-d? tol and ofenol, 2-p? er capl? an i 1 na; compounds containing at least one thiol group and at least one hydroxyl group, for example 4- i dr? Li? Phenol and monothio derivatives of polyhydric alcohols before / nene; amino alcohols such as ethanolamine, N-NIELLO LleLau? lamina, the N-Llelanolam ina, -bu lil eLanol din Lna, 2-amino-1-propanol, 2-amino-l-phenylethanol, polyols monoami? or poiJa Jno cjue fill more and two groups hiuroxilo aliphatically bound, for example tris (hydroxymethyl.}. methylamine, cj 1 ucaiii i na, N, N '-bis (2-hi OXJ NIELLO r i 1) i lenaJ amine. It is also possible to use mixtures of two or more of the VI-defined compounds in the Timer le.

According to the present invention, the aforementioned VT compounds are condensed with a carboxylic acid or sulphonic acid VTI containing at least one free radical polymerizable functional group or? N derived therefrom or a mixture of two or more thereof, in which reaction at least one, preferably all, of the free groups capable of condensation within the compounds VI are condensed with the compound VII. The carboxylic acids or sulphonic acids VTT which can be used for the purposes of the present invention are in principle all carboxylic and sulphonic acids containing at least one radical polymerizable functional group, and also their derivatives. The term "derivatives" used herein encompasses both compounds that are derived from a carboxylic acid or sulonic acid and in which the acid function is modified, for example, esters, acid halides or acid anhydrides and compounds to be derived from. they start from a carboxylic or sulphonic acid and in which the skeleton and carbons of the carboxylic or sulphonic acid are modified, for example halocarboxylic acids or hydrophilic acids. Examples of compound VII are, in particular: unsaturated α, β-carboxylic acids or unsaturated β, α-carboxylic acids. The unsaturated α, β-carboxylic acids which are suitable for this purpose are those of the formula I PJ PJ I I I i C = C i i R3 COOH where PJ, R2 and Rs are hydrogen or alkyl radicals of CT-C ,; among these, preference is given to acrylic acid and methacrylic acid; other suitable compounds are cinnamic acid, maleic acid, fumaric acid, itaconic acid or p-vi n Iben / oi co acid, and also derivatives thereof, for example anhydrides such as maleic anhydride or anhydride i Lacon i co; halides, in particular chlorides, such as aeryloyl chloride or methyl chloride; esters such as (meta) crilates of (cyclo) alkyl which have up to 20 carbon atoms in the alkyl radical, for example methyl, ethyl, propyl, butyl, hexyl (meth) acrylate, 2-yi ihe 1 o, esio io, iauriio, ciciohexilo, bencilo, trifluoromethyl, hexafl? Oropropi 1 oo tetr afl uor opropjlo, mono (met) acr Polypropylene glycol liabilities, mono (meth) acrylates polyethylene glycol, poli ( methacrylates of polyhydric alcohols, for example di (mel) acr. i! glyceryl, di (meth) acrylate trimethylolpropane, di- or tri- (meth) acrii Lo de pentaeri trit Lio, bi s (carbonate to mono (2- ac i loxiet i 1 o)) di ethyl ngl i cabbage, poly (met) acri! alcohols which in themselves contain a radically free polymerizable group, for example esters of (meth) acrylic acid and vinyl and / or allylic alcohol; vinyl esters of other aliphatic or aromatic carboxylic acids, for example vinyl acetate, vinyl propionate, vinyl butyrate, vinyl hexanoate, vinyl octanoate, vinyl decanoate, vinyl stearate, vinyl palmitate, vinyl crotonate , divinyl adipate, divinyl sebacate, vinyl 2-ethylhexanoate, vinyl trifluoroacetate; allyl esters of other aliphatic or aromatic carboxylic acids, for example allyl acetate, allyl propionate, allyl butyrate, allyl hexanoate, allyl octanoate, allyl decanoate, allyl stearate, allyl palmitate, allyl crotonate, allyl salicylate, allyl, allyl lactate, diallyl oxalate. diallyl malonate, diallyl succinate, diallyl glutarate, dyallyl adipate, diallyl pimelate, dyallyl cinatri.c. arboxylate, allyl trifluoroacetate, allyl perfluorobutyrate, allyl peruiooctanoate; unsaturated ß, α-carboxylic acids or their derivatives, for example, vi i 1 -citric acid, 2-methylvinylacetic acid, isobutyl 3-butenoate, allyl 3-butenoate, allyl-2-hydroxy-3-butenoate, di chitin; sulfonic acids such as vinylsulfonic acid, allylsulfonic and methyl-sulphonic acids, and also their esters and halides, vinyl benzenesulfonate, 4-vinylbenzenesulfonamide. It is also possible to use mixtures of two or more of the above-described carboxylic and / or sulfonic acids. Specific examples of compound X which is capable of free radical polymerization and which can be used to prepare polymer IX are: olefinic hydrocarbons such as ethylene, propylene, butylene, isobutene, hexene or higher homologs and vinylcyclohexane; (meth) acrylonitrile; halogen-containing olefinic compounds, such as vinylidene fluoride, vinylidene chloride, vinyl fluoride, vinyl chloride, hexafluoropropene, trifluoropropene, i, 2-dichloroetienene, 1,2-difluoroethylene and tetrafluoroethylene; vinyl alcohol, vinyl acetate, N-vinylpyrrolidone, N-vinylimidazole, vinylformamide; phosphonitrile chlorides such as hexachloro (triphosphazene), and also derivatives thereof which are partially or completely substituted by alkoxy, phenoxy, amino and fluoroalkoxy groups, ie compounds which can be polymerized to form polyphosphores; aromatic, olefinic compounds, such as styrene, α-methylstyrene; vinyl ethers such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, hexyl, octyl, decyl, dodecyl, 2-ethexyl, cyclohexyl, benzyl, trifluoromethyl, hexafluoropropyl, and vinyl tetrafluoropropyl. It is also possible, of course, to use mixtures of the above X compounds, resulting in copoiímeros in which the monomers are, depending on the method of preparation randomly distributed or arranged in blocks. Here preference is given to using polymers and copolymers of vinyl chloride, acrylonitrile, vinylidene fluoride, vinyl chloride and vinylidene chloride, vinyl chloride and acrylonitrile, vinylidene chloride with hexafluoropropylene, vinylidene fluoride, with hexafluoropropylene and a selected member from the group consisting of vinyol fluoride, tetrafluoroethylene and a trifluoroethylene, as described, for example, in US ,540,741 and US 5,478,668 whose descriptions in this regard are fully incorporated for reference within the present application. Among these, preference is given to the copolymers of vinylidene fluoride (1,1-difluoroethene) and hexafiuoropro, more preferably random copolymers of vinylidene fluoride and hexafluoropro, in which the weight ratio of vinylidene fluoride is from 75 to 92% and that of hexafluoropro is from 8 to 25%. These compounds X and the condensation products V are polymerized by conventional methods well known to those skilled in the art, preferably polymerized by a free radical mechanism; with respect to the molecular weights obtained, what is said subsequently applies to compounds VII. Suitable compounds VIII are, first and foremost, compounds having an average molecular weight (average number) of at least 5000, preferably from 5,000 to 20,000,000, in particular from 100,000 to 6,000,000 which are capable of solvating lithium cations and function as binders. Examples of suitable compounds VIII are polyethers and copolymers comprising at least 30% by weight of the following structural unit, based on the total weight of compound VIII: Where R1, R ", R'3 and R4 are aryl groups, alkyl groups, preferably methyl or hydrogen groups and can be identical or different and contain heteroatoms such as oxygen, nitrogen sulfur or silicon.

Such compounds are described, for example, in M.B. Armand et al., Fast Ion Transport in Solids, Elservier, New York, 1979, pp. 131-136 or in FR-A 7832976. Compound VIII may also consist of a mixture of two or more such compounds. The polymer composition IV defined above or polymer IX may also be in the form of a foam, in which case solid III is present as a dispersion therein. The mixtures should, according to the present invention, consist of from 1 to 95% by weight, preferably from 25 to 90% by weight and in particular from 30 to 70% by weight, of a solid III and from 5 to 99% by weight, preferably from 10 to 75% by weight and in particular from 30 to 70% by weight, of a polymeric composition IV, and compound VIII of the polymeric composition IV should advantageously have a mean molecular weight (average number) of 5000 to 100,000,000, preferably from 50,000 to 8,000,000. The polymeric composition IV can be obtained by reacting from 5 to 100% by weight, preferably from 30 to 70% by weight based on the polymeric composition IV, of a compound V with from 0 to 95% by weight, in particular 30% by weight. to 70% by weight, based on the polymeric composition IV, of a compound VIII. The mixtures Ilb should, according to the present invention, consist of from 1 to 95% by weight, preferably from 25 to 90% by weight and in particular from 30 to 70% by weight, of a solid III and from 5 to 99% by weight, preferably from 10 to 75% by weight and in particular from 30 to 70% by weight, of a polymer IX, and compound VIII of polymer IX should advantageously have a mean molecular weight (number average) of from 5,000 to 100,000,000 , preferably from 50,000 to 8,000,000. Polymer IX can be obtained by reacting from 5 to 75% by weight, preferably from 30 to 70% by weight, based on polymer IX, of a compound X with from 25 to 95% by weight, in particular from 30 to 95% by weight. 70% by weight, based on polymer IX of a compound VIII. In the following, the mixtures la and Ib used according to the present invention and the mixtures lia and Ilb used according to the present invention are discussed together and are referred to as "mixture used according to the present invention" and "mixture used in accordance with the present invention". the present invention "respectively. To prepare the mixture used according to the present invention which should comprise a mixture used according to the present invention in an amount of 1 to 100% by weight, preferably 35 to 100% by weight and in particular 30 to 70% by weight, weight, based on the mixture used according to the present invention, a mixture of a solid III, a condensation product V and, if desired, a compound VIII or a mixture of a solid III, a compound X, a compound VIII and customary additives such as plasticizers, preferably plasticizers comprising polyethylene oxide or polypropylene oxide, can be prepared.

Anodic layer B and cathodic layer C As polymeric binder in these layers B and C, use is made of the following polymers. The polymeric binders used in layers B and C may be identical or different from one another. Particular mention may be made of: 1) Homopolymers, copolymers or block copolymers IVa (polymers IVa) obtainable by polymerization of the mixtures defined above or Ib. 2) polycarbonates such as polyethylene carbonate, polypropylene carbonate, polybutadiene carbonate, polyvinylidene carbonate. 3) block homopolymers, copolymers and copolymers prepared from a) olphinic hydrocarbons such as ethylene propylene, butylene isobutene, propene, hexene or higher homologs, butadiene, cyclopentene, cyclohexene, norbornene, vinylcyclohexane; b) aromatic hydrocarbons such as styrene and methylstyrene; c) esters of acrylic acid or methacrylic acid, for example methyl, ethyl, propyl, isopropyl, butyl, isobutyl, hexyl, octyl, decyl, dodecyl, 2-ethylhexyl, cyclohexyl, benzyl, trifluoromethyl, hexafluoropropyl or tetrafluoropropyl acrylate or methacrylate; d) acrylonitrile, methacrylonitrile, N-m.ethylpyrrolidone, N-vinylimidazole, vinyl acetate; e) vinyl ethers such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, hexyl, octyl, decyl, dodecyl, 2-ethylhexyl, cyclohexyl, benzyl, tri-fluorophenyl, hexafluoropropyl or tetrafluoropropyl vinyl; f) halogen-containing olefinic compounds, such as vinyl chloride, vinyl fluoride, vinylidene fluoride, vinylidene chloride, hexafluoropropene, trifluoropropene 1,2-dichloroethene, 1,2-difluoroethene, tetrafluoroethene. 4) polyurethanes, for example obtainable by reacting a) organic diisocyanates having from 6 to 30 carbon atoms, for example aliphatic acyclic diisocyanates such as 1,5-hexamethylene diisocyanate and 1,6-hexamethylene diisocyanate, aliphatic cyclic diisocyanates as cyclohexylene 1,4-diisocyanate, dicyclohexylmethane diisocyanate and isophorone diisocyanate or aromatic diisocyanates such as 2,4-toluene diisocyanate 2,6-toluene diisocyanate, m-tetramethylxylene diisocyanate, p-tetramethylxylene diisocyanate, 1 5-tetrahydronaphthylene diisocyanate, and 4,4'-diphenylmethane diisocyanate or mixtures of such compounds, with b) polyhydric alcohols such as polyesterols, polyetherols and diols. Polyesterols are advantageously predominantly linear polymers having terminal OH groups, preferably those having two or three, in particular 2, final OH groups. The number of acids of the polyesterols is less than 10 and preferably less than 3. The polyesterols can be prepared in a simple form by esterification of aliphatic or aromatic dicarboxylic acids having 4 to 15 carbon atoms, preferably 4 to 6 atoms. carbon, with glycols, preferably glycols having from 2 to 25 carbon atoms, or by polymerization of lactones having from 3 to 20 carbon atoms. Examples of dicarboxylic acids which can be used are glutaric acid, pimelic acid, suberic acid, sebasic acid, dodecanoic acid and preferably adipic 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, for example diphenic acid, sebasic acid, succinic acid and adipic acid. The dicarboxylic acids can be used individually or as a mixture. To prepare the polyesterols, it may be advantageous to use the corresponding acid derivatives such as carboxylic anhydrides or carboxylic chlorides in place of the dicarboxylic acids. Examples of suitable glycols are diethylene glycol, 1,5-pentanediol, 1, 10-decanediol and 2,2,4-trimethylpentan-1,5-diol. Preference is given to using 1,2-ethanediol, 1,3-propanediol, 2-methylpropan-1, 3-diol, 1,4-butanediol, 1,6-hexanediol, 2,2-dimethylpropan-1,3-diol , 1,4-dimethylolcyclohexane, 1,4-diethanolcyclohexane and ethoxylated or propoxylated products of 2,2-bis (4-hydroxyphenyl) propane (bisphenol A). Depending on the desired properties of the polyurethanes, the polyols can be used alone or as a mixture in various mixing proportions. Suitable lactones for preparing the polyesterols are, for example, a, α-dimethyl-β-propiolactone, β-butyrolactone and preferably e-caprolactone. Polyetherols are essentially linear substances that have terminal hydroxyl groups and contain ether linkages. Suitable polyetherols can be easily prepared by polymerization of cyclic ethers such as tetrahydrofuran or by reacting one or more alkylene oxides having from 2 to 4 carbon atoms in the alkylene radical with an initiator molecule containing two active hydrogen atoms in the form of union in the alkylene radical. Examples of 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, alternatively, in succession 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, amines such as ethylenediamine, hexamethylenediamine and 4,4'-diaminodiphenylmethane and amino alcohols such as ethanolamine. Suitable polyesterols and polyetherols and their preparation are described, for example, in EP-B 416 386; Suitable polycarbonate diols, preferably those based on 1,6-hexanediol, and their preparation are described, for example, in US Pat. No. 4,131,731. Advantageously, use can be made of up to 30% by weight, based on the total mass of the alcohols, of aliphatic diols having from 2 to 20, preferably from 2 to 10, carbon atoms, for example 1,2-ethanediol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol , 1, 5-pentanediol, 1, 10-decanediol, 2-methylpropan-l, 3-diol, 2,2-dimethylpropan-l, 3-diol, 2-methyl-2-butylpropan-l, 3-diol, 2 , 2-dimethylbutan-l, 4-diol, 1,4-dimethylolcyclohexane, neopentyl glycol hydroxypivalate, diethylene glycol, triethylene glycol and methyldiethanolamine or aliphatic aromatic or aromatic cycloaliphatic diols having from 8 to 30 carbon atoms where the possible aromatic structures are of heterocyclic rings or preferably isocyclic ring systems, for example naphthalene or, in particular, benzene derivatives such as bis enol A, symmetrically diethoxylated bisphenol A, symmetrically dipropoxylated bisphenol A, bisphenol A derivatives or higher ethoxylated or propoxylated bisphenol F derivatives, and also mixtures of such compounds. Advantageously, use can be made of up to 5% by weight, based on the total mass of the alcohols, of aliphatic triols having from 3 to 15, preferably from 3 to 10 carbon atoms, for example trimethylolpropane or glycerol, the product of reaction of such compounds with ethylene oxide and / or propylene oxide, and also mixtures of such compounds. The polyhydric alcohols can carry functional groups, for example neutral groups such as xyloxane groups, basic groups such as, in particular, amino groups or acid groups or their salts or groups which are easily converted into acid groups, these groups are introduced by means of a polyhydric alcohol. Preference is given to using diol components bearing such groups, for example N-methyldiethanolamine, diethyl, N, N-bis (hydroxyethyl) aminomethylphosphonate or N, N-bis (hydroxyethyl) -2-amino-acetate-3-sulfopropyl, or dicarboxylic acids carrying such groups and can be used for the preparation of polyesterols, for example 5-sulfoisophthalic acid. The acid groups are, in particular, phosphoric acid, phosphonic acid, sulfuric acid, sulfonic acid, carboxyl group or ammonium. Groups which are easily converted to acidic groups are, for example, ester groups or salts, preferably alkali metals such as lithium, sodium or potassium. 5) The polyesterols described above in themselves; care must be taken to ensure that molecular weights in the range of 10,000 to 2,000,000, preferably 50,000 to 1,000,000, are obtained. 6) polyamines, polysiloxanes and polyphosphazenes, in particular those which have already been discussed in the description of the polymer IVb 7) the polyetherols as described, for example, in the previous discussion of the polymer IVa as compound IX or in the discussion of the polyurethanes. The cathodic layer C comprises an electrochemically active electron-conducting compound customarily used for cathodes (cathode compound) which is capable of collecting electrons when charged, preferably a lithium compound. Particular examples that can be mentioned are: LiCo02, LiNi02LiNixCOv02, LiNixCOyAl202, where 0 < x, y, z < l, LixMnO2 (0 <x <l), LixMn20 (0 <x <2), LixMo02 (0 <x <2), LixMn03 (0 <x = l), LixMn02 (0 <x <2), LYNMn204 (0 <x <2), LixV204 (0 <x <2.5), LixV203 (0 <x <3.5), LixV02 (0 <x <l), LixW02 (0 <X <1), LixW03 (0 <x = l); LixTi02 (0 <x = l), LixTi204 (0 <x <2), LixRu02 (0 <x <l), LixFe203 (0 <x <2) LixFe304 (0 <x <x) 2), LixCr203 (0 <x <3), LixCr304 (0 <x <3.8), LixV3S5 (0 <x <1.8), LixTa2S2 (0 <x <l), LixFeS (0 < x < l), LÍXFeS2 (0 < x < l), LixNbS2 (0 < x < 2.4), LixMoS (0 < x < 3), LixTiS2 (0 < x < 2 ), LixZrS2 (0 <x <2), LixNbSe2 (0 <x <3), LixVse2 (0 <x <1), LixNiPS2 (0 <x <1.5), LixFePS2 (0 <; x < 1.5). The anodic layer C comprises an electrochemically active electron-conducting compound known from the prior art (anodic compound) which is capable of releasing electrons upon charging; Particular examples that may be mentioned are: lithium, metal alloys containing lithium, micronized carbon black, natural and synthetic graphite, synthetic graphitized carbon powder and carbon fibers, oxides such as titanium oxide, zinc oxide, tin oxide, molybdenum oxide, tungsten oxide, carbonates such as titanium carbonate, molybdenum carbonate and zinc carbonate. The anodic layer C additionally comprises up to 30% by weight, based on the total weight of the materials present therein (polymeric binder plus anodic compound), of conductive black and, if desired, customary additives. The cathodic layer B comprises, based on the total weight of the materials present therein (polymeric binder plus cathodic compound), from 0.1 to 20% by weight conductive black.

Binding layer D As a binding layer D, it is possible in principle to use all the materials which are capable of joining the first layer or layers, as defined above, and the second layer or layers, as defined above, the one with the other. The joining layer is, in particular if the layers in question are joined to each other by hot rolling, generally a material having a melting point which is lower, preferably from 20 to 50 ° C lower, than those of the Aa / Ab separating layer or layers or the cathodic (B) or anodic layer or layers C or the Aa / Ab separating layer or layers and the cathodic (B) and anodic C. layer (s). The melting point of these materials - is generally from 25 to 250 ° C, preferably from 50 to 200 ° C and in particular from 70 to 180 ° C.

The tie layer D may also comprise a solid III. The amounts of the solid correspond essentially to the amounts specified for the additional layers A to C, in each case based on the material forming the tie layer. As such materials forming the tie layer, it is possible to use all the materials customarily used as adhesives. Of course, it has to be possible to apply these materials to the layers A and / or B by customary methods of layering, for example by printing, emptying, spraying, extruding coating scraper sheets, etc. Preference is given to using polymeric compounds as materials that form the tie layer. Mention may be made herein of: melt adhesives such as those based on ethylene-vinyl acetate copolymers which are generally further mixed with resins and / or waxes or paraffins to vary their melt flow index, those based on (co) polyethylene of low molecular weight, (co) atactic polypropylene, ethylene-acrylic ester copolymers and styrene-butadiene-styrene-isoprene block copolymers, polyisobutylene and also poly (meth) acrylates and polyesters such as polyethylene terephthalate which can also case mixed with plasticizers, in particular those mentioned herein, to vary their melt flow rate; adhesive plastisols which are mixed essentially from a dispersion of finely divided polyvinyl chloride in plasticizers and low molecular weight materials which are reactive under the action of heat and act as binding agents, for example epoxy resin compounds, phenolic resins, etc; heat sealing adhesives such as those based on copolymers of vinyl chloride or vinylidene chloride, copolymers of vinylidene fluoride and hexafluoropropene (for example Kynarflex®), copolymers of vinyl acetate, polymethacrylic esters, polyurethanes and polyesters which can be also mixed with other polymers or resins; 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 components used are mainly polychloroprene, nitrile or SBR rubbers and the resins used are mainly phenolic resins, rosin and also hydrocarbon resins; pressure sensitive adhesives such as those based on synthetic and natural rubber, poly (meth) acrylic esters, polyvinyl ethers and polyisobutylene, in each case again in combination with modified natural resins, phenol-formaldehyde resins or hydrocarbon resins; pressure sensitive dispersion adhesives such as those based on poly (meth) acrylic esters; cold-curing, heat-cured (approximately 80 to approximately 100 ° C) and hot-curing (approximately 100 to approximately 250 ° C) reaction adhesives such as one component or two component polymerization adhesives, the polymers used for the two-component polymerization adhesives are, in particular, synthetic rubbers, such as polychloroprene, styrene-butadiene rubber, butyl rubber, polystyrene, polymethacrylates with accelerators such as those based on amines and, for example, peroxide of benzoyl as a hardener, and examples of one-component polymerization adhesives are those based on cyanoacrylate; epoxy adhesives such as those based on condensation products of epichlorohydrin and polyhydric phenols such as bisphenol A; aminoplastics; phenolic resin adhesives; reactive polyurethane adhesives; polymethylol compounds; silicone adhesives; and polyimides and polyimidazoles such as polyamine amide and polybenzimidazole. Specific examples are: Polyethylene oxide; polyvinyl ethers such as poly (methyl vinyl ether), poly (ethyl vinyl ether), poly (propyl vinyl ether), poly (butyl vinyl ether), poly (isobutyl vinyl ether); (co) polyacrylates and (co) polymethacrylates, giving preference to those having relatively long alkyl chains, for example polybutyl (meth) acrylate or polyhexyl (meth) acrylate; polyvinylpyrrolidone, polyurethanes, wherein the aforementioned polyurethanes can be used equally; (co) polyolefins similar to wax, such as polyethylene, polypropylene and polyisoprene waxes; rubber-like materials; polyisobutylene; and also mixtures of two or more thereof. Further details regarding the materials that can be used according to the present invention in the link layer can be found in an article entitled "Kleben und Klebestoffe" (Chemie in unserer Zeit, number 4 (1980), and also Ullmann, Encyklopádie der technischen Chemie, 4- edition (1977), volume 14, pp 227-268 and also the literature cited in the present, whose contents referring to materials having adhesive properties are incorporated for reference within the present application.

In particular, the present invention provides compounds having the following structure: cathodic layer B, bonding layer D, separation layer Aa, additional bonding layer D which can be identical to or different from the first bonding layer D, and anodic layer C, compounds having the following structure: - cathodic layer B - bonding layer D - spacer layer Aa, - additional bonding layer D which can be identical to or different from the first bonding layer D, - additional layer of a conventional separator, - third joining layer D which can be identical to or different from the first and / or second joining layer D, and anodic layer C, and also compounds having the following structure: - cathodic layer B, - layer bonding D - additional layer of a conventional separator - additional bonding layer D which may be identical to or different from the first bonding layer D - separation layer Aa, - third bonding layer D which may be identical to or of the first and / or second junction layer D, and - anodic layer C, where the cathodic layers B and / or the anodic layers C are preferably firmly attached to a metal layer as an electron collector. The layer of a conventional separator that can also be used according to the present invention includes layers of all conventional separators, wherein in particular the following can be mentioned: - separators based on microporous polyolefin films whose microporosity is achieved by spreading and / or leaching additives such as waxes; these are commercially available, for example under the tradenames Celgard®, Hipore®, and are described, inter alia, in EP-A 0 715 364, both of which are fully incorporated for reference within the present application; polyethylene and polypropylene films and films comprising combinations of polyethylene or polypropylene with additional polymers are equally well suited; Microporous polytetrafluoroethylene (PTFE) films from Goretex are as described, for example, in EP-A 0 798 791 which is likewise incorporated for reference within the present application; - felts, fibers and non-woven fabrics, known as "nonwovens", which can all be produced using fibrous polymeric materials such as polyolefin, polyamide and polyester fibers; - films obtainable under the trade name Nafion®. The compound of the present invention may additionally comprise a plasticizer. Suitable plasticizers of this type are described in PCT / EP98 / 06394 and PCT / EP98 / 06237. The plasticizers which are preferably used are dimethyl carbonate, diethyl carbonate, dipropyl carbonate, diisopropyl carbonate, dibutyl carbonate, ethylene carbonate, propylene carbonate; ethers such as dibutyl ether, diterbutyl ether, dipentyl ether, dihexyl ether, diheptyl ether, dioctyl ether, dinonyl ether, didecyl ether, didodecyl ether, ethylene glycol dimethyl ether, diethylene glycol ether, 1-tert-butoxy-2-methoxyethane, l- tert-butoxy-2-ethoxyethane, 1,2-dimethoxypropane, 2-methoxyethyl ether, 2-ethoxyethyl ether, oligoalkylene oxide ethers, such as diethylene glycol dibutyl ether, dimethylene glycol tert-butyl methyl ether, triethylene glycol dimethyl ether, tetraethyl glycol dimethyl ether, ? -butyrolactone, dimethylformamide; hydrocarbons of the formula CnH2n + 2 where 7 < n < fifty; organic phosphorus compounds, in particular phosphates and phosphonates such as trimethyl phosphate, triethyl phosphate, tripropyl phosphate, tributyl phosphate, triisobutyl phosphate, tripentyl phosphate, trihexyl phosphate, trioctyl phosphate, tri (2-) phosphate ethylhexyl), tridecyl phosphate, diethyl n-butyl phosphate, tri (butoxyethyl) phosphate, tris (2-methoxyethyl) phosphate, tris (tetrahydrofuryl) phosphate, trisphosphate (H, OH, 5H-octafluoropentyl), tris (lH, lH-trifluoroethyl) phosphate, tris (2- (diethylamino) ethyl) phosphate, diethylethylphosphonate, dipropylpropylphosphonate, dibutyl butylphosphonate, dihexyl hexylphosphonate, dioctyl octylphosphonate, ethyl dimethyl phosphonate, methyl diethylphosphonoacetate, triethylphosphonacetate, dimethyl (2-oxo) phosphate -propyl) phosphonate, diethyl (2-oxopropyl) phosphonate, dipropyl (2-oxopropyl) phosphonate, ethyl diethoxyphosphinylformate, trimethylphosphonoacetate, triethylphosphonoacetate, tripropylphosphonoacetate, tributylphosphonoacetate or. Preference is given to trialkyl phosphates and carbonates. The plasticizer content of the respective layer is based on the mixture present therein or the material forming the layer (polymeric binder plus cathodic or anodic material), from 0 to 200% by weight, preferably from 0 to 100% by weight and more preferably from 0 to 70% by weight. The initial materials used for the respective layers can be dissolved or dispersed in an inorganic or preferably organic liquid diluent, wherein the resulting solution should have a viscosity of preferably 100 to 50,000 mPas, and subsequently applied in a known manner, for example by spray coating, pouring, submerging, spin coating, roller coating or printing, gravure, planographic or screen printing or extrusion, if desired for a support material, ie configured to form a film-like structure. The additional processing can be carried out in a customary manner, for example by removing the diluent and curing the materials. Suitable organic diluents are aliphatic ethers, in particular tetrahydrofuran and dioxane, hydrocarbons, in particular a mixture of hydrocarbons such as petroleum extract, toluene and xylene, aliphatic esters, in particular ethyl acetate and butyl acetate, and ketones, in particular acetone. , ethylmethyl ketone and cyclohexanone. It is also possible to use combinations of such diluents. Suitable support materials are materials customarily used for electrodes, preferably metals such as aluminum and copper. It is also possible to use coated glass substrates, in particular glass substrates coated with ITO or temporary intermediate supports such as films, in particular polyester films such as polyethylene terephthalate films. Such films can be advantageously provided with a release layer, preferably polysiloxanes. Likewise, the production of the individual films which then form the layers within the compound of the present invention can be carried out thermoplastically, for example by injection molding, melt-pouring, pressing, kneading or extrusion, if desired with a subsequent satin step. After the formation of the film, volatile components such as solvents or plasticizers can be removed. If crosslinking of the layers is desired, this can be carried out in a manner known per se, for example by irradiation with ionic or ionizing radiation, an electron beam, preferably at an acceleration voltage of 20 to 2000 kV and a dose radiation of 5 to 50 Mrad, UV or visible light, wherein, in a customary manner, an initiator such as benzyl dimethyl ketal or 1,3,5-trimethylbenzoyltriphenylphosphine oxide can be advantageously added in amounts of, in particular, at most 1% by weight based on the constituents to be crosslinked in the initial materials and the crosslinking can advantageously be carried out for a period, generally 0.5 to 15 minutes, advantageously under inert gas such as nitrogen or argon; by polymerization of thermal free radicals, preferably above 60 ° C, where an initiator such as azobisisobutyronitrile can be advantageously added in amounts of, in general to more than 5% by weight, preferably 0.05 to 1% by weight, based on the constituents to be crosslinked in the initial materials, by electrochemically induced polymerization, or by ionic polymerization, for example by acid-catalyzed cationic polymerization, wherein the suitable catalysts are, first and foremost, acids, Preference is given to Lewis acids such as BF3 or, in particular, LiBF4 or LiPF6.Catalysts containing lithium ions, for example LiBF4 or LiPFß can advantageously remain in the solid electrolyte or separator as the conductive salt. comprising a dissociable compound containing lithium cations, namely a conductive salt, and, if desired, additives. such as, in particular, organic solvents, namely an electrolyte. Some or all of these materials may be added to the mixture during layer production or may be introduced into the layer after the production of the latter. The conductive salts which can be used are the generally known conductive salts which are described, for example, in EP-A 0 096 629. According to the present invention, the conductive salt used is preferably LiPF6, LÍBF4, LÍC104, LiAsF6, LÍCF3S03, LiC (CF3S02) 3, LiN (CF3S02) 2, LiN (S02CnF2m + 1) 2, LiC [(CnF2n + 1) S02] 3, Li (CnF2n +?) S03, where n is in each case from 2 to 20, LiN (S02F) 2, LiAlCl4, LiSiF6, LiSbF6 or a mixture of two or more thereof, with particular preference being given to using LiBF4 or LiPF6 as the conductive salt. These conductive salts are used in amounts of 0.1 to 50% by weight, preferably 0.1 to 20% by weight, in particular 1 to 10% by weight, based in each case on the material forming the respective layer. The layers forming the compound of the present invention generally have a thickness of 5 to 500 μm, preferably of 10 to 500 μm, more preferably of 10 to 200 μm. The compound, which may have, for example, the shape of a film, a cuboid, a cylinder, a zig-zag roller or a flat roller (for example with oval side faces), generally has a total thickness of 100 μm up to a few cm. Furthermore, the present invention also provides a process for producing a compound according to the invention, which comprises joining the separating layer or layers Aa / Ab, the cathodic layer or layers B, the anodic layer or layers C and, if present, the layer or tie layers D of one another by rolling by means of pressure and / or temperature.

It must be ensured that, depending on the material used for the bonding layer, the bonding can always be carried out at room temperature or at temperatures of up to 50 ° C or by hot rolling. In hot or cold rolling, all customary techniques such as roll melt, simple press lamination and extrusion methods can be employed. In the case of hot rolling, the temperatures used are generally from about 50 ° C to about 250 ° C, preferably from about 70 ° C to about 200 ° C and more preferably from about 100 ° C to about 180 ° C. C. In detail, the following procedure can be employed: First, a tie layer D is applied, for example, to a temporary support film, as defined above, which can be removed or later removed. The supporting film can also be one that does not have to be removed. Particular mention should be made of the films of one of the conventional separators defined above which become ion-conducting as a result of expansion or are intrinsically ion-conducting or contain micropores, for example the microporous PE films defined above as well, foam films of open cells, non-woven and woven fabrics. This first compound is subsequently transferred, for example by means of heat and / or pressure to a cathodic or anodic D / C layer or a separating layer Aa / Ab. This gives a laminated composite that can be laminated with additional layers as defined herein. This procedure can be repeated as many times as necessary to obtain the desired compound of the present invention. In this form, it is possible to obtain a compound comprising a cathode, an anode and a separator and can thus be transferred directly into a battery housing. For this purpose, the chain or roller obtained after the aforementioned forming steps is joined by the action of heat and pressure, giving a welded electrode chain or roller firmly. The heat required for this can be generated inter alia, by thermal radiation, ultrasound, friction, microwave energy. This chain or roller can then be inserted into a battery housing. Yes, in the production of the chain or roller two electrode films coated on one side meet and as a result, for example, two terminal front metals are supported on top of each other, another bonding layer D can be introduced between these two films to produce a non-positive connection between these two layers as well. Figure 1 shows a roller produced in this form and will be discussed further below with reference to Example 2 according to the present invention. In addition, the present invention provides for the use of a compound, as defined above, to produce an electrochemical cell, in a sensor, an electrochromic window, an exhibitor, a capacitor or an ion conducting film. Additionally it provides an electrochemical cell comprising a compound of the present invention or a combination of two or more thereof. Organic electrolytes suitable for this purpose are the compounds discussed above under "plasticizers", preference being given to using customary organic electrolytes, preferably esters such as ethylene carbonate, propylene carbonate, dimethyl carbonate and diethyl carbonate or mixtures of such compounds The filling of such compounds with an electrolyte and conductive salt can be carried out before or preferably after putting the layers together, if desired after providing suitable collecting electrodes, for example a metallic thin sheet, which even after the introduction of the composed inside a battery housing. The particular microporous structure of the layers when the mixture of the present invention is used, in particular as a result of the presence of the solid defined above in the respective layers, makes it possible to collect the electrolyte and conductive salt and air in the pores that are to be displaced. The filling can be carried out from 0 ° C to approximately 100 ° C, depending on the electrolyte used. The filling with the electrolyte and the conductive salt is preferably carried out after the introduction of the compound into the battery housing. The electrochemical cells of the present invention can be used, in particular, as automotive batteries, instrument batteries, flat batteries, on-board batteries, batteries for static applications, batteries for electrotraction or polymer batteries.

EXAMPLES Example 1 First, an anode film was produced for a lithium ion battery. For this purpose, a 100 μm thick graphite layer consisting of 96% by weight of carbon and 4% by weight of polyisobutylene as a binder on a 15 μm thick copper film as an electron collector was coated with a layer 3 μm thick bond consisting of 93.5% by weight of PEO (Mw = 2,000,000 g / mol), 6% by weight of polyethylene glycol 600 dimethacrylate and 0.5% by weight of benzoyl peroxide on a film of PET support of 75 μm thickness (whose surface had been provided with a silicone anti-adhesion layer of 0.5 μm thickness) at 90 ° C in a hot-rolling unit (minisatinado having a pair of heated rubber rollers, diameter 2 cm) at a feed rate of 1 m / min. A cathodic film for a lithium ion battery was produced as follows: A 200 μm thick layer consisting of 80 wt.% Cobalt-lithium oxide, 10 wt.% Conductive carbon black and 10 wt.% of polyvinylidene chloride as a binder on a thin sheet of aluminum 15 μm thick, as an electron collector, was coated with a 3 μm thick binding layer consisting of 93.5% by weight of PEO (Mw = 2, 000 , 000), 6% by weight of polyethylene glycol 600 dimethacrylate and 0.5% by weight of benzoyl peroxide on a PET support film of 75 μm in thickness (the surface of which was provided with a 0.5 μm thick silicone anti-adhesion layer). ) 90 ° C in a hot rolling unit (minisatinado having a pair of heated rubber rollers, diameter 2 cm) at a feed rate of 1 m / min. The separating film was produced as follows: 80 g of a wollastonite which had been hydrophobicized with methacrylsilane, which had an average particle size of 3 μm and whose aqueous dispersion had a pH of 8.5 was dispersed in 200 g of tetrahydrofuran ( THF) using a high speed agitator. Subsequently, 15 g of a polyethylene oxide having a mean molecular weight (number average) of 2,000,000 (Polyox®, Union Carbide), 5 g of a methallyl diester of a propylene oxide block copolymer was added to the mixture. ethylene oxide (Pluriol® PE600, BASF Aktiengesellschaft) and 0.05 q of benzyldimethyl ilketal. The mixture was then applied by means of a scraper blade to a siliconized release paper at 60 ° C, the solvent was removed for a period of 5 minutes and the dried coating was extracted to give a film of approximately 25 μm in thickness which photographed under a nitrogen atmosphere by illumination for 10 minutes at a distance of 5 cm under a field of superactinic rescent tubes (TL 09, Philips). The separating layer described above was laid between a pair of the anodic and cathodic films described above each having the metal sides facing outwards, in such a way that the anodic and cathodic films do not come into contact, to avoid a short circuit. This assembly was subsequently laminated together by means of the minisatination described above at the indicated rate of advance to give a chain of electrodes having a sandwich structure. The binding layers were crosslinked by storing this electrode chain at 120 ° C for 60 minutes so as to give a compact, tightly attached electrode chain. This electrode chain was placed in a film bag and the contacts were fixed to the front electrode electrodes of the electrodes by friction welding and passage of the bag. Subsequently, a 1 molar solution of LiPF6 in ethylene carbonate / diethyl carbonate was introduced and the housing was sealed by welding. The electrolyte was absorbed by the electrode chain for a period of approximately 30 minutes as a result of capillary forces, associated with the displacement of air previously present therein.

Example 2 First, an anode film and a cathodic film are produced as described in Example 1. These are wound together with the separating layer also described in Example 1 in such a way as to form a rectangular roll, as shown in the Figure 1. In the figure, the numbers correspond to the layers of: 1 Lithium Cobaltate 2 Aluminum 3 Separator 4 Graphite 5 Copper This roller was pressed in a press heated to 120 ° C for 60 minutes. This resulted in the hot rolling of the anodic and cathodic films with the solid electrolyte layer with the simultaneous crosslinking of the tie layers. This gave a compact, firmly attached roller that could be used as a finished component in the construction of a lithium ion battery. The electrode roll was subsequently placed in a stainless steel housing in the form of a c? Boid, after the contacts had been previously fixed to the metal front end films of the anodic and cathodic films by friction welding and had been passed from the accommodation. Subsequently, a 1 molar solution of LiPF6 in EC / DEC was introduced and the housing sealed by laser welding. The introduced electrolyte was absorbed by the electrode roll during a period of about 30 minutes as a result of capillary forces, the air previously present being displaced therein.

Example 3 First, an anode film was produced as described in Example 1. Subsequently, a cathodic film for a lithium ion battery was produced as follows: A 200 μm thick layer consisting of 80 wt. lithium-cobalt, 10% by weight of conductive carbon black and 10% by weight of poly inylidene chloride as binders on a 15 μm thick aluminum foil as an electron harvester was coated with a 3 μm bond layer of a polyvinylidene-hexafluoropropylene fluoride copolymer, in which the hexafluoropropylene content was 10% by weight, on a 75 μm thick PET film as a support (the surface of which was provided with a 0.5 μm silicone anti-adhesion layer). thickness) at 140 ° C in a hot rolling unit at a feed rate of 1 m / min. Subsequently, the anodic and cathodic films were rolled up from the middle together with an interleaved separator as described in Example 1 using the central winding technique in such a way that the anodic terminal metal (copper) did not come into contact with the front metal cathode (aluminum). The firmly attached cylindrical compact electrode roll obtained in this manner was subsequently heated to 160 ° C for 60 minutes. Due to the resulting hot lamination of the electrodes with the solid electrolytes and the simultaneous crosslinking of the bonding layer between the electrodes and the solid electrolyte, a compact, tightly connected electrode roller was obtained. This was placed in a cylindrical stainless steel housing, as described in Example 2, filled with an electrolyte and the housing sealed with subsequent welding.

Claims (13)

1. A compound comprising Aa) at least one spacer layer Aa comprising a mixture, comprising a mixture Ia consisting of a) from 1 to 95% by weight of a solid III, preferably a basic solid III, having a size of primary particle from 5 nm to 20 μm and b) from 5 to 99% by weight of a polymeric composition IV obtainable by the polymerization of b) from 5 to 100% by weight based on composition IV, of a condensation product V of a) at least one compound VI which is capable of reacting with a carboxylic acid or a sulfonic acid or a derivative or a mixture of the two or more thereof, and ß) at least 1 mole per mole of the VT compound of? n carboxylic acid or sulfonic acid VII containing at least a radically free polymerizable functional group, or a derivative thereof or a mixture of two or more thereof, and b2) from 0 to 95% by weight based on the composition TV, of additional compound VIII having an average molecular weight (average number) of at least 5000 and polyether segments in the main chain or a secondary chain, wherein the weight ratio of the mixture in the mixture is from 1 to 100% by weight, and the layer is free of an electron-conducting electrochemically active compound, and B) at least one cathodic layer B comprising an electron-conducting electrochemically active compound which is capable of releasing lithium ions at charged, C) at least one anodic layer C comprising an electrochemical compound carrying electrons which is capable of collecting lithium ions upon charging.

2. A compound comprising Ab) at least one spacer layer Ab comprising a mixture Tb comprising an Ilb mixture consisting of a) from 1 to 95% by weight of a solid III, preferably a basic solid , which has a primary particle size of 5 nm to 20 μm and b ^ from 5 to 99% by weight of a polymer IX obtainable by the polymerization of b) from 5 to 75% by weight based on the polymer TX of a radically free polymerizable compound X which is different from the carboxylic acid or the phonic acid? t? or? n derived therefrom, or a mixture of two or more thereof, and b2) from 25 to 95% by weight, based on the polymer TX, of an additional compound VIII which has a mean molecular weight (average number) of at least 5000 and polyether segments in the main chain or a secondary chain, wherein the weight ratio of the mixture IIb in the mixture Ib is from 1 to 100% by weight and the layer is free of an electron-conducting electrochemically active compound, and at least one cathodic layer B and at least one anodic layer C, each as defined in claim 1.

3. The compound comprising at least one separating layer Aa or at least one separating layer Ab or at least one separating layer Aa and at least one separating layer Ab, at least one cathodic layer B, at least one anodic layer C, each as defined in claim 1 or 2, and D) at least one tie layer D.

4. The compound as claimed in claim 3, wherein the tie layer or layers D has / have a melting point that is less than of fusion of the aao layers epar doras Aa / Ab or the a or cathodic layers B or the anodic layer or layers C or the cathodic layer or layers B, the anodic layer or layers C and the separating layer or layers Aa / Ab. The compound as claimed in claims 3 or 4, wherein the bonding layer or layers D is / are a polyethylene oxide, a polyvinyl ether, a polyacrylate, a polymethacrylate, polyvinylpyrrolidone, a polyurethane, a polyolefin similar to wax, a material similar to rubber, polyisobutylene or a mixture of two or more thereof. 6. A compound as claimed in any of claims 3 to 5, characterized in that the tie layer or layers D comprise or comprise a solid III, a plasticizer or a combination of two or more thereof. 7. A compound as claimed in any of claims 3 to 6 having the following structure: cathodic layer B, - joining layer D, - separating layer Aa, - additional joining layer D which can be identical to or different from the first joining layer D, and - anodic layer C, or - cathodic layer B, - joining layer D, - separating layer Aa, - additional joining layer D which can be identical to or different from the first tie layer D, additional layer of conventional separator, - third tie layer D which can be identical to or different from the first and / or the second bonding layer D, and anodic layer C, or - cathode layer B, - bonding layer D, - additional layer of a conventional spacer, bonding layer D which may be identical to or different from the first bonding layer D , - a mixed spacer layer Aa, a third joining layer D which can be identical to or different from the first and / or second joining layer D, and anodic layer C. 8. The compound as claimed in claim 7, Which has an additional layer of a conventional separator and an adi D, wherein the D-layer and the conventional separator and the additional bonding layer are located between the first bonding layer D and the separation layer Aa or between the additional bonding layer D and the anodic layer C. 9. A process for producing a compound as claimed in any one of claims 1 to 8, which comprises joining with one another the separating layer or layers Aa / Ab, the cathodic layer or layers B, the anodic layer or layers C and, if present, the bonding layer or layers D by hot rolling. 10. A process as claimed in claim 9, wherein, in a first step, the separating layer or layers Aa / Ab, the cathodic layer or layers B, the anodic layer or layers C and, if the layer or layer is present. Dlinking layers D come into contact with each other and are subjected to a patterned step, and subsequently joined together with one another by rolling heat and / or pressure. 11. The use of a compound as claimed in any of claims 1 to 8, for producing an electrochemical cell, in a sensor, an electrochromic window, an exhibitor, a capacitor or an ion conducting film. 12. The electrochemical cell comprising a compound as claimed in any of claims 1 to 8, or a combination of two or more thereof. 13. The use of the electrochemical cell as claimed in claim 12, such as a car battery, instrument battery, flat battery, on-board battery, battery for static applications, electrotraction battery or polymer battery. SUMMARY The invention relates to a composite body having: Aa) at least one spacer layer (Aa) comprising a mixture (Ia? Q? E comprises a mixture (ITa) consisting of a) from 1 to 95% by weight of a solid (III), preferably a basic solid (III), with a primary particle size ranging from 5 nm to 20 μm and b) 5 to 99% by weight of a polymeric material (IV) obtained by the polymerization of bl) 5 to 100% by weight relative to the material (IV), of a condensation product (V) which consists of a) at least one compound (VI) capable of reacting with a carboxylic acid or a sulfonic acid or a derivative or a mixture of two or more thereof, and ß) at least 1 mole per mole of the compound (VI) of a carboxylic acid or a < sulfonic acid (VTT having at least one radically polymerizable functional group, or a derivative thereof or a mixture of two or more thereof, and b2) 0 to 95% by weight, relative to the material (IV), of an additional compound (VIII) having an average molecular weight (number average) of at least 5000 with polyether segments in 1 to main or side chain, wherein the weight ratio of the mixture (lia) contained in the mixture (Ta ) varies between 1 and 100% by weight, of a conductive electrochemically active compound; B) at least one cathodic layer IB) containing an electrically conductive electrochemically active compound capable of releasing lithium ions during charging; C) at least one anodic layer C containing an electron-conducting electrochemical compound capable of receiving lithium ions during charging.