DE102009002680A1 - Production and use of ceramic composite materials based on polymer carrier film - Google Patents

Abstract

The invention relates to a ceramic composite material (1), comprising a planar carrier substrate (2) and a porous coating (4) applied to the carrier substrate (2) and comprising ceramic particles (3). The invention is based on the object to further develop a ceramic composite material of this genus while maintaining their high thermal and mechanical stability so that it achieves lower strengths. This object is achieved by a ceramic composite material, wherein the carrier substrate (2) is a polymer film (2), wherein the carrier substrate (2) is provided with a perforation, which consists of a plurality of regularly arranged holes (6), and wherein the perforation is obscured by the porous coating (4) at least on one side of the carrier substrate (2).

Description

The The present invention relates to a ceramic composite material. comprising a flat carrier substrate and a on the carrier substrate applied, ceramic particles having, porous coating. Furthermore, the invention relates a method for producing such a ceramic composite material as well an electrochemical cell containing such a ceramic composite material includes.

Under the term "electrochemical cell" in the sense The present application is an electrical energy storage to be understood, both rechargeable and non-rechargeable can be. In that regard, the notification text does not distinguish between the terms "accumulator / secondary battery" on the one hand and "battery / primary battery" on the other. Under the term "electrochemical cell" in the According to the application also falls a capacitor. An electrochemical Cell goes further than the minimum functional unit of the Energy storage. In technical practice is common a plurality of electrochemical cells connected in series or in parallel, to increase the total energy capacity of the store. In this context one speaks of multiple cells. A technical Running battery can therefore a single or a Variety of parallel or series connected electrochemical cells exhibit. As this is not the case for the present invention is relevant, the terms "battery" and "electrochemical Cell "henceforth used synonymously.

Regarding The character of a battery is between high-performance batteries and high energy batteries distinguished. A high performance battery is a memory that stores its electrical energy in a particularly short time Gives off time, he develops high discharge currents. A High energy battery has related to their weight or their volume a very large storage capacity.

The Electrochemical cell as an elementary functional unit comprises two opposite pole electrodes, namely the negative anode and the positive cathode. Both electrodes are separated by the Separator arranged against the electrodes against short circuit from each other isolated. The cell is with an electrolyte - so one liquid, gel or sometimes solid ion conductor - filled. The separator is ion-permeable and thus allows one Exchange of ions between anode and cathode in the charge or discharge cycle.

traditionally, A separator is a thin, porous, electrical insulating material with high ion permeability, good mechanical strength and long-term stability against the in the system, eg In the electrolyte of the electrochemical cell Chemicals and solvents. He is supposed to be in electrochemical cells completely electrically insulate the cathode from the anode. In addition, he must be permanently elastic and the movements follow in the system, not only by external loads, but also by "breathing" the electrodes when Storage and removal of the ions occur.

The separator significantly determines the life and safety of an electrochemical cell. The development of rechargeable electrochemical cells or batteries is therefore significantly influenced by the development of suitable separator materials. General information about electrical separators and batteries can z. B. at JO Besenhard in "Handbook of Battery Materials" (VCH-Verlag, Weinheim 1999) be read.

High energy batteries are used in various applications where it is on arrives, the largest possible amount of electrical To have energy available. Be high energy batteries used for driving vehicles (traction batteries) the off-grid, stationary power supply with the help of batteries (Auxillary Power Systems), in the case of uninterruptible Power supply, in the provision of control energy, for portable electronic devices such as laptops, mobile phones and Cameras and power tools. The energy density is often in weight [Wh / kg] or in volume [Wh / L] sizes indicated. Becoming instant in high energy batteries energy densities of 350 to 400 Wh / L and reached from 150 to 200 Wh / kg. The requested performance at such Batteries are not that big, so you can compromise on that of the internal resistance can do. That means that the Conductivity of the electrolyte-filled separator For example, it does not have to be as big as high-performance batteries, so that thereby also other Separatorkonzepte be possible.

So For high-energy systems, polymer electrolytes can also be used can be used, with 0.1 to 2 mS / cm but a very small Possess conductivity. Such polymer electrolyte cells however, they can not be used as high-performance batteries become.

Separators for use in high-performance battery systems must have the following characteristics They must be as thin as possible, to ensure a low specific space requirement, and to keep the internal resistance small. In order to ensure these low internal resistances, it is important that the separator also has a high porosity, because a large porosity favors the ion permeability. Furthermore, separators must be light in order to achieve a low specific gravity. In addition, the wettability for electrolyte must be high, since otherwise form electrolyte-free dead zones, which increase the internal resistance.

In many, especially mobile applications are very large Energy required (eg in traction batteries for fully electric vehicles). The batteries in these applications store a large amount of energy when fully charged, in case of malfunction of the battery, such. B. Overload or short circuit, or in an accident not uncontrollably released may be, as this inevitably leads to the explosion of cell and vehicle would result under fire phenomenon. separators for mobile applications must therefore special Be sure that the battery of a crashed vehicle is not exploded.

rechargeable High-performance batteries and high-energy batteries are on today Built up lithium-ion base. Since lithium is a highly reactive metal is and the components of a lithium-ion battery easily flammable are modern lithium-ion or lithium-metal batteries or hermetically sealed batteries. Such battery cells are sensitive against mechanical impairments, which for example can lead to internal short circuits. By internal short circuit and in contact with air can Lithium-ion batteries or lithium-metal batteries ignite. Because of its extraordinarily high storage capacity with a relatively small footprint are lithium-ion-based battery cells especially for the manufacture of batteries suitable for electric vehicles. The installation of batteries in vehicles therefore makes special demands to protect the battery cells against mechanical and thermal damage.

It is easy to imagine that for electric vehicles batteries must be provided, which is a proportionate high storage capacity and a relative have large terminal voltage. Especially for the automotive industry, eg. B. for full electric vehicles, the battery cells must be correspondingly large and possess due to the high specific gravity of the electrodes a high absolute weight. As mentioned above, For example, battery cells on lithium-ion or lithium-metal-based mechanically sensitive, so that when installed in a car special Measures are to be taken to make the battery cells more mechanical To protect impairment. In a modern Cars are accelerating forces during normal operating cycles from two to three times the gravitational acceleration in each axis expected. Such forces contribute to the vehicle Acceleration, deceleration, cornering and driving over of bumps. In addition, it is essential a built in a motor vehicle battery before impact mechanical effects and impact forces due to impact to secure. Next are the batteries and thus the battery cells and their compounds exposed to vehicle-induced vibration.

These Boundary conditions make high demands on the separator, he must be the trade-off between high ionic conductivity and low weight on the one hand and high mechanical / thermal On the other hand, solve stability.

Regarding their material can be the currently used separators subdivided into three classes: Fully Organic Separators, All-Ceramic Separators and organic / inorganic composite separators.

There are two different separator types in terms of their structure: textile separators and layer separators. The textile structure is usually nonwovens. Nonwovens (non-wovens) belong to the class of textile fabrics and are according to ISO 9092: 1988 defined as sheet materials, nets or mats consisting of randomly or regularly arranged fibers held together by friction or cohesion or adhesion. Textile separators can be thought of as felt. The voids between their fibers give them their porosity. Layer separators are in the form of plates or films and have a homogeneous structure. They get their porosity through a variety of pores or cavities, which are distributed disorderly in the full material, similar to a sponge.

In order to obtain a comparatively flexible separator in spite of the low elasticity of the ceramic materials, all-ceramic separators are generally built up textile. They consist of inorganic nonwovens, such. B. fleeces of glass or ceramic materials or ceramic papers. These are made by different companies. Important producers are: Binzer, Mitsubishi, Daramic and others.

The Separators of inorganic nonwovens or of ceramic paper are mechanically very unstable and lead easily too short, so no long life can be achieved.

Fully organic separators are used both in textile and in layered structure. Typical textile separators on an organic basis consist for. B. polypropylene fibers. The companies Celgard, Tonen, Ube and Asahi produce fully organic separators. An example is the fully organic Schichtseparator, which is offered by the company Celgard, LLC under the name Celgard ^® 2320th It is a three-layer, microporous layer of polypropylene, polyethylene, and polypropylene. The term microporosity derives from the classification of the pore size of materials and is carried out according to IUPAC. This subdivides the pore size into the following three groups: For example, microporous materials contain pores with a size smaller than 2 nm. Pores with a size between 2 and 50 nm can be found in mesoporous materials. Materials with pores larger than 50 nm are defined as macroporous.

One The big disadvantage of organic polyolefin separators is their low thermal load of less than 170 ° C. Nice a short-lived achievement of the melting point of these polymers leads to a substantial melting of the separator and to a short circuit in the electrochemical cell, such a Separator uses. The use of such separators is therefore general not sure. Because when reaching higher temperatures, in particular above 150 ° C or even 180 ° C These separators are destroyed. Fully organic separators are therefore not suitable for use in high energy or high-performance batteries. For this are all-ceramic or organic / inorganic composite separators required. Regarding her mechanical properties are the organic / inorganic composite separators superior to the all-ceramic separators and therefore come especially in mobile applications.

Organic / inorganic composite separators are z. In DE 102 08 277 . DE 103 47 569 . DE 103 47 566 or DE 103 47 567 described. To prepare these separators, a suspension of inorganic material is applied to an organic carrier substrate in the form of a PET nonwoven. The substrate thus receives its porosity through its textile structure. The pore distribution in the substrate is determined by the textile manufacturing process and is disordered. By crosslinking inorganic binder, the ceramic is fixed on the nonwoven. Such separators are sold by Evonik Degussa GmbH under the product name SEPARION ^®.

Another method of making organic / inorganic composite separators is disclosed in the documents WO 02/15299 and WO 02/071509 described. In this case, a suspension of an inorganic material is applied from a polymeric material. The suspension is based in this case on an organic solvent, organic binders, in particular fluorine-containing polymers such. As polyvinylidene fluoride (PVdF) or fluorine-containing copolymers such. As polyvinylidene fluoride-hexafluoropropylene Copoylmer (PVdF-co-HFP) used. Due to the presence of ceramic components in the separators their safety is increased, since complete destruction of the separator is prevented even at temperatures above 200 ° C by the ceramic. The pore size of the separators obtained is essentially influenced by an additional stretching process, which takes place after the coating of the polymeric carrier material. There is the danger that non-reclosable large pores or cracks will form on non-pressurized stretching. When stretched under pressure and high temperature even the smallest pores can be closed again by filling with polymer. A uniform pore size distribution can not be achieved with this method.

From the DE 103 43 535 B3 a separator for a lithium-polymer battery is known, which is provided with a defined surface profiling. This happens during the production process with the help of rollers. The rolls shown have, for example, a knurling or nubs. Thus, a regular surface structure is impressed on the separator, wherein the surface structure consists of crater-like depressions or elevations. The separator is profiled in its entirety so that the crater-like depressions or elevations remain uncovered in the surface.

From the EP 1 038 329 B1 and the US 6432576 B1 a lithium secondary battery is known, the separator is provided with a defined structure of holes. Both electrodes have corresponding hole patterns; the layers are stacked with aligned holes. Through the aligned holes extend bridges of polymeric material, which flanks the electrodes from the outside. The hole-penetrating, polymeric material is therefore not part of the separator, but rather represents the Serving of the cell.

The DE 199 21 955 A1 discloses a regularly perforated lead-acid battery separator. The perforation is formed by passages that serve to exchange gas in the cell. The separator described there consists of textile material or microporous powder; a ceramic coating is not apparent. For safety reasons, such perforated separators for lithium cells with high energy density are by no means usable: namely, the open holes within the separator promote the formation of dendrites, which short the electrodes and easily destroy the cell. To prevent this, teaches the DE 199 21 955 A1 the addition of alkali sulfate such as Na ₂ SO ₄ in the electrolyte, since this salt prevents too high a concentration of lead ions at the end of the discharge. However, this teaching is not transferable to the cell chemistry of a lithium-ion battery. It is therefore to be feared that the dendrites the passages of in DE 199 21 955 A1 pierced separator and lead to a fatal short circuit. Due to the significantly higher energy density of lithium batteries used in particular in automotive applications, the regularly perforated separator shown here is completely unsuitable.

The WO 06/068428 A1 shows a separator that is suitable for a lithium battery with high energy density. This is an organic / inorganic composite separator consisting of a polyolefin carrier substrate and a porous coating having ceramic particles applied thereto. The carrier substrate may be in the form of fibers or as a membrane. A carrier substrate in the form of fibers is understood by the person skilled in the art as a textile fabric, in particular as a nonwoven fabric. What is meant by a membrane, does not become apparent from the document; possibly the term "membrane" does not refer to another embodiment of the support structure but is used synonymously for the same fibrous textile structure. This comes to light insofar as known microfiltration membranes are usually designed as a textile fabric. However the support structure is constructed according to this teaching, it is porous and has a uniform but disordered pore distribution. The separator shown can be very thin, it has a preferred thickness of 1 to 30 microns, the minimum thickness of the substrate should be 1 micron, better still at 5 microns. The document indicates that at these low material thicknesses, no large porosity can be achieved, since otherwise the mechanical stability of the separator would be impaired. The limited porosity, in turn, limits the ion permeability of the separator and, ultimately, the output of the cell constructed with the separator. This is a disadvantage of in the WO 06/068428 A1 shown organic / inorganic composite separator.

The WO 06/004366 A1 also discloses a composite separator having an organic support substrate and an inorganic coating applied thereon. The carrier substrate, like the coating, has disordered pores; the coating is anchored in the carrier substrate. Incidentally, the above applies to this separator.

The WO 06/025662 A1 Figure 5 shows, in one embodiment, a porous organic / inorganic composite separator constructed homogeneously without the use of a carrier substrate. Ceramic particles are bonded to a polymeric binder for this purpose. Such homogeneous separators can achieve very low strengths, but their mechanical stability leaves something to be desired. Other embodiments are similar to the objects of WO 06/004366 A1 or the WO 06/068428 A1 ,

The WO 08/097013 A1 also shows a separator with a polyolefin, porous carrier substrate and a coating having on at least one side, ceramic particles having. The carrier substrate may be a membrane. The pores are randomly distributed in the carrier substrate.

In the practice made separators today have at least one Thickness of about 20 microns. in principle it is desirable, as thin as possible separators to obtain. As a result, on the one hand, the proportion of components a battery that does not contribute to their activity, be reduced. On the other hand, the reduction of strength at the same time an improvement of the ionic conductivity. The low wall thickness, however, lowers the mechanical stability and with it the security.

The best solution to this conflict of objectives in the field of high-energy / high-performance batteries has hitherto been seen in organic / inorganic composite separators which have a planar, textile-organic carrier substrate and a porous-ceramic coating applied thereto. Examples include the aforementioned SEPARION ^® products or the subject matter of WO 06/068428 A1 , Both can be assumed here as generic.

At this point and below is for the term separator the term used is ceramic composite material. Starting from the above-described prior art, the invention is the Task based, a ceramic composite material of the beginning mentioned genus while maintaining their high thermal and mechanical stability to form so that they lower Strengths achieved.

Solved This object is achieved in that as a carrier substrate a Polymer film is provided, wherein the carrier substrate is provided with a perforation, which from a variety regularly arranged holes, and wherein the perforation at least on one side of the carrier substrate from the porous Coating is covered.

object The invention is therefore a ceramic composite material, which a flat carrier substrate and one on the Carrier substrate applied, having ceramic particles, porous coating, in the carrier substrate it is a polymer film which is perforated is that of a variety regularly arranged Holes, the perforation at least on one Side of the carrier substrate of the porous coating is covered.

A The basic idea of the present invention is as a carrier substrate to use a polymer film that has its ion permeability obtained by turning it into an ion-impermeable Closed original film in compliance with a defined geometric Patterns targeted a hole was introduced, which is the film first made ion permeable. Consequently one uses according to the invention a uniform perforated perforated foil whose ion permeability due to the regularity of the hole pattern the entire surface of the film is constant.

This has the decisive advantage that the through the punching caused mechanical weakening of the film over their entire surface is just as constant as their ion permeability. The Invariant weakening allows the strength to minimize the size of the film so that just for the necessary carrying capacity of the polymer film is required is: In the absence of a statistical distribution of porosity lacks a static distribution of carrying capacity, so that the large security surcharges at the Dimensioning of the film thickness are no longer necessary.

Indeed shows that ceramic composite materials according to the invention, on a regularly perforated polymer film as a carrier substrate, at the same thermal and mechanical stability significantly lower overall strengths achieve as conventional organic / inorganic, on textile carrier substrate constructive composite separators.

Across from Separators obtained by stretching a film, have the ceramic composite materials according to the invention the advantage that dispenses with the step of stretching can be. Another advantage is that over the particle size used the pore size the ceramic composite material can be set relatively accurately while that produced by drawing ceramic Composite materials the pore size of the drawing process is dependent. Another advantage is that the Porosity of the ceramic composite material not alone through the coating material, but also through the perforation the perforated film can be modified: hole density and hole size can be specified exactly. When using the perforated sheets as a carrier substrate there is a further advantage that the thickness of the film can be set very variable. Preferably, films having a thickness of at least 1 μm used. In contrast to the polyolefin film has the present ceramic composite further has an advantage good wetting of the surface by battery electrolytes. By Use of foil as support as well as ceramic as coating material become the advantages of the ceramic (high porosity, ideal Pore width, small thickness, low basis weight, very good wetting behavior, high safety), as well as the polymeric Separator types (low basis weight, small thickness, high bend flexibility).

advantageously, the holes are made essentially round and the distance between the centers of two adjacent holes is chosen to be constant within the perforation is. Compliance with these geometric specifications leads to a particularly regularly perforated ceramic Composite material, which with regard to the constancy of the ion permeability highest expectations fulfilled. Round means in circular or elliptical or oval in this context. A circular one Hole cross-section is preferred, however, because circular holes thanks to their ideal symmetry a high regularity create and are technically easy to manufacture. But it is the same conceivable to choose hole cross-sections, the lower degree of symmetry reach such as ovals or elliptical holes, or holes, their cross section through a regular polygon is described.

The ceramic composite material according to the invention the coating only on one side of the polymer substrate or on both sides of the polymer substrate as well as in the holes exhibit. Preferably, the inventive ceramic composite the coating on both sides of the Polymer substrate and in the holes. Thus, the Coated on both sides of the carrier substrate, so that it passes through the coating holes. This increases the load capacity of the ceramic composite material and improves its homogeneity. This embodiment also has the advantage that when using the ceramic composite material for the separation of anode and cathode in each case the coating with the cathode or anode mass is in contact.

The ceramic particles of the coating are preferably over an inorganic binder connected together. The binder increases the cohesion of the coating and thus the mechanical strength. The use of an inorganic binder positively influences the Temperature resistance of the ceramic composite material.

When Inorganic binders are suitable silanes, ie compounds that composed of silicon and hydrogen.

alternative An organic binder can be used to make the ceramic Particles of the coating to connect with each other. The usage an organic binder has a positive effect on the flexibility of the ceramic composite material: This is how the ceramic material stands out Composite material with organically bound particles by an improved Bendability and a higher buckling tolerance such separators whose ceramic particles over inorganic binders are bonded. It is advantageous here that the Crosslinking of the ceramic particles does not have a different ceramic takes place, but that the polymeric organic binder takes over this task. The polymer is over a wide compared to the ceramic Temperature range much more flexible. Another advantage of the organic bonded ceramic composite material is that in the Cutting significantly less ceramic dust accumulates, than when Cutting of conventional ceramic separators.

One Another advantage of the organic binder is that it not only the ceramic particles among themselves, but also the ceramic ones Particles with the polymer film to connect. This will increases the adhesion of the coating to the carrier substrate, so that the coating during installation of the finished ceramic composite material in the cell is not damaged. Therefore, it is preferred an embodiment in which the organic binder at least a portion of the ceramic particles of the coating with the polymer film combines.

As an organic binder can z. Example, a polymer or a copolymer, preferably a fluorine-containing polymer or copolymer in the ceramic composite material according to the invention may be present. Preferably, the ceramic composite material of the present invention contains as the fluorine-containing organic binder at least one compound selected from polyvinylidene fluoride, polyvinylidene fluoride-hexafluoropropylene copolymer or polyvinylidene fluoride-chlorotrifluoroethylene copolymer. In the ceramic composite material according to the invention, polyvinylidene fluoride is particularly preferred as the fluorine-containing polymer or as copolymer a polyvinylidene fluoride-hexafluoropropylene copolymer. Suitable organic binder is the polyvinylidene fluoride-hexafluoropropylene copolymer available under the name Kynar ^Flex® 2801 from Arkema.

• a) Polyethylenterephthalat,
• b) Polyacrylnitril,
• c) Polyester,
• d) Polyamid,
• e) aromatisches Polyamid (Aramid),
• f) Polyolefin,
• g) Polytetraflourethylen,
• h) Polystyrol,
• i) Polycarbonat,
• k) Acrylnitril-Butadien-Styrol,
• l) Zellulosehydrat.

As polymer substrates, in particular films of such polymers or copolymers may be present, which preferably have a melting point of greater than 100 ° C, in particular greater than 130 ° C and particularly preferably greater than 150 ° C. Preferably, films of such polymer are present as a polymer substrate in the ceramic composite having a crystallinity of from 20 to 95%, preferably from 40 to 80%. Particular preference is given to using films of at least one of the following plastics as the carrier substrate:

• a) polyethylene terephthalate,
• b) polyacrylonitrile,
• c) polyester,
• d) polyamide,
• e) aromatic polyamide (aramid),
• f) polyolefin,
• g) polytetrafluoroethylene,
• h) polystyrene,
• i) polycarbonate,
• k) acrylonitrile-butadiene-styrene,
• l) cellulose hydrate.

suitable non-perforated Urfolien z. By DTF (DuPont-Teijin-Films) be obtained.

Such plastic films are prepared in a conventional manner by flat or tube extrusion or by casting from solutions. In this way you get a closed original film, which is to be perforated. A suitable laser-assisted process for perforating the closed polymer film is disclosed in US Pat US 7,083,837 described. Also suitable is the process filed by GR Advanced Materials Limited under the title "Microperforated Film" at the British Patent Office at the same time as the present application. Reference is made to the teaching of these documents to that extent.

It may be advantageous if the polymer film is a starch of less than 25 microns, preferably less than 15 microns and more preferably from 1 to 15 microns. By the very small thickness of the carrier substrate can be achieved that the entire ceramic composite material a Thickness of less than 25 microns. preferred ceramic composite materials according to the invention have a thickness of less than 25 microns, in particular a thickness of 4 to 20 microns. The strenght of the ceramic composite material has a great influence on its properties, because on the one hand the flexibility, on the other hand, the sheet resistance of the electrolyte impregnated ceramic composite material of starch of the ceramic composite material is dependent. By the low strength becomes a particularly low electrical Resistance of the ceramic composite material in the application with achieved an electrolyte. The ceramic composite itself of course has a very high electrical resistance because it itself must have insulating properties. moreover allow thinner ceramic composite materials increased Packing density in a battery pack, so that in the same Volume can store a larger amount of energy.

The Carrier substrate which is a perforated film has preferably holes with a diameter smaller than 500 μm, preferably less than 300 microns and more preferably from 40 up to 150 μm. Dodges the cross-sectional geometry of the holes from the preferred circular shape, so is below the aforementioned diameter each the maximum extent of the hole, so the diameter of the perimeter, understood.

The perforated film preferably has so many holes and so big holes on that, the percentage of holes on the total area of the polymer film is 10 to 90%. Thus, the polymer substrate has a perforated surface from 10-90% on, that is, the sum of the Cross sectional area of the individual holes 10 to 90% of the total area within the outer contour of the carrier substrate. Preferably, the polymer substrate an open area of 10 to 80%, more preferred from 20 to 75% on.

at smoother and more regular Distribution of circular holes with a uniform diameter in the film, the hole density in ppi (pores per inch) specified become. The choice of hole diameter and distance between The hole density is determined by the individual holes. For details, This will be described in the embodiments.

It may be advantageous if the polymer substrate the holes with a density greater than 30 ppi, preferably greater 40 ppi, and most preferably from 50 to 700 ppi. By a sufficiently large number of holes per unit area will be a sufficiently large Porosity of the substrate is achieved, leaving the substrate even the ionic line has the lowest possible resistance opposes.

The ceramic particles contained in the coating of the ceramic composite material according to the invention preferably have an average particle size d _{50 of} from 0.01 to 10 μm, preferably from 0.1 to 8 μm and particularly preferably from 0.1 to 5 μm. The mean particle size of the ceramic particles can be determined by means of small laser angle scattering in the production of the ceramic composite material or by separating the polymeric constituents of the ceramic composite material, for. B. be determined by dissolving the polymers of the ceramic particles.

It may be advantageous if the ceramic particles have a maximum particle size of 10 microns, preferably less than 10 microns and more preferably of less than 7.5 microns. By limiting the maximum particle size, it can be ensured that the ceramic composite material does not exceed a certain thickness. The maximum particle size and the particle size distribution can be determined, for example, by laser diffraction or as filter residue of a corresponding test sieve. In principle, all ceramic particles which are not electrically conductive can be present in the ceramic composite material as ceramic particles. Preferably, ceramic particles selected from the oxides of magnesium, silicon, boron, aluminum and zirconium or mixtures thereof are present in the ceramic composite material. The ceramic particles are preferably oxide particles of magnesium, barium, boron, aluminum, zirconium, titanium, hafnium, zinc, silicon, or mixed oxides of these metals, in particular B ₂ O ₃ , Al ₂ O ₃ , ZrO ₂ , BaTiO ₃ , ZnO , MgO, TiO ₂ and SiO ₂ .

The ceramic composite materials according to the invention can be bent without damage preferably to any radius down to 100 mm, preferably to a radius of 100 mm down to 50 mm and most preferably to a radius of 50 mm down to 0.5 mm. Also kinking survives the inventive ceramic composite harmless. The ceramic composite materials according to the invention are also distinguished by the fact that they preferably have a tensile strength (measured with a tension gauge from Zwick, according to Method ASTM D882 ) of at least 1 N / cm, preferably of at least 3 N / cm and most preferably of greater than 5 N / cm. The high tensile strength and good bendability of the ceramic composite material according to the invention has the advantage that changes occurring in the charging and discharging of a battery of the geometries of the electrodes can be through the ceramic composite material, without this being damaged. The flexibility also has the advantage that commercially standardized wound cells can be produced with this ceramic composite material. In these cells, the electrode / ceramic composite material layers are helically wound and contacted with each other in a standardized size.

The inventive ceramic composite material preferably has a porosity of from 30 to 60%, preferably from 40 to 50%. The porosity refers to the achievable, ie open pores. The porosity can by means of the known method of mercury porosimetry (based on DIN 66 133 ).

• a) Bereitstellen einer geschlossenen Polymerfolie,
• b) Lochen der Polymerfolie, sodass die Polymerfolie eine Perforation erhält, welche aus einer Vielzahl regelmäßig angeordneter Löcher besteht,
• c) Aufbringen einer keramische Partikel aufweisenden, porösen Beschichtung auf mindestens einer Seite der perforierten Polymerfolie.

The ceramic composite material according to the invention can be produced in various ways. The inventive ceramic composite material is preferably obtainable by the process according to the invention described below or is obtained by a process comprising the following steps:

• a) providing a closed polymer film,
• b) punching the polymer film so that the polymer film receives a perforation consisting of a plurality of regularly arranged holes,
• c) applying a ceramic coating having porous coating on at least one side of the perforated polymer film.

object The invention is therefore also a method for producing a ceramic composite material with the just listed Steps.

The application of the coating to the perforated polymer film is preferably carried out by applying and solidifying a dispersion onto the perforated polymer film, wherein the dispersion disperses ceramic particles in a solution, and the solution contains a preferably fluorine-containing organic binder dissolved in an organic solvent , In addition, the dispersion preferably contains an acid such as HNO ₃ . Dispersions according to the invention are also slip.

Preferably is used a dispersion containing a proportion of ceramic Particles in the total dispersion of 10 to 60 mass%, preferably from 15 to 40 and more preferably from 20 to 30% by mass.

In With respect to the binder, a dispersion is preferably used, a proportion of preferably fluorine-containing organic binder from 0.5 to 20% by mass, preferably from 1 to 10% by mass, and especially preferably from 1 to 5% by mass.

For the preparation of the dispersion, particular preference is given to using aluminum oxide particles as oxide particles, which preferably have an average particle size of from 0.1 to 10 μm, preferably from 0.1 to 5 μm. Furthermore, in the ceramic dispersion and lithium-containing compounds, in particular Li ₂ CO ₃ , LiCl, LiPF ₆ , LiBF ₄ , LiAsF ₆ , LiClO ₄ , LiTf (lithium trifluoromethylsulfonat), LiTFSI (lithium bis (trifluoromethanesulfonylimide)) introduced, and thus applied to the carrier substrate. Aluminum oxide particles in the range of preferred particle sizes are obtained, for example, from Martinswerke under the designations MZS3, MZS1, MDS6 and DN206 and from AlCoA under the name CT3000 SG, CL3000 SG, CL4400 FG, CT1200 SG, CT800SG and HVA SG.

to Preparation of the solution is the organic binder, preferably the fluorine-containing organic binder in a solvent solved. The amount of binder to be dissolved is determined depending on the above-mentioned proportion of binder in the finished dispersion. All compounds can be used as solvent which are able to dissolve the organic binder. As a solvent, for. An organic compound, selected from 1-methyl-2-pyrrolidone (NMP), acetone, ethanol, n-propanol, 2-propanol, n-butanol, cyclohexanol, diacetone alcohol, n-hexane, petroleum ether, cyclohexane, diethyl ether, dimethylformamide, Dimethylacetamide, tetrahydrofuran, dioxane, dimethyl sulfoxide, benzene, Toluene, xylene, dimethyl carbonate, ethyl acetate, chloroform or dichloromethane or a mixture of these compounds. Especially preferred solvents are acetone, isopropanol and / or Ethanol used. It may be advantageous if the production the solution with gentle heating, preferably at 30 to 55 ° C takes place. By heating the Solvent can accelerate the dissolution of the binder become.

The Solidification of the dispersion is preferably carried out by removal of the solvent. The removal of the solvent is preferably carried out by evaporation or evaporation of the solvent. Removal of the solvent may be at room temperature or at elevated temperature. Removing the Solvent at elevated temperature may be preferred be if the solvent should be removed quickly. For ecological and / or economic reasons it may be advantageous to remove the solvent removed by evaporation to collect, condense and re-solvent to use in the process according to the invention.

In the process of the invention, the dispersion applied to both sides or only on one side of the polymer film and be solidified there. Will open to get a coating Both sides of the polymer film, the dispersion on both sides of Applied polymer film and solidified there, so this can in one Work step done. But it can also be advantageous if the dispersion is first applied to one side of the film and solidified, and then the dispersion the other side of the film is applied and solidified.

In the process of the invention, the application can the dispersion on the polymer film z. B. by imprinting, pressing on, Pressing Rolling up, doctoring, painting, dipping, spraying or infusion. Particularly preferred, in particular if both sides of the polymer film to be coated takes place the application of the dispersion by immersing the polymer film in the dispersion.

The inventive method for the preparation of ceramic composite material may, for. B. carried out so be that the polymer film is unrolled from a roll, with a speed of 1 m / h to 2 m / s, preferably with a Speed of 0.5 m / min. up to 20 m / min through at least one Apparatus which disperses on one or two sides of the film applies and / or brings in the film, such as. B. a roller, and at least one other apparatus, which solidifies the Dispersion allows such. B. a possibly heated fan passes through and the ceramic composite material thus prepared rolled up on a second roll. That's the way it is possible, the ceramic composite material in a continuous process manufacture. Also possibly necessary pretreatment steps, such as As the perforation of the film can in a continuous process under Maintaining the mentioned parameters are carried out.

The ceramic composite materials according to the invention or the ceramic produced according to the invention Composite materials can be used as ceramic composite materials in batteries, in particular as ceramic composite materials in Lithium batteries (lithium-ion batteries), preferably lithium high-performance and high energy batteries are used. They then serve for insulation an anode to a cathode within an electrochemical Cell.

object Therefore, the invention is also a ceramic composite produced by the method according to the invention, and the Use of a ceramic according to the invention Composite materials for insulating an anode from one another Cathode inside an electrochemical cell.

object The invention further comprises an electrochemical cell an anode, a cathode, an electrolyte and an intermediate the anode and the cathode arranged ceramic according to the invention Composite material.

at the electrochemical cell is preferably a lithium-ion secondary battery.

The use of the ceramic composite materials according to the invention can be carried out by simple folding between the electrodes, but also by lamination of a stack consisting of anode - ceramic composite material - cathode. Such lithium batteries can be used as electrolytes z. B. have lithium salts with large anions in carbonates as a solvent. Suitable lithium salts are, for. LiClO ₄ , LiBF ₄ , LiAsF ₆ or LiPF ₆ , with LiPF _{6 being} particularly preferred. As solvents suitable organic carbonates are, for. Example, ethylene carbonate, propylene carbonate, dimethyl carbonate, ethyl methyl carbonate or diethyl carbonate or mixtures thereof.

Lithium batteries a ceramic composite material according to the invention can, in particular, in vehicles with full electric drive or a hybrid drive technology can be used, such. B. full electric cars, Hybrid cars or electric bicycles, but also in portable electronic devices such as laptops, cameras, mobile phones, as well as in portable power tools.

As well can the lithium batteries with the inventive ceramic composite material in stationary applications be used as in the off-grid, stationary Power supply by means of batteries (Auxillary Power Systems), in the uninterruptible power supply and in the provision of control energy.

embodiments

The The present invention will now be described by way of the following examples explained in more detail with the aid of the accompanying drawings without departing from the invention to the described embodiments is limited. Show it:

1 : Ceramic composite material according to the invention in cross-section;

2 : Hole pattern with offset holes;

3 : Hole pattern with aligned holes;

4 : Gurley apparatus;

5 : Diagram charging behavior;

table 1: data of powder types.

1 shows a schematic representation through the cross section of a ceramic composite material according to the invention 1 , The ceramic composite material 1 comprises a planar carrier substrate in the form of a polymer film 2 and one on the carrier substrate (polymer film 2 ) applied, ceramic particles 3 having, porous coating 4 , The ceramic particles 3 are connected by a binder, the bridges 5 between the particles 3 formed. The polymer film 2 is provided with a perforation consisting of a plurality of regularly arranged holes 6 consists. These are the holes 6 around through holes. The coating 4 is arranged on both sides of the carrier substrate, so that the perforation of the polymer film 2 concealed on both sides. Some of the over the binder bridges 5 interconnected particles 3 are in the holes 6 so the coating 4 the perforations forming holes 6 be upheld. The organic binder connects with its bridges 5 not just the ceramic particles 3 among themselves but also part of the particles 3 with the organic perforated foil 2 ,

In the schematic representation of 1 the diameter d of the holes is 5 μm. The mean particle size d ₅₀ is 1 μm. The thickness f of the film is 5 μm.

There the carrier substrate on both sides with about five particle layers is coated, the total thickness is S of ceramic composite material only 15 microns.

2 shows a perforated polymer film 2 in plan view for the purpose of explaining a first embodiment of the hole pattern in the context of the invention. The polymer film 2 has a variety of circular holes 6 which form a perforation in their entirety. Each of the holes 6 has a unit diameter d. The hole pattern is due to equilateral triangle, on whose vertices the holes are arranged. The distance D between two adjacent holes 6 measured between the centers of the holes is constant within the perforation. The holes 6 are arranged offset from each other.

3 shows a perforated polymer film 2 in plan view for explaining a second embodiment of the hole pattern in the context of the invention. The polymer film 2 has a variety of circular holes 6 which form a perforation in their entirety. Each of the holes 6 has a unit diameter d. The hole pattern is due to a square, on whose vertices the holes are arranged. The distance D between two adjacent holes 6 measured between the centers of the holes is constant within the perforation. The holes are aligned in the plane. In this square embodiment, with a hole diameter of 5 μm, a hole pitch D of 6.26 μm is selected to obtain an open area of 50%.

A ceramic composite material according to the invention can be produced as follows:
First, an unperforated PET polymer film is provided and punched, so that the polymer film as in the 2 or 3 shown perforation receives. A laser-assisted process for perforating the closed polymer film is known in US 7,083,837 described. Also suitable is the process filed by GR Advanced Materials Limited under the title "Microperforated Film" at the British Patent Office at the same time as the present application. Reference is made to the disclosure of these documents. For example, a PET film from DuPont-Teijin Films (DTF) can be used, which has a thickness f of 1.7 microns and which is perforated with holes with a diameter d of about 70 microns.

thereupon a slip is made. This will be a first 10% by mass solution of a polyvinylidene fluoride-hexafluoropropylene copolymer (PVdF-co-HFP) with a molar monomer ratio of 9 to 1, the company Arkema, product name Kynar Flex 2801, in acetone produced. To 4500 mL of this solution is added with stirring 3153 g of a 55% by mass mixture of alumina from the company Alcoa, product name CT3000, and acetone and 4 g nitric acid mixed in. The stirrer is a sash agitator used. For mixing, it is stirred for 1 hour at 300 rpm. For further comminution of agglomerates, the so obtained Mixture subjected to sonication (about 2 hours). For this purpose, the device UP 400 S Hielscher be used. The treatment is done so long until the slurry no particles are present, the one particle size of> 10 μm exhibit. This can be done by filtering through a filter cloth with 10 μm mesh size and by evaporation of the solvent be ensured with subsequent visual inspection.

It has been found to be the use of commercial Oxide particles may lead to unsatisfactory results leads, as often a very broad or polymodal Grain size distribution is present. It will therefore preferably metal oxide particles used by a conventional Method, such. For example, air classification and hydroclassification have been classified. Preference is given to using such fractions as oxide particles, in which the coarse grain fraction, which is up to 10% of the total amount characterized, was separated by wet sieving. This disturbing Coarse grain, which also by the production of the suspension typical processes such as milling (ball mill, attritor mill, Mortar mill), dispersing (Ultra-Turrax, ultrasound), Grinding or chopping is not or only very difficult crushed can be, for. B. consist of aggregates, hard agglomerates, Grinding media attritus. The above measures will ensures that the coating is a very uniform Having pore size distribution.

Table 1 gives an overview of how the choice of the different aluminas affects the porosity and the resulting pore size of the respective porous coating. To determine these data, the corresponding slips (suspensions or dispersions) were prepared and dried as pure moldings at 200 ° C and solidified. Al ₂ O ₃ type Porosity in% Avg. Pore size in nm AlCoA CL3000SG 51 755 AlCoA CT800SG 53.1 820 AlCoA HVA SG 53.3 865 AlCoA CL4400FG 44.8 1015 Martinsw. DN 206 42.9 1025 Martinsw. MDS 6 40.8 605 Martinsw. MZS 1 + Martinsw. MTS 3 = 1: 1 47 445 Martinsw. MTS 3 48 690 Table 1: Typical data of ceramics depending on the type of powder used

The mean pore size and the porosity mean the average pore size and the porosity, which can be determined by the known method of mercury porosimetry, z. Using a Porosimeter 4000 from Carlo Erba Instruments. Mercury porosimetry is based on the Washburn equation ( EW Washburn, "Note to a Method of Determining the Distribution of Pore Sizes in a Porous Material", Proc. Natl. Acad. Sci., 7, 115-16 (1921) ).

In the preparation of the ceramic dispersions, unsatisfactory results may possibly be obtained. In that case, it may be advantageous to use dispersing aids (eg Dolapix CE64 from Zschimmer and Schwarz) and / or deaerators and / or defoamers and / or wetting agents (the last three may be, for example, organically modified silicones, Fluorosurfactants or polyethers which are obtainable, for example, from Evonik Degussa GmbH or TEGO) and / or silanes, thereby achieving improved processability and, in the product, crosslinking of the ceramic. These silanes have the general formula R _x -Si (OR) _4-x with x = 1 or 2 and R = organic radical, optionally fluorine-containing organic radicals, where the radicals R may be the same or different and their reactive hydroxyalkyl groups are capable of reacting to form a covalent bond. Preferred silanes carry z. An amino group (3-aminopropyltriethoxysilane, AMEO), glycidyl group (3-glycidyloxypropyltrimethoxysilane, GLYMO) or an unsaturated group (methacryloxypropyltrimethoxysilane, MEMO) on the alkyl radical. In order to obtain a sufficient effect of the silanes, they may be added in a proportion of 0.1 to 20%, preferably 0.5 to 5% of the dispersion.

It may be advantageous, the finished dispersion before application to treat the polymer film. So it can be particularly beneficial be to treat the dispersion with ultrasound to possibly. smash formed agglomerates and thus ensure that in the suspension only particles, with the desired maximum Particle size are present. In any case it is necessary to stop or

re-agglomerate To prevent the ceramic particles by continuous stirring.

Of the Slip is then applied to the already perforated, as a carrier substrate serving PET film applied. The application of the slip on The film is made by manually dipping the film in the slurry. To the withdrawal of the film from the slurry is held vertically drained. After draining excess Slip is the film coated with the slurry in the air dried at room temperature for 12 hours.

A ceramic composite prepared in this way was analyzed.
Determination of the Gurley Number: The Gurley Number is a measure of the gas permeability of a porous material. It is defined as the time required for 100 cm ^{3 of} air to diffuse through one inch ^{2 of} a sample at a pressure of 12.2 inches and 30.988 cm of water, respectively. A schematic representation of the Gurley apparatus is in 4 displayed.

With a punching iron (15 mm after DIN 7200 ) was first a sample of the ceramic composite material separated and installed in the Gurley apparatus: On the apparatus is a NS29 ground sleeve. To install the sample, remove the complete cut from the apparatus. The first sample is inserted between the seal and the thread. The entire grinding is clamped to the glass apparatus with a grounding clip. Now bring the three-way cock on the apparatus in the correct position. With the pressure ball, the meniscus of ethylene glycol is roughly adjusted to the lower ring mark. Move the three-way cock to the correct position and set exactly to the ring mark using the vent valve.

execution the measurement: Now the two-way cock on the ground sleeve open. Once the meniscus of ethylene glycol the second Ring mark passes the stopwatch is started and at the third Ring mark stopped. The two-way cock must be closed again. There is a repetition of the measurement.

Calculation: The density of polyethylene glycol 400 is 1.113 g / cm ³ . The factor for the density correction is thus 0.885. The diameter of the membrane in the measurement is 1 cm. This results in an area of 0.785 cm ² . Since the Gurley number refers to an area of the ceramic composite of 1 inch ² , the time is divided by the area. Furthermore, instead of 100 cm ³ only 10 cm ^{3 is used} as the measurement volume. Thus, the equation for the Gurley number is:

In a first sample, after coating with the slurry, a material having a thickness S of 8 μm, a basis weight of 31 g / m ^2, and a Gurley number of 73 seconds was obtained.

In a second sample, the film was additionally laminated to a carrier fleece. After coating with the slurry, a material was obtained which has a thickness S of 20 μm, a basis weight of 52 g / m ² and a Gurley number of 89 seconds.

The investigation of the applicability of the ceramic composite material as described produced by construction of an electrochemical cell in the form of a lithium-ion flat battery. The battery consisted of a positive mass (LiCoO ₂ ), a negative mass (graphite) and an electrolyte of 1 mol / L LiPF ₆ in ethylene carbonate / dimethyl carbonate (weight ratio 1: 1). To produce the electrodes, positive (3% carbon black (Timcal, Super P), 3% PVdF (Arkema, Kynar 761), 50% N-methylpyrrolidone) or negative (1% carbon black (Timcal , Super P), 4% PVdF (Arkema, Kynar 761), 50% methylpyrrolidone) in a layer thickness of 100 microns on aluminum (Tokai 20 microns) or copper foil (Microhard, 15 microns) aufgerakelt and dried to weight consistency at 110 ° C. The two above-mentioned samples were used as a ceramic composite material between the electrodes of the battery. The battery ran stably for more than 100 cycles.

A diagram (capacity vs. charge / discharge cycle) of charging behavior is in 5 displayed.

1

ceramic composite

2

polymer film as a carrier substrate

3

particle

4

coating

5

bridges of the binder

6

holes, forming the perforation

d

diameter hole

D

distance two adjacent holes

d ₅₀

middle particle size

f

Strength the foil

S

Strength of the ceramic composite material

QUOTES INCLUDE IN THE DESCRIPTION

This list The documents listed by the applicant have been automated generated and is solely for better information recorded by the reader. The list is not part of the German Patent or utility model application. The DPMA takes over no liability for any errors or omissions.

Cited patent literature

• - DE 10208277 [0020]
• - DE 10347569 [0020]
• - DE 10347566 [0020]
• - DE 10347567 [0020]
• WO 02/15299 [0021]
• WO 02/071509 [0021]
• - DE 10343535 B3 [0022]
• - EP 1038329 B1 [0023]
• - US 6432576 B1 [0023]
• - DE 19921955 A1 [0024, 0024, 0024]
• WO 06/068428 A1 [0025, 0025, 0027, 0030]
• WO 06/004366 A1 [0026, 0027]
• WO 06/025662 A1 [0027]
• WO 08/097013 A1 [0028]
• US 7083837 [0047, 0087]

Cited non-patent literature

• - JO Besenhard in "Handbook of Battery Materials" (VCH-Verlag, Weinheim 1999) [0006]
• - ISO 9092: 1988 [0015]
• ASTM D882 [0055]
• - DIN 66 133 [0056]
• - EW Washburn, "Note to a Method of Determining the Distribution of Pore Sizes in a Porous Material", Proc. Natl. Acad. Sci., 7, 115-16 (1921) [0091]
• - DIN 7200 [0097]

Claims (30)

Ceramic composite material ( 1 ), comprising a planar carrier substrate ( 2 ) and one on the carrier substrate ( 2 ) applied, ceramic particles ( 3 ), porous coating ( 4 ), characterized in that it is in the carrier substrate ( 2 ) around a polymer film ( 2 ), that the carrier substrate ( 2 ) is provided with a perforation, which consists of a plurality of regularly arranged holes ( 6 ), and that the perforation at least on one side of the carrier substrate ( 2 ) of the porous coating ( 4 ) is covered. Ceramic composite material according to claim 1, characterized in that the holes ( 6 ) are substantially round, and that the distance (D) of the centers of two adjacent holes ( 6 ) is constant within the perforation. Ceramic composite material according to claim 1 or 2, characterized in that the coating ( 4 ) on both sides of the carrier substrate ( 2 ) and that the coating ( 4 ) the holes ( 6 ). Ceramic composite material according to one of claims 1 to 3, characterized in that the ceramic particles ( 3 ) of the coating ( 4 ) via a binder ( 5 ), whereby the binder ( 5 ) is an inorganic compound. Ceramic composite material according to claim 4, characterized in that the binder ( 5 ) contains a silane. Ceramic composite material according to one of claims 1 to 3, characterized in that the ceramic particles ( 3 ) of the coating ( 4 ) via a binder ( 5 ), whereby the binder ( 5 ) is an organic compound. Ceramic composite material according to claim 6, characterized in that at least a part of the ceramic particles ( 3 ) of the coating ( 4 ) over the organic binder ( 5 ) are connected to the polymer film. Ceramic composite material according to claim 6 or 7, characterized in that the binder ( 5 ) contains a fluorine-containing polymer. Ceramic composite material according to claim 8, characterized characterized in that the fluorine-containing polymer is polyvinylidene fluoride is. Ceramic composite material according to claim 6 or 7, characterized in that the binder ( 5 ) contains a fluorine-containing copolymer. Ceramic composite material according to claim 10, characterized characterized in that the fluorine-containing copolymer is um Polyvinylidene fluoride-hexafluoropropylene is. Ceramic composite material according to one of claims 1 to 11, characterized in that the polymer film ( 2 ) contains at least one of the following plastics: a) polyethylene terephthalate, b) polyacrylonitrile, c) polyester, d) polyamide, e) aromatic polyamide (aramid), f) polyolefin, g) polytetrafluoroethylene, h) polystyrene, i) polycarbonate, k) Acrylonitrile-butadiene-styrene, l) cellulose hydrate. Ceramic composite material according to one of claims 1 to 12, characterized in that the Thickness of the polymer film is less than 25 microns. Ceramic composite material according to one of claims 2 to 13, characterized in that the diameter (d) of each hole ( 6 ) of the perforation is less than 500 microns. Ceramic composite material according to one of the claims 1 to 14, characterized in that the proportion of holes on the total area of the polymer film is 10 to 90%. Ceramic composite material according to one of claims 1 to 15, characterized in that the ceramic particles ( 3 ) have a mean particle size d50 of 0.01 to 10 microns. Ceramic composite material according to claim 16, characterized in that the ceramic particles ( 3 ) have a maximum particle size of 10 microns. Ceramic composite material according to at least one of claims 1 to 17, characterized in that the Coating ceramic particles includes the oxides or mixed oxides of at least one of the following are: lithium, boron, Magnesium, aluminum, silicon, titanium, zinc, zirconium, niobium, barium, Hafnium. Method for producing a ceramic composite material, in particular a ceramic composite material according to one of Claims 1 to 18, characterized by the following Steps: a) providing a closed polymer film, b) Punch the polymer film so that the polymer film has a perforation which receives from a variety regularly arranged holes, c) applying a ceramic Particles having porous coating on at least one side of the perforated polymer film. Process according to claim 19 for the production of a ceramic composite material according to any one of claims 6 to 18, in which the application of the coating on the polymer film characterized in that a dispersion on the perforated polymer film is applied and solidified, wherein the dispersion ceramic particles dispersed in a solution, and wherein the solution an organic solvent dissolved in an organic Binder contains. Method according to claim 20, characterized in that that a dispersion is used which has a content of ceramic Particles in the total dispersion of 10 to 60% by mass. Method according to claim 20 or 21, characterized that a dispersion is used which contains a proportion of organic Binder of 0.5 to 20 mass% has. Method according to one of claims 20 to 22, characterized in that the solvent is an organic Compound selected from 1-methyl-2-pyrrolidone (NMP), Acetone, ethanol, n-propanol, 2-propanol, n-butanol, cyclohexanol, Diacetone alcohol, n-hexane, petroleum ether, cyclohexane, diethyl ether, Dimethylformamide, dimethylacetamide, tetrahydrofuran, dioxane, dimethyl sulphoxide, Benzene, toluene, xylene, dimethyl carbonate, ethyl acetate, chloroform or dichloromethane or a mixture of these compounds becomes. Method according to one of claims 20 to 23, characterized in that the solidification of the dispersion by removing the solvent. Method according to one of claims 20 to 24, characterized in that the dispersion on both sides applied to the polymer film and introduced into the holes and solidified. Method according to claim 25, characterized in that that the dispersion first on one side of the polymer film applied and introduced into their holes and solidified and then the dispersion on the other side the film is applied and solidified. Ceramic composite material ( 1 ) prepared by a process according to any one of claims 19 to 26. Use of a ceramic composite material ( 1 ) according to any one of claims 1 to 18 or claim 27 for isolating an anode from a cathode within an electrochemical cell. Electrochemical cell, with a cathode, with a Anode, with an electrolyte and with a between cathode and Anode arranged ceramic composite material, characterized in that that the ceramic composite material is a ceramic Composite material according to one of the claims 1 to 18 or according to claim 27. An electrochemical cell according to claim 29, characterized characterized in that the electrochemical cell is a Lithium secondary battery is.