EP2807209A1 - Composite, its production and its use in separators for electrochemical cells - Google Patents

Abstract

A composite which comprises at least one base body composed of nonwoven as component (A), at least one nanocomposite as component (B), at least one polyether or at least one polyether-comprising radical as component (C) and optionally a lithium salt as component (D) is provided. A process for producing the composite, its use in separators for electrochemical cells and compounds which can be used for producing nanocomposites (B) are also provided.

Description

 Composite material, its preparation and its use in separators for electrochemical cells

description

The present invention relates to a novel composite material comprising at least one base body of nonwoven fabric as component (A), at least one nanocomposite material as component (B), at least one polyether or at least one polyether-containing radical as component (C) and optionally a lithium salt as component (D).

Furthermore, the invention also relates to a process for the preparation of the new composite material, its use in separators for electrochemical cells and special starting compounds which can be used for the production of nanocomposite material (B).

Saving energy has long been an object of growing interest. Electro-chemical cells, for example batteries or accumulators, can serve to store electrical energy. Of particular interest since recently the so-called lithium-ion batteries. They are superior in some technical aspects to conventional batteries. So you can create with them voltages that are not accessible with batteries based on aqueous electrolytes.

However, conventional lithium-ion secondary batteries having a carbon anode and a metal oxide-based cathode are limited in their energy density. New dimensions in energy density were opened by lithium-sulfur cells. In lithium-sulfur cells, sulfur in the sulfur cathode is reduced via polysulfide ions to S ^2_ , which are oxidized again during charging of the cell to form sulfur-sulfur bonds.

In electrochemical cells, the positively and negatively charged electrode masses are mechanically separated from one another by nonelectrically conductive layers, so-called separators, to avoid an internal discharge. Due to their porous structure, these separators enable the transport of ionic charges as a basic requirement for the ongoing current drain during battery operation. Basic requirements for separators consist in the chemical and electrochemical stability compared to the active electrode materials and the electrolyte. In addition, there must be a high mechanical load capacity compared with the tensile forces occurring during the battery cell production process. At a structural level, high porosity is required to absorb the electrolyte to ensure high ionic conductivity. At the same time, pore size and the structure of the channels must effectively suppress the growth of metal dendrites to avoid shorting, as described in Journal Power Sources 2007, 164, 351-364.

Separators as microporous layers often consist of either a polymer membrane or a nonwoven fabric. Currently, polymer membranes based on polyethylene and polypropylene are commonly used as separators in electrochemical cells, which membranes exhibit a lack of resistance at elevated temperatures of 130 to 150 ° C. An alternative to the frequently used polyolefin separators are separators based on nonwovens, which are filled with ceramic particles and additionally fixed with an inorganic binder of oxides of the elements silicon, aluminum and / or zirconium, as in DE10255122 A1, DE10238941 A1, DE10208280 A1, DE10208277 A1 and WO 2005/038959 A1. However, the nonwovens filled with ceramic particles have increased surface weights and greater thicknesses in comparison with the unfilled nonwovens.

WO 2009/033627 discloses a sheet which can be used as a separator for lithium-ion batteries. It comprises a nonwoven as well as embedded in the nonwoven particles, which consist of organic polymers and optionally partly of inorganic material. Such separators are intended to avoid short circuits caused by metal dendrites. In WO 2009/033627, however, no long-term cyclization experiments are disclosed.

WO 2009/103537 discloses a sheet having a base body having pores, the sheet further comprising a binder which is crosslinked. In a preferred embodiment, the base body is at least partially filled with particles. The disclosed layers can be used as separators in batteries. In WO 2009/103537, however, no electrochemical cells are produced and investigated with the layers described. WO 201/000858 describes a porous film material comprising at least one carbon-containing Halbmetalloxidphase and can be used as a separator in rechargeable lithium-ion cells. The carbonaceous semimetal oxide phase is obtained by a so-called twin polymerization described by S. Spange et al. in Angew. Chem. Int Ed., 46 (2007) 628-632.

The separators known from the literature have with regard to one or more of the desired properties for the separators such as low thickness, low basis weight, good mechanical stability during processing, for. As high flexibility or low abrasion, or in battery operation against metal dendrite growth, good temperature resistance, low shrinkage behavior, high porosity, good ion conductivity and good wettability with the electrolyte liquids, still deficits. Finally, some of the deficiencies of the separators are responsible for a reduced lifetime of the electrochemical cells containing them. Furthermore, separators must in principle be not only mechanically but also chemically stable with respect to the cathode materials, the anode materials and the electrolyte. In the field of lithium-sulfur cells separators are desired, which also prevent the early cell death of lithium-sulfur cells, which is favored in particular by the migration of polysulfide ions from the cathode to the anode. It is an object of the present invention to provide a low-cost separator for a long-lived electrochemical cell, in particular a lithium-sulfur cell, which has advantages over one or more properties of a known separator, in particular a separator having a good lithium-ion permeability, high temperature stability and good mechanical properties shows.

This object is achieved by a composite material comprising components

(A) at least one base body made of nonwoven fabric;

(B) at least one nanocomposite material containing

 (a) at least one inorganic or (semi-) organometallic phase (a) containing at least one metal or metalloid M; and

 (b) at least one organic polymer phase (b), wherein the organic polymer phase (b) and the inorganic or (semi-) metal organic phase (a) form substantially co-continuous phase domains, wherein the mean distance between two adjacent domains of identical phases maximum 100 nm;

(C) at least one polyether or at least one polyether-containing radical, wherein the polyether-containing radical is covalently bound to the (semi-) organometallic phase (a) or organic polymer phase (b); and

(D) optionally at least one lithium salt dissolved.

The composite materials according to the invention are composite materials which in the context of the present invention are also called composite materials according to the invention. Composite materials are generally understood to mean materials which are solid mixtures which can not be separated manually and which have different properties than the individual components. Specifically, composite materials according to the invention are fiber composites.

Depending on the total volume of the base body made of nonwoven fabric (A) to the total volume of the nanocomposite material (B) and depending on the method for contacting the component (A) with the component (B), the main body of nonwoven fabric (A) partially to completely from the Nanocomposite matenal (B) be penetrated. In this case, the main body of nonwoven fabric can be penetrated symmetrically or asymmetrically, that is, opposite sides of the body of nonwoven fabric can differ from each other.

In one embodiment of the present invention, the composite material according to the invention is characterized in that the base body of nonwoven fabric (A) is at least partially, preferably more than 50%, in particular completely penetrated by the nanocomposite material (B). The composite material according to the invention comprises as component (A) at least one main body made of nonwoven fabric, also referred to as nonwoven fabric (A) in the context of the present invention. Nonwovens and their preparation are known in the art. Commercially, a wide range of nonwovens is available. Thus, a nonwoven fabric of inorganic or organic materials, preferably made of organic materials.

Examples of inorganic nonwovens are glass fiber nonwovens and ceramic fiber nonwovens.

Examples of organic polymers for producing nonwovens are polyolefins, in particular polyethylene or polypropylene, polymers of heteroatom-containing vinyl monomers, in particular polyacrylonitrile, polyvinylpyrrolidone or polyvinylidene fluoride, polyesters, in particular polybutyl terephthalate, polyethylene terephthalate or polyethylene naphthalate, polyamides, in particular PA 6, PA 11 , PA 12, PA 6.6, PA 6.10 or PA 6.12, polyimides, polyetheretherketones, polysulfones or polyoxymethylene.

In one embodiment of the present invention, the composite material according to the invention is characterized in that the main body of nonwoven fabric (A) is made of organic polymers which are selected from the group of polymers consisting of polyolefins, in particular polyethylene and polypropylene, polymers of heteroatom-containing Vinyl monomers, in particular polyacrylonitrile, polyvinylpyrrolidone and polyvinylidene fluoride, polyesters, in particular polybutyl terephthalate, polyethylene terephthalate and polyethylene naphthalate, polyamides, in particular PA 6, PA 11, PA 12, PA 6.6, PA 6.10 and PA 6.12, polyimides, polyether ether ketones, polysulfones and polyoxymethylene are. Particular preference is given to nonwovens (A) which are made of polyester, in particular of polyethylene terephthalate.

The base body made of nonwoven fabric is preferably a sheet-like basic body, wherein in the context of the present invention the term "sheet-like" means that the basic body described, a three-dimensional body, in one of its three spatial dimensions (expansions), namely Thickness is smaller than in the other two dimensions, the length and the width.Usually, the thickness of the main body is at least a factor of 5, preferably at least a factor of 10, more preferably at least 20 times smaller than the second largest extent.

Accordingly, the composite material containing the main body (A) also preferably constitutes a sheet-like body.

In one embodiment of the present invention, the composite material according to the invention is characterized in that the composite material is a sheet-like body. The base body of nonwoven preferably has a thickness in the range of 5 to 100 μηη, particularly preferably 10 to 50 μηη, in particular 15 to 25 μηη on. The fibers from which the nonwoven fabric is made usually have a fiber length which exceeds the mean diameter of the fibers by at least two times, preferably a multiple. The average diameter of at least 90% of the fibers contained in the non-woven is preferably at most 20 μηη, more preferably at most 12 μηη, in particular between 4 and 6 μηη. The porosity of the base body of nonwoven fabric is preferably in the range of 50 to 80%, preferably in the range of 50 to 60%. Furthermore, the composite material according to the invention comprises as component (B) at least one nanocomposite material, in the context of the present invention also called nanocomposite (B) for short, which

 (a) at least one inorganic or (semi-) organometallic phase (a) containing at least one metal or metalloid M; and

(b) at least one organic polymer phase (b), wherein the organic polymer phase (b) and the inorganic or (semi-) metal organic phase (a) form substantially co-continuous phase domains, wherein the mean distance between two adjacent domains of identical phases not more than 100 nm, preferably not more than 40 nm, more preferably not more than 10 nm, in particular not more than 5 nm.

Nanocomposites (B), as defined above, are known in principle and are accessible in different macroscopic forms, the microscopic structure of phases (a) and phases (b) being substantially identical, that is, phase (a) and phase (b) being substantially identical. form substantially co-continuous phase domains, wherein the average distance between two adjacent domains of identical phases is at most 100 nm.

 WO2010 / 1 12581, pages 30 to 31 describes various nanocomposites (B) as solids. In WO 2010/128144, page 38, line 1 to page 41, line 26, particulate nanocomposites (B) are described, and in WO 201 1/000858, page 6, line 24 to page 12, line 28, nanocomposites (B) are described as porous Foil materials described. With regard to the preferred embodiments of the nanocomposite (B) and the explanations concerning the terms of the phases and phase domains, reference is made in full to those parts of the text which are hereby made part of the description of the present invention. The metal or semimetal M in the inorganic or (semi-) organometallic phase (a) is preferably selected from B, Al, Si, Ti, Zr, Hf, Ge, Sn, Pb, V, As, Sb, Bi and mixtures thereof , M is especially selected from B, Al, Si, Ti, Zr and Sn, preferably from Al, Si, Ti and Zr, in particular Si. Particularly preferred are at least 90 mol%, especially at least 99 mol% or the total amount of all metals or semimetals M is equal to silicon.

In one embodiment of the present invention, the composite material according to the invention is characterized in that the metal or metalloid M of phase (a) is selected among B, Al, Si, Ti, Zr, Hf, Ge, Sn, Pb, V, As, Sb, Bi and mixtures thereof, is preferably selected from B, Al, Si, Ti, Zr and Sn, is particularly preferably selected among Al, Si, Ti and Zr, in particular, is selected from Si. In a further embodiment of the present invention, the composite material according to the invention is characterized in that the metal or semimetal M comprises at least 90 mol%, in particular at least 99 mol%, based on the total amount of M, silicon. Furthermore, the composite material according to the invention comprises as component (C) at least one polyether or at least one polyether-containing radical, the polyether-containing radical being covalently bound to the (semi-) organometallic phase (a) or organic polymer phase (b). Polyethers and their preparation are known in principle to the person skilled in the art. Thus, a variety of polyethers is commercially available. Preferably, many of these polyethers contain the monomer units ethylene oxide or propylene oxide, in particular ethylene oxide. Both cyclic and linear polyethers are known. An example of a defined cyclic polyether is, for example, [18] crown-6. Examples of linear polyethers are in particular polyalkylene glycols, preferably poly-C 1 -C 4 -alkylene glycols and in particular polyethylene glycols. Polyethylene glycols may contain up to 20 mol% of one or more C 1 -C 4 -alkylene glycols in copolymerized form. Preferably, polyalkylene glycols are polyalkylene glycols double capped with methyl or ethyl. The molecular weight M _w of suitable polyalkylene glycols and in particular of suitable polyethylene glycols may be in the range of at least 200 g / mol up to 100,000 g / mol, preferably from 400 g / mol up to 10,000 g / mol. Polyethers preferred as component (C) are selected from the group of polyethylene glycols, polypropylene glycols and copolymers of ethylene oxide and propylene oxide.

Polyether-containing radicals, their production and handling are also known to the person skilled in the art. Since polyether-containing radicals are derived in principle from a polyether as described above, for example by abstraction of a hydrogen atom from a hydrocarbon fragment or preferably an OH group of the relevant polyether, the polyether-containing radicals are based in particular on the monomer units ethylene oxide or propylene oxide, in particular ethylene oxide ,

The polyether-containing radical which is covalently bound to the (semi-) organometallic phase (a) or organic polymer phase (b) is preferably directly via an oxygen atom of the polyether-containing radical or in particular via a divalent hydrocarbon fragment, for example a methylene group, Ethylene group, propylene group or a Phenylengrup- pe connected to one of the two phases. Particular preference is given to a polyether-containing radical which contains monomer units selected from the group consisting of ethylene oxide and propylene oxide via a C atom with the (semi-) organometallic phase (a), in particular with the metal or semimetal M of the (semi-) organometallic phase (a), in particular with Si, connected.

The proportion by weight of the entire component (C), that is to say of the at least one polyether or of the at least one polyether-containing radical, based on the total weight of the composite material, is preferably between 5 and 60% by weight, particularly preferably between 30 and 50% by weight. , The proportion by weight of the total nanocomposite material (B) based on the total weight of the composite material is preferably at least 20% by weight, more preferably at least 30% by weight and may be up to a maximum of 99% by weight, preferably up to 95% by weight. -%.

The composite material according to the invention may optionally comprise at least one lithium salt as component (D). The composite material according to the invention preferably comprises at least one lithium salt as component (D).

In particular, component (D) is such a lithium salt which is commonly used as a conductive salt in lithium-ion cells. The lithium salt (D) is particularly preferably selected from the group consisting of lithium hexafluorophosphate, lithium perchlorate, lithium hexafluoroarsenate, lithium trifluoromethylsulfonate, lithium (bis (trifluoromethylsulfonyl) imide) and lithium tetrafluoroborate.

In a further embodiment of the present invention, the composite material according to the invention is characterized in that the lithium salt (D) is selected from the group consisting of lithium hexafluorophosphate, lithium perchlorate, lithium hexafluoroarsenate, lithium trifluoromethylsulfonate, lithium (bis (trifluoromethylsulfonyl) imide) and lithium tetrafluoroborate.

To increase the temperature stability, the composite material according to the invention may comprise as further constituent a component (E) which is at least one inorganic (semi-) metal oxide in the form of particles. Examples of such inorganic (semi-) metal oxides are silicates, aluminates, titanium dioxides, barium titanate, zirconium dioxide or yttrium oxide.

The component (B) of the composite material according to the invention, namely the nanocomposite (B), is preferably a polymerization product of at least one monomer AB, which

at least one first cationically polymerizable monomer unit A, which has a metal or semimetal M, and

 at least one second cationically polymerizable organic monomer unit B, which is connected via one or more covalent chemical bonds to the polymerizable monomer unit A,

wherein the polymerization product is obtained under cationic polymerization conditions under which both the polymerizable monomer unit A and the polymerizable monomer unit B polymerize to break the bond between A and B, and wherein the Monomer AB in the presence of the main body of nonwoven fabric (A), the polyether or the polyether-containing radical (C) and optionally the lithium salt (D) is polymerized.

In a further embodiment of the present invention, the composite material according to the invention is characterized in that the nanocomposite material (B) is a polymerization product of at least one monomer AB which

 at least one first cationically polymerizable monomer unit A, which has a metal or semimetal M, and

 at least one second cationically polymerisable organic monomer unit B which is connected via one or more covalent chemical bonds to the polymerizable monomer unit A,

wherein the polymerization product is obtained under cationic polymerization conditions under which polymerize both the polymerizable monomer unit A and the polymerizable monomer unit B breaking the bond between A and B, and wherein the monomer AB in the presence of the base body of nonwoven fabric (A), the polyether or the polyether-containing radical (C) and optionally the lithium salt (D) is polymerized.

The preparation of the composite materials according to the invention is achieved by a process which comprises a so-called twin polymerization of the monomers AB explained in more detail below under cationic polymerization conditions, wherein the monomer AB in the presence of the main body of nonwoven fabric (A), the polyether or the polyether-containing radical ( C) and optionally the lithium salt (D) is polymerized. The components (A), (C) and (D) have already been explained in detail above. The principle of the twin polymerization of so-called "twin monomers" is described, for example, in WO 2010/112581, page 2, line 16 to page 4, line 11 or in WO 201 1/000858, page 14, line 29 to page 16, line 7 A twin copolymerization of two different (twin) monomers is explained in detail, for example, in WO 201 1/000858, page 16, line 9 to page 24, line 11.

Another object of the present invention is therefore also a method for producing a composite material comprising the components

 (A) at least one base body made of nonwoven fabric;

 (B) at least one nanocomposite material containing

 (a) at least one inorganic or (semi-) organometallic phase (a) containing at least one metal or metalloid M; and

 (b) at least one organic polymer phase (b);

 in particular, a nanocomposite material wherein the organic polymer phase (b) and the inorganic or (semi-) metal organic phase (a) form substantially co-continuous phase domains, wherein the mean distance between two adjacent domains of identical phases is at most 100 nm;

(C) at least one polyether or at least one polyether-containing radical, wherein the polyether-containing radical is covalently bonded to the (semi-) organometallic phase (a) or organic polymer phase (b); and (D) optionally a lithium salt; by polymerization of at least one monomer AB, the

 at least one first cationically polymerizable monomer unit A, which has a metal or semimetal M, and

 at least one second cationically polymerizable organic monomer unit B, which is connected via one or more covalent chemical bonds to the polymerizable monomer unit A,

under cationic polymerization conditions under which both the polymerizable monomer unit A and the polymerizable monomer unit B polymerize while breaking the bond between A and B, wherein the polymerization in the presence of the base body of nonwoven fabric (A), the polyether or the polyether-containing radical (C) and optionally the lithium salt (D) is carried out. The description and preferred embodiments of the components (A), (B), (C) and (D) in the method according to the invention are consistent with the above description of these components for the composite material according to the invention.

The metal or semimetal M of the monomer unit A in the monomers AB is preferably selected from B, Al, Si, Ti, Zr, Hf, Ge, Sn, Pb, V, As, Sb, Bi and mixtures thereof. M is in particular selected from B, Al, Si, Ti, Zr and Sn, preferably from Al, Si, Ti and Zr, in particular Si. Particularly preferred are at least 90 mol%, especially at least 99 mol% or the total amount of all metals or semimetals M is equal to silicon. In one embodiment of the present invention, the method according to the invention for producing a composite material is characterized in that the metal or semimetal M of the monomer unit A in the monomers AB is selected from B, Al, Si, Ti, Zr, Hf, Ge, Sn, Pb, V, As, Sb, Bi and mixtures thereof, preferably selected from B, Al, Si, Ti, Zr and Sn, more preferably selected from Al, Si, Ti and Zr, in particular is selected from Si.

In a further embodiment of the present invention, the method according to the invention for producing a composite material is characterized in that the metal or semimetal M of the monomer unit A is at least 90 mol%, in particular at least 99 mol%, based on the total amount of M, silicon includes.

In the process according to the invention for producing a composite material, preference is given to using those monomers AB which have at least one monomer unit A and at least one monomer unit B and which are described by the general formula I

wherein

M is a metal or semimetal;

R, R ^{2 may be the} same or different and each represents a radical

Ar-C (R ^a , R ^b ) - where Ar is an aromatic or heteroaromatic ring which optionally has 1 or 2 substituents which are halogen, CN, C 1 -C 6 -alkyl, C 1 -C 6 -alkoxy and phenyl R ^a , R ^b independently of one another represent hydrogen or methyl or together denote an oxygen atom or a methylidene group (= CH 2),

or the radicals R ¹ Q and R ² G together represent a radical of the formula Ia

where A is an aromatic or heteroaromatic ring fused to the double bond, m is 0, 1 or 2, the radicals R may be identical or different and are halogen, CN, C 1 -C 6 -alkyl, C 1 -C 6 -alkoxy and phenyl are selected and R ^a , R ^{b have} the meanings given above;

G is O, S or NH, in particular O;

 Q is O, S or NH, in particular O;

q corresponding to the valence of M is 0, 1 or 2,

 X, Y may be the same or different and each is O, S, NH or a chemical

 Bond, in particular O or a chemical bond;

R ¹ ', R ² ' may be the same or different and each is C ¹ -C 6 -alkyl, C 3 -C 6 -cycloalkyl, a polyether-containing radical containing monomer units selected from the group consisting of ethylene oxide and propylene oxide, and aryl or a radical Ar '-C (R ^a ', R ^b ') - are in which Ar' has the meanings given for Ar and R ^a ', R ^b ' have the meanings given for R ^a , R ^b or R ¹ ', R ² ' together with

X and Y are a radical of the formula Ia as defined above; or, when X is oxygen, the radical R ¹ 'is a radical of the formula Ib: in which q, R ¹ , R ² , R ^{2 '} , Y, Q and G have the meanings given above and # denotes the bond to X.

In the monomers of the formula I, the moieties corresponding to the radicals R ¹ and R ² G form polymerisable unit (s) B. If X and Y are different from a chemical bond and R ^{1 '} X and R ^2' do not represent inert radicals such as C i C6-alkyl, C3-C6-cycloalkyl or aryl, the radicals R ^{1 '} X and R ^2' Y also form polymerizable unit (s) B. On the other hand forms the metal atom M, optionally together with the groups Q and Y, the Main component of the monomer unit A.

In the context of the invention, an aromatic radical, or aryl, is understood to mean a carbocyclic aromatic hydrocarbon radical, such as phenyl or naphthyl.

In the context of the invention, a heteroaromatic radical or hetaryl is understood as meaning a heterocyclic aromatic radical which generally has 5 or 6 ring members, one of the ring members being a heteroatom which is selected from nitrogen, oxygen and sulfur and, if appropriate 1 or 2 further ring members may be a nitrogen atom and the remaining ring members are carbon. Examples of heteroaromatic radicals are furyl, thienyl, pyrrolyl, pyrazolyl, imidazolyl, oxazolyl, isoxazolyl, pyridyl, pyrimidyl, pyrdazinyl or thiazolyl.

For the purposes of the invention, a condensed aromatic radical or ring is understood as meaning a carbocyclic aromatic, divalent hydrocarbon radical, such as o-phenylene (benzo) or 1,2-naphthylene (naphtho).

For the purposes of the invention, a fused heteroaromatic radical or ring is understood as meaning a heterocyclic aromatic radical as defined above, in which two adjacent C atoms form the double bond shown in formula Ia or in the formulas I I and I I I. The metal or metalloid M in formula I is in particular for the preferred embodiments of M. given in connection with the description of the composite material.

According to a first embodiment of the monomers of the formula I, the groups R ¹ Q and R ² G together represent a radical of the formula Ia as defined above, in particular a radical of the formula Iaa:

wherein #, m, R, R ^a and R ^{b have} the meanings given above. In the formulas la and laa, the variable m is, in particular, 0. If m is 1 or 2, R is in particular a methyl or methoxy group. In formulas Ia and laa, R ^a and R ^{b are} in particular hydrogen. In formula Ia, Q is in particular oxygen. In the formulas Ia and Ia, G stands in particular for oxygen or NH, in particular for oxygen.

Among the monomers of the first embodiment, particular preference is given to those monomers of the formula I in which q = 1 and in which the groups XR ^{1 '} and YR ^2' together represent a radical of the formula Ia, in particular a radical of the formula Iaa. Such monomers can be described by the following formulas II or IIa:

Among the twin monomers of the first embodiment, preference is furthermore given to those monomers of the formula I in which q is 0 or 1 and in which the group XR ^{1 'is} a radical of the formula Ia' or Iaa ':

wherein m, A, R, R ^a , R ^b , G, Q, X ", Y, R ^{2 '} and q have the abovementioned meanings, in particular those mentioned as being preferred. Such monomers can be described by the following formulas II 'or IIa':

In formulas II and II 'the variables have the following meanings:

 M is a metal or semimetal, preferably B, Al, Si, Ti, Zr, Hf, Ge, Sn, Pb, V,

 As, Sb or Bi, particularly preferably B, Al, Si, Ti, Zr or Sn, very particularly preferably Al, Si, Ti or Zr, in particular Si;

A, A 'independently represent an aromatic or heteroaromatic ring fused to the double bond;

m, n are independently 0, 1 or 2, in particular 0;

G, G 'independently represent O, S or NH, in particular O or NH and especially O;

 Q, Q 'independently represent O, S or NH, in particular O;

R, R 'are independently halogen, CN, Ci-C6-alkyl, Ci-C6-alkoxy and

 In particular, independently of one another, are methyl or methoxy;

R ^a , R ^b , R ^{a '} , R ^b' are independently selected from hydrogen and methyl or

R ^a and R ^b and / or R ^a and R ^{b '} each, together, represent an oxygen atom o = = CH 2; in particular, R ^a , R ^b , R ^{a '} , R ^{b' are} each hydrogen;

L represents a group (YR ^{2 '} ) _q in which Y, R ^2' and q have the meanings given above and

 X "has one of the meanings given for Q and in particular represents oxygen. In formulas IIa and IIa ', the variables have the following meanings:

 M is a metal or semimetal, preferably B, Al, Si, Ti, Zr, Hf, Ge, Sn, Pb, V,

 As, Sb or Bi, particularly preferably B, Al, Si, Ti, Zr or Sn, very particularly preferably Al, Si, Ti or Zr, in particular Si;

m, n are independently 0, 1 or 2, in particular 0;

G, G 'independently represent O, S or NH, in particular O or NH and especially O; R, R 'are independently selected from halogen, CN, C 1 -C 6 -alkyl, C 1 -C 6 -alkoxy and phenyl and are in particular methyl or methoxy;

R ^a , R ^b , R ^{a '} , R ^b' are independently selected from hydrogen and methyl or

R ^a and R ^b and / or R ^a and R ^{b '} are each together an oxygen atom; in particular, R ^a , R ^b , R ^{a '} , R ^{b' are} each hydrogen;

L is a group (YR ^{2 '} ) _q , wherein Y, R ^2' and q have the meanings given above.

An example of a monomer of the formula II or IIa is 2,2'-spirobis [4H-1,2,2-benzodioxasiline] (compound of the formula IIa where M = Si, m = n = 0, G = G ' = O, R ^a = R ^b = R ^{a '} = R ^b' = hydrogen). Such monomers are known from WO2009 / 083082 and WO2009 / 083083 or can be prepared by the methods described therein. Another example of a monomer IIa is 2,2-spirobi [4H-1,2,2-benzodioxaborine] (Bull. Chem. Soc. Jap. 51 (1978) 524): (compound of the formula IIa where M = B, m = n = 0, G = O, R ^a = R ^b = R ^{a '} = R ^b' = hydrogen). Another example of a monomer IIa 'is bis (4H-1,2,2-benzodioxaborin-2-yl) oxide (compound of formula IIa' with M = B, m = n = 0, L absent (q = 0 ), G = O, R ^a = R ^b = R ^{a '} = R ^b' = hydrogen, Bull Chem., Soc., 51 (1978) 524).

In the monomers II and IIa, the moiety MQQ 'or MO2 forms the polymerizable unit A, whereas the remaining portions of the monomers II and IIa, i. the groups of the formulas Ia and Iaa minus the atoms Q and Q '(or minus the oxygen atom in laa) form the polymerizable units B.

Formula III, the variables have the following meanings

M is a metal or semimetal, preferably B, Al, Si, Ti, Zr, Hf, Ge, Sn, Pb, V,

 As, Sb or Bi, particularly preferably B, Al, Si, Ti, Zr or Sn, very particularly preferably Al, Si, Ti or Zr, in particular Si;

 A is an aromatic or heteroaromatic ring fused to the double bond;

m is 0, 1 or 2, in particular 0;

 G is O, S or NH, in particular O or NH and especially O;

Q is O, S or NH, in particular O;

q, corresponding to the valency and charge of M, is 0, 1 or 2; R is independently selected from halogen, CN, C 1 -C 6 -alkyl, C 1 -C 6 -alkoxy and phenyl and is in particular methyl or methoxy;

R ^a , R ^b are independently selected from hydrogen and methyl or R ^a and

R ^b may together represent an oxygen atom or = CH 2, and in particular both represent hydrogen;

R ^c , R ^d are identical or different and are each selected from C 1 -C 6 -alkyl, C 3 -C 6 -cycloalkyl, polyether-containing radical containing monomer units selected from the group consisting of ethylene oxide and propylene oxide, and aryl and are in particular methyl ,

In formula I la the variables have the following meanings:

 M is a metal or semimetal, preferably B, Al, Si, Ti, Zr, Hf, Ge, Sn, Pb, V,

 As, Sb or Bi, particularly preferably B, Al, Si, Ti, Zr or Sn, very particularly preferably Al, Si, Ti or Zr, in particular Si;

m is 0, 1 or 2, in particular 0;

 G is O, S or NH, in particular O or NH and especially O;

 Radicals R are independently halogen, CN, Ci-C6-alkyl, Ci-C6-alkoxy and

 Phenyl selected and are in particular methyl or methoxy;

R ^a , R ^b are independently selected from hydrogen and methyl or R ^a and

R ^b may together represent an oxygen atom or = CH 2, and in particular both represent hydrogen;

R ^c , R ^d are identical or different and in each case selected from Ci-C6-alkyl, C3-C6-cycloalkyl, polyether-containing radical containing monomer units selected from the group consisting of ethylene oxide and propylene oxide, and aryl and are in particular for methyl.

Examples of monomers of the formula III or IIIa are 2,2-dimethyl-4H-1,3,2-benzodioxasiline (compound of the formula III with M = Si, q = 1, m = 0, G = O, R ^a = R ^b = hydrogen, R ^c = R ^d = methyl), 2,2-dimethyl-4H-1, 3,2-benzooxazasiline, (compound of the formula IIIa where M = Si, q = 1, m = 0 , G = NH, R ^a = R = hydrogen, R ^c = R ^d = methyl), 2,2-dimethyl-4-oxo-1, 3,2-benzodioxasiline (compound of the formula Ia with M = Si, q = 1, m = 0, G = O, R ^a + R ^b = O, R ^c = R ^d = methyl) and 2,2-dimethyl-4-oxo-1,3,2-benzooxazasiline, (compound of formula Ia where M = Si, q = 1, m = 0, G = NH, R ^a + R ^b = O, R ^c = R ^d = methyl). Such monomers are known, for example, from Wieber et al. Journal of Organometallic Chemistry, 1, 1963, 93, 94. Further examples of monomers Ia are 2,2-diphenyl [4H-1,2,2-benzodioxasiline] (J. Organomet. Chem. 71 (1974) 225);

 2,2-di-n-butyl [4H-1,2,2-benzodioxastannin] (Bull Soc Soc., Belg., 97 (1988) 873);

2,2-dimethyl [4-methylidene-1,3,2-benzodioxasiline] (J. Organomet. Chem., 244, C5-C8 (1983)); 2-Methyl-2-vinyl [4-oxo-1,2,2-benzodioxazasiline]. The monomers of the formula III or IIIa are preferably not copolymerized alone but in combination with the monomers of the formulas II or IIa.

According to a further embodiment, the monomers AB of the general formula I are those which are described by the general formula IV,

wherein

 M is a metal or semimetal, preferably B, Al, Si, Ti, Zr, Hf, Ge, Sn, Pb, V,

 As, Sb or Bi, particularly preferably B, Al, Si, Ti, Zr or Sn, very particularly preferably Al, Si, Ti or Zr, in particular Si;

 Ar, Ar 'are the same or different and are each an aromatic or heteroaromatic ring which optionally has 1 or 2 substituents which are listed under

Halogen, CN, Ci-C6-alkyl, Ci-C6-alkoxy and phenyl are selected;

R ^a , R ^b , R ^{a '} , R ^{b' are} independently selected from hydrogen and methyl or

R ^a and R ^b and / or R ^{a '} and R ^b' each together represent an oxygen atom; q corresponding to the valence of M is 0, 1 or 2;

X, Y may be the same or different and represent O, S, NH or a chemical bond; and

R ^{1 '} , R ^{2' may be the} same or different and each is C ¹ -C 6 -alkyl, C 3 -C 6 -cycloalkyl, a polyether-containing radical containing monomer units selected from the group consisting of ethylene oxide and propylene oxide, and aryl or a radical Ar "-C (R ^a" , R ^{b "} ) - in which Ar" has the meanings given for Ar and R ^{a "} ,

R ^{b "have} the meanings given for R ^a , R ^b or R ^{1 '} , R ^2' together with X and Y represent a radical of the formula A as defined above.

In a preferred embodiment of the process according to the invention, the monomer AB is not copolymerized alone but in combination with at least one monomer A1 B1, wherein the monomer AB is at least a first cationically polymerizable monomer unit A, which is a metal or semimetal M and at least one of M covalently via a C atom-bonded radical selected from the group Ci-C2o hydrocarbon radical and polyether-containing radical having.

In a preferred embodiment of the present invention, the method according to the invention for producing a composite material is characterized in that it is in the polymerization of at least one monomer AB to a copolymerization of at least one monomer AB, the

 at least one first cationically polymerizable monomer unit A, which is a metal or metalloid M and at least one M bonded to M, bonded via a carbon atom selected from the group Ci-C2o-hydrocarbon radical, preferably Ci-C4-alkyl, especially methyl, and polyether -containing radical, in particular a polyether-containing radical containing monomer units selected from the group consisting of ethylene oxide and propylene oxide, preferably ethylene oxide, and

 at least one second cationically polymerisable organic monomer unit B, which is connected via one or more covalent chemical bonds to the polymerisable unit A,

with at least one monomer A1 B1, the

 at least one first cationically polymerizable monomer unit A1, which has a metal or semimetal M, and

at least one second cationically polymerizable organic monomer unit B1 which is connected to the polymerizable monomer unit A1 via one or more covalent chemical bonds,

wherein the copolymerization under cationic polymerization conditions, under which polymerize both the polymerizable monomer units A and A1 and the polymerizable monomer units B and B1 with breaking of the bond between A and B and breaking the bond between A1 and B1.

In a preferred embodiment, the copolymerization of the monomers AB with the monomers A1 B1 is characterized in that M in the monomers AB and in the monomers A1 B1 independently of one another represents Si, Al, Ti or Zr, in particular Si, and the cationically polymerizable organic Monomer units B and B1 in the corresponding monomers AB and A1 B1 are each covalently bonded to M via one or more oxygen atoms.

In a further preferred embodiment, the copolymerization of the monomers AB with the monomers A1 B1 is characterized in that in the monomer AB the metal or semimetal M is Si and the monomer unit A is two identical or different, in each case via a carbon atom Si has bonded radicals which are selected from the group consisting of C 1 -C 18 -alkyl, vinyl, C 6 -C 10 -aryl, C 7 -C 14 -alkylaryl and polyether-containing radical containing monomer units selected from the group consisting of ethylene oxide and propylene oxide, in particular special ethylene oxide.

The monomer A1 B1 is in principle defined as the monomer AB and can generally also be described by the general formula I. More preferably, the monomer A1 B1 is characterized by the general formulas II or IIa described above. As monomers AB or A1 B1 of the general formula I, preference is given to 2,2'-spiro [4H-1,2,2-benzodioxasiline], 2,2-dimethyl- [4H-1,2,2-benzodioxasiline], 2 2-diphenyl- [41-1-1,2,2-benzodioxasiline], 2,2-dialkyl- [4H-1,2,2-benzodioxasiline], 2-alkyl-2-methyl- [4H-1,3 , 2-benzodioxasilin], 2-methyl-2-vinyl- [4H-1, 3,2-benzodioxasilin] or the compounds mentioned in WO 201/000858 on page 20, lines 7 to 18 in the polymerization step for the preparation of the inventive Composite material used. The processes for preparing various monomers AB or A1 B2 are described in the respective descriptions and experimental parts of the above-mentioned publications WO 2010/1 12581, WO 2010/128144 and WO 201 1/000858 already mentioned.

In the case of a copolymerization of the monomers AB and A1 B1, the molar ratio of the two monomers can be varied within a wide range. Usually, the molar ratio of the monomers AB and A1 B1 to one another is in the range from 5:95 to 9: 1, frequently in the range from 1: 9 to 4: 1 or 1: 4 to 2: 1, in particular in the range from 1: 2 to 6: 4. In particular, in the cases where AB is a monomer containing a polyether-containing radical of AB are used at most 50 wt .-% based on the total weight of the monomers used and at the same time at least 50 wt .-% of a Monomers A1 B1 of the general formula II or IIa used. It has been found that the polymerization of at least one monomer AB or the copolymerization of at least one monomer AB with at least one monomer A1 B1 can advantageously be carried out in the presence of a polyether, whereby the component (C) contained in the composite material is then added to the polyether used in the process equivalent. In this case, the monomer AB does not have to contain a polyether-containing radical. The polyethers which can be used as component (C) and their preferred embodiments have already been explained in connection with the description of component (C) of the composite material according to the invention.

In a further embodiment of the present invention, the process according to the invention for producing a composite material is characterized in that component (C) is a polyether selected from the group comprising polyethylene glycols, polypropylene glycols and copolymers of ethylene oxide and propylene oxide.

In a further embodiment of the present invention, the inventive method for producing a composite material is characterized in that the polymerization in the presence of another component (E), which is at least one inorganic (semi-) metal oxide in the form of particles is performed. Examples of such particles have already been mentioned above in connection with the description of component (E) of the composite material according to the invention.

The polymerization conditions are selected in the process according to the invention such that in the copolymerization of the monomers AB and A1 B1 the monomer units which carry the inorganic form nic or (semi-) organometallic phase (a), and polymerize monomer units which form the organic polymer phase (b), ie the cationically polymerizable organic moiety synchronously. The term "synchronous" does not necessarily mean that the polymerization of the first and second monomer units proceeds at the same rate. Rather, "synchronous" means that the polymerization of the first and second monomer units are kinetically coupled and triggered by the same polymerization conditions.

In the case of the monomers AB and A1 B1, a synchronous polymerization is ensured if the copolymerization is carried out under cationic polymerization conditions. The copolymerization of the monomers AB and A1 B1, in particular the copolymerization of the monomers of the previously defined general formulas III or IIIa with monomers of the general formulas II or IIa, is carried out in particular under protic catalysis or in the presence of aprotic Lewis acids. Preferred catalysts here are Bronsted acids, for example organic carboxylic acids such as. Trifluoroacetic acid, trichloroacetic acid, formic acid, chloroacetic acid, dichloroacetic acid, hydroxyacetic acid (glycolic acid), lactic acid, cyanoacetic acid, 2-chloropropanoic acid, 2,3-bishydroxypropanoic acid, malic acid, tartaric acid, mandelic acid, benzoic acid or o-hydroxybenzoic acid, as well as organic sulfonic acids such as methanesulfonic acid, trifluoromethanesulfonic acid or toluenesulfonic acid. Also suitable are inorganic Bronsted acids such as HCl, H2SO4 or HCIO4. As the Lewis acid, for example, BF3, BC, SnCU, TiCU, or AICI3 can be used. The use of complexed or dissolved in ionic liquids Lewis acids is also possible. The acid is usually used in an amount of 0.1 to 10 wt .-%, preferably 0.5 to 5 wt .-%, based on the total weight of the monomers.

Preferred catalysts are organic carboxylic acids, in particular organic carboxylic acids having a pKa value (25 ° C) in the range of 0 to 5, especially 1 to 4, z. Trifluoroacetic acid, trichloroacetic acid, formic acid, chloroacetic acid, dichloroacetic acid, hydroxyacetic acid (glycolic acid), lactic acid, cyanoacetic acid, 2-chloropropanoic acid, 2,3-bishydroxypropanoic acid, malic acid, tartaric acid or o-hydroxybenzoic acid.

The polymerization or copolymerization carried out under cationic conditions in the presence of the main body of nonwoven fabric (A), the polyether or the polyether-containing radical (C), optionally the lithium salt (D) and optionally the inorganic (semi-) metal oxide in the form of Particles (E) performed.

In principle, the polymerization can be carried out in bulk or preferably at least partially in an inert solvent or diluent. Suitable solvents or diluents are organic solvents, for example halogenated hydrocarbons such as dichloromethane, trichloromethane, dichloroethene, chlorobutane or chlorobenzene, aromatic hydrocarbons such as toluene, xylenes, cumene or tert-butylbenzene, aliphatic and cycloaliphatic hydrocarbons such as cyclohexane or hexane, cyclic or alicyclic Ethers such as tetrahydrofuran, dioxane, diethyl ether, methyl tert-butyl ether, ethyl tert-butyl ether, diisopropyl ether and mixtures of the abovementioned organic solvents. Preference is given to those organic solvents in which the monomers AB and A1B1 are sufficiently soluble under polymerization conditions (solubility at 25 ° C. at least 10% by weight). These include in particular aromatic hydrocarbons, cyclic and alicyclic ethers and mixtures of these solvents.

Preferably, the polymerization of the monomer AB or the copolymerization of the monomers AB and A1 B1 is carried out in the substantial absence of water, i. H. the concentration of water at the beginning of the polymerization is less than 0.1% by weight. Accordingly, as monomers AB and A1 B1 or as monomers of the formula I those monomers are preferred which do not split off any water under polymerization conditions. These include in particular the monomers of the formulas II, IIa, III and IIIa. The polymerization can in principle be carried out in a wide temperature range, preferably in the range from 0 to 200 ° C., in particular in the range from 20 to 120 ° C.

In a further embodiment of the present invention, the inventive method for producing a composite material is characterized in that the polymerization is carried out at a temperature between 0 and 200 ° C.

The process according to the invention for producing a composite material is preferably carried out in such a way that the composite material which forms during the polymerization is produced directly in the form of a thin layer.

According to a first embodiment, first a base body of nonwoven fabric with the starting compounds of the other components, that is in particular the monomer AB or the monomers AB and A1 B1 and optionally the polyether as component (C), the conductive salt (D) and / or the loaded inorganic (half) metal oxide particles (E) and in a second process step, the monomer AB or the monomers AB and A1 B1 to the nanocomposite material (B) is reacted in which the components (C), (D) and (E ) are chemically embedded unchanged.

Methods for producing filled nonwoven fabrics are known in principle to the person skilled in the art. Thus, for example, a nonwoven fabric can be loaded or filled partially or completely with the necessary starting components by impregnation, brushing, doctor blade methods, calendering methods or combinations thereof. A nonwoven fabric filled in this way is then subjected to conditions under which the polymerization or copolymerization takes place.

The resulting composite materials are particularly suitable as a separator or as part of a separator in electrochemical cells. Under an electrochemical cell or battery are understood in the context of this invention, batteries, capacitors and batteries (secondary batteries) of any kind, especially alkali metal cells or batteries such. As lithium, lithium ion, lithium-sulfur and alkaline earth batteries and accumulators and in the form of high-energy or high-performance systems, as well as electrolytic capacitors and double-layer capacitors, which are called Supercaps, Goldcaps, BoostCaps or Ultracaps are known.

Another object of the present invention is a use of the above-described composite material according to the invention as a separator or as part of a separator in electrochemical cells, fuel cells or supercapacitors.

Likewise provided by the present invention is a separator for an electrochemical cell, in particular consisting of the above-described composite material according to the invention.

Likewise provided by the present invention is a fuel cell, a battery or a capacitor, comprising at least one separator according to the invention, as described above. Preferably, the composite materials according to the invention are suitable for electrochemical cells which are based on the transfer of alkali metal ions, in particular for lithium metal, lithium sulfur and lithium ion cells or batteries and especially for lithium ion secondary cells or Secondary batteries. Particularly suitable are the composite materials according to the invention for electrochemical cells from the group of lithium-sulfur cells.

The subject of the present invention is an electrochemical cell containing

at least one separator according to the invention, as described above, and (X) at least one cathode, and

(Y) at least one anode.

The electrochemical cell according to the invention, in particular a rechargeable electrochemical cell, is preferably one in which charge transport within the cell is decisively effected by lithium cations.

Particularly preferred electrochemical cells are therefore lithium-ion cells, in particular lithium-ion secondary cells, which have at least one separator layer, which is composed of the composite materials according to the invention. Such cells generally have at least one anode suitable for lithium-ion cells, a cathode suitable for lithium-ion cells, an electrolyte and at least one separator layer arranged between the anode and the cathode and comprising composite materials according to the invention. With regard to suitable cathode materials, suitable anode materials, suitable electrolytes and possible arrangements, reference is made to the relevant prior art, eg. B. on appropriate monographs and reference works: z. Wakihara et al. (Publisher): Lithiumion Batteries, 1st edition, Wiley VCH, Weinheim, 1998; David Linden: Handbook of Batteries (McGraw-Hill Handbooks). 3. Edition. Mcgraw-Hill Professional, New York 2008; JO Besenhard: Handbook of Battery Materials. Wiley-VCH, 1998.

Particularly suitable cathodes are cathodes in which the cathode material comprises a lithium transition metal oxide, eg. As lithium cobalt oxide, lithium nickel oxide, lithium cobalt nickel oxide, lithium manganese oxide (spinel), lithium nickel cobalt alumina, lithium nickel-cobalt manganese oxide, or lithium vanadium oxide, a lithium sulfide or lithium polysulfide such as L12S, L12S8, L12S6, L12S4, or L12S3, or a lithium transition metal phosphate such as lithium iron phosphate as the electroactive component. Also suitable are cathode materials containing iodine, oxygen, sulfur and the like as the electroactive component. However, if it is desired to use as cathode materials those containing polymers containing sulfur or polysulfide bridges, care must be taken that the anode is charged with Li ⁰ before such an electrochemical cell can be discharged and recharged. In addition to the separator according to the invention and the cathode (X), the electrochemical cell according to the invention also contains at least one anode (Y).

In one embodiment of the present invention, anode (Y) may be selected from anodes of carbon, anodes containing Sn or Si, and anodes containing lithium titanate of formula Li 4 + x Ti ₅ O 2 with x equal to a numerical value of> 0 to 3 , For example, carbon anodes may be selected from hard carbon, soft carbon, graphene, graphite, and especially graphite, intercalated graphite, and mixtures of two or more of the aforementioned carbons. Anodes containing Sn or Si can be selected, for example, from nanoparticulate Si or Sn powder, Si or Sn fibers, carbon-Si or carbon-Sn composite materials and Si-metal or Sn metal alloys.

In a further embodiment of the present invention, the electrochemical cell according to the invention is characterized in that anode (Y) is selected from anodes of carbon, anodes containing Sn or Si, and anodes, the lithium titanate of formula Li4 + xTi ₅ 0i2 with x being equal a numerical value of> 0 to 3.

In addition to the electroactive ingredients, the anodes and cathodes may also contain other ingredients, for example

 electrically conductive or electroactive components such as carbon black, graphite, carbon fibers, nanocarbon fibers, nanocarbon tubes or electrically conductive polymers;

Binder such as polyethylene oxide (PEO), cellulose, carboxymethylcellulose (CMC), polyethylene, polypropylene, polytetrafluoroethylene, polyacrylonitrile-methyl methacrylate, polytetrafluoroethylene rafluoroethylene, styrene-butadiene copolymers, tetrafluoroethylene-hexafluoropropylene copolymers, polyvinylidene difluoride (PVdF), polyvinylidene difluoride-hexafluoropropylene copolymers (PVdF-HFP), tetrafluoroethylene-hexafluoropropylene copolymers, tetrafluoroethylene, perfluoroalkyl-vinyl ether copolymers, vinylidene fluoride-hexafluoropropylene Copolymers, ethylene-tetrafluoroethylene copolymers, vinylidene fluoride-chlorotrifluoroethylene

Copolymers, ethylene-chlorofluoroethylene copolymers, ethylene-acrylic acid copolymers (with and without inclusion of sodium ions), ethylene-methacrylic acid copolymers (with and without inclusion of sodium ions), ethylene-methacrylic acid ester copolymers (with and without inclusion of sodium ions), Polyimides and polyisobutene.

The two electrodes, d. H. the anode and the cathode are connected together using a separator according to the invention and a liquid or else solid electrolyte in a manner known per se. For this purpose, for example, a composite material according to the invention on one of the two electrodes, which is provided with a current conductor, (anode or cathode) apply, for. B. laminate, soak with the electrolyte, and then apply the oppositely charged electrode, which is provided with a current collector, wrap the resulting sandwich if necessary, and bring in a battery case. It is also possible to proceed by sandwiching the layered or film-shaped constituents current collector, cathode, separator, anode, current conductor, optionally winding the sandwich, wrapping it in a battery housing, and then impregnating the arrangement with the electrolyte.

In particular, non-aqueous solutions (water content of generally <20 ppm) of lithium salts and molten Li salts are suitable as liquid electrolytes, eg. B. Solutions of lithium hexafluorophosphate, lithium perchlorate, Lithiumhexafluoroarsenat, lithium trifluoromethyl sulfonate, lithium (bis (trifluoromethylsulfonyl) imide) or lithium tetrafluoroborate, in particular lithium hexafluorophosphate or lithium tetrafluoroborate, in suitable aprotic solvents such as ethylene carbonate, propylene carbonate and mixtures thereof with one or more of the following solvents: Dimethyl carbonate, diethyl carbonate, dimethoxyethane, methyl propionate, ethyl propionate, butyrolactone, acetonitrile, ethyl acetate, methyl acetate, toluene and xylene, especially in a mixture of ethylene carbonate and diethyl carbonate.

Between the electrodes, a separator layer according to the invention is arranged, which is soaked in the rule with the liquid, in particular a liquid organic electrolyte.

Another object of the present invention is the use of electrochemical cells according to the invention in lithium-ion batteries. Another object of the present invention are lithium-ion batteries, containing at least one electrochemical cell according to the invention. Inventive electrochemical cells can be combined with one another in lithium-ion batteries according to the invention, for example in series connection or in parallel connection. Series connection is preferred. Another object of the present invention is the use of electrochemical cells according to the invention as described above in automobiles, electric motor-powered two-wheelers, aircraft, ships or stationary energy storage. Another object of the present invention is therefore also the use of lithium-ion batteries according to the invention in devices, in particular in mobile devices. Examples of mobile devices are vehicles, for example automobiles, two-wheeled vehicles, aircraft or watercraft, such as boats or ships. Other examples of mobile devices are those that you move yourself, such as computers, especially laptops, phones or electrical tools, for example, in the field of construction, in particular drills, cordless screwdrivers or cordless tackers.

The use of lithium ion batteries according to the invention, which contain separator according to the invention, in devices offers the advantage of a longer running time before recharging, a lower capacity loss with longer term and a reduced risk of self-discharge and destruction of the cell caused by short circuit. If one wanted to realize an equal running time with electrochemical cells with a lower energy density, then one would have to accept a higher weight for electrochemical cells. The monomers AB which can be used in the process according to the invention for producing the composite material according to the invention, which contain at least one polyether-containing radical, are new. Such special monomers AB can be prepared by known methods which can also be used for the preparation of the monomers AB known from the literature, the introduction of the polyether-containing radical being carried out by methods which are known to a person skilled in the art, in particular to an organic chemist.

Another object of the present invention is also a monomer AB, the

 at least one first cationically polymerizable monomer unit A, which has a metal or semimetal M, and

at least one second cationically polymerizable organic monomer unit B, which is connected via one or more covalent chemical bonds to the metal or metalloid M of the polymerizable monomer unit A,

characterized in that the monomer AB contains at least one polyether-containing radical.

Preference is given to a monomer AB according to the invention in which M is Si, the cationically polymerizable organic monomer unit B is covalently bonded to M via two oxygen atoms and the monomer unit A has two identical or different radicals which are bonded to Si via a carbon atom are from the group consisting of Ci-cis-alkyl, vinyl, C6-C10 aryl, C7-C14 alkylaryl and polyether-containing radical containing monomer units selected from the group consisting of ethylene oxide and propylene oxide, wherein at least one of the two via a C-atom bonded to Si is a polyether-containing radical. In one embodiment of the present invention, monomer AB is selected from compounds of general formula IIIa '

wherein

R may be the same or different and are selected from halogen, CN, C 1 -C 6 -alkyl, C 1 -C 6 -alkoxy and phenyl,

m is 0, 1 or 2, in particular 0,

R ^a , R ^b independently of one another represent hydrogen or methyl, in particular hydrogen,

Rr is C 1 -C 6 -alkyl, C 3 -C 6 -cycloalkyl, a polyether-containing radical bonded via a carbon atom, containing monomer units selected from the group consisting of ethylene oxide and propylene oxide, and aryl or a radical Ar'-C (R ^{a ').} , R ^{b '} ) - are, in which Ar' has the meanings given for Ar and R ^{a '} , R ^{b' have} the meanings given for R ^a , R ^b , and

R ^{2 'is} a bonded via a carbon atom polyether-containing radical containing monomer units selected from the group consisting of ethylene oxide and propylene oxide, in particular ethylene oxide.

In formula IIIa 'R is preferably C 1 -C 6 -alkyl, in particular methyl.

In a particularly preferred embodiment of the present invention, preferred monomer AB, as described above, is characterized in that the polyether-containing radical bonded to Si via a C atom is a radical of the formula C-PEG, wherein

o is 0 or an integer from 1 to 18, preferably 1 to 6, in particular 1, and n is an integer from 1 to 100, preferably 5 to 50, in particular 8 to 30. The invention is illustrated by the following, but not limiting examples of the invention.

Percentages are by weight in each case, unless expressly stated otherwise.

I. Preparation of monomers containing a polyether-containing radical

1.1 Synthesis of 2-methyl-2- (3- (polyethyleneglycol-500 ^ -methylether) -propanediyl-1) - [4H-1,2,2-benzodioxasiline]

with n = 1 1 1.1. a Hydrosilylation of polyethylene glycol a-allyl ether ^ -methyl ether with dichloromethylsilane

with n = 1 1 To remove water, 250 g (0.46 mol) of polyethylene glycol a-allyl ether .alpha.-methyl ether (commercially available as Uniox MA 500 of the NOF Cooperation; n = 11, M = 540 g) were added under a nitrogen blanket / mol, residual water content: 0.26 wt .-% determined by Karl Fischer titration) dissolved in 200 ml of anhydrous toluene and treated with 10 g (0.09 mol) of trimethylchlorosilane (M = 108.64 g / mol). The mixture was heated to 120 ° C for 3 hours. After cooling to 20 ° C, toluene and other volatile compounds such as hexamethyldisiloxane ((CH ₃ ) ₃ SiOSi (CH ₃ ) 3) were removed at 80 ° C / 5 mbar.

0.8 μΙ of a solution of 205 mg of hexachloroplatinum (IV) acid hydrate (F PtCle ^* 6H 2 O) in 0.5 ml of isopropanol was added to the dried allyl ether. 58.6 g (0.51 mol) of dichloromethylsilane (C SiH CHs), M = 15 g / mol) were added dropwise at 50 ° C. within 1 hour, and the reaction mixture was then further at 80 ° for 2 hours C stirred. There were obtained 301 g of product (M = 655 g / mol) in quantitative yield. H-NMR (CDCIs, 500 MHz): δ = 0.7 ppm (3H, CH 3 SCl 2 R), 1, 1 -1, 2 ppm (2 H, m,

RC SiCHZCHZCHZOR), 1, 6 - 1, 7 ppm (2 H, m, RC SiCHZCHZCHzOR), 3.3 ppm (3H, s, -OCH ₃ ), 3.4 - 3.5 ppm (2H, dd, RC SiCH 2 CHZORO), 3.5-3.7 (44H, m, R 1 CH 2 CH 3 nOCHs). 1.1. b Synthesis of 2-methyl-2- (3- (polyethyleneglycol-500 ^ -methylether -) -propanediyl-1) - [4H-1,2,2-benzodioxasiline]

 with n = 1 1

58.3 g (0.45 mol) of diisopropylethylamine (Hünig base, M = 129.24 g / mol), which had been previously distilled over calcium hydride, together with 28 g (0.22 mol) of 2-hydroxybenzyl alcohol ( Saligenin, M = 124.1 g / mol) in 150 ml of anhydrous toluene under a nitrogen atmosphere. 147 g (0.23 mol) of the example 1.1. a obtained dichlorosilane (n = 1 1, M = 655 g / mol) were dissolved in 150 ml of anhydrous toluene and added dropwise within 75 minutes to the first mixture, wherein the temperature did not exceed 40 ° C. Subsequently, the reaction mixture was heated to 80 ° C and stirred at this temperature for one hour. After cooling to 20 ° C, the hydrochloride of diisopropylamine was filtered off and the solvent removed at 80 ° C and 5 mbar. 140 g of the desired product (87%, M = 707 g / mol) were obtained. H-NMR (CD2Cl2, 500 MHz): δ = 0.15 ppm (3H, CH3S1-R), 0.55-0.65 (2H, m,

R3S1CH2CH2CH2OR), 1, 4-1, 5 ppm (2 H, m, R3S1CH2CH2CH2OR), 3.15 ppm (3H, s, _-OCH3), 3.2 - 3.3 ppm (2H, dd, R3S1CH2CH2CH2OR), 3, 3 - 3.5 (44H, m, R (OCH ₂ CH ₂ ) ₂ OCH 3), 4.75 ppm (2

H, s, Ar-CH ₂ -OR), 6.7-7.1 ppm (4H, m, Ar-H).

I.2 Synthesis of 2-methyl-2- (3- (polyethyleneglycol-1000) -methylether -) - propanediyl-1) - [4H-

1, 3,2-benzodioxasiline]

with n = 22 l.2.a Allylation of polyethylene glycol methyl ether with allyl chloride

1. NaH

 2. allyl chloride

with n = 22

Under a nitrogen atmosphere, 300 g (0.3 mol) of polyethylene glycol methyl ether (commercially available as Pluriol 1020 E from BASF SE, M = 1000 g / mol) were dissolved in 350 ml of anhydrous tetrahydrofuran. To this was added in small portions over a period of 45 minutes a total of 13.2 g (0.33 mol) of sodium hydride (M = 24.0 g / mol) as a 60% by weight dispersion in oil. To complete the reaction, the reaction mixture was then stirred for 75 minutes at 60 ° C. Solvent THF was removed on a rotary evaporator and dichloromethane was added to the residue. The organic phase was washed twice with water and dichloromethane removed by distillation. 247 g of the allylated polyethylene glycol (78%, M = 1040 g / mol) were obtained. H-NMR (CDCIs, 500 MHz): δ = 3.3 ppm (3H, s, -OCH _3), 3.4 to 3.6 (88H, m, _CH2 = CH- _CH2 (OCH2CH2) 220CH ₃ ), 3.9 ppm (2H, d, m (2H, d, CH 2 = CH-CH ₂ (OCH ₂ CH 2) 220CH3), 5.9 pp l.2.b Hydrosilylation of polyethylene glycol a-allyl ether, methyl ether with dichloromethylsilane

 with n = 22

Under a nitrogen atmosphere, 242 g (0.23 mol) of the obtained in Example l.2.a polyethylenglycol a-allyl ether ^ -methylether (n = 22, M = 1040 g / mol, residual water content: 0.26 wt. % by Karl Fischer titration) in 200 ml of dry toluene together with 6 g (0.06 mol) of trimethylchlorosilane (M = 108.64 g / mol) and heated to 120 ° C for 3 hours. After cooling to 20 ° C., toluene and further volatile compounds such as hexamethyldisiloxane ((CH ₃ ) 3SiOSi (CH ₃ ) 3) were removed at 80 ° C./4 mbar.

0.5 μΙ of a solution of 205 mg of hexachloroplatinum (IV) acid hydrate (H2PtCl6 ^* 6H2O) in 0.5 ml of isopropanol was added to the dried allyl ether. 29.7 g (0.26 mol) of dichloromethylsilane (CI ₂ SiH (CH ₃ ), M = 15 g / mol) were added dropwise at 50 ° C. within 1 hour, and the reaction mixture was then continued for 2 hours stirred at 80 ° C. There were obtained 272 g of product (M = 1 155 g / mol) in quantitative yield. H-NMR (CDCl3, 500 MHz): δ = 0.7 ppm (3H, CH3S1Cl2-R), 1, 1-1, 2 ppm (2H, m, RC SiCH2CH2CH2 OR), 1.6-7.7 ppm (2 H, m, SiCHzCHzCHzOR RC), 3.3 ppm (3H, s, -OCH _3), 3.4 to 3.5 ppm (2H, dd, RC SiCHzCHzCHzOR), 3.5 to 3.7 (88H , m, R (OCH ₂ CH 2) ₂₂ OCH ₃ ). I.2.C Synthesis of 2-methyl-2- (3- (polyethyleneglycol-1000-methylmethyl) -propanediyl-1) - [4H-1,2,2-benzodioxasiline]

 with n = 22

60.4 g (0.47 mol) of diisopropylethylamine (Hünig base, M = 129.24 g / mol), which had been previously distilled over calcium hydride, together with 29 g (0.224 mol) of 2-hydroxybenzyl alcohol (saligenin, M = 124.1 g / mol) in 160 ml of anhydrous toluene under a nitrogen atmosphere. 270.9 g (0.234 mol) of the dichlorosilane obtained in Example 1.2.b (n = 22, M = 1155 g / mol) were dissolved in 100 ml of anhydrous toluene and added dropwise to the first mixture within 30 minutes, the temperature did not exceed 40 ° C. Subsequently, the reaction mixture was heated to 80 ° C and stirred at this temperature for one hour. After cooling to 20 ° C, the hydrochloride of diisopropylamine was filtered off and the solvent removed at 80 ° C and 5 mbar. There were obtained 231 g of the desired product (82%, M = 1207 g / mol). H NMR (CD2Cl2, 500 MHz): δ = 0.05 ppm (3H, CH3S1-R), 0.55-0.65 (2H, m,

R3S1CH2CH2CH2OR), 1, 3 -1, 4 ppm (2 H, m, R3S1CH2CH2CH2OR), 3.05 ppm (3H, s, _-OCH3), 3.1-3.2 ppm (2H, dd, R3S1CH2CH2CH2OR) 3.3 to 3.5 (88H, m, R (OCH2CH2) ₂₂ OCH _3), 4.6 ppm (2 H, s, Ar-CH ₂ -O), 6.5 to 6.9 ppm (4H, m, Ar-H).

II. Production of Composite Materials According to the Invention

11.1 General procedure for the production of composite materials according to the invention

Polyethylene glycol methyl ether having a molecular weight of about 500 g / mol (commercially available as Pluriol A 500E ^® from BASF SE) and Lithiumtrifluorsulfonsäureimid (LiTFSI) were homo genie carbonized at 85 ° C. To this was added 266 mg (1.6 mmol) of 2,2-dimethyl- [4H-1,2,3-benzodioxasiline] (prepared according to Tetrahedron Lett. 24 (1983) 1273). The mixture was then transferred to 436 mg (1.6 mmol) of molten 2,2 '-spirobi [4H-1,2,2-benzodioxasiline] (prepared as described in WO 201/000858, page 28, lines 9-19 described). To initiate the polymerization, an initiator solution consisting of 5.45 mg of tin tetrachloride (SnCU) in 56 mg of d-chloroform (CDC) was added.

The reactive monomer mixture was polymerized for 10 minutes at 95 ° C. and fractionated onto a metal plate with PET nonwoven (commercially available as fleece "PES20" from APODIS Filtertechnik OHG, 8 g / m.sup.2, thickness ⁾ , prewarmed to 95 ° C. in the desiccator 20 μηι, 5 x 3.5 cm surface), so that sheet-like composite materials were obtained with layer thicknesses of 30 to 90 μηη then polymerized in a drying oven at 95 ° C for 3 h under a stream of nitrogen and then annealed at 195 ° C for After 30 minutes under vacuum.

Electrolyte: 1 M LiTFSI in dioxolane and dimethyl ether (1: 1 vol / vol)

Claims

claims Composite material comprising components (A) at least one base body made of nonwoven fabric;  (B) at least one nanocomposite material containing  (a) at least one inorganic or (semi-) organometallic phase (a) containing at least one metal or metalloid M; and  (b) at least one organic polymer phase (b), wherein the organic polymer phase (b) and the inorganic or (semi-) metal organic phase (a) form substantially co-continuous phase domains, wherein the mean distance between two adjacent domains of identical phases maximum 100 nm;  (C) at least one polyether or at least one polyether-containing radical, wherein the polyether-containing radical is covalently bound to the (semi-) organometallic phase (a) or organic polymer phase (b); and  (D) optionally at least one lithium salt. A composite material according to claim 1, wherein the nonwoven fabric main body (A) is at least partially penetrated by the nanocomposite material (B). A composite material according to claim 1 or 2, wherein the base body of nonwoven fabric (A) is made of organic polymers selected from the group of polymers consisting of polyolefins, polymers of heteroatom-containing vinyl monomers, polyesters, polyamides, polyimides, polyetheretherketones, Polysulfone and polyoxymethylene are selected. A composite material according to any one of claims 1 to 3, wherein the metal or metalloid M of phase (a) is selected from B, Al, Si, Ti, Zr, Hf, Ge, Sn, Pb, V, As, Sb, Bi and the like mixtures. A composite material according to any one of claims 1 to 4, wherein the metal or semimetal M comprises at least 90 mol%, based on the total amount of M, of silicon. A composite material according to any one of claims 1 to 5, wherein the lithium salt (D) is selected from the group consisting of lithium hexafluorophosphate, lithium perchlorate, lithium hexafluoroarsenate, lithium trifluoromethylsulfonate, lithium (bis (trifluoromethylsulfonyl) imide) and lithium tetrafluoroborate. A composite material according to any one of claims 1 to 6, wherein the nanocomposite material (B) is a polymerization product of at least one monomer AB which  at least one first cationically polymerizable monomer unit A, which is a Metal or metal M has, and at least one second cationically polymerizable organic monomer unit B, which is connected via one or more covalent chemical bonds to the polymerisable monomer unit A,  wherein the polymerization product is obtained under cationic polymerization conditions under which polymerize both the polymerizable monomer unit A and the polymerizable monomer unit B with breaking of the bond between A and B, and wherein the monomer AB in the presence of the body of nonwoven fabric (A), the polymer lyethers or the polyether-containing radical (C) and optionally the lithium salt (D) is polymerized. A method of making a composite material comprising the components (A) at least one base body made of nonwoven fabric;  (B) at least one nanocomposite material containing  (a) at least one inorganic or (semi-) organometallic phase (a) containing at least one metal or metalloid M; and  (b) at least one organic polymer phase (b);  (C) at least one polyether or at least one polyether-containing radical, wherein the polyether-containing radical is covalently bonded to the (semi-) organometallic phase (a) or organic polymer phase (b); and  (D) optionally a lithium salt; by polymerization of at least one monomer AB, the  at least one first cationically polymerizable monomer unit A, which has a metal or semimetal M, and  at least one second cationically polymerizable organic monomer unit B, which is connected via one or more covalent chemical bonds to the polymerisable monomer unit A,  under cationic polymerization conditions under which polymerize both the polymerizable monomer unit A and the polymerizable monomer unit B with breaking of the bond between A and B, wherein the polymerization in the presence of the base body of nonwoven fabric (A), the polyether or the polyether-containing radical (C ) and optionally the lithium salt (D) is carried out. A method according to claim 8, wherein the metal or metalloid M of the monomer unit A in the monomers AB is selected from B, Al, Si, Ti, Zr, Hf, Ge, Sn, Pb, V, As, Sb, Bi and mixtures thereof. 0. The method of claim 9, wherein the metal or metalloid M of the monomer unit A comprises at least 90 mol%, based on the total amount of M, of silicon. Method according to one of claims 8 to 10, wherein the monomers AB, which have at least one monomer unit A and at least one monomer unit B, are described by the general formula I: R ¹ - Q _/ XR ^{1 '}  (I) ₂ / \ ₂ , R ² - G (YR ² ) _Q wherein  M is a metal or semimetal; R ¹ , R ^{2 may be the} same or different and each represents a radical Ar-C (R ^a , R ^b ) - where Ar is an aromatic or heteroaromatic ring which optionally has 1 or 2 substituents which are halogen, CN, C 1 -C 6 -alkyl, C 1 -C 6 -alkoxy and phenyl are selected and R ^a , R ^b independently of one another represent hydrogen or methyl or together denote an oxygen atom or a methylidene group (= CH 2), or the radicals R ¹ Q and R ² G together represent a radical of the formula Ia where A is an aromatic or heteroaromatic ring fused to the double bond, m is 0, 1 or 2, the radicals R may be identical or different and are halogen, CN, C 1 -C 6 -alkyl, C 1 -C 6 -alkoxy and phenyl are selected and R ^a , R ^{b have} the meanings given above;  G is O, S or NH;  Q is O, S or NH; q corresponding to the valence of M is 0, 1 or 2,  X, Y may be the same or different and each represents O, S, NH or a chemical bond; R ^{1 '} , R ^{2' may be} identical or different and in each case represents C ¹ -C 6 -alkyl, C 3 -C 6 -alkyl, Cycloalkyl, a polyether-containing radical containing monomer units selected from the group consisting of ethylene oxide and propylene oxide, and aryl or a radical Ar'-C (R ^{a '} , R ^b' ) - are, wherein Ar 'has the meanings given for Ar and R ^{a '} , R ^{b' have} the meanings given for R ^a , R ^b or R ^{1 '} , R ^2' together with X and Y is a radical of the formula A as defined above; or, when X is oxygen, the radical R ^{1 'is} a radical of the formula Ib: R-Q #  M '(Ib)  2 \ 2 ' R-G (YR) _q may be where q, R ¹ , R ² , R ^{2 '} , Y, Q and G are as defined above and # is the bond to X. Process according to one of the preceding claims, wherein the polymerization of at least one monomer AB is a copolymerization of at least one monomer AB, the  at least one first cationically polymerizable monomer unit A, which has a metal or metalloid M and at least one radical bonded to M covalently bound via a carbon atom and selected from the group consisting of C 1 -C 20 -hydrocarbon radical and polyether-containing radical;  at least one second cationically polymerizable organic monomer unit B, which is connected via one or more covalent chemical bonds to the polymerisable unit A, with at least one monomer A1 B1, the  at least one first cationically polymerizable monomer unit A1, which has a metal or semimetal M, and  at least one second cationically polymerizable organic monomer unit B1, which is connected via one or more covalent chemical bonds to the polymerizable monomer unit A1, wherein the copolymerization under cationic polymerization conditions under which polymerize both the polymerizable monomer units A and A1 and the polymerizable monomer units B and B1 with breaking of the bond between A and B and breaking the bond between A1 and B1. A process according to claim 12, wherein M in the monomers AB and in the monomers A1 B1 independently of one another represents Si, Al, Ti or Zr and the cationically polymerizable organic monomer units B and B1 in the corresponding monomers AB and A1 B1 in each case via one or more Oxygen atoms are covalently bound to M A process as claimed in claim 12 or 13, wherein in the monomer AB the metal or semimetal M is Si and the monomer unit A has two identical or different radicals, each bonded via a carbon atom to Si, selected from the group consisting of Ci8-alkyl, vinyl, C6-C10 aryl, C7-Ci4-alkylaryl and polyether-containing radical containing monomer units selected from the group consisting of ethylene oxide and propylene oxide. 15. The method according to any one of claims 8 to 14, wherein the component (C) is a polyether selected from the group comprising polyethylene glycols, polypropylene glycols and copolymers of ethylene oxide and propylene oxide. 16. The method according to any one of claims 8 to 15, wherein the polymerization in the presence of another component (E), which is at least one inorganic (semi-) metal oxide in the form of particles, is carried out. 17. The method according to any one of claims 8 to 16, wherein the polymerization is carried out at a temperature between 0 and 200 ° C. 18. Use of the composite material according to any one of claims 1 to 7 as a separator o- as part of a separator in electrochemical cells, fuel cells or supercapacitors. 19. Separator for an electrochemical cell containing composite material according to one of claims 1 to 7. 20. An electrochemical cell, comprising at least one separator according to claim 19 and at least one cathode, and  at least one anode. Electrochemical cell according to claim 20, characterized in that anode (Y) is selected from anodes of carbon, anodes containing Sn or Si, and anodes, the lithium titanate of formula Li4 + xTi ₅ 0i2 with x equal to a number of> 0 to 3, included. Use of electrochemical cells according to claim 20 or 21 in lithium-ion batteries. 23. Lithium-ion battery containing at least one electrochemical cell according to claim 20 or 21. 24. Use of electrochemical cells according to claim 20 or 21 in automobiles, powered by electric motor two-wheelers, aircraft, ships or stationary energy storage. Monomer AB, the  at least one first cationically polymerizable monomer unit A, which has a metal or semimetal M, and  at least one second cationically polymerizable organic monomer unit B, which is connected via one or more covalent chemical bonds with the metal or semimetal M of the polymerizable monomer unit A, characterized in that the monomer AB at least one polyether-containing Contains rest. Monomer AB according to claim 25, wherein M is Si, the cationically polymerizable organic monomer unit B is covalently bonded to M via two oxygen atoms and the monomer unit A has two identical or different, each bonded via a carbon atom to Si radicals selected from the group consisting of C1-C18-alkyl, vinyl, C6-C10 aryl, Cz-Cu-alkylaryl and polyether-containing radical containing monomer units selected from the group consisting of ethylene oxide and propylene oxide, wherein at least one of the two via a carbon atom Si bonded radicals is a polyether-containing radical. Monomer AB selected from compounds of general formula IIIa ' wherein  R may be the same or different and is halogen, CN, Ci-C6-alkyl, C1- C6 alkoxy and phenyl are selected, m is 0, 1 or 2, R ^a , R ^b independently of one another represent hydrogen or methyl, R ^{1 'is} Ci-C6-alkyl, C3-C6-cycloalkyl, a bonded via a carbon atom polyether-containing radical containing monomer units selected from the group consisting of ethylene oxide and propylene oxide, and aryl or a radical Ar'-C (R ^{a '} , R ^b' ) - are, in which Ar 'has the meanings given for Ar, and R ^{a '} , R ^{b' have} the meanings given for R ^a , R ^b , and R ^{2 '} for a bonded via a carbon atom containing polyether-containing radical Monomer units selected from the group consisting of ethylene oxide and propylene oxide. Monomer AB according to Claim 26 or 27, in which the polyether-containing radical bonded to Si via a C atom is a radical of the formula C-PEG, wherein o stands for 0 or an integer from 1 to 18, and n is an integer from 1 to 100.