WO2015086461A1

WO2015086461A1 - Nitrogen-containing composite materials, production and use thereof

Info

Publication number: WO2015086461A1
Application number: PCT/EP2014/076744
Authority: WO
Inventors: Arno Lange; Gerhard Cox; Hannes Wolf; Szilard Csihony; Stefan Spange; Lysann KASSNER; Anja KNOBLAUCH
Original assignee: Basf Se
Priority date: 2013-12-13
Filing date: 2014-12-05
Publication date: 2015-06-18

Abstract

The invention relates to composite materials containing a) at least one nitrogen and (semi) metal-containing phase (a) and b) at least one organic polymer phase (b). The invention also relates to a method for producing said type of composite materials, to the use of said type of composite materials for producing electroactive materials and to electrochemical cells containing the electroactive materials.

Description

Description: The present invention relates to composite materials comprising a) at least one nitrogen and (semi-) metal-containing phase (a), and b) at least one organic polymer phase (b). Furthermore, the invention also relates to methods for producing such composite materials, the use of such composite materials for the production of electroactive materials and electrochemical cells containing the electroactive materials.

Secondary batteries, accumulators, rechargeable batteries or "rechargeable batteries" are only a few embodiments for storing and using electrical energy after production because of their significantly better power density, they have recently deviated from the water-based secondary batteries and developed such batteries. where charge transport in the electrical cell is accomplished by lithium ions.

In the lithium ion batteries currently being manufactured, the cathode usually contains a lithium-transition metal compound such as UC0O2 or LiFeP0 _4, and the anode usually contains graphite in which Li ^{0 is} intercalated during the charging process. To increase the capacity of the graphite-based anode, as shown in Angew. Chem. 2008, 120, 2972-2989, developed anodes containing lithium-metal alloys, for example lithium-tin or lithium-silicon alloys. Silicon and tin can absorb large amounts of lithium to form the alloys Li ₄ , ₄ Sn and Li ₄ , ₄ Si and show significantly higher capacities than a graphite electrode with intercalated Li ⁰ . In Angew. Chem. 2008, 120, 2972-2989 describes that the consequence of such a large accumulation of lithium, however, is a large volume contraction and expansion associated with electrochemical alloy formation. These changes quickly lead to the destruction of the electrode (cracking and eventually pulverization), so that the lifetimes extend only a few cycles of charge and discharge. However, the use of metal particles in the nanometer size range is said to reduce undesirable cracking within the electrode. Various processes have been used in the preparation of nanostructured metals that can form lithium alloys, including sol-gel processes, ball mills, and electrolytic deposition. Among these, electrodeposition is the most versatile because it allows easy control of electrode morphology by varying synthesis conditions such as current density and deposition time.

A further possibility for the preparation of nanostructured metals and metal compounds was achieved by the so-called twin polymerization (see, for example, Spange et al., Angew Chem. Int. Ed., 46 (2007) 628-632, WO 2009/083083, WO 2009/133086, WO 2010/1 12581 and WO2010 / 128144) in which composite materials containing nanostructured metals or metal compounds are formed. The twin polymerization provides composite materials typically having at least one oxide phase and at least one organic polymer phase wherein the phase domains have a co-continuous configuration and dimensions in the range of a few nanometers (spacing between adjacent identical phases). It is believed that the particular phasing and short spacing of adjacent phases is a consequence of the kinetic coupling of the polymerization of the arylmethylene units in the twin monomers, on the one hand, and the formation of the silica, on the other hand. As a result, the phase constituents form more or less synchronously, and phase separation into the inorganic phase and the organic phase takes place already during the polymerization of the twin monomers.

Preferred twin monomers are spiro-cyclic compounds, as described in WO 2009/083083. In these spirocyclic compounds, two 1-oxy-2- (oxymethyl) aryl groups are linked together via their oxygen atoms with a metal or semimetal atom to form a spirocyclic structure. An example of such a spiro-cyclic compound is 2,2'-spiro [4H-1,2,2-benzodioxasiline].

Likewise, similar structures from the reaction of tetraarylsiloxanes and formaldehyde (equivalents) are described in WO2012 / 098149.

DE 1816241 discloses the preparation of soluble metal- or semimetal-containing phenol-formaldehyde resins in which either certain metal or semimetal phenolates are reacted with substoichiometric amounts of formaldehyde or novolaks, ie phenol-formaldehyde condensates with selected inorganic metal or semimetal compounds - be implemented. The preparation of composite materials with a phase structure whose phase domains have dimensions in the nanometer range is not described.

Thus, methods are available with which by suitable choice of the educts Si-containing domains can be generated in an organic matrix. This is of commercial interest since elemental silicon is an essential element in photovoltaic or energy storage applications.

A disadvantage of all methods is that first oxygen-containing silicon domains are produced, which are difficult to convert into the desired elemental silicon or silicon suboxide in hybrid systems. At temperatures in the range of 1600 ° -1800 ° C, elemental Si can be produced from silica and carbon (S1O2 + 2C -> Si + 2 CO), but here one must rely on the exact adherence to the stoichiometry. Therefore, this method is unsuitable for C / Si composite materials since additional carbon forms SiC under these conditions, the hybrid structures are dissolved therewith, and / or elemental Si is converted to SiC. The object was thus to find new composite materials and processes for their preparation which reduce or eliminate the disadvantages described above. Furthermore, improved electroactive materials should be made available from the new composite materials.

This object is achieved by a composite material containing a) at least one nitrogen and (half) metal-containing phase (a), and

b) at least one organic polymer phase (b), wherein at least one organic polymer phase (b) having at least one nitrogen and (half) metal-containing phase (a), also called phase (a) for short forms phase domains and the average distance (the arithmetic mean of the distances) of two adjacent domains of identical phases, determined by means of small angle X-ray scattering, is substantially at most 200 nm.

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, the composite materials according to the invention are nanocomposite materials or so-called nanocomposites.

The composite material according to the invention is characterized in that the organic polymer phase (b) with the nitrogen and (half) metal-containing phase (a) forms phase domains and the average distance (the arithmetic mean of the distances) of two adjacent domains of identical phases , determined with the aid of small angle X-ray scattering, is substantially at most 200 nm, preferably at most 50 nm, in particular less than 10 nm. By adjacent phase domains of identical phases is meant two phase domains of two identical phases separated by a phase domain of the other phase, for example two phase domains of the nitrogen and (half) metal-containing phase (a) passing through a phase domain of the organic polymer phase ( b) are separated, or two phase domains of the polymer phase (b), by a phase domain of the nitrogen and

(Half) metal-containing phase (a) are separated. With regard to the preferred morphological embodiments of the composite material according to the invention and the explanations concerning the terms of the phases and phase domains, reference is made in its entirety to WO 2010/1 12581, page 24, line 22 to page 25, line 8 of the cited text, which is hereby incorporated into the Description of the present invention is explained. The (semi-) metal in the nitrogen and (half) metal-containing phase (a) is preferably selected from B, Al, Ga, In, Si, Ge, Sn, As, Sb, Se, Te, Ti, Zr, V, Cr, Mo, W, Mn and mixtures thereof. The (semi-) metal is more preferably selected from B, Al, Si, Ti, Zr and Sn, most preferably from Al, Si, Ti and Zr, in particular Si. Particularly preferred are at least 90 mol%, especially at least 99 mol% of all metals or semimetals M in phase (a), based on the total amount of all (semi-) metals, equal to silicon. In one embodiment of the present invention, the composite material according to the invention is characterized in that the (semi-) metal of the phase (a) is selected from B, Al, Ga, In, Si, Ge, Sn, As, Sb, Se, Te , Ti, Zr, V, Cr, Mo, W, Mn and mixtures thereof, is preferably selected from B, Al, Si, Ti, Zr and Sn, more preferably selected from Al, Si, Ti and Sn, in particular under Si.

In one embodiment of the present invention, the composite material according to the invention is characterized in that the (semi-) metal of phase (a) is at least 90 mol%, based on the total amount of (semi-) metal in phase (a), silicon includes. In the nitrogen and (half) metal-containing phase (a), the molar ratio of (semi) metal to nitrogen can vary within a wide range, depending on the stoichiometry of the compounds formed. Preferably, in phase (a), the molar ratio of (semi) metal to nitrogen is in the range of 1: 1 to 1: 4. The nitrogen in phase (a) is preferably formally present in the oxidation state -3. The nitrogen in phase (a), as N ^3_ (nitride) or HN ^{2 ~} or H2N ^" (amides), wherein H may also be replaced by a hydrocarbon radical, with the present in a positive oxidation state (half) metal compound form.

In one embodiment of the present invention, the composite material according to the invention is characterized in that in the phase (a) the molar ratio of (half) metal to nitrogen in the range of 1 to 1 to 1 to 4.

The nitrogen and (half) metal-containing phase (a) is further characterized by the fact that the oxygen content in phase (a) is very low, that is, the content of (half) metal-oxygen compounds such For example, oxides or hydroxides, determined by elemental analysis, is very low. Preferably, the phase (a) contains 0 to 1 wt .-%, preferably from 0 to 0.1 wt .-%, in particular 0 to 0.01 wt.% Oxygen based on the total mass of the phase (a). In one embodiment of the present invention, the composite material according to the invention is characterized in that phase (a) is from 0 to 1% by weight, preferably from 0 to 0.1% by weight, in particular 0 to 0.01% by weight, of oxygen , based on the total mass of the phase (a) contains. In one embodiment of the present invention, the inventive

Composite material in that 1. the (semi-) metal of the phase (a) is selected from Al, Si, Ti and Zr in particular Si, 2. the (semi-) metal of the phase (a) is at least 90 mol%, in particular especially at least 99 mol%, based on the total amount of (semi-) metal in phase (a), comprises silicon, 3. in phase (a) the molar ratio of (half) metal to nitrogen in the range of 1 to 1 to 1 to 4, and 4th phase (a) from 0 to 1 wt .-%, preferably from 0 to 0.1 wt .-%, in particular 0 to 0.01 wt.% Oxygen, based on the Total mass of phase (a) contains.

The composite material according to the invention is preferably obtainable by a so-called twin polymerization of a suitable starting compound, in particular by polymerization 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 covalently bound via one or more nitrogen atoms to the metal or semimetal atom M of the polymerizable monomer unit A,

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, or by copolymerization of

i) at least one compound C selected from arylamidometalates and arylamido-metallates, with

ii) at least one compound D selected from oxygen-free formaldehyde reaction products containing at least one methylene equivalent,

in a reaction medium which is substantially anhydrous, wherein the compound D is used in an amount such that the molar ratio of methylene equivalents in compound D to the arylamido groups in the compound C is at least 0.5: 1. In one embodiment of the present invention, the composite material according to the invention is characterized in that the composite material is obtainable by polymerization of at least one monomer AB, which

at least one second cationically polymerisable organic monomer unit B, which is covalently bound via one or more nitrogen atoms to the metal or semimetal atom M of the polymerisable monomer unit A,

under cationic polymerization conditions under which both the polymerizable monomer unit A and the polymerizable monomer unit B undergo breakage of the bond between A and B, or by copolymerization of

i) at least one compound C selected from arylamidometalates and acrylamido-semimetals, with

in a reaction medium which is substantially anhydrous, wherein the compound D is used in an amount such that the molar ratio of methylene equivalents in compound D to the arylamido groups in the compound C is at least 0.5: 1. The organic polymer phase (b) may in principle contain one or more polymers, wherein the polymers may be selected from a variety of different polymers having different structure and construction. The polymer phase (b) preferably contains at least one polymer which contains aryl units which are linked to further aryl units via at least one substituted or unsubstituted alkylene group. The polymer phase (b) particularly preferably contains at least one polymer which contains aryl units derived from aniline and which are linked via at least one methylene group to further such aniline-derived aryl units.

Another object of the present invention is also a process for the preparation of a composite material containing a) at least one nitrogen and (half) metal-containing phase, and

b) at least one organic polymer phase comprising a polymerization of at least one monomer AB, the

under cationic polymerization conditions under which both the polymerizable monomer unit A and the polymerizable monomer unit B undergo breakage of the bond between A and B, or a copolymerization of

i) at least one compound C selected from arylamidometalates and acrylamido-semimetals, with ii) at least one compound D selected from oxygen-free formaldehyde reaction products containing at least one methylene equivalent,

in a reaction medium which is substantially anhydrous, wherein the compound D is used in an amount such that the molar ratio of methylene equivalents in compound D to the arylamido groups in the compound C is at least 0.5: 1.

The description and preferred embodiments of the nitrogen and (semi-) metal-containing phase (a) and the organic polymer phase (b) in the process 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 or in the aryl amidometalate or arylamidohalbmetallat is preferably selected from B, Al, Ga, In, Si, Ge, Sn, As, Sb, Se, Te, Ti, Zr, V, Cr, Mo, W, Mn and mixtures thereof. The metal or semimetal M is particularly preferably selected from B, Al, Si, Ti, Zr and Sn, very particularly preferably from Al, Si, Ti and Zr, in particular Si. Particularly preferred are at least 90 mol%, especially at least 99 mol% of all metals or semimetals M in phase (a), based on the total amount of all (semi-) metals, 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 monomer AB or in the arylamidometalate or arylamidohalbmetallat is selected from B, Al, Ga, In, Si, Ge, Sn, As, Sb, Se, Te, Ti, Zr, V, Cr, Mo, W, Mn and mixtures thereof, is preferably selected from B, Al, Si, Ti, Zr and Sn, particularly preferably selected from Al, Si, Ti and Zr, especially selected from Si.

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 monomer AB or in the Arylamidometallat or Arylamido- halbmetallat at least 90 mol%, based on the total amount at M, silicon.

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

R ¹ -Q _{x /} XR ^{1 '}

(I)

₂ / \ ₂ ,

R ² - G (YR ² ) _q wherein

M is a metal or semimetal; , R ^{2 may be the} same or different and each represents a radical

Ar-C (R ^a , R ^b ) - are, where Ar is an aromatic or heteroaromatic ring which optionally has 1 or 2 substituents which are halogen, CN, Ci-C6-alkyl, Ci-C6-mono- or di-alkylamino 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

wherein A is an aromatic or heteroaromatic ring fused to the double bond, m is 0, 1, 2 or 3, the radicals R may be identical or different and are halogen, CN, Ci-C6-alkyl, Ci-C6 mono- or di-alkylamino and phenyl are selected and R ^a , R ^{b have} the meanings given above;

may be the same or different and each represents NR ³ ;

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

may be the same or different and each represents NR ³ or a chemical bond;

may be the same or different and are each C 1 -C 6 -alkyl, C 3 -C 6 -cycloalkyl, 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 is a radical of the formula (Ia), as defined above, and

are hydrogen, alkyl, alkenyl, cycloalkyl or aryl, wherein aryl is unsubstituted or may have one or more substituents which are defined as the radicals R, and a plurality of radicals R ^{3 may be} identical or different, in particular R ^{3 is in} each case hydrogen ,

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.

An aromatic ring or radical, or aryl, is understood in the context of the invention to mean a carbocyclic aromatic hydrocarbon radical, such as phenyl or naphthyl. In the context of the invention, a heteroaromatic ring or 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 nitrogen, oxygen and sulfur, preferably nitrogen , and optionally 1 or 2 further ring members may each be a nitrogen atom and the remaining ring members are carbon. Examples of preferred heteroaromatic radicals are, pyrrolyl, pyrazolyl, imidazolyl, pyridyl, pyrimidyl or pyrdazinyl.

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.

The metal or metalloid M in formula I stands 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 la as defined above, in particular for a radical of the formula Iaa:

wherein m, R, R ^a and R ^{b have} the meanings given above. In the formulas Ia and Iaa, the variable m is, in particular, 0. If m is 1 or 2, R is in particular a methyl or C 1 -C 6 mono- or di-alkylamino group, in particular methyl group. In formulas Ia and laa, R ^a and R ^{b are} in particular hydrogen. In formulas la and laa, Q and G are in particular NH.

In a further preferred embodiment of the method according to the invention for producing a composite material, use is made of 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 formulas II or III,

wherein

M is Si, Ti, Zr, Hf, Ge or Sn, preferably Si, Ti and Zr, in particular Si;

R, R 'are independently selected from halogen, CN, C 1 -C 6 -alkyl, C 1 -C 6 -mono- or di-alkylamino and phenyl and are preferably methyl or C 1 -C 6 -mono- or di-alkylamino, in particular methyl ;

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

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 or = CH 2; in particular, R ^a , R ^b , R ^{a '} , R ^{b' are} each hydrogen, R ^c , R ^d are the same or different and each of Ci-C6-alkyl, C3-C6-cycloalkyl and

Aryl selected and are in particular methyl, and

R ^{3 is} hydrogen, alkyl, alkenyl, cycloalkyl or aryl, wherein aryl is unsubstituted or may have one or more substituents which are defined as the radicals R, and a plurality of radicals R ^{3 may be the} same or different, in particular R ^{3 is in} each case Hydrogen stands.

In one embodiment of the present invention, the process according to the invention for producing a composite material according to a second process variant, namely by copolymerization of at least one compound C with at least one compound D, characterized in that the compound C, which is selected from Arylamidometallaten and aryl amido-semi-metalates, by which general formula IV or condensation products thereof are described,

[(ArNR ⁴ ) _r MO _s R ⁵ t] u (IV) where

M is a metal or semimetal, preferably Si, Ti, Zr, Hf, Ge or Sn, particularly preferably Si, Ti and Zr, in particular Si;

r stands for 1, 2, 3, 4, 5 or 6, preferably for 2, 3 or 4, in particular 4,

s is 0, 1 or 2, preferably 0, t is 0, 1 or 2, preferably 0,

u is an integer, e.g. 1, 2, 3, 4, 5 or 6, in particular 1,

r + 2s + t is 1, 2, 3, 4, 5 or 6 and corresponds to the valency of M,

Ar is phenyl or naphthyl, wherein the phenyl ring or the naphthyl ring are unsubstituted or may have one or more substituents R ⁶ , which are selected from Ci-C6-alkyl, C3-C6-cycloalkyl and NR ^e R ^f , wherein R is ^e and R ^f independently of one another represent hydrogen, C 1 -C 6 -alkyl or C 3 -C 6 -cycloalkyl;

R ^{4 is} hydrogen, C ¹ -C ⁶ -alkyl, C 3 -C ⁶ -cycloalkyl or aryl, wherein aryl is phenyl or naphthyl and is unsubstituted or may have one or more substituents which are defined as the radicals R ⁶ , and several radicals R ^{4 may be the} same or different, and

R ^{5 is} hydrogen, C ₁ -C ₆ -alkyl, C ₃ -C ₆ -cycloalkyl or aryl, wherein aryl is phenyl or naphthyl and is unsubstituted or may have one or more substituents which are defined as the radicals R ⁶ .

Preferred examples of compound C are tetraanilinosilane, tetra (4-methylanilino) silane, trinilinoborate, tetraanilinotitanium, tetraanilinostannane, methyl (trianilino) silane, dimethyl (dianilino) silane, trimethyl (anilino) silane, phenyl (trianilino) silane, Diphenyl (dianilino) silane, diani- linomethylsilane and dianilinosilane.

Particularly preferred are arylamidometallates and arylamidohalbmetallaten the general formula IV

wherein

M is Si, Ti and Zr, especially Si;

r is 4,

s is 0,

t is 0,

u stands for 1,

Ar is an unsubstituted phenyl radical;

R ^{4 is} hydrogen or methyl, in particular hydrogen, and

R ^{5 is} methyl.

Condensation products of the arylamidometallates and arylamido-half metalates of the formula (IV) are formed by dissolving two or more molecules of the compounds of the formula (IV) with u = 1 with elimination of one molecule each of ArNR ⁴ 2 per newly formed MN (Ar) -M bridge connect to linear or cyclic structures.

Examples of cyclic condensation products which can be used as compound C in the copolymerization are hexaanilinocyclotrisilazane or octaanilinocyclotetrasilazane.

In the case of compound D, which is selected from oxygen-free formaldehyde reaction products containing at least one methylene equivalent, it is preferable to use to completely dehydrated reaction products of formaldehyde with ammonia or primary amines, preferably with ammonia. Completely dehydrated reaction products are, for example, imines, which are the primary reaction products of the reaction, or higher condensation products, as in the case of the reaction of formaldehyde with ammonia, with hexamethylenetetramine, also called urotropin, being formed as a stable condensation product. Preference is given to using compound D as urotopine in copolymerization.

In a further embodiment of the present invention, the inventive method for producing a composite material according to the second Verfahrensvarian- te, namely by copolymerization of at least one compound C with at least one compound D, characterized in that hexamethylenetetramine, also called urotropin, selected as compound D. becomes.

The copolymerization of at least one compound C with at least one compound D according to the second process variant is carried out in a reaction medium which is essentially anhydrous, wherein the compound D is used in an amount such that the molar ratio of methylene equivalents in compound D to the arylamido groups in the compound C preferably in the range from 1: 2 to 10: 1, particularly preferably in the range from 1, 0: 2 to 5: 1, very particularly preferably in the range from 1, 0: 1, 5 to 2: 1, in particular in the range 1, 0: 1, 3 to 1, 5: 1.

The reaction medium in which the copolymerization is carried out can be formed solely by the components C and D used, for example by forming a melt at elevated temperatures. Alternatively, an inert solvent can be used as the anhydrous reaction medium in which the components C and D at least partially, preferably completely dissolve. Suitable solvents are, for example, halogenated hydrocarbons such as dichloromethane, trichloromethane, dichloroethene or hydrocarbons such as toluene, xylene or hexane and mixtures thereof. The term "anhydrous" in the context of the present invention, a water content of less than 0.1 wt .-%, preferably less than 0.01 wt .-% understood at the beginning of the polymerization or copolymerization, wherein the water content by Karl In the process according to the invention for producing the composite material according to the invention, both the polymerization of the monomer AB, the so-called twin polymerization, and the alternative copolymerization of the compound C with compound D can be carried out purely thermally or using at least one catalyst. The temperatures required for the polymerization are typically in the range from 50 to 250 ° C., in particular in the range from 80 to 200 ° C. In the case of a catalyzed polymerization, for example with acid or base, the polymerization temperatures are typically within Range of 50 to 200 ° C and in particular in the range of 80 to 150 ° C. In the thermally initiated polymerization, the polymerization temperatures are typically in the range of 120 to 250 ° C and especially in the range of 150 to 200 ° C. Proton acids or Lewis acids are particularly suitable as catalysts.

In a preferred embodiment of the process according to the invention, the polymerization of the compound C with the compound D takes place in the presence of catalytic amounts of an acid. Typically, the acid is used in an amount of from 0.1 to 10% by weight, in particular from 0.2 to 5% by weight, based on the compounds C. Preferred acids here are Bronsted acids without oxygen, for example inorganic Bronsted acids such as HCl. As the Lewis acid, for example, BF3, BCI3, SnC, SnCU, TiCU, or AICI3 can be used. The use of complexed or dissolved in ionic liquids Lewis acids is also possible.

The polymerization can also be catalyzed with bases. Examples are amines such as triethylamine or dimethylaniline, hydroxides and basic salts of alkali metals and alkaline earth metals such as LiOH, NaOH, KOH, Ca (OH) ₂ , Ba (OH) ₂ or Na ₃ P0 ₄ and alkoxides of alkali metals and alkaline earth metals such as Na methylate, Na ethylate, Kt.Butylat or Mg-ethylate.

Preferred catalysts for the polymerization or copolymerization are protic acids selected from the group of CH-acidic and NH-acidic compounds, such as dicyanamide. In one embodiment of the present invention, the process according to the invention for producing a composite material is characterized in that the polymerization or copolymerization is carried out in the presence of an acid selected from the group of CH-acidic and NH-acidic compounds. Both the twin polymerization and the copolymerization can in principle be carried out as a so-called batch or as an addition process. When carried out as a batch, the reaction components are introduced in the desired amount in the reaction vessel and brought to the conditions required for the polymerization. In the addition process, which is particularly applicable for the copolymerization, at least one of the two components, ie compound C and / or compound D is at least partially fed in the course of the polymerization until the desired ratio of compound C to compound D is reached. Optionally, the addition is followed by a post-reaction phase. Preference is given to carrying out the polymerization and the copolymerization as a batch. The polymerization of the monomer AB or the copolymerization of the compound C with compound D may be followed by purification steps and optionally drying steps.

The composite material according to the invention or the composite material produced by the process according to the invention can be converted by analogy with the materials described in WO 2009/083083 by oxidative removal of the organic polymer phase (b) into a nanoporous inorganic material, or the new composite material can be prepared by carbonation of the organic polymer phase (b) to an electroactive material which can be used in electrochemical cells are reacted.

A further subject of the present invention is accordingly the use of a composite material according to the invention as described in the introduction or of a composite material obtainable or obtained by the process according to the invention described above for producing an electroactive material for electrochemical cells.

The present invention also provides a method for producing an electroactive material for electrochemical cells comprising the carbonization of a composite material as described in the introduction, or a composite material obtainable or obtained by the method according to the invention described above.

By carbonizing the composite material of the present invention, an electroactive material can be obtained.

As a rule, the carbonization is carried out at a temperature in the range from 200 to 2000 ° C., preferably in the range from 300 to 1600 ° C., more preferably in the range from 400 to 1100 ° C., in particular in the range from 500 to 900 ° C. ,

The duration of carbonation can vary widely and, among other things, depends on the temperature at which the carbonation is carried out. The period of carbonation may be from 0.5 to 12 hours, preferably from 1 to 5 hours, in particular from 1 to 2 hours.

The carbonization of the composite material according to the invention can, in principle, be carried out in one or more stages, for example in one or two stages. In principle, a step of carbonization in the presence or absence of oxidizing agents, such as

Oxygen can be carried out as long as the oxidizing agent does not completely oxidize the carbon present in the composite material according to the invention. In order to suppress the oxidation of the carbon present in the composite material according to the invention as far as possible, it has proved to be advantageous to carry out the carbonization with substantial or complete exclusion of oxygen, preferably in the presence of inert gases or reducing to carry out the gases (reactive gas). In a multi-stage carbonation process, the various steps may be carried out in the presence of different gases and / or at different temperatures. For example, a first step in the presence of an inert gas such as argon or nitrogen and a second step in the presence of a reducing gas (reactive gas) such as hydrogen, ammonia, carbon monoxide or acetylene and mixtures thereof, such as synthesis gas (CO / H2) or forming gas (N2 / H2 or Ar / h).

The carbonization of the composite material according to the invention can in principle be carried out under reduced pressure, for example under reduced pressure, under normal pressure or under elevated pressure, for example a pressure autoclave. As a rule, the carbonization is carried out at a pressure in the range from 0.01 to 100 bar, preferably in the range from 0.1 to 10 bar, in particular in the range from 0.5 to 5 bar or 0.7 to 2 bar. The carbonation can be carried out in a closed system or in an open system in which evolved volatiles in a gas stream, inert gases or reducing gases are removed.

In a preferred embodiment of the process according to the invention for the production of an electroactive material, therefore, the carbonization of the composite material according to the invention is carried out in one or more stages, preferably in one stage, with extensive or complete, preferably complete, exclusion of oxygen. Complete exclusion of oxygen in this context means that in the gas space not more than 0.5% by volume, preferably less than 0.05, in particular less than 0.01% by volume of oxygen are present.

In a further, preferred embodiment of the method according to the invention for the production of an electroactive material, the carbonization of the composite material according to the invention in the presence of a protective or reactive gas selected from Ar, N2, H2, NH3, CO and C2H2 and mixtures thereof.

In a further, preferred embodiment of the method according to the invention for producing an electroactive material, the carbonization of the composite material according to the invention is carried out in the presence of air or oxygen. In the carbonation step, further, depending on the conditions used, the metal or semi-metal bound in the nitrogen and (semi-) metal-containing phase (a) can be partially or completely reduced. The reduction of the metal or semimetal originally present in an increased positive oxidation state preferably takes place in the presence of a reducing gas, here also called reactive gas, as stated above. In a further preferred embodiment of the process according to the invention for producing an electroactive material, the partial or complete reduction of metals or semimetals in an increased positive oxidation state in the presence of a reactive gas is therefore selected in the carbonation step from H, NH 3, CO and C 2 H 2 and the latter Mixtures performed.

In the method of producing an electroactive material according to the present invention, by appropriately selecting the composite material of the present invention and the conditions during carbonization, the content of metal or metalloid in the electroactive material can be varied in a wide range. In principle, a value for the content of metal or semimetal of almost 0 wt .-%, that is, that only traces of metal or semimetal in the carbon phase C are present, to almost 100 wt .-%, that is, that in the metal or semimetal only traces of a carbon phase C are present, can be varied, wherein the wt .-% indication refers to the total mass of the electroactive material.

However, an electroactive material is preferably produced in the process according to the invention, characterized in that the content of metal or semimetal in the electroactive material is 5 to 90 wt .-%, preferably 10 to 75 wt .-%, particularly preferably 15 to 55 wt. -%, in particular 20 to 40 wt .-% based on the total mass of the electroactive material.

In particular, the method according to the invention is suitable for producing technical electrode materials in continuous and / or discontinuous mode of operation. In batch mode, this means batch sizes over 10 kg, better> 100 kg, even better> 1000 kg or> 5000 kg. In continuous driving this means production volumes over

100 kg / day, better> 1000 kg / day, even better> 10 t / day or> 100 t / day.

The method and the electrode materials produced therewith are furthermore distinguished by the fact that battery cells can be produced which preferably have at least 5 cycles, more preferably at least 10 cycles, most preferably at least 50 cycles, in particular at least 100 cycles or at least 500 Cycles are stable. Likewise provided by the present invention are electroactive materials obtainable by carbonization of a composite material according to the invention as described above.

The electroactive materials of the invention include

i) a carbon phase C; ii) at least one metal- or semimetal-containing phase, wherein the metal or semimetal is present in a lower oxidation state than the composite material, in particular as elemental metal or semimetal,

wherein the carbon phase C and the metal or metalloid-containing phase form substantially co-continuous phase domains, wherein the mean distance between two adjacent domains of identical phases is at most 10 nm, in particular at most 5 nm and especially at most 2 nm.

The electroactive materials according to the invention correspond in their morphological structure to the electroactive materials described in WO 2010/1 12580, which were prepared starting from oxygen-containing composite materials.

Due to its composition and the special arrangement of the carbon phase C and the metal or semimetal-containing phase, the electroactive material according to the invention is particularly suitable as material for anodes in Li-ion cells, in particular in Li-ion cells.

Secondary cells or batteries suitable. In particular, when used in anodes of Li-ion cells and especially of Li-ion secondary cells, it is characterized by a high capacity and a good cycle stability and ensures low impedance in the cell. Furthermore, it probably has a high mechanical stability due to the special phase arrangement. In addition, it can be produced easily and with reproducible quality.

Another object of the present invention is also the use of the electroactive material according to the invention as described above as part of an electrode for an electrochemical cell.

The present invention accordingly also provides an electrode for an electrochemical cell comprising the electroactive material according to the invention as described above. This electrode is usually installed and used as an anode in an electrochemical cell. Therefore, in the following, the electrode which contains the electroactive material according to the invention will also be referred to as the anode.

In addition to the electroactive material of the invention, the anode usually comprises at least one suitable binder for solidification of the electroactive material according to the invention and optionally further electrically conductive or electroactive components. In addition, the anode usually has electrical contacts for the supply and discharge of charges. The amount of electroactive material according to the invention, based on the total mass of the anode material minus any current collector and electrical contacts, is generally at least 40% by weight, often at least 50% by weight and especially at least 60% by weight.

As further electrically conductive or electroactive components in the anodes according to the invention, carbon black, graphite, carbon fibers, nanocarbon fibers, nanocarbon tubes or electrically conductive polymers into consideration. Typically, about 2.5-40% by weight of the conductive material is used together with 50-97.5% by weight, often with 60-95% by weight, of the electroactive material of the present invention in the anode to the total mass of the anode material, less any current collector and electrical contacts.

Suitable binders for the production of an anode using the electroactive materials according to the invention are in particular the following polymeric materials: polyethylene oxide (PEO), cellulose, carboxymethyl cellulose, polyvinyl alcohol, polyethylene, polypropylene, polytetrafluoroethylene, polyacrylonitrile-methyl methacrylate copolymers, styrene-butadiene copolymers, Tetrafluoroethylene-hexafluoropropylene copolymers, vinylidene fluoride-hexafluoropropylene copolymers (PVdF-HFP), vinylidene fluoride-tetrafluoroethylene copolymers, perfluoroalkyl vinyl ether copolymers, ethylene-tetrafluoroethylene copolymers, vinylidene fluoride-chlorotrifluoroethylene copolymers, ethylene-chlorofluoroethylene copolymers, ethylene-acrylic acid copolymers , optionally at least partially neutralized with alkali metal salt or ammonia, ethylene-methacrylic acid copolymers, optionally at least partially neutralized with alkali metal salt or ammonia, ethylene (meth) acrylic acid ester copolymers, polyimides and polyisobes utes.

The selection of the binder is optionally carried out taking into account the properties of the solvent possibly used for the preparation. The binder is usually used in an amount of 1 to 10 wt .-% based on the total mixture of the anode material. Preferably, 2 to 8 wt .-%, in particular 3 to 7 wt .-% are used.

The electrode according to the invention containing the electroactive material according to the invention, also referred to as anode, usually comprises electrical contacts for the supply and discharge of charges, for example a current conductor, in the form of a metal wire, metal grid, metal mesh, expanded metal, or a metal foil or a Metal sheet can be designed. As metal foils in particular copper foils are suitable.

In one embodiment of the present invention, the anode has a thickness in the range of 15 to 200 μηη, preferably from 30 to 100 μηη, based on the thickness without Stromableiter.

The preparation of the anode can be carried out in a conventional manner by standard methods, as they are known from the cited prior art and from relevant monographs. For example, to produce the anode, the inventive electroactive material, optionally using an organic solvent (for example, N-methylpyrrolidinone or a hydrocarbon solvent) with the optionally further constituents of the anode material (electrically conductive components and / or organic binder) and mix if necessary, a shaping method subject or on an inert metal foil, eg. B. Cu film, apply. Optionally, it is then dried. For example, a temperature of 80 to 150 ° C is used. The drying process can take place even at reduced pressure and usually takes 3 to 48 hours. Optionally, one can also use a melting or sintering process for shaping.

A further subject of the present invention is also an electrochemical cell, in particular a lithium ion secondary cell, containing at least one electrode which has been produced from or using an electroactive material according to the invention as described above.

Such cells generally have at least one anode according to the invention, a cathode, in particular a cathode suitable for lithium-ion cells, an electrolyte and optionally a separator.

With regard to suitable cathode materials, suitable electrolytes, suitable separators and possible arrangements, reference is made to the relevant prior art, for. B. on the cited prior art and corresponding monographs and reference works: z. Wakihara et al. (Publisher) in Lithiumion Batteries, 1st Edition, Wiley VCH, Weinheim, 1998; David Linden: Handbook of Batteries (McGraw-Hill Handbooks). 3. Edition. Mcgraw-Hill Professional, New York 2008; J. O. Besenhard: Handbook of Battery Materials. Wiley-VCH, 1998.

Particularly suitable cathodes are cathodes in which the cathode material has lithium transition metal oxide, eg. As lithium-cobalt oxide, lithium-nickel oxide, lithium-cobalt-nickel oxide, lithium-manganese oxide (spinel), lithium-nickel-cobalt-aluminum oxide, lithium-nickel-cobalt-manganese oxide or lithium-vanadium oxide, or a lithium transition metal phosphate such as lithium iron phosphate. 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.

The two electrodes, ie the anode and the cathode, are connected together using a liquid or even solid 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, Lithiumtrifluormethylsulfonat, lithium (bis (trifluoromethylsulfonyl) imide) or lithium tetrafluoroborate, insbesondere lithium hexafluorophosphate or lithium tetrafluoroborate, in suitable aprotic solvents such as ethylene carbonate, propylene carbonate and mixtures thereof with a or more of the following solvents: dimethyl carbonate, ethyl methyl 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. For example, ionic conductive polymers can be used as solid electrolytes.

Between the electrodes, a separator may be arranged, which is impregnated with the liquid electrolyte. Examples of separators are in particular glass fiber webs and porous organic polymer films such as porous films of polyethylene, polypropylene, PVdF, etc.

Particularly suitable materials for separators are polyolefins, in particular film-shaped porous polyethylene and film-shaped porous polypropylene.

Polyolefin separators, particularly polyethylene or polypropylene, may have a porosity in the range of 35 to 45%. Suitable pore diameters are, for example, in the range from 30 to 500 nm. In another embodiment of the present invention, it is possible to select, as separators, PET nonwovens which are filled with inorganic particles. Such separators may have a porosity in the range of 40 to 55%. Suitable pore diameters are, for example, in the range from 80 to 750 nm. Electrochemical cells according to the invention usually also contain a housing which may have any shape, for example a cuboid or the shape of a cylinder. In another embodiment, electrochemical cells according to the invention have the shape of a prism. In one variant, a metal-plastic composite film developed as a bag is used as the housing.

For example, the cells may have a prismatic thin film structure in which a thin film solid electrolyte is interposed between a film that is an anode and a film that is a cathode. A central cathode current collector is disposed between each of the cathode films to form a dual-area cell configuration. In another embodiment, a single-surface cell configuration may be employed in which a single cathode current collector is associated with a single anode / separator / cathode element combination. In this configuration, an insulating film is typically disposed between individual anode / separator / cathode / current collector element combinations.

Inventive electrochemical cells provide a high voltage and are characterized by a high energy density and good stability. In particular, electrochemical cells according to the invention are characterized by only a very small loss of capacity with prolonged use and repeated cycling.

The electrochemical cells of the invention can be assembled into lithium-ion batteries. Accordingly, another object of the present invention is also the use of electrochemical cells according to the invention, as described above, in lithium-ion batteries. Another object of the present invention are lithium-ion batteries, comprising at least one inventive electrochemical cell, as described above. 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.

Inventive electrical cells are characterized by particularly high capacity, high performance even after repeated charging and greatly delayed cell death. Electric cells according to the invention are very suitable for use in automobiles, electric motor-driven two-wheeled vehicles, for example pedelecs, aircraft, ships or stationary energy storage devices. Such uses are a further subject of the present invention.

Another object of the present invention is the use of electrochemical cells according to the invention as described above in devices, especially in automobiles, electric motor-powered two-wheelers, aircraft, ships or stationary energy storage.

The use of lithium ion batteries in devices according to the invention offers the advantage of a longer running time before recharging and a lower capacity loss with longer running time. 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.

Another object of the present invention is therefore the use of inventive lithium-ion batteries in devices, especially 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.

Accordingly, a further subject matter of the present invention is also a device comprising at least one electrochemical cell according to the invention as described above.

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.

TEM investigations were carried out as HAADF-STEM using a Tecnai F20 transmission electron microscope (FEI, Eindhoven, NL) at a working voltage of 200 kV in ultrathin layer technique (embedding of the samples in synthetic resin as matrix).

I. Preparation of Monomers 1.1 Preparation of 2,2'-spirobi [3,4-dihydro-1H-1, 3,2-benzodiazasiline] -Monomer M1

80 mmol of 2-aminobenzylamine were dissolved in 200 ml of dried toluene in a 500 ml three-necked flask with reflux condenser, gas inlet and dropping funnel under argon atmosphere. To the solution, 200 mmol of triethylamine as a base was added. Subsequently, 40 mmol of silicon tetrachloride were dissolved in 100 ml of dried toluene in a dropping funnel and slowly added dropwise to the solution of 2-aminobenzylamine and triethylamine in toluene, so that the solution heated only slightly. Immediately, a white precipitate of triethylammonium hydrochloride precipitated. This was separated after about 16 hours under argon atmosphere. The solvent was removed in vacuo to give a light yellow solid in 82% yield.

2,2'-spirobi [3,4-dihydro-1H-1, 3,2-benzodiazasiline]: light yellow powder;

Elemental analysis for Ci ₄ Hi ₆ N ₄ Si, found (in theory) in%: C: 61, 96 (62.65), H: 6.57 (6.01), N: 20.13 (20.87), Si: 1 1, 34 (10.47);

H-NMR (CDCl 3): 7.06 (ddd, ³ J ₇₈ = 7.8 Hz, ³ J ₆₇ = 7.5 Hz, J ₅₇ = 1.4 Hz, 2 H, H ⁷ ), 6.95 ( d, ³ J ₅₆ = 7.1 Hz, 2 H, H ⁵ ), 6.74 (ddd, ³ J ₅₆ = 7.1 Hz, ³ J ₆₇ = 7.5 Hz, ⁴ J ₆₈ = 1, 1 Hz , 2 H, H ⁶ ), (d, ³ J ₇₈ = 7.8 Hz, 2 H, H ⁸ ), 4.14 (dd, ² J ₄₄ ^< = 5.3 Hz, ³ J ₃₄ = ³ J ₃₄ '= 14.9 Hz, H / H ^4' ), 4.05 (dd, ² J ₄₄ ^< = 5.8 Hz, ³ J ₃₄ = ³ J ₃₄ '= 14.9 Hz, H / H ^4' ) 3.90 (s, 2 H, H), 1, 68 (s, 2 H; H ^3);

3C-NMR (CDCl ₃ ) δ in ppm: 144.9, 127.9 (C ⁹ / C ¹⁰ ); 127.6 (C ⁷ ), 126.5 (C ⁵ ), 1 18.9 (C ⁶ ), 1 17.9 (C ⁸ ), 44.5 (C ⁴ );

²⁹ Si NMR (CDCl3) δ in ppm: -48.9;

ATR-FTIR ( '^"' in cm- ^1): 3374, 3328, 3274 (V _N-H), 3015 (V = _C-H), 2922, 2895, 2850 (v _as, s CH2), 1601, 1583 , 1493, 1459 (v _c = c), 1 194 (VSI-NH), 835 (v _as , si-N), 743 (y = c- _H );

ESI-MS: [m / z] (relative intensity), CH 2 Cl 2 / CH 3 CN, Ci ₄ Hi ₆ N ₄ Si (M): 267.1071 (3) [MH] ⁺ , 226.0852 (15) [Si ₃ Hi ₆ N ₉ ] ⁺ , 123.0842 (22) [M-SiC ₇ H ₆ N ₂ ] ⁺ , 106.0575 (100) [M-SiC ₇ H ₈ N ₃ ] ⁺ . I.2 Preparation of Tetraphenylaminosilane - Monomer M2

At RT, 149.1 g of aniline were initially charged with 100 ml of toluene under nitrogen and cooled to 1 to 3 ° C in an ice water bath. For this purpose, 34.1 g of tetrachlorosilane were slowly added dropwise. With the first drops, the reaction solution became cloudy and the internal temperature rose to 4 ° C. During the 2 hour dropping time, the reaction mixture was cooled with ice water. The formed suspension thickened continuously during this time. Upon completion of the addition of the tetrachlorosilane, a thin white pulp was formed. The reaction mixture was warmed to RT and then stirred at 30 ° C for a further 1 hour. The reaction mixture was filtered with suction through a frit and rinsed the amber filtrate with 100 ml of toluene. The solution was concentrated at 100 ° C. and 5 mbar. There was obtained 76 g of product as an oil which crystallized at RT. H-NMR (500 MHz, 16 scans, CD ₂ Cl ₂ ): 4.17 ppm (4x1 H, s, -NH-Si); 6.80 ppm (4X1 H, t, para-H); 6.91 ppm (4X2H, d, ortho-H); 7.16 ppm (4X2H, t, meta-H);

II. Production of Composite Materials

11.1 Preparation of composite material KM-1 starting from monomer M1

5 g of the monomer M1 from Example 1.1 were melted under argon and brought to the desired polymerization temperature, e.g. 250 ° C, heated. This temperature was kept constant for three hours. In the process, gas evolution was observed by the formation of ammonia. The melt or the composite material was yellow and clear to black, depending on the reaction temperature. The composite material KM-1 then had to be stored under argon atmosphere.

11.2 Preparation of composite material KM-2 starting from monomer M2

61 g of tetraphenylaminosilane (M2 from Example I.2) and 18.9 g of urotropin (40% excess) were placed under nitrogen in an I.L. round bottom flask and 500 ml of diisopropylnaphthalene were added. The flask was heated to 160 ° C. in an oil bath and the mixture was left in the oil bath at this temperature for 5.5 hours. The mixture was cooled to RT and filtered through a glass frit under nitrogen. The product was washed twice with 100 ml of toluene and twice with 100 ml of hexane under nitrogen. On a rotary evaporator, the solid was dried at 100 ° C and 5 mbar. There were obtained 26 g of composite material KM-2.

Claims

claims

Composite material comprising a) at least one nitrogen and (half) metal-containing phase (a), and

b) at least one organic polymer phase (b), wherein at least one organic polymer phase (b) having at least one nitrogen and (half) metal-containing phase (a) phase domains forms and the average distance (the arithmetic mean of the distances) of two adjacent Domains of identical phases, determined by means of X-ray small-angle scattering, is essentially at most 200 nm.

Composite material according to claim 1, characterized in that the (semi-) metal of the phase (a) is selected from B, Al, Ga, In, Si, Ge, Sn, As, Sb, Se, Te, Ti, Zr, V , Cr, Mo, W, Mn and mixtures thereof.

Composite material according to claim 1 or 2, characterized in that the

(Semi) metal of the phase (a) to at least 90 mol%, based on the total amount of (half) metal in phase (a) comprises silicon.

Composite material according to one of claims 1 to 3, characterized in that in the phase (a) the molar ratio of (half) metal to nitrogen in the range of 1 to 1 to 1 to 4.

Composite material according to one of claims 1 to 4, characterized in that phase (a) from 0 to 1 wt .-% oxygen.

Composite material according to one of claims 1 to 5, obtainable by polymerization of at least one monomer AB, the

at least one second cationically polymerizable organic monomer unit B covalently bonded via one or more nitrogen atoms to the metal or semi-metal atom M of the polymerizable monomer unit A under cationic polymerization conditions under which both the polymerizable monomer unit A and the polymerizable monomer unit B are disrupted Polymerize bond between A and B, or by copolymerization of

i) at least one compound C selected from arylamidometalates and arylamido-half-metalates, with

ii) at least one compound D selected from oxygen-free formaldehyde reaction products containing at least one methylene equivalent in a reaction medium which is substantially anhydrous, wherein the compound D is used in an amount such that the molar ratio of methylene equivalents in Compound D to the arylamido groups in compound C is at least 0.5: 1.

A process for producing a composite material comprising a) at least one nitrogen and (semi-) metal-containing phase, and

at least one second cationically polymerizable organic monomer unit B covalently bonded via one or more nitrogen atoms to the metal or semi-metal atom M of the polymerizable monomer unit A under cationic polymerization conditions under which both the polymerizable monomer unit A and the polymerizable monomer unit B are disrupted Polymerize bond between A and B, or a copolymerization of

A method according to claim 7, characterized in that the metal or semimetal M of the monomer unit A in the monomer AB or in the arylamidometalate or A- rylamidohalbmetallat is selected from B, Al, Ga, In, Si, Ge, Sn, As, Sb, Se, Te, Ti, Zr, V, Cr, Mo, W, Mn and mixtures thereof. A method according to claim 7 or 8, characterized in that the metal or semimetal M of the monomer unit A in the monomer AB or in the Arylamidometallat or Arylamidohalbmetallat comprises at least 90 mol%, based on the total amount of M, silicon.

Method according to one of claims 7 to 9, characterized in that the monomer AB, which has at least one monomer unit A and at least one monomer unit B, is described by the general formula I,

R ¹ -Q _{x /} 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

wherein A is an aromatic or heteroaromatic ring fused to the double bond, m is 0, 1, 2 or 3, the radicals R may be identical or different and are halogen, CN, Ci-C6-alkyl, Ci- C6 mono- or di-alkylamino and phenyl are selected and R ^a , R ^{b have} the meanings given above;

may be the same or different and each represents NR ³ ; corresponding to the valence of M is 0, 1 or 2,

may be the same or different and each represents NR ³ or a chemical bond;

may be the same or different and are each C 1 -C 6 -alkyl, C 3 -C 6 -cycloalkyl, 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 is a radical of the formula (Ia), as defined above, and R ^{3 is} hydrogen, alkyl, alkenyl, cycloalkyl or aryl, wherein aryl is unsubstituted or may have one or more substituents which are defined as the radicals R, and several radicals R ^{3 may be} identical or different.

1 . Method according to one of claims 7 to 9, characterized in that the monomer AB, which has at least one monomer unit A and at least one monomer unit B, by the general formulas II or III is described,

wherein

M is Si, Ti, Zr, Hf, Ge or Sn;

R, R 'are independently selected from halo, CN, Ci-C6-alkyl, Ci-C6-mono- or di-alkylamino and phenyl;

m, n are independently 0, 1 or 2,

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 or = CH 2,

R ^c , R ^d are the same or different and are each selected from ^C 1 -C 6 -alkyl, ^C 3 -C 6 -cycloalkyl and aryl, and

R ^{3 is} hydrogen, alkyl, alkenyl, cycloalkyl or aryl, wherein aryl is unsubstituted or may have one or more substituents, such as the

R radicals are defined, and a plurality of radicals R ^{3 may be the} same or different.

Process according to any one of Claims 7 to 9, characterized in that the compound C selected from arylamidometalates and arylamido-semimetals is described by the general formula (IV) or condensation products thereof,

[(ArNR ⁴ ) _r MO _s R ⁵ t] u (IV) where

M is a metal or semimetal;

r is 1, 2, 3, 4, 5 or 6, s is 0, 1 or 2,

t is 0, 1 or 2,

u is an integer, e.g. 1, 2, 3, 4, 5 or 6,

r + 2s + t is 1, 2, 3, 4, 5 or 6 and corresponds to the valency of M,

Ar is phenyl or naphthyl, wherein the phenyl ring or the naphthyl ring are unsubstituted or may have one or more substituents R ⁶ , which are selected from C 1 -C 6 -alkyl, C 3 -C 6 -cycloalkyl and NR ^e R ^f , wherein R ^e and R ^{f are} independently hydrogen, alkyl or cycloalkyl; are hydrogen, C 1 -C 6 -alkyl, C 3 -C 6 -cycloalkyl or aryl, where aryl

Is phenyl or naphthyl and is unsubstituted or may have one or more substituents which are defined as the radicals R ⁶ , and a plurality of radicals R ^{4 may be} identical or different, and

is hydrogen, C ¹ -C ⁶ -alkyl, C 3 -C ⁶ -cycloalkyl or aryl, wherein aryl is phenyl or naphthyl and is unsubstituted or may have one or more substituents which are defined as the radicals R ⁶ .

13. The method according to any one of claims 7 to 9, characterized in that hexamethyl-entetramine is selected as compound D. 14. The method according to any one of claims 7 to 13, characterized in that the polymerization or copolymerization is carried out in the presence of an acid selected from the group of CH-acidic and NH-acidic compounds.

15. Use of a composite material according to any one of claims 1 to 6, or obtainable by a process according to any one of claims 7 to 14 for the preparation of an electro-active material for electrochemical cells.

16. A method for producing an electroactive material for electrochemical cells comprising the carbonization of a composite material according to any one of claims 1 to 6, or a composite material obtainable by a method according to any one of claims 7 to 14.

17. Electroactive material obtainable according to claim 16. 18. An electrochemical cell, comprising at least one electrode, which contains at least one electroactive material according to claim 17.

19. Use of electrochemical cells according to claim 18 in devices. 20. Device comprising at least one electrochemical cell according to claim 18.