JP2015522681A - Composite material and manufacturing method thereof - Google Patents

Abstract

A process for making a composite material comprising a) at least one (semi) metallic phase and b) at least one organic polymer phase, forming at least one aryloxy (semi) metalate and / or oxo acid An aryloxy (semi) metalate of a nonmetallic aryloxyester (compound I) different from carbon and nitrogen with at least one ketone, formaldehyde and / or formaldehyde equivalent (compound II) A copolymer in the presence of at least one (semi) metal compound (compound III), wherein the weight of the (semi) metal in compound III is at least 5% by weight, based on the weight of compound I ,process.

Description

  The present invention relates to the field of composite materials comprising an inorganic (semi) metallic phase and a polymer or carbonaceous phase. This type of composite material is usually obtained by reactive twin polymerization. Such composite materials can be used in the manufacture of rechargeable batteries and energy storage. The invention further relates to the use of the novel composite material in electrodes and electrochemical cells.

Patent Document 1, carbon phase and at least one MO _x phase (M is a metal or a semimetal) discloses the electro-active material comprising a. These phases form a co-continuous phase domain and are produced by twin polymerization (followed by a calcination step). According to this document, M may be selected from B, Al, Si, Ti, Zr, Sn, Sb, or mixtures thereof. Si may be up to 90 mol% based on the total amount of M.

  Patent Document 2 lists a process for producing a nanocomposite material having at least one inorganic or organometallic phase and an organic polymer phase by twin polymerization. In addition, nanocomposites having a carbon phase and at least one inorganic phase of a metalloid / metal oxide or metalloid / metal nitride are described. The disclosed nanocomposites have co-continuous phase domains. It is disclosed that the metal or metalloid can be a combination of Si with at least one further metal atom, in particular Ti or Sn.

  U.S. Patent No. 6,057,031 describes a process for producing a composite material having at least one oxide phase and one organic polymer phase, which forms an aryloxy (semi) metallate or oxo acid. This is accomplished by copolymerization of metal aryloxyesters with formaldehyde or formaldehyde equivalents. Calcination of the copolymer results in an electroactive nanocomposite comprising a semi-metal / metal inorganic phase and a carbon phase, the phase occurring in the co-continuous phase domain.

  U.S. Patent No. 6,099,056 describes a process based on the reaction of tin-containing monomers by twin polymerization. The disclosed composite material has at least one tin oxide phase and an organic polymer phase, which may be present in the co-continuous phase domain. This composite material may be used for the production of a tin-carbon composite material as described in US Pat.

Patent Document 5, carbon phase, and (is x, is a number from 0 to 2) at least one SnO _x phase discloses an electroactive material comprising (a novolak, by reaction with the tin salt).

International Publication No. 2010/112580 Pamphlet International Publication No. 2010/112581 Pamphlet International Application PCT / EP2012 / 050690 Specification European Patent Application No. 11181795.3 European Patent Application No. 11178160.5

  There is a need for a simple, reproducible and inexpensive manufacturing method that enables anode materials based on composite materials having nanoscale carbon-containing phases and (semi) metal-containing phases to be manufactured on an industrial scale. This is also true for the reactants required for it. Also, adjustment of the properties of the composite material to be synthesized, in particular the (semi) metal content, should be possible by adjusting the process conditions and / or changes in the starting materials.

  The object of the present invention was to provide a composite material suitable as an anode material for lithium ion batteries. Also, according to the manufacturing method (process), it has been found that the composite material can be easily manufactured with reproducible quality and on an industrial scale. It has been found that it is possible to manufacture with starting materials that are reliable, inexpensive and readily available. Another objective was that the (semi) metal content could be adjusted within a very wide range of limits.

  The electrochemical cell made with this anode material had high capacity, cycle stability, efficiency and reliability, good mechanical stability, and low impedance. The process could also be used for many combinations of various (semi) metals, and (semi) metals could be used in a flexible ratio.

This purpose is
a) at least one (semi) metallic phase;
b) a process for producing a composite material comprising at least one organic polymer phase,
At least one aryloxy (semi) metallate and / or non-metal forming an oxoacid, wherein the non-metallic aryloxy ester (compound I) is different from carbon and nitrogen,
With at least one ketone, formaldehyde and / or formaldehyde equivalent (compound II),
Copolymerization in the presence of at least one (semi) metal compound (compound III) that is not an aryloxy (semi) metalate;
The weight of the (semi) metal in compound III is achieved by the process being at least 5% by weight, based on the weight of compound I.

The present invention further includes
a) at least one (semi) metallic phase;
b) a composite material comprising at least one organic polymer phase,
The at least one (semi) metallic phase comprises at least two different (semi) metals, and the weight of each (semi) metal in the composite material is at least 2% by weight, based on the weight of carbon in the composite material And at least one organic polymer phase forms a phase domain with at least one (semi) metallic phase, and the average distance (arithmetic mean of distance) between two adjacent domains of the same phase is a small angle X-ray A composite material is provided that is determined using scattering and is essentially 200 nm or less.

The present invention is similarly
a) at least one carbon phase;
b) a composite material (hereinafter also referred to as “electroactive material”) comprising at least one oxidic phase and / or (semi) metallic phase comprising at least two different (semi) metals,
The weight of each (semi) metal in the composite material is at least 2% by weight, based on the weight of carbon in the composite material, at least one oxidic phase and / or (semi) metallic phase, and at least one The carbon phase forms a phase domain, and the average distance between two adjacent domains of the same phase (arithmetic mean of distance) is essentially 10 nm or less, as determined using small angle X-ray scattering, And / or the oxidic and / or (semi) metallic phase is determined using small angle X-ray scattering and essentially forms a phase domain with an average diameter (arithmetic mean of diameter) of 20 μm or less. Provide material.

  A further embodiment of the present invention is an electrode for an electrochemical cell comprising the use of the electroactive material of the present invention as an electrode in an electrochemical cell and the electroactive material of the present invention. The present invention also provides an electrochemical cell comprising an electrode comprising the electroactive material of the invention, its use in a lithium ion battery and device (apparatus), and a device and lithium ion battery comprising the electrochemical cell of the invention. To do.

  The process according to the present invention has several advantages. Of particular importance are the readily available starting materials, the availability of various reactants, and the ability to produce flexible composite materials. For example, the nature of the organic polymer phase can be altered by copolymerizing various compounds I that differ in the nature of the aryloxy group. Similarly, the adjustment of the properties of the (semi) metallic phase can be achieved by using compound I containing different (semi) metals or nonmetals in combination with at least one compound III containing one or more (semi) metals. Is possible.

It is a TEM image of the obtained electroactive material sample. It is a TEM image which shows a characteristic site | part. It is a figure which shows the discharge capacity over 40 cycles of two cells. It is a figure which shows the plot of the differential capacity | capacitance with respect to a voltage.

  For the definition of the term “phase”, see Book A. D. McNought and A.M. See Wilkinson: IUPAC Compendium of Chemical Terminology, 2nd Edition, Blackwell Scientific Publications, Oxford, Version 2.3.1 (2012) 1062. The terms “phase domain” and “co-continuous”, “discontinuous”, and “continuous phase domain” are also used. Its exact description can be found in W.W. J. et al. Work et al. , Definitions of Terms Related to Polymer Blends, Composites and Multiphase Polymeric Materials (IUPAC Recommendations 2004), Pure Appl. Chem. 76 (2004) 1985-2007. For example, a co-continuous arrangement of a two-component mixture is a phase-separated arrangement of two phases or components in which all regions of the phase domain boundary can be connected to each other by a continuous path within one domain of each phase. However, a path is understood to mean a phase separation arrangement that does not intersect any phase boundary.

The abbreviation “(semi) metal” in the context of the present invention represents “metal and / or metalloid”; similarly, “(semi) metal” is Represents “metallic and / or semi-metallic”. “Oxidic” refers to a chemical unit containing (semi) metal and oxygen. Various binding forms are possible, for example oxides, hydroxides or mixed forms. And stoichiometry can also vary within wide limits. For example, forms with low oxygen content (eg, less than 10%, less than 7%, or less than 5% by weight based on the weight of the composite) are possible. Forms roughly corresponding to the stoichiometric composition of defined compounds (such as SnO or Fe ₂ O ₃ ^* H ₂ O), and high oxygen content (eg, greater than 15% by weight based on the weight of the composite) , More than 20 wt%, or more than 25 wt%) forms are also possible.

The terms “alkyl”, “alkenyl”, “cycloalkyl”, “alkoxy”, “cycloalkoxy” and “aryl” are generic names for monovalent organic radicals, and their definitions are conventional. Possible number of carbon atoms in the radical are generally identified by the prefix C _f -C _g, f has a minimum, g is the maximum number of carbon atoms.

  Alkyl is a saturated, linear or branched hydrocarbyl radical (hydrocarbyl group), generally having 1 to 20, often 1 to 10, especially 1 to 4 carbon atoms, for example methyl , Ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, 2-pentyl, 3-pentyl, 2-methylbutyl, 3-methylbutyl, 3-methylbut-2-yl 2-methylbut-2-yl, 2,2-dimethylpropyl, n-hexyl, 2-hexyl, 3-hexyl, 2-methylpentyl, 2-methylpent-3-yl, 2-methylpent-2-yl, 2 -Methylpent-4-yl, 3-methylpent-2-yl, 3-methylpent-3-yl, 3-methylpentyl, 2,2-di Butyl, 2,2-dimethylbut-3-yl, 2,3-dimethyl-but-2-yl, 2,3-dimethylbutyl, n-heptyl, 2-methylhexyl, 2-methylhex-2-yl, 2 -Methyl-hex-3-yl, 2-methylhex-5-yl, 3-methylhex-2-yl, 3-methylhexyl, 3-methylhex-3-yl, 3-methylhex-4-yl, 2-methylhexa- 4-yl, 2,2-dimethylpentyl, 2,2-dimethylpent-3-yl, 2,2-dimethylpent-4-yl, 2,3-dimethylpent-2-yl, 2,3-dimethylpenta -3-yl, 2,3-dimethylpent-4-yl, 2,3-dimethylpent-5-yl, 2,4-dimethylpentyl, 2,4-dimethylpent-2-yl, 2,4-dimethyl pen -3-yl, 2,4-dimethylpent-4-yl, 2,4-dimethylpent-5-yl, 3,3-dimethylpentyl, 3,3-dimethylpent-2-yl, 3-ethylpentyl, 3-ethylpent-2-yl, 3-ethylpent-3-yl, 2,2,3-trimethylbutyl, 2,2,3-trimethylbut-3-yl, 2,2,3-trimethylbut-4-yl N-octyl, 2-methylheptyl, 2-methylhept-2-yl, 2-methylhept-3-yl, 2-methylhept-4-yl, 2-methylhept-5-yl, 2-methylhept-6-yl, 2-methylhept-7-yl, 3-methylheptyl, 3-methylhept-2-yl, 3-methylhept-3-yl, 3-methylhept-4-yl, 3-methylhept-5-yl, 3-methyl Hept-6-yl, 3-methylhept-7-yl, 4-methylheptyl, 4-methylhept-2-yl, 4-methylhept-3-yl, 4-methylhept-4-yl, 2,2-dimethylhexyl, 2,2-dimethylhex-3-yl, 2,2-dimethylhex-4-yl, 2,2-dimethylhex-5-yl, 2,2-dimethylhex-6-yl, 2,3-dimethylhexyl 2,3-dimethylhex-3-yl, 2,3-dimethylhex-4-yl, 2,3-dimethylhex-5-yl, 2,3-dimethylhex-6-yl, 2,4-dimethyl Hexyl, 2,4-dimethylhex-3-yl, 2,4-dimethylhex-4-yl, 2,4-dimethylhex-5-yl, 2,4-dimethylhex-6-yl, 2,5- Dimethyl hexyl, 2, -Dimethylhex-3-yl, 2,5-dimethylhex-4-yl, 2,5-dimethylhex-5-yl, 2,5-dimethylhex-6-yl, 3,3-dimethylhexyl, 3, 3-dimethylhex-2-yl, 3,3-dimethylhex-4-yl, 3,3-dimethylhex-5-yl, 3,3-dimethylhex-6-yl, 3,4-dimethylhexyl, 3, , 4-Dimethylhex-2-yl, 3,4-dimethylhex-4-yl, 3,4-dimethylhex-3-yl, 3-ethylhexyl, 3-ethylhex-2-yl, 3-ethylhex-3- Yl, 3-ethylhex-4-yl, 3-ethylhex-5-yl, 3-ethyl-hex-6-yl, 2,2,3-trimethylpentyl, 2,2,3-trimethylpent-3-yl, 2,2,3 Trimethylpent-4-yl, 2,2,3-trimethylpent-5-yl, 2,2,4-trimethylpentyl, 2,2,4-trimethylpent-3-yl, 2,2,4-trimethylpenta -4-yl, 2,2,4-trimethylpent-5-yl, 2,3,3-trimethylpentyl, 2,3,3-trimethylpent-2-yl, 2,3,3-trimethylpenta-4 -Yl, 2,3,3-trimethylpent-5-yl, 2,3,4-trimethylpentyl, 2,3,4-trimethylpent-3-yl, 2,3,4-trimethylpent-2-yl 3-ethyl-2-methylpentyl, 3-ethyl-2-methylpent-2-yl, 3-ethyl-2-methylpent-3-yl, 3-ethyl-2-methylpent-4-yl, 3-ethyl- 2-methylpenta- 5-yl, 3-ethyl-3-methylpentyl, 3-ethyl-3-methylpent-2-yl, 2,2,3,3-tetramethylbutyl, n-nonyl, 2-methylnonyl or n-decyl, 3 -Propylheptyl.

  Alkenyl is an olefinically unsaturated, linear or branched hydrocarbyl radical (hydrocarbyl group), generally having 2 to 20, often 2 to 10, especially 2 to 6 carbon atoms. For example, vinyl, 1-propenyl, 2-propenyl, 2-methyl-1-propenyl, 2-methyl-2-propenyl, 1-pentenyl, 2-pentenyl, 2-methyl-1-butenyl, 3-methyl-1 -Butenyl, 1-methyl-2-butenyl, 2-methyl-2-butenyl, 3-methyl-2-butenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 2-methyl-1-pentenyl, 3-methyl -1-pentenyl, 4-methyl-1-pentenyl, 2-methyl-2-pentenyl, 3-methyl-2-pentenyl, 4-methyl-2-pentenyl, -Methyl-3-pentenyl, 3-methyl-3-pentenyl, 4-methyl-1-pentenyl, 2-methyl-1-pentenyl, 3,3-dimethyl-2-butenyl, 2,3-dimethyl-1-butenyl 2,3-dimethyl-2-butenyl, 3,3-dimethyl-1-butenyl, 2-ethyl-1-butenyl, 2-ethyl-2-butenyl, 1-heptenyl, 2-heptenyl, 3-heptenyl, 1 -Octyl, 2-octyl, 3-octyl, 4-octyl, 1-nonenyl, 2-nonenyl, 3-nonenyl, 4-nonenyl, 1-decenyl, 2-decenyl, 3-decenyl, 4-decenyl or 5-decenyl It is.

  Alkoxy is an alkyl radical (alkyl group), as defined above, bonded through an oxygen atom, generally containing 1 to 20, often 1 to 10, especially 1 to 4 carbon atoms. For example, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy, tert-butoxy, n-pentyloxy, 2-methylbutyloxy, 3-methylbutyloxy, n-hexyl Oxy, n-heptyloxy, n-octyloxy, 1-methylheptyloxy, 2-methylheptyloxy, 2-ethylhexyloxy, n-nonyloxy, 1-methylnonyloxy, n-decyloxy or 3-propylheptyloxy .

  Cycloalkyl is a monocyclic, bicyclic or tricyclic saturated alicyclic radical (saturated alicyclic group), generally containing 3 to 20, often 3 to 10, especially 5 or 6 carbon atoms. For example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, bicyclo [2.2.1] hept-1-yl, bicyclo [2.2.1] hept-2-yl, bicyclo [ 2.2.1] hepta-7-yl, bicyclo [2.2.2] octan-1-yl, bicyclo [2.2.2] octan-2-yl, 1-adamantyl or 2-adamantyl.

  Cycloalkyloxy is a monocyclic, bicyclic or tricyclic saturated alicyclic radical (saturated alicyclic group) bonded through an oxygen atom, generally from 3 to 20, often from 3 10, especially 5 or 6 carbon atoms, for example cyclopropyloxy, cyclobutyloxy, cyclopentyloxy, cyclohexyloxy, cycloheptyloxy, cyclooctyloxy, bicyclo [2.2.1] hept-1-yloxy , Bicyclo [2.2.1] hept-2-yloxy, bicyclo [2.2.1] hept-7-yloxy, bicyclo [2.2.2] octan-1-yloxy, bicyclo [2.2.2 ] Octan-2-yloxy, 1-adamantyloxy or 2-adamantyloxy.

  Aryl is an aromatic hydrocarbyl radical (aromatic hydrocarbyl group). The aromatic hydrocarbyl group may have a substituent. This is preferably not substituted. Aryl is, for example, phenyl, 1-naphthyl or 2-naphthyl.

  The aryloxy group contains a negatively charged oxygen atom, which is obtained by deprotonation of the hydroxyl group of an aromatic monohydroxy aromatic compound (eg, those described below).

  The process according to the invention comprises the copolymerization of compound I with compound II in the presence of compound III. In accordance with the present invention, Compound I is a non-metallic aryloxy ester that forms at least one aryloxy (semi) metalate and / or oxo acid, which is different from carbon and nitrogen. “Aryloxy (semi) metalates” and “aryloxyesters” are formally one or more, in particular 1, 2, 3, 4, 5 or 6 aryloxy groups, and metals, metalloids or It is understood to mean a compound having a nonmetal (forms an oxoacid).

  According to the present invention, the nonmetal is different from carbon and nitrogen. Each aryloxy group is bonded to a metal, metalloid or nonmetal (forms an oxoacid, different from carbon and nitrogen) via a deprotonated oxygen atom. These metal, metalloid or nonmetal atoms (which form oxoacids and differ from C and N) are also referred to below as central atoms. Similar to one or more aryloxy radicals (aryloxy groups), one or more further groups (eg one, two or three organic radicals (eg selected from alkyl, alkenyl, cycloalkyl and aryl)) Or may be bonded to one or two oxygen atoms.

Compound I may have a single central atom or multiple central atoms, and when there are multiple central atoms, it may have a linear, branched, monocyclic or polycyclic structure . Suitable monohydroxyaromatic compounds are in particular phenol, α-naphthol and β-naphthol, which are unsubstituted, ie, apart from the hydroxyl group, any other atom other than hydrogen is a benzene ring or It is neither bonded to the naphthalene ring nor has a single or multiple (eg, 1, 2, 3 or 4) substituents other than hydrogen. These substituents are in particular alkyl, cycloalkyl, alkoxy, cycloalkoxy and NR _a R _{b where} R _a and R _b are each independently a hydrogen atom or an alkyl or cycloalkyl radical (group)) group. is there.

  The total number of groups attached is generally determined by the valence of the central atom, ie, metal, metalloid or nonmetal, to which these groups are attached.

In general, the central atom of Compound I is an element from the following group of the periodic table other than carbon and nitrogen (for the purposes of the present invention, the 2011 IUPAC rules are used):
Group 1 (particularly from here Li, Na or K), Group 2 (particularly from here Mg, Ca, Sr or Ba), Group 4 (particularly from here Ti or Zr), Group 5 (particularly from here especially V ), Group 6 (here especially Cr, Mo or W), Group 7 (here especially Mn), Group 13 (here especially B, Al, Ga or In), Group 14 (here especially Si) , Ge, Sn or Pb), Group 15 (here especially P, As or Sb) and Group 16 (here especially S, Se or Te). Preferred central atoms of Compound I are elements derived from Group 4, 13, 14 or 15 of the periodic table other than carbon and nitrogen, and among these, those derived from the second, third and fourth periods in particular. The central atom is more preferably selected from B, Al, Si, Sn, Ti and P.

  In one embodiment of the present invention, one or more aryloxy semimetalates are used as compounds I, ie compounds of semimetals (such as B or Si). In certain embodiments of the invention, compound I comprises an aryloxy half-metalate, wherein the half-metal comprises an aryloxy half-metalate that is at least as much as 90 mol% silicon, based on the total amount of half-metal atoms.

Suitable compounds I according to the invention may in particular be described by the following formula I:
[(AryO) _m MO _n R _p ] q (I)
Where
M is a non-metal or (semi) metal that forms an oxoacid other than carbon and nitrogen;
m is an integer and is 1, 2, 3, 4, 5 or 6;
n is an integer, 0, 1 or 2;
p is an integer and is 0, 1, 2 or 3;
q is an integer from 1 to 20, in particular an integer from 3 to 6,
m + 2n + p is an integer, 1, 2, 3, 4, 5 or 6, corresponding to the valence of M;
Ary is phenyl or naphthyl, wherein the phenyl ring or naphthyl ring is unsubstituted or one or more selected from alkyl, cycloalkyl, alkoxy, cycloalkoxy and NR _a R _b , for example 1, 2 Or it may have three substituents,
R _a and R _b are each independently hydrogen, alkyl or cycloalkyl;
R is hydrogen, alkyl, alkenyl, cycloalkyl or aryl, where aryl is unsubstituted or substituted selected from one or more of alkyl, cycloalkyl, alkoxy, cycloalkoxy and NR _a R _b May have a group,
R _a and R _b are each as defined above.

  When m in formula I is 2, 3, 4, 5 or 6, the Ary radicals (Ary groups) may be the same or different, in which case the different Ary is the nature of the aromatic ring and The nature of the substitution pattern may be different. When p in formula I is 2 or 3, the R radicals (R groups) may be the same or different.

Formula I should be understood as an empirical formula; this is the type and number of structural units characteristic of Compound I, ie, the central atom M, and the group attached to the central atom (ie, an aryloxy group) AryO, oxygen atom O and carbon-bonded R radical (R group)), and the number of these units are shown. _{[(AryO) m MO n R} p] unit, if q is greater than 1, may form a monocyclic or polycyclic or linear structure. In Formula I, M is a nonmetal, metal or metalloid that forms an oxoacid other than carbon and nitrogen, and the metal, metalloid and nonmetal are usually the following groups of the periodic table other than carbon and nitrogen: Selected from elements of origin:
Group 1 (particularly from here Li, Na or K), Group 2 (particularly from here Mg, Ca, Sr or Ba), Group 4 (particularly from here Ti or Zr), Group 5 (particularly from here especially V ), Group 6 (here especially Cr, Mo or W), Group 7 (here especially Mn), Group 13 (here especially B, Al, Ga or In), Group 14 (here especially Si) , Ge, Sn or Pb), Group 15 (here especially P, As or Sb) and Group 16 (here especially S, Se or Te). M is preferably an element selected from elements derived from Groups 4, 13, 14 and 15 of the periodic table, other than carbon and nitrogen, and in particular, elements of the second, third and fourth periods. M is particularly preferably B, Al, Si, Sn, Ti and P. In a particularly highly preferred embodiment of the invention, M is B or Si, in particular Si.

  In a preferred embodiment of the invention, p in formula I is 0, ie the atom M does not have any R radicals (R groups). In a further preferred embodiment of the invention, p in formula I is 1 or 2, ie the atom M has at least one R radical (R group).

In accordance with the present invention, the process involves copolymerization of Compound I with Compound II in the presence of Compound III, ie, forming two or more aryloxy (semi) metalates, and / or oxo acids. It is also possible to use non-metallic aryloxy esters which are non-metallic and different from carbon and nitrogen. A preferred process involves the use of at least two aryloxy (semi) metalates and / or non-metallic aryloxy esters that form oxo acids that are different from carbon and nitrogen. For example, it is possible to use two or more compounds corresponding to formula I, differing by M, Ary and / or R and / or by the variables m, n, p and / or q. For example, in at least one of the compounds of formula I, the variable p = 0, and in at least one further compound of formula I, the variable p may be 1 or more. Preferably, one compound of formula I comprises as M, B, Si, Sn, Ti or P, in particular B, Si or Sn, m is 1, 2, 3 or 4 and n is 0 or 1 , In particular 0, p is 0 and q is 0, 1, 3 or 4. The second compound of formula I has Si or Sn as M, m is 2, n is 0, q is 0 and p is 1 or 2. Ary in these two compounds of formula I may be the same or different and Ary has the aforementioned definition, in particular the definition specified as preferred, and in particular unsubstituted, or Phenyl which may have 1, 2 or 3 substituents selected from alkyl, in particular C ₁ -C ₄ alkyl, and alkoxy, in particular C ₁ -C ₄ alkoxy. R is preferably a _C 1 -C _{6 alkyl,} C 3 _{-C 10} cycloalkyl or phenyl, especially _C 1 -C _{4 alkyl,} C 5 -C ₆ cycloalkyl or phenyl. In a further particular embodiment of the invention, one of the two compounds of formula I comprises Si as M, m is 2 or 4, n is 0, p is 0 and q is 1 3 or 4. The second of the two compounds having formula I has Si as M, m is 2, n is 0 and p is 1 or 2. Ary in the two compounds of formula I may be the same or different, Ary having the above-mentioned definition, in particular the definition specified as preferred, and in particular unsubstituted or alkyl , In particular C ₁ -C ₄ alkyl, and alkoxy, in particular phenyl having 1, 2 or 3 substituents selected from C ₁ -C ₄ alkoxy. R is preferably a _C 1 -C _{6 alkyl,} C 3 _{-C 10} cycloalkyl or phenyl, especially _C 1 -C _{4 alkyl,} C 5 -C ₆ cycloalkyl or phenyl.

The variables m, n, p, Ary and R in formula I are preferably defined as follows, alone or in combination, in particular in combination with one of the preferred and particularly preferred definitions of M:
m is an integer and is 2, 3 or 4;
n is an integer, 0 or 1;
p is an integer and is 0, 1 or 2;
Ary is unsubstituted, or alkyl, preferably _C 1 -C ₄ alkyl, more preferably methyl, cycloalkyl, especially _C 3 _{-C 10} cycloalkyl, alkoxy, preferably _C 1 -C ₄ alkoxy, more preferably Is phenyl which may have one, two or three substituents selected from methoxy, cycloalkoxy, in particular C ₃ -C ₁₀ cycloalkoxy, and NR _a R _b , R _a and R _b are each independently and hydrogen, alkyl, especially _C 1 -C ₄ alkyl, preferably methyl or cycloalkyl, in particular _C 3 _{-C 10} cycloalkyl,;
R _is a C 1 -C _{6 alkyl,} C 2 -C _{6 alkenyl,} C 3 _{-C 10} cycloalkyl or phenyl, especially _C 1 -C _{4 alkyl,} C 5 -C ₆ cycloalkyl or phenyl.

More particularly, the variables m, n, p, Ary and R in formula I are preferably defined as follows, alone or in combination, in particular in combination with one of the preferred and particularly preferred definitions of M: R:
m is an integer and is 2, 3 or 4;
n is an integer, 0;
p is an integer and is 0, 1 or 2;
Ary is unsubstituted or alkyl, especially _C 1 -C ₄ alkyl, and alkoxy, or phenyl which in particular a _C 1 -C ₄ 1, 2 or 3 substituents selected from alkoxy.

  Preferred embodiments of compound I include those of formula I wherein q is 1. Such compounds can be regarded as orthoesters of a parent oxo acid with a central atom M. In this compound, the variables m, n, p, M, Ary and R are each as defined above, particularly singly or in combination, specifically in combination, preferred or particularly preferred. Has one of the definitions.

Compound I is preferably such that M is Al, B, Si, Sn, Ti or P, m is 3 or 4, n is 0 or 1, p is 0, 1 or 2, q It may be a compound of formula I wherein is 1. Ary In it, the above definition, in particular, have the definitions specified as preferred, and in particular, unsubstituted or alkyl, especially C ₁ -C ₄ alkyl, and alkoxy, especially C ₁ -C It is phenyl optionally having 1, 2 or 3 substituents selected from ₄ alkoxy.

In a particularly highly preferred embodiment of Compound I, M is B, Si or Ti, m is 3 or 4, n is 0, p is 0, 1 or 2, and q is 1. Some of the compounds of formula I. Ary In it, the above definition, in particular, have the definitions specified as preferred, and in particular, unsubstituted or alkyl, especially C ₁ -C ₄ alkyl, and alkoxy, especially C ₁ -C It is phenyl optionally having 1, 2 or 3 substituents selected from ₄ alkoxy.

A particular embodiment of compound I is a compound of formula I wherein M is Si, m is 4, n is 0 and p is 0, 1 or 2. Ary In it, the above definition, in particular, have the definitions specified as preferred, and in particular, unsubstituted or alkyl, especially C ₁ -C ₄ alkyl, and alkoxy, especially C ₁ -C It is phenyl optionally having 1, 2 or 3 substituents selected from ₄ alkoxy.

  Examples of preferred compounds of formula I according to the invention in which q = 1 are tetraphenoxysilane, tetra (4-methylphenoxy) silane, triphenylborate, triphenylphosphate, tetraphenyl titanate, tetracresyl titanate, tetraphenyl There are stannates and triphenylaluminates.

  Further embodiments of compound I include compounds of formula I wherein the Ary radical (Ary group) is different. As a result, the melting point of Compound I is generally reduced, which can provide advantages in polymerization. Examples of preferred compounds of formula I according to the invention that differ in Ary include triphenoxy (4-methylphenoxy) silane, diphenoxybis (4-methylphenoxy) silane, triphenoxy (4-methylphenoxy) silane, diphenoxydi (4 -Methylphenoxy) silane, diphenyl 4-methylphenyl borate, triphenyl 4-methylphenyl titanate, and diphenylbis (4-methylphenyl) titanate, and mixtures thereof.

Further specific embodiments of compound I include those of compounds of formula I wherein M is Si, m is 1, 2 or 3, n is 0 and p is 4-m. Ary In it, the above definition, in particular, have the definitions specified as preferred, and in particular, unsubstituted or alkyl, especially C ₁ -C ₄ alkyl, and alkoxy, especially C ₁ -C It is phenyl optionally having 1, 2 or 3 substituents selected from ₄ alkoxy. In these compounds, R has the definition described for formula I; more particularly R is hydrogen, methyl, ethyl, phenyl, vinyl or allyl. Examples of preferred compounds I of this embodiment include diphenoxy silane, diphenoxymethyl silane, triphenoxy silane, methyl (triphenoxy) silane, dimethyl (diphenoxy) silane, trimethyl (phenoxy) silane, phenyl (triphenoxy) silane and There is diphenyl (diphenoxy) silane.

Suitable compounds I are also “condensates” of compounds of formula I where q = 1. These compounds usually have the formula I, where q is an integer greater than 1, for example an integer ranging from 2 to 20, in particular 3, 4, 5 or 6. Such compounds are derived formally through the condensation of compounds of formula I where q = 1. In the case of two AryO units, formal removal forms Ary-O-Ary molecules and M (OAry) _m-2 (O) _n + 1R _p units. They are therefore essentially formed from the components of the following formula (Ia):
-[-OA-]-(Ia)
Where
-A- is a M (AryO) _m-2 (O) _n (R) _p group, and M, Ary and R are each as defined above;
m is an integer, 3 or 4,
n is an integer, 0 or 1, in particular 0,
p is an integer, 0, 1 or 2;
m + 2n + p is an integer, 3, 4, 5 or 6, corresponding to the valence of M.

  Preferably, M in formula I is Si, Sn, B and P.

In preferred embodiments, the condensate is cyclic and q is 3, 4 or 5. Such compounds can in particular be described by the following structure:

k is 1, 2 or 3, and -A- is a M (AryO) _m-2 (O) _n (R) _p group. M, Ary and R each have the definition given above for formula I, and m, n and p satisfy the conditions given above for formula I.

In a more preferred embodiment, the condensate is linear and is filled by having AryO units at both ends. That is, such compounds can be described by the following structure Ic:
Ary-[-OAA] _q -OAry (Ic)

q is an integer ranging from 2 to 20, -A- is a M (AryO) _m-2 (O) _n (R) _p group, and M, Ary, and R are each as described above for Formula I. Where m, n and p are each as defined above for Formula I. This embodiment is particularly preferred when the compound has a distribution with respect to the number of repeating units, ie has a different q. For example, a mixture wherein at least 99%, at least 90%, at least 80%, or at least 60% by weight based on the mass of Compound I is present as an oligomer mixture, q = 2 to 6, q There may be mixtures where = 4 to 9, q = 6 to 15, or q = 12 to 20.

  Examples of such condensates are triphenyl metaborate, hexaphenoxycyclotrisiloxane, octaphenoxycyclotetrasiloxane, triphenoxycyclotrisiloxane, or tetraphenoxycyclotetrasiloxane.

  Compound I is known or can be prepared analogously to known methods for the preparation of phenoxides; see, for example, German Patent Application Publication No. 1816241, Z. Anorg. Allg. Chem. 551 (1987) 61-66, Z.M. Chem. 5 (1965) 122-130 and Houben-Weyl, volume VI-2 35-41.

  According to the present invention, the process comprises copolymerization of at least one compound I with at least one compound II.

  Compound II is at least one ketone (such as acetone), aldehyde (such as furfural), or an aldehyde equivalent (such as trioxane). These compounds can generally form polymer structures under condensation with phenol. In a preferred embodiment, compound II is formaldehyde or formaldehyde equivalent, or a mixture thereof. Of course, various formaldehyde equivalent compounds can be copolymerized. The polymerization is preferably carried out using compound II (hereinafter also referred to as formaldehyde source). Compound II is selected from at least one gaseous formaldehyde, trioxane and / or paraformaldehyde. Compound II is in particular trioxane.

  Compound I and formaldehyde or formaldehyde equivalent (compound II) are converted to the molar ratio of formaldehyde in compound II, ie, the amount of monomeric formaldehyde used, or the amount of formaldehyde present in the formaldehyde equivalent when formaldehyde equivalent is used. Is at least 0.7: 1, better 0.9: 1, preferably at least 1: 1, in particular at least 1.01: 1, more preferably relative to the aryloxy group AryO present in compound I Is preferably used in an amount of at least 1.05: 1, in particular at least 1.1: 1. Excessive formaldehyde in excess of this is usually not critical but unnecessary, and formaldehyde or formaldehyde equivalents generally have a molar ratio of formaldehyde, or a molar ratio of formaldehyde present in the formaldehyde equivalent, of compound I It is used in an amount not exceeding a value of 10: 1, preferably 5: 1, in particular 2: 1, relative to the aryloxy group AryO present therein. The molar ratio of formaldehyde or formaldehyde equivalents, or the molar ratio of formaldehyde present in the formaldehyde equivalents, ranges from 1: 1 to 10: 1 with respect to the aryloxy group AryO present in Compound I. In particular in the range from 1.01: 1 to 5: 1, in particular in the range from 1.05: 1 to 5: 1 or 1.1: 1 to 2: 1.

Formaldehyde equivalent is understood to mean a compound that releases formaldehyde under polymerization conditions. Formaldehyde equivalents are preferably formaldehyde oligomers or polymers, ie substances of the empirical formula (CH ₂ O) _{x, where} x indicates the degree of polymerization. These include in particular trioxane (three formaldehyde units) and paraformaldehyde (generally comprising 8 to 100 formaldehyde units).

  Compound III is at least one (semi) metal compound that is not an aryloxy (semi) metalate. The at least one (semi) metal compound may be essentially purely inorganic (eg, (semi) metal halide, sulfate, nitrate or phosphate), or may be essentially covalent. (Eg (semi) metal alkanoates or alkoxides).

  The (semi) metals present in compound III are in particular Group 1 (preferably Na, K), Group 2 (preferably Ca, Mg), Group 3 (preferably particularly Sc) of the periodic table. , Group 4 (preferably particularly Ti, Zr), Group 5 (preferably particularly V), Group 6 (preferably particularly Cr, Mo, W), Group 7 (preferably particularly Mn), Group 8 (Preferably Fe, Ru, Os), Group 9 (preferably particularly Co, Rh, Ir), Group 10 (preferably particularly Ni, Pd, Pt), Group 11 (preferably particularly Cu, Ag, Au), Group 12 (preferably particularly Zn, Cd), Group 13 (preferably particularly B, Al, Ga, In), Group 14 (preferably particularly Si, Sn), and Group 15 (preferably In particular, As, Sb, Bi). (Semi) metal Ti, V, Cr, Mo, W, Mn, Fe, Co, Ni, Cu, Zn, B, Si and / or Sn are preferred, especially (semi) metal Ti, Fe, Co, Cu, Si And / or Sn is preferred.

Inorganic (semi) metal compounds include (semi) metal halides, which may be selected from fluoride, chloride, bromide, iodide and astatine, and mixtures and hydrates thereof. Preferred (semi) metal halides to be used are TiCl ₄ , CrCl ₃ , MnCl ₂ , FeCl ₂ , FeCl ₃ , CoCl ₂ , NiCl ₂ , ZnCl ₂ , CuCl ₂ , SnCl ₂ and / or SnCl ₄ , especially TiCl _4. FeCl ₃ , CoCl ₂ , CuCl ₂ , SnCl ₂ and / or SnCl ₄ . Further embodiments are (semi) metal sulfates, nitrates, phosphates or carbonates. Here, “sulfate” is usually a sulfur oxo anion (eg, SO ₄ ²⁻ , SO ₃ ²⁻ , S ₂ O ₃ ²⁻ ), and “nitrate” is a nitrogen oxo anion (eg, NO ₃ , NO _2). ^- ), "Phosphate" represents the oxoanion of phosphorus, and "carbonate" represents the oxoanion of carbon. (Semi) metal sulfate or nitrate, in particular Cr ₂ (SO ₄ ) ₃ , MnSO ₄ , FeSO ₄ , Fe (NO ₃ ) ₃ , Co (NO ₃ ) ₂ , NiSO ₄ , Cu (NO ₃ ) ₂ , ZnSO ₄ and / Or Sn (NO ₃ ) ₂ is preferred.

When compound III comprises an organo (semi) metallic compound, the anion present in the organo (semi) metallic compound is, for example, a carboxylate (preferably acetate, butanoate, propanoate, palmitate, citrate, oxalate, acrylate), Alkoxylates (as already described above, preferably methoxylate, ethoxylate, n-propoxylate, isopropoxylate, n-butoxylate, sec-butoxylate, isobutoxylate and tert-butoxylate) and Thiolates (especially methanethiolate, ethanethiolate, propanethiolate, butanethiolate). In particular, carboxylates and alkoxylates are used, preferably acetate, methoxylate or ethoxylate. Preferred organo (semi) metallic compounds to be used are Fe (CH ₃ COO) ₂ , Zn (CH ₃ COO) ₂ , Cu (CH ₃ COO) ₂ , Si (OCH ₃ ) ₄ , especially Fe (CH ₃ COO ) ₂ or Si (OCH ₃ ) ₄ .

Preferred compounds for use in compound III are Fe (CH ₃ COO) ₂ , CoCl ₂ , CuCl ₂ , SnCl ₂ , FeCl ₃ , Si (OCH ₃ ) ₄ , TiCl ₄ and / or SnCl ₄ .

  In the process according to the invention, compound III has a weight of (semi) metal in compound III based on the weight of compound I of at least 5% by weight, usually more than 5% by weight, in particular at least 10% by weight, preferably at least It is used in an amount such that it is 15% by weight, more preferably at least 20% by weight.

In one embodiment of the process according to the invention, Compound I may be polymerized in the presence of a formaldehyde source, Compound II and a catalytic amount of acid. In general, the acid is used in an amount of from 0.1 to 10% by weight, in particular from 0.2 to 5% by weight, for example up to 4, 3, 2 or 1% by weight, based on the weight of compound I. Preferred acids are Bronsted acids such as organic carboxylic acids (such as trifluoroacetic acid, oxalic acid and lactic acid) and organic sulfonic acids. The latter are in particular C ₁ -C ₂₀ alkanesulfonic acids (such as methanesulfonic acid, octanesulfonic acid, decanesulfonic acid and dodecanesulfonic acid) and haloalkanesulfonic acids (such as trifluoromethanesulfonic acid). Benzene sulfonic acid or C ₁ -C ₂₀ alkyl benzene sulfonic acid (toluene sulfonic acid, nonyl benzene sulfonic acid, dodecyl benzene sulfonic acid, etc.) can also be used. Likewise suitable are inorganic Bronsted acids (such as HCl, H ₂ SO ₄ or HClO ₄ ). The Lewis acid used may preferably be BF ₃ , BCl ₃ , SnCl ₄ , TiCl ₄ and AlCl ₃ in particular. It is also possible to use complex-bound Lewis acids or Lewis acids that dissolve in ionic liquids.

The polymerization may be catalyzed by a base. For example, alkoxides, hydroxides, phosphates, carbonates and / or of alkali metals and / or alkaline earth metals and also of ammonia and / or of primary, secondary and / or tertiary amines or else mixtures thereof It is possible to use hydrogen carbonate. Examples of bases include sodium methoxide, sodium ethoxide, potassium tert-butoxide or magnesium ethoxide, NaOH, KOH, LiOH, Ca (OH) ₂ , Ba (OH) ₂ , Na ₃ PO ₄ , Na ₂ CO ₃ , There are K ₂ CO ₃ , Li ₂ CO ₃ , (CH ₃ ) ₃ N, (C ₂ H ₅ ) ₃ N, morpholine, dimethylaniline and piperidine. In general, the base is used in an amount of 0.1 to 10% by weight, in particular 0.2 to 5% by weight, for example up to 4, 3, 2 or 1% by weight, based on the weight of compound I.

  For economic reasons, the catalyst is used only in the amount required for the catalytic reaction and is generally less than 10% by weight, for example less than 4, 3, 2 or 1% by weight, based on the weight of Compound I. It is. (Semi) metal-containing acids and bases may be used as compound III. In this case, they are used in the amounts specified for compound III.

  The polymerization may be initiated thermally, in which case the polymerization is preferably carried out in the presence of compound III in the presence of compound III without adding a catalytic amount of acid or base. It means that it is carried out by heating with. The temperature required for the polymerization is generally in the range from 50 to 250 ° C., in particular in the range from 80 to 200 ° C. In the case of acid or base catalyzed polymerization, the polymerization temperature is generally in the range from 50 to 200 ° C., in particular in the range from 80 to 150 ° C. In the case of thermally initiated polymerization, the polymerization temperature is generally in the range from 120 to 250 ° C., in particular from 150 to 200 ° C.

  The polymerization of the present invention may be generally carried out under reduced pressure compared to standard pressure, such as in vacuum, standard pressure, or under pressure, such as in a pressure autoclave. In general, the polymerization is 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, more preferably in the range from 0.7 to 2 bar. At a pressure of

  The polymerization may be carried out generally in a batch and / or addition process. When carrying out a batch process, Compound I, Compound II and Compound III are initially charged in the desired amount in the reaction vessel and result in the conditions necessary for the polymerization. In the additive process, at least one of Compound I and Compound II is fed at least partially during polymerization until the desired ratio of Compound I to Compound II is achieved. In this case, compound III may be charged first and / or added during the polymerization. The addition may be followed by a continuous reaction phase.

  Preference is given to performing a batch process. It has proved advantageous to carry out the polymerization in one stage. This means that the polymerization is carried out as a batch with the total amount of Compound I, Compound II and Compound III. Otherwise, an addition process is employed in which compound I and compound II are added such that the polymerization conditions are not interrupted until the total amount of compound I and compound II is added to the reaction vessel. Compound III may be charged first and / or supplied during the polymerization.

  Polymerization of Compound I and Compound II in the presence of Compound III may be generally carried out in any and desired manner, but only if it is certain that the components can react with each other. Thus, the reaction may be carried out in bulk, eg in a melt, or in the presence of a reaction medium, in particular a solvent.

  Useful solvents generally include all solvents in which Compound III is in an at least partially dissolved form. This is understood to mean that the solubility of compound III in the solvent under the polymerization conditions is at least 50 g / l, in particular at least 100 g / l. In general, the solvent is selected such that the solubility of compound III at standard pressure and 20 ° C. is 50 g / l, in particular at least 100 g / l. More particularly, the solvent is selected such that Compound III is substantially or completely dissolved. That is, the ratio of solvent to compound III is such that, under polymerization conditions, at least 80% by weight, in particular at least 90% by weight, based on the weight of compound III or the total amount of compound III used, is in dissolved form. Is selected.

  In a preferred variant, the polymerization is carried out in a solvent. In this case, at least 60%, preferably at least 75%, more preferably at least 90%, most preferably at least 95% by weight of the total amount of Compound I, Compound II and Compound III is in dissolved form.

  Preferred solvents are alcohols, ethers and ketones, especially alcohols having 1 to 8 carbon atoms, ethers and ketones. Examples of suitable alcohols are methanol, ethanol, n- and isopropanol, n-, sec-, iso- and tert-butanol, pentanol and hexanol. Also suitable are both cyclic ethers (preferably especially dioxane, tetrahydrofuran) and acyclic ethers (such as methyl ethyl ether, dimethyl ether, diethyl ether, methyl tert-butyl ether, diisopropyl ether and di-n-butyl ether). Examples of suitable cyclic or acyclic ketones are acetone, butanone or cyclohexanone. Particularly preferred solvents are THF and ethanol.

  It is preferred that the polymerization of Compound I and Compound II is carried out in the presence of Compound III and substantially free of water. This means that the concentration of water at the start of the polymerization is less than 1% by weight, preferably less than 0.5% by weight, more preferably 0.1% by weight, based on the total weight of Compound I, Compound II and Compound III. Means less than. The polymerization is more preferably carried out with the exclusion of water, ie under anhydrous conditions.

For the production of particulate composites, it has been found useful to carry out the reaction of Compound I with Compound II in the presence of Compound III in an inert diluent. Preferred inert diluents are hydrocarbons, aromatic hydrocarbons (mono- or poly C ₁ -C ₄ alkyl-substituted benzene or naphthalene, preferably toluene, xylene, cumene or mesitylene, or C ₁ -C ₄ alkyl-naphthalene. Etc.), and also diluents of aliphatic and cycloaliphatic hydrocarbons (hexane, cyclohexane, heptane, cycloheptane, octane and its isomers, nonane and its isomers, decane and its isomers, etc.) and mixtures thereof Of at least about 80% by volume, in particular at least about 90% by volume, especially at least about 99% by volume or 100% by volume.

Polymerization of Compound I with Compound II in the presence of Compound III may be followed by a purification step and optionally a drying step. In one process variant, the composition of the inorganic phase is changed. For example, the content of anions derived from compound III can be reduced by a washing step and / or a purification step. For this purpose, it is advantageous to use bases such as alkali metals and / or alkaline earth metals, and also ammonia and / or primary, secondary and / or tertiary amines, or else mixtures thereof. , Alkoxides, hydroxides, phosphates, carbonates and / or hydrogen carbonates can be used. Examples of bases include sodium methoxide, sodium ethoxide, potassium tert-butoxide or magnesium ethoxide, NaOH, KOH, LiOH, Ca (OH) ₂ , Ba (OH) ₂ , Na ₃ PO ₄ , Na ₂ CO ₃ , _{K 2 CO 3, Li 2 CO} 3, NaHCO 3, KHCO 3, (CH 3) 3 N, there is a _{(C 2 H 5) 3 N} , morpholine, dimethylaniline and piperidine. These bases may be used in a solvent (such as water, alcohol or ether, or mixtures thereof) (eg in methanol, ethanol, isopropanol, diethyl ether or THF).

  The composite material obtained by the process according to the invention may also be heated. This is usually 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, most preferably in the range from 500 to 900 ° C. .

  In one embodiment, the carbonization is performed at a lower range, such as less than 600 ° C, less than 500 ° C, such as 380 to 400 ° C. This procedure makes it possible to obtain a co-continuous structure with a large area. In a further embodiment, the carbonization is performed at a higher range, for example at a temperature above 700 ° C., above 800 ° C., eg 950-1050 ° C. This procedure makes it possible to produce large area carbon matrix isolated metal domains, in which case it is possible advantageously to use a reducing gas.

  The heating period is variable and depends on factors including the temperature at which the heating is performed. The period is, for example, 0.5 to 50 hours, preferably 1 to 24 hours, in particular 2 to 12 hours.

  Heating may be performed in one or more stages, such as one or two stages. In many cases, the heating is carried out to the desired temperature at a rate of 1 ° C. to 10 ° C./min, preferably 2 ° C. to 6 ° C./min, for example 2 ° C., 3 ° C. or 4 ° C./min. Cooling may begin immediately after reaching this temperature, or this temperature may be maintained for 10 minutes to 10 hours. This holding time may last for example 0.5 hours, 1 hour, 2 hours, 3 hours, 4 hours or 5 hours. It is also possible to sandwich a heat treatment step before the carbonization process. This is to keep the temperature constant within the temperature range from 100 ° C. to 400 ° C., preferably from 150 ° C. to 300 ° C. until the heat treatment step is completed, ie for example 1 hour or 2 hours (eg approximately 200 ° C. or Approximately 250 ° C.). In addition, the heating rate is in the temperature range from 100 ° C. to 400 ° C., preferably from 150 ° C. to 300 ° C., for example to one half or one third of the heating rate selected at the start of heating. It is possible to lower.

Heating may be carried out with substantial or complete exclusion of oxygen, preferably in the presence of an inert gas and / or a reducing gas (reactive gas). In this case, the organic polymeric material formed in the polymerization is carbonized to provide a carbon phase and an electroactive material is formed. In a preferred embodiment of the process according to the invention, the polymerization is carried out in one stage, at a standard pressure, substantially or completely, preferably completely excluding oxygen. The complete exclusion of oxygen in this context means that in the gas space in which the polymerization takes place, based on this gas space, not more than 0.5% by volume, preferably less than 0.05% by volume, in particular less than 0.01% by volume. Means that only oxygen is present. In a multi-stage heating process, the steps may be performed in the presence of various gases and / or at various temperatures. For example, first, for example, in the first step, heating is performed in the presence of an inert gas (such as argon or nitrogen), and then, for example, in the second step, a reducing gas (reactive gas) (Ar, N ₂ , H ₂ , Heating in the presence of NH ₃ , CO and C ₂ H ₂ , and mixtures thereof (eg, synthesis gas (CO / H ₂ ) and forming gas (N ₂ / H ₂ and / or Ar / H ₂ )), etc. Is possible.

Polymerization of Compound I with Compound II in the presence of Compound III may be followed by oxidative removal of the organic polymer phase, wherein the organic polymer material formed in the polymerization of the organic constituents is oxidized, A nanoporous oxidic material is obtained. In this case, the heating is carried out in the presence of an inert gas under the preferred form of oxygen. In a multi-stage heating process, for example, the steps can be performed in the presence of various gases and / or at various other temperatures. For example, first, in the first step, for example, in the presence of an inert gas (such as argon or nitrogen), and then in the second step, for example, an oxidizing gas (such as O ₂ ) and a mixture thereof (such as air or synthesis). It is possible to heat in the presence of air.

  Heating of the composite material obtained by polymerization may be carried out generally under reduced pressure, for example in a vacuum, under standard pressure, or under pressure, for example in a pressure autoclave. In general, the heating 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 from 0.7 to 2 bar. The Heating may take place in a closed system or in an open system in which the volatile constituents formed are removed, preferably in a gas stream comprising at least one inert gas and / or reducing gas.

  More particularly, the process according to the invention is suitable for producing electroactive materials in continuous and / or batch mode. In batch mode, this means that the batch size is greater than 10 kg, preferably greater than 100 kg, particularly preferably greater than 1000 kg or greater than 5000 kg. In continuous mode, this means that the production rate exceeds 100 kg / day, preferably more than 1000 kg / day, more preferably more than 10 t / day, or more than 100 t / day.

In addition, disclosed herein is a composite material (K1), which can be produced, for example, by a process according to the invention, and a) at least one (semi) metallic phase;
b) a composite material (K1) comprising at least one organic polymer phase;
The content of each (semi) metal in the composite material (K1) is at least 2% by weight, based on the carbon content of the composite material (K1), and the at least one organic polymer phase has at least a phase domain, The average distance (arithmetic mean of distance) between two adjacent domains of the same phase, formed with one (semi) metallic phase, is essentially less than 200 nm as determined using small angle X-ray scattering . In a preferred embodiment, the at least one (semi) metallic phase comprises at least two different (semi) metals.

  “Identical phase” means firstly an organic polymer phase and secondly exclusively (semi) metallic phase. Adjacent phase domains of the same phase are two phase domains of the same phase separated by one phase domain of the other phase, preferably in particular a (semi) metallic that is separated by one phase domain of the organic polymer phase It is understood to mean two phase domains of a polymer phase separated by two phase domains of a phase or one phase domain of a (semi) metallic phase.

  The average distance between adjacent phase domains of the same phase is generally 200 nm or less, often 100 nm or less or 50 nm or less, in particular 10 nm or less or 5 nm or less. The average distance between adjacent identical phase domains is determined by small angle X-ray scattering (SAXS), with scattering vector q (transmission at 20 ° C., monochromated CuK radiation, 2D detector (image plate), slit collimation) Determination). The size of the phase region, and thus the distance between adjacent phase boundaries and the phase arrangement may be determined by transmission electron microscopy (TEM), in particular by HAADF-STEM (high angle annular dark field scanning electron microscopy) methodology.

  The (semi) metallic phase can generally include any element that forms an oxidic structure. (Semi) metal oxides are preferred, in particular the first group of the periodic table (preferably especially Na, K), the second group (preferably especially Ca, Mg), the third group (preferably especially Sc), the fourth Group (preferably Ti, Zr), Group 5 (preferably V), Group 6 (preferably especially Cr, Mo, W), Group 7 (preferably particularly Mn), Group 8 (preferably Especially Fe, Ru, Os), Group 9 (preferably Co, Rh, Ir), Group 10 (preferably particularly Ni, Pd, Pt), Group 11 (preferably especially Cu, Ag, Au), Group 12 (preferably especially Zn, Cd), Group 13 (preferably especially B, Al, Ga, In), Group 14 (preferably especially Si, Sn), and Group 15 (preferably especially As, Sb, Bi) elements are preferred. Among these, (semi) metal Ti, V, Cr, Mo, W, Mn, Fe, Co, Ni, Cu, Zn, B, Si and Sn are preferable, and in particular, (semi) metal Ti, Fe, Co, Cu, Si and Sn are preferred.

  The content of each (semi) metal in the composite material (K1) of the present invention is at least 2% by weight, preferably at least 3% by weight, more preferably at least 5% by weight, based on the carbon content of the composite material. is there.

  In the composite material (K1) of the present invention, the region where the co-continuous phase domain occurs is preferably at least 10% by volume of the composite material, more preferably at least 30% by volume, even more preferably at least 50% by volume, very preferably Occupies at least 70% by volume, in particular at least 80% by volume up to 100% by volume.

The composite material (K1) of the present invention can be easily processed to further provide the electroactive material of the present invention. This can be used in particular for electrodes of electrochemical cells. The present invention is also a composite material (electroactive material),
a) at least one carbon phase;
b) providing a composite material comprising at least one oxidic and / or (semi) metallic phase;
The weight of each (semi) metal in the electroactive material is at least 2% by weight, based on the weight of carbon in the electroactive material, at least one oxidic and / or (semi) metallic phase, and at least 1 Two carbon phases form a phase domain, and the average distance between two adjacent domains of the same phase (arithmetic mean of distance) is essentially less than 10 nm as determined using small angle X-ray scattering. And / or at least one oxidic and / or (semi) metallic phase, as determined using small angle X-ray scattering, forms a phase domain with an average diameter (arithmetic mean of diameter) of 20 μm or less. In a preferred embodiment, the at least one oxidic and / or (semi) metallic phase comprises at least two different (semi) metals.

  “Identical phase” means firstly exclusively the carbon phase and secondly exclusively the oxidic and / or (semi) metallic phase. Adjacent phase domains of the same phase are two phase domains of the same phase separated by one phase domain of the other phase, preferably in particular one phase domain of the oxidic and / or (semi) metallic phase It is understood to mean two phase domains of the carbon phase separated by, or two phase domains of the oxidic and / or (semi) metallic phase separated by one phase domain of the carbon phase. The average distance between adjacent phase domains of the same phase is generally 10 nm or less, often 7 nm or less, in particular 5 nm or less, preferably 3 nm or less. Oxidic and / or (semi) metallic phase domains generally have an average diameter of 20 μm or less, preferably 2 μm or less, even more preferably 500 nm or less, in particular 100 nm or less.

  The average distance between adjacent identical phase domains and the average diameter of at least one oxidic and / or (semi) metallic phase is determined by the scattering vector q (by HAADF-STEM or by small angle X-ray scattering (SAXS). Determination via transmission at 20 ° C., monochromated CuK radiation, 2D detector (image plate), slit collimation).

  In the electroactive material of the present invention, the range in which co-continuous phase domains occur is preferably at least 10% by volume, more preferably at least 30% by volume, even more preferably at least 50% by volume, based on the total capacity of the electroactive material. Very preferably at least 70% by volume, in particular at least 80% to 100% by volume.

  The at least one oxidic and / or (semi) metallic phase may generally comprise any element that forms an oxide for the oxidic phase. For at least one oxidic and / or (semi) metallic phase, preference is given to (semi) metal oxides and / or (semi) metals, more preferably group 1 of the periodic table (preferably especially Na, K). ), Group 2 (preferably Ca, Mg in particular), Group 3 (preferably in particular Sc), Group 4 (preferably in particular Ti, Zr), Group 5 (preferably in particular V), Group 6 ( Preferably, especially Cr, Mo, W), Group 7 (preferably Mn), Group 8 (preferably especially Fe, Ru, Os), Group 9 (preferably particularly Co, Rh, Ir), Group 10 Group (preferably Ni, Pd, Pt), Group 11 (preferably Cu, Ag, Au), Group 12 (preferably especially Zn, Cd), Group 13 (preferably particularly B, Al, Ga) , In), Group 14 (preferably In particular Si, Sn), and Group 15 (preferably in particular As, Sb, elements of Bi) (semi) metal oxide and / or (semi) metal. Among these, (semi) metal Ti, V, Cr, Mo, W, Mn, Fe, Co, Ni, Cu, Zn, B, Si and Sn are preferable, and in particular, (semi) metal Ti, Fe, Co, Cu, Si and Sn are preferred.

  In at least one carbon phase, the carbon is essentially present in elemental form, i.e. the proportion of non-carbon atoms in the phase, e.g. N, O, S, P and / or H, is the total amount of carbon in the phase. Is less than 10% by weight, in particular less than 5% by weight. The content of non-carbon atoms in the phase may be determined by X-ray photoelectron spectroscopy (X-ray PES). Similar to carbon, the carbon phase can contain only small amounts of N, O and / or H, in particular as a result of the preparation. The molar ratio of H to C usually does not exceed a value of 1: 2, in particular a value of 1: 3, in particular a value of 1: 4. The value may be 0 or substantially 0, for example 0.1 or less.

  In the carbon phase, carbon is probably present mainly in the form of amorphous or graphite, which is based on X-ray PES studies based on a characteristic binding energy (284.5 eV) and a characteristic asymmetric signal shape. Can be concluded. Carbon in the form of graphite is understood to mean that the carbon is at least partly present in a unique hexagonal layer arrangement of graphite and the layer can be curved or exfoliated.

  The content of each (semi) metal in the electroactive material according to the invention comprising at least one carbon phase is at least 2% by weight, preferably at least 3% by weight, more preferably based on the weight of carbon in the composite material Is at least 5% by weight.

  Both the composite material (K1) of the present invention and the electroactive material of the present invention are simple, reproducible quality, and can be manufactured on an industrial scale, are reliable, inexpensive and readily available It has the advantage that it can be manufactured with materials.

  The present invention further includes the use of an electroactive material of the present invention as part of an electrode for an electrochemical cell, and an electrode for an electrochemical cell (hereinafter also referred to as an anode) comprising the electroactive material of the present invention. provide.

  Due to the composition and unique arrangement of at least one carbon phase (a) and at least one oxidic and / or (semi) metallic phase (b), the electroactive material of the present invention is a lithium ion cell, in particular a lithium ion cell. It is particularly suitable as a material for the anode in an ion secondary cell or battery. In particular, when used in the anode of a lithium ion cell, especially a lithium ion secondary cell, high capacity and good cycle stability are prominent and low impedance in the cell is ensured. It is also mechanically stable, probably due to the unique phase arrangement. Furthermore, it can be manufactured from easily available starting materials with simple, renewable quality.

  In addition to the electroactive material of the present invention, the anode typically comprises at least one binder suitable for consolidation of the electroactive material of the present invention, and optionally further electrically conductive or electroactive constituents. Also, the anode typically has electrical contacts for supplying and removing charge. The amount of the electroactive material according to the invention, based on the total mass of the anode material (minus any current collector and electrical contacts), is usually at least 40% by weight, often at least 50% by weight, in particular at least 60% by weight. %.

  Additional electrically conductive or electroactive constituents useful in the anode of the present invention include carbon black (conductive black), graphite, carbon fiber, carbon nanofiber, carbon nanotube or electrically conductive polymer. Generally, about 2.5 to 40% by weight of the conductive material is 50 to 97.5% by weight, often 60 to 95% by weight of the electroactive material of the present invention (optional current collectors and electrical contacts). (Weight percent figures are based on the total mass of the anode material).

Binders useful in the manufacture of anodes using the electroactive materials of the present invention include, among others, the following polymeric materials:
Polyethylene oxide, cellulose, carboxymethyl cellulose, polyvinyl alcohol, polyvinylidene fluoride, polyethylene, polypropylene, polytetrafluoroethylene, polyacrylonitrile-methyl methacrylate copolymer, styrene-butadiene copolymer, tetrafluoroethylene-hexafluoropropylene copolymer, vinylidene fluoride-hexa Fluoropropylene copolymer, vinylidene fluoride-tetrafluoroethylene copolymer, perfluoroalkyl vinyl ether copolymer, ethylene-tetrafluoroethylene copolymer, vinylidene fluoride-chlorotrifluoroethylene copolymer, ethylene-chlorofluoroethylene copolymer, ethylene-acrylic acid copolymer (optional) And at least in part, Neutralized with Lucari metal salt or ammonia), ethylene methacrylic acid copolymer (optionally at least partially neutralized with alkali metal salt or ammonia), ethylene- (meth) acrylic acid ester copolymer, polyimide , And / or polyisobutene, and mixtures thereof.

  The choice of binder is often made taking into account the nature of any solvent used in the production. For example, when N-ethyl-2-pyrrolidone is used as a solvent, polyvinylidene fluoride is suitable. The binder is usually used in an amount of 1 to 10% by weight, based on the total mass of the anode material. It is preferable to use 2 to 8% by weight, particularly 3 to 7% by weight.

  The electrode of the present invention comprising the electroactive material of the present invention, also referred to above as an anode, usually comprises electrical contacts for supplying and removing charges, such as output conductors, metal wires, metal grids, metal meshes, It may be configured in the form of a spread metal, metal foil and / or metal sheet. Suitable metal foils include in particular copper foil.

  In one embodiment of the invention, the anode has a thickness (based on the thickness excluding the output conductor) in the range of 15 to 200 μm, preferably 30 to 100 μm.

  The anode can be manufactured by standard methods, as is customarily known per se in the relevant monograph. For example, the anode is an anode material (any additional constituent) of the electroactive material of the present invention, optionally using an organic solvent (eg, N-methylpyrrolidinone, N-ethyl-2-pyrrolidone or hydrocarbon solvent). Can be produced by mixing with an electrically conductive component and / or organic binder) and optionally subjecting it to a molding process or applying it to an inert metal foil (eg Cu foil). This is optionally followed by drying. This is done, for example, using a temperature of 80 to 150 ° C. The drying operation may be performed under reduced pressure and usually lasts 3 to 48 hours. Optionally, a melting or sintering process can be used for shaping.

  The present invention further provides an electrochemical cell, in particular a lithium ion secondary cell, comprising at least one electrode made of or using an electrode material as described above.

  Such cells typically have at least one anode, cathode of the present invention, 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 relevant prior art (eg, Wakihara et al .: Lithium Ion Batteries, 1st edition, Wiley VCH, Weinheim (1998); David; Linden: Handbook of Batteries, 3rd edition, McGraw-Hill Professional, New York (2008); J. O. Besenhard: Handbook of Battery Materials, Wiley 98 (Wiley 98) (19).

As a useful cathode, in particular, the cathode material is a lithium transition metal oxide such 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 Examples include cathodes containing vanadium oxide or lithium transition metal phosphates (such as lithium iron phosphate). However, if it is intended to use a cathode material containing a polymer comprising sulfur and a polysulfide bridge, from the anode is charged with Li ^0, it is the ensure that such electrochemical cells can be discharged and recharged There must be.

  The two electrodes, the anode and the cathode, are connected to each other using a liquid or other solid electrolyte. Useful liquid electrolytes include in particular non-aqueous solutions of lithium and molten Li salts (generally with a water content of less than 20 ppm), such as lithium hexafluorophosphate, lithium perchlorate, lithium hexafluoroarsenate, lithium trifluoromethylsulfonate A solution of lithium bis (trifluoromethylsulfonyl) imide or lithium tetrafluoroborate, in particular lithium hexafluorophosphate or lithium tetrafluoroborate (suitable aprotic solvents (ethylene carbonate, propylene carbonate, and one or more of these Solvents: dimethyl carbonate, ethyl methyl carbonate, diethyl carbonate, dimethoxyethane, methyl propionate, ethyl propionate, butyrolac Down, acetonitrile, ethyl acetate, methyl acetate, a mixture of toluene and xylene, in particular ethylene carbonate and a mixture of diethyl carbonate, etc.), those in) and the like. The solid electrolyte used may be, for example, an ion conductive polymer.

  A separator impregnated with a liquid electrolyte may be disposed between the electrodes. Examples of separators include in particular glass fiber nonwovens and porous organic polymer films (polyethylene, polypropylene and other porous films).

  Particularly suitable separator materials include polyolefins, particularly porous polyethylene films and porous polypropylene films.

  Polyolefin separators, especially those composed of polyethylene or polypropylene, should have a porosity in the range of 35 to 45%. Suitable pore sizes are, for example, in the range from 30 to 500 nm.

  In another embodiment of the present invention, there may be a separator composed of a polyethylene terephthalate nonwoven filled with inorganic particles. Such separators should have a porosity ranging from 40 to 55%. Suitable pore sizes are, for example, in the range from 80 to 750 nm.

  The electrochemical cell of the present invention further includes a housing, which may be of any shape, such as a cube or cylinder shape. In another embodiment, the electrochemical cell of the present invention has the shape of a prism. In one variant, the housing used is a metal-plastic composite film elaborately made as a pouch.

  The cell may have, for example, a prismatic thin film structure, and a thin film structure in which a solid thin film electrolyte is disposed between a film constituting an anode and a film constituting a cathode. A central cathode output conductor is disposed between each cathode film to form a double-sided cell configuration. In another embodiment, a single-sided cell configuration may be used, with a single cathode output conductor assigned to a single anode / separator / cathode element combination. In this configuration, an insulating film is typically disposed between the individual anode / separator / cathode / output conductor element combinations.

  The electrochemical cell of the present invention has high capacity, cycle stability, efficiency and reliability, good mechanical stability, and low impedance.

  The electrochemical cells of the present invention may be combined to form a lithium ion battery.

  Thus, the present invention further provides the use of the electrochemical cell of the present invention as described above in a lithium ion battery.

  The present invention further provides a lithium ion battery comprising at least one electrochemical cell of the present invention as described above. The electrochemical cells of the present invention may be combined in the lithium ion battery of the present invention with each other, for example in series connection or in parallel connection. A series connection is preferred.

  The electrochemical cell of the present invention is particularly high in capacity, high in power even after repeated charging, and notably slowing down the cell. The electrochemical cell of the present invention is very suitable for use in devices. The use of the electrochemical cell of the present invention in a device also forms part of the subject matter of the present invention. The device may be a stationary device or a mobile device. There are vehicles as mobile devices, for example used on land (preferably cars and bicycles / tricycles), in the air (preferably especially aircraft) and in water (preferably ships and boats in particular). Mobile devices also include mobile devices such as mobile phones, laptops, digital cameras, implantable medical devices and power tools, especially from the field of architecture such as drills, battery-operated drivers and battery-powered tackers. Stationary devices include, for example, stationary energy storage (eg, for wind and solar energy) and stationary electrical devices. Such use forms a further part of the subject matter of the present invention.

  Use of the lithium ion battery of the present invention in a device, such as an appliance, provides the advantage of a longer runtime before recharging and less capacity loss during extended runtime. If an equal runtime must be achieved by the electrochemical cell, the lower the energy density, the higher the weight of the electrochemical cell that can be accepted. Furthermore, the lithium ion battery of the present invention can be used as a small and light battery. The lithium ion battery of the present invention is also highly reliable and efficient as a result of high capacity and cycle stability and low temperature sensitivity and self-discharge rate. Further, the lithium ion battery can be used safely and can be manufactured at low cost. Furthermore, the lithium ion battery of the present invention exhibits advantageous electrokinetic properties, which is particularly beneficial in the case of electrically powered vehicles and hybrid vehicles.

  The present invention is specifically illustrated by the following examples, which do not limit the invention.

[Production Example 1]
1a) Manufacture of composite materials (K1.1)
50 g tetraphenoxysilane and 16.5 g trioxane were initially charged and melted at 70 ° C. Subsequently, 28.5 g of SnCl ₂ was dissolved in 70 ml of THF and homogenized with the melt. This solution was added dropwise to a mixture of 200 ml xylene and 2.5 g methanesulfonic acid (100 ° C.). A white solid precipitated out and was collected and washed with toluene and hexane. After drying, 40 g of white powder was obtained. This was treated with sodium bicarbonate solution, water and methanol and then dried.
Final weight: 35.3g

1b) Production of electroactive material (higher temperature)
6 g of composite material (K1.1) was heated under a hydrogen flow rate of 2 to 3 l / h in a tubular furnace equipped with a quartz glass tube. The oven was heated from 3 to 4 ° C./min to 800 ° C. and held at 800 ° C. for 2 hours. Cooled overnight under a nitrogen flow of 1 to 2 l / h.

  This gave 3.6 g of fine black powder.

  The resulting electroactive material sample was analyzed by TEM (see FIG. 1): The TEM study was performed as a HAADF-STEM with a Tecnai F20 transmission electron microscope, the operating voltage was 200 kV, and the ultrathin layer methodology (sample was Embedded in a synthetic resin and used as a matrix). The lighter colored sites are heavier elements (here Sn and Si- (semi) metallic phases) and the darker colored sites are carbon rich elements (carbon phase) from which the domain spacing is several nm ( It is clear that it is around 10 nm or less.

1c) Production of electroactive materials (lower temperature)
6.2 g of composite material (K1.1) was heated under a hydrogen flow rate of 2 to 3 l / h in a tubular furnace equipped with a quartz glass tube. The oven was heated from 3 to 4 ° C./min to 650 ° C. and held at 650 ° C. for 2 hours. Cooled overnight under a nitrogen flow of 1 to 2 l / h.

  This gave 3.7 g of fine black powder.

  A TEM image is shown in FIG. Arrows indicate characteristic sites.

1d) Manufacture of electrodes The electroactive material obtained in 1b) is then mixed with conductive black (Timcal's Super P Li) and a binder (polyvinylidene fluoride KYNAR FLEX® 2801) as solvent. A viscous coating material was obtained consisting of 87% by weight of electroactive material obtained in 1b), 6% by weight of conductive black, and 7% by weight of binder in N-ethyl-2-pyrrolidone. The amount of solvent used was 125% by weight of the solid content used. The coating material was stirred for 16 hours for better homogenization. Subsequently, the coating material was applied to a copper film having a thickness of 20 μm (purity: 99.9%) using a coating bar and dried under reduced pressure at 120 ° C. After drying, the resulting electrode (width 8 cm) was calendered with a line pressure of 9 N / mm and then introduced into an argon atmosphere (water content <1 ppm, oxygen content <10 ppm). Prior to cell construction, the electrodes were again dried overnight at 5 mbar 120 ° C. To build an electrochemical test cell (two electrode test arrangement similar to a button cell), a 20 mm diameter circular piece was punched out. Lithium foil was used as the counter electrode. The electrolyte used was 1M LiPF ₆ in a 1: 1 mixture of ethylene carbonate and ethyl methyl carbonate. The cell was connected to a Maccor Series 4000 battery cycle unit for electrochemical characterization. The cell was cycled at a specific current of 30 mA per gram of active material between 10 mV and 2 V for Li / Li ⁺ . After reaching 10 mV, the voltage was held constant for 30 minutes.

  FIG. 3 shows the discharge capacity over 40 cycles of two cells. The achieved capacity is above the achievable value for graphite. From the fact that the curve profiles of the two cells are substantially identical, it is clear that the reproducibility of the electrode from 1d) is good.

  FIG. 4 shows a plot of differential capacitance against voltage. The values shown were calculated from data measured from chronoamperometry analysis. In chronoamperometry, a constant current is determined and the change in voltage is recorded. From the resulting differential capacitance versus voltage plot, it is possible to describe characteristic electrochemical processes such as lithium combinations or discharges or electrolyte decomposition. The characteristic peak for tin electrochemical activity at 0.4V (lithium and tin combination or alloy formation: negative y-axis) is between 0.6 and 0.8 volts (lithium-tin The 3 peaks for lithium extraction from the alloy (positive y-axis) are evident.

  FIG. 4: Differential capacitance of electrodes from 1d) at a voltage of 0 to 2V.

[Production Example 2] Production of composite material (K1.2)
50 g tetraphenoxysilane and 16.5 g trioxane were initially charged and melted at 70 ° C. Subsequently, 13.45 g of CuCl ₂ was dissolved in 100 ml of ethanol and homogenized with the melt. This solution was added dropwise to a mixture of 500 ml of toluene and 2.5 g of methanesulfonic acid (100 ° C.). A purple solid precipitated and was collected and washed with toluene and hexane. After drying, 40 g of white powder was obtained. The powder was stirred with sodium hydrogen carbonate solution, filtered with suction, washed with water and methanol and then dried.

  Final weight: 46.7g

[Production Example 3]
3a) Manufacture of composite materials (K1.3)
25 g of tetraphenoxysilane, 8.25 g of trioxane and 13 g of tetraethoxysilane were melted. This solution was added dropwise to a mixture of 250 ml xylene and 2.5 g methanesulfonic acid (100 ° C.). A pink solid precipitated out and was collected and washed with toluene and hexane and then dried.

  Final weight: 28g

3b) Production of electroactive materials (lower temperature)
3.9 g of composite material (K1.3) was heated under a hydrogen flow rate of 2 to 3 l / hr in a tubular oven equipped with a quartz glass tube. The oven was heated from 3 to 4 ° C./min to 800 ° C. and held at 800 ° C. for 2 hours. Cooled overnight under a nitrogen flow of 1 to 2 l / h.

  This gave 2.2 g of fine black powder.

3c) Production of electroactive material (higher temperature)
3.8 g of composite material (K1.3) was heated in a tubular oven equipped with a quartz glass tube under hydrogen at a flow rate of 2 to 3 l / hour. The oven was heated from 3 to 4 ° C./min to 980 ° C. and held at 980 ° C. for 2 hours. Cooled overnight under a nitrogen flow of 1 to 2 l / h.

  This gave 2.1 g of fine black powder.

Claims (17)

a) at least one (semi) metallic phase;
b) a method for producing a composite material comprising at least one organic polymer phase,
A non-metallic aryloxy ester (compound I) that forms at least one aryloxy (semi) metalate and / or oxoacid that is different from carbon and nitrogen,
At least one ketone, formaldehyde and / or formaldehyde equivalent (compound II);
Copolymerizing in the presence of at least one (semi) metal compound (compound III) that is not an aryloxy (semi) metalate;
The process for producing, wherein the weight of the (semi) metal in compound III is at least 5% by weight, based on the weight of compound I.   The process according to claim 1, wherein compound III is dissolved in the reaction medium.   3. A process according to claim 1 or claim 2 wherein compound III is added to the melt of compound I and compound II.   Compound III is a manufacturing method as described in any one of Claims 1-3 which contains Ti, Fe, Co, Cu, Si, and / or Sn as said (semi) metal. Compound _{III, Fe (CH 3 COO) 2} , CoCl 2, CuCl 2, SnCl 2, FeCl 3, Si (OCH 3) 4, a TiCl ₄ and / or SnCl _4, any of claims 1 to 4 The manufacturing method according to claim 1. Said compound I is represented by formula I:
[(AryO) _m MO _n R _p ] q (I)
Where
M is a nonmetal or (semi) metal that forms an oxoacid other than carbon and nitrogen;
m is an integer of 1, 2, 3, 4, 5 or 6;
n is an integer of 0, 1 or 2;
p is an integer of 0, 1, 2 or 3;
q is an integer from 1 to 20,
m + 2n + p is an integer of 1, 2, 3, 4, 5 or 6 and corresponds to the valence of M;
Ary is phenyl or naphthyl, the phenyl ring or naphthyl ring is unsubstituted or has one or more substituents selected from alkyl, cycloalkyl, alkoxy, cycloalkoxy and NR _a R _b You can,
R _a and R _b are independently of each other hydrogen, alkyl or cycloalkyl;
R is hydrogen, alkyl, alkenyl, cycloalkyl or aryl, where aryl is one or more selected from the group consisting of unsubstituted, alkyl, cycloalkyl, alkoxy, cycloalkoxy and NR _a R _b May have a substituent of
_Ra and _Rb are the manufacturing methods as described in any one of Claims 1-5 which are respectively what was mentioned above.   The production method according to any one of claims 1 to 6, wherein the obtained copolymer is heated.   The manufacturing method according to any one of claims 1 to 7, wherein an oxidizing agent or a reducing agent can be allowed to act on the obtained copolymer. a) at least one (semi) metallic phase;
b) a composite material comprising at least one organic polymer phase,
The at least one (semi) metallic phase comprises at least two different (semi) metals, and the weight of each (semi) metal in the composite material is at least 2 weight based on the weight of carbon in the composite material At least one organic polymer phase forms a phase domain with at least one (semi) metallic phase;
A composite material in which the average distance (arithmetic mean of distance) between two adjacent domains of the same phase, measured using small angle X-ray scattering, is essentially 200 nm or less. a) at least one carbon phase;
b) a composite material comprising at least one oxidic phase and / or (semi) metallic phase comprising at least two different (semi) metals,
The weight of each (semi) metal in the composite material is at least 2% by weight, based on the weight of carbon in the composite material, and at least one oxidic phase and / or (semi) metallic phase, and at least One carbon phase forms a phase domain,
The average distance (arithmetic mean of distance) between two adjacent domains of the same phase, measured using small angle X-ray scattering, is essentially 10 nm or less and / or
The oxydic and / or (semi) metallic phase essentially forms a phase domain with an average diameter (arithmetic mean of diameter) measured using small angle X-ray scattering of 20 μm or less.   Use of the composite material according to claim 10 as part of an electrode for an electrochemical cell.   An electrode for an electrochemical cell comprising the composite material according to claim 10.   An electrochemical cell comprising at least one electrode according to claim 12.   Use of an electrochemical cell according to claim 13 in a lithium ion battery.   A lithium ion battery comprising at least one electrochemical cell according to claim 13.   A method of using an electrochemical cell according to claim 13 in a device.   A device comprising at least one electrochemical cell according to claim 13.

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