WO2014001949A1 - Matériaux composites et leur procédé de fabrication - Google Patents

Matériaux composites et leur procédé de fabrication Download PDF

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Publication number
WO2014001949A1
WO2014001949A1 PCT/IB2013/054939 IB2013054939W WO2014001949A1 WO 2014001949 A1 WO2014001949 A1 WO 2014001949A1 IB 2013054939 W IB2013054939 W IB 2013054939W WO 2014001949 A1 WO2014001949 A1 WO 2014001949A1
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WIPO (PCT)
Prior art keywords
semi
phase
metal
compound
carbon
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PCT/IB2013/054939
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German (de)
English (en)
Inventor
Arno Lange
Gerhard Cox
Hannes Wolf
Szilard Csihony
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Basf Se
Basf Schweiz Ag
Basf (China) Company Limited
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Application filed by Basf Se, Basf Schweiz Ag, Basf (China) Company Limited filed Critical Basf Se
Priority to KR1020157001719A priority Critical patent/KR20150032308A/ko
Priority to JP2015519401A priority patent/JP2015522681A/ja
Priority to EP13809585.6A priority patent/EP2865033A4/fr
Priority to CN201380034016.8A priority patent/CN104412422A/zh
Publication of WO2014001949A1 publication Critical patent/WO2014001949A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/137—Electrodes based on electro-active polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
    • H01M4/602—Polymers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention is in the field of composite materials having inorganic (semi-) metal-containing phases and either polymer phases or carbonaceous phases.
  • Composite materials of this type are generally accessible by reactive twin polymerization. Such composite materials can be used for the production of rechargeable batteries and energy storage.
  • the invention further describes the use of the novel composite materials in electrodes and electrochemical cells.
  • WO2010 / 1 12580 discloses an electroactive material containing a carbon phase and at least one MO x phase, wherein M is a metal or semimetal. These phases form co-continuous phase domains and are prepared by twin polymerization followed by a calcination step M be selected from B, Al, Si, Ti, Zr, Sn, Sb or mixtures thereof. In this case, Si may be up to 90 mol%, based on the total amount of M.
  • WO2010 / 12581 includes a process for producing a nanocomposite material having at least one inorganic or organometallic phase and one organic polymer phase by twin polymerization.
  • nanocomposite materials having a carbon phase and at least one inorganic phase of a half / metal oxide or half / metal nitride are described.
  • the disclosed nanocomposite materials have co-continuous phase domains. It is disclosed that the metals or semimetals can be a combination of Si with at least one further metal atom, in particular Ti or Sn.
  • PCT / EP2012 / 050690 discloses a process for producing a composite material having at least one oxide and one organic polymer phase, which is achieved by copolymerizing aryloxy (semi-) metal or aryloxy esters of oxo-acid-forming non-metals with formaldehyde or formaldehyde equivalents , Calcination of the copolymerate results in electroactive nanocomposite materials containing a semi-metal / inorganic metal phase and a carbon phase, which phases occur in co-continuous phase domains.
  • EP application no. 1 1 181795.3 describes a process based on the reaction of tin-containing monomers by twin polymerization.
  • the disclosed composite materials comprise at least one tin oxide phase and an organic polymer phase, wherein the phases may be in co-continuous phase domains.
  • This composite material can, as in EP application no. 1 1 181795.3, also be used for the production of a tin-carbon composite material.
  • EP application no. 1,171,8160.5 discloses an electroactive material comprising a carbon phase and at least one SnO x phase, where x is a number from 0 to 2, by reacting a novolak with a tin salt.
  • the present invention has for its object to provide a composite material which is suitable as anode material for lithium-ion batteries. Also, a process for its preparation should be found, whereby the composite material can be produced in a simple manner, with reproducible quality and on a large scale, the production should be safe, inexpensive and easily accessible starting materials feasible. The aim was also that the content of (semi) metal should be adjustable in the widest possible limits.
  • the electrochemical cells made with this anode material should have high capacitance, cycle stability, efficiency, reliability, good mechanical stability and low impedances.
  • the process should be applicable to a variety of combinations of different (semi-) metals that should be usable in a flexible ratio.
  • This object is achieved with a method for producing a composite material containing
  • aryloxy (semi-) metalate and / or aryloxy ester of an oxo acid-forming non-metal wherein the non-metal of carbon and nitrogen
  • Another object of the present invention is a composite material containing a) at least one (semi-) metal-containing phase and
  • At least one (semi-) metal-containing phase contains 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 organic polymer phase having at least of a (semi-) metal-containing phase forms phase domains and the average distance (the arithmetic mean of the distances) of two adjacent domain-identical phases, determined by means of small-angle X-ray scattering, is substantially at most 200 nm.
  • a composite material also referred to below as “electroactive material”
  • each (semi-) metal of the composite material is at least 2% by weight, based on the weight of carbon in the composite material
  • 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 10 nm and / or the oxide and / or (semi-) metallic phase essentially forms phase domains with an average diameter (the arithmetic mean of the diameters) of at most 20 ⁇ m, determined by means of small-angle X-ray scattering.
  • electroactive material according to the invention as electrodes in electrochemical cells and electrodes for electrochemical cells containing the electroactive material according to the invention.
  • electrochemical cells comprising an electrode containing the electroactive material according to the invention, their use in a lithium-ion battery and in a device and devices and lithium-ion batteries containing an electrochemical cell according to the invention, subject of this invention.
  • the process according to the invention has a number of advantages. Particularly noteworthy are the easily accessible starting materials, the variety of usable educts and the flexibility in terms of the composable materials. That's the way to do it
  • the properties of the organic polymer phase by copolymerizing different compounds I, which differ in the nature of the aryloxy group.
  • the properties of the (semi-) metal-containing phase can be achieved by simultaneous use of compounds I, which are different (semi-) metals or non-metals, in combination with at least one compound III, which contains one or more (semi-) metals control.
  • phase domain For a definition of the term “phase”, reference may be made to the book AD McNaught and A. Wilkinson: IUPAC Compendium of Chemical Terminology, 2nd Edition, Blackwell Scientific Publications, Oxford, Version 2.3.1 (2012) 1062. The terms will continue to be used "Phase domain” and “co-continuous,” “discontinuous,” and “continuous phase domain.” Their detailed description is in WJ 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.
  • a co-continuous arrangement of a two-component mixture is understood to mean a phase-separated arrangement of the two phases or components, wherein within a domain of the respective phase, each region of the Phase interface of the domain can be interconnected by a continuous path without the path passes through / crosses a phase interface.
  • (half) MetaH in the sense of this invention stands for “metal and / or half metaH”; analogously, "(semi-) metallic” stands for “metallic and / or semimetallic.”
  • Oxidic stands for a chemical entity which contains (semi-) metal and oxygen, whereby different bonding forms, eg, oxides, hydroxides or Mixed shapes are possible, and stoichiometry can also vary widely, such as forms with a low oxygen content, for example less than 10, less than 7 or less than 5% by weight, based on the weight of the composite material, as well as shapes which are approximately equal to stoichiometric composition of defined compounds, such as SnO or Fe203 correspond H20 *, and shapes with a high oxygen content, z. B. 15, about 20 or about 25 wt .-% based on the weight of the composite material.
  • alkyl alkenyl
  • cycloalkyl alkoxy
  • cycloalkoxy aryl
  • Alkyl is a saturated, linear or branched hydrocarbon radical which typically has 1 to 20, frequently 1 to 10 and in particular 1 to 4 carbon atoms and which is, 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-methylpentyl 3-yl, 3-methylpentyl, 2,2-dimethylbutyl, 2,2-dimethylbutyl, 2,2-dimethylbut
  • Alkenyl is an olefinically unsaturated, linear or branched hydrocarbon radical which typically has 2 to 20, often 2 to 10 and especially 2 to 6 carbon atoms and which is, 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,
  • Alkoxy is an alkyl radical bound via an oxygen atom, as defined above, which typically has 1 to 20, frequently 1 to 10 and in particular 1 to 4 carbon atoms and which is, for example, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec Butoxy, isobutoxy, tert-butoxy, n-pentyloxy, 2-methylbutyloxy, 3-methylbutyloxy, n-hexyloxy, n-heptyloxy, n-octyloxy, 1-methylheptyloxy, 2-methylheptyloxy, 2-ethylhexyloxy, n -nonyloxy, 1 - methylnonyloxy, n-decyloxy or 3-propyl heptyloxy.
  • Cycloalkyl is a mono-, bi- or tricyclic, saturated cycloaliphatic radical which typically has 3 to 20, often 3 to 10 and in particular 5 or 6 carbon atoms and which, 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] hept-7-yl, bicyclo [2.2.2] octan-1-yl , Bicyclo [2.2.2] octan-2-yl, 1-adamantyl or 2-adamantyl.
  • Cycloalkyloxy represents a mono-, bi- or tricyclic, saturated cycloaliphatic radical bonded via an oxygen atom, which has typically 3 to 20, often 3 to 10 and in particular 5 or 6 carbon atoms and which is, for example, cyclopropyloxy, cyclobutyloxy, cyclopentyloxy, cyclohexyloxy, cycloheptyloxy , Cyclooctyloxy, bicyclo [2.2.1] hept-1-yxyloxy, bicyclo [2.2.1] hept-2-yloxy, bicyclo [2.2.1] hept-7-yloxy, bicyclo [2.2.2] octane-1 -yloxy, bicyclo [2.2.2] octan-2-yloxy, 1-adamantyloxy or 2-adamantyloxy.
  • Aryl stands for an aromatic hydrocarbon radical.
  • the aromatic hydrocarbon radical may carry substituents. It is preferably unsubstituted.
  • Aryl is, for example, phenyl, 1-naphthyl or 2-naphthyl.
  • Aryloxy groups contain a negatively charged oxygen atom obtained by deprotonation of the hydroxyl groups of aromatic monohydroxyaromatics (e.g., those mentioned below).
  • the inventive method comprises the copolymerization of compound I with
  • compound I is at least one aryloxy (semi-) metalate and / or aryloxy ester of a non-metal oxo-acid-forming metal, the nonmetal being different from carbon and nitrogen.
  • aryloxy (semi-) metalates or “aryloxy esters” is meant compounds which formally one or more - in particular 1, 2, 3, 4, 5 or 6 - aryloxy groups and a metal, metalloid or non-metal which forms oxo acids , exhibit.
  • the non-metal is different from carbon and nitrogen.
  • Each aryloxy group is linked via the deprotonated oxygen atom to a metal, metalloid or non-metal which forms oxo acids and is different from carbon and nitrogen.
  • Form oxo acids and are different from C and N are also referred to as
  • aryloxy radical (s) may be bound to the central atom (s), for example 1, 2 or 3 organic radicals, e.g. are selected from alkyl, alkenyl, cycloalkyl or aryl, or 1 or 2 oxygen atoms.
  • Compound I may have one or more central atoms and, in the case of several central atoms, linear, branched, monocyclic or polycyclic structures.
  • Suitable monohydroxyaromatics are, above all, phenol, a-naphthol and .beta.-naphthol, which are unsubstituted, ie, other than the hydroxyl group, other than hydrogen other than benzene.
  • Naphthalene ring have bound atoms, or a single or multiple - eg 1, 2, 3 or 4 - substituents other than hydrogen.
  • substituents are in particular alkyl, cycloalkyl, alkoxy, cycloalkoxy and N RaRb groups in which Ra and Rb independently of one another represent a hydrogen atom, an alkyl or cycloalkyl radical.
  • the total number of bound groups is typically determined by the valence of the central atom, ie the metal, semi-metal or non-metal to which these groups are bound.
  • the central atoms of compound I of carbon and nitrogen are different elements of the following groups of the periodic table (for the entire invention, the IUPAC convention valid in 201 1 is used):
  • Group 1 (mainly Li, Na or K), Group 2 (mainly Mg, Ca, Sr or Ba), Group 4 (including mainly Ti or Zr), Group 5 (mainly V), Group 6 (especially Cr, Mo or W), group 7 (especially Mn), group 13 (mainly B, Al, Ga or In), group 14 (mainly Si, Ge, Sn or Pb), Group 15 (mainly P, As or Sb) and Group 16 (including especially S, Se or Te).
  • Preferred as the central atom of the compound I is an element other than carbon and nitrogen of the groups 4, 13, 14 or 15 of the periodic table and hereunder in particular from the 2nd, 3rd and 4th period.
  • the central atoms are particularly preferably selected from B, Al, Si, Sn, Ti and P.
  • one or more aryloxy-half-metalates are used, i. Compounds of semimetals such as B or Si.
  • the compound I contains aryloxy-half-metalates in which the semimetal is at least 90 mol%, based on the total amount of semimetal atoms, of silicon.
  • M for a metal, semi-metal or for an oxo acid-forming, of carbon
  • n 1 or 6
  • n is an integer and 0, 1 or 2
  • p is an integer and 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 and corresponds to the valency of M. .
  • Ary is phenyl or naphthyl, wherein the phenyl ring or the naphthyl ring
  • each other are hydrogen, alkyl or cycloalkyl
  • R is hydrogen, alkyl, alkenyl, cycloalkyl or aryl, where aryl is unsubstituted
  • R a and Rb have the meanings given above.
  • radicals Ary may be the same or different, wherein different Ary may differ in the type of the aromatic ring and / or in the nature of the substitution pattern.
  • radicals R may be the same or different.
  • Formula I is to be understood as so-called gross formula; it indicates the type and number of the structural units characteristic of the compound I, namely the central atom M and the groups attached to the central atom, ie the aryloxy group AryO, oxygen atoms O and the carbon-bonded radicals R, and the number of these units.
  • the units [(AryO) mMO n Rp] can form q greater than 1 mono-, polycyclic, or linear structures.
  • M is a metal or semimetal or a non-metal other than carbon or nitrogen which forms oxo acids, the metals, semi-metals and non-metals being selected, as a rule, from the elements other than nitrogen and carbon of the following groups of the periodic table:
  • M is an element selected from among elements other than carbon and nitrogen of groups 4, 13, 14 and 15 of the periodic table, in particular for a second, third and fourth period element. Particularly preferred for M are B, Al, Si, Sn, Ti and P. In a very particularly preferred embodiment of the invention, M is B or Si and especially Si.
  • p in formula I is 0, i. the
  • p in formula I is 1 or 2
  • the atom M carries at least one radical R.
  • the process comprises the copolymerization of compound I with compound II in the presence of compound III, ie it is also possible to use two or more aryloxy (semi-) metalates and / or aryloxy esters of a non-metal oxo acid, the nonmetal being different from carbon and nitrogen, be used.
  • a preferred method is to use at least two aryloxy (semi-) metalates and / or aryloxy esters of a non-metal oxo acid, wherein the nonmetal is different from carbon and nitrogen.
  • variable p 0 and in at least one further compound of the formula I the variable p may be greater than or equal to 1.
  • the compound of the formula I preferably contains MB, Si, Sn, Ti or P and in particular B, Si or Sn, where m is 1, 2, 3 or 4, n is 0 or 1, in particular 0, p is 0 and q are 0, 1, 3 or 4.
  • the second compound of formula I has for M Si or Sn, where m is 2, n is 0, q is 0 and p is 1 or 2.
  • Ary in these two compounds of the formula I may be identical or different, where Ary has the meanings mentioned above and in particular the preferred meanings and in particular represents phenyl which is unsubstituted or may have 1, 2 or 3 substituents which are alkyl, in particular C 1 -C 4 -alkyl, and alkoxy, in particular C 1 -C 4 -alkoxy.
  • R then preferably represents C 1 -C 6 -alkyl, C 3 -C 10 -cycloalkyl or phenyl, in particular C 1 -C 4 -alkyl, C 5 -C 6 -cycloalkyl or phenyl.
  • one of the two compounds of the formula I contains M Si, 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 the formula I has as M Si, m is equal to 2, n is 0 and p is 1 or 2.
  • Ary in the two compounds of formula I may be the same or different, wherein Ary has the meanings mentioned above and in particular the preferred meanings, and in particular is phenyl which is unsubstituted or may have 1, 2 or 3 substituents which are selected from alkyl, in particular C 1 -C 4 -alkyl and alkoxy, in particular C 1 -C 4 -alkoxy.
  • R then preferably represents C 1 -C 6 -alkyl, C 3 -C 10 -cycloalkyl or phenyl, in particular C 1 -C 4 -alkyl, C 6 -C 12 -cycloalkyl or phenyl.
  • n is an integer and stands for 2, 3 or 4;
  • n is an integer and stands for 0 or 1;
  • p is an integer and represents 0, 1 or 2;
  • alkyl under alkyl, preferably Ci-C4-alkyl, particularly preferably methyl, cycloalkyl, in particular C3-Cio-cycloalkyl, alkoxy, preferably Ci-C4-alkoxy, particularly preferably methoxy, cycloalkoxy, in particular C3-Cio-cycloalkoxy, and NRaRb selected in which Ra and Rb independently of one another are hydrogen, alkyl, in particular C 1 -C 4 -alkyl, preferably methyl, or cycloalkyl, in particular C 3 -C 10 -cycloalkyl;
  • R d-Ce-alkyl C 2 -C 6 alkenyl, C 3 -Cio cycloalkyl or phenyl, especially Ci-C4-alkyl, Cs-Ce cycloalkyl, or phenyl.
  • variables m, n, p, Ary and R in formula I taken alone or in combination, and in particular in combination with one of the preferred and particularly preferred meanings of M, preferably have the following meanings: m is an integer and stands for 2, 3 or 4; n is an integer and stands for 0;
  • p is an integer and represents 0, 1 or 2;
  • a preferred embodiment of the compound I are compounds of the formula I in which q is the number 1. Such compounds can be regarded as ortho-esters of the central atom M underlying oxo-acid.
  • the variables m, n, p, M, Ary and R have the abovementioned meanings and in particular, alone or in combination and especially in combination, one of the preferred or particularly preferred meanings.
  • compound I may be a compound of formula I wherein 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 and q is equal to 1.
  • Ary has the meanings mentioned above and in particular the preferred meanings and is in particular phenyl which is unsubstituted or may have 1, 2 or 3 substituents which are alkyl, in particular C 1 -C 4 -alkyl, and alkoxy, in particular C 1 -C 4 -alkyl. Alkoxy, are selected.
  • a most preferred embodiment of compound I are those compounds of formula I wherein M is B, Si or Ti, m is 3 or 4, n is 0, p is 0, 1 or 2 and q is 1.
  • M is B, Si or Ti, m is 3 or 4, n is 0, p is 0, 1 or 2 and q is 1.
  • this Ary has the meanings mentioned above and in particular the preferred meanings and in particular represents phenyl which is unsubstituted or may have 1, 2 or 3 substituents which are alkyl, in particular C 1 -C 4 -alkyl and alkoxy, in particular C 1 -C 4 -alkoxy , are selected.
  • a specific 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.
  • M is Si
  • m is 4, n is 0 and p is 0, 1 or 2.
  • Ary has the meanings mentioned above and in particular the preferred meanings and is in particular phenyl which is unsubstituted or may have 1, 2 or 3 substituents which are alkyl, in particular C 1 -C 4 -alkyl, and alkoxy, in particular C 1 -C 4 -alkyl. Alkoxy, are selected.
  • Tetraphenyltitanat Tetrakresyltitanat, tetraphenylstannate and triphenylaluminate.
  • Further embodiments of the compound I are those compounds of the general formula I in which the radicals Ary are different from one another. This generally lowers the melting point of the compound I, which may offer advantages in the polymerization.
  • inventively preferred compounds of the formula I having different aryl are triphenoxy- (4-methylphenoxy) silane, diphenoxy-bis (4-methylphenoxy) silane, triphenoxy- (4-methylphenoxy) silane, diphenoxy-di (4-methylphenoxy) silane, borate diphenyl (4-methylphenyl), Triphenyl (4-methylphenyl) titanate and diphenyl bis (4-methylphenyl) titanate and mixtures thereof.
  • compound I Another specific embodiment of compound I are those compounds of formula I wherein M is Si, m is 1, 2 or 3, n is 0 and p is 4 - m.
  • Ary has the meanings mentioned above and in particular the preferred meanings and is in particular phenyl which is unsubstituted or may have 1, 2 or 3 substituents which are alkyl, in particular C 1 -C 4 -alkyl, and alkoxy, in particular C 1 -C 4 -alkyl. Alkoxy, are selected.
  • R has the meanings described for formula I; in particular R is hydrogen, methyl, ethyl, phenyl, vinyl or allyl.
  • Examples of preferred compounds I of this embodiment are diphenoxysilane, diphenoxymethylsilane, triphenoxysilane, methyl (triphenoxy) silane, dimethyl (diphenoxy) silane, trimethyl (phenoxy) silane, phenyl (triphenoxy) silane and diphenyl (diphenoxy) silane.
  • -A- represents a group M (AryO) m -2 (0) n (R) p, where M, Ary and R have the meanings given above,
  • n is an integer and stands for 3 or 4,
  • n is an integer and stands for 0 or 1 and in particular 0,
  • p is an integer and 0, 1 or 2 means
  • m + 2n + p is an integer, stands for 3, 4, 5 or 6 and corresponds to the valency of M.
  • M in the formula I is Si, Sn, B and P.
  • the condensation product is cyclic and q
  • (AO) k k is 1, 2 or 3 and -A- is a group M (AryO) m-2 (0) n (R) p.
  • M, Ary and R have the meanings given above for formula I and m, n and p satisfy the conditions given previously in
  • condensation product is linear and saturated at the ends with an AryO unit.
  • AryO unit such compounds can be described by the following structure Ic:
  • Ary - [- 0-A-] q -OAry (Ic) q is an integer in the range of 2 to 20 and -A- is a group
  • M (AryO) m-2 (O) n (R) p in which M, Ary and R have the meanings given above for formula I and m, n and p have the meanings given above in connection with formula I.
  • condensation products are triphenylmetaborate, hexaphenoxycyclotrisiloxane, octaphenoxycyclotetrasiloxane, triphenoxycyclotrisiloxane or tetraphenoxycyclotetrasiloxane.
  • Compound I is known or can be prepared in analogy to known methods for the preparation of phenates, see e.g. DE 1816241, Z. Anorg. Gen. Chem. 551 (1987) 61-66, Z. Chem. 5 (1965) 122-130 and Houben-Weyl, Vol. VI-2 35-41.
  • the process comprises the copolymerization of at least one compound I with at least one compound II.
  • Compound II is at least one ketone, such as acetone, an aldehyde, such as furfural, or an aldehyde equivalent, such as trioxane. These compounds are generally capable of forming polymeric structures with phenols under condensation. In a preferred embodiment, the compound II is formaldehyde or a formaldehyde equivalent or a mixture thereof.
  • compounds of different formaldehyde equivalents can also be co-polymerized.
  • the polymerization is carried out using the compound II (hereinafter also called formaldehyde source), which is selected from at least one gaseous formaldehyde, trioxane and / or paraformaldehyde. In particular, it is trioxane.
  • Greater excesses of formaldehyde are usually not critical, but not necessary, so that one typically uses formaldehyde or the formaldehyde equivalent in an amount such that the molar ratio of formaldehyde or the molar ratio of the formaldehyde contained in the formaldehyde equivalent to those in the Compound I aryloxy AryO present does not exceed a value of 10: 1, preferably 5: 1 and in particular 2: 1.
  • formaldehyde or the formaldehyde equivalent in an amount such that the molar ratio of formaldehyde or the molar ratio of the formaldehyde contained in the formaldehyde equivalent to the aryloxy groups AryO present in the compound I is in the range from 1: 1 to 10: 1, in particular in the range of 1, 01: 1 to 5: 1 and especially in the range of 1, 05: 1 to 5: 1 or 1, 1: 1 to 2: 1.
  • a formaldehyde equivalent is meant a compound which releases formaldehyde under polymerization conditions.
  • the formaldehyde equivalent is preferably an oligomer or polymer of formaldehyde, ie a substance having the empirical formula (CH 2 O) X , where x denotes the degree of polymerization.
  • formaldehyde equivalent include, in particular, trioxane (3 formaldehyde units) and paraformaldehyde, which typically contains 8 to 100 formaldehyde units.
  • the compound III is at least one (semi-) metal compound which is not aryloxy (semi-) metalate.
  • the at least one (semi-) metal compound may be both purely inorganic in nature, for.
  • a halide sulfate, nitrate or phosphate of a (half) metal, as well as covalent nature, z.
  • an alkanoate or alkoxide of a (half) metal As an alkanoate or alkoxide of a (half) metal.
  • the (semi-) metal contained in compound III is in particular an element of group 1 (preferably above all Na, K), group 2 (preferably above all Ca, Mg), group 3 (preferably above all Sc), group 4 (preferred especially Ti, Zr), group 5 (preferably especially V), group 6 (preferably especially Cr, Mo, W), group 7 (preferably especially Mn), group 8 (preferably especially Fe, Ru, Os) , Group 9 (preferably above all Co, Rh, Ir), group 10 (preferably above all Ni, Pd, Pt), group 11 (preferably above all Cu, Ag, Au), group 12 (preferably above all Zn, Cd ), Group 13 (preferably above all B, Al, Ga, In), group 14 (preferably above all Si, Sn) and group 15 (preferably above all As, Sb, Bi) of the Periodic Table.
  • group 1 preferably above all Na, K
  • group 2 preferably above all Ca, Mg
  • group 3 preferably above all Sc
  • group 4 preferred especially Ti, Zr
  • group 5 preferably especially V
  • group 6 preferably especially
  • the (semi-) metals Ti, V, Cr, Mo, W, Mn, Fe, Co, Ni, Cu, Zn, B, Si and / or Sn and particularly preferably the (semi-) metals Ti, Fe, Co, Cu, Si and / or Sn.
  • the inorganic (half) metal compounds include (semi) metal halides, which halides can be selected from fluoride, chloride, bromide, iodide and astatine and mixtures and hydrates thereof.
  • the preferred (semi) metal halides used are TiCl, CrCl 3, MnC, FeC, FeCl 3, C0CI2, NiC, ZnC, CuC. SnC and / or SnCl 4 , in particular TiCl 4 , FeC, C0Cl 2, CuC, SnC and / or SnCl 4 .
  • Other embodiments are (semi) metal sulfates, nitrates, phosphates or carbonates.
  • sulfates here generally for oxoanions of sulfur (eg S0 4 2 “ , SO3 2” , S2O3 2 “ ),” nitrates “for oxo anions of nitrogen (eg NO3, NO2 " ), “phosphates” for oxoanions of phosphorus and “Carbonates” for oxoanions of carbon.
  • (semi-) metal sulfates or nitrates 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 , ZnS0 4 , and / or Sn (N0 3 ) 2 .
  • compound III contains a (semi-) organometallic compound
  • the anions contained in the (semi-) organometallic compound are, for example, carboxylates (preferably above all acetate, butanoate, propanoate, palmitate, citrate, oxalate, acrylate), Alko- xylate (as described above, preferably especially methoxylate, ethoxylate, n-propoxylate, isopropoxylate, n-butoxylate, sec-butoxylate, isobutoxylate and tert-butoxylate) and thiolates (especially methanethiolate, ethanethiolate, propanethiolate, butanethiolate, especially carboxylates and alkoxylates are used, preferably acetate, methoxylate or ethoxylate
  • the preferably used (semi-) organometallic compounds are Fe (CH 3 COO) 2, Zn (CH 3 COO) 2,
  • the preferred compounds used for the compound III are Fe (CH 3 COO) 2, C0Cl 2, CuCl 2 , SnCl 2 , FeCl 3 , Si (OCH 3 ) 4 , TiCl 4 and / or SnCl 4 .
  • compound III is used in an amount such that the weight of the (semi-) metal of compound III is at least 5% by weight, usually more than 5% by weight, in particular at least 10% by weight, preferably at least 15 wt .-% and particularly preferably at least 20 wt .-%, based on the weight of the compound I.
  • the polymerization of compound I with the formaldehyde source, compound II can be carried out in the presence of catalytic amounts of an acid.
  • the acid is used in an amount of 0.1 to 10 wt .-%, in particular 0.2 to 5 wt .-%, for example up to a maximum of 4 or 3 or 2 or 1 wt .-% based on the weight of the compound I am one.
  • Preferred acids are Bronsted acids, for example organic carboxylic acids such as trifluoroacetic acid, oxalic acid and lactic acid and also organic sulfonic acids.
  • C 1 -C 20 -alkanesulfonic acids such as methanesulfonic acid, octanesulfonic acid, decanesulfonic acid and dodecanesulfonic acid, and haloalkanesulfonic acids such as trifluoromethanesulfonic acid.
  • benzenesulfonic acid or C 1 -C 20 -alkylbenzenesulfonic acids such as toluenesulfonic acid, nonylbenzenesulfonic acid and dodecylbenzenesulfonic acid is possible.
  • inorganic Bronsted acids such as HCl, H 2 SO 4 or HClO 4 .
  • Lewis acid especially BF3, BCl3, SnCl 4, TiCl 4, and AlCl 3 may be preferably used.
  • the use of complexed or dissolved in ionic liquids Lewis acids is also possible.
  • the polymerization can also be catalyzed with bases.
  • bases for example, alcoholates, hydroxides, phosphates, carbonates and / or bicarbonates of alkali metals and / or alkaline earth metals as well as ammonia and / or primary, secondary and / or tertiary amines can be used as well as mixtures thereof.
  • bases are Na-methylate, Na-ethylate, K-tert-butylate or Mg-ethylate, NaOH, KOH, LiOH, Ca (OH) 2 , Ba (OH) 2 , Na 3 PO 4 , Na 2 CO 3 , K 2 C0 3 , Li 2 C0 3 , (CH 3 ) 3 N, (C 2 H 5 ) 3 N, morpholine, dimethylaniline and piperidine.
  • the base 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 a maximum of 4 or 3 or 2 or 1% by weight, based on the weight of the compound I am one.
  • Catalysts will be used for economic reasons only in the amount necessary for catalysis, typically at most 10 wt .-%, for example at most 4 or 3 or 2 or 1 wt .-%, based on the weight of the compound I. (half) metal-containing Acids and bases can also be used as compound III. In this case, they are used in the amounts mentioned for compound III.
  • the polymerization can also be initiated thermally, i. the polymerization is preferably carried out in the case without the addition of a catalytic amount of acid or base by heating a mixture of the compound I and the compound II in the presence of compound III.
  • the temperatures required for the polymerization are typically in the range of 50 to 250 ° C, in particular in the range of 80 to 200 ° C.
  • the polymerization temperatures are typically in the range from 50 to 200 ° C. and in particular in the range from 80 to 150 ° C.
  • the polymerization temperatures are typically in the range of 120 to 250 ° C and especially in the range of 150 to 200 ° C.
  • the polymerization according to the invention can in principle be carried out under a reduced pressure compared to normal pressure, for example under reduced pressure, under atmospheric pressure or under elevated pressure, for example in a pressure autoclave.
  • the polymerization 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 more preferably in the range from 0.7 up to 2 bar.
  • the polymerization can in principle be carried out in a batch and / or addition process.
  • the compounds I, II and III are introduced in the desired amount in the reaction vessel and brought to the conditions required for the polymerization.
  • the addition process at least one of the compounds I and II is at least partially fed in the course of the polymerization until the desired ratio of compound I to compound II is reached.
  • the compound III can be submitted and / or added in the course of the polymerization.
  • the addition is followed by a post-reaction phase. Preference is given to carrying out the batch process.
  • the polymerization is carried out as a batch with the total amount of the compounds 1, 11 and III or it works by an addition process in which the addition of the compounds I and II is carried out so that the polymerization conditions are not interrupted until the total amount of the compounds I and
  • Compound III can be initially charged and / or fed in the course of the polymerization.
  • the polymerization of the compounds I and II in the presence of the compound III can in principle be carried out in any desired way, as long as it is ensured that the components can react with one another.
  • the reaction can therefore be carried out in bulk, for example in a melt, or in the presence of a reaction medium, in particular a solvent.
  • Suitable solvents are, in principle, all solvents in which the compound III is at least partially present in dissolved form. This is understood to mean that the solubility of compound III in the solvent under polymerization conditions is at least 50 g / l, in particular at least 100 g / l.
  • the solvent is chosen so that the solubility of the compound III at atmospheric pressure and 20 ° C is 50 g / l, in particular at least 100 g / l.
  • the solvent is chosen such that compound III is substantially or completely soluble, i. the ratio of solvent to the compound III is chosen so that under polymerization at least 80 wt .-%, in particular at least 90 wt .-%, based on the weight of the compound III, or the completely used amount of the compound III are dissolved.
  • the polymerization is carried out in a solvent, wherein at least 60 wt .-%, preferably at least 75 wt .-%, more preferably at least 90 wt .-% and most preferably at least 95 wt .-% of the total amount of the compounds I, II and III are present in dissolved form.
  • Preferred solvents are alcohols, ethers and ketones, in particular alcohols, ethers and ketones having 1 to 8 carbon atoms.
  • suitable alcohols are methanol, ethanol, n- and iso-propanol, n-, sec-, iso- and tert-butanol, a pentanol and a hexanol.
  • cyclic preferably above all dioxane, tetrahydrofuran
  • acyclic ethers such as methyl ethyl ether, dimethyl ether, diethyl ether, methyl tert-butyl ether, diisopropyl ether and di-n-butyl ether.
  • suitable cyclic or acyclic ketones are acetone, butanone or cyclohexanone. Particularly preferred as the solvent is THF and ethanol.
  • the concentration of water at the beginning of the polymerization is less than 1 wt .-%, preferably less than 0.5 wt .-% and particularly preferably less than 0.1 wt .-% based on the total weight of the fertilize I, II and III.
  • the polymerization particularly preferably takes place in the absence of water, ie anhydrous.
  • inert diluents are those which are at least 80% by volume, in particular at least 90% by volume and especially at least 99% by volume or 100% by volume, based on the total amount of diluent, of the abovementioned Hydrocarbons, aromatic hydrocarbons such as one or more Ci-C-4-alkyl-substituted benzene or naphthalene, preferably especially toluene, xylene, cumene or mesitylene or Ci-C-4-alkylnaphthalenes, furthermore aliphatic and cycloaliphatic hydrocarbons such as hexane, cyclohexane , Heptane, cycloheptane, octane and its isomers, nonane and its isomers, decane and its iso
  • the polymerization of compound I with compound II in the presence of compound III may be followed by purification steps and optionally drying steps.
  • the composition of the inorganic phase is changed.
  • This can be used advantageously bases, z.
  • bases, z As alcoholates, hydroxides, phosphates, carbonates and / or bicarbonates of alkali metals and / or alkaline earth metals, and ammonia and / or primary, secondary and / or tertiary amines and mixtures thereof.
  • bases are Na-methylate, Na-ethylate, K-tert-butylate or Mg-ethylate, NaOH, KOH, LiOH, Ca (OH) 2 , Ba (OH) 2, Na 3 PO 4 , Na 2 CO 3 , K 2 C0 3 , U 2 CO 3 , NaHCOs, KHCOs, (CH 3 ) 3 N, (C 2 H 5 ) 3 N, morpholine, dimethylaniline and piperidine.
  • bases can also be used in a solvent such as water, alcohols or ethers or mixtures thereof, for example in methanol, ethanol, isopropanol, diethyl ether or THF.
  • the composite material obtained by the method of the present invention can be heated. This is usually carried out at temperatures in the range of 200 to 2000 ° C, preferably in the range of 300 to 1600 ° C, more preferably in the range of 400 to 1 100 ° C and most preferably in the range of 500 to 900 ° C. ,
  • carbonation is carried out at temperatures in the lower region, for. B. below 600 ° C, below 500 ° C or, for example, from 380 to 400 ° C. With this procedure one can obtain wide ranges of the co-continuous structures.
  • carbonization is carried out at temperatures in the higher range, for. B. above 700 ° C, above 800 ° C or for example from 950 to 1050 ° C. With this procedure, it is possible to produce isolated metal domains in a carbon matrix in a wide range, it being advantageous to use reducing gases.
  • the duration of heating is variable and depends inter alia on the temperature to be heated. The time period is, for example, between 0.5 and 50 h, preferably between 1 and 24 h, in particular between 2 and 12 h.
  • the heating can be carried out in one or more stages, for example in one or two stages. In many cases, it is heated at a rate of 1 ° to 10 ° C / min, preferably 2 ° to 6 ° C / min, for example, at 2 °, 3 ° or 4 ° C / min, up to the desired temperature. Cooling can be started immediately after this temperature has been reached, or this temperature can be maintained for 10 minutes to 10 hours. This holding time can z. B. 0.5 h, 1 h, 2 h, 3 h, 4 h or 5 h. Before the carbonization process, an annealing step can also be added.
  • the heating can be carried out with substantial or complete exclusion of oxygen, preferably in the presence of inert gases and / or reducing gases (reactive gases).
  • the organic polymeric material formed in the polymerization is carbonized to the carbon phase and electroactive material is formed.
  • the polymerization is carried out in one stage, under extensive or complete, preferably complete, exclusion of oxygen at atmospheric pressure.
  • Complete exclusion of oxygen in this context means that in the gas space in which the polymerization takes place, not more than 0.5 vol .-%, preferably less than 0.05 vol .-%, in particular less than 0.01 vol. -% oxygen, based on the mentioned gas space, are present.
  • the steps may be carried out in the presence of different gases and / or at different temperatures.
  • an inert gas such as argon or nitrogen heated
  • a reducing gas reactive gas
  • Ar reactive gas
  • N2, H2, NH3, CO and C2H2 and their mixtures such as synthesis gas (CO / H2) and forming gas (N2 / H2 and / or Ar / H2) are heated.
  • Polymerization of compound I with compound II in the presence of compound III may be followed by oxidative removal of the organic polymer phase so that the organic polymeric material formed in the polymerization of the organic constituents is oxidized to yield a nanoporous oxidic material.
  • the heating is carried out under oxygen, in a preferred form in the presence of inert gases.
  • the steps in the presence of different gases and / or at different temperatures are performed. For example, first, for example in a first step, in the presence of an inert gas such as argon or nitrogen and then, for example in a second step, in the presence of a oxidizing gas such as O2, and mixtures thereof, such as air or synthetic air, are heated.
  • the heating of the composite material obtained by the polymerization can in principle be carried out under reduced pressure, for example in vacuo, under normal pressure or under elevated pressure, for example in a pressure autoclave.
  • 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 0.7 to 2 bar.
  • the heating may be carried out in a closed system or in an open system in which evolved volatiles are removed in a gas stream which preferably contains at least one inert gas and / or reducing gas.
  • the method according to the invention is suitable for producing electroactive material in a continuous and / or discontinuous mode of operation.
  • batchwise operation this means batch sizes over 10 kg, preferably greater than 100 kg, particularly preferably greater than 1000 kg or greater than 5000 kg.
  • production quantities over 100 kg / day, preferably over 1000 kg / day, particularly preferably over 10 t / day or over 100 t / day.
  • composite material (K1) which can be prepared, for example, by the method of the invention and which contains
  • 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 at least one organic polymer phase having at least one (semi-) metal-containing phase forms phase domains, the average Distance (the arithmetic mean of the distances), determined by means of small angle X - ray scattering, of two adjacent domains of identical phases in the
  • the at least one (semi-) metal-containing phase contains at least two different (semi-) metals.
  • identical phases are meant on the one hand only organic polymer phases, on the other hand exclusively (semi-) metal-containing phases.
  • adjacent phase domains of identical phases is meant two phase domains of identical phase separated by a phase domain of the other phase, thus preferably two phase domains of the (semi-) metal-containing phase separated by a phase domain of the organic polymer phase, or two phase domains of the polymer phase separated by a phase domain of the (semi-) metal-containing phase.
  • the average spacing of adjacent phase domains of identical phases is typically at most 200 nm, often at most 100 nm or at most 50 nm and especially at most 10 nm or at most 5 nm.
  • the average distance between the domains of adjacent identical phases can be determined by X-ray small angle X-ray scattering Scattering (SAXS)) are determined via the scattering vector q (measurement in transmission at 20 ° C, monochromatized CuK radiation, 2D detector (image plate), slit collimation).
  • SAXS X-ray small angle X-ray scattering Scattering
  • the size of the phase regions and thus the distances between adjacent phase boundaries and the arrangement of the phase can also be determined by transmission electron microscopy (TEM), in particular by HAADF-STEM (high angle annular darkfield scanning electron microscopy) technique.
  • TEM transmission electron microscopy
  • HAADF-STEM high angle annular darkfield scanning electron microscopy
  • the (semi-) metal-containing phase can in principle contain any element which forms oxidic structures.
  • the oxides of (semi-) metals particularly preferably the elements of group 1 (preferably above all Na, K), group 2 (preferably above all Ca, Mg), group 3 (preferably above all Sc), group 4 (preferably above all Ti, Zr), group 5 (preferably above all V), 6 (preferentially above all Cr, Mo, W), group 7 (preferentially above all Mn), group 8 (prefers above all Fe, Ru, Os) , Group 9 (preferably above all Co, Rh, Ir), group 10 (preferably above all Ni, Pd, Pt), group 11 (preferably above all Cu, Ag, Au), group 12 (preferably above all Zn, Cd ), Group 13 (preferably especially B, Al, Ga, In), group 14 (preferably especially Si, Sn) and group 15 (preferably especially As, Sb, Bi) of the Periodic Table.
  • group 1 preferably above all Na, K
  • group 2 preferably above all Ca, Mg
  • each (semi-) metal in the composite material (K1) according to the invention is at least 2 wt .-%, preferably at least 3 wt .-%, more preferably at least 5 wt .-% based on the carbon content of the composite material.
  • the regions in which co-continuous phase domains occur are preferably at least 10% by volume, more preferably at least 30% by volume, most preferably at least 50% by volume, most preferably at least 70% Vol .-%, in particular at least 80 vol .-% to a maximum of 100 vol .-% of the composite material.
  • the composite material (K1) according to the invention can easily be further processed into the electroactive material according to the invention, which can be used in particular for electrodes of electrochemical cells.
  • a composite material (electroactive material) which has a) at least one carbon phase and
  • b) contains at least one oxidic and / or (semi-) metallic phase
  • each (semi) metal of the electroactive material is at least 2% by weight, based on the weight of carbon in the electroactive material, at least one oxide and / or (semi-) metallic phase and at least one carbon phase form phase domains
  • the average Distance (the arithmetic mean of the distances) of two adjacent domains of identical phases, determined with the aid of longitudinal narrow angle scattering is substantially at most 10 nm and / or the at least one oxidic and / or (semi-) metallic phase phase domains having an average diameter (arithmetic average diameter) of a maximum of 20 ⁇ m, determined by means of small-angle X-ray scattering.
  • the at least one oxidic and / or (semi-) metallic phase contains at least two different (semi-) metals.
  • identical phases are meant on the one hand exclusively carbon phases, on the other hand exclusively oxidic and / or (semi-) metallic phases.
  • adjacent phase domains of identical phases is meant two phase domains of identical phase separated by a phase domain of the other phase, thus preferably two phase domains of carbon phases separated by a phase domain of an oxide and / or (semi-) metallic phase or two phase domains of oxide and / or (semi-) metallic phases separated by a phase domain of the carbon phase.
  • the average spacing of adjacent phase domains of identical phases is typically at most 10 nm, often at most 7 nm, in particular at most 5 nm and preferably at most 3 nm.
  • the oxidic and / or (semi-) metallic phase domains typically have an average diameter of at most 20 ⁇ m, preferably of not more than 2 ⁇ m, very particularly preferably not more than 500 nm, in particular not more than 100 nm.
  • the average distance between the domains of adjacent identical phases and the average diameter of the at least one oxidic and / or (semi-) metallic phase can be determined by means of HAADF-STEM or by means of small angle X-ray scattering over the scattering vector q (measurement in transmission at 20 ° C , monochromatized CuK radiation, 2D detector (Image Plate), slit collimation) are determined.
  • the regions in which co-continuous phase domains occur are preferably at least 10% by volume, more preferably at least 30% by volume, most preferably at least 50% by volume, most preferably at least 70% by volume. -%, In particular at least 80 vol .-% to 100 vol .-% based on the total volume of the electroactive material.
  • the at least one oxidic and / or (semi-) metallic phase may, in principle, contain, for the oxide phase, any element which forms oxides.
  • Preferred for the at least one oxidic and / or (semi-) metallic phase are oxides of (semi-) metals and / or (semi-) metals, particularly preferably the oxides of the (semi-) metals and / or the (semis -) metals of the elements of group 1 (preferably above all Na, K), group 2 (preferably above all Ca, Mg), group 3 (preferably above all Sc), group 4 (preferably above all Ti, Zr), group 5 (preferably especially V), group 6 (preferably especially Cr, Mo, W), group 7 (preferably especially Mn), group 8 (preferably especially Fe, Ru, Os), group 9 (preferably especially Co, Rh, Ir), group 10 (preferably above all Ni, Pd, Pt), group 11 (preferably above all Cu, Ag, Au), group 12 (preferentially above all Zn, C
  • the carbon is essentially elementary, d. H.
  • the proportion of atoms other than carbon in the phase e.g. B. N, O, S, P and / or H, is less than 10 wt .-%, in particular less than 5 wt .-%, based on the total amount of carbon in the phase.
  • the content of the atoms other than carbon in the phase can be determined by X-ray photoelectron spectroscopy (X-ray PES).
  • the carbon phase may contain, in particular, small amounts of N, O and / or H as a result of the preparation.
  • the molar ratio of H to C will generally not exceed a value of 1: 2, in particular a value of 1: 3 and especially a value of 1: 4.
  • the value can also be 0 or nearly 0, e.g. B. less than or equal to 0.1.
  • Carbon in graphitic form is understood to mean that the carbon is present at least partially in a hexagonal layer arrangement typical of graphite, which layers may also be bent or exfoliated.
  • each (semi-) metal in the electroactive material containing at least one carbon phase according to the invention is at least 2% by weight, preferably at least 3% by weight and more preferably at least 5% by weight, based on the weight of carbon in the composite material.
  • Both the composite material (K1) according to the invention and the electroactive material according to the invention have the advantage that it can be produced in a simple manner, with reproducible quality and on an industrial scale, whereby the production can be carried out safely, inexpensively and with easily accessible starting materials.
  • Another object of the present invention is the use of the electroactive material according to the invention as part of an electrode for an electrochemical cell and an electrode (hereinafter also referred to as anode) for an electrochemical cell containing the electroactive material according to the invention.
  • the electroactive material according to the invention is particularly suitable as material for anodes in Li-ion cells, particularly suitable in Li-ion secondary cells or batteries. It is characterized by a high capacity and good cycle stability, especially when used in anodes of Li-ion cells and especially of Li-ion secondary cells low impedances in the cell. Furthermore, it has - probably due to the special phase arrangement - a high mechanical stability. In addition, it can be easily prepared from readily available starting materials with reproducible quality.
  • 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.
  • 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 collectors and electrical contacts, is generally at least 40% by weight, often at least 50% by weight and especially at least 60% by weight.
  • electrically conductive or electroactive constituents in the anodes according to the invention are carbon black (carbon black), graphite, carbon fibers, nanocarbon fibers, nanocarbon tubes or electrically conductive polymers.
  • carbon black carbon black
  • graphite carbon fibers
  • nanocarbon fibers nanocarbon tubes
  • electrically conductive polymers 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, cellulose, carboxymethyl cellulose, polyvinyl alcohol, polyvinylidene fluoride, polyethylene, polypropylene, polytetrafluoroethylene, polyacrylonitrile-methyl methacrylate copolymers, styrene-butadiene copolymers, tetrafluoroethylene Hexafluoropropylene copolymers, vinylidene fluoride-hexafluoropropylene copolymers, vinylidene fluoride-tetrafluoroethylene copolymers, perfluoroalkyl vinyl ether copolymers, ethylene-tetrafluoroethylene copolymers, vinylidene fluoride-chlorotrifluoroethylene copolymers, ethylene-chlorofluoroethylene copolymers, ethylene-acrylic acid copolymers, if appropriate at
  • binder is often made taking into account the properties of any solvent used in the preparation.
  • polyvinylidene fluorides are suitable when N-ethyl-2-pyrrolidone is used as the solvent.
  • the binder is usually used in an amount of 1 to 10 wt .-%, based on the total mass of the anode material. Preferably, 2 to 8 wt .-%, in particular 3 to 7 wt .-% are used.
  • the electrode according to the invention comprising the electroactive material according to the invention, also referred to above as anode, usually comprises electrical contacts to the supply and Discharge of charges, such as a current collector, which may be configured in the form of a metal wire, metal mesh, metal mesh, expanded metal, a metal foil and / or a metal sheet.
  • a current collector which may be configured in the form of a metal wire, metal mesh, metal mesh, expanded metal, a metal foil and / or a metal sheet.
  • metal foils in particular copper foils are suitable.
  • the anode has a thickness in the range of 15 to 200 .mu.m, preferably from 30 to 100 .mu.m, based on the thickness without Stromableiter.
  • the preparation of the anode can be done in a conventional manner by standard methods as they are known from relevant monographs.
  • the electroactive material according to the invention optionally using an organic solvent (for example N-methylpyrrolidinone, N-ethyl-2-pyrrolidone or a hydrocarbon solvent) with the optionally further constituents of the anode material (electrically conductive constituents and / or or organic binder) and optionally subjected to a molding process or to an inert metal foil, for. B. Cu film, apply.
  • it is then dried.
  • 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.
  • Another object of the present invention is an electrochemical cell, in particular a lithium ion secondary cell, containing at least one electrode, which was prepared from or using an electrode material, 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.
  • cathodes in which the cathode material comprises 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.
  • 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.
  • the cathode material comprises lithium transition metal oxide, eg.
  • lithium-cobalt oxide lithium-nickel oxide, lithium-cobalt-nickel oxide, lithium-mangan
  • the two electrodes ie the anode and the cathode, are connected together using a liquid or even solid electrolyte.
  • Suitable liquid electrolytes are in particular non-aqueous solutions (water content generally less than 20 ppm) of lithium salts and molten Li salts into consideration, for. B.
  • ionic conductive polymers can be used as solid electrolytes.
  • separator may be arranged, which is impregnated with the liquid electrolyte.
  • separators are in particular glass fiber webs and porous organic polymer films such as porous films of polyethylene, polypropylene, 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.
  • separators may be comprised of inorganic particle filled polyethylene terephthalate webs. Such separators may have a porosity in the range of 40 to 55%. Suitable pore diameters are for example in the range of 80 to 750 nm.
  • Electrochemical cells according to the invention furthermore contain a housing which can have any shape, for example 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 prepared as a bag is used as the housing.
  • 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.
  • 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 typical arranged between individual anode / separator / cathode / current collector element combinations.
  • the electrochemical cells according to the invention have a high capacity, cycle stability, efficiency and reliability, good mechanical stability and low impedances.
  • the electrochemical cells of the invention can be assembled into lithium-ion batteries.
  • 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 well suited for use in devices.
  • the use of electrochemical cells according to the invention in devices is also the subject of the present invention.
  • Devices can be stationary or mobile devices.
  • Mobile devices are, for example, vehicles that are used on the mainland (preferably primarily automobiles and two / three-wheelers), in the air (preferably aircraft in particular) and in the water (preferably ships and boats in particular).
  • mobile devices are also mobile devices such as mobile phones, laptops, digital cameras, implanted medical devices, and electrical hand tools, particularly in the field of construction, i. For example, drills, cordless drill and battery tacker.
  • Stationary devices are, for example, stationary energy storage devices, preferably for wind and solar energy, as well as stationary electrical devices. Such uses are a further subject of the present invention.
  • lithium-ion batteries according to the invention offers the advantage of a longer transit time before reloading and a lower capacity loss with a 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.
  • the lithium-ion batteries according to the invention can be used as small and light batteries.
  • the lithium-ion batteries according to the invention are also characterized by a high capacity and cycle stability, whereby they have a high reliability and efficiency due to a low temperature. turangkeit and self-discharge rate have.
  • the lithium-ion batteries according to the invention can be safely used and produced inexpensively.
  • the lithium-ion batteries according to the invention show advantageous electrokinetic properties, which is particularly noticeable in vehicles with electric drive and hybrid vehicles.
  • Samples of the electroactive material obtained were examined by TEM (see FIG. 1):
  • the TEM investigations were carried out as a HAADF-STEM with a Tecnai F20 transmission electron microscope at a working voltage of 200 kV in ultrathin layer technique (embedding of the samples in synthetic resin as matrix).
  • the bright spots are the heavier elements (here Sn and Si - (semi-) metallic phase), the dark ones are the carbon-rich (carbon) phase), indicating that the domain distances are in the range of a few nm (maximum 10 nm).
  • the electroactive material obtained in 1 b) was then mixed with conductive carbon black (Super P Li Timcal) and binder (polyvinylidene fluoride, KYNAR FLEX ® 2801) mixed to form a viscous coating composition consisting of 87 wt .-% of the obtained in 1 b) electro-active material To obtain 6 wt .-% Leitruß and 7 wt .-% binder in solvent N-ethyl-2-pyrrolidone. The amount of solvent used was 125 wt .-% of the solids used. For better homogenization, the coating composition was stirred for 16 h.
  • the coating composition was then applied to a 20 ⁇ thick copper foil (purity 99.9%) by knife coating and dried at 120 ° C under vacuum. After drying, the resulting electrodes (width 8 cm) were calendered with a line pressure of 9 N / mm and then placed in an argon atmosphere (water content ⁇ 1 ppm, oxygen content ⁇ 10 ppm). Before the cell construction, the electrodes were again dried at 5 mbar and 120 ° C overnight. For the construction of the electrochemical test cells (2-electrode measuring arrangement analogous to a button cell) circular pieces were punched with a diameter of 20 mm. Lithium foil was used as the counter electrode.
  • the electrolyte used was 1 M LiPF 6 in 1: 1 mixture of ethylenecarbonate and ethylmethylcarbonate.
  • the cells were connected to a Maccor Series 4000 battery cycler. Cells were cycled at a specific current of 30 mA per gram of active material between 10 mV and 2 V versus Li / Li + . After reaching 10 mV, the voltage was kept constant for 30 minutes.
  • Figure 3 shows the discharge capacity of two cells over 40 cycles. The achieved capacity is above achievable values for graphite. On the basis of the almost identical curve shape of the two cells, the good reproducibility of the electrodes from 1 d) becomes clear.
  • Figure 4 shows the variation of the differential capacitance across the voltage. The values shown were calculated from the measurement data of a chronoamperometaneous measurement. In chronoamperometry a constant current is given and the changes in the voltage are registered. The plot of the resulting differential capacitance across the voltage allows statements about characteristic electrochemical processes, such as lithium incorporation or removal, or decomposition of electrolyte.
  • the characteristic peaks for tin electrochemical activity are at 0.4 V (lithium alloy incorporation with tin: negative y-axis) and between 0.6 and 0.8 volts (three lithium-tin lithium extraction peaks) Alloy: positive y-axis).
  • Figure 4 Differential capacitance of the electrode from 1 d) at a voltage of 0 to 2 V.
  • Production Example 2 Production of a Composite Material (K1.2)

Abstract

L'invention concerne un procédé de production d'un matériau composite qui contient a) au moins une phase (semi)-métallique et b) au moins une phase polymère organique, comprenant la copolymérisation de - au moins un aryloxy(semi-)métallate et/ou aryloxyester d'un non-métal formant des oxoacides, le non-métal étant différent du carbone et de l'azote, (composé I), présentant - au moins une cétone, un formaldéhyde et/ou un équivalent du formaldéhyde (composé II) en présence de - au moins un composé (semi-)métallique qui n'est pas de l'aryloxy(semi-)métallate, (composé III), le poids en (semi-)métal du composé III étant au moins de 5 % en poids par rapport au poids du composé I.
PCT/IB2013/054939 2012-06-26 2013-06-17 Matériaux composites et leur procédé de fabrication WO2014001949A1 (fr)

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KR1020157001719A KR20150032308A (ko) 2012-06-26 2013-06-17 복합 물질 및 이의 제조 방법
JP2015519401A JP2015522681A (ja) 2012-06-26 2013-06-17 複合材料およびその製造方法
EP13809585.6A EP2865033A4 (fr) 2012-06-26 2013-06-17 Matériaux composites et leur procédé de fabrication
CN201380034016.8A CN104412422A (zh) 2012-06-26 2013-06-17 复合材料及其生产方法

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CN109238312B (zh) * 2018-09-07 2021-03-23 浙江理工大学 一种复合纤维基柔性压电传感器的制备方法

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JP2015522681A (ja) 2015-08-06
EP2865033A1 (fr) 2015-04-29

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