WO2015086461A1 - Matériaux composites contenant de l'azote, leur fabrication et utilisation - Google Patents

Matériaux composites contenant de l'azote, leur fabrication et utilisation Download PDF

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Publication number
WO2015086461A1
WO2015086461A1 PCT/EP2014/076744 EP2014076744W WO2015086461A1 WO 2015086461 A1 WO2015086461 A1 WO 2015086461A1 EP 2014076744 W EP2014076744 W EP 2014076744W WO 2015086461 A1 WO2015086461 A1 WO 2015086461A1
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metal
phase
monomer unit
compound
composite material
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PCT/EP2014/076744
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German (de)
English (en)
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Arno Lange
Gerhard Cox
Hannes Wolf
Szilard Csihony
Stefan Spange
Lysann KASSNER
Anja KNOBLAUCH
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Basf Se
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/005—Reinforced macromolecular compounds with nanosized materials, e.g. nanoparticles, nanofibres, nanotubes, nanowires, nanorods or nanolayered materials
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B21/00—Nitrogen; Compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C08L101/02—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
    • C08L101/025—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing nitrogen atoms
    • 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
    • H01M4/362—Composites
    • H01M4/364—Composites as mixtures
    • 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
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • 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
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/386—Silicon or alloys based on silicon
    • 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
    • H01M4/606—Polymers containing aromatic main chain polymers
    • H01M4/608—Polymers containing aromatic main chain polymers containing heterocyclic rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
    • C08G77/26—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen nitrogen-containing groups
    • 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
    • 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 relates to composite materials comprising a) at least one nitrogen and (semi-) metal-containing phase (a), and b) at least one organic polymer phase (b). Furthermore, the invention also relates to methods for producing such composite materials, the use of such composite materials for the production of electroactive materials and electrochemical cells containing the electroactive materials.
  • Secondary batteries, accumulators, rechargeable batteries or "rechargeable batteries” are only a few embodiments for storing and using electrical energy after production because of their significantly better power density, they have recently deviated from the water-based secondary batteries and developed such batteries. where charge transport in the electrical cell is accomplished by lithium ions.
  • the cathode usually contains a lithium-transition metal compound such as UC0O2 or LiFeP0 4, and the anode usually contains graphite in which Li 0 is intercalated during the charging process.
  • a lithium-transition metal compound such as UC0O2 or LiFeP0 4
  • the anode usually contains graphite in which Li 0 is intercalated during the charging process.
  • anodes containing lithium-metal alloys for example lithium-tin or lithium-silicon alloys. Silicon and tin can absorb large amounts of lithium to form the alloys Li 4 , 4 Sn and Li 4 , 4 Si and show significantly higher capacities than a graphite electrode with intercalated Li 0 .
  • twin polymerization provides composite materials typically having at least one oxide phase and at least one organic polymer phase wherein the phase domains have a co-continuous configuration and dimensions in the range of a few nanometers (spacing between adjacent identical phases).
  • phase constituents form more or less synchronously, and phase separation into the inorganic phase and the organic phase takes place already during the polymerization of the twin monomers.
  • Preferred twin monomers are spiro-cyclic compounds, as described in WO 2009/083083.
  • spiro-cyclic compounds two 1-oxy-2- (oxymethyl) aryl groups are linked together via their oxygen atoms with a metal or semimetal atom to form a spirocyclic structure.
  • An example of such a spiro-cyclic compound is 2,2'-spiro [4H-1,2,2-benzodioxasiline].
  • DE 1816241 discloses the preparation of soluble metal- or semimetal-containing phenol-formaldehyde resins in which either certain metal or semimetal phenolates are reacted with substoichiometric amounts of formaldehyde or novolaks, ie phenol-formaldehyde condensates with selected inorganic metal or semimetal compounds - be implemented.
  • the preparation of composite materials with a phase structure whose phase domains have dimensions in the nanometer range is not described.
  • a disadvantage of all methods is that first oxygen-containing silicon domains are produced, which are difficult to convert into the desired elemental silicon or silicon suboxide in hybrid systems.
  • elemental Si can be produced from silica and carbon (S1O2 + 2C -> Si + 2 CO), but here one must rely on the exact adherence to the stoichiometry. Therefore, this method is unsuitable for C / Si composite materials since additional carbon forms SiC under these conditions, the hybrid structures are dissolved therewith, and / or elemental Si is converted to SiC.
  • the object was thus to find new composite materials and processes for their preparation which reduce or eliminate the disadvantages described above. Furthermore, improved electroactive materials should be made available from the new composite materials.
  • phase (b) at least one organic polymer phase (b), wherein at least one organic polymer phase (b) having at least one nitrogen and (half) metal-containing phase (a), also called phase (a) for short forms phase domains and the average distance (the arithmetic mean of the distances) of two adjacent domains of identical phases, determined by means of small angle X-ray scattering, is substantially at most 200 nm.
  • the composite materials according to the invention are composite materials which in the context of the present invention are also called composite materials according to the invention.
  • Composite materials are generally understood to mean materials which are solid mixtures which can not be separated manually and which have different properties than the individual components.
  • the composite materials according to the invention are nanocomposite materials or so-called nanocomposites.
  • the composite material according to the invention is characterized in that the organic polymer phase (b) with the nitrogen and (half) metal-containing phase (a) forms phase domains and the average distance (the arithmetic mean of the distances) of two adjacent domains of identical phases , determined with the aid of small angle X-ray scattering, is substantially at most 200 nm, preferably at most 50 nm, in particular less than 10 nm.
  • adjacent phase domains of identical phases is meant two phase domains of two identical phases separated by a phase domain of the other phase, for example two phase domains of the nitrogen and (half) metal-containing phase (a) passing through a phase domain of the organic polymer phase ( b) are separated, or two phase domains of the polymer phase (b), by a phase domain of the nitrogen and
  • (Half) metal-containing phase (a) are separated.
  • the (semi-) metal in the nitrogen and (half) metal-containing phase (a) is preferably selected from B, Al, Ga, In, Si, Ge, Sn, As, Sb, Se, Te, Ti, Zr, V, Cr, Mo, W, Mn and mixtures thereof.
  • the (semi-) metal is more preferably selected from B, Al, Si, Ti, Zr and Sn, most preferably from Al, Si, Ti and Zr, in particular Si. Particularly preferred are at least 90 mol%, especially at least 99 mol% of all metals or semimetals M in phase (a), based on the total amount of all (semi-) metals, equal to silicon.
  • the composite material according to the invention is characterized in that the (semi-) metal of the phase (a) is selected from B, Al, Ga, In, Si, Ge, Sn, As, Sb, Se, Te , Ti, Zr, V, Cr, Mo, W, Mn and mixtures thereof, is preferably selected from B, Al, Si, Ti, Zr and Sn, more preferably selected from Al, Si, Ti and Sn, in particular under Si.
  • the composite material according to the invention is characterized in that the (semi-) metal of phase (a) is at least 90 mol%, based on the total amount of (semi-) metal in phase (a), silicon includes.
  • the molar ratio of (semi) metal to nitrogen can vary within a wide range, depending on the stoichiometry of the compounds formed.
  • the molar ratio of (semi) metal to nitrogen is in the range of 1: 1 to 1: 4.
  • the nitrogen in phase (a) is preferably formally present in the oxidation state -3.
  • N 3_ nitride
  • HN 2 ⁇ amides
  • H2N " amides
  • the composite material according to the invention is characterized in that in the phase (a) the molar ratio of (half) metal to nitrogen in the range of 1 to 1 to 1 to 4.
  • the nitrogen and (half) metal-containing phase (a) is further characterized by the fact that the oxygen content in phase (a) is very low, that is, the content of (half) metal-oxygen compounds such For example, oxides or hydroxides, determined by elemental analysis, is very low.
  • the phase (a) contains 0 to 1 wt .-%, preferably from 0 to 0.1 wt .-%, in particular 0 to 0.01 wt.% Oxygen based on the total mass of the phase (a).
  • the composite material according to the invention is characterized in that phase (a) is from 0 to 1% by weight, preferably from 0 to 0.1% by weight, in particular 0 to 0.01% by weight, of oxygen , based on the total mass of the phase (a) contains.
  • phase (a) is from 0 to 1% by weight, preferably from 0 to 0.1% by weight, in particular 0 to 0.01% by weight, of oxygen , based on the total mass of the phase (a) contains.
  • the composite material according to the invention is preferably obtainable by a so-called twin polymerization of a suitable starting compound, in particular by polymerization of at least one monomer AB which
  • At least one first cationically polymerizable monomer unit A which has a metal or semimetal M
  • At least one second cationically polymerizable organic monomer unit B which is covalently bound via one or more nitrogen atoms to the metal or semimetal atom M of the polymerizable monomer unit A,
  • the composite material according to the invention is characterized in that the composite material is obtainable by polymerization of at least one monomer AB, which
  • At least one first cationically polymerizable monomer unit A which has a metal or semimetal M
  • At least one second cationically polymerisable organic monomer unit B which is covalently bound via one or more nitrogen atoms to the metal or semimetal atom M of the polymerisable monomer unit A,
  • the organic polymer phase (b) may in principle contain one or more polymers, wherein the polymers may be selected from a variety of different polymers having different structure and construction.
  • the polymer phase (b) preferably contains at least one polymer which contains aryl units which are linked to further aryl units via at least one substituted or unsubstituted alkylene group.
  • the polymer phase (b) particularly preferably contains at least one polymer which contains aryl units derived from aniline and which are linked via at least one methylene group to further such aniline-derived aryl units.
  • Another object of the present invention is also a process for the preparation of a composite material containing a) at least one nitrogen and (half) metal-containing phase, and
  • At least one first cationically polymerizable monomer unit A which has a metal or semimetal M
  • At least one second cationically polymerisable organic monomer unit B which is covalently bound via one or more nitrogen atoms to the metal or semimetal atom M of the polymerisable monomer unit A,
  • the metal or semimetal M of the monomer unit A in the monomers AB or in the aryl amidometalate or arylamido anyway is preferably selected from B, Al, Ga, In, Si, Ge, Sn, As, Sb, Se, Te, Ti, Zr, V, Cr, Mo, W, Mn and mixtures thereof.
  • the metal or semimetal M is particularly preferably selected from B, Al, Si, Ti, Zr and Sn, very particularly preferably from Al, Si, Ti and Zr, in particular Si. Particularly preferred are at least 90 mol%, especially at least 99 mol% of all metals or semimetals M in phase (a), based on the total amount of all (semi-) metals, equal to silicon.
  • the method according to the invention for producing a composite material is characterized in that the metal or semimetal M of the monomer unit A in the monomer AB or in the arylamidometalate or arylamido anywaymetallat is selected from B, Al, Ga, In, Si, Ge, Sn, As, Sb, Se, Te, Ti, Zr, V, Cr, Mo, W, Mn and mixtures thereof, is preferably selected from B, Al, Si, Ti, Zr and Sn, particularly preferably selected from Al, Si, Ti and Zr, especially selected from Si.
  • the method according to the invention for producing a composite material is characterized in that the metal or semimetal M of the monomer unit A in the monomer AB or in the Arylamidometallat or Arylamido- rudmetallat at least 90 mol%, based on the total amount at M, silicon.
  • M is a metal or semimetal; , R 2 may be the same or different and each represents a radical
  • radicals R 1 Q and R 2 G together represent a radical of the formula Ia
  • R may be identical or different and are halogen, CN, Ci-C6-alkyl, Ci-C6 mono- or di-alkylamino and phenyl are selected and R a , R b have the meanings given above;
  • NR 3 may be the same or different and each represents NR 3 ;
  • corresponding to the valence of M is 0, 1 or 2
  • radicals R are hydrogen, alkyl, alkenyl, cycloalkyl or aryl, wherein aryl is unsubstituted or may have one or more substituents which are defined as the radicals R, and a plurality of radicals R 3 may be identical or different, in particular R 3 is in each case hydrogen ,
  • the moieties corresponding to the radicals R 1 and R 2 G form polymerisable unit (s) B. If X and Y are different from a chemical bond and R 1 ' X and R 2' do not represent inert radicals such as C i C6-alkyl, C3-C6-cycloalkyl or aryl, the radicals R 1 ' X and R 2' Y also form polymerizable unit (s) B. On the other hand forms the metal atom M, optionally together with the groups Q and Y, the Main component of the monomer unit A.
  • An aromatic ring or radical, or aryl is understood in the context of the invention to mean a carbocyclic aromatic hydrocarbon radical, such as phenyl or naphthyl.
  • a heteroaromatic ring or radical, or hetaryl is understood as meaning a heterocyclic aromatic radical which generally has 5 or 6 ring members, one of the ring members being a heteroatom which is nitrogen, oxygen and sulfur, preferably nitrogen , and optionally 1 or 2 further ring members may each be a nitrogen atom and the remaining ring members are carbon.
  • preferred heteroaromatic radicals are, pyrrolyl, pyrazolyl, imidazolyl, pyridyl, pyrimidyl or pyrdazinyl.
  • a condensed aromatic radical or ring is understood as meaning a carbocyclic aromatic, divalent hydrocarbon radical, such as o-phenylene (benzo) or 1,2-naphthylene (naphtho).
  • a fused heteroaromatic radical or ring is understood as meaning a heterocyclic aromatic radical as defined above, in which two adjacent C atoms form the double bond shown in formula Ia.
  • the metal or metalloid M in formula I stands in particular for the preferred embodiments of M. given in connection with the description of the composite material.
  • the groups R 1 Q and R 2 G together represent a radical of the formula la as defined above, in particular for a radical of the formula Iaa:
  • m, R, R a and R b have the meanings given above.
  • the variable m is, in particular, 0. If m is 1 or 2, R is in particular a methyl or C 1 -C 6 mono- or di-alkylamino group, in particular methyl group.
  • R a and R b are in particular hydrogen.
  • Q and G are in particular NH.
  • M is Si, Ti, Zr, Hf, Ge or Sn, preferably Si, Ti and Zr, in particular Si;
  • R, R ' are independently selected from halogen, CN, C 1 -C 6 -alkyl, C 1 -C 6 -mono- or di-alkylamino and phenyl and are preferably methyl or C 1 -C 6 -mono- or di-alkylamino, in particular methyl ;
  • n are independently 0, 1 or 2, in particular 0,
  • R a , R b , R a ' , R b' are independently selected from hydrogen and methyl or
  • Aryl selected and are in particular methyl
  • R 3 is hydrogen, alkyl, alkenyl, cycloalkyl or aryl, wherein aryl is unsubstituted or may have one or more substituents which are defined as the radicals R, and a plurality of radicals R 3 may be the same or different, in particular R 3 is in each case Hydrogen stands.
  • the process according to the invention for producing a composite material according to a second process variant namely by copolymerization of at least one compound C with at least one compound D, characterized in that the compound C, which is selected from Arylamidometallaten and aryl amido-semi-metalates, by which general formula IV or condensation products thereof are described,
  • M is a metal or semimetal, preferably Si, Ti, Zr, Hf, Ge or Sn, particularly preferably Si, Ti and Zr, in particular Si;
  • r stands for 1, 2, 3, 4, 5 or 6, preferably for 2, 3 or 4, in particular 4,
  • s is 0, 1 or 2, preferably 0, t is 0, 1 or 2, preferably 0,
  • u is an integer, e.g. 1, 2, 3, 4, 5 or 6, in particular 1,
  • r + 2s + t is 1, 2, 3, 4, 5 or 6 and corresponds to the valency of M
  • Ar is phenyl or naphthyl, wherein the phenyl ring or the naphthyl ring are unsubstituted or may have one or more substituents R 6 , which are selected from Ci-C6-alkyl, C3-C6-cycloalkyl and NR e R f , wherein R is e and R f independently of one another represent hydrogen, C 1 -C 6 -alkyl or C 3 -C 6 -cycloalkyl;
  • R 4 is hydrogen, C 1 -C 6 -alkyl, C 3 -C 6 -cycloalkyl or aryl, wherein aryl is phenyl or naphthyl and is unsubstituted or may have one or more substituents which are defined as the radicals R 6 , and several radicals R 4 may be the same or different, and
  • R 5 is hydrogen, C 1 -C 6 -alkyl, C 3 -C 6 -cycloalkyl or aryl, wherein aryl is phenyl or naphthyl and is unsubstituted or may have one or more substituents which are defined as the radicals R 6 .
  • compound C are tetraanilinosilane, tetra (4-methylanilino) silane, trinilinoborate, tetraanilinotitanium, tetraanilinostannane, methyl (trianilino) silane, dimethyl (dianilino) silane, trimethyl (anilino) silane, phenyl (trianilino) silane, Diphenyl (dianilino) silane, diani- linomethylsilane and dianilinosilane.
  • M is Si, Ti and Zr, especially Si
  • Ar is an unsubstituted phenyl radical
  • R 4 is hydrogen or methyl, in particular hydrogen
  • R 5 is methyl
  • cyclic condensation products which can be used as compound C in the copolymerization are hexaanilinocyclotrisilazane or octaanilinocyclotetrasilazane.
  • compound D which is selected from oxygen-free formaldehyde reaction products containing at least one methylene equivalent
  • Completely dehydrated reaction products are, for example, imines, which are the primary reaction products of the reaction, or higher condensation products, as in the case of the reaction of formaldehyde with ammonia, with hexamethylenetetramine, also called urotropin, being formed as a stable condensation product.
  • imines which are the primary reaction products of the reaction, or higher condensation products, as in the case of the reaction of formaldehyde with ammonia, with hexamethylenetetramine, also called urotropin, being formed as a stable condensation product.
  • hexamethylenetetramine also called urotropin
  • the inventive method for producing a composite material according to the second Maschinensvarian- te namely by copolymerization of at least one compound C with at least one compound D, characterized in that hexamethylenetetramine, also called urotropin, selected as compound D. becomes.
  • the copolymerization of at least one compound C with at least one compound D according to the second process variant is carried out in a reaction medium which is essentially anhydrous, wherein the compound D is used in an amount such that the molar ratio of methylene equivalents in compound D to the arylamido groups in the compound C preferably in the range from 1: 2 to 10: 1, particularly preferably in the range from 1, 0: 2 to 5: 1, very particularly preferably in the range from 1, 0: 1, 5 to 2: 1, in particular in the range 1, 0: 1, 3 to 1, 5: 1.
  • the reaction medium in which the copolymerization is carried out can be formed solely by the components C and D used, for example by forming a melt at elevated temperatures.
  • an inert solvent can be used as the anhydrous reaction medium in which the components C and D at least partially, preferably completely dissolve.
  • Suitable solvents are, for example, halogenated hydrocarbons such as dichloromethane, trichloromethane, dichloroethene or hydrocarbons such as toluene, xylene or hexane and mixtures thereof.
  • anhydrous in the context of the present invention, a water content of less than 0.1 wt .-%, preferably less than 0.01 wt .-% understood at the beginning of the polymerization or copolymerization, wherein the water content by Karl
  • both the polymerization of the monomer AB, the so-called twin polymerization, and the alternative copolymerization of the compound C with compound D can be carried out purely thermally or using at least one catalyst.
  • the temperatures required for the polymerization are typically in the range from 50 to 250 ° C., in particular in the range from 80 to 200 ° C.
  • the polymerization temperatures are typically within Range of 50 to 200 ° C and in particular in the range of 80 to 150 ° C. In the thermally initiated polymerization, the polymerization temperatures are typically in the range of 120 to 250 ° C and especially in the range of 150 to 200 ° C. Proton acids or Lewis acids are particularly suitable as catalysts.
  • the polymerization of the compound C with the compound D takes place in the presence of catalytic amounts of an acid.
  • the acid is used in an amount of from 0.1 to 10% by weight, in particular from 0.2 to 5% by weight, based on the compounds C.
  • Preferred acids here are Bronsted acids without oxygen, for example inorganic Bronsted acids such as HCl.
  • the Lewis acid for example, BF3, BCI3, SnC, SnCU, TiCU, or AICI3 can be used.
  • the use of complexed or dissolved in ionic liquids Lewis acids is also possible.
  • the polymerization can also be catalyzed with bases.
  • bases are amines such as triethylamine or dimethylaniline, hydroxides and basic salts of alkali metals and alkaline earth metals such as LiOH, NaOH, KOH, Ca (OH) 2 , Ba (OH) 2 or Na 3 P0 4 and alkoxides of alkali metals and alkaline earth metals such as Na methylate, Na ethylate, Kt.Butylat or Mg-ethylate.
  • amines such as triethylamine or dimethylaniline
  • hydroxides and basic salts of alkali metals and alkaline earth metals such as LiOH, NaOH, KOH, Ca (OH) 2 , Ba (OH) 2 or Na 3 P0 4
  • alkoxides of alkali metals and alkaline earth metals such as Na methylate, Na ethylate, Kt.Butylat or Mg-ethylate.
  • Preferred catalysts for the polymerization or copolymerization are protic acids selected from the group of CH-acidic and NH-acidic compounds, such as dicyanamide.
  • the process according to the invention for producing a composite material is characterized in that the polymerization or copolymerization is carried out in the presence of an acid selected from the group of CH-acidic and NH-acidic compounds.
  • Both the twin polymerization and the copolymerization can in principle be carried out as a so-called batch or as an addition process. When carried out as a batch, the reaction components are introduced in the desired amount in the reaction vessel and brought to the conditions required for the polymerization.
  • the addition process which is particularly applicable for the copolymerization
  • at least one of the two components, ie compound C and / or compound D is at least partially fed in the course of the polymerization until the desired ratio of compound C to compound D is reached.
  • the addition is followed by a post-reaction phase. Preference is given to carrying out the polymerization and the copolymerization as a batch.
  • the polymerization of the monomer AB or the copolymerization of the compound C with compound D may be followed by purification steps and optionally drying steps.
  • the composite material according to the invention or the composite material produced by the process according to the invention can be converted by analogy with the materials described in WO 2009/083083 by oxidative removal of the organic polymer phase (b) into a nanoporous inorganic material, or the new composite material can be prepared by carbonation of the organic polymer phase (b) to an electroactive material which can be used in electrochemical cells are reacted.
  • a further subject of the present invention is accordingly the use of a composite material according to the invention as described in the introduction or of a composite material obtainable or obtained by the process according to the invention described above for producing an electroactive material for electrochemical cells.
  • the present invention also provides a method for producing an electroactive material for electrochemical cells comprising the carbonization of a composite material as described in the introduction, or a composite material obtainable or obtained by the method according to the invention described above.
  • an electroactive material By carbonizing the composite material of the present invention, an electroactive material can be obtained.
  • the carbonization is carried out at a temperature in the range from 200 to 2000 ° C., preferably in the range from 300 to 1600 ° C., more preferably in the range from 400 to 1100 ° C., in particular in the range from 500 to 900 ° C. ,
  • the duration of carbonation can vary widely and, among other things, depends on the temperature at which the carbonation is carried out.
  • the period of carbonation may be from 0.5 to 12 hours, preferably from 1 to 5 hours, in particular from 1 to 2 hours.
  • the carbonization of the composite material according to the invention can, in principle, be carried out in one or more stages, for example in one or two stages.
  • Oxygen can be carried out as long as the oxidizing agent does not completely oxidize the carbon present in the composite material according to the invention.
  • the various steps may be carried out in the presence of different gases and / or at different temperatures.
  • a reducing gas reactive gas
  • hydrogen, ammonia, carbon monoxide or acetylene and mixtures thereof such as synthesis gas (CO / H2) or forming gas (N2 / H2 or Ar / h).
  • the carbonization of the composite material according to the invention can in principle be carried out under reduced pressure, for example under reduced pressure, under normal pressure or under elevated pressure, for example a pressure autoclave.
  • the carbonization is carried out at a pressure in the range from 0.01 to 100 bar, preferably in the range from 0.1 to 10 bar, in particular in the range from 0.5 to 5 bar or 0.7 to 2 bar.
  • the carbonation can be carried out in a closed system or in an open system in which evolved volatiles in a gas stream, inert gases or reducing gases are removed.
  • the carbonization of the composite material according to the invention is carried out in one or more stages, preferably in one stage, with extensive or complete, preferably complete, exclusion of oxygen.
  • Complete exclusion of oxygen in this context means that in the gas space not more than 0.5% by volume, preferably less than 0.05, in particular less than 0.01% by volume of oxygen are present.
  • the carbonization of the composite material according to the invention is carried out in the presence of air or oxygen.
  • the metal or semi-metal bound in the nitrogen and (semi-) metal-containing phase (a) can be partially or completely reduced.
  • the reduction of the metal or semimetal originally present in an increased positive oxidation state preferably takes place in the presence of a reducing gas, here also called reactive gas, as stated above.
  • the partial or complete reduction of metals or semimetals in an increased positive oxidation state in the presence of a reactive gas is therefore selected in the carbonation step from H, NH 3, CO and C 2 H 2 and the latter Mixtures performed.
  • the content of metal or metalloid in the electroactive material can be varied in a wide range.
  • a value for the content of metal or semimetal of almost 0 wt .-%, that is, that only traces of metal or semimetal in the carbon phase C are present, to almost 100 wt .-%, that is, that in the metal or semimetal only traces of a carbon phase C are present, can be varied, wherein the wt .-% indication refers to the total mass of the electroactive material.
  • an electroactive material is preferably produced in the process according to the invention, characterized in that the content of metal or semimetal in the electroactive material is 5 to 90 wt .-%, preferably 10 to 75 wt .-%, particularly preferably 15 to 55 wt. -%, in particular 20 to 40 wt .-% based on the total mass of the electroactive material.
  • the method according to the invention is suitable for producing technical electrode materials in continuous and / or discontinuous mode of operation.
  • batch mode this means batch sizes over 10 kg, better> 100 kg, even better> 1000 kg or> 5000 kg.
  • continuous driving this means production volumes over 10 kg, better> 100 kg, even better> 1000 kg or> 5000 kg.
  • continuous driving this means production volumes over 10 kg, better> 100 kg, even better> 1000 kg or> 5000 kg.
  • the method and the electrode materials produced therewith are furthermore distinguished by the fact that battery cells can be produced which preferably have at least 5 cycles, more preferably at least 10 cycles, most preferably at least 50 cycles, in particular at least 100 cycles or at least 500 Cycles are stable.
  • battery cells can be produced which preferably have at least 5 cycles, more preferably at least 10 cycles, most preferably at least 50 cycles, in particular at least 100 cycles or at least 500 Cycles are stable.
  • electroactive materials obtainable by carbonization of a composite material according to the invention as described above.
  • the electroactive materials of the invention include
  • a carbon phase C i) at least one metal- or semimetal-containing phase, wherein the metal or semimetal is present in a lower oxidation state than the composite material, in particular as elemental metal or semimetal,
  • carbon phase C and the metal or metalloid-containing phase form substantially co-continuous phase domains, wherein the mean distance between two adjacent domains of identical phases is at most 10 nm, in particular at most 5 nm and especially at most 2 nm.
  • the electroactive materials according to the invention correspond in their morphological structure to the electroactive materials described in WO 2010/1 12580, which were prepared starting from oxygen-containing composite materials.
  • the electroactive material according to the invention is particularly suitable as material for anodes in Li-ion cells, in particular in Li-ion cells.
  • Secondary cells or batteries suitable.
  • it when used in anodes of Li-ion cells and especially of Li-ion secondary cells, it is characterized by a high capacity and a good cycle stability and ensures low impedance in the cell. Furthermore, it probably has a high mechanical stability due to the special phase arrangement. In addition, it can be produced easily and with reproducible quality.
  • Another object of the present invention is also the use of the electroactive material according to the invention as described above as part of an electrode for an electrochemical cell.
  • the present invention accordingly also provides an electrode for an electrochemical cell comprising the electroactive material according to the invention as described above.
  • This electrode is usually installed and used as an anode in an electrochemical cell. Therefore, in the following, the electrode which contains the electroactive material according to the invention will also be referred to as the anode.
  • 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 collector 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 components in the anodes according to the invention carbon black, graphite, carbon fibers, nanocarbon fibers, nanocarbon tubes or electrically conductive polymers into consideration.
  • the conductive material is used together with 50-97.5% by weight, often with 60-95% by weight, of the electroactive material of the present invention in the anode to the total mass of the anode material, less any current collector and electrical contacts.
  • Suitable binders for the production of an anode using the electroactive materials according to the invention are in particular the following polymeric materials: polyethylene oxide (PEO), cellulose, carboxymethyl cellulose, polyvinyl alcohol, polyethylene, polypropylene, polytetrafluoroethylene, polyacrylonitrile-methyl methacrylate copolymers, styrene-butadiene copolymers, Tetrafluoroethylene-hexafluoropropylene copolymers, vinylidene fluoride-hexafluoropropylene copolymers (PVdF-HFP), vinylidene fluoride-tetrafluoroethylene copolymers, perfluoroalkyl vinyl ether copolymers, ethylene-tetrafluoroethylene copolymers, vinylidene fluoride-chlorotrifluoroethylene copolymers, ethylene-chlorofluoroethylene copolymers, ethylene-acrylic acid copolymers , optionally at
  • the selection of the binder is optionally carried out taking into account the properties of the solvent possibly used for the preparation.
  • the binder is usually used in an amount of 1 to 10 wt .-% based on the total mixture of the anode material. Preferably, 2 to 8 wt .-%, in particular 3 to 7 wt .-% are used.
  • the electrode according to the invention containing the electroactive material according to the invention also referred to as anode, usually comprises electrical contacts for the supply and discharge of charges, for example a current conductor, in the form of a metal wire, metal grid, metal mesh, expanded metal, or a metal foil or a Metal sheet can be designed.
  • a current conductor in the form of a metal wire, metal grid, metal mesh, expanded metal, or a metal foil or a Metal sheet can be designed.
  • metal foils in particular copper foils are suitable.
  • the anode has a thickness in the range of 15 to 200 ⁇ , preferably from 30 to 100 ⁇ , based on the thickness without Stromableiter.
  • the preparation of the anode can be carried out in a conventional manner by standard methods, as they are known from the cited prior art and from relevant monographs.
  • the inventive electroactive material optionally using an organic solvent (for example, N-methylpyrrolidinone or a hydrocarbon solvent) with the optionally further constituents of the anode material (electrically conductive components and / or organic binder) and mix if necessary, a shaping method subject or on an inert metal foil, eg. B. Cu film, apply.
  • a shaping method subject or on an inert metal foil, eg. 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.
  • a further subject of the present invention is also an electrochemical cell, in particular a lithium ion secondary cell, containing at least one electrode which has been produced from or using an electroactive material according to the invention as described above.
  • Such cells generally have at least one anode according to the invention, a cathode, in particular a cathode suitable for lithium-ion cells, an electrolyte and optionally a separator.
  • cathodes in which the cathode material has lithium transition metal oxide, eg. As lithium-cobalt oxide, lithium-nickel oxide, lithium-cobalt-nickel oxide, lithium-manganese oxide (spinel), lithium-nickel-cobalt-aluminum oxide, lithium-nickel-cobalt-manganese oxide or lithium-vanadium oxide, or a lithium transition metal phosphate such as lithium iron phosphate.
  • 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.
  • cathode materials those containing polymers containing sulfur or polysulfide bridges, care must be taken that the anode is charged with Li 0 before such an electrochemical cell can
  • the two electrodes ie the anode and the cathode, are connected together using a liquid or even solid electrolyte.
  • a liquid or even solid electrolyte e.g. 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, PVdF, etc.
  • Particularly suitable materials for separators are polyolefins, in particular film-shaped porous polyethylene and film-shaped porous polypropylene.
  • Polyolefin separators may have a porosity in the range of 35 to 45%. Suitable pore diameters are, for example, in the range from 30 to 500 nm. In another embodiment of the present invention, it is possible to select, as separators, PET nonwovens which are filled with inorganic particles. Such separators may have a porosity in the range of 40 to 55%. Suitable pore diameters are, for example, in the range from 80 to 750 nm. Electrochemical cells according to the invention usually also contain a housing which may have any shape, for example a cuboid or the shape of a cylinder. In another embodiment, electrochemical cells according to the invention have the shape of a prism. In one variant, a metal-plastic composite film developed as a bag is used as the housing.
  • 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.
  • an insulating film is typically disposed between individual anode / separator / cathode / current collector element combinations.
  • electrochemical cells provide a high voltage and are characterized by a high energy density and good stability.
  • electrochemical cells according to the invention are characterized by only a very small loss of capacity with prolonged use and repeated cycling.
  • the electrochemical cells of the invention can be assembled into lithium-ion batteries. Accordingly, another object of the present invention is also the use of electrochemical cells according to the invention, as described above, in lithium-ion batteries. Another object of the present invention are lithium-ion batteries, comprising at least one inventive electrochemical cell, as described above. Inventive electrochemical cells can be combined with one another in lithium-ion batteries according to the invention, for example in series connection or in parallel connection. Series connection is preferred.
  • Electric cells are characterized by particularly high capacity, high performance even after repeated charging and greatly delayed cell death.
  • Electric cells according to the invention are very suitable for use in automobiles, electric motor-driven two-wheeled vehicles, for example pedelecs, aircraft, ships or stationary energy storage devices. Such uses are a further subject of the present invention.
  • Another object of the present invention is the use of electrochemical cells according to the invention as described above in devices, especially in automobiles, electric motor-powered two-wheelers, aircraft, ships or stationary energy storage.
  • lithium ion batteries in devices according to the invention offers the advantage of a longer running time before recharging and a lower capacity loss with longer running time. If one wanted to realize an equal running time with electrochemical cells with a lower energy density, then one would have to accept a higher weight for electrochemical cells.
  • Another object of the present invention is therefore the use of inventive lithium-ion batteries in devices, especially in mobile devices.
  • mobile devices are vehicles, for example automobiles, two-wheeled vehicles, aircraft or watercraft, such as boats or ships.
  • Other examples of mobile devices are those that you move yourself, such as computers, especially laptops, phones or electrical tools, for example, in the field of construction, in particular drills, cordless screwdrivers or cordless tackers.
  • a further subject matter of the present invention is also a device comprising at least one electrochemical cell according to the invention as described above.

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  • Nanotechnology (AREA)
  • Manufacturing & Machinery (AREA)
  • Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)

Abstract

La présente invention concerne des matériaux composites contenant a) au moins une phase contenant de l'azote et un métal (ou métalloïde), et b) au moins une phase polymère organique (b). En outre, l'invention concerne également des procédés de préparation de tels matériaux composites, l'utilisation de tels matériaux composites pour la fabrication de matériaux électro-actifs, et des piles électrochimiques contenants les matériaux électro-actifs.
PCT/EP2014/076744 2013-12-13 2014-12-05 Matériaux composites contenant de l'azote, leur fabrication et utilisation WO2015086461A1 (fr)

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Cited By (1)

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CN109671925A (zh) * 2018-12-03 2019-04-23 三峡大学 一种GaV2O5/Ga2O3复合物锂离子电池负极材料的制备方法

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WO2009083083A1 (fr) 2007-12-27 2009-07-09 Merck Patent Gmbh Composés spiraniques
WO2009133086A2 (fr) 2008-04-30 2009-11-05 Bernhard Kutschi Élément élastique de soutien pour espaces creux
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WO2012098149A2 (fr) 2011-01-19 2012-07-26 Basf Se Procédé de production d'un matériau composite
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DE1816241A1 (de) 1967-12-20 1969-07-24 Nord Aviat Soc Nationale De Co Metall- oder metalloidhaltige Phenol-Formaldehydharze und Verfahren zu ihrer Herstellung
WO2009083083A1 (fr) 2007-12-27 2009-07-09 Merck Patent Gmbh Composés spiraniques
WO2009133086A2 (fr) 2008-04-30 2009-11-05 Bernhard Kutschi Élément élastique de soutien pour espaces creux
WO2010112580A1 (fr) 2009-04-03 2010-10-07 Basf Se Matière électroactive et son utilisation dans des anodes pour des cellules aux ions lithium
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WO2012098149A2 (fr) 2011-01-19 2012-07-26 Basf Se Procédé de production d'un matériau composite
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109671925A (zh) * 2018-12-03 2019-04-23 三峡大学 一种GaV2O5/Ga2O3复合物锂离子电池负极材料的制备方法
CN109671925B (zh) * 2018-12-03 2021-08-24 三峡大学 一种GaV2O5/Ga2O3复合物锂离子电池负极材料的制备方法

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