[go: up one dir, main page]

WO2013042034A1 - Matériaux composites polymères contenant de l'oxyde d'étain - Google Patents

Matériaux composites polymères contenant de l'oxyde d'étain Download PDF

Info

Publication number
WO2013042034A1
WO2013042034A1 PCT/IB2012/054928 IB2012054928W WO2013042034A1 WO 2013042034 A1 WO2013042034 A1 WO 2013042034A1 IB 2012054928 W IB2012054928 W IB 2012054928W WO 2013042034 A1 WO2013042034 A1 WO 2013042034A1
Authority
WO
WIPO (PCT)
Prior art keywords
tin
phase
carbon
composite material
formula
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/IB2012/054928
Other languages
English (en)
Inventor
Arno Lange
Gerhard Cox
Klaus Leitner
Hannes Wolf
Michael MEHRING
Christian Leonhardt
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF China Co Ltd
BASF SE
Original Assignee
BASF China Co Ltd
BASF SE
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by BASF China Co Ltd, BASF SE filed Critical BASF China Co Ltd
Priority to EP12833502.3A priority Critical patent/EP2759008A4/fr
Priority to KR1020147010222A priority patent/KR20140068202A/ko
Priority to JP2014530373A priority patent/JP2014532258A/ja
Priority to CN201280043102.0A priority patent/CN103782422A/zh
Publication of WO2013042034A1 publication Critical patent/WO2013042034A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C43/00—Ethers; Compounds having groups, groups or groups
    • C07C43/02—Ethers
    • C07C43/20—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring
    • C07C43/205—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring the aromatic ring being a non-condensed ring
    • C07C43/2055—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring the aromatic ring being a non-condensed ring containing more than one ether bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
    • C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
    • C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
    • C07D333/06—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring carbon atoms
    • C07D333/14—Radicals substituted by singly bound hetero atoms other than halogen
    • C07D333/16—Radicals substituted by singly bound hetero atoms other than halogen by oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/56—Organo-metallic compounds, i.e. organic compounds containing a metal-to-carbon bond
    • C08K5/57—Organo-tin compounds
    • 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
    • H01M4/387—Tin or alloys based on tin
    • 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
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • 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
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • 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
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/663—Selection of materials containing carbon or carbonaceous materials as conductive part, e.g. graphite, carbon fibres
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2231—Oxides; Hydroxides of metals of tin
    • 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 novel tin oxide-containing polymer composite materials, to a process for production thereof and to the use thereof for production of tin-carbon composite material composed of at least one inorganic tin-containing phase in which the tin is present in elemental form or in the form of tin (I I ) oxide or in the form of a mixture thereof; and of a carbon phase in which carbon is present in elemental form.
  • tin-carbon composite materials are particularly suitable for production of anode materials for electrochemical cells, especially lithium cells.
  • the invention also relates to compounds (monomers) for production of the inventive tin oxide-containing polymer composite materials. In an increasingly mobile society, mobile electrical devices are playing an ever greater role.
  • the cathode of a modern high-energy lithium battery now comprises, as an
  • electroactive material typically lithium-transition metal oxides or mixed oxides of the spinel type, for example LiCo0 2 , LiNi0 2 , LiNii- x -yCOxMy0 2 (0 ⁇ x ⁇ 1 , y ⁇ 1 , M e.g. Al or Mn) or LiMn204, or lithium iron phosphates, for example.
  • LiCo0 2 LiNi0 2
  • LiNii- x -yCOxMy0 2 (0 ⁇ x ⁇ 1 , y ⁇ 1 , M e.g. Al or Mn
  • LiMn204 lithium iron phosphates
  • a significant disadvantage of such alloys is the change in their dimensions in the course of charging/discharging, which leads to disintegration of the anode material.
  • a consequence which results from the resulting increase in the specific surface area of the anode material is losses of capacity caused by irreversible reaction of the anode material with the electrolyte, and increased sensitivity of the cell to thermal stress, which can lead in the extreme case to strongly exothermic destruction of the cell and is a safety risk.
  • EP 692 833 describes a carbon-containing insertion compound which, as well as carbon, comprises a metal or semimetal which forms alloys with lithium, especially silicon.
  • the preparation is effected by pyrolysis of polymers which comprise the metal or semimetal and hydrocarbyl groups, for example in the case of silicon-containing inclusion compounds by pyrolysis of polysiloxanes.
  • the pyrolysis requires severe conditions under which the primary polymers are first decomposed and then carbon and (semi)metal and/or (semi)metal oxide domains are formed.
  • the production of such materials generally leads to qualities of poor reproducibility, probably because the high energy input makes control of the domain structure possible only with difficulty, if at all.
  • nanoporous materials formed from Sn02 nanoparticles embedded between exfoliated graphite sheets are suitable as anode materials for Li ion batteries. They are produced by mixing exfoliated graphite sheets with Sn02 nanoparticles in ethylene glycol. The exfoliated graphite sheets were themselves produced by reduction of oxidized and exfoliated graphite. This process is comparatively inconvenient and costly. In addition, this process leads to results with poor reproducibility.
  • WO 2010/1 12580 describes electroactive materials which comprise a carbon phase C and at least one MO x phase in which M is a metal or semimetal, for example boron, silicon, titanium or tin, x is a number from 0 to ⁇ k/2 where k is the maximum valency of the metal or semimetal.
  • the electroactive materials are produced in two stages, a first stage involving production of a nanocomposite material from a (semi)metal oxide phase and an organic polymer phase by what is called twin polymerization, and a second stage carbonization of the nanocomposite material thus produced.
  • WO 2010/1 12581 describes a process for producing the nanocomposite materials, in which metal- or semimetal-containing monomers are copolymerized.
  • the monomers proposed include tin-containing monomers in which tin is present in the +4 oxidation state. The production of these monomers, especially in relatively large amounts, is difficult, and polymerization is problematic.
  • the anode materials which are based on carbon or based on lithium alloys and are known to date from the prior art are unsatisfactory in terms of specific capacity, charging/discharging kinetics and/or cycling stability, for example decrease in capacity and/or high or increasing impedance after several charging/discharging cycles.
  • the composite materials which have a particulate semimetal or metal phase and one or more carbon phases and have been proposed recently to solve these problems are capable of solving these problems only partially, and the quality of such composite materials, at least in the case of tin-containing materials, cannot be achieved in a reproducible manner.
  • the production thereof is generally so complex that economic utilization is impossible.
  • tin-containing polymer composite materials which provides these materials with low complexity and product quality of good reproducibility which allows further processing in tin-carbon composite materials.
  • the tin-carbon composite materials thus prepared should be suitable as anode material for Li ion batteries, especially for Li ion secondary batteries, and remedy the disadvantages of the prior art and should especially have at least one and especially more than one of the following properties:
  • the present invention accordingly relates to a process for producing a tin oxide- containing polymer composite material composed of
  • R 2 is Ci-Cio-alkyl or Cs-Cs-cycloalkyl or has one of the definitions given for R 1 ;
  • R 1 together with R 2 is a radical of the formula A:
  • R radicals may be the same or different and are selected from halogen, CN, C1-C6- alkyl, Ci-C6-alkoxy and phenyl, and R a , R b are each as defined above;
  • X is O, S or NH
  • Y is O, S or NH
  • the monomers of the formula I are novel and therefore likewise form part of the subject matter of the present invention.
  • they are easy to prepare, and they can also be prepared on the industrial scale.
  • they are more stable than corresponding tin(IV) compounds, and so the use thereof in the polymerization is associated with fewer problems.
  • the invention also provides a tin oxide-containing polymer composite material composed of
  • inventive tin oxide-containing polymer composite materials can be converted in a simple manner to tin-carbon composite materials, by carbonizing the organic polymer phase of the tin oxide-containing polymer composite materials obtainable in
  • the invention also provides a process for producing a tin-carbon composite material composed of at least one inorganic tin-containing phase in which the tin is present in the 0 or +2 oxidation state or in the form of a mixture thereof; and of a carbon phase in which carbon is present in elemental form; comprising
  • the invention further provides the tin-carbon composite material which is obtainable by this process and is composed of at least one inorganic tin-containing phase in which the tin is present in the +2 or 0 oxidation state or in the form of a mixture thereof; and of a carbon phase in which carbon is present in elemental form.
  • the tin-carbon composite material is particularly suitable as an electroactive material for anodes in Li ion cells, especially in Li ion secondary cells or batteries. More particularly, in the case of use in anodes of Li ion cells and especially of Li ion secondary cells, it is notable for a high capacity and a good cycling stability, and ensures low impedances in the cell. Moreover, probably because of the co-continuous phase arrangement, it has a high mechanical stability. In addition, it can be produced in a simple manner and with reproducible quality.
  • the invention therefore also provides for the use of the tin-carbon composite material in anodes for lithium ion cells, especially lithium ion secondary cells, and an anode for lithium ion cells, especially lithium ion secondary cells, which comprises an inventive tin-carbon composite material, and a lithium ion cell, especially a lithium ion secondary cell, which has at least one anode comprising an inventive tin-carbon composite material.
  • a tin oxide-containing polymer composite material is understood to mean a material which consists essentially, generally to an extent of at least 90% by weight, especially to an extent of at least 95% by weight, of tin oxide and an organic polymer phase, the phases being present distributed among one another.
  • the tin oxide phase generally consists essentially, i.e. generally to an extent of at least 90% by weight, especially to an extent of at least 95% by weight, of tin oxide or tin oxide hydrates.
  • the organic polymer phase is formed by a carbon-containing polymer other then elemental carbon.
  • composition of the organic polymer phase is defined by the Ar-C(R a ,R b ) groups, and so it typically comprises poly(het)arylformaldehyde condensates or polyarylcarbonates or mixtures thereof.
  • tin oxide in the context of the invention comprises the pure tin oxides of the stoichiometry SnO, e.g. a-SnO and ⁇ -SnO, Sn203 and Sn02, e.g. octagonal Sn02 and hexagonal Sn02, and oxide hydrates of di- and tetravalent tin such as Sn(OH)2 and stannic acid H2Sn(OH)6.
  • a carbon-tin composite material is understood to mean a material which consists essentially, generally to an extent of at least 90% by weight, especially to an extent of at least 95% by weight, of a tin-containing phase and elemental carbon, the tin-containing phase on the one hand and carbon on the other hand being present distributed among one another.
  • the carbon phase is formed by elemental carbon, and the carbon may have graphitic structural units.
  • alkyl alkoxy
  • cycloalkyl hydroxyalkyl
  • hydroxyalkyl should, just like the terms “aromatic ring” and “heteroaromatic ring”, be understood as generic collective terms which cover the substituents typically described by this term.
  • suffix Cn-Cm indicates the possible number of carbon atoms that the substituents summarized by this collective term may have.
  • Alkyl is accordingly a saturated linear or branched aliphatic hydrocarbyl radical having generally 1 to 10, frequently 1 to 6 and especially 1 to 4 carbon atoms.
  • Alkoxy is accordingly a saturated linear or branched aliphatic hydrocarbyl radical which is bonded via an oxygen atom and has generally 1 to 10, frequently 1 to 6 and especially 1 to 4 carbon atoms.
  • Hydroxyalkyl is accordingly a saturated aliphatic hydrocarbyl radical which is substituted by at least one OH group and has generally 1 to 10, frequently 1 to 6 and especially 1 to 4 carbon atoms.
  • hydroxyalkyl are hydroxymethyl, 1 - hydroxyethyl, 2-hydroxyethyl, 1 -hydroxypropyl, 2-hydroxypropyl, 3-hydroxylpropyl, 1 - hydroxy-1 -methylethyl, 2-hydroxy-1 -methylethyl, 4-hydroxybutyl etc.
  • Cycloalkyl is accordingly a saturated cycloaliphatic hydrocarbyl radical which has generally 3 to 10, frequently 3 to 8 and especially 3 to 6 carbon atoms and is optionally substituted by 1 to 4 methyl groups.
  • cycloalkyl examples include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, 1 -methylcyclopropyl, 2-methylcyclopropyl, 1 -, 2- or
  • an aromatic radical is understood to mean a carbocyclic aromatic hydrocarbyl radical such as phenyl or naphthyl.
  • a heteroaromatic radical is understood to mean a heterocyclic aromatic radical which generally has 5 or 6 ring members, one of the ring members being a heteroatom selected from nitrogen, oxygen and sulfur, and 1 or 2 further ring members optionally being a nitrogen atom and the remaining ring members being carbon.
  • heteroaromatic radicals are furyl, thienyl, pyrrolyl, pyrazolyl, imidazolyl, oxazolyl, isoxazolyl, pyridyl and thiazolyl.
  • a fused aromatic radical or ring is understood to mean a carbocyclic aromatic divalent hydrocarbylene radical such as o-phenylene (benzo) or 1 ,2-naphthylene (naphtho).
  • tin-containing monomers of the formula I are polymerized under reaction conditions under which both the Ar-C(R a ,R b ) radicals polymerize to form the organic polymer phase and the XSnY unit to form the tin oxide phase.
  • Such polymerization reactions are referred to as twin polymerization and are known, for example, from WO 2010/1 12580 and WO 2010/1 12581 .
  • WO 2010/1 12580 and WO 2010/1 12581 propose exclusively those monomers in which tin is in the +4 oxidation state.
  • Ar is preferably an aromatic or heteroaromatic radical selected from phenyl and furyl, where phenyl and furyl are unsubstituted or have 1 or 2 substituents selected from halogen, OH, CN, Ci-C6-alkyl, Ci-C6-alkoxy, Ci-C6-hydroxyalkyl and phenyl.
  • Ar is phenyl or furyl, where phenyl and furyl are each unsubstituted or optionally have 1 or 2 substituents selected from Ci-C6-alkyl, Ci-C6-hydroxyalkyl and Ci-C6-alkoxy, and especially from hydroxymethyl, methyl and methoxy.
  • Ar is phenyl which is unsubstituted or especially has 1 or 2 substituents selected from Ci-C6-alkyl and Ci-C6-alkoxy and especially from methyl and methoxy.
  • Examples of particularly preferred Ar groups are methoxyphenyl or 2,4- dimethoxyphenyl.
  • R 1 and R 2 are especially each independently (methoxyphenyl)methyl or (2,4-dimethoxyphenyl)methyl.
  • R 1 and R 2 groups together are a radical of the formula A, as defined above, especially a radical of the formula Aa:
  • the monomers of the formula I can be prepared in analogy to processes known per se for preparation of organotin compounds.
  • monomers or compounds of the formula I in which R 1 is an Ar-C(R a ,R b )- radical will be prepared by reacting a suitable tin(ll) compound, for example a tin(ll) halide such as tin(ll) chloride or a tin(ll) alkoxide, e.g.
  • tin(ll) methoxide Sn(OCH 3 )2
  • the reaction is typically effected in the presence of a tertiary amine as a base.
  • the compounds of the formula Ar-C(R a ,R b )-XH or Ar-C(R a ,R b )-YH are used in excess, based on the desired stoichiometry of the reaction.
  • monomers or compounds of the formula I in which R 1 is an Ar-C(R a ,R b )- radical will be prepared by reacting a suitable tin(ll) compound, for example a tin(ll) halide such as tin(ll) chloride or a tin(ll) alkoxide, e.g. tin(ll) methoxide (Sn(OCH 3 )2), with a compound of the formula AXHYH
  • a suitable tin(ll) compound for example a tin(ll) halide such as tin(ll) chloride or a tin(ll) alkoxide, e.g. tin(ll) methoxide (Sn(OCH 3 )2)
  • AXHYH in which m, A, X, Y, R, R a and R b are each as defined above.
  • the reaction is effected typically in the presence of a tertiary amine as a base.
  • the compound AXHYH is used in excess, based on the desired stoichiometry of the reaction.
  • a monomer of the formula I also referred to hereinafter as monomer I
  • monomer I can be polymerized alone (homopolymerization). It is also possible to copolymerize mixtures of different monomers I.
  • one or more monomers I with substances known to be suitable for copolymerization with the R 1 or R 2 radicals.
  • substances known to be suitable for copolymerization with the R 1 or R 2 radicals include in particular aliphatic, aromatic or heteroaromatic aldehydes such as benzaldehyde, furfural, formaldehyde or acetaldehyde, preference being given to using formaldehyde in gaseous form or in a nonaqueous oligomeric or polymeric form, for example in the form of trioxane or paraformaldehyde.
  • inventive monomers I with other monomers which are copolymerizable under the conditions of a twin polymerization and comprise oxide-forming semimetals, as described, for example, in WO 2010/1 12580 and WO 2010/112581 , and which may have a metal or semimetal other than tin.
  • monomers of the general formula I described in WO 2010/1 12580 and WO 2010/1 12581 hereinafter formula X
  • M is a metal or semimetal, preferably a metal or semimetal of main group 3 or
  • transition group 4 or 5 of the Periodic Table especially B, Al, Si, Ti, Zr, Hf, Ge, Sn, Pb, V, As, Sb or Bi, more preferably B, Si, Ti, Zr or Sn, even more preferably Si or Ti and especially Si;
  • R 1a , R 2a may be the same or different and are each an Ar-C(R a ,R b )- radical in which
  • R a , R b are each as defined above in connection with formula I, especially the definitions cited as preferred,
  • R 1a X and R 2a Y radicals together are a radical of the formula A'
  • X is O, S or NH and especially O
  • Y is O, S or NH and especially O;
  • q according to the valency or charge of M is 0, 1 or 2 and especially 1 ,
  • G, Q may be the same or different and are each O, S, NH or a chemical bond and especially oxygen or a chemical bond;
  • R 1' , R 2' may be the same or different and are each Ci-C6-alkyl, C3-C6-cycloalkyl, aryl or an Ar'-C(R a' ,R b' )- radical in which Ar' is as defined for Ar, and R a' , R b' are each as defined for R a , R b and are especially each hydrogen, or R 1' , R 2' together with G and Q are a radical of the formula A' as defined above; and especially the monomers of the general formulae II, lla, III, Ilia, IV, V, Va, VI or Via described in WO 2010/1 12580 and WO 2010/1 12581 .
  • the proportion of the monomers other than the monomers of the formula I will not exceed 20% by weight and especially 10% by weight, based on the total amount of the monomers to be polymerized, i.e. the monomers of the formula I make up at least 80% by weight and especially at least 90% by weight of the total amount of the monomers to be polymerized.
  • the proportion of the monomers of the formula I in the total amount of the monomers to be polymerized makes up 20 to 80% by weight, especially 30 to 70% by weight, and the proportion of the monomers other than the monomers of the formula I, for example the monomers of the formula X or the aforementioned aldehydes, is in the range from 20 to 80% by weight and especially in the range from 30 to 70% by weight, based on the total amount of the monomers to be polymerized.
  • the monomers of the formula I can be polymerized and copolymerized with different monomers in analogy to the processes described in WO 2010/1 12580 and
  • the monomers I are polymerized in an organic solvent or solvent mixture, especially in an organic aprotic solvent or solvent mixture.
  • aprotic solvents in which the polymer composite material formed is insoluble (solubility ⁇ 1 g/l at 25°C).
  • the polymerization can also be effected in substance.
  • the aprotic solvent is preferably selected such that the monomer I is at least partly soluble. This is understood to mean that the solubility of the monomer I in the solvent under polymerization conditions is at least 50 g/l, especially at least 100 g/l.
  • the organic solvent is selected such that the solubility of the monomers at 20°C is 50 g/l, especially at least 100 g/l. More particularly, the solvent is selected such that the monomers I are substantially or completely soluble therein, i.e. the ratio of solvent to monomer I is selected such that, under polymerization conditions, at least 80%, especially at least 90% or the entirety of the monomers I is present in dissolved form.
  • Aprotic means that the solvent used for polymerization comprises essentially no solvents which have one or more protons which are bonded to a heteroatom such as O, S or N and are thus more or less acidic.
  • the proportion of protic solvents in the solvent or solvent mixture used for the polymerization is accordingly less than 10% by volume, particularly less than 1 % by volume and especially less than 0.1 % by volume, based on the total amount of organic solvent.
  • the polymerization of the monomers I is preferably performed in the substantial absence of water, i.e. the concentration of water at the start of the polymerization is less than 500 ppm, based on the amount of solvent used.
  • the solvent may be inorganic or organic or be a mixture of inorganic and organic solvents. It is preferably an organic solvent.
  • Suitable aprotic organic solvents are halohydrocarbons such as dichloromethane, chloroform, dichloroethane, trichloroethane, 1 ,2-dichloroethane, 1 ,1 ,1 -trichloroethane, 1 -chlorobutane, chlorobenzene, dichlorobenzenes,
  • fluorobenzene and also pure hydrocarbons, which may be aliphatic, cycloaliphatic or aromatic, and mixtures thereof with halohydrocarbons.
  • pure hydrocarbons are acyclic aliphatic hydrocarbons having generally 2 to 8 and preferably 3 to 8 carbon atoms, especially alkanes such as ethane, iso- and n-propane, n-butane and isomers thereof, n-pentane and isomers thereof, n-hexane and isomers thereof, n-heptane and isomers thereof, and n-octane and isomers thereof, cycloaliphatic hydrocarbons such as cycloalkanes having 5 to 8 carbon atoms, such as cyclopentane,
  • methylcyclopentane cyclohexane, methylcyclohexane, cycloheptane
  • aromatic hydrocarbons such as benzene, toluene, xylenes, mesitylene, ethylbenzene, cumene (2-propylbenzene), isocumene (1 -propylbenzene) and tert-butylbenzene.
  • halogenated hydrocarbons such as halogenated aliphatic hydrocarbons, for example such as chloromethane, dichloromethane, trichloromethane, chloroethane, 1 ,2-dichloroethane and 1 ,1 ,1 -trichloroethane and 1 -chlorobutane, and halogenated aromatic hydrocarbons such as chlorobenzene, 1 ,2-dichlorobenzene and fluorobenzene.
  • halogenated hydrocarbons such as chloromethane, dichloromethane, trichloromethane, chloroethane, 1 ,2-dichloroethane and 1 ,1 ,1 -trichloroethane and 1 -chlorobutane
  • halogenated aromatic hydrocarbons such as chlorobenzene, 1 ,2-dichlorobenzene and fluorobenzene.
  • inorganic aprotic solvents are especially supercritical carbon dioxide, carbon oxide sulfide, carbon disulfide, nitrogen dioxide, thionyl chloride, sulfuryl chloride and liquid sulfur dioxide, the three latter solvents also being able to act as polymerization initiators.
  • the monomers I are typically polymerized in the presence of a polymerization initiator or catalyst.
  • the polymerization initiator or catalyst is selected such that it initiates or catalyzes a cationic polymerization of the monomers I, i.e. of the monomer units XR 1 and YR 2 , and the formation of the tin oxide phase.
  • the monomer units XR 1 and YR 2 on the one hand polymerize and the tin oxide phase on the other hand forms synchronously.
  • the term “synchronously” does not necessarily mean that the polymerization of the monomer units XR 1 and YR 2 and the formation of the tin oxide phase proceed at the same rate. Instead, “synchronously” means that these processes are coupled kinetically and are triggered by the cationic polymerization conditions.
  • Suitable polymerization initiators or catalysts are in principle all substances which are known to catalyze cationic polymerizations. These include protic acids (Bransted acids) and aprotic Lewis acids.
  • Preferred protic catalysts are Bransted acids, for example organic carboxylic acids, for example trifluoroacetic acid, oxalic acid or lactic acid, and especially organic sulfonic acids such as methanesulfonic acid, trifluoromethane- sulfonic acid or toluenesulfonic acid.
  • suitable are inorganic Bransted acids such as HCI, H2SO4 or HCIO4.
  • the Lewis acids used may, for example, be BF3, BC , SnCU, TiCU, or AICI3.
  • the use of Lewis acids bound in complex form or dissolved in ionic liquids is also possible.
  • the polymerization initiator or catalyst is used typically in an amount of 0.1 to 10% by weight, preferably 0.5 to 5% by weight, based on the monomer
  • the temperatures required for the polymerization of the monomers I are typically in the range from 0 to 150°C, particularly in the range from 20 to 140°C and especially in the range from 40 to 120°C.
  • the process according to the invention is especially suitable for industrial production of tin oxide-containing polymer composite materials in continuous and/or batchwise mode.
  • batchwise mode this means batch sizes of at least 10 kg, frequently at least 100 kg, especially at least 1000 kg or at least 5000 kg.
  • continuous mode this means production volumes of generally at least 100 kg/day, frequently at least 1000 kg/day, especially at least 10 t/day or at least 100 t/day.
  • the tin oxide-containing polymer composite materials obtainable by the process according to the invention consist essentially, i.e. generally to an extent of at least 90% by weight, especially to an extent of at least 95% by weight, of tin oxide and an organic polymer phase.
  • the tin oxide phase generally consists essentially, i.e.
  • the organic polymer phase is formed by a carbonaceous polymer other than elemental carbon.
  • the composition of the organic polymer phase is defined by the Ar-C(R a ,R b ) groups, and so they are typically poly(het)arylformaldehyde condensates or polyaryl carbonates or mixtures thereof.
  • tin oxide phase and the organic polymer phase are present in a co-continuous arrangement over wide ranges, which means that the respective phase essentially does not form any isolated phase domains surrounded by an optionally continuous phase domain. Instead, the two phases form spatially separate continuous phase domains which penetrate one another, as can be seen by examining the materials by means of transmission electron microscopy.
  • continuous phase domains discontinuous phase domains
  • discontinuous phase domains and “co-continuous phase domains”
  • a co-continuous arrangement of a two-component mixture is understood to mean a phase-separated arrangement of the two phases or components, in which within one domain of the particular phase a continuous path through either phase domain may be drawn to all phase boundaries without crossing any phase domain boundary.
  • the regions in which the organic polymer phase and the tin oxide phase form essentially co-continuous phase domains make up at least 50% by volume, frequently at least 80% by volume and especially at least 90% by volume of the polymer composite material.
  • the distances between adjacent phase interfaces, or the distances between the domains of adjacent identical phases are small and are on average not more than 100 nm, particularly not more than 20 nm and especially not more than 10 nm.
  • the distance between adjacent identical phases is, for example, the distance between two domains of the tin oxide phase separated from one another by a domain of the organic polymer phase, or the distance between two domains of the organic polymer phase separated from one another by a domain of the tin oxide phase.
  • the mean distance between the domains of adjacent identical phases can be determined by means of small-angle x-ray scattering (SAXS) via the scatter vector q (measurement in transmission at 20°C, monochromatized CuK a radiation, 2D detector (image plate), slit collimation).
  • SAXS small-angle x-ray scattering
  • HAADF- STEM high angle annular darkfield scanning electron microscopy.
  • comparatively heavy elements for example Sn relative to C
  • Preparation artifacts can likewise be seen since denser regions of the preparations appear brighter than less dense regions.
  • the present invention also relates to the production of tin- carbon composite materials from at least one inorganic tin-containing phase in which tin is present in the form of tin in the +2 or 0 oxidation state, especially in elemental form or in the form of tin (I I ) oxide or Sn(ll) oxide hydrates, or in the form of a mixture thereof.
  • a tin oxide-containing polymer composite material is provided by the process described above.
  • This tin oxide-containing polymer composite material is carbonized in a second step.
  • the organic polymer phase is converted here to a phase consisting essentially of elemental carbon.
  • the phase structure is essentially preserved.
  • the polymer composite material obtained in step i. is typically heated with substantial exclusion of oxygen to temperatures of at least 400°C, preferably at least 500°C, especially of at least 700°C, for example to temperatures in the range from 400 to 1800°C, preferably in the range from 500 to 1500°C, especially in the range from 700 to 1200°C.
  • substantial exclusion of oxygen means that the partial oxygen pressure in the reaction zone in which the carbonization is performed is low and will preferably not exceed 20 mbar, especially 10 mbar.
  • the carbonization is performed in an inert gas atmosphere, for example under nitrogen or argon.
  • the inert gas atmosphere will preferably comprise less than 1 % by volume and especially less than 0.1 % by volume of oxygen.
  • the carbonization is performed in the presence of so-called reducing gases.
  • the reducing gases include, as well as hydrogen (hb), hydrocarbon gases such as methane, ethane or propane, or ammonia (NH3).
  • the reducing gases can be used as such or as a mixture with an inert gas such as nitrogen or argon.
  • the particulate composite material is preferably used for carbonization in the form of a dry, i.e. substantially solvent-free, powder.
  • solvent-free means here and hereinafter that the composite material comprises less than 1 % by weight, especially less than 0.1 % by weight, of solvent.
  • the carbonization is performed in the presence of an oxidizing agent which promotes the formation of graphite, for example of a transition metal halide such as iron trichloride.
  • an oxidizing agent which promotes the formation of graphite
  • a transition metal halide such as iron trichloride.
  • the amount of such oxidizing agents is generally 1 to 20% by weight, based on the polymer composite material.
  • the procedure is typically to mix the polymer composite material and the oxidizing agent with one another and to carbonize the mixture in the form of a substantially solvent-free powder.
  • the oxidizing agent is optionally removed after the carbonization, for example by washing the oxidizing agent out, for example using a solvent or solvent mixture in which the oxidizing agent and reaction products thereof are soluble, or by vaporization.
  • a preferably particulate tin-carbon composite material composed of a carbon phase and at least one tin phase is obtained.
  • the inventive carbon-tin composite material consists generally to an extent of at least 90% by weight, especially to an extent of at least 95% by weight, of at least one tin phase and of elemental carbon.
  • the tin-containing phase consists generally essentially, i.e. generally to an extent of at least 90% by weight, especially to an extent of at least 95% by weight, of tin or tin oxide or tin oxide hydrates or a mixture thereof.
  • the tin-carbon composite material comprises a carbon phase (hereinafter also C phase) in which the carbon is present essentially in elemental form, which means that the proportion of the non-carbon atoms in the carbon phase, e.g. N, O, S, P and/or H, is less than 10% by weight, especially less than 5% by weight, based on the total amount of carbon in the C phase.
  • the content of non-carbon atoms in the C phase can be determined by means of x-ray photoelectron
  • the C phase may, as a result of the preparation, especially comprise small amounts of nitrogen, oxygen, sulfur and/or hydrogen.
  • the molar ratio of hydrogen to carbon will generally not exceed a value of 1 :3, particularly a value of 1 :5 and especially a value of 1 :10. The value may also be 0 or virtually 0, e.g. ⁇ 0.1.
  • the carbon is probably present predominantly in amorphous or graphitic form.
  • the presence of amorphous or graphitic carbon can be determined by means of ESCA studies with reference to the characteristic binding energy (284.5 eV) and the characteristic asymmetric signal shape.
  • Carbon in graphitic form is understood to mean that the carbon is at least partly in a hexagonal layer arrangement typical of graphite, where the layers may also be curved or exfoliated.
  • the inventive tin-carbon composite material comprises at least one tin phase (Sn phase), the tin in the tin phase being in the +2 or 0 oxidation state or in a mixed form thereof.
  • the Sn phase preferably consists essentially of elemental tin or tin (I I ) oxide or tin(ll) oxide hydrates such as tin(ll) hydroxide or a mixture thereof.
  • the proportion of non-tin and -oxygen atoms, for example other metals or semimetals and N, S, P and/or H is preferably less than 10% by weight, especially less than 5% by weight, based on the total amount of carbon in the Sn phase.
  • the tin may be in the form of tin in the +2 oxidation state or in the form of elemental tin, i.e. tin in the 0 oxidation state, or in the form of a mixed form thereof.
  • the tin is predominantly in the 0 oxidation state, which means that at least 50%, especially at least 80% or at least 90% of the tin atoms of the Sn phase are in the 0 oxidation state and especially in the form of elemental tin.
  • the C phase and the Sn phase form essentially co-continuous phase domains with irregular arrangement, the mean distance between two adjacent domains of the Sn phase, or the mean distance between two adjacent domains of the C phase, being not more than 100 nm, particularly not more than 20 nm, especially not more than 10 nm, and being, for example, in the range from 0.5 to 100 nm, particularly 0.7 to 20 nm and especially 1 to 10 nm.
  • the statements made above for the polymer composite material obtained in step i. apply in the same way.
  • the Sn phase is in the form of Sn domains which are embedded in an essentially isolated manner in a continuous carbon phase C as the matrix.
  • frequently more than 50% by volume of the Sn domains have a size in the range from 1 nm to 20 ⁇ , especially 1 nm to 1 ⁇ .
  • the tin content is 5 to 90% by weight, preferably 10 to 75% by weight, more preferably 15 to 55% by weight, especially 20 to 40% by weight, based on the total mass of the tin-carbon composite materials.
  • the process according to the invention is especially suitable for industrial production of tin-carbon composite materials in continuous and/or batchwise mode.
  • batchwise mode this means batch sizes of at least 10 kg, frequently at least 100 kg, especially at least 1000 kg or at least 5000 kg.
  • continuous mode this means production amounts of generally at least 100 kg/day, frequently at least 1000 kg/day, especially at least 10 t/day or at least 100 t day.
  • the inventive tin-carbon composite material is notable, as already stated, for particularly advantageous properties when employed in electrochemical cells, especially lithium ion cells, especially for a high specific capacity, good cycling stability, low tendency to self-discharge and to form lithium dendrites, and for advantageous kinetics with regard to the charging/discharging operation, such that high current densities can be achieved.
  • an electrochemical cell or battery is understood to mean batteries, capacitors and accumulators (secondary batteries) of any kind, especially alkali metal cells or batteries, for example lithium, lithium ion, lithium-sulfur and alkaline earth metal batteries and accumulators, specifically also in the form of high-energy or high-performance systems, and electrolytic capacitors and double layer capacitors known by the Supercaps, Goldcaps, BoostCaps or Ultracaps names.
  • the invention therefore also provides for the use of the tin-carbon composite material for production of electrochemical cells and more particularly for the use thereof in anodes for lithium ion cells, especially lithium ion secondary cells.
  • the invention accordingly also relates to an anode for lithium ion cells, especially lithium ion secondary cells, which comprises an inventive tin-carbon composite material.
  • the anode generally comprises at least one suitable binder for consolidation of the inventive tin-carbon composite material and optionally of further electrically conductive or electroactive constituents.
  • the anode generally has electrical contacts for supply and removal of charges.
  • the amount of inventive tin-carbon composite material, based on the total mass of the anode material, minus any current collectors and electrical contacts, is generally at least 40% by weight, frequently at least 50% by weight and especially at least 60% by weight.
  • Suitable further conductive or electroactive constituents are known from relevant monographs (see, for example, M.E. Spahr, Carbon Conductive Additives for Lithium- Ion Batteries, in M. Yoshio et al.
  • inventive anodes include carbon black, graphite, carbon fibers, carbon nanofibers, carbon nanotubes or electrically conductive polymers.
  • conductive material typically, about 2.5 to 40% by weight of the conductive material are used in the anode together with 50 to 97.5% by weight, frequently with 60 to 95% by weight, of the inventive electroactive material, the figures in % by weight being based on the total mass of the anode material, minus any current collectors and electrical contacts.
  • Useful binders for the production of an anode using the aforementioned tin-carbon composite materials and further electroactive materials in principle include all prior art binders suitable for anode materials, as known from relevant monographs (see, for example, A. Nagai, Applications of PVdF-Related Materials for Lithium-Ion Batteries, in M. Yoshio et al. (eds.) Lithium Ion Batteries, Springer Science + Business Media, New York 2009, p. 155-162 and literature cited therein, and also H. Yamamoto and H. Mori, SBR Binder (for negative electrode) and ACM Binder (for positive electrode), ibid., p. 163-180).
  • Useful binders include especially the following polymeric materials: polyethylene oxide (PEO), cellulose, carboxymethylcellulose (CMC), polyethylene, polypropylene, polytetrafluorethylene, polyacrylonitrile-methyl methacrylate, polytetrafluoroethylene, styrene-butadiene copolymers, tetrafluoroethylene- hexafluoroethylene copolymers, polyvinylidene difluoride (PVdF), polyvinylidene difluoride hexafluoropropylene copolymers (PVdF-HFP), tetrafluoroethylene hexa- fluoropropylene copolymers, tetrafluoroethylene, perfluoroalkyl-vinyl ether copolymers, vinylidene fluoride-hexafluoropropylene copolymers, ethylene-tetrafluoroethylene copolymers, vinylidene fluoride-chloro
  • the binder is optionally selected with consideration of the properties of any solvent used for the preparation.
  • the binder is generally used in an amount of 1 to 10% by weight, based on the overall mixture of the anode material, i.e. tin-carbon composite material and optionally further electroactive or conductive materials. Preferably 2 to 8% by weight and especially 3 to 7% by weight are used.
  • the anode can be produced in a manner customary per se by standard methods as known from the prior art cited at the outset and from relevant monographs (see, for example, R. J. Brodd, M. Yoshio, Production processes for Fabrication of Lithium-Ion Batteries, in M. Yoshio et al. (eds.) Lithium Ion Batteries, Springer Science + Business Media, New York 2009, p. 181 -194 and literature cited therein).
  • the anode can be produced by mixing the inventive electroactive material, optionally using an organic solvent (for example N-methylpyrrolidinone or a hydrocarbon solvent), with the optional further constituents of the anode material (electrically conductive constituents and/or organic binder), and optionally subjecting it to a shaping process or applying it to an inert metal foil, for example Cu foil.
  • an organic solvent for example N-methylpyrrolidinone or a hydrocarbon solvent
  • an inert metal foil for example Cu foil.
  • drying is optionally followed by drying. This is done, for example, using a temperature of 80 to 150°C. The drying operation can also take place under reduced pressure and lasts generally for 3 to 48 hours.
  • the present invention also provides lithium ion cells, especially lithium ion secondary cells which have at least one anode comprising an inventive tin-carbon composite material.
  • Such cells generally have at least one inventive anode, a cathode suitable for lithium ion cells, an electrolyte and optionally a separator.
  • a cathode suitable for lithium ion cells an electrolyte and optionally a separator.
  • suitable cathode materials suitable electrolytes and suitable separators, and to possible arrangements, reference is made to the relevant prior art, for example the prior art cited at the outset, and to appropriate monographs and reference works: for example Wakihara et al. (editor) in Lithium Ion Batteries, 1 st edition, Wiley VCH, Weinheim, 1998; David Linden: Handbook of Batteries (McGraw-Hill Handbooks), 3rd edition, McGraw-Hill Professional, New York 2008; J. O. Besenhard: Handbook of Battery Materials.
  • Useful cathodes include especially those cathodes in which the cathode material comprises at least one lithium-transition metal oxide, e.g.
  • 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.
  • Useful cathode materials also include sulfur and sulfur-containing composite materials, for example sulfur-carbon composite materials as known for lithium-sulfur cells.
  • the two electrodes i.e. the anode and the cathode, are connected to one another using a liquid or else solid electrolyte.
  • Useful liquid electrolytes include especially nonaqueous solutions (water content generally ⁇ 20 ppm) of lithium salts and molten Li salts, for example solutions of lithium hexafluorophosphate, lithium perchlorate, lithium hexafluoroarsenate, lithium trifluoromethylsulfonate, lithium bis(trifluoromethyl- sulfonyl)imide or lithium tetrafluoroborate, especially lithium hexafluorophosphate or lithium tetrafluoroborate, in suitable aprotic solvents, for example ethylene carbonate, propylene carbonate and mixtures thereof with one or more of the following solvents: dimethyl carbonate, diethyl carbonate, dimethoxyethane, methyl propionate, ethyl propionate, butyrolactone, acetonitrile
  • a separator impregnated with the liquid electrolyte may be arranged between the electrodes.
  • separators are especially glass fiber nonwovens and porous organic polymer films, such as porous films of polyethylene, polypropylene, PVdF etc.
  • These may have, for example, a prismatic thin film structure, in which a solid thin film electrolyte is arranged between a film which constitutes an anode and a film which constitutes a cathode.
  • a central cathode output conductor is arranged between each of the cathode films in order to form a double-faced cell configuration.
  • an insulating film is typically arranged between individual anode/separator/cathode/output conductor element combinations.
  • the TEM analyses were HAADF-STEM analyses conducted with a Tecnai F20 transmission electron microscope (FEI, Eindhoven, The Netherlands) at a working voltage of 200 kV in the ultrathin layer technique (embedding of the samples into synthetic resin as a matrix).
  • FEI Tecnai F20 transmission electron microscope
  • the small-angle x-ray scattering analyses were affected at 20°C in slit collimation using CuK a radiation monochromatized with Gobel mirrors. The data were collected against the background and sharpened in respect of the blurring caused by the slit collimation.
  • the abbreviations s, m and w stand for strong, moderate and weak, and indicate the relative intensity of the bands.
  • Example 1 Production of the polymer composite materials: Example 1 :
  • Example 3 In a manner analogous to example 1 , 0.52 g of the compound from preparation example 1 was polymerized using 10 mol% of trifluoroacetic acid as a catalyst. The polymer composite material was obtained as a colorless solid in a yield of 0.06 g (12%).
  • Example 3

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Composite Materials (AREA)
  • Materials Engineering (AREA)
  • Engineering & Computer Science (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Polyethers (AREA)
  • Electric Double-Layer Capacitors Or The Like (AREA)
  • Carbon And Carbon Compounds (AREA)

Abstract

La présente invention porte sur de nouveaux matériaux composites polymères contenant de l'oxyde d'étain, sur un procédé pour leur production et sur leur utilisation pour la production d'un matériau composite d'étain-carbone composé d'au moins une phase inorganique contenant de l'étain dans laquelle l'étain est présent sous forme élémentaire ou sous la forme d'oxyde d'étain(II) ou sous la forme d'un mélange de ceux-ci, et d'une phase carbonée dans laquelle le carbone est présent sous forme élémentaire. De tels matériaux composites d'étain-carbone sont particulièrement appropriés pour la fabrication de matériaux anodiques pour des piles électrochimiques, en particulier des piles au lithium.
PCT/IB2012/054928 2011-09-19 2012-09-18 Matériaux composites polymères contenant de l'oxyde d'étain Ceased WO2013042034A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
EP12833502.3A EP2759008A4 (fr) 2011-09-19 2012-09-18 Matériaux composites polymères contenant de l'oxyde d'étain
KR1020147010222A KR20140068202A (ko) 2011-09-19 2012-09-18 주석 옥사이드-함유 중합체 복합재
JP2014530373A JP2014532258A (ja) 2011-09-19 2012-09-18 酸化スズ含有ポリマー複合材料
CN201280043102.0A CN103782422A (zh) 2011-09-19 2012-09-18 包含氧化锡的聚合物复合材料

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP11181795 2011-09-19
EP11181795.3 2011-09-19

Publications (1)

Publication Number Publication Date
WO2013042034A1 true WO2013042034A1 (fr) 2013-03-28

Family

ID=47913955

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/IB2012/054928 Ceased WO2013042034A1 (fr) 2011-09-19 2012-09-18 Matériaux composites polymères contenant de l'oxyde d'étain

Country Status (5)

Country Link
EP (1) EP2759008A4 (fr)
JP (1) JP2014532258A (fr)
KR (1) KR20140068202A (fr)
CN (1) CN103782422A (fr)
WO (1) WO2013042034A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8865858B2 (en) 2012-06-26 2014-10-21 Basf Se Process for producing a composite material
WO2015032662A1 (fr) * 2013-09-06 2015-03-12 Basf Se Procédé de production de particules de dioxyde d'étain
CN114122512A (zh) * 2021-11-11 2022-03-01 合肥工业大学 固态电解质、其制备方法及包含其的固态二次电池

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103981506B (zh) * 2014-05-29 2015-12-30 武汉大学 一种碳-锡复合导电膜的制备方法
CN106847553B (zh) * 2017-01-11 2018-10-26 中南民族大学 孪生聚合法制备电极材料的方法
CN111883763B (zh) * 2020-08-07 2021-12-31 华东理工大学 一种氮掺杂碳纳米SnO2复合材料及其制备方法和应用

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA2754711A1 (fr) * 2009-04-03 2010-10-07 Basf Se Matiere electroactive et son utilisation dans des anodes pour des cellules aux ions lithium

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6740453B2 (en) * 2002-02-27 2004-05-25 Cyprus Amax Minerals Company Electrochemical cell with carbonaceous material and molybdenum carbide as anode
CN100423328C (zh) * 2005-01-14 2008-10-01 哈尔滨光宇电源股份有限公司 一种锂离子二次电池正极材料的制备方法及该锂离子二次电池
EP2414457B1 (fr) * 2009-04-03 2013-01-09 Basf Se Procédé pour produire des matériaux composites

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA2754711A1 (fr) * 2009-04-03 2010-10-07 Basf Se Matiere electroactive et son utilisation dans des anodes pour des cellules aux ions lithium

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP2759008A4 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8865858B2 (en) 2012-06-26 2014-10-21 Basf Se Process for producing a composite material
WO2015032662A1 (fr) * 2013-09-06 2015-03-12 Basf Se Procédé de production de particules de dioxyde d'étain
CN114122512A (zh) * 2021-11-11 2022-03-01 合肥工业大学 固态电解质、其制备方法及包含其的固态二次电池
CN114122512B (zh) * 2021-11-11 2023-07-25 合肥工业大学 固态电解质、其制备方法及包含其的固态二次电池

Also Published As

Publication number Publication date
CN103782422A (zh) 2014-05-07
JP2014532258A (ja) 2014-12-04
KR20140068202A (ko) 2014-06-05
EP2759008A1 (fr) 2014-07-30
EP2759008A4 (fr) 2015-03-18

Similar Documents

Publication Publication Date Title
US8992801B2 (en) Electroactive material, and use thereof in anodes for lithium-ion cells
US9099744B2 (en) Particulate porous carbon material and use thereof in lithium cells
KR20140018907A (ko) 미립자 다공성 탄소 물질 및 리튬 전지에서 그의 용도
US20200044240A1 (en) Graphite and Group IVA Composite Particles and Methods of Making
WO2013042034A1 (fr) Matériaux composites polymères contenant de l'oxyde d'étain
KR20160045378A (ko) 실리콘-실리콘 옥시카바이드 복합체, 이의 제조 방법, 이를 포함하는 음극 활물질 및 리튬이차전지
CN114599983A (zh) 预测包括碳基混合负极的二次电池的循环寿命的方法
TW201806860A (zh) 鋰離子二次電池用負極活性物質的製造方法
JP2023543864A (ja) 正極活物質、これを含む正極及びリチウム二次電池
WO2017028160A1 (fr) Procédé permettant de préparer un revêtement de carbone sur un matériau à base de silicium et composite silicium-carbone
KR102890300B1 (ko) 양극 활물질 분말, 이를 포함하는 양극 및 리튬 이차 전지
CN107851784A (zh) 锂离子二次电池用负极活性物质及其制造方法
US20130341559A1 (en) Composite materials and process for production thereof
US20130069021A1 (en) Tin oxide-containing polymer composite materials
EP4318625A1 (fr) Anode pour batterie secondaire au lithium et batterie secondaire au lithium la comprenant
US20130043427A1 (en) Novolac-based c-sn materials, production thereof and use thereof in electrochemical cells
JP7635400B2 (ja) 正極及びそれを含むリチウム二次電池
CN121359250A (zh) 用于制造用于锂离子电池的负极和负极材料的方法及其区分方法
JP2023532035A (ja) サイクル寿命性能が改善されたリチウム－硫黄電池
TW201323434A (zh) 包含氧化錫之聚合物複合材料
JP7785802B2 (ja) 負極活物質、前記負極活物質を含む負極、前記負極を含む二次電池、および前記負極活物質の製造方法
KR102867402B1 (ko) 양극 활물질 분말, 이를 포함하는 양극 및 리튬 이차 전지
JP2015522681A (ja) 複合材料およびその製造方法
JP7621484B2 (ja) リチウム二次電池用正極活物質、その製造方法、及びそれを含むリチウム二次電池
EP4645465A1 (fr) Particules composites, et procédé de fabrication ainsi qu?application de celles-ci

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 12833502

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2014530373

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

WWE Wipo information: entry into national phase

Ref document number: 2012833502

Country of ref document: EP

ENP Entry into the national phase

Ref document number: 20147010222

Country of ref document: KR

Kind code of ref document: A