WO2013027157A2 - Matières contenant du carbone et de l'étain à base de novolaque, leur fabrication et leur utilisation dans des cellules électrochimiques - Google Patents

Matières contenant du carbone et de l'étain à base de novolaque, leur fabrication et leur utilisation dans des cellules électrochimiques Download PDF

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WO2013027157A2
WO2013027157A2 PCT/IB2012/054156 IB2012054156W WO2013027157A2 WO 2013027157 A2 WO2013027157 A2 WO 2013027157A2 IB 2012054156 W IB2012054156 W IB 2012054156W WO 2013027157 A2 WO2013027157 A2 WO 2013027157A2
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novolak
phase
domains
electroactive material
sno
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PCT/IB2012/054156
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German (de)
English (en)
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WO2013027157A3 (fr
Inventor
Gerhard Cox
Klaus Leitner
Arno Lange
Rüdiger OESTEN
Markus HÖLZLE
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Basf Se
Basf (China) Company Limited
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Priority to KR1020147007109A priority Critical patent/KR20140058637A/ko
Priority to CN201280039224.2A priority patent/CN104114617A/zh
Priority to JP2014526579A priority patent/JP2015513169A/ja
Priority to EP12825111.3A priority patent/EP2850117A4/fr
Publication of WO2013027157A2 publication Critical patent/WO2013027157A2/fr
Publication of WO2013027157A3 publication Critical patent/WO2013027157A3/fr

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    • 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
    • C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
    • C08G8/04—Condensation polymers of aldehydes or ketones with phenols only of aldehydes
    • C08G8/08—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ
    • C08G8/24—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ with mixtures of two or more phenols which are not covered by only one of the groups C08G8/10 - C08G8/20
    • 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
    • C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
    • C08G8/04—Condensation polymers of aldehydes or ketones with phenols only of aldehydes
    • C08G8/08—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ
    • C08G8/12—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ with monohydric phenols having only one hydrocarbon substituent ortho on para to the OH group, e.g. p-tert.-butyl phenol
    • 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
    • C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
    • C08G8/04—Condensation polymers of aldehydes or ketones with phenols only of aldehydes
    • C08G8/08—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ
    • C08G8/20—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ with polyhydric phenols
    • 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
    • C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
    • C08G8/28—Chemically modified polycondensates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
    • C08L61/04—Condensation polymers of aldehydes or ketones with phenols only
    • C08L61/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
    • C08L61/12—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols with polyhydric phenols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
    • C08L61/04—Condensation polymers of aldehydes or ketones with phenols only
    • C08L61/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
    • C08L61/14—Modified phenol-aldehyde condensates
    • 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
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
    • 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
    • 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 a process for producing a Sn (II) crosslinked novolak material, the Sn (II) crosslinked novolak material obtainable by the process of the present invention, a process for producing an electroactive material comprising a carbon phase C and a tin Phase and / or tin oxide phase, comprising the process for producing a Sn (II) crosslinked novolak material and a subsequent carbonization step, the electroactive material obtainable by the process according to the invention, and electrochemical cells and batteries containing the electroactive material ,
  • 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-ion.
  • the cathode typically comprises a lithium transition metal compound such as UC0O2 or LiFePC and anode usually contains graphite, Li is 0 intercalated during the charging in the.
  • a lithium transition metal compound such as UC0O2 or LiFePC
  • anode usually contains graphite, Li is 0 intercalated during the charging in the.
  • anodes containing lithium-metal alloys for example lithium-tin or lithium-silicon alloys.
  • the alloys Li 4 , 4 Sn and Li 4 , 4 Si can absorb large amounts of lithium and show significantly higher capacities than a graphite electrode with intercalated Li 0 .
  • electroactive material is proposed, which is a co-continuously nanostructured hybrid material and which is obtainable starting from a material obtainable by a so-called twin polymerization with subsequent carbonation step.
  • WO 2010/1 12580 only silicon-containing electroactive materials starting from special soluble spirosilanes are described in the examples. Less easy it is, however, to prepare suitable soluble monomers such as 2,2 '-Spirobis [4H-1, 3,2-benzodioxastannin], since such tin derivatives have a tendency highly aggregated to form insoluble and refractory shapes, such as, for example, in Cotton Wilkinson "Advanced Inorganic Chemistry” John Wiley & Sons Inc. 6th Edition, page 280, 287 et seq.
  • CN 101428847 describes the synthesis of a tin-containing nanomaterial for lithium-ion batteries to obtain nanostructured tin oxide by heating an aqueous solution of tin chloride, resorcinol, hydrochloric acid and formaldehyde, separating the precipitated hybrid material and calcining in air.
  • a disadvantage of this process is, in particular, the formation in the literature of the extremely human carcinogenic bis-chloromethyl ether.
  • the task was thus to find technically feasible methods with which a nanostructured C / Sn-containing electroactive material which is suitable as anode material for lithium-ion batteries, in particular for lithium-ion secondary batteries, and its starting materials can be produced on a multitone scale and in reproducible quality can.
  • the methods must be economical, for example by avoiding expensive methods such as the CVD method, or also with regard to safety-relevant aspects, such as the avoidance of carcinogenic by-products which improve known methods.
  • a further object was to find new starting compounds for new nanostructured C / Sn-containing electroactive materials and the new electroactive materials that can be produced therefrom, which are easy to prepare or superior to the graphite or the alternatives discussed so far.
  • the electroactive material should have a high specific capacity, high cycle stability, low self-discharge and / or good mechanical stability.
  • Novolacs and their preparation have long been known to the skilled person and are described, for example, in Houben-Weyl, Methods of Organic Chemistry, Thieme Verlag, Stuttgart, Volume 14, Part 2: Macromolecular Substances, pages 193-212, 272-274 and Volume E20 , Pages 1800 - 1806 described in detail.
  • phenol or a substituted phenol is condensed with an aldehyde or a ketone, preferably an aldehyde, with formaldehyde under acidic or basic, preferably under acidic conditions with elimination of water to form linear, non-crosslinked oligomers or polymers.
  • a novolak molecule is a linear, non-crosslinked moiety which means that a single aryl moiety is linked to not more than two substituted or unsubstituted alkylene groups.
  • the phenol component used can be, for example, phenol, resorcinol, pyrocatechol, hydroquinone, pyrogallol, phoroglucinol, apionol, 1,2,4,5-tetrahydroxybenzene, cresols or also bisphenol A, and as aldehyde or ketone it is possible, for example (Para ) formaldehyde, trioxane, acetaldehyde, furfural or acetone use.
  • process step (a) comprises at least one novolak containing aryl units bearing two, three or four hydroxyl groups, at least two hydroxy groups being adjacent to one another at least one substituted or unsubstituted alkylene group are linked to further aryl units, reacted with at least one Sn (II) salt.
  • a novolak containing aryl moieties bearing two, three or four hydroxy groups wherein at least two hydroxy groups are adjacent to each other and which have at least one Substituted or unsubstituted alkylene group are linked to other aryl units, is known in principle.
  • US Pat. No. 5,859,153 describes a novolak composed of catechol and formaldehyde.
  • the aryl units which carry two, three or four hydroxyl groups, wherein at least two hydroxy groups are adjacent to one another, are derived from substituted or unsubstituted 1,2-bishydroxybenzene as the phenol component.
  • substituted or unsubstituted 1, 2-Bishydroxybenzol are 1, 2-dihydroxybenzene, 1, 2,3-trihydroxybenzene or 1, 2,4-trihydroxybenzene.
  • the phenol component used is preferably 1,2-bishydroxybenzene itself, which is also called catechol.
  • the novolac material may also contain amine nitrogen. This can be accomplished by adding a reactive amine component (e.g., 4-aminophenol) to the reaction mixture or allowing the novolac to react with such a component.
  • a reactive amine component e.g., 4-aminophenol
  • the substituted or unsubstituted alkylene group which links together two aryl units may be, for example, -CH 2 -, -CH (Me) -, -CH (l -furyl) - or -C (Me) 2-, preferably -CH 2 - act.
  • formaldehyde CH 2 O and its equivalents such as paraformaldehyde, aqueous formalin solution or trioxane, also referred to together below as formaldehyde (equivalent), are the preferred components for generating the preferred alkylene group -CH 2 -.
  • the novolak contains, as alkylene groups, methylene units which in each case link together two aryl units.
  • the linkage between the aryl moieties is accomplished by furfural or mixtures of furfural with formaldehyde (equivalent). Examples are mixtures with more than 20 mol% formaldehyde (equivalent) or better than 50 mol% formaldehyde (equivalent) or preferably over 75 mol% formaldehyde (equivalent) or more preferably over 90 mol% formaldehyde (equivalent).
  • the further aryl moieties may be identical to either the aryl moieties bearing two, three or four hydroxy groups wherein at least two hydroxy groups are adjacent to each other or derived from any other substituted phenols or phenol itself as the phenolic moiety.
  • a novolac such as the example shown in US Pat. No. 5,859,153 and shown above, consists, like virtually every engineered polymer, of polymer chains of different chain lengths, the polymer being indicated by the average chain length, for example by giving the average number n of monomer units per polymer chain or by specifying the weight average molecular weight M w tries to describe.
  • the novolak used in the process according to the invention may, in principle, comprise any number of aryl moieties per oligomer or polymer molecule, the lower limit being two, ie. H. that exactly two aryl units are linked together via exactly one substituted or unsubstituted alkylene group, in particular a methylene unit.
  • the maximum average number of aryl units of the novolak used is preferably up to 1000, particularly preferably up to 100, very particularly preferably up to 20, in particular up to 10.
  • a novolak is reacted which has on average from 2 to 10 aryl units, for example 3, 4, 5, 6, 7 or 8 units.
  • a novolak is reacted in process step (a), which is characterized in that at least 50%, preferably at least 80%, in particular at least 95% to at most 100% of the novolacs A rylariien two hydroxy groups which are adjacent and are at least 50%, preferably at least 80%, in particular at least 95% to at most 100% of the alkylene units methylene groups.
  • reaction of the novolak with the Sn (l l) salt can be carried out in any desired manner, as long as it is ensured that the two components can react with one another.
  • the reaction can therefore be carried out in bulk, for example in a melt, or in the presence of a solvent.
  • process step (a) is carried out in a solvent in which the novolak is present in dissolved form, particularly preferably in a solvent in which the novolak and the Sn (l l) salt are present in dissolved form.
  • the solvent used is preferably water, a C 1 -C 6 -alkanol, a cyclic or acyclic ether having 4 to 8 C atoms or a cyclic or acyclic ketone having 3 to 8 C atoms.
  • suitable C 1 -C 6 -alkanols are methanol, ethanol, n- or isopropanol, n-, sec-, iso- or tert-butanol, a pentanol or a hexanol.
  • Suitable cyclic or acyclic ethers having 4 to 8 C atoms are diethyl ether, methyl tert-butyl ether, diisopropyl ether, di-n-butyl ether, tetrahydrofuran or dioxane.
  • Suitable cyclic or acyclic ketones having 3 to 8 carbon atoms are acetone, butanone or cyclohexanone.
  • the Sn (II) salt is optionally initially charged in a solvent and the novolak, optionally in a solvent, is added.
  • the novolak is optionally initially charged in a solvent and the Sn (II) salt, if appropriate in a solvent, is added.
  • Sn (II) salts which can be used in the process according to the invention are known in principle to the person skilled in the art. These may be salts derived from both inorganic and organic Brönstedt acids. Preference is given to using those Sn (II) salts which dissolve in a melt of the novolak used or preferably dissolve in the same solvent as the novolak used.
  • the Sn (II) salt is preferably selected from the group of the salts consisting of SnC, SnBr2, Sn (acetate) 2, Sn-oxalate, SnS0 4 , Sn (NO 3 ) 2 and mixtures of these salts and also their salts hydrates; particularly preferred are SnC and Sn (acetate) 2.
  • an acid forms from a proton of a hydroxy group of the novolak and an anion of the Sn (II) salt.
  • the acid which forms can be trapped with a suitable base, which is usually selected by a person skilled in the art on the basis of their solubility in the reaction system.
  • process step (a) is carried out in the presence of a base.
  • a base In addition to alkali metal alcoholates, alkali metal hydroxides, alkali metal carbonates and alkali metal hydrogencarbonates, for example, ammonia or primary, secondary or tertiary amines can also be used as the base. Examples are NaOCH 3 , KO-tC 4 H 9 , NaOH, KOH, LiOH, Na 2 C0 3 , K 2 C0 3 , Li 2 C0 3 , NaHC0 3 , KHC0 3 , (CH 3 ) 3 N, (C 2 H 5 ) 3 N, morpholine, piperidine.
  • the order of addition can be varied within wide limits. So you can submit the novolac, add the base and then the Sn compound or Sn compound and base are separated but added simultaneously to a preparation of the novolac. Likewise, you can submit the novolac, add the Sn compound and then the base. Further, a novolak / base mixture may be added to a preparation of the Sn compound, or novolak and base may be added separately but simultaneously to a treatment of the Sn compound.
  • the ratio of the Sn (II) salt to the novolak can in principle be varied within a wide range.
  • a Sn (II) -linked novolak material theoretically a Sn (II) with two hydroxy groups from the novolak reacts. Because of the chelating effect of two hydroxy groups adjacent to an aryl moiety, it is envisioned that Sn (II) will preferentially bind in such an environment.
  • the tin In order to avoid the formation of tin oxides outside the polymer matrix, preference is given to converting only those amounts of Sn (II) salt with novolak, the tin also being more than 50%, preferably more than 70%, particularly preferably more than 90% % is bound up to 100% in the polymer matrix.
  • the proportion of tin bound in the polymer matrix may also vary at the same starting ratios of Sn (II) salt to novolaks, since in water, for example, the simple tin oxide formation competes with the reaction of the Sn (II) salt with the hydroxy groups of the novolak ,
  • the molar ratio of the Sn (II) salt to the aryl moieties from the novolak carrying two, three or four hydroxy groups, wherein at least two hydroxy groups are adjacent to each other is from 0.05 to 1 to 1 to 1 .
  • the ratio is 0.1 to 1 to 0.9 to 1, preferably 0.2 to 1 to 0.7 to 1, particularly preferably 0.3 to 1 to 0.6 to 1.
  • the "non (semi) metallic part" - ie for example the counterion - may be the same (eg SnC and SbC) or different (eg SnC and Pb (NO 3 ) 2 ).
  • the one or more (half) metal (s) may be the 1st, 2nd, 3rd, 4th, 5th, 6th, 7th, 8th, 9th, 10th, 1 1st, 12th, 13th ., 14th or 15th group of the Periodic Table of the Elements. Examples are: Li, Mg, Ca, La, Ti, V, Mo, Mn, Fe, Co, Ni, Cu, Ag, Zn, Al, Si, Ge, Pb, As, Sb, Bi. In one embodiment, there is then a mixture of Sn and Co, which composition may vary within the specified limits and comprises, for example, the range of weight ratios Sn / Co from 65/35 to 85/15.
  • a mixture of Sn and Fe is then present, it being possible for the composition to vary within the stated limits and, for example, to cover the range of the weight ratios Sn / Fe of 65/35 to 85/15.
  • a mixture of Sn and Mn is then present, it being possible for the composition to vary within the stated limits and, for example, to cover the range of the weight ratios Sn / Mn from 65/35 to 85/15.
  • a mixture of Sn and Cu is then present, it being possible for the composition to vary within the stated limits and, for example, to encompass the range of weight ratios Sn / Cu from 40/60 to 80/20.
  • an Sn (II) -linked novolak material optionally formed in the form of a powder can be isolated. Preference is given to the possibility of isolating the Sn (II) -linked novolak material formed in the form of a powder, if process step (a) was carried out in a solvent in which the novolak initially present in dissolved form and only by reaction with the Sn (II) salt of a Sn (II) -crosslinked novolak material in the solvent in the form of a powder.
  • Sn (II) - crosslinked novolak material in the form of a powder has an average particle size of 1 to 100 ⁇ , preferably from 10 to 60 ⁇ , in particular from 15 to 50 ⁇ on.
  • a further subject of the present invention is also a Sn (II) -crosslinked novolak material obtained by reacting a novolak containing aryl moieties bearing two, three or four hydroxyl groups, wherein at least two hydroxy groups are adjacent to each other, and which are at least a substituted or unsubstituted alkylene group is linked to other aryl units, with at least one Sn (II) salt, in particular in a solvent, is available.
  • R 1 and R 2 may be identical or different and each represents hydrogen, hydroxyl, halogen or an organic radical having 1 to 20 carbon atoms, in particular hydrogen,
  • R 3 and R 4 may be the same or different and each represents hydrogen or an organic radical having 1 to 20 carbon atoms, in particular hydrogen, the carbon atom bearing a hydrogen atom or having a bivalent radical C (R 3 ) (R 4 ), the is linked to another aryl moiety, and the carbon atom designated ** is connected to another aryl moiety.
  • organic radical having 1 to 20 carbon atoms denotes, for example, C 1 -C 20 -alkyl radicals, saturated C 3 -C 20 -heterocyclic radicals, C 6 -C 20 -aryl radicals, C 2 -C 20 -aromatic radicals or C 7 -C 20 -arylalkyl radicals in which the carbon-containing radical may contain further heteroatoms selected from the group of elements consisting of F, Cl, Br, I, N, P, Si, O and S and / or may be substituted by functional groups.
  • saturated heterocyclic radical denotes, for example, mono- or polycyclic, substituted or unsubstituted hydrocarbon radicals in which one or more carbon atoms, CH groups and / or CH 2 groups are substituted by heteroatoms, preferably selected from the group consisting of
  • substituted or unsubstituted saturated heterocyclic radicals are pyrrolidinyl, imidazolidinyl, pyrazolidinyl, piperidyl, piperazinyl, morpholinyl, tetrahydrofuranyl, tetrahydropyranyl, tetrahydrothiophenyl and the like, as well as with methyl -, ethyl, propyl, isopropyl and tert-butyl radicals substituted derivatives thereof.
  • the radicals R 1 and R 2 may be identical or different and each represent hydrogen, hydroxyl, halogen, such as fluorine, chlorine, bromine or iodine, or an organic radical having 1 to 20 Carbon atoms, such as Ci-C2o-alkyl, in particular methyl, ethyl, tert-butyl, C6-C2o-aryl, in particular phenyl, arylalkyl or alkylaryl having 1 to 10, preferably 1 to 4 carbon atoms in the alkyl radical and 6 to 14, preferably 6 to 10, in particular 6 carbon atoms in the aryl radical, a saturated heterocyclic radical having 3 to 20 carbon atoms, or a heteroaromatic radical having 3 to 20 carbon atoms each having at least one heteroatom selected from the group consisting of the elements N, PO and S, in particular N , O and S, where the heteroaromatic radical may be substituted by further radicals R 10 , where R 10 is an organic radical having 1 to 10, in particular 1 to
  • radicals R 1 and R 2 are the same and are each hydrogen.
  • the radicals R 3 and R 4 may be identical or different and each represent hydrogen, or an organic radical having 1 to 20 carbon atoms, such as, for example, C 1 -C 20 -alkyl, in particular methyl, C 6 -C 20 -aryl, in particular phenyl, arylalkyl or alkylaryl with 1 to 10, preferably 1 to 4 carbon atoms in the alkyl radical and 6 to 14, preferably 6 to 10, in particular 6 carbon atoms in the aryl radical, a saturated heterocyclic radical having 3 to 20 carbon atoms, in particular tetrahydrofuranyl, or a heteroaromatic radical having 3 to 20 carbon atoms in each case at least one heteroatom selected from the group consisting of the elements N, PO and S, in particular N, O and S, where the heteroaromatic radical may be substituted by further radicals R 10 , where R 10 is an organic radical having 1 to 10, in particular 1 to 6 carbon atoms, such as, for example, C 1 -C 4 -
  • radicals R 3 and R 4 are the same or different and are each hydrogen, methyl, phenyl or tetrahydrofuranyl, particularly preferably hydrogen or tetrahydrofuranyl.
  • radicals R 3 and R 4 are identical and each represents hydrogen.
  • the other aryl units as used above are, as described above in the process of the present invention for preparing a Sn (II) crosslinked novolak material, aryl moieties identical to either the aryl moieties, the two, three or four Wear hydroxyl groups, wherein at least two hydroxyl groups adjacent to each other, or those Arylechen derived from other, optionally substituted phenols, such as phenol, o-cresol, p-cresol, p-tert.-butylphenol as the phenol component.
  • the organic fraction of the hybrid material is reacted with crosslinkers.
  • novolak crosslinkers such as urotropin, 2,6-dimethyloi-4-methylphenol or 2,2'-bis (3,5-dimethy! Ol, 4-hydroxyphenyl) propane are known in the art and also described in the cited technical literature. For this one can add a crosslinker to the novolak before the reaction with the metal or you can implement the reaction product of novolac and metal with a crosslinker in an additional step.
  • an inventive Sn (II) -linked novolak material as described above, wherein the radicals R 1 , R 2 , R 3 and R 4 in formula (I) are each hydrogen, wherein the proportion of aryl units of the novolak, the correspond to the aryl unit shown in the structural section of the formula (I) (called portion A), can differ depending on the task.
  • fraction A is at least 50 mol%, preferably at least 80 mol%, in particular at least 95 up to 100 mol%.
  • ranges of 20-40% or 30-50% will be preferred for portion A, while low metal affinity novolaks will have a proportion A in the range of 5-15% or 10-25%.
  • At least one SnO x phase wherein x is a number from 0 to 2; wherein the carbon phase C and the SnO x phase form substantially co-continuous phase domains, wherein the mean distance between two adjacent domains of identical phases is at most 10 nm, or where the SnO x phase with x is less than 0.2 in the form of SnO x domains are present which are substantially embedded in a continuous carbon phase C as a matrix in which more than 50% of the SnO x domains have a size in the range from 1 nm to 20 ⁇ m, comprising the method steps,
  • the process for producing an electroactive material comprises process step (a) and optionally process step (b), which have already been described in detail above in the process according to the invention for producing a Sn (II) crosslinked novolak material.
  • the process for producing an electroactive material with respect to process steps (a) and / or (b) in one of the previously described embodiments is carried out to produce a Sn (II) crosslinked novolak material.
  • step (c) of the process according to the invention for producing an electroactive material carbonization of the Sn (II) -linked novolak material and optionally partial or complete reduction of Sn (II) to Sn (0) is carried out.
  • 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. ,
  • carbonization is carried out at temperatures in the lower range, for example below 600 ° C, below 500 ° C or around 400 ° C. With this procedure one can obtain wide ranges of the co-continuous structures.
  • carbonization is carried out at temperatures in the higher range, for example above 700 ° C, above 800 ° C or around 1000 ° C.
  • the duration of carbonation can vary widely and, among other things, depends on the temperature at which the carbonation is carried out.
  • the carbonization time can be from 0.5 to 50 hours, preferably from 1 to 24 hours, especially from 2 to 12 hours.
  • heating was carried out at a rate of 1-10.degree. C./min, preferably 2-6.degree. C./min, that is, for example, at 2.times.3 or 4.degree. C./min, up to the desired temperature. Cooling can be started immediately after this temperature has been reached, or this temperature can be maintained for 10 minutes to 10 hours. This hold time may be, for example, about 0.5 hours; 1 h; 2 h; 3 h; 4 hours or 5 hours. In a further embodiment, an annealing step is added before the carbonization process.
  • the carbonation of the Sn (II) -linked novolak material can, in principle, be carried out in one or more stages, for example in one or two stages.
  • a step of carbonization may be carried out in the presence or absence of oxidizing agents, such as oxygen, as long as the oxidizing agent does not completely oxidize the carbon present in the Sn (II) -linked novolak material.
  • 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 carbonation of the Sn (II) crosslinked novolak material can in principle be carried out under reduced pressure, for example in vacuo, under atmospheric pressure or under elevated pressure, for example in 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.
  • step (c) the carbonization of the Sn (II) - crosslinked novolak material is one or more stages, preferably one stage, with extensive or complete, preferably complete, exclusion of oxygen carried out.
  • 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.
  • step (c) the carbonation of the Sn (II) -linked novolak Matenals in the presence of a protective or reactive gas selected from Ar, N2, Hb, NH3, CO and C2H2 and their mixtures carried out.
  • a protective or reactive gas selected from Ar, N2, Hb, NH3, CO and C2H2 and their mixtures carried out.
  • the Sn (II) bound in the Sn (II) crosslinked novolak material can be converted to a SnO x phase, wherein x is a number from 0 to 2.
  • x is a number from 0 to 2.
  • the electroactive material particularly preferably has SnO x phases, in which x is less than 1, preferably less than 0.4, particularly preferably less than 0.2, in particular less than 0.05
  • the conversion of the originally present Sn (II) into Sn (0) preferably takes place in the presence of a reducing gas, here also called reactive gas, as well as listed above instead.
  • the partial or complete reduction of Sn (II) to Sn (O) in process step (c) is therefore selected in the presence of a reactive gas selected from H2, NH3, CO and C2H2 and their mixtures are carried out.
  • the content of tin in the electroactive material can be varied widely.
  • an electroactive material is produced in the process according to the invention, characterized in that the tin content 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 materials produced therewith are furthermore distinguished by the fact that battery cells according to the invention can be produced, which preferably have at least 5 cycles, particularly preferably at least 10 cycles, very particularly preferably at least 50 cycles, in particular over at least 100 cycles or over at least 500 cycles are stable.
  • a further subject of the present invention is also an electroactive material which is obtainable by the process according to the invention for producing an electroactive material as described above.
  • the method comprises the method steps a), b) and c) described above, in particular also with regard to preferred embodiments thereof.
  • an electroactive material comprising
  • At least one SnOx phase wherein x is a number from 0 to 2; wherein the carbon phase C and the SnO x phase form substantially co-continuous phase domains, wherein the average 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, or wherein the SnOx phase with x is less than 0.2 in the form of SnO x domains which are embedded in a substantially isolated manner in a continuous carbon phase C as a matrix, wherein more than 50% of the SnO x domains have a size in the range of 1 nm to 20 ⁇ , characterized in that the tin content in the electroactive material 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 electroactive material.
  • both the above-described electroactive material according to the invention and the above-described electroactive material, which is accessible by the corresponding method according to the invention, are characterized in that the number x of the SnO x phase of the electroactive material is a number less than 0.2, preferably less than 0.1, in particular less than 0.05.
  • the electroactive material according to the invention comprises a carbon phase C.
  • the carbon is essentially elementary, ie the proportion of atoms other than carbon in the phase, e.g. B. N, O, S, P and / or H, is less than 10 wt .-%, in particular less than 5 wt .-%, based on the total amount of carbon in the phase.
  • the content of the atoms different from carbon in the phase can be determined by X-ray photoelectron spectroscopy.
  • the carbon phase may contain, in particular, small quantities of nitrogen, oxygen and / or hydrogen, as a result of the preparation.
  • the molar ratio of hydrogen to carbon will usually not exceed a value of 1: 2, in particular a value of 1: 3 and especially a value of 1: 4.
  • the value can also be 0 or nearly 0, e.g. B. ⁇ 0.1.
  • the carbon is presumably predominantly in amorphous or graphitic form, as can be concluded from ESCA studies based on 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 present at least partially in a hexagonal layer arrangement typical of graphite, which layers may also be bent or exfoliated.
  • the electroactive material according to the invention furthermore comprises a phase having the stoichiometry SnOx, ie a phase consisting essentially of tin, which is present in oxidic and / or elemental form.
  • the number x of the SnO x phase of the electroactive material is a number less than 0.2, preferably less than 0.1, in particular less than 0.05.
  • the molar ratio of Sn atoms to carbon atoms C i. the molar ratio Sn: C, vary over wide ranges and is preferably in the range of 1: 1200 to 1: 3, in particular in the range of 1: 500 to 1: 7
  • the carbon phase C and the SnO x phase are present over a wide range in a co-continuous arrangement, ie, the respective phase essentially does not form isolated phase domains surrounded by an optionally continuous phase domain. Rather, both phases form spatially separated continuous phase domains that interpenetrate each other, as can be seen by examination of the materials by means of transmission electron microscopy.
  • continuous phase domain, discontinuous phase domain, and co-continuous phase domain also WJ Work et al. Definitions of Terms Related to Polymer Blends, Composites and Multiphase Polymeric Materials, (IUPAC Recommendations 2004), Pure Appl. Chem., 76 (2004), pp. 1985-2007, especially p. 2003.
  • the regions in which the carbon phase and the SnO x phase form substantially co-continuous phase domains preferably at least 50% by volume, more preferably at least 60% by volume, most preferably at least 70% by volume .-%, most preferably at least 80 vol .-%, in particular at least 90 vol .-% to at most 100 vol .-% of the electroactive material.
  • the distances between adjacent phase boundaries, or the distances between the domains of adjacent identical phases low and are on average at a maximum of 10 nm, in particular at a maximum of 5 nm and especially a maximum of 2 nm.
  • Under the distance of adjacent identical phases is z.
  • the mean distance between the domains of adjacent identical phases can be determined by means of small angle X-ray scattering (SAXS) via the scattering vector q (measurement in transmission at 20 ° C., monochromatized CuKc radiation, 2D detector (image plate) , Split collimation).
  • SAXS small angle X-ray scattering
  • Sn particles are embedded in a matrix of carbon.
  • the SnO x phase with x is less than 0.2, preferably less than 0.1, in particular less than 0.05 in the form of SnO x domains, which may also be referred to as Sn particles before in which the SnO x domains (Sn particles) are embedded in a substantially continuous manner in a continuous carbon phase C as matrix, in which more than 50%, preferably> 70%, particularly preferably> 80%, in particular> 90% up to a maximum of 100% the SnO x domains (Sn particles) have a size in the range from 1 nm to 20 ⁇ m, preferably in the range from 2 nm to 2 ⁇ m, particularly preferably in the range from 3 nm to 500 nm, very particularly preferably in the range of 4 nm to 100 nm, in particular in the range of 10 to 60 nm, for example about 10 nm, about 20 nm or about 40 nm or about 5 n
  • HAADF-STEM high angle annular darkfield scanning electron microscopy.
  • comparatively heavy elements such as Sn vs. C
  • Preparation artifacts can also be detected, as denser areas of the preparations appear lighter than less dense areas.
  • the electroactive material according to the invention is particularly suitable as a material for anodes in Li-ion cells, in particular in Li-ion secondary cells or batteries.
  • the electroactive material according to the invention 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 containing the electroactive material of the present 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 constituents in the anodes according to the invention are carbon black, graphite, carbon fibers, nanocarbon fibers, nanocarbon tubes or electrically conductive polymers.
  • conductive material typically, about 2.5-40% by weight of the conductive material is used together with 50-97.5% by weight, often with 60-95% by weight, of the electroactive material of the present invention in the anode to the total mass of the anode material, less any current collector and electrical contacts.
  • Suitable binders for the production of an anode using the electroactive materials according to the invention are in particular the following polymeric materials:
  • 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 configured.
  • 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 configured.
  • 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 constituents and / or organic binder) mix and optionally one Subject molding process 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, comprising at least one electrode which has been produced from or using an electrode material as described above.
  • Such cells generally have at least one anode according to the invention, a cathode, in particular a cathode suitable for lithium-ion cells, an electrolyte and optionally a separator.
  • cathodes in which the cathode material comprises lithium transition metal oxide, eg. As lithium-cobalt oxide, lithium-nickel oxide, lithium-cobalt-nickel oxide, lithium-manganese oxide (spinel), lithium-nickel-cobalt-aluminum oxide, lithium-nickel-cobalt-manganese oxide or lithium-vanadium oxide, or a lithium transition metal phosphate such as lithium iron phosphate.
  • lithium-cobalt oxide lithium-nickel oxide, lithium-cobalt-nickel oxide, lithium-manganese oxide (spinel), lithium-nickel-cobalt-aluminum oxide, lithium-nickel-cobalt-manganese oxide or lithium-vanadium oxide, or a lithium transition metal phosphate such as lithium iron phosphate.
  • the cathode material comprises lithium transition metal oxide, eg.
  • lithium-cobalt oxide lithium-nickel oxide, lithium-cobalt-nickel oxide, lithium-mangan
  • the two electrodes i. the anode and the cathode are connected together using a liquid or solid electrolyte.
  • a liquid or solid electrolyte e.g. non-aqueous solutions (water content of generally ⁇ 20 ppm) of lithium salts and molten Li salts are suitable as liquid electrolytes, eg. 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 particularly polyethylene or polypropylene, may have a porosity in the range of 35 to 45%. Suitable pore diameters are for example in the range from 30 to 500 nm.
  • Electrochemical cells according to the invention usually also contain a housing, which can have any shape, for example cuboidal 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.
  • Another object of the present invention is also the use of electrochemical cells according to the invention, as described above, in lithium-ion batteries.
  • Another object of the present invention are lithium-ion batteries, comprising at least one inventive electrochemical cell, as described above.
  • inventive electrochemical cells can be combined with one another in lithium-ion batteries according to the invention, for example in series connection or in parallel connection. Series connection is preferred.
  • Inventive electrical cells are characterized by particularly high capacity, high performance even after repeated charging and greatly delayed cell death.
  • Electric cells according to the invention are very suitable for use in automobiles, electric motor-driven two-wheeled vehicles, for example pedelecs, aircraft, ships or stationary energy storage devices. Such uses are a further subject of the present invention.
  • Another object of the present invention is the use of electrochemical cells according to the invention as described above in 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 as well as a lower capacity loss with a longer running time. If one wanted to realize an equal running time with electrochemical cells with a lower energy density, then one would have to accept a higher weight for electrochemical cells.
  • Another object of the present invention is therefore also the use of lithium-ion batteries according to the invention in devices, in particular 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.
  • the powder contains Sn oxide hydrates, which explains the high O / H content.
  • Example 5 Precipitation in Organic Solvent
  • HAADF-STEM High Angle Annular Darkfield - Scanning Transmission Electron Microscopy
  • the samples were calcined in a tube furnace, which was equipped with a gastight quartz tube, so that it could be worked without any problems in a pure H2 atmosphere.
  • the samples were calcined in a tube furnace, which was equipped with a gastight quartz tube, so that it could be worked without any problems in a pure H2 atmosphere.
  • 1 1
  • 5 g of the powder from Example 4 were heated in the quartz glass boat at a heating rate of 3 - 4 ° C / min under Ar (2 -3 l / h) to 780 ° C and held there for 1, 5 h. Then allowed to cool overnight in the IS stream.
  • the mixture was then heated to 400 ° C. at a heating rate of 3-4 ° C./min under H 2 to 3 l / h and held there for 2 hours. Then allowed to cool overnight in the N2 stream.
  • the active material AM1 obtained in Example 10 was then blended with conductive black (Super P Li, Timcal) and binder (polyvinylidene fluoride Kynarflex 2801) to obtain a viscous coating composition consisting of 85.4% by weight of the active material obtained in Example 10, 5 , 4 wt.% Leitruß and 9.2 wt.% Binder in solvent N-ethyl-2-pyrrolidone (NEP) to obtain.
  • the amount of solvent used was 125% by weight of the solids used.
  • the coating composition was stirred for 16 hours by means of a magnetic stirrer.
  • the coating composition was then applied by means of a film applicator (Erichsen Coatmaster 509 MC) to a 20 ⁇ strong Cu film (purity 99.9%) by knife coating and brought into a drying cabinet promptly. Drying took place at 120 ° C overnight under vacuum. After drying, the resulting electrodes (width 8 cm) were calendered with a line pressure of 9 N / mm, and then placed in a glove box (argon atmosphere, water content ⁇ 1 ppm, oxygen content ⁇ 10 ppm). Before cell building, the electrodes were dried again at 5 mbar and 120 ° C. overnight).
  • the electrochemical test cells For the construction of the electrochemical test cells (2-electrode measuring arrangement analogous to a button cell) circular pieces were punched with a diameter of 20 mm. A glass fiber separator (Whatman GF / D, 630 ⁇ thickness) was used and lithium foil was used as the counter electrode. The electrolyte used was 1 M LiPF 6 in 1: 1 mixture of ethylene carbonate and ethyl methyl carbonate.
  • the cells were connected to a Maccor Series 4000 battery cycler. Cells were cycled at a specific current of 30 mA per gram of active material between 10 mV and 2 V versus Li / Li * . After reaching 10 mV, the voltage was kept constant for 30 minutes.
  • the active material AM2 obtained in Example 12 was then blended with conductive black (Super P Li, Timcal) and binder (polyvinylidene fluoride Kynarflex 2801) to give a viscous coating composition consisting of 86.9% by weight of the active material obtained in Example 12, 5.3 wt. % Leitruß and 7.8 wt.% Binder in solvent N-ethyl-2-pyrrolidone (NEP). The amount of solvent used was 125% by weight of the solids used. For better homogenization, the coating composition was stirred for 16 hours by means of a magnetic stirrer.
  • the coating composition was then applied by means of a film applicator (Erichsen Coatmaster 509 MC) to a 20 ⁇ strong Cu film (purity 99.9%) by knife coating and brought into a drying cabinet promptly. Drying took place at 120 ° C overnight under vacuum. After drying, the resulting electrodes (width 8 cm) were calendered with a line pressure of 9 N / mm, and then placed in a glove box (argon atmosphere, water content ⁇ 1 ppm, oxygen content ⁇ 10 ppm). Before cell building, the electrodes were dried again at 5 mbar and 120 ° C. overnight).
  • the electrochemical test cells For the construction of the electrochemical test cells (2-electrode measuring arrangement analogous to a button cell) circular pieces were punched with a diameter of 20 mm. A glass fiber separator (Whatman GF / D, 630 ⁇ thickness) was used and lithium foil was used as the counter electrode. The electrolyte used was 1 M LiPF 6 in 1: 1 mixture of ethylene carbonate and ethyl methyl carbonate.
  • the cells were connected to a Maccor Series 4000 battery cycler. Cells were cycled at a specific current of 30 mA per gram of active material between 10 mV and 2 V versus Li / Li * . After reaching 10 mV, the voltage was kept constant for 30 minutes.
  • the active material AM3 obtained in Example 14 was then blended with conductive black (Super P Li, Timcal) and binder (polyvinylidene fluoride Kynarflex 2801) to give a viscous coating composition consisting of 85.3% by weight of the active material obtained in Example 14, 6.2 % By weight of carbon black and 8.5% by weight of binder in solvent N-ethyl-2-pyrrolidone (NEP). The amount of solvent used was 125% by weight of the solids used. For better homogenization, the coating composition was stirred for 16 hours by means of a magnetic stirrer.
  • the coating composition was then applied by means of a film applicator (Erichsen Coatmaster 509 MC) to a 20 ⁇ strong Cu film (purity 99.9%) by knife coating and brought into a drying cabinet promptly. Drying took place at 120 ° C overnight under vacuum. After drying, the resulting electrodes (width 8 cm) were calendered with a line pressure of 9 N / mm, and then placed in a glove box (argon atmosphere, water content ⁇ 1 ppm, oxygen content ⁇ 10 ppm). Before cell building, the electrodes were dried again at 5 mbar and 120 ° C. overnight).
  • the active material AM4 obtained in Example 16 was then blended with conductive black (Super P Li, Timcal) and binder (polyvinylidene fluoride Kynarflex 2801) to form a viscous coating composition consisting of 85% by weight of the active material obtained in Example 16, 6.4 % By weight of carbon black and 8.6% by weight of binder in solvent N-ethyl-2-pyrrolidone (NEP).
  • the amount of solvent used was 125% by weight of the solids used.
  • the coating composition was stirred for 16 hours by means of a magnetic stirrer.
  • the coating composition was then applied by means of a film applicator (Erichsen Coatmaster 509 MC) to a 20 ⁇ strong Cu film (purity 99.9%) by knife coating and brought into a drying cabinet promptly. Drying took place at 120 ° C overnight under vacuum. After drying, the resulting electrodes (width 8 cm) were calendered with a line pressure of 9 N / mm, and then placed in a glove box (argon atmosphere, water content ⁇ 1 ppm, oxygen content ⁇ 10 ppm). Before cell building, the electrodes were dried again at 5 mbar and 120 ° C. overnight).
  • the electrochemical test cells For the construction of the electrochemical test cells (2-electrode measuring arrangement analogous to a button cell) circular pieces were punched with a diameter of 20 mm. A glass fiber separator (Whatman GF / D, 630 ⁇ thickness) was used and lithium foil was used as the counter electrode. The electrolyte used was 1 M LiPF 6 in 1: 1 mixture of ethylene carbonate and ethyl methyl carbonate.
  • the cells were connected to a Maccor Series 4000 battery cycler. Cells were cycled at a specific current of 30 mA per gram of active material between 10 mV and 2 V versus Li / Li * . After reaching 10 mV, the voltage was kept constant for 30 minutes.
  • the active material AM5 obtained in Example 18 was then blended with conductive black (Super P Li, Timcal) and binder (polyvinylidene fluoride Kynarflex 2801) to obtain a viscous coating composition consisting of 86% by weight of the active material obtained in Example 18, 5.8% by weight. % Leitruß and 8.2% by weight of binder in solvent to obtain N-ethyl-2-pyrrolidone (NEP).
  • the amount of solvent used was 125% by weight of the solids used.
  • the coating composition was stirred for 16 hours by means of a magnetic stirrer.
  • the coating composition was then applied by means of a film applicator (Erichsen Coatmaster 509 MC) to a 20 ⁇ strong Cu film (purity 99.9%) by knife coating and brought into a drying cabinet promptly. Drying took place at 120 ° C overnight under vacuum. After drying, the resulting electrodes (width 8 cm) were calendered with a line pressure of 9 N / mm, and then placed in a glove box (argon atmosphere, water content ⁇ 1 ppm, oxygen content ⁇ 10 ppm). Before cell building, the electrodes were dried again at 5 mbar and 120 ° C. overnight).
  • the electrochemical test cells (2-electrode measuring arrangement analogous to a button cell) circular pieces were punched with a diameter of 20 mm. A fiberglass separator (Whatman GF / D, 630 ⁇ thickness) was used, and lithium foil used as a counter electrode. The electrolyte used was 1 M LiPF 6 in 1: 1 mixture of ethylene carbonate and ethyl methyl carbonate.
  • the cells were connected to a Maccor Series 4000 battery cycler. Cells were cycled at a specific current of 30 mA per gram of active material between 10 mV and 2 V versus Li / Li * . After reaching 10 mV, the voltage was kept constant for 30 minutes.
  • the active material AM6 obtained in Example 21 was then blended with conductive black (Super P Li, Timcal) and binder (polyvinylidene fluoride Kynarflex 2801) to obtain a viscous coating composition consisting of 84.3% by weight of the active material obtained in Example 21, 6
  • conductive black Super P Li, Timcal
  • binder polyvinylidene fluoride Kynarflex 2801
  • NEP N-ethyl-2-pyrrolidone
  • the amount of solvent used was 125% by weight of the solids used.
  • the coating composition was stirred for 16 hours by means of a magnetic stirrer.
  • the coating composition was then applied by means of a film applicator (Erichsen Coatmaster 509 MC) to a 20 ⁇ strong Cu film (purity 99.9%) by knife coating and brought into a drying cabinet promptly. Drying took place at 120 ° C overnight under vacuum. After drying, the resulting electrodes (width 8 cm) were calendered with a line pressure of 9 N / mm, and then placed in a glove box (argon atmosphere, water content ⁇ 1 ppm, oxygen content ⁇ 10 ppm). Before cell building, the electrodes were dried again at 5 mbar and 120 ° C. overnight).
  • the electrochemical test cells For the construction of the electrochemical test cells (2-electrode measuring arrangement analogous to a button cell) circular pieces were punched with a diameter of 20 mm. A glass fiber separator (Whatman GF / D, 630 ⁇ thickness) was used and lithium foil was used as the counter electrode. The electrolyte used was 1 M LiPF 6 in 1: 1 mixture of ethylene carbonate and ethyl methyl carbonate.
  • the cells were connected to a Maccor Series 4000 battery cycler. Cells were cycled at a specific current of 30 mA per gram of active material between 10 mV and 2 V versus Li / Li * . After reaching 10 mV, the voltage was kept constant for 30 minutes.
  • the active material AM7 obtained in Example 23 was then blended with conductive black (Super P Li, Timcal) and binder (polyvinylidene fluoride Kynarflex 2801) to obtain a viscous coating composition consisting of 86.2% by weight of the active material obtained in Example 23, 6% by weight. % Leitruß and 7.8 wt.% Binder in solvent N-ethyl-2-pyrrolidone (NEP).
  • NEP N-ethyl-2-pyrrolidone
  • the amount of solvent used was 125% by weight of the solids used.
  • the coating composition was stirred for 16 hours by means of a magnetic stirrer.
  • the coating composition was then applied by means of a film applicator (Erichsen Coatmaster 509 MC) to a 20 ⁇ strong Cu film (purity 99.9%) by knife coating and brought into a drying cabinet promptly. Drying took place at 120 ° C. overnight. The vacuum takes place. After drying, the resulting electrodes (width 8 cm) were calendered with a line pressure of 9 N / mm, and then placed in a glove box (argon atmosphere, water content ⁇ 1 ppm, oxygen content ⁇ 10 ppm). Before cell building, the electrodes were dried again at 5 mbar and 120 ° C. overnight).
  • the electrochemical test cells For the construction of the electrochemical test cells (2-electrode measuring arrangement analogous to a button cell) circular pieces were punched with a diameter of 20 mm. A glass fiber separator (Whatman GF / D, 630 ⁇ thickness) was used and lithium foil was used as the counter electrode. The electrolyte used was 1 M LiPF 6 in 1: 1 mixture of ethylene carbonate and ethyl methyl carbonate.
  • the cells were connected to a Maccor Series 4000 battery cycler. Cells were cycled at a specific current of 30 mA per gram of active material between 10 mV and 2 V versus Li / Li * . After reaching 10 mV, the voltage was kept constant for 30 minutes.
  • the active material AM8 obtained in Example 25 was then blended with conductive black (Super P Li, Timcal) and binder (polyvinylidene fluoride Kynarflex 2801) to obtain a viscous coating composition consisting of 87.6% by weight of the active material obtained in Example 25, 4 To obtain 8% by weight of conductive carbon black and 7.6% by weight of binder in solvent N-ethyl-2-pyrrolidone (NEP). The amount of solvent used was 125% by weight of the solids used. For better homogenization, the coating composition was stirred for 16 hours by means of a magnetic stirrer.
  • conductive black Super P Li, Timcal
  • binder polyvinylidene fluoride Kynarflex 2801
  • the coating composition was then applied by means of a film applicator (Erichsen Coatmaster 509 MC) to a 20 ⁇ strong Cu film (purity 99.9%) by knife coating and brought into a drying cabinet promptly. Drying took place at 120 ° C overnight under vacuum. After drying, the resulting electrodes (width 8 cm) were calendered with a line pressure of 9 N / mm, and then placed in a glove box (argon atmosphere, water content ⁇ 1 ppm, oxygen content ⁇ 10 ppm). Before cell building, the electrodes were dried again at 5 mbar and 120 ° C. overnight).
  • the electrochemical test cells For the construction of the electrochemical test cells (2-electrode measuring arrangement analogous to a button cell) circular pieces were punched with a diameter of 20 mm. A glass fiber separator (Whatman GF / D, 630 ⁇ thickness) was used and lithium foil was used as the counter electrode. The electrolyte used was 1 M LiPF 6 in 1: 1 mixture of ethylene carbonate and ethyl methyl carbonate.
  • the cells were connected to a Maccor Series 4000 battery cycler. Cells were cycled at a specific current of 30 mA per gram of active material between 10 mV and 2 V versus Li / Li * . After reaching 10 mV, the voltage was kept constant for 30 minutes.
  • FIG. 1 shows the discharge capacity (in mAh / g on the y-axis) for the 4 active materials AM1, AM2, AM3 and AM4 from Examples 10, 12, 14 and 16.
  • the capacity achieved is initially above achievable values for graphite however, a decline in capacity did detectable. However, differences between the materials are noticeable: while materials AM1 and AM2 are rapidly (continuously) decreasing to capacity values characteristic of the proportionately contained carbon in the materials, the decrease in capacity of the materials is AM3 and in particular Toned down AM4.
  • Figures 2a to 2d show the variation of the differential capacitance (in Ah / V on the y-axis) versus the voltage (in V on the x-axis). The values shown were calculated from the measurement data of a chronoamperometric measurement. In chronoamperometry, a constant current is given and the changes in voltage are registered. The plot of the resulting differential capacitance across the voltage allows statements about characteristic electrochemical processes, e.g. Storage or removal of lithium, or decomposition of electrolyte.
  • the characteristic peaks for tin electrochemical activity are at 0.4 V (lithium alloy incorporation with tin, negative y-axis) and between 0.6 and 0.8 volts (three lithium-tin lithium extraction peaks) Alloy, positive y-axis).
  • Figure 2a shows the differential capacitance across voltage for material AM1 of Example 10.
  • the first cycle is shown as a solid line and the tenth cycle as a dashed line.
  • the strong decrease in the electrochemical activity of the tin can be clearly seen.
  • Figure 2b shows the differential capacitance across voltage for material AM2 of Example 12.
  • the first cycle is shown as a solid line and the tenth cycle as a dashed line.
  • the strong decrease in the electrochemical activity of the tin can be clearly seen.
  • Figure 2c shows the differential capacitance across voltage for material AM3 of Example 14.
  • the first cycle is shown as a solid line and the tenth cycle as a dashed line.
  • the strong decrease in the electrochemical activity of the tin can be clearly seen.
  • Figure 2d shows the differential capacitance across voltage for material AM4 of Example 16.
  • the first cycle is shown as a solid line and the tenth cycle as a dashed line.
  • a decrease in the electrochemical activity of the tin can be seen. This is less strong than the materials AM1, AM2 and AM3.
  • Figure 3 shows the discharge capacity (in mAh / g on the y-axis) for the 3 active materials AM5, AM6 and AM7 from Examples 18, 21 and 23 over 25 cycles (number of cycles on the x-axis).
  • the capacity achieved is initially above achievable values for graphite for the materials AM6 and AM7, while the material AM5 is significantly below.
  • the differences are due to different Co-Sn compounds, which have different electrochemical activities.
  • AM6 and AM7 predominantly the CoSn2 phase is present while the material AM5 is present in the composition CoSn.
  • the capacity decreases only slightly during the first 25 cycles, which is a significant improvement over the materials without stabilizing cobalt (AM1, AM2, AM3, AM4).
  • Figures 4a to 4c show the variation of the differential capacitance (in Ah / V on the y-axis) versus the voltage (in V on the x-axis). The values shown were calculated from the measurement data of a chronoamperometric measurement. In chronoamperometry, a constant current is given and the changes in voltage are registered. The plot of the resulting differential capacitance across the voltage allows statements about characteristic electrochemical processes, such as lithium incorporation or removal, or decomposition of electrolyte.
  • the characteristic peaks for tin electrochemical activity are at 0.4 V (lithium alloy incorporation with tin, negative y-axis) and between 0.6 and 0.8 volts (three lithium-tin lithium extraction peaks) Alloy, positive y-axis).
  • Figure 4a shows the differential capacitance across voltage for material AM5 of Example 18.
  • the first cycle is shown as a solid line and the tenth cycle as a dashed line.
  • the high Co content leads to the formation of the CoSn phase. Only a minimal electrochemical activity of the Sn can be recognized, the majority of the capacity being due to lithium incorporation into carbon.
  • FIG. 4b shows the differential capacitance over voltage for material AM6 from example 21.
  • the first cycle is shown as a solid line and the tenth cycle as a dashed line.
  • Sn is predominantly present in CoSn2, and shows approximately constant high electrochemical activity.
  • Figure 4c shows the differential capacitance across voltage for material AM7 of Example 23.
  • the first cycle is shown as a solid line and the tenth cycle as a dashed line.
  • Sn shows almost constant high electrochemical activity, the contribution of carbon is low.
  • Figure 5 shows the discharge capacity (in mAh / g on the y-axis) for two cells of the material AM8 from Example 25 over 30 cycles (number of cycles on the x-axis).
  • the capacity achieved is below achievable values for graphite, and shows a moderate decline in the further course. On the basis of the uniformly running measuring points, the high reproducibility is recognizable.
  • Figure 6 shows the variation of the differential capacitance (in Ah / V on the y-axis) versus the voltage (in V on the x-axis) for material AM8 of Example 25.
  • the first cycle is as a solid line and the tenth cycle as shown dashed line.
  • the values shown were calculated from the measurement data of a chronoamperometric measurement. In chronoamperometry, a constant current is given and the changes in voltage are registered. The plot of the resulting differential capacitance across the voltage allows statements about characteristic electrochemical processes, such as lithium incorporation or removal, or decomposition of electrolyte.

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Abstract

La présente invention concerne un procédé de fabrication d'une matière novolaque réticulée avec Sn(II), la matière novolaque réticulée avec Sn(II) obtenue par le procédé selon l'invention, un procédé de fabrication d'une matière électroactive qui contient une phase carbone C et une phase étain et/ou une phase oxyde d'étain, comprenant le procédé de fabrication d'une matière novolaque réticulée avec Sn(II) et une étape de carbonisation postérieure, la matière électroactive obtenue par ledit procédé selon l'invention, ainsi que des cellules électrochimiques et des batteries contenant cette matière électroactive.
PCT/IB2012/054156 2011-08-19 2012-08-15 Matières contenant du carbone et de l'étain à base de novolaque, leur fabrication et leur utilisation dans des cellules électrochimiques WO2013027157A2 (fr)

Priority Applications (4)

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KR1020147007109A KR20140058637A (ko) 2011-08-19 2012-08-15 노볼락계 C-Sn 물질, 그의 제조 방법 및 전기화학 전지에서의 그의 용도
CN201280039224.2A CN104114617A (zh) 2011-08-19 2012-08-15 线型酚醛基C-Sn材料、其制备方法及其在电化学电池中的用途
JP2014526579A JP2015513169A (ja) 2011-08-19 2012-08-15 ノボラックをベースにしたＣ−Ｓｎ材料、その製造、および電気化学セルでのその使用
EP12825111.3A EP2850117A4 (fr) 2011-08-19 2012-08-15 Matières contenant du carbone et de l'étain à base de novolaque, leur fabrication et leur utilisation dans des cellules électrochimiques

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US8865858B2 (en) 2012-06-26 2014-10-21 Basf Se Process for producing a composite material

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US5859153A (en) * 1996-06-21 1999-01-12 Minnesota Mining And Manufacturing Company Novolak compounds useful as adhesion promoters for epoxy resins
CN101202340A (zh) * 2007-12-07 2008-06-18 广西师范大学 锂离子电池负极用锡碳纳米复合材料及其制备方法
WO2010112580A1 (fr) * 2009-04-03 2010-10-07 Basf Se Matière électroactive et son utilisation dans des anodes pour des cellules aux ions lithium
CN101626075B (zh) * 2009-08-03 2011-03-30 北京化工大学 锡碳复合纳米纤维薄膜负极材料及其制备方法
CN101800306B (zh) * 2010-03-25 2012-07-04 陕西师范大学 用于锂离子电池的氧化锡/碳复合电极材料的制备方法
CN101850959B (zh) * 2010-05-31 2012-03-28 奇瑞汽车股份有限公司 一种锂离子电池硅碳负极材料的制备方法
CN102255079B (zh) * 2011-05-17 2013-12-18 奇瑞汽车股份有限公司 一种锂离子电池负极用锡碳复合材料及其制备方法和锂离子电池

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* 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

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JP2015513169A (ja) 2015-04-30
CN104114617A (zh) 2014-10-22

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