TW201323434A - Tin oxide-containing polymer composite materials - Google Patents

Abstract

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(II) oxide or in the form of a mixture thereof; and of a carbon phase in which carbon is present in elemental form. Such 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) of the general formula I for production of the inventive tin oxide-containing polymer composite materials: R1-X-Sn-Y-R2 (I) in which R1 is an Ar-C(Ra, Rb)- radical in which Ar is an aromatic or heteroaromatic ring which optionally has 1 or 2 substituents, and Ra, Rb are each independently hydrogen or methyl or together are an oxygen atom or a methylidene group (=CH2), R2 is C1-C10-alkyl or C3-C8-cycloalkyl or has one of the definitions given for R1; or R1 together with R2 is a radical of the formula A: in which A is an aromatic or heteroaromatic ring fused to the double bond, m is 0, 1 or 2, the R radicals may be the same or different and are selected from halogen, CN, C1-C6-alkyl, C1-C6-alkoxy and phenyl, and Ra, Rb are each as defined above; X is O, S or NH; and Y is O, S or NH.

Description

Polymer composite containing tin oxide

The present invention relates to a novel polymer composite comprising tin oxide, a method of producing the same, and a use thereof for producing a tin-carbon composite, the tin-carbon composite comprising at least one inorganic tin-containing phase, wherein the tin is in elemental form Or in the form of tin (II) oxide or in the form of a mixture thereof; and a carbon phase in which the carbon system is present in elemental form. Such tin-carbon composites are particularly suitable for producing anode materials for electrochemical cells, particularly lithium batteries. The invention is also directed to compounds (monomers) useful in the production of the tin oxide-containing polymer composites of the present invention.

In a society where mobility is gradually increasing, mobile electric devices are playing an increasingly important role. Therefore, for many years, battery packs, particularly rechargeable battery packs (referred to as secondary battery packs or accumulators) have been found to be used in almost all areas of life. There are now complex characteristics of the secondary battery pack's need for its electrical and mechanical properties. For example, the electronics industry is demanding new, small, lightweight secondary batteries or battery packs with high capacitance and high cycle stability to achieve long life. In addition, thermal sensitivity and self-discharge rate should be low to ensure high reliability and efficiency. At the same time, it is necessary to have a high degree of security during use. The automotive industry is also particularly interested in lithium secondary battery packs having such properties and such battery packs may be used, for example, as energy storage devices in electrically operated vehicles or hybrid vehicles. In addition, there is a need for a battery pack having advantageous electromotive properties in order to achieve a high current density, and in the development of a novel battery pack system, it is also possible to produce a rechargeable battery pack in an inexpensive manner. It is of interest. Environmental aspects have also played a growing role in the development of new battery systems.

The cathode of a modern high-energy lithium battery pack now typically contains a spinel-type lithium-transition metal oxide or mixed oxide as an electroactive material, such as LiCoO ₂ , LiNiO ₂ , LiNi _1-xy Co _x M _y O ₂ (0 <x<1, y<1, M is, for example, Al or Mn) or LiMn ₂ O ₄ , or, for example, lithium iron phosphate. For the construction of the anode of modern lithium batteries, lithium-graphite intercalation compounds have been demonstrated in the past few years (Journal Electrochem. Soc. 1990, 2009). In addition, as an anode material, lithium-germanium intercalation compounds, lithium alloys, and lithium titanate have been examined (see KEAifantis, "Next generation anodes for secondary Li-ion batteries", High Energy Density Li-Batteries, Wiley-VCH, 2010, Pp. 129-162). The two electrodes are combined with each other using a liquid or solid electrolyte in a lithium battery. In (re)charging of a lithium battery pack, the cathode material is oxidized (for example according to the following equation: LiCoO ₂ →n Li ⁺ +Li _(1-n) CoO ₂ +ne ^- ). This releases lithium from the cathode material and migrates to the anode in the form of lithium ions, where lithium ions are closely related to the reduction of the anode material and are closely related to the reduction of graphite in the case of graphite inserted as lithium ions. In this case, lithium occupies the interlayer sites in the graphite structure. During discharge of the battery pack, lithium incorporated into the anode is removed from the anode as lithium ions and the anode material is oxidized. Lithium ions migrate to the cathode via the electrolyte and are associated therein with reduction of the cathode material. Lithium ions migrate through the spacer during discharge of the battery pack and during recharging of the battery pack.

However, significant disadvantages in the case of using graphite in Li-ion battery packs It lies in a rather low specific capacitance with a theoretical upper limit of 0.372 Ah/g. Graphite-like carbon materials other than graphite have similar properties, such as carbon black, such as acetylene black, lamp black, furnace black, flame black, cracked black, slot black or hot black, and bright carbon or hard carbon. In addition, these anode materials are not a problem in terms of safety.

A higher specific capacitance can be achieved in the case of using a lithium alloy such as Li _x Si, Li _x Pb, Li _x Sn, Li _x Al or Li _x Sb alloy. These alloys enable the charging capacitance to be up to 10 times the charging capacity of graphite (Li _x Si alloy; see RA Huggins, Proceedings of the Electrochemical Society 87-1, 1987, pp. 356-64). A significant disadvantage of these alloys is their dimensional change during charging/discharging, which causes the anode material to disintegrate. As a result of the increased specific surface area of the resulting anode material, the loss of capacitance caused by the irreversible reaction between the anode material and the electrolyte and the sensitivity of the battery to thermal stress increase, in extreme cases, it can cause strong exothermic damage of the battery and is a safety risk. .

The use of lithium as an electrode material is problematic for safety reasons. More specifically, lithium dendrites are formed on the anode material when lithium is deposited during the charging operation. These lithium dendrites can cause short circuits in the battery and thus cause uncontrolled damage to the battery.

EP 692 833 describes carbon-containing intercalation compounds which, besides carbon, also comprise metals or semimetals which form alloys with lithium, in particular helium. This preparation is achieved by pyrolysis of a polymer comprising a metal or a semimetal and a hydrocarbon group, for example by pyrolysis of a polyoxane in the case of a ruthenium containing compound. Pyrolysis requires harsh conditions under which the primary polymer first decomposes and subsequently forms Carbon and (semi)metal and / or (semi) metal oxide domains. The generation of such materials often results in poor reproducibility, which may be due to the high energy input that only makes control of the domain structure (if controlled) difficult.

I. Honma et al., Nano Lett., 9 (2009) describe nanoporous materials formed from SnO ₂ nanoparticles embedded in exfoliated graphite flakes. These materials are suitable for use as anode materials for Li-ion battery packs. It is produced by mixing exfoliated graphite flakes with SnO ₂ nanoparticles in ethylene glycol. The exfoliated graphite flakes are themselves produced by the reduction of oxidized and exfoliated graphite. This process is quite inconvenient and expensive. In addition, this process results in a result of poor reproducibility.

WO 2010/112580 describes electroactive materials comprising a carbon phase C and at least one MO _x phase, wherein M is a metal or semimetal, such as boron, ruthenium, titanium or tin, and x is a value from 0 to < k/2, wherein The maximal valence of k-based metal or semi-metal. According to WO 2010/112580, electroactive materials are produced in two stages, the first stage involving the production of nanocomposites from the (semi)metal oxide phase and the organic polymer phase by so-called double polymerization, and the second stage involves carbonization by This produces a nanocomposite. Although this process produces excellent results in most cases, it is difficult to obtain a monomer in the case of tin and may only make polymerization difficult, and thus the obtained polymer composite and the tin-carbon composite material produced therefrom do not have Satisfactory electrochemical properties.

WO 2010/112581 describes a process for producing a nanocomposite in which a metal or semimetal containing monomer is copolymerized. The proposed monomers include tin-containing monomers in which tin is present in the +4 oxidation state. The production of such monomers, especially in relatively large amounts, is difficult and the polymerization is problematic.

In summary, it can be stated that it is based on carbon or based on lithium alloys and has been Known anode materials are unsatisfactory in terms of specific capacitance, charge/discharge power, and/or cycle stability, such as reduced capacitance and/or higher or increased impedance after several charge/discharge cycles. A composite material having a particulate semi-metal or metal phase and one or more carbon phases and which has recently been proposed to solve such problems can only partially solve such problems, and at least in the case of tin-containing materials, the quality of such composite materials It cannot be achieved in a reproducible manner. In addition, its production is often too complicated to be economically utilized.

Accordingly, it is an object of the present invention to provide a method of producing a tin-containing polymer composite that provides low complexity and good reproducibility of the product qualities that allow for further processing in the tin-carbon composite. The tin-carbon composite thus prepared should be suitable as an anode material for a Li-ion battery, in particular for a Li-ion secondary battery, and corrects the disadvantages of the prior art and in particular should have at least one and in particular one or more of the following properties: - High specific capacitance, - High cycle stability, - Low self-discharge, - Good mechanical stability.

It has been found that these objects are surprisingly achieved by the methods detailed below and the polymer composites comprising tin oxide obtainable by such methods for producing at least one inorganic tin oxide phase and The organic polymer phase comprises a tin oxide-containing polymer composite.

Accordingly, the present invention is directed to a method of producing a polymer composite comprising tin oxide, the material comprising a) at least one inorganic tin oxide phase; and b) an organic polymer phase; the method comprising at least one Formula I under polymerization conditions Monomer polymerization R ¹ -X-Sn-YR ² (I) wherein R ¹ is an Ar-C(R ^a ,R ^b )- group, wherein an Ar-based aromatic or heteroaromatic ring, optionally having 1 or 2 substituents selected from the group consisting of halogen, OH, CN, C ₁ -C ₆ -alkyl, C ₁ -C ₆ -alkoxy and phenyl, and R ^a and R ^b are each independently hydrogen or methyl or Together they are an oxygen atom or a methylene group (=CH ₂ ); R ² is a C ₁ -C ₁₀ -alkyl group or a C ₃ -C ₈ -cycloalkyl group or has ^one of the definitions given for R ¹ ; R ¹ together with R ^{2 is a} group of formula A:

Wherein A is an aromatic or heteroaromatic ring fused to a double bond, m is 0, 1 or 2, and the R groups may be the same or different and are selected from the group consisting of halogen, CN, C ₁ -C ₆ -alkyl, C ₁ -C ₆ -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; under these polymerization conditions, Ar-C ( The R ^a , R ^b ) groups polymerize to form an organic polymer phase and the XSnY unit polymerizes to form a tin oxide phase.

The single system of the formula I is novel and thus likewise forms part of the subject matter of the invention. It is easy to prepare compared to known tin (IV) compounds, and it can also be prepared on an industrial scale. In addition, it is more stable than the corresponding tin (IV) compound, and thus its use in polymerization is accompanied by fewer problems.

The invention also provides a polymer composite comprising tin oxide comprising a) at least one inorganic tin oxide phase; and b) an organic polymer phase; which is obtainable by the process of the invention.

The organic polymer phase comprising the tin oxide-containing polymer composite obtained in accordance with the present invention by means of carbonization can be converted into a tin-carbon composite by the present invention comprising a tin oxide-containing polymer composite in a simple manner.

The present invention also provides a method of producing a tin-carbon composite comprising at least one inorganic tin-containing phase, wherein the tin is present in a 0 or +2 oxidation state or as a mixture thereof; and a carbon phase in which the carbon is an element Form exists; the method comprises: i. providing a polymer composite comprising tin oxide by the method described herein and hereinafter, and ii. an organic polymer phase comprising a polymer composition comprising tin oxide obtained in the carbonization step i .

The invention further provides a tin-carbon composite material obtainable by this method and comprising at least one inorganic tin-containing phase, wherein the tin is present in the +2 or 0 oxidation state or as a mixture thereof; and the carbon phase, wherein the carbon system Exists in the form of elements.

Due to the composition and specific arrangement of the carbon phase C and the self-generated tin-containing phase, Tin-carbon composites are particularly suitable for use as electroactive materials in anodes in Li-ion batteries, especially in Li-ion secondary batteries or batteries. More specifically, in the case of being used in an anode of a Li ion battery and particularly a Li ion secondary battery, attention is paid to high capacitance and good cycle stability, and a low impedance in the battery is ensured. In addition, it may have high mechanical stability due to the co-continuous phase alignment. In addition, it can be manufactured in a simple manner and in reproducible quality.

Accordingly, the present invention also provides the use of a tin-carbon composite material in an anode of a lithium ion battery, particularly a lithium ion secondary battery, and provides a tin-carbon composite comprising the present invention for a lithium ion battery, particularly a lithium ion secondary battery. The anode of the material, and a lithium ion battery, in particular a lithium ion secondary battery, having at least one anode comprising the tin-carbon composite of the invention.

Preferred embodiments of the process of the invention and the tin oxide-containing polymer composites and tin-carbon composites obtained therein are set forth in detail herein and in the scope of the patent application.

In the context of the present invention, a polymer composite comprising tin oxide is understood to mean substantially (generally at least 90% by weight, in particular at least 95% by weight) of a material consisting of tin oxide and an organic polymer phase, The phases are distributed in each other. The tin oxide phase generally consists essentially of (i.e. typically at least 90% by weight, in particular at least 95% by weight) consisting of tin oxide or tin oxide hydrate. The organic polymer phase is formed from a carbon-containing polymer other than elemental carbon. The composition of the organic polymer phase is defined by the Ar-C(R ^a , R ^b ) group, and thus it typically comprises a poly(hetero)aryl formaldehyde condensate or a polycarboxylate or a mixture thereof.

The term "tin oxide" in the context of the present invention comprises pure tin oxide of stoichiometric SnO (eg α-SnO and β-SnO, Sn ₂ O ₃ and SnO ₂ , such as octagonal SnO ₂ and hexagonal SnO ₂ ), Divalent and tetravalent tin oxide hydrates such as Sn(OH) ₂ and stannic acid H ₂ Sn(OH) ₆ .

In the context of the present invention, a carbon-tin composite is understood to mean substantially (generally at least 90% by weight, in particular at least 95% by weight) of a material consisting of a tin-containing phase and an elemental carbon, and on the one hand The tin phases and on the other hand carbon are distributed in each other. The carbon phase is formed of elemental carbon, and the carbon may have a graphite structural unit.

As the terms "aromatic ring" and "heteroaromatic ring", the terms "alkyl", "alkoxy", "cycloalkyl" and "hydroxyalkyl" are understood to encompass the terms generally referred to by this term. The general term for the substituents. In this context, the suffix _{Cn- Cm} indicates the number of possible carbon atoms that a substituent, as generally referred to herein, may have.

Thus, alkyl groups typically have a saturated straight or branched aliphatic hydrocarbon group of from 1 to 10, often from 1 to 6, and especially from 1 to 4 carbon atoms. Examples of alkyl groups are methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-butyl, 2-methylpropyl, 1,1-dimethylethyl (= tert-butyl ), n-pentyl, 2-pentyl, 2-methylbutyl, n-hexyl, 2-hexyl, n-heptyl, 2-heptyl, n-octyl, 2-octyl, 2-ethylhexyl, positive Indenyl, n-decyl, 1-methylindenyl and 2-propylheptyl.

Thus, alkoxy is a saturated straight or branched aliphatic hydrocarbon bonded via an oxygen atom and typically having from 1 to 10, often from 1 to 6, and especially from 1 to 4 carbon atoms. base. Examples of alkoxy groups are methoxy, ethoxy, n-propoxy, isopropoxy, n-butyloxy, 2-butyloxy, 2-methylpropoxy, 1,1-di Methyl ethoxy (=t-butoxy), n-pentyloxy, 2-pentyloxy, 2-methylbutoxy, n-hexyloxy, 2-hexyloxy, n-heptyloxy , 2-heptyloxy, n-octyloxy, 2-octyloxy, 2-ethylhexyloxy, n-decyloxy, n-decyloxy, 1-methyldecyloxy And 2-propylheptyloxy.

Thus, a hydroxyalkyl group is a saturated aliphatic hydrocarbon group which is substituted by at least one OH group and usually has 1 to 10, often 1 to 6, and especially 1 to 4 carbon atoms. Examples of hydroxyalkyl groups are hydroxymethyl, 1-hydroxyethyl, 2-hydroxyethyl, 1-hydroxypropyl, 2-hydroxypropyl, 3-hydroxypropyl, 1-hydroxy-1-methylethyl , 2-hydroxy-1-methylethyl, 4-hydroxybutyl, and the like.

Thus, a cycloalkyl system typically has a saturated cycloaliphatic hydrocarbon group of from 3 to 10, often from 3 to 8, and especially from 3 to 6 carbon atoms, optionally substituted with from 1 to 4 methyl groups. Examples of cycloalkyl groups are cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, 1-methylcyclopropyl, 2-methylcyclopropyl, 1-, 2- or 3-methyl. Cyclopentyl, 1-, 2-, 3- or 4-methylcyclohexyl, 1,2-dimethylcyclohexyl, 1,3-dimethylcyclohexyl, 2,3-dimethylcyclohexyl 2,2-dimethylcyclohexyl, 3,3-dimethylcyclohexyl, 4,4-dimethylcyclohexyl, and the like.

In the context of the present invention, an aromatic group is understood to mean a carbocyclic aromatic hydrocarbon group, for example a phenyl or naphthyl group.

In the context of the present invention, a heteroaromatic radical is understood to mean a heterocyclic aromatic radical which usually has 5 or 6 ring members, one of which is selected from nitrogen, oxygen and sulfur heteroatoms. And one or two of the other ring members The nitrogen atom and the remaining ring members are carbon. Examples of heteroaromatic groups are furyl, thienyl, pyrrolyl, pyrazolyl, imidazolyl, oxazolyl, isoxazolyl, pyridyl and thiazolyl.

In the context of the present invention, a fused aromatic group or ring is understood to mean a carbocyclic aromatic divalent hydrocarbon group, for example o-phenylene (benzo) or 1,2-naphthyl (naphthyl) ).

In the process of the invention, the tin-containing monomer of formula I is polymerized under the reaction conditions, under which the Ar-C(R ^a , R ^b ) groups are polymerized to form an organic polymer phase and the XSnY unit forms a tin oxide phase. These polymerizations are known as twin polymerization and are known from, for example, WO 2010/112580 and WO 2010/112581. In contrast to the process according to the invention, WO 2010/112580 and WO 2010/112581 exclusively propose monomers in which the tin is in the +4 oxidation state.

In the process of the invention, it is preferred to use one of the monomers of formula I, wherein at least one of the variables X and Y and especially two variables X and Y are oxygen.

In the process of the present invention, it is preferred to use a monomer of the formula I, wherein each of R ^a and R ^b in the Ar-C(R ^a , R ^b )-unit or the group of the formula A is hydrogen.

In the process of the present invention, it is preferred to use a monomer of the formula I, wherein R ¹ and R ^{2 are the} same or different and each of the groups of the formula Ar-C(R ^a , R ^b )-, preferably those of which Wherein R ^a and R ^b are each a group of the formula of hydrogen. When R ¹ and R ² are each an Ar-C(R ^a , R ^b )- group, Ar is preferably an aromatic or heteroaromatic group selected from a phenyl group and a furyl group, wherein phenyl and furyl groups are selected. Unsubstituted or having 1 or 2 substituents selected from the group consisting of halogen, OH, CN, C ₁ -C ₆ -alkyl, C ₁ -C ₆ -alkoxy, C ₁ -C ₆ -hydroxyalkyl and phenyl base. More specifically, the Ar-based phenyl or furyl group, wherein the phenyl and furyl groups are each unsubstituted or optionally have 1 or 2 selected from C ₁ -C ₆ -alkyl, C ₁ -C ₆ -hydroxyalkane And a C ₁ -C ₆ -alkoxy group and especially selected from the group consisting of a methylol group, a methyl group and a methoxy group. In a preferred embodiment, the Ar-based phenyl group is unsubstituted or in particular has 1 or 2 selected from the group consisting of C ₁ -C ₆ -alkyl and C ₁ -C ₆ -alkoxy and especially selected from methyl And a substituent of a methoxy group. Examples of particularly preferred Ar groups are methoxyphenyl or 2,4-dimethoxyphenyl. In particular, R ¹ and R ² are each independently (methoxyphenyl)methyl or (2,4-dimethoxyphenyl)methyl.

In a further embodiment of the monomer of formula I, the R ¹ and R ² groups together are a group of formula A as defined above, in particular a group of formula Aa: Wherein #, m, R, R ^a and R ^b are each as defined above. In the formulae A and Aa, the variable m is especially zero. When m is 1 or 2, R is especially hydroxymethyl, methyl or methoxy. In formulae A and Aa, R ^a and R ^b are each, in particular, hydrogen.

The monomers of formula I can be prepared in a manner similar to the methods known per se for the preparation of organotin compounds. In general, a monomer or compound of formula I (wherein R ¹ is an Ar-C(R ^a ,R ^b )- group) can be obtained by subjecting a suitable tin (II) compound (for example, tin (II) halide (such as tin chloride) (II)) or a tin (II) alkoxide (such as methanol tin (II) (Sn(OCH ₃ ) ₂ ))) and a compound of the formula Ar-C (R ^a , R ^b )-XH or the formula Ar-C ( A mixture of different compounds of R ^a , R ^b )-XH or Ar-C(R ^a , R ^b )-YH is prepared, wherein each of Ar, X, Y, R ^a and R ^b is as defined above. In the case of using tin (II) halide, the reaction is usually carried out in the presence of a tertiary amine as a base. Generally, a compound of the formula Ar-C(R ^a , R ^b )-XH or Ar-C(R ^a , R ^b )-YH is used in excess based on the desired stoichiometry of the reaction.

In a similar manner, a monomer or compound of formula I wherein R ¹ is an Ar-C(R ^a ,R ^b )- group can be obtained by subjecting a suitable tin (II) compound (eg, tin (II) halide (eg, chlorine) The tin (II) or tin (II) alkoxide (such as methanol (II) (Sn(OCH ₃ ) ₂ ))) is reacted with a compound of the formula AXHYH to obtain Wherein m, A, X, Y, R, R ^a and R ^b are each as defined above. In the case of using tin (II) halide, the reaction is usually carried out in the presence of a tertiary amine as a base. Typically, the compound AXHYH is used in excess based on the desired stoichiometry of the reaction.

To produce a polymer composite, the monomer of formula I (hereinafter also referred to as monomer I) can be polymerized separately (homopolymerization). Mixtures of different monomers can also be copolymerized. It is also possible to copolymerize one or more of the monomers I with a substance known to be copolymerizable with the R ¹ or R ² groups. In particular, such materials include aliphatic, aromatic or heteroaromatic aldehydes such as benzaldehyde, furfural, formaldehyde or acetaldehyde, preferably in gaseous form or in non-aqueous oligomeric or polymeric form (eg, trioxane) Formaldehyde in the form of heterocyclohexane or in the form of formaldehyde. The monomer I of the invention can likewise be copolymerized with other monomers which can be copolymerized under the conditions of the polymerization and comprise the semimetal forming the oxide, as described, for example, in WO 2010/112580 and WO 2010/112581. And it may have a metal or a semimetal other than tin. In particular, the materials include the monomers of the formula I described in WO 2010/112580 and WO 2010/112581, the following formula X Wherein M is a metal or a semimetal, preferably a metal or semimetal of the third or fourth main group or the fourth or fifth transition group 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 better Si or Ti and especially Si; R ^1a , R ^2a may be the same or different and each is Ar-C (R ^a , R ^b )- group, wherein each of Ar, R ^a , R ^{b is} as defined above in connection with formula I, especially as a preferred definition, or the R ^1a X and R ^2a Y groups together are a group of formula A'

Wherein A, R, m, R ^a , R ^b are each as defined above in connection with formula I, especially as a preferred definition, X is O, S or NH and especially O; Y is O, S or NH and especially O; q According to the valence of M or the charge system 0, 1 or 2 and especially 1, G, Q may be the same or different and each is O, S, NH or a chemical bond and especially an oxygen or chemical bond; R ^{1 '} and R ^{2 '} may be the same Or different and each is a C ₁ -C ₆ -alkyl, C ₃ -C ₆ -cycloalkyl, aryl or Ar'-C(R ^a' ,R ^b' )- group, wherein the Ar' Ar is defined, and R ^{a '} , R ^{b '} are each as defined for R ^a , R ^b and especially each is hydrogen, or R ^{1 '} , R ^{2 '} together with G and Q are as defined above for formula A' a group of the formula II, IIa, III, IIIa, IV, V, Va, VI or VIa as described in WO 2010/112580 and WO 2010/112581.

In a preferred embodiment, the proportion of the monomer other than the monomer of formula I (for example, the monomer of formula X or the above aldehyde) will not exceed 20% by weight and especially 10% by weight, based on the total amount of monomers to be polymerized, That is, the monomer of formula I accounts for at least 80% by weight and especially at least 90% by weight of the total amount of monomers to be polymerized. In another embodiment of the invention, the proportion of the monomer of the formula I in the total amount of monomers to be polymerized is from 20% by weight to 80% by weight, in particular from 30% by weight to 70% by weight, based on the monomers to be polymerized. The total amount of monomers other than the monomer of formula I (for example the monomer of formula X or the abovementioned aldehyde) is in the range from 20% to 80% by weight and in particular in the range from 30% to 70% by weight.

The monomers of formula I can be polymerized and copolymerized with different monomers in a manner similar to that described in WO 2010/112580 and WO 2010/112581.

In a preferred embodiment of the process of the invention, monomer I is polymerized in an organic solvent or solvent mixture, especially an organic aprotic solvent or solvent mixture. Preferred are the aprotic solvents in which the polymer composite formed is insoluble (solubility < 1 g/l at 25 ° C). Thus, particularly small particles of the polymer composite are formed under polymerization conditions. However, the polymerization can also be carried out in the substance.

It is assumed that the use of a polymer composite insoluble in the polymerization to form an aprotic solvent can promote particle formation in principle. If in the presence of particulate inorganic materials When polymerized, the formation of particles will likely be controlled by the presence of particulate inorganic materials, and this prevents the formation of coarse polymer composites.

The aprotic solvent is preferably selected such that monomer I is at least partially soluble. This is understood to mean that the solubility of monomer I in the solvent under polymerization conditions is at least 50 g/l, in particular at least 100 g/l. Typically, the organic solvent is selected such that the solubility of the monomer at 20 ° C is 50 g/l, especially at least 100 g/l. More specifically, the solvent is selected such that monomer I is substantially or completely soluble therein, i.e., the ratio of solvent to monomer I is selected such that at least 80%, especially at least 90% or all of the monomers are under polymerization conditions The I system is present in dissolved form.

By "aprotic" is meant that the solvent used for the polymerization contains substantially no solvent having one or more protons bonded to a hetero atom (e.g., O, S or N) and thus more or less acidic. The proportion of protic solvent in the solvent or solvent mixture used for the polymerization is therefore less than 10% by volume, in particular less than 1% by volume and especially less than 0.1% by volume, based on the total amount of organic solvent. The polymerization of monomer I is preferably carried out under substantially anhydrous conditions, i.e., the concentration of water at the beginning of the polymerization is less than 500 ppm, based on the amount of solvent used.

The solvent may be an inorganic or organic solvent or a mixture of an inorganic solvent and an organic solvent. It is preferably an organic solvent.

Examples of suitable aprotic organic solvents are halogenated hydrocarbons (for example dichloromethane, chloroform, dichloroethane, trichloroethane, 1,2-dichloroethane, 1,1,1-trichloroethane, 1 - chlorobutane, chlorobenzene, dichlorobenzene, fluorobenzene) and pure hydrocarbons (which may be aliphatic, cycloaliphatic or aromatic) and mixtures thereof with halogenated hydrocarbons. Examples of pure hydrocarbons are acyclic aliphatic hydrocarbons generally having 2 to 8 and preferably 3 to 8 carbon atoms, especially alkanes (e.g., ethane, isopropane and n-propane, n-butane and their isomers) , n-pentane and its isomers, n-hexane and its isomers, n-heptane and its isomers and n-octane and its isomers; cycloaliphatic hydrocarbons (for example with 5 to 8 carbons) Atom naphthenes such as cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, cycloheptane) and aromatic hydrocarbons (eg benzene, toluene, xylene, trimethylbenzene, ethyl) Benzene, cumene (2-propylbenzene), n-propylbenzene (1-propylbenzene) and t-butylbenzene). Also preferred are the above hydrocarbons and halogenated hydrocarbons (e.g., halogenated aliphatic hydrocarbons (e.g., methyl chloride, dichloromethane, chloroform, ethyl chloride, 1,2-dichloroethane, and 1,1,1-trichloro). A mixture of ethane and 1-chlorobutane) and a halogenated aromatic hydrocarbon such as chlorobenzene, 1,2-dichlorobenzene and fluorobenzene.

Examples of inorganic aprotic solvents are, in particular, supercritical carbon dioxide, carbon oxysulfide, carbon disulfide, nitrogen dioxide, sulfinium chloride, sulfonium chloride and liquid sulfur dioxide, and the latter three solvents can also function as polymerization initiators.

Monomer I is usually polymerized in the presence of a polymerization initiator or catalyst. The polymerization initiator or catalyst is selected such that it initiates or catalyzes the cationic polymerization of the monomer I (i.e., monomer units XR ¹ and YR ² ) and the formation of a tin oxide phase. Therefore, in the polymerization of the monomer I, on the one hand, the monomer units XR ¹ and YR ^{2 are} polymerized and on the other hand, the tin oxide phase is formed simultaneously. The term "synchronous" 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. Conversely, "synchronous" means that the processes are kinetically coupled and triggered by cationic polymerization conditions.

Suitable polymerization initiators or catalysts are in principle all materials which are known to catalyze cationic polymerization. Such materials include protonic acid (Brønsted acid) and aprotic Lewis acid. Preferred protonic catalysts are Brine acids, such as organic carboxylic acids such as trifluoroacetic acid, oxalic acid or lactic acid, and especially organic sulfonic acids such as methanesulfonic acid, trifluoromethane-sulfonic acid or toluenesulfonic acid. Inorganic Brinellic acids such as HCl, H ₂ SO ₄ or HClO _{4 are} likewise suitable. The Lewis acid used may be, for example, BF ₃ , BCl ₃ , SnCl ₄ , TiCl ₄ or AlCl ₃ . Lewis acid which is combined or dissolved in an ionic liquid in a complicated form can also be used. The polymerization initiator or catalyst is usually used in an amount of from 0.1% by weight to 10% by weight, based on the monomer M, preferably from 0.5% by weight to 5% by weight.

The temperature required for the polymerization of the monomer I is usually in the range of from 0 ° C to 150 ° C, specifically in the range of from 20 ° C to 140 ° C and especially in the range of from 40 ° C to 120 ° C.

The process of the invention is particularly suitable for the industrial manufacture of polymer composites comprising tin oxide in a continuous and/or batch mode. In batch mode, this means that the batch size is at least 10 kg, often at least 100 kg, especially at least 1000 kg or at least 5000 kg. In continuous mode, this means that the manufacturing volume is typically at least 100 kg/day, often at least 1000 kg/day, especially at least 10 t/day or at least 100 t/day.

The polymer composite comprising tin oxide obtainable by the process of the invention consists essentially (i.e. generally at least 90% by weight, in particular at least 95% by weight) composed of tin oxide and an organic polymer phase. The tin oxide phase generally consists essentially of (i.e. typically at least 90% by weight, in particular at least 95% by weight) consisting of tin oxide or tin oxide hydrate. Preferably, the tin oxide is present in an amount of at least 80% and especially at least 90% in the form of tin in the +2 oxidation state. The organic polymer phase is formed from a carbon-containing polymer other than elemental carbon. The composition of the organic polymer phase is defined by the Ar-C(R ^a , R ^b ) group, and thus it is typically a poly(hetero)aryl formaldehyde condensate or a polycarboxylate or a mixture thereof.

Another result of the process of the present invention is that the tin oxide phase and the organic polymer phase are present in a co-continuous arrangement over a wide range, which means that the individual phases do not substantially form any separate phase domains surrounded by the continuous phase domains as appropriate. Instead, the two phases form a phase domain that is spatially separated and penetrates each other, as evidenced by inspection of the material by means of a transmission electron microscope. For the terms "continuous phase domain", "discontinuous phase domain" and "co-continuous phase domain", reference is also made to WJWork 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 page 2003. Thus, a co-continuous arrangement of two component mixtures is understood to mean a phase separation arrangement of two phases or components, wherein in one domain of a particular phase, a continuous route through either phase can be pulled to an uncrossed All phase boundaries of any phase domain boundary.

In the polymer composite of the invention, the organic polymer phase and the tin oxide phase form a substantially co-continuous phase domain which comprises at least 50% by volume, often at least 80% by volume and especially at least 90% by volume of the polymer composite.

In the polymer composite of the invention, the distance between adjacent phase interfaces or the distance between domains adjacent to the same phase is small and on average does not exceed 100 nm, in particular does not exceed 20 nm and in particular does not exceed 10 nm. The distance between adjacent phases is, for example, the distance between two domains of the tin oxide phase separated from each other by the domain of the organic polymer phase or two organic polymer phases separated from each other by the domain of the tin oxide phase. The distance between the domains. The average distance between the domains adjacent to the same phase can be determined by means of small-angle x-ray scattering (SAXS) via the scattering vector q (for transmittance measurement at 20 ° C, monochromatic CuK _α radiation, 2D detector (image plate) ), the slit is collimated).

The size of the phase region can also be determined by a transmission electron microscope, in particular by means of HAADF-STEM technology (HAADF-STEM = high angle annular dark field scanning electron microscope) and thus the distance between the adjacent phase interfaces and the arrangement of the phases. In this imaging technique, relatively heavy elements (such as Sn, relative to C) appear to be lighter in color. Since the denser areas of the formulation appear to be less dense than the dense areas, the preparation of artifacts can be seen as well.

As already mentioned above, the invention also relates to the production of tin-carbon composites from at least one inorganic tin-containing phase, the tin in the inorganic tin-containing phase being in the form of tin in the form of +2 or 0 oxidation, in particular in elemental form or It is present in the form of tin (II) oxide or Sn(II) oxide hydrate or in the form of a mixture thereof. For this purpose, in a first step i, a polymer composite comprising tin oxide is provided by the above method. The tin oxide-containing polymer composite is carbonized in a second step. The organic polymer phase is here converted into a phase consisting essentially of elemental carbon. Basically save the phase structure.

For this purpose, the polymer composite obtained in step i is usually heated to a temperature of at least 400 ° C, preferably at least 500 ° C, especially at least 700 ° C, for example to a temperature in the range of from 400 ° C to 1800 ° C, substantially under exclusion of oxygen. The temperature in the range of preferably from 500 ° C to 1500 ° C, especially from 700 ° C to 1200 ° C. "Substantially excludes oxygen" means that a portion of the oxygen pressure in the reaction zone where carbonization is carried out is low and preferably does not exceed 20 mbar, especially 10 mbar.

In one embodiment of the invention, the carbonization is carried out in an inert gas atmosphere, such as 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. In another embodiment of the invention, the carbonization is carried out in the presence of a so-called reducing gas. In addition to hydrogen (H ₂ ), the reducing gas also includes a hydrocarbon gas such as methane, ethane or propane or ammonia (NH ₃ ). The reducing gas can be used as it is or in the form of a mixture with an inert gas such as nitrogen or argon.

The particulate composite is preferably used for carbonization in the form of a dry (i.e., substantially solvent free) powder. By "solvent free" herein and below is meant that the composite comprises less than 1% by weight, especially less than 0.1% by weight of solvent.

Carbonization is optionally carried out in the presence of an oxidizing agent which promotes the formation of graphite, for example a transition metal halide such as ferric chloride. This achieves the effect that the carbon in the carbon material of the present invention is mainly present in the form of graphite or graphene units, i.e., in the form of polycyclic fused structural units in which each carbon atom forms a covalent bond with three other carbon atoms. The amount of the oxidizing agents is usually from 1% by weight to 20% by weight based on the polymer composite. In the case where the oxidizing agent is used in carbonization, the procedure is generally a mixture of the polymer composite and the oxidizing agent mixed with each other and carbonized into a substantially solvent-free powder form. The oxidizing agent and its reaction product are soluble in the solvent or solvent mixture after carbonization by, for example, washing off the oxidizing agent using, for example, a solvent or solvent mixture or by evaporating.

In this manner, in step ii, a preferred particulate tin-carbon composite comprising a carbon phase and at least one tin phase is obtained. The carbon-tin composite of the invention generally consists of at least one tin phase and elemental carbon to the extent of at least 90% by weight, in particular at least 95% by weight. The tin-containing phase generally consists essentially of (i.e., typically at least 90% by weight, especially at least 95% by weight) consisting of tin or tin oxide or tin oxide hydrate or mixtures thereof.

According to the present invention, the tin-carbon composite material comprises a carbon phase (hereinafter also referred to as phase C), wherein the carbon is substantially present in the form of an element, which means that based on the total amount of carbon in the phase C, a non-carbon atom (for example, N, The proportion of O, S, P and/or H) in the carbon phase is less than 10% by weight, in particular less than 5% by weight. The content of non-carbon atoms in the phase C can be determined by means of an x-ray photoelectron spectrometer. Due to the preparation, in addition to carbon, the phase C may in particular comprise a small amount of nitrogen, oxygen, sulfur and/or hydrogen. The molar ratio of hydrogen to carbon will generally not exceed a value of 1:3, specifically a value of 1:5 and especially a value of 1:10. The value can also be 0 or almost 0, for example 0.1. In the C phase, carbon may be present mainly in the form of amorphous or graphite. The presence of amorphous or graphitic carbon can be determined by means of ESCA studies with reference to characteristic binding energy (284.5 eV) and characteristic asymmetric signal shapes. Carbon in the form of graphite is understood to mean that the carbon is at least partially arranged in a hexagonal layer typical of graphite, wherein the layers may also be bent or spalled.

In addition to the C phase, the tin-carbon composite of the present invention also contains at least one tin phase (Sn phase), and the tin in the tin phase is in a +2 or 0 oxidation state or in a mixed form thereof. The Sn phase is preferably substantially composed of elemental tin or tin (II) oxide or tin (II) oxide hydrate (e.g., tin (II) hydroxide) or a mixture thereof. In the Sn phase, the ratio of non-tin and non-oxygen atoms (for example other metals or semi-metals and N, S, P and/or H) is preferably less than 10% by weight, in particular less than the total amount of carbon in the Sn phase. 5 wt%. In the Sn phase, tin may be in the form of tin in the +2 oxidation state or in the form of elemental tin (i.e., the tin is in the oxidation state of 0) or in a mixed form. In a preferred embodiment, the tin is predominantly in the oxidation state of 0, which means that at least 50%, especially at least 80% or at least 90% of the tin atoms in the Sn phase are in the oxidation state of 0 and in particular in the form of elemental tin.

Generally, the C phase and the Sn phase form a co-continuous phase domain in an irregular arrangement, and the average distance between two adjacent domains of the Sn phase or the average distance between two adjacent domains of the C phase does not exceed 100 nm. In terms of no more than 20 nm, in particular no more than 10 nm, and, for example, in the range from 0.5 nm to 100 nm, in particular from 0.7 nm to 20 nm and especially from 1 nm to 10 nm. With regard to the average distance between the two adjacent domains of the Sn phase and the C phase, the above description for the polymer composite obtained in the step i applies in the same manner.

In yet another embodiment, the Sn phase is in the form of a Sn domain embedded in the continuous carbon phase C as a matrix in a substantially separate manner. In this embodiment, the size of the Sn domain of 50% by volume or more is often in the range of 1 nm to 20 μm, especially 1 nm to 1 μm. More specifically, in the tin-carbon composite materials of the present invention, the tin content is from 5% by weight to 90% by weight, preferably from 10% by weight to 75% by weight, based on the total mass of the tin-carbon composite material. It is preferably from 15% by weight to 55% by weight, especially from 20% by weight to 40% by weight.

The process of the invention is particularly suitable for the industrial manufacture of tin-carbon composites in a continuous and/or batch mode. In batch mode, this means that the batch size is at least 10 kg, often at least 100 kg, especially at least 1000 kg or at least 5000 kg. In continuous mode, this means that the amount produced is typically at least 100 kg/day, often at least 1000 kg/day, especially at least 10 t/day or at least 100 t/day.

As already stated, the tin-carbon composites according to the invention are particularly advantageous in the use in electrochemical cells, in particular lithium ion batteries, in particular due to high specific capacitance, high cycle stability, low self-discharge and formation of lithium dendrites. Trends and attention are drawn to the advantageous kinetics of charge/discharge operations in order to achieve high current densities.

In the context of the present invention, an electrochemical cell or battery pack is understood to mean any type of battery pack, capacitor and accumulator (secondary battery pack), in particular an alkali metal battery or battery pack (eg lithium, lithium ion, lithium-sulfur) And alkaline earth metal batteries and accumulators, especially in the form of high energy or high performance systems), and electrolytic capacitors and double layer capacitors known by Supercaps, Goldcaps under the name BoostCaps or Ultracaps.

Accordingly, the present invention also provides the use of a tin-carbon composite for the production of an electrochemical cell and more particularly for its use in the anode of a lithium ion battery, particularly a lithium ion secondary battery. Accordingly, the present invention is also directed to an anode for a lithium ion battery, particularly a lithium ion secondary battery, comprising the tin-carbon composite of the present invention.

In addition to the tin-carbon composite of the present invention, the anode typically comprises at least one binder suitable for consolidation of the tin-carbon composite of the present invention, and optionally other electrically conductive or electroactive components. In addition, the anode typically has electrical contacts for charge supply and removal. The amount of the tin-carbon composite of the present invention is typically at least 40% by weight, often at least 50% by weight and especially at least 60% by weight, based on the total mass of the anode material minus any current collectors and electrical contacts.

Other suitable conductive or electroactive components are known from autocorrelated monographs (see, for example, MESpahr, Carbon Conductive Additives for Lithium-Ion Batteries, M. Yoshio et al. (eds.) Lithium Ion Batteries, Springer Science+ Business Media, New York 2009, Pages 117-154 and the documents cited therein). Other conductive or electroactive components useful in the anode of the present invention include carbon black, graphite, carbon fibers, carbon nanofibers, carbon nanotubes or conductive polymers. Typically, about 2.5% by weight is used in the anode Up to 40% by weight of electrically conductive material and 50% to 97.5% by weight, often 60% to 95% by weight of the electroactive material of the invention, expressed in weight % based on the total mass of the anode material minus any current collectors and electrical contacts point.

Useful binders for producing anodes using the tin-carbon composites and other electroactive materials described above include, in principle, all prior art binders suitable for the anode material, as known from the autocorrelation monograph (see, for example, A. Nagai, Applications of PVdF- Related Materials for Lithium-Ion Batteries, M. Yoshio et al. (eds.) Lithium Ion Batteries, Springer Science+Business Media, New York 2009, pp. 155-162 and the literature on music, and H. Yamamoto and H. Mori , SBR adhesive (for negative electrode) and ACM adhesive (for positive electrode), ibid., pp. 163-180). Useful binders include, inter alia, the following polymeric materials: polyethylene oxide (PEO), cellulose, carboxymethyl cellulose (CMC), polyethylene, polypropylene, polytetrafluoroethylene, polyacrylonitrile-methyl methacrylate, Polytetrafluoroethylene, styrene-butadiene copolymer, tetrafluoroethylene-hexafluoroethylene copolymer, polydifluoroethylene ethylene (PVdF), polydifluoroethylene hexafluoropropylene copolymer (PVdF-HFP), four Fluoroethylene hexafluoropropylene copolymer, tetrafluoroethylene, perfluoroalkyl-vinyl ether copolymer, difluoroethylene-hexafluoropropylene copolymer, ethylene-tetrafluoroethylene copolymer, difluoroethylene-chlorotrifluoro Ethylene copolymer, ethylene-chlorofluoroethylene copolymer, ethylene-acrylic acid copolymer (including and excluding sodium ion), ethylene-methacrylic acid copolymer (including and excluding sodium ion), ethylene-methacrylate copolymer (including and excluding sodium ions), polyimine and polyisobutylene.

Select bonding if considering the nature of any solvent used for preparation Agent. The binder is typically used in an amount of from 1% to 10% by weight based on the total mixture of anode materials (i.e., tin-carbon composite and, optionally, other electrically active or electrically conductive materials). It is preferred to use from 2% by weight to 8% by weight and especially from 3% by weight to 7% by weight.

The anode can be manufactured by itself in a manner known per se as known from prior art and autocorrelated monographs cited in the opening paragraph (for example, see RJ Brodd, M. Yoshio, Production processes for Fabrication of Lithium-Ion Batteries, M. Yoshio). Et al. (eds.) Lithium Ion Batteries, Springer Science+Business Media, New York 2009, pp. 181-194 and references cited therein). For example, the anode can be produced by mixing an electroactive material of the present invention with an optional other component of the anode material (electrically conductive component and/or an organic solvent (for example, N-methylpyrrolidone or a hydrocarbon solvent) as the case may be. The organic binder), and optionally, is subjected to a forming process or an inert metal foil (such as a Cu foil) is applied thereto. Then dry as appropriate. This is carried out, for example, at a temperature of from 80 ° C to 150 ° C. The drying operation can also be carried out under reduced pressure and usually lasts from 3 to 48 hours. Forming may also be carried out by a melting or sintering process, as the case may be.

The invention also provides a lithium ion battery, in particular a lithium ion secondary battery, having at least one anode comprising the tin-carbon composite of the invention

Such batteries typically have at least one anode of the invention, a cathode suitable for a lithium ion battery, an electrolyte, and optionally a spacer.

For suitable cathode materials, suitable electrolytes and suitable spacers and possible arrangements, reference is made to the related prior art (for example, prior art cited at the outset), and appropriate monographs and reference works: for example, Wakihara et al. (editor), Lithium Ion Batteries , 1st Edition, Wiley VCH, Weinheim, 1998; David Linden: Handbook of Batteries (McGraw-Hill Handbooks), 3rd edition, McGraw-Hill Professional, New York 2008; JOBesenhard: Handbook of Battery Materials. Wiley-VCH, 1998; Yoshio et al. (eds.) Lithium Ion Batteries , Springer Science+Business Media, New York 2009; KIAifantis, SAHackney, RVKumar, (eds.), High Energy Density Lithium Ion Batteries , Wiley-VCH, 2010.

Useful cathodes include, inter alia, cathodes in which the cathode material comprises at least one lithium transition metal oxide (eg, 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 lithium transition metal phosphate (for example, lithium iron phosphate). Useful cathode materials also include sulfur and sulfur-containing composite materials such as, for example, sulfur-carbon composites known for lithium-sulfur batteries.

The two electrodes (i.e., the anode and the cathode) are connected to each other using a liquid or solid electrolyte. Useful liquid electrolytes include, inter alia, non-aqueous solutions of lithium salts and molten Li salts (typically <20 ppm water), such as lithium hexafluorophosphate, lithium perchlorate, lithium hexafluoroarsenate, lithium trifluoromethanesulfonate, bis (three) Lithium fluoromethylsulfonyl) guanidinium or lithium tetrafluoroborate (especially lithium hexafluorophosphate or lithium tetrafluoroborate) in one of the following solvents: a suitable aprotic solvent (eg, ethylene carbonate, propylene carbonate, and mixtures thereof) Or a solution in a plurality of: dimethyl carbonate, diethyl carbonate, dimethoxyethane, methyl propionate, ethyl propionate, butyrolactone, acetonitrile, ethyl acetate, methyl acetate, toluene and Xylene It is stored in a mixture of ethylene carbonate and diethyl carbonate. The solid electrolyte used may be, for example, an ion conductive polymer.

A spacer impregnated with a liquid electrolyte may be disposed between the electrodes. Examples of the spacer are, in particular, a glass fiber non-woven fabric and a porous organic polymer film such as a porous film of polyethylene, polypropylene, PVdF or the like.

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

The following examples are intended to illustrate the invention and should not be construed in a limiting sense.

TEM analysis was performed by a Tecnai F20 transmission electron microscope (FEI, Eindhoven, The Netherlands) at an operating voltage of 200 kV using an ultra-thin layer technique (incorporating a sample into a synthetic resin as a matrix) for HAADF-STEM analysis.

The ESCA study was performed using a FEI 5500 LS x-ray photoelectron spectrometer (Eindhoven, The Netherlands) from FEI.

Small angle x-ray scattering analysis was performed at 20 ° C in slit collimation using Cu _Kα radiation monochromated with a Göbel mirror. Data is collected against the background and sharpened with respect to blurring caused by slit collimation.

Regarding the IR spectrum, the abbreviations s, m, and w represent strong, medium, and weak, and indicate the relative strength of the bands.

I. Preparation of monomer I: Preparation Example 1: Bis(2-methoxyphenyl methoxide) tin (II) (monomer I, wherein X = Y = O; R ¹ = R ² = 2-methoxybenzyl)

a) 19.51 g (10.29 mol) of anhydrous SnCl _{2 was} dissolved in 250 ml of methanol. To this was added 57 ml (41.16 mol) of anhydrous triethylamine dropwise at room temperature. A colorless precipitate formed immediately. After the complete addition of triethylamine, the reaction mixture was stirred for additional 2 h and then the precipitate was filtered. The resulting colorless solid was washed three times with 20 ml of methanol each time and then three times with 20 ml of diethyl ether each time. 17.67 g (97.74 mmol, 95%) of sodium tin (II) (Sn(OCH ₃ ) ₂ ) in amorphous solid form was obtained.

IR[cm ^-1 ]: 2928(m)(CH), 2828(m)(CH),1594(s),1486(s),1455(s), 1362(m),1279(m),1233( s), 1111(s)(CO), 1011(s),814(m),,749(s),714(m),615(s),575(s)(Sn-O),478(m) ), 432 (m).

EA measured value (calculated value): C: 48.6% (C: 48.9%), H: 5.0% (H: 4.6%).

¹ H NMR (500.30 MHz, CDCl ₃ ) δ [ppm]: 3.78 (s, 3 H, CH ₃ O), 4.92 (s, 2 H, CH ₂ ), 6.82 (d, 1 H), 6.87 (dd, 1 H), 7.23 (dd, 1 H), 7.31 (d, 1H).

¹³ C NMR (125.81 MHz, CDCl ₃ ) δ [ppm]: 53.8 (CH ₃ O), 59.4 (CH ₂ ), 108.8, 119.4, 127.0, 127.2, 128.4, 155.9.

¹¹⁹ Sn NMR (186.53 MHz, CDCl ₃ ) δ [ppm]: -160.

¹³ C{ ¹ H}CP-MAS NMR (100.62 MHz) δ [ppm]: 55.9 (CH ₃ O), 61.2 (CH ₂ ), 109.3, 119.7, 125.5, 127.4, 131.7, 156.2.

¹¹⁹ Sn{ ¹ H}CP-MAS NMR (149.19 MHz) δ [ppm]: -351.

b) 3.00 g (16.59 mmol) of Sn(OCH ₃ ) _{2 was} suspended in 50 ml of toluene. After the addition of 4.82 g (34.85 mmol) of 2-methoxybenzyl alcohol, the suspension was heated and the released methanol was distilled off, during which the suspension material dissolved. After clarifying the toluene solution to about 15 ml, a colorless solid precipitated. The solid was washed repeatedly with diethyl ether and dried under high vacuum (10 ^-3 mbar). 4.73 g (12.04 mmol, 72.5%) of the title compound are obtained as a colorless solid, which can be identified based on its IR spectrum or ¹ H NMR spectrum.

Preparation Example 2: Preparation of bis(2,4-dimethoxyphenylmethane)tin (II) (monomer I, where X = Y = O; R ¹ = R ² = 2,4-dimethoxybenzyl)

2.00 g (11.06 mmol) of Sn(OCH ₃ ) _{2 was} suspended in 50 ml of toluene. After the addition of 3.91 g (23.25 mmol) of 2,4-dimethoxybenzyl alcohol, the suspension was heated and the released methanol was distilled off, during which the suspension material dissolved. The resulting clear solution was concentrated until a white solid precipitated. The solid was washed repeatedly with diethyl ether and dried under high vacuum (10 ^-3 mbar). This gave 3.98 g (8.78 mmol, 79.4%) of the title compound as a colourless solid.

IR[cm ^-1 ]: 2936(m)(CH), 2838(m)(CH), 1590(s), 1501(s), 1457(s), 1370(m), 1285(s), 1254( m), 1204(s), 1156(s), 1123(s)(CO v ), 1032(s), 986(s), 932(m), 822(s), 731(s), 695(m ), 627 (m), 571 (s) (Sn-O), 517 (m), 455 (s).

EA measured value (calculated value): C: 47.4% (C: 47.7%), H: 4.6% (H: 4.9%).

¹ H NMR (500.30 MHz, CDCl ₃ ) δ [ppm]: 3.75 (s, 3 H, 4-MeO), 3.80 (s, 3 H, 2-CH ₃ O), 4.76 (s, 2 H, CH ₂ ), 6.40 (dd, 2 H), 7.20 (s, 1 H).

¹³ C NMR (125.81 MHz, CDCl ₃ ) δ [ppm]: 55.3 (CH ₃ O), 60.6 (CH ₂ ), 98.3, 103.8, 124.6, 130.1, 158.2, 160.3.

¹¹⁹ Sn NMR (186.52 MHz, CDCl ₃ ) δ [ppm]: -161, - 269.

¹³ C{ ¹ H}CP-MAS NMR (100.62 MHz) δ [ppm]: 54.5 (CH ₃ O), 58.9 (CH ₂ ), 97.0, 108.1, 126.3, 133.4, 158.4, 160.8.

¹¹⁹ Sn{ ¹ H}CP-MAS NMR (149.17 MHz) δ [ppm]: -350.

Preparation Example 3: Preparation of bis((2-thienyl)dimethyloxide) tin (II) (Monomer I, wherein X = Y = O; R ¹ = R ² = 1 - (2-thienyl)-1-methylethyl)

2.00 g (11.06 mmol) of Sn(OCH ₃ ) _{2 was} suspended in 50 ml of toluene. After adding a solution of 3.15 g (22.12 mmol) of (2-thienyl)dimethylmethanol in 8 ml of toluene, the mixture was stirred at 23 ° C for 1 h and then the methanol formed in the reaction was removed under reduced pressure. The resulting clear solution was concentrated to dryness. The resulting colorless solid was crystallised from EtOAc (EtOAc)

Preparation Example 4: Preparation of 7-methoxybenzo[4 H -1,3,2-]dioxastannin

1.5 g (8.30 mmol) of Sn(OCH ₃ ) _{2 was} suspended in 50 ml of toluene. After the addition of 1.28 g (8.30 mmol) of 2-hydroxy-5-methoxybenzyl alcohol, the mixture was stirred at 23 ° C for 1 h and then the methanol formed in the reaction was removed by distillation. The resulting clear solution was concentrated to dryness under reduced pressure. This gave a yellow solid which was washed thoroughly with diethyl ether and dried under high vacuum (10 ^-3 mbar). This gave 1.83 g (6.72 mmol, 81%) of the title compound.

Preparation Example 5: Preparation of 6-methoxybenzo[4 H -1,3,2-]dioxastannane

This preparation was carried out analogously to the preparation of Example 4 except that 2-hydroxy-4-methoxybenzyl alcohol was used instead of 2-hydroxy-5-methoxybenzyl alcohol.

Yield: 1.65 g (6.06 mmol, 73%).

EA measured value (calculated value): C: 34.7% (C: 35.5%), H: 3.1% (H: 3.0%).

IR[cm ^-1 ]: 2933 (m) (CH), 2830 (m) (CH), 1601 (s), 1572 (s), 1489 (s), 1435 (s), 1273 (s), 1194 ( s), 1154(s), 1101(s)(CO v ), 1032(s), 957(s), 832(m), 789(m), 735(m), 488(s)(Sn-O ).

Preparation Example 6: Preparation of 7-methylbenzo[4 H -1,3,2-]dioxastannane

This preparation was carried out analogously to the preparation of Example 4 except that 2-hydroxy-5-methoxybenzyl alcohol was used instead of 2-hydroxy-5-methoxybenzyl alcohol.

Yield: 1.68 g (6.60 mmol, 79.5%).

Production of polymer composites:

Example 1:

0.5 g (1.27 mmol) of the compound of Preparation Example 1 (monomer 1) was dissolved in 16 ml of chloroform. To the solution, a monomer based on 10 mol% of trifluoromethanesulfonic acid was added as a catalyst while stirring, and the mixture was heated to 50 ° C for 5 days. During this process, a solid precipitated. The solid was filtered under suction. After repeated washing with diethyl ether and drying under high vacuum (10 ^-3 mbar), a colorless solid polymer composite was obtained in a yield of 0.22 g (43%).

Example 2:

The compound of Example 1 was prepared in a manner similar to that of Example 1 using 10 mol% of trifluoroacetic acid as a catalyst to polymerize 0.52 g. A colorless solid polymer composite was obtained in a yield of 0.06 g (12%).

Example 3:

0.94 g (2.09 mmol) of the compound of Preparation Example 2 (monomer 2) was dissolved in 14 ml of chloroform. To the solution was added a monomer based on 10 mol% of trifluoromethanesulfonic acid as a catalyst while stirring and the mixture was heated to 50 ° C for 24 h. During this process, a solid precipitated. The solid was filtered under suction. After repeated washing with diethyl ether and drying under high vacuum (10 ^-3 mbar), a colorless solid polymer composite was obtained in a yield of 0.84 g (89%).

Example 4:

A compound of Example 2 was prepared by polymerizing 0.6 g of 10 mol% of trifluoroacetic acid as a catalyst in a manner similar to Example 1. A colorless solid polymer composite was obtained in a yield of 0.19 g (32%).

Example 5:

0.91 g of the compound of Preparation Example 5 was dissolved in 6 ml of anhydrous chloroform and 10 mol% of trifluoromethanesulfonic acid dissolved in 2 ml of anhydrous chloroform was mixed. The reaction mixture was stirred at room temperature for a further 3 days. Thereafter, the purple precipitate was filtered and washed repeatedly with chloroform. Yield: 0.74 g (77%).

IR[cm ^-1 ]: 3600-3050 (m) (OH), 2965 (w) (CH), 2840 (w) (CH), 1605 (m), 1497 (m), 1447 (m), 1223 ( s), 1175(s), 1092(CO v )(s), 1021(s), 955(m), 835(m), 758(m), 631(s), 567(m), 507(m ), 426(s) (Sn-O).

Claims (27)

A compound of the formula I, R ¹ -X-Sn-YR ² (I) wherein R ¹ is an Ar-C(R ^a ,R ^b )- group, wherein an Ar-based aromatic or heteroaromatic ring a case having 1 or 2 substituents selected from the group consisting of halogen, OH, CN, C ₁ -C ₆ -alkyl, C ₁ -C ₆ -alkoxy and phenyl, and R ^a and R ^b are each independently hydrogen Or methyl or together an oxygen atom or a methylene group (=CH ₂ ), R ² is a C ₁ -C ₁₀ -alkyl group or a C ₃ -C ₈ -cycloalkyl group or has the definition given for R ¹ One; or R ¹ together with R ^{2 is a} group of formula A: Wherein A is an aromatic or heteroaromatic ring fused to a double bond, m is 0, 1 or 2, and the R groups may be the same or different and are selected from the group consisting of halogen, CN, C ₁ -C ₆ -alkyl, C ₁ -C ₆ -hydroxyalkyl, C ₁ -C ₆ -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 compound of claim 1, wherein each of X and Y in formula I is oxygen. The compound of claim 1, wherein the Ar-C(R ^a , R ^b )- unit or the R ^a and R ^b in the group of the formula A are each hydrogen. The compound of any one of claims 1 to 3, wherein R ¹ , R ^{2 are the} same or different and each is an Ar-C(R ^a , R ^b )- group. The compound according to any one of claims 1 to 3, wherein the Ar in the Ar-C(R ^a , R ^b )- unit is an aromatic or heteroaromatic group selected from the group consisting of a phenyl group and a furyl group, wherein benzene The base and the furyl group are unsubstituted or optionally have 1 or 2 substituents selected from the group consisting of halogen, CN, C ₁ -C ₆ -alkyl and C ₁ -C ₆ -alkoxy. The compound of claim 5, wherein the Ar system of the Ar-C(R ^a , R ^b )- unit has 1 or 2 selected from a C ₁ -C ₆ -alkyl group, a C ₁ -C ₆ -hydroxyalkyl group And a phenyl group having a substituent of a C ₁ -C ₆ -alkoxy group. The compound of claim 6, wherein the Ar-C(R ^a , R ^b )- unit is an Ar-based 2-methoxyphenyl group or a 2,4-dimethoxyphenyl group. The compound of any one of claims 1 to 3, wherein R ¹ and R ² together are a group of the formula A. The compound of any one of claims 1 to 3, wherein R ¹ and R ² together are a group of formula Aa Wherein m, R, R ^a and R ^b are each as defined above. The compound of claim 9, wherein m in the formula Aa is 0, 1 or 2, R is selected from the group consisting of methylol, methyl and methoxy, and each of R ^a and R ^b is hydrogen. A method of producing a polymer composite comprising tin oxide, the composite comprising a) at least one inorganic tin oxide phase; and b) an organic polymer phase; the method comprising at least one of claims 1 to 7 The compound of formula I is polymerized under polymerization conditions under which the Ar-C(R ^a ,R ^b ) groups are polymerized to form the organic polymer phase and the XSnY unit is polymerized to form the tin oxide phase. The method of claim 11, wherein the polymerization of the compound of formula I is carried out in an aprotic organic solvent. The method of any one of claims 11 and 12, wherein the polymerization of the compound of formula I is initiated by the addition of at least one acid. A polymer composite comprising tin oxide comprising a) at least one inorganic tin oxide phase; and b) an organic polymer phase; the polymer composite material obtainable by the method of any one of claims 11 to 13 . The polymer composite of claim 14, wherein the organic polymer phase and the inorganic tin oxide phase form a substantially co-continuous phase domain, and an average distance between two adjacent domains of the same phase does not exceed 100 nm. The polymer composite of claim 14 or 15, wherein the tin oxide phase is substantially present in the form of tin (II) oxide. A method of producing a tin-carbon composite material, the composite material comprising at least one inorganic tin-containing phase, wherein the tin is present in a +2 or 0 oxidation state or in a mixture thereof; and a carbon phase in which the carbon system exists in an elemental form The method comprises: i. providing oxidation comprising oxidation by the method of any one of claims 11 to 13 a polymer composite of tin comprising a) at least one inorganic tin oxide phase; and b) an organic polymer phase; and ii. the organic polymer phase of the polymer composite obtained in the carbonization step i . The method of claim 17, wherein the carbonization is carried out in a substantially oxygen-free atmosphere at a temperature in the range of from 400 °C to 1800 °C. The method of claim 17 or 18, wherein the carbonization is carried out in an atmosphere comprising a reducing gas at a temperature in the range of from 400 °C to 1800 °C. A tin-carbon composite comprising at least one inorganic tin-containing phase Z, wherein the tin is present in a +2 or 0 oxidation state or in a mixture thereof; and a carbon phase C, wherein the carbon system is substantially in elemental form; The composite material can be obtained by the method of any one of claims 17 to 19. The tin-carbon composite of claim 20, wherein the carbon phase C and the tin-containing phase Z form a substantially co-continuous phase domain, and an average distance between two adjacent domains of the same phase does not exceed 100 nm. The tin-carbon composite of claim 20, wherein the carbon phase C is continuous and the tin-containing phase Z forms a substantially separate domain, a domain having a size between 1 nm and 20 μm. A tin-carbon composite according to claim 20, 21 or 22, wherein the tin-containing phase Z consists essentially of elemental tin to an extent of at least 90%. A use of a tin-carbon composite material according to any one of claims 20 to 23 for producing an electrochemical cell. Use of a tin-carbon composite according to any one of claims 20 to 23 for use in an anode of a lithium ion battery, especially a lithium ion secondary battery. An anode for a lithium ion battery, comprising at least one tin-carbon composite material according to any one of claims 20 to 23. A lithium ion battery comprising at least one anode as claimed in claim 26.