JP2014532258A - Tin oxide-containing polymer composite material - Google Patents

Abstract

The present invention relates to a novel tin oxide-containing polymer composite material, a method for producing the same, and a method for using the tin oxide-containing polymer composite material for the production of a tin-carbon composite material. The tin-carbon composite material has at least one inorganic tin-containing phase (in which the tin is present in the elemental state or in the state of tin (II) oxide, or in a mixed state thereof); It is composed of a carbon phase in which carbon exists in an elemental state. Such tin-carbon composite materials are particularly suitable for the production of anode materials for electrochemical cells, in particular lithium cells. The invention also relates to compounds of the general formula I (monomers) used for the production of the tin oxide-containing polymer composites of the invention. R1-X-Sn-Y-R2 (I) (wherein R1 is an Ar-C (Ra, Rb) group (where Ar is halogen, OH, CN, C1-C6-alkyl, C1-C6-alkoxy) And an aromatic or heteroaromatic ring optionally having 1 or 2 substituents selected from phenyl, and Ra and Rb are each independently hydrogen or methyl, or both are an oxygen atom or a methylidene group (= CH2) and R2 is C1-C10-alkyl or C3-C8-cycloalkyl, or has one of the definitions of R1, or both R1 and R2 are groups of formula A Wherein A is an aromatic or heteroaromatic ring united with a double bond, m is 0, 1 or 2, and the R groups may be the same or different. Halogen, CN, C1-C6-alkyl, C1- Is selected from 6-alkoxy and phenyl, R1 and R2 being as respectively defined above.), And, X is O, S or NH, Y is O, S or NH.)

Description

  The present invention relates to a novel tin oxide-containing polymer composite, a method for producing the same, and a method of using the tin oxide-containing polymer composite for the production of a tin-carbon composite. The tin-carbon composite material has at least one inorganic tin-containing phase (in which the tin is present in the elemental state or in the state of tin (II) oxide, or in a mixed state thereof); It is composed of a carbon phase in which carbon exists in an elemental state. Such tin-carbon composite materials are particularly suitable for the production of anode materials for electrochemical cells, in particular lithium cells. The invention also relates to a compound (monomer) for the production of the tin oxide-containing polymer composite of the invention.

  Mobile electrical devices have played a major role in the expanding mobile society. In recent years, batteries, particularly rechargeable batteries (so-called secondary batteries or accumulators) have been used in almost every part of everyday life. Currently, secondary batteries are required to have complex characteristics with respect to electrical properties and mechanical properties. For example, in the electrical industry, in order to realize a long life, a new small and lightweight secondary battery or storage battery having a large capacity and excellent cycle stability is required. Furthermore, temperature sensitivity and self-discharge rate should be small to ensure high reliability and efficiency. At the same time, high safety standards are required for use. The lithium secondary battery having the above properties is particularly important for the automobile sector, and can be used, for example, as an energy storage device in an electric vehicle or a hybrid vehicle.

  Furthermore, in this case, in order to realize a high current density, a storage battery having preferable electrokinetic characteristics is required. In addition, when developing a new type of storage battery system, it is particularly important to be able to manufacture a rechargeable storage battery by an inexpensive method. Environmental aspects are also playing an increasingly important role in developing new storage battery systems.

The positive electrode of current high-energy lithium batteries nowadays typically includes lithium transition metal oxides or spinel type complex oxides as active materials. Examples of these are LiCoO ₂ , LiNiO ₂ , LiNi _1-xy Co _x MyO ₂ (0 <x <1, y <1, M is, for example, Al or Mn), or LiMn ₂ O ₄ , or lithium Iron phosphate. As for the structure of the negative electrode of the current lithium battery, it has been shown in recent years that a lithium graphite intercalation compound is used (Journal Electrochem. Soc. 1990, 2009). In addition, lithium silicon intercalation compounds, lithium alloys, and lithium titanates have been studied as negative electrode materials ("Next generation anodds for secondary Li-ion batteries" in High Energy Density Li-Batteries by KE Aifantis). , Wiley-VCH, 2010 ", pages 129-162).

These two electrodes are coupled to each other in a lithium battery using a liquid electrolyte or a solid electrolyte. When the lithium battery is (re) charged, the positive electrode material is oxidized (eg, according to the following formula: LiCoO ₂ → nLi ++ Li _(1-n) CoO ₂ + ne ⁻ ). Thereby, lithium is desorbed from the positive electrode material and moves to the negative electrode in the form of lithium ions. In this negative electrode, lithium ions are bound as the negative electrode material is reduced, and in the case of graphite, lithium ions are intercalated with the reduction of graphite. In this case, lithium is contained in an interlayer site having a graphite structure, and when the storage battery is discharged, lithium bonded to the negative electrode is released from the negative electrode in the form of lithium ions, and the negative electrode material is oxidized. Lithium ions move to the positive electrode through the electrolyte and are combined as the positive electrode is reduced. In the case of discharging the storage battery and in the case of recharging the storage battery, the lithium ions move through the separator.

  However, a significant drawback when using graphite in a lithium ion battery is that the theoretical upper limit is 0.372 Ah / g and the specific capacity is relatively low. Similar characteristics are seen with carbon materials similar to graphite other than graphite. For example, carbon black and shiny carbon or hard carbon such as acetylene black, lamp black, furnace black, frame black, cracking black, channel black or thermal black. Further, such a negative electrode material has a safety problem.

When a lithium alloy (for example, an alloy of Li _x Si, Li _x Pb, Li _x Sn, Li _x Al, or Li _x Sb) is used, a high specific capacity can be realized. These allow for a charge capacity up to 10 times that of graphite (see pages 356-64 of “Li _x Si alloy Processings of the Electrochemical Society 87-1, 1987” by RA Huggins). A significant drawback of such alloys is that their dimensions change during discharge and the negative electrode material is disintegrated. As a result of the increase in the specific surface area of the negative electrode material, the capacity decreases (due to the irreversible reaction between the negative electrode material and the electrolyte) and the sensitivity of the battery to thermal stress increases. In extreme cases, the battery will be severely damaged by heat, resulting in a safety risk.

  The use of lithium as an electrode material is problematic for safety reasons. More specifically, lithium dendrite forms on the negative electrode material when lithium is deposited during the charging operation. These will cause a short circuit in the battery, resulting in the battery becoming uncontrollable and destroyed.

  EP 692833 describes carbon-containing intercalation compounds, which, like carbon, contain metals or metalloids that form alloys with lithium, in particular silicon. This compound is produced, for example, by pyrolysis of a polymer containing metal or metalloid and hydrocarbyl groups so that a silicon-containing encapsulating compound is obtained by pyrolysis of polysiloxane. Examples include cases where a silicon-containing encapsulating compound is obtained. The pyrolysis requires harsh conditions, where the primary polymer first decomposes and then carbon and metalloid and / or metalloid oxide regions are formed. Production of such materials generally results in poor reproducibility. Even if it is possible to control the region structure by high energy input, it is considered to be difficult.

EP692833 WO 2010/112580 WO 2010/112581

“Nano Lett. 9 (2009)” by I. Honma et al. Describes nanoporous materials formed from nanoparticles of SnO ₂ embedded between expanded graphite sheets. These materials are suitable for the negative electrode material of a lithium ion storage battery. They are produced by mixing SnO ₂ nanoparticles in ethylene glycol and exfoliated graphite sheets. The exfoliated graphite sheet is itself oxidized and produced by reducing the exfoliated graphite. This method is relatively inconvenient and expensive. Furthermore, this method has low reproducibility.

  In WO 2010/112580, carbon phases C and M are metals or semimetals, for example, boron, silicon, titanium or tin, x is a number from 0 to k / 2, and k is a metal or semimetal. An active material containing at least one MOx phase, showing the maximum vacancy of the metal, is described. According to WO 2010/112580, the active material is produced in two stages, the first stage comprising the production of a nanocomposite material from a semi-metal oxide phase and an organic polymer layer by so-called twin polymerization and the thus produced nano It consists of the second stage, which is carbonization of the composite material. This method is very good in most cases, but in the case of tin it is difficult to obtain a monomer. Although polymerized if difficult, the resulting polymer composite and tin-carbon composite do not exhibit sufficient electrochemical properties.

  WO 2010/112581 describes a method for producing a nanocomposite material in which monomers containing metals or metalloids are copolymerized. Proposed monomers include tin-containing monomers in which tin is present in a tetravalent oxidation state. Production of these monomers is difficult and polymerization is problematic, especially when producing relatively large quantities.

  In general, it can be said that negative electrode materials based on carbon or lithium alloys and known from the prior art are not sufficient in terms of specific capacity, charge / discharge movement and / or cycle stability. For example, the capacity may decrease after several charge / discharge cycles and / or the resistance may increase or increase. Composite materials that have a semi-metallic or metallic particulate phase and one or more carbon phases and have recently been proposed to solve these problems only partially solve these problems. In the case of materials containing at least tin, the quality of such composites cannot be achieved in a reproducible manner. Furthermore, its production is generally very complex and cannot be economically used.

  However, it is an object of the present invention to provide a method for producing a tin-containing polymer composite, which is low in complexity and good reproducibility that can be further processed in a tin-carbon composite. The quality of the product is to provide these materials. The tin-carbon composite material thus produced is suitable for a negative electrode material of a lithium ion battery, in particular, a lithium ion secondary battery, and improves the above-mentioned drawbacks. Have more than one.

-Large specific capacity-Excellent cycle stability-Less self-discharge-Excellent mechanical stability

  The above object of the present invention is surprisingly obtained by the method described in detail below, that is, the production of a tin oxide-containing polymer composite material composed of at least one inorganic tin oxide phase and an organic polymer layer, and this method. It has been found to be achieved with tin oxide-containing polymer composites.

The present invention therefore comprises: a) at least one inorganic tin oxide phase, and b) an organic polymer phase,
A method for producing a tin oxide-containing polymer composite material comprising the polymerization of at least one monomer of formula I.

R ¹ —X—Sn—Y—R ² (I)
(Where
R ¹ is an Ar—C (R ^a , R ^b ) group (wherein Ar is selected from halogen, OH, CN, C ₁ -C ₆ -alkyl, C ₁ -C ₆ -alkoxy and phenyl 1 or 2 An aromatic or heteroaromatic ring optionally having one substituent, R ^a and R ^b are each independently hydrogen or methyl, or both are an oxygen atom or a methylidene group (═CH ₂ );
R ² _is, C 1 _{-C 10} - alkyl or _C 3 -C ₈ - cycloalkyl, or either has one of the definitions ^{R 1,} or ^{R 1} and ^{R 2} are both formula A Base of

（式中、Ａは二重結合と一体となった芳香族又はヘテロ芳香族環であり、ｍは０、１、又は２であり、Ｒ基は、同一でも異なっていてもよく、ハロゲン、ＣＮ、Ｃ_１−Ｃ_６−アルキル、Ｃ_１−Ｃ_６−アルコキシ及びフェニルから選択され、Ｒ^１とＲ^２はそれぞれ上記で定義されている通りである。）であり、
ＸはＯ、Ｓ又はＮＨであり、
ＹはＯ、Ｓ又はＮＨである。）

Wherein A is an aromatic or heteroaromatic ring united with a double bond, m is 0, 1, or 2, and the R groups may be the same or different, and may be halogen, CN , C ₁ -C ₆ -alkyl, C ₁ -C ₆ -alkoxy and phenyl, each of R ¹ and R ² is as defined above)
X is O, S or NH;
Y is O, S or NH. )

  The monomers of formula I are novel and therefore form part of the present invention. Compared to the known tin (IV) compounds, they are easy to produce and they can also be produced on an industrial scale. Furthermore, they are more stable than the corresponding tin (IV) compounds and are less problematic for their use under polymerization.

The present invention also provides a tin oxide-containing polymer composite material comprising a) at least one inorganic tin oxide phase and b) an organic polymer phase obtained by the method according to the present invention.

  The tin oxide-containing polymer composite of the present invention can be transformed into a tin-carbon composite by a simple method. It is due to carbonization of the organic polymer phase of the tin oxide-containing polymer composite obtained according to the invention in a manner known per se.

The present invention also relates to a tin-containing phase comprising at least one inorganic tin-containing phase in which tin is present in an oxidation state of 0 or +2 or a mixed state thereof, and a carbon phase in which carbon is present in elemental form. A method for producing a carbon composite material,
i. In the present invention, provision of a tin oxide-containing polymer composite material by the method described in detail below; Carbonizing the organic polymer phase of the tin oxide-containing polymer composite material obtained in step i,
Is included.

  Due to its configuration and the unique arrangement of the carbon phase C and tin-containing phase resulting from its manufacture, tin-carbon composites are particularly suitable as active materials for negative electrodes in lithium ion batteries, in particular lithium ion secondary batteries or batteries. Yes. More specifically, when used in a negative electrode of a lithium ion battery, particularly a lithium ion secondary battery, the tin-carbon composite material of the present invention is important for obtaining a large capacity and good cycle stability, And the low resistance in a battery is securable. Moreover, because of the co-continuous phase arrangement, the tin-carbon composite of the present invention has high mechanical stability, is produced in a simple manner and with good reproducibility.

  Accordingly, the present invention also provides a method for using a tin-carbon composite material in a negative electrode of a lithium ion battery, particularly a lithium ion secondary battery, and a lithium ion battery, particularly a lithium ion secondary battery, containing the inventive tin-carbon composite material. A lithium ion battery, particularly a lithium ion secondary battery, having at least one of the negative electrode and the negative electrode containing the tin-carbon composite material of the invention is provided.

  Preferred embodiments of the process described in the present invention and the tin oxide-containing polymer composite and the resulting tin-carbon composite are described in detail herein and in the claims.

In the present invention, the tin oxide-containing polymer composite material means the following materials. The material is basically composed of a tin oxide phase and an organic polymer phase which are generally at least about 90% by weight, in particular at least about 95% by weight, and these phases are mixed and distributed with each other. Yes. The tin oxide phase is generally composed essentially of tin oxide or hydrated tin oxide, ie generally at least on the order of 90 percent by weight, in particular on the order of 95 percent by weight. The organic polymer phase is formed by 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, which mainly contains poly (het) aryl formaldehyde condensates or polyaryl carbonates or mixtures thereof.

In the present invention, the term “tin oxide” refers to stoichiometric SnO (eg, α-SnO 2 and β-SnO, Sn ₂ O ₃ and SnO ₂ (eg, octagonal SnO ₂ and hexagonal SnO ₂ )). ) Pure tin oxide and divalent and tetravalent tin hydroxides such as Sn (OH) ₂ and stannic acid H ₂ Sn (OH) ₆ .

  In the present invention, the carbon-tin composite material is the following material. The material is basically constituted by a tin-containing phase and elemental carbon, generally on the order of at least 90 percent by weight, in particular at least 95 percent by weight, while the tin-containing phase and on the other hand carbon They are distributed in a mixed state. The carbon phase is formed of elemental carbon, and the carbon may have a structural unit of graphite.

The terms “alkyl”, “alkoxy”, “cycloalkyl” and “hydroxyalkyl” as well as “aromatic ring” and “heteroaromatic ring” are generic and collective including the substituents normally meant by this term. It should be understood as a general term. In the present invention, the suffix C _n -C _m indicates the number of carbon atoms that the substituent represented by this collective term may have.

  Thus, alkyl is a saturated linear or branched aliphatic hydrocarbon group generally having 1 to 10, often 1 to 6, especially 1 to 4 carbon atoms. Examples of alkyl are methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-butyl, 2-methylpropyl, 1,1-dimethylethyl (= tertbutyl), n-pentyl, 2-pentyl, 2-methylbutyl. N-hexyl, 2-hexyl, n-heptyl, 2-heptyl, n-octyl, 2-octyl, 2-ethylhexyl, n-nonyl, n-decyl, 1-methylnonyl and 2-propylheptyl.

  Thus, alkoxy is linked via an oxygen atom and is typically a saturated linear or branched aliphatic carbonization having 1 to 10, often 1 to 6 and especially 1 to 4 carbon atoms. It is a hydrogen group. Examples of alkoxy are methoxy, ethoxy, n-proxy, isoproxy, n-butoxy, 2-butoxy, 2-methylproxy, n-hexyloxy, 2-hexyloxy, n-heptyloxy, 2-heptyloxy, n-octyloxy, 2 -Octyloxy, 2-ethylhexyloxy, n-nonyloxy, n-decyloxy, 1-methylnonyloxy and 2-propylheptyloxy.

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

  Thus, cycloalkyl is generally a saturated alicyclic hydrocarbon having from 3 to 10, often from 3 to 8, and especially from 3 to 6, carbon atoms, optionally substituted by 1 to 4 methyl groups. It is a group. Examples of cycloalkyl are cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, 1-methylcyclopropyl, 2-methylcyclopropyl, 1-, 2- or 3-methylcyclopentyl, 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 present invention, an aromatic group is understood as meaning a carbocyclic aromatic hydrocarbon group such as phenyl or naphthyl.

  In the present invention, the heteroaromatic group generally has 5 or 6 ring members, and one of the ring members is a heteroatom selected from nitrogen, oxygen and sulfur, and is 1 or 2 or more The ring member of is optionally a nitrogen atom, and the remaining ring members represent a heterocyclic aromatic group that is carbon. Examples of heteroaromatic groups are furyl, thienyl, pyrrolyl, pyrazolyl, imidazolyl, oxazolyl, isozazolyl, pyridyl and thiazolyl.

  In the present invention, an integrated aromatic group or ring means a carbocyclic aromatic divalent hydrocarbylene group such as o-phenylene (benzo) or 1,2-naphthylene (naphtho). is there.

In the process according to the invention, the tin-containing monomer of formula I is polymerized in the Ar-C (R ^a , R ^b ) group to form an organic polymer phase, and the XSnY unit is polymerized to form a tin oxide phase. Polymerized under reaction conditions. Such a polymerization reaction is called twin polymerization and is known, for example, from WO2010 / 112580 and WO2010 / 112581. Unlike the method described in the present invention, WO2010 / 112580 and WO2010 / 112581 propose their monomers exclusively in the oxidation state of tin +4.

  In the process according to the invention, preference is given to using those monomers of the formula I in which at least one of the variables X and Y and in particular both variables X and Y are oxygen.

In the process according to the invention, preference is given to using those monomers of the formula I in which Ar a -C (R ^a , R ^b ) units or R ^a , R ^b in the group of formula A are each hydrogen. is there.

In the process according to the invention, preference is given to those of the formula I in which R ¹ and R ² are identical or different and are each a radical of the formula Ar—C (R ^a , R ^b ). The use of monomers. Preferred in the formula Ar—C (R ^a , R ^b ) is that those groups of the formula where Ra and Rb are each hydrogen. When R ¹ and R ² are each an Ar—C (R ^a , R ^b ) group, Ar is phenyl or furyl unsubstituted or halogen, OH, CN, C ₁ -C ₆ -alkyl, C ₁ -C 6 _- alkoxy, C 1 _-C 6 _- be an hydroxyalkyl and one or two selected from phenyl and furyl and substituted aromatic or heteroaromatic group selected from phenyl desirable. More specifically, Ar is phenyl or furyl, and phenyl and furyl are each unsubstituted or C ₁ -C ₆ -alkyl, C ₁ -C ₆ -hydroxyalkyl and C ₁ -C ₆ -alkoxy. And in particular optionally having one or two substituents selected from hydroxymethyl, methyl and methoxy. Preferred embodiments, Ar is or unsubstituted or substituted C ₁ -C 6 _- alkyl and C ₁ -C 6 _- alkoxy and, in particular, in particular having one or two substituents selected from methyl and methoxy Is phenyl. Particularly preferred examples of the Ar group are methoxyphenyl or 2,4-dimethoxyphenyl. R ¹ and R ² are in particular 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 are both groups of formula A, especially groups of formula Aa, as defined above.

（式中、＃、ｍ、Ｒ、Ｒ^ａ及びＲ^ｂはそれぞれ上記で定義された通りである。）式Ａ及びＡａにおいて、変数ｍは特に０である。ｍが１又は２であるとき、Ｒは特にヒドロキシメチル、メチル又はメトキシメチルである。式Ａ及びＡａにおいて、Ｒ^ａ及びＲ^ｂは特にそれぞれ水素である。

(Wherein #, m, R, R ^a and R ^b are each as defined above.) In formulas A and Aa, the variable m is especially 0. When m is 1 or 2, R is in particular hydroxymethyl, methyl or methoxymethyl. In the formulas A and Aa, R ^a and R ^b are in particular each hydrogen.

The monomer of the formula I is produced in the same manner as known methods for producing organotin compounds. In general, a monomer or compound of formula I wherein R ¹ is an Ar—C (R ^a , R ^b ) group is a suitable tin (II) compound (eg, a tin (II) halide such as tin (II) chloride). Or, for example, tin (II) alkoxide such as tin (II) methoxide (Sn (OCH ₃ ) ₂ ) and Ar—C (R ^a , R ^b ) —XH or the formula Ar—C (R ^a , R ^b ) -XH or a mixture of different compounds of Ar-C (R ^a , R ^b ) -YH (Ar, X, Y, R ^a and R ^b are as defined above) reacted Is done. When tin (II) halide is used, the reaction is generally performed in the presence of a tertiary amine as a base. Generally used in excess with respect to the desired stoichiometry of the formula ^{Ar-C (R a, R} b) -XH or ^{Ar-C (R a, R} b) compounds of -YH its reaction .

In a similar manner, a monomer or compound of formula I wherein R ¹ is an Ar—C (R ^a , R ^b ) group is converted to a suitable tin (II) compound (eg, a tin (II) such as tin (II) chloride). ) Halide or a tin (II) alkoxide such as tin (II) methoxide (Sn (OCH ₃ ) ₂ )) and a compound of formula AXHYH where m, A, X, Y, R, R ^a And R ^b are each as defined above).

  When tin (II) halide is used, the reaction is generally carried out in the presence of a tertiary amine as a base. In general, compound AXHYH is used in excess relative to the desired stoichiometry of the reaction.

In order to produce the polymer composite, the monomer of formula I (described below as monomer I) can be polymerized alone (homopolymerization). It is also possible to copolymerize mixtures of different monomers I. Alternatively, one or more monomers I having substituents known to be suitable for polymerization involving R ¹ or R ² groups can be polymerized. These include in particular aliphatic, aromatic or heteroaromatic aldehydes such as benzaldehyde, furfural, formaldehyde or acetaldehyde. Preference is given to using formaldehyde in the gaseous state or in the form of non-aqueous oligomers or polymers (for example in the form of trioxane or paraformaldehyde). Similarly, the monomer I of the present invention and other monomers can be copolymerized, and other monomers can be copolymerized under twin polymerization conditions, for example, in WO2010 / 112580 and WO2010 / 112581. It contains an oxide-forming metalloid as described. And other polymers may have a metal or a semimetal in addition to tin. These are in particular the monomers of the general formula I described in WO 2010/112580 and WO 2010/112581, the following formula X,

式中、
Ｍは金属又は半金属であり、望ましくは、周期表の主族３又は４、又は遷移族４又は５の金属又は半金属、特にＢ、Ａｌ、Ｓｉ、 Ｔｉ、Ｚｒ、Ｈｆ、Ｇｅ、Ｓｎ、Ｐｂ、Ｖ、Ａｓ、Ｓｂ又はＢｉ、さらに望ましいのはＢ、Ｓｉ、Ｔｉ、Ｚｒ又はＳｎ、さらにより望ましいのはＳｉ 又は Ｔｉであり、特にＳｉである。

Where
M is a metal or metalloid, preferably a metal or metalloid of main group 3 or 4 or transition group 4 or 5 of the periodic table, in particular B, Al, Si, Ti, Zr, Hf, Ge, Sn, Pb, V, As, Sb or Bi, more preferably B, Si, Ti, Zr or Sn, and still more preferably Si 2 or Ti, especially Si.

R ^1a and R ^2a may be the same or different, and they are each an Ar—C (R ^a , R ^b ) group, and Ar, R ^a , and R ^b are particularly cited as desirable definitions. Each as defined above in connection with Formula I, or the R ^1a X and R ^2a Y groups are both groups of Formula A ′.

（式中、Ａ、Ｒ、ｍ、Ｒ^ａ、Ｒ^ｂはそれぞれ式Ｉと関連して上記で定義した通りであり、特に、その定義は望ましいものとして引用されている。）

(Wherein A, R, m, R ^a and R ^b are each as defined above in connection with Formula I, and in particular, the definitions are cited as desirable.)

  X is O, S or NH, in particular O.

  Y is O, S or NH, especially O.

  G and Q may be the same or different and they are O, S, NH or chemical bonds, respectively, and in particular oxygen or chemical bonds.

R ^{1', R 2'is} identical or different and have good, they each _C 1 -C ₆ - _alkyl, C 3 -C ₆ - cycloalkyl, aryl or ^Ar '-C ^{(R a',} R ^b') group (wherein, Ar ^'is as defined for ^{Ar, R a',} R ^b'are each ^R a, as defined in ^{R b), R 1', R} 2 ^{'particularly} are each hydrogen, ^or, R 1', ^{R 2'is} a group of the formula A'defined above together with G and Q. )

  And in particular monomers of the general formula II, IIa, III, IIIa, IV, V, Va, VI or VIa described in WO 2010/112580 and WO 2010/112581.

  In a more preferred embodiment, the proportion of monomers other than the monomer of formula I (for example the monomer of formula X or the aldehyde mentioned above) does not exceed 20% by weight, in particular 10% by weight. This is based on the total weight of the monomer to be polymerized, i.e. the monomer of formula I forms at least 80% by weight and in particular 90% by weight of the total weight of the monomer to be polymerized. In other embodiments of the present invention, the proportion of the monomer of formula I in the total weight of the monomers to be polymerized is 20 to 80% by weight, in particular 30 to 70% by weight, The proportion of the monomer of formula X or the aldehyde mentioned above is in the range from 20 to 80% by weight, in particular in the range from 30 to 70% by weight, based on the total weight of the monomers to be polymerized.

  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 more preferred embodiment of the process according to the invention, the monomers are polymerized in an organic solvent or mixed solvent, in particular in an organic aprotic or mixed solvent. Preference is given to aprotic solvents in which the polymer composite formed is insoluble (solubility <I g / l at 25 ° C.). As a result, particularly small particles of the polymer composite are formed under polymerization conditions. In practice, however, polymerization is also carried out.

  The use of aprotic solvents in which the polymer composite formed by polymerization is insoluble is in principle assumed to promote particle formation. If the polymerization is carried out in the presence of particulate inorganic material, the formation of the particles will probably be controlled by the presence of the particulate inorganic material. This will then prevent the formation of a coarse polymer composite.

  Desirably, the aprotic solvent is selected such that monomer I can be at least partially dissolved. Under the polymerization conditions, the solubility of monomer I in the solvent is at least 50 g / l, in particular at least 100 g / l. In general, the organic solvent is selected such that the solubility of the monomer at 20 ° C. is 50 g / l, in particular at least 100 g / l. More specifically, the solvent is selected such that monomer I is substantially or completely soluble therein. That is, the ratio of solvent to monomer I is selected such that, under the polymerization conditions, at least 80%, in particular at least 90% of monomer I or all of monomer I is present dissolved.

  “Aprotic” has one or more protons attached to a heteroatom such as O, S or N and is essentially free of solvents that are more or less acidic in this way. Means the solvent used for the polymerization. Therefore, the proportion of the protic solvent in the solvent or mixed solvent used for the polymerization is 10% by volume or less, particularly 1% by volume or less and 0.1% by volume or less based on the total volume of the organic solvent. The polymerization of monomer I is desirably carried out in the substantial absence of water. That is, the concentration of water at the start of polymerization is 500 ppm or less based on the amount of solvent used.

  The solvent may be inorganic or organic or a mixture of inorganic and organic solvents. An organic solvent is desirable.

  Suitable aprotic organic solvents are, for example, halogenated hydrocarbons such as dichloromethane, chloroform, dichloroethane, trichloroethane, 1,2-dichloroethane, 1,1,1-trichloroethane, 1-chlorobutane, chlorobenzene, dichlorobenzene, fluorobenzene and the like. And pure hydrocarbons that are aliphatic, cycloaliphatic or aromatic, and mixtures of these hydrocarbons and halogenated hydrocarbons. Examples of pure hydrocarbons are generally acyclic aliphatic hydrocarbons having 2-8, preferably 3-8 carbon atoms, in particular ethane, iso- and n-propane, n-butane, and isomers thereof. , N-pentane and its isomers, n-hexane and its isomers, n-heptane and its isomers, and alkanes such as n-octane and its isomers, cyclopentane having 5 to 8 carbon atoms, Alicyclic hydrocarbons such as methylcyclopentane, cyclohexane, methylcyclohexane, and cycloalkanes such as cycloheptane, and benzene, toluene, xylene, mesitylene, ethylbenzene, cumene (2-propylbenzene), and isocumene (1-propylbenzene) And aromatic hydrocarbons such as tert-butylbenzene.

  Preferably, it is a mixture of the above-mentioned hydrocarbons and halogenated hydrocarbons, such as halogens such as chloromethane, dichloromethane, trichloromethane, chloroethane, 1,2-dichloroethane, 1,1,1-trichloroethane, and 1-chlorobutane. And halogenated aromatic hydrocarbons such as chlorobenzene, 1,2-dichlorobenzene, and fluorobenzene.

  Examples of inorganic protic solvents are in particular supercritical carbon dioxide, carbon oxysulfide, carbon disulfide, nitrogen dioxide, thionyl chloride, sulfuryl chloride, and liquid sulfur dioxide, and the latter acting as a polymerization initiator. Three solvents.

Monomer I is usually polymerized in the presence of a polymerization initiator or catalyst. The polymerization initiator or catalyst is selected to initiate the cationic polymerization of monomer I (ie, monomer units XR ¹ and YR ² ) and the formation of a tin oxide phase, or to function as a catalyst. Therefore, in the course of the polymerization of the monomer I, on the one hand, the monomer units XR ¹ and YR ² are polymerized, while at the same time a tin oxide phase is formed.

The term “simultaneously” 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. In other words, “simultaneously” means that these processes are kinetically coupled and caused by being in a cationic polymerization state.

Suitable polymerization initiators or catalysts are in principle all substituents known to catalyze cationic polymerization. These include protic acids (Bronsted acids) and aprotic Lewis acids. Desirable proton catalysts are Bronsted acids, such as organic carboxylic acids such as trifluoroacetic acid, oxalic acid or lactic acid, and especially organic sulfonic acids such as methanesulfonic acid, trifluoromethanesulfonic acid or toluenesulfonic acid. Also suitable are inorganic Bronsted acids such as HCl, H ₂ SO ₄ or HClO ₄ . The Lewis acid used may be, for example, BF ₃ , BCl ₃ , SnCl ₄ , TiCl ₄ or AlCl ₃ . It is also possible to use a Lewis acid which is bound in a complex manner or dissolved in an ionic liquid. The polymerization initiator or catalyst is usually used in an amount of 0.1 to 10% by mass, preferably 0.5 to 5% by mass, based on the monomer M.

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

  The process according to the invention is particularly suitable for industrial production of tin oxide-containing polymer composites in continuous mode and / or batch mode. In batch mode this means a batch size of at least 10 kg, often at least 100 kg, in particular at least 1000 kg or at least 5000 kg. In continuous mode, this is generally at least 100 kg / day, often at least 1000 kg / day, in particular at least 10 t / day or at least 100 t / day.

The tin oxide-containing polymer composite material obtained by the method according to the present invention is basically composed of a tin oxide phase and an organic polymer phase, ie generally at least about 90% by weight, in particular at least about 95% by weight. Has been. In general, the tin oxide phase is basically composed of tin oxide or tin oxide hydrate, ie generally at least about 90% by weight, in particular at least about 95% by weight. Here, the tin oxide is preferably present in the state of tin, which is at least about 80% and in particular about 90% in the +2 oxidation state. The organic polymer phase is formed by a carbon-based polymer other than elemental carbon. The composition of the organic polymer phase is defined by the Ar—C (R ^a , R ^b ) group and they are generally poly (het) aryl formaldehyde condensates or polyaryl carbonates or mixtures thereof.

  Another result of the method described in the present invention is that the tin oxide phase and the organic polymer phase exist in a co-continuous structure over a wide range, since each phase is essentially a phase that is arbitrarily continuous. This means that no isolated phase region surrounded by the region is formed. Instead, the two phases form a spatially separated continuous phase region that penetrates each other as can be seen by examining the material with a transmission electron microscope. Regarding the terms “continuous phase region”, “discontinuous phase region” and “co-continuous phase region”, J. et al. Work et al., “Definitions of Terms Related to Polymer Blends, Composites and Multiphase Polymeric Materials, (IUPAC Recommendations 2004), pp. 7-200, (Pure App. 4). Yes. Thus, a co-continuous structure of a binary mixture is understood to mean a phase separation structure of two phases or components in which any phase region is defined within one particular phase region. A continuous path through may be drawn at every phase boundary without intersecting any phase region boundary.

  In the polymer composite of the invention, the region in which the organic polymer phase and the tin oxide phase essentially form a co-continuous phase region is at least 50% by volume of the polymer composite, often at least 80% by volume and in particular at least 90% by volume. %.

In the polymer composite material of the present invention, the distance between the interfaces of adjacent phases or the distance between adjacent similar phase regions is small, on average 100 nm or less, particularly 20 nm or less, particularly 10 nm or less. The distance between adjacent similar phases, for example, the distance between two regions of the tin oxide phase is separated from each other by the region of the organic polymer phase, or the distance between two regions of the organic polymer phase is They are separated from each other by the region of the tin oxide phase. Average distance between regions of adjacent similar phases, the scattering vector q (measured in transmission at 20 ° C., monochromatic Cu K _a line, 2D detector (image edition), slit collimation) small-angle X-ray scattering via (SAXS).

  The size of the phase region and hence the distance between adjacent phase interfaces and the phase structure can also be measured by transmission electron microscopy, in particular HAADF-STEM technology (HAADF-STEM = high angle scattering annular dark field scanning transmission microscopy). Can be measured. In this imaging technique, relatively heavy elements (eg, Sn compared to C) appear brighter than light elements. Preparation artifacts are also observed as the dense regions of the preparation appear brighter than the less dense regions.

  As already mentioned above, the present invention also relates to the production of tin-carbon composites from at least one inorganic tin-containing phase. In at least one inorganic tin-containing phase, tin is present in the tin state in the +2 or 0 oxidation state, in particular in the elemental state or in the tin (II) oxide state or in the tin (II) oxide hydration Or a mixed state thereof. For this purpose, in a first step i, a tin oxide-containing polymer composite material is produced by the method described above. This tin oxide-containing polymer composite material is carbonized in the second step. The organic polymer phase here turns into a phase consisting mainly of elemental carbon. The phase structure is basically maintained.

  For this purpose, the polymer composite material obtained in step i is generally at least up to 400 ° C., preferably at least 500 ° C., in particular at least 700 ° C., for example 400, substantially excluding oxygen. It is heated to a range of from ℃ to 1200 ℃. The “substantially oxygen-excluded state” means that the oxygen partial pressure in the reaction range in which carbonization is carried out is small, desirably not exceeding 20 mbar, in particular not exceeding 10 mbar.

In one embodiment of the invention, carbonization is performed under an inert gas atmosphere such as nitrogen or argon. The inert gas atmosphere preferably contains 1% by volume or less, particularly 0.1% by volume or less of oxygen. In the other embodiment of the present invention, carbonization is carried out in the presence of a so-called reducing gas. The reducing gas contains hydrocarbon gas such as methane, ethane or propane, or ammonia (NH ₃ ), as well as hydrogen (H ₂ ). The reducing gas can be used as such or as a mixture with an inert gas such as nitrogen or argon.

  Desirably, the particulate composite material is used for carbonization in a dry state, ie, substantially free of solvent and in a powdered state. “No solvent” means here and below a composite material containing 1% by weight or less, in particular 0.1% by weight or less of solvent.

  Optionally, carbonization is performed in the presence of an oxidant that promotes the formation of graphite such as transition metal halides such as iron (III) chloride. This achieves the following effects. The carbon in the carbon material of the present invention is mainly in the state of a graphite or graphene unit, that is, in the state of a polycyclic structural unit in which each carbon atom is further covalently bonded to three carbon atoms. That is. The amount of such oxidizing agent is generally 1-20% by weight, based on the polymer composite material. When such an oxidant is used in carbonization, the procedure generally mixes the polymer composite and oxidant with each other and carbonizes the mixture in a powder that is substantially free of solvent. The oxidant is optionally removed after carbonization. The method is based on, for example, a method in which the oxidizing agent and its reaction product are soluble, a method of washing out the oxidizing agent using a solvent or a mixed solvent, or a method of vaporizing.

  In this way, in step ii, a tin-carbon composite material composed of a carbon phase and at least one tin phase is desirably obtained. The carbon-tin composite material of the present invention is generally composed of at least about 90% by mass, particularly at least about 95% by mass of at least one tin phase and elemental carbon. The tin-containing phase is generally composed essentially of, that is, generally at least about 90% by weight, in particular at least about 95% by weight of tin or tin oxide or tin oxide hydrate or mixtures thereof.

  According to the present invention, the tin-carbon composite material includes a carbon phase (hereinafter also referred to as C phase). In the C phase, the carbon exists essentially in the elemental state, which means that the proportion of non-carbon atoms in the carbon phase, for example N, O, S, P and / or H, of the carbon in the C phase It means 10% by mass or less, particularly 5% by mass or less, based on the total mass. The contents other than carbon in the C phase can be determined by X-ray photoelectron spectroscopy. In addition to carbon, phase C may contain, in particular, small amounts of nitrogen, oxygen, sulfur and / or hydrogen as a result of preparation. The molar ratio of hydrogen to carbon generally does not exceed values of 1: 3, in particular 1: 5 and in particular 1:10. The value may be 0 or substantially 0, for example 0.1 or less. In the C phase, carbon is probably present mainly in the form of amorphous or graphite. The presence of amorphous or graphitic carbon can be determined by ESCA studies that reference a characteristic binding energy (284.5 eV) and a characteristic asymmetric signal shape. Carbon in the form of graphite is understood to mean that the carbon is at least partly arranged in a hexagonal layer typical of graphite. There, the layer may also be curved or peeled off.

  In addition to the C phase, the tin-carbon composite material of the present invention includes at least one tin phase (Sn phase), and tin in the tin phase is in an oxidation state of +2 or 0 or a mixed state thereof. The tin phase desirably consists essentially of tin (II) oxide hydrates or mixtures thereof, such as elemental tin or tin (II) oxide or tin (II) hydroxide. In the tin phase, the proportion of atoms other than tin and oxygen atoms (eg, other metals or metalloids and nitrogen, oxygen, phosphorus, and / or hydrogen) is desirably based on the total mass of carbon in the tin phase. 10% by mass or less, particularly 5% by mass or less. In the tin phase, a +2 oxidation state tin or an elemental tin state, that is, 0 oxidation state tin or a mixed state thereof may be used. In a preferred embodiment, tin mainly means that at least 50%, in particular at least 80% or at least 90% of the tin atoms of the tin phase are in the oxidation state of 0 and in particular in the state of elemental tin. , 0 in the oxidation state.

  In general, the C phase and the tin phase form an essentially random arrangement of co-continuous phase regions, the average distance between two adjacent regions of the tin phase, or two adjacent ones of the C phase. The average distance between the regions is 100 nm or less, in particular 20 nm or less, in particular 10 nm or less and, for example, between 0.5 and 100 nm, in particular between 0.7 and 20 nm and in particular between 1 and 10 nm. For the determination of the average distance between two adjacent regions of tin phase or C phase, the above explanation for the polymer composite obtained in step i applies in the same way.

  In a further embodiment, the tin phase is in the tin region embedded in the continuous carbon phase C as a matrix, essentially in an isolated manner. In this embodiment, often 50% by volume or more of the tin region is between 1 nm and 20 μm, in particular between 1 nm and 1 μm. In particular, in these tin-carbon composites of this embodiment, the tin content is 5 to 90% by weight, in particular 10 to 75% by weight, more particularly based on the total weight of the tin-carbon composite. 15 to 55 mass%, preferably 10 to 75 mass%.

  The process according to the invention is particularly suitable for the industrial production of tin-carbon composite materials in continuous mode and / or batch mode. In batch mode, this means a batch size of at least 10 kg, in particular at least 100 kg, in particular at least 1000 kg or at least 5000 kg. In continuous mode, this generally means at least 100 kg / day, in particular at least 1000 kg / day, in particular at least 10 t / day or at least 100 t / day.

  It should be noted that the tin-carbon composite material of the present invention, as already mentioned, has particularly excellent properties when used in electrochemical cells, particularly lithium ion batteries. Its characteristics are particularly advantageous in that high specific capacity, good cycle stability, self-discharge and lithium dendrite tend not to form, and high current density is realized for charge / discharge operations. It should be noted that

  In the present invention, the electrochemical cell or accumulator is any type of accumulator, capacitor and accumulator (secondary cell) (especially an alkali metal cell or accumulator such as lithium, lithium ion, lithium-sulfur and alkaline earth metal accumulators. In particular, high-energy or high-performance systems and electrolytic capacitors and double-layer capacitors known under the names Supercaps, Goldcaps, BoostCaps or Ultracaps.

  Accordingly, the present invention also provides a method of using a tin-carbon composite material for the manufacture of an electrochemical cell and, in particular, a method of using a negative electrode for a lithium ion battery, particularly a lithium ion secondary battery. Therefore, the present invention also relates to a negative electrode for a lithium ion battery, in particular, a lithium ion secondary battery containing the inventive tin-carbon composite material.

  In addition to the tin-carbon composite of the present invention, the negative electrode is generally at least one suitable for consolidation of any further electrically conductive or electrically active component with the tin-carbon composite of the present invention. Contains a binder. In addition, the negative electrode generally has electrical contacts for supplying and removing charge. The amount of the tin-carbon composite material of the present invention is generally at least 40% by weight, often at least 50% by weight and in particular at least 60% by weight, based on the total weight of the negative electrode material minus any current collector rings and electrical contacts. %.

  Further suitable electrically conductive or electrically active components are known from the relevant research papers. (E.g., "M.E. Spahr, Carbon Conductive Additives for Lithium-Ion Batteries, in M. Yosio et al. (Eds.) Lithium Ion Batteries, Spr. (See the literature cited therein) More useful, conductive or electrically active components in the negative electrode of the present invention include carbon black, graphite, carbon fiber, carbon nanofiber, carbon nanotube, or conductive polymer. Is mentioned. Generally, about 2.5-40% by weight of conductive material is used in the negative electrode with 50-97.5% by weight, often 60-95% by weight of the active material of the present invention. The mass% numbers are based on the total mass of the negative electrode material minus any current collector rings and electrical contacts.

  Useful binders for the manufacture of negative electrodes for use in the aforementioned tin-carbon composite materials and more electrically active materials are in principle the relevant research papers (eg “A. Nagai, Applications of PVdF-Related Materials”). for Lithium-Ion Batteries, in M. Yoshio et al. (eds.) Lithium Ion Batteries, Springer Science + Business Media, New Media 2009 and References, pp. 155-16. “H. Yamamoto and H. Mori, SBR Binder (for negative electrode) and ACM Binder (for position) eve electrode), ibid. ”(see pages 163 to 180)), including all prior art binders suitable for negative electrode materials. Useful binders include in particular the following polymeric materials:

  Polyethylene oxide (PEO), cellulose, carboxymethyl cellulose (CMC), polyethylene, polypropylene, polytetrafluoroethylene, polyacrylonitrile-methyl methacrylate, polytetrafluoroethylene, styrene-butadiene copolymer, tetrafluoroethylene-hexafluoroethylene copolymer, polyfluorination Vinylidene (PBdF), polyvinylidene fluoride hexafluoropropylene copolymer (PVdF-HFP), tetrafluoroethylene hexafluoroethylene copolymer, tetrafluoroethylene, perfluoroalkyl-vinyl ether copolymer, vinylidene fluoride-hexafluoropropylene copolymer, ethylene-tetrafluoroethylene Copolymer, vinylidene fluoride-chlorotri Fluoroethylene copolymer, ethylene-chlorofluoroethylene copolymer, ethylene-acrylic acid copolymer (with or without sodium ion), ethylene-methacrylic acid copolymer (with or without sodium ion), ethylene-methacrylic acid Ester copolymers (with or without sodium ions), polyimides and polyisobutenes.

  The binder is arbitrarily selected in consideration of the nature of the solvent used for production. The binder is generally used in an amount of 1 to 10% by weight, based on the entire mixture of negative electrode materials, ie tin-carbon composite material and any further electroactive or conductive material. Desirably 2-8% by weight and especially 3-7% by weight are used.

  The negative electrode is known from the prior art and related research papers shown at the beginning (for example, “R. J. Brodd, M. Yoshio, Production processes for Fabrication of Lithium-Ion Batteries, in M. Yoshio et al.). (See pages 181-194 of Lithium Ion Batteries, Springer Science + Business Media, New York 2009)). For example, the negative electrode optionally uses an organic solvent (eg, N-methylpyrrolidinone or a hydrocarbon solvent), and the active material of the present invention and any other negative electrode material component (conductive component and / or organic binder). ), And optionally subjected to a forming step, or applied to an inert metal foil, such as Cu foil. Then, you may dry as needed. This is performed at a temperature of 80 to 150 ° C., for example. The drying operation is performed under reduced pressure, and is generally performed continuously for 3 to 48 hours. Moreover, the melting or sintering process for shaping | molding can be performed as needed.

  The present invention can also provide a lithium ion battery, in particular, a lithium ion secondary battery having at least one negative electrode containing the tin-carbon composite material of the present invention.

  Such batteries generally have at least one negative electrode of the present invention, a positive electrode suitable for lithium ion batteries, an electrolyte and optionally a separator.

  For suitable cathode materials, suitable electrolytes and suitable separators and possible arrangements, see related prior art, such as the prior art cited at the outset, and appropriate research papers and reference books (eg, “Wakihara et al. . (editor) in 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; J. O. Besenhard: Handbook of Battery Materials. Wiley-VCH, 1998; M. Yoshio et al. (ed.) Lithium Ion Batteries, Springer Science + Business Media, New York 2009; K. E. Afantis, S.A. hacker, R. V. Kumar, R. V. Kumar, R.V. Wiley-VCH, 2010 ".

  Useful positive electrodes include in particular those positive electrodes, the positive electrode material comprising at least one lithium-transition metal oxide (eg lithium-cobalt oxide, lithium-nickel oxide, lithium-cobalt-nickel oxide). Lithium-transition metals such as lithium-manganese oxide (spinel type), lithium-nickel-cobalt-aluminum oxide, lithium-nickel-cobalt-manganese oxide or lithium-vanadium oxide or lithium-iron phosphorous oxide (Phosphorus oxide). Useful positive electrode materials also include sulfur and sulfur-containing composite materials. The sulfur-containing composite material is, for example, a sulfur-carbon composite material as is known for lithium-sulfur batteries.

  The two electrodes, the negative electrode and the positive electrode, are bonded together using a liquid or other solid electrolyte. Useful liquid electrolytes include, in particular, lithium salts and non-aqueous solutions of molten lithium salts (usually having a water content of less than 20 ppm). For example, a suitable aprotic solvent (for example, ethylene carbonate, propylene carbonate, mixtures thereof and the solvents shown below (dimethyl carbonate, diethyl carbonate, dimethoxyethane, methyl propionate, ethyl propionate, butyrate). Loractone, acetonitrile, ethyl acetate, methyl acetate, toluene, and xylene) in combination with one or more solvents), especially in a mixture of ethylene carbonate and diethyl carbonate. Lithium fluorophosphate, lithium perchlorate, lithium hexafluoroarsenate, lithium trifluoride methylsulfonate, lithium bis (trifluoromethylsulfonyl) imide or lithium tetrafluoroborate, especially lithium hexafluorophosphate Alternatively, it is a solution of lithium tetrafluoroborate. The solid electrolyte used may be, for example, an ion conducting polymer.

  The separator impregnated with the liquid electrolyte may be arranged between the electrodes. Examples of separators are glass fiber nonwovens and porous organic polymer films such as porous films of polyethylene, polypropylene, PVdF, etc.

  For example, these may have a prism thin film structure in which a solid thin film electrolyte is disposed between a film constituting a negative electrode and a film constituting a positive electrode. A central positive output conductor is placed between each positive film to form a double-sided cell configuration. In other embodiments, a single-sided cell configuration can be used in which a single positive output conductor is assigned to a single negative / separator / positive element combination. In this configuration, the insulating film is basically disposed between the individual negative electrode / separator / positive output conductor element combinations.

  The following drawings and examples illustrate the invention, but should not be understood as being limited to each of these embodiments.

  The TEM analysis is a HAADF-STEM analysis performed using a Tecnai F20 transmission electron microscope with an ultra-thin layering technique (embedding of material inside a synthetic resin as a matrix) at an operating voltage of 200 kV.

  ESCA studies have been performed using an FEI 5500 LSX-ray photoelectron spectrometer from FEI (Eindhoven, The Netherlands).

  Small-angle X-ray scattering analysis was affected at 20 ° C. during slit collimation using CuK rays monochromatized with a Gobel mirror. The data was corrected for background and sharpened for blurring caused by slit collimation.

  For the IR spectrum, the abbreviations s, m and w represent strong, medium and weak, indicating the relative intensity of the bands.

1. Production of Monomer I Production Example 1: Tin (II) bis (2-methoxyphenylmethoxide) (in monomer I, X = Y = O; R ¹ = R ² = 2-methoxybenzyl)
a) 19.51 g (10.29 mol) of anhydrous tin chloride is dissolved in 250 ml of methanol. On the other hand, 57 ml (41.16 mol) of dry triethylamine is added dropwise at room temperature. A colorless precipitate then forms immediately. After complete addition of triethylamine, the reaction mixture is stirred for an additional 2 hours and the precipitate is filtered. The colorless solid obtained is washed 3 times with 20 ml of methanol and then 3 times with 20 ml of diethyl ether. Then, 17.67 g (97.74 mmol, 95%) of tin (II) methoxide (Sn (OCH ₃ ) ₂ ) is obtained in an amorphous solid state.

IR [cm ⁻¹ ]: 2928 (m) (CH), 2828 (m) (CH), 1594 (s), 1486 (s), 1455 (s), 1362 (m), 1279 (m), 1233 ( s), 1111 (s) (C—O), 1011 (s), 814 (m), 749 (s), 714 (m), 615 (s), 575 (s) (Sn—O), 478 ( m), 432 (m).
EA determined (calculated): C: 48.6% (C: 48.9%), H: 5.0% (H: 4.6%).
^I 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, 1 H).
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) Sn (OCH ₃ ) ₂ was suspended in 50 ml toluene. After adding 4.82 g (34.85 mmol) of 2-methoxybenzyl alcohol, while the suspended material was dissolved, the suspension was heated to distill off the released toluene. After the clear toluene solution concentration reached 15 ml, a colorless solid precipitated. This was washed repeatedly with diethyl ether and dried under high pressure (10 ⁻³ mbar).

This gave 4.73 g (12.04 mmol, 72.5%) of the title compound as a colorless solid. This was identified based on its IR spectrum or ^I H NMR spectrum.

Preparation Example 2: Tin (II) bis manufacture of (2,4-dimethoxyphenyl methoxide) (monomer ^{I, X = Y = O;} R 1 = R 2 = 2,4- dimethoxybenzyl)

2.00 g (11.06 mmol) Sn (OCH ₃ ) ₂ was suspended in 50 ml toluene. After adding 3.91 g (23.25 mmol) of 2,4-dimethoxybenzyl alcohol, while the suspended material was dissolved, the suspension was heated to distill off the released methanol. The resulting clear solution was concentrated until a white solid precipitated. This was washed repeatedly with diethyl ether and dried under high pressure (10 ⁻³ mbar). This gave 3.98 g (8.78 mmol, 79.4%) of the title compound as a colorless 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) (C-O v), 1032 (s), 986 (s), 932 (m), 822 (s), 731 (s), 695 (M), 627 (m), 571 (s) (Sn-O), 517 (m), 455 (s).
EA determined (calculated): C: 47.4% (C: 47.7%), H: 4.6% (H: 4.9%).
^I 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.

Production Example 3: Tin (II) bis ((2-thienyl) dimethylmethoxide) (in monomer I, X = Y = O; R ¹ = R ² = 1- (2-thienyl) -1-methylethyl)

2.00 g (11.06 mmol) Sn (OCH ₃ ) ₂ is suspended in 50 ml 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 hour, and the methanol produced during the reaction was removed under reduced pressure. Removed. The resulting clear solution was concentrated to dryness. By recrystallizing the colorless solid obtained from diethyl ether, 3.24 g (8.07 mmol, 73%) of the title compound can be obtained in the form of a colorless solid.

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

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

  Production Example 5: 6-methoxybenzo [4H-1,3,2-] dioxastannin

  The production is carried out in the same manner as in Production Example 4 except that 2-hydroxy-4-methoxybenzyl alcohol is used instead of 2-hydroxy-5-methoxybenzyl alcohol.

Yield: 1.65 g (6.06 mmol, 73%).
EA determined (calculated): 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) (C-O v), 1032 (s), 957 (s), 832 (m), 789 (m), 735 (m), 488 (s) (Sn -O).

  Production Example 6: 7-methylbenzo [4H-1,3,2-] dioxastannin

  The production is carried out in the same manner as in Production Example 4 except that 2-hydroxy-5-methylbenzyl alcohol is 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 from Preparation Example 1 (Monomer 1) was dissolved in 16 ml of chloroform. While stirring, 10 mol% of methyl trifluoride sulfonic acid was added to the solution as a catalyst, based on monomer 1, and the mixture was heated at 50 ° C. for 5 days. During this process, a solid precipitated. The solid was suction filtered. After repeated washing with diethyl ether and drying under high pressure (10 ⁻³ mbar), the polymer composite was obtained as a colorless solid in a yield of 0.22 g (43%).

Example 2:
In a manner similar to Example 1, 0.52 g of the compound from Preparation Example 1 was polymerized using 10 mol% trifluoroacetic acid as a catalyst. The polymer composite was obtained as a colorless solid in a yield of 0.06 g (12%).

Example 3:
0.94 g (2.09 mol) of the compound from Production Example 2 (Monomer 2) was dissolved in 14 ml of chloroform. While stirring, based on monomer 2, 10 mol% of methyl trifluoride sulfonic acid was added to the solution as a catalyst and the mixture was heated at 50 ° C. for 24 hours. In this process, a solid precipitated. The solid was suction filtered. After repeated washing with diethyl ether and drying under high pressure (10 ⁻³ mbar), the polymer composite was obtained as a colorless solid in a yield of 0.84 g (89%).

Example 4:
In a manner similar to Example 1, 0.6 g of the compound from Preparation 2 was polymerized using 10 mol% trifluoroacetic acid as a catalyst. The polymer composite was obtained as a colorless solid in a yield of 0.19 g (32%).

Example 5:
0.91 g of the compound from Preparation Example 5 was dissolved in 6 ml of dry chloroform and mixed with 10 mol% of trifluoromethanesulfonic acid dissolved in 2 ml of dry chloroform. The reaction mixture was stirred at room temperature for a further 3 days. Thereafter, the purple solid was filtered off 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 (C-O v) (s), 1021 (s), 955 (m), 835 (m), 758 (m), 631 (s), 567 (m), 507 (M), 426 (s) (Sn-O).

Claims (27)

Formula I
R ¹ —X—Sn—Y—R ² (I)
(Where
R ¹ is an Ar—C (R ^a , R ^b ) group (where Ar is selected from halogen, OH, CN, C ₁ -C ₆ -alkyl, C ₁ -C ₆ -alkoxy and phenyl, or 1 An aromatic or heteroaromatic ring optionally having two substituents, wherein R ^a and R ^b are each independently hydrogen or methyl, or both are oxygen atoms or methylidene groups (═CH ₂ ); Yes.)
R ² _is, C 1 _{-C 10} - alkyl or _C 3 -C ₈ - cycloalkyl, or either has one of the definitions ^{R 1,} or, ^{R 1} is of formula A with ^{R 2} Base

(In the formula, A is an aromatic or heteroaromatic ring integrated with a double bond, m is 0, 1 or 2, and the R groups may be the same or different, and may be halogen, CN, C, _1- C ₆ -alkyl, C ₁ -C ₆ -hydroxyalkyl, C ₁ -C ₆ -alkoxy and phenyl, each of R ^a and R ^b is as defined above).
X is O, S or NH;
Y is O, S or NH. )
A compound represented by   2. A compound according to claim 1, wherein X and Y in formula I are each oxygen. The compound according to claim 1 or 2, wherein R ^a and R ^b in the Ar-C (R ^a , R ^b ) unit or the group of formula A are each hydrogen. The compound according to any one of claims 1 to 3, wherein R ¹ and R ² are the same or different and each is an Ar-C (R ^a , R ^b ) group. Ar in the Ar—C (R ^a , R ^b ) unit is an aromatic or heteroaromatic group selected from phenyl and furyl, and the phenyl group and the furyl group are not substituted or halogen, CN, C ₁ -C 6 _- alkyl and C ₁ -C 6 _- a compound according to any one of claims 1 to 4, characterized in that it has one or two substituents selected from alkoxy optionally. ^{Ar-C (R a, R} b) Ar in the unit _is, C 1 -C ₆ - _alkyl, C 1 -C ₆ - hydroxyalkyl and _C 1 -C ₆ - 1 or 2 substituents selected from alkoxy 6. A compound according to claim 5, which is phenyl having The compound according to claim 6, wherein Ar in the Ar—C (R ^a , R ^b ) unit is 2-methoxyphenyl or 2,4-dimethoxyphenyl. R ¹ and R ² compound according to any one of claims 1 to 3, characterized in that a group of formula A. R ¹ and R ² are of formula Aa

(Wherein m, R, R ^a and R ^b are as defined above.)
The compound according to any one of claims 1 to 3, which is a group of 10. The compound according to claim 9, wherein m in formula Aa is 0, 1 or 2, R is selected from hydroxymethyl, methyl and methoxy, and R ^a and R ^b are each hydrogen. a) at least one inorganic tin oxide phase, and b) an organic polymer phase,
A method for producing a tin oxide-containing polymer composite material comprising:
8. The polymer composition according to claim 1, wherein Ar—C (R ^a , R ^b ) groups are polymerized to form an organic polymer phase, and XSnY units are polymerized to form a tin oxide phase. A process comprising polymerizing at least one compound of the formula I according to item 2.   The process according to claim 11, characterized in that the polymerization of the compound of formula I is carried out in an aprotic organic solvent.   13. A process according to any of claims 11 and 12, characterized in that the polymerization of the compound of formula I is initiated by adding at least one acid. Obtained by the method according to any one of claims 11 to 13,
a) at least one inorganic tin oxide phase, and b) an organic polymer phase,
A tin oxide-containing polymer composite material comprising:   The organic polymer phase and the inorganic tin oxide phase essentially form a co-continuous phase region, and the average distance between two adjacent regions of the same phase is 100 nm or less. Polymer composite material   16. The polymer composite material according to claim 14, wherein the tin oxide phase is essentially present in a state of tin (II) oxide. Production of a tin-carbon composite material comprising at least one inorganic tin-containing phase in which tin is present in an oxidation state of +2 or 0 or a mixed state thereof, and a carbon phase in which carbon is present in elemental form A method,
i. A method according to any one of claims 11 to 13,
providing a tin oxide-containing polymer composite comprising a) at least one inorganic tin oxide phase, and b) an organic polymer phase; and ii. Carbonizing the organic polymer phase of the polymer composite material obtained in step i,
The manufacturing method characterized by including.   The method according to claim 17, wherein the carbonization is performed at a temperature in the range of 400 ° C. to 1800 ° C. in an essentially oxygen-free atmosphere.   The method according to claim 17 or 18, wherein the carbonization is performed at a temperature in the range of 400 ° C to 1800 ° C in an atmosphere containing a reducing gas. Obtained by a method according to any one of claims 17 to 19,
At least one inorganic tin-containing phase in which tin is present in an oxidation state of +2 or 0 or a mixture thereof; and a carbon phase C in which carbon is present essentially in elemental form.
A tin-carbon composite material composed of   21. The tin according to claim 20, wherein the carbon phase C and the tin-containing phase Z essentially form a co-continuous phase region, and the average distance between two adjacent regions of the same phase is 100 nm or less. -Carbon composite material.   21. The tin according to claim 20, wherein the carbon phase C is continuous, the tin-containing phase Z forms an essentially isolated region, and the size of one region is 1 nm to 20 [mu] m. -Carbon composite material.   23. Tin-carbon composite material according to claim 20, 21 or 22, characterized in that the tin-containing phase Z consists essentially of at least 90% elemental tin.   24. A method of using a tin-carbon composite material according to any one of claims 20 to 23 for the manufacture of an electrochemical cell.   A method of using the tin-carbon composite material according to any one of claims 20 to 23 in a negative electrode for a lithium ion battery, particularly a lithium ion secondary battery.   A negative electrode for a lithium ion battery, comprising at least one tin-carbon composite material according to any one of claims 20 to 23.   27. A lithium ion battery comprising at least one negative electrode according to claim 26.