CN103782422A - Tin oxide-containing polymer composite materials - Google Patents

Tin oxide-containing polymer composite materials Download PDF

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CN103782422A
CN103782422A CN201280043102.0A CN201280043102A CN103782422A CN 103782422 A CN103782422 A CN 103782422A CN 201280043102 A CN201280043102 A CN 201280043102A CN 103782422 A CN103782422 A CN 103782422A
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tin
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A·郎格
G·科克斯
K·莱特纳
H·沃尔夫
M·梅林
C·莱昂哈特
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BASF SE
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    • H01M4/36—Selection of substances as active materials, active masses, active liquids
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    • C07C43/205—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring the aromatic ring being a non-condensed ring
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    • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
    • C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
    • C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
    • C07D333/06—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring carbon atoms
    • C07D333/14—Radicals substituted by singly bound hetero atoms other than halogen
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08K5/00—Use of organic ingredients
    • C08K5/56—Organo-metallic compounds, i.e. organic compounds containing a metal-to-carbon bond
    • C08K5/57—Organo-tin compounds
    • H—ELECTRICITY
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    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/387—Tin or alloys based on tin
    • H—ELECTRICITY
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    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
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    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
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    • H01M4/663—Selection of materials containing carbon or carbonaceous materials as conductive part, e.g. graphite, carbon fibres
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    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
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Abstract

Disclosed a novel tin oxide-containing polymer composite materials, a process for production thereof and 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 oxide (II) 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.

Description

The polymer composites that comprises tin oxide
Invention is described
The present invention relates to the new polymer composites that comprises tin oxide, its production method and the purposes in production tin-carbon composite thereof, this tin-carbon composite comprises at least one inorganic stanniferous phase, and wherein tin is with element form or with tin oxide (II) form or exist with its form of mixtures; With carbon phase, wherein carbon exists with element form.These tin-carbon composites are particularly suited for producing for electrochemical cell, the especially anode material of lithium battery.The invention still further relates to the compound (monomer) of the polymer composites that comprises tin oxide for the production of the present invention.
In the society increasing gradually in mobility, mobile electric installation role is increasing.Therefore, for many years, found battery pack, especially rechargeable battery (being called secondary battery or electric storage means) can be used in nearly all sphere of life.There is now the complex characteristics in the demand of its electricity and mechanical properties to secondary battery.For example, the positive demand of electronics industry has new, little, the lightweight secondary cell of high capacitance and high cyclical stability or battery pack to realize the long life-span.In addition, heat sensitivity and self-discharge rate should be lower to guarantee high reliability and efficiency.Meanwhile, need in use there is high lsafety level.Car industry also especially to have interested and these battery pack of the lithium secondary battery of these performances in the future can (for example) as energy accumulating device vehicle or the motor vehicle driven by mixed power for electricity operation.In addition, need to have favourable electronic performance herein to can realize the battery pack of high current density.In the research and development of new battery pack system, also to cherishing a special interest with inexpensive way production rechargeable battery.Environment aspect also plays ever-increasing effect in the research and development of new battery pack system.
The negative electrode of modern high-energy lithium battery group comprises spinel type lithium-transition metal oxide or the mixed oxide as electroactive material, for example LiCoO now conventionally 2, LiNiO 2, LiNi 1-x-yco xm yo 2(M is for example Al or Mn for 0<x<1, y<1) or LiMn 2o 4, or for example iron lithium phosphate.For the structure of the anode of modern lithium battery group, in the several years in past, prove to use lithium-graphite intercalation compound (Journal Electrochem.Soc.1990,2009).In addition, as anode material, lithium-silicon intercalation compound, lithium alloy and lithium titanate are detected (referring to K.E.Aifantis, " Next generation anodes for secondary Li-ion batteries ", High Energy Density Li-Batteries, Wiley-VCH, 2010, the 129-162 pages).In lithium battery group, use liquid or solid electrolyte by two electrode combinations with one another.In (again) charging of lithium battery group, cathode material is oxidized (for example, according to following equation: LiCoO 2→ nLi ++ Li (1-n)coO 2+ ne -).It discharges lithium by cathode material and it migrates to anode with lithium ion form, and wherein lithium ion is relevant to the reduction of anode material, and relevant to the reduction of graphite in the graphite situation of inserting with lithium ion form.Now, lithium occupies the interlayer sites in graphite-structure.In battery power discharge process, the lithium being bonded in anode is removed with lithium ion form by anode, and anode material is oxidized.Lithium ion via electrolyte to negative electrode and relevant with the reduction of cathode material therein.In battery power discharge process and in battery pack, recharge in process, lithium ion moves via distance piece.
But the significant drawbacks in the situation that of using graphite in Li ion battery group is the relatively low ratio electric capacity of the theoretical upper limit with 0.372Ah/g.Graphite-like material with carbon element except graphite also has similar performance, for example carbon black, for example acetylene black, dim, furnace black, flame black, break black (cracking black), channel black or thermals (thermal black), and shinny carbon (shiny carbon) or hard carbon.In addition, these anode materials not do not have problem at secure context.
Using lithium alloy (for example Li xsi, Li xpb, Li xsn, Li xal or Li xsb alloy) can realize compared with high specific capacitance in situation.These alloys make charging capacitor can for the charging capacitor of graphite up to 10 times of (Li xsi alloy; Referring to R.A.Huggins, Proceedings of the Electrochemical society 87-1,1987, the 356-64 pages).A significant drawbacks of these alloys is that its size changes in charge/discharge process, and this causes anode material disintegration.Be that capacitance loss and the battery being caused by anode material and electrolytical irreversible reaction increases the sensitiveness of thermal stress because the specific area of gained anode material increases the result producing, under extreme case, it can cause the strong heat release of battery to destroy and be security risk.
Use lithium as electrode material because security reason has problem.More specifically, in charging operations process, when lithium deposition, on anode material, form lithium skeleton.These lithium skeletons can cause short circuit and therefore cause the not controlled destruction of battery in battery.
EP692 833 has described the insertion compound of carbon containing, and outer its of de-carbon also comprises the metal or the semimetal that form alloy with lithium, especially silicon.The pyrolysis of the polymer of this preparation by comprising metal or semimetal and alkyl realizes, for example, realizing by the pyrolysis of polysiloxanes containing in silicon clathrate situation.Pyrolysis requires harsh conditions, and first main polymer decomposes under these conditions, and forms subsequently carbon and (partly) metal and/or (partly) metal oxide territory.The generation of these materials causes having the quality of bad reproducibility conventionally, and this may be because high-energy input only can make control (if control) difficulty to domain structure.
I.Honma etc., Nano Lett., 9 (2009) have described by embedding and have peeled off the SnO between graphite (exfoliated graphite) sheet 2the nano-porous materials that nano particle forms.These materials are suitable for as anode material for Li ion battery group.It by mixing and peel off graphite flake and SnO in ethylene glycol 2nano particle is produced.Peel off graphite flake itself by the also original production through being oxidized and peeling off graphite.The method is relatively inconvenient and expensive.In addition, the method causes having the result of bad reproducibility.
WO2010/112580 has described electroactive material, and it comprises carbon phase C and at least one MO xphase, wherein M is metal or semimetal, for example boron, silicon, titanium or tin, x is 0 to <k/2 numerical value, wherein k is metal or semimetallic maximum chemical valence.According to WO2010/112580, electroactive material is with two production modes, first stage relates to by so-called bifunctional polymerizable (twin polymerization) by (partly) metal oxide phase and organic polymer production nano composite material mutually, and second stage relates to the consequent nano composite material of carbonization.Although the method in most of the cases obtains extraordinary result, but in tin situation, be difficult to obtain monomer and also can only can make polymerization difficulty, and therefore resulting polymers composite material and the tin-carbon composite by its generation do not have gratifying chemical property.
WO2010/112581 has described the method for production nano composite material, wherein copolymerization containing metal or semimetallic monomer.The monomer that proposes comprises stanniferous monomer, and wherein tin exists with+4 oxidation state.The production of these monomers, it is difficult especially producing with relatively large amount, and polymerization has problem.
In a word, can illustrate based on carbon or based on lithium alloy and so far by the known anode material of prior art unsatisfactory aspect electric capacity, charge/discharge power and/or cyclical stability, for example after several charge/discharge cycle, electric capacity reduces and/or impedance is higher or increase.The composite material that has graininess semimetal or Metal Phase and one or more carbon phase and proposed recently to address these problems can only partly address these problems, and at least, the in the situation that of tin-containing material, the quality of these composite materials cannot reproduction mode realize.In addition, it is produced conventionally too complexity make can not economic utilization.
Therefore, object of the present invention is for the method for producing organotin polymers composite material is provided, and it provides the product quality of low-complexity and well reproduced for these materials, and it allows further processing in tin-carbon composite.Tin-the carbon composite of preparation should be suitable as anode material for Li ion battery group thus, in particular for Li ion secondary battery group, and overcomes the shortcoming of prior art, especially should have at least one in following performance, especially exceedes one:
-high specific capacitance,
-Gao cyclical stability,
-low self-discharge,
-good mechanical stability.
Find, these objects realize astoundingly by the method for the production of the polymer composites that comprises tin oxide that comprises at least one inorganic oxide tin phase and organic polymer phase of below illustrating in detail and the polymer composites that comprises tin oxide that can obtain by the method.
Therefore, the present invention relates to produce the method for the polymer composites that comprises tin oxide, this material comprises
A) at least one inorganic oxide tin phase; With
B) organic polymer phase;
The method is included in and under polymerizing condition, makes at least one formula I monomer polymerization
R 1-X-Sn-Y-R 2?(I)
Wherein
R 1for Ar-C (R a, R b) group, wherein Ar is aromatics or heteroaromatic rings, it optionally has 1 or 2 and is selected from halogen, OH, CN, C 1-C 6alkyl, C 1-C 6the substituting group of alkoxyl and phenyl, and
R a, R bbe hydrogen or methyl or together for oxygen atom or methylene (=CH independently of one another 2);
R 2for C 1-C 10alkyl or C 3-C 8cycloalkyl or have R 1one of definition providing; Or
R 1with R 2be the group of formula A together:
Figure BDA0000472950810000041
Wherein A is aromatics or the heteroaromatic rings that is fused to two keys, and m is 0,1 or 2, and radicals R can be identical or different and be selected from halogen, CN, C 1-C 6alkyl, C 1-C 6alkoxyl and phenyl, and R a, R bseparately as hereinbefore defined;
X is O, S or NH;
Y is O, S or NH;
Ar-C (R under these polymerizing conditions a, R b) group polymerization and be formed with organic polymer phase and XSnY unit polymerization and form tin oxide phase.
Formula I monomer is a part new and that therefore form equally theme of the present invention.With known tin (IV) Compound Phase ratio, it is easy to preparation, and it can also commercial scale preparation.In addition, it is more stable than corresponding tin (IV) compound, and therefore its use in polymerization has less problem.
The present invention also provides the polymer composites that comprises tin oxide that can obtain by the inventive method, and it comprises
A) at least one inorganic oxide tin phase; With
B) organic polymer phase.
The polymer composites that the organic polymer of the polymer composites that comprises tin oxide that can known way own obtain according to the present invention by carbonization comprises tin oxide with plain mode by the present invention is converted into tin-carbon composite.
The present invention also provides the method for production tin-carbon composite, and this composite material comprises at least one inorganic stanniferous phase, wherein tin with 0 or+2 oxidation state or exist with its form of mixtures; With carbon phase, wherein carbon exists with element form; The method comprises:
I. provide by method and hereinafter described the polymer composites that comprises tin oxide herein, and
The organic polymer phase of the polymer composites that comprises tin oxide ii. obtaining in carburising step i.
The present invention provides tin-carbon composite in addition, and it can be obtained and be comprised at least one inorganic stanniferous phase by the method, and wherein tin is with+2 or 0 oxidation state or exist with its form of mixtures; With carbon phase, wherein carbon exists with element form.
Due to carbon phase C with by the forming and particular arrangement of stanniferous phase of producing gained, tin-carbon composite is particularly suited for as electroactive material, for Li ion battery, being particularly useful in the anode in Li ion secondary battery or battery pack.More specifically, for Li ion battery, especially in the situation in the anode of Li ion secondary battery, due to high capacitance and good circulation stability and noticeable, and guarantee the Low ESR in battery.In addition, may arrange due to common continuous phase, it has high mechanical stability.In addition, it can plain mode and can reproduction quality producing.
Therefore, the present invention also provides tin-carbon composite at lithium ion battery, especially the purposes in the anode of lithium rechargeable battery, and be provided for lithium ion battery, especially the anode that comprises tin-carbon composite of the present invention of lithium rechargeable battery, and provide the lithium ion battery with at least one anode that comprises tin-carbon composite of the present invention, especially lithium rechargeable battery.
Illustrate in detail the inventive method and the preferred embodiment of the obtainable polymer composites that comprises tin oxide and tin-carbon composite wherein herein with in claims.
For the present invention, the polymer composites that comprises tin oxide is interpreted as meaning the basic (degree of at least 90 % by weight conventionally, especially the degree of at least 95 % by weight) by the material of tin oxide and organic polymer phase composition, these exist with the form in being distributed in each other.Tin oxide mutually conventionally substantially (i.e. degree, the especially degree of at least 95 % by weight of common at least 90 % by weight) is made up of tin oxide or tin oxide hydrate.The carbon polymer that contains that organic polymer is served as reasons mutually except elemental carbon forms.The composition of organic polymer phase is by Ar-C (R a, R b) group definition, and therefore it comprises poly-(mixing) aryl formaldehyde condensation product or poly carbonate aryl ester or its mixture conventionally.
For the present invention, term " tin oxide " comprises stoichiometry SnO pure zirconia tin (for example α-SnO and β-SnO, Sn 2o 3and SnO 2, for example octagon SnO 2with hexagon SnO 2), divalence and stannic oxide hydrate, for example Sn (OH) 2with stannic acid H 2sn (OH) 6.
For the present invention, carbon-tin composite material is interpreted as meaning the basic (degree of at least 90 % by weight conventionally, especially the degree of at least 95 % by weight) material that formed by stanniferous phase and elemental carbon, and on the one hand stanniferous phase and on the other hand carbon exist with the form in being distributed in each other.Carbon is formed by elemental carbon, and carbon can have graphite-structure unit.
As the same with " heteroaromatic rings " in term " aromatic ring ", term " alkyl ", " alkoxyl ", " cycloalkyl " and " hydroxyalkyl " are interpreted as containing conventionally by the substituent general collectivity term described in this term.Thus, suffix C n-C mrefer to the possible carbon number that can be had by the substituting group of this collectivity terminology overview.
Therefore, alkyl is for conventionally having 1 to 10, and often 1 to 6, the especially saturated straight chain of 1 to 4 carbon atom or branched aliphatic alkyl.The example of alkyl is methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, 2-butyl, 2-methyl-propyl, 1,1-the dimethyl ethyl (=tert-butyl group), n-pentyl, 2-amyl group, 2-methyl butyl, n-hexyl, 2-hexyl, n-heptyl, 2-heptyl, n-octyl, 2-octyl group, 2-ethylhexyl, n-nonyl, positive decyl, 1-methyl nonyl and 2-propylheptyl.
Therefore, alkoxyl is for via oxygen atom bonding and conventionally have 1 to 10, and often 1 to 6, the especially saturated straight chain of 1 to 4 carbon atom or branched aliphatic alkyl.The example of alkoxyl is methoxyl group, ethyoxyl, positive propoxy, isopropoxy, normal-butyl oxygen base, 2-butyl oxygen base, 2-methyl propoxyl group, 1,1-dimethyl ethyoxyl (=tert-butoxy), n-pentyl oxygen base, 2-amyl group oxygen base, 2-methyl butoxy, n-hexyl oxygen base, 2-hexyl oxygen base, n-heptyl oxygen base, 2-heptyl oxygen base, n-octyl oxygen base, 2-octyl group oxygen base, 2-ethylhexyl oxygen base, n-nonyl oxygen base, positive decyl oxygen base, 1-methyl nonyl oxygen base and 2-propylheptyl oxygen base.
Therefore, serve as reasons at least one OH group of hydroxyalkyl replaces and conventionally has 1 to 10, and often 1 to 6, the especially radical of saturated aliphatic alkyl of 1 to 4 carbon atom.The example of hydroxyalkyl is methylol, 1-ethoxy, 2-ethoxy, 1-hydroxypropyl, 2-hydroxypropyl, 3-hydroxypropyl, 1-hydroxyl-1-Methylethyl, 2-hydroxyl-1-Methylethyl, 4-hydroxyl butyl etc.
Therefore, cycloalkyl is for conventionally having 3 to 10, and often 3 to 8, especially 3 to 6 carbon atoms and optionally by 1 to 4 methyl substituted saturated rings aliphatic hydrocarbyl.The example of cycloalkyl is cyclopropyl, cyclobutyl, cyclopenta, cyclohexyl, ring octyl group, 1-methyl cyclopropyl, 2-methyl cyclopropyl, 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 etc.
For the present invention, aromatic group is interpreted as meaning carbocyclic aromatic alkyl, for example phenyl or naphthyl.
For the present invention, heteroaromatic group is interpreted as meaning conventionally to have the heterocyclic aromatic group of 5 or 6 ring memberses, wherein one of ring members is for being selected from the hetero-atom of nitrogen, oxygen and sulphur, and in other ring memberses 1 or 2 is optionally that nitrogen-atoms and residue ring member are carbon.The example of heteroaromatic group be furyl, thienyl, pyrrole radicals, pyrazolyl, imidazole radicals,
Figure BDA0000472950810000071
azoles base, different
Figure BDA0000472950810000072
azoles base, pyridine radicals and thiazolyl.
For the present invention, fused aromatic group or ring are interpreted as meaning carbocyclic aromatic divalent hydrocarbyl, for example adjacent phenylene (benzo) or 1,2-naphthylene (naphtho-).
In the methods of the invention, the stanniferous monomer of gathering I, under these conditions Ar-C (R under reaction condition a, R b) group polymerization and be formed with organic polymer phase and XSnY unit polymerization and form tin oxide phase.These polymerization reactions are called bifunctional polymerizable and for example, by () WO2010/112580 and WO2010/112581 known.Compared with the inventive method, those monomers of be+4 oxidation state that WO2010/112580 and WO2010/112581 only propose tin.
In the methods of the invention, preferably use those formulas I monomer, wherein at least one in variable X and Y, especially two variable X and Y are oxygen.
In the methods of the invention, preferably use those formulas I monomer, wherein Ar-C (R a, R b) R in unit or formula A group aand R bthe hydrogen of respectively doing for oneself.
In the methods of the invention, preferably use those formulas I monomer, wherein R 1and R 2identical or different and the formula Ar-C (R that respectively does for oneself a, R b)-group, preferably R wherein aand R brespectively the do for oneself group of those formulas of hydrogen.At R 1and R 2ar-C (R respectively does for oneself a, R b) when group, Ar is preferably the aromatics or the heteroaromatic group that are selected from phenyl and furyl, wherein phenyl and furyl are unsubstituted or have 1 or 2 and be selected from halogen, OH, CN, C 1-C 6alkyl, C 1-C 6alkoxyl, C 1-C 6the substituting group of hydroxyalkyl and phenyl.More specifically, Ar is phenyl or furyl, and wherein phenyl and furyl are unsubstituted separately or optionally have 1 or 2 and be selected from C 1-C 6alkyl, C 1-C 6hydroxyalkyl and C 1-C 6alkoxyl, is especially selected from the substituting group of methylol, methyl and methoxyl group.In a preferred embodiment, Ar is phenyl, and it is unsubstituted or especially has 1 or 2 and is selected from C 1-C 6alkyl and C 1-C 6alkoxyl, is especially selected from the substituting group of methyl and methoxyl group.Especially the example of preferred group Ar is methoxyphenyl or 2,4-Dimethoxyphenyl.R 1and R 2especially be (methoxyphenyl) methyl or (2,4-Dimethoxyphenyl) methyl independently of one another.
In the another embodiment of formula I monomer, radicals R 1and R 2be the group of formula A as hereinbefore defined, the especially group of formula Aa together:
Figure BDA0000472950810000081
Wherein #, m, R, R aand R bseparately as hereinbefore defined.In formula A and Aa, variable m is especially 0.Be 1 or 2 o'clock at m, R is especially methylol, methyl or methoxy.In formula A and Aa, R aand R bespecially the hydrogen of respectively doing for oneself.
Formula I monomer can be similar to the mode of the method known to the preparation of organo-tin compound itself to be prepared.Conventionally the monomer of formula I or compound (wherein R, 1for Ar-C (R a, R b) group) for example, for example, for example, by making suitable tin (II) compound (tin halides (II) (stannic chloride (II)) or tin (II) alkoxide (methyl alcohol tin (II) (Sn (OCH 3) 2))) and formula Ar-C (R a, R bthe compound of)-XH or formula Ar-C (R a, R b)-XH or Ar-C (R a, R bthe mixture reaction preparation of the different compounds of)-YH, wherein Ar, X, Y, R aand R bseparately as hereinbefore defined.In the situation that using tin halides (II), this reaction is carried out conventionally under the tertiary amine as alkali exists.Conventionally, based on the required stoichiometry of reaction, formula Ar-C (R a, R b)-XH or Ar-C (R a, R bthe compound of)-YH is with excessive use.
In a similar manner, the monomer of formula I or compound (wherein R 1for Ar-C (R a, R b) group) can for example, for example, for example, by making suitable tin (II) compound (tin halides (II) (stannic chloride (II)) or tin (II) alkoxide (methyl alcohol tin (II) (Sn (OCH 3) 2))) react preparation with the compound of formula AXHYH:
Figure BDA0000472950810000091
Wherein m, A, X, Y, R, R aand R bseparately as hereinbefore defined.Using in tin halides (II) situation, this reaction is carried out conventionally under the tertiary amine as alkali exists.Conventionally,, based on the required stoichiometry of reaction, compd A XHYH is with excessive use.
For producing polymer composites, monomer (being below also the called monomer I) polymerization separately (homopolymerization) of formula I.Also can make the mixture copolymerization of different monomers I.Also can make one or more monomer I and known being suitable for and R 1or R 2the material copolymerization of group copolymerization.Particularly, these materials comprise aliphatic series, aromatics or heteroaromatic aldehyde, for example benzaldehyde, furfural, formaldehyde or acetaldehyde, preferably use the formaldehyde that is gas form or is non-aqueous oligomeric or polymerized form (being for example trioxane (trioxane) or paraformaldehyde form).Can make equally monomer I of the present invention and other monomer copolymerizations, these monomers can be under bifunctional polymerizable condition copolymerization and comprise the semimetal that forms oxide, for example, described in WO2010/112580 and WO2010/112581, and it can have metal or semimetal beyond detin.Particularly, the monomer that these materials comprise the general formula I described in WO2010/112580 and WO2010/112581, is below formula X
Figure BDA0000472950810000092
Wherein
M is metal or semimetal, the 3rd or 4 main groups of preferred cycle table or metal or semimetal, especially B, Al, Si, Ti, Zr, Hf, Ge, Sn, Pb, V, As, Sb or the Bi of the 4th or 5 transition group, more preferably B, Si, Ti, Zr or Sn, even more preferably Si or Ti, especially Si;
R 1a, R 2aar-C (R can identical or different and respectively do for oneself a, R b) group, wherein Ar, R a, R bseparately as convolution I above defines, especially as the definition of preferably mentioning,
Or radicals R 1ax and R 2ay is the group of formula A ' together
Figure BDA0000472950810000101
Wherein A, R, m, R a, R bseparately as convolution I above defines, especially as the definition of preferably mentioning,
X is O, S or NH, especially O;
Y is O, S or NH, especially O;
Q is 0,1 or 2 according to the chemical valence of M or electric charge, especially 1,
G, Q can identical or different and respectively do for oneself O, S, NH or chemical bond, especially oxygen or chemical bond;
R 1 ', R 2 'c can identical or different and respectively do for oneself 1-C 6alkyl, C 3-C 6cycloalkyl, aryl or Ar '-C (R a ', R b ') group, wherein Ar ' by as Ar is defined to and R a ', R b 'respectively freely to R a, R binstitute defines, the hydrogen of especially respectively doing for oneself, or R 1 ', R 2 'be the group of formula A ' as hereinbefore defined together with Q with G;
Especially the monomer of general formula I I, IIa, III, IIIa, IV, V, Va, VI or the VIa described in WO2010/112580 and WO2010/112581.
In a preferred embodiment, based on the total amount of wanting polymerization single polymerization monomer, the ratio of the monomer (for example formula X monomer or above-mentioned aldehyde) except formula I monomer is no more than 20 % by weight, especially 10 % by weight, be that formula I monomer accounts at least 80 % by weight of wanting polymerization single polymerization monomer total amount, especially at least 90 % by weight.In another embodiment of the present invention, the ratio of formula I monomer in the total amount of wanting polymerization single polymerization monomer is 20 % by weight to 80 % by weight, especially 30 % by weight to 70 % by weight, and based on the total amount of wanting polymerization single polymerization monomer, the ratio of the monomer (for example formula X monomer or above-mentioned aldehyde) except formula I monomer is within the scope of 20 % by weight to 80 % by weight, especially within the scope of 30 % by weight to 70 % by weight.
Formula I monomer can be similar to mode and different monomers polymerization and the copolymerization of the method described in WO2010/112580 and WO2010/112581.
In a preferred embodiment of the inventive method, monomer I in organic solvent or solvent mixture, polymerization in especially organic non-protonic solvent or solvent mixture.Preferably those non-protonic solvents of the polymer composites that forms soluble (solubility <1g/l at 25 ℃).Therefore, under polymerizing condition, form the especially little particle of polymer composites.But polymerization also can be carried out in body.
Suppose that the non-protonic solvent that uses the polymer composites forming in polymerization to be insoluble in wherein can promote particle to form in principle.If carry out polymerization under particulate inorganic material exists, the formation of particle may be controlled by the existence of particulate inorganic material, and this can prevent from forming crude polymer composite material.
Non-protonic solvent is preferably through selecting so that monomer I is solvable at least partly.This is interpreted as meaning under polymerizing condition the solubility of monomer I in solvent at least 50g/l, especially at least 100g/l.Conventionally, organic solvent through select so that at 20 ℃ the solubility of monomer be 50g/l, especially at least 100g/l.More specifically, solvent is through selecting so that monomer I is basic or completely solvable therein, the ratio of solvent and monomer I through selection so that under polymerizing condition at least 80%, especially at least 90% or all monomer I exist with dissolved form.
" non-proton property " means substantially not comprise to have for the solvent of polymerization be one or morely bonded to the proton of hetero-atom (for example O, S or N) and therefore more or less have acid solvent.Based on the total amount of organic solvent, proton solvent therefore for being less than 10 volume %, is particularly less than 1 volume % in the ratio of the solvent for polymerization or solvent mixture, is especially less than 0.1 volume %.The polymerization of monomer I is preferably carried out under substantially anhydrous, i.e. the amount based on solvent for use, and in the time that polymerization starts, the concentration of water is less than 500ppm.
Solvent can be inorganic or organic solvent or the mixture for inorganic solvent and organic solvent.It is preferably organic solvent.
The example of suitable non-proton organic solvent is halogenated hydrocarbons (for example carrene, chloroform, dichloroethanes, trichloroethanes, 1,2-dichloroethanes, 1,1,1-trichloroethanes, 1-chlorobutane, chlorobenzene, dichloro-benzenes, fluorobenzene) and pure hydrocarbon (it can be aliphatic series, cyclic aliphatic or aromatics) and with the mixture of halogenated hydrocarbons.The example of pure hydrocarbon is for conventionally having 2 to 8, preferably non-annularity aliphatic hydrocarbon, the especially alkane of 3 to 8 carbon atoms (for example ethane, isopropyl alkane and n-propane, normal butane and isomers thereof, pentane and isomers thereof, n-hexane and isomers thereof, normal heptane and isomers thereof and normal octane and isomers thereof); Cycloaliphatic hydrocarbon (for example thering is the cycloalkane of 5 to 8 carbon atoms, for example pentamethylene, methyl cyclopentane, cyclohexane, hexahydrotoluene, cycloheptane) and aromatic hydrocarbon (for example benzene,toluene,xylene, mesitylene, ethylo benzene, cumene (2-propylbenzene), different cumene (1-propylbenzene) and tert-butyl benzene).Also preferred above-mentioned hydrocarbon and halogenated hydrocarbon (for example halogenation aliphatic hydrocarbon (for example chloromethanes, carrene, chloroform, chloroethanes, 1,2-dichloroethanes and 1,1,1-trichloroethanes and 1-chlorobutane) and halogenated aromatic hydrocarbon (for example chlorobenzene, 1,2-dichloro-benzenes and fluorobenzene)) mixture.
The example of inorganic non-protonic solvent is especially supercritical carbon dioxide, cos (carbon oxide sulfide), carbon disulfide, nitrogen dioxide, thionyl chloride, sulfonic acid chloride and sulfur dioxide liquid, and rear three kinds of solvents can also play polymerization initiator.
Monomer I is polymerization under polymerization initiator or catalyst existence conventionally.Polymerization initiator or catalyst are through selecting so that its initiation or catalysis monomer I (are monomeric unit XR 1and YR 2) cationic polymerization and the formation of tin oxide phase.Therefore, in monomer I polymerization process, monomeric unit XR on the one hand 1and YR 2polymerization and on the other hand tin oxide synchronised form.Term " synchronously " needn't mean monomeric unit XR 1and YR 2polymerization and the formation of tin oxide phase carry out with phase same rate.But " synchronously " means the coupling and being triggered by cationic polymerization condition in dynamics of these processes.
In suitable polymerization initiators or catalyst principle, be all substances of known catalysed cationic polymerization.These materials comprise Bronsted acid (Bronsted acid) and non-proton property lewis acid.Preferably proton catalyst is Bronsted acid, for example organic carboxyl acid, for example trifluoroacetic acid, oxalic acid or lactic acid, and especially organic sulfonic acid, for example Loprazolam, trifluoromethayl sulfonic acid or toluenesulfonic acid.Inorganic Bronsted acid (for example HCl, H 2sO 4or HClO 4) suitable equally.Lewis acid used can be (for example) BF 3, BCl 3, SnCl 4, TiCl 4or AlCl 3.Also can use with complex form bonding or be dissolved in the lewis acid in ionic liquid.Polymerization initiator or catalyst conventionally take based on monomer M as 0.1 % by weight to 10 % by weight, preferably the amount of 0.5 % by weight to 5 % by weight use.
The required temperature of monomer I polymerization conventionally at 0 ℃ within the scope of 150 ℃, particularly at 20 ℃ within the scope of 140 ℃, especially at 40 ℃ within the scope of 120 ℃.
The inventive method is particularly suited for polymer composites continuous and/or that batch mode industrial production comprises tin oxide.In batch mode, this means batch sizes for 10kg at least, often 100kg at least, especially at least 1000kg or at least 5000kg.In continuous mode, this means output and is generally at least 100kg/ days, often 1000kg/ days at least, especially at least 10 tons/days or at least 100 tons/days.
The polymer composites that comprises tin oxide basic (i.e. degree, the especially degree of at least 95 % by weight of common at least 90 % by weight) that can obtain by the inventive method is by tin oxide and organic polymer phase composition.Tin oxide mutually conventionally substantially (i.e. degree, the especially degree of at least 95 % by weight of common at least 90 % by weight) is made up of tin oxide or tin oxide hydrate.Preferably at least 80% degree, especially at least 90% degree exist with the tin form of be+2 oxidation state tin oxide herein.Organic polymer is by forming containing carbon polymer except elemental carbon.The composition of organic polymer phase is by Ar-C (R a, R b) group definition, and therefore it typically is poly-(mixing) aryl formaldehyde condensation product or poly carbonate aryl ester or its mixture.
Another result of the inventive method is that tin oxide phase and organic polymer exist with common continuous arrangement in wide region, this mean corresponding substantially do not form mutually any by optionally continuously phase region around separation phase region.But two form the continuous phase region penetrating each other separating on space mutually, as by visible by transmission electron microscope test material.With regard to term " phase region continuously ", " discontinuous phase region " and " continuous phase region altogether ", also with reference to W.J.Work etc., Definitions of Terms Related to Polymer Blends, Composites and Multiphase Polymeric Materials, (IUPAC Recommendations 2004), Pure Appl.Chem., 76 (2004), 1985-2007 page, especially the 2003rd page.Therefore, the common continuous arrangement of two component mixtures is interpreted as meaning the arrangement that is separated of two phases or component, wherein, in a territory of specific phase, the continuous approach through arbitrary phase region can be pulled to all phases border of not crossing over any phase region border.
In polymer composites of the present invention, organic polymer phase and tin oxide form the basic region of continuous phase region altogether and account at least 50 volume % of polymer composites, often at least 80 volume %, especially at least 90 volume % mutually.
In polymer composites of the present invention, distance between the territory of the distance between adjacent boundary or adjacent phase homophase is less and be on average no more than 100nm, is particularly no more than 20nm, is especially no more than 10nm.Distance between adjacent phase homophase is (for example) two by the distance between the territory of the spaced tin oxide phase in the territory of organic polymer phase or two by the distance between the territory of the spaced organic polymer phase in the territory of tin oxide phase.Average distance between the territory of adjacent phase homophase can be measured (with the transmissivity measurement at 20 ℃, monochromatization CuK via scattering vector q by small angle x ray scattering (SAXS) αradiation, 2D detector (image board), slit collimation (slit collimation)).
Also can pass through transmission electron microscope, especially determine the size of alpha region by HAADF-STEM technology (HAADF-STEM=high angle annular details in a play not acted out on stage, but told through dialogues scanning electron microscopy) and therefore determine distance between adjacent boundary and the arrangement of phase.In this imaging technique, the element of phase counterweight (for example Sn is with respect to C) seems that low weight element is bright.Due to preparation compared with the compact area not finer and close area bright that seems, so can see equally the false picture of preparation (preparation artifact).
As above mentioned, the invention still further relates to by least one inorganic stanniferous tin-carbon composite of producing mutually, this inorganic stanniferous mutually in tin with the tin form of be+2 or 0 oxidation state, especially with element form or with tin oxide (II) or Sn (II) oxide hydrate form or exist with its form of mixtures.For this reason, in first step i, provide the polymer composites that comprises tin oxide by said method.This polymer composites that comprises tin oxide of carbonization in second step.It is the phase substantially being formed by elemental carbon by organic polymer inversion of phases herein.Basic this phase structure of preserving.
For this reason, conventionally in basic the eliminating under oxygen, the polymer composites obtaining in step I is heated to at least 400 ℃, preferably at least 500 ℃, especially the temperature of at least 700 ℃, for example be heated within the scope of 400 ℃ to 1800 ℃, preferably within the scope of 500 ℃ to 1500 ℃, the especially temperature within the scope of 700 ℃ to 1200 ℃." get rid of under oxygen " partial pressure of oxygen in the reaction zone that means to carry out carbonization basic lower and be preferably no more than 20 millibars, especially 10 millibars.
In one embodiment of the invention, carbonization in inert gas atmosphere, for example, is carried out under nitrogen or argon gas.Inert gas atmosphere preferably comprises and is less than 1 volume %, is especially less than the oxygen of 0.1 volume %.In another embodiment of the present invention, carbonization is carried out under so-called reducing gas exists.Dehydrogenation (H 2) outside, reducing gas also comprises appropriate hydrocarbon gas as methane, ethane or propane or ammonia (NH 3).Reducing gas can former state uses or to use as the form of mixtures of nitrogen or argon gas with inert gas.
Granular composite material is preferably to be dried (substantially solvent-free) powder type for carbonization.Herein and below " solvent-free " means composite material and comprises and be less than 1 % by weight, is especially less than 0.1 % by weight solvent.
Optionally, carbonization is carried out under oxidant exists, and this oxidant promotes graphite, for example transition metal halide as the formation of ferric trichloride.This realizes following effect: the carbon in material with carbon element of the present invention mainly exists with graphite or Graphene unit form, condenses construction unit form with many rings of each carbon atom and three other carbon atoms formation covalent bonds and exists.Based on polymer composites, the amount of these oxidants is generally 1 % by weight to 20 % by weight.At this oxidant, when the carbonization, program is generally polymer composites and oxidant is mixed with each other and is the mixture of substantially solvent-free powder type with carbonization.Optionally after carbonization, for example, used (for example) solvent or solvent mixture washing oxidant or removed oxidant by evaporation by (), oxidant and product thereof dissolve in this solvent or solvent mixture.
In this way, in step I i, obtain the preferred particulates shape tin-carbon composite that comprises carbon phase and at least one tin phase.Carbon-tin composite material of the present invention with the degree of at least 90 % by weight, is especially made up of at least one tin phase and elemental carbon with the degree of at least 95 % by weight conventionally.Stanniferous (i.e. degree, the especially degree of at least 95 % by weight of common at least 90 % by weight) mutually conventionally is substantially by tin or tin oxide or tin oxide hydrate or its compositions of mixtures.
According to the present invention, tin-carbon composite comprises carbon phase (being below also called C phase), wherein carbon back originally exists with element form, this means the total amount of the carbon in mutually based on C, at carbon, the ratio in is mutually less than 10 % by weight to non-carbon atom (for example N, O, S, P and/or H), is especially less than 5 % by weight.Can measure by the sub-spectroscope of x ray photoelectric the content of the non-carbon atom of C in mutually.Due to preparation, outside de-carbon, C can especially comprise a small amount of nitrogen, oxygen, sulphur and/or hydrogen mutually.The mol ratio of hydrogen and carbon is no more than the value of the value of 1:3, particularly 1:5 conventionally, especially the value of 1:10.This value also can be 0 or be almost 0, for example≤0.1.C mutually in, carbon may mainly exist with unformed or graphite form.Can study reference feature and determine in conjunction with energy (284.5eV) and characteristic asymmetric signal shape by ESCA the existence of unformed or graphitic carbon.The carbon that is graphite form is interpreted as meaning carbon and is at least partly take graphite as typical hexagon layer and arranges, and wherein these layers also can be through bending or peel off.
Except C mutually, tin-carbon composite of the present invention also comprises at least one tin phase (Sn phase), tin be+2 or 0 oxidation state of tin in mutually or be its mixed form.Sn is mutually preferably substantially for example, by element tin or tin oxide (II) or tin oxide (II) hydrate (stannic hydroxide (II)) or its compositions of mixtures.Sn mutually in, the total amount of the carbon based on Sn in mutually, the ratio of Fei Xi and non-oxygen atom (for example other metals or semimetal and N, S, P and/or H) is preferably less than 10 % by weight, is especially less than 5 % by weight.Sn mutually in, the tin form of can be+2 oxidation state of tin or be element tin form (being that tin is 0 oxidation state) or be its mixed form.In a preferred embodiment, tin is mainly 0 oxidation state, and this means at least 50% in mutually of Sn, and especially at least 80% or at least 90% tin atom is 0 oxidation state, is especially element tin form.
Conventionally, C phase and Sn form altogether phase region continuously with irregular alignment mutually substantially, average distance between average distance between two adjacent domains of Sn phase or two adjacent domains of C phase is no more than 100nm, particularly be no more than 20nm, especially be no more than 10nm, and (for example), at 0.5nm to 100nm, in particularly 0.7nm to 20nm, especially 1nm to 10nm scope.With regard to the average distance between two adjacent domains of Sn phase and C phase, the explanation of above polymer composites obtaining in step I being carried out is suitable in the same manner.
In yet another embodiment, Sn is the Sn territory form embedding using basic separate mode as matrix in continuous carbon phase C mutually.In this embodiment, the size in Sn territories more than 50 volume % is through 1nm to the 20 μ m that is everlasting, especially within the scope of 1nm to 1 μ m.More specifically, in these tin-carbon composites of this embodiment, based on the gross mass of tin-carbon composite, tin content is 5 % by weight to 90 % by weight, preferably 10 % by weight to 75 % by weight, more preferably 15 % by weight to 55 % by weight, especially 20 % by weight to 40 % by weight.
The inventive method is particularly suited for continuous and/or batch mode industrial production tin-carbon composite.In batch mode, this means batch sizes for 10kg at least, often 100kg at least, especially at least 1000kg or at least 5000kg.In continuous mode, this means output and is generally at least 100kg/ days, often 1000kg/ days at least, especially at least 10 tons/days or at least 100 tons/days.
As described in, tin-carbon composite of the present invention is for electrochemical cell, especially in lithium ion battery time due to especially favourable performance, especially high specific capacitance, high cyclical stability, low self-discharge and formation lithium skeleton trend and the favourable dynamics with regard to charge/discharge operation and noticeable, to can obtain high current density.
For the present invention, electrochemical cell or battery pack are interpreted as meaning battery pack, capacitor and the electric storage means (secondary battery) of any kind, especially alkali metal battery or battery pack (for example lithium, lithium ion, lithium-sulphur and alkaline earth metal batteries group and electric storage means, particularly also be high-energy or high performance system form), and by Supercaps, Goldcaps with BoostCaps or known electrolytic capacitor and the double layer capacitor of Ultracaps title.
Therefore, the present invention also provides tin-carbon composite in the purposes of producing in electrochemical cell, more specifically provides it at lithium ion battery, especially the purposes in the anode of lithium rechargeable battery.Therefore, the invention still further relates to for lithium ion battery, the especially anode of lithium rechargeable battery, it comprises tin-carbon composite of the present invention.
Except tin-carbon composite of the present invention, anode conventionally comprises at least one and is suitable for the adhesive of fixed tin-carbon composite of the present invention and optionally other conductions or electroactive composition.In addition, anode conventionally has and electrically contacts for the supply of electric charge and remove.Gross mass based on anode material deducts any current-collector and electrically contacts, and the amount of tin-carbon composite of the present invention is generally at least 40 % by weight, often at least 50 % by weight, especially at least 60 % by weight.
By known other the suitable conductions of relevant monograph or electroactive composition (for example, referring to M.E.Spahr, Carbon Conductive Additives for Lithium-Ion Batteries, M.Yoshio etc. (editor) Lithium Ion Batteries, Springer Science+Business Media, New York 2009, the 117-154 pages and the document of wherein quoting).Other useful conductions or electroactive composition in anode of the present invention comprise carbon black, graphite, carbon fiber, carbon nano-fiber, carbon nano-tube or conducting polymer.Conventionally, in anode, use approximately 2.5 % by weight to 40 % by weight electric conducting materials and 50 % by weight to 97.5 % by weight, often 60 % by weight to 95 % by weight electroactive material of the present invention, the gross mass of the numerical value representing with % by weight based on anode material deducts any current-collector and electrically contacts.
The useful adhesive that uses above-mentioned tin-carbon composite and other electroactive materials to produce anode comprises all prior art adhesives that are suitable for anode material in principle, for example, as known (by relevant monograph, referring to A.Nagai, Applications of PVdF-Related Materials for Lithium-Ion Batteries, M.Yoshio etc. (editor) Lithium Ion Batteries, Springer Science+Business Media, New York2009, 155-162 page and the document of wherein quoting, and H.Yamamoto and H.Mori, SBR adhesive (to negative electrode) and ACM adhesive (to positive electrode), the same, 163-180 page).Useful adhesive especially comprises following polymeric material: polyethylene glycol oxide (PEO), cellulose, carboxymethyl cellulose (CMC), polyethylene, polypropylene, polytetrafluoroethylene, polyacrylonitrile-methyl methacrylate, polytetrafluoroethylene, Styrene-Butadiene, tetrafluoroethene-hexafluoroethylene copolymer, polyvinylidene fluoride (PVdF), polyvinylidene fluoride-hexafluoropropylene copolymer (PVdF-HFP), tetrafluoraoethylene-hexafluoropropylene copolymer, tetrafluoroethene, perfluoroalkyl-vinyl ether co-polymer, vinylidene difluoride-hexafluoropropylene copolymer, ethylene-tetrafluoroethylene copolymer, vinylidene fluoride-mono-chlorotrifluoroethylcopolymer copolymer, ethene-chlorine fluoride copolymers, ethylene-acrylic acid copolymer (comprising and do not comprise sodium ion), ethylene-methacrylic acid copolymer (comprising and do not comprise sodium ion), ethylene-methyl acrylate copolymer (comprising and do not comprise sodium ion), polyimides and polyisobutene.
Optionally consider for the preparation of the performance of any solvent under select adhesive.The adhesive conventionally amount take the total mixture based on anode material (be tin-carbon composite and optionally other electroactive or electric conducting materials) as 1 % by weight to 10 % by weight uses.Preferably use 2 % by weight to 8 % by weight, especially 3 % by weight to 7 % by weight.
Anode can common mode itself by as (for example produce by the prior art of quoting in beginning with by the standard method known to relevant monograph, referring to R.J.Brodd, M.Yoshio, Production processes for Fabrication of Lithium-Ion Batteries, M.Yoshio etc. (editor) Lithium Ion Batteries, Springer Science+Business Media, New York 2009, the 181-194 pages and the document of wherein quoting).For example, anode can be produced in the following manner: optionally with an organic solvent (for example 1-METHYLPYRROLIDONE or hydrocarbon solvent) mixes optional other compositions (conductive compositions and/or organic bond) of electroactive material of the present invention and anode material, and optionally makes it stand manufacturing process or it is applied to inert metal paper tinsel (for example Cu paper tinsel).Optionally dry afterwards.This (for example) is used the temperature of 80 ℃ to 150 ℃ to carry out.Drying process also can under reduced pressure be carried out and conventionally continue 3 to 48 hours.Optionally, also can adopt melting or sintering method to form.
The present invention also provides lithium ion battery, especially lithium rechargeable battery, and it has at least one anode that comprises tin-carbon composite of the present invention.
These batteries have at least one anode of the present invention, the negative electrode that is suitable for lithium ion battery, electrolyte and distance piece optionally conventionally.
With regard to suitable cathode materials, suitable electrolyte and appropriate interval part with regard to may arranging, for example, such as, with reference to related art (prior art of quoting in beginning) and suitable monograph and reference works: Wakihara etc. (editor), Lithium Ion Batteries, the 1st edition, Wiley VCH, Weinheim, 1998; David Linden:Handbook of Batteries (McGraw-Hill Handbooks), the 3rd edition, McGraw-Hill Professional, New York 2008; J.O.Besenhard:Handbook of Battery Materials.Wiley-VCH, 1998; M.Yoshio etc. (editor) Lithium Ion Batteries, Springer Science+Business Media, New York 2009; K.E.Aifantis, S.A.Hackney, R.V.Kumar, (editor), High Energy Density Lithium Ion Batteries, Wiley-VCH, 2010.
Useful negative electrode especially comprises that wherein cathode material comprises those following negative electrodes: at least one lithium transition-metal oxide (for example lithium and cobalt oxides, lithium nickel oxide, lithium-cobalt-nickel oxide, lithium manganese oxide (spinelle), lithium nickel cobalt aluminum oxide, lithium nickel cobalt manganese oxide or lithium-barium oxide) or lithium transition metal phosphates (for example iron lithium phosphate).Useful cathode material also comprises sulphur and S-containing composite, for example, as to the known sulphur-carbon composite of lithium-sulfur cell.
Use liquid or solid electrolyte that two electrodes (being anode and negative electrode) are connected to each other.Useful liquid electrolyte especially comprises the non-aqueous solution (the common <20ppm of water content) of lithium salts and melting Li salt, for example lithium hexafluoro phosphate, lithium perchlorate, hexafluoroarsenate lithium, trifluoromethyl sulfonic acid lithium, two (trifluoromethyl sulfonyl) imide lis or LiBF4 (especially lithium hexafluoro phosphate or LiBF4) for example, at suitable non-protonic solvent (ethylene carbonate, propylene carbonate and composition thereof) with following solvent in one or more in solution: dimethyl carbonate, diethyl carbonate, dimethoxy-ethane, methyl propionate, ethyl propionate, butyrolactone, acetonitrile, ethyl acetate, methyl acetate, toluene and dimethylbenzene, especially in the mixture of ethylene carbonate and diethyl carbonate.Solid electrolyte used can be (for example) ionic conductive polymer.
Distance piece through liquid electrolyte dipping can be arranged between electrode.The example of distance piece is especially the perforated membranes such as glass fibre non-woven fabric and porous organo polysilica compound film, such as polyethylene, polypropylene, PVdF.
These distance pieces can have (for example) prismatic films structure, and wherein solid thin film electrolyte is arranged on and forms the film of anode and form between the film of negative electrode.Central cathode output conductor is arranged between each cathodic coating to form double-side cell (double-faced cell) structure.In another embodiment, can use one side battery (single-faced cell) structure, wherein single negative electrode output conductor belongs to the combination of single anode/distance piece/cathode element.In this structure, conventionally between anode/distance piece/negative electrode/output conductor elements combination, dielectric film is being set separately.
The following drawings and embodiment are used for explaining the present invention and should not be understood with ways to restrain.
Tem analysis is for utilizing Tecnai F20 transmission electron microscope (FEI, Eindhoven, The Netherlands) HAADF-STEM that carries out using superthin layer technology (sample is embedded in the synthetic resin of matrix) under the operating voltage of 200kV analyzes.
ESCA research and utilization carries out from the sub-spectrometer of FEI5500LS x ray photoelectric (Eindhoven, The Netherlands) of FEI.
Small angle x ray scattering analysis is used warp at 20 ℃ in slit collimation
Figure BDA0000472950810000191
the Cu of mirror monochromatization k αradiation is carried out.For background collect data and just caused by slit collimation fuzzy to its sharpening.
For IR spectrum, a little less than abbreviation s, m and w represent by force, neutralize, and the relative intensity of index strip.
I. the preparation of monomer I:
Preparation Example 1: the preparation of tin (II) two (2-methoxyphenyl methoxyl group compounds)
(monomer I, wherein X=Y=O; R 1=R 2=2-methoxy-benzyl)
A) by the anhydrous SnCl of 19.51g (10.29mol) 2be dissolved in 250ml methyl alcohol.At room temperature drip wherein 57ml (41.16mol) anhydrous triethylamine.Form at once colourless precipitation.Adding completely after triethylamine, reactant mixture is being stirred to 2h and subsequent filtration precipitation again.Gained colorless solid is used to 20ml methanol wash three times at every turn and washed three times with 20ml ether subsequently at every turn.Obtain methyl alcohol tin (II) (Sn (OCH that 17.67g (97.74mmol, 95%) is unformed solid form 3) 2).
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 measured value (calculated value): C:48.6% (C:48.9%), H:5.0% (H:4.6%).
1H?NMR(500.30MHz,CDCl 3)δ[ppm]:3.78(s,3H,CH 3O),4.92(s,2H,CH 2),6.82(d,1H),6.87(dd,1H),7.23(dd,1H),7.31(d,1H)。
13C?NMR(125.81MHz,CDCl 3)δ[ppm]:53.8(CH 3O),59.4(CH 2),108.8,119.4,127.0,127.2,128.4,155.9。
119Sn?NMR(186.53MHz,CDCl 3)δ[ppm]:-160。
13C{ 1H}CP-MAS?NMR(100.62MHz)δ[ppm]:55.9(CH 3O),61.2(CH 2),109.3,119.7,125.5,127.4,131.7,156.2。
119Sn{ 1H}CP-MAS?NMR(149.19MHz)δ[ppm]:-351。
B) by 3.00g (16.59mmol) Sn (OCH 3) 2be suspended in 50ml toluene.Adding after 4.82g (34.85mmol) 2-methoxy-benzyl alcohol, add hot suspension and steam and remove discharged methyl alcohol, in this process, suspension material dissolves.Be concentrated into after about 15ml at clarification toluene solution, be settled out colorless solid.By this solid use ether repeated washing and in high vacuum (10 -3millibar) lower dry.Obtain 4.73g (12.04mmol, 72.5%) and be the title compound of colorless solid form, its can be based on its IR spectrum or 1h NMR spectrum discrimination.
Preparation Example 2: the preparation of tin (II) two (2,4-Dimethoxyphenyl methoxyl group compounds)
(monomer I, wherein X=Y=O; R 1=R 2=2,4-dimethoxy-benzyl)
By 2.00g (11.06mmol) Sn (OCH 3) 2be suspended in 50ml toluene.Adding 3.91g (23.25mmol) 2, after 4-dimethoxy-benzyl alcohol, adding hot suspension and steam and remove discharged methyl alcohol, in this process, suspension material dissolves.Concentrated gained settled solution is until be settled out white solid.By this solid use ether repeated washing and in high vacuum (10 -3millibar) lower dry.This obtains the title compound that 3.98g (8.78mmol, 79.4%) is colorless solid form.
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-Oν),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%).
1H?NMR(500.30MHz,CDCl 3)δ[ppm]:3.75(s,3H,4-MeO),3.80(s,3H,2-CH 3O),4.76(s,2H,CH 2),6.40(dd,2H),7.20(s,1H)。
13C?NMR(125.81MHz,CDCl 3)δ[ppm]:55.3(CH 3O),60.6(CH 2),98.3,103.8,124.6,130.1,158.2,160.3。
119Sn?NMR(186.52MHz,CDCl 3)δ[ppm]:-161,-269。
13C{ 1H}CP-MAS?NMR(100.62MHz)δ[ppm]:54.5(CH 3O),58.9(CH 2),97.0,108.1,126.3,133.4,158.4,160.8。
119Sn{ 1H}CP-MAS?NMR(149.17MHz)δ[ppm]:-350。
Preparation Example 3: the preparation of tin (II) two ((2-thienyl) dimethyl methoxy base compounds)
(monomer I, wherein X=Y=O; R 1=R 2=1-(2-thienyl)-1-Methylethyl)
By 2.00g (11.06mmol) Sn (OCH 3) 2be suspended in 50ml toluene.Adding after the solution of 3.15g (22.12mmol) (2-thienyl) dimethylcarbinol in 8ml toluene, mixture is being stirred at 23 ℃ to 1h and under reduced pressure remove subsequently the methyl alcohol forming in dereaction.Gained settled solution is concentrated into dry.Gained colorless solid, by ether recrystallization, obtains the title compound that 3.24g (8.07mmol, 73%) is colorless solid form.
The preparation of Preparation Example 4:7-methoxyl group benzo [4H-1,3,2-] dioxa stannane (dioxastannin)
Figure BDA0000472950810000211
By 1.5g (8.30mmol) Sn (OCH 3) 2be suspended in 50ml toluene.Adding after 1.28g (8.30mmol) 2-hydroxy-5-methyl oxy-benzyl alcohol the methyl alcohol forming in mixture being stirred at 23 ℃ to 1h and removing dereaction by distillation subsequently.Under reduced pressure gained settled solution is concentrated into dry.This obtains yellow solid, it is repeated to thoroughly washing with ether and in high vacuum (10 -3millibar) lower dry.This obtains 1.83g (6.72mmol, 81%) title compound.
The preparation of Preparation Example 5:6-methoxyl group benzo [4H-1,3,2-] dioxa stannane
Figure BDA0000472950810000221
This preparation is similar to Preparation Example 4 to be carried out, and different is to use 2-hydroxyl-4-methoxy-benzyl alcohol to replace 2-hydroxy-5-methyl oxy-benzyl alcohol.
Productive rate: 1.65g (6.06mmol, 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)(C-Oν),1032(s),957(s),832(m),789(m),735(m),488(s)(Sn-O)。
The preparation of Preparation Example 6:7-methyl benzo [4H-1,3,2-] dioxa stannane
Figure BDA0000472950810000222
This preparation is similar to Preparation Example 4 to be carried out, and different is to use 2-hydroxy-5-methyl oxy-benzyl alcohol to replace 2-hydroxy-5-methyl oxy-benzyl alcohol.
Productive rate: 1.68g (6.60mmol, 79.5%).
The production of polymer composites:
Embodiment 1:
The compound (monomer 1) of 0.5g (1.27mmol) Preparation Example 1 is dissolved in 16ml chloroform.Under agitation be heated to 50 ℃ and keep 5 days to trifluoromethane sulfonic acid that to add based on monomer 1 in solution be 10mol% as catalyst and by mixture.In this process, be settled out solid.Under suction, cross filter solid.At use ether repeated washing and in high vacuum (10 -3millibar) lower dry after, obtain with the productive rate of 0.22g (43%) polymer composites that is colorless solid form.
Embodiment 2:
Use the compound of 10mol% trifluoroacetic acid as polymerization catalyst 0.52g Preparation Example 1 to be similar to the mode of embodiment 1.Productive rate with 0.06g (12%) obtains the polymer composites that is colorless solid form.
Embodiment 3:
The compound (monomer 2) of 0.94g (2.09mmol) Preparation Example 2 is dissolved in 14ml chloroform.Under agitation be heated to 50 ℃ and keep 24h to trifluoromethane sulfonic acid that to add based on monomer 2 in solution be 10mol% as catalyst and by mixture.In this process, be settled out solid.Under suction, cross filter solid.At use ether repeated washing and in high vacuum (10 -3millibar) lower dry after, obtain with the productive rate of 0.84g (89%) polymer composites that is colorless solid form.
Embodiment 4:
Use the compound of 10mol% trifluoroacetic acid as polymerization catalyst 0.6g Preparation Example 2 to be similar to the mode of embodiment 1.Productive rate with 0.19g (32%) obtains the polymer composites that is colorless solid form.
Embodiment 5:
The compound of 0.91g Preparation Example 5 is dissolved in 6ml anhydrous chloroform and with the 10mol% trifluoromethayl sulfonic acid being dissolved in 2ml anhydrous chloroform and is mixed.Reactant mixture is at room temperature stirred 3 days again.Thereafter filtering purple, precipitates and uses chloroform repeated washing.Productive rate: 0.74g (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-Oν)(s),1021(s),955(m),835(m),758(m),631(s),567(m),507(m),426(s)(Sn-O)。

Claims (27)

1. a compound for general formula I,
R 1-X-Sn-Y-R 2?(I)
Wherein
R 1for Ar-C (R a, R b) group, wherein Ar is aromatics or heteroaromatic rings, it optionally has 1 or 2 and is selected from halogen, OH, CN, C 1-C 6alkyl, C 1-C 6the substituting group of alkoxyl and phenyl, and
R a, R bbe hydrogen or methyl or together for oxygen atom or methylene (=CH independently of one another 2),
R 2for C 1-C 10alkyl or C 3-C 8cycloalkyl or have R 1one of definition providing; Or
R 1with R 2be the group of formula A together:
Figure FDA0000472950800000011
Wherein A is aromatics or the heteroaromatic rings that is fused to two keys, and m is 0,1 or 2, and radicals R can be identical or different and be selected from halogen, CN, C 1-C 6alkyl, C 1-C 6hydroxyalkyl, C 1-C 6alkoxyl and phenyl, and R a, R bseparately as hereinbefore defined;
X is O, S or NH;
Y is O, S or NH.
2. according to the compound of claim 1, the X in its Chinese style I and the Y oxygen of respectively doing for oneself.
3. according to the compound of any one in aforementioned claim, its Ar-C (R a, R b) R in the group of unit or formula A aand R bthe hydrogen of respectively doing for oneself.
4. according to the compound of any one in aforementioned claim, wherein R 1, R 2identical or different and the Ar-C (R that respectively does for oneself a, R b) group.
5. according to the compound of any one in aforementioned claim, wherein Ar-C (R a, R b) Ar in unit is aromatics or the heteroaromatic group that is selected from phenyl and furyl, wherein phenyl and furyl are unsubstituted or optionally have 1 or 2 and be selected from halogen, CN, C 1-C 6alkyl and C 1-C 6the substituting group of alkoxyl.
6. according to the compound of claim 5, wherein Ar-C (R a, R b) Ar in unit is selected from C for having 1 or 2 1-C 6alkyl, C 1-C 6hydroxyalkyl and C 1-C 6the substituent phenyl of alkoxyl.
7. according to the compound of claim 6, wherein Ar-C (R a, R b) Ar in unit is 2-methoxyphenyl or 2,4-Dimethoxyphenyl.
8. according to the compound of any one in claim 1-3, wherein R 1and R 2be the group of formula A together.
9. according to the compound of any one in claim 1-3, wherein R 1and R 2be the group of formula Aa together:
Figure FDA0000472950800000021
Wherein m, R, R aand R bseparately as hereinbefore defined.
10. according to the compound of claim 9, the m in its Chinese style Aa be 0,1 or 2, R be selected from methylol, methyl and methoxyl group, R aand R bthe hydrogen of respectively doing for oneself.
The method of the polymer composites that 11. 1 kinds of production comprises tin oxide, this composite material comprises:
A) at least one inorganic oxide tin phase; With
B) organic polymer phase;
The method comprises makes at least one according to formula I compound polymerization under polymerizing condition of any one in claim 1-7, Ar-C (R under these conditions a, R b) group polymerization and form this organic polymer phase and XSnY unit polymerization and form this tin oxide phase.
12. according to the method for claim 11, and being aggregated in non-proton organic solvent of its Chinese style I compound carried out.
13. according to the method for claim 11 or 12, and the polymerization of its Chinese style I compound causes by adding at least one acid.
14. 1 kinds can, by the polymer composites that comprises tin oxide obtaining according to the method for any one in claim 11-13, comprise:
A) at least one inorganic oxide tin phase; With
B) organic polymer phase.
15. according to the polymer composites of claim 14, and wherein this organic polymer phase forms basic continuous phase region altogether mutually with this inorganic oxide tin, and the average distance between two adjacent domains of phase homophase is no more than 100nm.
16. according to the polymer composites of claims 14 or 15, and wherein this tin oxide exists with tin oxide (II) form mutually substantially.
Produce the method for tin-carbon composite for 17. 1 kinds, this composite material comprises at least one inorganic stanniferous phase, and wherein this tin is with+2 or 0 oxidation state or exist with its form of mixtures; With carbon phase, wherein carbon exists with element form; The method comprises:
I. by providing according to the method for any one in claim 11-13 the polymer composites that comprises tin oxide, this polymer composites comprises
A) at least one inorganic oxide tin phase; With
B) organic polymer phase; And
The organic polymer phase of the polymer composites ii. obtaining in carburising step i.
18. according to the method for claim 17, wherein at the temperature of carbonization within the scope of 400 ℃ to 1800 ℃, in the atmosphere of basic anaerobic, carries out.
19. according to the method for claim 17 or 18, in the atmosphere that is wherein comprising reducing gas at the temperature of carbonization within the scope of 400 ℃ to 1800 ℃, carries out.
20. 1 kinds can, by the tin-carbon composite obtaining according to the method for any one in claim 17-19, comprise:
At least one inorganic stanniferous phase Z, wherein tin is with+2 or 0 oxidation state or exist with its form of mixtures; With
Carbon phase C, wherein carbon back originally exists with element form.
21. according to the tin-carbon composite of claim 20, wherein this carbon phase C with this stanniferous mutually Z-shaped become continuous phase region substantially altogether, the average distance between two adjacent domains of phase homophase is no more than 100nm.
22. according to the tin-carbon composite of claim 20, and wherein this carbon phase C is territory continuous and that this stanniferous mutually Z-shaped one-tenth separates substantially, and the size in a territory is between 1nm and 20 μ m.
23. according to claim 20, tin-carbon composite of 21 or 22, and wherein this stanniferous phase Z is made up of element tin with at least 90% degree substantially.
24. according to the tin-carbon composite of any one in claim 20-23 in the purposes of producing in electrochemical cell.
25. according to the tin-carbon composite of any one in claim 20-23 for lithium ion battery, the purposes of the anode of lithium rechargeable battery especially.
26. 1 kinds of anodes for lithium ion battery, comprise at least one according to the tin-carbon composite of any one in claim 20-23.
27. 1 kinds of lithium ion batteries, comprise at least one according to the anode of claim 26.
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