CN104412422A - Composite materials and method for the production thereof - Google Patents
Composite materials and method for the production thereof Download PDFInfo
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- CN104412422A CN104412422A CN201380034016.8A CN201380034016A CN104412422A CN 104412422 A CN104412422 A CN 104412422A CN 201380034016 A CN201380034016 A CN 201380034016A CN 104412422 A CN104412422 A CN 104412422A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/137—Electrodes based on electro-active polymers
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
- H01M4/602—Polymers
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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Abstract
The invention relates to a method for producing a composite material, which contains a) at least one (semi)metal-containing phase and b) at least one organic polymer phase, comprising the copolymerization of at least one aryloxy (semi)metallate and/or aryloxy ester of a non-metal that forms oxoacids, wherein the non-metal is not carbon or nitrogen, (compound I), with at least one ketone, formaldehyde, and/or formaldehyde equivalent (compound II) in the presence of at least one (semi)metal compound that is not an aryloxy (semi)metallate, (compound III), wherein the weight of (semi)metal of compound III is at least 5 wt% in relation to the weight of compound I.
Description
The present invention is the field of the composite material comprising inorganic (partly) Metal Phase and polymer phase or carbon containing phase.This kind of composite material obtains by reactive bifunctional polymerizable usually.This kind of composite material can be used for production rechargeable battery and energy accumulator.The invention further relates to the purposes of new composite material in electrode and electro-chemical cell.
WO2010/112580 discloses and comprises carbon phase and at least one MO
xthe electroactive material of phase, wherein M is metal or semimetal.These phases form co-cable transmission farmland and by bifunctional polymerizable, calcining step produces subsequently.According to this file, M can be selected from B, Al, Si, Ti, Zr, Sn, Sb or its mixture.Si can be 90 % by mole at the most based on the total amount of M.
WO2010/112581 comprises the method by bifunctional polymerizable preparation with the nano composite material of at least one inorganic or organic metal phase and organic polymer phase.In addition, the nano composite material with carbon phase and at least one semimetal/metal oxide or semimetal/metal nitride inorganic phase is described.Described nano composite material has co-cable transmission farmland.Disclosing metal or semimetal can be Si and other metallic atom of at least one, the especially combination of Ti or Sn.
PCT/EP2012/050690 describes to produce has the method for the composite material of at least one oxide phase and an organic polymer phase, its nonmetallic aryloxy group ester by aryloxy group (partly) metal acid-salt and formation oxyacid and formaldehyde or formaldehyde equivalent copolymerization and realize.The calcining of copolymer causes the electroactive nano composite material comprising semimetal/metal inorganic phase and carbon phase, is wherein present in mutually in co-cable transmission farmland.
EP applies for that no.11181795.3 describes the method based on being made stanniferous monomer reaction by bifunctional polymerizable.Described composite material has at least one tin oxide phase and organic polymer phase, and can be present in co-cable transmission farmland mutually.As EP applies for as described in no.11181795.3, this composite material also can be used for producing tin-carbon composite.
EP apply for no.11178160.5 disclose reacted with pink salt by phenolic aldehyde and prepare comprise carbon phase and at least one SnO
xthe electroactive material of phase, wherein x is the number of 0-2.
In order to industrial-scale production based on the anode material with nanoscale carbon containing and the composite material containing (partly) Metal Phase, can need simply, can reproduce and cheap production method.This is also real for for this reason required reactant.In addition, the performance of synthesized composite material should be controlled by controllably improving technique condition and/or raw material, especially (partly) tenor.
The object of this invention is to provide the composite material being suitable for the anode material making Li-ion batteries piles.Also found its production method, described method allowed in a straightforward manner, reproducible quality and with industrial-scale production composite material, and can to produce to hold facile raw material in reliable and cheap mode.Another object is that (partly) tenor can adjust in the limit of non-constant width.
With the electro-chemical cell that this anode material is produced, there is high power capacity, cyclical stability, efficiency and reliability, and good mechanical stability and Low ESR.In addition, the method can be used for a large amount of combinations of difference (partly) metal, and described (partly) metal can with flexibly than use.
This object is realized by the method for producing composite material, and described composite material comprises:
A) at least one (partly) Metal Phase, and
B) at least one organic polymer phase,
Described method comprises to be made:
-at least one aryloxy group (partly) metal acid-salt and/or form the nonmetallic aryloxy group ester of oxyacid, is wherein nonmetally different from carbon and nitrogen (Compound I), with
-at least one ketone, formaldehyde and/or formaldehyde equivalent (Compound II per),
-at least one is not copolymerization under the existence of aryloxy group (partly) metal acid-salt (partly) metallic compound (compound III),
Wherein in compound III, the weight of (partly) metal is at least 5 % by weight based on the weight of Compound I.
The present invention further provides composite material, described composite material comprises:
A) at least one (partly) Metal Phase, and
B) at least one organic polymer phase,
Wherein at least one (partly) Metal Phase comprises at least two kinds of different (partly) metals, in composite material, the weight of each (partly) metal is at least 2 % by weight based on the weight of carbon in composite material, at least one organic polymer phase and at least one (partly) Metal Phase form phase domain, and the average distance (arithmetic mean of distance) between two of phase homophase adjacent farmlands is determined as by small angle x-ray scattering (SAXS) and is substantially not more than 200nm.
The present invention also provides composite material (hereinafter also referred to as " electroactive material "), and described composite material comprises:
A) at least one carbon phase, and
B) at least one comprises oxide phase and/or (partly) Metal Phase of at least two kinds of differences (partly) metal, wherein in composite material, the weight of each (partly) metal is at least 2 % by weight based on the weight of carbon in composite material, at least one oxide phase and/or (partly) Metal Phase form phase domain mutually with at least one carbon, average distance (arithmetic mean of distance) between two adjacent farmlands of phase homophase is determined as by small angle x-ray scattering (SAXS) and is substantially not more than 10nm and/or oxide and/or (partly) Metal Phase and basically forms average diameter (arithmetic mean of diameter) and be determined as the phase domain being not more than 20 μm by small angle x-ray scattering (SAXS).
Other embodiment of the present invention be electroactive material of the present invention as the purposes of electrode in electro-chemical cell, and comprise the electro-chemical cell electrode of electroactive material of the present invention.In addition, the invention provides the electro-chemical cell of the electrode comprised containing electroactive material of the present invention, and the purposes in Li-ion batteries piles and device, and comprise device and the Li-ion batteries piles of electro-chemical cell of the present invention.
The inventive method is relevant with dramatic benefit.Lay special stress on holds facile raw material, the kind of available reactant and the flexibility about producible composite material.Such as, the performance of organic polymer phase is by making the modification in the different different Compound I copolymerization of the properties of aryloxy group.In a similar fashion, comprise compound III that difference (partly) metal or nonmetallic Compound I and at least one comprise one or more (partly) metals and combine by using simultaneously and control the performance of (partly) Metal Phase.
About the definition of term " phase ", reference book A.D.McNaught and A.Wilkinson:IUPAC Compendium of Chemical Terminology, the 2nd edition, BlackwellScientific Publications, Oxford, version 2 .3.1 (2012) 1062.Also use term " phase domain " and " altogether continuously " " discontinuous " and " continuous phase domain ".It definitely describes can people such as W.J.Work, Definitions of Terms Related to Polymer Blends, Composites andMultiphase Polymeric Materials (IUPAC Recommendations 2004), PureAppl.Chem., find in 76 (2004) 1985-2007.Such as, the altogether continuously configuration of binary mixture is to be understood that the configuration that is separated meaning two phases and component, and wherein in a farmland of each phase, all regions of phase domain boundary are interconnected by continuous path, and wherein path does not intersect any phase boundary.
In the context of the present invention, dummy suffix notation " (partly) metal " expression " metal and/or semimetal "; Similarly, " (partly) metallicity " expression " metallicity and/or Half-metallic "." oxide " represents the chemical unit comprising (partly) metal and oxygen.Different combining form, such as oxide, hydroxide or mixed form are possible, and stoichiometry also can change in grace period.Such as, have low oxygen content, such as, form based on the weight less than less than 10 % by weight, less than 7 % by weight or 5 % by weight of composite material is possible, as be equivalent to appointed compound approx as SnO or Fe
2o
3* H
2the form of the coatings of stoichiometric composition of O, and there is elevated oxygen level, such as, based on the form of the weight more than more than 15 % by weight, more than 20 % by weight or 25 % by weight of composite material.
Term " alkyl ", " thiazolinyl ", " cycloalkyl ", " alkoxyl ", " cycloalkyloxy " and " aryl " are the collective term about the monovalent organic groups with its usual definition.Carbon atom number possible in group is usually by prefix C
f-C
gdescribe, wherein f is minimum carbon number and g is maximum carbon number.
Alkyl for having usual 1-20, usual 1-10, especially 1-4 carbon atom is saturated, linear or branched hydrocarbyl radical, and be such as methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, sec-butyl, isobutyl group, the tert-butyl group, n-pentyl, 2-amyl group, 3-amyl group, 2-methyl butyl, 3-methyl butyl, 3-methyl fourth-2-base, 2-methyl fourth-2-base, 2,2-dimethyl propyl, n-hexyl, 2-hexyl, 3-hexyl, 2-methyl amyl, 2-methylpent-3-base, 2-methylpent-2-base, 2-methylpent-4-base, 3-methylpent-2-base, 3-methylpent-3-base, 3-methyl amyl, 2,2-dimethylbutyl, 2,2-dimethyl butyrate-3-base, 2,3-dimethyl-Ding-2-base, 2,3-dimethylbutyl, n-heptyl, 2-methylhexyl, own-2-the base of 2-methyl, 2-methyl-own-3-base, own-5-the base of 2-methyl, own-2-the base of 3-methyl, 3-methylhexyl, own-3-the base of 3-methyl, own-4-the base of 3-methyl, own-4-the base of 2-methyl, 2,2-dimethyl amyl group, 2,2-dimethyl-penten-3-base, 2,2-dimethyl-penten-4-base, 2,3-dimethyl-penten-2-base, 2,3-dimethyl-penten-3-base, 2,3-dimethyl-penten-4-base, 2,3-dimethyl-penten-5-base, 2,4-dimethyl amyl group, 2,4-dimethyl-penten-2-base, 2,4-dimethyl-penten-3-base, 2,4-dimethyl-penten-4-base, 2,4-dimethyl-penten-5-base, 3,3-dimethyl amyl group, 3,3-dimethyl-penten-2-base, 3-ethyl pentyl group, 3-ethyl penta-2-base, 3-ethyl penta-3-base, 2,2,3-trimethyl butyl, 2,2,3-trimethyl fourth-3-base, 2,2,3-trimethyl fourth-4-base, n-octyl, 2-methylheptyl, 2-methyl-2-in heptan base, 2-methyl-3-in heptan base, 2-methyl-4-in heptan base, 2-methyl-5-in heptan base, 2-methyl-6-in heptan base, 2-methyl-7-in heptan base, 3-methylheptyl, 3-methyl-2-in heptan base, 3-methyl-3-in heptan base, 3-methyl-4-in heptan base, 3-methyl-5-in heptan base, 3-methyl-6-in heptan base, 3-methyl-7-in heptan base, 4-methylheptyl, 4-methyl-2-in heptan base, 4-methyl-3-in heptan base, 4-methyl-4-in heptan base, 2,2-dimethylhexanyl, own-3-the base of 2,2-dimethyl, own-4-the base of 2,2-dimethyl, own-5-the base of 2,2-dimethyl, own-6-the base of 2,2-dimethyl, 2,3-dimethylhexanyl, own-3-the base of 2,3-dimethyl, own-4-the base of 2,3-dimethyl, own-5-the base of 2,3-dimethyl, own-6-the base of 2,3-dimethyl, 2,4-dimethylhexanyl, own-3-the base of 2,4-dimethyl, own-4-the base of 2,4-dimethyl, own-5-the base of 2,4-dimethyl, own-6-the base of 2,4-dimethyl, 2,5-dimethylhexanyl, own-3-the base of 2,5-dimethyl, own-4-the base of 2,5-dimethyl, own-5-the base of 2,5-dimethyl, own-6-the base of 2,5-dimethyl, 3,3-dimethylhexanyl, own-2-the base of 3,3-dimethyl, own-4-the base of 3,3-dimethyl, own-5-the base of 3,3-dimethyl, own-6-the base of 3,3-dimethyl, 3,4-dimethylhexanyl, own-2-the base of 3,4-dimethyl, own-4-the base of 3,4-dimethyl, own-3-the base of 3,4-dimethyl, 3-ethylhexyl, 3-ethyl hexyl-2-base, 3-ethyl hexyl-3-base, 3-ethyl hexyl-4-base, 3-ethyl hexyl-5-base, 3-ethyl-own-6-base, 2,2,3-tri-methyl-amyl, 2,2,3-trimethyl penta-3-base, 2,2,3-trimethyl penta-4-base, 2,2,3-trimethyl penta-5-base, 2,2,4-tri-methyl-amyl, 2,2,4-trimethyl penta-3-base, 2,2,4-trimethyl penta-4-base, 2,2,4-trimethyl penta-5-base, 2,3,3-tri-methyl-amyl, 2,3,3-trimethyl penta-2-base, 2,3,3-trimethyl penta-4-base, 2,3,3-trimethyl penta-5-base, 2,3,4-tri-methyl-amyl, 2,3,4-trimethyl penta-3-base, 2,3,4-trimethyl penta-2-base, 3-Ethyl-2-Methyl amyl group, 3-Ethyl-2-Methyl penta-2-base, 3-Ethyl-2-Methyl penta-3-base, 3-Ethyl-2-Methyl penta-4-base, 3-Ethyl-2-Methyl penta-5-base, 3-ethyl-3-methyl amyl, 3-ethyl-3-methylpent-2-base, 2,2,3,3-tetramethyl butyl, n-nonyl, 2-Nonyl or positive decyl, 3-propylheptyl.
Thiazolinyl for usually there is 2-20, usual 2-10, especially the olefinic of 2-6 carbon atom is unsaturated, linear or branched hydrocarbyl radical, and be such as vinyl, 1-acrylic, 2-acrylic, 2-methyl-1-propylene base, 2-methyl-2-acrylic, 1-pentenyl, 2-pentenyl, 2-methyl-1-butene thiazolinyl, 3-methyl-1-butene base, 1-methyl-2-butene base, 2-methyl-2-butene base, 3-methyl-2-butene base, 1-hexenyl, 2-hexenyl, 3-hexenyl, 2-methyl-1-pentene thiazolinyl, 3-methyl-1-pentene thiazolinyl, 4-methyl-1-pentene base, 2-methyl-2-pentenyl, 3-methyl-2-pentenyl, 4-methyl-2-pentenyl, 2-methyl-3-pentenyl, 3-methyl-3-pentenyl, 4-methyl-1-pentene base, 2-methyl-1-pentene thiazolinyl, 3,3-dimethyl-2-cyclobutenyl, 2,3-dimethyl-1-cyclobutenyl, 2,3-dimethyl-2-cyclobutenyl, 3,3-dimethyl-1-cyclobutenyl, 2-ethyl-1-cyclobutenyl, 2-ethyl-2-cyclobutenyl, 1-heptenyl, 2-heptenyl, 3-heptenyl, 1-octyl group, 2-octyl group, 3-octyl group, 4-octyl group, 1-nonene base, 2-nonene base, 3-nonene base, 4-nonene base, 1-decene base, 2-decene base, 3-decene base, 4-decene base or 5-decene base.
Alkoxyl is combine via oxygen atom, there is usual 1-20, usual 1-10, especially the alkyl of 1-4 carbon atom, and be such as methoxyl group, ethyoxyl, positive propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy, tert-butoxy, n-pentyloxy, 2-methylbutoxy group, 3-methylbutoxy group, just own oxygen base, positive heptan oxygen base, n-octyloxy, 1-methyl oxygen in heptan base, 2-methyl oxygen in heptan base, 2-ethyl hexyl oxy, positive ninth of the ten Heavenly Stems oxygen base, 1-methyl oxygen in ninth of the ten Heavenly Stems base, n-decyloxy or 3-propyl group oxygen in heptan base.
Cycloalkyl is for usually to have 3-20, usual 3-10, especially the monocyclic, bicyclic or tricyclic saturated alicyclic group of 5 or 6 carbon atoms, and be such as cyclopropyl, cyclobutyl, cyclopenta, cyclohexyl, suberyl, ring octyl group, two rings [2.2.1]-1-in heptan base, two rings [2.2.1]-2-in heptan base, two rings [2.2.1]-7-in heptan base, two rings [2.2.2] pungent-1-base, the pungent-2-base of two rings [2.2.2], 1-adamantyl or 2-adamantyl.
Cycloalkyloxy is combine by oxygen atom, there is usual 3-20, usual 3-10, especially the monocyclic, bicyclic or tricyclic saturated alicyclic group of 5 or 6 carbon atoms, and be such as ring propoxyl group, cyclobutoxy group, cyclopentyloxy, cyclohexyloxy, ring oxygen in heptan base, ring octyloxy, two rings [2.2.1]-1-in heptan oxygen base, two rings [2.2.1]-2-in heptan oxygen base, two rings [2.2.1]-7-in heptan oxygen base, two rings [2.2.2] pungent-1-oxygen base, two rings [2.2.2] pungent-2-oxygen base, 1-Buddha's warrior attendant alkoxyl or 2-Buddha's warrior attendant alkoxyl.
Aryl is aromatic hydrocarbyl.Aromatic hydrocarbyl can with substituting group.It is preferably unsubstituted.Aryl is such as phenyl, 1-naphthyl or 2-naphthyl.
Aryloxy group comprises hydroxyl deprotonation by aromatics monohydroxyaromatic compound (such as hereafter mention those) and the elecrtonegativity oxygen atom obtained.
The inventive method comprises makes Compound I and Compound II per copolymerization under the existence of compound III.According to the present invention, Compound I is at least one aryloxy group (partly) metal acid-salt and/or forms the nonmetallic aryloxy group ester of oxyacid, is wherein nonmetally different from carbon and nitrogen." aryloxy group (partly) metal acid-salt " and " aryloxy group ester " be to be understood that mean to have in form one or more, especially 1,2,3,4,5 or 6 aryloxy group and form the metal of oxyacid, semimetal or nonmetallic compound.According to the present invention, be nonmetally different from carbon and nitrogen.Each aryloxy group by deprotonation oxygen atom be combined in form oxyacid and be different from the metal of carbon and nitrogen, semimetal or nonmetal on.Form oxyacid and be different from these metals of C and N, semimetal or non-metallic atom hereinafter also referred to as central atom.Except aryloxy group, other group can be combined on central atom, such as 1,2 or 3 organic group, and described organic group is selected from alkyl, thiazolinyl, cycloalkyl and aryl or 1 or 2 oxygen atom.
Compound I can have single central atom or multiple central atom, when multiple central atom, has linear, branching, monocycle or multiring structure.Suitable monohydroxyaromatic compound is phenol, alpha-Naphthol and betanaphthol particularly, it is unsubstituted, namely outside hydroxyl-removal, not there is other atom any being different from hydrogen be connected on benzene or naphthalene nucleus, such as, or have single substituting group or multiple, 1,2,3 or 4 is different from the substituting group of hydrogen.These substituting groups are alkyl, cycloalkyl, alkoxyl, cycloalkyloxy and NR especially
ar
bgroup, wherein Ra and Rb is hydrogen atom or alkyl or cycloalkyl independently of one another.
In conjunction with the sum of group usually by central atom, the metal that namely these groups are combined thereon, semimetal or nonmetallic chemical valence determine.
Usually, the central atom of Compound I is (for whole the present invention from periodic table, use 2011IUPAC agreement) following race and be different from the element of carbon and nitrogen: 1 race (wherein particularly Li, Na or K), 2 races (wherein particularly Mg, Ca, Sr or Ba), 4 races (wherein particularly Ti or Zr), 5 races (wherein particularly V), 6 races (wherein particularly Cr, Mo or W), 7 races (wherein particularly Mn), 13 races (wherein particularly B, Al, Ga or In), 14 races (wherein particularly Si, Ge, Sn or Pb), 15 races (wherein particularly P, As or Sb) and 16 races (wherein particularly S, Se or Te).The preferred center atom of Compound I is 4,13,14 or 15 races from periodic table and is different from the element of carbon and nitrogen, wherein particularly from the 2nd, the 3rd and the 4th cycle.Central atom is more preferably selected from B, Al, Si, Sn, Ti and P.
In one embodiment of the invention, one or more aryloxy group semimetal hydrochlorates are used as Compound I, and namely semimetal is as the compound of B or Si.In a specific embodiments of the present invention, Compound I comprises aryloxy group semimetal hydrochlorate, and wherein semimetal is silicon in the degree of the total amount at least 90 % by mole based on semimetal atom.
Can be described by following general formula I especially according to the Compound I that the present invention is suitable:
[(AryO)
mMO
nR
p]q (I)
Wherein:
What M was (partly) metal and formation oxyacid is different from the nonmetal of carbon and nitrogen;
M is integer and is 1,2,3,4,5 or 6,
N is integer and is 0,1 or 2,
P is integer and is 0,1,2 or 3,
Q is the integer of 1-20, especially the integer of 3-6,
M+2n+p is integer, is 1,2,3,4,5 or 6, and is equivalent to the chemical valence of M,
Ary is phenyl or naphthyl, and wherein phenyl ring or naphthalene nucleus are not substituted or can have one or more, such as 1,2 or 3 substituting group, and described substituting group is selected from alkyl, cycloalkyl, alkoxyl, cycloalkyloxy and NR
ar
b, wherein R
aand R
bbe hydrogen, alkyl or cycloalkyl independently of one another;
R is hydrogen, alkyl or cycloalkyl, thiazolinyl, cycloalkyl or aryl, and wherein aryl is not substituted or can has one or more substituting group, and described substituting group is selected from alkyl, cycloalkyl, alkoxyl, cycloalkyloxy and NR
ar
b, wherein R
aand R
bseparately as hereinbefore defined.
When the m in formula I be 2,3,4,5 or 6, Ary can be identical or different, in this case, different Ary can be different in the form of the form of aromatic ring and/or the mode of replacement.When the p in formula I is 2 or 3, R group can be identical or different.
Formula I should be understood to empirical formula; It represents type and the number of the construction unit feature of Compound I, i.e. central atom M and the group be combined on central atom, i.e. the R group of aryloxy group AryO, oxygen atom O and carbon combination and the number of these unit.When q is greater than 1, [(AryO)
mmO
nr
p] unit can form monocycle or many rings or linear structure.In formula I, M be metal or semimetal or form oxyacid be different from the nonmetal of carbon and nitrogen, metal, semimetal and be nonmetally usually selected from the following race from periodic table and be different from the element of carbon and nitrogen:
1 race (wherein particularly Li, Na or K), 2 races (wherein particularly Mg, Ca, Sr or Ba), 4 races (wherein particularly Ti or Zr), 5 races (wherein particularly V), 6 races (wherein particularly Cr, Mo or W), 7 races (wherein particularly Mn), 13 races (wherein particularly B, Al, Ga or In), 14 races (wherein particularly Si, Ge, Sn or Pb), 15 races (wherein particularly P, As or Sb) and 16 races (wherein particularly S, Se or Te).M is preferably selected from 4,13,14 and 15 races of periodic table and is different from the element of carbon and nitrogen, the especially element in the 2nd, the 3rd and the 4th cycle.For M, particularly preferably B, Al, Si, Sn, Ti and P.In the present invention's embodiment very particularly preferably, M is B or Si, especially Si.
In a preferred embodiment of the invention, the p in formula I is 0, and namely atom M is without any R group.In another preferred embodiment of the present invention, the p in formula I is 1 or 2, and namely atom M is with at least one R group.
According to the present invention, method comprises makes Compound I and Compound II per copolymerization under the existence of compound III, namely also can use two or more aryloxy group (partly) metal acid-salt and/or form the nonmetallic aryloxy group ester of oxyacid, being wherein nonmetally different from carbon and nitrogen.Preferred method relates to use at least two kinds of aryloxy group (partly) metal acid-salt and/or forms the nonmetallic aryloxy group ester of oxyacid, is wherein nonmetally different from carbon and nitrogen.Such as, can use two or more compounds, described compound is equivalent to formula I and difference is M, Ary and/or R and/or variable m, n, p and/or q.Such as, at least one formula I, variable p=0, in another formula I of at least one, variable p can for being more than or equal to 1.Preferably, a kind of formula I comprises B, Si, Sn, Ti or P, and especially B, Si or Sn are as M, wherein m be 1,2,3 or 4, n be 0 or 1, especially 0, p is 0, and q is 0,1,3 or 4.Second formula I has Si or Sn as M, and to be wherein 2, n be m that 0, q is 0 and p is 1 or 2.Ary in these two kinds of formula I can be identical or different, and wherein Ary has above-mentioned definition, and especially as the definition preferably described, be not especially substituted or can have 1,2 or 3 substituent phenyl, described substituting group is selected from alkyl, especially C
1-C
4alkyl, and alkoxyl, especially C
1-C
4alkoxyl.R is then preferably C
1-C
6alkyl, C
3-C
10cycloalkyl or phenyl, especially C
1-C
4alkyl, C
5-C
6cycloalkyl or phenyl.In another specific embodiments of the present invention, it is 2 or 4, n is that 0, p is 0 and q is 1,3 or 4 that the one in two kinds of formula I comprises Si as M, m.Two kinds of the second had in the compound of formula I have Si and are that 2, n is 0 as M, m and p is 1 or 2.Ary in two kinds of formula I can be identical or different, and wherein Ary has above-mentioned definition, and especially as the definition preferably described, be not especially substituted or can have 1,2 or 3 substituent phenyl, described substituting group is selected from alkyl, especially C
1-C
4alkyl and alkoxyl, especially C
1-C
4alkoxyl.R is then preferably C
1-C
6alkyl, C
3-C
10cycloalkyl or phenyl, especially C
1-C
4alkyl, C
5-C
6cycloalkyl or phenyl.
Variable m, n, p, Ary and R in formula I are alone or in combination, especially preferred with one of M and particularly preferred combinations of definitions ground preferred definition is as follows:
M is integer and is 2,3 or 4;
N is integer and is 0 or 1;
P is integer and is 0,1 or 2;
Ary is not for be substituted or can to have 1,2 or 3 substituent phenyl, and described substituting group is selected from alkyl, preferred C
1-C
4alkyl, more preferably methyl, cycloalkyl, especially C
3-C
10cycloalkyl, alkoxyl, preferred C
1-C
4alkoxyl, more preferably methoxyl group, cycloalkyloxy, especially C
3-C
10cycloalkyloxy, and NR
ar
b, wherein Ra and Rb is hydrogen, alkyl or cycloalkyl, especially C independently of one another
1-C
4alkyl, preferable methyl, or cycloalkyl, especially C
3-C
10cycloalkyl;
R is C
1-C
6alkyl, C
2-C
6-thiazolinyl, C
3-C
10cycloalkyl or phenyl, especially C
1-C
4alkyl, C
5-C
6cycloalkyl or phenyl.
More particularly, variable m, n, p, Ary and R in formula I are alone or in combination, especially preferred with one of M and particularly preferred combinations of definitions ground preferred definition is as follows:
M is integer and is 2,3 or 4;
N is integer and is 0;
P is integer and is 0,1 or 2;
Ary is not for be substituted or can to have 1,2 or 3 substituent phenyl, and described substituting group is selected from alkyl, especially C
1-C
4alkyl and alkoxyl, especially C
1-C
4alkoxyl.
A preferred embodiment of Compound I is that wherein q is the formula I of numeral 1.This compounds can be considered to the ortho esters of the parent oxyacid of central atom M.In these compounds, separately as hereinbefore defined, especially independent or combination, has a preferred or particularly preferred definition especially in combination for variable m, n, p, M, Ary and R.
Compound I can be preferably formula I, and wherein M is Al, B, Si, Sn, Ti or P, m be 3 or 4, n be 0 or 1, p be 0,1 or 2, and q is 1.Ary wherein has above-mentioned definition, and especially as the definition preferably described, be not especially substituted or can have 1,2 or 3 substituent phenyl, described substituting group is selected from alkyl, especially C
1-C
4alkyl and alkoxyl, especially C
1-C
4alkoxyl.
The embodiment very particularly preferably of Compound I is those formula I, and wherein M is B, Si or Ti, and m is 3 or 4, n is that 0, p is 0,1 or 2 and q is 1.Ary wherein has above-mentioned definition, and especially as the definition preferably described, be not especially substituted or can have 1,2 or 3 substituent phenyl, described substituting group is selected from alkyl, especially C
1-C
4alkyl, and alkoxyl, especially C
1-C
4alkoxyl.
A specific embodiments of Compound I is formula I, and to be wherein Si, m be M that 4, n is 0 and p is 0,1 or 2.Ary wherein has above-mentioned definition, and especially as the definition preferably described, be not especially substituted or can have 1,2 or 3 substituent phenyl, described substituting group is selected from alkyl, especially C
1-C
4alkyl, and alkoxyl, especially C
1-C
4alkoxyl.
Example according to the preferred wherein formula I of q=1 of the present invention is tetraphenoxy-silicane alkane, four (4-methylphenoxy) silane, triphenyl borine acid esters, triphenyl, tetraphenyl titanate esters, tetramethylphenyl titanate esters, tetraphenyltin acid esters and triphenyl aluminum acid esters.
Other embodiment of Compound I is that wherein Ary group is those different compound of Formula I.Therefore, the fusing point of Compound I reduces usually, and this can obtain advantage in polymerization.The example preferably according to the present invention with the formula I of different Ary is triple phenoxyl (4-methylphenoxy) silane, two (4-methylphenoxy) silane of two phenoxy groups, triple phenoxyl (4-methylphenoxy) silane, two phenoxy group two (4-methylphenoxy) silane, 4-methylphenylboronic acid diphenyl, 4-aminomethyl phenyl metatitanic acid triphenyl ester and two (4-aminomethyl phenyl) metatitanic acid diphenyl and composition thereof.
Another specific embodiments of Compound I for wherein M be Si, m is 1,2 or 3, and n is 0 and p is those formula I of 4-m.Ary wherein has above-mentioned definition, and especially as the definition preferably described, be not especially substituted or can have 1,2 or 3 substituent phenyl, described substituting group is selected from alkyl, especially C
1-C
4alkyl and alkoxyl, especially C
1-C
4alkoxyl.In these compounds, R has the definition described about formula I; More particularly, R is hydrogen, methyl, ethyl, phenyl, vinyl or pi-allyl.The example of the preferred compound I of this embodiment is hexichol TMOS, hexichol oxygen butyldimethylsilyl, triple phenoxyl silane, methyl (triple phenoxyl) silane, dimethyl (two phenoxy groups) silane, trimethyl (phenoxy group) silane, phenyl (triple phenoxyl) silane and diphenyl (two phenoxy groups) silane.
Suitable Compound I also has " condensation product " of the wherein formula I of q=1.These compounds have formula I usually, wherein q be greater than 1 integer, the integer of such as 2-20, especially 3,4,5 or 6.This compounds is in form derived from the condensation of the wherein formula I of q=1, and in often kind of situation, form removes two AryO unit to form Ary-O-Ary molecule and M (OAry) simultaneously
m-2(O)
n+ 1R
punit.Therefore, they are formed by the structural element of following formula (Ia) substantially:
-[-O-A-]- (Ia)
Wherein:
-A-is M (AryO)
m-2(O)
n(R)
pgroup, wherein M, Ary and R are separately as hereinbefore defined,
M is integer and is 3 or 4,
N is integer and is 0 or 1, especially 0,
P is integer and is 0,1 or 2,
M+2n+p is integer, is 3,4,5 or 6, and is equivalent to the chemical valence of M.
Preferably, the M in formula I is Si, Sn, B and P.
In a preferred embodiment, condensation product is ring-type, and q is 3,4 or 5.This compounds especially can be described by following structure:
K is 1,2 or 3 and-A-is M (AryO)
m-2(O)
n(R)
pgroup.M, Ary and R have the above definition provided about formula I separately, and m, n and p meet the above condition provided about formula I.
In another preferred embodiment of the present, condensation product is linear and is met by the AryO unit of end.In other words, this compounds can be described by following structure I c:
Ary-[-O-A-]
q-OAry (Ic)
Q is the integer of 2-20, and-A-is M (AryO)
m-2(O)
n(R)
pgroup, wherein M, Ary and R are each defined about formula I freely above, and m, n and p respectively defined about formula I freely above.When compound has the distribution of the number about repetitive, when namely there is different q, particularly preferably this embodiment.Such as, can there is mixture, the quality at least 99 % by weight, at least 90 % by weight, at least 80 % by weight or at least 60 % by weight wherein based on Compound I exists as the oligomer mixture of wherein q=2-6 or q=4-9 or q=6-15 or q=12-20.
The example of this kind of condensation product is triphenyl metaboric acid ester, six phenoxy group cyclotrisiloxane, eight phenoxy group cyclotetrasiloxanes, triple phenoxyl cyclotrisiloxane or four phenoxy group cyclotetrasiloxanes.
Compound I is known or can be similar to the known method preparation preparing phenoxide; For example, see DE 1816241, Z.Anorg.Allg.Chem.551 (1987) 61-66, Z.Chem.5 (1965) 122-130 and Houben-Weyl, VI-2 roll up, 35-41.
According to the present invention, the method comprises makes at least one Compound I and the copolymerization of at least one Compound II per.
Compound II per is at least one ketone, such as acetone, aldehyde, such as furfural, or aldehyde equivalent, such as three
alkane.These compounds can form polymer architecture with phenol usually under condensation.In a preferred embodiment, Compound II per is formaldehyde or formaldehyde equivalent or its mixture.Be to be understood that the compound copolymerization that also can make different formaldehyde equivalent.Polymerization preferably uses and is selected from least one gas formaldehyde, three
the Compound II per (hereinafter also referred to as formaldehyde material source) of alkane and/or paraformaldehyde carries out.It is especially three years old
alkane.
Preferably use the formaldehyde in Compound I and formaldehyde or formaldehyde equivalent (Compound II per) so that Compound II per with such amount, namely monomer formaldehyde used amount or be present in the amount of the formaldehyde in formaldehyde equivalent when using formaldehyde equivalent, be at least 0.7:1 relative to the mol ratio of the aryloxy group AryO be present in Compound I, 0.9:1 better, preferred at least 1:1, especially at least 1.01:1, more preferably at least 1.05:1, especially at least 1.1:1.Formaldehyde excessive is more greatly normally not crucial, but it is unnecessary, so formaldehyde or formaldehyde equivalent use consequently relative to the aryloxy group AryO be present in Compound I with such amount usually, the mol ratio of formaldehyde or the mol ratio of formaldehyde be present in formaldehyde equivalent are no more than 10:1, the value of preferred 5:1, especially 2:1.The formaldehyde that preferred use is measured like this or formaldehyde equivalent are consequently relative to the aryloxy group AryO be present in Compound I, the mol ratio of formaldehyde or the mol ratio being present in the formaldehyde in formaldehyde equivalent are 1:1-10:1, especially 1.01:1-5:1, especially 1.05:1-5:1 or 1.1:1-2:1.
Formaldehyde equivalent is to be understood that the compound meaning release formaldehyde under polymerization conditions.Formaldehyde equivalent is preferably oligomer or the polymer of formaldehyde, namely has empirical formula (CH
2o)
xmaterial, wherein x represents the degree of polymerization.These are particularly including three
alkane (3 formaldehyde units) and comprise the paraformaldehyde of a usual 8-100 formaldehyde unit.
Compound III is at least one is not aryloxy group (partly) metal acid-salt (partly) metallic compound.At least one (partly) metallic compound can be pure inorganic in nature, the halide of such as (partly) metal, sulfate, nitrate or phosphate, or be covalency in nature, the alkanoate of such as (partly) metal or alkoxide.
Be present in (partly) metal in compound III especially from the 1st race (particularly preferably Na of periodic table, K), 2nd race (particularly preferably Ca, Mg), 3rd race (particularly preferably Sc), 4th race (particularly preferably Ti, Zr), 5th race (particularly preferably V), 6th race (particularly preferably Cr, Mo, W), 7th race (particularly preferably Mn), 8th race (particularly preferably Fe, Ru, Os), 9th race (particularly preferably Co, Rh, Ir), 10th race (particularly preferably Ni, Pd, Pt), 11st race (particularly preferably Cu, Ag, Au), 12nd race (particularly preferably Zn, Cd), 13rd race (particularly preferably B, Al, Ga, In), 14th race (particularly preferably Si, Sn) the and 15th race (particularly preferably As, Sb, Bi) element.Preferably (partly) metal Ti, V, Cr, Mo, W, Mn, Fe, Co, Ni, Cu, Zn, B, Si and/or Sn, particularly preferably (partly) metal Ti, Fe, Co, Cu, Si and/or Sn.
Inorganic (partly), metallic compound comprised (partly) metal halide, and wherein halide can be selected from fluoride, chloride, bromide, iodide and astatine, and composition thereof and hydrate.(partly) metal halide of preferred use is preferably TiCl
4, CrCl
3, MnCl
2, FeCl
2, FeCl
3, CoCl
2, NiCl
2, ZnCl
2, CuCl
2, SnCl
2and/or SnCl
4, especially TiCl
4, FeCl
3, CoCl
2, CuCl
2, SnCl
2and/or SnCl
4.Other embodiment is (partly) metal sulfate, nitrate, phosphate or carbonate.Oxo anion (the such as SO of " sulfate " ordinary representation sulphur herein
4 2-, SO
3 2-, S
2o
3 2-), " nitrate " represents oxo anion (the such as NO of nitrogen
3, NO
2 -), " phosphate " represents the oxo anion of phosphorus, and " carbonate " represents the oxo anion of carbon.Preferably (partly) metal sulfate or nitrate, especially Cr
2(SO
4)
3, MnSO
4, FeSO
4, Fe (NO
3)
3, Co (NO
3)
2, NiSO
4, Cu (NO
3)
2, ZnSO
4and/or Sn (NO
3)
2.
When compound III comprises organic (partly) metallic compound, the anion be present in organic (partly) metallic compound is such as carboxylate radical (particularly preferably acetate, butyric acid root, propionate, palm acid group, citrate, oxalate, propylene acid group), alcoxylates is (as described above, particularly preferably methoxyl group compound, ethoxylate, positive propoxy compound, isopropoxy compound, n-butoxy compound, sec-butoxy compound, isobutoxy compound and tert-butoxy compound) and mercaptides (especially methyl mercaptan salt, ethyl mercaptan salt, rosickyite alkoxide, butyl mercaptan salt).Especially carboxylate and alcoxylates, especially acetate, methoxyl group compound or ethoxylate is used.Organic (partly) metallic compound of preferred use is Fe (CH
3cOO)
2, Zn (CH
3cOO)
2, Cu (CH
3cOO)
2, Si (OCH
3)
4, especially Fe (CH
3cOO)
2or Si (OCH
3)
4.
For compound III, the compound preferably used is Fe (CH
3cOO)
2, CoCl
2, CuCl
2, SnCl
2, FeCl
3, Si (OCH
3)
4, TiCl
4and/or SnCl
4.
In the methods of the invention, compound III uses with such amount so that in compound III, the weight of (partly) metal is at least 5 % by weight based on the weight of Compound I, usually more than 5 % by weight, and especially at least 10 % by weight, preferably at least 15 % by weight, more preferably at least 20 % by weight.
In an embodiment of the inventive method, can make Compound I and formaldehyde material source, Compound II per is polymerized under the existence of the acid of catalytic amount.Usually, acid is with the weight 0.1-10 % by weight based on Compound I, the especially amount of 0.2-5 % by weight, and such as the maximum of 4 or 3 or 2 or 1 % by weight uses at the most.Preferred acid is
acid, such as organic carboxyl acid is as trifluoroacetic acid, oxalic acid and lactic acid, and organic sulfonic acid.The latter is C especially
1-C
20alkanesulfonic acid, such as Loprazolam, perfluoroetane sulfonic acid, decane sulfonic acid and dodecane sulfonic acid, and halogenated alkane sulfonic acid, such as trifluoromethayl sulfonic acid.Also benzene sulfonic acid or C can be used
1-C
20alkyl benzene sulphonate, such as toluenesulfonic acid, nonylbenzene sulfonic acid and DBSA.Suitable is inorganic in addition
acid, such as HCl, H
2sO
4or HClO
4.Lewis acid used can preferred particularly BF
3, BCl
3, SnCl
4, TiCl
4and AlCl
3.The lewis acid that also can use the lewis acid of complex combination or be dissolved in ionic liquid.
Be polymerized also available bases catalysis.Such as can use the alkoxide of alkali metal and/or alkaline-earth metal, hydroxide, phosphate, carbonate and/or bicarbonate, and ammonia and/or primary, secondary and/or tertiary amine, or its mixture.The example of alkali is sodium methoxide, caustic alcohol, potassium tert-butoxide or magnesium ethylate, NaOH, KOH, LiOH, Ca (OH)
2, Ba (OH)
2, Na
3pO
4, Na
2cO
3, K
2cO
3, Li
2cO
3, (CH
3)
3n, (C
2h
5)
3n, morpholine, dimethylaniline and piperidines.Usually, alkali is with the weight 0.1-10 % by weight based on Compound I, the especially amount of 0.2-5 % by weight, and such as the maximum of 4 or 3 or 2 or 1 % by weight uses at the most.
Due to economic cause, catalyst is only with needed for catalysis, and the weight usually based on Compound I is not more than 10 % by weight, and the amount being such as not more than 4 or 3 or 2 or 1 % by weight uses.Bronsted lowry acids and bases bronsted lowry containing (partly) metal also can be used as compound III.In this case, they use with the amount described about compound III.
Polymerization also can heat cause, and this means to be polymerized the acid or the alkali that preferably do not add catalytic amount in this case, is undertaken by being heated under the existence of compound III by the mixture of Compound I and Compound II per.Temperature needed for polymerization is generally 50-250 DEG C, especially 80-200 DEG C.When acid or base catalyzed polymerization, polymerization temperature is generally 50-200 DEG C, especially 80-150 DEG C.When thermal-initiated polymerization, polymerization temperature is generally 120-250 DEG C, especially 150-200 DEG C.
Can under the pressure of reduction compared with normal pressure on convergence principle of the present invention, such as in a vacuum, under standard pressure or at an elevated pressure, such as, carry out in autoclave.Generally speaking, be aggregated in 0.01-100 bar, preferred 0.1-10 bar, carry out under the pressure that especially 0.5-5 clings to or more preferably 0.7-2 clings to.
On convergence principle can with in batches and/or addition method carry out.When carrying out batch processes, first Compound I, II and III to be loaded in reaction vessel and the condition reached needed for polymerization with aequum.In addition method, feed at least one in Compound I and II in the course of the polymerization process at least in part until obtain required compound I: Compound II per ratio.In this case, can first load in the course of the polymerization process and/or add compound III.It can be the successive reaction stage after adding.
Preferably carry out batch processes.Find advantageously to be polymerized in a single stage, this means to be polymerized and carries out as the Compound I of a collection of whole amount, II and III, or use addition method, wherein adds Compound I by this way and II does not consequently interrupt polymerizing condition until the Compound I of whole amount and II are added in reaction vessel.First load in the course of the polymerization process and/or feed compound III.
Compound I and II under the existence of compound III, convergence principle can carry out in any desired manner, and condition guarantees component mutually reactive.Therefore, reaction can body, such as, with melt, or at reaction medium, carries out under the existence of especially solvent.
It is all solvents of dissolved form wherein at least in part that useful solvent comprises compound III in principle.This be to be understood that mean compound III under polymerization conditions solubility be in a solvent at least 50g/l, especially at least 100g/l.Generally speaking, selective solvent makes the solubility of compound III at normal pressure and 20 DEG C be 50g/l, especially at least 100g/l.More particularly, selective solvent makes compound III be basic or completely soluble, and namely the ratio of selective solvent and compound III makes under polymerization conditions, based on the weight at least 80 % by weight of compound III, especially at least 90 % by weight, or the compound used therefor III of whole amount is dissolved form.
In a preferred variant, polymerization is carried out in a solvent, in this case, at least 60 % by weight of Compound I, II and III total amount, preferably at least 75 % by weight, more preferably at least 90 % by weight, most preferably at least 95 % by weight is dissolved form.
Preferred solvent is alcohol, ether and ketone, especially has the alcohol of 1-8 carbon atom, ether and ketone.The example of suitable alcohols be methyl alcohol, ethanol, normal propyl alcohol and isopropyl alcohol, n-, secondary-, iso-and the tert-butyl alcohol, amylalcohol and hexanol.Suitable also have ring-type (particularly preferably two
alkane, oxolane) and acyclic ethers, such as ethyl methyl ether, dimethyl ether, diethyl ether, methyl tertiary butyl ether(MTBE), Di Iso Propyl Ether and di-n-butyl ether.Suitable ring-type or be acetone, butanone or cyclohexanone without the example of cyclic ketones.Particularly preferred solvent is THF and ethanol.
Substantially the polymerization carrying out Compound I and II under water is there is not particularly preferably under the existence of compound III, this concentration meaning to be polymerized water when starting based on the total weight of Compound I, II and III for being less than 1 % by weight, preferably be less than 0.5 % by weight, be more preferably less than 0.1 % by weight.Polymerization more preferably gets rid of water, namely carries out in anhydrous conditions.
For producing particulate composite, find the reaction usefully carrying out Compound I and Compound II per under the existence of compound III in inert diluent.Preferred inert diluent is the degree of the total amount at least 80 volume % based on diluent, the especially degree of at least 90 volume %, especially the degree of at least 99 volume % or 100 volume % be made up of following component those: above-mentioned hydrocarbon, aromatic hydrocarbons are as single-or many-C
1-C
4alkyl substituted benzene or naphthalene, particularly preferably toluene, dimethylbenzene, cumene or mesitylene, or C
1-C
4alkyl naphthalene, and aliphatic and clicyclic hydrocarbon, such as hexane, cyclohexane, heptane, cycloheptane, octane and isomers thereof, nonane and isomers, decane and isomers thereof, and composition thereof.
Compound I can be purification step and optionally drying step after being polymerized under the existence of compound III with Compound II per.In a method change programme, change the composition of inorganic phase.Such as can reduce by washing and/or purification step the content being derived from the anion of compound III.For this reason, advantageously can use alkali, the alkoxide of such as alkali metal and/or alkaline-earth metal, hydroxide, phosphate, carbonate and/or bicarbonate, and ammonia and/or primary, secondary and/or tertiary amine, or its mixture.The example of alkali is sodium methoxide, caustic alcohol, potassium tert-butoxide or magnesium ethylate, NaOH, KOH, LiOH, Ca (OH)
2, Ba (OH)
2, Na
3pO
4, Na
2cO
3, K
2cO
3, Li
2cO
3, NaHCO
3, KHCO
3, (CH
3)
3n, (C
2h
5)
3n, morpholine, dimethylaniline and piperidines.These alkali also at solvent as in water, alcohol or ether or its mixture, such as, can use in methyl alcohol, ethanol, isopropyl alcohol, diethyl ether or THF.
In addition, the composite material heating that can will be obtained by the inventive method.This is usually at 200-2000 DEG C, preferred 300-1600 DEG C, more preferably 400-1100 DEG C, most preferably carries out at the temperature of 500-900 DEG C.
In one embodiment, carbonization in lower scope, such as, is carried out below 600 DEG C, at the temperature of less than 500 DEG C or 380-400 DEG C.Use this program, the common continuous structure with wide region can be obtained.In another embodiment, carbonization, in higher range, such as, is carried out at the temperature of more than 700 DEG C, more than 800 DEG C or 950-1050 DEG C.Use this program, the metal farmland be separated in the carbon base body of wide region can be produced, in this case, advantageously can use reducing gas.
The duration of heating is variable and depends on factor, comprises temperature when heating.Duration is such as 0.5-50 hour, preferred 1-24 hour, especially 2-12 hour.
Heating in one or more stage, such as, can be carried out in one or two stage.In many cases, heat with 1-10 DEG C/min, preferred 2-6 DEG C/min, namely the speed of such as 2 °, 3 ° or 4 DEG C/min proceeds to temperature required.Cooling can start immediately after this temperature of acquisition, or this temperature can keep 10 minutes to 10 hours.Sustainable such as 0.5 hour, 1 hour, 2 hours, 3 hours, 4 hours or 5 hours of this retention time.Before carbonization method, also heat treatment step can be inserted.This is undertaken by keeping the constant temperature (such as about 200 DEG C or about 250 DEG C) in 100-400 DEG C, preferred 150-300 DEG C temperature range, until heat treatment step completes, and namely such as 1 hour or 2 hours.Also at 100-400 DEG C, in preferred 150-300 DEG C temperature range, the rate of heat addition can be reduced, 1/2 or 1/3 of such as, when starting to the heating selected rate of heat addition.
Heating can get rid of oxygen substantially or completely, preferably carries out under the existence of inert gas and/or reducing gas (reactant gas).In this case, by the organic polymer material carbonization formed in polymerization to obtain carbon phase and to form electroactive material.In a preferred embodiment of the inventive method, polymerization is in a single stage, under standard pressure, basic or complete, preferably gets rid of oxygen completely and carries out.In this context, get rid of oxygen completely and mean carrying out in the gas compartment of being polymerized, exist and be not more than 0.5 volume % based on the mentioned gas compartment, be preferably less than 0.05 volume %, be especially less than the oxygen of 0.01 volume %.In multistage heating means, this step can be carried out under the existence of gas with various and/or at different temperature.Such as, can first, such as heat under the existence of inert gas as argon gas or nitrogen in a first step, then, such as in the second step at reducing gas (reactant gas) as Ar, N
2, H
2, NH
3, CO and C
2h
2and composition thereof as synthesis gas (CO/H
2) and forming gas (N
2/ H
2and/or Ar/H
2) existence under heat.
Compound I and Compound II per can also be the oxidation removal of organic polymer phase after being polymerized under the existence of compound III, make the organic polymer material formed in organic component polymerization be oxidized to obtain nano-pore oxide material.In this case, heating under oxygen, is carried out in its preferred form under the existence of inert gas.In multistage heating means, such as can carry out this step under the existence of gas with various and/or at different temperatures.Such as, can first, such as heat under the existence of inert gas as argon gas or nitrogen in a first step, then, such as in the second step at oxidizing gas as O
2and composition thereof as heated under the existence of air or synthesis of air.
In principle can under a reduced pressure by being polymerized the heating of composite material that obtains, such as under vacuo, under standard pressure or at an elevated pressure, such as, carry out in autoclave.Generally speaking, heat at 0.01-100 bar, preferred 0.1-10 bar, carry out under the pressure that especially 0.5-5 bar or 0.7-2 cling to.Heating can be carried out in closed system or in development system, and the volatile component wherein formed removes in the air-flow preferably comprising at least one inert gas and/or reducing gas.
More particularly, the inventive method is suitable for producing electroactive material with continuous and/or batch mode.In batch mode, this means, more than 10kg, to be preferably greater than 100kg, is especially preferably greater than 1000kg or is greater than the batch of 5000kg.In continuous mode, this means more than 100kg/ days, preferably greater than 1000kg/ days, more preferably above 10 tons/day or output more than 100 ton/day.
In addition, there is disclosed herein composite material (K1), it can such as be obtained by the inventive method and it comprises:
A) at least one (partly) Metal Phase, and
B) at least one organic polymer phase,
Wherein in composite material (K1), the content of each (partly) metal is at least 2 % by weight based on the carbon content of composite material (K1), and at least one organic polymer phase and at least one (partly) Metal Phase form phase domain, the average distance (arithmetic mean of distance) between two adjacent farmlands of wherein phase homophase is determined as by small angle x-ray scattering (SAXS) and is substantially not more than 200nm.In a preferred embodiment, at least one (partly) Metal Phase comprises at least two kinds of different (partly) metals.
" phase homophase " first only means organic polymer phase, secondly only means (partly) Metal Phase.The adjacent phase domain of phase homophase is to be understood that two phase domains meaning the phase homophase separated by another phase phase domain, two phase domains of (partly) Metal Phase particularly preferably separated by a phase domain of organic polymer phase, or two phase domains of the polymer phase of being separated by a phase domain of (partly) Metal Phase.
Average distance between the adjacent phase domain of phase homophase is generally and is not more than 200nm, is usually not more than 100nm or is not more than 50nm, is especially not more than 10nm or is not more than 5nm.Average distance between the farmland of adjacent phase homophase is by small angle x-ray scattering (SAXS) (SAXS), (measure in transmission at 20 DEG C by Scattering of Vector q, monochromatization CuK radiation, 2D detector (image plate), slit collimation) measure.The arrangement of the size of phase region and the Distance geometry phase therefore between two adjacent phase boundaries also by transmission electron microscope (TEM), especially can measure by HAADF-STEM (angle of elevation annular dark field scanning electron microscopy) method.
(partly) Metal Phase can comprise any element forming oxide structure in principle.Preferably (partly) metal, particularly preferably the 1st race (particularly preferably Na of periodic table, K), 2nd race (particularly preferably Ca, Mg), 3rd race (particularly preferably Sc), 4th race (particularly preferably Ti, Zr), 5th race (particularly preferably V), 6th race (particularly preferably Cr, Mo, W), 7th race (particularly preferably Mn), 8th race (particularly preferably Fe, Ru, Os), 9th race (particularly preferably Co, Rh, Ir), 10th race (particularly preferably Ni, Pd, Pt), 11st race (particularly preferably Cu, Ag, Au), 12nd race (particularly preferably Zn, Cd), 13rd race (particularly preferably B, Al, Ga, In), 14th race (particularly preferably Si, Sn) the and 15th race (particularly preferably As, Sb, Bi) oxide of element.In these, preferred (partly) metal Ti, V, Cr, Mo, W, Mn, Fe, Co, Ni, Cu, Zn, B, Si and Sn, particularly preferably (partly) metal Ti, Fe, Co, Cu, Si and Sn.
In composite material of the present invention (K1), the content of each (partly) metal is at least 2 % by weight based on the carbon content of composite material, preferably at least 3 % by weight, more preferably at least 5 % by weight.
In composite material of the present invention (K1), the region that wherein there is co-cable transmission farmland forms the preferred at least 10 volume % of composite material, more preferably at least 30 volume %, even more preferably at least 50 volume %, especially preferably at least 70 volume %, the especially maximum of at least 80 volume % to 100 volume %.
Composite material of the present invention (K1) can easily be processed to obtain electroactive material of the present invention, and described electroactive material can be particularly useful for the electrode of electro-chemical cell.
The present invention also provides composite material (electroactive material), and it comprises:
A) at least one carbon phase, and
B) at least one oxide and/or (partly) Metal Phase,
Wherein in electroactive material, the weight of each (partly) metal is at least 2 % by weight based on the weight of carbon in electroactive material, at least one oxide and/or (partly) Metal Phase form phase domain mutually with at least one carbon, and the average distance (arithmetic mean of distance) between two adjacent farmlands of phase homophase is determined as by small angle x-ray scattering (SAXS) and is substantially not more than 10nm and/or at least one oxide and/or (partly) Metal Phase and forms average diameter (arithmetic mean of diameter) and be determined as the phase domain being not more than 20 μm by small angle x-ray scattering (SAXS).In a preferred embodiment, at least one oxide and/or (partly) Metal Phase comprise at least two kinds of different (partly) metals.
" phase homophase " first only means carbon phase, secondly only means oxide and/or (partly) Metal Phase.The adjacent phase domain of phase homophase is to be understood that two phase domains meaning the phase homophase separated by another phase phase domain, two phase domains of the carbon phase of particularly preferably being separated by a phase domain of oxide and/or (partly) Metal Phase, or two phase domains of the oxide separated by a phase domain of carbon phase and/or (partly) Metal Phase.Average distance between the adjacent phase domain of phase homophase is generally and is not more than 10nm, is usually not more than 7nm, is especially not more than 5nm, be preferably not more than 3nm.Oxide and/or (partly) metal phase domain usually have and are not more than 20 μm, are preferably not more than 2 μm, even more preferably no more than 500nm, are especially not more than the average diameter of 100nm.
The average diameter of the average distance between the farmland of adjacent phase homophase and at least one oxide and/or (partly) Metal Phase is by HAADF-STEM or by small angle x-ray scattering (SAXS), (measure in transmission at 20 DEG C by Scattering of Vector q, monochromatization CuK radiation, 2D detector (image plate), slit collimation) measure.
In electroactive material of the present invention, there are cumulative volume preferably at least 10 volume %s, more preferably at least 30 volume %s, the even more preferably at least 50 volume %s of scope formation based on electroactive material on co-cable transmission farmland, especially preferably at least 70 volume %, especially at least 80 volume % to 100 volume %.
At least one oxide and/or (partly) Metal Phase, in principle for oxide phase, can comprise any element forming oxide.For at least one oxide and/or (partly) Metal Phase, the preferably oxide of (partly) metal and/or (partly) metal, more preferably periodic table the 1st race (particularly preferably Na, K), 2nd race (particularly preferably Ca, Mg), 3rd race (particularly preferably Sc), 4th race (particularly preferably Ti, Zr), 5th race (particularly preferably V), 6th race (particularly preferably Cr, Mo, W), 7th race (particularly preferably Mn), 8th race (particularly preferably Fe, Ru, Os), 9th race (particularly preferably Co, Rh, Ir), 10th race (particularly preferably Ni, Pd, Pt), 11st race (particularly preferably Cu, Ag, Au), 12nd race (particularly preferably Zn, Cd), 13rd race (particularly preferably B, Al, Ga, In), 14th race (particularly preferably Si, Sn) the and 15th race (particularly preferably As, Sb, Bi) (partly) metal of element and/or the oxide of (partly) metal.In these, preferred (partly) metal Ti, V, Cr, Mo, W, Mn, Fe, Co, Ni, Cu, Zn, B, Si and Sn, particularly preferably (partly) metal Ti, Fe, Co, Cu, Si and Sn.
At least one carbon mutually in, carbon back this exist with element form, namely mutually in non-carbon, the content of such as N, O, S, P and/or H for being less than 10 % by weight, is especially less than 5 % by weight based on the total amount of carbon in mutually.The content of mutually middle non-carbon measures by x-ray photoelectron spectroscopy (X ray PES).Due to preparation, outside de-carbon, carbon can comprise a small amount of N, O and/or H by it mutually.The mol ratio of H and C is no more than the value of 1:2 usually, especially the value of 1:3, especially the value of 1:4.Value can also be 0 or basic 0, such as, be less than or equal to 0.1.
Carbon mutually in, carbon may mainly exist with amorphous or form of graphite, combines as studied by X ray PES and can (284.5eV) and characteristic asymmetric signal shape infer based on characteristic.The carbon of form of graphite is to be understood that and means carbon at least in part to exist the typical hexagon layer arrangement of graphite, and its middle level for curve or can also come off.
The content comprising each (partly) metal in the electroactive material of the present invention of at least one carbon phase is at least 2 % by weight based on the weight of carbon in composite material, preferably at least 3 % by weight, more preferably at least 5 % by weight.
The advantage of composite material of the present invention (K1) and electroactive material of the present invention be they can in a straightforward manner, reproducible quality and commercial scale, the enforceability of producing in reliable and cheap mode and hold facile raw material and produce.
The present invention further provides the purposes of electroactive material of the present invention as the partial electrode of electro-chemical cell, and comprise the electro-chemical cell electrode (hereinafter also referred to as anode) of electroactive material of the present invention.
Due to its composition and the concrete arrangement of at least one carbon phase (a) and at least one oxide and/or (partly) Metal Phase (b), electroactive material of the present invention is particularly useful as in lithium ion battery, the anode material especially in lithium rechargeable battery or battery pack.Particularly for lithium ion battery, when in the anode of especially lithium rechargeable battery, it should be noted that high power capacity and good cyclical stability, and guarantee the Low ESR in battery.In addition, may owing to specifically arranging mutually, it has high mechanical stability.In addition, it can in a straightforward manner and with reproducible quality by hold facile raw material produce.
Except electroactive material of the present invention, anode comprises the suitable adhesive of at least one usually to reinforce electroactive material of the present invention, and optionally other conducts electricity or electroactive component.In addition, anode has electric contact usually for the supply of electric charge with remove.The amount of electroactive material of the present invention, based on the gross mass of anode material, deducts any current-collector and electric contact, is generally at least 40 % by weight, is usually at least 50 % by weight, and especially at least 60 % by weight.
Other conduction useful in anode of the present invention or electroactive component comprise carbon black (conductive black), graphite, carbon fiber, carbon nano-fiber, carbon nano-tube or conducting polymer.Usually, about 2.5-40 % by weight electric conducting material and 50-97.5 % by weight, usual 60-95 % by weight electroactive material of the present invention is used in anode, and the numeral represented with % by weight, based on the gross mass of anode material, deducts any current-collector and electric contact.
Useful adhesive for using electroactive material of the present invention to produce anode especially comprises following polymeric material:
Polyethylene glycol oxide, cellulose, carboxymethyl cellulose, polyvinyl alcohol, polyvinylidene fluoride, polyethylene, polypropylene, polytetrafluoroethylene, polyacrylonitrile-methylmethacrylate copolymer, Styrene-Butadiene, tetrafluoraoethylene-hexafluoropropylene copolymer, vinylidene difluoride-hexafluoropropylene copolymer, vinylidene fluoride-TFE copolymer, perfluoroalkyl vinyl ether copolymer, ethylene-tetrafluoroethylene copolymer, vinylidene fluoride-chlorotrifluoroethylcopolymer copolymer, ethene-chlorine fluoride copolymers, the ethylene-acrylic acid copolymer that optional alkali metal salt or ammonia neutralize at least partly, the ethylene-methacrylic acid copolymer that optional alkali metal salt or ammonia neutralize at least partly, ethene-(methyl) acrylate copolymer, polyimides and/or polyisobutene and composition thereof.
The selection of adhesive usually consider for the production of the performance of any solvent carry out.Such as, when N-ethyl-2-pyrrolidone is used as solvent, polyvinylidene fluoride is suitable.Adhesive uses with the amount of the gross mass 1-10 % by weight based on anode material usually.Preferred use 2-8 % by weight, especially 3-7 % by weight.
Comprise the electrode of the present invention of electroactive material of the present invention, hereinbefore also referred to as anode, usually comprise electric contact such as, for the supply of electric charge with remove, output conductor, it can with the form configuration of wire, metallic grid, wire netting, expanding metal, metal forming and/or sheet metal.Suitable metal forming especially Copper Foil.
In one embodiment of the invention, the thickness that anode has based on eliminating output conductor is 15-200 μm, the thickness of preferred 30-100 μm.
Anode can pass through as produced by standard method known in relevant monograph in common mode itself.Such as, electroactive material of the present invention mixes with other component optional (conductive component and/or organic bond) of anode material by optional with an organic solvent (such as 1-METHYLPYRROLIDONE, N-ethyl-2-pyrrolidone or hydrocarbon solvent) by anode, and optionally makes it stand forming method or it be applied over inert metal paper tinsel as Cu paper tinsel is produced.Optionally dry after this.This such as uses the temperature of 80-150 DEG C to carry out.Drying process also can be carried out under a reduced pressure and usually continue 3-48 hour.Optionally, also can use melting or sintering method shaping.
The present invention further provides and comprise at least one electro-chemical cell by electrode material described above or the electrode that uses electrode material described above to produce, especially lithium rechargeable battery.
This kind of battery has at least one anode of the present invention usually, and negative electrode is especially suitable for the negative electrode of lithium ion battery, electrolyte and optional spacers.
About suitable cathode material, suitable electrolyte, suitable spacer and possible arrangement, with reference to related art (for example, see people such as Wakihara: Lithium Ion Batteries, 1st edition, Wiley VCH, Weinheim (1998); David Linden:Handbook of Batteries, the 3rd edition, McGraw-Hill Professional, New York (2008); J.O.Besenhard:Handbook of Battery Materials, Wiley-VCH (1998)).
Useful negative electrode especially comprises those negative electrodes, wherein cathode material comprises lithium transition-metal oxide, such as 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, such as LiFePO4.But, comprise those cathode materials of sulphur if the present invention uses and comprise the polymer of polysulfide bridge, then must guarantee anode before this kind of electro-chemical cell can discharge and recharge with Li
0.
Two electrodes, namely anode and negative electrode use liquid or solid electrolyte to be interconnected.Useful liquid electrolyte especially comprises the non-aqueous solution (water content is less than 20ppm usually) of lithium salts and melting Li salt, such as lithium hexafluoro phosphate, lithium perchlorate, hexafluoroarsenate lithium, trifluoromethyl sulfonic acid lithium, two (trimethyl fluoride sulfonyl) imide li or LiBF4, especially lithium hexafluoro phosphate or LiBF4 at suitable aprotic solvent as ethylene carbonate, propylene carbonate and the mixture with one or more following solvents thereof: dimethyl carbonate, ethyl methyl carbonate, diethyl carbonate, dimethoxy-ethane, methyl propionate, ethyl propionate, butyrolactone, acetonitrile, ethyl acetate, methyl acetate, toluene and dimethylbenzene, solution in the mixture of especially ethylene carbonate and diethyl carbonate.Solid electrolyte used can be such as ionic conduction polymer.
Can arrange in-between the electrodes with the spacer of liquid electrolyte dipping.Example especially glass fibre non-woven and the porous organic polymer membrane of spacer, the perforated membrane of such as polyethylene, polypropylene etc.
Specially suitable material for spacer is polyolefin, especially porous polyethylene membrane and porous polypropylene film.
Polyolefin spacer, is especially made up of polyethylene or polypropylene, can have the porosity of 35-45%.Suitable aperture is such as 30-500nm.
In another embodiment of the present invention, the spacer be made up of the PETG being filled with inorganic particle can be there is.This kind of spacer can have the porosity of 40-55%.Suitable aperture is such as 80-750nm.
Electro-chemical cell of the present invention comprises shell further, and described shell can have any shape, such as cube, or cylindrical shape.In another embodiment, electro-chemical cell of the present invention has prism shape.In a change programme, shell used is the metal-plastic composite membrane being specifically described as bag.
Battery can have such as prismatic film structure, and wherein solid thin film electrolyte is arranged between the film forming oxygen base and the film forming negative electrode.Central cathode output conductor is arranged between each cathodic coating to form double-side cell structure.In another embodiment, can use one side battery structure, wherein single negative electrode output conductor is appointed as single anode/separator/cathode element combinations.In the structure shown here, dielectric film is arranged between independent anode/separator/cathode/output conductor element combinations usually.
Electro-chemical cell of the present invention has high power capacity, cyclical stability, efficiency and reliability, good mechanical stability and Low ESR.
Electro-chemical cell of the present invention is capable of being combined forms Li-ion batteries piles.
Therefore, the present invention also provides the purposes of electro-chemical cell of the present invention described above in Li-ion batteries piles further.
The present invention further provides the Li-ion batteries piles comprising at least one electro-chemical cell of the present invention described above.Electro-chemical cell of the present invention in Li-ion batteries piles of the present invention, such as, can be connected in series or is connected in parallel mutual combination.Preferably be connected in series.
Electro-chemical cell of the present invention it should be noted that extra high capacity, high power even after recharge and the battery obviously postponed dead.Electro-chemical cell of the present invention is highly suitable in device.Electro-chemical cell of the present invention purposes in the devices also forms a part for present subject matter.Device can be fixing or moving device.Moving device is the vehicles of (particularly preferably ship and ship) in (particularly preferably aircraft) and water in such as land (particularly preferably automobile and bicycle/tricycle), air.In addition, moving device also has mobile utensil, such as mobile phone, kneetop computer, digital camera, implantable medical apparatus and power tool, especially from building field, such as drilling machine, battery-powered screwdriver and battery-powered tacker.Immobilising device is such as fixed energies memory, such as, for wind energy and solar energy, and fixing electric device.This kind of purposes forms another part of present subject matter.
Li-ion batteries piles of the present invention in the devices, such as, compared with the long running time with in the advantage extending less energy loss in process running time before purposes is within the appliance provided in and recharges.If identical running time realizes compared with the electro-chemical cell of low energy densities to have, then electro-chemical cell must accept higher weight.In addition, Li-ion batteries piles of the present invention can be used as little and light weight batteries group and uses.Li-ion batteries piles of the present invention is noticeable also has high power capacity and cyclical stability, and due to low thermal sensitivity and self-discharge rate, they have high reliability and efficiency.In addition, Li-ion batteries piles can use safely and produce cheaply.In addition, Li-ion batteries piles of the present invention demonstrates favourable electrokinetic property, and this is particularly advantageous when electro-motive vehicle and motor vehicle driven by mixed power.
Set forth the present invention by following examples, but these do not limit the present invention.
Production example 1:
1a) the production of composite material (K1.1)
First 50g tetraphenoxy-silicane alkane and 16.5g tri-is loaded
alkane melting at 70 DEG C.Then by 28.5g SnCl
2to be dissolved in 70ml THF and and melt homogenization.This solution is dropwise added in the mixture of 200ml and 2.5g Loprazolam at 100 DEG C.Be settled out white solid, collect it and use toluene and hexanes wash.After drying, 40g white powder is obtained.By it with sodium bicarbonate solution, water and methyl alcohol process, then dry.
Final weight: 35.3g.
| Elementary analysis | C | H | Si | Cl | Sn |
| Measured value (% by weight) | 54.4 | 4.7 | 9.1 | 0.039 | 4.3 |
1b) the production of electroactive material (higher temperature)
Be heat under the hydrogen of 2-3 l/h at flow velocity in the tube furnace with quartz glass tube by 6g composite material (K1.1).Baking oven is heated to 800 DEG C with 3-4 DEG C/min and keeps 2 hours at 800 DEG C.Flow down at the nitrogen of 1-2 l/h and carry out cool overnight.
This obtains the thin black powder of 3.6g.
| Elementary analysis | C | H | O | Si | Sn |
| Measured value (% by weight) | 52.9 | 1.1 | 20.0 | 15.4 | 7.0 |
Study by tem analysis gained electroactive material sample (see Fig. 1): TEM uses superthin layer method (sample embeds in synthetic resin as matrix) to carry out as HAADF-STEM Tecnai F20 transmission electron microscope under the operating voltage of 200kV.Light tone position is heavier element (herein Sn and Si – (partly) Metal Phase), and dark-coloured position is rich carbon (carbon phase), proves that farmland spacing is in several nm (being not more than 10nm) scope thus.
1c) the production of electroactive material (lower temperature)
Be heat under the hydrogen of 2-3 l/h at flow velocity in the tube furnace with quartz glass tube by 6.2g composite material (K1.1).Baking oven is heated to 650 DEG C with 3-4 DEG C/min and keeps 2 hours at 650 DEG C.Flow down at the nitrogen of 1-2 l/h and carry out cool overnight.
This obtains the thin black powder of 3.7g.
| Elementary analysis | C | H | O | Si | Sn |
| Measured value (% by weight) | 53.0 | 1.7 | 20.8 | 15.0 | 7.0 |
TEM image is shown in Fig. 2.Arrow characterization position.
1d) the production of electrode
Subsequently by 1b) in the electroactive material that obtains and conductive black (the Super P Li from Timcal) and adhesive (polyvinylidene fluoride KYNAR
2801) mixing using obtain N-ethyl-2-pyrrolidone as in solvent by 87 % by weight 1b) in the adherent coatings that forms of gained electroactive material, 6 % by weight conductive blacks and 7 % by weight adhesives.The amount of solvent for use is 125 % by weight of solids content used.In order to homogenizing better, coating is stirred 16 hours.Dry at 120 DEG C under a reduced pressure on the copper film using coated rod coating to be applied to thickness 20 μm (purity 99.9%) subsequently.After drying, the electrode obtained (width 8cm) is rolled with the line pressure of 9N/mm, then introduce in argon atmospher (water content <1ppm, oxygen content <10ppm).Before formation battery, by electrode dried overnight again at 5 millibars and 120 DEG C.For forming electrochemical test cell (being similar to the bipolar electrode experimental rig of button cell), stamp out the disk that diameter is 20mm.Lithium paper tinsel is used as electrode.Electrolyte used is the 1M LiPF in the 1:1 mixture of ethylene carbonate and ethyl methyl carbonate
6.For electrochemical Characterization, battery is connected in Maccor series 4000 battery cyclic devices.Make battery under the ratio electric current of 30mA/g active material relative to Li/Li
+circulate between 10mV and 2V.After acquisition 10mV, by voltages keep constant 30 minutes.
Fig. 3 shows the discharge capacity of two batteries through 40 circulations.The capacity realized is more than the attainable value of graphite.The curve profile that two batteries are substantially identical clearly shows from 1d) the well reproduced of electrode.
Fig. 4 shows the figure of differential capacitance relative to voltage.The measurement data of institute's indicating value origin self clock ampere analytic approach calculates.In chronoamperometry, limit constant current and the change of recording voltage.Gained differential capacitance is admitted about characteristic electrochemical method relative to the figure of voltage, being incorporated to or discharging or the statement of electrolytical decomposition of such as lithium.Tin under 0.4V (lithium and tin be incorporated to or alloy is formed: negative y-axis) and between 0.6-0.8V the characteristic peak of the electro-chemical activity at (3 peaks about the lithium from lithium-ashbury metal extracts: just y-axis) be obviously.
Fig. 4: from 1d) the differential capacitance of electrode under the voltage of 0-2V.
Production example 2: the production of composite material (K1.2)
First 50g tetraphenoxy-silicane alkane and 16.5g tri-is loaded
alkane melting at 70 DEG C.Then by 13.45g CuCl
2to be dissolved in 100ml ethanol and and melt homogenization.This solution is dropwise added in the mixture of 500ml toluene and 2.5g Loprazolam at 100 DEG C.Be settled out violet solid, it collected and uses toluene and hexanes wash.After drying, 40g white powder is obtained.Stirred by powder sodium bicarbonate solution, suction strainer goes out, by water and methanol wash, then dry.
Final weight: 46.7g
| Elementary analysis | C | H | Si | Cu |
| Measured value (% by weight) | 56.4 | 4.5 | 6.0 | 6.0 |
Production example 3:
3a) the production of composite material (K1.3)
By 25g tetraphenoxy-silicane alkane, 8.25g tri-
alkane and the melting of 13g tetraethoxysilane.This solution is dropwise added in the mixture of 250ml dimethylbenzene and 2.5g Loprazolam at 100 DEG C.Be settled out pink solid, it collected and uses toluene and hexanes wash, then dry.
Final weight: 28g
| Elementary analysis | C | H | Si | O |
| Measured value (% by weight) | 58.5 | 5.0 | 10.2 | 25.6 |
3b) the production (lower temperature) of electroactive material
Be heat under the hydrogen of 2-3 l/h at flow velocity in the tube furnace with quartz glass tube by 3.9g composite material (K1.3).Baking oven is heated to 800 DEG C with 3-4 DEG C/min, and keeps 2 hours at 800 DEG C.Flow down at the nitrogen of 1-2 l/h and carry out cool overnight.
This obtains the thin black powder of 2.2g.
| Elementary analysis | C | H | O | Si |
| Measured value (% by weight) | 54.9 | 1.2 | 25.0 | 19.1 |
3c) the production (higher temperature) of electroactive material
Be heat under the hydrogen of 2-3 l/h at flow velocity in the tube furnace with quartz glass tube by 3.8g composite material (K1.3).Baking oven is heated to 980 DEG C with 3-4 DEG C/min, and keeps 2 hours at 980 DEG C.Flow down at the nitrogen of 1-2 l/h and carry out cool overnight.
This obtains the thin black powder of 2.1g.
| Elementary analysis | C | H | O | Si |
| Measured value (% by weight) | 55.6 | 0.7 | 24.0 | 19.6 |
Claims (17)
1. produce the method for composite material, described composite material comprises:
A) at least one (partly) Metal Phase, and
B) at least one organic polymer phase,
Described method comprises to be made
-at least one aryloxy group (partly) metal acid-salt and/or form the nonmetallic aryloxy group ester of oxyacid, wherein nonmetal be different from carbon and nitrogen (Compound I) with
-at least one ketone, formaldehyde and/or formaldehyde equivalent (Compound II per) exist
-at least one is not copolymerization under the existence of aryloxy group (partly) metal acid-salt (partly) metallic compound (compound III),
(partly) weight metal wherein in compound III is at least 5 % by weight based on the weight of Compound I.
2. method according to claim 1, is wherein dissolved in compound III in reaction medium.
3., according to the method for claim 1 and/or 2, wherein compound III is added in the melt of Compound I and II.
4. the method any one of aforementioned claim, wherein compound III comprises Ti, Fe, Co, Cu, Si and/or Sn as (partly) metal.
5. the method any one of aforementioned claim, wherein compound III is Fe (CH
3cOO)
2, CoCl
2, CuCl
2, SnCl
2, FeCl
3, Si (OCH
3)
4, TiCl
4and/or SnCl
4.
6. the method any one of aforementioned claim, wherein Compound I is described by general formula I:
[(AryO)
mMO
nR
p]q (I)
Wherein:
What M was (partly) metal or formation oxyacid is different from the nonmetal of carbon and nitrogen;
M is integer and is 1,2,3,4,5 or 6,
N is integer and is 0,1 or 2,
P is integer and is 0,1,2 or 3,
Q is the integer of 1-20,
M+2n+p is integer, is 1,2,3,4,5 or 6 and is equivalent to the chemical valence of M,
Ary is phenyl or naphthyl, and wherein phenyl ring or naphthalene nucleus are not substituted or can have one or more substituting group, and described substituting group is selected from alkyl, cycloalkyl, alkoxyl, cycloalkyloxy and NR
ar
b, wherein R
aand R
bbe hydrogen, alkyl or cycloalkyl independently of one another;
R is hydrogen, alkyl or cycloalkyl, thiazolinyl, cycloalkyl or aryl, and wherein aryl is not substituted or can has one or more substituting group, and described substituting group is selected from alkyl, cycloalkyl, alkoxyl, cycloalkyloxy and NR
ar
b, wherein R
aand R
bseparately as hereinbefore defined.
7. the method any one of aforementioned claim, wherein heats gained copolymer.
8. the method any one of aforementioned claim, wherein makes oxidation or reducing agent act on gained copolymer.
9. composite material, it comprises:
A) at least one (partly) Metal Phase, and
B) at least one organic polymer phase
Wherein at least one (partly) Metal Phase comprises at least two kinds of different (partly) metals, in composite material, the weight of each (partly) metal is at least 2 % by weight based on the weight of carbon in composite material, at least one organic polymer phase and at least one (partly) Metal Phase form phase domain, and the average distance (arithmetic mean of distance) between two of phase homophase adjacent farmlands is determined as by small angle x-ray scattering (SAXS) and is substantially not more than 200nm.
10. composite material, it comprises:
A) at least one carbon phase, and
B) at least one comprises oxide phase and/or (partly) Metal Phase of at least two kinds of differences (partly) metal,
Wherein in composite material, the weight of each (partly) metal is at least 2 % by weight based on the weight of carbon in composite material, at least one oxide phase and/or (partly) Metal Phase form phase domain mutually with at least one carbon, the average distance (arithmetic mean of distance) between two adjacent farmlands of phase homophase by small angle x-ray scattering (SAXS) be determined as substantially be not more than 10nm and/or oxide and/or (partly) Metal Phase basically form by small angle x-ray scattering (SAXS) measure average diameter (arithmetic mean of the diameter) phase domain for being not more than 20 μm.
11. composite materials according to claim 10 are as the purposes of the partial electrode of electro-chemical cell.
12. for the electrode of electro-chemical cell, and it comprises composite material according to claim 10.
13. electro-chemical cells comprising at least one electrode according to claim 12.
14. according to the purposes of electro-chemical cell in Li-ion batteries piles of claim 13.
15. Li-ion batteries piles comprising at least one electro-chemical cell according to claim 13.
16. electro-chemical cells according to claim 13 purposes in the devices.
17. devices comprising at least one electro-chemical cell according to claim 13.
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|---|---|---|---|
| EP12173568 | 2012-06-26 | ||
| EP12173568.2 | 2012-06-26 | ||
| PCT/IB2013/054939 WO2014001949A1 (en) | 2012-06-26 | 2013-06-17 | Composite materials and method for the production thereof |
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| CN104412422A true CN104412422A (en) | 2015-03-11 |
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|---|---|
| EP (1) | EP2865033A4 (en) |
| JP (1) | JP2015522681A (en) |
| KR (1) | KR20150032308A (en) |
| CN (1) | CN104412422A (en) |
| WO (1) | WO2014001949A1 (en) |
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| CN109238312A (en) * | 2018-09-07 | 2019-01-18 | 浙江理工大学 | A kind of preparation method of composite fibre base flexible piezoelectric sensors |
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| JP5503858B2 (en) * | 2008-09-22 | 2014-05-28 | 株式会社東芝 | Negative electrode active material for non-aqueous electrolyte battery and non-aqueous electrolyte battery |
| JP2010282942A (en) * | 2009-06-08 | 2010-12-16 | Tohoku Univ | Electrode material and manufacturing method of electrode material |
| KR101126202B1 (en) * | 2010-11-04 | 2012-03-22 | 삼성에스디아이 주식회사 | Negative active material for rechargeable lithium battery and rechargeable lithium battery comprising same |
| JP2014506608A (en) * | 2011-01-19 | 2014-03-17 | ビーエーエスエフ ソシエタス・ヨーロピア | Manufacturing method of composite material |
| US20120184702A1 (en) * | 2011-01-19 | 2012-07-19 | Basf Se | Process for producing a composite material |
| WO2013110985A1 (en) * | 2012-01-23 | 2013-08-01 | Basf Se | Composite, its production and its use in separators for electrochemical cells |
| US8865858B2 (en) * | 2012-06-26 | 2014-10-21 | Basf Se | Process for producing a composite material |
| US20130341559A1 (en) * | 2012-06-26 | 2013-12-26 | Basf Se | Composite materials and process for production thereof |
| SG11201408570TA (en) * | 2012-06-26 | 2015-01-29 | Basf Se | Process for producing a composite material |
-
2013
- 2013-06-17 KR KR1020157001719A patent/KR20150032308A/en not_active Application Discontinuation
- 2013-06-17 WO PCT/IB2013/054939 patent/WO2014001949A1/en active Application Filing
- 2013-06-17 JP JP2015519401A patent/JP2015522681A/en active Pending
- 2013-06-17 EP EP13809585.6A patent/EP2865033A4/en not_active Withdrawn
- 2013-06-17 CN CN201380034016.8A patent/CN104412422A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4055546A (en) * | 1971-10-29 | 1977-10-25 | Hitachi Chemical Company, Ltd. | Novel thermosetting resins and process for preparing the same |
| EP1032062A1 (en) * | 1999-02-23 | 2000-08-30 | Hitachi, Ltd. | Negative electrode-active material used in lithium secondary battery |
| US7094499B1 (en) * | 2003-06-10 | 2006-08-22 | The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration | Carbon materials metal/metal oxide nanoparticle composite and battery anode composed of the same |
| CN102388106A (en) * | 2009-04-03 | 2012-03-21 | 巴斯夫欧洲公司 | Method for producing composite material |
| CN102388488A (en) * | 2009-04-03 | 2012-03-21 | 巴斯夫欧洲公司 | Electroactive material, and use thereof in anodes for lithium-ion cells |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109238312A (en) * | 2018-09-07 | 2019-01-18 | 浙江理工大学 | A kind of preparation method of composite fibre base flexible piezoelectric sensors |
| CN109238312B (en) * | 2018-09-07 | 2021-03-23 | 浙江理工大学 | Preparation method of composite fiber-based flexible piezoelectric sensor |
Also Published As
| Publication number | Publication date |
|---|---|
| EP2865033A4 (en) | 2016-04-27 |
| JP2015522681A (en) | 2015-08-06 |
| KR20150032308A (en) | 2015-03-25 |
| WO2014001949A1 (en) | 2014-01-03 |
| EP2865033A1 (en) | 2015-04-29 |
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