CN1518544A - Piperazine derivative, process for producing the same, polymeric solid electrolyte and secondary battery - Google Patents

Piperazine derivative, process for producing the same, polymeric solid electrolyte and secondary battery Download PDF

Info

Publication number
CN1518544A
CN1518544A CNA018233686A CN01823368A CN1518544A CN 1518544 A CN1518544 A CN 1518544A CN A018233686 A CNA018233686 A CN A018233686A CN 01823368 A CN01823368 A CN 01823368A CN 1518544 A CN1518544 A CN 1518544A
Authority
CN
China
Prior art keywords
methyl
compound
solid electrolyte
formula
piperazine derivatives
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CNA018233686A
Other languages
Chinese (zh)
Inventor
青木忍
辅
石德武
志
诧摩启辅
信
大西仁志
昌弘
野木荣信
鸟井田昌弘
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Mitsui Chemicals Inc
Mitsui Chemical Industry Co Ltd
Original Assignee
Mitsui Chemical Industry Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Mitsui Chemical Industry Co Ltd filed Critical Mitsui Chemical Industry Co Ltd
Priority claimed from PCT/JP2001/005131 external-priority patent/WO2002102786A1/en
Publication of CN1518544A publication Critical patent/CN1518544A/en
Pending legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
    • C07D295/02—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms containing only hydrogen and carbon atoms in addition to the ring hetero elements
    • C07D295/027—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms containing only hydrogen and carbon atoms in addition to the ring hetero elements containing only one hetero ring
    • C07D295/03—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms containing only hydrogen and carbon atoms in addition to the ring hetero elements containing only one hetero ring with the ring nitrogen atoms directly attached to acyclic carbon atoms
    • 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
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
    • 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Dispersion Chemistry (AREA)
  • General Physics & Mathematics (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Secondary Cells (AREA)

Abstract

A novel piperazine derivative which is suitable for use as a hardener or crosslinking agent; a polymeric solid electrolyte which is obtained with the piperazine derivative and has high ionic conductivity and electrochemical stability; and a secondary battery employing the polymeric solid electrolyte. The piperazine derivative is novel piperazine derivative having per molecule two or more groups represented by the following formula: wherein R1 to R6 each is hydrogen or lower alkyl; and X is oxygen, sulfur, or NR6.

Description

Bridged piperazine derivatives, its manufacture method, polymer solid electrolyte and secondary cell
Technical field
The present invention relates to novel bridged piperazine derivatives and manufacture method thereof, have the polymer solid electrolyte that uses the premium properties that this bridged piperazine derivatives obtains and use this electrolytical secondary cell.
Background technology
Up to now, as the solidifying agent of epoxy or acrylate, use polyamines.Wherein, aliphatic polyamine has high reactivity, therefore has and can carry out the such availability of ambient cure.But,, also have vapour pressure height, the strong such problem of skin irritation for present aliphatic polyamine.
Present known aliphatic polyamine, it is primary amine mostly, though be reactive high, also having in ambient cure needs long-time such shortcoming.
The inventor is under such situation, and from hyperergy, the such viewpoint of low irritant, the exploitation of the solidifying agent of deeply improveing consequently, has found to have the bridged piperazine derivatives of the novelty of premium properties.
On the other hand, in electrochemical elements such as present primary cell, secondary cell, electrical condenser, use liquid electrolyte.If but use liquid electrolyte, owing to worry leakage, therefore, require to carry out in order to improve the improvement of reliability utilizing aspect the electrochemical element from product.
As a kind of improving one's methods wherein, studying the method that replaces liquid electrolyte and use solid electrolyte.If the use solid electrolyte does not just have the worry of leakage, so when the high element of reliability can be provided, small-sized, the light-weighted advantage that can seek element self is simultaneously arranged also.But in general, the ionic conduction degree of solid electrolyte is lower than liquid electrolyte, therefore is difficult to make the good battery of charge-discharge characteristic.
In recent years, even in solid electrolyte, polymer solid electrolyte also has pliability, thereby infers on the volume change that produces in electrode-electric is separated ion electronics exchange procedure between matter and also can flexibly adapt to, therefore gazed at, studied.
As such polymer solid electrolyte, proposed to have the mixture of an alkali metal salt of the polyoxyethylene of polyether structure and lithium salts etc., the diester compound of polyoxyalkylene, the ester cpds of polymethoxy oxyalkylene, and the cross-linked resin that constitutes with the multipolymer of oxycompound with two keys and inorganic salt are as the polymer solid electrolyte (spy opens flat 5-25353 number) of main constituent, by having the polymer solid electrolyte (spy opens flat 6-223842 number) that organic polymer material and the metal-salt of carbonate group as the functional group constitutes, polycarbonate dimethacrylate acrylate resin (spy opens flat 1-241764 number) or the like.
The inventor finds, uses oneself discovery novelty bridged piperazine derivatives and the polymer substance that obtains can provide the polymer solid electrolyte with premium properties.
Summary of the invention
The object of the present invention is to provide a kind of be suitable as solidifying agent or linking agent, the high and low pungency of vapour pressure and bridged piperazine derivatives with good reactive novelty.
The object of the present invention is to provide a kind of manufacture method of bridged piperazine derivatives of such novelty.
The object of the present invention is to provide a kind of use that above-mentioned bridged piperazine derivatives obtains have the macroion conductivity and keep the polymer solid electrolyte of electrochemical stability simultaneously.
In addition, the object of the present invention is to provide a kind of use that above-mentioned bridged piperazine derivatives obtains, low-cost, gel acceleration big and also with the reactive low polymer solid electrolyte of electrode.
The present invention also aims to provide a kind of secondary cell that uses such polymer solid electrolyte.
The invention provides a kind of compound that in 1 molecule, has 2 above piperazine skeletons, promptly in 1 molecule, have the bridged piperazine derivatives of the novelty of the base of representing with following formula (I) more than 2.
In the formula, R 1, R 2, R 3, R 4And R 5, can be identical, also can be different, expression hydrogen atom or low alkyl group; X represents Sauerstoffatom, sulphur atom or NR 6R 6Expression hydrogen atom or low alkyl group.* represent binding site (following identical).
The invention provides a kind of excellent process that can access the bridged piperazine derivatives of such novelty.
The invention provides a kind of polymer solid electrolyte, this polymer solid electrolyte in utilizing above-mentioned bridged piperazine derivatives and in molecule, having the formed polymkeric substance of Michael reaction of (methyl) more than 2 acrylate-based compound (X), the metal-salt that contains periodic table of elements IA family constitutes.
The present invention also provides a kind of secondary cell that uses such polymer solid electrolyte.
Embodiment
The inventor has carried out research in depth in order to solve above-mentioned problem, found that to have the compound of the base that is made of specific piperazine more than 2 in 1 molecule, has excellent characteristic as solidifying agent or linking agent, thereby has finished the present invention.
The bridged piperazine derivatives of novelty provided by the present invention is the compound that has the base of representing with following formula (I) more than 2 in 1 molecule.
Figure A0182336800071
In the formula, R 1, R 2, R 3, R 4And R 5, can be identical, also can be different, expression hydrogen atom or low alkyl group are preferably represented methyl; X represents Sauerstoffatom, sulphur atom or NR 6And, R 6Expression hydrogen atom or low alkyl group.
In the present invention, as low alkyl group, preferred carbonatoms is 1～6 alkyl, and wherein, carbonatomss such as preferable methyl, ethyl, propyl group, butyl are 1～4 alkyl.As particularly preferred low alkyl group, can enumerate methyl and ethyl.
Bridged piperazine derivatives of the present invention, so long as have more than 2 with the compound of the base of above-mentioned formula (I) expression just passablely, this base institute bonded base is had no particular limits, as this base institute bonded base, if enumerate preferred words, can enumerate and to contain heteroatomic alkyl.As heteroatoms, can enumerate oxygen, nitrogen, sulphur etc., but wherein special preferred oxygen.
As containing so heteroatomic alkyl, can enumerate as an example that can to contain heteroatomic carbonatoms be 2～100 alkylidene group.
Therefore, the preference of bridged piperazine derivatives of the present invention can be expressed as the compound of following formula (II).
Figure A0182336800081
In the formula, R is that can to contain heteroatomic carbonatoms be 2～100 alkyl; N is 2～10 integer; R 1, R 2, R 3, R 4And R 5, can be identical, also can be different, expression hydrogen atom or low alkyl group are preferably represented methyl; X represents Sauerstoffatom, sulphur atom or NR 6R 6Be hydrogen atom or low alkyl group.
The R of formula (II) is that can to contain heteroatomic carbonatoms be 2～100 alkyl, but such base both can have ehter bond, ester bond, carbonic acid ester bond or unsaturated link(age), can be again ring structure or branched structure.
As the preferred concrete example of R, can enumerate vinyl, propenyl, butenyl, 2, bases such as 2-dimethyl propylene thiazolinyl, pentenyl, 3-methylpent thiazolinyl, hexenyl, nonene base, cyclodecane base, the base of perhaps using following formula (1)～(9) to represent,
Figure A0182336800082
Perhaps use the base of following formula (10)～(13) expression etc.
*-CH 2CHR 7-(OCH 2CH 2CH 2CH 2) p- * (10)
(in the formula, R 7Expression hydrogen atom or methyl, p represents 1～20 integer.)
*-CH 2CH 2CH 2CH 2-(OCH 2CH 2CH 2CH 2) q- * (11)
(in the formula, q represents 1～20 integer.)
Figure A0182336800091
(in the formula, R 8The expression low alkyl group; R 9, R 10, R 11, can be identical, also can be different, expression hydrogen atom or methyl; R, s, t represent 0～10 integer respectively independently.)
Figure A0182336800092
(in the formula, R 12, R 13, R 14, can be identical, also can be different, expression hydrogen atom or methyl; U, v, w represent 0～10 integer respectively independently.)
As the concrete example of preferred bridged piperazine derivatives of the present invention, can enumerate compound with the chemical formulation of following (14) and (15).
Figure A0182336800093
Manufacture method as bridged piperazine derivatives of the present invention is not limited to these, makes the compound (A) that has the base of representing with following formula (III) more than 2 in 1 molecule but can enumerate
Figure A0182336800094
(in the formula, R 1And X is identical with above-mentioned formula (I)) and react the method for (Michael reaction) with the compound (B) that following formula (IV) is represented.
Figure A0182336800101
(in the formula, R 2, R 3, R 4And R 5(I) is identical with above-mentioned formula.)
In formula (I), R 2, R 3, R 4And R 5Be preferably hydrogen atom or methyl, especially preferably be both hydrogen atom.
Above-claimed cpd (A) is so long as have more than 2 with the compound of the base of formula (III) expression just passable, this base institute bonded base is had no particular limits, but,, can enumerate and to contain heteroatomic alkyl if enumerate preferred words as this base institute bonded base.As heteroatoms, can enumerate oxygen, nitrogen, sulphur etc., wherein preferred oxygen.
As containing so heteroatomic alkyl, can enumerate as an example that can to contain heteroatomic carbonatoms be 2～100 alkylidene group.
Therefore, the preferred example of above-claimed cpd (A) can be expressed as the compound of following formula V.
In the formula, R is that can to contain heteroatomic carbonatoms be 2～100 alkyl; N is 2～10 integer; R 1Expression hydrogen atom or low alkyl group are preferably represented methyl; X represents Sauerstoffatom, sulphur atom or NR 6R 6Expression hydrogen atom or low alkyl group.
Preferred object lesson as compound (A), can enumerate two (methyl) vinylformic acid glycol ester of (methyl) acrylate that is polyvalent alcohol, two (methyl) vinylformic acid glycol ether ester, two (methyl) vinylformic acid triethyleneglycol ester, two (methyl) vinylformic acid Tetraglycol 99 ester, two (methyl) vinylformic acid 1, the 2-propylene glycol ester, two (methyl) vinylformic acid 1, the ammediol ester, two (methyl) vinylformic acid dipropylene glycol ester, two (methyl) vinylformic acid tripropylene glycol ester, two (methyl) vinylformic acid DOPCP, neopentyl glycol hydroxyethyl ester two (methyl) acrylate, two (methyl) vinylformic acid 1, the 3-butanediol ester, two (methyl) vinylformic acid 1, the 4-butanediol ester, two (methyl) vinylformic acid 2-butylene-1, the 4-diol ester, two (methyl) vinylformic acid 1, the 5-pentadiol ester, two (methyl) vinylformic acid 1,6-hexylene glycol ester, two (methyl) vinylformic acid 3-methyl isophthalic acid, the 5-pentadiol ester, two (methyl) vinylformic acid 1,9-nonanediol ester, two (methyl) vinylformic acid 1,10-decanediol ester, two (methyl) vinylformic acid 1, the 4-cyclohexanedimethanoester ester, TriMethylolPropane(TMP) hydroxyethyl ester methyl ether two (methyl) acrylate, tetramethylolmethane two (methyl) acrylate monostearate, dihydroxyphenyl propane two (methyl) acrylate, dihydroxyphenyl propane-EO modification two (methyl) acrylate, Bisphenol F-EO modification two (methyl) acrylate, quinhydrones two (methyl) acrylate, two functional (methyl) acrylate of isocyanuric acid EO modification two (methyl) acrylate etc., perhaps, trimethylolethane trimethacrylate (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, TriMethylolPropane(TMP) EO modification three (methyl) acrylate, TriMethylolPropane(TMP) PO modification three (methyl) acrylate, glycerol PO modification three (methyl) acrylate, tetramethylolmethane three (methyl) acrylate, tetramethylolmethane four (methyl) acrylate, ditrimethylolpropane four (methyl) acrylate, isocyanuric acid EO modification three (methyl) acrylate, ditrimethylolpropane four (methyl) acrylate, Dipentaerythritol five (methyl) acrylate, polyfunctional (methyl) acrylate of Dipentaerythritol six (methyl) acrylate etc.Wherein, preferred Ethylene glycol dimethacrylate, trimethylolpropane trimethacrylate or TriMethylolPropane(TMP) EO modification trimethacrylate.
In addition, other concrete examples of compound (A) can be enumerated (methyl) acrylate of polyether glycol, polyester polyol, polycarbonate polyol.At this, polyether glycol is polyoxyethylene glycol, polypropylene glycol, gathers 1,4-butyleneglycol or their multipolymer etc.In addition, polyester polyol is to pass through beta-propiolactone, gamma-butyrolactone, δ-Wu Neizhi, the ring-opening polymerization of lactones such as 6-caprolactone and synthetic polyvalent alcohol, perhaps, pass through ethylene glycol, 1, the 2-propylene glycol, 1, ammediol, 1, the 3-butyleneglycol, 1, the 4-butyleneglycol, neopentyl glycol, 1, the 5-pentanediol, 1, the 6-hexylene glycol, the 3-methyl isophthalic acid, the 5-pentanediol, 1, the 8-ethohexadiol, 1, the 9-nonanediol, decamethylene-glycol, glycol ether, dipropylene glycol, 1, the 4-cyclohexanedimethanol, TriMethylolPropane(TMP), trimethylolethane, tetramethylolmethane, ditrimethylolpropane, Dipentaerythritol, glycerol, polyvalent alcohol and propanedioic acid such as minashi sugar alcohol, succsinic acid, pentanedioic acid, hexanodioic acid, fumaric acid, toxilic acid, hexanaphthene-1, the 2-dicarboxylic acid, hexanaphthene-1, the 3-dicarboxylic acid, hexanaphthene-1, the 4-dicarboxylic acid, the cis tetrahydrophthalic acid, phthalic acid, m-phthalic acid, the polycondensation of polycarboxylic acids such as terephthalic acid and synthetic polyvalent alcohol etc.In addition, polycarbonate polyol is to pass through ethylene glycol, glycol ether, triglycol, polyoxyethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, 1, the 3-butyleneglycol, 1, the 4-butyleneglycol, 1, the 5-pentanediol, the 3-methyl isophthalic acid, the 5-pentanediol, 1, the 6-hexylene glycol, 1, the 8-ethohexadiol, 1, two (2-hydroxyl-oxethyl) benzene of 3-, 1,4-(2-hydroxyl-oxethyl) benzene, neopentyl glycol, the 2-methyl isophthalic acid, the 8-ethohexadiol, 1, the 9-nonanediol, 1, the 4-cyclohexanediol, di-alcohols and TriMethylolPropane(TMP)s such as 1,4 cyclohexane dimethanol, trimethylolethane, tetramethylolmethane, ditrimethylolpropane, Dipentaerythritol, glycerol, the polycondensation of polyvalent alcohols such as minashi sugar alcohol and carbonic diester or carbonyl chloride and synthetic polyvalent alcohol.
Have again, object lesson as the compound (A) of base with formula (III), can enumerate 1,2-dithioglycol two (methyl) acrylate, 1,2-dimercaptopropane two (methyl) acrylate, 1,3-dimercaptopropane two (methyl) acrylate, 1,4-succinimide mercaptans two (methyl) acrylate, 1,6-ethanthiol two (methyl) acrylate, 2-mercapto ethyl sulphur two (methyl) acrylate, 2,2 '-oxydiethylene-sulphur two (methyl) acrylate, trimethylolpropane tris (2-mercaptoacetate) three (methyl) acrylate, trimethylolpropane tris (3-mercaptopropionic acid ester) three (methyl) acrylate, trimethylolethane trimethacrylate (2-mercaptoacetate) three (methyl) acrylate, trimethylolethane trimethacrylate (3-mercaptopropionic acid ester) three (methyl) acrylate, tetramethylolmethane four (2-mercaptoacetate) four (methyl) acrylate, thioesters such as tetramethylolmethane four (3-mercaptopropionic acid ester) four (methyl) acrylate, perhaps, N, N '-ethylenebis (methyl) acrylamide, N, two (methyl) acrylamides of N '-trimethylene, 1, two (methyl) acrylamides of 6-hexa-methylene, 1,4-two (methyl) acryloyl piperazine, 1,3,5-three (methyl) acryloyl hexahydro--S-triazine etc.
In addition,, can enumerate piperazine, 2-methylpiperazine, 2 as the object lesson of the above-mentioned bridged piperazine derivatives of representing with formula (IV), 3-lupetazin, 2,6-lupetazins etc. wherein are preferred with the piperazine.
For making compound (A) and compound (B) carry out Michael reaction and make bridged piperazine derivatives, can adopt method and the condition identical with common Michael reaction.
That is, in solvent or in solvent-free, mixing cpd (A) and compound (B) ,-20～150 ℃, preferably under 0～100 ℃ of temperature, react.The ratio of packing into of compound (A) and compound (B) will make the mol ratio of the conjugated double bond of compound (A) and compound (B) become 1: 5～1: 0.5, is preferably 1: 3～1: 0.75 scope.
Under the situation of using solvent, as solvent, for example can enumerate halohydrocarbon such as alcohols such as methyl alcohol, ethanol, propyl alcohol, butanols, ethylene glycol, methylene dichloride, chloroform, ethylene dichloride, esters such as carbonic ether, ethyl acetate, propyl acetate, butylacetate such as ethers such as aromatic hydrocarbon such as benzene,toluene,xylene, Anaesthetie Ether, tetrahydrofuran (THF), methylcarbonate, carbonic acid ethyl methyl esters, diethyl carbonate, dipropyl carbonate.The solvent usage quantity of this moment with respect to the gross weight of compound (A) and compound (B), is 0.5～20 times of weight, preferably 1～10 times of weight.
Reaction in order to remove unreacted raw material, can be carried out concentrating under reduced pressure after finishing.Even sneak into raw material,, do not need to concentrate to remove if no problem yet.
Resulting resultant is mixture normally, but need not carry out purification process especially, can be used as linking agent and uses.
Bridged piperazine derivatives of the present invention, normally therefore high viscosity, as required, is that linking agent mixes use with inert solvent or low viscous amine preferably.As inert solvent, can enumerate alcohols such as water or methyl alcohol, ethanol, propyl alcohol, butanols, ethylene glycol, esters such as carbonic ether, ethyl acetate, propyl acetate, butylacetate such as ethers such as aromatic hydrocarbon such as halohydrocarbon such as methylene dichloride, chloroform, ethylene dichloride, benzene,toluene,xylene, Anaesthetie Ether, tetrahydrofuran (THF), methylcarbonate, carbonic acid ethyl methyl esters, diethyl carbonate, dipropyl carbonate.Quantity of solvent with respect to bridged piperazine derivatives, is 0.05～10 times of weight, preferably 0.1～5 times of weight.
The present invention also provides and uses the resulting polymer solid electrolyte with premium properties of above-mentioned bridged piperazine derivatives.
Polymer solid electrolyte of the present invention, be by above-mentioned bridged piperazine derivatives with in molecule, have in the Michael reaction institute synthetic polymkeric substance of (methyl) more than 2 acrylate-based compound (below be called compound (X)), contain periodic table of elements IA family's metal-salt and the polymer solid electrolyte that constitutes.
In molecule, has (methyl) acrylate-based compound (X) more than 2
In the present invention, with the reaction of above-mentioned bridged piperazine derivatives in the compound (X) that uses be in 1 molecule, to have (methyl) acrylate-based compound more than 2.At this, it is acrylate-based that acrylate-based and methacrylate based merging is designated as (methyl).Compound (X), with Mw as its molecular weight, when representing (methyl) acrylate-based number with n, the value of Mw/n wishes it is 300～50,000, preferably 400～10,000, if in this scope, then distance just becomes appropriate between cross-linking set, therefore can access to protect the good and high gel electrolyte of intensity of fluidity.
As the example of such compound (X), can enumerate the acrylate or the methacrylic ester of high molecular weight polyols compound.That is, weight-average molecular weight is 900～100,000, preferably 1000～20, and 000 polyol compound, for example acrylate of polycarbonate polyol, polyester polyol, polyestercarbonate polyvalent alcohol or polyether glycol or (methyl) acrylate.Below, this acrylate or methacrylic ester are designated as (methyl) acrylate.These compounds (X) can use separately, also they can be used in combination.
(1) (methyl) acrylate of polycarbonate polyol compound
The polycarbonate polyol compound can synthesize by the polyvalent alcohol more than the binary and the polycondensation of carbonic diester or carbonyl chloride.By the esterification that resulting polyol compound carries out, can carry out with usual method and condition.For example have, in the presence of alkali, make polyol compound and vinylformic acid halogenide or methacrylic acid halogenide carry out the method for condensation, in the presence of oxygen catalyst, make the method for polyester polyols pure and mild acrylic or methacrylic acid carrying out condensation etc.
The concrete example of the polyvalent alcohol that can use below is shown.These polyvalent alcohols can use separately, or also can mix 2 kinds with on use.
(i) glycols: ethylene glycol, glycol ether, triglycol, polyoxyethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, 1,3 butylene glycol, 1,4-butyleneglycol, 1,5-pentanediol, 3-methyl isophthalic acid, 5-pentanediol, 1,6-hexylene glycol, 1,8-ethohexadiol, 1, two (2-hydroxyl-oxethyl) benzene, 1 of 3-, two (2-hydroxyl-oxethyl) benzene of 4-, neopentyl glycol, 2-methyl isophthalic acid, 8-ethohexadiol, 1,9-nonanediol, 1,4-cyclohexanediol, 1, the 4-cyclohexanedimethanol.
(ii) polyalcohols: TriMethylolPropane(TMP), trimethylolethane, tetramethylolmethane, ditrimethylolpropane, Dipentaerythritol, glycerol, minashi sugar alcohol.
(iii) with respect to the hydroxyl of these polyalcohols, have and make 1～5 normal oxyethane, propylene oxide or other oxirane carry out the alcohols of the hydroxyl of addition reaction.
As carbonic diester, can enumerate methylcarbonate, diethyl carbonate, carbonic acid diisopropyl ester, ethylene carbonate, Texacar PC etc., they can use separately, perhaps also can make up 2 kinds with on use.
(2) (methyl) acrylate of polyester polyol
Polyester polyol can perhaps synthesize by the polycondensation of polyvalent alcohol and polycarboxylic acid by the polycondensation of hydroxycarboxylic acid or lactone.
At this, as hydroxycarboxylic acid or lactone, can enumerate oxyacetic acid, lactic acid, beta-propiolactone, beta-butyrolactone, gamma-butyrolactone, γ-Wu Neizhi, γ-Ji Neizhi, γ-Geng Neizhi, γ-Xin Neizhi, γ-Ren Neizhi, γ-decalactone, δ-Wu Neizhi, Beta-methyl-δ-Wu Neizhi, δ-caprolactone, δ-Xin Neizhi, β-decalactone, δ-nonalactone, 6-caprolactone etc.When the polycondensation of these hydroxycarboxylic acids or lactone,, just can make terminal functional group become hydroxyl if add 2～6 yuan polyol as polymerization starter.
As polyvalent alcohol, can use (i) di-alcohols same as described above to reach (ii) polyalcohols.
As polycarboxylic acid, can enumerate propanedioic acid, succsinic acid, pentanedioic acid, hexanodioic acid, fumaric acid, toxilic acid, hexanaphthene-1,2-dicarboxylic acid, hexanaphthene-1,3-dicarboxylic acid, hexanaphthene-1,4-dicarboxylic acid, cis tetrahydrophthalic acid, phthalic acid, m-phthalic acid, terephthalic acid etc.In addition, replace dicarboxylic acid, also can use corresponding acid anhydrides or dicarboxylic acid dialkyl esters.
(3) (methyl) acrylate of polyestercarbonate polyvalent alcohol
The polyestercarbonate polyvalent alcohol, can be by above-mentioned polyester polyols pure and mild carbonic diester or carbonyl chloride synthesize.Under the situation of using carbonic diester, can methylcarbonate, diethyl carbonate, carbonic acid diisopropyl ester, diphenyl carbonate, ethylene carbonate, Texacar PC etc. be shown example, they can use separately, also can make up more than 2 kinds and use.To the conversion of the acrylate or the methacrylic ester of polyestercarbonate polyvalent alcohol, can carry out in the same manner with the esterification of polycarbonate polyol.
(4) (methyl) acrylate of polyether glycol
Polyether glycol can by make alkylene oxide polymerization or on polyvalent alcohol the addition oxirane obtain.As oxirane, can enumerate oxyethane, propylene oxide, trimethylene oxide, tetrahydrofuran (THF) etc., they can use separately, perhaps also can make up more than 2 kinds and use.As polyvalent alcohol, can use (i) di-alcohols same as described above or (ii) polyalcohols.And, to the conversion of the acrylate or the methacrylic ester of polyether glycol, can carry out in the same manner with the esterification of polycarbonate polyol.
As compound (X) if use (methyl) acrylate of the high molecular weight polyols that hereto describes in detail, then the cross-linking set spacing defection appropriateness of institute's synthetic polymkeric substance is elongated, therefore ionic conductivity uprises, and if form ionogen, then guarantor's fluidity of gel is good, thereby obtains excellent ionogen.
The manufacture method of polymkeric substance
The polymkeric substance that utilizes the Michael reaction of compound (X) and above-mentioned bridged piperazine derivatives and make, weight-average molecular weight is preferably more than 10,000.Especially, under situation, importantly form the high molecular weight crosslinked polymkeric substance low to the solvability of the solvent in the electrolytic solution as gel electrolyte.Manufacture method can be with carrying out with roughly the same method and the condition of common Michael reaction.
The reaction of compound (X) and above-mentioned bridged piperazine derivatives in solvent or in solvent-free, mixes both, at-20 ℃～150 ℃, is preferably under 0～100 ℃ the temperature and carries out.The compound (X) of this moment and the ratio of packing into of above-mentioned bridged piperazine derivatives, the ratio of the imido grpup of and above-mentioned bridged piperazine derivatives acrylate-based by (methyl) of compound (X) wishes it is 1: 5～5: 1, the scope of preferably 1: 3～3: 1 (mol ratio).
Under the situation of using solvent,, can enumerate following compound as its example.The solvent usage quantity with respect to the gross weight of compound (X) and above-mentioned bridged piperazine derivatives, is 0.5～20 times of weight, preferably 1～10 times of weight.
(a) alcohols: methyl alcohol, ethanol, propyl alcohol, butanols, ethylene glycol
(b) halogenated hydrocarbon: methylene dichloride, chloroform, ethylene dichloride
(c) arene: benzene,toluene,xylene
(d) saturated hydrocarbons: hexane, heptane, decane, hexanaphthene
(e) ethers: Anaesthetie Ether, tetrahydrofuran (THF)
(f) carbonates: ethylene carbonate, Texacar PC, methylcarbonate, carbonic acid ethyl methyl esters, diethyl carbonate, dipropyl carbonate
(g) ester class: ethyl acetate, propyl acetate, butylacetate, gamma-butyrolactone, δ-Wu Neizhi, 6-caprolactone
The polymkeric substance that generates after the Michael reaction obtains with shapes such as Powdered, film like, gels, can be used as the solid electrolyte utilization.If in the presence of solvent, react; resultant can form gel usually; but both this gelling material intactly can be used as the material of polymer electrolyte, can carry out drying as required again, use as the film like of removing solvent or pulverous polymkeric substance.
In addition, in order to form polymer solid electrolyte material, preferably in polymkeric substance, form cross-linking set with sufficient intensity.For this reason, part or all of compound (X) and above-mentioned bridged piperazine derivatives used in hope, use has (methyl) acrylate-based composition more than 3 in molecule as compound (X), perhaps uses the composition that has 3 above imido grpups in 1 molecule as above-mentioned bridged piperazine derivatives.
Polymer solid electrolyte
Polymer solid electrolyte of the present invention in the polymkeric substance of the Michael reaction manufacturing by above-mentioned compound (X) and above-mentioned bridged piperazine derivatives, contains the metal-salt of periodic table of elements IA family.
As the metal-salt of periodic table of elements IA family, be the compound of lithium, sodium, potassium etc., especially preferably be selected from LiClO 4, LiBF 4, LiPF 6, LiN (CF 3CF 2SO 2) 2, LiCF 3SO 3, LiN (CF 3SO 2) 2, LiC (CF 3SO 2) 3In one or more lithium salts.The concentration of the metal-salt in the solid electrolyte wishes it is 0.1～10 (mol/l).
In the present invention, the so-called metal-salt that in polymkeric substance, contains periodic table of elements IA family, mean utilize the method that might cooperate in this polymkeric substance, have this metal-salt.If for example, can be in advance undertaken by compound (X) and above-mentioned bridged piperazine derivatives polymkeric substance and the metal-salt of the periodic table of elements IA family metal-salt that carries out blended method or compound (X), above-mentioned bridged piperazine derivatives and the periodic table of elements IA family method of carrying out carrying out behind the uniform mixing Michael reaction etc. by the Michael reaction manufacturing.Particularly, if employing according to the latter's method, just obtains the solid electrolyte of homodisperse metal-salt in the polymkeric substance of being made by compound (X) and above-mentioned bridged piperazine derivatives easily, be preferred therefore.
For example, the metal-salt of compound (X), above-mentioned bridged piperazine derivatives, periodic table of elements IA family adds solvent as required and mixes, and after this its homogeneous mixture solotion of coating on smooth substrate, by heating, reacts and gelation as required.Make like this, just can access the solid electrolyte film that thickness is 0.1～1000 μ m.Under situation about heating, for example 30～100 ℃ of the Undec temperature ranges of electrolytic salt, be preferably under 40～90 ℃ of temperature and carry out.Moreover Michael reaction according to the chemical structure of compound that becomes raw material (X) and above-mentioned piperazine derivatives compounds, even at room temperature also can promptly carry out, therefore if select such compound, not necessarily needs heating.
In addition, polymer solid electrolyte of the present invention, except the metal-salt of the polymkeric substance made by compound (X) and above-mentioned bridged piperazine derivatives and periodic table of elements IA family, with respect to the polymkeric substance of 100 weight parts by compound (X) and the manufacturing of above-mentioned bridged piperazine derivatives, also can contain 0～5,000 weight part, be preferably the non-aqueous solvents such as carbonic ether of 100～2,000 weight part.In order in polymkeric substance, to contain non-aqueous solvent, when making polymer solid electrolyte, can under the state that makes the non-aqueous solvent coexistence, carry out Michael reaction, also can adopt the method for impregnation non-aqueous solvent after polymerization in addition.
As non-aqueous solvent, can suitably use carbonic ether or lactone.Example as carbonic ether, can enumerate chain or cyclic carbonates such as ethylene carbonate, Texacar PC, methylcarbonate, carbonic acid ethyl methyl esters, diethyl carbonate, dipropyl carbonate, as the example of lactone, can enumerate gamma-butyrolactone, δ-Wu Neizhi, 6-caprolactone etc. in addition.
Polymer solid electrolyte of the present invention is containing the state of non-aqueous solvent, protects the good and ionic conductivity height of fluidity.Such polymer solid electrolyte for example can be used for primary cell, secondary cell, electrical condenser, electricity and cause electrochemical element, medical power elements etc. such as colorful light-emitting display element.Especially, this polymer solid electrolyte is applicable to the instead purposes of the organic electrolyte of lithium-ion secondary cell.And, in order on current collector, to disperse and fixing powdered electrode material, also can be used as the matrix material utilization.
Secondary cell
Secondary cell of the present invention is made of the negative pole that contains negative electrode active material, the positive pole that contains positive active material, the above-mentioned polymer solid electrolyte that is configured in therebetween.
As negative electrode active material, can use metallic lithium, contain that lithium alloy maybe can mix and the material of dedoping lithium ion etc.As mixing and the material of the such lithium ion of dedoping, can from carbon material, stannic oxide, silicon, titanium oxide or transition metal nitride etc., suitably select.Wherein especially can mix and the carbon material of dedoping lithium ion serve as that preferably this carbon material can be a crystalline state carbon, also can be non-crystalline state carbon.Specifically, can activated carbon, carbon fiber, carbon black, middle carbon microballon, natural graphite be shown example.
As positive active material, can enumerate MoS 2, TiS 2, MnO 2, V 2O 5Deng transition metal oxide or transient metal sulfide, by LiCoO 2, LiMnO 2, LiMn 2O 4, LiNiO 2, LiNi xCo (1-x)O 2Deng lithium and the transition metal composite oxides, polyaniline, Polythiophene, polypyrrole, polyacetylene, polyacene (polyacene), the dimercaptothiodiazole/electroconductive polymer compounds such as polyaniline mixture that constitute, disulfide etc.Among these, especially the composite oxides that are made of lithium and transition metal are preferred.
When in secondary cell, using such polymer solid electrolyte, earlier polymer solid electrolyte is configured as film like, is clipped in again between positive pole and the negative pole, thus, just can make battery.Replace film like and dispose that to be pre-formed gelatinous polymer solid electrolyte also passable.
In addition, behind the three-layer structure that forms positive pole, barrier film, negative pole, have in the battery manufacturing processed of impregnation electrolytic solution process wherein, replace electrolytic solution to use by the metal-salt of compound (X), above-mentioned bridged piperazine derivatives, periodic table of elements IA family and the solution of non-aqueous solvent formation, after this this solution of impregnation adopt the method for gelation also to be fine.No matter which kind of situation if use the polymer solid electrolyte of the invention described above, can both suppress the transformation of present battery manufacturing processed to make secondary cell to inferior limit.
As the shape of battery, can select film shape, coin shape, round shape or shape arbitrarily such as square.
Embodiment
Specific embodiments of the invention below are described, but the present invention is not subjected to any restriction of these embodiment.
(synthesis example 1)
In the glass reactor of equipment stirrer, thermometer and rectifying tower etc., add 11.2g trimethylolpropane trimethacrylate (レ イ ヨ Application Co., Ltd. of Mitsubishi goods), 8.61g methyl alcohol and 8.87g piperazine, stirring at room 1 hour, stirred 3 hours at 80 ℃ again.After this, add the 20.0g diethyl carbonate, after the dissolving,, remove unreacted piperazine fully equably by under reduced pressure concentrating.Obtain colourless thickness oily mater as resultant.Output is 17.5g.
Resulting colourless thickness oily mater carried out NMR analyzes and the result of IR analysis, from following data as can be known resultant be trimethylolpropane trimethacrylate-piperazine affixture (TMP-Pi).
(1) 1HNMR analytical results: (σ ppm, CDCl 3)
0.91(3H)、1.10～1.17(9H)、1.45～1.58(2H)、1.76(3H)、2.2～2.9(33H)、4.06(6H)
(2) IR analytical results: (cm -1, polyethylene film)
3272、1739、1461、1376、1246、1173
By in resulting TMP-Pi, adding with the diethyl carbonate of weight and mixing, obtain the 50% diethyl carbonate solution of TMP-Pi.
(synthesis example 2)
In the glass reactor of equipment stirrer, thermometer and rectifying tower etc., add 9.90g Ethylene glycol dimethacrylate, 8.69g methyl alcohol and 8.61g piperazine,, stirred 3 hours at 80 ℃ again stirring at room 1 hour.After this, add the 20.0g diethyl carbonate, after the dissolving,, remove unreacted piperazine fully equably by under reduced pressure concentrating.Obtain colourless thickness oily mater as resultant.Output is 17.4g.
Resulting colourless thickness oily mater carried out NMR analyzes and the result of IR analysis, from following data as can be known resultant be Ethylene glycol dimethacrylate-piperazine affixture (EGDMA-Pi).
(1) 1HNMR analytical results: (σ ppm, CDCl 3)
1.12～1.17(6H)、1.45～1.58(2H)、2.2～2.9(24H)、4.29(4H)
(2) IR analytical results: (cm -1, polyethylene film)
2940、2808、1739、1460、1377、1243、1173
By in resulting EGDMA-Pi, adding with the diethyl carbonate of weight and mixing, obtain the 50% diethyl carbonate solution of EGDMA-Pi.
(synthesis example 3)
Ethylene oxide adduct (the OH valency: 433 that in the glass reactor of equipment stirrer, thermometer and Dienstag extractor, adds the 50.6g TriMethylolPropane(TMP), Japan emulsifying agent Co., Ltd. goods), 4-methoxyphenol and the 50ml toluene of 20g methacrylic acid, 1.01g tosic acid monohydrate, 26mg, reflux is 5 hours on one side, on one side the water that generates is removed to outside the reaction system.After making temperature reduce to 50 ℃, add 13.0g キ ヨ one ワ, one De 500 (Kyowa Chemical Industry Co., Ltd's goods), stirred 1 hour at 50 ℃.After being cooled to room temperature again, filter insolubles, under reduced pressure concentrated filtrate just obtains trimethacrylate (TMP-EOTMA) colorless oil as purpose.Output is 31.3g.
Then, in the glass reactor of equipment stirrer, thermometer and rectifying tower etc., add TMP-EOTMA, 6.5g methyl alcohol and the 6.24g piperazine that 15.0g obtains with above-mentioned reaction, stirring at room 1 hour, again 80 ℃ of stirrings 3 hours.After this, add the 15.0g diethyl carbonate, after the dissolving,, remove unreacted piperazine fully equably by under reduced pressure concentrating.Obtain colourless thickness oily mater as resultant.Output is 18.6g.
Resulting colourless thickness oily mater carried out NMR analyzes and the result of IR analysis, from following data as can be known resultant be the trimethacrylate-piperazine affixture (TMPEO-Pi) of TriMethylolPropane(TMP) ethylene oxide adduct.
(1) 1HNMR analytical results: (σ ppm, CDCl 3)
0.85(3H)、1.10～1.17(9H)、1.37～1.43(2H)、1.76(3H)、2.2～2.9(36H)、3.5～3.7(24H)、4.22(6H)
(2) IR analytical results: (cm -1, polyethylene film)
2940、2874、1736、1460、1376、1246、1118
By in resulting TMPEO-Pi, adding with the diethyl carbonate of weight and mixing, obtain the 50% diethyl carbonate solution of TMPEO-Pi.
(synthesis example 4)
In the glass reactor of equipment stirrer, thermometer and Dienstag extractor, add 40.3g polycaprolactonetriol (OH valency: 83.4, ダ イ セ Le chemical industry Co., Ltd. goods), 4-methoxyphenol and the 40ml toluene of 4.32g vinylformic acid, 0.80g tosic acid monohydrate, 0.08g, reflux is 5 hours on one side, on one side the water that generates is removed to outside the reaction system.After making temperature reduce to 50 ℃, add the 1.23g diacetyl oxide, continue to stir 1 hour in this temperature again.Then, add 4.0g キ ヨ one ワ, one De 500 (Kyowa Chemical Industry Co., Ltd's goods), stirred 1 hour at 50 ℃.After being cooled to room temperature again, filter insolubles, under reduced pressure concentrated filtrate just obtains polycaprolactone triacrylate (PCL-TA) colorless oil as purpose.Output is 41.0g.
Synthesizing of (synthesis example 5) polycarbonate polypropylene ester
In the glass reactor of equipment stirrer, thermometer and rectifying tower etc., mix 32.0g TriMethylolPropane(TMP)-EO affixture (compound of addition 3 mole ethylene oxides in 1 mole of trimethylol propane, Japanese emulsifying agent Co., Ltd. goods), 114.6g glycol ether, 124.3g methylcarbonate and as 28% methanol solution of sodium methylate 0.23g of catalyzer.This mixed solution under normal pressure, kept 2 hours at 95 ℃, after this, is warming up to 150 ℃ with 5 hours, heated 4 hours at 150 ℃ again, heat up in a steamer the methyl alcohol that in reaction, generates.Then, under the decompression of 5mmHg, remain on 150～155 ℃, stay the 10.3g glycol ether of following polyreaction to generate.After being cooled to room temperature then, add 100ml chloroform and 2.3g atlapulgite, stirred 1 hour at 55 ℃.After being cooled to room temperature again, the filter activity carclazyte by concentrated filtrate, just obtains the 145g polycarbonate polyol as thickness oily matter.The weight-average molecular weight of this resultant is 4,200 from the result of gpc analysis as can be known.
Then, in the glass reaction vessel of equipment stirrer, thermometer and dropping funnel, mix 30.1g above-mentioned polycarbonate polyol, 8.7g triethylamine and 100ml methylene dichloride after, be cooled to 5 ℃.With 20 minutes from the dropping funnel 7.8g acrylate chloride that drips, continue to stir 1 hour at 5 ℃ again.Be warming up to room temperature at leisure, again stirring at room 2 hours.Filtering reacting liquid is cleaned filtrate with saturated aqueous common salt, behind anhydrous magnesium sulfate drying, concentrates, and obtains the faint yellow thickness oily matter of 29.1g as the polycarbonate polyacrylic ester of purpose thus.
Synthesizing of (synthesis example 6) polyester triacrylate
In the glass reactor of equipment stirrer, thermometer and Dienstag extractor, add 40.0g by hexanodioic acid, 3-methyl isophthalic acid, 5-pentanediol and TriMethylolPropane(TMP) synthetic polyester polyol (OH valency: 84, Network ラ レ Co., Ltd. goods), 4-methoxyphenol and the 40ml toluene of 4.32g vinylformic acid, 0.80g tosic acid monohydrate, 0.08g, reflux is 5 hours on one side, on one side the water that generates is removed to outside the reaction system.After making temperature reduce to 50 ℃, add the 1.23g diacetyl oxide, continue to stir 1 hour in this temperature again.Then, add 4.0g magnesium oxide, stirred 1 hour at 50 ℃.After being cooled to room temperature again, filter insolubles, under reduced pressure concentrated filtrate just obtains the colorless oil as the polyester triacrylate of purpose.Output is 40.8g.
(embodiment 1)
In the sample plasma bottle of 10ml capacity, mix 0.313g at synthesis example 4 synthetic PCL-TA with in solvent, press 1mol/l and dissolve LiPF with 1: 1 mixed carbonic acid ethyl of volumetric ratio and diethyl carbonate 6Solution 4.40g after, in this solution, add 0.247g at synthesis example 1 synthetic TMP-Pi, mix in room temperature, be modulated into uniform solution.In room temperature, gelation takes place after 3 hours, completely solidified after 4 hours obtains the good gel of the unseparated guarantor's fluidity of liquid.
(embodiment 2)
Similarly mix 0.654g and press 1mol/l dissolving LiPF at synthesis example 4 synthetic PCL-TA with in solvent with 1: 1 mixed carbonic acid ethyl of volumetric ratio and diethyl carbonate 6Solution 1.854g after, in this solution, add 0.492g at synthesis example 2 synthetic EGDMA-Pi, mix in room temperature, be modulated into uniform solution.In room temperature, gelation takes place after 24 hours, completely solidified after 30 hours obtains the good gel of the unseparated guarantor's fluidity of liquid.
(embodiment 3)
Similarly mix 0.179g and press 1mol/l dissolving LiPF at synthesis example 4 synthetic PCL-TA with in solvent with 1: 1 mixed carbonic acid ethyl of volumetric ratio and diethyl carbonate 6Solution 2.979g after, in this solution, add 0.342g at synthesis example 3 synthetic TMPEO-Pi, mix in room temperature, be modulated into uniform solution.In room temperature, gelation takes place after 15 hours, completely solidified after 20 hours obtains the good gel of the unseparated guarantor's fluidity of liquid.
(comparative example 1)
Similarly mix 0.928g and press 1mol/l dissolving LiPF at synthesis example 4 synthetic PCL-TA with in solvent with 1: 1 mixed carbonic acid ethyl of volumetric ratio and diethyl carbonate 6Solution 3.927g after, in this solution, add the 0.0717g Diethylenetriamine, mix in room temperature, be modulated into uniform solution.In room temperature, through gelation not taking place yet, the liquid status when keeping being prepared into homogeneous solution after 1 week.
(comparative example 2)
Similarly mix 0.450g and press 1mol/l dissolving LiPF at synthesis example 4 synthetic PCL-TA with in solvent with 1: 1 mixed carbonic acid ethyl of volumetric ratio and diethyl carbonate 6Solution 2.050g after, in this solution, add 0.056g ジ ェ Off ァ one ミ Application (サ Application テ Network ノ ケ ミ カ Le society goods), mix in room temperature, be modulated into uniform solution.In room temperature, through gelation not taking place yet, the liquid status when keeping being prepared into homogeneous solution after 1 week.
(embodiment 4)
Mix 1.48g polycarbonate polyacrylic ester that synthesis example 5 is made and in the solvent of 1: 1 mixed carbonic acid ethyl of weight ratio and Texacar PC by the concentration dissolving LiPF of 1 (mol/l) 6Electrolytic solution 7.54g after, in this solution, be added in the 50% diethyl carbonate solution 1.03g of the TMP-Pi that synthesis example 1 makes, stir in room temperature with the electromagnetic type agitator.After about 30 minutes, become gel, lost flowability.Even this gel was placed 24 hours in room temperature, not observe liquid yet and separate, guarantor's fluidity is good.
Attaching internal diameter on glass substrate is the silastic moulding template of 20mm, the solution before the gelation that the 150 μ l that drip in mould plate modulate in advance.This substrate-placing on the hot-plate that is provided with in nitrogen box, was solidified by placing in room temperature, and forms polyelectrolyte film in 2 hours.
Resulting film thickness is 370 μ m.This film is struck out diameter 10mm, clamp with SUS system electrode, use ソ one ラ ト ロ Application 1255B, measure complex impedance, obtain the ionic conduction degree with resolving, the result is 2.039mS/cm.
(embodiment 5)
In embodiment 4, replace the polycarbonate polyacrylic ester that synthesis example 5 is made, carrying out 4 identical operations at the polyester triacrylate that synthesis example 6 is made except using 1.72g with embodiment, the result was solidified at about 1 hour.Even this gel was placed 24 hours in room temperature, do not observe liquid yet and separate, it is good protecting fluidity.In addition, make the polyelectrolyte film that thickness is 370 μ m in the same manner with embodiment 1.Obtain the ionic conduction degree of resulting polymer electrolyte, the result is 1.3mS/cm.
(embodiment 6)
In embodiment 4, except using 1.39g TriMethylolPropane(TMP) EO modification triacrylate (Xin Zhong village KCC goods, Mw=1600) replace carrying out 4 identical operations with embodiment beyond the polycarbonate polyacrylic ester that synthesis example 4 is made, the result was solidified at about 1 hour.Even this gel was placed 24 hours in room temperature, do not observe liquid yet and separate, it is good protecting fluidity.In addition, make the polyelectrolyte film that thickness is 370 μ m in the same manner with embodiment 4.Obtain the ionic conduction degree of resulting polymer electrolyte, the result is 3.0mS/cm.
(embodiment 7)
＜evenly the preparation of electrolytic solution 〉
Mix polyester polyacrylic ester that 1.48g makes in synthesis example 6 and in the solvent of 1: 1 mixed ethylene carbonate of volume ratio and diethyl carbonate by the concentration dissolving LiPF of 1.0 (mol/l) 6Nonaqueous electrolytic solution 7.54g, after this in this solution, be added in 50% diethyl carbonate solution 1.03g of trimethylolpropane trimethacrylate-piperazine affixture (TMP-Pi) that synthesis example 1 makes, stirring at room 10 minutes, be modulated into uniform solution.
The making of＜negative pole 〉
Middle carbon microballon (trade(brand)name: MCMB6-28, d002=0.337nm, the density 2.17g/cm that mix Osaka ガ ス (strain) system 3) carbon dust 90 weight parts and as poly(vinylidene fluoride) 10 weight parts of binding agent, be dispersed in the solvent N-Methyl pyrrolidone, be modulated into the cathode agent slurry of pasty state.Then, at thickness this cathode agent slurry of coating on the negative electrode collector of banded Copper Foil system of 20 μ m, carry out drying and just obtain zonal carbon negative pole.The thickness of dried cathode agent is 25 μ m.And it is the discoid of 15mm that this strip electrode is struck out diameter, carries out compression molding then, makes negative electrode.
＜anodal is made 〉
The LiCoO that mixes this village of 91 weight parts ケ ミ カ Le (strain) system 2(goods name: HLC-21, median size is 8 μ m) microparticle, 6 weight parts as the poly(vinylidene fluoride) of binding agent, are modulated into anode mixture as the graphite of electro-conductive material and 3 weight parts, are dispersed in the solvent N-Methyl pyrrolidone, obtain the anode mixture slurry.Be this slurry of coating on the banded aluminium foil system positive electrode collector of 20 μ m at thickness, carry out drying, just obtain banded anodal by compression molding.The thickness of dried anode mixture is 40 μ m.Then, it is the discoid of 15mm that this strip electrode is struck out diameter, makes anode electrode.
The making of＜battery 〉
Prepare discoid negative pole and the discoid positive pole obtain like this, also having by thickness is the barrier film that the polyester non-woven fabrics of 200 μ m is made.In the battery case of 2032 sizes of stainless steel, press negative pole, barrier film, anodal order with behind each lamination, to wherein injecting above-mentioned even electrolytic solution.After this, the plate (thickness 2.4mm, diameter 15.4mm) of stainless steel is contained in the battery case, is situated between again and helps the Airtight gasket of polypropylene system, battery case is covered ca(u)lk.Then, this battery was left standstill 12 hours in room temperature (25 ℃), the composition of the electrolytic solution of previous injection is solidified.Its result, bubble-tight, the diameter in the battery of can being maintained is 20mm, highly is the Coin-shape cell of 3.2mm.
The performance test of＜battery 〉
Use Manufactured button shaped secondary cell, make 20 circulations repeatedly that discharge and recharge of 1mA in room temperature, between 2.7V-4.2V.Its result, first loading capacity is the LiCoO of every 1g 2Be 140 (mAh/g), 20 round-robin capability retentions are 97%.
(reference example)
In embodiment 7, except using the concentration dissolving LiPF that in the solvent of 1: 1 mixed ethylene carbonate of volume ratio and diethyl carbonate, presses 1.0 (mol/l) 6Nonaqueous electrolytic solution replace beyond the employed even electrolytic solution, carry out the making of Coin-shape cell in the same manner with embodiment 4.Then, implement same battery performance test, first loading capacity is the LiCoO of every 1g 2Be 142 (mAh/g), 20 round-robin capability retentions are 97%.
Applicability on the industry
The bridged piperazine derivatives of novelty of the present invention is low-steam pressure, low irritant, as propylene Curing agent under the normal temperature of acid esters, crosslinking agent have good characteristic, and also can access institute The good polymeric solid of guarantor's fluidity of the gel that forms.
In addition, the reaction by compound of the present invention (X) and compound (B) obtains piperazine derivatives The method of thing is applicable to that efficient makes this novel bridged piperazine derivatives well.
Polymer solid electrolyte of the present invention has high ionic conduction degree, keeps simultaneously electricity The stability of chemistry. Its tympan has flexibility, and gelling material has good guarantor's liquid The property.
When the manufacturing of the polymer of the matrix that becomes this polymer solid electrolyte, do not use the spy Different device, and do not need during fabrication special high temperature can make bridged piperazine derivatives and dividing Have in the son that (methyl) acrylate-based compound (X) carries out easily and promptly more than 2 Reaction. And this polymer solid electrolyte can not produce electrolytical performance is impacted Accessory substance.
Therefore, this polymer solid electrolyte can be applicable to one-shot battery, secondary cell, electricity Container, electricity cause electrochemical element, the medical executive components etc. such as color development display element.
The secondary cell that particularly contains this polymer solid electrolyte, the electricity of charge-discharge characteristic etc. The pond function admirable, and almost do not have the worry of battery leakage, Reliability Enhancement.

Claims (14)

1. bridged piperazine derivatives, it is the compound that has in 1 molecule more than 2 with the base of formula (I) expression,
Figure A0182336800021
(in the formula, R 1, R 2, R 3, R 4And R 5, can be identical, also can be different, expression hydrogen atom or low alkyl group; X represents Sauerstoffatom, sulphur atom or NR 6R 6Expression hydrogen atom or low alkyl group; * represent binding site).
2. bridged piperazine derivatives according to claim 1 is characterized in that: in above-mentioned formula (I), and R 1, R 2, R 3, R 4And R 5, can be identical, also can be different, expression hydrogen atom or methyl.
3. bridged piperazine derivatives according to claim 1, wherein: described compound is the compound with following formula (II) expression,
(in the formula, R is that can to contain heteroatomic carbonatoms be 2～100 alkyl; N is 2～10 integer; R 1, R 2, R 3, R 4And R 5, can be identical, also can be different, expression hydrogen atom or low alkyl group; X represents Sauerstoffatom, sulphur atom or NR 6R 6Be hydrogen atom or low alkyl group).
4. bridged piperazine derivatives according to claim 3 is characterized in that: in described formula (II), and R 1, R 2, R 3, R 4And R 5, can be identical, also can be different, expression hydrogen atom or methyl.
5. polymer solid electrolyte is characterized in that: by by each described bridged piperazine derivatives in the claim 1～4 with have the metal-salt that contains periodic table of elements IA family in the polymkeric substance that the Michael reaction of (methyl) more than 2 acrylate-based compound (X) forms constitute in molecule.
6. polymer solid electrolyte according to claim 5 is characterized in that: described compound (X) is (methyl) acrylate that is selected from least a polyol compound in polycarbonate polyol, polyester polyol, polyestercarbonate polyvalent alcohol and the polyether glycol.
7. according to each described polymer solid electrolyte in claim 5 or 6, it is characterized in that: described polymkeric substance is that the imino-of bridged piperazine derivatives and (methyl) acrylate-based scope (mol ratio) at 1: 5～5: 1 of compound (X) are carried out the formed polymkeric substance of Michael reaction.
8. according to each described polymer solid electrolyte in the claim 5～7, it is characterized in that: the metal-salt of described periodic table of elements IA family is to be selected from LiClO 4, LiBF 4, LiPF 6, LiN (CF 3CF 2SO 2) 2, LiCF 3SO 3, LiN (CF 3SO 2) 2, LiC (CF 3SO 2) 3In at least a or more than one compound.
9. according to each described polymer solid electrolyte in the claim 5～8, it is characterized in that: described polymkeric substance is the gelling material that keeps non-aqueous solvent.
10. a secondary cell is characterized in that: contain each described polymer solid electrolyte in the claim 5～9.
11. a secondary cell is characterized in that: by: each described polymer electrolyte in the claim 5～9; Contain be selected from metallic lithium, contain lithium alloy, can mix and the carbon material of dedoping lithium ion, can mix and the stannic oxide of dedoping lithium ion, can mix and the silicon of dedoping lithium ion and can mix and the titanium oxide of dedoping lithium ion at least a negative pole as negative electrode active material; Contain the positive pole of the composite oxides of lithium and transition metal as positive active material; Constitute.
12. the manufacture method of the described bridged piperazine derivatives of claim 1 is characterized in that: make the compound (A) that in 1 molecule, has the base of representing with following formula (III) more than 2
Figure A0182336800041
(in the formula, R 1And X is identical with described formula (I))
With compound (B) with following formula (IV) expression
Figure A0182336800042
(in the formula, R 2, R 3, R 4And R 5(I) is identical with above-mentioned formula)
React.
13. the manufacture method of bridged piperazine derivatives according to claim 12 is characterized in that: the R of described formula (III) 1And the R of above-mentioned formula (IV) 2, R 3, R 4And R 5, can be identical, also can be different, expression hydrogen atom or methyl.
14. the manufacture method according to claim 12 or 13 described bridged piperazine derivatives is characterized in that: the ratio of packing into of described compound (A) and compound (B) is 1: 5～1: 0.5 in molar ratio.
CNA018233686A 2001-06-15 2001-06-15 Piperazine derivative, process for producing the same, polymeric solid electrolyte and secondary battery Pending CN1518544A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/JP2001/005131 WO2002102786A1 (en) 2000-08-01 2001-06-15 Piperazine derivative, process for producing the same, polymeric solid electrolyte, and secondary battery

Publications (1)

Publication Number Publication Date
CN1518544A true CN1518544A (en) 2004-08-04

Family

ID=34308178

Family Applications (1)

Application Number Title Priority Date Filing Date
CNA018233686A Pending CN1518544A (en) 2001-06-15 2001-06-15 Piperazine derivative, process for producing the same, polymeric solid electrolyte and secondary battery

Country Status (2)

Country Link
KR (1) KR20030051620A (en)
CN (1) CN1518544A (en)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103570873A (en) * 2013-10-23 2014-02-12 深圳新宙邦科技股份有限公司 Composition for gel polymer electrolyte, gel polymer electrolyte and electrochemical device
CN110137497A (en) * 2019-05-11 2019-08-16 珠海冠宇电池有限公司 A kind of negative electrode binder and preparation method thereof and lithium ion battery
CN111129596A (en) * 2019-12-26 2020-05-08 天目湖先进储能技术研究院有限公司 High-voltage additive and high-voltage electrolyte for lithium battery
CN111326792A (en) * 2018-12-14 2020-06-23 宁德时代新能源科技股份有限公司 Electrolyte and battery
CN115304725A (en) * 2022-07-26 2022-11-08 中山大学 Degradable solvent-free ionic conductive elastomer and preparation method and application thereof
CN117558975A (en) * 2024-01-11 2024-02-13 广东工业大学 Aza-addition polyether ester group all-solid polymer electrolyte and preparation method and application thereof

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101075319B1 (en) 2008-05-21 2011-10-19 삼성에스디아이 주식회사 Electrolyte for lithium ion secondary battery and lithium ion secondary battery comprising the same
KR102654578B1 (en) * 2023-04-19 2024-04-04 국립군산대학교산학협력단 Solid polymer electrolyte composition comprising polymer crosslinked with an ionic crosslinker and electronic component comprising the same

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103570873A (en) * 2013-10-23 2014-02-12 深圳新宙邦科技股份有限公司 Composition for gel polymer electrolyte, gel polymer electrolyte and electrochemical device
CN111326792A (en) * 2018-12-14 2020-06-23 宁德时代新能源科技股份有限公司 Electrolyte and battery
CN110137497A (en) * 2019-05-11 2019-08-16 珠海冠宇电池有限公司 A kind of negative electrode binder and preparation method thereof and lithium ion battery
CN110137497B (en) * 2019-05-11 2021-05-25 珠海冠宇电池股份有限公司 Negative electrode binder, preparation method thereof and lithium ion battery
CN111129596A (en) * 2019-12-26 2020-05-08 天目湖先进储能技术研究院有限公司 High-voltage additive and high-voltage electrolyte for lithium battery
CN111129596B (en) * 2019-12-26 2022-06-17 天目湖先进储能技术研究院有限公司 High-voltage additive and high-voltage electrolyte for lithium battery
CN115304725A (en) * 2022-07-26 2022-11-08 中山大学 Degradable solvent-free ionic conductive elastomer and preparation method and application thereof
CN117558975A (en) * 2024-01-11 2024-02-13 广东工业大学 Aza-addition polyether ester group all-solid polymer electrolyte and preparation method and application thereof
CN117558975B (en) * 2024-01-11 2024-03-15 广东工业大学 Aza-addition polyether ester group all-solid polymer electrolyte and preparation method and application thereof

Also Published As

Publication number Publication date
KR20030051620A (en) 2003-06-25

Similar Documents

Publication Publication Date Title
CN1246925C (en) Nonaqueous electrolyte secondary battery
CN101003630B (en) Cyclic carbonate-modified siloxane and method for producing the same, non-aqueous electrolyte solution, secondary cell and capacitor
CN1248960C (en) Spherical carbons and method for preparing the same
CN1311585C (en) Electrolyte for rechargeable lithium battery and rechargeable lithium battery comprising same
CN1840550A (en) Composition for electrolyte, high molecular weight electrolyte, and battery using it
CN1009043B (en) Secondary cell
CN1203462A (en) Cell
CN1820386A (en) Process for producing lithium-containing composite oxide for positive electrode for lithium secondary battery
CN1331843A (en) Composite bodies used as separators in electrochemical cells
CN1293126C (en) Polymer electrolyte and lithium secondary battery containing the polymer electrolyte
CN1428012A (en) Nonaqueous electrolyte lithium secondary cell
CN1800191A (en) Cyclic carbonate-modified organosilicon compound, non-aqueous electrolytic solution, secondary battery and capacitor
CN1300449A (en) Method for manufacturing active material of positive plate and method for manufacturing nanoqueous electrolyte secondary cell
CN101043093A (en) Sodium ion secondary battery
CN1770540A (en) Lithium polymer secondary battery
CN101080361A (en) Manufacturing method of difluorophosphate, non-aqueous electrolyte solution for secondary cell, and a non-aqueous electrolyte solution secondary cell
CN101069307A (en) Process for producing polyradical compound and battery
CN1350709A (en) Use of additives in electrolytes for electrochemical cells
CN1931863A (en) Cyclic carbonate-modified organosilicon compound, non-aqueous electrolytic solution comprising same, secondary battery, and capacitor
CN1294137C (en) Process for producing boric acid ester compound, electrolyte for electrochemical device, and secondary battery
CN1685556A (en) Nonaqueous electrolytic solution and nonaqueous electrolytic solution secondary battery using it
CN1728442A (en) Nonaqueous electrolyte secondary battery
CN1202019A (en) Non-aqueous electrolyte seondary battery and manufacture thereof
CN1518544A (en) Piperazine derivative, process for producing the same, polymeric solid electrolyte and secondary battery
CN1479402A (en) Polymer electrolyte able to effective anti-leakage and lithium cell using the electrolyte

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C02 Deemed withdrawal of patent application after publication (patent law 2001)
WD01 Invention patent application deemed withdrawn after publication