CN100376620C - Process for producing polyether polymer composition, polyether polymer composition, and solid electrolyte film - Google Patents
Process for producing polyether polymer composition, polyether polymer composition, and solid electrolyte film Download PDFInfo
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- CN100376620C CN100376620C CNB2003801093234A CN200380109323A CN100376620C CN 100376620 C CN100376620 C CN 100376620C CN B2003801093234 A CNB2003801093234 A CN B2003801093234A CN 200380109323 A CN200380109323 A CN 200380109323A CN 100376620 C CN100376620 C CN 100376620C
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Abstract
A process for producing a polyether polymer composition, which comprises preparing a slurry comprising an organic solvent and a polyether polymer dispersed therein, adding to the slurry an antioxidant which is insoluble in the organic solvent and/or a stabilizer which is soluble in the solvent to disperse or dissolve the antioxidant and/or stabilizer, and then removing the organic solvent. Also provided is a polyether polymer composition which comprises polyether polymer particles and an antioxidant insoluble in an organic solvent in which the polymer particles are insoluble and/or a stabilizer soluble in the organic solvent, the composition satisfying at least one of the following (1), (2), and (3): (1) most of the antioxidant is adherent to the surface of the polymer particles, (2) the polyether polymer has a gel content of 5 wt.% or lower, and (3) most of the stabilizer is present in the polymer particles. The polyether polymer composition obtained by the production process and the polyether polymer composition satisfying at least one of the requirements (1), (2), and (3) give a solid electrolyte film having excellent mechanical properties.
Description
Technical field
The present invention relates to contain the composition and method of making the same of polyether composition and antioxidant, and the solid electrolyte film that the said composition moulding is obtained.
Background technology
Mixed electrolyte salt compound in the polyether polymers such as known polyethylene oxide, poly(propylene oxide) then shows high ionic conductivity, is suitable as polymer solid electrolyte.Particularly having adopted in lithium ion battery etc. is the polymer solid electrolyte film of material with the polyether polymer.
For example in the Japanese kokai publication sho 63-136407 communique mixed alkali metal salt in PEP-101 has been proposed, as the trial of ionic conductivity solid electrolyte.In fact, existing report is pointed out: with PEP-101 and LiCF
3SO
3Be dissolved in acetonitrile and carry out curtain coating, remove acetonitrile in inert gas flow He under the reduced pressure, the film that obtains thus shows high ionic conductance.
In recent years, be accompanied by popularizing of polymer battery, needing can be at industrial High-efficient Production polymer solid electrolyte film.But, polyether polymer normally takes place to cut off the material that causes molecular weight to reduce because of molecular chain easily, therefore during for example by the extrusion moulding form film, storage is during as the polyether polymer of formed material and with this forming polymer the time, molecular weight reduces, and is difficult to obtain to have the film of sufficient mechanical strength.Therefore, for addressing this problem, the inventor attempts adding antioxidant when moulding in polyether polymer, by the extrusion moulding form film, but can not fully suppress the reduction of molecular weight.
In addition, make glycidyl allyl ether and PEP-101 copolymerization, carry out crosslinkedly with superoxide, can obtain outside the deionization conductivity, the also improved film of physical strengths such as flexibility, this for example has report in TOHKEMY 2000-123632 communique.But, through the inventor's research, found: when this polyether polymer being shaped to film by extrusion moulding etc. with inferior problem, the storage stage before moulding etc. has taken place partial cross-linked, gelation takes place, and difficult forming is even perhaps can its mechanical characteristics of moulding also descend.
Summary of the invention
The object of the present invention is to provide polyether polymer composition, obtain the suitable preparation method of said composition and the mechanical characteristics that the said composition moulding is obtained and the solid electrolyte film of ionic conductivity excellence, wherein said polyether polymer composition is as the solid electrolyte film formed material, when when long time stored or by forming process such as extrusion mouldings, becoming film in any case, can not cause molecular weight to reduce because of the cut-out of molecular chain, be not easy gelation yet.
The inventor mixes the method for antioxidant and has carried out research in depth for achieving the above object in the subtend polyether polymer.Found that: be scattered in the organic solvent and in the slurry that forms at polyether polymer, disperse to be not dissolved in the antioxidant of above-mentioned organic solvent, remove above-mentioned organic solvent then, even the polyether polymer composition that obtains thus is long time stored, and be shaped to film by extrusion moulding etc., the reduction of molecular weight also can not take place.In addition, again the method for mixed stabilizer in the polyether polymer is studied.Found that: be scattered in the organic solvent and in the slurry that forms at polyether polymer, dissolving is dissolvable in water the stablizer of this organic solvent, remove above-mentioned organic solvent then, even the polyether polymer composition that obtains thus is long time stored, and when being shaped to film by extrusion moulding etc., gelation can not take place yet.As mentioned above, use and to have mixed the polymer composition that antioxidant and/or stablizer obtain, the solid electrolyte film of making shows excellent mechanical characteristics and ionic conductivity thus, the present invention is based on above understanding and finishes.
A first aspect of the present invention provides the preparation method of polyether polymer composition, it is characterized in that: be scattered in the slurry that forms in the organic solvent at polyether polymer and add at least a of the stablizer that is selected from the antioxidant that is not dissolved in this organic solvent and is dissolvable in water this organic solvent and disperse or dissolve, remove above-mentioned organic solvent then.
Second aspect provides polyether polymer composition, it is characterized in that: it is to add at least a of the stablizer that is selected from the antioxidant that is not dissolved in this organic solvent and is dissolvable in water this organic solvent and disperse or dissolve by being scattered at polyether polymer in the slurry that forms in the organic solvent, removes above-mentioned organic solvent then and obtains.
The third aspect provides polyether polymer composition, it is characterized in that: described polyether polymer composition is to contain the polyether polymer particle and be selected from the antioxidant that is not dissolved in organic solvent and be dissolvable in water at least a polyether polymer composition that forms of the stablizer of this organic solvent, wherein said organic solvent does not dissolve described polymer beads, described polyether polymer composition satisfy following (1), (2) and (3) at least one of them:
(1) 50 weight % of this antioxidant total amount or the above polyether polymer particulate surface that is attached to;
(2) gel fraction of polyether polymer is 5 weight % or following;
(3) 50 weight % of this stablizer total amount or above being present in the polyether polymer particle.
Fourth aspect provides solid electrolyte film, the electrolytic salt compound that this solid electrolyte film contains the above-mentioned the 2nd or the 3rd polyether polymer composition and is dissolvable in water this polymer composition.
The preparation method of polyether polymer composition, it is characterized in that: be scattered in to be selected from the slurry that forms in chain stable hydrocarbon and the alicyclic organic solvent to add at polyether polymer and be selected from following (i) and at least a composition (ii) and disperse or dissolve, remove above-mentioned organic solvent then
(i) for being not dissolved in the antioxidant of this organic solvent, for being selected from least a antioxidant of hindered phenol anti-oxidants, amine-ketone antioxidant, secondary aromatic amine class antioxidant and benzimidazoles antioxidant;
(ii) for being dissolvable in water the stablizer of this organic solvent, for salt, hindered phenol compound, phosphorous acid ester based compound and the carbonatoms that is selected from the ring-type amidine is 5 or at least a stablizer of above lipid acid.
Polyether polymer composition, it is characterized in that: described polyether polymer composition contains the polyether polymer particle and is selected from following (i) and at least a composition (ii) forms, described polyether polymer composition satisfy following (1), (2) and (3) prerequisite at least one of them:
(i) for being not dissolved in to the undissolved antioxidant that is selected from chain stable hydrocarbon and alicyclic at least a organic solvent of this polymer beads, for being selected from least a antioxidant of hindered phenol anti-oxidants, amine-ketone antioxidant, secondary aromatic amine class antioxidant and benzimidazoles antioxidant;
(ii) for being dissolvable in water, for salt, hindered phenol compound, phosphorous acid ester based compound and the carbonatoms that is selected from the ring-type amidine is 5 or at least a stablizer of above lipid acid to the undissolved stablizer that is selected from chain stable hydrocarbon and alicyclic at least a organic solvent of this polymer beads;
(1) 50 weight % of this antioxidant (i) total amount or the above polyether polymer particulate surface that is attached to;
(2) gel fraction of polyether polymer is 5 weight % or following;
(3) this stablizer (ii) 50 weight % or above being present in the polyether polymer particle of total amount.
The best mode that carries out an invention
(preparation method of polyether polymer composition)
The preparation method's of polyether polymer composition of the present invention feature is: be scattered in the slurry that forms in the organic solvent at polyether polymer and add at least a of the stablizer that is selected from the antioxidant that is not dissolved in this organic solvent and is dissolvable in water this organic solvent and disperse or dissolve, remove above-mentioned organic solvent then.
Above-mentioned polyether polymer is so long as be that the unitary polymkeric substance of primary structure gets final product with the oxyalkylene repeat units, and there is no particular limitation as to it.By in the undissolved organic solvent of this polyether polymer, making alkylene oxide monomer carry out slurry polymerization, can this polyether polymer of efficient production, the directly conduct " polyether polymer is scattered in the slurry that organic solvent forms " of polymer slurries that generates by slurry polymerization, and be used for the preparation method of polyether polymer composition of the present invention.
Kind for the alkylene oxide monomer that uses in the slurry polymerization is not particularly limited, and preferably uses oxirane monomers (a) at least one composition as the alkylene oxide monomer that uses in the polymerization.More particularly, alkylene oxide monomer be preferably contain 70-99 mole % oxirane monomers (a) and 30-1 mole % can with the monomer mixture of the alkylene oxide monomer (b) of oxyethane copolymerization.
The amount of the oxirane monomers in the alkylene oxide monomer (a) is very few, then use the physical strength of the solid electrolyte film that the polyether polymer that obtained by this alkylene oxide monomer polymerization of mixtures makes not enough, on the contrary, cross the ionic conductance reduction of this solid electrolyte film at most, battery behavior may reduce.
Can with the alkylene oxide monomer (b) of oxyethane copolymerization have alkylene oxide, the carbonatoms 4-10 of carbonatoms 3-20 glycidyl ether, aromatic vinyl compound oxide compound and import bridging property alkylene oxide monomer that crosslinkable groups obtain etc. to these alkylene oxide monomers.
Can with these alkylene oxide monomers (b) of oxyethane copolymerization can be only with a kind of, also can be with 2 kinds or above being used in combination.Among the present invention, preferably use the alkylene oxide of carbonatoms 3-20 or/and at least a composition of the glycidyl ether of carbonatoms 4-10 as alkylene oxide monomer (b), wherein, most preferably uses the alkylene oxide of carbonatoms 3-20.The object lesson of the alkylene oxide of carbonatoms 3-20 has propylene oxide, 1,2-butylene oxide ring etc.
In the inventive method, as required, can use bridging property alkylene oxide monomer at least one composition as above-mentioned alkylene oxide monomer (b).When using the gained polyether polymer composition to use the ionic conductivity dielectric film, preferably use the bridging property alkylene oxide monomer as battery.The bridging property alkylene oxide monomer can use the monomer that imports crosslinkable groups in the alkylene oxide monomers such as glycidyl ether of the alkylene oxide of above-mentioned carbonatoms 3-20, carbonatoms 4-10.Especially preferably have vinyl, hydroxyl and anhydride group etc. and can wherein most preferably have the alkylene oxide monomer of vinyl by the bridging property alkylene oxide monomer of the crosslinkable groups of light or peroxide crosslinking.
Bridging property alkylene oxide monomer with vinyl for example has the unsaturated glycidyl ether of ethylenic, diene or polyenoid monoepoxide, the glycidyl ester class of alkene epoxide and ethylenic unsaturated carboxylic acid etc.The unsaturated glycidyl ether of ethylenic most preferably wherein.The object lesson of the unsaturated glycidyl ether of ethylenic has vinyl glycidyl ether, glycidyl allyl ether etc.
Among the present invention, except that above-mentioned can bridging property alkylene oxide monomer by light or peroxide crosslinking, can also be used in combination the alkylene oxide monomer (epihalohydrins) that Epicholorohydrin, epibromohydrin etc. have halogen atom.
Alkylene oxide monomer used in the present invention (b) contains the bridging property alkylene oxide monomer, particularly above-mentioned can be by the bridging property alkylene oxide monomer of light or peroxide crosslinking, then the gained polyether polymer is undertaken crosslinked by ultraviolet ray or heat easily.When alkylene oxide monomer (b) contained the bridging property alkylene oxide monomer, its amount was generally 9 moles of % or following, preferred 7 moles of % or following, more preferably 5 moles of % or following.
The polymerizing catalyst that uses in the slurry polymerization can use known ring-opening polymerization catalyst.The object lesson of such ring-opening polymerization catalyst has: the catalyzer (Japanese Patent Publication 35-15797 communique) that water and methyl ethyl diketone and organoaluminum reaction obtain, the catalyzer that phosphoric acid and triethylamine and triisobutyl reactive aluminum obtain (Japanese Patent Publication 46-27534 communique), the catalyzer that the organic acid salt of diazabicylo undecylene and phosphoric acid and triisobutyl reactive aluminum obtain (Japanese Patent Publication 56-51171 communique) etc., the catalyzer that wherein uses the organic acid salt of diazabicylo undecylene and phosphoric acid and triisobutyl reactive aluminum to obtain, then the generation of gel component reduces, thereby preferred.
Disperse the organic solvent of polyether polymer so long as do not dissolve the organic solvent of this polyether polymer and get final product, it is not limited, when obtaining polyether polymer by slurry polymerization, further preferably make the dissolving of above-mentioned alkylene oxide monomer and can not make the polymerizing catalyst inactivation, the organic solvent that the polyether polymer of generation is separated out.Such organic solvent for example has: chain stable hydrocarbon such as Skellysolve A, normal hexane; Alicyclic hydrocarbon such as pentamethylene, hexanaphthene; Or the like, wherein preferred chain stable hydrocarbon.
In these organic solvents, make above-mentioned alkylene oxide monomer carry out slurry polymerization by known method, then can obtain polyether polymer and be scattered in the polyether polymer slurry that forms in the above-mentioned organic solvent.
The gel fraction of the polyether polymer that is obtained by aforesaid method is 5 weight % or following, preferred 3% or below, most preferably 1% or below.Gel component in the polyether polymer is too much, difficulty when then using this forming polymer solid electrolyte film, and perhaps the mechanical characteristics of gained solid electrolyte film descends.Gel component in the polyether polymer is the cross-linking agent that generates in the polyether polymer, can be used as toluene insoluble and divides mensuration its content.
The weight-average molecular weight (Mw) of the polyether polymer that is obtained by aforesaid method is preferably 100,000-1,500,000, and more preferably 150,000-1,000,000, preferred especially 200,000-600,000.The weight-average molecular weight of polyether polymer is too small, then uses the flexibility and the physical strength of the solid electrolyte film of said composition to descend, and on the contrary, weight-average molecular weight is excessive, and then the ionic conductivity of this solid electrolyte film may descend.
The molecular weight distribution of polyether polymer (Mw/Mn, here, Mn is a number-average molecular weight) is preferably 1.5-13, more preferably 1.6-12.Preferred especially 1.7-11.
In the method for the present invention, be scattered in insoluble antioxidant of dispersion and/or soluble stabilizers in the slurry that forms in the above-mentioned organic solvent at polyether polymer.
The insoluble antioxidant that uses in the method for the present invention is the common material that uses as the antioxidant of rubber, can suppress to cut off because of molecular chain in each stage of preparation, storage and processing of above-mentioned polyether polymer composition the reduction of the molecular weight that causes, and get final product so long as be not dissolved in the organic solvent that constitutes slurry, it is not particularly limited.
The antioxidant that satisfies above-mentioned important document for example has: 4, and 4 '-thiobis (6-tertiary butyl meta-cresol), 4, the two hindered phenol anti-oxidants such as (6-tertiary butyl meta-cresols) of 4 '-butylidene; 2,2,4 trimethyl 1,2 dihydroquinoline polymer, 6-oxyethyl group-1,2-dihydro-2,2, amine-ketone such as 4-trimethylquinoline are antioxidant; N-phenyl-N '-sec.-propyl-Ursol D, N, N '-secondary aromatic amine such as two-2-naphthyl-Ursol D are antioxidant; Benzoglyoxalines such as 2 mercaptomethyl benzimidazole are antioxidant; Or the like.Wherein consider from suppressing the effect that the polyether polymer molecular chain cuts off, preferred hindered phenol anti-oxidants, preferred especially 4,4 '-thiobis (the 6-tertiary butyl-meta-cresol), 4,4 '-butylidene two (6-tertiary butyl meta-cresol).
Above-mentioned insoluble antioxidant can only use a kind separately, perhaps with 2 kinds or above being used in combination.The amount that is scattered in the antioxidant in the slurry is preferably 0.05-2 weight % with respect to the total amount of the polyether polymer in the slurry, more preferably 0.07-1.5 weight %, most preferably 0.1-1.2 weight %.The amount that is scattered in the antioxidant in the slurry is very few, and then polyether polymer in storage stage and formative stage the molecular weight reduction takes place easily probably.
Soluble stabilizers used in the method for the present invention shows the effect that suppresses gelation in each stage of preparation, storage and processing of above-mentioned polyether polymer composition.Particularly the ionic conductivity solid electrolyte film that is suitable as battery, make in the polyether polymer that the copolymerization of bridging property alkylene oxide monomer obtains, above-mentioned soluble stabilizers shows significant gelation restraining effect.The soluble stabilizers of using in the inventive method is the material that usually uses as the stablizer of rubber, shows the effect that suppresses gelation, and so long as be dissolvable in water getting final product of the organic solvent that constitutes slurry, there is no particular limitation as to it.
The preferred example that satisfies the stablizer of above-mentioned important document has: the salt of ring-type amidine, hindered phenol compound, phosphorous acid ester based compound and carbonatoms are 5 or above lipid acid.
The object lesson of ring-type amidine has: 1, and 4-diazabicylo (2,2,2) octane, 1,6-diazabicylo (3,4,0) nonene-5,1,8-diazabicylo (5,4,0) undecylene-7 etc.Use the organic acid salt of the oleic acid of these ring-type amidines, sad and 2 ethyl hexanoic acid etc. among the present invention.Wherein, preferably use 1, the oleate of 8-diazabicylo (5,4,0) undecylene-7.
The object lesson of hindered phenol compound has: octadecyl-3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic ester, 2,6-di-t-butyl-p-cresol, 4, two (octylsulfo the methyl)-ortho-cresols, 2 of 6-, 6-di-t-butyl-4-(4, two (octylsulfo)-1 of 6-, 3,5-triazine-2-base is amino) phenol, 2,2 '-methylene-bis (4-methyl-6-tert butyl phenol) etc., wherein preferred octadecyl-3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic ester and 4, two (octylsulfo the methyl)-ortho-cresols of 6-.
The object lesson of phosphorous acid ester based compound has: tridecyl phosphite, tricresyl phosphite (nonyl phenyl) ester etc., wherein preferred tridecyl phosphite.
Carbonatoms be 5 or above lipid acid have: tetradecanoic acid, palmitinic acid, stearic acid, lauric acid, linolic acid, oleic acid etc., wherein preferred tetradecanoic acid.
Above-mentioned soluble stabilizers can be used a kind separately, perhaps with 2 kinds or above being used in combination.The amount that is dissolvable in water the stablizer of slurry is preferably 0.05-2 weight % with respect to polyether polymer total amount in the slurry, more preferably 0.07-1.5 weight %, most preferably 0.1-1.2 weight %.The amount of stablizer that is dissolved in slurry is very few, then gelation may take place in storage stage and formative stage in polyether polymer easily, too much opposite, then the performance for the battery that uses solid electrolyte film has detrimentally affect, and wherein said solid electrolyte film is obtained by the polyether polymer composition moulding.
The method of disperseing in the slurry of polyether polymer and/or dissolving above-mentioned insoluble antioxidant and/or soluble stabilizers can be directly to add insoluble antioxidant and/or soluble stabilizers in this slurry, makes its dispersion and/or dissolving.But, preferably insoluble antioxidant is dissolved in advance in the solvent of this antioxidant of solubilized and makes solution, this solution is mixed with above-mentioned slurry, antioxidant is separated out in slurry and the dispersive method.Use this method, antioxidant can become thinner particle, is scattered in the slurry.In this method, the solvent of solubilized antioxidant for example can use aromatic hydrocarbons such as toluene or dimethylbenzene.Soluble stabilizers also can be to be dissolved in organic solvent in advance to make solution, and this solution is mixed with above-mentioned slurry.When using insoluble antioxidant and soluble stabilizers simultaneously, both can be dissolved in both solvents of solubilized and make solution, this solution is mixed with above-mentioned slurry.
After making the antioxidant dispersion and/or making the stablizer dissolving, preferably this slurry is stirred, be stirred in 0-80 ℃, preferred 10-50 ℃ and stirred 1-120 minute, preferably 5-60 minute.
Like this, by removing organic solvent, can obtain containing the polyether polymer composition of polyether polymer and antioxidant and/or stablizer from being dispersed with antioxidant and/or being dissolved with the polymer slurries of stablizer.Removing preferably of organic solvent carried out by the following method: with filtration polymer slurries such as wire nettings, reclaim the polyether polymer particle that is scattered in this slurry, keep heating and/or decompression state then.When directly reclaiming polymkeric substance, preferably at 30-45 ℃ of drying under reduced pressure with the particulate state.Temperature is low excessively, and then solvent is difficult to evaporation, and temperature is too high, then may adhere to caking between the polymer beads.
(polyether polymer composition)
Polyether polymer composition of the present invention comprises following two kinds of polyether polymer compositions (i), (ii).
(i) polyether polymer composition (below can be described as " polyether polymer composition (i) "), it is characterized in that: be scattered in to polyether polymer and add stablizer at least a that is selected from the antioxidant that is not dissolved in this organic solvent and is dissolvable in water this organic solvent in the slurry that organic solvent forms, disperse or dissolve, remove above-mentioned organic solvent then and obtain.
(ii) polyether polymer composition (below can be described as " polyether polymer composition (ii) ") is characterized in that: this polyether polymer composition contains the polyether polymer particle and at least a of stablizer of being selected from the antioxidant that is not dissolved in the organic solvent that does not dissolve described polymer beads and being dissolvable in water this organic solvent forms; Described polyether polymer composition satisfy following (1), (2) and (3) at least one of them:
(1) 50 weight % of this antioxidant total amount or the above polyether polymer particulate surface that is attached to;
(2) gel fraction of polyether polymer is 5 weight % or following;
(3) 50 weight % of this stablizer total amount or on be present in the polyether polymer particle.
Polyether polymer composition of the present invention can have (ii) both characteristics of polyether polymer composition (i) and polyether polymer composition concurrently.
In the polyether polymer composition (1), the content among the preparation method of the method for removing of the kind of the organic solvent of the kind of polyether polymer, its preparation method, slurry, antioxidant and stablizer, their dispersing method and organic solvent etc. and aforementioned polyether polymer composition of the present invention is identical.
When containing the polyether polymer composition (i) of insoluble antioxidant, the preferred, polyethers polymkeric substance comprises polymer beads, 50 weight % of antioxidant total amount or the above above-mentioned polyether polymer particulate surface that is attached in the said composition.In addition, when when containing the polyether polymer composition (i) of soluble stabilizers, the gel fraction of preferred, polyethers polymkeric substance is 5 weight % or following, also the preferred, polyethers polymkeric substance comprises polymer beads, 50 weight % of stablizer total amount or above being present in the above-mentioned polyether polymer particle in the said composition.
Polyether polymer composition (i) and the polyether polymer composition polyether polymer particle grain size in (ii) is generally 0.02-2mm, preferred 0.05-1mm, more preferably 0.1-0.5mm.
Antioxidant the adhesion amount of polyether polymer particle surface be preferably antioxidant total amount in the composition 70 weight % or more than, more preferably 80 weight % or more than.Antioxidant the polyether polymer particle surface to adhere to ratio big more, polyether polymer composition situation about reducing then at storage stage and the difficult more generation molecular weight of formative stage.Antioxidant can followingly be obtained at the adhesion amount of polyether polymer particle surface: the polyether polymer particle is washed with ether, with being attached to the antioxidant wash-out on surface, this diethyl ether solution is carried out ultraviolet spectral analysis, antioxidant concentration is carried out quantitatively.
The preferred 0.05-2.0 weight of the content % of polyether polymer composition (i) and the polyether polymer composition antioxidant in (ii), more preferably 0.07-1.5 weight %, most preferably 0.1-1.2 weight %.The content of antioxidant is very few, then at storage stage or formative stage, the molecular weight of polyether polymer reduces easily, too much opposite, then the performance for the battery that uses solid electrolyte film has detrimentally affect, and wherein said solid electrolyte film is obtained by this polyether polymer composition moulding.
The amount that is present in the stablizer in the polyether polymer particle be preferably the stablizer total amount in the composition 70 weight % or more than, more preferably 80 weight % or more than.The ratio that is present in the stablizer in the polyether polymer particle in the polyether polymer composition is big more, and then polyether polymer composition is in storage stage and the difficult more generation gelation of formative stage.The content that is present in the stablizer in the polyether polymer particle can followingly calculate: polyether polymer composition is washed with normal hexane, to be attached to the stablizer of polyether polymer particle surface or independently be present in the stablizer wash-out of this particle outside, measure the weight of this polymer beads, then, above-mentioned polymer beads is dissolved in water, filter gained solution, measure the weight that is trapped in the stablizer on the filter paper, calculate by these measured values.
The preferred 0.05-2.0 weight of the content % of polyether polymer composition (i) and the polyether polymer composition stablizer in (ii), more preferably 0.07-1.5 weight %, most preferably 0.1-1.2 weight %.The content of stablizer is very few, then at storage stage and formative stage, gelation takes place in polyether polymer easily, and is too much opposite, then the performance for the battery that uses solid electrolyte film has detrimentally affect, and wherein said solid electrolyte film is obtained by this polyether polymer composition moulding.
Because above-mentioned polyether polymer composition (i) and polyether polymer composition are (ii) in storage stage and forming process stage etc., the molecular weight of polyether polymer reduces and/or gelation has obtained inhibition, therefore, even be shaped to film like, also can obtain the film of mechanical characteristics excellence by heating and melting methods of forming such as extrusion mouldings.Thereby, preferred especially material as solid electrolyte film.
(solid electrolyte film)
Solid electrolyte film of the present invention contains and is selected from above-mentioned polyether polymer composition (i) and polyether polymer composition polyether polymer composition (ii) and the electrolytic salt compound that is dissolvable in water this polymer composition.
Electrolytic salt compound used among the present invention is the compound that positively charged ion is moved, so long as be dissolvable in water getting final product of the polyether polymer composition that uses among the present invention, is not particularly limited.The object lesson of such electrolytic salt compound has: contain halide-ions, high chloro acid ion, thiocyanate ion, trifluoromethanesulfonic acid ion (CF
3SO
3 -), two (fluoroform sulphonyl) imines ion (N (CF
3SO
2)
2 -), two (five fluorine, third sulphonyl) imines ion (N (C
2F
5SO
2)
2 -), trifluoro ス Le ホ Application ィ ミ De ion, Tetrafluoroboric acid ion (BF
4 -), nitrate ion, AsF
6 -, PF
6 -, metallic cation such as negatively charged ion such as stearic azochlorosulfonate acid ion, hot azochlorosulfonate acid ion and Li, Na, K, Rb, Cs salt.Wherein, during in particular as the solid electrolyte of lithium polymer battery, more preferably LiBF
4, LiPF
6, LiCF
3SO
3, LiN (CF
3SO
2)
2, LiN (C
2F
5SO
2)
2
These electrolytic salt compounds can use separately, perhaps with 2 kinds or above being used in combination.The electrolytic salt compound is with respect to the usage quantity of polyether polymer, i.e. (the basic metal mole number in the electrolytic salt compound)/(total mole number of ether oxygen atom in the polymkeric substance) is generally 0.001-5, preferred 0.005-3, the more preferably amount of 0.01-1.The usage quantity of electrolytic salt compound is too much, and then the physical strength of solid electrolyte film reduces sometimes, and perhaps ionic conductivity reduces.On the contrary, the amount of electrolytic salt compound is very few, and then the ionic conductivity of solid electrolyte film reduces sometimes, and battery performance reduces.
The method of above-mentioned polyether polymer composition being made film like can adopt following any means: (1) with roller or Banbury mixer etc., by known method in advance with above-mentioned polyether polymer composition and the electrolytic salt compound method of moulding then; (2) during moulding, all or part of of above-mentioned each composition for example mixed the method for an edge forming on one side in the forcing machine.
Forming method can adopt extrusion moulding, shaping method to suppress, injection moulding and solution casting method etc., among the present invention, considers from surface smoothing, the productive rate equal angles of solid electrolyte film, preferably adopts extrusion moulding.In addition, when carrying out film forming, most preferably use the die head extrusion molding of biaxial extruder by extrusion moulding.
Carry out crosslinkedly as required, can further improve mechanical characteristicies such as the flexibility of the film that obtains by aforesaid method or physical strength.Crosslinked method can adopt mixed cross-linker in polyether polymer composition, carries out crosslinked method by methods such as heating; Carry out crosslinked arbitrary method such as method with ultraviolet ray, electron rays isoreactivity energy-ray.Solid electrolyte film of the present invention is preferably undertaken crosslinked by ultraviolet ray.
The thickness of solid electrolyte film of the present invention is generally 1-200 μ m, preferred 2-100 μ m, more preferably 5-30 μ m.Thickness is thin excessively, and it is not enough, too thick on the contrary then to make stability, and then ionic conductivity reduces, and possibly can't improve the output of the battery that uses this film.
Solid electrolyte film of the present invention can be preferably uses as the solid electrolyte of battery.More particularly, can be used as the ion-conductive electrolyte film of battery and cathode thin film etc.
The battery variety of applicable solid electrolyte film of the present invention is not particularly limited, and basic metal class batteries such as lithium, potassium, sodium are for example arranged; Halogen batteries such as zinc-silver chloride, magnesium-silver chloride, magnesium-cupric chloride; Proton conduction type batteries such as nickel-hydrogen cell etc.Wherein, the preferred high-octane lithium cell of high-voltage.In addition, the form of battery most preferably ionogen does not contain electrolytic solution, only contains the battery of polymer solid electrolyte.
(embodiment)
Below provide embodiment, comparative example, be described more specifically the present invention, but the present invention is not limited by this.If no special instructions, part and the % in embodiment and the comparative example is weight basis.
(1) polymkeric substance is formed
The polymkeric substance of polyether polymer is formed H-NMR and the C that adopts 500MHz
13-NMR measures.
(2) weight-average molecular weight (Mw) and molecular weight distribution (Mw/Mn)
Mw and Mw/Mn adopt gel permeation chromatography (GPC) to measure according to following condition.
Device: eastern ソ-Co., Ltd. makes the GPC system
Post: eastern ソ-Co., Ltd. makes G7000HHR+GMHHR-H
Solvent: DMF (lithiumbromide 5mmol/L)
Flow velocity: 1ml/ minute column temperature: 40 ℃
Molecular weight standard thing: the polystyrene standard that Port リ マ-ラ ボ ラ ト リ-company makes
(3) stabiliser content in the polyether polymer particle
Polyether polymer composition is washed with normal hexane, to be attached to the stablizer of polyether polymer particle surface or independently be present in the stablizer wash-out of this particle outside, measure the weight of this polymer beads, then, above-mentioned polymer beads is dissolved in water, filter gained solution, measure the weight that is trapped in the stablizer on the filter paper, calculate by these measured values.
(4) gel fraction
With 0.2g polyether polymer composition and the 100ml toluene 100ml Erlenmeyer flask of packing into,, the solubilized composition is dissolved fully 40 ℃ of vibrations 3 hours, with 150 purpose metal mesh filters, remove the part that is dissolvable in water toluene, then with the resistates drying on the wire netting, calculated weight.The ratio of calculating this exsiccant resistates and original polymer weight is as gel fraction.
(5) antioxidant is at the adhesive rate on polymer beads surface
In the polyether polymer composition, antioxidant is obtained with respect to the ratio of total amount is following at the adhesion amount of polyether polymer particle surface.The polyether polymer particle that the surface is attached with antioxidant carries out quantitative sampling, with quantitative ether washing, wash-out goes out this antioxidant, and this diethyl ether solution is carried out ultraviolet spectral analysis, the dissolved antioxidant concentration is carried out quantitatively, calculate the amount that is dissolved in the antioxidant in the quantitative ether.
(6) package stability and processing stability
A) by inquiry with polyether polymer composition 40 ℃ store 70 hours after molecular weight have or not reduction, perhaps store gel fraction after 70 hours under the nitrogen atmosphere by measuring, estimate package stability.
B) whether there is after mixing 2 minutes molecular weight to reduce at 60 ℃ polyether polymer composition with Brabender by inquiry, perhaps measures with Brabender, estimate processing stability at 60 ℃ of gel fractions after mixing 3 minutes.
Whether there is molecular weight to reduce, can judges by the reduced rate of measuring the polyether polymer reducing viscosity that causes because of the molecular chain cut-out.The reducing viscosity of polyether polymer can followingly calculate: the 0.25g polyether polymer composition is dissolved in 100g toluene, measures the solution lowering time with Ubbelohde viscometer (viscometer No.1) at 25 ℃, calculated by following formula.
Reducing viscosity (η sp/C)=[(t-t
0)/t
0]/0.217
T: the lowering time of polyethers solution (second)
t
0: the lowering time of toluene (second)
(7) mechanical characteristics of solid electrolyte film
Use polyether polymer composition, with extrusion moulding formation solid electrolytic thin-membrane, measure and do not take place under the situation of crackle or fracture on the film this moment, the maximum winding speed in the coiling limit is estimated.
(8) ionic conductance
The mensuration of ionic conductance be with 30 ℃, 1mmHg or 72 hours solid electrolyte film of following vacuum-drying week platinum electrode clamp, with the AC method of 0.5V voltage, 5Hz-13MHz range of frequency, calculate ionic conductance by the complex impedance method.
Embodiment 1
Use oxyethane and propylene oxide, in normal hexane, carry out slurry polymerization by known method, the slurry that obtain ethylene oxide unit (EO) and be 90 moles of %, propylene oxide units (PO) and be 10 moles of %, weight-average molecular weight (Mw) and be 350,000, molecular weight distribution (Mw/Mn) is 10.2 polyether polymer (EO/PO).
Preparation antioxidant 4, the 0.05g/ml toluene solution of 4 '-thiobis (3 methy 6 tert butyl phenol) (the emerging chemical industry of imperial palace Co., Ltd. makes ノ Network ラ ッ Network 300), this solution is added in the slurry, the amount that makes antioxidant is 0.5% with respect to the amount of polyether polymer, stirred 30 minutes at 30 ℃, antioxidant is separated out.Then, with this slurry metal mesh filter,, obtain polyether polymer composition 35 ℃ of particle vacuum-dryings that will be trapped in the polyether polymer on the wire netting 4 hours.The amount of the antioxidant in the said composition is 0.45%, and wherein almost full dose (90% or more than) is attached to the polyether polymer particle surface.
Reduce package stability and the processing stability of estimating above-mentioned polyether polymer composition by checking that molecular weight has or not.The result is as shown in table 1.
Embodiment 2
Change the kind of antioxidant into 4,4 '-butylidene two (the 6-tertiary butyl-meta-cresol) (chemistry society of Kawaguchi makes ア Application テ-ジ W-500), its addition changes 0.4% into, in addition prepares polyether polymer composition similarly to Example 1.The amount of antioxidant is 0.37% in the said composition, and wherein almost full dose (90% or more than) is attached to the polyether polymer particle surface.
Reduce package stability and the processing stability of estimating above-mentioned polyether polymer composition by checking that molecular weight has or not.The result is as shown in table 1.
Comparative example 1
Adding octadecyl-3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic ester (Japanese チ バ ガ ィ ギ-company makes ィ Le ガ ノ ッ Network ス 1076) in the slurry by embodiment 1 gained as antioxidant, makes its amount be 0.5 weight % of polyether polymer.This antioxidant is dissolved in the solvent (normal hexane) of slurry fully.Stir 30 minutes these slurry at 35 ℃,,, obtain polyether polymer composition 35 ℃ of polyether polymer particle vacuum-dryings 4 hours that will be trapped on the wire netting then with this slurry of metal mesh filter.The amount of antioxidant is 0.15% in the composition, almost all is not attached to the polyether polymer particle surface.
Reduce package stability and the processing stability of estimating above-mentioned polyether polymer composition by checking that molecular weight has or not.The result is as shown in table 1.
Comparative example 2
The polymer slurries that is obtained by embodiment 1 is not added antioxidant, directly use metal mesh filter, 35 ℃ of particle vacuum-dryings that will be trapped in the polyether polymer on the wire netting 4 hours, adding is 4 of 0.5 weight % with respect to this polymer beads total amount, the powder of 4 '-thiobis (3 methy 6 tert butyl phenol), thorough mixing obtains polyether polymer composition.
Reduce package stability and the processing stability of estimating above-mentioned polyether polymer composition by checking that molecular weight has or not.The result is as shown in table 1.
Table 1
| Embodiment 1 | Embodiment 2 | Comparative example 1 | Comparative example 2 | |
| Polyether polymer | EO/PO | EO/PO | EO/PO | EO/PO |
| Slurry solvent | Normal hexane | Normal hexane | Normal hexane | Normal hexane |
| Oxidation preventive content | 0.45％ | 0.37％ | 0.15％ | 0.5％ |
| Antioxidant surface attachment rate | 90% or more than | 90% or more than | - | - |
| 40 ℃, store reducing viscosity reduced rate after 70 hours | 0.5％ | 1.2％ | 20％ | 35％ |
| The mixing back of Brabender reducing viscosity reduced rate | 2％ | 3％ | 50％ | 38％ |
As shown in Table 1: use in the polyether polymer composition of the antioxidant preparation that is dissolvable in water the insoluble organic solvent (being normal hexane in the present embodiment) of separating the slurry polymerization of polyether polymer, the antioxidant that adds in the slurry has only 30% of total amount to remain in the composition, and remaining antioxidant almost is not attached to the polyether polymer particle surface.Said composition is in the long storage stage, or mixing with brabender, all causes reducing viscosity to reduce (comparative example 1) because of molecular chain cuts off.
For the polyether polymer composition that only is mixed with the antioxidant powder in the polyether polymer particle, in the long storage stage, or mixing with brabender, all, molecular chain cause reducing viscosity to reduce (comparative example 2) because of cutting off.
And use in the polyether polymer composition of the antioxidant preparation that is not dissolved in the slurry polymerization organic solvent, add to antioxidant in the slurry 90% or abovely all remain in the composition, and as defined of the present invention, be attached with on the polyether polymer particle surface remaining antioxidant 90% or more than.The susceptible of proof said composition is in the long storage stage, or mixing with brabender, reduces little (embodiment 1,2) because of molecular chain cuts off the reducing viscosity that causes.
Embodiment 3
Add two fluoroform sulphonyl imido lithiums at 3000 parts in by the polyether polymer compositions of embodiment 1 preparation, make (the lithium atom mole number of electrolytic salt)/ratio of (the Sauerstoffatom mole number of polyether polymer) is 0.05, obtains the solid electrolyte composition.Said composition is supplied with biaxial extruder, extrude for 155 ℃ with 80 ℃ of extruder temperatures, revolution 150rpm, die head temperature.Be rolled into volume even the thickness of gained is the solid electrolyte film of 20 μ m with maximum winding speed 20m/ minute, also can not crack or rupture the physical strength excellence.In addition, ionic conductance is 1 * 10
-5, show excellent ionic conductivity.
Embodiment 4
Use oxyethane and propylene oxide and glycidyl allyl ether, in normal hexane, carry out slurry polymerization by known method, obtaining ethylene oxide unit (EO) is that 90 moles of %, propylene oxide units (PO) are that 5 moles of % and glycidyl allyl ether unit (AGE) are that 5 moles of %, weight-average molecular weight are 350,000, molecular weight distribution is the slurry of 10.2 polyether polymer (EO/PO/AGE).
In above-mentioned slurry, add stablizer 1,8-diazabicylo (5,4,0) oleate of undecylene-7 (サ Application ア ボ ッ ト Co., Ltd. makes U-CAT SA No.106), making its amount is 0.5% with respect to polyether polymer, stirs 30 minutes at 30 ℃, makes the stablizer dissolving.Then with this slurry metal mesh filter,, obtain polyether polymer composition 35 ℃ of particle vacuum-dryings that will be trapped in the polyether polymer on the wire netting 4 hours.Measure the gel fraction in the said composition, the result is 0.3 weight % with respect to polyether polymer.In addition, the amount of the stablizer in the composition is 0.46%.
Estimate the package stability and the processing stability of above-mentioned polyether polymer composition by measuring gel fraction.The result is as shown in table 2.
Embodiment 5
Change the kind of stablizer into tridecyl phosphite (the system ア デ カ ス of Asahi Denka Kogyo K. K Block 3010), making its addition is 0.7%, in addition prepares polyether polymer composition similarly to Example 4.Gel fraction in the said composition is 0.1 weight % with respect to polyether polymer.In addition, the amount of stablizer is 0.65% in the composition.
Estimate the package stability and the processing stability of above-mentioned polyether polymer composition by measuring gel fraction.The result is as shown in table 2.
Comparative example 3
Add stablizer 2 in by the slurry of embodiment 4 gained, 2-methylene-bis (4-methyl-6-tert butyl phenol) makes its amount be 0.5 weight % of polyether polymer.This stablizer is not dissolved in slurry, stirs 30 minutes these slurry at 30 ℃, then with this slurry of metal mesh filter, 35 ℃ of particle vacuum-dryings that will be trapped in the polyether polymer on the wire netting 4 hours, obtains polyether polymer composition.Gel fraction in the said composition is 6.5 weight % with respect to polyether polymer.
Estimate the package stability and the processing stability of above-mentioned polyether polymer composition by measuring gel fraction.The result is as shown in table 2.
Table 2
| Embodiment 4 | Embodiment 5 | Comparative example 3 | |
| Polyether polymer | EO/PO/AGE | EO/PO/AGE | EO/PO/AGE |
| Slurry solvent | Normal hexane | Normal hexane | Normal hexane |
| Gel fraction behind the heat drying | 0.1％ | 0.1％ | 6.5％ |
| Gel fraction after storing under the nitrogen condition | 0.1％ | 0.2％ | 8.2％ |
| The mixing back of Brabender gel fraction | 0.2％ | 0.3％ | 10.1％ |
As shown in Table 2: use the polyether polymer composition that is not dissolved in the stablizer preparation of the insoluble organic solvent of polyether polymer (being normal hexane in the present embodiment), from slurry recovery and heat drying the time, gel fraction has surpassed 5 weight %, and under the nitrogen condition, store afterwards, mixing with brabender, gel fraction increases (comparative example 3).
And use is dissolvable in water the polyether polymer composition of the present invention of the stablizer preparation of normal hexane, from slurry recovery and heat drying the time, gel fraction is less than 5 weight %, even and storage under the nitrogen condition, mixing with brabender afterwards, gel fraction increases (embodiment 4,5) hardly.
Embodiment 6
In 3000 parts of polyether polymer compositions that prepare by embodiment 4, add two fluoroform sulphonyl imido lithiums, make (the lithium atom mole number of electrolytic salt)/ratio of (the Sauerstoffatom mole number of polyether polymer) is 0.05, add 3 parts of benzyldimethylketals as Photoepolymerizationinitiater initiater, thorough mixing obtains the solid electrolyte composition.Said composition is supplied with biaxial extruder, extrude for 155 ℃ with 80 ℃ of extruder temperatures, revolution 150rpm, die head temperature.The film of extruding is attached on polypropylene (PP) film continuously, is undertaken crosslinked by uviolizing.Solid electrolyte film on the PP film is peeled off, be rolled into volume with maximum winding speed 20m/ minute, also can not crack or rupture the physical strength excellence even the thickness of gained is the solid electrolyte film of 20 μ m.In addition, ionic conductance is 1 * 10
-5, show excellent ionic conductivity.
Embodiment 7
In the slurry of the polyether polymer (EO/PO/AGE) for preparing by embodiment 4, add tridecyl phosphite (Asahi Denka Kogyo K. K makes ア デ カ ス Block 3010), make its amount be 0.7% of polyether polymer as stablizer.Refabrication is as 4 of antioxidant, the 0.05g/ml toluene solution of 4 '-thiobis (3 methy 6 tert butyl phenol) (the emerging chemical industry of imperial palace Co., Ltd. makes ノ Network ラ ッ Network 300), this solution is added in the slurry, and the amount that makes antioxidant is 0.5% with respect to the amount of polyether polymer.Stirred 30 minutes at 30 ℃, make the stablizer dissolving, antioxidant is separated out.Then, with this slurry of metal mesh filter,, obtain polyether polymer composition 35 ℃ of particle vacuum-dryings that will be trapped in the polyether polymer on the wire netting 4 hours.
The amount of antioxidant is 0.46% in the said composition, and wherein almost full dose (90% or more than) is attached to the polyether polymer particle surface.Measure the gel fraction in the said composition, the result is 0 weight % with respect to polyether polymer.The amount of the stablizer in the composition is 0.67%.
Do not reduce and the mensuration gel fraction by checking that molecular weight has, estimate the package stability and the processing stability of above-mentioned polyether polymer composition.The result is as follows.
Polyether polymer EO/PO/AGE
The slurry solvent normal hexane
Oxidation preventive content 0.46%
Antioxidant surface attachment rate 90% or more than
40 ℃ keep reducing viscosity reduced rate-0.1% after 70 hours
The mixing back of Brabender reducing viscosity reduced rate 0.2%
Gel fraction 0% behind the heat drying
Store back gel fraction 0% under the nitrogen condition
The mixing back of Brabender gel fraction 0.1%
* reducing viscosity increases 0.1%
By The above results as can be known: the antioxidant that will be not dissolved in normal hexane is used in combination with the stablizer that is dissolvable in water normal hexane, thus in Zhi Bei the polyether polymer composition of the present invention, add to antioxidant in the slurry 90% or more than remain in the composition, and remaining antioxidant 90% or more than be attached to the polyether polymer particle surface.Even said composition in the long storage stage reduction of the reducing viscosity cause can not take place to cut off because of molecular chain yet, reduction is arranged slightly only also when Brabender is mixing.Even reclaim from slurry and during heat drying, and when storing under the nitrogen condition afterwards, gel fraction does not all increase, and Brabender also increases when mixing hardly.
Industrial applicability
When the polyether polymer composition that is obtained by method of the present invention is shaped to film when storing with material as solid electrolyte film and by extrusion molding etc. in any case, can not occur to reduce because strand cuts off the molecular weight that causes, can not cause gelation yet, therefore the solid electrolyte film of mechanical property and ionic conductivity excellence can be provided.
Therefore, solid electrolyte film of the present invention can be preferably used as the solid electrolyte of battery. More particularly, can be used as ion-conductive electrolyte film, cathode thin film and the anode film etc. of battery.
Claims (8)
1. the preparation method of polyether polymer composition, it is characterized in that: be scattered in to be selected from the slurry that forms in chain stable hydrocarbon and the alicyclic organic solvent to add at polyether polymer and be selected from following (i) and at least a composition (ii) and disperse or dissolve, remove above-mentioned organic solvent then
(i) for being not dissolved in the antioxidant of this organic solvent, for being selected from least a antioxidant of hindered phenol anti-oxidants, amine-ketone antioxidant, secondary aromatic amine class antioxidant and benzimidazoles antioxidant;
(ii) for being dissolvable in water the stablizer of this organic solvent, for salt, hindered phenol compound, phosphorous acid ester based compound and the carbonatoms that is selected from the ring-type amidine is 5 or at least a stablizer of above lipid acid.
2. the preparation method of the polyether polymer composition of claim 1 wherein, mixes with above-mentioned slurry by the solution that will be dissolved with antioxidant, and antioxidant is scattered in the slurry.
3. the preparation method of the polyether polymer composition of claim 1, wherein, this antioxidant (i) is a hindered phenol anti-oxidants.
4. the preparation method of each polyether polymer composition among the claim 1-3, wherein, the organic solvent of slurry is the chain stable hydrocarbon.
5. polyether polymer composition, it is characterized in that: described polyether polymer composition contains the polyether polymer particle and is selected from following (i) and at least a composition (ii) forms, described polyether polymer composition satisfy following (1), (2) and (3) prerequisite at least one of them:
(i) for being not dissolved in to the undissolved antioxidant that is selected from chain stable hydrocarbon and alicyclic at least a organic solvent of this polymer beads, for being selected from least a antioxidant of hindered phenol anti-oxidants, amine-ketone antioxidant, secondary aromatic amine class antioxidant and benzimidazoles antioxidant;
(ii) for being dissolvable in water, for salt, hindered phenol compound, phosphorous acid ester based compound and the carbonatoms that is selected from the ring-type amidine is 5 or at least a stablizer of above lipid acid to the undissolved stablizer that is selected from chain stable hydrocarbon and alicyclic at least a organic solvent of this polymer beads;
(1) 50 weight % of this antioxidant (i) total amount or the above polyether polymer particulate surface that is attached to;
(2) gel fraction of polyether polymer is 5 weight % or following;
(3) this stablizer (ii) 50 weight % or above being present in the polyether polymer particle of total amount.
6. the polyether polymer composition of claim 5, described polyether polymer composition by be scattered at polyether polymer in the slurry that forms in the organic solvent add be selected from this antioxidant (i) and this stablizer (ii) at least a composition and disperse or dissolve, remove above-mentioned organic solvent then and obtain.
7. claim 6 or 7 polyether polymer composition, wherein, this antioxidant (i) is a hindered phenol anti-oxidants.
8. solid electrolyte film, this solid electrolyte film contain the polyether polymer composition of claim 5 and are dissolvable in water the electrolytic salt compound of this polymer composition.
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| JP2002348255A JP4360080B2 (en) | 2002-11-29 | 2002-11-29 | Method for producing polyether polymer composition |
| JP348330/2002 | 2002-11-29 |
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| CN101222055B (en) * | 2008-01-09 | 2011-08-17 | 清华大学 | Co-polymer based polymer electrolyte material for lithium battery, compound electrolyte film and its preparation method |
| TWI591670B (en) * | 2012-07-26 | 2017-07-11 | 財團法人工業技術研究院 | Electrolyte mixture, electrolytic capacitor using the same and oxidant mixture for conjugated polymer synthesis |
| WO2014133024A1 (en) * | 2013-02-27 | 2014-09-04 | ダイソー株式会社 | Positive electrode and nonaqueous electrolyte secondary battery |
| CN107924769B (en) * | 2015-09-30 | 2020-11-03 | 株式会社大阪曹達 | Composition for gel electrolyte |
| CN109755646B (en) * | 2019-01-22 | 2021-04-09 | 北京卫蓝新能源科技有限公司 | Organic material and preparation method thereof, organic solid electrolyte and preparation method and application thereof |
| CN112038693B (en) * | 2020-09-11 | 2022-05-17 | 惠州亿纬锂能股份有限公司 | Solid electrolyte and preparation method and application thereof |
| CN114426688A (en) * | 2020-10-15 | 2022-05-03 | 中国石油化工股份有限公司 | Method for preparing rubber aid dispersion liquid, brominated butyl rubber and preparation method thereof |
| CN114865076A (en) * | 2022-05-30 | 2022-08-05 | 远景动力技术(江苏)有限公司 | Electrolyte material and application thereof |
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| JPS564628A (en) * | 1979-06-26 | 1981-01-19 | Nippon Zeon Co Ltd | Production of epihalohydrin copolymer rubber |
| JPS63136407A (en) * | 1986-11-27 | 1988-06-08 | 日立マクセル株式会社 | Lithium ion conducting polymer electrolyte |
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| JP3104127B2 (en) * | 1997-05-23 | 2000-10-30 | 第一工業製薬株式会社 | Solid electrolyte |
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| JP2002105195A (en) * | 2000-09-28 | 2002-04-10 | Nippon Shokubai Co Ltd | Method for producing catalyst for alkylene oxide polymerization |
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| JP2004182778A (en) * | 2002-11-29 | 2004-07-02 | Nippon Zeon Co Ltd | Method for manufacturing polyether polymer composition, polyether polymer composition and solid electrolyte film |
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