CN1051569A - High-molecular composite solid electrolyte and method for making - Google Patents
High-molecular composite solid electrolyte and method for making Download PDFInfo
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- CN1051569A CN1051569A CN 89108502 CN89108502A CN1051569A CN 1051569 A CN1051569 A CN 1051569A CN 89108502 CN89108502 CN 89108502 CN 89108502 A CN89108502 A CN 89108502A CN 1051569 A CN1051569 A CN 1051569A
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Abstract
The present invention relates to a kind of at room temperature have than macroion select and conductive high-molecular composite solid electrolyte and method for making thereof.
The solid state electrolyte device is long because of its stable performance, life-span, has highly and be easy to advantage such as preparation than liquid electrolyte ionic conduction selectivity, thereby development in recent years is very fast.The invention provides compound anion conductor oxygen ion conductor and the proton conductor made of a kind of polynary organic ammonium and polymkeric substance, the specific conductivity height of the corresponding ionophore of making than prior art, its manufacture method, can heat under the Undec temperature of institute's doping near body material fusion, make solvent evaporates compression molding and making then.
Description
The present invention relates to a kind of at room temperature have higher ionic conduction selectivity and conductive high-molecular composite solid electrolyte and manufacture method thereof.
Device with solid state electrolyte is made owing to have stable performance, the life-span of making than liquid electrolyte long, has advantages such as ionic conduction selectivity, in recent years in solid dielectric electricity dielectric pond, electricity look device, digital telephone device, electrical condenser, gas pump, static inhibitor, ion selective electrode, ion(ic)activity time meter, transmitter, aspects such as heterogeneous catalysis high-temperature heating element all are applied.Development is the inorganic materials solid state electrolyte the earliest, has developed small molecules organic materials and inorganics compound organic composite solid ionogen subsequently, thereby has not only improved the physical and chemical performance of original material, and increased a lot of ionophore kinds.The high-molecular composite solid electrolyte of development in recent years is a kind of new type of solid state ionophore, and following several types is arranged: (1) can with the polymkeric substance of metal ion or inorganic ammonium complexing and the mixture of metal-salt or inorganic ammonium salt.(2) mixture of polycation or polyanion and polyoxyethylene glycol softening agent such as (PEG).(3) with the polycation quaternary ammonium, the mixture of uncle Liu Huo Phosphonium and polyanion is made body material, adds the lithium ion conductor of inorganic lithium salt.(4) with the bronsted mixture of part compatible polymers and bronsted acid perhaps mutually.(5) polar polymer, the mixture of metal-salt and solvent.
The present invention adopts small molecules organic ammonium and the compounded anion conductor of polymkeric substance, than the ionic conductivity height with inorganic materials anion conductor or polycation and polymer P EG compound anion conductor; Adopt the compounded oxygen ion conductor of small molecules amine oxide and polymkeric substance than the specific conductivity height made from inorganic materials; Adopt the protic acid salt of small molecules organic amine and the compounded proton conductor of polymkeric substance, its electroconductibility is than the height of the proton conductor of mixture inorganic materials or polymkeric substance and protonic acid.And have preparation easily with the solid state ionic conductor of manufacturing of the present invention, advantage such as product stability is good.
Organic ammonium during solid state electrolyte provided by the invention is formed has three types, is respectively applied for to make proton conductor, anion conductor and oxygen ion conductor.Used organic ammonium can be following three classes:
One, the protic acid salt of organic amine.Organic amine especially tertiary amine can be monobasic, polybasic or heterocyclic.The group that is connected with nitrogen-atoms can generally contain atoms such as one or several O, N for the saturated footpath of carbon number 1-10, how to be connected with aryl, or the aryl of carbon number 6-10, should be compatible with single kind or multiple polymers matrix.Protonic acid can be ortho-phosphoric acid, metaphosphoric acid, triphosphoric acid, tetra-sodium, Hypophosporous Acid, 50, Tripyrophosphoric acid, phosphorous acid, sulfuric acid, tosic acid, gifblaar poison, sulfonic acid trifluoromethane reach heteropolyacids such as 12 phosphomolybdate, 12 phospho-wolframic acids, 12 silicomolybdic acid, six tellurium molybdic acids.The positive ion of the protic acid salt of this tertiary amine can be (CH
3)
3N
+H, (C
2H
5)
3N
+H, (n-C
4H
9)
3N
+H, (CH
3)
2C
6H
5N
+H,
,
Deng.The object lesson of salt is: (CH
3)
3N1/3H
3PO
4, (C
2H
5)
3N
H1/3H
3PO
4, (n-C
4H
9)
3N1/3H
3PO
4, (CH
3)
2C
6H
5N1/3H
3PO
4,
1/3H
3PO
4Deng, the compound proton conductor that can be made into of the protic acid salt of this organic amine and polymkeric substance.
Two, quaternary ammonium salt (comprising quaternary ammonium hydroxide).Can be monobasic, polynary or heterocyclic, the protic acid salt of organic amine be identical in the group that is connected with nitrogen-atoms and above-mentioned.Negative ions in the quaternary ammonium salt respectively can be (CH
3)
4N
+, (C
2H
5)
4N
+, (n-C
4H
9)
4N
+, (CH
3)
3C
6H
5N
+,
Deng, and BF
- 4, PF
- 6, AsF
- 6, sbF
- 6, clo
- 4, I
-(I
- 3), Br
-, cl
-, F
-, CN
-, SCN
-Deng.The positive ion of quaternary ammonium hydroxide can be with quaternary ammonium salt identical, negative ion then is OH
-The object lesson of quaternary ammonium salt and quaternary ammonium hydroxide is: (CH
3)
4Ncl, (CH
3)
4NBF
4, (CH
3)
4NPF
6, (C
2H
5)
4Ncl, (C
2H
5)
4NBF
4, (C
2H
5)
4NPF
6, (n-C
4H
9)
4NclO
4(TBAP), (n-C
4H
9)
4Ncl, (n-C
4H
9)
4NPF
4, (n-C
4H
9)
4NPF
6,
, (CH
3)
3C
6H
5NBF
4, (C
2H
5)
4NOH, (n-C
4H
9)
4NOH etc.This quaternary ammonium salt or quaternary ammonium hydroxide and polymer-based carbon volume recombination can be made into anion conductor.
Three, tertiary amine oxide.Can be monobasic, polynary or heterocyclic, the protic acid salt of organic amine be identical in the group that is connected with nitrogen-atoms and above-mentioned.The object lesson of amine oxide is: (CH
3)
3NO, (C
2H
5)
3NO, (n-C
4H
9)
3NO,
, (CH
3)
2C
6H
5NO,
,
Deng.This amine oxide and polymer-based carbon volume recombination can be made into oxonium ion (O
2-) conductor.
The used polymeric matrix of the present invention is to have high specific inductivity, and is unbodied to moving iron inert material down to small part in service temperature.Can be by the chemical modification thing of homopolymer, multipolymer, homopolymer or multipolymer, perhaps the blend of above-mentioned various polymkeric substance is formed.Polymer materials can be following several:
(1) polyethers or polythioether.Can be polyoxyethylene (PEO), polyoxytrimethylene (PPO), polytetrahydrofuran, chlorohydrin rubber, poly-ethyl-sulfide etc.Especially contain the unitary multipolymer of EO and PO, PO content generally is higher than 5%, preferably is about 40%, and weight-average molecular weight is 5,000-500,000.Or the blend of PEO and PPO, wherein the weight ratio of PEO/PPO is 3-5/2.
(2) polyether oligomer or and the cross-linking products of the alkylene glycol ester of vinylformic acid (or derivatives thereof).Wherein polyether oligomer can be the polyoxyethylene glycol mono-methyl (PEG) that weight-average molecular weight is 200-700, and/or weight-average molecular weight is the polypropylene glycol mono-methyl (PPG) of 250-900, and the alkylene glycol ester of vinylformic acid or derivatives thereof can be vinylformic acid glycol ester, vinylformic acid propylene glycol ester, methacrylic acid glycol ester, methacrylic acid propylene glycol ester, ethylacrylic acid glycol ester, ethyl propylene acid propylene glycol ester.Linking agent wherein can be: phosphorus oxychloride POcl
3, phosphorus trichloride Pcl
3, sulfuryl chloride SO
2Cl
2, thionyl chloride SOcl
2, CH
2Ticl
3, (CH
3)
2Ticl
2, C
2H
5Ticl
3, (C
2H
5)
2Ticl
2, CH
3Sicl
3, (CH
3)
2Sicl
2, C
2H
5Sicl
3, (C
2H
5)
2Sicl
2, CH
3Bcl, C
2H
5Bcl, Ticl
4, how different eyeball acid esters as 2,4-toluene diisocyanate, thermosetting resin such as epoxy one polythiol or epoxy-polymeric amide etc.
(3) side chain contains the polymkeric substance of PEG and/or PPG.
(4) contain the ester group polymkeric substance.
(5) polymeric amide.
(6) poly-alkylene imines.
(7) the poly-imine phosphate acid esters of Qu Daiing can be that structure is
Polymkeric substance, wherein n is the polymerization degree, R, R ' they are the saturated footpath of carbon number 1-10, generally contain atoms such as one or several O, N, how to be connected with aryl.
(8) mixture of polycation and polyanion.
(9) contain the protic acid salt group (comprising polycation) of quaternary ammonium, Liu, Phosphonium, organic amine: and contain the amine sulphonyl
The polymkeric substance of (R wherein, the meaning of R ' is with in (7)).These groups can be introduced by the polymer chemistry reaction.
(10) with bronsted acid part compatible polymers perhaps mutually.The bronsted acid here is protonic acid.Such polymkeric substance can be: polyvinyl alcohol, polyacrylic acid, polymethyl acrylic acid, polyvinylsulfonic acid, phosphonic acids polyvinyl alcohol, cellulose acetate, poly-ethyleneimine, polyacrylamide, poly-(N-substituted acrylamide), phenol formaldehyde resin, oxidic polyethylene etc.
(11) polar polymer can be poly(vinylidene fluoride), trifluorochloroethylene-vinylidene fluoride copolymers, ethene-trifluoro-ethylene copolymer, polyvinyl formal etc.
(12) has the amorphous copolymer of above polymkeric substance chain link.
(13) blend of above homopolymer, multipolymer or its chemical modification thing.
More than polymkeric substance in all kinds of composite electrolytes, can be further crosslinked in order to following method: plasma body, high-power electron beam radiation, ultraviolet radiation, radical initiator also add bifunctional crosslinking agent such as methylene diacrylamine simultaneously, N, N '-diallyl alkene acid amides, the m-xylene acrylamide, N, N '-trimethylene diacrylamine etc. (forming the object polymkeric substance of interpenetrating(polymer)networks), with formaldehyde, acetaldehyde, butyraldehyde, phenyl aldehyde, or diglycidylether
(R is an alkyl), urea/phosphoric acid etc. carry out crosslinked to the polymkeric substance that contains active proton such as polyvinyl alcohol etc.
In the polymkeric substance of composite electrolyte, can add one or more additives, to increase electrolytical specific inductivity, make it have amorphous or the part amorphous structure, and/or help the consistency of compound moiety, mainly should add the additive that can increase the body material ionic conductivity.The additive that adds mainly is following several types:
(1) polymkeric substance mainly is above-mentioned each base polymer.
(2) softening agent mainly is the softening agent of high-k.Kind has: nitrile compounds, nitro-compound, halogenide, alcohol compound, organic acid acetic, inorganic acid ester, sulfone compound, heterogeneous ring compound, acid amides, carboxylic acid halides, ether compound etc.
(3) salt, be generally the salt of weak lattice energy, can be metal-salt, ammonium salt or quaternary ammonium salt.
(4) alkali, be generally quaternary ammonium hydroxide, also can be mineral alkali and add complexing agent.
(5) neutral additive can be the material that contains pyridine ring.
(6) complexing additive can be a crown ether such as 18-hat-6, diethylamine tetraacethyl, N,N,N, aluminum chloride etc.
(7) protonic acid can be phosphoric acid, sulfuric acid, heteropolyacid or its hydrochloric acid, uranyl phosphate, phosphorus uranyl acid lithium etc.
Can also add various fillers in the mixture: conductive filler materials such as carbon black, Graphite Powder 99, aluminium powder, magnetite powder; Polymkeric substance or inorganic inertia reinforced filling are as polystyrene etc.; And the inert material such as the TiO of energy scattered light
2, ZnO
2, Al
2O
3Deng.
The shape of mixture can be film like, and its thickness is generally less than 500 microns, be preferably the 30-100 micron; Also can be nettedly, especially can have the inert polymkeric substance to make screen cloth; Or has a film of rigidity or flexible thin porous supporter.The flexible support thing can be soaked with soak into solution solution is had the polymer materials of the loose flatulence of inert, making what contain mobile ion is the liquid or the gel of being lived by supporter supports mutually.Infiltrate is the salt that comprises mobile ion, and perhaps this salt is dissolved in the concentrated solution in the compatible solvent.
The method of making the solid state electrolyte mixture be with a kind of can dissolving or add additive after can the dissolve polymer matrix and with the solvent of salt, polymkeric substance is dissolved with salt mixes film forming behind the solvent flashing; Or with a kind of dissolution with solvents polymkeric substance, and another kind of dissolution with solvents or add additive after dissolving institute with salt, mix two kinds of solution then, the solvent flashing film forming.Film formation process can or be centrifuged into embrane method with general pouring method, at a certain temperature, and in the atmosphere of solvent, with inert gas flow or the drying and forming-film that outgases in a vacuum.Better method is behind pouring solution, near the matrix polymer material melts institute with salt and the Undec temperature of additive under, the heating make solvent evaporates, be shaped at the said temperature lower sheeting then.Also can carry out crosslinked again after the shaping drying or annealing.Solvent is pyridine, benzene, toluene, dimethyl formamide, methyl-sulphoxide, acetonitrile or water etc. preferably.To being used for the ionogen of some special purpose such as gas detector etc., on a face of solid state electrolyte or two faces, can adhere to one deck catalyzer, its structure can be porous, this layer catalyzer can be electronic conduction, can make electrode.The material that can be used as catalyst electrode material has three kinds:
(1) based on the material of carbon, as decolorizing carbon, graphite.
(2) be difficult for the metal of oxidation, belong to etc. as platinum, nickel, nickel bag graphite, nickel are covered with gold leaf.
(3) of the present invention have a solid state electrolyte corresponding mobile ion and that be mixed with conductive filler material.
The method for making of catalyst electrode can be:
(1) makes propping material with conduction or non electrically conductive material, add the corpuscle that has electronic conductance and catalysis efficiency simultaneously.
(2) make fabric with carbon as the electro-conductive material of major ingredient.
(3) make upholder with polymeric web, supporting the thin conductive polymer membrane of one deck, can add carbon black, graphite or other conductive filler materials in the film.
(4) metal powder is dispersed in polymer materials or the fabric.
(5) make body material with solid state electrolyte and add conductive filler material, it is become have ionic conduction and electrically conductive material, this material can be used as the electrode of this kind solid electrolyte.
(6) between loose gas-pervious electrode and ionogen, folder one deck has the ionic conduction of this kind ionogen mobile ion and the rete of electronic conduction.
(7), plate the loose gas-pervious catalyst electrode of one deck with the method for plated film.Film coating method can be vacuum plating, ion plating, plated film etc.
The as above catalyst electrode layer of Zhi Zuoing has ventilation property, catalytic (reduction of catalysis mobile ion or be oxidized to mobile ion to corresponding reducing gas), electronic conduction or has the ionic conductivity and the electronic conduction of mobile ion in the corresponding solid state electrolyte.
Embodiment 1, with PEO-PPO/TMABF
4Making for the complexes membrane of main component.
The PEO of 3.5 gram molecular weights 300,000 and 1.5 gram PPO, and 2 gram fluoroboric acid tetramethyl-ammonium (TMABF
4), be dissolved in an amount of pyridine, make the solution of about 50ml, shake pouring after 10-30 minute, drying and forming-film.This film is BF
- 4Conductor.
Embodiment 2, with PEO-PPO/LiBF
3/ TMABF
4Making for the complexes membrane of major ingredient.
The PEO of 4 gram molecular weights 300,000 and 2 gram PPO, and 1 gram lithium-fluoroborate LiBF
4With 2 gram fluoroboric acid tetramethyl-ammonium TMABF
4Be dissolved in an amount of pyridine, make the solution of about 50ml, shook pouring, drying and forming-film 10-30 minute.This film is BF
- 4And Li
+Conductor.
Embodiment 3, with PEO-PPO/LiBF
4/ TEAOH is the making of the complexes membrane of major ingredient.
Is 3.5 gram molecular weights 300,000 PEO and 1.5 gram PPO, and 1 gram lithium-fluoroborate LiBF
4, 2.3 the gram tetraethyl ammonium hydroxides (TEAOH) 10% aqueous solution, be dissolved in an amount of pyridine, make the solution of about 50ml, shake 10-30 minute after, pouring, drying, film forming.This film is OH
-And Li
+Conductor.
Embodiment 4, with PEO-PPO/TMABF
4/ TEDA0.67H
3PO
4Making for the complexes membrane of major ingredient.
Is 3.5 molecular weight 300,000 PEO and 2 gram PPO, and 1 gram fluoroboric acid tetramethyl-ammonium, 1.5 gram triethylenediamine phosphoric acid salt C
6H
12N
20.67H
3PO
4(be TEDA0.67H
3PO
4), be dissolved in an amount of pyridine, be made into the solution of about 50ml, shake 10-30 minute after, pouring, drying, film forming.This film is H
+And BF
- 4Conductor.
Embodiment 5.With PEO-PPO/LiBF
4/ TEDA20 is the making of the complexes membrane of major ingredient.
Is 4 gram molecular weights 300,000 PEO and 2 gram PPO, and 1 gram lithium-fluoroborate LiBF
4With 2.5 oxidation triethylenediamine C
6H
12N
2O
2(being TEDA20) is dissolved in an amount of pyridine, is made into the solution of about 50ml, shakes pouring then, drying, film forming 10-30 minute.This film is O
2-And Li
+Conductor.
The method for making of embodiment 6 oxygen ion conductor carbon cloth catalyst electrodes.
Press embodiment 5.Preparation oxygen ion conductor film.Prepared film is pressed between two carbon cloths, becomes the carbon cloth one complexes membrane one carbon cloth interlayer of sandwich formula.This sandwich complex is the oxygen ion conductor that two faces all have catalyst electrode.
Embodiment 7.The method for making of proton conductor platinum catalyst electrode.
Press embodiment 4.The preparation proton conductor film.In the two sides of prepared film difference, evaporation last layer platinum forms platinum-complexes membrane-platinum interlayer.This sandwich complex is the proton conductor that two masks have catalyst electrode.
Embodiment 8.The hydroxide radical conductor is made the method for making of catalyst electrode with hydroxide radical and electronic conductor.
Is 3.5 gram molecular weights 300,000 PEO and 1.5 gram PPO and 1 gram lithium-fluoroborate LiBF
4, 10% aqueous solution of 2.3 gram tetraethyl ammonium hydroxides (TEAOH) is dissolved in an amount of pyridine, makes the solution of about 50ml, shake 10-30 minute after, add 2 gram Graphite Powder 99s, pouring afterwards, drying, hot pressing (＜40 ℃) film forming stir.Promptly become hydroxide radical OH
-And the conductor thin film of electronics.Press embodiment 3 again, preparation hydroxide radical conductor thin film.Again above-mentioned hydroxide radical that makes and electronic conductor film are crimped on two faces of hydroxide radical conductor thin film.Become hydroxide radical and electronic conductor interlayer.Two faces are catalyst electrode.This sandwich complex is two hydroxide ion conductors that all have catalyst electrode.
Claims (14)
1, a kind of high-molecular composite solid electrolyte, it is characterized by and adopt monobasic or polynary, or heterocycle organic ammonium and polymkeric substance are made proton conductor, anion conductor, and oxygen ion conductor, polymkeric substance can be made up of the chemical modification thing of homopolymer, multipolymer, homopolymer or multipolymer or the blend of above various polymkeric substance substantially, can add one or more additives and filler in mixture.Especially following system: [PEO/PPO/ additive TBAP/ quaternary ammonium salt TMACL], [PEO/PPO/ additive LiBF
4/ quaternary ammonium salt TMABF
4], [PEO/PPO/ additive TBAP/ quaternary ammonium hydroxide TEAOH], [PEO/PPO/ additive TMABF
4The protic acid salt TEDA.0.67H of/organic amine
2PO
4], [PEO/PPO/ additive TEAOH or TBAP/ tertiary amine oxide TEDA.20].
2, according to the mixture described in the claim 1, the organic ammonium that it is characterized by in the composition can be the especially protic acid salt of tertiary amine of organic amine, quaternary ammonium salt, quaternary ammonium hydroxide, or tertiary amine oxide, these organic ammoniums can be monobasic, polybasic, or heterocyclic.The group that is connected with nitrogen-atoms can contain atoms such as at least one O, N for the saturated footpath of carbon number 1-10, is connected with aryl, or the aryl of carbon number 6-10, and compatible with single kind or multiple polymers matrix.Protonic acid can be ortho-phosphoric acid, metaphosphoric acid, triphosphoric acid, tetra-sodium, Hypophosporous Acid, 50, Tripyrophosphoric acid, phosphorous acid, sulfuric acid, tosic acid, trifluoroacetic acid, sulfonic acid trifluoromethane, 12 phosphomolybdate, 12 phospho-wolframic acids, 12 silicomolybdic acid, six tellurium molybdic acids.The protic acid salt of tertiary amine can for:
CH
3）
3N·1/3H
3PO
4、（C
2H
5）
5）
3N·1/3H
3PO
4、
、
、
、（n-C
4H
9）
3N·1/3H
3PO
4、（CH
3）
2C
6H
5N·1/3H
3PO
4。Quaternary ammonium salt can be (CH
3)
4Ncl, (CH
3)
4NBF
4, (CH
3)
4NPF
6, (C
2H
5)
4Ncl, (C
2H
5)
4NBF
4, (C
2H
5)
4NPF
6, (n-C
4H
9)
4Ncl, (n-C
4H
9)
4NBF
4, (n-C
4H
9)
4NPF
6,
, CH
3)
3C
6H
5NBF
4. quaternary ammonium hydroxide can be (n-C
4H
9)
4NOH, (C
2H
5)
4NOH.Ammonium oxide can be (CH
3)
3NO, (C
2H
5)
3NO, (n-C
4H
9)
3NO,
, (CH
3)
2C
6H
5NO,
3, according to the mixture described in the claim 1, it is characterized by wherein, polymer materials can contain: (1) polyethers or polythioether can be polyoxyethylene (PEO), polyoxytrimethylene (PPO), polytetrahydrofuran, chlorohydrin rubber, poly-ethyl-sulfide.Especially contain the unitary multipolymer of EO and PO, PO content is higher than 5%, is preferably 40%, and weight-average molecular weight is 5,000-500,000.Or the blend of PEO and PPO, wherein the weight ratio of PEO/PPO is 3-5/2.(2) polyether oligomer or and the cross-linking products of the alkylene glycol ester of vinylformic acid (or derivatives thereof), wherein linking agent can be: phosphorus oxychloride POcl
3, phosphorus trichloride Pcl
3, sulfuryl chloride SO
2Cl
2, thionyl chloride SOcl
2, CH
3Ticl
3, (CH
3)
2Ticl
2, C
2H
5Ticl
3, (C
2H
5)
2Ticl
2, C
2H
5)
2Ticl
2, CH
3Sicl
3, (CH
3)
2Sicl
2, CH
3Bcl
2, many isocyanide esters 2,4-toluene two different eyeball acid esters, thermosetting resin epoxy-polythiol or epoxy-polymeric amide.Wherein polyether oligomer is that weight-average molecular weight is the poly-ethanol list methyl alcohol (PEG) of 200-700, and/or weight-average molecular weight is the polypropylene glycol mono-methyl (PPG) of 250-900, and the alkylene glycol ester of vinylformic acid or derivatives thereof can be vinylformic acid glycol ester, vinylformic acid propylene glycol ester, methacrylic acid glycol ester, methacrylic acid propylene glycol ester, ethylacrylic acid glycol ester, ethyl propylene acid propylene glycol ester.(3) side chain contains the polymkeric substance of PEG and/or PPG.(4) contain the ester group polymkeric substance.(5) polymeric amide.(6) poly-alkylene imines.(7) the poly-imine phosphate acid esters of Qu Daiing can be
, wherein, n is the polymerization degree, R
1R ' for the stable hydrocarbon of carbon number 1-10, contain atoms such as at least one O, N, how to be connected with aryl.(8) mixture of polycation and polyanion.(9) contain the protic acid salt group (comprising polycation) of quaternary ammonium, Liu, Phosphonium, organic amine and contain sulfamic
The polymkeric substance of (wherein R, R ' meaning are with defined in (7)).(10) compatible part compatible polymers with protonic acid.Can be: polyvinyl alcohol, polyacrylic acid, polymethyl acrylic acid, polyvinylsulfonic acid, phosphonic acids polyvinyl alcohol, cellulose acetate, poly-ethyleneimine, polyacrylamide, poly-(N-substituted acrylamide), phenol formaldehyde resin, oxidic polyethylene.(11) polar polymer.Can be poly(vinylidene fluoride), trifluorochloroethylene-vinylidene fluoride copolymers, ethene-trifluoro-ethylene copolymer, polyvinyl formal, tetrafluoroethylene.
4, according to the polymkeric substance in the mixture described in claim 1 and 3, it is characterized by cross-linking method, can use: plasma body, high-power electron beam radiation, ultraviolet radiation, radical initiator and bifunctional crosslinking agent can be the methylene diacrylamines, N, N diallyl acrylamide, the m-xylene diacrylamine, N, N '-trimethylene diacrylamine (forming the object polymkeric substance of interpenetrating(polymer)networks).With formaldehyde, acetaldehyde, butyraldehyde, phenyl aldehyde or diglycidylether
/ HBF
4, urea/phosphoric acid carries out crosslinked to the polymkeric substance (can be polyvinyl alcohol) that contains active proton.
5, according to the mixture described in the claim 1, it is characterized by additive and can be: polymkeric substance, softening agent, salt, alkali, protonic acid, complexing additive and neutral additive.
6, according to the mixture described in the claim 1, it is characterized by and to add various fillers: carbon black, Graphite Powder 99, aluminium powder, magnetite powder conductive filler material, polymkeric substance or inorganic inertia reinforced filling, and TiO that can scattered light
2, ZnO
2, Al
2O
3Filler.
7, according to the mixture additive described in claim 1 and 5, it is characterized by wherein, softening agent can be: nitrile compounds, nitro-compound, halogenide, alcohol compound, organic acid acetic, inorganic acid ester, sulfone compound, heterogeneous ring compound, acid amides, carboxylic acid halides, ether compound.
8, according to the additive described in claim 1 and 5, the salt that it is characterized by wherein is the salt of weak lattice energy, can be metal-salt, ammonium salt or quaternary ammonium salt, and wherein alkali is generally quaternary ammonium hydroxide, also can be mineral alkali and adds complexing agent simultaneously; Neutral additive can be the material that contains pyridine ring; Wherein the complexing additive can be a crown ether 18-hat-6, ethylenediamine tetraacetic acid (EDTA), N,N,N, aluminum chloride; Protonic acid can be phosphoric acid, sulfuric acid, heteropolyacid or its salt, uranyl phosphate, phosphorus uranyl acid lithium.
9, according to the solid state electrolyte described in the claim 1, it is characterized by composite shape and can be film like, its thickness less than 500 microns, be preferably the 30-100 micron, also can especially can have the inert polymkeric substance to make screen cloth for netted; Or has a film of rigidity or flexible thin porous supporter.The flexible support thing can be soaked with soak into solution solution is had the polymer materials of the loose flatulence of inert, making what contain mobile ion is the liquid or the gel of being lived by supporter supports mutually.Infiltrate is the salt that comprises mobile ion, and perhaps this salt is dissolved in the concentrated solution in the compatible solvent.
10, a kind of method of making the described solid state electrolyte of claim 1 that is exclusively used in, comprise with a kind of can dissolving or add additive after can the dissolve polymer matrix and institute with the solvent of salt, make polymkeric substance and salt dissolve mixing, film forming behind the solvent flashing; Or with a kind of dissolution with solvents polymeric matrix, and another kind of dissolution with solvents or add additive after dissolving institute with salt, mix two kinds of solution then, the solvent flashing film forming.After above-mentioned film formation process is characterized by pouring, near body material fusing and institute with salt and the Undec temperature of additive under, heating is shaped at the said temperature lower sheeting then for solvent evaporates.Also can carry out crosslinked again after the shaping drying or annealing.The also available general pouring method of film formation process or be centrifuged into embrane method, under the certain temperature in solvent atmosphere, with inert gas or vacuum outgas, drying and forming-film.
11, according to the method for making of the solid state electrolyte described in the claim 10, it is characterized by preferably, solvent is: pyridine, benzene, toluene, dimethyl formamide, dimethyl sulfoxide (DMSO), acetonitrile or water.
12, according to the solid state electrolyte method for making described in the claim 10, it is characterized by, can adhere to one deck catalyzer on a face of solid state electrolyte or two faces, its structure can be porous, and this layer catalyzer can be electronic conduction, can be used as electrode.
13, according to the catalyst substance described in the claim 12, it is characterized by the catalyst electrode material can be: decolorizing carbon, Graphite Powder 99, platinum, palladium, nickel powder, nickel bag metal powder, or other are difficult for oxidized metal powder, or of the present invention solid state electrolyte corresponding mobile ion and that be mixed with conductive filler material are arranged.
14, according to the method for making of the catalyst electrode described in claim 10 and 12, it is characterized by following several method.(1) make propping material with conduction or non electrically conductive material, add the corpuscle that has electronic conductance and catalysis efficiency simultaneously, (2) make fabric with carbon as the electro-conductive material of major ingredient.(3) make upholder with polymeric web, supporting the thin conductive polymer membrane of one deck, film adds carbon black, graphite or other conductive filler materials.(4) metal powder is dispersed in polymer materials or the fabric.(5) make body material with solid state electrolyte and add conductive powder or electro-conductive fiber, making becomes the material with ion conducting and electronic conduction, and this material is as the electrode of this kind solid state electrolyte.(6) between loose gas-pervious electrode and ionogen, folder one deck has the ionic conduction of this kind ionogen mobile ion and the rete of electronic conductance.(7), plate the loose gas-pervious catalyst electrode of one deck with the method for plated film.Film coating method can be vacuum plating, ion plating, plated film.
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| Application Number | Priority Date | Filing Date | Title |
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| CN 89108502 CN1051569A (en) | 1989-11-07 | 1989-11-07 | High-molecular composite solid electrolyte and method for making |
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| Application Number | Priority Date | Filing Date | Title |
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| CN 89108502 CN1051569A (en) | 1989-11-07 | 1989-11-07 | High-molecular composite solid electrolyte and method for making |
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| CN1051569A true CN1051569A (en) | 1991-05-22 |
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| CN 89108502 Pending CN1051569A (en) | 1989-11-07 | 1989-11-07 | High-molecular composite solid electrolyte and method for making |
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