JP2004095255A - Solid electrolyte - Google Patents

Solid electrolyte Download PDF

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Publication number
JP2004095255A
JP2004095255A JP2002252682A JP2002252682A JP2004095255A JP 2004095255 A JP2004095255 A JP 2004095255A JP 2002252682 A JP2002252682 A JP 2002252682A JP 2002252682 A JP2002252682 A JP 2002252682A JP 2004095255 A JP2004095255 A JP 2004095255A
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Prior art keywords
solid electrolyte
compound
solution
film
raw material
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JP3649713B2 (en
Inventor
Yoshiyuki Tasaka
Shigeru Tsurumaki
Akihiko Yamada
山田 昭彦
弦巻 茂
田坂 佳之
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Mitsubishi Heavy Ind Ltd
三菱重工業株式会社
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    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies or technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/50Fuel cells
    • Y02E60/52Fuel cells characterised by type or design
    • Y02E60/521Proton Exchange Membrane Fuel Cells [PEMFC]
    • Y02E60/522Direct Alcohol Fuel Cells [DAFC]
    • Y02E60/523Direct Methanol Fuel Cells [DMFC]

Abstract

<P>PROBLEM TO BE SOLVED: To provide a solid electrolyte having a high ionic conductivity under a low humidity environment and a fuel cell using the solid electrolyte. <P>SOLUTION: The solid electrolyte contains a composition using at least a silane coupling agent having an organic substituent and a chemical compound having a phosphoric acid group as a raw material, a composition using at least an epoxy resin and a chemical compound having a phosphoric acid group as a raw material, or a composition formed by adding an additive polyimide resin or a resin having a phenolic hydroxyl to either of the compositions. <P>COPYRIGHT: (C)2004,JPO

Description

[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a solid electrolyte, and is used for, for example, a fuel cell, a secondary battery, a display element, a solar cell, and the like.
[0002]
[Prior art]
In recent years, application development of a polymer electrolyte fuel cell (hereinafter, referred to as “PEFC”) has been attempted in various fields. This is because the power generation principle of PEFC is different from the power generation principle of a conventional internal combustion engine generator, and the chemical energy of the fuel can be directly converted to electric energy by electrochemically oxidizing the fuel. This is because it has features of efficiency, small size, quietness and cleanness.
[0003]
Various compounds have been proposed as a polymer electrolyte which is a basic component of the PEFC. A typical example is a perfluorosulfonic acid polymer known by a trade name such as “Nafion (trade name)”, “Flemion (trade name)”, and “Aciplex (trade name)”.
[0004]
The perfluorosulfonic acid-based polymer has a main chain of a tetrafluoroethylene skeleton known as so-called “Teflon (trade name)”, and a side chain having a sulfonic acid group at a terminal via an ether bond is attached to the main chain. Has a bonded chemical structure.
[0005]
As described above, the perfluorosulfonic acid-based polymer has a hydrophobic tetrafluoroethylene chain portion and a hydrophilic sulfonic acid group side chain portion in the molecule. For this reason, microphase separation into a hydrophobic part and a hydrophilic part is performed, and proton conduction is performed through a hydrated sulfonic acid group which is a hydrophilic part.
[0006]
That is, the ionic conductivity of the perfluorosulfonic acid-based polymer depends on the water content, and it is necessary to keep the water content of the electrolyte high in order to obtain high ionic conductivity. As a result, when a perfluorosulfonic acid-based polymer is used as the electrolyte of the PEFC, it is generally necessary to provide a humidifying mechanism, and the reaction temperature is generally restricted to a range of 0 ° C. to 90 ° C.
[0007]
[Problems to be solved by the invention]
On the other hand, during the power generation operation of the PEFC, there is a problem that the performance is reduced due to the moisture added to the fuel gas or the oxygen gas by the humidifying mechanism and the moisture generated by the power generation reaction. This is because the water aggregates and blocks the gas flow path.
[0008]
For this reason, in the power generation operation of the PEFC, it is important to control the mechanism and operating conditions for keeping the water content of the electrolyte at an appropriate level, and it is required to appropriately control the water content according to the structure of the electrode laminate and the operating conditions. As described above, the conventional perfluorosulfonic acid-based polymer has excellent characteristics as an electrolyte of PEFC, but has a problem that appropriate water management is required during operation.
[0009]
In response to the above problems, development of an electrolyte exhibiting high ionic conductivity even under non-humidified conditions has been promoted. For example, a perfluorosulfonic acid-based polymer is mixed with a moisturizer such as molecular sieves, silica gel, or polyethylene oxide to moisturize it, or a catalyst such as platinum-supported titania or a low molecular weight sulfonic acid group-containing compound is mixed and moisturized. Method, a method using an electrolyte in which a phosphoric acid compound is mixed with a basic polymer, a method using an electrolyte in which a tin dioxide hydrate, a zinc dioxide hydrate, a tungsten trioxide hydrate, etc. are mixed with a polymer, A method using an inorganic electrolyte such as silicate gel has been proposed.
[0010]
Among these, inorganic electrolytes such as phosphosilicate gels have a feature that relatively high ionic conductivity can be obtained even under dry conditions because the mixed phosphate compound plays a role of proton conduction, and can be used under non-humidified conditions. It is attracting attention as an electrolyte. However, there is a problem that it is poor in flexibility and difficult to handle when used as an electrolyte of a fuel cell or the like.
[0011]
The present invention has been made in view of the above circumstances, and a solid electrolyte having better ion conductivity than a conventional perfluorosulfonic acid polymer in a low humidity environment (for example, a relative humidity of 10% or less) and the solid electrolyte An object of the present invention is to provide a solid oxide fuel cell using the same.
[0012]
[Means for Solving the Problems]
The present inventors have conducted intensive studies on the combination of a compound having a phosphate group and a resin exhibiting excellent ion conductivity in a low humidity environment, and as a result, at least a silane coupling agent having an organic substituent and a compound having a phosphate group And a composition containing at least an epoxy resin and a compound having a phosphate group as a raw material component, or an addition-type polyimide resin or a resin having a phenolic hydroxyl group added to each of the above compositions. The present inventors have found that the composition exhibits a high ionic conductivity under a low humidity environment, and have reached the present invention.
[0013]
A first invention is a solid electrolyte synthesized using a silane coupling agent having at least an organic substituent and a compound having a phosphate group as raw material components. The types of the silane coupling agent having an organic substituent and the compound having a phosphoric acid group, and the amounts of the two are appropriately selected depending on the required physical properties of the material and the form of use.
[0014]
Here, specific examples of the silane coupling agent having an organic substituent include vinyltrimethoxysilane, vinyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropylmethyl Diethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-β- (aminoethyl) -3-aminopropyltrimethoxysilane, N-β -(Aminoethyl) -3-aminopropyltriethoxysilane and the like.
[0015]
Specific examples of the compound having a phosphate group include orthophosphoric acid, polyphosphoric acid, diphenylphosphoric acid, and a phosmer series, that is, acid phosphoxyethyl methacrylate (trade name: Phosmer M), and 3 chloro 2-acid phosphoroxy. Propyl methacrylate (trade name: Phosmer CL), acid phosphoxypropyl methacrylate (trade name: Phosmer P), acid phosphoxyethyl acrylate (trade name: Phosmer A), acid phosphoxy polyoxyethylene glycol monomethacrylate (trade name: Phosmer) PE), acid phosphoxypolyoxypropylene glycol monomethacrylate (trade name: Phosmer PP), methacryloyloxyethyl acid phosphate monoethanolamine half salt (trade name: Phosmer MH), Data black yl oxyethyl acid phosphate Hastings preparative dimethylaminoethyl methacrylate half Salt (trade name: Phosmer DM), methacryloyl oxyethyl acid phosphate Hastings preparative diethylaminoethyl methacrylate half Salt (trade name: Phosmer DE), and the like.
[0016]
The second invention is a solid electrolyte synthesized using, as raw material components, a silane coupling agent having at least an organic substituent, a compound having a phosphate group, and an addition type polyimide resin.
[0017]
Here, examples of the addition type polyimide resin include PMR type and bismaleimide. When an addition type polyimide resin is used as a raw material component, basically, an alcohol solution obtained by dissolving an ester compound, a diamine compound, and a reactive terminal blocking agent obtained by reacting an alcohol with a tetracarboxylic dianhydride in an alcohol. As a raw material. In this alcohol solution, the tetracarboxylic acid ester compound and the diamine compound condense to form an oligomer. This oligomer exists in a state where amino groups and carboxyl groups at both ends are blocked by a reactive terminal blocking agent contained in the solution. By mixing a silane coupling agent having an organic substituent and a compound having a phosphate group into an alcohol solution containing the oligomer, a solid electrolyte containing an addition type polyimide resin as a component can be obtained.
[0018]
A third invention is a solid electrolyte synthesized using at least a silane coupling agent having an organic substituent, a compound having a phosphate group, and a compound having a phenolic hydroxyl group as raw material components.
[0019]
Here, specific examples of the resin having a phenolic hydroxyl group include polyparavinylphenol, a phenol resin, polyhydroquinone, and polybiphenol. By adding a silane coupling agent having an organic substituent and a compound having a phosphoric acid group directly or by dissolving it in an appropriate solvent to the resin having a phenolic hydroxyl group, the resin having a phenolic hydroxyl group is contained as a component. A solid electrolyte can be obtained.
[0020]
A fourth invention is a solid electrolyte synthesized using at least an epoxy resin and a compound having a phosphate group as raw material components. The type of the epoxy resin and the compound having a phosphoric acid group and the amount of the two are appropriately selected according to the required physical properties of the material and the form of use.
[0021]
Specific examples of the epoxy resin include glycidyl ether-based epoxy resins such as bisphenol A epoxy resin, hydrogenated bisphenol A epoxy resin, novolak epoxy resin, bisphenol F epoxy resin, brominated epoxy resin, and fluorine. Epoxy resin, cycloaliphatic epoxy resin, glycidyl ester epoxy resin, glycidylamine epoxy resin, heterocyclic epoxy resin, and the like.
[0022]
A fifth or sixth invention is a solid electrolyte synthesized by further adding, as a raw material component, an addition-type polyimide resin or a compound having a phenolic hydroxyl group to the raw material component of the solid electrolyte according to the fourth invention. Here, the addition type polyimide resin or the compound having a phenolic hydroxyl group is as described above.
[0023]
A seventh invention is the solid electrolyte according to any one of the first to sixth inventions, wherein the compound having a phosphate group is a phosmer (trade name). The phosmer (trade name) is a polymerizable monomer containing a phosphate group, and is a general term for the various phosmers described above.
[0024]
An eighth invention is the solid electrolyte according to any of the third or sixth invention, wherein the compound having a phenolic hydroxyl group is polyparavinylphenol or a phenol resin.
[0025]
A ninth invention is a solid oxide fuel cell having an electrolyte membrane formed by filming the solid electrolyte according to any one of the first to eighth inventions.
[0026]
BEST MODE FOR CARRYING OUT THE INVENTION
Hereinafter, preferred examples of the solid electrolyte according to the present invention will be described below, but the present invention is not limited to these examples. In the following description, “GPTMS” indicates 3-glycyloxypropyltrimethoxysilane, and “TMOS” indicates tetramethoxysilane.
[0027]
[Example 1]
Polyimide monomer / GPTMS / TMOS / phosphate sample
161.1 g of 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride, 225.2 g of methanol and a Teflon stirrer were placed in a 500 mL eggplant-shaped flask, and a water-cooled condenser and a calcium chloride drying tube were attached to the flask. Was. Then, while stirring with a Teflon stirrer, the contents are heated to a temperature at which the contents boil by an oil bath, and reacted for 5 hours. Then, 50 wt% methanol of 3,3′-dimethoxycarboxy-4,4′-dicarboxylbenzophenone is added. A solution was obtained. The resulting solution was orange and transparent. This solution is hereinafter referred to as A solution.
[0028]
In a 50 mL glass sample bottle, 1.09 g of 4,4′-diaminodiphenylmethane, 1.09 g of methanol, and a Teflon stirrer were put, and stirred at room temperature to dissolve. After 3.86 g of the solution A was added thereto, the mixture was further stirred for 10 minutes to obtain a uniform solution. This solution is hereinafter referred to as B solution.
[0029]
3.5 g of the B solution was put into a 20 mL glass sample bottle, and 4.28 g of methanol, 4.5 g of 3-glycyloxypropyltrimethoxysilane (GPTMS) and 2.86 g of tetramethoxysilane (TMOS) were further added and stirred. . On the other hand, 6.51 g of an 85% orthophosphoric acid aqueous solution was placed in a 10 mL Erlenmeyer flask, and 1.05 g of distilled water was further added and stirred. Next, while stirring the solution prepared in the 20 mL sample bottle, the phosphoric acid aqueous solution prepared in the 10 mL Erlenmeyer flask was dropped over 10 minutes. The solution thus obtained is hereinafter referred to as C solution.
[0030]
Next, 3 g of the solution C was cast on a 5 cm square square frame made of polypropylene, and left overnight at room temperature in a fume hood and air-dried. Subsequently, the mold was put into an oven and heated at 50 ° C. for 24 hours, at 100 ° C. for 24 hours, and at 150 ° C. for 5 hours to obtain a yellow opaque film.
[0031]
Both surfaces of the obtained film were sandwiched between platinum foils having a size of 5 mm × 10 mm, placed in an oven, and the ionic conductivity of the film was measured by an AC impedance method. As a result, the ionic conductivity of the film was 1.2 × 10 2 at 60 ° C. and 4.2% relative humidity. -4 S / cm and 4.7 × 10 at 80 ° C. and 1.5% relative humidity -4 2.7 × 10 at S / cm, 130 ° C. and 0.2% relative humidity -3 S / cm.
[0032]
[Example 2]
Polyimide oligomer / GPTMS / TMOS / phosphate sample
4.96 g of 4,4'-diaminodiphenylmethane, 4.96 g of methanol and a Teflon stirrer were placed in a 100 mL eggplant-shaped flask, and the mixture was stirred at room temperature to dissolve the solution. To the flask was added a water-cooled condenser and a calcium chloride drying tube. Next, while stirring with a Teflon stirrer, the contents were heated to a temperature at which the contents boiled by an oil bath and reacted for 5 hours. After the reaction, the solution was cooled to room temperature, and the solution was separated into two layers. Next, of the separated two layers, the methanol in the upper layer was removed to obtain a viscous liquid in the lower layer. The solid content concentration of this viscous liquid was 62% by weight. The viscous liquid thus obtained is hereinafter referred to as D liquid.
[0033]
4.6 g of the D liquid was placed in a 20 mL glass sample bottle, and 5.68 g of methanol, 5.9 g of 3-glycyloxypropyltrimethoxysilane (GPTMS), and 3.8 g of tetramethoxysilane (TMOS) were further added and stirred. . On the other hand, 8.64 g of an 85% orthophosphoric acid aqueous solution was put into a 10 mL Erlenmeyer flask, and 1.41 g of distilled water was further added and stirred. Next, while stirring the solution prepared in the 20 mL sample bottle, the phosphoric acid aqueous solution prepared in the 10 mL Erlenmeyer flask was dropped over 10 minutes. The solution thus obtained is hereinafter referred to as E solution.
[0034]
Next, 3 g of the E solution was cast on a 5 cm square square mold made of polypropylene, and left in a fume hood at room temperature overnight and air-dried. Subsequently, the mold was put into an oven and heated at 50 ° C. for 24 hours, at 100 ° C. for 24 hours, and at 150 ° C. for 5 hours to obtain a yellow opaque film.
[0035]
Both surfaces of the obtained film were sandwiched between platinum foils having a size of 5 mm × 10 mm, placed in an oven, and the ionic conductivity of the film was measured by an AC impedance method. As a result, the ionic conductivity of the film was 4.4 × 10 4 at 60 ° C. and 4.2% relative humidity. -5 S / cm and 2.2 × 10 2 at 80 ° C. and 1.5% relative humidity -4 S / cm and 1.4 × 10 at 130 ° C. and 0.2% relative humidity. -3 S / cm.
[0036]
[Example 3]
Polyimide oligomer / GPTMS / phosphate sample
1.9 g of the D liquid described in Example 2 was placed in a 20 mL glass sample bottle, and 4.02 g of methanol and 5.9 g of 3-glycyloxypropyltrimethoxysilane (GPTMS) were further added and stirred. On the other hand, 4.3 g of an 85% orthophosphoric acid aqueous solution was placed in a 10 mL Erlenmeyer flask, and 0.7 g of distilled water was further added thereto and stirred. Next, while stirring the solution prepared in the 20 mL sample bottle, the phosphoric acid aqueous solution prepared in the 10 mL Erlenmeyer flask was dropped over 10 minutes. The solution thus obtained is hereinafter referred to as F solution.
[0037]
Next, 3 g of the F solution was cast on a 5 cm square square frame made of polypropylene, and left overnight at room temperature in a fume hood and air-dried. Subsequently, the mold was put into an oven and heated at 50 ° C. for 24 hours, at 100 ° C. for 24 hours, and at 150 ° C. for 5 hours to obtain a yellow opaque film.
[0038]
Both surfaces of the obtained film were sandwiched between platinum foils having a size of 5 mm × 10 mm, placed in an oven, and the ionic conductivity of the film was measured by an AC impedance method. As a result, the ionic conductivity of the film was 1.3 × 10 3 at 80 ° C. and 1.3% relative humidity. -4 S / cm.
[0039]
[Example 4]
GPTMS / phosphate sample
In a 20 mL glass sample bottle, 11.8 g of 3-glycyloxypropyltrimethoxysilane (GPTMS) and 11.5 g of ethanol were put and stirred. On the other hand, 8.64 g of an 85% orthophosphoric acid aqueous solution was put in a 10 mL Erlenmeyer flask, and 1.42 g of distilled water was further added and stirred. Next, while stirring the solution prepared in the 20 mL sample bottle, the phosphoric acid aqueous solution prepared in the 10 mL Erlenmeyer flask was dropped over 10 minutes. The solution thus obtained is hereinafter referred to as a G solution.
[0040]
Next, 3 g of the G solution was cast on a 5 cm square square frame made of polypropylene, and left in a fume hood at room temperature overnight and air-dried. Subsequently, the mold was put into an oven and heated at 50 ° C. for 24 hours, at 100 ° C. for 24 hours, and at 150 ° C. for 5 hours to obtain a brown transparent film.
[0041]
Both surfaces of the obtained film were sandwiched between platinum foils having a size of 5 mm × 10 mm, placed in an oven, and the ionic conductivity of the film was measured by an AC impedance method. As a result, the ionic conductivity of the film was 3.3 × 10 3 at 60 ° C. and 3.8% relative humidity. -5 S / cm and 1.2 × 10 at 80 ° C. and 1.6% relative humidity -4 1.2 × 10 at 130 ° C. and 0.2% relative humidity -3 S / cm.
[0042]
[Example 5]
GPTMS / polyphosphate sample
In a 20 mL glass sample bottle, 11.8 g of 3-glycyloxypropyltrimethoxysilane (GPTMS), 11.5 g of ethanol, 7.34 g of polyphosphoric acid, and 2.72 g of distilled water were put and stirred. The solution thus obtained is hereinafter referred to as H solution.
[0043]
Next, 3 g of the H solution was cast on a 5 cm square square frame made of polypropylene, and left in a fume hood at room temperature overnight and air-dried. Subsequently, the mold was put into an oven and heated at 50 ° C. for 24 hours, at 100 ° C. for 24 hours, and at 150 ° C. for 5 hours to obtain a brown transparent film.
[0044]
Both surfaces of the obtained film were sandwiched between platinum foils having a size of 5 mm × 10 mm, placed in an oven, and the ionic conductivity of the film was measured by an AC impedance method. As a result, the ionic conductivity of the film was 1.1 × 10 4 at 60 ° C. and 3.9% relative humidity. -4 S / cm and 3.2 × 10 at 80 ° C. and 1.6% relative humidity -4 S / cm.
[0045]
[Example 6]
GPTMS / Phosmer M sample
2.36 g of 3-glycyloxypropyltrimethoxysilane (GPTMS), 2.3 g of ethanol, 3.15 g of Phosmer M (trade name) and 0.54 g of distilled water were placed in a 20 mL glass sample bottle and stirred. The solution thus obtained is hereinafter referred to as I solution.
[0046]
Next, 2 g of the I solution was cast on a 5 cm square square mold made of polypropylene, and left overnight at room temperature in a fume hood and air-dried. Subsequently, the mold was put into an oven and heated at 50 ° C. for 24 hours, at 100 ° C. for 24 hours, and at 150 ° C. for 5 hours to obtain a brown transparent film.
[0047]
Both surfaces of the obtained film were sandwiched between platinum foils having a size of 5 mm × 10 mm, placed in an oven, and the ionic conductivity of the film was measured by an AC impedance method. As a result, the ionic conductivity of the film was 5.6 × 10 6 at 60 ° C. and 3.6% relative humidity. -6 S / cm and 1.7 × 10 at 80 ° C. and 1.4% relative humidity. -5 S / cm and 2.2 × 10 2 at 130 ° C. and 0.2% relative humidity -4 S / cm.
[0048]
[Example 7]
Low molecular resole / GPTMS / phosphate sample
1.42 g of an 82 wt% methanol solution of low molecular resole, 5.9 g of 3-glycyloxypropyltrimethoxysilane (GPTMS) and 4 g of methanol were placed in a 20 mL glass sample bottle and stirred. On the other hand, 4.33 g of an 85% orthophosphoric acid aqueous solution was put into a 10 mL Erlenmeyer flask, and 0.7 g of distilled water was further added thereto and stirred. Next, while stirring the solution prepared in the 20 mL sample bottle, the phosphoric acid aqueous solution prepared in the 10 mL Erlenmeyer flask was added dropwise thereto over 10 minutes. The solution thus obtained is hereinafter referred to as J solution.
[0049]
Next, 3 g of the J solution was cast on a 5 cm square square mold made of polypropylene, and left overnight at room temperature in a fume hood and air-dried. Subsequently, the mold was put into an oven and heated at 50 ° C. for 24 hours, at 100 ° C. for 24 hours, and at 150 ° C. for 5 hours to obtain a brown transparent film.
[0050]
Both surfaces of the obtained film were sandwiched between platinum foils having a size of 5 mm × 10 mm, placed in an oven, and the ionic conductivity of the film was measured by an AC impedance method. As a result, the ionic conductivity of the film was 3.7 × 10 3 at 80 ° C. and 1.2% relative humidity. -4 S / cm.
[0051]
Example 8
Polymer resole / GPTMS / phosphate sample
In a 20 mL glass sample bottle, 2.12 g of a 54.8% by weight methanol solution of a polymer resole, 5.9 g of 3-glycyloxypropyltrimethoxysilane (GPTMS), and 3.2 g of methanol were added and stirred. On the other hand, 4.33 g of an 85% orthophosphoric acid aqueous solution was put into a 10 mL Erlenmeyer flask, and 0.7 g of distilled water was further added thereto and stirred. Next, while stirring the solution prepared in the 20 mL sample bottle, the phosphoric acid aqueous solution prepared in the 10 mL Erlenmeyer flask was added dropwise thereto over 10 minutes. The solution thus obtained is hereinafter referred to as K solution.
[0052]
Next, 3 g of the K solution was cast on a 5 mm square square mold made of polypropylene, and left overnight at room temperature in a fume hood and air-dried. Subsequently, the mold was put into an oven and heated at 50 ° C. for 24 hours, at 100 ° C. for 24 hours, and at 150 ° C. for 5 hours to obtain a brown transparent film.
[0053]
Both surfaces of the obtained film were sandwiched between platinum foils having a size of 5 mm × 10 mm, placed in an oven, and the ionic conductivity of the film was measured by an AC impedance method. As a result, the ionic conductivity of the film was 2.3 × 10 3 at 80 ° C. and 1.2% relative humidity. -4 S / cm.
[0054]
[Example 9]
Polyparavinylphenol / GPTMS / phosphate sample
1.16 g of polyparavinylphenol (molecular weight 9300) and 5.76 g of ethanol were put in a 20 mL glass sample bottle, stirred and dissolved, and then 5.9 g of 3-glycyloxypropyltrimethoxysilane (GPTMS) was added. And stirred. On the other hand, 4.33 g of an 85% orthophosphoric acid aqueous solution was put into a 10 mL Erlenmeyer flask, and 0.7 g of distilled water was further added thereto and stirred. Next, while stirring the solution prepared in the 20 mL sample bottle, the phosphoric acid aqueous solution prepared in the 10 mL Erlenmeyer flask was added dropwise thereto over 10 minutes. The solution thus obtained is hereinafter referred to as L solution.
[0055]
Next, 3 g of the L solution was cast on a 5 cm square square frame made of polypropylene, and left in a fume hood at room temperature overnight and air-dried. Subsequently, the mold was put into an oven and heated at 50 ° C. for 24 hours, at 100 ° C. for 24 hours, and at 150 ° C. for 5 hours to obtain a brown opaque film.
[0056]
Both surfaces of the obtained film were sandwiched between platinum foils having a size of 5 mm × 10 mm, placed in an oven, and the ionic conductivity of the film was measured by an AC impedance method. As a result, the ionic conductivity of the film was 1.7 × 10 at 80 ° C. and 1.1% relative humidity. -4 S / cm.
[0057]
[Example 10]
Polyparavinylphenol / GPTMS / phosphate sample
1.16 g of polyparavinylphenol (molecular weight: 20,000) and 5.76 g of ethanol were put into a 20 mL glass sample bottle, stirred and dissolved, and then 5.9 g of 3-glycyloxypropyltrimethoxysilane (GPTMS) was further added. In addition, the mixture was stirred. On the other hand, 4.33 g of an 85% orthophosphoric acid aqueous solution was put into a 10 mL Erlenmeyer flask, and 0.7 g of distilled water was further added thereto and stirred. Next, while stirring the solution prepared in the 20 mL sample bottle, the phosphoric acid aqueous solution prepared in the 10 mL Erlenmeyer flask was added dropwise thereto over 10 minutes. The solution thus obtained is hereinafter referred to as M solution.
[0058]
Next, 3 g of the M solution was cast on a 5 cm square square mold made of polypropylene, and left overnight at room temperature in a fume hood and air-dried. Subsequently, the mold was put into an oven and heated at 50 ° C. for 24 hours, at 100 ° C. for 24 hours, and at 150 ° C. for 5 hours to obtain a brown opaque film.
[0059]
Both surfaces of the obtained film were sandwiched between platinum foils having a size of 5 mm × 10 mm, placed in an oven, and the ionic conductivity of the film was measured by an AC impedance method. As a result, the ionic conductivity of the film was 1.0 × 10 2 at 80 ° C. and 1.2% relative humidity. -4 S / cm.
[0060]
[Example 11]
Bisphenol A type epoxy resin / Phosmer M sample
1.86 g of bisphenol A epoxy resin (epoxy equivalent 186) and 2.9 g of acetone were put into a 20 mL glass sample bottle, stirred and dissolved, and then 2.1 g of Phosmer M (trade name) was further added and stirred. . The solution thus obtained is hereinafter referred to as N solution.
[0061]
Next, 2 g of the N solution was cast on a 5 cm square square mold made of polypropylene, and left overnight in a fume hood at room temperature to air-dry. Subsequently, the mold was put into an oven and heated at 50 ° C. for 24 hours, at 100 ° C. for 24 hours, and at 150 ° C. for 5 hours to obtain an ocher transparent film.
[0062]
Both surfaces of the obtained film were sandwiched between platinum foils having a size of 5 mm × 10 mm, placed in an oven, and the ionic conductivity of the film was measured by an AC impedance method. As a result, the ionic conductivity of the film was 4.2 × 10 4 at 80 ° C. and 1.3% relative humidity. -6 S / cm.
[0063]
[Example 12]
Polyparavinyl phenol / epoxy resin / phosmer M sample
1.5 g of bisphenol A type epoxy resin (epoxy equivalent: 186) and 7.26 g of acetone were put in a 20 mL glass sample bottle, stirred and dissolved. After adding and dissolving 1.5 g of polyparavinylphenol (molecular weight 9300), 5.25 g of Phosmer M (trade name) was further added and stirred. The solution thus obtained is hereinafter referred to as O solution.
[0064]
Next, 2 g of the O solution was cast on a 5 cm square square mold made of polypropylene, and left overnight at room temperature in a fume hood and air-dried. Subsequently, the mold was put into an oven and heated at 50 ° C. for 24 hours, at 100 ° C. for 24 hours, and at 150 ° C. for 5 hours to obtain a film.
[0065]
Both surfaces of the obtained film were sandwiched between platinum foils having a size of 5 mm × 10 mm, placed in an oven, and the ionic conductivity of the film was measured by an AC impedance method. As a result, the ionic conductivity of the film was 8.9 × 10 8 at 80 ° C. and 1.2% relative humidity. -6 S / cm.
[0066]
Example 13
Polyparavinyl phenol / epoxy resin / phosmer M sample
1.5 g of bisphenol A type epoxy resin (epoxy equivalent: 186) and 7.26 g of acetone were put in a 20 mL glass sample bottle, stirred and dissolved. After 1.5 g of polyparavinylphenol (molecular weight: 20,000) was added and dissolved therein, 5.25 g of Phosmer M (trade name) was further added and stirred. The solution thus obtained is hereinafter referred to as P solution.
[0067]
Next, 2 g of the P solution was cast on a 5 cm square square mold made of polypropylene, and left overnight at room temperature in a fume hood to air dry. Subsequently, the mold was put into an oven and heated at 50 ° C. for 24 hours, at 100 ° C. for 24 hours, and at 150 ° C. for 5 hours to obtain a film.
[0068]
Both surfaces of the obtained film were sandwiched between platinum foils having a size of 5 mm × 10 mm, placed in an oven, and the ionic conductivity of the film was measured by an AC impedance method. As a result, the ionic conductivity of the film was 1.1 × 10 4 at 80 ° C. and 1.2% relative humidity. -5 S / cm.
[0069]
[Example 14]
Low molecular resole / epoxy resin / phosmer M sample
1.5 g of bisphenol A type epoxy resin (epoxy equivalent: 186) and 7.26 g of acetone were put in a 20 mL glass sample bottle, stirred and dissolved. 1.61 g of an 82% methanol solution of low molecular resole was added to and dissolved in this, and then 5.25 g of Phosmer M (trade name) was added and stirred. The solution thus obtained is hereinafter referred to as Q solution.
[0070]
Next, 2 g of the Q solution was cast on a 5 cm square square mold made of polypropylene and left in a fume hood at room temperature overnight and air-dried. Subsequently, the mold was put into an oven and heated at 50 ° C. for 24 hours, at 100 ° C. for 24 hours, and at 150 ° C. for 5 hours to obtain a film.
[0071]
Both surfaces of the obtained film were sandwiched between platinum foils having a size of 5 mm × 10 mm, placed in an oven, and the ionic conductivity of the film was measured by an AC impedance method. As a result, the ionic conductivity of the film was 7.3 × 10 at 80 ° C. and 1.2% relative humidity. -6 S / cm.
[0072]
[Example 15]
Polymer resole / epoxy resin / phosmer M sample
1.5 g of bisphenol A type epoxy resin (epoxy equivalent: 186) and 7.26 g of acetone were put in a 20 mL glass sample bottle, stirred and dissolved. After adding and dissolving 2.42 g of a 54.8% methanol solution of high molecular resol in methanol, 5.25 g of Phosmer M (trade name) was further added and stirred. The solution thus obtained is hereinafter referred to as R solution.
[0073]
Next, 2 g of the R solution was cast in a 5 cm square square frame made of polypropylene, and left overnight at room temperature in a fume hood and air-dried. Subsequently, the mold was put into an oven and heated at 50 ° C. for 24 hours, at 100 ° C. for 24 hours, and at 150 ° C. for 5 hours to obtain a film.
[0074]
Both surfaces of the obtained film were sandwiched between platinum foils having a size of 5 mm × 10 mm, placed in an oven, and the ionic conductivity of the film was measured by an AC impedance method. As a result, the ionic conductivity of the film was 8.5 × 10 8 at 80 ° C. and 1.4% relative humidity. -5 S / cm.
[0075]
[Example 16]
Polyimide oligomer / epoxy resin / phosmer M sample
1.23 g of the D liquid described in Example 2 was placed in a 20 mL glass sample bottle, and 2.51 g of methanol, 0.75 g of bisphenol A type epoxy resin (epoxy equivalent 186) and 2.65 g of Phosmer M (trade name) were further added. In addition, the mixture was stirred. The solution thus obtained is hereinafter referred to as S solution.
[0076]
Next, 2 g of the S solution was cast on a 5 mm square square mold made of polypropylene, and left overnight at room temperature in a fume hood and air-dried. Subsequently, the mold was put into an oven and heated at 50 ° C. for 24 hours, at 100 ° C. for 24 hours, and at 150 ° C. for 5 hours to obtain a yellow opaque film.
[0077]
Both surfaces of the obtained film were sandwiched between platinum foils having a size of 5 mm × 10 mm, placed in an oven, and the ionic conductivity of the film was measured by an AC impedance method. As a result, the ionic conductivity of the film was 1.6 × 10 6 at 80 ° C. and 2% relative humidity. -4 S / cm.
[0078]
[Comparative Example] Nafion
As a comparative example, an evaluation test was performed using Nafion (trade name), a perfluorosulfonic acid-based polymer that is a commercially available polymer electrolyte. A film of Nafion (trade name) was sandwiched between platinum foils having a size of 5 mm × 10 mm in the same manner as in the example, placed in an oven, and the ionic conductivity of the film was measured by an AC impedance method. As a result, the ionic conductivity of Nafion (trade name) was 4.1 × 10 4 at 60 ° C. and 4.1% relative humidity. -5 S / cm, and 8.8 × 10 at 80 ° C. and 1.3% relative humidity. -6 S / cm.
[0079]
Table 1 is a table summarizing the list of the measurement results of the ionic conductivity of the solid electrolytes according to Examples 1 to 16 and Comparative Example described above.
[0080]
[Table 1]
[0081]
From the above, it can be seen that the solid electrolyte according to this example has better ion conductivity in a low humidity environment than the conventional electrolyte composed of perfluorosulfonic acid-based polymer.
[0082]
Further, after the solid electrolyte according to the present example was formed into a film to form an electrolyte membrane, this electrolyte membrane was sandwiched between a pair of electrodes containing a platinum catalyst to produce a solid electrolyte fuel cell. The manufactured fuel cell was able to operate without a special humidification mechanism even under a low humidity condition of 10% or less in relative humidity. Furthermore, even in a use environment at approximately 0 ° C. to 200 ° C., a fuel cell having a reduced operating condition without a decrease in cell performance was obtained.
[0083]
【The invention's effect】
The invention according to claim 1 is a solid electrolyte characterized by being synthesized using at least a silane coupling agent having an organic substituent and a compound having a phosphate group as raw material components. Under low humidity conditions, it exhibits higher ionic conductivity than conventional perfluorosulfonic acid-based polymers, so when used as an electrolyte membrane for fuel cells, secondary batteries, display elements, solar cells, etc. The troublesomeness can be eliminated.
[0084]
The invention described in claim 2 is a solid electrolyte characterized by being synthesized using at least a silane coupling agent having an organic substituent, a compound having a phosphate group, and an addition type polyimide resin as raw material components, According to the present invention, the addition of an organic component has the effect of imparting flexibility to the material. In particular, the addition-type polyimide can be mixed with the raw material component according to claim 1 at the polymerizable monomer stage. A homogeneous composite can be obtained. In addition, polyimide resin is a material having high heat resistance, and an effect of increasing the thermal stability of the material can be expected by blending the polyimide resin.
[0085]
The invention according to claim 3 is a solid electrolyte characterized by being synthesized using at least a silane coupling agent having an organic substituent, a compound having a phosphate group, and a compound having a phenolic hydroxyl group as raw material components. According to the present invention, the effect of imparting flexibility to the material by adding an organic component is provided. In particular, since the phenolic hydroxyl group functions as a weak protonic acid, the composite is flexible without impairing the proton conductivity. The effect of imparting properties can be expected.
[0086]
The invention described in claim 4 is a solid electrolyte characterized by being synthesized using at least an epoxy resin and a compound having a phosphate group as raw material components. According to the present invention, the following effects are obtained. Can be. That is, the raw material component according to claim 1 is a silane coupling agent having an organic substituent, and more specifically, a compound having an epoxy group as an organic substituent is preferable. It is limited and the range of raw material selection is narrow. On the other hand, various and various epoxy resins can be obtained from the market, and the use of the epoxy resin has the effect of improving the properties of various composites.
[0087]
The invention according to claim 5 is a solid electrolyte characterized by being synthesized using at least an epoxy resin, a compound having a phosphate group, and an addition type polyimide resin as raw material components, wherein the addition type polyimide has a low molecular weight. According to the present invention, a composite material in which polyimide is homogeneously mixed with the raw material component according to claim 4 can be easily produced because the compound can be compounded at the stage. Further, the heat resistance of the polyimide resin is high, and the effect of increasing the thermal stability of the composite material can be expected.
[0088]
The invention according to claim 6 is a solid electrolyte characterized by being synthesized using at least an epoxy resin, a compound having a phosphoric acid group, and a compound having a phenolic hydroxyl group as raw material components, and the phenolic hydroxyl group is weak. Since it functions as a protonic acid, according to the present invention, the effect of imparting flexibility to the material without impairing the proton conductivity of the composite can be expected.
[0089]
The invention described in claim 7 is the solid electrolyte according to any one of claims 1 to 6, wherein the compound having a phosphate group is a phosmer (trade name). According to the invention, each of the above effects can be made more remarkable.
[0090]
The invention described in claim 8 is the solid electrolyte according to claim 3 or 6, wherein the compound having a phenolic hydroxyl group is a polyparavinylphenol or a phenol resin. According to the above, each of the effects can be made more remarkable.
[0091]
According to a ninth aspect of the present invention, there is provided a solid electrolyte fuel cell having an electrolyte membrane formed by film-forming the solid electrolyte according to any one of the first to eighth aspects. According to the invention, the solid electrolyte exhibits a higher ionic conductivity than conventional perfluorosulfonic acid-based polymers under low humidity conditions, so that the solid electrolyte fuel cell eliminates the hassle of water management. it can.

Claims (9)

  1. A solid electrolyte characterized by being synthesized using at least a silane coupling agent having an organic substituent and a compound having a phosphate group as raw material components.
  2. A solid electrolyte characterized by being synthesized using at least a silane coupling agent having an organic substituent, a compound having a phosphate group, and an addition type polyimide resin as raw material components.
  3. A solid electrolyte characterized by being synthesized using at least a silane coupling agent having an organic substituent, a compound having a phosphate group, and a compound having a phenolic hydroxyl group as raw material components.
  4. A solid electrolyte characterized by being synthesized using at least an epoxy resin and a compound having a phosphate group as raw material components.
  5. A solid electrolyte characterized by being synthesized using at least an epoxy resin, a compound having a phosphate group, and an addition type polyimide resin as raw material components.
  6. A solid electrolyte characterized by being synthesized using at least an epoxy resin, a compound having a phosphoric acid group and a compound having a phenolic hydroxyl group as raw material components.
  7. The solid electrolyte according to any one of claims 1 to 6, wherein the compound having a phosphate group is a phosmer (trade name).
  8. 7. The solid electrolyte according to claim 3, wherein the compound having a phenolic hydroxyl group is a polyparavinylphenol or a phenolic resin.
  9. A solid electrolyte fuel cell comprising an electrolyte membrane formed by filming the solid electrolyte according to any one of claims 1 to 8.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100976862B1 (en) 2007-11-21 2010-08-23 주식회사 엘지화학 secondary battery with improved storage characteristics and method for manufacturing the same

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100976862B1 (en) 2007-11-21 2010-08-23 주식회사 엘지화학 secondary battery with improved storage characteristics and method for manufacturing the same
US8277981B2 (en) 2007-11-21 2012-10-02 Lg Chem, Ltd. Secondary battery with improved storage characteristics and method for manufacturing the same
US8580419B2 (en) 2007-11-21 2013-11-12 Lg Chem, Ltd. Secondary battery with improved storage characteristics and method for manufacturing the same

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