WO2015155979A1 - Polymer electrolyte composition and polymer electrolyte membrane, polymer electrolyte membrane with catalyst layer, membrane electrode assembly, and polymer electrolyte fuel cell each using the same - Google Patents
Polymer electrolyte composition and polymer electrolyte membrane, polymer electrolyte membrane with catalyst layer, membrane electrode assembly, and polymer electrolyte fuel cell each using the same Download PDFInfo
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- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
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- H01M8/1025—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having only carbon and oxygen, e.g. polyethers, sulfonated polyetheretherketones [S-PEEK], sulfonated polysaccharides, sulfonated celluloses or sulfonated polyesters
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- H01M8/1018—Polymeric electrolyte materials
- H01M8/102—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer
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- H01M8/1039—Polymeric electrolyte materials halogenated, e.g. sulfonated polyvinylidene fluorides
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- H01M8/1041—Polymer electrolyte composites, mixtures or blends
- H01M8/1046—Mixtures of at least one polymer and at least one additive
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Definitions
- the present invention relates to a polymer electrolyte composition, a polymer electrolyte membrane, a membrane electrode assembly, and a polymer electrolyte fuel cell each using the same.
- Fuel cells are a kind of power generator which extracts electric energy through electrochemical oxidation of fuels such as hydrogen and methanol. In recent years, the fuel cells have drawn attention as a clean energy supply source.
- a polymer electrolyte fuel cell is operated at a low standard working temperature of approximately 100°C, and provides high energy density, and thus is expected to be widely applied as relatively small-scale distributed power facilities and as mobile power generator on automobile, ship, and the like.
- the polymer electrolyte fuel cell also draws attention as power source of small-scale mobile apparatus and portable apparatus, and is expected to be mounted on cell phone, personal computer, and the like, in place of secondary battery such as nickel-hydrogen battery and lithium-ion battery.
- a normal fuel cell is constituted by cell units, the cell unit having a configuration of a membrane electrode assembly (hereinafter referred to also as MEA) being sandwiched between separators, which MEA is constituted by an anode electrode and a cathode electrode in which a reaction of power generation occurs, and by a polymer electrolyte membrane serving as a proton conductor between the anode and the cathode.
- MEA membrane electrode assembly
- the main component of the polymer electrolyte membrane is an ionic group-containing polymer (polymer electrolyte material), there can also be used a polymer electrolyte composition containing an additive and the like, in order to increase the durability.
- the characteristics required of the polymer electrolyte membrane include, first, high proton conductivity, specifically high proton conductivity even under high temperature and low-humidification conditions. Since the polymer electrolyte membrane also functions as the barrier that prevents direct reaction between fuel and oxygen, low permeability of fuel is required. Other characteristics include chemical stability for withstanding strong oxidizing atmosphere during operation of fuel cell, mechanical strength and physical durability of being capable of withstanding thinning of membrane and repeated swell-drying cycles.
- Nafion registered trademark, manufactured by DuPont
- DuPont a perfluorosulfonic acid based polymer
- Nafion registered trademark
- Nafion there have been pointed out a problem of losing membrane mechanical strength and physical durability by swelling-drying, a problem in which the use at high temperatures is not possible because of low softening point, a problem of waste disposal after use, and further an issue of difficulty in recycling the material.
- hydrocarbon-based electrolyte membranes has been also actively conducted in recent years as a polymer electrolyte membrane having excellent membrane characteristics at a low price and being capable of substituting Nafion (registered trademark).
- Patent Literatures 1 and 2 propose polymer electrolyte compositions adding a phosphorous-based antioxidant. Specifically, a polymer electrolyte composition adding a phosphorous acid ester (phosphite)-based antioxidant to a sulfonic acid group-containing polyethersulfone-based polymer, and a polymer electrolyte composition adding a phosphonic acid group-containing polymer such as polyvinylphosphonic acid to a sulfonic acid group-containing polyethersulfone-based polymer or a sulfonic acid group-containing polyetherketone-based polymer are proposed.
- a polymer electrolyte composition adding a phosphorous acid ester (phosphite)-based antioxidant to a sulfonic acid group-containing polyethersulfone-based polymer
- a polymer electrolyte composition adding a phosphonic acid group-containing polymer such as polyvinylphosphonic acid to a sulfonic acid group-containing polyether
- Patent Literatures 3 to 5 propose electrolyte compositions adding sulfur-based, amine-based, phenol-based antioxidants and the like, in addition to phosphorous-based antioxidants. Specifically, a polymer electrolyte composition adding an antioxidant such as phosphorous acid ester (phosphite), thioether, hindered amine or hindered phenol to a sulfonic acid group-containing polyethersulfone-based polymer or a sulfonic acid group-containing polyarylene-based polymer are proposed.
- an antioxidant such as phosphorous acid ester (phosphite), thioether, hindered amine or hindered phenol to a sulfonic acid group-containing polyethersulfone-based polymer or a sulfonic acid group-containing polyarylene-based polymer are proposed.
- Patent Literature 6 proposes a polymer electrolyte composition adding cerium ion or manganese ion to a perfluorosulfonic acid-based polymer and a sulfonic acid group-containing polyetherketone-based polymer.
- Patent Literature 7 proposes a polymer electrolyte composition adding a phosphorus-containing additive selected from phosphine compounds and phosphinite compounds, and further a transition metal atom such as cerium or manganese.
- Patent Literature 8 proposes a peroxide decomposition catalyst coordinated to a base metal atom such as manganese or iron by a nitrogen atom such as imidazole or pyridine.
- Patent Literature 9 and Patent Literature 10 propose a polymer electrolyte composition adding a phenanthroline derivative or a complex of phenanthroline and cerium ion or manganese ion to a perfluoro-based electrolyte membrane.
- Patent Literature 1 Japanese Patent Laid-Open No. 2003-151346
- Patent Literature 2 Japanese Patent Laid-Open No. 2000-11756
- Patent Literature 3 Japanese Patent Laid-Open No. 2003-201403
- Patent Literature 4 Japanese Patent Laid-Open No. 2007-66882
- Patent Literature 5 Japanese Patent Laid-Open No. 2005-213325
- Patent Literature 6 Japanese Patent Laid-Open No. 2006-99999
- Patent Literature 7 WO 2013/94538
- Patent Literature 8 Japanese Patent Laid-Open No. 2007-38213
- Patent Literature 9 Japanese Patent Laid-Open No. 2007-38213
- Patent Literature 9 WO 2011/57768
- Patent Literature 10 WO 2011/57769 A
- Patent Literatures 1 to 5 a general antioxidant and a light stabilizer for suppressing deterioration of plastic materials due to heat and light are only added, and they cannot obtain satisfactory chemical stability and durability of polymer electrolyte compositions under the conditions like fuel cell operating environments (high temperature, humidified, strong acidity).
- 2,2’-bipyridyl and 1,10-phenanthroline described in Patent Literature 9 may be oxidized by hydrogen peroxide and hydroxy radical produced during operation and eluted outside of the membrane, thus they cannot be still said to obtain satisfactory chemical stability and durability.
- Patent Literature 6 because the sulfonic acid group is ion-exchanged by cerium ion or manganese ion that is a polyvalent metal, there are problems of deterioration of proton conductivity of the polymer electrolyte composition, deterioration of solvent solubility and solution membrane-forming ability due to ion cross-linking, and embrittlement of the membrane.
- a phosphorous-based additive in Patent Literature 7, 2,2’-bipyridyl in Patent Literature 8, 1,10-phenanthroline in Patent Literature 10 and the like are allowed to form a coordination (complex) structure with the metal, thereby relaxing the ion cross-linking, and improving durability while maintaining solvent solubility and membrane-forming ability.
- the complex structure is comparatively hydrophilic and may be eluted outside of the membrane during operation, thus they cannot be still said to obtain satisfactory chemical stability and durability.
- the polymer electrolyte compositions according to prior art are insufficient in economy, processability, proton conductivity, mechanical strength, chemical stability, and physical durability, thus they cannot serve as industrially useful polymer electrolyte compositions.
- the present invention provides a highly practically applicable polymer electrolyte composition having excellent chemical stability of being able to be resistant to a strong oxidizing atmosphere during operation of fuel cell, and being capable of achieving excellent proton conductivity under low-humidification conditions, excellent mechanical strength and physical durability, and provides a polymer electrolyte membrane, a membrane electrode assembly, and a polymer electrolyte fuel cell each using the same.
- the polymer electrolyte composition according to the present invention includes a polymer electrolyte composition comprising an ionic group-containing polymer (A), a phosphorus-containing additive (B) and a nitrogen-containing aromatic additive (C), the phosphorus-containing additive (B) being at least one kind selected from a compound represented by the following general formula (B1) and a compound represented by the following general formula (B2), and the nitrogen-containing aromatic additive (C) being at least one kind selected from a compound represented by the following general formula (C1) and a compound represented by the following general formula (C2).
- R 1 to R 7 each independently represent a substituent selected from hydrocarbon groups having a straight chain, a cyclic, or a branched structure, represented by the general formula C m H n (m and n are an integer number), alkoxy groups having a straight chain, a cyclic, or a branched structure, represented by the general formula OC m H n (m and n are an integer number), halogen atoms and a hydrogen atom;
- Z 1 represents a divalent substituent selected from hydrocarbon groups having a straight chain, a cyclic, or a branched structure, represented by the general formula C m H n (m and n are an integer number) and alkoxy groups having a straight chain, a cyclic, or a branched structure, represented by the general formula OC m H n (m and n are an integer number) or OC m H n O (m and n are an integer number);
- R 8 to R 23 each independently represent a substituent selected from hydrocarbon groups having a straight chain, a cyclic, or a branched structure, represented by the general formula C m H n (m and n are an integer number), alkoxy groups having a straight chain, a cyclic, or a branched structure, represented by the general formula OC m H n (m and n are an integer number), halogen atoms, a hydrogen atom, carboxyl groups, carboxylate groups, sulfonic acid groups, sulfate groups, hydroxyl groups, amino groups, cyano groups and nitro groups; and m and n are independent in each formula.
- the present invention can provide a practically excellent polymer electrolyte composition having excellent chemical stability of being resistant to strong oxidizing atmosphere, and achieving excellent proton conductivity under low-humidification conditions, excellent mechanical strength and physical durability; a polymer electrolyte membrane, a membrane electrode assembly, and a polymer electrolyte fuel cell each using the same.
- the present inventors have conducted detail study on the polymer electrolyte membrane in fuel cell and the like in order to solve the above problems, and have found out that the addition of a specific phosphorus-containing additive (B) to an ionic group-containing polymer (A), and further addition of a specific nitrogen-containing aromatic additive (C) make it possible to cause a polymer electrolyte composition, specifically a polymer electrolyte membrane for fuel cell, to express excellent performances in proton conductivity and power generation characteristics also under low-humidification conditions, processability such as membrane-forming, chemical durability such as oxidation resistance, radical resistance, and hydrolysis resistance, and physical durability such as mechanical strength of membrane and hot water resistance. Through further various examinations, the inventors have completed the present invention.
- the additive means a compound other than the ionic group-containing polymer (A) contained in the polymer electrolyte composition, and a compound mixed to the ionic group-containing polymer.
- the “additive” is one mainly functioning as an antioxidant, and is a compound having at least one of the functions described in, for example, “Polymer Additives Handbook” pp.
- metal inactivator metallic inactivator
- the phosphorus-containing additive functions as “metal inactivator”, and the nitrogen-containing aromatic additive functions as “peroxide decomposer” or “radical scavenger”.
- the oxide of a nitrogen-containing aromatic compound represented by the general formula (C1) or (C2) produced by detoxifying hydrogen peroxide or hydroxy radical is reduced by the phosphorus-containing additive represented by the general formula (B1) or (B2) to return to the original nitrogen-containing aromatic compound
- the oxide of the phosphorus-containing additive inferior in elution resistance is reduced by hydrogen generated during operation of fuel cell to return to the original phosphorus-containing additive.
- the phosphorus-containing additive (B) used in the present invention will be described.
- the compound used as the phosphorus-containing additive (B) is a compound represented by the following general formula (B1) or (B2).
- R 1 to R 7 each independently represent a substituent selected from hydrocarbon groups having a straight chain, a cyclic, or a branched structure, represented by the general formula C m H n (m and n are an integer number), alkoxy groups having a straight chain, a cyclic, or a branched structure, represented by the general formula OC m H n (m and n are an integer number), halogen atoms and a hydrogen atom;
- Z 1 represents a divalent substituent selected from hydrocarbon groups having a straight chain, a cyclic, or a branched structure, represented by the general formula C m H n (m and n are an integer number) and alkoxy groups having a straight chain, a cyclic, or a branched structure, represented by the general formula OC m H n (m and n are an integer number) or OC m H n O (m and n are an integer number);
- bidentate phosphorus-containing compounds (B2) having two phosphorus atoms are preferable, in terms of coordination ability to a metal, an ability of detoxifying hydrogen peroxide, hydroxy radical and peroxide radical, and reduction efficiency of a nitrogen-containing aromatic compound oxidant, and phosphine compounds having two phosphorus atoms are most preferable, from the viewpoint of hydrolysis resistance and elution resistance.
- the bidentate phosphorus-containing compound (B2) it is possible to enhance an effect as a metal inactivator by a chelate effect, enhance an effect as a peroxide decomposer or a radical scavenger, and enhance reduction efficiency of a nitrogen-containing aromatic compound oxidant, while maintaining elution resistance.
- amorphous polymer means a polymer which is not a crystalline polymer and which does not substantially progress the crystallization. Accordingly, even for a crystalline polymer, when the polymer does not sufficiently progress the crystallization, the polymer is in an amorphous state in some cases.
- a membrane electrode assembly (MEA) is prepared by a press
- a known method such as “Chemical Plating Methods”, described in Journal of Electrochemistry, 1985, 53, p. 269, (Electrochemical Society of Japan), and “Hot press joining of gas-diffusion electrode”, described in Electrochemical Science and Technology, 1988, 135, 9, p. 2209.
- the temperature and the pressure during pressing may be adequately selected depending on the thickness of electrolyte membrane, the water content, the catalyst layer, and the electrode substrate.
- press-composite can be applied even when the electrolyte membrane is in a dry state or in a state of absorbing water.
- Specific press method includes roll press that specifies pressure and clearance, flat press that specifies pressure and the like, and from the viewpoint of industrial productivity and suppression of thermal decomposition of polymer material having an ionic group, the press is preferably performed in a temperature range of 0°C to 250°C. From the viewpoint of protection of electrolyte membrane and of electrode, the press is preferably performed under lower pressure as much as possible, and in the case of flat press, 10 MPa or smaller pressure is preferred.
- a preferred selectable method is, from the viewpoint of prevention of short-circuit of anode and cathode electrodes, to join the electrode and the electrolyte membrane to thereby form the fuel cell without applying composite-formation by the press process. With that method, when power generation is repeated as the fuel cell, the deterioration of electrolyte membrane presumably originated from the short-circuit position tends to be suppressed, which improves the durability of the fuel cell.
- Hot water resistance of additive The hot water resistance of the additive was evaluated by determining the residual rate after immersion in 95°C hot water.
- the electrolyte membrane was cut to two rectangular pieces of each about 5 cm in length and about 10 cm in width.
- the cut sample was immersed in 95°C hot water for 8 hours to elute the additive.
- the electrolyte membrane before and after the immersion in hot water was cut to a size of 5 cm x 5 cm, respectively.
- Each of the cut samples was analyzed by the ICP Emission spectrophotometry to determine the content of the additive, and the hot water resistance was evaluated as the residual rate of the additive.
- a membrane electrode assembly was prepared using a similar method to the above, and the assembly was placed on the evaluation cell. Then, under similar conditions to the above, the accelerated degradation test in open circuit was performed. The time until the open circuit voltage decreased to 0.7 V or smaller was evaluated as the open circuit voltage holding time.
- the internal temperature was gradually increased to 120°C, and the heating was continued until the distilling of methyl formate, methanol, and orthotrimethyl formate completely stops.
- the reaction solution was diluted by ethyl acetate, and then the organic layer was rinsed with 100 mL of a 5% aqueous solution of potassium carbonate. After separating the solution, the solvent was distilled out. 80 mL of dichloromethane was added to the residue, crystal was deposited, then filtered and dried to obtain 52.0 g of 2,2-bis(4-hydroxyphenyl)-1,3-dioxolane. Through the GC analysis of the crystal, 99.8% of 2,2-bis(4-hydroxyphenyl)-1,3-dioxolane and 0.2% of 4,4’-dihydroxybenzophenone were confirmed.
- the precipitated product obtained was separated by filtration, followed by recrystallization by using an ethanol aqueous solution, and thus there was obtained disodium 3,3’-disulfonate-4,4’-difluorobenzophenone represented by the general formula (G2).
- the purity was 99.3%.
- the structure was confirmed by 1 H-NMR.
- the impurities were quantitatively analyzed by capillary electrophoresis (organic substances) and by ion chromatography (inorganic substances).
- the resultant content was dewatered in 300 mL of N-methylpyrrolidone (NMP) and 100 mL of toluene at 170°C. Then, the resultant content was heated to remove the toluene, and was polymerized at 180°C for 1 hour. Purification was performed by reprecipitation through the use of a large quantity of isopropyl alcohol, and thus there was obtained the oligomer containing an ionic group (terminal OM group), represented by the formula (G4). The number-average molecular weight was 29,000.
- the block polymer b1 contained 50 mol% of the constituent unit represented by the general formula (S1) as the segment (A1) containing an ionic group, and 100 mol% of the constituent unit represented by the general formula (S2) as the segment (A2) not containing an ionic group.
- the reaction mixture was added to 60 mL of methanol, and subsequently, 60 mL of 6 mol/L hydrochloric acid was added for agitation of the mixture for 1 hour.
- the deposited solid was separated by filtration, and the resultant solid was dried, and 1.75 g of a gray-white block copolymer precursor b2’ (polyarylene precursor) containing the segments represented by the following formula (G6) and the following formula (G7) was obtained at a yield of 97%.
- the weight-average molecular weight was 210,000.
- the weight-average molecular weight of thus obtained polyarylene was 190,000.
- the block copolymer b2 itself was the polymer electrolyte membrane
- the ion-exchange capacity obtained by the neutralization titration was 2.02 meq/g.
- reaction liquid After the obtained reaction liquid was allowed to stand for cooling, 100 mL of toluene was added thereto and the liquid was diluted. The precipitate of by-product inorganic compounds was removed by filtration, and the filtrate was charged into 2 L of methanol. The precipitated product was filtered, collected and dried, which was then dissolved in 250 mL of tetrahydrofuran. The mixture was reprecipitated in 2 L of methanol to obtain 109 g of the target oligomer. The number-average molecular weight of the oligomer was 8,000.
- the organic layer was rinsed with a solution of sodium chloride, followed by drying with magnesium sulfate, then the ethyl acetate was distilled out to obtain a light yellow crude crystal of 3-(2,5-dichlorobenzoyl)benzenesulfonic acid chloride.
- the crude crystal was used as is without purification, at the next step.
- the reaction system was heated under agitation (ultimately heated to a temperature of 82°C), and caused to react for 3 hours. During the reaction period, the viscosity increase in the reaction system was observed.
- the polymerized reaction solution was diluted with 180 mL of DMAc, and the resultant solution was agitated for 30 minutes, then, the reaction mixture was filtered using Celite as the filter aid. Using a 1 L three neck flask equipped with an agitator, 25.6 g (295 mmol) of lithium bromide was added to the filtrate three times (each one third of aliquot part) with an interval of 1 hour. The resultant mixture was caused to react at 120°C for 5 hours in nitrogen atmosphere.
- the mixture was cooled to room temperature and poured into 4 L of acetone for solidification.
- the solidified product was coagulated and air-dried, then crushed in a mixer, and the resultant substance was rinsed with 1500 mL of 1 N sulfuric acid under agitation. After filtration, the product was rinsed with ion-exchange water until the pH of the rinsing liquid became 5 or larger. Then, the product was dried at 80°C overnight, and thus 39.1 g of the target block copolymer b3 was obtained.
- the weight-average molecular weight of the block copolymer was 200,000.
- the ion-exchange capacity obtained by the neutralization titration was 2.3 meq/g.
- a 20 g of the block copolymer b1 obtained in Synthesis Example 1 was dissolved in 80 g of NMP. 200 mg of 1,2-bis(diphenylphosphino)ethane (hereinafter referred to as “DPPE”, manufactured by Aldrich) was added to the solution, then the mixture was agitated for 3 minutes using an agitator at 20,000 rpm to obtain a transparent solution of 20% by mass of the concentration of polymer. The solubility of the polymer was extremely good. The resulting solution was pressure-filtered using a glass fiber filter, followed by flow-casting coating on a glass substrate.
- DPPE 1,2-bis(diphenylphosphino)ethane
- the coating was heat-treated under nitrogen atmosphere at 150°C for 10 minutes to obtain a polyketalketone membrane (15 mm of membrane thickness).
- the membrane was immersed at 95°C for 24 hours in an aqueous solution of 10% by weight of sulfuric acid for proton substitution and deprotection reaction, and then the membrane was immersed for 24 hours in a large excessive volume of pure water for full rinsing.
- 5-amino-1,10-phenanthroline (1.5 mmol) was dissolved in pure water to prepare a 50 mmol/L 5-amino-1,10-phenanthroline solution in 30 L.
- 20 g of the polyether ketone membrane was immersed for 72 hours to contain 5-amino-1,10-phenanthroline, and thus the polymer electrolyte membrane was obtained.
- the obtained membrane was insoluble in NMP, the molecular weight retention rate was not able to be measured, and thus the open circuit voltage holding time was measured as the durability test. However, the evaluation was not completed within 3,000 hours, and thus the chemical durability of the electrolyte membrane was evaluated as the voltage retention rate. In addition, there were measured the ion-exchange capacity, the hot water resistance, and the proton conductivity at 80°C and 25% RH of the obtained electrolyte membrane. The result is shown in Table 1.
- the electrolyte membrane was obtained in the same manner as in Example 1 except that 5-amino-1,10-phenanthroline was changed to 0.28 g of 1,10-phenanthroline. Since the obtained membrane was insoluble in NMP, the molecular weight retention rate was not able to be measured, and thus the open circuit voltage holding time was measured as the durability test. However, the evaluation was not completed within 3,000 hours, and thus the chemical durability of the electrolyte membrane was evaluated as the voltage retention rate. In addition, there were measured the ion-exchange capacity, the hot water resistance, and the proton conductivity at 80°C and 25% RH of the obtained electrolyte membrane. The result is shown in Table 1.
- the electrolyte membrane was obtained in the same manner as in Example 1 except that 5-amino-1,10-phenanthroline was changed to 0.51 g of bathphenanthroline. Since the obtained membrane was insoluble in NMP, the molecular weight retention rate was not able to be measured, and thus the open circuit voltage holding time was measured as the durability test. However, the evaluation was not completed within 3,000 hours, and thus the chemical durability of the electrolyte membrane was evaluated as the voltage retention rate. In addition, there were measured the ion-exchange capacity, the hot water resistance, and the proton conductivity at 80°C and 25% RH of the obtained electrolyte membrane. The result is shown in Table 1.
- the electrolyte membrane was obtained in the same manner as in Example 1 except that 5-amino-1,10-phenanthroline was changed to 0.25 g of 2,2’-bipyridyl. Since the obtained membrane was insoluble in NMP, the molecular weight retention rate was not able to be measured, and thus the open circuit voltage holding time was measured as the durability test. However, the evaluation was not completed within 3,000 hours, and thus the chemical durability of the electrolyte membrane was evaluated as the voltage retention rate. In addition, there were measured the ion-exchange capacity, the hot water resistance, and the proton conductivity at 80°C and 25% RH of the obtained electrolyte membrane. The result is shown in Table 1.
- the electrolyte membrane was obtained in the same manner as in Example 1 except that 4 g of DPPE, 9 g of 5-amino-1,10-phenanthroline and 90 L of 5-amino-1,10-phenanthroline aqueous solution were used, and the immersion time of the polyether ketone membrane was changed to 120 hours. Since the obtained membrane was insoluble in NMP, the molecular weight retention rate was not able to be measured, and thus the open circuit voltage holding time was measured as the durability test. However, the evaluation was not completed within 3,000 hours, and thus the chemical durability of the electrolyte membrane was evaluated as the voltage retention rate. In addition, there were measured the ion-exchange capacity, the hot water resistance, and the proton conductivity at 80°C and 25% RH of the obtained electrolyte membrane. The result is shown in Table 1.
- the electrolyte membrane was obtained in the same manner as in Example 6 except that 2 mg of DPPE, 6 mg of 5-amino-1,10-phenanthroline and 15 L of 5-amino-1,10-phenanthroline aqueous solution were used. Since the obtained membrane was insoluble in NMP, the molecular weight retention rate was not able to be measured, and thus the open circuit voltage holding time was measured as the durability test. In addition, there were measured the ion-exchange capacity, the hot water resistance, and the proton conductivity at 80°C and 25% RH of the obtained electrolyte membrane. The result is shown in Table 1.
- the electrolyte membrane was obtained in the same manner as in Example 1 except that DPPE was changed to 1,2-bis(diphenylphosphino)benzene. Since the obtained membrane was insoluble in NMP, the molecular weight retention rate was not able to be measured, and thus the open circuit voltage holding time was measured as the durability test. However, the evaluation was not completed within 3,000 hours, and thus the chemical durability of the electrolyte membrane was evaluated as the voltage retention rate. In addition, there were measured the ion-exchange capacity, the hot water resistance, and the proton conductivity at 80°C and 25% RH of the obtained electrolyte membrane. The result is shown in Table 1.
- the electrolyte membrane was obtained in the same manner as in Example 1 except that DPPE was changed to 1,2-bis(diphenylphosphino)decane. Since the obtained membrane was insoluble in NMP, the molecular weight retention rate was not able to be measured, and thus the open circuit voltage holding time was measured as the durability test. However, the evaluation was not completed within 3,000 hours, and thus the chemical durability of the electrolyte membrane was evaluated as the voltage retention rate. In addition, there were measured the ion-exchange capacity, the hot water resistance, and the proton conductivity at 80°C and 25% RH of the obtained electrolyte membrane. The result is shown in Table 1.
- the electrolyte membrane was obtained in the same manner as in Example 1 except that DPPE was changed to diphenylmethoxyphosphine. Since the obtained membrane was insoluble in NMP, the molecular weight retention rate was not able to be measured, and thus the open circuit voltage holding time was measured as the durability test. In addition, there were measured the ion-exchange capacity, the hot water resistance, and the proton conductivity at 80°C and 25% RH of the obtained electrolyte membrane. The result is shown in Table 1.
- the electrolyte membrane was obtained in the same manner as in Example 1 except that DPPE was changed to dimethoxyphenylphosphine. Since the obtained membrane was insoluble in NMP, the molecular weight retention rate was not able to be measured, and thus the open circuit voltage holding time was measured as the durability test. In addition, there were measured the ion-exchange capacity, the hot water resistance, and the proton conductivity at 80°C and 25% RH of the obtained electrolyte membrane. The result is shown in Table 1.
- the electrolyte membrane was obtained in the same manner as in Example 1 except that DPPE was changed to triphenoxyphosphine. Since the obtained membrane was insoluble in NMP, the molecular weight retention rate was not able to be measured, and thus the open circuit voltage holding time was measured as the durability test. In addition, there were measured the ion-exchange capacity, the hot water resistance, and the proton conductivity at 80°C and 25% RH of the obtained electrolyte membrane. The result is shown in Table 1.
- the electrolyte membrane was obtained in the same manner as in Example 1 except that the block polymer b1 was changed to Nafion (registered trademark) NRE211CS (manufactured by DuPont) which is a fluorine-based electrolyte polymer. Since the obtained membrane was insoluble in NMP, the molecular weight retention rate was not able to be measured, and thus the open circuit voltage holding time was measured as the durability test. In addition, there were measured the ion-exchange capacity, the hot water resistance, and the proton conductivity at 80°C and 25% RH of the obtained electrolyte membrane. The result is shown in Table 1.
- the electrolyte membrane was obtained in the same manner as in Example 1 except that the block polymer b1 was changed to the PES-based block copolymer b2. Since the obtained membrane was soluble in NMP, the molecular weight retention rate was measured as the durability test. In addition, there were measured the ion-exchange capacity, the hot water resistance, and the proton conductivity at 80°C and 25% RH of the obtained electrolyte membrane. The result is shown in Table 1.
- the electrolyte membrane was obtained in the same manner as in Example 1 except that the block polymer b1 was changed to the polyarylene-based block copolymer b3. Since the obtained membrane was soluble in NMP, the molecular weight retention rate was measured as the durability test. In addition, there were measured the ion-exchange capacity, the hot water resistance, and the proton conductivity at 80°C and 25% RH of the obtained electrolyte membrane. The result is shown in Table 1.
- the electrolyte membrane was obtained in the same manner as in Example 1 except that DPPE was changed to the DPPE-Ce described above. Since the obtained membrane was insoluble in NMP, the molecular weight retention rate was not able to be measured, and thus the open circuit voltage holding time was measured as the durability test. However, the evaluation was not completed within 3,000 hours, and thus the chemical durability of the electrolyte membrane was evaluated as the voltage retention rate. In addition, there were measured the ion-exchange capacity, the hot water resistance, and the proton conductivity at 80°C and 25% RH of the obtained electrolyte membrane. The result is shown in Table 1.
- the electrolyte membrane was obtained in the same manner as in Example 1 except that DPPE was changed to dichloro[(R)-(+)-2,2’-bis(diphenylphosphino)-1,1’-binaphthyl]ruthenium(II) (BINAP-Ru). Since the obtained membrane was insoluble in NMP, the molecular weight retention rate was not able to be measured, and thus the open circuit voltage holding time was measured as the durability test. However, the evaluation was not completed within 3,000 hours, and thus the chemical durability of the electrolyte membrane was evaluated as the voltage retention rate. In addition, there were measured the ion-exchange capacity, the hot water resistance, and the proton conductivity at 80°C and 25% RH of the obtained electrolyte membrane. The result is shown in Table 1.
- the electrolyte membrane was obtained in the same manner as in Example 1 except that DPPE was changed to tetrakis(triphenylphosphine)platinum(0) complex. Since the obtained membrane was insoluble in NMP, the molecular weight retention rate was not able to be measured, and thus the open circuit voltage holding time was measured as the durability test. However, the evaluation was not completed within 3,000 hours, and thus the chemical durability of the electrolyte membrane was evaluated as the voltage retention rate. In addition, there were measured the ion-exchange capacity, the hot water resistance, and the proton conductivity at 80°C and 25% RH of the obtained electrolyte membrane. The result is shown in Table 1.
- Example 1 20 g of the electrolyte membrane obtained in Example 1 was immersed for 72 hours in 30 L of an aqueous solution obtained by dissolving 21.7 mg (0.125 mmol) of manganese acetate in pure water to contain manganese acetate, and thus the polymer electrolyte membrane was obtained. Since the obtained membrane was insoluble in NMP, the molecular weight retention rate was not able to be measured, and thus the open circuit voltage holding time was measured as the durability test. However, the evaluation was not completed within 3,000 hours, and thus the chemical durability of the electrolyte membrane was evaluated as the voltage retention rate. In addition, there were measured the ion-exchange capacity, the hot water resistance, and the proton conductivity at 80°C and 25% RH of the obtained electrolyte membrane. The result is shown in Table 1.
- the electrolyte membrane was obtained in the same manner as in Example 1 except that 5-amino-1,10-phenanthroline was changed to 0.63 g of (2,2’-bipyridine)dichloroplatinum(II). Since the obtained membrane was insoluble in NMP, the molecular weight retention rate was not able to be measured, and thus the open circuit voltage holding time was measured as the durability test. However, the evaluation was not completed within 3,000 hours, and thus the chemical durability of the electrolyte membrane was evaluated as the voltage retention rate. In addition, there were measured the ion-exchange capacity, the hot water resistance, and the proton conductivity at 80°C and 25% RH of the obtained electrolyte membrane. The result is shown in Table 1.
- the electrolyte membrane was obtained in the same manner as in Example 1 except that 5-amino-1,10-phenanthroline was changed to 0.67 g of dichloro(1,10-phenanthroline)platinum(II). Since the obtained membrane was insoluble in NMP, the molecular weight retention rate was not able to be measured, and thus the open circuit voltage holding time was measured as the durability test. However, the evaluation was not completed within 3,000 hours, and thus the chemical durability of the electrolyte membrane was evaluated as the voltage retention rate. In addition, there were measured the ion-exchange capacity, the hot water resistance, and the proton conductivity at 80°C and 25% RH of the obtained electrolyte membrane. The result is shown in Table 1.
- Example 3 20 g of the electrolyte membrane obtained in Example 3 was immersed for 72 hours in 30 L of an aqueous solution obtained by dissolving 32.7 mg (0.125 mmol) of ruthenium chloride trihydrate in pure water to contain ruthenium chloride, and thus the polymer electrolyte membrane was obtained. Since the obtained membrane was insoluble in NMP, the molecular weight retention rate was not able to be measured, and thus the open circuit voltage holding time was measured as the durability test. However, the evaluation was not completed within 3,000 hours, and thus the chemical durability of the electrolyte membrane was evaluated as the voltage retention rate. In addition, there were measured the ion-exchange capacity, the hot water resistance, and the proton conductivity at 80°C and 25% RH of the obtained electrolyte membrane. The result is shown in Table 1.
- Example 2 20 g of the electrolyte membrane obtained in Example 2 was immersed for 72 hours in 30 L of an aqueous solution obtained by dissolving 36.4 mg (0.125 mmol) of cobalt nitrate hexahydrate in pure water to contain cobalt nitrate, and thus the polymer electrolyte membrane was obtained. Since the obtained membrane was insoluble in NMP, the molecular weight retention rate was not able to be measured, and thus the open circuit voltage holding time was measured as the durability test. However, the evaluation was not completed within 3,000 hours, and thus the chemical durability of the electrolyte membrane was evaluated as the voltage retention rate. In addition, there were measured the ion-exchange capacity, the hot water resistance, and the proton conductivity at 80°C and 25% RH of the obtained electrolyte membrane. The result is shown in Table 1.
- the electrolyte membrane was obtained in the same manner as in Example 1 except that the amount of DPPE was changed to 0.4 g, and 5-amino-1,10-phenanthroline was not used. Since the obtained membrane was insoluble in NMP, the molecular weight retention rate was not able to be measured, and thus the open circuit voltage holding time was measured as the durability test. In addition, there were measured the ion-exchange capacity, the hot water resistance, and the proton conductivity at 80°C and 25% RH of the obtained electrolyte membrane. The result is shown in Table 1.
- the electrolyte membrane was obtained in the same manner as in Example 1 except that the amount of 5-amino-1,10-phenanthroline was changed to 0.6 g, and DPPE was not used. Since the obtained membrane was insoluble in NMP, the molecular weight retention rate was not able to be measured, and thus the open circuit voltage holding time was measured as the durability test. In addition, there were measured the ion-exchange capacity, the hot water resistance, and the proton conductivity at 80°C and 25% RH of the obtained electrolyte membrane. The result is shown in Table 1.
- the electrolyte membrane was obtained in the same manner as in Example 1 except that the amount of DPPE was changed to 0.8 g, and 5-amino-1,10-phenanthroline was not used. Since the obtained membrane was insoluble in NMP, the molecular weight retention rate was not able to be measured, and thus the open circuit voltage holding time was measured as the durability test. In addition, there were measured the ion-exchange capacity, the hot water resistance, and the proton conductivity at 80°C and 25% RH of the obtained electrolyte membrane. The result is shown in Table 1.
- the electrolyte membrane was obtained in the same manner as in Example 1 except that the amount of 5-amino-1,10-phenanthroline was changed to 1.2 g, and DPPE was not used. Since the obtained membrane was insoluble in NMP, the molecular weight retention rate was not able to be measured, and thus the open circuit voltage holding time was measured as the durability test. In addition, there were measured the ion-exchange capacity, the hot water resistance, and the proton conductivity at 80°C and 25% RH of the obtained electrolyte membrane. The result is shown in Table 1.
- the electrolyte membrane was obtained in the same manner as in Example 1 except that DPPE and 5-amino-1,10-phenanthroline were not used. Since the obtained membrane was insoluble in NMP, the molecular weight retention rate was not able to be measured, and thus the open circuit voltage holding time was measured as the durability test. In addition, there were measured the ion-exchange capacity and the proton conductivity at 80°C and 25% RH of the obtained electrolyte membrane. The result is shown in Table 1.
- the electrolyte membrane was obtained in the same manner as in Example 14 except that DPPE and 5-amino-1,10-phenanthroline were not used. Since the obtained membrane was insoluble in NMP, the molecular weight retention rate was not able to be measured, and thus the open circuit voltage holding time was measured as the durability test. In addition, there were measured the ion-exchange capacity and the proton conductivity at 80°C and 25% RH of the obtained electrolyte membrane. The result is shown in Table 1.
- the electrolyte membrane was obtained in the same manner as in Example 15 except that DPPE and 5-amino-1,10-phenanthroline were not used. Since the obtained membrane was soluble in NMP, the molecular weight retention rate was measured as the durability test. In addition, there were measured the ion-exchange capacity and the proton conductivity at 80°C and 25% RH of the obtained electrolyte membrane. The result is shown in Table 1.
- the electrolyte membrane was obtained in the same manner as in Example 16 except that 5-amino-1,10-phenanthroline was not used. Since the obtained membrane was soluble in NMP, the molecular weight retention rate was measured as the durability test. In addition, there were measured the ion-exchange capacity, the hot water resistance, and the proton conductivity at 80°C and 25% RH of the obtained electrolyte membrane. The result is shown in Table 1.
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Abstract
Description
Patent Literature 2: Japanese Patent Laid-Open No. 2000-11756
Patent Literature 3: Japanese Patent Laid-Open No. 2003-201403
Patent Literature 4: Japanese Patent Laid-Open No. 2007-66882
Patent Literature 5: Japanese Patent Laid-Open No. 2005-213325
Patent Literature 6: Japanese Patent Laid-Open No. 2006-99999
Patent Literature 7: WO 2013/94538 A
Patent Literature 8: Japanese Patent Laid-Open No. 2007-38213
Patent Literature 9: WO 2011/57768 A
Patent Literature 10: WO 2011/57769 A
1. A function-separated mechanism in which, while the phosphorus-containing additive represented by the general formula (B1) or (B2) exhibits high functions as “peroxide decomposer” or “radical scavenger” that scavenges, decomposes, and detoxifies hydroxy radical, peroxide radical and hydrogen peroxide having strong oxidizing power, the nitrogen-containing aromatic additive represented by the general formula (C1) or (C2) is strongly coordinated to a very small amount of metal which exists in the system to promote production of hydroxy radical and peroxide radicals and inactivats the metal to function as a “metal inactivator”. Alternatively, a function-separated mechanism in which, the phosphorus-containing additive functions as “metal inactivator”, and the nitrogen-containing aromatic additive functions as “peroxide decomposer” or “radical scavenger”.
2. While the oxide of a nitrogen-containing aromatic compound represented by the general formula (C1) or (C2) produced by detoxifying hydrogen peroxide or hydroxy radical is reduced by the phosphorus-containing additive represented by the general formula (B1) or (B2) to return to the original nitrogen-containing aromatic compound, the oxide of the phosphorus-containing additive inferior in elution resistance is reduced by hydrogen generated during operation of fuel cell to return to the original phosphorus-containing additive. A mechanism of suppressing elution of the additive oxide inferior in elution resistance and hot water resistance, whereby, and cyclically improving the decomposition efficiency of hydrogen peroxide, hydroxy radical and peroxide radical.
(1) An electrolyte membrane is proton-substituted, and fully rinsed with pure water. After wiping off the water on the surface of the electrolyte membrane, the membrane is vacuum-dried at 100°C for 12 hours or more, and the dry weight is obtained.
(2) 50 mL of an aqueous solution of 5% by weight of sodium sulfate is added to the electrolyte, and the resultant solution is allowed to stand for 12 hours for conducting ion-exchange.
(3) The generated sulfuric acid is titrated using an aqueous solution of 0.01 mol/L sodium hydroxide. A commercially available 0.1 w/v% phenolphthalein solution for titration is added as the indicator. A point where the color turns light purplish red is defined as the end point.
(4) The ion-exchange capacity is obtained from the following formula.
Ion-exchange capacity (meq/g) = [Concentration of aqueous solution of sodium hydroxide (mmol/mL) x Titrated amount (mL)]/Dry weight of sample (g)
(1) A method of dissolving or dispersing the phosphorus-containing additive (B) and the nitrogen-containing aromatic additive (C) in a solution or dispersion of the ionic group-containing polymer (A), and then forming a membrane by using the resultant solution to thereby prepare the polymer electrolyte membrane.
(2) A method of applying the liquid of dissolved phosphorus-containing additive (B) and/or the nitrogen-containing aromatic additive (C) on the polymer electrolyte membrane composed of the ionic group-containing polymer (A).
(3) A method of immersing the polymer electrolyte membrane composed of the ionic group-containing polymer (A) into the liquid of dissolved phosphorus-containing additive (B) and/or the nitrogen-containing aromatic additive (C).
The ion-exchange capacity was measured by neutralization titration described in the following (i) to (iv). The measurements were performed three times, and then the average of them was taken.
(i) An electrolyte membrane was proton-substituted, and fully rinsed with pure water. After wiping off the water on the surface of the electrolyte membrane, the membrane was vacuum-dried at 100°C for 12 hours or more, and the dry weight was obtained.
(ii) 50 mL of an aqueous solution of 5% by weight of sodium sulfate was added to the electrolyte, and the resultant solution was allowed to stand for 12 hours for conducting ion-exchange.
(iii) The generated sulfuric acid was titrated using an aqueous solution of 0.01 mol/L sodium hydroxide. A commercially available 0.1 w/v% phenolphthalein solution for titration was added as the indicator. A point where the color turned light purplish red was defined as the end point.
(iv) The ion-exchange capacity was obtained by the following formula.
Ion-exchange capacity (meq/g) = [Concentration of aqueous solution of sodium hydroxide (mmol/mL) x Titrated amount (mL)]/[Dry weight of sample (g)]
The membrane-shaped sample was immersed for 24 hours in pure water at 25°C. Then the sample was held in a thermo-hygrostat at 80°C and at a relative humidity of 25 to 95% for each 30 minutes at individual steps. After that, the proton conductivity was measured by the controlled potential AC impedance method. The measurement apparatus used was an electrochemical measurement system of Solartron Inc. (Solartron 1287 Electrochemical Interface and Solartron 1255B Frequency Response Analyzer). The controlled potential impedance measurement was performed by the 2-probe method and the proton conductivity was obtained. The AC amplitude was 50 mV. The sample used was a membrane of 10 mm in width and 50 mm in length. The measurement jig was fabricated by a phenol resin, and the measurement portion was opened. The electrode used was platinum plates (2 plates each having a thickness of 100 mm). The electrodes were arranged so as the distance therebetween to become 10 mm and so as to be in parallel each other and be orthogonal to the longitudinal direction of the sample membrane, on the front and rear side of the sample membrane.
The number-average molecular weight and the weight-average molecular weight of polymer were measured by GPC. As the integrated analyzer of an ultraviolet ray detector and a differential diffractometer, HLC-8022GPC manufactured by TOSOH Corporation was applied. As the GPC column, two columns of TSK gel Super HM-H (6.0 mm in inner diameter, 15 cm in length) manufactured by TOSOH Corporation were used. The measurement was done using an N-methyl-2-pyrrolidone solvent (an N-methyl-2-pyrrolidone solvent containing 10 mmol/L of lithium bromide) under a condition of 0.1% by weight of sample concentration, 0.2 mL/min of flow rate, at 40°C. The number-average molecular weight and the weight-average molecular weight were obtained in terms of standard polystyrene.
The measurement of membrane thickness was performed by ID-C112 manufactured by Mitsutoyo Co. mounted on a granite comparator stand BSG-20 manufactured by Mitsutoyo Co.
Quantitative analysis was performed by Gas chromatography (GC) under the following conditions.
Column: DB-5 (manufactured by J&W Inc.) L = 30 m, j = 0.53 mm, D = 1.50 mm
Carrier: Helium (Line velocity = 35.0 cm/sec)
Analytical conditions
Inj. temp.; 300°C
Detect. temp.; 320°C
Oven; 50°C x 1 min
Rate; 10°C/min
Final; 300°C x 15 min
SP ratio; 50 : 1
The added quantity of the additive in the electrolyte membrane was evaluated by Inductively Coupled Plasma (ICP) Emission spectrophotometric analysis. An electrolyte membrane was cut to a size of 5 cm x 5 cm, and the cut sample was dried at 110°C under reduced pressure for 2 hours. Then the dried sample was weighed precisely and was allowed to stand at 550°C for 2 days. The residual ash was dissolved in an aqueous solution of 0.1 N nitric acid to completely extract the additive. Thus treated liquid was analyzed by the ICP Emission spectrophotometry to determine the quantity of phosphorus, nitrogen and various metal elements, thereby the quantification of the additive was executed.
The hot water resistance of the additive was evaluated by determining the residual rate after immersion in 95°C hot water. The electrolyte membrane was cut to two rectangular pieces of each about 5 cm in length and about 10 cm in width. The cut sample was immersed in 95°C hot water for 8 hours to elute the additive. The electrolyte membrane before and after the immersion in hot water was cut to a size of 5 cm x 5 cm, respectively. Each of the cut samples was analyzed by the ICP Emission spectrophotometry to determine the content of the additive, and the hot water resistance was evaluated as the residual rate of the additive.
The 1H-NMR measurement was performed under the following conditions, to confirm the structure and to quantify the molar composition ratio of the segment (A1) containing an ionic group to the segment (A2) not containing an ionic group. The molar composition ratio was calculated from the integral peak values appearing at 8.2 ppm (originated from disulfonate-4,4’-difluorobenzophenone) and 6.5 to 8.0 ppm (originated from all aromatic protons except for disulfonate-4,4’-difluorobenzophenone).
Apparatus: EX-270 manufactured by JOEL Ltd.
Resonance frequency: 270 MHz (1H-NMR)
Measurement temperature: Room temperature
Dissolving solvent: DMSO-d6
Internal reference substance: TMS (0 ppm)
Cumulative number: 16 times
(A) Molecular weight retention rate
As to an electrolyte membrane soluble in N-methylpyrrolidone (NMP), the electrolyte membrane was deteriorated by the following method, and the chemical stability was evaluated by making a comparison of the molecular weight between before and after the degradation test.
As to an electrolyte membrane insoluble in NMP, the electrolyte membrane was deteriorated by the following method, and the chemical stability was evaluated by comparing the holding time of the open circuit voltage.
When even the above (B) evaluation of open circuit voltage holding time made it possible to maintain 0.7 V or larger voltage for 3,000 hours or longer period, the evaluation was stopped, and the chemical durability was evaluated as the voltage retention rate by making a comparison between the initial voltage and the voltage after 3,000 hours.
(Synthesis of 2,2-bis(4-hydroxyphenyl)-1,3-dioxolane (K-DHBP) represented by the following general formula (G1))
To a 1000 mL three neck flask equipped with an agitator, a nitrogen gas inlet tube, and a Dean-Stark trap, there were added 16.59 g of potassium carbonate (Aldrich reagent, 120 mmol), 25.8 g of K-DHBP (100 mmol), and 20.3 g of 4,4’-difluorobenzophenone (Aldrich reagent, 93 mmol). After nitrogen purge, the resultant content was dewatered in 300 mL of N-methylpyrrolidone (NMP) and 100 mL of toluene at 160°C. Then, the resultant content was heated to remove the toluene, and was polymerized at 180°C for 1 hour. Purification was performed by reprecipitation through the use of a large quantity of methanol, and thus there was obtained the oligomer not containing an ionic group (terminal OM group; meanwhile, the symbol M in the OM group signifies Na or K, and the subsequent expression follows this example). The number-average molecular weight was 10,000.
To a 1000 mL three neck flask equipped with an agitator, a nitrogen gas inlet tube, and a Dean-Stark trap, there were added 27.6 g of potassium carbonate (Aldrich reagent, 200 mmol), 12.9 g (50 mmol)of the K-DHBP, 9.3 g of 4,4’-biphenol (Aldrich reagent, 50 mmol), 40.6 g (96 mmol) of disodium 3,3’-disulfonate-4,4’-difluorobenzophenone, and 17.9 g of 18-crown-6-ether (82 mmol, Wako Pure Chemical Industries, Ltd.). After nitrogen purge, the resultant content was dewatered in 300 mL of N-methylpyrrolidone (NMP) and 100 mL of toluene at 170°C. Then, the resultant content was heated to remove the toluene, and was polymerized at 180°C for 1 hour. Purification was performed by reprecipitation through the use of a large quantity of isopropyl alcohol, and thus there was obtained the oligomer containing an ionic group (terminal OM group), represented by the formula (G4). The number-average molecular weight was 29,000.
To a 500 mL three neck flask equipped with an agitator, a nitrogen gas inlet tube, and a Dean-Stark trap, there were added 0.56 g of potassium carbonate (Aldrich reagent, 4 mmol), and 29 g (1 mmol) of the oligomer a2 containing an ionic group (terminal OM group). After nitrogen purge, the resultant content was dewatered at 100°C in 100 mL of N-methylpyrrolidone (NMP) and 30 mL of cyclohexane, and then the resultant content was heated to remove the cyclohexane. Furthermore, the addition of 11 g (1 mmol) of oligomer a1’ not containing an ionic group (terminal fluoro group) causes the solution to react at 105°C for 24 hours. Purification was performed by reprecipitation through the use of a large quantity of isopropyl alcohol, and thus there was obtained the block copolymer b1. The weight-average molecular weight was 400,000.
(Synthesis of polyethersulfone (PES)-based block copolymer precursor b2’, structured by the segment represented by the following formula (G6) and the segment represented by the following formula (G7))
1.78 g of anhydride nickel chloride were stirred in 15 mL of dimethylsulfoxide at 70°C. 2.37 g of 2,2’-bipyridyl was added to the mixture, and the resultant mixture was then agitated at the same temperature for 10 minutes to prepare a nickel-containing solution.
0.25 g of the block copolymer precursor b2’ was added to a mixed solution of 0.18 g of lithium bromide monohydrate and 8 mL of N-methyl-2-pyrrolidone, and the mixture was caused to react at 120°C for 24 hours. The reaction mixture was poured into 80 mL of 6 mol/L of hydrochloric acid for agitation for 1 hour. The deposited solid was separated by filtration. The separated solid was dried, and a gray-white block copolymer b2 structured by the segment represented by the formula (G7) and the segment represented by the following formula (G8) was obtained.
(Synthesis of hydrophobic oligomer represented by the following formula (G9))
2.5 g (6.28 mmol) of DPPE and 680 mg (1.57 mmol) of cerium nitrate hexahydrate were added to a 100 mL recovery flask. 50 mL of ethanol was poured into the mixture, and the mixture was agitated at 25°C for 24 hours. The white suspension was concentrated in a rotary evaporator, and the solvent was removed. Thus obtained white solid was used as is as the additive, without purification.
The electrolyte membrane was obtained in the same manner as in Example 1 except that DPPE was changed to the DPPE-Ce described above. Since the obtained membrane was insoluble in NMP, the molecular weight retention rate was not able to be measured, and thus the open circuit voltage holding time was measured as the durability test. However, the evaluation was not completed within 3,000 hours, and thus the chemical durability of the electrolyte membrane was evaluated as the voltage retention rate. In addition, there were measured the ion-exchange capacity, the hot water resistance, and the proton conductivity at 80°C and 25% RH of the obtained electrolyte membrane. The result is shown in Table 1.
Claims (15)
- A polymer electrolyte composition comprising an ionic group-containing polymer (A), a phosphorus-containing additive (B), and a nitrogen-containing aromatic additive (C), the phosphorus-containing additive (B) being at least one kind selected from a compound represented by the following general formula (B1) and a compound represented by the following general formula (B2), and the nitrogen-containing aromatic additive (C) being at least one kind selected from a compound represented by the following general formula (C1) and a compound represented by the following general formula (C2):
- The polymer electrolyte composition according to Claim 1, wherein the phosphorus-containing additive (B) is at least one kind selected from bis(diphenylphosphino)methane, bis(diphenylphosphino)ethane, bis(diphenylphosphino)propane, bis(diphenylphosphino)butane, bis(diphenylphosphino)pentane, bis(diphenylphosphino)hexane, bis(diphenylphosphino)pentane, bis(diphenylphosphino)octane, bis(diphenylphosphino)nonane, bis(diphenylphosphino)decane, bis[bis(pentafluorophenyl)phosphino]ethane, bis(diphenylphosphino)ethylene, bis(diphenylphosphino)acetylene, bis[(phenylpropane sulfonic acid)phosphine]butane and salts thereof, ((diphenylphosphino)phenyl)diphenylphosphine, bis(dimethylphosphino)methane, bis(dimethylphosphino)ethane, bis(diethylphosphino)ethane, bis(dicyclohexylphosphino)methane, bis(dicyclohexylphosphino)ethane, bis(dicyclohexylphosphino)propane, bis(dicyclohexylphosphino)butane, bis(diphenylphosphino)benzene, bis(diphenylphosphinophenyl)ether, bis(diphenylphosphino)benzophenone, BINAP, bis(diphenylphosphinomethyl)benzene, bis(dicyclohexylphosphinophenyl)ether, bis(dicyclohexylphosphino)benzophenone, phenylenebiphosphine, and tetraphenylbiphosphine.
- The polymer electrolyte composition according to Claim 1 or Claim 2, wherein the nitrogen-containing aromatic additive (C) is a compound in which at least one of R8 to R15 in the general formula (C1) is an amino group, or a compound in which at least one of R16 to R23 in the general formula (C2) is an amino group.
- The polymer electrolyte composition according to any of Claim 1 to Claim 4, wherein the total content of the phosphorus-containing additive (B) and the nitrogen-containing aromatic additive (C) is 0.01% by weight or larger and 15% by weight or smaller relative to the entire polymer electrolyte composition.
- The polymer electrolyte composition according to any of Claim 1 to Claim 5, further comprising at least one transition metal selected from the group consisting of Ce, Mn, Ti, Zr, V, Cr, Mo, W, Ru, Co, Rh, Ir, Ni, Pd, Pt, Ag, and Au.
- The polymer electrolyte composition according to any of Claim 1 to Claim 6, wherein the ionic group-containing polymer (A) is a hydrocarbon-based polymer having an aromatic ring in the main chain.
- The polymer electrolyte composition according to Claim 7, wherein the ionic group-containing polymer (A) is an aromatic polyetherketone-based polymer.
- The polymer electrolyte composition according to any of Claim 1 to Claim 8, wherein the ionic group-containing polymer (A) is a block polymer containing a segment (A1) containing an ionic group and a segment (A2) not containing an ionic group.
- The polymer electrolyte composition according to Claim 9, wherein the segment (A1) containing an ionic group contains a constituent unit represented by the following general formula (S1) and the segment (A2) not containing an ionic group contains a constituent unit represented by the following general formula (S2):
- The polymer electrolyte composition according to any of Claim 1 to Claim 10, wherein an ionic group of the ionic group-containing polymer (A) is a sulfonic acid group.
- A polymer electrolyte membrane, which is composed of the polymer electrolyte composition according to any of Claim 1 to Claim 11.
- A polymer electrolyte membrane with catalyst layer, which is composed of the polymer electrolyte composition according to any of Claim 1 to Claim 11.
- A membrane electrode assembly, which is composed of the polymer electrolyte composition according to any of Claim 1 to Claim 11.
- A polymer electrolyte fuel cell, which is composed of the polymer electrolyte composition according to any of Claim 1 to Claim 11.
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CN112436168A (en) * | 2020-11-30 | 2021-03-02 | 山东东岳未来氢能材料股份有限公司 | Long-life enhanced perfluorinated proton membrane and preparation method thereof |
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