WO2022030552A1 - Catalyseur d'électrode pour piles à combustible et pile à combustible - Google Patents

Catalyseur d'électrode pour piles à combustible et pile à combustible Download PDF

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WO2022030552A1
WO2022030552A1 PCT/JP2021/028967 JP2021028967W WO2022030552A1 WO 2022030552 A1 WO2022030552 A1 WO 2022030552A1 JP 2021028967 W JP2021028967 W JP 2021028967W WO 2022030552 A1 WO2022030552 A1 WO 2022030552A1
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fuel cell
catalyst
nitrogen
platinum
doped graphene
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PCT/JP2021/028967
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English (en)
Japanese (ja)
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聖志 金村
裕一 棟方
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東京都公立大学法人
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Priority to JP2022541592A priority Critical patent/JP7508139B2/ja
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/92—Metals of platinum group
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/96—Carbon-based electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Definitions

  • the present invention relates to an electrode catalyst for a fuel cell and a fuel cell using the same.
  • the operating temperature of fuel cells used for homes and automobiles is limited to about 80 ° C from room temperature.
  • the power generation efficiency is improved and the allowable range of the CO concentration in the fuel gas is also increased.
  • the catalyst for a fuel cell a catalyst in which fine particles of platinum or a platinum alloy are supported on carbon particles is generally used.
  • Such a fuel cell catalyst deteriorates faster as the temperature rises, and the catalytic activity is greatly reduced. Therefore, a fuel cell that operates at a high temperature of 100 ° C. or higher has not yet been put into practical use.
  • a decrease in catalytic activity with an increase in temperature in a fuel cell catalyst is a problem common to both the oxygen electrode and the fuel electrode.
  • the above-mentioned problem is caused by deterioration due to dissolution of fine particles of platinum and platinum alloy.
  • the dissolved platinum is deposited again.
  • the reprecipitated platinum and platinum alloy fine particles have a reduced surface area and a reduced catalytic activity.
  • Even if the fuel cell is not operated at a high temperature it is necessary to use a certain amount of excess platinum for the electrode catalyst in order to maintain the specified fuel cell performance for a long period of time. Such excess platinum is a factor in increasing the price of fuel cells.
  • the oxygen electrode there is also a problem that the carbon particles themselves are oxidized and the characteristics as an electrode are deteriorated.
  • Patent Document 1 proposes to provide a cathode catalyst for a fuel cell having good characteristics without using platinum. Specifically, Patent Document 1 proposes to use nitrogen-doped mesoporous carbon produced by the hard template method as a cathode catalyst for a proton exchange membrane fuel cell or the like.
  • Patent Document 2 obtains graphene having a very high charge carrier mobility by a method having the following steps (a), step (b), step (c), step (d) and step (e).
  • Graphene membranes have been proposed.
  • Step (a) A step of preparing a substrate.
  • Step (b) A step of epitaxially growing a metal layer on the surface of the substrate.
  • Step (c) A step of increasing the thickness of the metal layer obtained in the step (b) by growing the metal on the epitaxially grown metal layer as needed.
  • Step (d) A step of peeling the metal layer obtained in the step (b) or the step (c) carried out as necessary from the substrate.
  • Step (e) A step of laminating graphene on at least a part of the surface of the metal layer obtained in the step (d) which was in contact with the substrate until it was peeled off in the step (d).
  • Patent Document 3 proposes an oxygen reduction catalyst made of a carbon material doped with pyridine-type nitrogen or to which a pyridine-type nitrogen-containing molecule is attached.
  • This oxygen reduction catalyst has a high carbon dioxide occlusion function and a high catalytic performance for an oxygen reduction reaction, and substitutes for platinum.
  • this oxygen reduction catalyst has a function as a carbon dioxide occlusion material.
  • This oxygen reduction catalyst has a carbon material and a pyridine-type nitrogen doped at the edge thereof or a pyridine-type nitrogen-containing molecule adsorbed on the carbon material, and the content of the pyridine-type nitrogen is 0.04 at% or more. It is 10.00 at% or less.
  • Patent Document 4 proposes a fuel cell including an anode, a cathode, a non-precious metal catalyst, and an electrolyte.
  • the non-precious metal catalyst is in contact with the cathode.
  • the electrolyte comprises a protonic ionic liquid in contact with the non-precious metal catalyst.
  • Fuel cells are required to operate stably at higher temperatures, improve energy conversion efficiency, and increase the allowable CO concentration of fuel gas.
  • the present invention has been made in view of the above circumstances, and uses an electrode catalyst for a fuel cell that realizes high oxygen reduction activity, CO resistance, and oxidation resistance while reducing the amount of noble metal such as platinum used, and the like.
  • the purpose is to provide a fuel cell that has been used.
  • An electrode catalyst for a fuel cell comprising a conductive carrier and at least one of a metal and a metal compound supported on the conductive carrier, and for a fuel cell operating at a temperature of 100 ° C. or higher.
  • the heterologous element-doped graphene is nitrogen-doped, and the amount of nitrogen doped is 4 atom% or more, preferably 4 atom% or more and 10 atom% or less, in terms of atomic ratio with respect to the carbon on the surface of the heterogeneous element-doped graphene.
  • the electrode catalyst for a fuel cell according to [2] which is more preferably 6 atom% or more and 10 atom% or less.
  • the carrying amount of at least one of the metal and the metal compound is 1% by mass to 40% by mass, and when the metal is platinum, it is preferably 1.5% by mass to 5% by mass.
  • [6] A fuel cell having the electrode catalyst for a fuel cell according to any one of [1] to [5] and operating at 100 ° C. or higher.
  • a fuel cell comprising the electrode catalyst for a fuel cell according to any one of [1] to [5] and capable of allowing a fuel gas having a CO concentration of 10 ppm or more.
  • the fuel cell according to [6] or [7] which comprises an ionic liquid as an electrolyte.
  • the ionic liquid is dema-TfO, which is an equimolar mixture of trifluromethanesulphonic acid and N, N-diethylmethylamine.
  • the electrolyte further contains phosphoric acid.
  • the electrode catalyst for a fuel cell of the present invention high oxygen reduction activity, CO resistance and oxidation resistance can be realized while reducing the amount of precious metals such as platinum used. Further, the fuel cell of the present invention has high oxygen reduction activity, CO resistance and oxidation resistance while reducing the amount of precious metals such as platinum used.
  • FIG. 6 is a transmission electron micrograph of the catalyst obtained in Example 1.
  • 6 is a transmission electron micrograph of the catalyst obtained in Example 1.
  • 6 is a transmission electron micrograph of the catalyst obtained in Example 1.
  • It is an electron micrograph of each element constituting the catalyst obtained in Example 1.
  • FIG. It is a graph which shows the particle size distribution of the catalyst obtained in Example 2.
  • 6 is a transmission electron micrograph of the catalyst obtained in Example 2.
  • 6 is a transmission electron micrograph of the catalyst obtained in Example 2.
  • Example 6 is a transmission electron micrograph of the catalyst obtained in Example 2. It is an electron micrograph of each element constituting the catalyst obtained in Example 2.
  • FIG. It is a graph which shows the particle size distribution of the catalyst obtained in Example 3.
  • FIG. 3 is a transmission electron micrograph of the catalyst obtained in Example 3.
  • 3 is a transmission electron micrograph of the catalyst obtained in Example 3.
  • 3 is an electron micrograph of each element constituting the catalyst obtained in Example 3.
  • Test Example 1 it is a graph which shows the oxygen reduction reaction activity of the platinum-supported nitrogen-doped graphene obtained in Example 1-1 in the protonic ionic liquid dema-TfO at 120 ° C.
  • Test Example 1 it is a graph which shows the oxygen reduction reaction activity of the platinum-supported nitrogen-doped graphene obtained in Example 1-2 in the protonic ionic liquid dema-TfO at 120 ° C.
  • Test Example 1 it is a graph which shows the oxygen reduction reaction activity of the platinum-supported nitrogen-doped graphene obtained in Example 1-3 in the protonic ionic liquid dema-TfO at 120 ° C.
  • Test Example 1 it is a graph which shows the oxygen reduction reaction activity of the platinum-supported nitrogen-doped graphene obtained in Example 1-4 in the protonic ionic liquid dema-TfO at 120 ° C.
  • Test Example 1 it is a graph which shows the oxygen reduction reaction activity of the platinum-supported carbon catalyst of the comparative product in the protonic ionic liquid dema-TfO at 120 degreeC. It is a graph which shows the comparison of the oxygen reduction current density per unit area for each nitrogen doping amount in platinum-supported nitrogen-doped graphene or a commercially available Pt / C catalyst. It is a chart which shows the catalytic activity of the catalyst of Example 1-4, and shows the activity per catalyst unit area. It is a chart which shows the catalytic activity of the catalyst of Example 1-4, and shows the catalytic activity per unit platinum mass.
  • 6 is a chart showing the oxygen reduction reaction activity of the Pd-NG catalyst (Example 2) in the protonated ionic liquid dema-TfO at 120 ° C. 6 is a chart showing the oxygen reduction reaction activity of the Fe-NG catalyst (Example 3) in the protonic ionic liquid dema-TfO at 120 ° C. It is a transmission electron micrograph of a Pt / C catalyst (comparative product) before the durability test. It is a transmission electron micrograph of a Pt / C catalyst (comparative product) after a durability test. It is a chart which shows the Raman spectroscopic measurement result of the Pt / C catalyst before and after the durability test.
  • Test Example 5 it is a graph which shows the oxygen reduction reaction activity of platinum-supported nitrogen-doped graphene in a dema-TfO / PA mixed electrolyte, and shows the case where dema-TfO: PA is 1: 2 in molar ratio.
  • Test Example 5 it is a graph which shows the oxygen reduction reaction activity of platinum-supported nitrogen-doped graphene in a dema-TfO / PA mixed electrolyte, and shows the case where dema-TfO: PA is 1: 1 in molar ratio.
  • Test Example 5 it is a graph which shows the oxygen reduction reaction activity of platinum-supported nitrogen-doped graphene in a dema-TfO / PA mixed electrolyte, and shows the case where dema-TfO: PA is 2: 1 in molar ratio.
  • the electrode catalyst for a fuel cell according to an embodiment of the present invention includes a conductive carrier and at least one of a metal and a metal compound supported on the conductive carrier. , Is provided.
  • the catalyst according to one embodiment of the present invention is for a fuel cell operating at a temperature of 100 ° C. or higher.
  • the catalyst according to the embodiment of the present invention will be described in more detail.
  • ⁇ Conductive carrier> As the conductive carrier used in the electrode catalyst for a fuel cell according to an embodiment of the present invention, at least one of graphene and a heterologous element-doped graphene can be preferably used.
  • the graphene commercially available graphene can be used without particular limitation.
  • the graphene for example, a single-phase graphene membrane, graphene oxide, reduced graphene oxide and the like can be used.
  • Graphene oxide can be preferably used for doping with different elements.
  • the above-mentioned dissimilar element-doped graphene is graphene that is doped with an element other than carbon (dissimilar element).
  • dissimilar element doped with graphene for example, nitrogen, oxygen, boron, phosphorus, sulfur and the like can be used. Among these dissimilar elements, nitrogen is particularly preferable.
  • the doping amount of the above-mentioned different elements is 2.5 atom% in atomic ratio with respect to the carbon amount existing on the graphene surface before doping (meaning that 2.5 atoms out of 100 atoms are substituted).
  • the above is preferable, 4 atom% or more is more preferable, and 6 atom% or more is most preferable.
  • the upper limit of the doping amount of the dissimilar element is preferably 10 atom%. If the doping amount of the dissimilar element is less than the above lower limit, the catalytic activity is insufficient. If the doping amount of the dissimilar element exceeds 10 atom%, the graphene structure may not be maintained.
  • the nitrogen atom and other doping elements exist in a state in which the carbon of graphene is substituted.
  • dissimilar element-doped graphene as the conductive carrier, but if the doping amount of the dissimilar element as a whole of the conductive carrier is within the above range, undoped graphene is contained. Is also good.
  • the amount of undoped graphene is preferably 5 wt% or less of the total amount of the conductive carrier.
  • the metal supported on the conductive carrier examples include platinum (Pt), palladium (Pd), iron (Fe), ruthenium (Ru), cobalt (Co), nickel (Ni), titanium (Ti), and the like.
  • Examples thereof include tungsten (W), molybdenum (Mo), ruthenium (Os), rhodium (Rh), iridium (Ir), chromium (Cr), manganese (Mn), and niobium (Nb).
  • the metal at least one selected from the group consisting of platinum, palladium and iron can be preferably used.
  • the metal compound is a compound containing at least one of the metals, and examples thereof include alloy compounds, oxides, nitrides, oxynitrides, carbides, phospholides, fluorides, porphyrin compounds, and phthalocyanine compounds. be able to.
  • the particle shape of the metal or metal compound supported on the conductive carrier is preferably hemispherical or spherical.
  • the average particle size of the metal or the metal compound supported on the conductive carrier is preferably 2 nm to 20 nm, more preferably 2 nm to 10 nm.
  • the method for measuring the average particle size will be described in the column of Examples.
  • the amount of the metal or the metal compound carried varies depending on the type of the metal or the metal compound, but is 1% by mass (wt%) to 40% by mass (wt%) in the catalyst according to one embodiment of the present invention finally obtained. It is preferably wt%). Further, for example, when the metal is platinum, it is more preferably 1.5 wt% to 5 wt%.
  • the supporting position of the metal or the metal compound is preferably in the vicinity of the dissimilar element in the dissimilar element-doped graphene (for example, in the case of nitrogen-doped graphene, the vicinity of the doped nitrogen element).
  • a heterologous element-doped graphene is obtained as a conductive carrier.
  • a dissimilar element-introducing agent such as urea
  • the graphene oxide in which the dissimilar element-introducing agent is introduced is dried.
  • the graphene oxide introduced with the dissimilar element introducing agent is heat-treated at 500 ° C. to 1000 ° C. for 0.5 hours to 5 hours to obtain dissimilar element-doped graphene.
  • the obtained heterologous element-doped graphene is dispersed in a solvent such as water to prepare a dispersion liquid of the heterogeneous element-doped graphene.
  • a metal introducing agent for introducing a metal or a metal compound is added to the dispersion liquid to sufficiently disperse the dispersion.
  • the dispersion is heated at 50 ° C. to 300 ° C. for 1 hour to 15 hours while maintaining the dispersed state of the metal introducing agent.
  • the catalyst according to the embodiment of the present invention can be obtained.
  • heat treatment can be performed as follows.
  • the dispersion liquid to which the metal introducing agent is added is dried to obtain a powder.
  • the powder is heat-treated in an inert gas at 500 ° C. to 1000 ° C. for 0.5 to 5 hours.
  • the catalyst according to one embodiment of the present invention can be used as a catalyst for electrodes of a fuel cell.
  • the catalyst according to one embodiment of the present invention is preferably for a fuel cell using an ionic liquid as an electrolyte. Further, the catalyst according to the embodiment of the present invention is preferably for a fuel cell operating at a temperature of 100 ° C. or higher. The fuel cell will be described later.
  • the catalyst according to the embodiment of the present invention can be used for any electrode as long as it is an electrode of a fuel cell.
  • the catalyst according to one embodiment of the present invention is particularly useful as a catalyst for a cathode electrode.
  • the catalyst according to one embodiment of the present invention can be used as follows.
  • the electrode catalyst for a fuel cell is dispersed in a dispersion medium such as water to prepare electrode ink.
  • the obtained electrode ink is applied to an electrode usually used for a fuel cell such as a glassy carbon electrode and dried.
  • the amount of the electrode catalyst for a fuel cell used is preferably 0.3 mgcm -2 or less, more preferably 0.1 mgcm- 2 or less, in terms of the amount of metal in the carried metal or metal compound in the entire catalyst used. preferable.
  • the catalyst according to the embodiment of the present invention is contained in a film formed by applying the electrode ink to the electrodes.
  • the electrode having the catalyst according to the embodiment of the present invention can be used in the same manner as the electrode of a normal fuel cell.
  • the catalyst according to the embodiment of the present invention can stably carry out the fuel cell catalytic reaction at 100 ° C. or higher. As a result, the energy conversion efficiency of the fuel cell and the allowable CO concentration of the fuel gas can be improved, and the amount of precious metals such as platinum used can be reduced. Further, since the catalyst according to the embodiment of the present invention is configured as described above, it is particularly useful when an ionic liquid is used as an electrolyte. Moreover, the catalyst according to the embodiment of the present invention can exhibit sufficiently high catalytic activity with a small metal content as described above. In addition, the catalyst according to the embodiment of the present invention has high durability and can maintain high catalytic activity even after long-term use.
  • the fuel cell according to the embodiment of the present invention includes the electrode catalyst for the fuel cell according to the above-described embodiment of the present invention.
  • the fuel cell according to the embodiment of the present invention can be configured in the same manner as a normal fuel cell except that the fuel cell according to the embodiment of the present invention is provided with the electrode having the catalyst according to the embodiment of the present invention as described above.
  • the fuel cell according to the embodiment of the present invention is preferably a fuel cell that operates at 100 ° C. or higher.
  • the fuel cell according to the embodiment of the present invention is a fuel cell configured to allow a fuel gas having a CO concentration of 10 ppm or more.
  • a phosphoric acid type fuel cell corresponds to a fuel cell that operates at such a high temperature and a high CO concentration.
  • the catalyst according to the embodiment of the present invention having the above-mentioned configuration, deterioration of the catalyst is suppressed even at the above-mentioned high temperature and high CO concentration, and a fuel cell that operates stably for a long period of time is obtained.
  • the meaning of "operating at a temperature of 100 ° C. or higher” means that it operates well even at a temperature of 100 ° C. or higher, and does not mean that it does not operate at a temperature of 100 ° C. or higher. That is, with the conventional catalyst, good catalytic activity could not be exhibited in a fuel cell having a temperature condition of 100 ° C.
  • the fuel cell exhibits sufficient catalytic activity even under the condition of less than 100 ° C. or the fuel gas condition of CO concentration of less than 10 ppm. Further, when the catalyst according to the embodiment of the present invention is used, the fuel cell exhibits good catalytic activity even under the condition of 100 ° C. or higher or the fuel gas condition of CO concentration of 10 ppm or higher.
  • the fuel cell according to the embodiment of the present invention is configured in the same manner as a normal fuel cell except that it has a cathode electrode using the electrode catalyst for the fuel cell according to the above-described embodiment of the present invention. Is possible.
  • dema-TfO obtained by mixing trifluorescent acid acid and N, N-diethylmethylamine in an equimolar mixture, pentafluoromethelphonic acid and N, N-dithethylmethylamine mixed with N, N-dithethylmethylamine, and the like.
  • Dema-HfO obtained by equimolar mixing of acid and N, N-diethylmethylamine, or dema-FSI, demophilis obtained by equimolar mixing of bis (fluorosulphonyl) amide and N, N-diethylmethylamine.
  • Dema-TFSI obtained by equimolar mixing of amide and N, N-diethylmethylamine
  • dema-BET obtained by equimolar mixing of bis (pentafluoroanthanesulfonyl) amide and N, N-diethylmethylamine, etc. ..
  • 1-ethyl-3-methylmidazole medium EMIm-MsO
  • 1-butyl-3-methylmidazolium methylfonate BMIm-MsO
  • 1-hexyl-3-methylimide BMIm-MsO
  • 1-hexyl-3-methylimide EMIm-Mso
  • EMIm-TfO 1-butyl-3-methylimidazolium trifluromethanesulfonate
  • BMIm-TfO 1-hexyl-3-methylimidazolium trifluromethanesulfonate
  • HMIm-TfO 1-ethyl-3-methylimidazolium pentafluromethanesulfonate
  • EMIm -PfO 1-butyl-3-methylmidazolium pentafluromethanesulfonate
  • BMIm-PfO 1-butyl-3-methylmidazolium pentafluromethanesulfonate
  • BMIm-PfO 1-
  • the mixing ratio of the aprotic ionic liquid and the phosphoric acid is preferably 10: 1 to 1:10, more preferably 5: 1 to 1: 5 in terms of molar ratio, 2: 1. It is particularly preferable that it is ⁇ 1: 2.
  • the fuel cell according to the embodiment of the present invention includes the catalyst according to the above-mentioned embodiment of the present invention, it has excellent cost performance, reduces the amount of precious metals such as platinum used, and has high catalytic activity. , Excellent durability.
  • the nitrogen doping amount of the obtained nitrogen-doped graphene was confirmed by X-ray photoelectron spectroscopy (XPS). As a result, it was confirmed that four types of nitrogen-doped graphene having a nitrogen-doped amount of 2.9 atom%, 4.0 atom%, 6.5 atom% and 7.0 atom% were obtained.
  • the obtained nitrogen-doped graphene is schematically shown in FIG. As shown in FIG. 1, in the nitrogen-doped graphene 1, graphene 2 is doped with nitrogen 10.
  • the equipment and measurement conditions for using the X-ray photoelectron spectroscopy (XPS) are as follows.
  • the composition of nitrogen-doped graphene was analyzed using an X-ray photoelectron spectroscopy analyzer Kratos AXIS-NOVA (trade name) manufactured by Shimadzu Corporation. At that time, the 1s binding energy of carbon was corrected to 284.6 eV. Detailed component analysis of the XPS spectrum was performed using the fitting software CASAXPS of Casa Software, and the elemental ratio of carbon: nitrogen: oxygen was confirmed.
  • Example 1 Synthesis of platinum-supported nitrogen-doped graphene in which platinum was supported on each nitrogen-doped graphene by the reduction method (platinum-supported amount 2.6 wt%)) Platinum was supported on each of the four types of nitrogen-doped graphene obtained in Production Example 1 (platinum loading amount 2.6 wt%). By ultrasonic stirring for 15 minutes, 10 mg of nitrogen-doped graphene was dispersed in 10 mL of ultrapure water to obtain a dispersion liquid.
  • Example 1-1 was Pt-NG with a nitrogen doping amount of 2.9 atom%, Pt-NG with a nitrogen doping amount of 4.0 atom% was Example 1-2, and Pt-NG with a nitrogen doping amount of 6.5 atom%. Is Example 1-3, and Pt-NG having a nitrogen doping amount of 7.0 atom% is referred to as Example 1-4.
  • FIG. 2A A graph showing the particle size distribution of platinum particles on Pt-NG is shown in FIG. 2A.
  • Transmission electron micrographs of Pt-NG are shown in FIGS. 2B-2E.
  • the transmission electron micrographs are enlarged and shown in order from FIG. 2B to FIG. 2E.
  • An electron micrograph of each element constituting Pt-NG is shown in FIG. 2F.
  • FIG. 2A it can be seen that platinum particles having a size of several nm (average particle diameter of 3.3 nm) are uniformly supported on the nitrogen-doped graphene.
  • the average particle size was determined as follows. The diameters of each of the 300 platinum particles confirmed by observation with a transmission electron microscope were measured, and the average value was calculated and used as the average particle diameter.
  • Example 2 (Palladium was supported on nitrogen-doped graphene by the reduction method (palladium-supported amount is 24.6 wt% assuming that the total amount of charged palladium was supported) Synthesis of palladium-supported nitrogen-doped graphene) Palladium was supported on nitrogen-doped graphene having a nitrogen-doped amount of 7.0 atom% obtained by the reduction method. By ultrasonic stirring for 15 minutes, 10 mg of nitrogen-doped graphene was dispersed in 10 mL of ultrapure water to obtain a dispersion liquid.
  • Example 2 the state of carrying palladium particles on nitrogen-doped graphene was observed using a transmission electron microscope (manufactured by JEOL Ltd., trade name “JEM-ARM200F”) in the same manner as in Example 1.
  • a graph showing the particle size distribution of palladium particles on Pd-NG is shown in FIG. 3A.
  • Transmission electron micrographs of Pd-NG are shown in FIGS. 3B-3D.
  • An electron micrograph of each element constituting Pd-NG is shown in FIG. 3E.
  • FIG. 3A it can be seen that palladium particles having a size of several nm (average particle diameter of 3.6 nm) are uniformly supported on the nitrogen-doped graphene.
  • Example 3 Iron was supported on nitrogen-doped graphene by the reduction method (the amount of iron supported is 36.5 wt% assuming that the total amount of iron charged was supported).
  • Iron was supported on nitrogen-doped graphene having a nitrogen-doped amount of 7.0 atom% obtained by the reduction method.
  • 50 mg of nitrogen-doped graphene was dispersed in 15 mL of ultrapure water to obtain a dispersion liquid.
  • 100 mg of iron (II) acetate manufactured by Sigma-Aldrich
  • Example 2 With respect to the obtained Fe-NG, the state of carrying iron particles on nitrogen-doped graphene was observed using a transmission electron microscope (manufactured by JEOL Ltd., trade name “JEM-ARM200F”) in the same manner as in Example 1.
  • a graph showing the particle size distribution of iron particles on Fe-NG is shown in FIG. 4A.
  • the transmission electron micrographs of Fe-NG are shown in FIGS. 4B to 4D.
  • An electron micrograph of each element constituting Fe-NG is shown in FIG. 4E.
  • FIG. 4A it can be seen that iron particles having a size of several nm (average particle diameter of 15 nm) are uniformly supported on the nitrogen-doped graphene.
  • dema-TfO was sufficiently bubbled with nitrogen or oxygen gas in advance so as to be under a nitrogen atmosphere or oxygen saturated dissolution.
  • the catalysts are supported by the catalysts obtained in Examples 1 to 3 in 1 mL of a mixed solution containing ultrapure water and a Nafion dispersion (commercially available, manufactured by Sigma Aldrich) at a ratio of 9: 1 (mass ratio). 1 mg was added and ultrasonic dispersion was performed for 20 minutes to obtain electrode ink. 10 ⁇ L of this electrode ink was dropped onto a glassy carbon electrode and dried to obtain a working electrode (electrode) for testing. A fuel cell for testing was manufactured using the obtained electrodes and electrolyte. Further, an electrode ink was obtained in the same manner as described above except that a commercially available platinum-supported carbon catalyst (Pt / C, Pt-supported amount of 37.5 wt%) was used. This electrode ink was dropped onto a glassy carbon electrode and dried to obtain an electrode as a comparative product. Using this electrode (comparative product), a fuel cell was manufactured in the same manner as described above.
  • the electrode potential was swept within the specified range, and the catalytic activity was evaluated from the current value obtained at that time. Further, in order to reduce the influence of the diffusion of the reaction species and evaluate the catalytic activity in detail, the glassy carbon electrode on which each catalyst was deposited was rotated at a speed of 1600 rpm, and an electrochemical test was conducted. In these tests, the sweep rate of the electrode potential was set to 5 mVs -1 . In addition, the deterioration durability test of each catalyst was carried out by the method specified by the Fuel Cell Practical Use Promotion Council (JFCC). The potential sweep speed is 0.5 Vs -1 , and the potential sweep range is 1.0 V vs. RHE ⁇ 1.5V vs.
  • JFCC Fuel Cell Practical Use Promotion Council
  • the starting potential of the oxygen reduction reaction of the platinum-supported nitrogen-doped graphene of Examples 1-1 to 1-4 is noble as compared with the commercially available Pt / C catalyst (Pt-supported amount of 37.5 wt%). Further, the platinum-supported nitrogen-doped graphene of Examples 1-1 to 1-4 has an excellent oxygen reduction catalytic ability as compared with a commercially available Pt / C catalyst.
  • FIG. 6 shows a comparison of the oxygen reduction current densities per unit area for each nitrogen-doped amount in platinum-supported nitrogen-doped graphene or a commercially available Pt / C catalyst.
  • an increase in the oxygen reduction current density per unit area was observed as the nitrogen doping amount increased. This result suggests that the catalytically active sites increase with the increase in the amount of nitrogen doping.
  • the oxygen reduction current density of each platinum-supported nitrogen-doped graphene is higher than that of a commercially available Pt / C catalyst. Even after the durability test, the oxygen reduction current density of each platinum-supported nitrogen-doped graphene is higher than that of a commercially available Pt / C catalyst.
  • the oxygen reduction current was greatly reduced after the durability test.
  • the current value in RHE decreased from 1.18 mAcm -2 to about half 0.52 mA cm -2 .
  • FIG. 7 shows the catalytic activity of the Pt-NG catalyst (Example 1-4) having a nitrogen doping amount of 7.0 atom% in each of the electrolytic solutions obtained in Production Example 4.
  • FIG. 7A is a chart showing the catalytic activity of the catalyst of Example 1-4, showing the activity per catalyst unit area.
  • FIG. 7B is a chart showing the catalytic activity of the catalyst of Example 1-4, showing the catalytic activity per unit platinum mass. From the results shown in FIGS. 7A and 7B, the amount of Pt supported by the Pt-NG catalyst was determined by inductively coupled plasma (ICP) emission spectroscopic analysis, and the value was 2.6 wt%.
  • ICP inductively coupled plasma
  • the catalytic activity of the Pt-NG catalyst per unit amount is superior to that of the Pt / C catalyst.
  • the high catalytic activity per platinum mass means that the amount of platinum used in the fuel cell can be reduced, which clearly shows the superiority of the Pt-NG catalyst.
  • the electrolytic solution is replaced with the protonic ionic liquid dema-TfO from the sulfuric acid aqueous solution, the catalytic activity tends to decrease in the conventional Pt / C catalyst, but on the contrary, the catalytic activity tends to increase in the Pt-NG catalyst.
  • rice field This indicates that the Pt-NG catalyst is more suitable as the electrode catalyst for a fuel cell that operates in a high temperature range of 100 ° C. or higher.
  • FIGS. 11A to 11I Transmission electron micrographs of the catalysts obtained in Examples 1-4, 2-4 and 3-4 using nitrogen-doped graphene as a carrier after the durability test are shown in FIGS. 11A to 11I. .. From the results shown in FIGS. 11A to 11I, it can be seen that the structures shown in FIGS. 2B to 2F and 4B to 4E before the durability test are almost maintained. In addition, the state of nitrogen-doped graphene, which is a carrier, was investigated from Raman spectroscopy. The results are shown in FIGS. 12A and 12B. As is clear from the results shown in FIGS. 12A and 12B, there was almost no structural change in the carrier nitrogen-doped graphene before and after the durability test.
  • the oxygen reduction reaction activity of the platinum-supported nitrogen-doped graphene of Example 1-4 was evaluated in the prepared dema-TfO / PA mixed electrolyte.
  • the molar ratio of dema-TfO: PA is 1: 2
  • the oxygen reduction reaction activity of platinum-supported nitrogen-doped graphene in the dema-TfO / PA mixed electrolyte is shown in FIG. 13A.
  • the oxygen reduction reaction activity of platinum-supported nitrogen-doped graphene in the dema-TfO / PA mixed electrolyte is shown in FIG. 13B.
  • the oxygen reduction reaction activity of platinum-supported nitrogen-doped graphene in the dema-TfO / PA mixed electrolyte is shown in FIG. 13C.

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Abstract

Catalyseur d'électrode pour piles à combustible, ledit catalyseur d'électrode comprenant un support conducteur et un métal et/ou un composé métallique, qui est porté par le support conducteur. Ce catalyseur d'électrode pour piles à combustible est utilisé pour une pile à combustible qui fonctionne à une température de 100 °C ou plus. Le support conducteur du catalyseur d'électrode pour piles à combustible est composé d'un graphène et/ou d'un graphène dopé par un élément différent. Le graphène du catalyseur d'électrode pour piles à combustible est dopé par un élément différent, ledit graphène est dopé par de l'azote; la quantité d'azote dopé étant de 4 % atomique ou plus en termes de rapport atomique par rapport au carbone dans la surface du graphène dopé par un élément différent.
PCT/JP2021/028967 2020-08-05 2021-08-04 Catalyseur d'électrode pour piles à combustible et pile à combustible WO2022030552A1 (fr)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011065876A (ja) * 2009-09-17 2011-03-31 Dainippon Printing Co Ltd エッジシール付き触媒層−電解質膜積層体、エッジシール付き膜−電極接合体、及び固体高分子形燃料電池
JP2014188496A (ja) * 2013-03-28 2014-10-06 Panasonic Corp 触媒
JP2016131098A (ja) * 2015-01-14 2016-07-21 Tdk株式会社 電極、およびそれを用いた電気化学デバイス
JP2018538134A (ja) * 2016-02-02 2018-12-27 エルジー・ケム・リミテッド 担体−ナノ粒子複合体、これを含む触媒およびその製造方法
JP2019079796A (ja) * 2017-10-20 2019-05-23 コミッサリア ア レネルジー アトミーク エ オ ゼネルジ ザルタナテイヴ Ｐｅｍｆｃの拡散層としてカーボンナノチューブのマットを組み込んだ多層構造

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011065876A (ja) * 2009-09-17 2011-03-31 Dainippon Printing Co Ltd エッジシール付き触媒層−電解質膜積層体、エッジシール付き膜−電極接合体、及び固体高分子形燃料電池
JP2014188496A (ja) * 2013-03-28 2014-10-06 Panasonic Corp 触媒
JP2016131098A (ja) * 2015-01-14 2016-07-21 Tdk株式会社 電極、およびそれを用いた電気化学デバイス
JP2018538134A (ja) * 2016-02-02 2018-12-27 エルジー・ケム・リミテッド 担体−ナノ粒子複合体、これを含む触媒およびその製造方法
JP2019079796A (ja) * 2017-10-20 2019-05-23 コミッサリア ア レネルジー アトミーク エ オ ゼネルジ ザルタナテイヴ Ｐｅｍｆｃの拡散層としてカーボンナノチューブのマットを組み込んだ多層構造

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