WO2015098181A1 - 燃料電池用電極触媒の製造方法 - Google Patents
燃料電池用電極触媒の製造方法 Download PDFInfo
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- WO2015098181A1 WO2015098181A1 PCT/JP2014/072310 JP2014072310W WO2015098181A1 WO 2015098181 A1 WO2015098181 A1 WO 2015098181A1 JP 2014072310 W JP2014072310 W JP 2014072310W WO 2015098181 A1 WO2015098181 A1 WO 2015098181A1
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- gas
- bubbling
- catalyst
- electrode catalyst
- fuel cell
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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
- H01M4/90—Selection of catalytic material
- H01M4/92—Metals of platinum group
- H01M4/921—Alloys or mixtures with metallic elements
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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
- H01M4/88—Processes of manufacture
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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
- H01M4/90—Selection of catalytic material
- H01M4/92—Metals of platinum group
- H01M4/925—Metals of platinum group supported on carriers, e.g. powder carriers
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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
- H01M4/90—Selection of catalytic material
- H01M4/92—Metals of platinum group
- H01M4/928—Unsupported catalytic particles; loose particulate catalytic materials, e.g. in fluidised state
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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
- H01M4/90—Selection of catalytic material
- H01M4/92—Metals of platinum group
- H01M4/925—Metals of platinum group supported on carriers, e.g. powder carriers
- H01M4/926—Metals of platinum group supported on carriers, e.g. powder carriers on carbon or graphite
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- 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 a method for producing a fuel cell electrode catalyst, and more particularly to a method for producing a fuel cell electrode catalyst containing a platinum alloy.
- a polymer electrolyte fuel cell is a fuel in which a solid polymer electrolyte is sandwiched between an anode and a cathode, fuel is supplied to the anode, oxygen or air is supplied to the cathode, and oxygen is reduced at the cathode to extract electricity. It is a battery.
- platinum has been adopted as an electrode catalyst for fuel cells.
- alloys of platinum and other metal elements are also attracting attention as an alternative.
- other metal elements have problems that their catalytic activity is lower than platinum and their durability is low (elution occurs during the operation of the fuel cell).
- Non-Patent Document 1 discloses a method of potential-cycling a platinum / palladium alloy catalyst, and this method enables the activity and durability of the platinum / palladium alloy catalyst. It is described that there is a possibility of improving the performance.
- Patent Document 1 discloses that by dissolving catalyst particles containing platinum and palladium in an acid solution, dissolving easily soluble palladium, and depositing platinum on the (111) surface of palladium appearing on the outermost surface, It is described that catalyst particles having high durability (low platinum elution amount) can be obtained.
- Non-Patent Document 1 is not suitable industrially because it is difficult to treat a large amount of platinum / palladium alloy catalyst. Further, the method described in Patent Document 1 has room for improvement in terms of improving the catalytic activity.
- the present invention has been made in view of such problems in the prior art, and provides a method for producing a highly active fuel cell electrode catalyst containing a platinum alloy, which is industrially suitable for mass production.
- the purpose is that.
- the present invention relates to the following [1] to [5], for example.
- [1] A step of preparing a dispersion obtained by dispersing an electrode catalyst precursor for a fuel cell containing a platinum alloy (that is, an alloy containing platinum and other metal elements) in an electrolyte solution; and an oxidizing gas for the dispersion And bubbling of an inert gas or a reducing gas, and a method for producing a fuel cell electrode catalyst.
- a highly active electrode catalyst for a fuel cell containing a platinum alloy can be produced, and mass production can be performed industrially.
- the method for producing a fuel cell electrode catalyst according to the present invention comprises: A step of preparing a dispersion obtained by dispersing an electrode catalyst precursor for a fuel cell containing a platinum alloy in an electrolyte solution (hereinafter also referred to as a “dispersion preparation step”), and an oxidizing gas It includes a step of alternately performing bubbling and bubbling of an inert gas or a reducing gas (hereinafter also referred to as “bubbling step”).
- Dispersion preparation process In the dispersion preparation step, a dispersion is prepared by dispersing the electrode catalyst precursor in the electrolyte solution.
- a conventional fuel cell electrode catalyst containing a platinum alloy may be used as the electrode catalyst precursor. These may be a fuel cell electrode catalyst made of a platinum alloy, and the catalyst made of a platinum alloy is a carrier. It may be a supported fuel cell electrode catalyst supported on the catalyst.
- the supported platinum alloy particles preferably have an average particle diameter of 2 to 10 nm.
- the proportion of platinum alloy occupied is preferably 20 to 80% by mass.
- an average particle diameter shows the value measured, for example by analysis of the TEM image.
- the platinum alloy contains platinum element and other metal elements.
- the other metal element may be a noble metal element or a non-noble metal element.
- the noble metal include gold, silver, ruthenium, rhodium, palladium, osmium, and iridium, and ruthenium and palladium are preferable because a highly active catalyst is obtained.
- Non-noble metals include titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, manganese, iron, cobalt, nickel, copper, zinc, etc., and since a highly active catalyst is obtained, iron, cobalt and nickel That is, an iron group element is preferable.
- the platinum alloy may contain three or more metal elements including platinum element.
- the component ratio (molar ratio) is preferably adjusted so that a highly active catalyst is obtained.
- Pt: Pd 1: 0.5 to 0.8
- the carrier examples include carbon particles, a heat-treated product described in JP2013-116458A, containing a group 4 or group 5 transition metal element, carbon, nitrogen, and oxygen as constituent elements (the molar ratio of the constituent elements is the transition metal).
- element: carbon: nitrogen: oxygen 1: x: y: z, 0 ⁇ x ⁇ 7, 0 ⁇ y ⁇ 2, 0 ⁇ z ⁇ 3
- the heat-treated product is iron, nickel, chromium. , Cobalt, vanadium, and manganese
- the heat-treated product may be, for example, a transition metal compound (1) (a part or all of the group 4 or group 5 of the periodic table).
- the resulting solid Such particles consisting of minute residues of can be produced by a method comprising heat treatment at 500 ⁇ 1100 ° C..) It can be mentioned.
- the electrolyte solution is not limited as long as the electrolyte is dissolved therein.
- the liquid property may be acidic, neutral or alkaline, but is preferably an acidic solution, and examples thereof include sulfuric acid aqueous solution, nitric acid aqueous solution, hydrochloric acid, and perchloric acid aqueous solution. From the viewpoint that electrolyte ions are difficult to adsorb on the catalyst particle surface, a sulfuric acid aqueous solution, a nitric acid aqueous solution, and a perchloric acid aqueous solution are preferable, and a sulfuric acid aqueous solution and a perchloric acid aqueous solution are more preferable.
- the electrolyte solution may be an aqueous solution or a non-aqueous solution as long as the electrolyte is dissolved and the electrode catalyst precursor for a fuel cell can be dispersed. Since it is easy to handle and there are few side reactions to the solvent by the electrode catalyst precursor for fuel cells, an aqueous solution is preferred.
- the concentration of the electrocatalyst precursor in the dispersion is, for example, 1 to 80% by mass.
- an electrode catalyst for a fuel cell is used so that the electrode catalyst precursor for the fuel cell does not settle or form large aggregated particles in the bubbling step.
- the method is not particularly limited as long as it can sufficiently disperse the precursor, and examples thereof include stirring using a stirrer and dispersing using a ball mill or a homogenizer.
- oxidizing gas bubbling and inert gas or reducing gas bubbling are alternately performed on the dispersion. Either bubbling of oxidizing gas or bubbling of inert gas or reducing gas may be performed first.
- This step is performed to place the surface of the platinum alloy alternately in an atmosphere that can be in an oxidized state or a reduced state (non-oxidized state). At this time, not all of the surface of the platinum alloy may be in an oxidized state or a reduced state, and a part of the surface of the platinum alloy may be in an oxidized state or a reduced state.
- the electrode catalyst precursor for a fuel cell in which the platinum alloy is in an oxidized state is used and the oxidizing gas is bubbled first, in the subsequent bubbling, the bubbling of the inert gas or the reducing gas and the oxidizing gas are performed. It is preferable to perform at least one cycle with gas bubbling. When the bubbling of the inert gas or the reducing gas is performed first, it is necessary to perform the bubbling of the oxidizing gas at least once in the subsequent bubbling.
- the electrode catalyst precursor for a fuel cell in which the platinum alloy is in a reduced state is used and bubbling of the oxidizing gas is performed first, in the subsequent bubbling, at least bubbling of the inert gas or the reducing gas is performed. Must be done once.
- the inert gas or the reducing gas is bubbled first, it is preferable to perform at least one cycle of the oxidizing gas bubbling and the inert gas or reducing gas bubbling in the subsequent bubbling. .
- the action of the bubbling gas on the platinum alloy metal is shown below.
- the oxidizing gas When an oxidizing gas is used, the oxidizing gas is adsorbed on the surface of the platinum alloy, the surface potential of the platinum alloy contained in the electrode catalyst precursor is increased, and the surface of the platinum alloy is oxidized. At this time, if the platinum alloy is in an oxidized state, the oxidation proceeds further.
- the surface potential of the platinum alloy is lowered and the surface of the oxidized platinum alloy is reduced. At this time, if the platinum alloy is in a reduced state, it does not affect the reduced state of the surface of the platinum alloy, but it may be carried out because it has an effect of adjusting the surface such as removal of a slight remaining oxide.
- the bubbling with the acid active gas is preferably 0 in the potential difference of the electrocatalyst precursor (potential of the electrocatalyst precursor after bubbling-potential of the electrocatalyst precursor before starting bubbling) measured by the following method. It is performed until it becomes 0.03V or more.
- bubbling with an inert gas or a reducing gas is performed by measuring the potential difference of the electrocatalyst precursor (the potential of the electrocatalyst precursor after bubbling-the potential of the electrocatalyst precursor before starting bubbling) measured by the following method.
- the potential is preferably kept at ⁇ 0.03 V or less.
- the catalyst precursor particles are mixed with a 5% by mass Nafion (registered trademark) solution (DE521, DuPont) and water, and irradiated with ultrasonic waves to prepare a catalyst precursor ink. 20 ⁇ l of the catalyst precursor ink is dropped on a disk-type glassy carbon electrode (area: 0.196 cm 2 ) and air-dried to obtain an electrode.
- the electrode and a standard hydrogen electrode as a reference electrode are placed in the dispersion, and the potential of the electrode is measured.
- the oxidizing gas include oxygen gas and ozone gas. Oxygen gas is preferable because it can be easily produced industrially and has a small environmental load even when used in large quantities.
- the oxidizing gas may be supplied as a mixed gas (for example, air) diluted with an inert gas.
- the inert gas examples include nitrogen gas and rare gases (argon gas, etc.), and nitrogen gas is preferable from the viewpoint of availability.
- the reducing gas examples include hydrogen gas and carbon monoxide gas.
- the reducing gas may be supplied as a mixed gas with an inert gas.
- the amount of gas supplied for bubbling (hereinafter also referred to as “bubbling gas”) may be any condition as long as the above-described potential difference can be obtained. For example, it may be 20 to 200 mL / min per 100 mL of the dispersion. .
- the temperature of the dispersion during the bubbling step is, for example, 20 to 90 ° C., gas diffusion becomes faster, the potential of the catalyst precursor particles changes more quickly, and a highly active catalyst is produced in a shorter time. In terms of being able to be performed, the temperature is preferably 40 to 80 ° C.
- Time to perform bubbling of each gas that is, the time from the start of bubbling of oxidizing gas to the start of bubbling of inert gas or reducing gas, or the beginning of bubbling of inert gas or reducing gas to oxidizing gas
- the time until the start of bubbling is, for example, 5 to 30 minutes. If the bubbling time is relatively short, the longer the time, the higher the activity of the resulting catalyst.
- an effect can be obtained by performing a cycle comprising one bubbling of an oxidizing gas and one inert or reducing gas bubbling once, but this cycle may be performed a plurality of times.
- the number of cycles is, for example, 1 to 50 times, preferably 3 to 30 times. When the number of cycles is relatively small, the activity of the resulting catalyst increases as the number of cycles increases.
- Heat treatment may be performed after the bubbling, filtration, and drying. Examples of the atmosphere during the heat treatment include an inert gas or a mixed gas of 4% hydrogen and an inert gas.
- the temperature and time of the heat treatment are not particularly limited, but from the viewpoint of suppressing the aggregation of catalyst particles, the treatment temperature is preferably 150 ° C. to 800 ° C. and the treatment time is 20 minutes to 5 hours.
- the fuel cell electrode catalyst produced by the production method according to the present invention can be used in any of the anode catalyst layer and the cathode catalyst layer.
- the fuel cell catalyst layer preferably further includes an electron conductive powder and a polymer electrolyte. Any of those conventionally used in fuel cell catalyst layers can be used without particular limitation.
- the catalyst layer for a fuel cell can be used as a cathode and / or anode catalyst layer provided on an electrode of a membrane electrode assembly provided in a polymer electrolyte fuel cell.
- the electrode includes the fuel cell catalyst layer and a porous support layer (gas diffusion layer).
- the porous support layer gas diffusion layer
- those conventionally used in fuel cell catalyst layers can be used without particular limitation.
- the membrane electrode assembly is used in a fuel cell, preferably a polymer electrolyte fuel cell.
- Catalyst precursor particles prepared in Production Example, 5% by mass Nafion solution (DE521, DuPont) and water were mixed, and these were irradiated with ultrasonic waves to prepare a catalyst precursor ink of 20 ⁇ l of catalyst precursor.
- the body ink was dropped onto a disk-type glassy carbon electrode (area: 0.196 cm 2 ) and dried naturally to obtain an electrode.
- the amount of catalyst precursor particles was adjusted so that the total amount of Pd and Pt on the electrode was 33 ⁇ g / cm 2 .
- the above electrode and a standard hydrogen electrode as a reference electrode were placed in a dispersion, and changes in the potential of the electrode accompanying bubbling of various gases were measured.
- Catalyst activity evaluation The catalyst particles prepared in Examples or Comparative Examples were mixed with a Nafion solution having a concentration of 5% by mass (DE521, DuPont) and water, and these were irradiated with ultrasonic waves to prepare catalyst ink. 20 ⁇ l of catalyst ink was dropped onto a disk-type glassy carbon electrode (area: 0.196 cm 2 ) and air-dried to obtain an electrode. The amount of catalyst particles was adjusted so that the total amount of Pd and Pt on the electrode was 33 ⁇ g / cm 2 .
- Reference electrode Reversible hydrogen electrode (RHE)
- Counter electrode Pt wire
- Electrolytic solution 0.5 MH 2 SO 4 aqueous solution (Before starting the measurement, the electrolytic solution was saturated with oxygen for 1 hour.)
- i k (i d -i) / (i ⁇ i d) (Where i k is the standardized current density ( ⁇ A / cm 2 ), i is the current density at 0.9 V ( ⁇ A / cm 2 ), and i d is the diffusion current density ( ⁇ A / cm 2 ).) As the value of i k, the greater the oxygen reduction activity.
- the obtained dispersion was allowed to cool to room temperature (25 ° C.) and then filtered, and then the obtained solid was dried in an oven at 80 ° C. for 12 hours.
- the obtained dried product is pulverized in a mortar and baked in a quartz furnace in an atmosphere of a mixed gas of nitrogen gas and hydrogen gas (hydrogen gas concentration: 4% by volume) at 300 ° C. for 2 hours.
- Supported particles (hereinafter, also referred to as “catalyst precursor particles”) obtained by supporting the contained particles were obtained.
- Example 1-1 A dispersion is prepared by dispersing 0.5 g of the catalyst precursor particles in 100 mL of 0.5 M sulfuric acid aqueous solution, and nitrogen gas is bubbled through the dispersion for 10 minutes, followed by oxygen gas for 10 minutes. The bubbling of nitrogen gas for 10 minutes and the bubbling of oxygen gas for 10 minutes were repeated alternately under the following conditions for a total of 1 hour. . In the bubbling, gas was ejected using a straight pipe having an inner diameter of about 1 mm.
- the dispersion was filtered with suction using a filter having a pore size of 1 ⁇ m, washed thoroughly with pure water, and then dried in an oven at 80 ° C. for 10 hours to produce a powdered fuel cell electrode catalyst.
- Nitrogen gas supply rate 50 mL / min
- Oxygen gas supply rate 50 mL / min
- Temperature of dispersion maintained at 60 ° C. using a water bath.
- Table 1 shows changes in the potential of the catalyst precursor in the bubbling step.
- Table 2 shows various conditions and evaluation results of the obtained catalyst.
- Example 1-2 A fuel cell catalyst was produced in the same manner as in Example 1-1 except that the total time for bubbling oxygen gas and nitrogen gas was changed from 1 hour to 2 hours.
- Table 1 shows changes in the potential of the catalyst precursor in the bubbling step.
- Table 2 shows various conditions and evaluation results of the obtained catalyst.
- Examples 2-1 and 2-2 Examples 1-1 and 1 except that a commercially available platinum / cobalt alloy / carbon carrier catalyst (TEC36EA52, manufactured by Tanaka Kikinzoku Co., Ltd.) was used in place of the catalyst precursor particles obtained in Production Example 1 as catalyst precursor particles.
- TEC36EA52 platinum / cobalt alloy / carbon carrier catalyst
- Table 1 shows changes in the potential of the catalyst precursor in the bubbling step.
- Table 2 shows various conditions and evaluation results of the obtained catalyst.
- Example 1-1 In place of alternately performing bubbling of oxygen gas and bubbling of nitrogen gas, the same operation as in Example 1-1 was performed except that only bubbling of oxygen gas was performed for 1 hour, 2 hours, or 5 hours. A battery catalyst was produced. Table 1 shows changes in the potential of the catalyst precursor in the bubbling step. In addition, Table 2 shows various conditions and evaluation results of the obtained catalyst.
- Example 2-1 to 2-3 In place of alternately performing bubbling of oxygen gas and bubbling of nitrogen gas, the same operation as in Example 1-1 was performed except that only bubbling of nitrogen gas was performed for 2 hours or 5 hours.
- a catalyst was prepared. Table 1 shows changes in the potential of the catalyst precursor in the bubbling step. In addition, Table 2 shows various conditions and evaluation results of the obtained catalyst.
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Abstract
Description
[1]
白金合金(すなわち、白金および他の金属元素を含む合金)を含む燃料電池用電極触媒前駆体を電解質溶液に分散させてなる分散液を準備する工程、および
該分散液に対して、酸化性ガスのバブリングと、不活性ガスまたは還元性ガスのバブリングとを交互に実施する工程を含む
燃料電池用電極触媒の製造方法。
前記電解質溶液が、硫酸水溶液、過塩素酸水溶液、塩酸または硝酸水溶液である上記[1]に記載の燃料電池用電極触媒の製造方法。
前記酸化性ガスが酸素ガスまたは空気である上記[1]または[2]に記載の燃料電池用電極触媒の製造方法。
前記不活性ガスまたは還元性ガスが不活性ガスである上記[1]~[3]のいずれかに記載の燃料電池用電極触媒の製造方法。
前記不活性ガスが窒素ガスである上記[4]に記載の燃料電池用電極触媒の製造方法。
本発明に係る燃料電池用電極触媒の製造方法は、
白金合金を含む燃料電池用電極触媒前駆体を電解質溶液に分散させてなる分散液を準備する工程(以下「分散液準備工程」ともいう。)、および
該分散液に対して、酸化性ガスのバブリングと、不活性ガスまたは還元性ガスのバブリングとを交互に実施する工程(以下「バブリング工程」ともいう。)を含んでいる。
分散液準備工程では、電極触媒前駆体を電解質溶液に分散させてなる分散液を準備する。
白金合金は、白金元素と他の金属元素を含む。他の金属元素は貴金属元素であってもよく、非貴金属元素であってもよい。貴金属としては金、銀、ルテニウム、ロジウム、パラジウム、オスミウムおよびイリジウムが挙げられ、高活性の触媒が得られることから、ルテニウムおよびパラジウムが好ましい。
前記電極触媒前駆体を前記電解質溶液に分散させる方法としては、バブリング工程において燃料電池用電極触媒前駆体が沈降したり、大きな凝集粒を形成したりすることのないように、燃料電池用電極触媒前駆体を十分に分散させることのできる方法であれば特に制限はなく、たとえば、スターラーを用いた攪拌や、ボールミルやホモジナイザーを用いた分散方法が挙げられる。
バブリング工程では、前記分散液に対して、酸化性ガスのバブリングと、不活性ガスまたは還元性ガスのバブリングとを交互に実施する。なお、酸化性ガスのバブリングと、不活性ガスまたは還元性ガスのバブリングとはどちらを先に行ってもよい。
バブリングガスによる白金合金金属に対する作用を以下に示す。
酸活性ガスでのバブリングは、以下の方法で測定される前記電極触媒前駆体の電位差(バブリング後の電極触媒前駆体の電位-バブリングを開始する前の電極触媒前駆体の電位)が好ましくは0.03V以上となるまで行われる。
前記触媒前駆体粒子、5質量%の濃度のナフィオン(NAFION(登録商標))溶液(DE521、デュポン社)および水を混合し、これらに超音波を照射して、触媒前駆体インクを調製する。20μlの触媒前駆体インクを円盤型グラッシーカーボン電極(面積:0.196cm2)上に滴下し、自然乾燥させて電極を得る。
前記酸化性ガスとしては、たとえば酸素ガス、オゾンガスが挙げられ、工業的に容易に製造でき、大量に使用しても環境への負荷が小さいことから酸素ガスが好ましい。酸化性ガスは不活性ガスで希釈された混合ガス(例えば空気)として供給してもよい。
前記還元性ガスとしては、水素ガス、一酸化炭素ガスが挙げられる。還元性ガスは不活性ガスとの混合ガスとして供給してもよい。
上記バブリングを行い、濾過、乾燥後に、熱処理を行ってもよい。熱処理の際の雰囲気としては不活性ガスまたは4%水素と不活性ガスの混合ガスなどが挙げられる。熱処理の温度、時間は特に限定しないが、触媒粒子の凝集体を抑制の観点から、処理温度150℃~800℃、処理時間20分~5時間の範囲であることが好ましい。
前記燃料電池用触媒層は、好ましくは、電子伝導性粉末および高分子電解質をさらに含む。これらは、燃料電池用触媒層において従来使用されているものを特に制限なく使用できる。
前記膜電極接合体において、電極は前記燃料電池用触媒層と多孔質支持層(ガス拡散層)とを有する。多孔質支持層(ガス拡散層)としては、燃料電池用触媒層において従来使用されているものを特に制限なく使用できる。
前記膜電極接合体は、燃料電池、好ましくは固体高分子型燃料電池に使用される。
[評価方法]
触媒前駆体の電位評価:
製造例で作製した触媒前駆体粒子、5質量%の濃度のナフィオン溶液(DE521、デュポン社)および水を混合し、これらに超音波を照射して、触媒前駆体インクを調製した20μlの触媒前駆体インクを円盤型グラッシーカーボン電極(面積:0.196cm2)上に滴下し、自然乾燥させて電極を得た。なお、触媒前駆体粒子の量は、電極上のPdおよびPtの合計量が33μg/cm2となるように調整した。
各実施例または比較例において、上記の電極、および参照電極としての標準水素電極を分散液に入れて、各種ガスのバブリングに伴う上記電極の電位の変化を測定した。
実施例または比較例で作製した触媒粒子、5質量%の濃度のナフィオン溶液(DE521、デュポン社)および水を混合し、これらに超音波を照射して、触媒インクを調製した。20μlの触媒インクを円盤型グラッシーカーボン電極(面積:0.196cm2)上に滴下し、自然乾燥させて電極を得た。なお、触媒粒子の量は、電極上のPdおよびPtの合計量が33μg/cm2となるように調整した。
参照電極:可逆水素電極 (RHE)
対電極:Ptワイヤー
電解液:0.5M H2SO4水溶液(測定開始前に、電解液を1時間かけて酸素で飽和させた。)
回転速度:600rpm
測定電圧範囲:1.1V~0.3V
走査速度:5mV/s
得られたデータは、下式により標準化した。
ik=(id-i)/(i・id)
(式中、ikは標準化された電流密度(μA/cm2)、iは0.9Vにおける電流密度(μA/cm2)、idは拡散電流密度(μA/cm2)である。)
ikの値が大きいほど、酸素還元活性が高い。
燃料電池用触媒前駆体の製造:
500mLの水に担体粉末として0.4gのカーボンブラック担体(ケッチェンブラック EC600JD、ケッチェンブラックインターナショナル(株)製)を加え、40℃のウォーターバスで30分間撹拌した。得られた分散液に、56.6mlの(NH4)2PdCl4の水溶液(Pd濃度:0.19質量%)と103.1mlのH2PtCl6の水溶液(Pt濃度:0.19質量%)を添加し、40℃のウォーターバスで6時間撹拌した。なお、これらの添加操作および撹拌操作の間、Na2CO3の水溶液(濃度:4.2質量%)を加えることにより分散液のpHを9に維持した。
100mLの0.5M硫酸水溶液に、0.5gの前記触媒前駆体粒子を分散させて分散液を調製し、この分散液に対して10分間の窒素ガスのバブリングを行い、次いで10分間の酸素ガスのバブリングを行い、再び10分間の窒素ガスのバブリングを行う、というように10分間の窒素ガスのバブリングおよび10分間の酸素ガスのバブリングを、合計1時間、以下の条件下で交互に繰り返し行った。なお、バブリングの際は内径約1mmの直管を用いてガスを噴出させた。
窒素ガス供給量:50mL/分
酸素ガス供給量:50mL/分
分散液の温度:ウォーターバスを用いて60℃に維持した。
バブリング工程における触媒前駆体の電位の変化を表1に示す。また、各種条件および得られた触媒の評価結果を表2に示す。
酸素ガスのバブリングおよび窒素ガスのバブリングの合計の時間を1時間から2時間に変更したこと以外は実施例1-1と同様の操作を行い、燃料電池用触媒を製造した。
バブリング工程における触媒前駆体の電位の変化を表1に示す。また、各種条件および得られた触媒の評価結果を表2に示す。
触媒前駆体粒子として製造例1で得られた触媒前駆体粒子に替えて市販の白金・コバルト合金/カーボン担体触媒(TEC36EA52、田中貴金属社製)を用いたこと以外は実施例1-1、1-2と同様の操作を行い、燃料電池用触媒を製造した。
バブリング工程における触媒前駆体の電位の変化を表1に示す。また、各種条件および得られた触媒の評価結果を表2に示す。
酸素ガスのバブリングおよび窒素ガスのバブリングを交互に行うことに替えて、酸素ガスのバブリングのみを1時間、2時間または5時間行ったこと以外は実施例1-1と同様の操作を行い、燃料電池用触媒を製造した。
バブリング工程における触媒前駆体の電位の変化を表1に示す。また、各種条件および得られた触媒の評価結果を表2に示す。
酸素ガスのバブリングおよび窒素ガスのバブリングを交互に行うことに替えて、窒素ガスのバブリングのみを時間、2時間または5時間行ったこと以外は実施例1-1と同様の操作を行い、燃料電池用触媒を製造した。
バブリング工程における触媒前駆体の電位の変化を表1に示す。また、各種条件および得られた触媒の評価結果を表2に示す。
バブリング工程を行っていない製造例1の触媒前駆体粒子、白金・コバルト合金/カーボン担体触媒(TEC36EA52、田中貴金属社製)の触媒の評価結果を、それぞれ参考例1、参考例2として表2に示す。
一方、酸素ガスのみ、または窒素ガスのみのバブリングを行った比較例では、実施例と同程度の時間のバブリングを行っても、実施例ほど活性の高い触媒を得ることはできなかった。
Claims (5)
- 白金合金を含む燃料電池用電極触媒前駆体を電解質溶液に分散させてなる分散液を準備する工程、および
該分散液に対して酸化性ガスのバブリングと、不活性ガスまたは還元性ガスのバブリングとを交互に実施する工程
を含む燃料電池用電極触媒の製造方法。 - 前記電解質溶液が、硫酸水溶液、過塩素酸水溶液、塩酸または硝酸水溶液である請求項1に記載の燃料電池用電極触媒の製造方法。
- 前記酸化性ガスが酸素ガスである請求項1または2に記載の燃料電池用電極触媒の製造方法。
- 前記不活性ガスまたは還元性ガスが不活性ガスである請求項1~3のいずれかに記載の燃料電池用電極触媒の製造方法。
- 前記不活性ガスが窒素ガスである請求項4に記載の燃料電池用電極触媒の製造方法。
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US15/103,383 US9947940B2 (en) | 2013-12-27 | 2014-08-26 | Method for producing fuel cell electrode catalyst |
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JP2017029967A (ja) * | 2015-03-10 | 2017-02-09 | 学校法人同志社 | 白金触媒の製造方法及びそれを用いた燃料電池 |
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WO2020173909A1 (en) * | 2019-02-26 | 2020-09-03 | Umicore Ag & Co. Kg | Catalyst materials comprising nanoparticles on a carrier and methods for their production |
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