JP4326973B2 - Catalyst paste for fuel cell and method for producing the same - Google Patents
Catalyst paste for fuel cell and method for producing the same Download PDFInfo
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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
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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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
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Description
本発明は、固体高分子型燃料電池等の燃料電池の触媒層に塗布されて燃料電池の電極を形成するカーボンブラックを高分散させた触媒ペーストとその製造方法に関するものである。 The present invention relates to a catalyst paste in which carbon black which is applied to a catalyst layer of a fuel cell such as a polymer electrolyte fuel cell and forms an electrode of the fuel cell is highly dispersed, and a method for producing the same.
従来の固体高分子型燃料電池は高分子電解質を用いた燃料電池であって、水素を含有する燃料ガスと空気等酸素を含有する酸化剤ガスとを電気化学的に反応させることで、電力と熱とを同時に発生させるものである。その構造は、水素イオンを選択的に輸送する高分子電解質膜の両面に白金系の金属触媒を担持したカーボンブラックを触媒体とし、これに水素イオン伝導性高分子電解質を混合したもので触媒層を形成する。ここで、白金に代表される反応活性の高い金属触媒を数ナノメートルの非常に微細な粒子として、数１０〜数１，０００平方メートルの比表面積を持つ炭素微粉末としてのカーボンブラック上に担持し、触媒層中に高分散させることが行われてきた。 A conventional polymer electrolyte fuel cell is a fuel cell using a polymer electrolyte, and it is possible to react electric power with a fuel gas containing hydrogen and an oxidant gas containing oxygen such as air. It generates heat at the same time. The catalyst layer is composed of carbon black carrying a platinum-based metal catalyst on both sides of a polymer electrolyte membrane that selectively transports hydrogen ions, and a mixture of hydrogen ion conductive polymer electrolyte. Form. Here, a highly reactive metal catalyst represented by platinum is supported on carbon black as carbon fine powder having a specific surface area of several tens to several thousand square meters as very fine particles of several nanometers. High dispersion in the catalyst layer has been performed.
カーボンブラックを高分散させる方法としては、特許文献１に記載されているように、触媒ペーストを一旦固体にして乾式粉砕した後、再ペースト化する方法や、特許文献２に記載されているように、カーボンブラックを親水化処理させる方法が知られている。
しかしながら、特許文献１に記載されている触媒ペーストを乾式粉砕する方法は発火の恐れがあり危険であるだけでなく、触媒ペーストを一旦固体にする工程、乾式粉砕する工程、再ペースト化する工程と、工程が複雑になり製造に時間が掛かる。また、特許文献２に記載されているカーボンブラックを親水化処理させる方法は、分散工程以外に親水化処理工程が必要になってやはり製造に時間が掛かるという問題点があった。 However, the method of dry pulverizing the catalyst paste described in Patent Document 1 is not only dangerous because there is a risk of ignition, but the step of once solidifying the catalyst paste, the step of dry pulverizing, the step of re-pasting, The process becomes complicated and takes time to manufacture. In addition, the method of hydrophilizing carbon black described in Patent Document 2 has a problem in that it takes a long time for production because a hydrophilizing process is required in addition to the dispersing process.
そこで、本発明は、簡単な工程で時間を掛けずに従来以上に触媒担持カーボンブラックを高分散させた高安定性の燃料電池用触媒ペーストとその製造方法の提供を課題とするものである。 Accordingly, an object of the present invention is to provide a highly stable fuel cell catalyst paste in which a catalyst-supported carbon black is highly dispersed more than ever before in a simple process without taking time, and a method for producing the same.
請求項１の発明にかかる燃料電池用触媒ペーストは、触媒担持カーボンブラックとイオン交換樹脂と溶媒とを混合して、外部剪断機で外部剪断し、内部剪断機で内部剪断（液−液剪断）を行い、再度前記外部剪断機または別種の外部剪断機で外部剪断してなるものである。 The catalyst paste for a fuel cell according to the invention of claim 1 is obtained by mixing a catalyst-supporting carbon black, an ion exchange resin and a solvent, externally shearing with an external shearing machine, and internal shearing (liquid-liquid shearing) with an internal shearing machine. And externally shearing again with the external shearing machine or another type of external shearing machine.
請求項２の発明にかかる燃料電池用触媒ペーストの製造方法は、触媒担持カーボンブラックとイオン交換樹脂と溶媒とを混合して外部剪断を行う第１の工程と、内部剪断（液−液剪断）を行う第２の工程と、再度外部剪断を行う第３の工程とを具備するものである。 A method for producing a fuel cell catalyst paste according to a second aspect of the invention includes a first step of mixing a catalyst-supporting carbon black, an ion exchange resin, and a solvent to perform external shearing, and internal shearing (liquid-liquid shearing). And a third step of performing external shear again.
請求項３の発明にかかる燃料電池用触媒ペーストの製造方法は、触媒担持カーボンブラックとイオン交換樹脂と溶媒とを混合して、外部剪断機で外部剪断を行う第１の工程と、内部剪断機で内部剪断（液−液剪断）を行う第２の工程と、再度前記外部剪断機または別種の外部剪断機で外部剪断を行う第３の工程とを具備するものである。 According to a third aspect of the present invention, there is provided a method for producing a fuel cell catalyst paste comprising: a first step of mixing a catalyst-supporting carbon black, an ion exchange resin, and a solvent; The second step of performing internal shearing (liquid-liquid shearing) and the third step of performing external shearing again with the external shearing machine or another type of external shearing machine.
請求項４の発明にかかる燃料電池用触媒ペーストまたは燃料電池用触媒ペーストの製造方法は、請求項１または請求項３の構成において、前記外部剪断機はビーズミル、ボールミル、高速薄膜旋回型攪拌機または３本ロールであり、前記内部剪断機は超音波ホモジナイザー、回転式分散乳化機、高速攪拌剪断機、断続ジェット流式攪拌機またはジェットミルであるものである。 According to a fourth aspect of the present invention, there is provided the fuel cell catalyst paste or the fuel cell catalyst paste manufacturing method according to the first or third aspect, wherein the external shearing machine is a bead mill, a ball mill, a high-speed thin film swirling stirrer, or 3 In this roll, the internal shearing machine is an ultrasonic homogenizer, a rotary dispersion emulsifier, a high-speed stirring shearing machine, an intermittent jet flow type stirring machine, or a jet mill.
請求項５の発明にかかる燃料電池用触媒ペーストまたは燃料電池用触媒ペーストの製造方法は、請求項１または請求項４若しくは請求項２乃至請求項４のいずれか１つの構成において、前記触媒担持カーボンブラックとして貴金属担持カーボンブラックを、前記溶媒として純水のみまたは純水とエタノール、プロパノールを始めとする低級アルコールとの混合液を用いたものである。 According to a fifth aspect of the present invention, there is provided a fuel cell catalyst paste or a fuel cell catalyst paste manufacturing method according to the first aspect, the fourth aspect of the present invention, or the second aspect of the present invention. Noble metal-supporting carbon black is used as black, and pure water alone or a mixture of pure water and lower alcohols such as ethanol and propanol is used as the solvent.
請求項６の発明にかかる燃料電池用触媒ペーストの製造方法は、請求項２乃至請求項５のいずれか１つの構成において、前記第１の工程が終了した段階で、ペーストの粘度が粘度計の測定条件ずり速度５０ｓ-1において約５０ｍＰａ・ｓ〜約２５０ｍＰａ・ｓの範囲内であるものである。 According to a sixth aspect of the present invention, there is provided a method for producing a fuel cell catalyst paste according to any one of the second to fifth aspects, wherein when the first step is completed, the viscosity of the paste is measured by a viscometer. The measurement conditions are those within a range of about 50 mPa · s to about 250 mPa · s at a shear rate of 50 s −1 .
請求項１の発明にかかる燃料電池用触媒ペーストは、触媒担持カーボンブラックとイオン交換樹脂と溶媒とを混合して、外部剪断機で外部剪断し、内部剪断機で内部剪断を行い、再度前記外部剪断機または別種の外部剪断機で外部剪断してなり、こうして製造された触媒ペーストは触媒を担持するカーボンブラックに親水化処理等を施さなくても優れた分散安定性を持ち、また触媒担持カーボンブラックが高分散されたものとなる。 The catalyst paste for a fuel cell according to the invention of claim 1 is obtained by mixing a catalyst-supporting carbon black, an ion exchange resin and a solvent, externally shearing with an external shearing machine, performing internal shearing with an internal shearing machine, and again The catalyst paste produced by external shearing using a shearing machine or another type of external shearing machine has excellent dispersion stability even if the carbon black supporting the catalyst is not subjected to a hydrophilization treatment, etc. Black is highly dispersed.
この理由は、単に外部剪断機で外部剪断しただけでは触媒担持カーボンブラックの分散されない粒子の塊がかなり残るが、内部剪断（液−液剪断）を行うことによりこれらの塊も分割され、触媒担持カーボンブラックの粒子に分散される。しかし、この段階で処理を終了して放置すると分割された粒子はイオン交換樹脂に包まれていないので再び凝集してしまう。そこで、再度前記外部剪断機または別種の外部剪断機で外部剪断することによって、分割された粒子の間にもイオン交換樹脂が入り込み分割された粒子を包むので、放置しても再び凝集することなく優れた分散安定性を示すことになると考えられる。 The reason for this is that, even if external shearing is simply performed by an external shearing machine, a large amount of particles of the catalyst-supported carbon black that are not dispersed remains. However, by performing internal shearing (liquid-liquid shearing), these masses are also divided, Dispersed in carbon black particles. However, if the treatment is terminated at this stage and left as it is, the divided particles are not wrapped in the ion exchange resin, and thus aggregate again. Therefore, by externally shearing again with the external shearing machine or another type of external shearing machine, the ion-exchange resin enters between the divided particles and wraps the divided particles. It is considered that excellent dispersion stability is exhibited.
このようにして、外部剪断機と内部剪断機を用いた簡単な工程で時間を掛けずに従来以上に触媒担持カーボンブラックを高分散させた高安定性の燃料電池用触媒ペーストを製造できるので、大量生産が可能であり、また触媒粒子の安定性が良いため薄膜の触媒層形成が可能であり、触媒使用量を低減できる燃料電池用触媒ペーストとなる。 In this way, since it is possible to produce a highly stable catalyst paste for a fuel cell in which the catalyst-supported carbon black is highly dispersed in a simple process using an external shearing machine and an internal shearing machine without taking time, Mass production is possible, and since the catalyst particles have good stability, a thin catalyst layer can be formed, resulting in a fuel cell catalyst paste that can reduce the amount of catalyst used.
請求項２の発明にかかる燃料電池用触媒ペーストの製造方法は、触媒担持カーボンブラックとイオン交換樹脂と溶媒とを混合して外部剪断を行う第１の工程と、内部剪断を行う第２の工程と、再度外部剪断を行う第３の工程とを具備する。かかる製造方法で製造された燃料電池用触媒ペーストは、触媒を担持するカーボンブラックに親水化処理等を施さなくても優れた分散安定性を持ち、また触媒担持カーボンブラックが高分散される。 A method for producing a fuel cell catalyst paste according to a second aspect of the invention includes a first step of performing external shearing by mixing catalyst-supporting carbon black, an ion exchange resin, and a solvent, and a second step of performing internal shearing. And a third step of performing external shear again. The fuel cell catalyst paste produced by such a production method has excellent dispersion stability even when the catalyst-supporting carbon black is not subjected to a hydrophilic treatment or the like, and the catalyst-supported carbon black is highly dispersed.
この理由は、第１の工程の外部剪断だけでは触媒担持カーボンブラックの分散されない粒子の塊がかなり残るが、第２の工程の内部剪断を行うことによりこれらの塊も分割され、触媒担持カーボンブラックの粒子に分散される。そして、第３の工程の再度外部剪断によって、分割された粒子の間にもイオン交換樹脂が入り込み分割された粒子を包むので、放置しても再び凝集することなく優れた分散安定性を示すことになると考えられる。 The reason for this is that although a large amount of unsupported particles of the catalyst-supported carbon black remains only by the external shearing in the first step, these masses are also divided by performing the internal shearing in the second step. Dispersed in the particles. And, by the external shearing again in the third step, the ion-exchange resin enters between the divided particles and wraps the divided particles, so that excellent dispersion stability is exhibited without agglomeration again even if left standing. It is thought that it becomes.
このようにして、一般的な外部剪断と内部剪断と再外部剪断を含む簡単な工程で時間を掛けずに従来以上に触媒担持カーボンブラックを高分散させた高安定性の燃料電池用触媒ペーストを製造できるので、大量生産が可能であり、また触媒粒子の安定性が良いため薄膜の触媒層形成が可能であり、触媒使用量を低減できる燃料電池用触媒ペーストの製造方法となる。 In this way, a highly stable fuel cell catalyst paste in which catalyst-supported carbon black is more highly dispersed than in the past without taking time in a simple process including general external shear, internal shear, and re-external shear. Since it can be produced, mass production is possible, and since the catalyst particles have good stability, a thin-film catalyst layer can be formed, and the method for producing a fuel cell catalyst paste can reduce the amount of catalyst used.
請求項３の発明にかかる燃料電池用触媒ペーストの製造方法においては、触媒担持カーボンブラックとイオン交換樹脂と溶媒とを混合して、外部剪断機で外部剪断を行う第１の工程と、内部剪断機で内部剪断を行う第２の工程と、再度前記外部剪断機または別種の外部剪断機で外部剪断を行う第３の工程とを具備する。かかる製造方法で製造された燃料電池用触媒ペーストは、触媒を担持するカーボンブラックに親水化処理等を施さなくても優れた分散安定性を持ち、また触媒担持カーボンブラックが高分散される。 In the method for producing a fuel cell catalyst paste according to the invention of claim 3, the first step of mixing the catalyst-carrying carbon black, the ion exchange resin and the solvent and performing external shearing with an external shearing machine, and internal shearing A second step of performing internal shearing with a machine, and a third step of performing external shearing again with the external shearing machine or another type of external shearing machine. The fuel cell catalyst paste produced by such a production method has excellent dispersion stability even when the catalyst-supporting carbon black is not subjected to a hydrophilic treatment or the like, and the catalyst-supported carbon black is highly dispersed.
この理由は、第１の工程の外部剪断機による外部剪断だけでは触媒担持カーボンブラックの分散されない粒子の塊がかなり残るが、第２の工程の内部剪断機による内部剪断を行うことによりこれらの塊も分割され、触媒担持カーボンブラックの粒子に分散される。そして、第３の工程の外部剪断機による再度分散によって、分割された粒子の間にもイオン交換樹脂が入り込み分割された粒子を包むので、放置しても再び凝集することなく優れた分散安定性を示すことになると考えられる。 The reason for this is that a large amount of undispersed particles of the catalyst-supported carbon black remain only by external shearing by the external shearing machine in the first step, but these masses are obtained by performing internal shearing by the internal shearing machine in the second step. Are also divided and dispersed in particles of catalyst-supported carbon black. And by the dispersion again by the external shearing machine in the third step, since the ion exchange resin enters between the divided particles and wraps the divided particles, excellent dispersion stability without agglomeration even if left standing It is thought that will be shown.
このようにして、一般的な外部剪断機による外部剪断と内部剪断機による内部剪断と外部剪断機による再外部剪断を含む簡単な工程で時間を掛けずに従来以上に触媒担持カーボンブラックを高分散させた高安定性の燃料電池用触媒ペーストを製造できるので、大量生産が可能であり、また触媒粒子の安定性が良いため薄膜の触媒層形成が可能であり、触媒使用量を低減できる燃料電池用触媒ペーストの製造方法となる。 In this way, the catalyst-supported carbon black is more highly dispersed in a simple process including external shearing by a general external shearing machine, internal shearing by an internal shearing machine, and re-external shearing by an external shearing machine without taking time. The high-stability fuel cell catalyst paste can be manufactured, so that mass production is possible, and because the catalyst particles have good stability, a thin-film catalyst layer can be formed and the amount of catalyst used can be reduced. It becomes the manufacturing method of the catalyst paste for water.
請求項４の発明にかかる燃料電池用触媒ペーストまたは燃料電池用触媒ペーストの製造方法においては、外部剪断機としてビーズミル、ボールミル、高速薄膜旋回型攪拌機または３本ロールを用いて、内部剪断機として超音波ホモジナイザー、回転式分散乳化機、高速攪拌剪断機、断続ジェット流式攪拌機またはジェットミルを用いている。 In the fuel cell catalyst paste or the fuel cell catalyst paste manufacturing method according to the invention of claim 4, a bead mill, a ball mill, a high-speed thin film swirl stirrer or a three-roller is used as an external shear, and an ultra-high shear as an internal shear. A sonic homogenizer, a rotary dispersion emulsifier, a high-speed stirring shearing machine, an intermittent jet flow type stirring machine or a jet mill is used.
このようにして、外部剪断機として一般的なビーズミル等と内部剪断機として一般的な超音波ホモジナイザー等を用いた簡単な工程で時間を掛けずに従来以上に触媒担持カーボンブラックを高分散させた高安定性の燃料電池用触媒ペーストを製造できるので、大量生産が可能であり、また触媒粒子の安定性が良いため薄膜の触媒層形成が可能であり、触媒使用量を低減できる燃料電池用触媒ペーストまたはその製造方法となる。 In this way, the catalyst-supported carbon black was highly dispersed in a simple process using a general bead mill or the like as an external shear and a general ultrasonic homogenizer or the like as an internal shear without taking time. Highly stable fuel cell catalyst paste can be manufactured, so mass production is possible, and the catalyst particles have good stability, so that a thin catalyst layer can be formed and the amount of catalyst used can be reduced. It becomes a paste or its manufacturing method.
請求項５の発明にかかる燃料電池用触媒ペーストまたは燃料電池用触媒ペーストの製造方法においては、触媒担持カーボンブラックとして貴金属担持カーボンブラックを、溶媒として純水のみまたは純水とエタノール、プロパノールを始めとする低級アルコールとの混合液を用いている。白金を始めとする貴金属は反応活性の高い金属触媒であり、その数ナノメートルの非常に微細な粒子を比表面積の広いカーボンブラックに担持させることによって、燃料電池用触媒ペーストとして非常に優れた特性を発揮する。また、純水、純水とエタノール、プロパノールを始めとする低級アルコールとの混合液は、このように微小な貴金属担持カーボンブラックを高分散させるのに適した分散媒である。 In the fuel cell catalyst paste or the fuel cell catalyst paste manufacturing method according to the invention of claim 5, noble metal-supported carbon black is used as the catalyst-supported carbon black, and only pure water or pure water and ethanol, propanol are used as the solvent. A mixed solution with a lower alcohol is used. Noble metals such as platinum are highly reactive metal catalysts, and they have excellent properties as catalyst pastes for fuel cells by supporting very fine particles of several nanometers on carbon black with a large specific surface area. Demonstrate. Further, pure water or a mixed liquid of pure water and lower alcohol such as ethanol and propanol is a dispersion medium suitable for highly dispersing such a noble metal-supported carbon black.
これにイオン交換樹脂を加えて混合し、ビーズミル等による外部剪断、超音波ホモジナイザー等による内部剪断、そして再度外部剪断を行うことによって貴金属担持カーボンブラックが高分散され、再び凝集することなく優れた分散安定性を示す。 The ion-exchange resin is added and mixed, and the precious metal-supported carbon black is highly dispersed by external shearing using a bead mill, internal shearing using an ultrasonic homogenizer, and external shearing. Shows stability.
このようにして、簡単な工程で時間を掛けずに従来以上に貴金属担持カーボンブラックを高分散させた高安定性の燃料電池用触媒ペーストを製造できるので、大量生産が可能であり、また触媒粒子の安定性が良いため薄膜の触媒層形成が可能であり、触媒使用量を低減でき、触媒特性にも優れた燃料電池用触媒ペーストまたはその製造方法となる。 In this way, it is possible to produce a highly stable fuel cell catalyst paste in which noble metal-supported carbon black is more highly dispersed than in the past without requiring a simple process, so that mass production is possible. Therefore, it is possible to form a thin catalyst layer, reduce the amount of catalyst used, and provide a fuel cell catalyst paste excellent in catalyst characteristics or a method for producing the same.
請求項６の発明にかかる燃料電池用触媒ペーストの製造方法においては、第１の工程が終了した段階で、ペーストの粘度が粘度計の測定条件ずり速度５０ｓ-1において約５０ｍＰａ・ｓ〜約２５０ｍＰａ・ｓの範囲内である。第１の工程即ち外部剪断が終了した時点でペーストの粘度がかかる範囲内に入っていれば、第２の工程即ち内部剪断を行うことによって触媒担持カーボンブラックが充分に高分散して、第３の工程即ち再度外部剪断を行うことによって、再び凝集することなく優れた分散安定性を示す燃料電池用触媒ペーストとなる。 In the method for producing a fuel cell catalyst paste according to the invention of claim 6, when the first step is completed, the viscosity of the paste is about 50 mPa · s to about 250 mPas at a measuring condition shear rate of 50 s −1 of the viscometer. -Within the range of s. If the viscosity of the paste is within the range when the first step, that is, external shearing is completed, the catalyst-carrying carbon black is sufficiently dispersed by performing the second step, that is, internal shearing. By carrying out this step, that is, external shearing again, a fuel cell catalyst paste showing excellent dispersion stability without agglomeration again is obtained.
このようにして、簡単な工程で時間を掛けずに従来以上に触媒担持カーボンブラックを高分散させた高安定性の燃料電池用触媒ペーストを製造できるので、大量生産が可能であり、また触媒粒子の安定性が良いため薄膜の触媒層形成が可能であり、触媒使用量を低減できる燃料電池用触媒ペーストの製造方法となる。 In this way, a highly stable catalyst paste for a fuel cell in which the catalyst-supported carbon black is highly dispersed more than before can be produced in a simple process without taking time, so that mass production is possible, and catalyst particles can be produced. Therefore, the catalyst layer can be formed as a thin film, and the amount of catalyst used can be reduced.
以下、本発明の実施の形態について説明する。 Embodiments of the present invention will be described below.
まず、本実施の形態にかかる燃料電池用触媒ペーストの組成について説明する。白金５０％担持カーボンブラック２５重量部、５％イオン交換樹脂溶液２５０重量部、純水３７．５重量部、エタノール３７．５重量部を混合する。この燃料電池用触媒ペースト用の混合溶液の組成を、表１にまとめて示す。
First, the composition of the fuel cell catalyst paste according to the present embodiment will be described. 25 parts by weight of platinum 50% supported carbon black, 250 parts by weight of 5% ion exchange resin solution, 37.5 parts by weight of pure water, and 37.5 parts by weight of ethanol are mixed. Table 1 summarizes the composition of the mixed solution for the fuel cell catalyst paste.
この混合溶液を１０分間ディスパーにて攪拌を行った後、実施例１として第１の工程の外部剪断としてのビーズミル分散１０分、第２の工程の内部剪断（液−液剪断）としての超音波処理３分、そして第３の工程の再度外部剪断としての再度ビーズミル分散１０分の分散工程を行った。分散装置は、外部剪断機としてビーズミル ＤＩＳＰＥＲＭＡＴ ＳＬ−１２Ｃ、φ１ｍｍジルコニアビーズ８０％充填、ローター周速８ｍ／ｓ循環運転、内部剪断（液−液剪断）には内部剪断機として超音波ホモジナイザーＳＭＴ ＵＨ−３００を使用した。 After stirring this mixed solution with a disper for 10 minutes, as Example 1, 10 minutes of bead mill dispersion as external shear in the first step, and ultrasonic waves as internal shear (liquid-liquid shear) in the second step The dispersion process was performed for 3 minutes after the treatment, and the beads mill was dispersed again for 10 minutes as the external shear of the third process. The dispersion apparatus is a bead mill DISPERMAT SL-12C as an external shearing machine, filled with 80% φ1 mm zirconia beads, a rotor circumferential speed of 8 m / s circulation operation, and an internal homogenizer SMT UH- as an internal shearing machine for internal shearing (liquid-liquid shearing). 300 was used.
なお、比較のために、比較例１としてビーズミル分散２０分のみを行ったもの、比較例２として超音波処理３分の後ビーズミル分散１５分を行ったもの、比較例３としてビーズミル分散２０分の後超音波処理３分を行ったものについても、分散性を測定した。分散性は、粒度分布を測定して、得られた粒子径（メジアン径）によって示した（分散処理直後と２０℃で２週間保管後について測定した。）。粒度分布の測定には、堀場製作所 ＬＡ−９１０を使用した。比較例１，２，３と実施例１それぞれの分散工程の内容と分散性の測定結果を表２にまとめて示す。
For comparison, Comparative Example 1 was subjected only to bead mill dispersion for 20 minutes, Comparative Example 2 was subjected to ultrasonic treatment for 3 minutes and then bead mill dispersion for 15 minutes, and Comparative Example 3 was subjected to bead mill dispersion for 20 minutes. Dispersibility was also measured for those subjected to post-sonication for 3 minutes. The dispersibility was measured by measuring the particle size distribution and indicated by the obtained particle diameter (median diameter) (measured immediately after the dispersion treatment and after storage at 20 ° C. for 2 weeks). Horiba LA-910 was used for the measurement of the particle size distribution. Table 2 summarizes the contents of the dispersion steps and the measurement results of the dispersibility in Comparative Examples 1, 2, 3 and Example 1.
表２に示されるように、第１工程としてビーズミル分散１０分、第２工程として超音波処理３分、そして第３工程として再度ビーズミル分散１０分の分散工程を行った実施例１においては、分散処理直後の粒子径が０．３μｍと細かく高分散していることを示している。そして、２０℃で２週間保管後の粒子径も０．３μｍと変化しておらず高分散を保っており、分散安定性にも極めて優れていることを示した。 As shown in Table 2, in Example 1 in which a dispersion step of beads mill dispersion for 10 minutes was performed as the first step, ultrasonic treatment was performed for 3 minutes as the second step, and dispersion step of 10 minutes was performed again as the third step. It shows that the particle diameter immediately after the treatment is finely dispersed as fine as 0.3 μm. The particle diameter after storage at 20 ° C. for 2 weeks was not changed to 0.3 μm, and the dispersion was kept high, indicating that the dispersion stability was extremely excellent.
これに対して、ビーズミル分散２０分のみの比較例１においては、分散直後の粒子径が０．７μｍとやや粗く、２週間後の粒子径は１．５μｍとさらに粗くなっており、分散性にも分散安定性にも劣っていることが分かる。また、超音波処理３分の後ビーズミル分散１５分の比較例２においても、分散直後の粒子径が０．７μｍ、２週間後の粒子径は１．０μｍと、やはり分散性にも分散安定性にも劣っている。さらに、第１工程としてビーズミル分散２０分、第２工程として超音波処理３分の分散処理をした比較例３においては、分散直後の粒子径が０．５μｍとやや細かくなっているが、２週間後の粒子径は３．５μｍと、比較例１，２よりも粗くなっている。 On the other hand, in Comparative Example 1 with only 20 minutes of bead mill dispersion, the particle diameter immediately after dispersion is slightly coarse as 0.7 μm, and the particle diameter after 2 weeks is further coarsened as 1.5 μm, which makes the dispersibility It can be seen that the dispersion stability is also poor. Further, in Comparative Example 2 in which the bead mill dispersion is 15 minutes after the ultrasonic treatment 3 minutes, the particle diameter immediately after dispersion is 0.7 μm, and the particle diameter after 2 weeks is 1.0 μm. Also inferior. Furthermore, in Comparative Example 3 in which the dispersion process of the bead mill was 20 minutes as the first step and the ultrasonic treatment was 3 minutes as the second step, the particle diameter immediately after dispersion was slightly fine at 0.5 μm, but for 2 weeks The subsequent particle size is 3.5 μm, which is coarser than those of Comparative Examples 1 and 2.
以上の結果、超音波処理による分散効果は確かにあるが、その後第３工程として再度ビーズミル分散処理を行わないと、凝集が起こって分散安定性に欠けるペーストとなることが明らかになった。 As a result of the above, it has been clarified that there is a dispersion effect by the ultrasonic treatment, but if the bead mill dispersion treatment is not performed again as the third step, agglomeration occurs and the paste lacks dispersion stability.
このようにして、本実施の形態の実施例１においては、一般的なビーズミルと超音波ホモジナイザーを用いた簡単な工程で時間を掛けずに従来以上にカーボンブラックを高分散させた高安定性の燃料電池用触媒ペーストを製造できるので、大量生産が可能であり、また触媒粒子の安定性が良いため薄膜の触媒層形成が可能であり、触媒使用量を低減できるため低コスト化に繋げることができる。 In this way, in Example 1 of the present embodiment, a highly stable carbon black is more highly dispersed than in the past without taking time in a simple process using a general bead mill and an ultrasonic homogenizer. Since the catalyst paste for fuel cells can be manufactured, mass production is possible, and the catalyst particles can be formed because the stability of the catalyst particles is good, and the amount of catalyst used can be reduced, leading to lower costs. it can.
次に、実施例２として、内部剪断機として回転式分散乳化機を用いた例について説明する。燃料電池用触媒ペースト用の混合溶液の組成は、実施例１と同じく表１に示されるものである。この混合溶液を１０分間ディスパーにて攪拌を行った後、実施例２としてビーズミル分散１０分、回転式分散乳化処理１分、そして再度ビーズミル分散５分の分散工程を行った。分散装置は、ビーズミル ＤＩＳＰＥＲＭＡＴ ＳＬ−１２Ｃ、φ１ｍｍジルコニアビーズ８０％充填、ローター周速８ｍ／ｓ循環運転、回転式分散乳化処理には回転式分散乳化機 エムテック ＣＬＭ−１．５Ｓ ローターＲ４ スクリーンＳ１．５−２４−０２を使用した。 Next, as Example 2, an example using a rotary dispersion emulsifier as an internal shearing machine will be described. The composition of the mixed solution for the fuel cell catalyst paste is shown in Table 1 as in Example 1. After stirring this mixed solution with a disper for 10 minutes, as Example 2, a dispersion step of bead mill dispersion for 10 minutes, rotational dispersion emulsification treatment for 1 minute, and bead mill dispersion for 5 minutes was performed again. Dispersion equipment is bead mill DISPERMAT SL-12C, φ1mm zirconia beads 80% filling, rotor peripheral speed 8m / s circulation operation, rotary dispersion emulsification processing. MTEC CLM-1.5S rotor R4 screen S1.5 -24-02 was used.
比較例４として回転式分散乳化処理１分の後、ビーズミル分散１５分を行ったもの、比較例５としてビーズミル分散２０分の後、回転式分散乳化処理１分を行ったものについても分散性を測定した。 Dispersibility was also obtained for Comparative Example 4 after 1 minute of rotary dispersion emulsification treatment and 15 minutes of bead mill dispersion, and as Comparative Example 5 after 20 minutes of bead mill dispersion and 1 minute of rotary dispersion emulsification treatment. It was measured.
分散性は、粒度分布を測定して、得られた粒子径（メジアン径）によって示した（分散処理直後と２０℃で２週間保管後について測定した。）。粒度分布の測定には、堀場製作所 ＬＡ−９１０を使用した。比較例４，５と比較して実施例２の分散工程の内容と分散性の測定結果を表３にまとめて示す。
The dispersibility was measured by measuring the particle size distribution and indicated by the obtained particle diameter (median diameter) (measured immediately after the dispersion treatment and after storage at 20 ° C. for 2 weeks). Horiba LA-910 was used for the measurement of the particle size distribution. Table 3 summarizes the contents of the dispersion process of Example 2 and the measurement results of dispersibility in comparison with Comparative Examples 4 and 5.
表３に示されるように、第１工程としてビーズミル分散１０分、第２工程として回転式分散乳化処理１分、そして第３工程として再度ビーズミル分散５分の分散工程を行った実施例２においては、分散処理直後の粒子径が０．２μｍと細かく高分散していることを示している。そして、２０℃で２週間保管後の粒子径も０．２μｍと変化しておらず高分散を保っており、分散安定性にも極めて優れていることを示した。 As shown in Table 3, in Example 2 in which the dispersion step of bead mill dispersion was carried out for 10 minutes as the first step, the dispersion dispersion emulsification treatment for 1 minute as the second step, and the dispersion step of 5 minutes again as the third step. This shows that the particle size immediately after the dispersion treatment is fine and highly dispersed at 0.2 μm. The particle diameter after storage at 20 ° C. for 2 weeks was not changed to 0.2 μm, and the dispersion was kept high, indicating that the dispersion stability was extremely excellent.
これに対して、回転式分散乳化処理１分の後ビーズミル分散１５分の比較例４においては、分散直後の粒子径が０．７μｍ、２週間後の粒子径は１．０μｍと、分散性にも分散安定性にも劣っている。また、第１工程としてビーズミル分散２０分、第２工程として回転式分散乳化処理１分の分散処理をした比較例５においては、分散直後の粒子径は０．２μｍと細かくなっているが、２週間後の粒子径は１４μｍと、非常に粗くなっている。 On the other hand, in Comparative Example 4 after 1 minute of rotational dispersion emulsification treatment and 15 minutes of bead mill dispersion, the particle diameter immediately after dispersion is 0.7 μm, and the particle diameter after 2 weeks is 1.0 μm, which is dispersible. Are also inferior in dispersion stability. Further, in Comparative Example 5 in which the bead mill dispersion was performed for 20 minutes as the first step and the dispersion treatment was performed for 1 minute as the second step, the particle diameter immediately after dispersion was as small as 0.2 μm. The particle diameter after a week is 14 μm, which is very coarse.
以上の結果、回転式分散乳化処理による分散効果は確かにあるが、その後第３工程として再度ビーズミル分散処理を行わないと、凝集が起こって分散安定性に欠けるペーストとなることが明らかになった。 As a result of the above, it has been clarified that there is a dispersion effect by the rotational dispersion emulsification treatment, but if the bead mill dispersion treatment is not performed again as the third step, aggregation occurs and the paste lacks dispersion stability. .
このようにして、本実施の形態の実施例２においては、一般的なビーズミルと回転式分散乳化機を用いた簡単な工程で時間を掛けずに従来以上にカーボンブラックを高分散させた高安定性の燃料電池用触媒ペーストを製造できるので、大量生産が可能であり、また触媒粒子の安定性が良いため薄膜の触媒層形成が可能であり、触媒使用量を低減できるため低コスト化に繋げることができる。 In this way, in Example 2 of the present embodiment, high stability in which carbon black is more highly dispersed than in the past without taking time in a simple process using a general bead mill and a rotary dispersion emulsifier. The fuel cell catalyst paste can be manufactured, so mass production is possible, and the catalyst particles can be formed because the catalyst particles are stable, and the amount of catalyst used can be reduced, leading to lower costs. be able to.
本実施の形態においては、金属触媒として白金微粒子を用いているが、他の金属触媒を用いても良い。また、本実施の形態においては、溶媒として純水とエタノールを用いているが、必ずしもこの組み合わせに限られるものではなく、純水のみ、純水とイソプロパノールを始めとする低級アルコール、或いはその他の水溶性の有機溶媒との混合液等、他の溶媒を用いることもできる。 In this embodiment, platinum fine particles are used as the metal catalyst, but other metal catalysts may be used. In this embodiment, pure water and ethanol are used as the solvent. However, the present invention is not necessarily limited to this combination. Only pure water, pure water and lower alcohol such as isopropanol, or other water-soluble substances are used. Other solvents such as a mixed solution with a soluble organic solvent can also be used.
さらに、本実施の形態においては、ビーズミルのメディアとしてジルコニアビーズを用いているが、ビーズの材質については特に限定されるものではない。 Furthermore, in this embodiment, zirconia beads are used as the media of the bead mill, but the material of the beads is not particularly limited.
また、本実施の形態においては、外部剪断機としてビーズミルを用いているが、これに限られるものではなく、よりメディアの径の大きいボールミル等を用いても良く、第１の工程に限っては３本ロールを用いることもできる。さらに、内部剪断機として超音波ホモジナイザーまたは回転式分散乳化機を用いているが、ジェットミル等を用いても良い。 Further, in the present embodiment, a bead mill is used as an external shearing machine. However, the present invention is not limited to this, and a ball mill having a larger media diameter may be used, and only in the first step. Three rolls can also be used. Furthermore, although an ultrasonic homogenizer or a rotary dispersion emulsifier is used as the internal shearing machine, a jet mill or the like may be used.
燃料電池用触媒ペーストのその他の部分の組成、成分、配合量、材質、大きさ等についても、また燃料電池用触媒ペーストの製造方法のその他の工程についても、本実施の形態に限定されるものではない。 The composition, components, blending amount, material, size, etc. of other parts of the catalyst paste for fuel cells, and other steps of the method for producing the catalyst paste for fuel cells are also limited to this embodiment. is not.
Claims (6)
内部剪断（液−液剪断）を行う第２の工程と、
再度外部剪断を行う第３の工程と
を具備することを特徴とする燃料電池用触媒ペーストの製造方法。 A first step of mixing catalyst-carrying carbon black, an ion exchange resin, and a solvent to perform external shearing;
A second step of performing internal shearing (liquid-liquid shearing);
And a third step of performing external shearing again. A method for producing a fuel cell catalyst paste.
内部剪断機で内部剪断（液−液剪断）を行う第２の工程と、
再度前記外部剪断機または別種の外部剪断機で外部剪断を行う第３の工程と
を具備することを特徴とする燃料電池用触媒ペーストの製造方法。 A first step of mixing catalyst-carrying carbon black, an ion exchange resin, and a solvent, and performing external shearing with an external shearing machine;
A second step of performing internal shearing (liquid-liquid shearing) with an internal shearing machine;
And a third step of performing external shearing again with the external shearing machine or another type of external shearing machine, and a method for producing a catalyst paste for a fuel cell.
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| JP6196201B2 (en) * | 2014-09-25 | 2017-09-13 | 本田技研工業株式会社 | Method for producing catalyst ink |
| JP6746977B2 (en) * | 2016-03-14 | 2020-08-26 | 凸版印刷株式会社 | Method for producing catalyst ink |
| CN115872734A (en) * | 2022-10-27 | 2023-03-31 | 先导薄膜材料（广东）有限公司 | ITO powder reproduced from ITO waste target, high-density target and preparation method thereof |
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