JP2013026014A - Catalyst for fuel cell and manufacturing method of catalyst for fuel cell - Google Patents
Catalyst for fuel cell and manufacturing method of catalyst for fuel cell 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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Abstract
Description
本発明は、コアに貴金属を担持させた燃料電池用触媒及び燃料電池用触媒の製造方法に関する。 The present invention relates to a fuel cell catalyst in which a noble metal is supported on a core and a method for producing the fuel cell catalyst.
従来、燃料電池用電極として、白金等の触媒金属そのものや前記触媒金属を担持したカーボンを電解質樹脂と溶媒と混合してペースト状とし、電解質膜上に直接塗工するなどして形成するものが知られている（例えば、特許文献１参照）。 Conventionally, an electrode for a fuel cell is formed by mixing a catalyst metal itself such as platinum or carbon carrying the catalyst metal with an electrolyte resin and a solvent to form a paste, and directly coating the electrolyte film on the electrolyte membrane. It is known (see, for example, Patent Document 1).
ところで、電極内部の空隙の大きさは、水素や酸素等の電極に供給されるガスの拡散性や、電気化学反応により電極で生成する水の排出性に影響し、ひいては燃料電池の出力に影響を及ぼす。したがって、電極内部の空隙を所望の値に制御できることが望ましい。
しかしながら、上記従来の構成では、電極内部に存在する空隙の大きさを制御すること、特に空隙を大きくすることが困難であった。
本発明は、上述した事情に鑑みてなされたものであり、電極内部の空隙の大きさを制御可能な燃料電池用触媒及び燃料電池用触媒の製造方法を提供することを目的とする。
By the way, the size of the void inside the electrode affects the diffusivity of the gas supplied to the electrode such as hydrogen and oxygen, and the discharge of water generated at the electrode by an electrochemical reaction, and consequently the output of the fuel cell. Effect. Therefore, it is desirable that the gap inside the electrode can be controlled to a desired value.
However, in the above conventional configuration, it is difficult to control the size of the gap existing inside the electrode, and in particular to increase the gap.
The present invention has been made in view of the above-described circumstances, and an object of the present invention is to provide a fuel cell catalyst capable of controlling the size of the gap inside the electrode and a method for producing the fuel cell catalyst.
上記目的を達成するために、本発明は、樹脂製のコアの表面に貴金属触媒を担持させたことを特徴とする。
上記構成によれば、樹脂製のコアの径を制御することで、電極内部の空隙を所望の値に制御することができ、燃料電池の出力を向上させることができる。
In order to achieve the above object, the present invention is characterized in that a noble metal catalyst is supported on the surface of a resin core.
According to the said structure, the space | gap inside an electrode can be controlled to a desired value by controlling the diameter of resin-made cores, and the output of a fuel cell can be improved.
また本発明は、樹脂製のコアと貴金属触媒を溶媒中で混合することにより、前記コア材の表面に前記貴金属触媒を担持させることを特徴とする。
上記構成によれば、樹脂製のコアの表面に貴金属触媒を担持させることができるため、電極内部の空隙の大きさの制御が容易で、燃料電池の出力を向上させることができる燃料電池用触媒を容易に製造できる。
The present invention is also characterized in that the noble metal catalyst is supported on the surface of the core material by mixing a resin core and a noble metal catalyst in a solvent.
According to the above configuration, since the noble metal catalyst can be supported on the surface of the resin core, the size of the void inside the electrode can be easily controlled, and the output of the fuel cell can be improved. Can be easily manufactured.
また本発明は、樹脂製のコアと貴金属触媒を気流中で対向衝突させ、前記コア材の表面に前記貴金属触媒を担持させることを特徴とする。
上記構成によれば、樹脂製のコアの表面に貴金属触媒を担持させることができるため、電極内部の空隙の大きさの制御が容易で、燃料電池の出力を向上させることができる燃料電池用触媒を製造できる。
Further, the present invention is characterized in that a resin core and a noble metal catalyst are caused to face each other in an air flow, and the noble metal catalyst is supported on the surface of the core material.
According to the above configuration, since the noble metal catalyst can be supported on the surface of the resin core, the size of the void inside the electrode can be easily controlled, and the output of the fuel cell can be improved. Can be manufactured.
本発明によれば、樹脂製のコアを用いているため、コアの径を大きくすることで、燃料電池用電極中の空隙が大きくなるので、燃料電池の出力を向上させることができる。
また、樹脂製のコアの表面に貴金属触媒を担持させるため、電気化学反応に有効な貴金属触媒の表面積が広くなり、利用効率が向上した燃料電池用触媒を製造できる。
According to the present invention, since the resin core is used, the gap in the fuel cell electrode is increased by increasing the diameter of the core, so that the output of the fuel cell can be improved.
In addition, since the noble metal catalyst is supported on the surface of the resin core, the surface area of the noble metal catalyst effective for the electrochemical reaction is increased, and a fuel cell catalyst with improved utilization efficiency can be manufactured.
以下、図面を参照して本発明の実施の形態について説明する。
＜第１の実施の形態＞
図１は、第１の実施の形態に係る燃料電池用触媒を示す模式図である。
燃料電池用触媒１は、複数の触媒粒子２を備えている。各触媒粒子２は、樹脂製のコア３の表面に貴金属触媒４を担持させた複合体である。コア３の形状としては、例えば球状やファイバー状が好適である。コア３の材料には、例えば、ポリメチルメタクリレート（polymethylmethacrylate:ＰＭＭＡ）等のアクリル樹脂を用いることができる。本実施の形態のコア３には、積水化成品工業社製のアクリル樹脂（球状、直径約０．８μｍ）が用いられている。
貴金属触媒４は、複数の１次粒子４Ａが凝集して２次粒子（凝集体）４Ｂを形成してなる。２次粒子４Ｂ中には、１次粒子４Ａ間に微空隙Ａが形成されている。貴金属触媒４には、例えば白金黒（ＰｔＢ）を用いることができる。
Embodiments of the present invention will be described below with reference to the drawings.
<First Embodiment>
FIG. 1 is a schematic diagram showing a fuel cell catalyst according to the first embodiment.
The fuel cell catalyst 1 includes a plurality of catalyst particles 2. Each catalyst particle 2 is a composite in which a noble metal catalyst 4 is supported on the surface of a resin core 3. As the shape of the core 3, for example, a spherical shape or a fiber shape is suitable. As the material of the core 3, for example, an acrylic resin such as polymethylmethacrylate (PMMA) can be used. Acrylic resin (spherical, about 0.8 μm in diameter) manufactured by Sekisui Plastics Co., Ltd. is used for the core 3 of the present embodiment.
The noble metal catalyst 4 is formed by agglomerating a plurality of primary particles 4A to form secondary particles (aggregates) 4B. In the secondary particles 4B, fine voids A are formed between the primary particles 4A. For the noble metal catalyst 4, for example, platinum black (PtB) can be used.
図２は、燃料電池用触媒１の製造工程を示す模式図である。
まず、コア３と、貴金属触媒４（図１）を含む貴金属触媒インク１１を用意する。本実施の形態の貴金属触媒インク１１は、例えば、水７．４３ｇと、１−プロパノール（ノルマルプロピルアルコール：ＮＰＡ）１７．３５ｇとを混合した液（溶媒）に、ＰｔＢの貴金属触媒４を４３．６１ｇ混合し、この液を例えば湿式ジェットミルにて粉砕混合することで得られる。
FIG. 2 is a schematic diagram showing the manufacturing process of the fuel cell catalyst 1.
First, a noble metal catalyst ink 11 including a core 3 and a noble metal catalyst 4 (FIG. 1) is prepared. In the noble metal catalyst ink 11 of the present embodiment, for example, a PtB noble metal catalyst 4 is added to a liquid (solvent) obtained by mixing 7.43 g of water and 17.35 g of 1-propanol (normal propyl alcohol: NPA). It is obtained by mixing 61 g and pulverizing and mixing this liquid with, for example, a wet jet mill.
次いで、貴金属触媒インク１１にコア３を投入する（図２（Ａ））。本実施の形態では、例えば、貴金属触媒インク１１にＰＭＭＡのコア３を２ｇ投入することで、ＰＭＭＡに対するＰｔＢの重量比（ＰｔＢ／ＰＭＭＡ）が約１．８である混合液１２を得ている。
次に、混合液１２を超音波分散処理する（図２（Ｂ））。本実施の形態では、例えばブランソン社製の超音波ホモジナイザーを用いて、混合液１２に１０分間超音波分散処理を行うものとする。混合液１２中でコア３と貴金属触媒４を混合すると、ヘテロ凝集原理により、２次粒子４Ｂ（図１）がコア３の表面に凝集付着し、コア３と貴金属触媒４とが複合化した複合化インク１３（燃料電池用触媒１）が得られる。なお、本実施の形態では、超音波を用いて分散処理を行ったが、分散処理を行わなくとも前記複合化は可能である。しかし、複合化を促進するためには分散処理を行うことが好ましい。
そして、図２（Ｃ）に示すように、得られた複合化インク１３をポリエチレンテレフタレート（ＰＥＴ）や電解質膜等の基材５の両面に塗布した後乾燥することで、電極層（電極）６が形成される。電極層６の一方はアノード、他方はカソードとなり、アノードに還元剤（燃料）ガス（例えば、水素）が供給され、カソードには酸化剤ガス（例えば、酸素）が供給され、電極層６間で電気化学反応に基づいて発電されることとなる。
Next, the core 3 is put into the noble metal catalyst ink 11 (FIG. 2A). In the present embodiment, for example, 2 g of PMMA core 3 is added to the noble metal catalyst ink 11 to obtain a mixed liquid 12 having a PtB to PMMA weight ratio (PtB / PMMA) of about 1.8.
Next, the mixed liquid 12 is subjected to ultrasonic dispersion treatment (FIG. 2B). In this embodiment, for example, an ultrasonic dispersion process is performed on the mixed solution 12 for 10 minutes using an ultrasonic homogenizer manufactured by Branson. When the core 3 and the noble metal catalyst 4 are mixed in the mixed solution 12, the secondary particles 4B (FIG. 1) are aggregated and adhered to the surface of the core 3 due to the hetero-aggregation principle, and the core 3 and the noble metal catalyst 4 are combined. The ink 13 (fuel cell catalyst 1) is obtained. In this embodiment, the dispersion processing is performed using ultrasonic waves. However, the above-described combination is possible without performing the dispersion processing. However, it is preferable to perform a dispersion process in order to promote the composite.
And as shown in FIG.2 (C), the obtained composite ink 13 is apply | coated to both surfaces of base materials 5, such as a polyethylene terephthalate (PET) and an electrolyte film, Then, it is dried, The electrode layer (electrode) 6 Is formed. One of the electrode layers 6 is an anode, and the other is a cathode. A reducing agent (fuel) gas (for example, hydrogen) is supplied to the anode, and an oxidant gas (for example, oxygen) is supplied to the cathode. Electric power is generated based on the electrochemical reaction.
図３は、図２の製造工程で得られた燃料電池用触媒１を示す写真であり、図３（Ａ）は燃料電池用触媒１を倍率１万倍で示す写真であり、図３（Ｂ）は燃料電池用触媒１を倍率３万倍で示す写真である。
この図に示すように、燃料電池用触媒１においては、コア３の表面に２次粒子４Ｂが隙間なく、かつ、均一に担持されており、燃料電池用触媒１の歩留まりが高く（１００％に近く）、生産性が向上する。また、２次粒子４Ｂの構造は破壊されておらず、２次粒子４Ｂ中の微空隙Ａ（図１）は閉塞することなく保たれている。さらに、径が比較的大きいコア３により、触媒粒子２間に広い空隙Ｂが形成される。
FIG. 3 is a photograph showing the fuel cell catalyst 1 obtained in the manufacturing process of FIG. 2, and FIG. 3A is a photograph showing the fuel cell catalyst 1 at a magnification of 10,000 times, and FIG. ) Is a photograph showing the fuel cell catalyst 1 at a magnification of 30,000 times.
As shown in this figure, in the fuel cell catalyst 1, the secondary particles 4B are uniformly supported on the surface of the core 3 without any gaps, and the yield of the fuel cell catalyst 1 is high (100%). Near), productivity is improved. Further, the structure of the secondary particles 4B is not destroyed, and the microvoids A (FIG. 1) in the secondary particles 4B are kept without being blocked. Furthermore, wide voids B are formed between the catalyst particles 2 by the core 3 having a relatively large diameter.
ここで、水銀圧入法による燃料電池用触媒１の細孔分布を図４に示す。なお、図４において、Ｄ０は従来のＰｔＢ触媒の細孔分布を、Ｄ１は燃料電池用触媒１の細孔分布を示す。また、Ｐ０はＰｔＢ触媒の細孔容積が最も多い細孔径を、Ｐ１は燃料電池用触媒１の細孔容積が最も多い細孔径を示す。
ＰｔＢ触媒の細孔径Ｐ０と、燃料電池用触媒１の細孔径Ｐ１を比較すると、燃料電池用触媒１の方が細孔径が大きくなっている。
Here, the pore distribution of the fuel cell catalyst 1 by mercury porosimetry is shown in FIG. In FIG. 4, D0 represents the pore distribution of the conventional PtB catalyst, and D1 represents the pore distribution of the fuel cell catalyst 1. P0 represents the pore diameter with the largest pore volume of the PtB catalyst, and P1 represents the pore diameter with the largest pore volume of the fuel cell catalyst 1.
When the pore diameter P0 of the PtB catalyst and the pore diameter P1 of the fuel cell catalyst 1 are compared, the fuel cell catalyst 1 has a larger pore diameter.
このように、燃料電池用触媒１では、１次粒子４Ａ間と、触媒粒子２間とに比較的大きな細孔（微空隙Ａ、空隙Ｂ）が形成されるので、燃料電池用触媒１を用いて電極層６を形成すると、従来２次粒子の中心付近で反応に寄与していなかった１次粒子を少なくして貴金属触媒４の有効表面積を広くできるとともに、図１に矢印で示すように、例えば酸化剤ガスである酸素が１次粒子４Ａ間及び触媒粒子２間を円滑に拡散する。したがって、本実施の形態では、従来のＰｔＢ触媒と同等の導電性を確保できる上、従来のＰｔＢ触媒に場合に比べて電極層６の触媒の利用効率を向上させることができる。また、従来のＰｔＢ触媒では空隙の大きさを制御できなかったが、本実施の形態では、コア３の大きさにより触媒粒子２間の空隙Ｂを制御できる。 As described above, in the fuel cell catalyst 1, relatively large pores (fine voids A and voids B) are formed between the primary particles 4 </ b> A and between the catalyst particles 2, so that the fuel cell catalyst 1 is used. When the electrode layer 6 is formed, it is possible to increase the effective surface area of the noble metal catalyst 4 by reducing the number of primary particles that have not conventionally contributed to the reaction in the vicinity of the center of the secondary particles, and as indicated by arrows in FIG. For example, oxygen, which is an oxidant gas, smoothly diffuses between the primary particles 4A and between the catalyst particles 2. Therefore, in this embodiment, the same conductivity as that of the conventional PtB catalyst can be ensured, and the utilization efficiency of the catalyst of the electrode layer 6 can be improved as compared with the case of the conventional PtB catalyst. In addition, the conventional PtB catalyst cannot control the size of the void, but in the present embodiment, the void B between the catalyst particles 2 can be controlled by the size of the core 3.
形成された電極層６は黒色度が高く、見た目からもＰｔＢがＰＭＭＡに良好に被覆していることは明らかである。また、複合体インク３３をそのまま基材５に塗布すれば電極層６が得られるので、電極層６を容易に形成できる。
これに加え、コア３と貴金属触媒４との超音波による複合化には、市販の超音波ホモジナイザーを用いたため、例えばメカノケミカル処理等の物理的衝撃を与える大掛かりな専用装置が必要なく、コア３と貴金属触媒４とを容易に複合化できる。
The formed electrode layer 6 has high blackness, and it is clear from the appearance that PtB is well coated with PMMA. Moreover, since the electrode layer 6 is obtained if the composite ink 33 is applied to the substrate 5 as it is, the electrode layer 6 can be easily formed.
In addition, since the commercially available ultrasonic homogenizer is used for the composite of the core 3 and the noble metal catalyst 4 by the ultrasonic wave, a large dedicated device for applying a physical impact such as mechanochemical treatment is not necessary. And the noble metal catalyst 4 can be easily combined.
以上説明したように、本実施の形態によれば、樹脂製のコア３の表面に貴金属触媒４を担持させる構成とした。樹脂製のコア３を用いているため、コア３の径を大きくすることで、貴金属触媒４の有効表面積が広くなるとともに、燃料電池用触媒１の空隙Ｂが大きくなるので、利用効率を向上できる。 As described above, according to the present embodiment, the noble metal catalyst 4 is supported on the surface of the resin core 3. Since the resin core 3 is used, increasing the diameter of the core 3 increases the effective surface area of the noble metal catalyst 4 and increases the void B of the fuel cell catalyst 1, thereby improving the utilization efficiency. .
また、本実施の形態によれば、樹脂製のコア３と貴金属触媒４とを溶媒中で混合して、コア３の表面に貴金属触媒４を担持させて燃料電池用触媒１を製造した。この製造方法により、樹脂製のコア３の表面に貴金属触媒４を担持させることができるため、利用効率が向上した燃料電池用触媒１を製造できる。 Further, according to the present embodiment, the resin core 3 and the noble metal catalyst 4 are mixed in a solvent, and the noble metal catalyst 4 is supported on the surface of the core 3 to manufacture the fuel cell catalyst 1. By this production method, the noble metal catalyst 4 can be supported on the surface of the resin core 3, and therefore the fuel cell catalyst 1 with improved utilization efficiency can be produced.
但し、上記実施の形態は本発明の一態様であり、本発明の趣旨を逸脱しない範囲において適宜変更可能であるのは勿論である。
例えば、上記実施の形態では、燃料電池用触媒１を基材５に塗布して電極層６を形成したが、燃料電池用触媒１を乾燥させて粉末化してもよい。燃料電池用触媒１は、粉末状であってもＰｔＢがＰＭＭＡに良好に被覆している。
However, the above embodiment is an aspect of the present invention, and it is needless to say that the embodiment can be appropriately changed without departing from the gist of the present invention.
For example, in the above embodiment, the fuel cell catalyst 1 is applied to the base material 5 to form the electrode layer 6. However, the fuel cell catalyst 1 may be dried to be powdered. Even if the catalyst 1 for fuel cells is a powder form, PtB has coat | covered PMMA favorable.
また、上記実施の形態では、貴金属触媒４にＰｔＢを用いたが、貴金属触媒４の材料はこれに限定されるものではなく、例えば白金担持カーボン（ＰｔＣ）を用いてもよい。図５は、燃料電池用触媒１を拡大して示す図であり、図５（Ａ）は貴金属触媒４にＰｔＢを用いた燃料電池用触媒１を倍率５万倍及び１００万倍で示す写真であり、図５（Ｂ）は貴金属触媒４にＰｔＣを用いた燃料電池用触媒１を倍率５万倍及び５０万倍で示す写真である。この図に示すように、貴金属触媒４に白金担持カーボンを用いても、コア３と貴金属触媒４とを複合化できる。 Moreover, in the said embodiment, although PtB was used for the noble metal catalyst 4, the material of the noble metal catalyst 4 is not limited to this, For example, you may use platinum carrying | support carbon (PtC). FIG. 5 is an enlarged view of the fuel cell catalyst 1. FIG. 5A is a photograph showing the fuel cell catalyst 1 using PtB as the noble metal catalyst 4 at a magnification of 50,000 times and 1 million times. FIG. 5B is a photograph showing the fuel cell catalyst 1 using PtC as the noble metal catalyst 4 at a magnification of 50,000 times and 500,000 times. As shown in this figure, the core 3 and the noble metal catalyst 4 can be combined even if platinum-supported carbon is used for the noble metal catalyst 4.
＜第２の実施の形態＞
次に、本発明に係る第２の実施の形態を説明する。
図６は、第２の実施の形態に係る燃料電池用触媒を示す模式図である。なお、図６では、図１に示す燃料電池用触媒１と同一部分には同一の符号を付して説明を省略する。
燃料電池用触媒１００の貴金属触媒４は、複数の１次粒子４Ａが凝集して２次粒子（凝集体）１０４Ｂを形成してなる。２次粒子１０４Ｂは微空隙Ａが閉塞した２次粒子４Ｂ（図７参照）であり、２次粒子１０４Ｂ中には１次粒子４Ａ間に微空隙Ａが形成されていない。
<Second Embodiment>
Next, a second embodiment according to the present invention will be described.
FIG. 6 is a schematic view showing a fuel cell catalyst according to the second embodiment. In FIG. 6, the same parts as those of the fuel cell catalyst 1 shown in FIG.
The noble metal catalyst 4 of the fuel cell catalyst 100 is formed by agglomerating a plurality of primary particles 4A to form secondary particles (aggregates) 104B. The secondary particles 104B are secondary particles 4B (see FIG. 7) in which the fine voids A are closed, and no fine voids A are formed between the primary particles 4A in the secondary particles 104B.
図７は、燃料電池用触媒１００の製造工程を示す模式図である。
まず、図７（Ａ）に示すように、コア３及び貴金属触媒４を用意する。このとき、貴金属触媒４の２次粒子４Ｂ中には、１次粒子４Ａ間に微空隙Ａが形成されている。
これらのコア３及び貴金属触媒４を混合し、混合したコア３及び貴金属触媒４を高速気流衝突装置１２０によって高速気流中で対向衝突させる。高速気流衝突装置１２０には、例えば奈良機械製作所社製のハイブリダイゼーションシステムを用いることができる。高速気流衝突装置１２０は、円筒状のステータ１２１と、ステータ１２１内に回転可能に配置されるロータ１２２と、ロータ１２２の外周部からロータ１２２の回転中心部に延出する再循環パイプ１２３と、再循環パイプ１２３に形成された材料供給口１２４とを備えており、ステータ１２１の内側及び再循環パイプ１２３が処理室１２５を構成している。
FIG. 7 is a schematic diagram showing a manufacturing process of the fuel cell catalyst 100.
First, as shown in FIG. 7A, a core 3 and a noble metal catalyst 4 are prepared. At this time, in the secondary particles 4B of the noble metal catalyst 4, fine voids A are formed between the primary particles 4A.
The core 3 and the noble metal catalyst 4 are mixed, and the mixed core 3 and the noble metal catalyst 4 are opposed to each other in a high speed air current by the high speed air current collision device 120. For example, a hybridization system manufactured by Nara Machinery Co., Ltd. can be used for the high-speed airflow collision device 120. The high-speed airflow collision device 120 includes a cylindrical stator 121, a rotor 122 that is rotatably disposed in the stator 121, a recirculation pipe 123 that extends from the outer periphery of the rotor 122 to the rotation center of the rotor 122, The material supply port 124 formed in the recirculation pipe 123 is provided, and the inside of the stator 121 and the recirculation pipe 123 constitute a processing chamber 125.
混合したコア３及び貴金属触媒４を材料供給口１２４から処理室１２５に投入し、ロータ１０２を所定の回転速度で回転させると、実線矢印で示すように高速気流が生じ、コア３及び貴金属触媒４が分散するとともに、コア３と貴金属触媒４とが衝突することで、コア３の表面に貴金属触媒４が付着して、コア３と貴金属触媒４とが複合化する。
ロータ１２２の回転数（回転速度）は、高回転の方が複合化能力が高く、コア３の表面に貴金属触媒４が隙間なく付着する。２次粒子が破壊されやすい材料等を用いる場合には、ロータ１２２の回転数を低回転とするのがよい。また、実験によれば、処理時間が約３分でコア３と貴金属触媒４との複合化がほぼ完了する。
When the mixed core 3 and noble metal catalyst 4 are introduced into the processing chamber 125 from the material supply port 124 and the rotor 102 is rotated at a predetermined rotational speed, a high-speed air current is generated as indicated by the solid line arrow, and the core 3 and the noble metal catalyst 4 Is dispersed, and the core 3 and the noble metal catalyst 4 collide with each other, so that the noble metal catalyst 4 adheres to the surface of the core 3 and the core 3 and the noble metal catalyst 4 are combined.
The rotational speed (rotational speed) of the rotor 122 is higher when the rotational speed is higher, and the noble metal catalyst 4 adheres to the surface of the core 3 without a gap. In the case of using a material that easily breaks secondary particles, it is preferable to set the rotational speed of the rotor 122 to a low speed. Further, according to the experiment, the combination of the core 3 and the noble metal catalyst 4 is almost completed in about 3 minutes.
本実施の形態では、例えば、ＰＭＭＡのコア３を５ｇ、及び、ＰｔＢの貴金属触媒４を９．０１ｇ混合し、ＰＭＭＡに対するＰｔＢの重量比（ＰｔＢ／ＰＭＭＡ）を約１．８としている。そして、ロータ１２２の回転速度を約６０−１００メートル／秒とし、混合したコア３及び貴金属触媒４を窒素ガス中で約１０分間処理を行うものとする。これにより、図６に示すように、２次粒子１０４Ｂがコア３の表面に凝集付着し、コア３と貴金属触媒４とが複合化した燃料電池用触媒１００が得られる。
そして、この燃料電池用触媒１００を所定の液に投入して複合化インク１１３を生成し、図７（Ｂ）に示すように、生成した複合化インク１１３をポリエチレンテレフタレート（ＰＥＴ）や電解質膜等の基材５に塗布した後乾燥することで、電極層６が形成される。
In this embodiment, for example, 5 g of PMMA core 3 and 9.01 g of PtB noble metal catalyst 4 are mixed, and the weight ratio of PtB to PMMA (PtB / PMMA) is about 1.8. Then, the rotational speed of the rotor 122 is set to about 60-100 meters / second, and the mixed core 3 and noble metal catalyst 4 are treated in nitrogen gas for about 10 minutes. As a result, as shown in FIG. 6, the secondary particles 104 </ b> B aggregate and adhere to the surface of the core 3, and the fuel cell catalyst 100 in which the core 3 and the noble metal catalyst 4 are combined is obtained.
Then, the fuel cell catalyst 100 is put into a predetermined liquid to generate a composite ink 113. As shown in FIG. 7B, the generated composite ink 113 is made of polyethylene terephthalate (PET), an electrolyte membrane, or the like. The electrode layer 6 is formed by applying to the substrate 5 and drying.
図８は、図７の製造工程で得られた燃料電池用触媒１００を示す写真であり、図８（Ａ）は燃料電池用触媒１００を倍率１万倍で示す写真であり、図８（Ｂ）は燃料電池用触媒１００を倍率３万倍で示す写真である。
この図に示すように、燃料電池用触媒１００においては、２次粒子１０４Ｂ中の微空隙は閉塞し、コア３の表面に２次粒子１０４Ｂが隙間なく担持されている。また、径が比較的大きいコア３により、触媒粒子２間に広い空隙Ｂが形成される。
FIG. 8 is a photograph showing the fuel cell catalyst 100 obtained in the manufacturing process of FIG. 7, and FIG. 8A is a photograph showing the fuel cell catalyst 100 at a magnification of 10,000 times, and FIG. ) Is a photograph showing the fuel cell catalyst 100 at a magnification of 30,000 times.
As shown in this figure, in the fuel cell catalyst 100, the fine voids in the secondary particles 104B are closed, and the secondary particles 104B are supported on the surface of the core 3 without any gaps. Further, a wide void B is formed between the catalyst particles 2 by the core 3 having a relatively large diameter.
ここで、図４において、Ａ２は燃料電池用触媒１００の細孔分布を、Ｐ２は燃料電池用触媒１００の細孔容積が最も多い細孔径を示す。ＰｔＢ触媒の細孔径Ｐ０と、燃料電池用触媒１００の細孔径Ｐ２を比較すると、燃料電池用触媒１００の方が細孔径が大きくなっている。
このように、燃料電池用触媒１００では、触媒粒子２間に比較的大きな細孔（空隙Ｂ）が形成されるので、燃料電池用触媒１００を用いて電極層６を形成すると、従来２次粒子の中心付近で反応に寄与していなかった１次粒子を少なくして貴金属触媒４の有効表面積を広くできるとともに、図６に矢印で示すように、例えば酸化剤ガスである酸素が触媒粒子２間を円滑に拡散する。したがって、本実施の形態では、従来のＰｔＢ触媒と同等の導電性を確保できる上、従来のＰｔＢ触媒に場合に比べて電極層６の利用効率を向上させることができる。また、従来のＰｔＢ触媒では空隙の大きさを制御できなかったが、本実施の形態では、コア３の大きさにより触媒粒子２間の空隙Ｂを制御できる。
形成された電極層６は黒色度が高く、見た目からもＰｔＢがＰＭＭＡに良好に被覆していることは明らかである。
Here, in FIG. 4, A2 represents the pore distribution of the fuel cell catalyst 100, and P2 represents the pore diameter with the largest pore volume of the fuel cell catalyst 100. When the pore diameter P0 of the PtB catalyst is compared with the pore diameter P2 of the fuel cell catalyst 100, the fuel cell catalyst 100 has a larger pore diameter.
In this way, in the fuel cell catalyst 100, relatively large pores (voids B) are formed between the catalyst particles 2, so that when the electrode layer 6 is formed using the fuel cell catalyst 100, the conventional secondary particles are formed. The primary particles that have not contributed to the reaction in the vicinity of the center of the catalyst can be reduced to increase the effective surface area of the noble metal catalyst 4 and, for example, oxygen as an oxidant gas is present between the catalyst particles 2 as indicated by arrows in FIG. To diffuse smoothly. Therefore, in the present embodiment, the same conductivity as that of the conventional PtB catalyst can be ensured, and the utilization efficiency of the electrode layer 6 can be improved as compared with the case of the conventional PtB catalyst. In addition, the conventional PtB catalyst cannot control the size of the void, but in the present embodiment, the void B between the catalyst particles 2 can be controlled by the size of the core 3.
The formed electrode layer 6 has high blackness, and it is clear from the appearance that PtB is well coated with PMMA.
以上説明したように、本実施の形態によれば、樹脂製のコア３と貴金属触媒４を気流中で対向衝突させ、コア３の表面に貴金属触媒４を担持させて燃料電池用触媒１００を製造した。この製造方法により、樹脂製のコア３の表面に貴金属触媒４を担持させることができるため、利用効率が向上した燃料電池用触媒１００を製造できる。 As described above, according to the present embodiment, the resin core 3 and the noble metal catalyst 4 face each other in an air flow, and the noble metal catalyst 4 is supported on the surface of the core 3 to manufacture the fuel cell catalyst 100. did. With this manufacturing method, the noble metal catalyst 4 can be supported on the surface of the resin core 3, and therefore the fuel cell catalyst 100 with improved utilization efficiency can be manufactured.
＜第３の実施の形態＞
次に、本発明に係る第３の実施の形態を説明する。第３の実施の形態の燃料電池用触媒２００は、図６に示す燃料電池用触媒１００と同一の構成である。
図９は、第３の実施の形態の燃料電池用触媒２００の製造工程を示す模式図である。
まず、コア３及び貴金属触媒４を用意し、コア３及び貴金属触媒４を混合して得た処理粉体２１２を、ミル装置２２０によって高速気流中で衝突させる。ミル装置２２０には、例えばホソカワミクロン社製のノビルタ（NOB-MINI）を用いることができる。ミル装置２２０は、円筒状のステータ２２１と、ステータ２２１内に回転可能に配置されるロータ２２２とを備えている。
<Third Embodiment>
Next, a third embodiment according to the present invention will be described. The fuel cell catalyst 200 of the third embodiment has the same configuration as the fuel cell catalyst 100 shown in FIG.
FIG. 9 is a schematic diagram illustrating a manufacturing process of the fuel cell catalyst 200 according to the third embodiment.
First, the core 3 and the noble metal catalyst 4 are prepared, and the treated powder 212 obtained by mixing the core 3 and the noble metal catalyst 4 is collided in the high-speed air current by the mill device 220. As the mill device 220, for example, NOB-MINI manufactured by Hosokawa Micron Corporation can be used. The mill device 220 includes a cylindrical stator 221 and a rotor 222 that is rotatably disposed in the stator 221.
処理粉体２１２をミル装置２２０に投入し、ロータ２２２を所定の回転速度で回転させると、ステータ２２１の壁面２２１Ａとロータ２２２との間の剪断力によって分散するとともに、ステータ２２１の壁面２２１Ａとロータ２２２との間でコア３と貴金属触媒４とが衝突することで、コア３の表面に貴金属触媒４が付着して、コア３と貴金属触媒４とが複合化する。 When the treated powder 212 is put into the mill device 220 and the rotor 222 is rotated at a predetermined rotational speed, the processed powder 212 is dispersed by the shearing force between the wall surface 221A of the stator 221 and the rotor 222, and the wall surface 221A of the stator 221 and the rotor When the core 3 and the noble metal catalyst 4 collide with 222, the noble metal catalyst 4 adheres to the surface of the core 3 and the core 3 and the noble metal catalyst 4 are combined.
本実施の形態では、例えば、ＰＭＭＡのコア３を５ｇ、及び、ＰｔＢの貴金属触媒４を９．０１ｇ混合することで、ＰＭＭＡに対するＰｔＢの重量比（ＰｔＢ／ＰＭＭＡ）が約１．８である処理粉体２１２を得ている。そして、ロータ２２２の回転速度を約６０００−９０００ｒｐｍとし、処理粉体２１２を窒素ガス中で約１０分間処理を行うものとする。これにより、図６に示すように、２次粒子１０４Ｂがコア３の表面に凝集付着し、コア３と貴金属触媒４とが複合化した燃料電池用触媒２００が得られる。
そして、この燃料電池用触媒２００を所定の液に投入して複合化インク２１３を生成し、図９（Ｂ）に示すように、生成した複合化インク２１３をポリエチレンテレフタレート（ＰＥＴ）や電解質膜等の基材５に塗布した後乾燥することで、電極層６が形成される。
In the present embodiment, for example, 5 g of PMMA core 3 and 9.01 g of PtB noble metal catalyst 4 are mixed, whereby the weight ratio of PtB to PMMA (PtB / PMMA) is about 1.8. A powder 212 is obtained. Then, the rotational speed of the rotor 222 is about 6000 to 9000 rpm, and the treated powder 212 is treated in nitrogen gas for about 10 minutes. As a result, as shown in FIG. 6, the secondary particles 104B aggregate and adhere to the surface of the core 3, and the fuel cell catalyst 200 in which the core 3 and the noble metal catalyst 4 are combined is obtained.
Then, the fuel cell catalyst 200 is put into a predetermined liquid to generate a composite ink 213. As shown in FIG. 9B, the generated composite ink 213 is made of polyethylene terephthalate (PET), an electrolyte membrane, or the like. The electrode layer 6 is formed by applying to the substrate 5 and drying.
図１０は、図９の製造工程で得られた燃料電池用触媒２００を示す写真であり、図１０（Ａ）は燃料電池用触媒２００を倍率１万倍で示す写真であり、図１０（Ｂ）は燃料電池用触媒２００を倍率３万倍で示す写真である。
この図に示すように、燃料電池用触媒１００においては、２次粒子１０４Ｂ中の微空隙は閉塞し、コア３の表面に２次粒子１０４Ｂが担持されている。しかしながら、コア３と貴金属触媒４との複合化にはばらつきがあり、図８に示す燃料電池用触媒２００に比べて、複合化能力が低い。また、径が比較的大きいコア３により、触媒粒子２間に広い空隙Ｂが形成される。
FIG. 10 is a photograph showing the fuel cell catalyst 200 obtained in the manufacturing process of FIG. 9, and FIG. 10 (A) is a photograph showing the fuel cell catalyst 200 at a magnification of 10,000 times, and FIG. ) Is a photograph showing the fuel cell catalyst 200 at a magnification of 30,000 times.
As shown in this figure, in the fuel cell catalyst 100, the fine voids in the secondary particles 104 </ b> B are closed, and the secondary particles 104 </ b> B are supported on the surface of the core 3. However, the composite of the core 3 and the noble metal catalyst 4 varies, and the composite ability is low as compared with the fuel cell catalyst 200 shown in FIG. Further, a wide void B is formed between the catalyst particles 2 by the core 3 having a relatively large diameter.
このように、燃料電池用触媒２００では、触媒粒子２間に比較的大きな細孔（空隙Ｂ）が形成されるので、燃料電池用触媒２００を用いて電極層６を形成すると、従来２次粒子の中心付近で反応に寄与していなかった１次粒子を少なくして貴金属触媒４の有効表面積を広くできるとともに、図６に矢印で示すように、例えば酸化剤ガスである酸素が触媒粒子２間を円滑に拡散する。したがって、本実施の形態では、従来のＰｔＢ触媒と同等の導電性を確保できる上、従来のＰｔＢ触媒に場合に比べて電極層６の利用効率を向上させることができる。また、従来のＰｔＢ触媒では空隙の大きさを制御できなかったが、本実施の形態では、コア３の大きさにより触媒粒子２間の空隙Ｂを制御できる。
形成された電極層６は黒色度が高く、見た目からもＰｔＢがＰＭＭＡに良好に被覆していることは明らかである。
Thus, in the fuel cell catalyst 200, relatively large pores (voids B) are formed between the catalyst particles 2. Therefore, when the electrode layer 6 is formed using the fuel cell catalyst 200, conventional secondary particles are formed. The primary particles that have not contributed to the reaction in the vicinity of the center of the catalyst can be reduced to increase the effective surface area of the noble metal catalyst 4 and, for example, oxygen as an oxidant gas is present between the catalyst particles 2 as indicated by arrows in FIG. To diffuse smoothly. Therefore, in the present embodiment, the same conductivity as that of the conventional PtB catalyst can be ensured, and the utilization efficiency of the electrode layer 6 can be improved as compared with the case of the conventional PtB catalyst. In addition, the conventional PtB catalyst cannot control the size of the void, but in the present embodiment, the void B between the catalyst particles 2 can be controlled by the size of the core 3.
The formed electrode layer 6 has high blackness, and it is clear from the appearance that PtB is well coated with PMMA.
また、上記実施の形態では、樹脂製のコア３と貴金属触媒４を気流中で対向衝突させ、コア３の表面に貴金属触媒４を担持させて燃料電池用触媒２００を製造した。この製造方法により、樹脂製のコア３の表面に貴金属触媒４を担持させることができるため、耐食性に優れ利用効率が向上した燃料電池用触媒２００を製造できる。 Further, in the above-described embodiment, the fuel core catalyst 200 is manufactured by causing the resin core 3 and the noble metal catalyst 4 to face each other in an air flow and supporting the noble metal catalyst 4 on the surface of the core 3. By this production method, the noble metal catalyst 4 can be supported on the surface of the resin core 3, so that the fuel cell catalyst 200 having excellent corrosion resistance and improved utilization efficiency can be produced.
１，１００，２００ 燃料電池用触媒
３ コア
４ 貴金属触媒
1,100,200 Fuel cell catalyst 3 Core 4 Noble metal catalyst
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| JP2017084476A (en) * | 2015-10-23 | 2017-05-18 | 積水化学工業株式会社 | Resin particle, electrode material and fuel cell electrode |
| JP2020140843A (en) * | 2019-02-28 | 2020-09-03 | 正己 奥山 | Electrode and method for manufacturing the same |
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