JPH0465499B2 - - Google Patents
Info
- Publication number
- JPH0465499B2 JPH0465499B2 JP59223309A JP22330984A JPH0465499B2 JP H0465499 B2 JPH0465499 B2 JP H0465499B2 JP 59223309 A JP59223309 A JP 59223309A JP 22330984 A JP22330984 A JP 22330984A JP H0465499 B2 JPH0465499 B2 JP H0465499B2
- Authority
- JP
- Japan
- Prior art keywords
- paste
- base material
- electrode base
- roll
- water repellent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000000463 material Substances 0.000 claims description 70
- 239000005871 repellent Substances 0.000 claims description 57
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 53
- 230000002940 repellent Effects 0.000 claims description 41
- 238000000576 coating method Methods 0.000 claims description 19
- 239000000446 fuel Substances 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 19
- -1 polytetrafluoroethylene Polymers 0.000 claims description 19
- 239000011248 coating agent Substances 0.000 claims description 18
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 18
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 18
- 238000004821 distillation Methods 0.000 claims description 13
- 238000007789 sealing Methods 0.000 claims description 11
- 239000002270 dispersing agent Substances 0.000 claims description 6
- 238000005192 partition Methods 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 4
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical group [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 4
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 239000002562 thickening agent Substances 0.000 claims description 4
- 229910000166 zirconium phosphate Inorganic materials 0.000 claims description 4
- LEHFSLREWWMLPU-UHFFFAOYSA-B zirconium(4+);tetraphosphate Chemical compound [Zr+4].[Zr+4].[Zr+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LEHFSLREWWMLPU-UHFFFAOYSA-B 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 3
- 239000002736 nonionic surfactant Substances 0.000 claims description 3
- 238000002474 experimental method Methods 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 5
- 239000010419 fine particle Substances 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Substances OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 230000002093 peripheral effect Effects 0.000 description 3
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 2
- 241000519995 Stachys sylvatica Species 0.000 description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 description 2
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 2
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000010422 painting Methods 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 238000010248 power generation Methods 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 230000000007 visual effect Effects 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000001846 repelling effect Effects 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- RPACBEVZENYWOL-XFULWGLBSA-M sodium;(2r)-2-[6-(4-chlorophenoxy)hexyl]oxirane-2-carboxylate Chemical compound [Na+].C=1C=C(Cl)C=CC=1OCCCCCC[C@]1(C(=O)[O-])CO1 RPACBEVZENYWOL-XFULWGLBSA-M 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 230000003313 weakening effect Effects 0.000 description 1
Classifications
-
- 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
- H01M4/8878—Treatment steps after deposition of the catalytic active composition or after shaping of the electrode being free-standing body
- H01M4/8892—Impregnation or coating of the catalyst layer, e.g. by an ionomer
-
- 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
- H01M4/8663—Selection of inactive substances as ingredients for catalytic active masses, e.g. binders, fillers
-
- 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
- H01M4/8878—Treatment steps after deposition of the catalytic active composition or after shaping of the electrode being free-standing body
- H01M4/8882—Heat treatment, e.g. drying, baking
-
- 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
- H01M4/8878—Treatment steps after deposition of the catalytic active composition or after shaping of the electrode being free-standing body
- H01M4/8896—Pressing, rolling, calendering
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Coating Apparatus (AREA)
- Inert Electrodes (AREA)
Description
【発明の詳細な説明】
〔産業上の利用分野〕
この発明は、燃料電池用電極基材処理方法に関
し、特に電極基材の撥水処理およびシール処理方
法に関するものである。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a method for treating an electrode base material for a fuel cell, and particularly to a method for water repellent treatment and sealing treatment of an electrode base material.
燃料電池は火力発電に代わる発電システムに用
いられるものとして広く知られている。燃料電池
のような電気化学的電池においては、多数の電極
を積層して構成されており、その中の１つでも不
良の電極が存在すると電池全体の運転に支障をき
たす。従つて電極の製造プロセスにおいては良品
を大量に生産できることが必要となる。
Fuel cells are widely known as being used in power generation systems that replace thermal power generation. An electrochemical cell such as a fuel cell is constructed by laminating a large number of electrodes, and if even one of the electrodes is defective, the operation of the entire cell will be affected. Therefore, in the electrode manufacturing process, it is necessary to be able to produce a large number of good products.
第６図はリン酸型燃料電池の電極構成を示す断
面図である。図において、１は空気極、２は燃料
極で、この場合は空気極１と燃料極２を離して示
している。空気極１は、電極基材、例えば300〜
600μｍ程度の厚さのカーボンペーパー３と、50
〜200μｍ程度の触媒層４、およびフツ素ゴムよ
り成るパツキング５とで構成されている。また、
燃料極２はカーボンペーパー３、30〜150μｍ程
度の触媒層８、シール処理されたウエツトシール
部６、周辺ガスシール部７および150μｍ程度の
マトリツクス層９から成つている。なお、マトリ
ツクス層９は独立膜として形成される場合もあ
る。 FIG. 6 is a sectional view showing the electrode structure of a phosphoric acid fuel cell. In the figure, 1 is an air electrode, and 2 is a fuel electrode, and in this case, the air electrode 1 and the fuel electrode 2 are shown separated. The air electrode 1 has an electrode base material, e.g.
Carbon paper 3 with a thickness of about 600 μm and 50
It consists of a catalyst layer 4 of about 200 μm and a packing 5 made of fluorocarbon rubber. Also,
The fuel electrode 2 consists of a carbon paper 3, a catalyst layer 8 of about 30 to 150 .mu.m, a sealed wet seal section 6, a peripheral gas seal section 7, and a matrix layer 9 of about 150 .mu.m. Note that the matrix layer 9 may be formed as an independent film.
電極の製造プロセスとしては、空気極１の場合
カーボンペーパー３の撥水処理工程と触媒層４の
塗工工程の２つの工程があり、燃料極２の場合、
カーボンペーパー３の撥水処理工程、ウエツトシ
ール部６のシール処理工程、触媒層８の塗工工
程、周辺ガスシール部７の塗工工程、およびマト
リツクス層９の塗工工程の５つの工程がある。な
お燃料極２のウエツトシール部６と周辺ガスシー
ル部７は、ウエツトシール部６下部に設けらたた
リン酸補給機構（外部リザーバ）からマトリツク
ス層９へリン酸を補給する際の経路としても重要
な役割を持つている。 In the case of the air electrode 1, the manufacturing process of the electrode includes two steps: a water-repellent treatment step for the carbon paper 3 and a coating step for the catalyst layer 4, and in the case of the fuel electrode 2,
There are five steps: a water repellent treatment step for the carbon paper 3, a seal treatment step for the wet seal portion 6, a coating step for the catalyst layer 8, a coating step for the peripheral gas seal portion 7, and a coating step for the matrix layer 9. The wet seal portion 6 and the peripheral gas seal portion 7 of the fuel electrode 2 are also important routes for replenishing phosphoric acid from the phosphoric acid replenishment mechanism (external reservoir) provided at the bottom of the wet seal portion 6 to the matrix layer 9. have a role.
電極の製造プロセスの中で電極基材３の撥水処
理工程は、電解液によつて電極基材３が濡れて触
媒層４，８へのガス拡散が悪くなるのを防止する
と共に電極基材３の電解液による腐食を防ぐため
に必要となる。 In the electrode manufacturing process, the water-repellent treatment step for the electrode base material 3 prevents the electrode base material 3 from getting wet with the electrolyte and impairs gas diffusion to the catalyst layers 4 and 8, and also prevents the electrode base material 3 from becoming wet with the electrolytic solution. This is necessary to prevent corrosion caused by the electrolyte in step 3.
撥水処理は例えば電極基材３にポリテトラフル
オロエチレンの微粒子を付着させ、320℃以上の
温度でポリテトラフルオロエチレンの微粒子を電
極基材３に溶融密着させることによつて行なわれ
る。 The water repellent treatment is carried out, for example, by attaching polytetrafluoroethylene fine particles to the electrode base material 3 and melting and adhering the polytetrafluoroethylene fine particles to the electrode base material 3 at a temperature of 320° C. or higher.
従来、ポリテトラフルオロエチレンの微粒子を
電極基材３に付着せしめる方法としてハケ塗り、
スプレー法、および撥水処理ペースト浴に電極基
材３を沈め引き上げる方法などがあつた。 Conventionally, methods for attaching fine particles of polytetrafluoroethylene to the electrode base material 3 include brush coating,
The methods include a spray method and a method in which the electrode base material 3 is submerged in a water-repellent treatment paste bath and then pulled up.
ハケ塗りは、ハケに撥水処理ペーストを含ま
せ、電極基材３に撥水処理ペーストを塗り、電極
基材３に撥水処理ペーストを浸透付着せしめる方
法であり、撥水処理ペーストとしてはトリトン
X100を分散剤として含むポリテトラフルオロエ
チレンの水溶液（ポリテトラフルオロエチレン；
30重量パーセント）が用いられていた。このハケ
塗りによる撥水処理の場合、人手によつて行なわ
れるために非常に時間がかかる欠点があり、また
撥水の程度（電極基材３に付着するポリテトラフ
ルオロエチレンの量）が、ハケに含ませる撥水処
理ペーストの量によつて変化し、不均一になりや
すいという問題点があつた。 Brush coating is a method in which a brush is impregnated with a water-repellent treatment paste, the water-repellent treatment paste is applied to the electrode base material 3, and the water-repellent treatment paste is penetrated and adhered to the electrode base material 3.
Aqueous solution of polytetrafluoroethylene containing X100 as a dispersant (polytetrafluoroethylene;
30% by weight) was used. This water-repellent treatment by brushing has the drawback that it is very time-consuming because it is done manually, and the degree of water repellency (the amount of polytetrafluoroethylene adhering to the electrode base material 3) is There was a problem that the amount of water-repellent paste included in the water-repellent paste varied, and it tended to become non-uniform.
また、スプレー法による撥水処理は、ハケ塗り
と同様の撥水処理ペーストを霧のように電極基材
３に吹き付ける方法であるが、電極基材３が大変
ポーラスなために、吹き付ける圧力によつてペー
ストが電極基材３の下まで透過してしまい、電極
基材３の下層部の撥水性が弱くなるなどの問題点
があつた。 In addition, water repellent treatment by spraying is a method in which a water repellent treatment paste similar to brush painting is sprayed onto the electrode base material 3 like a mist, but since the electrode base material 3 is very porous, the spraying pressure is This caused problems such as the paste penetrating to the bottom of the electrode base material 3 and weakening the water repellency of the lower layer of the electrode base material 3.
また、撥水処理ペースト浴に電極基材３を一旦
沈め、電極基材３に充分撥水処理ペーストを含ま
せた後、電極基材３を引き上げる方法は、電極基
材３を引き上げる時に、電極基材３に含まれた撥
水処理ペーストが移動するため、引き上げる最初
の部分と最後の部分とで撥水の程度が異なり、最
後の部分の方が撥水性が強くなるという欠点があ
つた。 In addition, the method of pulling up the electrode base material 3 after once submerging the electrode base material 3 in a water repellent paste bath and fully soaking the electrode base material 3 with the water repellent treatment paste is such that when pulling up the electrode base material 3, Since the water-repellent paste contained in the base material 3 moves, the degree of water repellency differs between the first part and the last part to be pulled up, with the disadvantage that the last part has stronger water repellency.
なお、これらの方法によつてポリテトラフルオ
ロエチレンを付着せしめた電極基材３は80〜120
℃程度で水分の乾燥のため熱処理され最終的には
320℃以上の温度でポリテトラフルオロエチレン
を溶融させ、電極基材３に密着させる。 Note that the electrode base material 3 to which polytetrafluoroethylene is attached by these methods has a particle size of 80 to 120
It is heat treated to dry the moisture at around ℃ and finally
Polytetrafluoroethylene is melted at a temperature of 320° C. or higher and brought into close contact with the electrode base material 3.
上記のような従来の燃料電池用電極基材処理方
法は、いずれの場合も撥水処理量が不均一であ
り、撥水処理とシール処理とを同時に処理するこ
とができず、量産性が低く自動化が図れないとい
う問題点があつた。
In the conventional fuel cell electrode substrate treatment methods described above, the amount of water repellent treatment is uneven in each case, and water repellent treatment and sealing treatment cannot be performed at the same time, resulting in low mass productivity. There was a problem that automation could not be achieved.
この発明は、かかる問題点を解決するためにな
されたもので、撥水処理量を均一化し、撥水処理
とシール処理とを同時に処理し、量産性を高める
とともに、自動化を容易にすることを目的とす
る。 This invention was made to solve these problems, and aims to equalize the amount of water repellent treatment, process water repellent treatment and seal treatment at the same time, improve mass productivity, and facilitate automation. purpose.
この発明に係る燃料電池用電極基材処理方法
は、搬送ロールを回転させて電極基材を搬送し、
上記搬送ロールの回転と同方向に回転し、上記搬
送ロールに上記電極基材を介在させて対向するコ
ーテイングロールを有し、このコーテイングロー
ルとこれに調節可能な間〓を設けて対向するドク
ターロール間に、ペースト溜を仕切り板により仕
切つて３つのペースト溜分室を構成し、中央のペ
ースト溜分室より撥水処理ペーストを供給すると
同時に両端のペースト溜分室よりシール処理ペー
ストを供給し、上記コーテイングロールの回転に
伴つて上記２種類のペーストを同時に上記電極基
材上に転写し、上記電極基材に上記２種類のペー
ストを浸透させた後、熱処理するようにしたもの
である。
The fuel cell electrode base material processing method according to the present invention rotates a transport roll to transport the electrode base material,
A coating roll that rotates in the same direction as the rotation of the transport roll and faces the transport roll with the electrode base material interposed therebetween, and a doctor roll that faces the coating roll with an adjustable distance therebetween. In between, the paste reservoir is partitioned by a partition plate to form three paste distillation chambers, and at the same time, the water-repellent paste is supplied from the central paste distillation chamber, and the sealing paste is supplied from the paste distillation chambers at both ends. As the electrode base material rotates, the two types of pastes are simultaneously transferred onto the electrode base material, and after the two types of pastes are permeated into the electrode base material, heat treatment is performed.
この発明においては、搬送ロールとコーテイン
グロールの回転を同方向に回転させるリバースロ
ールコータ法を用い、コーテイングロールに対向
するドクターロール間に、ペースト溜を仕切り板
により仕切つて３つのペースト溜分室を構成し、
中央のペースト溜分室から撥水処理ペーストを供
給すると同時に両端のペースト溜分室からシール
処理ペーストを供給しているので、常に一定量の
撥水処理ペーストとシール処理ペーストとを同時
に電極基材上に転写し浸透でき、量産性を向上す
るとともに、各ロールを制御して容易に自動化で
きる。
In this invention, a reverse roll coater method is used in which the conveying roll and the coating roll are rotated in the same direction, and the paste reservoir is partitioned by a partition plate between the doctor rolls facing the coating roll to form three paste distillation chambers. death,
Since the water repellent paste is supplied from the central paste distillation chamber and the sealing paste is simultaneously supplied from the paste distillation chambers at both ends, a constant amount of water repellent paste and sealing paste are always deposited on the electrode base material at the same time. It can be transferred and infiltrated, improving mass production, and it can be easily automated by controlling each roll.
まず、この発明に関する予備実験の結果につい
て説明する。第１図および第２図は、この発明の
燃料電池用電極基材処理方法を用いて行なつた予
備実験装置を示す断面図および平面図である。こ
の装置は電極基材の撥水処理を行なうものであ
り、この予備実験は装置の基本性能の確認と揆水
処理ペースト組成の最適化のために行なつたもの
である。図において、１０は電極基材、１１は撥
水処理ペースト、１２はドクターロール（以下Ｄ
ロールと記す）、１３は矢印Ａ方向に回転するコ
ーテイングロール（以下Ｃロールと記す）、１４
は矢印Ｂ方向に回転する搬送ロール（以下Ｂロー
ルと記す）、１５は矢印Ｃ方向に回転するクリー
ニングロール、１６は撥水処理ペースト１１を収
納するペースト溜、１７はサイド板１８を支持す
る支持棒である。Ｄロール１２はＣロール１３と
の間に調節された間隙Ｓ１で固定されており、Ｃ
ロール１３の回転によつて撥水処理ペースト１１
がペースト溜１６から間隙を通つて引き出され
る。さらにペーストはＣロール１３の周りに沿つ
て展開され、Ｂロール１４により矢印Ｄ方向に搬
送される電極基材１０上に転写する。転写された
撥水処理ペーストが電極基材１０に浸透した後、
熱処理して撥水処理ペーストを電極基材１０に密
着させる。
First, the results of preliminary experiments regarding this invention will be explained. FIG. 1 and FIG. 2 are a sectional view and a plan view showing a preliminary experiment apparatus in which the method for treating a fuel cell electrode base material of the present invention was carried out. This device performs water repellent treatment on electrode base materials, and this preliminary experiment was conducted to confirm the basic performance of the device and to optimize the composition of the water repellent treatment paste. In the figure, 10 is an electrode base material, 11 is a water repellent treatment paste, and 12 is a doctor roll (hereinafter referred to as D).
13 is a coating roll (hereinafter referred to as C roll) rotating in the direction of arrow A, 14
15 is a cleaning roll that rotates in the direction of arrow C; 16 is a paste reservoir that stores the water-repellent paste 11; and 17 is a support that supports the side plate 18. It's a stick. The D roll 12 is fixed with an adjusted gap S1 between the C roll 13 and the C roll 12.
The water repellent paste 11 is formed by rotating the roll 13.
is withdrawn from the paste reservoir 16 through the gap. Further, the paste is spread around the C roll 13 and transferred onto the electrode base material 10 that is conveyed in the direction of arrow D by the B roll 14. After the transferred water repellent paste penetrates into the electrode base material 10,
The water repellent treatment paste is brought into close contact with the electrode base material 10 by heat treatment.
撥水処理ペーストの電極基材１０への転写量
は、Ｄロール１２とＣロール１３間の間隙Ｓ１
と、Ｃロール１３とＢロール１４の回転比によつ
て容易に調節でき、任意に定めることができる。
図中、各ロール１２，１３，１４，１５の中心に
おける矢印は、各ロール１２，１３，１４，１５
を設定する時の移動可能な方向を示している。 The amount of water repellent paste transferred to the electrode base material 10 is determined by the gap S1 between the D roll 12 and the C roll 13.
This can be easily adjusted by changing the rotation ratio of the C roll 13 and the B roll 14, and can be set arbitrarily.
In the figure, the arrows at the center of each roll 12, 13, 14, 15 indicate
Shows the possible directions of movement when setting.
撥水処理ペーストは、例えば、固形分としてポ
リテトラフルオロエチレンを主成分とする水溶液
で、ポリテトラフルオロエチレンは平均粒径0.3μ
ｍ程度の微粒子であることが望ましい。また、ポ
リテトラフルオロエチレンの重量比はペーストに
対して20〜40％が適当で、40％を越えると撥水量
が多過ぎて、電極基材１０の通気性を阻害するな
どの併害を生じる。また20％よりも少ないと撥水
量が少な過ぎて、電極基材１０に充分な撥水性を
与えることができない。また、ポリテトラフルオ
ロエチレンの微粒子を安定に分散させるため、分
散剤として非イオン性界面活性剤が必要である
が、これは例えばポリエチレングリコールオクチ
ルフエニルエーテルやポリエテレングリコールノ
ニルフエニルエーテル、ポリオキシエチレンアル
キルエーテルなどがあり、ペーストの重量に対し
て２〜６％程度含まれている必要がある。２％を
下廻るとポリテトラフルオロエチレンの微粒子の
分散が充分でなく、ペーストの安定性に問題が生
じる。また６％を上廻る場合にもペーストのゲル
化などの問題を生じる。さらにペーストには増粘
剤を加える必要がある。これは分散剤のみを含む
ポリテトラフルオロエチレンの水溶液では粘性が
低過ぎて、Ｃロール１３上に展開された時、下に
したたり落ちてしまうためである。この増粘剤と
してはセルロース誘導体がポリテトラフルオロエ
チレンとの相互作用が少なく適していた。セルロ
ース誘導体は、例えばカルボキシメチルセルロー
スNa塩やカルボキシメチルセルロースアンモニ
ウム塩、メチルセルロースなどがあるが、いずれ
の場合にもペーストに対して0.5〜３％程度加え
ることによつて適当な粘性を得ることができる。 The water repellent paste is, for example, an aqueous solution containing polytetrafluoroethylene as its main solid component, and the polytetrafluoroethylene has an average particle size of 0.3 μm.
It is desirable that the particles be of the order of m. In addition, the appropriate weight ratio of polytetrafluoroethylene to the paste is 20 to 40%; if it exceeds 40%, the amount of water repellent is too large, causing side effects such as inhibiting the air permeability of the electrode base material 10. . Further, if it is less than 20%, the amount of water repellent is too small and it is not possible to impart sufficient water repellency to the electrode base material 10. In addition, in order to stably disperse polytetrafluoroethylene fine particles, a nonionic surfactant is required as a dispersant. Ethylene alkyl ether, etc., must be contained in an amount of about 2 to 6% based on the weight of the paste. If it is less than 2%, the polytetrafluoroethylene fine particles will not be sufficiently dispersed, causing a problem with the stability of the paste. Further, when the amount exceeds 6%, problems such as gelation of the paste occur. Additionally, it is necessary to add a thickener to the paste. This is because an aqueous solution of polytetrafluoroethylene containing only a dispersant has too low a viscosity, and when it is spread on the C roll 13, it drips downward. Cellulose derivatives were suitable as this thickener because of their low interaction with polytetrafluoroethylene. Examples of cellulose derivatives include carboxymethylcellulose Na salt, carboxymethylcellulose ammonium salt, and methylcellulose. In any case, an appropriate viscosity can be obtained by adding about 0.5 to 3% to the paste.
0.5％よりも少ないと充分な粘性を得ることが
できず、３％を越えると粘性が高過ぎてペースト
の電極基材１０への浸透性が悪くなつた。 When it was less than 0.5%, sufficient viscosity could not be obtained, and when it exceeded 3%, the viscosity was too high and the permeability of the paste into the electrode base material 10 became poor.
このように調整された撥水処理ペーストを用い
て、第１図に示した装置により電極基材１０の撥
水処理を行ない、従来法のハケ塗りの場合と撥水
処理量の均一性の比較を行なつた。 Using the water repellent treatment paste prepared in this way, the electrode base material 10 was treated with water repellency using the apparatus shown in Figure 1, and the uniformity of the amount of water repellency treated was compared with that of the conventional method of brush painting. I did this.
第１図に示した装置において、間隙Ｓ１を
100μｍ、Ｂロールの回転速度を２ｍ／分、Ｃロ
ールの回転速度を３ｍ／分の条件下で、710×610
mm、厚さ0.4mmの電極基材１０の撥水処理を行な
つた。撥水処理ペーストのペースト溜１６への供
給は、撥水処理ペーストを入れたバケツ（図示せ
ず）からペースト溜１６にローラポンプ（図示せ
ず）を用いて自動的にペーストを供給し、連続的
に50枚の電極基材１０の撥水処理を行なつた。そ
の所要時間は約20分間であり、ペーストの利用率
（電極基材上に転写した重量／使用した重量）は
90％を越えた。電極基材１０は100℃で乾燥し、
表面を観察したが、目視による観察では、不均一
に撥水処理した場合にポリテトラフルオロエチレ
ンの偏在によつて生じる白い斑点などが全く見ら
れず、表裏共、同様の状態で撥水性が得られてい
た。また、その中の１枚を100×150mmの小片に切
断（もとの電極基材を24個の小片に切断）し、そ
の重量を測定した。この結果を0.05ｇ間隔の等高
線に置き換えたものを第３図に示す。この重量の
誤差は0.1ｇの範囲内に入つており、この誤差は
電極基材１０そのものの重量誤差と同じである。
従つて、非常に均一に撥水処理できたことが実証
された。 In the device shown in Fig. 1, the gap S1 is
100 μm, 710×610 under the conditions of B roll rotation speed 2 m/min and C roll rotation speed 3 m/min.
The electrode base material 10 with a thickness of 0.4 mm and a thickness of 0.4 mm was subjected to water repellent treatment. The water-repellent paste is continuously supplied to the paste reservoir 16 by automatically supplying the paste from a bucket (not shown) containing the water-repellent paste to the paste reservoir 16 using a roller pump (not shown). Specifically, 50 electrode substrates 10 were subjected to water repellent treatment. The time required is approximately 20 minutes, and the paste utilization rate (weight transferred onto the electrode base material/weight used) is
It exceeded 90%. The electrode base material 10 is dried at 100°C,
Visual observation of the surface showed that there were no white spots that occur due to the uneven distribution of polytetrafluoroethylene when non-uniform water repellent treatment was applied, and water repellency was obtained in the same condition on both the front and back surfaces. It was getting worse. In addition, one of the pieces was cut into small pieces of 100 x 150 mm (the original electrode base material was cut into 24 pieces), and the weight was measured. Figure 3 shows this result replaced with contour lines at 0.05 g intervals. This weight error is within a range of 0.1 g, and this error is the same as the weight error of the electrode base material 10 itself.
Therefore, it was verified that the water repellent treatment was carried out very uniformly.
一方、従来のハケ塗り方法により電極基材１０
の撥水処理を行ない、100℃で乾燥して電極基材
１０表面の観察を行なつた。目視による観察で
は、ポリテトラフルオロエチレンの偏在によつて
生じる白い斑点が至るところに見られ、基材１０
の表と裏では明らかに撥水性が異なつていた。ま
た100×150mmの小片に切断した後、その重量を測
定し、等高線に置き換えたものを第４図に示す。
100×150mmの平均重量はこの予備実験によるもの
とほぼ同一であつたが、重量誤差は大きくなり、
0.5ｇであつた。 On the other hand, the electrode base material 10 was coated using a conventional brush coating method.
The electrode base material 10 was subjected to water repellent treatment and dried at 100° C., and the surface of the electrode base material 10 was observed. Visual observation showed that white spots caused by uneven distribution of polytetrafluoroethylene were seen everywhere, and the base material 10
There was a clear difference in water repellency between the front and back sides. In addition, after cutting into small pieces of 100 x 150 mm, the weight was measured and the contour lines are shown in Figure 4.
The average weight of 100 x 150 mm was almost the same as that from this preliminary experiment, but the weight error became larger.
It was 0.5g.
以上の結果からこの発明の燃料電池用電極基材
処理方法に係る装置の基本的性能の確認と揆水処
理ペーストの最適化を行なうことができた。 Based on the above results, we were able to confirm the basic performance of the device related to the fuel cell electrode base material treatment method of the present invention and to optimize the water repellent treatment paste.
次に、この発明の一実施例を図について説明す
る。第５図はこの発明の燃料電池用電極基材処理
方法に係る装置の一実施例を示す平面図である。
なお、この装置を示す断面図は第１図と同様の構
成である。図において、１８は両端のサイド板で
あり、Ｃロール１３とＤロール１２との間隙Ｓ１
に２枚の仕切り板１９を設け、３つのペースト溜
分室を設けている。第５図は第６図に示した燃料
極２の電極基材３とウエツトシール部６の処理を
同時に行なうものである。 Next, an embodiment of the present invention will be described with reference to the drawings. FIG. 5 is a plan view showing an embodiment of the apparatus according to the method for treating a fuel cell electrode base material of the present invention.
Note that the sectional view showing this device has the same configuration as FIG. 1. In the figure, 18 is a side plate at both ends, and the gap S1 between the C roll 13 and the D roll 12 is
Two partition plates 19 are provided to provide three paste distillation chambers. FIG. 5 shows that the electrode base material 3 and wet seal portion 6 of the fuel electrode 2 shown in FIG. 6 are treated at the same time.
３つのペースト溜分室のうち中央のペースト溜
１６には撥水処理ペースト１１を入れ、他のペー
スト溜２０にはシール処理ペーストを入れる。２
１は例えばスウエーデン鋼でできたスクレーパー
である。スクレーパー２１はＣロール１３上やペ
ースト溜１６，２０にペーストが戻る際に２種類
のペーストが混合しないように、２液の接合部分
のペーストをＣロール１３上から取う去るための
ものであり、取り去つたペーストはペースト受け
２３に溜めて回収する。また、２２はスクレーパ
ー２１を固定するための棒である。 Of the three paste reservoirs, the water repellent paste 11 is placed in the central paste reservoir 16, and the sealing paste is placed in the other paste reservoirs 20. 2
1 is a scraper made of Swedish steel, for example. The scraper 21 is used to remove the paste at the joint of the two liquids from the top of the C roll 13 to prevent the two types of paste from mixing when the paste returns to the C roll 13 or the paste reservoirs 16 and 20. The removed paste is stored in a paste receiver 23 and recovered. Further, 22 is a rod for fixing the scraper 21.
以上の構成により、先の予備実験の場合と同様
に間〓Ｓ１を100μｍ、Ｂロールの回転速度を２
ｍ／分、Ｃロールの回転速度を３ｍ／分の条件下
で、710×610mm、厚さ0.4mmの電極基材１０の両
端30mmをシール処理、中央部を揆水処理として同
時に処理した。なお、シール処理ペーストの固形
分としては、炭化ケイ素イ、リン酸ジルコニウム
ロ、並びに炭化ケイ素及びリン酸ジルコニウムの
混合物のうちのいずれか１種を主成分とするもの
が適していた。予備実験の場合と同様に揆水処理
部とシール処理部の均一性を肉眼及び重量法で調
べ、充分に均一性が保たれていることを確認し
た。また、揆水処理部とシール処理部の間にはす
き間や重なりが生じていないことも確認された。 With the above configuration, as in the case of the previous preliminary experiment, the distance S1 is set to 100 μm, and the rotation speed of the B roll is set to 2.
3 m/min, and the rotation speed of the C roll was 3 m/min. Both ends of the electrode base material 10 having a size of 710 x 610 mm and a thickness of 0.4 mm were subjected to sealing treatment at 30 mm, and water repelling treatment at the center at the same time. As for the solid content of the sealing paste, it was suitable that the main component was any one of silicon carbide, zirconium phosphate, and a mixture of silicon carbide and zirconium phosphate. As in the case of the preliminary experiment, the uniformity of the water repellent treatment area and the seal treatment area was examined visually and gravimetrically, and it was confirmed that sufficient uniformity was maintained. It was also confirmed that there were no gaps or overlaps between the water purification treatment section and the seal treatment section.
この発明は以上説明したとおり、搬送ロールを
回転させて電極基材を搬送し、上記搬送ロールの
回転と同方向に回転し、上記搬送ロールに上記電
極基材を介在させて対向するコーテイングロール
を有し、このコーテイングロールとこれに調節可
能な間〓を設けて対向するドクターロール間に、
ペースト溜を仕切り板により仕切つて３つのペー
スト溜分室を構成し、中央のペースト溜分室より
撥水処理ペーストを供給すると同時に両端のペー
スト溜分室よりシール処理ペーストを供給し、上
記コーテイングロールの回転に伴つて上記２種類
のペーストを同時に上記電極基材上に転写し、上
記電極基材に上記２種類のペーストを浸透させた
後、熱処理するようにしたので、撥水処理量を均
一化し、ペーストを混合させることなく間〓を設
けることなく撥水処理とシール処理とを同時に処
理でき、量産性を高め自動化を容易にすることが
できる効果がある。
As explained above, the present invention rotates a conveyance roll to convey an electrode base material, rotates in the same direction as the rotation of the conveyance roll, and inserts the electrode base material between the conveyance rolls and the opposing coating roll. and between the coating roll and the opposing doctor roll with an adjustable gap,
The paste reservoir is divided by a partition plate to form three paste distillation chambers, and at the same time water-repellent paste is supplied from the central paste distillation chamber, sealing paste is supplied from the paste distillation chambers at both ends, and the coating roll is rotated. Accordingly, the above two types of pastes were simultaneously transferred onto the above electrode base material, and after the above two types of pastes were infiltrated into the above electrode base material, heat treatment was performed, so that the amount of water repellent treatment was made uniform and the paste The water repellent treatment and the seal treatment can be carried out simultaneously without mixing and without a pause, which has the effect of increasing mass productivity and facilitating automation.
第１図および第２図は、この発明の一実施例に
係る電極基材撥水処理方法を用いて行なつた予備
実験装置を示す断面図および平面図、第３図は予
備実験による電極基材の撥水処理結果で、撥水処
理量の重量の等高線図、第４図は従来の方法によ
る撥水処理量の重量の等高線図、第５図はこの発
明の一実施例に係る電極基材処理装置を示す平面
図、第６図は燃料電池の電極構成を示す断面図で
ある。
１０……電極基材、１１……撥水処理ペース
ト、１２……ドクターロール、１３……コーテイ
ングロール、１４……搬送ロール、１６……ペー
スト溜、１９……仕切り板、２０……ペースト溜
分室。なお、図中、同一符号は同一、又は相当部
分を示す。
FIGS. 1 and 2 are a sectional view and a plan view showing a preliminary experiment apparatus in which an electrode substrate water repellent treatment method according to an embodiment of the present invention was carried out, and FIG. 3 is an electrode substrate according to a preliminary experiment. The results of water repellent treatment of the material include a contour diagram of the weight of the amount of water repellent treated, FIG. 4 is a contour diagram of the weight of the amount of water repelled treated by the conventional method, and FIG. FIG. 6 is a plan view showing the material processing device, and a cross-sectional view showing the electrode structure of the fuel cell. 10... Electrode base material, 11... Water repellent treatment paste, 12... Doctor roll, 13... Coating roll, 14... Conveyance roll, 16... Paste reservoir, 19... Partition plate, 20... Paste reservoir Branch room. In addition, in the figures, the same reference numerals indicate the same or equivalent parts.
Claims (1)
記搬送ロールの回転と同方向に回転し、上記搬送
ロールに上記電極基材を介在させて対向するコー
テイングロールを有し、このコーテイングロール
とこれに調節可能な間〓を設けて対向するドクタ
ーロール間に、ペースト溜を仕切り板により仕切
つて３つのペースト溜分室を構成し、中央のペー
スト溜分室より撥水処理ペーストを供給すると同
時に両端のペースト溜分室よりシール処理ペース
トを供給し、上記コーテイングロールの回転に伴
つて上記２種類のペーストを同時に上記電極基材
上に転写し、上記電極基材に上記２種類のペース
トを浸透させた後、熱処理するようにした燃料電
池用電極基材処理方法。 ２ 撥水処理ペーストは、固形分としてポリテト
ラフルオロエチレンを主成分とし、分散剤と増粘
剤を含む水溶液であり、ポリテトラフルオロエチ
レンは、撥水処理ペーストの重量に対して20〜40
％含まれており、分散剤は非イオン性界面活性剤
であつて、撥水処理ペーストの重量に対して２〜
６％含まれており、増粘剤は、撥水処理ペースト
の重量に対して0.5〜３％含まれることを特徴と
する特許請求の範囲第１項記載の燃料電池用電極
基材処理方法。 ３ シール処理ペーストは、固形分として炭化ケ
イ素、リン酸ジルコニウム、並びに炭化ケイ素お
よびリン酸ジルコニウムを混合したもののいずれ
か１種を主成分とすることを特徴とする特許請求
の範囲第１項または第２項記載の燃料電池用電極
基材処理方法。[Claims] 1. A coating roll that rotates a conveyance roll to convey the electrode base material, rotates in the same direction as the rotation of the conveyance roll, and faces the conveyance roll with the electrode base material interposed therebetween. The paste reservoir is divided by a partition plate between the coating roll and the doctor roll facing each other with an adjustable gap between them, forming three paste distillation chambers, and the water-repellent paste is applied from the central paste distillation chamber. At the same time as the sealing paste is supplied from the paste distillation chambers at both ends, the two types of paste are simultaneously transferred onto the electrode base material as the coating roll rotates, and the two types of paste are transferred onto the electrode base material. A method for treating a fuel cell electrode base material, which comprises infiltrating a fuel cell electrode base material and then heat-treating the base material. 2. The water repellent paste is an aqueous solution containing polytetrafluoroethylene as the main solid component and a dispersant and a thickener.
%, and the dispersant is a nonionic surfactant, and the dispersant is a nonionic surfactant, and the amount of water repellent paste is 2 to
6%, and the thickener is contained in an amount of 0.5 to 3% based on the weight of the water repellent paste. 3. The sealing paste is characterized in that the solid content is silicon carbide, zirconium phosphate, or a mixture of silicon carbide and zirconium phosphate as a main component. 2. The method for treating a fuel cell electrode base material according to item 2.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59223309A JPS6199272A (en) | 1984-10-22 | 1984-10-22 | Method of treating electrode base for fuel cell |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59223309A JPS6199272A (en) | 1984-10-22 | 1984-10-22 | Method of treating electrode base for fuel cell |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6199272A JPS6199272A (en) | 1986-05-17 |
| JPH0465499B2 true JPH0465499B2 (en) | 1992-10-20 |
Family
ID=16796126
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP59223309A Granted JPS6199272A (en) | 1984-10-22 | 1984-10-22 | Method of treating electrode base for fuel cell |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6199272A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013161253A1 (en) * | 2012-04-25 | 2013-10-31 | Hitachi Zosen Corporation | Functional porous material, metal-air battery, and method for manufacturing functional porous material |
| CN102896066B (en) * | 2012-10-23 | 2014-08-27 | 重庆市璧山宏向汽配有限公司 | Gluing machine for automobile brake gasket |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS50155541A (en) * | 1974-06-06 | 1975-12-15 | ||
| JPS5512622A (en) * | 1978-07-11 | 1980-01-29 | Sanyo Electric Co Ltd | Manufacture of electrode for cell |
| JPS57124864A (en) * | 1981-01-28 | 1982-08-03 | Sanyo Electric Co Ltd | Gas diffusion electrode of fuel cell |
| JPS57156064A (en) * | 1981-03-20 | 1982-09-27 | Matsushita Electric Works Ltd | Roll coater |
| JPS5868873A (en) * | 1981-09-29 | 1983-04-23 | ユナイテツド・テクノロジ−ズ・コ−ポレイシヨン | Method of producing porous product made of carbon fiber coupled with resin |
| JPS58142764A (en) * | 1982-02-19 | 1983-08-24 | Matsushita Electric Ind Co Ltd | Manufacture of gas diffusion type air electrode |
| JPS6017863A (en) * | 1983-07-08 | 1985-01-29 | Matsushita Electric Ind Co Ltd | Manufacture of gas diffusion catalyst electrode |
-
1984
- 1984-10-22 JP JP59223309A patent/JPS6199272A/en active Granted
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS50155541A (en) * | 1974-06-06 | 1975-12-15 | ||
| JPS5512622A (en) * | 1978-07-11 | 1980-01-29 | Sanyo Electric Co Ltd | Manufacture of electrode for cell |
| JPS57124864A (en) * | 1981-01-28 | 1982-08-03 | Sanyo Electric Co Ltd | Gas diffusion electrode of fuel cell |
| JPS57156064A (en) * | 1981-03-20 | 1982-09-27 | Matsushita Electric Works Ltd | Roll coater |
| JPS5868873A (en) * | 1981-09-29 | 1983-04-23 | ユナイテツド・テクノロジ−ズ・コ−ポレイシヨン | Method of producing porous product made of carbon fiber coupled with resin |
| JPS58142764A (en) * | 1982-02-19 | 1983-08-24 | Matsushita Electric Ind Co Ltd | Manufacture of gas diffusion type air electrode |
| JPS6017863A (en) * | 1983-07-08 | 1985-01-29 | Matsushita Electric Ind Co Ltd | Manufacture of gas diffusion catalyst electrode |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6199272A (en) | 1986-05-17 |
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