JPS6319982B2 - - Google Patents
Info
- Publication number
- JPS6319982B2 JPS6319982B2 JP56011009A JP1100981A JPS6319982B2 JP S6319982 B2 JPS6319982 B2 JP S6319982B2 JP 56011009 A JP56011009 A JP 56011009A JP 1100981 A JP1100981 A JP 1100981A JP S6319982 B2 JPS6319982 B2 JP S6319982B2
- Authority
- JP
- Japan
- Prior art keywords
- graphite
- intercalation compound
- catalyst layer
- gas
- acid
- 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
Links
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 30
- 239000010439 graphite Substances 0.000 claims description 25
- 229910002804 graphite Inorganic materials 0.000 claims description 25
- 238000009830 intercalation Methods 0.000 claims description 17
- 239000003054 catalyst Substances 0.000 claims description 15
- 150000001875 compounds Chemical class 0.000 claims description 15
- 230000002687 intercalation Effects 0.000 claims description 15
- 238000009792 diffusion process Methods 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 8
- 239000000446 fuel Substances 0.000 claims description 7
- 239000002245 particle Substances 0.000 claims description 3
- 239000000758 substrate Substances 0.000 claims description 2
- 239000010410 layer Substances 0.000 description 23
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 12
- 239000007789 gas Substances 0.000 description 11
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 9
- 239000000843 powder Substances 0.000 description 7
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 5
- 239000011159 matrix material Substances 0.000 description 5
- 239000003792 electrolyte Substances 0.000 description 4
- 239000013626 chemical specie Substances 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 229910001508 alkali metal halide Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- -1 etc.) Inorganic materials 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 239000003350 kerosene Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- H01M4/96—Carbon-based electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Description
【発明の詳細な説明】
本発明は燃料電池用ガス拡散電極に関するもの
である。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a gas diffusion electrode for a fuel cell.
一般にガス拡散電極は、防水処理を施したカー
ボンペーパー（拡散層）上に触媒金属を含む黒鉛
を塗着するか予めシート状に成形して貼着し、拡
散層と触媒層の二重層に構成される。 Generally, gas diffusion electrodes are constructed by coating graphite containing catalyst metal on waterproofed carbon paper (diffusion layer) or by forming it into a sheet in advance and pasting it, forming a double layer consisting of a diffusion layer and a catalyst layer. be done.
酸性燃料電池は、陰陽のガス電極と電解液保持
マトリツクスとよりなる単位セル間に炭素質ガス
分離板を介し多数積層して使用されるが、触媒層
の電気抵抗による電圧降下が無視できなくなる。 Acid fuel cells are used by stacking a large number of unit cells with carbonaceous gas separation plates interposed between unit cells consisting of positive and negative gas electrodes and an electrolyte holding matrix, but the voltage drop due to the electrical resistance of the catalyst layer cannot be ignored.
本発明は、かかる点に鑑み、触媒層の基体とし
て通常用いられている黒鉛の代りに、黒鉛の層間
に酸を浸入させた黒鉛層間化合物を用いることに
より電気伝導性を改善することを目的とする。 In view of this, the present invention aims to improve electrical conductivity by using a graphite intercalation compound in which acid is infiltrated between graphite layers instead of graphite, which is normally used as a substrate for a catalyst layer. do.
黒鉛の結晶は炭素原子の六角板状面が層状に積
重なつた構造を持ち、各層面内の結合は強いが層
間の結合は弱く、多くの化学種が層間に入り、黒
鉛層間化合物を形成する。層間に侵入可能な化学
種としてアルカリ金属（Li、Na、Ｋ等）、金属ハ
ロゲン化物（AlCl3、MgCl2等）、酸（HNO3、
H2SO4、等）があるが、アルカリ金属・金属ハ
ロゲン化合物等の層間化合物は酸性電解液による
腐蝕のため使用できないので、酸を使用した。こ
れら層間化合物は黒鉛の平面構造は保たれたまゝ
であるが、黒鉛に比し電気伝導度は良くなる。 Graphite crystals have a structure in which hexagonal plate-like planes of carbon atoms are stacked in layers, and the bonds within each layer are strong, but the bonds between the layers are weak, and many chemical species enter between the layers, forming graphite intercalation compounds. do. Chemical species that can penetrate between layers include alkali metals (Li, Na, K, etc.), metal halides (AlCl 3 , MgCl 2 , etc.), acids (HNO 3 ,
H 2 SO 4 , etc.), but since intercalation compounds such as alkali metal/metal halide compounds cannot be used because they are corroded by acidic electrolytes, acids were used. These intercalation compounds maintain the planar structure of graphite, but have better electrical conductivity than graphite.
本発明によるガス拡散電極の作成例を説明す
る。化学種として硫酸を用いた黒鉛層間化合物の
場合、黒鉛と濃硫酸を乾燥雰囲気中で混合し、不
活性ガス中で300℃、５時間反応させた。この生
成物を粉砕し400メツシユパスの黒鉛層間化合物
微粉末を得る。次にこの微粉末50ｇに対し塩化白
金酸13ｇを水100c.c.に溶解した溶液を混合し、
過後真空乾燥を行い、ついで水素ガス中300〜350
℃で１時間還元して粒子表面に白金黒を付着させ
る。この処理済層間化合物粉末とフツ素樹脂粉末
とを重量比１：１で混合し、ケロシンを適量加え
てペースト状とした。これをローラーにかけてシ
ートとし、このシートを自然乾燥しケロシンを蒸
発させた。この触媒層シートを予め防水処理した
カーボンペーパー上に添着し加圧後加熱して二重
層電極とした。 An example of creating a gas diffusion electrode according to the present invention will be described. In the case of a graphite intercalation compound using sulfuric acid as a chemical species, graphite and concentrated sulfuric acid were mixed in a dry atmosphere and reacted at 300° C. for 5 hours in an inert gas. This product is crushed to obtain a graphite intercalation compound fine powder of 400 mesh passes. Next, a solution of 13 g of chloroplatinic acid dissolved in 100 c.c. of water was mixed with 50 g of this fine powder.
After evaporation, vacuum dry and then dry in hydrogen gas at 300~350℃.
Platinum black is attached to the particle surface by reduction at ℃ for 1 hour. This treated intercalation compound powder and fluororesin powder were mixed at a weight ratio of 1:1, and an appropriate amount of kerosene was added to form a paste. This was rolled to form a sheet, and this sheet was air-dried to evaporate the kerosene. This catalyst layer sheet was applied onto carbon paper that had been waterproofed in advance, and heated after pressurizing to form a double layer electrode.
又酸として燐酸を用いる場合、黒鉛と乾燥した
燐酸を乾燥雰囲気中で混合し、不活性ガス中で
400℃、24時間反応させた。この生成物を粉砕し
て400メツシユパスの黒鉛層間化合物の微粉末を
得る。この微粉末に微量の白金黒微粉末と結着剤
とを加えてペースト状とし、これを予め防水処理
したカーボンペーパー上に塗着する。 When using phosphoric acid as the acid, graphite and dry phosphoric acid are mixed in a dry atmosphere, and then mixed in an inert gas atmosphere.
The reaction was carried out at 400°C for 24 hours. This product is crushed to obtain a fine powder of graphite intercalation compound of 400 mesh passes. A small amount of platinum black fine powder and a binder are added to this fine powder to form a paste, and this is applied onto carbon paper that has been previously waterproofed.
第１図はマトリツクス型燃料電池の要部断面図
を示し、Ｎ，Ｐは陰・陽のガス電極で、１は本発
明による黒鉛層間化合物を基体とする触媒層、２
は防水カーボンペーパーよりなる拡散層である。
又Ｅは燐酸電解液を保持するマトリツクス、Ｓは
水素及び酸素の各ガス供給通路３，４を形成した
カーボン製のガス分離板である。 FIG. 1 shows a sectional view of the main parts of a matrix fuel cell, where N and P are negative and positive gas electrodes, 1 is a catalyst layer based on a graphite intercalation compound according to the present invention, and 2
is a diffusion layer made of waterproof carbon paper.
Further, E is a matrix holding a phosphoric acid electrolyte, and S is a carbon gas separation plate forming hydrogen and oxygen gas supply passages 3 and 4.
第２図、第３図は３セル積層電池について電流
密度と電圧との関係を示す放電特性図で、第２図
は硫酸を侵入させた黒鉛層間化物、第３図は燐酸
を侵入させた黒鉛層間化合物を夫々用いた場合で
ある。又比較のため従来の黒鉛を用いた場合を点
線で示した。 Figures 2 and 3 are discharge characteristic diagrams showing the relationship between current density and voltage for a 3-cell stacked battery. Figure 2 shows graphite intercalated with sulfuric acid, and Figure 3 shows graphite with phosphoric acid penetrated. This is a case where each intercalation compound is used. For comparison, the case where conventional graphite is used is shown by a dotted line.
これら特性図に見られるように本発明による電
池は従来電池に比し特性が向上したが、これは触
媒層の電気伝導度が改善されたためである。本発
明触媒層の抵抗値は黒鉛層間化合物の層間侵入種
として硫酸及び燐酸を使用したものは夫々４×
10-4Ω−cm、及び６×10-4Ω−cmであるに対し、
従来の黒鉛使用触媒層は１〜３×10-3Ωcmであつ
た。そのため積層セル数が増加すればする程抵抗
損失に差が生じる。 As seen in these characteristic diagrams, the battery according to the present invention has improved characteristics compared to the conventional battery, and this is due to the improved electrical conductivity of the catalyst layer. The resistance value of the catalyst layer of the present invention is 4× when sulfuric acid and phosphoric acid are used as the intercalating species of the graphite intercalation compound.
10 -4 Ω-cm, and 6 × 10 -4 Ω-cm, whereas
Conventional catalyst layers using graphite had a thickness of 1 to 3 x 10 -3 Ωcm. Therefore, as the number of stacked cells increases, the difference in resistance loss occurs.
上述の如く本発明によればガス電極触媒層の基
体として黒鉛の代りに、硫酸や燐酸などの酸を層
間侵入種とした黒鉛層間化合物を用いることによ
り、触媒層の電気伝導性を改善し、分極特性の良
好なガス拡散電極を提供して電池性能の向上が達
成される。 As described above, according to the present invention, the electrical conductivity of the catalyst layer is improved by using a graphite intercalation compound containing an interlayer intercalating acid such as sulfuric acid or phosphoric acid instead of graphite as the base of the gas electrode catalyst layer. Improved battery performance is achieved by providing a gas diffusion electrode with good polarization properties.
第１図は本発明電極を備えるマトリツクス型燃
料電池の要部断面図、第２図、第３図は同上電池
の放電特性比較図である。
Ｎ，Ｐ……陰・陽ガス拡散電極、１……触媒
層、２……拡散層、Ｅ……電解質マトリツクス、
Ｓ……ガス分離板。
FIG. 1 is a sectional view of a main part of a matrix type fuel cell equipped with an electrode of the present invention, and FIGS. 2 and 3 are comparison diagrams of discharge characteristics of the same battery. N, P... negative/positive gas diffusion electrode, 1... catalyst layer, 2... diffusion layer, E... electrolyte matrix,
S...Gas separation plate.
Claims (1)
せた黒鉛層間化合物を用いることを特徴とする燃
料電池のガス拡散電極。 ２ 前記黒鉛層間化合物は触媒を付着した粒子と
して結着されていることを特徴とする特許請求の
範囲第１項記載の燃料電池のガス拡散電極。 ３ 前記黒鉛層間化合物は、触媒粒子と混合して
結着されていることを特徴とする特許請求の範囲
第１項記載の燃料電池のガス拡散電極。[Scope of Claims] 1. A gas diffusion electrode for a fuel cell, characterized in that a graphite intercalation compound in which an acid is introduced between layers of graphite is used as a substrate of a catalyst layer. 2. The gas diffusion electrode for a fuel cell according to claim 1, wherein the graphite intercalation compound is bound as particles to which a catalyst is attached. 3. The gas diffusion electrode for a fuel cell according to claim 1, wherein the graphite intercalation compound is mixed with and bound to catalyst particles.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP56011009A JPS57124864A (en) | 1981-01-28 | 1981-01-28 | Gas diffusion electrode of fuel cell |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP56011009A JPS57124864A (en) | 1981-01-28 | 1981-01-28 | Gas diffusion electrode of fuel cell |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS57124864A JPS57124864A (en) | 1982-08-03 |
| JPS6319982B2 true JPS6319982B2 (en) | 1988-04-26 |
Family
ID=11766115
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP56011009A Granted JPS57124864A (en) | 1981-01-28 | 1981-01-28 | Gas diffusion electrode of fuel cell |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS57124864A (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60151968A (en) * | 1984-01-20 | 1985-08-10 | Mitsubishi Electric Corp | Manufacture of electrode for fuel cell |
| JPS60208057A (en) * | 1984-04-02 | 1985-10-19 | Hitachi Ltd | Fuel cell |
| DE3583170D1 (en) * | 1984-04-02 | 1991-07-18 | Hitachi Ltd | ELECTRODE FOR FUEL CELL, METHOD FOR PRODUCING THE SAME AND FUEL CELL USING THIS ELECTRODE. |
| JPS6199272A (en) * | 1984-10-22 | 1986-05-17 | Mitsubishi Electric Corp | Method of treating electrode base for fuel cell |
| JPS63139012A (en) * | 1986-11-29 | 1988-06-10 | Koa Sekiyu Kk | Production of graphitic material for electric cell |
| WO2001005268A1 (en) | 1999-07-21 | 2001-01-25 | Kanebo, Limited | Cosmetic material sheet and method for manufacture of the sheet and apparatus for use in the manufacture |
-
1981
- 1981-01-28 JP JP56011009A patent/JPS57124864A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS57124864A (en) | 1982-08-03 |
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