JPS6155226B2 - - Google Patents
Info
- Publication number
- JPS6155226B2 JPS6155226B2 JP56037846A JP3784681A JPS6155226B2 JP S6155226 B2 JPS6155226 B2 JP S6155226B2 JP 56037846 A JP56037846 A JP 56037846A JP 3784681 A JP3784681 A JP 3784681A JP S6155226 B2 JPS6155226 B2 JP S6155226B2
- Authority
- JP
- Japan
- Prior art keywords
- matrix
- fuel cell
- phosphoric acid
- present
- gas diffusion
- 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
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 40
- 239000000446 fuel Substances 0.000 claims description 27
- 239000011159 matrix material Substances 0.000 claims description 27
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 20
- 238000009792 diffusion process Methods 0.000 claims description 8
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 7
- 239000011230 binding agent Substances 0.000 claims description 6
- -1 polytetrafluoroethylene Polymers 0.000 claims description 5
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 5
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 5
- 229910001887 tin oxide Inorganic materials 0.000 claims description 5
- 239000003792 electrolyte Substances 0.000 claims description 4
- 239000007789 gas Substances 0.000 description 6
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 6
- 229910010271 silicon carbide Inorganic materials 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 3
- 239000005011 phenolic resin Substances 0.000 description 3
- 229920001568 phenolic resin Polymers 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000012212 insulator Substances 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910002090 carbon oxide Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000004094 surface-active agent Substances 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
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/02—Details
- H01M8/0289—Means for holding the electrolyte
- H01M8/0293—Matrices for immobilising electrolyte solutions
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0002—Aqueous electrolytes
- H01M2300/0005—Acid electrolytes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/44—Fibrous material
-
- 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
- Y02E60/10—Energy storage using batteries
-
- 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
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Fuel Cell (AREA)
Description
【発明の詳細な説明】
本発明は、リン酸を電解液とする燃料電池に係
り、特に一対のガス拡散電極間にリン酸を保持す
る燃料電池用マトリツクスを配置した構成の燃料
電池に関するものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a fuel cell using phosphoric acid as an electrolyte, and more particularly to a fuel cell having a structure in which a fuel cell matrix for holding phosphoric acid is arranged between a pair of gas diffusion electrodes. be.
従来、リン酸を電解液とする燃料電池において
は、リン酸を保持するマトリツクスとして、フエ
ノール樹脂の繊維布や炭化ケイ素粉末に結着剤と
してポリテトラフルオロエチレンを混合したもの
が用いられていた。しかしながら、これらのマト
リツクスにおいては以下のような欠点が存在して
いる。すなわち、フエノール樹脂の繊維布をマト
リツクスとして用いたものでは、燃料電池の作動
温度が130℃以上になると、フエノール樹脂が
徐々に炭化され、この結果、長期間の運転ができ
なくなるという欠点がある。このような欠点を除
去するためには、燃料電池の作動温度を低くする
ことが考えられるが、この場合燃料電池の出力が
著しく低下するという重大な問題が生じる。ま
た、燃料電池の温度制御に充分に注意し、部分的
に高温になることを防止しなければならないとい
う困難さもある。一方、炭化ケイ素をマトリツク
スとして用いるものでは、燃料電池の運転温度を
190〜200℃程度に高くすることができるという利
点を有するが、一方において、炭化ケイ素は完全
な絶縁物ではなく、比抵抗値が103〜107Ω・cmで
あり、電子導電性を有するという欠点がある。す
なわち、燃料電池内部で短絡を生じ、性能が劣る
という問題がある。さらに、炭化ケイ素では、そ
の製造時に炭素と酸化ケイ素を高温下で反応させ
るために、未反応の炭素が残留し、これによる電
子導電性も問題である。また、不純物として存在
する鉄により触媒の活性化を劣化させる等の悪影
響も大きな問題である。 Conventionally, in fuel cells using phosphoric acid as an electrolyte, a matrix for holding phosphoric acid has been used that is a mixture of phenolic resin fiber cloth or silicon carbide powder with polytetrafluoroethylene as a binder. However, these matrices have the following drawbacks. That is, in the case of using a phenolic resin fiber cloth as a matrix, when the operating temperature of the fuel cell exceeds 130° C., the phenolic resin gradually carbonizes, and as a result, long-term operation becomes impossible. In order to eliminate these drawbacks, it is conceivable to lower the operating temperature of the fuel cell, but in this case a serious problem arises in that the output of the fuel cell is significantly reduced. Another difficulty is that sufficient care must be taken to control the temperature of the fuel cell to prevent it from becoming partially high temperature. On the other hand, in those that use silicon carbide as a matrix, the operating temperature of the fuel cell is
Silicon carbide has the advantage of being able to be heated to temperatures as high as 190 to 200°C, but on the other hand, silicon carbide is not a perfect insulator, has a specific resistance value of 10 3 to 10 7 Ω・cm, and has electronic conductivity. There is a drawback. That is, there is a problem that a short circuit occurs inside the fuel cell, resulting in poor performance. Furthermore, in the case of silicon carbide, since carbon and silicon oxide are reacted at high temperatures during its manufacture, unreacted carbon remains, which causes problems in electronic conductivity. In addition, iron present as an impurity causes adverse effects such as deterioration of catalyst activation, which is a major problem.
本発明の目的は以上のような欠点に鑑みなされ
たもので、電池性能を大幅に向上させた燃料電池
を提供するにある。 The object of the present invention was made in view of the above-mentioned drawbacks, and it is an object of the present invention to provide a fuel cell with significantly improved cell performance.
このような目的を達成するために本発明は、一
対のガス拡散電極を備え、該ガス拡散電極間に電
解質であるリン酸を保持するマトリツクスを介在
させてなる燃料電池において、前記マトリツクス
は酸化スズを結着材で結合して構成されてなるこ
とを特徴とする燃料電池である。 To achieve such an object, the present invention provides a fuel cell comprising a pair of gas diffusion electrodes and a matrix holding phosphoric acid as an electrolyte interposed between the gas diffusion electrodes, wherein the matrix is made of tin oxide. This is a fuel cell characterized in that it is configured by bonding the following with a binding material.
以下、本発明について説明する。 The present invention will be explained below.
一般に、燃料電池用マトリツクスとしての重要
な性質は、(1)高温（190℃〜200℃）のリン酸に対
して安定していること（高温のリン酸に溶けない
こと）、(2)リン酸の保持力が大であること、(3)電
子導電性がないこと（絶縁物であること）、(4)リ
ン酸との親和性が大きいこと、が挙げられる。し
かるに、これらの性質を満足する物質について
種々検討したところ、酸化スズがこれらの諸条件
を満足することが明らかになつた。すなわち、酸
化スズの微粉末に結着剤としてポリテトラフルオ
ロエチレンの如くリン酸に対して安定した物質を
１〜15重量％混合したものをマトリツクスにした
ものである。このようにして作られたマトリツク
スは、高温のリン酸に対して安定しており、しか
も電子導電性を有せず、さらに、リン酸との親和
力が大で、リン酸の保持力も従来のマトリツクス
の約２倍近くに達するという特徴を有している。 In general, the important properties of a fuel cell matrix are (1) stability against phosphoric acid at high temperatures (190°C to 200°C) (not soluble in high-temperature phosphoric acid); (3) It has no electronic conductivity (being an insulator), and (4) It has a high affinity for phosphoric acid. However, after examining various substances that satisfy these properties, it became clear that tin oxide satisfies these conditions. That is, the matrix is made by mixing fine powder of tin oxide with 1 to 15% by weight of a substance stable against phosphoric acid, such as polytetrafluoroethylene, as a binder. The matrix made in this way is stable against high-temperature phosphoric acid, has no electronic conductivity, and has a high affinity for phosphoric acid, and its retention of phosphoric acid is better than that of conventional matrices. It has the characteristic that it is nearly twice as large.
以下、実施例によつて本発明を詳細に説明す
る。 Hereinafter, the present invention will be explained in detail with reference to Examples.
二酸化スズ微粉末（200メツシユの金網を通過
する）98ｇに、結着剤としてポリテトラフルオロ
エチレン微粉末を界面活性剤によつて水中に懸濁
させた溶液30mlを加えて、ペースト状物を作つ
た。ポリテトラフルオロエチレン微粉末量は約２
ｇである。次に、この混合物を200℃で約８時間
加熱して水分を除去した後、98％に濃縮したリン
酸を加えて、該リン酸を保持するマトリツクスを
得た。リン酸量は約70重量％である。このように
して作られたマトリツクスを、一方のガス拡散電
極上に厚さ0.3mmになるように塗布した後、他方
のガス拡散電極を重ねて一体化し、燃料電池を組
み立てた。第１図に本発明による燃料電池の構造
を示す。ガス拡散電極は、白金を担持した炭素粉
末をカーボンペーパ上に塗布したものである。第
１図において、符号１はリン酸を含浸したマトリ
ツクス、２はアノード（燃料極）、３はカソード
（空気極）であり、アノード２には水素が、また
カソード３には空気がそれぞれ接するようになつ
ている。第２図に本発明で得たマトリツクスを用
いた電池の電流密度−電圧特性を、第３図に
200mA／cm2の電流密度で連続放電させた時の電
流電圧の経時変化を各々記号Ａで示している。な
お、第２図および第３図には比較のために、従来
の炭化ケイ素をマトリツクスにしたものを用いた
燃料電池の特性をそれぞれ記号Ｂで示している。
第２図および第３図から明らかなように、本発明
のマトリツクスを用いると、従来のものに比較し
てすぐれた性能を得ることができる。この原因と
しては、本発明のマトリツクスには、電子導電性
がなく、かつリン酸の保持力が大であると共に、
リン酸との親和力も大で、しかもリン酸に対して
安定しているためと考えられる。 To 98 g of tin dioxide fine powder (passed through a 200-mesh wire mesh), 30 ml of a solution of fine polytetrafluoroethylene powder as a binder suspended in water with a surfactant was added to make a paste. Ivy. The amount of polytetrafluoroethylene fine powder is approximately 2
It is g. Next, this mixture was heated at 200° C. for about 8 hours to remove moisture, and then phosphoric acid concentrated to 98% was added to obtain a matrix retaining the phosphoric acid. The amount of phosphoric acid is approximately 70% by weight. The matrix thus produced was applied to a thickness of 0.3 mm on one gas diffusion electrode, and then the other gas diffusion electrode was stacked and integrated to assemble a fuel cell. FIG. 1 shows the structure of a fuel cell according to the present invention. The gas diffusion electrode is made by applying platinum-supported carbon powder onto carbon paper. In FIG. 1, reference numeral 1 is a matrix impregnated with phosphoric acid, 2 is an anode (fuel electrode), and 3 is a cathode (air electrode). The anode 2 is in contact with hydrogen, and the cathode 3 is in contact with air. It's getting old. Figure 2 shows the current density-voltage characteristics of a battery using the matrix obtained in the present invention, and Figure 3 shows the current density-voltage characteristics of a battery using the matrix obtained by the present invention.
The symbol A indicates the change in current voltage over time during continuous discharge at a current density of 200 mA/cm 2 . For comparison, the characteristics of a fuel cell using a conventional silicon carbide matrix are indicated by the symbol B in FIGS. 2 and 3, respectively.
As is clear from FIGS. 2 and 3, when the matrix of the present invention is used, superior performance can be obtained compared to the conventional one. This is because the matrix of the present invention has no electronic conductivity and has a large phosphoric acid retention capacity.
This is thought to be because it has a high affinity for phosphoric acid and is moreover stable against phosphoric acid.
以上述べたように本発明によれば、マトリツク
スを、酸化スズと結着剤から成る構成としたの
で、従来の欠点を除去したすぐれた燃料電池用マ
トリツクスを得ることができるようになり、した
がつて、電池の性能を大幅に向上させることがで
き、その実用的価値は極めて大である。 As described above, according to the present invention, since the matrix is made of tin oxide and a binder, it is possible to obtain an excellent matrix for fuel cells that eliminates the conventional drawbacks. Therefore, the performance of the battery can be greatly improved, and its practical value is extremely large.
第１図は本発明に係るマトリツクスを用いた燃
料電池の断面図、第２図は本発明のマトリツクス
を用いた燃料電池と従来のマトリツクスを用いた
燃料電池における電流密度と電圧との関係を示す
図、第３図は本発明のマトリツクスを用いた燃料
電池と従来のマトリツクスを用いた燃料電池にお
ける放電時間と電圧との関係を示す図である。
１……マトリツクス、２……アノード、３……
カソード。
Fig. 1 is a cross-sectional view of a fuel cell using the matrix of the present invention, and Fig. 2 shows the relationship between current density and voltage in a fuel cell using the matrix of the present invention and a fuel cell using a conventional matrix. 3 are diagrams showing the relationship between discharge time and voltage in a fuel cell using the matrix of the present invention and a fuel cell using a conventional matrix. 1...matrix, 2...anode, 3...
cathode.
Claims (1)
間に電解質であるリン酸を保持するマトリツクス
を介在させてなる燃料電池において、前記マトリ
ツクスは酸化スズを結着材で結合して構成されて
なることを特徴とする燃料電池。 ２ 特許請求の範囲第１項において、前記結着剤
はポリテトラフルオロエチレンであることを特徴
とする燃料電池。[Claims] 1. A fuel cell comprising a pair of gas diffusion electrodes and a matrix holding phosphoric acid as an electrolyte interposed between the gas diffusion electrodes, wherein the matrix binds tin oxide with a binder. A fuel cell characterized by comprising: 2. The fuel cell according to claim 1, wherein the binder is polytetrafluoroethylene.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP56037846A JPS57152680A (en) | 1981-03-18 | 1981-03-18 | Fuel cell |
| US06/357,278 US4493879A (en) | 1981-03-18 | 1982-03-11 | Fuel cell |
| EP82102131A EP0060560A1 (en) | 1981-03-18 | 1982-03-16 | Fuel cell |
| CA000398513A CA1171903A (en) | 1981-03-18 | 1982-03-16 | Fuel cell |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP56037846A JPS57152680A (en) | 1981-03-18 | 1981-03-18 | Fuel cell |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS57152680A JPS57152680A (en) | 1982-09-21 |
| JPS6155226B2 true JPS6155226B2 (en) | 1986-11-26 |
Family
ID=12508893
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP56037846A Granted JPS57152680A (en) | 1981-03-18 | 1981-03-18 | Fuel cell |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS57152680A (en) |
-
1981
- 1981-03-18 JP JP56037846A patent/JPS57152680A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS57152680A (en) | 1982-09-21 |
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