JPH0247062B2 - - Google Patents
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- Publication number
- JPH0247062B2 JPH0247062B2 JP58228959A JP22895983A JPH0247062B2 JP H0247062 B2 JPH0247062 B2 JP H0247062B2 JP 58228959 A JP58228959 A JP 58228959A JP 22895983 A JP22895983 A JP 22895983A JP H0247062 B2 JPH0247062 B2 JP H0247062B2
- Authority
- JP
- Japan
- Prior art keywords
- water
- negative electrode
- electrolyte
- battery
- positive electrode
- 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
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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
- H01M8/08—Fuel cells with aqueous electrolytes
-
- 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
- Fuel Cell (AREA)
- 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)
Description
【発明の詳細な説明】
本発明はアルカリマトリツクス型水素−酸素燃
料電池の改良に係り、その目的とするところは電
池の放電生成物である水を負極側から確実に系外
へ除去し得る方法を提供せんとするにある。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to improvement of an alkaline matrix hydrogen-oxygen fuel cell, and its purpose is to reliably remove water, which is a discharge product of the cell, from the negative electrode side to the outside of the system. I'm trying to provide a method.
アルカリマトリツクス型水素−酸素燃料電池は
電解液となる水酸化カリウム水溶液を保持させた
シート状のアスベストマトリツクスの両面に金、
白金、銀あるいはパラジウムブラツクを触媒する
正極を負極とを密着させ、電極の背面にはそれぞ
れ酸化剤となる酸素と燃料となる水素とを供給す
るためのガス室を有する構造からなつている。 In an alkaline matrix hydrogen-oxygen fuel cell, gold and gold are coated on both sides of a sheet-like asbestos matrix that holds an aqueous potassium hydroxide solution as an electrolyte.
The positive electrode, which uses platinum, silver, or palladium black as a catalyst, is brought into close contact with the negative electrode, and the backside of each electrode has a gas chamber for supplying oxygen, which serves as an oxidizing agent, and hydrogen, which serves as a fuel.
電池の起電反応は次のとおりである。 The electromotive reaction of the battery is as follows.
正極で１／2O2＋H2O＋2e→2HO-…(1)
負極でH2＋2OH-→2H2O＋2e …(2)
全体で１／2O2＋H2→H2O …(3)
(3)式から明らかなように、この電池では電極反
応の進行に伴ない水が生成するので、電池を安定
して作動させるためには生成水を系外へ迅速に除
去しなければならない。At the positive electrode, 1/2O 2 +H 2 O+2e→2HO - …(1) At the negative electrode, H 2 +2OH - →2H 2 O+2e …(2) Overall, 1/2O 2 +H 2 →H 2 O …(3) Equation (3) As is clear from the above, in this battery, water is generated as the electrode reaction progresses, so in order to operate the battery stably, the generated water must be quickly removed from the system.
(2)式から明らかなように、水の生成は負極側で
起るので、生成水の除去は負極側で行なうのが好
ましく、本願発明者らか、多孔性焼結ニツケル板
からなる水吸収板を負極背面に密着するように配
設して、この水吸収板の背面に加湿した水素を供
給するような構造の電池を提案した。 As is clear from equation (2), since water generation occurs on the negative electrode side, it is preferable to remove the generated water on the negative electrode side. We proposed a battery structure in which a plate is placed in close contact with the back surface of the negative electrode, and humidified hydrogen is supplied to the back surface of the water absorbing plate.
かかる構造の電池では、電解液と負極との界面
で生成した水は一旦上記水吸収板に吸いとられ、
しかる後に水素ガス中へ蒸発して、未反応水素ガ
スと共に系外へ除去される。 In a battery with such a structure, water generated at the interface between the electrolyte and the negative electrode is once absorbed by the water absorption plate,
Thereafter, it evaporates into hydrogen gas and is removed from the system together with unreacted hydrogen gas.
この時、水吸収板中の水だけが蒸発して電解液
の水が蒸発しないようにするために、水素は電解
液の飽和水蒸気圧に等しい水蒸気圧を持つように
加湿された後、電池に供給されるが、その供給量
は生成水を蒸発させるに充分な量でなければなら
ない。通常、この供給量は電池の放電反応による
消費量の数倍〜数10倍である。 At this time, in order to prevent only the water in the water absorption plate from evaporating and the water in the electrolyte to evaporate, the hydrogen is humidified so that it has a water vapor pressure equal to the saturated water vapor pressure of the electrolyte, and then is added to the battery. However, the amount supplied must be sufficient to evaporate the produced water. Usually, this supply amount is several times to several tens of times the amount consumed by the battery discharge reaction.
一方、酸素ガス室は行きどまりになつていて、
酸素は正極で消費された量だけが供給される。そ
れ故、かかる構造の電池に於ては正極側から生成
水が除去されることはなく、またあつてはならな
い。 Meanwhile, the oxygen gas chamber has reached a dead end.
Only the amount of oxygen consumed at the positive electrode is supplied. Therefore, in a battery having such a structure, generated water is not and must not be removed from the positive electrode side.
電池の放電時には正極側で水が消費され、負極
側で水が生成するので、マトリツクス中の電解液
濃度は、正極側に高く、負極側に低く分布する。
従来は上記電解液の濃度差を利用して、つまり、
負極側の電解液の粘度が正極側のそれよりも小さ
くなり、電極の細孔を通りやすくする性質を利用
して負極背面に生成水を押し出してした。しか
し、かかる方法は、電解液の微妙な性質を利用し
ているので、信頼性に欠け、事実、電池を長時間
運転したり、負荷を急激に変動させた場合には、
正極から電解液が漏出することがあつた。 When a battery is discharged, water is consumed on the positive electrode side and water is produced on the negative electrode side, so that the electrolyte concentration in the matrix is distributed high on the positive electrode side and low on the negative electrode side.
Conventionally, the difference in concentration of the electrolyte was used, that is,
The viscosity of the electrolyte on the negative electrode side is lower than that on the positive electrode side, and the produced water is pushed out to the back of the negative electrode by taking advantage of the property that it passes easily through the pores of the electrode. However, such methods are unreliable because they rely on the delicate properties of the electrolyte, and in fact, if the battery is operated for a long time or the load is changed rapidly,
Electrolyte sometimes leaked from the positive electrode.
この電解液の漏出は、マトリツクス中の電解液
濃度を低下させ、電池電圧の劣化をひきおこす。 This leakage of electrolyte reduces the concentration of electrolyte in the matrix and causes deterioration of battery voltage.
本発明は、従来、アルカリマトリツクス型水素
−酸素燃料電池がもつ上述の如き欠点を除去せん
とするものてある。 The present invention aims to eliminate the above-mentioned drawbacks of conventional alkaline matrix hydrogen-oxygen fuel cells.
即ち、従来の電池の電極には、撥水性に対する
考慮がなされておらず、正極と負極とは同一の製
法、従つて同一の撥水性をもつていたが、本発明
は正極の撥水性を負極のそれよりも相対的に大き
くして、電解液が正極の細孔よりも負極のそれを
通りやすくすることにより、正極からの電解液の
漏出を防止するものである。 That is, in conventional battery electrodes, no consideration was given to water repellency, and the positive electrode and negative electrode were manufactured using the same method and therefore had the same water repellency.However, in the present invention, the water repellency of the positive electrode is By making the pores relatively larger than those of the positive electrode so that the electrolyte passes through the pores of the negative electrode more easily than the pores of the positive electrode, leakage of the electrolyte from the positive electrode is prevented.
以下、本発明の一実施例を図面に沿つて詳述す
る。 Hereinafter, one embodiment of the present invention will be described in detail with reference to the drawings.
第１図は水吸収板を備えるアルカリマトリツク
ス型水素−酸素燃料電池の単セル基本構造図であ
り、図に於いて、１は触媒となる銀−パラジウム
ブラツク70部を、ポリ４フツ化エチレン30部を結
着剤として、100メツシユニツケル網に糊塗した
後、窒素雰囲気中で340℃、20分の熱処理をして
相対的に大きな撥水性をもたせた厚さ0.3mmの正
極、２は銀−パラジウムブラツク85部をポリ４フ
ツ化エチレン15部を結着剤として100メツシユニ
ツケル網に糊塗した後、正極と同じ熱処理をして
相対的に小さな撥水性をもたせた厚さ0.3mmの負
極、３は電解液となる30wt％水酸化カリウム水
溶液を保持させた厚さ0.5mmのアスベストマトリ
ツクス、４は負極２の背面に位置し、負極側の片
面に水素ガスの通路となる凹部５と該凹部並びに
負極へ水素ガスを供給するための貫通孔６とを有
する多孔性焼結ニツケル板からなる厚さ１mmの水
吸収板、７及び７′はニツケルエキスパンド網か
らなる集電網、８及び８′はステンレススチール
板からなる集電板、９及び９′は電池温度を一定
に保つために冷媒が流されるポリサルフオン樹脂
製のクーラントプレートである。酸素ガス室１０
は行きどまりになつていて、酸素ガスは消費され
た量だけが供給される。 Figure 1 is a basic structural diagram of a single cell of an alkaline matrix type hydrogen-oxygen fuel cell equipped with a water absorption plate. 30 parts as a binder, glued on a 100 mesh mesh net, and then heat treated in a nitrogen atmosphere at 340℃ for 20 minutes to give it relatively high water repellency. 2 is a silver-thick positive electrode. 85 parts of palladium black was glued onto a 100 mesh unit mesh using 15 parts of polytetrafluoroethylene as a binder, and then subjected to the same heat treatment as the positive electrode to give it relatively small water repellency. 3 is a 0.3 mm thick negative electrode. An asbestos matrix 4 with a thickness of 0.5 mm holding a 30wt% potassium hydroxide aqueous solution as an electrolyte, 4 is located on the back side of the negative electrode 2, and on one side of the negative electrode there is a recess 5 that serves as a passage for hydrogen gas, and the recess and A water absorbing plate with a thickness of 1 mm made of a porous sintered nickel plate having through holes 6 for supplying hydrogen gas to the negative electrode, 7 and 7' are current collection networks made of expanded nickel networks, and 8 and 8' are stainless steel. The current collector plates 9 and 9' made of steel plates are coolant plates made of polysulfon resin through which a coolant is flowed in order to keep the battery temperature constant. Oxygen gas chamber 10
has reached a dead end, and only the amount of oxygen gas consumed is supplied.
一方、水素ガス室１１には、加湿された水素ガ
スが供給され、その一部は水吸収板４の貫通孔６
及び水素ガス通路５を通つて負極２へ供給され
る。 On the other hand, humidified hydrogen gas is supplied to the hydrogen gas chamber 11, and a part of it is supplied to the through hole 6 of the water absorption plate 4.
and is supplied to the negative electrode 2 through the hydrogen gas passage 5.
この電池を放電すると、負極２と電解液との界
面で水が生成するので、マトリツクス３中の電解
液は体積膨脹して電極の細孔から外へ出ようとす
る。この時負極２の撥水性が正極１のそれよりも
相対的に小さいので、電解液の増加分は選択的に
負極の細孔を通つて負極背面に漏出し、正極側に
漏出することはない。 When this battery is discharged, water is generated at the interface between the negative electrode 2 and the electrolyte, so that the electrolyte in the matrix 3 expands in volume and tries to escape from the pores of the electrode. At this time, since the water repellency of negative electrode 2 is relatively smaller than that of positive electrode 1, the increased amount of electrolyte selectively leaks to the back of the negative electrode through the pores of the negative electrode, and does not leak to the positive electrode side. .
負極背面から漏出する電解液の増加分は電解液
の負極側最外端部、つまり、生成したばかりの水
であり一旦負極に密着するように配設された水吸
収板４に吸いとられた後、水素ガス中に蒸発して
未反応水素ガスと共に系外へ排出される。 The increased amount of the electrolyte leaking from the back of the negative electrode is absorbed by the outermost end of the electrolyte on the negative electrode side, that is, the water that has just been generated, and the water absorption plate 4 that is placed in close contact with the negative electrode. Thereafter, it evaporates into hydrogen gas and is discharged from the system together with unreacted hydrogen gas.
次に本発明の効果を確かめるために、電極作用
面積が25cm2の第１図に示すような本発明型電池Ａ
と、正極及び負極に第１図の２で示される同一の
撥水性を有する電極を用いた従来型電池Ｂとを放
電した結果について述べる。 Next, in order to confirm the effects of the present invention, a battery A of the present invention type as shown in FIG .
The following describes the results of discharging a conventional battery B using electrodes having the same water repellency as shown by 2 in FIG. 1 for the positive and negative electrodes.
第２図は上記Ａ，B2つの電池を、作動温度が
80℃、ガス圧が１気圧のもとで、80℃における湿
度が71.7％になるように加湿した水素を239c.c.／
min（於25℃）の速度で供給しながら、6.25Aの定
電流連続放電をした時の電池電圧の推移を示す図
である。 Figure 2 shows the above two batteries A and B at different operating temperatures.
At 80℃ and gas pressure of 1 atm, 239 c.c. of hydrogen was humidified so that the humidity at 80℃ was 71.7%.
FIG. 4 is a diagram showing the change in battery voltage when continuous constant current discharge of 6.25 A is performed while supplying at a rate of 25° C. min (at 25° C.).
図から明らかなように、２つの電池の電圧劣化
速度には大きな差が認められた。これは本発明型
電池Ａの正極からは電解液が漏出しないのに対
し、従来型電池Ｂの正極からは電解液が漏出して
電解液濃度が低下しているためである。念のた
め、試験終了後両者のマトリツクス中の電解液濃
度を測定したところ、Ａでは29.2wtBでは26.4wt
％なる値が得られた。 As is clear from the figure, a large difference was observed in the voltage deterioration rate of the two batteries. This is because the electrolyte does not leak from the positive electrode of the battery A of the present invention, whereas the electrolyte leaks from the positive electrode of the conventional battery B, resulting in a decrease in the concentration of the electrolyte. Just to be sure, we measured the electrolyte concentration in both matrices after the test, and found that A was 29.2wtB and 26.4wtB.
A value of % was obtained.
なお、上記実施例では撥水性の強さをポリ４フ
ツ化エチレンの混入比で調整したが、熱処理温度
やその時間を変えることによつても、更に、触媒
をニツケル網に糊塗した後加圧することによつて
も調整可能である。 In addition, in the above example, the strength of water repellency was adjusted by the mixing ratio of polytetrafluoroethylene, but it could also be done by changing the heat treatment temperature and time. It can also be adjusted by
また、撥水性の強さは電極に水圧をかけてい
き、該電極表面に水滴が現われた時の水圧で示す
ならば正極の撥水性は80〜120cm水柱、負極のそ
れは20〜60cm水柱がよい。 In addition, the strength of water repellency is expressed by applying water pressure to the electrode and measuring the water pressure when water droplets appear on the electrode surface.The water repellency of the positive electrode should be 80 to 120 cm water column, and that of the negative electrode should be 20 to 60 cm water column. .
以上詳述した如く、本発明は負極側での生成水
の除去が確実に行なえる寿命の長いアルカリマト
リツクス型水素−酸素燃料電池を提供するもので
あり、その工業的価値は極めて大である。 As detailed above, the present invention provides a long-life alkaline matrix hydrogen-oxygen fuel cell in which produced water can be reliably removed on the negative electrode side, and its industrial value is extremely large. .
第１図は本発明にかかるアルカリマトリツクス
型水素−酸素燃料電池の単セルの基本構造図であ
る。第２図定電流で連続放電した時の電池の電圧
の推移を示す図である。
１…正極、２…負極、３…電解液を保持させた
アスベストマトリツクス、４…水吸収板、５…水
素ガス通路、６…貫通孔、７，７′…集電網、８，
８′…集電板、９，９′…クーラントプレート、１
０…酸素ガス室、１１…水素ガス室、Ａ…本発明
型電池、Ｂ…従来型電池。
FIG. 1 is a basic structural diagram of a single cell of an alkaline matrix hydrogen-oxygen fuel cell according to the present invention. FIG. 2 is a diagram showing the change in battery voltage when continuously discharging at a constant current. 1...Positive electrode, 2...Negative electrode, 3...Asbestos matrix holding electrolyte, 4...Water absorption plate, 5...Hydrogen gas passage, 6...Through hole, 7, 7'... Current collector network, 8,
8'...Current plate, 9,9'...Coolant plate, 1
0...Oxygen gas chamber, 11...Hydrogen gas chamber, A...Battery of the present invention, B...Conventional battery.
Claims (1)
くしたことを特徴とするアルカリマトリツクス型
水素−酸素燃料電池。1. An alkaline matrix hydrogen-oxygen fuel cell characterized in that the water repellency of the positive electrode is relatively stronger than that of the negative electrode.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58228959A JPS60121678A (en) | 1983-12-02 | 1983-12-02 | Alkali matrix type hydrogen-oxygen fuel cell |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58228959A JPS60121678A (en) | 1983-12-02 | 1983-12-02 | Alkali matrix type hydrogen-oxygen fuel cell |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS60121678A JPS60121678A (en) | 1985-06-29 |
| JPH0247062B2 true JPH0247062B2 (en) | 1990-10-18 |
Family
ID=16884538
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP58228959A Granted JPS60121678A (en) | 1983-12-02 | 1983-12-02 | Alkali matrix type hydrogen-oxygen fuel cell |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS60121678A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100887817B1 (en) | 2007-11-13 | 2009-03-09 | 현대자동차주식회사 | Fuel Cell Stack with Internal Humidification |
-
1983
- 1983-12-02 JP JP58228959A patent/JPS60121678A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS60121678A (en) | 1985-06-29 |
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