JPS6313273A - Fuel cell using three layer structure gas diffusion electrode - Google Patents
Fuel cell using three layer structure gas diffusion electrodeInfo
- Publication number
- JPS6313273A JPS6313273A JP61155073A JP15507386A JPS6313273A JP S6313273 A JPS6313273 A JP S6313273A JP 61155073 A JP61155073 A JP 61155073A JP 15507386 A JP15507386 A JP 15507386A JP S6313273 A JPS6313273 A JP S6313273A
- Authority
- JP
- Japan
- Prior art keywords
- air electrode
- electrolyte
- substrate
- electrode
- voltage
- 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.)
- Granted
Links
- 239000000446 fuel Substances 0.000 title claims abstract description 15
- 238000009792 diffusion process Methods 0.000 title claims abstract description 10
- 239000003792 electrolyte Substances 0.000 claims abstract description 56
- 239000000758 substrate Substances 0.000 claims abstract description 42
- 239000005871 repellent Substances 0.000 claims abstract description 11
- 239000003054 catalyst Substances 0.000 claims description 27
- 230000000903 blocking effect Effects 0.000 claims description 12
- 229920000642 polymer Polymers 0.000 claims description 3
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 2
- 239000004917 carbon fiber Substances 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 239000010411 electrocatalyst Substances 0.000 claims 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 21
- 230000002940 repellent Effects 0.000 abstract 3
- 230000004888 barrier function Effects 0.000 abstract 2
- 230000000717 retained effect Effects 0.000 abstract 1
- 239000011148 porous material Substances 0.000 description 20
- 230000008859 change Effects 0.000 description 19
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- 238000010586 diagram Methods 0.000 description 11
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 11
- 239000004810 polytetrafluoroethylene Substances 0.000 description 11
- 239000003014 ion exchange membrane Substances 0.000 description 10
- 238000010521 absorption reaction Methods 0.000 description 9
- 230000007423 decrease Effects 0.000 description 9
- 230000000694 effects Effects 0.000 description 7
- 239000008151 electrolyte solution Substances 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 235000011149 sulphuric acid Nutrition 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 238000007605 air drying Methods 0.000 description 3
- 238000010790 dilution Methods 0.000 description 3
- 239000012895 dilution Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- 230000004044 response Effects 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000006230 acetylene black Substances 0.000 description 2
- 238000003411 electrode reaction Methods 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000005728 strengthening Methods 0.000 description 2
- 241000282326 Felis catus Species 0.000 description 1
- 229920006361 Polyflon Polymers 0.000 description 1
- -1 Polytetrafluoroethylene Polymers 0.000 description 1
- 239000000443 aerosol Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000003113 dilution method Methods 0.000 description 1
- 238000011038 discontinuous diafiltration by volume reduction Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- QLOAVXSYZAJECW-UHFFFAOYSA-N methane;molecular fluorine Chemical compound C.FF QLOAVXSYZAJECW-UHFFFAOYSA-N 0.000 description 1
- 238000011017 operating method Methods 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000036962 time dependent Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000009736 wetting Methods 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
-
- 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)
- Inert Electrodes (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、性能が安定化された燃料電池に関し、特に、
改良されたガス拡散電極を有する燃料電池に関する。[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a fuel cell with stabilized performance, and in particular,
FUEL CELLS WITH IMPROVED GAS DIFFUSION ELECTRODES.
燃料電池に用いられるガス拡散電極構造の一例としては
、特開昭５２−１５５３４２に記載されているものがあ
る。An example of a gas diffusion electrode structure used in a fuel cell is described in JP-A-52-155342.
上記発明は、リン酸型燃料電池に関するもので、カソー
ドとしての初期性能の良否を論じているにとどまってお
り、メタノール燃料電池にみられるようなイオン交換膜
とアノード（以下メタノール極と略記する）及びカソー
ド（以下空気極と略記する）という構成において、空気
極の電解液バランスや空気極への電解液のリザーブとい
う点については配慮がなされていなかった。これに対し
、本発明者らは、メタノール燃料電池の長寿命化に関し
、空気極の電解液バランスや電解液保持用マトリックス
の適用及び運転方法の最適化について検討を加え寿命の
改善を行ってきた。これらについては、既に出願済みで
あるが、以下には、これまで改良してきた基本的概念に
ついて述べ、新らたな問題点について記述する。The above invention relates to a phosphoric acid fuel cell, and only discusses the quality of its initial performance as a cathode. and a cathode (hereinafter abbreviated as air electrode), no consideration was given to the electrolyte balance of the air electrode or the reserve of electrolyte to the air electrode. In response, the present inventors have improved the lifespan of methanol fuel cells by examining the electrolyte balance of the air electrode, the application of an electrolyte retention matrix, and the optimization of operating methods. . Applications have already been filed for these, but below we will describe the basic concepts that have been improved so far and describe new problems.
メタノール燃料電池の性能低下原因を第４図と第５図に
示したモデルで説明する。これまでの研究結果から、初
期数百時間の電池電圧の低下は、空気極の電位低下に太
き（依存していることがわかっている。第４図には、電
池内の電極近傍の拡大モデル図と水の移動の律速過程を
示した。The causes of performance deterioration in methanol fuel cells will be explained using the models shown in FIGS. 4 and 5. From the results of previous research, we know that the drop in battery voltage during the initial several hundred hours is strongly dependent on the drop in potential at the air electrode. A model diagram and the rate-determining process of water movement are shown.
第４図囚において、空気室９から乾燥空気によって持ち
去られる水の移動速度をｒＩ ＋ イオン交換膜６を
透過するアノライト中の水の移動速度をｒ。In FIG. 4, the moving speed of water carried away by dry air from the air chamber 9 is rI + The moving speed of water in the anolyte that permeates through the ion exchange membrane 6 is r.
及びイオン交換膜を透過した水が空気極５にとり込まれ
る速度をｒ２とし、ｒ、）ｒ２りｒ３の関係を仮定した
考察をしてみる。第４囲いには、空気極５近傍のモデル
図を示すが、空気極５は電池の初期性能を発現するため
、電解液をあらかじめ所定量含浸しておく。この量的関
係を二次元的に示すが、このゾーンが反応の場８として
作用することになる。第４図回申イオン交換膜６側には
、アノライト（通常１．５ ＭＨ２ＳＯ４１，０ＭＣｌ
３０ＨＨｚＯ）が接しており、空気極側には、空気室９
に乾燥空気が供給される。このような状態で電池を作動
させたときの電解液のバランスのずれによる電圧変化の
状態を第５図に示す。第５図において、１１は電池を間
欠で運転した場合、１２は連続で作動させたときの電池
電圧の一般的変化を示した。図において初期の電圧から
徐々に低下する状態１３は、空気極の初期性能を発現さ
せるために含浸した電解液中のＨ２ＳＯ，が、イオン交
換膜のＨ２ＳＯ４電解液度と平衡状態を保つための排出
による現象である。このように電圧が低下した状態で電
池の作動を停止すると、イオン交換膜を透過してきたア
ノライト中のＨ２Ｏが空気極にとり込まれ空気極中の１
ｈｓＯ，の希釈による体積増加により第４図回申８の反
応の場が増大し、空気極の性能が向上するので、電圧は
上昇する。この電圧変化状態を表わしたのが図中１５に
相当する。Let r2 be the rate at which the water that has passed through the ion exchange membrane is taken into the air electrode 5, and a discussion will be made assuming the relationship r, )r2 - r3. A model diagram of the vicinity of the air electrode 5 is shown in the fourth box, and in order to develop the initial performance of the battery, the air electrode 5 is impregnated with a predetermined amount of electrolyte in advance. This quantitative relationship is shown two-dimensionally, and this zone acts as a reaction field 8. Figure 4. On the ion exchange membrane 6 side, an anolite (usually 1.5 MH2SO41.0MCl)
30HzO) is in contact with the air chamber 9 on the air electrode side.
dry air is supplied to the FIG. 5 shows the state of voltage change due to the imbalance of the electrolyte when the battery is operated in such a state. In FIG. 5, 11 shows the general change in battery voltage when the battery is operated intermittently, and 12 shows the general change in battery voltage when the battery is operated continuously. In the figure, state 13 where the voltage gradually decreases from the initial voltage is due to the discharge of H2SO in the electrolyte impregnated to develop the initial performance of the air electrode to maintain equilibrium with the H2SO4 electrolyte level in the ion exchange membrane. This is a phenomenon caused by When the battery operation is stopped with the voltage reduced in this way, the H2O in the anorite that has permeated through the ion exchange membrane is taken into the air electrode, and the 1
The increase in volume due to dilution of hsO increases the reaction field in Figure 4, Circulation 8, and improves the performance of the air electrode, so the voltage increases. This voltage change state corresponds to 15 in the figure.
電圧が上昇した状態で、電池を作動させると希釈された
空気極中のＨｚＳＯａは、連続的に乾燥空気を供給する
ことから、空気極中のＨ２ＳＯ４は、水分蒸発によって
濃縮される結果、体積の減少すなわち反応の場８の減少
によって電圧は徐々に低下する。間欠運転においては、
このくり返しで運転条件の変化に対応して一定の電圧を
維持することになる。一方連続運転においては、間欠運
転の希釈過程が発現しないだけで、最終的には電解液バ
ランスの平衡を保った状態で電圧も安定化する。ここで
前述の排出の概念について、空気極の撥水性・ の指標
となる電解液（＋１２ＳＯ，濃度）バランスとの関係に
おいて第６図を用いて説明する。第６図は、一般的に使
用される空気極と電解液として１．５ＭＨ２ＳＯ４を用
いたときの電解液バランスを示したもので、図中１６の
曲線は未処理の空気極を１．５ ＭＨｚＳＯ４水溶液に
触媒層を法例にして浮遊させたときのＨ２ＳＯ４の浸み
込む変化であり、１７は空気極にあらかじめ多量のＨ，
＋ＳＯ，を強制的に含浸し、同様の方法においてＨ２Ｓ
Ｏ，の排出の変化をみたものである。When the battery is operated with the voltage increased, the diluted HzSOa in the air electrode is continuously supplied with dry air, so the H2SO4 in the air electrode is concentrated by water evaporation, resulting in a decrease in volume. The voltage gradually decreases due to the reduction, ie the reduction of the reaction field 8. In intermittent operation,
By repeating this process, a constant voltage is maintained in response to changes in operating conditions. On the other hand, in continuous operation, the dilution process of intermittent operation does not occur, and the voltage is eventually stabilized with the electrolyte balance maintained. Here, the above-mentioned concept of discharge will be explained using FIG. 6 in relation to the electrolyte (+12SO, concentration) balance, which is an index of the water repellency of the air electrode. Figure 6 shows the electrolyte balance when a commonly used air electrode and 1.5 MHz SO4 are used as the electrolyte. 17 is the change in infiltration of H2SO4 when a catalyst layer is suspended in an aqueous solution.
+SO, and H2S in the same way.
The figure shows changes in O emissions.
測定温度は、電池の作動温度である６０℃である。The measurement temperature was 60° C., which is the operating temperature of the battery.
図中１６にみられるごとく、空気極は時間経過とともに
吸収量は増大し、１５０時間後においてほぼ一定の値を
示す。一方、初期に強制的にＨ２ＳＯ，含浸した空気極
は、時間経過とともにＨ２ＳＯ４を排出し、吸収曲線と
ほぼ重なり合う点で平衡になる。以上のように、ある条
件で作製した空気極と一定濃度のＨ２ＳＯ４電解液の間
には、その吸収量が平衡になる値があり、この値を電解
液平衡吸収量と定義しておく。As seen at 16 in the figure, the absorption amount of the air electrode increases over time, and shows a nearly constant value after 150 hours. On the other hand, the air electrode that is forcibly impregnated with H2SO at the beginning discharges H2SO4 over time and reaches equilibrium at a point where it almost overlaps with the absorption curve. As described above, there is a value at which the amount of absorption is balanced between the air electrode produced under certain conditions and the H2SO4 electrolyte of a constant concentration, and this value is defined as the equilibrium absorption amount of the electrolyte.
次に空気極中の電解液が濃縮したとき、空気極の電位が
どのように変化するかについて測定した結果について、
第７図を用いて説明する。第７図は空気極の単極電位を
測定するセルに電極をセントし、供給する乾燥空気の流
量を変化させたときの空気極電位を測定して示した。図
にみられるごとく、空気流量が約３ ｍＺ／ｍ１ｎ−ａ
ｎｔ以下においては、高い電位でほぼ一定の値を示すが
、空気流量が増大するにつれ電位は低下する。このこと
は、前述したごとく、乾燥空気を大量導入すると、空気
極に含まれる電解液中の水分が蒸発し、第４囲いに示し
た反応の場８の面積が減少するためである。Next, regarding the results of measuring how the potential of the air electrode changes when the electrolyte in the air electrode becomes concentrated,
This will be explained using FIG. FIG. 7 shows the air electrode potential measured when an electrode was placed in a cell for measuring the unipolar potential of the air electrode and the flow rate of dry air to be supplied was varied. As shown in the figure, the air flow rate is approximately 3 mZ/m1n-a
Below nt, the potential shows a nearly constant value at a high potential, but as the air flow rate increases, the potential decreases. This is because, as described above, when a large amount of dry air is introduced, the water in the electrolyte contained in the air electrode evaporates, and the area of the reaction field 8 shown in the fourth box decreases.
この減少は、第５図に示した１４の現象を間接的に証明
するものである。This decrease indirectly proves the 14 phenomena shown in FIG.
以上の実験事実をもとに電池電圧の低下を抑制する手段
として、空気極中の電解液の排出・希釈および濃縮に対
して、空気極の親水化により電解液の平衡吸収量を大き
くすること、運転において空気流量を最適化する又水の
移動速度や空気極−イオン交換膜界面の密着性の改善の
ため第４図■に示した１０の間隙に電解液含をペースト
を挿入するなどの手段を講じて電池の安定化を図ってき
た。Based on the above experimental facts, as a means to suppress the drop in battery voltage, the equilibrium absorption amount of the electrolyte can be increased by making the air electrode hydrophilic in response to the discharge, dilution, and concentration of the electrolyte in the air electrode. In order to optimize the air flow rate during operation and to improve the water movement speed and the adhesion between the air electrode and the ion exchange membrane interface, we introduced a paste containing electrolyte into the 10 gaps shown in Figure 4 (■). We have taken various measures to stabilize the battery.
ここで空気極の親水化という意味について考察しておく
。Let us now consider the meaning of making the air electrode hydrophilic.
一般的なガス拡散電極は、カーボン粉末上へ微細なｐｔ
粒子を高度に分散担持して活性を向上させた電極触媒と
ＩＣ水剤であるポリテトラフルオロエチレン（以下ＰＴ
ＦＥと略記する）の混合物を多孔質導電性基板上へ塗布
・焼成して作製される。A typical gas diffusion electrode uses fine PT on carbon powder.
Polytetrafluoroethylene (hereinafter referred to as PT) is an electrode catalyst with highly dispersed particles and improved activity, and an IC water agent.
It is manufactured by applying a mixture of FE (abbreviated as FE) onto a porous conductive substrate and baking it.
この種の電極においては、適度な撥水性を有し、反応の
場である液体−気体一固体の接する三相界面の面積の増
大と安定化を図る必要がある。In this type of electrode, it is necessary to have appropriate water repellency and to increase and stabilize the area of the three-phase interface where liquid-gas-solid contact, which is the site of reaction.
電極の撥水性すなわち電解液との濡れ性は、電解液の平
衡吸収量を測定し、その値を濡れ性の指標の一つとする
ことができる。一方電極の濡れ性と電極性能の関係につ
いては、電極触媒層細孔容積を占める電解液量を細孔占
有率と定義し、この細孔占有率との関係で整理できる。The water repellency of an electrode, that is, its wettability with an electrolytic solution, can be determined by measuring the equilibrium absorption amount of the electrolytic solution, and using the value as one of the wettability indicators. On the other hand, regarding the relationship between electrode wettability and electrode performance, the amount of electrolyte that occupies the pore volume of the electrode catalyst layer is defined as pore occupancy, and can be summarized in relation to this pore occupancy.
細孔占有率と空気極電位の関係をモデル的に第８図に示
す。第８図に示したごとく空気極電位は、細孔占有率が
ある範囲内で三相界面が理想的に形成されるため貰い性
能を示す。これに対し細孔占有率が小さい領域において
は、電解液による触媒層の濡れが不十分なためＨ゛移動
抵抗が大きくなり電位は低下する。逆に細孔占有率が大
きい所では、触媒層が電解液で十分覆われガスの拡散が
阻害される結果電位が低下することが予想される。The relationship between pore occupancy and air electrode potential is shown in FIG. 8 as a model. As shown in FIG. 8, the air electrode potential shows the yield performance because the three-phase interface is ideally formed within a certain range of pore occupancy. On the other hand, in a region where the pore occupancy is small, the wetting of the catalyst layer by the electrolytic solution is insufficient, so the H transfer resistance increases and the potential decreases. On the other hand, in areas where the pore occupancy is large, the catalyst layer is sufficiently covered with the electrolytic solution and gas diffusion is inhibited, resulting in a decrease in potential.
したがって性能の安定した空気極を得るためには、電池
の運転条件の変化によっても電位の安定した細孔占有率
領域からはずれない触媒層構造にする必要がある。Therefore, in order to obtain an air electrode with stable performance, it is necessary to have a catalyst layer structure that does not deviate from the pore occupancy region where the potential is stable even when the operating conditions of the battery change.
第８図１８に示した空気極は、第６図に示した空気極に
ついて示したものであり、１９はこれまでの検討結果に
より得られた親水化した空気極の値を示した。図中１８
に示す空気極は、電極性能がクリティカルな位置に存在
し、電池運転条件によって大きく変化することが予想さ
れるのに対し、１９に示した空気極では、性能のフラッ
トな部分に位置し、電池運転条件が多少変化しても空気
極性能が安定領域にあるのがわかる。The air electrode shown in FIG. 8 and 18 is the same as the air electrode shown in FIG. 6, and 19 indicates the value of the hydrophilic air electrode obtained from the results of previous studies. 18 in the diagram
The air electrode shown in 19 is located at a critical position for electrode performance and is expected to vary greatly depending on battery operating conditions, whereas the air electrode shown in 19 is located at a flat area of performance and is expected to vary greatly depending on battery operating conditions. It can be seen that the air electrode performance remains in a stable region even if the operating conditions change slightly.
以上の結果をまとめて、電池電圧の経時変化で評価して
みた。ちなみに、第６図に示した親水化の改良がなされ
ていない空気極を用いた場合の性能も、比較する意味で
示す。We summarized the above results and evaluated them based on changes in battery voltage over time. Incidentally, the performance when using the air electrode shown in FIG. 6 without the hydrophilic improvement is also shown for comparison.
第９図には、第６図に示した空気極を用いた電池の経時
変化を示すが、電池電圧は初期の値から掻く短時間で急
激に低下し、その後徐々に電圧は低下する傾向にある。Figure 9 shows the change over time of a battery using the air electrode shown in Figure 6. The battery voltage drops rapidly from its initial value in a short period of time, and then the voltage tends to gradually drop. be.
これに対し、第８図１９に示した性質をもつ親水化した
空気極を用いた電池電圧の経時変化を第１０図に示す。On the other hand, FIG. 10 shows the change in battery voltage over time using a hydrophilized air electrode having the properties shown in FIG. 8 and 19.
図にみられるごとく電圧変化は、従来までの傾向と異な
り、初期電圧は低い値を示すが時間経過とともに上昇し
、２１で示したごとく約０．３２Ｖで安定化する。図中
、２゜で示した破線は、空気極及びメタノール極それぞ
れの単極電位から求めた電位差を表わしており、理想的
な電池電圧は２０とほぼ同じ電圧を示すものである。As can be seen in the figure, the voltage change differs from the conventional trend in that the initial voltage shows a low value, but increases over time and stabilizes at about 0.32V as shown at 21. In the figure, the broken line shown at 2 degrees represents the potential difference determined from the monopolar potentials of the air electrode and the methanol electrode, and the ideal battery voltage is approximately the same voltage as 20.
以上述べてきたごとく、先に出願済みの改良技術におい
て、従来型まれてきた電池電圧の安定化については達成
できたが、単極差の電圧を発現できないという問題があ
った。本発明ではこの原因が何に起因するかについて考
察し、電池電圧の安定化と向上を図ることにある。As described above, although the previously applied improved technology was able to achieve the stabilization of battery voltage that had been achieved in the past, there was a problem in that it was unable to produce a voltage with a single pole difference. The present invention aims to consider what causes this and to stabilize and improve the battery voltage.
第１０図で用いた空気極構造を第１１図に示す。第４図
５では電極全体を空気極としたが、詳細にみれば第１１
図に示すごとく、多孔質導電性基板１上に触媒層２が部
分的に基板上にくい込んだ形で形成されており、厚さ関
係は基板１が約４００μｍで触媒層は約１００μｍであ
る。このような電極構成において、触媒層の親水化の程
度を増大すると、触媒層中の電解液及び発電にともなう
空気極からの生成水が基板中細孔に凝集する結果、ガス
拡散が阻害され、電池電圧が低下する。そこで本発明者
らは、これらの問題点を解決するため、基板１にあらか
じめＰＴＦＥ等の撥水性ポリマーを塗布し高温で焼成し
溶融させることによりＰＴＦＥの撥水性により、凝集を
抑制した。しかしながら、基板１のＰＴＦＥ処理によっ
て↑Ω水性は強化されるが、基板の細孔の大きさはほと
んど変化していないことが判明した。これらの関係を未
処理基板と比較してみる。FIG. 11 shows the air electrode structure used in FIG. 10. In Figure 4 and 5, the entire electrode is an air electrode, but if we look at the details, the 11th
As shown in the figure, a catalyst layer 2 is formed on a porous conductive substrate 1 so as to be partially embedded in the substrate, and the substrate 1 has a thickness of about 400 μm and the catalyst layer has a thickness of about 100 μm. In such an electrode configuration, when the degree of hydrophilization of the catalyst layer is increased, the electrolyte in the catalyst layer and the water generated from the air electrode during power generation aggregate in the pores in the substrate, thereby inhibiting gas diffusion. Battery voltage drops. Therefore, in order to solve these problems, the present inventors applied a water-repellent polymer such as PTFE to the substrate 1 in advance and baked and melted it at a high temperature, thereby suppressing agglomeration due to the water-repellent property of PTFE. However, it was found that although the ↑Ω aqueous property was strengthened by the PTFE treatment of the substrate 1, the pore size of the substrate was hardly changed. Let's compare these relationships with an untreated substrate.
表１
またＰＴＦＥ処理基板のＳＥＭの観察写真を第１２図に
示す。観察結果は３００倍である。図にみられるごとく
炭素繊維で三次元的に構成された基板にＰＴＦＥが溶融
してからみ合っている様がみられるが、比較的大きな細
孔が存在しているのがわかる。Table 1 Further, an SEM observation photograph of the PTFE-treated substrate is shown in FIG. The observation result is 300 times larger. As seen in the figure, it can be seen that PTFE is melted and intertwined with a substrate made of three-dimensional carbon fibers, and it can be seen that there are relatively large pores.
以上のように撥水化した基板を用いて、触媒層を親水化
したとき、短時間においては、基板の撥水液で電解液の
バランスが保たれるが、基板の細孔が大きいことから、
触媒層中の電解液が、細孔をすり抜けるという現象が生
じ、触媒層の電解液の溢流による電解液体積の減少や、
基板をすり抜けた電解液がガス通路に濃縮し閉塞すると
いう問題があり、電池電圧の低下や性能の不安定さを引
き起こす原因となっていた。When the catalyst layer is made hydrophilic using a water-repellent substrate as described above, the balance of the electrolyte is maintained by the water-repellent liquid on the substrate for a short time, but because the pores of the substrate are large, ,
A phenomenon occurs in which the electrolyte in the catalyst layer slips through the pores, and the electrolyte volume decreases due to overflow of the electrolyte in the catalyst layer.
There is a problem in that the electrolyte that has passed through the substrate condenses and blocks the gas passage, causing a drop in battery voltage and unstable performance.
しかるに本発明は、触媒層の電解液が基板をすり抜ける
現象をほぼ完全に阻止して、長期間電圧の安定した燃料
電池を提供しようとするものである。However, the present invention aims to provide a fuel cell with stable voltage for a long period of time by almost completely preventing the electrolyte in the catalyst layer from slipping through the substrate.
本発明では、前述の問題を解決するための技術的手段と
して、燃料電池のガス拡散電極において、基板の撥水化
処理に加えて、基板側に集電層をかね備えた電解液透過
阻止層を設けたことを。特徴とする。これは基板側のｔ
ｏ水力の強化とともに、層の細孔を微小化し毛管力によ
り電解液の透過を阻止するものである。In the present invention, as a technical means to solve the above-mentioned problem, in addition to water-repellent treatment of the substrate in a gas diffusion electrode of a fuel cell, an electrolyte permeation blocking layer that also has a current collecting layer on the substrate side is provided. that we have established Features. This is the t on the board side.
o In addition to strengthening hydraulic power, the pores in the layer are made smaller to prevent electrolyte from permeating through capillary force.
これにより空気極中の電解液は、常に定常に保たれるこ
とから、電池電圧が高く且つ安定した性能が得られる。As a result, the electrolyte in the air electrode is always kept constant, resulting in high battery voltage and stable performance.
本発明の作用については後述するが、その電極構造を第
１図に、電解液透過阻止層の表面ＳＥＭ写真を第２図に
示す。The effect of the present invention will be described later, and the electrode structure thereof is shown in FIG. 1, and the surface SEM photograph of the electrolyte permeation blocking layer is shown in FIG. 2.
第１図において、３は電解液透過阻止層を表わし、基板
に部分的にくいこんでおり、厚みは約１００μｍである
。この電解液透過阻止層を設けた基板の物性値を表１と
対比して以下に示す。In FIG. 1, numeral 3 represents an electrolyte permeation blocking layer, which is partially embedded in the substrate and has a thickness of approximately 100 μm. The physical property values of the substrate provided with this electrolyte permeation blocking layer are shown below in comparison with Table 1.
（来夏以下余白） 表２ 表２に示した撥水化基板は、以下の手順で作製した。(Left below next summer) Table 2 The water-repellent substrate shown in Table 2 was produced by the following procedure.
多孔質炭素基板に８■／ｃｄになるようにＰＴＦＥを含
浸し風乾後、基板１ ｃＴＡ当り２．５ ｍｇ Ｐ Ｔ
Ｆ Ｅと２，５■のアセチレンブラックの混合ペース
トを塗布した後、空気中３７０℃で０．５時間焼成した
。A porous carbon substrate was impregnated with PTFE to a rate of 8 μ/cd, and after air drying, 2.5 mg PT/cTA per substrate.
After applying a mixed paste of FE and 2.5 μm of acetylene black, it was baked in air at 370° C. for 0.5 hour.
表２中、ｔａ水性の評価を強力としたのは、第６図のよ
うな試験法を行ったとき、４０９時間浸漬後において電
解液透過阻止層への吸収量は微かに０．１■／ｃａｌで
あることから推定した判定に基づくものである。電解液
透過阻止層の特徴は、この撥水力の強化と同時に細孔径
分布が０，１μｍと非常に小さい方に移行したことにあ
り、これにより触媒層からの電解液のもれ出しが阻止さ
れるところにある。この層のＳＥＭ像を図１５に示すが
、第１２図に比し、非常に緻密な層が形成されているの
がわかる。なお観察倍率は、３００倍である。In Table 2, the reason why the ta aqueous property evaluation is strong is that when the test method shown in Figure 6 was carried out, the amount of absorption into the electrolyte permeation blocking layer after 409 hours of immersion was only 0.1 / This is based on the determination estimated from the fact that it is cal. The characteristic of the electrolyte permeation prevention layer is that at the same time as this water repellency is strengthened, the pore size distribution shifts to a very small 0.1 μm, which prevents the electrolyte from leaking out from the catalyst layer. It's located where you are. A SEM image of this layer is shown in FIG. 15, and it can be seen that a very dense layer is formed compared to FIG. 12. Note that the observation magnification is 300 times.
本発明技術の作用を、電池電圧が高く且つ安定化するた
め、空気極に必要な第１図の三層構造に関するそれぞれ
の性質について比較してみる。The effect of the technology of the present invention will be compared with respect to each property of the three-layer structure shown in FIG. 1, which is necessary for the air electrode in order to increase and stabilize the battery voltage.
表３
表３には、三層構造電極のそれぞれの箇所の性質の相対
比較をした。これにより、電解液透過阻止層は名称の通
りの作用をし、基板の空隙は触媒層から電解液が排出さ
れる状態のときリザーバとして働き且つ触媒層の電解液
が不足のときは供給源としての作用をもつ。Table 3 Table 3 shows a relative comparison of the properties of each location of the three-layer structure electrode. As a result, the electrolyte permeation blocking layer works as its name suggests, and the voids in the substrate act as a reservoir when the electrolyte is being drained from the catalyst layer, and as a supply source when the electrolyte in the catalyst layer is insufficient. It has the effect of
以下には本発明の実施例について記述するが、本発明は
以下の実施例に限定されるものではない。Examples of the present invention will be described below, but the present invention is not limited to the following examples.
実施例１
本実施例では、各種三層構造電極の作製と６０ｍＡ／ｄ
の電流密度における空気極の単極電位を従来電極と比較
して示す。以下に三層構造電極の作製手順の代表例を記
す。Example 1 In this example, we will fabricate various three-layer structure electrodes and
The monopolar potential of the air electrode at a current density of is compared with that of a conventional electrode. A typical example of the procedure for producing a three-layer structure electrode is described below.
導電性多孔質基板へ８■ＰＴＦＥ／ｃｊになるようにポ
リフロンディスパージョンを含浸・風乾後、基板１ｃ１
１当り（２，５ｗＰＴＦＥと２．５■アセチレンブラン
ク）になるように水ペーストを塗布風乾後、空気中にて
３７０℃−０，５時間焼成して電解液透過阻止層付基板
とする。その後（３■ｃａｔ／ｃｎｌ−４■ＰＴＦＥエ
アロゾル／−）の混合ペーストを反対側に塗布し、風乾
後、空気中にて２００℃−０，５時間焼成し空気極とし
た。このようにして作製した空気極について、１．５
ＭＨ！ＳＯ４電解液中、６０℃において６０ｍＡ／ｃｏ
！の電流密度のときの空気極電位を測定した。その結果
を表４に示す。After impregnating the conductive porous substrate with Polyflon dispersion to a concentration of 8■PTFE/cj and air drying, the substrate 1c1
A water paste was applied in an amount of 1/2 (2.5 w PTFE and 2.5 w acetylene blank), air-dried, and then baked in air at 370° C. for 0.5 hours to obtain a substrate with an electrolyte permeation blocking layer. Thereafter, a mixed paste of (3■cat/cnl-4■PTFE aerosol/-) was applied to the opposite side, and after air drying, it was baked in air at 200°C for 0.5 hours to form an air electrode. Regarding the air electrode produced in this way, 1.5
MH! 60 mA/co at 60°C in SO4 electrolyte
! The air electrode potential was measured at a current density of . The results are shown in Table 4.
（来夏以下余白） 表４中、ＡＢはアセチレンブラック、（ＣＦ）、。(Left below next summer) In Table 4, AB is acetylene black, (CF).
はフッ化黒鉛の略号である。フッ化黒鉛はＰＴＦＥより
撥水性の強い物質であり、層の撥水性を強化する目的で
添加した。また電極中触媒層中の白金量は０．９■／ｄ
である。is the abbreviation for fluorinated graphite. Graphite fluoride is a substance with stronger water repellency than PTFE, and was added for the purpose of strengthening the water repellency of the layer. In addition, the amount of platinum in the catalyst layer in the electrode is 0.9■/d
It is.
実施例２
実施例１で作製した空気極（表４中隘８）を用いてメタ
ノール極及びイオン交換膜を組合せた単位電池を構成し
、寿命試験を行ってみた。その結果を第３図に示す。第
３図において用いた電極の有効面積は１３Ｍ、アノライ
トは１．５ ＭＨｚＳＯ＊ １ＭＣＨ３０Ｈで運転は
６０℃で行った。Example 2 A unit battery was constructed by combining a methanol electrode and an ion exchange membrane using the air electrode prepared in Example 1 (Table 4, middle column 8), and a life test was conducted. The results are shown in FIG. The effective area of the electrode used in FIG. 3 was 13 M, the anolyte was 1.5 MHz SO* 1 MCH30H, and the operation was performed at 60°C.
第３図によれば、電池電圧は、初期０．３Ｖから時間経
過とともに徐々に上昇し、約４０時間からほぼ一定にな
り、０．３８Ｖと貰い電圧を２００時間以上に亘って維
持している。また、この電圧の維持は少なくとも５００
時間まで確認されており、従来のものに比べて寿命は約
２．５倍以上のびている。なお、このときの電池の負荷
は、電流密度６０ｍＡ／ｃ＋Ｊと一定放電したときの値
である。According to Figure 3, the battery voltage gradually increased over time from an initial value of 0.3V, became almost constant after about 40 hours, and maintained the received voltage of 0.38V for over 200 hours. . Also, this voltage must be maintained for at least 500
It has been confirmed that the lifespan is approximately 2.5 times longer than that of conventional products. Note that the load on the battery at this time is the value when the battery is discharged at a constant current density of 60 mA/c+J.
実施例３
実施例１で作製した空気極（表４中４５．６゜７、 ９
．１０．１１及び１２）を用いて、実施例２と同様、単
位電池の寿命評価を行ったところ、第３図とほぼ同様の
傾向を示し、電池電圧はいずれの場合においても０．３
８Ｖ±０．０１ Ｖ （６０ｍＡ／ｃｎｔ）の範囲に落
ちつき、従来のものにくらべ少なくとも２．５倍の時間
安定した性能を示した。Example 3 The air electrode prepared in Example 1 (45.6°7, 9 in Table 4)
．． 10.11 and 12) were used to evaluate the lifespan of the unit battery in the same manner as in Example 2. The results showed almost the same tendency as in Figure 3, and the battery voltage was 0.3 in both cases.
It settled in the range of 8V±0.01V (60mA/cnt) and showed stable performance for at least 2.5 times longer than the conventional one.
本発明によれば、ガス拡散電極触媒層に保持させた電解
液が、基板の外側に漏れ出すのを抑制すると同時に、触
媒層と電解液透過阻止層間の基板空隙が触媒層中の電解
液の溢流に対し、リザーバ効果を発揮するので、電池を
長期間に亘ワて安定して高い電圧を維持する効果がある
。According to the present invention, the electrolytic solution held in the gas diffusion electrode catalyst layer is suppressed from leaking to the outside of the substrate, and at the same time, the substrate gap between the catalyst layer and the electrolytic solution permeation blocking layer is Since it exerts a reservoir effect against overflow, it has the effect of maintaining a stable high voltage of the battery over a long period of time.
第１図は本発明による空気極の構造を示す図、第２図は
本発明による空気極の電解液透過阻止層の表面のＳＥＭ
像、第３図は本発明による空気極を用いた単位電池の経
時変化を示す図、第４図囚は、従来の単位電池の空気極
近傍の拡大図、■は水の移動のモデル図、第５図は電池
電圧の経時変化を示す図、第６図は空気極の電解液平衡
吸収量曲線を示す図、第７図は空気流量と空気極電位変
化の関係を示す図、第８図は空気極のもつ細孔占有率と
電位の関係を示す図、第９図は占有率の小さい空気極を
用いた単位電池の経時変化を示す図、第１０図は占有率
の大きい空気極を用いた単位電池の経時変化を示す図、
第１１図は従来の空気極の構造を示す図、第１２図は従
来の基板側のＳＥＭ像である。
１・・・多孔質導電性基板、２・・・空気極触媒層、３
・・・電解液透過阻止層、４・・・本発明による三層構
造空気極を用いた単位電池電圧の経時変化、５・・・空
気極、６・・・イオン交換膜、７・・・アノライト、８
・・・空気極の反応の場、９・・・空気室、１０・・・
空気極とイオン交換膜の空隙、１１・・・電池の間欠運
転における電池電圧の経時変化、１２・・・電池の連続
運転における電圧の経時変化、１３・・・触媒層の電解
液の排出による電圧低下現象、１４・・・触媒層中の電
解液の濃縮による体積の減少による電圧低下現象、１５
・・・触媒層中の電解液の水の希釈による体積の増加に
よる電圧上昇現象、１６・・・空気極の電解液吸収曲線
、１７・・・空気極の電解液排出曲線、１８・・・は電
解液細孔占有率の小さい空気極の特性、１９・・・細孔
占有率の大きい空気極の特性、２０・・・空気極及びメ
タノール極の電位差から求めた電圧、２１・・・親水化
した空気極を用いた単位電池の電圧の経時変化。
特許出願人 株式会社日立製作所
代理人 弁理士 平 木 祐 輔
ｉ−−−−一多孔質導電性基板
２−−−−一空気極触媒層
３−−−−一電解液透過阻止層
第２図
第３図
運転時間（ｈ）
第４図
（Ａ） （Ｂ）
Ｕ
５−一一一空気極
６−一一一 イオン交換膜
７−−−−７ノライト
８−一一一空気極の反応の場
９−一一一空気室
１０−−−一空気極とイオン交換摸の空隙第５図
２ 第６図
浸漬時間（ｈ）
第７図
空気流量（ｍｌ／ｍｉｎ−ａｍ２）
細孔占有率（’／、）
第９図
運転時間（ｈ）
第１○図
運転時間（ｈ）
第１１図
１−一一一多孔質導電性基板
２−一一一空気極触媒層FIG. 1 is a diagram showing the structure of the air electrode according to the present invention, and FIG. 2 is an SEM of the surface of the electrolyte permeation blocking layer of the air electrode according to the present invention.
Figure 3 is a diagram showing the change over time of a unit battery using the air electrode according to the present invention, Figure 4 is an enlarged view of the vicinity of the air electrode of a conventional unit battery, ■ is a model diagram of water movement, Fig. 5 shows the change in battery voltage over time, Fig. 6 shows the electrolyte equilibrium absorption curve of the air electrode, Fig. 7 shows the relationship between air flow rate and air electrode potential change, and Fig. 8 is a diagram showing the relationship between the pore occupancy of the air electrode and the potential, Figure 9 is a diagram showing the change over time of a unit battery using an air electrode with a small occupancy, and Figure 10 is a diagram showing the relationship between the air electrode with a large pore occupancy. A diagram showing the change over time of the unit battery used,
FIG. 11 is a diagram showing the structure of a conventional air electrode, and FIG. 12 is an SEM image of the conventional substrate side. 1... Porous conductive substrate, 2... Air electrode catalyst layer, 3
... Electrolyte permeation blocking layer, 4... Time-dependent change in unit cell voltage using the three-layer air electrode according to the present invention, 5... Air electrode, 6... Ion exchange membrane, 7... Anorite, 8
...Air electrode reaction field, 9...Air chamber, 10...
Gap between the air electrode and the ion exchange membrane, 11... Change in battery voltage over time during intermittent operation of the battery, 12... Change over time in voltage during continuous operation of the battery, 13... Due to discharge of electrolyte from the catalyst layer Voltage drop phenomenon, 14... Voltage drop phenomenon due to volume reduction due to concentration of electrolyte in catalyst layer, 15
... Voltage increase phenomenon due to volume increase due to dilution of water in electrolyte in catalyst layer, 16... Electrolyte absorption curve of air electrode, 17... Electrolyte discharge curve of air electrode, 18... is the characteristic of the air electrode with a small electrolyte pore occupancy, 19... the characteristic of the air electrode with a large pore occupancy, 20... the voltage determined from the potential difference between the air electrode and the methanol electrode, 21... hydrophilicity Voltage change over time of a unit battery using a modified air electrode. Patent applicant Hitachi, Ltd. Representative Patent attorney Yusuke Hiraki - Porous conductive substrate 2 - Air electrode catalyst layer 3 - Electrolyte permeation blocking layer 2nd Figure 3 Operating time (h) Figure 4 (A) (B) U 5-111 air electrode 6-111 Ion exchange membrane 7---7 Norite 8-111 air electrode reaction Field 9-111 Air chamber 10---1 Gap between air electrode and ion exchanger Figure 5 Figure 2 Figure 6 Immersion time (h) Figure 7 Air flow rate (ml/min-am2) Pore occupancy ('/,) Figure 9 Operating time (h) Figure 1○ Operating time (h) Figure 11 1-111 Porous conductive substrate 2-111 Air electrode catalyst layer
Claims (1)
処理し、該基質片側に集電層をかね備えた電解液阻止層
と前記基質他方に電極触媒−撥水性ポリマー混合物の触
媒層を配したことから成る三層構造を有するガス拡散電
極を用いたことを特徴とする燃料電池。 ２、基質が炭素繊維からな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。 ３、燃料電池が液体燃料電池であ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。[Claims] 1. A substrate having a three-dimensional network structure is treated with a water-repellent polymer, and one side of the substrate is treated with an electrolyte blocking layer that also includes a current collecting layer, and the other side of the substrate is provided with an electrocatalyst and a water-repellent polymer. A fuel cell characterized by using a gas diffusion electrode having a three-layer structure comprising a catalyst layer of a mixture. 2. The fuel cell according to claim 1, wherein the substrate is made of carbon fiber. 3. The fuel cell according to claim 1, wherein the fuel cell is a liquid fuel cell.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61155073A JPH0665039B2 (en) | 1986-07-03 | 1986-07-03 | Fuel cell using three-layer gas diffusion electrode |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61155073A JPH0665039B2 (en) | 1986-07-03 | 1986-07-03 | Fuel cell using three-layer gas diffusion electrode |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6313273A true JPS6313273A (en) | 1988-01-20 |
| JPH0665039B2 JPH0665039B2 (en) | 1994-08-22 |
Family
ID=15598061
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61155073A Expired - Lifetime JPH0665039B2 (en) | 1986-07-03 | 1986-07-03 | Fuel cell using three-layer gas diffusion electrode |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0665039B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1775788A4 (en) * | 2004-06-21 | 2009-11-11 | Nissan Motor | Gas diffusion electrode and solid polymer electrolyte fuel cell |
| CN110676465A (en) * | 2018-07-03 | 2020-01-10 | 夏普株式会社 | Air electrode, metal-air battery, and method for manufacturing air electrode |
-
1986
- 1986-07-03 JP JP61155073A patent/JPH0665039B2/en not_active Expired - Lifetime
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1775788A4 (en) * | 2004-06-21 | 2009-11-11 | Nissan Motor | Gas diffusion electrode and solid polymer electrolyte fuel cell |
| CN110676465A (en) * | 2018-07-03 | 2020-01-10 | 夏普株式会社 | Air electrode, metal-air battery, and method for manufacturing air electrode |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0665039B2 (en) | 1994-08-22 |
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