JPH06260207A - Stack of phosphate type fuel cell - Google Patents
Stack of phosphate type fuel cellInfo
- Publication number
- JPH06260207A JPH06260207A JP5040321A JP4032193A JPH06260207A JP H06260207 A JPH06260207 A JP H06260207A JP 5040321 A JP5040321 A JP 5040321A JP 4032193 A JP4032193 A JP 4032193A JP H06260207 A JPH06260207 A JP H06260207A
- Authority
- JP
- Japan
- Prior art keywords
- stack
- platinum
- cell
- carbon monoxide
- fuel
- 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.)
- Pending
Links
- 239000000446 fuel Substances 0.000 title claims abstract description 59
- 229910019142 PO4 Inorganic materials 0.000 title 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 title 1
- 239000010452 phosphate Substances 0.000 title 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 95
- 239000003054 catalyst Substances 0.000 claims abstract description 52
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 45
- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 14
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 11
- 239000000956 alloy Substances 0.000 claims abstract description 11
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 29
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 15
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 6
- 239000011159 matrix material Substances 0.000 claims description 5
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 229910052707 ruthenium Inorganic materials 0.000 claims description 4
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052737 gold Inorganic materials 0.000 claims description 3
- 239000010931 gold Substances 0.000 claims description 3
- 229910052763 palladium Inorganic materials 0.000 claims description 3
- 229910052702 rhenium Inorganic materials 0.000 claims description 3
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 claims description 3
- 229910052703 rhodium Inorganic materials 0.000 claims description 3
- 239000010948 rhodium Substances 0.000 claims description 3
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 abstract description 29
- 229910002091 carbon monoxide Inorganic materials 0.000 abstract description 29
- 239000007789 gas Substances 0.000 abstract description 16
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 14
- 239000001257 hydrogen Substances 0.000 abstract description 14
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 11
- 238000006722 reduction reaction Methods 0.000 abstract description 8
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 230000003247 decreasing effect Effects 0.000 abstract 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical group O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 8
- 229910052799 carbon Inorganic materials 0.000 description 8
- 239000002737 fuel gas Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 229910002092 carbon dioxide Inorganic materials 0.000 description 5
- 239000001569 carbon dioxide Substances 0.000 description 5
- 239000000470 constituent Substances 0.000 description 3
- 150000002431 hydrogen Chemical group 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 230000007423 decrease Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 231100000614 poison Toxicity 0.000 description 2
- 230000007096 poisonous effect Effects 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 208000001408 Carbon monoxide poisoning Diseases 0.000 description 1
- 208000005374 Poisoning Diseases 0.000 description 1
- 229910001260 Pt alloy Inorganic materials 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229940018951 carbon dioxide 20 % Drugs 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 229910000923 precious metal alloy Inorganic materials 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
Classifications
-
- 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
- Inert Electrodes (AREA)
- Fuel Cell (AREA)
Abstract
(57)【要約】
【目的】電池の製造コストを余り増大させることなく、
燃料改質ガス中の一酸化炭素による電池出力の低下を防
ぐ。
【構成】スタック最上部および最下部からそれぞれ３番
目までの各セルの燃料極触媒層に、白金と貴金属との合
金触媒を用い、または、前記各セルの燃料極触媒層の白
金量を過剰にしておくことにより、合金触媒を用いる場
合は、一酸化炭素を貴金属元素の方に吸着させて、白金
が一酸化炭素により被毒されるのを抑え、白金量を過剰
にしておく場合は、燃料極における水素の還元反応に十
分足るだけ、一酸化炭素の吸着しない白金を保持し、ス
タックを構成する全てのセルについて触媒に貴金属を用
い、または、白金量を過剰にするのに比べて、電池の製
造コストを余り増大させることなく、電池の出力低下を
防ぐことができる。
(57) [Summary] [Purpose] Without significantly increasing the manufacturing cost of the battery,
Prevents reduction in cell output due to carbon monoxide in the fuel reformed gas. [Structure] An alloy catalyst of platinum and a noble metal is used in the fuel electrode catalyst layers of each cell from the top and the bottom of the stack to the third, or the amount of platinum in the fuel electrode catalyst layer of each cell is made excessive. If an alloy catalyst is used, carbon monoxide will be adsorbed on the noble metal element to prevent platinum from being poisoned by carbon monoxide. In comparison with using platinum as a catalyst for all the cells that make up the stack, or by using an excess amount of platinum, it holds platinum that does not adsorb carbon monoxide and is sufficient for the reduction reaction of hydrogen at the electrodes. It is possible to prevent the output of the battery from decreasing without increasing the manufacturing cost of the battery.
Description
【０００１】[0001]
【産業上の利用分野】本発明は燐酸形燃料電池のスタッ
クの構成に関する。FIELD OF THE INVENTION The present invention relates to the construction of a phosphoric acid fuel cell stack.
【０００２】[0002]
【従来の技術】燐酸形燃料電池のスタックは単電池を上
下方向に多数積層したものであり、図１に燐酸形燃料電
池スタックの外観を模式斜視図で示すが、図１は説明の
便宜上一部を剥離した状態で示してある。図１におい
て、この燐酸形燃料電池スタックは、空気極、燃料極お
よびマトリックスからなる各セル（単電池）１を、セパ
レータ板２、および一部に温度調節のための冷却板３を
介在させて多数積層し、上下に締付板４を取り付け、側
面に反応ガスを供給し排気するための空気マニホルド５
と燃料マニホルド６とを配置してある。2. Description of the Related Art A phosphoric acid fuel cell stack is a stack of a plurality of unit cells vertically, and FIG. 1 is a schematic perspective view showing the appearance of the phosphoric acid fuel cell stack. It is shown in a state where the parts are peeled off. In FIG. 1, this phosphoric acid fuel cell stack has cells (unit cells) 1 each consisting of an air electrode, a fuel electrode and a matrix, a separator plate 2 and a cooling plate 3 for temperature control partially interposed. An air manifold 5 for stacking a large number of layers, attaching clamping plates 4 on the top and bottom, and supplying and exhausting reaction gas on the side surface.
And a fuel manifold 6 are arranged.
【０００３】図２は、セル１の構成部材を示す部分的な
模式断面図であり、図２（ａ）は構成部材を示し、図２
（ｂ）はそのうちの触媒層の一部を拡大して示した模式
断面図である。図２（ａ）において、空気極７はカーボ
ン基材８と、触媒１４［図２（ｂ）］をバインダーのフ
ッ素樹脂９で結着した空気極触媒層１０とからなり、燃
料極１１は同様にカーボン基材８と、触媒１４をフッ素
樹脂９で結着した燃料極触媒層１２からなり、空気極７
と燃料極１１がマトリックス１３を挟持している。触媒
１４は図２（ｂ）に示すように、カーボン担体１５上に
白金１６を担持する。FIG. 2 is a partial schematic cross-sectional view showing the constituent members of the cell 1, and FIG. 2 (a) shows the constituent members.
(B) is a schematic cross-sectional view showing an enlarged part of the catalyst layer. In FIG. 2 (a), the air electrode 7 comprises a carbon base material 8 and an air electrode catalyst layer 10 in which a catalyst 14 [FIG. 2 (b)] is bound by a fluororesin 9 as a binder, and the fuel electrode 11 is the same. Is composed of a carbon base material 8 and a fuel electrode catalyst layer 12 in which a catalyst 14 is bound with a fluororesin 9, and the air electrode 7
And the fuel electrode 11 sandwiches the matrix 13. As shown in FIG. 2B, the catalyst 14 carries platinum 16 on a carbon carrier 15.
【０００４】[0004]
【発明が解決しようとする課題】以上のセル１を多数積
層した燃料電池のスタックについて、下記のような問題
がある。電池に供給される燃料の改質ガス、即ち、燃料
改質器により天然ガスや石油ガスなどを改質して得られ
る水素リッチなガスの中には、電池の運転条件によって
も異なるが、１％程度の一酸化炭素が含まれることがあ
り、問題は、その一酸化炭素が燃料極１１の触媒１４中
の白金１６の表面に吸着して、水素の還元反応を阻害す
るので、触媒１４に対して被毒物質となり、電池の出力
を低下させることである。The fuel cell stack in which a large number of the above cells 1 are stacked has the following problems. The reformed gas of the fuel supplied to the battery, that is, the hydrogen-rich gas obtained by reforming natural gas or petroleum gas by the fuel reformer, varies depending on the operating conditions of the battery. % Carbon monoxide may be contained, and the problem is that the carbon monoxide adsorbs on the surface of the platinum 16 in the catalyst 14 of the fuel electrode 11 and inhibits the hydrogen reduction reaction. On the other hand, it is a poisonous substance and reduces the output of the battery.
【０００５】一般に、燐酸形燃料電池はスタックに積層
した各セル１の温度が２００℃程度になるように、温度
を調節して運転を行なう。しかし、スタックの上部と下
部に位置するセル１は、上下の締付板４からの大きな放
熱の影響を受け、その他のセル１に比べて温度が１０〜
３０℃程度低下する。一酸化炭素の白金１６表面上への
吸着量は、温度が１７０℃以上になれば減少し、通常、
２００℃程度の電池の運転条件では、一酸化炭素によっ
て燃料極１１の触媒１４が被毒される影響は無視できる
程小さい。しかし、温度の低いスタック上部と下部に位
置するセル１では、一酸化炭素による触媒１４の被毒を
無視することができなくなり、電池の出力低下が著し
い。Generally, the phosphoric acid fuel cell is operated by adjusting the temperature so that the temperature of each cell 1 stacked in the stack is about 200.degree. However, the cells 1 located at the upper and lower parts of the stack are affected by the large heat radiation from the upper and lower tightening plates 4, and the temperature is 10 to 10 compared to the other cells 1.
It drops about 30 ° C. The amount of carbon monoxide adsorbed on the surface of platinum 16 decreases when the temperature rises above 170 ° C.
Under the operating condition of the battery at about 200 ° C., the influence of carbon monoxide poisoning the catalyst 14 of the fuel electrode 11 is negligible. However, in the cells 1 located above and below the stack where the temperature is low, poisoning of the catalyst 14 by carbon monoxide cannot be ignored, and the output of the battery is significantly reduced.
【０００６】そこで、燃料極１１の触媒１４には、白金
とルテニウム，パラジウム，ロジウム，レニウム，金な
どの貴金属合金をカーボン担体１５に担持した触媒を用
い、これら合金元素の方に一酸化炭素を吸着させ、白金
１６自体が侵されないようにし、白金１６への一酸化炭
素吸着の影響をなくすことも考えらるが、全ての触媒１
４に貴金属を用いるのは、電池の製造コストを増大させ
ることから好ましくない。Therefore, for the catalyst 14 of the fuel electrode 11, a catalyst in which platinum and a precious metal alloy such as ruthenium, palladium, rhodium, rhenium, and gold are supported on a carbon carrier 15 is used, and carbon monoxide is added to these alloy elements. It may be considered that platinum 16 itself is not attacked by adsorption so that the effect of carbon monoxide adsorption on platinum 16 is eliminated, but all catalysts 1
It is not preferable to use a noble metal for No. 4 because it increases the manufacturing cost of the battery.
【０００７】本発明は上述の点に鑑みてなされたもので
あり、その目的は、電池のコストを余り増大させること
なく、燃料改質ガス中に含まれる一酸化炭素によつて電
池出力が低下しないように構成した燐酸形燃料電池のス
タックを提供することにある。The present invention has been made in view of the above points, and an object thereof is to reduce the cell output by carbon monoxide contained in the fuel reformed gas without significantly increasing the cost of the cell. Another object of the present invention is to provide a stack of phosphoric acid fuel cells configured not to do so.
【０００８】[0008]
【課題を解決するための手段】以上の課題を解決するた
めに、本発明の燐酸形燃料電池のスタックは、スタック
最上部および最下部からそれぞれ３番目までの各セルの
燃料極触媒層に、白金とルテニウム，パラジウム，ロジ
ウム，レニウム，または金などの貴金属との合金触媒を
用いる。または、このスタック最上部および最下部から
それぞれ３番目までの各セルの燃料極触媒層の白金量
を、あらかじめ他のセルに比べて２倍にしておく。In order to solve the above-mentioned problems, the stack of the phosphoric acid fuel cell of the present invention has a fuel electrode catalyst layer of each cell from the top and the bottom of the stack to the third, respectively. An alloy catalyst of platinum and a noble metal such as ruthenium, palladium, rhodium, rhenium, or gold is used. Alternatively, the amount of platinum in the fuel electrode catalyst layer of each cell from the top and the bottom of the stack to the third is doubled in advance as compared with the other cells.
【０００９】[0009]
【作用】上記のように、本発明の燐酸形燃料電池のスタ
ックは、運転温度が低くなるスタック最上部および最下
部からそれぞれ３番目までの各セルの燃料極触媒層に、
白金と貴金属との合金触媒を用いることにより、燃料の
改質ガス中に含まれる一酸化炭素が貴金属元素の方に吸
着し、白金が一酸化炭素により被毒されるのを抑えるこ
とができ、スタックを構成する全てのセルに白金と貴金
属との合金触媒を用いるのに比べて、電池の製造コスト
を余り増大させることなく、一酸化炭素に起因する電池
の出力低下を防ぐことができる。As described above, in the stack of the phosphoric acid fuel cell of the present invention, the fuel electrode catalyst layer of each cell from the top and the bottom of the stack where the operating temperature becomes low to the third,
By using an alloy catalyst of platinum and a noble metal, carbon monoxide contained in the reformed gas of the fuel is adsorbed on the noble metal element, and it is possible to prevent platinum from being poisoned by carbon monoxide. Compared to using an alloy catalyst of platinum and a noble metal for all the cells constituting the stack, it is possible to prevent the output reduction of the battery due to carbon monoxide without significantly increasing the manufacturing cost of the battery.
【００１０】または、スタック最上部および最下部から
それぞれ３番目までの各セルの燃料極触媒層の白金量
を、あらかじめ他のセルに比べて過剰にしておくことに
より、一酸化炭素の吸着していない白金が、燃料極にお
ける水素の還元反応に十分足りるだけ保持されるので、
上記と同様に、電池の製造コストを余り増大させること
なく、一酸化炭素に起因する電池の出力低下を防ぐこと
ができる。[0010] Alternatively, carbon monoxide is adsorbed by making the amount of platinum in the fuel electrode catalyst layer of each cell from the top and the bottom of the stack to the third to be excessive compared with other cells in advance. Since there is enough platinum retained for the hydrogen reduction reaction at the fuel electrode,
Similar to the above, it is possible to prevent a decrease in the output of the battery due to carbon monoxide without significantly increasing the manufacturing cost of the battery.
【００１１】[0011]
【実施例】以下、本発明を実施例に基づき説明する。は
じめに、電極面積２０００ｃｍ2 ，セル積層数２１のシ
ョートスタックセルを作製したが、スタックの構造は図
１に示したものと、基本的には同じであるからその説明
は省略する。このスタックの各セルの燃料極には、Ｃａ
ｂｏｔ社製の商品名Ｖｕｌｃａｎ ＸＣ−７２のカーボ
ン担体に１０ｗｔ％の白金を担持した触媒を用い、電極
触媒層の単位面積当たりの白金重量（以下、単に白金量
とする）を０．５ｍｇ−Ｐｔ／ｃｍ2 とした。各セルに
挿入した熱電対で温度をモニターしたところ、スタック
の最上部に位置するセルは１８１℃、上から２番目のセ
ルは１８６℃、３番目のセルは１９２℃であり、スタッ
クの最下部に位置するセルは１７５℃、下から２番目の
セルは１８１℃、３番目のセルは１９０℃であった。ス
タックの中間にあるその他の１５セルの温度は、２００
±５℃である。EXAMPLES The present invention will be described below based on examples. First, a short stack cell having an electrode area of 2000 cm 2 and a cell stack number of 21 was prepared, but since the structure of the stack is basically the same as that shown in FIG. 1, its description is omitted. The fuel electrode of each cell of this stack has Ca
A platinum carrier with a trade name of Vulcan XC-72 manufactured by Bot Co., which carries 10 wt% of platinum, is used, and the platinum weight per unit area of the electrode catalyst layer (hereinafter, simply referred to as platinum amount) is 0.5 mg-Pt. / Cm 2 . When the temperature was monitored with a thermocouple inserted in each cell, the cell at the top of the stack was 181 ° C, the second cell from the top was 186 ° C, and the third cell was 192 ° C. The cell located at was 175 ° C, the second cell from the bottom was 181 ° C, and the third cell was 190 ° C. The temperature of the other 15 cells in the middle of the stack is 200
± 5 ° C.
【００１２】このショートスタックセルに燃料ガスとし
て、水素８０％／二酸化炭素２０％の組成を持つガスを
流したときの全セル電圧は、１３．８Ｖである。しか
し、燃料ガスとして、改質ガスを模擬した水素８０％／
二酸化炭素１９％／一酸化炭素１％の組成を持つガスを
流したとき、全セル電圧は１３．２Ｖに低下した。次
に、このショートスタックセルを解体し、セル温度の低
い上下の各３セルの燃料極触媒層として、前述のＶｕｌ
ｃａｎ ＸＣ−７２カーボン担体に、白金５０％／ルテ
ニウム５０％の合金を２０ｗｔ％担持した触媒を用い、
触媒層の白金量を０．５ｍｇ−Ｐｔ／ｃｍ2 とした燃料
極に取り替えて、ショートスタックセルを組み直した。
このように構成したスタックに、燃料ガスとして、水素
８０％／二酸化炭素２０％の組成を持つガスを流したと
きの全セル電圧は、前回と同じく１３．８Ｖであった。
また、燃料ガスを、改質ガスを模擬した水素８０％／二
酸化炭素１９％／一酸化炭素１％の組成を持つガスとし
て流したとき、全セル電圧は１３．７Ｖであり、ほぼ同
じ電池出力が得られた。The total cell voltage is 13.8 V when a gas having a composition of hydrogen 80% / carbon dioxide 20% is passed as a fuel gas into the short stack cell. However, as fuel gas, hydrogen 80% / simulating reformed gas
When a gas having a composition of carbon dioxide 19% / carbon monoxide 1% was passed, the total cell voltage dropped to 13.2V. Next, this short stack cell was disassembled, and the above-mentioned Vul was used as the fuel electrode catalyst layers of the upper and lower three cells with low cell temperature.
Using a catalyst in which 20 wt% of an alloy of platinum 50% / ruthenium 50% is supported on a can XC-72 carbon carrier,
The platinum in the catalyst layer was replaced with a fuel electrode having 0.5 mg-Pt / cm 2, and the short stack cell was reassembled.
The total cell voltage when a gas having a composition of 80% hydrogen / 20% carbon dioxide was passed through the stack configured as described above was 13.8 V as in the previous time.
Further, when the fuel gas was made to flow as a gas having a composition of hydrogen 80% / carbon dioxide 19% / carbon monoxide 1% simulating a reformed gas, the total cell voltage was 13.7 V, and the battery output was almost the same. was gotten.
【００１３】一方、スタック上部および下部のセルの燃
料極のみ、あらかじめ触媒の白金量を過剰にしておき、
一酸化炭素を含む燃料ガスを供給しておくことにより、
白金粒子表面に一酸化炭素が吸着した場合でも、一酸化
炭素が吸着していない白金粒子として、燃料極における
水素の還元反応に十分足りるだけの白金量を保持させる
ようにすることもできる。On the other hand, only the fuel electrodes of the cells at the top and bottom of the stack have an excessive amount of platinum in the catalyst in advance,
By supplying the fuel gas containing carbon monoxide,
Even if carbon monoxide is adsorbed on the surface of the platinum particles, the platinum particles not adsorbing carbon monoxide can be made to retain a sufficient amount of platinum for the hydrogen reduction reaction at the fuel electrode.
【００１４】そこで、上記のショートスタックセルを再
び解体し、セル温度の低いスタック上下の各３セルの燃
料極触媒層として、前述のＶｕｌｃａｎ ＸＣ−７２カ
ーボン担体に１０ｗｔ％の白金を担持した触媒を用い、
この上下各３セルのみ、触媒層の白金量を１．０ｍｇ−
Ｐｔ／ｃｍ2 とした燃料極に取り替えて、ショートスタ
ックセルを組み直した。これに、燃料ガスとして、水素
８０％／二酸化炭素２０％の組成を持つガスを流したと
きの全セル電圧は、前回と同じく１３．８Ｖであり、ま
た、燃料ガスを、改質ガスを模擬した水素８０％／二酸
化炭素１９％／一酸化炭素１％の組成を持つガスとして
流したとき、全セル電圧は１３．７Ｖであり、前回とほ
ぼ同様の結果を得ることができた。Therefore, the above short stack cells were disassembled again, and the above-mentioned Vulcan XC-72 carbon carrier loaded with 10 wt% platinum was used as the fuel electrode catalyst layers of the upper and lower three cells of the stack having a low cell temperature. Used,
The platinum amount in the catalyst layer was 1.0 mg
The fuel electrode was changed to Pt / cm 2 and the short stack cell was reassembled. The total cell voltage when a gas having a composition of 80% hydrogen / 20% carbon dioxide was passed as the fuel gas was 13.8 V, the same as the previous time, and the fuel gas simulated the reformed gas. When a gas having a composition of 80% hydrogen / 19% carbon dioxide / 1% carbon monoxide was passed, the total cell voltage was 13.7 V, and almost the same result as the previous time could be obtained.
【００１５】この場合は、スタック上下の各３セルの
み、燃料極触媒層の白金量を０．５ｍｇ−Ｐｔ／ｃｍ2
から１．０ｍｇ−Ｐｔ／ｃｍ2 としており、スタックの
中間に属するセルと比べて、白金量を２倍としたことに
より、上下３セルを白金−貴金属の合金触媒としたとき
と同じ効果が得られる。以上のように、本発明では燃料
電池スタックの温度が低くなるセル、即ち、スタックの
冷却板を用いない領域である最上部および最下部から３
番目までの各セルについて、燃料極触媒層に白金−貴金
属合金を担持した触媒を用い、または触媒に白金を用い
るときは、スタックの最上部および最下部から３番目ま
での各セルの燃料極触媒層の白金量をあらかじめ過剰に
しておき、いずれの場合も、燃料の改質ガスの一酸化炭
素によって触媒が被毒されて電池出力が低下するのを防
ぐようにスタックを構成したものである。In this case, the amount of platinum in the fuel electrode catalyst layer is 0.5 mg-Pt / cm 2 only in each of the three cells above and below the stack.
From 1.0 mg-Pt / cm 2 and the amount of platinum is doubled compared to the cells belonging to the middle of the stack, and the same effect as when the upper and lower three cells are made of platinum-noble metal alloy catalyst can be obtained. To be As described above, according to the present invention, the cells in which the temperature of the fuel cell stack becomes low, that is, 3 from the top and bottom of the stack, which are regions where no cooling plate is used,
For each of the cells up to the 3rd, when a catalyst supporting a platinum-noble metal alloy is used in the anode catalyst layer, or when platinum is used as the catalyst, the anode catalysts of the cells from the top and bottom to the 3rd of the stack are used. The amount of platinum in the layer is set to an excessive amount in advance, and in any case, the stack is configured to prevent the catalyst output from being poisoned by carbon monoxide, which is a reformed gas of the fuel, and lowering the cell output.
【００１６】[0016]
【発明の効果】燐酸形燃料電池に供給する燃料の水素リ
ッチな改質ガスに含まれる一酸化炭素が含まれ、その一
酸化炭素が燃料極の触媒中の白金表面に吸着して、水素
の還元反応を阻害するので、触媒に対して被毒物質とな
り、電池の出力を低下させることがあり、これに対して
本発明の燐酸形燃料電池のスタックは、スタック最上部
および最下部からそれぞれ３番目までの各セルの燃料極
の触媒層に、白金と貴金属との合金触媒を用いることに
より 一酸化炭素を貴金属元素の方に吸着させて、白金
が一酸化炭素により被毒されるのを抑えることができ
る。The carbon monoxide contained in the hydrogen-rich reformed gas of the fuel supplied to the phosphoric acid fuel cell is contained, and the carbon monoxide is adsorbed on the platinum surface in the catalyst of the fuel electrode to generate hydrogen. Since it inhibits the reduction reaction, it may become a poisonous substance to the catalyst and reduce the output of the cell. On the other hand, the phosphoric acid fuel cell stack of the present invention has three stacks from the top and bottom of the stack, respectively. By using an alloy catalyst of platinum and a noble metal in the catalyst layers of the fuel electrodes of each cell up to the third, carbon monoxide is adsorbed by the noble metal element and platinum is prevented from being poisoned by carbon monoxide. be able to.
【００１７】また、スタックの各セルに白金触媒を用い
るときは、スタック最上部および最下部からそれぞれ３
番目までの各セルの燃料極の触媒層の白金量を、あらか
じめ他のセルに比べて過剰にしておくことにより、燃料
極における水素の還元反応に十分足るだけ、一酸化炭素
が吸着していない白金が残るようになる。いずれの場合
も、スタックを構成する全てのセルに白金と貴金属との
合金触媒を用い、または、スタックを構成する全てのセ
ルの白金量を過剰にしておくのに比べて、本発明による
スタック構成は、電池の製造コストを余り増大させるこ
となく、一酸化炭素に起因する電池の出力低下を防ぐこ
とができる。When a platinum catalyst is used in each cell of the stack, the top 3 and the bottom 3 of the stack are used respectively.
By setting the amount of platinum in the catalyst layer of the fuel electrode of each cell up to the second to be excessive compared with other cells in advance, carbon monoxide is not adsorbed enough to reduce hydrogen in the fuel electrode. Platinum will remain. In any case, as compared with using an alloy catalyst of platinum and a noble metal in all cells forming the stack, or making the amount of platinum in all cells forming the stack excessive, the stack structure according to the present invention is used. Can prevent the output reduction of the battery due to carbon monoxide without significantly increasing the manufacturing cost of the battery.
【図１】燐酸形燃料電池スタックの外観を示す模式斜視
図FIG. 1 is a schematic perspective view showing the appearance of a phosphoric acid fuel cell stack.
【図２】（ａ）はセルの構成部材を示す部分模式断面
図、（ｂ）は触媒層の一部を拡大して示した模式断面図FIG. 2A is a partial schematic cross-sectional view showing constituent members of a cell, and FIG. 2B is a schematic cross-sectional view showing a part of a catalyst layer in an enlarged manner.
１ セル ２ セパレータ ３ 冷却板 ４ 締付板 ５ 空気マニホルド ６ 燃料マニホルド７ 空気極 ８ カーボン基材 ９ フッ素樹脂 １０ 空気極触媒層１１ 燃料極 １２ 燃料極触媒層 １３ マトリックス １４ 触媒 １５ カーボン担体 １６ 白金1 Cell 2 Separator 3 Cooling Plate 4 Tightening Plate 5 Air Manifold 6 Fuel Manifold 7 Air Electrode 8 Carbon Base Material 9 Fluororesin 10 Air Electrode Catalyst Layer 11 Fuel Electrode 12 Fuel Electrode Catalyst Layer 13 Matrix 14 Catalyst 15 Carbon Carrier 16 Platinum
Claims (3)
るセルを、セパレータ板および冷却板を介在させて多数
積層した燐酸形燃料電池のスタックであって、このスタ
ック最上部および最下部からそれぞれ３番目までの各セ
ルの燃料極の触媒層に、白金と貴金属との合金触媒を用
いることを特徴とする燐酸形燃料電池のスタック。1. A stack of a phosphoric acid fuel cell in which a large number of cells composed of an air electrode, a fuel electrode and a matrix are stacked with a separator plate and a cooling plate interposed, and the stack is the third from the top and the bottom of the stack. A stack of a phosphoric acid fuel cell characterized by using an alloy catalyst of platinum and a noble metal in the catalyst layer of the fuel electrode of each cell up to.
において、貴金属はルテニウム，パラジウム，ロジウ
ム，レニウム，または金のうちのいずれか一つであるこ
とを特徴とする燐酸形燃料電池のスタック。2. The phosphoric acid fuel cell stack according to claim 1, wherein the noble metal is any one of ruthenium, palladium, rhodium, rhenium, and gold. .
るセルを、セパレータ板および冷却板を介在させて多数
積層した燐酸形燃料電池のスタックであって、このスタ
ック最上部および最下部からそれぞれ３番目までの各セ
ルの燃料極の触媒層の白金量を、他のセルに比べて２倍
とすることを特徴とする燐酸形燃料電池のスタック。3. A stack of a phosphoric acid fuel cell in which a large number of cells composed of an air electrode, a fuel electrode and a matrix are laminated with a separator plate and a cooling plate interposed, and the stack is the third from the top and the bottom of the stack. Up to twice the amount of platinum in the catalyst layer of the fuel electrode of each cell compared to other cells.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5040321A JPH06260207A (en) | 1993-03-02 | 1993-03-02 | Stack of phosphate type fuel cell |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5040321A JPH06260207A (en) | 1993-03-02 | 1993-03-02 | Stack of phosphate type fuel cell |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH06260207A true JPH06260207A (en) | 1994-09-16 |
Family
ID=12577353
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5040321A Pending JPH06260207A (en) | 1993-03-02 | 1993-03-02 | Stack of phosphate type fuel cell |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH06260207A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1989005031A1 (en) * | 1987-11-26 | 1989-06-01 | Max-Planck-Gesellschaft Zur Förderung Der Wissensc | SINTERED Fe-Nd-B MAGNET |
| JPH10270055A (en) * | 1997-03-25 | 1998-10-09 | Mitsubishi Electric Corp | Electrochemical catalyst, and electrochemical reactor, electrochemical element, phosphoric fuel cell, and methanol-direct fuel cell using it |
| JPH11250918A (en) * | 1997-12-19 | 1999-09-17 | Degussa Ag | Platinum/ruthenium alloy catalyst, its manufacture, gas diffusion electrode, membrane electrode unit, and proton conductive polymer membrane for pem fuel cell |
| US6326098B1 (en) | 1998-04-23 | 2001-12-04 | N. E. Chemcat Corporation | Electrocatalyst, and electrodes, membrane-electrode assembly and solid polymer electrolyte fuel cells, using said electrocatalyst |
| JP2005142001A (en) * | 2003-11-06 | 2005-06-02 | Toyota Motor Corp | Fuel cell having a stack structure |
-
1993
- 1993-03-02 JP JP5040321A patent/JPH06260207A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1989005031A1 (en) * | 1987-11-26 | 1989-06-01 | Max-Planck-Gesellschaft Zur Förderung Der Wissensc | SINTERED Fe-Nd-B MAGNET |
| JPH10270055A (en) * | 1997-03-25 | 1998-10-09 | Mitsubishi Electric Corp | Electrochemical catalyst, and electrochemical reactor, electrochemical element, phosphoric fuel cell, and methanol-direct fuel cell using it |
| JPH11250918A (en) * | 1997-12-19 | 1999-09-17 | Degussa Ag | Platinum/ruthenium alloy catalyst, its manufacture, gas diffusion electrode, membrane electrode unit, and proton conductive polymer membrane for pem fuel cell |
| JP4582594B2 (en) * | 1997-12-19 | 2010-11-17 | ユミコア・アクチエンゲゼルシャフト・ウント・コムパニー・コマンディットゲゼルシャフト | Platinum / ruthenium alloy catalyst, process for producing the same, gas diffusion electrode, membrane electrode unit and proton conducting polymer membrane for PEM fuel cell |
| US6326098B1 (en) | 1998-04-23 | 2001-12-04 | N. E. Chemcat Corporation | Electrocatalyst, and electrodes, membrane-electrode assembly and solid polymer electrolyte fuel cells, using said electrocatalyst |
| JP2005142001A (en) * | 2003-11-06 | 2005-06-02 | Toyota Motor Corp | Fuel cell having a stack structure |
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