JPS6355864A - Fuel detector of fuel cell - Google Patents
Fuel detector of fuel cellInfo
- Publication number
- JPS6355864A JPS6355864A JP61198858A JP19885886A JPS6355864A JP S6355864 A JPS6355864 A JP S6355864A JP 61198858 A JP61198858 A JP 61198858A JP 19885886 A JP19885886 A JP 19885886A JP S6355864 A JPS6355864 A JP S6355864A
- Authority
- JP
- Japan
- Prior art keywords
- fuel
- diaphragm
- blower
- gas detector
- concentration
- 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 79
- 238000001514 detection method Methods 0.000 claims abstract description 41
- 239000007791 liquid phase Substances 0.000 claims abstract description 3
- 239000007788 liquid Substances 0.000 claims description 6
- 239000007789 gas Substances 0.000 abstract description 30
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 abstract description 6
- 230000007797 corrosion Effects 0.000 abstract description 2
- 238000005260 corrosion Methods 0.000 abstract description 2
- 230000007423 decrease Effects 0.000 abstract description 2
- 239000002737 fuel gas Substances 0.000 abstract description 2
- 239000012466 permeate Substances 0.000 abstract 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 238000000034 method Methods 0.000 description 8
- 239000012071 phase Substances 0.000 description 7
- 238000010586 diagram Methods 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 125000004122 cyclic group Chemical group 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000002828 fuel tank Substances 0.000 description 2
- 238000005192 partition Methods 0.000 description 2
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 229920006361 Polyflon Polymers 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000001934 delay Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 210000003127 knee Anatomy 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 239000005871 repellent Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000725 suspension Substances 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
- H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
- H01M8/04082—Arrangements for control of reactant parameters, e.g. pressure or concentration
- H01M8/04186—Arrangements for control of reactant parameters, e.g. pressure or concentration of liquid-charged or electrolyte-charged reactants
- H01M8/04194—Concentration measuring 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
- 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)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は液体燃料を直接電気化学反応させて、電気エネ
ルギを発電する燃料電池に係り、中の燃料濃度を精度良
く検出する装置に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a fuel cell that generates electrical energy by directly electrochemically reacting liquid fuel, and to a device that accurately detects the fuel concentration therein.
液体を燃料とする燃料電池のアノライト中の燃料濃度の
検出方法は間接的及び直接的手法がとられている。間接
的手法は燃料及びアノライトの循環系統の気相部にガス
検出装置を設置する方法である。直接的手法は、たとえ
ば、特開昭５６−１１８２７３号公報に記載のように小
形の燃料電池を設けて、電池性能で燃料濃度を評価する
方法や燃料の電解反応を利用したサイクリックポルタン
メトリー法がある。Indirect and direct methods are used to detect the fuel concentration in an anorite of a fuel cell using liquid as fuel. An indirect method is to install a gas detection device in the gas phase of the fuel and anolite circulation system. Direct methods include, for example, a method in which a small fuel cell is installed and the fuel concentration is evaluated based on the cell performance, as described in JP-A No. 56-118273, and cyclic portammetry that utilizes the electrolytic reaction of fuel. There is a law.
液体を燃料とする燃料電池の燃料の循環系路及び従来の
間接的手法によるアノライト中の燃料濃度検出方法を第
２図に示す。燃料及びアノライトの循環系路について説
明すると、燃料と電解液の混合液アノライト１３はポン
プ５により、供給通路３Ａを通して積ｍ’ｔａ池本体１
に設けられている燃料室３を径で戻り通路３Ｂを通って
アノライト溜１２に回収される。燃料室３で燃料力曽肖
費され発電に供される。この液体を燃料とする燃料電池
では負荷電流を一定にとった場合、電池電圧は燃料濃度
の強く依存する。燃料濃度が低いと燃料不足をきたして
電池電圧が低くなり、逆に燃料濃度が高いところでは反
応にあずからない燃料が空気極において直接燃焼を起す
ため電池電圧の低下を招き、温度上昇をもたらす等の弊
害が生じるようになる、このため、アノライト中の燃料
濃度は精度良く制御する必要がある。FIG. 2 shows a fuel circulation system for a fuel cell using a liquid as fuel and a conventional method for detecting the concentration of fuel in an anorite using an indirect method. To explain the fuel and anolyte circulation system, the fuel and electrolyte mixture anolyte 13 is fed to the m'ta pond main body 1 through the supply passage 3A by the pump 5.
The fuel is collected into the anorite reservoir 12 through the return passage 3B through the fuel chamber 3 provided therein. The fuel power is extracted in the fuel chamber 3 and used for power generation. In a fuel cell using this liquid as fuel, when the load current is kept constant, the cell voltage strongly depends on the fuel concentration. If the fuel concentration is low, there will be a fuel shortage and the cell voltage will be low; conversely, if the fuel concentration is high, the fuel that does not participate in the reaction will burn directly at the air electrode, leading to a drop in the cell voltage and a rise in temperature. Therefore, it is necessary to control the fuel concentration in the anorite with high precision.
従来は、アノライト溜１２の上部に設置したガス検出装
置により、アノライト溜中の燃料蒸気を検知する方法を
とっている。すなわち、アノライト中の燃料濃度と気相
中の燃料蒸気圧の相関に係を利用したものである。とこ
ろで、アノライト１３の気相部にガス検知装置を！２置
する方法では、気相の蒸気圧変化が、燃料蒸気の拡散速
度に大きく依存するためアノライト中の燃料濃度の変化
が早くなると、気相部の燃料蒸気圧が追従できなくなり
、ガス検出装［７で検出した濃度値と実際のアノライト
１３中の燃料濃度に大巾なずれが生じる欠点があった。Conventionally, a gas detection device installed above the anorite reservoir 12 is used to detect fuel vapor in the anorite reservoir. That is, it utilizes the correlation between the fuel concentration in the anorite and the fuel vapor pressure in the gas phase. By the way, there is a gas detection device in the gas phase of anorite 13! In the two-position method, the vapor pressure change in the gas phase largely depends on the diffusion rate of the fuel vapor, so if the fuel concentration in the anorite changes quickly, the fuel vapor pressure in the gas phase cannot follow it, and the gas detection device [There was a drawback that there was a large discrepancy between the concentration value detected in step 7 and the actual fuel concentration in the anorite 13.
すなわち、第３図に示すように。That is, as shown in FIG.
燃料としてメタノールを用いた場合について、アノライ
ト中のメタノール濃度を２１１０Ｑ／Ωから１＋ｍ。When methanol is used as fuel, the methanol concentration in the anolite is 2110Q/Ω to 1+m.
Ｑ／Ｑ に十分間で減少させたときのアノライト中の
メタノール濃度は曲線ａで示される。これに対して、ガ
ス検知装置７で示したメタノール濃度値は、曲線Ｃで示
されるように、実際濃度と大きくずれて検出精度が悪い
、また、一般に、ガス検出装置はガスの吸脱着を利用す
るため、高濃度の燃料蒸気にさらされると燃料蒸気の脱
着に長時間かかること等も精度を悪くする原因となって
いる。The methanol concentration in the anolyte when reduced to Q/Q over a tenth period is shown by curve a. On the other hand, as shown by curve C, the methanol concentration value indicated by the gas detection device 7 deviates greatly from the actual concentration, resulting in poor detection accuracy.In addition, gas detection devices generally utilize gas adsorption and desorption. Therefore, when exposed to high-concentration fuel vapor, it takes a long time to desorb the fuel vapor, which also causes deterioration in accuracy.
電解液は酸性形では硫酸などの腐食性の強いものが使わ
れるため、このような雰囲気ではガス検出装置が腐食さ
れるために寿命が短かく、信頼性に欠ける問題がある。If the electrolyte is acidic, a highly corrosive substance such as sulfuric acid is used, so in such an atmosphere the gas detection device will be corroded, resulting in a short lifespan and a lack of reliability.
また、この他にも濃度検出装置として、電解電流を利用
したサイクリックポルタンメトリ法やたとえば、特開昭
５６−１１８２７３号公報に記載のように小型電池を設
けて濃度検出装置として用いるもの等もあるが、これら
は検出感度とは別に検出系システムが複雑になって小形
化に難があるとともに信頼性に欠ける嫌いがある。In addition, other concentration detection devices include cyclic portammetry using electrolytic current, and a concentration detection device equipped with a small battery as described in JP-A-56-118273. However, in addition to the detection sensitivity, these systems have complicated detection systems, making it difficult to miniaturize them and lacking in reliability.
上記問題点は燃料及びアノライトの供給系統の液相部に
隔膜壁１４を設け、この隔膜壁１４を透過した燃料蒸気
を送風装置１５によってガス検知装置７に送って検知す
る手法により解決できる。The above problem can be solved by providing a partition wall 14 in the liquid phase portion of the fuel and anolite supply system, and sending the fuel vapor that has permeated through the partition wall 14 to the gas detection device 7 using the blower device 15 for detection.
すなわち、隔膜を透過する燃料蒸気の透過量は、アノラ
イト中の燃料濃度と気相側の燃料蒸気分圧および温度で
一義的に定まることを利用したものである。また、送風
装置１５を設けることにより、気相側の拡散による遅れ
をなくすことができる。That is, this method utilizes the fact that the amount of fuel vapor permeating through the diaphragm is uniquely determined by the fuel concentration in the anorite, the fuel vapor partial pressure on the gas phase side, and the temperature. Furthermore, by providing the blower device 15, delays due to diffusion on the gas phase side can be eliminated.
また、ガス検知装置７に送風することにより、検知装置
内の燃料濃度の履歴を解消し応答のよい燃料濃度の測定
か可能となる。In addition, by blowing air to the gas detection device 7, the history of fuel concentration within the detection device is eliminated, making it possible to measure the fuel concentration with good response.
隔膜を透過した燃料ガスは送風装置で、即時、ガス検知
装置に送られるため、アノライト中の燃料濃度とのずれ
がなく精度よく検出することができる。また、隔膜を介
しているため、硫酸の放出がなくなり、ガス検出装置７
の腐食による信頼性の低下がなくなる。The fuel gas that has passed through the diaphragm is immediately sent to the gas detection device by the blower, so it can be detected accurately without any deviation from the fuel concentration in the anorite. In addition, since the diaphragm is used, no sulfuric acid is released, and the gas detection device 7
This eliminates the reduction in reliability due to corrosion.
実施例を第１図で説明する。 An example will be explained with reference to FIG.
積層電池本体１の両側に空気室２および燃料室３を配列
し、燃料室３にはポンプ５により電解液１３を供給通路
３Ａ、３Ｂを通じて循環する。又、空気室２にはファン
４により酸化剤となる空気を供給通路２Ａを通して供給
させて燃料電池を運転する。An air chamber 2 and a fuel chamber 3 are arranged on both sides of the stacked battery body 1, and an electrolytic solution 13 is circulated into the fuel chamber 3 by a pump 5 through supply passages 3A and 3B. Further, the fuel cell is operated by supplying air as an oxidizing agent to the air chamber 2 through the supply passage 2A by the fan 4.
アノライト１３と接しているアノライト溜１２の壁面に
隔膜１４を設置する。隔膜１４を設置した部分を囲った
検出箱１６を設け、検出箱１６の下部間り部に送風装置
１５および上部間り部にガス検出装置７、ガス検出装置
の検出値の温度補償に用いるサーミスタ８を配し、検出
回路６に接続する。A diaphragm 14 is installed on the wall surface of the anolyte reservoir 12 that is in contact with the anolyte 13. A detection box 16 surrounding the part where the diaphragm 14 is installed is provided, and a blower 15 is installed in the lower part of the detection box 16, a gas detection device 7 is provided in the upper part of the detection box 16, and a thermistor is used for temperature compensation of the detected value of the gas detection device. 8 is arranged and connected to the detection circuit 6.
隔膜１４を透過した燃料蒸気は送風装置１５によってガ
ス検知装置７に送られて検知される。検知濃度が設定値
より低下すれば検出回路６を介して燃料供給バルブ１１
が開いて燃料タンク９より燃料１０がアノライト溜１２
へ供給される。The fuel vapor that has passed through the diaphragm 14 is sent to the gas detection device 7 by the blower device 15 and detected. If the detected concentration falls below the set value, the fuel supply valve 11 is activated via the detection circuit 6.
opens and fuel 10 flows from the fuel tank 9 into the anorite reservoir 12.
supplied to
本方式によれば第３図の曲ｇｂで示されるように、電解
液中の燃料濃度と（濃度曲線ａ）とガス検出装置７によ
って検知した燃料濃度がよく一致し、良好な検出精度を
得ることができる。このことからアノライト溜１２中の
アノライト１３中の燃料濃度の低下が、即時、検知され
、不足分の燃料が供給されることにより、アノライト中
の燃料濃度を一定に保持することができる。According to this method, as shown by curve gb in Fig. 3, the fuel concentration in the electrolyte (concentration curve a) and the fuel concentration detected by the gas detection device 7 match well, and good detection accuracy is obtained. be able to. From this, a decrease in the fuel concentration in the anolite 13 in the anolite reservoir 12 is immediately detected, and by supplying fuel for the shortage, the fuel concentration in the anolite can be maintained constant.
ニーで、隔膜１４は７ノライト及び燃料の液体を通さず
に気体蒸気を通す機能をもつ膜であれば良く四弗化エチ
レン樹脂製多孔質、たとえば、ボアテックス（ジャパン
ボアテックス製部品名）。At the knee, the diaphragm 14 may be a porous membrane made of tetrafluoroethylene resin, as long as it has the function of passing gaseous vapor without passing through the 7-norite and fuel liquid, such as VORETEX (part name manufactured by Japan VORETEX).
ポリフロンペーパ（ダイキン工業製商品名）、セルボア
（種水化学工業製商品名）等が十分機能を果す。又、カ
ーボン繊維をすいて紙状にしたものに、弾撥水性の四弗
化エチレン微粒子の懸濁液を処理し焼成したものも良い
。送風装置はファンやブロアー等の小型品で十分可能で
ある。Polyflon paper (trade name manufactured by Daikin Industries), Cellbore (trade name manufactured by Tanemizu Chemical Industry), etc. function adequately. Alternatively, a paper made of carbon fibers may be treated with a suspension of elastic and water-repellent tetrafluoroethylene fine particles and fired. A small fan or blower can be used as the blower.
Ｃ発明の効果〕
本発明によれば、検呂精度がよく、信頼性の高い燃料電
池の燃料検出装置を得ることができる。C Effects of the Invention] According to the present invention, a fuel detection device for a fuel cell with good test accuracy and high reliability can be obtained.
第１図は本発明の一実施例の燃料濃度検出装置応用の燃
料電池の運転系統図、第２図は従来型の燃料濃度検出装
置応用の燃料電池の運転系統図。
第３図は本発明及び従来型燃料濃度検出装置の応答特性
の比較を示す図である。
１・・・積層電池本体、２・・・空気室、３・・・燃料
室、４・・・ファン、Ｓ・・・ポンプ、６・・・検出回
路、７・・・ガス検出装置、８・・・サーシスタ、９・
・・燃料タンク、１０・・・燃料、１１・・・燃料供給
バルブ、１２・・・アノライト溜、１３・・・７ノライ
ト、１４・・・隔膜、１５・・・送風装置、１６・・・
検出箱。 １１１．１ 、′二丁
代理人 弁理士 小川勝男 ｔ−ｔ：；＋光３区FIG. 1 is an operation system diagram of a fuel cell to which a fuel concentration detection device according to an embodiment of the present invention is applied, and FIG. 2 is an operation system diagram of a fuel cell to which a conventional fuel concentration detection device is applied. FIG. 3 is a diagram showing a comparison of the response characteristics of the present invention and the conventional fuel concentration detection device. DESCRIPTION OF SYMBOLS 1... Laminated battery main body, 2... Air chamber, 3... Fuel chamber, 4... Fan, S... Pump, 6... Detection circuit, 7... Gas detection device, 8・・・Sirsista, 9・
...Fuel tank, 10...Fuel, 11...Fuel supply valve, 12...Anolyte reservoir, 13...7 norite, 14...Diaphragm, 15...Blower, 16...
detection box. 111.1 ,'Nichō Agent Patent Attorney Katsuo Ogawa t-t:;+Hikari 3rd Ward
Claims (1)
膜壁を設置し、前記隔膜壁を透過した燃料蒸気を移送す
る送風装置と前記燃料蒸気を検知するガス検知装置とを
設けたことを特徴とする燃料電池の燃料検出装置。1. A diaphragm wall is installed in the liquid phase part of the liquid fuel and anorite supply system, and a blower device for transferring the fuel vapor that has passed through the diaphragm wall and a gas detection device for detecting the fuel vapor are provided. A fuel detection device for a fuel cell.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61198858A JPS6355864A (en) | 1986-08-27 | 1986-08-27 | Fuel detector of fuel cell |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61198858A JPS6355864A (en) | 1986-08-27 | 1986-08-27 | Fuel detector of fuel cell |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS6355864A true JPS6355864A (en) | 1988-03-10 |
Family
ID=16398085
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61198858A Pending JPS6355864A (en) | 1986-08-27 | 1986-08-27 | Fuel detector of fuel cell |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6355864A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000026978A2 (en) * | 1998-11-03 | 2000-05-11 | Forschungszentrum Jülich GmbH | Method for adjusting the fuel concentration of a fuel mixture containing alcohol or ether as fuel and water, used by a fuel cell and a fuel cell system |
| JP2007095679A (en) * | 2005-09-28 | 2007-04-12 | Samsung Sdi Co Ltd | Fuel cell system, and device and method for controlling same |
-
1986
- 1986-08-27 JP JP61198858A patent/JPS6355864A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000026978A2 (en) * | 1998-11-03 | 2000-05-11 | Forschungszentrum Jülich GmbH | Method for adjusting the fuel concentration of a fuel mixture containing alcohol or ether as fuel and water, used by a fuel cell and a fuel cell system |
| WO2000026978A3 (en) * | 1998-11-03 | 2002-10-24 | Forschungszentrum Juelich Gmbh | Method for adjusting the fuel concentration of a fuel mixture containing alcohol or ether as fuel and water, used by a fuel cell and a fuel cell system |
| AU756379B2 (en) * | 1998-11-03 | 2003-01-09 | Forschungszentrum Julich Gmbh | Method for adjusting the fuel concentration of a fuel mixture containing alcohol or ether as fuel and water, used by a fuel cell and a fuel cell system |
| JP2007095679A (en) * | 2005-09-28 | 2007-04-12 | Samsung Sdi Co Ltd | Fuel cell system, and device and method for controlling same |
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