200415816 玖、發明說明： 【發明所屬之技術領域】 本發明係有關於一種直接改質型燃料電池系統。 【先前技術】 、傳統上，在日本經審查專利公告（案）第2,654,648號中揭示 度計，為如所知之用於量測位於水與乙醇溶液内之乙 2濃度的技術。該傳統技術包含接觸液體樣本的石英共振 斋，及用於設疋石英共振器之等效電路的電阻元件，供作 液體樣本黏度指數之黏度量測裝置，其在石英共振器頻率 附近之頻率量測阻抗值，用以由所計算之阻抗值計算出黏 【發明 直接 裝置， 含一燃 氣電極 液、及 燃料電 之甲醇 液體層 薄膜。 内容】 改貝型燃料電池系統使用黏度計供作燃料電池量測 具有圖18顯示之結構。直接改質型燃料電池系統包 料電池卜一空氣泵2用於供應空氣給燃料電池丨之空 11所需、—甲醇/水容器3用於容裝供作燃料之甲醇^ 一甲醇/水泵4用於由甲醇/水容器3供應燃料電池工之 :12所需之甲醇溶液。同時，一用於監視位於燃料 /辰度的甲醇量測器5，被設置在位於甲醇/水容器3之 處。位於燃料電池1之數字13，標示固態聚合電解質 播淪如何’在此型式之直接改質型燃料電池系統，合供 作燃料之乙醇濃度需要被偵:越 決。 τ ，从卜 < 問題需要解 (1)附著於甲醇量測器5之氣泡為問題之 87698 200415816 [化學反應式1] CH3OH+H2O— 6H++6e +C〇2 當上述反應在燃料電池之陽JiT 1 、 私/ %極電極（燃料電極12)由於發 電產生時，混合有二氧化碳之汝、为 、 岭硬為持續地被後送至甲醇/ 水谷^§ 3。因此，二氧化碳負治备 乳/包會傾向於附著在甲醇/水容 器3之甲醇量測器5。當錄料雷、冰〗；=、 田竹包池1又反應溫度為相對地高，200415816 (1) Description of the invention: [Technical field to which the invention belongs] The present invention relates to a directly modified fuel cell system. [Prior art] Traditionally, a meter is disclosed in Japanese Examined Patent Publication (Case) No. 2,654,648, which is a technique for measuring the concentration of ethylene 2 in a water and ethanol solution, as is known. The traditional technology includes a quartz resonance cavity that contacts a liquid sample, and a resistance element for an equivalent circuit of a quartz resonator, which is used as a viscosity measurement device for the viscosity index of a liquid sample, and its frequency is near the frequency of the quartz resonator. The measured impedance value is used to calculate the viscosity from the calculated impedance value. [Invented a direct device, containing a gas electrode liquid and a fuel liquid methanol liquid layer film. Content] The Gabe fuel cell system uses a viscometer for fuel cell measurement. It has the structure shown in Figure 18. Fuel cell system for direct modification fuel cell. An air pump 2 is used to supply air to the fuel cell. The space 11 is required. The methanol / water container 3 is used to hold methanol for fuel ^ A methanol / water pump 4 It is used to supply methanol solution required by fuel cell workers: 12 from methanol / water container 3. At the same time, a methanol measuring device 5 for monitoring the fuel / Chen degree is provided at the methanol / water container 3. The number 13 on the fuel cell 1 indicates how solid polymer electrolytes are propagated. In this type of directly modified fuel cell system, the ethanol concentration of the cooperative fuel needs to be detected: the more decided. τ From the following, the problem needs to be solved. (1) The bubbles attached to the methanol measuring device 5 are the problem 87678 200415816 [Chemical reaction formula 1] CH3OH + H2O— 6H ++ 6e + C〇2 When the above reaction is in the fuel cell When the Zhiyang JiT 1 and the private /% electrode (fuel electrode 12) are generated due to power generation, the mixture of carbon dioxide, solid, and hard solids is continuously sent to methanol / Mizutani ^ § 3. Therefore, the carbon dioxide negative preparation milk / pack will tend to adhere to the methanol measuring device 5 of the methanol / water container 3. When recording thunder and ice; =, Tianzhu Baochi 1 has a relatively high reaction temperature,
溶液將傾向蒸發，同時甲醇齑、冶 A 丁丁畔乳泡與霧汽會傾向於發生附 著。因此，將降低？醇量測器5之偵測準確度。 (2) 附著於甲醇量測器之雜質為問題之一。 甲醇/水般溶液為停留在甲醇/水容器3且流動量為較小， 以致雜質會傾㈣附著在甲醇量測器5。因此，會降低甲醇 量測器5之偵測準確度。 因為，前述之問題及傳統黏度計之特性，具有以下之 題： α ⑴即使當濃度為相同時’振盪頻率會隨著所將量測液體之 溫度而不同，因此應充份的調校此項差異。 ⑺如果雜質附著於石英共振器零件，將無法量測。因此， 應該採用估算。 (3) 當燃料電池之發電反應、，在供作燃料之甲醇溶液中產生 氣泡時，應在此之前取得量測，不致受其影響。 (4) 當甲醇溶液溫度昇高日争，將惡化石英共振曰器之偵測 性’應降低至適當溫度。 在考慮此等傳統技術問題之下完成本發明，本發明之一 項物件為提供一種直接改質型燃料電池系統，可以量測有 87698 200415816 關溶液之溫度與溶液之氣泡，以準確地量測甲醇濃度。 本發明申請專利範圍第丨項之一種直接改質型燃料電池 系統的特徵為包含一直接改質型燃料電池、一空氣泵用於 供應空氣給燃料電池之空氣電極、一甲醇/水容器用於容裝 混合有供作燃料之甲醇與水的甲醇/水般溶液、一甲醇/水泵 用於由甲醇/水容器供應甲醇/水般溶液給燃料電池之燃料 電極、一控制電路用於補充甲醇，使得在燃料電池内循環 <甲醇/水般溶液的甲醇濃度位於參考範圍之内、及一甲醇 里測备用於監.視在甲醇/水般溶液内之甲醇的濃度，其中該 甲醇量測器被設置在甲醇/水泵出口與燃料電池之燃料入 口 <間的官件處，或在甲醇/水容器與甲醇/水泵之間的管件 處。 本發明申請專利範圍第2項之—種直接改質型燃料電池 系統的特徵為包含—直接改質型燃料電池、—空氣系用於 τ尤二氣給燃料電池之空氣電極、—曱醇/水容器用於容裝 1有供作燃料之甲醇與水的甲醇/水般溶液、—甲醇/水栗 :^由甲醇/水容器供應甲醇/水般溶液給燃料電池之燃料 電極、-控制電路用於補充甲醇，使得在燃料電池内循環 = 水般溶液的甲醇濃度位於參考範圍之内、及一甲醇 =咨用於監視在甲醇/水般溶液内之甲醇的濃度，其中該 醇量測器被設置在一室處’其位於以流體相通於在甲醇/ 與燃料電池之燃料人口之間的管件處，或被設置 至處，其位於以流體相通於在甲醇/水容器與 <間的管件處。 87698 200415816 本發明中請專利範固第3項之—種直接改質型燃料電池 系統如申請專利範圍第2項之直接改質型燃料電池系統，其 中泫皇配備有一散熱鳍狀片。 本發明^請專利範圍第4項之—種直接改質型燃料電池 «、統的特徵為包含一直接改質型燃料電池' 供應空氣給燃料電池之空氣電極、—甲醇/水容器== 混合有供作燃料之甲醇與水的〒醇/水般溶液、—甲醇/水菜 =由甲醇/水容器供應甲醇/水般溶液給燃料 Γ二=電路用於補充甲醇，使得在燃料電池内循環 ' :又'合履的甲醇濃度位於參考範圍之内、及_ τ醇 :測器用於監視在甲醇/水般溶液内之甲醇 器被設置在-氣體位置，該位置在正常操丄 二=/水容器之甲醇/水般溶液下端；且其中當 體水平面昇二:停止甲醇/水栗;且在液 / 、、、 ^ 仔甲醇里測益在甲醇/水容器之甲醇 :又’合’夜下端時，量測甲醇濃度。 請專利範圍第5項之—種直接改質型燃料電池 系、、先的特徵為包各一亩 所 供應空氣給燃料;池之 然料電池、一空氣泵用於 混合有供作蛛料、田， 一甲醇/水容器用於容裝 用 （甲醇與水的甲醇/水般溶液、-甲醇/水系 4 水容器供應甲醇/水般溶液給燃料電池之燃料 二制電路用於補充甲醇，使得在燃料電池内循環 心液的甲醇濃度位於參考範圍之内、一正常操 月間供甲醇/水般溶液使用之循環通路、-具有較大容量 87698 200415816 之支路、及一關於在正常 之通路切換裝置、以及…乍趟吏用《循壤遇路與支路 溶液内之甲醇濃度，其-視在甲知/水般 丁成〒醇I測焱被設罾名一 孩位置在正常操作期間位又置纟位置， , 7醇水/谷咨之甲醇/水船、分、、 的下端；且其中該控制 4兒略在正常操作期間，經 環通路可令甲醇/水船& + + 、、二由切換循 〒知/水瓜/合夜在支路流動； 測甲醇濃度期間，鲈由、s物 τ砰里W态ϊ 、工、路裝置切換甲醇/水般溶液至古 路，位於甲酶/々女哭、、、 彳力又岭夜土支 抑又液體水平面被降低，甲醇量測哭接 觸氣體時，接著以诵跋4边 吁里仏」斋接 ^ 、路切換裝置將其由支路回復至正常矜 作之循環通路，以循护田# 土止吊才木. ^ ^ ^^^ 衣醇/水般溶液，且在甲醇量測器回 奴土低於梗體後之狀態了，量測甲醇濃度。 本各明：凊專利範園第6項之一種直接改質型燃料電池 系統的特徵為包本一亩 口直接改負型燃料電池、一空氣泵用於 應2氣給燃料電池之空氣電極、-甲醇/水容器用於容裝 -合有供作燃料之甲醇與水的甲醇/水般溶液、一甲醇/水泵 用於由甲醇/水容器供應甲醇/水般溶液給燃料電池之蛛料 電極控制電路料補充甲醇，使得在燃料電池内循環 :甲水般溶液的甲醇濃度位於參考範圍之内、及—甲醇 j时用於監視在甲醇/水般溶液内之甲醇的濃度，其中該 曱醇里測為被設置在—管件處，在甲醇/水泵操作期間可將 振動傳送至此。 本發明申請專利範圍第7項之一種直接改質型燃料電池 :、冼的特徵為包含一直接改質型燃料電池、一空氣泵用於 仏應窆氣給燃料電池之空氣電極、一甲醇/水容器用於容裝 87698 200415816 此：有供作燃料之甲醇與水的甲醇/水般溶液、—甲醇/水泵 兩由甲醇/水谷益供應甲醇/水般溶液給燃料電池之燃料 電極^一控制電路用於補充甲醇，使得在燃料電池内循環 j甲醇/水般落液的甲醇濃度位於參考範圍之内、及一甲醇 量測器用於監視在甲醇/水般溶液内之甲醇的濃度，其中該 甲醇里測态之設置處，使其平行於在該配置位置之甲醇/水 般溶液的流動。 本泰月申明專利範圍第8項之一種直接改質型燃料電池 系統如申凊專.利範圍第7項之直接改質型燃料電池系統，其 中孩甲醇量測器覆蓋有一篩孔或多孔過濾器。 在申清專利範圍第丨至8項任一項之直接改質型燃料電池 系統中，配置甲醇量測器在一甲醇/水般溶液循環通路之二 乳化碳氣體量為較小之位置處、設置甲醇量測器平行於甲 醇/水般溶液之流動、及附接一過濾器於甲醇量測器，避免 二氧化碳氣泡或雜質附著於甲醇量測器之表面，由是可以 高度準確的偵測甲醇之濃度。 本發明申請專利範園第9項之一種直接改質型燃料電池 系統如申請專利範圍第丨至8項任一項之直接改質型燃料電 池系統，具有一量測甲醇/水般溶液之溫度的溫度量測器與 甲醇f測為，其中控制電路具有用於調校溫度補償計算功 能，其使用溫度量測器所偵測之溫度信號，依據甲醇量測 器之偵測信號計算甲醇濃度。甲醇之濃度將隨著甲醇/水般 溶液之溫度情形而不同，甲醇之濃度可藉由調校準確地量 測出來，不會在使用諸如石英共振型式或超音波型式之甲 87698 -10- 200415816 醇量測器時，在經由液體之黏度計算出甲醇之濃度時，受 到溫度情形之影響。 本發明申請專利範圍第10項之一種直接改質型燃料電池 系統的特徵為包含一直接改質型燃料電池、一空氣泵用於 供應空氣給燃料電池之空氣電極、一甲醇/水容器用於容裝 混合有供作燃料之甲醇與水的甲醇/水般溶液、一甲醇/水泵 用於由甲醇/水容器供應甲醇/水般溶液給燃料電池之燃料 電極、一溫度量測器用以量測燃料電池之溫度、一電流/電 壓量測裝置用·以量測燃料電池之電流與電壓值、一控制電. 路用於補充甲醇，使得在燃料電池内循環之甲醇/水般溶液 的甲醇濃度位於參考範圍之内、及一甲醇量測器用於監視 在甲醇/水般溶液内之甲醇的濃度，其中控制電路具有相對 應於在燃料電池發電所產生電流與電壓以及溫度條件的效 率對照圖，依據經由溫度量測器所量測之溫度以及經由電 流/電壓量測裝置所量測之電流與電壓值，參考效率對照圖 預估所消耗之甲醇數量，及計算相等之甲醇數量且控制補 充之。 本發明申請專利範圍第10項之直接改質型燃料電池系統 中，控制電路具有相對應於在燃料電池發電產生之電流與 電壓以及溫度條件的效率對照圖，依據經由溫度量測器量 測之溫度以及經由電流/電壓量測裝置所量測之電流與電 壓值，參考效率對照圖預估所消耗之甲醇數量，及計算相 等之甲醇數量且控制補充之，由是可保持甲醇濃度正確地 位於參考範圍之内。 87698 -11 - 200415816 本發明申請專利範圍第11項之一種直接改質型燃料電池 系統的特徵為包含一直接改質型燃料電池、一空氣泵用於 供應空氣給燃料電池之空氣電極、一甲醇/水容器用於容裝 混合有供作燃料之甲醇與水的甲醇/水般溶液、一甲醇/水泵 用於由甲醇/水容器供應甲醇/水般溶液給燃料電池之燃料 電極、一溫度量測器用以量測燃料電池之溫度、一電流/電 壓量測裝置用以量測燃料電池之電流與電壓值、一控制電 路用於補充甲醇，使得在燃料電池内循環之甲醇/水般溶液 的甲醇濃度位.於參考範圍之内、及一甲醇量測器用於監視. 在甲醇/水般溶液内之甲醇的濃度，其中控制電路依據在燃 料電池發電所產生之電流與電壓以及溫度條件，及事先登 錄之預定參數，計算所消耗之甲醇數量，及控制相等甲醇 數量之補充。 本發明申請專利範圍第11項之直接改質型燃料電池系統 中，控制電路依據在燃料電池發電產生之電流與電壓以及 溫度條件，及事先登錄之預定參數，計算所消耗之甲醇數 量，及控制相等甲醇數量之補充，由是可保持甲醇濃度正 確地位於參考範圍之内。 【實施方式】 本發明之具體實例將參考圖式詳細說明。圖1顯示依據本 發明直接改質型燃料電池系統之第一具體實例。該具體實 例之燃料電池系統包含一聚合電解質燃料電池1、一空氣泵 2用於供應空氣給燃料電池之空氣電極、一甲醇/水容器3用 於容裝供作燃料之甲醇與水的溶液、及一甲醇/水泵4用於 87698 -12- 200415816 til 燃料電極12、及 合電解質㈣電池1包含-空氣電極！！ 如同電解質薄膜之固態聚合物薄膜13 ( 置Π二於監視在燃料中甲醇濃度的甲醇量測器5,被配 ί ·水泵4出口與燃料電池1之燃料入口之間的二7 氧2 7料“1期間’供作燃料之甲醇被消耗且產生-氣化蚊H。二氧化碳14由燃料電池i被集中至甲 ： 3,且夕自容器3經由排放管6釋放進入大氣。因為燃料電池: m屋生水的結果’操作期間在甲醇/水般溶液之水 量，保持持續地增加。為了保持燃料電池有效地反應 甲醇/水般合液《甲醇濃度應該保持在或大约為4%，以及者 :醇之濃度降低時，—預定數量之娜甲醇濃度由甲醇： 森（未於圖中示出）被供應至甲醇/水容器3，使得甲醇之濃度 才拴制住以保持在或大約4%。為完成此，被供應至燃料電 2 1、<燃料電極12之供作燃料液體的甲醇/水般溶液之甲醇 濃度應該被監視，且以甲醇量測器5監視甲醇之濃度。 在第一具體實例之直接改質型燃料電池系統中，用於監 視在甲醇/水泵4出口與燃料電池1的燃料入口之間的管件7 處乏甲醇濃度的甲醇量測器5之位置如前所述般，以致可獲 得以下優點。 又 (1)由於甲醇量測器5之配置位置，位於甲醇/水般溶液之壓 力為較高處，且在燃料循環通路所產生之氣泡14數量為較 少；由於氣泡14之影響性較少，可高度準確的量測甲醇之 87698 -13- 200415816 濃度。 (2) T醇量測器5被配置在靠近位於燃料電池1之燃料電極12 的入口，也就是說剛好位於燃料電池發生反應之位置的前 端，以致可以準確地控制甲醇/水般溶液之溫度與溶液之濃 度。 接著，依據本發明之第二具體實例的直接改質型燃料電 池系統，將參考圖2說明。燃料電池系統之第二具體實例的 特徵在於室9被設置在以流體相通於在甲醇/水容器3與甲 醇/水泵4之間的管件8處，及甲醇量測器5被設置在室9。如. 果有必要的話，可在室8形成一散熱鰭狀片10。在其他元件 方面，相同數字同第一具體實例之相同元件。 在室9中以流體相通於管件8，在甲醇溶液之二氧化碳14 的影響性為較少，甲醇之濃度可以隔離開混合有氣泡14之 燃料液體的情形下測得。如果散熱鰭狀片10之設置用於冷 卻在室9之物件，可降低所產生之氣泡14數量，且可進一步 降低氣泡14之影響性。 另一實施例，室9可被設置在流體相通於管件7處如第一 具體實例般，且亦可設置鰭狀片10。以如此方式，可獲得 同第二具體實例之相似技術優點。 接著，依據本發明之第三具體實例的直接改質型燃料電 池系統，將參考圖3說明。第三具體實例之其特徵在於設置 在管件7之甲醇量測器5Α，如圖1顯示之第一具體實例，及 甲醇量測器5Β亦被設置在室9，以流體相通於管件8處，如 圖2顯示之第二具體實例。 87698 -14- 200415816 第三具體實例之構造，由於可採用二個甲醇量測器5A與 5B，在量測甲醇濃度將具有量測資料冗餘的優點。使用以 甲醇量測器5A量測之濃度值，其可量測靠近燃料電池1之甲 醇/水般溶液中的甲醇濃度；也就是說，當系統起動時剛好 被供應至燃料電池1之甲醇濃度；以及使用甲醇量測器5B量 測室9之濃度值，其可量出適於在分級輸出時偵測甲醇濃度 之溫度，由是可以執行濃度之量測數值的切換。 接著，依據本發明之第四具體實例的直接改質型燃料電 池系統，將參考圖4說明。第四具體實例之特徵為控制功 能。在圖1至圖3顯示之第一至第三具體實例之每一者，由 於燃料電池1之發電反應在燃料電極12處產生的二氧化 碳，混合有燃料溶液如同氣泡14般，且由燃料電池1被傳送 至甲醇/水容器3。在甲醇/水容器3中，大部分二氧化碳之氣 泡14為氣體/液體分離器所分離，且經由排放管6排放進入大 氣。無論如何，微小量二氧化碳14被混在溶液中，且隨同 甲醇/水般溶液循環。因此，在燃料電池系統第一至第三具 體實例之每一者，甲醇量測器5被設置在管件7、管件8或以 流體相通於管件之室9處，其中少量氣泡14存在於甲醇/水般 溶液之循環路徑，不致於為氣泡14所影響。 無論如何，無法避免在溶液中留存有微量氣泡，在燃料 循環通路中循環流動，及一點一點的附著於甲醇量測器5。 在本具體實例之燃料電池系統中，當在量測甲醇濃度 時，一控制電路20用以控制數個輔助裝置之至少一個（諸如 空氣泵2或甲醇/水泵4)停止，以在量測甲醇濃度之情形下， 87698 -15- 200415816 避免在甲醇/水容器3產生氣泡14。 控制電路20包含-驅動電路21及一輸出控制電路22，以開 二或關閉及控制空氣泵2與甲醇/水泵4之速度、及用於控制 這些程式之中央處理單元23。 同時在此具骨豆貫例中，室9之設置為流體相通於由甲醇/ 杈泵I伸土燃料私池丨之燃料入口的管件7，及甲醇濃度量 測裝置％具有一濃度量測器31與-位於室9之溫度量測器32 以量測甲醇濃度。 、接：’本具.體實例之直接改質型燃料電池系統的甲醇濃 度（量測與控制，將參考圖5顯*之流程圖說明。 μ步驟1:類似空氣泵2、甲醇泵4、或相當數量之產生器(本 靶例為2氣泵)之至少一個被控制停止，以抑制發電反應， 防止產生二氧化碳，使得當量測濃度時抑制在 3所產生之氣泡。 砰尺合為 步驟八採用曱醇量測器5以及在室9以流體相通於 之溫度量表25計算甲醇濃度。 步驟3:當所計算甲醇濃度之結果在事先設定之來 内，確定甲醇濃度之結果當為正值，及移至步驟5 ^ 負值，移至步驟4。 疋 步騍4 ·當氣泡可能附著於量測器5或25時，改變甲 系3之操作量以去除氣泡。在此控制之後，再次回復至牛： 2以量測甲醇濃度。 ν % 系統之補助設 步知5 ·凡成甲醇濃度之量測及回復產生器 備至正常操作。 87698 -16- 200415816 在第四具體實例之直接改質型燃料電池系統中，在操作 期間當氣泡傾向於附著於甲醇濃度量測器或相似者，在燃 料電池停止操作之後或在模式改變為可限制產生氣泡之 後，量測甲醇之濃度與溫度，且由結果計算出甲醇濃度。 因此，所量測甲醇濃度具有高度準確性。 用於第四具體實例之甲醇濃度量測裝置30，具有圖6顯示 之構造，包含一諸如石英共振器之濃度量測器31與一經由 固定構件33固定於室9之分離壁面9A處的一般溫度感測設 備之溫度量測·器32，以及一位於室9外側用於供應搖動電壓 於濃度量測器31之界面34，可抽取共振信號，及同時供應 電流於溫度量測器32且抽取溫度感測信號。 日本經審查專利公告（案）第2,654,648號之先前技術中，未 敘述關於黏度計之溫度補償。無論如何，（1)用於濃度量測 器3之石英共振器之振盪頻率的改變端視溫度情形而異，溫 度補償在實用上為必要的，及（2)濃度量測器32應該被設置 在非常靠近濃度量測器31處，因為有必要量測在濃度量測 器31周圍之溫度，藉以完成濃度量測器31之溫度補償。. 在考慮此項技術之必要性，本具體實例之燃料電池系統 中，濃度量測器31為藉由固定構件33結合於溫度量測器32， 及用於控制此等量測器之界面34亦結合於甲醇濃度量測裝 置30。 控制界面34傳送以溫度量測器32所偵測之溫度信號加上 濃度量測器31之共振頻率信號至控制電路20。控制電路20 具有用於溫度補償數值之表格。中央處理單元23參考在表 87698 -17- 200415816 格之資料，調校濃度量測器31之共振頻率，以計算真的共 振頻率、計算等效之甲醇濃度、及控制在甲醇/水循環之甲 醇/水般溶液中的甲醇濃度位於或大約在4%處。 如圖6所示結構之甲醇濃度量測裝置30，可被用於取代在 第一至第三具體實例之甲醇量測器5，或可被用於如下敘述 之每一具體實例中。 為了防止氣泡附著於燃料電池之第一至第四具體實例之 每一者的甲醇濃度量測裝置30的甲醇量測器5處或濃度量 測器31處，其表面粗糙度由數百個nm之階數，以研磨改變 成為數十個nm階數。量測器之表面亦可塗敷含水材料。 後一方法所使用之塗敷材料，可使用矽（二氧化矽）、氧 化鈦、氧化锆、鋁或這些材料之組合。表1顯示塗敷材料、 塗敷方法及所應用表面之情形。 [表1] 產品 製造商 基底溶液型式 特性 Frescera Matsushita Denko 矽、氧化鈦 浸泡方式、透明 Heatless Glass Nikko Science 矽(二氧化矽） 浸泡方式、透明 SAG/S-100 Daiso 矽(二氧化矽） 浸泡方式、透明 Cerastatts Parker Processing 矽(二氧化矽） 噴灑方式、具顏色/ 透明 AE-800 Hoden Seimitsu 矽(二氧化矽） 噴灑方式、具顏色/ 透明 Super Coat H Fine Chemical Japan 矽(二氧化矽） 耐熱塗料、噴灑罐、 透明 Tonetsu polysirazane Tonetsu 矽(SixNy) 多功能塗料、透明 Ceramic Coating Nippan Kenkyujo 矽、氧化锆 抗熱塗漆、黑白色、 無光澤 87698 -18- 200415816The solution will tend to evaporate, and at the same time methanol tritium, butadiene milk foam and mist will tend to adhere. So will it decrease? Detection accuracy of the alcohol measuring device 5. (2) Impurities attached to the methanol measuring device are one of the problems. The methanol / water-like solution stays in the methanol / water container 3 and has a small amount of flow, so that impurities may pour on the methanol measuring device 5. Therefore, the detection accuracy of the methanol measuring device 5 will be reduced. Because the aforementioned problems and the characteristics of traditional viscometers have the following problems: α ⑴ Even when the concentration is the same, the 'oscillation frequency will vary with the temperature of the liquid being measured, so this should be fully adjusted. difference. ⑺If foreign matter adheres to the quartz resonator part, it cannot be measured. Therefore, estimates should be used. (3) When the power generation reaction of the fuel cell generates bubbles in the methanol solution used as fuel, the measurement should be obtained before this, and it will not be affected by it. (4) When the temperature of the methanol solution rises, the contention of the quartz resonator should be reduced to an appropriate temperature. The present invention has been completed in consideration of such conventional technical problems. An object of the present invention is to provide a directly modified fuel cell system, which can measure the temperature of the solution and the bubbles of the solution in 87678 200415816 to accurately measure Methanol concentration. A direct reformed fuel cell system according to item 1 of the present invention is characterized by including a direct reformed fuel cell, an air pump for supplying air to an air electrode of the fuel cell, and a methanol / water container for Holds a methanol / water-like solution mixed with methanol and water for fuel, a methanol / water pump for supplying a methanol / water-like solution from a methanol / water container to a fuel electrode of a fuel cell, and a control circuit for replenishing methanol, Make the concentration of methanol in the fuel cell circulating < methanol / water-like solution within the reference range, and measure in a methanol for monitoring. The concentration of methanol in the methanol / water-like solution, where the methanol measuring device It is installed at the official part between the methanol / water pump outlet and the fuel inlet of the fuel cell, or at the pipe between the methanol / water container and the methanol / water pump. The second item of the scope of patent application of the present invention—a direct-modified fuel cell system is characterized by including—the direct-modified fuel cell, —the air electrode used for τyou two-gas fuel cell, and —methanol / The water container is used to hold a methanol / water-like solution containing methanol and water as fuel, methanol / water chestnut: ^ The methanol / water container supplies the methanol / water-like solution to the fuel cell fuel electrode, and the control circuit Used to replenish methanol so that the concentration of methanol in a fuel cell cycle = water-like solution is within the reference range, and one methanol = is used to monitor the concentration of methanol in a methanol / water-like solution, where the alcohol meter Is located in a chamber 'which is in fluid communication with a pipe between the methanol / fuel cell population of the fuel cell, or is located everywhere which is in fluid communication between the methanol / water container and the < At the fittings. 87698 200415816 In the present invention, patent No. 3, a direct modification fuel cell system of the patent application, such as the direct modification fuel cell system in the second patent application scope, in which the emperor is equipped with a cooling fin. The present invention ^ asks for the scope of patent No. 4-a direct modification type fuel cell «, which is characterized by including a direct modification type fuel cell 'air electrode for supplying air to the fuel cell,-methanol / water container == mixed There is a methanol / water-like solution of methanol and water for fuel,-methanol / water dish = methanol / water-like solution is supplied from the methanol / water container to fuel Γ = = circuit is used to replenish methanol and circulate in the fuel cell ' : Again, the methanol concentration within the range is within the reference range, and _ alcohol: The detector is used to monitor the methanol in a methanol / water-like solution. The methanol device is set to the -gas position, which is in normal operation. = / Water The lower end of the methanol / water-like solution in the container; and when the body level rises: stop the methanol / water chestnut; and in the liquid / ,,, and ^ methanol, measure the methanol in the methanol / water container: again At this time, measure the methanol concentration. Please refer to item 5 of the patent scope-a direct modification type fuel cell system. The first feature is to pack one acre each of the air supplied to the fuel; the pool of fuel cells and an air pump are used for mixing A methanol / water container is used for holding (a methanol / water-like solution of methanol and water, -methanol / water system 4 water container supplies a methanol / water-like solution to the fuel cell's fuel secondary circuit for replenishing methanol, so that The methanol concentration of the circulating cardiac fluid in the fuel cell is within the reference range, a circulation path for methanol / water-like solution during normal operation,-a branch with a large capacity 87698 200415816, and a device for switching between normal paths , And ... At first, the officials used the "methanol concentration in the following roads and branch road solutions, which-apparently known as water / butyrobutanol I test, was set to have a child's position during normal operation. Set the position, the lower end of the methanol / water boat, alcohol, water, and alcohol; and where the control 4 is slightly during normal operation, the methanol / water boat can be accessed via the loop path. Two by switching cycle through the know / water melon / Heye in the branch Flow; During the measurement of methanol concentration, the sea bass switched from methanol, water-like solutions to ancient roads from industrial and road devices, and was located at the formazan / sister-in-law crying. The liquid level was lowered. When the methanol was measured and contacted with the gas, it was then used to recite the four sides of the road, and said, "Zaijie", the road switching device will return it from the branch road to the normal circulation cycle to follow the field. # 土 止 吊 才 木. ^ ^ ^^^ ^ Alcohol / water-like solution, and measure the methanol concentration after the methanol measuring device returns to the state where the soil is lower than the stem. Ben Mingming: 凊 Patent Fan Yuan A direct modification fuel cell system of item 6 is characterized by a 1-mu port direct modification of a negative fuel cell, an air pump for the air electrode of the fuel cell for 2 gas, and a methanol / water container for the capacity. Equipped with a methanol / water-like solution combining methanol and water for fuel, and a methanol / water pump for supplying a methanol / water-like solution from a methanol / water container to the spider electrode control circuit of the fuel cell to replenish methanol, so that Fuel cell internal circulation: the methanol concentration of the formazan solution is within the reference range, —Methanol is used to monitor the concentration of methanol in a methanol / water-like solution, where the methanol is measured as being set at a pipe fitting, and vibration can be transmitted to it during the operation of the methanol / water pump. A direct reformed fuel cell of item 7: The plutonium is characterized by including a direct reformed fuel cell, an air pump for the air electrode that responds to the gas to the fuel cell, and a methanol / water container for the container. 87678 200415816 This: There is a methanol / water-like solution of methanol and water for fuel, and a methanol / water pump. The methanol / water pump supplies the methanol / water-like solution to the fuel cell fuel electrode. A control circuit is used to supplement the methanol. So that the methanol concentration of the methanol / water-like liquid circulated in the fuel cell is within the reference range, and a methanol measuring device is used to monitor the methanol concentration in the methanol / water-like solution, where Place it so that it flows parallel to the methanol / water-like solution at this location. This month stated that a direct-modification fuel cell system in item 8 of the patent scope, such as the direct modification fuel cell system in item 7 of the patent scope, wherein the methanol measuring device is covered with a sieve or porous filter Device. In the direct-improved fuel cell system according to any of claims Nos. 丨 8, a methanol measuring device is arranged at a position where the amount of emulsified carbon gas in the second circulation path of a methanol / water-like solution is small, Set the methanol measuring device parallel to the flow of the methanol / water-like solution and attach a filter to the methanol measuring device to prevent carbon dioxide bubbles or impurities from attaching to the surface of the methanol measuring device, so that the methanol can be detected with high accuracy. Its concentration. A direct reformed fuel cell system according to item 9 of the present application for a patent, such as a direct reformed fuel cell system according to any one of claims 1-4, has a measurement temperature of a methanol / water-like solution. The temperature measuring device and methanol f are measured. The control circuit has a function for adjusting the temperature compensation calculation. It uses the temperature signal detected by the temperature measuring device to calculate the methanol concentration based on the detection signal of the methanol measuring device. The concentration of methanol will vary with the temperature of the methanol / water-like solution. The concentration of methanol can be accurately measured by adjustment. It will not be used such as the quartz resonance type or the ultrasonic type. 87678 -10- 200415816 When measuring the alcohol concentration, the concentration of methanol is calculated from the viscosity of the liquid, which is affected by the temperature. A direct modification fuel cell system according to item 10 of the present invention is characterized by including a direct modification fuel cell, an air pump for supplying air to an air electrode of the fuel cell, and a methanol / water container for Holds a methanol / water-like solution mixed with methanol and water for fuel, a methanol / water pump for supplying a methanol / water-like solution from a methanol / water container to a fuel cell fuel electrode, and a temperature measuring device for measuring Fuel cell temperature, a current / voltage measurement device, to measure the current and voltage of the fuel cell, a control circuit. The circuit is used to replenish methanol, so that the methanol concentration of the methanol / water-like solution circulating in the fuel cell It is located within the reference range and a methanol measuring device is used to monitor the concentration of methanol in a methanol / water-like solution. The control circuit has an efficiency map corresponding to the current, voltage, and temperature conditions generated by the fuel cell power generation. Based on the temperature measured by the temperature measuring device and the current and voltage values measured by the current / voltage measuring device, refer to the efficiency comparison chart to estimate It is equal to the number of methanol consumption quantity of methanol, and the calculation and the control supplement. In the direct-modified fuel cell system according to item 10 of the present invention, the control circuit has an efficiency comparison chart corresponding to the current, voltage, and temperature conditions generated by the fuel cell power generation. The temperature and the current and voltage values measured by the current / voltage measurement device, the reference efficiency comparison chart is used to estimate the amount of methanol consumed, and the equivalent amount of methanol is calculated and controlled to supplement it, so that the methanol concentration can be kept correctly located Within the reference range. 87698 -11-200415816 A direct modification fuel cell system according to item 11 of the scope of patent application of the present invention is characterized by including a direct modification fuel cell, an air electrode for supplying air to the fuel cell, an methanol electrode, and a methanol A water / water container is used to hold a methanol / water-like solution mixed with methanol and water for fuel, a methanol / water pump is used to supply a methanol / water-like solution from a methanol / water container to a fuel electrode of a fuel cell, and a temperature is measured. The detector is used to measure the temperature of the fuel cell, a current / voltage measuring device is used to measure the current and voltage of the fuel cell, and a control circuit is used to replenish methanol, so that the methanol / water-like solution circulating in the fuel cell Methanol concentration level. Within the reference range and a methanol measuring device for monitoring. The concentration of methanol in a methanol / water-like solution, where the control circuit is based on the current and voltage and temperature conditions generated by the fuel cell power generation, and Pre-registered predetermined parameters, calculate the amount of methanol consumed, and control the supplementation of the equivalent amount of methanol. In the direct-modified fuel cell system according to item 11 of the present invention, the control circuit calculates the amount of methanol consumed based on the current and voltage and temperature conditions generated by the fuel cell power generation, and predetermined parameters registered in advance, and controls The equivalent amount of methanol is added to keep the methanol concentration within the reference range. [Embodiment] A specific example of the present invention will be described in detail with reference to the drawings. Fig. 1 shows a first specific example of a direct-modified fuel cell system according to the present invention. The fuel cell system of this specific example includes a polyelectrolyte fuel cell 1, an air pump 2 an air electrode for supplying air to the fuel cell, a methanol / water container 3 for containing a solution of methanol and water for fuel, And a methanol / water pump 4 for 87698 -12- 200415816 til fuel electrode 12, and electrolyte ㈣ battery 1 contains-air electrode! !! The solid polymer film 13 (like an electrolyte film) is placed on a methanol measuring device 5 that monitors the concentration of methanol in the fuel. It is equipped with two oxygen compounds between the water pump 4 outlet and the fuel cell 1 fuel inlet. "1 period 'of methanol used as fuel is consumed and generated-gasification mosquito H. Carbon dioxide 14 is concentrated by the fuel cell i to A: 3, and released from the container 3 through the exhaust pipe 6 into the atmosphere. Because the fuel cell: m The result of the raw water is that the amount of water in the methanol / water-like solution keeps increasing continuously during the operation. In order to keep the fuel cell effectively reacting with the methanol / water-like solution, the methanol concentration should be maintained at or about 4%, and: When the concentration of alcohol is reduced, a predetermined amount of methanol concentration is supplied from methanol: Sen (not shown in the figure) to the methanol / water container 3 so that the concentration of methanol is tethered to remain at or about 4%. To accomplish this, the methanol concentration of the methanol / water-like solution supplied as the fuel liquid to the fuel electrode 21 < the fuel electrode 12 should be monitored, and the methanol concentration is monitored by the methanol measuring device 5. In the first Direct modification of specific examples Type fuel cell system, the position of the methanol measuring device 5 for monitoring the concentration of methanol-depleted at the pipe 7 between the outlet of the methanol / water pump 4 and the fuel inlet of the fuel cell 1 is as described above, so that the following advantages can be obtained (1) Because of the configuration position of the methanol measuring device 5, the pressure of the methanol / water-like solution is higher, and the number of bubbles 14 generated in the fuel circulation path is relatively small; It can measure the concentration of methanol from 87698 -13 to 200415816 with high accuracy. (2) The T-alcohol measuring device 5 is arranged near the entrance of the fuel electrode 12 located at the fuel cell 1, which means that the reaction occurs just at the fuel cell. The front end of the position is such that the temperature and concentration of the methanol / water-like solution can be accurately controlled. Next, a direct-modified fuel cell system according to a second embodiment of the present invention will be described with reference to FIG. 2. Fuel cell system The second specific example is characterized in that the chamber 9 is provided in fluid communication with the pipe 8 between the methanol / water container 3 and the methanol / water pump 4, and the methanol measuring device 5 is provided in the chamber 9. For example, If necessary, a heat-dissipating fin 10 can be formed in the chamber 8. In terms of other elements, the same numerals are the same as those in the first specific example. In the chamber 9, fluid communication with the pipe 8 and carbon dioxide 14 in the methanol solution The influence is relatively small, and the concentration of methanol can be measured in the case of the fuel liquid mixed with the air bubbles 14. If the heat dissipation fins 10 are provided to cool the objects in the chamber 9, the generated air bubbles 14 can be reduced. The number can be further reduced, and the influence of the air bubbles 14 can be further reduced. In another embodiment, the chamber 9 can be provided in fluid communication with the pipe 7 as in the first specific example, and a fin 10 can also be provided. A technical advantage similar to that of the second specific example is obtained. Next, a directly modified fuel cell system according to a third specific example of the present invention will be described with reference to FIG. 3. The third specific example is characterized by a methanol measuring device 5A provided in the pipe 7 as shown in the first specific example shown in FIG. 1, and a methanol measuring device 5B is also provided in the chamber 9 in fluid communication with the pipe 8. Figure 2 shows a second specific example. 87698 -14- 200415816 The structure of the third specific example, because two methanol measuring devices 5A and 5B can be used, measuring the concentration of methanol will have the advantage of measuring data redundancy. Using the concentration value measured by the methanol measuring device 5A, it can measure the methanol concentration in a methanol / water-like solution close to the fuel cell 1; that is, the methanol concentration that is just supplied to the fuel cell 1 when the system is started And using the methanol measuring device 5B to measure the concentration value of the chamber 9, which can measure the temperature suitable for detecting the methanol concentration during the classification output, so that the switching of the concentration measurement value can be performed. Next, a direct modification type fuel cell system according to a fourth embodiment of the present invention will be described with reference to FIG. 4. The fourth specific example is characterized by a control function. In each of the first to third specific examples shown in FIGS. 1 to 3, the carbon dioxide generated at the fuel electrode 12 due to the power generation reaction of the fuel cell 1 is mixed with the fuel solution like bubbles 14 and the fuel cell 1 It is transferred to a methanol / water container 3. In the methanol / water container 3, most of the carbon dioxide gas bubbles 14 are separated by a gas / liquid separator, and are discharged into the atmosphere through a discharge pipe 6. In any case, a minute amount of carbon dioxide 14 is mixed in the solution and circulated with the methanol / water-like solution. Therefore, in each of the first to third specific examples of the fuel cell system, the methanol measuring device 5 is disposed at the pipe 7, the pipe 8, or the chamber 9 in fluid communication with the pipe, in which a small amount of air bubbles 14 exists in the methanol / The circulation path of the water-like solution is not affected by the air bubbles 14. In any case, it is unavoidable that microbubbles remain in the solution, circulate in the fuel circulation path, and adhere to the methanol measuring device 5 little by little. In the fuel cell system of this specific example, when measuring the methanol concentration, a control circuit 20 is used to control at least one of the auxiliary devices (such as the air pump 2 or the methanol / water pump 4) to stop to measure the methanol. In the case of concentration, 87698 -15- 200415816 avoids generating bubbles 14 in the methanol / water container 3. The control circuit 20 includes a drive circuit 21 and an output control circuit 22 to open or close and control the speed of the air pump 2 and the methanol / water pump 4 and a central processing unit 23 for controlling these programs. At the same time, in this example, the chamber 9 is provided with a pipe 7 in fluid communication with the fuel inlet of the private fuel pool extending from the methanol / branch pump I, and the methanol concentration measuring device has a concentration measuring device. 31 and-a temperature measuring device 32 located in the chamber 9 to measure the methanol concentration. , Then: 'The methanol concentration of the direct-modified fuel cell system of this example. (Measurement and control will be described with reference to the flow chart shown in Figure 5.) μStep 1: Similar to air pump 2, methanol pump 4, Or at least one of a considerable number of generators (the target is 2 air pumps) is controlled to stop to suppress the power generation reaction and prevent the generation of carbon dioxide, so that the bubbles generated at 3 are suppressed when the concentration is measured. The bang ruler is step eight Calculate the methanol concentration using the methanol measuring device 5 and the temperature gauge 25 in fluid communication with the chamber 9. Step 3: When the result of the calculated methanol concentration is set in advance, the result of determining the methanol concentration is positive. , And move to step 5 ^ negative value, move to step 4. 疋 Step 骒 4 · When bubbles may be attached to the measuring device 5 or 25, change the operation amount of the A series 3 to remove bubbles. After this control, again Return to cattle: 2 to measure the methanol concentration. Ν% system subsidy steps 5 · Fancheng methanol concentration measurement and recovery generator is ready for normal operation. 87698 -16- 200415816 Direct modification in the fourth specific example Fuel cell system During operation, when bubbles tend to adhere to the methanol concentration measuring device or the like, after the fuel cell stops operating or after the mode is changed to limit the generation of bubbles, measure the methanol concentration and temperature, and calculate the methanol concentration from the results Therefore, the measured methanol concentration is highly accurate. The methanol concentration measuring device 30 used in the fourth specific example has a structure shown in FIG. 6 and includes a concentration measuring device 31 such as a quartz resonator and a fixed The component 33 is a temperature measuring device 32 of a general temperature sensing device fixed to the separation wall surface 9A of the chamber 9 and an interface 34 located outside the chamber 9 for supplying a shaking voltage to the concentration measuring device 31, which can extract resonance signals , And at the same time supply current to the temperature measuring device 32 and extract the temperature sensing signal. In the prior art of Japanese Examined Patent Publication (Case) No. 2,654,648, the temperature compensation of the viscometer is not described. In any case, (1) uses The change of the oscillation frequency of the quartz resonator of the concentration measuring device 3 varies depending on the temperature situation, temperature compensation is practically necessary, and (2) the concentration The measuring device 32 should be located very close to the concentration measuring device 31, because it is necessary to measure the temperature around the concentration measuring device 31 to complete the temperature compensation of the concentration measuring device 31. When considering this technology, Necessity. In the fuel cell system of this specific example, the concentration measuring device 31 is combined with the temperature measuring device 32 through the fixing member 33, and the interface 34 for controlling these measuring devices is also combined with the methanol concentration measurement. Device 30. The control interface 34 transmits the temperature signal detected by the temperature measuring device 32 plus the resonance frequency signal of the concentration measuring device 31 to the control circuit 20. The control circuit 20 has a table for temperature compensation values. The central processing unit 23Refer to the data in Table 87698 -17- 200415816 to adjust the resonance frequency of the concentration meter 31 to calculate the true resonance frequency, calculate the equivalent methanol concentration, and control the methanol / water-like solution in the methanol / water cycle. The methanol concentration in is at or about 4%. The methanol concentration measuring device 30 having a structure as shown in FIG. 6 may be used instead of the methanol measuring device 5 in the first to third specific examples, or may be used in each specific example described below. In order to prevent bubbles from adhering to each of the first to fourth specific examples of the fuel cell, the methanol concentration measuring device 30 of the methanol concentration measuring device 30 or the concentration measuring device 31 has a surface roughness of hundreds of nm. The order of tens of nanometers is changed by polishing. The surface of the measuring device can also be coated with water-containing material. The coating material used in the latter method may be silicon (silicon dioxide), titanium oxide, zirconia, aluminum, or a combination of these materials. Table 1 shows the conditions of the coating material, the coating method and the applied surface. [Table 1] Product manufacturer base solution type characteristics Frescera Matsushita Denko Silicon, titanium oxide immersion method, transparent Heatless Glass Nikko Science silicon (silicon dioxide) immersion method, transparent SAG / S-100 Daiso silicon (silicon dioxide) immersion method , Transparent Cerastatts Parker Processing Silicon (silicon dioxide) Spray method, colored / transparent AE-800 Hoden Seimitsu Silicon (silicon dioxide) Spray method, colored / transparent Super Coat H Fine Chemical Japan Silicon (silicon dioxide) Heat-resistant coating , Spray can, transparent Tonetsu polysirazane Tonetsu silicon (SixNy) multifunctional coating, transparent Ceramic Coating Nippan Kenkyujo silicon, zirconia heat-resistant paint, black and white, matte 87698 -18- 200415816
Ceramic Coating Tsuchiya 矽、氧化锆 浸泡、抗腐蝕塗料、 透明 Atron Nippon Soda 矽(二氧化矽） 表面保護、防銹、抗 腐蝕塗料、透明 Sumiceram 朝曰化學 (Asahi Chemical) 矽、鋁 抗熱塗漆耐熱溫度 800°C、黑色 Pre Ceramic Coating SRI International 矽(SixNy) 抗熱保護性塗料、透 明 Porcelain enamel Fuji Porcelain Enamel 二氧化矽+α 抗熱、彩色 電漿汽相沉積 (Plasma CVD) Dipsol 氧化矽 分批 接著，依據本發明之第五具體實例的直接改質型燃料電 池系統，將參考圖7說明。如前所述，如果氣泡或雜質附著 於甲醇量測器5或濃度量測器31之表面，可能發生誤差。為 防止氣泡之附著，當氣泡附著於量測器5之表面時，由溶液 拉起f測為5將是有效的。 因此，在第五具體實例之燃料電池系統中，甲醇量測器5 (或甲醇濃度量測裝置30)被設置在甲醇/水容器3 —高度 處，其中量測器在正常操作下為位於氣體處。控制電碜20 控制甲醇/水泵4之操作，使得在燃料電池之操作期間泵4為 在操作中，如圖中（a)所顯示，藉以定置甲醇量測器5在甲醇 /水容器3之氣體中，僅當在偵測甲醇濃度時停止甲醇/水泵4 以收集在甲醇/水容器3之大部分甲醇/水甲醇/水般溶液，及 昇高位於容器中液體之水平面，使得甲醇量測器5在液體之 下，當在量測甲醇濃度時，用以防止氣泡附著於量測器之 表面，藉以正確地量測甲醇濃度，如圖中（b)所顯示。 因此在正常操作期間，甲醇量測器5不會接觸於液體且可 87698 -19- 防止氣泡附著於甘主 、 度期間位於、、、w /、、面。吓可令甲醇量測器5在量測甲醇濃 準確的量、、目,1 : 〈下，不會受到氣泡影響，以致可以高度 、j里/則甲醇濃度。 接著，依攄+欠 池系統 纟明之第六具體實例的直接改質型燃料電 面，其暫=8說明。第六具料例之特徵為功能方 藉以移除附著t應甲醇/水般溶液至具有不同長度之通路， 如圖8所亍"；甲醇量測器5之氣泡且拉起量測器5。 路41 、 在正常操作期間除了循環通路40外另加一支 變通路電路20依據正常操作或量測濃度而改 甲酸桫趾疋，、支路41之容積大於正常通路40之容積；當 料落液在支路41流動時，在甲醇/水容哭3 體水平面將大幅 甲水……的視 山、 牛低使仔位於容器3之甲醇量測哭5， 由液體改變至氣體處。 岬里 在弟具體實例之丨钬料兩 電，η碎/下〜 + 中，在燃料電池完成發 二/時在正㈣作期間，溶液在正常通路倾環，如圖Ceramic Coating Tsuchiya silicon, zirconia immersion, anti-corrosion coating, transparent Atron Nippon Soda silicon (silicon dioxide) surface protection, rust prevention, anti-corrosion coating, transparent Sumiceram Asahi Chemical silicon, aluminum heat-resistant paint heat-resistant Temperature 800 ° C, black Pre Ceramic Coating SRI International silicon (SixNy) heat-resistant protective coating, transparent Porcelain enamel Fuji Porcelain Enamel silicon dioxide + α heat-resistant, color plasma vapor deposition (Plasma CVD) Dipsol silicon oxide batch Next, a direct modification type fuel cell system according to a fifth specific example of the present invention will be described with reference to FIG. 7. As described above, if bubbles or impurities adhere to the surface of the methanol measuring device 5 or the concentration measuring device 31, an error may occur. In order to prevent the bubbles from adhering, when the bubbles are attached to the surface of the measuring device 5, it is effective to measure f to be 5 by pulling up from the solution. Therefore, in the fuel cell system of the fifth specific example, the methanol measuring device 5 (or the methanol concentration measuring device 30) is set at a height of the methanol / water container 3, where the measuring device is located in a gas under normal operation. Office. The control battery 20 controls the operation of the methanol / water pump 4 so that the pump 4 is in operation during the operation of the fuel cell. As shown in (a) of the figure, the gas of the methanol measuring device 5 in the methanol / water container 3 is set. During the methanol concentration detection, stop the methanol / water pump 4 to collect most of the methanol / water methanol / water-like solution in the methanol / water container 3 and raise the level of the liquid in the container to make the methanol measuring device 5 Under the liquid, when measuring the methanol concentration, it is used to prevent bubbles from adhering to the surface of the measuring device, so as to correctly measure the methanol concentration, as shown in (b) of the figure. Therefore, during normal operation, the methanol measuring device 5 does not come into contact with the liquid and can prevent air bubbles from adhering to the main body. It can make the methanol measuring device 5 accurately measure the concentration of methanol, and it will not be affected by the air bubbles, so that the methanol concentration can be high, j mile / then. Next, according to the sixth specific example of the direct modification fuel cell based on the 摅 + under-cell system 其 Ming, its temporary = 8 description. The sixth example is characterized in that the functional party removes the adhesion of the methanol / water-like solution to the paths with different lengths, as shown in Fig. 8; the bubbles of the methanol measuring device 5 and the measuring device 5 is pulled up. . Road 41. During the normal operation, in addition to the circulation path 40, another variable path circuit 20 is used to change the formic acid according to normal operation or measured concentration. The volume of the branch 41 is greater than the volume of the normal path 40; When the liquid flows in the branch 41, at the methanol / water volume 3, the level of the body will be greatly reduced. The sight of the mountain, the cow is low, so that the baby is located in the container 3, and the methanol measurement is 5. The liquid is changed to the gas. In the specific example of the cape, I have two materials, η broken / down ~ +, when the fuel cell completes the development 2 / hour during the normal operation, the solution tilts in the normal path, as shown in the figure
示。下在此情形，位於甲醇，水容器…量測J 當里測位於落液之甲酸、、择命奸 從<甲知辰度期間，改變通路使得溶液 支路41流動，藉以降低在甲醇/水容器3之液體水平面，以致 使甲醇量測H5離開液體且接觸於氣體，如圖咐)所示。 .接著，、改變通路使得溶液在正常通路40中流動，藉以昇 南在甲醇/水容器3之液體永承工 、 夜奴水千面，以致使甲醇量測器5在液 體中，且在此情形下量測甲醇濃度，如圖㈣所示。 因此依據第六具體實例之燃料電池系統，氣泡附著於位 87698 -20- 200415816 f液拉4 :的甲醇量測器5之表面，且使其離開液體以接觸 氣體’由是清除氣治，芬士在# ^ 飞包及接耆可令甲醇量測器5在液體之 下’且在^:到較少氣、泡影響下量測甲醇濃度。因此可以高 度準確地量測甲醇濃度。 在此具體實例中，田龄/ 1 m & … 甲％ /水甲醇/水般溶液在支路41的流 動：在正常操作情形下是不會使用的，因此不會受到發電 反尤所產生^熱！的加熱’以致支路Μ之操作如同一冷卻 通路〃在里4甲醇濃度期間可暫時性地降低甲醇/水 /水般^容液溫度，由是可提昇量測之準確度。 接著，依據本發明> @ ^ j 4罘七具禮貫例的直接改質型燃料電 池系統，將參考圖9說明。燃料電池系統之具體實例的特徵 在於設置在〒醇/水泵4之輸出口的甲醇量測器5,及甲醇/ 水系輸人口端與輸出口端以管件7、8及振動吸收接頭51 與52所連接。參考號碼53為代表㈣泵*之阻尼。 在‘作，、月間甲醇/水系4振動。因此，其輸出口—起振動， 且士果曱醇里測态5被設置在輸出口處，附著於其表面 泡；雜質可：甲醇/她振動所清除，使得它的表面； 水返保持乾淨。 Q此依據第七具體實例的直接改質型燃料電池系統， 可防止氣泡與雜質附著於f醇量測器5且可 量測甲醇濃度。 ^確的 、接著，依據本發明之第八具體實例的直接改質型燃料恭 池系統，將參考圖10說明。該具體實例之特徵為所設置； _之万位。請參照圖1〇(a)顯示之甲醇量測器5被詨 87698 -21 - 200415816 置在管件60 ;其中甲醇/水甲醇 感測面為平行於液體61之流動 /水般溶液的流動 方向。 使得它的 W較於圖10(b)所 1且用於液體 向的万式，此可降低氣泡與雜質之附著數量。 在此具體實例中，圖丨丨顯示締 mi 、、 、下師孔或多孔過滤器63，其排 列不a干涉液體之流動，使得並 κ于其後盍甲醇量測器5，由是可 進一步降低附著於甲醇量測哭5矣品、尸 拉— 里」⑽5表面<氣泡與雜質數量。 接耆’依據本發明之第九且髀余 、旦貝例的直接改質型燃料電 池系、、无’將參考圖丨2至14說明。备 ^ 田甲蚌/水甲醇/水般溶液之 /置度由於發電之反應而變的較 一 吾甽甲舻、、曲忐 /、難以經由甲醇量測器 的特徵在：又：此’圖12_示燃料電池系統之具體實例 欲在於控制電路2°’具有經由發電之電流量、所輸入 ==效率對照圖、溶液之循環流量、在系統外釋放之甲 二广：< 溫度’預估及計”醇濃度之功能。 圖頭…接改質型燃料電池系統包含如第一且p 例夂固態聚合物燃料電池丨、一而# " ^ 料電池^之空氣電極u、一甲醇栗2用於供應空氣給燃 之甲醇與㈣液、及—於容裝供作燃料 甲醇溶液給燃料電池之熾料 、水奋斋3供應 川共應供作燃料之f醇至甲醇由w“ 於檢祖兩a，、 &合w 3。參考號碼73為連接 万；九、、科电池1芡氣體/液體分離器。 此具體實例之燃料電池系統包本 制電路20。控制電路2〇具有：：空，驅動設備之控 22 , φ m ^ 恥動电路21、一輸出控制電路 ^、中央處理早元23、及一对*漱⑽ 效率對照圖儲存部分24,以及控 87698 -22- 200415816 制甲醇/水甲醇/水般溶液之甲醇濃度與發電功率之輸出。為 了執行此控制，其被建構出甲醇濃度信號由甲醇量測器5 輸入以及電池溫度信號與所產生電流/電壓信號為來自於 溫度量測器74之輸入，如同必要之資訊。 為了監視溶液之溫度，甲醇濃度量測裝置30具有圖7顯示 之可安裝結構；但在此具體實例中，被設置用以監視燃料 電池1反應之電池溫度量測器74的溫度信號，連同設置在甲 醇/水容器3之甲醇量測器5使用。 如圖13所示.，當直接改質型燃料電池系統被用於充電在. 電氣輔助腳踏車之第二電瓶，當鎳鎘電瓶被使用如同第二 電瓶，在再次充電之前電瓶可被自行放電，以充電第二電 瓶。控制電路20監視第二電瓶之放電情形，以及當它完全 地被放電，起動燃料電池系統以再充電電瓶（自行放電監視 模式（i)，低耗電模式（ii))。當電氣輔助腳踏車在運轉中，該 模式被切換至驅動模式（iii) ’且控制電路20反應於第二電瓶 之充電情形，控制燃料電池系統所產生之電力。 在驅動模式（iii)中，當燃料電池系統反應以產生電力，甲 醇/水甲醇/水般溶液之溫度昇高。因此，溫度可能昇高而高 於超音波型式或石英共振型式之一般甲醇量測器5的允許 溫度，其造成難以量測甲醇濃度。 因此在此具體實例之燃料電池系統中，控制電路20監視 甲醇/水甲醇/水般溶液之溫度，如圖14流程圖所示（步驟 S11);當溫度位於可以量測濃度之範圍内量測濃度、依據 所量測甲醇濃度計算所應供應甲醇之數量、以及控制由甲 87698 -23- 200415816 知谷器71供應給甲醇/水容器3所需要之 另-方面，如果在步驟su之溫产 1 y驟扣）。 量測器5執行濃度量測之 皿古了？、里出可用於T醇 生電力數量、所輸入之？醇 器5由所產 gi,. ^ %數里或相似者（步驟Sl3)ff估Ψ ^辰度，及依據濃度之預估控 3)預估Τ S14)。 丨H、Κ ▼醉數量（步驟 預估甲醇濃度之程序， 效率對F R 十 ' 电流、所輸入甲醇數量、 双手對恥圖、落〉夜循環數 里 據圖16流程圖之无外釋放《數量、及依 ㈡ 合夜，皿度預估甲醇濃度。 ⑴在系統起動且溫度低時量測甲醇二度 考值（步驟S21)。 者存t、作參 ⑺確定溫度情況是否適於量測(步職)。 (3) 例如，當在監視第二電池 可被量測之情形，量測甲醇 ’：、幻農度處於 (步驟S22、S23)。 a，水濃度且更新參考值 (4) 量測燃料電池1之電壓、電流、電池溫度，經由事先呑 錄如圖15顯示之相關於電壓、 、w ^ 兒 ’皿度的效率對照圖24 預估甲醇之消耗量（步驟S24)。 午I、、圖24 預估之理論’敛述如下： &每—ml甲醇所產生之熱量為18_2[U/ml]。 b.燃料電池之電.電流x操作間距=所產生之能量[j]。 c·所消耗（曱醇數量以上述之數值乘上效率計算之。 所產生之能量/效率/每—單位所產生之 耗甲醇之數量。 ~ ’ I Μ 87698 •24- 200415816 (5)如果溫度條件為不適杏 的計算是依據事先吞錄二、…无卜釋放之甲醇數量 以調校所留存4醇ί=爾-蒸發對照圖所計算，藉 卞< r知！（步驟S25)。 ()依據（3)所量測之甲醇漠声斗苜碎十 且错存為—來考度〇所需補充之甲醇數量 〶補无之甲醇數量(步驟S26)。 …數！計算所 (7)依據（6)計算所需補充之數量 至甲醇/水容器3(步驟S27)。 添加甲醇 在操作期間.’—非常小數量之甲醇由系統 知對照圖之值增+ π 、 睪攻’但可 以調校。…以調整’或簡單的外加-預定數量予 鐘里Si::度之循環時間可以是固定間㉛’諸如每分 刀里及母十分鐘，及事先被設定在系統中。 依據第九具體實例之燃料電池系統，即使者甲_ 水甲醇/水船、、六、—、 丨從田T知 益、、、，备履爻溫度昇高而太高，且一般甲醇量測器: ’里測/辰度時，所消耗之甲醇量，可在控制電路20中預Show. In this case, located in the methanol, water container ... Measurement J When measuring the formic acid located in the falling liquid, and the life-span from <A Zhichen degree, change the path so that the solution branch 41 flows, thereby reducing the methanol / The liquid level of the water container 3 is such that the methanol measurement H5 leaves the liquid and contacts the gas, as shown in the figure). Then, change the path so that the solution flows in the normal path 40, so that the liquid in the methanol / water container 3 will be perpetually worked, and the Yemen water will make the methanol measuring device 5 in the liquid, and here Measure the methanol concentration under the circumstances, as shown in Figure ㈣. Therefore, according to the fuel cell system of the sixth specific example, bubbles are attached to the surface of the methanol measuring device 5 at 87678 -20- 200415816 f liquid pull 4: and leave it away from the liquid to contact the gas.士 在 # 飞 Flying bag and connection can make the methanol measuring device 5 under the liquid 'and measure the methanol concentration under the influence of less gas and bubbles. Therefore, the methanol concentration can be measured with high accuracy. In this specific example, the flow of Tianling / 1 m & A% / water methanol / water-like solution on branch 41: it will not be used under normal operating conditions, so it will not be caused by power generation ^ Hot! The heating ′ is such that the operation of the branch M is the same as the cooling channel. During the methanol concentration, the temperature of the methanol / water / water can be temporarily reduced, so the measurement accuracy can be improved. Next, a direct modification fuel cell system according to the present invention > @ ^ j 4 罘 7 will be described with reference to FIG. 9. The specific example of the fuel cell system is characterized by a methanol measuring device 5 provided at the output port of the methanol / water pump 4, and pipe / pipe 7, 8 and vibration absorbing joints 51 and 52 at the methanol / water system inlet and outlet ends. connection. Reference number 53 is the damping of the pump. During the operation, the methanol / water system 4 vibrates during the month. Therefore, its output port is vibrated, and the test state 5 in Scopolamine is set at the output port and is attached to the surface of the bubble; impurities can be removed by methanol / her vibration, so that its surface is kept clean . This direct modification fuel cell system according to the seventh specific example can prevent bubbles and impurities from adhering to the alcohol measuring device 5 and can measure the methanol concentration. Indeed, next, a direct modification fuel cell system according to an eighth embodiment of the present invention will be described with reference to FIG. 10. The characteristics of this specific example are set; Please refer to Fig. 10 (a). The methanol measuring device 5 is shown in Fig. 10 (87698-21) to 200415816 and placed on the pipe 60. The methanol / water methanol sensing surface is parallel to the flow direction of the liquid 61 / water-like solution. This makes its W larger than that shown in Figure 10 (b) and used for the liquid direction. This can reduce the number of bubbles and impurities attached. In this specific example, the figure shows the associated pores or porous filters 63, the arrangement of which does not interfere with the flow of the liquid, so that it is followed by the methanol measuring device 5, which can be further Decrease the amount of bubbles and impurities on the surface of the methanol measuring 哭 5 矣, dead pull — li⑽5⑽. Then, according to the ninth and remaining examples of the present invention, the direct-density fuel cell system of the denier case, and no, will be described with reference to FIGS. 2 to 14. ^ ^ T. mussel / water methanol / water-like solution / placement changes due to the power generation reaction is more difficult than meguchi, 忐, /, difficult to pass through the methanol measuring device features: again: this' Figure 12_ shows the specific example of the fuel cell system is that the control circuit 2 ° 'has the amount of current through power generation, the input == efficiency comparison chart, the circulating flow rate of the solution, and the Jia Erguang released outside the system: < temperature' The function of estimating "alcohol concentration" is shown in the figure ... The modified fuel cell system includes the first and second examples of solid polymer fuel cells, and the air electrode of the battery and methanol. Chestnut 2 is used to supply air to the burning methanol and mash, and-to contain the fuel used as a fuel methanol solution to the fuel cell, and Fenzhai 3 to supply Sichuan ’s fuel alcohol to methanol from w " Yu Jianzu two a, & together w 3. Reference number 73 is for connecting 10,000; IX battery, 1 芡 gas / liquid separator. The fuel cell system of this specific example includes a manufacturing circuit 20. The control circuit 20 has: the control 22 of the air-driving device, φ m ^ shame circuit 21, an output control circuit ^, the central processing early element 23, and a pair of * washing efficiency map storage section 24, and the control 87698 -22- 200415816 Methanol concentration of methanol / water methanol / water solution and output of power generation. To perform this control, it is constructed that the methanol concentration signal is input by the methanol measuring device 5 and the battery temperature signal and the generated current / voltage signal are input from the temperature measuring device 74 as necessary information. In order to monitor the temperature of the solution, the methanol concentration measuring device 30 has a mountable structure as shown in FIG. 7; but in this specific example, a temperature signal of a battery temperature measuring device 74 for monitoring the reaction of the fuel cell 1 is provided together with the setting The methanol measuring device 5 is used in a methanol / water container 3. As shown in Figure 13, when the direct-modified fuel cell system is used to charge the second battery of the electric-assisted bicycle, when the nickel-cadmium battery is used like the second battery, the battery can be discharged by itself before recharging. To charge the second battery. The control circuit 20 monitors the discharge condition of the second battery, and when it is completely discharged, starts the fuel cell system to recharge the battery (self-discharge monitoring mode (i), low power consumption mode (ii)). When the electric-assisted bicycle is running, the mode is switched to the driving mode (iii) 'and the control circuit 20 controls the power generated by the fuel cell system in response to the charging condition of the second battery. In the driving mode (iii), when the fuel cell system reacts to generate electricity, the temperature of the methanol / water methanol / water-like solution increases. Therefore, the temperature may rise higher than the allowable temperature of the general methanol measuring device 5 of the ultrasonic type or the quartz resonance type, which makes it difficult to measure the methanol concentration. Therefore, in the fuel cell system of this specific example, the control circuit 20 monitors the temperature of the methanol / water methanol / water-like solution, as shown in the flowchart of FIG. 14 (step S11); when the temperature is within the range of the measurable concentration, it is measured. Concentration, calculation of the amount of methanol to be supplied based on the measured methanol concentration, and the other aspects required to control the supply of the methanol / water container 3 by the chiller 71 to 87678 -23- 200415816, if it is produced at step su 1 y snap). Is the dish 5 that the measuring device 5 performs concentration measurement ancient? What is the amount of electricity that can be used for T alcohol generation? The alcohol container 5 is estimated from the gi,. ^% Produced or similar (step S13), the estimated degree, and the estimated control based on the concentration 3) the estimated T S14).丨 H, KK ▼ The amount of drunk (the procedure for estimating the concentration of methanol, the efficiency versus the FR ten 'current, the amount of methanol entered, the number of hands on the shame, and the number of night cycles) according to the flowchart in Figure 16 , And according to the night, the degree of methanol is estimated. 量 Measure the second degree of methanol when the system is started and the temperature is low (step S21). Save the parameters and determine whether the temperature is suitable for the measurement ( (3) For example, when monitoring the situation where the second battery is measurable, measuring the methanol ':, the phantom degree is in (steps S22, S23). A. The water concentration and the reference value is updated (4) Measure the voltage, current, and battery temperature of the fuel cell 1, and record the efficiency related to the voltage, voltage, and battery temperature shown in Figure 15 in advance as shown in Figure 15 to estimate the methanol consumption (step S24). I. Figure 24 The estimated theory is summarized as follows: & The amount of heat produced per ml of methanol is 18_2 [U / ml]. B. Electricity of fuel cell. Current x operating distance = generated energy [j ]. C. Consumption (The amount of methanol is calculated by multiplying the above value by the efficiency. Energy produced / Efficiency per unit—the amount of methanol consumed per unit. ~ 'I ML 87698 • 24- 200415816 (5) If the temperature conditions are not suitable, the calculation is based on the amount of methanol released in advance. The remaining 4 alcohols are calculated from the comparison chart of evaporation-by-evaporation, and are known by "<r!" (Step S25). () According to (3) the methanol infestation of alfalfa is broken into ten pieces and misstored as-to test The amount of methanol to be replenished is equal to the amount of methanol to be replenished (step S26) .... The number! The calculation office (7) calculates the amount of replenishment to methanol / water container 3 according to (6) (step S27). Add methanol During the operation. '—A very small amount of methanol is increased by the value of the system's control map + π, tapping', but can be adjusted .... to adjust 'or simply add-a predetermined amount to the cycle of Si :: degrees in the clock The time can be a fixed interval, such as ten minutes per minute and the mother, and it is set in the system in advance. According to the ninth specific example of the fuel cell system, even if the water is methanol / water boat, six,-,丨 From Tian T Zhiyi ,,,, the temperature of the preparation shoes is too high, and the general amount of methanol Is: When the amount of methanol 'in the measurement / e degree of consumption, the control circuit 20 may be in the pre-
及補充相等數量；因此位於甲醇/水般溶液之甲醇濃产 保持在適當值。 又J 、接著，依據本發明之第十具體實例的直接改質型燃料電 二系統，將參考圖丨7說明。此具體實例之燃料電池系統特 知在於具有經由計算程序取代如第九具體實例之效率對照 圖’以控制甲醇濃度之功能。其硬體構造如圖12所示，柏 似於第九具體實例。 依據燃料電池系統之具體實例的甲醇濃度控制，執行如 87698 -25- 200415816 下： (1) 固定地量測電流值，且將電流乘上時間間距計算出電 流量（步驟S31)。 (2) 能量轉換為電流之計算如下（步騾S32)。 首先，燃料電池之反應如下。 [化學反應式2] CH30H+H20— 6H+ + 6e- + C〇2 ··..··在陽極反應（燃料電極） 6H+ + 6e' + 3/2 02-> 3H20······在陰極反應（空氣電極）。 其中每一電子之帶電荷為1.6〇xl(T19 C，每一 mol甲醇之帶電 荷得知大約為57.8xl04 C。由於電流為每一單位時間之帶電 荷，如果監視電流量，可計算出轉換成為電流之甲醇量。 電流量/每一 mol之帶電荷=轉換成為電流之能量數。 (3) 接著，計算出化學反應熱熱量（損失）（步騾S33)。發生 於陰極（空氣電極）與陽極（燃料電極）之化學反應所產生之 熱量，也就是如所知之熵損失（B)，事先登錄在控制電路20。 (4) 接著，由燃料電池之電壓計算出效率（步騾S34)。單一 電池之理論電壓如所知為1.2 V，以致電壓損失之計算，可 以由燃料電池電壓計算出單一電池電壓之電壓損失。 (1.2—所量測單一電池之電壓）/1.2 =電壓損失（C)。 (5) 接著，計算出甲醇所產生之能量（步騾S35)。 (A)/(C) + (B) =所消耗之能量（D)。 (6) 接著由甲醇所產生之能量計算出所消耗之甲醇量（E)。 (D)/甲醇之熱量總量18·2 kJ/m卜所消耗甲醇數量（E)。 持續地監視在燃料電池1所產生之電流與電壓，且如同上 87698 -26- 200415816 述計算出所消耗之甲醇量。所消耗甲醇之等效量，以甲醇 泵72由甲醇容器71補充至甲醇/水容器3。 在起動時甲醇量測器5量測甲醇濃度。如果該數值不是位 糸參考範圍之内，使用感測器用於補充必要數量之甲醇。 依據具體實例之燃料電池系統，在甲醇/水甲醇/水般溶液 之甲醇濃度，以甲醇量測器5之最小濃度量測，可保持位於 參考範圍之内。 本發明每一具體實例中，可採用超音波型式如同甲醇量 測斋5，或將甲醇濃度計量裝置30之溫度量測器32予以取代 為石英共振型式。 、依據本發明第丨至8項任一項之直接改質型燃料電池系 f，配置甲醇量測器在一甲醇/水般溶液循環通路之二氧化 奴乳體量為較小之位置處、設置甲醇量測器平行於甲醇/水 叙4液之流動、及附接一過濾器於甲醇量測器，避免二氧 化碳氣泡或雜質附著於甲醇量測器之表面，由是可以高产 率確的偵測甲醇之濃度，且可以控制甲醇濃度。 依據本發明申請專利範圍第9項之直接改質型燃料電池 系、、、先，由於甲醇之濃度將隨著甲醇/水般溶液之溫度情形而 不同，甲醇之濃度可藉由調校準確地量測出來且予以栌 =，不會在使用諸如石英共振型式或超音波型式之甲醇^ 測器時，在經由液體之黏度計算出甲醇之濃度時，受到= 度情形之影響。 依據本發明申請專利範圍第10項之直接改質型燃料電池 系統，控制電路具有相對應於在燃料電池發電產生之^流 87698 -27- 200415816 與電壓以及溫度條件的效率對照圖，依據經由溫度量測器 量測之溫度以及經由電流/電壓量測裝置所量測之電流與 電壓值，參考效率對照圖預估所消耗之甲醇數量，及計算 相等之甲醇數量且控制補充之，以致可保持甲醇濃度正確 地位於參考範圍之内。 依據本發明申請專利範圍第11項之直接改質型燃料電池 系統，控制電路依據在燃料電池發電產生之電流與電壓以 及溫度條件，及事先登錄之預定參數，計算所消耗之甲醇 數量，及控制.相等甲醇數量之補充，以致可保持甲醇濃度 正確地位於參考範圍之内。 【圖式簡單說明】 圖1為本發明第一具體實例之方塊圖。 圖2為本發明第二具體實例之方塊圖。 圖3為本發明第三具體實例之方塊圖。 圖4為本發明第四具體實例之方塊圖。 圖5為依據第四具體實例量測甲醇濃度程序之流程圖。 圖6為用於第四具體實例之甲醇濃度量測設備之方塊圖。 圖7(a)、（b)為本發明第五具體實例之方塊圖。 圖8(a)、（b)為本發明第六具體實例之方塊圖。 圖9為本發明第七具體實例之方塊圖。 圖10(a)、（b)為本發明第八具體實例之剖面圖，其顯示一 甲醇量測器之安裝情形。 圖11為顯示第八具體實例一變異體的剖面圖，其甲醇量 測器覆蓋有一過濾器。 87698 -28- 200415816 圖12為本發明第九具體實例之方塊圖。 圖13為用於第九具體實例之圖表，其顯示燃料電池之驅 動模式。 圖14為依據第九具體實例量測甲醇濃度程序之流程圖。 圖15為用於第九具體實例控制電路之效率對照圖的圖 表。 圖16為依據第九具體實例在量測甲醇濃度程序中預估甲 醇濃度之程序的流程圖。 圖17為依據.第十具體實例量測甲醇濃度程序之流程圖。 圖18為所提出一種直接改質型燃料電池系統之方塊圖。 【圖式代表符號說明】 1 燃料電池 2 空氣泵 3 甲醇/水般溶液容器 4 甲醇/水泵 5 甲醇量測器 5 a 甲醇量測器 5b 甲醇量測器 6 排放管 7 管件 8 管件、氣室 9 室 9A分離壁面 10鳍狀片 11空氣電極 87698 -29- 200415816 1 2燃料電極 1 3數字、固態聚合電解質薄膜 1 4氣泡 '二氧化碳 20控制電路 2 1 驅動電路 22輸出控制電路 23中央處理單元 24效率對照圖 25溫度量表 3 0量測裝置 3 1 ·濃度量測器 3 2溫度量測器 33固定構件 34界面 40正常循環通路 41 支路 5 1 振動吸收接頭 52振動吸收接頭 60管件 61液體 63過濾器 71 甲醇容器 72 甲醇泵 73氣體液體分離器 74溫度量測器 -30- 87698And replenish the same amount; therefore, the concentration of methanol in a methanol / water-like solution is maintained at an appropriate value. J. Next, a direct-modified fuel-electricity two system according to a tenth specific example of the present invention will be described with reference to Figs. The fuel cell system of this specific example is known to have the function of controlling the methanol concentration by replacing the efficiency comparison chart of the ninth specific example through a calculation program. The hardware structure is shown in Fig. 12, which is similar to the ninth specific example. According to the methanol concentration control of the specific example of the fuel cell system, the implementation is as follows: 87698 -25- 200415816: (1) Measure the current value fixedly, and multiply the current by the time interval to calculate the electric flow (step S31). (2) The calculation of energy conversion into current is as follows (step S32). First, the reaction of the fuel cell is as follows. [Chemical reaction formula 2] CH30H + H20— 6H + + 6e- + C〇2 ······ Anode reaction (fuel electrode) 6H + + 6e '+ 3/2 02- > 3H20 ····· Reaction at the cathode (air electrode). The charge of each electron is 1.60 × l (T19 C, and the charge of each mol of methanol is about 57.8 × 104 C. Since the current is the charge per unit time, if you monitor the amount of current, you can calculate the conversion The amount of methanol that becomes the current. The amount of current / the charge per mol = the number of energy converted into the current. (3) Next, calculate the heat (loss) of the chemical reaction (step S33). It occurs at the cathode (air electrode) The heat generated by the chemical reaction with the anode (fuel electrode), which is the entropy loss (B) as known, is registered in the control circuit 20 in advance. (4) Next, the efficiency is calculated from the voltage of the fuel cell (step S34) ). The theoretical voltage of a single cell is known as 1.2 V, so that the voltage loss of a single cell can be calculated from the fuel cell voltage. (1.2—the measured single cell voltage) /1.2 = voltage loss (C). (5) Next, calculate the energy produced by methanol (step S35). (A) / (C) + (B) = energy consumed (D). (6) Next produced by methanol The energy calculated the amount of methanol consumed (E). (D) / Total amount of heat of methanol 18 · 2 kJ / m. The amount of methanol consumed (E). The current and voltage generated in fuel cell 1 are continuously monitored, and the consumption is calculated as described in 87678 -26- 200415816 above. The methanol equivalent. The equivalent amount of methanol consumed is supplemented by a methanol pump 72 from a methanol container 71 to a methanol / water container 3. The methanol measuring device 5 measures the methanol concentration at startup. If the value is not within the reference range The sensor is used to replenish the necessary amount of methanol. According to the specific example of the fuel cell system, the methanol concentration in a methanol / water methanol / water solution is measured with the minimum concentration of the methanol measuring device 5, which can be kept at the reference Within each specific example of the present invention, the ultrasonic type can be adopted as the methanol measurement test 5 or the temperature measuring device 32 of the methanol concentration measuring device 30 can be replaced by a quartz resonance type. Direct modification fuel cell system f of any of 8 items, equipped with a methanol measuring device in a methanol / water-like solution circulation path where the amount of the milk of the slave dioxide is small, and a methanol measuring device is provided. In the flow of 4 liquids of methanol / water, and attach a filter to the methanol measuring device to prevent carbon dioxide bubbles or impurities from attaching to the surface of the methanol measuring device, so that the methanol concentration can be accurately detected with high yield, and The concentration of methanol can be controlled. According to the direct modification fuel cell system of the scope of application for patent of the present invention, first, because the concentration of methanol will vary with the temperature of the methanol / water-like solution, the concentration of methanol can be borrowed Measured accurately by the calibration and 栌 =, it will not be affected by the degree of methanol when the methanol concentration is calculated from the viscosity of the liquid when using a methanol ^ detector such as a quartz resonance type or an ultrasonic type. . According to the direct-improved fuel cell system according to item 10 of the present application, the control circuit has an efficiency comparison chart corresponding to the current generated by the fuel cell power generation 87678 -27- 200415816 and voltage and temperature conditions. The temperature measured by the measuring device and the current and voltage values measured by the current / voltage measuring device, the estimated amount of methanol consumed with reference to the efficiency comparison chart, and the equivalent amount of methanol calculated and supplemented so that it can be maintained The methanol concentration is correctly within the reference range. According to the direct-improved fuel cell system according to item 11 of the present invention, the control circuit calculates the amount of methanol consumed and controls based on the current and voltage and temperature conditions generated by the fuel cell power generation, and predetermined parameters registered in advance, and controls . Complementation of equal methanol quantities so that the methanol concentration is kept correctly within the reference range. [Brief Description of the Drawings] FIG. 1 is a block diagram of a first specific example of the present invention. FIG. 2 is a block diagram of a second embodiment of the present invention. FIG. 3 is a block diagram of a third embodiment of the present invention. FIG. 4 is a block diagram of a fourth embodiment of the present invention. FIG. 5 is a flowchart of a methanol concentration measurement procedure according to a fourth specific example. FIG. 6 is a block diagram of a methanol concentration measuring device used in a fourth specific example. 7 (a) and 7 (b) are block diagrams of a fifth specific example of the present invention. 8 (a) and 8 (b) are block diagrams of a sixth specific example of the present invention. FIG. 9 is a block diagram of a seventh embodiment of the present invention. Figs. 10 (a) and (b) are cross-sectional views of an eighth embodiment of the present invention, which show the installation of a methanol measuring device. Fig. 11 is a sectional view showing a variant of the eighth specific example, in which the methanol measuring device is covered with a filter. 87698 -28- 200415816 Fig. 12 is a block diagram of a ninth specific example of the present invention. Fig. 13 is a diagram for a ninth specific example showing a driving mode of a fuel cell. FIG. 14 is a flowchart of a procedure for measuring methanol concentration according to a ninth specific example. Fig. 15 is a diagram showing an efficiency comparison chart of a control circuit for a ninth specific example. Fig. 16 is a flowchart of a procedure for estimating methanol concentration in a methanol concentration measurement program according to a ninth specific example. FIG. 17 is a flowchart of a procedure for measuring methanol concentration according to the tenth specific example. FIG. 18 is a block diagram of a direct modification fuel cell system. [Illustration of representative symbols in the figure] 1 Fuel cell 2 Air pump 3 Methanol / water-like solution container 4 Methanol / water pump 5 Methanol measuring device 5 a Methanol measuring device 5b Methanol measuring device 6 Drain pipe 7 Pipe fitting 8 Pipe fitting, air chamber 9 chamber 9A separation wall 10 fins 11 air electrode 87698 -29- 200415816 1 2 fuel electrode 1 3 digital, solid polyelectrolyte film 1 4 air bubble 'carbon dioxide 20 control circuit 2 1 drive circuit 22 output control circuit 23 central processing unit 24 Efficiency comparison Figure 25 Temperature gauge 3 0 Measuring device 3 1 · Concentration measuring device 3 2 Temperature measuring device 33 Fixing member 34 Interface 40 Normal circulation path 41 Branch 5 1 Vibration absorbing joint 52 Vibration absorbing joint 60 Pipe fitting 61 Liquid 63 filter 71 methanol container 72 methanol pump 73 gas-liquid separator 74 temperature measuring device -30- 87698