200832500 九、發明說明： 【發明所屬之技術領域】 本發明是關於固態氧化燃料電池(s〇FC)金屬雙極 (metalllclnterconnects)之性能改良，尤其是一種利用 ，，複合塗層作為金屬雙極板的保護，使金屬雙^ ^ 南溫氧化性提升’並長時間維持原有的金屬高導電性。几 【先前技術】 近年來固態氧化燃料電池的雙極板元件，改採用價 低廉且易加工的耐高溫合金，此類合金材料通常都含有cl和 A1的添加’使表面形成緻密的Cr2〇3與Aha保護合金。雖= 此類的氧化皮膜可提升金屬雙極板抗高溫氧化性，並雷 阻率都相當局’且隨在高溫操作溫度愈長氧化皮臈厚产命 厚導致金屬雙極板的電阻大幅度上升，將阻礙_氧^: 料電池的電流傳送，進而使其發電效率下降。 本人先别研究將鈣鈦礦（per〇vskite)結構氧化物 taKxSrxMn03披覆在金屬雙極板表面，隔絕合金底材的周圍氣 氛，減少氧對合金底材的人侵，可以減緩合金的高溫氧化^ 但是Lai_xSrxMn〇3在高溫中會分解成其他氧化物，分解的氧 化物其電阻較高，故在降低電阻的技術課題方面有改善空間。 【發明内容】 本啦明目的在改善金屬雙極板表面之導電率，使披覆在 ^屬雙極板表面之鈣鈦礦結構氧化物Lai_xSrxMn〇3的導^率 提升’避免La^SrxMnO3保護層因在燒結過程中，發生分解 成其他高電阻的氧化物，並藉由增加電洞的形成，以增加金 5 200832500 屬雙極板表面之導電率。 本發明之保護塗層結構主要是在金屬雙極板及 LakS^MnC^ (以下簡稱LSM〇)高溫氧化保護層間，於LSM〇 燒結刚，予金屬鍍層或塗層，藉由金屬添加㈣整體導電 性。所選擇的金屬鍍層或塗層與耐高溫合金及lsm〇熱膨服 係數的差異不可太大，範圍約lOxlOVc〜20xl〇-Vc，以避 免燒結過程中保護塗層破裂。 本發明之保護塗層製造方法主要的步驟··提供金屬雙極 板、披覆導電金屬於金屬雙極板、塗覆LSM〇漿料於導電鍍 層表面、烘乾及去除結合劑、燒結，以獲得金屬和lsm〇之 複合塗層。 【實施方式】 實施例1 請參閱『第1 II』所示，係本發明於金屬或合金基材上賤 鑛或層’再塗覆La〇7Sl^MnC)3陶雜護層之製 作流程圖。本發明之實施例賴金屬層方式並未受限制，可用 各式的賤鑛機及塗覆方式，只要膜厚控制在0.5 μιη〜6〇 μιη即 可。而LSMO粉末製作方式也林受到制限制，也是只要 製備出來的粉末粒徑約在丨μιη即可。 本么月之孟屬雙極板是採用而才高溫合金，可為鎳美人☆ 鉻基合金或鐵基不錄鋼。本實施例使用的金屬雙極板商 用430不_⑼下_侧s)及測雙相不顯（以下^稱 6 200832500 2205DSS)，此金屬雙極板與鍍層間熱膨脹係數(Thermal Expansion Coefficient，TEC)應能匹配。耐高溫合金與金屬鑛層 及LSMO熱膨脹係數的差異不可太大，範圍約i〇xi〇·6 /〇c〜 20xKT6 /QC，如此將可避免燒結過程，金屬鑛層及LSM〇保護 塗層間的破裂。本實施例使用的合金材料成分與熱膨脹係數如 表1所示。 表1本實施例使用的材料與熱膨脹係數與合金成分(加〇/0) 材料 Μη Ni Cr Mo Fe TEC (xlO'6/°C) 30°C 〜1200°C 2205DSS 1.46 5.20 22.73 2.83 Bal. 18.05 430SS 0.48 - 15.97 Bal. 15.57 Ag - - 19.70 Cu 16.50 LSMO 12.26 在LSMO與金屬雙極板底材間的金屬預鑛層，是在43〇ss 與2205DSS表面濺鍍銀層（以下各簡稱為43〇-Ag⑸及 2205-Ag(S))。採用脈衝直流磁控濺鍍系統的直流電源供應器 與脈衝產生器(SPIK 2000A，Shen Chang Electric Co.，Taiwan) 串連，以供應1個3吋的銀靶(純度為99.99%)。金屬雙極板基材 於濺鍍過程中承受-100 V之脈衝直流偏壓，偏壓脈衝產生器型 7 200832500 號為Sparc-le V (Advanced Energies Industries，USA)。本實施例 之實施步驟分別如下所示·· 1·首先將硏磨拋光完成的430SS或2205DSS放置於酒精，用 超音波清洗機進行3分鐘清洗，以除去表面之氧化鋁拋光粉 與污物。 2·將430SS或2205DSS擺放置於試片基座上，並開始調整試 片位置。確認無誤之後將試片固定置於基座，關上真空腔門 抽真空，至背景壓力真空度達6xi〇-6torr。 3·達到月景壓力真空度後，開始通入氬氣並進行表面钮刻以清 潔試片表面(試片基材偏壓-500 V，氬氣流量20 seem，蝕刻 時間10分鐘）。 4·蝕刻結束後，開啟直流電源供應器開關，使其產生電漿並且 等待電漿狀態穩定約5分鐘過後，開始在試片表面上濺鍍鍍 上一層純銀薄膜。工作壓力為3·〇χ1(Γ3 t〇rr，靶材與試片之 脈衝頻率設定分別為2〇〇 w與2〇 mz，濺鍍時間為如及 50分鐘。 5·濺鍍時間結束後，關閉乾材電源供應器、試片基材偏壓與氬 虱’持續抽真空使試片置於真空腔内緩冷至室溫。 6·達至室溫後，取$ 430_Ag⑸或22〇5_Ag⑸。以咖量測 銀薄膜厚度，依濺鑛時間，測得銀薄膜厚度分別為2 _及 5 μηι ° 8 200832500 應〇粉末制多種物財混合，製作出具倾礦 (Per〇VSkite)結構的LSM〇粉末，製備流程請參閱『第2圖』所 示，所使用的氧化物粉末如表2所示，為Μ、SrC〇3、論〇2。 為了不讓La2〇3氧化驗末轴缝的影響，導致化學性質改 變或是體積重量的變化，在㈣使用前必須把u2o3粉末進行 550 烘乾5小時。決定好欲配製之總重，依計量算出各個氧 化物粉末所需要的重量’利用電子微量天平將氧化物粉末分別 秤重祥重好的氧化物粉末置入球磨筒，同時置入ι/2瓶高的 氧化錯球與溶劑(本實施例使用的溶劑為無水酒精），其中溶劑 應覆蓋過氧化錯球以及氧化物粉末。最後將密封好的球磨筒固 定於行星式的球磨機，進行24小時的濕球磨。濕球磨最主要的 目的是在於可均勻地混合所有的氧化物粉末，減少粉團的形 成。濕球磨完成讀，過濾出氧化鍅球和含有粉末的液體，再 將含有粉末的液體置入90 〇C烘箱内烘烤，讓多餘的溶劑完全 蒸發’取得乾燥的粉末。乾燥後的粉末利用400 mesh的篩網過 篩，使粉末的顆粒大小均勻。過篩之後的粉末進行11〇〇 、 3.5小時的煆燒(Caldnati〇n)處理。煆燒的主要目的有三：⑴去 除粉末内的碳酸物、水份、酯類等碳氳化合物或任何受熱不穩 疋的4貝，（2)藉著熱化學反應達到氧化物形成最終的固溶 體，得到結晶相；（3)經過煆燒反應後，可減少在燒結時體積 的收縮。為了確定得到所需之粒徑與預結晶相之粉末，必須將 200832500 3:=:=:::= 表2 粉末名稱 L&2〇3 SrCO, 之氧化物粉末成分表200832500 IX. Description of the Invention: [Technical Field] The present invention relates to a performance improvement of solid oxide fuel cell (s〇FC) metalllclnterconnects, in particular, a composite coating as a metal bipolar plate The protection of the metal double ^ ^ South temperature oxidation improves 'and maintains the high conductivity of the original metal for a long time. [Prior Art] In recent years, the bipolar plate components of solid-state oxidized fuel cells have been replaced by low-cost and easy-to-process high-temperature resistant alloys. These alloy materials usually contain the addition of cl and A1 to form a dense Cr2〇3 surface. Protected alloy with Aha. Although the oxide film of this type can improve the high temperature oxidation resistance of the metal bipolar plate, and the lightning resistance rate is the same as the pressure of the high temperature operating temperature, the resistance of the metal bipolar plate is greatly increased. Ascending, it will hinder the current transfer of the _ oxygen battery, which will reduce the power generation efficiency. I will not study the per-vskite structure oxide taKxSrxMn03 on the surface of the metal bipolar plate, insulate the surrounding atmosphere of the alloy substrate, reduce the human invasion of the alloy substrate by oxygen, and slow down the high temperature oxidation of the alloy. ^ However, Lai_xSrxMn〇3 decomposes into other oxides at high temperatures, and the decomposed oxide has a high electrical resistance, so there is room for improvement in the technical issue of reducing electrical resistance. SUMMARY OF THE INVENTION The purpose of the present invention is to improve the conductivity of the surface of a metal bipolar plate, so that the conductivity of the perovskite oxide Lai_xSrxMn〇3 coated on the surface of the bipolar plate is improved to avoid La^SrxMnO3 protection. The layer is decomposed into other high-resistance oxides during the sintering process, and by increasing the formation of holes, the conductivity of the surface of the gold plate 200832500 is increased. The protective coating structure of the present invention is mainly between a metal bipolar plate and a high temperature oxidation protective layer of LakS^MnC^ (hereinafter referred to as LSM(R)), which is sintered in LSM, pre-metal plating or coating, and is electrically conductive by metal addition (4). Sex. The difference between the selected metal coating or coating and the high temperature resistant alloy and the thermal expansion coefficient of lsm〇 is not too large, and the range is about lOxlOVc~20xl〇-Vc to avoid cracking of the protective coating during sintering. The main steps of the protective coating manufacturing method of the present invention include: providing a metal bipolar plate, coating a conductive metal on a metal bipolar plate, coating a LSM 〇 slurry on the surface of the conductive plating layer, drying and removing the bonding agent, and sintering, A composite coating of metal and lsm〇 is obtained. [Embodiment] Embodiment 1 Please refer to the "1st II", which is a flow chart of the present invention for preparing a tantalum or layer 'recoating La〇7Sl^MnC)3 ceramic protective layer on a metal or alloy substrate. . The embodiment of the present invention is not limited in the manner of the metal layer, and various types of radon machines and coating methods can be used as long as the film thickness is controlled to be 0.5 μm to 6 μm. The LSMO powder production method is also limited by the system, as long as the prepared powder has a particle size of about 丨μιη. This month's Meng Bipolar plate is a high-temperature alloy that can be used for nickel beauty ☆ chromium-based alloy or iron-based non-recorded steel. The metal bipolar plate commercial 430 used in this embodiment is not _(9) lower _ side s) and the measured double phase is not obvious (hereinafter referred to as 6 200832500 2205DSS), the coefficient of thermal expansion between the metal bipolar plate and the plating layer (Thermal Expansion Coefficient, TEC ) should match. The difference between the high temperature resistant alloy and the metal ore layer and the LSMO thermal expansion coefficient is not too large, and the range is about i〇xi〇·6 /〇c~ 20xKT6 /QC, which will avoid the sintering process, the metal ore layer and the LSM〇 protective coating. The rupture. The alloy material composition and thermal expansion coefficient used in this example are shown in Table 1. Table 1 Materials used in this example and thermal expansion coefficient and alloy composition (twisted / 0) Material Ni Ni Cr Mo Fe TEC (xlO'6 / ° C) 30 ° C ~ 1200 ° C 2205DSS 1.46 5.20 22.73 2.83 Bal. 18.05 430SS 0.48 - 15.97 Bal. 15.57 Ag - - 19.70 Cu 16.50 LSMO 12.26 The metal pre-mineral layer between LSMO and the metal bipolar plate substrate is a silver-plated layer on the surface of 43〇ss and 2205DSS (hereinafter referred to as 43〇) -Ag(5) and 2205-Ag(S)). A DC power supply using a pulsed DC magnetron sputtering system was connected in series with a pulse generator (SPIK 2000A, Shen Chang Electric Co., Taiwan) to supply a 3 吋 silver target (purity of 99.99%). The metal bipolar plate substrate is subjected to a pulsed DC bias of -100 V during sputtering, and the bias pulse generator type 7 200832500 is Sparc-le V (Advanced Energies Industries, USA). The implementation steps of this embodiment are as follows: 1. First, the honed and polished 430SS or 2205DSS is placed in alcohol, and the ultrasonic cleaning machine is used for 3 minutes to remove the surface alumina polishing powder and dirt. 2. Place the 430SS or 2205DSS on the base of the test piece and start adjusting the position of the test piece. After confirming the error, the test piece is fixed on the base, and the vacuum chamber door is closed and vacuumed to a background pressure of 6 xi -6 Torr. 3. After reaching the monthly vacuum pressure, argon gas was introduced and surface stamping was performed to clean the surface of the test piece (sample substrate bias -500 V, argon flow 20 seem, etching time 10 minutes). 4. After the etching is finished, turn on the DC power supply switch to generate plasma and wait for the plasma state to stabilize for about 5 minutes, then start to deposit a layer of pure silver film on the surface of the test piece. The working pressure is 3·〇χ1 (Γ3 t〇rr, the pulse frequency of the target and the test piece is set to 2〇〇w and 2〇mz respectively, and the sputtering time is as long as 50 minutes. 5. After the sputtering time is over, Turn off the dry material power supply, test piece substrate bias and argon argon. Continue to vacuum the test piece in a vacuum chamber and slowly cool to room temperature. 6. After reaching room temperature, take $430_Ag(5) or 22〇5_Ag(5). The thickness of the silver film was measured by the amount of coffee, and the thickness of the silver film was measured by the sputtering time of 2 _ and 5 μηι ° 8 200832500. The LSM of the structure of the per〇VSkite was prepared by mixing various kinds of materials. For the preparation process of the powder, please refer to the “Fig. 2”. The oxide powder used is shown in Table 2. It is Μ, SrC〇3, and 〇2. In order to prevent the influence of La2〇3 oxidation on the axial joint. In order to change the chemical properties or the change in volume and weight, the u2o3 powder must be 550-dried for 5 hours before use. Determine the total weight to be prepared, and calculate the weight required for each oxide powder by measurement. The balance will balance the oxide powder with the oxide powder. The ball mill cylinder is simultaneously filled with ι/2 bottles of high oxidation ball and solvent (the solvent used in this embodiment is anhydrous alcohol), wherein the solvent should cover the peroxide ball and the oxide powder. Finally, the sealed ball mill barrel is fixed. For a 24-hour wet ball mill in a planetary ball mill, the main purpose of the wet ball mill is to uniformly mix all the oxide powders to reduce the formation of the powder. The wet ball mill finishes reading, filtering out the cerium oxide balls and containing the powder. The liquid, and then the liquid containing the powder is placed in a 90 〇C oven for baking, and the excess solvent is completely evaporated to obtain a dry powder. The dried powder is sieved through a 400 mesh sieve to make the powder have a uniform particle size. The sieved powder is subjected to 11 〇〇, 3.5 hours of calcination (Caldnati〇n) treatment. The main purpose of simmering is three: (1) removal of carbonate, water, esters and other carbon ruthenium compounds in the powder or any heat Unstable 4 b, (2) by thermochemical reaction to achieve the final solid solution of oxide to obtain a crystalline phase; (3) after calcination, can reduce the volume during sintering . To determine the shrinkage to obtain a powder of the desired particle size and phase of the pre-crystallization must be 2008325003: =: = = 2 ::: powder Name Table L & 2〇3 of SrCO, the oxide powder composition table
MnO^ 規格/成分 -———— 200 mesh / 99.9% 100 mesh / 99.5% ---———_ 200 mesh / 99.9% 製造商 Cerac，U.S.A·MnO^ Specifications/Ingredients -———— 200 mesh / 99.9% 100 mesh / 99.5% -----_ 200 mesh / 99.9% Manufacturer Cerac,U.S.A·
Cerac，U.SA· ---- Cerac, U.S.A. 本實施例之LSMO漿料調配程序如下：將過筛後的 LSMO粉末依照所要調配的總量，計算所需要的粉末、溶劑 與結合劑的量，其重量比為1G : 4 : G 2(LSM⑽末：松油醇： 乙基纖維素），先行將松油醇與乙基纖維素充分攪拌均勻後， 再倒入LSMO粉末進行混合，其後倒入三滾筒混料機中，依 序使用二種不同的滾輪間隙去除凝團。各階段重複6次，膠 體完成放置於密封罐，並於低溫冷藏備用。Cerac, U.SA·- Cerac, USA The LSMO slurry preparation procedure of this example is as follows: Calculate the amount of powder, solvent and binder required for the LSMO powder after screening according to the total amount to be formulated. The weight ratio is 1G : 4 : G 2 (LSM (10) end: terpineol: ethyl cellulose), first stir the terpineol and ethyl cellulose thoroughly, then pour into LSMO powder for mixing, then Pour into the three-roller mixer and use two different roller gaps to remove the agglomerates. The stages were repeated 6 times, and the gel was placed in a sealed canister and refrigerated at low temperature for use.
LSMO漿料的塗覆作業為··將LSMO漿料塗覆於 430-Ag⑸與 2205-Ag(S)表面(以下各簡稱為 43〇-Ag(S)-LSMO 和2205_Ag(S)-LSMO)。本實施例使用網印技術來塗覆lsmo 裝料，為利於控制LSMO之膜厚於10〜80 μηι之間，網印使 200832500 用60 mesh的網布塗佈3〇 μπι感光乳劑的尼龍網版，並將網 版挾持於網印台上。利用平刮刀將LSM〇漿料網印於 430-Ag(S)與2205-Ag(S)表面，再置入13〇 〇c烤箱烘烤使漿料 溶劑揮發後，將試片置於高溫管型氣氛爐燒結，先進行抽真 空，將管型爐中的空氣抽出，再通入氮氣。第一階段先將溫 度升到500 °C持溫1小時，使膠體中的溶劑完全揮發，再將 溫度升溫至1100 °C持溫1.5小時將LSMO完整地燒結。升 降溫速率皆為100 °C/hr，冷卻至室溫後即完成燒結。 430_Ag(S)_LSMO 與 2205_Ag(S)-LSMO 燒結完後的橫截 面形貌各請參閱『第3圖、第4圖』。如圖所見，層η與層 21在1100 °C燒結1.5小時後，其厚度都約4〇 μηι。經EDS 與XRD分析，層11仍維持鈣鈦礦結構，而層21主要有鈣鈦 礦結構並發現部分的銀和(Cr，Mn)304尖晶石相氧化物。在層 12及層22經由XRD分析，皆為銀、〇2〇3和(Cr,Mn)304尖 晶石相氧化物所組成。因21層在燒結期間已有銀及氧化物散 佈於21層，導致LSMO有了較多空隙與孔洞，使得22〇5-Ag(S) 氧化皮膜較厚於430-Ag(S)氧化皮膜並呈現較不規則狀。 為進行 430_Ag(S)-LSMO 與 2205-Ag(S)-LSMO 於空氣氣 氛之咼溫電阻量測，本實施例於500 〇C〜800 °C間每隔50 °C 量測430_Ag(S)-LSMO及2205-Ag(S)-LSMO於高溫氧化狀態 之電阻。量測結果請分別參閱『第5圖、第6圖』。橫軸為量 200832500 測的溫度，縱軸為試片截面積的電阻改變量(μ·)。顯示曲 線34、42、43(具Ag及LSM〇複合_相較於曲線⑽(具 LSMO塗層），於高溫時有較高的導電率，當溫度低於霞 時’曲線33與轉34電崎差財大；但當溫度高於霞 後’曲線34的電阻值有大幅下降。其原因依氧化物晶體缺陷 理論’當η型或p型氧化物半導體參雜不同價數的金屬陽離 子時，會因為所參雜的金屬陽離子價數的高低而產生不同的 導電率和氧化速率。若她_ A㈣人⑽3氧化層時， 可增加電洞濃度，使⑽3氧化層增加了由電洞所貢獻的導 電度，再者’ (Mn，Cr)3〇4導電率高於&2〇3，故參雜Α§+後的 試片能使導電率提升；此外，対魏的銀，於高溫中以金 屬狀態存在，财散布於高電阻之氧化層内，形成電子的通 路，降低整體的電阻。 實施例2 "本實施讎用侧S作為金屬雙極板材料，金屬預鑛層的 施作是在43GSS表面先麟-層銅雜上__層銀，其後塗覆 、命一吨保護層（以下簡稱430_CuAg⑻_LSM〇)進行高溫 燒結。在本實施例t，LSM0粉末製作方法、以湯聚料調配、 LSMO塗佈方法、燒結方式及高溫電阻量測皆與實施例i相同。 鍍銅目的是要改善銀與430SS間的潤濕附著性，銅的熱膨 12 200832500 脹係數’如表1所示。濺鍍銅銀是採用脈衝直流磁控濺鍍系統 的直流電源供應器與脈衝產生器（SHK 2000A，Shen ChangThe coating operation of the LSMO slurry is to apply the LSMO slurry to the surface of 430-Ag(5) and 2205-Ag(S) (hereinafter referred to as 43〇-Ag(S)-LSMO and 2205_Ag(S)-LSMO) . This embodiment uses a screen printing technique to coat the lsmo charge, in order to facilitate control of the LSMO film thickness between 10 and 80 μηι, screen printing to make 200832500 with a 60 mesh mesh cloth coated with 3 〇 μπι emulsion emulsion nylon screen And keep the screen on the screen printing station. The LSM crucible slurry was screen printed on the surface of 430-Ag(S) and 2205-Ag(S) by a flat scraper, and then placed in a 13 °c oven to bake the solvent of the slurry, and then the test piece was placed in a high temperature tube. The atmosphere furnace is sintered, first evacuated, and the air in the tubular furnace is withdrawn, and then nitrogen gas is introduced. In the first stage, the temperature was raised to 500 ° C for 1 hour, the solvent in the colloid was completely volatilized, and the temperature was raised to 1100 ° C for 1.5 hours to completely sinter the LSMO. The rate of rise and fall is 100 °C / hr, and sintering is completed after cooling to room temperature. For the cross-sectional shapes of 430_Ag(S)_LSMO and 2205_Ag(S)-LSMO after sintering, please refer to "Fig. 3, Fig. 4". As can be seen, the layer η and the layer 21 were sintered at 1100 ° C for 1.5 hours and had a thickness of about 4 μm. After EDS and XRD analysis, layer 11 still maintained the perovskite structure, while layer 21 mainly had a perovskite structure and found part of the silver and (Cr, Mn) 304 spinel phase oxide. The layers 12 and 22 were analyzed by XRD and were composed of silver, 〇2〇3 and (Cr, Mn) 304 spinel phase oxides. Since the 21 layers have silver and oxide dispersed in the 21 layer during sintering, the LSMO has more voids and pores, making the 22〇5-Ag(S) oxide film thicker than the 430-Ag(S) oxide film. Presenting a more irregular shape. For the measurement of the temperature resistance of 430_Ag(S)-LSMO and 2205-Ag(S)-LSMO in air atmosphere, this example measures 430_Ag(S) at 50 °C between 500 °C and 800 °C. - LSMO and 2205-Ag(S)-LSMO resistance in high temperature oxidation state. Please refer to "Figure 5, Figure 6" for the measurement results. The horizontal axis is the measured temperature of 200832500, and the vertical axis is the resistance change amount (μ·) of the cross-sectional area of the test piece. Display curves 34, 42, 43 (with Ag and LSM 〇 composite _ compared to curve (10) (with LSMO coating), have higher conductivity at high temperatures, when the temperature is lower than Xia 'curve 33 and turn 34 Sakisaki is rich; but when the temperature is higher than Xia', the resistance value of curve 34 is greatly reduced. The reason is based on oxide crystal defect theory. When η-type or p-type oxide semiconductors are mixed with metal cations of different valences, Different conductivity and oxidation rate will occur due to the valence of the metal cations involved. If she _ A (four) human (10) 3 oxide layer, the hole concentration can be increased, so that the (10)3 oxide layer is increased by the hole. Conductivity, and the conductivity of '(Mn,Cr)3〇4 is higher than &2〇3, so the test piece after 参++ can increase the conductivity; in addition, the silver of Wei Wei is in high temperature. In the state of metal, the money is dispersed in the high-resistance oxide layer to form an electron path, which reduces the overall resistance. Example 2 "This embodiment uses the side S as a metal bipolar plate material, and the metal pre-mineral layer is applied. It is on the surface of the 43GSS first lin-layer copper miscellaneous __ layer silver, after which it is coated and ordered one ton. The sheath (hereinafter referred to as 430_CuAg(8)_LSM〇) is subjected to high-temperature sintering. In the present embodiment t, the LSM0 powder preparation method, the soup aggregate preparation, the LSMO coating method, the sintering method, and the high-temperature resistance measurement are the same as in the example i. The purpose is to improve the wet adhesion between silver and 430SS. The thermal expansion of copper 12200832500 expansion coefficient is shown in Table 1. Sputtered copper silver is a DC power supply and pulse generation using pulsed DC magnetron sputtering system. (SHK 2000A, Shen Chang
Electric Co·，Taiwan)串連，以供應1個3吋的銀靶(純度為99.99%) 與1個3吋的銅靶(純度為99.99%)。基材(金屬雙極板)於濺鍍過 程中承受-100 V之脈衝直流偏壓，偏壓脈衝產生器型號為 Sparc-leV (Advanced Energies Industries, USA)，本實施例金屬 預鍍層之實施步驟分別如下所示： 1·首先將硏磨拋光完成的430SS放置於酒精，用超音波清洗機 進行3分鐘清洗，以除去表面之氧化鋁抛光粉與污物。 2·將430SS擺放置於試片基座上，並開始調整試片位置。確認 無誤之後將試片固定置於基座，關上真空腔門抽真空，至背 景壓力真空度達6xl〇_6 torr 〇 3·達到月景壓力真空度後’開始通入氬氣並進行表面钱刻以清 潔試片表面(試片基材偏壓-500 V，氬氣流量20 sccm，蝕刻 時間10分鐘）。 4·蝕刻結束後，開啟直流電源供應器開關，使其產生電漿並且 等待電漿狀態穩定約5分鐘過後，開始在試片表面上濺鍍鍍 上層純銅薄膜。工作壓力為3·〇χ1〇3 torr，革巴材與試片之 脈衝頻率設定分別為200 W與20 kHz，濺鑛時間為2〇分 鐘。濺鍍銅之後，將試片轉至銀靶前，開始濺鍍銀薄膜，工 作壓力為3·0χ1(Γ3 torr，靶材與基材之脈衝頻率設定分別為 13 200832500 2〇〇 W與20 kHz，濺鍍時間為2〇分鐘。 戈錢日可間結束後，關閉靶材電源供應器、試片基材偏壓與氬 軋持續抽真空使試片置於真空腔内緩冷至室溫。 達至至溫後，取出試片，以SEM量測銅與銀薄膜之厚度， 分別為鋼2μιη、銀2·5μιη。 濺鍍銅、銀後，塗覆LSMO漿料，再置於1100 %氮氣氣 氛燒結1.5小時。430-CuAg(S)-LSMO燒結完後之橫截面形貌 "月i閱第7圖』，顯示各鍍層與基材間均有很好的附著性。 層51的厚度約40 μιη，經EDS與XRD分析，LSMO已有少 部份分解成其他氧化物。層52經EDS與XRD分析，顯示此 層主要為銅、銀及(Mn，Cr)304，並包含少許的Cr2〇3、LaCu〇4 與CuCr〇2。顯示銅在燒結的過程中發生了微量的氧化，並有 少i的氧化銅與LSMO中的La反應形成LaCu04散佈於氧化 層中。由於氧化層中連續性的(Mn，Cr)304與Cr203仍具有保護 性’使得合金基材在高溫燒結過程中不致產生嚴重的氧化。 430_CuAg(S)-LSMO金屬雙極板高溫電阻量測結果請參閱 『第5圖』之曲線32。由於銅在1100 °C的燒結過程中發生氧 化並與LSMO反應，形成LaCu〇4與CuCr02，此高電阻氧化 層的產生，增加了整體的電阻，導致曲線32的電阻在各階段 溫度之量測皆高於曲線34(僅先預鍍銀的金屬雙極板），但仍比 沒有塗層者(曲線31)具有較低的電阻。顯示由於銀的存在，可 200832500 降低整體的電阻，但若再纖罐層，可增加麵金屬層、 LSMO與合金底材的附著性，但對導電性則有負面的效果。 綜合而言，添加銅鍍層對於整體的影響：（1)增加預鍍金 屬層、LSMO與合金底材的附著性；（2)銅於11〇〇 %燒結過 程中會產生氧化而提高整體的電阻；（3)氧化銅會與lsm〇中 的La產生反應，促使LSM〇產生分解，而提高整體的電阻。 實施例3 本實施例採用2205DSS作為金屬雙極板材料，金屬預塗 層疋於2205DSS表面網印銀膠與銀把膠 (95wt%Ag-5wt%Pd)。其中，銀膠與銀鈀膠為一般市售之導電 膠體。而後再塗覆La^Si^MnO3保護層（以下簡稱 2205-Ag(G)-LSMO 與 2205-AgPd(G)-LSMO)接著進行高溫燒 結。在本實施例，LSMO粉末製作方法、LSM〇漿料調配^ LSMO塗佈方法、高溫電阻量測皆與實施例丨相同。網印銀 膠與銀鈀膠之過程及燒結參數的改變，依序說明如下·· 1·金屬底材備製··將硏磨拋光完成的2205DSS試片放置於酒 精，用超音波清洗機進行3分鐘清洗，以除去表面之氧化 銘拋光粉與污物後，烘乾備用。 2·網印銀膠··本實施例使用網印技術來塗覆銀膠，以利於將 銀膜之厚度控制於〇·5〜60μηι之間。網印使用6〇的 15 200832500 網布塗佈30 μιη感光乳劑的尼龍網版，並將網版挾持於網 印台上。使用刮勺將銀膠酌量置於網印圖案左側，利用平 刮刀將銀膠網印於2205DSS表面後，置入130 °C烤箱烘烤 使漿料溶劑揮發。 3·網印LSMO :將已塗覆完銀膠的2205DSS試片置於網印台 上’再一次於2205-Ag(G)表面網印塗覆LSMO漿料，置入 130 °C之烤箱烘烤使漿料溶劑揮發。 4· LSMO燒結：將22〇5_Ag(G)_LSM〇放入管型氣氛爐燒結。 先進行抽真空，將管型爐中的空氣抽出，再通入氮氣。第 一階段先將溫度升到4〇〇。(：，持溫1小時，使膠體中的溶 劑完全揮發。再將溫度升溫至1100 持溫1.5小時。升降 溫速率皆為5 °C/min冷卻至室溫即完成燒結。 本實施例之網印銀鈀膠與2205_AgPd(G>LSM〇之燒結過 权，如上述網印銀膠手法一樣，在此不再重覆贅述。 2205-Ag(G)-LSMO燒結完後之橫截面形貌請參閱『第8 圖』。2205_Ag(G)-LSMO經由EDS與XRD分析，層61主要 有鈣鈦礦結構及發現部分的銀和(Cr，M_4尖晶石相氧化 物。層62為銀、〇^〇3和(Cr，Mn)3〇4尖晶石相氧化物所組成， 且銀呈現球團綠，絲紅有部分碰錢留於遍〇層 中。其中’銀呈球團樣貌原因分析為··⑴銀層經u〇〇〇c高 溫燒結已超過銀的賴968。(：，因而發生銀之_聚集和揮 16 200832500 發，使銀層的厚度不均勻；⑺銀膠採用網印方式塗覆試片， 附者性及均雜都不如賴方式，且轉體也因溶劑於高溫 揮發，使得銀層*再緻密均勻。22〇5_Ag(G>LSM〇電阻量測 結果請參閱『第6圖』之曲線42。雖然銀在燒結過程中=約 有50〇/〇揮發或殘留於LSM〇層中，但其從電阻量測值，顯示 其電阻值皆低於曲線41(未施予中間銀塗層之試樣）。其原^ 如上述所提之氧化物晶體缺陷理論之外，也因層61已有銀及 具導電性(Mn，Cr)3〇4尖晶石相氧化物的存在，使得試片導電 性大大的提升。亦即’銀的職層不論是藉由频或網印= 式，皆能提高整體試片的導電性。 22〇5_AgPd(G)_LSMO燒結完後之橫截面形貌請參閱『第 9圖』，各鏟層_紐良好且銀解財槪而完整保留。 其原因是攀)在高溫中能牽制銀，抑制銀的液化及揮發。 攸上述貫侧1〜3料歸，在金屬雙極板及lsm〇高溫 氧化保護層間’於LSM0燒結前施予含銀之鑛層或塗層，不 管銀層的施作是藉由濺鑛方式或網印方式，均顯示出銀的添 加有助於整體導電性的提升。 200832500 【圖式簡單說明】 第1圖為本發明金屬和LSMO複合塗層製造方法之流程圖。 第2圖為本發明LSMO粉末製作流程圖。 第3圖為本發明430-Ag(S)-LSMO燒結後之SEM橫截面圖。 第4圖為本發明2205-Ag(S)-LSMO燒結後之SEM橫截面圖。 第5圖為430-Ag(S)-LSMO於高溫氧化狀態之電阻。 第6圖為2205-Ag(S)-LSMO於高溫氧化狀態之電阻。 第7圖為本發明430-CuAg(S)-LSMO燒結後之SEM橫截面圖。 第8圖為本發明2205-Ag(G)-LSMO燒結後之SEM橫截面圖。 第9圖為本發明2205-AgPd(G)_LSMO燒結後之SEM橫截面圖。 【主要元件符號說明】 11、 2卜 51、61、71 LSMO 層； 12、 22、52、62、72中間金屬層； 13、 23、53、63、73 金屬基材； 31 430SS ； 32 430SS_CuAg(S)-LSMO 之試樣； 33 430SS-LSMO(未施予中間金屬塗層)之試樣； 34 430SS-Ag(S)_LSMO 之試樣； 41 2205-LSMO(未施予中間金屬塗層)之試樣； 18 200832500 42 2205-Ag(G)_LSMO 之試樣； 43 2205-Ag(S)-LSMO 之試樣。Electric Co·, Taiwan) is connected in series to supply a 3-inch silver target (purity of 99.99%) and a 3-inch copper target (purity of 99.99%). The substrate (metal bipolar plate) is subjected to a pulsed DC bias of -100 V during the sputtering process, and the bias pulse generator model is Sparc-leV (Advanced Energies Industries, USA), the implementation steps of the metal pre-plating layer of this embodiment The results are as follows: 1. First, honing and polishing the 430SS in alcohol, and cleaning with an ultrasonic cleaner for 3 minutes to remove the surface of the alumina polishing powder and dirt. 2. Place the 430SS pendulum on the test strip base and begin to adjust the test strip position. After confirming the error, fix the test piece on the base, close the vacuum chamber door and vacuum it to the background pressure vacuum level up to 6xl〇_6 torr 〇3·After reaching the monthly pressure vacuum degree, 'start to argon gas and carry out surface money The surface of the test piece was cleaned (the test piece substrate biased -500 V, the argon flow rate was 20 sccm, and the etching time was 10 minutes). 4. After the etching is finished, turn on the DC power supply switch to generate plasma and wait for the plasma state to stabilize for about 5 minutes, then start sputtering the upper layer of pure copper film on the surface of the test piece. The working pressure is 3·〇χ1〇3 torr, and the pulse frequency of the leather material and the test piece are set to 200 W and 20 kHz, respectively, and the sputtering time is 2 〇 minutes. After the copper is sputtered, the test piece is transferred to the silver target, and the silver film is sputtered. The working pressure is 3·0χ1 (Γ3 torr, the pulse frequency setting of the target and the substrate is 13 200832500 2〇〇W and 20 kHz respectively). The sputtering time is 2 minutes. After the end of the money, the target power supply is turned off, the test piece substrate bias and the argon rolling are continuously evacuated, and the test piece is placed in a vacuum chamber and slowly cooled to room temperature. After reaching the temperature, the test piece was taken out and the thickness of the copper and silver films was measured by SEM, which were respectively steel 2 μm and silver 2·5 μm. After sputtering of copper and silver, the LSMO slurry was applied and then placed at 1100% nitrogen. The atmosphere was sintered for 1.5 hours. The cross-sectional morphology of the 430-CuAg(S)-LSMO after sintering was shown in Figure 7 and showed good adhesion between the coating and the substrate. Approximately 40 μm, analyzed by EDS and XRD, LSMO has been partially decomposed into other oxides. Layer 52 was analyzed by EDS and XRD, which showed that the layer was mainly copper, silver and (Mn, Cr) 304, and contained a little Cr2〇3, LaCu〇4 and CuCr〇2. It shows that a small amount of oxidation occurs during the sintering of copper, and there are less copper oxide and LSMO. The La reaction forms LaCu04 dispersed in the oxide layer. Since the continuous (Mn, Cr) 304 and Cr203 in the oxide layer are still protective, the alloy substrate does not cause severe oxidation during high-temperature sintering. 430_CuAg(S)- For the high-temperature resistance measurement results of LSMO metal bipolar plates, please refer to the curve 32 of Figure 5. Since the copper is oxidized during the sintering process at 1100 °C and reacts with LSMO to form LaCu〇4 and CuCr02, the high-resistance oxide layer The generation increases the overall resistance, resulting in the resistance of curve 32 being measured at various stages higher than curve 34 (only pre-plated metal bipolar plates), but still better than no coating (curve 31). It has a low resistance. It shows that due to the presence of silver, 200832500 can reduce the overall resistance. However, if the tank layer is re-coated, the adhesion of the surface metal layer, LSMO and alloy substrate can be increased, but the conductivity is negative. In general, the effect of adding copper plating on the whole: (1) increasing the adhesion of the pre-plated metal layer, LSMO and the alloy substrate; (2) the copper will generate oxidation during the 11% sintering process to improve the overall Resistance; (3) oxidation Copper reacts with La in lsm〇 to promote decomposition of LSM(R) and increase overall electrical resistance.Example 3 This example uses 2205DSS as metal bipolar plate material, metal pre-coating on 2205DSS surface screen printing silver paste Glue (95wt% Ag-5wt% Pd) with silver paste, wherein silver paste and silver palladium paste are generally commercially available conductive colloids, and then coated with La^Si^MnO3 protective layer (hereinafter referred to as 2205-Ag(G) - LSMO and 2205-AgPd(G)-LSMO) followed by high temperature sintering. In the present embodiment, the LSMO powder production method, the LSM slurry preparation method, the LSMO coating method, and the high temperature resistance measurement are the same as in the embodiment. The process of screen printing silver paste and silver palladium glue and the change of sintering parameters are as follows: 1. Metal substrate preparation · The 2205DSS test piece finished by honing and polishing is placed in alcohol, and the ultrasonic cleaning machine is used. After 3 minutes of cleaning, remove the surface of the oxidized polished powder and dirt, and then dry for use. 2. Screen printing silver glue · This embodiment uses a screen printing technique to coat the silver paste to facilitate controlling the thickness of the silver film between 〇·5 and 60 μm. The screen printing was applied to a nylon screen of 30 μιη sensitizing emulsion using a 6 〇 15 200832500 mesh cloth, and the screen was held on the screen printing table. The silver paste was placed on the left side of the screen printing pattern by using a spatula. The silver plastic mesh was printed on the surface of the 2205DSS by a flat blade, and then placed in an oven at 130 ° C to evaporate the slurry solvent. 3. Screen printing LSMO: Place the 2205DSS test piece coated with silver glue on the screen printing table. Once again, apply LSMO slurry on 2205-Ag(G) surface and place it in the oven at 130 °C. The slurry solvent is volatilized. 4. LSMO sintering: 22〇5_Ag(G)_LSM〇 was placed in a tubular atmosphere furnace for sintering. Vacuuming is first performed to extract the air in the tubular furnace, and then nitrogen is introduced. In the first stage, the temperature is raised to 4 先. (:, holding the temperature for 1 hour, the solvent in the colloid is completely volatilized. The temperature is raised to 1100 and the temperature is maintained for 1.5 hours. The temperature rise and fall is 5 °C/min, and the temperature is cooled to room temperature to complete the sintering. The printing of silver palladium glue and 2205_AgPd (G> LSM 烧结 sintering right, as the above screen printing silver glue method, will not repeat them here. 2205-Ag (G)-LSMO cross-section after sintering please Refer to Figure 8. 2205_Ag(G)-LSMO is analyzed by EDS and XRD. Layer 61 mainly has perovskite structure and found part of silver and (Cr, M_4 spinel phase oxide. Layer 62 is silver, antimony ^〇3 and (Cr,Mn)3〇4 spinel phase oxides, and silver presents green pellets, and some of the silk reds are left in the ruthenium layer. The analysis is as follows: (1) The silver layer has been super-sintered by u〇〇〇c. It has exceeded the silver 968. (:, so the silver_aggregation and the wave 16200832500 occur, making the thickness of the silver layer uneven; (7) the silver glue adopts the net Printed test strips are not inferior to the method, and the rotating body is also volatilized by the solvent at high temperature, so that the silver layer* is dense and uniform. 22〇5_Ag (G> LSM 〇 resistance measurement results, please refer to curve 42 of Figure 6. Although silver is about 50 〇 / 〇 volatilization during the sintering process or remains in the LSM 〇 layer, but its resistance measurement, It is shown that the resistance value is lower than the curve 41 (the sample without the intermediate silver coating). In addition to the oxide crystal defect theory mentioned above, the layer 61 has silver and is electrically conductive ( The presence of Mn,Cr)3〇4 spinel phase oxide greatly enhances the conductivity of the test piece. That is to say, 'the silver layer can improve the overall test piece by frequency or screen printing. Conductivity. 22〇5_AgPd(G)_LSMO After cross-section, please refer to “Picture 9”. Each shovel layer is good and the silver is well-received. The reason is that it can be climbed at high temperature. The silver is restrained and the liquefaction and volatilization of the silver are inhibited. 攸 The above-mentioned side 1~3 material returns, and the silver-containing ore layer or coating is applied before the sintering of the LSM0 between the metal bipolar plate and the lsm〇 high temperature oxidation protective layer, regardless of the silver. The layer is applied by splashing or screen printing, both of which show that the addition of silver contributes to the overall conductivity. 200832500 [ BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a flow chart of a method for producing a metal and LSMO composite coating of the present invention. Fig. 2 is a flow chart of the LSMO powder production of the present invention. Fig. 3 is a 430-Ag(S)-LSMO sintered according to the present invention. SEM cross-sectional view. Fig. 4 is a SEM cross-sectional view of the 2205-Ag(S)-LSMO sintered according to the present invention. Fig. 5 is a resistance of 430-Ag(S)-LSMO in a high temperature oxidation state. It is the resistance of 2205-Ag(S)-LSMO in a high temperature oxidation state. Fig. 7 is a SEM cross-sectional view of the 430-CuAg(S)-LSMO after sintering of the present invention. Figure 8 is a SEM cross-sectional view of the 2205-Ag(G)-LSMO sintered according to the present invention. Figure 9 is a SEM cross-sectional view of the 2205-AgPd(G)_LSMO sintered according to the present invention. [Main component symbol description] 11, 2, 51, 61, 71 LSMO layer; 12, 22, 52, 62, 72 intermediate metal layer; 13, 23, 53, 63, 73 metal substrate; 31 430SS; 32 430SS_CuAg ( S)-LSMO sample; 33 430SS-LSMO (no intermediate metal coating) sample; 34 430SS-Ag(S)_LSMO sample; 41 2205-LSMO (no intermediate metal coating applied) Samples; 18 200832500 42 2205-Ag(G)_LSMO sample; 43 2205-Ag(S)-LSMO sample.