TWI286579B

TWI286579B - Preparation of polymer composite bipolar plate having improved electric conductivity for fuel cell

Info

Publication number: TWI286579B
Application number: TW093141542A
Authority: TW
Inventors: Chen-Chi Martin Ma; Wei-Jen Chen; Chuan-Yu Yen; Yu-Feng Lin; Shu-Hang Liao
Original assignee: Univ Tsinghua
Priority date: 2004-12-30
Filing date: 2004-12-30
Publication date: 2007-09-11
Also published as: TW200624604A

Abstract

A polymer composite bipolar plate for a polymer electrolyte membrane fuel cell (PEMFC) is prepared as follows: (a) compounding phenolic resin and carbon fillers to form bulk molding compound (BMC) material, the BMC material containing 60 to 80 wt% graphite powder, 1 to 10 wt% carbon fiber; and one ore more conductive carbon fillers selected from: 5 to 30 wt% Ni-planted graphite powder, 2 to 8 wt% Ni-planted carbon fiber and 0.01 to 0.3 wt% carbon nanotubes, based on the weight of the phenolic resin, provided that the sum of the amounts of the carbon fiber and Ni-planted carbon fiber is not greater than 10 wt%; (b) molding the BMC material from step (a) to form a bipolar plates having a desired shape at 80-200 DEG C and 500-4000 psi.

Description

1286579 九、發明說明：發明所屬之技術領域本發明係關於一種燃料電池用的碳填料/高分子複合材料雙極板之製備方法，尤其有關一種以塊狀模塑成型 (BMC)的方式製備燃料電池的導電碳填料/高分子複合材料雙極板的方法。先前技術我國專利公告第399348號揭示一種生產雙極隔板之方法，包含：混合至少一導電子材料，至少一樹脂與至少適合質子交換膜燃料電池使用之親水劑，形成一大致均質之混合物，其包含所述至少一導電子材料，其量依所述混合物重量為於約50%至約95%之範圍，所述至少一樹脂其1依所述混合物重量為至少約5%;及模鑄所述混合物成所要形狀，其於約250°F與約500QF之溫度範圍與約 500PS1與約4〇〇〇psi之壓力範圍，形成雙極板。其中所述至少一樹脂為從由熱硬化樹脂、熱塑性樹脂、及其混合物所組成之群組中選出；所述至少一導電子材料為從由石墨、碳黑、碳纖維、及其混合物所組成之群組中還出。美國專利US6248467揭示一種燃料電池的複合材料雙極板’其中石墨粉末的粒徑主要在8〇網目〜325網目之間，此專利教導當石墨粉末的粒徑大於丨5〇μιη時，在加工時會與樹脂混合不均勻的問題。 WO 00/5 7506揭示一種用於模塑燃料電池的雙極板之 1286579 高導電性模塑組合物，其中所使用的石墨粉末的粒徑範圍主要介於44μηι與150μπι之間，其中大於15〇μπι要少於 10%，小於44μηι亦少於10%。我國專利公告發明第221039號揭示一種燃料電池的複合材料雙極板之製備方法，包含下列步驟：a)捏合石墨粉末與一乙烯酯樹脂，形成一均質之模塑混合物，其中包含60至80重量％的所述石墨粉末以該模塑混合物的重量為基準；b)於80-200〇C之溫度與5〇〇-4〇〇〇psi之壓力下模塑步驟a)的模塑混合物形成一具有想要形狀的雙極板；其中該石墨粉末的粒徑介於1〇-8〇網目。至目前為止，業界仍在持續尋找一種兼具高導電性、優異機械性質及高熱穩定性的燃料電池的雙極板。發明内容本發明的—主要目的在提供-種兼具高導電性、優機械性質及高熱穩定性的燃料電池的雙極板。本發明的另-目的在提供一種兼具高導電性、優異械質及高熱穩定性的燃料電池的雙極板之製備方法。、本發明中採用㈣樹脂與導電碳填料用塊狀模塑成 (BMC)的方法，製備複合材料雙極板，其中料電碳填的合適例子有鍍鎳石墨粉末，硝不反佘未官，及鍍鎳碳纖維本發明可提升複合材料雙極板叉徑叙之導電性，機械性質，並合防火難燃及抗腐蝕性質。 1286579 實施方式本發明揭示一種燃料電池的複合材料雙極板之製備方法包3下列步驟· a)捏合碳填料與一酚醛樹脂，形成一均質之模塑混合物，該模塑混合物包含石墨粉末6〇至8〇重里，碳纖維1至1 〇重量％ ;及選自以下導電碳填料族群的一種或多種：該族群由鍍鎳石墨粉末5至3〇重量％，石厌奈米管0.01至〇·3重量％，及鍍鎳碳纖維2至8重量％所組成，該等重量％以該酚醛樹脂的重量為基準，但該碳纖維及鍍鎳碳纖維的含量總和不大於重量％ ; b)於 80-200°C之溫度與50-4000 psi之壓力下模塑步驟a)的模塑混合物形成一具有想要形狀的雙極板。車父佳的’該石墨粉末為粒徑介於丨〇_8〇網目的石墨粉末’該鍍鎳石墨粉末未鍍鎳前具有介於1〇_8〇網目的粒徑，及該鑛鎳石墨粉末的表面鍍鎳含量為20〜80重量。/。，以未鍍鎳前的重量為基準。較佳的’該碳纖維及鍍鎳碳纖維長度為1-1〇 mm，及纖維束為5〜24 K，其中鍍鎳碳纖維表面鍍鎳含量為10〜30 重量°/。，以未鍍鎳前的重量為基準。較佳的’該奈米碳管為單壁或多壁，其具有碳管直徑為0.7〜50 nm，碳管長度為1〜1〇〇〇 μιη，及碳管比表面積為 40〜300 m2/g。較佳的’於步驟a)之前將一改質劑預先與該酚醛樹脂混合’該改質劑的用量為〇· 1-5重量。/〇，以該酚醛樹脂重量為基準。更佳的，該改質劑為聚環氧乙烷（P〇ly(ethylene 1286579 oxide))、聚乙稀酵（Poly(vinyl alcohol)、聚乙二醇 (Polyethylene glycol)或聚環氧丙烷（Poly propylene oxide)。最佳的，該改質劑為聚環氧乙烧。較佳的，於步驟a)之前將一偶合劑預先與該酚醛樹脂混合，該偶合劑的用量為0 · 1- 5重量％，，以該紛酿樹脂重量為基準，其中該偶合劑之化學式則可以下列表示之 (ROn-Ti-CROm 或（RL-Si-CDm，其中 n&m 為〇至 4 的整數及η及m的和為4;R為C1_C4烷氡基；及1為C1-C6烷基或環烷基。更佳的，該偶合劑為四異丙基鈦酸鹽 (tetra-isopropyl titanate，TPT)。較佳的，該酚醛樹脂為清漆型（Novalac)或是可熔型 (Resol type)酚醛樹脂，且其黏度介於1〇〇〜2〇〇 cps/25<t，及固形份介於50〜70%。於下列的對照例及實施例中使用以下的酚醛樹脂：酚醛樹脂型號：PF-650，台灣長春人造樹脂股份有限公司 (Chang Chun CO.) ’台北市松江路3〇1號七樓。對照例la-Id 石墨粉末的粒徑範圍為大於4〇網目（直徑42〇"m)不超過10%，40網目〜60網目（直徑在42〇"111〜25(^111之間）大約佔40% , 60網目〜80網目（直徑在25〇^ m〜177"瓜之間）大約佔50%。塊狀模塑材料與試片之製備 1·將500的克酚醛脂樹脂以2〇ml的丙酮為溶劑配製成的溶 1286579 液，並加入2(^的ΤΒΤ作為偶合劑，加入2〇克的pE〇為改質劑。 2·將上述溶液利用馬達攪拌器在室溫下的環境下攪拌分鐘。 3·將上述溶液、375克（75重量％，以該紛搭樹脂的重量為基準）的上述石墨粉末及10克（2重量％，以該酚醛樹脂的重置為基準）的碳纖維（長度為i 3 mm;纖維束為1〇〜12 κ)倒入團狀模塑材料（Bulk Molding c〇mp〇und ’簡稱 BMC)的捏合機中利用正轉、反轉使其混合均勻，捏合時間大約為30分鐘。停止捏合動作，將團料取出收集，置於冷凍櫃中存放。 4·熱壓忒片前先取出團料，分成數團，每團重量為1〇〇克的團狀模塑材料。 5·將平板試片模固定在熱壓機之上、下工作台上，預熱模溫設定在165。(：，溫度到達後，將團料置於模具正中央，以3000pSi的壓力壓製試片，15〇〇秒後模子會自行打開，接者將試片取出。重覆上述步驟i至5，但將上述石墨粉末的用量改變為3 25克（65重量％)、4〇〇克（80重量％)及425克（85重量 %) 〇實施例1 a_ 1 d (碳奈米管）重覆對照例1的步驟1至5，但將上述石墨粉末的用量固定為375克（7 5重量％)及進一步於步驟3中加入0.01 1286579 至0·3重量。/〇的碳奈米管，以該酚醛樹脂的重量為基準。所使用之奈米碳管為多壁碳奈米管；2)碳管直捏為2〇 nm ; 3) 碳管長度為1 μηι ; 4)碳管比表面積為1 70 m2/g。實施例2a-2d (鍍鎳石墨粉末）重覆對照例1的步驟1至5，但將上述石墨粉末的用量固定為375克（75重量％)及進一步於步驟3中加入5至 3 0重量％的鍍鎳石墨粉末，以該酚醛樹脂的重量為基準。所使用之鍍鎳石墨粉末在未鍍鎳前具有53網目的粒徑，及鍍鎳石墨粉末表面鍍鎳成分為60重量〇/〇。實施例3a-3d (鍍鎳碳纖維）重覆對照例1的步驟1至5，但將上述石墨粉末的用里固疋為375克（75重量❶/〇)及進一步於步驟3中加入2至8 重量％的鍍鎳碳纖維，以該酚醛樹脂的重量為基準。所使用之鍍鎳碳纖維在未鍍鎳前具有長度為13 mm;纖維束為 12K’及鍵錄碳纖維表面鑛鎳成分為28重量％。電氣性質測試方法：、，四點探針電阻儀所利用的原理為施加電壓和電流於待 ==品表面上，在另一端測量出其通過待測物之電壓值和 w值’利用歐姆定律可得知待測物之體積電阻值p。將四點探針求得的試片的表面電阻，利用式i進而求出體積 1286579 電阻（P ) ’ p = 7* WF (式l)，v為通過試片的電壓值] K >{的電流值’二者之比值即為表面電阻，w為試二之厚度’CF為校正因子。本實施例及對照例中所熱壓的 j片大約為100 mm X 100 mm，厚度為3mm，該試片之CF 扠子因子的數值CF = 4·5,而由式1求出的體積電阻(P), 將體積電阻倒數即為試片之導電率。結果表1為固定樹脂配方，固定碳纖維含量在2重量％，。石墨：量分麟65重量％、75重量％、8〇重量％、85重量 /〇的同分子複合材料雙極板的導電測試值結果。其導電測試值分別為 19S/Cm、24S/Cm、70S/cm、ms/cm。隨石墨添加篁的增加，可知高分子複合材料雙極板以形成極佳的導電通路，導電率也隨之上升。表2為固疋樹脂配方，固定碳纖維含量在2重量％，固疋石墨含量在75重量％。添加並改變碳奈米管的含量，分別為0.01重量％、〇·〇5重量％、〇丨重量％、〇 3重量％的高分子複合材料雙極板的導電測試值結果。其導電測試值分別為 137 S/cm、158 S/cm、169 S/Cm、i81 S/cm。當碳奈米管的添加量達一定比例後，使得導電率大幅提升。表3為固定樹脂配方，固定碳纖維含量在2重量％，固定石墨含量在75重量％。並添加鍍鎳石墨，其含量分別為5重量％、15重量％、2〇重量％、3〇重量％的高分子複合材料雙極板的導電測試值結果。其導電測試值分別為78 11 1286579 :/⑽、116 s/cm、124 s/cm、165 鍍鎳石墨摻混比例 :。5重量。/。時導電率為78 s/cm、未鐘鎳石墨粉末的75重篁％時導電率為24S/em (表1的對照例lb)，兩者導電率相比較之下，可知只需要極少的含量的鑛鎳石墨，即可在複 :材：電雙極板令建立導電通路，亦可降低石墨的含里匕著鍍鎳石墨摻混比例增加，其導電性呈線性提升。表4為固定樹脂配方，固定碳纖維含量在2重量％，疋石墨3里在75重量❶/。。並添加鍍鎳碳纖維，其含量分別為2重量％、4重量％、6重量％、8重量％的高分子複合材料雙極板的導電測試值結果。其導電測試值分別為Μ 〜⑽旦76s/cm、149s/cm、195S/cm。鑛錄碳纖維含量在 4重量％時、導電率在76 S/cm，與石墨粉末75重量％、鍍 2石墨粉末5重量％的導電率相差無幾（表3的實施例2幻。田鍍鎳奴纖維含量在8重量％時、導電率提升至i95 s/cm。隨著鍍鎳碳纖維的增加，其導電率也隨之升高。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for preparing a carbon filler/polymer composite bipolar plate for a fuel cell, and more particularly to a method for preparing a fuel by bulk molding (BMC). A method of conducting a carbonaceous/polymer composite bipolar plate for a battery. Prior Art Chinese Patent Publication No. 399,348 discloses a method for producing a bipolar separator comprising: mixing at least one conductive sub-material, at least one resin and at least a hydrophilic agent suitable for use in a proton exchange membrane fuel cell to form a substantially homogeneous mixture, The at least one conductive sub-material is included in an amount ranging from about 50% to about 95% by weight of the mixture, the at least one resin of which is at least about 5% by weight of the mixture; and die-casting The mixture is in a desired shape which forms a bipolar plate at a temperature ranging from about 250 °F to about 500 QF and a pressure range of about 500 PS1 and about 4 psi. Wherein the at least one resin is selected from the group consisting of a thermosetting resin, a thermoplastic resin, and a mixture thereof; the at least one conductive sub-material is composed of graphite, carbon black, carbon fiber, and a mixture thereof Also in the group. U.S. Patent No. 6,248,467 discloses a composite bipolar plate of a fuel cell in which the particle size of the graphite powder is mainly between 8 〇 mesh and 325 mesh. This patent teaches that when the particle size of the graphite powder is larger than 丨5 〇 μιη, during processing The problem of uneven mixing with the resin. WO 00/5 7506 discloses a 1286579 highly conductive molding composition for a bipolar plate for molding a fuel cell, wherein the graphite powder used has a particle size range of mainly between 44 μm and 150 μm, wherein more than 15 〇 Μπι is less than 10%, less than 44μηι is also less than 10%. China Patent Publication No. 221039 discloses a method for preparing a composite bipolar plate for a fuel cell, comprising the steps of: a) kneading a graphite powder and a vinyl ester resin to form a homogeneous molding mixture comprising 60 to 80 weights. % of the graphite powder is based on the weight of the molding mixture; b) molding the molding mixture of step a) at a temperature of 80-200 ° C and a pressure of 5 〇〇 -4 psi A bipolar plate having a desired shape; wherein the graphite powder has a particle size of from 1 〇 to 8 Å. So far, the industry is still looking for a bipolar plate for fuel cells that combines high electrical conductivity, excellent mechanical properties and high thermal stability. SUMMARY OF THE INVENTION The main object of the present invention is to provide a bipolar plate for a fuel cell having both high electrical conductivity, excellent mechanical properties and high thermal stability. Another object of the present invention is to provide a method for producing a bipolar plate of a fuel cell having high electrical conductivity, excellent mechanical properties and high thermal stability. In the present invention, a composite bipolar plate is prepared by using (4) a resin and a conductive carbon filler by a block molding (BMC) method, wherein a suitable example of the electric carbon filling is nickel-plated graphite powder, and the nitrate is not ruthless. And nickel-plated carbon fiber The invention can improve the conductivity and mechanical properties of the composite bipolar plate fork diameter, and combine the fire retardant and anti-corrosion properties. 1286579 Embodiments The present invention discloses a method for preparing a composite bipolar plate for a fuel cell. The following steps: a) kneading a carbon filler with a phenolic resin to form a homogeneous molding mixture comprising graphite powder. Up to 8 〇, carbon fiber 1 to 1% by weight; and one or more selected from the group of conductive carbon fillers: 5 to 3 % by weight of nickel-plated graphite powder, 0.01 to 〇 · 3 % by weight, and 2 to 8 wt% of nickel-plated carbon fiber, the weight % is based on the weight of the phenolic resin, but the total content of the carbon fiber and the nickel-plated carbon fiber is not more than wt%; b) at 80-200° The molding mixture of molding step a) at a temperature of C and a pressure of 50-4000 psi forms a bipolar plate having a desired shape. Checheng Jia's 'The graphite powder is a graphite powder with a particle size of 丨〇8〇 mesh'. The nickel-plated graphite powder has a particle size of 1〇_8〇 before it is nickel-plated, and the nickel graphite of the ore The surface of the powder is plated with a nickel content of 20 to 80 parts by weight. /. , based on the weight before nickel plating. Preferably, the carbon fiber and the nickel-plated carbon fiber have a length of 1-1 〇 mm, and the fiber bundle is 5 to 24 K, wherein the nickel-plated carbon fiber has a nickel plating content of 10 to 30 wt%. , based on the weight before nickel plating. Preferably, the carbon nanotube is single-walled or multi-walled, and has a carbon tube diameter of 0.7 to 50 nm, a carbon tube length of 1 to 1 〇〇〇μιη, and a carbon tube specific surface area of 40 to 300 m2/ g. Preferably, a modifier is previously mixed with the phenolic resin prior to step a. The modifier is used in an amount of from 1-5 lbs. /〇, based on the weight of the phenolic resin. More preferably, the modifier is polyethylene oxide (P〇ly (ethylene 1286579 oxide)), polyethylene (polyvinyl vinyl), polyethylene glycol (polyethylene glycol) or polypropylene oxide ( Preferably, the modifier is a poly(ethylene oxide). Preferably, a coupling agent is previously mixed with the phenolic resin before the step a), and the amount of the coupling agent is 0 · 1- 5% by weight, based on the weight of the broth resin, wherein the chemical formula of the coupling agent can be expressed as follows (ROn-Ti-CROm or (RL-Si-CDm, where n&m is an integer from 〇 to 4 and The sum of η and m is 4; R is a C1_C4 alkyl fluorenyl group; and 1 is a C1-C6 alkyl group or a cycloalkyl group. More preferably, the coupling agent is tetra-isopropyl titanate (TPT). Preferably, the phenolic resin is a varnish type (Novalac) or a resol type phenolic resin, and the viscosity thereof is between 1 〇〇 2 〇〇 cps / 25 lt; t, and the solid content is between 50 to 70%. The following phenolic resins were used in the following comparative examples and examples: phenolic resin model: PF-650, Taiwan Changchun Synthetic Resin Co., Ltd. (Chang Chun CO.) '7th Floor, No.1, No.1, Songjiang Road, Taipei City. Comparative Example la-Id Graphite powder has a particle size range of more than 4〇 mesh (diameter 42〇"m) not more than 10%, 40 mesh~ 60 mesh (diameter between 42 〇 " 111 ~ 25 (^ 111) accounted for about 40%, 60 mesh ~ 80 mesh (diameter between 25 〇 ^ m ~ 177 " between melons) accounted for about 50%. Preparation of molding material and test piece 1. Dissolve 1286579 solution of 500 gram of phenolic resin with 2 〇ml of acetone as solvent, and add 2 (^ as a coupling agent, add 2 gram of pE〇 is a modifier. 2. The solution is stirred for a minute at room temperature using a motor agitator. 3. The above solution, 375 g (75% by weight based on the weight of the resin) The above graphite powder and 10 g (2% by weight, based on the reset of the phenolic resin) of carbon fibers (length i 3 mm; fiber bundles of 1 〇 to 12 κ) were poured into a bulk molding material (Bulk Molding c) 〇mp〇und 'BMC for short) uses a forward rotation and a reverse rotation to make it evenly mixed, and the kneading time is about 30 minutes. Stop the kneading action. The aggregates are taken out and collected and stored in a freezer. 4. Before the hot pressed slabs, the aggregates are taken out and divided into several groups, and the weight of each group is 1 gram of the mass molding material. The mold is fixed on the upper and lower table of the hot press, and the preheating mold temperature is set at 165. (: After the temperature arrives, place the dough in the center of the mold, press the test piece at a pressure of 3000 pSi, and the mold will open itself after 15 seconds, and the test piece will be taken out. Repeat steps i to 5 above, but The amount of the above graphite powder was changed to 3 25 g (65 wt%), 4 g (80 wt%) and 425 g (85 wt%). Example 1 a_ 1 d (carbon nanotube) Repeated comparison Steps 1 to 5 of Example 1, but fixing the amount of the above graphite powder to 375 g (75 wt%) and further adding 0.01 1286579 to 0.3 wt% of the carbon nanotubes in step 3. Based on the weight of the phenolic resin, the carbon nanotube used is a multi-wall carbon nanotube; 2) the carbon tube is pinched at 2 〇 nm; 3) the carbon tube is 1 μηι; 4) the carbon tube has a specific surface area of 1 70 m2/g. Example 2a-2d (nickel-plated graphite powder) Steps 1 to 5 of Comparative Example 1 were repeated, but the amount of the above graphite powder was fixed to 375 g (75% by weight) and further 5 to 30 weights were added in Step 3. % nickel-plated graphite powder based on the weight of the phenolic resin. The nickel-plated graphite powder used had a mesh size of 53 mesh before nickel plating, and the nickel plating component of the nickel-plated graphite powder had a weight of 60 weight 〇/〇. Example 3a-3d (nickel-plated carbon fiber) Steps 1 to 5 of Comparative Example 1 were repeated, but the above-mentioned graphite powder was solidified to 375 g (75 wt./〇) and further added to step 3 to 2 8 wt% of nickel-plated carbon fiber based on the weight of the phenolic resin. The nickel-plated carbon fiber used had a length of 13 mm before the nickel plating; the fiber bundle was 12 K' and the nickel content of the surface of the carbon fiber was 28% by weight. Electrical property test method: The principle of the four-point probe resistor is to apply voltage and current to the surface of the product to be tested, and to measure the voltage value and w value of the object to be tested at the other end. The volume resistance value p of the object to be tested can be known. The surface resistance of the test piece obtained by the four-point probe is further determined by the formula i to obtain the volume 1286579 resistance (P) ' p = 7* WF (formula l), and v is the voltage value passing through the test piece] K > The current value 'the ratio of the two is the surface resistance, and w is the thickness of the test 2' CF is the correction factor. In the present embodiment and the comparative example, the j-sheet which is hot-pressed is approximately 100 mm X 100 mm, and the thickness is 3 mm. The CF fork factor value CF = 4·5 of the test piece, and the volume resistance obtained by the formula 1 is obtained. (P), the reciprocal of the volume resistance is the conductivity of the test piece. Results Table 1 shows a fixed resin formulation with a fixed carbon fiber content of 2% by weight. Graphite: The test results of the conductivity test of the same molecular composite bipolar plate of 65 wt%, 75 wt%, 8 wt%, and 85 wt/〇. The conductivity test values were 19S/Cm, 24S/Cm, 70S/cm, and ms/cm, respectively. With the increase in the addition of strontium, it is known that the polymer composite bipolar plate forms an excellent conductive path and the electrical conductivity increases. Table 2 shows a solid resin formulation having a fixed carbon fiber content of 2% by weight and a solid graphite content of 75% by weight. The results of the conductivity test results of the polymer composite bipolar plates of 0.01% by weight, 〇·〇5 wt%, 〇丨 wt%, and 〇3 wt% were added and changed. The conductivity test values were 137 S/cm, 158 S/cm, 169 S/Cm, and i81 S/cm, respectively. When the amount of carbon nanotubes added reaches a certain ratio, the electrical conductivity is greatly increased. Table 3 shows a fixed resin formulation having a fixed carbon fiber content of 2% by weight and a fixed graphite content of 75% by weight. Further, nickel-plated graphite was added, and the content of the conductive test results of the polymer composite bipolar plates of 5 wt%, 15 wt%, 2 wt%, and 3 wt%, respectively. The conductivity test values are 78 11 1286579 : / (10), 116 s / cm, 124 s / cm, 165 nickel-plated graphite blending ratio: . 5 weight. /. The conductivity was 78 s/cm, and the conductivity was 24 S/em at 75 篁% of the nickel graphite powder (Comparative Example lb of Table 1). Compared with the conductivity of the two, it was found that only a small amount was required. The mineral nickel graphite can be used to establish a conductive path in the composite material: the electric bipolar plate can also reduce the proportion of graphite in the inclusion of nickel-plated graphite, and the conductivity is linearly improved. Table 4 shows the fixed resin formulation with a fixed carbon fiber content of 2% by weight and a ruthenium graphite of 35% by weight. . Further, nickel-plated carbon fibers were added, and the contents thereof were 2% by weight, 4% by weight, 6% by weight, and 8% by weight of the conductive test results of the polymer composite bipolar plates. The conductivity test values are Μ ~ (10) denier 76s / cm, 149s / cm, 195S / cm. When the carbon content of the mineral recording is 4% by weight, the electrical conductivity is 76 S/cm, which is almost the same as the conductivity of 75% by weight of graphite powder and 5% by weight of the graphite powder. (Example 2 of Table 3 is magical. When the fiber content is 8% by weight, the electrical conductivity is increased to i95 s/cm. As the nickel-plated carbon fiber increases, the electrical conductivity also increases.

表1 石墨（重量〇/〇) 導電值（S/cm) 與照例1 a 65 19 —照例 1 b 75 24 _ 對照例1 c * 80 70 對照例1 d 85 171 12 1286579Table 1 Graphite (weight 〇 / 〇) Conductivity (S / cm) and as usual 1 a 65 19 - as usual 1 b 75 24 _ Comparative Example 1 c * 80 70 Comparative Example 1 d 85 171 12 1286579

表2Table 2

j^^(S/cm) 158 169 ' ΓδΊ~ 碳奈木#%) 0.01j^^(S/cm) 158 169 ' ΓδΊ~ Carbon Nano##) 0.01

表3 例 2aTable 3 Example 2a

例 2 c 例 2dExample 2 c Example 2d

例 3b 鍍鎳石~Example 3b nickel-plated stone~

導電值（S/cm) " 78~~ ^~~ 116 124 165~ 表4 2 4 6 8 導電值（S/cm) ——31 ——76 — —149 —195~ 機械性質：抗曲強度測誠〆則試方法：ASTM D790 結果：表5為固定樹脂配方，固定碳纖維含量在2重量。/〇，改變石墨含量在65重量％、75重量％、8〇重量％、85重量 %的高分子複合材料雙極板的抗曲強度測試值結果。在塊狀模造成型裡’導電填充物含量相對於樹脂含量會直接影響到抗折強度的表現。再加上石墨多孔狀的表面具有較大 13 1286579 的比表面積吸附大量的樹脂。因此，可以看出石墨含量辦加抗折強度隨之下降。表ό為固定樹脂配方’固定碳纖維含量在2重量％，固定石墨含量在75重量％。並添加碳奈米管，其含量分別為0.01重量％、〇·〇5重量。/〇、0.1重量。/❹、〇·3重量％的高分子複合材料雙極板的抗曲強度測試值結果。隨著碳奈米管比例的增加，抗折強度隨之下降，主要是奈米材料有較高的比例的表層原子配位不足與極強的凡德瓦爾作用力能大幅提升奈米複合材料的力學性質。但是，樹脂具有膠著的功用’而碳奈米管有較大的比表面積和表面原子配位不足’與相同材質的大塊材料相比有較強的吸附能力。碳奈米管極佳的吸附特性，使得石墨表面樹脂吸附不足。隨著碳奈米管比例增加，其抗折強度也隨之下降。表7為固定樹脂配方，固定碳纖維含量在2重量〇/〇，固定石墨含量在75重量。/。。並添加鍍鎳石墨，其含量分別為5重量％、15重量。/〇、20重量％、30重量❶/〇的高分子複合材料雙極板的抗曲強度測試值結果。同樣的，在塊狀模造成型裡，導電填充物含量相對於樹脂含量會直接影響到抗折強度的表現。因此，同表5可以看出隨著鍍鎳石墨含量增加，抗折強度隨之下降。表8為固定樹脂配方，固定碳纖維含量在2重量〇/。，固定石墨含量在75重量❶/❶。並添加鍍鎳碳纖維，其含量分別為2重量％、4重量。/〇、6重量％、8重量％的高分子複合材料雙極板的抗曲強度測試值結果。隨著鍍鎳碳纖維含 1286579 量增加，抗折強度隨之增加，對於高分子複合材料雙極板而言，添加適量的纖維使得其抗折強度大幅提升，也不會發生浮纖的問題。可看出抗折強度隨著鍍鎳碳纖維含量增加而增加。Conductivity (S/cm) " 78~~ ^~~ 116 124 165~ Table 4 2 4 6 8 Conductivity (S/cm) ——31 ——76 — —149 —195~ Mechanical properties: Flexural strength Test Method: Test Method: ASTM D790 Results: Table 5 shows the fixed resin formula with a fixed carbon fiber content of 2%. /〇, The results of the flexural strength test values of the polymer composite bipolar plates having a graphite content of 65% by weight, 75% by weight, 8% by weight, and 85% by weight were changed. In the block mold type, the conductive filler content directly affects the flexural strength with respect to the resin content. In addition, the graphite porous surface has a large specific surface area of 13 1286579 to adsorb a large amount of resin. Therefore, it can be seen that the graphite content increases the bending strength. The surface is a fixed resin formulation. The fixed carbon fiber content is 2% by weight, and the fixed graphite content is 75% by weight. A carbon nanotube was added in an amount of 0.01% by weight and 〇·〇5 by weight, respectively. /〇, 0.1 weight. /❹,〇·3 wt% of the high-molecular composite bipolar plate test results of the flexural strength test results. As the proportion of carbon nanotubes increases, the flexural strength decreases, mainly because of the high proportion of surface atoms in the nanomaterials, and the strong van der Waals force can greatly enhance the nanocomposites. Mechanical properties. However, the resin has a glue function and the carbon nanotube has a large specific surface area and a surface atomic coordination is insufficient. Compared with a bulk material of the same material, it has a strong adsorption capacity. The excellent adsorption characteristics of the carbon nanotubes make the graphite surface resin insufficiently adsorbed. As the proportion of carbon nanotubes increases, the flexural strength decreases. Table 7 shows a fixed resin formulation having a fixed carbon fiber content of 2 wtm/〇 and a fixed graphite content of 75 wt%. /. . Nickel-plated graphite was added in an amount of 5% by weight and 15 parts by weight, respectively. /〇, 20% by weight, 30% by weight/〇 of the polymer composite bipolar plate test results of the flexural strength test results. Similarly, in the block mode, the conductive filler content directly affects the flexural strength relative to the resin content. Therefore, as shown in Table 5, it can be seen that as the nickel-plated graphite content increases, the flexural strength decreases. Table 8 shows the fixed resin formulation with a fixed carbon fiber content of 2 wt%. The fixed graphite content is 75 ❶/❶. Nickel-plated carbon fibers were added in an amount of 2% by weight and 4% by weight, respectively. /〇, 6% by weight, 8% by weight of the polymer composite bipolar plate test results of the flexural strength test value. As the amount of nickel-plated carbon fiber increased by 1,286,579, the flexural strength increased. For the polymer composite bipolar plate, the addition of an appropriate amount of fiber greatly increased the flexural strength and the problem of floating fiber did not occur. It can be seen that the flexural strength increases as the nickel-plated carbon fiber content increases.

表5 石墨（重量％) 抗曲強度（MPa) 對照例1 a 65 122 對照例lb 75 98.3 對照例1 c 80 97.1 對照例1 d 85 95 表6 碳奈米管（重量％) 抗曲強度（MPa) 實施例1 a 0.01 78.66 實施例1 b 0.05 76.92 實施例1 c 0.1 73.54 實施例1 d 0.3 72.42 —--- 表7 -____ 鍍鎳石墨（重量％)— 楚^強度（MPa) 90.33 實施例2a 5 一實施例2b 15 ._ 76.74 72.34 實施例2c 20 ~ Λ她例2d 30 52.64 15 1286579Table 5 Graphite (% by weight) Flexural strength (MPa) Comparative Example 1 a 65 122 Comparative Example lb 75 98.3 Comparative Example 1 c 80 97.1 Comparative Example 1 d 85 95 Table 6 Carbon nanotubes (% by weight) Flexural strength ( MPa) Example 1 a 0.01 78.66 Example 1 b 0.05 76.92 Example 1 c 0.1 73.54 Example 1 d 0.3 72.42 —--- Table 7 -____ Nickel-plated graphite (% by weight) - Chu ^ strength (MPa) 90.33 Implementation Example 2a 5 - Example 2b 15 ._ 76.74 72.34 Example 2c 20 ~ Λ her case 2d 30 52.64 15 1286579

機械性質：耐衝擊強度測定測試方法：ASTMD256 結果：表9為固定樹脂配方，固定碳纖維含量在2重量％，改變石墨含量S65重量％、75重量％、8〇重量％、85重量 =的尚分子複合材料雙極板的艾氏缺σ耐衝擊性質測試值 Τ果。隨著石墨粉末含量增加’相對的樹脂含量也減少。樹脂含量較少，材料的機械強度較弱，樹脂扮演的是膠聯作用。就-般塊狀模造成型法而言石墨含^ 65 4量％已經偏高。隨著石墨粉末含量增加’耐衝擊強度也隨之下降。表10為固定樹脂配方，固定碳纖維含量在2重量％，固定石墨含量在75重量％。並添加碳奈米管，其含量分別為0.01重量％、0.05重量％、0.1重量％、〇 3重量％的高分子複合材料雙極板的艾氏缺口耐衝擊性質測試值結果。隨著碳奈米管比例的增加，抗折強度隨之下降，主要是奈米材料有較高的比例的表層原子配位不足與極強的凡德瓦爾作用力能大幅提升奈米複合材料的力學性質。但是，樹脂具有膠著的功用’而碳奈米管有較大的比表面積和表面原子配位不足，與相同材質的大塊材料相比有較強的吸附能 1286579 力。碳奈米管極佳的吸附特性，使得石墨表面樹脂吸附不足。隨著碳奈米管比例增加，其耐衝擊強度也隨之下降。表11為固定樹脂配方，固定碳纖維含量在2重量0/〇，、=構不似石墨般的多孔片狀結構。且錄鎳石墨顆粒較石墨顆粒來的小，在承受衝擊應力時有較好的效果。Mechanical properties: Determination of impact strength Test method: ASTM D256 Results: Table 9 is a fixed resin formulation with a fixed carbon fiber content of 2% by weight, a change in graphite content of S65 wt%, 75 wt%, 8 wt%, 85 wt = still molecular The test results of the erbium-deficient impact resistance of the composite bipolar plate. As the graphite powder content increases, the relative resin content also decreases. The resin content is less, the mechanical strength of the material is weaker, and the resin acts as a glue. In the case of the -block-like mold-forming method, the graphite content is already high. As the graphite powder content increases, the impact strength also decreases. Table 10 shows a fixed resin formulation having a fixed carbon fiber content of 2% by weight and a fixed graphite content of 75% by weight. The carbon nanotubes were added in an amount of 0.01% by weight, 0.05% by weight, 0.1% by weight, and 3% by weight of the high-molecular composite bipolar plate of the Ehrlich notched impact resistance test results. As the proportion of carbon nanotubes increases, the flexural strength decreases, mainly because of the high proportion of surface atoms in the nanomaterials, and the strong van der Waals force can greatly enhance the nanocomposites. Mechanical properties. However, the resin has a function of adhesion. The carbon nanotube has a large specific surface area and insufficient surface atom coordination, and has a strong adsorption energy of 1286579 compared with a bulk material of the same material. The excellent adsorption characteristics of the carbon nanotubes make the graphite surface resin insufficiently adsorbed. As the proportion of carbon nanotubes increases, the impact strength also decreases. Table 11 shows a fixed resin formulation having a fixed carbon fiber content of 2 wt%/〇, = a graphite-like porous sheet structure. Moreover, the nickel graphite particles are smaller than the graphite particles and have a good effect when subjected to impact stress.

固定石墨含量在75重量％。並添加鍍鎳石墨，其含量分別為5重量％、15重量％、20重量％、3〇重量％的高分子複口材料雙極板的艾氏缺口耐衝擊測試值結果。隨著鍍鎳石墨摻混比例增加，其耐衝擊強度趨勢是緩緩上升。利用電子顯微鏡（SEM) m察鍍鎳石墨，其表面是緊密的顆粒狀表12為固定樹脂配方，固定碳纖維含量在2重量％固定石墨含量在75重量％。並添加鍍鎳碳纖維，重量％、4重量％、6重量％、8重量％的高分子 ==的艾氏缺口耐衝擊測試值結果。隨著錄錄耐衝擊制碳纖維㈣衝擊強纽起樹脂The fixed graphite content was 75% by weight. The results of the Ehrlich notch impact resistance test of the polymer composite bipolar plate having a nickel-plated graphite content of 5 wt%, 15 wt%, 20 wt%, and 3 wt%, respectively, were added. As the nickel-plated graphite blending ratio increases, the impact strength trend tends to rise slowly. Nickel-plated graphite was examined by electron microscopy (SEM), and its surface was tightly granulated. Table 12 shows a fixed resin formulation with a fixed carbon fiber content of 2% by weight and a fixed graphite content of 75% by weight. And adding nickel-plated carbon fiber, weight%, 4% by weight, 6% by weight, 8% by weight of the polymer == Ehrlich notched impact test value results. With the record of impact-resistant carbon fiber (four) impact strong new resin

導電雙極r 添加料碳纖維可顯著提升複合材导電雙極板的耐衝擊強度及導電率。Conductive bipolar r Addition carbon fiber can significantly improve the impact strength and electrical conductivity of composite conductive bipolar plates.

17 1286579 表ίο 碳奈米管（重量％) '" "T---—_—-— —^_ _____ 1.8 實施例1 a 0.01 實施例lb 0.05 實施例1 c 0.1 1 7 實施例Id 0.3 -- 表11 鍍鎳石墨（重篁％) ^缺口衝擊強度實施例2a 5 —------zr J 實施例2b 15 ___3.0 實施例2c 20 實施例2d 30 — 表12 錢鎳石反纖維（重里％ ) ^氏缺口衝擊強度實施例3a 2 ----- /_____ __ 2.0 實施例3b 4 2.4 實施例3 c 6 實施例3d 8 3.9 腐蝕性質：測試方法：ASTM G5_94 結果：表13為固定樹脂配方’固定碳纖維含量在2重量％，改變石墨含量在65重量％、75重量％、80重量％、85重量 %的高分子複合材料雙極板的耐腐蚀性質測試結果。在不同石墨含量的高分子複合材料雙極板的腐蚀電流非常小， 18 1286579 石墨含量在65重量％以上幾乎是不腐蝕的材料。表14為固定樹脂配方，固定碳纖維含量在2重量0/〇，固定石墨含量在75重量°/〇。並添加碳奈米管，其含量分別為0.01重量❶/❶、〇·〇5重量％、〇el重量。/。、〇 3重量％的高分子複合材料雙極板的财腐敍性質測試值結果。改變不同的碳奈米管含量，其腐蝕電流變化不大，其抗腐蝕性質極佳，幾乎沒有腐姑現象發生。添加不同比例的碳奈米管有極佳的抗腐蝕性質。表15為固定樹脂配方，固定碳纖維含量在2重量0/〇，固定石墨含量在75重量％。並添加鍍鎳石墨，其含量分別為5重量％、15重量％、20重量❶/。、30重量。/。的高分子複合材料雙極板的耐腐蝕性質測試值結果。在不同比例的鍍鎳石墨含量下，其腐蝕電流仍然非常小。但是，鍍鎳石墨中的鎳金屬會影響其腐蝕電流，原因是鎳金屬會受到酸液腐蝕而影響高分子複合材料雙極板的腐蝕性質。就整體而言，仍然保有極佳的抗腐蝕性質。表16為固定樹脂配方，固定碳纖維含量在2重量％，固定石墨含量在75重量。/。。並添加鍍鎳碳纖維，其含量分別為2重量％、4重量％、6重量％、8重量％的高分子複合材料雙極板的财腐#性質測試值結果。隨著鍍鎳碳纖維含量增加，高分子複合材料雙極板的腐蝕電流也隨之增加，腐蝕電流在l〇-3 Amps/cm2* 10-5Amps/em2之間，其原因是鍍鎳碳纖維中的金屬鎳容易受到酸液的腐蝕，而影響到分子複合材料雙極板的腐蝕性質。和石墨相較之下仍然偏 19 1286579 低，但是同樣具有财餘性質。表13 石墨（重量％) 腐蝕電流值 (Amps/cm2) 對照例1 a 65 2.84x10° 對照例lb 75 1.77x10° 對照例1 c 80 9.92xl0'b 對照例Id 85 1.70x10° 表14 碳奈米管（重量％) 腐蝕電流值 (Amps/cm ) 實施例la 0.01 4.1x10° 實施例lb 0.05 3.47x10° 實施例1 c 0.1 2.81xl〇·5 實施例Id 0.3 4.43xl〇·5 表15 鍍鎳石墨（重量％) 腐蝕電流值 (Amps/cm2) 實施例2a 5 1·74χ1(Γ4 實施例2b 15 8.34x10° 實施例2c 20 1.89xl〇·4 實施例2d 30 2.42xl〇·4 表16 鍍鎳碳纖維（重量％) 腐蝕電流值 (Amps/cm ) 實施例3a 2 9·69χ10_5 實施例3b 4 6.47χ1(Γ4 實施例3 c 6 1·29χ10·3 實施例3 d 8 1.46x10° 20 1286579 防燃難燒性質·· UL-94測試測試方法：ASTMD-3801 結果：難燃性測試規範中的垂直燃燒法，以測試不同試片之難燃程度為94V-0、94V-1或94V-2。本實施例及對照例中所製備之試片在測試的過程中均不會產生熔融滴垂物，因此也不會引起脫脂棉的燃燒。表17為固定樹脂配方，固定碳纖維含量在2重量％，改變石墨含量在65重量％、75重量％、80重量％、85重量〇/〇的南分子複合材料雙極板的防燃難燒性質結果。石墨含量在65重量％以上即具有防火難燃性，在UL_94測試中符合 94V-0。表1 8為固定樹脂配方，固定碳纖維含量在2重量％，固定石墨含量在7 5重量％。並添加碳奈米管，其含量分別為0.01重量❶/〇、〇·〇5重量％、（M重量％、〇 3重量％的高分子複合材料雙極板的防燃難燒性質測試結果。在UL_94測試中符合94V-0。表19為固疋树脂配方，固定碳纖維含量在2重量％，固定石墨含量在75重量％。並添加鍍鎳石墨，其含量分別為5重量％、15重量。/〇、20重量。/。、30重量％的高分子複合材料雙極板的防燃難燒性質測試結果。在UL-94測試中符合94V-0。表2 0為固疋树脂配方，固定碳纖維含量在2重量％， 21 1286579 固定石墨含量在75重量。/〇。並添加鍍鎳碳纖維，其含量分別為2重量％、4重量％、6重量％、8重量％的高分子複合材料雙極板的防燃難燒性質測試結果。在UL-94測試中符合 94V-0。表17 石墨 (重量％) 熔融滴垂脫脂棉燃燒 UL-94標準對照例1 a 65 N/A N/A 94V-0 對照例lb 75 N/A N/A 94V-0 對照例1 c 80 N/A N/A 94V-0 對照例Id 85 N/A N/A 94V-0 N/A :未測得表18 碳奈米管 (重量％) 熔融滴垂脫脂棉燃燒 UL-94標準實施例la 0.01 N/A N/A 94V-0 實施例lb 0.05 N/A N/A 94V-0 實施例lc 0.1 N/A N/A 94V-0 實施例Id 0.3 N/A N/A 94V-0 N/A :未測得表19 鍍鎳石墨 (重量％) 熔融滴垂脫脂棉燃燒 UL-94標準實施例2a 5 N/A N/A 94V-0 實施例2b 15 N/A N/A 94V-0 實施例2c 20 N/A N/A 94V-0 實施例2d 30 N/A N/A 94V-0 N / A :未測得 22 1286579 表20 鍍鎳碳纖維 (重量％) 炼融滴垂脫脂棉燃燒 UL-94標準實施例3a 2 N/A N/A 94V-0 實施例3b 4 N/A N/A 94V-0 實施例3 c 6 N/A N/A 94V-0 實施例3d 8 N/A N/A 94V-0 N/A :未測得防燃難燒性質：極限氧氣指數（Limit Oxygen Index，L.O.I.) 測試測試方法·· ASTM D-2863 結果：對於高分子基材的難燃特性進行評估，最常使用的方法即為極限氧氧指數法（Limiting Oxygen Index，L.O.I·)。一般氧指數測試定義如下式所示： LOI: [〇2][〇2] + [N2] 100 其中[02]與[N2]分別為氧氣與氮氣之體積流速 (ml/sec)，而氧指數和燃燒性的關係，一般區分為三個等級： LOI 21 θ 可燃性 LOI = 22 〜25 ->自熄性（不易燃燒） LOI 26 — 難燃性極限氧氣指數值可鑑定材料於室溫下在流動的氧氣、氮氣混合系統中，能讓火焰持續燃燒所需的最低氧氣濃度。 23 1286579 表2!為固定樹脂配方，g^碳_含改變石墨含量在65重量％、75重量％、8。重里2重量％，。/❶的高分子複合材料雙極板的防燃難燒性質。、85重量量在65重量。以上即具有防火難燃性，其l〇;二表22為固定樹脂配方，固定碳纖維含量在2重量％，固定石墨含量在75重量％。並添加碳奈米管，其含量分別為〇.〇1重量❶/。、0.05重量％、〇丨重量％、〇 3重量％的高分子複合材料雙極板的防燃難燒性質測試結果。其l〇i值皆大於50。表23為固定樹脂配方，固定碳纖維含量在2重量％，固疋石墨含量在75重量％。並添加鍍鎳石墨，其含量分別二重羞〆〇、15重量0/〇、20重量。/〇、3〇重量0/〇的高分子複口材料雙極板的防燃難燒性質測試結果。其LOI值皆大於 50 〇 ' 表24為固定樹脂配方，固定碳纖維含量在2重量％， φ 、墨3 i在7 5重量％。並添加鍍錄碳纖維，其含量分人為2重里％、4重量％、6重量％、$重量。/❶的高分子複材料雙極板的防燃難燒性質測試結果。豆LOI值皆大於 50 〇〆、 24 1286579 表21 石墨 (重量％) 熔融滴垂脫脂棉燃燒極限氧指數 L.O.I 對照例1 a 65 N/A N/A >50 對照例1 b 75 N/A N/A >50 對照例1 c 80 N/A N/A >50 對照例1 d 85 N/A N/A >50 N/A :未測得表22 碳奈米管 (重量％) 熔融滴垂脫脂棉燃燒極限氧指數 L.O.I 實施例1 a 0.01 N/A N/A >50 實施例lb 0.05 N/A N/A >50 實施例lc 0.1 N/A N/A >50 實施例Id 0.3 N/A N/A >50 N/A :未測得17 1286579 Table ο Carbon nanotubes (% by weight) '""T----_----^______ 1.8 Example 1 a 0.01 Example lb 0.05 Example 1 c 0.1 1 7 Example Id 0.3 -- Table 11 Nickel-plated graphite (% by weight) ^ Notched impact strength Example 2a 5 -------zr J Example 2b 15 ___3.0 Example 2c 20 Example 2d 30 - Table 12 Stone anti-fiber (% by weight) 缺口 notched impact strength Example 3a 2 ----- /_____ __ 2.0 Example 3b 4 2.4 Example 3 c 6 Example 3d 8 3.9 Corrosion properties: Test method: ASTM G5_94 Result: Table 13 shows the results of the corrosion resistance test of the polymer composite bipolar plate in which the fixed resin formulation 'fixed carbon fiber content was 2% by weight and the graphite content was changed to 65 wt%, 75 wt%, 80 wt%, and 85% by weight. The corrosion current of polymer composite bipolar plates with different graphite contents is very small, and 18 1286579 graphite content of more than 65% by weight is almost non-corrosive material. Table 14 shows a fixed resin formulation having a fixed carbon fiber content of 2 wt%/〇 and a fixed graphite content of 75 wt%/〇. A carbon nanotube was added in an amount of 0.01 wt%/❶, 〇·〇5 wt%, and 〇el weight, respectively. /. 〇〇 3% by weight of the high-molecular composite bipolar plate test results. When the content of different carbon nanotubes is changed, the corrosion current does not change much, and the corrosion resistance is excellent, and almost no corrosion occurs. The addition of different proportions of carbon nanotubes has excellent corrosion resistance. Table 15 shows a fixed resin formulation having a fixed carbon fiber content of 2 wt%/〇 and a fixed graphite content of 75 wt%. Nickel-plated graphite was added in an amount of 5% by weight, 15% by weight, and 20% by weight. 30 weight. /. The results of the corrosion resistance test results of the polymer composite bipolar plate. The corrosion current is still very small at different ratios of nickel-plated graphite. However, the nickel metal in the nickel-plated graphite affects the corrosion current because the nickel metal is corroded by the acid to affect the corrosion properties of the polymer composite bipolar plate. As a whole, it still retains excellent corrosion resistance. Table 16 shows a fixed resin formulation having a fixed carbon fiber content of 2% by weight and a fixed graphite content of 75% by weight. /. . Further, nickel-plated carbon fibers were added, and the contents thereof were 2% by weight, 4% by weight, 6% by weight, and 8% by weight of the polymer composite bipolar plate. As the content of nickel-plated carbon fiber increases, the corrosion current of the polymer composite bipolar plate also increases, and the corrosion current is between l〇-3 Amps/cm2* 10-5Amps/em2, which is due to the nickel-plated carbon fiber. Metal nickel is susceptible to corrosion by acid, which affects the corrosive nature of molecular composite bipolar plates. Compared with graphite, it is still lower than 19 1286579, but it also has a financial nature. Table 13 Graphite (% by weight) Corrosion current value (Amps/cm2) Comparative Example 1 a 65 2.84×10° Comparative Example lb 75 1.77×10° Comparative Example 1 c 80 9.92×10′b Comparative Example Id 85 1.70×10° Table 14 Carbon Rice tube (% by weight) Corrosion current value (Amps/cm) Example la 0.01 4.1x10° Example lb 0.05 3.47x10° Example 1 c 0.1 2.81xl〇·5 Example Id 0.3 4.43xl〇·5 Table 15 Plating Nickel graphite (% by weight) Corrosion current value (Amps/cm2) Example 2a 5 1·74χ1 (Γ4 Example 2b 15 8.34x10° Example 2c 20 1.89xl〇·4 Example 2d 30 2.42xl〇·4 Table 16 Nickel-plated carbon fiber (% by weight) Corrosion current value (Amps/cm) Example 3a 2 9·69χ10_5 Example 3b 4 6.47χ1 (Γ4 Example 3 c 6 1·29χ10·3 Example 3 d 8 1.46x10° 20 1286579 Flame-proof and hard-to-burn properties · UL-94 test test method: ASTM D-3801 Result: The vertical combustion method in the flame retardance test specification to test the flame retardancy of different test pieces is 94V-0, 94V-1 or 94V- 2. The test pieces prepared in the examples and the comparative examples did not produce molten drip during the test, and therefore did not cause absorbent cotton. Table 17 is a fixed resin formulation with a fixed carbon fiber content of 2% by weight. It is difficult to prevent the burning of the south molecular composite bipolar plate with a graphite content of 65 wt%, 75 wt%, 80 wt%, and 85 wt〇〇. The result of burning property. The graphite content is more than 65% by weight, which is fireproof and flame retardant, and meets 94V-0 in the UL_94 test. Table 1 is a fixed resin formula with fixed carbon fiber content of 2% by weight and fixed graphite content of 75 weight. And adding carbon nanotubes, the content of which is 0.01 wt./❶, 〇·〇5 wt%, (M wt%, 〇3 wt% of the polymer composite bipolar plate The results were 94V-0 in the UL_94 test. Table 19 shows the solid resin formulation with a fixed carbon fiber content of 2% by weight and a fixed graphite content of 75% by weight. The nickel-plated graphite was added at a content of 5% by weight, respectively. Weight./〇, 20% by weight, 30% by weight of the polymer composite bipolar plate test results of flameproof and hard-to-burn properties. In the UL-94 test, it meets 94V-0. Table 2 0 is the solid resin formulation , fixed carbon fiber content in 2 % Amount, 211,286,579 graphite content is fixed at 75 wt. /〇. Further, nickel-plated carbon fibers were added, and the contents thereof were 2% by weight, 4% by weight, 6% by weight, and 8% by weight, respectively, of the test results of the flame retardant properties of the polymer composite bipolar plates. In the UL-94 test, it meets 94V-0. Table 17 Graphite (% by weight) Melt drip cotton wool burning UL-94 Standard Comparative Example 1 a 65 N/AN/A 94V-0 Comparative Example lb 75 N/AN/A 94V-0 Comparative Example 1 c 80 N/AN/ A 94V-0 Comparative Example Id 85 N/AN/A 94V-0 N/A : Not measured Table 18 Carbon nanotubes (% by weight) Melt drip cotton wool burning UL-94 Standard Example la 0.01 N/AN/ A 94V-0 Example lb 0.05 N/AN/A 94V-0 Example lc 0.1 N/AN/A 94V-0 Example Id 0.3 N/AN/A 94V-0 N/A : Not measured Table 19 Nickel graphite (% by weight) Melt drip cotton wool burning UL-94 Standard Example 2a 5 N/AN/A 94V-0 Example 2b 15 N/AN/A 94V-0 Example 2c 20 N/AN/A 94V- 0 Example 2d 30 N/AN/A 94V-0 N / A : not measured 22 1286579 Table 20 Nickel-plated carbon fiber (% by weight) smelting drip cotton wool burning UL-94 standard Example 3a 2 N/AN/A 94V-0 Example 3b 4 N/AN/A 94V-0 Example 3 c 6 N/AN/A 94V-0 Example 3d 8 N/AN/A 94V-0 N/A : Undetected fireproof Burning properties: Limit Oxygen Index (LOI) Test and Test Methods·· ASTM D-2863 Result: For the flame retardant properties of polymer substrates Evaluation method most commonly used is the oxygen limiting oxygen index (Limiting Oxygen Index, L.O.I ·). The general oxygen index test is defined as follows: LOI: [〇2][〇2] + [N2] 100 where [02] and [N2] are the volumetric flow rates of oxygen and nitrogen, respectively (ml/sec), and the oxygen index The relationship with flammability is generally divided into three levels: LOI 21 θ flammability LOI = 22 ～25 -> self-extinguishing (non-flammable) LOI 26 — flame retardant limit oxygen index value identifiable material at room temperature The minimum oxygen concentration required to sustain the flame in a flowing oxygen and nitrogen mixing system. 23 1286579 Table 2! is a fixed resin formulation, g^carbon _ contains a change in graphite content of 65% by weight, 75% by weight, 8. 2% by weight, /❶The polymer composite bipolar plate has a flame-proof and hard-to-burn property. 85 weight is 65 weight. The above is fire retardant, and it is the same as the fixed resin formulation, the fixed carbon fiber content is 2% by weight, and the fixed graphite content is 75% by weight. And a carbon nanotube is added, and the content thereof is 〇.〇1 weight ❶/. The test results of the flame retardant and hard-to-burn properties of the high molecular composite bipolar plate of 0.05% by weight, 〇丨% by weight, and 〇3% by weight. Its l〇i values are all greater than 50. Table 23 shows a fixed resin formulation having a fixed carbon fiber content of 2% by weight and a solid graphite content of 75% by weight. And added nickel-plated graphite, the content of which is double shy, 15 weight 0 / 〇, 20 weight. /〇, 3〇 weight 0/〇 polymer composite material bipolar plate test results of flame retardant properties. The LOI value is greater than 50 〇 ' Table 24 is a fixed resin formulation with a fixed carbon fiber content of 2% by weight, φ, and ink 3 i at 75 % by weight. The plated carbon fiber was added in an amount of 2% by weight, 4% by weight, 6% by weight, and by weight. The test results of the flame retardant and hard-to-burn properties of the polymer composite bipolar plate. Beans LOI values are greater than 50 〇〆, 24 1286579 Table 21 Graphite (% by weight) Melt drip cotton wool burning limit oxygen index LOI Comparative Example 1 a 65 N/AN/A > 50 Comparative Example 1 b 75 N/AN/A >50 Comparative Example 1 c 80 N/AN/A > 50 Comparative Example 1 d 85 N/AN/A > 50 N/A : Not determined Table 22 Carbon nanotubes (% by weight) Molten drip cotton Combustion Limit Oxygen Index LOI Example 1 a 0.01 N/AN/A > 50 Example lb 0.05 N/AN/A > 50 Example lc 0.1 N/AN/A > 50 Example Id 0.3 N/AN/ A >50 N/A : not measured

表23 鍍鎳石墨 (重量％) 熔融滴垂脫脂棉燃燒極限氧指數 L.O.I 實施例2a 5 N/A N/A >50 實施例2b 15 N/A N/A >50 實施例2c 20 N/A N/A >50 實施例2d 30 N/A N/A >50 N/A :未測得Table 23 Nickel-plated graphite (% by weight) Melt drip cotton wool burning limit oxygen index LOI Example 2a 5 N/AN/A > 50 Example 2b 15 N/AN/A > 50 Example 2c 20 N/AN/ A > 50 Example 2d 30 N/AN/A > 50 N/A : not measured

25 1286579 表24 鍍鎳碳纖維 (重量％) 溶融滴垂脫脂棉燃燒極限氧指數 L.O.I 實施例3 aj 2 N/A Ν/Α >50 實施例3 b 4 ~~νΤα νΤα >50 實施例3 c tiu /d Ο 1 6 ν7α~~ N/A >50 實施例3 d 8 ~~νΤα N/A >50 N/A ··未測得 — 以上對照例與實施例在BMC捏合的成份相同的，實施例石墨比例皆佔75重量％，主裏添加了碳奈米管、鍍鎳石墨、鍍鎳碳纖維等導配方是完全 1的差別是各 -電碳化物，並改變其添加比例。由實施例的導電度分析可知，隨著碳奈米管、石墨、鍍鎳碳纖維、鍍鎳石墨的增加，其導電率也隨之升高。碳奈米官的導電性也隨著其含量增加而升高，其導電率在I” S/cm〜18i S/cm之間，鍍鎳石墨含量增加其導電率也隨之增加，導電率在78S/cm〜165s/cm之間。鍍鎳碳纖維的導電率隨著其含量增加而增加，導電率在31 s/cm〜195 S/cm之間。由實施例的抗折強度分析可知BMC塊狀模造成型裡，導電填充物含量相對於樹脂含量會直接影響到抗折強度的表現。碳奈米管添加量增加，抗折性質變差，抗折強度數值在72.42 MPa〜78.66 MPa之間。鍍鎳石墨添加量增加，抗折性質變差，抗折強度數值在52·64 MPa〜9〇3〇 Μρ& 之間。隨著鍍鎳碳纖維含量增加，抗折強度隨之增加，抗 26 1286579 折強度數值在53.22 MPa〜73 _44 MPa之間。由實施例的耐衝擊強度分析可知，隨著碳奈米管含量25 1286579 Table 24 Nickel-plated carbon fiber (% by weight) melted drip cotton wool burning limit oxygen index LOI Example 3 aj 2 N/A Ν/Α > 50 Example 3 b 4 ~~νΤα νΤα > 50 Example 3 c Tiu /d Ο 1 6 ν7α~~ N/A > 50 Example 3 d 8 ~~νΤα N/A > 50 N/A ··Not measured - The above comparative examples are the same as the examples in the BMC kneading In the example, the ratio of graphite is 75% by weight. The main formula is carbon nanotube, nickel-plated graphite, nickel-plated carbon fiber, etc. The difference is that the difference is the individual-electric carbide, and the addition ratio is changed. From the conductivity analysis of the examples, it is known that as the carbon nanotubes, graphite, nickel-plated carbon fibers, and nickel-plated graphite increase, the electrical conductivity also increases. The conductivity of carbon nanotubes also increases with the increase of its content, and its conductivity is between I" S / cm ~ 18i S / cm. The conductivity of nickel-plated graphite increases, and the conductivity increases. Between 78S/cm and 165s/cm, the conductivity of nickel-plated carbon fiber increases with the increase of its content, and the conductivity is between 31 s/cm and 195 S/cm. The BMC block is known from the flexural strength analysis of the example. In the shape of the mold, the content of the conductive filler relative to the resin content will directly affect the performance of the flexural strength. The addition of carbon nanotubes increases, the flexural properties deteriorate, and the flexural strength values range from 72.42 MPa to 78.66 MPa. The addition of nickel-plated graphite increases, the flexural strength deteriorates, and the flexural strength value is between 52·64 MPa~9〇3〇Μρ&. As the content of nickel-plated carbon fiber increases, the flexural strength increases, anti-26 1286579 The flexural strength value is between 53.22 MPa and 73 _44 MPa. From the impact strength analysis of the examples, it is known that with the carbon nanotube content

提升，使得耐衝擊強度也陆夕τ^ . L 之下降。艾氏缺口衝擊強度在 1.6 ft_lb/in 〜2.4 ft-lb/in 夕 pq ^ .A ^ ^ ib/ln之間。由於，碳奈米管有較大的比表面積和表面原子配位不^，與相同材質的大塊材料相比有軚強的吸附能力。碳奈米管極佳的吸附特性，使得樹脂含量明顯不足。隨著鍍鎳石墨添加量增加，耐衝擊強度增加，艾氏缺口衝擊強度在2.40ft_lb/in〜3 31 fMb/in之間。隨著鍍鎳碳纖維含量增加，耐衝擊強度也隨之增加。艾氏缺口衝擊強度在53 ft-lb/in〜73 ft-lb/in之間，由於纖維含量的增加其耐衝擊強度也增加。由實施例的防火難燃特性分析得知以酚醛樹脂為基材的高分子複合材料本身即具備防火難燃的特性，在添加不同比例的碳奈米管、鍍鎳石墨、鍍鎳碳纖維均保有防火難然的特性，且符合UL-94V0規範、L.O.I值> 50。由實施例的耐腐餘性質得知，石墨添加量在75重量 % ’添加不同比例的碳奈米管、鑛鎳石墨、鍍鎳碳纖維的高分子複合材料導電雙極板均有耐腐蝕的特性。本發明已被描述於上，熟悉本技術的人士仍可作出未脫離下列申請專利範圍的多種變化及修飾。 27Lifting, so that the impact strength is also reduced. The Ebbs impact strength is between 1.6 ft_lb/in and 2.4 ft-lb/in pq ^ .A ^ ^ ib/ln. Because the carbon nanotubes have a large specific surface area and surface atom coordination, they have a strong adsorption capacity compared with bulk materials of the same material. The excellent adsorption characteristics of the carbon nanotubes make the resin content significantly insufficient. As the amount of nickel-plated graphite added increases, the impact strength increases, and the Izod notched impact strength is between 2.40 ft/lb/in and 3 31 fMb/in. As the nickel-plated carbon fiber content increases, the impact strength also increases. The Epstein's notched impact strength is between 53 ft-lb/in and 73 ft-lb/in, and the impact strength is also increased due to the increase in fiber content. According to the analysis of the fire retardant characteristics of the examples, the polymer composite material based on phenolic resin has the characteristics of fire retardant and flame retardant, and is added with different proportions of carbon nanotubes, nickel-plated graphite and nickel-plated carbon fibers. Fire-resistant features, and in line with UL-94V0 specification, LOI value > 50. According to the corrosion resistance of the examples, the graphite addition amount is 75% by weight. The corrosion-resistant characteristics of the polymer composite bipolar plates with different proportions of carbon nanotubes, ore-nickel graphite and nickel-plated carbon fibers are added. . The invention has been described above, and many variations and modifications may be made without departing from the scope of the following claims. 27

Claims

1286579 (2006 _ 6月修正）十、申請專利範圍： 1. 一種燃料電池的複合材料雙極板之製備方法，包含下列步驟：a)捏合碳填料與一酚醛樹脂，形成一均質之模塑混合物，該模塑混合物包含石墨粉末60至80重量％ ; 碳纖維1至10重量％ ;及選自以下導電碳填料族群的一種或多種：該族群由鍍鎳石墨粉末5至30重量％，碳奈米管〇·〇1至0·3重量。/〇，及鍍鎳碳纖維2至8重量％所組成，該等重量％以該酚醛樹脂的重量為基準，但該碳纖維及鍍鎳碳纖維的含量總和不大於10重量。/。，其中該酚醛樹脂為清漆型（Novalac)或是可熔型（Res〇itype)酚醛樹脂，且其黏度介於100〜200 cps/25°C，及固形份介於50〜70% ;該碳纖維及鍍鎳破纖維長度為1-1〇 mm，及纖維束為5〜24 K，該鑛鎳碳纖維表面鍍鎳含量為10〜30重量％，以未鍍鎳前的重量為基準；及該奈米碳管為單壁或多壁，其具有碳管直徑為0.7〜50 nm，碳管長度為！〜1〇〇〇 μπι，及碳管比表面積為40〜300 m2/g ; b)以熱壓方式於80_200°C之溫度與 50-4000 psi之壓力下模塑步驟a)的模塑混合物形成一具有想要形狀的雙極板。 2·如申請專利範圍帛i項的方法，其中該石墨粉末為粒仪；丨於10-80網目的石墨粉末，該鍍鎳石墨粉末未鍍鎳前具有介力10-80網目的粒徑，及該鍍鎳石墨粉末的表面鍍鎳含量為20〜80重量％，以未鍍鎳前的重量為基準。 28 .1286579 (2006年6月修正) 3.如申請專利範圍第i項的方法，其中於步驟心之前將一改質劑預先與該酚醛樹脂混合，該改質劑的用量為 0_1_5重量。/〇，以該酚醛樹脂重量為基準。 —4.如中請專利範圍帛3項的方法，其中該改f劑為聚環氧乙烧（P〇ly(ethylene oxide))、聚乙烯醇（p〇ly(vinyi alcohol)、聚乙二醇（Polyethylene glyc〇1)或聚環氧丙烧印叫 propylene oxide)。 5·如申請專利範圍第4項的方法，其中該改質劑為聚環氧乙烷。人 6·如申請專利範圍第丨項的方法，於步驟“之前將一偶合劑預先與該酚醛樹脂混合，該偶合劑的用量為重量。/。，，以該酚醛樹脂重量為基準，其中該偶合劑之化學式則可以下列表示之（R)n_Ti_(Rl)m或（R)n_Si_(Ri、，其中 η及m為0至4的整數及n&m的和為4;尺為^^々烷氣基；及R!為C1-C6烷基或環烷基。 7.如申請專利範圍第6項的方法，其中該偶合劑為四異丙基鈦酸鹽（tetra-isopropyl titanate，TPT )。 291286579 (2006 _ June Amendment) X. Patent Application Range: 1. A method for preparing a composite bipolar plate for a fuel cell, comprising the steps of: a) kneading a carbon filler and a phenolic resin to form a homogeneous molding mixture; The molding mixture comprises 60 to 80% by weight of graphite powder; 1 to 10% by weight of carbon fibers; and one or more selected from the group of conductive carbon fillers: 5 to 30% by weight of nickel-plated graphite powder, carbon nano Tube 〇〇 1 to 0·3 weight. /〇, and nickel-plated carbon fiber is composed of 2 to 8% by weight, and the weight% is based on the weight of the phenol resin, but the total content of the carbon fiber and the nickel-plated carbon fiber is not more than 10% by weight. /. The phenolic resin is a varnish type (Novalac) or a fusible type (Res〇itype) phenolic resin, and has a viscosity of 100 to 200 cps/25 ° C, and a solid content of 50 to 70%; the carbon fiber And the length of the nickel-plated broken fiber is 1-1〇mm, and the fiber bundle is 5~24 K, and the nickel-carbon fiber surface has a nickel plating content of 10~30% by weight, based on the weight before the nickel plating; and the nai The carbon tube is single-walled or multi-walled, and has a carbon tube diameter of 0.7 to 50 nm, and the length of the carbon tube is! ~1〇〇〇μπι, and the specific surface area of the carbon tube is 40~300 m2/g; b) molding the molding mixture of step a) by hot pressing at a temperature of 80-200 ° C and a pressure of 50-4000 psi A bipolar plate with the desired shape. 2. The method of claim 帛i, wherein the graphite powder is a granule; the graphite powder of 10-80 mesh is used, and the nickel-plated graphite powder has a particle size of 10-80 mesh before being nickel-plated. And the surface nickel plating content of the nickel-plated graphite powder is 20 to 80% by weight based on the weight before nickel plating. 28 .1286579 (amended June 2006) 3. The method of claim i, wherein a modifier is pre-mixed with the phenolic resin prior to the step, the modifier being used in an amount of 0_1_5 by weight. /〇, based on the weight of the phenolic resin. —4. The method of claim 3, wherein the agent is P〇ly (ethylene oxide), polyvinyl alcohol (p〇ly (vinyi alcohol), polyethylene 2 Alcohol (Polyethylene glyc 〇 1) or poly propylene acrylate (called propylene oxide). 5. The method of claim 4, wherein the modifier is polyethylene oxide. The method of claim 6 is as follows: in the step “pre-mixing a coupling agent with the phenolic resin in advance, the coupling agent is used in an amount of weight, based on the weight of the phenolic resin, wherein The chemical formula of the coupling agent may be represented by (R)n_Ti_(Rl)m or (R)n_Si_(Ri, where η and m are integers of 0 to 4 and the sum of n&m is 4; the ruler is ^^々 Alkyl group; and R! is a C1-C6 alkyl group or a cycloalkyl group. 7. The method of claim 6, wherein the coupling agent is tetra-isopropyl titanate (TPT). 29