WO2023097587A1 - Method for preparing bipolar plate for electrochemical fuel cell - Google Patents

Method for preparing bipolar plate for electrochemical fuel cell Download PDF

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WO2023097587A1
WO2023097587A1 PCT/CN2021/134945 CN2021134945W WO2023097587A1 WO 2023097587 A1 WO2023097587 A1 WO 2023097587A1 CN 2021134945 W CN2021134945 W CN 2021134945W WO 2023097587 A1 WO2023097587 A1 WO 2023097587A1
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bipolar plate
bipolar
substrate
thickness
flow channel
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PCT/CN2021/134945
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French (fr)
Chinese (zh)
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许哲荣
李志宏
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中兴电工机械股份有限公司
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Priority to PCT/CN2021/134945 priority Critical patent/WO2023097587A1/en
Publication of WO2023097587A1 publication Critical patent/WO2023097587A1/en

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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00Fuel cells; Manufacture thereof
    • H01M8/02Details
    • H01M8/0202Collectors; Separators, e.g. bipolar separators; Interconnectors
    • H01M8/0204Non-porous and characterised by the material
    • H01M8/0213Gas-impermeable carbon-containing materials
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30Hydrogen technology
    • Y02E60/50Fuel cells

Abstract

The present application provides a bipolar plate for a fuel cell. The bipolar plate is formed by laminating a substrate. The substrate is made of a soft graphite plate. The soft graphite plate has a density of 0.8-1.3 g/cm3, a carbon content of greater than 98% and an ash content of less than 2%; and based on the thickness of the substrate before lamination, the thickness compression ratio of the bipolar plate is 40-50%.

Description

电化学燃料电池双极板制备方法Electrochemical fuel cell bipolar plate preparation method 技术领域technical field
本发明实施例涉及燃料电池,且特别涉及燃料电池的双极板。Embodiments of the present invention relate to fuel cells, and in particular to bipolar plates for fuel cells.
背景技术Background technique
随着人口的增长和工业的发展,人类对于能源的需求也随之暴增。一直以来,石化燃料被重度依赖为最主要的能量来源,石油的使用带动了运输、科技与文明的进展,却也在各地造成了空气污染、引发了环境危机。由于能源与环境的双重压力,燃料电池的发展越来越受到各国政府的重视与支持。With the growth of population and the development of industry, human's demand for energy has also skyrocketed. For a long time, fossil fuels have been heavily relied on as the main source of energy. The use of petroleum has driven the progress of transportation, technology and civilization, but it has also caused air pollution and triggered environmental crises in various places. Due to the dual pressure of energy and the environment, the development of fuel cells has received more and more attention and support from governments.
质子交换膜燃料电池(Proton Exchange Membrane Fuel Cell,PEMFC)为目前各种燃料电池中,发展较为成熟者。质子交换膜燃料电池将燃料和空气中的化学能直接、连续地转化成电能。它的基本原理是在阳极侧通入燃料(例如氢气或者甲醇等),在阴极侧通入氧化剂(氧气或者空气等),并使之分别在催化剂的作用下发生电化学反应,生成水并产生电能。Proton Exchange Membrane Fuel Cell (PEMFC) is a relatively mature one among various fuel cells at present. Proton exchange membrane fuel cells convert the chemical energy in fuel and air directly and continuously into electrical energy. Its basic principle is to pass fuel (such as hydrogen or methanol, etc.) on the anode side and oxidant (oxygen or air, etc.) on the cathode side, and make them electrochemically react under the action of the catalyst to generate water and electrical energy.
双极板(阳极板、阴极板)在质子交换膜燃料电池中主要负责输送反应气体至触媒反应区进行电化学反应,并使反应气体均匀分布于膜电极组上,同时传导电化学反应产生的电流,另外在电池堆中,双极板亦有散热的功能。在质子交换膜燃料电池运作时,其内部的工作温度处于60~80℃之间,内部相对湿度通常为100%,且因电化学反应产生氢质子的关系,内部为一酸性环境(pH=2~3)。综合以上几点,可得知双极板材质必须具高导电性、良好的导热性及较佳的抗腐蚀能力,另外考虑到双极板上的流道加工,选用双极板材料时亦须考虑其加工特性。The bipolar plate (anode plate, cathode plate) in the proton exchange membrane fuel cell is mainly responsible for transporting the reaction gas to the catalyst reaction area for electrochemical reaction, and making the reaction gas evenly distributed on the membrane electrode group, and at the same time conducting the electrochemical reaction. In addition, in the battery stack, the bipolar plate also has the function of heat dissipation. When the proton exchange membrane fuel cell is in operation, its internal working temperature is between 60 and 80°C, the internal relative humidity is usually 100%, and due to the hydrogen protons generated by the electrochemical reaction, the internal is an acidic environment (pH=2 ~3). Based on the above points, it can be known that the material of the bipolar plate must have high electrical conductivity, good thermal conductivity and better corrosion resistance. In addition, considering the processing of the flow channel on the bipolar plate, it is also necessary to select the material of the bipolar plate. Consider its processing characteristics.
目前最常用的双极板材料是石墨,因其材料性质符合以上几个特点,但其缺点是材料成本高、机械强度较差、易脆及受限的加工性。石墨的机械特性使得大部分厂商对石墨双极板采取CNC(Computer Numerical Control)铣床加工,加工后的石墨双极板有着板件厚、体积大、重量重(传统石墨板重量约占电池堆总重的50~60%)等缺点,难以作为未来小型化及轻量化燃料电池的双极板材料。另外,由于CNC铣床加工过程复杂,加工周期较长,使石墨双极板的加工成本也难以降低。At present, the most commonly used bipolar plate material is graphite, because its material properties meet the above characteristics, but its disadvantages are high material cost, poor mechanical strength, brittleness and limited processability. Due to the mechanical properties of graphite, most manufacturers use CNC (Computer Numerical Control) milling machines to process graphite bipolar plates. The processed graphite bipolar plates are thick, bulky, and heavy (the weight of traditional graphite plates accounts for about 50% to 60% heavy) and other shortcomings, it is difficult to be used as a bipolar plate material for future miniaturization and lightweight fuel cells. In addition, due to the complex machining process of CNC milling machines and the long machining cycle, it is difficult to reduce the machining cost of graphite bipolar plates.
金属材料同样具有高导电性及良好的导热性,而其优异的延展性使其能以冲压或液压等方式成型,使板件的厚度可有效降低,因此使用金属双极板可进一步减少电池堆的体积与重 量,使电池堆单位体积和单位重量的功率密度能够提升。另外,金属双极板具有较好的抗震能力,可增加燃料电池动力系统未来应用于载具上的竞争力。除了以上较佳的机械性质所带来的优点外,金属的成本亦较石墨低,冲压成型方法亦可大幅缩短双极板生产的时间,因此可降低量产阶段的电池成本。但金属双极板的缺点是低抗腐蚀性,于高温、高湿度及酸性的燃料电池环境下,金属表面容易因腐蚀及氧化反应生成钝化层,进而使得接触阻抗增加,降低燃料电池发电效率,另一方面,金属离子亦可能伤害膜电极组性能。Metal materials also have high electrical conductivity and good thermal conductivity, and its excellent ductility enables it to be formed by stamping or hydraulic pressure, so that the thickness of the plate can be effectively reduced, so the use of metal bipolar plates can further reduce the battery stack The volume and weight of the battery stack can increase the power density per unit volume and unit weight. In addition, metal bipolar plates have good shock resistance, which can increase the competitiveness of fuel cell power systems applied to vehicles in the future. In addition to the advantages brought by the above better mechanical properties, the cost of metal is also lower than that of graphite, and the stamping method can also greatly shorten the production time of bipolar plates, thus reducing the cost of batteries in the mass production stage. However, the disadvantage of metal bipolar plates is low corrosion resistance. Under high temperature, high humidity and acidic fuel cell environments, the metal surface is prone to form a passivation layer due to corrosion and oxidation reactions, which in turn increases the contact resistance and reduces the power generation efficiency of the fuel cell. , On the other hand, metal ions may also damage the performance of MEA.
因此,目前双极板的开发技术仍面临许多问题。如何以低成本、高效率的方式提供耐久性的双极板仍是业界亟待解决的课题。Therefore, the current development technology of bipolar plates still faces many problems. How to provide durable bipolar plates in a low-cost and high-efficiency manner is still an urgent problem to be solved in the industry.
发明内容Contents of the invention
本发明实施例提供一种用于燃料电池的双极板,由基板压合而形成,其中基板由软性石墨板形成,软性石墨板的密度为0.8~1.3g/cm 3、碳含量>98%且灰分<2%,且以压合前的基板的厚度为基准,双极板的厚度压缩率为40~50%。 An embodiment of the present invention provides a bipolar plate for a fuel cell, which is formed by laminating substrates, wherein the substrate is formed of a flexible graphite plate, the density of the flexible graphite plate is 0.8-1.3g/cm 3 , and the carbon content> 98% and ash content<2%, and based on the thickness of the substrate before pressing, the thickness compression rate of the bipolar plate is 40-50%.
在一些实施例中,以压合前的基板的厚度为基准,双极板的厚度变形量为0.5~1mm。In some embodiments, based on the thickness of the substrate before lamination, the thickness deformation of the bipolar plate is 0.5-1 mm.
在一些实施例中,软性石墨板的含硫量<1000ppm且含氯量<50ppm。In some embodiments, the flexible graphite plate has a sulfur content of <1000 ppm and a chlorine content of <50 ppm.
在一些实施例中,双极板的密度为1~3g/cm 3In some embodiments, the density of the bipolar plates is 1-3 g/cm 3 .
在一些实施例中,双极板的流道深度<1mm。In some embodiments, the flow channel depth of the bipolar plate is <1 mm.
在一些实施例中,双极板的流道为回旋型流道、蛇型流道、指叉型流道、网格状流道或平行流道。In some embodiments, the flow channel of the bipolar plate is a convoluted flow channel, a serpentine flow channel, an interdigitated flow channel, a grid-like flow channel or a parallel flow channel.
本发明实施例还提供一种燃料电池,包括:质子交换膜;一对触媒层,分别设置于质子交换膜的两侧;一对双极板,分别设置于触媒层的外侧,将质子交换膜及触媒层夹持于中间,其中双极板为上述实施例中任一例的双极板。The embodiment of the present invention also provides a fuel cell, comprising: a proton exchange membrane; a pair of catalyst layers, respectively arranged on both sides of the proton exchange membrane; a pair of bipolar plates, respectively arranged on the outside of the catalyst layer, the proton exchange membrane And the catalyst layer is clamped in the middle, wherein the bipolar plate is the bipolar plate of any example in the above-mentioned embodiments.
本发明实施例又提供一种用于燃料电池的双极板的制造方法,包括:刀模裁切步骤,将软性石墨板裁切成基板;匹配步骤,将基板放置于模具中;压合步骤,将放置有基板的模具进行压合;以及脱模步骤,将压合后的基板与模具分离,以得到双极板,其中软性石墨板的密度为0.8~1.3g/cm 3、碳含量>98%且灰分<2%,且以压合前的基板的厚度为基准,双极板的厚度压缩率为40~50%。 An embodiment of the present invention further provides a method for manufacturing a bipolar plate for a fuel cell, including: a die cutting step, cutting the soft graphite plate into a substrate; a matching step, placing the substrate in a mold; pressing step, pressing the mold on which the substrate is placed; and a demolding step, separating the pressed substrate from the mold to obtain a bipolar plate, wherein the density of the soft graphite plate is 0.8-1.3g/cm 3 , carbon The content is >98% and the ash content is <2%, and based on the thickness of the substrate before lamination, the thickness compression rate of the bipolar plate is 40-50%.
在一些实施例中,模具具有1~10°的拔模角。In some embodiments, the mold has a draft angle of 1-10°.
在一些实施例中,压合步骤的压合磅数为300~1500kg/cm 2In some embodiments, the pressing weight of the pressing step is 300-1500 kg/cm 2 .
在一些实施例中,压合步骤在常温下进行。In some embodiments, the pressing step is performed at room temperature.
在一些实施例中,压合步骤的持续时间为0.05~3min。In some embodiments, the duration of the pressing step is 0.05-3 minutes.
附图说明Description of drawings
以下将配合附图详述本发明实施例。应注意的是,依据在本领域的标准做法,各种特征并未按照比例绘制且仅用以说明例示。事实上,可任意地放大或缩小元件的尺寸,以清楚地表现出本发明实施例的特征。Embodiments of the present invention will be described in detail below with reference to the accompanying drawings. It should be noted that, in accordance with standard practice in the art, the various features are not drawn to scale and are used for illustrative purposes only. In fact, the dimensions of the elements may be arbitrarily expanded or reduced to clearly illustrate the features of the embodiments of the invention.
图1A~1E为根据一些实施列,绘示出双极板的流道的局部示意图。1A-1E are partial schematic diagrams illustrating flow channels of a bipolar plate, according to some embodiments.
图2为根据一些实施列,绘示出燃料电池的局部示意图。FIG. 2 is a partial schematic diagram illustrating a fuel cell, according to some embodiments.
图3A为根据一些实施列,绘示基板放置于模具中并进行压合的示意图。FIG. 3A is a schematic diagram illustrating a substrate placed in a mold and pressed together, according to some embodiments.
图3B为根据一些实施列,绘示出脱模后所获得双极板的示意图。FIG. 3B is a schematic diagram illustrating a bipolar plate obtained after demolding, according to some embodiments.
图4A~4B为根据一些实施列,绘示出模具的局部侧视图。4A-4B are partial side views illustrating a mold, according to some embodiments.
附图标记reference sign
10:双极板;10: bipolar plate;
10a:阳极板;10a: anode plate;
10b:阴极板;10b: cathode plate;
12:流道;12: runner;
12a:流道;12a: runner;
12b:流道;12b: runner;
13:流道;13: runner;
13a:流道;13a: runner;
13b:流道;13b: runner;
14:流道入口;14: Runner entrance;
16:流道出口;16: runner outlet;
20:质子交换膜;20: proton exchange membrane;
30a:阳极触媒层;30a: anode catalyst layer;
30b:阴极触媒层;30b: cathode catalyst layer;
50:基板;50: substrate;
100:燃料电池;100: fuel cell;
300:模具;300: mold;
d1:厚度;d1: thickness;
d2:厚度d2: thickness
具体实施方式Detailed ways
以下揭露提供了许多的实施例或范例,用于实施所提供的目标物的不同元件。各元件和其配置的具体范例描述如下,以简化本发明实施例的说明。当然,这些仅仅是范例,并非用以限定本发明实施例。举例而言,叙述中若提及第一元件形成在第二元件之上,可能包含第一和第二元件直接接触的实施例,也可能包含额外的元件形成在第一和第二元件之间,使得它们不直接接触的实施例。此外,本发明实施例可能在各种范例中重复参考数值或字母。如此重复是为了简明和清楚的目的,而非用以表示所讨论的不同实施例或配置之间的关系。The following disclosure provides a number of embodiments or examples for implementing different elements of the provided object. Specific examples of each element and its configuration are described below to simplify the description of the embodiments of the present invention. Of course, these are just examples, not intended to limit the embodiments of the present invention. For example, if the description mentions that a first element is formed on a second element, it may include an embodiment in which the first and second elements are in direct contact, or may include an additional element formed between the first and second elements , so that they are not in direct contact with the example. In addition, the embodiments of the present invention may repeat reference numerals or letters in various examples. This repetition is for the purpose of brevity and clarity and not to show the relationship between the different embodiments or configurations discussed.
再者,其中可能用到与空间相对用词,例如“在……之下”、“下方”、“较低的”、“上方”、“较高的”等类似用词,是为了便于描述图中一个(些)部件或特征与另一个(些)部件或特征之间的关系。空间相对用词用以包括使用中或操作中的装置的不同方位,以及图中所描述的方位。当装置被转向不同方位时(旋转90度或其他方位),其中所使用的空间相对形容词也将依转向后的方位来解释。Furthermore, words relative to space may be used, such as "below", "below", "lower", "above", "higher" and similar words, for the convenience of description The relationship between one component or feature(s) and another component(s) or feature(s) in the drawings. Spatially relative terms are intended to encompass different orientations of the device in use or operation, as well as the orientations depicted in the figures. When the device is turned to a different orientation (rotated 90 degrees or otherwise), the spatially relative adjectives used therein shall also be interpreted in accordance with the turned orientation.
本揭露提供一种用于燃料电池的双极板,其主要特点是,所述双极板是由软性石墨板直接压合而形成,可以低成本、高效率的方式提供高耐久性的燃料电池双极板。The disclosure provides a bipolar plate for a fuel cell, the main feature of which is that the bipolar plate is formed by direct pressing of a soft graphite plate, which can provide high-durability fuel in a low-cost and high-efficiency manner Battery bipolar plates.
本案中所称之“软性石墨板”是指密度0.8~1.3g/cm 3、抗拉强度40~50kg/cm 2、碳含量>98%、灰分<2%的石墨板。根据一些实施例,软性石墨板可以为例如膨胀石墨材料制作而成。根据一些实施例,膨胀石墨材料可为例如,由天然鳞片石墨经插层处理、水洗、干燥、高温膨胀制得。膨胀石墨特殊的结构和特性使其拥有天然石墨的性质外,还具有其它优良的性质,例如:高耐压性、柔韧性、可塑性和自润滑性;高抗高温、低温、抗腐蚀、抗辐射特性;高抗震特性;高电导率;高抗老化、抗扭曲的特性等。根据一些实施例,软性石墨板的密度为约0.8~1.3g/cm 3(例如0.9~1g/cm 3、0.95~1.2g/cm 3)。根据一些实施例,软性石墨板的碳含量>98%(例如>98.5%、>99%、>99.5%)且灰分<2%(例如<1.5%、<1%、<0.5%)。本案通过软性石墨板高含碳量的性质达到高导热及导电特性,以符合燃料电池电化学反应的需求。 The "soft graphite plate" referred to in this case refers to a graphite plate with a density of 0.8-1.3 g/cm 3 , a tensile strength of 40-50 kg/cm 2 , a carbon content >98%, and an ash content <2%. According to some embodiments, the flexible graphite plate may be made of expanded graphite material, for example. According to some embodiments, the expanded graphite material can be, for example, made of natural flake graphite through intercalation treatment, water washing, drying, and high-temperature expansion. The special structure and characteristics of expanded graphite make it not only have the properties of natural graphite, but also have other excellent properties, such as: high pressure resistance, flexibility, plasticity and self-lubrication; high resistance to high temperature, low temperature, corrosion resistance, radiation resistance Characteristics; high shock resistance; high electrical conductivity; high anti-aging, anti-distortion characteristics, etc. According to some embodiments, the flexible graphite plate has a density of about 0.8-1.3 g/cm 3 (eg, 0.9-1 g/cm 3 , 0.95-1.2 g/cm 3 ). According to some embodiments, the flexible graphite plate has a carbon content >98% (eg >98.5%, >99%, >99.5%) and an ash content <2% (eg <1.5%, <1%, <0.5%). In this case, the high carbon content of the flexible graphite plate achieves high thermal conductivity and electrical conductivity, so as to meet the needs of the electrochemical reaction of the fuel cell.
根据一些实施例,软性石墨板经过裁切而形成基板。根据一些实施例,软性石墨板中不含树脂,故裁切后的基板直接压合而形成的双极板能够维持高电导率的特性。根据一些实施例,软性石墨板的抗拉强度为约40~50kg/cm 2(例如42~45kg/cm 2、43~48kg/cm 2)。根据一些实施例,软性石墨板的压缩率>40%(例如>50%、>60%)。 According to some embodiments, the flexible graphite sheet is cut to form the substrate. According to some embodiments, the flexible graphite plate does not contain resin, so the bipolar plate formed by directly pressing the cut substrates can maintain the characteristic of high electrical conductivity. According to some embodiments, the tensile strength of the flexible graphite sheet is about 40-50 kg/cm 2 (eg, 42-45 kg/cm 2 , 43-48 kg/cm 2 ). According to some embodiments, the compressibility of the flexible graphite sheet is >40% (eg >50%, >60%).
根据一些实施例,以压合前的基板的厚度为基准,双极板的厚度压缩率为40~50%(例 如42~45%、43~48%),即以压合前的基板的厚度为比较基准,压合后形成的双极板的厚度减少了40~50%。其中,所述基板的厚度为基板整体的最大厚度,所述双极板的厚度为双极板整体的最大厚度。根据一些实施例,以压合前的基板的厚度为基准,双极板的厚度变形量为0.5~1mm(例如0.6~0.9mm、0.7~0.8mm)。一般而言,软性石墨需要经过树脂的浸渍,以获得较高的机械强度,然而,本案通过控制双极板的厚度压缩率及/或双极板的厚度变形量,可使软性石墨形成的双极板获得足够的钢性的前提下保持不碎裂。若双极板的厚度压缩率过低,则会造成双极板的强度过低、阻抗值过高。若双极板的厚度压缩率过高,则会造成双极板脱模难度增加,且容易在压缩过程中碎裂。根据一些实施例,双极板的密度为约1~3g/cm 3(例如1.2~2.5g/cm 3、1.6~2g/cm 3)。 According to some embodiments, based on the thickness of the substrate before lamination, the thickness compression rate of the bipolar plate is 40-50% (such as 42-45%, 43-48%), that is, based on the thickness of the substrate before lamination As a comparison basis, the thickness of the bipolar plate formed after pressing is reduced by 40-50%. Wherein, the thickness of the substrate is the maximum thickness of the entire substrate, and the thickness of the bipolar plate is the maximum thickness of the entire bipolar plate. According to some embodiments, based on the thickness of the substrate before lamination, the thickness deformation of the bipolar plate is 0.5-1 mm (eg, 0.6-0.9 mm, 0.7-0.8 mm). Generally speaking, soft graphite needs to be impregnated with resin to obtain higher mechanical strength. However, in this case, the soft graphite can be formed by controlling the thickness compressibility of the bipolar plate and/or the thickness deformation of the bipolar plate. Under the premise of obtaining sufficient rigidity, the bipolar plate remains unbroken. If the thickness compressibility of the bipolar plate is too low, the strength of the bipolar plate will be too low and the impedance value will be too high. If the thickness compression rate of the bipolar plate is too high, it will increase the difficulty of demolding the bipolar plate, and it is easy to break during the compression process. According to some embodiments, the density of the bipolar plates is about 1-3 g/cm 3 (eg, 1.2-2.5 g/cm 3 , 1.6-2 g/cm 3 ).
根据一些实施例,软性石墨板的含硫量<1000ppm且含氯量<50ppm,通过控制软性石墨板中含硫量及含氯量,可以抑制对燃料电池中触媒的影响,从而提高燃料电池的耐久性。According to some embodiments, the sulfur content of the flexible graphite plate<1000ppm and the chlorine content<50ppm, by controlling the sulfur content and the chlorine content in the flexible graphite plate, the impact on the catalyst in the fuel cell can be suppressed, thereby improving fuel efficiency. battery durability.
可以根据不同的模具设计而获得具有不同流道的双极板。参考图1A~1E,根据一些实施例,双极板10具有流道12、流道入口14及流道出口16等。流道12可为例如回旋型流道(如图1A)、蛇型流道(如图1B)、指叉型流道(如图1C)、网格状流道(如图1D)或平行流道(如图1E)等。根据一些实施例,双极板10的流道深度约<1mm(例如<0.8mm、<0.5mm)。Bipolar plates with different flow channels can be obtained according to different mold designs. Referring to FIGS. 1A-1E , according to some embodiments, a bipolar plate 10 has flow channels 12 , flow channel inlets 14 , flow channel outlets 16 , and the like. The flow channel 12 can be, for example, a convoluted flow channel (as shown in Figure 1A), a serpentine flow channel (as shown in Figure 1B), an interdigitated flow channel (as shown in Figure 1C), a grid-shaped flow channel (as shown in Figure 1D) or a parallel flow channel Road (as shown in Figure 1E) and so on. According to some embodiments, the channel depth of the bipolar plate 10 is about <1 mm (eg <0.8 mm, <0.5 mm).
根据一些实施例,本案的双极板可以作为燃料电池的双极板(阳极板及/或阴极板)。根据一些实施例,本案双极板上的流道可以作为气体流道(例如氢气、空气等)及/或液体流道(例如冷却液或甲醇等)。根据一些实施例,双极板可以在两面上皆具有流道。根据一些实施例,双极板可以在单面上具有流道。According to some embodiments, the bipolar plate of the present application can be used as a bipolar plate (anode plate and/or cathode plate) of a fuel cell. According to some embodiments, the flow channels on the bipolar plate of the present invention can be used as gas flow channels (such as hydrogen, air, etc.) and/or liquid flow channels (such as cooling liquid or methanol, etc.). According to some embodiments, bipolar plates may have flow channels on both sides. According to some embodiments, a bipolar plate may have flow channels on a single face.
参照图2,根据一些实施例,图2为使用本案双极板的燃料电池100的局部示意图。根据一些实施例,燃料电池100可为多个单电池串接而成。根据一些实施例,燃料电池100包括质子交换膜20。根据一些实施例,燃料电池100包括一对触媒层(阳极触媒层30a及阴极触媒层30b),分别设置于质子交换膜20的两侧。根据一些实施例,燃料电池100包括一对双极板(阳极板10a及阴极板10b),分别设置于阳极触媒层30a及阴极触媒层30b的外侧,并将质子交换膜20、阳极触媒层30a及阴极触媒层30b夹持于中间。根据一些实施例,氢气从阳极板10a的进气口进入流道12a,并通过气体扩散层(未绘示)扩散至阳极触媒层30a。根据一些实施例,空气从阴极板10b的进气口进入流道12b,并通过气体扩散层(未绘示)扩散至阴极触媒层30b。经由阳极触媒层30a的作用,使阳极的氢原子分解成两个氢质子与两个电子,其中质子被“吸引”到质子交换膜20的另一边,电子则经由外电路形成电流后,到达阴极。在阴极触媒层30b之作用下,氢质子、氧及电子反应形成水分子。根据一些实施例, 阳极触媒层30a可包括例如Pt、Ru、Ni等。根据一些实施例,阴极触媒层30b可包括例如Pt、Ni等。根据一些实施例,燃料电池100的阳极板10a及阴极板10b还可分别具有流道13a及流道13b。根据一些实施例,流道13a及流道13b为冷却液的流道。虽然燃料电池较传统内燃机有较佳转移效率,但仍有约50%的能量以废热形式逸散。因此,流道13a及13b可使冷却液分别在阳极板10a及阴极板10b的表面上流量分布均匀,达到散热均匀的效果。应可理解的是,燃料电池100可更包括集电板、端板、密封层等其他现有元件,为简化起见,在此不予详述。Referring to FIG. 2 , according to some embodiments, FIG. 2 is a partial schematic diagram of a fuel cell 100 using a bipolar plate of the present invention. According to some embodiments, the fuel cell 100 may be composed of multiple single cells connected in series. According to some embodiments, fuel cell 100 includes proton exchange membrane 20 . According to some embodiments, the fuel cell 100 includes a pair of catalyst layers (an anode catalyst layer 30 a and a cathode catalyst layer 30 b ), respectively disposed on two sides of the proton exchange membrane 20 . According to some embodiments, the fuel cell 100 includes a pair of bipolar plates (anode plate 10a and cathode plate 10b), which are respectively arranged on the outside of the anode catalyst layer 30a and the cathode catalyst layer 30b, and the proton exchange membrane 20, the anode catalyst layer 30a And the cathode catalyst layer 30b is sandwiched in the middle. According to some embodiments, the hydrogen enters the channel 12a from the gas inlet of the anode plate 10a, and diffuses to the anode catalyst layer 30a through the gas diffusion layer (not shown). According to some embodiments, the air enters the channel 12b from the air inlet of the cathode plate 10b, and diffuses to the cathode catalyst layer 30b through a gas diffusion layer (not shown). Through the action of the anode catalyst layer 30a, the hydrogen atoms at the anode are decomposed into two hydrogen protons and two electrons, among which the protons are "attracted" to the other side of the proton exchange membrane 20, and the electrons reach the cathode through an external circuit to form a current . Under the action of the cathode catalyst layer 30b, hydrogen protons, oxygen and electrons react to form water molecules. According to some embodiments, the anode catalyst layer 30a may include, for example, Pt, Ru, Ni, or the like. According to some embodiments, the cathode catalyst layer 30b may include, for example, Pt, Ni, or the like. According to some embodiments, the anode plate 10a and the cathode plate 10b of the fuel cell 100 may further have a flow channel 13a and a flow channel 13b respectively. According to some embodiments, the flow channel 13a and the flow channel 13b are cooling liquid flow channels. Although fuel cells have better transfer efficiency than conventional internal combustion engines, about 50% of the energy is still dissipated as waste heat. Therefore, the flow channels 13a and 13b can make the flow distribution of the cooling liquid on the surface of the anode plate 10a and the cathode plate 10b respectively uniform, so as to achieve the effect of uniform heat dissipation. It should be understood that the fuel cell 100 may further include collector plates, end plates, sealing layers and other existing components, which are not described in detail here for simplicity.
以下,将进一步描述双极板的制造方法。Hereinafter, the manufacturing method of the bipolar plate will be further described.
根据一些实施例,双极板的制造包括刀模裁切步骤,将软性石墨板裁切成基板。软性石墨板可以直接使用市售的软性石墨板。根据一些实施例,裁切前的软性石墨板的尺寸可为例如长约20~40cm(例如约23~35cm、25~30cm)、宽约20~40cm(例如约23~35cm、25~30cm)、高约0.3~3cm(例如约1~2.8cm、1.5~2.5cm)。裁切后的基板的大小可以根据需求而设定,可为例如长约3~30cm(例如约10~28cm、15~20cm)、宽约3~30cm(例如约10~28cm、15~20cm)、高约0.3~3cm(例如约1~2.8cm、1.5~2.5cm)。另外,可以裁切出流道出口、流道入口(气体出、入口及/或冷却液出、入口),并可根据实际产品需求,设定裁切的流道出口、流道入口的位置及大小。According to some embodiments, the fabrication of the bipolar plates includes a die cutting step, cutting the flexible graphite plates into substrates. As the soft graphite plate, a commercially available soft graphite plate can be directly used. According to some embodiments, the size of the flexible graphite plate before cutting can be, for example, about 20-40 cm long (for example, about 23-35 cm, 25-30 cm), and about 20-40 cm wide (for example, about 23-35 cm, 25-30 cm ), about 0.3-3cm high (for example about 1-2.8cm, 1.5-2.5cm). The size of the cut substrate can be set according to requirements, for example, it can be about 3-30cm long (for example, about 10-28cm, 15-20cm), and about 3-30cm wide (for example, about 10-28cm, 15-20cm) , about 0.3-3cm in height (for example about 1-2.8cm, 1.5-2.5cm). In addition, the runner outlet and runner inlet (gas outlet and inlet and/or coolant outlet and inlet) can be cut out, and the position and location of the cut runner outlet and runner inlet can be set according to actual product requirements. size.
根据一些实施例,在刀模裁切步骤之后进行匹配步骤,如图3A所示,将基板50放置于模具300中,其中基板50的厚度为d1。根据一些实施例,可以根据需求制造并挑选合适的模具300,通过设定模具300上的纹路,可以决定压合后所形成的双极板的流道形状,并通过模具外框设定双极板的大小。According to some embodiments, a matching step is performed after the die cutting step. As shown in FIG. 3A , the substrate 50 is placed in the mold 300 , wherein the thickness of the substrate 50 is d1 . According to some embodiments, a suitable mold 300 can be manufactured and selected according to requirements. By setting the texture on the mold 300, the shape of the flow path of the bipolar plate formed after lamination can be determined, and the bipolar plate can be set by the outer frame of the mold. board size.
根据一些实施例,在匹配步骤之后进行压合步骤,将放置有基板50的模具300进行压合。通过压力的施加,使基板50随着模具300的纹路变形,从而形成具有特定流道的形状。根据一些实施例,压合步骤的压合磅数约为300~1500kg/cm 2(例如500~1300kg/cm 2、650~1200kg/cm 2、700~1000kg/cm 2)。通过将压合磅数控制在此范围内,可控制双极板的厚度压缩率及/或厚度变形量,使双极板具有足够刚性。根据一些实施例,压合步骤在常温下进行且压合步骤的持续时间约为0.05~3min(例如1~2.5min、1.5~2.3min)。 According to some embodiments, a pressing step is performed after the matching step, and the mold 300 on which the substrate 50 is placed is subjected to pressing. Through the application of pressure, the substrate 50 is deformed along with the pattern of the mold 300 to form a shape with a specific flow channel. According to some embodiments, the pressing weight of the pressing step is about 300-1500 kg/cm 2 (eg, 500-1300 kg/cm 2 , 650-1200 kg/cm 2 , 700-1000 kg/cm 2 ). By controlling the pressing weight within this range, the thickness compressibility and/or thickness deformation of the bipolar plate can be controlled, so that the bipolar plate has sufficient rigidity. According to some embodiments, the pressing step is performed at normal temperature and the duration of the pressing step is about 0.05-3 minutes (eg, 1-2.5 minutes, 1.5-2.3 minutes).
根据一些实施例,在压合步骤之后进行脱模步骤,通过大力往下撞击脱模底座,将压合后的基板50与模具300分离,得到具有流道12及流道13的双极板10,如图3B所示,其中双极板10整体的最大厚度为d2。根据一些实施例,以压合前的基板50的厚度d1为基准,双极板10的厚度压缩率为40~50%,即(d2/d1)×100%=40~50%。根据一些实施例,整个 制程的过程不超过5min(例如1~4min、2~3min),大大缩短了双极板的加工时间。According to some embodiments, the demoulding step is performed after the pressing step, and the pressed substrate 50 is separated from the mold 300 by vigorously hitting the demoulding base downward, so as to obtain the bipolar plate 10 having the flow channel 12 and the flow channel 13 , as shown in FIG. 3B , wherein the maximum thickness of the bipolar plate 10 as a whole is d2. According to some embodiments, based on the thickness d1 of the substrate 50 before lamination, the thickness compression rate of the bipolar plate 10 is 40-50%, ie (d2/d1)×100%=40-50%. According to some embodiments, the entire manufacturing process takes no more than 5 minutes (such as 1-4 minutes, 2-3 minutes), which greatly shortens the processing time of the bipolar plate.
根据一些实施例,压力合磅数与双极板的厚度变形量具有如表1的关系。其中,实施例中使用的基板的长约5~25cm、宽约5~25cm、高约0.5~2cm,压合时间为1~2min。According to some embodiments, the combined pressure in pounds and the thickness deformation of the bipolar plate have a relationship as shown in Table 1. Wherein, the substrate used in the embodiment has a length of about 5-25 cm, a width of about 5-25 cm, and a height of about 0.5-2 cm, and the pressing time is 1-2 min.
表1Table 1
油压缸总输力(kgf)Total output force of hydraulic cylinder (kgf) 压合磅数(kg/cm 2) Pressing pounds (kg/cm 2 ) 厚度变形量(mm)Thickness deformation (mm)
00 00 00
5,0005,000 312.5312.5 0.8030.803
10,00010,000 625625 0.9190.919
15,00015,000 937.5937.5 0.9460.946
20,00020,000 1,2501,250 0.9890.989
根据一些实施例,模具具有1~10°的拔模角。根据一些实施例,模具更具有导/圆角的设计。拔模角也就是脱模斜度,是为了方便出模而在模膛两侧设计的斜度。为了让成型品可以顺利顶出脱离模具,在与模具开闭相同方向的壁面,必须设定拔模角以利脱模。由于软性石墨板较容易沾黏在模具上,通过将模具的拔模角设定在1~10°的范围,可以降低脱模时的摩擦力,使双极板完整脱离。传统直角设计的模具,不具拔模角,在之后的脱模上较为困难。以下参照图4A~4B。根据一些实施例,图4A为模具300的局部侧视图。其中模具300侧壁与其垂直方向上的夹角即为拔模角s。具有拔模角s的模具300在脱模时可以减少模具与被压合材料在垂直方向上的摩擦力,因此可以使被压合材料在脱模上更为容易。根据一些实施例,拔模角s可为约1~约10°(例如约2~8°、约3~6°)。根据一些实施例,模具300除了拔模角之外,还具有导/圆角的设计,如图4B所示,进一步降低了摩擦力。According to some embodiments, the mold has a draft angle of 1-10°. According to some embodiments, the mold has a lead/rounded design. The draft angle is the slope of the mold, which is the slope designed on both sides of the cavity for the convenience of mold release. In order to allow the molded product to be ejected from the mold smoothly, the draft angle must be set on the wall in the same direction as the opening and closing of the mold to facilitate demoulding. Since the soft graphite plate is easier to stick to the mold, by setting the draft angle of the mold in the range of 1-10°, the friction force during demolding can be reduced, and the bipolar plate can be completely separated. The mold with traditional right-angle design does not have a draft angle, which makes it difficult to demould later. 4A to 4B are referred to below. Figure 4A is a partial side view of mold 300, according to some embodiments. The angle between the side wall of the mold 300 and its vertical direction is the draft angle s. The mold 300 with the draft angle s can reduce the friction between the mold and the material to be pressed in the vertical direction during demoulding, so that the material to be pressed can be released from the mold more easily. According to some embodiments, the draft angle s may be about 1° to about 10° (eg, about 2° to 8°, about 3° to 6°). According to some embodiments, in addition to the draft angle, the mold 300 also has a lead/round corner design, as shown in FIG. 4B , which further reduces friction.
根据一些实施例,在脱模后,可透过各个物理检测,以确认双极板的成品规格符合产品的要求。例如,可利用厚度计对双极板进行厚度检测;利用深度规对双极板进行流道深度的检测;利用卡尺对双极板进行长度的检测。根据一些实施例,可将双极板贴合进行漏气检测。根据一些实施例,可对双极板进行抗阻试验及电性测试。According to some embodiments, after demoulding, various physical inspections can be performed to confirm that the finished specification of the bipolar plate meets the requirements of the product. For example, a thickness gauge can be used to detect the thickness of the bipolar plate; a depth gauge can be used to detect the depth of the flow channel of the bipolar plate; a caliper can be used to detect the length of the bipolar plate. According to some embodiments, bipolar plates may be bonded for gas leak detection. According to some embodiments, an impedance test and an electrical test may be performed on the bipolar plate.
由于石墨材质易碎,故石墨所制造的双极板加工难度大,且加工时间长,一片纯石墨双极板需要数小时的加工时间。相对于此,本案的软性石墨板具有较高的可塑性,仅需在常温 下进行短时间的压合即可完成双极板的加工(例如<5min),大大降低了双极板加工的时间及成本,节省了至少90%的加工时间,90.2%的加工成本。且由于软性石墨板的柔韧性,比起石墨材料,具有较佳的抗震性,更适合运用在例如电动车等的载具上。另外,石墨的价格较高,一片纯石墨双极板仅材料费就需要上千元,而软性石墨板所制作的双极板的材料费只需几十元,节省了至少90%的材料成本。另外,本案通过软性石墨板制造的双极板可通过气密检测及电性测试证明其材料对燃料电池性能不会造成影响。即,通过本案通过软性石墨板压合而形成的双极板,可以在不降低燃料电池性能的情况下,节省制造费用,并且缩短制造时间。Due to the fragility of graphite, the processing of bipolar plates made of graphite is difficult and takes a long time. A piece of pure graphite bipolar plate requires several hours of processing time. In contrast, the soft graphite plate in this case has high plasticity, and the processing of the bipolar plate can be completed only by short-term pressing at room temperature (for example, <5min), which greatly reduces the processing time of the bipolar plate And cost, saving at least 90% of the processing time, 90.2% of the processing cost. Moreover, due to the flexibility of the soft graphite plate, compared with the graphite material, it has better shock resistance, and is more suitable for use on vehicles such as electric vehicles. In addition, the price of graphite is relatively high. The material cost of a pure graphite bipolar plate costs thousands of yuan, while the material cost of a bipolar plate made of soft graphite plate is only tens of yuan, saving at least 90% of the material. cost. In addition, the bipolar plate made of flexible graphite plate in this case can pass the airtight test and electrical test to prove that its material will not affect the performance of the fuel cell. That is to say, the bipolar plate formed by pressing the soft graphite plate in this application can save the manufacturing cost and shorten the manufacturing time without reducing the performance of the fuel cell.
金属双极板虽然可通过冲压制程而迅速的完成加工,且金属的成本亦较石墨低,但在燃料高温、高湿度及酸性的环境下,金属双极板容易发生氧化,须另外施作(镀)抗氧化表面处理,故其耐久性较低。而本案使用的软性石墨板不会有氧化的问题,更适合在长期使用的产品中。Although the metal bipolar plate can be processed quickly through the stamping process, and the cost of the metal is lower than that of graphite, but in the environment of high temperature, high humidity and acidity of the fuel, the metal bipolar plate is prone to oxidation, and additional processing is required ( Plating) anti-oxidation surface treatment, so its durability is low. However, the soft graphite plate used in this case will not have the problem of oxidation, and is more suitable for long-term use products.
总上所述,本案由软性石墨板制成的双极板具有成本低廉、加工快速、耐久性佳等优点。In summary, the bipolar plate made of soft graphite plate in this case has the advantages of low cost, fast processing, and good durability.
以上概述数个实施例的部件,以便本领域技术人员可更易理解本发明实施例的观点。本领域技术人员应理解,他们能以本发明实施例为基础,设计或修改其他制程和结构,以达到与在此介绍的实施例相同的目的或优势。本领域技术人员也应理解到,此类等效的制程和结构并无悖离本发明的精神与范围,且他们能在不违背本发明之精神和范围之下,做各式各样的改变、取代和替换。The components of several embodiments are summarized above so that those skilled in the art can understand the viewpoints of the embodiments of the present invention more easily. Those skilled in the art should understand that they can design or modify other processes and structures based on the embodiments of the present invention, so as to achieve the same purpose or advantages as the embodiments introduced here. Those skilled in the art should also understand that such equivalent processes and structures do not depart from the spirit and scope of the present invention, and they can make various changes without departing from the spirit and scope of the present invention , Replace and Replace.
尽管已经用特定于结构特征或方法动作的语言描述了目标物,但是应该理解,所请求范围的目标物不必限于上述特定特征或动作。而是,上述特定特征和动作作为实现至少一些请求范围的范例形式被揭露。Although objects have been described in language specific to structural features or methodological acts, it is to be understood that objects of claimed scope are not necessarily limited to the specific features or acts described above. Rather, the specific features and acts described above are disclosed as example forms of implementing at least some of the claimed scope.

Claims (12)

  1. 一种用于燃料电池的双极板,由一基板压合而形成,其特征在于,所述的基板由软性石墨板形成,所述的软性石墨板的密度为0.8~1.3g/cm 3、碳含量>98%且灰分<2%,且以压合前的该基板的厚度为基准,所述的双极板的厚度压缩率为40~50%。 A bipolar plate for a fuel cell, formed by pressing a substrate, characterized in that the substrate is formed of a flexible graphite plate, and the density of the flexible graphite plate is 0.8 to 1.3 g/cm 3. The carbon content is >98% and the ash content is <2%, and based on the thickness of the substrate before lamination, the thickness compressibility of the bipolar plate is 40-50%.
  2. 根据权利要求1所述的双极板,其特征在于,以压合前的该基板的厚度为基准,所述的双极板的厚度变形量为0.5~1mm。The bipolar plate according to claim 1, characterized in that, based on the thickness of the substrate before lamination, the thickness deformation of the bipolar plate is 0.5-1 mm.
  3. 根据权利要求1所述的双极板,其特征在于,所述的软性石墨板的含硫量<1000ppm且含氯量<50ppm。The bipolar plate according to claim 1, characterized in that the sulfur content of the flexible graphite plate is <1000ppm and the chlorine content is <50ppm.
  4. 根据权利要求1所述的双极板,其特征在于,所述的双极板的密度为1~3g/cm 3The bipolar plate according to claim 1, characterized in that, the density of the bipolar plate is 1˜3 g/cm 3 .
  5. 根据权利要求1所述的双极板,其特征在于,所述的双极板的流道深度<1mm。The bipolar plate according to claim 1, characterized in that, the flow channel depth of the bipolar plate is <1 mm.
  6. 根据权利要求1所述的双极板,其特征在于,所述的双极板的流道为回旋型流道、蛇型流道、指叉型流道、网格状流道或平行流道。The bipolar plate according to claim 1, wherein the flow channel of the bipolar plate is a convoluted flow channel, a serpentine flow channel, an interdigitated flow channel, a grid-like flow channel or a parallel flow channel .
  7. 一种燃料电池,其特征在于,包括:A fuel cell, characterized in that it comprises:
    质子交换膜;Proton exchange membrane;
    一对触媒层,分别设置于所述的质子交换膜的两侧;A pair of catalyst layers are respectively arranged on both sides of the proton exchange membrane;
    一对双极板,分别设置于所述的一对触媒层的外侧,将所述的质子交换膜及所述的一对触媒层夹持于中间,其中所述的一对双极板为权利要求1~6中任一项的双极板。A pair of bipolar plates are respectively arranged on the outside of the pair of catalyst layers, sandwiching the proton exchange membrane and the pair of catalyst layers in the middle, wherein the pair of bipolar plates are right Any bipolar plate from 1 to 6 is required.
  8. 一种用于燃料电池的双极板的制备方法,其特征在于,包括:A method for preparing a bipolar plate for a fuel cell, characterized in that it comprises:
    刀模裁切步骤,将软性石墨板裁切成基板;Die cutting step, cutting the soft graphite plate into a substrate;
    匹配步骤,将所述的基板放置于模具中;Matching step, placing the substrate in the mold;
    压合步骤,将放置有所述的基板的该模具进行压合;以及A pressing step of pressing the mold on which the substrate is placed; and
    脱模步骤,将压合后的该基板与所述的模具分离,以得到所述的双极板,其中所述的软性石墨板的密度为0.8~1.3g/cm 3、碳含量>98%且灰分<2%,且以压合前的该基板的厚度为基准,所述的双极板的厚度压缩率为40~50%。 The demolding step is to separate the laminated substrate from the mold to obtain the bipolar plate, wherein the flexible graphite plate has a density of 0.8-1.3 g/cm 3 and a carbon content of >98 % and the ash content <2%, and based on the thickness of the substrate before lamination, the thickness compressibility of the bipolar plate is 40-50%.
  9. 根据权利要求8所述的双极板的制备方法,其特征在于,所述的模具具有1~10°的拔模角。The method for preparing a bipolar plate according to claim 8, wherein the mold has a draft angle of 1-10°.
  10. 根据权利要求8所述的双极板的制备方法,其特征在于,所述的压合步骤的压合磅数为300~1500kg/cm 2The preparation method of the bipolar plate according to claim 8, characterized in that, the pressing weight of the pressing step is 300-1500 kg/cm 2 .
  11. 根据权利要求8所述的双极板的制备方法,其特征在于,所述的压合步骤在常温下进行。The preparation method of the bipolar plate according to claim 8, characterized in that, the pressing step is carried out at normal temperature.
  12. 根据权利要求11所述的双极板的制备方法,其特征在于,所述的压合步骤的持续时间为0.05~3min。The method for preparing a bipolar plate according to claim 11, characterized in that the duration of the pressing step is 0.05-3 minutes.
PCT/CN2021/134945 2021-12-02 2021-12-02 Method for preparing bipolar plate for electrochemical fuel cell WO2023097587A1 (en)

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JP2000021422A (en) * 1998-06-30 2000-01-21 Toshiba Corp Manufacture of separator for fuel cell, and the separator for fuel cell
JP3054600B2 (en) * 1997-03-14 2000-06-19 株式会社東芝 Separator for solid polymer electrolyte fuel cell and method for producing the same
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US20090061191A1 (en) * 2007-09-04 2009-03-05 Aruna Zhamu Recompressed exfoliated graphite articles
CN111689491A (en) * 2020-05-29 2020-09-22 浙江国泰萧星密封材料股份有限公司 Flexible graphite manufacturing process for hydrogen fuel cell bipolar plate

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JP3054600B2 (en) * 1997-03-14 2000-06-19 株式会社東芝 Separator for solid polymer electrolyte fuel cell and method for producing the same
JP2000021422A (en) * 1998-06-30 2000-01-21 Toshiba Corp Manufacture of separator for fuel cell, and the separator for fuel cell
US20020127390A1 (en) * 2000-12-07 2002-09-12 Oswin Ottinger Acrylic resin-impregnated bodies formed of expanded graphite, process for producing such bodies and sealing elements, fuel cell components and heat-conducting elements formed of the bodies
US20020174782A1 (en) * 2001-05-11 2002-11-28 Klug Jeremy H. Process to reduce warping of graphite articles
US20090061191A1 (en) * 2007-09-04 2009-03-05 Aruna Zhamu Recompressed exfoliated graphite articles
CN111689491A (en) * 2020-05-29 2020-09-22 浙江国泰萧星密封材料股份有限公司 Flexible graphite manufacturing process for hydrogen fuel cell bipolar plate

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