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摘要: 雙極板作為質子交換膜燃料電池（PEMFCs）的重要組成部件，對電池堆的重量、體積、效率、耐久度、成本起著決定性作用。目前，金屬板與石墨板電堆制備技術相對成熟，已經廣泛應用于商用車、乘用車領域，但復合雙極板的生產制造因原料配方未完全實現國產化、無法大批量流水線生產、成本較高等在我國仍未大批量投入市場，尋找低成本的原材料、優化原料配比及加工條件、縮短加工周期對復合雙極板的產業化具有重要意義。本文首先比較了金屬雙極板、石墨雙極板和復合雙極板的特點，介紹了復合雙極板的模壓工藝及優點，然后概述了碳基復合材料模壓雙極板的研究進展，包括以酚醛樹脂、環氧樹脂和乙烯基酯樹脂等熱固性樹脂為黏結劑的樹脂/石墨復合雙極板和炭黑、碳纖維、碳納米管增強復合雙極板，重點總結了原料種類、配比和成型工藝條件對雙極板性能的影響，最后梳理了復合雙極板的產業化現狀，提出國內外主要雙極板研發企業面臨的問題，并對復合雙極板的發展方向進行了展望。Abstract: Bipolar plates are significant components in proton exchange membrane fuel cells (PEMFCs), thus playing a decisive role in the weight, volume, efficiency, durability, and cost of battery stacks. At present, the preparation technologies of metal and graphite plate stacks have become relatively mature, and have been widely used in the fields of commercial and passenger vehicles. However, production of composite material bipolar plates has not been marketed on a large scale in China due to the incomplete localization of raw material formulation, absence of mass production lines and high production cost. Therefore, it is of great significance to find low-cost raw materials, screen raw material compositions and ratios, optimize processing conditions including molding temperature, pressure and time, and shorten the processing cycle for the industrialization of composite bipolar plates. In this review, the characteristics of metal bipolar plates, graphite bipolar plates and composite material bipolar plates were compared. Moreover, the molding process and its advantages in composite bipolar plate production were introduced. Subsequently, recent progress in research of carbon-based composite molded bipolar plates was summarized. This includes resin/graphite composite bipolar plates using thermosetting resins such as phenol formaldehyde resin, epoxy resin and vinyl ester resin as the binder, and carbon black, carbon fiber and carbon nanotube reinforced composite bipolar plates. The effects of the types and ratios of raw materials and molding process conditions on the performance of bipolar plates were emphasized. Finally, the industrialization status of composite bipolar plates was discussed, and the problems faced by major composite bipolar plate manufacturers at home and abroad were pointed out. Prospects in the development of composite bipolar plates were also explored. Additionally, unified performance test standards for composite bipolar plates were recommended to make the performance of products developed by different enterprises comparable.
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圖 1 石墨板與不同甲醇含量（質量分數）的酚醛樹脂的接觸角圖像（a～e）及接觸角與甲醇含量的關系曲線（f）。（a）酚醛樹脂（甲醇含量0%）；（b）甲醇（甲醇含量100%）；（c）含25%甲醇的酚醛樹脂；（d）含33%甲醇的酚醛樹脂；（e）含50%甲醇的酚醛樹脂[29]
Figure 1. Contact angle images of graphite plate and phenolic resin mixtures with different mass fractions of methanol (a–e) and contact angles as function of methanol content (f): (a) phenolic resin (0% methanol); (b) methanol (0% methanol); (c?e) phenolic resin mixtures with the methanol content of 25% (c), 33% (d) and 50% (e)[29]
圖 7 石墨顆粒、炭黑、碳纖維、碳納米管增強復合雙極板導電性與力學性能原理圖。（a）膨脹石墨為唯一導電介質時復合雙極板的導電通路；（b）添加石墨顆粒、炭黑、碳纖維、碳納米管時復合雙極板的導電通路；（c）改性碳纖維/碳納米管表面官能團與樹脂官能團形成共價鍵
Figure 7. Schematic for the reinforced conductivity and mechanical properties of composite bipolar plate by graphite particles, carbon black, carbon fiber and carbon nanotube: (a) conductive path of composite bipolar plate using expanded graphite as the only conductive medium (b) adding graphite particles, carbon black, carbon fiber and carbon nanotubes; (c) the form of covalent bonds between surface functional groups of modified carbon fiber/carbon nanotube and those of resin
表 1 國內外主要企業研發的復合雙極板的性能
Table 1. Performances of composite bipolar plates produced by main domestic and foreign enterprises
Performance Jiangsu Shenzhou Carbon Products Co., Ltd. Wuhan Himalaya Optoelectronics Technology Co., Ltd Huizhou Hailong Mold Plastic Products Co., Ltd. Huizhou Duke New Material Co., Ltd. Foshan Nanhai Baotan Graphite Products Co., Ltd. Ensinger, Germany Bulk density/(g·cm?3) ≥1.85 1.8–1.95 — — 1.89 2 Conductivity/(S·cm?1) — — 220 >300 95 142 Resistivity/(μΩ·m) ≤40 16 — — — 70.4 Compressive strength /
MPa≥80 >50 >55 >100 70 — Flexural strength/MPa ≥40 >51 >45 >40 45 40 Shore hardness, HS ≥30 48–51 — — — — Proper temperature/℃ ?4–200 — >120 ?55–150 — 200–240 Contact resistance /
(mΩ·cm2)— — <8 <6 — — Corrosion current density/(μA·cm?2) — — ≤0.5 <0.5 — — Gas permeability/ [cm3·(s·cm2·Pa)?1] — — <1.3×10?14 3.76×10?12 — — Porosity/% ≤0.2 ≤0.12 — — — — 
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