Department of Materials Science and Engineering and ‡Department of Chemistry and Chemical Biology, Cornell University , Ithaca, New York 14850, United States.
ACS Nano. 2014 Jan 28;8(1):731-43. doi: 10.1021/nn405392t. Epub 2013 Dec 19.
Ordered mesoporous carbons with high pore accessibility are of great interest as electrodes in energy conversion and storage applications due to their high electric and thermal conductivity, chemical inertness, and low density. The metal- and halogen-free synthesis of gyroidal bicontinuous mesoporous carbon materials with uniform and tunable pore sizes through bottom-up self-assembly of block copolymers thus poses an interesting challenge. Four double gyroidal mesoporous carbons with pore sizes of 12, 15, 20, and 39 nm were synthesized using poly(isoprene)-block-poly(styrene)-block-poly(ethylene oxide) (ISO) as structure-directing triblock terpolymer and phenol-formaldehyde resols as carbon precursors. The highly ordered materials were thermally stable to at least 1600 °C with pore volumes of up to 1.56 cm(3) g(-1). Treatment at this temperature induced a high degree of sp(2)-hybridization and low microporosity. Increasing the resols/ISO ratio led to hexagonally packed cylinders with lower porosity. A single gyroid carbon network with high porosity of 80 vol % was obtained using a similar synthesis strategy. Furthermore, we present a method to fabricate monolithic materials of the gyroidal carbons with macroscopic shape and thickness control that exhibit an open and structured surface with gyroidal features. The gyroidal materials are ideally suited as electrode materials in fuel cells, batteries, and supercapacitors as their high, three-dimensionally connected porosity is expected to allow for good fuel or electrolyte accessibility and to prevent total pore blockage.
有序介孔碳因其高导电性和热导率、化学惰性和低密度，在能量转换和存储应用中作为电极材料具有很大的吸引力。通过无金属和无卤素的自下而上的嵌段共聚物自组装合成具有均匀和可调孔径的旋转双连续介孔碳材料是一个有趣的挑战。通过使用聚异戊二烯-嵌段-聚苯乙烯-嵌段-聚氧化乙烯（ISO）作为结构导向三嵌段共聚物和酚醛树脂作为碳前体制备了四种孔径分别为 12、15、20 和 39nm 的双旋转介孔碳。这些高度有序的材料在至少 1600°C 的温度下热稳定，孔体积高达 1.56cm³g-1。在该温度下处理会导致 sp2 杂化程度高和微孔率低。增加树脂/ISO 比会导致具有较低孔隙率的六方堆积圆柱。使用类似的合成策略获得了具有高孔隙率 80 体积%的单旋转碳网络。此外，我们提出了一种制造具有宏观形状和厚度控制的旋转碳整体材料的方法，该材料具有开放的和结构化的表面，具有旋转特征。这些旋转材料非常适合用作燃料电池、电池和超级电容器的电极材料，因为其高的、三维连通的孔隙率有望允许良好的燃料或电解质可及性，并防止总孔堵塞。
