物理化学学报2020，Vol.36Issue(2)：53-71,19.DOI:10.3866/PKU.WHXB201904025
新碳源制备活性炭和石墨烯及其非等电极电容水系超级电容器
New Precursors Derived Activated Carbon and Graphene for Aqueous Supercapacitors with Unequal Electrode Capacitances
摘要
Abstract
Carbon materials can offer various micro- and nanostructures as well as bulk and surface functionalities; hence, they remain the most popular for manufacturing supercapacitors. This article critically reviews recent developments in the preparation of carbon materials from new precursors for supercapacitors. Typical examples are activated carbon (AC) and graphene, which can be prepared from various conventional and new precursors such as biomass, polymers, graphite oxide, CH4, and even CO2 via innovative processes to achieve low-cost and/or high specific capacitance. Specifically, when producing AC from natural biomasses or synthetic polymers, either new, spent, or waste,popular activation agents, such as KOH and ZnCl2, are often used to process the ACs derived from these new precursors while the respective activation mechanisms always attract interest. The traditional two-step calcination process at high temperatures is widely employed to achieve high performance, with or without retaining the morphology of the precursors. The three-step calcination, including a post-vacuum treatment, is also the preferred choice in many cases, but it can increase the cost per capacity (kWh·g?1). More recently, one-step molecular activation promises a better and more economical approach to the commercial application of AC, although further increase of the yield is necessary. In addition to activation, graphitization, N doping, and template control can further improve ACs in terms of the charging and discharging rates, or pseudocapacitance, or both. Considerations are also given to material structure design, and carbon regeneration during activation. Metal-organic frameworks, which were initially used as templates, have been found to be good direct carbon precursors. Various graphene structures, including powders, films, aerogels, foams, and fibers, can be produced from graphite oxide, CO2, and CH4. Similar to AC, graphene can possess micropores by activation. Self-propagating high-temperature synthesis and molten salt processing are newly-reported methods for fabrication of mesoporous graphene. Macroporous graphene hydrogels can be produced by hydrothermal treatment of graphite oxide suspension, which can also be transferred into films. Hierarchically porous structures can be achieved by H2O2 etching or ZnCl2 activation of the macroporous graphene precursor. Sponges as templates combined with KOH activation are applied to create both micro- and macropores in graphene foams. Graphene can grow on fibers and textiles by electrodeposition, dip-coating, or filtration, which can be woven into clothes with a large area or thick loading, illuminating the potential application in flexible and wearable supercapacitors. The key obstacles in AC and graphene production are high cost, low yield, low packing density, and low working potential range. Most Carbon materials derived from new precursors work very well with aqueous electrolytes. Charge storage occurs not only in the electric double layer (i.e., the "carbon | electrolyte"interface), but also via redox activity in association with the bulk and surface functionalities, and the resulting partial delocalization of valence electrons. The analysis of the capacitive electrode has shown a design defect that prevents the working voltage of a symmetrical supercapacitor from reaching the full potential window of the carbon material. This defect can be avoided in AC-based supercapacitors with unequal electrode capacitances, leading to higher cell voltages and hence higher specific energy than their symmetrical counterparts. There are also emerging ways to raise the energy capacity of AC supercapacitors, such as the use of redox electrolytes to enable the Nernstian charge storage mechanism, and of the three dimensional printing method for a desirable electrode structure. All these developments are promising carbon materials from various precursors of new and waste sources for a more affordable and sustainable supercapacitor technology.关键词
新碳源/活性炭/石墨烯/水系电容器/非等电极电容Key words
New precursor/Activated carbon/Graphene/Aqueous supercapacitor/Unequal electrodecapacitance分类
化学化工引用本文复制引用
陈尧,陈政..新碳源制备活性炭和石墨烯及其非等电极电容水系超级电容器[J].物理化学学报,2020,36(2):53-71,19.基金项目
The project was supported by State Key Laboratory of Materials Processing and the Die & Mould Technology, Huazhong University of Science and Technology, China (P2019-014) and the Ningbo Municipal Government, China (3315 Plan, and 2014A35001-1).华中科技大学材料成形与模具技术国家重点实验室开放基金(P2019-014)、宁波市政府(3315计划和2014A35001-1)资助项目 （P2019-014）
