Nagai Atsushi, Indrawan Radian Febi, Devendran Arthisree, Shahmirzaee Mozhgan, Sharma Sandhya, Alipour Hassan, Łyczko Krzysztof, Matsuda Atsunori
Next-Generation Energy Systems Group, Centre of Excellence ENSEMBLE3 sp. z o.o., Wolczynska 133, Warsaw 01-919, Poland.
Department of Electrical and Electronic Information Engineering, Toyohashi University of Technology, 1-1 Hibarigaoka, Tempaku-cho, Toyohashi, Aichi 441-8580, Japan.
ACS Omega. 2025 Aug 22;10(35):39841-39849. doi: 10.1021/acsomega.5c03968. eCollection 2025 Sep 9.
In this study, two PI-COFs, PI-TAPA-PMDI (twisted triphenylamine node) and PI-TAPB-PMDI (non-twisted triphenylbenzene node), were pelletized (∼10 mm diameter) under 90 MPa and carbonized at 600 °C in argon for 2-50 h. Carbonization produced nitrogen-doped, defective porous carbons with an enhanced electronic conductivity. Electrochemical impedance spectroscopy showed that PI-TAPB-PMDI COF-600 heated for 50 h had significantly lower resistance ( ≈ 14.14 Ω and ≈ 61.66 Ω) compared to shorter heating treatments ( ≈ 27.70 Ω), indicating improved electron transport and better interaction with a Fe-(CN) /Fe-(CN) redox couple system. The XRD patterns verified the crystalline structure of PI-TAPA-PMDI and PI-TAPB-PMDI COFs, which reduces to an amorphous state during the carbonization progress. The XPS and FTIR results confirmed nitrogen incorporation and hydrogen bonding, while Raman and BET analyses revealed superior structural ordering and porosity in the PI-TAPB-PMDI COF compared to PI-TAPA-PMDI, respectively. For PI-TAPB-PMDI COF-600, increasing carbonization time raised BET surface area (up to 510 mg) and promoted mesoporosity, with a pore size of 2.8 nm after 50 h treatment. In summary, PI-TAPB-PMDI COF-600 With a nitrogen content of 0.5% and conductivity of 3.02 × 10 S cm demonstrates strong potential as a high-performance, functionalized graphite oxide-like material for energy storage applications.
在本研究中,两种PI-COF,即PI-TAPA-PMDI(扭曲的三苯胺节点)和PI-TAPB-PMDI(非扭曲的三苯基苯节点),在90MPa压力下压制成丸(直径约10mm),并在氩气中于600℃碳化2 - 50小时。碳化产生了具有增强电子导电性的氮掺杂、有缺陷的多孔碳。电化学阻抗谱表明,与较短加热处理(约27.70Ω)相比,加热50小时的PI-TAPB-PMDI COF-600具有显著更低的电阻(约14.14Ω和约61.66Ω),这表明电子传输得到改善,并且与Fe-(CN)₆³⁻/Fe-(CN)₆⁴⁻氧化还原偶体系的相互作用更好。XRD图谱验证了PI-TAPA-PMDI和PI-TAPB-PMDI COF的晶体结构,其在碳化过程中转变为非晶态。XPS和FTIR结果证实了氮的掺入和氢键的存在,而拉曼光谱和BET分析分别表明PI-TAPB-PMDI COF相比于PI-TAPA-PMDI具有更优异结构有序性和孔隙率。对于PI-TAPB-PMDI COF-600,增加碳化时间会提高BET表面积(高达510m²/g)并促进中孔率,50小时处理后孔径为2.8nm。总之,氮含量为0.5%且电导率为3.02×10⁻³S/cm的PI-TAPB-PMDI COF-600作为一种用于储能应用的高性能、功能化类氧化石墨材料具有巨大潜力。