添加碳纳米颗粒对磷氮双掺杂石墨烯电化学特性的影响

doi:10.11949/0438-1157.20191135

摘要/Abstract

摘要：

燃料电池作为新型清洁能源技术具有高效的能源转化效率和环境友好等优点，在诸如交通运输以及航空航天等领域有着重要而广泛的应用。在影响燃料电池性能的众多因素中，电极的高效催化与稳定性对于整个燃料电池系统的性能至关重要。近年来，石墨烯材料由于优异的电学与力学性质为低铂高效催化研究提供了理论上的可行性。本研究以六氯环三磷腈（HCCP）为原料设计了一步热还原合成法实验制备了磷氮双掺杂石墨烯，并通过添加碳纳米颗粒增加了石墨烯层间间距，改善了石墨烯层间的团聚效应，提高了氧化还原（ORR）性能。研究结果表明，当AC添加含量与GO的质量比为10%时，其比表面积与电化学性能提升最为明显，极限电流密度达到-6.89 mA·cm^-2并且氧化活性能保持80%以上。因此，使用添加碳纳米颗粒对磷氮双掺杂石墨烯作为燃料电池非金属催化剂材料的进一步探索具有巨大的潜力。

关键词: 燃料电池, 掺杂石墨烯, 碳纳米颗粒, 电化学, 催化剂

Abstract:

Fuel cell as a new clean energy technology has the characteristics of high energy conversion efficiency and environmental protection. It has been widely used in transportation, aerospace and other fields. Among the factors affecting the performance of fuel cell, the efficient catalysis and stability of electrodes are most importantly for the performance of the fuel cell system. In recent years, graphene based materials have provided theoretical feasibility for the study of low platinum (Pt) and high efficiency catalysis due to their excellent electrical and mechanical properties. In this study, phosphorus-nitrogen double-doped graphene was prepared with a one-step thermal reduction synthesis by using hexachlorocyclotriphosphazonitrile (HCCP) as the raw material. With adding the active carbon nanoparticles, the spacing between graphene layers was increased, and the agglomeration between graphene layers was also decrease, which result in a significantly promotion of the oxidation reduction reactions (ORR) performance. The results show that when the mass ratio of AC to GO is 10%, the specific surface area and electrochemical performance are improved most obviously with the limiting current density is -6.89 mA·cm^-2 and the oxidation activity can be maintained above 80%. Therefore, the material we prepared for phosphorus-nitrogen double-doped graphene has great potential as the non-metallic catalyst material for fuel cells.

Key words: fuel cell, doped graphene, active carbon nanoparticles, electrochemistry, catalyst

中图分类号:

O 646.541

韩超灵, 陈振乾. 添加碳纳米颗粒对磷氮双掺杂石墨烯电化学特性的影响[J]. 化工学报, 2020, 71(S1): 448-453.

Chaoling HAN, Zhenqian CHEN. Effect of active carbon nanoparticles on electrochemical properties of phosphorus-nitrogen double-doped graphene[J]. CIESC Journal, 2020, 71(S1): 448-453.

图/表 5

图1 P,N-G的制备过程

Fig.1 Synthesis procedures of P,N-G with AC

图2 未添加AC(a)、添加10% AC(b)条件下P,N-G的微观形貌和元素映射图[(c)、(d)]

Fig.2 SEM image of P,N-G samples: microstructure of AC (0)@P,N-G (a), microstructure of AC (10%)@P,N-G (b), elemental mapping images of N and P [(c),(d)]

图3 AC (0)@P,N-G的XRD谱图(a)和AC (0)@P,N-G的拉曼光谱图(b)

Fig.3 XRD patterns of AC (0)@P,N-G (a) and Raman spectra of AC (0)@P,N-G (b)

图4 P,N-G的N2吸脱附曲线(a)和孔径分布(b)

Fig.4 Nitrogen adsorption-desorption isotherms of P,N-G under different contents of AC (a) and DFT pore size distributions of P,N-G under different contents of AC (b)

图5 不同碳纳米颗粒含量(AC=0, 5%, 10%, 30%和50%)下的磷氮掺杂石墨烯CV曲线(a); 1600 r·min-1转速下不同碳纳米颗粒含量(AC=0, 5%, 10%, 30%和50%)下的磷氮掺杂石墨烯LSV曲线(b); 10%碳纳米颗粒含量下的磷氮掺杂石墨烯不同扫速LSV曲线(c); 10%碳纳米颗粒含量下的磷氮掺杂石墨烯K-L曲线(d); 由(d)计算得到的电子转移数(e); 10%碳纳米颗粒含量下的磷氮掺杂石墨烯循环稳定性(f)

Fig.5 Comparison of CV curves of AC@P,N-G (AC=0, 5%, 10%, 30% and 50%) (a). LSV plots of AC@P,N-G (AC=0, 5%, 10%, 30% and 50%) and Pt/C at rotation rate of 1600 r·min-1 at scan rate of 10 mV·s-1 (b). LSV plots of AC (10%)@P,N-G at different rotating rates from 400 r·min-1 to 2400 r·min-1 (c). K-L plots of AC (10%)@P,N-G at different potentials (d). Electron transfer number (n) of AC (10%)@P,N-G at different potentials (e). Durability test of AC (10%)@P,N-G and Pt/C (f)

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