(398bm) 3D Vertically-Aligned CNT/Graphene Hybrids from Layer-By-Layer Transfer for Supercapacitors

3D Vertically-Aligned CNT/Graphene Hybrids from Layer-by-Layer Transfer for Supercapacitors

Dr. Enoch A. Nagelli^1*, Dr. Liang Huang², Dr. Feng Du², and Prof. Liming Dai²

¹Department of Chemistry & Life Science

United States Military Academy, West Point, New York 10996

²Center of Advanced Science and Engineering for Carbon (Case4Carbon)

Department of Chemical and Biomolecular Engineering

Department of Macromolecular Science and Engineering

Case Western Reserve University, Cleveland, OH

^*Corresponding Author: Dr. Enoch Nagelli, Email: enoch.nagelli@usma.edu

Exceptional properties such as stable crystal structure, optical transparency, and superior electronic properties from high electron mobility make graphene a nanomaterial with promising applications.^{[1, 2]} Among the many methods employed for producing graphene films, mechanical cleavage of HOPG^[3] or exfoliation of graphite crystals,^[4,5] chemical vapor deposition,^[6] solvent thermal reaction,^[7,8] and chemical routes via carbon nanotubes (CNTs), graphite intercalation compounds (GIC) or graphite oxide (GO) are the most widely recognized and used methods to produce single- and few-layer graphene.^[9-12] Moreover, the oxidation and reduction of graphite is one of the most used methods for mass production of graphene for industrial applications. However, the reduction of graphene oxide results in a decrease in hydrophilicity, which in turn leads to greater aggregation and precipitation thus, losing its unique 2D characteristics.^[13] Both chemical functionalization and electrostatic stabilization have been employed to reduce the agglomeration of graphene in order to utilize its unique properties.^[14]

 Furthermore, there is a need to integrate graphene into 3D macroscopic architectures while maintaining its superior intrinsic properties. Graphene and carbon nanotubes have been combined to form transparent conductive films^[15] and electrodes for rechargeable lithium ion secondary batteries.^[16] Researchers recently designed a computational model of the novel 3D structure consisting of parallel graphene layers stabilized by vertically aligned CNTs (VA-CNTs) in between the graphene planes.^[17]  However, experimental fabrication of the 3D graphene/VA-CNT hybrid structure via the transfer assembly process remains challenging. In addition, on the basis of our previous work^[18] on the tunable 3D pillared VA-CNT/graphene architectures through intercalated growth of VA-CNTs into thermally expanded highly ordered pyrolytic graphite (HOPG) by the pyrolysis of iron phthalocyanine, we report a novel strategy to prepare 3D graphene/VA-CNT hybrid structures by a contact film transfer process, which utilizes attractive intermolecular-surface forces e.g., van der Waals of graphene and VA-CNTs. For the first time, we demonstrate a novel yet facile technique to develop three dimensional hybrid graphene/VA-CNT nanostructure via free-standing film transfer through the hydrophobic-hydrophobic interactions. As a result, supercapacitors based on the 3D graphene/VA-CNT hybrid formed via the transfer process were developed.

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