English

Biomass Hydroxyapatite-templated Synthesis of 3D Graphene

• WANG Kexin ^1, ,
• SHI Liurong ^1, ,
• WANG Mingzhan ^1, ,
• YANG Hao ^2, ,
• LIU Zhongfan ^{1,3, ,} ,
• PENG Hailin ^{1,3, ,}

• 1.

  Center for Nanochemistry (CNC), Beijing National Laboratory for Molecular Sciences, State Key Laboratory for Structural Chemistry of Unstable and Stable Species, College of Chemistry and Molecular Engineering, Peking University, Beijing 100871, P. R. China

• 2.

  Academy for Advanced Interdisciplinary Studies, Peking University, Beijing 100871, P. R. China

• 3.

  Beijing Graphene Institute (BGI), Beijing 100095, P. R. China

Corresponding author: LIU Zhongfan, zfliu@pku.edu.cn PENG Hailin, hlpeng@pku.edu.cn

• Received Date: 14 May 2018
  Accepted Date: 26 June 2018
  Revised Date: 22 June 2018
  Available Online: 15 October 2019
• Fund Project:

  The project was supported by the Beijing Municipal Science & Technology Commission, China (Z161100002116002, Z161100002116021), the National Basic Research Program of China (2014CB932500, 2016YFA0200101), and the National Natural Science Foundation of China (21525310, 51432002, 51520105003)

Abstract: As a new 2D material with excellent chemical stability, good electric conductivity, and high specific surface area, graphene has been widely used in energy storage and conversion devices. However, 2D graphene layers are easily stacked, which may significantly reduce the surface area and degrade the excellent electrical properties of graphene. To avoid this, one of the most effective methods is to construct 3D graphene (3DG) with specific porous microstructures. Chemical vapor deposition (CVD) is an important method for the synthesis of high-quality 3DG, where templates play a defining role in controlling the structure and cost of 3DG. Metallic materials with 3D microstructures, such as nickel foam, have proven to be useful as substrates for the growth of high-quality 3DG. However, metal substrates are usually expensive, and the pickling solution generated after etching may cause environmental problems. Therefore, non-metallic substrate materials with lower costs have been investigated for the preparation of 3DG. Herein, we developed a novel template material, mammal bone ashes, for the CVD preparation of 3DG. Mammal bone ash is an inexpensive and abundant biomass hydroxyapatite. During the high-temperature CVD reaction, the bone ash powders were slightly sintered to form a continuous porous structure with graphene coating. The morphology of 3DG is inherited from the microstructure of bone ash templates. After removing the bone ash template with hydrochloric acid, the template-grown 3DG was obtained with a unique bicontinuous structure, i.e. both the graphene framework and the void space were continuous. In addition, the pickling solution of the bone ash templates after etching was exactly the same as that for the raw materials for the production of phosphoric acid to achieve high atom utilization. We further optimized the graphitization degrees, layer number, and porous morphology of 3DGs. The microstructure evolution of 3DG is highly relevant to the layer thickness and uniformity of graphene layers. A short growth time would lead to a non-uniform and thin layer of graphene, which is not able to support a complex 3D porous structure. In contrast, a uniform graphene layer with proper thickness is capable of forming a robust 3D architecture. In addition, the facile CVD method can be extended to a series of metal phosphate templates, including tricalcium phosphate [Ca₃(PO₄)₂], trimagnesium phosphate [Mg₃(PO₄)₂], and aluminum phosphate [AlPO₄]. 3DG with bicontinuous morphology is promising as a conductive frame material in electrochemical energy storage devices. As an illustration, high-performance Li-S batteries were fabricated by the uniform composition of an S cathode on 3DG. In comparison with heavily stacked 2D graphene sheets in reduced graphene oxide / S composite, the non-flat structure of 3DGs remained unchanged even after the harsh melt-diffusion process of high-viscosity liquid sulfur. The resulting 3DG/S cathode delivered a high specific capacity of ~550 mAh∙g^-1 at a high current rate (2C). Our work opens an avenue to the low-cost and high-utility production of 3D graphene, which could be integrated with the well-developed phosphorus chemical industry.

Key words:
• 3D graphene
•  /  Chemical vapor deposition
•  /  Bio-waste
•  /  Hydroxyapatite
•  /  Li-S battery

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