Historical perspective
Three dimensional graphene based materials: Synthesis and applications from energy storage and conversion to electrochemical sensor and environmental remediation

https://doi.org/10.1016/j.cis.2015.04.005Get rights and content

Highlights

  • Recent studies on synthetic pathways of 3D graphene-based materials are reviewed.

  • Applications of 3D graphene-based materials are discussed and summarized.

  • Challenges and outlook about 3D graphene-based materials are presented.

Abstract

With superior electrical/thermal conductivities and mechanical properties, two dimensional (2D) graphene has become one of the most intensively explored carbon allotropes in materials science. To exploit the inherent properties fully, 2D graphene sheets are often fabricated or assembled into functional architectures (e.g. hydrogels, aerogels) with desired three dimensional (3D) interconnected porous microstructures. The 3D graphene based materials show many excellent characteristics including increased active material per projected area, accessible mass transport or storage, electro/thermo conductivity, chemical/electrochemical stability and flexibility. It has paved the way for practical requirements in electronics, adsorption as well as catalysis related system. This review shows an extensive overview of the main principles and the recent synthetic technologies about fabricating various innovative 3D graphene based materials. Subsequently, recent progresses in electrochemical energy devices (lithium/lithium ion batteries, supercapacitors, fuel cells and solar cells) and hydrogen energy generation/storage are explicitly discussed. The up to date advances for pollutants detection and environmental remediation are also reviewed. Finally, challenges and outlooks in materials development for energy and environment are suggested.

Introduction

Energy shortage, fossil fuels usage and environmental pollution have become important and urgent global problems due to urbanization, industrialization and the changing lifestyles of people [1], [2]. Given the recognized threats, critical challenges and driving global research have attracted extensive attention by scientific community [3]. Accompanied with the more stringent rules and regulations concerning energy usage and environmental protection, various technologies are urgently needed to satisfy the increasing demand in energy and environment field. In parallel, enhancing nanotechnology and nano-materials hold out great promise for the immense improvements [4].

In recent years, emerging as a new class of carbon nano-materials, graphene has attracted tremendous attention and becomes a rapidly developing area. It displays versatile properties including thermal conductivity, mobility of charge carriers, electrical and mechanical properties, magnetism and so on [5]. These features as well as large surface area play a crucial role in electronics, optoelectronics, and electrochemical and biomedical applications [6]. Most importantly, the recent focus on graphene as a general platform for various composites has inspired many possibilities in energy and environmental aspect [4]. However, two dimensional graphene sheets are limited for many specific fields due to that (i) the weak absorption for light and the low capacitance of graphene; (ii) the easy stack and agglomeration in solvent; (iii) the zero-gap semi-metal nature of graphene [4], [6], [7]. Realizing these shortages, a growing exploration to modify graphene surface and construct dimension-tailored functional graphene structures, including graphene quantum dots (0D), graphene fibers (1D), graphene sheets/films (2D) and graphene gel (3D), has been exerted to expand the scope of application in quantum computing, catalysis, sensors and even more [8].

Among them, graphene-based macroscopic materials with three-dimensional (3D) porous network have received increasing attention for energy and environmental field. Compared with carbon nanotube-based 3D architectures, graphene-based 3D materials offer more advantages, including easy preparation, high efficiency and economical devices [9]. The integration of individual chemically modified 2D graphene sheets into monoliths with 3D macroporous structures through various gelation technologies could be referred as 3D graphene-based materials (3D GBMs), which can be further classified into hydrogels and aerogels (sponges or foams) throughout this review. The gels could achieve long range order and conductivity between the individual graphene sheets, and have more “space” towards the transportation or storage for the electron/ion, gas and liquid [10]. This will be important for maintaining graphene’s properties in bulk and to enhance graphene utilization for practical applications. Moreover, the resulting gels present strong mechanical strengths/flexibility, surface hydrophobicity, good electrical conductivity and electrochemical performance, fast mass and electron transport kinetics, and self-healing performance [11]. Such bulk materials with desired structures and properties hold the key to the realization of their extensive potential applications for energy storage and conversion, and environmental remediation [12], [13], [14], [15], [16], [17]. As shown in Fig. 1, the number of publications (according to ISI Web of KnowledgeSM) on 3D GBMs over the past five years increases dramatically after 2011. In particular, the impact in energy and environmental applications has been realized well.

Although the existence of several reviews highlights the applications of 3D GBMs [7], [8], [9], [10], [18], [19], [20], [21], [22], a review from materials synthesis to both energy and environmental-related applications is still missing. This review article has presented the recent progresses related to the synthesis of innovative 3D graphene based materials, followed by placing the emphases on recent advancements about the applications in the fields of energy storage devices (supercapacitors, lithium batteries, fuel cells, solar cell, etc.), hydrogen energy production and environment protection (pollutants detection and environmental remediation). Challenges and outlook are offered to inspire more exciting developments in future.

Section snippets

Synthesis of 3D graphene-based materials

The morphology and structure of 3D graphene-based architecture not only makes up the shortages of individual graphene sheets during assembling process but also provides sufficient adsorption space and contact area between electrolyte and electrode [10]. Chemically modified 2D graphene sheets can be intergrated into 3D macroporous structures via various gelation technologies to form graphene-based gels, which could be referred as hydrogels and aerogels (sponges or foams). The 3D networks of

3D graphene-based materials for energy applications

Nowadays, the ever-reducing dependence on fossil fuels has sparked the great interest in the development of exploiting clean and recyclable energy. Apparently, the achievements of material science are critical for development of energy conversion and storage techniques. With exceptional porous structure, larger surface area, excellent electronic conductivity and mechanical strength, 3D graphene-based materials have been intensively explored for applications in energy storage and conversion

3D graphene-based materials for environmental application

3D graphene-based monolith can be used as a general platform for sensing pollutants in water or air, and also as a platform for removing hazardous species by the means of adsorption or catalytic degradation. Compared with functionalized graphene sheets featured with 2D layer structure, large surface area, conjugated domains and oxygenated groups, 3D GBMs with a high porosity have more advantages, including the improved adsorption and catalytic capability, and the ease of separation from

Conclusions and outlook

3D GBMs with macro-, micro- and nano-structures have been applied to construct various attractive electrochemistry energy devices, sorbents and catalysts. A variety of methods including hydrothermal/solvothermal reaction, self-assembly, organic sol–gel reaction and template guided growth have been developed for preparing 3D graphene-based materials. The 3D architectures do not only assemble graphene nanosheets into macroscopic materials for practical applications but also provide fundamental

Acknowledgements

The authors gratefully acknowledge the financial support provided by the National Water Pollution Control and Management Technology Major Project of China (No. 2009ZX07212-001-02), the National Natural Science Foundation of China (No. 21276069, 71221061), and the Hunan Province Innovation Foundation for Postgraduate (No. CX2014B142).

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