Biomass derived hierarchical porous carbons as high-performance anodes for sodium-ion batteries
Graphical abstract
Introduction
Fabricating devices for high-performance energy storage has great importance for the solvation of energy shortage and related environmental issues [1]. Lithium ion batteries, as one of the most important energy storage systems, have been widely applied in electric vehicles, portable devices and grid storage owing to their long cycle life and high energy density [2]. However, as the use of large format lithium ion batteries, there is increasing concern regarding lithium's cost and continued availability [3]. Recently, sodium ion batteries are attracting renewed interest as a potentially lower cost alternative to lithium ion batteries because of the widespread distribution of sodium resources [4], [5], [6]. Because the sodium ion has a larger ionic radius than that of the lithium ion, the design of suitable host materials with larger space for intercalating and accommodating sodium ions is very difficult [7], [8].
Currently, carbon is recognized as one of the promising electrode materials for energy storage systems due to its low cost, high electrical conductivity, stable physicochemical property, and long cycle life. It is well acknowledged that the commonly-used commercial graphite anode in todays lithium ion batteries shows a low reversible capacity in sodium ion batteries due to the graphene interlayer spacing that cannot host the larger Na ions [2], [9]. On the other hand, a variety of carbon materials including carbon black [10], hard carbon [11], [12], carbon spheres [13], [14], hollow carbon nanowires [15], carbon nanofibers [16], [17], carbon nanotubes [9], [18], and graphene [19], [20] were found to facilitate the insertion/extraction of sodium ions and accelerate solid-state diffusion kinetics. Charge storage in carbons as anodes for sodium ion batteries can be clarified into several mechanisms, including chemisorption on surface heteroatoms or at defect sites, physisorption on the surface of pores, intercalation between graphene layers, and metal pore fillings [9], [15], [21]. Recent results indicate that the improvement of electrochemical performance of carbon anodes for sodium ion batteries strongly depend on their morphology, pore structure, and heteroatom doping. Noteworthy examples of high performance carbon anodes include nitrogen-doped carbon naofibers (a capacity of 134 mAh g1 after 200 cycles at 0.2 A g1) [16], nitrogen-doped porous carbon sheets (a capacity of 155 mAh g1 after 260 cycles at 0.05 A g1) [8], peat moss derived carbon nanosheet (a capacity of 255 mAh g1 after 200 cycles at 0.1 A g1) [22], hollow carbon nanowire (a capacity of 206 mAh g1 after 400 cycles at 0.05 A g1) [15], nitrogen-doped graphene foams (a capacity of 594 mAh g1 after 150 cycles at 0.05 A g1) [23]. Besides, carbon material can be used as a promising matrix for loading of nanostructured metals, metal oxides, and sulfides, to increase the electronic conductivity, accommodate the volume change during cycling, and improve the rate capability [24], [25].
Recently, extensive attention has been focused on using natural biomass to construct carbon materials [26], [27], [28], [29], [30], [31], [32], [33], [34], [35], [36], [37], [38], [39], [40], [41]. Such carbon electrodes derived from biomass waste would be truly green. In terms of the preparation technique and the electrochemical performance, some biomass derived activated carbons with microscale particulates and tortuous pore networks exhibited similar electrochemical performance with commercial activated carbon products [42], [43]. In the present work, we selected peanut skin as the precursor to design nanostructured carbons by using two different synthesis routes. Approximately more than 30 million metric tons of peanut produced per year in the word [44]. Peanut skin is the by-product of the manufacturing of peanut-based products, such as peanut butter, snack peanuts and confectionary. Peanut skin contains about 12% protein, 16% fat, and 72% carbohydrate [45]. Although the peanut skin, to some extent, is nutritive and expensive than other biomass precursors, we selected peanut skin as the precursor in the present work in order to give a case study that marrying the intrinsic structure/composition of the precursor to a tailored synthesis route can prepare sheet-like porous carbons [32]. The obtained hierarchical porous carbon (HPC) with sheet-like structure and high surface area (>1400 m2 g1) derived from peanut skin delivers a reversible capacity as high as 148 mAh g1 at a current density of 0.5 A g1 after 200 cycles, and maintains a capacity of 47 mAh g1 even at a very high current density of 10 A g1. The observed excellent electrochemical performance of the obtained carbon anodes in sodium ion batteries can be attributed to synergistic effects associated with the sheet-like morphology with a well-defined porosity, large surface area, and enlarged lattice spacing between graphene layers.
Section snippets
Material preparation
Hierarchical porous carbons were prepared by carbonization and activation of peanut skin with and without hydrothermal pretreatment. The employed peanut skins were peeled off from peanuts grown in the Shandong region of China. Route one: 2.0 g of peanut skin and 50 mL of diluted sulfuric acid were placed in a 100 mL stainless steel autoclave. The autoclave was heated at 180 °C for 24 h and then cooled down naturally. The resulting biochar was collected by filtration, washed with distilled water, and
Physicochemical characterization
The decision to employ two different synthesis strategies for hierarchical porous carbons was based on the plant structure, and how it can be transformed to final carbons with unique structures. Fig. 1 illustrates the material synthesis process employed for the electrodes, as well as the relevant charge storage mechanisms (discussed later). For route one, the hydrothermal pretreatment of biomass was firstly applied before carbonization/activation. The hydrothermal process involves hydrolysis,
Conclusions
We created hierarchical porous carbons with sheet-like morphologies that were derived from peanut skin. The unique structural feature endows the hierarchical porous carbons with excellent electrochemical performance, that is, a high initial reversible capacity of 431 mAh g1 at 0.1 A g1, a good cycling stability with a capacity retention of 8386% after 200 cycles, and a high rate capability of 47 mAh g1 at a current density of 10 A g1. The storage of sodium in carbons can be roughly divided into
Acknowledgements
The authors are grateful to financial supports from the National Natural Science Foundation of China (No. 21471139, and 51402272), China Postdoctoral Science Foundation (No. 2014M560581, and 2015T80747), Shandong Province Outstanding Youth Scientist Foundation Plan (No. BS2014CL024), Qingdao Postdoctoral Science Foundation, Seed Fund from Ocean University of China, and Fundamental Research Funds for the Central Universities.
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