High-capacity nanocarbon anodes for lithium-ion batteries
Graphical abstract
Introduction
Lithium-ion batteries (LIBs) are one of the most important and widely used rechargeable battery with advantages of high voltage, low self-discharge, long cycling life, low toxicity, and high reliability [1], [2], [3]. The most commonly anode materials employed in LIBs are lithium intercalation compounds like graphite [4]. However, graphite has a limited theoretical capacity of 372 mA h g−1 and low rate-capability [5]. Achievement of higher energy and power density, longer life, and better operational safety for next-generation LIBs become much more important as the demand for hybrid electrical vehicle, plug-in hybrid electrical vehicle and mobile electronic device back-up increases while graphite falls shorts of fulfilling all these necessities [6], [7]. To address these issues, development of new materials for electrodes is an alternative choice. In recent years, some materials including carbon nanostructures (called nanocarbons), lithium alloys and metal oxides with high specific capacity have been intensively investigated and shown good promise to replace conventionally used graphite anodes [8], [9], [10]. Among these materials, nanocarbons hold the advantage of low volume expansion during lithiation/de-lithiation and thus provide longer life.
Some nanocarbons including fullerene, carbon nanotube (CNT), graphene, amorphous carbon, and porous carbon have been proved to deliver >600 mA h g−1 [11], [12], [13], [14], [15], [16]. The improved capacity may originate from some different storage mechanisms. Fullerene with hydrogen atom can adsorb more lithium ions in the form of Li–H [11]; CNT and graphene exhibited considerable capacity when the potential is far away from that of lithium intercalated graphite; some porous carbons show much high capacity than that of graphite through lithium storage in micropores, at defects or as a result of nanosize effects [17]. In recent years, nanocarbons especially graphene oxide with functionalized groups exhibit high capacity while still suffer from poor cycling stability [18], [19], [20], [21]. Besides delivering high capacity, nanocarbon anodes are capable to improve the rate performance of LIBs by decreasing the diffusion length [22]. On the other hand, design of an optimal porous structure, which is helpful to decrease the transport pathways, for nanocarbons would offer the chemistry and structure to store lithium ions, and ensure the accessibility of the electrolyte ions [23]. Hence, developing novel electrode materials as the host of the lithium insertion and transport is imperative to realize high energy and power of LIBs.
In the present work, we report that nanocarbons including mesoporous graphene (MPG), carbon tubular nanostructures (CTN), and hollow carbon nanoboxes (HCB) are good candidate for LIB anodes. The nanocarbon electrodes have capacity of ∼1100 mA h g−1, about two times higher than theoretical capacity of graphite. Furthermore, the nanocarbon electrodes show very long-time cycling stability.
Section snippets
Sample preparation
The preparation of nanocarbon samples was reported elsewhere [24]. Basically, MPG, CTN, and HCB samples were fabricated through direct conversion of carbon dioxide. Transmission electron microscopy (TEM) was performed with a JEOL JSM-2100 operating at an accelerating voltage of 200 kV. Surface area measurements of carbon materials were carried out with Micromeritics ASAP 2020 HD88 surface area and pore size analyzer using nitrogen gas adsorption–desorption isotherm at −196 °C. Scanning electron
Results and discussion
The electrochemical lithium storage properties of nanocarbon electrodes were evaluated by GCD measurements. Fig. 1 depicts the first five cycles of the MPG, CTN, and HCB electrodes at GCD current density of 0.1 A g−1. The average discharge capacities of 1110, 594, and 494 mA h g−1 were obtained for MPG, CTN, and HCB electrodes (see Fig. 1A–C). It is interesting that the capacity of MPG is higher than previously reported reduced graphene oxide (RGO), RGO-based composites and comparable to many metal
Conclusions
LIB anodes based on nanocarbons show large capacity and long-term cyclic stability. The nanocarbon materials, which are composed of few-layer graphene, mesopores-rich, and have high-purity and high surface area, realize insertion and extraction of lithium ions similar to graphite anode, shorten transport length because of its edge structure, and adsorb solvated lithium ions to enhance capacity at high potential. Herein a challenge is still present because the capacity contribution for
Acknowledgement
This work was supported by the “National Natural Science Foundation of China” under Project Nos. 51307167, 51472238 and 51025726, and the Open Project Program of State Key Laboratory of Chemical Resource Engineering (CRE-2014-C-102).
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