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Materials and Interfaces
Iron-modified Graphites towards Boosted Lithium/ Sodium Storage Performance and Long-Term Cyclability Si Chen, Li-Ping Lv, Suo Xiao, Weiwei Sun, Xiaopeng Li, and Yong Wang Ind. Eng. Chem. Res., Just Accepted Manuscript • DOI: 10.1021/acs.iecr.8b01091 • Publication Date (Web): 28 Jun 2018 Downloaded from http://pubs.acs.org on June 28, 2018
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Industrial & Engineering Chemistry Research
Iron-Modified Graphites towards Boosted Lithium/Sodium Storage Performance and Long-Term Cyclability Si Chen1†, Li-Ping Lv1†, Suo Xiao1, Weiwei Sun1, Xiaopeng Li2 and Yong Wang1* 1
Department of Chemical Engineering, School of Environmental and Chemical Engineering, Shanghai University, 99 Shangda Road, Shanghai, 200444, P. R. China 2
CAS Key Laboratory of Low-Carbon Conversion Science and Engineering, Shanghai Advanced Research Institute (SARI), Chinese Academy of Sciences (CAS), Shanghai 201210, P. R. China
ABSTRACT In this report, we deploy a facile ball-milling technique to produce modified graphites towards boosted lithium/sodium storage performance and long-term cyclability. Specifically, the modified graphite after ball-milling for 120 h (BMNG-120h) shows best performances. It delivers a reversible Li-storage capacity of ~ 842 mA h g-1 (500 cycles, 1 C) and Na-storage capacity of ~ 150 mA h g-1 (250 cycles, 0.1 C). These superior performances can be firstly ascribed to the decreased sheet size and thickness, increased surface area and interlayer spacing of the graphites upon ball-milling. Moreover, cyclic voltammetry tests imply that the diffusion and capacitive-controlled process co-exist and contribute to the high capacity. Galvanostatic Intermittent Titration Technique measurements further indicate a faster Li+ diffusion process. Finally,
the
introduction
of
oxygen-containing
groups
and
iron-modified
characteristics during the ball-milling process may also accelerate the ion and electron transportation, thus together leading to a superior performance of the electrode.
KEYWORDS: Graphite, Anode, Ball-milling, Lithium storage, Sodium storage
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1. INTRODUCTION Scientific researchers are paying great efforts to develop sustainable and efficient energy storage system with low cost due to the diminished traditional energy source. Lithium ion batteries (LIBs) are currently the most popular power sources owing to their superior energy density, long lasting life for service and environmental friendly.1-3 Similar to lithium, sodium also gains extensive attractions for sodium ion batteries (SIBs) due to its abundance, low-cost and typical properties of alkali metals.4-6 As commonly used anode material for commercial LIBs, graphite shows several advantages including good electrical conductivity, reliable cycle stability, and cost effectiveness. Nevertheless, its relatively low Li-storage capacity (theoretically 372 mAh g-1) still hinders its application for commercial electric vehicles with a high capacity requirement.7-12 Moreover, graphite shows also inadequacy when considered as anode materials for SIBs.4 Therefore, modifications such as functionalization,13 compositing,7 oxidizing,14 et al. have been applied to improve their electrochemical performances. In addition to the above-mentioned methods which usually involve multiple synthetic procedures, ball-milling is a more facile and direct technique that can be easily realized for a scalable production with low cost. Indeed, reports using ball-milling to produce graphitic materials with increased capacities were performed a long time ago.12, 15-20 The ball-milling process was reported to facilitate the generation of thinner and disordered graphites with more structural defects and specific surface areas that would benefit the capacity of the graphites. More recently, ball-milling was reported to produce edge-functionalized graphene nanoplatelets for energy storage.21 The graphene nanoplatelets are generated owing to the significant kinetic energy transferred by ball-milling travelling at high speed which is able to unzip the graphitic layers of graphites. Through ball-milling, the graphene nanoplatelets can be 2
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Industrial & Engineering Chemistry Research
simultaneously functionalized by mechanochemical reactions with halogens such as F2, Cl2, Br2 or I2. The finally obtained edge-halogenated graphene nanoplatelets electrodes display good performance in LIBs. 22, 23
In addition to the above-mentioned reports with halogen-modified edges, there are also several other reports on the doping or functional graphite/graphene prepared by ball-milling graphite and doping agents.24-27 Meanwhile, for the other ball-milled graphite materials that are not functionalized or doping, merits coming from functionalization on electrode behavior of rechargeable batteries therefore cannot be relied on. Nevertheless, ball-milling time is believed to be another key factor that plays roles on the electrochemical performance of the milled graphite.12, 28 Different times have been already found to be applied for ball-milling of graphites in previous reports. However, most of them are based on short term of milling (
