Binghui Xua,
Hao Wua,
C. X. (Cynthia) Lina,
Bo Wangab,
Zhi Zhangc and
X. S. Zhao*a
aSchool of Chemical Engineering, The University of Queensland, St. Lucia, Brisbane, QLD 4072, Australia. E-mail: george.zhao@uq.edu.au
bSchool of Chemical Engineering and Technology, Harbin Institute of Technology, Xidazhi Street, 150001 Harbin, China
cMaterials Engineering, The University of Queensland, St. Lucia, Brisbane, QLD 4072, Australia
First published on 24th March 2015
The severe volume change and aggregation of silicon nanoparticles (SiNPs) when used as an anode for lithium ion batteries (LIBs) are the key issue. Here, we demonstrate a novel approach to wrapping SiNPs in three-dimensional reduced graphene oxide (RGO) aerogel. The RGO aerogel not only provides a porous network for entrapping SiNPs to accommodate the volume change during cycling, but also facilitates electrolyte transport. Furthermore, the continuous RGO network is favourable for electron transfer. The graphene-wrapped SiNPs were stable and displayed an excellent rate capacity, delivering a reversible capacity of about 2000 mA h g−1 after 40 cycles.
Graphene, a monolayer of carbon atoms arranged in a two-dimensional (2D) honeycomb network, has been used to improve the stability and electric conductivity of nanostructured Si electrodes for LIBs.24 Due to its high electronic conductivity, superior mechanical strength and flexibility, graphene can improve electron transport and Li+ diffusion, thus enhancing the electrochemical performance of SiNPs for lithium ion storage.23,25–27 In spite of the observed improvement of the electrochemical performance of SiNPs by graphene, SiNPs still tend to aggregate. As a result, the performance of the graphene–SiNPs composites inevitably degrades during charge/discharge. Recently, three-dimensional (3D) graphene materials, including hydrogels and aerogels, have been shown to possess advantages, such as high surface area and good electrical conductivity.28–30 These 3D graphene materials may be favourable for stabilizing SiNPs.
This paper describes a method for preparing graphene-stabilized SiNPs on the basis of electrostatic interactions. Because both graphene oxide (GO) and SiNPs (there is a thin layer of SiO2 on the surface of the SiNPs) are negatively charged in a wide pH range, the SiNPs used in this work were firstly modified using poly(diallydimethylammonium chloride) (PDDA, a positively charged polyelectrolyte) to change the surface charge nature from being negative to being positive following a protocol described elsewhere.23 As schematically illustrated in Scheme 1, the PDDA-modified SiNPs interacted strongly with negatively charged GO sheets to form a Si–GO composite (hereinafter designated as Si@GO). Because of the flexibility of GO sheets, SiNPs were wrapped in by the GO sheets. The GO in the Si@GO suspension was then reduced using gallic acid (GA, a natural plant phenolic acid; see Fig. S1A† for its structure) in an oil bath at 95 °C for 4 h. It has been reported that in the presence of natural phenolic acid, GO can be reduced to assemble into RGO hydrogels driven by the enhancing hydrophobicity and π–π interactions among the nanosheets during the reduction.28,31 During this GA reduction process, yellow-brown-coloured Si@GO suspension gradually turned transparent to form a dark grey gel separating from the suspension, indicating that the GO had been reduced to reduced graphene oxide (RGO) and the SiNPs had been wrapped by the RGO architecture. In order to understand the stabilization effect of RGO sheets on SiNPs, the obtained Si@RGO hydrogel was crushed and redispersed in an aqueous GO suspension, which was further reduced with GA at 95 °C for 12 h. After freeze-drying and thermal reduction at 700 °C for 2 h under H2/Ar atmosphere, a black 3D RGO aerogel with confined SiNPs, designated as Si/RGO-AG, was obtained. For comparison purpose, another two samples were prepared. One of them, designated as Si/RGO, was prepared by mixing SiNPs with aqueous GO suspension, followed by filtration and thermal reduction at 700 °C for 2 h under H2/Ar atmosphere. The other one, designated as Si/RGO-SWAG (SiNPs were wrapped by RGO aerogel in a single step), was prepared according to the same procedure of preparing sample Si/RGO-AG except for without Step 3 (see Scheme 1).
Fig. 1A and B are the SEM images of Si/RGO-AG under different magnifications. SiNPs with an average diameter of 100 nm dispersed the 3D RGO aerogel framework can be clearly seen. On contrast, severe aggregation of SiNPs can be observed from pure SiNPs (Fig. S3A†), sample Si/RGO (Fig. S3B†) and sample Si/RGO-SWAG (Fig. S3C and S3D†). In particular, the SiNPs in sample Si/RGO formed micro-sized aggregates. After a single-step wrapping by RGO, the aggregation of SiNPs was not significant. However, some SiNPs were not fully wrapped by RGO and aggregates can be still observed. This explains the capacity fading of sample Si/RGO-SWAG. The elemental analysis results of Si/RGO-AG (Fig. S4†) confirmed the existence of major elements Si and C and their homogeneous distribution in the 3D aerogel. In this Si/RGO-AG composite, the graphene aerogel provides a porous network for the entrapped SiNPs, thus is beneficial for accommodating the volume change of these SiNPs during electrochemical reactions. The porous network also facilitates electrolyte transport, potentially enhancing the rate capacity of LIBs. Besides, the continuous interconnected graphene network creates favourable electron pathways against cycling processes. The HRTEM image shown in Fig. 1C also clearly demonstrates the existence of a continuous RGO network with SiNPs entrapped. The HRTEM image in Fig. 1D shows that SiNPs were well-encapsulated within the RGO aerogel network.
Fig. 2A shows the X-ray diffraction (XRD) patterns of Si/RGO-AG and SiNPs. All diffraction peaks due to SiNPs can be seen from sample Si/RGO-AG, indicating that the silicon crystalline structure in the Si/RGO-AG composite retained after the freeze-drying and thermal reduction treatments. Fig. 2B presents the Raman spectra of Si/RGO-AG and pristine SiNPs. The absorption bands due to SiNPs can be seen from Si/RGO-AG, confirming the presence of crystalline Si particles in the composite. There are two more absorption bands at 1350 and 1596 cm−1, respectively. These two peaks are assigned to the D band and G band of graphene, respectively,35 confirming the presence of RGO in the composite.
Fig. S5† presents the C1s XPS spectra of samples. As can be seen, GO showed three peaks at 284.9, 286.8, and 289.0 eV, corresponding to CC in aromatic rings, C–O–C in epoxy and alkoxy, and C
O in carbonyl and carboxyl groups, respectively. It is clearly seen that the peak intensity due to C–O–C and C
O bonds of sample Si/RGO-AG is significantly lower than that of sample GO. The intensity of the peak ascribed to C
C however increased after reduction. These data suggest that the oxygen-containing groups on GO were largely removed, and most of the conjugated bonds were restored by GA reduction and thermal treatment.
The N2 adsorption/desorption isotherms of the Si/RGO-AG composite (see Fig. 2C) showed a type IV isotherm with an H3 hysteresis loop, indicating a mesoporous structure of the material. The Brunauer–Emmett–Teller (BET) surface area and pore volume of the composite was measured to be 125 m2 g−1 and 0.37 cm3 g−1, respectively, much higher than that of pure SiNPs (25 m2 g−1 and 0.055 cm3 g−1, respectively, see Fig. S6A†). The Barrett–Joyner–Halenda (BJH) pore size distribution curve of Si/RGO-AG (see Fig. 2D) demonstrates that Si/RGO-AG composite had a mesoporous structure with two pore systems. The intensive peak around 5.0 nm is due to the presence of small gaps among randomly stacked graphene sheets, while the broad peak centred at about 26 nm may be due to the large voids between inter-twisted graphene sheets.36 The high surface area along with the existence of mesopores in Si/RGO-AG should offer a large material–electrolyte contact area and promote the diffusion of Li+ ions if Si/RGO-AG is used as electrode materials for lithium storage.
Thermal gravimetric analysis (TGA) was carried out in air and the results are shown in Fig. S6B.† It can be seen that the mass of the pristine SiNPs increased slightly with a mass gain of about 0.150 wt% at 700 °C. This gain was due to the oxidation of Si by O2 to form SiO2. At 700 °C, the residual of the RGO aerogel was about 3.02 wt%, which was due to the impurities in the GO sample. The weight loss of the Si/RGO-AG composite at 700 °C was about 19.3 wt%. Based on the TGA data, the Si/RGO-AG composite was calculated to contain about 80.0 wt% SiNPs and 20.0 wt% RGO aerogel.
The electrochemical performance of the Si/RGO-AG composite as an anode was assembled and tested in a CR2032 coin cell where lithium foil was used as a counter electrode. For comparison, the cycling performance of electrode Si/RGO was also tested under the same experimental conditions. Fig. 3A shows typical cyclic voltammetry (CV) curves of electrode Si/RGO-AG in the potential range of 0.02–1.20 V (vs. Li+/Li) at a scan rate of 0.1 mV s−1 of the first two cycles, starting at the open circuit potential of 1.59 V. A broad cathodic peak in the first cycle appeared at 0.69 V, indicating the formation of solid electrolyte interphase (SEI).8 This cathodic peak disappeared in the second cycle and correlated to an initial capacity loss. The main cathodic part of the second cycle displayed a peak at 0.19 V, corresponding to the formation of Li–Si alloy phases.37 The anodic part showed two peaks at 0.34 and 0.52 V, corresponding to the phase transition from Li–Si alloys to amorphous Si.8,23
Fig. 3B displays the discharge/charge profiles of the initial three cycles of electrode Si/RGO-AG under a current density of 150 mA g−1 in the voltage window of 0.02 to 1.2 V (vs. Li+/Li). The onset slope at about 0.7 V in the initial discharging curve, which disappeared in the following cycles, corresponds to the SEI formation.8 Besides, the main discharge plateau is around 0.2 V and the charge plateau is around 0.5 V. All these features are in good agreement with the CV results discussed above. The specific capacity was calculated based on the total mass of Si/RGO-AG. The initial discharge/charge capacities were 3446 and 2535 mA h g−1, respectively, to give an initial coulombic efficiency of 73.6%. The initial irreversible capacity of electrode Si/RGO-AG can be attributed to the formation SEI, the unexpected reaction of the remaining oxygen-containing groups in the RGO aerogel and SiO2 layer on the surface of SiNPs with Li ions.27,38 After the second cycle, the coulombic efficiency tended to increase and stabilize. It is interesting to note that the curves of the second and third cycles almost overlapped each other, which indicates a good cycling stability of the electrode. The reversible capacities of the second and third cycles compared with the first cycle were slightly increased, which can be attributed to the activation of the SiNPs in the Si/RGO-AG composite.
Fig. 3C shows the cycling performance of Si/RGO-AG at a current density of 150 mA g−1, together with electrodes Si/RGO-SWAG and Si/RGO. It can be seen that the initial charge and discharge capacities of electrode Si/RGO were the lowest among the three electrodes studied. This poor performance of electrode Si/RGO was probably due to severe aggregation of the SiNPs, indicating the RGO sheets did not stabilize the SiNPs well. After about 20 cycles, the reversible capacity dropped drastically to about 450 mA h g−1, confirming that the SiNPs were not stabilized well by the RGO sheets. These results suggest that the physical mixing method is not a good approach to stabilizing SiNPs. While the initial discharge/charge capacities of electrode Si/RGO-SWAG reached to 3360 and 2450 mA h g−1, respectively, its reversible capacity decreased to about 615 mA h g−1 after 40 cycles. The improved performance of electrode Si/RGO-SWAG indicates the single-step wrapping method illustrated in Scheme 1 is advantageous over the physical mixing method. This fast capacity fading however indicates that the single-step wrapping method still could not afford efficient stabilization of SiNPs. On contrast, the Si/RGO-AG electrode showed a significantly improved cycling performance with the highest initial charge/discharge capacities and delivered a reversible capacity of 1984 mA h g−1 after 40 cycles.
Fig. 3D demonstrates the rate capability of the Si/RGO-AG at current densities ranging from 170 mA g−1 to 2500 mA g−1. The battery delivered a reversible capacity of about 1000 and 600 mA h g−1 at the current densities of 2000 and 2500 mA g−1, respectively. Furthermore, the capacity reached around 2000 mA h g−1 when the current density was decreased to 170 mA g−1 after having been cycled at higher current densities, indicating a good cycling stability of Si/RGO-AG.
Fig. S7A† shows the SEM image of electrode Si/RGO-AG after 40 cycles. As can be seen, the Si/RGO-AG composite maintained its integrity and porous structure. In addition, the SiNPs were entrapped by the RGO framework, contributing to the significantly improved cycling performance of Si/RGO-AG. The Nyquist plots of the Si/RGO-AG electrode are presented in Fig. S7B.† The depressed semicircle in the high-frequency region represents the resistance of the SEI film and the charge-transfer resistance, while the straight lines in the low-frequency region corresponds to the diffusion kinetics of lithium ions. No obvious impedance increase is observed after cycling due to the stable SEI. The impedance decrease may be attributed to the gradual electrolyte transport into the electrode and the increasing conductivity of the SiNPs after lithiation.
The improved cycle performance and enhanced rate capability of Si/RGO-AG can be attributed to the following reasons: (i) the Si/RGO-AG composite created sufficient space and efficiently accommodated the drastic volume change of the entrapped SiNPs during cycling; (ii) the interconnected 3D RGO aerogel network maintained the integrity of the electrode structure, prohibited the detachment of the SiNPs from the current collector and improved the electrical conductivity of the electrode; (iii) the existence of meso- and macro- pores provided an efficient pathway for electrolyte transport and facilitated Li+ diffusion, thus enhancing the rate performance.
Footnote |
† Electronic supplementary information (ESI) available. See DOI: 10.1039/c5ra00566c |
This journal is © The Royal Society of Chemistry 2015 |