Fabrication of core/shell ZnWO4/carbon nanorods and their Li electroactivity
© Shim et al; licensee Springer. 2012
Received: 2 September 2011
Accepted: 5 January 2012
Published: 5 January 2012
Carbon-coated ZnWO4 [C-ZW] nanorods with a one-dimensional core/shell structure were synthesised using hydrothermally prepared ZnWO4 and malic acid as precursors. The effects of the carbon coating on the ZnWO4 nanorods are investigated by thermogravimetry, high-resolution transmission electron microscopy, and Raman spectroscopy. The coating layer was found to be in uniform thickness of approximately 3 nm. Moreover, the D and G bands of carbon were clearly observed at around 1,350 and 1,600 cm-1, respectively, in the Raman spectra of the C-ZW nanorods. Furthermore, lithium electroactivities of the C-ZW nanorods were evaluated using cyclic voltammetry and galvanostatic cycling. In particular, the formed C-ZW nanorods exhibited excellent electrochemical performances, with rate capabilities better than those of bare ZnWO4 nanorods at different current rates, as well as a coulombic efficiency exceeding 98%. The specific capacity of the C-ZW nanorods maintained itself at approximately 170 mAh g-1, even at a high current rate of 3 C, which is much higher than pure ZnWO4 nanorods.
Since Poizot et al. reported that select transition metal-based oxides exhibit high capacities , new anode materials based on metal oxides have been extensively studied [2, 3] as promising alternatives to carbon-based materials used as anode materials in commercial Li-ion batteries [LIBs]. However, in spite of all the research, some challenges to overcome still remain, such as large volume changes during Li+ insertion and extraction.
Tailoring nanostructures is one popular approach for improving the electrochemical performance of these materials, such as cyclic retention and rate capability [4, 5]. Thus far, considerable efforts have been devoted to overcome these problems by using the active/inactive composite concepts, including core-shell nanostructures, in which the inactive phase serves as a buffer and partly alleviates mechanical stress caused by the volume change of the active phase [6, 7]. Carbon coating can be also derived from this concept because carbon materials are often of low activity. Numerous previous studies have demonstrated carbon coating as an effective route to improve the electrochemical performance of metal oxide-based anode materials for LIBs. However, most of the previous methods for producing carbon-coated materials were limited, using glucose and sucrose as carbon precursors to obtain the carbon-rich polysaccharide, as well as relatively complicated [8–10].
Recently, Hassan et al.  have reported carbon-coated MoO3 nanobelts using malic acid as a new carbon source. However, other metal oxide-based materials for application to anodes of LIBs are rarely reported although the method of carbon coating using malic acid has been published. Herein, the authors report on a simple preparation of one-dimensional core/shell ZnWO4 nanorods with homogeneous carbon coating and their enhanced electrochemical performance versus that of lithium as a new anode material for LIBs. Furthermore, when used as anode materials in LIBs, the carbon-coated ZnWO4 nanorods exhibited significantly improved rate capabilities when compared to pure ZnWO4 nanorods. The result demonstrates that a suitable carbon coating is an effective strategy to improve the rate capabilities of the oxide-based anode materials in LIBs. From a survey of the literature, this is the first report on carbon-coated ZnWO4 nanorods.
Carbon-coated ZnWO4 nanorods were achieved in two stages: first, ZnWO4 nanorods as core parts were prepared using a hydrothermal process with adjusting pH values at 180°C for 12 h; this was followed by general washing and drying steps. Zinc nitrate hexahydrate (Zn(NO3)2·6H2O, 15 mM, 99.0%, Aldrich Chemicals, St. Louis, MO, USA) and an equal amount of sodium tungstate dehydrate (Na2WO4·2H2O, 15 mM, 99.0%, High Purity Chemicals, Tarapur, Maharashtra, India) were used as starting materials. The ZnWO4 nanorods thus obtained were then coated with carbon. Malic acid (C4H6O5, 99.0%, Aldrich Chemicals, St. Louis, MO, USA) was used as the carbon source. The malic acid was first dispersed in toluene (C7H8, 99.5%, Alfa Chemicals, Berkshire, UK), and the ZnWO4 nanorods obtained from the hydrothermal technique were added to toluene while stirring at room temperature for 2 h. Subsequently, the slurry was dried at 120°C for 4 h and then 180°C for 6 h under vacuum.
The weight fraction of the coated carbon was determined by thermogravimetric analysis [TGA] (model DTG-60 H, Shimadzu, Kyoto, Japan). The crystalline phase of the prepared samples was carried out using powder X-ray diffraction [XRD] (model D/max-2500 V/PC, Rigaku, Tokyo, Japan), and the distinct properties of the carbon-coated sample were confirmed within the wavelength range of 1,250 to 1,650 cm-1 using laser Raman spectrometry (spectrometer model SPEX-1403, SPEX, Seoul, South Korea). The microstructures of the carbon-coated samples were examined using transmission electron microscopy [TEM] (model JEM-2100F, JEOL, Tokyo, Japan). High-resolution transmission microscopy [HRTEM] was performed for further sample analysis. The electrochemical performance of the samples versus that of lithium was measured by means of a multichannel potentiostatic/galvanostatic system (model WBCS 3000, WonATech, Seoul, South Korea). All samples were galvanostatically cycled as anodes and recorded in a voltage window between 0.01 and 3.0 V.
Results and discussions
More importantly, the Raman analysis results can confirm the presence of carbon loading in the C-ZW nanorod samples. As depicted in Figure 3b, the spectrum of the C-ZW nanorods in the wavelength range of 1,250 to 1,650 cm-1, which is magnified from the dash box in Figure 3a, exhibited obvious differences from the pure ZW nanorods. The peaks indexed by black arrows at approximately 1,370 and 1,580 cm-1 are related to carbon, which are designated in terms of D and G bands. These peaks are in good correspondence with the Raman spectra of the amorphous carbon reported in the literature [16–18].
To further confirm the carbon coating on the surface of ZnWO4 nanorods, C-ZW nanorods were studied using TEM, as shown in Figure 4. The C-ZW nanorods obviously sustained the original, rod-like morphology of pure ZW (Figure 4a). A thin carbon layer was homogeneously coated onto the surface of each pure ZW (Figures 4b, c), without deposition of isolated carbon islands by excess carbon pile-up. This resulted in the formation of a hybrid ZnWO4/carbon core/shell structure (inset of Figure 4c). The uniform thickness of carbon was approximately 3 nm, based on the HRTEM images (Figures 4d, e) of the individual nanorod, which was taken from the open-square regions in Figure 4c. The surface of the core ZnWO4 was very clear and clean, and the magnified view shows the highly crystalline structure of the ZnWO4[19, 20]. In Figure 4e, the C-ZW nanorods were structurally uniform, with interplanar spacing of roughly 0.468, 0.362, and 0.284 nm, corresponding to the (100), (110), and (020) lattice spacings of the ZnWO4 structure. In addition, the indexed selected area electron diffraction [SAED] pattern via the <001> zone axis revealed the single-crystal nature of the nanorods and further confirmed preferential growth along the  direction of the nanorod structures (Figure 4f), as previously reported in the hydrothermal synthesis of pure ZW nanorods . As a result, such uniform carbon loading on ZnWO4 is expected to improve the electronic conductivity and electrochemical performance of the pure ZW nanorods.
In summary, we have demonstrated the synthesis of carbon-coated ZnWO4 nanorods with a one-dimensional core/shell structure using a simple hydrothermal route and subsequent carbon coating, and their enhanced Li-storage performance compared with pure ZW nanorods. The uniform loading of amorphous carbon onto the ZnWO4 nanorods was clearly confirmed through Raman spectra and HRTEM observations. In particular, the C-ZW nanorods exhibited better capacity delivery than pure ZW nanorods at different current rates and a coulombic efficiency greater than 98%. The specific capacity held steady at approximately 170 mAh g-1 even at a current rate as high as 3 C. Therefore, these C-ZW nanorods may offer an exciting potential for the development of new anode materials for Li-ion batteries.
This work was supported by the National Research Foundation of Korea (NRF) grant funded by the Korean government (MEST) (No. 2011-0019119 & 2011-0030300).
- Poizot P, Laruelle S, Grugeon S, Dupont L, Tarascon JM: Nano-sized transition-metal oxides as negative-electrode materials for lithium-ion batteries. Nature 2000, 407: 496. 10.1038/35035045View Article
- Sharma Y, Sharma N, Subba Rao GV, Chowdari BVR: Nanophase ZnCo2O4as a high performance anode material for Li-ion batteries. Adv Funct Mater 2007, 17: 2855. 10.1002/adfm.200600997View Article
- Shim HW, Cho IS, Hong KS, Cho WI, Kim DW: Li electroactivity of iron (II) tungstate nanorods. Nanotechnology 2010, 21: 465602. 10.1088/0957-4484/21/46/465602View Article
- Arico AS, Bruce P, Scrosati B, Tarascon JM, Van Schalkwijk W: Nanostructured materials for advanced energy conversion and storage devices. Nat Mater 2005, 4: 366. 10.1038/nmat1368View Article
- Park KS, Kang JG, Choi YJ, Lee SJ, Kim DW, Park JG: Long-term, high-rate lithium storage capabilities of TiO2nanostructured electrodes using 3D self-supported indium tin oxide conducting nanowire arrays. Energy Environ Sci 2011, 4: 1796. 10.1039/c0ee00804dView Article
- Kim DW, Ko YD, Park JG, Kim BK: Formation of lithium-driven active/inactive nanocomposite electrodes on Ca3Co4O9nanoplates. Angew Chem Int Ed 2007, 46: 6654. 10.1002/anie.200701628View Article
- Hassoun J, Panero S, Simon P, Taberna PL, Scrosati B: High-rate, long-life Ni-Sn nanostructured electrodes for lithium-ion batteries. Adv Mater 2007, 19: 1632. 10.1002/adma.200602035View Article
- Chou SL, Wang JZ, Zhong C, Rahman MM, Liu HK, Dou SX: A facile route to carbon-coated SnO2nanoparticles combined with a new binder for enhanced cyclability of Li-ion rechargeable batteries. Electrochim Acta 2009, 54: 7519. 10.1016/j.electacta.2009.08.006View Article
- Sun X, Liu J, Li Y: Oxides@C core-shell nanostructures: one-pot synthesis, rational conversion, and Li storage property. Chem Mater 2006, 18: 3486. 10.1021/cm052648mView Article
- He X, Pu W, Wang L, Ren J, Jiang C, Wan C: Synthesis of spherical nano tin encapsulated pyrolytic polyacrylonitrile composite anode material for Li-ion batteries. Solid State Ionics 2007, 178: 833. 10.1016/j.ssi.2007.02.013View Article
- Hassan MF, Guo ZP, Chen Z, Liu HK: Carbon-coated MoO2nanobelts as anode materials for lithium-ion batteries. J Power Sources 2010, 195: 2372. 10.1016/j.jpowsour.2009.10.065View Article
- Shim HW, Cho IS, Hong KS, Lim AH, Kim DW: Wolframite-type ZnWO4nanorods as new anodes for Li-ion batteries. J Phys Chem C 2011, 115: 16228. 10.1021/jp204656vView Article
- Errandonea D, Manjón FJ, Garro N, Rodríguez-Hernández P, Radescu S, Mujica A, Muñoz A, Tu CY: Combined Raman scattering and ab initio investigation of pressure-induced structural phase transitions in the scintillator ZnWO4. Phys Rev B 2008, 78: 054116.View Article
- Kalinko A, Kuzmin A: Raman and photoluminescence spectroscopy of zinc tungstate powders. J Lumin 2009, 129: 1144. 10.1016/j.jlumin.2009.05.010View Article
- Siriwong P, Thongtem T, Phuruangrat A, Thongtem S: Hydrothermal synthesis, characterization, and optical properties of wolframite ZnWO4nanorods. Cryst Eng Comm 2011, 13: 1564.View Article
- Pasteris JD, Wopenka B: Necessary, but not sufficient: Raman identification of disordered carbon as a signature of ancient life. Astrobiology 2003, 3: 727. 10.1089/153110703322736051View Article
- Yang CJ, Jiang JL, Ping DJ, Fei ZH: In situ Raman spectroscopy study on dissociation of methane at high temperatures and at high pressures. Chin Phys Lett 2008, 25: 780. 10.1088/0256-307X/25/2/116View Article
- Guedes A, Ribeiro N, Oliveria M, Noronha F, Abreu I: Comparison between urban and rural pollen of Chenopodium alba and characterization of adhered pollutant aerosol particles. J Aerosol Sci 2009, 40: 81. 10.1016/j.jaerosci.2008.07.012View Article
- Yu SH, Liu B, Mo MS, Huang JH, Liu XM, Qian YT: General synthesis of single-crystal tungstate nanorods/nanowires a facile, low-temperature solution approach. Adv Funct Mater 2003, 13: 639. 10.1002/adfm.200304373View Article
- Shi R, Wang Y, Li D, Xu J, Zhu Y: Synthesis of ZnWO4nanorods with  orientation and enhanced photocatalytic properties. Appl Catal B-Environ 2010, 100: 173. 10.1016/j.apcatb.2010.07.027View Article
This article is published under license to BioMed Central Ltd. This is an Open Access article distributed under the terms of the Creative Commons Attribution License (http://creativecommons.org/licenses/by/2.0), which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.