T. Taoa,
M. M. Rahmana,
T. Ramireddya,
J. Sunarsob,
Y. Chena and
A. M. Glushenkov*ac
aInstitute for Frontier Materials, GTP, Deakin University, Geelong Waurn Ponds Campus, Locked Bag 20000, Geelong, VIC 3220, Australia. E-mail: alexey.glushenkov@deakin.edu.au
bDepartment of Chemistry, University of Waterloo, 200 University Avenue West, Waterloo, ON N2L 3G1, Canada
cMelbourne Centre for Nanofabrication, 151 Wellington Rd, Clayton, VIC 3168, Australia
First published on 7th August 2014
Some of the prospective electrode materials for lithium-ion batteries are known to have electronic transport limitations preventing them from being used in the electrodes directly. In many cases, however, these materials may become practical if they are applied in the form of nanocomposites with a carbon component, e.g. via incorporating nanoparticles of the phase of interest into a conducting network of carbon nanotubes. A simple way to prepare oxide–carbon nanotube composites suitable for the electrodes of lithium-ion batteries is presented in this paper. The method is based on low-energy ball milling. An electrochemically active but insulating phase of LiFeTiO4 is used as a test material. It is demonstrated that the LiFeTiO4–carbon nanotube composite is not only capable of having significantly higher capacity (∼105–120 mA h g−1 vs. the capacity of ∼65–70 mA h g−1 for the LiFeTiO4 nanoparticles) at a slow current rate but may also operate at reasonably high current rates.
An alternative way to overcome the issue of limited electronic conductivity in the electrode materials is to use networks of carbon nanotubes that can be mixed with the active material to form nanocomposites.9–11 This is particularly beneficial for situations where improvements in rate capability are required.10,11 The nanotubes act as conducting cables to provide electron transport from current collectors through the bulk of the electrode in an efficient manner. There are a few reported techniques to incorporate networks of nanotubes into the electrodes of Li-ion batteries. For example, hydrothermal method,12,13 vacuum filtration method14 and deposition in anodised alumina templates15 have been employed. Some authors have also attempted to grow active electrode materials directly on carbon nanotubes.16
In this paper, a simple method for the preparation of oxide–carbon nanotube composite electrodes is presented. The method is based on a low-energy ball milling treatment. LiFeTiO4 is used as a test electrode material. This phase exhibits reversible electrochemical reactivity with lithium17–20 but is known to have an insulating nature.18 A theoretical capacity of 153.5 mA h g−1 has been suggested.18 It can normally display only limited capacity even when used in the form of nanoparticles. We demonstrate that significant improvement is achieved when the composite of LiFeTiO4 and MWCNTs is prepared by the suggested method and used as an electrode material. Considerably higher capacity is displayed by the composite electrode (∼105–120 mA h g−1 instead of ∼65–70 mA h g−1 for the LiFeTiO4 nanoparticles), and the electrode is capable of operating under relatively fast charge–discharge rates (currents of up to 500 mA g−1 were evaluated). The results indicate that the proposed method for preparing composite electrodes can indeed significantly improve the characteristics of the model electrode based on an insulating phase.
Scanning electron microscopy (SEM, Carl Zeiss SUPRA55VP electron microscope) and transmission electron microscopy (TEM, JEOL JEM-2100F instrument operating at 200 kV) were used to investigate the structure, size, and morphology of the samples. Energy-filtered TEM (EFTEM) elemental maps were obtained using a Gatan Quantum ER 965 Imaging Filter installed on the JEOL JEM-2100F instrument. The three window method was used for the acquisition of the elemental maps. The Branauer–Emmett–Teller (BET) surface area of the sample was determined using a Micromeritics Tristar 3000 adsorption instrument. Thermal gravimetric analysis (TGA, Q50-1534 instrument, air flow, 20 °C min−1 heating rate) was used to estimate the carbon content in the sample.
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Fig. 1 SEM images of LiFeTiO4–carbon nanocomposite (a and b) and XRD patterns of LiFeTiO4 nanoparticles and LiFeTiO4–carbon nanocomposites (c). |
A longer XRD scan was conducted to collect data suitable for Rietveld refinement. Fig. 2a shows Rietveld refinement plot of LiFeTiO4 which contains minor phase impurities, most probably due to Li2O3Ti (JCPDS no. 98-016-2215) and Fe3O4 (JCPDS no. 00-003-0863). Except for the peaks from impurities, the refinements converged into a reasonably low reliability factor (Rwp) of 3.05, indicating a good fit. LiFeTiO4 exhibits spinel structure with intermixed Li and Fe cations due to their almost similar size.25 Rietveld refinement was performed to obtain the approximate distribution of Li and Fe in the tetrahedral sites (8a) and octahedral sites (16a) (Fig. 2b and Table 1) of which Li occupies around 34% of the octahedral sites while Fe occupies around 56% of the tetrahedral sites, leading to a formula of (Li0.44Fe0.56)(Li0.68Fe0.32Ti)O4. This implies a larger amount of Li in octahedral site and overall, a formation of a non-stoichiometric compound with a slight excess of Li (relative to Fe) – compare with the ideal stoichiometric formula of (Li0.5Fe0.5)(Li0.5Fe0.5Ti)O4.
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Fig. 2 Rietveld refinement of the crystal structure: (a) refinement plot of LiFeTiO4 between 15–100°, (b) Structure of LiFeTiO4 (drawn using VESTA).26 |
LiFeTiO4 | ||||||
---|---|---|---|---|---|---|
Space group | Fd-3m | |||||
Space group no. | 227 | |||||
a (Å) | 8.356(4) | |||||
Atom | Np | x | y | z | Occ. | biso (Å2) |
Ti | 16 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 |
Li | 16 | 0.5 | 0.5 | 0.5 | 0.34(1) | 0.5 |
Fe | 16 | 0.5 | 0.5 | 0.5 | 0.16(1) | 0.5 |
Li | 8 | 0.125 | 0.125 | 0.125 | 0.44(7) | 0.5 |
Fe | 8 | 0.125 | 0.125 | 0.125 | 0.56(7) | 0.5 |
O | 32 | 0.2514(5) | 0.2514(5) | 0.2514(5) | 1 | 0.5 |
χ2 | 1.41 | |||||
Rp (%) | 2.31 | |||||
Rwp (%) | 3.05 | |||||
Rexp (%) | 2.17 | |||||
RBragg (%) | 0.95 |
The measured BET surface area of the LiFeTiO4–carbon nanocomposite was 58.3 m2 g−1. Fig. 3 shows the plot of the adsorbed amount vs. pressure points used for the calculation of BET area.
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Fig. 3 The plot of the adsorbed amount vs. pressure points used for the calculation of BET surface area. |
The TEM characterisation further confirms these findings. Indeed, a bright-field image shown in Fig. 4a displays a mixture of metal oxide particles (possessing a typical darker contrast) and MWCNTs. A selected area electron diffraction pattern (Fig. 4b) includes a number of rings, consistent with the presence of a polycrystalline structure or a large number of randomly oriented nanoparticles. The pattern can be indexed in line with the diffraction rings of the LiFeTiO4 phase, which correlates well with the XRD data. The crystallographic Miller indices corresponding to the visible rings in the electron diffraction pattern are labelled in Fig. 4b.
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Fig. 4 TEM characterisation of the nanocomposite: (a) bright-field image; (b) selected area diffraction pattern. |
Energy-filtered TEM was employed to demonstrate the degree of mixing of LiFeTiO4 particles and MWCNTs directly. A bright-field image is shown in Fig. 5a and it displays rather confusing contrast due to the overlap between various components of the composite. Extracting chemical information via the filtering of electron energy helps to visualise the location of LiFeTiO4 material and carbon nanotubes in the sample. Individual elemental maps of carbon, iron oxygen and titanium are shown in Fig. 5b–e. For obvious reasons, the Fe, O and Ti maps show similar distributions of these elements. One of the maps (Ti) was selected and plotted together with the carbon map in a colour-coded plot (Fig. 5f). The overlay of the Ti and carbon maps (Fig. 5f) displays the chemical information required for the correct interpretation of the bright-field image in Fig. 5a and provides direct visualisation of the location of MWCNTs and LiFeTiO4 nanoparticles in the sample. LiFeTiO4 and CNT components are well-mixed in the nanocomposite. We believe that the LiFeTiO4 particles are simply connected to each other via mechanical force. As it follows from TEM images (Fig. 4 and 5), the sample represents aggregates of inorganic nanoparticles with nanotubes in which the network of nanotubes squeeze particles between individual nanotubes. It is also possible that some nanoparticles of LiFeTiO4 may become cold welded to each other, as it is a well-known phenomenon in ball milling.
Fig. 6 shows the TGA plot of the LiFeTiO4–MWCNT composite in air. The low temperature weight loss (25–300 °C) is related to the departure of moisture and other adsorbed species as well as processes in the impurities present in the sample (<5 wt.%, according to the specification of MWCNTs). It is reasonable to attribute weight loss above 300 °C to the oxidation of nanotubes. Indeed, as Hsieh et al.27 have shown by differential scanning calorimetry, the onset of the oxidation for the multiwalled carbon nanotubes is above 300 °C. We therefore attribute weight changes above 300 °C predominantly to the oxidation of carbon nanotubes. According to Fig. 6, the weight loss between 300 and 500 °C is approximately 17.5 wt.% while 69.5 wt.% of the sample remains intact above 500 °C. We can estimate from this measurement that the weight ratio of LiFeTiO4 to MWCNTs in the produced sample is likely to be about 3.97:
1, close to the ratio of 4
:
1 between the initial ingredients for the preparation of the composite.
Fig. 7a shows the discharge capacities versus cycle number for LiFeTiO4 and the LiFeTiO4–MWCNT composite at a current rate of 25 mA g−1. The LiFeTiO4–C nanocomposite exhibits a stable discharge capacity of about 110 mA h g−1 after 100th cycles, which is much higher than that of LiFeTiO4 nanoparticles (about 70 mA h g−1). The Coulombic efficiencies of the two electrodes are also plotted in the same graph. The corresponding selected discharge–charge voltage profiles for the nanocomposite electrode from the first 50 cycles are shown in Fig. 7b. The shape of the profiles does not change significantly during cycling, indicating good capacity retention at slow current rates. The rate capabilities of both the LiFeTiO4 and LiFeTiO4–MWCNT electrodes were tested at various current densities between 12.5 and 500 mA g−1 (Fig. 7c and d). It is apparent that the capacity retention for the composite electrode is superior, and the discharge capacities of 135, 122, 112, 97, 76, and 65 mA h g−1 were recorded for this electrode after 20 cycles at current densities of 12.5, 25, 50, 100, 200, and 500 mA g−1, respectively. The composite electrode can obviously operate at up to 500 mA g−1 currents and retain capacity equal to or above that of LiFeTiO4 nanoparticles at a slow current rate of 25 mA g−1.
It is important to note that the capacity of the LiFeTiO4 and LiFeTiO4–MWCNT electrodes depends on the chosen potential range and will be smaller if the potential range of 2.0–4.5 is used. To complete the electrochemical characterisation, we have also included the CV curves for LiFeTiO4 and LiFeTiO4–MWCNT electrodes here (Fig. 8).
Electrochemical impedance spectroscopy measurements were carried out for the assembled cells (open circuit potential state) to investigate the rate of electron transfer in the LiFeTiO4 and LiFeTiO4–MWCNT electrodes. Typical Nyquist plots recorded for both electrodes are presented in Fig. 9. Both plots display one compressed semicircle in the high to medium frequency region and a sloped line in the low-frequency region. The diameter of each semicircle is related to the charge transfer resistance (Rct). The smaller the diameter, the smaller the charge transfer resistance is, and this parameter is a function of the electronic conductivity in the electrodes.28,29 It is clearly observed that diameter of the composite LiFeTiO4–MWCNT electrode is much smaller than that of the LiFeTiO4-based electrode. The values of Rct for the LiFeTiO4 and LiFeTiO4–MWCNT electrodes were calculated to be 829 Ω and 199 Ω, respectively. This indicates that LiFeTiO4 particles mixed with carbon nanotubes in a composite provide much easier charge transfer at the electrode/electrolyte interface, and that consequently decreases the overall battery internal resistance, enabling higher reactivity and lower polarisation.30,31 The underlying reason is the significant enhancement of the electronic conductivity in the electrode based on the LiFeTiO4–MWCNT composite; the nanotubes provide conductive paths in the vicinity of the LiFeTiO4 nanoparticles, and this is a key factor in improving the discharge capacity and rate capability of the LiFeTiO4–MWCNT electrode in respect to those of a more conventional LiFeTiO4 electrode.
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Fig. 9 Electrochemical impedance spectra for the assembled coin cells incorporating working electrodes based on LiFeTiO4 nanoparticles and the LiFeTiO4–MWCNT composite. |
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