Copper Nanoparticle-Incorporated Carbon Fibers as Free-Standing Anodes for Lithium-Ion Batteries
© Han et al. 2016
Received: 18 February 2016
Accepted: 22 March 2016
Published: 31 March 2016
Copper-incorporated carbon fibers (Cu/CF) as free-standing anodes for lithium-ion batteries are prepared by electrospinning technique following with calcination at 600, 700, and 800 °C. The structural properties of materials are characterized by X-ray diffraction (XRD), Raman, thermogravimetry (TGA), scanning electron microscopy (SEM), transmission electron microscope (TEM), and energy dispersive X-ray spectrometry (EDS). It is found that the Cu/CF composites have smooth, regular, and long fibrous morphologies with Cu nanoparticles uniformly dispersed in the carbon fibers. As free-standing anodes, the unique structural Cu/CF composites show stable and high reversible capacities, together with remarkable rate and cycling capabilities in Li-ion batteries. The Cu/CF calcined at 800 °C (Cu/CF-800) has the highest charge/discharge capacities, long-term stable cycling performance, and excellent rate performance; for instance, the Cu/CF-800 anode shows reversible charge/discharge capacities of around 800 mAh g−1 at a current density of 100 mA g−1 with stable cycling performance for more than 250 cycles; even when the current density increases to 2 A g−1, the Cu/CF-800 anode can still deliver a capacity of 300 mAh g−1. This excellent electrochemical performance is attributed to the special 1D structure of Cu/CF composites, the enhanced electrical conductivity, and more Li+ active positions by Cu nanoinclusion.
Rechargeable lithium-ion batteries are used extensively due to their high energy and power densities [1–3]. State-of-the-art lithium secondary batteries are composed of graphite anode, which has low theoretical specific capacity (372 mAh g−1) and limited rate capability . Thus, new carbon-based anode materials such as carbon nanotube , nanofiber , nanobead , hollow nanosphere , graphene , and their hybrids  with enhanced Li+ storage capacities and high rate performance have been explored as alternative candidates for anode of Li-ion batteries. Among them, one-dimensional (1D)-structured materials such as fibers, rods, and nanotubes can usually improve the physical or chemical interactions of the electrodes with lithium ions since their large surface-to-volume ratio and fast electronic conducting pathway.
Furthermore, with the recent improvements in lightweight and flexible battery for potential applications in portable and bendable electronic equipment, for example, wearable devices, implantable medical devices, distributed sensors, and soft free-standing electrode-active materials without binder and conductive agent are significantly for such flexible batteries. Many advanced techniques have been developed to fabricate flexible free-standing carbonous electrodes, for instance, vacuum filtration [11, 12], aerosol pyrolysis [13, 14], anodic oxidation , chemical vapor deposition , sol-gel deposition [17–19], sputtering , and spreading . Electrospinning also turns out to be a simple and versatile method for generating ultrathin fibers and hollow fibers [22–26]. Several researchers have successfully applied the electrospinning technique for the fabrication of non-woven film electrodes in lithium-ion batteries [26–29].
In the present work, we prepared copper-incorporated carbon fibers (Cu/CF) by electrospinning Cu(NO3)2 and polyacrylonitrile (PAN)-mixed solution and subsequent thermal treatment at different temperatures. The structural and electrochemical properties of the flexible non-woven Cu/CF films were systematically investigated. The Cu/CF composites show smooth, regular, and long fibrous morphologies with Cu nanoparticles uniformly dispersed in the carbon fibers. The Cu/CF sample annealed at 800 °C (Cu/CF-800) shows higher charge/discharge capacities and long-term stable cycling performance (250 deep charge-discharge cycles) under the current density of 100 mA g−1 and excellent rate performance, which is attributed to 1D continues cross-link structure of the film, together with increased electrical conductivity and active position for Li+ intercalation/de-intercalation with Cu nanoparticles implanted into fibers.
Preparation of Cu/CF Composites
Polyacrylonitrile (PAN, MW = 150000 g mol−1, Scientific Polymer Products) and N,N-dimethylformamide (DMF, 99 %) were purchased and used as received from Sigma-Aldrich. Copper dinitrate, Cu(NO3)2·3H2O (Aldrich), was used as the copper precursor.
First, 1 g of PAN was added into 10 mL of DMF to form a homogeneous and transparent polymeric solution after it was vigorously stirred for 3 h. Subsequently, 1 g of the Cu(NO3)2·3H2O was dissolved in above polymeric PAN solution. This solution was continuously stirred for 24 h at room temperature conditions leading to the formation of pale blue-colored copper hydroxide/PAN sol. The as-prepared sol was transferred to 10 mL syringe with a hypodermic needle (diameter 27 G) in a controlled electrospinning setup. The electrospinning process was then carried out with a high voltage (18 kV) at a flow rate of 0.5 mL h−1. A white, ultrafine membrane consisting of fibers could be collected on the alumina foil 15 cm away from the needle tip. The fibrous mat was further dried in the oven at 80 °C to evaporate all DMF solvent.
The as-prepared electrospun fibers were first stabilized in an ambient pressure at 280 °C for 2 h at a ramping rate of 2 °C min−1 and then carbonized at 600, 700, and 800 °C for 2 h under the protection of argon atmosphere, respectively. The corresponding products obtained were noted as Cu/CF-600, Cu/CF-700, and Cu/CF-800, respectively. For comparison, we also obtained bare CF-600, CF-700, and CF-800, not adding Cu(NO3)2·3H2O in the same conditions. To obtain the actual copper content in the Cu/CF samples, TGA was performed with a heating rate of 10 °C min−1 and highly pure N2 as the purge gas.
XRD patterns were recorded on Rigaku D/max 2400, Japan, with Cu Kα radiation in the 2-theta range from 10°–80°. Raman spectra were scanned from 2850 to 100 cm−1 on a high-resolution dispersive Raman spectroscopic microscope (Horiba Jobin Yvon, USA). Scanning electron microscopy (SEM) images were obtained on a Hitachi S-4700, Japan, operating at 15 kV and equipped with an EDAX lithium-drifted silicon X-ray energy-dispersive spectrometer (XEDS). The transmission electron microscope (TEM) samples were examined in a JEOL (Japan) 2100F field emission TEM equipped with an energy dispersive X-ray spectrometry (EDS).
The non-woven Cu/CF films were cut into several wafers with a diameter of 14 mm as electrodes directly. Then, the Cu/CF electrodes were dried under vacuum at 100 °C for 12 h. Lithium metal foil (Kyokuto metal Co., Japan) as a counter electrode, 1 M LiPF6 in ethylene carbonate (EC), diethylcarbonate (DEC) (1:1 in volume) (Merck) as an electrolyte, and Celgard 2502 membrane as separator were assembled together with testing electrodes to obtain 2032-type coin cells in an argon-filled glove box (MBRAUN, Germany). Before all electrochemical measurements, cells were aged for 12 h and then tested for cyclic voltammetry (CV) measurement, charge-discharge cycling, rate performance, and electrochemical impedance spectra (EIS) studies. The charge and discharge performances of the batteries were tested with using LAND CT2001A battery test instrument (LAND Electronic Co., China), and potential ranges were controlled between 0.005 and 3 V (vs. Li/Li+) at ambient temperature. The specific capacity was calculated on the basis of the total quality of Cu/CF. The cyclic voltammetry (CV) measurement was conducted with a Gamry Reference 3000 (Gamry Co., USA) at a scan rate of 0.05 mV s−1. EIS was measured on the cell with a Gamry Reference 3000 at room temperature. The frequency ranged from 100 kHz to 100 mHz.
Results and Discussion
Morphology and Characterization
Raman spectroscopy is a powerful and widely used technique for characterization of graphitization . As shown in Fig. 3b, Raman spectra reveal the graphitization of Cu/CF treated under different carbonization temperature. All the samples display two prominent peaks, centered at about 1350 and 1600 cm−1, which correspond to the well-documented G band (E2g mode of graphite) and D band (defect-induced mode). The intensity ratio of ID/IG of Cu/CF-600, Cu/CF-700, and Cu/CF-800 is calculated to be 1.17, 1.00, and 0.91, respectively, which indicates that the degree of graphitization is increased with the increase of carbonization temperature. Based on the TGA result shown in Fig. 3c, the weight content of Cu in Cu/CF-800 is about 29.4 %, which is higher than Cu/CF-700 (19.9 %) and Cu/CF-600 (16.6 %). Combine with the above results, it is found that the carbonation temperature of 800 °C eliminates the residue organic of Cu(NO3)2/PAN precursor more efficiently.
In summary, free-standing Cu nanoparticle-implanted carbon fiber electrodes have been successfully fabricated via electrospun and calcination techniques. The flexible non-woven Cu/CF composites have smooth, regular, and long fibrous morphologies with Cu nanoparticles percolating throughout the carbon matrix and show stable and high reversible capacity, together with remarkable rate and cycling capabilities as free-standing anodes in Li-ion batteries; especially, the Cu/CF sample calcined at 800 °C (Cu/CF-800) shows the highest charge/discharge capacities, long-term stable cycling performance, and excellent rate performance. Combining with the unique 1D structure of carbon fibers, the introduction of Cu nanoinclusions enhancing the reversible Li+ active intercalation/de-intercalation positions and electronic conductivity is believed to be responsible for these.
We gratefully acknowledge the support of the National Science Foundation of China (51472161, 51472160, 21403139), the Shanghai Pujiang Program (14PJ1407100), the Key Program for the Fundamental Research of the Science and Technology Commission of Shanghai Municipality (15JC1490800, 12JC1406900), and the International Cooperation Program of the Science and Technology Commission of Shanghai Municipality (14520721700). We acknowledge the support of the Program for Professor of Special Appointment (Eastern Scholar) at Shanghai Institutions of Higher Learning (TP2014048) and the Hujiang Foundation of China (B14006). We wish to express our thanks to Dr. Brenda Sancnez-Vazquez from University College London for the kind help with the English composition.
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