Nanowire modified carbon fibers for enhanced electrical energy storage

Mohammad Arif Ishtiaque Shuvo, Tzu-Liang (Bill) Tseng, Md. Ashiqur Rahaman Khan, Hasanul Karim, Philip Morton et al. Citation: J. Appl. Phys. 114, 104306 (2013); doi: 10.1063/1.4820942 View online: http://dx.doi.org/10.1063/1.4820942 View Table of Contents: http://jap.aip.org/resource/1/JAPIAU/v114/i10 Published by the AIP Publishing LLC.

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JOURNAL OF APPLIED PHYSICS 114, 104306 (2013)

Nanowire modified carbon fibers for enhanced electrical energy storage

Mohammad Arif Ishtiaque Shuvo,1 Tzu-Liang (Bill) Tseng,2 Md. Ashiqur Rahaman Khan,1 Hasanul Karim,1 Philip Morton,1 Diego Delfin,1 and Yirong Lin1,a)
Department of Mechanical Engineering, The University of Texas at El Paso, El Paso, Texas 79968, USA Department of Industrial, Manufacturing & Systems Engineering, The University of Texas at El Paso, El Paso, Texas 79968, USA
2 1

(Received 5 July 2013; accepted 24 August 2013; published online 11 September 2013) The study of electrochemical super-capacitors has become one of the most attractive topics in both academia and industry as energy storage devices because of their high power density, long life cycles, and high charge/discharge efciency. Recently, there has been increasing interest in the development of multifunctional structural energy storage devices such as structural supercapacitors for applications in aerospace, automobiles, and portable electronics. These multifunctional structural super-capacitors provide structures combining energy storage and load bearing functionalities, leading to material systems with reduced volume and/or weight. Due to their superior materials properties, carbon ber composites have been widely used in structural applications for aerospace and automotive industries. Besides, carbon ber has good electrical conductivity which will provide lower equivalent series resistance; therefore, it can be an excellent candidate for structural energy storage applications. Hence, this paper is focused on performing a pilot study for using nanowire/carbon ber hybrids as building materials for structural energy storage materials; aiming at enhancing the charge/discharge rate and energy density. This hybrid material combines the high specic surface area of carbon ber and pseudo-capacitive effect of metal oxide nanowires, which were grown hydrothermally in an aligned fashion on carbon bers. The aligned nanowire array could provide a higher specic surface area that leads to high electrode-electrolyte contact area thus fast ion diffusion rates. Scanning Electron Microscopy and X-Ray Diffraction measurements are used for the initial characterization of this nanowire/carbon ber hybrid material system. Electrochemical testing is performed using a potentio-galvanostat. The results show that gold sputtered nanowire carbon ber hybrid provides 65.9% higher energy C 2013 AIP Publishing LLC. density than bare carbon ber cloth as super-capacitor. V [http://dx.doi.org/10.1063/1.4820942] metal oxides2830 inclusion with carbonaceous material have been used for developing exible electrodes. Chen et al. fabricated hybrid In2O3 nanowires/carbon nanotubes lms on polyethylene terephthalate (PET) as exible electrodes for super-capacitor with 1 M LiClO4 as electrolyte.31 Transparent graphene/PET lm was used as exible electrodes for super-capacitor with 2 M KCl as electrolyte by Yu et al.15 Single wall carbon nanotube suspension was coated on both sides of a printing paper pretreated by polyvinylidine uoride (PVDF) for exible paper based electrodes by Hu et al.32 For this approach, they used coffee bag to encapsulate the electrodes and electrolyte for super-capacitor fabrication. But all these developed super-capacitors could not carry mechanical loads. Recently, Lin et al. developed a ZnO/Carbon ber hybrid that has shown improved structural properties,33 however, its energy storage property has not been studied yet. Therefore, this paper investigates electrochemical performance of ZnO/Carbon ber hybrid for supercapacitor electrode, aiming at developing multifunctional composites with embedded energy storage functionalities. Herein, we report a simple two-step hydrothermal method for growing uniformly distributed ZnO nanowires (ZnO NWs) on carbon ber cloth, compared with bare carbon ber for super-capacitor electrode. This low temperature growth of ZnO NWs on carbon ber cloth is biocompatible,
C 2013 AIP Publishing LLC V

I. INTRODUCTION

The evolving interest on portable and exible electronic devices in recent times has intrigued researchers for developing lightweight, bendable, and environment friendly energy storage devices, such as batteries1,2 and super-capacitors35 The electrical double layer capacitor (EDLC) or supercapacitor has become an excellent candidate among these devices with fast charging/discharging rate, high power density, sustainable cycling life and excellent cycling stability.37 It has higher capacitance than general capacitor and can deliver more power than batteries.8,9 However, conventional super-capacitors are typically separated parts from load bearing structures, besides, they are heavy and bulky thus leading to system complexity and extra add-on weight.10 Therefore, there is an increasing need to embed these energy storage devices such as super-capacitor into the load bearing structures to form multifunctional materials. Prototypes of some thin exible super-capacitors have been proposed in literature.11,12 Carbonaceous material such as graphene1317 and carbon nanotubes,1820 hybrid composites,2123 conducting polymers2427 and transition
a)

Author to whom correspondence should be addressed. Electronic mail: ylin3@utep.edu

0021-8979/2013/114(10)/104306/4/$30.00

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environmentally friendly and could provide more specic surface area for highly efcient super-capacitor.3438 For improved performance, Au was coated on nanowire/carbon ber electrode and bare carbon ber electrode. Coated nanowire/carbon ber electrode showed about 65.9% better performance than bare carbon ber cloth in super-capacitor application with 5.5 M KOH aqueous electrolyte.
II. EXPERIMENTAL DETAILS A. Carbon fiber/zinc oxide nanowire hybrids synthesis
FIG. 1. Two-electrode test cell conguration.

The ZnO nanowire growth is a two-step hydrothermal growth method including seeding and nanowire growth. Briey, ZnO nanoparticle seeds were rst synthesized in an organic solution, and then the seeding process was performed to coat ZnO nanoparticles onto carbon ber cloth. The seeded carbon cloth was transferred to ZnO nanowire hydrothermal growth solution at elevated temperature and atmospheric pressure. After the nanowire growth, the nanowire/carbon ber was rinsed extensively and dried in air for super-capacitor assembly.
1. ZnO seed particles

Both bare carbon ber (CF) and ZnO NWs on carbon ber samples were sputtered with gold (Au) for 120 s to prepare four kinds of electrodes, i.e., (a) CF, (b) carbon ber coated with Au (CF-Au), (c) ZnO nanowires on carbon ber (ZnO-CF), and (d) ZnO nanowires on carbon ber coated with Au (ZnO-CF-Au). A hand punch with 19 mm diameter was used for preparing circular electrodes and copper tape was used as current collector. An aqueous solution of 5.5 M KOH was prepared for electrolyte and Celgard 3501 was used as separator.
III. RESULTS AND DISCUSSION

Carbon cloth (made of carbon ber, diameter 7 lm) of 50 mm 30 mm was glued (Devcon, 5 min epoxy) on the edges. Then carbon cloth was rst cleaned in bath sonication (Branson, 2510). Acetone, Deionized water (DI) and ethanol were used as cleaning solvent. Carbon cloth was placed in a beaker with cleaning solvent and bath sonication was performed for 10 min using each solvent. Then carbon cloth was dried at ambient temperature in open air. The clean carbon cloth was taken on a glass petri dish to soak in the nanoparticle solution for 10 min and subsequently annealed on a hot plate at 150  C for 10 min to enhance adhesion between the substrates and nanoparticles. This soaking and annealing was repeated two more times to ensure the mass coating of ZnO nanoparticle all over the carbon bers.33,39
2. ZnO nanowires

After seeding, hydrothermal growth of ZnO nanowires was performed using a low temperature hydrothermal method detailed elsewhere.4 Briey, an aqueous solution of 25 mM zinc nitrate hexahydrate (Zn(NO3)26H2O, 99.9% purity, Sigma-Aldrich), 25 mM hexamethylenetetramine (HMTA) (C6H12N4, 99.9% purity, Sigma-Aldrich), and 57 mM Polyethylenemine (PEI, Branched) were prepared at room temperature. Carbon ber cloth was immersed in growth solution when the temperature was at 85  C. The time duration of this growth was 2 h for all the carbon ber samples. After the reaction had been completed, carbon ber samples were taken out of the solution and rinsed with DI water and dried at 100  C on a hot plate for 2 h.
B. Super-capacitor fabrication

The morphology of zinc oxide nanowires grown on carbon cloth was analyzed with scanning electron microscope as shown in Figure 2. As indicated by the gure, ZnO nanowires were grown uniformly throughout the carbon ber. The nanowires had a length between 1 and 3.14 lm and diameter between 40 and 110 nm. No residue or ower was found. The X-Ray Diffraction (XRD) scanning result of the ZnO nanowires on carbon cloth is shown in Figure 3. The asterisk (*) marked peak represents carbon of rhombohedra crystal structure. The scan result matched with the standard card JCPDS (01-075-0444) and has lattice parameters of a 2.29597, b 2.29597, and c 10.15404. The rest of the peaks represent zinc oxide which matched with the standard card JCPDS (01-070-8070). The lattice parameters for hexagonal zinc oxide are a 3.24890, b 3.24890, and c 5.20490. No other peaks were found which indicates the sample has only zinc oxide and carbon.

A two electrode testing set up was prepared as shown in Figure 1 because it provides most accurate measure for an electrodes performance for electrochemical capacitors.40

FIG. 2. SEM images, (a, b, and d) ZnO/carbon ber, (c) bare carbon ber.

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FIG. 3. XRD result for ZnO NWs coated carbon cloth. Asterisk (*) peak is for carbon. The rest of the peaks belong to ZnO.

Four types of electrodes (CF, carbon ber coated with Au [CF-Au], ZnO NWs on carbon ber [CF-ZnO], and ZnO NWs on carbon ber coated with Au [CF-ZnO-Au]) were prepared for the two-electrode testing setup of the supercapacitor. The electrochemical properties of the supercapacitors in 5.5 M KOH aqueous electrolyte were evaluated by cyclic voltammetry (CV) and galvanostatic charge

discharge method using a potentio-galvanostat from EZ-stat. Figures 4(a)4(d) show cyclic voltammetry for the four different samples at different scan rates of 50 mV/s, 100 mV/s, 250 mV/s, and 500 mV/s with a scan range between 0 and 500 mV. Area under each CV curve suggests that all fabricated super-capacitors have good electrochemical stability and capacitance. Top left corner and bottom right corner of each CV curve indicate the presence of little resistive properties due to equivalent series resistance (ESR).43 Moderate leakage resistance of each sample was perceived as low leakage resistance would skew all CV curves vertically.42 Pseudo-capacitive behavior of all samples had been observed which can be ensured by the mirror like image at the anodic and cathodic regimes.43 Six cycles of galvanostatic charging-discharging curves for all four samples at 56 lA are shown in Figures 4(e)4(h) within the potential window of 00.5 V. Capacitance for the four ber super-capacitors or nanowire hybrid ber supercapacitors originates either at the electrolyte/ber interface or electrolyte/nanowire interface, which is indicated by the typical triangular nature of the curves. The chargingdischarging curves for all four samples showed very symmetric nature indicating good electrochemical capacitive

FIG. 4. Typical cyclic voltammograms of (a) CF, (b) CF-Au, (c) CF-ZnO, (d) CF-ZnO-Au electrode super-capacitor and galvanostatic charge discharge curve at 56 lA within a voltage window of 00.5 V for (e) CF, (f) CF-Au, (g) CF-ZnO, (h) CF-ZnO-Au electrode super-capacitor.

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property and high reversibility, consistent with earlier CV observation. Specic capacitance for the super-capacitors can be calculated by the following equation:41 Cs 4I Dt ; m DV (1)

where I is the discharging current, t is the discharging time, V is the discharging voltage, and m is the mass of active material in the electrodes. Specic capacitance for the samples was calculated from the discharge slope of the galvanostatic charge discharge curve.40 Carbon ber coated with Au (CF-Au) has a specic capacitance value of 2.35 F/g which is about 7% higher than that of bare CF (2.2 F/g). ZnO NWs on carbon ber could provide more surface area for the pseudo-capacitance of the electrodes, therefore, provided 16% higher specic capacitance (2.55 F/g) than CF. Highest specic capacitance value was obtained from ZnO NWs on carbon ber coated with gold which showed about 65.9% higher value (3.65 F/g) than CF. We also measured specic capacitance in exible/twisted condition for all the samples but no apparent change was observed which conrms highly exible nature of the electrodes. To improve the value of the specic capacitance of the electrochemical capacitor further optimization might be done, i.e., matching the pore sizes and ion size of the electrolyte, controlling the density of ZnO NWs.
IV. CONCLUSION

Multifunctional structural energy storage devices are one of the key research interests of recent time to obtain load bearing and energy storage capability in one structure. It has been demonstrated nanowire carbon ber hybrid could provide better mechanical strength than bare carbon ber for composites. In this pilot research project, we have incorporated the same nanowire hybrid carbon ber for electrode materials to examine its electrochemical properties for potential structural energy applications. A low temperature hydrothermal method has been utilized to synthesize ZnO nanowires on carbon ber cloth and sputtered for high performance super-capacitor electrode. Scanning Electron Microscopy (SEM) images demonstrated good coverage of uniformly distributed nanowires all over carbon ber cloth. XRD analysis result conrmed existence of carbon and ZnO only. The growth of nanowires has a positive synergistic effect which helps pathways for better ion diffusion incrementing electrode-electrolyte contact area. Based on the obtained result and previous report, it is obvious that ZnO NWs on carbon ber has a promising future for structural energy storage with appropriate solid electrolyte. This simple method can be utilized for making high performance structural super-capacitor for next generation aerospace, automobile and electronic application.
ACKNOWLEDGMENTS

The authors would like to thank Celgard for providing the Celgard 3501 separator.

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