High-Performance Lithium-Ion Battery and SymmetricSupercapacitors Based on FeCo2O4 Nanoflakes ElectrodesSaad Gomaa Mohamed,†,‡ Chih-Jung Chen,† Chih Kai Chen,† Shu-Fen Hu,*,§ and Ru-Shi Liu*,†,⊥

†Department of Chemistry, National Taiwan University, Taipei 106, Taiwan‡Nanoscience and Technology Program, Taiwan International Graduate Program, Institute of Physics, Academia Sinica and NationalTaiwan University, Taipei 106, Taiwan§Department of Physics, National Taiwan Normal University, Taipei 116, Taiwan⊥Department of Mechanical Engineering and Graduate Institute of Manufacturing Technology, National Taipei University ofTechnology, Taipei 106, Taiwan

*S Supporting Information

ABSTRACT: A successive preparation of FeCo2O4 nanoflakesarrays on nickel foam substrates is achieved by a simplehydrothermal synthesis method. After 170 cycles, a highcapacity of 905 mAh g−1 at 200 mA g−1 current density andvery good rate capabilities are obtained for lithium-ion batterybecause of the 2D porous structures of the nanoflakes arrays.The distinctive structural features provide the battery withexcellent electrochemical performance. The symmetric super-capacitor on nonaqueous electrolyte demonstrates high specificcapacitance of 433 F g−1 at 0.1 A g−1 and 16.7 F g−1 at highscan rate of 5 V s−1 and excellent cyclic performance of 2500cycles of charge−discharge cycling at 2 A g−1 current density,revealing excellent long-term cyclability of the electrode evenunder rapid charge−discharge conditions.

KEYWORDS: FeCo2O4, nanoflakes, Li-ion battery, supercapacitors

1. INTRODUCTION

Lithium-ion batteries (LIBs) and supercapacitors (SCs) haveenticed worldwide interest as two main devices of electricenergy storage on account of their needful use as predominantenergy sources for transportable electronics and theirprominent prospect to electric vehicles and large-scale electricnetworks.1 Both of them are categorized as electrochemicalenergy storing systems and have numerous resemblances instructure with an anode, an utilized electrolyte, and a cathode.2

Fundamentally, the storing of energy in those electrochemicalcells is based on the reversible electrochemical reactions andthe mechanism of charge storing in the electrode materials. Theions travel toward the electrodes across the electrolytes,whereas the electrons flow over the outer circuit during theelectrochemical processes.1

In consequence of their outstanding physical and chemicalproperties and considerable prospective for several applicationsin technological fields, mixed transition metal oxides(MTMOs) have lately enticed research interest, extendingfrom material for electrodes to catalysts. MTMOs normallystore lithium through conversion reaction in case of using asanode materials for LIBs, which causes the reversible formationof metallic particles implanted in a Li2O matrix.1,3,4 In case ofusing as electrode for SCs, the storing of charges in MTMO

electrodes primarily originates from the pseudocapacitance thatinitiates from the fast surface redox reactions.1,5 Aside fromsimple binary metal oxides, ternary transition metal oxides havedrawn growing attention for electrochemical energy storage inrecent years. They show many unique properties that originatefrom the coexistence of two different cations in a single crystalstructure,6 as well as partial replacement of M in spinel M3O4

with other 3d-transition metals (Mn, Fe, Co, or Ni) that canenhance the catalytic activity, selectivity, stabilization, andoxides withstanding against the catalytic or electrocatalyticpoisoning.7 For example, ternary MnCo2O4, NiCo2O4,CuCo2O4, and ZnCo2O4 have been widely reviewed aspromising electrodes for LIBs and SCs because of their higherconductivity and electrochemical activities in comparison withcorresponding MxOy and Co3O4.

8−14 Furthermore, cobaltbased oxides are to some extent expensive and toxic. Hence,beneficial attempts have been exerted toward partly displacingthe cobalt in Co3O4 with cheaper and more environmentallyfriendly alternate elements without losing its high electro-chemical effectiveness.1

Received: October 4, 2014Accepted: December 1, 2014Published: December 1, 2014

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Recently, the two-dimensional (2D) nanostructures, such asgraphene, metal oxides, metal, chalcogenides, and hydroxides,have attracted tremendous attention because of their attractivephysical and chemical properties for great potential applicationsin in catalysis and energy devices. Nanosheets have a largesurface area, which provides high efficient electrochemicalactive sites, reduces the ions and electron diffusion path,increases the electronic conductivity, and improves thestructural stability. Thus, the ultrathin 2D nanostructuresrepresent a great potential for application in next generationbatteries and supercapacitors.15,16

Very few studies have been reported on the utilization ofFeCo2O4 as electrode material for energy-related applications.Laouini et al.17 investigated the electrochemical behavior andthe catalytic activity for oxygen evolution and reduction ofFeCo2O4 thin film coatings. Sharma et al.18 studied theelectrochemical lithium storage properties of FeCo2O4 powder(submicron particles) and concluded that the iron ion is activealongside the cobalt ion. Their findings exhibited that Fe ismore proper matrix ion than Mg, and FeCo2O4 showed the firstdischarge capacity of 1155 mAh g−1 and retained 90% of thefirst charging capacity of 827 mAh g−1 after 50 cycles at acurrent density of 60 mA g−1. These results reveal the potentialand possible use of FeCo2O4 as LIB electrode. No studyregarding the application of FeCo2O4 as an electrode for SCapplication has been reported.In this work, FeCo2O4 nanoflakes (FCO-NFs) were directly

grown onto nickel substrate (free from adding binder orconductivity agent) through urea combustion hydrothermalsynthesis then calcining for 2 h at 400 °C. To the best of ourknowledge, this work is the first to examine the functioning ofFCO-NFs as LIBs and SCs electrode system. Compared withthree-electrode structure, measurement by means of two-electrode shape is more suitable for estimating the operation ofSC test cells because they simulate the physical configuration,interior voltages, and charging transference in existent SC uses,accordingly providing the best evaluation of the rendering ofsuch electrode materials.19 on the contrary, the workingelectrode of a three-electrode cell has twice the potentialrange applied as is applied to the electrodes in a two electrodecell and this results in a doubling of the calculated capacitance,besides, the heightened sensitivity of the three electrodeconfiguration can lead to large errors when projecting theenergy storage capability of an electrode material forsubercapacitors use.20 Therefore, we fabricated our SC cellusing two-electrode configuration (symmetric SC) in organicelectrolyte. We investigated the electrochemical energy storageof FCO-NFs as electrodes both in LIBs and in SCs. As anodematerials for LIBs, the electrode displays high first dischargecapacity and maintain a high reversible capacity of 905 mAh g−1

at 200 mA g−1 rate after 170 cycles. When evaluated as SCelectrode, they demonstrate high capacitance and good cyclingconstancy at high rates and high charge−discharge stability for2500 cycles. These outstanding results indicate that the unique2D-arrayed FCO-NFs structures on nickel foam are promisingin electrochemical energy storage purposes.

2. EXPERIMENTAL SECTION2.1. Hydrothermal Synthesis of FCO-NFs. FeCo2O4 prepared

by dissolving a proper weight 1 mmol ferrous chloride tetrahydrate[FeCl2·4H2O, 99%, J. T. Baker], 2 mmol cobalt nitrate hexahydrate[Co(NO3)2·6H2O, 99%, ACROS], 5 mmol urea [CO(NH2)2, 99%,Sigma-Aldrich], and 2 mmol ammonium fluoride (NH4F, 98%,

Merck) in 50 mL of deionized water (DIW). Nickel foam substrate(2 cm × 3 cm piece, Kunshan Desike Electronic, China) wasultrasonically cleaned with ethanol, DIW, and acetone (30 min ofsuccessive sonication in each). The solution with the nickel foam (topside was masked by kapton tape) kept on top was next transmitteddirectly into a 100 mL Teflon-lined stainless autoclave that then wassealed and kept for 7 h at 140 °C. After the autoclave was left to cooldown naturally to room temperature, the as-synthesized material onnickel substrate was taken from reaction media, washed, dried, andthen the product calcination was done at 400 °C for 2 h in air with 3°C min−1 heating rate. .

2.2. Characterizations. The crystallographic data of the sampleswas investigated through Synchrotron X-ray diffraction [(SXRD,BL01C2 beamline at NSRRC, Taiwan), supported with Mar345imaging plate and X-ray wavelength of 0.77491 Å X-ray, and thentransferred to λ = 1.54178 Å X-ray by WinPLOTR software]. Theirmorphologies, structures and compositional investigations wereexamined by FESEM (JEOL JSM-6700F, with EDS instruments),TEM) and HRTEM (JEOL, JEM-2100F).

Surface analysis of samples was investigated using X-ray photo-electron spectroscopy (PHI Quantera) under Al Kα radiation (λ =8.3406 Å). Co K-edge XANES spectra were examined at BL01C1beamline of the NSRRC.

2.3. Electrochemical Measurements. For electrochemicalmeasurements, the mass of active material was calculated bysubtracting the mass of Ni foam sample before and after FCO-NFsgrowth. For confirmation, the pristine Ni substrate, without FCO-NFsgrowth, was cleaned, underwent hydrothermal reaction (without ironand cobalt precursors), heat-treated under the same experimentalconditions, and weighted to ensure the correct mounted FCO-NFsgrown mass. The mass loadings of the actual samples for lithium-ionbattery and supercapacitor tests were 1.9 ± 0.3 mg cm−2.

2.3.1. Li-ion Battery Measurement. Electrochemical experimentswere carried out under room temperature with two-electrode coin cells(CR 2032), with lithium foil as both counter and reference electrode.A nickel foam piece mounted by FCO-NFs was directly utilized as theworking electrode without addition of any polymeric binder orconductive materials. A glass fiber (18 mm in diameter, PallCorporation) was employed as separator. Afterward, 1 M LiPF6 inethylene carbonate and dimethyl carbonate (1:1 by volume) was usedas the electrolyte. The cell assembly was carried out in an argon-filledglovebox with both moisture and oxygen content below 1 ppm.Galvanostatic charge−discharge was carried out using a battery tester(AcuTech Systems Co., Ltd., Taiwan) with a voltage window of 0.01to 3.0 V at a current density of 200 mA g−1. Cyclic voltammetry (CV)test was conducted in the potential window of 0.01 to 3.0 V at a scanrate of 0.3 mV s−1 using an electrochemical workstation (AUTOLABPGST30, Eco Chemie).

2.3.2. Supercapacitor Measurement. The electrochemical per-formance of the prepared FCO-NFs/Ni foam electrode for symmetricSC was investigated using two-electrode coin-type cells (CR 2032)assembled in an argon-filled glovebox. A pair of electrodes wasassembled with a glass fiber separator with 1 M LiClO4 in propylenecarbonate organic electrolyte. The electrochemical properties of theSC were studied using cyclic voltammetry (CV), galvanostatic charge−discharge, and electrochemical impedance spectroscopy (EIS) using760D (CH Instruments). The CV tests were carried out in thepotential range of 0 to 2.5 V at different scan rates ranging from 1 mVs−1 to 5 V s−1. The chrono charge−discharge measurements were alsoconducted at various current densities (0.1 to 20 A g−1) in potentialrange of 0−2.5 V. The EIS measurements were performed in thefrequency range of 1 MHz to 1 Hz (amplitude of 5 mV). The EIS datawere analyzed using Nyquist plots. The specific capacitance (C, F g−1)was then calculated from the CV curves according to the equation C =i/m ΔV, where m (g) is the mass of active materials, ΔV (V s−1) is thepotential sweep rate, and i (A) is the current response obtainedthrough integrating the area of the CV curve.21 Energy density (Ed)and power density (Pd) were calculated from the capacitance (C) valueobtained by cyclic voltamatry according to these equations:22,23

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energy density

=−E CV(W h K g ) 1/8d1 2

power density

= Δ =−P E V V(W K g ) / (V voltage window)d1

3. RESULTS AND DISCUSSION3.1. FCO-NFs Characterazation. The X-ray diffraction

(XRD) pattern of FCO-NFs developed on nickel foam afterheat treatment at 400 °C for 2 h is presented Figure 1a.

Excluding the two peaks resulting from metallic Ni atapproximately 2θ of 44.5° and 51.9° (JCPDS 04-0850),whole diffraction peaks could be apparently indexed toFeCo2O4 spinel phase (Fd3m space group); they demonstrategood agreement with the reported values in prior reports.17,18,24

No further peaks, related to NiO, MnO2, or CoO, are detectedin the produced material, indicating the uniform growth ofFeCo2O4 on the surface of nickel substrate. The morphology ofFCO−NFs grown on nickel foam was investigated by fieldemission scan electron microscopy (FE-SEM). Figures 1b−dshow the characteristic morphology of the FCO-NFs on nickelfoam. As shown, the nanoflakes are homogeneously grown onnickel foam, developing a uniform coating on the surface(Figure 1b) and forming an enlarged petal-like nanoflakestructure. These features are connected to one another, and thisformation results in a cross-linked structure that might possesshigh mechanical strength. Further information on the FCO-NFs microstructure can be attained from the transmissionelectron microscopy (TEM) images in Figure 2. The image oflow magnification (Figure 2a) implies that the nanoflakes areincessant. They have a coarse surface in which theinterconnected nanoparticles form sheet-like structures. Themagnified image (Figure 2c) clearly shows that pores aredistributed throughout the surface of the nanoflakes. Theformation of the pores in the nanoflakes could be related to theliberation of gases during thermal treatment during thedecomposition of the precursors.25 The resolved lattice fringesshown in Figure 2c are about 0.24 and 0.47 nm, which could be

assigned to the (311) and (111) planes of the FeCo2O4 cubicphase. This result further confirms the formation of crystallineFCO-NFs, and has a consistency with the XRD pattern.Moreover, the corresponding selected area electron diffraction(SAED) pattern (Figure 2c inset) indicates the single-crystalline character of the nanoflakes, Energy-dispersive X-ray spectrometry (EDS) microanalysis of the NFs (Figure 2d)displays that the nanoflakes comprises only Fe, Co, and Oelements with atomic ratio of almost of 1:2:4, indicating theformation of pure FeCo2O4.The chemical composition and the purity of the FCO-Nfs

product were investigated using X-ray photoelectron spectros-copy (XPS). Figure 3a elucidates the XPS spectra of Fe 2p. Thepeak deconvolution and fittings were carried out usingGaussian−Lorentzian shaped peaks based on the Shirleybackground correction. Two peaks are observed at 709.5 and722.6 eV, consistent with spin−orbit peaks of the Fe 2p3/2 andFe 2p1/2, in addition to the presence of a “shoulder” satellitepeak at 714.6 eV. These results indicate the presence of Fe2+.26

As can be seen in Figure 3b, the Co 2p pattern demonstratestwo peaks at 779.2 (main peak, Co3+) and 785.1 eV (satellitepeak, Co2+), that could be ascribed to Co 2p3/2 and its satellitepeak. Another peaks are detected at 794.6 (main peaks, Co3+)and 801.7 eV (satellite peak, Co2+/Co3+) that could be ascribedto Co 2p1/2 and its satellite peak.18 From the binding energiesof Co 2p main lines and the splitting due to the spin−orbitcoupling, besides the energy gaps separating the main lines andsatellite peaks, it can be said that Co(II) and Co(III) cationstogether are exist. The O 1s XPS spectrum (Figure 3c) displaystwo strong main peaks at about 529.6 eV (corresponding to acharacteristic bond between metal and oxygen) and at 531.1 eVwhich is corresponding to the OH− groups oxygen, revealing ofhydroxylation of the material surface. The X-ray absorptionnear edge structure (XANES) spectrum shown in Figure 3dand its inset (Co K-edge and per edge region) show thatFeCo2O4 is close to Co3O4 mixed valence (Co2+ and Co3+),

Figure 1. (a) XRD pattern and (b−d) typical FE-SEM images atdifferent magnifications of FCO-NFs on nickel foam after calcinationat 400 °C for 2 h in air.

Figure 2. TEM and HRTEM analysis of the FCO-NFs detached fromnickel foam: (a) morphology at low magnification, (b) morphology athigh magnification (noticing of the porous features), (c) HRTEMimage with the corresponding SAED pattern (inset), and (d) EDSmicroanalysis of FCO-NFs on Ni foam.

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indicating the coexistence of both Co2+ and Co3+ cations inFeCo2O4. This result is consistent with that of the XPS spectra.3.2. FCO-NFs Electrochemical Performance. The

electrochemical performance of the FCO-NFs grown on nickelfoam is estimated as conductive agent and binder-free electrodefor LIBs and SCs. For LIB anode, the electrochemicalproperties of FCO-NFs electrode was first investigated throughcyclic voltammetry (CV) to discern the charge and dischargereaction potentials. Figure 4a displays the initially three CV

curves of FCO-NFs on nickel foam electrode obtained at 0.3mV s−1 scan rate and potential range of 0.01−3.0 V. Thevoltammogram for the first cycle is noticeably different amongthese ones of the subsequent cycles, and no considerablevariation is noticed between the second and third cycles. In thefirst cycle, a single intense reduction current peak is detected at0.42 V in the cathodic scan. This peak could be ascribed to Li

intercalation into the crystal structure after that FeCo2O4crystal lattice destructed (amorphous phase formation) anddevelopment of the corresponding metal nanoparticles4

(reduction of Co3+ to Co2+, Co2+ to metallic Co, and Fe2+ tometallic Fe in FeCo2O4 crystals). In addition to these processesis the forming of amorphous Li2O, along with growing of solidelectrolyte interphase (SEI) layer as a result of thedisintegration of electrolyte.8,18,27 The cathodic irreversiblepeak could be explicated by eq 1. The first-charge sweep showsa doublet peak at potentials ∼1.69 and ∼2.2 V, which isascribed to the oxidation of Co to Co2+ and Co3+ and of Fe toFe2+. The reduction peaks in the second and third cycles moveto 0.72 and 1.57 V, differing significantly from that electro-chemical reaction occurred irreversibly in the first cycle duringdischarge. These peaks are induced by the reduction reactionsof FeO, CoO, and Co3O4 to Fe and Co metals. In theconsecutive cycles, two reversible anodic peaks are observableat 1.68 and 2.25 V, which could be ascribed to the oxidation ofFe0 to Fe2+ and of Co0 to Co2+/Co3+, respectively, indicatingthat reversible oxidation−reduction processes take place in thecharge−discharge cycles. Based on the displacive redoxmechanism, these processes could be described by eqs 2 to4.18,27

+ + → + ++ −FeCo O 8Li 8e Fe 2Co 4Li O2 4 2 (1)

+ ↔ + ++ −Fe Li O FeO 2Li 2e2 (2)

+ ↔ + ++ −2Co 2Li O 2CoO 4Li 4e2 (3)

+ ↔ + ++ −2CoO 2/3Li O 2/3Co O 4/3Li 4/3e2 3 4 (4)

Thereafter The FCO-NFs were evaluated as anode for LIBs,representative charge−discharge characters of the 1st, 2nd, 3rd,and 20th cycles at current density of 200 mA g−1 are presentedin Figure 4b. This electrode exhibits first discharge and chargecapacities of 2445 and 1870 mAh g−1, respectively, correspond-ing to 76.5% of the first Coulombic efficiency. The highdischarge capacity of first cycle might as well be correlated tothe Li+ diffusion distance shortening alongside increasing thenumber of diffused ions as a result of the porous structure of2D NF’s arrays, besides to the influence of the partly reversibleformation−decomposition of the SEI and formation of gelpolymeric layer resulted from electrolyte dissolution,18,28 Theplateau of first discharge cycle exists at ∼0.89 V, correspondingintercalating of Li ion into the FeCo2O4 crystal system, at whichthe crystal lattice turns to amorphous constitution followed bythe formation of the metallic nanoparticles through a two-phasereaction formation. Accordingly, the charging operation(extraction of Li from Fe−Co−Li2O composite) will not resultin the reformation of the spinel structure, but only theindividual oxides, FeO or CoO (Co3O4), are formed. Enablingthe realization of larger reversible capacity and giving stable andnear theoretical capacities on long-term cycling of the FeCo2O4by conversion reaction,4 which are coherent with the CVperformance. In the following cycles, the plateau at 0.89 V shiftsfrom 1.2 to 1.3 V, indicating that the irreversible reactionsoccurred throughout the first cycle. The findings also confirmthat different electrochemical reactions regulate the followingcycles. The second, third, and 20th cycles’ discharge capacitiesof the electrode are 1877, 1831, and 1713 mA g−1, respectively,demonstrating the great stability of the electrode material. Theloss in capacity (irreversibility) in the first cycle (23.2%) couldbe ascribed to the SEI forming and reduction of metal oxides to

Figure 3. XPS and XANES spectra for the FCO-NFS detached fromnickel foam: (a) Fe 2p XPS, (b) Co 2p XPS, (c) O 1s XPS, and (d) CoK-edge XANES and pre-edge region (inset).

Figure 4. Electrochemical performance of FCO-NFs electrode forLIBs: (a) CVs of the first three cycles at 0.3 mV s−1 scan rate andvoltage of 0.01 to 3.0 V; (b) discharge/charge profiles for the selectedcycles (at 200 mA g−1); (c) cycle performance at 200 mA g−1; and (d)rate capability test at different current densities.

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its corresponding metal atoms beside Li2O formation, that isusually noticed in several electrode materials.29 Figure 4cdisplays the charge−discharge capacity of the FCO-NFselectrode versus the cycles number at cycling current densityof 200 mA g−1. Within 170 cycles, the capacity fades up to 70cycles. Thereafter, the reversible capacities stabilize and slightlyincrease gradually up to 170 cycles (∼905 mAh g−1 for cycle170 discharge capacity) with a significant improvement inCoulombic efficiency. The obtained Coulombic efficiencyimplies that the charge−discharge process steadily steadies.To investigate the performance rate of the FCO-NFs, the ratecapabilities were investigated using multiple-step charging/discharging at several current densities (200 to 800 mA g−1).Figure 4d shows that the cell has good rate capability withaverage discharge capacities of 1570, 1433, and 1222 mA h g−1,once the current density raised from 200 to 400 and 800 mAg−1, respectively. By varying the current density back to 400 and200 mA g−1, an average discharge capacity as high as 1324 and1330 mAh g−1 could be recovered. These results show that theFCO-NFs anode for LIB has significantly high cyclingperformance, capacity retention and rate capability.The electrochemical performance of the FCO-NFs on nickel

foam is also evaluated for application as electrodes for SCs. Toconfirm the effectiveness of the material for charge storing,testing of electrochemical capacitance was examined throughcyclic voltammetry (CV) and the charge−discharge techniquein a symmetrical two electrode system containing FCO-NFs onnickel foam electrodes and 1 M LiClO4/PC nonaqueouselectrolyte at potential window of 0 to 2.5 V. The CV curvesfound by varying the scan rate from 1 to 100 mV s−1 are shownin Figure 5a. The CV curves are deviated rectangular-like

character and exhibit nearly perfect capacitive performances atsweep rates up to 100 mV s−1 (Figure S1, SupportingInformation), indicating the rapid current response to voltagereversal (small contact resistance) and reveals the pseudocapa-citive behavior of the electrodes.30 The CV curves differ fromthat rectangular nature at higher scan rates (500−5000 mV s−1,Figure S1, Supporting Information) and exhibit an ovoid shape

instead, that could be attributed to the electrode inherentresistance. This resistance can be ascribed to intensifiedpolarization, fast transfer of charges, and diffusion of captions.The CV testing of the electrode under high sweep rates of 0.5,1, and 5 V s−1 suggests potential use of such material in SCsused in high-power applications. The symmetric cell made fromFCO-NFs on nickel foam electrode shows high specificcapacitances of 433, 225, 184, 150.8, 129.2, 109.6, 65.1, and46.6 F g−1 at scan rates of 1, 5, 10, 25, 50, 100, 500, and 1000mV s−1, respectively (Table S1, Supporting Information).Additionally, cycling at high scan rate of 5000 mV s−1,capacitive performance can even be detected with a 16.7 F g−1

specific capacitance. For additional estimation of the electro-chemical performance of the FCO-NFs on nickel foamelectrode, chrono charge−discharge tests were done at variouscurrent densities. Electrode Charge−discharge performance iscrucial in the examination and estimation of the performance ofthe active material under real operational circumstances.19 Theconstant current charge−discharge curves for the SC electrodesat 0.1 A g−1 in the potential range of 0−2.5 V are shown inFigure 5b (first five cycles; see also Figure S2, SupportingInformation). Through the charge−discharge processes, thecurve of charging step is not quite symmetrical with its relateddischarging step, showing a small decline in internal resistance(IR drop) and indicating pseudocapacitive behavior. Theanodic charging segment is consistent with cathodic dischargingsegment with nearly triangular shape-like curve in the chronocharge−discharge performance as shown in Figure S2,Supporting Information, (except for the first 2 cycles in 0.1 Ag−1 because of internal resistance at low charging currentdensity, Figure 5b), which is suggestive of a highly reversiblecharge−discharge reaction or a very good reversible capacitivematerial. These results indicate that the cell potential is linearlychanged with time, signifying the pseudocapacitive character ofthe electrode obtaining from storage of charges throughadsorption−desorption at the electrode−electrolyte interface,in addition to double-layer contributions and probable Li+

insertion/extraction mechanism between the electrode and theLiClO4/PC electrolyte.31 Figures 5c and d shows the charge−discharge curves of different characteristic current cycling rates(0.1, 0.3, 0.5, 1, 5, 10, 15, and 20 A g−1). Whole curves exhibitsymmetrical characters of the charging and dischargingcounterparts, suggesting the perfect pseudocapacitive characterof rapid charge/discharge processes.30

The cycle performances are important for electrochemicalSCs. The electrode durable stability was studied by chronocharge−discharge technique at current density of 2 A g−1 in thepotential ranging between 0 and 2.5 V for 2500 cycles. The firstand the last 10 charge−discharge curves are showed in Figures6a and b, which display nearly the same shape, revealingoutstanding long-term stability of the electrode even underrapid charge−discharge situations. Supporting InformationFigure S3a shows the plots of Coulombic efficiency vs cycle’snumber. Coulombic efficiency is calculated by dividing thedischarge current on charging current (td/tc of the 2500 cyclesat current density of 2 A g−1). The Coulombic efficiency isclose to 100%, indicating the stability of and symmetry of theelectrode under long-cycling test.The energy density and power density of the supercapacitor

are calculated from CV using the equation given in theExperimental Section and the typical Ragone plot is shown inS3b, Supporting Information. The values of energy densitiesand the power densities are shown in Table S1, Supporting

Figure 5. Electrochemical performance of FCO-NFs electrode forsymmetric SCs: (a) CV responses at different scan rates of 1−100 mVs−1; (b) charge−discharge curves of the first 5 cycles of the SCs at 0.1A g−1; (c and d) symmetric SC’s first cycle behavior at differentcurrent densities.

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Information. The energy density of FCO-NFs electrode at scanrate of 1 mV s−1 can approach 93.9 Wh kg−1 at a power of135.3 W kg−1. A strong drop in the energy density withincreasing the power densities can also be observed byincreasing the scan rate. Even at a high power density of26093.7 W kg−1, the energy density still can be kept atapproximately 3.6 Wh kg−1 (at scan rate of 5 V s−1), whichreveals a large power range that can be achieved withmaintaining a suitable energy density.To further quantitatively examine the interfacial electro-

chemical behavior of the SC electrode−electrolyte interface,electrochemical impedance spectroscopy (EIS) measurementswere conducted before and after the galvanostatic charging−discharging test. Figure 6c displays the Nyquist plots ofsymmetrical SC cells which fabricated based on FCO-NFs onnickel foam electrodes before and after 2500 charge−dischargecycling. The Nyquist plot mainly consists on a semicircular

section above the real axis, and then a straight line in the low-frequency section. The line at lower frequencies is nearlystraight, indicating the diffusion-controlled process withprominent capacitive performances with a tiny resistance fordiffusion.8,32 The semicircle intercept at high frequency on theplot real axis (Z′) reflects a joined resistance, that contains theinherent electrode resistance, electrolyte resistance, and contactresistance. The semicircle radius relates to the Faradaic chargetransfer resistance and EDLC at the electrode−electrolyteinterface.32 At the low-frequency area, the linear part isassociated with resistance (Warburg resistance Wo,) ofelectrolyte and ionic diffusion/transport into the electrodesurface. The diffusion line is nearly perpendicular to the realaxis in the impedance imaginary portion at the low-frequencysection, representing the ionic diffusion swift in the electrolyteand adsorption on the electrode surface, suggesting the idealcapacitive performance of the electrodes.33 The inset of Figure6 illustrates the symmetrical SC equivalent circuit, in thatequivalent circuit, R1 is connected in series to a capacitance ofthe double-layer (CFE, a CPE is often used in a model ratherthan a capacitor to compensate for nonhomogeneity in thesystem), which is connected in parallel to R2 and Wo. By fittingthe experimental data using ZviewTM software (Figure S4,Supporting Information), Rs values of 7.6 and 8 Ω and Rct

values of 47.5 and 52 Ω can be obtained from the electrodebefore and after 2500 cycles of charging/discharging experi-ments. The values of R1 are almost the same, whereas the valuesof R2 vary insignificantly. A minimal slope differences isobserved from the vertical diffusion lines, indicating theexcellent capacitive performance of the electrode before andafter long-term charging/discharging.The high capacitive performance might be ascribed to the

nanoflakes 2D structure that eases rapid transport of electronsbetween the active materials and the charge collecting substrate.The nanoflakes could act as 2D transport routes for storage andtransfer of the electrical charges from/to the electrodes. Inaddition, the nanoflakes have large specific surface areas andporous features which could enlarge the efficient liquid/solidinterfacial area, resulting in effective use of the active materialby increasing the number of electroactive sites. Therefore,FCO-NFs supported on flexible conductive nickel foam candirectly serve as free conductive agents and binder electrodesfor energy storage systems such as LIBs and symmetric SCs.

4. CONCLUSIONS

Interconnected FCO-NFS were productively developed onnickel foam substrates through a facile hydrothermal methodaccompanied by the calcination at 400 °C in air. The LIB anodefabricated from the FCO- NFs on nickel foam exhibits a firstdischarge capacity as high as 2445 mAh g−1 at 200 mA g−1

current density. This LIB anode also shows significant long-term cycling and rate capabilities performance. The symmetricSC assembled from FCO-NFs on nickel foam electrode exhibitselectrochemical capacitance as high as 433 and 225 F g−1 atscan rates of 1 and 5 mV s−1, respectively. This symmetric SCelectrode also shows capacitance activities under high scan ratesof 1000 and 5000 mV s−1. Such highly integrated binder- andadditive-free electrodes made by direct growth of electroactiveFCO-NFS on conductive substrates have a great potential forthe assembly of high rendering energy storage devices.

Figure 6. (a and b) First and last 10 charge−discharge curves at 2 Ag−1 current density in the potential range between 0 and 2.5 V for2500 cycles, and (c) Nyquist plot recorded for symmetrical SC cellscontaining FCO-NF/Ni foam before and after cycling to 2500 cycles(inset shows equivalent circuit of the FCO-NFs/Ni foam-basedsymmetric SC).

ACS Applied Materials & Interfaces Research Article

dx.doi.org/10.1021/am5068244 | ACS Appl. Mater. Interfaces 2014, 6, 22701−2270822706

■ ASSOCIATED CONTENT*S Supporting InformationCV curves of symmetrical supercapacitor containing FCO-NF/Ni foam electrode, first five cycles of galvanostatic charge−discharge of symmetric supercapacitor containing FCO-NFs/Ni foam electrode, Coulombic efficiency, Ragone plot andfitting results of experimental data with equivalent circuit of thesymmetric FCO-NFs/Ni foam SC electrode. This material isavailable free of charge via the Internet at http://pubs.acs.org.

■ AUTHOR INFORMATIONCorresponding Authors*Tel.: +886-2-77346088. E-mail: sfhu.hu@gmail.com.*E-mail: rsliu@ntu.edu.tw. Tel.: +886-2-33661169. Fax: +886-2-3366 8671.NotesThe authors declare no competing financial interest.

■ ACKNOWLEDGMENTSThe authors would like to thank the National Science Councilof the Ministry of Science and Technology of Taiwan(Contract Nos. MOST 103-2112-M-003-009-MY3 andMOST 101-2113-M-002-014-MY3) for financially supportingthis work. The financial support from the economic affairs of101-EC-17-A-08-S1-183 is also appreciated.

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ACS Applied Materials & Interfaces Research Article

dx.doi.org/10.1021/am5068244 | ACS Appl. Mater. Interfaces 2014, 6, 22701−2270822707

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ACS Applied Materials & Interfaces Research Article

dx.doi.org/10.1021/am5068244 | ACS Appl. Mater. Interfaces 2014, 6, 22701−2270822708