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Article
Fe2O3/RGO/Fe3O4 Composite in-situ Grown on
Fe Foil for High performance Supercapacitors
Chongjun Zhao, Xiaoxiao Shao, Yuxiao Zhang, and Xiuzhen Qian
ACS Appl. Mater. Interfaces, Just Accepted Manuscript • Publication Date (Web): 19 Oct 2016
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Page 1 of 33 ACS Applied Materials & Interfaces

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4 Fe2O3/RGO/Fe3O4 Composite in-situ Grown on Fe Foil for
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6 High performance Supercapacitors
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9 Chongjun Zhao*, Xiaoxiao Shao, Yuxiao Zhang, Xiuzhen Qian
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11 Key Laboratory for Ultrafine Materials of Ministry of Education, School of Materials Science and Engineering,
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14 East China University of Science and Technology, Shanghai 200237, P.R. China, Tel: +86-21-6425 0838; E-mail:
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16 chongjunzhao@ecust.edu.cn
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4 Abstract: A Fe2O3/RGO/Fe3O4 nanocomposite in-situ grown on Fe foil was synthesized via a
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6 simple one-step hydrothermal growth process, where the iron foil served as support, reductant of
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9 GO, Fe source of Fe3O4 and also the current collector of electrode. When it was directly acted as
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11 the electrode of a supercapacitor, as-synthesized Fe2O3/RGO/Fe3O4@Fe exhibited excellent
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14 electrochemical performance with high capability of 337.5 mF/cm2 at 20 mA/cm2 and superior
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16 cyclability with 2.3 % of capacity loss from 600th cycle to 2000th cycle.
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19 Key words: Fe2O3/RGO/Fe3O4, Fe foil, Graphene oxide, Hydrothermal process, Supercapacitor
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4 1. Introduction
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6 As the environmental problems and energy crisis become increasingly serious, it
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9 is essential to develop the new energy resource and also energy storage devices.
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11 Supercapacitor (i.e., electrochemical capacitor), as a member of the most important
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14 energy storage devices, is thought to be a promising candidate for storing energy due
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16 to its distinctive merits, i.e., high power density, excellent cycle stability, low
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19 equivalent series resistance, and superior rate capacity.1-3 According to charge storage
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21 mechanisms, supercapacitors can be classified into pseudocapacitors and electrical
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24 double layer capacitors (EDLCs). Pseudocapacitors rely on the fast Faradaic reaction
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26 to store charge, while EDLCs store charge depending on the static electricity force on
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29 the basis of the electrical double layer.4 Compared with the EDLCs, the
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31 pseudocapacitor possesses higher specific capacitance and energy density to satisfy
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34 the practical power application.
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36 The electrode materials play an important role in developing excellent
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39 performance supercapacitors.5-6 Referring to pseudocapacitor material, it mainly
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includes conducting polymers and transition metal oxides (TMOs).7 TMOs are
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44 regarded as the popular electrode materials for pseudocapacitors because of their good
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redox reversibility and large theoretical specific capacitance.8-11 Many TMOs
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49 including RuO2,12 NiO,13 Co3O4,14 MnO2,15 SnO2,16 ZnO,17 and WO318, have been
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researched to increase the energy density and the specific capacitance of
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54 pseudocapacitors. Unfortunately, all these metal oxides are confined within positive
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electrode materials, while for comparison, a few efficient transitional metal oxides are
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4 paid attention, e.g., TiO2,19 V2O5,20 Fe2O3,21 which are used as the negative electrode
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6 of supercapacitors.
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9 Recently, Fe2O3 has been intensively researched for application of electrode
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11 materials in supercapacitors due to variable oxidation states, good stability, abundance
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14 in nature, non-toxicity, low cost and non-pollution.7, 22-23
Nevertheless, Fe2O3
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16 generally suffers from poor conductivity (10-14 S cm-1) and low specific surface area,
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19 which leads the Fe2O3 electrode to exhibiting low specific capacitance, poor rate
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21 capability and cycling stability.24 For comparison, for another iron oxide, Fe3O4 shows
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24 excellent conductivity (102~103 S cm-1) which makes Fe3O4 become promising
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26 conductive support. To overcome poor electrical conductivity and optimize the
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29 electrochemical performance of Fe2O3 electrode, Fe3O4 have been introduced and
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31 combine with Fe2O3 to produce hybrid metal oxide composites. Chen et al.25 reported
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34 a α-Fe2O3/Fe3O4 heterostructure nanoparticle. Tang et al.26 fabricated hierarchical
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36 Fe2O3@Fe3O4 core shell nanorod arrays, in which Fe3O4 was used as a conductive
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39 support. These composites exhibited superior electrochemical performance to single
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component of Fe2O3 or Fe3O4, due to the synergistic effect of two kinds metal
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44 oxide.25-28
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Graphene, a two-dimensional (2D) carbon material, is usually introduced and
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49 combined with other materials because of its high conductivity (16,000 S/m) and
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specific surface area of 2,630 m2/g, as well as superior mechanical properties.29-31
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54 Also, due to its intrinsic electronic structure, the graphene can effectively prevent the
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agglomeration of nanoparticles, well-accommodate the volume changes of
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4 nanoparticles and maintain the integrity of electrode.32-33 Following this strategy, iron
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6 oxides can also be integrated with graphene to improve the electrochemical
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9 performances. Wang et al.34 found that Fe2O3 mesocrystal/graphene nanohybrid had
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11 higher specific capacitance than pure reduced graphene oxide (RGO). Lee at al.35
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14 reported that the specific capacitance of Fe2O3 nanotubes anchored on RGO was 8
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16 times as much as that of original Fe2O3. It was found by Wang et al.36 that
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19 graphene/Fe2O3 composite had much better cyclability than Fe2O3 (75% after 200
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21 cycles, vs. 49 % after 70 cycles). Yang et al.37 prepared a 3D Fe2O3/m-RGO film as
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24 the negative electrode of asymmetric supercapacitor which showed higher capacitance
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26 than the 3D m-RGO and RGO films.
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29 Moreover, in conventional method, powdery iron oxides as active material are
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31 often synthesized and thus further electrode preparation processes (e.g., grinding,
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34 slurry-coating) are necessary, which increases the cost and time. As far as we know, in
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36 supercapacitors, there is still no report on directly growth of iron oxide/graphene
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39 electrode materials on Fe foil or other conductive substrate, let alone through an
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in-situ redox reaction between reductive iron foil and oxidative graphene oxide (GO)
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44 in the absence of any other agents.
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In this work, a Fe2O3/RGO/Fe3O4 nanocomposite was in-situ grown on Fe foil
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49 via one-step hydrothermal growth process by means of the redox reaction among
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GO and Fe2+, as well as iron foil. Here, the iron foil acts as support, reductant of GO,
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54 iron source of Fe3O4 and also the current collector of electrode.38 To finally achieve
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hybrid metal oxide, the Fe2+ was added to use as the iron source of Fe2O3 because
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4 Fe2+ can be easily adsorbed on the surface of GO sheets because of the electrostatic
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6 force, in which Fe2+ was oxidized by GO.39 Benefited from the Fe-O bonding between
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9 FexOy particles and RGO, the agglomeration of FexOy particles is suppressed, and the
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11 electrons and ions transportation is also promoted.40 Thus, the as-prepared
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14 Fe2O3/RGO/Fe3O4@Fe with a hierarchical structure exhibited excellent
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16 electrochemical performance when directly acted as supercapacitor electrode.
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21 2. Experiment
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24 2.1 Materials and reagents
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26 Pristine graphite powder, anhydrous ethanol, iron sulfate heptahydrate
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29 (FeSO4·7H2O) were purchased from Sinopharm Chemical Reagent Company.
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31 Sulfuric acid (H2SO4, 95-98 wt%), hydrochloric acid (HCl, 36.0-38.0 wt%), hydrogen
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34 peroxide (H2O2, 30 wt%), potassium permanganate (KMnO4), phosphorus pentoxide
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36 (P2O5), potassium persulfate (K2S2O8) and potassium hydroxide (KOH, 30 wt%) were
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39 obtained from Shanghai Ling Feng Chemical Reagent Company.
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2.2 Synthesis of Fe2O3/RGO/Fe3O4 and RGO/Fe3O4 composites on iron foil
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44 Graphene oxide was synthesized through a modified Hummer’s method.41 Iron
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foil was cleaned with acetone and anhydrous ethanol under ultrasound irradiation to
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49 remove surface impurities, respectively.
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The synthesis of Fe2O3/RGO/Fe3O4 composites was conducted via a
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54 hydrothermal progress by immerging the iron foil in a mixture solution consisting of
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GO and iron salt. Typically, FeSO4·7H2O (2 mmol) was added in 38 ml DI water with
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4 stirring for 30 min. Then 2 ml of GO aqueous dispersion (5 mg·ml-1) was mixed
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6 homogeneously with the above solution under stirring. The above mixture was
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9 transferred into a Teflon-lined stainless steel autoclave (100 ml). Subsequently, the
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11 cleaned iron foil with a area of 1×1 cm2 was immerged in the solution, heating at
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14 150˚C for 12 h. In experiments, the effect of FeSO4 content and temperature on
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16 Fe2O3/RGO/Fe3O4 was investigated, and the obtained samples were denoted as
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19 F1RF-150 (1 mmol FeSO4·7H2O, 150˚C), F2RF-150 (2 mmol FeSO4·7H2O),
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21 F3RF-150 (3 mmol FeSO4·7H2O), F2RF-120 (120˚C), F2RF-180 (180˚C),
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24 respectively. The final product was washed with DI water and dried in a vacuum oven
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26 at 80˚C. For comparison, RGO/Fe3O4 (RF-150) composite was synthesized at the
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29 same conditions in the absence of FeSO4·7H2O.
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31 2.3 Characterization
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34 The X-ray diffraction (XRD) measurements were carried out using a X-ray
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36 diffractiometer with Cu Kα (λ = 0.15406 nm). Raman spectra were obtained on an
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39 INVIA Raman microprobe (Renishaw Instruments, England) with a 514 nm laser
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excitation. The X-ray photoelectron spectroscopy (XPS) spectra were performed on a
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44 PHI5300 instrument. The morphology and structure of products were investigated by
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a field-emission scanning electron microscope (FESEM, JEOL JSM-7800F),
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49 transmission electron microscopy (TEM, JEOL JEM-2100), respectively.
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2.4 Electrochemical measurement
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54 The electrochemical performance of as-synthesized electrodes was measured by
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cyclic voltammetry (CV), galvanostatic charge/discharge (GCD) and electrochemical
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4 impedance spectroscopy (EIS). All electrochemical measurements were carried out on
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6 an electrochemical workstation (CHI 660e, Shanghai) with a typical three electrode
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9 system in 2 M KOH. The as-prepared electrode materials with an apparent area of
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11 1×1 cm2, a platinum foil electrode, and a saturated calomel electrode (SCE) were
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14 acted as the working electrode, counter electrode, and reference electrode,
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16 respectively. When the electrochemical measurements finished, the loading amount of
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19 Fe2O3/RGO/Fe3O4 on iron foil was determined according to the weight difference.38
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21 2.5 Fabrication and electrochemical performance of asymmetric supercapacitor
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23 (ASC)
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25 In a two electrode system, an ASC device was assembled by directly using the
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28 Fe2O3/RGO/Fe3O4@Fe foil as negative electrode and Ni(OH)2 (Synthetic method was
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30 given in Supporting Information)as positive electrode. Briefly, the positive electrode
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33 was fabricated by mixing Ni(OH)2 powder (80 %) with acetylene (10 %) and
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35 poly(tetrafluoroethylene) (10 %), and the above mixture was coated on a Nickel foam
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38 (1×1 cm2). Then the positive electrode was dried at 80˚C for 12 h. The weights of
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40 active materials for negative and positive electrodes were about 4.3 mg and 2.1 mg,
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43 respectively. The electrochemical performance of ASC was tested in 2 M KOH.
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48 3. Results and discussion
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50 3.1. XRD patterns, Raman and XPS spectra of Fe2O3/RGO/Fe3O4 (FRF)
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53 nanocomposites
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55 Fig.1 shows the XRD patterns of RF-150 and F2RF-150. There are two
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58 diffraction peaks at 44.7° and 65.0°, which are assigned to the (110) and (220) planes
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4 of Fe (JCPDS No. 06-0696) arising from the iron foil substrate. Diffraction peaks at
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6 19.1°, 30.1°, 35.5°, 37.0°, 43.1°, 57.0°, and 62.6° for F2RF-150 and RF-150 are
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9 assigned to the (111), (220), (311), (222), (400), (511), and (440) planes of Fe3O4
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11 (JCPDS No. 75-1609). For F2RF-150, the other diffraction peaks at 24.1°, 33.2°,
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14 35.6°, 40.9°, 49.5°, 54.1°, 62.4° and 64.0° are assigned to the (012), (104), (110),
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16 (113), (024), (116), (214) and (300) planes of Fe2O3 (JCPDS No.33-0664),
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19 respectively. The existence of Fe2O3 and Fe3O4 can also be verified by the later
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21 Raman and XPS spectra of F2RF-150. In addition, the broad hump of RGO between
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24 20°~30° is not obvious, which is due to its highly disordered structure and low
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8 F2RF-150 ♣ Fe O
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•
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Intensity (a.u.)
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♥ ♣ ♥
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•
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21 •
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31 Fig. 1 XRD Patterns of F2RF-150 and RF-150.
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34 The presence of RGO can be verified by Raman spectra of RF-150 and
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36 F2RF-150 composites, as displayed in Fig. 2 and there are two obvious broad peaks
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39 for these two composites. The G band of 1598 cm−1corresponds to the vibration of
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sp2-bonded carbon atoms, and the D band of 1354 cm−1 originates from the defects.
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44 The ratio of G band (~1598 cm-1) and the D band (~1354 cm-1) can be used to
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semi-quantitatively determine the reduction extent of GO.43 In Fig. 2, the intensity
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49 ratio of D to G band (ID/IG) for composites (RF-150: 1.18; F2RF-150: 1.44) are
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remarkably higher than that for GO (0.88) or pure RGO (0.98), confirming the
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54 reduction of GO. On the other hand, there are also other peaks appearing in the low
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wavenumber range in the Raman spectra of RF-150 and F2RF-150. For RF-150, it is
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4 clear to see an apparent peak at 664 cm−1 with two weak ones at 308 and 531 cm−1,
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6 which are attributed to the fundamental Raman vibration of Fe3O4, assigned to the Eg,
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9 T2g, and A1g vibrational mode, respectively.44 These results indicate the formation of
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11 the composite of RGO and Fe3O4 in RF-150. For F2RF-150, besides the peaks for GO
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14 and Fe3O4, there are five additional peaks in the low wavenumber range, which
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16 correspond to the fundamental Raman vibration of Fe2O3, that is, 217 cm−1
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19 corresponds to A1g symmetry, 284, 395, 495, 592 cm−1 for Eg symmetry.45 These
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24 According to the results of XRD and Raman, the F2RF-150 is composed of Fe2O3,
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217 395 592
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50 Raman shfit (cm-1)
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Fig. 2 Raman spectra of GO, RGO, RF-150 and F2RF-150.
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4 Fig. 3 shows the X-ray photoelectron spectroscopy (XPS) of F2RF-150 that can
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6 further identify the chemical composition of the nanocomposite. The survey spectrum
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9 (0-1000 eV) of F2RF-150 (Fig. 3a) mainly shows Fe 2p, O 1s and C 1speaks, which
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11 indicates the existence of Fe, O and C elements in the sample. As presented in Fig. 3b,
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14 it is appropriate to divide the C 1s spectrum of F2RF-150 into three peaks at 284.6
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19 respectively.39 In Fig. 3c, the peaks from F2RF-150 for Fe 2p1/2 and Fe 2p2/3 appear at
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21 724.3 eV and 710.3 eV. For the Fe 2p1/2, it consists of two peaks, at 724.2 eV and
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24 722.4 eV. Similarly, the Fe 2p3/2 is composed of two peaks at 710.8 eV and 709.3 eV,
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26 respectively. Peaks at 722.4 eV and 709.3 eV are ascribed to the Fe3+ from Fe2O3,
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29 while the two peaks at 724.2 eV and 710.8 eV are resulted from Fe2+ of Fe3O4.46-47
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31 There is also a satellite peaks at 718 eV which correspond to the fingerprint of
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34 electronic structure of Fe2O3,48 confirming the existence of Fe2O3 in the F2RF-150
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36 again. The results of XRD, Raman and XPS convincingly suggest that the
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39 Fe2O3/RGO/Fe3O4 composite is successfully synthesized.
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6 a b C 1s
7 O KLL
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Intensity (a.u.)

Intensity (a.u.)
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C-C
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C 1s
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Fitted
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17 1000 800 600 400 200 0 294 292 290 288 286 284 282 280 278
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Fe 2p1/2
Fe 2p2/3
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718 eV 709.3 eV
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724.2 eV
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35 Binding energy (eV)
36 Fig. 3 XPS spectra of F2RF-150: (a) survey spectrum, (b) C 1s spectrum, and (c) Fe 2p spectrum.
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3.2. FESEM, TEM images and BET results of Fe2O3/RGO/Fe3O4(FRF) composites
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44 Fig. 4 presents the FESEM images of RF-150, F2RF-150, F2RF-120 and
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F2RF-180. In Fig.4a, it is found that the spherical Fe3O4 particles are anchored on the
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49 Fe substrate. Obviously, the number of these Fe3O4 spheres is not enough to cover the
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whole substrate surface, which leads to a low load amount and thus low specific
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54 capacitance. For comparison, the SEM image of F2RF-150 (Fig. 4b) is distinct
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difference: (1) No Fe substrate is observed, i.e., it is well decorated by the subsequent
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4 deposition of Fe2O3 from the Fe2+ ions. (2) Particles with interconnected 3D network
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9 nanosheets, and these hierarchical structures potentially facilitate fast electron
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11 transport and fast electrolyte ions diffusion. The formation process of Fe3O4/RGO and
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14 Fe2O3/RGO/Fe3O4@Fe composites is illustrated in Scheme 1. According to Fig. 4b-d,
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16 the morphology of Fe2O3/RGO/Fe3O4 nanocomposites is distinctly dependence of the
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19 hydrothermal synthesis temperatures (from 120 to 180ºC). At 120ºC (Fig. 4c), the
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21 space among Fe2O3 particles is bigger than 150ºC (Fig. 4b) because the reaction rate
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24 is slower so as only form a 2D coating layer of Fe2O3 nanoparticles. Therefore, the
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26 specific surface area of F2RF-120 is lower than that of F2RF-150, which is
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29 unfavorable to fully utilize the electrolyte ions. However, referring to F2RF-180 (Fig.
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31 4d), ununiform and dense Fe2O3 particles are clearly seen due to the overgrowth at
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34 high temperature (i.e., 180ºC), which somewhat hinders the electrolyte ions from
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36 entering into the active materials easily. Therefore, the porous structure ensures
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39 F2RF-150 nanocomposite to exhibit the superior electrochemical performances.
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As shown in Fig. 5, the structure of as-synthesized Fe2O3/RGO/Fe3O4
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44 nanocomposite is further investigated by transmission electron microscope (TEM).
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Compared with the TEM image of pure RGO in Fig. 5a, the interconnected Fe2O3
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49 nanosheets are well decorated on the two-dimensional graphene sheets as seen in the
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Fig. 5b. A few Fe3O4 particles can be observed in Fig. 5b, because the Fe3O4 in-situ
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irradiation condition. In the Fe2O3/RGO/Fe3O4 nanocomposite, graphene sheets not
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9 iron oxides electrodes.49
10
11 The N2 adsorption-desorption isotherm of Fe2O3/RGO/Fe3O4 composite is shown
12
13
14 in Fig. S1. The narrow hysteresis loop suggests the porosity of materials and the BET
15
16 surface area of Fe2O3/RGO/Fe3O4 composite is about 16.93 m2/g.
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Fig. 4 FESEM images of (a) RF-150, (b) F2RF-150, (c) F2RF-120, and (d) F2RF-180
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42 Scheme 1.Schematic diagram of preparation of the RF and FRF composites.
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47 3.3. Electrochemical performance of Fe2O3/RGO/Fe3O4 (FRF) nanocomposites
48
49 Fig. 6a presents the CV curves of F2RF-150 ranging from 5 to 50 mV/s and
50
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52 every curve has a reduction peak and two oxidation peaks in range from -1.2 to -0.4 V
53
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because of the conversion between Fe2+ and Fe3+, suggesting the pseudocapacitive
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4 corresponds to the formation of Fe(OH)2, while the other oxidation peak at -0.65 V is
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6 ascribed to the formation of FeOOH. The arising of reduction peak at -1.1 V results
7
8
9 from the reduction from FeOOH to Fe(OH)2.21 In Fig. 6a, it is notable that these CV
10
11 curves maintain a similar shape and the current response increases as the scan rate
12
13
14 varies from 5 to 50 mV/s, indicating that the composite is beneficial for fast and
15
16 reversible redox reactions.39
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19 The CV curves of RF-150, F1RF-150, F2RF-150 and F3RF-150 at 10mV/s are
20
21 shown in Fig. 6c. It is clear that F2RF-150 has higher current response than others, i.e.,
22
23
24 it has the highest specific capacitance, while the RF-150 composite has the lowest
25
26 specific capacitance. This result is relative with the loading of Fe2O3 on the surface of
27
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29 RGO, which increases the content of active materials and improve capacitance.
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31 However, the specific capacitance decreases when the addition of Fe2+ is increased to
32
33
34 3 mmol (i.e., F3RF-150), because more Fe2O3 could not be utilized fully in the redox
35
36 process and results in the growth of dead active materials.50 Fig. 6e presents the CV
37
38
39 curves at 10 mV/s of composites synthesized at different temperatures (i.e., F2RF-120,
40
41
F2RF-150, F2RF-180). The F2RF-150 also exhibits the best performance.
42
43
44 Fig. 6b displays the GCD performance of F2RF-150 at different current density
45
46
of 5, 10, 20, 30, 50, and 100 mA/cm2 (corresponding to 1.16, 2.33 4.65, 6.98, 11.63
47
48
49 and 23.26 A/g) with potential window from -1.2 to -0.4 V. All these GCD curves have
50
51
the platforms which demonstrates that the capacitance is mainly governed by the
52
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54 redox reaction in according with the pseudocapacitive characteristic reflecting in the
55
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CV curve of F2RF-150 (Fig. 6a).51
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4 Similar to CV curves, Fig. 6c and 6f show the GCD curves at 20 mA/cm2 for
5
6 those composites prepared at different conditions (Fe2+ content and reaction
7
8
9 temperature). It can be seen that the F2RF-150 has the longest discharge time, so this
10
11 nanocomposite holds the highest specific capacitance, corresponding to the results of
12
13
14 CV curves.
15
16 The specific capacitance (Cs) of all composites can be calculated using the
17
18
19 following equation:52
20
21 C I * ∆t
CS = = (1)
22 S ∆V * S
23
24 Where I (A) is the charge-discharge current, ∆t (s) is the discharge time, ∆V (V)
25
26 is the potential window and S (cm2) is the geometric surface area of working
27
28
29 electrodes.
30
31 Table 1 lists the specific capacitance at 20 mA/cm2 for all composites, and the
32
33
34 F2RF-150 exhibits the best capacity (337.5 mF/cm2, 78.49 F/g). The F2RF-150
35
36 electrode also shows better rate capability than RF-150, F1RF-150 and F3RF-150, as
37
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39 shown in Fig. 6g.
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4 0.05
a 5mV/s -0.4 b 5mA/cm
2

5 0.04 10mV/s
-0.5 10mA/cm
2

20mV/s 2
6 0.03 20mA/cm
Current density (A/cm )
2

Potentital vs. SCE (V)

30mV/s -0.6 2
7 0.02 30mA/cm
50mV/s 2
50mA/cm
8 0.01 -0.7
2
100mA/cm
9 0.00
-0.8
10 -0.01
-0.9
11 -0.02
-0.03 -1.0
12
-0.04
13 -1.1
-0.05
14 -1.2
-1.2 -1.1 -1.0 -0.9 -0.8 -0.7 -0.6 -0.5 -0.4 0 10 20 30 40 50 60 70 80 90 100 110
15
Potentital vs. SCE (V) Time (s)
16
17 RF-150
18 0.02 c -0.4 d RF-150
F1RF-150 F1RF-150
-0.5
19 F2RF-150 F2RF-150
Current density (A/cm2)

F3RF-150 F3RF-150

Potentital vs. SCE (V)

20 0.01 -0.6
21 -0.7
22 0.00
-0.8
23
24 -0.01
-0.9

25 -1.0
26 -1.1
-0.02
27
-1.2
28 -1.2 -1.1 -1.0 -0.9 -0.8 -0.7 -0.6 -0.5 -0.4 0 2 4 6 8 10 12 14 16 18 20 22 24 26
29 Potential vs. SCE (V) Time (s)
30
31 e -0.4
f F2RF-120
0.02
32 -0.5
F2RF-150
F2RF-180
33 F2RF-120
Current density(A/cm )
2

Potentital vs. SCE (V)

0.01 -0.6
34 F2RF-150
F2RF-180
35 -0.7

36 0.00 -0.8
37 -0.9
38 -0.01
-1.0
39
40 -0.02 -1.1

41 -1.2
-1.2 -1.1 -1.0 -0.9 -0.8 -0.7 -0.6 -0.5 -0.4 0 2 4 6 8 10 12 14 16 18 20 22 24 26
42
Potentital vs. SCE (V) Time (s)
43
44 400
45 g RF-150
350 F1RF-150
46
Specific capacitance (mF/cm2)

F2RF-150
47 300
F3RF-150
48 250
49
200
50
51 150

52 100
53
50
54
55 0
0 10 20 30 40 50
56 Current density (mA/cm2)
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4 Fig. 6 (a) Cyclic voltammetry (CV) curves at different scan rates, and (b) Galvanostatic
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6 charge/discharge (GCD) curves under various current densities for F2RF-150. (c) CV curves at
7
8
9 scan rate of 10 mV/s,and (d) GCD discharge curves at current density of 20 mA/cm2 for RF-150,
10
11 F1RF-150, F2RF-150 and F3RF-150. (e) CV curves at scan rate of 10 mV/s and (f) GCD
12
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14 discharge curves at 20 mA/cm2 for F2RF-120, F2RF-150, and F2RF-180. (g) The specific
15
16 capacitance of RF-150, F1RF-150, F2RF-150 and F3RF-150 electrodes under different current
17
18
19 density.
20
21
22
23
24 Table.1 Specific capacitances for various composites at 20 mA/cm2.
25
26 Samples RF-150 F1RF-150 F2RF-150 F3RF-150 F1RF-120 F1RF-180
27
28
29 Area capacitance
55 95 337.5 130 87.5 170
30 (mF/cm2)
31
32
33
34
35 The F2RF-150 exhibits excellent cycle stability and Fig. 7 shows the cycling
36
37 performance of F2RF-150 electrode after 2000 cycles of charge/discharge at 20
38
39
40 mA/cm2. It can be observed that the specific capacitance of F2RF-150 electrode
41
42 increases obviously in the first 600 cycles (from 337.5 to 524.5 mF/cm2) and then
43
44
45 remain stable until 2000 cycles (512.5 mF/cm2). There is only 2.3 % capacity loss
46
47 from 600th cycle to 2000th cycle. The increase of specific capacitance may be
48
49
50 attributed to the activation process which enable the trapped ions to diffuse out, while
51
52 the expansion of interlayer spacing of RGO sheet facilitates the intercalation of
53
54
55 counter ion.35 For comparison, the capacity decay of RF-150 electrode is up to 42.11%
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after 2000 cycles at 20 mA/cm2, which is much worse than F2RF-150. Furthermore,
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4 the F2RF-150 electrode still remains 95 % retention of the maximum capacity even
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6 after 5000 cycles (Fig. 7 inset). Compared with the SEM image of F2RF-150 before
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9 cycling test (Fig. 4b), the Fe2O3 particles after cycling become smaller and distribute
10
11 more uniformly, as shown in Fig. S2. Also, the Coulombic efficiency always keeps
12
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14 above 90 % during the whole cycling process, which suggests the good reversibility
15
16 of F2RF-150 electrode material.53
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19
20
21
22 600
Specific Capacitance (mF cm-2)

23 F2RF-150
24 RF-150
25 500
26 1400 100
27
Specific Capacitance (mF cm-2)

28 400 1200

Coulombic Efficiency (%)

80
29 1000
30 300 800 60
31
600
32 40

33 200 400

34 200
20

35
36 100 0
0 1000 2000 3000 4000
0
5000
Cycle number
37
38
0
39 0 200 400 600 800 1000 1200 1400 1600 1800 2000
40
41 Cycle number
42
43
Fig. 7 Cyclability of the RF-150 and F2RF-150 electrodes at 20 mA/cm2. Inset: the
44
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46 coulombic efficiency and 5000 cycle curve of F2RF-150 at 20 mA/cm2.
47
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49 The EIS measurements were conducted at open circuit potential (OCP). Fig. 8
50
51 gives the Nyquist plots of F1RF-150, F2RF-150 and F3RF-150 electrodes collected
52
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54 with an sinusoidal signal of 5 mV, in the frequency vary from 100 kHz to 0.01 Hz. In
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56 Nyquist plots, the X-intercept of semicircle represents the equivalent series
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4 resistances (Rs), which are 0.9, 1.1, 2.1 Ω for the F1RF-150, F2RF-150, and
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6 F3RF-150, respectively. With the increase of Fe2+, Rs values increase because the
7
8
9 content of poor electrical conductivity Fe2O3 in the nanocomposites grows. In Fig. 8,
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11 the diameter of semicircle is a characteristic of charge transfer resistance (Rct) at
12
13
14 electrolyte/electrode interface, and the order of Rct value is: F1RF-150 > F2RF-150 >
15
16 F3RF-150. Comprehensively, the F2RF-150 holds more moderate resistance than
17
18
19 other two materials and exhibits the best electrochemical performance. After 5000
20
21 cycles, there is a little change for the Nyquist plot of F2RF-150 (Fig. S2) and the
22
23
24 internal resistance even become smaller than 1st cycle, which can further confirm the
25
26 exceptional cyclability of F2RF-150 electrode.
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29
30
31
32
33
34
35 50
36
37
38 40
39
40
-Z"/ohm

41 30
42 12
F1RF-150
43 F1RF-150 10
F2RF-150
F3RF-150

44 20 F2RF-150 8
-Z"/ohm

45 F3RF-150
6

46 4

47 10 2

48 0
0 2 4 6 8 10 12
49 Z'/ohm
50 0
0 10 20 30 40 50
51
52 Z'/ohm
53
54
Fig. 8 Nyquist plots of F1RF-150, F2RF-150, F3RF-150. Inset: the date of high frequency region
55
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4 3.4 Electrochemical performances of asymmetric supercapacitors
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6 In an ASC device, the Ni(OH)2 and F2RF-150 were employed as positive and
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9 negative electrodes, respectively (denoted as Ni(OH)2//F2RF-150). The
10
11 electrochemical performances of Ni(OH)2 electrode measured in 2 M KOH using a
12
13
14 three electrode system are given in Fig. 9. Fig. 9a displays the CV curves of
15
16 Ni(OH)2 electrode and every curve has a pair of redox peaks, suggesting that the
17
18
19 capacitance of Ni(OH)2 is mainly contributed by Faradic reaction.54 Non-linear GCD
20
21 curves (Fig. 9b) further confirm the pseudocapacitance of Ni(OH)2. In Fig. 9c, the
22
23
24 mass specific capacitance of Ni(OH)2 is 260.4, 203.1, 153.6 and 62.6 F/g at a current
25
26 density of 5.2, 7.8, 13 and 26 A/g, respectively.
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5 a b
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6 10 mV/s
30 mA/cm2
7 0.04 20 mV/s
Current density (A/cm )

50 mA/cm2

Potentital vs. SCE (V)

2

30 mV/s 0.4
8
0.02 50 mV/s 100 mA/cm2
9
0.3
10 0.00
11
12 -0.02 0.2

13
-0.04
14 0.1

15 -0.06
16 0.0 0.1 0.2 0.3 0.4 0.5
0.0
0 10 20 30 40 50 60
17 Potentital vs. SCE (V) Time (s)
18
19 c
250
20
21
Mass specific capacitance (F/g)

22 200

23
24 150

25
26 100
27
28 50
29
30 0
1 2 3 4
31
Current density (A/g)
32
33
34 Fig. 9 (a) CV curves at different scan rates, (b) GCD curves under various current densities and (c)
35
36 The mass specific capacitance under different current density of Ni(OH)2 electrode.
37
38
39
40
41
To achieve the optimal performance of asymmetric supercapacitor, the charge
42
43
44 should be balanced between the two electrodes according to Q+= Q −. The mass
45
46
loading of Ni(OH)2 is calculated according to the following equation:
47
48
49 Cୱି ∆Vି = C୫ା ∆Vା mା (2)
50
51
52
Where CS— (mF/cm2) and Cm+ (F/g) represent the specific capacitance of negative
53
54 electrode and positive electrode. ∆V— (V) and ∆V+ (V) are the potential window of
55
56
57
negative and positive electrodes. S (cm2) is the area of Fe2O3/RGO/Fe3O4 electrode,
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4 m+ (mg) is the loading mass of Ni(OH)2.55 According to the above equation, the
5
6 optimal loading mass of Ni(OH)2 is determined to be 2.1 mg in the asymmetric
7
8
9 supercapacitor.
10
11 The CV curves of F2RF-150 and Ni(OH)2 electrodes at scan rate of 20 mV/s in
12
13
14 three electrodes system are displayed in Fig. 10a. The potential window of F2RF-150
15
16 and Ni(OH)2 electrodes are -1.2~-0.4 V and 0~0.5 V, respectively. This indicates that
17
18
19 the cell voltage of Ni(OH)2//F2RF-150 can be extended to 1.7 V in 2 M KOH. The
20
21 CV curves of Ni(OH)2//F2RF-150 in different cell voltage at 50 mV/s are given in Fig.
22
23
24 10b, in which the potential window is 0~1.7 V for the ASC.
25
26
27 0.02
28 0.04 a F2RF-150
b
29 0.03 Ni(OH)2
Current density (mA/cm2)
Current density (mA/cm2)

30 0.02 0.01
31 0.01
32
0.00
33 0.00
34 -0.01

35 -0.02
36 -0.03 -0.01
37
-0.04
38
-1.2 -1.0 -0.8 -0.6 -0.4 -0.2 0.0 0.2 0.4 0.6 0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6 1.8
39
Potential vs. SCE (V) Voltage (V)
40
41 Fig. 10 (a) CV curves of F2RF-150 and Ni(OH)2 electrodes at 20 mV/s in three electrodes
42
43
44 system. (b) CV curves of Ni(OH)2// F2RF-150 in different cell voltage at 50 mV/s.
45
46
47
48
49 Fig. 11a and Fig. 11b show the CV and GCD curves of Ni(OH)2//F2RF-150 ASC
50
51
device. According to GCD curves (Fig. 11b), the specific capacitance of the ASC
52
53
54 device is 66.2 mF/cm2 (10.3 F/g), 44.1 mF/cm2 (6.9 F/g), 36.5 mF/cm2 (5.7 F/g),
55
56
57
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6 Ni(OH)2//F2RF-150 was conducted for 2000 cycles under 20 mA/cm2 and the specific
7
8
9 capacitance increases from 45.9 mF/cm2 to 152.9 mF/cm2. Fig. 11e is the Nyquist plot
10
11 of ASC device, where the equivalent series resistance is only 1.5 Ω. To evaluate the
12
13
14 electrochemical performances of supercapacitors, the energy density (E) and power
15
16 density (P) are two key factors, which can be calculated by the following equations:
17
18
19
20
21 E = (C × ∆V ଶ )/2 (3)
22
23
24 P = E/∆t (4)
25
26 Where E (Wh/kg) is energy density, C (F/g) is mass specific capacitance, ∆V (V) is
27
28
29 cell voltage of ASC, P (W/kg) is power density, and ∆t (s) is discharging time.55 The
30
31 Ragone plot of Ni(OH)2//F2RF-150 is displayed in Fig. 11f, in which the energy
32
33
34 density is 4.1, 2.8, 2.3, 2.2, 2.2 Wh/kg at the power density of 661.5, 1329.4, 2656.9,
35
36 3973.8, 6600 W/kg, correspondingly.
37
38
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5 a 1.8 b 5 mA/cm2
0.010
6 1.6
10 mA/cm2
7 20 mA/cm2
Current density (mA/cm2)

1.4 30 mA/cm2
8 0.005
50 mA/cm2
1.2
9

Voltage (V)
10 0.000 1.0

11 0.8

12 -0.005
5 mV/s 0.6
10 mV/s
13 20 mV/s 0.4
14 -0.010
30 mV/s
0.2
15 50 mV/s
0.0
16 0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6 1.8 0 10 20 30 40 50
Time (s)
17 Voltage (V)
18 70 12 160
19 c d
140
20

Specific capacitance (mF/cm2)

Mass specific capaciance (F/g)
Specific capacitance (mF/cm2)

10 120
21 60
100
22
8
23 80
50
24 60
6
25 40
26 40 20
27 4
0
28
29 30 2 -20
0 500 1000 1500 2000
0 10 20 30 40 50
30
Current density (mA/cm2) Cycle number
31
800
32 e
10
f
33 8
4
6
34 600
Energy density (Wh/kg)

4
35 2
36
-Z"/ohm

0
0 2 4 6 8 10
37 400 3

38
39
200
40
2
41
42 0
0 2000 4000 6000
43 0 200 400 600 800
Z'/ohm Power density (W/kg)
44
45
46
Fig. 11 (a) CV curves at different scan rates, (b) GCD curves under different current densities, (c)
47
48
49 Cyclability at 20 mA/cm2, (d) The specific capacitance and mass specific capacitance at different
50
51
current densities, (e) Nyquist plot (Inset: the data of high-frequency region) and (f) Ragone plot
52
53
54 related to energy and power density of Ni(OH)2//F2RF-150 ASC device.
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4 4. Conclusions
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6 In summary, a Fe2O3/RGO/Fe3O4 nanocomposite in-situ grown on Fe foil was
7
8
9 successfully synthesized through a one-step hydrothermal synthesis process. Both
10
11 Fe2+ content and temperature affected the nanostructures and electrochemical
12
13
14 performances of Fe2O3/RGO/Fe3O4 nanocomposite. F2RF-150 electrode exhibits the
15
16 best electrochemical performance based on the synergistic effect of Fe2O3, Fe3O4 and
17
18
19 RGO. The specific capacitance of this electrode can achieve 337.5 mF/cm2 at 20
20
21 mA/cm2 in 2 M KOH solution, and only 2.3 % capacity loss was observed from 600th
22
23
24 cycle to 2000th cycle. An asymmetric supercapacitor of Ni(OH)2//F2RF-150 was
25
26 assembled and delivered energy density of 4.1, 2.8, 2.3, 2.2, 2.2 Wh/kg at the power
27
28
29 density of 661.5, 1329.4, 2656.9, 3973.8, 6600 W/kg, respectively.
30
31
32
33
34 Acknowledgement: We are grateful for the support of Shanghai Natural Science
35
36 Foundation (No. 13ZR1411900), and Shanghai Key Laboratory Project
37
38
39 (08DZ2230500).
40
41
42
43
44 SUPPORTING INFORMATION
45
46
Synthesis of Ni(OH)2; the N2 adsorption-desorption isotherm of Fe2O3/RGO/Fe3O4
47
48
49 composite; SEM image of F2RF-150 after 5000 cycles; Nyquist plots of F2RF-150
50
51
electrode after 1st and 5000th cycle; CV curves for the F2RF-150 electrode in the
52
53
54 KOH solution with different concentrations.
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4 References
5
(1) Winter, M.; Brodd, R. J., What Are Batteries, Fuel Cells, and Supercapacitors? Chem. Rev.
6
7 2004,104 (10), 4245-4270.
8 (2) Peng, X.; Peng, L. L.; Wu, C. Z.; Xie, Y., Two Dimensional Nanomaterials for Flexible
9 Supercapacitors. Chem. Soc. Rev. 2014,43 (10), 3303-3323.
10
11 (3) Zhang, X. J.; Shi, W. H.; Zhu, J. X.; Zhao, W. Y.; Ma, J.; Mhaisalkar, S.; Maria, T. L.; Yang, Y. H.;
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