A High-Performance Energy Storage Device Based on Triple-shelled

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A High-Performance Energy Storage Device Based on Triple-shelled Cobalt Gallium Oxide Hollow Spheres and Graphene Wrapped Copper Iron Disulfide Porous Spheres Akbar Mohammadi Zardkhoshoui, Saied Saeed Hosseiny Davarani, Mona Maleka Ashtiani, and Morteza Sarparast ACS Sustainable Chem. Eng., Just Accepted Manuscript • DOI: 10.1021/ acssuschemeng.9b00549 • Publication Date (Web): 18 Mar 2019 Downloaded from http://pubs.acs.org on March 18, 2019

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ACS Sustainable Chemistry & Engineering

A High-Performance Energy Storage Device Based on Triple-shelled Cobalt Gallium Oxide Hollow Spheres and Graphene Wrapped Copper Iron Disulfide Porous Spheres Akbar Mohammadi Zardkhoshoui1, Saied Saeed Hosseiny Davarani1*, Mona Maleka Ashtiani2, Morteza Sarparast2. 1Department

of Chemistry, Shahid Beheshti University, Daneshjou Blvd, Shahid Chamran

Highway, 1983963113, Evin, Tehran, Iran. 2Department

of Chemistry, Michigan State University, 578 S Shaw Ln, East Lansing, Michigan

48824-1322, USA. *Corresponding author, Tel: +98 21 22431661; Fax: +98 21 22431661. E-mail address: [email protected] (S.S.H. Davarani)

ABSTRACT Demanding more reliable power sources causes a huge development of modern electronic and optoelectronic devices with a high energy density (ENDE) and exceptional durability. Accordingly, designing modern electrode materials with outstanding structures can improve the construction of a new generation of electronic devices. Transition metal oxides hollow structures (TMOHS) have received considerable attention as appropriate materials for supercapacitors due to their structural properties and electrochemical performances. As a fascinating TMOHS, we make a new highly porous triple-shelled cobalt gallium oxide (CoGa2O4) hollow spheres (HTS-

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CGOHS) with triple narrow shells, and pseudocapacitive graphene wrapped CuFeS2 hollow spheres (GW@CFSHS) as developed positive and negative electrodes, respectively in an energy storage device. The HTS-CGOHS electrode shows specific capacitance (SpCa) of 1724.30 F g-1 (239.5 mAh g-1) at 1 A g-1 which maintains as high as 1198.40 F g-1 (166.44 mAh g-1) at 24 A g-1, and reasonable durableness (96.80% capacity retention at 12 A g-1) owing to the low internal resistance, fast kinetics, reversibility, high surface area (104.30 m2 g-1), and numerous active sites. Moreover, the GW@CFSHS advanced negative electrode reveals electrochemical performance comprising a SpCa of 621.20 F g-1 (172.6 mAh g-1), rate performance of 58% and excellent durableness, which are superior to that of CuFeS2 hollow sphere (CFSHS) electrode. According to the electrochemical nature of the as-obtained pseudocapacitive electrode materials, an energy storage device (ESD) based on the HTS-CGOHS as a cathode and GW@CFSHS as an anode was studied. The HTS-CGOHS//GW@CFSHS device shows SpCa of 376.40 F g-1 (153.1 mAh g-1), high ENDE of 114.8 W h kg-1, and notable durableness (only 6.3% decrease after 5000 cycles at 6 A g-1). Keywords: CoGa2O4; Hollow sphere; Energy storage device; Graphene; CuFeS2.

INTRODUCTION Greenhouse gas generation is an inevitable consequence of an energy infrastructure that relies on combustion of fossil fuels.1-4 Thus, finding practical solutions that replacing fossil fuels with sustainable and clean energy sources is desirable. Renewable energy sources like wind and solar can generate electricity intermittently but store and distributing that energy for use on demand


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is challenging.5-7 Therefore, this challenge highlights the significance of energy storage technologies. Supercapacitors as favorable energy storage devices are of considerable current interest due to their reversibility, durableness, and power densities.8-12 Electrochemical double layer capacitors (EDLCs) and pseudocapacitors are two categories of supercapacitors divided by various charge storage mechanisms. EDLCs generate capacitance by the electrostatic charge that is aggregated at electrode-electrolyte interfaces, such as graphene, carbon nanotubes, and activated carbon. 13-15 In pseudocapacitor, faradic reactions are produced due to the electroactive species, such as conducting polymers, hydroxides, and transition metal oxides (TMOs).16-19 Consequently, unlike batteries, supercapacitors charging is not restricted by the diffusion of ions, and thus superior power densities can be obtained in supercapacitors.20,21 However, the considerable challenge for supercapacitors is their low energy density (ENDE), which barricades their applications substantially when superb ENDE is needed. The ENDE of the supercapacitor is directly proportional to the operating potential window (OPW) and specific capacitance (SpCa).22-24 Therefore, a better performance of supercapacitor can be obtained using the materials with pseudocapacitive properties (e.g., hydroxides/transition metal oxides), and high surface area (SA). Hollow nanomaterials (HNM) are of great interest for engineering energy storage systems because of their surface permeability, huge SA, porosity, and low mass density.25-30 Recently, HNMs such as hollow cubes,31 nanocages,32 needles,33 tubes,34 and spheres,35,36 has attracted significant attention in different energy storage and biomedical applications. Apart from the decreased transfer passageway for electrons/ions and diminished agglomeration of materials, the complex internals of the hollow particles can increase the ENDE of the electrode via improving the weight fraction of the active materials.37,38. Among the diverse kinds of HNMs, porous hollow


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spheres (PHS) are more attractive due to their huge SA, short transport pathway, similar shell thickness and well-defined hollow internal.39 In recent decades, transition metal oxides (TMOs) with different metals, have developed as a proper group of materials for various electrochemical demands containing electrocatalysts, supercapacitors, and lithium-ion batteries.40,41 Among the variant TMOs, cobalt-based spinels with the formula of CoM2O4 (M= Fe and Mn) have been extremely examined for supercapacitors, owing to their chemical affinity with the surface of nickel substrates, environmental amiability, redox reaction properties, and theoretical SpCa.42 The durableness and rate capability obtained by cobalt-based supercapacitors are typically low, due to their insignificant chemical-mechanical stability and electronic conductivity. Thus, employing favorable elements such as gallium (Ga) in electrode materials can enhance the electrochemical performance of the cobalt-based supercapacitors. Recently, Liu et al. reported NiGa2O4 nanosheets that illustrate SpCa of 1508 F g-1, and great durability with ENDE of 45.2 Wh kg-1 for the ASC.43 Furthermore, our group prepared CuGa2O4 spinels on bare nickel foam (BNF) with the SpCa of 1210.40 F g-1, excellent durableness with ENDE of 63.15 Wh kg-1 for the ASC.44 To the best of authors knowledge, there is only one report on using Cobalt gallium oxide (CGO) as a cathode electrode for ASC. Chai et al. proposed CGO spinels with the SpCa of 642.4 C g-1, remarkable durableness with ENDE of 36.71 Wh kg-1 for the ASC.45 Thus, to enhance the electrochemical properties of CGO, the fabrication of HNMs with large SA can be efficient. Particularly, triple-shelled nanostructures (TSNS) with highly porous texture possess a huge SA, which can create numerous active sites for electrochemical reaction. Unlike the symmetric or traditional supercapacitors, asymmetric supercapacitors (ASC) are consist of two different electrode materials for cathode and anode. By such assembly, both


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specific capacitance and energy density of the device enhance in the aqueous electrolyte by increasing the working cell voltage beyond the thermodynamic breakdown potential of water. Therefore, the asymmetric devices have remarkably higher power and energy density in comparison with the symmetric devices. Thus, herein, for the positive electrode, we designed and constructed a highly porous triple-shelled cobalt gallium oxide (CoGa2O4) hollow spheres (HTSCGOHS) with SA of 104.2 m2 g-1 which can deliver SpCa of 1724.30 F g-1 1 (239.5 mAh g-1) with 69.50% rate performance, and notable durableness, indicating its capability as a superior positive electrode material for devices. Besides, for the negative electrode, we used graphene wrapped copper-iron disulfide hollow spheres (GW@CFSHS) due to the electrochemical properties of CuFeS2 in the negative potential area improved by the graphene nanosheets. The GW@CFSHS electrode illustrated electrochemical properties comprising SpCa of 621.20 F g-1 (172.6 mAh g-1) and superb durableness, which are better than previous iron-based electrodes. Furthermore, a developed ESD was constructed by HTS-CGOHS as the cathode and GW@CFSHS as the anode, indicating high ENDE of 114.8 Wh kg-1 based on the prepared mass of active materials. The HTSCGOHS//GW@CFSHS device also indicated SpCa of 376.40 F g-1 (153.1 mAh g-1) and wonderful durableness. Eventually, we used 2- HTS-CGOHS//GW@CFSHS devices collected in series for powering up a green light emitting diode for illustrating their capability as a modern device for new generation of electronic systems.

EXPERIMENTAL SECTION Materials and Reagents. All materials were procured from Merck and Sigma-Aldrich corporations including 1,3,5-Benzenetricarboxylic acid (C₆H₃-1,3,5-(COOH)₃), Hydrogen peroxide (H2O2), Cobalt(II) nitrate hexahydrate (Co(NO3)2·6H2O), Iron(II) sulfate heptahydrate


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(Fe(NO3)2·6H2O), Sulfuric acid (H2SO4), Gallium(III) nitrate hydrate (Ga(NO3)3·xH2O), Copper(II) sulfate pentahydrate (CuSO4·5H2O), Hydrochloric acid (HCl), Sodium thiosulfate pentahydrate (Na2S2O3·5H2O), Sodium nitrate (NaNO3), Sulfur powder, Powdered graphite, Dimethylformamide (DMF, (CH3)2NC(O)H), Potassium permanganate (KMnO4). Bare Nickel foam (BNF) is utilized as the current collector. Synthesis of the HTS-CGOHS. To fabricate the HTS-CGOHS, 270.65 mg Co(NO3)2·6H2O, 475.67 mg Ga(NO3)3·xH2O (NG), and 131.3 mg 1,3,5-benzenetricarboxylic acid (BTC) were separately mixed in 10 ml DMF, then stirred for two hours. The NG mixture was gradually added to the Co-BTC solution and stirred for one hour. The solution was transferred to a glass tube and reacted to CoGa-BTC precursors at 150 oC for one hour under microwave-irradiation. After cooling down to room temperature, the as-fabricated CoGa-BTC precursors were separated by centrifugation, washed several times using ethanol and dried at 60 °C. The obtained CoGa-BTC powder was annealed at 500 oC for two hours with a heating rate of 5 oC min-1. Synthesis of the CFSHS. At first, 120.8 mg of Cu(NO3)2.3H2O, 144 mg of Fe(NO3)2.6H2O and 152.25 mg of thiourea were mixed in the solution of 20 mL isopropyl alcohol and 20 mL ethylene glycol. The solution kept in the autoclave at 180 °C for eleven hours. The product was gathered through centrifugation, washed by ethanol, and dried at 80 °C, and then calcined at 350 °C for two hours under N2 to obtain CFSHSs. Synthesis of the GW@CFSHS. Graphene oxide was made from powder's graphite through a Hummer's route.46 To make GW@CFSHS, 0.3 g of the as-fabricated CFSHSs were dispersed into a mixture including 30 mL isopropanol and 0.3 mL APTES, followed by stirring 24 hours to produce positively charged surface-modified CFSHSs. After washing by ethanol, the residue was


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dispersed into 60 mL water and then mixed with 90 mL aqueous GO suspension (0.3 mg mL-1). After stirring for three hours, the products were obtained by centrifugation and then kept at 500 °C for four hours under Ar atmosphere for reduction of GO. Characterization. X-ray diffraction (XRD) characterization of the products was examined by a Philips X’ pert diffractometer with Cu Kα radiation. To measure the electron states of the HTSCGOHS and GW@CFSHS samples the X-ray photoelectron spectroscopy (XPS) with an ESCALAB 250Xi X-ray photoelectron spectrometer was employed. To find the SA and pore size distributions of as-constructed materials, a Micromeritics ASAP-2010 system with Brunauer– Emmett-Teller (BET) and Barrett–Joyner–Halenda (BJH) techniques were applied. The morphologies of the HTS-CGOHS and GW@CFSHS samples were tested by field emission scanning electron microscopy (FE-SEM) and transmission electron microscope (TEM). Electrochemical evaluation. The electrochemical investigation of advanced electrodes was accomplished in a 3-electrode arrangement, with a Pt (counter) and an Ag/AgCl (reference) in 6 M KOH. To fabricate the working electrodes of HTS-CGOHS and GW@CFSHS, a sticky paste was produced via mixing HTS-CGOHS and/or GW@CFSHS with polyvinylidene fluoride and acetylene black in N-methyl pyrrolidone with a weight ratio of 85:5:10. This paste was covered onto the surface of BNF substrate with 1×1 cm2 efficient geometric surface area and dried at 80 oC

for 12 hours. Under the charge/discharge (CD) plots, the SpCa (Csc) of new electrode materials

were calculated by equation 1.

C sp 

It mV

(1)

Where m (g) is the weight of the HTS-CGOHS and/or GW@CFSHS materials on the BNF, ΔV (V) is the potential windows, Δt (s) and I (A) are the discharge time and current, respectively.


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Construction of the HTS-CGOHS//GW@CFSHS energy storage device. To test the practical application, the ESD device was fabricated using HTS-CGOHS, and GW@CFSHS electrodes as cathode and anode electrodes, respectively, in 6 M KOH with single cellulose paper as a separator. To approach the best performance, the optimal mass correlation between HTS-CGOHS and GW@CFSHS electrodes (m+/m−) acquired via charge balance theory (Q+=Q−) is around 0.71. Thus, the developed electrodes with 2.3 mg of HTS-CGOHS and 3.2 mg of GW@CFSHS were produced. Therefore, the total weight of the two electrode materials was 5.5 mg cm-2, based on the following equation:

m C   V  m C   V

(2)

The energy and power densities were obtained from the discharge plots by the equations 3 and 4:

ED  PD 

C sp  V 2 2 ED t

(3)

(4)

RESULTS AND DISCUSSION Characterizations of the HTS-CGOHS. To characterize the HTS-CGOHS sample, XRD test was conducted (Figure 1a). The XRD spectrum of HTS-CGOHS agrees with the cobalt gallium oxide patterns (JCPDS Card No.11-0698).47 The XPS study is one of the informational procedure useful in the examination of the composition of the diverse samples. The XPS survey illustrates the presence of cobalt (Co), gallium (Ga) and oxygen (O) elements in the HTS-CGOHS sample (Figure S1a, Supporting Information). The Co 2p XPS pattern of the HTS-CGOHS sample depicts two basic peaks at 780.35 eV and 795.71 eV with splitting space of 15.36 eV, illustrating the existence of Co2+ and Co3+.48 In the Ga 2p XPS spectrum, the presence of two major peaks at


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1117.65 and 1144.43 eV, with the splitting energy of 26.78 eV, describing the Ga 2p3/2 and Ga 2p1/2 respectively (Figure 1b).49 Furthermore, the Ga 3d XPS illustrates two peaks at 19.67 eV and 21.94 eV related to Ga 3d5/2 and Ga 3d3/2, respectively.50 The O1s XPS was separated into

h

200 nm

Figure. 1 (a) The XRD of HTS-CGOHS sample, (b) the Co 2p and Ga 2p XPS spectra of HTS-CGOHS sample, (c) the Ga 3d and O 1s XPS spectra of HTS-CGOHS sample, (d) the BET of HTS-CGOHS sample and its corresponding BJH curve (inset), (e and f) the FE-SEM images of HTS-CGOHS sample, and (g and h) the TEM images of HTSCGOHS sample.

three peaks marked as O1, O2, and O3 which can be attributed to metal–O bonds, OH groups and adsorbed H2O (Figure 1c).51 To further affirm the superiority of space pores and surface area, the HTS-CGOHS sample was characterized using Nitrogen adsorption/desorption (NAD) evaluation. The NAD isotherms of the HTS-CGOHS sample and its BJH plot (inset) represent a form of IV isotherm with a hysteresis loop, confirming nanoporosity of sample (Figure 1d). The SA of the HTS-CGOHS sample obtained by BET plot is 104.3 m2 g-1, which is significantly better than those of other


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TMOs.52,53 The nanoporous structure of the HTS-CGOHS sample was further clarified through the BJH method. The small pores with an average diameter of 2.7 nm belong to the pores on the shells, while the large pores with the mean size of 3.5 nm attribute to the empty rooms between the shells. The FE-SEM images of HTS-CGOHS sample shows that it has hollow microsphere structures, with roughness surface and numerous pores (Figure 1e and f). TEM images also confirm that the inner structure of the HTS-CGOHS sample has a porous triple-shelled structure (Figure 1g and h). To testify the porous structure of HTS-CGOHS sample, higher magnification TEM image of the HTS-CGOHS sample illustrates in Supporting Information (Figure S2). Having multi-shell structure can improve the electrochemical performance of the electrode because the spaces among the shells can serve as ion buffering reservoirs. Besides, the connection parts and the joints between shells can improve the structural stability of materials during electrochemical reactions. Formation of the triple-shelled structure. We first employ a straightforward way to construct the CoGa-BTC solid microsphere as explained in experimental section. The construction of the HTS-CGOHS sample is owing to heat treatment by the thermal decomposition of CoGa-BTC solid microspheres. The TEM images with a detailed schematic illustration of the microspheres throughout the heat treatment, from the CoGa-BTC solid microspheres to HTS-CGOHS sample, are indicated in (Figures 2a-d). The CoGa-BTC solid microspheres were fabricated by the bonding of Co and Ga metal ions with the BTC. The solid microsphere structure of the CoGa-BTC sample with a smooth surface and no pores was characterized by TEM (Figure 2a). After heating at 250 °C for two hours, there is a clear split between a solid core and well-defined shell, fabricating a core-shell structure (Figure 2b). By increasing the heating to 350 °C, the roughness of the surface and number of the pores on the surface of core-shell structure increases (Figure 2c). When the


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250 ℃

350 ℃

c

b

a

200 nm

500 ℃

200 nm

200 nm

d h

200 nm

Figure 2 (top): The schematic of the highly porous triple-shelled structure formation process, (bottom): (a) the TEM image of CoGa-BTC sample, (b) the TEM image of CoGa-BTC sample after calcination at 250 °C, (c) the TEM image of CoGa-BTC sample after calcination at 350 °C, (d) the TEM image of CoGa-BTC sample after calcination at 500 °C.

temperature of the reaction reaches to 500 °C, the reaction is completed, and triple-shelled is formed (Figure 2d). Characterizations of the GW@CFSHS. The general procedure for synthesizing GW@CFSHS is shown in scheme 1.

Scheme 1. The schematic illustration of GW@CFSHS formation


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After formation of CFSHS and GW@CFSHS, the crystal structure of the as-fabricated CFSHS and GW@CFSHS samples were demonstrated using XRD (Figure 3a). The CFSHS sample indicates diffraction peaks quite match with the CuFeS2 reported (JCPDS Card No. 411404).54 Also, a broad peak at 2θ of 25° in the GW@CFSHS XRD spectrum reveals the presence of graphene which causes a small change in the patterns of CFSHS due to the amorphous structure of graphene.55 The comprehensive electronic states of the GW@CFSHS sample were further explored through XPS (Figure 3b and c). The presence of carbon (C), iron (Fe) and sulfide (S) elements in GW@CFSHS sample is affirmed by the survey spectrum (Figure S1b, SI). The C 1s XPS plot of GW@CFSHS exhibits multiple peaks after deconvolution due to presence of C=O, O−C=O, C−O, and C–C (Figure 3b).56 Furthermore, the Cu 2p spectrum comprised of two considerable peaks at 933.95 and 954.05 eV correlating with Cu 2p3/2 and Cu 2p1/2, respectively (Figure 3b).57 The Fe 2p XPS patterns of the GW@CFSHS sample represents two important peaks at 710.82 and 724.12 eV which can be allocated as Fe 2p3/2 and Fe 2p1/2.58 Moreover, two basic peaks at 161.20 eV and 162.55 eV, which are correlated with S 2p3/2 and S 2p1/2, respectively, can be ascribed to the metal-S bonding and the existence of S2- in a low coordination state at the surface (Figure 3c).59 The surface area and pore distribution of the asfabricated in CFSHS and GW@CFSHS samples were studied via BET and BJH techniques. The CFSHS and GW@CFSHS samples have an appearance IV isotherm and hysteresis loops in the 0.5 to 1. As revealed via BET, the SA for GW@CFSHS is 68.3 m2 g−1 which is substantially higher than that of CFSHS (36.2 m2 g−1). Besides, the BJH plots show a pore size distribution centered at 7.2 nm for CFSHS, while the GW@CFSHS sample has more noticeable pores with larger size (Figure 3d). Improved SA and porosity in GW@CFSHS compared to those in CFSHS can be due to the presence of graphene nanosheets, and secondary pores formed between the CFSHS and


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e

f

500 nm

g

200 nm

h

500 nm

i

200 nm

j

200 nm

500 nm

Figure. 3 (a) The XRD spectra of CFSHS and GW@CFSHS samples, (b) the C 1s and Cu 2p XPS spectra of GW@CFSHS sample, (c) the Fe 2p and S 2p XPS spectra of GW@CFSHS sample, (d) the BET plots of CFSHS and GW@CFSHS samples and their BJH curves (inset), (e and f) the FE-SEM and TEM images of CFSHS before calcination, (g and h) the FE-SEM and TEM images of CFSHS after calcination, (i and j) the FE-SEM and TEM images of GW@CFSHS.


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coated graphene nanosheets. Additionally, the morphological study of the samples was investigated with FE-SEM and TEM. Before annealing, the structure of CFS shows uniform solid spheres and very smooth surface with no significant pores; while after annealing, the CSF sample exhibits a much rougher surface which might be due to the attachment of numerous small nanoparticles, and hollow spherical structure (Figure 3e-h). Moreover, the FE-SEM images of the GW@CFSHS sample indicates an excellent wrapping of CFSHS sample with graphene network (Figure 3i and j). This morphology can reduce the dissolution and protect the CFSHS from decomposition by the electrolyte. Moreover, it can increase both interfaces contact and surface area, which can enhance the electron transfer route. Electrochemical properties of HTS-CGOHS and GW@CFSHS. To evaluate the performance of HTS-CGOHS as cathode and GW@CFSHS as anode electrodes, all electrochemical experiments have been carried out in a 3-electrode system using a 6 M KOH solution as the electrolyte. The cyclic voltammetry (CV) measurements of bare nickel foam (BNF) and HTSCGOHS at various scan rates are shown in Figure 4a. The BNF substrate demonstrates a negligible current, indicating it does not assist in the performance of the electrode. The CV and CD plots of the polyvinylidene fluoride and acetylene black without active materials illustrates in Figure S3 (SI). Furthermore, redox peaks demonstrate the existence of faradaic redox reactions. The pair of redox peaks observed in CV of CoGa2O4 can mainly be attributed to the redox reactions related to Co–O/Co–O–OH probably associated and/or mediated by the OH− ions in the alkaline electrolyte.47 Thus, the pseudocapacitance comes from the faradic redox reaction of both Co and Ga, and Ga does not participate in any redox reaction. This is in good accordance with the previous reports about NiGa2O4 as electrode materials for supercapacitors.43 Moreover, no significant change in plots shape with increasing the scan rate not only reveals reversible faradaic redox


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reaction but also exhibit the remarkable capacitive behavior and charge collection. To get a better insight into the performance of the HTS-CGOHS electrode, the CD tests were examined at different current densities (Figure 4b). The nonlinear shape of CD plot confirms the pseudocapacitive behavior of HTS-CGOHS electrodes. The SpCas of HTS-CGOHS electrode estimated by CD plots are 1724.3 F g-1 (239.5 mAh g-1), 1656.2 F g-1 (230.0 mAh g-1), 1543.3 F g-1 (214.3 mAh g-1), 1312.1 F g-1 (182.2 mAh g-1), and 1198.4 F g-1 (166.4 mAh g-1) at current densities of 1, 2, 6, 12 and 24 A g-1, respectively. Therefore, the HTS-CGOHS electrode remained 69.5% of its SpCa after the current density was increased by a factor of 24 (from 1 to 24 A g-1), affirming excellent rate capability of as-fabricated nanomaterial (Figure 4c). The durability of HTS-CGOHS electrode also measured with 5000 consecutive charging and discharging cycles at a current density of 12 A g-1 (Figure 4d). The HTS-CGOHS electrode can deliver high stability with only 3.2% loss in SpCa, demonstrating the wonderful durableness of the HTS-CGOHS electrode. Besides, the EIS measurements of HTS-CGOHS electrode show only 0.14 Ω increase in semicircle diameter (Rct) after 5000 cycles, further confirming superior durability of the HTSCGOHS electrode (Figure 4d). To explore the electrochemical performance of the GW@CFSHS, CV, CD, and EIS tests were investigated. The CV plots of GW@CFSHS electrode at different scan rates ranging from 5 to 50 mV s−1 with the potential window of −1 to 0 V reveal a couple of symmetrical redox peaks, which demonstrate its complete electrochemical reversibility (Figure 4e). Besides, with the increasing of the scan rate, the CV plots indicate a small potential shift with shape retention even at high scan rates, demonstrating a satisfactory rate capability. One possible mechanism for electrochemical reaction of CuFeS2 in the presence of KOH can be as follows:60 𝐶𝑢𝐹𝑒𝑆2 + 3𝑂𝐻 ― ↔ 2𝐶𝑢𝑆2 + 𝐹𝑒𝑂𝑂𝐻 + 𝐻2𝑂 + 3𝑒 ―


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Furthermore, the CD plots of GW@CFSHS electrode at different current densities indicate symmetric characteristics which confirm the high coulombic efficiency of the electrode during continuous CD process (Figure 4f). Notably, as shown in Figure 4g the calculated SpCas from CD plots demonstrate remarkably higher capacitive behavior of GW@CFSHS electrode (621.2 F g−1 or 172.6 mAh g-1 at 1 A g−1) compared to the CFSHS electrode (403 F g−1 or 112.0 mAh g-1 at 1 A g-1). Moreover, with the increasing of current density up to 25 A g−1, the GW@CFSHS electrode can still achieve a superior capacitance retention of 58% (360.3 F g−1 or 100.1 mAh g-1) in comparison with 49% (197.5 F g−1 or 54.9 mAh g-1) for the CFSHS electrode, which manifests the satisfactory rate capability of the GW@CFSHS electrode. Also, EIS tests were performed to get a

Figure. 4 (a) The CVs of BNF substrate at 50 mV s-1 and HTS-CGOHS electrode at diverse scan rates, (b) the CDs of HTS-CGOHS electrode at different current densities, (c) Rate capability of HTS-CGOHS electrode, (d) Durability test of the HTS-CGOHS electrode and Nyquist plots of the HTS-CGOHS electrode before and after cycling, (e) the CVs of GW@CFSHS electrode at various scan rates, (f) the CDs of GW@CFSHS electrode at diverse current densities, (g) Rate capability of CFSHS and GW@CFSHS electrodes, (h) Durability tests of the CFSHS and GW@CFSHS electrodes and Nyquist plots of the CFSHS and GW@CFSHS electrodes.


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better insight into the electrochemical properties of the CFSHS and GW@CFSHS electrodes (Figure 4h). The Rct of the GW@CFSHS electrode is smaller than the CFSHS electrode, indicating the GW@CFSHS electrode demonstrates faster kinetics than the CFSHS electrode. Additionally, applying 5000 cycles within a voltage range from -1 to 0 V at a current density of 9 A g-1 shows only 12.5% decay in the SpCa of GW@CFSHS electrode, which is superior to that of CFSHS electrode with 23% loss (Figure 4h).

Fabrication of HTS-CGOHS//GW@CFSHS ESD. To investigate the practical application of the as-constructed HTS-CGOHS and GW@CFSHS electrodes, an energy storage device was fabricated by assembling HTS-CGOHS and GW@CFSHS electrodes as the cathode and anode, respectively. After charge balancing, the potential windows of the GW@CFSHS and HTSCGOHS electrodes found −1 to 0 and 0 to 0.50 V, respectively, based on the CV plots at 50 mV s−1 (Figure 5a). Thus, the potential window of the HTS-CGOHS//GW@CFSHS ESD can be as high as 1.50 V in 6 M KOH electrolyte. The GW@CFSHS and HTS-CGOHS electrodes have pseudocapacitance CV plots. The CV plots of the HTS-CGOHS//GW@CFSHS ESD taken at different scan rates ranging from 5 to 100 mV s−1 with the operational potential windows from 0 to 1.50 V, represent a pair of redox peaks ascribing to the reversible electrochemical reactions (Figure 5b). Besides, the CV plots with shape retention at all scan rates demonstrate a wonderful rate performance as a result of the electronic and ionic transmission in the electrodes. The CD plots of the HTS-CGOHS//GW@CFSHS ESD at diverse current densities of 1–24 A g−1 reveal the approximately symmetric charge/discharge specifications which indicate excellent coulombic efficiency (Figure 5c). Also, voltage plateaus of the CD plots prove the capacitance properties arise from the pseudocapacitive behaviors of the HTS-CGOHS and GW@CFSHS electrodes, which is in agreement with CV studies. In Figure 5d, The SpCas of the HTS-


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CGOHS//GW@CFSHS ESD calculated by the CD plots are indicated as a function of the current density. As shown the as-fabricated ESD delivers a SpCa as high as 367.4 F g−1 (153.8 mAh g-1) at 1 A g−1, and it only decreases to 238.8 F g−1 (99.5 mAh g-1) even at 24 A g−1, offering an outstanding capability for the device. The reducing in SpCa at high current densities can be due to inadequate redox reactions as a consequence of slow ion diffusion. The long-term stability and durability of the ESD device was also examined through a degradation experiment carried out at the current density of 6 A g-1, which shows 93.7% retention in SpCa after 5000 cycles (Figure 5e).

Figure. 5 (a) The CV plots of GW@CFSHS and HTS-CGOHS electrodes in 3-electrode system at scan rate 50 mV s-1, (b) the CV plots of HTS-CGOHS//GW@CFSHS at diverse scan rates, (c) the CD plots of HTSCGOHS//GW@CFSHS at different current densities, (d) Rate capability of HTS-CGOHS//GW@CFSHS, (e) Durability test of the HTS-CGOHS//GW@CFSHS, (f) the comparison between Ragone plot of

HTS-

CGOHS//GW@CFSHS device with several previous devices.

To illustrate the overall performance of the HTS-CGOHS//GW@CFSHS device, a Ragone plot indicating the ENDE and PODE at different current densities reveals a maximum ENDE of 114.8


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W h kg-1 at a PODE of 750.4 W kg−1 (Figure. 5f). The obtained ENDE is higher than previously reported devices such as CoNi2S4//CNTs@Fe2O3@C (90.5 Wh kg-1 at 1840W kg-1),61, NiCo2O4//MoO2-C (41.8 Wh kg-1 at 19922.2W kg-1),62 LaMnO3/RGO/PANI//RGO (50 Wh kg-1 at 2250W kg-1),63 BFO-RGO//BFO-RGO (18.62 Wh kg-1 at 750W kg-1),64 S0.5-6h-EW//AC (58.7 Wh kg-1 at 532 W kg-1),65 ZnO/Co3O4//AC (47.7 Wh kg-1 at 7500W kg-1)66. To highlight the performance of the HTS-CGOHS electrodes in 3- and 2-electrode cells, a comparison with the previously reported electrodes are shown in Table S1 (Supporting Information).

The excellent performance of the HTS-CGOHS//GW@CFSHS ESD can be due to (i) spinel CoGa2O4 has richer electrochemical redox reaction than that of single metal oxide, in cathode electrode; (ii) The hollow structures not only provide high surface area but also facilitate the transport of electrolyte through the entire structure owing to penetration of the ion into the inner surface and proceeding as ion-buffering reservoirs; (iii) The shells increase kinetics by decreasing the diffusion length path; (iv) The graphene sheets reduce metal ion dissolution during the charge-discharge process, thereby hindering the degradation of the CFSHS which causes a long cycle life. Finally, a green light emitting diode (LED) was lighten up by two HTSCGOHS//GW@CFSHS ESD connected in series (inset of Figure 5f). These results can show the practical application of the HTS-CGOHS//GW@CFSHS ESD as high energy density storage system.

CONCLUSION In summary, we fabricated an energy storage device by employing highly porous tripleshelled cobalt gallium oxide (CoGa2O4) hollow spheres (HTS-CGOHS) as a cathode, and graphene wrapped CuFeS2 hollow spheres (GW@CFSHS) as an anode electrode, through a simple


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strategy. The HTS-CGOHS cathode illustrates incredible performance including low internal resistance, reversibility, SpCa of 1724.3 F g-1 (239.5 mAh g-1), rate capability of 69.5% at 24 A g-1, and significant durableness. The GW@CFSHS anode reveals SpCa of 621.20 F g-1 (172.6 mAh g-1), superior durableness and rate capability of 58% at 25 A g-1. More importantly, an ESD (HTS-CGOHS//GW@CFSHS) was constructed with substantial performance, superior ENDE of 114.8 W h kg−1 at 750.4 W kg−1, and wonderful durability. This work not only suggests a favorable strategy for designing the advanced electrode materials for supercapacitors but also confirms the potential application of the device that opens a new approach for fabricating the next-generation of energy storage devices.

Supporting Information: Supplementary characterization and electrochemical data, and a benchmark table to compare the performance of the as-prepared device with previously reported studies are presented in supporting information.

Notes The authors declare no competing financial interest.

Acknowledgment The authors gratefully acknowledge the support of this work by Research councils of Shahid Beheshti University.

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(62) Li, Y.; Tang, F.; Wang, R.; Wang, C.; Liu, J. A Novel Dual-Ion Hybrid Supercapacitor Based on NiCo2O4 Nanowire Cathode and MoO2-C Nanofilm Anode. ACS Appl Mater Interfaces 2016, 8, 30232–30238, DOI: 10.1021/acsami.6b10249. (63) Shafi, P. M.; Ganesh, V.; Bose, A. C. LaMnO3/RGO/PANI Ternary nanocomposite for Supercapacitor Electrode Application and Their Outstanding Performance in All-Solid-State Asymmetrical Device Design. ACS Appl. Energy Mater. 2018, 1, 2802–2812, DOI: 10.1021/acsaem.8b00459. (64) Moitra, D.; Anand, C.; Ghosh, B. K.; Chandel, M.; Ghosh, N. N. One-Dimensional BiFeO3 Nanowire-Reduced Graphene Oxide Nanocomposite as Excellent Supercapacitor Electrode Material. ACS Appl. Energy Mater. 2018, 1, 464–474, DOI: 10.1021/acsaem.7b00097. (65) Dan, H.; Tao, K.; Zhou, Q.; Gong, Y.; Lin, J. Ni-doped cobalt phosphite, Co11(HPO3)8(OH)6 with different morphologies grown on Ni foam hydro(solvo)thermally for high performance supercapacitor.

ACS

Appl.

Mater.

Interfaces

2018,

10,

31340–31354,

DOI:

10.1021/acsami.8b09836. (66) Gao, M.; Wang, W.-K.; Rong, Q.; Jiang, J.; Zhang, Y.-J.; Yu, H.-Q. Porous ZnO-Coated Co3O4 Nanorod as a High-Energy-Density Supercapacitor Material. ACS Appl. Mater. Interfaces 2018, 10, 23163–23173, DOI: 10.1021/acsami.8b07082.


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TOC

This work introduces a high-performance energy storage device composed of triple-shelled CoGa2O4 hollow spheres as a cathode, and graphene wrapped CuFeS2 hollow spheres as an anode.


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A High-Performance Energy Storage Device Based on Triple-shelled

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