Quasi 2D Mesoporous Carbon Microbelts Derived from Fullerene

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Quasi 2D mesoporous carbon microbelts derived from fullerene crystals as an electrode material for electrochemical supercapacitors Qin Tang, Partha Bairi, Rekha Goswami Shrestha, Jonathan P Hill, Katsuhiko Ariga, Haibo Zeng, Qingmin Ji, and Lok Kumar Shrestha ACS Appl. Mater. Interfaces, Just Accepted Manuscript • DOI: 10.1021/acsami.7b13277 • Publication Date (Web): 06 Dec 2017 Downloaded from http://pubs.acs.org on December 6, 2017

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ACS Applied Materials & Interfaces

Quasi 2D mesoporous carbon microbelts derived from fullerene crystals as an electrode material for electrochemical supercapacitors Qin Tang,† Partha Bairi, ‡ Rekha Goswami Shrestha, ‡ Jonathan P. Hill, ‡ Katsuhiko Ariga‡‖ Haibo Zeng, ♯ Qingmin Ji*†♯ and Lok Kumar Shrestha*‡ †

.Herbert Gleiter Institute of Nanoscience, Nanjing University of Science & Technology, 200

Xiaolingwei, Nanjing 210094, China. ‡

.Supermolecules Group, International Center for Materials Nanoarchitectonics (WPI-MANA),

National Institute for Materials Science (NIMS), 1-1 Namiki, Tsukuba, Ibaraki 305-0044, Japan. ‖

. Department of Advanced Materials Science, Graduate School of Frontier Sciences, The

University of Tokyo, 5-1-5 Kashiwanoha, Kashiwa, Chiba 277-8561, Japan. ♯

.MIIT Key Laboratory of Advanced Display Materials and Devices, Nanjing University of

Science and Technology, Nanjing, 210094, China

ACS Paragon Plus Environment

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ABSTRACT: Fullerene C60 microbelts were fabricated using liquid-liquid interfacial precipitation method and converted into quasi 2D mesoporous carbon microbelts by heat-treatment at elevated temperatures of 900 and 2000 C. The carbon microbelts obtained by heat-treatment of fullerene C60 microbelts at 900 C showed excellent electrochemical supercapacitive performance exhibiting high specific capacitances ca. 360 F g–1 (at 5 mV s–1) and 290 F g–1 (at 1 A g–1) due to the enhanced surface area and robust mesoporous framework structure. Additionally, the heattreated carbon microbelt showed good rate performance retaining 49% of capacitance at the high scan rate of 10 A g–1. The carbon belts exhibit super cyclic stability. Capacity loss was not observed even after 10,000 charge/discharge cycles. These results demonstrate that the quasi 2D mesoporous carbon microbelts derived from π-electron rich carbon source, fullerene C60 crystals could be used as a new candidate material for electrochemical supercapacitor applications.

KEYWORDS: fullerene, microbelts, liquid-liquid interfacial precipitation (LLIP), heattreatment, supercapacitors


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INTRODUCTION Due to the increasing demands and dependence of current modern society on the portable energy storage devices, searching for the new and better supercapacitor or electrochemical double-layer capacitor (EDLCs) materials for the applications in electrochemical energy storage devices has received significant attention. EDLCs are advantageous due to their high energy storage capacity, long cycle life, safety and environmental friendliness.1-5 However, the performances of supercapacitors generally suffer from a limited energy density (about 5 Wh kg−1) compared to batteries (> 50 Wh kg−1).6-8 Since the overall performances of supercapacitors (based on their specific capacitance, rate capability, cycle life and charge storage) ultimately depend on the type of electrode materials,9, 10 development of novel materials for this application is an essential aspect in the improvement of the performances of supercapacitor devices.11-13 Of the various available electrode materials, carbon-based nanomaterials lie on the top, which have been broadly investigated and used in EDLCs.14-17 The commonly used carbon-based materials include conventional activated carbons, mesoporous carbons spheres, carbon-based composites, carbon aerogels and graphene.18-21 Recently, advances in the area of the 2D carbon material graphene has revealed that its energy density can approach the level of batteries due to its high surface area, good conductivity, ultralight mass and strong mechanical property.22-30 However, due to strong π-π interactions graphene tend to aggregate or self-restack during the electrode preparation, as a result there is a substantial loss of active surface area and decrease in the performance of the materials or the devices.31-33 To alleviate this problem, 3D graphene nanomaterials are being developed, in which continuous interconnected porous framework structures may prevent the self-restacking of graphene thus increasing device performances.34-37


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Mesoporous/microporous carbons are widely used as electrode materials in commercial supercapacitor devices. Therefore, extensive efforts have been made to obtain suitable porous carbon framework structures to improve the specific capacitances and energy densities of the supercapacitors. Extensive investigations have been carried out for the production of high quality carbons in terms of high surface areas and large pore volumes using hard- and soft-templating methods. However, these methods require additional procedures for the removal of templates making them unsuitable for scale-up due to substantial and expensive material losses.38-42 Therefore, alternative more simple and convenient methods would be more attractive for the synthesis of porous carbon nanomaterials having effective porosities, surface areas and high electrical conductivities advantageous for supercapacitor applications. Fullerene (C60), a truncated icosahedron (Ih) containing carbon atoms located at the nodes of hexagons (20) and pentagons (12) arranged in a cage lattice (with size of ~ 0.8 nm), is a πconjugated molecule and can be considered an essentially zero-dimensional (0D) nanocarbon.43-45 Contrary to other nanocarbons including 1D carbon nanotubes (CNT) and 2D graphene, fullerene C60 functions as an unique building block and undergoes supramolecular self-assembly into various nanostructures in the bulk or at interfaces. For example, fullerenes have been selfassembled into dimensionally integrated nanostructures, including 0D spheroids, 1D nanorods and nanotubes, 2D nanosheets and nanodisks, and 3D nanocubes through mutual π-π stacking interactions using simple liquid-liquid interfacial precipitation (LLIP) method.46-50 Recent studies have shown that these dimensionally-controlled fullerene crystals serve as an unique π-electron rich carbon source that can be directly converted into highly graphitic mesoporous carbons with robust frameworks.43,44 The resulting novel porous carbon materials are advantageous for energy storage applications due to their enhanced surface areas and the extended conjugated π-systems.


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Herein, we report the first example of supramolecular assembly of fullerene C60 into high aspect ratio quasi-2D microbelts at a liquid-liquid interface between the carbon disulfide (CS2) solution of C60 and isopropyl alcohol (IPA) at ambient temperature. The length of the fullerene C60 microbelts (FMBs) could be controlled according to the synthetic conditions. Under certain conditions, centimeter long FMBs could be produced. Although the liquid-liquid interfacial precipitation (LLIP) method is a well-developed method for the controlled fabrication of fullerene crystals,51-53 centimeter length scale 2D nanostructure of C60 had not previously been observed. In contrast to 1D assembly (nanorod or nanotube),54 the quasi 2D structure (microbelt) is expected to possess excellent mechanical stability, flexibility, transparency and chemical stability.8,55-57 FMBs were converted into mesoporous carbon microbelts (MCMBs) possessing an amorphous or graphitic framework structure by carbonization at 900 or 2000 C (Scheme 1).

Scheme. 1 Schematic representation of the fabrication of fullerene microbelt (FMB) crystals at a liquid-liquid interface and its conversion into mesoporous carbon microbelts (MCMB) during heat-treatment at elevated temperatures. The resulting mesoporous carbon microbelts (FMB_900) exhibited high specific capacitances ca. 360 F g–1 (at 5 mV s–1) and 290 F g–1 (at 1 A g–1). A high rate performance retaining about 49% of capacitance at scan rate of 10 A g–1 together with outstanding cyclic stability without losing any capacitance even after 10,000 charging/discharging cycles indicate that the MCMBs derived from


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π-electron rich carbon source fullerene C60 could be used as a new candidate material for advanced electrochemical supercapacitors.

EXPERIMENT METHODS Synthesis of fullerene C60 microbelts (FMBs). Fullerene C60 microbelts (FMBs) were synthesized using the static liquid-liquid interfacial precipitation (LLIP) method. As received pristine C60 (80 mg: 99.5 % pure, MTR Ltd., USA) was dissolved in carbon disulfide (CS2: 40 mL) by ultrasonication for 1 h. The stock solution (2 mg mL–1) was stored at 25 C. In a typical synthesis of fullerene crystals, isopropyl alcohol (IPA: 3 mL) stored separately at 25 C was added slowly to CS2 solution of C60s (2 mg mL–1, 1 mL) in a clean and dry glass bottle. The mixture solution was then incubated at 25 C for 24 h to fully grow the FMBs. The resulting FMBs were washed three times with IPA. In order to control the aspect ratio of FMBs, crystals were grown with different initial volumes of C60 solution (0.5, 1, 2 and 3 mL) keeping the mixing volume ratios of C60 solution and IPA at 1:3.

Synthesis of mesoporous carbon microbelts (MCMB). FMBs were heated at 900 or 2000 C for the conversion into mesoporous carbon microbelts (MCMBs). Heat-treatment at 900 C was carried out in a tubular furnace (KOYO, Tokyo Japan) under a constant flow of nitrogen gas (120 cc min–1) at a heating speed of 5 C min–1. FMBs were heated for 1 h at 900 C. This product is referred to as FMB_900. Heat-treatment at 2000 C was carried out in vacuum (7 × 10−3 Pa) using furnace FTR-20-3VH (Fujidempa Kogyo Co., Ltd, Osaka, Japan) and the obtained product is referred to as FMB_2000.


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Characterizations Surface morphology of FMB and MCMBs were studied by scanning electron microscopy (Hitachi Model S-4800) operating at 10 kV and 10 µA. The samples were spread on the surface of the cutted pieces of silicon wafer and dried under vacuum at 80 C for 6 h before SEM observation. All SEM samples were platinum coated (approx. 2 nm) by Hitachi S-2030 ion coater to avoid charging during imaging. Transmission electron microscopy (TEM) observation and selected area electron diffraction patterns (SAED) analysis is taken by JEOL Model JEM-2100F, and operated at voltage 200 kV. For the preparation of the TEM samples, a small drop of the dilute suspension of FMBs and MCMBs in IPA was placed onto a carbon-coated copper microgrid (NISSIN EM Co. Ltd. Tokyo, Japan). After dried at room temperature, the TEM samples were further dried under the reduced pressure at 80 C for 12 h before the TEM observations. 3D Laser Scanning Microscope (Keyence, model VK-X200) was used to perform surface profile measurements and to evaluate the thickness of carbon microbelts. FT-IR spectra were taken on Nicolet 4700 FT-IR spectrophotometer. The powder X-ray diffraction (pXRD) patterns were measured by Rigaku RINT2000 diffractometer with Cu-Kα radiation (λ = 0.1541 nm) at 25 C. Raman spectra were taken on the Raman spectrometer of Jobin-Yvon T64000 using an excitation wavelength of 514.5 nm and under 0.01 mW power. X-ray photoelectron spectroscopy (XPS) survey spectra and XPS core level C 1s, O 1s and S 2p were measured on a Theta Probe spectrometer (Thermo Electron Co., Germany) using monochromatic Al-Kα radiation (photon energy: 15 keV, maximum energy resolution: 0.47 eV). Thermogravimetry (TG) analysis was recorded by SII Instrument (Model Exstar 600) in the temperature ranging from 25 to 400 oC with the heating rate of 10 C min−1 under an inert atmosphere of argon. The specific surface areas and pore size distributions were


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analyzed based on the nitrogen adsorption–desorption isotherms, which were measured by Quantachrome Instruments, (Autosorb-iQ2, USA).

Cyclic voltammetry (CV) and chronopotentiometry Using

cyclic

voltammetry

(CV)

and

chronopotentiometry

(charge/discharge

(CD))

electrochemical supercapacitive performances were studied in an aqueous H2SO4 electrolyte (1 M) at 25 C by using a three-electrode system. For the preparation of working electrodes modified with FMB or MCMBs, first FMB, FMB-900 and FMB_2000 were dispersed in water-ethanol mixtures (4:1 v/v) by adding 1 mg of each in 1 mL of water-ethanol solution. The dispersion (5 μL) was then drop-casted on the glassy carbon electrode and dried in over at 60 ºC for 1h. Nafion solution (in ethanol: 0.5 % w/v, 5 μL) was added on top of the dried FMB-modified electrode as a binder and further dried at 60 ºC for 12 h. CV and CD curves were recorded on ALS/CH Model 850D Electrochemical Analyzer in the potential range of 0 to 0.8 V (vs. Ag/AgCl). From CV data, specific capacitances (Cs) of the electrode material were calculated from equation (1): ∫ 𝐼𝑑𝑉

𝐶𝑠 = 𝑚𝑆∆𝑉………………………… (1) where I (A), S (mV s−1), ΔV (V) and m (g) represents current, scan rate, operating potential window, and mass of the active electrode material, respectively. Cs was also estimated by galvanostatic charge-discharge plots based on the equation (2): 𝐼×𝑡

𝐶𝑠 = 𝑚×∆𝑉………………………... (2) where I (A) and t (s) represents the discharge current, and the discharge time, respectively. ΔV (V) and m (g) represents the potential difference during the discharge process and the mass of the active electrode material, respectively.


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RESULTS AND DISCUSSION Using the static LLIP method, we have fabricated fullerene C60 microbelts (FMBs) at 25 ºC. With the slowly and carefully addition of IPA (3 mL) on the top of CS2 solution of C60s (2 mg mL–1: 1 mL), a clear interface between C60 solution and IPA was formed and C60 crystals began growth at this interface. The resulting mixture was then placed in an incubator at 25 C for 24 h avoiding mechanical disturbances. Fully grown FMBs were observed by polarized optical microscopy (POM, Figure 1a and b). A photograph of FMBs in a glass bottle after 24 h incubation is shown in Figure 1c. Dimensions of FMBs could be relatively easily controlled by varying the volume of C60 solution in CS2 keeping the volume ratio of C60/CS2 solution and IPA fixed at 1:3. This indicated that the growth of FMBs depends on the initial volume of C60/CS2 solution (Figure S1): larger volumes of C60 solution result in the formation of longer FMBs. The relatively narrow distribution of length also implies that FMBs are grown from the interface and in the direction of IPA penetration into the CS2 solution (Figure S2). Average lengths and widths of the FMB are ca.172 µm and 26 µm, respectively. SEM images clearly reveal the flatness of the surfaces of FMB (Figure 1d, 1e and S3). Observations made using 3D laser scanning microscopy indicate the nonuniformity in thickness of FMBs with it being in range 0.2 µm – 2 µm (Figure S4).


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Figure. 1 (a) and (b) Polarized optical microscopic images of FMB, (c) digital image of as prepared FMB in a glass bottle, (d and e) SEM images of FMB, (f and g) SEM images of FMB_900 and (h and i) SEM images of FMB_2000.

Although the original belt-like morphology was essentially retained after high temperature heattreatment at 900 or 2000 C (Figure 1f, 1h, S5 and S6), both surface roughness and porosity increased in the FMB_900 and FMB_2000 samples. High temperature heat-treatment causes the release of CS2 solvent from the solvated FMB and also breaks the chemical structure of the fullerene molecules. As a result, porous amorphous or graphitic carbon materials depending on the heat-treatment temperature is formed. A strong absorption peak observed at 1520 cm–1 in the FTIR spectrum of FMB corresponds to the S=C=S asymmetric stretching band, which indicates the presence of CS2 in the crystalline FMBs (Figure S7). XPS measurements further confirmed the


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presence of CS2 in FMBs (Figure S8). The quantity of CS2 in FMB was estimated to be 6 wt% (Figure S9). TEM images reveal the non-porous structure of FMBs before heat-treatment (Figure 2a, 2b and S10b). They are highly crystalline materials as revealed by HR-TEM (Figure 2b, S10c and S10d). Clear extended lattice fringes of the packed C60 can be observed in HR-TEM, indicating the crystalline nature of FMB (Figure 2b and S10d). The calculated lattice spacing of 0.447 ± 0.002 nm can be assigned to the (022) plane of the monoclinic structure of FMB. In contrast, both the FMB_900 (Figure 2c) and FMB_2000 (Figure 2e); the heat-treated samples, have irregular edges, rough surfaces and porous structures. HR-TEM images confirmed that heat-treatment at 900 C causes the conversion of FMBs into an amorphous carbon structure (Figure 2d and S11f). While 2000 C heat-treatment of FMB causes the development of a graphitic structure with dense packing of graphene layers (Figure 2f, S12e and S12f).


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Figure. 2 (a) TEM and (b) HR-TEM images of FMB, (c) TEM and (d) HR-TEM images of FMB_900, (e) TEM and (f) HR-TEM images FMB_2000. Inset of panels (b), (d) and (f) shows SAED pattern of FMB, FMB_900, and FMB_2000, respectively.

Surface textural properties (surface area and pore volume) of the FMB before and after heattreatments (FMB_900 and FMB_2000) were studied by nitrogen sorption measurements. Nitrogen sorption isotherms of FMB_900 and FMB_2000 display Type IV behaviour with an H3 hysteresis loop, indicating the presence of a mesoporous structure (Figure S13). A steep nitrogen adsorption at lower relative pressure suggests a microporous structure for FMB_900 and FMB_2000, i.e., these samples exhibit bimodal micro- and mesoporous structures. The pore size distribution curves (obtained by Barrett-Joyner-Halenda (BJH) and density functional theory (DFT)) further confirm the presence of micropores and mesopores in the heat-treated samples (Figure S13b and S13c). For FMB_2000, the pore size distribution is much narrower and centered around 2 nm indicating


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the shrinkage of pores caused by the higher temperature treatment at 2000 C. The Brunauer– Emmett–Teller (BET) surface area of FMB_900 ca. 980 m2 g–1 which is much higher than that of FMB (ca. 106 m2 g–1) and FMB_2000 (ca. 297 m2 g–1). Similarly, the total pore volume of FMB_900 ca. 2.09 cc m2 g–1 is larger than that of FMB_2000 (ca. 0.46 cc g–1). The relatively poor surface area and pore volume of FMB_2000 can be attributed to the formation of dense graphitic structures caused by the high temperature heat-treatment. Generally, C60 molecules prefer stacking along the [100] direction and are inclined to form a tightly packed 1D chain due to strong π-π interactions. However, the cage-like structures may form at the periphery of 1D chains in the presence of CS2, which may cause rigidifying of these 1D structures and the formation of primary 2D plates.54 Structural details of FMBs and FMB_900 and FMB_2000 were studied by powder XRD, Raman scattering and XPS. XRD pattern of pristine C60 shows diffraction peaks at 2θ = 10.78o, 17.64o, 20.74o, 21.68o, 27.34o, 28.10o, 30.86o and 32.78o, corresponding respectively to (111), (022), (113), (222), (133), (024), (224) and (333) planes (Figure 3a). The lattice parameter is calculated to be a = 1.4206 nm with V = 2.867 nm3, which is assigned to the face-centered cubic (fcc). structure.58,59 X-ray powder diffraction patterns confirm that FMBs are of mixed fcc and monoclinic crystal phase. The XRD powder pattern of FMB heat-treated at 900

o

C (FMB_900) shows a broad peak at 24o with two additional low

intensity peaks corresponding to (024) and (333) planes of FMB crystals indicating amorphous and partial crystalline structure. This indicates that C60 molecules are not completely converted into amorphous carbon upon heating at 900

o

C for 1h. Observed broad diffraction peaks of

FMB_2000 centered at 24.46o and 44.46o (Figure 3a) can be assigned to the (002) and (101) planes corresponding to the graphitic carbon. The (101) plane in FMB_2000 is strong evidence of weak interlayer ordering of the graphene layers.


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Raman spectra of pC60 and FMB contain eight vibration bands corresponding to two Ag and six Hg bands (Figure 3b).60,61 Raman bands at 495.5 (Ag(1): breathing mode) and 1464 cm–1 (Ag(2): pentagonal pinch mode correspond to the Raman scattering spectrum of the C60 molecule.62 Raman bands as highlighted by arrows at 271, 431, 709.5, 771.5, 1421 and 1566.5 cm–1 correspond to the six vibration modes: Hg(1), Hg(2), Hg(3), Hg(4), Hg(7), and Hg(8), respectively. Raman peaks corresponding to C60 are not present in the FMB_900 and FMB_2000 samples. Rather, two strong bands appeared at 1335 cm–1 (D) and 1582 cm–1 (G) are commonly observed in carbon materials. The sharper D band and clear 2D band (at 2672 cm–1) found in FMB_2000 implies that the presence of locally crystalline graphitic carbon, while FMB_900 has a more disordered structure.63

Figure. 3 (a) Powder XRD patterns and (b) Raman scattering spectra of pC60, FMB, FMB_900 and FMB_2000. (111) plane of (fcc) structure is marked with *.

XPS survey spectra (Figure 4a) reveal the presence of carbon (C 1s) and oxygen (O 1s) indicating that the surface of the pC60 is oxidized. Although the relative intensity of O 1s peak in FMB and pC60 is comparable, it is weaker in FMB_900 and FMB_2000 samples (Figure 4a). It should be noted that due to the presence of oxygen the intrinsic conductivity of pC60 and as prepared FMBs


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decreases.64,65 Deconvoluted XPS C 1s peaks for pC60, FMB, FMB_900 and FMB_2000 samples confirm the C–C (sp3), C=C (sp2) and O–C=O or C–O bonding states (Figure 4b). Corresponding XPS O 1s core level spectra with deconvoluted peaks for all the samples are shown in Figure 4c.

Figure. 4 (a) XPS survey spectra of pC60, FMB, FMB_900 and FMB_2000, (b) XPS C 1s core level spectra of pC60, FMB, FMB_900 and FMB_2000 with deconvoluted peaks, and (c) the corresponding XPS O 1s core level spectra with deconvoluted peaks.

Figure 5 and S14 show the electrochemical supercapacitive properties of FMB, FMB_900 and FMB_2000. In Figure 5a current density of FMB, FMB_900 and FMB_2000 are compared at a fixed scan rate of 5 mV s–1. As it can be seen, FMB_900 exhibits higher current density than FMB and FMB_2000, indicating the potentially higher energy storage capacity of FMB_900. CV curves of FMB_900 (Figure 5b) display quick current response and exhibit have rectangular shape even at very high scan rates, both of which are the typical features of EDLCs. Note that CV curves


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deviate slightly from the ideal rectangular shape particularly at higher scan rates. This deviation can be attributed to the obstructed diffusion of electrolyte ions in the microbelts. Using Eq. 1 specific capacitances of FMB, FMB_900 and FMB_200 were calculated. It was found that the specific capacitance of FMB_900 (ca. 360 F g–1 at 5 mV s–1) is approximately 9.4 and 5.8 times higher than that of the FMB (38.4 F g–1) and FMB_2000 (61.4 F g–1), respectively. Moreover, due to better surface textural properties (surface area (980 m2 g–1) and large pore volume (2.09 cc g– 1

)) FMB_900 retains high specific capacitance at high scan rates. Approximately 42% capacitance

was sustained at 500 mV s–1.

Figure. 5 (a) CV curves of FMB, FMB_900 and FMB_2000 at a scan rate of 5 mV s–1, (b) CV curves of FMB_900 at different scan rates (5 – 500 mV s–1) as typical example of EDLC, (c) specific capacitance vs. scan rates from CV curves for FMB, FMB_900 and FMB_2000, (d) CD curves for FMB_900 at different current densities (1 – 10 A g–1) as typical example, (e) comparison of specific capacitance obtained from CD curves for FMB, FMB_900 and FMB_2000 and (f) cyclic stability curves up to 10,000 charge/discharge cycles.


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Electrochemical performances of FMB, FMB_900 and FMB_2000 modified electrodes were also tested by chronopotentiometry recording galvanostatic charge-discharge (CD) curves (Figure 5d, Figure S14c and Figure S14d). The typically quasi-triangular shaped CD curves of FMB_900 further confirm its characteristic EDLC behaviour (Figure 5d). Similar CD curves were obtained for FMB and FMB_2000 (Figure S14). Specific capacitance of FMB_900 is ca. 290 F g–1 at current density of 1 A g–1. Good rate capability of FMB_900 can be judged from the obtained 48.8% capacitance retention at high current density of 10 A g–1. To investigate the cycle life of the electrode, cyclic stability test of the FMB_900 electrode was performed over 10,000 charge/discharge cycles at 10 A g–1. Positive cyclic stability is observed after 10,000 cycles (Figure 5f), which can be attributed to further activation of intercalation or de-intercalation of electrochemical species during the charging/discharging cycles.66 Overall, our novel bimodal porous FMB_900 carbon material derived from a crystalline πelectron rich carbon source, fullerene crystals, by high temperature heat-treatment, exhibits excellent electrochemical supercapacitive performance including a higher specific capacitance than pure graphene,67,68 conventional mesoporous carbon and other similar carbon materials.69,70 The observed superior supercapacitive performance of FMB_900 compared to FMB and FMB_2000 can be ascribed to the high surface area and large pore volume of the mesoporous carbon microbelts, and quasi 2D structure which may reduce the efficient diffusion path. 71,72 Moreover, the quasi 2D microbelt morphology with large pore volume may enhance charge transport in supercapacitor electrodes. Thus, we believe that this novel quasi 2D mesoporous carbon microbelts derived from fullerene crystals could be a potential material in energy storage applications.


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CONCLUSIONS In conclusion, we have prepared unusually long quasi two-dimensional (2D) crystalline fullerene C60 microbelts (FMBs) using the static liquid-liquid interfacial precipitation (LLIP) method under ambient temperature and pressure. These π-electron rich FMBs were then converted into mesoporous carbon microbelts by high temperature heat-treatments at 900 and 2000 oC. Depending on the heat-treatment temperature, FMBs were converted into amorphous carbon (900 o

C) or dense graphitic carbon (2000 oC) structures. The microbelts heat-treated at 900 oC

(FMB_900) showed excellent electrochemical supercapacitive performance due to their enhanced surface area, pore volume and mesoporous frameworks. High specific capacitance of 360 F g–1 and 290 F g–1 was found at 5 mV s–1 and 1 A g–1, respectively. Furthermore, FMB_900 showed high rate capability essential for supercapacitor devices retaining about 49% of capacitance at the high scan rate of 10 A g–1, together with excellent cyclic stability without any capacitance loss after 10,000 charge/discharge cycles. The carbon microbelts allow efficient storage and rapid ions transport throughout the carbonaceous matrix due to their hierarchical bimodal pore structures. These results indicate that the quasi 2D mesoporous carbon microbelts derived from π-electron rich fullerene C60 crystals could be an efficient material to be used in electrochemical supercapacitor applications. Fullerene microbelts and the mesoporous carbons derived from them may also bring new insights for the development of fullerene superstructures in energy storage and related applications.

ASSOCIATED CONTENT Supporting Information


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Additional polarizing optical images, additional SEM, TEM and HR-TEM images, histogram of length and width distribution of FMBs, FTIR, TGA and XPS data, and additional CV data.

AUTHOR INFORMATION Corresponding Author *E-mail: [email protected] *E-mail: [email protected]

ACKNOWLEDGMENT This work was partially supported by the National Natural Science Foundation of China (Grant No. 51572128), JSPS KAKENHI (Coordination Asymmetry) (Grant No. JP16H06518), and CREST JST (Grant No. JPMJCR1665). Q. J thanks the ﬁnancial support from “the Fundamental Research Funds for the Central Universities”, No. 30916015108; Science and Technology Program of Jiangsu Province: BK20151484 and AD41572.

REFERENCES (1)

Kang, J.; Wen, J.; Jayaram, S. H.; Yu, A.; Wang, X. Development of an Equivalent Circuit

Model for Electrochemical Double Layer Capacitors (EDLCs) with Distinct Electrolytes. Electrochim. Acta 2014, 115, 587–598. (2)

Béguin, F.; Presser, V.; Balducci, A.; Frackowiak, E. Carbons and Electrolytes for

Advanced Supercapacitors. Adv. Mater. 2014, 26, 2219–2251. (3)

Zhi, M.; Xiang, C.; Li, J.; Li, M.; Wu, N. Nanostructured Carbon–Metal Oxide Composite

Electrodes for Supercapacitors: a Review. Nanoscale 2013, 5, 72–88.


19


(4)

Page 20 of 29

Zhong, C.; Deng, Y.; Hu, W.; Qiao, J.; Zhang, L.; Zhang, J. A Review of Electrolyte

Materials and Compositions for Electrochemical Supercapacitors. Chem. Soc. Rev. 2015, 44, 7484–7539. (5)

Faraji, S.; Ani, F. N. Microwave-assisted Synthesis of Metal Oxide/Hydroxide Composite

Electrodes for High Power Supercapacitors–A Review. J. Power Sources 2014, 263, 338–360. (6)

Dubal, D. P.; Ayyad, O.; Ruiz, V.; Gomez-Romero, P. Hybrid Energy Storage: The

Merging of Battery and Supercapacitor Chemistries. Chem. Soc. Rev. 2015, 44, 1777–1790. (7)

Simon, P.; Gogotsi, Y.; Dunn, B. Where do Batteries End and Supercapacitors Begin?

Science 2014, 343, 1210–1211. (8)

Hou, J.; Cao, C.; Idrees, F.; Ma, X. Hierarchical Porous Nitrogen-Doped Carbon

Nanosheets Derived From Silk for Ultrahigh-Capacity Battery Anodes and Supercapacitors. ACS Nano 2015, 9, 2556–2564. (9)

Yulian, N.; Ruiyi, L.; Zaijun, L.; Yinjun, F.; Junkang, L. High-Performance

Supercapacitors Materials Prepared via in Situ Growth of NiAl-Layered Double Hydroxide Nanoflakes on Well-activated Graphene Nanosheets. Electrochim. Acta 2013, 94, 360–366. (10)

Wang, G.; Zhang, L.; Zhang, J. A Review of Electrode Materials for Electrochemical

Supercapacitors. Chem. Soc. Rev. 2012, 41, 797–828. (11)

Deng, Y.; Xie, Y.; Zou, K.; Ji, X. Review on Recent Advances in Nitrogen-Doped Carbons:

Preparations and Applications in Supercapacitors. J. Mater. Chem. A 2016, 4, 1144–1173. (12)

Huang, P.; Lethien, C.; Pinaud, S.; Brousse, K.; Laloo, R.; Turq, V.; Respaud, M.;

Demortiere, A.; Daffos, B.; Taberna, P.-L. On-chip and Freestanding Elastic Carbon Films for Micro-Supercapacitors. Science 2016, 351, 691–695.


20

Page 21 of 29 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


(13)

Tan, Z.; Ni, K.; Chen, G.; Zeng, W.; Tao, Z.; Ikram, M.; Zhang, Q.; Wang, H.; Sun, L.;

Zhu, X. Incorporating Pyrrolic and Pyridinic Nitrogen into a Porous Carbon Made from C60 Molecules to Obtain Superior Energy Storage. Adv. Mater. 2017, 29, 1603414–1603422. (14)

Shrestha, L. K.; Adhikari, L.; Shrestha, R. G.; Adhikari, M. P.; Adhikari, R.; Hill, J. P.;

Pradhananga, R. R.; Ariga, K. Nanoporous Carbon Materials with Enhanced Supercapacitance Performance and Non-Aromatic Chemical Sensing with C1/C2 Alcohol Discrimination. Sci. Technol. Adv. Mater. 2016, 17, 483–492. (15)

Liu, B.; Jin, L.; Zheng, H.; Yao, H.; Wu, Y.; Lopes, A.; He, J. Ultrafine Co-based

Nanoparticle@Mesoporous Carbon Nanospheres toward High-Performance Supercapacitors. ACS Appl. Mater. Interfaces 2017, 9, 1746–1758. (16)

Shang, P.; Zhang, J.; Tang, W.; Xu, Q.; Guo, S. 2D Thin Nanoflakes Assembled on

Mesoporous Carbon Nanorods for Enhancing Electrocatalysis and for Improving Asymmetric Supercapacitors. Adv. Funct. Mater. 2016, 26, 7766–7774. (17)

Liu, Q. C.; Li, L.; Xu, J. J.; Chang, Z. W.; Xu, D.; Yin, Y. B.; Yang, X. Y.; Liu, T.; Jiang,

Y. S.; Yan, J. M. Flexible and Foldable Li–O2 Battery Based on Paper‐Ink Cathode. Adv. Mater. 2015, 27, 8095–8101. (18)

Wang, G.; Wang, H.; Lu, X.; Ling, Y.; Yu, M.; Zhai, T.; Tong, Y.; Li, Y. Solid‐state

Supercapacitor Based on Activated Carbon Cloths Exhibits Excellent Rate Capability. Adv. Mater. 2014, 26, 2676–2682. (19)

Lee, J.; Yoon, S.; Oh, S. M.; Shin, C. H.; Hyeon, T. Development of a New Mesoporous

Carbon Using an HMS Aluminosilicate Template. Adv. Mater. 2000, 12, 359–362.


21


(20)

Page 22 of 29

Jung, N.; Kwon, S.; Lee, D.; Yoon, D. M.; Park, Y. M.; Benayad, A.; Choi, J. Y.; Park, J.

S. Synthesis of Chemically Bonded Graphene/Carbon Nanotube Composites and Their Application in Large Volumetric Capacitance Supercapacitors. Adv. Mater. 2013, 25, 6854–6858. (21)

Yu, D.; Goh, K.; Wang, H.; Wei, L.; Jiang, W.; Zhang, Q.; Dai, L.; Chen, Y. Scalable

Synthesis of Hierarchically Structured Carbon Nanotube-Graphene Fibers for Capacitive Energy Storage. Nat. Nanotechnol. 2014, 9, 555–562. (22)

Chen, W.; Rakhi, R.; Alshareef, H. N. Capacitance Enhancement of Polyaniline Coated

Curved-graphene Supercapacitors in a Redox-active Electrolyte. Nanoscale 2013, 5, 4134–4138. (23)

Yoo, J. J.; Balakrishnan, K.; Huang, J.; Meunier, V.; Sumpter, B. G.; Srivastava, A.;

Conway, M.; Mohana Reddy, A. L.; Yu, J.; Vajtai, R. Ultrathin Planar Graphene Supercapacitors. Nano Lett. 2011, 11, 1423–1427. (24)

Khan, A. H.; Ghosh, S.; Pradhan, B.; Dalui, A.; Shrestha, L. K.; Acharya, S.; Ariga, K.

Two-Dimensional (2D) Nanomaterials towards Electrochemical Nanoarchitectonics in EnergyRelated Applications. Bull. Chem. Soc. Jpn. 2017, 90, 627–648. (25)

Ambrosi, A.; Chua, C. K.; Bonanni, A.; Pumera, M. Electrochemistry of Graphene and

Related Materials. Chem. Rev. 2014, 114, 7150–7188. (26)

Wang, L.; Pumera, M. Electrochemical Catalysis at Low Dimensional Carbons: Graphene,

Carbon Nanotubes and Beyond-A Review. App. Mater. Today 2016, 5, 134–141. (27)

Ambrosi, A.; Pumera, M. Electrochemically Exfoliated Graphene and Graphene Oxide for

Energy Storage and Electrochemistry Applications. Chem. Eur. J. 2016, 22, 153–159. (28)

Jankovský, O.; Marvan P.; Nováček, M.; Luxa, J.; Mazánek, V.; Klímová, K.;

Sedmidubský, D.; Sofer, Z. Synthesis Procedure and Type of Graphite Oxides Strongly Influence Resulting Graphene Properties. Appl. Mater. Today 2016, 4, 45–53.


22

Page 23 of 29 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


(29)

Pumera, M. Electrochemistry of Graphene, Graphene Oxide and Other Graphenoids:

Review. Electrochem. Commun. 2013, 36, 14–18. (30)

Hu, P.; Meng, D.; Ren, G.; Yan, R.; Peng, X. Nitrogen-Doped Mesoporous Carbon Thin

Film for Binder-Free Supercapacitor. Appl. Mater. Today 2016, 5, 1–8. (31)

Cheng, Q.; Tang, J.; Ma, J.; Zhang, H.; Shinya, N.; Qin, L.-C. Graphene and Carbon

Nanotube Composite Electrodes for Supercapacitors with Ultra-High Energy Density. Phys. Chem. Chem. Phys. 2011, 13, 17615–17624. (32)

Cao, J.; Wang, Y.; Zhou, Y.; Ouyang, J.-H.; Jia, D.; Guo, L. High Voltage Asymmetric

Supercapacitor Based on MnO2 and Graphene Electrodes. J. Electroanal. Chem. 2013, 689, 201– 206. (33)

Cao, X.; Shi, Y.; Shi, W.; Lu, G.; Huang, X.; Yan, Q.; Zhang, Q.; Zhang, H. Preparation

of Novel 3D Graphene Networks for Supercapacitor Applications. Small 2011, 7, 3163–3168. (34)

Choi, B. G.; Yang, M.; Hong, W. H.; Choi, J. W.; Huh, Y. S. 3D Macroporous Graphene

Frameworks for Supercapacitors with High Energy and Power Densities. ACS Nano 2012, 6, 4020–4028. (35)

Zhang, L.; Zhang, F.; Yang, X.; Long, G.; Wu, Y.; Zhang, T.; Leng, K.; Huang, Y.; Ma,

Y.; Yu, A. Porous 3D Graphene-Based Bulk Materials with Exceptional High Surface Area and Excellent Conductivity for Supercapacitors. Sci. Rep. 2013, 3, 1408–1417. (36)

Fan, Z.; Yan, J.; Zhi, L.; Zhang, Q.; Wei, T.; Feng, J.; Zhang, M.; Qian, W.; Wei, F. A

Three‐dimensional Carbon Nanotube/Graphene Sandwich and its Application as Electrode in Supercapacitors. Adv. Mater. 2010, 22, 3723–3728.


23


(37)

Page 24 of 29

Chen, Z.; Ren, W.; Gao, L.; Liu, B.; Pei, S.; Cheng, H.-M. Three-dimensional Flexible and

Conductive Interconnected Graphene Networks Grown by Chemical Vapour Deposition. Nat. Mater. 2011, 10, 424–428. (38)

Soler-Illia, G. J. D. A. A.; Sanchez, C.; Lebeau, B.; Patarin, J. Chemical Strategies To

Design Textured Materials: From Microporous and Mesoporous Oxides to Nanonetworks and Hierarchical Structures. Chem. Rev. 2002, 102, 4093–4138. (39)

Yoon, S. B.; Sohn, K.; Kim, J. Y.; Shin, C. H.; Yu, J. S.; Hyeon, T. Fabrication of Carbon

Capsules with Hollow Macroporous Core/Mesoporous Shell Structures. Adv. Mater. 2002, 14, 19– 21. (40)

Tang, J.; Liu, J.; Li, C.; Li, Y.; Tade, M. O.; Dai, S.; Yamauchi, Y. Synthesis of Nitrogen‐

Doped Mesoporous Carbon Spheres with Extra‐ Large Pores through Assembly of Diblock Copolymer Micelles. Angew. Chem. Int. Ed. 2015, 54, 588–593. (41)

Yan, X.; Yang, Y.; Hu, X.; Zhou, M.; Komarneni, S. Synthesis of Mesoporous Carbons

with Narrow Pore Size Distribution from Metal-organic Framework MIL-100(Fe). Microporous Mesoporous Mater. 2016, 234, 162–165. (42)

Ma, Z.; Kyotani, T.; Tomita, A. Preparation of a High Surface Area Microporous Carbon

Having the Structural Regularity of Y Zeolite. Chem. Commun. 2000, 2, 2365–2366. (43)

Shrestha, L. K.; Shrestha, R. G.; Yamauchi, Y.; Hill, J. P.; Nishimura, T.; Miyazawa, K.;

Kawai, T.; Okada, S.; Wakabayashi, K.; Ariga, K. Nanoporous Carbon Tubes from Fullerene Crystals as the π-electron Carbon Source. Angew. Chem. Int. Ed. 2015, 54, 951–955. (44)

Bairi, P.; Shrestha, R. G.; Hill, J. P.; Nishimura, T.; Ariga, K.; Shrestha, L. K. Mesoporous

Graphitic Carbon Microtubes Derived from Fullerene C70 Tubes as a High Performance Electrode Material for Advanced Supercapacitors. J. Mater. Chem. A 2016, 4, 13899–13906.


24

Page 25 of 29 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


(45)

Zheng, S.; Ju, H.; Lu, X. A High‐Performance Supercapacitor Based on KOH Activated

1D C70 Microstructures. Adv. Energy Mater. 2016, 5, 1500871–1500879. (46)

Shrestha, R. G.; Shrestha, L. K.; Khan, A. H.; Kumar, G. S.; Acharya, S.; Ariga, K.

Demonstration of Ultrarapid Interfacial Formation of 1D Fullerene Nanorods with Photovoltaic Properties. ACS Appl. Mater. Interfaces 2014, 6, 15597–15603. (47)

Kim, J.; Park, C.; Song, I.; Lee, M.; Kim, H.; Choi, H. C. Unique Crystallization of

Fullerenes: Fullerene Flowers. Sci. Rep. 2016, 6, 32205–32213. (48)

Bairi, P.; Minami, K.; Nakanishi, W.; Hill, J. P.; Ariga, K.; Shrestha, L. K. Hierarchically

Structured Fullerene C70 Cube for Sensing Volatile Aromatic Solvent Vapors. ACS Nano 2016, 10, 6631–6637. (49)

Park, C.; Yoon, E.; Kawano, M.; Joo, T.; Choi, H. C. Self‐Crystallization of C70 Cubes

and Remarkable Enhancement of Photoluminescence. Angew. Chem. Int. Ed. 2010, 49, 9670– 9675. (50)

Tang, Q.; Zhang, S.; Liu, X.; Sumita, M.; Ishihara, S.; Fuchs, H.; Ji, Q.; Shrestha, L. K.;

Ariga, K. Manipulation of Fullerene Superstructures by Complexing with Polycyclic Aromatic Compounds. Phys. Chem. Chem. Phys. 2017, 19, 29099–29105. (51)

Bairi, P.; Minami, K.; Hill, J. P.; Ariga, K.; Shrestha, L. K. Intentional Closing/Opening of

“Hole-in-Cube” Fullerene Crystals with Microscopic Recognition Properties. ACS Nano 2017, 11, 7790–7796. (52)

Shrestha, L. K.; Shrestha, R. G.; Hill, J. P.; Tsuruoka, T.; Ji, Q.; Nishimura, T.; Ariga, K.

Surfactant-Triggered Nanoarchitectonics of Fullerene C60 Crystals at a Liquid-Liquid Interface. Langmuir 2016, 32, 12511–12519.


25


(53)

Page 26 of 29

Park, C.; Song, H. J.; Choi, H. C. The Critical Effect of Solvent Geometry on the

Determination of Fullerene (C60) Self-Assembly into Dot, Wire and Disk Structures. Chem. Commun. 2009, 32, 4803–4805. (54)

Wei, L.; Yao, J.; Fu, H. Solvent-Assisted Self-Assembly of Fullerene into Single-Crystal

Ultrathin Microribbons as Highly Sensitive UV-visible Photodetectors. ACS Nano 2013, 7, 7573– 7582. (55)

Sun, Y.; Wu, Q.; Shi, G. Graphene Based New Energy Materials. Energy Environ. Sci.

2011, 4, 1113–1132. (56)

Wu, Z. S.; Zhou, G.; Yin, L. C.; Ren, W.; Li, F.; Cheng, H. M. Graphene/Metal Oxide

Composite Electrode Materials for Energy Storage. Nano Energy 2012, 1, 107–131. (57)

Liu, D.; Wang, X.; Wang, X.; Tian, W.; Liu, J.; Zhi, C.; He, D.; Bando, Y.; Golberg, D.

Ultrathin Nanoporous Fe3O4–Carbon Nanosheets with Enhanced Supercapacitor Performance. J. Mater. Chem. A 2013, 1, 1952–1955. (58)

Shrestha, L. K.; Yamauchi, Y.; Hill, J. P.; Miyazawa, K.; Ariga, K. Fullerene Crystals with

Bimodal Pore Architectures Consisting of Macropores and Mesopores. J. Am. Chem. Soc. 2013, 135, 586–589. (59)

Qu, Y.; Liang, S.; Zou, K.; Li, S.; Liu, L.; Zhao, J.; Piao, G. Effect of Solvent Type on the

Formation of Tubular Fullerene Nanofibers. Mater. Lett. 2011, 65, 562–564. (60)

Shrestha, L. K.; Ji, Q.; Mori, T.; Miyazawa, K.; Yamauchi, Y.; Hill, J. P.; Ariga, K.

Fullerene Nanoarchitectonics: From Zero to Higher Dimensions. Chem. Asian J. 2013, 8, 1662– 1679.


26

Page 27 of 29 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


(61)

Shrestha, L. K.; Hill, J. P.; Tsuruoka, T.; Miyazawa, K.; Ariga, K. Surfactant-Assisted

Assembly of Fullerene (C60) Nanorods and Nanotubes Formed at a Liquid–Liquid Interface. Langmuir 2013, 29, 7195–7202. (62)

Vimalanathan, K.; Shrestha, R. G.; Zhang, Z.; Zou, J.; Nakayama, T.; Raston, C. L.

Surfactant‐free Fabrication of Fullerene C60 Nanotubules Under Shear. Angew. Chem. Int. Ed. 2017, 56, 8389–8401. (63)

Jin, Z. Y.; Lu, A. H.; Xu, Y. Y.; Zhang, J. T.; Li, W. C. Ionic Liquid-Assisted Synthesis of

Microporous Carbon Nanosheets for Use in High Rate and Long Cycle Life Supercapacitors. Adv. Mater. 2014, 26, 3700–3705. (64)

Assink, R. A.; Schirber, J. E.; Loy, D. A.; Morosin, B.; Carlson, G. A. Intercalation of

Molecular Species into the Interstitial Sites of Fullerene. J. Mater. Res. 1992, 7, 2136–2143. (65)

Eloi, C. C.; Robertson, J. D.; Rao, A. M.; Zhou, P.; Wang, K. A.; Eklund, P. C. An

Investigation of Photo-Assisted Diffusion of Oxygen in Solid C60 films Using Resonant AlphaScattering. J. Mater. Res. 1993, 8, 3085–3089. (66)

Zhou, J.; Lian, J.; Li, H.; Zhang, J.; Gou, H.; Xia, M.; Zhao, Y.; Strobel, T. A.; Lu, T.; Gao,

F. Ultrahigh Volumetric Capacitance and Cyclic Stability of Fluorine and Nitrogen Co-doped Carbon Microspheres. Nat. Commun. 2015, 6, 8503–8511. (67)

Wu, Z. S.; Chen, L.; Liu, J.; Parvez, K.; Liang, H.; Shu, J.; Sachdev, H.; Graf, R.; Feng,

X.; Müllen, K. High-Performance Electrocatalysts for Oxygen Reduction Derived From Cobalt Porphyrin-Based Conjugated Mesoporous Polymers. Adv. Mater. 2014, 26, 1450–1455. (68)

Chen, R.; Zhao, T.; Wu, W.; Wu, F.; Li, L.; Qian, J.; Xu, R.; Wu, H.; Albishri, H. M.;

Albogami,

A.

S.

Free-Standing

Hierarchically

Sandwich-type

Tungsten

Disulfide

Nanotubes/Graphene Anode for Lithium-ion Batteries. Nano Lett. 2014, 14, 5899–5904.


27


(69)

Page 28 of 29

Lu, H.; Dai, W.; Zheng, M.; Li, N.; Ji, G.; Cao, J. Electrochemical Capacitive Behaviors

of Ordered Mesoporous Carbons with Controllable Pore Sizes. J. Power Sources 2012, 209, 243– 250. (70)

Qu, D.; Hang, S. Studies of Activated Carbons Used in Double-Layer Capacitors. J. Power

Sources 1998, 74, 99–107. (71)

Sevilla, M.; Fuertes, A. B. Direct Synthesis of Highly Porous Interconnected Carbon

Nanosheets and Their Application as High-Performance Supercapacitors. ACS Nano 2014, 8, 5069–5078. (72)

Fuertes, A. B.; Sevilla, M. Hierarchical Microporous/Mesoporous Carbon Nanosheets for

High-Performance Supercapacitors. ACS Appl. Mater. Interfaces 2015, 7, 4344–4353.


28

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Quasi 2D Mesoporous Carbon Microbelts Derived from Fullerene

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