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Hydrothermal synthesis and activation of graphene-incorporated nitrogen-rich carbon composite for high-performance supercapacitors
Xiaoming Fan, Chang Yu, Juan Yang, Zheng Ling, Jieshan Qiu
*

Carbon Research Laboratory, Liaoning Key Lab for Energy Materials and Chemical Engineering, State Key Lab of Fine Chemicals, Dalian University of Technology, Dalian 116024, PR China

A R T I C L E I N F O

A B S T R A C T

Article history: Received 3 October 2013 Accepted 25 December 2013 Available online 8 January 2014

Graphene-incorporated nitrogen-rich carbon composite with nitrogen content of ca. 10 wt.% has been synthesized by an effective yet simple hydrothermal reaction of glucosamine in the presence of graphene oxide (GO). The nitrogen content of carbon composite is nearly twice as high as that of hydrothermal carbon without graphene. GO is favorable for the high nitrogen doping in the carbon composite by the reaction between the glucosamine-released ammonia and GO. The hydrothermal carbon composite is further activated by KOH, and graphene in the activated carbon composite demonstrates a positive effect of increasing specic surface area, pore volume and electrical conductivity, resulting in superior electrochemical performance. The activated carbon composite with higher specic surface area and micropore volume possesses higher specic capacitance with a value of 300 F g1 at 0.1 A g1 in 6 M KOH aqueous solution in the two electrode cell. Larger mesopore volume and higher conductivity of the activated carbon composite will provide fast ion and electron transfer, thus leading to higher rate capacity with a capacitance retention of 76% at 8 A g1 in comparison to the activated hydrothermal carbon without graphene. 2014 Elsevier Ltd. All rights reserved.

1.

Introduction

Carbon electrode materials for supercapacitors have been studied extensively in past decades due to their low cost, high surface area, excellent electrochemical stability and electrical conductivity [13]. Capacitive behavior on the carbon based supercapacitors can be mainly classied into electrical double-layer capacitance, which arises from the electrostatic attraction between ions and the charged surface of carbon electrode. However, these pure carbon-based electrical double-layer capacitors (EDLC) cannot meet the requirements in high energy storage eld. An efcient approach to solve this problem is to incorporate heteroatoms into carbon materials to enhance the capacitance, in which additional

contributions derived from pseudocapacitance associated with Faradaic charge transfer reactions between the heteroatoms and the electrolytes are present. It has been found that heteroatom dopants such as oxygen, nitrogen, boron, phosphorus and sulfur can improve the capacitance to a certain degree [412]. Of these available dopants, nitrogen doping has attracted much attention and shows a signicant improvement for higher energy storage ability. Nitrogen species in the carbon materials can not only act as an electron donor due to its ve valence electrons which result in a shift of the Fermi level to the valence band but also introduce functional groups containing nitrogen and oxygen atoms [1316]. Moreover, the combined and positive effects of nitrogen and oxygen containing groups on the electrochemical

* Corresponding author. E-mail address: jqiu@dlut.edu.cn (J. Qiu). 0008-6223/$ - see front matter 2014 Elsevier Ltd. All rights reserved. http://dx.doi.org/10.1016/j.carbon.2013.12.081

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performance are also present in the microporous activated carbon electrode for supercapacitors [5]. Functional carbon materials can be synthesized using various carbon-containing sources such as hydrocarbon, polymer, biomass and so on. From the point of view of sustainable chemistry, biomass and its derivatives are considered as one of highly potential candidates for the production of functional carbon materials. To convert biomass to nanostructured carbon, hydrothermal carbonization has been considered as an efcient method operated in an environmentally friendly process [17,18]. Nitrogen-containing hydrothermal carbons (HTCs) have been prepared from different types of biomasses or derivatives such as chitin, chitosan, glucosamine (GA), microalgae and so on [1921]. Moreover, the nitrogen-free biomass and nitrogencontaining molecules such as ovalbumin, glycine, and ethylenediamine are also employed to fabricate nitrogen-containing HTCs [2224]. It has also been demonstrated that HTCs are rich in oxygen groups and the oxygen content can be tuned by different operating conditions. With this in mind, HTCs have been considered as a promising candidate of electrode materials for supercapacitors. Titirici et al. recently found that GA-derived nitrogen-containing HTCs chemically activated by KOH exhibited superior performance in supercapacitors [25]. Interestingly, HTCs with the networks of uniformly distributed oxygen-containing groups can be efciently transformed into microporous carbons with the optimum pore size distribution by chemically activation. The activated carbon materials from natural polysaccharides-derived HTCs exhibited excellent potential for supercapacitor applications with rather high specic capacitance and rapid chargingdischarging capability [26]. Graphene is a two dimensional carbon material with high surface area, electrical conductivity, mechanical strength and chemical stability, and considered as a promising candidate of electrode materials for supercapacitors [27,28]. Graphene has also been used as an additive in the activated carbon, mesoporous carbon, carbon nanober to improve their electrochemical performance in supercapacitors [2932]. Chen et al. also reported porous graphene-based bulk materials produced by KOH activation of the sucrose-derived HTCs and graphene composite. Graphene in the graphene-based bulk materials is in favor of increasing their surface area and electrical conductivity, resulting in superior supercapacitve performance in the ionic liquid electrolyte [33]. Nevertheless, few work has been reported to investigate the role of graphene oxide (GO) as an additive in the hydrothermal reaction of nitrogen-containing carbohydrate. Herein, we report an effective yet simple hydrothermal method to fabricate nitrogen-rich graphene-incorporated HTC (GHTC) using GA as a nitrogen-containing carbohydrate precursor (Fig. S1). GO is in favor of increasing the nitrogen content of the GHTC (ca. 10 wt.%) to a great degree in the hydrothermal process. The HTC and GHTC were further activated by KOH, and the electrochemical performance of the activated products as electrode materials for supercapacitors was investigated. It was found that graphene demonstrates a positive effect of increasing the surface area, pore volume and electrical conductivity of the activated GHTC, leading to high specic capacitance and rate capacity.

2.
2.1. 2.1.1.

Experimental
Sample preparation Synthesis of the HTC and GHTC

GO was prepared according a modied Hummers method which has been described in the previous reports [3436]. The GHTC composite was synthesized by a hydrothermal method, the details of which are described below. A 30 mL GO solution (3 mg mL1) was mixed with a solution which contained 8 g GA hydrochloride (C6H13NO5HCl) dissolved in 60 mL deionized water. The pH of the reaction system was adjusted to 11 with NaOH aqueous solution to obtain welldispersed mixture [37], and then the mixture was transferred to a Teon autoclave and treated at 180 C for 12 h. After cooling, the product was washed with deionized water and dried at 80 C. For comparison, the nitrogen-doped HTC without graphene was also prepared by directly hydrothermal treatment of GA at 180 C for 12 h.

2.1.2.

Activation of the HTC and GHTC by KOH

The HTC and GHTC samples were activated by KOH at 600 C for 4 h in a nitrogen atmosphere with a mass ratio of KOH to carbonaceous materials 2:1. The as-obtained products were then treated with diluted hydrochloric acid and deionized water and then dried at 80 C overnight. The activated samples were denoted as HTC-a and GHTC-a, respectively.

2.2.

Characterization methods

Morphologies and microstructures of samples before and after KOH activation were observed by eld emission scanning electron microscopy (FESEM) (FEI NOVA NanoSEM 450) at 3 kV and transmission electron microscopy (TEM) (FEI Tecnai G220 and TF30). Specic surface area and pore size distribution were calculated based on the data recorded on physical sorption instrument (Micromeritics ASAP 2020). The samples were degassed at 150 C prior to nitrogen sorption measurement. Element compositions were measured using Elementar varioEL III. The data of X-ray photoelectron spectroscopy were collected on Thermo ESCALAB 250. The electrical conductivities were calculated according the results measured by the four-probe method using a S-2A four-probe station and Keithley 2400 Sourcemeter.

2.3.

Electrochemical measurements

Active materials and binder poly(tetrauoroethylene) with the mass ratio of 95:5 pressed onto the nickel foam were used as the working electrode. Hg/HgO electrode and Pt foil electrode were used as reference electrode and counter electrode, respectively. Working electrodes mentioned above with the same mass were symmetrically assembled to two electrode cell. Cyclic voltammetry was carried out using a CHI 660D (Shanghai Chenhua, China) electrochemical workstation in a three electrode cell with 6 M KOH as electrolyte solution. Galvanostatic chargedischarge proles and electrochemical impedance spectroscopy were also recorded in a two electrode cell with 6 M KOH as electrolyte solution using a CHI

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660D electrochemical workstation. Gravimetric specic capacitances of the cells Ccell were calculated at different current densities according to galvanostatic charge/discharge proles based on the following equations: Ccell I mtotal dv=dt 1

where Ccell is the specic capacitance of the two electrode cell, I is the discharge current, dv/dt is the average slope of the discharge curve, and mtotal is the total mass of active materials in the two electrode cell. The specic capacitance of single electrode could be obtained by multiplying the Ccell by four. Energy density and power density of the cells were calculated based on the following equations: Ecell Pcell Ccell DV2 1000 2 3600 Ecell 3600 Dt 2

where Ecell and Pcell are the energy density and power density of two electrode cell, respectively, DV is the voltage window from the end of IR drop to the end of discharge and Dt is the discharge time. Galvanostatic cycling was performed by 1000 cycles at the current density of 1 A g1.

3.
3.1.

Results and discussion

Enhanced nitrogen doping in GHTC composite

Great changes occur during the hydrothermal reaction of GA in the presence of a small amount of GO, in which GA was transformed to carbonaceous materials and GO was reduced to graphene simultaneously [20,38]. The typical SEM images

of the HTC and GHTC are shown in Fig. 1. The HTC (Fig. 1a and b) has a compact network assembled by smaller carbon particles and displays a rough surface. In the case of the GHTC, a relatively smoother surface can be observed and the graphene layers cover onto the surface of the HTC particles, of which the edge can be clearly seen in the ellipse shown in Fig. 1d. The further TEM images in Fig. 2a and b reveal that the HTC from GA is consisted of agglomerated smaller carbon particles with an amorphous structure, which is consistent with the SEM results. For the GHTC, the graphene layers curl up to some degree and are uniformly dispersed in the resulting carbon composite, which are marked in Fig. 2c. The compositions of the HTC and GHTC were rstly determined by the element analysis (Table S1). The two hydrothermal products both have relatively low carbon content and high oxygen content, which is similar to the results reported in the literatures [20,39]. It is interesting that the weight content of nitrogen in the GHTC nearly reaches 10.0 wt.%, being an increase of twice in comparison to that in the HTC. The nitrogen content in the GHTC remains a high value up to 10.1 wt.% even if the sample is further treated at 600 C for 4 h under the nitrogen atmosphere. It is also noted that the carbon content also increases while the oxygen content decreases a lot after heat treatment. This indicates that carbonaceous material with high and stable nitrogen content can be achieved through a GO assisted hydrothermal reaction of nitrogen-containing carbohydrates. The content of the element C, O, N on the surface of the HTC and GHTC was also evaluated using X-ray photoelectron spectroscopy (XPS) and the detailed information is summarized in Table 1. It is very surprising that the atom content of N in the GHTC is 3.5 times as much as that in the HTC from the XPS results. The N/C ratio of the GHTC also increases by

Fig. 1 SEM images of (a, b) HTC and (c, d) GHTC. (A color version of this gure can be viewed online.)

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Fig. 2 TEM images of (a, b) HTC and (c, d) GHTC. (A color version of this gure can be viewed online.)

Table 1 Surface compositions of the samples before and after KOH activation determined by XPS. Sample HTC GHTC HTC-a GHTC-a C/at.% 79.1 77.1 85.9 86.0 N/at.% 1.8 6.3 2.3 2.2 O/at.% 19.1 16.7 11.8 11.8 N/C 0.023 0.082 0.027 0.026 O/C 0.24 0.22 0.14 0.14

3.5 times but the O/C ratio decreases slightly. This indicates that the reaction pathway corresponding to nitrogen-containing functional groups may change to some degree in the presence of GO during the hydrothermal process, which will be further discussed in the following section. Further information about the changes of surface chemistry has been obtained from the deconvoluted high-resolution XPS spectra of three interesting regions (C, O, and N) (Fig. 3 and Fig. S2). The C1s spectra of the HTC and GHTC in Fig. 3a and b can be deconvoluted into ve components, and the carbon species correspond to carbide carbon (283.9 eV); graphite carbon (284.6 eV); carbon in COC or ROH (285.3 eV); carbon in C@O (286.2 eV); and carbon in COOH or C(O)OC (288.5 eV) (Fig. 3a and b) [40,41]. No obvious differences are observed in the carbon components of the two samples. However, there exist the differences between the O1s spectra of the HTC and GHTC to some extent. The oxygen species of the HTC repre-

sent oxygen double bonded to carbon (C@O) (531.8 eV), oxygen single bonded to carbon in CO (532.8 eV) and oxygen in hydroxyl OH (533.7 eV), while the O1s region of the GHTC contains three components, corresponding to quinone (530.7 eV), C@O (531.8 eV) and CO (532.9 eV) (Fig. 3c and d) [5,41]. Great changes of nitrogen components in the HTC and GHTC are very obvious, which is in agreement with element analysis results. The nitrogen content of the HTC on the surface is 1.8 at.%, and the N1s peak shows four components at 398.4, 399.5, 400.3 and 401.3 eV, which can be ascribed to pyridinic (N-6, 0.7 at.%), amine (NH2, 0.5 at.%), pyrrolic/pyridone (N-5, 0.3 at.%) and quaternary (N-Q, 0.3 at.%) nitrogen, respectively (Fig. 3c and d) [5,13]. In the case of the GHTC, the surface nitrogen content increases up to 6.3 at.%. The nitrogen species include N-6 (2.0 at.%), NH2 (2.5 at.%), and N-5 (1.7 at.%) (Fig. 3e and f), nevertheless, the characteristic peak of the N-Q nitrogen disappears. Based

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Fig. 3 Deconvoluted high-resolution (a, b) C1s, (c, d) O1s and (e, f) N1s spectra of the HTC and GHTC. (A color version of this gure can be viewed online.)

on the above results, we conclude that GO will provide a new possibility to increase the nitrogen doping in the HTC composite. GO is favorable for the nitrogen xation and the nitrogen-doping enhancement in the HTC composite with increasing the content of pyridinic, amine and pyrrolic nitrogen (Fig. 3e and f). The possible mechanism of the enhanced nitrogen doping in the GHTC composite has been proposed here. The degradation of GA in water at high temperature has been investigated in many literatures, in which GA is transformed into hydroxymethyl furfural (HMF) and releases ammonia in solution simultaneously (Fig. 4a); subsequently, ammonia reacts with HMF to form different type of nitrogen-containing molecules (Fig. 4b (1)) [20,42,43]. When GO was added in the hydrothermal reaction of GA, new reaction between GO and the released ammonia from GA would occur simultaneously in the system. Gao et al. reported that the urea decomposes and releases ammonia, and the released ammonia reacts with the oxygen functional groups (carboxylic acid and epoxide) on the GO surface to form the intermediates (amide and amine) under the hydrothermal conditions. These nitrogen-

containing intermediates can further pass through the reaction of dehydration (pyridine or pyridone) or decarbonylation (pyrrole) to form more stable structures (Fig. 4b (2)) [44]. That is to say, the competitive reaction for ammonia would occur between GO and the GA-released HMF, which may also change the elemental composition of the nal product in the system. Furthermore, it is worth pointing out that HMF is the main reactive compound in the hydrothermal process resulting in the formation of carbonaceous material with the furane rings, which is abundant in the nal nitrogendoped product (Fig. 4b (3)) [23,45]. On the basis of the discussion mentioned above, the released ammonia from GA undergoes two reactions simultaneously in which ammonia reacts with HMF and GO, and the possible mechanism is proposed and illustrated in Fig. 4c.

3.2.

KOH activation of HTC and GHTC

KOH activation is a general method applied to increase the specic area and pore volume in carbon materials, which contributes to obtaining electrode materials with high capacitance in

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Fig. 4 (a) Degradation reaction of GA to HMF and ammonia. (b) (1, 2) Possible reactions of HMF and GO for ammonia; (3) Main reaction of HMF transformed into carbonaceous material with furanic structure. (c) Schematic representation of the hydrothermal progress of HMF, GO and ammonia to fabricate graphene-incorporated nitrogen-doped carbon composite. (A color version of this gure can be viewed online.)

supercapacitor application. The HTC and GHTC were activated by KOH with a mass ratio of KOH to the carbonaceous materials 2:1 at 600 C for 4 h to obtain the products HTC-a and GHTC-a. The activation mechanism follows several simultaneous/consecutive reactions of carbon and KOH below 700 C [46]. Fig. 5 shows the morphologies of the HTC-a and GHTC-a, in which the two samples both exhibit the typical morphologies of activated carbon composed of the broken carbon particles. The differences that can be observed in the GHTC-a are that the graphene layers are incorporated in the carbon matrix and cover onto the carbon particles (marked by the ellipse in Fig. 5d). This is also why the GHTC-a has a high conductivity, nearly being three orders of magnitude in comparison to that of the HTC-a (Table 2). Further TEM examination of the GHTC-a reveals that the micropores with a very small diameter are present in the carbon particle in Fig. 6b, which will provide the possibility for enhancing the capacitance of carbon composite, while the graphene layers in the carbon composite are wrinkled and stacked with multilayers (marked by the ellipse in Fig. 6d).

The porous structures of the HTC-a and GHTC-a were analyzed by nitrogen sorption technique and their nitrogen adsorption/desorption isotherms are shown in Fig. 7a. The two samples both exhibit a combined characteristics of type I/IV isotherms, indicating that the samples contain micropores and mesopores. Pore size distributions of the two samples are obtained using the density functional theory (DFT) method, which are shown in Fig. 7b. It can be seen that most of the pore volumes of the two samples arise from micropores. Compared to the HTC-a, the GHTC-a contains a large volume of micropores with pore size below 0.7 nm that is considered as very active for double layer capacitance [47]. Moreover, the micropore size of the HTC-a concentrates in the pore size region below 1 nm, whereas the GHTC-a contains more pores with the size larger than 1 nm including mesopores. This will be a positive factor for rate capability of the GHTCa in the supercapacitor application [48]. Pore volume and BrunauerEmmettTeller (BET) specic surface area are calculated from the isotherms data and the results are shown in Table 2. It is noted that specic surface area, total pore

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Fig. 5 SEM images of (a, b) HTC-a and (c, d) GHTC-a. (A color version of this gure can be viewed online.)

Table 2 Porous properties and electrical conductivity values of the HTC-a and GHTC-a. Sample HTC-a GHTC-a
a b

SBET/m2 g1 1147 1646

Vta/cm3 g1 0.60 0.82

Vmb/cm3 g1 0.37 0.54

Conductivity/S m1 0.013 15.1

Single point total pore volume (Vt) from adsorption isotherms at P/P0  0.99. Micropore volume (Vm) calculated using the DFT method.

Fig. 6 TEM images of the GHTC-a. (A color version of this gure can be viewed online.)

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components in the GHTC bonded to the edge carbon atoms of graphene layers may be etched more easily in the KOH activation process. How to immobilize nitrogen during the KOH activation process needs to be further investigated in the future. Nevertheless, the similar surface chemistry leads one to believe that the supercapacitve performances between the activated HTC-a and GHTC-a should be governed by the improved physical properties such as pore structure and electrical conductivity.

3.3.

Electrochemical behaviors of HTC-a and GHTC-a

Fig. 7 (a) Nitrogen adsorption/desorption isotherms and (b) pore size distributions of the HTC-a and GHTC-a. (A color version of this gure can be viewed online.)

volume and micropore volume of the GHTC-a are higher than that of the HTC-a, demonstrating that graphene has a positive effect on the enhancement of surface area and porosity of the activated carbon composite. Nevertheless, the graphene-induced enhancement of specic surface area and porosity depends on the content and existence form of graphene in carbon composite [30,33]. The surface chemical properties of the activated carbon materials are of importance to their supercapacitive behaviors. The changes of the surface compositions in the as-prepared KOH-activated carbon materials obtained from XPS measurement are also shown in Table 1. It can be seen that the values of N/C and O/C ratios in the two activated carbon materials are nearly equal, demonstrating the similar surface chemical compositions, which can be further conrmed by the detailed high-resolution XPS spectra of each element. Fig. 8 shows the deconvoluted high-resolution C1s, O1s and N1s XPS spectra of the HTC-a and GHTC-a, and the details of each identied component of the two samples are shown in Fig. S3. Compared to the HTC-a, the GHTC-a possesses more than 18% of sp2 carboncarbon bonds corresponding to the graphite carbon at 284.6 eV, which can be ascribed to the presence of graphene layers. This is also why the GHTCa has an enhanced electrical conductivity. Moreover, the oxygen species of the two samples only have a slight difference in the percentage of each component. An obvious change of surface chemical compositions for the samples before and after the process of KOH activation is that the two activated samples have almost the same nitrogen species, although the nitrogen content of the GHTC is 3.5 times higher than that of the HTC. The reason for this could be that the nitrogen

The electrochemical performances of the HTC-a and GHTC-a were analyzed using the technologies of cyclic voltammetry, galvanostatic chargedischarge and electrochemical impedance spectroscopy in the 6 M KOH aqueous solution. Fig. 9 illustrates cyclic voltammograms (CVs) of the HTC-a and GHTC-a measured in the three-electrode cell at different scan rates. Both the two samples exhibit a typical capacitive behavior with quasi-rectangular shaped voltammetry characteristics as well as broad humps in the CVs at a low scan rate of 5 mV s1, indicating that the capacitance results from the combination of electrical double-layer capacitance and pseudocapacitance related to redox reactions of the heteroatoms in the electrode materials. The redox peaks observed more obviously in acidic electrolyte in the CVs (Fig. S4) further reveal the presence of the pseudocapacitance. Moreover, for the GHTC-a containing graphene sheets in the carbon matrix, a faster electrochemical response can be observed, revealing that graphene in the GHTC-a reduces the resistance of the electrode materials to achieve faster current response, and induces the GHTC-a to possess a better EDLC behavior. It is also noted that the CVs of the GHTC-a maintain more rectangular shape than those of the HTC-a with increasing the scan rate; meanwhile, the specic capacitances of the GHTC-a remain a higher value according to the areas of the CVs. It is helpful for determining the intrinsic electrochemical characteristics of an electrode material in the three-electrode system. However, to reproduce the physical conguration, internal voltages, and charge transfer occurred in a packaged supercapacitor, a two-electrode cell test is preferred to provide the best indication of the electrochemical performance [49]. In this respect, galvanostatic chargedischarge technique was performed in the two-electrode cell symmetrically assembled by the HTC-a or GHTC-a electrodes to further investigate their capacitive behavior and cycling stability, the results of which are shown in Fig. 10. The chargedischarge proles at different current loads from 0.2 to 2 A g1 are shown in Fig. 10a and b. Unlike linear characteristics, the deviations from the linear curves can be observed in the chargedischarge tests of the HTC-a and GHTC-a, indicating the presence of redox reactions during the chargedischarge process [50]. This is consistent with the results of cyclic voltammetry. It can be also found that the Ohmic drop of the GHTC-a electrode is smaller than that of the HTC-a electrode, proving the higher electrical conductivity of the GHTC-a, which is in agreement with the results shown in Table 2. The specic capacitances of the two samples calculated from the results of chargedischarge proles are shown in Fig. 10c. The GHTC-a possesses a specic capacitance of 300 F g1 at

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Fig. 8 Deconvoluted high-resolution (a, b) C1s, (c, d) O1s and (e, f) N1s spectra of the HTC-a and GHTC-a. (A color version of this gure can be viewed online.)

Fig. 9 Cyclic voltammograms of the (a) HTC-a and (b) GHTC-a at different scan rates of 5, 10, 20, 50 and 100 mV s1 in the three-electrode cell. (A color version of this gure can be viewed online.) 0.1 A g1 in the 6 M KOH aqueous solution, the value of which is 20% higher than that of the HTC-a. This can be attributed to the fact that the GHTC-a has larger specic area and micropore volume than HTC-a since the GHTC-a and HTC-a have the similar surface chemical properties to eliminate the im-

pact of surface functional groups. Moreover, the GHTC-a retains higher capacitance retention of 76% (228 F g1 at 8 A g1) in comparison to the HTC-a (88 F g1 at 8 A g1). The higher mesopore volume and electrical conductivity of the GHTC-a will provide a faster ions and electron migration in

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Fig. 10 Galvanostatic chargedischarge curves of the (a) HTC-a and (b) GHTC-a in the two-electrode cell; (c) Specic capacitances of the HTC-a and GHTC-a at various current densities measured in the two-electrode cell (the results were calculated from the specic capacitance of the cell multiplied by four); (d) Capacitance retention of the GHTC-a measured at 1 A g1 in the two-electrode cell. (A color version of this gure can be viewed online.)

the chargedischarge process resulting in a higher capacitance retention. The GHTC-a also shows good cycling stability, exhibiting a 90% capacitance retention when cycling 1000 times at 1 A g-1 (Fig. 10d). Fig. 11a shows the electrochemical impedance spectroscopy measured in the range from 0.01 to 100 kHz in the two-electrode cell. The equivalent series resistance of the GHTC-a is slightly smaller than that of the HTC-a. The semicircle of the Nyquist plot in the high-frequency range is associated with the surface properties of the porous electrode and corresponds to the charge transfer resistance. The smaller diameter of semicircle corresponds to the lower charge transfer resistance. The diameter of semicircle in the Nyquist plot of GHTC-a is much smaller than that of HTC-a, indicating that the GHTC-a electrode containing graphene sheets can offer

faster charge transportation, which can be contributed to the improved pore structure and electrical conductivity as discussed above. The line of the Nyquist plot in the low-frequency range is related to the capacitive behavior of the electrode. Compared to the HTC-a, a nearly vertical line can be observed on the Nyquist plot of the GHTC-a electrode, which reects a better supercapacitive behavior. The relationship between the imaginary part of gravimetric capacitance and frequency is also shown in Fig. 11b, which is calculated from the results of electrochemical impedance spectroscopy according to the method reported by Gogotsi et al. [51]. The imaginary part of capacitance reaches the maximum at the frequency f0, the reciprocal of which yields a time constant, s, that is a quantitative measure of how fast the device can be charged and discharged reversibly. The GHTC-a has a time

Fig. 11 (a) Nyquist plots of the HTC-a and GHTC-a measured in the two-electrode cell; (b) The correlation of imaginary parts of specic capacitances with frequency for the HTC-a and GHTC-a resulted from the Nyquist plots. (A color version of this gure can be viewed online.)

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Appendix A. Supplementary data

Supplementary data associated with this article can be found, in the online version, at http://dx.doi.org/10.1016/j.carbon. 2013.12.081.

R E F E R E N C E S

Fig. 12 Ragone plots of the HTC-a and GHTC-a measured in the two-electrode cell. (A color version of this gure can be viewed online.)

constant s of 15 s, which is much smaller than that of the HTC-a (48 s). This implies that the GHTC-a exhibit a faster frequency response and a better chargedischarge behavior at a high current load. Fig. 12 demonstrates the relationship between the power density and energy density measured in the two-electrode cell symmetrically assembled by the HTCa or GHTC-a electrode. The energy density of the GHTC-a reaches 8.4 W h kg1 at a power density of 22.5 W kg1, being higher than that of the HTC-a, and the GHTC-a maintains a much higher energy density than the HTC-a when the power density increases to the relatively high value.

4.

Conclusions

Graphene-incorporated nitrogen-rich carbon composite has been successfully fabricated from the mixture of GA and GO by an effective yet simple hydrothermal method. The morphologies, microstructures and surface chemistry of the asmade products are governed by the existing graphene. The presence of GO in the hydrothermal reaction of GA provides an additional reaction pathway between the ammonia and GO, resulting in the enhancement of nitrogen doping in the GHTC. After KOH activation, the GHTC-a exhibits higher specic capacitance with a value of 300 F g1 at 0.1 A g1 and rate capacity with a capacitance retention of 76% at 8 A g1 in comparison to the HTC-a because of the larger surface area, enhanced mesopore volume and electrical conductivity of the GHTC-a. In general, graphene-incorporated carbon composite from low-cost biomass by an effective yet simple hydrothermal method coupled with KOH activation will provide a promising candidate to gain high-performance activated carbon material for the applications in supercapacitor and other elds.

Acknowledgements
This work was partly supported by the National Natural Science Foundation of China (Nos. 20923006, 21336001 and U1203292) and Dalian Municipal Science & Technology Project of China (No. 2011A15GX023).

[1] Ghosh A, Lee YH. Carbon-based electrochemical capacitors. ChemSusChem 2012;5(3):48099. [2] Simon P, Gogotsi Y. Capacitive energy storage in nanostructured carbon-electrolyte systems. Acc Chem Res 2013;46(5):1094103. [3] Zhai Y, Dou Y, Zhao D, Fulvio PF, Mayes RT, Dai S. Carbon materials for chemical capacitive energy storage. Adv Mater 2011;23(42):482850. [4] Lota G, Grzyb B, Machnikowska H, Machnikowski J, Frackowiak E. Effect of nitrogen in carbon electrode on the supercapacitor performance. Chem Phys Lett 2005;404(1 3):538. [5] Hulicova-Jurcakova D, Seredych M, Lu GQ, Bandosz TJ. Combined effect of nitrogen- and oxygen-containing functional groups of microporous activated carbon on its electrochemical performance in supercapacitors. Adv Funct Mater 2009;19(3):43847. [6] Wang D-W, Li F, Chen Z-G, Lu GQ, Cheng H-M. Synthesis and electrochemical property of boron-doped mesoporous carbon in supercapacitor. Chem Mater 2008;20(22):7195200. [7] Guo H, Gao Q. Boron and nitrogen co-doped porous carbon and its enhanced properties as supercapacitor. J Power Sources 2009;186(2):5516. [8] Iyyamperumal Eswaramoorthi, Wang S, Dai L. Vertically aligned BCN nanotubes with high capacitance. ACS Nano 2012;6(6):525965. [9] Wu ZS, Winter A, Chen L, Sun Y, Turchanin A, Feng X, et al. Three-dimensional nitrogen and boron co-doped graphene for high-performance all-solid-state supercapacitors. Adv Mater 2012;24(37):51305. [10] Zhao X, Wang A, Yan J, Sun G, Sun L, Zhang T. Synthesis and electrochemical performance of heteroatom-incorporated ordered mesoporous carbons. Chem Mater 2010;22(19):546373. [11] Tsubota T, Takenaka K, Murakami N, Ohno T. Performance of nitrogen- and sulfur-containing carbon material derived from thiourea and formaldehyde as electrochemical capacitor. J Power Sources 2011;196(23):1045560. [12] Hulicova-Jurcakova D, Kodama M, Shiraishi S, Hatori H, Zhu ZH, Lu GQ. Nitrogen-enriched nonporous carbon electrodes with extraordinary supercapacitance. Adv Funct Mater 2009;19(11):18009. [13] Wang D-W, Li F, Yin L-C, Lu X, Chen Z-G, Gentle IR, et al. Nitrogen-doped carbon monolith for alkaline supercapacitors and understanding nitrogen-induced redox transitions. Chem Eur J 2012;18(17):534551. [14] Seredych M, Hulicova-Jurcakova D, Lu GQ, Bandosz TJ. Surface functional groups of carbons and the effects of their chemical character, density and accessibility to ions on electrochemical performance. Carbon 2008;46(11):147588. [15] Hulicova-Jurcakova D, Seredych M, Jin Y, Lu GQ, Bandosz TJ. Specic anion and cation capacitance in porous carbon blacks. Carbon 2010;48(6):176778. [16] Hulicova-Jurcakova D, Fiset E, Lu GQ, Bandosz TJ. Changes in surface chemistry of carbon materials upon electrochemical

CARBON

7 0 (2 0 1 4) 1 3 014 1

141

[17]

[18]

[19]

[20]

[21]

[22]

[23]

[24]

[25]

[26]

[27]

[28]

[29]

[30]

[31]

[32]

[33]

[34]

measurements and their effects on capacitance in acidic and neutral electrolytes. ChemSusChem 2012;5(11):218899. Hu B, Wang K, Wu L, Yu SH, Antonietti M, Titirici M-M. Engineering carbon materials from the hydrothermal carbonization process of biomass. Adv Mater 2010;22(7):81328. Titirici M-M, Antonietti M. Chemistry and materials options of sustainable carbon materials made by hydrothermal carbonization. Chem Soc Rev 2010;39(1):10316. White RJ, Antonietti M, Titirici M-M. Naturally inspired nitrogen doped porous carbon. J Mater Chem 2009;19(45):864550. Zhao L, Baccile N, Gross S, Zhang Y, Wei W, Sun Y, et al. Sustainable nitrogen-doped carbonaceous materials from biomass derivatives. Carbon 2010;48(13):377887. Falco C, Sevilla M, White RJ, Rothe R, Titirici M-M. Renewable nitrogen-doped hydrothermal carbons derived from microalgae. ChemSusChem 2012;5(9):183440. Baccile N, Antonietti M, Titirici M-M. One-step hydrothermal synthesis of nitrogen-doped nanocarbons: albumine directing the carbonization of glucose. ChemSusChem 2010;3(2):24653. Baccile N, Laurent G, Coelho C, Babonneau F, Zhao L, Titirici M-M. Structural insights on nitrogen-containing hydrothermal carbon using solid-state magic angle spinning 13C and 15N nuclear magnetic resonance. J Phys Chem C 2011;115(18):897682. Liu Z, Zhang C, Luo L, Chang Z, Sun X. One-pot synthesis and catalyst support application of mesoporous N-doped carbonaceous materials. J Mater Chem 2012;22(24):1214954. Zhao L, Fan LZ, Zhou MQ, Guan H, Qiao S, Antonietti M, et al. Nitrogen-containing hydrothermal carbons with superior performance in supercapacitors. Adv Mater 2010;22(45):52026. Wei L, Sevilla M, Fuertes AB, Mokaya R, Yushin G. Hydrothermal carbonization of abundant renewable natural organic chemicals for high-performance supercapacitor electrodes. Adv Energy Mater 2011;1(3):35661. Zhu Y, Murali S, Stoller MD, Ganesh KJ, Cai W, Ferreira PJ, et al. Carbon-based supercapacitors produced by activation of graphene. Science 2011;332(6037):153741. El-Kady MF, Strong V, Dubin S, Kaner RB. Laser scribing of high-performance and exible graphene-based electrochemical capacitors. Science 2012;335(6074):132630. Zhang K, Ang BT, Zhang LL, Zhao XS, Wu J. Pyrolyzed graphene oxide/resorcinol-formaldehyde resin composites as high-performance supercapacitor electrodes. J Mater Chem 2011;21(8):266370. Seredych M, Chen R, Bandosz TJ. Effects of the addition of graphite oxide to the precursor of a nanoporous carbon on the electrochemical performance of the resulting carbonaceous composites. Carbon 2012;50(11): 41444154. Tai Z, Yan X, Lang J, Xue Q. Enhancement of capacitance performance of exible carbon nanober paper by adding graphene nanosheets. J Power Sources 2012;199:3738. Lei Z, Zhang J, Zhao XS. Ultrathin MnO2 nanobers grown on graphitic carbon spheres as high-performance asymmetric supercapacitor electrodes. J Mater Chem 2012;22(1): 15360. Zhang L, Zhang F, Yang X, Long G, Wu Y, Zhang T, et al. Porous 3D graphene-based bulk materials with exceptional high surface area and excellent conductivity for supercapacitors. Sci Rep 2013;3:1408. Hummers Jr WS, Offeman RE. Preparation of graphitic oxide. J Am Chem Soc 1958;80(6):1339.

[35] Stankovich S, Dikin DA, Piner RD, Kohlhaas KA, Kleinhammes A, Jia Y, et al. Synthesis of graphene-based nanosheets via chemical reduction of exfoliated graphite oxide. Carbon 2007;45(7):155865. [36] Li D, Muller MB, Gilje S, Kaner RB, Wallace GG. Processable aqueous dispersions of graphene nanosheets. Nat Nanotechnol 2008;3(2):1015. [37] Bai Y, Rakhi RB, Chen W, Alshareef HN. Effect of pH-induced chemical modication of hydrothermally reduced graphene oxide on supercapacitor performance. J Power Sources 2013;233:3139. [38] Zhou Y, Bao Q, Tang LAL, Zhong Y, Loh KP. Hydrothermal dehydration for the green reduction of exfoliated graphene oxide to graphene and demonstration of tunable optical limiting properties. Chem Mater 2009;21(13):29506. [39] Yu L, Falco C, Weber J, White RJ, Howe JY, Titirici M-M. Carbohydrate-derived hydrothermal carbons: a thorough characterization study. Langmuir 2012;28(33):1237383. [40] Puziy AM, Poddubnaya OI, Socha RP, Gurgul J, Wisniewski M. XPS and NMR studies of phosphoric acid activated carbons. Carbon 2008;46(15):211323. [41] Arrigo R, Vecker MH, Wrabetz S, Blume R, Lerch M, McGregor J, et al. Tuning the acid-base properties of nanocarbons by functionalization via amination. J Am Chem Soc 2010;132(28):961630. [42] Shu C-K. Degradation products formed from glucosamine in water. J Agric Food Chem 1998;46(3):112931. [43] Jun M, Shao Y, Ho C-T, Koetter U, Lech S. Structural identication of nonvolatile dimerization products of glucosamine by gas chromatographymass spectrometry, liquid chromatographymass spectrometry, and nuclear magnetic resonance analysis. J Agric Food Chem 2003;51(21):63406. [44] Sun L, Wang L, Tian C, Tan T, Xie Y, Shi K, et al. Nitrogendoped graphene with high nitrogen level via a one-step hydrothermal reaction of graphene oxide with urea for superior capacitive energy storage. RSC Adv 2012;2(10):4498506. [45] Falco C, Perez Caballero F, Babonneau F, Gervais C, Laurent G, Titirici M-M, et al. Hydrothermal carbon from biomass: structural differences between hydrothermal and pyrolyzed carbons via 13C solid state NMR. Langmuir 2011;27(23):1446071. [46] Otowa T, Tanibata R, Itoh M. Production and adsorption characteristics of MAXSORB: high-surface-area active carbon. Gas Sep Purif 1993;7(4):2415. [47] Seredych M, Koscinski M, Sliwinska-Bartkowiak M, Bandosz TJ. Active pore space utilization in nanoporous carbon-based supercapacitors: effects of conductivity and pore accessibility. J Power Sources 2012;220:24352. [48] Wang D-W, Li F, Liu M, Lu GQ, Cheng H-M. 3D Aperiodic hierarchical porous graphitic carbon material for high-rate electrochemical capacitive energy storage. Angew Chem Int Ed 2007;47(2):3736. [49] Stoller MD, Ruoff RS. Best practice methods for determining an electrode materials performance for ultracapacitors. Energy Environ Sci 2010;3(9):1294301. [50] Gu W, Sevilla M, Magasinski A, Fuertes AB, Yushin G. Sulfurcontaining activated carbons with greatly reduced content of bottle neck pores for double-layer capacitors: a case study for pseudocapacitance detection. Energy Environ Sci 2013;6(8):246576. [51] Chmiola J, Yushin G, Dash R, Gogotsi Y. Effect of pore size and surface area of carbide derived carbons on specic capacitance. J Power Sources 2006;158(1):76572.