Res Chem Intermed (2010) 36:591602 DOI 10.

1007/s11164-010-0167-9

Preparation and characterization of electrospun LiFePO4/carbon complex improving rate performance at high C-rate
Sei-Hyun Lee Min-Jung Jung Ji Sun Im Kyou-Yoon Sheem Young-Seak Lee

Received: 15 December 2009 / Accepted: 6 February 2010 / Published online: 18 September 2010 Springer Science+Business Media B.V. 2010

Abstract LiFePO4/carbon complexes were prepared by electrospinning to improve rate performance at high C-rate and their electrochemical properties were investigated to be used as a cathode active material for lithium ion battery. The LiFePO4/carbon complexes were prepared by the electrospinning method. The prepared samples were characterized by SEM, EDS, XRD, TGA, electrometer, and electrochemical analysis. The LiFePO4/carbon complexes prepared have a continuous structure with carbon-coated LiFePO4 and the LiFePO4 in LiFePO4/carbon complex has improved thermal stability from carbon coating. The conductivity of LiFePO4/carbon complex heat-treated at 800 C is measured as 2.23 9 10-2 S cm-1, which is about 106107 times more than that of raw LiFePO4. The capacity ratio of coin cell manufactured from raw LiFePO4 is 40%, whereas the capacity ratio of coin cell manufactured from LiFePO4/carbon complex heat-treated at 800 C is 61% (10 C/0.1 C). The improved rate performance of LiFePO4/carbon complex heat-treated at 800 C is due to the carbon coating and good electrical connection. Keywords High C-rate Rate performance LiFePO4/carbon complex Electrospinning

S.-H. Lee Department of Electrical and Electronic Engineering, Korea Polytechnic College, Daejeon 300-702, Republic of Korea M.-J. Jung J. S. Im Y.-S. Lee (&) Department of Applied Chemistry and Biological Engineering, Chungnam National University, Daejeon 305-764, Republic of Korea e-mail: youngslee@cnu.ac.kr K.-Y. Sheem Energy Lab., CRD Center, Samsung SDI, Suwon, Gyeonggi-do 443-390, Republic of Korea

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Introduction Recently, lithium-ion batteries have drawn an interest to be used for electric vehicles (EVs), hybrid electric vehicles (HEVs), dispersed energy storage systems, etc. [1]. Such applications require safety, high-rate performance, and energy density [2]. Especially good rate performance at high C-rate is essential for batteries of electric vehicles [3]. Lithium-ion batteries consist of a cathode, an anode, and an electrolyte. Among several components of the lithium-ion batteries, cathode materials are a major concern for the improvement of rate performance at high C-rate. Cobalt or manganese-based oxides, such as LiCoO2 and Li2MnO4, are generally used as cathode materials of commercial lithium-ion batteries. The cobalt-based oxides have disadvantages of high cost and toxicity [4], whereas manganese-based oxides have advantages of low cost and low toxicity. However, they suffer from important capacity fading during cycling, especially at high temperatures [5]. Since the study of Padhi et al. [6], the olivine structure of lithium iron phosphate (LFP, LiFePO4) has attracted great interest as a substitute for conventional cathode materials. It has many advantages of high energy density, high theoretic capacity, low cost, safety, and environmental friendliness [7]. However, LiFePO4 has poor conductivity. This disadvantage results from the low lithium-ion diffusion rate and low electronic conductivity in the LiFePO4 phase. In order to improve the electronic conductivity of LiFePO4, some methods have been studied, including coating conductive carbon [810] or metals [1113] on LiFePO4 surface or doping ions in the crystalline lattice of LiFePO4 [1416]. Above all, the carbon-coating method is very efcient in increasing conductivity of LiFePO4 due to high electronic conductivity of carbon, and the increase of the electronic conductivity of LiFePO4 surface is expected to provide a good rate performance at high C-rate [1719]. The LiFePO4/carbon complex has been prepared by the solgel method, hydrothermal method, freezedrying method, spray-pyrolysis method, etc. [2024]. For improvement of the rate performance at high C-rate, LiFePO4 and carbon must be connected effectively. Therefore, the ameliorated method is necessary to manufacture a well-connected LiFePO4/carbon complex. Electrospinning is well known as a simple and effective method for fabrication of complex [25, 26]. It is expected that LiFePO4/carbon complex is manufactured well-connected form of carbon and LiFePO4. In this study, LiFePO4/carbon complexes for a cathode active material of a lithium-ion battery were prepared by the electrospinning method in order to improve rate performance at high C-rate, and their electrochemical characteristics were also evaluated.

Materials and methods Preparation of LiFePO4/carbon complexes by electrospinning method Carbon precursor, PAN (polyacrylonitrile, mW 80,000, Aldrich, USA) was dissolved in DMF (N,N-dimethyl formamide, Acros, USA) at 80 C, and its concentration was 10 wt%.

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An active material of cathode, LiFePO4 (lithium iron phosphate (LFP), Postech, Korea) was added to PAN solution to produce a mixture solution with a PAN:LiFePO4 ratio of 1:4, and then the solution was spun out of bers with the electrospinning experiment. The electrospinning conditions were as followings; 3 ml/h of solution feeding rate and 15 kV of applied electric power. The details of the electrospinning method have been presented elsewhere [27]. After electrospinning, as-spun bers were stabilized at a temperature of 250 C for 5 h in air with a heating rate of 1 C/min. The stabilized bers were then heated at 600 and 800 C for 1 h in nitrogen atmosphere (heating rate: 10 C/min) to investigate electrochemical property changes with different heat-treatment temperatures. The prepared samples were named as follows; r-LFP (raw LiFePO4), LFP/C600 (LiFePO4/carbon complex heat-treated at 600 C), and LFP/C800 (LiFePO4/carbon complex heattreated at 800 C). Characterizations of LiFePO4/carbon complexes The morphologies of the samples were observed with eld emission scanning electron microscope (SEM, S-5500, Hitachi, Japan). Elemental mapping was carried out with energy dispersive spectroscopy (EDS) images. Crystal structures of samples were investigated by X-ray diffraction (XRD, D/MAX-2200 Ultima/PC, Rigaku International Corporation, Japan) with a Cu cathode (CuKa radiation ) at room temperature. Carbon content was evaluated by the k = 1.54056 A thermogravimetric analysis (TGA, 2960SDT, TA Instruments, USA) in air and nitrogen from room temperature to 600 C with a heating rate of 5 C min-1. The conductivity of LiFePO4/carbon complexes was measured in air at ambient temperature with an electrometer (6514 system electrometer, Keithley, USA). Electrochemical analysis of LiFePO4/carbon complex LiFePO4/carbon complex electrodes were fabricated by mixing the prepared electrospun LiFePO4/carbon complex (80 wt%) and polyvinylidene uoride (PVDF, Aldrich) binder (20 wt%). LiFePO4 electrode was fabricated by mixing r-LFP (70 wt%), PVDF (20 wt%), and carbon black (10 wt%, Super-P, MMM Carbon) as a conductive material. The disc electrodes, having a diameter of 16 mm, were cut out of the coating lm and cast onto metal foil current collector using a punch. The coin half cells (CR2016 standard size) were assembled in an argon-lled glove box at room temperature. The electrolyte was prepared by mixing ethylene carbonate (EC, Aldrich), ethyl methyl carbonate (EMC, Aldrich), and dimethyl carbonate (DMC, Aldrich) with a ratio of EC:EMC:DMC = 3:3:4 to assemble the coin cells. Electrochemical investigations were performed by using a CC/CV mode. The coin cells were named as follows; C-rLFP (coin cell manufactured from r-LFP), CLC600 (coin cell manufactured from LFP/C600), and C-LC800 (coin cell manufactured from LFP/C800). The ratio of coin cells with each sample are presented in Table 1.

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594 Table 1 The ratio of coin cells with each sample The ratio of coin cell (wt%) LiFePO4 Conducting material CB C-rLFP C-LC600 C-LC800
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Binder
a

Real weight of LiFePO4 in cell (g)

PBC 8.9 7.8

70.0 71.1 72.2

10.0

20.0 20.0 20.0

0.0060 0.0037 0.0047

PAN-based carbon

Results and discussion Morphology of electrospun LiFePO4/carbon complexes Figure 1 shows SEM images of r-LFP and LiFePO4/carbon complex samples prepared with different heat-treatment temperatures. As shown in Fig. 1a, r-LFP is observed with uniform oval-shaped particles. It conrms many clusters of small particles that have an average particle size with a major axis of about 200 nm. Manufactured LFP/C600 and LFP/C800 by electrospinning (Fig. 1b, c) are brous with a rough surface. The average diameter of LiFePO4/carbon complexes is about 5 0.8 lm. The surfaces of the LiFePO4/carbon complexes become rougher with increasing heat-treatment temperature. The surface of LFP/C800 is more porous than that of LFP/C600 because the PAN shrank during heat-treatment [28]. Since PAN shrinks more at higher heat-treatment temperature [29], LFP/C800 is more

Fig. 1 SEM images of a r-LFP, b LFP/C600, c LFP/C800, d a cross-section of LFP/C600 and e a crosssection of LFP/C800

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porous than LFP/C600. It is expected to have more chances for electrolyte to be absorbed into an internal electrode, improving rate performance. The schematic diagrams of r-LFP, prepared LiFePO4/carbon complex, and electron transfer pathway of the prepared complex in this study is suggested in Fig. 2. r-LFP is observed as a form of clusters, without any connection between each LiFePO4 particle. However, LiFePO4/carbon complexes are observed as a continuous structure with LiFePO4 particles coated and linked with PAN-based carbon. As shown in the cross section of LiFePO4/carbon complexes (Fig. 1d, e), it is also observed that LiFePO4 particles are dispersed uniformly in LiFePO4/carbon complex and coated and connected with carbon. In addition, LiFePO4/carbon complexes have a high-density ber structure due to the effect of the electrospinning method. As shown in Fig. 2b, these carbon coatings and connections ensure that LiFePO4 particles get electrons effectively, and could further alleviate this polarization phenomenon [30]. In the EDS images (Fig. 3), carbon is observed as white spots on the surface of LiFePO4/carbon complexes. This can be another evidence for the existence of carbon coating on the LiFePO4/carbon complex surface. XRD analysis Figure 4 shows the XRD patterns of r-LFP and LiFePO4/carbon complexes. The XRD pattern of r-LFP (Fig. 4a) is identied as an orthorhombic system in Pnma space group (JCPDS card No. 81-1137) and it is almost similar to those of LiFePO4/ carbon complexes (Fig. 4b,c), not showing the presence of crystalline carbon. It is hard to observe the crystalline carbon peak (002) in the XRD patterns of the complexes due to the overlapping of the crystalline carbon peak with LiFePO4 peak (111). According to previous studies [31], XRD pattern of LiFePO4/carbon complex treated at 800 C exhibited the impurity peaks caused by reduction of LiFePO4, such as Fe2P (22, 23) or Li3PO4 (41, 44). The presence of impurities causes the decrease of ionic conductivity, capacity, and cycling rates [3234]. In this study, structural changes of LiFePO4 are not observed in the XRD patterns of the LiFePO4/ carbon complexes (Fig. 1b, c). This result suggests that carbon coating contributes to increasing thermal stability of LiFePO4. It is expected that electrochemical properties of LiFePO4 in LiFePO4/carbon complexes are not affected by impurities.

Fig. 2 The schematic diagrams of a r-LFP, b prepared LiFePO4/carbon complex, and c electron transfer pathway of the LiFePO4/carbon complex

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Fig. 3 EDS images of a LFP/C600, b LFP/C800, c C mapping of LFP/C600, and d C mapping of LFP/ C800

111

101

020

(c)
200

311 121 410 102, 221 112 321, 212

LiFePO4
022 131 231 412, 610 331 430 040 213 701 313

Intensity (a. u.)

(b)

(a)

20

210 011

30

301

40

50

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2 (Degree)
Fig. 4 X-ray diffraction patterns of (a) r-LFP, (b) LFP/C600, and (c) LFP/C800

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TGA and electrical conductivity analysis Figure 5 shows TGA curves of r-LFP, LiFePO4/carbon complexes, and PAN-based electrospun carbon ber under air ow, and stabilized electrospun PAN ber under N2 ow. As shown in the TGA curve of r-LFP (Fig. 5a), it is observed that oxidation of r-LFP started at around 250 C. As it has been previously reported by Belharouak [35], r-LFP is oxidized with two steps of weight increment and formatted two phases, Li3Fe2(PO4)3 and Fe2O3. In addition, the TGA curve shows a weight gain of 2.2% for the r-LFP after oxidation. As shown in Fig. 4b and c, LiFePO4 in LiFePO4/ carbon complexes is also oxidized at or above 400 C. The LiFePO4 oxidation peak of LFP/C600 and LFP/C800 is shifted to a higher temperature than that of r-LFP, which means that the carbon coating will be able to delay oxidation of LiFePO4 and

(a)
Residual mass (%)

100 80 60

(b)
(1)

40 20 0 100

(2) (3) (4) (5)

200 300 400 500
o

600

700

800

Temperature (C )

(b) 105
Residual mass (%)
100

95

90

(1) (2) (3)

85 100 200 300 400

o

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600

Temperature (C )
Fig. 5 TGA results of prepared samples (a) and expansion of selected area (b); (1) r-LFP observed in air, (2) LFP/C600 observed in air, (3) LFP/C800 observed in air, (4) PAN-based electrospun carbon ber observed in air, and (5) stabilized electrospun PAN ber in observed nitrogen

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improve thermal stability. The improved thermal stability of active material is a very important factor to determine the safety of Li-ion batteries. This result is similar to XRD patterns of the LiFePO4/carbon complexes, where no structural changes of LiFePO4 were observed. Below 400 C, the weight loss of LFP/C800 is faster than that of LFP/C600 because LFP/C800 is more porous than LFP/C600, as explained above. Rapid weight loss of LFP/C600 and LFP/C800 is observed at around 400 and 450 C, respectively. The starting temperature of rapid weight loss of LiFePO4/carbon complexes increases with increasing heat-treatment temperature. Weight loss of LiFePO4/carbon complexes occurs because of decomposition of existing carbon in LiFePO4/carbon complexes. It is also observed in TGA curve of PAN-based electrospun carbon ber (Fig. 5d). A weight loss of LiFePO4/carbon complexes is associated with oxidation of carbon and some organic compounds, which means that carbon contents of the LiFePO4/C complex can be calculated from weight loss of the complex and the amount of carbon coated on the LFP/C600 and LFP/C800 is calculated to be around 11.1 and 9.8 wt%, respectively. The carbon amount of LiFePO4/carbon complexes is calculated theoretically using TGA curve of stabilized electrospun PAN ber. According to the TGA curve of stabilized electrospun PAN ber (Fig 5e), the carbon yield of PAN in LFP/C600 and LFP/ C800 is estimated to be around 43.5 and 34.7 wt%, respectively. The theoretical amount of carbon coated on the LFP/C600 and LFP/C800 is calculated to be around 9.8 and 7.9 wt%, respectively. Even though LFP/C600 contains a larger percentage of carbon than LFP/C800, crystallinity of carbon in LFP/C800 would be higher than that of carbon in LFP/ C600 because crystallinity and conductivity of carbon increases with increasing heat-treatment temperature [36]. Therefore, it is expected that conductivity of LFP/ C800 has higher than that of LFP/C600. Actually, the conductivity of LFP/C600 and LFP/C800 is measured at 5.62 9 10-4 and 2.23 9 10-2 S cm-1, respectively. LFP/ C800 has improved conductivity about 40 times more than LFP/C600. Therefore, it suggests that increasing the heat-treatment temperature in this experiment led to an increase in the conductivity. Compared to low electrical conductivity of LiFePO4 about 10-910-10 S cm-1 [37], conductivity of LFP/C800 is considerably increased about 107108 times. As each LiFePO4 particle is coated with carbon, a conductive network is formed between the LiFePO4 particles. Therefore, conductivity of the material can dramatically increase. It is expected to improve rate performance at a high C-rate. Electrochemical performance Figures 6, 7, 8, and 9 and Table 2 show the discharge proles of the coin cells measured from 4.5 and 2.0 V vs. Li at different discharge rates of 0.1, 1, 5, and 10 C. The cells are cycled between 2.4 and 4.1 V. In case of C-LC600, it shows a poor electrochemical property with the discharge capacities of 0.08 mAh g-1 at 0.1 C, which is much lower than the discharge capacities of C-rLFP, 153.18 mAh g-1 at 0.1 C. This is the conductivity difference between conductive materials used for cell manufacturing. C-rLFP was manufactured with carbon black as a conductive

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Preparation and characterization of electrospun LiFePO4/carbon complex Fig. 6 The discharge curves at 0.1 C

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4.0

Voltage (V vs. Li/Li )

3.6 3.2 2.8 2.4 0 20 40 60

C-rLFP C-LC600 C-LC800

80 100 120 140 160

-1

Capacity (mAh g )
Fig. 7 The discharge curves at 1 C

4.0

Voltage (V vs. Li/Li )

3.6 3.2 2.8 2.4 0 20 40 60

C-rLFP C-LC600 C-LC800

80 100 120 140 160

-1

Capacity (mAh g )

Fig. 8 The discharge curves at 5 C

4.0

Voltage (V vs. Li/Li )

3.6 3.2 2.8 2.4 0 20 40 60 80

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C-rLFP C-LC600 C-LC800

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Capacity (mAh g )

material, which usually has a conductivity of 10-1102 S cm-1 [38], whereas C-LC600 was manufactured with heat-treated PAN bers at 600 C, which has a measured conductivity of 3.34 9 10-3 S cm-1. Therefore, due to the low conductivity of heat-treated PAN ber at 600 C, the conductivity of C-LC600 is

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600 Fig. 9 The discharge curves at 10 C

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4.0

Voltage (V vs. Li/Li )

3.6 3.2 2.8 2.4 0 20 40 60

-1

C-rLFP C-LC600 C-LC800

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Capacity (mAh g )

Table 2 Discharge capacity with different discharge rate

Discharge capacity (mAh g-1) 0.1 C C-rLFP C-LC600 C-LC800 153.18 0.08 139.95 1C 146.23 0.04 112.23 5C 105.12 0.03 93.52 10 C 61.06 0.03 85.60

expected to be signicantly lower than that of C-rLFP, causing low discharge capacity of C-LC600. The low conductivity of heat-treated PAN ber at 600 C is due to the presence of a large amount of amorphous carbon in the ber heat-treated at relatively low temperature and the amorphous carbon obstructs movement of lithium ion inside of the active materials. The discharge capacities of C-rLFP are 153.18 mAh g-1 (0.1 C) and 61.06 mAh -1 g (10 C), and the capacity ratio of 10 C/0.1 C is 40%. In case of C-LC800, discharge capacities are 139.95 mAh g-1 (0.1 C) and 85.60 mAh g-1 (10 C), and the capacity ratio of 10 C/0.1 C is 61%. The high rate performance reveals that the LiFePO4/carbon complex would be suited for cathode material of a high-power lithium-ion battery. The high rate performance in the high discharge rate condition is attributed to dramatic conductivity improvement through carbon coating and connecting. At a high discharge rate, the lithium ion diffusion is restricted inside of active materials [5]. For this reason, discharge capacity and rate performance of cell is greatly inuenced by surface conductivity of active materials and connection of active materials at high discharge rate. There are continuities between restricting of lithium-ion diffusion and change of the voltage plateau region [5]. As Figs. 6, 7, 8, and 9 show, the voltage plateau of C-rLFP is changed dramatically with increasing discharge rate. However, the C-LC800 has an excellent at voltage plateau around 3.23.4 V in most discharge rates. This effect can be attributed to the improved lithium-ion diffusion at active material surface, due to the carbon coating and connecting.

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Conclusions Electrospun LiFePO4/carbon complexes are manufactured as high dense bers with continuous structure of LiFePO4 particles which are linked with PAN-based carbon coating. In this study, structural changes of LiFePO4 are not observed in the XRD patterns of LiFePO4/carbon complexes. As shown in the TGA curves, the LiFePO4 oxidation peak of LiFePO4/carbon complexes are shifted to higher temperatures than that of r-LFP. These results suggest that carbon coating contributes to increasing thermal stability of LiFePO4. The amount of carbon coated on the LFP/ C600 and LFP/C800 is calculated to be around 11.19.8 wt%, respectively, from TGA curves. The conductivity of LFP/C600 and LFP/C800 is measured to be 5.62 9 10-4 and 2.23 9 10-2 S cm-1, respectively. Even though LFP/C600 contains a larger percentage of carbon than LFP/C800, crystallinity of carbon in LFP/ C800 would be higher than that of carbon in LFP/C600 because of crystallinity and conductivity of carbon increase with increasing heat-treatment temperature. Therefore, conductivity of LFP/C800 is higher than that of LFP/C600. The discharge capacities of C-rLFP are 153.18 mAh g-1 (0.1 C) and 61.06 mAh g-1 (10 C), and the capacity ratio of 10 C/0.1 C is 40%. In case of C-LC800, discharge capacities are 139.95 mAh g-1 (0.1 C) and 85.60 mAh g-1 (10 C), and the capacity ratio of 10 C/0.1 C is 61%. The improved rate performance of C-LC800 can be explained with increased conductivity of active materials and network between active materials caused by carbon coating and connecting.
Acknowledgments This work was partially supported by Samsung SDI, Korea.

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