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PII: S0378-7753(09)02211-3
DOI: doi:10.1016/j.jpowsour.2009.11.138
Reference: POWER 12645
Please cite this article as: K. Karthikeyan, V. Aravindan, S.B. Lee, I.C. Jang, H.H.
Lim, G.J. Park, M. Yoshio, Y.S. Lee, Electrochemical Performance of Carbon-Coated
Li2 MnSiO4 /Activated Carbon for an Asymmetric Hybrid Supercapacitor, Journal of
Power Sources (2008), doi:10.1016/j.jpowsour.2009.11.138
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Supercapacitor
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K. Karthikeyana, V. Aravindanb, S.B. Leea, I.C. Janga, H.H. Lima,
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G.J. Parkc, M. Yoshioc, and Y.S. Leea, *
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Faculty of Applied Chemical Engineering, b The Research Institute for Catalysis,
material presents a well developed orthorhombic crystal structure with a Pmn21 space
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group, although there is a small impurity of MnO. The maximum specific capacitance
This cell delivers a specific energy as high as 54 Whkg-1 at a specific power of 150
Wkg-1 and also exhibits an excellent cycle performance with more than 99 % columbic
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carbon; Organic electrolyte.
* Corresponding author. Tel.: +82 62 530 1904; Fax: +82 62 530 1909.
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1. Introduction
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Electrochemical capacitors (ECs) as energy storage devices are garnering much
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attention due to their higher power densities relative to batteries and conventional
capacitors. Such ECs have been widely used in many electric applications, including
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uninterruptible power supplies, portable devices, hybrid electric vehicles (HEV), and
fuel cells [1-2]. Recently, many studies have focused on asymmetric hybrid
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supercapacitors possessing increased energy density over electrochemical capacitors. It
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is well known that a useful approach to develop hybrid supercapacitors is the transition
voltage and the high energy density of the battery material result in a significant
research groups have reported that fabrication of hybrid capacitors with lithium metal
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oxides as the electrode is drawing increased attention given their high specific energy
[3-5].
lithium ion batteries have recently generated much interest for their intrinsic stability
and natural abundance [6-7]. In the case of Li2MnSiO4, the extraction of more than one
lithium ion is possible, resulting in the higher Mn oxidation state (Mn4+) that favors
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formation of the MnIVSiO4 phase during the delithiation process. Provided that the
structure of this compound is stable, a reversible exchange of up to two lithium ions per
formula unit (exploration of MnII/MnIII and MnIII/MnIV redox couples) would become
possible. Sofar, few works has been reported for the utilization of Li2MnSiO4 as positive
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electrode material in lithium secondary batteries [6, 7]. So far, there is no proper
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optimization has been reported for the synthesis of Li2MnSiO4, which leads to the
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debatable results. For example, Kokalj et al. [8] reported the discharge capacity
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exceeding 200 mAh/g and poor life cycle, which was observed sporadically.
Nevertheless, Liu et al. [9] reported the Li2MnSiO4/C electrodes and it exhibited the
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discharge capacity around 125 mAh/g only. In this context, we optimized the
appropriate synthesis condition for Li2MnSiO4 by solid state route with good cycle life.
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However, it is also well known that the Li2MnSiO4 material still requires more
intensive study before being adopted as a cathode material for a practical lithium ion
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battery, due in part to the low practical capacity and very poor cyclability in the full
working voltage region (4.8-1.5 V). Therefore, we focused on one interesting factor of
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the Li2MnSiO4 material that shows excellent cycle retention in the lower voltage region
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(0–3 V), even though the discharge capacity is very small and difficult to use for the
lithium secondary battery. To our best knowledge, no other work has reported upon the
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applications.
In this work, we firstly report the development of the Li2MnSiO4 material as the
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2. Experimental
state method. High purity LiOH (Junsei, Japan), MnCO3 (Aldrich, USA), and SiO2
(Junsei, Japan) were used as starting materials. Adipic acid (C6H10O4, Dae-Jung, Korea)
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was used as a carbon source material (0.2 mol against the total metal ions present in the
compound). Stoichiometric amounts of starting materials with adipic acid were ground
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and heated at 400 oC for 4 h in air. After cooling down to room temperature, the
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mixtures were ground and finally calcined at 900 oC for 12 h under an argon atmosphere.
The carbon content of the resulting carbon-coated Li2MnSiO4 material (0.52 wt%) was
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determined using an elemental analyzer (CHN Flash EA series, CE Instruments, Italy).
Brunauer, Emmett, and Teller (BET) surface area measurements were made by a
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specific surface area of the Li2MnSiO4 and activated carbon was 0.282 and 1676 m2g-1,
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with an assembled CR 2032 coin type cell. The positive electrode was prepared by
mixing 70% Li2MnSiO4, 20 % ketjen black (KB) as the conductive additive, and 10 %
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Teflonized acetylene black (TAB) as the binder. This was then pressed on 200 mm-2
stainless steel meshes that acted as the current collector. The negative electrode was also
TAB. The mass ratio of the cathode to anode was approximately 2:1. The LMS/AC cell
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LiPF6/EC:DMC (Vol 1:1) electrolyte. The cyclic voltammogram study of the LMS/AC
– 3 V and at a current density of 1 mAcm-2 using a cycle tester (WBCS 3000, Won-A-
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Tech, Korea).
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3. Results and Discussion
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Fig. 1 presents the XRD pattern of the prepared LMS power. The peaks observed
were assigned to the Li2MnSiO4 phase, which had an orthorhombic crystal structure
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with a Pmn21 space group [10]. However, additional peaks were observed in the
diffractrogram and identified with MnO (ICSD-76086). There were some low intensity
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peaks possibly originating from the presence of Li and Mn silicate, as reported by
Fig. 2 shows the cyclic voltammogram (CV) results of the LMS/AC cell
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investigate the ideal capacitive behavior of the electrochemical system. All curves
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exhibit rectangular mirror like images with respect to the zero-current line and a rapid
current response on voltage reversal at each end potential. This implies that the hybrid
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V. From the CV curves, the potential difference between the peaks increased with scan
rates, indicating the presence of the electric polarization phenomenon. Upon increasing
the scan rate, the electric polarization phenomena became more serious. The possible
energy storage mechanism of the LMS/AC is as follows: the AC cathode forms double
layers to store energy while the Li2MnSiO4 anode exploits the intercalated/extracted Li+
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ions to produce pseudocapacitance and realize storage of energy. During the charge
process, Li+ ions are extracted from the Li2MnSiO4 electrode, adhering on the surface of
state, the Li+ ions de-adsorb from the AC surface and intercalate into Li2MnSiO4
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electrode via the electrolyte.
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Fig. 3(a) shows the galvanostatic charge/discharge curves of the LMS/AC cell
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at a constant current density of 1 mAcm-2 between 0 and 3 V. The discharge profile
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generally consists of three parts: a small voltage drop (IR drop) due to the internal
Li2MnSiO4 battery material in the longer time region. The results showed that the
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hybrid system exhibited a combination of a double layer capacitor and battery
characteristics. It can be seen from the charge/discharge curves that the potential is
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linearly varied with time during charge and discharge with a constant slope for the
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that the LMS/AC cell has excellent cycle performance and high electrochemical
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current density. Fig. 3(b) shows that this hybrid supercapacitor exhibits an excellent
cycle life with a specific capacitance maintaining over 85% of its initial value after 1000
cycles. The coulombic efficiency ( ) of the LMS/AC cell is also shown in Fig. 3(b),
which was calculated according to the equation: = ( tD/ tC) x 100, where, tD and tC
are the discharge and charge times, respectively. The hybrid cell showed a very stable
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For the comparison, electrochemical performances of Li2MnSiO4 vs lithium
reference electrode was fabricated and described in figure 4. The cycling performances
were carried out between 0-3 V at ambient temperature. The Li2MnSiO4/Li cell
exhibited the initial discharge capacity of 482 mAh/g. During the second discharge, the
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capacity drastically reduced to 181 mAh/g in the same conditions described above. The
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irreversible capacity may be due to the formation solid electrolyte interface during the
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cycling process [13-15]. In addition, the Li2MnSiO4 material presented a reasonable
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cycling profile, when using metallic lithium as reference electrode.
gradually with increasing current density. The specific capacitance is decreased from
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43.2 to 29.6 Fg-1 at a current density from 1 to 10 mAcm-2. The reason for capacitance
loss at high current densities could be mainly from two aspects: (a) a large IR drop at
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higher current densities leads to small capacitance values; (b) activation and
active materials. Table 1 clearly reveals that the LMS/AC hybrid supercapacitor
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exhibited a high charge/discharge rate capability, a high specific energy, and stable
4. Conclusion
activated carbon as the positive electrode in 1.0 M LiPF6/EC:DMC electrolyte has been
developed. To our best knowledge, this is the first report on the assembly of an
asymmetric supercapacitor with Li2MnSiO4 as the electrode material for the hybrid
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supercapacitor. The initial specific capacitance obtained from the charge/discharge
curve was 43.2 Fg-1 at a 1 mAcm-2 current density. The specific capacitance that
decreased slightly with increasing current density revealed that the LMS/AC cell has a
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approximately 85 % of its initial capacitance value and exhibited a good cycleability
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with high coulombic efficiency greater than 99 %, even after 1000 cycles.
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Acknowledgements
This work was supported by the Korea Research Foundation Grant funded by the
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Korean Government (MOEFRD) (KRF-2007-412-J02003).
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References
[1] B.E. Conway, in: A. Chen, M.Q. Wu, X.L. Zhang, N.W. Gao (Eds.),
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[2] R. Kotz, M. Carlen, Electrochim. Acta 45 (2000) 2483 - 2498.
[3] S.B. Ma, K.W. Nam, W.S. Yoon, X.Q. Yang, K.Y. Ahn, K.H. Oh, K.B. Kim,
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Electrochem. Commun. 9 (2007) 2807-2811.
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[4] Y. Zhao, Y.Y. Wang, Q.Y. Lai, L.M. Chen, Y.J. Hao, X.Y. Ji, Synt. Mater. 159
(2009) 331-337.
[5]
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J.Y. Luo, Y.Y. Xia, J. Power Sources 186 (2009) 224-227.
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[13] I. Plitz, A. Dupasquier, F. Badway, J. Gural, N. Pereira, A. Gmitter, G.G.
[15] N. Kalaiselvi, C.H. Doh, C.W. Park, S.I. Moon, M.S. Yun, Electrochem.
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Commun. 6 (2004) 1110-1113
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Figure Captions
Fig. 3. (a) Charge/discharge curves of the LMS/AC cell; (b) Discharge capacitance and
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coulombic efficiency as a function of cycle numbers at a 1 mAcm-2 current density.
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Fig. 4. Electrochemical performance of Li2MnSiO4/Li cell (a) charge-discharge and (b)
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cycling profile
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Table(s) 1
Table 1
Specific capacitance (Cs) and specific energy (E) and power (P) densities of LMS/AC
cell at various current densities.
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Current density CS (F/g) E (Wh/kg) P (W/kg)
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(mA/cm )
1 43.2 54 150
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2 34.8 43 300
4 33.5 41 600
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6 32 40 900
8 30.6 38 1200
10 29.6 an 37 1500
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Figure(s) 1-4
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