Anda di halaman 1dari 4

www.advenergymat.

de
www.MaterialsViews.com

COMMUNICATION

Disodium Terephthalate (Na2C8H4O4) as High Performance


Anode Material for Low-Cost Room-Temperature
Sodium-Ion Battery
Liang Zhao, Junmei Zhao, Yong-Sheng Hu* Hong Li, Zhibin Zhou, Michel Armand,
and Liquan Chen
In the field of energy storage, lithium (Li)-ion batteries dominate
the portable consumer electronic market because of their high
energy density. Recently, however, the sodium (Na)-ion battery
has again aroused interest for large-scale energy storage due to
Na abundance.[16] Conventionally, the chemistry behind Li-ion
and Na-ion batteries involves transition metal elements,[4,6] thus
giving rise to problems of cost and environmental concern.
Therefore, intensive efforts have been aimed at the development
of new Li storage materials shifting from inorganic to organic
compounds.[7] Numerous advantages exist in using organic
materials as electrodes for energy storage, such as their tremendous chemical compounds, the tuning of the redox potential in
a wide range, possible multi-electron reactions, the abundant
resources from biomass, and ease in recycling.[712] A number
of Li-containing organic compounds have been demonstrated
to have high lithium storage capacity, good cycleability, and
moderate rate capability, making them promising applications
in Li-ion batteries.[7,1012] However, there is no report on the use
of such organic compounds in Na-ion batteries.
In this contribution, a carboxylate-based organic material,
disodium terephthalate (Na2C8H4O4), is introduced as a novel
anode material for low-cost room-temperature Na-ion batteries. To the best of our knowledge, this is the first time that
an organic compound is reported for the use as an anode material for Na-ion batteries. This material exhibits a low Na insertion voltage at 0.29 V vs. Na+/Na and a high reversible capacity
of 250 mAh/g with excellent cycleability. It is found that Na

L. Zhao, Profs. Y.-S. Hu, H. Li, M. Armand, L. Q. Chen


Key Laboratory for Renewable Energy
Beijing Key Laboratory for New
Energy Materials and Devices
Beijing National Laboratory for Condensed Matter Physics
Institute of Physics
Chinese Academy of Sciences
Beijing 100190, China
E-mail: yshu@aphy.iphy.ac.cn
Dr. J. M. Zhao
Key Laboratory of Green Process and Engineering
Institute of Process Engineering
Chinese Academy of Sciences
Beijing 100190, China
Prof. Z. B. Zhou
School of Chemistry and Chemical Engineering
Huazhong University of Science and Technology
Wuhan 430074, China

DOI: 10.1002/aenm.201200166

962

wileyonlinelibrary.com

storage performance can be further improved by a thin layer of


Al2O3 coating on the Na2C8H4O4 electrode surface.
Scheme 1 shows the molecular structure of Na2C8H4O4.
The existence of two carbonyl groups allows for the insertion
and deinsertion of two Na ions, corresponding to a theoretical
capacity of 255 mAh/g. In order to confirm the purity of the
as-received Na2C8H4O4, nuclear magnetic resonance (NMR),
Fourier transform infrared spectroscopy (FTIR), and X-ray diffraction (XRD) measurements were performed. Both NMR and
FTIR results as shown in Figures S1 and S2 reveal the high
purity of the sample. The Na2C8H4O4 has an orthorhombic
structure and can be indexed in space group Pbc21, according
to JCPDS card No. 00-052-2146 (Figure S3).[13] The lattice
constants of Na2C8H4O4 are a = 3.5480 , b = 10.8160 , and
c = 18.9943 , and its lattice volume is V = 728.92 3. The
XRD pattern of as-received Na2C8H4O4 showed preferentially
oriented (006) and (008) planes. Thus, refining the structure is
difficult. This can be evidenced by the scanning electron microscopy (SEM) image in Figure 1b, where the as-received sample
is shown to have a flake-like structure with very large size near
100 m. To reduce the particle size and increase electronic conductivity, the sample was ball-milled with 20 wt.% Ketjen black
(KB). After ball-milling, the particle size decreases to 50 nm to
600 nm, which is responsible for the broadening of the XRD
pattern (Figure 1a). Moreover, the preferential orientation
of the (006) and (008) planes of the ball-milled sample disappears. The transmission electron microscopy (TEM) image in
Figure 1c shows that the particles are surrounded by KB and
that the sample is also porous, resulting in the formation of a
mixed conducting network for both electron and ion transport.
The electrochemical performance of Na2C8H4O4 was tested
at a voltage range of 0.1 V to 2 V vs. Na+/Na at a current rate
of 0.1 C (0.1 C refers to 2 mol Na insertion into Na2C8H4O4
per formula unit in 10 h). The dischargecharge curves for the
first 10 cycles are shown in Figure 2. During the initial discharge process, the voltage sharply dropped to 0.7 V, following
a sloped range between 0.7 and 0.23 V with a capacity of about
200 mAh/g. A flat plateau was then observed at 0.29 V with a
capacity of 270 mAh/g, in accordance with two Na insertion
(255 mAh/g). The charge plateau was located at 0.56 V, and the
initial coulombic efficiency was 50.3%. In contrast, in its counterpart Li2C8H4O4/Li cell,[12] the dischargecharge plateaus were
located at higher values of 0.8 and 1.0 V. The factor contributing to this large difference is unknown at present, but may be
related to the mutual electrostatic repulsion of bulky Na+ ions.
The low coulombic efficiency in the first scan is mainly resulted

2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

Adv. Energy Mater. 2012, 2, 962965

www.advenergymat.de
www.MaterialsViews.com

COMMUNICATION

Scheme 1. Molecular structure of disodium terephthalate (Na2C8H4O4)


and the Na insertion/deinsertion mechanism.

from the large irreversible capacity of the sloped region, which


disappears in subsequent cycles. For comparison, the nonball-milled sample also delivered an irreversible capacity of
75 mAh/g in the sloped region of the first discharge process,
as shown in Figure S4. This value is significantly lower than
that of the Na2C8H4O4/KB composite electrode, but still noticeable. The large irreversible capacity indicates the formation of a
solid electrolyte interphase (SEI).[5] Figure S5 presents the TEM
image of electrodes after discharging to 0.01 V. Compared with
Figure 1c, the active material and KB can no longer be distinguished, and the electrode is surrounded by an amorphous layer.
The large irreversible capacity is attributed mainly to the severe
electrocatalysis of electrolyte reduction by KB and possibly by
Na2C8H4O4 itself. The distinct plateaus could be assumed to
be structural changes from Na2C8H4O4 to Na4C8H4O4 with Na
ions bonding to the two carbonyl groups in Na2C8H4O4 in the
Na insertion process.

Figure 1. Structure characterizations: (a) XRD pattern of the pristine


Na2C8H4O4 and the ball-milled Na2C8H4O4/KB composite; (b) SEM
image of the pristine Na2C8H4O4; and (c) TEM image of the ball-milled
Na2C8H4O4/KB composite.
Adv. Energy Mater. 2012, 2, 962965

Figure 2. The first 10 discharge-charge cycles of the Na2C8H4O4/KB


composite electrode, the voltage range is between 0.1 V and 2 V.

Surface modification of electrode materials is an effective


way to improve the performance of Li-ion batteries.[6,14,15] This
has been achieved in both anode materials, such as natural
graphite[16] and silicon,[17] and high voltage cathode materials,
such as LiMn2O4 and LiCoO2,[16,18] by metal-oxide coating
applied in terms of long term cycling and rate capability.
Among the approaches for surface coating, atomic layer deposition (ALD) is an easy means to form a uniform coating layer on
the surface of active materials.[19] More importantly, the protective metal-oxide coating layer can be applied without disrupting
inter-particle electronic contact through the ALD method.[16]
Here, the Na2C8H4O4 electrode was coated through the ALD
method for 20 cycles ( ca. 2 nm) and 50 cycles ( ca.5 nm).
Figure 3 displays the initial discharge and charge curves of
the electrodes coated by ALD for 20 and 50 cycles (denoted
as ALD20 and ALD50). The capacities of the sloped region

Figure 3. The initial discharge-charge curves of the untreated Na2C8H4O4


electrode and the ALD20 and ALD50 electrodes in the voltage range
between 0.1 V and 2 V; the corresponding coulombic efficiencies are
50.3%, 62.5% and 60.6%, respectively.

2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

wileyonlinelibrary.com

963

www.advenergymat.de

COMMUNICATION

www.MaterialsViews.com

decreased to 159 and 143 mAh/g for the ALD20 and ALD50
electrodes, respectively, with no decrease in reversible capacities. Correspondingly, the initial coulombic efficiencies respectively increased to 62.5% and 60.6% for the ALD20 and ALD50
electrodes. The increased efficiency can be attributed to the fact
that the Al2O3 layer mitigates the formation of SEI on the electrode surface through the reductive decomposition of electrolytes during initial discharge.
Figure 4a, b, and c show the dischargecharge curves of
untreated and Al2O3-coated electrodes at different current
rates. All cells were successively discharged and charged with
increasing current rates from 0.05 C to 2 C for five cycles at
each rate. It is found that the Al2O3-coating is also effective in
improving rate capability (see Figure 4 and S6). For the ALD20
electrode, 91.1%, 86.2%, 64.9%, and 52.8% of the capacity at
0.05 C were still accessible at current rates of 0.1, 0.2, 1, and 2 C,
respectively. In the case of the ALD50 electrode, 91.3%, 87.3%,
67.2%, and 57.0% of the capacity at 0.05 C were achieved, compared with capacity retentions of 87.9%, 80.2%, 52.4%, and
31.5% for the untreated electrode. Moreover, cycling at high
current density does not permanently damage the structure of
the electrode, given that the capacity is restored when the rate is
reduced to a low current rate (0.1 C). As it is well known, Al2O3 is
an insulated coating layer, however, this characteristic is not contradictory to the enhanced rate performance, because the Al2O3
coating layer can reduce the formation of SEI layer on electrode
surface, which results in large impedance; and the Al2O3 coating
layer is also beneficial to the structure maintenance of the electrode. Finally, the cycling performance is also improved after
Al2O3 coating of the electrode (Figure 4d). The untreated electrode presented an initial charge capacity of 258 mAh/g, which
slowly faded to 192 mAh/g after 50 cycles, with a capacity retention of 74.4%. The ALD20 and ALD50 electrodes exhibited initial
charge capacities of 282 and 255 mAh/g, which decayed to 225
and 211 mAh/g, with capacity retentions of 79.8% and 82.7%,
respectively. A thin layer of Al2O3 coating through the ALD technique on the electrode surface has been shown to effectively
improve the performance of inorganic electrodes. This is the
first example to demonstrate the effectiveness of this technique
in enhancing the performance of an organic electrode.
In conclusion, Na2C8H4O4 is firstly introduced as a novel
anode material for low-cost rechargeable room-temperature
Na-ion batteries. The material exhibits low Na insertion voltage
at 0.29 V. The Na2C8H4O4/KB composite electrode shows a
reversible capacity of 250 mAh/g, corresponding to a twoelectron transfer, with excellent cycling performance. By performing ALD Al2O3 coating on the surface of the Na2C8H4O4/
KB electrode, Na storage performance is significantly improved
in terms of initial coulombic efficiency, rate capability, and
cycling performance. Future work on the further reduction of
the irreversible capacity during the initial chargedischarge
process and on exploring Na storage mechanism is currently
in progress.

Experimental Section
Na2C8H4O4 was purchased from Alfa Aesar Company and used without
further treatment. Na2C8H4O4 and Ketjen black (EC-600JD, Ketjenblack
International, Japan) (80:20) were ball-milled in a planetary ball mill

964

wileyonlinelibrary.com

Figure 4. Discharge curves of the untreated Na2C8H4O4 electrode (a) and


the ALD20 (b) and ALD50 (c) electrodes at different discharge-charge
current rates, the curves shown here are the end ones of each five cycles.
(d) The cycling performance of the untreated Na2C8H4O4 electrode and
the ALD20 and ALD50 electrodes tested at 0.1C, the voltage range is
between 0.01 V and 2 V.
(PM 200) at 400 rpm for 15 min. The structure of Na2C8H4O4 samples was
characterized by XPert Pro MPD X-ray diffractometer (Philips, Holland)
using Cu-Ka radiation (1.5405 ). The morphologies of the samples were

2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

Adv. Energy Mater. 2012, 2, 962965

www.advenergymat.de
www.MaterialsViews.com

[5]

[6]

[7]

Supporting Information
Supporting Information is available from the Wiley Online Library or
from the author.

Acknowledgements
This work was supported by the National High Technology Research
and Development Program of China (Grant No. 2009AA033101), the
National Basic Research Program of China (Grant No. 2009CB220104),
the National Natural Science Foundation of China (Grant No.50972164),
Chinese Academy of Sciences Project (Grant No. KJCX2-YW-W26), and
the Hundred-Talent Project of the Chinese Academy of Sciences.
Received: March 9, 2012
Published online: May 11, 2012

[1] M. Armand, J. M. Tarascon, Nature 2008, 451, 652.


[2] Z. G. Yang, J. L. Zhang, M. C. W. Kintner-Meyer, X. C. Lu, D. W. Choi,
J. P. Lemmon, J. Liu, Chem. Rev. 2011, 111, 3577.
[3] a) V. L. Chevrier, G. Ceder, J. Electrochem. Soc. 2011, 158, 4;
b) S. P. Ong, V. L. Chevrier, G. Hautier, A. Jain, C. Moore, S. Kim,
X. H. Ma, G. Ceder, Energy Environ. Sci. 2011, 4, 3680.
[4] a) R. Berthelot, D. Carlier, C. Delmas, Nature Mater. 2010, 10, 74;
b) Z. L. Jian, L. Zhao, H. L. Pan, Y. S. Hu, H. Li, W. Chen,
L. Q. Chen, Electrochem. Commun. 2012, 14, 86; c) D. Kim, S.-H. Kang,

Adv. Energy Mater. 2012, 2, 962965

[8]
[9]
[10]
[11]
[12]
[13]
[14]
[15]
[16]
[17]
[18]
[19]

COMMUNICATION

observed using a scanning electron microscope (SEM) (Hitachi S-4800)


and a transmission electron microscope (TEM) (JEOL 2010). Fourier
transform infrared spectroscopy (FTIR) measurements were performed
on a Bruker Tensor 27 Spectrometer using KBr pellets. NMR experiments
were conducted on a Bruker Avance 600 spectrometer. The sample was
dissolved in D2O and the solution was sealed in a 5 mm NMR tube.
Both pristine and ball-milled sample electrodes were prepared with
active materials, carbon black, and binder (poly (vinylidene difluoride)
(PVdF) is dissolved in N-methyl pyrrolidinone (NMP)) at a weight ratio
of 80:10:10. The slurry was cast on the Cu foil and dried at 100 C in
vacuum for 10 h. The active material in the composite electrode is
64 wt.%. The specific capacity was calculated based on the mass of
Na2C8H4O4. The coil cells CR2032 were assembled with pure sodium foil
as counter electrode, glass fiber separator and 1M Na[N(SO2F)2] (NaFSI)
EC:DEC (4:6) electrolyte in an argon-filled glove box. The discharge and
charge measurements were carried out on a Land BT2000 battery test
system (Wuhan, China). The discharged electrode was washed with
anhydrous DMC several times and then dispersed in DME and dripped
in copper grid in the glove box for TEM observation.
A Savannah-100 ALD system (Cambridge NanoTech Inc.) was used
for the Al2O3 layer deposition. The deposition process was performed
at 200 C using trimethyl aluminum (TMA) and H2O as precursors. The
thickness of Al2O3 layer was about 1 for each precursor pulse cycle.

M. Slater, S. Rood, J. T. Vaughey, N. Karan, M. Balasubramanian,


C. S. Johnson, Adv. Energy Mater. 2011, 1, 333; d) Y. Kawabe,
N. Yabuuchi, M. Kajiyama, N. Fukuhara, T. Inamasu, R. Okuyama,
I. Nakai, S. Komaba, Electrochem. Commun. 2011, 13, 1225;
e) D. Kim, E. Lee, M. Slater, W. Q. Lu, S. Rood, C. S. Johnson, Electrochem. Commun. 2012, 18, 66.
a) J. F. Qian, M. Zhou, Y. L. Cao, X. P. Ai, H. X. Yang, Adv. Energy
Mater. 2012, 2, 410; b) L. Cao, L. F. Xiao, W. Wang, D. W. Choi,
Z. M. Nie, J. G. Yu, L. V. Saraf, Z. G. Yang, J. Liu, Adv. Mater.
2011, 23, 3155; c) S. Wenzel, T. Hara, J. Janek, P. Adelhelm,
Energy. Environ. Sci. 2011, 4, 3342; d) S. Komaba, W. Murata,
T. Ishikawa, N. Yabuuchi, T. Ozeki, T. Nakayama, A. Ogata, K. Gotoh,
K. Fujiwara, Adv. Funct. Mater. 2011, 21, 3859; e) Q. Sun,
Q. Q. Ren, H. Li, Z. W. Fu, Electrochem. Commun. 2011, 13, 1462;
f) L. Zhao, H. L. Pan, Y. S. Hu, H. Li, L. Q. Chen, Chin. Phys. B
2012, 21, 028201; g) P. Senguttuvan, G. Rousse, V. Seznec,
J. M. Tarascon, M. R. Palacin, Chem. Mater. 2011, 23, 4109;
h) H. Xiong, M. D. Slater, M. Balasubramanian, C. S. Johnson,
T. Rajh, J. Phys. Chem. Lett. 2011, 2, 2560.
a) H. Li, Z. X. Wang, L. Q. Chen, X. J. Huang, Adv. Mater. 2009, 21,
4593; b) Y. G. Guo, J. S. Hu, L. J. Wan, Adv. Mater. 2008, 20, 2878;
c) B. L. Ellis, K. T. Lee, L. F. Nazar, Chem. Mater. 2010, 22, 691;
d) V. Etacheri, R. Marom, R. Elazari, G. Salitra, D. Aurbach, Energy
Environ. Sci. 2011, 4, 3243.
a) P. Novak, K. Muller, K. S. V. Santhanam, O. Haas, Chem. Rev.
1997, 97, 207; b) B. Genorio, K. Pirnat, R. Cerc-Korosec, R. Dominko,
M. Gaberscek, Angew. Chem.Int. Ed. 2010, 49, 7222; c) W. Walker,
S. Grugeon, H. Vezin, S. Laruelle, M. Armand, J. M. Tarascon,
F. Wudl, Electrochem. Commun. 2010, 12, 1348; d) J. Geng,
J.-P. Bonnet, S. Renault, F. Dolhem, P. Poizot, Energy Environ. Sci.
2010, 3, 1929; e) K. Liu, J. Zheng, G. Zhong, Y. Yang, J. Mater. Chem.
2011, 21, 4125; f) Z. Song, H. Zhan, Y. Zhou, Angew. Chem. Int. Ed.
2011, 49, 8444.
B. Dunn, H. Kamath, J. M. Tarascon, Science 2011, 334, 928.
T. Le Gall, K. H. Reiman, M. C. Grossel, J. R. Owen, J. Power Sources
2003, 119, 316.
H. Chen, M. Armand, G. Demailly, F. Dolhem, P. Poizot,
J. M. Tarascon, ChemSusChem 2008, 1, 348.
H. Y. Chen, M. Armand, M. Courty, M. Jiang, C. P. Grey, F. Dolhem,
J. M. Tarascon, P. Poizot, J. Am. Chem. Soc. 2009, 131, 8984.
M. Armand, S. Grugeon, H. Vezin, S. Laruelle, P. Ribiere, P. Poizot,
J. M. Tarascon, Nature Mater. 2009, 8, 120.
J. A. Kaduk, Acta Crystal. Sec. B 2000, 56, 474.
H. Q. Li, H. S. Zhou, Chem. Commun. 2012, 48, 1201.
L. Zhao, Y. S. Hu, H. Li, Z. X. Wang, L. Q. Chen, Adv. Mater. 2011,
23, 1385.
Y. S. Jung, A. S. Cavanagh, L. A. Riley, S. H. Kang, A. C. Dillon,
M. D. Groner, S. M. George, S. H. Lee, Adv. Mater. 2010, 22, 2172.
Y. He, X. Q. Yu, Y. H. Wang, H. Li, X. J. Huang, Adv. Mater. 2011, 23,
4938.
a) S. Lim, J. Cho, Chem. Comm. 2008, 37, 4472; b) D. S. Guan,
J. A. Jeevarajan, Y. Wang, Nanoscale 2011, 3, 1465.
S. M. George, Chem. Rev. 2010, 110, 111.

2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

wileyonlinelibrary.com

965