Electrochemistry Communications 9 (2007) 3134 www.elsevier.

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Room temperature Na/S batteries with sulfur composite cathode materials

Jiulin Wang
b

a,b,*

, Jun Yang b, Yanna Nuli b, Rudolf Holze

a,*

a Chemnitz University of Technology, Institute of Chemistry, Chemnitz D-09111, Germany Shanghai Jiao Tong University, Department of Chemical Engineering, Shanghai 200240, China

Received 24 July 2006; received in revised form 15 August 2006; accepted 16 August 2006 Available online 18 September 2006

Abstract Sodium/sulfur (Na/S) batteries were assembled with a sodium metal anode, liquid electrolyte and a sulfur composite cathode. Their electrochemical characteristics have been investigated at room temperature. Their charge/discharge curves indicate that sodium can reversibly react with sulfur at room temperature. The specic capacity of the sulfur composite cathode material in the rst cycle was initially about 655 mA h g1 and stayed at about 500 mA h g1 up to the 18th cycle with about 100% charge/discharge eciency. 2006 Elsevier B.V. All rights reserved.
Keywords: Na/S battery; Na anode; Sulfur composite cathode; Room temperature battery

1. Introduction The sodium/sulfur (Na/S) battery shows various significant advantages: high energy density (theoretical specic energy density of 760 W h kg1), low cost material (abundant resources of sulfur and sodium in nature), low rate of self-discharge and high power density [13]. A typical Na/S battery consists of sulfur at the positive electrode and sodium at the negative electrode separated by a solid beta alumina ceramic electrolyte. This type of Na/S battery must be operated at about 300 C to ensure sucient Na+ conductivity in the electrolyte. At this operation temperature, both sulfur and sodium electrodes are in the liquid (molten) state. Considering potentially extensive or even explosive reactions between liquid sulfur and liquid sodium, safety is an issue for the high temperature Na/S battery. Moreover, active cathode materials (sulfur and

sodium polysulde) are corrosive, this was considered as one of the major failure reasons for Na/S batteries [4]. Based on the successful development of lithium ion batteries, several groups begun to develop room temperature sodium ion batteries which are promising substitutes for lithium ion batteries in various application areas [57]. In a low temperature Na/S battery, the sulfur cathode will encounter the same problems as Li/S batteries: low utilization of active material, poor rechargeability and dissolution of polysuldes into the electrolyte [8]. In previous papers [9,10], we reported on sulfur composite cathode materials with sulfur embedded in a polymer matrix, which exhibited good electrochemical performances in lithium batteries. In this paper, sulfur composite materials were used as cathodes for room-temperature Na/S battery with liquid electrolyte. 2. Experimental 2.1. Preparation and characterization of sulfur composite materials Sulfur composite materials were prepared as previously reported [9]. Typically, sublimed sulfur (with purity of 99.99%) was thoroughly mixed with polyacrylonitrile

Corresponding authors. Address: Chemnitz University of Technology, Institute of Chemistry, Chemnitz D-09111, Germany. Tel.: +49 371 531 21260x31509; fax: +49 371 531 21269. E-mail addresses: jiulin.wang@chemie.tu-chemnitz.de (J. Wang), rudolf.holze@chemie.tu-chemnitz.de (R. Holze). 1388-2481/$ - see front matter 2006 Elsevier B.V. All rights reserved. doi:10.1016/j.elecom.2006.08.029

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J. Wang et al. / Electrochemistry Communications 9 (2007) 3134

(PAN, Aldrich). Ethanol was used as dispersant to improve the mixing of sulfur and PAN. After drying, the mixture was heated to 300 C and dwelled for 6 h under Ar gas. A black, powdery material was obtained. Scanning electron microscopy (SEM, JEOL JSM6700F) and X-ray diraction (XRD, D/max 2550 V) were used to characterize the morphology and crystalline state of composite materials, respectively. TGA and DSC tests were carried out with a TGA instrument Pyris 1 (Perkin Elmer) at a heating rate of 10 C min1 under N2 protection. 2.2. Cell assembly and testing Room temperature Na/S batteries were assembled similar to Li/S batteries. NaClO4, ethylene carbonate (EC) and dimethyl carbonate (DMC, Aldrich) were used as received. EC and DMC were rstly mixed at a weight ratio of 2:1, and then NaClO4 was dissolved in solvents to get 1 M NaClO4 EC-DMC liquid electrolyte. To fabricate cathodes, 70 wt% above-mentioned sulfur composite containing 42 wt% sulfur was mixed with 20 wt% acetylene black and 10 wt% polytetrauoroethylene (PTFE), with ethanol serving as dispersant. The mixture was rolled into lms approximately 100 lm thin. A disk punched out of the lm, with approximately 1.1 cm2 in area and 5 mg in weight, was pressed into a nickel foam. After drying at 100 C, a CR2016-type coin battery was assembled in a glove bag lled with Ar gas. A sodium metal sheet was used as anode. Charge and discharge performances of the batteries were investigated with LAND cycler (Wuhan, China) at a current density of 0.1 mA cm2 between 0.8 and 2.5 V at room temperature. 3. Results and discussion The results of SEM test showed an average particle size of the composite material of about 200 nm. In addition, there were some aggregated nano-particles [9]. XRD patterns indicated that the composites with sulfur content below 50 wt% is amorphous [10]. Sulfur might be embedded, as nano-particles or even at the molecular level, in sulfurized PAN matrix. Fig. 1 shows the thermal properties of elemental sulfur and PAN, and the composite material with sulfur content of about 45 wt%. Sulfur is easy to sublimate and almost all is evaporated at 280 C. Under N2 gas protection, PAN shrunk and decomposed at 296 C, and kept about 68 wt% of its original mass at 350 C. Compared to the starting materials, the sulfur composite exhibits excellent thermal stability. The composite material with a sulfur content of about 45 wt% slowly lost weight, but retained above 90% of its original mass even at 400 C. The result of DSC analysis of the composite gave a horizontal line (as the green line shown in Fig. 2). Almost no endothermic and exothermic process occurred up to the temperature of 400 C, which indicates that the sulfur composite materials

Fig. 1. TGA of sulfur composite material, sulfur and PAN.

possess excellent thermal stability. In a previous paper [9], solid state NMR (Nuclear Magnetic Resonance) was used to characterize the structure of sulfur composite materials. The 13C NMR spectra suggested the formation of heterocyclic structures in PAN during reaction with sulfur. Thus it is possible that heterocyclic structures in sulfurized PAN restrained the evaporation of sulfur which was embedded in the polymer matrix. It is also possible that sulfur might react with PAN and graft to the chains of sulfurized PAN at high temperature. The charge and discharge proles of Na/S battery with composite cathode material containing 45 wt% sulfur are shown in Fig. 3. The Na/S battery exhibited an open-circuit voltage (OCV) of 2.36 V at room temperature. During the rst discharge process, the specic capacity was 654.8 mA h g1 based on the composite cathode material. The average voltage based on half of specic capacity was 1.33 V. Considering the 45 wt% sulfur content in the composite material, the calculated discharge capacity of

Fig. 2. DSC of sulfur composite material, sulfur and PAN.

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pure sulfur was 1455 mA h g1. The charge and discharge reactions of Na/S battery can be written as: 2Na + xS M Na2Sx. When x is equal to 1, the theoretical capacity of the sulfur cathode is 1672 mA h g1. Accordingly, 87% of sulfur in the composite material took part in the reaction with sodium to form Na2S during the rst discharge process, assuming that the sulfurized PAN matrix stayed inert during the charge/discharge process. In a Na/b-Al2O3/S battery, Na2S2 solid will jam the ionic channel of b-Al2O3 electrolyte and discharge process will be ended before the formation of Na2S2. As a result, the specic capacity of sulfur is actually less than 836 mA h g1 for a Na/b-Al2O3/S battery. This problem did not exist in the Na/S cells described here and sulfur could be reduced to S2 (Na2S). As shown in Fig. 3, the specic capacities were about 520 mA h g1 during the following two cycles, which indicates that 69% of sulfur remained in reversible reaction with sodium. There was no obvious voltage plateau in the cycle proles. Average charge and discharge voltage was 1.8 and 1.4 V, respectively. Fig. 4 exhibits the rechargeability of Na/S battery. The specic capacity of the sulfur composite cathode decreased slowly with the progressive cycles and retained about 500 mA h g1 after 18 cycles. It was remarkable that the charge and discharge eciency of the battery was close to 100% except for the rst discharge process, which indicated that the sulfur in the composite exhibited good electrochemical reversibility via the reaction, 2Na + xS M Na2Sx at room temperature. After opening the battery in an argon-lled glove bag, it was found that thick black moss, so-called sodium dendrite, covered the surface of the sodium anode. Sulfur composite cathodes could be still well charged and discharged with a fresh sodium anode. A similar phenomenon was observed in previously reported Li/S batteries [10]. This phenomenon indicates that the dendrite is also a critical problem for room temperature Na/S batteries. In view

Fig. 4. The cycle characteristics of Na/S battery.

of the fact that the melting point of sodium is 98 C and the sulfur composite materials keep stable up to 300 C, we are developing Na/S batteries with cross-linked PEO and new types of polymer electrolytes, which are expected to overcome the sodium dendrite problem in a operational temperature range between 110 and 150 C [11,12]. Moreover, Na+ ionic liquid could be expected to perform the similar function [13]. 4. Conclusions Charge and discharge performances of Na/S batteries were reported in this paper. Na/S batteries were assembled with a sodium metal anode, liquid electrolyte and a sulfur composite cathode. The charge/discharge curves of Na/S batteries indicated that Na could reversibly react with sulfur embedded in the sulfurized polymer matrix at room temperature and the reactions of Na/S battery could be written as: 2Na + xS M Na2Sx. During the rst discharge process, the specic capacity was 654.8 mA h g1 based on the composite cathode materials and the calculated discharge capacity of pure sulfur was 1455 mA h g1. The reversible specic capacity of sulfur composite cathode was about 500 mA h g1 and kept stable in the following cycles with about 100% charge/discharge eciencies. Average charge and discharge voltage was 1.8 and 1.4 V, respectively. Similar to lithium batteries, dendrite was also a critical problem for room temperature Na/S batteries. Acknowledgement We are grateful to the Alexander von Humboldt Foundation for a research fellowship for one of us (J.L.W.). References

Fig. 3. The charge/discharge proles of Na/S battery at room temperature.

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