Nano SnO2–Al2O3 mixed oxide and SnO2–Al2O3–carbon composite oxides as new and novel electrodes for supercapacitor applications

doi:10.1016/j.jpowsour.2005.10.091

Journal of Power Sources

Volume 158, Issue 2, 25 August 2006, Pages 1538-1543

https://doi.org/10.1016/j.jpowsour.2005.10.091 Get rights and content

Abstract

New nano-materials like SnO₂–Al₂O₃ and SnO₂–Al₂O₃–carbon were synthesized by a single step hydrothermal method in searching for novel mixed oxides with high electrochemical double layer capacitance. A SnO₂–Al₂O₃–carbon sample was calcined at 600 °C and tested for its performance. The source of carbon was tetrapropyl ammonium hydroxide. The capacitive behavior of SnO₂ was compared to the performance of SnO₂–Al₂O₃, SnO₂–Al₂O₃–carbon and calcined SnO₂–Al₂O₃–carbon using the techniques of cyclic voltammetry, double potential step, chronopotentiometry and E–log I polarization. In 0.1 M NaCl solutions, SnO₂–Al₂O₃ gave the best performance with a value of 119 Fg⁻¹ and cycled 1000 times. The nano-material mixed oxides were characterized by TEM, XRD, ICP-AES and SEM-EDAX.

Introduction

A recently rejuvenated interest in the development of super or ultra or electrochemical double layer capacitors (EDLC) is due to the power requirements of a number of applications that have exceeded the capability of batteries available in the market to-day. As an alternative power source, EDLC is being intensively investigated in the United States, Japan, Europe and Russia. To increase the power delivery at least by one order of magnitude higher than existing capacitors, metal oxides and mixed metal oxides has been introduced as electrodes which also deliver pseudo-capacitance. For an ideal double layer capacitor, the charge is transferred into the double layer and there are no Faradaic reactions between the solid material and the electrolyte. In this case, the capacitance is constant and independent of voltage. On the other hand, for capacitors that use metal oxides, pseudo-capacitance due to Faradaic reactions between the solid material and the electrolyte arises and it is voltage dependent. The double layer capacitance has a typical value of 10–40 μF cm⁻² for a real surface, while pseudo-capacitance may be 10–100 times greater. Prototypes made of ruthenium and tantalum oxides have been highly successful and are commercialized [1]. As ruthenium is highly expensive, alternative metal oxides are explored.

Lead Pb/Ru pyrochlore (Pb₂Ru₂O_6.5) was synthesized as a new electrode material for aqueous electrolyte capacitors and the performance was similar to ruthenium oxide electrodes [2]. Nano-porous vanadium oxide (V₂O₅) prepared by the sol–gel method was shown to have a maximum capacitance of 214 Fg⁻¹ obtained at a scan rate of 5 mV s⁻¹ in 2 M KCl [3]. Studies on a solid-state capacitor based on Ppy (polypyrrole)/Al₂O₃/Al prepared by the constant current method revealed that three stages, namely the formation of Al₂O₃ and the nucleation of Ppy within the pores of Al₂O₃, the propagation of Ppy on the Al₂O₃ barrier layer and the over-oxidation of Ppy located in the pores of Al₂O₃, play a vital role on the performance of the capacitor [4]. Amorphous MnO₂ was synthesized using the sol–gel method and a maximum capacitance of 110 Fg⁻¹ was obtained at a scan rate of 5 mV s⁻¹ in 2 M NaCl solution [5]. MnO₂ grown from MnSO₄ solutions mixed with acetate based electrolytes has been studied for electrochemical capacitor applications and has shown a consistent decrease in specific capacitance from 260 to 50 Fg⁻¹as the material thickness increases [6]. Hydrous IrO₂ has been found to perform in electrochemical capacitor applications with a specific capacitance close to 550 Fg⁻¹ [7]. SrCoO_2.5 was tested to be a potential active electrode material for an electrochemical capacitor and a specific capacitance of 168.5 Fg⁻¹ could be obtained in the range of 0.1–0.7 V [8]. Sb-doped SnO₂ and composite electrodes of SnO₂ in combination with ruthenium oxide and iron oxide have been studied for their suitability as electrodes for supercapacitors and SnO₂–Fe₃O₄ was shown to have specific capacitance comparable with the carbon electrodes but with a much higher capacitance density [9]. Pseudo-capacitive behavior of Ti/RhO_x + Co₃O₄ electrodes in acidic medium revealed that the electrochemical performance depends on the composition of the oxides. A decrease in the voltammetric charge with cycle number was observed for 5–10 mol% Rh electrodes which has been related to the cathodic dissolution of CoO [10]. NiO/RuO₂ composite materials were prepared for use in electrochemical capacitors (ECs) by a co-precipitation method and a maximum specific capacitance of 210 Fg⁻¹ was obtained for NiO-based composite electrode with 10 wt.% RuO₂ in the voltage range from −0.4 to 0.5 V in 1 M KOH solution [11]. Ir_0.3Mn_0.7O₂ electrodes perform well in electrochemical capacitor applications with a specific capacitance close to 550 Fg⁻¹ [12].

Nano-crystalline metal oxides that have high surface area, high conductivity, electrochemical stability and pseudo-capacitive behavior can be highly significant in this aspect. Capacitors based on activated carbon materials have been successfully commercialized using non-aqueous electrolytes to increase the operating potential of the devices. To combine mixed metal oxides and carbon in a single electrode as a composite nano-material could achieve all the benefits. Alumina is a widely used support due to the good mechanical properties of alumina and its ability to disperse the active oxide phase. Substrate–metal (Al₂O₃/Pd) charge transfer induced by the dipoles at the interface was proven to play a crucial role in increasing the CO adsorption and dissociation [13]. In this communication, we synthesized a SnO₂–Al₂O₃ mixed oxide and a SnO₂–Al₂O₃–carbon composite mixed oxide by a single step hydrothermal method. Urea was used as the hydrolytic agent. These nano-materials were characterized by XRD, TEM, ICP-AES and SEM-EDAX. Electrochemical characterization by cyclic voltammetry, double step chronopotentiometry and E versus log I polarization measurements were done to evaluate the use of these nano-materials as potential electrodes for supercapacitor applications. The electrochemical performance of single SnO₂ was compared to these composite electrodes under identical conditions to understand the beneficial effects of Al₂O₃ and carbon.

Section snippets

Experimental

Chemical syntheses of all the mixed oxides were done in a single step hydrothermal process involving urea as the hydrolytic agent. SnO₂–Al₂O₃–carbon was calcined at 600 °C and the sample was tested for electrochemical performance. SnO₂–Al₂O₃, SnO₂–Al₂O₃–carbon and calcined SnO₂–Al₂O₃–carbon oxides were designated as Sn–Al, Sn–Al–C and Sn–Al–CC, respectively.

Characterization of nano-materials

An XRD pattern of hydrothermally synthezised Sn–Al sample is shown in Fig. 1. The XRD pattern matches the standard file of SnO₂ (JCPDS card no. 21-1250). The pattern proves the crystalline nature of SnO₂ nano-particles compared to AlOOH/Al₂O₃ which was highly amorphous as indicated by the absence of peaks in the XRD. Fig. 2 shows the TEM images of SnO₂–Al₂O₃ nanoparticles. The amorphous phase Al₂O₃ was clearly shown by the cloudy alignment of super fine particles while the darker spherical

Conclusions

In this communication, we synthesized nano-SnO₂–Al₂O₃ and SnO₂–Al₂O₃–carbon composites via a simple single step hydrothermal route. In 0.1 M NaCl solutions, the electrochemical double layer capacitance of SnO₂–Al₂O₃ was much greater than of the pure SnO₂ and the electrode was electrochemically and chemically stable even after cycling1000 times. The performance of the carbon added composites was better than SnO₂ but lower than SnO₂–Al₂O₃. The expectation that added carbon would enhance the

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Short communicationNano SnO2–Al2O3 mixed oxide and SnO2–Al2O3–carbon composite oxides as new and novel electrodes for supercapacitor applications

Abstract

Introduction

Section snippets

Experimental

Characterization of nano-materials

Conclusions

J. Power Sources

J. Power Sources

J. Power Sources

Electrochim. Acta

Electrochim. Acta

Mater. Chem. Phy.

Mater. Chem. Phys.

Electrochim. Acta

Electrochim. Acta

Electrochim. Acta

Surf. Sci.

Thin Solid Films

Short communication
Nano SnO₂–Al₂O₃ mixed oxide and SnO₂–Al₂O₃–carbon composite oxides as new and novel electrodes for supercapacitor applications