Electrochemical performance studies of MnO2 nanoflowers recovered from spent battery

doi:10.1016/j.materresbull.2014.08.008

Materials Research Bulletin

Volume 60, December 2014, Pages 5-9

https://doi.org/10.1016/j.materresbull.2014.08.008 Get rights and content

Highlights

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MnO₂ is recovered from spent zinc–carbon batteries as nanoflowers structure.
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Recovered MnO₂ nanoflowers show high specific capacitance.
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Recovered MnO₂ nanoflowers show stable electrochemical cycling up to 900 cycles.
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Recovered MnO₂ nanoflowers show low resistance in EIS data.

Abstract

The electrochemical performance of MnO₂ nanoflowers recovered from spent household zinc–carbon battery is studied by cyclic voltammetry, galvanostatic charge/discharge cycling and electrochemical impedance spectroscopy. MnO₂ nanoflowers are recovered from spent zinc–carbon battery by combination of solution leaching and electrowinning techniques. In an effort to utilize recovered MnO₂ nanoflowers as energy storage supercapacitor, it is crucial to understand their structure and electrochemical performance. X-ray diffraction analysis confirms the recovery of MnO₂ in birnessite phase, while electron microscopy analysis shows the MnO₂ is recovered as 3D nanostructure with nanoflower morphology. The recovered MnO₂ nanoflowers exhibit high specific capacitance (294 F g⁻¹ at 10 mV s⁻¹; 208.5 F g⁻¹ at 0.1 A g⁻¹) in 1 M Na₂SO₄ electrolyte, with stable electrochemical cycling. Electrochemical data analysis reveal the great potential of MnO₂ nanoflowers recovered from spent zinc–carbon battery in the development of high performance energy storage supercapacitor system.

Graphical abstract

Introduction

Zinc–carbon battery is frequently used in electronic and electrical appliances as it is the least expensive battery among primary batteries. Fresh zinc–carbon battery consists of Zn metal as anode and MnO₂ powder as cathode. In discharged form, Zn is present as ZnO, while Mn is present as Mn₂O₃ and Mn₃O₄ [1], [2], [3]. Research shows that Zn and Mn contents are 28.3% and 26.3%, respectively of the total mass in a spent zinc–carbon battery [2]. Such high Zn and Mn contents highlight the importance of battery recycling, both from economy and environment perspectives. Battery recycling can be divided into pyrometallurgical process and hydrometallurgical process. The former involves selective volatization of scrapped battery at elevated temperature followed by condensation for metal recovery. It is the most popular battery recycling process in industry due to its simplicity as battery dismantling is not required [3], [4], [5], [6]. On the other hand, hydrometallurgical process involves dismantling, pre-treatment followed by metal ions leaching and precipitation. Hydrometallurgical process is more efficient in metal recovery and environmental friendly as its energy consumption is lower [7], [8]. A comparison of these processes is reported elsewhere [9], with detail technical information about battery treatment. However, battery recycling activities are not favored all the time as the economic interests normally supersede the environmental obligations. Therefore, recycling spent battery into valuable product is expected to be a solution in this context. In this work, we study the feasibility of recovered MnO₂ from spent zinc–carbon battery in supercapacitor application.

Supercapacitor is an energy storage device that stores energy via ion adsorption (electrochemical double layer capacitor) or fast surface redox reaction (pseudocapacitor). It has attracted worldwide research interests, mainly attributed to its high power capability, fast charging time, excellent reversibility and long cycle life [10]. In terms of energy and power aspects, supercapacitor positions between battery and conventional capacitor where it is preferred when high power load is needed. Recent years, various materials have been developed for supercapacitor electrode and they can be categorized into carbon-based materials (activated carbon, carbon nanotubes, graphene, fullerene) [11], [12], [13], [14], transition metal oxides (RuO₂·H₂O, MnO₂, Co₃O₄, V₂O₅) [15], [16], [17], [18], and conductive polymers (polyaniline, polypyrrole) [19], [20]. Among these materials, transition metal oxides show superiority over the rest due to their high specific capacitance. RuO₂·H₂O is a remarkable transition metal oxide as it can contribute specific capacitance up to 1585 F g⁻¹ [15]. Nonetheless, its commercial application is dampened due to its toxicity and high cost. Various efforts have been attempted to find a cheap yet environmental friendly material to replace RuO₂·H₂O as supercapacitor electrode. MnO₂ is found to be a potential candidate for this purpose due to its environmental friendly nature, low cost and high pseudocapacitance with reversible redox transition between III and IV oxidation states [21], [22]. Various synthesis routes for MnO₂ have been developed, such as hydrothermal [23], thermal decomposition [24], sol–gel [25], electrodeposition [26] and microwave-assisted [27] syntheses. In addition, different morphologies such as nanowires [28], nanorods [29], nanoflowers [30] and nanoflakes [31] have been prepared as the pseudocapacitance of MnO₂ is highly influenced by its morphology. Regardless of the synthesis routes or the MnO₂ morphologies, all the reported works used manganese precursors such as MnSO₄, KMnO₄ or Mn(CH₃COO)₂ from the commercial chemical source. To the best of our knowledge, the preparation of MnO₂ from waste source has not been reported yet. The aim of the present work is to study the electrochemical performance of MnO₂ recovered from spent household zinc–carbon battery and to evaluate its potential as energy storage supercapacitor.

Section snippets

Experimental section

A spent Zn–C battery (EVEREADY^® D cell) was dismantled and the cathode black paste was used for subsequent process. The cathode black paste was dried at 130 °C for 24 h, ground well in a mortar, and then sieved using a 200 μm mesh. The sieved powder was later washed with deionized water (solid to liquid ratio 1:10) to remove NH₄Cl electrolyte in the battery and finally dried at 105 °C for 24 h. The dried powder (20 g) was subsequently dissolved in H₂SO₄ (200 mL, 2 M), followed by addition of H₂C₂O₄

Structural and morphology characterization

In Fig. 1, XRD analysis shows that Mn₂O₃ and Mn₃O₄ are the major phases in dried cathode powder. A sharp peak observed at 11.54° for dried cathode powder could be related to the Zn₅(OH)₈Cl₂·H₂O [8]. After electrowinning, dark precipitate of MnO₂ shows broad peaks at 12.58°, 37.14°, and 66.18°, correspond to (0 0 2), (0 0 6) and (1 1 9) planes of birnessite-type MnO₂ (JCPDS No. 00-018-0802), respectively [31], [32], [33], [34]. No other peaks related to the impurities can be found. According to

Conclusions

MnO₂ with nanoflower morphology is successfully recovered from zinc–carbon battery by combination of leaching and electrowinning techniques. CV and charge/discharge results show that the MnO₂ nanoflowers possess good capacitive behavior (294 F g⁻¹ at 10 mV s⁻¹; 208.5 F g⁻¹ at 0.1 A g⁻¹) with stable cycling up to 900 cycles. In addition, EIS analysis suggests that the MnO₂ nanoflowers could be potential candidate for fast charge/discharge supercapacitor with low charge transfer resistance and low time

Acknowledgements

KF Chong and co-workers would like to acknowledge the funding from the Ministry of Education Malaysia in the form of MTUN-COE grant RDU121212 and RDU121213 and Ministry of Science, Technology and Innovation in the form of eScienceFund RDU140501.

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Electrochemical performance studies of MnO2 nanoflowers recovered from spent battery

Highlights

Abstract

Graphical abstract

Introduction

Section snippets

Experimental section

Structural and morphology characterization

Conclusions

Acknowledgements

Hydrometallurgy

J. Hazard. Mater.

J. Hazard. Mater.

J. Power Sources

J. Power Sources

J. Power Sources

J. Power Sources

Int. J. Hydrogen Energy

J. Power Sources

Electrochim. Acta

J. Power Sources

Mater. Res. Bull.

Mater. Res. Bull.

Electrochim. Acta

Mater. Res. Bull.

J. Power Sources

Chem. Commun.

J. Solid State Electrochem.

J. Power Sources

Electrochim. Acta

Mater. Chem. Phys.

Electrochemical performance studies of MnO₂ nanoflowers recovered from spent battery