A Rechargeable Tin–Air PEM Battery Using SnSO₄ as an Anode-active Material

Abstract

SnSO 4 was employed as an anode-active material for rechargeable batteries, where Sn 4+ and Sn 2+ ions are reduced to Sn 2+ and Sn, respectively during charge while the inverse reactions occur during discharge. Undesired hydrogen production was substantially avoided by adjusting the charge voltage to 1.5 V. The resulting cell functioned as a battery with an electrical capacity of 258 mA h g ¹1 at 10 mA cm ¹2 and as a fuel cell with power densities of 55125 mW cm ¹2 at 0.8 V.Hydrogen is a promising energy medium capable of storing and supplying electricity through water-electrolysis/fuel-cell operation.1 The primary application of this system is the control of surplus power when the electric power produced by natural energy sources exceeds that required by an energy consumer. 2Hydrogen storage is currently carried out by the liquefaction and compression of hydrogen, or by the physical and chemical adsorption of hydrogen atoms or molecules onto materials such as activated carbon and metal or organic chemical hydrides. However, these processes require some external form of energy for hydrogen storage and release, which increases the electric power costs.In the present study, we address this challenge through the use of Sn 4+ /Sn2+ and Sn 2+ /Sn redox couples as energy carriers for rechargeable fuel cell operation.The counter reaction occurring at the cathode is:where protons migrate through the proton-exchange membrane (PEM) to control the charge balance between Reactions (1) or (2) and (3) during charge and discharge.The theoretical open-circuit voltage (OCV) is 1.03 V for (1) and 1.36 V for (2) under standard conditions. Although the theoretical discharge capacity is 231 mA h g ¹1 for (1) and (2), it increases to 462 mA h g ¹1 when Sn 4+ ions are reduced to tin metal via Reaction (2).To further enhance the volumetric energy density, we integrate the metal redox couple with a fuel cell, so that this system no longer requires tanks, plumbing, and circulation pumping of the redox couple media. Such an electrochemical cell should not be classified as a fuel cell because the fuel is an integral part of the device. 5 Considering that both the anode and cathode potentials are determined based on the respective equilibrium thermodynamic reactions, it should be designated as a rechargeable PEM battery (RPB). This study examined the electrochemical properties of RPBs using SnSO 4 as an anodeactive material at room temperature. Here, it should be noted that Sn 2+ ions are in equilibrium with Sn 4+ ions, depending on the anode potential. 6Sn 0.9 In 0.1 P 2 O 7 (SIPO) was used as the proton conductor because this material has a proton conductivity of ca. 0.05 S cm ¹1 without excess humidification. 7 The electrolyte membrane was prepared by mixing SIPO powder (1.00 g) with poly(tetrafluoroethylene) (PTFE) powder (0.04 g) in a mortar, followed by cold-rolling the mixture to a thickness of ca. 350¯m using a laboratory rolling mill. The anode-active material was 0.25 M SnSO 4 in 1 M H 2 SO 4 . 0.5 g of the solution was dispers...

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Figure 6 I - V characteristic curves of the oxygen sensor in different temperature in an oxygen concentration of 4.70%.

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