Voltammetric and discharge characteristics of hydrogen-chlorate current generator with sulfuric acid electrolyte

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Abstract

Operation of a single cell of redox-flow hydrogen-halogenate current generator which converts the energy of the oxidation reaction of gaseous hydrogen by sodium chlorate in aqueous sulfuric-acid solution into electric energy with the use of a membrane-electrode assembly of the composition: (–) H2, Pt–C // PEM // NaClO3, C (+) has been studied. A combined load operation regime (which includes stages of potentio- and galvanostatic control) has been applied, in order to take into account specific features of the chlorate electroreduction half-reaction, i. e. its redox-mediator autocatalytic mechanism (EC-autocat). For aqueous electrolytes containing various sulfuric acid contents, the system parameters determining the power and efficiency of the hydrogen-chlorate current generator have been established: faradaic and energy efficiencies, average discharge power and time to reach the steady-state mode. It has been found that the hydrogen-chlorate cell under study functions most efficiently for the 5 M sulfuric-acid electrolyte: such a cell has reached the constant-current mode to generate the 0.25 A/cm2 current density within one and a half minutes; it has been able to convert the chemical energy into the electric one with the 55% efficiency at the average specific discharge power of 0.23 W/cm2.

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O. I. Istakova

Federal Research Center of Problems of Chemical Physics and Medicinal Chemistry, Russian Academy of Sciences; Frumkin Institute of Physical Chemistry and Electrochemistry, Russian Academy of Sciences

Author for correspondence.
Email: dkfrvzh@yandex.ru
Russian Federation, Chernogolovka; Moscow

D. V. Konev

Federal Research Center of Problems of Chemical Physics and Medicinal Chemistry, Russian Academy of Sciences; Frumkin Institute of Physical Chemistry and Electrochemistry, Russian Academy of Science

Email: dkfrvzh@yandex.ru
Russian Federation, Chernogolovka; Moscow

M. A. Vorotyntsev

Frumkin Institute of Physical Chemistry and Electrochemistry, Russian Academy of Sciences

Email: mivo2010@yandex.com
Russian Federation, Moscow

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3. Fig. 1. (a) Cyclic voltammograms of a hydrogen-chlorate battery cell (platinum load on the anode 0.47 mg/см2, Nafion 212 membrane) with an electrolyte of the composition 1 M NaClO3 + 4 M H2SO4, 5 voltage sweep cycles from the NRZ to 0.1 V at a rate of 0.005 V/s, the curve numbers correspond to the cycle number. The terminal of the working electrode of the potentiostat is connected to the chlorate electrode through which the cathode current flows. (b) Current dependences on time during the measurement of cyclic voltammograms of a hydrogen-chlorate battery cell with electrolytes of the composition 1 M NaClO3 and different sulfuric acid contents: 1 – 4 M; 2 – 5 M; 3 – 6 M. The measurement conditions correspond to Fig. 1a; in particular, curve 1 in Fig. 1b is a representation of the data from Fig. 1a in current-time coordinates. The arrows in the figures show the direction of voltage change in each half-cycle, the numbers next to the arrows in Fig. 1b are the cycle numbers

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4. Fig. 2. (a) Volt-ampere characteristics of the discharge cell for electrolytes with 1 M NaClO3 at different sulfuric acid contents: 1 – 4 M; 2 – 5 M; 3 – 6 M. Platinum load on the anode is 0.47 mg/cm2,, Nafion 212 membrane, voltage sweep rate is 0.005 V/s. Measurements were started on a freshly prepared electrolyte, steady-state responses of the cell are shown (fifth cycle). (b) Dependence of the specific discharge power on the current density according to the data of Fig. 2a, sulfuric acid content: 1 – 4 M; 2 – 5 M; 3 – 6 M.

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5. Fig. 3. (a) Current-voltage characteristics of the discharge cell for electrolytes with 1 M NaClO3 + 5 M H2SO4 at different platinum loadings on the anode: 1 – 0.23 mg/cm2; 2 – 0.47 mg/cm2; 3 – 1.04 mg/cm2. Nafion 212 membrane, voltage sweep rate 0.005 V/s. Measurements were started on a freshly prepared electrolyte, the figure shows the steady-state cycles. (b) Dependence of the specific discharge power on the current density according to the data of Fig. 3a, platinum loading on the anode: 1 – 0.23 mg/cm2; 2 – 0.47 mg/cm2; 3 – 1.04 mg/cm2.

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6. Fig. 4. (a) Current-voltage characteristics of the discharge cell for 1 M NaClO3 + 5 M H2SO4 electrolyte with membranes of different thicknesses, membranes: 1 – Nafion 211; 2 – Nafion 212; 3 – GP-IEM-105. Platinum loading on the anode is 0.47 mg/cm2, voltage sweep rate is 0.005 V/s. Measurements were started on freshly prepared electrolyte, the figure shows steady-state cycles. (b) Dependence of the specific discharge power on the current density according to the data of Fig. 4a, membranes: 1 – Nafion 211; 2 – Nafion 212; 3 – GP-IEM-105.

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7. Fig. 5. (a) Current versus time at stage 2 (“ignition”) for a hydrogen-chlorate battery cell with different catholyte compositions: 1 M NaClO3 + X M H2SO4, X = 4 (1); 5 (2); 6 (3). (b) Discharge voltage–passed charge curves during stage 3 (selection of constant discharge current with a density of 250 mA/cm2) for catholytes with different sulfuric acid contents: 1 M NaClO3 - X M H2SO4, X = 4 (1); 5 (2); 6 (3). Platinum loading of 0.47 mg/cm2 at the anode, Nafion 212 membrane.

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