Single cell hydrogen-vanadium flow battery of high specific discharge power

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Hybrid flow chemical power source: (Pt–C)H2|Nafion|VO2+(C) has been studied where the membrane-electrode assembly combines the gas-diffusion anode of hydrogen-air fuel cell (FC) and the cathode of vanadium redox flow battery (VRFB). Concept of such a hydrogen-vanadium flow battery (HVFB) had been proposed earlier (in 2013) as an alternative to VRFB, also designed for large-scale electrical energy storage but its practical implementation has so far been limited to single cells having the active area within several tens of cm2. The goal of this work has been to establish the factors limiting the specific discharge power of such hybrid. HVFB cells which is inferior to both hydrogen-air FC and VRFBs, even though the HVFB cell represents a combination of their more reversible half-cells. The object of the study has been a cell of 2cm × 2cm membrane-electrode assembly equipped with Luggin’s capillary on the vanadium electrolyte side. Measurements of the current-voltage characteristics of the cell as a whole as well as the polarizations of its half-cells have been performed with the use of the six-electrode scheme of the cell connection for various circulation rates of the vanadium electrolyte and cathode materials (carbon felts 4.6 or 2.5 mm thick as well as carbon paper). It has been established that the contribution of the hydrogen gas diffusion electrode to the total DC resistance of the HVFB cell is twice that of the flow-through vanadium cathode. A record high specific discharge power has been achieved: 0.75 W cm–2, for the cell based on the commercially available material, Sigracell GFD 2.5 EA carbon felt, as the cathode material, without its special surface modification.

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Sobre autores

O. Istakova

Federal Research Center of Problems of Chemical Physics and Medicinal Chemistry RAS

Email: dkfrvzh@yandex.ru
Rússia, Chernogolovka

D. Konev

Federal Research Center of Problems of Chemical Physics and Medicinal Chemistry RAS; A.N. Frumkin Institute of Physical Chemistry and Electrochemistry of the Russian Academy of Sciences

Autor responsável pela correspondência
Email: dkfrvzh@yandex.ru
Rússia, Chernogolovka; Moscow

D. Tolstel

M.V. Lomonosov Moscow State University

Email: dkfrvzh@yandex.ru
Rússia, Moscow

E. Ruban

Federal Research Center of Problems of Chemical Physics and Medicinal Chemistry RAS; A.N. Frumkin Institute of Physical Chemistry and Electrochemistry of the Russian Academy of Sciences

Email: dkfrvzh@yandex.ru
Rússia, Chernogolovka; Moscow

M. Krasikova

Federal Research Center of Problems of Chemical Physics and Medicinal Chemistry RAS

Email: dkfrvzh@yandex.ru
Rússia, Chernogolovka

M. Vorotyntsev

A.N. Frumkin Institute of Physical Chemistry and Electrochemistry of the Russian Academy of Sciences

Email: mivo2010@yandex.com
Rússia, Moscow

Bibliografia

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2. Fig. 1. (a) The design of the VVPB cell with the Luggin capillary in isometric projection and the cross-section of its MEA, see the explanation of the symbols in the text; (b) the diagram of the distribution channels for the electrolyte supply in the limiting frames of the electrode spaces 6, the color scale shows the calculated distribution of the linear velocity of the electrolyte flow (left) and the pressure (right); (c) the components of the internal resistance of the MEA cell to the passage of direct current RMEA cell and the diagram of its connection to the potentiostat during electrochemical measurements.

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3. Fig. 2. Polarization characteristics of the negative half-cell of the VVPB cell (a, c), obtained by the galvanodynamic method (50 mA/s) at a circulation rate of H2 media of 300 ml/min, 3 M H2SO4 – 120 ml/min (a), 3 M H2SO4 and vanadium electrolyte with an equivalent content of vanadyl and vanadate cations – 120 ml/min (c) for MEA of different compositions: (a) Nafion 211, Pt–C 0.226 mg/cm2 (1); Nafion 211, Pt–C 0.516 mg/cm2 (2); Nafion 211, Pt–C 1.04 mg/cm2 (3); Nafion 212, Pt–C 0.226 mg/cm2 (4); (c) H2/H2SO4 (1), H2/V_SOC 0.5 (2). Cyclic voltammograms of the negative half-cell of the VVPB cell (b, d) with the MEA of the Pt–C composition (x, mg/cm2: 0.226 (1); 0.516 (2); 1.04 (3))|Nafion 211|CF 4.6 EA-TA, obtained by filling the anode space with argon and circulating through the cathode 3 M H2SO4 – 120 ml/min (b), 3 M H2SO4 (1) and vanadium electrolyte with an equivalent content of vanadyl and vanadate cations (2) – 120 ml/min (d). Potential scan rate is 20 mV/s.

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4. Fig. 3. (a) Open-circuit voltage and half-cell potentials (see legend) as a function of the state of charge for a VTB cell with a Pt–C (0.226 mg/cm2)|Nafion 211|CF 2.5 EA-TA MEA, obtained at a hydrogen circulation rate of 300 ml/min and a vanadium electrolyte flow rate of 65 ml/min during the vanadyl-vanadate conversion (hollow dots) and in the opposite direction (filled dots). (b) Hydrogen half-cell potential in an enlarged scale along the potential axis.

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5. Fig. 4. Current-voltage characteristics of the VVPB cell in the charge/discharge mode (a-c) and polarization characteristics of its half-cells relative to the Ag/AgCl reference electrode at SOC = 0.5 for a linear velocity of vanadium electrolyte flow of 3 cm/s through a cathode made of different carbon materials: CP 6 × 0.28 mm (a), CF 2.5 mm (b), CF 4.6 mm (c); dependences of the specific charge/discharge power of the VVPB cell on the velocity of electrolyte circulation through the cathode made of different carbon materials in the range of 0.5 – 3 cm/s: CP 6 × 0.28 mm (d), CF 2.5 mm (d), CF 4.6 mm (e). Volumetric flow rates, ml/min: 1 – 51, 2 – 34, 3 – 17, 4 – 10 (d); 1 – 65, 2 – 43, 3 – 22, 4 – 11 (d); 1 – 120, 2 – 80, 3 – 40, 4 – 20 (f).

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6. Fig. 5. Impedance hodographs of the VVPB cell and its half-cells relative to the Ag/AgCl reference electrode, obtained at an open-circuit voltage in the frequency range of 50 kHz … 0.03 Hz (amplitude 10 mV) at SOC = 0.5 for a linear velocity of vanadium electrolyte flow of 3 cm/s through a cathode made of different carbon materials (indicated in the legend). The equivalent circuit of the VVPB cell half-cell, used to determine the components of its internal resistance to direct current, is shown above the figure.

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7. Fig. 6. Dependences of the voltage (a) of the VVPB cell with the MEA of the composition Pt-C (0.226 mg/cm2)|Nafion 211|CP 6 x 0.28 mm and the potentials of its half-cells relative to the Ag/AgCl reference electrode (b) during the galvanostatic charge/discharge test at ±0.8 A (±200 mA/cm2) for a linear flow rate of vanadium electrolyte of 3 cm/s (65 ml/min), 6th cycle. Solid lines are the curves obtained during charging, dashed lines are during discharging. Dots are the result of measuring the voltage and open-circuit potentials of half-cells at different SOC (data from Fig. 3).

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