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

封面

如何引用文章

全文:

开放存取 开放存取
受限制的访问 ##reader.subscriptionAccessGranted##
受限制的访问 订阅存取

详细

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.

全文:

受限制的访问

作者简介

O. 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

编辑信件的主要联系方式.
Email: dkfrvzh@yandex.ru
俄罗斯联邦, Chernogolovka; Moscow

D. 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
俄罗斯联邦, Chernogolovka; Moscow

M. Vorotyntsev

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

Email: mivo2010@yandex.com
俄罗斯联邦, Moscow

参考

  1. Olabi, A.G., Onumaegbu, C., Wilberforce, T., Ramadan, M., Abdelkareem, M.A., and Al-Alami, A.H., Critical review of energy storage systems, Energy, 2021, vol. 214, Article number 118987.
  2. Rabuni, M.F., Li, T., Othman, M.H.D., Adnan, F.H., and Li, K., Progress in Solid Oxide Fuel Cells with Hydrocarbon Fuels, Energies, 2023, vol. 16, no. 17, Article number 6404.
  3. Lee, A.P.C. and Lee, C., It's time for an update – A perspective on fuel cell electrodes. Can. J. Chem. Eng., 2023, vol. 101, no. 11, p. 6050.
  4. Belhaj, I., Faria, M., Sljukic, B., Geraldes, V., and Santos, D.M., Bipolar Membranes for Direct Borohydride Fuel Cells – A Review, Membranes, 2023, vol. 13, no. 8, Article number 730.
  5. Muller, K., Thiele, S., and Wasserscheid, P., Evaluations of concepts for the integration of fuel cells in liquid organic hydrogen carrier systems, Energy & fuels, 2019, vol. 33, no. 10, p. 10324.
  6. Hassan, Q., Azzawi, I.D., Sameen, A.Z., and Salman, H.M., Hydrogen fuel cell vehicles: Opportunities and challenges, Sustainability, 2023, vol. 15, no. 15, Article number 11501.
  7. Braun, K., Wolf, M., De Oliveira, A., Preuster, P., Wasserscheid, P., Thiele, S., Weiss, L., and Wensing, M., Energetics of Technical Integration of 2‐Propanol Fuel Cells: Thermodynamic and Current and Future Technical Feasibility, Energy technol., 2022, vol. 10, no. 8, Article number 2200343.
  8. Cho, K.T., Tucker, M.C., and Weber, A.Z., A review of hydrogen/halogen flow cells, Energy Technol., 2016, vol. 4, no. 6, p. 655.
  9. Rubio-Garcia, J., Kucernak, A., Zhao, D., Li, D., Fahy, K., Yufit, V., Brandon, N., and Gomez-Gonzalez, M., Hydrogen/manganese hybrid redox flow battery, J. Phys. Energy, 2018, vol. 1, no. 1, Article number 015006.
  10. Preger, Y., Gerken, J.B., Biswas, S., Anson, C.W., Johnson, M.R., Root, T.W., and Stahl, S.S., Quinone-mediated electrochemical O2 reduction accessing high power density with an off-electrode Co–N/C catalyst, Joule, 2018, vol. 2, no. 12, p. 2722.
  11. Lin, G., Chong, P.Y., Yarlagadda, V., Nguyen, T.V., Wycisk, R.J., Pintauro, P.N., Bates, M., Mukerjee, S., Tucker, M.C., and Weber, A.Z., Advanced hydrogen-bromine flow batteries with improved efficiency, durability and cost, J. Electrochem. Soc., 2015, vol. 163, no. 1, p. A5049.
  12. Gunn, N.L., Ward, D.B., Menelaou, C., Herbert, M.A., and Davies, T.J., Investigation of a chemically regenerative redox cathode polymer electrolyte fuel cell using a phosphomolybdovanadate polyoxoanion catholyte, J. Power Sources, 2017, vol. 348, p. 107.
  13. Ge, G., Zhang, C., and Li, X., Multi-electron transfer electrode materials for high-energy-density flow batteries, Next Energy, 2023, vol. 1, no. 3, Article number 100043.
  14. Chen, R., Redox flow batteries for energy storage: Recent advances in using organic active materials, Curr. Opin. Electrochem., 2020, vol. 21, p. 40.
  15. VanGelder, L.E., Kosswattaarachchi, A.M., Forrestel, P.L., Cook, T.R., and Matson, E.M., Polyoxovanadate-alkoxide clusters as multi-electron charge carriers for symmetric non-aqueous redox flow batteries, Chem. Sci., 2018, vol. 9, no. 6, p. 1692.
  16. Laramie, S.M., Milshtein, J.D., Breault, T.M., Brushett, F.R., and Thompson, L.T., Performance and cost characteristics of multi-electron transfer, common ion exchange non-aqueous redox flow batteries, J. Power Sources, 2016, vol. 327, p. 681.
  17. Fang, X., Cavazos, A.T., Li, Z., Li, C., Xie, J., Wassall, S.R., Zhang, L., and Wei, X., Six-electron organic redoxmers for aqueous redox flow batteries, Chem. Commun., 2022, vol. 58, no. 95, p. 13226.
  18. Tolmachev, Y.V. and Vorotyntsev, M.A., Fuel cells with chemically regenerative redox cathodes, Russ. J. Electrochem., 2014, vol. 50, p. 403.
  19. Han, S.B., Kwak, D.H., Park, H.S., Choi, I.A., Park, J.Y., Kim, S.J., Kim, M.C., Hong, S., and Park, K.W., High‐Performance Chemically Regenerative Redox Fuel Cells Using a NO3–/NO Regeneration Reaction, Angew. Chem. Int. Ed., 2017, vol. 56, no. 11, p. 2893.
  20. Cho, K.T. and Razaulla, T., Redox-mediated bromate based electrochemical energy system, J. Electrochem. Soc., 2019, vol. 166, no. 2, p. A286.
  21. Chinannai, M.F. and Ju, H., Analysis of performance improvement of hydrogen/bromine flow batteries by using bromate electrolyte, Int. J. Hydrogen Energy, 2021, vol. 46, no. 26, p. 13760.
  22. Tolmachev, Y.V., Piatkivskyi, A., Ryzhov, V.V., Konev, D.V., and Vorotyntsev, M.A., Energy cycle based on a high specific energy aqueous flow battery and its potential use for fully electric vehicles and for direct solar-to-chemical energy conversion, J. Solid State Electrochem., 2015, vol. 19, p. 2711.
  23. Vorotyntsev, M.A., Antipov, A.E., and Konev, D.V., Bromate anion reduction: novel autocatalytic (EC″) mechanism of electrochemical processes. Its implication for redox flow batteries of high energy and power densities, Pure Appl. Chem., 2017, vol. 89, no. 10, p. 1429.
  24. Modestov, A.D., Konev, D.V., Antipov, A.E., Petrov, M.M., Pichugov, R.D., and Vorotyntsev, M.A., Bromate electroreduction from sulfuric acid solution at rotating disk electrode: Experimental study, Electrochim. Acta, 2018, vol. 259, p. 655.
  25. Modestov, A.D., Konev, D.V., Tripachev, O.V., Antipov, A.E., Tolmachev, Y.V., and Vorotyntsev, M.A., A Hydrogen–Bromate Flow Battery for Air‐Deficient Environments, Energy Technol., 2018, vol. 6, no. 2, p. 242.
  26. Modestov, A.D., Konev, D.V., Antipov, A.E., and Vorotyntsev, M.A., Hydrogen-bromate flow battery: can one reach both high bromate utilization and specific power? J. Solid State Electrochem., 2019, vol. 23, p. 3075.
  27. Campbell, A.N. and Paterson, W.G., The conductances of aqueous solutions of lithium chlorate at 25.00°C and at 131.8°C, Can. J. Chem., 1958, vol. 36, no. 6, p. 1004.
  28. Campbell, A.N., Kartzmark, E.M., and Maryk, W.B., The systems sodium chlorate-water-dioxane and lithium chlorate-water-dioxane, at 25°, Can. J. Chem., 1966, vol. 44, no. 8, p. 935.
  29. Hanley, J., Chevrier, V.F., Berget, D.J., and Adams, R.D., Chlorate salts and solutions on Mars, Geophys. Res. Lett., 2012, vol. 39, no. 8, Article number L08201.
  30. Konev, D.V., Goncharova, O.A., Tolmachev, Y.V., and Vorotyntsev, M.A., The Role of Chlorine Dioxide in the Electroreduction of Chlorates at low pH, Russ. J. Electrochem., 2022, vol. 58, no. 11, p. 978.
  31. Konev, D.V., Istakova, O.I., Ruban, E.A., Glazkov, A.T., and Vorotyntsev, M.A., Hydrogen-Chlorate Electric Power Source: Feasibility of the Device, Discharge Characteristics and Modes of Operation, Molecules, 2022, vol. 27, no. 17, Article number 5638.
  32. Kieffer, R.G. and Gordon, G., Disproportionation of chlorous acid. I. Stoichiometry, Inorg. Chem., 1968, vol. 7, no. 2, p. 235.
  33. Romanova, N.V., Konev, D.V., Muratov, D.S., Ruban, E.A., Tolstel, D.O., Galin, M.Z., Kuznetsov, V.V., and Vorotyntsev, M.A., Characteristics of the Charge–Discharge Cycle of Hydrogen–Bromine Battery with IrO2–TiO2-Titanium Felt Cathode Operating in the Full Capacity Utilization Mode, Russ. J. Electrochem., 2024, vol. 60, no. 12, p. 1061.

补充文件

附件文件
动作
1. JATS XML
下载
2. Supplementary
下载 (234KB)
索引源数据
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

下载 (250KB)
索引源数据
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.

下载 (303KB)
索引源数据
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.

下载 (252KB)
索引源数据
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.

下载 (276KB)
索引源数据
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.

下载 (182KB)
索引源数据

版权所有 © Russian Academy of Sciences, 2025