Coulometric analysis method for determining the concentration and degree of oxidation of vanadium in the electrolyte of a vanadium flow battery using a hydrogen vanadium cell

Elina A. Petukhova; Valeria S. Ershova; Alexander V. Terentyev; Evgeniy A. Ruban; Roman D. Pichugov; Dmitry V. Konev; Andrey A. Usenko

doi:10.17308/kcmf.2025.27/12490

Elina A. Petukhova Federal Research Center of Problems of Chemical Physics and Medicinal Chemistry, 1 Academician Semenov ave., Chernogolovka 142432, Russian Federation; InEnergy LLC, 2-nd Kotlyakovskiy Lane 18, Moscow 115201, Russian Federation https://orcid.org/0000-0003-2875-0324
Valeria S. Ershova Federal Research Center of Problems of Chemical Physics and Medicinal Chemistry, 1 Academician Semenov ave., Chernogolovka 142432, Russian Federation https://orcid.org/0009-0003-8261-3475
Alexander V. Terentyev Federal Research Center of Problems of Chemical Physics and Medicinal Chemistry, 1 Academician Semenov ave., Chernogolovka 142432, Russian Federation; InEnergy LLC, 2-nd Kotlyakovskiy Lane 18, Moscow 115201, Russian Federation https://orcid.org/0000-0002-7591-9973
Evgeniy A. Ruban Federal Research Center of Problems of Chemical Physics and Medicinal Chemistry, 1 Academician Semenov ave., Chernogolovka 142432, Russian Federation https://orcid.org/0000-0003-3832-1611
Roman D. Pichugov InEnergy LLC, 2-nd Kotlyakovskiy Lane 18, Moscow 115201, Russian Federation; D. I. Mendeleev Russian University of Chemical Technology, 9 Miusskaya pl., Moscow 125047, Russian Federation https://orcid.org/0000-0001-7353-2938
Dmitry V. Konev Federal Research Center of Problems of Chemical Physics and Medicinal Chemistry, 1 Academician Semenov ave., Chernogolovka 142432, Russian Federation https://orcid.org/0000-0002-2188-9254
Andrey A. Usenko Federal Research Center of Problems of Chemical Physics and Medicinal Chemistry, 1 Academician Semenov ave., Chernogolovka 142432, Russian Federation; InEnergy LLC, 2-nd Kotlyakovskiy Lane 18, Moscow 115201, Russian Federation https://orcid.org/0000-0002-4119-5292

DOI: https://doi.org/10.17308/kcmf.2025.27/12490

Keywords: Vanadium electrolyte, Vanadium flow batteries, Coulometry, Hydrogen electrode, Concentration, Degree of oxidation of vanadium

Abstract

Determining the vanadium content and the average degree of oxidation of vanadium ions in an electrolyte is a highly important task, both in the production and operation of vanadium flow batteries and in scientific research aimed at improving the performance characteristics of electrolytes throughout their entire life cycle. This article proposes a solution to this issue using the coulometric analysis of electrolyte samples circulating through a cell with a membrane-electrode unit consisting of a gas diffusion hydrogen electrode, a proton exchange membrane, and a liquid flow electrode. The coulometric analysis involves the oxidation of the sample to the highest degree of vanadium oxidation with further reduction to an oxidation state of +4. The parameters of the procedure (polarization modes and completion conditions) were chosen in order to minimize the relative error in determining the concentration of vanadium up to 5% and the average degree of oxidation up to 2% based on model composition electrolytes with different concentrations and degrees of vanadium oxidation, including sulfuric acid, as well as mixed acid (H₂SO₄ + HCl) compositions

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Author Biographies

Elina A. Petukhova, Federal Research Center of Problems of Chemical Physics and Medicinal Chemistry, 1 Academician Semenov ave., Chernogolovka 142432, Russian Federation; InEnergy LLC, 2-nd Kotlyakovskiy Lane 18, Moscow 115201, Russian Federation

Research Engineer, Federal Research Center of Problems of Chemical Physics and Medicinal Chemistry (Chernogolovka, Russian Federation)

Valeria S. Ershova, Federal Research Center of Problems of Chemical Physics and Medicinal Chemistry, 1 Academician Semenov ave., Chernogolovka 142432, Russian Federation

Laboratory Assistant, Federal Research Center of Problems of Chemical Physics and Medicinal Chemistry (Chernogolovka, Russian Federation)

Alexander V. Terentyev, Federal Research Center of Problems of Chemical Physics and Medicinal Chemistry, 1 Academician Semenov ave., Chernogolovka 142432, Russian Federation; InEnergy LLC, 2-nd Kotlyakovskiy Lane 18, Moscow 115201, Russian Federation

Engineer, Federal Research Center of Problems of Chemical Physics and Medicinal Chemistry (Chernogolovka, Russian Federation)

Evgeniy A. Ruban, Federal Research Center of Problems of Chemical Physics and Medicinal Chemistry, 1 Academician Semenov ave., Chernogolovka 142432, Russian Federation

Junior Research Fellow, Federal Research Center of Problems of Chemical Physics and Medicinal Chemistry (Chernogolovka, Russian Federation)

Roman D. Pichugov, InEnergy LLC, 2-nd Kotlyakovskiy Lane 18, Moscow 115201, Russian Federation; D. I. Mendeleev Russian University of Chemical Technology, 9 Miusskaya pl., Moscow 125047, Russian Federation

Cand. Sci. (Phys.–Math.), Associate Professor, D. I. Mendeleev Russian University of Chemical Technology (Moscow, Russian Federation)

Dmitry V. Konev, Federal Research Center of Problems of Chemical Physics and Medicinal Chemistry, 1 Academician Semenov ave., Chernogolovka 142432, Russian Federation

Cand. Sci. (Chem.), Senior Research Fellow, Federal Research Center of Problems of Chemical Physics and Medicinal Chemistry (Chernogolovka, Russian Federation)

Andrey A. Usenko, Federal Research Center of Problems of Chemical Physics and Medicinal Chemistry, 1 Academician Semenov ave., Chernogolovka 142432, Russian Federation; InEnergy LLC, 2-nd Kotlyakovskiy Lane 18, Moscow 115201, Russian Federation

Cand. Sci. (Phys.–Math.), Research Fellow, Federal Research Center of Problems of Chemical Physics and Medicinal Chemistry (Chernogolovka, Russian Federation)

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