The poor operational stability of electrolytes is a persistent impediment in building redox flow battery technology; choosing suitable stability additives is usually the research direction to solve this problem. The effects of five phosphate containing additives (including 1-hydroxyethylidene-1,1-diphosphonic acid (HEDP), hexamethylene diamine tetramethylene phosphonic acid (HDTMPA), amino trimethylene phosphonic acid (ATMPA), sodium ethylenediamine tetramethylene phosphonate (EDTMPS), and diethyl triamine pentamethylene phosphonic acid (DTPMP)) on the thermal stability and electrochemical performance of the positive electrolyte of vanadium redox flow battery were investigated. With 0.5 wt% addition, most of the selected additives were able to improve the thermal stability of the electrolyte. HEDP and HDTMPA extended the stability time of the pentavalent vanadium electrolyte at 50 °C from 5 days (blank sample) to 30 days and 15 days, respectively. The electrochemical performance of the electrolyte was further investigated by cyclic voltammetry, steady state polarization, and electrochemical impedance spectroscopy tests. It was found that most of the additives enhanced the electrochemical activity of the positive electrolyte, and the diffusion coefficients, exchange current densities, and reaction rate constants of V(IV) species became larger with the addition of these additives. It is verified that the thermal stability and electrochemical stability of the electrolyte are significantly improved by the combination of ATMPA + HEDP or ATMPA + HDTMPA. This study provides a new approach to improve the stability of the positive electrolyte for vanadium redox flow battery.

Natisite (Na₂TiSiO₅) is a layered sodium titanosilicate containing TiO₅ square pyramids. The structure evolution of natisite in water and acid solutions is the basis for its potential applications. With Na₂SiO₃ as the silicon source, natisite with the shape of the square sheet was selectively prepared from the hydrothermal method with 14.3 mol/L NaOH solution at 240 °C. Natisite has 20 Raman active modes and 22 infrared active modes from the first-principles calculations within density functional theory, and the calculated Raman and infrared spectra agree well with the experimental ones. The characteristic Raman peak at 844 cm⁻¹ is caused by the symmetric stretching of the apical Ti–O bond in the TiO₅ unit, assigning to A_1g and B_2g modes. Natisite remains relatively stable in water with a sodium leaching percentage of lower than 6%. When washing with sulfuric acid solutions, the interlayer spacing of natisite is reduced due to the extensive removal of sodium ions, and an intermediate composed of SiO₄ and newly formed TiO₆ units may be formed. Moreover, after washing with water and acid solutions, 95.5%, 63.4%, and 35.2% of Na, Si, and Ti in natisite can be leached in total, respectively, resulting in the structural disintegration of natisite.

This review focuses on the existing technologies for preparing V ^3.5+ electrolyte for vanadium flow batteries and related capacity recovery strategies which share similar chemical principles and technologies.