Given the strong demands for high purity vanadium products dedicated for all-vanadium redox flow battery (VRFB), numerous preparation technologies have been developed. One of them, the chloride process that using vanadium oxytrichloride (VOCl 3 ) as purification intermediate presents distinct technical advantages. The intermediate is readily purified via distillation process to remove most of the impurities. However, the trace titanium tetrachloride (TiCl 4 ) is difficult to be removed, due to close saturated vapor pressures. In present work, based on thermodynamic calculation and analyses, we found that TiCl 4 reacts with water significant preferentially to form the corresponding oxide, compared with VOCl 3 . Then we proposed a novel method to remove trace TiCl 4 from VOCl 3 by selective hydrolysis – distillation. The related experiments were conducted and validated the feasibility of the innovative process. Vanadium pentoxide (V 2 O 5 ) with purity higher than 99.99 wt% (4N) was further prepared from the purified VOCl 3 by precipitation – calcination .
In the context of the global energy transition, the intermittency and instability of renewable energy have become major bottlenecks limiting its large-scale application. Vanadium redox flow batteries (VRFBs), recognized for their long cycle life, high safety, and environmental benefits, are ideal solutions for large-scale energy storage. The cost and performance of the electrolyte are critical factors determining the efficiency and economic viability of the battery. However, the preparation of vanadium electrolytes faces challenges, including complex production processes and high costs. Thus, developing high-concentration, high-performance, and low-cost vanadium electrolytes while ensuring green production of raw materials is an urgent technical challenge. This study presents a short-process clean method for the production of high-purity VOCl 3 from NaVO 3 extracted from vanadium slag, which is applied to the sulfate-chloride electrolyte system of VRFBs. In this system, VOCl 3 serves as the Cl − source, significantly reducing production costs by eliminating the need for additional HCl. Compared to traditional vanadium raw materials (e.g., V 2 O 5 and VOSO 4 ), the energy efficiency (EE) of the electrolyte is improved by 13.6 %. This research presents an efficient and cost-effective approach for the sustainable production of vanadium electrolytes, providing significant support for the advancement of high-performance and economically viable VRFB technology.
Yang Shuyi,Xing Zhenqiang,E Tao,Liu Lin,Qian Jianhua
Organic reagent is considered as one of the most promising reductants for deeply removing vanadium (V) trichloride oxide (VOCl 3 ) from crude titanium tetrachloride (TiCl 4 ). Nevertheless, indeterminate active component and unclearly removal mechanisms appear to be the obstacles to separate VOCl 3 from TiCl 4 using organic reagent. Herein we conduct the experiment to explore it. Firstly, the organic reagents are obtained from enterprise (noted as EOR 1 –EOR 7 ), and then it is determined that carbon aromatic (C A ) is the active component for removing VOCl 3 . Furthermore, modified organic reagents (noted as MOR 1 –MOR 4 ) are prepared via adding aromatic hydrocarbon oil and stearic acid to EOR 7 , then indicating that MOR 3 is endowed with the best capacity to remove VOCl 3 . In addition, the residues obtained from distillation experiment are comprehensively analyzed (using X-ray diffraction (XRD), transmission electron microscope (TEM) and scanning electron microscope (SEM) etc.), revealing that porous amorphous carbon that deriving from MOR, plays an excellent role in removing VOCl 3 from TiCl 4 system. Therefore, the removal mechanisms can be explained like that porous amorphous carbon reduces VOCl 3 into insoluble vanadium (III) chloride (VCl 3 ) and vanadium (IV) oxide dichloride (VOCl 2 ), and then they are separated via adsorption process, with the help of porous amorphous carbon.
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