Methods for the preparation of electrolytes for chromium-iron redox flow batteries
A method for preparing a redox flow battery electrolyte is provided. In some embodiments, the method includes the processing of raw materials containing sources of chromium ions in a high oxidation state. In some embodiments, a solution of the raw materials in an acidic aqueous solution is subjected to a reducing process to reduce the chromium in a high oxide state to an aqueous electrolyte containing chromium (III) ions. In some embodiments, the reducing process is electrochemical process. In some embodiments, the reducing process is addition of an inorganic reductant. In some embodiments, the reducing process is addition of an organic reductant. In some embodiments, the inorganic reductant or the organic reductant includes iron powder.
1. A method for preparing a redox battery electrolyte, comprising:
dissolving a raw material that includes at least one source of chromium ions in a first oxidation state in an acidic aqueous liquid to form a solution of chromium ions;
reducing the chromium ions in the solution to a second oxidation state that is lower than the first oxidation state by subjecting the solution to a reductant until substantially all of the chromium ions in the first oxidation state are reduced to the second oxidation state, wherein the chromium ions in the first oxidation state comprise chromium(VI) ions and the chromium ions in the second oxidation state comprise chromium (III) ions; and
after reducing the chromium ions in the solution, adding a source of iron (II) ions to the solution, the source of iron (II) ions comprising iron powder, to form the redox battery electrolyte.
2. The method of claim 1 , further comprising filtering the solution.
3. The method of claim 2 , wherein filtering the solution includes filtering with a solid filter and a filter aid.
4. The method of claim 1 , wherein subjecting the solution to a reductant includes reducing the chromium ions in the solution with an electrochemical reaction using at least one electrode.
5. The method of claim 4 , wherein the at least one electrode is comprised of at least one material from the set of titanium, carbon felt, glassy carbon, graphite, polypropylene graphite composite, iron, steel, and mixed metal oxide.
6. The method of claim 1 , wherein the at least one source of chromium ions includes a soluble dichromate salt of sodium or potassium.
7. The method of claim 1 , wherein the at least one source of chromium ions includes a soluble chromate salt of sodium or potassium.
8. The method of claim 1 , wherein the at least one source of chromium ions includes chromium trioxide.
9. The method of claim 1 , wherein the at acidic solution includes at least one of the acids chosen from the set of hydrochloric acid, hydrobromic acid, sulfuric acid, sulfonic acid, phosphoric acid, phosphonic acid, perchloric acid, and carboxylic acids.
10. The method of claim 1 , wherein the acidic solution includes hydrochloric acid.
11. The method of claim 1 , wherein subjecting the solution to a reductant includes adding an inorganic reducing agent to the solution.
12. The method of claim 11 , wherein the inorganic reducing agent includes at least one of the set sodium dithionite, sodium bisulfate, sodium metabisulfite, and sodium sulfite.
13. The method of claim 11 , wherein adding an inorganic reducing agent to the solution includes adding less than a stoichiometric amount of the inorganic reducing agent to the solution.
14. The method of claim 1 , wherein subjecting the solution to a reductant includes adding an organic reducing agent to the solution.
15. The method of claim 13 , wherein the organic reducing agent includes at least one of the set formic acid, oxalic acid, methanol, ethanol, lower alcohol, ethylene glycol, glucose, sucrose, raw sugar, and molasses.
16. The method of claim 14 , wherein less than stoichiometric amount of the organic reducing agent is added to the solution.
17. The method of claim 16 , wherein one equivalent of the organic reducing agent is used.
18. The method of claim 1 , wherein subjecting the solution to a reductant includes adding iron powder to the solution.
19. The method of claim 1 , further including adjusting an acid concentration of the solution to form an electrolyte.
20. The method of claim 4 , wherein electrochemical reduction occurs until an electrochemical current is reduced indicating a substantial reduction of all the chromium ion in the first oxidation state.