IP Library Granted Patent US 12,451,528
Granted Patent B2
US 12,451,528 · App. 17/171,272 · Granted Oct 21, 2025

In-situ electrolyte preparation in flow battery

Inventors: Weina Li (South Glastonbury, CT); Michael L. Perry (Glastonbury, CT)
Assignee: RTX CORPORATION
H01M10/446H01M8/188H01M8/20H01M10/0563H02J7/00H01M2300/002Y02E60/50
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Quick Facts
Patent No.
US 12,451,528
App. No.
17/171,272
Granted
Oct 21, 2025
Kind
B2
Abstract

A method of in-situ electrolyte preparation in a flow battery includes providing a vanadium-based electrolyte solution having vanadium ions of predominantly vanadium V 4+ to a first electrode and a second electrode of at least one cell of a flow battery. The vanadium V 4+ at the first electrode is converted to vanadium V 3+ and the vanadium V 4+ at the second electrode is converted to vanadium V 5+ by providing electrical energy to the electrodes. A reducing agent is then provided to the vanadium V 5+ at the second electrode to reduce the V 5+ to vanadium V 4+ . The vanadium V 3+ at the first electrode is then converted to vanadium V 2+ and the vanadium V 4+ at the second electrode is then converted to vanadium V 5+ by providing electrical energy to the electrodes. A simple method to produce predominantly vanadium V 4+ electrolyte from a V 5+ source, such as V 2 O 5 , is also taught.

Claims (15)

1. A method of in-situ electrolyte preparation in a flow battery, the method comprising:

(a) providing equal parts of a vanadium-based electrolyte solution having vanadium ions of predominantly vanadium V 4+ to a first electrode and a second electrode of at least one cell of a flow battery, the second electrode being spaced apart from the first electrode, with an electrolyte separator layer arranged between the first electrode and the second electrode;

(b) while the vanadium-based electrolyte solution is in the at least one cell of the flow battery, converting the vanadium V 4+ in the vanadium-based electrolyte solution at the first electrode to vanadium V 3+ and converting the vanadium V 4+ in the vanadium-based electrolyte solution at the second electrode to vanadium V 5+ by providing electrical energy through an electric circuit to the first electrode and the second electrode;

(c) after said step (b), while the vanadium-based electrolyte solution is in the at least one cell of the flow battery, providing a reducing agent to the vanadium-based electrolyte solution of the second electrolyte to reduce the vanadium V 5+ to vanadium V 4+ ; and

(d) after said step (c), while the vanadium-based electrolyte solution is in the at least one cell of the flow battery, establishing the flow battery to be in a fully charged state by converting the vanadium V 3+ of said step (b) in the vanadium-based electrolyte solution at the first electrode to vanadium V 2+ and converting the vanadium V 4+ of said step (c) in the vanadium-based electrolyte solution at the second electrode to vanadium V 5+ by providing electrical energy through the electric circuit to the first electrode and the second electrode.

2. The method as recited in claim 1 , wherein the vanadium ions of said step (a) have a concentration of 90% or greater of the vanadium V 4+ .

3. The method as recited in claim 1 , wherein the vanadium ions of said step (a) have a concentration of 95% or greater of vanadium V 4+ .

4. The method as recited in claim 1 , wherein the vanadium-based electrolyte solution includes sulfuric acid.

5. The method as recited in claim 1 , wherein the concentration of the vanadium V 2+ of said step (d) in the vanadium-based electrolyte solution at the first electrode is equal to the concentration of the vanadium V 5+ of said step (d) in the vanadium-based electrolyte solution at the second electrode within +/−5%.

6. The method as recited in claim 1 , further comprising preparing the vanadium-based electrolyte solution having vanadium ions of predominantly vanadium V 4+ of said step (a) by:

(i) providing a first solution and a second solution, at least one of the first solution and the second solution including vanadium V 5+ , at least one of the first solution and the second solution including a reducing agent, and a ratio of moles of the reducing agent to moles of vanadium V 5+ is 2:1 or greater; and

(ii) combining the first solution and the second solution, the reducing agent reducing the vanadium V 5+ to the vanadium V 4+ .

7. The method as recited in claim 1 , wherein the reducing agent includes at least one of oxalic acid, formic acid, and alcohol.

8. The method as recited in claim 1 , further comprising, after said step (d), discharging the flow battery by drawing electrical energy through the electric circuit from the first electrode and the second electrode to convert the vanadium V 2+ to V 3+ and to convert the vanadium V 5+ to V 4+ .

9. The method as recited in claim 1 , further comprising, after said step (d), repeatedly discharging and charging the flow battery by, respectively, drawing electrical energy through the electric circuit from the first electrode and the second electrode to convert the vanadium V 2+ to V 3+ and to convert the vanadium V 5+ to V 4+ and providing electrical energy through the electric circuit to the first electrode and the second electrode to convert the vanadium V 3+ to V 2+ and convert the vanadium V 4+ to V 5+ .

Assignments (1)
CHANGE OF NAME Recorded Oct 4, 2023
From: RAYTHEON TECHNOLOGIES CORPORATION
To: RTX CORPORATION
Reel/Frame 065121/0036 →
Continuity (2)
Continuation 14892586
Related Publication 20210167433A1 · Jun 3, 2021
References Cited (45)
US 5318865A · Kaneko et al. · 1994 [cited by applicant]
US 5648184A · Inoue et al. · 1997 [cited by applicant]
US 9166243B2 · Perry · 2015 [cited by applicant]
US 20060183016A1 · Kazacos · 2006 [cited by applicant]
US 20080274393A1 · Markoski et al. · 2008 [cited by applicant]
US 20080292938A1 · Perry et al. · 2008 [cited by applicant]
US 20090136789A1 · Pien et al. · 2009 [cited by applicant]
US 20130084482A1 · Chang · 2013 [cited by applicant]
US 20130095362A1 · Keshavarz · 2013 [cited by applicant]
JP S5419228 · 1979 [cited by applicant]
JP H02148659 · 1990 [cited by applicant]
JP 2006156029 · 2006 [cited by applicant]
WO 1989005528 · 1988 [cited by applicant]
WO 1989005363 · 1989 [cited by applicant]
WO 2013027076 · 2013 [cited by applicant]
WO 2013054921 · 2013 [cited by applicant]
File History for U.S. Appl. No. 13/513,651 now U.S. Pat. No. 9,166,243 issued Oct. 20, 2015. [cited by applicant]
Certified Translation. Japanese Publication of Examined Patent Application No. S54-102887 published Jul. 13, 1979. [cited by applicant]
Certified Translation. Japanese Unexamined Patent Application No. H2-148659 published Jun. 7, 1990. [cited by applicant]
Certified Translation. Japanese Unexamined Patent Application No. 2006-156029 published Jun. 15, 1990. [cited by applicant]
Linden, D. and Reddy, T.B. Eds. (2002). Handbook of batteries. New York, NY: McGraw-Hill. pp. 37.12, 18-23, 42.3-42.13, 43.11-43.3, Appendix A. [cited by applicant]
Laramini, J. and Dicks, A. (2003). Fuel cell systems explained. Chichester, England: John Wiley & Sons Inc. pp. xv, xvi, 18-19, 88-89, 94-96. [cited by applicant]
Haar, D. (2016). Dan Haar: United Technologies battery could upend the power business. Hartford Courant. Retrieved Feb. 22, 2017 from: http://www.courant.com/business/dan-haar/hc-haar-united-technologies-battery-for-ele… [cited by applicant]
Aricò, A.S., Cretì, P., Baglio, V., Modica, E., and Antonucci, V. (2000). Influence of flow field design on the performance of a direct methanol fuel cell. Journal of Power Sources vol. 91. 2000. pp. 202-209. [cited by applicant]
Li, X. and Sabir, I. (2004). Review of bipolar plates in PEM fuel cells: Flow-field designs. International Journal of Hydrogen Energy vol. 30. 2005. pp. 359-371. [cited by applicant]
Negishi, A. (2003). Redox flow battery. (Certified Translation). Fuel Cells vol. 2(4). 2003. pp. 69-74. [cited by applicant]
Yi, J.S., and Nguyen T.V. (1996). Abstract: Hydrodynamics of reactant gas in the electrode of PEM fuel cells with inter-digitated flow fields. The Electrochemical Society, Inc. Meeting Abstracts. Fall Meeting, San Anton… [cited by applicant]
Kazim, A., Liu, H.T., and Forges, P. (1999). Modelling of performance of PEM fuel cells with conventional and interdigitated flow fields. Journal of Applied Electrochemistry vol. 29(12). 1999. pp. 1409-1416. [cited by applicant]
Wang, L. and Liu, H. (2004). Performance studies of PEM fuel cells with interdigitated flow fields. Journal of Power Sources vol. 134(2). 2004. pp. 185-196. [cited by applicant]
Guo, S.M. (2005). The simulation of a PEMFC with an interdigitated flow field design. Computational Science 5th International Conference. May 2005. pp. 104-111. [cited by applicant]
He, W., Yi, J.S., Nguyen, T.V. (2000). Two-phase flow model of the cathode of PEM fuel ceels using interdigitated flow fields. AIChE Journal vol. 46(10). Oct. 2000. pp. 2053-2064. [cited by applicant]
Nozaki, K., Hamamoto, O., Kaneko, H., and Ozawa, T. (1975). (Certified Translation). Prospect of power storage using redox flow type secondary battery. Electrochemical/Electro-thermal Study Group Material. The Institute… [cited by applicant]
Declaration of Dr. Toru Kato, Ph.D. In re U.S. Pat. No. 9,166,243. Executed Feb. 23, 2017. pp. 1-89. [cited by applicant]
Prior Art Claim Chart for U.S. Pat. No. 9,166,243, Oct. 20, 2015. [cited by applicant]
Ponce de León, C., Frías-Ferrer, A., González-García, Szánto, D.A., and Walsh, F.C. (2006). Redox flow cells for energy conversion. Journal of Power Sources vol. 160. 2006. pp. 716-732. [cited by applicant]
Negishi, A. (2003). Redox flow battery. Fuel Cells vol. 2(4). 2003. pp. 69-74. [cited by applicant]
Nozaki, K., Hamamoto, O., Kaneko, H., and Ozawa, T. (1975). Prospect of power storage using redox flow type secondary battery. Electrochemical/Electro-thermal Study Group Material. The Institute of Electrical Engineers … [cited by applicant]
Shigematsu, T. (2011). Redox flow battery for energy storage. SEI Technical Review No. 73. Oct. 2011. pp. 4-13. [cited by applicant]
Tokuda, N., Kanno, T., Hara, T., Shigematsu, T., Tsutsui, Y., Ikeuchi, A., Itou, T., et al. (2000). Development of a redox flow battery system. SEI Technical Review No. 73. Jun. 2000. pp. 88-94. [cited by applicant]
Hagedorn, N.H. (1984). NASA redox storage system development project. Final Report. DOE/NASA/12726-24. Oct. 1984. pp. 1-43. [cited by applicant]
Sumitomo Electric. Redox Flow Battery. Technical Document. Retrieved May 8, 2017 from: http://global-sei.com/products/redox/pdf/redox-flow-battery.pdf. [cited by applicant]
Petition for Inter Partes Review of U.S. Pat. No. 9,166,243. [cited by applicant]
International Preliminary Report of Patentability for PCT Application No. PCT/US2013/042174 mailed May 28, 2015. [cited by applicant]
M. Bobtelsky. The Rate of Reduction of Vanadium Pentoxide in Concentrated Acid Solutions. Reduction of Vanadium Pentoxide by Arsenious Acid, Oxalic Acid, Formaldehyde and Ethyl Alcohol. Journal of the American Chemical … [cited by applicant]
International Search Report for PCT Application No. PCT/US2013/042174 mailed Oct. 21, 2013. [cited by applicant]