IP Library › Granted Patent US 12,368,177
Granted Patent B2
US 12,368,177 · App. 17/961,831 · Granted Jul 22, 2025

Flow batteries with insoluble polymer supported redox active materials

Inventor: Thomas Vaid (Ann Arbor, MI)
Assignee: REGENTS OF THE UNIVERSITY OF MICHIGAN
H01M8/18H01M8/023
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Quick Facts
Patent No.
US 12,368,177
App. No.
17/961,831
Granted
Jul 22, 2025
Kind
B2
Abstract

A redox matched flow battery utilizes insoluble functionalized catholyte and anolyte beads to store charge on redox-active moieties tethered to the beads, with charge being transferred between the electrodes and the bead using a soluble, redox-matched mediator.

Claims (23)

1. A redox-matched flow battery, comprising:

an anolyte reservoir comprising anolyte beads immersed in an electrolyte solution;

a catholyte reservoir comprising catholyte beads immersed in the electrolyte solution;

an electrochemical cell in fluid communication with the anolyte reservoir and the catholyte reservoir, the cell comprising a separator dividing the cell into an anolyte chamber and a catholyte compartment, an anode arranged in the anolyte chamber and a cathode arranged in the catholyte compartment, wherein the anolyte reservoir is in fluid communication with the anolyte compartment to circulate the electrolyte solution as an anolyte solution through the anolyte compartment and the catholyte reservoir is in fluid communication with the catholyte compartment to circulate the electrolyte solution as a catholyte solution through the catholyte compartment,

wherein:

the anolyte beads are polymer beads insoluble in the electrolyte solution functionalized with a negative redox-active moiety,

the catholyte beads are polymer beads insoluble in the electrolyte solution functionalized with a positive redox-active moiety,

the electrolyte solution comprises a first soluble mediator having a redox potential substantially the same as a redox potential of the negative redox-active moiety, and a second soluble mediator having a redox potential substantially the same as a redox potential of the positive redox-active moiety,

in the anolyte reservoir, the first soluble mediator is adapted to undergo redox exchange with the negative redox-active moiety of the anolyte beads while the second soluble mediator remains inactive in the redox exchange;

in the catholyte reservoir, the second soluble mediator is adapted to undergo redox exchange with the positive redox-active moiety while the first soluble mediator remains inactive in the redox exchange, and

the catholyte and anolyte beads are adapted to swell in the electrolyte solution.

2. The battery of claim 1 , wherein the first soluble mediator and the second soluble mediator are present in the electrolyte solution in a 1:1 molar ratio.

3. The battery of claim 1 , wherein the insoluble polymer of one or both of the anolyte beads and the catholyte beads comprises polystyrene.

4. The battery of claim 3 , wherein the insoluble polymer is poly(chloromethylstyrene-co-styrene-co-divinylbenzene).

5. The battery of claim 1 , wherein the negative redox-active moiety and the first soluble mediator each comprises a viologen.

6. The battery of claim 5 , wherein the viologen is [Bn-bpy-Me 2+ ][PF 6 − ] 2 .

7. The battery of claim 1 , wherein the positive redox-active moiety and the second soluble mediator each comprises a ferrocene and/or a cyclopropenium.

8. The battery of claim 7 , wherein the ferrocene is Methyl ferrocenecarboxylate.

9. The battery of claim 7 , wherein the cyclopropenium is amino cyclopropenium.

10. The battery of claim 1 , wherein the anolyte reservoir comprises a porous divider upon which with the anolyte beads are disposed, the porous divider is adapted to prevent the anolyte beads from flowing through the divider, but allow the electrolyte solution to flow there-through, and the electrolyte from a region below the divider is flowed from the anolyte reservoir into the cell and electrolyte collected from the cell is flowed back to into the anolyte reservoir at a region above the divider.

11. The battery of claim 1 , wherein the catholyte reservoir comprises a porous divider upon which with the catholyte beads are disposed, the porous divider is adapted to prevent he catholyte beads from flowing through the divider, but allow the electrolyte solution to flow there-through, and the electrolyte from a region below the divider is flowed from the catholyte reservoir into the cell and electrolyte collected from the cell is flowed back to into the catholyte reservoir at a region above the divider.

12. The battery of claim 1 , wherein the separator is an ion exchange membrane.

13. The battery of claim 1 , wherein the electrolyte comprises 25 mM or less of each of the first and second soluble mediators.

Assignments (2)
CONFIRMATORY LICENSE Recorded Jun 25, 2024
From: UNIVERSITY OF MICHIGAN
To: U.S. DEPARTMENT OF ENERGY
Reel/Frame 067826/0285 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Oct 13, 2022
From: VAID, THOMAS
To: REGENTS OF THE UNIVERSITY OF MICHIGAN
Reel/Frame 061415/0838 →
Continuity (2)
Provisional Application 63262325 · Oct 8, 2021
Related Publication 20230122822A1 · Apr 20, 2023
References Cited (41)
US 20210273252A1 · Ito et al. · 2021 [cited by examiner]
US 20230178784A1 · Sevov et al. · 2023 [cited by examiner]
Duan et al., “Wine-Dark Sea” in an Organic Flow Battery: Storing Negative Charge in 2, 1,3-Benzothiadiazole Radicals Leads to Improved Cyclability, ACS Energy Lett., 2:1156-1161 (2017). [cited by applicant]
Duan, W., et al., A symmetric organic-based nonaqueous redox flow battery and its state of charge diagnostics by FTIR†, J. Mater. Chem. A, 4:5448-5456 (2016). [cited by applicant]
Hendriks, K. H., et al., High-Performance Oligomeric Catholytes for Effective Macromolecular Separation in Nonaqueous Redox Flow Batteries, ACS Cent. Sci., 4(2):189-196 (2018). [cited by applicant]
Hu et al., Long-Cycling Aqueous Organic Redox Flow Battery (AORFB) toward Sustainable and Safe Energy Storage, J. Am. Chem. Soc., 139:1207-1214 (2017). [cited by applicant]
Huang, Q., Reversible chemical delithiation/lithiation of LifePO4: towards a redox flow lithium-ion battery, Phys.Chem. Chem. Phys., 15:5 (1973). [cited by applicant]
Jennings, J. R., et al., Kinetics of LixFePO4 Lithiation/Delithiation by Ferrocene-Based Redox Mediators: An Electrochemical Approach, J. Phys. Chem. C, 119:17522-17528 (2015). [cited by applicant]
Jia, C., et al., High-energy density nonaqueous all redox flow lithium battery enabled with a polymeric membrane, Sci. Adv., 1:e1500886 (2015). [cited by applicant]
Kita et al., Hydrophilic Polymer Supports for Solid-Phase Synthesis: Preparation of Poly(ethylene glycol) Methacrylate Polymer Beads Using “Classical” Suspension Polymerization in Aqueous Medium and Their Application in… [cited by applicant]
Kowalski J. A., et al., A Method for Evaluating Soluble Redox Couple Stability Using Microelectrode Voltammetry, Journal of The Electrochemical Society, 167:160513 (2020). [cited by applicant]
Liang, Z., et al., Comparison of Separators vs Membranes in Nonaqueous Redox Flow Battery Electrolytes Containing Small Molecule Active Materials, ACS Appl. Energy Mater., 4:5443-5451 (2021). [cited by applicant]
M. Darling et al., Pathways to low-cost electrochemical energy storage: a comparison of aqueous and nonaqueous flow batteries, Energy Environ. Sci., 7:3459-3477 (2014). [cited by applicant]
McElvan, S. M., et al., Piperidine Derivatives. XX. The Preparation and Reactions of 1-Methyl-3-piperidone, J. Am. Chem. Soc., 71(3): 896-900 (1949). [cited by applicant]
Moutet, J., et al., Symmetric, Robust, and High-Voltage Organic Redox Flow Battery Model Based on a Helical Carbenium lon Electrolyte, ACS Appl. Energy Mater., 4(1):9-14 (2021). [cited by applicant]
Nchimi-Nono et al., Radical-Cation Dimerization Overwhelms Inclusion in [n]Pseudorotaxanes, Chem. Eur. J., 20:7334-7344 (2014). [cited by applicant]
Noack et al., The Chemistry of Redox-Flow Batteries, Angew. Chem. Int. Ed., 54:9776-9809 (2015). [cited by applicant]
Pan, F., et al., Redox Targeting of Anatase TiO 2 for Redox Flow Lithium-Ion Batteries, Adv. Energy Mater., 4:1-7 (2014). [cited by applicant]
Potash, R. A., et al., On the Benefits of a Symmetric Redox Flow Battery, Journal of The Electrochemical Society, 163(3):A338-A344 (2016). [cited by applicant]
Robinson et al., Developing a Predictive Solubility Model for Monomeric and Oligomeric Cyclopropenium-Based Flow Battery Catholytes, J. Am. Chem. Soc., 141:10171-10176 (2019). [cited by applicant]
Shrestha, A., et al., Realization of an Asymmetric Non-Aqueous Redox Flow Battery through Molecular Design to Minimize Active Species Crossover and Decomposition, Chemistry-A European Journal, 26:5369-5373 (2020). [cited by applicant]
Silcox et al., Transferability of Performance Metrics for Redox-Active Molecules, J. Phys. Chem. C., 123:16516-16524 (2019). [cited by applicant]
Ue et al., Electrochemical Properties of Organic Liquid Electrolytes Based on Quaternary Onium Salts for Electrical Double-Layer Capacitors, J. Electrochem. Soc., 141:2989-2996 (1994). [cited by applicant]
Vaid et al., An organic super-electron-donor as a high energy density negative electrolyte for nonaqueous flow batteries, Chem. Commun., 55:11037-11040 (2019). [cited by applicant]
Vaino, A. R., et al., Solid-Phase Organic Synthesis: A Critical Understanding of the Resin, J. Comb. Chem., 2:579-596 (2000). [cited by applicant]
Wang et al., Functionalized Cross-Linked Poly(vinyl alcohol) Resins as Reaction Scavengers and as Supports for Solid-Phase Organic Synthesis, J. Comb. Chem., 6:961-966 (2004). [cited by applicant]
Wang, Q., et al., Redox Targeting of Insulating Electrode Materials: A New Approach to High-Energy-Density Batteriest, Angew. Chem. Int. Ed., 118(48):8377-8380 (2006). [cited by applicant]
Winsberg et al., Redox-Flow Batteries: From Metals to Organic Redox-Active Materials, Angew. Chem. Int. Ed., 56:686-711 (2017). [cited by applicant]
Wong, C. M., et al., All-Organic Storage Solids and Redox Shuttles for Redox-Targeting Flow Batteries, ACS Energy Lett., 6:1271-1279 (2021). [cited by applicant]
Xiao et al., Revisiting the IspH Catalytic System in the Deoxyxylulose Phosphate Pathway: Achieving High Activity, J. Am. Chem. Soc., 131:9931-9933 (2009). [cited by applicant]
Xing et al., All-Liquid Electroactive Materials for High Energy Density Organic Flow Battery, ACS Appl. Energy Mater., 2:2364-2369 (2019). [cited by applicant]
Yan et al., Bis(diisopropylamino)cyclopropenium-arene Cations as High Oxidation Potential and High Stability Catholytes for Non-aqueous Redox Flow Batteries, J. Am. Chem. Soc., 142:17564-17571 (2020). [cited by applicant]
Yan et al., Mechanism-Based Design of a High-Potential Catholyte Enables a 3.2 V All-Organic Nonaqueous Redox Flow Battery, J. Am. Chem. Soc., 141:15301-15306 (2019). [cited by applicant]
Ye, J., et al., Redox targeting-based flow batteries, Journal of Physics D: Applied Physics, 52(44):18 (2019). [cited by applicant]
Yu, J., et al., A robust anionic sulfonated ferrocene derivative for pH-neutral aqueous flow battery, Energy Storage Materials, 29:216-222 (2020). [cited by applicant]
Zanzola, E., et al., Redox Solid Energy Boosters for Flow Batteries: Polyaniline as a Case Study, Electrochimica Acta, 235:664-671 (2017). [cited by applicant]
Zeng et al., A comparative study of all-vanadium and iron-chromium redox flow batteries for large-scale energy storage, J, Pow. Sour., 300:438-443 (2015). [cited by applicant]
Zhang et al., Solution Properties and Practical Limits of Concentrated Electrolytes for Nonaqueous Redox Flow Batteries, J. Phys. Chem. C., 122:8159-8172 (2018). [cited by applicant]
Zhou, M., et al., Nemstian-Potential-Driven Redox-Targeting Reactions of Battery Materials, Chem., 3(6):1036-1049 (2017). [cited by applicant]
Zhou, M., et al., Single-Molecule Redox-Targeting Reactions for a pH-Neutral Aqueous Organic Redox Flow Battery, Angew. Chem. Int. Ed., 59:14286-14291 (2020). [cited by applicant]
Zhu, Y. G., et al., Unleashing the Power and Energy of LiFePO4-Based Redox Flow Lithium Battery with a Bifunctional Redox Mediator, J. Am. Chem. Soc., 139:6286-6289 (2017). [cited by applicant]