Letter | Published:

An aqueous, polymer-based redox-flow battery using non-corrosive, safe, and low-cost materials

Nature volume 527, pages 7881 (05 November 2015) | Download Citation

Abstract

For renewable energy sources such as solar, wind, and hydroelectric to be effectively used in the grid of the future, flexible and scalable energy-storage solutions are necessary to mitigate output fluctuations1. Redox-flow batteries (RFBs) were first built in the 1940s2 and are considered a promising large-scale energy-storage technology1,3,4. A limited number of redox-active materials4,5,6,7,8,9,10—mainly metal salts, corrosive halogens, and low-molar-mass organic compounds—have been investigated as active materials, and only a few membrane materials3,5,11,12,13,14, such as Nafion, have been considered for RFBs. However, for systems that are intended for both domestic and large-scale use, safety and cost must be taken into account as well as energy density and capacity, particularly regarding long-term access to metal resources, which places limits on the lithium-ion-based and vanadium-based RFB development15,16. Here we describe an affordable, safe, and scalable battery system, which uses organic polymers as the charge-storage material in combination with inexpensive dialysis membranes, which separate the anode and the cathode by the retention of the non-metallic, active (macro-molecular) species, and an aqueous sodium chloride solution as the electrolyte. This water- and polymer-based RFB has an energy density of 10 watt hours per litre, current densities of up to 100 milliamperes per square centimetre, and stable long-term cycling capability. The polymer-based RFB we present uses an environmentally benign sodium chloride solution and cheap, commercially available filter membranes instead of highly corrosive acid electrolytes and expensive membrane materials.

Access optionsAccess options

Rent or Buy article

Get time limited or full article access on ReadCube.

from$8.99

All prices are NET prices.

References

  1. 1.

    , & Electrical energy storage for the grid: a battery of choices. Science 334, 928–935 (2011)

  2. 2.

    Verfahren zur Speicherung von elektrischer Energie. German patent DE 914 264 (1949)

  3. 3.

    et al. Electrochemical energy storage for green grid. Chem. Rev. 111, 3577–3613 (2011)

  4. 4.

    , & Redox flow batteries for the storage of renewable energy: a review. Renew. Sustain. Energy Rev. 29, 325–335 (2014)

  5. 5.

    et al. Recent progress in redox flow battery research and development. Adv. Funct. Mater. 23, 970–986 (2013)

  6. 6.

    et al. A metal-free organic–inorganic aqueous flow battery. Nature 505, 195–198 (2014)

  7. 7.

    , , , & An inexpensive aqueous flow battery for large-scale electrical energy storage based on water-soluble organic redox couples. J. Electrochem. Soc. 161, A1371–A1380 (2014)

  8. 8.

    et al. TEMPO-based catholyte for high-energy density nonaqueous redox flow batteries. Adv. Mater. 26, 7649–7653 (2014)

  9. 9.

    , & An all-organic non-aqueous lithium-ion redox flow battery. Adv. Energy Mater. 2, 1390–1396 (2012)

  10. 10.

    et al. Progress in redox flow batteries, remaining challenges and their applications in energy storage. RSC Adv. 2, 10125–10156 (2012)

  11. 11.

    , , , & Membranes for redox flow battery applications. Membranes 2, 275–306 (2012)

  12. 12.

    , , , & Ion exchange membranes for vanadium redox flow battery (VRB) applications. Energy Environ. Sci. 4, 1147–1160 (2011)

  13. 13.

    , & A review of current developments in non-aqueous redox flow batteries: characterization of their membranes for design perspective. RSC Adv. 3, 9095–9116 (2013)

  14. 14.

    et al. Membrane development for vanadium redox flow batteries. ChemSusChem 4, 1388–1406 (2011)

  15. 15.

    & On the importance of reducing the energetic and material demands of electrical energy storage. Energy Environ. Sci. 6, 1083–1092 (2013)

  16. 16.

    & Building better batteries. Nature 451, 652–657 (2008)

  17. 17.

    et al. Anthraquinone with tailored structure for a nonaqueous metal–organic redox flow battery. Chem. Commun. 48, 6669–6671 (2012)

  18. 18.

    et al. Impact of redox-active polymer molecular weight on the electrochemical properties and transport across porous separators in nonaqueous solvents. J. Am. Chem. Soc. 136, 16309–16316 (2014)

  19. 19.

    et al. Electrochemical properties of an all-organic redox flow battery using 2,2,6,6-tetramethyl-1-piperidinyloxy and N-methylphthalimide. Electrochem. Solid-State Lett. 14, A171–A173 (2011)

  20. 20.

    , , & Expanding the dimensionality of polymers populated with organic robust radicals toward flow cell application: synthesis of TEMPO-crowded bottlebrush polymers using anionic polymerization and ROMP. Macromolecules 47, 8611–8617 (2014)

  21. 21.

    , , , & Nanofiltration (NF) membranes: the next generation separators for all vanadium redox flow batteries (VRBs)? Energy Environ. Sci. 4, 1676–1679 (2011)

  22. 22.

    et al. Solvent responsive silica composite nanofiltration membrane with controlled pores and improved ion selectivity for vanadium flow battery application. J. Power Sources 274, 1126–1134 (2015)

  23. 23.

    , , , & The use of polybenzimidazole membranes in vanadium redox flow batteries leading to increased coulombic efficiency and cycling performance. Electrochim. Acta 153, 492–498 (2015)

  24. 24.

    Advanced functional polymer membranes. Polymer 47, 2217–2262 (2006)

  25. 25.

    , & Powering up the future: radical polymers for battery applications. Adv. Mater. 24, 6397–6409 (2012)

  26. 26.

    , & Environmentally benign batteries based on organic radical polymers. Pure Appl. Chem. 81, 1961–1970 (2009)

  27. 27.

    , , & Substituent effects on electrochemical reduction of viologen dimer and trimer with ethylene spacer. J. Electroanal. Chem. 239, 397–403 (1988)

  28. 28.

    , , & The role of intramolecular association in the electrochemical reduction of viologen dimers and trimers. J. Electroanal. Chem. 243, 143–160 (1988)

  29. 29.

    et al. Redox flow batteries: a review. J. Appl. Electrochem. 41, 1137–1164 (2011)

  30. 30.

    , , , & Long-lived charge-separation by retarding reverse flow of charge-balancing cation and zeolite-encapsulated Ru(bpy)32+ as photosensitized electron pump from zeolite framework to externally placed viologen. J. Am. Chem. Soc. 124, 7123–7135 (2002)

  31. 31.

    , , , & Characterization of cationic polymers by asymmetric flow field-flow fractionation and multi-angle light scattering—a comparison with traditional techniques. J. Chromatogr. A 1325, 195–203 (2014)

  32. 32.

    , & A consideration of the application of Koutecký–Levich plots in the diagnoses of charge-transfer mechanisms at rotated disk electrodes. Electroanalysis 14, 165–171 (2002)

  33. 33.

    , & A comparison of electrochemical and electrokinetic parameters determined for cellophane membranes in contact with NaCl and NaNO3 solutions. J. Colloid Interface Sci. 246, 150–156 (2002)

  34. 34.

    , , , & Capital cost sensitivity analysis of an all-vanadium redox-flow battery. J. Electrochem. Soc. 159, A1183–A1188 (2012)

  35. 35.

    et al. Cost and performance model for redox flow batteries. J. Power Sources 247, 1040–1051 (2014)

  36. 36.

    & Economics of vanadium redox flow battery membranes. J. Power Sources 286, 247–257 (2015)

  37. 37.

    et al. A metal-free and all-organic redox flow battery with polythiophene as the electroactive species. J. Mater. Chem. A 2, 19994–19998 (2014)

Download references

Acknowledgements

We acknowledge the European Regional Development Fund for Thuringia (EFRE), the Thüringer Aufbaubank (TAB), the Thuringian Ministry for Economic Affairs, Science and Digital Society (TMWWdG), and the Fonds der Chemischen Industrie for financial support. We thank J. Stammer, C. Oder, K. Wolkersdörfer, C. Stolze, C. Schmerbauch, B. Häupler, M. Wagner, T. Buś, A. Ignaszak, and F. Schacher for their assistance and comments.

Author information

Affiliations

  1. Laboratory of Organic and Macromolecular Chemistry (IOMC), Friedrich Schiller University Jena, Humboldtstrasse 10, 07743 Jena, Germany

    • Tobias Janoschka
    • , Christian Friebe
    • , Sabine Morgenstern
    • , Hannes Hiller
    • , Martin D. Hager
    •  & Ulrich S. Schubert
  2. Center for Energy and Environmental Chemistry Jena (CEEC Jena), Friedrich Schiller University Jena, Philosophenweg 7a, 07743 Jena, Germany

    • Tobias Janoschka
    • , Christian Friebe
    • , Sabine Morgenstern
    • , Hannes Hiller
    • , Martin D. Hager
    •  & Ulrich S. Schubert
  3. JenaBatteries GmbH, Botzstrasse 5, 07743 Jena, Germany

    • Norbert Martin
    •  & Udo Martin

Authors

  1. Search for Tobias Janoschka in:

  2. Search for Norbert Martin in:

  3. Search for Udo Martin in:

  4. Search for Christian Friebe in:

  5. Search for Sabine Morgenstern in:

  6. Search for Hannes Hiller in:

  7. Search for Martin D. Hager in:

  8. Search for Ulrich S. Schubert in:

Contributions

T.J., M.D.H., and U.S.S. conceived the studies. N.M., C.F., and T.J. contributed to performing all electrochemical experiments and interpreting the results. S.M. and H.H. performed synthesis under the supervision of T.J. The test cell was designed by U.M. All authors discussed the results and commented on the manuscript. T.J., C.F., M.D.H., and U.S.S wrote the manuscript.

Competing interests

U.S.S. is associated with JenaBatteries GmbH as a scientific advisor and T.J., M.D.H. and U.S.S. are co-founders of the company. The intellectual property based upon the present data will be transferred from the Friedrich Schiller University Jena to the JenaBatteries GmbH.

Corresponding author

Correspondence to Ulrich S. Schubert.

Extended data

About this article

Publication history

Received

Accepted

Published

DOI

https://doi.org/10.1038/nature15746

Further reading

Comments

By submitting a comment you agree to abide by our Terms and Community Guidelines. If you find something abusive or that does not comply with our terms or guidelines please flag it as inappropriate.

Newsletter Get the most important science stories of the day, free in your inbox. Sign up for Nature Briefing