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Due to the high standard electrode potentials of both zinc and cerium redox reactions in aqueous media, the open-circuit cell voltage was as high as 2.43 V.<ref>R.L. Clarke, B.J. Dougherty, S. Harrison, P.J. Millington, S. Mohanta, US 2004/ 0202925 A1, Cerium Batteries, (2004).</ref> Among the other proposed [[flow battery]] systems, this system has the largest cell voltage and power density per electrode area. Methanesulfonic acid was used as the supporting electrolyte, as it allows both zinc (2.16 M) <ref>M.D. Gernon, M. Wu, T. Buszta, P. Janney, Green Chem. 1 (1999) 127-140.</ref> and cerium electroactive species to dissolve at concentration larger than 1 M.<ref>R.P. Kreh, R.M. Spotnitz, J.T. Lundquist, J. Org. Chem. 54 (1989) 1526-1531.</ref>
Due to the high standard electrode potentials of both zinc and cerium redox reactions in aqueous media, the open-circuit cell voltage was as high as 2.43 V.<ref>R.L. Clarke, B.J. Dougherty, S. Harrison, P.J. Millington, S. Mohanta, US 2004/ 0202925 A1, Cerium Batteries, (2004).</ref> Among the other proposed [[flow battery]] systems, this system has the largest cell voltage and power density per electrode area. Methanesulfonic acid was used as the supporting electrolyte, as it allows both zinc (2.16 M) <ref>M.D. Gernon, M. Wu, T. Buszta, P. Janney, Green Chem. 1 (1999) 127-140.</ref> and cerium electroactive species to dissolve at concentration larger than 1 M.<ref>R.P. Kreh, R.M. Spotnitz, J.T. Lundquist, J. Org. Chem. 54 (1989) 1526-1531.</ref>


Sinc zinc is electroplated during charge at the negative electrode and redox reactions of Ce(III)/ Ce(IV) take places at the positive electrode, this system is often classified as a '''hybrid flow battery'''. Unlike the chemistry used in [[Zinc-bromine flow battery|zinc-bromine]]and zinc-chlorine redox flow batteres, no condensation device is needed to dissolve the halogen gases.
Sinc zinc is electroplated during charge at the negative electrode and redox reactions of Ce(III)/ Ce(IV) take places at the positive electrode, this system is often classified as a '''hybrid flow battery'''. Unlike the chemistry used in [[Zinc-bromine flow battery|zinc-bromine]] and zinc-chlorine redox flow batteres, no condensation device is needed to dissolve the halogen gases.




Revision as of 20:35, 11 June 2011

File:Zn-ce flow battery.jpg
Zn-Ce redox flow battery

Zinc-cerium redox flow battery was first developed by Plurion Inc. (UK) during the 2000s.[1][2] Negative zinc electrolyte and positive cerium electrolyte are stored in two separated reservoirs and are circulated during the operation. Negative and positive electrolyte compartments are separated by a Nafion cation-exchange membrane.

Due to the high standard electrode potentials of both zinc and cerium redox reactions in aqueous media, the open-circuit cell voltage was as high as 2.43 V.[3] Among the other proposed flow battery systems, this system has the largest cell voltage and power density per electrode area. Methanesulfonic acid was used as the supporting electrolyte, as it allows both zinc (2.16 M) [4] and cerium electroactive species to dissolve at concentration larger than 1 M.[5]

Sinc zinc is electroplated during charge at the negative electrode and redox reactions of Ce(III)/ Ce(IV) take places at the positive electrode, this system is often classified as a hybrid flow battery. Unlike the chemistry used in zinc-bromine and zinc-chlorine redox flow batteres, no condensation device is needed to dissolve the halogen gases.


Cell chemistry

At the negative electrode, zinc is electroplated and stripped on the carbon polymer electrodes during charge and discharge, respectively.[6]

Zn2+ + 2 e- ↔ Zn ( - 0.76 V vs. NHE)

At the positive electrode( titanium based materials or carbon felt electrode), Ce(III) oxidation and Ce(IV) reduction take place during charge and discharge, respectively.

2 Ce3+ - 2 e- ↔ 2 Ce4+ ( between + 1.28 and + 1.72 V vs. NHE)

Despite the large cell voltage, hydrogen ( 0 V vs. NHE) and oxygen ( + 1.23 V vs. NHE) could theoretically evolve as the side reactions during the operation.


History and development

Zinc-cerium redox flow battery was first proposed by Clarke and co-workers in 2004,[7][8] which has been the core technology of Plurion Inc. (UK). In 2008, Plurion Inc. suffered a liquidity crisis and was under liquidation in 2010. However, the information of the experimental conditions and charge-discharge performance described in the early patents of Plurion Inc. are limited. Since 2010s, the electrochemical properties and the characterisation of a zinc-cerium redox flow battery have been identified by the researchers of Southampton and StrathclydeUniversities. During charge/discharge cycles at 50 mA cm−2, the coulombic and voltage efficiencies of the zinc-cerium redox flow battery were reported to be 92 and 68 %, respectively.[9] In 2011, a membraneless (undivided) zinc-cerium system based on low acid concentration electrolyte using compressed pieces of carbon felt positive electrode was proposed by Leung and co-workers. Discharge cell voltage and round trip d.c. energy efficiency were reported to be approximately 2.1 V and 75 %, respectively. With such undivided configuration (single electrolyte compartment), self-discharge of zinc (zinc dissolution) was reported to be relatively slow at low concentrations of cerium and acid.[10] Major installation of the zinc-cerium redox flow battery was the > 2 kW testing facility in Glenrothes, Scotland, installed by Plurion Inc.


References

  1. ^ R.L. Clarke, B.J. Dougherty, S. Harrison, P.J. Millington, S. Mohanta, US 2004/ 0202925 A1, Cerium Batteries, (2004).
  2. ^ R.L. Clarke, B.J. Dougherty, S. Harrison, J.P. Millington, S. Mohanta, US 2006/0063065 A1, Battery with bifunctional electrolyte, (2005).
  3. ^ R.L. Clarke, B.J. Dougherty, S. Harrison, P.J. Millington, S. Mohanta, US 2004/ 0202925 A1, Cerium Batteries, (2004).
  4. ^ M.D. Gernon, M. Wu, T. Buszta, P. Janney, Green Chem. 1 (1999) 127-140.
  5. ^ R.P. Kreh, R.M. Spotnitz, J.T. Lundquist, J. Org. Chem. 54 (1989) 1526-1531.
  6. ^ G. Nikiforidis, L. Berlouis, D. Hall, D. Hodgson, J. Power Sources (2011)doi:10.1016/j.jpowsour.2011.01.036.
  7. ^ R.L. Clarke, B.J. Dougherty, S. Harrison, P.J. Millington, S. Mohanta, US 2004/ 0202925 A1, Cerium Batteries, (2004).
  8. ^ R.L. Clarke, B.J. Dougherty, S. Harrison, J.P. Millington, S. Mohanta, US 2006/0063065 A1, Battery with bifunctional electrolyte, (2005).
  9. ^ P.K. Leung, C. Ponce-de-Leon, C. Lo, A.A. Shah, F.C. Walsh, J. Power Sources (2011),11, pp. 5174 -5185, Characterization of a zinc-cerium flow battery'.
  10. ^ P.K. Leung, C. Ponce-de-Leon, F.C. Walsh, Electrochem. Comm. (2011), An undivided zinc–cerium redox flow battery operating at room temperature (295 K) ' , doi:10.1016/j.elecom.2011.04.011
  • [1]Plurion Inc.(UK)
  • [2]University of Southampton
  • [3] International Flow Battery Forum
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