(Invited) Dendrite-Free Rechargeable Zinc-Based Batteries: Solving a Chronic Impediment through Architectural Design in 3D

The international effort to move beyond lithium-ion batteries—present-day’s ubiquitous electrochemical energy storage (EES) device—arises from the unending safety threat posed courtesy of flammable electrolytes and oxygen-releasing cathodes. The oft-posited “Beyond Lithium” as an R&D rationale for next-generation batteries needs to bypass not just lithium-ion, but Li-based batteries. Zinc-based batteries offer a compelling alternative thanks to nonflammable aqueous electrolytes augmented by the high domestic abundance of Zn and the high energy density of Zn-based batteries (comparable to or greater than Li-ion). The present performance, however, of traditional Zn-based batteries is hindered by suboptimal Zn utilization (typically <60% of theoretical capacity) and poor rechargeability—thanks to the complex dissolution/precipitation processes that accompany Zn/Zn²⁺cycling in alkaline electrolytes. We adapt the promise of three-dimensional (3D) battery architectures [1–3] to address these limitations by redesigning the zinc anode as a porous, highly conductive, and 3D-wired “sponge” architecture. These aperiodic electrode architectures achieve >90% Zn utilization when discharged in primary Zn–air cells, while retaining the 3D monolithic framework and exhibiting an impedance characteristic of the metal with uniform deposition of charge/discharge products at the external and internal surfaces [4]. We further show that the structural characteristics of the Zn sponge promote greater rechargeability when cycled in prototype Ag–Zn and Ni–Zn cells, even thwarting dendrite formation when cycled in a symmetric Zn–Zn cell at an applied current density twice that of the critical current density necessary to form dendrites [5]. Our results show that all Zn-based chemistries can now be reformulated for next-generation rechargeable, Li-free batteries.

The information, data, or work presented herein was funded in part by the Office of Naval Research and by the Advanced Research Projects Agency–Energy (ARPA–E), U.S. Department of Energy, under Award Number DE-AR-0000391; the work has been Approved for Public Release, Distribution Unlimited.

[1]   R.W. Hart, H.S White, B. Dunn, D.R. Rolison, Electrochem. Commun. 5(2003) 120–123.

[2]   J.W. Long, B. Dunn, D.R. Rolison, H.S. White, Chem. Rev. 104(2004) 4463–4492.

[3]   D.R. Rolison, J.W. Long, J.C. Lytle, A.E. Fischer, C.P. Rhodes, T.M. McEvoy, M.E. Bourg, A.M. Lubers, Chem. Soc. Rev. 38(2009) 226–252.

[4]  J.F. Parker, E.S. Nelson, M.D. Wattendorf, C.N. Chervin, J.W. Long, D.R. Rolison, ACS Appl. Mater. Interfac., in the press.

[5]   J.F. Parker, C.N. Chervin, E.S. Nelson, J.W. Long, D.R. Rolison, Energy Environ. Sci. 7 (2014) 1117–1124.