Case Studies on Nonaqueous Zn2+ Ion Chemistry with a Reversible Intercalation Cathodes for the Development of Multivalent Metal Batteries

Wednesday, 4 October 2017
Prince George's Exhibit Hall D/E (Gaylord National Resort and Convention Center)
S. D. Han (JCESR at Argonne National Laboratory), P. Senguttuvan (Joint Center for Energy Storage Research), S. Tepavcevic (Argonne National Laboratory), N. N. Rajput (Lawrence Berkeley National Laboratory), X. Qu (Joint Center for Energy Storage Research (JCESR)), S. Kim (Argonne National Laboratory), H. D. Yoo (JCESR at University of Illinois at Chicago), A. L. Lipson (JCESR at Argonne National Laboratory), H. Wang (Joint Center for Energy Storage Research), P. J. Phillips (University of Illinois at Chicago), R. F. Klie (University Of Illinois At Chicago), B. Key, B. J. Ingram (JCESR at Argonne National Laboratory), J. Cabana (University of Illinois at Chicago), T. T. Fister (Chemical Sciences and Engineering Division), K. A. Persson (University of California at Berkeley), N. M. Markovic (Argonne National Laboratory), C. Johnson (Chemical Sciences and Engineering Division), A. K. Burrell (Joint Center for Energy Storage Research), and J. T. Vaughey (JCESR at Argonne National Laboratory)
Recently, new energy storage chemistries based on nonaqueous electrolytes and multivalent metals (e.g., Mg, Zn, Ca and Al) have drawn the attention of the researchers as a promising advanced energy storage technology due to their higher theoretical volumetric capacity, limited dendrite formation and low cost.1 A major developmental need for these systems is the identification of electrolytes compatible with both electrodes while showing reversible deposition/dissolution on an anode and multivalent intercalation into a cathode.1,2 In the case of nonaqueous Mg or Ca ion-based systems, electrolyte compatibility issues (e.g., low Coulombic efficiency, a high overpotential and corrosion) have held back the development of Mg or Ca metal batteries.3 However, the nonaqueous Zn2+ ion chemistry utilized in a Zn metal cells with a reversible intercalation cathode is an exception with a number of promising features including highly-efficient reversible Zn deposition/dissolution on a Zn metal anode with a wide electrochemical window,3 similar ionic radius compared with Li+ and Mg2+ ions,4 relatively lower activation barrier energy for diffusion in cathode materials (e.g., FePO4, CoO2 and V2O5)5 and high volumetric capacity.1 Considering these advantages, a nonaqueous Zn system provides an opportunity to delve into the mechanisms in multivalent-ion cell chemistry and solve the present issues in multivalent cell design and prototyping.3

In this study, the intercalation chemistry on a variety of cathodes materials (e.g., V2O5, Mn2O4 and FePO4) have been investigated in various nonaqueous Zn electrolytes. The electrochemical and transport properties of the electrolytes (e.g., reversible Zn deposition, anodic/cathodic stability, ionic conductivity and diffusion coefficient) were characterized utilizing the experimental and computational analysis.3 Among various Zn metal cells, a Zn/nanostructured bilayered V2O5 cell with a selected acetonitrile(AN)-Zn(TFSI)2 electrolyte demonstrates good reversibility and stability for 120+ cycles with nearly 100% Coulombic efficiency and ~170 mAhg-1 of gravimetric capacity, albeit operating at a cell voltage of 0.7 V vs. Zn/Zn2+.6 A Zn/nanostructured layered δ-MnO2 cell with an AN-Zn(TFSI)2 electrolyte also shows good reversibility (~100% Coulombic efficiency) and stability for 50+ cycles with ~100 mAhg-1 capacity with an operating voltage of 1.2 V vs. Zn/Zn2+.7 By utilizing a combination of analytical tools, we address numerous factors affecting capacity fade, and issues associated with the second phase formation including Mn dissolution in Zn/δ-MnO2 cells that have been extensively cycled.7


1. J. Muldoon, C. B. Bucur and T. Gregory, Chem. Rev. 2014, 114, 11683-11720.

2. H. D. Yoo, I. Shterenberg, Y. Gofer, G. Gershinsky, N. Pour and D. Aurbach, Energy Environ. Sci. 2013, 6, 2265-2279.

3. S.-D. Han, N. N. Rajput, X. Qu, B. Pan, M. He, M. S. Ferrandon, C. Liao, K. A. Persson and A. K. Burrell, ACS Appl. Mater. Inter. 2016, 8, 3021-3031.

4. R. D. Shannon, Acta Cryst. 1976, A32, 751-767.

5. Z. Rong, R. Malik, P. Canepa, G. Gautam, M. Liu, A. Jain, K. Persson and G. Ceder, Chem. Mater. 2015, 27, 6016-6021.

6. P. Senguttuvan, S.-D. Han, S. Kim, A. L. Lipson, S. Tepavcevic, T. T. Fister, I. D. Bloom, A. K. Burrell and C. S. Johnson, Adv. Energy Mater. 2016, 6, 1600826.

7. S.-D. Han, S. Kim, D. Li, V. Petkov, H. D. Yoo, P. J. Phillips, H. Wang, J. J. Kim, K. L. More, B. Key, R. F. Klie, J. Cabana, V. Stamenkovic, T. T. Fister, N. M. Markovic, A. K. Burrell, S. Tepavcevic, J. T. Vaughey, 2017, in revision.