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Mesoporous Manganese Oxide Nanowires for High-Capacity, High-Rate, Hybrid Electrical Energy Storage

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Wenbo Yan†, Talin Ayvazian†, Jungyun Kim†, Yu Liu‡, Keith C. Donavan†, Wendong Xing†, Yongan Yang†, John C. Hemminger†, and Reginald M. Penner†§*

^†Department of Chemistry, ^‡Department of Physics and Astronomy, and ^§Department of Chemical Engineering and Materials Science, University of California, Irvine, California 92697, United States.

ACS Nano, 2011, 5 (10), pp 8275–8287

DOI: 10.1021/nn2029583

Publication Date (Web): September 26, 2011

Address correspondence to rmpenner@uci.edu.

¶ Author Present Address

Department of Chemistry and Geochemistry, Colorado School of Mines, Golden, Colorado 80401.

Section:

Electrochemical, Radiational, and Thermal Energy Technology

Abstract

Arrays of mesoporous manganese dioxide, mp-MnO₂, nanowires were electrodeposited on glass and silicon surfaces using the lithographically patterned nanowire electrodeposition (LPNE) method. The electrodeposition procedure involved the application, in a Mn(ClO₄)₂-containing aqueous electrolyte, of a sequence of 0.60 V (vs MSE) voltage pulses delineated by 25 s rest intervals. This “multipulse” deposition program produced mp-MnO₂ nanowires with a total porosity of 43–56%. Transmission electron microscopy revealed the presence within these nanowires of a network of 3–5 nm diameter fibrils that were X-ray and electron amorphous, consistent with the measured porosity values. mp-MnO₂ nanowires were rectangular in cross-section with adjustable height, ranging from 21 to 63 nm, and adjustable width ranging from 200 to 600 nm. Arrays of 20 nm × 400 nm mp-MnO₂ nanowires were characterized by a specific capacitance, C_sp, of 923 ± 24 F/g at 5 mV/s and 484 ± 15 F/g at 100 mV/s. These C_sp values reflected true hybrid electrical energy storage with significant contributions from double-layer capacitance and noninsertion pseudocapacitance (38% for 20 nm × 400 nm nanowires at 5 mV/s) coupled with a Faradaic insertion capacity (62%). These two contributions to the total C_sp were deconvoluted as a function of the potential scan rate.

Keywords:

lithium ion; cathode; battery; electrodeposition; photolithography; electrodeposition; pseudocapacitance

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History

Published In Issue October 25, 2011
Article ASAPOctober 03, 2011
Just Accepted ManuscriptSeptember 26, 2011
Received: August 03, 2011
Accepted: September 26, 2011

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