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We investigate the impact of using a carbon based gas diffusion layer (GDL) as the current collector for Li-O2 batteries. It is shown that the GDL actively participates in ORR during discharge conditions and, if its mass is not accounted for, can lead to inflated discharge capacity figures compared to inert cathode supports. SEM and XRD analyses show that Li2O2 discharge products form on cathodes composed of as-received GDL in a similar manner to that observed for carbon on stainless steel (SS) current collectors (at applied currents of 100 μA cm−2 or less). The relative activity of the GDL, carbon on GDL and carbon-on-stainless steel current collectors from voltammetric measurements confirmed ORR and OER processes to be similar at all carbon-based surfaces. When heated above 300◦C, degradation of the binder in the GDL and associated loss of carbon from the substrate surface leads to reduced discharge times compared to the pristine GDL substrates. The data highlight the importance of the contribution to ORR/OER in carbon-based active current collector substrates when determining gravimetric capacities of Li-O2 batteries. © 2014 The Electrochemical Society. [DOI: 10.1149/2.0021414jes] All rights reserved.

Current lithium-ion battery anode research involves significant investigations of semiconducting materials, particularly Si as its theoretical specific capacity is >4000 mAh/g1. Previous theoretical studies showed that porous Si with a large pore size and high porosity can maintain its structure after Li ion induced alloying and swelling. Metal-assisted chemical (MAC) etching is shown here to form internally mesoporous nanowires in the form of a layer, etched from highly doped Si2-4. Some porous materials are well known to exhibit pseudocapacitive behaviour in aqueous electrolytes5,6. Maintaining the structure without stress-induced cracked caused by volumetric changes in material is crucial in achieving a high capacity and long cycle retention. Almost all investigations of nanoscale Si involve their deposition onto a metallic current collector electrode within the battery cell. Here, we demonstrate that pseudocapacitive behaviour can be harnessed when Si nanowires are etched to maximum mesoporosity, forming an electrically dead layer on silicon current collector electrodes. This limits insertion or alloying processes to form Li-Si phases7and charge is stored within the electric double layer, even in Li-ion containing electrolytes. Measurements using cyclic and linear voltammetry supported by Raman scattering spectroscopy and electron microscopy confirm surface charge storage mechanisms; pseudocapacitance is not observed when the same nanowires are used on stainless steel current collectors. In such cases, the rate of lithiation is shown to be related to the degree of porosity and the net surface electronic density of the porous silicon in accumulation mode during charging. References C. K. Chan, H. Peng, G. Liu, K. McIlwrath, X. F. Zhang, R. A. Huggins and Y. Cui, Nat. Nanotechnol. 3, 31 (2008). W. McSweeney, O. Lotty, N. Mogili, C. Glynn, H. Geaney, D. Tanner, J. Holmes and C. O'Dwyer, J. Appl. Phys. 114,034309 (2013). A. I. Hochbaum, D. Gargas, Y. J. Hwang, P. Yang, Nano Lett. 9, 3550 (2009). W. McSweeney, O. Lotty, J. D. Holmes and C. O'Dwyer, ECS Trans., 35, 25 (2011). P. Simon and Y. Gogotsi, Nat. Mater. 7, 845 (2008). T. Brezesinski, J. Wang, S. H. Tolbert and B. Dunn, Nat. Mater. 9, 146 (2010). W. McSweeney, O. Lotty, C. Glynn, H. Geaney, J. D. Holmes and C. O'Dwyer, Electrochim. Acta, 135, 356 (2014).