(Invited) New Solar and Chemical Energy Conversion Mechanisms Enabled By Nanocarbon Systems

Our laboratory at MIT has been interested in how nanocarbon systems, such as carbon nanotubes and graphene, can enable new energy conversion mechanisms.  This presentation will highlight two such conversion schemes: chemical energy conversion via reactivity waves and solar energy harvesting using nanotube based photovoltaics.  Towards the former, spatially propagating reaction waves are already central to a variety of energy applications, such as high temperature solid phase or combustion synthesis, and thermopower waves. In this work, we identify and study a previously unreported property of such waves, specifically that they can generate temperatures far in excess of the adiabatic limit. We show that this superadiabaticity occurs when a reaction wave in either one dimension (1D) or two dimensions (2D) impinges upon an adiabatic boundary under specific reaction and heat transfer conditions. This property is studied analytically and computationally for a series of 1D and 2D example systems, producing an estimate of the upper bound for excess temperature rise as high as 1.8 times the adiabatic limit, translating to temperatures approaching 2000 K for some practical materials. We show that superadiabaticity may enable several new types of energy conversion mechanisms, including thermophotovoltaic wave harvesting, which we analyze for efficiency and power density.  Towards the second application, photovoltaics using single-walled carbon nanotubes (SWNTs) as near-infrared photo-absorbers have seen rapid recent progress, offering promise for long-wavelength light harvesting devices. Despite this interest the fundamental design questions remain, such as optimal device thickness, nanotube orientation, density, and the impact of impurities. To address this challenge, we develop a deterministic model of SWNT PVs derived directly from SWNT photophysics using photon, exciton, and charge carrier population balances. The model accounts for arbitrary distributions of nanotube chiralities, lengths, orientations, defect types and concentrations, bundle fraction and size, and density. We show that feasible devices can achieve external quantum efficiencies above 60%. We reveal a sharply optimal device thickness that is a function of nanotube density, orientation, and quenching site concentration. This thickness stems from a tradeoff between exciton generation and diffusion to the electrodes, and is at a minimum at the limit of close-packed nanotube density. We show that this minimum characterizes a given device design and scales with mean nanotube length to exponent 0.4. The normalized difference between optimal thickness and this close-packed limit scales inversely with density to the 0.24 power. Practically, in-plane aligned nanotube configurations yield optimal thicknesses less than 10 nm, increasing to a range of 50 to 200 nm for vertical alignment. Due to weak inter-SWNT exciton transport relative to exceptional intra-SWNT diffusion, vertically-aligned films are unambiguously favored at densities above 3% of the close-packed limit; at lower densities however an optimum emerges at an intermediate angle to compensate for weaker light absorption of vertical nanotubes. Comparison to published experimental devices displays the model’s utility for device design.