Anton L. Cottrill

Sustainable power sources based on high efficiency thermopower wave devices

There is a pressing need to find alternatives to conventional batteries such as Li-ion, which contain toxic metals, present recycling difficulties due to harmful inorganic components, and rely on elements in finite global supply. Thermopower wave (TPW) devices, which convert chemical to electrical energy by means of self-propagating reaction waves guided along nanostructured thermal conduits, have the potential to address this demand. Herein, we demonstrate orders of magnitude higher chemical-to-electrical conversion efficiency of thermopower wave devices, in excess of 1%, with sustainable fuels such as sucrose and NaN3 for the first time, that produce energy densities on par with Li-ion batteries operating at 80% efficiency (0.2 MJ L−1versus 0.8 MJ L−1). We show that efficiency can be increased significantly by selecting fuels such as sodium azide or sucrose with potassium nitrate to offset the inherent penalty in chemical potential imposed by strongly p-doping fuels, a validation of the predictions of Excess Thermopower theory. Such TPW devices can be scaled to lengths greater than 10 cm and durations longer than 10 s, an over 5-fold improvement over the highest reported values, and they are capable of powering a commercial LED device. Lastly, a mathematical model of wave propagation, coupling thermal and electron transport with energy losses, is presented to describe the dynamics of power generation, explaining why both unipolar and bipolar waveforms can be observed. These results represent a significant advancement toward realizing TPW devices as new portable, high power density energy sources that are metal-free.

Electrical Energy Generation via Reversible Chemical Doping on Carbon Nanotube Fibers

Chemically modified carbon nanotube fibers enable unique power sources driven entirely by a chemical potential gradient. Electrical current (11.9 μA mg-1 ) and potential (525 mV) are reversibly produced by localized acetonitrile doping under ambient conditions. An inverse length-scaling of the maximum power as L-1.03 that creates specific powers as large as 30.0 kW kg-1 highlights the potential for microscale energy generation.

Ultra-high thermal effusivity materials for resonant ambient thermal energy harvesting

Materials science has made progress in maximizing or minimizing the thermal conductivity of materials; however, the thermal effusivity—related to the product of conductivity and capacity—has received limited attention, despite its importance in the coupling of thermal energy to the environment. Herein, we design materials that maximize the thermal effusivity by impregnating copper and nickel foams with conformal, chemical-vapor-deposited graphene and octadecane as a phase change material. These materials are ideal for ambient energy harvesting in the form of what we call thermal resonators to generate persistent electrical power from thermal fluctuations over large ranges of frequencies. Theory and experiment demonstrate that the harvestable power for these devices is proportional to the thermal effusivity of the dominant thermal mass. To illustrate, we measure persistent energy harvesting from diurnal frequencies, extracting as high as 350 mV and 1.3 mW from approximately 10 °C diurnal temperature differences.Ambient environmental thermal fluctuations offer an abundant yet difficult to harvest renewable energy source, when compared to static thermal gradients. Here, by tuning the thermal effusivity of composite phase change materials, the authors are able to harvest energy from diurnal ambient temperature changes.

Colloidal nanoelectronic state machines based on 2D materials for aerosolizable electronics

A previously unexplored property of two-dimensional electronic materials is their ability to graft electronic functionality onto colloidal particles to access local hydrodynamics in fluids to impart mobility and enter spaces inaccessible to larger electronic systems. Here, we demonstrate the design and fabrication of fully autonomous state machines built onto SU-8 particles powered by a two-dimensional material-based photodiode. The on-board circuit connects a chemiresistor circuit element and a memristor element, enabling the detection and storage of information after aerosolization, hydrodynamic propulsion to targets over 0.6 m away, and large-area surface sensing of triethylamine, ammonia and aerosolized soot in inaccessible locations. An incorporated retroreflector design allows for facile position location using laser-scanning optical detection. Such state machines may find widespread application as probes in confined environments, such as the human digestive tract, oil and gas conduits, chemical and biosynthetic reactors, and autonomous environmental sensors.Colloidal state machines, composed of 2D nanoelectronics grafted onto submillimetre-sized particles, act as autonomous electronic circuits capable of logical operation and information storage.

Observation of the Marcus Inverted Region of Electron Transfer from Asymmetric Chemical Doping of Pristine (n,m) Single-Walled Carbon Nanotubes

The concept of electrical energy generation based on asymmetric chemical doping of single-walled carbon nanotube (SWNT) papers is presented. We explore 27 small, organic, electron-acceptor molecules that are shown to tune the output open-circuit voltage (VOC) across three types of pristine SWNT papers with varying (n,m) chirality distributions. A considerable enhancement in the observed VOC, from 80 to 440 mV, is observed for SWNT/molecule acceptor pairs that have molecular volume below 120 Å3 and lowest unoccupied molecular orbital (LUMO) energies centered around -0.8 eV. The electron transfer (ET) rate constants driving the VOC generation are shown to vary with the chirality-associated Marcus theory, suggesting that the energy gaps between SWNT and the LUMO of acceptor molecules dictate the ET process. When the ET rate constants and the maximum VOC are plotted versus the LUMO energy of the acceptor organic molecule, volcano-shaped dependencies, characteristic of the Marcus inverted region, are apparent for three distinct sources of SWNT papers with modes in diameter distributions of 0.95, 0.83, and 0.75 nm. This observation, where the ET driving force exceeds reorganization energies, allows for an estimation of the outer-sphere reorganization energies with values as low as 100 meV for the (8,7) SWNT, consistent with a proposed image-charge modified Born energy model. These results expand the fundamental understanding of ET transfer processes in SWNT and allow for an accurate calculation of energy generation through asymmetric doping for device applications.