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August 22, 2011

Rice University developing solid-state, nanotube-based supercapacitors

Carbon nanotube bundles are at the center of supercapacitors developed at Rice University. Arrays of nanotube bundles are coated via atomic layer deposition to create thousands of microscopic devices in a single array. The electron microscope images at right show the three-layer construction of one of the supercapacitors, which are about 100 nanometers wide.

A Rice team grew an array of 15-20 nanometer bundles of single-walled carbon nanotubes up to 50 microns long into a supercapacitor

Carbon journal - Three dimensional solid-state supercapacitors from aligned single-walled carbon nanotube array templates


We demonstrate the fabrication of solid-state dielectric energy storage materials from self-assembled, aligned single-walled carbon nanotube arrays (VA-SWNTs). The arrays are transferred as intact structures to a conductive substrate and the nanotubes are conformally coated with a thin metal-oxide dielectric and a conductive counter-electrode layer using atomic layer deposition. Experimental results yield values in agreement with those obtained through capacitive modeling using Al2O3 dielectric coatings (C over 20 mF/cm3), and the solid-state dielectric architecture enables the operation of these devices at substantially higher frequencies than conventional electrolyte-based capacitor designs. Furthermore, modeling of supercapacitor architectures utilizing other dielectric layers suggests the ability to achieve energy densities above 10 W h/kg while still exhibiting power densities comparable to conventional solid-state capacitor devices. This device design efficiently converts the high surface area available in the conductive VA-SWNT electrode to space for energy storage while boasting a robust solid-state material framework that is versatile for use in a range of conditions not practical with current energy storage technology.




A method developed at Rice University allows bundles of vertically aligned single-wall carbon nanotubes to be transferred intact to a conductive substrate. Metallic layers added via atomic layer deposition create a solid-state supercapacitor that can stand up to extreme environments.

The array was then transferred to a copper electrode with thin layers of gold and titanium to aid adhesion and electrical stability. The nanotube bundles (the primary electrodes) were doped with sulfuric acid to enhance their conductive properties; then they were covered with thin coats of aluminum oxide (the dielectric layer) and aluminum-doped zinc oxide (the counterelectrode) through a process called atomic layer deposition (ALD). A top electrode of silver paint completed the circuit.

"Essentially, you get this metal/insulator/metal structure," Pint said. "No one's ever done this with such a high-aspect-ratio material and utilizing a process like ALD."

Hauge said the new supercapacitor is stable and scaleable. "All solid-state solutions to energy storage will be intimately integrated into many future devices, including flexible displays, bio-implants, many types of sensors and all electronic applications that benefit from fast charge and discharge rates," he said.

Pint said the supercapacitor holds a charge under high frequency cycling and can be naturally integrated into materials. He envisioned an electric car body that is a battery, or a microrobot with an onboard, nontoxic power supply that can be injected for therapeutic purposes into a patient's bloodstream.

Pint said it would be ideal for use under the kind of extreme conditions experienced by desert-based solar cells or in satellites, where weight is also a critical factor. "The challenge for the future of energy systems is to integrate things more efficiently. This solid-state architecture is at the cutting edge," he said.

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