Optimizing Carbon Nanotube Electrodes

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Using electrodes made of carbon nanotubes (CNTs) can significantly improve the performance of devices ranging from capacitors and batteries to water desalination systems. But figuring out the physical characteristics of vertically aligned CNT arrays that yield the most benefit has been difficult.

Now an MIT team has developed a method that can help. By combining simple benchtop experiments with a model describing porous materials, the researchers have found they can quantify the morphology of a CNT sample, without destroying it in the process.

In a series of tests, the researchers confirmed that their adapted model can reproduce key measurements taken on CNT samples under varying conditions. They’re now using their approach to determine detailed parameters of their samples — including the spacing between the nanotubes — and to optimize the design of CNT electrodes for a device that rapidly desalinates brackish water.

A common challenge in developing energy storage devices and desalination systems is finding a way to transfer electrically charged particles onto a surface and store them there temporarily. In a capacitor, for example, ions in an electrolyte must be deposited as the device is being charged and later released when electricity is being delivered. During desalination, dissolved salt must be captured and held until the cleaned water has been withdrawn.

One way to achieve those goals is by immersing electrodes into the electrolyte or the saltwater and then imposing a voltage on the system. The electric field that's created causes the charged particles to cling to the electrode surfaces. When the voltage is cut, the particles immediately let go.

"Whether salt or other charged particles, it’s all about adsorption and desorption," says Heena Mutha PhD '17, a senior member of technical staff at the Charles Stark Draper Laboratory. "So the electrodes in your device should have lots of surface area as well as open pathways that allow the electrolyte or saltwater carrying the particles to travel in and out easily."

One way to increase the surface area is by using CNTs. In a conventional porous material, such as activated charcoal, interior pores provide extensive surface area, but they're irregular in size and shape, so accessing them can be difficult. In contrast, a CNT "forest" is made up of aligned pillars that provide the needed surfaces and straight pathways, so the electrolyte or saltwater can easily reach them.

However, optimizing the design of CNT electrodes for use in devices has proven tricky. Experimental evidence suggests that the morphology of the material — in particular, how the CNTs are spaced out — has a direct impact on device performance. Increasing the carbon concentration when fabricating CNT electrodes produces a more tightly packed forest and more abundant surface area. But at a certain density, performance starts to decline, perhaps because the pillars are too close together for the electrolyte or saltwater to pass through easily.

Designing for device performance

"Much work has been devoted to determining how CNT morphology affects electrode performance in various applications," says Evelyn Wang, the Gail E. Kendall Professor of Mechanical Engineering. "But an underlying question is, 'How can we characterize these promising electrode materials in a quantitative way, so as to investigate the role played by such details as the nanometer-scale interspacing?'"

Inspecting a cut edge of a sample can be done using a scanning electron microscope (SEM). But quantifying features, such as spacing, is difficult, time-consuming, and not very precise. Analyzing data from gas adsorption experiments works well for some porous materials, but not for CNT forests. Moreover, such methods destroy the material being tested, so samples whose morphologies have been characterized can't be used in tests of overall device performance.

For the past two years, Wang and Mutha have been working on a better option. "We wanted to develop a nondestructive method that combines simple electrochemical experiments with a mathematical model that would let us 'back calculate' the interspacing in a CNT forest," Mutha says. "Then we could estimate the porosity of the CNT forest — without destroying it."


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