Tag Archives: Pulickel M. Ajayan

Graphene euphoria, heat sinks, diamonds, and Rice University’s Ajayan Group

Pulickel Ajayan, at Rice University (Texas), must have one of the most active laboratories in the US where nanotechnology-based research and announcements about it are concerned and I imagine it’s an exciting place to work. Whoever wrote the May 28, 2013 Rice University news release on EurekAlert seems to have caught some of the Ajayan Group’s excitement,

What may be the ultimate heat sink is only possible because of yet another astounding capability of graphene. The one-atom-thick form of carbon can act as a go-between that allows vertically aligned carbon nanotubes to grow on nearly anything.

That includes diamonds. A diamond film/graphene/nanotube structure was one result of new research carried out by scientists at Rice University and the Honda Research Institute USA, reported today in Nature’s online journal Scientific Reports.

The heart of the research is the revelation that when graphene is used as a middleman, surfaces considered unusable as substrates for carbon nanotube growth now have the potential to do so. Diamond happens to be a good example, according to Rice materials scientist Pulickel Ajayan and Honda chief scientist Avetik Harutyunyan.

Here’s an image the team has provided,

Rice University and the Honda Research Institute use single-layer graphene to grow forests of nanotubes on virtually anything. The image shows freestanding carbon nanotubes on graphene that has been lifted off of a quartz substrate. One hybrid material created by the labs combines three allotropes of carbon – graphene, nanotubes and diamond – into a superior material for thermal management. (Credit: Honda Research Institute)

Rice University and the Honda Research Institute use single-layer graphene to grow forests of nanotubes on virtually anything. The image shows freestanding carbon nanotubes on graphene that has been lifted off of a quartz substrate. One hybrid material created by the labs combines three allotropes of carbon – graphene, nanotubes and diamond – into a superior material for thermal management. (Credit: Honda Research Institute)

The news release provides more information about the diamond-carbon nanotube-graphene hybrid material,

Diamond conducts heat very well, five times better than copper. But its available surface area is very low. By its very nature, one-atom-thick graphene is all surface area. The same could be said of carbon nanotubes, which are basically rolled-up tubes of graphene. A vertically aligned forest of carbon nanotubes grown on diamond would disperse heat like a traditional heat sink, but with millions of fins. Such an ultrathin array could save space in small microprocessor-based devices.

“Further work along these lines could produce such structures as patterned nanotube arrays on diamond that could be utilized in electronic devices,” Ajayan said. Graphene and metallic nanotubes are also highly conductive; in combination with metallic substrates, they may also have uses in advanced electronics, he said.

To test their ideas, the Honda team grew various types of graphene on copper foil by standard chemical vapor deposition. They then transferred the tiny graphene sheets to diamond, quartz and other metals for further study by the Rice team.

They found that only single-layer graphene worked well, and sheets with ripples or wrinkles worked best. The defects appeared to capture and hold the airborne iron-based catalyst particles from which the nanotubes grow. The researchers think graphene facilitates nanotube growth by keeping the catalyst particles from clumping.

Ajayan thinks the extreme thinness of graphene does the trick. In a previous study, the Rice lab found graphene shows materials coated with graphene can get wet, but the graphene provides protection against oxidation. “That might be one of the big things about graphene, that you can have a noninvasive coating that keeps the property of the substrate but adds value,” he said. “Here it allows the catalytic activity but stops the catalyst from aggregating.”

Testing found that the graphene layer remains intact between the nanotube forest and the diamond or other substrate. On a metallic substrate like copper, the entire hybrid is highly conductive.

Such seamless integration through the graphene interface would provide low-contact resistance between current collectors and the active materials of electrochemical cells, a remarkable step toward building high-power energy devices, said Rice research scientist and co-author Leela Mohana Reddy Arava.

Here’s a link to and a citation for the paper,

Graphene as an atomically thin interface for growth of vertically aligned carbon nanotubes by Rahul Rao, Gugang Chen, Leela Mohana Reddy Arava, Kaushik Kalaga, Masahiro Ishigami, Tony F. Heinz, Pulickel M. Ajayan, & Avetik R. Harutyunyan. Scientific Reports 3, Article number: 1891 doi:10.1038/srep01891 Published 28 May 2013

Scientific Reports, a Nature publication, provides open access to its papers.

Mad about Madder in lithium-ion batteries

It hasn’t happened yet but it looks like the future might hold greener lithium-ion (Li-ion) batteries. According to the Dec. 11, 2012 news release on EurekAlert,

Scientists at Rice University and the City College of New York have discovered that the madder plant, aka Rubia tinctorum, is a good source of purpurin, an organic dye that can be turned into a highly effective, natural cathode for lithium-ion batteries. The plant has been used since ancient times to create dye for fabrics.

The goal, according to lead author Arava Leela Mohana Reddy, a research scientist in the Rice lab of materials scientist Pulickel Ajayan, is to create environmentally friendly batteries that solve many of the problems with lithium-ion batteries in use today.

Purpurin, left, extracted from madder root, center, is chemically lithiated, right, for use as an organic cathode in batteries. The material was developed as a less expensive, easier-to-recycle alternative to cobalt oxide cathodes now used in lithium-ion batteries. Credit: Ajayan Lab/Rice University

The Dec. 11, 2012 Rice University news release by Mike Williams, the origin for the one on EurekAlert, describes why the researchers are so interested in a more environmentally-friendly cathode,

While lithium-ion batteries have become standard in conventional electronics since their commercial introduction in 1991, the rechargeable units remain costly to manufacture, Reddy said. “They’re not environmentally friendly. They use cathodes of lithium cobalt oxide, which are very expensive. You have to mine the cobalt metal and manufacture the cathodes in a high-temperature environment. There are a lot of costs.

“And then, recycling is a big issue,” he said. “In 2010, almost 10 billion lithium-ion batteries had to be recycled, which uses a lot of energy. Extracting cobalt from the batteries is an expensive process.”

Reddy and his colleagues came across purpurin while testing a number of organic molecules for their ability to electrochemically interact with lithium and found purpurin most amenable to binding lithium ions. With the addition of 20 percent carbon to add conductivity, the team built a half-battery cell with a capacity of 90 milliamp hours per gram after 50 charge/discharge cycles. The cathodes can be made at room temperature, he said.

“It’s a new mechanism we are proposing with this paper, and the chemistry is really simple,” Reddy said. He suggested agricultural waste may be a source of purpurin, as may other suitable molecules, which makes the process even more economical.

Innovation in the battery space is needed to satisfy future demands and counter environmental issues like waste management, “and hence we are quite fascinated by the ability to develop alternative electrode technologies to replace conventional inorganic materials in lithium-ion batteries,” said Ajayan, Rice’s Benjamin M. and Mary Greenwood Anderson Professor in Mechanical Engineering and Materials Science and of chemistry.

“We’re interested in developing value-added chemicals, products and materials from renewable feedstocks as a sustainable technology platform,” said co-lead author George John, a professor of chemistry at the City College of New York-CUNY and an expert on bio-based materials and green chemistry. “The point has been to understand the chemistry between lithium ions and the organic molecules. Now that we have that proper understanding, we can tap other molecules and improve capacity.”

For anyone who’s interested, you can read the researchers’ article (open access),

Lithium storage mechanisms in purpurin based organic lithium ion battery electrodes by Arava Leela Mohana Reddy,  Subbiah Nagarajan, Porramate Chumyim, Sanketh R. Gowda, Padmanava Pradhan, Swapnil R. Jadhav, Madan Dubey,  George John & Pulickel M. Ajayan in Scientific Reports 2 Article number: 960 doi:10.1038/srep00960

You might also want to check out Dexter Johnson’s Nov. 26, 2012 posting (on Nanoclast, an IEEE [Institute of Electrical and Electronics Engineers] blog)where he mentions a technical deficiency (recharging becomes increasingly difficult) with the current Li-ion batteries in the context of his description of a new imaging technique.