15 Jan 2016
Rice University researchers who pioneered the development of laser-induced graphene have configured their discovery into flexible, solid-state microsupercapacitors that rival the best available for energy storage and delivery.
The devices developed in the lab of Rice chemist James Tour are geared toward electronics and apparel. They are the subject of a new paper in the journal Advanced Materials.
Microsupercapacitors are not batteries, but inch closer to them as the technology improves. Traditional capacitors store energy and release it quickly (as in a camera flash), unlike common lithium-ion batteries that take a long time to charge and release their energy as needed.
Supercapacitors can be charged and discharged tens of thousands of times, but their relatively low energy density compared to conventional batteries limits their application for energy storage. Now, A*STAR researchers have developed an ‘asymmetric’ supercapacitor based on metal nitrides and graphene that could be a viable energy storage solution (“All Metal Nitrides Solid-State Asymmetric Supercapacitors”).
|llustration of the asymmetric supercapacitor, consisting of vertically aligned graphene nanosheets coated with iron nitride and titanium nitride as the anode and cathode, respectively. (©WILEY-VCH Verlag)|
|A supercapacitor’s viability is largely determined by the materials of which its anodes and cathodes are comprised. These electrodes must have a high surface area per unit weight, high electrical conductivity and capacitance and be physically robust so they do not degrade during operation in liquid or hostile environments.|
|Unlike traditional supercapacitors, which use the same material for both electrodes, the anode and cathode in an asymmetric supercapacitor are made up of different materials. Scientists initially used metal oxides as asymmetric supercapacitor electrodes, but, as metal oxides do not have particularly high electrical conductivities and become unstable over long operating cycles, it was clear that a better alternative was needed.|
|Metal nitrides such as titanium nitride, which offer both high conductivity and capacitance, are a promising alternative, but they tend to oxidize in watery environments that limits their lifetime as an electrode. A solution to this is to combine them with more stable materials.|
|Hui Huang from A*STAR’s Singapore Institute of Manufacturing Technology and his colleagues from Nanyang Technological University and Jinan University, China, have fabricated asymmetric supercapacitors which incorporate metal nitride electrodes with stacked sheets of graphene.|
|To get the maximum benefit from the graphene surface, the team used a precise method for creating thin-films, a process known as atomic layer deposition, to grow two different materials on vertically aligned graphene nanosheets: titanium nitride for their supercapacitor’s cathode and iron nitride for the anode. The cathode and anode were then heated to 800 and 600 degrees Celsius respectively, and allowed to slowly cool. The two electrodes were then separated in the asymmetric supercapacitor by a solid-state electrolyte, which prevented the oxidization of the metal nitrides.|
|The researchers tested their supercapacitor devices and showed they could cycle 20,000 times and exhibited both high capacitance and high power density. “These improvements are due to the ultra-high surface area of the vertically aligned graphene substrate and the atomic layer deposition method that enables full use of it,” says Huang. “In future research, we want to enlarge the working-voltage of the device to increase energy density further still,” says Huang.|
Schematic diagrams showing the synthesis and microstructures of a 3D graphene-RACNT fiber. (A) Aluminum wire. (B) Surface anodized aluminum wire (AAO wire). (C) 3D graphene-RACNT structure on the AAO wire. (D) Schematic representation of …more
An international team of scientists has developed what may be the first one-step process for making seamless carbon-based nanomaterials that possess superior thermal, electrical and mechanical properties in three dimensions.
The research holds potential for increased energy storage in high efficiency batteries and supercapacitors, increasing the efficiency of energy conversion in solar cells, for lightweight thermal coatings and more. The study is published today in the online journal Science Advances.
In early testing, a three-dimensional (3D) fiber-like supercapacitor made with the uninterrupted fibers of carbon nanotubes and graphene matched or bettered—by a factor of four—the reported record-high capacities for this type of device.
Used as a counter electrode in a dye-sensitized solar cell, the material enabled the cell to convert power with up to 6.8 percent efficiency and more than doubled the performance of an identical cell that instead used an expensive platinum wire counter electrode.
Carbon nanotubes could be highly conductive along the 1D nanotube length and two-dimensional graphene sheets in the 2Dplane. But the materials fall short in a three-dimensional world due to the poor interlayer conductivity, as do two-step processes melding nanotubes and graphene into three dimensions.
“Two-step processes our lab and others developed earlier lack a seamless interface and, therefore, lack the conductance sought,” said Liming Dai, the Kent Hale Smith Professor of Macromolecular Science and Engineering at Case Western Reserve University and a leader of the research.
“In our one-step process, the interface is made with carbon-to-carbon bonding so it looks as if it’s one single graphene sheet,” Dai said. “That makes it an excellent thermal and electrical conductor in all planes.”
Dai has worked for nearly four years with Zhong Lin Wang, the Hightower Chair in Materials Science and Engineering, and Yong Ding, a senior research scientist, at Georgia Institute of Technology; and Zhenhai Xia, professor of materials science and engineering, at the University of North Texas; Ajit Roy, principal materials research engineer in the Materials and Manufacturing Directorate, Air Force Research Laboratory, Dayton; and others on a U.S. Department of Defense-Multidisciplinary University Research Initiative (MURI) program (Joycelyn Harrison, Program Manager). Close collaboration was also made with Yuhua Xue, the Research Associate at CWRU and visiting scholar from the Institute of Advanced Materials for Nano-Bio Applications, School of Ophthalmology & Optometry, Wenzhou Medical University, along with Jia Qu and Hao Chen, professors in the Wenzhou Medical University.
To make the 3-D material, the researchers etched radially aligned nanoholes along the length and circumference of a tiny aluminum wire, then used chemical vapor deposition to cover the surface with graphene using no metal catalyst that could remain in the structure.
“Radially-aligned nanotubes grow in the holes. The graphene that sheathes the wire and nanotube arrays are covalently bonded, forming pure carbon-to-carbon nodal junctions that minimize thermal and electrical resistance,” Wang said.
The architecture yields a huge surface area, adding to the transport properties, the researchers say. Using the Brunauer, Emmett and Teller theory, they calculate the surface area of this architecture to be nearly 527 square meters per gram of material.
Testing showed the material makes an ideal electrode for highly efficient energy storage. Capacitance by area reached as high as 89.4 millifarads per square centimeter and by length, up to 23.9 millifarads per centimeter in the fiber-like supercapacitor.
The properties can be customized. With the one-step process, the material can be made very long, or into a tube with a wider or narrower diameter, and the density of nanotubes can be varied to produce materials with differing properties for different needs.
The material can be used for charge storage in capacitors and batteries or the large surface could enable storage of hydrogen. “The properties could be used for an even wider variety of applications, including sensitive sensors, wearable electronics, thermal management and multifunctional aerospace systems”, Roy said.
The scientists are continuing to explore the properties that can be derived from these single 3D graphene layer fibers and are developing a process for making multilayer fibers.
Explore further: Researchers bring clean energy a step closer
More information: Rationally designed graphene-nanotube 3D architectures with a seamless nodal junction for efficient energy conversion and storage, Science Advances, advances.sciencemag.org/content/1/8/e1400198