Tag Archives: capacitors

Wooden supercapacitors: a cellulose nanofibril story

A May 24, 2018 news item on Nanowerk announces a technique for making sustainable electrodes (Note: A link has been removed),

Carbon aerogels are ultralight, conductive materials, which are extensively investigated for applications in supercapacitor electrodes in electrical cars and cell phones. Chinese scientists have now found a way to make these electrodes sustainably. The aerogels can be obtained directly from cellulose nanofibrils, the abundant cell-wall material in wood, finds the study reported in the journal Angewandte Chemie (“Wood-Derived Ultrathin Carbon Nanofiber Aerogels”).

A May 24, 2018 Wiley Publications press release, which originated the news item, explains further,

Supercapacitors are capacitors that can take up and release a very large amount of energy in a very short time. Key requirements for supercapacitor electrodes are a large surface area and conductivity, combined with a simple production method. Another growing issue in supercapacitor production–mainly for smartphone and electric car technologies–is sustainability. However, sustainable and economical production of carbon aerogels as supercapacitor electrode materials is possible, propose Shu-Hong Yu and colleagues from the University of Science and Technology of China, Hefei, China.

Carbon aerogels are ultralight conductive materials with a very large surface area. They can be prepared by two production routes: the first and cheapest starts from mostly phenolic components and produces aerogels with improvable conductivity, while the second route is based on graphene- and carbon-nanotube precursors. The latter method delivers high-performance aerogels but is expensive and non-environmentally friendly. In their search for different precursors, Yu and colleagues have found an abundant, far less expensive, and sustainable source: wood pulp.

Well, not really wood pulp, but its major ingredient, nanocellulose. Plant cell walls are stabilized by fibrous nanocellulose, and this extractable material has very recently stimulated substantial research and technological development. It forms a highly porous, but very stable transparent network, and, with the help of a recent technique–oxidation with a radical scavenger called TEMPO–it forms a microporous hydrogel of highly oriented cellulose nanofibrils with a uniform width and length. As organic aerogels are produced from hydrogels by drying and pyrolysis, the authors attempted pyrolysis of supercritically or freeze-dried nanofibrillated cellulose hydrogel.

As it turns out, the method was not as straightforward as expected because ice crystal formation and insufficient dehydration hampered carbonization, according to the authors. Here, a trick helped. The scientists pyrolyzed the dried gel in the presence of the organic acid catalyst para-toluenesulfonic acid. The catalyst lowered the decomposition temperature and yielded a “mechanically stable and porous three-dimensional nanofibrous network” featuring a “large specific surface area and high electrical conductivity,” the authors reported.

The authors also demonstrated that their wood-derived carbon aerogel worked well as a binder-free electrode for supercapacitor applications. The material displayed electrochemical properties comparable to commercial electrodes. The method is an interesting and innovative way in which to fabricate sustainable materials suitable for use in high-performance electronic devices.

This is the first time I’ve seen work on wood-based nanocellulose from China. Cellulose according to its Wikipedia entry is: ” … the most abundant organic polymer on Earth.” For example, there’s more cellulose in cotton than there is wood. So, I find it interesting that in a country not known for its forests, nanocellulose (in this project anyway) is being derived from wood.

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

Wood‐Derived Ultrathin Carbon Nanofiber Aerogels by Si‐Cheng Li, Bi‐Cheng Hu, Dr. Yan‐Wei Ding, Prof. Hai‐Wei Liang, Chao Li, Dr. Zi‐You Yu, Dr. Zhen‐Yu Wu, Prof. Wen‐Shuai Chen, Prof. Shu‐Hong Yu. Angewandt Chemie First published: 23 April 2018 DOI: https://doi.org/10.1002/anie.201802753

This paper is behind a paywall.

Want better energy storage materials? Add salt

An April 22, 2016 news item on Nanowerk reveals a secret to better energy storage materials,

The secret to making the best energy storage materials is growing them with as much surface area as possible. Like baking, it requires just the right mixture of ingredients prepared in a specific amount and order at just the right temperature to produce a thin sheet of material with the perfect chemical consistency to be useful for storing energy. A team of researchers from Drexel University, Huazhong University of Science and Technology (HUST) and Tsinghua University recently discovered a way to improve the recipe and make the resulting materials bigger and better and soaking up energy — the secret? Just add salt.

An April 22, 2016 Drexel University news release (also on EurekAlert), which originated the news item, provides more detail,

The team’s findings, which were recently published in the journal Nature Communications, show that using salt crystals as a template to grow thin sheets of conductive metal oxides make the materials turn out larger and more chemically pure — which makes them better suited for gathering ions and storing energy.

“The challenge of producing a metal oxide that reaches theoretical performance values is that the methods for making it inherently limit its size and often foul its chemical purity, which makes it fall short of predicted energy storage performance,” said Jun Zhou, a professor at HUST’s Wuhan National Laboratory for Optoelectronics and an author of the research. Our research reveals a way to grow stable oxide sheets with less fouling that are on the order of several hundreds of times larger than the ones that are currently being fabricated.”

In an energy storage device — a battery or a capacitor, for example — energy is contained in the chemical transfer of ions from an electrolyte solution to thin layers of conductive materials. As these devices evolve they’re becoming smaller and capable of holding an electric charge for longer periods of time without needing a recharge. The reason for their improvement is that researchers are fabricating materials that are better equipped, structurally and chemically, for collecting and disbursing ions.

In theory, the best materials for the job should be thin sheets of metal oxides, because their chemical structure and high surface area makes it easy for ions to attach — which is how energy storage occurs. But the metal oxide sheets that have been fabricated in labs thus far have fallen well short of their theoretical capabilities.

According to Zhou, Tang [?] and the team from HUST, the problem lies in the process of making the nanosheets — which involves either a deposition from gas or a chemical etching — often leaves trace chemical residues that contaminate the material and prevent ions from bonding to it. In addition, the materials made in this way are often just a few square micrometers in size.

Using salt crystals as a substrate for growing the crystals lets them spread out and form a larger sheet of oxide material. Think of it like making a waffle by dripping batter into a pan versus pouring it into a big waffle iron; the key to getting a big, sturdy product is getting the solution — be it batter, or chemical compound — to spread evenly over the template and stabilize in a uniform way.

“This method of synthesis, called ‘templating’ — where we use a sacrificial material as a substrate for growing a crystal — is used to create a certain shape or structure,” said Yury Gogotsi, PhD, University and Trustee Chair professor in Drexel’s College of Engineering and head of the A.J. Drexel Nanomaterials Institute, who was an author of the paper. “The trick in this work is that the crystal structure of salt must match the crystal structure of the oxide, otherwise it will form an amorphous film of oxide rather than a thing, strong and stable nanocrystal. This is the key finding of our research — it means that different salts must be used to produce different oxides.”

Researchers have used a variety of chemicals, compounds, polymers and objects as growth templates for nanomaterials. But this discovery shows the importance of matching a template to the structure of the material being grown. Salt crystals turn out to be the perfect substrate for growing oxide sheets of magnesium, molybdenum and tungsten.

The precursor solution coats the sides of the salt crystals as the oxides begin to form. After they’ve solidified, the salt is dissolved in a wash, leaving nanometer-thin two-dimensional sheets that formed on the sides of the salt crystal — and little trace of any contaminants that might hinder their energy storage performance. By making oxide nanosheets in this way, the only factors that limit their growth is the size of the salt crystal and the amount of precursor solution used.

“Lateral growth of the 2D oxides was guided by salt crystal geometry and promoted by lattice matching and the thickness was restrained by the raw material supply. The dimensions of the salt crystals are tens of micrometers and guide the growth of the 2D oxide to a similar size,” the researchers write in the paper. “On the basis of the naturally non-layered crystal structures of these oxides, the suitability of salt-assisted templating as a general method for synthesis of 2D oxides has been convincingly demonstrated.”

As predicted, the larger size of the oxide sheets also equated to a greater ability to collect and disburse ions from an electrolyte solution — the ultimate test for its potential to be used in energy storage devices. Results reported in the paper suggest that use of these materials may help in creating an aluminum-ion battery that could store more charge than the best lithium-ion batteries found in laptops and mobile devices today.

Gogotsi, along with his students in the Department of Materials Science and Engineering, has been collaborating with Huazhong University of Science and Technology since 2012 to explore a wide variety of materials for energy storage application. The lead author of the Nature Communications article, Xu Xiao, and co-author Tiangi Li, both Zhou’s doctoral students, came to Drexel as exchange students to learn about the University’s supercapacitor research. Those visits started a collaboration, which was supported by Gogotsi’s annual trips to HUST. While the partnership has already yielded five joint publications, Gogotsi speculates that this work is only beginning.

“The most significant result of this work thus far is that we’ve demonstrated the ability to generate high-quality 2D oxides with various compositions,” Gogotsi said. “I can certainly see expanding this approach to other oxides that may offer attractive properties for electrical energy storage, water desalination membranes, photocatalysis and other applications.”

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

Scalable salt-templated synthesis of two-dimensional transition metal oxides by Xu Xiao, Huaibing Song, Shizhe Lin, Ying Zhou, Xiaojun Zhan, Zhimi Hu, Qi Zhang, Jiyu Sun, Bo Yang, Tianqi Li, Liying Jiao, Jun Zhou, Jiang Tang, & Yury Gogotsi. Nature Communications 7, Article number:  11296 doi:10.1038/ncomms11296 Published 22 April 2016

This is an open access paper.