Tag Archives: supercapacitors

It’s a very ‘carbony’ time: graphene jacket, graphene-skinned airplane, and schwarzite

In August 2018, I been stumbled across several stories about graphene-based products and a new form of carbon.

Graphene jacket

The company producing this jacket has as its goal “… creating bionic clothing that is both bulletproof and intelligent.” Well, ‘bionic‘ means biologically-inspired engineering and ‘intelligent‘ usually means there’s some kind of computing capability in the product. This jacket, which is the first step towards the company’s goal, is not bionic, bulletproof, or intelligent. Nonetheless, it represents a very interesting science experiment in which you, the consumer, are part of step two in the company’s R&D (research and development).

Onto Vollebak’s graphene jacket,

Courtesy: Vollebak

From an August 14, 2018 article by Jesus Diaz for Fast Company,

Graphene is the thinnest possible form of graphite, which you can find in your everyday pencil. It’s purely bi-dimensional, a single layer of carbon atoms that has unbelievable properties that have long threatened to revolutionize everything from aerospace engineering to medicine. …

Despite its immense promise, graphene still hasn’t found much use in consumer products, thanks to the fact that it’s hard to manipulate and manufacture in industrial quantities. The process of developing Vollebak’s jacket, according to the company’s cofounders, brothers Steve and Nick Tidball, took years of intensive research, during which the company worked with the same material scientists who built Michael Phelps’ 2008 Olympic Speedo swimsuit (which was famously banned for shattering records at the event).

The jacket is made out of a two-sided material, which the company invented during the extensive R&D process. The graphene side looks gunmetal gray, while the flipside appears matte black. To create it, the scientists turned raw graphite into something called graphene “nanoplatelets,” which are stacks of graphene that were then blended with polyurethane to create a membrane. That, in turn, is bonded to nylon to form the other side of the material, which Vollebak says alters the properties of the nylon itself. “Adding graphene to the nylon fundamentally changes its mechanical and chemical properties–a nylon fabric that couldn’t naturally conduct heat or energy, for instance, now can,” the company claims.

The company says that it’s reversible so you can enjoy graphene’s properties in different ways as the material interacts with either your skin or the world around you. “As physicists at the Max Planck Institute revealed, graphene challenges the fundamental laws of heat conduction, which means your jacket will not only conduct the heat from your body around itself to equalize your skin temperature and increase it, but the jacket can also theoretically store an unlimited amount of heat, which means it can work like a radiator,” Tidball explains.

He means it literally. You can leave the jacket out in the sun, or on another source of warmth, as it absorbs heat. Then, the company explains on its website, “If you then turn it inside out and wear the graphene next to your skin, it acts like a radiator, retaining its heat and spreading it around your body. The effect can be visibly demonstrated by placing your hand on the fabric, taking it away and then shooting the jacket with a thermal imaging camera. The heat of the handprint stays long after the hand has left.”

There’s a lot more to the article although it does feature some hype and I’m not sure I believe Diaz’s claim (August 14, 2018 article) that ‘graphene-based’ hair dye is perfectly safe ( Note: A link has been removed),

Graphene is the thinnest possible form of graphite, which you can find in your everyday pencil. It’s purely bi-dimensional, a single layer of carbon atoms that has unbelievable properties that will one day revolutionize everything from aerospace engineering to medicine. Its diverse uses are seemingly endless: It can stop a bullet if you add enough layers. It can change the color of your hair with no adverse effects. [emphasis mine] It can turn the walls of your home into a giant fire detector. “It’s so strong and so stretchy that the fibers of a spider web coated in graphene could catch a falling plane,” as Vollebak puts it in its marketing materials.

Not unless things have changed greatly since March 2018. My August 2, 2018 posting featured the graphene-based hair dye announcement from March 2018 and a cautionary note from Dr. Andrew Maynard (scroll down ab out 50% of the way for a longer excerpt of Maynard’s comments),

Northwestern University’s press release proudly announced, “Graphene finds new application as nontoxic, anti-static hair dye.” The announcement spawned headlines like “Enough with the toxic hair dyes. We could use graphene instead,” and “’Miracle material’ graphene used to create the ultimate hair dye.”

From these headlines, you might be forgiven for getting the idea that the safety of graphene-based hair dyes is a done deal. Yet having studied the potential health and environmental impacts of engineered nanomaterials for more years than I care to remember, I find such overly optimistic pronouncements worrying – especially when they’re not backed up by clear evidence.

These studies need to be approached with care, as the precise risks of graphene exposure will depend on how the material is used, how exposure occurs and how much of it is encountered. Yet there’s sufficient evidence to suggest that this substance should be used with caution – especially where there’s a high chance of exposure or that it could be released into the environment.

The full text of Dr. Maynard’s comments about graphene hair dyes and risk can be found here.

Bearing in mind  that graphene-based hair dye is an entirely different class of product from the jacket, I wouldn’t necessarily dismiss risks; I would like to know what kind of risk assessment and safety testing has been done. Due to their understandable enthusiasm, the brothers Tidball have focused all their marketing on the benefits and the opportunity for the consumer to test their product (from graphene jacket product webpage),

While it’s completely invisible and only a single atom thick, graphene is the lightest, strongest, most conductive material ever discovered, and has the same potential to change life on Earth as stone, bronze and iron once did. But it remains difficult to work with, extremely expensive to produce at scale, and lives mostly in pioneering research labs. So following in the footsteps of the scientists who discovered it through their own highly speculative experiments, we’re releasing graphene-coated jackets into the world as experimental prototypes. Our aim is to open up our R&D and accelerate discovery by getting graphene out of the lab and into the field so that we can harness the collective power of early adopters as a test group. No-one yet knows the true limits of what graphene can do, so the first edition of the Graphene Jacket is fully reversible with one side coated in graphene and the other side not. If you’d like to take part in the next stage of this supermaterial’s history, the experiment is now open. You can now buy it, test it and tell us about it. [emphasis mine]

How maverick experiments won the Nobel Prize

While graphene’s existence was first theorised in the 1940s, it wasn’t until 2004 that two maverick scientists, Andre Geim and Konstantin Novoselov, were able to isolate and test it. Through highly speculative and unfunded experimentation known as their ‘Friday night experiments,’ they peeled layer after layer off a shaving of graphite using Scotch tape until they produced a sample of graphene just one atom thick. After similarly leftfield thinking won Geim the 2000 Ig Nobel prize for levitating frogs using magnets, the pair won the Nobel prize in 2010 for the isolation of graphene.

Should you be interested, in beta-testing the jacket, it will cost you $695 (presumably USD); order here. One last thing, Vollebak is based in the UK.

Graphene skinned plane

An August 14, 2018 news item (also published as an August 1, 2018 Haydale press release) by Sue Keighley on Azonano heralds a new technology for airplans,

Haydale, (AIM: HAYD), the global advanced materials group, notes the announcement made yesterday from the University of Central Lancashire (UCLAN) about the recent unveiling of the world’s first graphene skinned plane at the internationally renowned Farnborough air show.

The prepreg material, developed by Haydale, has potential value for fuselage and wing surfaces in larger scale aero and space applications especially for the rapidly expanding drone market and, in the longer term, the commercial aerospace sector. By incorporating functionalised nanoparticles into epoxy resins, the electrical conductivity of fibre-reinforced composites has been significantly improved for lightning-strike protection, thereby achieving substantial weight saving and removing some manufacturing complexities.

Before getting to the photo, here’s a definition for pre-preg from its Wikipedia entry (Note: Links have been removed),

Pre-preg is “pre-impregnated” composite fibers where a thermoset polymer matrix material, such as epoxy, or a thermoplastic resin is already present. The fibers often take the form of a weave and the matrix is used to bond them together and to other components during manufacture.

Haydale has supplied graphene enhanced prepreg material for Juno, a three-metre wide graphene-enhanced composite skinned aircraft, that was revealed as part of the ‘Futures Day’ at Farnborough Air Show 2018. [downloaded from https://www.azonano.com/news.aspx?newsID=36298]

A July 31, 2018 University of Central Lancashire (UCLan) press release provides a tiny bit more (pun intended) detail,

The University of Central Lancashire (UCLan) has unveiled the world’s first graphene skinned plane at an internationally renowned air show.

Juno, a three-and-a-half-metre wide graphene skinned aircraft, was revealed on the North West Aerospace Alliance (NWAA) stand as part of the ‘Futures Day’ at Farnborough Air Show 2018.

The University’s aerospace engineering team has worked in partnership with the Sheffield Advanced Manufacturing Research Centre (AMRC), the University of Manchester’s National Graphene Institute (NGI), Haydale Graphene Industries (Haydale) and a range of other businesses to develop the unmanned aerial vehicle (UAV), which also includes graphene batteries and 3D printed parts.

Billy Beggs, UCLan’s Engineering Innovation Manager, said: “The industry reaction to Juno at Farnborough was superb with many positive comments about the work we’re doing. Having Juno at one the world’s biggest air shows demonstrates the great strides we’re making in leading a programme to accelerate the uptake of graphene and other nano-materials into industry.

“The programme supports the objectives of the UK Industrial Strategy and the University’s Engineering Innovation Centre (EIC) to increase industry relevant research and applications linked to key local specialisms. Given that Lancashire represents the fourth largest aerospace cluster in the world, there is perhaps no better place to be developing next generation technologies for the UK aerospace industry.”

Previous graphene developments at UCLan have included the world’s first flight of a graphene skinned wing and the launch of a specially designed graphene-enhanced capsule into near space using high altitude balloons.

UCLan engineering students have been involved in the hands-on project, helping build Juno on the Preston Campus.

Haydale supplied much of the material and all the graphene used in the aircraft. Ray Gibbs, Chief Executive Officer, said: “We are delighted to be part of the project team. Juno has highlighted the capability and benefit of using graphene to meet key issues faced by the market, such as reducing weight to increase range and payload, defeating lightning strike and protecting aircraft skins against ice build-up.”

David Bailey Chief Executive of the North West Aerospace Alliance added: “The North West aerospace cluster contributes over £7 billion to the UK economy, accounting for one quarter of the UK aerospace turnover. It is essential that the sector continues to develop next generation technologies so that it can help the UK retain its competitive advantage. It has been a pleasure to support the Engineering Innovation Centre team at the University in developing the world’s first full graphene skinned aircraft.”

The Juno project team represents the latest phase in a long-term strategic partnership between the University and a range of organisations. The partnership is expected to go from strength to strength following the opening of the £32m EIC facility in February 2019.

The next step is to fly Juno and conduct further tests over the next two months.

Next item, a new carbon material.

Schwarzite

I love watching this gif of a schwarzite,

The three-dimensional cage structure of a schwarzite that was formed inside the pores of a zeolite. (Graphics by Yongjin Lee and Efrem Braun)

An August 13, 2018 news item on Nanowerk announces the new carbon structure,

The discovery of buckyballs [also known as fullerenes, C60, or buckminsterfullerenes] surprised and delighted chemists in the 1980s, nanotubes jazzed physicists in the 1990s, and graphene charged up materials scientists in the 2000s, but one nanoscale carbon structure – a negatively curved surface called a schwarzite – has eluded everyone. Until now.

University of California, Berkeley [UC Berkeley], chemists have proved that three carbon structures recently created by scientists in South Korea and Japan are in fact the long-sought schwarzites, which researchers predict will have unique electrical and storage properties like those now being discovered in buckminsterfullerenes (buckyballs or fullerenes for short), nanotubes and graphene.

An August 13, 2018 UC Berkeley news release by Robert Sanders, which originated the news item, describes how the Berkeley scientists and the members of their international  collaboration from Germany, Switzerland, Russia, and Italy, have contributed to the current state of schwarzite research,

The new structures were built inside the pores of zeolites, crystalline forms of silicon dioxide – sand – more commonly used as water softeners in laundry detergents and to catalytically crack petroleum into gasoline. Called zeolite-templated carbons (ZTC), the structures were being investigated for possible interesting properties, though the creators were unaware of their identity as schwarzites, which theoretical chemists have worked on for decades.

Based on this theoretical work, chemists predict that schwarzites will have unique electronic, magnetic and optical properties that would make them useful as supercapacitors, battery electrodes and catalysts, and with large internal spaces ideal for gas storage and separation.

UC Berkeley postdoctoral fellow Efrem Braun and his colleagues identified these ZTC materials as schwarzites based of their negative curvature, and developed a way to predict which zeolites can be used to make schwarzites and which can’t.

“We now have the recipe for how to make these structures, which is important because, if we can make them, we can explore their behavior, which we are working hard to do now,” said Berend Smit, an adjunct professor of chemical and biomolecular engineering at UC Berkeley and an expert on porous materials such as zeolites and metal-organic frameworks.

Smit, the paper’s corresponding author, Braun and their colleagues in Switzerland, China, Germany, Italy and Russia will report their discovery this week in the journal Proceedings of the National Academy of Sciences. Smit is also a faculty scientist at Lawrence Berkeley National Laboratory.

Playing with carbon

Diamond and graphite are well-known three-dimensional crystalline arrangements of pure carbon, but carbon atoms can also form two-dimensional “crystals” — hexagonal arrangements patterned like chicken wire. Graphene is one such arrangement: a flat sheet of carbon atoms that is not only the strongest material on Earth, but also has a high electrical conductivity that makes it a promising component of electronic devices.

schwarzite carbon cage

The cage structure of a schwarzite that was formed inside the pores of a zeolite. The zeolite is subsequently dissolved to release the new material. (Graphics by Yongjin Lee and Efrem Braun)

Graphene sheets can be wadded up to form soccer ball-shaped fullerenes – spherical carbon cages that can store molecules and are being used today to deliver drugs and genes into the body. Rolling graphene into a cylinder yields fullerenes called nanotubes, which are being explored today as highly conductive wires in electronics and storage vessels for gases like hydrogen and carbon dioxide. All of these are submicroscopic, 10,000 times smaller than the width of a human hair.

To date, however, only positively curved fullerenes and graphene, which has zero curvature, have been synthesized, feats rewarded by Nobel Prizes in 1996 and 2010, respectively.

In the 1880s, German physicist Hermann Schwarz investigated negatively curved structures that resemble soap-bubble surfaces, and when theoretical work on carbon cage molecules ramped up in the 1990s, Schwarz’s name became attached to the hypothetical negatively curved carbon sheets.

“The experimental validation of schwarzites thus completes the triumvirate of possible curvatures to graphene; positively curved, flat, and now negatively curved,” Braun added.

Minimize me

Like soap bubbles on wire frames, schwarzites are topologically minimal surfaces. When made inside a zeolite, a vapor of carbon-containing molecules is injected, allowing the carbon to assemble into a two-dimensional graphene-like sheet lining the walls of the pores in the zeolite. The surface is stretched tautly to minimize its area, which makes all the surfaces curve negatively, like a saddle. The zeolite is then dissolved, leaving behind the schwarzite.

soap bubble schwarzite structure

A computer-rendered negatively curved soap bubble that exhibits the geometry of a carbon schwarzite. (Felix Knöppel image)

“These negatively-curved carbons have been very hard to synthesize on their own, but it turns out that you can grow the carbon film catalytically at the surface of a zeolite,” Braun said. “But the schwarzites synthesized to date have been made by choosing zeolite templates through trial and error. We provide very simple instructions you can follow to rationally make schwarzites and we show that, by choosing the right zeolite, you can tune schwarzites to optimize the properties you want.”

Researchers should be able to pack unusually large amounts of electrical charge into schwarzites, which would make them better capacitors than conventional ones used today in electronics. Their large interior volume would also allow storage of atoms and molecules, which is also being explored with fullerenes and nanotubes. And their large surface area, equivalent to the surface areas of the zeolites they’re grown in, could make them as versatile as zeolites for catalyzing reactions in the petroleum and natural gas industries.

Braun modeled ZTC structures computationally using the known structures of zeolites, and worked with topological mathematician Senja Barthel of the École Polytechnique Fédérale de Lausanne in Sion, Switzerland, to determine which of the minimal surfaces the structures resembled.

The team determined that, of the approximately 200 zeolites created to date, only 15 can be used as a template to make schwarzites, and only three of them have been used to date to produce schwarzite ZTCs. Over a million zeolite structures have been predicted, however, so there could be many more possible schwarzite carbon structures made using the zeolite-templating method.

Other co-authors of the paper are Yongjin Lee, Seyed Mohamad Moosavi and Barthel of the École Polytechnique Fédérale de Lausanne, Rocio Mercado of UC Berkeley, Igor Baburin of the Technische Universität Dresden in Germany and Davide Proserpio of the Università degli Studi di Milano in Italy and Samara State Technical University in Russia.

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

Generating carbon schwarzites via zeolite-templating by Efrem Braun, Yongjin Lee, Seyed Mohamad Moosavi, Senja Barthel, Rocio Mercado, Igor A. Baburin, Davide M. Proserpio, and Berend Smit. PNAS August 14, 2018. 201805062; published ahead of print August 14, 2018. https://doi.org/10.1073/pnas.1805062115

This paper appears to be open access.

Bristly hybrid materials

Caption: [Image 1] A carbon fiber covered with a spiky forest of NiCoHC nanowires. Credit: All images reproduced from reference 1 under a Creative Commons Attribution 4.0 International License© 2018 KAUST

It makes me think of small, cuddly things like cats and dogs but it’s not. From an August 7, 2018 King Abdullah University of Science and Technology (KAUST; Saudi Arabia) news release (also published on August 12, 2018 on EurekAlert),

By combining multiple nanomaterials into a single structure, scientists can create hybrid materials that incorporate the best properties of each component and outperform any single substance. A controlled method for making triple-layered hollow nanostructures has now been developed at KAUST. The hybrid structures consist of a conductive organic core sandwiched between layers of electrocatalytically active metals: their potential uses range from better battery electrodes to renewable fuel production.

Although several methods exist to create two-layer materials, making three-layered structures has proven much more difficult, says Peng Wang from the Water Desalination and Reuse Center who co-led the current research with Professor Yu Han, member of the Advanced Membranes and Porous Materials Center at KAUST. The researchers developed a new, dual-template approach, explains Sifei Zhuo, a postdoctoral member of Wang’s team.

The researchers grew their hybrid nanomaterial directly on carbon paper–a mat of electrically conductive carbon fibers. They first produced a bristling forest of nickel cobalt hydroxyl carbonate (NiCoHC) nanowires onto the surface of each carbon fiber (image 1). Each tiny inorganic bristle was coated with an organic layer called hydrogen substituted graphdiyne (HsGDY) (image 2 [not included here]).

Next was the key dual-template step. When the team added a chemical mixture that reacts with the inner NiCoHC, the HsGDY acted as a partial barrier. Some nickel and cobalt ions from the inner layer diffused outward, where they reacted with thiomolybdate from the surrounding solution to form the outer nickel-, cobalt-co-doped MoS2 (Ni,Co-MoS2) layer. Meanwhile, some sulfur ions from the added chemicals diffused inwards to react with the remaining nickel and cobalt. The resulting substance (image 3 [not included here]) had the structure Co9S8, Ni3S2@HsGDY@Ni,Co-MoS2, in which the conductive organic HsGDY layer is sandwiched between two inorganic layers (image 4 [not included here]).

The triple layer material showed good performance at electrocatalytically breaking up water molecules to generate hydrogen, a potential renewable fuel. The researchers also created other triple-layer materials using the dual-template approach

“These triple-layered nanostructures hold great potential in energy conversion and storage,” says Zhuo. “We believe it could be extended to serve as a promising electrode in many electrochemical applications, such as in supercapacitors and sodium-/lithium-ion batteries, and for use in water desalination.”

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

Dual-template engineering of triple-layered nanoarray electrode of metal chalcogenides sandwiched with hydrogen-substituted graphdiyne by Sifei Zhuo, Yusuf Shi, Lingmei Liu, Renyuan Li, Le Shi, Dalaver H. Anjum, Yu Han, & Peng Wang. Nature Communicationsvolume 9, Article number: 3132 (2018) DOI: https://doi.org/10.1038/s41467-018-05474-0 Published 07 August 2018

This paper is open access.

 

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.

Mixing the unmixable for all new nanoparticles

This news comes out of the University of Maryland and the discovery could led to nanoparticles that have never before been imagined. From a March 29, 2018 news item on ScienceDaily,

Making a giant leap in the ‘tiny’ field of nanoscience, a multi-institutional team of researchers is the first to create nanoscale particles composed of up to eight distinct elements generally known to be immiscible, or incapable of being mixed or blended together. The blending of multiple, unmixable elements into a unified, homogenous nanostructure, called a high entropy alloy nanoparticle, greatly expands the landscape of nanomaterials — and what we can do with them.

This research makes a significant advance on previous efforts that have typically produced nanoparticles limited to only three different elements and to structures that do not mix evenly. Essentially, it is extremely difficult to squeeze and blend different elements into individual particles at the nanoscale. The team, which includes lead researchers at University of Maryland, College Park (UMD)’s A. James Clark School of Engineering, published a peer-reviewed paper based on the research featured on the March 30 [2018] cover of Science.

A March 29, 2018 University of Maryland press release (also on EurekAlert), which originated the news item, delves further (Note: Links have been removed),

“Imagine the elements that combine to make nanoparticles as Lego building blocks. If you have only one to three colors and sizes, then you are limited by what combinations you can use and what structures you can assemble,” explains Liangbing Hu, associate professor of materials science and engineering at UMD and one of the corresponding authors of the paper. “What our team has done is essentially enlarged the toy chest in nanoparticle synthesis; now, we are able to build nanomaterials with nearly all metallic and semiconductor elements.”

The researchers say this advance in nanoscience opens vast opportunities for a wide range of applications that includes catalysis (the acceleration of a chemical reaction by a catalyst), energy storage (batteries or supercapacitors), and bio/plasmonic imaging, among others.

To create the high entropy alloy nanoparticles, the researchers employed a two-step method of flash heating followed by flash cooling. Metallic elements such as platinum, nickel, iron, cobalt, gold, copper, and others were exposed to a rapid thermal shock of approximately 3,000 degrees Fahrenheit, or about half the temperature of the sun, for 0.055 seconds. The extremely high temperature resulted in uniform mixtures of the multiple elements. The subsequent rapid cooling (more than 100,000 degrees Fahrenheit per second) stabilized the newly mixed elements into the uniform nanomaterial.

“Our method is simple, but one that nobody else has applied to the creation of nanoparticles. By using a physical science approach, rather than a traditional chemistry approach, we have achieved something unprecedented,” says Yonggang Yao, a Ph.D. student at UMD and one of the lead authors of the paper.

To demonstrate one potential use of the nanoparticles, the research team used them as advanced catalysts for ammonia oxidation, which is a key step in the production of nitric acid (a liquid acid that is used in the production of ammonium nitrate for fertilizers, making plastics, and in the manufacturing of dyes). They were able to achieve 100 percent oxidation of ammonia and 99 percent selectivity toward desired products with the high entropy alloy nanoparticles, proving their ability as highly efficient catalysts.

Yao says another potential use of the nanoparticles as catalysts could be the generation of chemicals or fuels from carbon dioxide.

“The potential applications for high entropy alloy nanoparticles are not limited to the field of catalysis. With cross-discipline curiosity, the demonstrated applications of these particles will become even more widespread,” says Steven D. Lacey, a Ph.D. student at UMD and also one of the lead authors of the paper.

This research was performed through a multi-institutional collaboration of Prof. Liangbing Hu’s group at the University of Maryland, College Park; Prof. Reza Shahbazian-Yassar’s group at University of Illinois at Chicago; Prof. Ju Li’s group at the Massachusetts Institute of Technology; Prof. Chao Wang’s group at Johns Hopkins University; and Prof. Michael Zachariah’s group at the University of Maryland, College Park.

What outside experts are saying about this research:

“This is quite amazing; Dr. Hu creatively came up with this powerful technique, carbo-thermal shock synthesis, to produce high entropy alloys of up to eight different elements in a single nanoparticle. This is indeed unthinkable for bulk materials synthesis. This is yet another beautiful example of nanoscience!,” says Peidong Yang, the S.K. and Angela Chan Distinguished Professor of Energy and professor of chemistry at the University of California, Berkeley and member of the American Academy of Arts and Sciences.

“This discovery opens many new directions. There are simulation opportunities to understand the electronic structure of the various compositions and phases that are important for the next generation of catalyst design. Also, finding correlations among synthesis routes, composition, and phase structure and performance enables a paradigm shift toward guided synthesis,” says George Crabtree, Argonne Distinguished Fellow and director of the Joint Center for Energy Storage Research at Argonne National Laboratory.

More from the research coauthors:

“Understanding the atomic order and crystalline structure in these multi-element nanoparticles reveals how the synthesis can be tuned to optimize their performance. It would be quite interesting to further explore the underlying atomistic mechanisms of the nucleation and growth of high entropy alloy nanoparticle,” says Reza Shahbazian-Yassar, associate professor at the University of Illinois at Chicago and a corresponding author of the paper.

“Carbon metabolism drives ‘living’ metal catalysts that frequently move around, split, or merge, resulting in a nanoparticle size distribution that’s far from the ordinary, and highly tunable,” says Ju Li, professor at the Massachusetts Institute of Technology and a corresponding author of the paper.

“This method enables new combinations of metals that do not exist in nature and do not otherwise go together. It enables robust tuning of the composition of catalytic materials to optimize the activity, selectivity, and stability, and the application will be very broad in energy conversions and chemical transformations,” says Chao Wang, assistant professor of chemical and biomolecular engineering at Johns Hopkins University and one of the study’s authors.

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

Carbothermal shock synthesis of high-entropy-alloy nanoparticles by Yonggang Yao, Zhennan Huang, Pengfei Xie, Steven D. Lacey, Rohit Jiji Jacob, Hua Xie, Fengjuan Chen, Anmin Nie, Tiancheng Pu, Miles Rehwoldt, Daiwei Yu, Michael R. Zachariah, Chao Wang, Reza Shahbazian-Yassar, Ju Li, Liangbing Hu. Science 30 Mar 2018: Vol. 359, Issue 6383, pp. 1489-1494 DOI: 10.1126/science.aan5412

This paper is behind a paywall.

A candy cane supercapacitor?

Courtesy: Queen Mary University of London

It takes a lot more imagination than I have to describe the object on the right as resembling the  candy cane on the left, assuming that’s what was intended when it was used to illustrate the university’s press release. I like being pushed to see resemblances to things that are not immediately apparent to me. This may never look like a candy cane to me but I appreciate that someone finds it to be so. An August 16, 2017 news item on ScienceDaily announces the ‘candy cane’ supercapacitor,

Supercapacitors promise recharging of phones and other devices in seconds and minutes as opposed to hours for batteries. But current technologies are not usually flexible, have insufficient capacities, and for many their performance quickly degrades with charging cycles.

Researchers at Queen Mary University of London (QMUL) and the University of Cambridge have found a way to improve all three problems in one stroke.

Their prototyped polymer electrode, which resembles a candy cane usually hung on a Christmas tree, achieves energy storage close to the theoretical limit, but also demonstrates flexibility and resilience to charge/discharge cycling.

The technique could be applied to many types of materials for supercapacitors and enable fast charging of mobile phones, smart clothes and implantable devices.

The Aug. 16, 2017 Queen Mary University of London (QMUL) press release (also on EurekAlert), which originated the news item, provides more detail about the technology,

Pseudocapacitance is a property of polymer and composite supercapacitors that allows ions to enter inside the material and thus pack much more charge than carbon ones that mostly store the charge as concentrated ions (in the so-called double layer) near the surface.

The problem with polymer supercapacitors, however, is that the ions necessary for these chemical reactions can only access the top few nanometers below the material surface, leaving the rest of the electrode as dead weight. Growing polymers as nano-structures is one way to increase the amount of accessible material near the surface, but this can be expensive, hard to scale up, and often results in poor mechanical stability.

The researchers, however, have developed a way to interweave nanostructures within a bulk material, thereby achieving the benefits of conventional nanostructuring without using complex synthesis methods or sacrificing material toughness.

Project leader, Stoyan Smoukov, explained: “Our supercapacitors can store a lot of charge very quickly, because the thin active material (the conductive polymer) is always in contact with a second polymer which contains ions, just like the red thin regions of a candy cane are always in close proximity to the white parts. But this is on a much smaller scale.

“This interpenetrating structure enables the material to bend more easily, as well as swell and shrink without cracking, leading to greater longevity. This one method is like killing not just two, but three birds with one stone.”

The outcomes

The Smoukov group had previously pioneered a combinatorial route to multifunctionality using interpenetrating polymer networks (IPN) in which each component would have its own function, rather than using trial-and-error chemistry to fit all functions in one molecule.

This time they applied the method to energy storage, specifically supercapacitors, because of the known problem of poor material utilization deep beneath the electrode surface.

This interpenetration technique drastically increases the material’s surface area, or more accurately the interfacial area between the different polymer components.

Interpenetration also happens to solve two other major problems in supercapacitors. It brings flexibility and toughness because the interfaces stop growth of any cracks that may form in the material. It also allows the thin regions to swell and shrink repeatedly without developing large stresses, so they are electrochemically resistant and maintain their performance over many charging cycles.

The researchers are currently rationally designing and evaluating a range of materials that can be adapted into the interpenetrating polymer system for even better supercapacitors.

In an upcoming review, accepted for publication in the journal Sustainable Energy and Fuels, they overview the different techniques people have used to improve the multiple parameters required for novel supercapacitors.

Such devices could be made in soft and flexible freestanding films, which could power electronics embedded in smart clothing, wearable and implantable devices, and soft robotics. The developers hope to make their contribution to provide ubiquitous power for the emerging Internet of Things (IoT) devices, which is still a significant challenge ahead.

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

Semi-Interpenetrating Polymer Networks for Enhanced Supercapacitor Electrodes by Kara D. Fong, Tiesheng Wang, Hyun-Kyung Kim, R. Vasant Kumar, and Stoyan K. Smoukov. ACS Energy Lett., 2017, 2, pp 2014–2020 DOI: 10.1021/acsenergylett.7b00466 Publication Date (Web): August 14, 2017

Copyright © 2017 American Chemical Society

This paper is behind a paywall.

Energy storage inspired by a fern’s fractal patterns

Australian researchers have come up with a bio-inspired approach to making solar energy storage more viable according to a March 31, 2017 news item on Nanowerk (Note: A link has been removed),

Inspired by an American fern, researchers have developed a groundbreaking prototype that could be the answer to the storage challenge still holding solar back as a total energy solution (Science Express, “Bioinspired fractal electrodes for solar energy storages”).

The breakthrough electrode prototype (right) can be combined with a solar cell (left) for on-chip energy harvesting and storage. (Image: RMIT University)

A March 31, 2017 RMIT University press release, which originated the news item on Nanowerk, provides more detail (Note: A link has been removed),

The new type of electrode created by RMIT University researchers could boost the capacity of existing integrable storage technologies by 3000 per cent.

But the graphene-based prototype also opens a new path to the development of flexible thin film all-in-one solar capture and storage, bringing us one step closer to self-powering smart phones, laptops, cars and buildings.

The new electrode is designed to work with supercapacitors, which can charge and discharge power much faster than conventional batteries. Supercapacitors have been combined with solar, but their wider use as a storage solution is restricted because of their limited capacity.

RMIT’s Professor Min Gu said the new design drew on nature’s own genius solution to the challenge of filling a space in the most efficient way possible – through intricate self-repeating patterns known as “fractals”.

“The leaves of the western swordfern are densely crammed with veins, making them extremely efficient for storing energy and transporting water around the plant,” said Gu, Leader of the Laboratory of Artificial Intelligence Nanophotonics and Associate Deputy Vice-Chancellor for Research Innovation and Entrepreneurship at RMIT.

“Our electrode is based on these fractal shapes – which are self-replicating, like the mini structures within snowflakes – and we’ve used this naturally-efficient design to improve solar energy storage at a nano level.

“The immediate application is combining this electrode with supercapacitors, as our experiments have shown our prototype can radically increase their storage capacity – 30 times more than current capacity limits.

“Capacity-boosted supercapacitors would offer both long-term reliability and quick-burst energy release – for when someone wants to use solar energy on a cloudy day for example – making them ideal alternatives for solar power storage.”

Combined with supercapacitors, the fractal-enabled laser-reduced graphene electrodes can hold the stored charge for longer, with minimal leakage.

The fractal design reflected the self-repeating shape of the veins of the western swordfern, Polystichum munitum, native to western North America.

Lead author, PhD researcher Litty Thekkekara, said because the prototype was based on flexible thin film technology, its potential applications were countless.

“The most exciting possibility is using this electrode with a solar cell, to provide a total on-chip energy harvesting and storage solution,” Thekkekara said.

“We can do that now with existing solar cells but these are bulky and rigid. The real future lies in integrating the prototype with flexible thin film solar – technology that is still in its infancy.

“Flexible thin film solar could be used almost anywhere you can imagine, from building windows to car panels, smart phones to smart watches. We would no longer need batteries to charge our phones or charging stations for our hybrid cars.

“With this flexible electrode prototype we’ve solved the storage part of the challenge, as well as shown how they can work with solar cells without affecting performance. Now the focus needs to be on flexible solar energy, so we can work towards achieving our vision of fully solar-reliant, self-powering electronics.”

The repeating pattern of veins in the leaves of the western swordfern, as seen here magnified 400 times, served as the inspiration for the new high-density electrode(Credit: RMIT University)

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

Bioinspired fractal electrodes for solar energy storages by Litty V. Thekkekara & Min Gu. Scientific Reports 7, Article number: 45585 (2017) doi:10.1038/srep45585 Published online: 31 March 2017

This is an open access paper.

Mimicking the architecture of materials like wood and bone

Caption: Microstructures like this one developed at Washington State University could be used in batteries, lightweight ultrastrong materials, catalytic converters, supercapacitors and biological scaffolds. Credit: Washington State University

A March 3, 2017 news item on Nanowerk features a new 3D manufacturing technique for creating biolike materials, (Note: A link has been removed)

Washington State University nanotechnology researchers have developed a unique, 3-D manufacturing method that for the first time rapidly creates and precisely controls a material’s architecture from the nanoscale to centimeters. The results closely mimic the intricate architecture of natural materials like wood and bone.

They report on their work in the journal Science Advances (“Three-dimensional microarchitected materials and devices using nanoparticle assembly by pointwise spatial printing”) and have filed for a patent.

A March 3, 2017 Washington State University news release by Tina Hilding (also on EurekAlert), which originated the news item, expands on the theme,

“This is a groundbreaking advance in the 3-D architecturing of materials at nano- to macroscales with applications in batteries, lightweight ultrastrong materials, catalytic converters, supercapacitors and biological scaffolds,” said Rahul Panat, associate professor in the School of Mechanical and Materials Engineering, who led the research. “This technique can fill a lot of critical gaps for the realization of these technologies.”

The WSU research team used a 3-D printing method to create foglike microdroplets that contain nanoparticles of silver and to deposit them at specific locations. As the liquid in the fog evaporated, the nanoparticles remained, creating delicate structures. The tiny structures, which look similar to Tinkertoy constructions, are porous, have an extremely large surface area and are very strong.

Silver was used because it is easy to work with. However, Panat said, the method can be extended to any other material that can be crushed into nanoparticles – and almost all materials can be.

The researchers created several intricate and beautiful structures, including microscaffolds that contain solid truss members like a bridge, spirals, electronic connections that resemble accordion bellows or doughnut-shaped pillars.

The manufacturing method itself is similar to a rare, natural process in which tiny fog droplets that contain sulfur evaporate over the hot western Africa deserts and give rise to crystalline flower-like structures called “desert roses.”

Because it uses 3-D printing technology, the new method is highly efficient, creates minimal waste and allows for fast and large-scale manufacturing.

The researchers would like to use such nanoscale and porous metal structures for a number of industrial applications; for instance, the team is developing finely detailed, porous anodes and cathodes for batteries rather than the solid structures that are now used. This advance could transform the industry by significantly increasing battery speed and capacity and allowing the use of new and higher energy materials.

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

Three-dimensional microarchitected materials and devices using nanoparticle assembly by pointwise spatial printing by Mohammad Sadeq Saleh, Chunshan Hu, and Rahul Panat. Science Advances  03 Mar 2017: Vol. 3, no. 3, e1601986 DOI: 10.1126/sciadv.1601986

This paper appears to be open access.

Finally, there is a video,

Understanding how carbon nanotubes grow and self-organize is key to better production

This research may help to commercialize use of carbon nanotubes (CNTs), a  ‘magical’ nanoscale material with great promise and great difficulties (standardizing production being one of the main difficulties). A Feb. 10, 2017 news item on phys.org describes how researchers at the Lawrence Livermore National Laboratory (LLNL) and other collaborators have recorded carbon nanotubes self-organizing,

For the first time, Lawrence Livermore National Laboratory scientists and collaborators have captured a movie of how large populations of carbon nanotubes grow and align themselves.

Understanding how carbon nanotubes (CNT) nucleate, grow and self-organize to form macroscale materials is critical for application-oriented design of next-generation supercapacitors, electronic interconnects, separation membranes and advanced yarns and fabrics.

A Feb. 9, 2017 LLNL news release, which originated the news item, provides more information about the research (Note: Links have been removed),

New research by LLNL scientist Eric Meshot and colleagues from Brookhaven National Laboratory (link is external) (BNL) and Massachusetts Institute of Technology (link is external) (MIT) has demonstrated direct visualization of collective nucleation and self-organization of aligned carbon nanotube films inside of an environmental transmission electron microscope (ETEM).

In a pair of studies reported in recent issues of Chemistry of Materials (link is external) and ACS Nano (link is external), the researchers leveraged a state-of-the-art kilohertz camera in an aberration-correction ETEM at BNL to capture the inherently rapid processes that govern the growth of these exciting nanostructures.

Among other phenomena discovered, the researchers are the first to provide direct proof of how mechanical competition among neighboring carbon nanotubes can simultaneously promote self-alignment while also frustrating and limiting growth.

“This knowledge may enable new pathways toward mitigating self-termination and promoting growth of ultra-dense and aligned carbon nanotube materials, which would directly impact several application spaces, some of which are being pursued here at the Laboratory,” Meshot said.

Meshot has led the CNT synthesis development at LLNL for several projects, including those supported by the Laboratory Directed Research and Development (LDRD) program and the Defense Threat Reduction Agency (link is external) (DTRA) that use CNTs as fluidic nanochannels for applications ranging from single-molecule detection to macroscale membranes for breathable and protective garments.

Here’s a link to and a citation for the both of the papers mentioned in the news release,

Measurement of the Dewetting, Nucleation, and Deactivation Kinetics of Carbon Nanotube Population Growth by Environmental Transmission Electron Microscopy by Mostafa Bedewy, B. Viswanath, Eric R. Meshot, Dmitri N. Zakharov, Eric A. Stach, and A. John Hart. Chem. Mater., 2016, 28 (11), pp 3804–3813 DOI: 10.1021/acs.chemmater.6b00798 Publication Date (Web): May 23, 2016

Copyright © 2016 American Chemical Society

Real-Time Imaging of Self-Organization and Mechanical Competition in Carbon Nanotube Forest Growth by Viswanath Balakrishnan, Mostafa Bedewy, Eric R. Meshot, Sebastian W. Pattinson, Erik S. Polsen, Fabrice Laye, Dmitri N. Zakharov, Eric A. Stach, and A. John Hart. ACS Nano, 2016, 10 (12), pp 11496–11504 DOI: 10.1021/acsnano.6b07251 Publication Date (Web): November 23, 2016

Copyright © 2016 American Chemical Society

Both papers are behind a paywall.

The researchers have also provided this image which allows you to appreciate the difference between a ‘scientific’ version of the work and an artistic version,

This transmission electron microscope image shows growth of a dense carbon nanotube population. Courtesy: LLNL

South Africa, energy, and nanotechnology

South African academics Nosipho Moloto, Associate Professor, Department of Chemistry, University of the Witwatersrand and Siyabonga P. Ngubane, Lecturer in Chemistry, University of the Witwatersrand have written a Feb. 17, 2016 article for The Conversation (also available on the South African Broadcasting Corporation website) about South Africa’s energy needs and its nanotechnology efforts (Note: Links have been removed),

Energy is an economic driver of both developed and developing countries. South Africa over the past few years has faced an energy crisis with rolling blackouts between 2008 and 2015. Part of the problem has been attributed to mismanagement by the state-owned utility company Eskom, particularly the shortcomings of maintenance plans on several plants.

But South Africa has two things going for it that could help it out of its current crisis. By developing a strong nanotechnology capability and applying this to its rich mineral reserves the country is well-placed to develop new energy technologies.

Nanotechnology has already shown that it has the potential to alleviate energy problems. …

It can also yield materials with new properties and the miniaturisation of devices. For example, since the discovery of graphene, a single atomic layer of graphite, several applications in biological engineering, electronics and composite materials have been identified. These include economic and efficient devices like solar cells and lithium ion secondary batteries.

Nanotechnology has seen an incredible increase in commercialisation. Nearly 10,000 patents have been filed by large corporations since its beginning in 1991. There are already a number of nanotechnology products and solutions on the market. Examples include Miller’s beer bottling composites, Armor’s N-Force line bulletproof vests and printed solar cells produced by Nanosolar – as well as Samsung’s nanotechnology television.

The advent of nanotechnology in South Africa began with the South African Nanotechnology Initiative in 2002. This was followed by the a [sic] national nanotechnology strategy in 2003.

The government has spent more than R450 million [Rand] in nanotechnology and nanosciences research since 2006. For example, two national innovation centres have been set up and funding has been made available for equipment. There has also been flagship funding.

The country could be globally competitive in this field due to the infancy of the technology. As such, there are plenty of opportunities to make novel discoveries in South Africa.

Mineral wealth

There is another major advantage South Africa has that could help diversify its energy supply. It has an abundance of mineral wealth with an estimated value of US$2.5 trillion. The country has the world’s largest reserves of manganese and platinum group metals. It also has massive reserves of gold, diamonds, chromite ore and vanadium.

Through beneficiation and nanotechnology these resources could be used to cater for the development of new energy technologies. Research in beneficiation of minerals for energy applications is gaining momentum. For example, Anglo American and the Department of Science and Technology have embarked on a partnership to convert hydrogen into electricity.

The Council for Scientific and Industrial research also aims to develop low cost lithium ion batteries and supercapacitors using locally mined manganese and titanium ores. There is collaborative researchto use minerals like gold to synthesize nanomaterials for application in photovoltaics.

The current photovoltaic market relies on importing solar cells or panels from Europe, Asia and the US for local assembly to produce arrays. South African UV index is one of the highest in the world which reduces the lifespan of solar panels. The key to a thriving and profitable photovoltaic sector therefore lies in local production and research and development to support the sector.

It’s worth reading the article in its entirety if you’re interested in a perspective on South Africa’s energy and nanotechnology efforts.

Wearable tech for Christmas 2015 and into 2016

This is a roundup post of four items to cross my path this morning (Dec. 17, 2015), all of them concerned with wearable technology.

The first, a Dec. 16, 2015 news item on phys.org, is a fluffy little piece concerning the imminent arrival of a new generation of wearable technology,

It’s not every day that there’s a news story about socks. But in November [2015], a pair won the Best New Wearable Technology Device Award at a Silicon Valley conference. The smart socks, which track foot landings and cadence, are at the forefront of a new generation of wearable electronics, according to an article in Chemical & Engineering News (C&EN), the weekly newsmagazine of the American Chemical Society [ACS].

That news item was originated by a Dec. 16, 2015 ACS news release on EurekAlert which adds this,

Marc S. Reisch, a senior correspondent at C&EN, notes that stiff wristbands like the popular FitBit that measure heart rate and the number of steps people take have become common. But the long-touted technology needed to create more flexible monitoring devices has finally reached the market. Developers have successfully figured out how to incorporate stretchable wiring and conductive inks in clothing fabric, program them to transmit data wirelessly and withstand washing.

In addition to smart socks, fitness shirts and shoe insoles are on the market already or are nearly there. Although athletes are among the first to gain from the technology, the less fitness-oriented among us could also benefit. One fabric concept product — designed not for covering humans but a car steering-wheel — could sense driver alertness and make roads safer.

Reisch’s Dec. 7, 2015 article (C&EN vol. 93, issue 48, pp. 28-90) provides more detailed information and market information such as this,

Materials suppliers, component makers, and apparel developers gathered at a printed-electronics conference in Santa Clara, Calif., within a short drive of tech giants such as Google and Apple, to compare notes on embedding electronics into the routines of daily life. A notable theme was the effort to stealthily [emphasis mine] place sensors on exercise shirts, socks, and shoe soles so that athletes and fitness buffs can wirelessly track their workouts and doctors can monitor the health of their patients.

“Wearable technology is becoming more wearable,” said Raghu Das, chief executive officer of IDTechEx [emphasis mine], the consulting firm that organized the conference. By that he meant the trend is toward thinner and more flexible devices that include not just wrist-worn fitness bands but also textiles printed with stretchable wiring and electronic sensors, thanks to advances in conductive inks.

Interesting use of the word ‘stealthy’, which often suggests something sneaky as opposed to merely secretive. I imagine what’s being suggested is that the technology will not impose itself on the user (i.e., you won’t have to learn how to use it as you did with phones and computers).

Leading into my second item, IDC (International Data Corporation), not to be confused with IDTechEx, is mentioned in a Dec. 17, 2015 news item about wearable technology markets on phys.org,

The global market for wearable technology is seeing a surge, led by watches, smart clothing and other connected gadgets, a research report said Thursday [Dec. 16, 2015].

IDC said its forecast showed the worldwide wearable device market will reach a total of 111.1 million units in 2016, up 44.4 percent from this year.

By 2019, IDC sees some 214.6 million units, or a growth rate averaging 28 percent.

A Dec. 17, 2015 IDC press release, which originated the news item, provides more details about the market forecast,

“The most common type of wearables today are fairly basic, like fitness trackers, but over the next few years we expect a proliferation of form factors and device types,” said Jitesh Ubrani , Senior Research Analyst for IDC Mobile Device Trackers. “Smarter clothing, eyewear, and even hearables (ear-worn devices) are all in their early stages of mass adoption. Though at present these may not be significantly smarter than their analog counterparts, the next generation of wearables are on track to offer vastly improved experiences and perhaps even augment human abilities.”

One of the most popular types of wearables will be smartwatches, reaching a total of 34.3 million units shipped in 2016, up from the 21.3 million units expected to ship in 2015. By 2019, the final year of the forecast, total shipments will reach 88.3 million units, resulting in a five-year CAGR of 42.8%.

“In a short amount of time, smartwatches have evolved from being extensions of the smartphone to wearable computers capable of communications, notifications, applications, and numerous other functionalities,” noted Ramon Llamas , Research Manager for IDC’s Wearables team. “The smartwatch we have today will look nothing like the smartwatch we will see in the future. Cellular connectivity, health sensors, not to mention the explosive third-party application market all stand to change the game and will raise both the appeal and value of the market going forward.

“Smartwatch platforms will lead the evolution,” added Llamas. “As the brains of the smartwatch, platforms manage all the tasks and processes, not the least of which are interacting with the user, running all of the applications, and connecting with the smartphone. Once that third element is replaced with cellular connectivity, the first two elements will take on greater roles to make sense of all the data and connections.”

Top Five Smartwatch Platform Highlights

Apple’s watchOS will lead the smartwatch market throughout our forecast, with a loyal fanbase of Apple product owners and a rapidly growing application selection, including both native apps and Watch-designed apps. Very quickly, watchOS has become the measuring stick against which other smartwatches and platforms are compared. While there is much room for improvement and additional features, there is enough momentum to keep it ahead of the rest of the market.

Android/Android Wear will be a distant second behind watchOS even as its vendor list grows to include technology companies (ASUS, Huawei, LG, Motorola, and Sony) and traditional watchmakers (Fossil and Tag Heuer). The user experience on Android Wear devices has been largely the same from one device to the next, leaving little room for OEMs to develop further and users left to select solely on price and smartwatch design.

Smartwatch pioneer Pebble will cede market share to AndroidWear and watchOS but will not disappear altogether. Its simple user interface and devices make for an easy-to-understand use case, and its price point relative to other platforms makes Pebble one of the most affordable smartwatches on the market.

Samsung’s Tizen stands to be the dark horse of the smartwatch market and poses a threat to Android Wear, including compatibility with most flagship Android smartphones and an application selection rivaling Android Wear. Moreover, with Samsung, Tizen has benefited from technology developments including a QWERTY keyboard on a smartwatch screen, cellular connectivity, and new user interfaces. It’s a combination that helps Tizen stand out, but not enough to keep up with AndroidWear and watchOS.

There will be a small, but nonetheless significant market for smart wristwear running on a Real-Time Operating System (RTOS), which is capable of running third-party applications, but not on any of these listed platforms. These tend to be proprietary operating systems and OEMs will use them when they want to champion their own devices. These will help within specific markets or devices, but will not overtake the majority of the market.

The company has provided a table with five-year CAGR (compound annual growth rate) growth estimates, which can be found with the Dec. 17, 2015 IDC press release.

Disclaimer: I am not endorsing IDC’s claims regarding the market for wearable technology.

For the third and fourth items, it’s back to the science. A Dec. 17, 2015 news item on Nanowerk, describes, in general terms, some recent wearable technology research at the University of Manchester (UK), Note: A link has been removed),

Cheap, flexible, wireless graphene communication devices such as mobile phones and healthcare monitors can be directly printed into clothing and even skin, University of Manchester academics have demonstrated.

In a breakthrough paper in Scientific Reports (“Highly Flexible and Conductive Printed Graphene for Wireless Wearable Communications Applications”), the researchers show how graphene could be crucial to wearable electronic applications because it is highly-conductive and ultra-flexible.

The research could pave the way for smart, battery-free healthcare and fitness monitoring, phones, internet-ready devices and chargers to be incorporated into clothing and ‘smart skin’ applications – printed graphene sensors integrated with other 2D materials stuck onto a patient’s skin to monitor temperature, strain and moisture levels.

Detail is provided in a Dec. 17, 2015 University of Manchester press release, which originated the news item, (Note: Links have been removed),

Examples of communication devices include:

• In a hospital, a patient wears a printed graphene RFID tag on his or her arm. The tag, integrated with other 2D materials, can sense the patient’s body temperature and heartbeat and sends them back to the reader. The medical staff can monitor the patient’s conditions wirelessly, greatly simplifying the patient’s care.

• In a care home, battery-free printed graphene sensors can be printed on elderly peoples’ clothes. These sensors could detect and collect elderly people’s health conditions and send them back to the monitoring access points when they are interrogated, enabling remote healthcare and improving quality of life.

Existing materials used in wearable devices are either too expensive, such as silver nanoparticles, or not adequately conductive to have an effect, such as conductive polymers.

Graphene, the world’s thinnest, strongest and most conductive material, is perfect for the wearables market because of its broad range of superlative qualities. Graphene conductive ink can be cheaply mass produced and printed onto various materials, including clothing and paper.

“Sir Kostya Novoselov

To see evidence that cheap, scalable wearable communication devices are on the horizon is excellent news for graphene commercial applications.

Sir Kostya Novoselov (tweet)„

The researchers, led by Dr Zhirun Hu, printed graphene to construct transmission lines and antennas and experimented with these in communication devices, such as mobile and Wifi connectivity.

Using a mannequin, they attached graphene-enabled antennas on each arm. The devices were able to ‘talk’ to each other, effectively creating an on-body communications system.

The results proved that graphene enabled components have the required quality and functionality for wireless wearable devices.

Dr Hu, from the School of Electrical and Electronic Engineering, said: “This is a significant step forward – we can expect to see a truly all graphene enabled wireless wearable communications system in the near future.

“The potential applications for this research are huge – whether it be for health monitoring, mobile communications or applications attached to skin for monitoring or messaging.

“This work demonstrates that this revolutionary scientific material is bringing a real change into our daily lives.”

Co-author Sir Kostya Novoselov, who with his colleague Sir Andre Geim first isolated graphene at the University in 2004, added: “Research into graphene has thrown up significant potential applications, but to see evidence that cheap, scalable wearable communication devices are on the horizon is excellent news for graphene commercial applications.”

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

Highly Flexible and Conductive Printed Graphene for Wireless Wearable Communications Applications by Xianjun Huang, Ting Leng, Mengjian Zhu, Xiao Zhang, JiaCing Chen, KuoHsin Chang, Mohammed Aqeeli, Andre K. Geim, Kostya S. Novoselov, & Zhirun Hu. Scientific Reports 5, Article number: 18298 (2015) doi:10.1038/srep18298 Published online: 17 December 2015

This is an open access paper.

The next and final item concerns supercapacitors for wearable tech, which makes it slightly different from the other items and is why, despite the date, this is the final item. The research comes from Case Western Research University (CWRU; US) according to a Dec. 16, 2015 news item on Nanowerk (Note: A link has been removed),

Wearable power sources for wearable electronics are limited by the size of garments.

With that in mind, researchers at Case Western Reserve University have developed flexible wire-shaped microsupercapacitors that can be woven into a jacket, shirt or dress (Energy Storage Materials, “Flexible and wearable wire-shaped microsupercapacitors based on highly aligned titania and carbon nanotubes”).

A Dec. 16, 2015 CWRU news release (on EurekAlert), which originated the news item, provides more detail about a device that would make wearable tech more wearable (after all, you don’t want to recharge your clothes the same way you do your phone and other mobile devices),

By their design or by connecting the capacitors in series or parallel, the devices can be tailored to match the charge storage and delivery needs of electronics donned.

While there’s been progress in development of those electronics–body cameras, smart glasses, sensors that monitor health, activity trackers and more–one challenge remaining is providing less obtrusive and cumbersome power sources.

“The area of clothing is fixed, so to generate the power density needed in a small area, we grew radially-aligned titanium oxide nanotubes on a titanium wire used as the main electrode,” said Liming Dai, the Kent Hale Smith Professor of Macromolecular Science and Engineering. “By increasing the surface area of the electrode, you increase the capacitance.”

Dai and Tao Chen, a postdoctoral fellow in molecular science and engineering at Case Western Reserve, published their research on the microsupercapacitor in the journal Energy Storage Materials this week. The study builds on earlier carbon-based supercapacitors.

A capacitor is cousin to the battery, but offers the advantage of charging and releasing energy much faster.

How it works

In this new supercapacitor, the modified titanium wire is coated with a solid electrolyte made of polyvinyl alcohol and phosphoric acid. The wire is then wrapped with either yarn or a sheet made of aligned carbon nanotubes, which serves as the second electrode. The titanium oxide nanotubes, which are semiconducting, separate the two active portions of the electrodes, preventing a short circuit.

In testing, capacitance–the capability to store charge–increased from 0.57 to 0.9 to 1.04 milliFarads per micrometer as the strands of carbon nanotube yarn were increased from 1 to 2 to 3.

When wrapped with a sheet of carbon nanotubes, which increases the effective area of electrode, the microsupercapactitor stored 1.84 milliFarads per micrometer. Energy density was 0.16 x 10-3 milliwatt-hours per cubic centimeter and power density .01 milliwatt per cubic centimeter.

Whether wrapped with yarn or a sheet, the microsupercapacitor retained at least 80 percent of its capacitance after 1,000 charge-discharge cycles. To match various specific power needs of wearable devices, the wire-shaped capacitors can be connected in series or parallel to raise voltage or current, the researchers say.

When bent up to 180 degrees hundreds of times, the capacitors showed no loss of performance. Those wrapped in sheets showed more mechanical strength.

“They’re very flexible, so they can be integrated into fabric or textile materials,” Dai said. “They can be a wearable, flexible power source for wearable electronics and also for self-powered biosensors or other biomedical devices, particularly for applications inside the body.” [emphasis mine]

Dai ‘s lab is in the process of weaving the wire-like capacitors into fabric and integrating them with a wearable device.

So one day we may be carrying supercapacitors in our bodies? I’m not sure how I feel about that goal. In any event, here’s a link and a citation for the paper,

Flexible and wearable wire-shaped microsupercapacitors based on highly aligned titania and carbon nanotubes by Tao Chen, Liming Dai. Energy Storage Materials Volume 2, January 2016, Pages 21–26 doi:10.1016/j.ensm.2015.11.004

This paper appears to be open access.