Tag Archives: supercapacitors

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.

Shape memory in a supercapacitor fibre for ‘smart’ textiles (wearable tech: 1 of 3)

Wearable technology seems to be quite trendy for a grouping not usually seen: consumers, fashion designers, medical personnel, manufacturers, and scientists.

The first in this informal series concerns a fibre with memory shape. From a Nov. 19, 2015 news item on Nanowerk (Note: A link has been removed),

Wearing your mobile phone display on your jacket sleeve or an EKG probe in your sports kit are not off in some distant imagined future. Wearable “electronic textiles” are on the way. In the journal Angewandte Chemie (“A Shape-Memory Supercapacitor Fiber”), Chinese researchers have now introduced a new type of fiber-shaped supercapacitor for energy-storage textiles. Thanks to their shape memory, these textiles could potentially adapt to different body types: shapes formed by stretching and bending remain “frozen”, but can be returned to their original form or reshaped as desired.

A Nov. 19, 2015 Wiley Publishers press release, which originated the news item, provides context and detail about the work,

Any electronic components designed to be integrated into textiles must be stretchable and bendable. This is also true of the supercapacitors that are frequently used for data preservation in static storage systems (SRAM). SRAM is a type of storage that holds a small amount of data that is rapidly retrievable. It is often used for caches in processors or local storage on chips in devices whose data must be stored for long periods without a constant power supply. Some time ago, a team headed by Huisheng Peng at Fudan University developed stretchable, pliable fiber-shaped supercapacitors for integration into electronic textiles. Peng and his co-workers have now made further progress: supercapacitor fibers with shape memory.

Any electronic components designed to be integrated into textiles must be stretchable and bendable. This is also true of the supercapacitors that are frequently used for data preservation in static storage systems (SRAM). SRAM is a type of storage that holds a small amount of data that is rapidly retrievable. It is often used for caches in processors or local storage on chips in devices whose data must be stored for long periods without a constant power supply.
Some time ago, a team headed by Huisheng Peng at Fudan University developed stretchable, pliable fiber-shaped supercapacitors for integration into electronic textiles. Peng and his co-workers have now made further progress: supercapacitor fibers with shape memory.

The fibers are made using a core of polyurethane fiber with shape memory. This fiber is wrapped with a thin layer of parallel carbon nanotubes like a sheet of paper. This is followed by a coating of electrolyte gel, a second sheet of carbon nanotubes, and a final layer of electrolyte gel. The two layers of carbon nanotubes act as electrodes for the supercapacitor. Above a certain temperature, the fibers produced in this process can be bent as desired and stretched to twice their original length. The new shape can be “frozen” by cooling. Reheating allows the fibers to return to their original shape and size, after which they can be reshaped again. The electrochemical performance is fully maintained through all shape changes.

Weaving the fibers into tissues results in “smart” textiles that could be tailored to fit the bodies of different people. This could be used to make precisely fitted but reusable electronic monitoring systems for patients in hospitals, for example. The perfect fit should render them both more comfortable and more reliable.

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

A Shape-Memory Supercapacitor Fiber by Jue Deng, Ye Zhang, Yang Zhao, Peining Chen, Dr. Xunliang Cheng, & Prof. Dr. Huisheng Peng. Angewandte Chemie International Edition  DOI: 10.1002/anie.201508293  First published: 3 November 2015

This paper is behind a paywall.

Cellulose nanocrystals and supercapacitors at McMaster University (Canada)

Photos: Xuan Yang and Kevin Yager.

Photos: Xuan Yang and Kevin Yager. Courtesy McMaster University

I love that featherlike structure holding up a tiny block of something while balanced on what appears to be a series of medallions. What it has to do with supercapacitors (energy storage) and cellulose nanocrystals is a mystery but that’s one of the images you’ll find illustrating an Oct. 7, 2015 news item on Nanotechnology Now featuring research at McMaster University,

McMaster Engineering researchers Emily Cranston and Igor Zhitomirsky are turning trees into energy storage devices capable of powering everything from a smart watch to a hybrid car.

The scientists are using cellulose, an organic compound found in plants, bacteria, algae and trees, to build more efficient and longer-lasting energy storage devices or supercapacitors. This development paves the way toward the production of lightweight, flexible, and high-power electronics, such as wearable devices, portable power supplies and hybrid and electric vehicles.

A Sept. 10, 2015 McMaster University news release, which originated the news item, describes the research in more detail,

Cellulose offers the advantages of high strength and flexibility for many advanced applications; of particular interest are nanocellulose-based materials. The work by Cranston, an assistant chemical engineering professor, and Zhitomirsky, a materials science and engineering professor, demonstrates an improved three-dimensional energy storage device constructed by trapping functional nanoparticles within the walls of a nanocellulose foam.

The foam is made in a simplified and fast one-step process. The type of nanocellulose used is called cellulose nanocrystals and looks like uncooked long-grain rice but with nanometer-dimensions. In these new devices, the ‘rice grains’ have been glued together at random points forming a mesh-like structure with lots of open space, hence the extremely lightweight nature of the material. This can be used to produce more sustainable capacitor devices with higher power density and faster charging abilities compared to rechargeable batteries.

Lightweight and high-power density capacitors are of particular interest for the development of hybrid and electric vehicles. The fast-charging devices allow for significant energy saving, because they can accumulate energy during braking and release it during acceleration.

For anyone interested in a more detailed description of supercapacitors, there’s my favourite one which involves Captain America’s shield along with some serious science in my April 28, 2014 posting.

Getting back to the research at McMaster, here’s a link to and a citation for the paper,

Cellulose Nanocrystal Aerogels as Universal 3D Lightweight Substrates for Supercapacitor Materials by Xuan Yang, Kaiyuan Shi, Igor Zhitomirsky, and Emily D. Cranston. Advanced Materials DOI: 10.1002/adma.201502284View/save citation First published online 2 September 2015

This paper is behind a paywall.

One final bit, cellulose nanocrystals (CNC) are sometimes referred to as nanocrystalline cellulose (NCC).

Wearable technologies, electric vehicles and conundrums at Wollongong University (Australia)

A July 25, 2015 news item on Nanowerk announces research at the University of Wollongong designed to address a conundrum (Note: A link has been removed),

UOW’s Institute for Superconducting and Electronic Materials (ISEM) has successfully pioneered a way to construct a flexible, foldable and lightweight energy storage device that provides the building blocks for next-generation batteries needed to power wearable electronics and implantable medical devices (ACS Central Science, “Self-Assembled Multifunctional Hybrids: Toward Developing High-Performance Graphene-Based Architectures for Energy Storage Devices”).

The conundrum researchers have faced in developing miniature energy storage devices, such as batteries and supercapacitors, has been figuring out how to increase the surface area of the device, to store more charge, without making it larger.

A July 27, 2015 University of Wollongong news release by Grant Reynolds, which originated the news item, describes the research in more detail,

To solve this problem, a team of PhD students, led by Dr Konstantin Konstantinov under the patronage of ISEM Director Professor Shi Xue Dou and with the support of Professor Hua Kun Liu, the head of ISEM Energy Storage Division, have developed a three-dimensional structure using a flat-pack self-assembly of three components: graphene, a conductive polymer and carbon nanotubes, which are atom-thick lattice-like networks of carbon formed into cylinders.

Graphene, made from single atom-thick layers of graphite, was a suitable candidate due its electronic performance and mechanical strength.

“We knew in theory that if you can make a sort of carbon skeleton you have a greater surface area and greater surface area means more charge,” Dr Konstantinov said. “If we could efficiently separate the layers of carbon we could then use both surfaces of each layer for charge accumulation. The problem we faced was that fabricating these 3D shapes in practice, not just theory, is a challenging, if not impossible task.”

The solution was to flat-pack the components by building the 3D shape layer-by-layer, much like a miniature exercise in cake decoration. The graphene in liquid form was mixed with the conductive polymer and reduced to solid and the carbon nanotubes carefully inserted between the graphene layers to form a self-assembled flat-packed, wafer-thin supercapacitor material.

“The real challenge was how to assemble these three components into a single structure with the best use of the space available,” PhD student Monirul Islam said. “Getting the proportions or ratios of the components appropriately in order to obtain a composite material with maximum energy storage performance was another challenge.”

Wrong proportions of either ingredient result in a lumpy mess, or a 3D shape that isn’t strong enough to retain the needed flexibility as well as the charge storage ability. There’s also elegance in the simplicity of the team’s design: the researchers dispersed the components in liquid crystalline, which enabled natural chemical interactions to prevent the graphene layers clumping together.

The result was a 3D shape with, thanks to the carbon nanotubes, a massive surface area, excellent charge capacity that is also foldable. It can also be cheaply and easily fabricated without the need for expensive vacuum chambers or sophisticated equipment.

“Our graphene-based flexible composite is highly conductive, lightweight, is able to fold like a roll or stack like a paper in electronic devices to store a huge amount of charge,” Monirul said. “This material can store charge in a second and deliver the charge in superfast speed and will be more lightweight than traditional batteries used in present day’s electronics.”

The ISEM study has been financially supported by the Automotive Australia 2020 CRC as part of its research into electric vehicles. ISEM is the program leader for electrification and plays crucial role for design of next generation electric vehicles A key to unlocking the electric vehicle’s capability is a lightweight and powerful battery pack.

“Our simple fabrication method of eco-friendly materials with increased performance has great potential to be scaled up for use supercapacitor and battery technology. Our next step is to use this material to fabricate flexible wearable supercapacitors with high power density and energy density as well as large scale supercapacitors for electric vehicles.”

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

Self-Assembled Multifunctional Hybrids: Toward Developing High-Performance Graphene-Based Architectures for Energy Storage Devices by Md. Monirul Islam, Seyed Hamed Aboutalebi, Dean Cardillo, Hua Kun Liu, Konstantin Konstantinov, and Shi Xue Dou. ACS Cent. Sci., 2015, 1 (4), pp 206–216 DOI: 10.1021/acscentsci.5b00189 Publication Date (Web): July 2, 2015

Copyright © 2015 American Chemical Society

This appears to be an open access paper.