Tag Archives: wearable electronics

The new knitting: electronics and batteries

Researchers from China have developed a new type of yarn for flexible electronics. A March 28, 2018 news item on Nanowerk announces the work, (Note: A link has been removed),

When someone thinks about knitting, they usually don’t conjure up an image of sweaters and scarves made of yarn that can power watches and lights. But that’s just what one group is reporting in ACS Nano (“Waterproof and Tailorable Elastic Rechargeable Yarn Zinc Ion Batteries by a Cross-Linked Polyacrylamide Electrolyte”). They have developed a rechargeable yarn battery that is waterproof and flexible. It also can be cut into pieces and still work.

A March 28, 2018 2018 American Chemical Society (ACS) news release (also on EurekAlert), which originated the news item, expands on the theme (Note: Links have been removed),

Most people are familiar with smartwatches, but for wearable electronics to progress, scientists will need to overcome the challenge of creating a device that is deformable, durable, versatile and wearable while still holding and maintaining a charge. One dimensional fiber or yarn has shown promise, since it is tiny, flexible and lightweight. Previous studies have had some success combining one-dimensional fibers with flexible Zn-MnO2 batteries, but many of these lose charge capacity and are not rechargeable. So, Chunyi Zhi and colleagues wanted to develop a rechargeable yarn zinc-ion battery that would maintain its charge capacity, while being waterproof and flexible.

The group twisted carbon nanotube fibers into a yarn, then coated one piece of yarn with zinc to form an anode, and another with magnesium oxide to form a cathode. These two pieces were then twisted like a double helix and coated with a polyacrylamide electrolyte and encased in silicone. Upon testing, the yarn zinc-ion battery was stable, had a high charge capacity and was rechargeable and waterproof. In addition, the material could be knitted and stretched. It also could be cut into several pieces, each of which could power a watch. In a proof-of-concept demonstration, eight pieces of the cut yarn battery were woven into a long piece that could power a belt containing 100 light emitting diodes (known as LEDs) and an electroluminescent panel.

The authors acknowledge funding from the National Natural Science Foundation of China and the Research Grants Council of Hong Kong Joint Research Scheme, City University of Hong Kong and the Sichuan Provincial Department of Science & Technology.

Here’s an image the researchers have used to illustrate their work,


Courtesy: American Chemical Society

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

Waterproof and Tailorable Elastic Rechargeable Yarn Zinc Ion Batteries by a Cross-Linked Polyacrylamide Electrolyte by Hongfei Li, Zhuoxin Liu, Guojin Liang, Yang Huang, Yan Huang, Minshen Zhu, Zengxia Pe, Qi Xue, Zijie Tang, Yukun Wang, Baohua Li, and Chunyi Zhi. ACS Nano, Article ASAP DOI: 10.1021/acsnano.7b09003 Publication Date (Web): March 28, 2018

Copyright © 2018 American Chemical Society

This paper is behind a paywall.

Do you want that coffee with some graphene on toast?

These scientists are excited:

For those who prefer text, here’s the Rice University Feb. 13, 2018 news release (received via email and available online here and on EurekAlert here) Note: Links have been removed),

Rice University scientists who introduced laser-induced graphene (LIG) have enhanced their technique to produce what may become a new class of edible electronics.

The Rice lab of chemist James Tour, which once turned Girl Scout cookies into graphene, is investigating ways to write graphene patterns onto food and other materials to quickly embed conductive identification tags and sensors into the products themselves.

“This is not ink,” Tour said. “This is taking the material itself and converting it into graphene.”

The process is an extension of the Tour lab’s contention that anything with the proper carbon content can be turned into graphene. In recent years, the lab has developed and expanded upon its method to make graphene foam by using a commercial laser to transform the top layer of an inexpensive polymer film.

The foam consists of microscopic, cross-linked flakes of graphene, the two-dimensional form of carbon. LIG can be written into target materials in patterns and used as a supercapacitor, an electrocatalyst for fuel cells, radio-frequency identification (RFID) antennas and biological sensors, among other potential applications.

The new work reported in the American Chemical Society journal ACS Nano demonstrated that laser-induced graphene can be burned into paper, cardboard, cloth, coal and certain foods, even toast.

“Very often, we don’t see the advantage of something until we make it available,” Tour said. “Perhaps all food will have a tiny RFID tag that gives you information about where it’s been, how long it’s been stored, its country and city of origin and the path it took to get to your table.”

He said LIG tags could also be sensors that detect E. coli or other microorganisms on food. “They could light up and give you a signal that you don’t want to eat this,” Tour said. “All that could be placed not on a separate tag on the food, but on the food itself.”

Multiple laser passes with a defocused beam allowed the researchers to write LIG patterns into cloth, paper, potatoes, coconut shells and cork, as well as toast. (The bread is toasted first to “carbonize” the surface.) The process happens in air at ambient temperatures.

“In some cases, multiple lasing creates a two-step reaction,” Tour said. “First, the laser photothermally converts the target surface into amorphous carbon. Then on subsequent passes of the laser, the selective absorption of infrared light turns the amorphous carbon into LIG. We discovered that the wavelength clearly matters.”

The researchers turned to multiple lasing and defocusing when they discovered that simply turning up the laser’s power didn’t make better graphene on a coconut or other organic materials. But adjusting the process allowed them to make a micro supercapacitor in the shape of a Rice “R” on their twice-lased coconut skin.

Defocusing the laser sped the process for many materials as the wider beam allowed each spot on a target to be lased many times in a single raster scan. That also allowed for fine control over the product, Tour said. Defocusing allowed them to turn previously unsuitable polyetherimide into LIG.

“We also found we could take bread or paper or cloth and add fire retardant to them to promote the formation of amorphous carbon,” said Rice graduate student Yieu Chyan, co-lead author of the paper. “Now we’re able to take all these materials and convert them directly in air without requiring a controlled atmosphere box or more complicated methods.”

The common element of all the targeted materials appears to be lignin, Tour said. An earlier study relied on lignin, a complex organic polymer that forms rigid cell walls, as a carbon precursor to burn LIG in oven-dried wood. Cork, coconut shells and potato skins have even higher lignin content, which made it easier to convert them to graphene.

Tour said flexible, wearable electronics may be an early market for the technique. “This has applications to put conductive traces on clothing, whether you want to heat the clothing or add a sensor or conductive pattern,” he said.

Rice alumnus Ruquan Ye is co-lead author of the study. Co-authors are Rice graduate student Yilun Li and postdoctoral fellow Swatantra Pratap Singh and Professor Christopher Arnusch of Ben-Gurion University of the Negev, Israel. Tour is the T.T. and W.F. Chao Chair in Chemistry as well as a professor of computer science and of materials science and nanoengineering at Rice.

The Air Force Office of Scientific Research supported the research.

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

Laser-Induced Graphene by Multiple Lasing: Toward Electronics on Cloth, Paper, and Food by Yieu Chyan, Ruquan Ye†, Yilun Li, Swatantra Pratap Singh, Christopher J. Arnusch, and James M. Tour. ACS Nano DOI: 10.1021/acsnano.7b08539 Publication Date (Web): February 13, 2018

Copyright © 2018 American Chemical Society

This paper is behind a paywall.

h/t Feb. 13, 2018 news item on Nanowerk

Liquid circuitry, shape-shifting fluids and more

I’d have to see it to believe it but researchers at the US Dept. of Energy (DOE) Lawrence Berkeley National Laboratory (LBNL) have developed a new kind of ‘bijel’ which would allow for some pretty nifty robotics. From a Sept. 25, 2017 news item on ScienceDaily,

A new two-dimensional film, made of polymers and nanoparticles and developed by researchers at the Department of Energy’s Lawrence Berkeley National Laboratory (Berkeley Lab), can direct two different non-mixing liquids into a variety of exotic architectures. This finding could lead to soft robotics, liquid circuitry, shape-shifting fluids, and a host of new materials that use soft, rather than solid, substances.

The study, reported today in the journal Nature Nanotechnology, presents the newest entry in a class of substances known as bicontinuous jammed emulsion gels, or bijels, which hold promise as a malleable liquid that can support catalytic reactions, electrical conductivity, and energy conversion.

A Sept. 25, 2017 LBNL news release (also on EurekAlert), which originated the news item, expands on the theme,

Bijels are typically made of immiscible, or non-mixing, liquids. People who shake their bottle of vinaigrette before pouring the dressing on their salad are familiar with such liquids. As soon as the shaking stops, the liquids start to separate again, with the lower density liquid – often oil – rising to the top.

Trapping, or jamming, particles where these immiscible liquids meet can prevent the liquids from completely separating, stabilizing the substance into a bijel. What makes bijels remarkable is that, rather than just making the spherical droplets that we normally see when we try to mix oil and water, the particles at the interface shape the liquids into complex networks of interconnected fluid channels.

Bijels are notoriously difficult to make, however, involving exact temperatures at precisely timed stages. In addition, the liquid channels are normally more than 5 micrometers across, making them too large to be useful in energy conversion and catalysis.

“Bijels have long been of interest as next-generation materials for energy applications and chemical synthesis,” said study lead author Caili Huang. “The problem has been making enough of them, and with features of the right size. In this work, we crack that problem.”

Huang started the work as a graduate student with Thomas Russell, the study’s principal investigator, at Berkeley Lab’s Materials Sciences Division, and he continued the project as a postdoctoral researcher at DOE’s Oak Ridge National Laboratory.

Creating a new bijel recipe

The method described in this new study simplifies the bijel process by first using specially coated particles about 10-20 nanometers in diameter. The smaller-sized particles line the liquid interfaces much more quickly than the ones used in traditional bijels, making the smaller channels that are highly valued for applications.

Illustration shows key stages of bijel formation. Clockwise from top left, two non-mixing liquids are shown. Ligands (shown in yellow) with amine groups are dispersed throughout the oil or solvent, and nanoparticles coated with carboxylic acids (shown as blue dots) are scattered in the water. With vigorous shaking, the nanoparticles and ligands form a “supersoap” that gets trapped at the interface of the two liquids. The bottom panel is a magnified view of the jammed nanoparticle supersoap. (Credit: Caili Huang/ORNL)

“We’ve basically taken liquids like oil and water and given them a structure, and it’s a structure that can be changed,” said Russell, a visiting faculty scientist at Berkeley Lab. “If the nanoparticles are responsive to electrical, magnetic, or mechanical stimuli, the bijels can become reconfigurable and re-shaped on demand by an external field.”

The researchers were able to prepare new bijels from a variety of common organic, water-insoluble solvents, such as toluene, that had ligands dissolved in it, and deionized water, which contained the nanoparticles. To ensure thorough mixing of the liquids, they subjected the emulsion to a vortex spinning at 3,200 revolutions per minute.

“This extreme shaking creates a whole bunch of new places where these particles and polymers can meet each other,” said study co-author Joe Forth, a postdoctoral fellow at Berkeley Lab’s Materials Sciences Division. “You’re synthesizing a lot of this material, which is in effect a thin, 2-D coating of the liquid surfaces in the system.”

The liquids remained a bijel even after one week, a sign of the system’s stability.

Russell, who is also a professor of polymer science and engineering at the University of Massachusetts-Amherst, added that these shape-shifting characteristics would be valuable in microreactors, microfluidic devices, and soft actuators.

Nanoparticle supersoap

Nanoparticles had not been seriously considered in bijels before because their small size made them hard to trap in the liquid interface. To resolve that problem, the researchers coated nano-sized particles with carboxylic acids and put them in water. They then took polymers with an added amine group – a derivative of ammonia – and dissolved them in the toluene.

At left is a vial of bijel stabilized with nanoparticle surfactants. On the right is the same vial after a week of inversion, showing that the nanoparticle kept the liquids from moving. (Credit: Caili Huang/ORNL)

This configuration took advantage of the amine group’s affinity to water, a characteristic that is comparable to surfactants, like soap. Their nanoparticle “supersoap” was designed so that the nanoparticles join ligands, forming an octopus-like shape with a polar head and nonpolar legs that get jammed at the interface, the researchers said.

“Bijels are really a new material, and also excitingly weird in that they are kinetically arrested in these unusual configurations,” said study co-author Brett Helms, a staff scientist at Berkeley Lab’s Molecular Foundry. “The discovery that you can make these bijels with simple ingredients is a surprise. We all have access to oils and water and nanocrystals, allowing broad tunability in bijel properties. This platform also allows us to experiment with new ways to control their shape and function since they are both responsive and reconfigurable.”

The nanoparticles were made of silica, but the researchers noted that in previous studies they used graphene and carbon nanotubes to form nanoparticle surfactants.

“The key is that the nanoparticles can be made of many materials,” said Russell.  “The most important thing is what’s on the surface.”

This is an animation of the bijel

3-D rendering of the nanoparticle bijel taken by confocal microscope. (Credit: Caili Huang/ORNL [Oak Ridge National Laboratory] and Joe Forth/Berkeley Lab)

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

Bicontinuous structured liquids with sub-micrometre domains using nanoparticle surfactants by Caili Huang, Joe Forth, Weiyu Wang, Kunlun Hong, Gregory S. Smith, Brett A. Helms & Thomas P. Russell. Nature Nanotechnology (2017) doi:10.1038/nnano.2017.182 25 September 2017

This paper is behind a paywall.

A flexible, organic battery from Northern Ireland

A team from Northern Ireland seems to have made a splash in the race to develop a flexible, environmentally friendly battery. From a Sept. 13, 2017 news item on phys.org,

Experts at Queen’s University Belfast have designed a flexible and organic alternative to the rigid batteries that power up medical implants.

Currently, devices such as pacemakers and defibrillators are fitted with rigid and metal based batteries, which can cause patient discomfort.

Dr Geetha Srinivasan and a team of young researchers from Queen’s University Ionic Liquid Laboratories (QUILL) Research Centre, have now developed a flexible supercapacitor with a longer cycle life, which could power body sensors.

Courtesy: Queen’s University Belfast

A Sept. 13, 2017 Queen’s University Belfast press release (also on EurekAlert), which originated the news item, delves further,

The flexible device is made up of non-flammable electrolytes and organic composites, which are safe to the human body. It can also be easily decomposed without incurring the major costs associated with recycling or disposing off metal based batteries.

The findings, which have been published in Energy Technology and Green Chemistry, show that the device could be manufactured using readily available natural feedstock, rather than sophisticated and expensive metals or semiconductors.

Dr Srinivasan explains: “In modern society, we all increasingly depend on portable electronics such as smartphones and laptops in our everyday lives and this trend has spread to other important areas such as healthcare devices.

“In medical devices such as pacemakers and defibrillators there are two implants, one which is fitted in the heart and another which holds the metal based, rigid batteries – this is implanted under the skin.

“The implant under the skin is wired to the device and can cause patients discomfort as it is rubs against the skin. For this reason batteries need to be compatible to the human body and ideally we would like them to be flexible so that they can adapt to body shapes.”

Dr Srinivasan adds: “At Queen’s University Belfast we have designed a flexible energy storage device, which consists of conducting polymer – biopolymer composites as durable electrodes and ionic liquids as safer electrolytes.

“The device we have created has a longer life-cycle, is non-flammable, has no leakage issues and above all, it is more flexible for placing within the body.”

Environmentally friendly

While the findings show that there are many advantages in the medical world, the organic storage device could also provide solutions in wearable electronics and portable electronic devices, making these more flexible.

Ms Marta Lorenzo, PhD researcher on the project at Queen’s University Belfast, commented: “Although this research could be a potential solution to a global problem, the actual supercapacitor assembly is a straightforward process.”

Dr Srinivasan says: “There is also opportunity to fabricate task-specific supercapacitors. This means that their properties can be tuned and also manufactured using environmentally friendly methods, which is important if they are to be produced on a large scale, for example in powering portable personal electronic devices.”

Here are links and citations to the two papers mentioned in the press release,

Durable Flexible Supercapacitors Utilizing the Multifunctional Role of Ionic Liquids by Marta Lorenzo and Dr Geetha Srinivasan. Energy Technology. DOI: 10.1002/ente.201700407 First published: 23 August 2017

Intrinsically flexible electronic materials for smart device applications by Marta Lorenzo, Biyun Zhu, and Geetha Srinivasan. Green Chem., 2016,18, 3513-3517 DOI: 10.1039/C6GC00826G First published on 20 May 2016

The first paper is open access and the second paper is behind a paywall.

Vampire nanogenerators: 2017

Researchers have been working on ways to harvest energy from bloodstreams. I last wrote about this type of research in an April 3, 2009 posting about ‘vampire batteries ‘(for use in pacemakers). The latest work according to a Sept. 8, 2017 news item on Nanowerk comes from China,

Men build dams and huge turbines to turn the energy of waterfalls and tides into electricity. To produce hydropower on a much smaller scale, Chinese scientists have now developed a lightweight power generator based on carbon nanotube fibers suitable to convert even the energy of flowing blood in blood vessels into electricity. They describe their innovation in the journal Angewandte Chemie (“A One-Dimensional Fluidic Nanogenerator with a High Power Conversion Efficiency”)

A Sept. 8, 2017 Wiley Publishing news release (also on EurekAlert), which originated the news item, expands on the theme,

For thousands of years, people have used the energy of flowing or falling water for their purposes, first to power mechanical engines such as watermills, then to generate electricity by exploiting height differences in the landscape or sea tides. Using naturally flowing water as a sustainable power source has the advantage that there are (almost) no dependencies on weather or daylight. Even flexible, minute power generators that make use of the flow of biological fluids are conceivable. How such a system could work is explained by a research team from Fudan University in Shanghai, China. Huisheng Peng and his co-workers have developed a fiber with a thickness of less than a millimeter that generates electrical power when surrounded by flowing saline solution—in a thin tube or even in a blood vessel.

The construction principle of the fiber is quite simple. An ordered array of carbon nanotubes was continuously wrapped around a polymeric core. Carbon nanotubes are well known to be electroactive and mechanically stable; they can be spun and aligned in sheets. In the as-prepared electroactive threads, the carbon nanotube sheets coated the fiber core with a thickness of less than half a micron. For power generation, the thread or “fiber-shaped fluidic nanogenerator” (FFNG), as the authors call it, was connected to electrodes and immersed into flowing water or simply repeatedly dipped into a saline solution. “The electricity was derived from the relative movement between the FFNG and the solution,” the scientists explained. According to the theory, an electrical double layer is created around the fiber, and then the flowing solution distorts the symmetrical charge distribution, generating an electricity gradient along the long axis.

The power output efficiency of this system was high. Compared with other types of miniature energy-harvesting devices, the FFNG was reported to show a superior power conversion efficiency of more than 20%. Other advantages are elasticity, tunability, lightweight, and one-dimensionality, thus offering prospects of exciting technological applications. The FFNG can be made stretchable just by spinning the sheets around an elastic fiber substrate. If woven into fabrics, wearable electronics become thus a very interesting option for FFNG application. Another exciting application is the harvesting of electrical energy from the bloodstream for medical applications. First tests with frog nerves proved to be successful.

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

A One-Dimensional Fluidic Nanogenerator with a High Power Conversion Efficiency by Yifan Xu, Dr. Peining Chen, Jing Zhang, Songlin Xie, Dr. Fang Wan, Jue Deng, Dr. Xunliang Cheng, Yajie Hu, Meng Liao, Dr. Bingjie Wang, Dr. Xuemei Sun, and Prof. Dr. Huisheng Peng. Angewandte Chemie International Edition DOI: 10.1002/anie.201706620 Version of Record online: 7 SEP 2017

© 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

This paper is behind a paywall.

Making wearable technology more comfortable—with green tea for squishy supercapacitor

Researchers in India have designed a new type of wearable technology based on green team. From a Feb. 15, 2017 news item on plys.org,

Wearable electronics are here—the most prominent versions are sold in the form of watches or sports bands. But soon, more comfortable products could become available in softer materials made in part with an unexpected ingredient: green tea. Researchers report in ACS’ The Journal of Physical Chemistry C a new flexible and compact rechargeable energy storage device for wearable electronics that is infused with green tea polyphenols.

A Feb. 15, 2017 American Chemical Society (ACS) news release, (also on EurekAlert), which originated the news item, provides a little more information about the squishy supercapacitors (Note: Links have been removed),

Powering soft wearable electronics with a long-lasting source of energy remains a big challenge. Supercapacitors could potentially fill this role — they meet the power requirements, and can rapidly charge and discharge many times. But most supercapacitors are rigid, and the compressible supercapacitors developed so far have run into roadblocks. They have been made with carbon-coated polymer sponges, but the coating material tends to bunch up and compromise performance. Guruswamy Kumaraswamy, Kothandam Krishnamoorthy and colleagues wanted to take a different approach.

The researchers prepared polymer gels in green tea extract, which infuses the gel with polyphenols. The polyphenols converted a silver nitrate solution into a uniform coating of silver nanoparticles. Thin layers of conducting gold and poly(3,4-ethylenedioxythiophene) were then applied. And the resulting supercapacitor demonstrated power and energy densities of 2,715 watts per kilogram and 22 watt-hours per kilogram — enough to operate a heart rate monitor, LEDs or a Bluetooth module. The researchers tested the device’s durability and found that it performed well even after being compressed more than 100 times.

The authors acknowledge funding from the University Grants Commission of India, the Council of Scientific and Industrial Research (India) and the Board of Research in Nuclear Sciences (India).

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

Elastic Compressible Energy Storage Devices from Ice Templated Polymer Gels treated with Polyphenols by Chayanika Das, Soumyajyoti Chatterjee, Guruswamy Kumaraswamy, and Kothandam Krishnamoorthy. J. Phys. Chem. C, Article ASAP DOI: 10.1021/acs.jpcc.6b12822 Publication Date (Web): January 26, 2017

Copyright © 2017 American Chemical Society

This paper is behind a paywall.

High speed fabrication of adhesive and flexible electronics

For a university that celebrated its opening in Sept. 2009 (mentioned in my Sept. 24, 2009 posting; scroll down about 40% of the way; look for a reference to the House of Wisdom), the King Abdullah University of Science and Technology (KAUST) has made some impressive announcements including this one in a Jan. 3, 2017 press release on EurekAlert,

The healthcare industry forecasts that our wellbeing in the future will be monitored by wearable wirelessly networked sensors. Manufacturing such devices could become much easier with decal electronics. A KAUST-developed process prints these high-performance silicon-based computers on to soft, sticker-like surfaces that can be attached anywhere1.

Fitting electronics on to the asymmetric contours of human bodies demands a re-think of traditional computer fabrications. One approach is to print circuit patterns on to materials such as polymers or cellulose using liquid ink made from conductive molecules. This technique enables high-speed roll-to-roll assembly of devices and packaging at low costs.

Flexible printed circuits, however, require conventional silicon components to handle applications such as digitizing analog signals. Such rigid modules can create uncomfortable hot spots on the body and increase device weight.

For the past four years, Muhammad Hussain and his team from the KAUST Computer, Electrical and Mathematical Science and Engineering Division have investigated ways to improve the flexibility of silicon materials while retaining their performance.

“We are trying to integrate all device components–sensors, data management electronics, battery, antenna–into a completely compliant system,” explained Hussain. “However, packaging these discrete modules on to soft substrates is extremely difficult.”

Searching for potential electronic skin applications, the researchers developed a sensor containing narrow strips of aluminum foil that changes conductivity at different bending states.

The devices, which could monitor a patient’s breathing patterns or activity levels, feature high-mobility zinc oxide nanotransistors on silicon wafers thinned down lithographically to microscale dimensions for maximum flexibility. Using three-dimensional (3-D) printing techniques, the team encapsulated the silicon chips and foils into a polymer film backed by an adhesive layer.

Hussain and his colleagues found a way to make the e-sticker sensors work in multiple applications. They used inkjet printing to write conductive wiring patterns on to different surfaces, such as paper or clothing. Custom-printed decals were then attached or re-adhered to each location.

“You can place a pressure-sensing decal on a tire to monitor it while driving and then peel it off and place it on your mattress to learn your sleeping patterns,” said Galo Torres Sevilla, first author of the findings and a KAUST Ph.D. graduate.

The robust performance and high-throughput manufacturing potential of decal electronics could launch a number of innovative sensor deployments, noted Hussain.

“I believe that electronics have to be democratized–simple to learn and easy to implement. Electronic decals are a right step in that direction,” Hussain said.

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

Decal Electronics: Printable Packaged with 3D Printing High-Performance Flexible CMOS Electronic Systems by Galo A. Torres Sevilla, Marlon D. Cordero, Joanna M. Nassar, Amir N. Hanna, Arwa T. Kutbee, Arpys Arevalo, and Muhammad M. Hussain. Advanced Materials Technologies DOI: 10.1002/admt.201600175 Version of Record online: 13 OCT 2016

© 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

This paper is behind a paywall.

Graphene and silly putty combined to create ultra sensitive sensors

One of my favourite kinds of science story is the one where scientists turn to a children’s toy for their research. In this case, it’s silly putty. Before launching into the science part of this story, here’s more about silly putty from its Wikipedia entry (Note: A ll links have been removed),

During World War II, Japan invaded rubber-producing countries as they expanded their sphere of influence in the Pacific Rim. Rubber was vital for the production of rafts, tires, vehicle and aircraft parts, gas masks, and boots. In the U.S., all rubber products were rationed; citizens were encouraged to make their rubber products last until the end of the war and to donate spare tires, boots, and coats. Meanwhile, the government funded research into synthetic rubber compounds to attempt to solve this shortage.[10]

Credit for the invention of Silly Putty is disputed[11] and has been attributed variously to Earl Warrick,[12] of the then newly formed Dow Corning; Harvey Chin; and James Wright, a Scottish-born inventor working for General Electric in New Haven, Connecticut.[13] Throughout his life, Warrick insisted that he and his colleague, Rob Roy McGregor, received the patent for Silly Putty before Wright did; but Crayola’s history of Silly Putty states that Wright first invented it in 1943.[10][14][15] Both researchers independently discovered that reacting boric acid with silicone oil would produce a gooey, bouncy material with several unique properties. The non-toxic putty would bounce when dropped, could stretch farther than regular rubber, would not go moldy, and had a very high melting temperature. However, the substance did not have all the properties needed to replace rubber.[1]

In 1949 toy store owner Ruth Fallgatter came across the putty. She contacted marketing consultant Peter C.L. Hodgson (1912-1976).[16] The two decided to market the bouncing putty by selling it in a clear case. Although it sold well, Fallgatter did not pursue it further. However, Hodgson saw its potential.[1][3]

Already US$12,000 in debt, Hodgson borrowed US$147 to buy a batch of the putty to pack 1 oz (28 g) portions into plastic eggs for US$1, calling it Silly Putty. Initially, sales were poor, but after a New Yorker article mentioned it, Hodgson sold over 250,000 eggs of silly putty in three days.[3] However, Hodgson was almost put out of business in 1951 by the Korean War. Silicone, the main ingredient in silly putty, was put on ration, harming his business. A year later the restriction on silicone was lifted and the production of Silly Putty resumed.[17][9] Initially, it was primarily targeted towards adults. However, by 1955 the majority of its customers were aged 6 to 12. In 1957, Hodgson produced the first televised commercial for Silly Putty, which aired during the Howdy Doody Show.[18]

In 1961 Silly Putty went worldwide, becoming a hit in the Soviet Union and Europe. In 1968 it was taken into lunar orbit by the Apollo 8 astronauts.[17]

Peter Hodgson died in 1976. A year later, Binney & Smith, the makers of Crayola products, acquired the rights to Silly Putty. As of 2005, annual Silly Putty sales exceeded six million eggs.[19]

Silly Putty was inducted into the National Toy Hall of Fame on May 28, 2001. [20]

I had no idea silly putty had its origins in World War II era research. At any rate, it’s made its way back to the research lab to be united with graphene according to a Dec. 8, 2016 news item  on Nanowerk,

Researchers in AMBER, the Science Foundation Ireland-funded materials science research centre, hosted in Trinity College Dublin, have used graphene to make the novelty children’s material silly putty® (polysilicone) conduct electricity, creating extremely sensitive sensors. This world first research, led by Professor Jonathan Coleman from TCD and in collaboration with Prof Robert Young of the University of Manchester, potentially offers exciting possibilities for applications in new, inexpensive devices and diagnostics in medicine and other sectors.

A Dec. 9, 2016 Trinity College Dublin press release (also on EurekAlert), which originated the news item, describes their ‘G-putty’ in more detail,

Prof Coleman, Investigator in AMBER and Trinity’s School of Physics along with postdoctoral researcher Conor Boland, discovered that the electrical resistance of putty infused with graphene (“G-putty”) was extremely sensitive to the slightest deformation or impact. They mounted the G-putty onto the chest and neck of human subjects and used it to measure breathing, pulse and even blood pressure. It showed unprecedented sensitivity as a sensor for strain and pressure, hundreds of times more sensitive than normal sensors. The G-putty also works as a very sensitive impact sensor, able to detect the footsteps of small spiders. It is believed that this material will find applications in a range of medical devices.

Prof Coleman said, “What we are excited about is the unexpected behaviour we found when we added graphene to the polymer, a cross-linked polysilicone. This material as well known as the children’s toy silly putty. It is different from familiar materials in that it flows like a viscous liquid when deformed slowly but bounces like an elastic solid when thrown against a surface. When we added the graphene to the silly putty, it caused it to conduct electricity, but in a very unusual way. The electrical resistance of the G-putty was very sensitive to deformation with the resistance increasing sharply on even the slightest strain or impact. Unusually, the resistance slowly returned close to its original value as the putty self-healed over time.”

He continued, “While a common application has been to add graphene to plastics in order to improve the electrical, mechanical, thermal or barrier properties, the resultant composites have generally performed as expected without any great surprises. The behaviour we found with G-putty has not been found in any other composite material. This unique discovery will open up major possibilities in sensor manufacturing worldwide.”

Dexter Johnson in a Dec. 14, 2016 posting on his Nanoclast blog (on the IEEE [Institute of Electrical and Electronics Engineers]) puts this research into context,

For all the talk and research that has gone into exploiting graphene’s pliant properties for use in wearable and flexible electronics, most of the polymer composites it has been mixed with to date have been on the hard and inflexible side.

It took a team of researchers in Ireland to combine graphene with the children’s toy Silly Putty to set the nanomaterial community ablaze with excitement. The combination makes a new composite that promises to make a super-sensitive strain sensor with potential medical diagnostic applications.

“Ablaze with excitement,” eh? As Dexter rarely slips into hyperbole, this must be a big deal.

The researchers have made this video available,

For the very interested, here’s a link to and a citation for the paper,

Sensitive electromechanical sensors using viscoelastic graphene-polymer nanocomposites by Conor S. Boland, Umar Khan, Gavin Ryan, Sebastian Barwich, Romina Charifou, Andrew Harvey, Claudia Backes, Zheling Li, Mauro S. Ferreira, Matthias E. Möbius, Robert J. Young, Jonathan N. Coleman. Science  09 Dec 2016: Vol. 354, Issue 6317, pp. 1257-1260 DOI: 10.1126/science.aag2879

This paper is behind a paywall.

Self-healing lithium-ion batteries for textiles

It’s easy to forget how hard we are on our textiles. We rip them, step on them, agitate them in water, splatter them with mud, and more. So, what happens when we integrate batteries and electronics into them? An Oct. 20, 2016 news item on phys.org describes one of the latest ‘textile batter technologies’,

Electronics that can be embedded in clothing are a growing trend. However, power sources remain a problem. In the journal Angewandte Chemie, scientists have now introduced thin, flexible, lithium ion batteries with self-healing properties that can be safely worn on the body. Even after completely breaking apart, the battery can grow back together without significant impact on its electrochemical properties.


© Wiley-VCH

An Oct. 20, 2016 Wiley Angewandte Chemie International Edition press release (also on EurekAlert), which originated the news item, describes some of the problems associated with lithium-ion batteries and this new technology designed to address them,

Existing lithium ion batteries for wearable electronics can be bent and rolled up without any problems, but can break when they are twisted too far or accidentally stepped on—which can happen often when being worn. This damage not only causes the battery to fail, it can also cause a safety problem: Flammable, toxic, or corrosive gases or liquids may leak out.

A team led by Yonggang Wang and Huisheng Peng has now developed a new family of lithium ion batteries that can overcome such accidents thanks to their amazing self-healing powers. In order for a complicated object like a battery to be made self-healing, all of its individual components must also be self-healing. The scientists from Fudan University (Shanghai, China), the Samsung Advanced Institute of Technology (South Korea), and the Samsung R&D Institute China, have now been able to accomplish this.

The electrodes in these batteries consist of layers of parallel carbon nanotubes. Between the layers, the scientists embedded the necessary lithium compounds in nanoparticle form (LiMn2O4 for one electrode, LiTi2(PO4)3 for the other). In contrast to conventional lithium ion batteries, the lithium compounds cannot leak out of the electrodes, either while in use or after a break. The thin layer electrodes are each fixed on a substrate of self-healing polymer. Between the electrodes is a novel, solvent-free electrolyte made from a cellulose-based gel with an aqueous lithium sulfate solution embedded in it. This gel electrolyte also serves as a separation layer between the electrodes.

After a break, it is only necessary to press the broken ends together for a few seconds for them to grow back together. Both the self-healing polymer and the carbon nanotubes “stick” back together perfectly. The parallel arrangement of the nanotubes allows them to come together much better than layers of disordered carbon nanotubes. The electrolyte also poses no problems. Whereas conventional electrolytes decompose immediately upon exposure to air, the new gel is stable. Free of organic solvents, it is neither flammable nor toxic, making it safe for this application.

The capacity and charging/discharging properties of a battery “armband” placed around a doll’s elbow were maintained, even after repeated break/self-healing cycles.

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

A Self-Healing Aqueous Lithium-Ion Battery by Yang Zhao, Ye Zhang, Hao Sun, Xiaoli Dong, Jingyu Cao, Lie Wang, Yifan Xu, Jing Ren, Yunil Hwang, Dr. In Hyuk Son, Dr. Xianliang Huang, Prof. Yonggang Wang, and Prof. Huisheng Peng. Angewandte Chemie International Edition DOI: 10.1002/anie.201607951 Version of Record online: 12 OCT 2016

© 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

This paper is behind a paywall.

Carrying a solar cell on a pencil or glass slide?

Caption: Ultra-thin solar cells are flexible enough to bend around small objects, such as the 1mm-thick edge of a glass slide, as shown here. Credit: Juho Kim, et al/ APL

Caption: Ultra-thin solar cells are flexible enough to bend around small objects, such as the 1mm-thick edge of a glass slide, as shown here. Credit: Juho Kim, et al/ APL

Yes, this is another wearable electronics story and this time, it’s from South Korea. A June 20, 2016 news item on ScienceDaily announces remarkably thin and flexible photovoltaics,

Scientists in South Korea have made ultra-thin photovoltaics flexible enough to wrap around the average pencil. The bendy solar cells could power wearable electronics like fitness trackers and smart glasses. …

A June 20, 2016 American Institute of Physics news release on EurekAlert, which originated the news item, expands on the theme,

Thin materials flex more easily than thick ones – think a piece of paper versus a cardboard shipping box. The reason for the difference: The stress in a material while it’s being bent increases farther out from the central plane. Because thick sheets have more material farther out they are harder to bend.

“Our photovoltaic is about 1 micrometer thick,” said Jongho Lee, an engineer at the Gwangju Institute of Science and Technology in South Korea. One micrometer is much thinner than an average human hair. Standard photovoltaics are usually hundreds of times thicker, and even most other thin photovoltaics are 2 to 4 times thicker.

The researchers made the ultra-thin solar cells from the semiconductor gallium arsenide. They stamped the cells directly onto a flexible substrate without using an adhesive that would add to the material’s thickness. The cells were then “cold welded” to the electrode on the substrate by applying pressure at 170 degrees Celcius and melting a top layer of material called photoresist that acted as a temporary adhesive. The photoresist was later peeled away, leaving the direct metal to metal bond.

The metal bottom layer also served as a reflector to direct stray photons back to the solar cells. The researchers tested the efficiency of the device at converting sunlight to electricity and found that it was comparable to similar thicker photovoltaics. They performed bending tests and found the cells could wrap around a radius as small as 1.4 millimeters.

The team also performed numerical analysis of the cells, finding that they experience one-fourth the amount of strain of similar cells that are 3.5 micrometers thick.

“The thinner cells are less fragile under bending, but perform similarly or even slightly better,” Lee said.

A few other groups have reported solar cells with thicknesses of around 1 micrometer, but have produced the cells in different ways, for example by removing the whole substract by etching.

By transfer printing instead of etching, the new method developed by Lee and his colleagues may be used to make very flexible photovoltaics with a smaller amount of materials.

The thin cells can be integrated onto glasses frames or fabric and might power the next wave of wearable electronics, Lee said.

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

Ultra-thin flexible GaAs photovoltaics in vertical forms printed on metal surfaces without interlayer adhesives by Juho Kim, Jeongwoo Hwang, Kwangsun Song, Namyun Kim, Jae Cheol Shin, and Jongho Lee. Appl. Phys. Lett. 108, 253101 (2016); http://dx.doi.org/10.1063/1.4954039

This paper is open access.