Tag Archives: R. Vasant Kumar

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.

Smartphone battery inspired by your guts?

The conversion of bacteria from an enemy to be vanquished at all costs to a ‘frenemy’, a friendly enemy supplying possible solutions for problems is fascinating. An Oct. 26, 2016 news item on Nanowerk falls into the ‘frenemy’ camp,

A new prototype of a lithium-sulphur battery – which could have five times the energy density of a typical lithium-ion battery – overcomes one of the key hurdles preventing their commercial development by mimicking the structure of the cells which allow us to absorb nutrients.

Researchers have developed a prototype of a next-generation lithium-sulphur battery which takes its inspiration in part from the cells lining the human intestine. The batteries, if commercially developed, would have five times the energy density of the lithium-ion batteries used in smartphones and other electronics.

An Oct. 26, 2016 University of Cambridge press release (also on EurekAlert), which originated the news item, expands on the theme and provides some good explanations of how lithium-ion batteries and lithium-sulphur batteries work (Note: A link has been removed),

The new design, by researchers from the University of Cambridge, overcomes one of the key technical problems hindering the commercial development of lithium-sulphur batteries, by preventing the degradation of the battery caused by the loss of material within it. The results are reported in the journal Advanced Functional Materials.

Working with collaborators at the Beijing Institute of Technology, the Cambridge researchers based in Dr Vasant Kumar’s team in the Department of Materials Science and Metallurgy developed and tested a lightweight nanostructured material which resembles villi, the finger-like protrusions which line the small intestine. In the human body, villi are used to absorb the products of digestion and increase the surface area over which this process can take place.

In the new lithium-sulphur battery, a layer of material with a villi-like structure, made from tiny zinc oxide wires, is placed on the surface of one of the battery’s electrodes. This can trap fragments of the active material when they break off, keeping them electrochemically accessible and allowing the material to be reused.

“It’s a tiny thing, this layer, but it’s important,” said study co-author Dr Paul Coxon from Cambridge’s Department of Materials Science and Metallurgy. “This gets us a long way through the bottleneck which is preventing the development of better batteries.”

A typical lithium-ion battery is made of three separate components: an anode (negative electrode), a cathode (positive electrode) and an electrolyte in the middle. The most common materials for the anode and cathode are graphite and lithium cobalt oxide respectively, which both have layered structures. Positively-charged lithium ions move back and forth from the cathode, through the electrolyte and into the anode.

The crystal structure of the electrode materials determines how much energy can be squeezed into the battery. For example, due to the atomic structure of carbon, each carbon atom can take on six lithium ions, limiting the maximum capacity of the battery.

Sulphur and lithium react differently, via a multi-electron transfer mechanism meaning that elemental sulphur can offer a much higher theoretical capacity, resulting in a lithium-sulphur battery with much higher energy density. However, when the battery discharges, the lithium and sulphur interact and the ring-like sulphur molecules transform into chain-like structures, known as a poly-sulphides. As the battery undergoes several charge-discharge cycles, bits of the poly-sulphide can go into the electrolyte, so that over time the battery gradually loses active material.

The Cambridge researchers have created a functional layer which lies on top of the cathode and fixes the active material to a conductive framework so the active material can be reused. The layer is made up of tiny, one-dimensional zinc oxide nanowires grown on a scaffold. The concept was trialled using commercially-available nickel foam for support. After successful results, the foam was replaced by a lightweight carbon fibre mat to reduce the battery’s overall weight.

“Changing from stiff nickel foam to flexible carbon fibre mat makes the layer mimic the way small intestine works even further,” said study co-author Dr Yingjun Liu.

This functional layer, like the intestinal villi it resembles, has a very high surface area. The material has a very strong chemical bond with the poly-sulphides, allowing the active material to be used for longer, greatly increasing the lifespan of the battery.

“This is the first time a chemically functional layer with a well-organised nano-architecture has been proposed to trap and reuse the dissolved active materials during battery charging and discharging,” said the study’s lead author Teng Zhao, a PhD student from the Department of Materials Science & Metallurgy. “By taking our inspiration from the natural world, we were able to come up with a solution that we hope will accelerate the development of next-generation batteries.”

For the time being, the device is a proof of principle, so commercially-available lithium-sulphur batteries are still some years away. Additionally, while the number of times the battery can be charged and discharged has been improved, it is still not able to go through as many charge cycles as a lithium-ion battery. However, since a lithium-sulphur battery does not need to be charged as often as a lithium-ion battery, it may be the case that the increase in energy density cancels out the lower total number of charge-discharge cycles.

“This is a way of getting around one of those awkward little problems that affects all of us,” said Coxon. “We’re all tied in to our electronic devices – ultimately, we’re just trying to make those devices work better, hopefully making our lives a little bit nicer.”

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

Advanced Lithium–Sulfur Batteries Enabled by a Bio-Inspired Polysulfide Adsorptive Brush by Teng Zhao, Yusheng Ye, Xiaoyu Peng, Giorgio Divitini, Hyun-Kyung Kim, Cheng-Yen Lao, Paul R. Coxon, Kai Xi, Yingjun Liu, Caterina Ducati, Renjie Chen, R. Vasant Kumar. Advanced Functional Materials DOI: 10.1002/adfm.201604069 First published: 26 October 2016

This paper is behind a paywall.

Caption: This is a computer visualization of villi-like battery material. Credit: Teng Zhao

Caption: This is a computer visualization of villi-like battery material. Credit: Teng Zhao