Tag Archives: li-ion batteries

Hydro-Québec, lithium-ion batteries, and silicate-based nanoboxes

Hydro-Québec (Canada) is making a bit of a splash these days (this is the third mention within less than a week) on my blog, if nowhere else. The latest development was announced in a Feb. 24, 2015 news item on Nanowerk (Note: A link has been removed),

Researchers from Singapore’s Institute of Bioengineering and Nanotechnology (IBN) of A*STAR and Quebec’s IREQ (Hydro-Québec’s research institute) have synthesized silicate-based nanoboxes that could more than double the energy capacity of lithium-ion batteries as compared to conventional phosphate-based cathodes (“Synthesis of Phase-Pure Li2MnSiO4@C Porous Nanoboxes for High-Capacity Li-Ion Battery Cathodes”). This breakthrough could hold the key to longer-lasting rechargeable batteries for electric vehicles and mobile devices.

A Feb. 24, 2015 Hydro-Québec press release (also on Canadian News Wire), which originated the news item, describe the research and the relationship between the two institutions,

“IBN researchers have successfully achieved simultaneous control of the phase purity and nanostructure of Li2MnSiO4 for the first time,” said Professor Jackie Y. Ying, IBN Executive Director. “This novel synthetic approach would allow us to move closer to attaining the ultrahigh theoretical capacity of silicate-based cathodes for battery applications.”

“We are delighted to collaborate with IBN on this project. IBN’s expertise in synthetic chemistry and nanotechnology allows us to explore new synthetic approaches and nanostructure design to achieve complex materials that pave the way for breakthroughs in battery technology, especially regarding transportation electrification,” said Dr. Karim Zaghib, Director – Energy Storage and Conservation at Hydro-Québec.

Lithium-ion batteries are widely used to power many electronic devices, including smart phones, medical devices and electric vehicles. Their high energy density, excellent durability and lightness make them a popular choice for energy storage. Due to a growing demand for long-lasting, rechargeable lithium-ion batteries for various applications, significant efforts have been devoted to improving the capacity of these batteries. In particular, there is great interest in developing new compounds that may increase energy storage capacity, stability and lifespan compared to conventional lithium phosphate batteries.

The five-year research collaboration between IBN and Hydro-Québec was established in 2011. The researchers plan to further enhance their new cathode materials to create high-capacity lithium-ion batteries for commercialization.

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

Synthesis of phase-pure Li2MnSiO4@C porous nanoboxes for high-capacity Li-ion battery cathodes by Xian-Feng Yang, Jin-Hua Yang, Karim Zaghib, Michel L. Trudeau, and Jackie Y. Ying. Nano Energy Volume 12, March 2015, Pages 305–313 doi:10.1016/j.nanoen.2014.12.021

This paper is behind a paywall.

Here are my two most recent mentions of Hydro-Québec and lithium-ion batteries (both Grafoid and NanoXplore have deals with Hydro-Québec),

Investment in graphene (Grafoid), the Canadian government, and a 2015 federal election (Feb. 23, 2015)

NanoXplore: graphene and graphite in Québec (Canada) (Feb. 20, 2015)

Investment in graphene (Grafoid), the Canadian government, and a 2015 federal election

The federal government of Canada is facing an election this year and many analysts believe it will be held in October 2015. Interestingly, there have been a few recent announcements about funding, also referred to as contributions, for technology companies in the provinces of Ontario and Québec. (You need to win at least one of these provinces if you want to enjoy a majority government.) My Cellulose nanocrystals (CNC), also known as nanocrystalline cellulose (NCC), and toxicity; some Celluforce news; anti-petroleum extremists posted on Feb. 19, 2015 includes my observations (scroll down past the toxicity topic) about the government’s ‘clean technology’ promotional efforts and the rebranding of environmentalism into an ‘anti-petroleum’ movement.

This latest announcement about a ‘non-repayable grant’ is to be found in a Feb. 20, 2015 news item on Azonano,

The Hon. Greg Rickford, Minister of Natural Resources and Minister Responsible for Sustainable Development Technology Canada (SDTC) announced today the award of $8.1 million to Grafoid Inc. – Canada’s leading graphene technologies and applications developer – to automate Grafoid’s production of its low-cost, high-purity MesoGraf™ graphene.

“Our government is investing in advanced clean energy technologies that create well-paying jobs and generate economic opportunities. Today’s announcement contributes to economic prosperity and a cleaner environment in Ontario and across Canada,” said Mr. Rickford, who is also the Minister Responsible for Federal Economic Development Initiative for Northern Ontario.

The contribution from SDTC is an $8.1 million non-repayable grant to design and test the automation system for the production of constant quality MesoGraf™. Further, the grant enables the testing of pre-commercial products using MesoGraf™ graphene from the automated system.

The minister announced the funding at a news conference in Toronto attended by Grafoid and five other Canadian non graphene-related technology companies.

Ottawa-based [Ottawa is in the province of Ontario] Grafoid, the developer of a diverse range of renewable energy, industrial, military and consumer applications from its MesoGraf™ materials is the first Canadian graphene technologies developer to partner with the Canadian Government.

A Feb. 20, 2015 Grafoid news release on Marketwired.com, which originated the news item, describes how this makes Canada like other constituencies and gives a bit more detail about the company and its aims,

Canada joins the European Union, the United States, China and South Korea in providing funding assistance to privately-held graphene enterprises.

Grafoid Founding Partner and CEO Gary Economo praised Canada’s decision to stake its claim in the graphene space as the world races toward the commercialization of a potentially disruptive, pan-industrial nanomaterial.

“This is a great day for the Canadian graphene industry and for Grafoid, in particular, because it leads us out of the laboratory and into the automated manufacturing of the world’s new wonder material,” he told the news conference.

“Effectively, today’s $8.1million Federal government funding grant enables us to take a giant leap towards graphene’s broader commercialization,” Mr. Economo said. “It will permit us to increase MesoGraf™ production output from kilograms to tonnes within our global technology centre in Kingston, Ontario.

“For this we are truly appreciative of Canada’s actions in recognizing our science and commercial objectives. In the past three years Grafoid has travelled the globe staking our unique position in the graphene revolution. Today we are gratified to do this going forward with the Government of Canada,” Mr. Economo said.

Grafoid produces MesoGraf™ directly from high-grade graphite ore on a safe, economically scalable, environmentally sustainable basis. Its patent pending one-step process is unique in the industry, producing single layer, bi-layer and tri-layer graphene.

It is then adapted – or functionalized – by Grafoid for use in biomedical, renewable energy storage and production, military, aerospace and automotive, additive materials for 3D printing, water purification, construction, lubricants, solar solutions, coatings, sporting equipment and other sectoral applications.

At one atom thin, graphene is a two-dimensional pure carbon derived from graphite.

It is the strongest material known to science, is barely visible to the naked eye, yet it holds the potential to become a disruptive technology across all industrial sectors and ultimately, for the benefit of humanity.

Grafoid’s Game-Changing Process

Grafoid’s unique graphite ore-to-graphene process produces a material that eliminates cost barriers to graphene’s broad commercialization in a number of industries, some of which include building materials, automotive, aerospace, military, biomedical, renewable energy and sporting equipment.

In order to bring those application developments to market Grafoid’s partners require a scaling up of MesoGraf™ production to supply their needs for pre-production development testing and commercial production, and; the expansion of Grafoid’s research and development.

The automation of bulk MesoGraf™ graphene production is a global first. Uniformity and consistency are critical to the development of mass produced commercial applications.

One of the company’s first-to-market MesoGraf™ developments is in the renewable energy storage and power generation sectors. The market for quick charge long-life batteries is vast, and growing.

Hydro-Quebec – one of the world’s premier patent holders and suppliers of renewable energy technologies – is one of Grafoid’s first long-term sustainable technology development partners. [emphasis mine]

Within six months of development, multiple patents were filed and initial tests of the joint venture’s MesoGraf™ lithium-iron phosphate materials resulted in extreme gains in power performance over conventional batteries.

Grafoid’s corporate goal is not to simply be a graphene supplier but a global partner in commercial application development. With the ability to ramp up graphene output the company’s long-term financial prospects are secured from royalties and licensing fees from jointly developed technologies.

Competitive cost advantages built into an automated MesoGraf™ graphene production regime results in anticipated cost advantages to customers and licensees.

The Hydro-Québec deal with Grafoid was mentioned here in a Nov. 27, 2012 posting which includes this nugget,

There’s also the announcement of a joint venture between Grafoid (a company where, I believe, 40% is owned by Focus Graphite) with the University of Waterloo, from the Apr. 17, 2013 news item on Azonano,

Focus Graphite Inc. on behalf of Grafoid Inc. (“Grafoid”) is pleased to announce the signing of a two-year R&D agreement between Grafoid Inc. and the University of Waterloo to investigate and develop a graphene-based composite for electrochemical energy storage for the automotive and/or portable electronics sectors.

Given the company information included in the news release, there seems to have been a change in the corporate relationship between Grafoid and Focus Graphite. At the very least, Grafoid announcements are now generated by Grafoid itself,

About Grafoid Inc.

Incorporated in late 2011, Grafoid invested in a novel process that transforms raw, unprocessed, high grade graphite ore from its sister company, Focus Graphite to produce single layer, bi-layer and tri-layer MesoGraf™ graphene.

Today, Grafoid, a private company, sits as Canada’s innovation leader and standard-bearer in the global graphene technology space.

The company’s diverse commercial application developments include more than 15 global corporate partnerships – including Fortune 500 companies.

With 17 active projects under development with 11 universities and laboratories, and; some 64 patent applications filed or in development, Grafoid’s business goes beyond scientific R&D.

Grafoid’s Canadian-developed technologies are exported globally.

During the last three years Grafoid has experienced exponential growth as a global enterprise through joint-venture partnerships with Hydro-Quebec, Japan’s Mitsui & Company and other multinational corporations in the United States and Europe.

Grafoid’s wholly-owned subsidiaries Alcereco of Kingston, Ontario and Braille Battery, of Sarasota, Florida extend the company’s capabilities into graphene related material science and nano-engineering.

Braille is a world leader in ultra lightweight Lithium-ion high performance battery production and is a supplier to Formula 1, NASCAR and IndyCar racing vehicles.

The sister company, Focus Graphite also based in Ottawa, which provides Grafoid’s graphite flakes, owns a deposit in the northeastern part of Québec. (You can read more about graphite deposits and mines in my Feb. 20, 2015 post, NanoXplore: graphene and graphite in Québec (Canada).

Of course, this flurry of announcements may point to a Spring 2015 election.

NanoXplore: graphene and graphite in Québec (Canada)

For the second time this week I’m going to be mentioning the province of Québec (Canada) in relation to its ‘nanotechnology’ businesses (see: Cellulose nanocrystals (CNC), also known as nanocrystalline cellulose (NCC), and toxicity; some Celluforce news; anti-petroleum extremists posted on Feb. 19, 2015). A Feb. 20, 2015 news item on Azonano announces a graphene production facility in the Montréal area,

Group NanoXplore Inc., a Montreal-based company specialising in the production and application of graphene and its derivative materials, announced today that its graphene production facility is in full operation with a capacity of 3 metric tonnes per year. This is the largest graphene production capacity in Canada and, outside of China, one of the 5 largest in the world.

A Feb. 19, 2015 NanoXplore news release on MarketWire, which originated the news item, provides a bit more detail in amidst the promotional hype,

NanoXplore’s production process is unique and the core of the company’s competitive advantage. The proprietary process gently and efficiently creates pristine graphene from natural flake graphite without creating the crystalline defects that can limit performance. The process also functionalises the graphene material during production making subsequent mixing with a broad range of industrial materials simple and efficient. NanoXplore’s facility is routinely producing several standard grades of graphene as well as derivative products such as a unique graphite-graphene composite suitable for anodes in Li-ion batteries. [emphasis mine]

Another graphite connection in Québec

Interestingly, back in 2012 Hydro-Québec signed a deal with another Québec-based company, Focus Graphite (which owns a graphite deposit in the northeastern part of the province) to explore ways to produce more efficient lithium-ion batteries (my Nov 27, 2012 posting).

Getting back to the news release, it also provides a summary description of NanoXplore,

NanoXplore is a privately held advanced materials company focused on the large-scale production of high quality graphene and the integration of graphene into real world industrial products. NanoXplore achieves significant improvements in performance for its customers with very low levels of graphene because its material is of high quality (few defects, highly dispersible), because the production process can easily tune the dimensions of the graphene platelets, and because NanoXplore has specific expertise in dispersing graphene in a broad range of industrial materials. NanoXplore partners with its customers to integrate graphene into their products and processes, providing them with innovative products and a strong competitive advantage.

Graphite mines

NanoXplore, too, has some sort of relationship with a graphite mine or, in this case mining company, Mason Graphite (from the NanoXplore website’s Investors’ page),

FROM MINE TO PRODUCT

Partnered with Canadian mining company Mason Graphite, NanoXplore has access to lower quartile graphite/graphene production costs as well as a stable, long term, large flake source of raw material. Local government bodies have embraced the graphite-graphene cluster. With production and R&D centrally located in Montreal, NanoXplore offers world class innovation and true intellectual property safety for its formulation partners.

By the way, Benoit Gascon, NanoXplore’s board chair (scroll down to the bottom  of the team list) is also Mason Graphite’s Chief Executive Officer (CEO). The company has recently announced a detailed study on large-scale production of value-added graphite products (from a Feb. 11, 2015 Mason Graphite news release),

Mason Graphite Inc. (“Mason Graphite” or the “Company”) (TSX VENTURE:LLG)(OTCQX:MGPHF) announces that it has initiated a detailed study for large scale processing of value-added graphite products.

Value-added processing includes micronization, additional purification, spheronization and coating, resulting in graphite products that are suitable for a wide range of electrochemical applications (including alkaline batteries, lithium-ion batteries and fuel cells), technical applications (including carbon brushes, brake linings, plastics and lubricants), and other specialized uses.

The development and validation of the fabrication processes for these graphite products will be carried out by the National Research Council of Canada (“NRC”) along with Hatch, and is expected to conclude by the end of 2015. Following initial scoping work, equipment trials and product testing, the Company intends to provide preliminary results and an updated work program by mid-2015.

The NRC is the Government of Canada’s premier research and technology organization. Hatch is an engineering firm located in Montreal which is already working closely with Mason Graphite on the development of the Lac Gueret Graphite Project.

Other parts of Canada and the graphite/graphene enterprise

NanoXplore and Focus Graphite are not the only companies with connections to a graphite mine in Québec. There’s also Vancouver (Canada)-based Lomiko Metals (mentioned here in an April 17, 2013 posting [for the first time]. A. Paul Gill, Lomiko’s CEO, seems to be pursuing a similar business strategy in that Lomiko, too, has a number of business alliances, e.g., the mine, a research and development laboratory, etc. Moving out of Québec, there is also a graphite mine in Ontario owned by Northern Graphite (my Feb. 6, 2012 posting). It seems Canadians in eastern Canada have a valuable resource in graphite flakes.

Kevlar-wrapped batteries on an airplane

Researchers at the University of Michigan are not trying to bulletproof lithium-ion batteries with kevlar. Rather, they’re trying prevent fires. From a Jan. 27, 2015 University of Michigan news release (also on EurekAlert),

New battery technology from the University of Michigan should be able to prevent the kind of fires that grounded Boeing 787 Dreamliners in 2013.

The innovation is an advanced barrier between the electrodes in a lithium-ion battery.

Made with nanofibers extracted from Kevlar, the tough material in bulletproof vests, the barrier stifles the growth of metal tendrils that can become unwanted pathways for electrical current.

A U-M team of researchers also founded Ann Arbor-based Elegus Technologies to bring this research from the lab to market. Mass production is expected to begin in the fourth quarter 2016.

“Unlike other ultra strong materials such as carbon nanotubes, Kevlar is an insulator,” said Nicholas Kotov, the Joseph B. and Florence V. Cejka Professor of Engineering. “This property is perfect for separators that need to prevent shorting between two electrodes.”

Lithium-ion batteries work by shuttling lithium ions from one electrode to the other. This creates a charge imbalance, and since electrons can’t go through the membrane between the electrodes, they go through a circuit instead and do something useful on the way.

But if the holes in the membrane are too big, the lithium atoms can build themselves into fern-like structures, called dendrites, which eventually poke through the membrane. If they reach the other electrode, the electrons have a path within the battery, shorting out the circuit. This is how the battery fires on the Boeing 787 are thought to have started.

“The fern shape is particularly difficult to stop because of its nanoscale tip,” said Siu On Tung, a graduate student in Kotov’s lab, as well as chief technology officer at Elegus. “It was very important that the fibers formed smaller pores than the tip size.”

While the widths of pores in other membranes are a few hundred nanometers, or a few hundred-thousandths of a centimeter, the pores in the membrane developed at U-M are 15-to-20 nanometers across. They are large enough to let individual lithium ions pass, but small enough to block the 20-to-50-nanometer tips of the fern-structures.

The researchers made the membrane by layering the fibers on top of each other in thin sheets. This method keeps the chain-like molecules in the plastic stretched out, which is important for good lithium-ion conductivity between the electrodes, Tung said.

“The special feature of this material is we can make it very thin, so we can get more energy into the same battery cell size, or we can shrink the cell size,” said Dan VanderLey, an engineer who helped found Elegus through U-M’s Master of Entrepreneurship program. “We’ve seen a lot of interest from people looking to make thinner products.”

Thirty companies have requested samples of the material.

Kevlar’s heat resistance could also lead to safer batteries as the membrane stands a better chance of surviving a fire than most membranes currently in use.

While the team is satisfied with the membrane’s ability to block the lithium dendrites, they are currently looking for ways to improve the flow of loose lithium ions so that batteries can charge and release their energy more quickly.

For anyone unfamiliar with the Boeing 787 Dreamliner fires, caused by lithium-ion batteries, these Boeing fires and others are mentioned in my May 29, 2013 post (Life-cycle assessment for electric vehicle lithium-ion batteries and nanotechnology is a risk analysis) scroll down about 50% of the way.

As for the research paper, here’s a link and a citation,

A dendrite-suppressing composite ion conductor from aramid nanofibres by Siu-On Tung, Szushen Ho, Ming Yang, Ruilin Zhang, & Nicholas A. Kotov. Nature Communications 6, Article number: 6152 doi:10.1038/ncomms7152 Published 27 January 2015

This paper is behind a paywall.

You can find out more about Elegus Technologies here.

Supercapacitors* on automobiles

Queensland University of Technology* (QUT; Australia) researchers are hopeful they can adapt supercapacitors in the form of a fine film tor use in electric vehicles making them more energy-efficient. From a Nov. 6, 2014 news item on ScienceDaily,

A car powered by its own body panels could soon be driving on our roads after a breakthrough in nanotechnology research by a QUT team.

Researchers have developed lightweight “supercapacitors” that can be combined with regular batteries to dramatically boost the power of an electric car.

The discovery was made by Postdoctoral Research Fellow Dr Jinzhang Liu, Professor Nunzio Motta and PhD researcher Marco Notarianni, from QUT’s Science and Engineering Faculty — Institute for Future Environments, and PhD researcher Francesca Mirri and Professor Matteo Pasquali, from Rice University in Houston, in the United States.

A Nov. 6, 2014 QUT news release, which originated the news item, describes supercapacitors, the research, and the need for this research in more detail,

The supercapacitors – a “sandwich” of electrolyte between two all-carbon electrodes – were made into a thin and extremely strong film with a high power density.

The film could be embedded in a car’s body panels, roof, doors, bonnet and floor – storing enough energy to turbocharge an electric car’s battery in just a few minutes.

“Vehicles need an extra energy spurt for acceleration, and this is where supercapacitors come in. They hold a limited amount of charge, but they are able to deliver it very quickly, making them the perfect complement to mass-storage batteries,” he said.

“Supercapacitors offer a high power output in a short time, meaning a faster acceleration rate of the car and a charging time of just a few minutes, compared to several hours for a standard electric car battery.”

Dr Liu said currently the “energy density” of a supercapacitor is lower than a standard lithium ion (Li-Ion) battery, but its “high power density”, or ability to release power in a short time, is “far beyond” a conventional battery.

“Supercapacitors are presently combined with standard Li-Ion batteries to power electric cars, with a substantial weight reduction and increase in performance,” he said.

“In the future, it is hoped the supercapacitor will be developed to store more energy than a Li-Ion battery while retaining the ability to release its energy up to 10 times faster – meaning the car could be entirely powered by the supercapacitors in its body panels.

“After one full charge this car should be able to run up to 500km – similar to a petrol-powered car and more than double the current limit of an electric car.”

Dr Liu said the technology would also potentially be used for rapid charges of other battery-powered devices.

“For example, by putting the film on the back of a smart phone to charge it extremely quickly,” he said.

The discovery may be a game-changer for the automotive industry, with significant impacts on financial, as well as environmental, factors.

“We are using cheap carbon materials to make supercapacitors and the price of industry scale production will be low,” Professor Motta said.

“The price of Li-Ion batteries cannot decrease a lot because the price of Lithium remains high. This technique does not rely on metals and other toxic materials either, so it is environmentally friendly if it needs to be disposed of.”

A Nov. 10, 2014 news item on Azonano describes the Rice University (Texas, US) contribution to this work,

Rice University scientist Matteo Pasquali and his team contributed to two new papers that suggest the nano-infused body of a car may someday power the car itself.

Rice supplied high-performance carbon nanotube films and input on the device design to scientists at the Queensland University of Technology in Australia for the creation of lightweight films containing supercapacitors that charge quickly and store energy. The inventors hope to use the films as part of composite car doors, fenders, roofs and other body panels to significantly boost the power of electric vehicles.

A Nov. 7, 2014 Rice University news release, which originated the news item, offers a few technical details about the film being proposed for use as a supercapacitor on car panels,

Researchers in the Queensland lab of scientist Nunzio Motta combined exfoliated graphene and entangled multiwalled carbon nanotubes combined with plastic, paper and a gelled electrolyte to produce the flexible, solid-state supercapacitors.

“Nunzio’s team is making important advances in the energy-storage area, and we were glad to see that our carbon nanotube film technology was able to provide breakthrough current collection capability to further improve their devices,” said Pasquali, a Rice professor of chemical and biomolecular engineering and chemistry. “This nice collaboration is definitely bottom-up, as one of Nunzio’s Ph.D. students, Marco Notarianni, spent a year in our lab during his Master of Science research period a few years ago.”

“We built on our earlier work on CNT films published in ACS Nano, where we developed a solution-based technique to produce carbon nanotube films for transparent electrodes in displays,” said Francesca Mirri, a graduate student in Pasquali’s research group and co-author of the papers. “Now we see that carbon nanotube films produced by the solution-processing method can be applied in several areas.”

As currently designed, the supercapacitors can be charged through regenerative braking and are intended to work alongside the lithium-ion batteries in electric vehicles, said co-author Notarianni, a Queensland graduate student.

“Vehicles need an extra energy spurt for acceleration, and this is where supercapacitors come in. They hold a limited amount of charge, but with their high power density, deliver it very quickly, making them the perfect complement to mass-storage batteries,” he said.

Because hundreds of film supercapacitors are used in the panel, the electric energy required to power the car’s battery can be stored in the car body. “Supercapacitors offer a high power output in a short time, meaning a faster acceleration rate of the car and a charging time of just a few minutes, compared with several hours for a standard electric car battery,” Notarianni said.

The researchers foresee such panels will eventually replace standard lithium-ion batteries. “In the future, it is hoped the supercapacitor will be developed to store more energy than an ionic battery while retaining the ability to release its energy up to 10 times faster – meaning the car would be powered by the supercapacitors in its body panels,” said Queensland postdoctoral researcher Jinzhang Liu.

Here’s an image of graphene infused with carbon nantoubes used in the supercapacitor film,

A scanning electron microscope image shows freestanding graphene film with carbon nanotubes attached. The material is part of a project to create lightweight films containing super capacitors that charge quickly and store energy. Courtesy of Nunzio Motta/Queensland University of Technology - See more at: http://news.rice.edu/2014/11/07/supercharged-panels-may-power-cars/#sthash.0RPsIbMY.dpuf

A scanning electron microscope image shows freestanding graphene film with carbon nanotubes attached. The material is part of a project to create lightweight films containing super capacitors that charge quickly and store energy. Courtesy of Nunzio Motta/Queensland University of Technology

Here are links to and citations for the two papers published by the researchers,

Graphene-based supercapacitor with carbon nanotube film as highly efficient current collector by Marco Notarianni, Jinzhang Liu, Francesca Mirri, Matteo Pasquali, and Nunzio Motta. Nanotechnology Volume 25 Number 43 doi:10.1088/0957-4484/25/43/435405

High performance all-carbon thin film supercapacitors by Jinzhang Liu, Francesca Mirri, Marco Notarianni, Matteo Pasquali, and Nunzio Motta. Journal of Power Sources Volume 274, 15 January 2015, Pages 823–830 DOI: 10.1016/j.jpowsour.2014.10.104

Both articles are behind paywalls.

One final note, Dexter Johnson provides some insight into issues with graphene-based supercapacitors and what makes this proposed application attractive in his Nov. 7, 2014 post on the Nanoclast blog (on the IEEE [Institute of Electrical and Electronics Engineers] website; Note: Links have been removed),

The hope has been that someone could make graphene electrodes for supercapacitors that would boost their energy density into the range of chemical-based batteries. The supercapacitors currently on the market have on average an energy density around 28 Wh/kg, whereas a Li-ion battery holds about 200Wh/kg. That’s a big gap to fill.

The research in the field thus far has indicated that graphene’s achievable surface area in real devices—the factor that determines how many ions a supercapacitor electrode can store, and therefore its energy density—is not any better than traditional activated carbon. In fact, it may not be much better than a used cigarette butt.

Though graphene may not help increase supercapacitors’ energy density, its usefulness in this application may lie in the fact that its natural high conductivity will allow superconductors to operate at higher frequencies than those that are currently on the market. Another likely benefit that graphene will yield comes from the fact that it can be structured and scaled down, unlike other supercapacitor materials.

I recommend reading Dexter’s commentary in its entirety.

*’University of Queensland’ corrected to “Queensland University of Technology’ on Nov. 10, 2014 at 1335 PST.

* ‘super-capacitor’ changed to ‘supercapacitor’ on April 29, 2015.

Friendlier (halogen-free) lithium-ion batteries

An Oct. 24, 2014 news item on ScienceDaily mentions a greener type of lithium-ion battery from a theoretical (keep reading till you reach the first paragraph of the university news release) perspective,

Physics researchers at Virginia Commonwealth University have discovered that most of the electrolytes used in lithium-ion batteries — commonly found in consumer electronic devices — are superhalogens, and that the vast majority of these electrolytes contain toxic halogens.

At the same time, the researchers also found that the electrolytes in lithium-ion batteries (also known as Li-ion batteries) could be replaced with halogen-free electrolytes that are both nontoxic and environmentally friendly.

“The significance [of our findings] is that one can have a safer battery without compromising its performance,” said lead author Puru Jena, Ph.D., distinguished professor in the Department of Physics of the College of Humanities and Sciences. “The implication of our research is that similar strategies can also be used to design cathode materials in Li-ion batteries.”

An Oct. 24, 2014 Virginia Commonwealth University news release by Brian McNeill (also on EurekAlert), which originated the news item, describes the researchers’ hopes and the inspiration for this work,

“We hope that our theoretical prediction will stimulate experimentalists to synthesize halogen-free salts which will then lead manufacturers to use such salts in commercial applications,” he said.

The researchers also found that the procedure outlined for Li-ion batteries is equally valid for other metal-ion batteries, such as sodium-ion or magnesium-ion batteries.

Jena became interested in the topic several months ago when he saw a flyer on Li-ion batteries that mentioned the need for halogen-free electrolytes.

“I had not done any work on Li-ion batteries at the time, but I was curious to see what the current electrolytes are,” he said. “I found that the negative ions that make up the electrolytes are large and complex in nature and they contain one less electron than what is needed for electronic shell closure.”

Jena had already been working for more than five years on superhalogens, a class of molecules that mimic the chemistry of halogens but have electron affinities that are much larger than that of the halogen atoms.

“I knew of many superhalogen molecules that do not contain a single halogen atom,” he said. “My immediate thought was first to see if the anionic components of the current electrolytes are indeed superhalogens. And, if so, do the halogen-free superhalogens that we knew serve the purpose as halogen-free electrolytes? Our research proved that to be the case.”

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

Superhalogens as Building Blocks of Halogen-Free Electrolytes in Lithium-Ion Batteries by Dr. Santanab Giri, Swayamprabha Behera and Prof. Puru Jena. Angewandte Chemie, DOI: 10.1002/ange.201408648 Article first published online: 14 OCT 2014

© 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

This paper is behind a paywall.

Sand and nanotechnology

There’s some good news coming out of the University of California, Riverside regarding sand and lithium-ion (li-ion) batteries, which I will temper with some additional information later in this posting.

First, the good news is that researchers have a new non-toxic, low cost way to produce a component in lithium-ion (li-ion) batteries according to a July 8, 2014 news item on ScienceDaily,

Researchers at the University of California, Riverside’s Bourns College of Engineering have created a lithium ion battery that outperforms the current industry standard by three times. The key material: sand. Yes, sand.

“This is the holy grail — a low cost, non-toxic, environmentally friendly way to produce high performance lithium ion battery anodes,” said Zachary Favors, a graduate student working with Cengiz and Mihri Ozkan, both engineering professors at UC Riverside.

The idea came to Favors six months ago. He was relaxing on the beach after surfing in San Clemente, Calif. when he picked up some sand, took a close look at it and saw it was made up primarily of quartz, or silicon dioxide.

His research is centered on building better lithium ion batteries, primarily for personal electronics and electric vehicles. He is focused on the anode, or negative side of the battery. Graphite is the current standard material for the anode, but as electronics have become more powerful graphite’s ability to be improved has been virtually tapped out.

A July 8, 2014 University of California at Riverside news release by Sean Nealon, which originated the news item, describes some of the problems with silicon as a replacement for graphite and how the researchers approached those problems,

Researchers are now focused on using silicon at the nanoscale, or billionths of a meter, level as a replacement for graphite. The problem with nanoscale silicon is that it degrades quickly and is hard to produce in large quantities.

Favors set out to solve both these problems. He researched sand to find a spot in the United States where it is found with a high percentage of quartz. That took him to the Cedar Creek Reservoir, east of Dallas, where he grew up.

Sand in hand, he came back to the lab at UC Riverside and milled it down to the nanometer scale, followed by a series of purification steps changing its color from brown to bright white, similar in color and texture to powdered sugar.

After that, he ground salt and magnesium, both very common elements found dissolved in sea water into the purified quartz. The resulting powder was then heated. With the salt acting as a heat absorber, the magnesium worked to remove the oxygen from the quartz, resulting in pure silicon.

The Ozkan team was pleased with how the process went. And they also encountered an added positive surprise. The pure nano-silicon formed in a very porous 3-D silicon sponge like consistency. That porosity has proved to be the key to improving the performance of the batteries built with the nano-silicon.

Now, the Ozkan team is trying to produce larger quantities of the nano-silicon beach sand and is planning to move from coin-size batteries to pouch-size batteries that are used in cell phones.

The research is supported by Temiz Energy Technologies. The UCR Office of Technology Commercialization has filed patents for inventions reported in the research paper.

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

Scalable Synthesis of Nano-Silicon from Beach Sand for Long Cycle Life Li-ion Batteries by Zachary Favors, Wei Wang, Hamed Hosseini Bay, Zafer Mutlu, Kazi Ahmed, Chueh Liu, Mihrimah Ozkan, & Cengiz S. Ozkan. Scientific Reports 4, Article number: 5623 doi:10.1038/srep05623 Published 08 July 2014

While this is good news, it does pose a conundrum of sorts. It seems that supplies of sand are currently under siege. A documentary, Sand Wars (2013) lays out the issues (from the Sand Wars website’s Synopsis page),

Most of us think of it as a complimentary ingredient of any beach vacation. Yet those seemingly insignificant grains of silica surround our daily lives. Every house, skyscraper and glass building, every bridge, airport and sidewalk in our modern society depends on sand. We use it to manufacture optical fiber, cell phone components and computer chips. We find it in our toothpaste, powdered foods and even in our glass of wine (both the glass and the wine, as a fining agent)!

Is sand an infinite resource? Can the existing supply satisfy a gigantic demand fueled by construction booms?  What are the consequences of intensive beach sand mining for the environment and the neighboring populations?

Based on encounters with sand smugglers, barefoot millionaires, corrupt politicians, unscrupulous real estate developers and environmentalists, this investigation takes us around the globe to unveil a new gold rush and a disturbing fact: the “SAND WARS” have begun.

Dr. Muditha D Senarath Yapa of John Keells Research at John Keells Holdings comments on the situation in Sri Lanka in his June 22, 2014 article (Nanotechnology – Depleting the most precious minerals for a few dollars) for The Nation,

Many have written for many years about the mineral sands of Pulmoddai. It is a national tragedy that for more than 50 years, we have been depleting the most precious minerals of our land for a few dollars. There are articles that appeared in various newspapers on how the mineral sands industry has boomed over the years. I hope the readers understand that it only means that we are depleting our resources faster than ever. According to the Lanka Mineral Sands Limited website, 90,000 tonnes of ilmenite, 9,000 tonnes of rutile, 5,500 tonnes of zircon, 100 tonnes of monazite and 4,000 tonnes of high titanium ilmenite are produced annually and shipped away to other countries.

… It is time for Sri Lanka to look at our own resources with this new light and capture the future nano materials market to create value added materials.

It’s interesting that he starts with the depletion of the sands as a national tragedy and ends with a plea to shift from a resource-based economy to a manufacturing-based economy. (This plea resonates strongly here in Canada where we too are a resource-based economy.)

Sidebar: John Keells Holdings is a most unusual company, from the About Us page,

In terms of market capitalisation, John Keells Holdings PLC is one of the largest listed conglomerate on the Colombo Stock Exchange. Other measures tell a similar tale; our group companies manage the largest number of hotel rooms in Sri Lanka, own the country’s largest privately-owned transportation business and hold leading positions in Sri Lanka’s key industries: tea, food and beverage manufacture and distribution, logistics, real estate, banking and information technology. Our investment in Sri Lanka is so deep and widely diversified that our stock price is sometimes used by international financial analysts as a benchmark of the country’s economy.

Yapa heads the companies research effort, which recently celebrated a synthetic biology agreement (from a May 2014 John Keells news release by Nuwan),

John Keells Research Signs an Historic Agreement with the Human Genetics Unit, Faculty of Medicine, University of Colombo to establish Sri Lanka’s first Synthetic Biology Research Programme.

Getting back to sand, these three pieces, ‘sand is good for li-ion batteries’, ‘sand is a diminishing resource’, and ‘let’s stop being a source of sand for other countries’ lay bare some difficult questions about our collective future on this planet.

Charging portable electronics in 10 minutes (hopefully) with a 3D (silicon-decorated) carbon nanotube cluster

I sometimes think there’s a worldwide obsession with lithium-ion batteries as hardly a day passes without at least one story about them. To honour that obsession, here’s a June 11, 2014 news item on Azonano describing a new technique which could lead to a faster charging time for mobile electronics,

Researchers at the University of California, Riverside [UCR] Bourns College of Engineering have developed a three-dimensional, silicon-decorated, cone-shaped carbon-nanotube cluster architecture for lithium ion battery anodes that could enable charging of portable electronics in 10 minutes, instead of hours.

A June 10, 2014 UCR news release by Sean Nealon, which originated the news item, notes the ubiquity of lithium-ion batteries in modern electronics and explains why silicon was used in this research,

Lithium ion batteries are the rechargeable battery of choice for portable electronic devices and electric vehicles. But, they present problems. Batteries in electric vehicles are responsible for a significant portion of the vehicle mass. And the size of batteries in portable electronics limits the trend of down-sizing.

Silicon is a type of anode material that is receiving a lot of attention because its total charge capacity is 10 times higher than commercial graphite based lithium ion battery anodes. Consider a packaged battery full-cell. Replacing the commonly used graphite anode with silicon anodes will potentially result in a 63 percent increase of total cell capacity and a battery that is 40 percent lighter and smaller.

The news release then provides a very brief description of the technology,

…, UC Riverside researchers developed a novel structure of three-dimensional silicon decorated cone-shaped carbon nanotube clusters architecture via chemical vapor deposition and inductively coupled plasma treatment.

Lithium ion batteries based on this novel architecture demonstrate a high reversible capacity and excellent cycling stability. The architecture demonstrates excellent electrochemical stability and irreversibility even at high charge and discharge rates, nearly 16 times faster than conventionally used graphite based anodes.

The researchers believe the ultrafast rate of charge and discharge can be attributed to two reasons, said Wei Wang, lead author of the paper.

One, the seamless connection between graphene covered copper foil and carbon nanotubes enhances the active material-current collector contact integrity which facilitates charge and thermal transfer in the electrode system.

Two, the cone-shaped architecture offers small interpenetrating channels for faster electrolyte access into the electrode which may enhance the rate performance.

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

Silicon Decorated Cone Shaped Carbon Nanotube Clusters for Lithium Ion Battery Anodes by Wei Wang, Isaac Ruiz, Kazi Ahmed, Hamed Hosseini Bay, Aaron S. George, Johnny Wang, John Butler, Mihrimah Ozkan, and Cengiz S. Ozkan. Small DOI: 10.1002/smll.201400088 Article first published online: 19 APR 2014

© 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

This paper is behind a paywall.

A new artform: folded lithium-ion batteries made of paper coated with carbon nanotubes

The above image illustrates the architecture of a foldable lithium-ion battery ASU engineers have constructed using paper coated with carbon nanotubes. They began with a porous, lint-free paper towel, coated it with polyvinylidene difluoride to improve adhesion of carbon nanotubes and then immersed the paper into a solution of carbon nanotubes. Powders of lithium titanate oxide and lithium cobalt oxide — standard lithium battery electrodes — are sandwiched between two sheets of the paper. Thin foils of copper and aluminum are placed above and below the sheets of paper to complete the battery.. Courtesy: Arizona State University

The above image illustrates the architecture of a foldable lithium-ion battery ASU engineers have constructed using paper coated with carbon nanotubes. They began with a porous, lint-free paper towel, coated it with polyvinylidene difluoride to improve adhesion of carbon nanotubes and then immersed the paper into a solution of carbon nanotubes. Powders of lithium titanate oxide and lithium cobalt oxide — standard lithium battery electrodes — are sandwiched between two sheets of the paper. Thin foils of copper and aluminum are placed above and below the sheets of paper to complete the battery.. Courtesy: Arizona State University

Despite the fact that I’m wondering about what happened to A (in the illustration), here’s the Oct. 22, 2013 Arizona State University news release by Joe Kullman (h/t Azonano) which describes the ‘origami’ breakthrough,

Arizona State University engineers have constructed a lithium-ion battery using paper coated with carbon nanotubes that provide electrical conductivity.

Using an origami-folding pattern similar to how maps are folded, they folded the paper into a stack of 25 layers, producing a compact, flexible battery that provides significant energy density —  or the amount of energy stored in a given system or space per unit of volume of mass.

Their research paper in the journal Nano Letters has drawn attention from websites that focus on news of technological breakthroughs.

The researchers have also developed a new process to incorporate a polymer binder onto the carbon nanotube-coated paper. The polymer binder improves adhesion of the structure’s active materials.

The achievements open up possibilities of using the origami technique to create new forms of paper-based energy storage devices, including batteries, light-emitting diodes, circuits and transistors, says Candace Chan, who led the research team.

Here’s a link to and a citation for article in Nano Letters,

Folding Paper-Based Lithium-Ion Batteries for Higher Areal Energy Densities by Qian Cheng, Zeming Song, Teng Ma, Bethany B. Smith, Rui Tang, Hongyu Yu, Hanqing Jiang, and Candace K. Chan. Nano Lett., 2013, 13 (10), pp 4969–4974 DOI: 10.1021/nl4030374 Publication Date (Web): September 23, 2013
Copyright © 2013 American Chemical Society

This article is behind a paywall.

Keeping it together—new glue for lithium-ion batteries

Glue isn’t the first component that comes to my mind when discussing ways to make lithium-ion (Li-ion) batteries more efficient but researchers at SLAC National Accelerator Laboratory at Stanford University have proved that the glue used to bind a Li-ion battery together can make a difference to its efficiency (from the Aug. 20, 2013 news item on phys.org),

When it comes to improving the performance of lithium-ion batteries, no part should be overlooked – not even the glue that binds materials together in the cathode, researchers at SLAC and Stanford have found.

Tweaking that material, which binds lithium sulfide and carbon particles together, created a cathode that lasted five times longer than earlier designs, according to a report published last month in Chemical Science. The research results are some of the earliest supported by the Department of Energy’s Joint Center for Energy Storage Research.

“We were very impressed with how important this binder was in improving the lifetime of our experimental battery,” said Yi Cui, an associate professor at SLAC and Stanford who led the research.

The Aug. 19, 2013 SLAC news release by Mike Ross, which originated the news item, provides context for this accidental finding about glue and Li-ion batteries,

Researchers worldwide have been racing to improve lithium-ion batteries, which are one of the most promising technologies for powering increasingly popular devices such as mobile electronics and electric vehicles. In theory, using silicon and sulfur as the active elements in the batteries’ terminals, called the anode and cathode, could allow lithium-ion batteries to store up to five times more energy than today’s best versions. But finding specific forms and formulations of silicon and sulfur that will last for several thousand charge-discharge cycles during real-life use has been difficult.

Cui’s group was exploring how to create a better cathode by using lithium sulfide rather than sulfur. The lithium atoms it contains can provide the ions that shuttle between anode and cathode during the battery’s charge/discharge cycle; this in turn means the battery’s other electrode can be made from a non-lithium material, such as silicon. Unfortunately, lithium sulfide is also electrically insulating, which greatly reduces any battery’s performance. To overcome this, electrically conducting carbon particles can be mixed with the sulfide; a glue-like material – the binder – holds it all together.

Scientists in Cui’s [Yi Cui, an associate professor at SLAC and Stanford who led the research] group devised a new binder that is particularly well-suited for use with a lithium sulfide cathode ­– and that also binds strongly with intermediate polysulfide molecules that dissolve out of the cathode and diminish the battery’s storage capacity and useful lifetime.

The experimental battery using the new binder, known by the initials PVP, retained 94 percent of its original energy-storage capacity after 100 charge/discharge cycles, compared with 72 percent for cells using a conventionally-used binder, known as PVDF. After 500 cycles, the PVP battery still had 69 percent of its initial capacity.

Cui said the improvement was due to PVP’s much stronger affinity for lithium sulfide; together they formed a fine-grained lithium sulfide/carbon composite that made it easier for lithium ions to penetrate and reach all of the active material within the cathode. In contrast, the previous binder, PVDF, caused the composite to grow into large clumps, which hindered the lithium ions’ penetration and ruined the battery within 100 cycles

Even the best batteries lose some energy-storage capacity with each charge/discharge cycle. Researchers aim to reduce such losses as much as possible. Further enhancements to the PVP/lithium sulfide cathode combination will be needed to extend its lifetime to more than 1,000 cycles, but Cui said he finds it encouraging that improving the usually overlooked binder material produced such dramatic benefits.

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

Stable cycling of lithium sulfide cathodes through strong affinity with a bifunctional binder by Zhi Wei Seh, Qianfan Zhang, Weiyang Li, Guangyuan Zheng, Hongbin Yaoa, and Yi Cui. Chem. Sci., 2013,4, 3673-3677 DOI: 10.1039/C3SC51476E First published online 11 Jul 2013

There’s a note on the website stating the article is free but the instructions for accessing the article are confusing seeming to suggest you need a subscription of some sort or you need to register for the site.

I have written about Yi Cui’s work with lithium-ion batteries before including this Jan. 9, 2013 posting, How is an eggshell like a lithium-ion battery?, which also features a news release by Mike Ross.