Leaving lab status: Graphene’s various routes to industrial application

By IM Staff
Published: Friday, 20 March 2015

The commercialisation of graphene is complicated by the many forms in which it can be obtained as well as its multifarious potential applications. Marko Spasenovic takes a look at the present state of the industry and assesses how the material is progressing from the research market to industrial products.

The first production of graphene in a University of Manchester laboratory in 2004 (see pp26-27), using the now famous 'scotch tape’ method, captured the interest of a large body of scientific researchers. 

Nearly all of graphene’s spectacular predicted properties have since been confirmed experimentally. The scotch-tape, or exfoliation production technique, yields graphene of a very high quality, but only in a small quantity, with an area generally of only a few tens of micrometers squared. One would typically be lucky to find several flakes of that size on a 1cm2 substrate. The low yield obtained with the exfoliation method has not been a problem for testing fundamental science, however it would be too small for any conceivable application.

In 2006, researchers succeeded in growing large-area graphene by chemical vapour deposition (CVD), the first method of mass producing graphene. CVD yields almost 100% coverage of metal films with monolayer graphene. The method of CVD growth on metal and subsequent transfer of graphene to various useful substrates has rapidly overcome many hurdles, recently yielding a continuous film of graphene on a 100 metre roll.

The growing number of graphene researchers coupled with the wide accessibility of CVD growth chambers quickly led to a blossoming of the number of companies marketing graphene sheets. The end user has for the most part been the lab researcher, with almost no excursion into the industrial space. 

The primary reason for the relatively slow inclusion of industry has of course been the price of graphene, which is still higher than that of silicon, and orders of magnitude higher than the price of competing transparent conductor material, indium tin oxide (ITO). It is expected that graphene will beat the price of bulk silicon in 2016, but it probably will not match the price of ITO before 2020. Since graphene-based devices could not beat the price of devices based on more mature materials, the young graphene industry has been looking for those applications where graphene can offer novel benefits or unprecedented functionality.

In more recent years, graphene obtained with chemical methods, such as liquid phase exfoliation or the modified Hummers method, has become an instant hit with lab researchers as well as a myriad of companies. Chemically exfoliated graphene is of lower quality than sheet graphene, however it is cheaper to produce and is readily obtained in large volumes. Graphene made using these methods is typically in the form of a powder, which means it can be used as an additive in composites, opening a door to a much larger market than the graphene research space, spreading across the automotive, sporting, construction, aeronautic and other traditional large industries, but also entering developing technologies such as 3D printing, wearable clothing and printed electronics. 

This most recent development pushed graphene closer to real-world applications and ignited a new direction for the market to expand into, enabling a step up in production volumes and a further reduction of the price of graphene.

Graphene2 

Early graphene market  focused on research

The early graphene market (2009-2012) revolved around feeding the appetite of the rapidly growing graphene research community. Probably the first company to offer graphene in its product catalog was Graphene Supermarket, established in 2009 in Calverton, New York State, US. The 'supermarket’ was the sales outpost of Graphene Laboratories, a research startup run by a group of scientists turned entrepreneurs.

Graphene Supermarket offered CVD-grown graphene on copper substrates and on the most commonly used silicon dioxide/silicon (SiO2/Si) substrate, which allows tuning the carrier concentration by back gating. The initial offering was basic, the only other item in the catalog being clean SiO2/Si wafers for customers to do their own exfoliation. However, due to the exploding demand and Graphene Supermarket’s ability to deliver high-quality graphene in a hassle-free manner, the recipe was a highly effective one.

This simple yet effective approach soon spread to Europe and the Far East, with the establishment of Graphenea in Spain in 2010 and Graphene Square in South Korea in early 2012. Together with Graphene Supermarket, these companies managed to quickly master CVD growth and establish themselves as the default graphene suppliers across three continents, setting any latecomers at the disadvantage of having to invent advanced applications for an immature material. 

Still, with the low entry cost of CVD machines (in the order of $100k) and quick maturing of the technology of CVD growth, even these three companies had to keep inventing to alleviate the effect of research labs and universities performing their own CVD growth.

In fact, in the short term of the early graphene market, it turned out to be more profitable to provide CVD chambers themselves than the graphene made in those chambers, as exemplified by the success of Texas, US-based planarTECH. 

planarTECH started in 2012 to sell CVD chambers specially tuned for graphene and by 2014 had already surpassed $1m in revenue (the entire graphene market turnover in 2013 was €6.6m ($6.95m**)). planarTECH aims to double its revenue in 2015. Since similar chambers can be used to grow other monolayer materials such as transition metal dichalcogenides which are gaining popularity, marketing CVD machines should prove to be solid business in the medium term as well.

Overall, there are about 44 graphene producers on the market now, and the graphene news website Graphene Tracker’s business directory contains over 80 entries.

Graphene3 

Recognising the potential of graphene

In the long term, graphene holds enormous potential, but the trick for success lies in recognising the correct applications of each variant of graphene and aligning to the needs of the target customer accordingly. 

Because the applications are so many, as are the forms and variants of the material itself, we have recently witnessed the rise of several group efforts to categorise and organise graphene products, applications and future directions. The most notable of these organisations are the European Graphene Flagship consortium, funded around 50% by the European Commission and 50% by European businesses, and the Graphene Stakeholders Association, a US-based non-profit organisation. The Flagship has been selected as one of two of Europe’s key Future Emerging Technologies (FETs), with a promise of €1bn in funding across 10 years.

Early this year, the Graphene Flagship published its science and technology roadmap, targeting research areas designed to take graphene and related 2D materials from academic laboratories into society.

Clearly, the majority of the application basis will be completed in about a decade, but we expect to see a growth of niche applications in which graphene enhances existing products throughout the years. 

There is very little graphene in end-user products at present, but that has been changing in recent years, and even months. Although there have been rumors recently about Samsung mobile devices using graphene as part of their touchscreen, there has been no official confirmation of this from Samsung. 

The first commercial product to contain any graphene was the HEAD Graphene Speed Pro tennis racket, introduced in 2013. The racket was at that time being promoted by the likes of top Serbian tennis player Novak Djokovic and Russia’s Maria Sharapova, giving a boost to graphene’s already immense popularity. The inclusion of a small amount of graphene apparently made certain regions of the rackets lighter, giving the player’s swing more power. HEAD seems to be satisfied with the success of graphene, having recently launched the JOY range of skis, which also incorporate the nanocarbon.

Generally the trend of using graphene in sports equipment is expected to continue, given the material’s low density (which is made even smaller in specialty nanostructures such as the graphene aerogel), excellent flexibility and durability.

Another application area that graphene has excelled in is conductive ink technology. Vorbeck is the pioneer in this field, having first introduced Vor-Ink, following up with Vor-Power (flexible battery, presented in the form of a bag strap), Vor-Flex (graphene-enhanced durable rubber) and Vor-Tag (RFID tags). The company has partnered with Crawford composites to produce a prototype formula race car enhanced by graphene, sporting graphene tyres, batteries, antennae, body, printed on-wheel circuitry, and various sensors. Clearly, the car is a prototype, aimed at popularising graphene and showcasing its potential reach, but the technology is simply too expensive at the moment to be applied in commercial products. Nevertheless, defence applications are sure to follow in the near term, with civilian use arriving shortly after that.

Graphene1 

Sports equipment maker HEAD used tennis stars Maria Sharapova
(pictured) and Novak Djokovic to promote its graphene-doped tennis rackets.
Marianne Bevis

Predicting market volumes

Given graphene’s relatively young age and limited current commercial use, it is hard or impossible to predict future market volumes to any reasonable accuracy. Adding to the difficulty is the lack of standardisation for graphene, with the name being loosely applied to an entire spectrum of materials ranging from monolayer atomic sheets of carbon to crumpled-up carbon-based microparticles. 

The first of these is expected to be of great use in microelectronics, sensing, and transparent flexible electronics, whereas materials closer to the large side of that spectrum should open up novel applications in 3D printing, flexible batteries, enhanced composites, construction, aerospace and the automotive industry, amongst others.

Nevertheless, there have been a few estimates of the potential size of the graphene market in the coming years. These include $150m in 2020, with a $43m share in North America, according to Allied Market Research, and $400m in 2024 on the material level, up from $20m in 2014, according to IDTechEx. However, these numbers address only
the amount of raw material sold, and do not include the potentially enormous expansion of user industries. 

For example, Research and Markets predicts 3D printing to grow from $2bn in 2012 to $12bn in 2020. IDTechEx predicts that wearable technology will grow at a similar or slightly faster pace. If graphene were to be used by these two industries in the same proportion as it is today, and assuming that the same kind of expansion occurs in all other graphene user industries, this would mean that over the next decade, the market for graphene would grow to around six- or sevenfold its present size, putting the value of the volume sold at $100-150m. Of course, one would expect new applications to arise and if graphene manages to gain supremacy over other technologies for at least one of these applications, the market volume could explode to several billion dollars.

Taking advantage of the disproportionate hype-to-current-market-volume ratio, there have been several attempts to form "graphene investment funds" or similar "get rich quick" schemes, even including proposals to buy graphene and store it in a warehouse for future resale. 

But graphene is not a commodity and its price is bound to decrease with time. It is a very exciting nanomaterial with many potential uses, however it requires strong technical expertise and top-notch business skills to make and sell.

To conclude, graphene is a supremely interesting material, with potential impact on most of our daily lives. That said, the material’s present early stage of development means that graphene has been used mostly for research purposes, with real-world applications just starting to emerge. In a rapidly changing world with disruptive technologies being invented by the day, it is hard to predict exactly how and how much graphene will be used, but it seems certain that graphene and related materials will enhance everything from paper to space shuttles to gizmos that are hard to imagine today. Investing in graphene is therefore a tough call, which will require careful analysis and plenty of patience.

*Marko Spasenovic holds a PhD in Physics from the University of Twente, the Netherlands. He is the founder, owner and administrator of Graphene Tracker, a graphene business news website. He is also Assistant Professor at the Institute of Physics in Belgrade, Serbia, as well as blogger and online content manager for Graphenea and is on the Advisory Board of the Graphene Stakeholders Association.

**Conversion made March 2015