Arguments
G R A P H E N E
Posted on 10 November 2015 by Riduna
Have you heard of Sir Andre Geim?
You should have heard of him. In 2004 he, together with his research colleague Sir Konstantin Novoselov, made what is likely to prove the most momentous achievement of the 21st century. They isolated the 2 dimensional material graphene, identified many of its extraordinary properties and subsequently described other 2 dimensional materials. Their work is of such importance that both were awarded the 2010 Nobel Prize in Physics, knighted by the Queen and by the King of the Netherlands and over the past decade have been showered with numerous honours and awards.
Properties
Graphene does not occur naturally. It is produced from pure graphite by stripping away layers of the material until left with a single layer – a feat initially achieved using adhesive tape. It comprises atoms of carbon linked together in a hexagonal pattern forming a sheet one atom (0.35 nm) thick. 1 gram of graphene is sufficient to cover an area of 2,630 square metres and one square metre weighs 0.77 milligrams.
Fig. 1 Atomic structure of graphene. Each atom in the hexagon lattice is only 0.14 nm apart, preventing passage of any molecule. Source: Wikipedia.
It is a very stable, chemically inert material which has x200 the strength of steel yet is malleable - its surface area can be stretched by 20%. It can be folded and crumpled, vastly increasing its surface area within the confines of a very small space. Graphene is an excellent thermal conductor and in its pure form is 97.7% transparent.
Inability to produce graphene on an industrial scale initially limited development of technology into an ever-growing range of applications. These problems have now been overcome, even to the extent that a graphene ink has been developed enabling the printing of graphene sheets and other items containing graphene. Sir Andre rightly describes Graphene as the foundation of far reaching disruptive technology. It has the potential to replace and bring about the rapid demise of fossil fuels as an energy source, possibly within a decade and this alone justifies its description as a ‘wonder material’.
Solar Panels
The best commercially available photovoltaic panels are silicon based and have an efficiency of ~21%. The best efficiency in converting photons in sunlight to an electron flow was 25.6% achieved with crystalline silicon photovoltaic cells, a record held until December 2014 when multi-junction cells achieved efficiency of 46%, the present record. Subsequent research shows that graphene absorbs photons from a wider spectrum of sunlight and that each photon absorbed produces multiple electrons indicating the possibility of achieving an efficiency of 60% without the need for solar concentration.
It is likely that photovoltaic cells with an efficiency x2 that of cells presently in use could be widely available by 2020. It is probable that development of graphene solar cells may also be commercialized by then. They will revolutionize solar panel cost-efficiency and significantly reduce the cost of generating electricity from sunlight, adding to their competitive advantage over fossil fuelled power stations.
Solar panel power stations would then have telling advantages over fossil fuelled generators because: 1) their capital cost is far less, 2) operating costs are far less since their fuel, sunlight, is free, 3) maintenance costs are low because solar panels are durable and easily replaced and 4) they are not limited to being located near a fossil fuel source but can be located anywhere and supply either a national or local grid. However, unlike fossil fuelled power stations, they would still not be able to provide power 24/7 without durable and cost-efficient energy storage, probably in excess of 24 hours supply.
Electricity Storage
Graphene has already been used to vastly improve the recharge time (reportedly 15 minutes) and increased the capacity (by as much as x10) of Lithium batteries, supercapacitors and recently developed supercapacitor-battery hybrids. Testing of holey graphene oxide shows ultra-high capacitances of 283 Farads/gram and 234 Farads/cm3. By combining graphene with Manganese Dioxide (MnO2) capacitance of 1,100 Farads/ cm3 have been achieved. 
Fig. 2 Holey Graphene is a 3D material that has tiny holes in it. Close-up view of framework film; arrows highlight ion-transport pathway short-cut. Source: NanoWerk and Graphene Info
UCLA researchers have developed a new graphene based material, holey graphene, enabling production of a capacitor that has unparalleled energy density, x10 that of currently available supercapacitors. Holey graphene features superior electrical conductivity, exceptional mechanical flexibility and unique hierarchical porosity, making it ideal for use as a cathode in electro-chemical capacitors and batteries. These characteristics may give some credence to claims that a 10,000 Farad ultra-supercapacitor, smaller than a paperback book, has been produced – a major development if true and one with revolutionary potential for electric propulsion.
Less clear is the period required for commercialization of these achievements. The commercial imperative is to take the market from Tesla’s PowerWall (now selling) and Porsches 500km/charge sports car (coming), with graphene based products. With superior durability, storage capacity and the best recharge time for any supercapacitor-battery hybrid it seems possible that graphene competition in the world market could begin in 2018, possibly sooner. It could be well established, offering vastly improved, efficient and very competitively priced energy storage products by 2025.
Over the following decade, this is likely to have two far reaching effects: a) It will be possible to store large amounts of electricity more efficiently generated from solar energy by more efficient solar panels and: b) the range, recharge time and reliability of electric vehicles (EV’s) of all descriptions will be vastly improved and much cheaper.
Effect on Power Stations
By using enhanced solar panels, power stations will be able to generate and store electricity in sufficient quantity to ensure continuous 24/7 supply to a local or national grid and do so more cheaply and cleanly than fossil fuels. Fossil fuelled power stations are likely to be rapidly replaced and production of their fuel will decline with similar rapidity, leaving both as stranded assets of low or no commercial value.
Existing fossil fuelled power stations in Australia are now largely fully amortised. Given the advances described above, it is unlikely that any will be replaced, other than by solar power stations. New fossil fuelled power stations are most unlikely to be built.
Effect on Oil Refining
The Oil Industry will only flourish as long as constraints on use of EV’s remain in place. They are vehicle price (at present often double for EV’s), refueling time (over 40 hours from standard mains) and kilometres per charge (usually under 200 km. only Tesla offers 450 km). The price for EV’s is so high because of the cost of its batteries but availability of relatively inexpensive graphene batteries and supercapacitors immediately overcome these constraints.
By 2020 it is likely that graphene batteries and supercapacitors will store sufficient electricity to enable an EV to accelerate rapidly, travel at least 500 km on a single charge and recharge in a time dictated largely by available current supply. As soon as these vehicles become available to the public, uptake will be rapid, market driven and by 2025 EV’s could be the vehicle of choice. It is possible that by 2030 most passenger vehicles propelled by an internal combustion engine will have been consigned to history.
It is reasonable to expect that from 2020-2030 demand for crude oil and oil based motor fuels will decline and be accompanied by contraction in the number of refineries engaged in fuel production.
Conclusion
As long as profit is to be made from production and use of fossil fuels they will be exploited. Even if some governments attempt to curb emissions, others will not. Even if global agreement on limiting emissions is achieved, implementation is unlikely to be.
The only way to curb production of fossil fuels and ultimately end their use is to replace them with an affordable, reliable alternative. That alternative is electricity generated from an emissions-free source, possibly from Generation IV nuclear reactors, certainly and more likely from solar energy because it is free of radio-active waste and its fuel is free.
To-date, the constraint on renewable energy remains a cost-effective way of storing electricity in sufficient quantity to provide 24/7 supply or, in the case of transport, to ensure readily available, rapid recharge after a vehicle has travelled a minimum of 500 km/charge. As outlined above, graphene technology has the potential to remove these constraints.
Commercialisation of graphene technology has begun and is continuing to make advances which are likely to see the electric motor (95% efficient) replace the internal combustion engine (20% efficient) and fossil fuelled power stations in the 2020’s. These disruptions could be largely completed by 2030 followed by clean electrification of the most demanding of industries and equipment.
The fundamental reason why graphene technology will succeed is displacing fossil fuels, where other technologies have failed, is because of the extraordinary properties of graphene and its composites. These make it comparatively efficient in the generation and storage of electricity and, for many other applications, it is a cheaper and more versatile material.
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"The only way to curb production of fossil fuels and ultimately end their use is to replace them with an affordable, reliable alternative."
Certainly, this is an important element in moving away from ffs. But we also need to increase efficiency and decrease total use. As Kevin Anderson has pointed out, these can be done much more quickly and radically than a build out of a whole new energy generation system. And time is one thing we don't really have enough of!
www.youtube.com/watch?feature=player_embedded&v=KumLH9kOpOI
"Graphene does not occur naturally"
Does that mean it can't be broken down by natural processes? Don't we already have problems with pollution from nano-tubes etc. Is this going to add to that problem?
According to the paper about the discovery of superconducting lithium decorated monolayer graphene, it is superconducting at 5.9 K.
http://arxiv.org/abs/1508.05925
[PS] Fixed Link, html.
When I was in college, a common saying was that it was not too urgent to quit smoking, because science was about ready to bring us "safe" cigarettes. And when I was in high school, Lewis Strauss, Chairman of the Atomic Energy Commission, promised us "electricity too cheap to meter." And we hear about the limitless inexpensive energy we'll get from fusion power.
"Graphene Power" might well be the answer to the billion+ maidens' prayers. But time scales for implementation? I fear that under the best of lucky-but-reality-based dreams, we gotta quit smoking, diet, exercise, drink more water and less alcohol... and walk/bike/bus, wear long underwear in season, etc.
2,630 m2/g seems ~right based on the calculation I've done using Avogardo constant (2.022E23 atoms per mole, i.e. 12g in case of C)
But 0.77 mg per m2 looks like a mistake. 1000mg over 2,630 m2 reduces to 0.38mg over 1 m2. Unless "1 m2" cannot exist in a single layer but for a strange reason, two layers are needed.
Typo in my previous post: of course Avogardo constant is 6.022E23 atoms per mole
And what will the Koch brothers do to stop this technology?
As Ed pointed out - 5.9K - a wee bit cooler than most rooms. Still, it's good to know there is innovation in the pipeline with the potential to make electric ships, trucks and planes as well as cars, solar homes and businesses not merely possible but the superior option. Not all innovation makes it to commercialisation let alone ubiquitous utilisation but there is no sign that the well is drying out.
http://www.nano.northwestern.edu/research/carbon-nanotubes-and-graphene
Perhaps I am mistaken but if carbon nanos are graphene, then how is the toxicity to human cells going to be overcome?
[PS] fixed link, but carbon nanotubes are not graphene. A link concerning potential toxicity from applications as discussed would be more useful.
chriskoz – I don't know. The literature does not show how graphene mass is calculated. It may be as you suggest that mass can only be calculated for a 3D material, or it may be due to each hexagonal containing only 2 atoms. I have e-mailed Manachester University seeking clarification.
Ken in Oz@8
I would not be so optimistic about all electric transport including trucks & planes.
For starters, the energy density of 10kF supercapacitor weighing as muchs a "paperback book" (let's give it a mass of half pounr or 250g) and maximum voltage say 3V (most supercapacitor support even max breakdown voltage of 2.7V and this one seems no exception, Riduna please confirm), the energy yield is:
1/2 * 10kF * (3V)2
which is 45kJ per 250g or 0.18MJ/kg (I think I've overestimated it but Riduna might provide that detail, missing in the original OP)
which is still behind the existing battery technologies (e.g. Li-Ion up to 0.875MJ/kg) and far behind the miraculous energy density of burning petrol (44.4MJ/kg) or gas or other liquid FF.
https://en.wikipedia.org/wiki/Energy_density
So while graphene may be an important step forward in energy storage technology (I'm especially excited about the prospect of superfast recharge of say 15mins in an average EV), it is not a universal solution to all transportation at this stage. You cannot load 100 tons of charged graphene on board of a jumbo jet and expect it to fly a few Mm between continents or fill in a 100t truck or 1000t train and expect it to roll for 1 Mm accross the desert. There is simply not enough energy for that. FFs are the only realistic sorces of energy in those scenarios.
"The Oil Industry will only flourish as long as constraints on use of EV’s remain in place. They are vehicle price (at present often double for EV’s), refueling time (over 40 hours from standard mains) and kilometres per charge (usually under 200 km."
Here in Australia, there are a few EV's at attainable prices: The Leaf and the BMW i3 for example. Both of those vehicles charge to full in a few (6-8) hours from standard 240v 10A power points, so easily overnight. Not sure where you found 40 hours? With a 32A EVSE, the i3 charges in under 4 hours, and with the DC charge option it charges to 80% in 20 minutes. (well, once DC chargers become common)
Less than 200km range is the current norm, and it does cause range anxiety until you actually use an EV. Most commuters travel way less than 100km in a day, so having less than 200km is hardly a big issue for most. The owner involvement in refuelling the EV is a minute at home (just plug it in) Compare that to your FF vehicle. If your trip is 50-60km, why would you need to lug around a large vehicle with a 450km battery like the Tesla?
I'm sure that as battery tech improves we will see greater range on these EV's. Nissan is apparently about to release an extended range Leaf to solve the range anxiety issue.
" FFs are the only realistic sorces of energy in those scenarios."
If you are only going to liquid fuels for planes and trains, then biofuels are an alternative. Lot of work going into woody feedstock. Just a little matter of pricing...
Andrew:
The fastest trains in the world are electric. You just have to think differently. Many jobs currently done by trucks could be done using electric trains. Trucks could do the short haul. Just because it is not how we do it now does not mean that it cannot be done.
If we could get rid of subsidies for coal and other fossil fuels, this and other types of green electric generation and storage would happen more quickly. Or, we could help Dr. James Hansen.
Dr. James Hansen, from NASA says, “Most impressive is the work of Citizens’ Climate Lobby… If you want to join the fight to save the planet, to save creation for your grandchildren, there is no more effective step you could take than becoming an active member of this group.”
A revenue neutral fossil fuel tax (that increases every year) and dividend law would create 2.1 million jobs in ten years - not hurt the economy.
To learn more about the tax carbon, pay people plan, (and hopefully join us) click here: https://citizensclimatelobby.org/carbon-fee-and-dividend/
The issue with subsidies for fossil fools is: ..THAT OF GREASING THE PALMS OF INDUSTRY...aka: TOO BIG TOO FAIL!
[JH] The use of "all caps" constitutes shouting and is prohibited by the SkS Comments Policy.
@ 11,
So not even graphene will make electric airplane travel possible?
Graphene is a technology that is still in the laboratory and like so many similar technologies is surrounded by all the hype which is employed to attract the attention of the movers & shakers. The technology is at the point of demonstrating laboratory devises comparable in weight to lead-acid batteries but being capacitors rather than batteries they have blindingly fast charge/discharge rates. This achievement allows talk of matching lithium-ion batteries for weight, although such batteries are themselves also a developing technology. Yet rapid charging rates make the total on-vehicle capacity of graphene capacitors (and thus its weight) a different priority than it is for batteries. I don't think graphene is being seen anywhere as powering airliners. However there is another very interesting applcation mentioned in this SkS post. Being made of carbon rather than lead, the technology could be more amenable to scaling up in capacity to allow the useful storage of renewable power and enabling that 24/7 supply.
Regarding ultracapacitors, batteries, etc - the best solution for electric transportation will likely be a mix. Hybrid electric storage designs have a lot of advantages.
A combination of the two permits complete regenerative braking and avoids oversizing battery packs for acceleration - a win-win situation.
Ultracapacitors are currently in use on about 1 million 'micro-hybrid' cars to run stop/start cycles, where the fossil fuel engine is shut down when stopped instead of idling in traffic.
Katesisco @ 9– The US Materials Safety Data Sheet warns against inhalation of pure graphine particulates (dust) which causes cellular damage in the lungs resulting in emphysema. It describes skin and eye contact with dust as a mild irritant and gives no information on carcinogenic effects, if any. More work on its industrial use is needed since it does not address graphene compounds.
[PS] A reference would help please.
Some graphene related MSDS:
Graphene
Graphene films on SiO2/Si substrate:
Graphene oxide:
Reduced Graphene Oxide:
Graphene Films, TEM grid:
The upshot appears to be that there is no evidence of significant toxicity from graphene itself, although doping agents can make it toxic. It does act as an irritant (as does any fine dust), but that is not a major problem.
I'm worried by the possibilty that cells could be damaged by the phsical presence of sharp particles in similar ways to asbestos. For now I think it wight be a good idea to use similar precautions to those used in dealing with asbestos. There is the potential for cancers which take a long time to develop,
MA Rodger @ 18. … Graphene is a technology that is still in the laboratory
Difficult to say because for commercial reasons, its users tend not to announce their activities. Market demand for significantly improved energy storage and the huge profits to be made from its provision, makes it likely that commercial use of graphene technology will occur sooner than later. A 15 year time span for its wide commercialization is an informed guess. It may be wrong.
That Tesla batteries will use graphene technology is speculative – we don’t know. That Porsche will use graphene in batteries for its ‘Mission E’ (2018) sportscar is more likely given its claim of a 15 minute recharge time (1). The explicit statement of Sunvault-Edison that it will use graphene technology to power its Electron-1 car, (2016) if true, may indicate early commercialization (2).
(1) http://www.drive.com.au/it-pro/porsche-unveils-allelectric-mission-e-sports-car-20150916-gjog22.
(2) http://www.teslamotorsclub.com/showthread.php/52844-Edison-Electron-One
I want to reinforce the comment of Mark Welsch @15. There's no need to wait until graphene is commercialized. In some locations, renewable energy with current technology (wind, solar) is already better than fossil-fuel energy in terms of price. With a gentle push from a steadily rising fee on fossil fuels, based on their CO2 emissions, and with all of the fee revenue (minus a few percent for administration) being returned to legal residents on a per capita basis to cushion against the rising price of energy, renewable energy will gradually become the superior energy choice throughout the world. By joining and working with Citizens' Climate Lobby (CCL), everyone reading this post can contribute to this essential acceleration of the transition away from fossil fuels. Since I joined CCL last April, I've been increasingly impressed by the quality and effectiveness of its work. It's a non-partisan, international organization that, in the United States, works constructively with both Republicans and Democrats. I'm optimistic that it will succeed in getting "carbon fee and dividend" legislation passed in the United States, even in a Republican-dominated Congress, within the next few year. By joining and working with CCL, you can help accelerate this process.
Ed Wiebe @ 3 icorrectly points out that Superconductivity of Graphene coated with Lithium is achieved at K5.9, not room temperature.
The sentence: ‘When coated with Lithium it becomes a superconductor, having no resistance to an electric current at room temperature’ is wrong and the text has been modified to show deletion of the sentence.
The current global fleet of 90000 cargo vessels consumes a high proportion of the oil that is being extracted around the globe by various means. Global trade and so the economies of many countries is very dependent on this unsustainabel transportation process. Focussing on the selected role of graphene does not contribute to tackling this emerging major predicament or to the other ones, over population, unsustainable food and potable water supply, global warming and ocean acidifcation are warming together with replacing the thousands of jet powered aircraft, including airliners.
It is open to question as to whether the innovative technology described here will have a significant impact on the inevitable powering down of civilization as the predicamnts hit hard in coming decades.
Graphene technology certainly does not - and can not - address the rapidly growing problem of population increase or the pressure this puts on the food supply required for their survival. However, it may provide clean water through its potential use as a membrane filter. Graphene technology is not claimed to be a universal panacea. It may slow but will not stop carbon emissions from a warming Arctic.
Given the present state of technology, it is difficult to see graphene technology replacing aviation fuel with stored electric energy. On the other hand, pending this development, it is possible to replace fossil fuel with bio-fuel. Graphene does have potential to slow, possibly reduce, ocean acidification by reducing greenhouse gas emissions.
The essay examines the potential for graphene technology to displace fossil fuel for electricity generation and storage, land transport and, eventually, on vessels now dependent on bunker oil for propulsion. It will be developed. If it is not, there appears to be no other candidate able to displace fossil fuels. The consequences of not displacing them may make large parts of the globe uninhabitable by our species.
In #13, scaddenp mentioned biofuels as a source of energy for jets. The following may be of interest...
"We used a chemical process called olefin metathesis, which earned its developers, Robert Grubbs and Richard Schrock, the Nobel Prize in Chemistry in 2005. In our newly published study, we showed that it selectively cleaves carbon-carbon double bonds of alkenones. The double bonds—and hence the cleaving—are ideally positioned in alkenones to produce fragments with shorter lengths similar to compounds used for fossil-based jet fuels."
Jet Fuel from Algae?
Scientists probe fuel potential in common ocean plant
By Chris Reddy, Greg O'Neil :: Originally published online January 28, 2015
http://www.whoi.edu/oceanus/feature/jet-fuel-from-algae
And yes, currently price would appear to be a bit of a problem:
"So we have isolated alkenones as a product with biodiesel oils and can use these unusual compounds made by a common algae to produce jet fuel. But based on the current cost of Isochrysis sold by a handful of vendors for purpose of shellfish feed (about $400 per kilogram), the fuels we have produced would cost at least $10,000 per gallon."
O'Neil, Gregory W., et al. "Production of jet fuel range hydrocarbons as a coproduct of algal biodiesel by butenolysis of long-chain alkenones." Energy & Fuels 29.2 (2015): 922-930.
http://pubs.acs.org/doi/abs/10.1021/ef502617z
MA Rodger @ 18 suggests that graphene technology has yet to leave the lab. However, graphene technology is leaving the lab and being commercialized. Evidence of this is provided by the decision of Grapheno to produce batteries using graphene polymer in electrodes at a new 7,000 m2 factory in Spain(1). The batteries are reported to be ~5 times more efficient than existing batteries.
(1) http://www.graphene-info.com/graphenano-announces-launch-manufacturing-plant-graphene-based-batteries