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Tuesday, November 30, 2021

Hydrogen vehicle

From Wikipedia, the free encyclopedia
 
The 2015 Toyota Mirai is one of the first hydrogen fuel cell vehicles to be sold commercially. The Mirai is based on the Toyota fuel cell vehicle (FCV) concept car (shown).

A hydrogen vehicle is a type of alternative fuel vehicle that uses hydrogen fuel for motive power. Hydrogen vehicles include hydrogen-fueled space rockets, as well as automobiles and other transportation vehicles. Power is generated by converting the chemical energy of hydrogen to mechanical energy, either by reacting hydrogen with oxygen in a fuel cell to power electric motors or, less commonly, by burning hydrogen in an internal combustion engine.

As of 2021, there are two models of hydrogen cars publicly available in select markets: the Toyota Mirai (2014–), which is the world's first mass-produced dedicated fuel cell electric vehicle (FCEV), and the Hyundai Nexo (2018–). The Honda Clarity was produced from 2016 to 2021. Most companies that had been testing hydrogen cars have switched to battery electric cars; Volkswagen has expressed that the technology has no future in the automotive space, mainly because a fuel cell electric vehicle consumes about three times more energy than a battery electric car for each mile driven. As of December 2020, there were 31,225 passenger FCEVs powered with hydrogen on the world's roads.

As of 2019, 98% of hydrogen is produced by steam methane reforming, which emits carbon monoxide. It can be produced by thermochemical or pyrolytic means using renewable feedstocks, but the processes are currently expensive. Various technologies are being developed that aim to deliver costs low enough, and quantities great enough, to compete with hydrogen production using natural gas.

The benefits of hydrogen technology are fast refueling time (comparable to gasoline) and long driving range on a single tank. The drawbacks of hydrogen use are high carbon emissions when hydrogen is produced from natural gas, capital cost burden, low energy content per unit volume at ambient conditions, production and compression of hydrogen, the investment required in filling stations to dispense hydrogen, transportation of hydrogen to filling stations, and lack of ability to produce or dispense hydrogen at home.

Vehicles

Honda FCX Clarity, a hydrogen fuel cell demonstration vehicle introduced in 2008

Automobiles, buses, forklifts, trains, PHB bicycles, canal boats, cargo bikes, golf carts, motorcycles, wheelchairs, ships, aeroplanes, submarines, and rockets can already run on hydrogen, in various forms. NASA used hydrogen to launch Space Shuttles into space. A working toy model car runs on solar power, using a regenerative fuel cell to store energy in the form of hydrogen and oxygen gas. It can then convert the fuel back into water to release the solar energy. Since the advent of hydraulic fracturing the key concern for hydrogen fuel cell vehicles is consumer and public policy confusion concerning the adoption of natural gas powered hydrogen vehicles with heavy hidden emissions to the detriment of environmentally friendly transportation.

Automobiles

As of 2021, there are two hydrogen cars publicly available in select markets: the Toyota Mirai and the Hyundai Nexo. The Honda Clarity was produced from 2016 to 2021.

The Hyundai Nexo is a hydrogen fuel cell-powered crossover SUV

In 2013 the Hyundai Tucson FCEV was launched, it was a conversion of the Tucson and available in left-hand drive only and became the first commercially mass-produced vehicle of its type in the world. Hyundai Nexo, which succeeded the Tucson in 2018, was selected as the "safest SUV" by the Euro NCAP in 2018 and was rated as "Good" in a side crash test conducted by the Insurance Institute for Highway Safety (IIHS)

Toyota launched the world's first dedicated mass-produced fuel cell vehicle (FCV), the Mirai, in Japan at the end of 2014 and began sales in California, mainly the Los Angeles area and also in selected markets in Europe, the UK, Germany and Denmark later in 2015. The car has a range of 312 mi (502 km) and takes about five minutes to refill its hydrogen tank. The initial sale price in Japan was about 7 million yen ($69,000). Former European Parliament President Pat Cox estimated that Toyota would initially lose about $100,000 on each Mirai sold. At the end of 2019, Toyota had sold over 10,000 Mirais. Many automobile companies have introduced demonstration models in limited numbers (see List of fuel cell vehicles and List of hydrogen internal combustion engine vehicles).

In 2013 BMW leased hydrogen technology from Toyota, and a group formed by Ford Motor Company, Daimler AG, and Nissan announced a collaboration on hydrogen technology development. By 2017, however, Daimler had abandoned hydrogen vehicle development, and most of the automobile companies developing hydrogen cars had switched their focus to battery electric vehicles. By 2020, all but three automobile companies had abandoned plans to manufacture hydrogen cars.

Auto racing

A record of 207.297 miles per hour (333.612 km/h) was set by a prototype Ford Fusion Hydrogen 999 Fuel Cell Race Car at the Bonneville Salt Flats, in August 2007, using a large compressed oxygen tank to increase power. The land-speed record for a hydrogen-powered vehicle of 286.476 miles per hour (461.038 km/h) was set by Ohio State University's Buckeye Bullet 2, which achieved a "flying-mile" speed of 280.007 miles per hour (450.628 km/h) at the Bonneville Salt Flats in August 2008.

In 2007, the Hydrogen Electric Racing Federation was formed as a racing organization for hydrogen fuel cell-powered vehicles. The organization sponsored the Hydrogen 500, a 500-mile race.

Buses

Solaris Urbino 12 bus near the factory In Bolechowo, Poland

Fuel-cell buses are being trialed by several manufacturers in different locations, for example, the Ursus Lublin. Solaris Bus & Coach introduced its Urbino 12 hydrogen electric buses in 2019. Several dozen have been ordered and are expected to be delivered in 2020 and 2021.

Trams and trains

In March 2015, China South Rail Corporation (CSR) demonstrated the world's first hydrogen fuel cell-powered tramcar at an assembly facility in Qingdao. The chief engineer of the CSR subsidiary CSR Sifang Co Ltd., Liang Jianying, said that the company is studying how to reduce the running costs of the tram. Tracks for the new vehicle have been built in seven Chinese cities. China plans to spend 200 billion yuan ($32 billion) through 2020 to increase tram tracks to more than 1,200 miles.

In northern Germany in 2018 the first fuel-cell powered Coradia iLint trains were placed into service; excess power is stored in lithium-ion batteries.

An experimental "Hydroflex" train, British Rail Class 799, began tests in Great Britain in June 2019.

Ships

As of 2019 Hydrogen fuel cells are not suitable for propulsion in large long-distance ships, but they are being considered as a range-extender for smaller, short-distance, low-speed electric vessels, such as ferries. Hydrogen in ammonia is being considered as a long-distance fuel.

Bicycles

PHB hydrogen bicycle

In 2007, Pearl Hydrogen Power Source Technology Co of Shanghai, China, demonstrated a PHB hydrogen bicycle. In 2014, Australian scientists from the University of New South Wales presented their Hy-Cycle model. The same year, Canyon Bicycles started to work on the Eco Speed concept bicycle.

In 2017, Pragma Industries of France developed a bicycle that was able to travel 100 km on a single hydrogen cylinder. In 2019, Pragma announced that the product, "Alpha Bike", has been improved to offer an electrically assisted pedalling range of 150 km, and the first 200 of the bikes are to be provided to journalists covering the 45th G7 summit in Biarritz, France. If successful, Lloyd Alter of TreeHugger responded to the announcement, asking "why … go through the trouble of using electricity to make hydrogen, only to turn it back into electricity to charge a battery to run the e-bike [or] pick a fuel that needs an expensive filling station that can only handle 35 bikes a day, when you can charge a battery powered bike anywhere. [If] you were a captive fleet operator, why [not] just swap out batteries to get the range and the fast turnover?"

Military vehicles

General Motors' military division, GM Defense, focuses on hydrogen fuel cell vehicles. Its SURUS (Silent Utility Rover Universal Superstructure) is a flexible fuel cell electric platform with autonomous capabilities. Since April 2017, the U.S. Army has been testing the commercial Chevrolet Colorado ZH2 on its U.S. bases to determine the viability of hydrogen-powered vehicles in military mission tactical environments.

Motorcycles and scooters

ENV develops electric motorcycles powered by a hydrogen fuel cell, including the Crosscage and Biplane. Other manufacturers as Vectrix are working on hydrogen scooters. Finally, hydrogen-fuel-cell-electric-hybrid scooters are being made such as the Suzuki Burgman fuel-cell scooter and the FHybrid. The Burgman received "whole vehicle type" approval in the EU. The Taiwanese company APFCT conducted a live street test with 80 fuel-cell scooters for Taiwan's Bureau of Energy.

Auto rickshaws

Hydrogen auto rickshaw concept vehicles have been built by Mahindra HyAlfa and Bajaj Auto.

Quads and tractors

Autostudi S.r.l's H-Due is a hydrogen-powered quad, capable of transporting 1-3 passengers. A concept for a hydrogen-powered tractor has been proposed.

Aeroplanes

The Boeing Fuel Cell Demonstrator powered by a hydrogen fuel cell

Companies such as Boeing, Lange Aviation, and the German Aerospace Center pursue hydrogen as fuel for manned and unmanned aeroplanes. In February 2008 Boeing tested a manned flight of a small aircraft powered by a hydrogen fuel cell. Unmanned hydrogen planes have also been tested. For large passenger aeroplanes, The Times reported that "Boeing said that hydrogen fuel cells were unlikely to power the engines of large passenger jet aeroplanes but could be used as backup or auxiliary power units onboard."

In July 2010, Boeing unveiled its hydrogen-powered Phantom Eye UAV, powered by two Ford internal-combustion engines that have been converted to run on hydrogen.

In Britain, the Reaction Engines A2 has been proposed to use the thermodynamic properties of liquid hydrogen to achieve very high speed, long distance (antipodal) flight by burning it in a precooled jet engine.

Fork trucks

A hydrogen internal combustion engine (or "HICE") forklift or HICE lift truck is a hydrogen fueled, internal combustion engine-powered industrial forklift truck used for lifting and transporting materials. The first production HICE forklift truck based on the Linde X39 Diesel was presented at an exposition in Hannover on May 27, 2008. It used a 2.0 litre, 43 kW (58 hp) diesel internal combustion engine converted to use hydrogen as a fuel with the use of a compressor and direct injection.

A fuel cell forklift (also called a fuel cell lift truck) is a fuel cell powered industrial forklift truck. In 2013 there were over 4,000 fuel cell forklifts used in material handling in the US. The global market was estimated at 1 million fuel cell powered forklifts per year for 2014–2016. Fleets are being operated by companies around the world. Pike Research stated in 2011 that fuel-cell-powered forklifts will be the largest driver of hydrogen fuel demand by 2020.

Most companies in Europe and the US do not use petroleum powered forklifts, as these vehicles work indoors where emissions must be controlled and instead use electric forklifts. Fuel-cell-powered forklifts can provide benefits over battery powered forklifts as they can be refueled in 3 minutes. They can be used in refrigerated warehouses, as their performance is not degraded by lower temperatures. The fuel cell units are often designed as drop-in replacements.

Rockets

Many large rockets use liquid hydrogen as fuel, with liquid oxygen as an oxidizer (LH2/LOX). An advantage of hydrogen rocket fuel is the high effective exhaust velocity compared to kerosene/LOX or UDMH/NTO engines. According to the Tsiolkovsky rocket equation, a rocket with higher exhaust velocity uses less propellant to accelerate. Also the energy density of hydrogen is greater than any other fuel. LH2/LOX also yields the greatest efficiency in relation to the amount of propellant consumed, of any known rocket propellant.

A disadvantage of LH2/LOX engines is the low density and low temperature of liquid hydrogen, which means bigger and insulated and thus heavier fuel tanks are needed. This increases the rocket's structural mass which reduces its delta-v significantly. Another disadvantage is the poor storability of LH2/LOX-powered rockets: Due to the constant hydrogen boil-off, the rocket must be fueled shortly before launch, which makes cryogenic engines unsuitable for ICBMs and other rocket applications with the need for short launch preparations.

Overall, the delta-v of a hydrogen stage is typically not much different from that of a dense fuelled stage, but the weight of a hydrogen stage is much less, which makes it particularly effective for upper stages, since they are carried by the lower stages. For first stages, dense fuelled rockets in studies may show a small advantage, due to the smaller vehicle size and lower air drag.

LH2/LOX were also used in the Space Shuttle to run the fuel cells that power the electrical systems. The byproduct of the fuel cell is water, which is used for drinking and other applications that require water in space.

Heavy trucks

United Parcel Service began testing of a hydrogen powered delivery vehicle in 2017. US Hybrid, Toyota, and Kenworth also plan to test Class 8 drayage hydrogen fuel cell trucks.

In 2020, Hyundai began commercial production of its Xcient fuel cell trucks and has shipped ten of them to Switzerland. It plans to sell to additional markets, including the US by 2022.

Internal combustion vehicle

Hydrogen internal combustion engine cars are different from hydrogen fuel cell cars. The hydrogen internal combustion car is a slightly modified version of the traditional gasoline internal combustion engine car. These hydrogen engines burn fuel in the same manner that gasoline engines do; the main difference is the exhaust product. Gasoline combustion results in emissions of mostly carbon dioxide and water, plus trace amounts of carbon monoxide, NOx, particulates and unburned hydrocarbons, while the main exhaust product of hydrogen combustion is water vapor.

In 1807 Francois Isaac de Rivaz designed the first hydrogen-fueled internal combustion engine. In 1965, Roger Billings, then a high school student, converted a Model A to run on hydrogen. In 1970 Paul Dieges patented a modification to internal combustion engines which allowed a gasoline-powered engine to run on hydrogen US 3844262.

Mazda has developed Wankel engines burning hydrogen, which are used in the Mazda RX-8 Hydrogen RE. The advantage of using an internal combustion engine, like Wankel and piston engines, is the lower cost of retooling for production.

HICE forklift trucks have been demonstrated based on converted diesel internal combustion engines with direct injection.

Fuel cell

Fuel cell cost

Hydrogen fuel cells are relatively expensive to produce, as their designs require rare substances, such as platinum, as a catalyst, In 2014, former European Parliament President Pat Cox estimated that Toyota would initially lose about $100,000 on each Mirai sold. In 2020, researchers at the University of Copenhagen's Department of Chemistry are developing a new type of catalyst that they hope will decrease the cost of fuel cells. This new catalyst uses far less platinum because the platinum nano-particles are not coated over carbon which, in conventional hydrogen fuel cells, keeps the nano-particles in place but also causes the catalyst to become unstable and denatures it slowly, requiring even more platinum. The new technology uses durable nanowires instead of the nano-particles. "The next step for the researchers is to scale up their results so that the technology can be implemented in hydrogen vehicles."

Freezing conditions

The problems in early fuel-cell designs at low temperatures concerning range and cold start capabilities have been addressed so that they "cannot be seen as show-stoppers anymore". Users in 2014 said that their fuel cell vehicles perform flawlessly in temperatures below zero, even with the heaters blasting, without significantly reducing range. Studies using neutron radiography on unassisted cold-start indicate ice formation in the cathode, three stages in cold start and Nafion ionic conductivity. A parameter, defined as coulomb of charge, was also defined to measure cold start capability.

Service life

The service life of fuel cells is comparable to that of other vehicles. Polymer-electrolyte membrane (PEM) fuel cell service life is 7,300 hours under cycling conditions.

Hydrogen

Hydrogen does not exist in convenient reservoirs or deposits like fossil fuels or helium. It is produced from feedstocks such as natural gas and biomass or electrolyzed from water. A suggested benefit of large-scale deployment of hydrogen vehicles is that it could lead to decreased emissions of greenhouse gases and ozone precursors. However, as of 2014, 95% of hydrogen is made from methane. It can be produced by thermochemical or pyrolitic means using renewable feedstocks, but that is an expensive process. Renewable electricity can however be used to power the conversion of water into hydrogen: Integrated wind-to-hydrogen (power to gas) plants, using electrolysis of water, are exploring technologies to deliver costs low enough, and quantities great enough, to compete with traditional energy sources.

According to Ford Motor Company, a hydrogen fuel-cell vehicle would generate only three-fifths as much carbon dioxide as a comparable vehicle running on gasoline blended to 10 percent ethanol. Although methods of hydrogen production that do not use fossil fuel would be more sustainable, currently renewable energy represents only a small percentage of energy generated, and power produced from renewable sources can be used more efficiently in electric vehicles and for non-vehicle applications.

The challenges facing the use of hydrogen in vehicles include chiefly its storage on board the vehicle. While the well-to-wheel efficiency for hydrogen from the least efficient manner of producing it (electrolysis) is less than 25 percent, it still exceeds that of vehicles based on internal combustion engines.

Production

The molecular hydrogen needed as an onboard fuel for hydrogen vehicles can be obtained through many thermochemical methods utilizing natural gas, coal (by a process known as coal gasification), liquefied petroleum gas, biomass (biomass gasification), by a process called thermolysis, or as a microbial waste product called biohydrogen or Biological hydrogen production. 95% of hydrogen is produced using natural gas, and 85% of hydrogen produced is used to remove sulfur from gasoline. Hydrogen can also be produced from water by electrolysis at working efficiencies of 65–70%. Hydrogen can also be made by chemical reduction using chemical hydrides or aluminum. Current technologies for manufacturing hydrogen use energy in various forms, totaling between 25 and 50 percent of the higher heating value of the hydrogen fuel, used to produce, compress or liquefy, and transmit the hydrogen by pipeline or truck.

Environmental consequences of the production of hydrogen from fossil energy resources include the emission of greenhouse gasses, a consequence that would also result from the on-board reforming of methanol into hydrogen. Analyses comparing the environmental consequences of hydrogen production and use in fuel-cell vehicles to the refining of petroleum and combustion in conventional automobile engines do not agree on whether a net reduction of ozone and greenhouse gasses would result. Hydrogen production using renewable energy resources would not create such emissions, but the scale of renewable energy production would need to be expanded to be used in producing hydrogen for a significant part of transportation needs. As of 2016, 14.9 percent of U.S. electricity was produced from renewable sources. In a few countries, renewable sources are being used more widely to produce energy and hydrogen. For example, Iceland is using geothermal power to produce hydrogen, and Denmark is using wind.

Storage

Compressed hydrogen storage mark

Compressed hydrogen in hydrogen tanks at 350 bar (5,000 psi) and 700 bar (10,000 psi) is used for hydrogen tank systems in vehicles, based on type IV carbon-composite technology.

Hydrogen has a very low volumetric energy density at ambient conditions, compared with gasoline and other vehicle fuels. It must be stored in a vehicle either as a super-cooled liquid or as highly compressed gas, which require additional energy to accomplish. In 2018, researchers at CSIRO in Australia powered a Toyota Mirai and Hyundai Nexo with hydrogen separated from ammonia using a membrane technology. Ammonia is easier to transport safely in tankers than pure hydrogen.

Infrastructure

Hydrogen car fueling
 
Hydrogen fueling

The hydrogen infrastructure consists of hydrogen-equipped filling stations, which are supplied with hydrogen via compressed hydrogen tube trailers, liquid hydrogen tank trucks or dedicated onsite production, and some industrial hydrogen pipeline transport. The distribution of hydrogen fuel for vehicles throughout the U.S. would require new hydrogen stations that would cost between 20 billion dollars in the US, (4.6 billion in the EU). and half trillion dollars in the US.

As of 2021, there were 49 publicly accessible hydrogen refueling stations in the US, 48 of which were located in California (compared with 42,830 electric charging stations). By 2017, there were 91 hydrogen fueling stations in Japan.

Codes and standards

Hydrogen codes and standards, as well as codes and technical standards for hydrogen safety and the storage of hydrogen, have been an institutional barrier to deploying hydrogen technologies. To enable the commercialization of hydrogen in consumer products, new codes and standards must be developed and adopted by federal, state and local governments.

Official support

U.S. initiatives

In 2003, George W. Bush announced an initiative to promote hydrogen-powered vehicles. In 2009, President Obama and his Energy Secretary Steven Chu stripped the funding of fuel cell technology after concluding that the technology was still decades away. Under heavy criticism, the funding was partially restored.

In 2013, Senator Byron L. Dorgan said that "The Energy and Water Appropriations bill makes investments in our nation’s efforts to develop safe, homegrown energy sources that will reduce our reliance on foreign oil. And, because ongoing research and development is necessary to develop game-changing technologies, this bill also restores funding for Hydrogen energy research." The same year, the U.S. Department of Energy gave 9 million dollars in grants to speed up technology development, 4.5 million for advanced fuel cell membranes, $3 million to 3M to work on membranes with improved durability and performance, and 1.5 million to the Colorado School of Mines for work on simpler and more affordable fuel cell membranes. US investments in fueling were planned in 2014.

Other efforts

In Japan, hydrogen is mainly to be sourced from outside Japan.

Norway plans a series of hydrogen refueling stations along the main roads.

Criticism

Critics claim the time frame for overcoming the technical and economic challenges to implementing wide-scale use of hydrogen cars is likely to last for at least several decades. They claim that the focus on the use of the hydrogen car is a dangerous detour from more readily available solutions to reducing the use of fossil fuels in vehicles. In May 2008, Wired News reported that "experts say it will be 40 years or more before hydrogen has any meaningful impact on gasoline consumption or global warming, and we can't afford to wait that long. In the meantime, fuel cells are diverting resources from more immediate solutions."

Critiques of hydrogen vehicles are presented in the 2006 documentary, Who Killed the Electric Car?. According to former U.S. Department of Energy official Joseph Romm, "A hydrogen car is one of the least efficient, most expensive ways to reduce greenhouse gases." Asked when hydrogen cars will be broadly available, Romm replied: "Not in our lifetime, and very possibly never." The Los Angeles Times wrote, in 2009, "Hydrogen fuel-cell technology won't work in cars. ... Any way you look at it, hydrogen is a lousy way to move cars." The Economist magazine, in 2008, quoted Robert Zubrin, the author of Energy Victory, as saying: "Hydrogen is 'just about the worst possible vehicle fuel'". The magazine noted the withdrawal of California from earlier goals: "In [2008] the California Air Resources Board, an agency of California's state government and a bellwether for state governments across America, changed its requirement for the number of zero-emission vehicles (ZEVs) to be built and sold in California between 2012 and 2014. The revised mandate allows manufacturers to comply with the rules by building more battery-electric cars instead of fuel-cell vehicles." The magazine also noted that most hydrogen is produced through steam methane reformation, which creates at least as much emission of carbon per mile as some of today's gasoline cars. On the other hand, if the hydrogen could be produced using renewable energy, "it would surely be easier simply to use this energy to charge the batteries of all-electric or plug-in hybrid vehicles." As of 2019, 98% of hydrogen is produced by steam methane reforming, which emits carbon dioxide.

A 2009 study at UC Davis, published in the Journal of Power Sources, similarly found that, over their lifetimes, hydrogen vehicles will emit more carbon than gasoline vehicles. This agrees with a 2014 analysis. The Washington Post asked in 2009, "[W]hy would you want to store energy in the form of hydrogen and then use that hydrogen to produce electricity for a motor, when electrical energy is already waiting to be sucked out of sockets all over America and stored in auto batteries"? The Motley Fool stated in 2013 that "there are still cost-prohibitive obstacles [for hydrogen cars] relating to transportation, storage, and, most importantly, production."

Volkswagen's Rudolf Krebs said in 2013 that "no matter how excellent you make the cars themselves, the laws of physics hinder their overall efficiency. The most efficient way to convert energy to mobility is electricity." He elaborated: "Hydrogen mobility only makes sense if you use green energy", but ... you need to convert it first into hydrogen "with low efficiencies" where "you lose about 40 percent of the initial energy". You then must compress the hydrogen and store it under high pressure in tanks, which uses more energy. "And then you have to convert the hydrogen back to electricity in a fuel cell with another efficiency loss". Krebs continued: "in the end, from your original 100 percent of electric energy, you end up with 30 to 40 percent." The Business Insider commented:

Pure hydrogen can be industrially derived, but it takes energy. If that energy does not come from renewable sources, then fuel-cell cars are not as clean as they seem. ... Another challenge is the lack of infrastructure. Gas stations need to invest in the ability to refuel hydrogen tanks before FCEVs [fuel cell electric vehicles] become practical, and it's unlikely many will do that while there are so few customers on the road today. ... Compounding the lack of infrastructure is the high cost of the technology. Fuel cells are "still very, very expensive".

In 2014, Joseph Romm devoted three articles to updating his critiques of hydrogen vehicles made in his book The Hype about Hydrogen. He stated that fuel cell vehicles still had not overcome the high cost of the vehicles, high fueling cost, and lack of fuel-delivery infrastructure. "It would take several miracles to overcome all of those problems simultaneously in the coming decades." Moreover, he wrote, "FCVs aren't green" because of escaping methane during natural gas extraction and when hydrogen is produced, as 95% of it is, using the steam reforming process. He concluded that renewable energy cannot economically be used to make hydrogen for an FCV fleet "either now or in the future." GreenTech Media's analyst reached similar conclusions in 2014. In 2015, Clean Technica listed some of the disadvantages of hydrogen fuel cell vehicles as did Car Throttle. Another Clean Technica writer concluded that "while hydrogen may have a part to play in the world of energy storage (especially seasonal storage), it looks like a dead end when it comes to mainstream vehicles." A 2016 study in the November issue of the journal Energy by scientists at Stanford University and the Technical University of Munich concluded that, even assuming local hydrogen production, "investing in all-electric battery vehicles is a more economical choice for reducing carbon dioxide emissions, primarily due to their lower cost and significantly higher energy efficiency."

A 2017 analysis published in Green Car Reports concluded that the best hydrogen-fuel-cell vehicles consume "more than three times more electricity per mile than an electric vehicle ... generate more greenhouse gas emissions than other powertrain technologies ... [and have] very high fuel costs. ... Considering all the obstacles and requirements for new infrastructure (estimated to cost as much as $400 billion), fuel-cell vehicles seem likely to be a niche technology at best, with little impact on U.S. oil consumption. The US Department of Energy agrees, for fuel produced by grid electricity via electrolysis, but not for most other pathways for generation. A 2019 video by Real Engineering noted that, notwithstanding the introduction of vehicles that run on hydrogen, using hydrogen as a fuel for cars does not help to reduce carbon emissions from transportation. The 95% of hydrogen still produced from fossil fuels releases carbon dioxide, and producing hydrogen from water is an energy-consuming process. Storing hydrogen requires more energy either to cool it down to the liquid state or to put it into tanks under high pressure, and delivering the hydrogen to fueling stations requires more energy and may release more carbon. The hydrogen needed to move a FCV a kilometer costs approximately 8 times as much as the electricity needed to move a BEV the same distance. Also in 2019, Katsushi Inoue, the president of Honda Europe, stated, "Our focus is on hybrid and electric vehicles now. Maybe hydrogen fuel cell cars will come, but that’s a technology for the next era."

A 2020 assessment concluded that hydrogen vehicles are still only 38% efficient, while battery EVs are 80% efficient. A 2021 assessment by CleanTechnica concluded that while hydrogen cars are far less efficient than electric cars, the vast majority of hydrogen being produced is polluting grey hydrogen, and delivering hydrogen would require building a vast and expensive new infrastructure, the remaining two "advantages of fuel cell vehicles – longer range and fast fueling times – are rapidly being eroded by improving battery and charging technology."

Safety and supply

Hydrogen fuel is hazardous because of the low ignition energy (see also Autoignition temperature) and high combustion energy of hydrogen, and because it tends to leak easily from tanks. Explosions at hydrogen filling stations have been reported. Hydrogen fuelling stations generally receive deliveries of hydrogen by truck from hydrogen suppliers. An interruption at a hydrogen supply facility can shut down multiple hydrogen fuelling stations.

Comparison with other types of alternative fuel vehicle

Hydrogen vehicles compete with various proposed alternatives to the modern fossil fuel powered vehicle infrastructure.

Plug-in hybrids

Plug-in hybrid electric vehicles, or PHEVs, are hybrid vehicles that can be plugged into the electric grid and contain an electric motor and also an internal combustion engine. The PHEV concept augments standard hybrid electric vehicles with the ability to recharge their batteries from an external source, enabling increased use of the vehicle's electric motors while reducing their reliance on internal combustion engines. The infrastructure required to charge PHEVs is already in place, and transmission of power from grid to car is about 93% efficient. This, however, is not the only energy loss in transferring power from grid to wheels. AC/DC conversion must take place from the grid's AC supply to the PHEV's DC. This is roughly 98% efficient. The battery then must be charged. As of 2007, the Lithium iron phosphate battery was between 80 and 90% efficient in charging/discharging. The battery needs to be cooled. As of 2009, "the total well-to-wheels efficiency with which a hydrogen fuel cell vehicle might utilize renewable electricity is roughly 20%. ... The well-to-wheels efficiency of charging an onboard battery and then discharging it to run an electric motor in a PHEV or EV, however, is 80%... four times more efficient than current hydrogen fuel cell vehicle pathways." A December 2009 study at UC Davis found that, over their lifetimes, PHEVs will emit less carbon than current vehicles, while hydrogen cars will emit more carbon than gasoline vehicles.

Natural gas

Internal combustion engine-based compressed natural gas(CNG), HCNG, LPG or LNG vehicles (Natural gas vehicles or NGVs) use methane (Natural gas or Biogas) directly as a fuel source. Natural gas has a higher energy density than hydrogen gas. NGVs using biogas are nearly carbon neutral. Unlike hydrogen vehicles, CNG vehicles have been available for many years, and there is sufficient infrastructure to provide both commercial and home refueling stations. Worldwide, there were 14.8 million natural gas vehicles by the end of 2011. The other use for natural gas is in steam reforming which is the common way to produce hydrogen gas for use in electric cars with fuel cells.

All-electric vehicles

A 2008 Technology Review article stated, "Electric cars—and plug-in hybrid cars—have an enormous advantage over hydrogen fuel-cell vehicles in utilizing low-carbon electricity. That is because of the inherent inefficiency of the entire hydrogen fueling process, from generating the hydrogen with that electricity to transporting this diffuse gas long distances, getting the hydrogen in the car, and then running it through a fuel cell—all for the purpose of converting the hydrogen back into electricity to drive the same exact electric motor you'll find in an electric car." Thermodynamically, each additional step in the conversion process decreases the overall efficiency of the process.

A 2013 comparison of hydrogen and battery electric vehicles agreed with the 25% figure from Ulf Bossel in 2006 and stated that the cost of an electric vehicle battery "is rapidly coming down, and the gap will widen further", while there is little "existing infrastructure to transport, store and deliver hydrogen to vehicles and would cost billions of dollars to put into place, everyone's household power sockets are "electric vehicle refueling" station and the "cost of electricity (depending on the source) is at least 75% cheaper than hydrogen." By 2018, the cost of EV batteries had fallen to below $150 per kWh.

Early electric car designs offered limited driving range causing range anxiety. For example, the 2013 Nissan Leaf had a range of 75 mi (121 km), More recent EV models generally have considerably greater range; for example, the 2020 Tesla Model S has a range of more than 400 mi (640 km). Most US commutes are 30–40 miles (48–64 km) per day round trip, and in Europe, most commutes are around 20 kilometres (12 mi) round-trip

In 2013 John Swanton of the California Air Resources Board, who saw EVs and hydrogen vehicles as complementary technologies, stated that EVs had the jump on fuel-cell autos, which "are like electric vehicles were 10 years ago. EVs are for real consumers, no strings attached. With EVs you have a lot of infrastructure in place. The Business Insider, in 2013 commented that if the energy to produce hydrogen "does not come from renewable sources, then fuel-cell cars are not as clean as they seem. ... Gas stations need to invest in the ability to refuel hydrogen tanks before FCEVs become practical, and it's unlikely many will do that while there are so few customers on the road today. ... Compounding the lack of infrastructure is the high cost of the technology. Fuel cells are "still very, very expensive", even compared to battery-powered EVs.

 

Johnson thermoelectric energy converter

From Wikipedia, the free encyclopedia

A Johnson thermoelectric energy converter or JTEC is a type of solid-state heat engine that uses the electrochemical oxidation and reduction of hydrogen in a two-cell, thermal cycle that approximates the Ericsson cycle. It is under investigation as a viable alternative to conventional thermoelectric conversion. Lonnie Johnson invented it and claims the converter exhibits an energy conversion efficiency of as much as 60%, however, this claim is at a theoretical level based on comparison with a Carnot cycle and assumes a temperature gradient of 600 °C. It was originally proposed for funding to the Office of Naval Research but was refused. Johnson obtained later funding by framing the engine as a hydrogen fuel cell. Johnson had been collaborating with PARC on development of the engine.

Mechanism of action

The JTEC converts is a form of heat engine that converts thermal energy into electrical energy by compressing and expanding hydrogen gas. It operates as a closed system with no moving classical mechanical parts, requires no input of fuel, and creates no exhaust. The engine consists of two stages: A low-temperature compression stage and a high-temperature power stage. Each stage consists of a working fluid chamber that a copper lined membrane electrode assembly (MEA) bisects. A MEA is a proprietary ceramic proton exchange membrane (PEM) that is sandwiched between two electrodes.

The operation is similar to an alkali-metal thermal to electric converter, using hydrogen as the working fluid rather than the highly-reactive molten alkali metals, which are difficult to work with. In the high-temperature power stage, expanding high pressure hydrogen from the compression stage converts the heat energy into electrical energy via the MEA. As the high-temperature, high pressure hydrogen is forced through the PEM it is ionized, producing protons and electrons. The protons pass through the membrane while the electrodes expel the electrons through a load. After passing through the PEM, the protons recombine with the electrons to produce low pressure hydrogen gas that flows out to the compression stage. From the perspective of the high-temperature stage, the load consists of the external load on the engine and the low-temperature compression stage. In the compression stage, electrical potential is applied across the MEA and forces protons to flow through the PEM to produce high pressure hydrogen. As the hydrogen travels between the stages, it passes through a heat exchanger that increases efficiency by helping to keep the high-temperature stage hot and the low-temperature stage cool.

The amount of energy available to the external load is the difference in electrical potential between that needed to compress hydrogen at low-temperature and that which expanding it at high temperature generates. Unlike other heat pump devices, the JTEC requires an initial input of electrical energy to start the compression stage and initiate the cycle. In principle, the engine can also be operated in reverse to convert electrical energy into a temperature differential, for example in HVAC applications. In one proposed application, solar irradiance would heat the power stage, and the compression stage would connect to an ambient temperature heat sink.

Applications

The scalability of the engine leads its developers to claim that its potential applications range from providing power for microelectromechanical systems (MEMS) to functioning as large-scale power plants.

The converter can use many diverse forms of fuel without the need for fuel-specific customization as seen in internal combustion engines, and can generate power from fuel combustion, solar irradiance, low grade waste heat from industry, or such other power generation systems as fuel cells, internal combustion engines, or turbines, because it functions as an external combustion engine.

 

Graphene

From Wikipedia, the free encyclopedia
 
Graphene is an atomic-scale hexagonal lattice made of carbon atoms

Graphene (/ˈɡræfn/) is an allotrope of carbon consisting of a single layer of atoms arranged in a two-dimensional honeycomb lattice nanostructure. The name is derived from "graphite" and the suffix -ene, reflecting the fact that the graphite allotrope of carbon contains numerous double bonds.

Each atom in a graphene sheet is connected to its three nearest neighbors by a σ-bond, and contributes one electron to a conduction band that extends over the whole sheet. This is the same type of bonding seen in carbon nanotubes and polycyclic aromatic hydrocarbons, and (partially) in fullerenes and glassy carbon. These conduction bands make graphene a semimetal with unusual electronic properties that are best described by theories for massless relativistic particles. Charge carriers in graphene show linear, rather than quadratic, dependence of energy on momentum, and field-effect transistors with graphene can be made that show bipolar conduction. Charge transport is ballistic over long distances; the material exhibits large quantum oscillations and large and nonlinear diamagnetism. Graphene conducts heat and electricity very efficiently along its plane. The material strongly absorbs light of all visible wavelengths, which accounts for the black color of graphite; yet a single graphene sheet is nearly transparent because of its extreme thinness. The material is also about 100 times stronger than would be the strongest steel of the same thickness.

Photograph of a suspended graphene membrane in transmitted light. This one-atom-thick material can be seen with the naked eye because it absorbs approximately 2.3% of light.

Scientists theorized the potential existence and production of graphene for decades. It has likely been unknowingly produced in small quantities for centuries, through the use of pencils and other similar applications of graphite. It was originally observed in electron microscopes in 1962, but only studied while supported on metal surfaces.

In 2004 the material was rediscovered, isolated and investigated at the University of Manchester, by Andre Geim and Konstantin Novoselov. In 2010 Geim and Novoselov were awarded the Nobel Prize in Physics for their "groundbreaking experiments regarding the two-dimensional material graphene". High-quality graphene proved to be surprisingly easy to isolate.

Graphene has become a valuable and useful nanomaterial due to its exceptionally high tensile strength, electrical conductivity, transparency, and being the thinnest two-dimensional material in the world. The global market for graphene was $9 million in 2012, with most of the demand from research and development in semiconductor, electronics, electric batteries, and composites.

The IUPAC (International Union for Pure and Applied Chemistry) recommends use of the name "graphite" for the three-dimensional material, and "graphene" only when the reactions, structural relations or other properties of individual layers are discussed. A narrower definition, of "isolated or free-standing graphene" requires that the layer be sufficiently isolated from its environment, but would include layers suspended or transferred to silicon dioxide or silicon carbide.

History

A lump of graphite, a graphene transistor, and a tape dispenser. Donated to the Nobel Museum in Stockholm by Andre Geim and Konstantin Novoselov in 2010.

Structure of graphite and its intercalation compounds

In 1859 Benjamin Brodie noted the highly lamellar structure of thermally reduced graphite oxide. In 1916, Peter Debije and P. Scherrer determined the structure of graphite by powder X-ray diffraction. The structure was studied in more detail by V. Kohlschütter and P. Haenni in 1918, who also described the properties of graphite oxide paper. Its structure was determined from single-crystal diffraction in 1924.

The theory of graphene was first explored by P. R. Wallace in 1947 as a starting point for understanding the electronic properties of 3D graphite. The emergent massless Dirac equation was first pointed out in 1984 separately by Gordon Walter Semenoff, and by David P. DiVincenzo and Eugene J. Mele. Semenoff emphasized the occurrence in a magnetic field of an electronic Landau level precisely at the Dirac point. This level is responsible for the anomalous integer quantum Hall effect.

Observations of thin graphite layers and related structures

Transmission electron microscopy (TEM) images of thin graphite samples consisting of a few graphene layers were published by G. Ruess and F. Vogt in 1948. Eventually, single layers were also observed directly. Single layers of graphite were also observed by transmission electron microscopy within bulk materials, in particular inside soot obtained by chemical exfoliation.

In 1961–1962, Hanns-Peter Boehm published a study of extremely thin flakes of graphite, and coined the term "graphene" for the hypothetical single-layer structure. This paper reports graphitic flakes that give an additional contrast equivalent of down to ~0.4 nm or 3 atomic layers of amorphous carbon. This was the best possible resolution for 1960 TEMs. However, neither then nor today is it possible to argue how many layers were in those flakes. Now we know that the TEM contrast of graphene most strongly depends on focusing conditions. For example, it is impossible to distinguish between suspended monolayer and multilayer graphene by their TEM contrasts, and the only known way is to analyze the relative intensities of various diffraction spots. The first reliable TEM observations of monolayers are probably given in refs. 24 and 26 of Geim and Novoselov's 2007 review.

Starting in the 1970s, C. Oshima and others described single layers of carbon atoms that were grown epitaxially on top of other materials. This "epitaxial graphene" consists of a single-atom-thick hexagonal lattice of sp2-bonded carbon atoms, as in free-standing graphene. However, there is significant charge transfer between the two materials, and, in some cases, hybridization between the d-orbitals of the substrate atoms and π orbitals of graphene; which significantly alter the electronic structure compared to that of free-standing graphene.

The term "graphene" was used again in 1987 to describe single sheets of graphite as a constituent of graphite intercalation compounds, which can be seen as crystalline salts of the intercalant and graphene. It was also used in the descriptions of carbon nanotubes by R. Saito and Mildred and Gene Dresselhaus in 1992, and of polycyclic aromatic hydrocarbons in 2000 by S. Wang and others.

Efforts to make thin films of graphite by mechanical exfoliation started in 1990. Initial attempts employed exfoliation techniques similar to the drawing method. Multilayer samples down to 10 nm in thickness were obtained.

In 2002, Robert B. Rutherford and Richard L. Dudman filed for a patent in the US on a method to produce graphene by repeatedly peeling off layers from a graphite flake adhered to a substrate, achieving a graphite thickness of 0.00001 inches (2.5×10−7 metres). The key to success was high-throughput visual recognition of graphene on a properly chosen substrate, which provides a small but noticeable optical contrast.

Another U.S. patent was filed in the same year by Bor Z. Jang and Wen C. Huang for a method to produce graphene based on exfoliation followed by attrition.

Full isolation and characterization

Andre Geim and Konstantin Novoselov at the Nobel Laureate press conference, Royal Swedish Academy of Sciences, 2010.

Graphene was properly isolated and characterized in 2004 by Andre Geim and Konstantin Novoselov at the University of Manchester. They pulled graphene layers from graphite with a common adhesive tape in a process called either micromechanical cleavage or the Scotch tape technique. The graphene flakes were then transferred onto thin silicon dioxide (silica) layer on a silicon plate ("wafer"). The silica electrically isolated the graphene and weakly interacted with it, providing nearly charge-neutral graphene layers. The silicon beneath the SiO
2
could be used as a "back gate" electrode to vary the charge density in the graphene over a wide range.

This work resulted in the two winning the Nobel Prize in Physics in 2010 "for groundbreaking experiments regarding the two-dimensional material graphene." Their publication, and the surprisingly easy preparation method that they described, sparked a "graphene gold rush". Research expanded and split off into many different subfields, exploring different exceptional properties of the material—quantum mechanical, electrical, chemical, mechanical, optical, magnetic, etc.

Exploring commercial applications

Since the early 2000s, a number of companies and research laboratories have been working to develop commercial applications of graphene. In 2014 a National Graphene Institute was established with that purpose at the University of Manchester, with a 60 million GBP initial funding. In North East England two commercial manufacturers, Applied Graphene Materials and Thomas Swan Limited have begun manufacturing. Cambridge Nanosystems is a large-scale graphene powder production facility in East Anglia.

Structure

Bonding

Carbon orbitals 2s, 2px, 2py form the hybrid orbital sp2 with three major lobes at 120°. The remaining orbital, pz, is sticking out of the graphene's plane.
Sigma and pi bonds in graphene. Sigma bonds result from an overlap of sp2 hybrid orbitals, whereas pi bonds emerge from tunneling between the protruding pz orbitals.

Three of the four outer-shell electrons of each atom in a graphene sheet occupy three sp2 hybrid orbitals – a combination of orbitals s, px and py — that are shared with the three nearest atoms, forming σ-bonds. The length of these bonds is about 0.142 nanometers.

The remaining outer-shell electron occupies a pz orbital that is oriented perpendicularly to the plane. These orbitals hybridize together to form two half-filled bands of free-moving electrons, π and π∗, which are responsible for most of graphene's notable electronic properties. Recent quantitative estimates of aromatic stabilization and limiting size derived from the enthalpies of hydrogenation (ΔHhydro) agree well with the literature reports.

Graphene sheets stack to form graphite with an interplanar spacing of 0.335 nm (3.35 Å).

Graphene sheets in solid form usually show evidence in diffraction for graphite's (002) layering. This is true of some single-walled nanostructures. However, unlayered graphene with only (hk0) rings has been found in the core of presolar graphite onions. TEM studies show faceting at defects in flat graphene sheets and suggest a role for two-dimensional crystallization from a melt.

Geometry

Scanning probe microscopy image of graphene

The hexagonal lattice structure of isolated, single-layer graphene can be directly seen with transmission electron microscopy (TEM) of sheets of graphene suspended between bars of a metallic grid Some of these images showed a "rippling" of the flat sheet, with amplitude of about one nanometer. These ripples may be intrinsic to the material as a result of the instability of two-dimensional crystals, or may originate from the ubiquitous dirt seen in all TEM images of graphene. Photoresist residue, which must be removed to obtain atomic-resolution images, may be the "adsorbates" observed in TEM images, and may explain the observed rippling.

The hexagonal structure is also seen in scanning tunneling microscope (STM) images of graphene supported on silicon dioxide substrates The rippling seen in these images is caused by conformation of graphene to the subtrate's lattice, and is not intrinsic.

Stability

Ab initio calculations show that a graphene sheet is thermodynamically unstable if its size is less than about 20 nm and becomes the most stable fullerene (as within graphite) only for molecules larger than 24,000 atoms.

Properties

Electronic

Electronic band structure of graphene. Valence and conduction bands meet at the six vertices of the hexagonal Brillouin zone and form linearly dispersing Dirac cones.

Graphene is a zero-gap semiconductor, because its conduction and valence bands meet at the Dirac points. The Dirac points are six locations in momentum space, on the edge of the Brillouin zone, divided into two non-equivalent sets of three points. The two sets are labeled K and K'. The sets give graphene a valley degeneracy of gv = 2. By contrast, for traditional semiconductors the primary point of interest is generally Γ, where momentum is zero. Four electronic properties separate it from other condensed matter systems.

However, if the in-plane direction is no longer infinite, but confined, its electronic structure would change. They are referred to as graphene nanoribbons. If it is "zig-zag", the bandgap would still be zero. If it is "armchair", the bandgap would be non-zero.

Graphene's hexagonal lattice can be regarded as two interleaving triangular lattices. This perspective was successfully used to calculate the band structure for a single graphite layer using a tight-binding approximation.

Electronic spectrum

Electrons propagating through graphene's honeycomb lattice effectively lose their mass, producing quasi-particles that are described by a 2D analogue of the Dirac equation rather than the Schrödinger equation for spin-12 particles.

Dispersion relation

Electronic band structure and Dirac cones, with effect of doping

The cleavage technique led directly to the first observation of the anomalous quantum Hall effect in graphene in 2005, by Geim's group and by Philip Kim and Yuanbo Zhang. This effect provided direct evidence of graphene's theoretically predicted Berry's phase of massless Dirac fermions and the first proof of the Dirac fermion nature of electrons. These effects had been observed in bulk graphite by Yakov Kopelevich, Igor A. Luk'yanchuk, and others, in 2003–2004.

When the atoms are placed onto the graphene hexagonal lattice, the overlap between the pz(π) orbitals and the s or the px and py orbitals is zero by symmetry. The pz electrons forming the π bands in graphene can therefore be treated independently. Within this π-band approximation, using a conventional tight-binding model, the dispersion relation (restricted to first-nearest-neighbor interactions only) that produces energy of the electrons with wave vector k is

with the nearest-neighbor (π orbitals) hopping energy γ02.8 eV and the lattice constant a2.46 Å. The conduction and valence bands, respectively, correspond to the different signs. With one pz electron per atom in this model the valence band is fully occupied, while the conduction band is vacant. The two bands touch at the zone corners (the K point in the Brillouin zone), where there is a zero density of states but no band gap. The graphene sheet thus displays a semimetallic (or zero-gap semiconductor) character, although the same cannot be said of a graphene sheet rolled into a carbon nanotube, due to its curvature. Two of the six Dirac points are independent, while the rest are equivalent by symmetry. In the vicinity of the K-points the energy depends linearly on the wave vector, similar to a relativistic particle. Since an elementary cell of the lattice has a basis of two atoms, the wave function has an effective 2-spinor structure.

As a consequence, at low energies, even neglecting the true spin, the electrons can be described by an equation that is formally equivalent to the massless Dirac equation. Hence, the electrons and holes are called Dirac fermions. This pseudo-relativistic description is restricted to the chiral limit, i.e., to vanishing rest mass M0, which leads to interesting additional features:

Here vF ~ 106 m/s (.003 c) is the Fermi velocity in graphene, which replaces the velocity of light in the Dirac theory; is the vector of the Pauli matrices, is the two-component wave function of the electrons, and E is their energy.

The equation describing the electrons' linear dispersion relation is

where the wavevector q is measured from the Brillouin zone vertex K, , and the zero of energy is set to coincide with the Dirac point. The equation uses a pseudospin matrix formula that describes two sublattices of the honeycomb lattice.

Single-atom wave propagation

Electron waves in graphene propagate within a single-atom layer, making them sensitive to the proximity of other materials such as high-κ dielectrics, superconductors and ferromagnetics.

Ambipolar electron and hole transport

When the gate voltage in a field effect graphene device is changed from positive to negative, conduction switches from electrons to holes. The charge carrier concentration is proportional to the applied voltage. Graphene is neutral at zero gate voltage and resistivity is at its maximum because of the dearth of charge carriers. The rapid fall of resistivity when carriers are injected shows their high mobility, here of the order of 5000 cm2/Vs. n-Si/SiO₂ substrate, T=1K.

Graphene displays remarkable electron mobility at room temperature, with reported values in excess of 15000 cm2⋅V−1⋅s−1. Hole and electron mobilities are nearly the same. The mobility is independent of temperature between 10 K and 100 K, and shows little change even at room temperature (300 K), which implies that the dominant scattering mechanism is defect scattering. Scattering by graphene's acoustic phonons intrinsically limits room temperature mobility in freestanding graphene to 200000 cm2⋅V−1⋅s−1 at a carrier density of 1012 cm−2.

The corresponding resistivity of graphene sheets would be 10−6 Ω⋅cm. This is less than the resistivity of silver, the lowest otherwise known at room temperature. However, on SiO
2
substrates, scattering of electrons by optical phonons of the substrate is a larger effect than scattering by graphene's own phonons. This limits mobility to 40000 cm2⋅V−1⋅s−1.

Charge transport has major concerns due to adsorption of contaminants such as water and oxygen molecules. This leads to non-repetitive and large hysteresis I-V characteristics. Researchers must carry out electrical measurements in vacuum. The protection of graphene surface by a coating with materials such as SiN, PMMA, h-BN, etc., have been discussed by researchers. In January 2015, the first stable graphene device operation in air over several weeks was reported, for graphene whose surface was protected by aluminum oxide. In 2015 lithium-coated graphene exhibited superconductivity, a first for graphene.

Electrical resistance in 40-nanometer-wide nanoribbons of epitaxial graphene changes in discrete steps. The ribbons' conductance exceeds predictions by a factor of 10. The ribbons can act more like optical waveguides or quantum dots, allowing electrons to flow smoothly along the ribbon edges. In copper, resistance increases in proportion to length as electrons encounter impurities.

Transport is dominated by two modes. One is ballistic and temperature independent, while the other is thermally activated. Ballistic electrons resemble those in cylindrical carbon nanotubes. At room temperature, resistance increases abruptly at a particular length—the ballistic mode at 16 micrometres and the other at 160 nanometres (1% of the former length).

Graphene electrons can cover micrometer distances without scattering, even at room temperature.

Despite zero carrier density near the Dirac points, graphene exhibits a minimum conductivity on the order of . The origin of this minimum conductivity is still unclear. However, rippling of the graphene sheet or ionized impurities in the SiO
2
substrate may lead to local puddles of carriers that allow conduction. Several theories suggest that the minimum conductivity should be ; however, most measurements are of order or greater and depend on impurity concentration.

Near zero carrier density graphene exhibits positive photoconductivity and negative photoconductivity at high carrier density. This is governed by the interplay between photoinduced changes of both the Drude weight and the carrier scattering rate.

Graphene doped with various gaseous species (both acceptors and donors) can be returned to an undoped state by gentle heating in vacuum. Even for dopant concentrations in excess of 1012 cm−2 carrier mobility exhibits no observable change. Graphene doped with potassium in ultra-high vacuum at low temperature can reduce mobility 20-fold. The mobility reduction is reversible on heating the graphene to remove the potassium.

Due to graphene's two dimensions, charge fractionalization (where the apparent charge of individual pseudoparticles in low-dimensional systems is less than a single quantum) is thought to occur. It may therefore be a suitable material for constructing quantum computers using anyonic circuits.

Chiral half-integer quantum Hall effect

Landau levels in graphene appear at energies proportional to √N, in contrast to the standard sequence that goes as N+½.

The quantum Hall effect is a quantum mechanical version of the Hall effect, which is the production of transverse (perpendicular to the main current) conductivity in the presence of a magnetic field. The quantization of the Hall effect at integer multiples (the "Landau level") of the basic quantity (where e is the elementary electric charge and h is Planck's constant). It can usually be observed only in very clean silicon or gallium arsenide solids at temperatures around K and very high magnetic fields.

Graphene shows the quantum Hall effect with respect to conductivity quantization: the effect is unordinary in that the sequence of steps is shifted by 1/2 with respect to the standard sequence and with an additional factor of 4. Graphene's Hall conductivity is , where N is the Landau level and the double valley and double spin degeneracies give the factor of 4. These anomalies are present not only at extremely low temperatures but also at room temperature, i.e. at roughly 20 °C (293 K).

This behavior is a direct result of graphene's chiral, massless Dirac electrons. In a magnetic field, their spectrum has a Landau level with energy precisely at the Dirac point. This level is a consequence of the Atiyah–Singer index theorem and is half-filled in neutral graphene, leading to the "+1/2" in the Hall conductivity. Bilayer graphene also shows the quantum Hall effect, but with only one of the two anomalies (i.e. ). In the second anomaly, the first plateau at N=0 is absent, indicating that bilayer graphene stays metallic at the neutrality point.

Chiral half-integer quantum Hall effect in graphene. Plateaux in transverse conductivity appear at half integers of 4e²/h.

Unlike normal metals, graphene's longitudinal resistance shows maxima rather than minima for integral values of the Landau filling factor in measurements of the Shubnikov–de Haas oscillations, whereby the term integral quantum Hall effect. These oscillations show a phase shift of π, known as Berry's phase. Berry's phase arises due to chirality or dependence (locking) of the pseudospin quantum number on momentum of low-energy electrons near the Dirac points. The temperature dependence of the oscillations reveals that the carriers have a non-zero cyclotron mass, despite their zero effective mass in the Dirac-fermion formalism.

Graphene samples prepared on nickel films, and on both the silicon face and carbon face of silicon carbide, show the anomalous effect directly in electrical measurement. Graphitic layers on the carbon face of silicon carbide show a clear Dirac spectrum in angle-resolved photoemission experiments, and the effect is observed in cyclotron resonance and tunneling experiments.

Strong magnetic fields

In magnetic fields above 10 tesla or so additional plateaus of the Hall conductivity at σxy = νe2/h with ν = 0, ±1, ±4 are observed. A plateau at ν = 3 and the fractional quantum Hall effect at ν = 13 were also reported.

These observations with ν = 0, ±1, ±3, ±4 indicate that the four-fold degeneracy (two valley and two spin degrees of freedom) of the Landau energy levels is partially or completely lifted.

Casimir effect

The Casimir effect is an interaction between disjoint neutral bodies provoked by the fluctuations of the electrodynamical vacuum. Mathematically it can be explained by considering the normal modes of electromagnetic fields, which explicitly depend on the boundary (or matching) conditions on the interacting bodies' surfaces. Since graphene/electromagnetic field interaction is strong for a one-atom-thick material, the Casimir effect is of growing interest.

Van der Waals force

The Van der Waals force (or dispersion force) is also unusual, obeying an inverse cubic, asymptotic power law in contrast to the usual inverse quartic.

'Massive' electrons

Graphene's unit cell has two identical carbon atoms and two zero-energy states: one in which the electron resides on atom A, the other in which the electron resides on atom B. However, if the two atoms in the unit cell are not identical, the situation changes. Hunt et al. show that placing hexagonal boron nitride (h-BN) in contact with graphene can alter the potential felt at atom A versus atom B enough that the electrons develop a mass and accompanying band gap of about 30 meV [0.03 Electron Volt(eV)].

The mass can be positive or negative. An arrangement that slightly raises the energy of an electron on atom A relative to atom B gives it a positive mass, while an arrangement that raises the energy of atom B produces a negative electron mass. The two versions behave alike and are indistinguishable via optical spectroscopy. An electron traveling from a positive-mass region to a negative-mass region must cross an intermediate region where its mass once again becomes zero. This region is gapless and therefore metallic. Metallic modes bounding semiconducting regions of opposite-sign mass is a hallmark of a topological phase and display much the same physics as topological insulators.

If the mass in graphene can be controlled, electrons can be confined to massless regions by surrounding them with massive regions, allowing the patterning of quantum dots, wires, and other mesoscopic structures. It also produces one-dimensional conductors along the boundary. These wires would be protected against backscattering and could carry currents without dissipation.

Permittivity

Graphene's permittivity varies with frequency. Over a range from microwave to millimeter wave frequencies it is roughly 3.3. This permittivity, combined with the ability to form both conductors and insulators, means that theoretically, compact capacitors made of graphene could store large amounts of electrical energy.

Optical

Graphene's unique optical properties produce an unexpectedly high opacity for an atomic monolayer in vacuum, absorbing πα ≈ 2.3% of light, from visible to infrared. Here, α is the fine-structure constant. This is a consequence of the "unusual low-energy electronic structure of monolayer graphene that features electron and hole conical bands meeting each other at the Dirac point... [which] is qualitatively different from more common quadratic massive bands." Based on the Slonczewski–Weiss–McClure (SWMcC) band model of graphite, the interatomic distance, hopping value and frequency cancel when optical conductance is calculated using Fresnel equations in the thin-film limit.

Although confirmed experimentally, the measurement is not precise enough to improve on other techniques for determining the fine-structure constant.

Multi-Parametric Surface Plasmon Resonance was used to characterize both thickness and refractive index of chemical-vapor-deposition (CVD)-grown graphene films. The measured refractive index and extinction coefficient values at 670 nm (6.7×10−7 m) wavelength are 3.135 and 0.897, respectively. The thickness was determined as 3.7Å from a 0.5mm area, which agrees with 3.35Å reported for layer-to-layer carbon atom distance of graphite crystals. The method can be further used also for real-time label-free interactions of graphene with organic and inorganic substances. Furthermore, the existence of unidirectional surface plasmons in the nonreciprocal graphene-based gyrotropic interfaces has been demonstrated theoretically. By efficiently controlling the chemical potential of graphene, the unidirectional working frequency can be continuously tunable from THz to near-infrared and even visible. Particularly, the unidirectional frequency bandwidth can be 1– 2 orders of magnitude larger than that in metal under the same magnetic field, which arises from the superiority of extremely small effective electron mass in graphene.

Graphene's band gap can be tuned from 0 to 0.25 eV (about 5 micrometre wavelength) by applying voltage to a dual-gate bilayer graphene field-effect transistor (FET) at room temperature. The optical response of graphene nanoribbons is tunable into the terahertz regime by an applied magnetic field. Graphene/graphene oxide systems exhibit electrochromic behavior, allowing tuning of both linear and ultrafast optical properties.

A graphene-based Bragg grating (one-dimensional photonic crystal) has been fabricated and demonstrated its capability for excitation of surface electromagnetic waves in the periodic structure by using 633 nm (6.33×10−7 m) He–Ne laser as the light source.

Saturable absorption

Such unique absorption could become saturated when the input optical intensity is above a threshold value. This nonlinear optical behavior is termed saturable absorption and the threshold value is called the saturation fluence. Graphene can be saturated readily under strong excitation over the visible to near-infrared region, due to the universal optical absorption and zero band gap. This has relevance for the mode locking of fiber lasers, where fullband mode locking has been achieved by graphene-based saturable absorber. Due to this special property, graphene has wide application in ultrafast photonics. Moreover, the optical response of graphene/graphene oxide layers can be tuned electrically.

Saturable absorption in graphene could occur at the Microwave and Terahertz band, owing to its wideband optical absorption property. The microwave saturable absorption in graphene demonstrates the possibility of graphene microwave and terahertz photonics devices, such as a microwave saturable absorber, modulator, polarizer, microwave signal processing and broad-band wireless access networks.

Nonlinear Kerr effect

Under more intensive laser illumination, graphene could also possess a nonlinear phase shift due to the optical nonlinear Kerr effect. Based on a typical open and close aperture z-scan measurement, graphene possesses a giant nonlinear Kerr coefficient of 10−7 cm2⋅W−1, almost nine orders of magnitude larger than that of bulk dielectrics. This suggests that graphene may be a powerful nonlinear Kerr medium, with the possibility of observing a variety of nonlinear effects, the most important of which is the soliton.

Excitonic

First-principle calculations with quasiparticle corrections and many-body effects are performed to study the electronic and optical properties of graphene-based materials. The approach is described as three stages. With GW calculation, the properties of graphene-based materials are accurately investigated, including bulk graphene, nanoribbons, edge and surface functionalized armchair oribbons, hydrogen saturated armchair ribbons, Josephson effect in graphene SNS junctions with single localized defect and armchair ribbon scaling properties.

Spin transport

Graphene is claimed to be an ideal material for spintronics due to its small spin–orbit interaction and the near absence of nuclear magnetic moments in carbon (as well as a weak hyperfine interaction). Electrical spin current injection and detection has been demonstrated up to room temperature. Spin coherence length above 1 micrometre at room temperature was observed, and control of the spin current polarity with an electrical gate was observed at low temperature.

Magnetic properties

Strong magnetic fields

Graphene's quantum Hall effect in magnetic fields above 10 Teslas or so reveals additional interesting features. Additional plateaus of the Hall conductivity at with are observed. Also, the observation of a plateau at and the fractional quantum Hall effect at were reported.

These observations with indicate that the four-fold degeneracy (two valley and two spin degrees of freedom) of the Landau energy levels is partially or completely lifted. One hypothesis is that the magnetic catalysis of symmetry breaking is responsible for lifting the degeneracy.

Spintronic and magnetic properties can be present in graphene simultaneously. Low-defect graphene nanomeshes manufactured by using a non-lithographic method exhibit large-amplitude ferromagnetism even at room temperature. Additionally a spin pumping effect is found for fields applied in parallel with the planes of few-layer ferromagnetic nanomeshes, while a magnetoresistance hysteresis loop is observed under perpendicular fields.

Magnetic substrates

In 2014 researchers magnetized graphene by placing it on an atomically smooth layer of magnetic yttrium iron garnet. The graphene's electronic properties were unaffected. Prior approaches involved doping graphene with other substances. The dopant's presence negatively affected its electronic properties.

Thermal conductivity

Thermal transport in graphene is an active area of research, which has attracted attention because of the potential for thermal management applications. Following predictions for graphene and related carbon nanotubes, early measurements of the thermal conductivity of suspended graphene reported an exceptionally large thermal conductivity up to 5300 W⋅m−1⋅K−1, compared with the thermal conductivity of pyrolytic graphite of approximately 2000 W⋅m−1⋅K−1 at room temperature. However, later studies primarily on more scalable but more defected graphene derived by Chemical Vapor Deposition have been unable to reproduce such high thermal conductivity measurements, producing a wide range of thermal conductivities between 15002500 W⋅m−1⋅K−1 for suspended single layer graphene . The large range in the reported thermal conductivity can be caused by large measurement uncertainties as well as variations in the graphene quality and processing conditions. In addition, it is known that when single-layer graphene is supported on an amorphous material, the thermal conductivity is reduced to about 500600 W⋅m−1⋅K−1 at room temperature as a result of scattering of graphene lattice waves by the substrate, and can be even lower for few layer graphene encased in amorphous oxide. Likewise, polymeric residue can contribute to a similar decrease in the thermal conductivity of suspended graphene to approximately 500600 W⋅m−1⋅K−1 for bilayer graphene.

It has been suggested that the isotopic composition, the ratio of 12C to 13C, has a significant impact on the thermal conductivity. For example, isotopically pure 12C graphene has higher thermal conductivity than either a 50:50 isotope ratio or the naturally occurring 99:1 ratio. It can be shown by using the Wiedemann–Franz law, that the thermal conduction is phonon-dominated. However, for a gated graphene strip, an applied gate bias causing a Fermi energy shift much larger than kBT can cause the electronic contribution to increase and dominate over the phonon contribution at low temperatures. The ballistic thermal conductance of graphene is isotropic.

Potential for this high conductivity can be seen by considering graphite, a 3D version of graphene that has basal plane thermal conductivity of over a 1000 W⋅m−1⋅K−1 (comparable to diamond). In graphite, the c-axis (out of plane) thermal conductivity is over a factor of ~100 smaller due to the weak binding forces between basal planes as well as the larger lattice spacing. In addition, the ballistic thermal conductance of graphene is shown to give the lower limit of the ballistic thermal conductances, per unit circumference, length of carbon nanotubes.

Despite its 2-D nature, graphene has 3 acoustic phonon modes. The two in-plane modes (LA, TA) have a linear dispersion relation, whereas the out of plane mode (ZA) has a quadratic dispersion relation. Due to this, the T2 dependent thermal conductivity contribution of the linear modes is dominated at low temperatures by the T1.5 contribution of the out of plane mode. Some graphene phonon bands display negative Grüneisen parameters. At low temperatures (where most optical modes with positive Grüneisen parameters are still not excited) the contribution from the negative Grüneisen parameters will be dominant and thermal expansion coefficient (which is directly proportional to Grüneisen parameters) negative. The lowest negative Grüneisen parameters correspond to the lowest transverse acoustic ZA modes. Phonon frequencies for such modes increase with the in-plane lattice parameter since atoms in the layer upon stretching will be less free to move in the z direction. This is similar to the behavior of a string, which, when it is stretched, will have vibrations of smaller amplitude and higher frequency. This phenomenon, named "membrane effect," was predicted by Lifshitz in 1952.

Mechanical

The (two-dimensional) density of graphene is 0.763 mg per square meter.

Graphene is the strongest material ever tested, with an intrinsic tensile strength of 130 GPa (19,000,000 psi) (with representative engineering tensile strength ~50-60 GPa for stretching large-area freestanding graphene) and a Young's modulus (stiffness) close to 1 TPa (150,000,000 psi). The Nobel announcement illustrated this by saying that a 1 square meter graphene hammock would support a 4 kg cat but would weigh only as much as one of the cat's whiskers, at 0.77 mg (about 0.001% of the weight of 1 m2 of paper).

Large-angle-bent graphene monolayer has been achieved with negligible strain, showing mechanical robustness of the two-dimensional carbon nanostructure. Even with extreme deformation, excellent carrier mobility in monolayer graphene can be preserved.

The spring constant of suspended graphene sheets has been measured using an atomic force microscope (AFM). Graphene sheets were suspended over SiO
2
cavities where an AFM tip was used to apply a stress to the sheet to test its mechanical properties. Its spring constant was in the range 1–5 N/m and the stiffness was 0.5 TPa, which differs from that of bulk graphite. These intrinsic properties could lead to applications such as NEMS as pressure sensors and resonators. Due to its large surface energy and out of plane ductility, flat graphene sheets are unstable with respect to scrolling, i.e. bending into a cylindrical shape, which is its lower-energy state.

As is true of all materials, regions of graphene are subject to thermal and quantum fluctuations in relative displacement. Although the amplitude of these fluctuations is bounded in 3D structures (even in the limit of infinite size), the Mermin–Wagner theorem shows that the amplitude of long-wavelength fluctuations grows logarithmically with the scale of a 2D structure, and would therefore be unbounded in structures of infinite size. Local deformation and elastic strain are negligibly affected by this long-range divergence in relative displacement. It is believed that a sufficiently large 2D structure, in the absence of applied lateral tension, will bend and crumple to form a fluctuating 3D structure. Researchers have observed ripples in suspended layers of graphene, and it has been proposed that the ripples are caused by thermal fluctuations in the material. As a consequence of these dynamical deformations, it is debatable whether graphene is truly a 2D structure. It has recently been shown that these ripples, if amplified through the introduction of vacancy defects, can impart a negative Poisson's ratio into graphene, resulting in the thinnest auxetic material known so far.

Graphene nanosheets have been incorporated into a Ni matrix through a plating process to form Ni-graphene composites on a target substrate. The enhancement in mechanical properties of the composites is attributed to the high interaction between Ni and graphene and the prevention of the dislocation sliding in the Ni matrix by the graphene.

Fracture toughness

In 2014, researchers from Rice University and the Georgia Institute of Technology have indicated that despite its strength, graphene is also relatively brittle, with a fracture toughness of about 4 MPa√m. This indicates that imperfect graphene is likely to crack in a brittle manner like ceramic materials, as opposed to many metallic materials which tend to have fracture toughnesses in the range of 15–50 MPa√m. Later in 2014, the Rice team announced that graphene showed a greater ability to distribute force from an impact than any known material, ten times that of steel per unit weight. The force was transmitted at 22.2 kilometres per second (13.8 mi/s).

Polycrystalline graphene

Various methods – most notably, chemical vapor deposition (CVD), as discussed in the section below - have been developed to produce large-scale graphene needed for device applications. Such methods often synthesize polycrystalline graphene. The mechanical properties of polycrystalline graphene is affected by the nature of the defects, such as grain-boundaries (GB) and vacancies, present in the system and the average grain-size. How the mechanical properties change with such defects have been investigated by researchers, theoretically and experimentally.

Graphene grain boundaries typically contain heptagon-pentagon pairs. The arrangement of such defects depends on whether the GB is in zig-zag or armchair direction. It further depends on the tilt-angle of the GB. In 2010, researchers from Brown University computationally predicted that as the tilt-angle increases, the grain boundary strength also increases. They showed that the weakest link in the grain boundary is at the critical bonds of the heptagon rings. As the grain boundary angle increases, the strain in these heptagon rings decreases, causing the grain-boundary to be stronger than lower-angle GBs. They proposed that, in fact, for sufficiently large angle GB, the strength of the GB is similar to pristine graphene. In 2012, it was further shown that the strength can increase or decrease, depending on the detailed arrangements of the defects. These predictions have since been supported by experimental evidences. In a 2013 study led by James Hone's group, researchers probed the elastic stiffness and strength of CVD-grown graphene by combining nano-indentation and high-resolution TEM. They found that the elastic stiffness is identical and strength is only slightly lower than those in pristine graphene. In the same year, researchers from UC Berkeley and UCLA probed bi-crystalline graphene with TEM and AFM. They found that the strength of grain-boundaries indeed tend to increase with the tilt angle.

While the presence of vacancies is not only prevalent in polycrystalline graphene, vacancies can have significant effects on the strength of graphene. The general consensus is that the strength decreases along with increasing densities of vacancies. In fact, various studies have shown that for graphene with sufficiently low density of vacancies, the strength does not vary significantly from that of pristine graphene. On the other hand, high density of vacancies can severely reduce the strength of graphene.

Compared to the fairly well-understood nature of the effect that grain boundary and vacancies have on the mechanical properties of graphene, there is no clear consensus on the general effect that the average grain size has on the strength of polycrystalline graphene. In fact, three notable theoretical/computational studies on this topic have led to three different conclusions. First, in 2012, Kotakoski and Myer studied the mechanical properties of polycrystalline graphene with "realistic atomistic model", using molecular-dynamics (MD) simulation. To emulate the growth mechanism of CVD, they first randomly selected nucleation sites that are at least 5A (arbitrarily chosen) apart from other sites. Polycrystalline graphene was generated from these nucleation sites and was subsequently annealed at 3000K, then quenched. Based on this model, they found that cracks are initiated at grain-boundary junctions, but the grain size does not significantly affect the strength. Second, in 2013, Z. Song et al. used MD simulations to study the mechanical properties of polycrystalline graphene with uniform-sized hexagon-shaped grains. The hexagon grains were oriented in various lattice directions and the GBs consisted of only heptagon, pentagon, and hexagonal carbon rings. The motivation behind such model was that similar systems had been experimentally observed in graphene flakes grown on the surface of liquid copper. While they also noted that crack is typically initiated at the triple junctions, they found that as the grain size decreases, the yield strength of graphene increases. Based on this finding, they proposed that polycrystalline follows pseudo Hall-Petch relationship. Third, in 2013, Z. D. Sha et al. studied the effect of grain size on the properties of polycrystalline graphene, by modelling the grain patches using Voronoi construction. The GBs in this model consisted of heptagon, pentagon, and hexagon, as well as squares, octagons, and vacancies. Through MD simulation, contrary to the fore-mentioned study, they found inverse Hall-Petch relationship, where the strength of graphene increases as the grain size increases. Experimental observations and other theoretical predictions also gave differing conclusions, similar to the three given above. Such discrepancies show the complexity of the effects that grain size, arrangements of defects, and the nature of defects have on the mechanical properties of polycrystalline graphene.

Chemical

Graphene has a theoretical specific surface area (SSA) of 2630 m2/g. This is much larger than that reported to date for carbon black (typically smaller than 900 m2/g) or for carbon nanotubes (CNTs), from ≈100 to 1000 m2/g and is similar to activated carbon. Graphene is the only form of carbon (or solid material) in which every atom is available for chemical reaction from two sides (due to the 2D structure). Atoms at the edges of a graphene sheet have special chemical reactivity. Graphene has the highest ratio of edge atoms of any allotrope. Defects within a sheet increase its chemical reactivity. The onset temperature of reaction between the basal plane of single-layer graphene and oxygen gas is below 260 °C (530 K). Graphene burns at very low temperature (e.g., 350 °C (620 K)). Graphene is commonly modified with oxygen- and nitrogen-containing functional groups and analyzed by infrared spectroscopy and X-ray photoelectron spectroscopy. However, determination of structures of graphene with oxygen- and nitrogen- functional groups requires the structures to be well controlled.

In 2013, Stanford University physicists reported that single-layer graphene is a hundred times more chemically reactive than thicker multilayer sheets.

Graphene can self-repair holes in its sheets, when exposed to molecules containing carbon, such as hydrocarbons. Bombarded with pure carbon atoms, the atoms perfectly align into hexagons, completely filling the holes.

Biological

Despite the promising results in different cell studies and proof of concept studies, there is still incomplete understanding of the full biocompatibility of graphene based materials. Different cell lines react differently when exposed to graphene, and it has been shown that the lateral size of the graphene flakes, the form and surface chemistry can elicit different biological responses on the same cell line.

There are indications that graphene has promise as a useful material for interacting with neural cells; studies on cultured neural cells show limited success.

Graphene also has some utility in osteogenics. Researchers at the Graphene Research Centre at the National University of Singapore (NUS) discovered in 2011 the ability of graphene to accelerate the osteogenic differentiation of human Mesenchymal Stem Cells without the use of biochemical inducers.

Graphene can be used in biosensors; in 2015 researchers demonstrated that a graphene-based sensor be can used to detect a cancer risk biomarker. In particular, by using epitaxial graphene on silicon carbide, they were repeatably able to detect 8-hydroxydeoxyguanosine (8-OHdG), a DNA damage biomarker.

Support substrate

The electronics property of graphene can be significantly influenced by the supporting substrate. Studies of graphene monolayers on clean and hydrogen(H)-passivated silicon (100) (Si(100)/H) surfaces have been performed. The Si(100)/H surface does not perturb the electronic properties of graphene, whereas the interaction between the clean Si(100) surface and graphene changes the electronic states of graphene significantly. This effect results from the covalent bonding between C and surface Si atoms, modifying the π-orbital network of the graphene layer. The local density of states shows that the bonded C and Si surface states are highly disturbed near the Fermi energy.

Forms

Monolayer sheets

In 2013 a group of Polish scientists presented a production unit that allows the manufacture of continuous monolayer sheets. The process is based on graphene growth on a liquid metal matrix. The product of this process was called High Strength Metallurgical Graphene. In a new study published in Nature, the researchers have used a single layer graphene electrode and a novel surface sensitive non-linear spectroscopy technique to investigate the top-most water layer at the electrochemically charged surface. They found that the interfacial water response to applied electric field is asymmetric with respect to the nature of the applied field.

Bilayer graphene

Bilayer graphene displays the anomalous quantum Hall effect, a tunable band gap and potential for excitonic condensation –making it a promising candidate for optoelectronic and nanoelectronic applications. Bilayer graphene typically can be found either in twisted configurations where the two layers are rotated relative to each other or graphitic Bernal stacked configurations where half the atoms in one layer lie atop half the atoms in the other. Stacking order and orientation govern the optical and electronic properties of bilayer graphene.

One way to synthesize bilayer graphene is via chemical vapor deposition, which can produce large bilayer regions that almost exclusively conform to a Bernal stack geometry.

It has been shown that the two graphene layers can withstand important strain or doping mismatch which ultimately should lead to their exfoliation.

Turbostratic graphene

Turbostratic graphene exhibits weak interlayer coupling, and the spacing is increased with respect to Bernal-stacked multilayer graphene. Rotational misalignment preserves the 2D electronic structure, as confirmed by Raman spectroscopy. The D peak is very weak, whereas the 2D and G peaks remain prominent. A rather peculiar feature is that the I2D/IG ratio can exceed 10. However, most importantly, the M peak, which originates from AB stacking, is absent, whereas the TS1 and TS2 modes are visible in the Raman spectrum. The material is formed through conversion of non-graphenic carbon into graphenic carbon without providing sufficient energy to allow for the reorganization through annealing of adjacent graphene layers into crystalline graphitic structures.

Graphene superlattices

Periodically stacked graphene and its insulating isomorph provide a fascinating structural element in implementing highly functional superlattices at the atomic scale, which offers possibilities in designing nanoelectronic and photonic devices. Various types of superlattices can be obtained by stacking graphene and its related forms. The energy band in layer-stacked superlattices is found to be more sensitive to the barrier width than that in conventional III–V semiconductor superlattices. When adding more than one atomic layer to the barrier in each period, the coupling of electronic wavefunctions in neighboring potential wells can be significantly reduced, which leads to the degeneration of continuous subbands into quantized energy levels. When varying the well width, the energy levels in the potential wells along the L-M direction behave distinctly from those along the K-H direction.

A superlattice corresponds to a periodic or quasi-periodic arrangement of different materials, and can be described by a superlattice period which confers a new translational symmetry to the system, impacting their phonon dispersions and subsequently their thermal transport properties. Recently, uniform monolayer graphene-hBN structures have been successfully synthesized via lithography patterning coupled with chemical vapor deposition (CVD). Furthermore, superlattices of graphene-hBN are ideal model systems for the realization and understanding of coherent (wave-like) and incoherent (particle-like) phonon thermal transport.

Graphene nanoribbons

Names for graphene edge topologies
 
GNR Electronic band structure of graphene strips of varying widths in zig-zag orientation. Tight-binding calculations show that they are all metallic.
 
GNR Electronic band structure of graphene strips of various widths in the armchair orientation. Tight-binding calculations show that they are semiconducting or metallic depending on width (chirality).

Graphene nanoribbons ("nanostripes" in the "zig-zag"/"zigzag" orientation), at low temperatures, show spin-polarized metallic edge currents, which also suggests applications in the new field of spintronics. (In the "armchair" orientation, the edges behave like semiconductors.)

Graphene quantum dots

A graphene quantum dot (GQD) is a graphene fragment with size less than 100 nm. The properties of GQDs are different from 'bulk' graphene due to the quantum confinement effects which only becomes apparent when size is smaller than 100 nm.

Graphene oxide

Graphene oxide is usually produced through chemical exfoliation of graphite. A particularly popular technique is the improved Hummer's method. Using paper-making techniques on dispersed, oxidized and chemically processed graphite in water, the monolayer flakes form a single sheet and create strong bonds. These sheets, called graphene oxide paper, have a measured tensile modulus of 32 GPa. The chemical property of graphite oxide is related to the functional groups attached to graphene sheets. These can change the polymerization pathway and similar chemical processes. Graphene oxide flakes in polymers display enhanced photo-conducting properties. Graphene is normally hydrophobic and impermeable to all gases and liquids (vacuum-tight). However, when formed into graphene oxide-based capillary membrane, both liquid water and water vapor flow through as quickly as if the membrane was not present.

Chemical modification

Photograph of single-layer graphene oxide undergoing high temperature chemical treatment, resulting in sheet folding and loss of carboxylic functionality, or through room temperature carbodiimide treatment, collapsing into star-like clusters.

Soluble fragments of graphene can be prepared in the laboratory through chemical modification of graphite. First, microcrystalline graphite is treated with an acidic mixture of sulfuric acid and nitric acid. A series of oxidation and exfoliation steps produce small graphene plates with carboxyl groups at their edges. These are converted to acid chloride groups by treatment with thionyl chloride; next, they are converted to the corresponding graphene amide via treatment with octadecylamine. The resulting material (circular graphene layers of 5.3 Å or 5.3×10−10 m thickness) is soluble in tetrahydrofuran, tetrachloromethane and dichloroethane.

Refluxing single-layer graphene oxide (SLGO) in solvents leads to size reduction and folding of individual sheets as well as loss of carboxylic group functionality, by up to 20%, indicating thermal instabilities of SLGO sheets dependent on their preparation methodology. When using thionyl chloride, acyl chloride groups result, which can then form aliphatic and aromatic amides with a reactivity conversion of around 70–80%.

Boehm titration results for various chemical reactions of single-layer graphene oxide, which reveal reactivity of the carboxylic groups and the resultant stability of the SLGO sheets after treatment.

Hydrazine reflux is commonly used for reducing SLGO to SLG(R), but titrations show that only around 20–30% of the carboxylic groups are lost, leaving a significant number available for chemical attachment. Analysis of SLG(R) generated by this route reveals that the system is unstable and using a room temperature stirring with HCl (< 1.0 M) leads to around 60% loss of COOH functionality. Room temperature treatment of SLGO with carbodiimides leads to the collapse of the individual sheets into star-like clusters that exhibited poor subsequent reactivity with amines (c. 3–5% conversion of the intermediate to the final amide). It is apparent that conventional chemical treatment of carboxylic groups on SLGO generates morphological changes of individual sheets that leads to a reduction in chemical reactivity, which may potentially limit their use in composite synthesis. Therefore, chemical reactions types have been explored. SLGO has also been grafted with polyallylamine, cross-linked through epoxy groups. When filtered into graphene oxide paper, these composites exhibit increased stiffness and strength relative to unmodified graphene oxide paper.

Full hydrogenation from both sides of graphene sheet results in graphane, but partial hydrogenation leads to hydrogenated graphene. Similarly, both-side fluorination of graphene (or chemical and mechanical exfoliation of graphite fluoride) leads to fluorographene (graphene fluoride), while partial fluorination (generally halogenation) provides fluorinated (halogenated) graphene.

Graphene ligand/complex

Graphene can be a ligand to coordinate metals and metal ions by introducing functional groups. Structures of graphene ligands are similar to e.g. metal-porphyrin complex, metal-phthalocyanine complex, and metal-phenanthroline complex. Copper and nickel ions can be coordinated with graphene ligands.

Graphene fiber

In 2011, researchers reported a novel yet simple approach to fabricate graphene fibers from chemical vapor deposition grown graphene films. The method was scalable and controllable, delivering tunable morphology and pore structure by controlling the evaporation of solvents with suitable surface tension. Flexible all-solid-state supercapacitors based on this graphene fibers were demonstrated in 2013.

In 2015 intercalating small graphene fragments into the gaps formed by larger, coiled graphene sheets, after annealing provided pathways for conduction, while the fragments helped reinforce the fibers. The resulting fibers offered better thermal and electrical conductivity and mechanical strength. Thermal conductivity reached 1,290 W/m/K (1,290 watts per metre per kelvin), while tensile strength reached 1,080 MPa (157,000 psi).

In 2016, Kilometer-scale continuous graphene fibers with outstanding mechanical properties and excellent electrical conductivity are produced by high-throughput wet-spinning of graphene oxide liquid crystals followed by graphitization through a full-scale synergetic defect-engineering strategy. The graphene fibers with superior performances promise wide applications in functional textiles, lightweight motors, microelectronic devices, etc.

Tsinghua University in Beijing, led by Wei Fei of the Department of Chemical Engineering, claims to be able to create a carbon nanotube fibre which has a tensile strength of 80 GPa (12,000,000 psi).

3D graphene

In 2013, a three-dimensional honeycomb of hexagonally arranged carbon was termed 3D graphene, and self-supporting 3D graphene was also produced. 3D structures of graphene can be fabricated by using either CVD or solution based methods. A 2016 review by Khurram and Xu et al. provided a summary of then-state-of-the-art techniques for fabrication of the 3D structure of graphene and other related two-dimensional materials. In 2013, researchers at Stony Brook University reported a novel radical-initiated crosslinking method to fabricate porous 3D free-standing architectures of graphene and carbon nanotubes using nanomaterials as building blocks without any polymer matrix as support. These 3D graphene (all-carbon) scaffolds/foams have applications in several fields such as energy storage, filtration, thermal management and biomedical devices and implants.

Box-shaped graphene (BSG) nanostructure appearing after mechanical cleavage of pyrolytic graphite was reported in 2016.[225] The discovered nanostructure is a multilayer system of parallel hollow nanochannels located along the surface and having quadrangular cross-section. The thickness of the channel walls is approximately equal to 1 nm. Potential fields of BSG application include: ultra-sensitive detectors, high-performance catalytic cells, nanochannels for DNA sequencing and manipulation, high-performance heat sinking surfaces, rechargeable batteries of enhanced performance, nanomechanical resonators, electron multiplication channels in emission nanoelectronic devices, high-capacity sorbents for safe hydrogen storage.

Three dimensional bilayer graphene has also been reported.

Pillared graphene

Pillared graphene is a hybrid carbon, structure consisting of an oriented array of carbon nanotubes connected at each end to a sheet of graphene. It was first described theoretically by George Froudakis and colleagues of the University of Crete in Greece in 2008. Pillared graphene has not yet been synthesised in the laboratory, but it has been suggested that it may have useful electronic properties, or as a hydrogen storage material.

Reinforced graphene

Graphene reinforced with embedded carbon nanotube reinforcing bars ("rebar") is easier to manipulate, while improving the electrical and mechanical qualities of both materials.

Functionalized single- or multiwalled carbon nanotubes are spin-coated on copper foils and then heated and cooled, using the nanotubes themselves as the carbon source. Under heating, the functional carbon groups decompose into graphene, while the nanotubes partially split and form in-plane covalent bonds with the graphene, adding strength. π–π stacking domains add more strength. The nanotubes can overlap, making the material a better conductor than standard CVD-grown graphene. The nanotubes effectively bridge the grain boundaries found in conventional graphene. The technique eliminates the traces of substrate on which later-separated sheets were deposited using epitaxy.

Stacks of a few layers have been proposed as a cost-effective and physically flexible replacement for indium tin oxide (ITO) used in displays and photovoltaic cells.

Moulded graphene

In 2015, researchers from the University of Illinois at Urbana-Champaign (UIUC) developed a new approach for forming 3D shapes from flat, 2D sheets of graphene. A film of graphene that had been soaked in solvent to make it swell and become malleable was overlaid on an underlying substrate "former". The solvent evaporated over time, leaving behind a layer of graphene that had taken on the shape of the underlying structure. In this way they were able to produce a range of relatively intricate micro-structured shapes. Features vary from 3.5 to 50 μm. Pure graphene and gold-decorated graphene were each successfully integrated with the substrate.

Graphene aerogel

An aerogel made of graphene layers separated by carbon nanotubes was measured at 0.16 milligrams per cubic centimeter. A solution of graphene and carbon nanotubes in a mold is freeze dried to dehydrate the solution, leaving the aerogel. The material has superior elasticity and absorption. It can recover completely after more than 90% compression, and absorb up to 900 times its weight in oil, at a rate of 68.8 grams per second.

Graphene nanocoil

In 2015 a coiled form of graphene was discovered in graphitic carbon (coal). The spiraling effect is produced by defects in the material's hexagonal grid that causes it to spiral along its edge, mimicking a Riemann surface, with the graphene surface approximately perpendicular to the axis. When voltage is applied to such a coil, current flows around the spiral, producing a magnetic field. The phenomenon applies to spirals with either zigzag or armchair patterns, although with different current distributions. Computer simulations indicated that a conventional spiral inductor of 205 microns in diameter could be matched by a nanocoil just 70 nanometers wide, with a field strength reaching as much as 1 tesla.

The nano-solenoids analyzed through computer models at Rice should be capable of producing powerful magnetic fields of about 1 tesla, about the same as the coils found in typical loudspeakers, according to Yakobson and his team – and about the same field strength as some MRI machines. They found the magnetic field would be strongest in the hollow, nanometer-wide cavity at the spiral's center.

A solenoid made with such a coil behaves as a quantum conductor whose current distribution between the core and exterior varies with applied voltage, resulting in nonlinear inductance.

Crumpled graphene

In 2016, Brown University introduced a method for 'crumpling' graphene, adding wrinkles to the material on a nanoscale. This was achieved by depositing layers of graphene oxide onto a shrink film, then shrunken, with the film dissolved before being shrunken again on another sheet of film. The crumpled graphene became superhydrophobic, and, when used as a battery electrode, the material was shown to have as much as a 400% increase in electrochemical current density.

Production

A rapidly increasing list of production techniques have been developed to enable graphene's use in commercial applications.

Isolated 2D crystals cannot be grown via chemical synthesis beyond small sizes even in principle, because the rapid growth of phonon density with increasing lateral size forces 2D crystallites to bend into the third dimension. In all cases, graphene must bond to a substrate to retain its two-dimensional shape.

Small graphene structures, such as graphene quantum dots and nanoribbons, can be produced by "bottom up" methods that assemble the lattice from organic molecule monomers (e. g. citric acid, glucose). "Top down" methods, on the other hand, cut bulk graphite and graphene materials with strong chemicals (e. g. mixed acids).

Mechanical

Mechanical exfoliation

Geim and Novoselov initially used adhesive tape to pull graphene sheets away from graphite. Achieving single layers typically requires multiple exfoliation steps. After exfoliation the flakes are deposited on a silicon wafer. Crystallites larger than 1 mm and visible to the naked eye can be obtained.

As of 2014, exfoliation produced graphene with the lowest number of defects and highest electron mobility.

Alternatively a sharp single-crystal diamond wedge penetrates onto the graphite source to cleave layers.

In 2014 defect-free, unoxidized graphene-containing liquids were made from graphite using mixers that produce local shear rates greater than 10×104.

Shear exfoliation is another method which by using rotor-stator mixer the scalable production of the defect-free Graphene has become possible  It has been shown that, as turbulence is not necessary for mechanical exfoliation, low speed ball milling is shown to be effective in the production of High-Yield and water-soluble graphene.

Ultrasonic exfoliation

Dispersing graphite in a liquid medium can produce graphene by sonication followed by centrifugation, producing concentrations 2.1 mg/ml in N-methylpyrrolidone. Using a suitable ionic liquid as the dispersing liquid medium produced concentrations of 5.33 mg/ml. Restacking is an issue with this technique.

Adding a surfactant to a solvent prior to sonication prevents restacking by adsorbing to the graphene's surface. This produces a higher graphene concentration, but removing the surfactant requires chemical treatments.

Sonicating graphite at the interface of two immiscible liquids, most notably heptane and water, produced macro-scale graphene films. The graphene sheets are adsorbed to the high energy interface between the materials and are kept from restacking. The sheets are up to about 95% transparent and conductive.

With definite cleavage parameters, the box-shaped graphene (BSG) nanostructure can be prepared on graphite crystal.

Splitting monolayer carbon

Nanotube slicing

Graphene can be created by opening carbon nanotubes by cutting or etching. In one such method multi-walled carbon nanotubes are cut open in solution by action of potassium permanganate and sulfuric acid.

In 2014, carbon nanotube-reinforced graphene was made via spin coating and annealing functionalized carbon nanotubes.

Fullerene splitting

Another approach sprays buckyballs at supersonic speeds onto a substrate. The balls cracked open upon impact, and the resulting unzipped cages then bond together to form a graphene film.

Chemical

Graphite oxide reduction

P. Boehm reported producing monolayer flakes of reduced graphene oxide in 1962. Rapid heating of graphite oxide and exfoliation yields highly dispersed carbon powder with a few percent of graphene flakes.

Another method is reduction of graphite oxide monolayer films, e.g. by hydrazine with annealing in argon/hydrogen with an almost intact carbon framework that allows efficient removal of functional groups. Measured charge carrier mobility exceeded 1000 cm/Vs (10m/Vs).

Burning a graphite oxide coated DVD produced a conductive graphene film (1738 siemens per meter) and specific surface area (1520 square meters per gram) that was highly resistant and malleable.

A dispersed reduced graphene oxide suspension was synthesized in water by a hydrothermal dehydration method without using any surfactant. The approach is facile, industrially applicable, environmentally friendly and cost effective. Viscosity measurements confirmed that the graphene colloidal suspension (Graphene nanofluid) exhibit Newtonian behavior, with the viscosity showing close resemblance to that of water.

Molten salts

Graphite particles can be corroded in molten salts to form a variety of carbon nanostructures including graphene. Hydrogen cations, dissolved in molten lithium chloride, can be discharged on cathodically polarized graphite rods, which then intercalate, peeling graphene sheets. The graphene nanosheets produced displayed a single-crystalline structure with a lateral size of several hundred nanometers and a high degree of crystallinity and thermal stability.

Electrochemical synthesis

Electrochemical synthesis can exfoliate graphene. Varying a pulsed voltage controls thickness, flake area, number of defects and affects its properties. The process begins by bathing the graphite in a solvent for intercalation. The process can be tracked by monitoring the solution's transparency with an LED and photodiode. 

Hydrothermal self-assembly

Graphene has been prepared by using a sugar (e.g. glucose, sugar, fructose, etc.) This substrate-free "bottom-up" synthesis is safer, simpler and more environmentally friendly than exfoliation. The method can control thickness, ranging from monolayer to multilayers, which is known as "Tang-Lau Method".

Sodium ethoxide pyrolysis

Gram-quantities were produced by the reaction of ethanol with sodium metal, followed by pyrolysis and washing with water.

Microwave-assisted oxidation

In 2012, microwave energy was reported to directly synthesize graphene in one step. This approach avoids use of potassium permanganate in the reaction mixture. It was also reported that by microwave radiation assistance, graphene oxide with or without holes can be synthesized by controlling microwave time. Microwave heating can dramatically shorten the reaction time from days to seconds.

Graphene can also be made by microwave assisted hydrothermal pyrolysis.

Thermal decomposition of silicon carbide

Heating silicon carbide (SiC) to high temperatures (1100 °C) under low pressures (c. 10−6 torr, or 10−4 Pa) reduces it to graphene.

Chemical vapor deposition

Epitaxy

Epitaxial graphene growth on silicon carbide is wafer-scale technique to produce graphene. Epitaxial graphene may be coupled to surfaces weakly enough (by Van der Waals forces) to retain the two dimensional electronic band structure of isolated graphene.

A normal silicon wafer coated with a layer of germanium (Ge) dipped in dilute hydrofluoric acid strips the naturally forming germanium oxide groups, creating hydrogen-terminated germanium. CVD can coat that with graphene.

The direct synthesis of graphene on insulator TiO2 with high-dielectric-constant (high-κ). A two-step CVD process is shown to grow graphene directly on TiO2 crystals or exfoliated TiO2 nanosheets without using any metal catalyst.

Metal substrates

CVD graphene can be grown on metal substrates including ruthenium, iridium, nickel and copper.

Roll-to-roll

In 2014 a two-step roll-to-roll manufacturing process was announced. The first roll-to-roll step produces the graphene via chemical vapor deposition. The second step binds the graphene to a substrate.

Large-area Raman mapping of CVD graphene on deposited Cu thin film on 150 mm SiO2/Si wafers reveals >95% monolayer continuity and an average value of ∼2.62 for I2D/IG. The scale bar is 200 μm.

Cold wall

Growing graphene in an industrial resistive-heating cold wall CVD system was claimed to produce graphene 100 times faster than conventional CVD systems, cut costs by 99% and produce material with enhanced electronic qualities.

Wafer scale CVD graphene

CVD graphene is scalable and has been grown on deposited Cu thin film catalyst on 100 to 300 mm standard Si/SiO2 wafers on an Axitron Black Magic system. Monolayer graphene coverage of >95% is achieved on 100 to 300 mm wafer substrates with negligible defects, confirmed by extensive Raman mapping.

Carbon dioxide reduction

A highly exothermic reaction combusts magnesium in an oxidation–reduction reaction with carbon dioxide, producing carbon nanoparticles including graphene and fullerenes.

Supersonic spray

Supersonic acceleration of droplets through a Laval nozzle was used to deposit reduced graphene-oxide on a substrate. The energy of the impact rearranges that carbon atoms into flawless graphene.

Laser

In 2014, a CO
2
infrared laser was used to produce patterned porous three-dimensional laser-induced graphene (LIG) film networks from commercial polymer films. The resulting material exhibits high electrical conductivity and surface area. The laser induction process is compatible with roll-to-roll manufacturing processes. A similar material, laser-induced graphene fibers (LIGF), was reported in 2018.

Flash Joule heating

In 2019, flash Joule heating (transient high-temperature electrothermal heating) was discovered to be a method to synthesize turbostratic graphene in bulk powder form. The method involves electrothermally converting various carbon sources, such as carbon black, coal, and food waste into micron-scale flakes of graphene. More recent works demonstrated the use of mixed plastic waste, waste rubber tires, and pyrolysis ash as carbon feedstocks. The graphenization process is kinetically controlled, and the energy dose is chosen to preserve the carbon in its graphenic state (excessive energy input leads to subsequent graphitization through annealing).

Ion implantation

Accelerating carbon ions inside an electrical field into a semiconductor made of thin nickel films on a substrate of SiO2/Si, creates a wafer-scale (4 inches (100 mm)) wrinkle/tear/residue-free graphene layer at a relatively low temperature of 500 °C.

CMOS-compatible graphene

Integration of graphene in the widely employed CMOS fabrication process demands its transfer-free direct synthesis on dielectric substrates at temperatures below 500 °C. At the IEDM 2018, researchers from University of California, Santa Barbara, demonstrated a novel CMOS-compatible graphene synthesis process at 300 °C suitable for back-end-of-line (BEOL) applications. The process involves pressure-assisted solid-state diffusion of carbon through a thin-film of metal catalyst. The synthesized large-area graphene films were shown to exhibit high-quality (via Raman characterization) and similar resistivity values when compared with high-temperature CVD synthesized graphene films of same cross-section down to widths of 20 nm.

Simulation

In addition to experimental investigation of graphene and graphene-based devices, their numerical modeling and simulation have been an important research topic. The Kubo formula provides an analytic expression for the graphene's conductivity and shows that it is a function of several physical parameters including wavelength, temperature, and chemical potential. Moreover, a surface conductivity model, which describes graphene as an infinitesimally thin (two sided) sheet with a local and isotropic conductivity, has been proposed. This model permits derivation of analytical expressions for the electromagnetic field in the presence of a graphene sheet in terms of a dyadic Green function (represented using Sommerfeld integrals) and exciting electric current. Even though these analytical models and methods can provide results for several canonical problems for benchmarking purposes, many practical problems involving graphene, such as design of arbitrarily shaped electromagnetic devices, are analytically intractable. With the recent advances in the field of computational electromagnetics (CEM), various accurate and efficient numerical methods have become available for analysis of electromagnetic field/wave interactions on graphene sheets and/or graphene-based devices. A comprehensive summary of computational tools developed for analyzing graphene-based devices/systems is proposed.

Graphene analogs

Graphene analogs (also referred to as "artificial graphene") are two-dimensional systems which exhibit similar properties to graphene. Graphene analogs are studied intensively since the discovery of graphene in 2004. People try to develop systems in which the physics is easier to observe and to manipulate than in graphene. In those systems, electrons are not always the particles which are used. They might be optical photons, microwave photons, plasmons, microcavity polaritons, or even atoms. Also, the honeycomb structure in which those particles evolve can be of a different nature than carbon atoms in graphene. It can be, respectively, a photonic crystal, an array of metallic rods, metallic nanoparticles, a lattice of coupled microcavities, or an optical lattice.

Applications

(a) The typical structure of a touch sensor in a touch panel. (Image courtesy of Synaptics, Incorporated.) (b) An actual example of 2D Carbon Graphene Material Co.,Ltd's graphene transparent conductor-based touchscreen that is employed in (c) a commercial smartphone.

Graphene is a transparent and flexible conductor that holds great promise for various material/device applications, including solar cells, light-emitting diodes (LED), touch panels, and smart windows or phones. Smartphone products with graphene touch screens are already on the market.

In 2013, Head announced their new range of graphene tennis racquets.

As of 2015, there is one product available for commercial use: a graphene-infused printer powder. Many other uses for graphene have been proposed or are under development, in areas including electronics, biological engineering, filtration, lightweight/strong composite materials, photovoltaics and energy storage. Graphene is often produced as a powder and as a dispersion in a polymer matrix. This dispersion is supposedly suitable for advanced composites, paints and coatings, lubricants, oils and functional fluids, capacitors and batteries, thermal management applications, display materials and packaging, solar cells, inks and 3D-printers' materials, and barriers and films.

In 2016, researchers have been able to make a graphene film that can absorb 95% of light incident on it.

Graphene is also getting cheaper. In 2015, scientists at the University of Glasgow found a way to produce graphene at a cost that is 100 times less than the previous methods.

On August 2, 2016, BAC's new Mono model is said to be made out of graphene as a first of both a street-legal track car and a production car.

In January 2018, graphene based spiral inductors exploiting kinetic inductance at room temperature were first demonstrated at the University of California, Santa Barbara, led by Kaustav Banerjee. These inductors were predicted to allow significant miniaturization in radio-frequency integrated circuit applications.

The potential of epitaxial graphene on SiC for metrology has been shown since 2010, displaying quantum Hall resistance quantization accuracy of three parts per billion in monolayer epitaxial graphene. Over the years precisions of parts-per-trillion in the Hall resistance quantization and giant quantum Hall plateaus have been demonstrated. Developments in encapsulation and doping of epitaxial graphene have led to the commercialisation of epitaxial graphene quantum resistance standards.

Toxicity

One review on graphene toxicity published in 2016 by Lalwani et al. summarizes the in vitro, in vivo, antimicrobial and environmental effects and highlights the various mechanisms of graphene toxicity. Another review published in 2016 by Ou et al. focussed on graphene-family nanomaterials (GFNs) and revealed several typical mechanisms such as physical destruction, oxidative stress, DNA damage, inflammatory response, apoptosis, autophagy, and necrosis.

A 2020 study showed that the toxicity of graphene is dependent on several factors such as shape, size, purity, post-production processing steps, oxidative state, functional groups, dispersion state, synthesis methods, route and dose of administration, and exposure times.

In 2014 research at Stony Brook University showed that graphene nanoribbons, graphene nanoplatelets and graphene nano–onions are non-toxic at concentrations up to 50 μg/ml. These nanoparticles do not alter the differentiation of human bone marrow stem cells towards osteoblasts (bone) or adipocytes (fat) suggesting that at low doses graphene nanoparticles are safe for biomedical applications. In 2013 research at Brown University found that 10 μm few-layered graphene flakes are able to pierce cell membranes in solution. They were observed to enter initially via sharp and jagged points, allowing graphene to be internalized in the cell. The physiological effects of this remain uncertain, and this remains a relatively unexplored field.

American Philosophical Society

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