New material for lithium-ion storage - Graphdiyne

Researchers has devised new two-dimensional carbon based materials – called Graphydiyne.  

Carbon is the anode material in lithium-ion batteries. Its layered structure allows lithium ions to travel in and out of the spaces between layers during battery cycling. Carbon has a highly conductive two-dimensional hexagonal crystal lattice, and they form a stable, porous network for efficient electrolyte penetration. However, the fine-tuning of the structural and electrochemical properties is difficult as these carbon materials are mostly prepared from polymeric carbon matter in a top-down synthesis.

Graphdiyne being a hybrid two-dimensional network made of hexagonal carbon rings bridged by two acetylene units, has been used as a nanoweb membrane for the separation of isotopes. However, its distinct electronic properties and web-like structure also make graphdiyne suitable for electrochemical applications. Changshui Huang from the Chinese Academy of Sciences, Beijing, and colleagues have investigated the lithium-storage capabilities and electrochemical properties of tailor-made, electronically adjusted graphdiyne derivatives.

The scientists synthesized the graphdiyne derivatives in a bottom-up approach by adding precursors on a copper foil, which self-organized to form ordered layered nanostructures with distinct electrochemical and morphological properties.

Among these functional groups, those exerting electron-withdrawing effects reduced the band gap of graphdiyne and increased its conductivity, the authors reported. The cyano group was especially effective and, when used as an anodic material, the cyano-modified graphdiyne demonstrated excellent lithium-storage capacity and was stable for thousands of cycles, as the authors reported.

The authors conclude that modified graphdiyne can be prepared by a bottom-up strategy, which is also best suited to build functional two-dimensional carbon material architectures for batteries, capacitors, and other electrocatalytic devices.

 

Mechanosensation device by molybdenum disulfide (MoS2)

In a breakthrough invention, scientists have successfully executed an experiment of piezoelectricity and the piezotronic effect in an atomically thin material, molybdenum disulfide (MoS₂), resulting in a unique electric generator and mechanosensation devices; although the piezoelectric effect in this material had already been predicted theoretically.

Piezoelectricity is defined as a phenomenon in which pressure generates an electrical voltage in a material or vice-versa. But no experimental observation of piezoelectricity has been made yet for few atom thickness material. The observation of molybdenum disulfide material has unfolded the potential for new types of mechanically controlled electronic devices.

In an interesting application of this phenomenon, this material could be made as a wearable device, integrated into clothing, to convert energy from your body movement to electricity and power wearable sensors or medical devices, or perhaps supply enough energy to charge cell phone.

There are two keys to using molybdenum disulfide for generating current: using an odd number of layers and flexing it in the proper direction. The material is highly polar, but an even number of layers cancels out the piezoelectric effect. The material's crystalline structure also is piezoelectric in only certain crystalline orientations.

Group of researchers placed thin flakes of MoS₂ on flexible plastic substrates and determined how their crystal lattices were oriented using optical techniques. They then patterned metal electrodes onto the flakes and measure current flow as the samples were mechanically deformed. They monitored the conversion of mechanical to electrical energy, and observed voltage and current outputs.

The researchers also noted that the output voltage reversed sign when they changed the direction of applied strain, and that it disappeared in samples with an even number of atomic layers, confirming theoretical predictions published last year. The presence of piezotronic effect in odd layered MoS₂ was also observed for the first time.

To be piezoelectric, a material must break central symmetry. A single atomic layer of MoS₂ has such a structure, and should be piezoelectric. However, in bulk MoS₂, successive layers are oriented in opposite directions, and generate positive and negative voltages that cancel each other out and give zero net piezoelectric effect.

In fact, MoS₂ is just one of a group of 2D semiconducting materials known as transition metal dichalcogenides, all of which are predicted to have similar piezoelectric properties. These are part of an even larger family of 2D materials whose piezoelectric materials remain unexplored. The research could lead to complete atomic-thick nanosystems that are self-powered by harvesting mechanical energy from the environment. This study also reveals the piezotronic effect in two-dimensional materials for the first time, which greatly expands the application of layered materials for human-machine interfacing, robotics, MEMS, and active flexible electronics.

New nanomaterial for longer battery life

An architecture nanostructured material has been recently developed by researchers at the University of California using nanocrystalline ruthenium oxide coupled with graphene. This technology could improve the quality of the supercapacitors leading to long lasting battery life in portable electronics.

 

The present study showed that two times more energy and power can be achieved with this material compared to commercial supercapacitors. The electrode and/or supercapacitors made with above mentioned nanomaterial can be cycled over 8000 times without any fatigue because of its high energy density. Nanostructured materials also rendered large surface area, high electrical conductivity, short ion diffusion pathways and excellent interfacial integrity, making these high energy supercapacitor electrodes ideal for future energy storage applications.

New material for fuel cell catalyst

Efficient, robust and economical catalyst materials hold the key to achieving a breakthrough in fuel cell technology. Scientists from Jülich and Berlin have developed a material for converting hydrogen and oxygen to water using a tenth of the typical amount of platinum that was previously required. With the aid of state-of-the-art electron microscopy, the researchers discovered that the function of the nanometre-scale catalyst particles is decisively determined by their geometric shape and atomic structure. This discovery opens up the opportunity for further improved catalysts for energy conversion and storage. 

Hydrogen-powered fuel cells are regarded as a clean alternative to conventional combustion engines, as the only substance produced during operation is water. At present, the implementation of hydrogen fuel cells is being hindered by the high material costs of platinum. Large quantities of the expensive noble metal are still required for the electrodes in the fuel cells at which the chemical conversion processes take place. Without the catalytic effect of the platinum, it is not currently possible to achieve the necessary conversion rates.

As catalysis takes place at the surface of the platinum only, material can be saved and, simultaneously, the efficiency of the electrodes improved by using platinum nanoparticles, thus increasing the ratio of platinum surface to material required. Although the tiny particles are around ten thousand times smaller than the diameter of a human hair, the surface area of a kilogram of such particles is huge.

However, more platinum can be saved by mixing it with nickel or copper. Scientist have succeeded in developing efficient metallic catalyst particles for converting hydrogen and oxygen to water using only a tenth of the typical amount of platinum that was previously required. 

The new catalyst consists of octrahedral-shaped nanoparticles of a platinum-nickel alloy. The researchers discovered that the unique manner in which the platinum and nickel atoms arrange themselves on the surfaces to accelerate the chemical reaction between hydrogen and oxygen to form water. Round or cubic particles have different atomic arrangements at the surface and are therefore less effective catalysts for the chemical reaction, which could be compensated by using increased amounts of noble metal.

“Antenna” like InP nanowires for high solar efficiency

In a recent study, researchers from Lund University in Sweden have shown how nanowires could pave the way for more efficient and cheaper solar cells. This finding first shows that it is possible to use nanowires to manufacture solar cells.

Research on solar cell nanowires is on the rise globally. Until now the unattained dream figure was ten per cent efficiency; but now scientists are able to report an efficiency of 13.8 per cent.

The nanowires are made of the semiconductor material indium phosphide and work like antennae that absorb sunlight and generate power. The nanowires are assembled on surfaces of one square millimetre which can hold four million nanowires. A nanowire solar cell can produce an effect per active surface unit several times greater than today's silicon cells.

Nanowire solar cells have not yet made it beyond the laboratory, but the plan is that the technology could be used in large solar power plants in sunny regions.

The Lund researchers have now managed to identify the ideal diameter of the nanowires and how to synthesize them.

The right size is essential for the nanowires to absorb as many photons as possible. If they are just a few tenths of a nanometre, their function is significantly impaired. The silicon solar cells that are used to supply electricity for domestic use are relatively cheap, but inefficient because they are only able to utilise a limited part of the effect of the sunlight. The reason is that one single material can only absorb part of the spectrum of the light.

Research carried out alongside that on nanowire technology therefore aims to combine different types of semiconductor materials to make efficient use of a broader part of the solar spectrum. The disadvantage of this is that they become extremely expensive and can therefore only be used in applications such as on satellites and military planes.

However, this is not the case with nanowires. Because of their small dimensions, the same sort of material combinations can be created with much less effort, which offers higher efficiency at a low cost. The process is also less complicated. In this study, the researchers have shown that the nanowires can generate power at the same level as a thin film of the same material, even if they only cover around 10 per cent of the surface rather than 100 per cent.

 

For further studies:

http://www.sciencemag.org/content/early/2013/01/16/science.1230969

Molybdenum disulfide (MoS2): New nanomaterial with several advantages

The discovery of graphene, a material just one atom thick and possessing exceptional strength and other novel properties, started an avalanche of research around its use for everything from electronics to optics to structural materials. But new research suggests that was just the beginning: A whole family of two-dimensional materials may open up even broader possibilities for applications that could change many aspects of modern life.

The latest new material, molybdenum disulfide (MoS₂) was first described just a year ago by researchers in Switzerland. But in that year, researchers at MIT who struggled for several years to build electronic circuits out of graphene with very limited results (have already succeeded in making a variety of electronic components from MoS₂. They say the material could help usher in radically new products, from whole walls that glow to clothing with embedded electronics to glasses with built-in display screens.

 Researchers think graphene and MoS₂ are just the beginning of a new realm of research on two-dimensional materials. Like graphene, itself a 2-D form of graphite, molybdenum disulfide has been used for many years as an industrial lubricant. But it had never been seen as a 2-D platform for electronic devices until last year, when scientists at the Swiss university produced a transistor on the material.

 Then MIT researchers found a good way to make large sheets of the material using a chemical vapor deposition process. As there are lots of hindrance in making electronic products out of graphene due to lack of bandgap, MoS₂ just naturally comes with large band gap.

 MoS₂ is widely produced as a lubricant and as others are working on making it into large sheets, scaling up production of the material for practical uses should be much easier than with other new materials. People are able to fabricate a variety of basic electronic devices on the material: an inverter, which switches an input voltage to its opposite; a NAND gate, a basic logic element that can be combined to carry out almost any kind of logic operation; a memory device, one of the key components of all computational devices; and a more complex circuit called a ring oscillator, made up of 12 interconnected transistors, which can produce a precisely tuned wave output.

One potential application of the new material is large-screen displays such as television sets and computer monitors, where a separate transistor controls each pixel of the display. Because the material is just one molecule thick, unlike the highly purified silicon that is used for conventional transistors and must be millions of atoms thick, even a very large display would use only an infinitesimal quantity of the raw materials. This could potentially reduce cost and weight and improve energy efficiency.

Further reading:

arxiv.org/pdf/1208.1078 

 

In the future, it could also enable entirely new kinds of devices. The material could be used, in combination with other 2-D materials, to make light-emitting devices. Instead of producing a point source of light from one bulb, an entire wall could be made to glow, producing softer, less glaring light. Similarly, the antenna and other circuitry of a cellphone might be woven into fabric, providing a much more sensitive antenna that needs less power and could be incorporated into clothing.

 The material is so thin that it's completely transparent, and it can be deposited on virtually any other material. For example, MoS₂ could be applied to glass, producing displays built into a pair of eyeglasses or the window of a house or office.

Newest Material for Optical Applications

Researchers have been successful in developing a structure that could bring optical advances including ultrapowerful microscopes, computers and solar cells. They have shown how to create the metamaterials without the traditional silver or gold previously required. Using the metals is impractical for industry because of high cost and incompatibility with semiconductor manufacturing processes. The metals also do not transmit light efficiently, causing much of it to be lost. The Purdue researchers replaced the metals with an aluminum-doped zinc oxide (AZO).

This new metamaterial consists of 16 layers alternating between AZO and zinc oxide. Light passing from the zinc oxide to the AZO layers encounters an extreme anisotropy, causing its dispersion to become hyperbolic, which dramatically changes the light's behaviour. The doped oxide brings not only enhanced performance but also is compatible with semiconductors. Metamaterials can be applied in optical microscopes that would make them 10 times more powerful and able to see objects as small as DNA; and also useful in advanced sensors; more efficient solar collectors; quantum computing; and cloaking devices. The AZO also modulate the optical properties of metamaterials by varying the concentration of aluminium in the AZO and also by applying an electric filed to the fabricated metamaterial. This switching ability might usher in a new class of metamaterials that could be turned hyperbolic and non-hyperbolic at the flip of a switch.

This could actually lead to a whole new family of devices that can be tuned or switched. AZO can go from dielectric to metallic. So at one specific wavelength, at one applied voltage, it can be metal and at another voltage it can be dielectric. This would lead to tremendous changes in functionality.

The researcher doped zinc oxide with aluminum, meaning the zinc oxide is impregnated with aluminum atoms to alter the material's optical properties. Doping the zinc oxide causes it to behave like a metal at certain wavelengths and like a dielectric at other wavelengths.

The material has been shown to work in the near-infrared range of the spectrum, which is essential for optical communications, and could allow researchers to harness optical black holes to create a new generation of light-harvesting devices for solar energy applications.

 Current optical technologies are limited because, for the efficient control of light, components cannot be smaller than the size of the wavelengths of light. Metamaterials are able to guide and control light on all scales, including the scale of nanometers, or billionths of a meter.

Unlike natural materials, metamaterials are able to reduce the index of refraction to less than one or less than zero. Refraction occurs as electromagnetic waves, including light, bend when passing from one material into another. It causes the bent-stick-in-water effect, which occurs when a stick placed in a glass of water appears bent when viewed from the outside. Each material has its own refraction index, which describes how much light will bend in that particular material and defines how much the speed of light slows down while passing through a material

Natural materials typically have refractive indices greater than one. Metamaterials, however, can make the index of refraction vary from zero to one, which possibly will enable applications including the hyperlens.

Alternative plasmonic materials such as AZO overcome the bottleneck created by conventional metals in the design of optical metamaterials and enable more efficient devices.

Solar Cell fabricated by High Bandgap Inorganic Zinc Oxide Nanowire Arrays

Arrays of core/shell nanowires had previously been theorized as a potential structure that, while composed of chemically more stable large bandgap inorganic materials, should also be capable of absorbing the broad range of the wavelengths present in sunlight. High bandgap semiconductors are generally considered not effective at absorbing most of the available wavelengths in solar radiation by themselves. For instance, high bandgap zinc oxide (ZnO) is transparent in the visible but absorptive in the ultraviolet range, and thus is widely used in sunscreens but was not considered useful in solar cells.

In the report, a team of researchers from Xiamen University in China and the University of North Carolina at Charlotte describe successfully creating zinc oxide (ZnO) nanowires with a zinc selenide (ZnSe) coating to form a material structure known as a type-II heterojunction that has a significantly lower bandgap than either of the original materials. The team reported that arrays of the structured nanowires were subsequently able to absorb light from the visible and near-infrared wavelengths, and show the potential use of wide bandgap materials for a new kind of affordable and durable solar cell.

"High bandgap materials tend to be chemically more stable than the lower bandgap semiconductors that we currently have," noted team member Yong Zhang, a Bissell Distinguished Professor in the Department of Electrical and Computer Engineering and in the Energy Production and Infrastructure Center (EPIC) at the University of North Carolina at Charlotte.

And these nanowire structures can be made using a very low cost technology, using a chemical vapor deposition (CVD) technique to grow the array," he added. "In comparison, solar cells using silicon and gallium arsenide require more expensive production techniques.

Past attempts to use high band gap materials did not actually use the semiconductors to absorb light but instead involved coating them with organic molecules (dyes) that accomplished the photo absorption and simply transmitted electrons to the semiconductor material. In contrast, the team's heterojunction nanowires absorb the light directly and efficiently conduct a current through nano-sized "coaxial" wires, which separate charges by putting the excited electrons in the wires' zinc oxide cores and the "holes" in the zinc selenide shells.

"By making a special heterojunction architecture at the nanoscale, we are also making coaxial nanowires which are good for conductivity," said Zhang. "Even if you have good light absorption and you are creating electron-hole pairs, you need to be able to take them out to the circuit to get current, so we need to have good conductivity. These coaxial nanowires are similar to the coaxial cable in electrical engineering. So basically we have two conducting channels -- the electron going one way in the core and the hole going the other way in the shell."

The nanowires were created by first growing an array of six-sided zinc oxide crystal "wires" from a thin film of the same material using vapor deposition. The technique created a forest of smooth-sided needle-like zinc oxide crystals with uniform diameters (40 to 80 nanometers) along their length (approximately 1.4 micrometers). A somewhat rougher zinc selenide shell was then deposited to coat all the wires. Finally, an indium tin oxide (ITO) film was bonded to the zinc selenide coating, and an indium probe was connected to the zinc oxide film, creating contacts for any current generated by the cell.

"We measured the device and showed the photoresponse threshold to be 1.6 eV," Zhang said, noting that the cell was thus effective at absorbing light wave wavelengths from the ultraviolet to the near infrared, a range that covers most of the solar radiation reaching earth's surface.

Though the use of the nanowires for absorbing light energy is an important innovation, perhaps even more important is the researchers' success in using stable high bandgap inorganic semiconductor materials for an inexpensive but effective solar energy device.

"This is a new mechanism, since these materials were previously not considered directly useful for solar cells," Zhang said. He stressed that the applications for the concept do not end there but open the door to considering a larger number of high bandgap semiconductor materials with very desirable material properties for various solar energy related applications, such as hydrogen generation by photoelectrochemical water splitting.

"The expanded use of type II nanoscale heterostructures also extends their use for other applications as well, such as photodetectors -- IR detector in particular," he noted.

 

Nanosilver

Nanosilver is not a new discovery by nanotechnologists - it has been used in various products for over a hundred years,. The antimicrobial effects of minute silver particles, which were then known as "colloidal silver", were known from the earliest days of its use.

As early as the 19th century, minute silver particles were used, for example in antibacterial water filters.

Numerous nanomaterials are currently at the focus of public attention. In particular silver nanoparticles are being investigated in detail, both by scientists as well as by the regulatory authorities. The assumption behind this interest is that they are dealing with a completely new substance. However, nanosilver is by no means the discovery of the 21st century. Silver particles with diameters of seven to nine nm were mentioned as early as 1889. They were used in medications or as biocides to prevent the growth of bacteria on surfaces, for example in antibacterial water filters or in algaecides for swimming pools.

The nanoparticles were known as colloidal silver in those days, but now - extremely small particles of silver. The only new aspect is the use today of the prefix nano. "However," according to Bernd Nowack, "nano does not mean something new, and nor does it mean something that is harmful." When colloidal silver" became available on the market in large quantities in the 1920s it was the topic of numerous studies and subject to appropriate regulation by the authorities. Even in those days the significance of the discovery of nanoparticles and how they worked was realized. But that does not mean that the possible side-effects of nanoparticles on humans and the environment should be played down or ignored. It is important to characterize in exact detail the material properties of nanosilver and not just to use without verifying.

The term nanoparticle is understood to refer to particles whose dimensions are less than 100 nm. Because of their minute size nanoparticles have different properties than those of larger particles of the same material. For example, for a given volume nanoparticles have a much greater surface area, so they are frequently much more reactive than the bulk material. In addition, even in small quantities nanosilver produces more silver ions than solid silver. These silver ions are toxic to bacteria. Whether or not nanosilver represents a risk to humans and the environment is currently the subject of a great deal of investigation.

NEW HORIZON IN TITANIUM DIOXIDE

There is growing interest in smaller, truly nano-sized titanium dioxide particles with well-defined crystallinity and a range of geometries from spheres to rods and tubes, that are relevant to applications in composites, photovoltaics, sensors, and catalysis. High aspect ratios, in particular, introduce high surface to volume ratios, network forming abilities, and opportunities to control anisotropic properties.

At NSTI (Nano Science and Technology Institute) Nanotech 2008, different synthetic strategies were reported for producing high aspect ratio titanium dioxide nanostructures. Titanium dioxide is commonly obtained via hydrolysis of metal alkoxides or halides; however, enhanced control over the reaction can be achieved in non-hydrous conditions. Dimensions of the resulting nanorods, and even their crystal phase, can be adjusted using different structure directing agents to adsorb to the growing surfaces. Typical products are small, single crystal nanorods of anatase (~ 3 25 nm), although aging reactions under suitable conditions yield single crystal rutile nanorods (15 x 135 nm). The more conventional hydrolytic synthesis can be dramatically accelerated (can around an order of magnitude) when performed on a microfluidic chip, as compared to the conventional bulk reaction. This first example of an on-chip synthesis of nanorods showed that the rapid mixing and controlled environment provides useful benefits, even though monodispersity was not significantly affected.

More recently using a novel, phase transfer process, in suspension, natural photocatalytic properties have been exploited of titania to remove the structure directing ligands without causing agglomeration. After the reaction, the nanorods can be fully dispersed in aqueous solution, or functionalised as desired. The nanorods can be dispersed in a range of polymers to create optically clear nanocomposites with UV-filtering characteristics; by functionalising the titania with a monolayer of silane, the degradation of the matrix can be suppressed. The nanorods also offer valuable advantages in photovoltaic devices.

ABOUT NANOMATERIALS

Over the past decade, nanomaterials have been the subject of enormous interest. These materials, notable for their extremely small feature size, have the potential for wide-ranging industrial, biomedical, and electronic applications. As a result of recent improvement in technologies to see and manipulate these materials, the nanomaterials field has seen a huge increase in funding from private enterprises and government, and academic researchers within the field have formed many partnerships.
Nanomaterials can be metals, ceramics, polymeric materials, or composite materials. Their defining characteristic is a very small feature size in the range of 1-100 nanometers (nm). The unit of nanometer derives its prefix nano from a Greek word meaning dwarf or extremely small. One nanometer spans 3-5 atoms lined up in a row. By comparison, the diameter of a human hair is about 5 orders of magnitude larger than a nanoscale particle. Nanomaterials are not simply another step in miniaturization, but a different arena entirely; the nanoworld lies midway between the scale of atomic and quantum phenomena, and the scale of bulk materials. At the nanomaterial level, some material properties are affected by the laws of atomic physics, rather than behaving as traditional bulk materials do.
Although widespread interest in nanomaterials is recent, the concept was raised over 40 years ago. Physicist Richard Feynman delivered a talk in 1959 entitled "There's Plenty of Room at the Bottom", in which he commented that there were no fundamental physical reasons that materials could not be fabricated by maneuvering individual atoms. Nanomaterials have actually been produced and used by humans for hundreds of years - the beautiful ruby red color of some glass is due to gold nanoparticles trapped in the glass matrix. The decorative glaze known as luster, found on some medieval pottery, contains metallic spherical nanoparticles dispersed in a complex way in the glaze, which give rise to its special optical properties. The techniques used to produce these materials were considered trade secrets at the time, and are not wholly understood even now.
Development of nanotechnology has been spurred by refinement of tools to see the nanoworld, such as more sophisticated electron microscopy and scanning tunneling microscopy. By 1990, scientists at IBM had managed to position individual xenon atoms on a nickel surface. In the mid-1980s a new class of material - hollow carbon spheres - was discovered. These spheres were called buckyballs or fullerenes, in honor of architect and futurist Buckminster Fuller, who designed a geodesic dome with geometry similar to that found on the molecular level in fullerenes. The C60 (60 carbon atoms chemically bonded together in a ball-shaped molecule) buckyballs inspired research that led to fabrication of carbon nanofibers, with diameters under 100 nm. In 1991 S. Iijima of NEC in Japan reported the first observation of carbon nanotubes1, which are now produced by a number of companies in commercial quantities. The world market for nanocomposites (one of many types of nanomaterials) grew to millions of pounds by 1999 and is still growing fast.
The variety of nanomaterials is great, and their range of properties and possible applications appear to be enormous, from extraordinarily tiny electronic devices, including miniature batteries, to biomedical uses, and as packaging films, super absorbants, components of armor, and parts of automobiles. General Motors claims to have the first vehicle to use the materials for exterior automotive applications, in running boards on its mid-size vans.
What makes these nanomaterials so different and so intriguing? Their extremely small feature size is of the same scale as the critical size for physical phenomena. Fundamental electronic, magnetic, optical, chemical, and biological processes are also different at this level. Where proteins are 10-1000 nm in size, and cell walls 1-100 nm thick, their behavior on encountering a nanomaterial may be quite different from that seen in relation to larger-scale materials. Nanocapsules and nanodevices may present new possibilities for drug delivery, gene therapy, and medical diagnostics.
Surfaces and interfaces are also important in explaining nanomaterial behavior. In bulk materials, only a relatively small percentage of atoms will be at or near a surface or interface (like a crystal grain boundary). In nanomaterials, the small feature size ensures that many atoms, perhaps half or more in some cases, will be near interfaces. Surface properties such as energy levels, electronic structure, and reactivity can be quite different from interior states, and give rise to quite different material properties.