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OAK RIDGE, Tenn., March 16, 2016 — Researchers at theDepartment of Energy’s Oak Ridge National Laboratory have combined advanced in-situ microscopy and theoretical calculations to uncover important clues to the properties of a promising next-generation energy storage material for supercapacitors and batteries.

ORNL’s Fluid Interface Reactions, Structures and Transport (FIRST) research team, using scanning probe microscopy made available through the Center for Nanophase Materials Sciences (CNMS) user program, have observed for the first time at the nanoscale and in a liquid environment how ions move and diffuse between layers of a two-dimensional electrode during electrochemical cycling. This migration is critical to understanding how energy is stored in the material, called MXene, and what drives its exceptional energy storage properties.

“We have developed a technique for liquid environments that allows us to track how ions enter the interlayer spaces. There is very little information on how this actually happens,” said Nina Balke, one of a team of researchers working with Drexel University’s Yury Gogotsi in the FIRST Center, a DOE Office of Science Energy Frontier Research Center.

“The energy storage properties have been characterized on a microscopic scale, but no one knows what happens in the active material on the nanoscale in terms of ion insertion and how this affects stresses and strains in the material,” Balke said.

The so-called MXene material — which acts as a two-dimensional electrode that could be fabricated with the flexibility of a sheet of paper — is based on MAX-phase ceramics, which have been studied for decades. Chemical removal of the “A” layer leaves two-dimensional flakes composed of transition metal layers — the “M” — sandwiching carbon or nitrogen layers (the “X”) in the resulting MXene, which physically resembles graphite.

These MXenes, which have exhibited very high capacitance, or ability to store electrical charge, have only recently been explored as an energy storage medium for advanced batteries.

“The interaction and charge transfer of the ion and the MXene layers is very important for its performance as an energy storage medium. The adsorption processes drive interesting phenomena that govern the mechanisms we observed through scanning probe microscopy,” said FIRST researcher Jeremy Come.

The researchers explored how the ions enter the material, how they move once inside the materials and how they interact with the active material. For example, if cations, which are positively charged, are introduced into the negatively charged MXene material, the material contracts, becoming stiffer.

That observation laid the groundwork for the scanning probe microscopy-based nanoscale characterization. The researchers measured the local changes in stiffness when ions enter the material. There is a direct correlation with the diffusion pattern of ions and the stiffness of the material.

Come noted that the ions are inserted into the electrode in a solution.

“Therefore, we need to work in liquid environment to drive the ions within the MXene material. Then we can measure the mechanical properties in-situ at different stages of charge storage, which gives us direct insight about where the ions are stored,” he said.

Until this study the technique had not been done in a liquid environment.

The processes behind ion insertion and the ionic interactions in the electrode material had been out of reach at the nanoscale until the CNMS scanning probe microscopy group’s studies. The experiments underscore the need for in-situ analysis to understand the nanoscale elastic changes in the 2D material in both dry and wet environments and the effect of ion storage on the energy storage material over time.

The researchers’ next steps are to improve the ionic diffusion paths in the material and explore different materials from the MXene family. Ultimately, the team hopes to understand the process’s fundamental mechanism and mechanical properties, which would allow tuning the energy storage as well as improving the material’s performance and lifetime.

ORNL’s FIRST research team also provided additional calculations and simulations based on density functional theory that support the experimental findings. The work was recently published in the Journal Advanced Energy Materials.

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The research team in addition to Balke and Come and Drexel’s Gogotsi included Michael Naguib, Stephen Jesse, Sergei V. Kalinin, Paul R.C. Kent and Yu Xie, all of ORNL.

The FIRST Center is an Energy Frontier Research Center supported by the DOE Office of Science (Basic Energy Sciences). The Center for Nanophase Materials Sciences and the National Energy Research Scientific Computing Center are DOE Office of Science User Facilities.

UT-Battelle manages ORNL for the DOE’s Office of Science. The Office of Science is the single largest supporter of basic research in the physical sciences in the United States, and is working to address some of the most pressing challenges of our time. For more information, please visit http://science.energy.gov/.

Image:https://www.ornl.gov/sites/default/files/news/images/JCome_MXene.jpg

Image cutline: When a negative bias is applied to a two-dimensional MXene electrode, Li+ ions from the electrolyte migrate in the material via specific channels to the reaction sites, where the electron transfer occurs. Scanning probe microscopy at Oak Ridge National Laboratory has provided the first nanoscale, liquid environment analysis of this energy storage material.

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IMAGEIMAGE: A surfactant template guides the self-assembly of functional polymer structures in an aqueous solution. view more

Credit: Image credit: Oak Ridge National Laboratory, U.S. Dept. of Energy; image by Youngkyu Han and Renee Manning.

OAK RIDGE, Tenn., Oct. 5, 2015–The efficiency of solar cells depends on precise engineering of polymers that assemble into films 1,000 times thinner than a human hair.

Today, formation of that polymer assembly requires solvents that can harm the environment, but scientists at the Department of Energy’s Oak Ridge National Laboratory have found a “greener” way to control the assembly of photovoltaic polymers in water using a surfactant– a detergent-like molecule–as a template. Their findings are reported in Nanoscale, a journal of the Royal Society of Chemistry.

“Self-assembly of polymers using surfactants provides huge potential in fabricating nanostructures with molecular-level controllability,” said senior author Changwoo Do, a researcher at ORNL’s Spallation Neutron Source (SNS).

The researchers used three DOE Office of Science User Facilities–the Center for Nanophase Materials Sciences (CNMS) and SNS at ORNL and the Advanced Photon Source (APS) at Argonne National Laboratory–to synthesize and characterize the polymers.

“Scattering of neutrons and X-rays is a perfect method to investigate these structures,” said Do.

The study demonstrates the value of tracking molecular dynamics with both neutrons and optical probes.

“We would like to create very specific polymer stacking in solution and translate that into thin films where flawless, defect-free polymer assemblies would enable fast transport of electric charges for photovoltaic applications,” said Ilia Ivanov, a researcher at CNMS and a corresponding author with Do. “We demonstrated that this can be accomplished through understanding of kinetic and thermodynamic mechanisms controlling the polymer aggregation.”

The accomplishment creates molecular building blocks for the design of optoelectronic and sensory materials. It entailed design of a semiconducting polymer with a hydrophobic (“water-fearing”) backbone and hydrophilic (“water-loving”) side chains. The water-soluble side-chains could allow “green” processing if the effort produced a polymer that could self-assemble into an organic photovoltaic material. The researchers added the polymer to an aqueous solution containing a surfactant molecule that also has hydrophobic and hydrophilic ends. Depending on temperature and concentration, the surfactant self-assembles into different templates that guide the polymer to pack into different nanoscale shapes–hexagons, spherical micelles and sheets.

In the semiconducting polymer, atoms are organized to share electrons easily. The work provides insight into the different structural phases of the polymer system and the growth of assemblies of repeating shapes to form functional crystals. These crystals form the basis of the photovoltaic thin films that provide power in environments as demanding as deserts and outer space.

“Rationally encoding molecular interactions to rule the molecular geometry and inter-molecular packing order in a solution of conjugated polymers is long desired in optoelectronics and nanotechnology,” said the paper’s first author, postdoctoral fellow Jiahua Zhu. “The development is essentially hindered by the difficulty of in situ characterization.”

In situ, or “on site,” measurements are taken while a phenomenon (such as a change in molecular morphology) is occurring. They contrast with measurements taken after isolating the material from the system where the phenomenon was seen or changing the test conditions under which the phenomenon was first observed. The team developed a test chamber that allows them to use optical probes while changes occur.

Neutrons can probe structures in solutions

Expertise and equipment at SNS, which provides the most intense pulsed neutron beams in the world, made it possible to discover that a functional photovoltaic polymer could self-assemble in an environmentally benign solvent. The efficacy of the neutron scattering was enhanced, in turn, by a technique called selective deuteration, in which specific hydrogen atoms in the polymers are replaced by heavier atoms of deuterium–which has the effect of heightening contrasts in the structure. CNMS has a specialty in the latter technique.

“We needed to be able to see what’s happening to these molecules as they evolve in time from some solution state to some solid state,” author Bobby Sumpter of CNMS said. “This is very difficult to do, but for molecules like polymers and biomolecules, neutrons are some of the best probes you can imagine.” The information they provide guides design of advanced materials.

By combining expertise in topics including neutron scattering, high-throughput data analysis, theory, modeling and simulation, the scientists developed a test chamber for monitoring phase transitions as they happened. It tracks molecules under conditions of changing temperature, pressure, humidity, light, solvent composition and the like, allowing researchers to assess how working materials change over time and aiding efforts to improve their performance.

Scientists place a sample in the chamber and transport it to different instruments for measurements. The chamber has a transparent face to allow entry of laser beams to probe materials. Probing modes–including photons, electrical charge, magnetic spin and calculations aided by high-performance computing–can operate simultaneously to characterize matter under a broad range of conditions. The chamber is designed to make it possible, in the future, to use neutrons and X-rays as additional and complementary probes.

“Incorporation of in situ techniques brings information on kinetic and thermodynamic aspects of materials transformations in solutions and thin films in which structure is measured simultaneously with their changing optoelectronic functionality,” Ivanov said. “It also opens an opportunity to study fully assembled photovoltaic cells as well as metastable structures, which may lead to unique features of future functional materials.”

Whereas the current study examined phase transitions (i.e., metastable states and chemical reactions) at increasing temperatures, the next in situ diagnostics will characterize them at high pressure. Moreover, the researchers will implement neural networks to analyze complex nonlinear processes with multiple feedbacks.

The title of the Nanoscale paper is “Controlling molecular ordering in solution-state conjugated polymers.”

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Zhu, Do and Ivanov led the study. Zhu, Ivanov and Youngkyu Han conducted synchrotron X-ray scattering and optical measurements. Sumpter, Rajeev Kumar and Sean Smith performed theory calculations. Youjun He and Kunlun Hong synthesized the water-soluble polymer. Peter Bonnesen conducted thermal nuclear magnetic resonance analysis on the water-soluble polymer. Do, Han and Greg Smith performed neutron measurement and analysis of the scattering results. This research was conducted at CNMS and SNS, which are DOE Office of Science User Facilities at ORNL. Moreover, the Advanced Photon Source, a DOE Office of Science User Facility at Argonne National Laboratory, was used to perform synchrotron X-ray scattering on the polymer solution. Laboratory Directed Research and Development funds partially supported the work.

UT-Battelle manages ORNL for DOE’s Office of Science. The single largest supporter of basic research in the physical sciences in the United States, the Office of Science is working to address some of the most pressing challenges of our time. For more information, please visit http://science.energy.gov/.

Graphene Mem 050815 3-anewapproach Massachusetts Institute of Technology

 Summary: For faster, longer-lasting water filters, some scientists are looking to graphene –thin, strong sheets of carbon — to serve as ultrathin membranes, filtering out contaminants to quickly purify high volumes of water.

 

Graphene’s unique properties make it a potentially ideal membrane for water filtration or desalination. But there’s been one main drawback to its wider use: Making membranes in one-atom-thick layers of graphene is a meticulous process that can tear the thin material — creating defects through which contaminants can leak. Now engineers have devised a process to repair these leaks.

 

Graphene Mem 050815 3-anewapproach

Graphene’s unique properties make it a potentially ideal membrane for water filtration or desalination. But there’s been one main drawback to its wider use: Making membranes in one-atom-thick layers of graphene is a meticulous process that can tear the thin material — creating defects through which contaminants can leak.

Now engineers at MIT, Oak Ridge National Laboratory, and King Fahd University of Petroleum and Minerals (KFUPM) have devised a process to repair these leaks, filling cracks and plugging holes using a combination of chemical deposition and polymerization techniques. The team then used a process it developed previously to create tiny, uniform pores in the material, small enough to allow only water to pass through.

Combining these two techniques, the researchers were able to engineer a relatively large defect-free graphene membrane — about the size of a penny. The membrane’s size is significant: To be exploited as a filtration membrane, graphene would have to be manufactured at a scale of centimeters, or larger.

In experiments, the researchers pumped water through a graphene membrane treated with both defect-sealing and pore-producing processes, and found that water flowed through at rates comparable to current desalination membranes. The graphene was able to filter out most large-molecule contaminants, such as magnesium sulfate and dextran.

Rohit Karnik, an associate professor of mechanical engineering at MIT, says the group’s results, published in the journal Nano Letters, represent the first success in plugging graphene’s leaks.

“We’ve been able to seal defects, at least on the lab scale, to realize molecular filtration across a macroscopic area of graphene, which has not been possible before,” Karnik says. “If we have better process control, maybe in the future we don’t even need defect sealing. But I think it’s very unlikely that we’ll ever have perfect graphene — there will always be some need to control leakages. These two [techniques] are examples which enable filtration.”

Sean O’Hern, a former graduate research assistant at MIT, is the paper’s first author. Other contributors include MIT graduate student Doojoon Jang, former graduate student Suman Bose, and Professor Jing Kong.

A delicate transfer

“The current types of membranes that can produce freshwater from saltwater are fairly thick, on the order of 200 nanometers,” O’Hern says. “The benefit of a graphene membrane is, instead of being hundreds of nanometers thick, we’re on the order of three angstroms — 600 times thinner than existing membranes. This enables you to have a higher flow rate over the same area.”

O’Hern and Karnik have been investigating graphene’s potential as a filtration membrane for the past several years. In 2009, the group began fabricating membranes from graphene grown on copper — a metal that supports the growth of graphene across relatively large areas. However, copper is impermeable, requiring the group to transfer the graphene to a porous substrate following fabrication.

However, O’Hern noticed that this transfer process would create tears in graphene. What’s more, he observed intrinsic defects created during the growth process, resulting perhaps from impurities in the original material.

Plugging graphene’s leaks

To plug graphene’s leaks, the team came up with a technique to first tackle the smaller intrinsic defects, then the larger transfer-induced defects. For the intrinsic defects, the researchers used a process called “atomic layer deposition,” placing the graphene membrane in a vacuum chamber, then pulsing in a hafnium-containing chemical that does not normally interact with graphene. However, if the chemical comes in contact with a small opening in graphene, it will tend to stick to that opening, attracted by the area’s higher surface energy.

The team applied several rounds of atomic layer deposition, finding that the deposited hafnium oxide successfully filled in graphene’s nanometer-scale intrinsic defects. However, O’Hern realized that using the same process to fill in much larger holes and tears — on the order of hundreds of nanometers — would require too much time.

Instead, he and his colleagues came up with a second technique to fill in larger defects, using a process called “interfacial polymerization” that is often employed in membrane synthesis. After they filled in graphene’s intrinsic defects, the researchers submerged the membrane at the interface of two solutions: a water bath and an organic solvent that, like oil, does not mix with water.

In the two solutions, the researchers dissolved two different molecules that can react to form nylon. Once O’Hern placed the graphene membrane at the interface of the two solutions, he observed that nylon plugs formed only in tears and holes — regions where the two molecules could come in contact because of tears in the otherwise impermeable graphene — effectively sealing the remaining defects.

Using a technique they developed last year, the researchers then etched tiny, uniform holes in graphene — small enough to let water molecules through, but not larger contaminants. In experiments, the group tested the membrane with water containing several different molecules, including salt, and found that the membrane rejected up to 90 percent of larger molecules. However, it let salt through at a faster rate than water.

The preliminary tests suggest that graphene may be a viable alternative to existing filtration membranes, although Karnik says techniques to seal its defects and control its permeability will need further improvements.

“Water desalination and nanofiltration are big applications where, if things work out and this technology withstands the different demands of real-world tests, it would have a large impact,” Karnik says. “But one could also imagine applications for fine chemical- or biological-sample processing, where these membranes could be useful. And this is the first report of a centimeter-scale graphene membrane that does any kind of molecular filtration. That’s exciting.”


Story Source:

The above story is based on materials provided by Massachusetts Institute of Technology. Note: Materials may be edited for content and length.


Journal Reference:

  1. Sean C. O’Hern, Doojoon Jang, Suman Bose, Juan-Carlos Idrobo, Yi Song, Tahar Laoui, Jing Kong, Rohit Karnik. Nanofiltration across Defect-Sealed Nanoporous Monolayer Graphene. Nano Letters, 2015; 150427124208006 DOI: 10.1021/acs.nanolett.5b00456

graphene-nanonporous-mem-ornlledteamd Less than 1 percent of Earth’s water is drinkable. Removing salt and other minerals from our biggest available source of water—seawater—may help satisfy a growing global population thirsty for fresh water for drinking, farming, transportation, heating, cooling and industry. But desalination is an energy-intensive process, which concerns those wanting to expand its application.

Now, a team of experimentalists led by the Department of Energy’s Oak Ridge National Laboratory has demonstrated an energy-efficient desalination technology that uses a porous made of strong, slim graphene—a carbon honeycomb one atom thick. The results are published in the March 23 advance online issue of Nature Nanotechnology.

“Our work is a proof of principle that demonstrates how you can desalinate saltwater using free-standing, porous graphene,” said Shannon Mark Mahurin of ORNL’s Chemical Sciences Division, who co-led the study with Ivan Vlassiouk in ORNL’s Energy and Transportation Science Division.

“It’s a huge advance,” said Vlassiouk, pointing out a wealth of travels through the porous graphene membrane. “The flux through the current graphene membranes was at least an order of magnitude higher than [that through] state-of-the-art polymeric membranes.”

Current methods for purifying water include distillation and reverse osmosis. Distillation, or heating a mixture to extract volatile components that condense, requires a significant amount of energy. Reverse osmosis, a more energy-efficient process that nonetheless requires a fair amount of energy, is the basis for the ORNL technology.

Making pores in the graphene is key. Without these holes, water cannot travel from one side of the membrane to the other. The water molecules are simply too big to fit through graphene’s fine mesh. But poke holes in the mesh that are just the right size, and water molecules can penetrate. Salt ions, in contrast, are larger than and cannot cross the membrane. The allows osmosis, or passage of a fluid through a semipermeable membrane into a solution in which the solvent is more concentrated. “If you have saltwater on one side of a porous membrane and freshwater on the other, an osmotic pressure tends to bring the water back to the saltwater side. But if you overcome that, and you reverse that, and you push the water from the saltwater side to the freshwater side—that’s the reverse osmosis process,” Mahurin explained.

Graphene Nanonporous Mem ornlledteamd

Researchers created nanopores in graphene (red, and enlarged in the circle to highlight its honeycomb structure) that are stabilized with silicon atoms (yellow) and showed their porous membrane could desalinate seawater. Orange represents a …more

Today reverse-osmosis filters are typically polymers. A filter is thin and resides on a support. It takes significant pressure to push water from the saltwater side to the freshwater side. “If you can make the membrane more porous and thinner, you can increase the flux through the membrane and reduce the pressure requirements, within limits,” Mahurin said. “That all serves to reduce the amount of energy that it takes to drive the process.”

Graphene to the rescue Graphene is only one-atom thick, yet flexible and strong. Its mechanical and chemical stabilities make it promising in membranes for separations. A porous graphene membrane could be more permeable than a , so separated water would drive faster through the membrane under the same conditions, the scientists reasoned. “If we can use this single layer of graphene, we could then increase the flux and reduce the membrane area to accomplish that same purification process,” Mahurin said.

To make graphene for the membrane, the researchers flowed methane through a tube furnace at 1,000 degrees C over a copper foil that catalyzed its decomposition into carbon and hydrogen. The chemical vapor deposited carbon atoms that self-assembled into adjoining hexagons to form a sheet one atom thick.

The researchers transferred the graphene membrane to a silicon nitride support with a micrometer-sized hole. Then the team exposed the graphene to an oxygen plasma that knocked carbon atoms out of the graphene’s nanoscale chicken wire lattice to create pores. The longer the graphene membrane was exposed to the plasma, the bigger the pores that formed, and the more made.

The prepared membrane separated two water solutions—salty water on one side, fresh on the other. The silicon nitride chip held the graphene membrane in place while water flowed through it from one chamber to the other. The membrane allowed rapid transport of water through the membrane and rejected nearly 100 percent of the salt ions, e.g., positively charged sodium atoms and negatively charged chloride atoms.

To figure out the best pore size for desalination, the researchers relied on the Center for Nanophase Materials Sciences (CNMS), a DOE Office of Science User Facility at ORNL. There, aberration-corrected scanning transmission electron microscopy (STEM) imaging, led by Raymond Unocic, allowed for atom-resolution imaging of graphene, which the scientists used to correlate the porosity of the graphene membrane with transport properties. They determined the optimum pore size for effective desalination was 0.5 to 1 nanometers, Mahurin said.

They also found the optimal density of pores for desalination was one pore for every 100 square nanometers. “The more pores you get, the better, up to a point until you start to degrade any mechanical stability,” Mahurin said.

Vlassiouk said making the porous membranes used in the experiment is viable on an industrial scale, and other methods of production of the pores can be explored. “Various approaches have been tried, including irradiation with electrons and ions, but none of them worked. So far, the oxygen plasma approach worked the best,” he added. He worries more about gremlins that plague today’s reverse osmosis membranes—growths on membrane surfaces that clog them (called “biofouling”) and ensuring the mechanical stability of a membrane under pressure.

Explore further: Imperfect graphene opens


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