Brookhaven National Lab: The rapid self-assembly of nanoscale patterns for next-generation materials: From Electronics and Computing to Energy and Medicine

Brookhaven II 10-nanoparticleThe ability to quickly generate ultra-small, well-ordered nanopatterns over large areas on material surfaces is critical to the fabrication of next-generation technologies in many industries, from electronics and computing to energy and medicine. For example, patterned media, in which data are stored in periodic arrays of magnetic pillars or bars, could significantly improve the storage density of hard disk drives.

Scientists can coax thin films of self-assembling materials called block copolymers—chains of chemically distinct macromolecules (polymer “blocks”) linked together—into desired nanoscale patterns through heating (annealing) them on a substrate. However, defective structures that deviate from the regular pattern emerge early on during self-assembly.

Brookhaven6-acceleratingMaterials scientist Gregory Doerk preparing a sample for electron microscopy at Brookhaven Lab’s Center for Functional Nanomaterials. The scanning electron microscope image on the computer screen shows a cross-sectional view of line …more

The presence of these defects inhibits the use of block copolymers in the nanopatterning of technologies that require a nearly perfect ordering—such as magnetic media, computer chips, antireflective surfaces, and medical diagnostic devices. With continued annealing, the block copolymer patterns can reconfigure to remove the imperfections, but this process is exceedingly slow. The polymer blocks do not readily mix with each other, so they must overcome an extremely large energy barrier to reconfigure.

Adding small things with a big impact

Now, scientists from the Center for Functional Nanomaterials (CFN)—a U.S. Department of Energy (DOE) Office of Science User Facility at Brookhaven National Laboratory—have come up with a way to massively speed up the ordering process. They blended a line-forming block copolymer with significantly smaller polymer chains made of only one type of molecule (homopolymers) from each of the two constituent blocks. The electron microscopy images they took after annealing the films for only a few minutes show that the addition of these two smaller homopolymers dramatically increases the size of well-ordered line-pattern areas, or “grains.”

Accelerating the self-assembly of nanoscale patterns for next-generation materials
As shown in the illustration, a block copolymer consists of different molecule chains (red and blue) linked together; a homopolymer chain consists of identical molecules (red or blue). In this study, scientists blended a block copolymer …more

“Without the homopolymers, the same block copolymer cannot produce grains with these sizes,” said CFN materials scientist Gregory Doerk, who led the work, which was published online in an ACS Nano paper on December 1. “Blending in homopolymers that are less than one-tenth of the size of the block copolymer greatly accelerates the ordering process. In the resulting line patterns, there is a constant spacing between each of the lines, and the same directions of line-pattern orientations—for example, vertical or horizontal—persist over longer distances.”

Doerk and coauthor Kevin Yager, leader of the Electronic Nanomaterials Group at CFN, used image analysis software to calculate the grain size and repeat spacing of the line patterns.

While blending different concentrations of homopolymer to determine how much was needed to achieve the accelerated ordering, they discovered that the ordering sped up as more homopolymer was added. But too much homopolymer actually resulted in disordered patterns.

Accelerating the self-assembly of nanoscale patterns for next-generation materials
The scanning electron microscope images taken after thermal annealing at around 480 degrees Fahrenheit for five minutes show that the block copolymer/homopolymer blend generates a line pattern with a significantly higher degree of …more

“The homopolymers accelerate the self-assembly process because they are small enough to uniformly distribute throughout their respective polymer blocks,” said Doerk. “Their presence weakens the interface between the two blocks, lowering the energy barrier associated with the block copolymer reconfiguring to remove the defects. But if the interface is weakened too much through the addition of too much homopolymer, then the blocks will mix together, resulting in a completely disordered phase.”

Guiding the self-assembly of useful nanopatterns in minutes

To demonstrate how the rapid ordering in the blended system could accelerate the self-assembly of well-aligned nanopatterns over large areas, Doerk and Yager used line-pattern templates they had previously prepared through photolithography. Used to build almost all of today’s digital devices, photolithography involves projecting light through a mask (a plate containing the desired pattern) that is positioned over a wafer (usually made of silicon) coated with a light-sensitive material. This template can then be used to direct the self-assembly of block copolymers, which fill in the spaces between the template guides. In this case, after only two minutes of annealing, the polymer blend self-assembles into lines that are aligned across these gaps. However, after the same annealing time, the unblended block copolymer self-assembles into a mostly unaligned pattern with many defects between the gaps.

Accelerating the self-assembly of nanoscale patterns for next-generation materials
The unblended block copolymer aligns well close to the template guides (“sidewalls”), but this alignment degrades further in, as evident by the appearance of the fingerprint-like pattern in the center of the scanning electron microscope …more

“The width of the gaps is more than 80 times the repeat spacing, so the fact that we got this degree of alignment with our polymer blend is really exciting because it means we can use templates with huge gaps, created with very low-resolution lithography,” said Doerk. “Typically, expensive high-resolution lithography equipment is needed to align block copolymer patterns over this large of an area.”

For these patterns to be useful for many nanopatterning applications, they often need to be transferred to other more robust materials that can withstand harsh manufacturing processes—for example, etching, which removes layers from silicon wafer surfaces to create integrated circuits or make the surfaces antireflective. In this study, the scientists converted the nanopatterns into a metal-oxide replica. Through chemical etching, they then transferred the replica  into a silicon dioxide layer on a silicon wafer, achieving clearly defined line patterns.

Doerk suspects that blending homopolymers with other  will similarly yield accelerated assembly, and he is interested in studying blended polymers that self-assemble into more complicated patterns. The x-ray scattering capabilities at the National Synchrotron Light Source II—another DOE Office of Science User Facility at Brookhaven—could provide the structural information needed to conduct such studies.

Accelerating the self-assembly of nanoscale patterns for next-generation materials
A scanning electron microscope image showing a cross-sectional view of the line patterns transferred into a silicon dioxide layer. Credit: Brookhaven National Laboratory

“We have introduced a very simple and easily controlled way of immensely accelerating self-assembly,” concluded Doerk. “Our approach should substantially reduce the number of defects, helping to meet the demands of the semiconductor industry. At CFN, it opens up possibilities for us to use block copolymer self-assembly to make some of the new functional materials that we envision.”

 Explore further: Self-assembling polymers provide thin nanowire template

More information: Gregory S. Doerk et al. Rapid Ordering in “Wet Brush” Block Copolymer/Homopolymer Ternary Blends, ACS Nano (2017). DOI: 10.1021/acsnano.7b06154



Berkeley Lab – DOE – Argonne – “Holy Grail” for Batteries: Solid-State Magnesium Battery a Big Step Closer


Berkeley Lab leads discovery of the fastest magnesium-ion solid-state conductor to date.


A team of Department of Energy (DOE) scientists at the Joint Center for Energy Storage Research (JCESR) has discovered the fastest magnesium-ion solid-state conductor, a major step towards making solid-state magnesium-ion batteries that are both energy dense and safe.

Argonne scientist Baris Key, shown on left at work in his nuclear magnetic resonance lab, worked with researchers at Berkeley Lab on the discovery of the fastest ever magnesium-ion solid-state conductor. (Credit: Argonne National Laboratory)

The electrolyte, which carries charge back and forth between the battery’s cathode and anode, is a liquid in all commercial batteries, which makes them potentially flammable, especially in lithium-ion batteries. A solid-state conductor, which has the potential to become an electrolyte, would be far more fire-resistant.

Researchers at DOE’s Lawrence Berkeley National Laboratory (Berkeley Lab) and Argonne National Laboratory were working on a magnesium battery, which offers higher energy density than lithium, but were stymied by the dearth of good options for a liquid electrolyte, most of which tend to be corrosive against other parts of the battery. “Magnesium is such a new technology, it doesn’t have any good liquid electrolytes,” said Gerbrand Ceder, a Berkeley Lab Senior Faculty Scientist. “We thought, why not leapfrog and make a solid-state electrolyte?”

The material they came up with, magnesium scandium selenide spinel, has magnesium mobility comparable to solid-state electrolytes for lithium batteries. Their findings were reported in Nature Communications in a paper titled, “High magnesium mobility in ternary spinel chalcogenides.”JCESR, a DOE Innovation Hub, sponsored the study, and the lead authors are Pieremanuele Canepa and Shou-Hang Bo, postdoctoral fellows at Berkeley Lab.

“With the help of a concerted effort bringing together computational materials science methodologies, synthesis, and a variety of characterization techniques, we have identified a new class of solid conductors that can transport magnesium ions at unprecedented speed,” Canepa said.

Collaboration with MIT and Argonne

The research team also included scientists at MIT, who provided computational resources, and Argonne, who provided key experimental confirmation of the magnesium scandium selenide spinel material to document its structure and function.

Co-author Baris Key, a research chemist at Argonne, conducted nuclear magnetic resonance (NMR) spectroscopy experiments. These tests were among the first steps to experimentally prove that magnesium ions could move through the material as rapidly as the theoretical studies had predicted.

“It was crucial to confirm the fast magnesium hopping experimentally. It is not often that the theory and the experiment agree closely with each other,” Key said. “The solid state NMR experiments for this chemistry were very challenging and would not be possible without dedicated resources and a funding source such as JCESR.

As we’ve shown in this study, an in-depth understanding of short- and long-range structure and ion dynamics will be the key for magnesium ion battery research.”

NMR is akin to magnetic resonance imaging (MRI), which is routinely used in medical settings, where it shows hydrogen atoms of water in human muscles, nerves, fatty tissue, and other biological substances. But researchers can also tune NMR frequency to detect other elements, including the lithium or magnesium ions that are found in battery materials.

The NMR data from the magnesium scandium selenide material, however, involved material of unknown structure with complex properties, making them challenging to interpret.

Canepa noted the challenges of testing materials that are so new. “Protocols are basically non-existent,” he said. “These findings were only possible by combining a multi-technique approach (solid-state NMR and synchrotron measurements at Argonne) in addition to conventional electrochemical characterization.”

Doing the impossible

The team plans to do further work to use the conductor in a battery. “This probably has a long way to go before you can make a battery out of it, but it’s the first demonstration you can make solid-state materials with really good magnesium mobility through it,” Ceder said. “Magnesium is thought to move slowly in most solids, so nobody thought this would be possible.”

Additionally, the research identified two related fundamental phenomena that could significantly affect the development of magnesium solid electrolytes in the near future, namely, the role of anti-site defects and the interplay of electronic and magnesium conductivity, both published recently in Chemistry of Materials.

Bo, now an assistant professor at Shanghai Jiao Tong University, said the discovery could have a dramatic effect on the energy landscape. “This work brought together a great team of scientists from various scientific disciplines, and took the first stab at the formidable challenge of building a solid-state magnesium battery,” he said. “Although currently in its infancy, this emerging technology may have a transformative impact on energy storage in the near future.”

Gopalakrishnan Sai Gautam, another co-author who was an affiliate at Berkeley Lab and is now at Princeton, said the team approach made possible by a DOE hub such as JCESR was critical. “The work shows the importance of using a variety of theoretical and experimental techniques in a highly collaborative environment to make important fundamental discoveries,” he said.

Ceder was excited at the prospects for the finding but cautioned that work remains to be done. “There are enormous efforts in industry to make a solid-state battery. It’s the holy grail because you would have the ultimate safe battery. But we still have work to do. This material shows a small amount of electron leakage, which has to be removed before it can be used in a battery.”

Funding for the project was provided by the DOE Office of Science through the Joint Center for Energy Storage Research, a Department of Energy Innovation Hub. The Advanced Photon Source, a DOE Office of Science User Facility at Argonne, added vital data to the study regarding the structure of the solid conductor.

The National Energy Research Scientific Computing Center (NERSC), a DOE Office of Science User Facility at Berkeley Lab, provided computing resources. Other co-authors on the paper are Juchaun Li of Berkeley Lab, William Richards and Yan Wang of MIT, and Tan Shi and Yaosen Tian of UC Berkeley.

# # #

Lawrence Berkeley National Laboratory addresses the world’s most urgent scientific challenges by advancing sustainable energy, protecting human health, creating new materials, and revealing the origin and fate of the universe. Founded in 1931, Berkeley Lab’s scientific expertise has been recognized with 13 Nobel Prizes. The University of California manages Berkeley Lab for the U.S. Department of Energy’s Office of Science. For more, visit

Argonne National Laboratory seeks solutions to pressing national problems in science and technology. The nation’s first national laboratory, Argonne conducts leading-edge basic and applied scientific research in virtually every scientific discipline. Argonne researchers work closely with researchers from hundreds of companies, universities, and federal, state, and municipal agencies to help them solve their specific problems, advance America’s scientific leadership, and prepare the nation for a better future. With employees from more than 60 nations, Argonne is managed by UChicago Argonne, LLC for the U.S. Department of Energy’s Office of Science.

DOE’s 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

The Joint Center for Energy Storage Research (JCESR), a DOE Energy Innovation Hub, is a major partnership that integrates researchers from many disciplines to overcome critical scientific and technical barriers and create new breakthrough energy storage technology. Led by the U.S. Department of Energy’s Argonne National Laboratory, partners include national leaders in science and engineering from academia, the private sector, and national laboratories. Their combined expertise spans the full range of the technology-development pipeline from basic research to prototype development to product engineering to market delivery.

‘Magnesium Mystery’ for (Lithium-Based) Rechargeable Batteries Solved: DOE

Molecular models shows the initial state of battery chemistry that leads to instability in a test cell featuring a magnesium anode

Rechargeable batteries based on magnesium, rather than lithium, have the potential to extend electric vehicle range by packing more energy into smaller batteries. But unforeseen chemical roadblocks have slowed scientific progress.
And the places where solid meets liquid – where the oppositely charged battery electrodes interact with the surrounding chemical mixture known as the electrolyte – are the known problem spots.

Now, a research team at the U.S. Department of Energy’s Joint Center for Energy Storage Research, led by scientists at Lawrence Berkeley National Laboratory (Berkeley Lab), has discovered a surprising set of chemical reactions involving magnesium that degrade battery performance even before the battery can be charged up.

The findings could be relevant to other battery materials, and could steer the design of next-generation batteries toward workarounds that avoid these newly identified pitfalls.

The team used X-ray experiments, theoretical modeling, and supercomputer simulations to develop a full understanding of the chemical breakdown of a liquid electrolyte occurring within tens of nanometers of an electrode surface that degrades battery performance. Their findings are published online in the journal Chemistry of Materials (“Instability at the Electrode/Electrolyte Interface Induced by Hard Cation Chelation and Nucleophilic Attack”).

The battery they were testing featured magnesium metal as its negative electrode (the anode) in contact with an electrolyte composed of a liquid (a type of solvent known as diglyme) and a dissolved salt, Mg(TFSI)2.

While the combination of materials they used were believed to be compatible and nonreactive in the battery’s resting state, experiments at Berkeley Lab’s Advanced Light Source (ALS), an X-ray source called a synchrotron, uncovered that this is not the case and led the study in new directions.

These molecular models show the initial state of battery chemistry that leads to instability in a test cell featuring a magnesium (Mg) anode. (Credit: Berkeley Lab)

“People had thought the problems with these materials occurred during the battery’s charging, but instead the experiments indicated that there was already some activity,” said David Prendergast, who directs the Theory of Nanostructured Materials Facility at the Molecular Foundry and served as one of the study’s leaders.

“At that point it got very interesting,” he said. “What could possibly cause these reactions between substances that are supposed to be stable under these conditions?”

Molecular Foundry researchers developed detailed simulations of the point where the electrode and electrolyte meet, known as the interface, indicating that no spontaneous chemical reactions should occur under ideal conditions, either. The simulations, though, did not account for all of the chemical details.

“Prior to our investigations,” said Ethan Crumlin, an ALS scientist who coordinated the X-ray experiments and co-led the study with Prendergast, “there were suspicions about the behavior of these materials and possible connections to poor battery performance, but they hadn’t been confirmed in a working battery.”

Commercially popular lithium-ion batteries, which power many portable electronic devices (such as mobile phones, laptops, and power tools) and a growing fleet of electric vehicles, shuttle lithium ions – lithium atoms that become charged by shedding an electron – back and forth between the two battery electrodes. These electrode materials are porous at the atomic scale and are alternatively loaded up or emptied of lithium ions as the battery is charged or discharged.

In this type of battery, the negative electrode is typically composed of carbon, which has a more limited capacity for storing these lithium ions than other materials would.

So increasing the density of stored lithium by using another material would make for lighter, smaller, more powerful batteries. Using lithium metal in the electrode, for example, can pack in more lithium ions in the same space, though it is a highly reactive substance that burns when exposed to air, and requires further research on how to best package and protect it for long-term stability.

Magnesium metal has a higher energy density than lithium metal, meaning you can potentially store more energy in a battery of the same size if you use magnesium rather than lithium.

Magnesium is also more stable than lithium. Its surface forms a self-protecting “oxidized” layer as it reacts with moisture and oxygen in the air. But within a battery, this oxidized layer is believed to reduce efficiency and shorten battery life, so researchers are looking for ways to avoid its formation.

To explore the formation of this layer in more detail, the team employed a unique X-ray technique developed recently at the ALS, called APXPS (ambient pressure X-ray photoelectron spectroscopy). This new technique is sensitive to the chemistry occurring at the interface of a solid and liquid, which makes it an ideal tool to explore battery chemistry at the surface of the electrode, where it meets the liquid electrolyte.

Magnesium Batt id48371_2

Simulations show the weakening of a bond in a liquid solvent due to the presence of free-floating hydroxide ions, which contain a single oxygen atom bound to a hydrogen atom. In this illustration, atoms are color-coded: hydrogen (white), oxygen (red), carbon (light blue), magnesium (green), nitrogen (dark blue), sulfur (yellow), fluorine (brown). This process degrades battery performance. (Credit: Berkeley Lab)

Even before a current was fed into the test battery, the X-ray results showed signs of chemical decomposition of the electrolyte, specifically at the interface of the magnesium electrode. The findings forced researchers to rethink their molecular-scale picture of these materials and how they interact.

What they determined is that the self-stabilizing, thin oxide surface layer that forms on the magnesium has defects and impurities that drive unwanted reactions.

“It’s not the metal itself, or its oxides, that are a problem,” Prendergast said. “It’s the fact you can have imperfections in the oxidized surface. These little disparities become sites for reactions. It feeds itself in this way.”

A further round of simulations, which proposed possible defects in the oxidized magnesium surface, showed that defects in the oxidized surface layer of the anode can expose magnesium ions that then act as traps for the electrolyte’s molecules.

If free-floating hydroxide ions – molecules containing a single oxygen atom bound to a hydrogen atom that can be formed as trace amounts of water react with the magnesium metal – meet these surface-bound molecules, they will react.

This wastes electrolyte, drying out the battery over time. And the products of these reactions foul the anode’s surface, impairing the battery’s function.

It took several iterations back and forth, between the experimental and theoretical members of the team, to develop a model consistent with the X-ray measurements. The efforts were supported by millions of hours’ worth of computing power at the Lab’s National Energy Research Scientific Computing Center.

Researchers noted the importance of having access to X-ray techniques, nanoscale expertise, and computing resources at the same Lab.

The results could be relevant to other types of battery materials, too, including prototypes based on lithium or aluminum metal. Prendergast said, “This could be a more general phenomenon defining electrolyte stability.”

Crumlin added, “We’ve already started running new simulations that could show us how to modify the electrolyte to reduce the instability of these reactions.” Likewise, he said, it may be possible to tailor the surface of the magnesium to reduce or eliminate some of the unwanted chemical reactivity.

“Rather than allowing it to create its own interface, you could construct it yourself to control and stabilize the interface chemistry,” he added. “Right now it leads to uncontrollable events.”

Source: By Glenn Roberts Jr., Lawrence Berkeley National Laboratory



NREL: Demonstrating and Advancing Benefits of Hydrogen Technology

by Bryan S. Pivovar, Ph.D, H2@Scale Lead/Group Manager, Chemistry and Nanosciences Center, National Renewable Energy Laboratory

Over the past several decades, technological advancements and cost reductions have dramatically changed the economic potential of hydrogen in our energy system. 
Fuel cell electric vehicles are now available for commercial sale and hydrogen stations are open to the public (more than 2,000 fuel cell vehicles are on the road and more than 30 fueling stations are open to the public in California). 

Low-cost wind and solar power are quickly changing the power generation landscape and creating a need for technologies that enhance the flexibility of the grid in the mid- to long-term.

The vision of a clean, sustainable energy system with hydrogen serving as the critical centerpiece is the focus of H2@Scale, a major initiative involving multiple U.S. Department of Energy (DOE) program offices, led by DOE’s Fuel Cell Technologies Office in the Office of Energy Efficiency and Renewable Energy, and 14 DOE national laboratories. 

H2@Scale expands the focus of hydrogen technologies beyond power generation and transportation, to grid services and industrial processes that use hydrogen.

The Energy Systems Integration Facility (ESIF) at the National Renewable Energy Laboratory (NREL) serves as a world-class, sophisticated testbed to evaluate and advance the H2@Scale concept. 

The ESIF is a DOE user facility interacting with multiple industrial stakeholders to accelerate the adoption of clean energy, including hydrogen-based technologies. Many of the barriers for making the H2@Scale vision a reality are being addressed today within ESIF by NREL researchers along with other industrial and national laboratory collaborators. 

The unique testbed capabilities at NREL and collaborating national labs are now available for use by industry and several partnerships are currently in development.
Within the ESIF, NREL researchers use electrons and water to produce hydrogen at rates of up to 100 kg/day (enough to fuel ~6,000 miles of travel in today’s fuel cell electric vehicles or more than 20 cars) with plans to expand capacity to four times this level. 

The hydrogen produced is compressed and stored in the 350 kg of on-site storage available at pressures as high as 12,500 psi. The hydrogen is used in multiple applications at the ESIF, including fueling fuel cell electric vehicles, testing and validating hydrogen infrastructure components and systems, producing renewable natural gas (through biological reaction with carbon dioxide), and as a feedstock for fuel cell power generation and research and development efforts.

To accelerate the H2@Scale concept, the cost, performance, and durability of hydrogen production, infrastructure (distribution and storage), and end use technologies need to be improved. NREL researchers, along with other labs, are actively demonstrating and advancing hydrogen technology in a number of areas including low-temperature electrolysis, biological production of renewable natural gas, and infrastructure.

Renewable hydrogen via low-temperature electrolysis

Today’s small-scale electrolysis systems are capable of producing several kilograms (kg) of hydrogen per day, but can cost as much as $10 per watt. At larger scale, megawatt (MW) systems producing more than 400 kg per day can cost under $2 per watt. However, for low-temperature electrolyzer systems to compete with the established steam methane reforming process for hydrogen production, the capital cost needs to be reduced to far below $1 per watt.

NREL has ongoing collaborations with Idaho National Laboratory (INL) to demonstrate control of a 250-kW electrolyzer system in a real-time grid simulation using a hardware-in-the-loop (HIL)-based approach to verify the performance of electrolyzer systems in providing grid support. HIL couples modeling and hardware in real-time simulations to better understand the performance of complex systems. 

The electrolyzer system, a building block for megawatt-scale deployment, was remotely controlled based on simulations of signals from a power grid. NREL and INL engineers demonstrated the ability of an electrolyzer to respond to grid signals in sub-seconds, making electrolyzers a viable candidate for “demand response” technologies that help control frequency and voltage on the grid by adjusting their power intake based on grid signals. 

A key enabler of low-cost electrolysis will be for electrolyzer technologies to respond dynamically to grid signals, such that they access low-cost power when available. The potential performance and durability implications of such dynamic operation are being elucidated in ongoing tests. Such experiments are essential to assess the potential for electrolyzers to support grid resiliency and to identify remaining R&D needs toward this value proposition.
NREL’s scientists are developing and exploring new materials for electrolysis systems, including advanced catalysts based on nanowire architecture and alkaline membranes, and approaches for integrating these materials into low-cost, durable membrane electrode assemblies.  

Graphene-wrapped nanocrystals may open door toward next-gen fuel cells

Ultra-Thin  oxide layer (oxygen atoms shown in red) coating graphene-wrapped magnesium nanoparticles (orange) still allows in hydrogen atoms (blue) for hydrogen storage applications

Researchers at the Department of Energy’s Lawrence Berkeley National Laboratory have developed a mix of metal nanocrystals wrapped in graphene that may open the door to the creation of a new type of fuel cell by enabling enhanced hydrogen storage properties.

Graphene-Wrapped Nanocrystals Make Inroads Toward Next-Gen Fuel Cells

Ultra-thin oxide layer (oxygen atoms shown in red) coating graphene-wrapped magnesium nanoparticles (orange) still allows in hydrogen atoms (blue) for hydrogen storage applications

The team studied how graphene can be used as both selective shielding, as well as a performance increasing factor in terms of hydrogen storage. 

The study drew upon a range of Lab expertise and capabilities to synthesize and coat the magnesium crystals, which measure only 3-4 nanometers (billionths of a meter) across; study their nanoscale chemical composition with X-rays; and develop computer simulations and supporting theories to better understand how the crystals and their carbon coating function together.

Reduced graphene oxide (or rGO) has nanoscale holes that permit hydrogen to pass through while keeping larger molecules away. This carbon wrapping was intended to prevent the magnesium – which is used as a hydrogen storage material – from reacting with its environment, including oxygen, water vapor and carbon dioxide. 

Such exposures could produce a thick coating of oxidation that would prevent the incoming hydrogen from accessing the magnesium surfaces. 

The study, however, suggests that an atomically thin layer of oxidation did form on the crystals during their preparation. Surprisingly, this oxide layer doesn’t seem to degrade the material’s performance.

The study’s lead author stated “Most people would suspect that the oxide layer is bad news for hydrogen storage, which it turns out may not be true in this case. Without this oxide layer, the reduced graphene oxide would have a fairly weak interaction with the magnesium, but with the oxide layer the carbon-magnesium binding seems to be stronger. 

That’s a benefit that ultimately enhances the protection provided by the carbon coating. There doesn’t seem to be any downside”.

The researchers noted that the current generation of hydrogen-fueled vehicles power their fuel cell engines using compressed hydrogen gas. “This requires bulky, heavy cylindrical tanks that limit the driving efficiency of such cars”, and the nanocrystals offer one possibility for eliminating these bulky tanks by storing hydrogen within other materials.

NREL, Swiss Scientists Power Past Solar Efficiency Records

NREL scientist Adele Tamboli, co-author of a recent article on silicon-based multijunction solar cells, stands in front of an array of solar panels. Credit: Dennis Schroeder

August 25, 2017

Second collaborative effort proves silicon-based multijunction cells that reach nearly 36% efficiency

Collaboration between researchers at the U.S. Department of Energy’s National Renewable Energy Laboratory (NREL), the Swiss Center for Electronics and Microtechnology (CSEM), and the École Polytechnique Fédérale de Lausanne (EPFL) shows the high potential of silicon-based multijunction solar cells.

The research groups created tandem solar cells with record efficiencies of converting sunlight into electricity under 1-sun illumination. The resulting paper, “Raising the One-Sun Conversion Efficiency of III–V/Si Solar Cells to 32.8% for Two Junctions and 35.9% for Three Junctions,” appears in the new issue of Nature Energy. Solar cells made solely from materials in Groups III and V of the Periodic Table have shown high efficiencies, but are more expensive.

Stephanie Essig, a former NREL post-doctoral researcher now working at EPFL in Switzerland, is lead author of the newly published research that details the steps taken to improve the efficiency of the multijunction cell. While at NREL, Essig co-authored “Realization of GaInP/Si Dual-Junction Solar Cells with 29.8% 1-Sun Efficiency,” which was published in the IEEE Journal of Photovoltaics a year ago.

In addition to Essig, authors of the new research paper are Timothy Remo, John F. Geisz, Myles A. Steiner, David L. Young, Kelsey Horowitz, Michael Woodhouse, and Adele Tamboli, all with NREL; and Christophe Allebe, Loris Barraud, Antoine Descoeudres, Matthieu Despeisse, and Christophe Ballif, all from CSEM.

“This achievement is significant because it shows, for the first time, that silicon-based tandem cells can provide efficiencies competing with more expensive multijunction cells consisting entirely of III-V materials,” Tamboli said. “It opens the door to develop entirely new multijunction solar cell materials and architectures.”

In testing silicon-based multijunction solar cells, the researchers found that the highest dual-junction efficiency (32.8%) came from a tandem cell that stacked a layer of gallium arsenide (GaAs) developed by NREL atop a film of crystalline silicon developed by CSEM. An efficiency of 32.5% was achieved using a gallium indium phosphide (GaInP) top cell, which is a similar structure to the previous record efficiency of 29.8% announced in January 2016. 

A third cell, consisting of a GaInP/GaAs tandem cell stacked on a silicon bottom cell, reached a triple-junction efficiency of 35.9%—just 2% below the overall triple-junction record.

The existing photovoltaics market is dominated by modules made of single-junction silicon solar cells, with efficiencies between 17% and 24%. 

The researchers noted in the report that making the transition from a silicon single-junction cell to a silicon-based dual-junction solar cell will enable manufacturers to push efficiencies past 30% while still benefiting from their expertise in making silicon solar cells.

The obstacle to the adoption of these multijunction silicon-based solar cells, at least in the near term, is the cost. Assuming 30% efficiency, the researchers estimated the GaInP-based cell would cost $4.85 per watt and the GaAs-based cell would cost $7.15 per watt. 

But as manufacturing ramps up and the efficiencies of these types of cells climbs to 35%, the researchers predict the cost per watt could fall to 66 cents for a GaInP-based cell and to 85 cents for the GaAs-based cell. 

The scientists noted that such a precipitous price drop is not unprecedented; for instance, the cost of Chinese-made photovoltaic modules fell from $4.50 per watt in 2006 to $1 per watt in 2011.

The cost of a solar module in the United States accounts for 20% to 40% of the price of a photovoltaic system. Increasing cell efficiency to 35%, the researchers estimated, could reduce the system cost by as much as 45 cents per watt for commercial installations. 

However, if the costs of a III-V cell cannot be reduced to the levels of the researchers’ long-term scenario, then the use of cheaper, high-efficiency materials for the top cell will be needed to make them cost-competitive in general power markets.

The funding for the research came from the Energy Department’s SunShot Initiative—which aims to make solar energy a low-cost electricity source for all Americans through research and development efforts in collaboration with public and private partners—and from the Swiss Confederation and the initiative.

NREL is the U.S. Department of Energy’s primary national laboratory for renewable energy and energy efficiency research and development. NREL is operated for the Energy Department by The Alliance for Sustainable Energy, LLC.

UC Berkeley Labs: A Semiconductor That Can Beat the Heat

Berkeley Lab, UC Berkeley scientists discover unique thermoelectric properties in cesium tin iodide

JULY 31, 2017

A newly discovered collective rattling effect in a type of crystalline semiconductor blocks most heat transfer while preserving high electrical conductivity – a rare pairing that scientists say could reduce heat buildup in electronic devices and turbine engines, among other possible applications.

A team led by scientists at the Department of Energy’s Lawrence Berkeley National Laboratory (Berkeley Lab) discovered these exotic traits in a class of materials known as halide perovskites, which are also considered promising candidates for next-generation solar panels, nanoscale lasers, electronic cooling, and electronic displays.

These interrelated thermal and electrical (or “thermoelectric”) properties were found in nanoscale wires of cesium tin iodide (CsSnI3). The material was observed to have one of the lowest levels of heat conductivity among materials with a continuous crystalline structure.

Image – Rattling structures of halide perovskites: cesium tin iodide (left) and cesium lead iodide (right). (Credit: Berkeley Lab/UC Berkeley)

This so-called single-crystal material can also be more easily produced in large quantities than typical thermoelectric materials, such as silicon-germanium, researchers said.

“Its properties originate from the crystal structure itself. It’s an atomic sort of phenomenon,” said Woochul Lee, a postdoctoral researcher at Berkeley Lab who was the lead author of the study, published the week of July 31 in the Proceedings of the National Academy of Sciences journal. These are the first published results relating to the thermoelectric performance of this single crystal material.

Researchers earlier thought that the material’s thermal properties were the product of “caged” atoms rattling around within the material’s crystalline structure, as had been observed in some other materials. Such rattling can serve to disrupt heat transfer in a material.

“We initially thought it was atoms of cesium, a heavy element, moving around in the material,” said Peidong Yang, a senior faculty scientist at Berkeley Lab’s Materials Sciences Division who led the study.

Jeffrey Grossman, a researcher at the Massachusetts Institute of Technology, then performed some theory work and computerized simulations that helped to explain what the team had observed. 

Researchers also used Berkeley Lab’s Molecular Foundry, which specializes in nanoscale research, in the study.

“We believe there is essentially a rattling mechanism, not just with the cesium. It’s the overall structure that’s rattling; it’s a collective rattling,” Yang said. “The rattling mechanism is associated with the crystal structure itself,” and is not the product of a collection of tiny crystal cages. “It is group atomic motion,” he added.

Within the material’s crystal structure, the distance between atoms is shrinking and growing in a collective way that prevents heat from easily flowing through.

But because the material is composed of an orderly, single-crystal structure, electrical current can still flow through it despite this collective rattling. Picture its electrical conductivity is like a submarine traveling smoothly in calm underwater currents, while its thermal conductivity is like a sailboat tossed about in heavy seas at the surface.

Yang said two major applications for thermoelectric materials are in cooling, and in converting heat into electrical current. For this particular cesium tin iodide material, cooling applications such as a coating to help cool electronic camera sensors may be easier to achieve than heat-to-electrical conversion, he said.

A challenge is that the material is highly reactive to air and water, so it requires a protective coating or encapsulation to function in a device.

Cesium tin iodide was first discovered as a semiconductor material decades ago, and only in recent years has it been rediscovered for its other unique traits, Yang said. “It turns out to be an amazing gold mine of physical properties,” he noted.

SEM images of suspended micro-island devices. Individual AIHP NW is suspended between two membranes. (Credit: Berkeley Lab/UC Berkeley)

To measure the thermal conductivity of the material, researchers bridged two islands of an anchoring material with a cesium tin iodide nanowire. The nanowire was connected at either end to micro-islands that functioned as both a heater and a thermometer. 
Researchers heated one of the islands and precisely measured how the nanowire transported heat to the other island.

They also performed scanning electron microscopy to precisely measure the dimensions of the nanowire. They used these dimensions to provide an exacting measure of the material’s thermal conductivity. The team repeated the experiment with several different nanowire materials and multiple nanowire samples to compare thermoelectric properties and verify the thermal conductivity measurements.

“A next step is to alloy this (cesium tin iodide) material,” Lee said. “This may improve the thermoelectric properties.”

Also, just as computer chip manufacturers implant a succession of elements into silicon wafers to improve their electronic properties – a process known as “doping” – scientists hope to use similar techniques to more fully exploit the thermoelectric traits of this semiconductor material. This is relatively unexplored territory for this class of materials, Yang said.

The research team also included other scientists from Berkeley Lab’s Materials Sciences Division and the Molecular Foundry, the Kavli Energy NanoScience Institute at UC Berkeley and Berkeley Lab, and UC Berkeley’s Department of Chemistry.

The Molecular Foundry is a DOE Office of Science User Facility that provides free access to state-of-the-art equipment and multidisciplinary expertise in nanoscale science to visiting scientists from all over the world.

This work was supported by the Department of Energy’s Office of Basic Energy Sciences.
More information about Peidong Yang’s research group:

Lawrence Berkeley National Laboratory addresses the world’s most urgent scientific challenges by advancing sustainable energy, protecting human health, creating new materials, and revealing the origin and fate of the universe. Founded in 1931, Berkeley Lab’s scientific expertise has been recognized with 13 Nobel Prizes. The University of California manages Berkeley Lab for the U.S. Department of Energy’s Office of Science. For more, visit
DOE’s 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

Finding Ways to Cure the Energy Dense but Short-Lived Lithium-Sulfur Battery – A ‘First-Time Look’

Lithium Sulfur I chemistsseek

Everyone’s heard the phrase about seeing both the details and the big picture, and that struggle comes into sharp relief for those studying how to create batteries that hold more energy and cost less. It’s difficult to see the details of atomic and topographical changes as a battery operates.

For DOE’s Joint Center for Energy Storage Research (JCESR), Vijay Murugesan and his colleagues at Pacific Northwest National Laboratory and Texas A&M University found a way. The result? They saw the products of the parasitic electrolyte decomposition reactions. The reactions led to a layer that smothers the electrode in energy-dense-but short-lived-lithium-sulfur batteries (Chemistry of Materials, “In-Situ Chemical Imaging of Solid-Electrolyte Interphase Layer Evolution in Li-S Batteries”).
This research is thanks, in part, to a new device that let the team track the progression of sulfur in a vacuum inside a powerful scientific instrument. “We can now realistically probe the reactions happening and view how the products actually spread,” said Murugesan, PNNL researcher.
The Forest, the Trees and Parasitic Reactions in Batteries
The Forest, the Trees and Parasitic Reactions in Batteries. Researchers built a new stage and created a designer electrolyte to obtain both detailed and broad overviews of a troubling layer that causes promising lithium-sulfur batteries to fail. (Image: Nathan Johnson, PNNL)

Better batteries affect everything from how you get to work to how long you can work on your laptop computer before finding an outlet. The results from this fundamental study benefit energy storage in two ways. First, to do the work, the team created a new “stage.” This device let scientists determine the atomic composition and electronic and chemical state of the atoms on the electrode while the battery was running. Scientists can use this device to obtain a detailed view of other batteries.

“Doing this measurement is challenging,” said Vaithiyalingam Shutthanandan, a PNNL scientist who worked on the research. “This is the first time we could access this level of quantity and quality data while batteries were charging and discharging.”
The second benefit of this study is the potential to solve the fading issue in lithium-sulfur batteries. “Sulfur is significantly cheaper than current cathode materials in lithium-ion batteries,” said Murugesan. “So the total cost of a lithium-sulfur battery will be low. Simultaneously, the energy density will be a huge advantage-approximately five times more than lithium-ion batteries.”
The team achieved the results thanks to a combination of scientific innovation and serendipity. The innovation came in building the unique stage for the X-ray photoelectron spectroscopy (XPS) instrument. The researchers needed to track the sulfur in the battery, but sulfur volatilizes in a vacuum. All samples in an XPS are studied under vacuum. Combining the newly designed stage and ionic liquids as electrolyte media let the team operate the battery inside the XPS and monitor the growth of sulfur-based compounds to see the parasitic reactions.
“We designed a completely new capability for the XPS system,” said Ashleigh Schwarz, who performed many of the XPS scans on the battery and helped determine the electrolyte to use on the stage.
The electrolyte’s composition is crucial, as it must survive the vacuum used by XPS. Schwarz and her colleagues tested different compositions to see how well the electrolyte performed in the XPS. The team’s choice contained 20 percent of the traditional solvent (DOL/DME) combined with an ionic solvent.
Using the XPS in analysis or spectroscopy mode, the team obtained the atomic information, including the atoms present and the chemical bonds between them. Switching over to an imaging or microscopic mode, the researchers acquired topological views of the solid-electrolyte interphase (SEI) layer forming. This view let them see where the elements were on the surface and more. The combination of views let them obtain critical information over a wide range of spatial resolutions, spanning from angstroms to micrometers as the battery drained and charged.
The XPS resides in EMSL, the Environmental Molecular Sciences Laboratory, a DOE Office of Science user facility at PNNL.
Lithium Sulfur II bg-applications-1In addition, the team benefited from a serendipitous meeting at a national scientific conference. Murugesan was talking with Perla Balbuena, Texas A&M University, about her research into lithium-sulfur batteries. The pair quickly realized that her work on ab initio molecular dynamics modeling would benefit the experiments. Balbuena and her colleague Luis Camacho-Forero worked with the experimentalists to interpret the results and test new ideas about how the SEI layer forms. Knowing how the layer forms could lead to options that stop its formation altogether and greatly extend the battery life cycle.
As part of JCESR, the team is continuing to answer tough questions necessary to create the next generation of energy storage technologies.
Source: Pacific Northwest National Laboratory


Long-lasting flow battery could run for more than a decade with minimum upkeep – Harvard Paulson School of Engineering 

Battery stores energy in nontoxic, noncorrosive aqueous solutions

Researchers from the Harvard John A. Paulson School of Engineering and Applied Sciences (SEAS) have developed a new flow battery that stores energy in organic molecules dissolved in neutral pH water.

This new chemistry allows for a non-toxic, non-corrosive battery with an exceptionally long lifetime and offers the potential to significantly decrease the costs of production.

The research, published in ACS Energy Letters, was led by Michael Aziz, the Gene and Tracy Sykes Professor of Materials and Energy Technologies and Roy Gordon, the Thomas Dudley Cabot Professor of Chemistry and Professor of Materials Science.

Flow batteries store energy in liquid solutions in external tanks — the bigger the tanks, the more energy they store.

Flow batteries are a promising storage solution for renewable, intermittent energy like wind and solar but today’s flow batteries often suffer degraded energy storage capacity after many charge-discharge cycles, requiring periodic maintenance of the electrolyte to restore the capacity.

By modifying the structures of molecules used in the positive and negative electrolyte solutions, and making them water soluble, the Harvard team was able to engineer a battery that loses only one percent of its capacity per 1000 cycles.

“Lithium ion batteries don’t even survive 1000 complete charge/discharge cycles,” said Aziz.

“Because we were able to dissolve the electrolytes in neutral water, this is a long-lasting battery that you could put in your basement,” said Gordon.



“If it spilled on the floor, it wouldn’t eat the concrete and since the medium is noncorrosive, you can use cheaper materials to build the components of the batteries, like the tanks and pumps.”

This reduction of cost is important. The Department of Energy (DOE) has set a goal of building a battery that can store energy for less than $100 per kilowatt-hour, which would make stored wind and solar energy competitive with energy produced from traditional power plants.

“If you can get anywhere near this cost target then you change the world,” said Aziz. “It becomes cost effective to put batteries in so many places. This research puts us one step closer to reaching that target.”

“If you can get anywhere near this cost target then you change the world,” said Aziz. “It becomes cost effective to put batteries in so many places. This research puts us one step closer to reaching that target.”

“This work on aqueous soluble organic electrolytes is of high significance in pointing the way towards future batteries with vastly improved cycle life and considerably lower cost,” said Imre Gyuk, Director of Energy Storage Research at the Office of Electricity of the DOE.

“I expect that efficient, long duration flow batteries will become standard as part of the infrastructure of the electric grid.”

The key to designing the battery was to first figure out why previous molecules were degrading so quickly in neutral solutions, said Eugene Beh, a postdoctoral fellow and first author of the paper.

By first identifying how the molecule viologen in the negative electrolyte was decomposing, Beh was able to modify its molecular structure to make it more resilient.

Next, the team turned to ferrocene, a molecule well known for its electrochemical properties, for the positive electrolyte.

“Ferrocene is great for storing charge but is completely insoluble in water,” said Beh. “It has been used in other batteries with organic solvents, which are flammable and expensive.”

But by functionalizing ferrocene molecules the same way as the viologen, the team was able to turn an insoluble molecule into a highly soluble one that could be cycled stably.

“Aqueous soluble ferrocenes represent a whole new class of molecules for flow batteries,” said Aziz.

The neutral pH should be especially helpful in lowering the cost of the ion-selective membrane that separates the two sides of the battery.

Most flow batteries today use expensive polymers that can withstand the aggressive chemistry inside the battery. They can account for up to one-third of the total cost of the device. 

With essentially salt water on both sides of the membrane, expensive polymers can be replaced by cheap hydrocarbons. 

This research was coauthored by Diana De Porcellinis, Rebecca Gracia, and Kay Xia. It was supported by the Office of Electricity Delivery and Energy Reliability of the DOE and by the DOE’s Advanced Research Projects Agency-Energy.

With assistance from Harvard’s Office of Technology Development (OTD), the researchers are working with several companies to scale up the technology for industrial applications and to optimize the interactions between the membrane and the electrolyte.

Harvard OTD has filed a portfolio of pending patents on innovations in flow battery technology.

DOE: One small change makes Quantum Dot solar cells more efficient

The quest for more efficient solar cells has led to the search of new materials. For years, scientists have explored using tiny drops of designer materials, called quantum dots.

Now, we know that adding small amounts of manganese decreases the ability of quantum dots to absorb light but increases the current produced by an average of 300%. Under certain conditions, the current produced increased by 700%.

The enhancement is due to the faster rate that the electrons move from the quantum dot to the balance of the solar cell (what the scientists call the electron tunneling rate) in the presence of the manganese atoms at the interface.

Importantly, this observation is confirmed by theory, opening up possibilities for applying this approach to other systems (Applied Physics Letters, “Giant photocurrent enhancement by transition metal doping in quantum dot sensitized solar cells”).

The power conversion efficiency of quantum dot solar cells has reached about 12%. However, the overall efficiency of quantum dot solar cells is relatively low compared to photovoltaic systems in use today that are based on silicon. In addition, quantum dot solar cells are not as efficient as emerging next-generation solar cells.

The results obtained in this work point to a surprisingly straightforward alternative route. Scientists can significantly improve the performance of this family of solar cells by adding small amounts of alternate metals.

In the quest to replace more traditional solar materials, such as silicon, with more efficient and high-performing options, scientists have been studying quantum dot solar cells as an alternative to harvest sunlight for conversion to electricity.

In this solar cell design, quantum dots are used as the material that absorbs sunlight and converts it to electricity. Quantum dots are very small, nanometer-sized, particles, whose solar conversion properties, in this case a characteristic gap in the energy levels of the electrons called the “bandgap,” are tunable by changing the size or chemical composition.

This is in contrast to bulk materials whose bandgap is fixed by the chemical composition or choice of material(s) alone. This size dependence of bandgap makes quantum dots attractive for multi-junction solar cells, whose efficiency is enhanced by using a variety of materials that absorb different parts of the “rainbow” of wavelengths of light found in the solar spectrum.

This research team discovered that adding small amounts of the transition metal manganese (Mn), or “doping,” resulted in a huge enhancement in the efficiency rate of changing light to electricity for lead sulfide (PbS) quantum dot sensitized solar cells.

Relatively small concentrations of Mn (4 atomic percent) cause the current to increase by an average of 300% with a maximum increase of up to 700%.

Moreover, the mechanism by which this occurs cannot be explained by the light absorption alone because both the experimental and theoretical absorption spectra demonstrate a several times decrease in the absorption coefficient on the addition of Mn.

The team proposes that the dramatic increase is due to a mechanism of increased electron tunneling through the atom pairs at the quantum dot interface with the next layer of the solar cell.

The team used ab initio calculations, which is a computational approach that can describe new phenomena without the need to fit or extrapolate experimental data, to confirm this mechanism.

While typical doping approaches focus on improving exciton lifetime and light absorption channels, results obtained in this study provide an alternative route for significant improvement on the efficiency of quantum dot sensitized solar cells.

Source: U.S. Department of Energy, Office of Science