Solar Energy

Tuning electrode surfaces to optimize solar fuel production

Published

3 years ago

February 21, 2021

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Tuning electrode surfaces to optimize solar fuel production

Scientists have demonstrated that modifying the topmost layer of atoms on the surface of electrodes can have a remarkable impact on the activity of solar water splitting. As they reported in Nature Energy on Feb. 18, bismuth vanadate electrodes with more bismuth on the surface (relative to vanadium) generate higher amounts of electrical current when they absorb energy from sunlight.

This photocurrent drives the chemical reactions that split water into oxygen and hydrogen. The hydrogen can be stored for later use as a clean fuel. Producing only water when it recombines with oxygen to generate electricity in fuel cells, hydrogen could help us achieve a clean and sustainable energy future.

“The surface termination modifies the system’s interfacial energetics, or how the top layer interacts with the bulk,” said co-corresponding author Mingzhao Liu, a staff scientist in the Interface Science and Catalysis Group of the Center for Functional Nanomaterials (CFN), a U.S. Department of Energy (DOE) Office of Science User Facility at Brookhaven National Laboratory. “A bismuth-terminated surface exhibits a photocurrent that is 50-percent higher than a vanadium-terminated one.”

“”Studying the effects of surface modification with an atomic-level understanding of their origins is extremely challenging, and it requires tightly integrated experimental and theoretical investigations,” said co-corresponding author Giulia Galli from the University of Chicago and DOE’s Argonne National Laboratory.

“It also requires the preparation of high-quality samples with well-defined surfaces and methods to probe the surfaces independently from the bulk,” added co-corresponding author Kyoung-Shin Choi from the University of Wisconsin-Madison.

Choi and Galli, experimental and theoretical leaders in the field of solar fuels, respectively, have been collaborating for several years to design and optimize photoelectrodes for producing solar fuels. Recently, they set out to design strategies to illuminate the effects of electrode surface composition, and, as CFN users, they teamed up with Liu.

“The combination of expertise from the Choi Group in photoelectrochemistry, the Galli Group in theory and computation, and the CFN in material synthesis and characterization was vital to the study’s success,” commented Liu.

Bismuth vanadate is a promising electrode material for solar water splitting because it strongly absorbs sunlight across a range of wavelengths and remains relatively stable in water. Over the past few years, Liu has perfected a method for precisely growing single-crystalline thin films of this material. High-energy laser pulses strike the surface of polycrystalline bismuth vanadate inside a vacuum chamber. The heat from the laser causes the atoms to evaporate and land on the surface of a base material (substrate) to form a thin film.

“To see how different surface terminations affect photoelectrochemical activity, you need to be able to prepare crystalline electrodes with the same orientation and bulk composition,” explained co-author Chenyu Zhou, a graduate researcher from Stony Brook University working with Liu. “You want to compare apples to apples.”

As grown, bismuth vanadate has an almost one-to-one ratio of bismuth to vanadium on the surface, with slightly more vanadium. To create a bismuth-rich surface, the scientists placed one sample in a solution of sodium hydroxide, a strong base.

“Vanadium atoms have a high tendency to be stripped from the surface by this basic solution,” said first author Dongho Lee, a graduate researcher working with Choi. “We optimized the base concentration and sample immersion time to remove only the surface vanadium atoms.”

To confirm that this chemical treatment changed the composition of the top surface layer, the scientists turned to low-energy ion scattering spectroscopy (LEIS) and scanning tunneling microscopy (STM) at the CFN.

In LEIS, electrically charged atoms with low energy – in this case, helium – are directed at the sample. When the helium ions hit the sample surface, they become scattered in a characteristic pattern depending on which atoms are present at the very top. According to the team’s LEIS analysis, the treated surface contained almost entirely bismuth, with an 80-to-20 ratio of bismuth to vanadium.

“Other techniques such as x-ray photoelectron spectroscopy can also tell you what atoms are on the surface, but the signals come from several layers of the surface,” explained Liu. “That’s why LEIS was so critical in this study – it allowed us to probe only the first layer of surface atoms.”

In STM, an electrically conductive tip is scanned very close to the sample surface while the tunneling current flowing between the tip and sample is measured. By combining these measurements, scientists can map the electron density – how electrons are arranged in space – of surface atoms. Comparing the STM images before and after treatment, the team found a clear difference in the patterns of atomic arrangements corresponding to vanadium- and bismuth-rich surfaces, respectively.

“Combining STM and LEIS allowed us to identify the atomic structure and chemical elements on the topmost surface layer of this photoelectrode material,” said co-author Xiao Tong, a staff scientist in the CFN Interface Science and Catalysis Group and manager of the multiprobe surface analysis system used in the experiments. “These experiments demonstrate the power of this system for exploring surface-dominated structure-property relationships in fundamental research applications.”

Simulated STM images based on surface structural models derived from first-principle calculations (those based on the fundamental laws of physics) closely matched the experimental results.

“Our first-principle calculations provided a wealth of information, including the electronic properties of the surface and the exact positions of the atoms,” said co-author and Galli Group postdoctoral fellow Wennie Wang. “This information was critical to interpreting the experimental results.”

After proving that the chemical treatment successfully altered the first layer of atoms, the team compared the light-induced electrochemical behavior of the treated and nontreated samples.

“Our experimental and computational results both indicated that the bismuth-rich surfaces lead to more favorable surface energetics and improved photoelectrochemical properties for water splitting,” said Choi. “Moreover, these surfaces pushed the photovoltage to a higher value.”

Many times, particles of light (photons) do not provide enough energy for water splitting, so an external voltage is needed to help perform the chemistry. From an energy-efficiency perspective, you want to apply as little additional electricity as possible.

“When bismuth vanadate absorbs light, it generates electrons and electron vacancies called holes,” said Liu. “Both of these charge carriers need to have enough energy to do the necessary chemistry for the water-splitting reaction: holes to oxidize water into oxygen gas, and electrons to reduce water into hydrogen gas. While the holes have more than enough energy, the electrons don’t. What we found is that the bismuth-terminated surface lifts the electrons to higher energy, making the reaction easier.”

Because holes can easily recombine with electrons instead of being transferred to water, the team did additional experiments to understand the direct effect of surface terminations on photoelectrochemical properties. They measured the photocurrent of both samples for sulfite oxidation. Sulfite, a compound of sulfur and oxygen, is a “hole scavenger,” meaning it quickly accepts holes before they have a chance to recombine with electrons. In these experiments, the bismuth-terminated surfaces also increased the amount of generated photocurrent.

“It’s important that electrode surfaces perform this chemistry as quickly as possible,” said Liu. “Next, we’ll be exploring how co-catalysts applied on top of the bismuth-rich surfaces can help expedite the delivery of holes to water.”

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Solar Energy

3D-printed microstructure forest enhances solar steam desalination

Published

3 days ago

July 24, 2024

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3D-printed microstructure forest enhances solar steam desalination

by Clarence Oxford

Los Angeles CA (SPX) Jul 24, 2024

To address the global freshwater scarcity issue, researchers in Singapore have developed advanced solar steam generators (SSGs) for seawater desalination. This method, powered by renewable energy, mimics the natural water cycle by using solar energy to evaporate and purify water, offering a potentially cost-effective solution compared to traditional, energy-intensive desalination techniques. However, current SSG technologies face limitations due to the complexity of fabricating designs that maximize surface area for optimal water evaporation.

Drawing inspiration from nature, the team utilized 3D printing to create innovative SSGs. Their findings, published in Applied Physics Reviews, highlight a novel technique for manufacturing efficient SSGs and introduce a groundbreaking method for printing functional nanocomposites using multi-jet fusion (MJF).

“We created SSGs with exceptional photothermal performance and self-cleaning properties,” said Kun Zhou, a professor of mechanical engineering at Nanyang Technological University. “Using a treelike porous structure significantly enhances water evaporation rates and ensures continuous operation by preventing salt accumulation – its performance remains relatively stable even after prolonged testing.”

The technology works by converting light to thermal energy, where SSGs absorb solar energy and convert it to heat to evaporate water. The porous structure of the SSGs aids in self-cleaning by removing accumulated salt, ensuring sustained desalination performance.

“By using an effective photothermal fusing agent, MJF printing technology can rapidly create parts with intricate designs,” Zhou added. “To improve the photothermal conversion efficiency of fusing agents and printed parts, we developed a novel type of fusing agent derived from metal-organic frameworks.”

The SSGs feature miniature tree-shaped microstructures that mimic plant transpiration, forming an efficient, heat-distributing forest.

“Our bioinspired design increases the surface area of the SSG,” Zhou explained. “Using a treelike design increases the surface area of the SSG, which enhances the water transport and boosts evaporation efficiency.”

In both simulated environments and field trials, the SSGs exhibited a high rate of water evaporation. The desalinated water consistently met drinking water standards, even after extended testing.

“This demonstrates the practicality and efficiency of our approach,” Zhou said. “And it can be quickly and easily mass-produced via MJF commercial printers.”

The team’s work shows significant potential for tackling freshwater scarcity.

“Our SSGs can be used in regions with limited access to freshwater to provide a sustainable and efficient desalination solution,” said Zhou. “Beyond desalination, it can be adapted for other applications that require efficient solar energy conversion and water purification.”

Research Report:3D printing of bio-inspired porous polymeric solar steam generators for efficient and sustainable desalination

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Solar Energy

Renewables overproduction turns electricity prices negative

Published

3 days ago

July 24, 2024

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Renewables overproduction turns electricity prices negative

By Nathalie Alonso and Catherine Hours

Paris (AFP) July 24, 2024

With the proliferation of solar panels and wind turbines an unusual phenomenon is becoming more and more frequent: wholesale electricity prices turn negative.

While that may brighten the mood of consumers whose power bills have surged in recent years, it could undermine the further development of renewables, a key element in the fight against global warming.

The increasingly frequent phenomenon is “extremely problematic” for the wind and solar sector, said Mattias Vandenbulcke, strategy director of the renewables industry group France Renouvelables.

“It allows some to have harmful, even dangerous rhetoric which says ‘renewables are useless’,” Vandenbulcke said.

In southern Australia, wholesale electricity prices have been negative some 20 percent of the time since last year, according to the International Energy Agency.

The share of negatively priced hours in southern California was above 20 percent in the first half of the year, more than triple from the same period in 2023, the IEA said.

In the first six months of the year in France, there were negative prices around five percent of the time, beating the record set last year, according to the electricity grid operator RTE.

In Switzerland the price tumbled as far as -400 euros (-$436) per megawatt hour on July 14. The lowest prices are usually recorded around midday during the summer when solar production is at its peak.

– ‘A warning signal’ –

The trend has been accelerating for the past three years as demand in Europe has unexpectedly dropped since the Covid pandemic and the war in Ukraine.

Prices turn negative on the spot wholesale electricity market when production is strong while demand is weak.

Around a fifth of the total is traded on this market, where electricity is bought for the following day.

Negative prices help reduce the bills of consumers, said Rebecca Aron, head of electricity markets at French renewables firm Valorem, but the impact is delayed and difficult to discern among the other factors that send prices higher and lower.

Large, industrial consumers that can shift production to times when prices are negative and buy on wholesale markets can reap the biggest rewards.

Negative prices are “a warning signal that there is way too much production on the electrical grid”, said energy analyst Nicolas Goldberg at Colombus Consulting.

Electricity grids need to be kept constantly in balance. Too much can lead to the electricity to increase in frequency beyond norms for some equipment. Too little can lead to some or all customers losing power.

There are currently few options to stock surplus electricity production so producers have to reduce output.

Many renewable producers stop their output when prices are set to turn negative. It takes one minute to stop output at a solar park, two to three minutes for a wind turbine.

But not all stop their production.

– Tripling renewables –

“Renewable energy can be controlled, but depending on production contracts, there might not necessarily be an incentive to stop,” said Mathieu Pierzo at French grid operator RTE, which has the responsibility for balancing the electricity load.

Some producers are paid a fixed price under their contract or are compensated by the state if prices fall below a certain level.

Fossil fuel and nuclear power plants can adjust their production to some extent, but halting and restarting output is costly.

In the future, solar and wind will also have to “participate more in balancing the electricity system”, Pierzo said.

Solar and wind production is set to rise further as nations agreed at the COP28 climate conference last year to triple renewable energy capacity by 2030 as part of efforts to limit warming to 1.5 degrees Celsius compared with pre-industrial levels.

“Rising frequency of negative prices sends an urgent signal that greater flexibility of supply and demand is needed,” the Paris-based IEA warned last week.

“The appropriate regulatory frameworks and market designs will be important to allow for an uptake in flexibility solutions such as demand response and storage,” it said.

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Solar Energy

NREL explores long-term strategies for sustainable perovskite solar panels

Published

3 days ago

July 24, 2024

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NREL explores long-term strategies for sustainable perovskite solar panels

by Clarence Oxford

Los Angeles CA (SPX) Jul 24, 2024

Researchers at the National Renewable Energy Laboratory (NREL) are examining the future of perovskite solar panels, focusing on scaling, deploying, and designing panels to be recyclable.

Perovskite solar panels could play a key role in global efforts to reduce greenhouse gas emissions. With the technology still in its developmental stages, researchers are emphasizing the importance of designing these panels to minimize environmental impact.

“When you have a technology in its very early stages, you have the ability to design it better. It’s a cleaner slate,” said Joey Luther, a senior research fellow at the U.S. Department of Energy’s (DOE’s) National Renewable Energy Laboratory (NREL) and coauthor of the newly published article in the journal Nature Materials. “Pushing perovskite PV toward enhanced sustainability makes more sense at this stage. We’re thinking about how we can make sure we have a sustainable product now rather than dealing with sustainability issues toward the end of its practical life.”

The article highlights the PV research community’s influential position to prioritize remanufacturing, recycling, and reliability efforts, aiming to make perovskite PV one of the most sustainable energy sources available.

“Perovskites could unlock the next evolution of high-efficiency PV, and it is our responsibility to assure they are manufactured, used, and recycled sustainably,” said the lead author of the study, Kevin Prince, a former graduate researcher at NREL who now researches perovskites at Helmholtz Zentrum Berlin in Germany.

While silicon solar panels dominate the industry and cadmium telluride (CdTe) panels have established recycling programs, perovskites are at a critical point where sustainability issues can be addressed from the start.

The most effective circular economy begins at the design stage, considering materials sourcing, product lifetime, and end-of-life management. Researchers suggest assessing environmental impacts by looking at carbon emissions during production, embodied energy, sustainable material sourcing, and module circularity.

The journal article identifies critical sustainability concerns for each component of a perovskite solar panel. For instance, lead can be diluted with metals like tin to reduce lead content, though this may affect PV efficiency and durability. Expensive precious metals such as silver and gold could be replaced with cheaper alternatives like aluminum, copper, or nickel. Fluorine-tin oxide is recommended over the scarcer indium-tin oxide for front electrodes.

“We want to have the lowest amount of embodied energy in the fabrication,” Luther said. “We want to have the lowest amount of emissions in the fabrication. At this stage, now is the chance to look at those components. I don’t think we have to change anything. It’s more a matter of what decisions should be made, and these arguments should certainly be discussed.”

The authors discuss various ways to improve the circularity of perovskite panels. Remanufacturing involves reusing parts from old modules to make new ones, while recycling converts waste materials into raw materials for reuse. Attention is needed for the specialized glass used in perovskite modules, which is crucial for structural support and protection while allowing maximum sunlight penetration. Establishing a recycling pathway for this glass will be essential as PV deployment increases.

Silvana Ovaitt, a PV researcher and coauthor of the paper, noted that cleaner electricity grids will lead to cleaner manufacturing processes, further reducing emissions.

“Another concern is the transportation of the final modules and the raw glass because those are the heaviest items,” Ovaitt said. “Local manufacturing will be a great way to reduce those carbon impacts.”

The researchers explain that increasing the durability of PV modules, thereby extending their useful life, is a more effective approach to reducing net energy, energy payback, and carbon emissions than designing for circularity alone. A longer lifespan means panels won’t need to be recycled as often.

“Ultimately, we want to make them as durable as possible,” Luther said. “But we also want to consider the aspects of whenever that time does come. We want to be deliberate about how to take them apart and to reuse the critical components.”

Research Report:Sustainability pathways for perovskite photovoltaics