oxygen – Lightsources.org

Explosive Prevention for 1,000km Next-Gen Battery!

2025/03/212025/03/25

A solution to the gas-filling problem of the next-generation long-distance battery¹⁾ has emerged.
A team led by Professor Lee Hyun-wook of UNIST’s Department of Energy and Chemical Engineering has identified the cause of Oxygen generation in olig Lithium of a new anode material for batteries and presented material design principles to solve this problem.

Overlithium materials can theoretically store 30% to 70% more energy in batteries than before through high-pressure charging of 4.5V or higher. In terms of electric vehicle mileage, you can go up to 1,000 kilometers on a single charge. However, this material has a problem of increasing the risk of explosion as Oxygen (O^-2) held inside the material is oxidized and released as gas (O₂) during the actual high-pressure charging process.

The research team analyzed that Oxygen is oxidized near 4.25V, causing partial structural deformation and releasing Oxygen gas. They proposed an electrode material design method that fundamentally prevents the oxidation of Oxygen. This strategy involves replacing some of the transition metals²⁾ of Lithium materials with transition metal elements with lower electronegativity.

The difference in electronegativity between the two metal elements causes the number of available electrons in the transition metal to increase, and Oxygen does not oxidize when electrons are concentrated around the highly electronegativity element. On the other hand, when the number of available electrons in the transition metal is insufficient, Oxygen gives electrons instead. It is oxidized to be discharged in the form of a gas.

The first author, Kim Min-ho (Currently a postdoctoral researcher at UCLA), explained “the difference between existing research that has focused on stabilizing Oxygen and preventing it from being discharged in the form of gas, whereas present research has focused on preventing the oxidizing process itself.”

In addition, this change in electron density increases the charging voltage through an Inductive Effect³⁾, thereby increasing the high energy density attainable. Since the energy density is proportional to the number of available electrons and the charging voltage, it is possible to store more energy per unit weight of the battery to replace the transition metal. This phenomenon is similar to the principle that if there’s more water in the dam and the drop is more significant, more energy is stored.

The researchers experimentally confirmed the transition metal substitution strategy’s inhibitory effect on Oxygen oxidation. Accelerator-based X-ray analysis showed that the generation of Oxygen gas was significantly reduced when a part of Ruthenium was replaced with Nickel. Furthermore, they theoretically demonstrated that charge rearrangement occurs through density functional calculation (DFT).

This study was conducted by Professor Seo Dong-hwa of KAIST, Chung-Ang University, Pohang Accelerator Laboratory, Professor Yu Zhang Li of UCLA, UC Berkeley, and Lawrence Berkeley Research Institute. The accelerator-based X-ray analysis was conducted by Professor Jang Hae-sung of Chung-Ang University (Co-first author), and the DFT theoretical calculation was led by Dr. Lee Eun-ryul (Co-first author) of the Lawrence Berkeley Institute in the United States.

Professor Lee Hyun-wook said, “We presented the direction of material development to cathode material researchers by librarying technology through various experiments and theoretical analysis,” adding, “It will help to develop long-distance driving battery materials without explosions with increased energy density.”

The study was carried out with the support of the National Research Foundation of Korea (NRF)’s international cooperation and development project on source technology. The results were published online on Feb. 19 in ‘Science Advances’, a sister paper of the world-renowned journal ‘Science’ published by the American Science Association (AAAS).

Read more on PAL website

Diamond celebrates 14,000th paper – A breakthrough in lithium-ion battery research

2025/01/172025/01/17

A new understanding of the role oxygen plays could revolutionise battery development

Diamond Light Source stands as one of the leading research facilities globally, driving scientific advancements. The 14,000th paper published as a result of innovative experiments undertaken at the UK’s national synchrotron highlights the profound impact science can have in addressing the world’s most urgent challenges. A team of researchers from WMG at the University of Warwick, in collaboration with academic partners in the Faraday Institution’s Degradation and FutureCat projects, has conducted a ground-breaking study that bridges the gap between academic models and real-world battery performance.

Their work, recently published in Joule, used a trio of synchrotron techniques – Resonant Inelastic soft X-ray Scattering (RIXS), hard and soft X-ray absorption spectroscopy (XAS) – to investigate the charge compensation mechanism of lithium-ion (Li-ion) battery cathodes during high-voltage operation. This study demonstrates that oxygen plays a significant role through a metal-ligand redox process, emphasising the importance of focusing on surface passivation strategies to mitigate oxygen reactivity with electrolytes, reducing degradation and enhancing safety. By using pilot-line fabricated pouch cells, this work aligns fundamental research with commercial applications and offers crucial insights to improve energy density and cycling stability.

Challenges and Opportunities for High-Energy-Density Batteries

The global transition to a low-carbon future requires the development of low-cost, reliable and long-range electric vehicles, with Li-ion batteries playing a crucial role. However, traditional models of the electronic charge compensation mechanism in layered metal oxide cathodes are insufficient for developing next-generation batteries with increased energy density through high-voltage operation.

Prof Louis Piper explained:

When we talk about trying to increase the energy density of a battery, what that means is being able to remove as many electrons as possible, In a lithium-ion battery, Li-ions move between the anode and a cathode, releasing an equal number of electrons as current. In a commercial layered metal oxide battery, we can pull out about two-thirds of the accessible lithium ions, and therefore, two-thirds of the available electrons. That means the battery is always below its theoretical capacity, but it’s engineered that way to prevent the degradation that occurs when you pull more out. Replacing cobalt with nickel increases the practical capacity of the battery, but it pushes it closer to the point where you see accelerated degradation. Traditional models attribute charge compensation solely to transition metal oxidation, but if that’s true then why does replacing cobalt with nickel change things, and why do we have more problems with safety and oxygen loss as we increase the energy density? We need a better understanding of the metal-ligand redox process to develop safe, stable, higher performance Li-ion cells.

Innovating Battery Research with Real-World Testing

WMG is home to a Battery Scale-Up pilot facility, a suite of cell production equipment covering the full production process cell assembly and testing. It allows researchers to manufacture battery cells in a variety of different formats.

RIXS Shows Why Li-rich Batteries Fade

2024/09/172024/09/20

High-resolution resonant inelastic X-ray scattering uncovers the role that oxygen plays in voltage fade in next-gen battery materials

As part of the transition to net zero, the Faraday Institution’s CATMAT (Lithium Ion Cathode Materials) project is focusing on improving lithium-ion battery energy density and electric vehicle (EV) range. Its scope includes adding to our understanding of lithium-rich (Li-rich) oxygen-redox cathodes and novel anion-chemistry cathodes, as well as developing scalable synthesis routes for these materials. As part of this project, researchers from the University of Oxford are working with Diamond’s I21 beamline to explore the cause of voltage fade in Li-rich cathodes, using high-resolution resonant inelastic X-ray scattering (RIXS) spectroscopy. In work recently published in Nature Materials, they followed the oxygen redox reaction in Li-rich cathodes over cycling and quantitatively measured the O₂ trapped within the material. Their results show that a gradual increase in electrochemically inactive O₂ and the loss of O₂ from voids near the cathode surface lead to a reduction in the O redox capacity and the observed voltage fade. These important insights could lead to innovations in cathode chemistry and aid the transition to low-carbon energy sources.

Powering net zero: understanding lithium-rich battery cathodes

The net zero transition necessary to limit the effects of climate change requires dramatic cuts to carbon emissions. One of the cornerstones of the UK’s transition will be switching to fossil-free transport, with electric vehicles (EV) one of the most developed options. However, the cathode is a critical limiting factor in efforts to increase the energy density of lithium-ion (Li-ion) batteries for EV applications. As changes to the chemistry of the cathode are likely to lead to improvements in battery performance, such as boosting battery life, storing greater energy to improve range, reducing battery cost and increasing the power available to the EV during acceleration, developing next-generation lithium-ion cathodes is a major priority. “Lithium-ion batteries are very critical to the net zero transition, enabling electric vehicles and grid storage, says Dr Robert House, at the University of Oxford.

In order to get better batteries, we need new materials which are able to store more energy in the same volume and the same mass – an increase the energy density. One of the biggest limitations is the cathode material. These typically have layered structures with alternating layers of transition metal oxide and lithium ions. The best-known cathode materials are NMCs, named for the combination of nickel, cobalt and manganese within the transition metal layer.

Dr Robert House

Lithium-rich cathodes are next-generation materials which have higher concentrations of lithium within the cathode structure, replacing some of the transition metals. They have a higher capacity because they store energy via oxidation of the oxygen in the structure as well as the transition metal. However, although these materials were first discovered over twenty years ago, a long-standing question has been how the oxygen undergoes charge storage. Dr House says:

Over the past few years, working on the CATMAT project, we’ve uncovered that the oxideoxygen anion converts to O₂ molecules, which are trapped within the crystal structure of the cathode. And this discovery of the exact nature of the oxygen was first made possible by using high resolution RIXS on the I21 beamline.

Elusive missing step in the final act of photosynthesis

2023/05/032023/05/04

After decades of effort and help from SLAC’s X-ray laser, scientists have finally seen the process by which nature creates the oxygen we breathe.

Photosynthesis plays a crucial role in shaping and sustaining life on Earth, yet many aspects of the process remain a mystery. One such mystery is how Photosystem II, a protein complex in plants, algae and cyanobacteria, harvests energy from sunlight and uses it to split water, producing the oxygen we breathe. Now researchers from the Department of Energy’s SLAC National Accelerator Laboratory and Lawrence Berkeley National Laboratory, together with collaborators from Uppsala University, Humboldt University, and other institutions have succeeded in cracking a key secret of Photosystem II.

Using SLAC’s Linac Coherent Light Source (LCLS) and the SPring-8 Angstrom Compact free electron LAser (SACLA) in Japan, they captured for the first time in atomic detail what happens in the final moments leading up to the release of breathable oxygen. The data reveal an intermediate reaction step that had not been observed before.

Find out more on the SLAC website

Protein family shows how life adapted to oxygen

2022/10/042022/10/12

Cornell scientists have created an evolutionary model that connects organisms living in today’s oxygen-rich atmosphere to a time, billions of years ago, when Earth’s atmosphere had little oxygen – by analyzing ribonucleotide reductases (RNRs), a family of proteins used by all free-living organisms and many viruses to repair and replicate DNA.

“By understanding the evolution of these proteins, we can understand how nature adapts to environmental changes at the molecular level. In turn, we also learn about our planet’s past,” said Nozomi Ando, associate professor of chemistry and chemical biology in the College of Arts and Sciences and corresponding author of the study. “Comprehensive phylogenetic analysis of the ribonucleotide reductase family reveals an ancestral clade” published in eLife Digest Oct. 4.

Co-first authors of the study are Audrey Burnim and Da Xu, doctoral students in chemistry and chemical biology, and Matthew Spence, Research School of Chemistry, Australian National University, Canberra. Colin J. Jackson, professor of chemistry, Australian National University, Canberra, is a corresponding author.

This undertaking involved a large dataset of 6,779 RNR sequences; the phylogeny took several high-performance computers a combined seven months (1.4 million CPU hours) to calculate. Made possible by computing advances, the approach opens up a new way to study other diverse protein families that have evolutionary or medical significance.

RNRs have adapted to changes in the environment over billions of years to conserve their catalytic mechanism because of their essential role for all DNA-based life, Ando said. Her lab studies protein allostery – how proteins are able to change activity in response to the environment. The evolutionary information in a phylogeny gives us a way to study the relationship between the primary sequence of a protein and its three-dimensional structure, dynamics and function.

Read more on the CHESS website

Image: Tree inference on a ribonucleotide reductase (RNR) sequence dataset as included in the original report, “Comprehensive phylogenetic analysis of the ribonucleotide reductase family reveals an ancestral clade“.

Beryllium configuration with neighbouring oxygen atoms revealed

2019/06/252019/06/26

High-pressure experiments prove 50-year-old theoretical prediction.

In high-pressure experiments at DESY’s X-ray light source PETRA III, scientists have observed a unique configuration of beryllium for the first time: At pressures nearly a million times the average atmospheric pressure, beryllium in a phosphate crystal acquires six neighbouring atoms instead of the usual four. This six-fold coordination had been predicted by theory more than 50 ago, but could not be observed until now in inorganic compounds. DESY scientist Anna Pakhomova and her collaborators report their results in the journal Nature Communications.
“Originally, chemistry textbooks stated that elements like beryllium from the second period of the periodic table could never have more than four neighbours, due to their electron configuration”, explains Pakhomova. “Then around 50 years ago theorists discovered that higher coordinations could actually be possible, but these have adamantly evaded experimental proof in inorganic compounds.” Inorganic compounds are typically those without carbon – apart from a few exceptions like carbon dioxide and carbon monoxide.

Image: Transformation of the usual fourfold coordination of beryllium to five- and sixfold with increasing pressure. (Credit: DESY, Anna Pakhomova)

Did plate tectonics aid the development of life on Earth?

2018/01/242018/01/29

The appearance of plate tectonics 2.5 billion years ago, favouring the internal dynamics of the Earth, would have allowed a significant release of oxygen in the atmosphere inducing the development of life on our planet, according to a study published by the journal Geochemical Perspectives.

The Earth’s atmosphere remained anoxic for two billion years after the formation of our planet. Then, its oxygen content increased drastically during a well-identified Great Oxygenation Event. It is generally believed that the release of free oxygen was due to the biosphere itself, in relation with the evolution of life on Earth. An international team of researchers from Laboratoire Magmas et Volcans (Université Clermont-Ferrand, CNRS-IRD-OPGC), Géosciences Montpellier (Université de Montpellier, CNRS), the laboratory Conditions Extrêmes et Matériaux: Haute Température et Irradiation (CNRS), and involving five scientists from the ESRF propose a completely different scenario. Based on the experimental observation of a significant amount of ferric iron in the deep Earth’s mantle, they suggest an ascent toward the Earth’s surface of a primordial oxidised-mantle material, inducing the arrival of oxygen into the atmosphere. The upwelling movements would have been hampered during the Archean eon, which was dominated by floating micro-plates at the Earth’s surface. Then, major mantle mixing started when modern plate tectonics and deep slab subduction were established about 2.5 billion years ago, enabling the release of oxygen to the Earth’s surface.

>Read more on the ESRF website