Unraveling the structural transformation of Li-rich materials in lithium-batteries

Lithium-Ion Batteries (LIBs) are essentials in everyday life in mobile applications as well as in hybrid/electric mobility. The extraordinary market success of this technology is forcing hard the need of LIBs with improved energy density, environmental compatibility and safety, making necessary to push this technology beyond the current state of the art. In this framework, Co-poor Lithium Rich Layered Oxides (LRLOs) are the most strategic alternative to current Co-rich layered oxide positive electrode materials thanks to the excellent combination of large specific capacity (>250 mAhg-1), high energy density (up to 900 WhKg-1), small costs and improved environmental benignity. The excellent performance of LRLOs derives from the peculiar combination of redox processes originated from the transition metals and the oxygen anions sublattice. The practical use of LRLOs is hindered by several drawbacks, such as voltage decay, capacity fading, and an irreversible capacity lost in the first cycle. These issues are related to structural rearrangements in the lattice upon cycling.

In this work, we demonstrate a new family of LRLOs with general formula Li1.2+xMn0.54Ni0.13Cox-yAl0.03O2 (0.03 ≤ x ≤ 0.08 and 0.03 ≤ y ≤ 0.05), obtained from the replacement of cobalt with lithium and aluminum and we highlight how the balancing of the metal blend can lead to improvements of the Coulombic efficiency in the first cycle, a better capacity retention and reduced voltage decay. To shed light on the complex crystal-chemistry of this class of LRLOs we studied the Co-poorest member of this homologue material series, namely Li1.28Mn0.54Ni0.13Co0.02Al0.03O2, in order to prove the structural evolution occurring upon charge/discharge in lithium cell. To these aims, electrodes have been recovered during the first cycle, the second cycle and after ten cycles of charge/discharge by de-assembling lithium cells into an Ar-filled glove box. These post mortem materials have been sealed in borosilicate capillary tubes (see Fig. 1a) and studied ex situ by X-ray powder diffraction at the MCX beamline.

Read more on the Elettra website

Image: Fig. 1b shows the potential curves vs time for the first two cycles and highlights the points, marked with A, B, C and so on, where the charge or discharge step was stopped and the materials recovered for analysis. According to the diffraction data (Fig. 1c), structural alterations of Li1.28Mn0.54Ni0.13Co0.02Al0.03O2 start with a fast broadening and a shift of the peaks suggesting a smooth lattice modification. When the cell reaches 4.8V vs Li+, a second phase can be identified. In the discharge process opposite structural transformations occur.

Scientists confirm the presence of rare diamond in stony meteorites

Australian and international researchers have used ANSTO’s Australian Synchrotron to confirm the presence of an unusual diamond found in stony meteorites.

The ureilite meteorites contain a rare hexagonal form of diamond, lonsdaleite, that may have been formed shortly after an ancient dwarf planet collided with a large asteroid about 4.5 billion years ago.

The team of scientists from Monash UniversityRMIT UniversityCSIRO, the Australian Synchrotron and Plymouth University confirmed the existence of lonsdaleite and clarified how it was formed in a paper in the Proceedings of the National Academy of Sciences (PNAS) journal. The study was led by geologist Professor Andy Tomkins from Monash University.

Beamline scientists Dr Andrew Langendam and Dr Helen Brand assisted the team with experiments on the powder diffraction beamline.

“Information that indicated the presence of lonsdaleite was gained by other methods but what was needed most was confirmation of lonsdaleite,” explained Dr Langendam.

“Our powder diffraction beamline is able to differentiate complex mineral phases, such as those found in the meteorites.

“X-ray diffraction revealed a series of peaks representing pyroxene, goethite, olivine and lonsdaleite,” he added.

Read more on the ANSTO website

Image: Mineral map highlighting the partial replacement of lonsdaleite by diamond 

Credit: Authors Sequential Lonsdaleite to Diamond Formation in Ureilite Meteorites via In Situ Chemical Fluid/Vapor Deposition PNAS  119 (38) e2208814119

Improving the production of batteries for electric vehicles

A research lead by the company BASF has characterized a new methodology to produce nickel-rich cathode materials used in lithium-ion batteries that optimizes the conventional production process. The proposed model leads to an increase in throughput by a factor of three, representing a considerable increase in the efficiency of future cathode active materials production for battery electric vehicles. The contributions of the MSPD beamline at ALBA have been key in these findings.

Batteries of electric vehicles still have not reached full cost competitiveness with respect to cars powered by combustion engines. This is mainly due to the increase in the cost of the raw materials used to produce the cathode of the batteries. In the search for low-cost materials for cathodes, the research on efficient manufacturing is of utmost importance.

A research led by the company BASF, in collaboration with different German universities and research centers, has studied how to optimize the conventional production process of nickel-rich cathode materials for lithium-ion batteries. This process is a thermal treatment called calcination. More specifically, researchers wanted to obtain a deeper understanding of the lithiation mechanism itself. And also, whether a two-stage calcination process, including a partial-lithiation step, can be used to synthesize cathode active materials with similar properties to those of a conventional one-stage calcination protocol.

The proposed calcination concept leads to an increase in throughput by a factor of three, increasing the efficiency of future cathode active materials production without modifying their physico-chemical properties and electrochemical behavior. Moreover, further advantages of the partial-lithiation process regarding homogeneity of the composition and crystallite size of the cathode active materials are believed to come into view as soon as large-scale sample amounts are investigated, which will be part of future work.

To further characterize the samples after the partial-lithiation step, synchrotron X-ray powder diffraction (XRD) measurements were performed at the MSPD beamline of the ALBA Synchrotron. This is the first report on the composition of the lithium-containing residual needles, which are indicative of an incomplete reaction. By combination of XRD, and other characterization techniques, the presence of Lithium hydroxide was confirmed in the samples prepared with the conventional method but not on the samples obtained with the novel two-stage methodology.

Read more on the ALBA website

Promising new extra-large pore zeolite

An international research team, led in Spain by CSIC scientist Miguel A. Camblor, has discovered a stable aluminosilicate zeolite with a three dimensional system of interconnected extra-large pores, named ZEO-1.

Zeolites are crystalline porous materials with important industrial applications, including uses in catalytic processes. The pore apertures limit the access of molecules into and out of the inner confined space of zeolites, where reactions occur.

The research, published in Science, proved that ZEO-1 possesses these “extra-large” pores of around 10 Å (1 angstrom equals one ten billionth of a meter), but also smaller pores of around 7 Å, which is actually the size of traditional “large” pores.

Because of its porosity, strong acidity and high stability, ZEO-1 may find applications as a catalyst in fine chemistry for the production of pharmaceutical intermediates, in controlled substance release, for pollution abatement or as a support for the encapsulation of photo- or electroactive species (they react to light or an electric field).

“The crossings of its cages delimit super boxes, open spaces that can be considered nanoreactors to carry out chemical reactions in their confined space”, explains Miguel A. Camblor, researcher at the Instituto de Ciencia de Materiales de Madrid – CSIC.

To prove that this new zeolite may be useful in applications involving bigger molecules, researchers measured the adsorption to the inner surface of the zeolite of the dye Nile red – a big molecule. Moreover, they tested its performance in fluid catalytic cracking of heavy oil, a process the world still relies on to produce fuels. In both processes, the new zeolite performed better than the conventional large pore zeolite used nowadays.

This research is the result of an international collaboration between eight research centers in China, the USA, Sweden and Spain. The team was led by Fei-Jian Chen (Bengbu Medical College, China), Xiaobo Chen (China University of Petroleum), Jian Li (Stockholm University) and Miguel A. Camblor (Instituto de Ciencia de Materiales de Madrid, CSIC).

Structure determination with synchrotron light

The zeolite was discovered following a high-throughput screening methodology. The structure solution was challenging because the zeolite has a very complex structure, with a small crystal size (<200nm) but an exceedingly large cell volume.

“The combination of electron diffraction data with synchrotron powder X-ray diffraction data collected at the MSPD beamline of the ALBA Synchrotron and the Argonne National Laboratory (USA) made possible the accurate structure determination of ZEO-1″, says Camblor.

Read more on the ALBA website

Image: A perspective view of the extra-large pore of ZEO-1 along (100)

Unexpected Transformations Reinforce Roman Concrete

Researchers used the Advanced Light Source (ALS) to study binding phases in Roman architectural concrete, revealing reactions and profound transformations that contribute to the material’s long-term cohesion and durability.

The findings add to our growing understanding of cementing processes in Roman concretes, informing resilient materials of the future.

Marie Jackson, a research associate professor at the University of Utah, has devoted much of her career to understanding the scientific mysteries underlying the exceptional durability of Roman concretes. The ALS has been essential to her and her colleagues’ studies, helping to reveal the chemical and microstructural evolution of the materials.

Concrete is made of rock aggregates and a binder. Modern concretes typically use Portland cement—made by burning a mixture of limestone and clay at high temperature—as binder. Roman concretes, in contrast, consist of coarse volcanic rock (or brick) aggregate bound with mortar made from hydrated lime and reactive tephra—the particles ejected from explosive volcanic eruptions.

In this study, Jackson, along with collaborators Admir Masic and Linda Seymour of the Massachusetts Institute of Technology and Nobumichi Tamura of the ALS, examined mortar samples from the Tomb of Caecilia Metella in Rome. The team hoped that the 2,050-year-old monument would provide insights into how Roman builders’ selections of reactive volcanic rock influenced the material characteristics of the very robust concrete.

Read more on the ALS website

Image: The Tomb of Caecilia Metella on the Via Appia Antica in Rome. The edifice is one of the most refined concrete and dimension stone structures of the latest Roman Republican era.

Credit: Emmanuel Brunner

Rotation and axial motion system IV (RAMS IV) load frame

In spring 2021, the fourth generation of Rotation and Axial Motion System (RAMS IV) load frame was commissioned with X-rays at the Structural Materials Beamline (SMB)


The main objectives of commissioning were to enable communication between the existing control system of the beamline (SPEC) and the new control system of RAMS IV (Aerotech), and to synchronize triggering of X-ray detectors with positions of the rotation stages on RAMS IV. To this end, a number of new scripts were written and tested for both SPEC and Aerotech for executing commands, exchanging experimental parameters, interlocking and “handshaking” between the two systems. During the last few days of commissioning, a series of X-ray measurements were performed on a sample mounted on RAMS IV to test the main functionalities of the new load frame.


The RAMS load frame series collectively form the gold standard for high-impact, precision in-situ X-ray mechanical testing at high-energy synchrotrons. The longstanding collaboration between Air Force Research Laboratory (AFRL) and Pulseray Inc. has delivered a new design and controls system.

Two RAMS IV frames were built: (1) a CHESS design for in-situ X-ray studies, and (2) an AFRL design for ex-situ studies. The AFRL machine can be used for ex-situ proof-of-concept, preparatory loading, or longer mechanical loading tests that can complement and inform work that is done in situ on the CHESS machine.

RAMS IV is optimized for simultaneous tension, torsion, and fatigue loading. Torsion and fatigue loadings are new features over the second generation of RAMS (RAMS II) that has been (and is still being) used with many user experiments at CHESS.

Read more on the CHESS website

Image: Staff Scientists Kelly Nygren and Peter Ko worked in tandem with AFRL to commission the RAMS IV

Researchers identify lithium hydride and a new form of lithium fluoride in the interphase of lithium metal anodes

A team of researchers led by chemists at the U.S. Department of Energy’s (DOE) Brookhaven National Laboratory has identified new details of the reaction mechanism that takes place in batteries with lithium metal anodes. The findings, published today in Nature Nanotechnology, are a major step towards developing smaller, lighter, and less expensive batteries for electric vehicles.

Recreating lithium metal anodes

Conventional lithium-ion batteries can be found in a variety of electronics, from smartphones to electric vehicles. While lithium-ion batteries have enabled the widespread use of many technologies, they still face challenges in powering electric vehicles over long distances.

To build a battery better suited for electric vehicles, researchers across several national laboratories and DOE-sponsored universities have formed a consortium called Battery500, led by DOE’s Pacific Northwest National Laboratory (PNNL). Their goal is to make battery cells with an energy density of 500 watt-hours per kilogram, which is more than double the energy density of today’s state-of-the-art batteries. To do so, the consortium is focusing on batteries made with lithium metal anodes.

Read more on the BNL website

Image: Brookhaven chemists Enyuan Hu (left, lead author) and Zulipiya Shadike (right, first author) are shown holding a model of 1,2-dimethoxyethane, a solvent for lithium metal battery electrolytes.

SESAME’s Materials Science beamline starts full user operation

On 17 December 2020, SESAME opened the doors of its Materials Science (MS) beamline to a team from the Royal Scientific Society (RSS) in Jordan, making this instrument, which is dedicated to structural studies with X-ray powder diffraction, the third of the Centre’s beamlines to be fully operational and hosting users.

“We are looking at the first diffraction pattern ever measured for a user sample on the newly-commissioned MS beamline at SESAME. RSS has a place in the history of SESAME”, said HRH Princess Sumaya bint El Hassan, President of the RSS.

The RSS team consists of Kyle Cordova, Executive Director of Scientific Research and Assistant for Research and Development to HRH Princess Sumaya bint El Hassan, and his colleague, the Junior Staff Scientist Ala’a Al-Ghourani. “Our research is focused on discovering new, highly-porous materials for use in mitigating the effects of climate change. Understanding our material’s structure at the atomic level is critical for ensuring that the target application can be met. SESAME’s MS beamline allows us to do this – through X-ray diffraction we can solve the chemical structure in order to improve our material’s end performance” indicated Kyle Cordova, adding “Being the first users is an immense honour. I am proud to be representing Jordan’s largest applied research institution, the Royal Scientific Society, in this historic first!”

Read more on the SESAME website

Image: Ala’a Al-Ghourani and Mahmoud Abdellatief preparing to mount a sample for study in the experimental hutch of the MS beamline.

Credit: Royal Scientific Society

Titanium-based potassium-ion battery positive electrode

Small energy storage devices (like the ones used in cell phones, tablets, and laptops) based on the mature Lithium-ion technology have become a key element of our daily life. Facing the pressing challenges posed by Global Warming, the increasing demand of storage systems for the large-scale automotive industry will soon clash with the sparse provision of lithium in the Earth’s crust.
In this panorama, the development of economically feasible emerging battery technologies based on alternative, earth-abundant, elements, is thus highly desirable.
Potassium-ion batteries could represent a viable substitute to Lithium-ion technology in a large-scale green economy. However, the key problem preventing the success of the K-ion technology is linked to the low efficiency of cathode materials. 

>Read more on the Elettra website

Image: Structural evolution of KTiPO4F. (a) Initial crystal structure (b) In operando SXPD: phase transformations. (c) Corresponding charge-discharge profile

Expertise in characterising materials for lithium ion batteries

Pioneering work on materials for energy production, such as lithium ion batteries, has made ANSTO a centre of specialist capabilities and expertise.

In addition to the research on lithium-ion batteries; the team also investigates other types of batteries that can reversibly host ions, such as sodium and potassium ion batteries. 
Dr Christophe Didier, a post-doc working with Peterson at the ACNS and shared with Peterson’s University of Wollongong collaborators, published work in Advanced Energy Materials providing structural insights into layered manganese oxide electrodes for potassium-Ion batteries.
“In this case, we were able to use X-rays on an operating battery at the Australian Synchrotron,  because potassium has a lot more electrons than lithium.”
These results again confirm the importance of understanding the detailed structural evolution that underpins performance that will inform the strategic design of electrode materials for high-performance potassium ion batteries. “We do have many collaborators but we are always interested in new projects.  Because we are knowledgeable in the materials themselves, we can contribute to the selection of suitable materials as well as leading the characterisation effort.

>Read more on the Australian Synchrotron (ANSTO) website

Image: Powder diffraction instrument scientist, Dr Qinfen Gu at the Australian Synchrotron.

Cathode ‘defects’ improve battery performance

A counterintuitive finding revealed by high-precision powder diffraction analyses suggests a new strategy for building better batteries

UPTON, NY—Engineers strive to design smartphones with longer-lasting batteries, electric vehicles that can drive for hundreds of miles on a single charge, and a reliable power grid that can store renewable energy for future use. Each of these technologies is within reach—that is, if scientists can build better cathode materials.

To date, the typical strategy for enhancing cathode materials has been to alter their chemical composition. But now, chemists at the U.S. Department of Energy’s (DOE) Brookhaven National Laboratory have made a new finding about battery performance that points to a different strategy for optimizing cathode materials. Their research, published in Chemistry of Materials and featured in ACS Editors’ Choice, focuses on controlling the amount of structural defects in the cathode material.

“Instead of changing the chemical composition of the cathode, we can alter the arrangement of its atoms,” said corresponding author Peter Khalifah, a chemist at Brookhaven Lab and Stony Brook University.

>Read more on the NSLS-II at Brookhaven Lab website

Image: Corresponding author Peter Khalifah (left) with his students/co-authors Gerard Mattei (center) and Zhuo Li (right) at one of Brookhaven’s chemistry labs.

Using uranium to create order from disorder

The first demonstration of reversible symmetry lowering phase transformation with heating.

ANSTO’s unique landmark infrastructure has been used to study uranium, the keystone to the nuclear fuel cycle. The advanced instruments at the Australian Synchrotron and the Australian Centre for Neutron Scattering  have not only provided high resolution and precision, but also allowed in situ experiments to be carried out under extreme sample environments such as high temperature, high pressure and controlled gas atmosphere.

As part of his joint PhD studies at the University of Sydney and ANSTO, Gabriel Murphy has been investigating the condensed matter chemistry of a crystalline material, oxygen-deficient strontium uranium oxide, SrUO4-x, which exhibits the unusual property of having ordered defects at high temperatures.

“Strontium uranium oxide is potentially relevant to spent nuclear fuel partitioning and reprocessing,” said Dr Zhaoming Zhang, Gabriel’s ANSTO supervisor and a co-author on the paper with Prof Brendan Kennedy of the University of Sydney that was published recently in Inorganic Chemistry.
Uranium oxides can access several valence states, from tetravalent— encountered commonly in UO2 nuclear fuels, to pentavalent and hexavalent—encountered in both fuel precursor preparation and fuel reprocessing conditions.
Pertinent to the latter scenario, the common fission daughter Sr-90 may react with oxidised uranium to form ternary phases such as SrUO4.

>Read more on the Australian Synchrotron website

Image: Dr Zhaoming Zhang and Gabriel Murphy.

Tripling the energy storage of lithium-ion batteries

Scientists have synthesized a new cathode material from iron fluoride that surpasses the capacity limits of traditional lithium-ion batteries.

As the demand for smartphones, electric vehicles, and renewable energy continues to rise, scientists are searching for ways to improve lithium-ion batteries—the most common type of battery found in home electronics and a promising solution for grid-scale energy storage. Increasing the energy density of lithium-ion batteries could facilitate the development of advanced technologies with long-lasting batteries, as well as the widespread use of wind and solar energy. Now, researchers have made significant progress toward achieving that goal.

A collaboration led by scientists at the University of Maryland (UMD), the U.S. Department of Energy’s (DOE) Brookhaven National Laboratory, and the U.S. Army Research Lab have developed and studied a new cathode material that could triple the energy density of lithium-ion battery electrodes. Their research was published on June 13 in Nature Communications.

>Read more on the NSLS-II at Brookhaven National Lab website

Image: Brookhaven scientists are shown at the Center for Functional Nanomaterials. Pictured from left to right are: (top row) Jianming Bai, Seongmin Bak, and Sooyeon Hwang; (bottom row) Dong Su and Enyuan Hu.

The power of Metal-Organic Frameworks

Trapping nuclear waste at the molecular level

Nuclear power currently supplies just over 10% of the world’s electricity. However one factor hindering its wider implementation is the confinement of dangerous substances produced during the nuclear waste disposal process. One such bi-product of the disposal process is airborne radioactive iodine that, if ingested, poses a significant health risk to humans.  The need for a high capacity, stable iodine store that has a minimised system volume is apparent – and this collaborative research project may have found a solution.

Researchers have successfully used ultra-stable MOFs to confine large amounts of iodine to an exceptionally dense area. A number of complementary experimental techniques, including measurements taken at Diamond Light Source and ISIS Neutron and Muon Source, were coupled with theoretical modelling to understand the interaction of iodine within the MOF pores at the molecular level.

High resolution x-ray powder diffraction (PXRD) data were collected at Diamond’s I11 beamline. The stability and evolution of the MOF pore was monitored as the iodine was loaded into the structure. Comparison of the loaded and empty samples revealed the framework not only adsorbed but retained the iodine within its structure.

>Read more on the Diamond Light Source website

Illustration: Airborne radioactive iodine is one of the bi-products of the nuclear waste disposal process. A recent study involving Diamond Light Source and ISIS Neutron and Muon Source showed how MOFs can capture and store iodine which may have implications for the future confinement of these hazardous substances.

Prehistoric Iranian glass under synchrotron light

Scientists from University of Isfahan in Iran have analysed in the ALBA Synchrotron how were made ancient Iranian glass objects that date back to 2.500 BC. These decorative glass pieces were excavated from the ziggurat of Chogha-Zanbil, a type of stepped pyramidal monument, inscribed on the UNESCO World Heritage List.

Ziggurats, the most distinct architectural feature of the Mesopotamian, are a type of massive stone structure built thousand years ago as a temple where deities lived. Nevertheless, Chogha-Zanbil, near Susa (Iran), is one of the few existent ziggurats found outside the Mesopotamian area. During ancient times Chogha-Zanbil was known as Dur Untaš, and may had been a sacred city of the Elamite Kingdom, an ancient Pre-Iranian civilization centred in the far West and Southwest of what is now modern-day Iran.

In order to determine the chemical composition of these unique samples, including one piece of ceramics and one piece of metallurgical crucible, a team of Iranian scientists came to ALBA Synchrotron to analyse them using X-Rays Powder Diffraction at the MSPD beamline. The MSPD analyses were carried out on more than 100 points on the glass objects. Synchrotron light enabled them to obtain high resolution diffraction patterns, from whose interpretation researchers have deduced the exact composition of the clay based structure as well as glassy part of the samples.

>Read more on the ALBA website

Image: The glass objects were originally used at the walls and doors of the tempel Chogha-Zanbil.
Credit: Mohammadamin Emami