Nuclear Magnetic Resonance Spectrometer (Local contact: Janez Plavec)

Nuclear Magnetic Resonance (NMR) spectroscopy exploits atomic nuclei with non-zero magnetic moments to act as a tiny probe for detecting the local structure, dynamics, reaction state and chemical environment within molecules. It is a valuable tool for studying the local structure and dynamics in a variety of solid systems, being also used to confirm the identity of a substance. The Slovenian NMR Centre offers infrastructure and expertise in the field of solid- and liquid-state NMR spectroscopy. Battery research is lively and touches many different areas relevant for battery research and technology, including oxides, phosphates, silicates and sulfur-based batteries or their components. The facility is strongly committed to improving its analytical capacity in this field.

Watch our videos about Liquid-State and Solid-State Nuclear Magnetic Resonance.

HRTEM/EPR (Local contact HRTEM: Corneliu Ghica):

Transmission Electron Microscopy (TEM) is a microscopy technique in which a beam of electrons is transmitted through an ultra-thin specimen, interacting with it as it passes through. TEM is capable of imaging at a significantly higher resolution than light microscopes, thus enabling the instrument’s user to examine fine details, even as small as a single column of atoms. TEM is a fundamental analysis method in various scientific fields, in both physical and biological sciences. Electron Paramagnetic Resonance (EPR) spectroscopy is used to study chemical species with unpaired electrons, called paramagnetic centres. EPR spectroscopy can be used in top research fields, such as the physical phenomena in nanometric particles, characterisation of bulk and nanostructured semiconductor and insulating materials, with applications in nanoelectronics and nanophotonics. Both TEM and EPR are techniques of interest for the study of battery materials.

Watch our introduction video about HRTEM and EPR.

Ion beam analysis can be employed for battery studies and allows for in situ operando measurements. It can be used as a non-destructive method to map lithium distribution with micrometric lateral and depth-profiling capability down to several tens of nm. This feature is of interest for battery technology since it gives quantitative access to diffusion processes that control several aspects of battery performance, such as capacity, cyclability and charging rate.

Nuclear Microprobe (Local contact: Milko Jakšić):

A nuclear microprobe is a device that uses a system of quadrupole lenses to focus an ion beam to the micrometre size. This beamline enables applications of almost all available ion beam analysis techniques: PIXE, PIGE, RBS, ERDA, Nuclear Reaction Analysis (NRA), Ion Beam Induced Charge and Scanning Transmission Ion Microscopy (STIM). All these techniques can be applied for:

• Elemental distributions;
• Quantitative analysis;
• Measurement of lithium distribution of cathode materials.

Rutherford Backscattering (RBS)/Particle-induced X-ray Emission (PIXE) (Local contact: Milko Jakšić):

PIXE is a technique used for the determination of the elemental composition of a material or sample. Its analytic specificity is related to the emission of characteristic X-rays. Highly energetic ions can also interact with atomic nuclei through elastic collisions; thus, the detection of back-scattered ions can be used to determine the concentration and depth profile of elements in the near-surface region of the sample exposed to the ion beam. Generally, concentrations of elements ranging from sodium to uranium can be detected with limits of ca. 1 ppm. RBS is particularly sensitive to light element concentrations and thus complementary to PIXE, which is more responsive to heavier elements.

Ex situ RBS has already been employed to characterise lithium intercalation in a series of cathode materials. In contrast, ex situ PIGE/PIXE has been used to investigate the lithium distribution in different battery components.

Time-of-flight Elastic Recoil Detection Analysis (ToF-ERDA) (Local contact: Milko Jakšić):

ToF-ERDA is a spectroscopic technique for measuring elemental concentration and their depth profiles in unknown samples down to ca. 500 nm. ERDA is used to obtain elemental concentration depth profiles in thin films. Additionally, it provides information about the depth profile of the sample for a wide range of elements, from hydrogen to rare-earth elements with similar sensitivity and depth resolution. Concentrations of 0,1% can be detected routinely. Energy and time of flight of the recoiled nuclei are measured in coincidence, enabling the separation of all elements by energy and mass.

In combination with RBS, ERD has been used to measure Li⁺ and H⁺ distribution at the anodic and cathodic electrode-electrolyte interfaces of lithium-ion batteries with ceramic electrolytes.

Material Test Diffractometer (MTEST) (Local contact: Alex Szakál, Tamás Veres):

MTEST is a general-purpose neutron powder diffractometer. It implements the methods of NPD and total scattering analysis with thermal neutrons. The usual samples are 1.2 cm³. Neutron diffraction studies in Neutron Powder Diffraction (NPD) and Neutron Total Scattering modes can be employed for battery studies. NPD can yield the following type of battery-relevant information:

• Crystalline structure analyses of anodes, cathodes and solid-state electrolytes;
• Phase composition;
• Metastable phases developing during charge/discharge;
• Micro stress;
• Crystalline structure distortion;
• Lattice defects; atomic ordering;
• Li⁺ diffusion/migration paths.

This instrument has been involved in the ex situ study of raw battery materials with total scattering diffraction and the corresponding data modelling.

Neutron Diffractometer with Position-Sensitive Detector system (PSD) (Local contact: Margit Fábián):

The PSD neutron diffractometer is dedicated to atomic structure investigations of amorphous materials, liquids, and crystalline materials with moderate resolution requirements. PSD is a 2-axis diffractometer equipped with a linear position-sensitive detector system. The detector assembly is mounted on the diffractometer arm, and it spans a scattering angle range of 25° at a given detector position. The present configuration of the instrument is suitable for both ex situ and in situ battery work but not for in operando experiments.

Watch our video on Neutron Diffractometry.

Neutron Reflectometer with Polarised Beam Option (GINA) (Local contact: Dániel Merkel):

The Gina neutron reflectometer is a constant-energy angle-dispersive, vertical-sample instrument. It investigates elemental/isotopic surface and depth profiles. Neutron reflectometry in general, and GINA in particular, are suitable for battery-related studies allowing high sensitivity to light elements, strong isotope contrast and matching depth resolution to typical functional battery features.

Examples of battery studies include:

• Structure and kinetics at/close to interfaces;
• Variation of composition in depth;
• Formation and evolution of interfacial phases;
• Evolution of solid-liquid electrolyte interfaces;
• Study of electrochemical reaction mechanisms.

Prompt Gamma Activation Analysis (PGAA) (Local contact: László Szentmiklósi):

PGAA is used for non-destructive elemental analysis of samples by detection of neutron-capture prompt gamma rays. Regarding batteries, this approach has been employed for different studies, such as:

• Precise determination of the proton content in pristine and chemically delithiated Ni-based oxides and in as-fabricated Co-containing cathode materials;
• Correlation of long-term Mn dissolution and capacity retention in LFP/graphite and LFMP/graphite cells.

Radioactive tracing can be used as a method to follow the mobility of certain battery elements.

Watch the video about Prompt Gamma Activation Analysis.

Small Angle Neutron Scattering (SANS) (Local contact: László Almásy, Len Adèl):

The SANS diffractometer Yellow Submarine allows probing structures at length scales from 5 Å to 1500 Å. It has a wide range of applications, including studies of defects and precipitates in materials, alloy segregation, polymers, etc. Small-angle neutron scattering (SANS) investigates structure at length scales in the range of nm÷µm. This approach has been used in battery studies to assess the following:

• Materials nanostructure
• Follow microstructure evolution and formation of interfacial phases (e.g., SEI)
• Characterise porosities and heterogeneity in cathodes
• Analyse morphology and phase separation in polymeric electrolytes
• Investigate ion solvation.

Watch our introduction video to Small Angle Neutron Scattering.

Thermal Neutron Three-Axis spectrometer and Neutron Holographic Instrument (TAST/HOLO) (Local contact: Alex Szakal):

TAST is a thermal neutron three-axis spectrometer. Quasi-elastic and inelastic neutron scattering can be used in battery research to measure local structural and vibrational dynamics, probing mobility as a function of spatial scale. Li⁺ conductivity in polymeric and ceramic electrolytes, as well as in amorphous anodic materials, have been correlated with lattice dynamics.

Thermal Radiography Station (RAD) (Local contact: Zoltán Kis):

The facility offers two measurement positions along the neutron beam path with a beam diameter of approximately 200 mm, used for dynamic (DNR) and static (SNR) imaging with a measured L/D ratio of approximately 250. Neutron imaging, tomography, in particular, is gaining momentum for battery studies, owing to the penetrating power and sensitivity to lithium.

Neutron radiography, tomography and Bragg-edge imaging have been used to monitor Li⁺ transport and spatial distribution, the evolution of Li⁺ concentration, distribution of Li⁺-containing electrolyte and gas-evolution phenomena.

Time Of Flight Diffractometer (TOF-ND) (Local contact: György Káli):

TOF-ND is a general-purpose high-resolution time-of-flight powder diffractometer. It is typically employed for: structure determination and refinement, peak profile analysis, phase and texture analysis of crystalline materials and diffraction in liquids.

Deep X-ray lithography (Local contact: Benedetta Marmiroli):

Deep X-ray lithography (DXLR) is a manufacturing process based on the capacity of specific materials to change their dissolution rate in a liquid solvent once exposed to high-energy irradiation. With this method a pattern can be transferred through an X-ray mask on the material. The beamline performs irradiation of samples with controlled X-ray doses, allowing for high-resolution, high intensity and extreme parallelism.

Examples of application of this technique include:

• Design and fabrication of micro moulds, microelectrodes, and microdevices;
• Development of new materials with improved performances upon controlled irradiation.

Watch our introduction video about Deep X-ray Lithography.

ESCAmicroscopy beamline (Local contact: Luca Gregoratti):

ESCAmicroscopy detects and analyses the X-ray emitted photoelectrons in terms of their kinetic energy. The beamline hosts a Scanning Photoelectron Microscope (SPEM) which combines surface sensitivity and high spatial resolution. The spot size can be defined down to 120 nm with an energy sensitivity within 180 meV. This technique has been extensively employed for battery-related works and other studies of interest for electrochemical energetics. The instrument allows for space-dependent quantitative and qualitative chemical characterisation of complex materials, and typical experiments include:

• Chemical and electrochemical reactions;
• Morphology and electronic properties of materials;
• Monitoring of in situ dynamic processes, such as metal mobility on a surface as a function of temperature and/or electrical/electrochemical bias.

Gas-Phase Photoemission (GAPH) (Local contact: Kevin C. Prince):

GAPH beamline is the only one at Elettra specifically devoted to research on gaseous systems. It offers a unique approach for investigating the electronic properties of free atoms, molecules and clusters in the photon energy range of 13-900 eV. The broad energy range, high resolving power and flux, the purpose-built end-stations make this facility ideal for investigating the spectroscopy and dynamics of various processes relevant to several areas of science and technology. Molecules adsorbed on surfaces are usually studied, and the obtained results are used as a reference for further experiments on the Material Science Beamline. The synergy between GAPH and MSB beamlines can be beneficial for battery-related studies.

High-Resolution Core-level Photoemission Spectroscopy (SuperESCA beamline) (Local contact: Luciano Lizzit):

The SuperESCA beamline implements high-resolution core-level photoemission spectroscopy (HR-XPS). This method allows in-depth investigations on various samples’ electronic and structural properties, ranging from single crystals to thin films and nanostructured materials. SuperESCA combines high-resolution capabilities with a high flux of linearly polarised photons in the 90 to 1500 eV range, allowing to obtain high-resolution spectra (also for low-density systems) and follow real-time surface processes and reactions. SuperESCA is an excellent tool for XPS investigations of the correlation between structural and electronic properties of surfaces and nanostructured materials surface and for the structural determination of thin-film, using X-ray photoelectron diffraction.

High-Resolution Field Emission Scanning Electron Microscope (FESEM) (Local contact: Iva Matolínová):

Compared to SEM, the Field Emission Scanning Electron Microscope (FESEM) can produce less electrostatically distorted images with a spatial resolution down to 1 nm. This instrument is designed for high-vacuum operations and allows for back-scattering spectroscopy and high-energy dispersion X-ray spectroscopy for the chemical element mapping of surfaces with sub-micron resolution.  Samples need to be compatible with the ultra-high vacuum.

FESEM can also be applied to investigate ex situ electrodes for retrieving information on the morphology and chemical distribution within sub-micron particles.

Inelastic Scattering with Ultraviolet Radiation (IUVS) (Local contact: Barbara Rossi):

IUVS beamline is dedicated to the study of inelastic scattering with ultraviolet radiation in the time-space domain with an incident photon energy in the range of 5-11 eV. It is composed of two separate branch lines devoted to UV Brillouin and Resonant Raman Scattering. The acquisition of information about the structure and dynamic of the matter is possible over different length scales. In both synchrotron-based and offline modes, the beamline is ready to accept battery-relevant materials and cells for both ex situ and in situ experiments.

Lab Small Angle X-ray Scattering Facility (Local contact: Manfred Kriechbaum):

The Laboratory-SAXS facility consists of a sealed tube X-ray generator with three opening ports and shutters where three independent SAXSess cameras are connected, one of which can also be used for grazing incidence (GISAXS) studies. Available measurement modes include:

• SAXS
• SWAXS
• Continuous SWAX

This technique is more suitable for classical battery studies than synchrotron SAXS in case very rapid time scales are not needed.

Light Scattering (Local contact: Angela Chemelli):

This includes static (SLS) and dynamic (DLS) light scattering. Dynamic light scattering can be used to determine the size distribution profile of small particles in suspension or polymers in solution.

Materials Science Beamline (Local contacts: Nataliya Tsud; Tomas Skala):

MSB is a versatile beamline offering classical UPD and XPS with high energy resolution and tunable excitation energy for experiments in materials science, surface physics, and more. The tunability of the photon energy ranges from 22 to 1000 eV, and the beamline allows for resonant photoemission (RESPES) and near-edge X-ray absorption fine structure (NEXAFS) spectroscopies in TEY mode. Sample rotation about two axes allows angle-resolved photoemission studies.

Don’t miss our video about the Materials Science Beamline.

Materials characterization by X-ray diffraction (MCX) (Local contact: Jasper Plaisier):

MCX beamline is a general-purpose X-ray diffraction beamline with a sizeable useful range spanning from 4 to 21 keV. The research activity in batteries is lively and includes research on layered transition metal oxides, Prussian blue analogues, Li cathodes, and LiO₂ systems. The systems that can be investigated include organic and inorganic thin films, thermally and/or mechanically modified surfaces of mechanic components, polymers, highly disordered materials in the form of thin films, powders, fibres, etc. This beamline allows for a wide range of non-single-crystal diffraction experiments, such as:

• Grazing angle diffraction and reflectivity
• Residual stress and texture analysis
• Phase identification
• Structural and kinetic studies.

Near Ambient Pressure X-ray Photoelectron Spectroscopy (Local contacts: Břetislav Šmíd; Mykhailo Vorokhta):

X-ray photoelectron spectroscopy (XPS) is a surface-sensitive quantitative technique. The spectra are obtained by irradiating a material with an X-ray beam while simultaneously measuring the energy and the number of electrons escaping from the top 10 nm of the sample material. NAP-XPS can operate at pressures of a few tens of millibar, allowing for the study of chemical interactions on the atomic level for vapour-solid surfaces. Thanks to this technique can be derived information on:

• Elemental composition
• Empirical formula
• Chemical state
• Electronic state

An electrochemical cell equipped with platinum wire as counter electrode and AgCl as a reference is available to the user community.

Watch our video about NAP-XPS technique.

PEEM/XAS (Local contacts: Marcin Zajac):

The PEEM/XAS beamline is dedicated to microscopy and spectroscopy in the absorption of soft X-rays (200-2000 eV). It is equipped with two end-stations: a photoemission electron microscope (PEEM) and a universal station for X-ray absorption spectroscopy (XAS). The PEEM end-station is a fully equipped “surface science laboratory” including a load-lock and an entrance chamber for fast sample transfer from air into ultra-high vacuum. XPEEM samples needs to be UHV compatible, flat, and not charge under illumination. The XAS end-station is also a UHV system equipped with two chambers for spectroscopy and preparation. The Soft-XAS technique can be employed for battery studies and represents an exciting option in this field of research.

Check out our videos about XAS at the PIRX beamline and PEEM at the DEMETER beamline.

Soft X-ray Transmission and Emission Microscope (TwinMic) (Local contact: Alessandra Gianoncelli):

TwinMic is a soft-X ray microscope that integrates the advantages of complementary scanning and full-field imaging modes into a single instrument. Its end station has the unique capability to operate both as a transmission and as a scanning X-ray microscope. Both modes can be employed to implement coherent diffractive imaging approaches. TwinMic combines high lateral resolution with X-ray absorption contrast, particularly between organic matter and water, allowing imaging of specimens in their natural liquid environment. The highest lateral resolution can be achieved with the full-field imaging mode, which is currently about 20 nm using special objective lenses. This beamline systematically hosts electrochemical work, including the investigation of batteries.

Watch our video about TwinMic beamline.

Spectromicroscopy beamline (Local contact: Alexey Barinov):

This beamline houses a unique microscope designed for studies of the local band structure of materials. A low photon energy beam below 100 eV is focused on a submicrometric spot, and electrons arising from the photoemission process are collected analysed in terms of their energetic and angular distribution (ARPES). Samples can be measured in the temperature range of 40-470 K and must be solid and with a flat surface since the instrument operates in ultra-high vacuum.

Battery-related studies include the mapping of lithium distribution on pristine materials.

Synchrotron Infrared Source for Spectroscopy and Imaging (SISSI) (Local contacts: Lisa Vaccari, Giovanni Birarda):

SISSI infrared beamline employs the infrared and the visible components of synchrotron emission to perform spectroscopy and microspectroscopy. It implements two branch lines aiming at Materials and Life Sciences, respectively. Materials Science branch line (SISSI-MAT) is equipped with a spectrometer for measurements over a broad spectral range and can mount different detectors on the infrared microscope, allowing to exploit a diffraction-limited beam from the visible down to the terahertz. The beamline is equipped with cryostats and diamond anvil cells, allowing one to explore the behaviour of matter at extreme temperature and pressure conditions.

Synchrotron Small Angle X-ray Scattering (Local contact: Heinz Amenitsch):

Synchrotron SAXS is a well-known standard method for studying the structure of various objects in the spatial range from 1 to 1000 nm. It’s an exciting tool for studying batteries allowing for time-resolved studies in the sub-millisecond time scale with a SAXS resolution from 1 to 140 nm in real space and GISAXS measurements for studying the structure of thin films.

Watch our video about the SAXS technique.

TomoLab (Local contact: Diego Dreossi):

X-ray computed microtomography (micro-CT) allows imaging of the internal microstructure of different objects and materials, measuring the sample’s three-dimensional X-ray attenuation coefficient map. This technique enables regions with different densities and/or chemical compositions inside the sample to be visualised through virtual slicing or 3D volume rendering procedures. Micro-CT analysis is capable of analysing, among others, failure mechanisms, micro-cracks formation and propagation, internal defects, and morphological details. It is useful when a correlation between physical and microscopic properties is required.

X-ray Absorption Spectroscopy (XAFS) (Local contact: Giuliana Aquilanti):

The XAFS beamline is dedicated to X-ray Absorption Spectroscopy, and it’s designated to cover a wide energy range, from 2.4 to 27 keV. Being site-selective and having a local character, this technique provides information at the same time on the electronic structure and on the local environment of the absorbing atom. Thanks to the accessible energy range, the XAFS beamline covers the principal needs for battery research and therefore has been widely exploited by the battery community. In particular, XAFS plays an important role in supporting the research on the Li-S batteries due to their high stability and reproducibility at S K-edge energy.

X-ray and UV Photoelectron Diffraction (Local contact: Kateřina Veltruská):

XPD is a crystallographic technique that delivers information on a sample material’s morphology, electronic structure, and chemical composition. The suitable sample must be electrically conducting, ultra-high vacuum compatible and with negligible roughness. It is best suited for applications on periodic surfaces. In situ sample preparation is mandatory.

X-ray Diffraction (XRD1 beamline) (Local contact: Maurizio Polentarutti):

X-ray diffraction is a tool used to identify the atomic and molecular structure of a crystal. Crystalline atoms cause a beam of incident X-rays to diffract into many specific directions. By measuring the angles and intensities of these diffracted beams, a crystallographer can produce a three-dimensional picture of the density of electrons within the crystal. From the electron density, the mean position of the atoms can be determined, as well as their chemical bonds, disorder and other information. The light source of the XRD1 beamline is a multipole wiggler with a useful range from 4 to 21 keV, allowing the optimisation of the anomalous signal of several heavy atoms (up to the calcium edge) and offering the enhancement of the anomalous sulphur signal. Such a wide energy range allows both reflection and transmission geometry for a tunable penetration depth. Thanks to the energy range and 2D detector, the beamline can be exploited for operando XRD studies on batteries. The experimental setup allows for cooling the sample in the temperature range of 80-400 K.