Coordination of dissolved transition metals in pristine battery electrolyte solutions determined by NMR and EPR spectroscopy.

The solvation of dissolved transition metal ions in lithium-ion battery electrolytes is not well-characterised experimentally, although it is important for battery degradation mechanisms governed by metal dissolution, deposition, and reactivity in solution. This work identifies the coordinating species in the Mn and Ni solvation spheres in LiPF/LiTFSI-carbonate electrolyte solutions by examining the electron-nuclear spin interactions, which are probed by pulsed EPR and paramagnetic NMR spectroscopy. These techniques investigate solvation in frozen electrolytes and in the liquid state at ambient temperature, respectively, also probing the bound states and dynamics of the complexes involving the ions.

Chemical Prelithiated 3D Lithiophilic/-Phobic Interlayer Enables Long-Term Li Plating/Stripping.

The up-to-date lifespan of zero-excess lithium (Li) metal batteries is limited to a few dozen cycles due to irreversible Li-ion loss caused by interfacial reactions during cycling. Herein, a chemical prelithiated composite interlayer, made of lithiophilic silver (Ag) and lithiophobic copper (Cu) in a 3D porous carbon fiber matrix, is applied on a planar Cu current collector to regulate Li plating and stripping and prevent undesired reactions. The Li-rich surface coating of lithium oxide (LiO), lithium carboxylate (RCOLi), lithium carbonates (ROCOLi), and lithium hydride (LiH) is formed by soaking and directly heating the interlayer in -butyllithium hexane solution.

U(V) Stabilization via Aliovalent Incorporation of Ln(III) into Oxo-salt Framework.

Pentavalent uranium compounds are key components of uranium's redox chemistry and play important roles in environmental transport. Despite this, well-characterized U(V) compounds are scarce primarily because of their instability with respect to disproportionation to U(IV) and U(VI). In this work, we provide an alternate route to incorporation of U(V) into a crystalline lattice where different oxidation states of uranium can be stabilized through the incorporation of secondary cations with different sizes and charges.

Machine Learning Isotropic Values of Radical Polymers.

Methods for electronic structure computations, such as density functional theory (DFT), are routinely used for the calculation of spectroscopic parameters to establish and validate structure-parameter correlations. DFT calculations, however, are computationally expensive for large systems such as polymers. This work explores the machine learning (ML) of isotropic values, , obtained from electron paramagnetic resonance (EPR) experiments of an organic radical polymer.

Post-treatment strategies for pyrophoric KOH-activated carbon nanofibres.

The effect of two atmospheric post-treatment conditions directly after the KOH activation of polyacrylonitrile-based nanofibres is studied in this work. As post-treatment different N : O flow conditions, namely high O-flow and low O-flow, are applied and their impact on occurring reactions and carbon nanofibres' properties is studied by thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), scanning electron microscopy (SEM), Raman spectroscopy, elemental analysis and CO and Ar gas adsorption. At high O-flow conditions a pyrophoric effect was observed on the KOH-activated carbon nanofibers.

Multimodal investigation of electronic transport in PTMA and its impact on organic radical battery performance.

Organic radical batteries (ORBs) represent a viable pathway to a more sustainable energy storage technology compared to conventional Li-ion batteries. For further materials and cell development towards competitive energy and power densities, a deeper understanding of electron transport and conductivity in organic radical polymer cathodes is required. Such electron transport is characterised by electron hopping processes, which depend on the presence of closely spaced hopping sites.

Insights into the Lithium Nucleation and Plating/Stripping Behavior in Ionic Liquid-Based Electrolytes.

Rechargeable lithium-metal batteries (LMBs) are anticipated to enable enhanced energy densities, which can be maximized when minimizing the amount of excess lithium in the cell down to zero, also referred to as "zero excess" LMBs. In this case, the only source of lithium is the positive electrode active material─just like in lithium-ion batteries. However, this requires the fully reversible deposition of metallic lithium, i.

Gauging the importance of structural parameters for hyperfine coupling constants in organic radicals.

The identification of fundamental relationships between atomic configuration and electronic structure typically requires experimental empiricism or systematic theoretical studies. Here, we provide an alternative statistical approach to gauge the importance of structure parameters, , bond lengths, bond angles, and dihedral angles, for hyperfine coupling constants in organic radicals. Hyperfine coupling constants describe electron-nuclear interactions defined by the electronic structure and are experimentally measurable, for example, by electron paramagnetic resonance spectroscopy.

Laplace inverted pulsed EPR relaxation to study contact between active material and carbon black in Li-organic battery cathodes.

The addition of conductive additives during electrode fabrication is standard practice to mitigate a low intrinsic electronic conductivity of most cathode materials used in Li-ion batteries. To ensure an optimal conduction pathway, these conductive additives, which generally consist of carbon particles, need to be in good contact with the active compounds. Herein, we demonstrate how a combination of pulsed electron paramagnetic resonance (EPR) relaxometry and inverse Laplace transform (ILT) can be used to study such contact.

Understanding of the structural chemistry in the uranium oxo-tellurium system under HT/HP conditions.

The study of phase formation in the U-Te-O systems with mono and divalent cations under high-temperature high-pressure (HT/HP) conditions has resulted in four new inorganic compounds: K [(UO) (TeO)], Mg [(UO) (TeO)], Sr [(UO) (TeO)] and Sr [(UO) (TeO)]. Tellurium occurs as Te, Te, and Te in these phases which demonstrate the high chemical flexibility of the system. Uranium VI) adopts a variety of coordinations, namely, UO in K [(UO) (TeO), UO in Mg [(UO) (TeO)] and Sr [(UO) (TeO)], and UO in Sr [(UO) (TeO)].

Forced Disorder in the Solid Solution LiP-LiS: A New Class of Fully Reduced Solid Electrolytes for Lithium Metal Anodes.

All-solid-state batteries based on non-combustible solid electrolytes are promising candidates for safe energy storage systems. In addition, they offer the opportunity to utilize metallic lithium as an anode. However, it has proven to be a challenge to design an electrolyte that combines high ionic conductivity and processability with thermodynamic stability toward lithium.

Understanding the role of flux, pressure and temperature on polymorphism in ThBO.

A novel polymorph of ThBO, denoted as β-ThBO, was synthesised under high-temperature high-pressure (HT/HP) conditions. single crystal X-ray diffraction measurements, β-ThBO was found to form a three-dimensional (3D) framework structure where thorium atoms are ten-fold oxygen coordinated forming tetra-capped trigonal prisms. The only other known polymorph of ThBO, denoted α, synthesised herein using a known borax, BO-NaBO, high temperature solid method, was found to transform to the β polymorph when exposed to conditions of 4 GPa and ∼900 °C.

The Structure of the Electric Double Layer of the Protic Ionic Liquid [Dema][TfO] Analyzed by Atomic Force Spectroscopy.

Protic ionic liquids are promising electrolytes for fuel cell applications. They would allow for an increase in operation temperatures to more than 100 °C, facilitating water and heat management and, thus, increasing overall efficiency. As ionic liquids consist of bulky charged molecules, the structure of the electric double layer significantly differs from that of aqueous electrolytes.

Oxygen Nonstoichiometry and Valence State of Manganese in La Ca MnO.

Perovskites of the ABO type, such as LaMnO, can be used as air electrodes in solid oxide fuel cells and electrolyzers. Their properties can be tuned by A- and B-site substitutions. The influence of La substitution by Ca on the oxygen nonstoichiometry has been investigated frequently, but the results depend highly on the synthesis and atmospheric conditions.

Tilting and Distortion in Rutile-Related Mixed Metal Ternary Uranium Oxides: A Structural, Spectroscopic, and Theoretical Investigation.

A systematic investigation examining the origins of structural distortions in rutile-related ternary uranium UO oxides using a combination of high-resolution structural and spectroscopic measurements supported by calculations is presented. The structures of β-CdUO, MnUO, CoUO, and MgUO are determined at high precision by using a combination of neutron powder diffraction (NPD) and synchrotron X-ray powder diffraction (S-XRD) or single crystal X-ray diffraction. The structure of β-CdUO is best described by space group whereas MnUO, CoUO, and MgUO are described by the lower symmetry space group and are isostructural with the previously reported β-NiUO [Murphy et al.

DFTB Modeling of Lithium-Intercalated Graphite with Machine-Learned Repulsive Potential.

Lithium ion batteries have been a central part of consumer electronics for decades. More recently, they have also become critical components in the quickly arising technological fields of electric mobility and intermittent renewable energy storage. However, many fundamental principles and mechanisms are not yet understood to a sufficient extent to fully realize the potential of the incorporated materials.

SABRE polarized low field rare-spin spectroscopy.

High-field nuclear magnetic resonance (NMR) spectroscopy is an indispensable technique for identification and characterization of chemicals and biomolecular structures. In the vast majority of NMR experiments, nuclear spin polarization arises from thermalization in multi-Tesla magnetic fields produced by superconducting magnets. In contrast, NMR instruments operating at low magnetic fields are emerging as a compact, inexpensive, and highly accessible alternative but suffer from low thermal polarization at a low field strength and consequently a low signal.

Chemical shift reference scale for Li solid state NMR derived by first-principles DFT calculations.

For studying electrode and electrolyte materials for lithium ion batteries, solid-state (SS) nuclear magnetic resonance (NMR) of lithium moves into focus of current research. Theoretical simulations of magnetic resonance parameters facilitate the analysis and interpretation of experimental Li SS-NMR spectra and provide unique insight into physical and chemical processes that are determining the spectral profile. In the present paper, the accuracy and reliability of the theoretical simulation methods of Li chemical shielding values is benchmarked by establishing a reference scale for Li SS-NMR of diamagnetic compounds.

Ab Initio Simulation of pH-Sensitive Biomarkers in Magnetic Resonance Imaging.

An ab initio simulation scheme is introduced as a theoretical prescreening approach to facilitate and enhance the research for pH-sensitive biomarkers. The proton H and carbon C nuclear magnetic resonance (NMR) chemical shifts of the recently published marker for extracellular pH, [1,5-C]zymonic acid (ZA), and the as yet unpublished ( Z)-4-methyl-2-oxopent-3-enedioic acid (OMPD) were calculated with ab initio methods as a function of the pH. The influence of the aqueous solvent was taken into account either by an implicit solvent model or by explicit water molecules, where the latter improved the accuracy of the calculated chemical shifts considerably.

Electrochemical and Electronic Charge Transport Properties of Ni-Doped LiMn₂O₄ Spinel Obtained from Polyol-Mediated Synthesis.

LiNiMnO₄ (LNMO) spinel has been extensively investigated as one of the most promising high-voltage cathode candidates for lithium-ion batteries. The electrochemical performance of LNMO, especially its rate performance, seems to be governed by its crystallographic structure, which is strongly influenced by the preparation methods. Conventionally, LNMO materials are prepared via solid-state reactions, which typically lead to microscaled particles with only limited control over the particle size and morphology.

Deuteration of Hyperpolarized C-Labeled Zymonic Acid Enables Sensitivity-Enhanced Dynamic MRI of pH.

Aberrant pH is characteristic of many pathologies such as ischemia, inflammation or cancer. Therefore, a non-invasive and spatially resolved pH determination is valuable for disease diagnosis, characterization of response to treatment and the design of pH-sensitive drug-delivery systems. We recently introduced hyperpolarized [1,5- C ]zymonic acid (ZA) as a novel MRI probe of extracellular pH utilizing dissolution dynamic polarization (DNP) for a more than 10000-fold signal enhancement of the MRI signal.

3D printed sample holder for in-operando EPR spectroscopy on high temperature polymer electrolyte fuel cells.

Electrochemical cells contain electrically conductive components, which causes various problems if such a cell is analyzed during operation in an EPR resonator. The optimum cell design strongly depends on the application and it is necessary to make certain compromises that need to be individually arranged. Rapid prototyping presents a straightforward option to implement a variable cell design that can be easily adapted to changing requirements.

Electron spin coherence near room temperature in magnetic quantum dots.

We report on an example of confined magnetic ions with long spin coherence near room temperature. This was achieved by confining single Mn(2+) spins in colloidal semiconductor quantum dots (QDs) and by dispersing the QDs in a proton-spin free matrix. The controlled suppression of Mn-Mn interactions and minimization of Mn-nuclear spin dipolar interactions result in unprecedentedly long phase memory (TM ~ 8 μs) and spin-lattice relaxation (T1 ~ 10 ms) time constants for Mn(2+) ions at T = 4.