Probing Jahn-Teller Distortions and Antisite Defects in LiNiO2 with 7Li NMR Spectroscopy and Density Functional Theory.

The long- and local-range structure and electronic properties of the high-voltage lithium-ion cathode material for Li-ion batteries, LiNiO2, remain widely debated, as are the degradation phenomena at high states of delithiation, limiting the more widespread use of this material. In particular, the local structural environment and the role of Jahn-Teller distortions are unclear, as are the interplay of distortions and point defects and their influence on cycling behavior. Here, we use ex situ7Li NMR measurements in combination with density functional theory (DFT) calculations to examine Jahn-Teller distortions and antisite defects in LiNiO2. We calculate the 7Li Fermi contact shifts for the Jahn-Teller distorted and undistorted structures, the experimental 7Li room-temperature spectrum being ascribed to an appropriately weighted time average of the rapidly fluctuating structure comprising collinear, zigzag, and undistorted domains. The 7Li NMR spectra are sensitive to the nature and distribution of antisite defects, and in combination with DFT calculations of different configurations, we show that the 7Li resonance at approximately -87 ppm is characteristic of a subset of Li-Ni antisite defects, and more specifically, a Li+ ion in the Ni layer that does not have an associated Ni ion in the Li layer in its 2nd cation coordination shell. Via ex situ7Li MAS NMR, X-ray diffraction, and electrochemical experiments, we identify the 7Li spectral signatures of the different crystallographic phases on delithiation. The results imply fast Li-ion dynamics in the monoclinic phase and indicate that the hexagonal H3 phase near the end of charge is largely devoid of Li.

Steric Control of Luminescence in Phenyl-Substituted Trityl Radicals.

Triphenylmethyl (trityl) radicals have shown potential for use in organic optoelectronic applications, but the design of practical trityl structures has been limited to donor/radical charge-transfer systems due to the poor luminescence of alternant symmetry hydrocarbons. Here, we circumvent the symmetry-forbidden transition of alternant hydrocarbons via excited-state symmetry breaking in a series of phenyl-substituted tris(2,4,6-trichlorophenyl)methyl (TTM) radicals. We show that 3-fold phenyl substitution enhances the emission of the TTM radical and that steric control modulates the optical properties in these systems. Simple ortho-methylphenyl substitution boosts the photoluminescence quantum efficiency from 1% (for TTM) to 65% at a peak wavelength of 612 nm (for 2-T3TTM) in solution. In the crystalline solid state, the neat 2-T3TTM radical shows a remarkably high photoluminescence quantum efficiency of 25% for emission peaking at 706 nm. This has implications in the design of aryl-substituted radical structures where the electronic coupling of the substituents influences variables such as emission, charge transfer, and spin interaction.

Role of Salt Concentration in Stabilizing Charged Ni-Rich Cathode Interfaces in Li-Ion Batteries.

The cathode-electrolyte interphase (CEI) in Li-ion batteries plays a key role in suppressing undesired side reactions while facilitating Li-ion transport. Ni-rich layered cathode materials offer improved energy densities, but their high interfacial reactivities can negatively impact the cycle life and rate performance. Here we investigate the role of electrolyte salt concentration, specifically LiPF6 (0.5-5 m), in altering the interfacial reactivity of charged LiN0.8Mn0.1Co0.1O2 (NMC811) cathodes in standard carbonate-based electrolytes (EC/EMC vol %/vol % 3:7). Extended potential holds of NMC811/Li4Ti5O12 (LTO) cells reveal that the parasitic electrolyte oxidation currents observed are strongly dependent on the electrolyte salt concentration. X-ray photoelectron and absorption spectroscopy (XPS/XAS) reveal that a thicker LixPOyFz-/LiF-rich CEI is formed in the higher concentration electrolytes. This suppresses reactions with solvent molecules resulting in a thinner, or less-dense, reduced surface layer (RSL) with lower charge transfer resistance and lower oxidation currents at high potentials. The thicker CEI also limits access of acidic species to the RSL suppressing transition-metal dissolution into the electrolyte, as confirmed by nuclear magnetic resonance (NMR) spectroscopy and inductively coupled plasma optical emission spectroscopy (ICP-OES). This provides insight into the main degradation processes occurring at Ni-rich cathode interfaces in contact with carbonate-based electrolytes and how electrolyte formulation can help to mitigate these.

The Interplay of Solvation and Polarization Effects on Ion Pairing in Nanoconfined Electrolytes.

The nature of ion-ion interactions in electrolytes confined to nanoscale pores has important implications for energy storage and separation technologies. However, the physical effects dictating the structure of nanoconfined electrolytes remain debated. Here we employ machine-learning-based molecular dynamics simulations to investigate ion-ion interactions with density functional theory level accuracy in a prototypical confined electrolyte, aqueous NaCl within graphene slit pores. We find that the free energy of ion pairing in highly confined electrolytes deviates substantially from that in bulk solutions, observing a decrease in contact ion pairing but an increase in solvent-separated ion pairing. These changes arise from an interplay of ion solvation effects and graphene's electronic structure. Notably, the behavior observed from our first-principles-level simulations is not reproduced even qualitatively with the classical force fields conventionally used to model these systems. The insight provided in this work opens new avenues for predicting and controlling the structure of nanoconfined electrolytes.

Structural disorder determines capacitance in nanoporous carbons.

The difficulty in characterizing the complex structures of nanoporous carbon electrodes has led to a lack of clear design principles with which to improve supercapacitors. Pore size has long been considered the main lever to improve capacitance. However, our evaluation of a large series of commercial nanoporous carbons finds a lack of correlation between pore size and capacitance. Instead, nuclear magnetic resonance spectroscopy measurements and simulations reveal a strong correlation between structural disorder in the electrodes and capacitance. More disordered carbons with smaller graphene-like domains show higher capacitances owing to the more efficient storage of ions in their nanopores. Our findings suggest ways to understand and exploit disorder to achieve highly energy-dense supercapacitors.

Understanding Sorption of Aqueous Electrolytes in Porous Carbon by NMR Spectroscopy.

Ion adsorption at solid-water interfaces is crucial for many electrochemical processes involving aqueous electrolytes including energy storage, electrochemical separations, and electrocatalysis. However, the impact of the hydronium (H3O+) and hydroxide (OH-) ions on the ion adsorption and surface charge distributions remains poorly understood. Many fundamental studies of supercapacitors focus on non-aqueous electrolytes to avoid addressing the role of functional groups and electrolyte pH in altering ion uptake. Achieving microscopic level characterization of interfacial mixed ion adsorption is particularly challenging due to the complex ion dynamics, disordered structures, and hierarchical porosity of the carbon electrodes. This work addresses these challenges starting with pH measurements to quantify the adsorbed H3O+ concentrations, which reveal the basic nature of the activated carbon YP-50F commonly used in supercapacitors. Solid-state NMR spectroscopy is used to study the uptake of lithium bis(trifluoromethanesulfonyl)-imide (LiTFSI) aqueous electrolyte in the YP-50F carbon across the full pH range. The NMR data analysis highlights the importance of including the fast ion-exchange processes for accurate quantification of the adsorbed ions. Under acidic conditions, more TFSI- ions are adsorbed in the carbon pores than Li+ ions, with charge compensation also occurring via H3O+ adsorption. Under neutral and basic conditions, when the carbon's surface charge is close to zero, the Li+ and TFSI- ions exhibit similar but lower affinities toward the carbon pores. Our experimental approach and evidence of H3O+ uptake in pores provide a methodology to relate the local structure to the function and performance in a wide range of materials for energy applications and beyond.

Suppression of Dexter transfer by covalent encapsulation for efficient matrix-free narrowband deep blue hyperfluorescent OLEDs.

Hyperfluorescence shows great promise for the next generation of commercially feasible blue organic light-emitting diodes, for which eliminating the Dexter transfer to terminal emitter triplet states is key to efficiency and stability. Current devices rely on high-gap matrices to prevent Dexter transfer, which unfortunately leads to overly complex devices from a fabrication standpoint. Here we introduce a molecular design where ultranarrowband blue emitters are covalently encapsulated by insulating alkylene straps. Organic light-emitting diodes with simple emissive layers consisting of pristine thermally activated delayed fluorescence hosts doped with encapsulated terminal emitters exhibit negligible external quantum efficiency drops compared with non-doped devices, enabling a maximum external quantum efficiency of 21.5%. To explain the high efficiency in the absence of high-gap matrices, we turn to transient absorption spectroscopy. It is directly observed that Dexter transfer from a pristine thermally activated delayed fluorescence sensitizer host can be substantially reduced by an encapsulated terminal emitter, opening the door to highly efficient 'matrix-free' blue hyperfluorescence.

Jahn-Teller Distortions and Phase Transitions in LiNiO2: Insights from Ab Initio Molecular Dynamics and Variable-Temperature X-ray Diffraction.

The atomistic structure of lithium nickelate (LiNiO2), the parent compound of Ni-rich layered oxide cathodes for Li-ion batteries, continues to elude a comprehensive understanding. The common consensus is that the material exhibits local Jahn-Teller distortions that dynamically reorient, resulting in a time-averaged undistorted R3̅m structure. Through a combination of ab initio molecular dynamics (AIMD) simulations and variable-temperature X-ray diffraction (VT-XRD), we explore Jahn-Teller distortions in LiNiO2 as a function of temperature. Static Jahn-Teller distortions are observed at low temperatures (T < 250 K) via AIMD simulations, followed by a broad phase transition that occurs between 250 and 350 K, leading to a highly dynamic, displacive phase at high temperatures (T > 350 K), which does not show the four short and two long bonds characteristic of local Jahn-Teller distortions. These transitions are followed in the AIMD simulations via abrupt changes in the calculated pair distribution function and the bond-length distortion index and in X-ray diffraction via the monoclinic lattice parameter ratio, amon/bmon, and δ angle, the fit quality of an R3̅m-based structural refinement, and a peak sharpening of the diffraction peaks on heating, consistent with the loss of distorted domains. Between 250 and 350 K, a mixed-phase regime is found via the AIMD simulations where distorted and undistorted domains coexist. The repeated change between the distorted and undistorted states in this mixed-phase regime allows the Jahn-Teller long axes to change direction. These pseudorotations of the Ni-O long axes are a side effect of the onset of the displacive phase transition. Antisite defects, involving Li ions in the Ni layer and Ni ions in the Li layer, are found to pin the undistorted domains at low temperatures, impeding cooperative ordering at a longer length scale.

Unlocking Li superionic conductivity in face-centred cubic oxides via face-sharing configurations.

Oxides with a face-centred cubic (fcc) anion sublattice are generally not considered as solid-state electrolytes as the structural framework is thought to be unfavourable for lithium (Li) superionic conduction. Here we demonstrate Li superionic conductivity in fcc-type oxides in which face-sharing Li configurations have been created through cation over-stoichiometry in rocksalt-type lattices via excess Li. We find that the face-sharing Li configurations create a novel spinel with unconventional stoichiometry and raise the energy of Li, thereby promoting fast Li-ion conduction. The over-stoichiometric Li-In-Sn-O compound exhibits a total Li superionic conductivity of 3.38 × 10-4 S cm-1 at room temperature with a low migration barrier of 255 meV. Our work unlocks the potential of designing Li superionic conductors in a prototypical structural framework with vast chemical flexibility, providing fertile ground for discovering new solid-state electrolytes.

Controlling the Superconductivity of Nb2PdxS5 via Reversible Li Intercalation.

The Nb2PdxS5 (x ≈ 0.74) superconductor with a Tc of 6.5 K is reduced by the intercalation of lithium in ammonia solution or electrochemically to produce an intercalated phase with expanded lattice parameters. The structure expands by 2% in volume and maintains the C2/m symmetry and rigidity due to the PdS4 units linking the layers. Experimental and computational analysis of the chemically synthesized bulk sample shows that Li occupies triangular prismatic sites between the layers with an occupancy of 0.33(4). This level of intercalation suppresses the superconductivity, with the injection of electrons into the metallic system observed to also reduce the Pauli paramagnetism by ∼40% as the bands are filled to a Fermi level with a lower density of states than in the host material. Deintercalation using iodine partially restores the superconductivity, albeit at a lower Tc of ∼5.5 K and with a smaller volume fraction than in fresh Nb2PdxS5. Electrochemical intercalation reproduces the chemical intercalation product at low Li content (<0.4) and also enables greater reduction, but at higher Li contents (≥0.4) accessed by this route, phase separation occurs with the indication that Li occupies another site.

Exploring the Landscape of Heterocyclic Quinones for Redox Flow Batteries.

Redox flow batteries (RFBs) rely on the development of cheap, highly soluble, and high-energy-density electrolytes. Several candidate quinones have already been investigated in the literature as two-electron anolytes or catholytes, benefiting from fast kinetics, high tunability, and low cost. Here, an investigation of nitrogen-rich fused heteroaromatic quinones was carried out to explore avenues for electrolyte development. These quinones were synthesized and screened by using electrochemical techniques. The most promising candidate, 4,8-dioxo-4,8-dihydrobenzo[1,2-d:4,5-d']bis([1,2,3]triazole)-1,5-diide (-0.68 V(SHE)), was tested in both an asymmetric and symmetric full-cell setup resulting in capacity fade rates of 0.35% per cycle and 0.0124% per cycle, respectively. In situ ultraviolet-visible spectroscopy (UV-Vis), nuclear magnetic resonance (NMR), and electron paramagnetic resonance (EPR) spectroscopies were used to investigate the electrochemical stability of the charged species during operation. UV-Vis spectroscopy, supported by density functional theory (DFT) modeling, reaffirmed that the two-step charging mechanism observed during battery operation consisted of two, single-electron transfers. The radical concentration during battery operation and the degree of delocalization of the unpaired electron were quantified with NMR and EPR spectroscopy.

Engineering considerations for practical lithium-air electrolytes.

Lithium-air batteries promise exceptional energy density while avoiding the use of transition metals in their cathodes, however, their practical adoption is currently held back by their short lifetimes. These short lifetimes are largely caused by electrolyte breakdown, but despite extensive searching, an electrolyte resistant to breakdown has yet to be found. This paper considers the requirements placed on an electrolyte for it to be considered usable in a practical cell. We go on to examine ways, through judicious cell design, of relaxing these requirements to allow for a broader range of compounds to be considered. We conclude by suggesting types of molecules that could be explored for future cells. With this work, we aim to broaden the scope of future searches for electrolytes and inform new cell design.

Insights into soft short circuit-based degradation of lithium metal batteries.

The demand for electric vehicles with extended ranges has created a renaissance of interest in replacing the common metal-ion with higher energy-density metal-anode batteries. However, the potential battery safety issues associated with lithium metal must be addressed to enable lithium metal battery chemistries. A considerable performance gap between lithium (Li) symmetric cells and practical Li batteries motivated us to explore the correlation between the shape of voltage traces and degradation. We coupled impedance spectroscopy and operando NMR and used the new approach to show that transient (i.e., soft) shorts form in realistic conditions for battery applications; however, they are typically overlooked, as their electrochemical signatures are often not distinct. The typical rectangular-shaped voltage trace, widely considered ideal, was proven, under the conditions studied here, to be a result of soft shorts. Recoverable soft-shorted cells were demonstrated during a symmetric cell polarisation experiment, defining a new type of critical current density: the current density at which the soft shorts are not reversible. Moreover, we demonstrated that soft shorts, detected via electrochemical impedance spectroscopy (EIS) and validated via operando NMR, are predictive towards the formation of hard shorts, showing the potential use of EIS as a relatively low-cost and non-destructive method for early detection of catastrophic shorts and battery failure while demonstrating the strength of operando NMR as a research tool for metal plating in lithium batteries.

Binder-Free Cnt Cathodes for Li-O2 Batteries with More Than One Life.

Li-O2 batteries (LOB) performance degradation ultimately occurs through the accumulation of discharge products and irreversible clogging of the porous electrode during the cycling. Electrode binder degradation in the presence of reduced oxygen species can result in additional coating of the conductive surface, exacerbating capacity fading. Herein, a facile method to fabricate free-standing is established, binder-free electrodes for LOBs in which multi-wall carbon nanotubes form cross-linked networks exhibiting high porosity, conductivity, and flexibility. These electrodes demonstrate high reproducibility upon cycling in LOBs. After cell death, efficient and inexpensive methods to wash away the accumulated discharge products are demonstrated, as reconditioning method. The second life usage of these electrodes is validated, without noticeable loss of performance. These findings aim to assist in the development of greener high energy density batteries while reducing manufacturing and recycling costs.

Solvent-dependent iodide interactions in LiO2 electrolytes - a molecular dynamics study.

Iodide-based redox mediation in Li-O2 batteries is regarded as a promising system due to its relatively high round-trip efficiency, compared to alternative systems. Here we explore the role of electrolyte composition in the solvation of I-, which has been shown to be critical for the efficient operation of this redox mediator, using a molecular dynamics approach. A combinatorial exploration of I- and H2O concentrations was performed, for a fixed concentration of Li+, across a series of glymes, with increasing chain length (mono- to tetraglyme). The resulting radial distribution functions show that shorter glymes allow for a closer packing of the I- redox mediator. Furthermore, increasing the I- concentration also reduces the solvation of Li+ in the glymes, especially in G2. The presence of water further pulls the I- and Li+ together. With increasing water content, its presence in the iodide's coordination shell increases markedly - an effect most pronounced for monoglyme. Competition between Li+ and I- for the coordination of water is modulated by the different solvents as they perturb the local coordination shell of these important complexes, with longer chain lengths being less affected by increases in water concentrations.

Spiers Memorial Lecture: Lithium air batteries - tracking function and failure.

The lithium-air battery (LAB) is arguably the battery with the highest energy density, but also a battery with significant challenges to be overcome before it can be used commercially in practical devices. Here, we discuss experimental approaches developed by some of the authors to understand the function and failure of lithium-oxygen batteries. For example, experiments in which nuclear magnetic resonance (NMR) spectroscopy was used to quantify dissolved oxygen concentrations and diffusivity are described. 17O magic angle spinning (MAS) NMR spectra of electrodes extracted from batteries at different states of charge (SOC) allowed the electrolyte decomposition products at each stage to be determined. For instance, the formation of Li2CO3 and LiOH in a dimethoxyethane (DME) solvent and their subsequent removal on charging was followed. Redox mediators have been used to chemically reduce oxygen or to chemically oxidise Li2O2 in order to prevent electrode clogging by insulating compounds, which leads to lower capacities and rapid degradation; the studies of these mediators represent an area where NMR and electron paramagnetic resonance (EPR) studies could play a role in unravelling reaction mechanisms. Finally, recently developed coupled in situ NMR and electrochemical impedance spectroscopy (EIS) are used to characterise the charge transport mechanism in lithium symmetric cells and to distinguish between electronic and ionic transport, demonstrating the formation of transient (soft) shorts in common lithium-oxygen electrolytes. More stable solid electrolyte interphases are formed under an oxygen atmosphere, which helps stabilise the lithium anode on cycling.