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.

Proton-coupled electron transfer at SOFC electrodes.

Understanding the charge transfer processes at solid oxide fuel cell (SOFC) electrodes is critical to designing more efficient and robust materials. Activation losses at SOFC electrodes have been widely attributed to the ambipolar migration of charges at the mixed ionic-electronic conductor-gas interface. Empirical Butler-Volmer kinetics based on the transition state theory is often used to model the current-voltage relationship, where charged particles transfer classically over an energy barrier. However, the hydrogen oxidation/water electrolysis reaction H2(g) + O2- ⇌ H2O(g) + 2e- must be modeled through concerted electron and proton tunneling events, where we unify the theory of the electrostatic surface potential with proton-coupled electron transfer kinetics. We derive a framework for the reaction rate that depends on the electrostatic surface potential, adsorbate dipole moment, the electronic structure of the electron donor/acceptor, and vibronic states of the hydrogen species. This theory was used to study the current-voltage characteristics of the Ni/gadolinium-doped ceria electrode in H2/H2O(g), where we find excellent validation of this novel model. These results yield the first reported quantification of the solvent reorganization energy for an SOFC material and suggest that the three-phase boundary mechanism is the dominant pathway for charge transfer at cermet electrodes.

Neutron diffraction and DFT studies of oxygen defect and transport in higher-order Ruddlesden-Popper phase materials.

A series of higher-order Ruddlesden-Popper phase materials - La3PrNi3O10-δ , La2Pr2Ni3O10-δ and LaPr3Ni3O10-δ - were synthesised and investigated by neutron powder diffraction to understand the oxygen defect structure and propose possible pathways for oxygen transport in these materials. Further complimentary DFT calculations of the materials were performed to support the experimental analysis. All of the phases were hypostoichiometric and it was observed that the majority of the oxygen vacancies were confined to the perovskite layers, with a preference for equatorial oxygen sites. A particular preference for vacancies in O(1) and O(5) sites at high temperatures was observed from neutron diffraction measurements which were further complimented by DFT calculations wherein the vacancy formation energy was found to be lowest at the O(1) site. Also, a preference for a curved oxygen transport pathway around the NiO6 octahedra was observed which agrees with the published literature for Ruddlesden-Popper phase materials. Lattice parameters for all three compositions showed a linear increase with increasing temperature, but the increase was greatest in the c parameter while the b parameter showed only a slight increase when compared to the a parameter. The thermal expansion coefficient was calculated for all compositions and was found to be in the range 13.0-13.4 × 10-6 °C-1, which is compatible with the commonly used electrolyte materials for solid oxide fuel cells.

Understanding and Engineering Interfacial Adhesion in Solid-State Batteries with Metallic Anodes.

High performance alkali metal anode solid-state batteries require solid/solid interfaces with fast ion transfer that are morphologically and chemically stable upon electrochemical cycling. Void formation at the alkali metal/solid-state electrolyte interface during alkali metal stripping is responsible for constriction resistances and hotspots that can facilitate dendrite propagation and failure. Both externally applied pressures (35-400 MPa) and temperatures above the melting point of the alkali metal have been shown to improve the interfacial contact with the solid electrolyte, preventing the formation of voids. However, the extreme pressure and temperature conditions required can be difficult to meet for commercial solid-state battery applications. In this review, we highlight the importance of interfacial adhesion or 'wetting' at alkali metal/solid electrolyte interfaces for achieving solid-state batteries that can withstand high current densities without cell failure. The intrinsically poor adhesion at metal/ceramic interfaces poses fundamental limitations on many inorganics solid-state electrolyte systems in the absence of applied pressure. Suppression of alkali metal voids can only be achieved for systems with high interfacial adhesion (i. e. 'perfect wetting') where the contact angle between the alkali metal and the solid-state electrolyte surface goes to θ=0°. We identify key strategies to improve interfacial adhesion and suppress void formation including the adoption of interlayers, alloy anodes and 3D scaffolds. Computational modeling techniques have been invaluable for understanding the structure, stability and adhesion of solid-state battery interfaces and we provide an overview of key techniques. Although focused on alkali metal solid-state batteries, the fundamental understanding of interfacial adhesion discussed in this review has broader applications across the field of chemistry and material science from corrosion to biomaterials development.

Operando Characterization and Theoretical Modeling of Metal|Electrolyte Interphase Growth Kinetics in Solid-State Batteries. Part II: Modeling.

Understanding the interfacial dynamics of batteries is crucial to control degradation and increase electrochemical performance and cycling life. If the chemical potential of a negative electrode material lies outside of the stability window of an electrolyte (either solid or liquid), a decomposition layer (interphase) will form at the interface. To better understand and control degradation at interfaces in batteries, theoretical models describing the rate of formation of these interphases are required. This study focuses on the growth kinetics of the interphase forming between solid electrolytes and metallic negative electrodes in solid-state batteries. More specifically, we demonstrate that the rate of interphase formation and metal plating during charge can be accurately described by adapting the theory of coupled ion-electron transfer (CIET). The model is validated by fitting experimental data presented in the first part of this study. The data was collected operando as a Na metal layer was plated on top of a NaSICON solid electrolyte (Na3.4Zr2Si2.4P0.6O12 or NZSP) inside an XPS chamber. This study highlights the depth of information which can be extracted from this single operando experiment and is widely applicable to other solid-state electrolyte systems.

Operando Characterization and Theoretical Modeling of Metal|Electrolyte Interphase Growth Kinetics in Solid-State Batteries. Part I: Experiments.

To harness all of the benefits of solid-state battery (SSB) architectures in terms of energy density, their negative electrode should be an alkali metal. However, the high chemical potential of alkali metals makes them prone to reduce most solid electrolytes (SE), resulting in a decomposition layer called an interphase at the metal|SE interface. Quantitative information about the interphase chemical composition and rate of formation is challenging to obtain because the reaction occurs at a buried interface. In this study, a thin layer of Na metal (Na0) is plated on the surface of an SE of the NaSICON family (Na3.4Zr2Si2.4P0.6O12 or NZSP) inside a commercial X-ray photoelectron spectroscopy (XPS) system while continuously analyzing the composition of the interphase operando. We identify the existence of a solid electrolyte interphase at the Na0|NZSP interface, and more importantly, we demonstrate for the first time that this protocol can be used to study the kinetics of interphase formation. A second important outcome of this article is that the surface chemistry of NZSP samples can be tuned to improve their stability against Na0. It is demonstrated by XPS and time-resolved electrochemical impedance spectroscopy (EIS) that a native Na x PO y layer present on the surface of as-sintered NZSP samples protects their surface against decomposition.

Superstructure and Correlated Na+ Hopping in a Layered Mg-Substituted Sodium Manganate Battery Cathode are Driven by Local Electroneutrality.

In this work, we present a variable-temperature 23Na NMR and variable-temperature and variable-frequency electron paramagnetic resonance (EPR) analysis of the local structure of a layered P2 Na-ion battery cathode material, Na0.67[Mg0.28Mn0.72]O2 (NMMO). For the first time, we elucidate the superstructure in this material by using synchrotron X-ray diffraction and total neutron scattering and show that this superstructure is consistent with NMR and EPR spectra. To complement our experimental data, we carry out ab initio calculations of the quadrupolar and hyperfine 23Na NMR shifts, the Na+ ion hopping energy barriers, and the EPR g-tensors. We also describe an in-house simulation script for modeling the effects of ionic mobility on variable-temperature NMR spectra and use our simulations to interpret the experimental spectra, available upon request. We find long-zigzag-type Na ordering with two different types of Na sites, one with high mobility and the other with low mobility, and reconcile the tendency toward Na+/vacancy ordering to the preservation of local electroneutrality. The combined magnetic resonance methodology for studying local paramagnetic environments from the perspective of electron and nuclear spins will be useful for examining the local structures of materials for devices.

17O NMR Spectroscopy in Lithium-Ion Battery Cathode Materials: Challenges and Interpretation.

Modern studies of lithium-ion battery (LIB) cathode materials employ a large range of experimental and theoretical techniques to understand the changes in bulk and local chemical and electronic structures during electrochemical cycling (charge and discharge). Despite its being rich in useful chemical information, few studies to date have used 17O NMR spectroscopy. Many LIB cathode materials contain paramagnetic ions, and their NMR spectra are dominated by hyperfine and quadrupolar interactions, giving rise to broad resonances with extensive spinning sideband manifolds. In principle, careful analysis of these spectra can reveal information about local structural distortions, magnetic exchange interactions, structural inhomogeneities (Li+ concentration gradients), and even the presence of redox-active O anions. In this Perspective, we examine the primary interactions governing 17O NMR spectroscopy of LIB cathodes and outline how 17O NMR may be used to elucidate the structure of pristine cathodes and their structural evolution on cycling, providing insight into the challenges in obtaining and interpreting the spectra. We also discuss the use of 17O NMR in the context of anionic redox and the role this technique may play in understanding the charge compensation mechanisms in high-capacity cathodes, and we provide suggestions for employing 17O NMR in future avenues of research.

Electric Fields and Charge Separation for Solid Oxide Fuel Cell Electrodes.

Activation losses at solid oxide fuel cell (SOFC) electrodes have been widely attributed to charge transfer at the electrode surface. The electrostatic nature of electrode-gas interactions allows us to study these phenomena by simulating an electric field across the electrode-gas interface, where we are able to describe the activation overpotential using density functional theory (DFT). The electrostatic responses to the electric field are used to approximate the behavior of an electrode under electrical bias and have found a correlation with experimental data for three different reduction reactions at mixed ionic-electronic conducting (MIEC) electrode surfaces (H2O and CO2 on CeO2; O2 on LaFeO3). In this work, we demonstrate the importance of decoupled ion-electron transfer and charged adsorbates on the performance of electrodes under nonequilibrium conditions. Finally, our findings on MIEC-gas interactions have potential implications in the fields of energy storage and catalysis.

Structural Origins of Voltage Hysteresis in the Na-Ion Cathode P2-Na0.67[Mg0.28Mn0.72]O2: A Combined Spectroscopic and Density Functional Theory Study.

P2-layered sodium-ion battery (NIB) cathodes are a promising class of Na-ion electrode materials with high Na+ mobility and relatively high capacities. In this work, we report the structural changes that take place in P2-Na0.67[Mg0.28Mn0.72]O2. Using ex situ X-ray diffraction, Mn K-edge extended X-ray absorption fine structure, and 23Na NMR spectroscopy, we identify the bulk phase changes along the first electrochemical charge-discharge cycle-including the formation of a high-voltage "Z phase", an intergrowth of the OP4 and O2 phases. Our ab initio transition state searches reveal that reversible Mg2+ migration in the Z phase is both kinetically and thermodynamically favorable at high voltages. We propose that Mg2+ migration is a significant contributor to the observed voltage hysteresis in Na0.67[Mg0.28Mn0.72]O2 and identify qualitative changes in the Na+ ion mobility.

Theory of the electrostatic surface potential and intrinsic dipole moments at the mixed ionic electronic conductor (MIEC)-gas interface.

The local activation overpotential describes the electrostatic potential shift away from equilibrium at an electrode/electrolyte interface. This electrostatic potential is not entirely satisfactory for describing the reaction kinetics of a mixed ionic-electronic conducting (MIEC) solid-oxide cell (SOC) electrode where charge transfer occurs at the electrode-gas interface. Using the theory of the electrostatic potential at the MIEC-gas interface as an electrochemical driving force, charge transfer at the ceria-gas interface has been modelled based on the intrinsic dipole potential of the adsorbate. This model gives a physically meaningful reason for the enhancement in electrochemical activity of a MIEC electrode as the steam and hydrogen pressure is increased in both fuel cell and electrolysis modes. This model was validated against operando XPS data from previous literature to accurately predict the outer work function shift of thin film Sm0.2Ce0.8O1.9 in a H2/H2O atmosphere as a function of overpotential.

Metal chalcogenide hollow polar bipyramid prisms as efficient sulfur hosts for Na-S batteries.

Sodium sulfur batteries require efficient sulfur hosts that can capture soluble polysulfides and enable fast reduction kinetics. Herein, we design hollow, polar and catalytic bipyramid prisms of cobalt sulfide as efficient sulfur host for sodium sulfur batteries. Cobalt sulfide has interwoven surfaces with wide internal spaces that can accommodate sodium polysulfides and withstand volumetric expansion. Furthermore, results from in/ex-situ characterization techniques and density functional theory calculations support the significance of the polar and catalytic properties of cobalt sulfide as hosts for soluble sodium polysulfides that reduce the shuttle effect and display excellent electrochemical performance. The polar catalytic bipyramid prisms sulfur@cobalt sulfide composite exhibits a high capacity of 755 mAh g-1 in the second discharge and 675 mAh g-1 after 800 charge/discharge cycles, with an ultralow capacity decay rate of 0.0126 % at a high current density of 0.5 C. Additionally, at a high mass loading of 9.1 mg cm-2, sulfur@cobalt sulfide shows high capacity of 545 mAh g-1 at a current density of 0.5 C. This study demonstrates a hollow, polar, and catalytic sulfur host with a unique structure that can capture sodium polysulfides and speed up the reduction reaction of long chain sodium polysulfides to solid small chain polysulfides, which results in excellent electrochemical performance for sodium-sulfur batteries.

Pair-distribution-function guided optimization of fingerprints for atom-centered neural network potentials.

Atom-centered neural network (ANN) potentials have shown promise in computational simulations and are recognized as both efficient and sufficiently accurate to describe systems involving bond formation and breaking. A key step in the development of ANN potentials is to represent atomic coordinates as suitable inputs for a neural network, commonly described as fingerprints. The accuracy and efficiency of the ANN potentials depend strongly on the selection of these fingerprints. Here, we propose an optimization strategy of atomic fingerprints to improve the performance of ANN potentials. Specifically, a set of fingerprints is optimized to fit a set of pre-selected template functions in the f*g space, where f and g are the fingerprint and the pair distribution function for each type of interatomic interaction (e.g., a pair or 3-body). With such an optimization strategy, we have developed an ANN potential for the Pd13H2 nanoparticle system that exhibits a significant improvement to the one based upon standard template functions. We further demonstrate that the ANN potential can be used with the adaptive kinetic Monte Carlo method, which has strict requirements for the smoothness of the potential. The algorithm proposed here facilitates the development of better ANN potentials, which can broaden their application in computational simulations.

Intrinsic Kinetic Limitations in Substituted Lithium-Layered Transition-Metal Oxide Electrodes.

Substituted Li-layered transition-metal oxide (LTMO) electrodes such as LixNiyMnzCo1-y-zO2 (NMC) and LixNiyCo1-y-zAlzO2 (NCA) show reduced first cycle Coulombic efficiency (90-87% under standard cycling conditions) in comparison with the archetypal LixCoO2 (LCO; ∼98% efficiency). Focusing on LixNi0.8Co0.15Al0.05O2 as a model compound, we use operando synchrotron X-ray diffraction (XRD) and nuclear magnetic resonance (NMR) spectroscopy to demonstrate that the apparent first-cycle capacity loss is a kinetic effect linked to limited Li mobility at x > 0.88, with near full capacity recovered during a potentiostatic hold following the galvanostatic charge-discharge cycle. This kinetic capacity loss, unlike many capacity losses in LTMOs, is independent of the cutoff voltage during delithiation and it is a reversible process. The kinetic limitation manifests not only as the kinetic capacity loss during discharge but as a subtle bimodal compositional distribution early in charge and, also, a dramatic increase of the charge-discharge voltage hysteresis at x > 0.88. 7Li NMR measurements indicate that the kinetic limitation reflects limited Li transport at x > 0.86. Electrochemical measurements on a wider range of LTMOs including Lix(Ni,Fe)yCo1-yO2 suggest that 5% substitution is sufficient to induce the kinetic limitation and that the effect is not limited to Ni substitution. We outline how, in addition to a reduction in the number of Li vacancies and shrinkage of the Li-layer size, the intrinsic charge storage mechanism (two-phase vs solid-solution) and localization of charge give rise to additional kinetic barriers in NCA and nonmetallic LTMOs in general.

Ionic and Electronic Conduction in TiNb2O7.

TiNb2O7 is a Wadsley-Roth phase with a crystallographic shear structure and is a promising candidate for high-rate lithium ion energy storage. The fundamental aspects of the lithium insertion mechanism and conduction in TiNb2O7, however, are not well-characterized. Herein, experimental and computational insights are combined to understand the inherent properties of bulk TiNb2O7. The results show an increase in electronic conductivity of seven orders of magnitude upon lithiation and indicate that electrons exhibit both localized and delocalized character, with a maximum Curie constant and Li NMR paramagnetic shift near a composition of Li0.60TiNb2O7. Square-planar or distorted-five-coordinate lithium sites are calculated to invert between thermodynamic minima or transition states. Lithium diffusion in the single-redox region (i.e., x ≤ 3 in LixTiNb2O7) is rapid with low activation barriers from NMR and DLi = 10-11 m2 s-1 at the temperature of the observed T1 minima of 525-650 K for x ≥ 0.75. DFT calculations predict that ionic diffusion, like electronic conduction, is anisotropic with activation barriers for lithium hopping of 100-200 meV down the tunnels but ca. 700-1000 meV across the blocks. Lithium mobility is hindered in the multiredox region (i.e., x > 3 in LixTiNb2O7), related to a transition from interstitial-mediated to vacancy-mediated diffusion. Overall, lithium insertion leads to effective n-type self-doping of TiNb2O7 and high-rate conduction, while ionic motion is eventually hindered at high lithiation. Transition-state searching with beyond Li chemistries (Na+, K+, Mg2+) in TiNb2O7 reveals high diffusion barriers of 1-3 eV, indicating that this structure is specifically suited to Li+ mobility.

Vanadium(III) Acetylacetonate as an Efficient Soluble Catalyst for Lithium-Oxygen Batteries.

High donor number (DN) solvents in Li-O2 batteries that dissolve superoxide intermediates in lithium peroxide (Li2 O2 ) formation facilitate high capacities at high rates and avoid early cell death. However, their beneficial characteristics also result in an instability towards highly reactive superoxide intermediates. Furthermore, Li-O2 batteries would deliver a superior energy density, but the multiphase electrochemical reactions are difficult to achieve when operating with only solid catalysts. Herein we demonstrate that vanadium(III) acetylacetonate (V(acac)3 ) is an efficient soluble catalyst that can address these problems. During discharge, V(acac)3 integrates with the superoxide intermediate, accelerating O2 reduction kinetics and reducing side reactions. During charge, V(acac)3 acts as a redox mediator that permits efficient oxidation of Li2 O2 . The cells with V(acac)3 exhibit low overpotential, high rate performance, and considerable cycle stability.

Short-range ordering in a battery electrode, the 'cation-disordered' rocksalt Li1.25Nb0.25Mn0.5O2.

Cation order, with a local structure related to γ-LiFeO2, is observed in the nominally cation-disordered Li-excess rocksalt Li1.25Nb0.25Mn0.5O2via X-ray diffraction, neutron pair distribution function analysis, magnetic susceptibility and NMR spectroscopy. The correlation length of ordering depends on synthesis conditions and has implications for the electrochemistry of these phases.

Na3MnZr(PO4)3: A High-Voltage Cathode for Sodium Batteries.

Sodium batteries have been regarded as promising candidates for large-scale energy storage application, provided cathode hosts with high energy density and long cycle life can be found. Herein, we report NASICON-structured Na3MnZr(PO4)3 as a cathode for sodium batteries that exhibits an electrochemical performance superior to those of other manganese phosphate cathodes reported in the literature. Both the Mn4+/Mn3+ and Mn3+/Mn2+ redox couples are reversibly accessed in Na3MnZr(PO4)3, providing high discharge voltage plateaus at 4.0 and 3.5 V, respectively. A high discharge capacity of 105 mAh g-1 was obtained from Na3MnZr(PO4)3 with a small variation of lattice parameters and a small volume change on extraction of two Na+ ions per formula unit. Moreover, Na3MnZr(PO4)3 exhibits an excellent cycling stability, retaining 91% of the initial capacity after 500 charge/discharge cycles at 0.5 C rate. On the basis of structural analysis and density functional theory calculations, we have proposed a detailed desodiation pathway from Na3MnZr(PO4)3 where Mn and Zr are disordered within the structure. We further show that the cooperative Jahn-Teller distortion of Mn3+ is suppressed in the cathode and that Na2MnZr(PO4)3 is a stable phase.

Mixed X-Site Formate-Hypophosphite Hybrid Perovskites.

Following the recent discovery of a new family of hybrid ABX3 perovskites where X=(H2 POO)- (hypophosphite), this work reports a facile synthesis for mixed X-site formate perovskites of composition [GUA]Mn(HCOO)3-x (H2 POO)x , with two crystallographically distinct, partially ordered intermediate phases with x=0.84 and 1.53, corresponding to ca. 30 and 50 mol % hypophosphite, respectively. These phases are characterised by single-crystal XRD and solid-state NMR spectroscopy, and their magnetic properties are reported.

Enabling multi-electron reaction of ε-VOPO4 to reach theoretical capacity for lithium-ion batteries.

By controlling the morphology and particle size of the epsilon polymorph of vanadyl phosphate, ε-VOPO4, it can fully reversibly intercalate two Li-ions and reach the theoretical capacity of 305 mA h g-1 over two voltage plateaus at about 4.0 and 2.5 V.