Correlative operando microscopy of oxygen evolution electrocatalysts.

Transition metal (oxy)hydroxides are promising electrocatalysts for the oxygen evolution reaction1-3. The properties of these materials evolve dynamically and heterogeneously4 with applied voltage through ion insertion redox reactions, converting materials that are inactive under open circuit conditions into active electrocatalysts during operation5. The catalytic state is thus inherently far from equilibrium, which complicates its direct observation. Here, using a suite of correlative operando scanning probe and X-ray microscopy techniques, we establish a link between the oxygen evolution activity and the local operational chemical, physical and electronic nanoscale structure of single-crystalline ß-Co(OH)2 platelet particles. At pre-catalytic voltages, the particles swell to form an α-CoO2H1.5·0.5H2O-like structure-produced through hydroxide intercalation-in which the oxidation state of cobalt is +2.5. Upon increasing the voltage to drive oxygen evolution, interlayer water and protons de-intercalate to form contracted ß-CoOOH particles that contain Co3+ species. Although these transformations manifest heterogeneously through the bulk of the particles, the electrochemical current is primarily restricted to their edge facets. The observed Tafel behaviour is correlated with the local concentration of Co3+ at these reactive edge sites, demonstrating the link between bulk ion-insertion and surface catalytic activity.

Coulombically-stabilized oxygen hole polarons enable fully reversible oxygen redox.

Stabilizing high-valent redox couples and exotic electronic states necessitate an understanding of the stabilization mechanism. In oxides, whether they are being considered for energy storage or computing, highly oxidized oxide-anion species rehybridize to form short covalent bonds and are related to significant local structural distortions. In intercalation oxide electrodes for batteries, while such reorganization partially stabilizes oxygen redox, it also gives rise to substantial hysteresis. In this work, we investigate oxygen redox in layered Na2-XMn3O7, a positive electrode material with ordered Mn vacancies. We prove that coulombic interactions between oxidized oxideanions and the interlayer Na vacancies can disfavor rehybridization and stabilize hole polarons on oxygen (O-) at 4.2 V vs. Na/Na+. These coulombic interactions provide thermodynamic energy saving as large as O-O covalent bonding and enable ~ 40 mV voltage hysteresis over multiple electrochemical cycles with negligible voltage fade. Our results establish a complete picture of redox energetics by highlighting the role of coulombic interactions across several atomic distances and suggest avenues to stabilize highly oxidized oxygen for applications in energy storage and beyond.

Metal-oxygen decoordination stabilizes anion redox in Li-rich oxides.

Reversible high-voltage redox chemistry is an essential component of many electrochemical technologies, from (electro)catalysts to lithium-ion batteries. Oxygen-anion redox has garnered intense interest for such applications, particularly lithium-ion batteries, as it offers substantial redox capacity at more than 4 V versus Li/Li+ in a variety of oxide materials. However, oxidation of oxygen is almost universally correlated with irreversible local structural transformations, voltage hysteresis and voltage fade, which currently preclude its widespread use. By comprehensively studying the Li2-xIr1-ySnyO3 model system, which exhibits tunable oxidation state and structural evolution with y upon cycling, we reveal that this structure-redox coupling arises from the local stabilization of short approximately 1.8 Å metal-oxygen π bonds and approximately 1.4 Å O-O dimers during oxygen redox, which occurs in Li2-xIr1-ySnyO3 through ligand-to-metal charge transfer. Crucially, formation of these oxidized oxygen species necessitates the decoordination of oxygen to a single covalent bonding partner through formation of vacancies at neighbouring cation sites, driving cation disorder. These insights establish a point-defect explanation for why anion redox often occurs alongside local structural disordering and voltage hysteresis during cycling. Our findings offer an explanation for the unique electrochemical properties of lithium-rich layered oxides, with implications generally for the design of materials employing oxygen redox chemistry.

Fluid-enhanced surface diffusion controls intraparticle phase transformations.

Phase transformations driven by compositional change require mass flux across a phase boundary. In some anisotropic solids, however, the phase boundary moves along a non-conductive crystallographic direction. One such material is LiXFePO4, an electrode for lithium-ion batteries. With poor bulk ionic transport along the direction of phase separation, it is unclear how lithium migrates during phase transformations. Here, we show that lithium migrates along the solid/liquid interface without leaving the particle, whereby charge carriers do not cross the double layer. X-ray diffraction and microscopy experiments as well as ab initio molecular dynamics simulations show that organic solvent and water molecules promote this surface ion diffusion, effectively rendering LiXFePO4 a three-dimensional lithium-ion conductor. Phase-field simulations capture the effects of surface diffusion on phase transformation. Lowering surface diffusivity is crucial towards supressing phase separation. This work establishes fluid-enhanced surface diffusion as a key dial for tuning phase transformation in anisotropic solids.

Coupling between oxygen redox and cation migration explains unusual electrochemistry in lithium-rich layered oxides.

Lithium-rich layered transition metal oxide positive electrodes offer access to anion redox at high potentials, thereby promising high energy densities for lithium-ion batteries. However, anion redox is also associated with several unfavorable electrochemical properties, such as open-circuit voltage hysteresis. Here we reveal that in Li1.17-x Ni0.21Co0.08Mn0.54O2, these properties arise from a strong coupling between anion redox and cation migration. We combine various X-ray spectroscopic, microscopic, and structural probes to show that partially reversible transition metal migration decreases the potential of the bulk oxygen redox couple by > 1 V, leading to a reordering in the anionic and cationic redox potentials during cycling. First principles calculations show that this is due to the drastic change in the local oxygen coordination environments associated with the transition metal migration. We propose that this mechanism is involved in stabilizing the oxygen redox couple, which we observe spectroscopically to persist for 500 charge/discharge cycles.

Persistent State-of-Charge Heterogeneity in Relaxed, Partially Charged Li1- x Ni1/3 Co1/3 Mn1/3 O2 Secondary Particles.

Ex situ transmission X-ray microscopy reveals micrometer-scale state-of-charge heterogeneity in solid-solution Li1- x Ni1/3 Co1/3 Mn1/3 O2 secondary particles even after extensive relaxation. The heterogeneity generates overcharged domains at the cutoff voltage, which may accelerate capacity fading and increase impedance with extended cycling. It is proposed that optimized secondary structures can minimize the state-of-charge heterogeneity by mitigating the buildup of nonuniform internal stresses associated with volume changes during charge.

Effects of Particle Size, Electronic Connectivity, and Incoherent Nanoscale Domains on the Sequence of Lithiation in LiFePO4 Porous Electrodes.

High-resolution X-ray microscopy is used to investigate the sequence of lithiation in LiFePO4 porous electrodes. For electrodes with homogeneous interparticle electronic connectivity via the carbon black network, the smaller particles lithiate first. For electrodes with heterogeneous connectivity, the better-connected particles preferentially lithiate. Correlative electron and X-ray microscopy also reveal the presence of incoherent nanodomains that lithiate as if they are separate particles.