Swapna Ganapathy

Nature of Li2O2 Oxidation in a Li–O2 Battery Revealed by Operando X-ray Diffraction

Fundamental research into the Li-O2 battery system has gone into high gear, gaining momentum because of its very high theoretical specific energy. Much progress has been made toward understanding the discharge mechanism, but the mechanism of the oxygen evolution reaction (OER) on charge (i.e., oxidation) remains less understood. Here, using operando X-ray diffraction, we show that oxidation of electrochemically generated Li2O2 occurs in two stages, but in one step for bulk crystalline (commercial) Li2O2, revealing a fundamental difference in the OER process depending on the nature of the peroxide. For electrochemically generated Li2O2, oxidation proceeds first through a noncrystalline lithium peroxide component, followed at higher potential by the crystalline peroxide via a Li deficient solid solution (Li(2-x)O2) phase. Anisotropic broadening of the X-ray Li2O2 reflections confirms a platelet crystallite shape. On the basis of the evolution of the broadening during charge, we speculate that the toroid particles are deconstructed one platelet at a time, starting with the smallest sizes that expose more peroxide surface. In the case of in situ charged bulk crystalline Li2O2, the Li vacancies preferentially form on the interlayer position (Li1), which is supported by first-principle calculations and consistent with their lower energy compared to those located next to oxygen (Li2). The small actively oxidizing fraction results in a gradual reduction of the Li2O2 crystallites. The fundamental insight gained in the OER charge mechanism and its relation to the nature of the Li2O2 particles is essential for the design of future electrodes with lower overpotentials, one of the key challenges for high performance Li-air batteries.

Nanosize Storage Properties in Spinel Li4Ti5O12 Explained by Anisotropic Surface Lithium Insertion

Nanosizing is a frequently applied strategy in recent years to improve storage properties of Li-ion electrodes and facilitate novel storage mechanisms. Due to particle size reduction, surface effects increasingly dominate, which can drastically change the storage properties. Using density functional theory calculations we investigate the impact of the surface environment on the Li-ion insertion properties in defective spinel Li(4+x)Ti(5)O(12), a highly promising negative electrode material. The calculations reveal that the storage properties strongly depend on the surface orientation. The lowest energy (1 1 0) surface is predicted to be energetically favorable for Li-ion insertion into the vacant 16c sites. The (1 1 1) surface allows capacities that significantly exceed the bulk capacity Li(7)Ti(5)O(12) at voltages greater than 0 V by occupation of 8a sites in addition to the fully occupied 16c sites. One of the key findings is that the surface environment extends nanometers into the storage material, leading to a distribution of voltages responsible for the curved voltage profile commonly observed in nanosized insertion electrode materials. Both the calculated surface-specific voltage profiles and the calculated particle size dependent voltage profiles are in good agreement with the experimental voltage profiles reported in literature. These results give a unique insight into the impact of nanostructuring and further possibilities of tailoring the Li-ion voltage profiles and capacities in lithium insertion materials.

Unravelling Li-Ion Transport from Picoseconds to Seconds: Bulk versus Interfaces in an Argyrodite Li6PS5Cl–Li2S All-Solid-State Li-Ion Battery

One of the main challenges of all-solid-state Li-ion batteries is the restricted power density due to the poor Li-ion transport between the electrodes via the electrolyte. However, to establish what diffusional process is the bottleneck for Li-ion transport requires the ability to distinguish the various processes. The present work investigates the Li-ion diffusion in argyrodite Li6PS5Cl, a promising electrolyte based on its high Li-ion conductivity, using a combination of (7)Li NMR experiments and DFT based molecular dynamics simulations. This allows us to distinguish the local Li-ion mobility from the long-range Li-ion motional process, quantifying both and giving a coherent and consistent picture of the bulk diffusion in Li6PS5Cl. NMR exchange experiments are used to unambiguously characterize Li-ion transport over the solid electrolyte-electrode interface for the electrolyte-electrode combination Li6PS5Cl-Li2S, giving unprecedented and direct quantitative insight into the impact of the interface on Li-ion charge transport in all-solid-state batteries. The limited Li-ion transport over the Li6PS5Cl-Li2S interface, orders of magnitude smaller compared with that in the bulk Li6PS5Cl, appears to be the bottleneck for the performance of the Li6PS5Cl-Li2S battery, quantifying one of the major challenges toward improved performance of all-solid-state batteries.

Accessing the bottleneck in all-solid state batteries, lithium-ion transport over the solid-electrolyte-electrode interface

Solid-state batteries potentially offer increased lithium-ion battery energy density and safety as required for large-scale production of electrical vehicles. One of the key challenges toward high-performance solid-state batteries is the large impedance posed by the electrode–electrolyte interface. However, direct assessment of the lithium-ion transport across realistic electrode–electrolyte interfaces is tedious. Here we report two-dimensional lithium-ion exchange NMR accessing the spontaneous lithium-ion transport, providing insight on the influence of electrode preparation and battery cycling on the lithium-ion transport over the interface between an argyrodite solid-electrolyte and a sulfide electrode. Interfacial conductivity is shown to depend strongly on the preparation method and demonstrated to drop dramatically after a few electrochemical (dis)charge cycles due to both losses in interfacial contact and increased diffusional barriers. The reported exchange NMR facilitates non-invasive and selective measurement of lithium-ion interfacial transport, providing insight that can guide the electrolyte–electrode interface design for future all-solid-state batteries.The large impedance at the interface between electrode and electrolyte poses a challenge to the development of solid-state batteries. Here the authors utilize two-dimensional lithium-ion exchange-NMR to monitor the spontaneous lithium-ion transport, providing insight into the interface design.

Equilibrium Lithium‐Ion Transport Between Nanocrystalline Lithium‐Inserted Anatase TiO2 and the Electrolyte

The power density of lithium-ion batteries requires the fast transfer of ions between the electrode and electrolyte. The achievable power density is directly related to the spontaneous equilibrium exchange of charged lithium ions across the electrolyte/electrode interface. Direct and unique characterization of this charge-transfer process is very difficult if not impossible, and consequently little is known about the solid/liquid ion transfer in lithium-ion-battery materials. Herein we report the direct observation by solid-state NMR spectroscopy of continuous lithium-ion exchange between the promising nanosized anatase TiO(2) electrode material and the electrolyte. Our results reveal that the energy barrier to charge transfer across the electrode/electrolyte interface is equal to or greater than the barrier to lithium-ion diffusion through the solid anatase matrix. The composition of the electrolyte and in turn the solid/electrolyte interface (SEI) has a significant effect on the electrolyte/electrode lithium-ion exchange; this suggests potential improvements in the power of batteries by optimizing the electrolyte composition.

Na-ion dynamics in tetragonal and cubic Na3PS4, a Na-ion conductor for solid state Na-ion batteries

Tetragonal and cubic phase Na3PS4 sodium electrolytes were successfully prepared by a relatively low rotation speed mechanical milling (400 rpm) route, aiming at homogeneous materials. The influence of the mechanical milling and annealing on the structure and ionic conductivity are studied by XRD and impedance spectroscopy, giving insight into the optimal mechanical synthesis conditions. Fourier analysis of the XRD data, compared to DFT based MD simulations reflects the diffusion pathway, where the simulations indicate a vacancy induced high bulk Na-ion mobility in both cubic and tetragonal phases. 23Na solid-state NMR relaxation experiments were applied to investigate the Na-ion bulk diffusion in both the cubic and tetragonal phases, showing reasonable agreement with the MD simulation results. The MD simulations indicate that the bulk mobility of both phases may be further improved by introducing more Na vacancies. The macroscopic ionic conductivity probed by impedance spectroscopy is much smaller than that predicted by the bulk Na-ion mobility, in particular for the tetragonal phase, suggesting a large impact of amorphous phase fractions and/or grain boundaries on the macroscopic Na-ion conductivity. In particular in the less crystalline cubic phase, the amorphous fraction present as a consequence of the lower annealing temperature suggests that this phase may lead to a decrease in grain boundary resistance, which may be further exploited to improve the performance of all solid state Na-ion batteries with the Na3PS4 solid electrolyte.

Understanding the Electrochemical Formation and Decomposition of Li2O2 and LiOH with Operando X-ray Diffraction

The lithium air, or Li–O2, battery system is a promising electrochemical energy storage system because of its very high theoretical specific energy, as required by automotive applications. Fundamental research has resulted in much progress in mitigating detrimental (electro)chemical processes; however, the detailed structural evolution of the crystalline Li2O2 and LiOH discharge products, held at least partially responsible for the limited reversibility and poor rate performance, is hard to measure operando under realistic electrochemical conditions. This study uses Rietveld refinement of operando X-ray diffraction data during a complete discharge–charge cycle to reveal the detailed structural evolution of Li2O2 and LiOH crystallites in 1,2-dimethoxyethane (DME) and DME/LiI electrolytes, respectively. The anisotropic broadened reflections confirm and quantify the platelet crystallite shape of Li2O2 and LiOH and show how the average crystallite shape evolves during discharge and charge. Li2O2 is shown to form via a nucleation and growth mechanism, whereas the decomposition appears to start at the smallest Li2O2 crystallite sizes because of their larger exposed surface. In the presence of LiI, platelet LiOH crystallites are formed by a particle-by-particle nucleation and growth process, and at the end of discharge, H2O depletion is suggested to result in substoichiometric Li(OH)1–x, which appears to be preferentially decomposed during charging. Operando X-ray diffraction proves the cyclic formation and decomposition of the LiOH crystallites in the presence of LiI over multiple cycles, and the structural evolution provides key information for understanding and improving these highly relevant electrochemical systems.

Operando Nanobeam Diffraction to Follow the Decomposition of Individual Li2O2 Grains in a Nonaqueous Li-O2 Battery.

Intense interest in the Li-O2 battery system over the past 5 years has led to a much better understanding of the various chemical processes involved in the functioning of this battery system. However, detailed decomposition of the nanostructured Li2O2 product, held at least partially responsible for the limited reversibility and poor rate performance, is hard to measure operando under realistic electrochemical conditions. Here, we report operando nanobeam X-ray diffraction experiments that enable monitoring of the decomposition of individual Li2O2 grains in a working Li-O2 battery. Platelet-shaped crystallites with aspect ratios between 2.2 and 5.5 decompose preferentially via the more reactive (001) facets. The slow and concurrent decomposition of individual Li2O2 crystallites indicates that the Li2O2 decomposition rate limits the charge time of these Li-O2 batteries, highlighting the importance of using redox mediators in solution to charge Li-O2 batteries.

Revealing the relation between the structure, Li-ion conductivity and solid-state battery performance of the argyrodite Li6PS5Br solid electrolyte

Based on its high Li-ion conductivity, argyrodite Li6PS5Br is a promising solid electrolyte for all-solid-state batteries. However, more understanding is required on the relation between the solid electrolyte conductivity and the solid-state battery performance with the argyrodite structure, crystallinity and particle size that depend on the synthesis conditions. In the present study, this relationship is investigated using neutron and X-ray diffraction to determine the detailed structure and impedance as well as 7Li solid state NMR spectroscopy to study the Li-ion kinetics. It is found that depending on the synthesis conditions the distribution of the Br dopant over the crystallographic sites in Li6PS5Br is inhomogeneous, and that this may be responsible for a larger mobile Li-ion fraction at the interface regions in the annealed argyrodite materials. Comparing the bulk and interface properties of the differently prepared Li6PS5Br materials, it is proposed that optimal solid-state battery performance requires a different particle size for the solid electrolyte only region and the solid electrolyte in the cathode mixture. In the electrolyte region, the grain boundary resistance is minimized by annealing the argyrodite Li6PS5Br resulting in relatively large crystallites. In the cathode mixture however, additional particle size reduction of the Li6PS5Br is required to provide abundant Li6PS5Br-Li2S interfaces that reduce the resistance of this rate limiting step in Li-ion transport. Thereby the results give insight in how to improve solidstate battery performance by controlling the solid electrolyte structure.

Toward Optimal Performance and In-Depth Understanding of Spinel Li4Ti5O12 Electrodes through Phase Field Modeling

Computational modeling is vital for the fundamental understanding of processes in Li-ion batteries. However, capturing nanoscopic to mesoscopic phase thermodynamics and kinetics in the solid electrode particles embedded in realistic electrode morphologies is challenging. In particular for electrode materials displaying a first order phase transition, such as LiFePO