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Summarizing work completed by multi-lab/university thrust group examining heterogeneity within VTO extreme fast charging project. The thrust group is examining how local heterogeneity can lead to early onset of lithium plating.
Empowering extreme fast charging (XFC) requires a comprehensive understanding of its application with advanced anode and cathode materials in lithium-ion batteries. No report exists for the full extent of limitations for the anode with crosstalk effect from paired cathode as well as Li plating due to electrode loading under XFC. In this study, a combination of cell testing and multiple length characterization is used to investigate XFC aging mechanism in cells with a low loading of 1.5 mAh cm -2 and high loading of 2.5 mAh cm -2 for graphite (Gr)/Ni-rich LiNi x Mn y Co 1-x-y O 2 (NMCs). Operando XRD mappings show 1.5 mAh cm -2 loadings result in higher strain in graphite for all three cathode types. Among the three NMC cathodes, the graphite from NMC532 and NMC811 cells show comparable strain. Scanning electron microscopy (SEM) images show distinct differences between 6-C-charged anodes in two loadings. Significantly increased electrode thickness can be seen due to more damage in the graphite bulk and accumulation of the electrolyte decomposition products in electrode pores. X-ray photoelectron spectroscopy (XPS) reveals both cathode chemistry and Li plating influence the non-uniform SEI composition on graphite surface. We report higher Ni content in NMC811 promotes the higher levels of salt decomposition on the SEI and formation of higher mass of electrolyte aging products.
Iron/chromium hydroxide coprecipitation controls the fate and transport of toxic chromium (Cr) in many natural and engineered systems. Organic coatings on soil and engineered surfaces are ubiquitous; however, mechanistic controls of these organic coatings over Fe/Cr hydroxide coprecipitation are poorly understood. Here, Fe/Cr hydroxide coprecipitation was conducted on model organic coatings of humic acid (HA), sodium alginate (SA), and bovine serum albumin (BSA). The organics bonded with SiO 2 through ligand exchange with carboxyl (-COOH), and the adsorbed amounts and pK(a) values of -COOH controlled surface charges of coatings. The adsorbed organic films also had different complexation capacities with Fe/Cr ions and Fe/Cr hydroxide particles, resulting in significant differences in both the amount (on HA > SA(-COOH) >> BSA(-NH 2 )) and composition (Cr/Fe molar ratio: on BSA(-NH2) >> HA > SA(-COOH)) of heterogeneous precipitates. Negatively charged -COOH attracted more Fe ions and oligomers of hydrolyzed Fe/Cr species and subsequently promoted heterogeneous precipitation of Fe/Cr hydroxide nanoparticles. Organic coatings containing -NH 2 were positively charged at acidic pH because of the high pK(a) value of the functional group, limiting cation adsorption and formation of coprecipitates. Meanwhile, the higher local pH near the -NH 2 coatings promoted the formation of Cr(OH) 3 . Finally, this study advances fundamental understanding of heterogeneous Fe/Cr hydroxide coprecipitation on organics, which is essential for successful Cr remediation and removal in both natural and engineered settings, as well as the synthesis of Cr-doped iron (oxy)hydroxides for material applications.
An assessment is presented of current knowledge concerning the role and importance of neutral and charged clusters in atmospheric heterogeneous catalysis, with a view to the recommendation of future studies needed for progress in the quantification of aerosol formation and catalytic reactivity. It is established that nucleation from the gaseous to the aerosol state commences via the formation of clusters among molecules participating in the phase-transformation process. Nucleation may proceed in some cases by way of the formation of prenucleation embryos, which then evolve through the energy barrier and undergo phase transformation. In other cases, cluster-cluster interaction among neutral particles or stagewise building of alternate-sign ion clusters may be important in the gas-to-particle conversion process.
An electrode in cylindrical or pouch cell batteries contains millions of active particles embedded in a conductive network. Battery performance, such as voltage, capacity, and cyclic efficiency, is a collective response of the particle network. We use optical microscopy to measure the local, heterogeneous state of charge of individual particles upon charging and discharging. The optical reflectivity is proportional to Li composition in the ternary oxide LiNi x Mn y Co z O 2 (NMC) cathode. Through clustering analysis, we determine the scale of heterogeneity where a representative volume in the composite electrode contains 100 to 1,000 particles. The heterogeneous activity in the particle network can be described by Weibull defect population at the particle interface with the conductive matrix.
Semiconductor photocatalyst particles convert solar energy to fuels like H 2 . The particles are often assumed to provide crystalline-facet-dependent electron-hole separation. A common strategy is to deposit HER electrocatalyst on electron-selective facets and OER electrocatalyst on hole-selective facets. A precise understanding of how charge-carrier-selective contacts emerges and how they rationally designed, however, is missing. Using a combination of ex-situ and in-situ conducting-AFM experiments and new ionomer/catalyst-semiconductor test structures, we show how heterogeneity in charge-carrier selectivity can be measured at the nanoscale. We discover that the presence of interface water/electrolyte is critical to induce hole selectivity between the CoO x water-oxidation catalyst and the BiVO 4 light absorber. pH-dependent measurements suggest that negative surface charge on the semiconductor is central to inducing hole selectivity. Furthermore, the work also demonstrates a new approach to control local pH and introduce water using thin-film ionomers compatible with conductive-AFM measurements.
Side reactions involving surface reduction play a critical role in the failure of LiNi 0.8 Co 0.15 Al 0.05 O 2 to reach its theoretical capacity as a cathode material for Li-ion batteries. While macroscopic consequences are known, the underlying nanoscopic mechanisms are not fully elucidated. By coupling X-ray spectroscopy with several X-ray microscopy modalities, we have spatially resolved the extent of Ni oxidation at several states of charge and uncovered heterogeneity that is hidden when considering ensemble measurements alone. The use of morphologically controlled particles enabled high-resolution imaging of these materials, uncovering gradients of Ni oxidation states within individual primary particles. At high states of charge, these gradients revealed regions of possible oxygen deficiency extending deeper into the particle than previously observed. Surface-sensitive X-ray coupled scanning tunneling microscopy allows oxidation states to be measured at the material's surface, showing predominantly Ni II in the first atomic layer and mixtures of Ni II with Ni III /Ni IV already appearing 1.5 nm into the particle. These results reveal the subtle interplay between irreversible surface transformations and the bulk reactions that ultimately define function, which will refine strategies of surface passivation that are key to overcoming current performance limitations.
Realization of extreme fast charging (XFC, ≤15 minutes) of lithium-ion batteries is imperative for the widespread adoption of electric vehicles. However, dramatic capacity fading is associated with XFC, limiting its implementation. To quantitatively elucidate the effects of irreversible lithium plating and other degradation mechanisms on the cell capacity, it is important to understand the links between lithium plating and cell degradation at both the local and global (over the full cell) scales. Here, we study the nature of local lithium plating after hundreds of XFC cycles (charging C-rates ranging from 4C to 9C) in industrially-relevant pouch cells using spatially resolved X-ray diffraction. Our results reveal a spatial correlation at the mm scale between irreversible lithium plating on the anode, inactive lithiated graphite phases, and local state-of-charge of the cathode. In regions of plated lithium, additional lithium is locally and irreversibly trapped as lithiated graphite, contributing to the loss of lithium inventory (LLI) and to a local loss of active anode material. The total LLI in the cell from irreversibly plated lithium is linearly correlated to the capacity loss in the batteries after XFC cycling, with a non-zero offset originating from other parasitic side reactions. Finally, at the global (cell) scale, LLI drives the capacity fade, rather than electrode degradation. We anticipate that the understanding of lithium plating and other degradation mechanisms during XFC gained in this work will help lead to new approaches towards designing high-rate batteries in which irreversible lithium plating is minimized.
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A microstructure scale electrochemical LIB model was used to investigate lithium plating onset, material non-uniform utilization, and in-plane heterogeneities for an NMC-graphite full cell. Model predicts active material particle surface roughness and size distribution (respectively, non-uniform curvature within and between particles) initiate in-plane heterogeneity, and that particle size heterogeneity at the separator interface controls the lithium plating preferential deposition ("Where"). These in-plane heterogeneities are then exacerbated by through-plane heterogeneities induced at fast charge as electrolyte depletion occurs and concentrates intercalation reaction near the anode-separator interface. Also, magnitude and occurrence of lithium plating is controlled by effective, or macroscale, microstructure parameters ("When"). As local states of charge start to diverge between nearby active material regions, overpotential differences induced by OCP difference kick in and contribute to reduce these SOC local heterogeneities. However, for staged materials such as graphite, with OCP profile alternating between plateaus and varying regions, this balancing mechanism is, respectively, inactive and active. This leads to a dynamic, non-monotonic, in-plane heterogeneity time evolution for state of charge and Faraday current density, for which their respective in-plane heterogeneity magnitude alternates. Such behavior has been modeled both for the whole electrode at the microstructure scale and at the particle scale. In-plane heterogeneities are usually considered to be detrimental, as they result in material non-uniform utilization (i.e., under and over stressed regions) and earlier degradations. However, this work provides a more granular approach as it discriminates between a harmful in-plane heterogeneity (non-uniform curvature) that triggers SOC in-plane heterogeneity, and a beneficial in-plane heterogeneity (Faraday current density) that contributes to reduce SOC in-plane heterogeneity. This work comprehensively explains the mechanisms that initiate, exacerbate, and regulate heterogeneity at the microstructure scale, while providing some design suggestions to reduce both in-plane and through-plane heterogeneities, as summarized in the graphical abstract.
To prepare for rapid growth in global electric vehicle adoption, grid and policy planners depend on detailed forecasts of future charging demand. In this paper we propose a novel holistic, scalable, probabilistic framework to produce large-scale estimates of electric vehicle charging load for long-term planning that capture real drivers’ charging patterns. Our framework captures the uncertainty and stochasticity in charging demand by taking a graphical modeling approach. It has three core elements: driver groups, charging segment choices, and charging session time and energy requirements. The framework uses hierarchical clustering to group drivers by their charging histories, capturing their heterogeneous behaviors and preferences across different segments or types of charging. The framework uses probabilistic mixture models for each driver group’s sessions to identify the unique charging behaviors observed within each segment. We illustrate its application with a large data set from California, profiling the charging patterns and unique driver clusters it identifies. Using the model knobs representing drivers’ battery capacities, behavior, and segment access we present scenarios for California’s charging demand in 2030 with 8 million passenger electric vehicles. Peak charging demand ranged from 3.3 to 8.7 GW across scenarios. Furthermore, each was calculated in under 45 s on a laptop computer.
Direct visualization and quantitative evaluation of charge filling in grain boundary (GB) traps of hybrid metal halide perovskites require dynamic conductivity imaging simultaneously at the terahertz (THz) frequency and nanometer (nm) spatial scales not accessible by conventional transport and imaging methods used thus far. Here, in this study, we apply a THz near-field nanoconductivity mapping to the archetypal metal halide perovskite photovoltaic films and demonstrate that it is a powerful tool to reveal distinct dielectric heterogeneity due to charge trapping and degradation at the single GB level. Our approach visualizes the filled defect ion traps by local THz charge conductivity and allows for extracting a quantitative profile of trapping density in the vicinity of GBs with sub-20 nm resolution. Furthermore, imaging material degradation by tracking local nanodefect distributions overtime identifies a distinct degradation pathway that starts from the GBs and propagates inside the grains over time. The single GB, nano-THz conductivity imaging demonstrated here can be extended to benchmark various perovskite materials and devices for their global photoenergy conversion performance and local charge transfer proprieties of absorbers and interfaces.
All-solid-state batteries (ASSBs) employing Li-metal anodes and inorganic solid electrolytes are attracting great attention due to high safety and energy density for next-generation energy storage devices. However, the volume change of cathode active materials can cause contact loss, resulting in charge carrier isolation, heterogeneous current distribution, and poor electrochemical properties in ASSBs. Here, a simple, yet effective, solvent-free electrode engineering approach with polytetrafluoroethylene (PTFE) as a binder for ASSBs is reported, enabling intimate contact and stable interfaces with the cathode. It is substantiated that the crystallinity of PTFE can be controlled depending on the heat history, and highly crystalline PTFE displays robust mechanical properties. High-nickel LiNi 0.8 Mn 0.1 Co 0.1 O 2 cathode prepared with crystalline PTFE show improved cycle and rate performances in ASSBs. In addition, it is revealed that the intimate contact between cathode particles with a stable cathode electrolyte layer is maintained during cycling by postmortem studies. Furthermore, this simple engineering method can be applied to prepare cathodes with a variety of active materials and solid electrolytes in ASSBs.
The role of nanoscale chemomechanical behavior in the macroscopic performance of functional materials is well recognized. For lithium-ion battery cathodes, tremendous effort has been devoted to the development of new chemistry and structure, yet fundamental understanding of the correlation between redox processes and mechanical properties of the novel materials lags behind. In the present study, we prepare large discrete single grains of Li-excess cation-disordered rocksalts (DRX) and investigate their chemomechanical behavior at the particle level, using nanoresolution X-ray and electron-based spectro-imaging and chemical mapping techniques. While irregular cracking upon lithium extraction leads to the eventual breakdown of the baseline DRX oxide (Li 1.2 Ti 0.4 Mn 0.4 O 2 ) particles at a high delithiation state, the fluorinated-DRX (Li 1.3 Ti 0.3 Mn 0.4 O 1.7 F 0.3 ) clearly displays aligned cracking along the <001> direction. The resulting periodicity in the cracking pattern enables the particles to retain their integrity and, consequently, improved electrochemical stability. Density functional theory (DFT) calculations showed that fluorination leads to increased concentration of Li+ on the (001) planes and preferential Li movements along the <001>-family directions, revealing the underlying mechanism for directional cracking. Overall, our study demonstrates the unique role of fluorine in modulating nanoscale chemomechanics, which in turn influences the evolution of charge and strain heterogeneity at the particle level. These insights provide important design guidelines in further improving DRX cathode materials.
Ultrafast stimuli can stabilize metastable states of matter inaccessible by equilibrium means. Establishing the spatiotemporal link between ultrafast excitation and metastability is crucial to understand these phenomena. Here, in this work, we utilize single-shot optical pump–X-ray probe measurements to capture snapshots of the emergence of a persistent polar vortex supercrystal in a heterostructure that hosts a fine balance between built-in electrostatic and elastic frustrations by design. By perturbing this balance with photoinduced charges, an initially heterogeneous mixture of polar phase disorders within a few picoseconds, leading to a state composed of disordered ferroelectric and suppressed vortex orders. On the picosecond–nanosecond timescales, transient labyrinthine fluctuations develop, accompanied by the recovery of the vortex order. On longer timescales, these fluctuations are progressively quenched by dynamical strain modulations, which drive the collective emergence of a single vortex supercrystal phase. Our results, corroborated by dynamical phase-field modelling, reveal non-equilibrium pathways following the ultrafast excitation of designer systems to persistent metastability.
Discussion of an analytical model which leads to predictions of reductions in electron concentrations in reentry flow fields due to the injection of electrophilic liquids and water. The processes incorporated into the model are: penetration and breakup of the liquid jet, droplet acceleration and vaporization, expansion of the liquid spray due to droplet vaporization, electrophilic vapor diffusion, heterogeneous and homogeneous charged species recombination kinetics and homogeneous electron attachment kinetics. Spray boundary calculations are shown to be in good agreement with photographic observations of water and Freon E-3 sprays in wind tunnel tests of a scale model RAM C-III flight vehicle. Fixed-bias electrostatic probe data taken during the RAM C-III flight are interpreted in terms of effective jet penetration distances - which are shown to be consistent with calculations using the present model.
The tobacco mosaic viral capsid protein (TMV) is a frequent target for derivatization for myriad applications, including drug delivery, biosensing, and light harvesting. However, solutions of the stacked disk assembly state of TMV are difficult to characterize quantitatively due to their large size and multiple assembled states. Charge detection mass spectrometry (CDMS) addresses the need to characterize heterogeneous populations of large protein complexes in solution quickly and accurately. Using CDMS, previously unobserved assembly states of TMV, including 16-monomer disks and odd-numbered disk stacks, have been characterized. We additionally employed a peptide-protein conjugation reaction in conjunction with CDMS to demonstrate that modified TMV proteins do not redistribute between disks. Finally, this technique was used to discriminate between protein complexes of near-identical mass but different configurations. In conclusion, we have gained a greater understanding of the behavior of TMV, a protein used across a broad variety of fields and applications, in the solution state.
Abstract Understanding how various redox activities evolve and distribute in disordered rocksalt oxides (DRX) can advance insights into manipulating materials properties for achieving stable, high‐energy batteries. Herein, the authors present how the reaction kinetics and spatial distribution of redox activities are governed by the particle size of DRX materials. The size‐dependent electrochemical performance is attributed to the distinct cationic and anionic reaction kinetics at different sizes, which can be tailored to achieve optimal capacity and stability. Overall, the local charged domains in DRX particles display random heterogeneity caused by the isotropic delithiation pathways. Owing to the kinetic limitation, the micron‐sized particles exhibit a holistic “core‐shell” charge distribution, whereas sub‐micron particles show more uniform redox reactions throughout the particles and ensembles. Sub‐micron DRX particles exhibit increasing anionic redox activities yet inferior cycling stability. In summary, engineering particle size can effectively modulate how cationic and anionic redox activities evolve and distribute in DRX materials.