From Bulk to Interface: Solvent Exchange Dynamics and Their Role in Ion Transport and the Interfacial Model of Rechargeable Magnesium Batteries.

Multivalent battery chemistries have been explored in response to the increasing demand for high-energy rechargeable batteries utilizing sustainable resources. Solvation structures of working cations have been recognized as a key component in the design of electrolytes; however, most structure-property correlations of metal ions in organic electrolytes usually build upon favorable static solvation structures, often overlooking solvent exchange dynamics. We here report the ion solvation structures and solvent exchange rates of magnesium electrolytes in various solvents by using multimodal nuclear magnetic resonance (NMR) analysis and molecular dynamics/density functional theory (MD/DFT) calculations. These magnesium solvation structures and solvent exchange dynamics are correlated to the combined effects of several physicochemical properties of the solvents. Moreover, Mg2+ transport and interfacial charge transfer efficiency are found to be closely correlated to the solvent exchange rate in the binary electrolytes where the solvent exchange is tunable by the fraction of diluent solvents. Our primary findings are (1) most battery-related solvents undergo ultraslow solvent exchange coordinating to Mg2+ (with time scales ranging from 0.5 µs to 5 ms), (2) the cation transport mechanism is a mixture of vehicular and structural diffusion even at the ultraslow exchange limit (with faster solvent exchange leading to faster cation transport), and (3) an interfacial model wherein organic-rich regions facilitate desolvation and inorganic regions promote Mg2+ transport is consistent with our NMR, electrochemistry, and cryogenic X-ray photoelectron spectroscopy (cryo-XPS) results. This observed ultraslow solvent exchange and its importance for ion transport and interfacial properties necessitate the judicious selection of solvents and informed design of electrolyte blends for multivalent electrolytes.

Chemical Reaction Networks Explain Gas Evolution Mechanisms in Mg-Ion Batteries.

Out-of-equilibrium electrochemical reaction mechanisms are notoriously difficult to characterize. However, such reactions are critical for a range of technological applications. For instance, in metal-ion batteries, spontaneous electrolyte degradation controls electrode passivation and battery cycle life. Here, to improve our ability to elucidate electrochemical reactivity, we for the first time combine computational chemical reaction network (CRN) analysis based on density functional theory (DFT) and differential electrochemical mass spectroscopy (DEMS) to study gas evolution from a model Mg-ion battery electrolyte─magnesium bistriflimide (Mg(TFSI)2) dissolved in diglyme (G2). Automated CRN analysis allows for the facile interpretation of DEMS data, revealing H2O, C2H4, and CH3OH as major products of G2 decomposition. These findings are further explained by identifying elementary mechanisms using DFT. While TFSI- is reactive at Mg electrodes, we find that it does not meaningfully contribute to gas evolution. The combined theoretical-experimental approach developed here provides a means to effectively predict electrolyte decomposition products and pathways when initially unknown.

Understanding the Solvation-Dependent Properties of Cyclic Ether Multivalent Electrolytes Using High-Field NMR and Quantum Chemistry.

Efforts to expand the technological capability of batteries have generated increased interest in divalent cationic systems. Electrolytes used for these electrochemical applications often incorporate cyclic ethers as electrolyte solvents; however, the detailed solvation environments within such systems are not well-understood. To foster insights into the solvation structures of such electrolytes, Ca(TFSI)2 and Zn(TFSI)2 dissolved in tetrahydrofuran (THF) and 2-methyl-tetrahydrofuran were investigated through multi-nuclear magnetic resonance spectroscopy (17O, 43Ca, and 67Zn NMR) combined with quantum chemistry modeling of NMR chemical shifts. NMR provides spectroscopic fingerprints that readily couple with quantum chemistry to identify a set of most probable solvation structures based on the best agreement between the theoretically predicted and experimentally measured values of chemical shifts. The multi-nuclear approach significantly enhances confidence that the correct solvation structures are identified due to the required simultaneous agreement between theory and experiment for multiple nuclear spins. Furthermore, quantum chemistry modeling provides a comparison of the solvation cluster formation energetics, allowing further refinement of the preferred solvation structures. It is shown that a range of solvation structures coexist in most of these electrolytes, with significant molecular motion and dynamic exchange among the structures. This level of solvation diversity correlates with the solubility of the electrolyte, with Zn(TFSI)2/THF exhibiting the lowest degree of each. Comparisons of analogous Ca2+ and Zn2+ solvation structures reveal a significant cation size effect that is manifested in significantly reduced cation-solvent bond lengths and thus stronger solvent bonding for Zn2+ relative to Ca2+. The strength of this bonding is further reduced by methylation of the cyclic ether ring. Solvation shells containing anions are energetically preferred in all the studied electrolytes, leading to significant quantities of contact ion pairs and consequently neutrally charged clusters. It is likely that the transport and interfacial de-solvation/re-solvation properties of these electrolytes are directed by these anion interactions. These insights into the detailed solvation structures, cation size, and solvent effects, including the molecular dynamics, are fundamentally important for the rational design of electrolytes in multivalent battery electrolyte systems.

Concentration-dependent ion correlations impact the electrochemical behavior of calcium battery electrolytes.

Ion interactions strongly determine the solvation environments of multivalent electrolytes even at concentrations below that required for practical battery-based energy storage. This statement is particularly true of electrolytes utilizing ethereal solvents due to their low dielectric constants. These solvents are among the most commonly used for multivalent batteries based on reactive metals (Mg, Ca) due to their reductive stability. Recent developments in multivalent electrolyte design have produced a variety of new salts for Mg2+ and Ca2+ that test the limits of weak coordination strength and oxidative stability. Such electrolytes have great potential for enabling full-cell cycling of batteries based on these working ions. However, the ion interactions in these electrolytes exhibit significant and non-intuitive concentration relationships. In this work, we investigate a promising exemplar, calcium tetrakis(hexafluoroisopropoxy)borate (Ca(BHFIP)2), in the ethereal solvents 1,2-dimethoxyethane (DME) and tetrahydrofuran (THF) across a concentration range of several orders of magnitude. Surprisingly, we find that effective salt dissociation is lower at relatively dilute concentrations (e.g. 0.01 M) than at higher concentrations (e.g. 0.2 M). Combined experimental and computational dielectric and X-ray spectroscopic analyses of the changes occurring in the Ca2+ solvation environment across these concentration regimes reveals a progressive transition from well-defined solvent-separated ion pairs to de-correlated free ions. This transition in ion correlation results in improvements in both conductivity and calcium cycling stability with increased salt concentration. Comparison with previous findings involving more strongly associating salts highlights the generality of this phenomenon, leading to important insight into controlling ion interactions in ether-based multivalent battery electrolytes.

Quantifying Species Populations in Multivalent Borohydride Electrolytes.

Multivalent batteries represent an important beyond Li-ion energy storage concept. The prospect of calcium batteries, in particular, has emerged recently due to novel electrolyte demonstrations, especially that of a ground-breaking combination of the borohydride salt Ca(BH4)2 dissolved in tetrahydrofuran. Recent analysis of magnesium and calcium versions of this electrolyte led to the identification of divergent speciation pathways for Mg2+ and Ca2+ despite identical anions and solvents, owing to differences in cation size and attendant flexibility of coordination. To test these proposed speciation equilibria and develop a more quantitative understanding thereof, we have applied pulsed-field-gradient nuclear magnetic resonance and dielectric relaxation spectroscopy to study these electrolytes. Concentration-dependent variation in anion diffusivities and solution dipole relaxations, interpreted with the aid of molecular dynamics simulations, confirms these divergent Mg2+ and Ca2+ speciation pathways. These results provide a more quantitative description of the electroactive species populations. We find that these species are present in relatively small quantities, even in the highly active Ca(BH4)2/tetrahydrofuran electrolyte. This finding helps interpret previous characterizations of metal deposition efficiency and morphology control and thus provides important fundamental insight into the dynamic properties of multivalent electrolytes for next-generation batteries.

Energy storage emerging: A perspective from the Joint Center for Energy Storage Research.

Energy storage is an integral part of modern society. A contemporary example is the lithium (Li)-ion battery, which enabled the launch of the personal electronics revolution in 1991 and the first commercial electric vehicles in 2010. Most recently, Li-ion batteries have expanded into the electricity grid to firm variable renewable generation, increasing the efficiency and effectiveness of transmission and distribution. Important applications continue to emerge including decarbonization of heavy-duty vehicles, rail, maritime shipping, and aviation and the growth of renewable electricity and storage on the grid. This perspective compares energy storage needs and priorities in 2010 with those now and those emerging over the next few decades. The diversity of demands for energy storage requires a diversity of purpose-built batteries designed to meet disparate applications. Advances in the frontier of battery research to achieve transformative performance spanning energy and power density, capacity, charge/discharge times, cost, lifetime, and safety are highlighted, along with strategic research refinements made by the Joint Center for Energy Storage Research (JCESR) and the broader community to accommodate the changing storage needs and priorities. Innovative experimental tools with higher spatial and temporal resolution, in situ and operando characterization, first-principles simulation, high throughput computation, machine learning, and artificial intelligence work collectively to reveal the origins of the electrochemical phenomena that enable new means of energy storage. This knowledge allows a constructionist approach to materials, chemistries, and architectures, where each atom or molecule plays a prescribed role in realizing batteries with unique performance profiles suitable for emergent demands.

Ion Pairing and Redissociaton in Low-Permittivity Electrolytes for Multivalent Battery Applications.

Detailed speciation of electrolytes as a function of chemical system and concentration provides the foundation for understanding bulk transport as well as possible decomposition mechanisms. In particular, multivalent electrolytes have shown a strong coupling between anodic stability and solvation structure. Furthermore, solvents that are found to exhibit reasonable stability against alkaline-earth metals generally exhibit low permittivity, which typically increases the complexity of the electrolyte species. To improve our understanding of ionic population and associated transport in these important classes of electrolytes, the speciation of Mg(TFSI)2 in monoglyme and diglyme systems is studied via a multiscale thermodynamic model using first-principles calculations for ion association and molecular dynamics simulations for dielectric properties. The results are then compared to Raman and dielectric relaxation spectroscopies, which independently confirm the modeling insights. We find that the significant presence of free ions in the low-permittivity glymes in the concentration range from 0.02 to 0.6 M is well-explained by the low-permittivity redissociation hypothesis. Here, salt speciation is largely dictated by long-range electrostatics, which includes permittivity increases due to polar contact ion pairs. The present results suggest that other low-permittivity multivalent electrolytes may also reach high conductivities as a result of redissociation.

Probing calcium solvation by XAS, MD and DFT calculations.

The solvation shell structures of Ca2+ in aqueous and organic solutions probed by calcium L-edge soft X-ray absorption spectroscopy (XAS) and DFT/MD simulations show the coordination number of Ca2+ to be negatively correlated with the electrolyte concentration and the steric hindrance of the solvent molecule. In this work, the calcium L-edge soft XAS demonstrates its sensitivity to the surrounding chemical environment. Additionally, the total electron yield (TEY) mode is surface sensitive because the electron penetration depth is limited to a few nanometers. Thus this study shows its implications for future battery studies, especially for probing the electrolyte/electrode interface for electrochemical reactions under in situ/operando conditions.

Tuning the Selectivity and Activity of Electrochemical Interfaces with Defective Graphene Oxide and Reduced Graphene Oxide.

Engineered solid-liquid interfaces will play an important role in the development of future energy storage and conversion (ESC) devices. In the present study, defective graphene oxide (GO) and reduced graphene oxide (rGO) structures were used as engineered interfaces to tune the selectivity and activity of Pt disk electrodes. GO was deposited on Pt electrodes via the Langmuir-Blodgett technique, which provided compact and uniform GO films, and these films were subsequently converted to rGO by thermal reduction. Electrochemical measurements revealed that both GO and rGO interfaces on Pt electrodes exhibit selectivity toward the oxygen reduction reaction (ORR), but they do not have an impact on the activity of the hydrogen oxidation reaction in acidic environments. Scanning transmission electron microscopy at atomic resolution, along with Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), and scanning electron microscopy (SEM), revealed possible diffusion sites for H2 and O2 gas molecules and functional groups relevant to the selectivity and activity of these surfaces. Based on these insights, rGO interfaces are further demonstrated to exhibit enhanced activity for the ORR in nonaqueous environments and demonstrate the power of our ex situ engineering approach for the development of next-generation ESC devices.

Elucidating Non-aqueous Solvent Stability and Associated Decomposition Mechanisms for Mg Energy Storage Applications From First-Principles.

Rational design of novel electrolytes with enhanced functionality requires fundamental molecular-level understanding of structure-property relationships. Here we examine the suitability of a range of organic solvents for non-aqueous electrolytes in secondary magnesium batteries using density functional theory (DFT) calculations as well as experimental probes such as cyclic voltammetry and Raman spectroscopy. The solvents considered include ethereal solvents (e.g., glymes) sulfones (e.g., tetramethylene sulfone), and acetonitrile. Computed reduction potentials show that all solvents considered are stable against reduction by Mg metal. Additional computations were carried out to assess the stability of solvents in contact with partially reduced Mg cations (Mg2+ → Mg+) formed during cycling (e.g., deposition) by identifying reaction profiles of decomposition pathways. Most solvents, including some proposed for secondary Mg energy storage applications, exhibit decomposition pathways that are surprisingly exergonic. Interestingly, the stability of these solvents is largely dictated by magnitude of the kinetic barrier to decomposition. This insight should be valuable toward rational design of improved Mg electrolytes.

Nanoporous Polymer Films with a High Cation Transference Number Stabilize Lithium Metal Anodes in Light-Weight Batteries for Electrified Transportation.

To suppress dendrite formation in lithium metal batteries, high cation transference number electrolytes that reduce electrode polarization are highly desirable, but rarely available using conventional liquid electrolytes. Here, we show that liquid electrolytes increase their cation transference numbers (e.g., ∼0.2 to >0.70) when confined to a structurally rigid polymer host whose pores are on a similar length scale (0.5-2 nm) as the Debye screening length in the electrolyte, which results in a diffuse electrolyte double layer at the polymer-electrolyte interface that retains counterions and reject co-ions from the electrolyte due to their larger size. Lithium anodes coated with ∼1 µm thick overlayers of the polymer host exhibit both a low area-specific resistance and clear dendrite-suppressing character, as evident from their performance in Li-Li and Li-Cu cells as well as in post-mortem analysis of the anode's morphology after cycling. High areal capacity Li-S cells (4.9 mg cm-2; 8.2 mAh cm-2) implementing these high transference number polymer-hosted liquid electrolytes were remarkably stable, considering ∼24 µm of lithium was electroreversibly deposited in each cycle at a C-rate of 0.2. We further identified a scalable manufacturing path for these polymer-coated lithium electrodes, which are drop-in components for lithium metal battery manufacturing.

Enhanced Stability of the Carba- closo-dodecaborate Anion for High-Voltage Battery Electrolytes through Rational Design.

Future energy applications rely on our ability to tune liquid intermolecular interactions and achieve designer electrolytes with highly optimized properties. In this work, we demonstrate rational, combined experimental-computational design of a new carba- closo-dodecaborate-based salt with enhanced anodic stability for Mg energy storage applications. We first establish, through a careful examination using a range of solvents, the anodic oxidation of a parent anion, the carba- closo-dodecaborate anion at 4.6 V vs Mg0/2+ (2.0 vs Fc0/+), a value lower than that projected for this anion in organic solvent-based electrolytes and lower than weakly associating bis(trifluoromethylsulfonyl)imide and tetrafluoroborate anions. Solvents such as acetonitrile, 3-methylsulfolane, and 1,1,1,3,3,3-hexafluoroisopropanol are shown to enable the direct measurement of carba- closo-dodecaborate oxidation, where the resultant neutral radical drives passive film formation on the electrode. Second, we employ computational screening to evaluate the impact of functionalization of the parent anion on its stability and find that replacement of the carbon-vertex proton with a more electronegative fluorine or trifluoromethyl ligand increases the oxidative stability and decreases the contact-ion pair formation energy while maintaining reductive stability. This predicted expansion of the electrochemical window for fluorocarba- closo-dodecaborate is experimentally validated. Future work includes evaluation of the viability of these derivative anions as efficient and stable carriers for energy storage as a function of the ionic transport through the resulting surface films formed on candidate cathodes.

Directly Formed Alucone on Lithium Metal for High-Performance Li Batteries and Li-S Batteries with High Sulfur Mass Loading.

Lithium metal is considered the "holy grail" of next-generation battery anodes. However, severe parasitic reactions at the lithium-electrolyte interface deplete the liquid electrolyte and the uncontrolled formation of high surface area and dendritic lithium during cycling causes rapid capacity fading and battery failure. Engineering a dendrite-free lithium metal anode is therefore critical for the development of long-life batteries using lithium anodes. In this study, we deposit a conformal, organic/inorganic hybrid coating, for the first time, directly on lithium metal using molecular layer deposition (MLD) to alleviate these problems. This hybrid organic/inorganic film with high cross-linking structure can stabilize lithium against dendrite growth and minimize side reactions, as indicated by scanning electron microscopy. We discovered that the alucone coating yielded several times longer cycle life at high current rates compared to the uncoated lithium and achieved a steady Coulombic efficiency of 99.5%, demonstrating that the highly cross-linking structured material with great mechanical properties and good flexibility can effectively suppress dendrite formation. The protected Li was further evaluated in lithium-sulfur (Li-S) batteries with a high sulfur mass loading of ∼5 mg/cm2. After 140 cycles at a high current rate of ∼1 mA/cm2, alucone-coated Li-S batteries delivered a capacity of 657.7 mAh/g, 39.5% better than that of a bare lithium-sulfur battery. These findings suggest that flexible coating with high cross-linking structure by MLD is effective to enable lithium protection and offers a very promising avenue for improved performance in the real applications of Li-S batteries.

Lithium Self-Discharge and Its Prevention: Direct Visualization through In Situ Electrochemical Scanning Transmission Electron Microscopy.

To understand the mechanism that controls low-aspect-ratio lithium deposition morphologies for Li-metal anodes in batteries, we conducted direct visualization of Li-metal deposition and stripping behavior through nanoscale in situ electrochemical scanning transmission electron microscopy (EC-STEM) and macroscale-cell electrochemistry experiments in a recently developed and promising solvate electrolyte, 4 M lithium bis(fluorosulfonyl)imide in 1,2-dimethoxyethane. In contrast to published coin cell studies in the same electrolyte, our experiments revealed low Coulombic efficiencies and inhomogeneous Li morphology during in situ observation. We conclude that this discrepancy in Coulombic efficiency and morphology of the Li deposits was dependent on the presence of a compressed lithium separator interface, as we have confirmed through macroscale (not in the transmission electron microscope) electrochemical experiments. Our data suggests that cell compression changed how the solid-electrolyte interphase formed, which is likely responsible for improved morphology and Coulombic efficiency with compression. Furthermore, during the in situ EC-STEM experiments, we observed direct evidence of nanoscale self-discharge in the solvate electrolyte (in the state of electrical isolation). This self-discharge was duplicated in the macroscale, but it was less severe with electrode compression, likely due to a more passivating and corrosion-resistant solid-electrolyte interphase formed in the presence of compression. By combining the solvate electrolyte with a protective LiAl0.3S coating, we show that the Li nucleation density increased during deposition, leading to improved morphological uniformity. Furthermore, self-discharge was suppressed during rest periods in the cycling profile with coatings present, as evidenced through EC-STEM and confirmed with coin cell data.

Directing the Lithium-Sulfur Reaction Pathway via Sparingly Solvating Electrolytes for High Energy Density Batteries.

The lithium-sulfur battery has long been seen as a potential next generation battery chemistry for electric vehicles owing to the high theoretical specific energy and low cost of sulfur. However, even state-of-the-art lithium-sulfur batteries suffer from short lifetimes due to the migration of highly soluble polysulfide intermediates and exhibit less than desired energy density due to the required excess electrolyte. The use of sparingly solvating electrolytes in lithium-sulfur batteries is a promising approach to decouple electrolyte quantity from reaction mechanism, thus creating a pathway toward high energy density that deviates from the current catholyte approach. Herein, we demonstrate that sparingly solvating electrolytes based on compact, polar molecules with a 2:1 ratio of a functional group to lithium salt can fundamentally redirect the lithium-sulfur reaction pathway by inhibiting the traditional mechanism that is based on fully solvated intermediates. In contrast to the standard catholyte sulfur electrochemistry, sparingly solvating electrolytes promote intermediate- and short-chain polysulfide formation during the first third of discharge, before disproportionation results in crystalline lithium sulfide and a restricted fraction of soluble polysulfides which are further reduced during the remaining discharge. Moreover, operation at intermediate temperatures ca. 50 °C allows for minimal overpotentials and high utilization of sulfur at practical rates. This discovery opens the door to a new wave of scientific inquiry based on modifying the electrolyte local structure to tune and control the reaction pathway of many precipitation-dissolution chemistries, lithium-sulfur and beyond.

Phase Boundary Propagation in Li-Alloying Battery Electrodes Revealed by Liquid-Cell Transmission Electron Microscopy.

Battery cycle life is directly influenced by the microstructural changes occurring in the electrodes during charge and discharge cycles. Here, we image in situ the nanoscale phase evolution in negative electrode materials for Li-ion batteries using a fully enclosed liquid cell in a transmission electron microscope (TEM) to reveal early degradation that is not evident in the charge-discharge curves. To compare the electrochemical phase transformation behavior between three model materials, thin films of amorphous Si, crystalline Al, and crystalline Au were lithiated and delithiated at controlled rates while immersed in a commercial liquid electrolyte. This method allowed for the direct observation of lithiation mechanisms in nanoscale negative electrodes, revealing that a simplistic model of a surface-to-interior lithiation front is insufficient. For the crystalline films, a lithiation front spread laterally from a few initial nucleation points, with continued grain nucleation along the growing interface. The intermediate lithiated phases were identified using electron diffraction, and high-resolution postmortem imaging revealed the details of the final microstructure. Our results show that electrochemically induced solid-solid phase transformations can lead to highly concentrated stresses at the laterally propagating phase boundary which should be considered for future designs of nanostructured electrodes for Li-ion batteries.

Passivation Dynamics in the Anisotropic Deposition and Stripping of Bulk Magnesium Electrodes During Electrochemical Cycling.

Although rechargeable magnesium (Mg) batteries show promise for use as a next generation technology for high-density energy storage, little is known about the Mg anode solid electrolyte interphase and its implications for the performance and durability of a Mg-based battery. We explore in this report passivation effects engendered during the electrochemical cycling of a bulk Mg anode, characterizing their influences during metal deposition and dissolution in a simple, nonaqueous, Grignard electrolyte solution (ethylmagnesium bromide, EtMgBr, in tetrahydrofuran). Scanning electron microscopy images of Mg foil working electrodes after electrochemical polarization to dissolution potentials show the formation of corrosion pits. The pit densities so evidenced are markedly potential-dependent. When the Mg working electrode is cycled both potentiostatically and galvanostatically in EtMgBr these pits, formed due to passive layer breakdown, act as the foci for subsequent electrochemical activity. Detailed microscopy, diffraction, and spectroscopic data show that further passivation and corrosion results in the anisotropic stripping of the Mg {0001} plane, leaving thin oxide-comprising passivated side wall structures that demark the {0001} fiber texture of the etched Mg grains. Upon long-term cycling, oxide side walls formed due to the pronounced crystallographic anisotropy of the anodic stripping processes, leading to complex overlay anisotropic, columnar structures, exceeding 50 µm in height. The passive responses mediating the growth of these structures appear to be an intrinsic feature of the electrochemical growth and dissolution of Mg using this electrolyte.

Mechanical Properties of Water-Assembled Graphene Oxide Langmuir Monolayers: Guiding Controlled Transfer.

Liquid-phase transfer of graphene oxide (GO) and reduced graphene oxide (RGO) monolayers is investigated from the perspective of the mechanical properties of these films. Monolayers are assembled in a Langmuir-Blodgett trough, and oscillatory barrier measurements are used to characterize the resulting compressive and shear moduli as a function of surface pressure. GO monolayers are shown to develop a significant shear modulus (10-25 mN/m) at relevant surface pressures while RGO monolayers do not. The existence of a shear modulus indicates that GO is acting as a two-dimensional solid driven by strong interaction between the individual GO sheets. The absence of such behavior in RGO is attributed to the decrease in oxygen moieties on the sheet basal plane, permitting RGO sheets to slide across one another with minimum energy dissipation. Knowledge of this two-dimensional solid behavior is exploited to successfully transfer large-area, continuous GO films to hydrophobic Au substrates. The key to successful transfer is the use of shallow-angle dipping designed to minimize tensile stress present during the insertion or extraction of the substrate. A shallow dip angle on hydrophobic Au does not impart a beneficial effect for RGO monolayers, as these monolayers do not behave as two-dimensional solids and do not remain coherent during the transfer process. We hypothesize that this observed correlation between monolayer mechanical properties and continuous film transfer success is more universally applicable across substrate hydrophobicities and could be exploited to control the transfer of films composed of two-dimensional materials.

Lithium Electrodeposition Dynamics in Aprotic Electrolyte Observed in Situ via Transmission Electron Microscopy.

Electrodeposited metallic lithium is an ideal negative battery electrode, but nonuniform microstructure evolution during cycling leads to degradation and safety issues. A better understanding of the Li plating and stripping processes is needed to enable practical Li-metal batteries. Here we use a custom microfabricated, sealed liquid cell for in situ scanning transmission electron microscopy (STEM) to image the first few cycles of lithium electrodeposition/dissolution in liquid aprotic electrolyte at submicron resolution. Cycling at current densities from 1 to 25 mA/cm(2) leads to variations in grain structure, with higher current densities giving a more needle-like, higher surface area deposit. The effect of the electron beam was explored, and it was found that, even with minimal beam exposure, beam-induced surface film formation could alter the Li microstructure. The electrochemical dissolution was seen to initiate from isolated points on grains rather than uniformly across the Li surface, due to the stabilizing solid electrolyte interphase surface film. We discuss the implications for operando STEM liquid-cell imaging and Li-battery applications.

Intercalation pathway in many-particle LiFePO4 electrode revealed by nanoscale state-of-charge mapping.

The intercalation pathway of lithium iron phosphate (LFP) in the positive electrode of a lithium-ion battery was probed at the ∼40 nm length scale using oxidation-state-sensitive X-ray microscopy. Combined with morphological observations of the same exact locations using transmission electron microscopy, we quantified the local state-of-charge of approximately 450 individual LFP particles over nearly the entire thickness of the porous electrode. With the electrode charged to 50% state-of-charge in 0.5 h, we observed that the overwhelming majority of particles were either almost completely delithiated or lithiated. Specifically, only ∼2% of individual particles were at an intermediate state-of-charge. From this small fraction of particles that were actively undergoing delithiation, we conclude that the time needed to charge a particle is ∼1/50 the time needed to charge the entire particle ensemble. Surprisingly, we observed a very weak correlation between the sequence of delithiation and the particle size, contrary to the common expectation that smaller particles delithiate before larger ones. Our quantitative results unambiguously confirm the mosaic (particle-by-particle) pathway of intercalation and suggest that the rate-limiting process of charging is initiating the phase transformation by, for example, a nucleation-like event. Therefore, strategies for further enhancing the performance of LFP electrodes should not focus on increasing the phase-boundary velocity but on the rate of phase-transformation initiation.