Chemical and Electrochemical Characterization of Hot-Pressed Li6PS5Cl Solid State Electrolyte: Operating Pressure-Invariant High Ionic Conductivity.

Sulfide solid state electrolytes (SSE) are among the most promising materials in the effort to replace liquid electrolytes, largely due to their comparable ionic conductivities. Among the sulfide SSEs, Argyrodites (Li6PS5X, X=Cl, Br, I) further stand out due to their high theoretical ionic conductivity (~1×10-2 S cm-1) and interfacial stability against reactive metal anodes such as lithium. Generally, solid state electrolyte pellets are pressed from powder feedstock at room temperature, however, pellets fabricated by cold pressing consistently result in low bulk density and high porosity, facilitating interfacial degradation reactions and allowing dendrites to propagate through the pores and grain boundaries. Here, we demonstrate the mechanical and electrochemical implications of hot-pressing standalone LPSCl SSE pellets with near-theoretical ionic conductivity, superior cycling performance, and enhanced mechanical stability. X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), and x-ray diffraction spectroscopy (XRD) analysis reveal no chemical changes to the Argyrodite surface after hot pressing up to 250 °C. Moreover, we use electrochemical impedance spectroscopy (EIS) to understand mechanical stability of Argyrodite SSE pellets as a function of externally applied pressure, demonstrating for the first time pressed standalone Argyrodite pellets with near-theoretical conductivities at external pressures below 14 MPa.

Dynamic Electrode-Electrolyte Intermixing in Solid-State Sodium Nano-Batteries.

Nanostructured solid-state batteries (SSBs) are poised to meet the demands of next-generation energy storage technologies by realizing performance competitive to their liquid-based counterparts while simultaneously offering improved safety and expanded form factors. Atomic layer deposition (ALD) is among the tools essential to fabricate nanostructured devices with challenging aspect ratios. Here, we report the fabrication and electrochemical testing of the first nanoscale sodium all-solid-state battery (SSB) using ALD to deposit both the V2O5 cathode and NaPON solid electrolyte followed by evaporation of a thin-film Na metal anode. NaPON exhibits remarkable stability against evaporated Na metal, showing no electrolyte breakdown or significant interphase formation in the voltage range of 0.05-6.0 V vs Na/Na+. Electrochemical analysis of the SSB suggests intermixing of the NaPON/V2O5 layers during fabrication, which we investigate in three ways: in situ spectroscopic ellipsometry, time-resolved X-ray photoelectron spectroscopy (XPS) depth profiling, and cross-sectional cryo-scanning transmission electron microscopy (cryo-STEM) coupled with electron energy loss spectroscopy (EELS). We characterize the interfacial reaction during the ALD NaPON deposition on V2O5 to be twofold: (1) reduction of V2O5 to VO2 and (2) Na+ insertion into VO2 to form NaxVO2. Despite the intermixing of NaPON-V2O5, we demonstrate that NaPON-coated V2O5 electrodes display enhanced electrochemical cycling stability in liquid-electrolyte coin cells through the formation of a stable electrolyte interphase. In all-SSBs, the Na metal evaporation process is found to intensify the intermixing reaction, resulting in the irreversible formation of mixed interphases between discrete battery layers. Despite this graded composition, the SSB can operate for over 100 charge-discharge cycles at room temperature and represents the first demonstration of a functional thin-film solid-state sodium-ion battery.

Bacterial chemotaxis in static gradients quantified in a biopolymer membrane-integrated microfluidic platform.

Chemotaxis is a fundamental bacterial response mechanism to changes in chemical gradients of specific molecules known as chemoattractant or chemorepellent. The advancement of biological platforms for bacterial chemotaxis research is of significant interest for a wide range of biological and environmental studies. Many microfluidic devices have been developed for its study, but challenges still remain that can obscure analysis. For example, cell migration can be compromised by flow-induced shear stress, and bacterial motility can be impaired by nonspecific cell adhesion to microchannels. Also, devices can be complicated, expensive, and hard to assemble. We address these issues with a three-channel microfluidic platform integrated with natural biopolymer membranes that are assembled in situ. This provides several unique attributes. First, a static, steady and robust chemoattractant gradient was generated and maintained. Second, because the assembly incorporates assembly pillars, the assembled membrane arrays connecting nearby pillars can be created longer than the viewing window, enabling a wide 2D area for study. Third, the in situ assembled biopolymer membranes minimize pressure and/or chemiosmotic gradients that could induce flow and obscure chemotaxis study. Finally, nonspecific cell adhesion is avoided by priming the polydimethylsiloxane (PDMS) microchannel surfaces with Pluronic F-127. We demonstrated chemotactic migration of Escherichia coli as well as Pseudomonas aeruginosa under well-controlled easy-to-assemble glucose gradients. We characterized motility using the chemotaxis partition coefficient (CPC) and chemotaxis migration coefficient (CMC) and found our results consistent with other reports. Further, random walk trajectories of individual cells in simple bright field images were conveniently tracked and presented in rose plots. Velocities were calculated, again in agreement with previous literature. We believe the biopolymer membrane-integrated platform represents a facile and convenient system for robust quantitative assessment of cellular motility in response to various chemical cues.

Nanoscale Li, Na, and K ion-conducting polyphosphazenes by atomic layer deposition.

A key trailblazer in the development of thin-film solid-state electrolytes has been lithium phosphorous oxynitride (LiPON), the success of which has led to recent progress in thin-film ion conductors. Here we compare the structural, electrochemical, and processing parameters between previously published LiPON and NaPON ALD processes with a novel ALD process for the K analogue potassium phosphorous oxynitride (KPON). In each ALD process, alkali tert-butoxides and diethylphosphoramidate are used as precursors. To understand the ALD surface reactions, this work proposes a reaction mechanism determined by in-operando mass spectrometry for the LiPON process as key to understanding the characteristics of the APON (A = Li, Na, K) family. As expected, NaPON and LiPON share similar reaction mechanisms as their structures are strikingly similar. KPON, however, exhibits similar ALD process parameters but the resulting film composition is quite different, showing little nitrogen incorporation and more closely resembling a phosphate glass. Due to the profound difference in structure, KPON likely undergoes an entirely different reaction mechanism. This paper presents a comprehensive summary of ALD ion conducting APON films as well as a perspective that highlights the versatility of ALD chemistries as a tool for the development of novel thin film ion-conductors.

Atomic Layer Deposition of Sodium Phosphorus Oxynitride: A Conformal Solid-State Sodium-Ion Conductor.

The development of novel materials that are compatible with nanostructured architectures is required to meet the demands of next-generation energy-storage technologies. Atomic layer deposition (ALD) allows for the precise synthesis of new materials that can conformally coat complex 3D structures. In this work, we demonstrate a thermal ALD process for sodium phosphorus oxynitride (NaPON), a thin-film solid-state electrolyte (SSE), for sodium-ion batteries (SIBs). NaPON is analogous to the commonly used lithium phosphorus oxynitride SSE in lithium-ion batteries. The ALD process produces a conformal film with a stoichiometry of Na4PO3N, corresponding to a sodium polyphosphazene structure. The electrochemical properties of NaPON are characterized to evaluate its potential in SIBs. The NaPON film exhibited a high ionic conductivity of 1.0 × 10-7 S/cm at 25 °C and up to 2.5 × 10-6 S/cm at 80 °C, with an activation energy of 0.53 eV. In addition, the ionic conductivity is comparable and even higher than the ionic conductivities of ALD-fabricated Li+ conductors. This promising result makes NaPON a viable SSE or passivation layer in solid-state SIBs.

Enhancing Lithium Insertion with Electrostatic Nanoconfinement in a Lithography Patterned Precision Cell.

The rapidly growing demand for portable electronics, electric vehicles, and grid storage drives the pursuit of high-performance electrical energy storage (EES). A key strategy for improving EES performance is exploiting nanostructured electrodes that present nanoconfined environments of adjacent electrolytes, with the goal to decrease ion diffusion paths and increase active surface areas. However, fundamental gaps persist in understanding the interface-governed electrochemistry in such nanoconfined geometries, in part because of the imprecise and variable dimension control. Here, we report quantification of lithium insertion under nanoconfinement of the electrolyte in a precise lithography-patterned nanofluidic cell. We show a mechanism that enhances ion insertion under nanoconfinement, namely, selective ion accumulation when the confinement length is comparable to the electrical double layer thickness. The nanofabrication approach with uniform and accurate dimensional control provides a versatile model system to explore fundamental mechanisms of nanoscale electrochemistry, which could have an impact on practical energy storage systems.

Kinetics-Controlled Degradation Reactions at Crystalline LiPON/Lix CoO2 and Crystalline LiPON/Li-Metal Interfaces.

Detailed understanding of solid-solid interface structure-function relationships is critical for the improvement and wide deployment of all-solid-state batteries. The interfaces between lithium phosphorous oxynitride (LiPON) solid electrolyte material and lithium metal anode, and between LiPON and Lix CoO2 cathode, have been reported to generate solid-electrolyte interphase (SEI)-like products and/or disordered regions. Using electronic structure calculations and crystalline LiPON models, we predict that LiPON models with purely P-N-P backbones are kinetically inert towards lithium at room temperature. In contrast, transfer of oxygen atoms from low-energy Lix CoO2 (104) surfaces to LiPON is much faster under ambient conditions. The mechanisms of the primary reaction steps, LiPON structural motifs that readily reacts with lithium metal, experimental results on amorphous LiPON to partially corroborate these predictions, and possible mitigation strategies to reduce degradations are discussed. LiPON interfaces are found to be useful case studies for highlighting the importance of kinetics-controlled processes during battery assembly at moderate processing temperatures.

Three-Dimensional Solid-State Lithium-Ion Batteries Fabricated by Conformal Vapor-Phase Chemistry.

Three-dimensional thin-film solid-state batteries (3D TSSB) were proposed by Long et al. in 2004 as a structure-based approach to simultaneously increase energy and power densities. Here, we report experimental realization of fully conformal 3D TSSBs, demonstrating the simultaneous power-and-energy benefits of 3D structuring. All active battery components-electrodes, solid electrolyte, and current collectors-were deposited by atomic layer deposition (ALD) onto standard CMOS processable silicon wafers microfabricated to form arrays of deep pores with aspect ratios up to approximately 10. The cells utilize an electrochemically prelithiated LiV2O5 cathode, a very thin (40-100 nm) Li2PO2N solid electrolyte, and a SnN x anode. The fabrication process occurs entirely at or below 250 °C, promising compatibility with a variety of substrates as well as integrated circuits. The multilayer battery structure enabled all-ALD solid-state cells to deliver 37 µAh/cm2·µm (normalized to cathode thickness) with only 0.02% per-cycle capacity loss. Conformal fabrication of full cells over 3D substrates increased the areal discharge capacity by an order of magnitude while simulteneously improving power performance, a trend consistent with a finite element model. This work shows that the exceptional conformality of ALD, combined with conventional semiconductor fabrication methods, provides an avenue for the successful realization of long-sought 3D TSSBs which provide power performance scaling in regimes inaccessible to planar form factor cells.

Nanoscale Protection Layers To Mitigate Degradation in High-Energy Electrochemical Energy Storage Systems.

In the pursuit of energy storage devices with higher energy and power, new ion storage materials and high-voltage battery chemistries are of paramount importance. However, they invite-and often enhance-degradation mechanisms, which are reflected in capacity loss with charge/discharge cycling and sometimes in safety problems. Degradation mechanisms are often driven by fundamentals such as chemical and electrochemical reactions at electrode-electrolyte interfaces, volume expansion and stress associated with ion insertion and extraction, and profound inhomogeneity of electrochemical behavior. While it is important to identify and understand these mechanisms at some reasonable level, it is even more critical to design strategies to mitigate these degradation pathways and to develop means to implement and validate the strategies. A growing set of research highlights the mitigation benefits achievable by forming thin protection layers (PLs) intentionally created as artificial interphase regions at the electrode-electrolyte interface. These advances illustrate a promising-perhaps even generic-pathway for enabling higher-energy and higher-voltage battery configurations. In this Account, we summarize examples of such PLs that serve as mitigation strategies to avoid degradation in lithium metal anodes, conversion-type electrode materials, and alloy-type electrodes. Examples are chosen from a larger body of electrochemical degradation research carried out in Nanostructures for Electrical Energy Storage (NEES), our DOE Energy Frontier Research Center. Overall, we argue on the basis of experimental and theoretical evidence that PLs effectively stabilize the electrochemical interfaces to prevent parasitic chemical and electrochemical reactions and mitigate the structural, mechanical, and compositional degradation of the electrode materials at the electrode-electrolyte interfaces. The evidenced improvement in performance metrics is accomplished by (1) establishing a homogeneous interface for ion insertion and extraction, (2) providing mechanical constraints to maintain structural integrity and robust electronic and ionic conduction pathways, and (3) introducing spatial confinements on the electrode material matrix to alter the phase transformation (delaying the occurrence of the conversion reaction) upon Li insertion, which results in superior electrode performance, excellent capacity retention, and improved reversibility. Taken together, these examples portray a valuable role for thin protection layers synthesized over electrode surfaces, both for their benefit to cycle stability and for revealing insights into degradation and mitigation mechanisms. Furthermore, they underscore the impact of complex electrochemical behavior at nanoscale materials and nanostructure interfaces in modulating the behavior of energy storage devices at the mesoscale and macroscale.

High performance asymmetric V2O5-SnO2 nanopore battery by atomic layer deposition.

Here we report the high performance and cyclability of an asymmetric full cell nanopore battery, comprised of V2O5 as the cathode and prelithiated SnO2 as the anode, with integrated nanotubular Pt current collectors underneath each nanotubular storage electrode, confined within an anodized aluminium oxide (AAO) nanopore. Enabled by atomic layer deposition (ALD), this coaxial nanotube full cell is fully confined within a high aspect ratio nanopore (150 nm in diameter, 50 µm in length), with an ultra-small volume of about 1 fL. By controlling the amount of lithium ion prelithiated into the SnO2 anode, we can tune the full cell output voltage in the range of 0.3 V to 3 V. When tested as a massively parallel device (∼2 billion cm-2), this asymmetric nanopore battery array displays exceptional rate performance and cyclability: when cycled between 1 V and 3 V, capacity retention at the 200C rate is ∼73% of that at 1C, and at 25C rate only 2% capacity loss occurs after more than 500 charge/discharge cycles. With the increased full cell output potential, the asymmetric V2O5-SnO2 nanopore battery shows significantly improved energy and power density over the previously reported symmetric cell, 4.6 times higher volumetric energy and 5.2 times higher power density - an even more promising indication that controlled nanostructure designs employing nanoconfined environments with large electrode surface areas present promising directions for future battery technology.

Perspectives in flow-based microfluidic gradient generators for characterizing bacterial chemotaxis.

Chemotaxis is a phenomenon which enables cells to sense concentrations of certain chemical species in their microenvironment and move towards chemically favorable regions. Recent advances in microbiology have engineered the chemotactic properties of bacteria to perform novel functions, but traditional methods of characterizing chemotaxis do not fully capture the associated cell motion, making it difficult to infer mechanisms that link the motion to the microbiology which induces it. Microfluidics offers a potential solution in the form of gradient generators. Many of the gradient generators studied to date for this application are flow-based, where a chemical species diffuses across the laminar flow interface between two solutions moving through a microchannel. Despite significant research efforts, flow-based gradient generators have achieved mixed success at accurately capturing the highly subtle chemotactic responses exhibited by bacteria. Here we present an analysis encompassing previously published versions of flow-based gradient generators, the theories that govern their gradient-generating properties, and new, more practical considerations that result from experimental factors. We conclude that flow-based gradient generators present a challenge inherent to their design in that the residence time and gradient decay must be finely balanced, and that this significantly narrows the window for reliable observation and quantification of chemotactic motion. This challenge is compounded by the effects of shear on an ellipsoidal bacterium that causes it to preferentially align with the direction of flow and subsequently suppresses the cross-flow chemotactic response. These problems suggest that a static, non-flowing gradient generator may be a more suitable platform for chemotaxis studies in the long run, despite posing greater difficulties in design and fabrication.

Interconnected mesoporous V2O5 electrode: impact on lithium ion insertion rate.

Here we introduce a strategy for creating nanotube array electrodes which feature periodic regions of porous interconnections providing open pathways between adjacent nanotubes within the array, utilizing a combination of anodized aluminum oxide growth modification (AAO) and atomic layer deposition. These porous interconnected structures can then be used as testbed electrodes to explore the influence of mesoscale structure on the electrochemical properties of the interconnected mesoporous electrodes. Critically, these unique structures allow the solid state lithium diffusion pathways to be held essentially constant, while the larger structure is modified. While it was anticipated that this strategy would simply provide increased mass loading, the kinetics of the Li+ ion insertion reaction in the porous interconnected electrodes are dramatically improved, demonstrating significantly better capacity retention at high rates than their aligned counterparts. We utilize a charge deconvolution method to explore the kinetics of the charge storage reactions. We are able to trace the origin of the structural influence on rate performance to electronic effects within the electrodes.

Electrochemical Thin Layers in Nanostructures for Energy Storage.

Conventional electrical energy storage (EES) electrodes, such as rechargeable batteries, are mostly based on composites of monolithic micrometer sized particles bound together with polymeric and conductive carbon additives and binders. The kinetic limitations of these monolithic chunks of material are inherently linked to their electrical properties, the kinetics of ion insertion through their interface and ion migration in and through the composite phase. Redox chemistry of nanostructured materials in EES systems offer vast gains in power and energy. Furthermore, due to their thin nature, ion and electron transport is dramatically increased, especially when thin heterogeneous conducting layers are employed synergistically. However, since the stability of the electrode material is dictated by the nature of the electrochemical reaction and the accompanying volumetric and interfacial changes from the perspective of overall system lifetime, research with nanostructured materials has shown often indefinite conclusions: in some cases, an increase in unwanted side-reactions due to the high surface area (bad). In other cases, results have shown significantly better handling of mechanical stress that results from lithiation/delithiation (good). Despite these mixed results, scientifically informed design of thin electrode materials, with carefully chosen architectures, is considered a promising route to address many limitations witnessed in EES systems by reducing and protecting electrodes from parasitic reactions, accommodating mechanical stress due to volumetric changes from electrochemical reactions, and optimizing charge carrier mobilities from both the "ionic" and "electronic" points of view. Furthermore, precise nanoscale control over the electrode structure can enable accurate measurement through advanced spectroscopy and microscopy techniques. This Account summarizes recent findings related to thin electrode materials synthesized by atomic layer deposition (ALD) and electrochemical deposition (ECD), including nanowires, nanotubes, and thin films. Throughout the Account, we will show how these techniques enabled us to synthesize electrodes of interest with precise control over the structure and composition of the material. We will illustrate and discuss how the electrochemical response of thin electrodes made by these techniques can facilitate new mechanisms for ion storage, mediate the interfacial electrochemical response of the electrode, and address issues related to electrode degradation over time. The effects of nanosizing materials and their electrochemical response will be mechanistically reviewed through two categories of ion storage: (1) pseudocapacitance and (2) ion insertion. Additionally, we will show how electrochemical processes that are more complicated because of accompanying volumetric changes and electrode degradation pathways can be mediated and controlled by application of thin functional materials on the electrochemically active interface; examples include conversion electrodes, reactive lithium metal anodes, and complex reactions in a Li/O2 cathode system. The goal of this Account is to illustrate how careful design of thin materials either as active electrodes or as mediating layers can facilitate desirable interfacial electrochemical activity and resolve or shed light on mechanistic limitations of electrochemical processes related to micrometer size particles currently used in energy storage electrodes.

The reaction current distribution in battery electrode materials revealed by XPS-based state-of-charge mapping.

Morphologically complex electrochemical systems such as composite or nanostructured lithium ion battery electrodes exhibit spatially inhomogeneous internal current distributions, particularly when driven at high total currents, due to resistances in the electrodes and electrolyte, distributions of diffusion path lengths, and nonlinear current-voltage characteristics. Measuring and controlling these distributions is interesting from both an engineering standpoint, as nonhomogenous currents lead to lower utilization of electrode material, as well as from a fundamental standpoint, as comparisons between theory and experiment are relatively scarce. Here we describe a new approach using a deliberately simple model battery electrode to examine the current distribution in a electrode material limited by poor electronic conductivity. We utilize quantitative spatially resolved X-ray photoelectron spectroscopy to measure the spatial distribution of the state-of-charge of a V2O5 model electrode as a proxy measure for the current distribution on electrodes discharged at varying current densities. We show that the current at the electrode-electrolyte interface falls off with distance from the current collector, and that the current distribution is a strong function of total current. We compare the observed distributions with a simple analytical model which reproduces the dependence of the distribution on total current, but fails to predict the correct length scale. A more complete numerical simulation suggests that dynamic changes in the electronic conductivity of the V2O5 concurrent with lithium insertion may contribute to the differences between theory and experiment. Our observations should help inform design criteria for future electrode architectures.

A Rechargeable Al/S Battery with an Ionic-Liquid Electrolyte.

Aluminum metal is a promising anode material for next generation rechargeable batteries owing to its abundance, potentially dendrite-free deposition, and high capacity. The rechargeable aluminum/sulfur (Al/S) battery is of great interest owing to its high energy density (1340 Wh kg(-1) ) and low cost. However, Al/S chemistry suffers poor reversibility owing to the difficulty of oxidizing AlSx . Herein, we demonstrate the first reversible Al/S battery in ionic-liquid electrolyte with an activated carbon cloth/sulfur composite cathode. Electrochemical, spectroscopic, and microscopic results suggest that sulfur undergoes a solid-state conversion reaction in the electrolyte. Kinetics analysis identifies that the slow solid-state sulfur conversion reaction causes large voltage hysteresis and limits the energy efficiency of the system.

Solid Electrolyte Lithium Phosphous Oxynitride as a Protective Nanocladding Layer for 3D High-Capacity Conversion Electrodes.

Materials that undergo conversion reactions to form different materials upon lithiation typically offer high specific capacity for energy storage applications such as Li ion batteries. However, since the reaction products often involve complex mixtures of electrically insulating and conducting particles and significant changes in volume and phase, the reversibility of conversion reactions is poor, preventing their use in rechargeable (secondary) batteries. In this paper, we fabricate and protect 3D conversion electrodes by first coating multiwalled carbon nanotubes (MWCNT) with a model conversion material, RuO2, and subsequently protecting them with conformal thin-film lithium phosphous oxynitride (LiPON), a well-known solid-state electrolyte. Atomic layer deposition is used to deposit the RuO2 and the LiPON, thus forming core double-shell MWCNT@RuO2@LiPON electrodes as a model system. We find that the LiPON protection layer enhances cyclability of the conversion electrode, which we attribute to two factors. (1) The LiPON layer provides high Li ion conductivity at the interface between the electrolyte and the electrode. (2) By constraining the electrode materials mechanically, the LiPON protection layer ensures electronic connectivity and thus conductivity during lithiation/delithiation cycles. These two mechanisms are striking in their ability to preserve capacity despite the profound changes in structure and composition intrinsic to conversion electrode materials. This LiPON-protected structure exhibits superior cycling stability and reversibility as well as decreased overpotentials compared to the unprotected core-shell structure. Furthermore, even at very low lithiation potential (0.05 V), the LiPON-protected electrode largely reduces the formation of a solid electrolyte interphase.

Enhancing the reversibility of Mg/S battery chemistry through Li(+) mediation.

Mg metal is a promising anode material for next generation rechargeable battery due to its dendrite-free deposition and high capacity. However, the best cathode for rechargeable Mg battery was based on high molecular weight MgxMo3S4, thus rendering full cell energetically uncompetitive. To increase energy density, high capacity cathode material like sulfur is proposed. However, to date, only limited work has been reported on Mg/S system, all plagued by poor reversibility attributed to the formation of electrochemically inactive MgSx species. Here, we report a new strategy, based on the effect of Li(+) in activating MgSx species, to conjugate a dendrite-free Mg anode with a reversible polysulfide cathode and present a truly reversible Mg/S battery with capacity up to 1000 mAh/gs for more than 30 cycles. Mechanistic insights supported by spectroscopic and microscopic characterization strongly suggest that the reversibility arises from chemical reactivation of MgSx by Li(+).

DMSO-Li2O2 Interface in the Rechargeable Li-O2 Battery Cathode: Theoretical and Experimental Perspectives on Stability.

One of the greatest obstacles for the realization of the nonaqueous Li-O2 battery is finding a solvent that is chemically and electrochemically stable under cell operating conditions. Dimethyl sulfoxide (DMSO) is an attractive candidate for rechargeable Li-O2 battery studies; however, there is still significant controversy regarding its stability on the Li-O2 cathode surface. We performed multiple experiments (in situ XPS, FTIR, Raman, and XRD) which assess the stability of the DMSO-Li2O2 interface and report perspectives on previously published studies. Our electrochemical experiments show long-term stable cycling of a DMSO-based operating Li-O2 cell with a platinum@carbon nanotube core-shell cathode fabricated via atomic layer deposition, specifically with >45 cycles of 40 h of discharge per cycle. This work is complemented by density functional theory calculations of DMSO degradation pathways on Li2O2. Both experimental and theoretical evidence strongly suggests that DMSO is chemically and electrochemically stable on the surface of Li2O2 under the reported operating conditions.

Next-Generation Lithium Metal Anode Engineering via Atomic Layer Deposition.

Lithium metal is considered to be the most promising anode for next-generation batteries due to its high energy density of 3840 mAh g(-1). However, the extreme reactivity of the Li surface can induce parasitic reactions with solvents, contamination, and shuttled active species in the electrolyte, reducing the performance of batteries employing Li metal anodes. One promising solution to this issue is application of thin chemical protection layers to the Li metal surface. Using a custom-made ultrahigh vacuum integrated deposition and characterization system, we demonstrate atomic layer deposition (ALD) of protection layers directly on Li metal with exquisite thickness control. We demonstrate as a proof-of-concept that a 14 nm thick ALD Al2O3 layer can protect the Li surface from corrosion due to atmosphere, sulfur, and electrolyte exposure. Using Li-S battery cells as a test system, we demonstrate an improved capacity retention using ALD-protected anodes over cells assembled with bare Li metal anodes for up to 100 cycles.