Neuromorphic sensorimotor loop embodied by monolithically integrated, low-voltage, soft e-skin.

Artificial skin that simultaneously mimics sensory feedback and mechanical properties of natural skin holds substantial promise for next-generation robotic and medical devices. However, achieving such a biomimetic system that can seamlessly integrate with the human body remains a challenge. Through rational design and engineering of material properties, device structures, and system architectures, we realized a monolithic soft prosthetic electronic skin (e-skin). It is capable of multimodal perception, neuromorphic pulse-train signal generation, and closed-loop actuation. With a trilayer, high-permittivity elastomeric dielectric, we achieved a low subthreshold swing comparable to that of polycrystalline silicon transistors, a low operation voltage, low power consumption, and medium-scale circuit integration complexity for stretchable organic devices. Our e-skin mimics the biological sensorimotor loop, whereby a solid-state synaptic transistor elicits stronger actuation when a stimulus of increasing pressure is applied.

A Cation-Tethered Flowable Polymeric Interface for Enabling Stable Deposition of Metallic Lithium.

A fundamental challenge, shared across many energy storage devices, is the complexity of electrochemistry at the electrode-electrolyte interfaces that impacts the Coulombic efficiency, operational rate capability, and lifetime. Specifically, in energy-dense lithium metal batteries, the charging/discharging process results in structural heterogeneities of the metal anode, leading to battery failure by short-circuit and capacity fade. In this work, we take advantage of organic cations with lower reduction potential than lithium to build an electrically responsive polymer interface that not only adapts to morphological perturbations during electrodeposition and stripping but also modulates the lithium ion migration pathways to eliminate surface roughening. We find that this concept can enable prolonging the long-term cycling of a high-voltage lithium metal battery by at least twofold compared to bare lithium metal.

Valence-Dependent Electrical Conductivity in a 3D Tetrahydroxyquinone-Based Metal-Organic Framework.

Electrically conductive metal-organic frameworks (cMOFs) have become a topic of intense interest in recent years because of their great potential in electrochemical energy storage, electrocatalysis, and sensing applications. Most of the cMOFs reported hitherto are 2D structures, and 3D cMOFs remain rare. Herein we report FeTHQ, a 3D cMOF synthesized from tetrahydroxy-1,4-quinone (THQ) and iron(II) sulfate salt. FeTHQ exhibited a conductivity of 3.3 ± 0.55 mS cm-1 at 300 K, which is high for 3D cMOFs. The conductivity of FeTHQ is valence-dependent. A higher conductivity was measured with the as-prepared FeTHQ than with the air-oxidized and sodium naphthalenide-reduced samples.

Structure, Rheology, and Electrokinetics of Soft Colloidal Suspension Electrolytes.

When ion transport in a binary liquid electrolyte is driven at potentials above the thermal voltage, an extended space charge region forms at the electrolyte/electrode interface and triggers the hydrodynamic instability termed electroconvection. We experimentally show that this instability can be completely arrested in soft colloidal suspension electrolytes composed of low concentrations of polymer-grafted nanoparticles in a liquid host. The mechanism is revealed by means of X-ray scattering, Brownian dynamics calculations, and linear stability analysis to involve overlap of the soft particles at low particle fractions to create a jammed, nanoporous medium that resists convective flow by a Darcy-Brinkman like drag on the electrolyte solvent.

Regulating electrodeposition morphology of lithium: towards commercially relevant secondary Li metal batteries.

Lithium, the lightest and most electronegative metallic element, has long been considered the ultimate choice as a battery anode for mobile, as well as in some stationary applications. The high electronegativity of Li is, however, a double-edged sword-it facilitates a large operating voltage when paired with essentially any cathode, promising a high cell-level energy density. It is also synonymous with a high chemical reactivity and low reduction potential. The interfaces a Li metal anode forms with any other material (liquid or solid) in an electrochemical cell are therefore always mediated by one or more products of its chemical or electrochemical reactions with that material. The physical, crystallographic, mechanical, electrochemical, and transport properties of the resultant new material phases (interphases) regulate all interfacial processes at a Li metal anode, including electrodeposition during battery recharge. This Review takes recent efforts aimed at manipulating the structure, composition, and physical properties of the solid electrolyte interphase (SEI) formed on an Li anode as a point of departure to discuss the structural, electrokinetic, and electrochemical requirements for achieving high anode reversibility. An important conclusion is that while recent reports showing significant advances in the achievement of highly reversible Li anodes, e.g. as measured by the coulombic efficiency (CE), raise prospects for as significant progress towards commercially relevant Li metal batteries, the plateauing of achievable CE values to around 99 ± 0.5% apparent from a comprehensive analysis of the literature is problematic because CE values of at least 99.7%, and preferably >99.9% are required for Li metal cells to live up to the potential for higher energy density batteries offered by the Li metal anode. On this basis, we discuss promising approaches for creating purpose-built interphases on Li, as well as for fabricating advanced Li electrode architectures for regulating Li electrodeposition morphology and crystallinity. Considering the large number of physical and chemical factors involved in achieving fine control of Li electrodeposition, we believe that achievement of the remaining ∼0.5% in anode reversibility will require fresh approaches, perhaps borrowed from other fields. We offer perspectives on both current and new strategies for achieving such Li anodes with the specific aim of engaging established contributors and newcomers to the field in the search for scalable solutions.

Nucleation and Early Stage Growth of Li Electrodeposits.

The morphologies that metal electrodeposits form during the earliest stages of electrodeposition are known to play a critical role in the recharge of electrochemical cells that use metals as anodes. Here we report results from a combined theoretical and experimental study of the early stage nucleation and growth of electrodeposited lithium at liquid-solid interfaces. The spatial characteristics of lithium electrodeposits are studied via scanning electron microscopy (SEM) in tandem with image analysis. Comparisons of Li nucleation and growth in multiple electrolytes provide a comprehensive picture of the initial nucleation and growth dynamics. We report that ion diffusion in the bulk electrolyte and through the solid electrolyte interphase (SEI) formed spontaneously on the metal play equally important roles in regulating  Li nucleation and growth. We show further that the underlying physics dictating bulk and surface diffusion are similar across a range of electrolyte chemistries and measurement conditions, and that fluorinated electrolytes produce a distinct flattening of Li electrodeposits at low rates. These observations are rationalized using X-ray photoelectron spectroscopy (XPS), electrochemical impedance spectroscopy (EIS), and contact angle goniometry to probe the interfacial chemistry and dynamics. Our results show that high interfacial energy and high surface ion diffusivity are necessary for uniform Li plating.

Solid-state polymer electrolytes for high-performance lithium metal batteries.

Electrochemical cells based on alkali metal anodes are receiving intensive scientific interest as potentially transformative technology platforms for electrical energy storage. Chemical, morphological, mechanical and hydrodynamic instabilities at the metal anode produce uneven metal electrodeposition and poor anode reversibility, which, are among the many known challenges that limit progress. Here, we report that solid-state electrolytes based on crosslinked polymer networks can address all of these challenges in cells based on lithium metal anodes. By means of transport and electrochemical analyses, we show that manipulating thermodynamic interactions between polymer segments covalently anchored in the network and "free" segments belonging to an oligomeric electrolyte hosted in the network pores, one can facilely create hybrid electrolytes that simultaneously exhibit liquid-like barriers to ion transport and solid-like resistance to morphological and hydrodynamic instability.

Stabilizing polymer electrolytes in high-voltage lithium batteries.

Electrochemical cells that utilize lithium and sodium anodes are under active study for their potential to enable high-energy batteries. Liquid and solid polymer electrolytes based on ether chemistry are among the most promising choices for rechargeable lithium and sodium batteries. However, uncontrolled anionic polymerization of these electrolytes at low anode potentials and oxidative degradation at working potentials of the most interesting cathode chemistries have led to a quite concession in the field that solid-state or flexible batteries based on polymer electrolytes can only be achieved in cells based on low- or moderate-voltage cathodes. Here, we show that cationic chain transfer agents can prevent degradation of ether electrolytes by arresting uncontrolled polymer growth at the anode. We also report that cathode electrolyte interphases composed of preformed anionic polymers and supramolecules provide a fundamental strategy for extending the high voltage stability of ether-based electrolytes to potentials well above conventionally accepted limits.

Electrolytic vascular systems for energy-dense robots.

Modern robots lack the multifunctional interconnected systems found in living organisms and are consequently unable to reproduce their efficiency and autonomy. Energy-storage systems are among the most crucial limitations to robot autonomy, but their size, weight, material and design constraints can be re-examined in the context of multifunctional, bio-inspired applications. Here we present a synthetic energy-dense circulatory system embedded in an untethered, aquatic soft robot. Modelled after redox flow batteries, this synthetic vascular system combines the functions of hydraulic force transmission, actuation and energy storage into a single integrated design that geometrically increases the energy density of the robot to enable operation for long durations (up to 36 hours). The fabrication techniques and flexible materials used in its construction enable the vascular system to be created with complex form factors that continuously deform with the robot's movement. This use of electrochemical energy storage in hydraulic fluids could facilitate increased energy density, autonomy, efficiency and multifunctionality in future robot designs.

Cryo-STEM mapping of solid-liquid interfaces and dendrites in lithium-metal batteries.

Solid-liquid interfaces are important in a range of chemical, physical and biological processes1-4, but are often not fully understood owing to the lack of high-resolution characterization methods that are compatible with both solid and liquid components5. For example, the related processes of dendritic deposition of lithium metal and the formation of solid-electrolyte interphase layers6,7 are known to be key determinants of battery safety and performance in high-energy-density lithium-metal batteries. But exactly what is involved in these two processes, which occur at a solid-liquid interface, has long been debated8-11 because of the challenges of observing such interfaces directly. Here we adapt a technique that has enabled cryo-transmission electron microscopy (cryo-TEM) of hydrated specimens in biology-immobilization of liquids by rapid freezing, that is, vitrification12. By vitrifying the liquid electrolyte we preserve it and the structures at solid-liquid interfaces in lithium-metal batteries in their native state, and thus enable structural and chemical mapping of these interfaces by cryo-scanning transmission electron microscopy (cryo-STEM). We identify two dendrite types coexisting on the lithium anode, each with distinct structure and composition. One family of dendrites has an extended solid-electrolyte interphase layer, whereas the other unexpectedly consists of lithium hydride instead of lithium metal and may contribute disproportionately to loss of battery capacity. The insights into the formation of lithium dendrites that our work provides demonstrate the potential of cryogenic electron microscopy for probing nanoscale processes at intact solid-liquid interfaces in functional devices such as rechargeable batteries.

Confining electrodeposition of metals in structured electrolytes.

Electrochemical cells based on alkali metal (Li, Na) anodes have attracted significant recent attention because of their promise for producing large increases in gravimetric energy density for energy storage in batteries. To facilitate stable, long-term operation of such cells a variety of structured electrolytes have been designed in different physical forms, ranging from soft polymer gels to hard ceramics, including nanoporous versions of these ceramics that host a liquid or molten polymer in their pores. In almost every case, the electrolytes are reported to be substantially more effective than anticipated by early theories in improving uniformity of deposition and lifetime of the metal anode. These observations have been speculated to reflect the effect of electrolyte structure in regulating ion transport to the metal electrolyte interface, thereby stabilizing metal electrodeposition processes at the anode. Here we create and study model structured electrolytes composed of covalently linked polymer grafted nanoparticles that host a liquid electrolyte in the pores. The electrolytes exist as freestanding membranes with effective pore size that can be systematically manipulated through straightforward control of the volume fraction of the nanoparticles. By means of physical analysis and direct visualization experiments we report that at current densities approaching the diffusion limit, there is a clear transition from unstable to stable electrodeposition at Li metal electrodes in membranes with average pore sizes below 500 nm. We show that this transition is consistent with expectations from a recent theoretical analysis that takes into account local coupling between stress and ion transport at metal-electrolyte interfaces.

Design Principles of Functional Polymer Separators for High-Energy, Metal-Based Batteries.

Next-generation rechargeable batteries that offer high energy density, efficiency, and reversibility rely on cell configurations that enable synergistic operations of individual components. They must also address multiple emerging challenges,which include electrochemical stability, transport efficiency, safety, and active material loss. The perspective of this Review is that rational design of the polymeric separator, which is used widely in rechargeable batteries, provides a rich set of opportunities for new innovations that should enable batteries to meet many of these needs. This perspective is different from the conventional view of the polymer separator as an inert/passive unit in a battery, which has the sole function to prevent direct contact between electrically conductivecomponents that form the battery anode and cathode. Polymer separators, which serve as the core component in a battery, bridge the electrodes and the electrolyte with a large surface contact that can be utilized to apply desirable functions. This Review focuses specifically on recent advances in polymer separator systems, with a detailed analysis of several embedded functional agents that are incorporated to improve mechanical robustness, regulate ion and mass transport, and retard flammability. The discussion is also extended to new composite separator concepts that are designated traditionally as polymer/gel electrolytes.

Dynamics of Nanoparticles in Entangled Polymer Solutions.

The mean square displacement ⟨r2⟩ of nanoparticle probes dispersed in simple isotropic liquids and in polymer solutions is interrogated using fluorescence correlation spectroscopy and single-particle tracking (SPT) experiments. Probe dynamics in different regimes of particle diameter (d), relative to characteristic polymer length scales, including the correlation length (ξ), the entanglement mesh size (a), and the radius of gyration (Rg), are investigated. In simple fluids and for polymer solutions in which d ≫ Rg, long-time particle dynamics obey random-walk statistics ⟨r2⟩:t, with the bulk zero-shear viscosity of the polymer solution determining the frictional resistance to particle motion. In contrast, in polymer solutions with d < Rg, polymer molecules in solution exert noncontinuum resistances to particle motion and nanoparticle probes appear to interact hydrodynamically only with a local fluid medium with effective drag comparable to that of a solution of polymer chain segments with sizes similar to those of the nanoparticle probes. Under these conditions, the nanoparticles exhibit orders of magnitude faster dynamics than those expected from continuum predictions based on the Stokes-Einstein relation. SPT measurements further show that when d > a, nanoparticle dynamics transition from diffusive to subdiffusive on long timescales, reminiscent of particle transport in a field with obstructions. This last finding is in stark contrast to the nanoparticle dynamics observed in entangled polymer melts, where X-ray photon correlation spectroscopy measurements reveal faster but hyperdiffusive dynamics. We analyze these results with the help of the hopping model for particle dynamics in polymers proposed by Cai et al. and, on that basis, discuss the physical origins of the local drag experienced by the nanoparticles in entangled polymer solutions.

Building Organic/Inorganic Hybrid Interphases for Fast Interfacial Transport in Rechargeable Metal Batteries.

We report a facile in situ synthesis that utilizes readily accessible SiCl4 cross-linking chemistry to create durable hybrid solid-electrolyte interphases (SEIs) on metal anodes. Such hybrid SEIs composed of Si-interlinked OOCOR molecules that host LiCl salt exhibit fast charge-transfer kinetics and as much as five-times higher exchange current densities, in comparison to their spontaneously formed analogues. Electrochemical analysis and direct optical visualization of Li and Na deposition in symmetric Li/Li and Na/Na cells show that the hybrid SEI provides excellent morphological control at high current densities (3-5 mA cm-2 ) for Li and even for notoriously unstable Na metal anodes. The fast interfacial transport attributes of the SEI are also found to be beneficial for Li-S cells and stable electrochemical cycling was achieved in galvanostatic studies at rates as high as 2 C. Our work therefore provides a promising approach towards rational design of multifunctional, elastic SEIs that overcome the most serious limitations of spontaneously formed interphases on high-capacity metal anodes.

Electrochemical Interphases for High-Energy Storage Using Reactive Metal Anodes.

Stable electrochemical interphases play a critical role in regulating transport of mass and charge in all electrochemical energy storage (EES) systems. In state-of-the-art rechargeable lithium ion batteries, they are rarely formed by design but instead spontaneously emerge from electrochemical degradation of electrolyte and electrode components. High-energy secondary batteries that utilize reactive metal anodes (e.g., Li, Na, Si, Sn, Al) to store large amounts of charge by alloying and/or electrodeposition reactions introduce fundamental challenges that require rational design in order to stabilize the interphases. Chemical instability of the electrodes in contact with electrolytes, morphological instability of the metal-electrolyte interface upon plating and stripping, and hydrodynamic-instability-induced electroconvection of the electrolyte at high currents are all known to cause metal electrode-electrolyte interfaces to continuously evolve in morphology, uniformity, and composition. Additionally, metal anodes undergo large changes in volume during lithiation and delithiation, which means that even in the rare cases where spontaneously formed solid electrode-electrolyte interphases (SEIs) are in thermodynamic equilibrium with the electrode, the SEI is under dynamic strain, which inevitably leads to cracking and/or rupture during extended battery cycling. There is an urgent need for interphases that are able to overcome each of these sources of instability with minimal losses of electrolyte and electrode components. Complementary chemical synthesis strategies are likewise urgently needed to create self-limited and mechanically durable SEIs that are able to flex and shrink to accommodate volume change. These needs are acute for practically relevant cells that cannot utilize large excesses of anode and electrolyte as employed in proof-of-concept-type experiments reported in the scientific literature. This disconnect between practical needs and research practices makes it difficult to translate promising literature results, underscoring the importance of research designed to reveal principles for good interphase design. This Account considers the fundamental processes involved in interphase formation, stability, and failure and on that basis identifies design principles, synthesis procedures, and characterization methods for enabling stable metal anode-electrolyte interfaces for EES. We first review results from experimental, continuum theoretical, and computational analyses of interfacial transport to identify fundamental connections between the composition of the SEI at metal-electrolyte interfaces and stability. Design principles and tools for creating stable artificial solid-electrolyte interphases (ASEIs) based on polymers, ionic liquids, ceramics, nanoparticles, salts, and their combinations are subsequently discussed. Interphases composed of a second electrochemically active material that stores charge by different processes from the underlying metal electrode emerge as particularly attractive routes toward so-called hybrid electrodes that enable facile scale-up of ASEI designs for commercially relevant EES.

Designing solid-liquid interphases for sodium batteries.

Secondary batteries based on earth-abundant sodium metal anodes are desirable for both stationary and portable electrical energy storage. Room-temperature sodium metal batteries are impractical today because morphological instability during recharge drives rough, dendritic electrodeposition. Chemical instability of liquid electrolytes also leads to premature cell failure as a result of parasitic reactions with the anode. Here we use joint density-functional theoretical analysis to show that the surface diffusion barrier for sodium ion transport is a sensitive function of the chemistry of solid-electrolyte interphase. In particular, we find that a sodium bromide interphase presents an exceptionally low energy barrier to ion transport, comparable to that of metallic magnesium. We evaluate this prediction by means of electrochemical measurements and direct visualization studies. These experiments reveal an approximately three-fold reduction in activation energy for ion transport at a sodium bromide interphase. Direct visualization of sodium electrodeposition confirms large improvements in stability of sodium deposition at sodium bromide-rich interphases.The chemistry at the interface between electrolyte and electrode plays a critical role in determining battery performance. Here, the authors show that a NaBr enriched solid-electrolyte interphase can lower the surface diffusion barrier for sodium ions, enabling stable electrodeposition.

Electroless Formation of Hybrid Lithium Anodes for Fast Interfacial Ion Transport.

Rechargeable batteries based on metallic anodes are of interest for fundamental and application-focused studies of chemical and physical kinetics of liquids at solid interfaces. Approaches that allow facile creation of uniform coatings on these metals to prevent physical contact with liquid electrolytes, while enabling fast ion transport, are essential to address chemical instability of the anodes. Here, we report a simple electroless ion-exchange chemistry for creating coatings of indium on lithium. By means of joint density functional theory and interfacial characterization experiments, we show that In coatings stabilize Li by multiple processes, including exceptionally fast surface diffusion of lithium ions and high chemical resistance to liquid electrolytes. Indium coatings also undergo reversible alloying reactions with lithium ions, facilitating design of high-capacity hybrid In-Li anodes that use both alloying and plating approaches for charge storage. By means of direct visualization, we further show that the coatings enable remarkably compact and uniform electrodeposition. The resultant In-Li anodes are shown to exhibit minimal capacity fade in extended galvanostatic cycling when paired with commercial-grade cathodes.

Designer interphases for the lithium-oxygen electrochemical cell.

An electrochemical cell based on the reversible oxygen reduction reaction: 2Li+ + 2e - + O2↔ Li2O2, provides among the most energy dense platforms for portable electrical energy storage. Such Lithium-Oxygen (Li-O2) cells offer specific energies competitive with fossil fuels and are considered promising for electrified transportation. Multiple, fundamental challenges with the cathode, anode, and electrolyte have limited practical interest in Li-O2 cells because these problems lead to as many practical shortcomings, including poor rechargeability, high overpotentials, and specific energies well below theoretical expectations. We create and study in-situ formation of solid-electrolyte interphases (SEIs) based on bromide ionomers tethered to a Li anode that take advantage of three powerful processes for overcoming the most stubborn of these challenges. The ionomer SEIs are shown to protect the Li anode against parasitic reactions and also stabilize Li electrodeposition during cell recharge. Bromine species liberated during the anchoring reaction also function as redox mediators at the cathode, reducing the charge overpotential. Finally, the ionomer SEI forms a stable interphase with Li, which protects the metal in high Gutmann donor number liquid electrolytes. Such electrolytes have been reported to exhibit rare stability against nucleophilic attack by Li2O2 and other cathode reaction intermediates, but also react spontaneously with Li metal anodes. We conclude that rationally designed SEIs able to regulate transport of matter and ions at the electrolyte/anode interface provide a promising platform for addressing three major technical barriers to practical Li-O2 cells.

Highly Stable Sodium Batteries Enabled by Functional Ionic Polymer Membranes.

A sodium metal anode protected by an ion-rich polymeric membrane exhibits enhanced stability and high-Columbic efficiency cycling. Formed in situ via electropolymerization of functional imidazolium-type ionic liquid monomers, the polymer membrane protects the metal against parasitic reactions with electrolyte and, for fundamental reasons, inhibits dendrite formation and growth. The effectiveness of the membrane is demonstrated using direct visualization of sodium electrodeposition.

Interactions, Structure, and Dynamics of Polymer-Tethered Nanoparticle Blends.

We report on the structure, jamming, and dynamics of blends of self-suspended hairy silica nanoparticles grafted with poly(ethylene glycol) (PEG) and poly(methyl methacrylate) (PMMA). We find that favorable enthalpic attraction between tethered PEG and PMMA chains augment previously reported entropic attractions between tethered polymer chains in self-suspended suspensions to enhance particle-particle correlations, increase jamming, and slow down chain dynamics. As with their single-component counterparts, the hairy SiO2-PEG/SiO2-PMMA nanoparticle blends exhibit soft glassy rheological behavior and both the energy dissipated at yielding and the plateau elastic modulus display strong maxima in the symmetric case. A comparison of the small angle X-ray scattering (SAXS) measurements with theoretical analysis from density functional theory (DFT) reveals that the addition of SiO2-PMMA to a self-suspended SiO2-PEG suspension initially leads to a higher degree of stretching of the corona chains, which produces stronger interdigitation of the tethered chains, enhanced jamming, and slower polymer relaxation than observed in the single-component materials. By means of an analysis of the heat of mixing released upon blending tethered and untethered PEG and PMMA chains, we find that the strong enthalpic attraction between the grafted polymer chains enhances entropic attractive forces produced by the space-filling constraint on tethered ligands in self-suspended suspensions to produce entangled-polymer-like physical properties in polymers with molecular weights below the thresholds normally associated with the transition to an entangled state.