Electrifying Carbon Capture by Developing Nanomaterials at the Interface of Molecular and Process Engineering.

ConspectusCarbon capture is an indispensable step toward closing the anthropogenic carbon cycle. However, the large-scale implementation of conventional thermochemical carbon capture technologies is hindered by their low energy efficiency, limited sorbent stability, and complexity in infrastructure integration. A mechanistically different alternative, commonly known as electrochemically mediated carbon capture (EMCC), has garnered increasing research traction over the past few years and relies on electrochemical stimuli instead of thermal or pressure swings for the capture and release of carbon dioxide (CO2). Compared to conventional methods, EMCC can be operated under mild conditions driven by intermittent renewable energy sources and has a flexible design to meet the multiscale demands of carbon capture, offering a potentially sustainable, energy-efficient, and cost-effective solution to CO2 concentration from dilute mixtures or the ambient environment.Nanomaterials have played a crucial role in carbon capture research. For instance, nanoporous materials can provide increased free volumes, surface areas, and active sites for carbon capture through physical or chemical adsorption from the gaseous phase. In contrast, EMCC relies on chemical absorption via acid-base interactions using solubilized CO2 in electrolytes. Therefore, most EMCC sorbents and mediators explored so far have been developed as molecules rather than nanomaterials. In recent years, our team has been focusing on electrifying the carbon capture processes at the molecular, materials, and process levels. We seek to address the most pressing issues associated with EMCC, either in fixed-bed or flow systems, that prevent their practical use. These issues include parasitic reactions with molecular oxygen, insufficient electrode capacity utilization, sorbent crossover, etc. To address these problems, there is an urgent need to develop rationally designed nanomaterials at the interface of molecular electrochemistry and device engineering. This Account provides an overview of recent progress on developing new chemistries and engineering batch/continuous processes for EMCC. We discuss the limitations of current EMCC technology and emphasize why nanomaterials are critical for electrifying carbon capture. First, we introduce the design principles for EMCC sorbents based on redox-active organic CO2 carriers and discuss metrics for their performance evaluation. Second, we showcase how molecular design can tackle problems of sorbent solubility, oxygen stability, and electrolyte compatibility in EMCC. Third, we discuss the early results of nanomaterials as solid sorbents in fixed-bed systems, nonswelling membranes for flow systems, and high-surface-area gas-liquid contactors. Finally, building on the foundation we established through our prior work, we offer perspectives on future directions for nanomaterials to help address the challenges in EMCC.

Development of an Accelerated Rotator-based Drug Release Method for the Evaluation of Bupivacaine Multivesicular Liposomes.

PURPOSE: A multivesicular liposome (MVL) is a liposomal vehicle designed to achieve sustained release characteristics for drugs with short half-lives. For example, a commercial MVL formulation of bupivacaine has been approved by the U.S. Food and Drug Administration for local and regional analgesia. For complex formulations like those containing MVLs, challenges in developing an in vitro release testing (IVRT) method may hinder generic development and regulatory approval. In this study, we developed an accelerated rotator-based IVRT method with the ability to discriminate bupivacaine MVLs with different quality attributes. METHODS: Three IVRT experimental setups including mesh tube, horizontal shaker, and vertical rotator were screened to ensure that at least 50% of bupivacaine can release from MVLs in 24 h. Sample dilution factors, incubation temperature, and the release media pH were optimized for the IVRT. The reproducibility of the developed IVRT method was validated with commercial bupivacaine MVLs. The discriminative capacity was assessed via comparing commercial and compromised bupivacaine MVL formulations. RESULTS: The rotator-based release setup was chosen due to the capability to obtain 70% of drug release within 24 h. The optimized testing conditions were chosen with a 50-fold dilution factor, a temperature of 37ºC, and a media pH of 7.4. CONCLUSIONS: An accelerated rotator-based IVRT method for bupivacaine MVLs was developed in this study, with the discriminatory ability to distinguish between formulations of different qualities. The developed IVRT method was a robust tool for generic development of MVL based formulations.

Photochromic Polyurethane Coatings with Cross-Linked Structure and Self-Healing Behavior Based on the FRET Effect.

Intelligent fluorescent coatings have received widespread attention in the encryption technique field such as anti-counterfeit, while the traditional fluorescent coatings are easy to be damaged by external force. In this study, the fluorescent and self-healing anti-counterfeit coatings are prepared after rational molecular design. Two polymers containing fluorescent groups, including polyurethane containing the anthracene (AN) side group and polyimide containing the naphthalenediimide (NDI) structure are synthesized to realize multiple color changes with fluorescence through simply blending. Due to the overlapping fluorescence spectra of the groups, enabling the fluorescence resonance energy transfer effect (FRET), the coating with different group ratios exhibits tunable fluorescence under the same excitation light, providing diverse patterns. Moreover, due to the reversible photo-crosslinking and thermal de-dimerization properties of anthracene, the recording, erasure, and rewriting of the surface pattern can be realized, and the fluorescent anti-counterfeit coatings exhibit excellent self-healing properties after cross-linking due to the FRET effect, which solves the problem of poor healing and ensures the stability and integrity. The fluorescent coating with cross-linked structure and self-healing behavior based on the FRET effect greatly expands the functional applications of traditional polyurethane materials.

Underpotential lithium plating on graphite anodes caused by temperature heterogeneity.

Rechargeability and operational safety of commercial lithium (Li)-ion batteries demand further improvement. Plating of metallic Li on graphite anodes is a critical reason for Li-ion battery capacity decay and short circuit. It is generally believed that Li plating is caused by the slow kinetics of graphite intercalation, but in this paper, we demonstrate that thermodynamics also serves a crucial role. We show that a nonuniform temperature distribution within the battery can make local plating of Li above 0 V vs. Li0/Li+ (room temperature) thermodynamically favorable. This phenomenon is caused by temperature-dependent shifts of the equilibrium potential of Li0/Li+ Supported by simulation results, we confirm the likelihood of this failure mechanism during commercial Li-ion battery operation, including both slow and fast charging conditions. This work furthers the understanding of nonuniform Li plating and will inspire future studies to prolong the cycling lifetime of Li-ion batteries.

Fenretinide combines perturbation of signaling kinases, cell-extracellular matrix interactions and matrix metalloproteinase activation to inhibit invasion in oral squamous cell carcinoma cells.

Basement membrane invasion defines malignant transformation of surface premalignancy. Treatment of oral squamous cell carcinoma (OSCC) cells with the synthetic vitamin A derivative, fenretinide (4HPR), induces numerous cancer-preventive effects including suppression of basement membrane invasion, elimination of anchorage-independent growth, disruption of actin cytoskeletal components and inhibition of the invasion-enabling focal adhesive kinase. The purpose of this study was to elucidate 4HPR's effects on additional invasion-relevant mechanisms including matrix metalloproteinase (MMP) activation and function, cell-extracellular matrix (ECM) attachments and interaction with a kinase that is essential for the epithelial-myoepithelial transformation i.e. c-Jun NH2-terminal kinase (JNK). Our data revealed that 4HPR binds with high affinity to the ATP-binding site of all three JNK isoforms with concurrent suppression of kinase function. Additional studies showed 4HPR treatment inhibited both OSCC cell-ECM adhesion and MMP activation and function. JNK downregulation and induced expression studies confirmed that the JNK3 isoform conveyed that largest impact on OSCC migration and invasion. Biodegradable polymeric implants formulated to preserve 4HPR's function and bioavailability were employed to assess 4HPR's chemopreventive impact on an OSCC tumor induction model. These studies revealed 4HPR local delivery significantly inhibited OSCC tumor size, mitotic indices and expression of the endothelial marker, erythroblast transformation-specific-related gene with concurrent increases in tumor apoptosis (cleaved caspase-3). Collectively, these data show that 4HPR suppresses invasion at multiple sites including 'outside-in' signaling, cell-ECM interactions and suppression of MMPs. These functions are also essential for physiologic function. Regulation is therefore essential and reinforces the pharmacologic advantage of local delivery chemopreventive formulations. .

Synthetic high-density lipoprotein nanoparticles delivering rapamycin for the treatment of age-related macular degeneration.

Synthetic high-density lipoprotein (sHDL) and rapamycin (Rap) have both been shown to be potential treatments for age-related macular degeneration (AMD). The low aqueous solubility of Rap, however, limits its therapeutic utility. Here we used an Apolipoprotein A-I mimetic peptide and phospholipid-based sHDL for the intravitreal delivery of Rap. By incorporation of Rap in sHDL nanoparticles (sHDL-Rap), we achieve 125-fold increase in drug aqueous concentration. When applied in vitro to retinal pigment epithelium cells, sHDL-Rap exhibited the abilities to efflux cholesterol, neutralize endotoxin, and suppress NF-κB activation. As an mTOR inhibitor, Rap induced autophagy and inhibited NF-κB-mediated pro-inflammatory signaling. Additionally, a greater reduction in lipofuscin accumulation and increased anti-inflammatory effects were achieved by sHDL-Rap relative to free drug or sHDL alone. In vivo studies demonstrated that sHDL reached the target retina pigment epithelium (RPE) layer following intravitreal administration in rats. These results suggest that sHDL-Rap holds potential as a treatment for AMD.

Three-dimensional stable lithium metal anode with nanoscale lithium islands embedded in ionically conductive solid matrix.

Rechargeable batteries based on lithium (Li) metal chemistry are attractive for next-generation electrochemical energy storage. Nevertheless, excessive dendrite growth, infinite relative dimension change, severe side reactions, and limited power output severely impede their practical applications. Although exciting progress has been made to solve parts of the above issues, a versatile solution is still absent. Here, a Li-ion conductive framework was developed as a stable "host" and efficient surface protection to address the multifaceted problems, which is a significant step forward compared with previous host concepts. This was fulfilled by reacting overstoichiometry of Li with SiO. The as-formed LixSi-Li2O matrix would not only enable constant electrode-level volume, but also protect the embedded Li from direct exposure to electrolyte. Because uniform Li nucleation and deposition can be fulfilled owing to the high-density active Li domains, the as-obtained nanocomposite electrode exhibits low polarization, stable cycling, and high-power output (up to 10 mA/cm2) even in carbonate electrolytes. The Li-S prototype cells further exhibited highly improved capacity retention under high-power operation (∼600 mAh/g at 6.69 mA/cm2). The all-around improvement on electrochemical performance sheds light on the effectiveness of the design principle for developing safe and stable Li metal anodes.

Catalytic oxidation of Li2S on the surface of metal sulfides for Li-S batteries.

Polysulfide binding and trapping to prevent dissolution into the electrolyte by a variety of materials has been well studied in Li-S batteries. Here we discover that some of those materials can play an important role as an activation catalyst to facilitate oxidation of the discharge product, Li2S, back to the charge product, sulfur. Combining theoretical calculations and experimental design, we select a series of metal sulfides as a model system to identify the key parameters in determining the energy barrier for Li2S oxidation and polysulfide adsorption. We demonstrate that the Li2S decomposition energy barrier is associated with the binding between isolated Li ions and the sulfur in sulfides; this is the main reason that sulfide materials can induce lower overpotential compared with commonly used carbon materials. Fundamental understanding of this reaction process is a crucial step toward rational design and screening of materials to achieve high reversible capacity and long cycle life in Li-S batteries.

Wrinkled Graphene Cages as Hosts for High-Capacity Li Metal Anodes Shown by Cryogenic Electron Microscopy.

Lithium (Li) metal has long been considered the "holy grail" of battery anode chemistry but is plagued by low efficiency and poor safety due to its high chemical reactivity and large volume fluctuation, respectively. Here we introduce a new host of wrinkled graphene cage (WGC) for Li metal. Different from recently reported amorphous carbon spheres, WGC show highly improved mechanical stability, better Li ion conductivity, and excellent solid electrolyte interphase (SEI) for continuous robust Li metal protection. At low areal capacities, Li metal is preferentially deposited inside the graphene cage. Cryogenic electron microscopy characterization shows that a uniform and stable SEI forms on the WGC surface that can shield the Li metal from direct exposure to electrolyte. With increased areal capacities, Li metal is plated densely and homogeneously into the outer pore spaces between graphene cages with no dendrite growth or volume change. As a result, a high Coulombic efficiency (CE) of ∼98.0% was achieved under 0.5 mA/cm2 and 1-10 mAh/cm2 in commercial carbonate electrolytes, and a CE of 99.1% was realized with high-concentration electrolytes under 0.5 mA/cm2 and 3 mAh/cm2. Full cells using WGC electrodes with prestored Li paired with Li iron phosphate showed greatly improved cycle lifetime. With 10 mAh/cm2 Li metal deposition, the WGC/Li composite anode was able to provide a high specific capacity of ∼2785 mAh/g. With its roll-to-roll compatible fabrication procedure, WGC serves as a highly promising material for the practical realization of Li metal anodes in next-generation high energy density secondary batteries.

Metallurgically lithiated SiOx anode with high capacity and ambient air compatibility.

A common issue plaguing battery anodes is the large consumption of lithium in the initial cycle as a result of the formation of a solid electrolyte interphase followed by gradual loss in subsequent cycles. It presents a need for prelithiation to compensate for the loss. However, anode prelithiation faces the challenge of high chemical reactivity because of the low anode potential. Previous efforts have produced prelithiated Si nanoparticles with dry air stability, which cannot be stabilized under ambient air. Here, we developed a one-pot metallurgical process to synthesize LixSi/Li2O composites by using low-cost SiO or SiO2 as the starting material. The resulting composites consist of homogeneously dispersed LixSi nanodomains embedded in a highly crystalline Li2O matrix, providing the composite excellent stability even in ambient air with 40% relative humidity. The composites are readily mixed with various anode materials to achieve high first cycle Coulombic efficiency (CE) of >100% or serve as an excellent anode material by itself with stable cyclability and consistently high CEs (99.81% at the seventh cycle and ∼99.87% for subsequent cycles). Therefore, LixSi/Li2O composites achieved balanced reactivity and stability, promising a significant boost to lithium ion batteries.

Composite lithium metal anode by melt infusion of lithium into a 3D conducting scaffold with lithiophilic coating.

Lithium metal-based battery is considered one of the best energy storage systems due to its high theoretical capacity and lowest anode potential of all. However, dendritic growth and virtually relative infinity volume change during long-term cycling often lead to severe safety hazards and catastrophic failure. Here, a stable lithium-scaffold composite electrode is developed by lithium melt infusion into a 3D porous carbon matrix with "lithiophilic" coating. Lithium is uniformly entrapped on the matrix surface and in the 3D structure. The resulting composite electrode possesses a high conductive surface area and excellent structural stability upon galvanostatic cycling. We showed stable cycling of this composite electrode with small Li plating/stripping overpotential (<90 mV) at a high current density of 3 mA/cm(2) over 80 cycles.

Vertically Aligned and Continuous Nanoscale Ceramic-Polymer Interfaces in Composite Solid Polymer Electrolytes for Enhanced Ionic Conductivity.

Among all solid electrolytes, composite solid polymer electrolytes, comprised of polymer matrix and ceramic fillers, garner great interest due to the enhancement of ionic conductivity and mechanical properties derived from ceramic-polymer interactions. Here, we report a composite electrolyte with densely packed, vertically aligned, and continuous nanoscale ceramic-polymer interfaces, using surface-modified anodized aluminum oxide as the ceramic scaffold and poly(ethylene oxide) as the polymer matrix. The fast Li+ transport along the ceramic-polymer interfaces was proven experimentally for the first time, and an interfacial ionic conductivity higher than 10-3 S/cm at 0 °C was predicted. The presented composite solid electrolyte achieved an ionic conductivity as high as 5.82 × 10-4 S/cm at the electrode level. The vertically aligned interfacial structure in the composite electrolytes enables the viable application of the composite solid electrolyte with superior ionic conductivity and high hardness, allowing Li-Li cells to be cycled at a small polarization without Li dendrite penetration.

In Situ Investigation on the Nanoscale Capture and Evolution of Aerosols on Nanofibers.

Aerosol-induced haze problem has become a serious environmental concern. Filtration is widely applied to remove aerosols from gas streams. Despite classical filtration theories, the nanoscale capture and evolution of aerosols is not yet clearly understood. Here we report an in situ investigation on the nanoscale capture and evolution of aerosols on polyimide nanofibers. We discovered different capture and evolution behaviors among three types of aerosols: wetting liquid droplets, nonwetting liquid droplets, and solid particles. The wetting droplets had small contact angles and could move, coalesce, and form axisymmetric conformations on polyimide nanofibers. In contrast, the nonwetting droplets had a large contact angle on polyimide nanofibers and formed nonaxisymmetric conformations. Different from the liquid droplets, the solid particles could not move along the nanofibers and formed dendritic structures. This study provides an important insight for obtaining a deep understanding of the nanoscale capture and evolution of aerosols and benefits future design and development of advanced filters.

Design of Complex Nanomaterials for Energy Storage: Past Success and Future Opportunity.

The development of next-generation lithium-based rechargeable batteries with high energy density, low cost, and improved safety is a great challenge with profound technological significance for portable electronics, electric vehicles, and grid-scale energy storage. Specifically, advanced lithium battery chemistries call for a paradigm shift to electrodes with high Li to host ratio based on a conversion or alloying mechanism, where the increased capacity is often accompanied by drastic volumetric changes, significant bond breaking, limited electronic/ionic conductivity, and unstable electrode/electrolyte interphase. Fortunately, the rapid progress of nanotechnology over the past decade has been offering battery researchers effective means to tackle some of the most pressing issues for next-generation battery chemistries. The major applications of nanotechnology in batteries can be summarized as follows: First, by reduction of the dimensions of the electrode materials, the cracking threshold of the material upon lithiation can be overcome, at the same time facilitating electron/ion transport within the electrode. Second, nanotechnology also provides powerful methods to generate various surface-coating and functionalization layers on electrode materials, protecting them from side reactions in the battery environment. Finally, nanotechnology gives people the flexibility to engineer each and every single component within a battery (separator, current collector, etc.), bringing novel functions to batteries that are unachievable by conventional methods. Thus, this Account aims to highlight the crucial role of nanotechnology in advanced battery systems. Because of the limited space, we will mainly assess representative examples of rational nanomaterials design with complexity for silicon and lithium metal anodes, which have shown great promise in constraining their large volume changes and the repeated solid-electrolyte interphase formation during cycling. Noticeably, the roadmap delineating the gradual improvement of silicon anodes with a span of 11 generations of materials designs developed in our group is discussed in order to reflect how nanotechnology could guide battery research step by step toward practical applications. Subsequently, we summarize efforts to construct nanostructured composite sulfur cathodes with improved electronic conductivity and effective soluble species encapsulation for maximizing the utilization of active material, cycle life, and system efficiency. We emphasize carbon-based materials and, importantly, materials with polar surfaces for sulfur entrapment. We then briefly discuss nanomaterials strategies to improve the ionic conductivity of solid polymer electrolytes by means of incorporating high-surface-area and, importantly, high-aspect-ratio secondary-phase fillers for continuous, low-tortuosity ionic transport pathways. Finally, critical innovations that have been brought to the area of grid-scale energy storage and battery safety by nanotechnology are also succinctly reviewed.

Dual Receptor Targeting Cell Penetrating Peptide Modified Liposome for Glioma and Breast Cancer Postoperative Recurrence Therapy.

PURPOSE: Cell penetrating peptides (CPPs) were widely used as motifs for drug delivery to tumor. In former study, an RGD reverse sequence dGR was used to develop active-targeting liposome R8dGR-Lip, which showed well penetrating ability and treatment efficiency on glioma model. However, recurrence after tumor resection caused by post-operative residual cancer cells was a huge obstacle in tumor treatment. In consideration of the effective anti-cancer effect of PTX-R8dGR-Lip when treating glioma in former study, we decide to evaluate its pharmacodynamics on tumor resection models, which were more invasive and resistant. METHOD: In vitro, the effectiveness of PTX-R8dGR-Lip in reducing tumor initiating cell (TIC) was investigated using mammosphere formation. In vivo, the inhibition efficiency of PTX-R8dGR-Lip on C6 glioma recurrence and 4 T1 breast cancer recurrence model were evaluated, including tumor bioluminescence imaging, survival rate and immumohistochemical staining, etc.. RESULTS: C6 mammosphere formation rate of PTX-R8dGR-Lip group was 48.06 ± 2.72%, and 4 T1 mammosphere formation rate of PTX-R8dGR-Lip group was 39.51 ± 4.02% when PBS group was set as 100%. C6 and 4 T1 bioluminescent tumor resected model were established, then effectiveness of different PTX-loaded preparations were evaluated on these two models. PTX-R8dGR-Lip could obviously inhibit tumor recurrence, prolong survival rate and reduce tumor tissue invasion. CONCLUSION: PTX-R8dGR-Lip could reduce post-operative recurrence rate, prolong survival time, and decrease the proliferation of residual cancer cells through regulating the expression of recurrence-related cytokines.

Proliferation of Bilateral Nerve Fibers Following Thalamic Infarction Contributes to Neurological Function Recovery: A Diffusion Tensor Imaging (DTI) Study.

BACKGROUND The aim of this study was to investigate the reorganization in ipsilesional and contralesional thalamic radiation fibers after unilateral focal thalamic stroke in sensory disturbance patients. MATERIAL AND METHODS We recruited 12 patients with acute unilateral thalamic infarction and sensory disturbance and 12 healthy age- and sex-matched controls. All patients underwent diffusion tensor imaging (DTI) and were assessed with National Institutes of Health stroke scale (NIHSS), Barthel index (BI), and paragraph 8 of NIHSS (NIHSS8) at 1 week (W1), 4 weeks (W4), 3 months (M3), and 6 months (M6) after thalamic infraction. The relationship between FA changes and the clinical scores changes were then examined. RESULTS NIHSS and NIHSS8 scores decreased while BI scores increased gradually from W1 to M6 in patients, but not in controls. FA values of the patients gradually increased in ipsilesional and contralesional thalamic radiation fibers from W1 to M6. In addition, the FA values in patients were significantly higher at M3 and M6 compared to W1. No significant changes were observed in the controls. Regarding the relationship between FA changes and the clinical scores changes, the FA increases were negatively correlated with NIHSS and NIHSS8 decrease while FA increases were positively correlated with BI increases. CONCLUSIONS Our results indicate that reorganization occurred after unilateral focal thalamic infarct not only in ipsilesional, but also in contralesional thalamic radiation fibers in patients with sensory disturbance. In addition, the results suggested that the reorganization can support and promote stroke restoration.

Conformal Lithium Fluoride Protection Layer on Three-Dimensional Lithium by Nonhazardous Gaseous Reagent Freon.

Research on lithium (Li) metal chemistry has been rapidly gaining momentum nowadays not only because of the appealing high theoretical capacity, but also its indispensable role in the next-generation Li-S and Li-air batteries. However, two root problems of Li metal, namely high reactivity and infinite relative volume change during cycling, bring about numerous other challenges that impede its practical applications. In the past, extensive studies have targeted these two root causes by either improving interfacial stability or constructing a stable host. However, efficient surface passivation on three-dimensional (3D) Li is still absent. Here, we develop a conformal LiF coating technique on Li surface with commercial Freon R134a as the reagent. In contrast to solid/liquid reagents, gaseous Freon exhibits not only nontoxicity and well-controlled reactivity, but also much better permeability that enables a uniform LiF coating even on 3D Li. By applying a LiF coating onto 3D layered Li-reduced graphene oxide (Li-rGO) electrodes, highly reduced side reactions and enhanced cycling stability without overpotential augment for over 200 cycles were proven in symmetric cells. Furthermore, Li-S cells with LiF protected Li-rGO exhibit significantly improved cyclability and Coulombic efficiency, while excellent rate capability (∼800 mAh g-1 at 2 C) can still be retained.

Solid-State Lithium-Sulfur Batteries Operated at 37 °C with Composites of Nanostructured Li7La3Zr2O12/Carbon Foam and Polymer.

An all solid-state lithium-ion battery with high energy density and high safety is a promising solution for a next-generation energy storage system. High interface resistance of the electrodes and poor ion conductivity of solid-state electrolytes are two main challenges for solid-state batteries, which require operation at elevated temperatures of 60-90 °C. Herein, we report the facile synthesis of Al3+/Nb5+ codoped cubic Li7La3Zr2O12 (LLZO) nanoparticles and LLZO nanoparticle-decorated porous carbon foam (LLZO@C) by the one-step Pechini sol-gel method. The LLZO nanoparticle-filled poly(ethylene oxide) electrolyte shows improved conductivity compared with filler-free samples. The sulfur composite cathode based on LLZO@C can deliver an attractive specific capacity of >900 mAh g-1 at the human body temperature 37 °C and a high capacity of 1210 and 1556 mAh g-1 at 50 and 70 °C, respectively. In addition, the solid-state Li-S batteries exhibit high Coulombic efficiency and show remarkably stable cycling performance.

Lithium Metal Anodes with an Adaptive "Solid-Liquid" Interfacial Protective Layer.

Lithium metal is an attractive anode for the next generation of high energy density lithium-ion batteries due to its high specific capacity (3,860 mAh g-1) and lowest overall anode potential. However, the key issue is that the static solid electrolyte interphase cannot match the dynamic volume changes of the Li anode, resulting in side reactions, dendrite growth, and poor electrodeposition behavior, which prevent its practical applications. Here, we show that the "solid-liquid" hybrid behavior of a dynamically cross-linked polymer enables its use as an excellent adaptive interfacial layer for Li metal anodes. The dynamic polymer can reversibly switch between its "liquid" and "solid" properties in response to the rate of lithium growth to provide uniform surface coverage and dendrite suppression, respectively, thereby enabling the stable operation of lithium metal electrodes. We believe that this example of engineering an adaptive Li/electrolyte interface brings about a new and promising way to address the intrinsic problems of lithium metal anodes.

Identifying the Active Surfaces of Electrochemically Tuned LiCoO2 for Oxygen Evolution Reaction.

Identification of active sites for catalytic processes has both fundamental and technological implications for rational design of future catalysts. Herein, we study the active surfaces of layered lithium cobalt oxide (LCO) for the oxygen evolution reaction (OER) using the enhancement effect of electrochemical delithiation (De-LCO). Our theoretical results indicate that the most stable (0001) surface has a very large overpotential for OER independent of lithium content. In contrast, edge sites such as the nonpolar (112̅0) and polar (011̅2) surfaces are predicted to be highly active and dependent on (de)lithiation. The effect of lithium extraction from LCO on the surfaces and their OER activities can be understood by the increase of Co4+ sites relative to Co3+ and by the shift of active oxygen 2p states. Experimentally, it is demonstrated that LCO nanosheets, which dominantly expose the (0001) surface show negligible OER enhancement upon delithiation. However, a noticeable increase in OER activity (∼0.1 V in overpotential shift at 10 mA cm-2) is observed for the LCO nanoparticles, where the basal plane is greatly diminished to expose the edge sites, consistent with the theoretical simulations. Additionally, we find that the OER activity of De-LCO nanosheets can be improved if we adopt an acid etching method on LCO to create more active edge sites, which in turn provides a strong evidence for the theoretical indication.