Electrolyte and Interphase Design for Magnesium Anode: Major Challenges and Perspectives.

The rechargeable magnesium battery (RMB) is regarded as a high-energy, safe, and cost-effective alternative for conventional batteries. Unfortunately, the passivation and uneven Mg growth not only raise the voltage hysteresis but also shorten the cycle life of RMBs. In this review, Mg passivation induced by electrolytes/contaminants, growth patterns of high dimensional Mg0 , and mechanisms of Mg anode degradation are discussed. The recent efforts on suppressing electrolyte decomposition and uneven Mg growth including electrolyte/interphase modifications through additives, weakly coordinating anions, artificial interphases, and 3D magnesiophilic hosts are summarized. Finally, the future directions in stabilizing Mg anode and realizing high-performance RMBs are highlighted.

Molecular crowding electrolytes for high-voltage aqueous batteries.

Developing low-cost and eco-friendly aqueous electrolytes with a wide voltage window is critical to achieve safe, high-energy and sustainable Li-ion batteries. Emerging approaches using highly concentrated salts (21-55 m (mol kg-1)) create artificial solid-electrode interfaces and improve water stability; however, these approaches raise concerns about cost and toxicity. Molecular crowding is a common phenomenon in living cells where water activity is substantially suppressed by molecular crowding agents through altering the hydrogen-bonding structure. Here we demonstrate a 'molecular crowding' electrolyte using the water-miscible polymer poly(ethylene glycol) as the crowding agent to decrease water activity, thereby achieving a wide electrolyte operation window (3.2 V) with low salt concentration (2 m). Aqueous Li4Ti5O12/LiMn2O4 full cells with stable specific energies between 75 and 110 W h kg-1 were demonstrated over 300 cycles. Online electrochemical mass spectroscopy revealed that common side reactions in aqueous Li-ion batteries (hydrogen/oxygen evolution reactions) are virtually eliminated. This work provides a path for designing high-voltage aqueous electrolytes for low-cost and sustainable energy storage.

A high-rate and long-life organic-oxygen battery.

Alkali metal-oxygen batteries promise high gravimetric energy densities but suffer from low rate capability, poor cycle life and safety hazards associated with metal anodes. Here we describe a safe, high-rate and long-life oxygen battery that exploits a potassium biphenyl complex anode and a dimethylsulfoxide-mediated potassium superoxide cathode. The proposed potassium biphenyl complex-oxygen battery exhibits an unprecedented cycle life (3,000 cycles) with a superior average coulombic efficiency of more than 99.84% at a high current density of 4.0 mA cm-2. We further reduce the redox potential of biphenyl by adding the electron-donating methyl group to the benzene ring, which successfully achieved a redox potential of 0.14 V versus K/K+. This demonstrates the direction and opportunities to further improve the cell voltage and energy density of the alkali-metal organic-oxygen batteries.

Reverse Electrodialysis Chemical Cell for Energy Harvesting from Controlled Acid-Base Neutralization.

We report a novel reverse electrodialysis (RED) chemical cell that integrates RED with acid/base neutralization. This RED neutralization process (REDn) approximately doubled the power density compared to a conventional RED stack (REDc), thanks to the additional salinity gradients established by H+ and OH- ions as a result of the neutralization reaction. Detailed analysis shows that the power performance, i.e., the open circuit voltage and power density, of the REDn cell was greatly limited by concentration polarization and uphill transport of ions. Addressing these issues could potentially lead to an order of magnitude improvement in power density as predicted by the Nernst equation. The current study provides a simple strategy for effectively extracting energy from the neutralization of waste acid and base solutions. Future studies shall further explore the treatment of acid mine drainage and landfill leachate with the RED chemical cell as well as its extension to a wider range of reactions.

Isotopic Labeling Reveals Active Reaction Interfaces for Electrochemical Oxidation of Lithium Peroxide.

The unresolved debate on the active reaction interface of electrochemical oxidation of lithium peroxide (Li2 O2 ) prevents rational electrode and catalyst design for lithium-oxygen (Li-O2 ) batteries. The reaction interface is studied by using isotope-labeling techniques combined with time-of-flight secondary ion mass spectrometry (ToF-SIMS) and on-line electrochemical mass spectroscopy (OEMS) under practical cell operation conditions. Isotopically labelled microsized Li2 O2 particles with an Li2 16 O2 /electrode interface and an Li2 18 O2 /electrolyte interface were fabricated. Upon oxidation, 18 O2 was evolved for the first quarter of the charge capacity followed by 16 O2 . These observations unambiguously demonstrate that oxygen loss starts from the Li2 O2 /electrolyte interface instead of the Li2 O2 /electrode interface. The Li2 O2 particles are in continuous contact with the catalyst/electrode, explaining why the solid catalyst is effective in oxidizing solid Li2 O2 without losing contact.

Cation-Directed Selective Polysulfide Stabilization in Alkali Metal-Sulfur Batteries.

Alkali metal sulfur redox chemistry offers promising potential for high-energy-density energy storage. Fundamental understanding of alkali metal sulfur redox reactions is the prerequisite for rational designs of electrode and electrolyte. Here, we revealed a strong impact of alkali metal cation (Li+, Na+, K+, and Rb+) on polysulfide (PS) stability, redox reversibility, and solid product passivation. We employed operando UV-vis spectroscopy to show that strongly negatively charged short-chain PS (e.g., S42-/S32-) is more stabilized in the electrolyte with larger cation (e.g., Rb+) than that with the smaller cation (e.g., Li+), which is attributed to a stronger cation-anion electrostatic interaction between Rb+ and S42-/S32- owing to its weaker solvation energy. In contrast, Li+ is much more strongly solvated by solvent and thus exhibits a weaker electrostatic interaction with S42-/S32-. The stabilization of short-chain PS in K+-, Rb+-sulfur cells promotes the reduction of long-chain PS to short-chain PS, leading to high discharge potential. However, it discourages the oxidation of short-chain PS to long-chain PS, leading to poor charge reversibility. Our work directly probes alkali metal-sulfur redox chemistry in operando and provides critical insights into alkali metal sulfur reaction mechanism.

Non-covalent interactions in electrochemical reactions and implications in clean energy applications.

Understanding and controlling non-covalent interactions associated with solvent molecules and redox-inactive ions provide new opportunities to enhance the reaction entropy changes and reaction kinetics of metal redox centers, which can increase the thermodynamic efficiency of energy conversion and storage devices. Here, we report systematic changes in the redox entropy of one-electron transfer reactions including [Fe(CN)6]3-/4-, [Fe(H2O)6]3+/2+ and [Ag(H2O)4]+/0 induced by the addition of redox inactive ions, where approximately twenty different known structure making/breaking ions were employed. The measured reaction entropy changes of these redox couples were found to increase linearly with higher concentration and greater structural entropy (having greater structure breaking tendency) for inactive ions with opposite charge to the redox centers. The trend could be attributed to the altered solvation shells of oxidized and reduced redox active species due to non-covalent interactions among redox centers, inactive ions and water molecules, which was supported by Raman spectroscopy. Not only were these non-covalent interactions shown to increase reaction entropy, but they were also found to systematically alter the redox kinetics, where increasing redox reaction energy changes associated with the presence of water structure breaking cations were correlated linearly with the greater exchange current density of [Fe(CN)6]3-/4-.

Superoxide Stabilization and a Universal KO2 Growth Mechanism in Potassium-Oxygen Batteries.

Rechargeable potassium-oxygen (K-O2 ) batteries promise to provide higher round-trip efficiency and cycle life than other alkali-oxygen batteries with satisfactory gravimetric energy density (935 Wh kg-1 ). Exploiting a strong electron-donating solvent, for example, dimethyl sulfoxide (DMSO) strongly stabilizes the discharge product (KO2 ), resulting in significant improvement in electrode kinetics and chemical/electrochemical reversibility. The first DMSO-based K-O2 battery demonstrates a much higher energy efficiency and stability than the glyme-based electrolyte. A universal KO2 growth model is developed and it is demonstrated that the ideal solvent for K-O2 batteries should strongly stabilize superoxide (strong donor ability) to obtain high electrode kinetics and reversibility while providing fast oxygen diffusion to achieve high discharge capacity. This work elucidates key electrolyte properties that control the efficiency and reversibility of K-O2 batteries.

Critical Role of Redox Mediator in Suppressing Charging Instabilities of Lithium-Oxygen Batteries.

Redox mediators have been widely applied to reduce the charge overpotentials of lithium-oxygen (Li-O2) batteries. Here, we reveal the critical role of redox mediator in suppressing the charging instability of Li-O2 batteries. Using high temporal resolution online electrochemical mass spectrometry, we show that charging with redox mediators (using lithium bromide as a model system) significantly reduces parasitic gas evolution and improves oxygen recovery efficiency. Using redox mediator transforms the charge reactions from electrochemical pathways to chemical pathways, which unexpectedly bypasses the formation of highly reactive intermediates upon electro-oxidation of lithium peroxide (Li2O2). Such transformation reduces self-amplifying degradation reactions of electrode and electrolyte in Li-O2 cells. We further show that the improved stability associated with the redox mediator is much more pronounced at higher charging rates, owing to fast charge-transfer kinetics of the redox mediator. Together, we show that employing redox mediator not only reduces the charge overpotential but also suppresses side reactions of Li-O2 cells with improved charging rate. Our work demonstrates that transforming electro-oxidation of Li2O2 to chemical oxidation of Li2O2 is a promising strategy to simultaneously mitigate charging side reactions and achieve low overpotential for the Li-O2 batteries.

Exome sequencing identifies GNB4 mutations as a cause of dominant intermediate Charcot-Marie-Tooth disease.

Charcot-Marie-Tooth disease (CMT) is a heterogeneous group of inherited neuropathies. Mutations in approximately 45 genes have been identified as being associated with CMT. Nevertheless, the genetic etiologies of at least 30% of CMTs have yet to be elucidated. Using a genome-wide linkage study, we previously mapped a dominant intermediate CMT to chromosomal region 3q28-q29. Subsequent exome sequencing of two affected first cousins revealed heterozygous mutation c.158G>A (p.Gly53Asp) in GNB4, encoding guanine-nucleotide-binding protein subunit beta-4 (Gß4), to cosegregate with the CMT phenotype in the family. Further analysis of GNB4 in an additional 88 unrelated CMT individuals uncovered another de novo mutation, c.265A>G (p.Lys89Glu), in this gene in one individual. Immunohistochemistry studies revealed that Gß4 was abundant in the axons and Schwann cells of peripheral nerves and that expression of Gß4 was significantly reduced in the sural nerve of the two individuals carrying the c.158G>A (p.Gly53Asp) mutation. In vitro studies demonstrated that both the p.Gly53Asp and p.Lys89Glu altered proteins impaired bradykinin-induced G-protein-coupled-receptor (GPCR) signaling, which was facilitated by the wild-type Gß4. This study identifies GNB4 mutations as a cause of CMT and highlights the importance of Gß4-related GPCR signaling in peripheral-nerve function in humans.

The influence of transition metal oxides on the kinetics of Li2O2 oxidation in Li-O2 batteries: high activity of chromium oxides.

Reducing the energy loss associated with Li2O2 electrochemical oxidation is paramount to the development of efficient rechargeable lithium-oxygen (Li-O2) batteries for practical use. The influence of a series of perovskites with different eg filling on the kinetics of Li2O2 oxidation was examined using Li2O2-prefilled electrodes. While LaCrO3 is inactive for oxygen evolution upon water oxidation in alkaline solution, it was found to provide the highest specific current towards Li2O2 oxidation among all the perovskites examined. Further exploration of Cr-based catalysts showed that Cr nanoparticles (Cr NP) with an average particle size of 40 nm, having oxidized surfaces, had comparable surface area activities to LaCrO3 but much greater mass activities. Unlike Pt/C and Ru/C that promote electrolyte oxidation in addition to Li2O2 oxidation, no evidence of enhanced electrolyte oxidation was found for Cr NP relative to Vulcan carbon. X-ray absorption spectroscopy at the O K and Cr L edge revealed a redox process of Cr(3+) ↔ Cr(6+) on the surface of Cr NP upon Li2O2 oxidation, which might be responsible for the enhanced oxidation kinetics of Li2O2 and the reduced charging voltages of Li-O2 batteries.

Ether-Based High-Voltage Lithium Metal Batteries: The Road to Commercialization.

Ether-based high-voltage lithium metal batteries (HV-LMBs) are drawing growing interest due to their high compatibility with the Li metal anode. However, the commercialization of ether-based HV-LMBs still faces many challenges, including short cycle life, limited safety, and complex failure mechanisms. In this Review, we discuss recent progress achieved in ether-based electrolytes for HV-LMBs and propose a systematic design principle for the electrolyte based on three important parameters: electrochemical performance, safety, and industrial scalability. Finally, we summarize the challenges for the commercial application of ether-based HV-LMBs and suggest a roadmap for future development.

Designing Nonflammable Liquid Electrolytes for Safe Li-Ion Batteries.

Li-ion batteries are essential technologies for electronic products in the daily life. However, serious fire safety concerns that are closely associated with the flammable liquid electrolyte remains a key challenge. Tremendous effort has been devoted to designing nonflammable liquid electrolytes. It is critical to gain comprehensive insights into nonflammability design and inspire more efficient approaches for building safer Li-ion batteries. This review presents current mechanistic understanding of safety issues and discusses state-of-the-art nonflammable liquid electrolytes design for Li-ion batteries based on molecule, solvation, and battery compatibility level. Various safety test methods are discussed for reliable safety risk evaluation. Finally, the challenges and perspectives of the nonflammability design for Li-ion electrolytes are summarized.

Mutations in KCND3 cause spinocerebellar ataxia type 22.

OBJECTIVE: To identify the causative gene in spinocerebellar ataxia (SCA) 22, an autosomal dominant cerebellar ataxia mapped to chromosome 1p21-q23. METHODS: We previously characterized a large Chinese family with progressive ataxia designated SCA22, which overlaps with the locus of SCA19. The disease locus in a French family and an Ashkenazi Jewish American family was also mapped to this region. Members from all 3 families were enrolled. Whole exome sequencing was performed to identify candidate mutations, which were narrowed by linkage analysis and confirmed by Sanger sequencing and cosegregation analyses. Mutational analyses were also performed in 105 Chinese and 55 Japanese families with cerebellar ataxia. Mutant gene products were examined in a heterologous expression system to address the changes in protein localization and electrophysiological functions. RESULTS: We identified heterozygous mutations in the voltage-gated potassium channel Kv4.3-encoding gene KCND3: an in-frame 3-nucleotide deletion c.679_681delTTC p.F227del in both the Chinese and French pedigrees, and a missense mutation c.1034G>T p.G345V in the Ashkenazi Jewish family. Direct sequencing of KCND3 further identified 3 mutations, c.1034G>T p.G345V, c.1013T>C p.V338E, and c.1130C>T p.T377M, in 3 Japanese kindreds. Immunofluorescence analyses revealed that the mutant p.F227del Kv4.3 subunits were retained in the cytoplasm, consistent with the lack of A-type K(+) channel conductance in whole cell patch-clamp recordings. INTERPRETATION: Our data identify the cause of SCA19/22 in patients of diverse ethnic origins as mutations in KCND3. These findings further emphasize the important role of ion channels as key regulators of neuronal excitability in the pathogenesis of cerebellar degeneration.

Working at room temperature.

A solid-state electrolyte enables a lithium-air battery to operate at 25°C.

Targeting pathogenic macrophages by the application of SHP-1 agonists reduces inflammation and alleviates pulmonary fibrosis.

Idiopathic pulmonary fibrosis is a progressive fibrotic disorder with no cure that is characterized by deterioration of lung function. Current FDA-approved drugs for IPF delay the decline in lung function, but neither reverse fibrosis nor significantly improve overall survival. SHP-1 deficiency results in hyperactive alveolar macrophages accumulating in the lung, which contribute to the induction of pulmonary fibrosis. Herein, we investigated whether employing a SHP-1 agonist ameliorates pulmonary fibrosis in a bleomycin-induced pulmonary fibrosis murine model. Histological examination and micro-computed tomography images showed that SHP-1 agonist treatment alleviates bleomycin-induced pulmonary fibrosis. Reduced alveolar hemorrhage, lung inflammation, and collagen deposition, as well as enhanced alveolar space, lung capacity, and improved overall survival were observed in mice administered the SHP-1 agonist. The percentage of macrophages collected from bronchoalveolar lavage fluid and circulating monocytes in bleomycin-instilled mice were also significantly reduced by SHP-1 agonist treatment, suggesting that the SHP-1 agonist may alleviate pulmonary fibrosis by targeting macrophages and reshaping the immunofibrotic niche. In human monocyte-derived macrophages, SHP-1 agonist treatment downregulated CSF1R expression and inactivated STAT3/NFκB signaling, culminating in inhibited macrophage survival and perturbed macrophage polarization. The expression of pro-fibrotic markers (e.g., MRC1, CD200R1, and FN1) by IL4/IL13-induced M2 macrophages that rely on CSF1R signaling for their fate-determination was restricted by SHP-1 agonist treatment. While M2-derived medium promoted the expression of fibroblast-to-myofibroblast transition markers (e.g., ACTA2 and COL3A1), the application of SHP-1 agonist reversed the transition in a dose-dependent manner. Our report indicates that pharmacological activation of SHP-1 ameliorates pulmonary fibrosis via suppression of CSF1R signaling in macrophages, reduction of pathogenic macrophages, and the inhibition of fibroblast-to-myofibroblast transition. Our study thus identifies SHP-1 as a druggable target for the treatment of IPF, and suggests that the SHP-1 agonist may be developed as an anti-pulmonary fibrosis medication that both suppresses inflammation and restrains fibroblast-to-myofibroblast transition.

Evidence of catalyzed oxidation of Li2O2 for rechargeable Li-air battery applications.

The oxidation kinetics of Li(2)O(2) was studied in a carbonate-free electrolyte using electrodes consisting of non-catalyzed and catalyzed Vulcan carbon (VC) and chemically synthesized Li(2)O(2) particles. VC and Au nanoparticles supported on VC (Au/C) were fairly inactive for catalyzing the oxidation of Li(2)O(2), where oxidation currents greater than 10 mA g(carbon)(-1) were found only at voltages equal to and greater than 4.0 V vs. Li (V(Li)). Pt and Ru nanoparticles supported on VC (Pt/C and Ru/C) could significantly increase the kinetics of Li(2)O(2) oxidation, where Li(2)O(2) could be removed largely at voltages below 4 V(Li). In addition, Pt/C and Ru/C showed quick initiation of Li(2)O(2) oxidation in contrast to VC and Au/C.

Carbon-Nitride-Based Materials for Advanced Lithium-Sulfur Batteries.

Lithium-sulfur (Li-S) batteries are promising candidates for next-generation energy storage systems owing to their high energy density and low cost. However, critical challenges including severe shuttling of lithium polysulfides (LiPSs) and sluggish redox kinetics limit the practical application of Li-S batteries. Carbon nitrides (CxNy), represented by graphitic carbon nitride (g-C3N4), provide new opportunities for overcoming these challenges. With a graphene-like structure and high pyridinic-N content, g-C3N4 can effectively immobilize LiPSs and enhance the redox kinetics of S species. In addition, its structure and properties including electronic conductivity and catalytic activity can be regulated by simple methods that facilitate its application in Li-S batteries. Here, the recent progress of applying CxNy-based materials including the optimized g-C3N4, g-C3N4-based composites, and other novel CxNy materials is systematically reviewed in Li-S batteries, with a focus on the structure-activity relationship. The limitations of existing CxNy-based materials are identified, and the perspectives on the rational design of advanced CxNy-based materials are provided for high-performance Li-S batteries.

Stabilization of AURKA by the E3 ubiquitin ligase CBLC in lung adenocarcinoma.

CBL family proteins (CBL, CBLB and CBLC in mammals) are E3 ubiquitin ligases of protein tyrosine kinases. CBL mediates the lysosomal degradation of activated EGFR through K63-linked ubiquitination, while CBLC has an oncogenic function by positively regulating EGFR activation through K6 and K11-linked ubiquitination in EGFR mutant lung adenocarcinoma (LAD). Here, we used immunoprecipitation and mass spectrometry to study the CBLC interactome, and found that CBLC is also involved in cell cycle regulation by stabilizing Aurora kinase A (AURKA). CBLC interacted with the kinase domain of AURKA and positively regulated the stability of AURKA by conjugating monoubiquitination and K11/K63-linked polyubiquitination, which are protective from degrading K11/K48 polyubiquitination. CBLC depletion markedly decreased the half-life of AURKA in cycloheximide-treated LAD cells. When LAD cells were synchronized with double thymidine block at the G1/S boundary and then released into mitotic arrest, CBLC depletion delayed the accumulation and activation of AURKA and prevented cancer cells from entering mitosis. CBLC deficiency significantly delayed cell cycle progression, reduced the mitotic population, and increased apoptosis of LAD cells. Targeting CBLC inhibited tumor growth of LAD cells and enhanced their sensitivity to paclitaxel in xenograft models. Immunohistochemical staining of the tissue microarray also revealed a positive correlation between the expression of CBLC and AURKA in normal and LAD tissues, further supporting the positive regulation of AURKA expression by CBLC. In summary, these findings indicate that the oncogenic E3 ligase CBLC plays a role in mitotic entry by stabilizing AURKA via ubiquitination in LAD. This work demonstrates that targeting CBLC combined with paclitaxel might be a potential option for the treatment of LAD patients who have no available targeted therapies.