Marking the counterfactual: ERP evidence for pragmatic processing of German subjunctives

Counterfactual conditionals are frequently used in language to express potentially valid reasoning from factually false suppositions. Counterfactuals provide two pieces of information: their literal meaning expresses a suppositional dependency between an antecedent (If the dice had been rigged…) and a consequent (… then the game would have been unfair). Their second, backgrounded meaning refers to the opposite state of affairs and suggests that, in fact, the dice were not rigged and the game was fair. Counterfactual antecedents are particularly intriguing because they set up a counterfactual world which is known to be false, but which is nevertheless kept to when evaluating the conditional's consequent. In the last years several event-related potential (ERP) studies have targeted the processing of counterfactual consequents, yet counterfactual antecedents have remained unstudied. We present an EEG/ERP investigation which employed German conditionals to compare subjunctive mood (which marks counterfactuality) with indicative mood at the critical point of mood disambiguation via auxiliary introduction in the conditional's antecedent. Conditional sentences were presented visually one word at a time. Participants completed an acceptability judgment and probe detection task which was not related to the critical manipulation of linguistic mood. ERPs at the point of mood disambiguation in the antecedent were compared between indicative and subjunctive. Our main finding is a transient negative deflection in frontal regions for subjunctive compared to indicative mood in a time-window of 450–600 ms. We discuss this novel finding in respect to working memory requirements for rule application and increased referential processing demands for the representation of counterfactuals' dual meaning. Our result suggests that the counterfactually implied dual meaning is processed without any delay at the earliest point where counterfactuality is marked by subjunctive mood

In Situ Ambient Pressure X-ray Photoelectron Spectroscopy Studies of Lithium-Oxygen Redox Reactions

The lack of fundamental understanding of the oxygen reduction and oxygen evolution in nonaqueous electrolytes significantly hinders the development of rechargeable lithium-air batteries. Here we employ a solid-state Li4+xTi5O12/LiPON/LixV2O5 cell and examine in situ the chemistry of Li-O2 reaction products on LixV2O5 as a function of applied voltage under ultra high vacuum (UHV) and at 500 mtorr of oxygen pressure using ambient pressure X-ray photoelectron spectroscopy (APXPS). Under UHV, lithium intercalated into LixV2O5 while molecular oxygen was reduced to form lithium peroxide on LixV2O5 in the presence of oxygen upon discharge. Interestingly, the oxidation of Li2O2 began at much lower overpotentials (~240 mV) than the charge overpotentials of conventional Li-O2 cells with aprotic electrolytes (~1000 mV). Our study provides the first evidence of reversible lithium peroxide formation and decomposition in situ on an oxide surface using a solid-state cell, and new insights into the reaction mechanism of Li-O2 chemistry.National Science Foundation (U.S.) (Materials Research Science and Engineering Center (MRSEC) Program, Award DMR-0819762)United States. Dept. of Energy (Assistant Secretary for Energy Efficiency and Renewable Energy, Office of FreedomCAR and Vehicle Technologies of the U. S. Department of Energy under contract no. DE-AC03-76SF00098)Lawrence Berkeley National LaboratoryUnited States. Dept. of Energy (Office of Basic Energy Sciences, Materials Sciences and Engineering

Rate-Dependent Nucleation and Growth of NaO2 in Na-O2 Batteries

Understanding the oxygen reduction reaction kinetics in the presence of Na ions and the formation mechanism of discharge product(s) is key to enhancing Na–O2 battery performance. Here we show NaO2 as the only discharge product from Na–O2 cells with carbon nanotubes in 1,2-dimethoxyethane from X-ray diffraction and Raman spectroscopy. Sodium peroxide dihydrate was not detected in the discharged electrode with up to 6000 ppm of H2O added to the electrolyte, but it was detected with ambient air exposure. In addition, we show that the sizes and distributions of NaO2 can be highly dependent on the discharge rate, and we discuss the formation mechanisms responsible for this rate dependence. Micron-sized (∼500 nm) and nanometer-scale (∼50 nm) cubes were found on the top and bottom of a carbon nanotube (CNT) carpet electrode and along CNT sidewalls at 10 mA/g, while only micron-scale cubes (∼2 μm) were found on the top and bottom of the CNT carpet at 1000 mA/g, respectively.Seventh Framework Programme (European Commission) (Marie Curie International Outgoing Fellowship, 2007-2013))National Science Foundation (U.S.) (MRSEC Program, award number DMR-0819762)Robert Bosch GmbH (Bosch Energy Research Network (BERN) Grant)China Clean Energy Research Center-Clean Vehicles Consortium (CERC-CVC) (award number DE-PI0000012)Skolkovo Institute of Science and Technology (Skoltech-MIT Center for Electochemical Energy Storage

Current status and future perspectives of lithium metal batteries

With the lithium-ion technology approaching its intrinsic limit with graphite-based anodes, Li metal is recently receiving renewed interest from the battery community as potential high capacity anode for next-generation rechargeable batteries. In this focus paper, we review the main advances in this field since the first attempts in the mid-1970s. Strategies for enabling reversible cycling and avoiding dendrite growth are thoroughly discussed, including specific applications in all-solid-state (inorganic and polymeric), Lithium–Sulfur (Li–S) and Lithium-O2 (air) batteries. A particular attention is paid to recent developments of these battery technologies and their current state with respect to the 2030 targets of the EU Integrated Strategic Energy Technology Plan (SET-Plan) Action 7

Materials challenges in rechargeable lithium-air batteries

Y.S-H., N.O.-V. and D.G.K. acknowledge the Robert Bosch Company for a Bosch Energy Research Network Grant, the CERC-CVC US China Clean Energy Research Center-Clean Vehicles Consortium of the Department of Energy (under award number DE—PI0000012), and the MRSEC program of the National Science Foundation for their support (under award number DMR—0819762). N.O.-V. acknowledges a Marie Curie International Outgoing Fellowship within the seventh European Community Framework Programme (2012). P.G.B. acknowledges the EPSRC for financial support, including the SUPERGEN program. S.A.F. acknowledges financial support by the Austrian Federal Ministry of Economy, Family and Youth and the Austrian National Foundation for Research, Technology and Development.Lithium-air batteries have received extraordinary attention recently owing to their theoretical gravimetric energies being considerably higher than those of Li-ion batteries. There are, however, significant challenges to practical implementation, including low energy efficiency, cycle life, and power capability. These are due primarily to the lack of fundamental understanding of oxygen reduction and evolution reaction kinetics and parasitic reactions between oxygen redox intermediate species and nominally inactive battery components such as carbon in the oxygen electrode and electrolytes. In this article, we discuss recent advances in the mechanistic understanding of oxygen redox reactions in nonaqueous electrolytes and the search for electrolytes and electrode materials that are chemically stable in the oxygen electrode. In addition, methods to protect lithium metal against corrosion by water and dendrite formation in aqueous lithium-air batteries are discussed. Further materials innovations lie at the heart of research and development efforts that are needed to enable the development of lithium-oxygen batteries with enhanced round-trip efficiency and cycle life.Publisher PDFPeer reviewe

H2O2 Decomposition Reaction as Selecting Tool for Catalysts in Li-O2 Cells

The decomposition reaction of H2O2 aqueous solutions (H2O2 → H2O+ 1/2 O2) catalyzed by transition metal oxide powders has been compared with the charging voltage of nonaqueous Li-O2 cells containing the same catalyst. An inverse linear relationship between Ln k (rate constant for the H2O 2 decomposition) and the charging voltage has been found, despite differences in media and possible mechanistic differences. The results suggest that the H2O2 decomposition may be a reliable, useful, and fast screening tool for materials that promote the charging process of the Li-O2 battery and may ultimately give insight into the charging mechanism. © 2010 The Electrochemical Society

Electrochemical Oxidation of Lithium Carbonate Generates Singlet Oxygen.

Solid alkali metal carbonates are universal passivation layer components of intercalation battery materials and common side products in metal-O2 batteries, and are believed to form and decompose reversibly in metal-O2 /CO2 cells. In these cathodes, Li2 CO3 decomposes to CO2 when exposed to potentials above 3.8 V vs. Li/Li+ . However, O2 evolution, as would be expected according to the decomposition reaction 2 Li2 CO3 →4 Li+ +4 e- +2 CO2 +O2 , is not detected. O atoms are thus unaccounted for, which was previously ascribed to unidentified parasitic reactions. Here, we show that highly reactive singlet oxygen (1 O2 ) forms upon oxidizing Li2 CO3 in an aprotic electrolyte and therefore does not evolve as O2 . These results have substantial implications for the long-term cyclability of batteries: they underpin the importance of avoiding 1 O2 in metal-O2 batteries, question the possibility of a reversible metal-O2 /CO2 battery based on a carbonate discharge product, and help explain the interfacial reactivity of transition-metal cathodes with residual Li2 CO3