Cycling Li-O₂ batteries via LiOH formation and decomposition.

The rechargeable aprotic lithium-air (Li-O2) battery is a promising potential technology for next-generation energy storage, but its practical realization still faces many challenges. In contrast to the standard Li-O2 cells, which cycle via the formation of Li2O2, we used a reduced graphene oxide electrode, the additive LiI, and the solvent dimethoxyethane to reversibly form and remove crystalline LiOH with particle sizes larger than 15 micrometers during discharge and charge. This leads to high specific capacities, excellent energy efficiency (93.2%) with a voltage gap of only 0.2 volt, and impressive rechargeability. The cells tolerate high concentrations of water, water being the dominant proton source for the LiOH; together with LiI, it has a decisive impact on the chemical nature of the discharge product and on battery performance.This work was partially supported by the Assistant Secretary for Energy Efficiency and Renewable Energy, Office of Vehicle Technologies of the U.S. Department of Energy under Contract No. DE-AC02-05CH11231, under the Batteries for Advanced Transportation Technologies (BATT) Program subcontract #7057154 (WY, ML, PB), EPSRC (TL), Johnson Matthey (AM) and Marie Curie Actions (PB and ML).This is the author accepted manuscript. The final version is available from AAAS via http://dx.doi.org/10.1126/science.aac773

TCGM: An Information-Theoretic Framework for Semi-Supervised Multi-Modality Learning

Fusing data from multiple modalities provides more information to train machine learning systems. However, it is prohibitively expensive and time-consuming to label each modality with a large amount of data, which leads to a crucial problem of semi-supervised multi-modal learning. Existing methods suffer from either ineffective fusion across modalities or lack of theoretical guarantees under proper assumptions. In this paper, we propose a novel information-theoretic approach, namely \textbf{T}otal \textbf{C}orrelation \textbf{G}ain \textbf{M}aximization (TCGM), for semi-supervised multi-modal learning, which is endowed with promising properties: (i) it can utilize effectively the information across different modalities of unlabeled data points to facilitate training classifiers of each modality (ii) it has theoretical guarantee to identify Bayesian classifiers, i.e., the ground truth posteriors of all modalities. Specifically, by maximizing TC-induced loss (namely TC gain) over classifiers of all modalities, these classifiers can cooperatively discover the equivalent class of ground-truth classifiers; and identify the unique ones by leveraging limited percentage of labeled data. We apply our method to various tasks and achieve state-of-the-art results, including news classification, emotion recognition and disease prediction.Comment: ECCV 2020 (oral

Fluoroethylene Carbonate and Vinylene Carbonate Reduction: Understanding Lithium-Ion Battery Electrolyte Additives and Solid Electrolyte Interphase Formation

We have synthesized the products of fluoroethylene carbonate (FEC) and vinylene carbonate (VC) via lithium naphthalenide reduction. By analyzing the resulting solid precipitates and gas evolution, our results confirm that both FEC and VC decomposition products include HCO$_2$Li, Li$_2$C$_2$O$_4$, Li$_2$CO$_3$, and polymerized VC. For FEC, our experimental data supports a reduction mechanism where FEC reduces to form VC and LiF, followed by subsequent VC reduction. In the FEC reduction product, HCO$_2$Li, Li$_2$C$_2$O$_4$, and Li$_2$CO$_3$ were found in smaller quantities than in the VC reduction product, with no additional fluorine environments being detected by solid-state nuclear magnetic resonance or X-ray photoelectron spectroscopy analysis. With these additives being practically used in higher (FEC) and lower (VC) concentrations in the base electrolytes of lithium-ion batteries, our results suggest that the different relative ratios of the inorganic and organic reduction products formed by their decomposition may be relevant to the chemical composition and morphology of the solid electrolyte interphase formed in their presence.This work was partially supported by the Assistant Secretary for Energy Efficiency and Renewable Energy, Office of Vehicle Technologies of the U.S. Department of Energy under Contract No. DE-AC02-05CH11231, under the Batteries for Advanced Transportation Technologies (BATT) Program subcontract #7057154. This work was partially supported by the U.S. Department of Energy EPSCoR Implementation Award Grant DE-SC0007074 for B.L.L., B.S.P., and T.Y. A.L.M. is an awardee of a Schiff Foundation Studentship and a nanoDTC Associate. M.L. is an awardee of the Weizmann Institute of Science - National Postdoctoral Award for Advancing Women in Science and thanks the EU Marie Curie intra-European fellowship for funding

Ab initio structure search and in situ 7Li NMR studies of discharge products in the Li-S battery system.

The high theoretical gravimetric capacity of the Li-S battery system makes it an attractive candidate for numerous energy storage applications. In practice, cell performance is plagued by low practical capacity and poor cycling. In an effort to explore the mechanism of the discharge with the goal of better understanding performance, we examine the Li-S phase diagram using computational techniques and complement this with an in situ (7)Li NMR study of the cell during discharge. Both the computational and experimental studies are consistent with the suggestion that the only solid product formed in the cell is Li2S, formed soon after cell discharge is initiated. In situ NMR spectroscopy also allows the direct observation of soluble Li(+)-species during cell discharge; species that are known to be highly detrimental to capacity retention. We suggest that during the first discharge plateau, S is reduced to soluble polysulfide species concurrently with the formation of a solid component (Li2S) which forms near the beginning of the first plateau, in the cell configuration studied here. The NMR data suggest that the second plateau is defined by the reduction of the residual soluble species to solid product (Li2S). A ternary diagram is presented to rationalize the phases observed with NMR during the discharge pathway and provide thermodynamic underpinnings for the shape of the discharge profile as a function of cell composition.Fellowship support to KAS from the ConvEne IGERT Program of the National Science Foundation (DGE 0801627) is gratefully acknowledged. AJM acknowledges the support from the Winton Programme for the Physics of Sus-tainability. PDM and DSW thank the UK-EPSRC for financial support. This research made use of the shared experimental facilities of the Materials Research Laboratory (MRL), sup-ported by the MRSEC Program of the NSF under Award No. DMR 1121053. The MRL is a member of the NSF-funded Mate-rials Research Facilities Network (www.mrfn.org). CPG and ML thank the U.S. DOE Office of Vehicle Technologies (Con-tract No. DE-AC02-05CH11231) and the EU ERC (via an Ad-vanced Fellowship to CPG) for funding.This is the final published version. It first appeared at http://pubs.acs.org/doi/abs/10.1021/ja508982p

Theory and practice: bulk synthesis of C3B and its H2- and Li-storage capacity.

Previous theoretical studies of C3B have suggested that boron-doped graphite is a promising H2- and Li-storage material, with large maximum capacities. These characteristics could lead to exciting applications as a lightweight H2-storage material for automotive engines and as an anode in a new generation of batteries. However, for these applications to be realized a synthetic route to bulk C3B must be developed. Here we show the thermolysis of a single-source precursor (1,3-(BBr2)2C6H4) to produce graphitic C3B, thus allowing the characteristics of this elusive material to be tested for the first time. C3B was found to be compositionally uniform but turbostratically disordered. Contrary to theoretical expectations, the H2- and Li-storage capacities are lower than anticipated, results that can partially be explained by the disordered nature of the material. This work suggests that to model the properties of graphitic materials more realistically, the possibility of disorder must be considered.We thank the ERC (Advance Investigator awards for D.S.W., C.P.G.), the EPSRC (T.C.K., P.D.M., H.G., J.C.), and the Spanish Ministerio de Economia y Competitividad (under grants ENE2011-24-412 and IPT-2011-1553-420000). We thank John Bulmer for Raman spectroscopy and Keith Parmenter for glass blowing. We thank the Schlumberger Gould Research Centre for XPS analysis.This is the author accepted manuscript. The final version is available from Wiley via http://dx.doi.org/10.1002/anie.20141220

Comprehensive study of the CuF<inf>2</inf> conversion reaction mechanism in a lithium ion battery

Conversion materials for lithium ion batteries have recently attracted considerable attention due to their exceptional specific capacities. Some metal fluorides, such as CuF2, are promising candidates for cathode materials owing to their high operating potential, which stems from the high electronegativity of fluorine. However, the high ionicity of the metal–fluorine bond leads to a large band gap that renders these materials poor electronic conductors. Nanosizing the active material and embedding it within a conductive matrix such as carbon can greatly improve its electrochemical performance. In contrast to other fluorides, such as FeF2 and NiF2, good capacity retention has not, however, been achieved for CuF2. The reaction mechanisms that occur in the first and subsequent cycles and the reasons for the poor charge performance of CuF2 are studied in this paper via a variety of characterization methods. In situ pair distribution function analysis clearly shows CuF2 conversion in the first discharge. However, few structural changes are seen in the following charge and subsequent cycles. Cyclic voltammetry results, in combination with in situ X-ray absorption near edge structure and ex situ nuclear magnetic resonance spectroscopy, indicate that Cu dissolution is associated with the consumption of the LiF phase, which occurs during the first charge via the formation of a Cu1+ intermediate. The dissolution process consequently prevents Cu and LiF from transforming back to CuF2. Such side reactions result in negligible capacity in subsequent cycles and make this material challenging to use in a rechargeable battery.We acknowledge the funding from the U.S. DOE BES via funding to the EFRC NECCES, an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences under Award Number DE-SC0001294 (support for Rosa Robert and Lin-Shu Du) and EPSRC via the “nanoionics” programme grant (support for Xiao Hua). Use of the National Synchrotron Light Source (NSLS), Brookhaven National Laboratory (BNL), was supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, under Contract No. DE-AC02-98CH10886. Use of the Advanced Photon Source, an Office of Science User Facility operated for the U.S. Department of Energy (DOE) Office of Science by Argonne National Laboratory, was supported by the U.S. DOE under Contract No. DE-AC02-06CH11357.This is the final published version of the article. It first appeared at http://pubs.acs.org/doi/abs/10.1021/jp503902z and is posted here under the terms of ACS's Editors' Choice scheme (http://pubs.acs.org/page/policy/authorchoice_termsofuse.html)