Office Of Biological Research Articles

Towards quantifying microbial dispersal in the environment.

Towards quantifying microbial dispersal in the environment.

Coccidioidomycosis (Valley Fever) Case Data for the Southwestern United States

We compiled a coccidioidomycosis (Valley fever) case database for three states in the southwestern United States (US). Currently, county-level, monthly case counts are available from 2000–2015 for Arizona, California, and Nevada. We collected these data from each respective state public health agency. The Valley fever case database is available on GitHub, at https://github.com/valleyfever/valleyfevercasedata. This database may be used to examine relationships between the number of Valley fever cases and hypothesized explanatory variables such as environmental conditions, social determinants, human behavior, occupational activities, public policies, or other risk factors. We aim to provide regular updates to this database and include more states as data become available. Funding statement: M. E. Gorris received support from a Department of Defense (DoD), National Defense Science & Engineering Graduate Fellowship (32 CFR 168a). M. E. Gorris, L. A. Cat, and M. Matlock thank the UC Irvine Data Science Initiative for their funding and support. L. A. Cat acknowledges funding and support from the UC-Mexico Initiative. M. Matlock is also supported by Water UCI and the UCI Graduate Division. K. K. Treseder is supported by US NSF (EAR-1411942 and DEB-1457160) and the US Department of Energy, Office of Science, Office of Biological and Environmental Research (BER), under Award Numbers DE-PS02-09ER09-25 and DE-SC001641. J. T. Randerson received support from the Gordon and Betty Moore Foundation (GBMF#3269), NASA Soil Moisture and Interdisciplinary Science Program, and the U.S. Dept. of Energy Office of Science RUBISCO Science Focus Area. C. S. Zender acknowledges support from the Borrego Valley Endowment Fund and DOE ACME DE-SC0012998.

(Invited) Development of Dual-Salts/Carbonate-Solvents Electrolytes for Fast Charging and Stable Cycling Lithium Metal Batteries

Rechargeable lithium (Li) metal batteries have received increasing attentions in recent years because of their high theoretical energy densities from the contribution of Li metal anode that has an ultrahigh theoretical specific capacity (3860 mAh g-1), the lowest redox potential (-3.040 V vs. the standard hydrogen electrode) and a low gravimetric density (0.534 g cm-3). However, significant challenges including Li dendrite growth and low Coulombic efficiency still impede the successful deployment of rechargeable Li metal batteries. A lot of efforts have been made in the past 45 years to address these problems, including the application of polymer electrolytes, solid-state electrolytes, ionic liquids, highly concentrated liquid electrolytes, additives, protecting layers, interlayers between Li and separator, nanoscale design, selective deposition, Li-reduced graphene oxide composites, and so on. Although some progresses have been achieved the challenges still remain. It has been reported that ether-based electrolytes are relatively stable with Li metal anode and can allow Li metal anodes to be cycled at reasonably high charging current densities, but these electrolytes are not stable at voltages above 4 V vs. Li/Li+. The conventional Li-ion battery electrolytes based on LiPF6/carbonate-solvents are stable at least up to 4.3 V but they suffer from the low Coulombic efficiency and poor charging current densities due to the reactivity of Li metal with LiPF6 salt and carbonate solvents. In the talk, we present the development of electrolytes based on LiTFSI-LiBOB dual-salt in carbonate solvent mixtures for rechargeable Li metal batteries with conventional Li-ion battery cathodes. It has been found that the dual-salt electrolytes greatly enhance the performances of Li metal batteries in terms of long-term cycling stability and fast charging capability over the conventional LiPF6/carbonate electrolytes. The dual-salt electrolytes also protect Li metal anodes by suppressing the corrosions of Li metal caused by the reactions of Li metal and electrolytes. Certain additives at a small amount level can even further significantly protect the Li metal anode and improve the battery performances. The possible mechanisms have been proposed based on the comprehensive characterizations. The details of the results will be reported at the meeting. Acknowledgements The research has been supported by the Assistant Secretary for Energy Efficiency and Renewable Energy, Office of Vehicle Technologies of the U.S. Department of Energy (DOE) through the Advanced Battery Materials Research (BMR) Program and the Battery500 Consortium. The microscopy and spectroscopy measurements were performed at the Environmental Molecular Sciences Laboratory, a national scientific user facility sponsored by the DOE’s Office of Biological and Environmental Research and located at Pacific Northwest National Laboratory.

(Invited) CsPF6 and Propylene Carbonate in Conventional LiPF6/Carbonate Electrolytes for Enhanced Lithium-Ion Battery Performances in Wide Temperature Range

Lithium-ion batteries (LIBs) have achieved great successes in portable electronic devices and have now started to enter the large-scale energy storage applications in transportations (such as pure electric vehicles and plug-in hybrid electric vehicles) and smart grid. Graphite is widely used as the anode material in the state-of-the-art LIBs. However, the graphite anode is usually only compatible with an ethylene carbonate (EC)-based electrolyte. In a propylene carbonate (PC)-containing electrolyte, which is advantageous over the EC-based counterpart due to its wider temperature range and lower cost, the graphite anode experiences significant exfoliation problem by the PC intercalation during the Li+ intercalation at charging steps. Thus a PC-containing electrolyte cannot be used in LIBs with graphite anode unless some solid electrolyte interphase (SEI) film-formation additives are included in the electrolytes. Such SEI formation additives normally contain unsaturated bonds or are unstable cyclic compounds, e.g. vinylene carbonate (VC), fluoroethylene carbonate (FEC), and lithium bis(oxalato)borate (LiBOB). They play an important role in the protection of the graphite structure from destruction by PC intercalation. However, these additives usually result in a thick SEI layer, which greatly reduces rate capability, limits low-temperature performance and hampers cycling stability at elevated temperatures through additional impedance and poor thermal stability.Recently, we have demonstrated that cesium cation (Cs+) as a novel electrolyte additive can direct the formation of a uniform, ultrathin and compact SEI layer on graphite electrode surface in EC-PC-containing electrolytes.[1] This SEI can not only significantly improve the compatibility between graphite anode and PC-containing electrolyte, but also lead to superior rate capability, enhanced low-temperature discharge performance, and excellent cycling stability at elevated temperatures.We also foundthat PC content in the electrolytes has great effect on the performances of graphite anode in half cells and full cells, and an optimal PC content of 20% by weight in solvent mixtures is identified.[2] The synergistic effects of Cs+ additive and appropriate amount of PC enable the formation of a robust, ultrathin and compact SEI layer on the surface of graphite electrode, which is only permeable for de-solvated Li+ ions and allows fast Li+ transport through it. In the continuation study, we further optimized the electrolyte formulations with CsPF6 additive by adjusting the EC and PC contents in electrolytes and evaluated the performances of graphite||LiNi0.80Co0.15Al0.05O2 full cells in terms of cycling at room temperature and elevated temperature, rate capacity and low-temperature discharge. One optimized electrolyte formulation is found to give about 70% discharge capacity retention at -40°C when compared to the room temperature discharge of the full cells, and simultaneously maintains other excellent performances. It is indicated that the optimal electrolyte consisting of CsPF6 and PC in conventional LiPF6/EC-based electrolyte is of great potential use in the state-of-the-art LIBs. The details of the results will be reported at the meeting. Acknowledgements This work was supported by the Assistant Secretary for Energy Efficiency and Renewable Energy, Office of Vehicle Technologies, the Advanced Battery Materials Research Programs of the U.S. Department of Energy (DOE), and the Laboratory Directed Research and Development (LDRD) Project under the Technology Investment Program at Pacific Northwest National Laboratory (PNNL). The microscopy and spectroscopy measurements were performed at the Environmental Molecular Sciences Laboratory, a national scientific user facility sponsored by the DOE’s Office of Biological and Environmental Research and located at PNNL.

The Effects of Synthesis Conditions on the Performances of Ni-Rich LiNixMnyCozO2 Cathode Materials for Lithium-Ion Batteries

Rechargeable lithium-ion batteries (LIBs) have become the dominant power sources not only for the consumer electronic devices but also for the pure electric vehicles (EVs) and plug-in electric vehicles (PHEVs) because of their high energy density, light weight and long cycle life. The increasing need on minimizing global warming and environmental pollution have accelerated the development of EVs. With the state of the art LIBs used in automobile industry, the driving range of EVs is still far behind those of conventional vehicles using internal combustion engines. Therefore, there is an urgent need to further improve both energy density and power capability of LIBs, to improve the driving range and decrease the recharging time. To meet these requirements, a lot of effort has been made in the search of high energy density electrode materials, especially the cathode materials. Recently, Ni-rich layered cathode materials LiNixMnyCozO2 (x ≥ 0.6) have received great attention as a potential cathode alternative due to their high achievable discharge capacity (200~220 mAh g-1),1 representing a significant improvement in energy density (~780 Wh kg-1) as compared to LiCoO2 (~570 Wh kg-1) and spinel LiMn2O4 (~440 Wh kg-1). Ni-rich cathode materials also show much higher lithium ion diffusion coefficients, signifying a superior power density as compared to other LiNixMnyCozO2 cathodes with lower Ni contents.2 The other advantage of Ni-rich cathode materials is the reduction of production cost owing to the reduced Co content. However, there are still some technical challenges hindering the mass applications of Ni-rich cathode materials, including (i) Li/Ni cation mixing due to the difficulty in maintaining all the Ni in 3+ valence state, (ii) micro strain and micro crack formation due to the significant volume variation during charge/discharge processes, (iii) safety issue because of the aggressive thermal reactions between the delithiated Ni-rich materials and the electrolyte. Much effort has been devoted to improving the electrochemical performance of the Ni-rich cathode materials.3 Representative approaches include lattice doping, surface treatment/modification, tuning the material compositions, and a smart design of core-shell or concentration gradient structures. Other than these useful treatment and design, the synthetic conditions, such as co-precipitation pH value, particle size, lithium content, calcination temperature, calcination atmosphere (O2, air etc.), heating/cooling rates, also play an important role in manipulating the material structural properties and thus influencing the electrochemical performances of prepared Ni-rich cathode materials. Herein, we systematically investigated the effects of calcination temperature on the primary particle size, cation mixing and the electrochemical performances of Ni-rich cathode materials. It is found that higher calcination temperature leads to considerable increase of primary particle size, which is supposed to largely reduce the side reactions between cathode material and the electrolytes. However, the materials prepared at high temperatures exhibited much poorer long-term cycling stability both at room temperature and high temperature of 60oC, in addition to their inferior rate performance. Therefore, the fundamental reasons behind this phenomenon are investigated in detail, which will be presented and discussed during the meeting. Acknowledgements This work was supported by the Assistant Secretary for Energy Efficiency and Renewable Energy, Office of Vehicle Technologies, the Advanced Battery Materials Research Programs of the U.S. Department of Energy (DOE). The microscopy and spectroscopy measurements were performed at the Environmental Molecular Sciences Laboratory, a national scientific user facility sponsored by the DOE’s Office of Biological and Environmental Research and located at Pacific Northwest National Laboratory. References 1) A. Manthiram, J.C. Knight, S-T, Myung, S-M Oh, Y-K Sun, Adv. Energy Mater., 1501010 (2015). 2) Y. Wei, J. Zheng, S. Cui, X. Song, Y. Su, W. Deng, Z. Wu, X. Wang, W. Wang, M. Rao, Y. Lin, C. Wang, K. Amine, F. Pang, J. Am. Chem. Soc., 137, 8364 (2015). 3) W. Liu, P. Oh, X. Liu, M-J Lee, W. Cho, S. Chae, Y. Kim, J. Cho, Angew. Chem. Int. Ed., 54, 4440 (2015).

A Stable Carbon-Free Cathode for Rechargeable Lithium-Oxygen Battery with Long Cycle Performance

Lithium-oxygen (Li-O2) batteries have extremely high theoretical specific capacities and energy densities than Li-ion batteries. It is estimated that a practical Li-O2 battery could provide 3-5 times gravimetric energy density of conventional Li-ion batteries. The cathode active material (oxygen) is not stored in the Li-O2 battery and can be obtained from the environment outside the batteries. However, the cycle performances of these Li-O2 batteries are still limited by the stability of the air electrode and the electrolyte. Carbon-based electrodes are believed to decompose during charge and promote electrolyte decomposition as well. The fabrication of a stable and highly active carbon-free cathode for both the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) becomes a great challenge at present for the development of rechargeable Li-O2battery. Recently, some carbon-free cathode materials have been reported, including noble metals,1 oxides,2 and carbides.3 Metal oxides have low conductivities and are mainly utilized at low current densities. Noble metals show outstanding performance but may not be applicable due to the high cost and high density. Carbides can achieve good bi-functional activities for ORR and OER and be with low cost. However, only TiC was reported to achieve high cycle performance as a carbon-free cathode for Li-O2 batteries so far. Here we report the application of a novel material for the carbon-free cathode of Li-O2 batteries. The battery can be stably operated for more than 200 cycles with a stable voltage profile under the capacity-limited condition. With the aid of structure and composition characterizations, the mechanism of discharge and charge process is also investigated. This novel material is very promising for the use as an alternative carbon-free cathode, as well as for studying and exploring the stable electrolyte in rechargeable Li-O2batteries. Acknowledgements This work was supported by the Assistant Secretary for Energy Efficiency and Renewable Energy, Office of Vehicle Technologies, the Advanced Battery Materials Research Programs of the U.S. Department of Energy (DOE). The microscopy and spectroscopy measurements were performed at the Environmental Molecular Sciences Laboratory, a national scientific user facility sponsored by the DOE’s Office of Biological and Environmental Research and located at Pacific Northwest National Laboratory. References Z. Peng, S. A. Freunberger, Y. Chen, P. G. Bruce, A Reversible and Higher-Rate Li-O2 Battery, Science., 337, 563 (2012). M. M. O. Thotiyl, S. A. Freunberger, Z. Peng, Y. Chen, Z. Liu, P. G. Bruce, A stable cathode for the aprotic Li-O2 battery, Nature Materials, 12, 1050 (2013). F. Li, D.M. Tang, Y. Chen, D. Golberg, H. Kitaura, T. Zhang, A. Yamada, H. Zhou, Ru/ITO: A Carbon-Free Cathode for Nonaqueous Li-O2 Battery, Nano Lett., 13, 4702 (2013).

Stable Operation of Lithium Metal Batteries by the Formation of Transient High Concentration Electrolyte Layer during Fast Discharge

Lithium (Li) metal anode has an ultrahigh theoretical capacity of 3860 mAh/g and the lowest electrochemical potential at -3.040 V vs. standard hydrogen electrode, which makes the rechargeable Li metal batteries as the “holy grail” of energy storage systems.1 However, the development and application of rechargeable Li metal batteries has been hindered in the past decades mainly due to two major problems¾the Li dendrite growth on Li anode during repeated charge/discharge processes and the low Coulombic efficiency. Although several approaches have been reported to suppress Li dendrite growth on Li metal, including forming Li alloys, adding electrolyte additives, using blocking electrolyte membranes, and to improve Coulombic efficiency, the enhancement on Li protection so far is not satisfactory. Recently, highly concentrated ether-based electrolyte has been reported to be more compatible with Li metal anode because high concentration of Li+ ions in these electrolytes facilities the fast Li deposition/stripping even at high current density conditions.2,3 However, ether-based electrolytes may not be suitable for use at charge cutoff voltage higher than ~4.0 V due to their poor stability against oxidation. In this work, we report for the first time the significantly improved performances of Li metal batteries using a LiNi1/3Mn1/3Co1/3O2 (NMC) cathode and a conventional carbonate solvent-based electrolyte by an appropriate cycling protocol to generate a transient, highly concentrated Li+ ion solution layer in the vicinity of Li metal surface. The highly concentrated electrolyte formed in the vicinity of Li anode surface facilitates the formation of an SEI layer with considerably enhanced stability. It is demonstrated that a high capacity retention >80% after 500 cycles can be achieved for the moderately high areal-capacity Li metal batteries at an optimized charging/discharging process. Based on the results of morphology observation and the composition characterization of the cycled Li metal anodes, a more profound understanding of the underlying mechanism behind the improved performances has been obtained. The fundamental findings of this work provide new insights for the further development of high energy density and long cycle life Li metal batteries. Details of the investigations will be reported and discussed in the presentation. Acknowledgements This work was supported by the Assistant Secretary for Energy Efficiency and Renewable Energy, Office of Vehicle Technologies, the Advanced Battery Materials Research Programs of the U.S. Department of Energy (DOE). The microscopy and spectroscopy measurements were performed at the Environmental Molecular Sciences Laboratory, a national scientific user facility sponsored by the DOE’s Office of Biological and Environmental Research and located at Pacific Northwest National Laboratory. References A. Zhanmu, G. Chen, C. Liu, D. Neff, Q. Fang, Z. Yu, W. Xiong, Y. Wang, X. Wang, and B. Z. Jang, Energy Environ. Sci., 5, 5701 (2012). L. Suo, Y.-S. Hu, H. Li, M. Armand, and L. Chen, Nat. Commun., 4, 1481 (2013). J. Qian, W. A. Henderson, W. Xu, P. Bhattacharya, M. Engelhard, O. Borodin, and J.-G. Zhang, Nat. Commun., 6, 6362 (2015).

Behind the Stability of Graphite Anode in PC-Containing Electrolytes with a New Additive

Lithium-ion battery (LIB) is one of the most promising power sources for electronic devices and electric vehicles because of their high energy densities and relatively long lifetime. Graphite is widely used as the anode electrode material in the state-of-the-art LIBs. However, a graphite anode is usually only compatible with an ethylene carbonate (EC)-based electrolyte. In a propylene carbonate (PC)-containing electrolyte, which is advantageous over the EC-based counterpart due to its wider temperature range and higher low-temperature conductivity, the graphite anode experiences significant exfoliation problem during the initial lithium intercalation step. Thus a PC-containing electrolyte cannot be used in LIBs with graphite as the anode unless some solid electrolyte interphase (SEI) film-formation additives are included in the electrolytes. Usually these additives are electrochemically reduced predominantly on the graphite anode surface before PC is intercalated and reduced. Such additives normally contain unsaturated bonds or are unstable cyclic compounds, for instance, vinylene carbonate (VC) and fluoroethylene carbonate (FEC). They play an important role in the protection of the graphitic anode structure from destruction by PC reduction. However, these additives also have certain shortcomings. Usually these additives result in a thick SEI layer, which significantly reduces the rate capability and limits low-temperature performance and cycling stability at elevated temperatures through additional impedance and poor thermal stability. Recently, we developed a novel electrolyte additive that can suppress the PC reductive decomposition on the graphite anode without forming a thick and resistant SEI film. As shown in Figure 1, this additive can not only significantly improve the compatibility between graphite anode and PC-containing electrolyte, but also exhibit superior rate capability and excellent cycling stability at elevated temperatures.This new electrolyte additive can be applied to LIBs and other electrochemical systems using PC-containing electrolytes and graphite anodes. In this work, we systematically investigated the mechanism of the SEI formation by this additive and the protection of graphite anode in PC-containing electrolytes. Several techniques, including computational calculations and simulations, 17O nuclear magnetic resonance (NMR), “soft” electrospray ionization mass spectrometry (ESI-MS), time of flight second ion mass spectrometry (ToF-SIMS), etc. have been used to reveal the reasons behind the compatibility and stability of graphite anode in PC-containing electrolytes with this new additive. The details of the results will be reported at the meeting. Acknowledgements This work was supported by the Assistant Secretary for Energy Efficiency and Renewable Energy, Office of Vehicle Technology of the U.S. Department of Energy (DOE). The 17O NMR and ToF-SIMS measurements were performed at the Environmental Molecular Sciences Laboratory, a national scientific user facility sponsored by the DOE’s Office of Biological and Environmental Research and located at PNNL. Figure 1

SEI-Film-Suppression Additive for Enhancing Compatibility and Electrochemical Stability of Graphite Anode in PC-Based Electrolytes

Lithium-ion batteries (LIBs) are one of the most promising power sources for electric vehicles because of their high energy density and long lifetime. Graphite is widely used as anode electrode material in the state-of-the-art LIBs. However, a graphite anode is usually only compatible with an ethylene carbonate (EC)-based electrolyte. When contacting with a propylene carbonate (PC)-based electrolyte, which is advantageous over the EC-based one for its wider temperature range and higher low-temperature conductivity, the graphite anode may suffer from substantial exfoliation problem during the initial lithium intercalation step. Consequently, a PC-based electrolyte cannot be used in LIBs with graphite as the anode unless some solid electrolyte interphase (SEI) film-formation additives are introduced into the electrolytes. Usually this type of additives is reduced predominantly on the graphite electrode surface before PC is intercalated and reduced. These additives mainly contain some functional groups such as vinylene or cyclic unsaturated compounds. For example, vinylene carbonate (VC) and fluoroethylene carbonate (FEC) have been widely studied and used as additives for PC-based electrolytes. They play an important role in the protection of the structure of the graphitic anode from destruction by PC, but they also have some shortcomings. Usually these additives result in a thick SEI protective layer, which could significantly reduce the rate capability and limit low-temperature performance and cycling stability at elevated temperatures because of its additional impedance and poor thermal stability. Recently, we developed a novel electrolyte additive that can suppress the PC reductive decomposition on the graphite anode without a thick and resistant SEI film. The additive may provide a novel protective mechanism for the graphite anode in the PC-containing electrolytes without or with suppressed SEI film formation. The SEI-film-suppression additive can not only significantly improve the compatibility between graphite anode and PC-containing electrolyte, but also exhibit superior rate capability and excellent cycling stability at elevated temperatures.We believe that this new electrolyte additive can be applied to LIBs and other electrochemical systems using PC-containing electrolytes and graphite anodes. The details of the results will be reported. Acknowledgements This work was supported by the Assistant Secretary for Energy Efficiency and Renewable Energy, Office of Vehicle Technology of the U.S. Department of Energy (DOE). The electron microscopy and XRD measurements were performed at the Environmental Molecular Sciences Laboratory, a national scientific user facility sponsored by the DOE’s Office of Biological and Environmental Research and located at PNNL.

Optimization of High-Energy-Density Aqueous Zinc-Polyiodide Redox Flow Battery

Unlike traditional batteries, flow-based electrochemical energy storage systems separate the energy storage and power generation by storing the electro-active species in externally flowing electrolytes (i.e., the anolyte and catholyte) while maintaining the redox reactions at the electrode surface inside a stack. This unique architecture permits the redox flow batteries (RFBs) to independently scale the power and/or energy—a characteristic advantage along with high safety coveted by the energy industry for intermittent renewable energy integration and other grid services. Despite continuous progress, the energy density of traditional aqueous RFBs is considerably lower than that of low-end Li-ion batteries such as those with LiFePO4 cathodes. Traditional aqueous RFBs, such as all-vanadium (VRB) and Fe/Cr systems, are generally limited to < 25 Wh L-1 by both the low voltage owing to water electrolysis and the relatively low solubility of the active species. Recent research on the non-aqueous electrolyte has offered wider electrochemical stability windows and thus higher cell voltages (>2.0V), but the low solubility of the active redox species in the non-aqueous electrolytes has largely prevented the high energy densities from being achieved (in most cases less than 0.1 M, corresponding to an energy density of 5 Wh L-1 even at a higher cell voltage). Other challenges also include flammable nature, requirement of hermetic sealing, and low conductivity (which leads to current density at least one order of magnitude lower than the current aqueous system (< 0.5 mA cm-2)) of the non-aqueous electrolytes, which further limit the development of the non-aqueous systems. A high energy density aqueous flow battery with high safety is therefore still critically needed.Here, as shown in Fig. 1, we demonstrate that the zinc-polyiodide electrolyte possesses the desired ambipolar and bifunctional characteristics, as well as high solubility and benign nature, thus enabling a high-energy-density aqueous hybrid RFB. Capitalizing on the high solubility of the I-/Ix - redox species, the zinc-polyiodide flow battery (ZIB) has a theoretical energy density of ~322 Wh L-1 at the solubility limit of ZnI2 in the water (4500 g L-1, 7.0 M). We demonstrate here a discharge energy density of 166.7 Wh L-1 with 5.0 M ZnI2 electrolytes, nearly 7 times that of the current aqueous RFBs (VRB: ~25 Wh L-1) and approaching the energy density of low-end LiFePO4 cathode-based Li-ion batteries. The ZIB system is further optimized in terms of membranes and electrodes, enabling it more competitive in energy storage market. Because of the absence of highly oxidative V5+ and Br2, low-cost hydrocarbon cation exchange membranes are applied in the ZIB thus replacing the expensive Nafion membrane, making the ZIB system more attractive from a cost prospective. In addition, the catalysts or modification of current graphite felts at the cathode side can effective increase the kinetics of I-/Ix - redox couples, which enhances the energy efficiency of ZIB cell run at high current density. Acknowledgements The authors would like to acknowledge financial support from the U.S. Department of Energy’s (DOE) Office of Electricity Delivery and Energy Reliability (OE) (under Contract No. 57558). The NMR work was carried out at the Environmental and Molecular Science Laboratory at Pacific Northwest National Laboratory (PNNL), a national scientific user facility sponsored by the DOE’s Office of Biological and Environmental Research (BER). PNNL is a multi-program national laboratory operated by Battelle for DOE under Contract DE-AC05-76RL01830. Figure 1

Invited Talk: Development of Nonaqueous Redox Flow Battery Technologies

Nonaqueous redox flow batteries are generally considered to have higher energy densities than their aqueous counterparts because of their wider voltage windows. However, their performance has lagged far behind their inherent capability due to the combined limitations of redox chemistry, solubility of redox species, and cell design. Here we report a high-performance nonaqueous lithium–organic redox flow battery with a structure-modified ferrocene cathode. The ionic-liquid derivatization of ferrocene increases the solubility by more than 20 times in the supporting electrolyte (0.85 M as opposed to 0.04 M for pristine ferrocene). This improvement is confirmed by solvation chemistry studies through nuclear magnetic resonance analysis and density functional theory calculation. When coupled with a lithium-graphite hybrid anode, the flow battery exhibits a cell voltage of 3.49 V and energy efficiency over 75% (Figure 1). The method of material modification proved to be a viable way to prepare high-performance electrolyte for nonaqueous redox flow batteries.Development on the total-organic redox flow battery will also be presented. Acknowledgements The authors would like to acknowledge financial support primarily from the U.S. Department of Energy’s (DOE’s) Office of Electricity Delivery and Energy Reliability (OE) (under Contract No. 57558) and the support from Laboratory-Directed Research and Development Program (LDRD) of the Pacific Northwest National Laboratory (PNNL). The NMR characterization was supported as part of the Joint Center for Energy Storage Research, an Energy Innovation Hub funded by the U.S. Department of Energy, Office of Science, Basic Energy Sciences, and was conducted in the William R. Wiley Environmental Molecular Sciences Laboratory (EMSL), a national scientific user facility sponsored by DOE’s Office of Biological and Environmental Research and located at PNNL. PNNL is a multi-program national laboratory operated by Battelle for DOE under Contract DE-AC05-76RL01830.

Mitigating Voltage Fade in Cathode Materials By Improving Atomic Level Spatial Uniformity of Chemical Species

Lithium- and manganese-rich (LMR) layered-structure cathode materials deliver a much higher energy density than traditional cathode materials such as LiMn2O4 spinel and LiCoO2. However, significant challenges, including voltage fade and limited cycle life in LMR cathodes still remain to be overcome prior to their large-scale market penetration.Here, we report on the direct correlation between voltage fade and atomic level spatial distribution of chemical species among LMR cathode materials (Li[Li0.2Ni0.2M0.6]O2) prepared by several methods, including co-precipitation (CP), sol-gel (SG) and hydrothermal assisted (HA) methods. Quantitative chemical composition analysis was performed on these materials using large-area X-ray energy dispersive spectroscopy (XEDS) mapping. Meanwhile, we used aberration-corrected scanning transmission electron microscopy (STEM) combined with electron energy loss spectroscopy (EELS) to acquire detailed crystallographic data on Li[Li0.2Ni0.2Mn0.6]O2 cathode prepared by different methods. The atomic contrast in high-angle annular dark field (HAADF) STEM imaging identified the details of stacking and ordering in the particles while EELS chemical analysis revealed important chemistry information. We found that the materials prepared by the CP and SG methods exhibit a relatively high propensity for Ni segregation, leading to fast voltage fade and poor cycling stability. However, material prepared by the HA method exhibits very uniform Ni distribution and greatly reduced voltage fade. To the best of our knowledge, this is the first direct atomic-scale evidence to correlate atomic level cation uniformities with the electrochemical performance of cathode materials. More importantly, the voltage fade and energy degradation of LMR cathode materials can be significantly mitigated by improving the uniformity of chemical species in atomic level that are strongly affected by the preparation methods and synthesis conditions. These results also shine the light on the current debate regarding to the average/local structure of LMR cathode materials. LMR cathodes prepared by co-precipitation and sol-gel methods exhibit significant Ni segregation and dominated by LiMO2 R-3m phase, where the preferential segregation of Ni blocks lithium ion diffusion channels, weaken nickel-manganese interactions, lead to easy reduction of the manganese ions and fast voltage/capacity fade. In contrast, LMR cathodes prepared by the hydrothermal assisted method form a solid solution dominated by Li2MO3C2/m monoclinic symmetry with largely suppressed Ni segregation and are more stable against excessive lithium ion removal, enhance Ni-Mn interaction and stabilize crystal structure, leads to greatly reduced voltage fade and excellent cycling stability of LMR cathodes. Therefore, LMR cathodes with uniform distribution of chemical species (minimal Ni segregation) are very promising for use in high-energy Li-ion batteries for large-scale practical applications. The fundamental correlation between the atomic level spatial distribution of the chemical species and the functional stability of the materials found in this work also provides new perspective on the design and development of other functional materials with significantly enhanced stability. Acknowledgements This work is 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, Subcontract No. 18769, under the Batteries for Advanced Transportation Technologies program. The microscopic study described in this paper is supported by the Laboratory Directed Research and Development Program as part of the Chemical Imaging Initiative at Pacific Northwest National Laboratory (PNNL). The work was conducted in the William R. Wiley Environmental Molecular Sciences Laboratory (EMSL), a national scientific user facility sponsored by DOE’s Office of Biological and Environmental Research and located at PNNL. PNNL is operated by Battelle for the DOE under Contract DE-AC05-76RLO1830. The authors also would like to thank M. M. Thackeray for useful discussions.

Verification of O2 -• Formation during Oxygen Reduction Reaction in Li-O2 Batteries

Li-O2 battery has been regarded as one of the most promising energy storage systems for the next generation of electrical vehicles and large scale stationary applications.1 It has very high theoretical energy density compared to those of other rechargeable batteries. However, the research for Li-O2 batteries so far is still in its early stage. Significant problems on the stability of electrolyte, cathode and Li anode used in Li-O2 battery still need to be solved before its practical applications.2 In this regards, selection of stable electrolytes, substrates, and efficient catalysts are at the heart of all concerns, without which the rechargeable Li- O2 batteries will not be successful. In order to search stable electrolyte and develop highly efficient catalyst and consequently improve the cycle life of the Li-O2 battery, it is necessary to have a deep understanding on the mechanism of oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) in non-aqueous electrolytes. The mechanism of ORR and OER greatly depends on the activity of catalysts and the types of electrolyte solution environments. Superoxide radical anion (O2 -•) has been proposed as an intermediate during the discharge process, followed by a disproportionation reaction. However, no direct evidence has been found to prove this mechanism because the lifetime of superoxide radical is extremely short at room temperature and it is difficult to visualize the existence of O2 -• by using spectroscopic techniques. Recently, we have studied ORR and OER mechanisms in a non-aqueous Li-O2 battery using ex-situ electron paramagnetic resonance (EPR) technique and have successfully detected the formation of O2 -• during the ORR process (Figure 1). In the charging process, nearly no formation of O2 -•has been found during the OER process. Details of the investigations will be reported and discussed in the presentation. Acknowledgements This work was supported by the Joint Center for Energy Storage Research, an Energy Innovation Hub funded by the Basic Energy Sciences, Office of Science of the U.S. DOE. The EPR measurements were performed in the Environmental Molecular Sciences Laboratory, a national scientific user facility sponsored by the DOE’s Office of Biological and Environmental Research and located at PNNL.1. P. G. Bruce, S. A. Freunberger, L. J. Hardwick and J.-M. Tarascon, Nat Mater, 2012, 11, 19-29.2. Y. Shao, F. Ding, J. Xiao, J. Zhang, W. Xu, S. Park, J.-G. Zhang, Y. Wang and J. Liu, Adv Funct Mater, 2013, 23, 987-1004.

Introduction: Validation methods for function genome annotation

This supplement comprises a report on progress during 2007-10 on an outstanding and continuing problem. What are effective and high throughput methodologies for validating the function of genes, newly displayed within DNA sequences? The display of genomes as DNA sequence is becoming increasingly cheap and fast. Sequence comparison methodologies do serve for computationally recognizing homologues between genes in a newly displayed genome, with those of previously analyzed genomes. This is a first automated step in annotation of newly recognized, candidate genes. But there are abundant examples that follow through experimentation is needed to improve and often also to correct the first outputs of computational annotation. For newly displayed microbial genomes, about a third of the genes do not thus acquire any functional assignment. For the more complex genomes of higher species, gene coverage by automated annotation is even poorer. The DOE Office of Biological and Environmental Research (BER) participated in a 2006 workshop sponsored by the NIH National Center for Biological Information (NCBI). Numerous limitations of computational annotation were discussed. DOE responded with a call for research applications in May 2007: http://www.sc.doe.gov/grants/FAPN07-14.html . Completely solving the long standing problem of validating annotation was certainly not feasible. Rather BER sought methods which could be applied in high throughput modes, with particularly applicability to gene families or genomes related to DOE missions. Validation projects initiated through the FAPN07-14 call and review process are included herein, with complementation by a few cogent projects started earlier. Validation of gene function certainly remains an outstanding problem arena. But the suite of accomplishments and methods reported herein will surely be useful to those considering validation battles.

Crystal Structure of FolD Bifunctional Protein, a Methylenetetrahydrofolate Dehydrogenase/Cyclohydrolase from Campylobacter jejuni

Tetrahydrofolate (THF) plays a crucial role as a molecule for the production and utilization of monocarbon units in various oxidation states. Enzymes involved in THF metabolism are of pharmaceutical interest, as their function is crucial for amino acid and DNA synthesis. The interconversion of two major one‐carbon donors, methylene and methenyl groups, occurs through the sequential activities of NAD(P)‐dependent methylenetetrahydrofolate dehydrogenase (MTHFD) and methenyltetrahydrofolate cyclohydrolase (MTHFC). These activities frequently coexist as a part of a bifunctional enzyme in prokaryotes. In higher organisms, MTHFR and MTHFC are often linked together with another protein, formyl‐THF synthetase (FTHFS) and operate as a trifunctional enzyme. We have determined the crystal structure of a FolD protein, a predicted MTHFR/MTHFC from Campylobacter jejuni at 2.20 Å resolution. The protein exists as a dimer and each subunit is composed of two α/β domains that assemble to form a wide, largely hydrophobic cleft. Comparison with the structure of the homologous enzyme domain from a trifunctional human protein allowed the identification of a highly conserved cluster of basic residues that most likely participate in the binding of a THF substrate. Exploring the differences between the active sites of bacterial and human enzymes might allow the development of inhibitors specific to the bacterial target. This research was supported by the NIH contract No. HHSN272200700058C, and by the U.S. DOE, Office of Biological and Environmental Research, contract DE‐AC02‐06CH11357.

Synchrotron radiation needs for molecular environmental science

Synchrotron facilities provide exceptionally high brightness, tunable X‐ray sources that make possible a range of novel techniques allowing molecular‐scale and sometimes time‐resolved characterization of diverse types of materials. Focusing the X‐ray beam to nanometer to micrometer sizes enables spectroscopic and scattering measurements at high spatial resolution, thereby allowing study of complex, heterogeneous environmental samples in which elements of interest are commonly dilute. Such molecular‐scale characterization provides the basis for understanding fundamental reaction mechanisms, chemical speciation of trace and major elements, contaminant mobility/bioavailability, and element cycling in the hydrosphere.It is no surprise therefore that synchrotron radiation techniques, such as X‐ray absorption spectroscopy and scattering, have become core techniques in the fields of molecular environmental science (MES) and low‐temperature geochemistry (LTG). The synchrotron user group EnviroSync organized a workshop in Rockville, Md., to assess current capabilities at U.S. synchrotron facilities and future needs for these communities. Sponsorship was provided by the U.S. Department of Energy's Office of Basic Energy Sciences and Office of Biological and Environmental Remediation and by the U.S. National Science Foundation's Earth Sciences Directorate. The 50+ participants included academic and national laboratory researchers, beam line scientists, instrument designers, and facility directors and representatives. Program managers from funding agencies provided perspectives from Washington.

The nonmycorrhizal root – a strategy for survival in nutrient‐impoverished soils

The nonmycorrhizal root – a strategy for survival in nutrient‐impoverished soils

NASA RESEARCH REEVALUATED

FOR MANY YEARS, THE NATIONAL Aeronautics & Space Administration's research program has been under fire over its value and its relevance. Critics of the research efforts, administered by NASA's Office of Biological & Physical Research (OBPR), question whether the science being conducted on the space shuttle missions and the International Space Station (ISS) is important enough to justify the enormous cost. But recent events have brought into question an even more basic issue: Are human missions into space necessary? The loss of the space shuttle Columbia and its seven-member crew in the skies over the Southwest U.S. on Feb. 1 has prompted NASA to ground its remaining shuttle fleet— threatening the future of the space station—and Congress to initiate a thorough investigation of the accident and the overall space program. NASA, however, believes that, following a brief hiatus during the investigations, it will be able to get back on track with its long-range plans. I ...

The plaque-neutralization test as a measure of prior exposure to measles virus.

Journal Article The Plaque-Neutralization Test as a Measure of Prior Exposure to Measles Virus Get access Walter A. Orenstein, Walter A. Orenstein Division of Immunization, Center for Prevention Services, and the Division of Viral Diseases, Center for Infectious Diseases, Centers for Disease Control, Atlanta, Georgia; the Office of Biologics, Research and Review, the Food and Drug Administration, Bethesda, Maryland; and the Office of Health (AID), U S. Department of State, Washington, D. C. Please address requests for reprints to the Technical Information Services (WAO), Center for Prevention Services, Centers for Disease Control, Atlanta, Georgia 30333. Search for other works by this author on: Oxford Academic PubMed Google Scholar Paul Albrecht, Paul Albrecht Division of Immunization, Center for Prevention Services, and the Division of Viral Diseases, Center for Infectious Diseases, Centers for Disease Control, Atlanta, Georgia; the Office of Biologics, Research and Review, the Food and Drug Administration, Bethesda, Maryland; and the Office of Health (AID), U S. Department of State, Washington, D. C. Search for other works by this author on: Oxford Academic PubMed Google Scholar Kenneth L. Herrmann, Kenneth L. Herrmann Division of Immunization, Center for Prevention Services, and the Division of Viral Diseases, Center for Infectious Diseases, Centers for Disease Control, Atlanta, Georgia; the Office of Biologics, Research and Review, the Food and Drug Administration, Bethesda, Maryland; and the Office of Health (AID), U S. Department of State, Washington, D. C. Search for other works by this author on: Oxford Academic PubMed Google Scholar Roger Bernier, Roger Bernier Division of Immunization, Center for Prevention Services, and the Division of Viral Diseases, Center for Infectious Diseases, Centers for Disease Control, Atlanta, Georgia; the Office of Biologics, Research and Review, the Food and Drug Administration, Bethesda, Maryland; and the Office of Health (AID), U S. Department of State, Washington, D. C. Search for other works by this author on: Oxford Academic PubMed Google Scholar Kenneth J. Bart, Kenneth J. Bart Division of Immunization, Center for Prevention Services, and the Division of Viral Diseases, Center for Infectious Diseases, Centers for Disease Control, Atlanta, Georgia; the Office of Biologics, Research and Review, the Food and Drug Administration, Bethesda, Maryland; and the Office of Health (AID), U S. Department of State, Washington, D. C. Search for other works by this author on: Oxford Academic PubMed Google Scholar Elizabeth Z. Rovira Elizabeth Z. Rovira Division of Immunization, Center for Prevention Services, and the Division of Viral Diseases, Center for Infectious Diseases, Centers for Disease Control, Atlanta, Georgia; the Office of Biologics, Research and Review, the Food and Drug Administration, Bethesda, Maryland; and the Office of Health (AID), U S. Department of State, Washington, D. C. Search for other works by this author on: Oxford Academic PubMed Google Scholar The Journal of Infectious Diseases, Volume 155, Issue 1, January 1987, Pages 146–149, https://doi.org/10.1093/infdis/155.1.146 Published: 01 January 1987 Article history Received: 02 April 1986 Revision received: 25 July 1986 Published: 01 January 1987

Influenza immunization changes for elderly?

The elderly (arbitrarily defined as persons over 65 years of age) suffer influenza morbidity and mortality in disproportionate numbers. Researchers are now suggesting that changes in the dosage and/or timing of influenza immunization might help ease that burden. Older persons less often manifest an adequate immunologic response to influenza vaccination than do members of other age groups ( JAMA 1985; 253:1136-1139). Consequently, they fall victim to 90% of the excess deaths during influenza epidemics ( JAMA [LEADS FROM THE MMWR] 1985;253:3521-3535). At the Interscience Conference on Antimicrobial Agents and Chemotherapy, held in Minneapolis, two groups of scientists presented results of work aimed at achieving better protection from influenza for the elderly. Peter A. Gross, MD, director of infectious diseases, Hackensack (NJ) Medical Center, and professor of medicine at the New Jersey Medical School. Newark, NJ, aided by coworkers from Cornell University Medical College, New York City, and the Office of Biologics, Research,