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Real-time changes in the composition and structure of bismuth electrodes used for catalytic conversion of CO2 into CO were examined via X-ray absorption spectroscopy (including XANES and EXAFS), electrochemical quartz crystal microbalance (EQCM), and in situ X-ray reflectivity (XR). Measurements were performed with bismuth electrodes immersed in acetonitrile (MeCN) solutions containing a 1-butyl-3-methylimidazolium ([BMIM]+) ionic liquid promoter or electrochemically inactive tetrabutylammonium supporting electrolytes (TBAPF6 and TBAOTf). Altogether, these measurements show that bismuth electrodes are originally a mixture of bismuth oxides (including Bi2O3) and metallic bismuth (Bi0) and that the reduction of oxidized bismuth species to Bi0 is fully achieved under potentials at which CO2 activation takes place. Furthermore, EQCM measurements conducted during cyclic voltammetry revealed that a bismuth-coated quartz crystal exhibits significant shifts in resistance (ΔR) prior to the onset of CO2 reduction n...

The thermal expansion (TE) coefficients of the lithium-stable lithium-ion conducting garnet lithium lanthanum zirconium oxide (LLZ) and the effect of aluminum substitution were measured from room temperature up to 700 °C by a synchrotron-based X-ray diffraction. The typical TE value measured for the most reported composition (LLZ doped with 0.3 wt.% or 0.093 mol% aluminum) was 15.498 × 10 −6 K −1 , which is approximately twice the value reported for other garnet-type structures. As the Al(III) concentration has been observed to strongly affect the structure observed and the ionic conductivity, we also assessed its role on thermal expansion and noted only a small variation with increasing dopant concentration. The materials implications for using LLZ in a solid state battery are discussed.

One of the challenges associated with silicon as an anode material for Li-ion batteries is the formation of an unstable solid-electrolyte interphase which, forms continuously while consuming lithium and other components; and consequently contributes to irreversible capacity. To elucidate some of the details of the formation and subsequent dissolution of species formed during lithiation of silicon anodes we have produced thin film silicon electrodes and analyzed them during lithiation and delithiation using an electrochemical quartz microbalance with in-situ dissipation (EQCM-D). Measurements were conducted on electrodes with silicon alone and silicon with a silicon dioxide coating, and in EC:EMC and EC:DEC:FEC based electrolytes. Mass loss during lithiation was observed in both solvents systems when an oxide layer was present on the surface of the electrode. Solid state and solution NMR measurements indicate that the formation and dissolution of Li2O is the most likely cause of mass loss.

Recently a new class of solid lithium ion conductors was reported based on the anti-perovskite structure, notably Li3OCl and Li3OBr. For many beyond lithium-ion battery uses, the solid electrolyte is envisioned to be in direct contact with liquid electrolytes and lithium metal. In this study we evaluated the stability of the Li3OBr phase against common battery solvents electrolytes, including diethylcarbonate (DEC) and dimethylcarbonate (DMC), as well as a LiPF6 containing commercial electrolyte. In contact with battery-grade organic solvents, Li3OBr was typically found to be insoluble but lost its crystallinity and reacted with available protons and in some cases with the solvent. A low temperature heat treatment was able to restore crystallinity of the samples; however evidence of proton ion exchange was conserved.

Mg battery operates with Chevrel phase (Mo6S8, ∼1.1 V vs Mg) cathodes that apply Grignard-based or derived electrolytes, which allow etching of the passivating oxide coating forms at the magnesium metal anode. Majority of Mg electrolytes studied to date are focused on developing new synthetic strategies to achieve a better reversible Mg deposition. While most of these electrolytes contain chloride as a component, and there is a lack of literature which investigates the fundamental role of chloride in Mg electrolytes. Further, ease of preparation and potential safety benefits have made simple design of magnesium electrolytes an attractive alternative to traditional air sensitive Grignard reagents-based electrolytes. Work presented here describes simple, non-Grignard magnesium electrolytes composed of magnesium bis(trifluoromethane sulfonyl)imide mixed with magnesium chloride (Mg(TFSI)2-MgCl2) in tetrahydrofuran (THF) and diglyme (G2) that can reversibly plate and strip magnesium. Based on this discovery, the effect of chloride in the electrolyte complex was investigated. Electrochemical properties at different initial mixing ratios of Mg(TFSI)2 and MgCl2 showed an increase of both current density and columbic efficiency for reversible Mg deposition as the fraction content of MgCl2 increased. A decrease in overpotential was observed for rechargeable Mg batteries with electrolytes with increasing MgCl2 concentration, evidenced by the coin cell performance. In this work, the fundamental understanding of the operation mechanisms of rechargeable Mg batteries with the role of chloride content from electrolyte could potentially bring rational design of simple Mg electrolytes for practical Mg battery.

CpCo(CO) 2 catalyzes the cocyclization of ortho-diethynylthiophenes and -pyridines with alkynes to construct the corresponding thia- and azaphenylenes. This strategy is applied to the synthesis of linear 1-aza[3]phenylene, the first higher heterophenylene.

A multivalent successor to lithium ion batteries will likely incorporate a metal anode. However, many electrodeposition processes are prone to energy losses from side reactions and overpotentials for plating or stripping. To develop a link between the kinetics of crystal growth/dissolution with electrochemical data, we have followed electrodeposition of Mg and Zn with operando x-ray diffraction using a variety of electrolytes and current collectors. In some cases we find that alloying or passivation competes with metal deposition and can dramatically alter the morphology of the deposited metal, as seen by texture analysis of the diffraction.

One of the more promising cathode materials for high-energy high-voltage lithium ion batteries (LIBs) are Ni-rich layered cathode materials such as LiNixMnyCozO2 (where x + y + z = 1). Although these cathode materials are attractive from a high capacity standpoint, they commonly suffer from poor structural stability at highly delithiated (charged) states leading to poor electrochemical performance.1-3 To help aid these issues, surface coatings are becoming a widely adopted method to improve the cycling performance of high-voltage cathode materials. More widely investigated coating materials include oxide coatings (Al2O3, TiO2, etc.)4 while comparatively fewer studies have investigated organic monomer or polymer coatings (PEDOT, polyimide, etc.).5 In this work, the surface of LiNi0.5Mn0.3Co0.2O2 cathode materials were coated with organosilane reagents to investigate their effect on cell electrochemical performance. The impact of the weight percentage of organosilane used and the functionality of the organosilane used will be presented. Characterization of the organosilane coating using XRD, XPS and FTIR confirm the presence of a Si-containing coating. Cycling performance for half cells (Li/ LiNi0.5Mn0.3Co0.2O2) using the organosilane coated cathodes will be shown. In conclusion, a new type of organic coating was utilized on Ni-rich cathode materials and this research explores a new type of coating for high voltage cathodes. 1) Son, I. H.; Park, J. H.; Kwon, S.; Mun, J. and Choi, J. W. Chem. Mat. 2015, 27, 7370-7379. 2) Bak, S.-M.; Hu, E.; Zhou, Y.; Yu, X.; Senanayake, S. D.; Cho, S.-J.; Kim, K.-B.; Chung, K. Y.; Yang, X.-Q. and Nam, K.-W. ACS Appl. Mater. Interfaces 2014, 6, 22594-22601. 3) Lin, F.; Markus, I. M.; Doeff, M. M.; Xin, H. L. Sci. Rep., 2014, 4, 5694. 4) Xu, S.; Jacobs, R. M.; Nguyen, H. M.; Hao, S.; Mahanthappa, M.; Wolverton, C.; Morgan, D. J. Mater. Chem. A, 2015, 3, 17248. 5) Zhang, J.; Lu, Q.; Fang, J.; Wang, J.; Yang, J. and NuLi, Y. ACS Appl. Mater. Interfaces 2014, 6, 17965-17973.

One of the more promising cathode materials for high-energy high-voltage lithium ion batteries (LIBs) are Ni-rich layered cathode materials such as LiNixMnyCozO2 (where x + y + z = 1). Although these cathode materials are attractive from a high capacity standpoint, they commonly suffer from poor structural stability at highly delithiated (charged) states leading to poor electrochemical performance.1-3 While incorporation of additives into the electrolyte provides one way to improve cycling performance in LIBs, surface coatings are becoming a widely adopted method to improve the cycling performance of high-voltage cathode materials. More widely investigated coating materials include oxide coatings (Al2O3, TiO2, etc.)4 while comparatively fewer studies have investigated organic monomer or polymer coatings (PEDOT, polyimide, etc.).5 Additionally, the mechanism of the coating interaction with the material is intriguing due to its importance in creating a performance-enhancing coating. In this work, the surface of LiNi0.5Mn0.3Co0.2O2 cathode materials were coated with organosilane reagents to investigate their effect on cell electrochemical performance. The impact of the cathode pretreatment, the weight percentage of organosilane used and the functionality of the organosilane used will be presented. Characterization of the organosilane coating using SEM shows a slight morphological change in the cathode surface while EDX and FTIR confirm the presence of a Si-containing coating. Half cells (Li/ LiNi0.5Mn0.3Co0.2O2) using the organosilane coated cathodes operating in the voltage window of 3.0 - 4.4 V showed similar cycling behavior to that of non-coated material. In conclusion, a new type of organic coating was utilized on Ni-rich cathode materials and this research explores a new type of coating for high voltage cathodes. References 1) Son, I. H.; Park, J. H.; Kwon, S.; Mun, J. and Choi, J. W. Chem. Mat. 2015, 27, 7370-7379. 2) Bak, S.-M.; Hu, E.; Zhou, Y.; Yu, X.; Senanayake, S. D.; Cho, S.-J.; Kim, K.-B.; Chung, K. Y.; Yang, X.-Q. and Nam, K.-W. ACS Appl. Mater. Interfaces 2014, 6, 22594-22601. 3) Lin, F.; Markus, I. M.; Doeff, M. M.; Xin, H. L. Sci. Rep., 2014, 4, 5694. 4) Xu, S.; Jacobs, R. M.; Nguyen, H. M.; Hao, S.; Mahanthappa, M.; Wolverton, C.; Morgan, D. J. Mater. Chem. A, 2015, 3, 17248. 5) Zhang, J.; Lu, Q.; Fang, J.; Wang, J.; Yang, J. and NuLi, Y. ACS Appl. Mater. Interfaces 2014, 6, 17965-17973.

Energy storage materials – lithium-based portable energy storage technologies are an area of research that was born in the late 1960s / early 1970s, went global in the 1990s with portable consumer electronics, and is now being adapted to a variety of markets including electrification of vehicles, space flight, and grid storage. While showing promise, these new applications may have different requirements (e.g. power, cost, volume) than ones optimized for consumer markets. To increase energy density, many researchers are exploring ways to incorporate silicon into a battery. Elemental silicon has many properties that make it a top candidate to replace graphitic carbon in next generation lithium-ion batteries. It has (1) very high gravimetric capacity (~3600 mAh/g), (2) high volumetric capacity (~7400 mAh/L), and (3) low insertion cell voltage. It also has many problems that must be overcome including (1) high volume expansion on lithiation, (2) an unstable SEI layer, and (3) instability of the fully charged anode to the electrolyte. Although significant effort has been focused on silicon-based electrodes, e.g. understanding the role of morphology, particle size, or local structure – our work has been concentrated on electrode level interactions. Using the knowledge gained from the materials level studies we are addressing what happens when the silicon is made into an electrode and exposed to the contents of an electrochemical cell [1-3]. Previous work by the Edstrom group [4-5] has shown that the normal passivation layer of silicon, namely silica, is in fact electrochemically active on the first charging cycle. On first lithiation it reacts to form Li4SiO4. This phase does not directly participate in the electrochemistry after this point, but does interact chemically with its environment to effect cycle efficiency and SEI stability [6]. In this talk we will discuss how, upon formation, it interacts with its environment and track these changes by FTIR, 29Si NMR, 7Li NMR, and PXRD with eventual formation of Li6Si2O7 and Li2SiO3. [1] C. Joyce, L.Trahey, S.A. Bauer, F. Dogan, and J, T. Vaughey Journal of The Electrochemical Society, 159,A909-A914 (2012). [2] F. Dogan, C. Joyce, and J. T. Vaughey Journal of The Electrochemical Society, 160, A312-A319 (2013). [3] F. R. Brushett, L.Trahey, X. Xiao, J. T. Vaughey ACS Appl. Mater. Interfaces , 6, 4524−4534 (2014). [4] B. Philippe, R. DedryveÌre, M. Gorgoi, H. Rensmo, D. Gonbeau, K. Edström J. Am. Chem. Soc., 135, 9829−9842 (2013). [5] ] B. Philippe, R. DedryveÌre, M. Gorgoi, H. Rensmo, D. Gonbeau, K. Edström Chem. Mater., 25,394−404 (2013). [6] A. A. Hubaud, Z. Z. Yang , D. J. Schroeder, F. Dogan, L. Trahey, J. T. Vaughey Journal of Power Sources 282, 639-644 (2015) Figure 1

One of the challenges associated with silicon as an anode material for Li-ion batteries is the formation of an unstable solid-electrolyte interphase which, forms continuously while consuming lithium and other components; and consequently contributes to irreversible capacity. To elucidate some of the details of the formation and subsequent dissolution of species that form during lithiation of silicon anodes we have produced thin film silicon electrodes with and without an oxide layer and analyzed these during lithiation and delithiation using an electrochemical quartz microbalance with in- situ dissipation (EQCM-D). Measurements were conducted both in EC:EMC and EC:DEC:FEC based electrolytes. Mass loss during lithiation was observed in both solvents systems when an oxide layer was present on the electrode and this was found to be associated with Li2O dissolution using solution and solid state NMR.

The lithium lanthanum zirconium oxide garnet, Li7La3Zr2O12 (LLZ), has received significant attention in recent years due to its high room temperature lithium ion conductivity and its stability against lithium metal. Together these features make it a promising electrolyte candidate for a high energy all solid-state battery. Previous studies have shown that incorporation of aluminum cations during the synthesis stabilizes the higher conductivity cubic phase of LLZ; however the incorporation process and its effect on the phase transition are still unclear. In the present study, we have combined powder X-ray diffraction (XRD), 27Al and 7Li MAS NMR and high-resolution X-ray diffraction (HRXRD) to determine the disposition of Al cations during the formation of low temperature cubic LLZ. At temperatures as low as 700 °C, the aluminum is incorporated into amorphous or nanocrystalline grain boundary phases. Above 700 °C, the Al cations are associated with a poorly crystalline anti-fluorite phase Li5AlO4, composed of molecular [AlO4]5− anions. This phase then reacts with tetragonal LLZ to form cubic LLZ over a 25 hour period at 850 °C. Although the reaction appears complete by powder X-ray diffraction, 27Al NMR spectra showed overlapping resonances suggesting multiple Al environments due to uneven substitution of the 24d Li(1) site. This was confirmed by high-resolution XRD and was consistent with a series of closely related cubic LLZ phases with slightly different Al concentrations, indicating the slower Al(III) diffusion within the lattice has not reached equilibrium in the time allotted. The disorder over the two crystallographic tetrahedral sites by lithium and aluminum cations at this temperature contributes to the observed lattice enlargement associated with the low temperature cubic phase.