Differences in Interfacial Reactivity of Graphite and Lithium Metal Battery Electrodes Investigated Via Operando Gas Analysis.

Gases evolved from lithium batteries can drastically affect their performance and safety; for example, cell swelling is a serious safety issue. Here, we combine operando pressure measurements and online electrochemical mass spectrometry measurements to identify the nature and quantity of gases formed in batteries with graphite and lithium metal electrodes. We demonstrate that ethylene, a main gas evolved in SEI formation reactions, is quickly consumed at lithium metal electrodes unless they have been pretreated in the electrolyte.

Two electrolyte decomposition pathways at nickel-rich cathode surfaces in lithium-ion batteries.

Preventing the decomposition reactions of electrolyte solutions is essential for extending the lifetime of lithium-ion batteries. However, the exact mechanism(s) for electrolyte decomposition at the positive electrode, and particularly the soluble decomposition products that form and initiate further reactions at the negative electrode, are still largely unknown. In this work, a combination of gas measurements and solution NMR was used to study decomposition reactions of the electrolyte solution at NMC (LiNi Mn Co O) and LCO (LiCoO) electrodes.

Negating the Interfacial Resistance between Solid and Liquid Electrolytes for Next-Generation Lithium Batteries.

The combination of solid and liquid electrolytes enables the development of safe and high-energy batteries where the solid electrolyte acts as a protective barrier for a high-energy lithium metal anode, while the liquid electrolyte maintains facile electrochemical reactions with the cathode. However, the contact region between the solid and liquid electrolytes is associated with a very high resistance, which severely limits the specific energy that can be practically delivered. In this work, we demonstrate a suitable approach to virtually suppress such interfacial resistance.

Current Challenges and Routes Forward for Nonaqueous Lithium-Air Batteries.

Nonaqueous lithium-air batteries have garnered considerable research interest over the past decade due to their extremely high theoretical energy densities and potentially low cost. Significant advances have been achieved both in the mechanistic understanding of the cell reactions and in the development of effective strategies to help realize a practical energy storage device. By drawing attention to reports published mainly within the past 8 years, this review provides an updated mechanistic picture of the lithium peroxide based cell reactions and highlights key remaining challenges, including those due to the parasitic processes occurring at the reaction product-electrolyte, product-cathode, electrolyte-cathode, and electrolyte-anode interfaces.

Using polyoxometalates to enhance the capacity of lithium-oxygen batteries.

The Keggin-type polyoxometalate α-SiW12O404- increases the discharge capacity and potential of lithium-oxygen batteries, by facilitating the reduction of O2 to Li2O2, as confirmed by in situ electrochemical pressure measurements and XRD. Compared to organic redox mediators, polyoxometalates have higher chemical and structural stability, which could lead to longer cycling lithium-oxygen batteries.

Mechanistic Insight into the Superoxide Induced Ring Opening in Propylene Carbonate Based Electrolytes using in Situ Surface-Enhanced Infrared Spectroscopy.

Understanding the mechanistic details of the superoxide induced solvent degradation, is important in the development of stable electrolytes for lithium-oxygen (Li-O2) batteries. Propylene carbonate (PC) decomposition on a model electrode surface is studied here using in situ attenuated total reflectance surface enhanced infrared absorption spectroscopy (ATR-SEIRAS). The sensitivity of the SEIRAS technique to the interfacial region allows investigation of subtle changes in the interface region during electrochemical reactions.

Electrochemical studies of capping agent adsorption provide insight into the formation of anisotropic gold nanocrystals.

The ability of the 4-dimethylaminopyridine (DMAP) to stabilize and control the formation of anisotropic gold nanocrystals produced via the borohydride reduction of gold(III) salts is reported here. Electrochemical measurements of DMAP electrosorption on different low-index single crystal and polycrystalline electrodes is provided and shows a propensity for DMAP to preferentially adsorb on {100} facets. Measuring the electrochemical potential during nanocrystal formation shows that experimental conditions can easily be manipulated so that the growth of nanoseeds occurs at potentials that support preferential DMAP adsorption on {100} surfaces giving rise to highly anisotropic nanocrystals (nanorods, bipyramids, and nanopods).

Quaternary ammonium bromide surfactant adsorption on low-index surfaces of gold. 2. Au(100) and the role of crystallographic-dependent adsorption in the formation of anisotropic nanoparticles.

A qualitative and quantitative description of the coadsorption of a quaternary ammonium bromide surfactant on Au(100) has been determined using electrochemical techniques. Cyclic voltammetry reveals that both the cationic surfactant ion and its halide counterion are adsorbed on the surface of unreconstructed Au(100) over a wide range of electrode potentials or charge densities. The relative Gibbs excesses of the cationic and anionic components of octyltrimethylammonium (OTA(+)) bromide have been determined using the thermodynamics of ideally polarized electrodes.

Quaternary ammonium bromide surfactant adsorption on low-index surfaces of gold. 1. Au(111).

The coadsorption of the anionic and cationic components of a model quaternary ammonium bromide surfactant on Au(111) has been measured using the thermodynamics of an ideally polarized electrode. The results indicate that both bromide and trimethyloctylammonium (OTA(+)) ions are coadsorbed over a broad range of the electrical state of the gold surface. At negative polarizations, the Gibbs surface excess of the cationic surfactant is largely unperturbed by the presence of bromide ions in solution.

Surface enhanced infrared absorption spectroscopy studies of DMAP adsorption on gold surfaces.

Attenuated total reflectance surface enhanced infrared absorption spectroscopy (ATR-SEIRAS) measurements have been employed to study the adsorption of dimethylaminopyridine (DMAP) and its conjugate acid (DMAPH+) on gold surfaces as a function of applied potential and solution pH. Based on our transmission measurements, we have been able to demonstrate that the acid/base forms of this pyridine derivative can be readily differentiated due to their distinct IR signals. When the solution pH is equal to the pKa of DMAPH+, we demonstrate that the adsorbing species is DMAP, oriented with its heterocyclic ring perpendicular to the electrode surface.

Electron transfer behavior of monolayer protected nanoclusters and nanowires of silver and gold.

Understanding the electron transfer behavior of nanometer sized, both metallic and semiconducting particles and wires is important due to the fundamental interest in size and shape dependent electronic properties and also because of its applications in nano-electronic devices like single electron transistors and molecular switches. Monolayer protected nanoclusters enable one simple and elegant method of synthesis of these types of metallic and semiconducting materials using interfacial chemistry as has been successfully used in several applications ranging from catalysis to molecular electronics. The success of this type of nanostructured materials is due in part to the well known protecting/stabilizing action of the ligands (also known as surface passivating/capping agents), which facilitate the synthesis and processing of these hydrophobic colloids in solution form.