Eduard Nasybulin

Lithium metal anodes for rechargeable batteries

Lithium (Li) metal is an ideal anode material for rechargeable batteries due to its extremely high theoretical specific capacity (3860 mA h g−1), low density (0.59 g cm−3) and the lowest negative electrochemical potential (−3.040 V vs. the standard hydrogen electrode). Unfortunately, uncontrollable dendritic Li growth and limited Coulombic efficiency during Li deposition/stripping inherent in these batteries have prevented their practical applications over the past 40 years. With the emergence of post-Li-ion batteries, safe and efficient operation of Li metal anodes has become an enabling technology which may determine the fate of several promising candidates for the next generation energy storage systems, including rechargeable Li–air batteries, Li–S batteries, and Li metal batteries which utilize intercalation compounds as cathodes. In this paper, various factors that affect the morphology and Coulombic efficiency of Li metal anodes have been analyzed. Technologies utilized to characterize the morphology of Li deposition and the results obtained by modelling of Li dendrite growth have also been reviewed. Finally, recent development and urgent need in this field are discussed.

Dendrite-Free Lithium Deposition with Self-Aligned Nanorod Structure

Suppressing lithium (Li) dendrite growth is one of the most critical challenges for the development of Li metal batteries. Here, we report for the first time the growth of dendrite-free lithium films with a self-aligned and highly compacted nanorod structure when the film was deposited in the electrolyte consisting of 1.0 M LiPF6 in propylene carbonate with 0.05 M CsPF6 as an additive. Evolution of both the surface and the cross-sectional morphologies of the Li films during repeated Li deposition/stripping processes were systematically investigated. It is found that the formation of the compact Li nanorod structure is preceded by a solid electrolyte interphase (SEI) layer formed on the surface of the substrate. Electrochemical analysis indicates that an initial reduction process occurred at ∼ 2.05 V vs Li/Li(+) before Li deposition is responsible for the formation of the initial SEI, while the X-ray photoelectron spectroscopy indicates that the presence of CsPF6 additive can largely enhance the formation of LiF in this initial SEI. Hence, the smooth Li deposition in Cs(+)-containing electrolyte is the result of a synergistic effect of Cs(+) additive and preformed SEI layer. A fundamental understanding on the composition, internal structure, and evolution of Li metal films may lead to new approaches to stabilize the long-term cycling stability of Li metal and other metal anodes for energy storage applications.

Formation of Interfacial Layer and Long-Term Cyclability of Li–O2 Batteries

The long-term operation of Li-O2 batteries under full discharge/charge conditions is investigated in a glyme-based electrolyte. The formation of stable interfacial layer on the electrode surface during the initial cycling stabilizes reaction products at subsequent cycling stages as demonstrated by quantitative analyses of the discharge products and the gases released during charging. There is a quick switch from the predominant formation of Li2O2 to the predominant formation of side products during the first few cycles. However, after the formation of the stable interfacial layer, the yield of Li2O2 in the reaction products is stabilized at about 33-40%. Extended cycling under full discharge/charge conditions is achievable upon selection of appropriate electrode materials (carbon source and catalyst) and cycling protocol. Further investigation on the interfacial layer, which in situ forms on air electrode, may increase the long-term yield of Li2O2 during the cycling and enable highly reversible Li-O2 batteries required for practical applications.

The Mechanisms of Oxygen Reduction and Evolution Reactions in Nonaqueous Lithium–Oxygen Batteries

A fundamental understanding of the mechanisms of both the oxygen reduction reaction (ORR) and the oxygen evolution reaction (OER) in nonaqueous lithium-oxygen (Li-O2) batteries is essential for the further development of these batteries. In this work, we systematically investigate the mechanisms of the ORR/OER reactions in nonaqueous Li-O2 batteries by using electron paramagnetic resonance (EPR) spectroscopy, using 5,5-dimethyl-pyrroline N-oxide as a spin trap. The study provides direct verification of the formation of the superoxide radical anion (O2(˙-)) as an intermediate in the ORR during the discharge process, while no O2(˙-) was detected in the OER during the charge process. These findings provide insight into, and an understanding of, the fundamental reaction mechanisms involving oxygen and guide the further development of this field.

In-situ electrochemical transmission electron microscopy for battery research.

The recent development of in-situ liquid stages for (scanning) transmission electron microscopes now makes it possible for us to study the details of electrochemical processes under operando conditions. As electrochemical processes are complex, care must be taken to calibrate the system before any in-situ/operando observations. In addition, as the electron beam can cause effects that look similar to electrochemical processes at the electrolyte/electrode interface, an understanding of the role of the electron beam in modifying the operando observations must also be understood. In this paper we describe the design, assembly, and operation of an in-situ electrochemical cell, paying particular attention to the method for controlling and quantifying the experimental parameters. The use of this system is then demonstrated for the lithiation/delithiation of silicon nanowires.

Potentiometric monitoring DNA hybridization with polyaniline/Nylon-6 working electrode

Electrically conducting polymers are useful in various applications such as transistors and sensors. A potentiometric pH meter has been developed using polyaniline based working electrode and with improved selectivity using ionophores, the polyaniline based potentiometer has been applied to monitor various ions mainly in environmental applications. The polyaniline working electrode can be used to monitor not only the binding of a biological ionic macromolecules on polyaniline surface but also the binding of the adsorbed macromolecule with another macromolecule. We present first how the working electrode was prepared by polymerization of aniline in Nylon-6 matrix to provide the mechanical strength and then how single strand oligonucleotide probe binds with polyaniline surface. We then present how an electrode modification with mercaptoethanol results in a surface protected against non-specific binding and then finally we present the results of monitoring the complimentary strand binding leading to the formation of the double strand DNA.

Structure and Characteristics of Composite Materials Based on Polyaniline and Nylon-6

A comparative systematic study addresses the specific features of polymerization of aniline adsorbed on the Nylon matrices in the solutions containing monomer and in the monomer-free solutions. The characteristics of the formed composite materials are investigated. In the presence of aniline in the solution, a uniform and conducting composite material is obtained and its electrical conductivity reversibly depends on pH of the medium and is several orders of magnitude higher than the electrical conductivity of the composite material prepared by the polymerization of aniline in the Nylon matrix in the monomer-free solution.

Direct Observation of Li2O2 Nucleation and Growth with In-Situ Liquid ec-(S)TEM

1. Fundamental and Computational Sciences Directorate, Pacific Northwest National Laboratory, Richland, USA 2. Energy and Environment Directorate, Pacific Northwest National Laboratory, Richland, USA 3. Environmental and Molecular Sciences Laboratory, Pacific Northwest National Laboratory, Richland, USA 4. Department of Chemical and Biological Engineering, University of WisconsinMadison, Madison, USA