Gregory Salitra

Challenges in the development of advanced Li-ion batteries: a review

Li-ion battery technology has become very important in recent years as these batteries show great promise as power sources that can lead us to the electric vehicle (EV) revolution. The development of new materials for Li-ion batteries is the focus of research in prominent groups in the field of materials science throughout the world. Li-ion batteries can be considered to be the most impressive success story of modern electrochemistry in the last two decades. They power most of todays portable devices, and seem to overcome the psychological barriers against the use of such high energy density devices on a larger scale for more demanding applications, such as EV. Since this field is advancing rapidly and attracting an increasing number of researchers, it is important to provide current and timely updates of this constantly changing technology. In this review, we describe the key aspects of Li-ion batteries: the basic science behind their operation, the most relevant components, anodes, cathodes, electrolyte solutions, as well as important future directions for R&D of advanced Li-ion batteries for demanding use, such as EV and load-leveling applications.

On the Surface Chemical Aspects of Very High Energy Density, Rechargeable Li–Sulfur Batteries

Li(metal)-sulfur (Li-S) systems are among the rechargeable batteries of the highest possible energy density due to the high capacity of both electrodes. The surface chemistry developed on Li electrodes in electrolyte solutions for Li-S batteries was rigorously studied using Fourier transform infrared and X-ray photoelectron spectroscopies. A special methodology was developed for handling the highly reactive Li samples. It was possible to analyze the contribution of solvents such as 1-3 dioxolane, the electrolyte LiN(SO 2 CF 3 ) 2 , polysulfide (Li 2 S n ), and LiNO 3 additives to protective surface films that are formed on the Li electrodes. The role of LiNO 3 as a critical component whose presence in solutions prevents a shuttle mechanism that limits the capacity of the sulfur electrodes is discussed and explained herein.

Sulfur‐Impregnated Activated Carbon Fiber Cloth as a Binder‐Free Cathode for Rechargeable Li‐S Batteries

A route for the preparation of binder-free sulfur-carbon cathodes is developed for lithium sulfur batteries. The method is based on the impregnation of elemental sulfur into the micropores of activated carbon fibers. These electrodes demonstrate good electrochemical performance at high current density attributed to the uniform dispersion of sulfur inside the carbon fiber.

Common electroanalytical behavior of Li intercalation processes into graphite and transition metal oxides

This paper compares the electroanalytical behavior of lithiated graphite, Li x CoO 2 , Li x NiO 2 , and Li x Mn 2 O 4 spinel electrodes. Slow scan rate cyclic voltammetry (SSCV), potentiostatic intermittent titration (PITT), and electrochemical impedance spectroscopy (EIS) were applied in order to study the potentiodynamic behavior, the variation of the solid-state diffusion coefficient, and the impedance of these electrodes. In addition, X-ray diffractometry and Fourier transform infrared (FTIR) spectroscopy were used in order to follow structural and surface chemical changes of these electrodes upon cycling. It was found that all four types of electrodes behave very similarly. Their SSCV are characterized by narrow peaks which may reflect phase transition between intercalation stages, and the potential-dependent Li chemical diffusion coefficient is a function with sharp minima in the vicinity of the CV peak potentials, in which the differential electrode capacity is maximal. The impedance spectra of these electrodes reflect an overall process of various steps in series. These include Li + ion migration through surface films, charge transfer which depends strongly on the potential, solid-state diffusion and, finally, accumulation of the intercalants in their sites in the bulk of the active mass, which appears as a strongly potential-dependent, low-frequency capacitive element. It is demonstrated that the above electroanalytical response, which can be considered as the electrochemical fingerprint of these electrodes, may serve as a good in situ tool for the study of capacity fading mechanisms.

Carbon electrodes for double-layer capacitors. I. Relations between ion and pore dimensions

We characterized activated carbon electrodes for electrical double-layer capacitor (EDLC) systems. High-surface-area carbons were prepared by carbonization of cotton cloth at elevated temperatures (up to 1050°C), followed by activation at 900°C by oxidation with CO 2 during different time periods. Specific surface areas and characteristic pore sizes obtained from gas adsorption isotherms were correlated with those obtained from ion electroadsorption at the electrical double layer. Electrolytes studied included aqueous LiCI, NaCI, and KCl solutions and nonaqueous propylene carbonate solutions with LiBF 4 and (C 2 H 5 ) 4 NBF 4 salts. We found clear evidence that the porous carbons thus formed exhibit ion sieving properties, and that increasing activation time systematically increases the average pore sizes of these carbons. The electric double layer (EDL) capacity of these samples (calculated from voltammetric measurements) depends strongly on the adsorption interaction of the ions in the pores, and hence the relationship between the average pore size and the effective ion size determines the specific EDL capacitance of these samples. The following order of dimension of adsorbed species was found, based on the ion sieving of the various synthesized carbons of different average pore size N 2 ; Na + (aq); Cl - (3.6 A) < BF 4 - < TEA + (PC) < Li + (PC).

Morphological and Structural Studies of Composite Sulfur Electrodes upon Cycling by HRTEM, AFM and Raman Spectroscopy

In this work, structural and morphological changes in composite sulfur electrodes were studied due to their cycling in rechargeable Li-S cells produced by Sion Power Inc. Composite sulfur cathodes, comprising initially elemental sulfur and carbon, undergo pronounced structural and morphological changes during discharge-charge cycles due to the complicated redox behavior of sulfur in nonaqueous electrolyte solutions that contain Li ions. Nevertheless, Li―S cells can demonstrate prolonged cycling. To advance this technology, it is highly important to understand the evolution of the structure and morphology of sulfur cathodes as cycling proceeds. High resolution scanning and tunneling microscopy, scanning probe microscopy, and Raman spectroscopy were used in conjunction with the electrochemical measurements. A special methodology for slicing composite sulfur electrodes and their cross sectioning and depth profiling was developed. The gradual changes in the structure of sulfur cathodes due to cycling is described and discussed herein. Important phenomena include changes in the surface electrical conductivity of sulfur electrodes and pronounced morphological changes due to the irreversibility of the sulfur redox reactions. Based on the observations presented in this work, it may be possible to outline guidelines for improving Li-S battery technology and extending its cycle life.

Comparing the Behavior of Nano- and Microsized Particles of LiMn1.5Ni0.5O4 Spinel as Cathode Materials for Li-Ion Batteries

We report on a rigorous comparative study of nano- and microparticles of Limn 1.5 Ni 0.5 O 4 spinel as cathode materials for Li-ion batteries. The stability of these materials in LiPF 6 /alkyl carbonate solutions in temperatures up to 70°C was explored. Capacity, cycling, rate capabilities, and impedance behavior were also studied. The methods included X-ray diffraction, Raman, X-ray photelectron, Fourier transform infrared, and electron paramagnetic resonance spectroscopies, and electron microscopy, in conjunction with standard electrochemical techniques: voltammetry, chronopotentiometry, and impedance spectroscopy. These materials show an impressive stability in solutions at elevated temperature. The use of nanomaterials was advantageous for obtaining a better rate capability of LiMn 1.5 Ni 0.5 O 4 electrodes. LiMn 1.5 Ni 0.5 O 4 particles develop a unique surface chemistry in solutions that passivates and protects them from detrimental interactions with solution species at elevated temperatures.

Fluoroethylene carbonate as an important component in electrolyte solutions for high-voltage lithium batteries: role of surface chemistry on the cathode.

The effect of fluorinated ethylene carbonate (FEC) as a cosolvent in alkyl carbonates/LiPF6 on the cycling performance of high-voltage (5 V) cathodes for Li-ion batteries was investigated using electrochemical tools, X-ray photoelectron spectroscopy (XPS), and high-resolution scanning electron microscopy (HRSEM). An excellent cycling stability of LiCoPO4/Li, LiNi0.5Mn1.5O4/Si, and LiCoPO4/Si cells and a reasonable cycling of LiCoPO4/Si cells was achieved by replacing the commonly used cosolvent ethylene carbonate (EC) by FEC in electrolyte solutions for high-voltage Li-ion batteries. The roles of FEC in the improvement of the cycling performance of high-voltage Li-ion cells and of surface chemistry on the cathode are discussed.

Electrochemical quartz crystal microbalance (EQCM) studies of ions and solvents insertion into highly porous activated carbons.

Electrochemical quartz crystal microbalance (EQCM) technique provides a direct assessment to the behavior of electroadsorbed ions and solvent molecules confined in micropores of activated carbon electrodes in contact with practically important aprotic electrolyte solutions. The estimated value of the solvation number equal to 3 is evident for a partial desolvation of Li(+) cations when adsorbed in carbon micropores.

Assessing the Solvation Numbers of Electrolytic Ions Confined in Carbon Nanopores under Dynamic Charging Conditions.

We propose herein a new reliable approach to assess solvation numbers of ions confined in carbon nanopores based on dynamic quartz crystal measurements. This was proved for the entire families of alkaline, alkaline-earth cations, and halogen anions. As-assessed hydration numbers appear in the sequence characteristic of a transition from the cosmotropic to a chaotropic-type behavior with the decrease of the ions charge-to-size ratio. The information on the behavior of ions confined in nanometric space of different (especially charged) carbon materials is in high demand for the development of powerful supercapacitors, nanofiltration membranes, and chemical/biochemical sensors.