Boris Markovsky

On the correlation between surface chemistry and performance of graphite negative electrodes for Li ion batteries

This paper discusses some important aspects of the correlation between surface chemistry, 3D structure, and the electrochemical behavior of lithiated graphite electrodes. By reviewing results obtained with diAerent electrolyte solutions (e.g. ethylene carbonate-based solutions, propylene carbonate solutions, and ether-based systems), we describe the stabilization and capacity fading mechanisms of graphite electrodes. One of the failure mechanisms occurs at potentials >0.5 V Li/Li + , and relates to an increase in the electrode’s impedance due to improper passivation and a simultaneous change in the electrode’s morphology, probably due to gas formation. At low potentials (depending on the electrolyte solution involved), phenomena such as exfoliation and amorphization of the graphite electrodes can be observed. Stabilization mechanisms are also discussed. In general, surface stabilization of the graphite is essential for obtaining reversible lithiation and a long electrode cycle life. The latter usually relates to precipitation of highly compact and insoluble surface species, which adhere well, and irreversibly, to the active surface. Hence, the choice of appropriate electrolyte solutions in terms of solvents, salts and additives is very critical for the use of graphite anodes in Li batteries. The major analytical tools for this study included FTIR and impedance spectroscopies, XPS, and in situ and ex situ XRD in conjunction with standard electrochemical techniques. # 1999 Elsevier Science Ltd. All rights reserved.

On the use of vinylene carbonate (VC) as an additive to electrolyte solutions for Li-ion batteries

Vinylene carbonate (VC) was tested as an additive to electrolyte solutions for Li-ion batteries. For the model electrodes, synthetic graphite was chosen as the anode material, while LiMn2O4 spinel and LiNiO2 were chosen as the cathode materials. The test solution was 1 M LiAsF6 in a 1:1 mixture of ethylene and dimethyl carbonates (EC–DMC). Cyclic voltammetry (CV), chronopotentiometry, impedance spectroscopy, electrochemical quartz crystal microbalance (EQCM), FTIR and X-ray photoelectron spectroscopies have been used in this study. It was found that VC is a reactive additive that reacts on both the anode and the cathode surfaces. The influence of this additive on the behavior of Li–graphite anodes is very positive, since it improves their cyclability, especially at elevated temperatures, and reduces the irreversible capacity. The spectroscopic studies indicate that VC polymerizes on the lithiated graphite surfaces, thus forming poly alkyl Li-carbonate species that suppress both solvent and salt anion reduction. The presence of VC in solutions reduces the impedance of the LiMn2O4 and LiNiO2 cathodes at room temperature. However, we have not yet found any pronounced impact of VC on the cycling behavior of the cathodes, either at room temperature or at elevated temperatures. Thus, VC can be considered as a desirable additive for the anode side in Li-ion batteries, one which has no adverse effect on the cathode side.

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.

Solid‐State Electrochemical Kinetics of Li‐Ion Intercalation into Li1 − x CoO2: Simultaneous Application of Electroanalytical Techniques SSCV, PITT, and EIS

The electroanalytical behavior of thin electrodes is elucidated by the simultaneous application of three electroanalytical techniques: slow‐scan‐rate cyclic voltammetry (SSCV), potentiostatic intermittent titration technique, and electrochemical impedance spectroscopy. The data were treated within the framework of a simple model expressed by a Frumkin‐type sorption isotherm. The experimental SSCV curves were well described by an equation combining such an isotherm with the Butler‐Volmer equation for slow interfacial Li‐ion transfer. The apparent attraction constant was −4.2, which is characteristic of a quasi‐equilibrium, first‐order phase transition. Impedance spectra reflected a process with the following steps: ion migration in solution, ion migration through surface films, strongly potential‐dependent charge‐transfer resistance, solid‐state diffusion, and accumulation of the intercalants into the host materials. An excellent fit was found between these spectra and an equivalent circuit, including a Voigt‐type analog ( migration through multilayer surface films and charge transfer) in series with a finite‐length Warburg‐type element ( solid‐state diffusion), and a capacitor (Li accumulation). In this paper, we compare the solid‐state diffusion time constants and the differential intercalation capacities obtained by the three electroanalytical techniques.

The Study of Electrolyte Solutions Based on Ethylene and Diethyl Carbonates for Rechargeable Li Batteries II . Graphite Electrodes

The electrochemical behavior of Li-graphite intercalation anodes in ethylene and diethyl carbonates (EC-DEC) solutions was studied using surface sensitive Fourier transform infrared spectroscopy (FTIR) and impedance spectroscopy in conjunction with standard electrochemical techniques. Three different solvent combinations, four different salts: LiBF{sub 4}, LiPF{sub 6}, LiClO{sub 4}, and LiAsF{sub 6}, and the influence of the presence of CO{sub 2} were investigated. Graphite electrodes could be cycled hundreds of times obtaining a reasonable reversible capacity. The best electrolyte was found to be LiAsF{sub 6} and the presence of CO{sub 2} in solutions considerably increased the reversible capacity upon cycling. This improved performance is due to precipitation of the ethylene carbonate reduction product, (CH{sub 2}OCO{sub 2}Li){sub 2}, which is an excellent passivating agent, on the electrode surface. Aging processes of these surface films and their influence on the electrode properties are discussed.

Recent studies on the correlation between surface chemistry, morphology, three-dimensional structures and performance of Li and Li-C intercalation anodes in several important electrolyte systems

Abstract This paper reviews some advances in the comparative study of lithium and graphite electrodes in a large matrix of solvents, salts and additives. The major purpose of this work was to support RD (ii) successful and useful application of AFM and EQCM in order to study the surface film formation and Li-deposition processes; (iii) understanding the correlation between the reversibility and stability of graphite electrodes in Li-intercalation processes and their surface chemistry, and (iv) finding an interesting correlation between the three-dimensional structure of graphite electrodes, the diffusion coefficient of Li + and their voltammetric behaviour in Li-intercalation processes.

New insights into the interactions between electrode materials and electrolyte solutions for advanced nonaqueous batteries

Abstract In this paper we review some recent work with Li metal and Li–graphite anodes and Li x MO y cathodes (M=transition metals such as Ni, Co, Mn). The emphasis was on the study of surface phenomena using in situ and ex situ FTIR spectroscopy, atomic force microscopy (in situ AFM), electrochemical quartz crystal microbalance (EQCM) and impedance spectroscopy (EIS). The performance of Li metal and Li–carbon anodes in secondary batteries depends on the nature of the surface films that cover them. The use of Li metal anodes requires the formation of highly uniform and elastic surface films. Thus, most of the commonly used liquid electrolyte solutions are not suitable for Li metal-based rechargeable batteries. In the case of Li–C-based batteries, the passivating films need not be elastic. Channeling the Li–C electrode surface chemistry towards the formation of Li 2 CO 3 surface films provides adequate passivation for these electrodes. This can be achieved through the use of EC-based solutions of low EC concentration (cosolvents should be less reactive than EC). An interesting finding is that the behavior of many commonly used cathodes also depends on their surface chemistry, and that their overall Li insertion processes include the step of Li ion migration through surface films. Their origin is discussed herein, as well as possible oxidation processes of the relevant solutions.

LiMnPO4 as an Advanced Cathode Material for Rechargeable Lithium Batteries

LiMnPO4 nanoparticles synthesized by the polyol method were examined as a cathode material for advanced Li-ion batteries. The structure, surface morphology, and performance were characterized by X-ray diffraction, high resolution scanning electron microscopy, high resolution transmission electron microscopy, Raman, Fourier transform IR, and photoelectron spectroscopies, and standard electrochemical techniques. A stable reversible capacity up to 145 mAh g(-1) could be measured at discharge potentials > 4 V vs Li/Li+, with a reasonable capacity retention during prolonged charge/discharge cycling. The rate capability of the LiMnPO4 electrodes studied herein was higher than that of LiNi0.5Mn0.5O2 and LiNi0.8Co0.15Al0.05O2 (NCA) in similar experiments and measurements. The active mass studied herein seems to be the least surface reactive in alkyl carbonate/LiPF6 solutions. We attribute the low surface activity of this material, compared to the lithiated transition-metal oxides that are examined and used as cathode materials for Li-ion batteries, to the relatively low basicity and nucleophilicity of the oxygen atoms in the olivine compounds. The thermal stability of the LiMnPO4 material in solutions (measured by differential scanning calorimetry) is much higher compared to that of transition-metal oxide cathodes. This is demonstrated herein by a comparison with NCA electrodes

The Study of Electrolyte Solutions Based on Ethylene and Diethyl Carbonates for Rechargeable Li Batteries I . Li Metal Anodes

The behavior of Li electrodes was studied in ethylene and diethyl carbonates (EC-DEC) solutions of LiAsF{sub 6}, LiClO{sub 4}, LiBF{sub 4}, and LiPF{sub 6}. The correlation of the surface chemistry to the interfacial properties, morphology, and Li cycling efficiency was investigated using surface sensitive Fourier transform infrared spectroscopy and impedance spectroscopy, scanning electron microscopy, X-ray energy dispersive microanalysis, and standard electrochemical techniques. The Li surface chemistry is initially dominated by EC reduction to an insoluble species, probably (CH{sub 2}OCO{sub 2}Li){sub 2}. Upon storage, several aging processes may take place, depending on the salt used. Their mechanisms are discussed. Although EC-DEC solutions were found to be adequate for Li ion rechargeable batteries, this work indicates that they are not suitable as electrolyte solutions for batteries with Li metal electrodes. This is mostly because Li electrodes cannot be considered stable in these systems and Li deposition is highly dendritic.

LiMn0.8Fe0.2PO4: An Advanced Cathode Material for Rechargeable Lithium Batteries†

Keywords: cathode materials ; lithium batteries ; nanoparticles ; surface chemistry ; thermal stability ; Performance ; Electrodes Reference EPFL-ARTICLE-159236doi:10.1002/anie.200903587View record in Web of Science Record created on 2010-11-30, modified on 2017-05-12