In situ monitoring of discharge/charge processes in Li–O2 batteries by electrochemical impedance spectroscopy

Landa‐Medrano, Imanol; Larramendi, Idoia Ruiz de; Ortiz‐Vitoriano, Nagore; Pinedo, Ricardo; Larramendi, J.I. Ruiz de; Rojo, Teófilo

doi:10.1016/j.jpowsour.2013.10.077

Cited by 53 publications

(35 citation statements)

References 37 publications

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“…36 Ethanol was used as the dispersing agent to form slurry that was kept under stirring overnight. The slurry was air-brushed over a stainless steel mesh (Alfa Aesar, 0.05 mm wire diameter), which works as current collector at the cathode side, and left drying at room temperature for a week in air.…”

Section: Methodsmentioning

confidence: 99%

Monitoring the Location of Cathode-Reactions in Li-O₂Batteries

Landa‐Medrano

Pinedo

Larramendi

et al. 2015

J. Electrochem. Soc.

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The performance of Li-O 2 batteries is typically evaluated by specific capacity and cyclability in order to facilitate quantitative comparison in literature. The accuracy of such comparison is limited, however, due to the wide range of factors which control the reported specific capacities. These comparisons are not always fair as some factors, which can highly influence the obtained specific capacities, are often neglected. A rigorous and systematic study has been conducted in order to identify the isolated effect of diverse parameters on the performance of these promising batteries. The analysis of cells with different carbon contents reveals that the discharge reactions do not necessarily take place throughout the electrode mass, but instead occur preferentially in closest proximity to the oxygen gas-electrolyte interface. The effective activity of the cathode material is therefore reduced as distance from this interface increases. This work demonstrates that the lack of standardized measurement protocols hinders the rapid development of this technology due to the difficulties inherent in the direct comparison of cells with wide-ranging measurement conditions. In addition, it has been demonstrated that both the employed carbon loading and current rate critically affect cycling lifetime. Lithium-oxygen (Li-O 2 ) rechargeable batteries with organic electrolytes have recently received extraordinary attention due to their potential to provide high gravimetric energies (∼3500 Wh/kg based on the cell reaction, 2Li + O 2 ↔ Li 2 O 2 ; 2.96 V vs Li/Li + ). 1 Consequently, these batteries are considered one of the most promising candidates for high energy storage devices such as electric vehicles (EVs) or hybrid electric vehicles (HEVs), which have become of special interest due to the fossil fuel depletion and the demand of a cheaper, nontoxic and environmentally friendly energetic model. This technology is still however in its early stages and some challenges need to be overcome in order to make them commercially available.2-12 Although existing lithium-ion technology was initially adopted in order to start investigating these relatively new batteries, numerous problems reveal that this is not always suitable. For example, the carbonate based solvents, commonly used in Li-ion batteries, 13 were not appropriate for Li-O 2 batteries because of their susceptibility to nucleophilic attack by reduced O 2 − species.10,14-17Li-O 2 batteries usually consist of a lithium foil anode, a lithium salt dissolved in an organic solvent as electrolyte and a porous carbonbased cathode. During the discharge metallic lithium anode releases lithium ions (Li + ) to the electrolyte, while electrons are transported to the cathode through an external circuit.Meanwhile, oxygen molecules are reduced (oxygen reduction reaction, (ORR)) at the cathode.18 The global reaction taking place in the battery is:Solubility and diffusion rate of oxygen in the electrolyte play key roles in determining battery performance. 21,22 Zhang et al. proposed a liqu...

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Section: Methodsmentioning

confidence: 99%

Monitoring the Location of Cathode-Reactions in Li-O₂Batteries

Landa‐Medrano

Pinedo

Larramendi

et al. 2015

J. Electrochem. Soc.

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“…Finally, the W element is the Warburg impedance representing the diffusion process. [22][23][24] Such equivalent circuit parameters (R s , R 1 and R 2 ) of rutile and anatase TiO 2 NFs were presented in Fig. S8.…”

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confidence: 99%

Polymorphism-induced catalysis difference of TiO₂nanofibers for rechargeable Li–O₂batteries

et al. 2014

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The polymorphic change of TiO 2 nanofiber catalysts from anatase to rutile enabled Li-O 2 cells to have higher round-trip efficiency and lower overpotential followed by a better cyclic retention. This is due to enhanced catalytic activity probably associated with the smaller Li + chemisorption energy and band gap of the rutile phase compared with the anatase phase.For the sustainable future of human beings, economical energy consumption and the development of advanced energy conversion/storage systems are considered as urgent global tasks, which must be accomplished as soon as possible for the modern society suffering from environmental concerns and climate changes. In this regard, for the purpose of reducing not only the consumption of natural resources but also the environmental pollution from internal combustion-engines, much effort has been dedicated to developing new energy storage systems (ESS) and electric vehicles (EVs) powered by various batteries, fuel cells and hybrid systems. However, there are several stringent requirements such as high power/energy density, good safety, and high reliability against environmental conditions. Even in terms of power/energy density, the state-ofthe-art lithium rechargeable battery has obvious limitations although extensive research has been conducted to meet the requirements for the next-generation battery. Li-O 2 batteries have attracted intensive attention owing to their high theoretical energy density comparable to those of fossil fuel engines.

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“…29 The decrease of almost one order of the extended dl C indicates that the adsorption of O2 displaces the previous adsorbed Li The main differences of our equivalent circuit model with others proposed in the literature for Li-O2 batteries are two: the identification of the electrostatic capacitance related to the Li + adsorption, extended dl C , and the identification of the ORR related phenomena only at voltages and frequencies below 2.7 V and 10 mHz. In particular, three steps are also identified in the equivalent circuit models proposed previously, 30,31 but assigned to different physical processes. In any way, the detailed analysis of the extended dl C can be a useful tool to evaluate the mechanism of a cathode performance loss: clog of the porosity or coverage of the electric conductive substrate by the electrically insulating products (Li2O2 and Li2CO3) as it has been reported in other studies.…”

Section: Li-o 2 Impedance Responsementioning

confidence: 99%

New approaches to the lithiation kinetics in reaction-limited battery electrodes through electrochemical impedance spectroscopy

2018

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Electrochemical impedance spectroscopy is a widely employed technique probing kinetic limitations in the charging of battery electrodes. Hindrance mechanisms locate at the interfaces between the active material and the electrolyte, and in the bulk of the reacting compound. Rate-limiting mechanisms are viewed as resistive circuit elements and can be extracted by standard impedance analyzers. Classical impedance models consider charge transport, mainly ion diffusion as slower carrier, as the principal kinetic limitation impeding full electrode charging. This is indeed the case for many technologically relevant battery compounds. In other instances, instead of being diffusion-limited, electrodes may undergo charging limitation caused by the kinetics of the reduction reaction itself. Specific impedance models for reaction-limited mechanisms are summarized here and proved for relevant electrode compounds, in particular for conversion or alloying electrodes in which Li + intake produces a full rearrangement of the lattice structure with significant atomic displacement.

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In situ monitoring of discharge/charge processes in Li–O2 batteries by electrochemical impedance spectroscopy

Cited by 53 publications

References 37 publications

Monitoring the Location of Cathode-Reactions in Li-O₂Batteries

Monitoring the Location of Cathode-Reactions in Li-O₂Batteries

Polymorphism-induced catalysis difference of TiO₂nanofibers for rechargeable Li–O₂batteries

New approaches to the lithiation kinetics in reaction-limited battery electrodes through electrochemical impedance spectroscopy

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In situ monitoring of discharge/charge processes in Li–O2 batteries by electrochemical impedance spectroscopy

Cited by 53 publications

References 37 publications

Monitoring the Location of Cathode-Reactions in Li-O2Batteries

Monitoring the Location of Cathode-Reactions in Li-O2Batteries

Polymorphism-induced catalysis difference of TiO2nanofibers for rechargeable Li–O2batteries

New approaches to the lithiation kinetics in reaction-limited battery electrodes through electrochemical impedance spectroscopy

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Product

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Monitoring the Location of Cathode-Reactions in Li-O₂Batteries

Monitoring the Location of Cathode-Reactions in Li-O₂Batteries

Polymorphism-induced catalysis difference of TiO₂nanofibers for rechargeable Li–O₂batteries