Conversion mechanisms of cobalt oxide anode for Li-ion battery: In situ X-ray absorption fine structure studies

Chae, Byung-Mok; Oh, Eun‐Suok; Lee, Yong‐Kul

doi:10.1016/j.jpowsour.2014.10.108

Cited by 60 publications

(39 citation statements)

References 38 publications

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“…The normalized Co K‐edge XAFS spectra of initial, discharged, and charged CNT@Co 3 O 4 and CNT/Co 3 O 4 air electrodes are shown in Figure a. It can be observed that the Co XAS of all electrodes exhibited a similar features and are well matched with Co K‐edge XAS spectra reported in previous studies, indicating that the Co species in the initial and electrochemical reacted air electrodes mainly exist as Co 3 O 4 . The X‐ray absorption near edge structure (XANES) spectra of the air electrodes (shown in Figure S4 in the Supporting Information) also clearly demonstrate that the oxidation state of these electrodes remain throughout the electrochemical process.…”

Section: Resultssupporting

confidence: 70%

Atomic Layer Deposited Non‐Noble Metal Oxide Catalyst for Sodium–Air Batteries: Tuning the Morphologies and Compositions of Discharge Product

Sun

Liu

et al. 2017

Adv Funct Materials

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Catalysts can play a critical role in the development of sodium–air batteries (SABs). Atomic layer deposition (ALD) technology enables rational design and atomic utilization of catalyst by homogenously distributing catalytically active material on a variety of substrates. Here, a novel hierarchical nanostructured Co3O4 is decorated on carbon nanotubes by ALD (CNT@Co3O4) and used as a catalyst for SABs. CNT@Co3O4 demonstrates better performance and longer cycle life than a mechanically mixed CNT/Co3O4 nanocomposite. Well‐dispersed ALD Co3O4 catalyst on CNTs, which serves as functionalized active sites, enables rapid electron exchange and high oxygen reduction/evolution activities. Synchrotron‐based X‐ray analysis including X‐ray absorption near edge structure, extended X‐ray absorption fine structure, and scanning transmission X‐ray microscopy characterization techniques have been employed to elucidate the activity of Co3O4 and to investigate the nanoscale discharge product distribution found in SABs. This analysis reveals that Co3O4 catalyst can promote the electrochemical decomposition of sodium peroxide, superoxide, and carbonates. The role of the catalyst in SABs is clarified and discussed in detail.

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Section: Resultssupporting

confidence: 70%

Atomic Layer Deposited Non‐Noble Metal Oxide Catalyst for Sodium–Air Batteries: Tuning the Morphologies and Compositions of Discharge Product

Sun

Liu

et al. 2017

Adv Funct Materials

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“…When the voltage decreases to 0.6 V, the intensity of the pre-edge increases in the XANES spectra and the intensity of the white line is decreased, demonstrating that the local structure has changed at the end of the discharge process. 49 During the charge process, the Co K-edge shi exhibits the inverse trend, but it is not fully recovered to the original state in the pristine sample. In addition, an increase in voltage up to 3.0 V led to a rise in the white line peak at 7724 eV, with a decrease in the shoulder at 7710 eV, suggesting that the local structure and coordination of Co in the charged products are quite different from those in pristine (Fig.…”

Section: 4748mentioning

confidence: 95%

Formation of graphene-encapsulated CoS₂hybrid composites with hierarchical structures for high-performance lithium-ion batteries

et al. 2017

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Transition metal sulfides (TMSs) are considered as the most promising alternative anode materials for advanced lithium-ion batteries (LIBs). Here, we report a hierarchically structured CoS 2 nanosphere/graphene (CoS 2 /G) composite, fabricated by a simple hydrothermal method. This composite, assembled with CoS 2 nanoparticles uniformly distributed on the graphene, exhibits excellent electrochemical performance. In particular, the CoS 2 /G electrode material delivers a high rate capability of around 398 mA h g À1 at a current density of 3500 mA g À1. Moreover, a discharge capacity of about 400 mA h g À1 can be obtained after 1000 cycles at a current density of 500 mA g À1. X-ray absorption spectroscopy is used to characterize the sample for the first time, and the results demonstrate that CoS 2 /G is reduced to metallic Co and Li 2 S when discharged to 0.01 V. In subsequent charge-discharge processes, the metallic Co cannot be fully oxidized to CoS 2 , which is the main cause of capacity loss for the CoS 2 electrode.

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“…Also the reversibility of conversion reaction is a point of discussion and determined by several thermodynamic and kinetic factors . For instance, the classical conversion reaction for Co 3 O 4 is stated as Co 3 O 4 +8Li + +8e − →4Li 2 O+3Co, but also subsequent reactions according to Co+Li 2 O→CoO+2Li, or a coexistence of Co 3 O 4 and CoO for the following cycles were reported . A further example is provided by mesoporous Cr 2 O 3 electrodes for that a preferred formation of chromium monoxide (CrO 1‐x ) instead of Cr 2 O 3 could be evidenced during recharge .…”

Section: Introductionmentioning

confidence: 99%

Interfacial Phenomena/Capacities Beyond Conversion Reaction Occurring in Nano‐sized Transition‐Metal‐Oxide‐Based Negative Electrodes in Lithium‐Ion Batteries: A Review

Keppeler

Srinivasan

2017

ChemElectroChem

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Nano‐sized transition‐metal oxides are of topical interest in current research towards high‐capacity negative electrodes for rechargeable lithium‐ion batteries. Schematically, an interaction with Li+ through a conversion reaction is commonly accepted. However, experimentally observed capacities often significantly exceed the correlating theoretical quantity of transferred charge carriers based on the conversion reaction. The origin of the additional capacity is under intense debate, although the indispensability of interfacial phenomena and material dimensions in the nanometer regime for concrete explanations are widely observed. Scenarios associated with additional capacities are electrode/electrolyte interphases (solid‐electrolyte interphase, polymer/gel‐like film), additional Li+ accommodation through reaction with grain boundary phases in nanostructures, interfacial Li+ accommodation along with charge separation at phase boundaries, or additional Li+ uptake in unique structural architectures with high specific surface areas that often exhibit an extensive hierarchical meso‐ and/or nanoporous system. In addition, interfacial phenomena are strongly related to battery safety, and hence a topic of highest relevance. As the number of related articles has become so intense, this Review article provides an up‐to‐date summary, and a first attempt is made to systematically classify capacity profiles of nano‐sized transition‐metal oxides that exhibit additional capacities beyond the theoretical value based on the concept of conversion reaction.

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Conversion mechanisms of cobalt oxide anode for Li-ion battery: In situ X-ray absorption fine structure studies

Cited by 60 publications

References 38 publications

Atomic Layer Deposited Non‐Noble Metal Oxide Catalyst for Sodium–Air Batteries: Tuning the Morphologies and Compositions of Discharge Product

Atomic Layer Deposited Non‐Noble Metal Oxide Catalyst for Sodium–Air Batteries: Tuning the Morphologies and Compositions of Discharge Product

Formation of graphene-encapsulated CoS₂hybrid composites with hierarchical structures for high-performance lithium-ion batteries

Interfacial Phenomena/Capacities Beyond Conversion Reaction Occurring in Nano‐sized Transition‐Metal‐Oxide‐Based Negative Electrodes in Lithium‐Ion Batteries: A Review

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Conversion mechanisms of cobalt oxide anode for Li-ion battery: In situ X-ray absorption fine structure studies

Cited by 60 publications

References 38 publications

Atomic Layer Deposited Non‐Noble Metal Oxide Catalyst for Sodium–Air Batteries: Tuning the Morphologies and Compositions of Discharge Product

Atomic Layer Deposited Non‐Noble Metal Oxide Catalyst for Sodium–Air Batteries: Tuning the Morphologies and Compositions of Discharge Product

Formation of graphene-encapsulated CoS2hybrid composites with hierarchical structures for high-performance lithium-ion batteries

Interfacial Phenomena/Capacities Beyond Conversion Reaction Occurring in Nano‐sized Transition‐Metal‐Oxide‐Based Negative Electrodes in Lithium‐Ion Batteries: A Review

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Formation of graphene-encapsulated CoS₂hybrid composites with hierarchical structures for high-performance lithium-ion batteries