Soft X-Ray Irradiation Effects of Li2O2, Li2CO3 and Li2O Revealed by Absorption Spectroscopy

Qiao, Ruimin; Chuang, Yi‐De; Yan, Shishen; Yang, Wanli

doi:10.1371/journal.pone.0049182

Cited by 166 publications

(203 citation statements)

References 52 publications

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“…4C), and its fraction increases as a function of charge capacity. Additionally, the peak at around 530 eV is in good agreement with that of Li 2 O 2 (21 (24). In the literature for these layered materials, the changes in the spectra were mainly found in the early stage of charge, and these changes can be partly contributed by the oxidation of transition metals, as also observed in this study.…”

Section: +supporting

confidence: 88%

High-capacity electrode materials for rechargeable lithium batteries: Li ₃ NbO ₄ -based system with cation-disordered rocksalt structure

Yabuuchi

Takeuchi

Nakayama

et al. 2015

Proc. Natl. Acad. Sci. U.S.A.

454

560

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Rechargeable lithium batteries have rapidly risen to prominence as fundamental devices for green and sustainable energy development. Lithium batteries are now used as power sources for electric vehicles. However, materials innovations are still needed to satisfy the growing demand for increasing energy density of lithium batteries. In the past decade, lithium-excess compounds, Li 2 MeO 3 (Me = Mn 4+ , Ru 4+ , etc.), have been extensively studied as highcapacity positive electrode materials. Although the origin as the high reversible capacity has been a debatable subject for a long time, recently it has been confirmed that charge compensation is partly achieved by solid-state redox of nonmetal anions (i.e., oxide ions), coupled with solid-state redox of transition metals, which is the basic theory used for classic lithium insertion materials, such as LiMeO 2 (Me = Co 3+ , Ni 3+ , etc.). Herein, as a compound with further excess lithium contents, a cation-ordered rocksalt phase with lithium and pentavalent niobium ions, Li 3 NbO 4 , is first examined as the host structure of a new series of high-capacity positive electrode materials for rechargeable lithium batteries. Approximately 300 mAh·g −1 of high-reversible capacity at 50°C is experimentally observed, which partly originates from charge compensation by solid-state redox of oxide ions. It is proposed that such a charge compensation process by oxide ions is effectively stabilized by the presence of electrochemically inactive niobium ions. These results will contribute to the development of a new class of high-capacity electrode materials, potentially with further lithium enrichment (and fewer transition metals) in the close-packed framework structure with oxide ions.battery | lithium | anion redox | positive electrode T o realize sustainable energy development in the future, it is widely admitted that the substitution of energy sources for fossil fuels must be considered. An efficient energy storage system using an electrochemical method, such as rechargeable lithium batteries (Li-ion batteries, LIBs), potentially provides the solution to meet these tough challenges. Now, electric vehicles equipped with an electric motor and LIB have been launched in the market, and LIBs are starting to substitute for fossil fuels as power sources in the transportation system using the technology of internal combustion engines. Since their first appearance as power sources for portable electronic devices in 1991, the technology of LIBs has now become sufficiently sophisticated. Nevertheless, the demands for a further increase in energy density are still growing to extend the driving distance for electric vehicles.In 1980, LiCoO 2 with a cation-ordered rocksalt structure (layered type) was first proposed as a positive electrode material for LIBs (1) , etc.), which are also classified as having cation-ordered rocksalt-type structures (2), have been extensively studied as potential high-capacity electrode materials, especially for the Mn 4+ system (Li 2 MnO 3 ) (3-7). Li 2 MnO 3...

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Section: +supporting

confidence: 88%

High-capacity electrode materials for rechargeable lithium batteries: Li ₃ NbO ₄ -based system with cation-disordered rocksalt structure

Yabuuchi

Takeuchi

Nakayama

et al. 2015

Proc. Natl. Acad. Sci. U.S.A.

454

560

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“…We have obtained images of the precipitate with different local O K-edge XANES spectra. By inspection of the spectra at different points of the images we concluded that locally rather pure phases of both Li 2 O 2 and Li 2 CO 3 coexisted, being the first in agreement with the literature [24], and the second with a commercial sample we measured. LiO 2 can only be hardly obtained in a pure The support is a carbonaceous inverse opal [23].…”

Section: Reference Samplessupporting

confidence: 88%

“…Qiao et al [24] specifically studied the effect of irradiating lithium peroxide, oxide, and carbonate with soft X-rays at room temperature. They found that carbonate and peroxide evolve toward oxide within several minutes of irradiation.…”

Section: Radiation Damagementioning

confidence: 99%

Studies of Lithium-Oxygen Battery Electrodes by Energy- Dependent Full-Field Transmission Soft X-Ray Microscopy

Tonti¹,

Olivares-Marín²,

Sorrentino³

et al. 2017

X-Ray Characterization of Nanostructured Energy Materials by Synchrotron Radiation

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Energy-dependent full-field transmission soft X-ray microscopy is a powerful technique that provides chemical information with spatial resolution at the nanoscale. Oxygen K-level transitions can be optimally detected, and we used this technique to study the discharge products of lithium-oxygen batteries, where this element undergoes a complex chemistry, involving at least three different oxidation states and formation of nanostructured deposits. We unambiguously demonstrated the presence of significant amounts of superoxide forming a composite with peroxide, and secondary products such as carbonates or hydroxide. In this chapter, we describe the technique from the fundamental to the observation of discharged electrodes to illustrate how this tool can help obtaining a more comprehensive view of the phenomena taking place in metal air batteries and any system involving nanomaterials with a complex chemistry.

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“…4b, the characteristic O K-edge peak associated with the Ni3d-O2p hybridization state is significantly degraded. In contrast, the intensity related to p*(C ¼ O) 41 experiences dramatic enhancement in the cycled electrode (red spectrum in Fig. 4b).…”

Section: Morphology and Electronic Structure Of Nio Nanosheetsmentioning

confidence: 93%

Phase evolution for conversion reaction electrodes in lithium-ion batteries

et al. 2014

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The performance of battery materials is largely governed by structural and chemical evolutions during electrochemical reactions. Therefore, resolving spatially dependent reaction pathways could enlighten mechanistic understanding, and enable rational design for rechargeable battery materials. Here, we present a phase evolution panorama via spectroscopic and three-dimensional imaging at multiple states of charge for an anode material (that is, nickel oxide nanosheets) in lithium-ion batteries. We reconstruct the threedimensional lithiation/delithiation fronts and find that, in a fully electrolyte immersion environment, phase conversion can nucleate from spatially distant locations on the same slab of material. In addition, the architecture of a lithiated nickel oxide is a bent porous metallic framework. Furthermore, anode-electrolyte interphase is found to be dynamically evolving upon charging and discharging. The present study has implications for resolving the inhomogeneity of the general electrochemically driven phase transition (for example, intercalation reactions) and for the origin of inhomogeneous charge distribution in large-format battery electrodes.

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Soft X-Ray Irradiation Effects of Li2O2, Li2CO3 and Li2O Revealed by Absorption Spectroscopy

Cited by 166 publications

References 52 publications

High-capacity electrode materials for rechargeable lithium batteries: Li ₃ NbO ₄ -based system with cation-disordered rocksalt structure

High-capacity electrode materials for rechargeable lithium batteries: Li ₃ NbO ₄ -based system with cation-disordered rocksalt structure

Studies of Lithium-Oxygen Battery Electrodes by Energy- Dependent Full-Field Transmission Soft X-Ray Microscopy

Phase evolution for conversion reaction electrodes in lithium-ion batteries

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Soft X-Ray Irradiation Effects of Li2O2, Li2CO3 and Li2O Revealed by Absorption Spectroscopy

Cited by 166 publications

References 52 publications

High-capacity electrode materials for rechargeable lithium batteries: Li 3 NbO 4 -based system with cation-disordered rocksalt structure

High-capacity electrode materials for rechargeable lithium batteries: Li 3 NbO 4 -based system with cation-disordered rocksalt structure

Studies of Lithium-Oxygen Battery Electrodes by Energy- Dependent Full-Field Transmission Soft X-Ray Microscopy

Phase evolution for conversion reaction electrodes in lithium-ion batteries

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High-capacity electrode materials for rechargeable lithium batteries: Li ₃ NbO ₄ -based system with cation-disordered rocksalt structure

High-capacity electrode materials for rechargeable lithium batteries: Li ₃ NbO ₄ -based system with cation-disordered rocksalt structure