Charge compensation mechanisms in Li1.16Ni0.15Co0.19Mn0.50O2 positive electrode material for Li-ion batteries analyzed by a combination of hard and soft X-ray absorption near edge structure

Oishi, Masatsugu; Fujimoto, Takahiro; Takanashi, Yu; Orikasa, Yuki; Kawamura, Atsushi; Ina, Toshiaki; Yamashige, Hisao; Takamatsu, Daiko; Satô, Kenji; Murayama, Haruno; Tanida, Hajime; Arai, Hajime; Ishii, Hideshi; Yogi, Chihiro; Watanabe, Ichiro; Ohta, Toshiaki; Mineshige, Atsushi; Uchimoto, Yoshiharu; Ogumi, Zempachi

doi:10.1016/j.jpowsour.2012.08.023

Cited by 129 publications

(158 citation statements)

References 25 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.

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429

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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.

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429

560

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“…[ 16,[18][19][20][21][22][23] However, these materials do not retain their structural integrity, owing to the holes generated on the 2p band of the O ions. Therefore, the high reversible capacity exhibited by lithium-rich compound Li 2 RuO 3 with similar layer structure seems to be counterintuitive.…”

Section: Introductionmentioning

confidence: 99%

“…DFT calculations were performed to confi rm the fi ne structural changes observed. Lithium removal of Li 16 Ru 8 O 24 supercell is performed one by one till Ru 8 O 24 is reached after determining the delithiation sequence of the two different Li sites ( Figure S5, Supporting Information). During the delithiation, the total structure remains to be stable and no metal atoms hopping happen.…”

Section: Introductionmentioning

confidence: 99%

“…[8][9][10][11][12][13][14] The common feature accounting for the high capacities of these lithium-rich layered oxides is the two redox processes involving both of cation and anion. [ 10,13,15,16 ] Despite the same process of partly charge compensation by oxygen during deep charging/discharging process, the lithiumrich layered oxides can deliver much higher reversible capacity than that of conventional cathode materials. To the best of our knowledge, such difference on the structural stability between the conventional and lithium-rich layered oxides has attracted limited attention.…”

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confidence: 99%

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Understanding the Stability for Li‐Rich Layered Oxide Li₂RuO₃ Cathode

Shao

Yan

et al. 2016

Adv Funct Materials

123

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wileyonlinelibrary.comcathode materials with well-ordered structures where most of doping metal atoms exist in the transition-metal sublattice. However, the conventional layered oxide cathode after modifi cation can only deliver a practical capacity of less than 200 mAh g −1 .In recent years, lithium-rich layered oxides based on Li 2 MO 3 (M = Mn, Ru etc.) with layered structure are considered as promising cathodes for Li-ion batteries due to their higher capacity of more than 220 mAh g −1 and higher stability at high voltage as compared with the conventional LiMO 2 layered oxides, provoking worldwide attentions. [8][9][10][11][12][13][14] The common feature accounting for the high capacities of these lithium-rich layered oxides is the two redox processes involving both of cation and anion. [ 10,13,15,16 ] Despite the same process of partly charge compensation by oxygen during deep charging/discharging process, the lithiumrich layered oxides can deliver much higher reversible capacity than that of conventional cathode materials. To the best of our knowledge, such difference on the structural stability between the conventional and lithium-rich layered oxides has attracted limited attention. It is of high importance that there must be some unknown mechanism leading to the stability difference since the geometric and electronic structure between these two kinds of layered materials are similar, except for the superlattice structure. In present work, we elucidate why lithium-rich layered oxides Li 2 RuO 3 exhibit high capacities without undergoing a structural collapse for a certain number of cycles by tracking the electronic and geometric structural changes induced in Li 2 RuO 3 during charging/discharging. Backed up with the density functional theory (DFT) calculations and a series of in situ experiments, we unravel that the presence of the lithium atoms in the transition metal layer could make the lithium-rich structure fl exible, facilitating the formation of O 2 2− -like species, which favors the structural integrity and providing high capacity. Results and DiscussionWe chose Li 2 RuO 3 as the model lithium-rich compound because it contains a single metal, making it convenient to track the electronic and geometric structural changes during charging/discharging process without interference. In addition,

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“…6,32,38,39 The oxidation of oxide ions results in partial oxygen loss, and tetravalent manganese ions are in part reduced to the trivalent state on the discharge after charge beyond the voltage plateau. 6,32,34 Moreover, similar to pure Li 2 MnO 3 , the electrode performance of the solid-solution samples highly depends on the particle size. The extent of oxygen loss vs. hole stabilization (and/or the formation of peroxide ions) is significantly influenced by the particle size.…”

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confidence: 99%

Solid-state Redox Reaction of Oxide Ions for Rechargeable Batteries

Yabuuchi¹

2017

Chem. Lett.

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Research interest for a solid-state redox reaction of oxide ions (oxygen) is rapidly increasing for rechargeable battery applications. This article reviews the history and development of charge compensation mechanisms with oxide ions for electrode materials of batteries. Reversible and irreversible processes are observed after the oxidation of oxide ions, and it highly depends on the natures of chemical bonds between transition metals and oxide ions. Future possibility of high-energy lithium/sodium batteries with the oxide ion redox is also discussed.

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Charge compensation mechanisms in Li1.16Ni0.15Co0.19Mn0.50O2 positive electrode material for Li-ion batteries analyzed by a combination of hard and soft X-ray absorption near edge structure

Cited by 129 publications

References 25 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

Understanding the Stability for Li‐Rich Layered Oxide Li₂RuO₃ Cathode

Solid-state Redox Reaction of Oxide Ions for Rechargeable Batteries

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Charge compensation mechanisms in Li1.16Ni0.15Co0.19Mn0.50O2 positive electrode material for Li-ion batteries analyzed by a combination of hard and soft X-ray absorption near edge structure

Cited by 129 publications

References 25 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

Understanding the Stability for Li‐Rich Layered Oxide Li2RuO3 Cathode

Solid-state Redox Reaction of Oxide Ions for Rechargeable 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

Understanding the Stability for Li‐Rich Layered Oxide Li₂RuO₃ Cathode