A New Sealed Lithium-Peroxide Battery with a Co-Doped Li2O Cathode in a Superconcentrated Lithium Bis(fluorosulfonyl)amide Electrolyte

Okuoka, Shin Ichi; Ogasawara, Yasushi; Suga, Yosuke; Hibino, Mitsuhiro; Kudo, Tetsuichi; Ono, Hironobu; Yonehara, Koji; Sumida, Yasutaka; Yamada, Yuki; Yamada, Atsuo; Oshima, Masaharu; Tochigi, Eita; Shibata, Naoya; Ikuhara, Yuichi; Mizuno, Noritaka

doi:10.1038/srep05684

Cited by 77 publications

(73 citation statements)

References 25 publications

(26 reference statements)

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“…Many oxides containing Li + , which had been originally thought to be electrochemically inactive, such as Li 3 NbO 4 , can potentially be used as the new host structures for high-capacity electrode materials. Recently, Codoped Li 2 O prepared by ball milling has been proposed as electrode materials with the concept of oxide ion redox even though the practical reversible capacity is limited to 200 mAh·g −1 (25). We believe that our finding will lead to material innovations on positive electrode materials for rechargeable batteries, beyond the restriction of the solid-state redox reaction based on the transition metals used for the past three decades.…”

Section: Discussionmentioning

confidence: 84%

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.

444

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: Discussionmentioning

confidence: 84%

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.

444

560

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“…Oxygen redox activity has been proposed as a possible source of the excess lithium extraction capacity in Li-excess-TM-oxide intercalation materials, such as Li 2 MnO 3 -LiMO 2 , [16,17] [4,18,19] , Co doped Li 2 O [20] Li x Ni 2-4x/3 Sb x/3 O 2 [21] and Li-Nb-M-O [22,23] systems. Such…”

Section: Introductionmentioning

confidence: 99%

“…However, the aforementioned materials exhibit a surplus capacity that cannot be explained by the TM redox couples but is commonly attributed to oxygen redox activity. [4,[16][17][18][19][20]22] Reversible charge transfer to oxygen in bulk electrode materials may become an exciting new pathway for energy storage with increased energy density.…”

Section: Introductionmentioning

confidence: 99%

Calibrating transition-metal energy levels and oxygen bands in first-principles calculations: Accurate prediction of redox potentials and charge transfer in lithium transition-metal oxides

2015

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Transition metal (TM) oxides play an increasingly important role in technology today including applications such as catalysis, solar energy harvesting, and energy storage. In many of these applications, the details of their electronic structure near the Fermi level are critically important for their properties. We propose a first-principles based computational methodology for the accurate prediction of oxygen charge transfer in TM oxides and lithium TM (Li-TM) oxides. To obtain accurate electronic structures, the Heyd-Scuseria-Ernzerhof (HSE06) hybrid functional is adopted and the amount of exact Hartree-Fock exchange (mixing parameter) is adjusted to reproduce reference band gaps.We show that the HSE06 functional with optimal mixing parameter yields not only improved electronic densities of states but also better energetics (Li-intercalation voltages) for LiCoO 2 and LiNiO 2 as compared to GGA, GGA+U and standard HSE06.We find that the optimal mixing parameters for TM oxides are system-specific and correlate with the covalency (ionicity) of the TM species. Strong covalent (ionic) nature of TM-O bonding leads to lower (higher) optimal mixing parameters. We find that optimized HSE06 functionals predict stronger hybridization of the Co 3d and O 2p orbitals than GGA, resulting in a greater contribution from oxygen states to charge compensation upon delithiation in LiCoO 2 . We also find that the band gaps of Li-TM oxides increase linearly with the mixing parameter, enabling the straightforward determination of optimal mixing parameters based on GGA (α = 0.0) and HSE06 (α = 0.25) calculations. Our results also show that G 0 W 0 @GGA+U band gaps of TM oxides (MO, M = Mn, Co, Ni) and LiCoO 2 agree well with experimental references, suggesting that G 0 W 0 calculations can be used as a reference for the calibration of the mixing parameter in case no experimental band gap has been reported. 3

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“…Solid-state redox reaction of oxide ions is also activated in Li 4 FeSbO 6 , and a reductive coupling mechanism as an irreversible process has been evidenced in this system. As a non-rocksalt system, the use of Co-doped Li 2 O has been also proposed26. Although many articles now describes the anion redox for battery materials, the border between reversibility and irreversibility for the solid-state redox reaction of oxide ions remains unclear, and it is a critical point to understand the factors affecting reversibility of anion redox.…”

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confidence: 99%

Origin of stabilization and destabilization in solid-state redox reaction of oxide ions for lithium-ion batteries

et al. 2016

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Further increase in energy density of lithium batteries is needed for zero emission vehicles. However, energy density is restricted by unavoidable theoretical limits for positive electrodes used in commercial applications. One possibility towards energy densities exceeding these limits is to utilize anion (oxide ion) redox, instead of classical transition metal redox. Nevertheless, origin of activation of the oxide ion and its stabilization mechanism are not fully understood. Here we demonstrate that the suppression of formation of superoxide-like species on lithium extraction results in reversible redox for oxide ions, which is stabilized by the presence of relatively less covalent character of Mn4+ with oxide ions without the sacrifice of electronic conductivity. On the basis of these findings, we report an electrode material, whose metallic constituents consist only of 3d transition metal elements. The material delivers a reversible capacity of 300 mAh g−1 based on solid-state redox reaction of oxide ions.

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A New Sealed Lithium-Peroxide Battery with a Co-Doped Li2O Cathode in a Superconcentrated Lithium Bis(fluorosulfonyl)amide Electrolyte

Cited by 77 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

Calibrating transition-metal energy levels and oxygen bands in first-principles calculations: Accurate prediction of redox potentials and charge transfer in lithium transition-metal oxides

Origin of stabilization and destabilization in solid-state redox reaction of oxide ions for lithium-ion batteries

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A New Sealed Lithium-Peroxide Battery with a Co-Doped Li2O Cathode in a Superconcentrated Lithium Bis(fluorosulfonyl)amide Electrolyte

Cited by 77 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

Calibrating transition-metal energy levels and oxygen bands in first-principles calculations: Accurate prediction of redox potentials and charge transfer in lithium transition-metal oxides

Origin of stabilization and destabilization in solid-state redox reaction of oxide ions for 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