Solid-state Redox Reaction of Oxide Ions for Rechargeable Batteries

Yabuuchi, Naoaki

doi:10.1246/cl.161044

Cited by 60 publications

(59 citation statements)

References 72 publications

(56 reference statements)

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“…However, the fact is that Li 2 MnO 3 is electrochemically active associated with the contribution of anions (oxide ions) for the charge compensation process ,. Detailed reaction mechanisms of Li 2 MnO 3 are found in the literature . Historically, charge compensation by non‐cationic species has been already known in sulfides before 1990 .…”

Section: Materials Design Concept Of Li‐excess Rocksalt Oxidessupporting

confidence: 83%

Material Design Concept of Lithium‐Excess Electrode Materials with Rocksalt‐Related Structures for Rechargeable Non‐Aqueous Batteries

Yabuuchi

2018

The Chemical Record

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Dependence on lithium‐ion batteries for automobile applications is rapidly increasing, and further improvement, especially for positive electrode materials, is indispensable to increase energy density of lithium‐ion batteries. In the past several years, many new lithium‐excess high‐capacity electrode materials with rocksalt‐related structures have been reported. These materials deliver high reversible capacity with cationic/anionic redox and percolative lithium migration in the oxide/oxyfluoride framework structures, and recent research progresses on these electrode materials are reviewed. Material design strategies for these lithium‐excess electrode materials are also described. Future possibility of high‐energy non‐aqueous batteries with advanced positive electrode materials is discussed for more details.

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Section: Materials Design Concept Of Li‐excess Rocksalt Oxidessupporting

confidence: 83%

Material Design Concept of Lithium‐Excess Electrode Materials with Rocksalt‐Related Structures for Rechargeable Non‐Aqueous Batteries

Yabuuchi

2018

The Chemical Record

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“…It is worth noting that no diffraction peaks attributed to the starting materials were observed. Only broad peaks assigned to the cation-disordered rock-salt phase [34][35][36][37] with a space group of Fm 3 m were observed at all of the compositions. Figure 1b shows scanning electron microscopy (SEM) images of the NMC532 and Li 2 SO 4 crystals.…”

Section: Synthesis and Structural Analysis Of The Amorphous Materialsmentioning

confidence: 99%

Amorphous Ni‐Rich Li(Ni₁₋_x₋_yMn_xCo_y)O₂–Li₂SO₄ Positive Electrode Materials for Bulk‐Type All‐Oxide Solid‐State Batteries

Nagao

Sakuda

Hayashi

et al. 2019

Adv Materials Inter

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typical organic liquid electrolytes. [1][2][3] Although the safety and reliability of batteries can be potentially improved by utilizing solid electrolytes instead of liquid electrolytes, there are still several challenges in sulfide-type all-solidstate batteries, such as H 2 S generation and chemical reaction with active materials. [4][5][6][7] On the other hand, oxide-type all-solid-state batteries have been regarded as one of the leading candidates to overcome these problems owing to the high chemical and electrochemical stabilities of oxide electrolytes. Despite the merits, the construction of all-oxide solid-state batteries is quite difficult owing to the lack of deformability of the typical crystalline oxide electrolytes, which leads to a poor contact between the active material and solid electrolyte particles. [8] Therefore, high-temperature sintering is required to achieve a good contact. Even if a good contact is achieved, unfavorable chemical reactions between the active material and solid electrolyte might proceed at the high temperature, leading to generation of a highly resistive layer. [9,10] Therefore, formation of an excellent electrode/ electrolyte interface without high-temperature sintering is important for the operation of all-oxide solid-state batteries. In order to achieve a good formability in oxide electrolytes, we have focused on materials with lower melting points such as Li 3 BO 3 . [11] A mechanochemically prepared Li 3 BO 3 glass electrolyte exhibited a relatively high conductivity of 10 −7 S cm −1 at room temperature and good formability. In addition, we previously developed ductile oxide glass-ceramic electrolytes of the pseudobinary system Li 3 BO 3 -Li 2 SO 4 . The Li 2.9 B 0.9 S 0.1 O 3.1 (90Li 3 BO 3 ·10Li 2 SO 4 (mol%)) glass-ceramic electrolyte exhibited a high conductivity of ≈10 −5 S cm −1 at room temperature. [12,13] A good contact with electrode active materials was successfully achieved simply by pressing at room temperature, which was enabled by the excellent formability of the electrolyte.Crystalline materials such as layered, [14,15] spinel, [16] and olivine [17] structures have been utilized as positive electrode materials in typical lithium-ion and all-solid-state batteries. Amorphous materials are also candidates for electrode materials, which generally exhibit higher conductivities than those of the All-solid-state batteries attract significant attention owing to their potential to realize an energy storage system with high safety and energy density. In this paper, a mechanochemical synthesis of novel amorphous positive electrode materials of the Ni-rich LiNi 1−x−y Mn x Co y O 2 (NMC)-Li 2 SO 4 system suitable for oxide-type all-solid-state batteries is reported. Through the mechanochemical treatment with Li 2 SO 4 , excellent formabilities of the electrode materials as those of ductile solid electrolytes are obtained. Owing to the deformability of the active material, a good electrode/electrolyte interface is provided simply by pressing at room temperature. In all...

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“…Nevertheless, the energy density of these as‐prepared electrode materials is not competitive to LiMn 2 O 4 and LiFePO 4 used as cost‐effective positive electrode materials for Li batteries. Moreover, emerging chemistry of anionic redox for Li‐excess compounds, Li 2 MnO 3 and its derivatives, potentially further boosts the energy density of Li batteries . Instead of transition metal ions with d‐electrons, oxide ions, as noncationic species in the structure, donate electrons upon charge compensation during electrochemical Li extraction (oxidation).…”

mentioning

confidence: 99%

“…Moreover, emerging chemistry of anionic redox for Li-excess compounds, Li 2 MnO 3 and its derivatives, potentially further boosts the energy density of Li batteries. [13][14][15][16] Instead of transition metal ions with d-electrons, oxide ions, as noncationic species in the structure, donate electrons upon charge compensation during electrochemical Li extraction (oxidation). The development of electrode materials, which simultaneously use classical cationic and anionic redox, is accelerating throughout the world.…”

mentioning

confidence: 99%

Nanosize Cation‐Disordered Rocksalt Oxides: Na₂TiO₃–NaMnO₂ Binary System

Kobayashi

Zhao

Rajendra

et al. 2019

Small

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To realize the development of rechargeable sodium batteries, new positive electrode materials without less abundant elements are explored. Enrichment of sodium contents in host structures is required to increase the theoretical capacity as electrode materials, and therefore Na‐excess compounds are systematically examined in a binary system of Na2TiO3–NaMnO2. After several trials, synthesis of Na‐excess compounds with a cation disordered rocksalt structure is successful by adapting a mechanical milling method. Among the tested electrode materials, Na1.14Mn0.57Ti0.29O2 in this binary system delivers a large reversible capacity of ≈200 mA h g−1, originating from reversible redox reactions of cationic Mn3+/Mn4+ and anionic O2−/On− redox confirmed by X‐ray absorption spectroscopy. Holes in oxygen 2p orbitals, which are formed by electrochemical oxidation, are energetically stabilized by electron donation from Mn ions. Moreover, reversibility of anionic redox is significantly improved compared with a former study on a binary system of Na3NbO3–NaMnO2 tested as model electrode materials.

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Solid-state Redox Reaction of Oxide Ions for Rechargeable Batteries

Cited by 60 publications

References 72 publications

Material Design Concept of Lithium‐Excess Electrode Materials with Rocksalt‐Related Structures for Rechargeable Non‐Aqueous Batteries

Material Design Concept of Lithium‐Excess Electrode Materials with Rocksalt‐Related Structures for Rechargeable Non‐Aqueous Batteries

Amorphous Ni‐Rich Li(Ni₁₋_x₋_yMn_xCo_y)O₂–Li₂SO₄ Positive Electrode Materials for Bulk‐Type All‐Oxide Solid‐State Batteries

Nanosize Cation‐Disordered Rocksalt Oxides: Na₂TiO₃–NaMnO₂ Binary System

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Solid-state Redox Reaction of Oxide Ions for Rechargeable Batteries

Cited by 60 publications

References 72 publications

Material Design Concept of Lithium‐Excess Electrode Materials with Rocksalt‐Related Structures for Rechargeable Non‐Aqueous Batteries

Material Design Concept of Lithium‐Excess Electrode Materials with Rocksalt‐Related Structures for Rechargeable Non‐Aqueous Batteries

Amorphous Ni‐Rich Li(Ni1−x−yMnxCoy)O2–Li2SO4 Positive Electrode Materials for Bulk‐Type All‐Oxide Solid‐State Batteries

Nanosize Cation‐Disordered Rocksalt Oxides: Na2TiO3–NaMnO2 Binary System

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Amorphous Ni‐Rich Li(Ni₁₋_x₋_yMn_xCo_y)O₂–Li₂SO₄ Positive Electrode Materials for Bulk‐Type All‐Oxide Solid‐State Batteries

Nanosize Cation‐Disordered Rocksalt Oxides: Na₂TiO₃–NaMnO₂ Binary System