Li4/3Ni1/3Mo1/3O2– LiNi1/2Mn1/2O2Binary System as High Capacity Positive Electrode Materials for Rechargeable Lithium Batteries

Zhao, Wenwen; Yamaguchi, Kazuma; Sato, Takuma; Yabuuchi, Naoaki

doi:10.1149/2.0661807jes

Cited by 9 publications

(12 citation statements)

References 40 publications

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“…Although both compounds have similar redox potentials in oxidation, the Ni-based compound shows a lower average reduction potential of 3 V that is due to a sudden drop in voltage of 1.5 V, compared to 3.2 V for the Mn-based one. Interestingly, this phenomenon can be observed in many Ni-based rock salt oxides (Table S1) ,,− but never in Mn-based compounds. The origin of such a feature has been investigated in only two studies: (i) Lee et al attributed this phenomenon to the formation of a Li-poor layer at the surface of the material during charge, impeding Li diffusion for Li 1.2 Ni 0.33 Ti 0.33 Mo 0.13 O 2 , and (ii) Zhao et al proposed the reduction of Mn/Mo due to oxygen release in Li 1.2 Ni 0.4 Mn 0.2 Mo 0.2 O 2 .…”

Section: Introductionmentioning

confidence: 97%

“…This mainly calls for the design of new cathode materials with higher capacity and working potential. Along that line, Li-excess disordered rocksalt oxides (DRS) are interesting materials since they show very high capacity, 300 mAh/g for Li 1 3,5,[7][8][9][10] , but never in Mn-based compounds. The origin of such feature has been investigated in only two studies: i) Lee compounds, and ii) probe the role of Ta 5+ (5d 0 ) substitution in the overall redox processes, compared to Nb 5+ and Mo 6+ (4d 0 ), or Ti 4+ (3d 0 ).…”

Section: Introductionmentioning

confidence: 99%

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Charge Transfer Band Gap as an Indicator of Hysteresis in Li-Disordered Rock Salt Cathodes for Li-Ion Batteries

et al. 2019

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Disordered rocksalt compounds showing both anionic and cationic redox are being extensively studied for their very high energy storage capacity. While the Mn-based disordered rocksalt compounds show decent energy efficiency, it is drastically lower in the Ni-based materials due to different voltage hysteresis, 0.5 V and 2 V, respectively. To understand the origin of this difference, we herein report the design of two model compounds Li 1.3 Ni 0.27 Ta0. 43 O 2 and Li 1.3 Mn 0.4 Ta 0.3 O 2 and study their charge compensation mechanism through the uptake and removal of Li via an arsenal of analytical techniques. We show that different voltage hysteresis with Ni or Mn substitution is due to differences in the way anionic redox proceeds. We rationalized such a finding by DFT calculations and propose this drastic difference to be nested in the smaller charge transfer band gap of the Ni-based compounds compared to the Mn ones. Altogether these findings provide vital guidelines for designing high capacity disordered rocksalt cathode materials based on anionic redox activity for next generation of Li-ion batteries.

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Section: Introductionmentioning

confidence: 97%

Section: Introductionmentioning

confidence: 99%

Charge Transfer Band Gap as an Indicator of Hysteresis in Li-Disordered Rock Salt Cathodes for Li-Ion Batteries

et al. 2019

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“…Redox reactions of such anionic species dramatically change the requirements of the host materials and hence the material design strategies for energy storage applications. − New lithium-excess and high-capacity positive electrode materials have appeared in the past several years. − Among them, binary systems with LiMnO 2 have been proposed as a new class of electrode materials, including Li 3 NbO 4 –LiMnO 2 , Li 2 TiO 3 –LiMnO 2 , and LiF–LiMnO 2 , , and these Li-excess electrode materials effectively utilize the anionic redox coupled with the cationic redox of Mn 3+ /Mn 4+ . In these cases, the end-members of Li 3 NbO 4 , Li 2 TiO 3 , and LiF are known as electrochemically inactive because of the absence of conductive electrons.…”

Section: Introductionmentioning

confidence: 99%

Nanostructured LiMnO₂ with Li₃PO₄ Integrated at the Atomic Scale for High-Energy Electrode Materials with Reversible Anionic Redox

et al. 2020

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Nanostructured LiMnO 2 integrated with Li 3 PO 4 was successfully synthesized by the mechanical milling route and examined as a new series of positive electrode materials for rechargeable lithium batteries. Although uniform mixing at the atomic scale between LiMnO 2 and Li 3 PO 4 was not anticipated because of the noncompatibility of crystal structures for both phases, our study reveals that phosphorus ions with excess lithium ions dissolve into nanosize crystalline LiMnO 2 as first evidenced by elemental mapping using STEM-EELS combined with total X-ray scattering, solid-state NMR spectroscopy, and a theoretical ab initio study. The integrated phase features a low-crystallinity metastable phase with a unique nanostructure; the phosphorus ion located at the tetrahedral site shares faces with adjacent lithium ions at slightly distorted octahedral sites. This phase delivers a large reversible capacity of ∼320 mA h g –1 as a high-energy positive electrode material in Li cells. The large reversible capacity originated from the contribution from the anionic redox of oxygen coupled with the cationic redox of Mn ions, as evidenced by operando soft XAS spectroscopy, and the superior reversibility of the anionic redox and the suppression of oxygen loss were also found by online electrochemical mass spectroscopy. The improved reversibility of the anionic redox originates from the presence of phosphorus ions associated with the suppression of oxygen dimerization, as supported by a theoretical study. From these results, the mechanistic foundations of nanostructured high-capacity positive electrode materials were established, and further chemical and physical optimization may lead to the development of next-generation electrochemical devices.

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“…In this oxide, Li‐ion transports between two different octahedral sites, passing through an activated tetrahedral site where Li has a lower migration energy barrier and makes the diffusion of Li‐ion smooth 21‐24 . Based on this mechanism, some Li‐excess cation‐disordered rock‐salt structure (DRS) oxides and fluorides have been synthesized and studied in the past decade 25‐29 . Most of them belong to Li‐M‐O based systems (M, high valent transition ion, eg, Mn 4+ , Ti 4+ , Nb 5+ , Mo 6+ , or Ru 6+ ) which have great specific capacities with excess lithium contents 30‐34 .…”

Section: Introductionmentioning

confidence: 99%

“…[21][22][23][24] Based on this mechanism, some Liexcess cation-disordered rock-salt structure (DRS) oxides and fluorides have been synthesized and studied in the past decade. [25][26][27][28][29] Most of them belong to Li-M-O based systems (M, high valent transition ion, eg, Mn 4+ , Ti 4+ , Nb 5+ , Mo 6+ , or Ru 6+ ) which have great specific capacities with excess lithium contents. [30][31][32][33][34] Compared with the traditional cation-ordered oxides, DRS materials have some highlights that make DRS become a very active field of high-capacity cathodes.…”

mentioning

confidence: 99%

Synthesis and electrochemical properties of cation‐disordered rock‐salt x Li ₃ NbO ₄ ·(1 − x ) NiO compounds for Li‐ion batteries

Luo

Lin

et al. 2020

Int J Energy Res

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In this study, Li-excess cation-disordered rock-salt cathode materials, xLi 3 NbO 4 Á(1 − x) NiO (LNNO, 0.55 ≤ x ≤ 0.7), are synthesized to explore the effect of composition on the structure and electrochemical performance using a sol-gel method for the first time. X-ray diffraction results combined with Rietveld refinements demonstrate that pure cation-disordered rock-salt structure can be obtained at x ≥ 0.6. The electron microscopy results of samples demonstrate the irregular particles with size of 1 to 10 μm and rock-salt structure is further confirmed. The samples with x = 0.6, 0.65, and 0.7, respectively, exhibit the much higher reversible capacity than their theoretical Ni 2+ /Ni 3+ capacity attributing to anionic redox reaction. The LNNO6 sample deliver the first discharge capacity 155.35 mAh/g and 82.9% capacity retention after 40 cycles. In addition, X-ray photoelectron spectroscopy analyses and dV/dQ measurements are utilized to investigate the restricted electrochemical behaviors and performances which are constrained by the competition between Ni 2+ /Ni 3+ and O 2− /O −. K E Y W O R D S cation-disordered, electrochemical performance, lithium ion battery, Li 3 NbO 4-based rock-salt structure 1 | INTRODUCTION With the advantages of low pollution, high energy density, and long cycle life, lithium-ion batteries have become the most popular rechargeable batteries in portable electronics and vehicles. 1-5 To solve the crisis of energy resource and environmental pollution, some promising materials, such as transition metal (TM) oxides, metal-organic frameworks (MOFs), and Si-based materials are designed for the areas of lithium batteries, catalysis, supercapacitor, and optical devices. 6-16 Therefore, aiming at the application of Li-ion batteries for advanced energy powers, researchers around the world have paid a lot of efforts to develop cathode materials, especially the ordered TM oxides, such as LiMO 2 and Li 1 + x M 1 − x O 2 (M = Mn, Ni, Co, etc.). 17-19 It was generally accepted in the past several decades that wellordered structure between Li and the TM sublattice is good for Li diffusion and then improve the electrochemical performance effectively. However, most of layered cathode materials suffer from instability and oxygen release in the charging process as the result of cations mixing and phase change. Recently, cation-disordered materials have attracted more attention because of unique lithium migration

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Li_4/3Ni_1/3Mo_1/3O₂– LiNi_1/2Mn_1/2O₂Binary System as High Capacity Positive Electrode Materials for Rechargeable Lithium Batteries

Cited by 9 publications

References 40 publications

Charge Transfer Band Gap as an Indicator of Hysteresis in Li-Disordered Rock Salt Cathodes for Li-Ion Batteries

Charge Transfer Band Gap as an Indicator of Hysteresis in Li-Disordered Rock Salt Cathodes for Li-Ion Batteries

Nanostructured LiMnO₂ with Li₃PO₄ Integrated at the Atomic Scale for High-Energy Electrode Materials with Reversible Anionic Redox

Synthesis and electrochemical properties of cation‐disordered rock‐salt x Li ₃ NbO ₄ ·(1 − x ) NiO compounds for Li‐ion batteries

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Li4/3Ni1/3Mo1/3O2– LiNi1/2Mn1/2O2Binary System as High Capacity Positive Electrode Materials for Rechargeable Lithium Batteries

Cited by 9 publications

References 40 publications

Charge Transfer Band Gap as an Indicator of Hysteresis in Li-Disordered Rock Salt Cathodes for Li-Ion Batteries

Charge Transfer Band Gap as an Indicator of Hysteresis in Li-Disordered Rock Salt Cathodes for Li-Ion Batteries

Nanostructured LiMnO2 with Li3PO4 Integrated at the Atomic Scale for High-Energy Electrode Materials with Reversible Anionic Redox

Synthesis and electrochemical properties of cation‐disordered rock‐salt x Li 3 NbO 4 ·(1 − x ) NiO compounds for Li‐ion batteries

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Li_4/3Ni_1/3Mo_1/3O₂– LiNi_1/2Mn_1/2O₂Binary System as High Capacity Positive Electrode Materials for Rechargeable Lithium Batteries

Nanostructured LiMnO₂ with Li₃PO₄ Integrated at the Atomic Scale for High-Energy Electrode Materials with Reversible Anionic Redox

Synthesis and electrochemical properties of cation‐disordered rock‐salt x Li ₃ NbO ₄ ·(1 − x ) NiO compounds for Li‐ion batteries