Direct observation of reversible charge compensation by oxygen ion in Li-rich manganese layered oxide positive electrode material, Li1.16Ni0.15Co0.19Mn0.50O2

Oishi, Masatsugu; Yogi, Chihiro; Watanabe, Ichiro; Ohta, Toshiaki; Orikasa, Yuki; Uchimoto, Yoshiharu; Ogumi, Zempachi

doi:10.1016/j.jpowsour.2014.11.104

Cited by 143 publications

(144 citation statements)

References 31 publications

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“…22 Such a plateau, shown in Li-rich manganese layered oxides, is associated with simultaneous Li + and O 2¹ removal, 1 cation migration 5,6 and/or oxidation of oxygen. 10 Moreover, the discharge voltage decreased monotonously. The LMR delivered initial charge and discharge capacity of 290 mAh g ¹1 (1.6 Li) and 210 mAh g ¹1 (1.2 Li), respectively.…”

Section: Resultsmentioning

confidence: 98%

“…[1][2][3][4] Many studies have been devoted to investigate the mechanism underlying the higher initial charging capacity which is irreversible in the subsequent cycle. 1,[5][6][7][8][9][10] Several models have been proposed regarding the initially high irreversible charging capacity such as simultaneous Li + and O 2¹ removal, 1 cation migration 5,6 and the participation of oxygen redox species. 10 Further studies have also been widely done to unravel the mechanism underlying the intrinsic voltage decay upon subsequent cycling of Li-rich manganese layered oxide.…”

Section: Introductionmentioning

confidence: 99%

“…1,[5][6][7][8][9][10] Several models have been proposed regarding the initially high irreversible charging capacity such as simultaneous Li + and O 2¹ removal, 1 cation migration 5,6 and the participation of oxygen redox species. 10 Further studies have also been widely done to unravel the mechanism underlying the intrinsic voltage decay upon subsequent cycling of Li-rich manganese layered oxide. [11][12][13][14] Recently, we first reported that the solid solution of Li 2 Mn 1¹x Ru x O 3 exhibit high capacity of about 200 mAh g ¹1 and lower electrical resistivity five order of magnitude than Li 2 MnO 3 , indicating that the substitution of Ru is effective to enhance the electrochemical as well as electrical properties.…”

Section: Introductionmentioning

confidence: 99%

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Relationship between Cyclic Properties and Charge-discharge Condition for Li2Mn0.4Ru0.6O3 and Li2RuO3

et al. 2015

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Capacity and voltage retentions upon subsequent cycles for Li 2 RuO 3 and Li 2 Mn 0.4 Ru 0.6 O 3 (LMR) under various cutoff voltages have been investigated. The change in average and local structures upon electrochemical cycling were examined by ex-situ XRD and Ru L 3 -edge XANES measurements, and the relationship between the cyclic capabilities and the structural changes is discussed. The deteriorations of discharge capacity and average discharge voltage in the subsequent cycles of LMR with a charge cut-off voltage of 4.8 V vs. Li/Li + are remarkably smaller than that with the voltage of 4.2 V. Moreover, LMR exhibits higher average discharge voltage than Li 2 RuO 3 under a charge cut-off voltage of 4.8 V. The phase transition behavior of LMR was not similar to Li 2 RuO 3 upon electrochemical cycling. Ru L 3 -edge XANES spectra measurements reveal that RuO 6 octahedra in LMR charged at 4.2 V are much distorted. The local structure of RuO 6 octahedra is associated with the cyclic capability of LMR and Li 2 RuO 3 .

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Section: Resultsmentioning

confidence: 98%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Relationship between Cyclic Properties and Charge-discharge Condition for Li2Mn0.4Ru0.6O3 and Li2RuO3

et al. 2015

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“…5 This extra capacity originates from anionic redox, as validated recently by Density Functional Theory (DFT) calculations 9 and direct experimental proofs with soft X-ray absorption spectroscopy (XAS) 10,11 and X-ray photoelectron spectroscopy. 12,13 Despite the promise of large capacities, unfortunately, a decade long research effort in commercializing LR-NMCs has remained unsuccessful because the extra capacity comes with undesirable practical drawbacks, such as voltage fade, voltage hysteresis, and poor rate capability.…”

mentioning

confidence: 83%

Editors' Choice—Practical Assessment of Anionic Redox in Li-Rich Layered Oxide Cathodes: A Mixed Blessing for High Energy Li-Ion Batteries

Assat

Delacourt

Corte

et al. 2016

J. Electrochem. Soc.

144

200

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Li-rich layered oxides, e.g. Li [Li 0.20 Ni 0.13 Mn 0.54 Co 0.13 ]O 2 (LR-NMC), lead high energy density Li-ion battery cathodes, thanks to the reversible redox of oxygen anions that boost charge storage capacity. Unfortunately, their commercialization has been stalled by practical issues (i.e. voltage hysteresis, poor rate capability, and voltage fade) and hence it is necessary to investigate whether these problems are intrinsically inherent to anionic redox and its structural consequences. To this end, the 'model' Li-rich layered oxide Li 2 Ru 0.75 Sn 0.25 O 3 (LRSO) is here used as a fertile test-bed for scrutinizing the effects of cationic and anionic redox independently since they are neatly isolated at low and high potentials, respectively. Through an arsenal of electrochemical techniques, we demonstrate that voltage hysteresis is triggered by anionic redox and grows progressively with deeper oxidation of oxygen in conjunction with the deterioration of both interfacial charge-transfer kinetics and bulk diffusion coefficient. We equally show that this anionic-driven poor kinetics keeps deteriorating further with cycling and we also find that voltage fades faster if oxygen is kept oxidized for longer. Our findings, which are in fact harsher for LR-NMC, convey caution that anionic redox risks practical problems; hence, when chasing larger capacities with this class of materials, we encourage considering real-world applications.

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“…2,48-52 Involvement of oxide in reversible redox activity is supported by XANES O k-edge spectra, 46,47 EXAFS describing Mn-O bond changes, 14 HAADF STEM images showing peroxo dimer formation 48 and by ab-initio molecular orbital calculations. 2,48 The involvement of O 2− anionic redox is thought to have slower kinetics than cationic redox, as well as enhances the materials' voltage hysteresis and fade.…”

Section: Redox Designations Of Li-rich Materialsmentioning

confidence: 94%

Review—Recent Advances and Remaining Challenges for Lithium Ion Battery Cathodes

Erickson

Schipper

Penki

et al. 2017

J. Electrochem. Soc.

153

103

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Electrodes prepared from lithium-rich (Li-rich) xLi 2 MnO 3 ·(1-x)LiNi a Co b Mn c O 2 materials (a + b + c = 1) show extremely high discharge capacities, arising from excess Li + present in their Li 2 MnO 3 component, and the ability to reversibly store charge with O 2− anions. These electrodes suffer serious voltage and capacity fading however, due to the migration of transition metals to the Li-layer at advanced states of charging, partial structural layered-to-spinel transformation and other reasons. In this focus paper, the current understanding of the above materials is summarized, briefly concluding with attempts by our groups to mitigate the voltage and capacity fade of these electrodes.

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Direct observation of reversible charge compensation by oxygen ion in Li-rich manganese layered oxide positive electrode material, Li1.16Ni0.15Co0.19Mn0.50O2

Cited by 143 publications

References 31 publications

Relationship between Cyclic Properties and Charge-discharge Condition for Li<sub>2</sub>Mn<sub>0.4</sub>Ru<sub>0.6</sub>O<sub>3</sub> and Li<sub>2</sub>RuO<sub>3</sub>

Relationship between Cyclic Properties and Charge-discharge Condition for Li<sub>2</sub>Mn<sub>0.4</sub>Ru<sub>0.6</sub>O<sub>3</sub> and Li<sub>2</sub>RuO<sub>3</sub>

Editors' Choice—Practical Assessment of Anionic Redox in Li-Rich Layered Oxide Cathodes: A Mixed Blessing for High Energy Li-Ion Batteries

Review—Recent Advances and Remaining Challenges for Lithium Ion Battery Cathodes

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