Understanding Long-Term Cycling Performance of Li1.2Ni0.15Mn0.55Co0.1O2–Graphite Lithium-Ion Cells

Li, Yan; Bettge, Martin; Polzin, Bryant J.; Zhu, Ye; Balasubramanian, Mahalingam; Abraham, Daniel P.

doi:10.1149/2.002305jes

Cited by 167 publications

(205 citation statements)

References 52 publications

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“…The charged graphite electrode was reassembled against Li 2 VO 2 F cathode. Figure 5e shows [29] These preliminary results confirm that a high reversible capacity/energy-density can be still obtained for the Li 2 VO 2 F when using a Li-free anode.…”

supporting

confidence: 70%

Disordered Lithium‐Rich Oxyfluoride as a Stable Host for Enhanced Li⁺ Intercalation Storage

Chen

Ren

Knapp

et al. 2015

Advanced Energy Materials

195

294

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Keywords: Li-ion batteries, intercalation cathodes, disordered rock salt, Li 2 VO 2 F Advanced cathode materials with superior energy storage capability are highly demanded for mobile and stationary applications. The inherent structural feature of Li + hosts is critical for the battery performance. High-capacity conversion cathode materials often encounter large voltage hysteresis (low energy efficiency) accompanied with the structural reconstruction.[1]The current commercial cathode materials are still dominated by intercalation materials with intrinsic structural integrity for accommodating Li + .[2] However, the known intercalation materials have limited theoretical capacity (< 300 mAh g -1 ). [3] In addition, structural transition/degradation have often been observed for the common intercalation hosts with ordered Li + / transition metal (TM) lattice sites. Antisite disorder (Li + sites/layers occupied by TM ions) in olivines can block the one-dimensional Li + diffusion path.[4] The activation barrier for Li + diffusion in layered oxides is sensitive to the Li-content, the spacing of the

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supporting

confidence: 70%

Disordered Lithium‐Rich Oxyfluoride as a Stable Host for Enhanced Li⁺ Intercalation Storage

Chen

Ren

Knapp

et al. 2015

Advanced Energy Materials

195

294

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“…[36][37][38] Moreover, the extent of the crystal structure changes in LMR-NMC also depend on the cycling voltage window and relative ratio of Li 2 MnO 3 and LiMO 2 phases. 52 Cycling at elevated temperature does appear to have a deleterious effect on the carbon black conductive additive even within our limited cycling conditions (100 cycles, 50 mA/g, and 60…”

Section: Resultsmentioning

confidence: 71%

“…The changes in the electrochemical profile are typical of LMR-NMC and support a change in crystal structure, especially after extended cycling at elevated temperature. 52 The specific structural transformations that occur in LMR-NMC with high voltage electrochemical cycling are widely debated. Some groups observe the formation of spinel or distorted spinel phases using X-ray and electron diffraction.…”

Section: Resultsmentioning

confidence: 99%

Raman Microscopy of Lithium-Manganese-Rich Transition Metal Oxide Cathodes

Ruther

Callender

Zhou

et al. 2014

J. Electrochem. Soc.

129

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Lithium-rich and manganese-rich (LMR) layered transition metal (TM) oxide composites with general formula xLi 2 MnO 3 · (1-x)LiMO 2 (M = Ni, Co, Mn) are promising cathode candidates for high energy density lithium ion batteries. Lithium-manganese-rich TM oxides crystallize as a nanocomposite layered phase whose structure further evolves with electrochemical cycling. Raman spectroscopy is a powerful tool to monitor the crystal chemistry and correlate phase changes with electrochemical behavior. While several groups have reported Raman spectra of lithium rich TM oxides, the data show considerable variability in terms of both the vibrational features observed and their interpretation. In this study, Raman microscopy is used to investigate lithium-rich and manganese-rich TM cathodes as a function of voltage and electrochemical cycling at various temperatures. No growth of a spinel phase is observed within the cycling conditions. However, analysis of the Raman spectra does indicate the structure of LMR-NMC deviates significantly from an ideal layered phase. The results also highlight the importance of using low laser power and large sample sizes to obtain consistent data sets. Lithium-manganese-rich TM oxides form as the integrated structure of two layered phases: xLi 2 MnO 3 with C2/m space group symmetry and (1-x)LiMO 2 (M = Co, Mn, Ni, Fe, Cr) with R3m space group symmetry. While the exact structure of lithium-rich TM oxides has been the subject of much debate, a number of recent studies conclude that the material forms as the composite of these two distinct phases with nanoscale domains of Li 2 MnO 3 and LiMO 2 character. 1-6The intense interest in lithium excess cathodes stems from the potential to deliver very large reversible capacities (>200 mAh g −1 ) when charged beyond 4.5 V vs. Li 0 /Li + . 7 Part of the capacity derives from electrochemical activation of the Li 2 MnO 3 component at voltages beyond 4.4 V. Two mechanisms have been proposed for this activation. The dominant mechanism appears to be the simultaneous removal of lithium and oxygen to form a composition similar to MnO 2 . [8][9][10][11] Protons from electrolyte decomposition may also exchange for lithium. This secondary mechanism becomes more significant at higher temperature.12-14 Despite the promise of lithium rich TM oxides to deliver very high capacities, one significant limitation remains the large voltage and capacity fade observed upon extended electrochemical cycling. 15,16 A number of studies have attempted to link structural changes in lithium-rich TM oxides with electrochemical stability and cycling behavior.9,17-25 In particular, several groups have applied Raman microscopy to understand the structure and structural evolution of lithium-rich, manganese-rich TM oxides of nickel, manganese, and cobalt (hereafter LMR-NMC). 18,19,24,[26][27][28][29][30][31] Raman microscopy offers high spatial resolution (< 1μm 3 ), large field of view, and chemical specificity, making it an ideal tool to investigate both the pristine material and comp...

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“…Nevertheless, we remind the reader that the recent study of Shin et al 26 did suggest that most Mn becomes deposited relatively close to the graphite surface as opposed to the SEI surface, precisely in the manner envisioned in Figure 12. Another important consideration is that in some cycling experiments, 79 ca. 50% of Mn was deposited after the initial cycles, which guarantees significant "seeding" concentration of Mn II ions near the graphite surface, where these ions can be reduced.…”

Section: -78mentioning

confidence: 99%

Transition Metal Dissolution, Ion Migration, Electrocatalytic Reduction and Capacity Loss in Lithium-Ion Full Cells

Gilbert

Shkrob

Abraham

2017

J. Electrochem. Soc.

419

513

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Continuous operation of full cells with layered transition metal (TM) oxide positive electrodes (NCM523) leads to dissolution of TM ions and their migration and incorporation into the solid electrolyte interphase (SEI) of the graphite-based negative electrode. These processes correlate with cell capacity fade and accelerate markedly as the upper cutoff voltage (UCV) exceeds 4.30 V. At voltages ≥4.4 V there is enhanced fracture of the oxide during cycling that creates new surfaces and causes increased solvent oxidation and TM dissolution. Despite this deterioration, cell capacity fade still mainly results from lithium loss in the negative electrode SEI. Among TMs, Mn content in the SEI shows a better correlation with cell capacity loss than Co and Ni contents. As Mn ions become incorporated into the SEI, the kinetics of lithium trapping change from power to linear at the higher UCVs, indicating a large effect of these ions on SEI growth and implicating (electro)catalytic reactions. We estimate that each Mn II ion deposited in the SEI causes trapping of ∼10 2 additional Li + ions thereby hastening the depletion of cyclable lithium ions. Using these results, we sketch a mechanism for cell capacity fade, emphasizing the conceptual picture over the chemical detail. Increasing the energy and power density of Li-ion batteries (LIBs) for transportation applications is desirable for extending driving range and for providing the burst of power required for vehicle acceleration.1-3 Layered transition metal (TM) oxides containing Co, Mn, and Ni are promising high-energy electrode materials, as they exhibit theoretical oxide-specific capacities >200 mAh/g and can be cycled to potentials exceeding 4.50 V vs. Li/Li + . 4,5 However, the performance deterioration of full cells, in which these oxides are paired with a graphite (Gr) negative electrode, increases markedly at potentials exceeding 4.30 V, limiting their wider use as high-energy cathode materials.6,7 Therefore, it is imperative to examine the causes for their performance loss at high voltages. In this study we aim at understanding both the phenomenology and mechanism of capacity loss; mitigation of this loss will be the focus of future articles.Several possible causes for cell performance degradation have been identified over the years. These causes include, but are not limited to (i) TM oxide structure changes leading to voltage fade, 8 (ii) buildup of electrode surface films, especially the solid-electrolyte interphases (SEIs) 9,10 at the negative electrode, leading to Li + inventory depletion and/or impedance rise, 11-13 (iii) decomposition of the electrolyte, [14][15][16] (iv) pitting corrosion of aluminum current collectors, 17-19 (v) binder destabilization leading to delamination of electrode coatings, and (vi) dissolution of electrode-active materials. [20][21][22][23] This last source, especially the dissolution of Mn and its deposition in the negative electrode SEI, has been shown to be particularly detrimental to cell performance. [24][25][26] All steps o...

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Understanding Long-Term Cycling Performance of Li_1.2Ni_0.15Mn_0.55Co_0.1O₂–Graphite Lithium-Ion Cells

Cited by 167 publications

References 52 publications

Disordered Lithium‐Rich Oxyfluoride as a Stable Host for Enhanced Li⁺ Intercalation Storage

Disordered Lithium‐Rich Oxyfluoride as a Stable Host for Enhanced Li⁺ Intercalation Storage

Raman Microscopy of Lithium-Manganese-Rich Transition Metal Oxide Cathodes

Transition Metal Dissolution, Ion Migration, Electrocatalytic Reduction and Capacity Loss in Lithium-Ion Full Cells

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Understanding Long-Term Cycling Performance of Li1.2Ni0.15Mn0.55Co0.1O2–Graphite Lithium-Ion Cells

Cited by 167 publications

References 52 publications

Disordered Lithium‐Rich Oxyfluoride as a Stable Host for Enhanced Li+ Intercalation Storage

Disordered Lithium‐Rich Oxyfluoride as a Stable Host for Enhanced Li+ Intercalation Storage

Raman Microscopy of Lithium-Manganese-Rich Transition Metal Oxide Cathodes

Transition Metal Dissolution, Ion Migration, Electrocatalytic Reduction and Capacity Loss in Lithium-Ion Full Cells

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Product

Resources

About

Understanding Long-Term Cycling Performance of Li_1.2Ni_0.15Mn_0.55Co_0.1O₂–Graphite Lithium-Ion Cells

Disordered Lithium‐Rich Oxyfluoride as a Stable Host for Enhanced Li⁺ Intercalation Storage

Disordered Lithium‐Rich Oxyfluoride as a Stable Host for Enhanced Li⁺ Intercalation Storage