Mitigation of Layered to Spinel Conversion of a Li-Rich Layered Metal Oxide Cathode Material for Li-Ion Batteries

Ateş, Mehmet Nurullah; Jia, Qingying; Shah, Ankita; Busnaina, Ahmed; Mukerjee, Sanjeev; Abraham, K. M.

doi:10.1149/2.040403jes

Cited by 183 publications

(164 citation statements)

References 51 publications

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“…[8][9][10]16,25,52 The transformation from layered to spinel is expected to be accelerated by cycling at elevated temperature. [53][54][55] Interestingly enough the high frequency mode around 630 to 650 cm…”

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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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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“…Moreover, higher Ni concentrations result in highly unstable Ni 3+ and Ni 4+ ions remaining in the layered structure, and their reaction with the electrolyte speeds up 2 Journal of Nanomaterials degradation of the materials and batteries [10,11]. In order to solve these problems, the small amounts of dopants at the cationic sites have been considered; for example, it has been reported that the addition of small amounts of Cl, Mg, F, and Na improves the capacity and cycle performance [12][13][14][15][16][17].…”

Section: Introductionmentioning

confidence: 99%

Effect of Metal (Mn, Ti) Doping on NCA Cathode Materials for Lithium Ion Batteries

Wan

Fan

Baasanjav

et al. 2018

Journal of Nanomaterials

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NCA (LiNi 0.85 Co 0.10 Al 0.05−x M x O 2 , M=Mn or Ti, < 0.01) cathode materials are prepared by a hydrothermal reaction at 170 ∘ C and doped with Mn and Ti to improve their electrochemical properties. The crystalline phases and morphologies of various NCA cathode materials are characterized by XRD, FE-SEM, and particle size distribution analysis. The CV, EIS, and galvanostatic charge/discharge test are employed to determine the electrochemical properties of the cathode materials. Mn and Ti doping resulted in cell volume expansion. This larger volume also improved the electrochemical properties of the cathode materials because Mn 4+and Ti 4+ were introduced into the octahedral lattice space occupied by the Li-ions to expand the Li layer spacing and, thereby, improved the lithium diffusion kinetics. As a result, the NCA-Ti electrode exhibited superior performance with a high discharge capacity of 179.6 mAh g −1 after the first cycle, almost 23 mAh g −1 higher than that obtained with the undoped NCA electrode, and 166.7 mAh g −1 after 30 cycles. A good coulombic efficiency of 88.6% for the NCA-Ti electrode is observed based on calculations in the first charge and discharge capacities. In addition, the NCA-Ti cathode material exhibited the best cycling stability of 93% up to 30 cycles.

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“…19,22,23 However, to obtain such a capacity, these materials must be cycled over a wide potential range of 2.5-4.6 V (vs. Li + /Li), which may be challenging for the current carbonate-based electrolytes. Major issues such as large irreversible capacity (IRC), 19,33,34 voltage fade upon cycling 22,[35][36][37][38][39][40] and poor rate capability 22,41,42 have hindered the application of these materials. * Electrochemical Society Student Member.…”

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confidence: 99%

Study of the Failure Mechanisms of LiNi_0.8Mn_0.1Co_0.1O₂Cathode Material for Lithium Ion Batteries

Downie

et al. 2015

J. Electrochem. Soc.

443

372

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LiNi 0.8 Mn 0.1 Co 0.1 O 2 (NMC811) can deliver a high capacity of ∼200 mAh/g with an average discharge potential of ∼3.8 V (vs. Li + /Li), making it a promising positive electrode material for high energy density lithium ion batteries. However, electrochemical tests from half cells and full cells show poor cycling performance when charged to potentials above 4.2 V. The calendar and cycle lifetimes of cells are affected by the structural stability of the active electrode materials as well as the parasitic reactions that occur in lithium ion batteries. In order to explore the major failure mechanisms of the material, half cells (coin cells) with control electrolyte and full cells (pouch cells) with control electrolyte and with selected electrolyte additives were tested over four different potential ranges. Isothermal microcalorimetry was used to explore the parasitic reactions and their potential dependence. In-situ and ex-situ X-ray diffraction and scanning electron microscopy were used to investigate the structural and morphological degradation of the materials over cycling. It was found that the dramatic c-axis change of the active material during charge and discharge may not be the major problem for cells that are cycled to higher potentials. The parasitic reactions that arise from the interactions between the electrolyte and the highly reactive delithiated cathode surface at high potentials are suggested as the main reason for the failure of cells cycled above 4.2 V. It should be possible to further improve the performance of NMC811 at high potentials by modifying the cathode surface and/or identifying and using electrolyte blends which reduce parasitic reactions. High energy density lithium ion batteries (LIBs) that are cheaper, safer, and with longer lifetimes need to be developed in order to meet the increasing demand for applications such as electric vehicles and large scale stationary energy storage. The energy density of LIBs can be increased by increasing the specific capacity and average potential of the cells. The calendar and cycle lifetimes of cells are affected by the structural stability of the active electrode materials as well as the parasitic reactions that occur in lithium ion batteries. The degree of lithium utilization of LiCoO 2 is limited to ∼70% in order avoid the O3 -H1-3 -O1 phase transformation when charged above 4.45 V.1 Parasitic reactions such as electrolyte oxidation at the cathode-electrolyte interface can ultimately cause cell failure.2-5 The rate of the parasitic reactions is related to both the catalytic role of the cathode surface which depends on its composition and surface area, 3,6 as well as on the stability of the electrolyte.2-5 Methods such as the use of electrolyte additives 7-11 and core-shell positive electrode materials [12][13][14] have been developed and studied to reduce the rate and extent of parasitic reactions, and hence increase capacity retention and lifetime of high-voltage Li-ion cells. The layered lithium Ni-Mn-Co oxides Li 1+x (Ni y Mn z Co (1-y-z) ) 1...

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Mitigation of Layered to Spinel Conversion of a Li-Rich Layered Metal Oxide Cathode Material for Li-Ion Batteries

Cited by 183 publications

References 51 publications

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

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

Effect of Metal (Mn, Ti) Doping on NCA Cathode Materials for Lithium Ion Batteries

Study of the Failure Mechanisms of LiNi_0.8Mn_0.1Co_0.1O₂Cathode Material for Lithium Ion Batteries

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Mitigation of Layered to Spinel Conversion of a Li-Rich Layered Metal Oxide Cathode Material for Li-Ion Batteries

Cited by 183 publications

References 51 publications

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

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

Effect of Metal (Mn, Ti) Doping on NCA Cathode Materials for Lithium Ion Batteries

Study of the Failure Mechanisms of LiNi0.8Mn0.1Co0.1O2Cathode Material for Lithium Ion Batteries

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Study of the Failure Mechanisms of LiNi_0.8Mn_0.1Co_0.1O₂Cathode Material for Lithium Ion Batteries