Study of the electrochemical behavior of the “inactive” Li2MnO3

Amalraj, S. Francis; Markovsky, Boris; Sharon, Daniel; Talianker, M.; Zinigrad, Ella; Persky, Rachel; Haik, Ortal; Grinblat, Judith; Lampert, Jordan; Schulz‐Dobrick, Martin; Garsuch, Arnd; Burlaka, Luba; Aurbach, Doron

doi:10.1016/j.electacta.2012.05.144

Cited by 135 publications

(78 citation statements)

References 33 publications

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“…The discharge specific capacity of 160 mAh g −1 increases to a value of 175 mAh g −1 in about eight cycles and a steady capacity is then observed, even after 100 cycles in the case of LiNi 0.33 Mn 0.54 Co 0.13 O 2 cathodes (Figure i). The initial increase in the discharge capacity can be attributed to the presence of Li 2 MnO 3 , which takes a few cycles to become activated …”

Section: Resultssupporting

confidence: 78%

Multiphase LiNi_0.33Mn_0.54Co_0.13O₂ Cathode Material with High Capacity Retention for Li‐Ion Batteries

et al. 2015

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An integrated layered‐spinel LiNi0.33Mn0.54Co0.13O2 material was synthesized through a self‐combustion reaction (SCR), characterized by using X‐ray diffraction, scanning electron microscopy, transmission electron microscopy (TEM), and Raman spectroscopy. It was studied as a cathode material for Li‐ion batteries and its electrochemical performance was compared with that of the layered cathode material LiNi0.33Mn0.33Co0.33O2 when operated over a wide potential window. The Rietveld analysis of LiNi0.33Mn0.54Co0.13O2 indicated the presence of monoclinic Li[Li1/3Mn2/3]O2 (31 %) and rhombohedral (LiNixMnyCozO2) (62 %) phases as the major components, and the spinel (LiNi0.5Mn1.5O4) (7 %) as a minor component, which is supported by TEM and electron diffraction analyses. A discharge specific capacity of about 170 mAh g−1 is obtained in the potential range of 2.3–4.9 V versus Li at low rate (C/10) with excellent capacity retention upon cycling. On the other hand, LiNi0.33Mn0.33Co0.33O2 (NMC111) synthesized through SCR exhibits an initial discharge capacity of about 208 mAh g−1 in the potential range of 2.3–4.9 V, which decreases to a value of 130 mAh g−1 after only 50 cycles. In turn, the multiphase structure of LiNi0.33Mn0.54Co0.13O2 seems to stabilize the behavior of this cathode material, even when polarized to high potentials. LiNi0.33Mn0.54Co0.13O2 shows superior retention of the average discharge voltage upon cycling, as compared to that of LiNi0.33Mn0.33Co0.33O2 when cycled over a wide potential range. Overall, LiNi0.33Mn0.54Co0.13O2 can be considered as a promising low‐cobalt‐content cathode material for Li‐ion batteries.

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Section: Resultssupporting

confidence: 78%

Multiphase LiNi_0.33Mn_0.54Co_0.13O₂ Cathode Material with High Capacity Retention for Li‐Ion Batteries

et al. 2015

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“…No evidence of electrochemically active structural protons were detected in this work for the electrochemically active electrode materials investigated, as opposed to proton insertion mechanisms proposed for Li-rich transition metal oxides. 11,28,34 …”

Section: Resultsmentioning

confidence: 98%

Solid State NMR Studies of Li₂MnO₃and Li-Rich Cathode Materials: Proton Insertion, Local Structure, and Voltage Fade

Doğan

Croy

Balasubramanian

et al. 2014

J. Electrochem. Soc.

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High energy densities of lithium-rich transition metal oxides cannot be sufficiently maintained on cycling due to high-voltage firstcycle activation and the subsequent structural changes. These changes can be seen as a continuous decrease of the average voltage with cycling, known as voltage fade. Electrochemical and chemical insertion of protons has been reported suggesting that protons generated in the electrolyte could be involved in electrochemical cycling which could play a similar role in the "Li 2 MnO 3 component" of lithium rich transition metal oxides. Here, electrochemical insertion of structural protons, changes in lithium occupancy at various states of charge, and changes in local structure have been investigated via a combination of local probes including solid state NMR, X-ray absorption spectroscopy and first principle calculations. While significant evidence is found for the deposition of non-structural proton-bearing species on electrodes, which accumulate with extensive cycling, structural proton insertion is not found to be a significant process directly effecting voltage fade. The electrochemical activity of disordered Li 2 MnO 3 , synthesized at low temperature, is also investigated and its Li removal/insertion properties measured quantitatively with NMR. Major reordering of Li sites and subsequent local structural transitions are observed by NMR and are found to be synchronous with voltage fade.Among the most challenging issues confronting large scale integration of rechargeable batteries into electric vehicles is the lack of low-cost, high-performance cathode materials. To this end, recent developments have identified several promising candidates including high-voltage/high-rate spinels, high-rate olivines, and high-capacity lithium-and manganese-rich nickel, manganese, cobalt-containing composites (which will be referred to as LMR-NMCs in this article for simplicity). 1-3 LMR-NMC type, transition metal (TM) oxides are particularly attractive because, depending on composition and electrochemical cycling conditions, the output energy densities can be pushed beyond 900 Wh/kg. 4 However, these high energy densities cannot be maintained due to a high-voltage, first-cycle activation step and the subsequent structural changes that are manifested as a continuous decrease of the average voltage with cycling, known as voltage fade. [4][5][6] This, in turn, results in an overall loss of energy output of cells on extended cycling. Several structural and non-structural causes for voltage fade have been postulated. 5,6 For example, non-structural causes such as surface and/or impedance effects caused by surface-species formation upon cycling, possibly related to the effects of electrolytes and additives have been investigated. 4 These composites have layered structures derived from LiCoO 2 (space group R-3m) 7 with alternating TM, oxygen, and lithium layers in octahedral configurations in an hexagonal lattice; however, the additional Li ions present in the TM layers induce intraplanar cation ordering. T...

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“…Electrodes for electrochemical testing were punched as discs (14 mm in diameter) from the electrode strips (bare and LAO coated) and used for fabrication of two-and three-electrode 2325 coin-type cells, as described in previous papers. 46,47 Lithium foil (200 μm thick) and Celgard PP2500 polypropylene membrane served as anode and separator, respectively. We also prepared pouch cells comprising NCA-bare or NCA/LAO electrodes of the geometric surface area ∼35 × 30 mm (loading ∼5 mg/cm 2 ) and lithium foil and Li-chip as counter and reference electrodes.…”

Section: Methodsmentioning

confidence: 99%

Studies of the Electrochemical Behavior of LiNi_0.80Co_0.15Al_0.05O₂Electrodes Coated with LiAlO₂

Srur-Lavi

Miikkulainen

Markovsky

et al. 2017

J. Electrochem. Soc.

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In this paper, we studied the influence of LiAlO 2 coatings of 0.5, 1 and 2 nm thickness prepared by Atomic Layer Deposition onto LiNi 0.8 Co 0.15 Al 0.05 O 2 electrodes, on their electrochemical behavior at 30 and 60 • C. It was demonstrated that upon cycling, 2 nm LiAlO 2 coated electrodes displayed ∼3 times lower capacity fading and lower voltage hysteresis comparing to bare electrodes. We established a correlation among the thickness of the LiAlO 2 coating and parameters of the self-discharge processes at 30 and 60 • C. Significant results on the elevated temperature cycling and aging of bare and LiAlO 2 coated electrodes at 4.3 V were obtained and analyzed for the first time. By analyzing of X-ray diffraction patterns of bare and 2 nm coated LiNi 0.8 Co 0.15 Al 0.05 O 2 electrodes after cycling, we concluded that cycled materials preserved their original structure described by R-3m space group and no additional phases were detected. The lithium-ion batteries (LIB) market nowadays has expanded widely from cellular phones, computers and other electronic devices to the automotive industry. Positive electrodes for LIBs to be explored in electric vehicles are mainly based on lithiated transition-metal oxides comprising Ni, Co and Mn (LiNi y Co x Mn 1-y-x O 2 ) and designated as NCM.1,2 They have attracted much attention as promising materials and therefore many research projects have been dedicated to them in the past 20 years. [3][4][5][6][7][8][9][10][11][12][13] In studies of LiNi 1/3 Co 1/3 Mn 1/3 O 2 (NCM333) cathodes, it was demonstrated 4-6 that they provided a capacity of 200 mAh/g in the voltage range of 2.5-4.6 V, or ∼155 mAh/g if the cutoff voltage is limited by 4.3 V.7 A substantially improved high-voltage performance of NCM333 electrodes (up to 4.6 V) was achieved by introducing tris(2,2,2-trifluoroethyl) borate additive in the electrolyte solution.8 These authors suggest that the additive takes part in the formation of the solid-electrolyte interface by lowering and stabilization of the interfacial resistance. NCM333 and NCM424 materials were studied in our group from the viewpoint of their electrochemical behavior, aging mechanisms, thermal properties, and surface chemistry developed upon cycling in ethylene carbonate-dimethyl carbonate/LiPF 6 based solutions.9 LiNi y Co x Mn 1-y-x O 2 materials with higher Ni content (y > 5) are important due to high capacity that can be extracted by charging up to 4.3 V only. However, Ni-rich NCMs suffer from their low cycling stability especially for compositions with Ni ≥ 60%, severe capacity fading and impedance increase during cycling at elevated temperatures (e.g. 45• C). One of the effective ways to stabilize the structure of NCM materials, to increase cycling activity and to diminish the heat evolution of the electrodes in a charged 14 There is a consensus in the literature that the above drawbacks originate from the unstable Ni 4+ ions developed in the charge state (high anodic potential, most Li + extracted from NCA). These Ni-ions can be readily reduce...

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Study of the electrochemical behavior of the “inactive” Li2MnO3

Cited by 135 publications

References 33 publications

Multiphase LiNi_0.33Mn_0.54Co_0.13O₂ Cathode Material with High Capacity Retention for Li‐Ion Batteries

Multiphase LiNi_0.33Mn_0.54Co_0.13O₂ Cathode Material with High Capacity Retention for Li‐Ion Batteries

Solid State NMR Studies of Li₂MnO₃and Li-Rich Cathode Materials: Proton Insertion, Local Structure, and Voltage Fade

Studies of the Electrochemical Behavior of LiNi_0.80Co_0.15Al_0.05O₂Electrodes Coated with LiAlO₂

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Study of the electrochemical behavior of the “inactive” Li2MnO3

Cited by 135 publications

References 33 publications

Multiphase LiNi0.33Mn0.54Co0.13O2 Cathode Material with High Capacity Retention for Li‐Ion Batteries

Multiphase LiNi0.33Mn0.54Co0.13O2 Cathode Material with High Capacity Retention for Li‐Ion Batteries

Solid State NMR Studies of Li2MnO3and Li-Rich Cathode Materials: Proton Insertion, Local Structure, and Voltage Fade

Studies of the Electrochemical Behavior of LiNi0.80Co0.15Al0.05O2Electrodes Coated with LiAlO2

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Multiphase LiNi_0.33Mn_0.54Co_0.13O₂ Cathode Material with High Capacity Retention for Li‐Ion Batteries

Multiphase LiNi_0.33Mn_0.54Co_0.13O₂ Cathode Material with High Capacity Retention for Li‐Ion Batteries

Solid State NMR Studies of Li₂MnO₃and Li-Rich Cathode Materials: Proton Insertion, Local Structure, and Voltage Fade

Studies of the Electrochemical Behavior of LiNi_0.80Co_0.15Al_0.05O₂Electrodes Coated with LiAlO₂