Layered LiNi x Mn y Co z O 2 (NMC) is a widely used class of cathode materials with LiNi 1/3 Mn 1/3 Co 1/3 O 2 (NMC111) being the most common representative. However, Ni-rich NMCs are more and more in the focus of current research due to their higher specific capacity and energy. In this work we will compare LiNi 1/3 Mn 1/3 Co 1/3 O 2 (NMC111), LiNi 0.6 Mn 0.2 Co 0.2 O 2 (NMC622), and LiNi 0.8 Mn 0.1 Co 0.1 O 2 (NMC811) with respect to their cycling stability in NMC-graphite full-cells at different end-of-charge potentials. It will be shown that stable cycling is possible up to 4.4 V for NMC111 and NMC622 and only up to 4.0 V for NMC811. At higher potentials, significant capacity fading was observed, which was traced back to an increase in the polarization of the NMC electrode, contrary to the nearly constant polarization of the graphite electrode. Furthermore, we show that the increase in the polarization occurs when the NMC materials are cycled up to a high-voltage feature in the dq/dV plot, which occurs at ∼4.7 V vs. Li/Li + for NMC111 and NMC622 and at ∼4.3 V vs. Li/Li + for NMC811. For the latter material, this feature corresponds to the H2 → H3 phase transition. Contrary to the common understanding that the electrochemical oxidation of carbonate electrolytes causes the CO 2 and CO evolution at potentials above 4.7 V vs. Li/Li + , we believe that the observed CO 2 and CO are mainly due to the chemical reaction of reactive lattice oxygen with the electrolyte. This hypothesis is based on gas analysis using On-line Electrochemical Mass Spectrometry (OEMS), by which we prove that all three materials release oxygen from the particle surface and that the oxygen evolution coincides with the onset of CO 2 and CO evolution. Interestingly, the onsets of oxygen evolution for the different NMCs correlate well with the high-voltage redox feature at ∼4.7 V vs. Li/Li + for NMC111 and NMC622 as well as at ∼4.3 V vs. Li/Li + for NMC811. To support this hypothesis, we show that no CO 2 or CO is evolved for the LiNi 0.43 Mn 1.57 O 4 (LNMO) spinel up to 5 V vs. Li/Li + , consistent with the absence of oxygen release. Lastly, we demonstrate by the use of 13 C labeled conductive carbon that it is the electrolyte rather than the conductive carbon which is oxidized by the released lattice oxygen. Taking these findings into consideration, a mechanism is proposed for the reaction of released lattice oxygen with ethylene carbonate yielding CO 2 , CO, and Li-Ion batteries have recently been used as power supply for electric vehicles (EVs). In order to penetrate the mass market, a significant reduction in costs and further performance improvements have to be achieved to realize a longer driving range of EVs.1 The latter highly depends on the choice of the cathode active material, for which several potential materials exist, 2 of which layered lithium nickel manganese cobalt oxide (LiNi x Mn y Co z O 2 , NMC) is one of the most promising class of cathode materials.3 This is due to the high specific capacity and good stability of the lay...
We compare the stability of alkyl carbonate electrolyte on NMC111, -622, and -811, LNMO, and conductive carbon electrodes. We prove that CO and CO evolution onset potentials depend on the electrode material and increase in the order NMC811 < NMC111 ≈ NMC622 < conductive carbon ≈ LNMO, which we rationalize by two fundamentally different oxidation mechanisms, the chemical and the electrochemical electrolyte oxidation. Additionally, in contrast to the widespread understanding that transition metals in cathode active materials catalyze the electrolyte oxidation, we will prove that such a catalytic effect on the electrochemical electrolyte oxidation does not exist.
is one of the high-energy positive electrode (cathode) materials for next generation Li-ion batteries. However, compared to the structurally similar LiNi 1/3 Mn 1/3 Co 1/3 O 2 (NMC111), it can suffer from a shorter lifetime due to its higher surface reactivity. This work studied and compared the formation of surface contaminations on NMC811 and NMC111 when stored under ambient conditions using electrochemical cycling, Raman spectroscopy, and X-ray photoelectron spectroscopy. NMC811 was found to develop a surface layer of up to ∼10 nm thickness that was mostly composed of nickel carbonate species mixed with minor quantities of hydroxide and water after ambient storage for 1 year, while no significant changes were observed on the NMC111 surface. The amount of carbonate species was quantified by gas chromatographic (GC) detection of carbon dioxide generated when the NMC particles were dispersed in hydrochloric acid. Surface impurity species formed on NMC811 upon ambient storage not only lead to a significant delithiation voltage peak in the first charge, but also markedly reduce the cycling stability of NMC811-graphite cells due to significantly growing polarization of the NMC811 electrode.
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