2013
DOI: 10.1038/ncomms3437
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Mn(II) deposition on anodes and its effects on capacity fade in spinel lithium manganate–carbon systems

Abstract: Dissolution and migration of manganese from cathode lead to severe capacity fading of lithium manganate-carbon cells. Overcoming this major problem requires a better understanding of the mechanisms of manganese dissolution, migration and deposition. Here we apply a variety of advanced analytical methods to study lithium manganate cathodes that are cycled with different anodes. We show that the oxidation state of manganese deposited on the anodes is +2, which differs from the results reported earlier. Our resul… Show more

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Cited by 448 publications
(406 citation statements)
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References 42 publications
(54 reference statements)
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“…For example, the Mn dissolution rate from LMO is greater at high potentials (above 4 V vs. Li/Li + ) than at lower potentials (below 4 V vs. Li/Li + ), a fact which is inconsistent with the disproportionation concept, since the fraction of Mn 4+ cations in the LMO lattice increases with increasing potential. 13,17 While a very large number of studies in the literature report a variety of results on the oxidation state of Mn species in the negative or positive electrodes of cycled LMO-graphite cells, 11,[18][19][20][21] Mitigation measures for Mn dissolution.-Several mitigation measures for the dissolution of Mn ions and its consequences were proposed in the literature over the past two decades: electrolyte optimization by a judicious choice of additives; [26][27][28][29][30][31][32][33] elemental substitutions in the LMO lattice, 7,13,17,34,35 in order to increase the average oxidation state of the Mn ions; surface coatings on the active material powder or electrodes, in order to avoid direct contacts between electrode and electrolyte solution, and thus prevent HF and other acid attack on the active material; [36][37][38][39][40][41][42] chemically active binders; [43][44][45][46][47][48][49][50] an inorganic Mn ions scavenging barrier layer such as lithium titanate 51 or a solid Li-ion conducting and Mn ions blocking membrane 52 placed in the inter-electrode space; and the utilization of chemically activ...…”
Section: A6316mentioning
confidence: 99%
“…For example, the Mn dissolution rate from LMO is greater at high potentials (above 4 V vs. Li/Li + ) than at lower potentials (below 4 V vs. Li/Li + ), a fact which is inconsistent with the disproportionation concept, since the fraction of Mn 4+ cations in the LMO lattice increases with increasing potential. 13,17 While a very large number of studies in the literature report a variety of results on the oxidation state of Mn species in the negative or positive electrodes of cycled LMO-graphite cells, 11,[18][19][20][21] Mitigation measures for Mn dissolution.-Several mitigation measures for the dissolution of Mn ions and its consequences were proposed in the literature over the past two decades: electrolyte optimization by a judicious choice of additives; [26][27][28][29][30][31][32][33] elemental substitutions in the LMO lattice, 7,13,17,34,35 in order to increase the average oxidation state of the Mn ions; surface coatings on the active material powder or electrodes, in order to avoid direct contacts between electrode and electrolyte solution, and thus prevent HF and other acid attack on the active material; [36][37][38][39][40][41][42] chemically active binders; [43][44][45][46][47][48][49][50] an inorganic Mn ions scavenging barrier layer such as lithium titanate 51 or a solid Li-ion conducting and Mn ions blocking membrane 52 placed in the inter-electrode space; and the utilization of chemically activ...…”
Section: A6316mentioning
confidence: 99%
“…27-29 for a review). The released Mn can be directly observed in the SEI on delithiated graphite electrodes harvested from cycled cells using fluorescence, 30 X-ray absorption, 28,29,31 and magnetic resonance spectroscopies. 29 In the SEI the Mn II ion is coordinated by six oxygen atoms, and has several Li + ions nearby; further away from the ion, fluorine atoms and protons are observed.…”
mentioning
confidence: 99%
“…This "dialog" between both electrodes was proposed as creating a "shuttle" which could damage cell performance. 6 Li et al recently found that oxidized species from LiNi 0.5 Mn 1.5 O 4 caused severe parasitic reactions on the Li 4 Ti 5 O 12 electrode using an innovative "pseudo-full cell" configuration. 7 When NMC/graphite Li-ion cells are operated at a cutoff potential higher than 4.2 V, severe impedance increase can be the main contributor to cell failure instead of conventional mechanisms, like loss of Li inventory, that dominate in low voltage cells.…”
mentioning
confidence: 99%
“…This interaction has been shown to be detrimental to cell performance. [2][3][4][5] Another proposed example is CO 2 generation at the positive electrode followed by reduction at the negative electrode. This "dialog" between both electrodes was proposed as creating a "shuttle" which could damage cell performance.…”
mentioning
confidence: 99%