Proton insertion and lithium-proton exchange in spinel lithium manganates

Ammundsen, Brett; Aitchison, Phillip; Burns, Gary R.; Jones, Deborah J.; Rozière, Jacqués

doi:10.1016/s0167-2738(97)00065-9

Cited by 76 publications

(73 citation statements)

References 15 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…8 It is interesting to note that while proton incorporation occurs readily into the layered oxide lattice during the aqueous delithiation process, it does not occur with the spinel lattice even in the proton-rich aqueous acid medium. These results are in agreement with the earlier literature reports [31][32][33] that an incorporation of protons by an ion-exchange mechanism occurs only into lithium rich Li 1+y Mn 2Ày O 4 spinels with all the manganese present in the 4+ oxidation state. If Mn 3+ ions are present in the structure as in the case of LiMn 2 O 4 , then the chemical lithium extraction takes place only by a redox mechanism involving the oxidation of Mn 3+ to Mn 4+ .…”

Section: Chemical Delithiation Of Spinel Limn 2 Osupporting

confidence: 93%

Investigation of the possible incorporation of protons into oxide cathodes during chemical delithiation

Venkatraman

Manthiram

2004

Journal of Solid State Chemistry

View full text Add to dashboard Cite

Section: Chemical Delithiation Of Spinel Limn 2 Osupporting

confidence: 93%

Investigation of the possible incorporation of protons into oxide cathodes during chemical delithiation

Venkatraman

Manthiram

2004

Journal of Solid State Chemistry

View full text Add to dashboard Cite

“…The pH of the solution was adjusted with diluted hydrochloric acid and sodium hydroxide solutions using a pH meter. Batch studies were carried out by mixing HMS with LiCl solution at different pH initial (2)(3)(4)(5)(6)(7)(8)(9)(10)(11)(12) and shaking in a rotary shaker with glass flasks. All of the parameters, adsorbent concentration (1 g/L), temperature (20 • C), initial Li + concentration (10-200 mg/L), and contact time (24 h), were kept constant respectively at each pH value.…”

Section: Batch Experimentsmentioning

confidence: 99%

“…Spinel-type lithium manganese oxides show excellent selectivity and capacity for the adsorption of Li + after topotactic extraction of Li + with an acid, such as -MnO 2 , MnO 2 ·0.31H 2 [5][6][7][8][9][10]. The adsorptive properties make the material practicable as a Li + adsorbent, a cathode material for lithium batteries and electrode for selective electroinsertion of Li + [11].…”

Section: Introductionmentioning

confidence: 99%

Adsorption behavior of Li+ onto nano-lithium ion sieve from hybrid magnesium/lithium manganese oxide

Tian

Mei

2010

Chemical Engineering Journal

129

View full text Add to dashboard Cite

“…In particular, there is abundant literature on H + /Li + ion exchange in closely related materials, such as α-LiAlO 2 , 25 Li 2 MnO 3 , 26 and LiMn 2 O 4 . 27 The outward migration of Li + ions and the inward migration of protons into the oxide bulk would drive equilibrium Reactions 1 and 2 to the right side, and facilitate Reaction 3.…”

mentioning

confidence: 99%

Chemical Weathering of Layered Ni-Rich Oxide Electrode Materials: Evidence for Cation Exchange

Shkrob

Gilbert

Phillips

et al. 2017

J. Electrochem. Soc.

141

160

View full text Add to dashboard Cite

Lithiated ternary oxides containing nickel, cobalt, and manganese are intercalation compounds that are used as positive electrodes in high-energy lithium-ion batteries. These oxides undergo changes, when they are stored in humid air or exposed to moisture, that adversely affect their electrochemical performance. There is a new urgency to better understanding of these "weathering" mechanisms as manufacturing moves toward a more environmentally benign aqueous processing of the positive electrode. Delithiation of the oxide and the formation of lithium salts (such as hydroxides and carbonates) coating the surface, are known to occur during moisture exposure. The redox reactions which follow this delithiation are believed to trigger all the other transformations. In this article we suggest another possibility: namely, the proton -lithium exchange. We argue that this hypothesis provides a simple, comprehensive rationale for our observations, which include contraction of the c-axis (unit cell) lattice parameter, rock salt phase formation in the subsurface regions, presence of amorphous surface films, and the partial recovery of oxide capacity during electrochemical relithiation. The detrimental effects of water exposure need to be mitigated before aqueous processing of the positive electrode can find widespread adoption during cell manufacturing. Improving the performance of lithium-ion batteries (LIBs) for electrically powered vehicles gives urgency to the development of high-capacity, high-voltage electrode materials, and layered Ni-rich oxides are presently among the most technological advanced materials that allow operation above +4.0 V vs Li + /Li. 1 Such materials (also known as NCMxyz materials) have the general composition of LiNi x/10 Co y/10 Mn z/10 O 2 , where x+y+z = 10. In these ternary oxides, the manganese stays in the Mn 4+ state during cell cycling, and the capacity mainly originates from the Ni 2+ /Ni 3+ and Ni 3+ /Ni 4+ redox couples. The monolayers of octahedra containing transition metal (TM) ions form a structural scaffold with the layers of mobile Li + ions placed in between. The crystalline material retains the structure of the progenitor material of the family, viz. α-LiCoO 2 , 2 with the unit cell belonging to the rhombohedral R(-3)m space group. During electrochemical cycling, the lithium ions intercalate into (and deintercalate from) the layered crystals as the redox state of (mainly the) nickel ions changes to provide the overall charge neutrality.In this study, we examine one such material, NCM523, which represents a particular trade-off between the cycling rate (that improves with Co content), safety (that improves with Mn content), and capacity (that increases with Ni content).1 The safety concerns mainly relate to the thermal and chemical stability, including oxidation of the organic electrolyte by catalytic centers at the oxide surface 3 and phase transitions in the delithiated material that occur when a significant fraction of nickel ions is reduced to Ni 2+ ions and molecular oxygen ...

show abstract

Proton insertion and lithium-proton exchange in spinel lithium manganates

Cited by 76 publications

References 15 publications

Investigation of the possible incorporation of protons into oxide cathodes during chemical delithiation

Investigation of the possible incorporation of protons into oxide cathodes during chemical delithiation

Adsorption behavior of Li+ onto nano-lithium ion sieve from hybrid magnesium/lithium manganese oxide

Chemical Weathering of Layered Ni-Rich Oxide Electrode Materials: Evidence for Cation Exchange

Contact Info

Product

Resources

About