Cycling Behavior of a High Voltage Spinel Using an Original Three Electrodes Li 1-x Ni 0.4 Mn 1.6 O 4 //Li//LiNi 0.4 Mn 1.6 O 4 Symmetric Cell: Application to LiNi 0.4 Mn 1.6 O 4 Electrolyte Interface Degradation Studies

• Published in: ECS transactions Vol. 50; no. 26; pp. 73 - 85
• Main Authors: Demeaux, Julien, Lemordant, Daniel, Caillon-Caravanier, Magaly, Galiano, Hervé, Claude-Montigny, Bénédicte
• Format: Journal Article
• Language: English
• Published: 01.04.2013
• ISSN: 1938-5862; 1938-6737
• DOI: 10.1149/05026.0073ecst

The interface between LiNi0.4Mn1.6O4 and alkylcarbonate-based electrolytes is investigated by ab initio calculations, ICP-AES measurements and electrochemical tests. Interface degradation is known to occur by both the electrolyte oxidation and the Mn n+ and Ni n+ ion dissolution. Nevertheless, EC or PC oxidation, leading to a polymeric film formation, is able to contribute to the interface stabilization. Besides Li//LiNi 0.4 Mn 1.6 O 4 half-cells, Li 1-x Ni 0.4 Mn 1.6 O 4 //LiNi 0.4 Mn 1.6 O 4 symmetric cells are used in order to eliminate the effects from the strong reducing nature of lithium on the electrolyte. Systematic comparisons of fading and coulombic efficiency show that the main degradation mechanism in half-cells is the electrolyte oxidation, as a consequence of the continuous precipitation of metal ion-based compounds on the lithium electrode. The symmetric cell studies indicate that redox shuttles (M n+ ↔ M (n-1)+ , M=Mn or Ni) are mainly responsible for the LiNi 0.4 Mn 1.6 O 4 /electrolyte interface degradation despite the possible presence of a polymeric film. Symmetric cells also confirm EC superiority over other alkylcarbonates at the LiNi 0.4 Mn 1.6 O 4 interface.