Understanding the Role of Prop-1-ene-1,3-Sultone and Vinylene Carbonate in LiNi_1/3Mn_1/3Co_1/3O₂/Graphite Pouch Cells: Electrochemical, GC-MS and XPS Analysis

Abstract

The role of prop-1-ene-1,3-sultone (PES) used alone or in combination with vinylene carbonate (VC) in LiNi1/3Mn1/3Co1/3O2(NMC)/graphite pouch cells was studied by correlating data from differential capacity (dQ/dV) analysis, gas chromatography/mass spectroscopy (GC−MS), ultrahigh precision coulometry, storage experiments and X-ray photoelectron spectroscopy. VC formed more stable and protective SEI films at both graphite and NMC surfaces due to the formation of a polymer of VC. For PES-containing electrolytes, the preferential reaction of PES led to the formation of SEI films with higher oxygen content at both graphite and NMC surfaces due to the additional oxygen contribution of sulfite species and substantially less LiF compared to control and VC electrolytes. PES also led to thicker SEI films at the NMC surface. When VC was combined with PES, features of the SEI films from both VC and PES were observed. The SEI film features for VC and PES used alone or in combination can explain the improved electrochemical performance as well as the lower production of gas observed with these additives compared to control electrolyte.

Studies of the Capacity Fade Mechanisms of LiCoO2/Si-Alloy: Graphite Cells

“…48,51,52,67,75,76 It is then possible that the transesterification of EMC occurs during the sudden failure of the LCO/Si:gr cells because of the absence of FEC. However FEC could, in principle, prevent the transesterification of EMC in two different ways.…”

Prescribing Functional Additives for Treating the Poor Performances of High‐Voltage (5 V‐class) LiNi0.5Mn1.5O4/MCMB Li‐Ion Batteries

“…Specifically speaking, functional additives with a higher HOMO energy than carbonate solvents will be preferentially oxidized to modify the cathode SEI layer, while those with a lower LUMO energy than carbonate solvents will be preferentially reduced to modify the anode SEI layer. [31,32,[54][55][56][57][58][59] The most typical electrochemical reduction species of these organic sulfur-containing compounds are passivating ROSO 2 Li and Li 2 SO 3 , which can facilitate lithium ion diffusion through SEI layer and prevent the excessive reductive decomposition of carbonate solvents (such as propylene carbonate). [35,[48][49][50][51][52][53] With a higher HOMO energy relative to carbonate solvents, TMSP easily undergoes electrochemi cal oxidations and promotes the formation of a protective SEI layer on the surface of high-voltage cathode materials (such as LiNi 0.5 Mn 1.5 O 4 , LiNi 0.5 Co 0.2 Mn 0.3 O 2 , overlithiated layered oxide).…”

The Effects of a Ternary Electrolyte Additive System on the Electrode/Electrolyte Interfaces in High Voltage Li-Ion Cells

“…More recently, using XPS experiments, Madec et al 27 showed that in NMC/graphite pouch cells balanced for 4.2 V, PES forms more protective and stable SEI films at both graphite and NMC surfaces which might explain the improved electrochemical * Electrochemical Society Student Member. * * Electrochemical Society Fellow.…”

“…More recently, using XPS experiments, Madec et al 27 showed that in NMC/graphite pouch cells balanced for 4.2 V, PES forms more protective and stable SEI films at both graphite and NMC surfaces which might explain the improved electrochemical performance as well as the lower production of gas observed with PES compared to control electrolyte. They attributed these results to the preferential reaction of PES at both graphite and NMC surfaces that led to an additional contribution of sulfite species and substantially less LiF compared to control electrolyte.…”