The Effect of Electrolyte Additives upon Lithium Plating during Low Temperature Charging of Graphite-LiNiCoAlO₂ Lithium-Ion Three Electrode Cells

Abstract

The effects of lithium-ion electrolyte additives in ester-rich low temperature electrolyte blends, including vinylene carbonate (VC), lithiuma bis(oxalato) borate (LiBOB), lithium difluoro(oxalato)borate (LiDFOB), propane sultone (PS) and lithium bis(fluorosulfonyl)imide (LiFSI), upon the likelihood of lithium plating are investigated in graphite-LiNiCoAlO2 three-electrode cells. Although metallic lithium is generally absent in lithium-ion cells, certain conditions, particularly charging at low temperature and/or at high rate, can lead to lithium metal plating on the surface rather than intercalating into the carbon anode. Metallic lithium reacts with the electrolyte and forms dendrites upon continuous plating, which can lead to cell shorting and capacity loss. The type of carbon anode, electrolyte, and solid-electrolyte-interphase (SEI) all influence this behavior. SEI stabilizing additives are generally detrimental to low temperature charging performance, however, 0.1 M LiFSI was found to be advantageous to low temperature charging. When charged at a C/5 rate to 4.10 V, lithium plating was evident at ∼20 °C higher temperature with VC and LiBOB additives compared to the baseline electrolyte without any additives (plating appears at −10 °C rather than −30 °C with the baseline electrolyte). In contrast, the cell containing 0.10 M LiFSI as an additive did not display lithium plating until −40 °C, or 10 °C lower than the baseline cell.

Electrolyte Design for Lithium Metal Anode‐Based Batteries Toward Extreme Temperature Application

“…Jones et al. [ 68 ] further examined the polarization resistance on the cathode with different types of Li salts additives. The electrolyte with LiBOB additive produced the lowest polarization resistance at −40 °C (2.42 Ω), indicating the best charge transfer kinetics.…”

A review of thermal physics and management inside lithium-ion batteries for high energy density and fast charging

“…Abe et al [228]showed that in two types of preformed SEI at the interface of HOPG-Electrolyte (1M LiClO4 in 1:1 EC:DEC), the activation energy for the charge transfer through the SEI formed with Pentafluorostyrene (PFS) additive was 40 kJ/mol compared to 52 kJ/mol for SEI formed without the additive. Various other experiments [228,233] supported that changing SEI/CEI composition through electrolyte additives 1 exp( )…”

Liquid electrolyte development for low-temperature lithium-ion batteries

“…The most common recent development, however, has seen ester-based formulations paired with interface-modifying additives, including VC, 91,102-104 FEC 103,105 and others. 74,104 For instance, Jones et al tested a series of additives for their ability to inhibit lithium plating during low-temperature charge in a MP-rich electrolyte, finding 0.1 M LiFSI to be most effective. 104 In at least one case, additives have made it possible to eliminate EC from the electrolyte entirely, with a MP : VC 95 : 5 w/w electrolyte allowing acceptable capacity retention during 40 1C cycling of Gr8NMC 111 pouch cells and enabling significantly-improved rate performance at À14 1C compared to an EC/EMC/VC mixture.…”