Engineering Papers⌕ Search

Engineering topics

Abraham, Daniel P.

Publications and source records attributed to Abraham, Daniel P..

Significant Improvements to Si Calendar Lifetime Using Rapid Electrolyte Screening via Potentiostatic Holds

Silicon-based lithium-ion batteries exhibit severe time-based degradation resulting in poor calendar lives. This has been identified as the major impediment towards commercialization with cycle life considered a solved issue through nanosizing and protective coatings allowing over 1000 cycles of life to be achieved. In this work, rapid screening of sixteen electrolytes for calendar life extension of Si-rich systems (70 wt% Si) is performed using the voltage hold (V-hold) protocol. V-hold significantly shortens the testing duration over the traditional open circuit voltage reference performance test allowing us to screen electrolytes within a span of two months. We find a novel ethylene carbonate (EC) free electrolyte formulation containing lithium hexafluorophosphate (LiPF 6 ) salt, and binary solvent mix of fluoroethylene carbonate (FEC), ethyl methyl carbonate (EMC) that extends calendar life of Si cells as compared to conventional EC based electrolyte. Our coupled experimental-theoretical analysis framework provides a decoupling of the parasitic currents during V-hold, allowing us to extrapolate the capacity loss to predict semiquantitative calendar lifetimes. Subsequently, cycle aging and oxidative stability tests of the EC free system also show enhanced performance over baseline electrolyte.

25 ENERGY STORAGE↗

Inactive Overhang in Silicon Anodes

Li-ion batteries contain excess anode area to improve manufacturability and prevent Li plating. These overhang areas in graphite electrodes are active but experience decreased Li + flux during cycling. Over time, the overhang and the anode portions directly opposite to the cathode can exchange Li + , driven by differences in local electrical potential across the electrode, which artificially inflates or decreases the measured cell capacity. Here, we show that lithiation of the overhang is less likely to happen in silicon anodes paired with layered oxide cathodes. The large voltage hysteresis of silicon creates a lower driving force for Li + exchange as lithium ions transit into the overhang, rendering this exchange highly inefficient. For crystalline Si particles, Li + storage at the overhang is prohibitive, because the low potential required for the initial lithiation can act as thermodynamic barrier for this exchange. We use micro-Raman spectroscopy to demonstrate that crystalline Si particles at the overhang are never lithiated even after cell storage at 45 °C for four months. Because the anode overhang can affect the forecasting of cell life, cells using silicon anodes may require different methodologies for life estimation compared to those used for traditional graphite-based Li-ion batteries.

25 ENERGY STORAGE↗