Mengyun Nie

Hard X-ray Photoelectron Spectroscopy (HAXPES) Investigation of the Silicon Solid Electrolyte Interphase (SEI) in Lithium-Ion Batteries

Binder-free silicon (BF-Si) nanoparticle anodes were cycled with 1.2 M LiPF6 in ethylene carbonate (EC), fluoroethylene carbonate (FEC), or EC with 15% FEC (EC:FEC), extracted from cells and analyzed by Hard X-ray Photoelectron Spectroscopy (HAXPES). All of the electrolytes generate an SEI which is integrated with Si containing species. The EC and EC:FEC electrolytes result in the generation of LixSiOy after the first cycle while LixSiOy is only observed after five cycles for the FEC electrolyte. The SEI initially generated from the EC electrolyte is primarily composed of lithium ethylene dicarbonate (LEDC) and LiF. However, after five cycles, the composition changes, especially near the surface of silicon because of decomposition of the LEDC. The SEI generated from the EC:FEC electrolytes contains LEDC, LiF, and poly(FEC) and small changes are observed upon additional cycling. The SEI generated with the FEC electrolyte contains LiF and poly(FEC) and small changes are observed upon additional cycling. The stability of the SEI correlates with the observed capacity retention of the cells.

High Capacity, Stable Silicon/Carbon Anodes for Lithium-Ion Batteries Prepared Using Emulsion-Templated Directed Assembly

Silicon (Si) is a promising candidate for lithium ion battery anodes because of its high theoretical capacity. However, the large volume changes during lithiation/delithiation cycles result in pulverization of Si, leading to rapid fading of capacity. Here, we report a simple fabrication technique that is designed to overcome many of the limitations that deter more widespread adoption of Si based anodes. We confine Si nanoparticles in the oil phase of an oil-in-water emulsion stabilized by carbon black (CB). These CB nanoparticles are both oil- and water-wettable. The hydrophilic/hydrophobic balance for the CB nanoparticles also causes them to form a network in the continuous aqueous phase. Upon drying this emulsion on a current collector, the CB particles located at the surfaces of the emulsion droplets form mesoporous cages that loosely encapsulate the Si particles that were in the oil. The CB particles that were in the aqueous phase form a conducting network connected to the CB cages. The space within the cages allows for Si particle expansion without transmitting stresses to the surrounding carbon network. Half-cell experiments using this Si/CB anode architecture show a specific capacity of ∼1300 mAh/g Si + C and a Coulombic efficiency of 97.4% after 50 cycles. Emulsion-templating is a simple, inexpensive processing strategy that directs Si and conducts CB particles to desired spatial locations for superior performance of anodes in lithium ion batteries.