No abstract

A series of experiments is presented that establishes for the first time the role of some of the key design parameters of porous carbons including surface area, pore volume, and pore size on battery performance. A series of hierarchical porous carbons is used as a model system with an open, 3D, interconnected porous framework and highly controlled porosity. Specifically, carbons with surface areas ranging from ≈500–2800 m2 g−1, pore volume from ≈0.6–5 cm3 g−1, and pore size from micropores (≈1 nm) to large mesopores (≈30 nm) are synthesized and tested. At high sulfur loadings (≈80 wt% S), pore volume is more important than surface area with respect to sulfur utilization. Mesopore size, in the range tested, does not affect the sulfur utilization. No relationship between porosity and long‐term cycle life is observed. All systems fail after 200–300 cycles, which is likely due to the consumption of the LiNO3 additive over cycling. Moreover, cryo‐scanning transmission electron microscopy imaging of these carbon–sulfur composites combined with X‐ray diffraction (XRD) provides further insights into the effect of initial sulfur distribution on sulfur utilization while also revealing the inadequacy of the indirect characterization techniques alone in reliably predicting distribution of sulfur within porous carbon matrices.

An epoxy group was successfully attached to the surface of silicon nanoparticle (SiNPs) via a silanization reaction between silanol-enriched SiNPs and functional silanes. The epoxy-functionalized SiNPs showed a much improved cell performance compared with the pristine SiNPs because of the increased stability with electrolyte and the formation of a covalent bond between the epoxy group and the polyacrylic acid binder. Furthermore, the anode laminate made from epoxy-SiNPs showed much enhanced adhesion strength. Post-test analysis shed light on how the epoxy-functional group affects the physical and electrochemical properties of the SiNP anode.

Replacing N-methyl-2-pyrrolidone (NMP) with water for processing of lithium-ion battery (LIB) electrodes has both cost and environmental benefits, which include reduced drying time, lower dryer capital cost, elimination of NMP recovery capital equipment, and no release of volatile organic compounds (VOCs) into the environment. However, aqueous-processed thick cathodes (≳4 mAh/cm2) typically exhibit detrimental cracking during drying that is not observed for the NMP-based counterpart. The reasons for cracking of these water-based thick electrodes are still not well understood due to the complex nature of the colloidal dispersions used in the LIB electrode processing steps. In this work, the contributions of various factors responsible for cracking are discussed. We show that eliminating hydrogen evolution due to corrosion of the aluminum current collector eliminated the majority of the cracks regardless of the coating thickness, identifying the gas evolution as the primary reason for electrode cracking. Some secondary cracks and pinhole-type defects remained after addressing the aluminum current collector corrosion, which are thought to be caused by an inferior binding network formed by carbon black and binder in aqueous-processed cathodes compared to those processed with NMP. The thick aqueous processed cathodes are not able to sufficiently withstand the drying stresses without crack formation. We demonstrate reduction of these secondary defects by either improving the binding network or by reducing the drying stress. The former was achieved by replacing carbon black with vapor grown graphite tubes (VGGTs) that caused a more efficient utilization of the emulsion binder. The latter was achieved by adding a small amount of IPA as a co-solvent that has been shown to reduce capillary stresses.

Electrode cross-talk in lithium-ion batteries has been increasingly recognized in recent years as an explanation for several performance trends during cycling. However, little is known about the nature of such cross-talk species/reactions. In an attempt to further that understanding, we constructed a two-compartment lithium-ion cell using a solid-state lithium-ion conductor as the separator to block the movement of species generated at one electrode to the other. After a long-term hold at a high voltage, the electrolytes extracted from each side were analyzed via high-performance liquid chromatography coupled with electrospray ionization mass spectrometry and nuclear magnetic resonance spectroscopy. We compared these results with those from a coin cell made with a regular porous separator. Extra species were present in the coin cell, which were absent in both compartments of the two-compartment cell, and we identified them as cross-talk species. We propose chemical structures for such species and show that these species likely have carbon–carbon double bonds and fluorinated carbons. We also confirm that the organophosphate-type species proposed by several groups previously are indeed generated at the anode.