The rapid development of mobile electronics, electric-vehicles and intermittent power generation relies on the availability of advanced electrochemical energy storage systems such as high capacity lithium ion batteries (LIBs). Although the state-of-the-art commercial LIBs have impressive electrochemical performance, they are suffering from relative low capacities due to the usage of host materials for storing lithium ions safely and reproducibly. The host material for LIB anode is dominated by graphite with a theoretical capacity of 372 mAh g-1. To further improve the capacity and energy density of LIBs, revolutionary changes in electrode materials, electrolytes, additives, binders and cell design are much needed. Alloying anode materials like Si, Ge and Sn have much higher theoretical capacities (4200, 1600 and 990 mAh g-1 for Si, Ge and Sn, respectively) as compared to graphite. However, a high capacity inevitably leads to a large electrode volume change during lithiation and de-lithiation process (e.g. 300% for Si-based anodes). Such a huge volume change can cause electrode pulverization, detachment of active materials from conductive additives, unstable solid-electrolyte interphase, and eventually result in a rapid, permanent capacity loss. Although Si-based anode has caught much research attention, formidable challenges remain to develop an electrode fabrication method that is efficient, low-cost, scalable, highly reproducible, and self-assembled, thus boosting the commercialization potential of Si-based anodes. As inspired by the hollow fiber membrane technology that has been successfully commercialized in the last decades to provide billions of gallons of purified drinking water worldwide, we report the use of carbonized asymmetric membrane electrodes (fiber and thin film types) that contain silicon, silicon monoxide, germanium, tin dioxide or vanadium (V) oxide to significantly increase LIB electrode capacity while maintaining a long cycling life and an excellent rate performance. These asymmetric membrane electrodes are fabricated using a modified reverse-osmosis membrane technology, the phase-inversion method combined with dip-coating and carbonization. The asymmetric membrane electrodes have a thin, nanoporous top layer (up to several microns) and a thick, macroporous bottom layer (up to 200 µm). The top layer can prevent fractured anode materials from falling away, while the bottom layer can efficiently accommodate the large volume changes of high capacity alloying anodes. 90% capacity of thin film asymmetric membrane at 1000 mAh g-1 containing Si nanoparticles can be retained after 200 cycles with an initial capacity loss of ~ 30%. Combining phase inversion with sol-gel chemistry, this method can be extended to obtain SnO2 and V2O5 asymmetric membranes. Thin film SnO2 asymmetric membrane electrode demonstrates a specific capacity of 500 mAh g-1 a current density of 280 mA g-1 (~0.5C) with >96% capacity retention after 400 cycles. When the current density is increased from 28 to 560 mA g-1, more than 65% capacity can be retained. The V2O5 electrode can be cycled at 0.5C with a capacity of 160 mAh g-1 for 380 times with ~100% capacity retention. The same method can be employed to stabilize micron-size Ge and Si alloying anodes with >80% capacity retention in 100 cycles. Most recently, our group has successfully fabricated various fibrous Si and Sn asymmetric membrane electrodes whose electrochemical performance is compared to thin film Si and Sn asymmetric membrane electrodes. e.g. ~90 % initial capacity at ~1,200 mAh g-1 can be maintained in 300 cycles applying a current density of 400 mA g-1 with an initial capacity loss less than 15%. These asymmetric membrane electrodes have been systematically characterized using extensive instruments spanning from scanning electron microscope (SEM), energy dispersive X-ray spectroscopy (EDS), Raman spectroscopy, powder X-ray diffractometer (PXRD), thermogravimetric analyzer (TGA), surface area analyzer (BET method) to X-ray photoelectron spectroscopy (XPS), as well as various electrochemical tests such as cycling and rate performance, cyclic voltammetry, and electrochemical impedance spectroscopy, purposing to understand the relationship between structure, chemical composition and electrochemical properties for these asymmetric membrane electrodes.
Search from 250 M+ research papersSearch from 250 M+ research papers
Sep 13, 2024
Yajun Huang + 6
Open Access