Regulating Li Nucleation and Growth Heterogeneities via Near-Surface Lithium-Ion Irrigation for Stable Anode-Less Lithium Metal Batteries.

The inhomogeneous nucleation and growth of Li dendrite combined with the spontaneous side reactions with the electrolytes dramatically challenge the stability and safety of Li metal anode (LMA). Despite tremendous endeavors, current success relies on the use of significant excess of Li to compensate the loss of active Li during cycling. Herein, a near-surface Li+ irrigation strategy is developed to regulate the inhomogeneous Li deposition behavior and suppress the consequent side reactions under limited Li excess condition. The conformal polypyrrole (PPy) coating layer on Cu surface via oxidative chemical vapor deposition technique can induce the migration of Li+ to the interregional space between PPy and Cu, creating a near-surface Li+-rich region to smooth diffusion of ion flux and uniform the deposition. Moreover, as evidenced by multiscale characterizations including synchrotron high-energy X-ray diffraction scanning, a robust N-rich solid-electrolyte interface (SEI) is formed on the PPy skeleton to effectively suppress the undesired SEI formation/dissolution process. Strikingly, stable Li metal cycling performance under a high areal capacity of 10 mAh cm-2 at 2.0 mA cm-2 with merely 0.5 × Li excess is achieved. The findings not only resolve the long-standing poor LMA stability/safety issues, but also deepen the mechanism understanding of Li deposition process.

Two-Dimensional Cobalt Sulfide/Iron-Nitrogen-Carbon Holey Sheets with Improved Durability for Oxygen Electrocatalysis.

Transition-metal sulfide as a promising bifunctional oxygen electrocatalyst alternative to scarce platinum-group metals has attracted much attention, but it suffers activity loss over time owing to poor structural/compositional stability during catalysis. Herein, we report a self-template method for preparing a two-dimensional cobalt sulfide holey sheet superstructure with hierarchical porosity followed by the encapsulation of thin iron-nitrogen-carbon as a protective layer. The iron-nitrogen-carbon layer to some degree precludes the phase transition of cobalt sulfide underneath and preserves the structural integrity during catalysis, therefore rendering an exceptional durability in terms of no obvious activity loss after 10,000 cycles of the accelerated durability test. It also noticeably enhances the intrinsic activity of cobalt sulfide and does not influence its exposure into the electrolyte, resulting in showing an extraordinary electrochemical performance in terms of a potential difference of 0.69 V for the overall oxygen redox. A rechargeable zinc-air battery assembled by a cobalt sulfide/iron-nitrogen-carbon air cathode delivers approximately 4.2 times higher power density than that without an iron-nitrogen-carbon layer and stably operates for 300 h with a high voltaic efficiency. This work gives a facile and effective strategy for improving the long-term durability of transition-metal sulfide electrocatalysts.

Pd Nanoparticles Decorated N-Doped Graphene Quantum Dots@N-Doped Carbon Hollow Nanospheres with High Electrochemical Sensing Performance in Cancer Detection.

The development of carbon based hollow-structured nanospheres (HNSs) materials has stimulated growing interest due to their controllable structure, high specific surface area, large void space, enhanced mass transport, and good biocompatibility. The incorporation of functional nanomaterials into their core and/or shell opens new horizons in designing functionalized HNSs for a wider spectrum of promising applications. In this work, we report a new type of functionalized HNSs based on Pd nanoparticles (NPs) decorated double shell structured N-doped graphene quantum dots (NGQDs)@N-doped carbon (NC) HNSs, with ultrafine Pd NPs and "nanozyme" NGQDs as dual signal-amplifying nanoprobes, and explore their promising application as a highly efficient electrocatalyst in electrochemical sensing of a newly emerging biomarker, i.e., hydrogen peroxide (H2O2), for cancer detection. Due to the synergistic effect of the robust and conductive HNS supports and catalytically active Pd NPs and NGQD in facilitating electron transfer, the NGQD@NC@Pd HNS hybrid material exhibits high electrocatalytic activity toward the direct reduction of H2O2 and can promote the electrochemical reduction reaction of H2O2 at a favorable potential of 0 V, which effectively restrains the redox of most electroactive species in physiological samples and eliminates interference signals. The resultant electrochemical H2O2 biosensor based hybrid HNSs materials demonstrates attractive performance, including low detection limit down to nanomole level, short response time within 2 s, as well as high sensitivity, reproducibility, selectivity, and stability, and have been used in real-time tracking of trace amounts of H2O2 secreted from different living cancer cells in a normal state and treated with chemotherapy and radiotherapy.