Neuron-Like Silicone Nanofilaments@Montmorillonite Nanofillers of PEO-Based Solid-State Electrolytes for Lithium Metal Batteries with Wide Operation Temperature.

Poly(ethylene oxide) (PEO)-based composite solid electrolytes (CSEs) are promising to accelerate commercialization of solid-state lithium metal batteries (SSLMBs). Nonetheless, this is hindered by the CSEs' limited ion conductivity at room temperature. Here, we propose design, synthesis, and application of the bioinspired neuron-like nanofillers for PEO-based CSEs. The neuron-like superhydrophobic nanofillers are synthesized by controllably grafting silicone nanofilaments onto montmorillonite nanosheets. Compared to various reported fillers, the nanofillers can greatly improve ionic conductivity (4.9×10-4 S cm-1, 30 °C), Li+ transference number (0.63), oxidation stability (5.3 V) and mechanical properties of the PEO-based CSEs because of the following facts. The distinctive neuron-like structure and the resulting synaptic-like connections establish numerous long-distance continuous channels over various directions in the PEO-based CSEs for fast and uniform Li+ transport. Consequently, the assembled SSLMBs with the CSEs and LiFePO4 or NCM811 cathodes display superior cycling stability over a wide temperature range of 50 °C to 0 °C. Surprisingly, the pouch batteries with the large-scale prepared CSEs kept working after being repeatedly bent, folded, cut or even punched in air. We believe that design of neuron-like nanofillers is a viable approach to produce CSEs with high room temperature ionic conductivity for SSLMBs.

Plant Leaf-Inspired Separators with Hierarchical Structure and Exquisite Fluidic Channels for Dendrite-Free Lithium Metal Batteries.

Lithium (Li) metal batteries are among the most promising devices for high energy storage applications but suffer from severe and irregular Li dendrite growth. Here, it is demonstrated that the issue can be well tackled by precisely designing the leaf-like membrane with hierarchical structure and exquisite fluidic channels. As a proof of concept, plant leaf-inspired membrane (PLIM) separators are prepared using natural attapulgite nanorods. The PLIM separators feature super-electrolyte-philicity, high thermal stability and high ion-selectivity. Thus, the separators can guide uniform and directed Li growth on the Li anode. The Li//PLIM//Li cell with limited Li anode shows high Coulombic efficiency and cycling stability over 1500 h with small overpotential and interface impedance. The Li//PLIM//S battery exhibits high initial capacity (1352 mAh g-1 ), cycling stability (0.019% capacity decay per cycle at 1 C over 500 cycles), rate performance (673 mAh g-1 at 4 C), and high operating temperature (65 °C). The separators can also effectively improve reversibility and cycling stability of the Li/Li cell and Li//LFP battery with carbonate-based electrolyte. As such, this work provides fresh insights into the design of bioinspired separators for dendrite-free metal batteries.

Design of advanced separators for high performance Li-S batteries using natural minerals with 1D to 3D microstructures.

Lithium-sulfur (Li-S) batteries are of great interest due to their high energy density. However, polysulfides shuttle and low S loading severely impede their practical applications. Here, we report design of advanced separators for Li-S batteries using natural minerals with 1D to 3D microstructures. Four natural minerals with different microstructures including 1D halloysite nanotubes, 1D attapulgite nanorods, 2D Li+-montmorillonite (Mmt) nanosheets and 3D porous diatomite were used together with carbon black (CB) for preparation of the mineral/CB-Celgard separators. The Si-OH groups of the minerals act as Lewis acid sites, which could effectively absorb polysulfides by forming LiO and OS bonds with polysulfides. Among all the separators, the Mmt/CB-Celgard separator endowed the Li-S battery with the highest upper plateau discharge capacity (369 mA h g-1), initial reversible capacity (1496 mA h g-1 at 0.1 C), rate performance and cycling stability (666 mA h g-1 after 500 cycles at 1.0 C with 0.046% capacity decay per cycle). The Mmt/CB-Celgard separator also enabled stable cycling of the Li-S battery with high S loading (8.3 mg cm-2) cathode. This work will provide inspiration for future development of advanced separators for high-energy-density Li-S batteries.

A separator based on natural illite/smectite clay for highly stable lithium-sulfur batteries.

In spite of high theoretical specific capacity and specific energy of lithium-sulfur (Li-S) batteries, the poor cycle stability caused by polysulfides shuttle severely hinders their real-world applications. Here, a natural clay mineral (illite/smectite, ISC) and carbon black (C) coated Celgard@2400 (ISC/C@Celgard) separator is reported. The separator shows super-electrolyte-philicity and good mechanical stability. The low-cost and eco-friendly ISC with abundant -OH groups can quickly trap a lot of polysulfides by Li-O and Li-S bonding with polysulfides. The ISC/C layer with uniform nanopores can also inhibit polysulfides shuttle by physical shield. Moreover, good electrical conductivity of the ISC/C layer can reactivate the adsorbed polysulfides and thus enhance S utilization. So, the separator endows the Li-S battery with very high initial reversible capacity (1322 mA h g-1) at 0.1 C and excellent cycle stability with low capacity decay rate (0.054% per cycle) during 500 cycles at 1.0 C. Furthermore, a very high areal capacity (5.9 mAh cm-2) is achieved for the battery composed of the separator and the self-supporting high S loading (8.9 mg cm-2) CNT/S cathode at 0.32 mA cm-2. This study opens the possibility of developing advanced separators using natural clay minerals for highly stable Li-S batteries.