Hetero-Polyionic Hydrogels Enable Dendrites-Free Aqueous Zn-I2 Batteries with Fast Kinetics.

Rechargeable aqueous Zn-I2 batteries (ZIB) are regarded as a promising energy storage candidate. However, soluble polyiodide shuttling and rampant Zn dendrite growth hamper its commercial implementation. Herein, a hetero-polyionic hydrogel is designed as the electrolyte for ZIBs. On the cathode side, iodophilic polycationic hydrogel (PCH) effectively alleviates the shuttle effect and facilitates the redox kinetics of iodine species. Meanwhile, polyanionic hydrogel (PAH) toward Zn metal anode uniformizes Zn2+ flux and prevents surface corrosion by electrostatic repulsion of polyiodides. Consequently, the Zn symmetric cells with PAH electrolyte demonstrate remarkable cycling stability over 3000 h at 1 mA cm-2 (1 mAh cm-2 ) and 800 h at 10 mA cm-2 (5 mAh cm-2 ). Moreover, the Zn-I2 full cells with PAH-PCH hetero-polyionic hydrogel electrolyte deliver a low-capacity decay of 0.008 ‰ per cycle during 18 000 cycles at 8 C. This work sheds light on hydrogel electrolytes design for long-life conversion-type aqueous batteries.

Enhanced Polysulfide Trapping and Conversion by Amorphous-Crystalline Heterostructured MnO2 Interlayers for Li-S Batteries.

The practical application of lithium-sulfur batteries (LSBs) is still hindered by several technical issues, including severe polysulfide shuttling and sluggish redox kinetics, which reduces the sulfur utilization and further results in low energy density. Herein, amorphous-crystalline heterostructured MnO2 (ACM) prepared through a simple calcination process was employed as the functional interlayer to play a double role as effective trapper and multifunctional electrocatalyst for LSBs. ACM not only combines the strong sulfur chemisorption of the amorphous MnO2 (AM) and fast Li+ transportation of the crystalline MnO2(CM) but also accelerates the interface charge transfer at the amorphous/crystalline interfaces. The LSBs with such unique interlayer exhibited an excellent rate performance of 1155.5 mAh·g-1 at 0.2 C and 692.9 mAh·g-1 at 3 C and a low decay rate of 0.071% per cycle over 500 cycles at 0.5 C. Even for a high sulfur loading of 5 mg·cm-2 at 0.1 C, a high capacity retention of 92.3% could also be achieved after 100 cycles. The concept of amorphous-crystalline heterostructures prepared by crystallization regulation might also be used for other electronic devices and catalyst designs.

Atomically Dispersed Fe-N4 and Ni-N4 Independent Sites Enable Bidirectional Sulfur Redox Electrocatalysis.

Single-atom catalysts (SACs) with high atom utilization and outstanding catalytic selectivity are useful for improving battery performance. Herein, atomically dispersed Ni-N4 and Fe-N4 dual sites coanchored on porous hollow carbon nanocages (Ni-Fe-NC) are fabricated and deployed as the sulfur host for Li-S battery. The hollow and conductive carbon matrix promotes electron transfer and also accommodates volume fluctuation during cycling. Notably, the high d band center of Fe in Fe-N4 site demonstrates strong polysulfide affinity, leading to an accelerated sulfur reduction reaction. Meanwhile, Li2S on the Ni-N4 site delivers a metallic property with high S 2p electron density of states around the Femi energy level, enabling a low sulfur evolution reaction barrier. The dual catalytic effect on Ni-Fe-NC endows sulfur cathode high energy density, prolonged lifespan, and low polarization.

Built-In Electric Field on the Mott-Schottky Heterointerface-Enabled Fast Kinetics Lithium-Sulfur Batteries.

Lithium-sulfur (Li-S) batteries (LSBs) have been considered one of the most potential candidates to substitute traditional Li-ion batteries (LIBs), owing to their high theoretical energy density and low cost. Nevertheless, the shuttle effect and the sluggish redox kinetics of lithium polysulfides (LiPSs) have long been obstacles to realizing stable LSBs with high reversible capacity. In this study, we proposed a metal-semiconductor (Mo and MoO2) heterostructure with the hollow microsphere morphology as an effective Mott-Schottky electrocatalyst to boost sulfur electrochemistry. The hollow structure can physically inhibit the shuttling of LiPSs and accommodate the volume fluctuation during cycling. More importantly, the built-in electric field at the heterointerfacial sites can effectively accelerate the reduction of LiPSs and oxidation of Li2S, thereby reaching a high sulfur utilization. With the assistance of the Mo/MoO2 catalyst, the cell exhibited prominent rate capability and stable long-term cycling performance, showing a high capacity of 630 mA h·g-1 at 4 C and a low decay of 0.073% at 1 C after 500 cycles. Even with high areal sulfur loading of 10.0 mg·cm-2, high capacity and good cycle stability were achieved at 0.2 C under lean electrolyte conditions (E/S ratio of 6 µL·mg-1).

Rich Heterointerfaces Enabling Rapid Polysulfides Conversion and Regulated Li2S Deposition for High-Performance Lithium-Sulfur Batteries.

The practical uses of lithium-sulfur batteries are greatly restricted by the sluggish reaction kinetics of lithium polysulfides (LiPSs), leading to low sulfur utilization and poor cyclic stability. Using the heterostructure catalysts is an effective way to solve the above problems, but how to further enhance the conversion efficiency and avoid the surface passivation by the insulative Li2S has not been well investigated. Herein, a heterostructure catalyst with rich heterointerfaces was prepared by modifying Mo2N microbelt with SnO2 nanodots. The formed rich interfaces with high accessibility act as the profitable nucleation sites guiding the Li2S 3D growth, which avoids the catalyst surface passivation and facilitates the LiPS conversion. The introduction of SnO2 nanodots also enhances the LiPS adsorption. Thus, the assembled battery with the above catalyst as the cathode additive shows a high capacity of 738.3 mAh g-1 after 550 cycles at 0.5 C with an ultralow capacity decay of 0.025% per cycle. Even with high sulfur loading of 9.0 mg cm-2, good cyclic stability is also achieved at 0.5 C with a low E/S ratio of 5 µL mgs-1. This work shows an effective way to enhance the LiPS conversion kinetics and guide Li2S deposition in Li-S batteries.