Multifunctional Catalytic Hierarchical Interfaces of Ni12 P5 -Ni2 P Porous Nanosheets Enabled Both Sulfides Reaction Promotion and Li-Dendrite Suppression for High-Performance Li-S Full Batteries.

The development of lithium-sulfur (Li-S) batteries is very promising and yet faces the issues of hindered polysulfides conversion and Li dendrite growth. Different from using different materials strategies to overcome these two types of problems, here multifunctional catalytic hierarchical interfaces of Ni12 P5 -Ni2 P porous nanosheets formed by Ni2 P partially in situ converted from Ni12 P5 are proposed. The unique electronic structure in the interface endows Ni12 P5 -Ni2 P effective electrocatalysis effect toward both sulfides' reduction and oxidation through reducing Gibbs free energies, indicating a bidirectional conversion acceleration. Importantly, Ni12 P5 -Ni2 P porous nanosheets with hierarchical interfaces also reduced the Li nucleation energy barrier, and a dendrite-free Li deposition is realized during the overall Li deposition and stripping steps. To this end, Ni12 P5 -Ni2 P decorated carbon nanotube/S cathode showing a high capacity of over 1500 mAh g-1 , and a high rate capability of 8 C. Moreover, the coin full cell delivered a high capacity of 1345 mAh g-1 at 0.2 C and the pouch full cell delivered a high capacity of 1114 mAh g-1 at 0.2 C with high electrochemical stability during 180° bending. This work inspires the exploration of hierarchical structures of 2D materials with catalytically active interfaces to improve the electrochemistry of Li-S full battery.

In Situ 1D Carbon Chain-Mail Catalyst Assembly for Stable Lithium-Sulfur Full Batteries.

The main obstacles for the commercial application of Lithium-Sulfur (Li-S) full batteries are the large volume change during charging/discharging process, the shuttle effect of lithium polysulfide (LiPS), sluggish redox kinetics, and the indisciplinable dendritic Li growth. Especially the overused of metal Li leads to the low utilization of active Li, which seriously drags down the actual energy density of Li-S batteries. Herein, an efficient design of dual-functional CoSe electrocatalyst encapsulated in carbon chain-mail (CoSe@CCM) is employed as the host both for the cathode and anode regulation simultaneously. The carbon chain-mail constituted by carbon encapsulated layer cross-linking with carbon nanofibers protects CoSe from the corrosion of chemical reaction environment, ensuring the high activity of CoSe during the long-term cycles. The Li-S full battery using this carbon chain-mail catalyst with a lower negative/positive electrode capacity ratio (N/P < 2) displays a high areal capacity of 9.68 mAh cm-2 over 150 cycles at a higher sulfur loading of 10.67 mg cm-2 . Additionally, a pouch cell is stable for 80 cycles at a sulfur loading of 77.6 mg, showing the practicality feasibility of this design.

Dual-Functional Lithiophilic/Sulfiphilic Binary-Metal Selenide Quantum Dots Toward High-Performance Li-S Full Batteries.

The commercial viability of lithium-sulfur batteries is still challenged by the notorious lithium polysulfides (LiPSs) shuttle effect on the sulfur cathode and uncontrollable Li dendrites growth on the Li anode. Herein, a bi-service host with Co-Fe binary-metal selenide quantum dots embedded in three-dimensional inverse opal structured nitrogen-doped carbon skeleton (3DIO FCSe-QDs@NC) is elaborately designed for both sulfur cathode and Li metal anode. The highly dispersed FCSe-QDs with superb adsorptive-catalytic properties can effectively immobilize the soluble LiPSs and improve diffusion-conversion kinetics to mitigate the polysulfide-shutting behaviors. Simultaneously, the 3D-ordered porous networks integrated with abundant lithophilic sites can accomplish uniform Li deposition and homogeneous Li-ion flux for suppressing the growth of dendrites. Taking advantage of these merits, the assembled Li-S full batteries with 3DIO FCSe-QDs@NC host exhibit excellent rate performance and stable cycling ability (a low decay rate of 0.014% over 2,000 cycles at 2C). Remarkably, a promising areal capacity of 8.41 mAh cm-2 can be achieved at the sulfur loading up to 8.50 mg cm-2 with an ultra-low electrolyte/sulfur ratio of 4.1 µL mg-1. This work paves the bi-serve host design from systematic experimental and theoretical analysis, which provides a viable avenue to solve the challenges of both sulfur and Li electrodes for practical Li-S full batteries.

Selective Nitridation Crafted a High-Density, Carbon-Free Heterostructure Host with Built-In Electric Field for Enhanced Energy Density Li-S Batteries.

To achieve both high gravimetric and volumetric energy densities of lithium-sulfur (Li-S) batteries, it is essential yet challenging to develop low-porosity dense electrodes along with diminishment of the electrolyte and other lightweight inactive components. Herein, a compact TiO2 @VN heterostructure with high true density (5.01 g cm-3 ) is proposed crafted by ingenious selective nitridation, serving as carbon-free dual-capable hosts for both sulfur and lithium. As a heavy S host, the interface-engineered heterostructure integrates adsorptive TiO2 with high conductive VN and concurrently yields a built-in electric field for charge-redistribution at the TiO2 /VN interfaces with enlarged active locations for trapping-migration-conversion of polysulfides. Thus-fabricated TiO2 @VN-S composite harnessing high tap-density favors constructing dense cathodes (≈1.7 g cm-3 ) with low porosity (<30 vol%), exhibiting dual-boosted cathode-level peak volumetric-/gravimetric-energy-densities nearly 1700 Wh L-1 cathode /1000 Wh kg-1 cathode at sulfur loading of 4.2 mg cm-2 and prominent areal capacity (6.7 mAh cm-2 ) at 7.6 mg cm-2 with reduced electrolyte (<10 µL mg-1 sulfur ). Particular lithiophilicity of the TiO2 @VN is demonstrated as Li host to uniformly tune Li nucleation with restrained dendrite growth, consequently bestowing the assembled full-cell with high electrode-level volumetric/gravimetric-energy-density beyond 950 Wh L-1 cathode+anode /560 Wh kg-1 cathode+anode at 3.6 mg cm-2 sulfur loading alongside limited lithium excess (≈50%).