Healable and conductive sulfur iodide for solid-state Li-S batteries.

Solid-state Li-S batteries (SSLSBs) are made of low-cost and abundant materials free of supply chain concerns. Owing to their high theoretical energy densities, they are highly desirable for electric vehicles1-3. However, the development of SSLSBs has been historically plagued by the insulating nature of sulfur4,5 and the poor interfacial contacts induced by its large volume change during cycling6,7, impeding charge transfer among different solid components. Here we report an S9.3I molecular crystal with I2 inserted in the crystalline sulfur structure, which shows a semiconductor-level electrical conductivity (approximately 5.9 × 10-7 S cm-1) at 25 °C; an 11-order-of-magnitude increase over sulfur itself. Iodine introduces new states into the band gap of sulfur and promotes the formation of reactive polysulfides during electrochemical cycling. Further, the material features a low melting point of around 65 °C, which enables repairing of damaged interfaces due to cycling by periodical remelting of the cathode material. As a result, an Li-S9.3I battery demonstrates 400 stable cycles with a specific capacity retention of 87%. The design of this conductive, low-melting-point sulfur iodide material represents a substantial advancement in the chemistry of sulfur materials, and opens the door to the practical realization of SSLSBs.

Toward a quantitative interfacial description of solvation for Li metal battery operation under extreme conditions.

The future application of Li metal batteries (LMBs) at scale demands electrolytes that endow improved performance under fast-charging and low-temperature operating conditions. Recent works indicate that desolvation kinetics of Li+ plays a crucial role in enabling such behavior. However, the modulation of this process has typically been achieved through inducing qualitative degrees of ion pairing into the system. In this work, we find that a more quantitative control of the ion pairing is crucial to minimizing the desolvation penalty at the electrified interface and thus the reversibility of the Li metal anode under kinetic strain. This effect is demonstrated in localized electrolytes based on strongly and weakly bound ether solvents that allow for the deconvolution of solvation chemistry and structure. Unexpectedly, we find that maximum degrees of ion pairing are suboptimal for ultralow temperature and high-rate operation and that reversibility is substantially improved via slight local dilution away from the saturation point. Further, we find that at the optimum degree of ion pairing for each system, weakly bound solvents still produce superior behavior. The impact of these structure and chemistry effects on charge transfer are then explicitly resolved via experimental and computational analyses. Lastly, we demonstrate that the locally optimized diethyl ether-based localized-high-concentration electrolytes supports kinetic strained operating conditions, including cycling down to -60 °C and 20-min fast charging in LMB full cells. This work demonstrates that explicit, quantitative optimization of the Li+ solvation state is necessary for developing LMB electrolytes capable of low-temperature and high-rate operation.

Damage-Tolerant Wood Layers for Corrosion Protection of Metal Structures.

Mechanically strong and damage-tolerant corrosion protection layers are of great technological importance. However, corrosion protection layers with high modulus (>1.5 GPa) and tensile strength (>100 MPa) are rare. Here, we report that a 130 µm thick densified wood veneer with a Young's modulus of 34.49 GPa and tensile strength of 693 MPa exhibits both low diffusivity for metal ions and the ability of self-recovery from mechanical damage. Densified wood veneer is employed as an intermediate layer to render a mechanically strong corrosion protection structure, referred to as "wood corrosion protection structure", or WCPS. The corrosion rate of low-carbon steel protected by WCPS is reduced by 2 orders of magnitude than state-of-the-art corrosion protection layers during a salt spray test. The introduction of engineered wood veneer as a thin and mechanically strong material points to new directions of sustainable corrosion protection design.

Hierarchically porous Au nanostructures with interconnected channels for efficient mass transport in electrocatalytic CO2 reduction.

Electrocatalytic CO2 reduction is a promising way to provide renewable energy from gaseous CO2 The development of nanostructures improves energy efficiency and selectivity for value-added chemicals, but complex nanostructures limit the CO2 conversion rates due to poor mass transport during vigorous electrolysis. Herein, we propose a three-dimensional (3D) hierarchically porous Au comprising interconnected macroporous channels (200-300 nm) and nanopores (∼10 nm) fabricated via proximity-field nanopatterning. The interconnected macropores and nanopores enable efficient mass transport and large active areas, respectively. The roles of each pore network are investigated using reliable 3D nanostructures possessing controlled pore distribution and size. The hierarchical nanostructured electrodes show a high CO selectivity of 85.8% at a low overpotential of 0.264 V and efficient mass activity that is maximum 3.96 times higher than that of dealloyed nanoporous Au. Hence, the systematic model study shows the proposed hierarchical nanostructures have important value in increasing the efficiency of expensive Au.

Three-Dimensional, Submicron Porous Electrode with a Density Gradient to Enhance Charge Carrier Transport.

Rapid charging capability is a requisite feature of lithium-ion batteries (LIBs). To overcome the capacity degradation from a steep Li-ion concentration gradient during the fast reaction, electrodes with tailored transport kinetics have been explored by managing the geometries. However, the traditional electrode fabrication process has great challenges in precisely controlling and implementing the desired pore networks and configuration of electrode materials. Herein, we demonstrate a density-graded composite electrode that arises from a three-dimensional current collector in which the porosity gradually decreases to 53.8% along the depth direction. The density-graded electrode effectively reduces energy loss at high charging rates by mitigating polarization. This electrode shows an outstanding capacity of 94.2 mAh g-1 at a fast current density of 59.7 C (20 A g-1), which is much higher than that of an electrode with a nearly constant density gradient (38.0 mAh g-1). Through these in-depth studies on the pore networks and their transport kinetics, we describe the design principle of rational electrode geometries for ultrafast charging LIBs.