Ambient-air-stable Li3InCl6 halide solid electrolyte, with high ionic conductivity of 1.49 × 10−3 S cm−1 at 25 °C, delivers essential advantages over commercial sulfide-based solid electrolyte.
This review focuses on fundamental understanding, various synthesis routes, chemical/electrochemical stability of halide-based lithium superionic conductors, and their potential applications in energy storage as well as related challenges.
Han et al. have prepared a type of organic-inorganic hybrid material by templatedirected polymerization of cobalt phthalocyanine on carbon nanotubes for a selective CO 2 reduction reaction to CO with a large faradic efficiency, exceptional turnover frequency, and excellent long-term durability.
The development of nonprecious metal based electrocatalysts for hydrogen evolution reaction (HER) has received increasing attention over recent years. Previous studies have established MoC as a promising candidate. Nevertheless, its preparation requires high reaction temperature, which more than often causes particle sintering and results in low surface areas. In this study, we show supporting MoC nanoparticles on the three-dimensional scaffold as a possible solution to this challenge and develop a facile two-step preparation method for ∼3 nm MoC nanoparticles uniformly dispersed on carbon microflowers (MoC/NCF) via the self-polymerization of dopamine. The resulting hybrid material possesses large surface areas and a fully open and accessible structure with hierarchical order at different levels. MoO was found to play an important role in inducing the formation of this morphology presumably via its strong chelating interaction with the catechol groups of dopamine. Our electrochemical evaluation demonstrates that MoC/NCF exhibits excellent HER electrocatalytic performance with low onset overpotentials, small Tafel slopes, and excellent cycling stability in both acidic and alkaline solutions.
Reversible electrochemical storage of alkali metal ions is the basis of many secondary batteries. Over years, various electrode materials are developed and optimized for a specific type of alkali metal ions (Li , Na , or K ), yet there are very few (if not none) candidates that can serve as a universal host material for all of them. Herein, a facile solvothermal method is developed to prepare VS nanosheet assemblies. Individual nanosheets are featured with a few atomic layer thickness, and they are hierarchically arranged with minimized stacking. Electrochemical measurements show that VS nanosheet assemblies enable the rapid and durable storage of Li , Na , or K ions. Most remarkably, the large reversible specific capacity and great cycling stability observed for both Na and K are extraordinary and superior to most existing electrode materials. The experimental results of this study are further supported by density functional theory calculations showing that the layered structure of VS has large adsorption energy and low diffusion barriers for the intercalation of alkali metal ions.
Active and durable electrocatalysts for methanol oxidation reaction are of critical importance to the commercial viability of direct methanol fuel cell technology. Unfortunately, current methanol oxidation electrocatalysts fall far short of expectations and suffer from rapid activity degradation. Here we report platinum–nickel hydroxide–graphene ternary hybrids as a possible solution to this long-standing issue. The incorporation of highly defective nickel hydroxide nanostructures is believed to play the decisive role in promoting the dissociative adsorption of water molecules and subsequent oxidative removal of carbonaceous poison on neighbouring platinum sites. As a result, the ternary hybrids exhibit exceptional activity and durability towards efficient methanol oxidation reaction. Under periodic reactivations, the hybrids can endure at least 500,000 s with negligible activity loss, which is, to the best of our knowledge, two to three orders of magnitude longer than all available electrocatalysts.
There has been a continuous call for active, durable, and low‐cost electrocatalysts for a range of energy applications. Among many different nonprecious metal based candidates, transition metal nanoparticles encapsulated in graphene layers have gained increasing attention over recent years. In this study, it is demonstrated that metallic cobalt nanoparticles sheathed by multilayered nitrogen‐enriched graphene shells can be facilely prepared using cobalt‐containing Prussian blue colloids as the single precursor. These metallic cobalt cores can be readily leached out by HCl treatment, resulting in hollow graphene spheres. Products with or without acid leaching exhibit great bifunctional activities for electrocatalytic oxygen reduction and hydrogen evolution in both alkaline and acidic electrolytes. Most importantly, it is found that the removal of the metallic cores does not deteriorate but rather enhances the electrocatalytic performance. Based on this and other experimental observations, Co‐N‐C moieties are proposed as the catalytically active sites. At last, it is shown that these catalysts can be employed as the air catalyst of primary zinc–air batteries with excellent current density, power density, and operation durability.
Sulfide‐based solid‐state electrolytes (SSEs) for all‐solid‐state Li metal batteries (ASSLMBs) are attracting significant attention due to their high ionic conductivity, inherently soft properties, and decent mechanical strength. However, the poor incompatibility with Li metal and air sensitivity have hindered their application. Herein, the Sn (IV) substitution for P (V) in argyrodite sulfide Li6PS5I (LPSI) SSEs is reported, in the preparation of novel LPSI‐xSn SSEs (where x is the Sn substitution percentage). Appropriate aliovalent element substitutions with larger atomic radius (R > R
) provides the optimized LPSI‐20Sn electrolyte with a 125 times higher ionic conductivity compared to that of the LPSI electrolyte. The high ionic conductivity of LPSI‐20Sn enables the rich I‐containing electrolyte to serve as a stabilized interlayer against Li metal in sulfide‐based ASSLMBs with outstanding cycling stability and rate capability. Most importantly, benefiting from the strong Sn–S bonding in Sn‐substituted electrolytes, the LPSI‐20Sn electrolyte shows excellent structural stability and improved air stability after exposure to O2 and moisture. The versatile Sn substitution in argyrodite LPSI electrolytes is believed to provide a new and effective strategy to achieve Li metal‐compatible and air‐stable sulfide‐based SSEs for large‐scale applications.
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