Manipulated Fluoro-Ether Derived Nucleophilic Decomposition Products for Mitigating Polarization-Induced Capacity Loss in Li-Rich Layered Cathode.

Electrolyte engineering is a fascinating choice to improve the performance of Li-rich layered oxide cathodes (LRLO) for high-energy lithium-ion batteries. However, many existing electrolyte designs and adjustment principles tend to overlook the unique challenges posed by LRLO, particularly the nucleophilic attack. Here, we introduce an electrolyte modification by locally replacing carbonate solvents in traditional electrolytes with a fluoro-ether. By benefit of the decomposition of fluoro-ether under nucleophilic O-related attacks, which delivers an excellent passivation layer with LiF and polymers, possessing rigidity and flexibility on the LRLO surface. More importantly, the fluoro-ether acts as "sutures", ensuring the integrity and stability of both interfacial and bulk structures, which contributed to suppressing severe polarization and enhancing the cycling capacity retention from 39 % to 78 % after 300 cycles for the 4.8 V-class LRLO. This key electrolyte strategy with comprehensive analysis, provides new insights into addressing nucleophilic challenge for high-energy anionic redox related cathode systems.

On-chip gas reaction nanolab for in situ TEM observation.

The catalysis reaction mechanism at nano/atomic scale attracted intense attention in the past decades. However, most in situ characterization technologies can only reflect the average information of catalysts, which leads to the inability to characterize the dynamic changes of single nanostructures or active sites under operando conditions, and many micro-nanoscale reaction mechanisms are still unknown. The combination of in situ transmission electron microscopy (TEM) holder system with MEMS chips provides a solution for it, where the design and fabrication of MEMS chips are the key factors. Here, with the aid of finite element simulation, an ultra-stable heating chip was developed, which has an ultra-low thermal drift during temperature heating. Under ambient conditions within TEM, atomic resolution imaging was achieved during the heating process or at high temperature up to 1300 °C. Combined with the developed polymer membrane seal technique and nanofluidic control system, it can realize an adjustable pressure from 0.1 bar to 4 bar gas environment around the sample. By using the developed ultra-low drift gas reaction cells, the nanoparticle's structure evolution at atomic scale was identified during reaction.

Liquid cell transmission electron microscopy study of platinum iron nanocrystal growth and shape evolution.

We study solution growth of platinum iron nanocrystals in situ in a liquid cell by using transmission electron microscopy. By varying the oleylamine concentration, we observed that platinum iron nanoparticle growth follows different trajectories with diverse shape evolution. With 20% oleylamine, three stages of growth were observed: (i) nucleation and growth of platinum iron nanoparticles in the precursor solution; (ii) nanowire formation by shape-directed nanoparticle attachment; and (iii) breakdown or shrinkage of the nanowires into individual nanoparticles with large size distribution. With 30% oleylamine, formation of platinum iron nanowires similar to that with 20% oleylamine was observed. However, those nanowires do not break down or shrink, which suggests that nanowires are stabilized by oleylamine as surfactant binding on the surface. With 50% oleylamine, after the individual nanoparticles are formed, they do not merge into nanowires. The shape of the nanoparticle is strongly influenced by the neighboring nanoparticles due to stereo-hindrance effects. Real-time observation of the dynamic growth process sheds light on the controllable synthesis of nanomaterials.