Accumulation of Sulfonic Acid Groups Anchored in Covalent Organic Frameworks as an Intrinsic Proton-Conducting Electrolyte.

Covalent organic frameworks (COFs) are a novel class of crystalline porous polymers, which possess high porosity, excellent stability, and regular nanochannels. 2D COFs provide a 1D nanochannel to form the proton transport channels. The abovementioned features afford a powerful potential platform for designing materials as proton transportation carriers. Herein, the authors incorporate sulfonic acid groups on the pore walls as proton sources for enhancing proton transport conductivity in the 1D channel. Interestingly, the sulfonic acid COFs (S-COFs) electrolytes being binder free exhibit excellent proton conductivity of ≈1.5 × 10-2 S cm-1 at 25 ℃ and 95% relative humidity (RH), which rank the excellent performance in standard proton-conducting electrolytes. The S-COFs electrolytes keep the high proton conduction over the 24 h. The activation energy is estimated to be as low as 0.17 eV, which is much lower than most reported COFs. This research opens a new window to evolve great potential of structural design for COFs as the high proton-conducting electrolytes.

A review of composite solid-state electrolytes for lithium batteries: fundamentals, key materials and advanced structures.

All-solid-state lithium ion batteries (ASSLBs) are considered next-generation devices for energy storage due to their advantages in safety and potentially high energy density. As the key component in ASSLBs, solid-state electrolytes (SSEs) with non-flammability and good adaptability to lithium metal anodes have attracted extensive attention in recent years. Among the current SSEs, composite solid-state electrolytes (CSSEs) with multiple phases have greater flexibility to customize and combine the advantages of single-phase electrolytes, which have been widely investigated recently and regarded as promising candidates for commercial ASSLBs. Based on existing investigations, herein, we present a comprehensive overview of the recent developments in CSSEs. Initially, we introduce the historical development from solid-state ionic conductors to CSSEs, and then summarize the fundamentals including mechanisms of lithium ion transport, key evaluation parameters, design principles, and key materials. Four main types of advanced structures for CSSEs are classified and highlighted according to the recent progress. Moreover, advanced characterization and computational simulation techniques including machine learning are reviewed for the first time, and the main challenges and perspectives of CSSEs are also provided for their future development.

Lyotropic Liquid Crystalline Property and Organized Structure in High Proton-Conductive Sulfonated Semialicyclic Oligoimide Thin Films.

Fully aromatic sulfonated polyimides with a rigid backbone can form lamellar structures under humidified conditions, thereby facilitating the transmission of protons in ionomers. Herein, we synthesized a new sulfonated semialicyclic oligoimide composed of 1,2,3,4-cyclopentanetetracarboxylic dianhydride (CPDA) and 3,3'-bis-(sulfopropoxy)-4,4'-diaminobiphenyl to investigate the influence of molecular organized structure and proton conductivity with lower molecular weight. The weight-average molecular weight (M w) determined by gel permeation chromatography was 9300. Humidity-controlled grazing incidence X-ray scattering revealed that one scattering was observed in the out-of-plane direction and showed that the scattering position shifted to a lower angle as the humidity increased. A loosely packed lamellar structure was formed by lyotropic liquid crystalline properties. Although the ch-pack aggregation of the present oligomer was reduced by substitution to the semialicyclic CPDA from the aromatic backbone, the formation of a distinct organized structure in the oligomeric form was observed because of the linear conformational backbone. This report is the first-time observation of the lamellar structure in such a low-molecular-weight oligoimide thin film. The thin film exhibited a high conductivity of 0.2 (±0.01) S cm-1 under 298 K and 95% relative humidity, which is the highest value compared to the other reported sulfonated polyimide thin films with comparable molecular weight.

Nanoporous bimetallic metal-organic framework (FeCo-BDC) as a novel catalyst for efficient removal of organic contaminants.

In this work, we report on the synthesis and characterization of nanoporous bimetallic metal-organic frameworks (FeCo-BDC). Effects of synthesis time and temperature on the structures, morphology, and catalytic performance of FeCo-BDC were investigated. Scanning Electron Microscopy (SEM), Transmission electron microscopy (TEM) and Brunauer-Emmett-Teller (BET) were used to reveal the morphological and textural characteristics. The crystal structure and chemical composition of FeCo-BDC were determined by means of X-ray powder diffraction (XRD), Fourier Transform Infrared Spectroscopy (FT-IR), X-ray Photoelectron Spectroscopy (XPS), and Inductively Coupled Plasma Mass Spectrometry (ICP-MS) measurements. Interestingly, FeCo-BDC grew into the same crystal structure with different morphology in the temperature of 110-150 °C with 12-48 h. The heterogeneous catalytic activity of FeCo-BDC was tested to activate peroxydisulfate (PDS) and peroxymonosulfate (PMS) for removal of methylene blue (MB). The results found that FeCo-BDC synthesized at 150 °C with 24 h exhibited the best catalytic performance for PMS and obtained 100% of MB removal within 15 min. The abundant unsaturated metal active sites of Fe(II) and Co(II) in the skeleton of FeCo-BDC made a great contribution to the generation of sulfate () and hydroxyl radicals (OH), which resulted in the excellent performance for MB degradation.

Hierarchical NiCo2O4 Micro- and Nanostructures with Tunable Morphologies as Anode Materials for Lithium- and Sodium-Ion Batteries.

NiCo2O4 microrods with open structures are successfully synthesized using a solvothermal method. Compared with those of dense microspheres, the one-dimensional (1D) porous microrods show much higher capacities and stability for both Li- and Na-ion batteries due to the 1D open structure facilitating fast ion transport and buffering volumetric change during charge/discharge. This work demonstrates that the electrochemical performance of NiCo2O4 is highly dependent on morphologies of the active material.

Hollow Porous Hierarchical-Structured 0.5Li2MnO3·0.5LiMn0.4Co0.3Ni0.3O2 as a High-Performance Cathode Material for Lithium-Ion Batteries.

We report a novel hollow porous hierarchical-architectured 0.5Li2MnO3·0.5LiMn0.4Co0.3Ni0.3O2 (LLO) for lithium-ion batteries (LIBs). The obtained lithium-rich layered oxides possess a large inner cavity, a permeable porous shell, and excellent structural robustness. In LIBs, such unique features are favorable for fast Li+ transportation and can provide sufficient contact between active materials and electrolytes, accommodate more Li+, and improve the kinetics of the electrochemical reaction. The as-prepared LLO displays an extremely high initial discharge capacity (296.5 mAh g-1 at 0.2 C), high rate capability (162.6 mAh g-1 at 10 C), and excellent cycling stability (237.6 mAh g-1 after 100 cycles at 0.5 C and 153.8 mAh g-1 after 200 cycles at 10 C). These values are superior to most literature data.