Selection and Surface Modifications of Current Collectors for Anode-Free Polymer-Based Solid-State Batteries.

Anode-free batteries (AFB) have attracted increasing interest in recent times because they allow the elimination of the conventional anode from the cell, exploiting lithium inventory from a lithiated cathode. This implies a much simpler, cost-effective, and sustainable approach. The AFB configuration with liquid electrolytes is being explored widely in research but rarely using solid electrolytes. One of the main issues of AFB is the poor reversibility of the lithium-plating/striping process at the anode side. Therefore, in this work, different metal foils have been tested as anode current collectors (CC), and copper foil has been selected as the most promising one. Surface modifications of the selected copper foil have been achieved by its coating using composite layers made of carbon and different metal nanoparticles-such as Ag, Sn, or Zn-in different proportions and with different amounts of a binder. The impact of such coatings and their thickness on the electrochemical performance of single-layer solid-state anode-free pouch cells, based on a PEO electrolyte and a LiFePO4 cathode has been systematically studied. Consequently, a post-mortem analysis of the investigated solid-state AFB is also presented, trying to identify and elucidate possible failure mechanisms to enhance the electrochemical performance of solid-state AFB in the future.

High Performance Polymer/Ionic Liquid Thermoplastic Solid Electrolyte Prepared by Solvent Free Processing for Solid State Lithium Metal Batteries.

A polymer/ionic liquid thermoplastic solid electrolyte based on poly(ethylene oxide) (PEO), modified sepiolite (TPGS-S), lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), and 1-Butyl-1-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide (PYR14TFSI) ionic liquid is prepared using solvent free extrusion method. Its physical-chemical, electrical, and electrochemical properties are comprehensively studied. The investigated solid electrolyte demonstrates high ionic conductivity together with excellent compatibility with lithium metal electrode. Finally, truly Li-LiFePO4 solid state coin cell with the developed thermoplastic solid electrolyte demonstrates promising electrochemical performance during cycling under 0.2 C/0.5 C protocol at 60 °C.

Perturbation-Theory and Machine Learning (PTML) Model for High-Throughput Screening of Parham Reactions: Experimental and Theoretical Studies.

Machine learning (ML) algorithms are gaining importance in the processing of chemical information and modeling of chemical reactivity problems. In this work, we have developed a perturbation-theory and machine learning (PTML) model combining perturbation theory (PT) and ML algorithms for predicting the yield of a given reaction. For this purpose, we have selected Parham cyclization, which is a general and powerful tool for the synthesis of heterocyclic and carbocyclic compounds. This reaction has both structural (substitution pattern on the substrate, internal electrophile, ring size, etc.) and operational variables (organolithium reagent, solvent, temperature, time, etc.), so predicting the effect of changes on substrate design (internal elelctrophile, halide, etc.) or reaction conditions on the yield is an important task that could help to optimize the reaction design. The PTML model developed uses PT operators to account for perturbations under experimental conditions and/or structural variables of all the molecules involved in a query reaction, compared to a reaction of reference. Thus, a dataset of >100 reactions has been collected for different substrates and internal electrophiles, under different reaction conditions, with a wide range of yields (0-98%). The best PTML model found using General Linear Regression (GLR) has R = 0.88 in training and R = 0.83 in external validation series for 10 000 pairs of query and reference reactions. The PTML model has a final R = 0.95 for all reactions using multiple reactions of reference. We also report a comparative study of linear versus nonlinear PTML models based on artificial neural network (ANN) algorithms. PTML-ANN models (LNN, MLP, RBF) with R ≈ 0.1-0.8 do not outperform the first PMTL model. This result confirms the validity of the linearity of the model. Next, we carried out an experimental and theoretical study of nonreported Parham reactions to illustrate the practical use of the PTML model. A 500 000-point simulation and a Hammett analysis of the reactivity space of Parham reactions are also reported.

New Redox Polymers that Exhibit Reversible Cleavage of Sulfur Bonds as Cathode Materials.

Two new cathode materials based on redox organosulfur polymers were synthesized and investigated for rechargeable lithium batteries as a proof-of-concept study. These cathodes offered good cycling performance owing to the absence of polysulfide solubility, which plagues Li/S systems. Herein, an aliphatic polyamine or a conjugated polyazomethine was used as the base to tether the redox-active species. The activity comes from the cleavage and formation of S-S or N-S bonds, which is made possible by the rigid conjugated backbone. The synthesized polymers were characterized through FTIR spectroscopy and thermogravimetric analysis (TGA). Galvanostatic measurements were performed to evaluate the discharge/charge cycles and characterize the performance of the lithium-based cells, which displayed initial discharge capacities of approximately 300 mA h g-1 at C/5 over 100 cycles with approximately 98 % Coulombic efficiency.

All-Solid-State Lithium-Ion Batteries with Grafted Ceramic Nanoparticles Dispersed in Solid Polymer Electrolytes.

Lithium-based rechargeable batteries offer superior specific energy and power, and have enabled exponential growth in industries focused on small electronic devices. However, further increases in energy density, for example for electric transportation, face the challenge of harnessing the lithium metal as negative electrode instead of limited-capacity graphite and its heavy copper current collector. All-solid-state batteries utilize solid polymer electrolytes (SPEs) to overcome the safety issues of liquid electrolytes. We demonstrate an all-solid-state lithium-ion battery by using plasticized poly(ethylene oxide)-based SPEs comprising anions grafted or co-grafted onto ceramic nanoparticles. This new approach using grafted ceramic nanoparticles enables the development of a new generation of nanohybrid polymer electrolytes with high ionic conductivity as well as high electrochemical and mechanical stability, enabling Li-ion batteries with long cycle life.