Lithium Borate Polycarbonates for High-Capacity Solid-State Composite Cathodes.

Improving composite cathode function is key to the success of the solid-state battery. Maximizing attainable cathode capacity and retention requires integrating suitable polymeric binders that retain a sufficiently high ionic conductivity and long-term chemo-mechanical stability of the cathode active material-solid-electrolyte-carbon mixture. Herein, we report block copolymer networks composed of lithium borate polycarbonates and poly(ethylene oxide) that improved the capacity (200 mA h g-1 at 1.75 mA cm-2) and capacity retention (94% over 300 cycles) of all-solid-state composite cathodes with nickel-rich LiNi0.8Co0.1Mn0.1O2 cathode active material, Li6PS5Cl solid electrolyte, and carbon. Tetrahedral B(OR)2(OH)2- anions immobilized on the polycarbonate segments provide hydrogen-bonding chain crosslinking and selective Li-counterion conductivity, parameterized by Li-ion transference numbers close to unity (tLi+ ~ 0.94). With 90 wt% polycarbonate content and a flexible low glass transition temperature backbone, the single-ion conductors achieved high Li-ion conductivities of 0.2 mS cm-1 at 30°C. The work should inform future binder design for improving the processability of cathode composites towards commercialising solid-state batteries, and allow use in other cell configurations, such as lithium-sulphur cathode designs.

Alternatives to fluorinated binders: recyclable copolyester/carbonate electrolytes for high-capacity solid composite cathodes.

Optimising the composite cathode for next-generation, safe solid-state batteries with inorganic solid electrolytes remains a key challenge towards commercialisation and cell performance. Tackling this issue requires the design of suitable polymer binders for electrode processability and long-term solid-solid interfacial stability. Here, block-polyester/carbonates are systematically designed as Li-ion conducting, high-voltage stable binders for cathode composites comprising of single-crystal LiNi0.8Mn0.1Co0.1O2 cathodes, Li6PS5Cl solid electrolyte and carbon nanofibres. Compared to traditional fluorinated polymer binders, improved discharge capacities (186 mA h g-1) and capacity retention (96.7% over 200 cycles) are achieved. The nature of the new binder electrolytes also enables its separation and complete recycling after use. ABA- and AB-polymeric architectures are compared where the A-blocks are mechanical modifiers, and the B-block facilitates Li-ion transport. This reveals that the conductivity and mechanical properties of the ABA-type are more suited for binder application. Further, catalysed switching between CO2/epoxide A-polycarbonate (PC) synthesis and B-poly(carbonate-r-ester) formation employing caprolactone (CL) and trimethylene carbonate (TMC) identifies an optimal molar mass (50 kg mol-1) and composition (wPC 0.35). This polymer electrolyte binder shows impressive oxidative stability (5.2 V), suitable ionic conductivity (2.2 × 10-4 S cm-1 at 60 °C), and compliant viscoelastic properties for fabrication into high-performance solid composite cathodes. This work presents an attractive route to optimising polymer binder properties using controlled polymerisation strategies combining cyclic monomer (CL, TMC) ring-opening polymerisation and epoxide/CO2 ring-opening copolymerisation. It should also prompt further examination of polycarbonate/ester-based materials with today's most relevant yet demanding high-voltage cathodes and sensitive sulfide-based solid electrolytes.

Quantitative analysis of steric effects on the regioselectivity of the Larock heteroannulation reaction.

Alkylphenylacetylene derivatives were synthesized and used as reactants in the Larock heteroannulation reaction to investigate the steric influence on regioselectivity. Large alkyl groups preferentially yielded 2-alkyl-3-phenylindole products, while smaller alkyl groups provided 3-alkyl-2-phenylindole as major products. The logarithm of regioisomeric product ratios exhibited good correlations with various steric parameters. Notably, the Charton values provided the best correlation when excluding the cyclopropyl group. In addition, the Boltzmann-weighted Sterimol parameter (wSterimol) was utilized to generate a good predictive model, indicating the B1 wSterimol as the significant regiochemical determining parameter with no obvious deviation for the cyclopropyl group. Relative atomic distances within the DFT-optimized transition state structures revealed good correlations with the logarithm of regioisomeric ratios. Furthermore, the cyclopropyl adsorption complex indicated electronic contribution, explaining the peculiar behavior of this substituent in the experimental observation.

Dissecting the Electronic Contribution to the Regioselectivity of the Larock Heteroannulation Reaction in the Oxidative Addition and Carbopalladation Steps.

Substituted 2-iodoaniline derivatives were prepared and utilized as reactants, along with asymmetric diarylacetylenes, to synthesize a series of 6-substituted-2,3-diarylindole derivatives via the Larock heteroannulation reaction. Electron-donating substituents on the 2-iodoaniline derivatives retarded the reaction, while electron-withdrawing substituents provided a complete conversion to the indole products. In addition, the electronic properties of the substituted 2-iodoaniline reactants displayed no influence toward regioselectivity. On the contrary, the electronic effect from unsymmetrical diarylacetylenes significantly influenced the regiochemical outcome of the reaction. Density functional theory calculations of the oxidative addition and carbopalladation steps revealed the electronic influences of the substituted 2-iodoaniline derivatives toward the overall rate of the reaction. In contrast, the electronic properties of the asymmetric diarylacetylene remained the critical product-determining factor of regioselectivity.