RESUMO
Organic electrodes are promising candidates for next-generation lithium-ion batteries due to their low cost and sustainable nature; however, they often suffer from very low conductivity and active material loadings. The conventional binder used in organic-based Li-ion batteries is poly(vinylidene fluoride) (PVDF), yet it is electrochemically inactive and thus occupies volume and mass without storing energy. Here, we report an organic mixed ionic-electronic conducting polymer, poly[norbornene-1,2-bis(C(O)OPEDOT)]25-b-[norbornene-1,2-bis-(C(O)PEG12)]25 denoted PEDOT-b-PEG for simplicity, as a cathode binder to address the aforementioned issues. The polymer contains a poly(3,4-ethylenedioxythiophene) (PEDOT) functionality to provide electronic conductivity, as well as poly(ethylene glycol) (PEG) chains to impart ionic conductivity to the cathode composite. We compare electrodes containing a perylene diimide (PDI) active material, conductive carbon, and a polymeric binder (either PVDF or PEDOT-b-PEG) with different weight ratios to study the impact of active material loading and type of binder on the performance of the cell. The lithium-ion cells prepared with the PEDOT-b-PEG polymer binder result in higher capacities and decreased impedance at all active material loadings compared to cathodes prepared with the PVDF-containing electrodes, demonstrating potential as a new binder to achieve higher active material loadings in organic electrodes. The strategy of preparing these polymers should be broadly applicable to other classes of mixed polymer conductors.
RESUMO
Thionated naphthalene diimides (NDIs) are promising materials for n-type organic semiconductors; despite their potential, synthetic routes to thionated NDIs are generally lengthy, nonselective, and low yielding and their polymeric analogues have yet to be reported in the literature. Here, we describe the rapid and selective thionation of thiophene- and selenophene-flanked NDIs using microwave irradiation and excess Lawesson's reagent. Remarkably, >99% conversion to the trans-dithionated product is observed by NMR within 45 min. Steric effects imparted by NDI core substituents prevent excess thionation, simplifying purification procedures. We apply this methodology to the postpolymerization thionation of NDI-based polymers to afford a series of polymers with varying degrees of thionation. Thionated NDIs exhibit bathochromic shifts of up to â¼100 nm in localized absorption maxima and increased electron affinities.