RESUMO
In this research, we aim to investigate a flexible composite lithium-ion-conducting membrane (FC-LICM) consisting of poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP) and titanium dioxide (TiO2) nanoparticles with a TiO2-rich configuration. PVDF-HFP was selected as the host polymer owing to its chemically compatible nature with lithium metal. TiO2 (40-60 wt%) was incorporated into the polymer matrix, and the FC-LICM charge transfer resistance values (Rct) were reduced by two-thirds (from 1609 Ω to 420 Ω) at the 50 wt% TiO2 loading compared with the pristine PVDF-HFP. This improvement may be attributed to the electron transport properties enabled by the incorporation of semiconductive TiO2. After being immersed in an electrolyte, the FC-LICM also exhibited a Rct that was lower by 45% (from 141 to 76 Ω), suggesting enhanced ionic transfer upon the addition of TiO2. The TiO2 nanoparticles in the FC-LICM facilitated charge transfers for both electron transfer and ionic transport. The FC-LICM incorporated at an optimal load of 50 wt% TiO2 was assembled into a hybrid electrolyte Li-air battery (HELAB). This battery was operated for 70 h with a cut-off capacity of 500 mAh g-1 in a passive air-breathing mode under an atmosphere with high humidity. A 33% reduction in the overpotential of the HELAB was observed in comparison with using the bare polymer. The present work provides a simple FC-LICM approach for use in HELABs.
RESUMO
In this study, a dense polyvinylidene fluoride-hexafluoropropylene (PVDF-HFP) coating is fabricated on a lithium (Li) anode sheet, which acts as a synergistic protective layer and electrolyte separator for Li-oxygen (Li-O2) batteries. This thin coating is dried through slow solvent evaporation and vacuum drying methods. The solvent-free, dense PVDF-HFP coating has a thickness of 45 µm and can absorb 62% of electrolyte. The battery containing the PVDF-HFP coating demonstrates a maximum peak power density of 3 mW cm-2, significantly higher than that of the battery with the PVDF coating (0.8 mW cm-2) but lower than that without coating (equipped with a commercial glass fiber separator, 7.3 mW cm-2). However, the PVDF-HFP coating enables the Li-O2 battery to reach a capacity of 4400 mA h g-1, much higher than that without the coating (glass fiber separator, 850 mA h g-1). The symmetric Li-Li cells further confirm steady and low overpotentials using the anode coating at a high current density of 1.0 mA cm-2, indicating stable Li plating/stripping process. The PVDF-HFP-coated battery has a longer cycling lifetime (1700 h) than those with the PVDF coating (120 h) and a glass fiber separator (670 h). The Raman spectra show that there are lithium compounds (mainly lithium hydroxide) and residual PVDF-HFP on the aged anode surface. The dense PVDF-HFP coating on the Li anode plays dual roles: it creates a strong protective layer for stabilizing the solid-electrolyte interface (in the solid phase), and acts as a separator for modulating the Li metal deposition and stripping behaviors in liquid electrolyte.
RESUMO
A potent cathode catalyst of octahedral cobalt oxide (Co3O4) was synthesized onto graphene (GR) nanosheets via a two-step preparation method. The precursor cobalt solution reacted with GR during the initial hydrolysis step to form intermediates. A subsequent hydrothermal reaction promoted Co3O4 crystallinity with a crystalline size of 73 nm, resulting in octahedral particles of 100-300 nm in size. Scanning electron microscopy, Raman spectroscopy, and X-ray diffraction analysis confirmed the successful formation of the Co3O4/GR composite. This catalyst composite was sprayed onto a carbon cloth to form a cathode for the hybrid electrolyte lithium-air battery (HELAB). This catalyst demonstrated improved oxygen reduction and oxygen evolution capabilities. The HELAB containing this catalyst showed a higher discharge voltage and stable charge voltage, resulting in a 34% reduction in overall over-potential compared to that without the Co3O4/GR composite. The use of saturated LiOH in 11.6 M LiCl aqueous electrolyte at the cathode further reduced the over-potential by 0.5 V. It is proposed that the suppressed dissociation of LiOH expedites the charging reaction from un-dissociated LiOH. This Co3O4/GR composite is a promising bi-functional catalyst, suitable as a cathode material for a HELAB operating in high relative humidity and highly alkaline environment.