RESUMO
Many problems of potassium-ion batteries (PIBs) are hidden under a low mass load of the active material. However, developing research based on areal capacity is challenging for PIBs, due to the lack of an anode capable of delivering a stable capacity of more than 1 mAh cm-2. This work investigates the K+ storage behavior of highly graphitized carbon fibers (HG-CF), which exhibit automatic structural adjustments to mitigate voltage polarization. The created defects and residual K+ in the structure favor the reversible insertion/deinsertion of K+. HG-GF after structural adjustment realizes a capacity of 2 mAh (1.13 cm-2) without K deposition and a stable cyclic stability (>500 h). In situ X-ray diffraction and in situ Raman spectra were used to detect defect formation and structural evolution during cycles. This work demonstrates the feasibility of HG-GF as an anode for PIBs and provides a suitable anode for further research of PIBs based on areal capacity.
RESUMO
Graphite is the most commonly used anode material for not only commercialized lithium-ion batteries (LIBs) but also the emerging potassium-ion batteries (PIBs). However, the graphite anode in PIBs using traditional dilute ester-based electrolyte systems shows obvious capacity fading, which is in contrast with the extraordinary cyclic stability in LIBs. More interestingly, the graphite in concentrated electrolytes for PIBs exhibits outstanding cyclic stability. Unfortunately, this significant difference in cycling performance has not raised concern up to now. In this work, by comparing the cyclic stability and graphitization degree of the graphite anode upon cycling, we reveal that the underlying mechanism of the capacity fading of the graphite anode in PIBs is not the larger volume expansion of graphite caused by the intercalation of potassium ions but the continual accumulation of the solid electrolyte interphase (SEI) on the surface of graphite. By X-ray photoelectron and nuclear magnetic resonance spectroscopies combined with chemical synthesis, it is concluded that the accumulation of the SEI may mainly come from the continual deposition of a kind of oligomer component, which blocks intercalation and deintercalation of potassium ions in graphite anodes. The designed SEI-cleaning experiment further verifies the above conclusion. This finding clarifies the crucial factor determining the cyclic stability of graphite and provides scientific guidance for application of the graphite anode for PIBs.
RESUMO
Prussian blue (PB) is a very promising cathode for K-ion batteries but its low electronic conductivity and deficiencies in the framework aggravate electrochemical performances. Compositing with conductive reduced graphene oxide (rGO) is an effective solution to address this problem. Nevertheless, little attention was paid to the loss of oxygen-containing functional groups on the rGO substrate during the compositing process, which weakens the interaction between PB and rGO and leads to poor electrochemical performance of PB/rGO. Herein, this interaction effect associated with surface functional groups is first openly debated. Two commonly used carbon substrates, graphene oxide (GO) and rGO, are investigated. A more stable interaction between PB and GO contributes to a higher capacity retention (91.8%) than that of PB/rGO (69.7%) after 300 cycles at a current density of 5 C. Meanwhile, polyvinylpyrrolidone (PVP) is employed to repair the weak interaction between PB and rGO substrates. PB is anchored to the rGO surface through the stable covalent linking of amide groups in PVP. A superior rate capability of 72 mA h g-1 at 10 C and an improved capacity retention of 96.5% over 800 cycles at 5 C are obtained by as-prepared PB/PVP-rGO. This study provides a deeper understanding of fabricating PB/carbon composites with a robust connection.
