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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.

Nowadays, alkali metal-oxygen batteries such as Li-, Na-, and K-O 2 batteries have been investigated extensively because of their ultrahigh energy density. However, the oxygen crossover of oxygen batteries and the intrinsic drawbacks of the metal anodes (i.e., large volume changes and dendrite issues) have still been unsolved key problems. Here, we demonstrate a novel design of the K-ion oxygen battery using a graphite intercalation composite as the anode in a highly concentrated ether-based electrolyte. Instead of the metal K anode, the potassium graphite intercalation compound as the anode is depotassiated/potassiated in a binary form below 0.3 V (vs. K + /K); correspondingly, the discharged product KO 2 is formed/decomposed at the carbon nanotube cathode, and an all-carbon full cell exhibits impressive cycling stability with a working voltage of 2.0 V. Furthermore, the utilization of graphite intercalation chemistry has been demonstrated to be applicable in Li-O 2 batteries as well. Therefore, this study may provide a new strategy to resolve the key problems of the alkali metal-oxygen batteries.

Potassium-ion batteries (PIBs) are considered to be potential alternatives to the conventional lithium-ion batteries (LIBs) due to the similar working mechanism and abundant potassium (K) resource. However, it still remains challenging to directly apply commercial graphite anodes for PIBs owing to the large K ions, which may impede the electrochemical intercalation of K ions into the graphite interlayer and result in a poor cyclic stability and rate capability. Reduced graphene oxide (rGO) has shown remarkable electrochemical performance as an anode material for PIBs due to the fact that rGO possesses more active sites with an enlarged interlayer distance. Understanding the microstructure of rGO is crucial for optimizing its K-ion storage capabilities. Herein, it is revealed that the K-ion storage behavior of rGO is strongly dependent on the thermal treatment temperature on account of the difference in microstructure. rGO graphitized at 2500 °C exhibits a superior long-term cyclic stability for 2500 cycles due to the expanded interlayer distance and the unique graphite-like structure in a long range, enabling it to endure the huge volume change during uninterrupted K-ion intercalation/deintercalation processes.

Understanding the electrochemical property of superoxides in alkali metal oxygen batteries is critical for the design of a stable oxygen battery with high capacity and long cycle performance. In this work, a KO 2 -decorated binder-free cathode is fabricated by a simple and efficient electrochemical strategy. KO 2 nanoparticles are uniformly coated on the carbon nanotube film (CNT-f) through a controllable discharge process in the K-O 2 battery, and the KO 2 -decorated CNT-f is innovatively introduced into the Li-O 2 battery as the O 2 diffusion electrode. The Li-O 2 battery based on the KO 2 -decorated CNT-f cathode can deliver enhanced discharge capacity, reduced charge overpotential, and more stable cycle performance compared with the battery in the absence of KO 2 . In situ formed KO 2 particles on the surface of CNT-f cathode assist to form Li 2 O 2 nanosheets in the Li-O 2 battery, which contributes to the improvement of discharge capacity and cycle life. Interestingly, the analysis of KO 2 -decorated CNT-f cathodes, after discharge and cycle tests, reveals that the electrochemically synthesized KO 2 seems not a conventional electrocatalyst but a partially dissolvable and decomposable promoter in Li-O 2 batteries.

The formation of the insulated film-like discharge products (Li 2 O 2 ) on the surface of the carbon cathode gradually hinders the oxygen reduction reaction (ORR) process, which usually leads to the premature death of the Li-O 2 battery. In this work, by introducing the molecular sieve powder into the ether electrolyte, the Li-O 2 battery exhibits a largely improved discharge capacity (63 times) compared with the one in the absence of this inorganic oxide additive. Meanwhile, XRD and SEM results qualitatively demonstrate the generation of the toroid Li 2 O 2 as the dominated discharge products, and the chemical titration quantifies a higher yield of the Li 2 O 2 with the presence of the molecular sieve additive. The addition of the molecular sieve controls the amount of the free water in the electrolyte, which distinguishes the effect of the molecular sieve and the free water on the discharge process. Hence, a possible mechanism has been proposed that the adsorption of the molecular sieves toward the soluble lithium superoxides improves the disproportionation of the lithium superoxides and consequently enhances the solution-growth of the lithium peroxides in the low donor number ether electrolyte. In general, the application of the molecular sieve triggers further studies concerning the improvement of the discharge performance in the Li-O 2 battery by adding the inorganic additives.

Amorphous silicon thin films having various thicknesses were investigated as a negative electrode material for lithium-ion batteries. Electrochemical characterization of the 20 nm thick thin silicon film revealed a very low first cycle Coulombic efficiency, which can be attributed to the silicon oxide layer formed on both the surface of the as-deposited Si thin film and the interface between the Si and the substrate. Among the investigated films, the 100 nm Si thin film demonstrated the best performance in terms of first cycle efficiency and cycle life. Observations from scanning electron microscopy demonstrated that the generation of cracks was inevitable in the cycled Si thin films, even as the thickness of the film was as little as 20 nm, which was not predicted by previous modeling work. However, the cycling performance of the 20 and 100 nm silicon thin films was not detrimentally affected by these cracks. The poor capacity retention of the 1 μm silicon thin film was attributed to the delamination.

The safety issue caused by the dendrite growth is not only a key research problem in lithium-ion batteries but also a critical concern in alkali metal (i.e., Li, Na, and K)-oxygen batteries where a solid metal is usually used as the anode. Herein, we demonstrate the first dendrite-free K-O 2 battery at ambient temperature based on a liquid Na-K alloy anode. The unique liquid-liquid connection between the liquid alloy and the electrolyte in our alloy anode-based battery provides a homogeneous and robust anode-electrolyte interface. Meanwhile, we manage to show that the Na-K alloy is only compatible in K-O 2 batteries but not in Na-O 2 batteries, which is mainly attributed to the stronger reducibility of potassium and relatively more favorable thermodynamic formation of KO 2 over NaO 2 during the discharge process. It is observed that our K-O 2 battery based on a liquid alloy anode shows a long cycle life (over 620 h) and a low discharge-charge overpotential (about 0.05 V at initial cycles). Moreover, the mechanism investigation into the K-O 2 cell degradation shows that the O 2 crossover effect and the ether-electrolyte instability are the critical problems for K-O 2 batteries. In a word, this study provides a new route to solve the problems caused by the dendrite growth in alkali metal-oxygen batteries.