Lithium-sulfur (Li-S) batteries are expected to overcome the limit of current energy storage devices by delivering high specific energy with low material cost. However, the potential of Li-S batteries has not yet been realized because of several technical barriers. Poor electrochemical performance is mainly attributed to the low electrical conductivity of the fully charged and discharged species, the irreversible loss of polysulfide anions and the decrease in the number of electrochemically active reaction sites during battery operation. Here, we report that the introduction of graphene quantum dots (GQDs) into the sulfur cathode dramatically enhanced sulfur/sulfide utilization, yielding high performance. In addition, the GQDs induced structural integrity of the sulfur-carbon electrode composite by oxygen-rich functional groups. This hierarchical architecture enabled fast charge transfer while minimizing the loss of lithium polysulfides, which is attributed to the physicochemical properties of GQDs. The mechanisms through which excellent cycling and rate performance are achieved were thoroughly studied by analyzing capacity versus voltage profiles. Furthermore, experimental observations and theoretical calculations further clarified the role played by GQDs by proving that C-S bonding occurs. Thus, the introduction of GQDs into Li-S batteries will provide an important breakthrough allowing their use as high-performance and low-cost batteries for next-generation energy storage systems. INTRODUCTIONRechargeable lithium-ion batteries are widely used in various applications, such as portable devices, bio-medical implants and electric vehicles, because of their high energy and power density. 1,2 However, current lithium-ion batteries based on the graphite and transition metal oxide couple have nearly reached their ceiling with respect to storage capability because of the limitations associated with their electrical properties and crystal structure. Therefore, breakthroughs in new energy storage systems that can surpass the current performance barrier of lithium-ion batteries should be brought about in a timely manner. Recently, Li-S batteries that can operate by the reversible electrochemical transformation between sulfur (S 8 ) and dilithium sulfide (Li 2 S) have attracted great attention because they can deliver high energy with a moderate voltage owing to the direct use of

It is unmistakably paradoxical that the weakest point of the photoactive organic-inorganic hybrid perovskite is its instability against light. Why and how perovskites break down under light irradiation and what happens at the atomistic level of these materials during the degradation process still remains unanswered. In this paper, we revealed the fundamental origin and mechanism for irreversible degradation of hybrid perovskite materials from our new experimental results and ab initio molecular dynamics (AIMD) simulations. We found that the charges generated by light irradiation and trapped along the grain boundaries of the perovskite crystal result in oxygen-induced irreversible degradation in air even in the absence of moisture. The present result, together with our previous experimental finding on the same critical role of trapped charges in the perovskite degradation under moisture, suggests that the trapped charges are the main culprit in both the oxygen-and moisture-induced degradation of perovskite materials. More detailed roles of oxygen and water molecules were investigated by tracking the atomic motions of the oxygen-or water-covered methylammonium lead triiodide (MAPbI3 for CH3NH3PbI3) perovskite crystal surface with trapped charges via AIMD simulation. In the first few picoseconds of our simulation, trapped charges start disrupting the crystal structure, leading to a close-range interaction between oxygen or water molecules and the compositional ions of MAPbI3. We found that there are different degradation pathways depending both on the polarity of the trapped charge and on the kind of gas molecule. Especially, the deprotonation of organic cations was theoretically predicted for the first time in the presence of trapped anionic charges and water molecules. Additionally, we confirmed that a more structurally stable, multi-component perovskite material (with the composition of MA0.6FA0.4PbI2.9Br0.1) exhibited a much longer lifespan than MAPbI3 under light irradiation even in 100% oxygen ambience or humid air.

The breakdown process of CH3NH3PbI3 perovskite crystals by localized charges and its polarity-dependency have been revealed.

Excited state dynamics of common yellow dye quinophthalone (QPH) was probed by femtosecond transient absorption spectroscopy. Multi-exponential decay of the excited state and significant change of rate constants upon deuterium substitution indicate that uncommon nitrogen-to-oxygen excited state intramolecular proton transfer (ESIPT) occurs. By performing density functional theory (DFT) and time-dependent density functional theory (TDDFT) calculations, we found that adiabatic surface crossing between the S1 and S2 states takes place in the photoreaction. Unlike most cases of ESIPT, QPH does not exhibit tautomer emission, possibly due to internal conversion or back-proton transfer. The ESIPT of QPH presents a highly interesting case also because the moieties participating in ESIPT, quinoline and aromatic carbonyl, are both traditionally considered as photobases.