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Whereas standard transmission electron microscopy studies are unable to preserve the native state of chemically reactive and beam-sensitive battery materials after operation, such materials remain pristine at cryogenic conditions. It is then possible to atomically resolve individual lithium metal atoms and their interface with the solid electrolyte interphase (SEI). We observe that dendrites in carbonate-based electrolytes grow along the <111> (preferred), <110>, or <211> directions as faceted, single-crystalline nanowires. These growth directions can change at kinks with no observable crystallographic defect. Furthermore, we reveal distinct SEI nanostructures formed in different electrolytes.

Metallic lithium is a promising anode candidate for future high-energy-density lithium batteries. It is a light-weight material, and has the highest theoretical capacity (3,860 mAh g(-1)) and the lowest electrochemical potential of all candidates. There are, however, at least three major hurdles before lithium metal anodes can become a viable technology: uneven and dendritic lithium deposition, unstable solid electrolyte interphase and almost infinite relative dimension change during cycling. Previous research has tackled the first two issues, but the last is still mostly unsolved. Here we report a composite lithium metal anode that exhibits low dimension variation (∼20%) during cycling and good mechanical flexibility. The anode is composed of 7 wt% 'lithiophilic' layered reduced graphene oxide with nanoscale gaps that can host metallic lithium. The anode retains up to ∼3,390 mAh g(-1) of capacity, exhibits low overpotential (∼80 mV at 3 mA cm(-2)) and a flat voltage profile in a carbonate electrolyte. A full-cell battery with a LiCoO2 cathode shows good rate capability and flat voltage profiles.

Lithium metal has shown great promise as an anode material for high-energy storage systems, owing to its high theoretical specific capacity and low negative electrochemical potential. Unfortunately, uncontrolled dendritic and mossy lithium growth, as well as electrolyte decomposition inherent in lithium metal-based batteries, cause safety issues and low Coulombic efficiency. Here we demonstrate that the growth of lithium dendrites can be suppressed by exploiting the reaction between lithium and lithium polysulfide, which has long been considered as a critical flaw in lithium-sulfur batteries. We show that a stable and uniform solid electrolyte interphase layer is formed due to a synergetic effect of both lithium polysulfide and lithium nitrate as additives in ether-based electrolyte, preventing dendrite growth and minimizing electrolyte decomposition. Our findings allow for re-evaluation of the reactions regarding lithium polysulfide, lithium nitrate and lithium metal, and provide insights into solving the problems associated with lithium metal anodes.

The ability to intercalate guest species into the van der Waals gap of 2D layered materials affords the opportunity to engineer the electronic structures for a variety of applications. Here we demonstrate the continuous tuning of layer vertically aligned MoS 2 nanofilms through electrochemical intercalation of Li + ions. By scanning the Li intercalation potential from high to low, we have gained control of multiple important material properties in a continuous manner, including tuning the oxidation state of Mo, the transition of semiconducting 2H to metallic 1T phase, and expanding the van der Waals gap until exfoliation. Using such nanofilms after different degree of Li intercalation, we show the significant improvement of the hydrogen evolution reaction activity. A strong correlation between such tunable material properties and hydrogen evolution reaction activity is established. This work provides an intriguing and effective approach on tuning electronic structures for optimizing the catalytic activity.2D materials | layer vertically standing | electrochemical catalysis L ayer-structured 2D materials are an interesting family of materials with strong covalent bonding within molecular layers and weak van der Waals interaction between layers. Beyond intensively studied graphene-related materials (1-4), there has been recent strong interest in other layered materials whose vertical thickness can be thinned down to less than few nanometers and horizontal width can also be reduced to nanoscale (5-9). The strong interest is driven by their interesting physical and chemical properties (2, 10) and their potential applications in transistors, batteries, topological insulators, thermoelectrics, artificial photosynthesis, and catalysis (4,(11)(12)(13)(14)(15)(16)(17)(18)(19)(20)(21)(22)(23)(24)(25).One of the unique properties of 2D layered materials is their ability to intercalate guest species into their van der Waals gaps, opening up the opportunities to tune the properties of materials. For example, the spacing between the 2D layers could be increased by intercalation such as lithium (Li) intercalated graphite or molybdenum disulfide (MoS 2 ) and copper intercalated bismuth selenide (26-29). The electronic structures of the host lattice, such as the charge density, anisotropic transport, oxidation state, and phase transition, may also be changed by different species intercalation (26,27).As one of the most interesting layered materials, MoS 2 has been extensively studied in a variety of areas such as electrocatalysis (20)(21)(22)(30)(31)(32)(33)(34)(35)(36). It is known that there is a strong correlation between the electronic structure and catalytic activity of the catalysts (20,(37)(38)(39)(40)(41). It is intriguing to continuously tune the morphology and electronic structure of MoS 2 and explore the effects on MoS 2 hydrogen evolution reaction (HER) activity. Very recent studies demonstrated that the monolayered MoS 2 and WS 2 nanosheets with 1T metallic phase synthesized by chemical exfoliation exhibited superio...

For future applications in portable electronics, electric vehicles and grid storage, batteries with higher energy storage density than existing lithium ion batteries need to be developed. Recent efforts in this direction have focused on high-capacity electrode materials such as lithium metal, silicon and tin as anodes, and sulphur and oxygen as cathodes. Lithium metal would be the optimal choice as an anode material, because it has the highest specific capacity (3,860 mAh g(-1)) and the lowest anode potential of all. However, the lithium anode forms dendritic and mossy metal deposits, leading to serious safety concerns and low Coulombic efficiency during charge/discharge cycles. Although advanced characterization techniques have helped shed light on the lithium growth process, effective strategies to improve lithium metal anode cycling remain elusive. Here, we show that coating the lithium metal anode with a monolayer of interconnected amorphous hollow carbon nanospheres helps isolate the lithium metal depositions and facilitates the formation of a stable solid electrolyte interphase. We show that lithium dendrites do not form up to a practical current density of 1 mA cm(-2). The Coulombic efficiency improves to ∼ 99% for more than 150 cycles. This is significantly better than the bare unmodified samples, which usually show rapid Coulombic efficiency decay in fewer than 100 cycles. Our results indicate that nanoscale interfacial engineering could be a promising strategy to tackle the intrinsic problems of lithium metal anodes.

We present the results of a thorough study of wet chemical methods for transferring chemical vapor deposition grown graphene from the metal growth substrate to a device-compatible substrate. On the basis of these results, we have developed a "modified RCA clean" transfer method that has much better control of both contamination and crack formation and does not degrade the quality of the transferred graphene. Using this transfer method, high device yields, up to 97%, with a narrow device performance metrics distribution were achieved. This demonstration addresses an important step toward large-scale graphene-based electronic device applications.

Two-dimensional (2D) layered materials exhibit high anisotropy in materials properties due to the large difference of intra- and interlayer bonding. This presents opportunities to engineer materials whose properties strongly depend on the orientation of the layers relative to the substrate. Here, using a similar growth process reported in our previous study of MoS2 and MoSe2 films whose layers were oriented vertically on flat substrates, we demonstrate that the vertical layer orientation can be realized on curved and rough surfaces such as nanowires (NWs) and microfibers. Such structures can increase the surface area while maintaining the perpendicular orientation of the layers, which may be useful in enhancing various catalytic activities. We show vertically aligned MoSe2 and WSe2 nanofilms on Si NWs and carbon fiber paper. We find that MoSe2 and WSe2 nanofilms on carbon fiber paper are highly efficient electrocatalysts for hydrogen evolution reaction (HER) compared to flat substrates. Both materials exhibit extremely high stability in acidic solution as the HER catalytic activity shows no degradation after 15 000 continuous potential cycles. The HER activity of MoSe2 is further improved by Ni doping.