Recovery of isolated lithium through discharged state calendar ageing.

Rechargeable Li-metal batteries have the potential to more than double the specific energy of the state-of-the-art rechargeable Li-ion batteries, making Li-metal batteries a prime candidate for next-generation high-energy battery technology1-3. However, current Li-metal batteries suffer from fast cycle degradation compared with their Li-ion battery counterparts2,3, preventing their practical adoption. A main contributor to capacity degradation is the disconnection of Li from the electrochemical circuit, forming isolated Li4-8. Calendar ageing studies have shown that resting in the charged state promotes further reaction of active Li with the surrounding electrolyte9-12. Here we discover that calendar ageing in the discharged state improves capacity retention through isolated Li recovery, which is in contrast with the well-known phenomenon of capacity degradation observed during the charged state calendar ageing. Inactive capacity recovery is verified through observation of Coulombic efficiency greater than 100% on both Li||Cu half-cells and anode-free cells using a hybrid continuous-resting cycling protocol and with titration gas chromatography. An operando optical setup further confirms excess isolated Li reactivation as the predominant contributor to the increased capacity recovery. These insights into a previously unknown pathway for capacity recovery through discharged state resting emphasize the marked impact of cycling strategies on Li-metal battery performance.

Correlating chemistry and mass transport in sustainable iron production.

Steelmaking contributes 8% to the total CO2 emissions globally, primarily due to coal-based iron ore reduction. Clean hydrogen-based ironmaking has variable performance because the dominant gas-solid reduction mechanism is set by the defects and pores inside the mm- to nm-sized oxide particles that change significantly as the reaction progresses. While these governing dynamics are essential to establish continuous flow of iron and its ores through reactors, the direct link between agglomeration and chemistry is still contested due to missing measurements. In this work, we directly measure the connection between chemistry and agglomeration in the smallest iron oxides relevant to magnetite ores. Using synthesized spherical 10-nm magnetite particles reacting in H2, we resolve the formation and consumption of wüstite (Fe1-xO)-the step most commonly attributed to whiskering. Using X-ray diffraction, we resolve crystallographic anisotropy in the rate of the initial reaction. Complementary imaging demonstrated how the particles self-assemble, subsequently react, and grow into elongated "whisker" structures. Our insights into how morphologically uniform iron oxide particles react and agglomerate in H2 reduction enable future size-dependent models to effectively describe the multiscale aspects of iron ore reduction.

Ni Anchored to Hydrogen-Substituted Graphdiyne for Lithium Sulfide Cathodes in Lithium-Sulfur Batteries.

Lithium-sulfur (Li-S) batteries are promising candidates for next-generation energy storage systems due to their high theoretical energy density and the low cost of sulfur. However, slow conversion kinetics between the insulating S and lithium sulfide (Li2S) remains as a technical challenge. In this work, we report a catalyst featuring nickel (Ni) single atoms and clusters anchored to a porous hydrogen-substituted graphdiyne support (termed Ni@HGDY), which is incorporated in Li2S cathodes. The rapidly synthesized catalyst was found to enhance ionic and electronic conductivity, decrease the reaction overpotential, and promote more complete conversion between Li2S and sulfur. The addition of Ni@HGDY to commercial Li2S powder enabled a capacity of over 516 mAh gLi2S-1 at 1 C for over 125 cycles, whereas the control Li2S cathode managed to maintain just over 200 mAh gLi2S-1. These findings highlight the efficacy of Ni as a metal catalyst and demonstrate the promise of HGDY in energy storage devices.

In Situ Prelithiation by Direct Integration of Lithium Mesh into Battery Cells.

Silicon (Si)-based anodes are promising for next-generation lithium (Li)-ion batteries due to their high theoretical capacity (∼3600 mAh/g). However, they suffer quantities of capacity loss in the first cycle from initial solid electrolyte interphase (SEI) formation. Here, we present an in situ prelithiation method to directly integrate a Li metal mesh into the cell assembly. A series of Li meshes are designed as prelithiation reagents, which are applied to the Si anode in battery fabrication and spontaneously prelithiate Si with electrolyte addition. Various porosities of Li meshes tune prelithiation amounts to control the degree of prelithiation precisely. Besides, the patterned mesh design enhances the uniformity of prelithiation. With an optimized prelithiation amount, the in situ prelithiated Si-based full cell shows a constant >30% capacity improvement in 150 cycles. This work presents a facile prelithiation approach to improve battery performance.

Proximity Matters: Interfacial Solvation Dictates Solid Electrolyte Interphase Composition.

The composition of the solid electrolyte interphase (SEI) plays an important role in controlling Li-electrolyte reactions, but the underlying cause of SEI composition differences between electrolytes remains unclear. Many studies correlate SEI composition with the bulk solvation of Li ions in the electrolyte, but this correlation does not fully capture the interfacial phenomenon of SEI formation. Here, we provide a direct connection between SEI composition and Li-ion solvation by forming SEIs using polar substrates that modify interfacial solvation structures. We circumvent the deposition of Li metal by forming the SEI above Li+/Li redox potential. Using theory, we show that an increase in the probability density of anions near a polar substrate increases anion incorporation within the SEI, providing a direct correlation between interfacial solvation and SEI composition. Finally, we use this concept to form stable anion-rich SEIs, resulting in high performance lithium metal batteries.

Dissolution of the Solid Electrolyte Interphase and Its Effects on Lithium Metal Anode Cyclability.

At >95% Coulombic efficiencies, most of the capacity loss for Li metal anodes (LMAs) is through the formation and growth of the solid electrolyte interphase (SEI). However, the mechanism through which this happens remains unclear. One property of the SEI that directly affects its formation and growth is the SEI's solubility in the electrolyte. Here, we systematically quantify and compare the solubility of SEIs derived from ether-based electrolytes optimized for LMAs using in-operando electrochemical quartz crystal microbalance (EQCM). A correlation among solubility, passivity, and cyclability established in this work reveals that SEI dissolution is a major contributor to the differences in passivity and electrochemical performance among battery electrolytes. Together with our EQCM, X-ray photoelectron spectroscopy (XPS), and nuclear magnetic resonance (NMR) spectroscopy results, we show that solubility depends on not only the SEI's composition but also the properties of the electrolyte. This provides a crucial piece of information that could help minimize capacity loss due to SEI formation and growth during battery cycling and aging.

Resolving Current-Dependent Regimes of Electroplating Mechanisms for Fast Charging Lithium Metal Anodes.

Poor fast-charge capabilities limit the usage of rechargeable Li metal anodes. Understanding the connection between charging rate, electroplating mechanism, and Li morphology could enable fast-charging solutions. Here, we develop a combined electroanalytical and nanoscale characterization approach to resolve the current-dependent regimes of Li plating mechanisms and morphology. Measurement of Li+ transport through the solid electrolyte interphase (SEI) shows that low currents induce plating at buried Li||SEI interfaces, but high currents initiate SEI-breakdown and plating at fresh Li||electrolyte interfaces. The latter pathway can induce uniform growth of {110}-faceted Li at extremely high currents, suggesting ion-transport limitations alone are insufficient to predict Li morphology. At battery relevant fast-charging rates, SEI-breakdown above a critical current density produces detrimental morphology and poor cyclability. Thus, prevention of both SEI-breakdown and slow ion-transport in the electrolyte is essential. This mechanistic insight can inform further electrolyte engineering and customization of fast-charging protocols for Li metal batteries.

Correlating Kinetics to Cyclability Reveals Thermodynamic Origin of Lithium Anode Morphology in Liquid Electrolytes.

The rechargeability of lithium metal batteries strongly depends on the electrolyte. The uniformity of the electroplated Li anode morphology underlies this dependence, so understanding the main drivers of uniform plating is critical for further electrolyte discovery. Here, we correlate electroplating kinetics with cyclability across several classes of electrolytes to reveal the mechanistic influence electrolytes have on morphology. Fast charge-transfer kinetics at fresh Li-electrolyte interfaces correlate well with uniform morphology and cyclability, whereas the resistance of Li+ transport through the solid electrolyte interphase (SEI) weakly correlates with cyclability. These trends contrast with the conventional thought that Li+ transport through the electrolyte or SEI is the main driver of morphological differences between classes of electrolytes. Relating these trends to Li+ solvation, Li nucleation, and the charge-transfer mechanism instead suggests that the Li/Li+ equilibrium potential and the surface energy─thermodynamic factors modulated by the strength of Li+ solvation─underlie electrolyte-dependent trends of Li morphology. Overall, this work provides an insight for discovering functional electrolytes, tuning kinetics in batteries, and explaining why weakly solvating fluorinated electrolytes favor uniform Li plating.

Potentiometric Measurement to Probe Solvation Energy and Its Correlation to Lithium Battery Cyclability.

The electrolyte plays a critical role in lithium-ion batteries, as it impacts almost every facet of a battery's performance. However, our understanding of the electrolyte, especially solvation of Li+, lags behind its significance. In this work, we introduce a potentiometric technique to probe the relative solvation energy of Li+ in battery electrolytes. By measuring open circuit potential in a cell with symmetric electrodes and asymmetric electrolytes, we quantitatively characterize the effects of concentration, anions, and solvents on solvation energy across varied electrolytes. Using the technique, we establish a correlation between cell potential (Ecell) and cyclability of high-performance electrolytes for lithium metal anodes, where we find that solvents with more negative cell potentials and positive solvation energies-those weakly binding to Li+-lead to improved cycling stability. Cryogenic electron microscopy reveals that weaker solvation leads to an anion-derived solid-electrolyte interphase that stabilizes cycling. Using the potentiometric measurement for characterizing electrolytes, we establish a correlation that can guide the engineering of effective electrolytes for the lithium metal anode.

Incorporating the Nanoscale Encapsulation Concept from Liquid Electrolytes into Solid-State Lithium-Sulfur Batteries.

Solid-state Li-S batteries are attractive due to their high energy density and safety. However, it is unclear whether the concepts from liquid electrolytes are applicable in the solid state to improve battery performance. Here, we demonstrate that the nanoscale encapsulation concept based on Li2S@TiS2 core-shell particles, originally developed in liquid electrolytes, is effective in solid polymer electrolytes. Using in situ optical cell and sulfur K-edge X-ray absorption, we find that polysulfides form and are well-trapped inside individual particles by the nanoscale TiS2 encapsulation. This TiS2 encapsulation layer also functions to catalyze the oxidation reaction of Li2S to sulfur, even in solid-state electrolytes, proven by both experiments and density functional theory calculations. A high cell-level specific energy of 427 W·h·kg-1 is achieved by integrating the Li2S@TiS2 cathode with a poly(ethylene oxide)-based electrolyte and a lithium metal anode. This study points to the fruitful direction of borrowing concepts from liquid electrolytes into solid-state batteries.

Two-dimensional gallium nitride realized via graphene encapsulation.

The spectrum of two-dimensional (2D) and layered materials 'beyond graphene' offers a remarkable platform to study new phenomena in condensed matter physics. Among these materials, layered hexagonal boron nitride (hBN), with its wide bandgap energy (∼5.0-6.0 eV), has clearly established that 2D nitrides are key to advancing 2D devices. A gap, however, remains between the theoretical prediction of 2D nitrides 'beyond hBN' and experimental realization of such structures. Here we demonstrate the synthesis of 2D gallium nitride (GaN) via a migration-enhanced encapsulated growth (MEEG) technique utilizing epitaxial graphene. We theoretically predict and experimentally validate that the atomic structure of 2D GaN grown via MEEG is notably different from reported theory. Moreover, we establish that graphene plays a critical role in stabilizing the direct-bandgap (nearly 5.0 eV), 2D buckled structure. Our results provide a foundation for discovery and stabilization of 2D nitrides that are difficult to prepare via traditional synthesis.

LiH formation and its impact on Li batteries revealed by cryogenic electron microscopy.

Little is known about how evolved hydrogen affects the cycling of Li batteries. Hypotheses include the formation of LiH in the solid-electrolyte interphase (SEI) and dendritic growth of LiH. Here, we discover that LiH formation in Li batteries likely follows a different pathway: Hydrogen evolved during cycling reacts to nucleate and grow LiH within already deposited Li metal, consuming active Li. We provide the evidence that LiH formed in Li batteries electrically isolates active Li from the current collector that degrades battery capacity. We detect the coexistence of Li metal and LiH also on graphite and silicon anodes, showing that LiH forms in most Li battery anode chemistries. Last, we find that LiH has its own SEI layer that is chemically and structurally distinct from the SEI on Li metal. Our results highlight the formation mechanism and chemical origins of LiH, providing critical insight into how to prevent its formation.

Hydrogen-substituted graphdiyne-assisted ultrafast sparking synthesis of metastable nanomaterials.

Metastable nanomaterials, such as single-atom and high-entropy systems, with exciting physical and chemical properties are increasingly important for next-generation technologies. Here, we developed a hydrogen-substituted graphdiyne-assisted ultrafast sparking synthesis (GAUSS) platform for the preparation of metastable nanomaterials. The GAUSS platform can reach an ultra-high reaction temperature of 3,286 K within 8 ms, a rate exceeding 105 K s-1. Controlling the composition and chemistry of the hydrogen-substituted graphdiyne aerogel framework, the reaction temperature can be tuned from 1,640 K to 3,286 K. We demonstrate the versatility of the GAUSS platform with the successful synthesis of single atoms, high-entropy alloys and high-entropy oxides. Electrochemical measurements and density functional theory show that single atoms synthesized by GAUSS enhance the lithium-sulfur redox reaction kinetics in all-solid-state lithium-sulfur batteries. Our design of the GAUSS platform offers a powerful way to synthesize a variety of metastable nanomaterials.

Onboard early detection and mitigation of lithium plating in fast-charging batteries.

Fast-charging is considered as one of the most desired features needed for lithium-ion batteries to accelerate the mainstream adoption of electric vehicles. However, current battery charging protocols mainly consist of conservative rate steps to avoid potential hazardous lithium plating and its associated parasitic reactions. A highly sensitive onboard detection method could enable battery fast-charging without reaching the lithium plating regime. Here, we demonstrate a novel differential pressure sensing method to precisely detect the lithium plating event. By measuring the real-time change of cell pressure per unit of charge (dP/dQ) and comparing it with the threshold defined by the maximum of dP/dQ during lithium-ion intercalation into the negative electrode, the onset of lithium plating before its extensive growth can be detected with high precision. In addition, we show that by integrating this differential pressure sensing into the battery management system (BMS), a dynamic self-regulated charging protocol can be realized to effectively extinguish the lithium plating triggered by low temperature (0 °C) while the conventional static charging protocol leads to catastrophic lithium plating at the same condition. We propose that differential pressure sensing could serve as an early nondestructive diagnosis method to guide the development of fast-charging battery technologies.

Electrochemical generation of liquid and solid sulfur on two-dimensional layered materials with distinct areal capacities.

It has recently been shown that sulfur, a solid material in its elementary form S8, can stay in a supercooled state as liquid sulfur in an electrochemical cell. We establish that this newly discovered state could have implications for lithium-sulfur batteries. Here, through in situ studies of electrochemical sulfur generation, we show that liquid (supercooled) and solid elementary sulfur possess very different areal capacities over the same charging period. To control the physical state of sulfur, we studied its growth on two-dimensional layered materials. We found that on the basal plane, only liquid sulfur accumulates; by contrast, at the edge sites, liquid sulfur accumulates if the thickness of the two-dimensional material is small, whereas solid sulfur nucleates if the thickness is large (tens of nanometres). Correlating the sulfur states with their respective areal capacities, as well as controlling the growth of sulfur on two-dimensional materials, could provide insights for the design of future lithium-sulfur batteries.

Growth and Tunable Surface Wettability of Vertical MoS2 Layers for Improved Hydrogen Evolution Reactions.

Layered materials, especially the transition metal dichalcogenides (TMDs), are of interest for a broad range of applications. Among the class of TMDs, molybdenum disulfide (MoS2) is perhaps the most studied because of its natural abundance and use in optoelectronics, energy storage and energy conversion applications. Understanding the fundamental structure-property relations is key for tailoring the enhancement in the above-mentioned applications. Here, we report a controlled powder vaporization synthesis of MoS2 flower-like structures consisting of vertically grown layers of MoS2 exhibiting exposed edges. This growth is readily achievable on multiple substrates, such as graphite, silicon, and silicon dioxide. The resulting MoS2 flowers are highly crystalline and stoichiometric. Further observations using contact angle indicate that MoS2 flowers exhibit the highest reported contact angle of ∼160 ± 10°, making the material super hydrophobic. This surface wettability was further tuned by changing the edge chemistry of the MoS2 flowers using an ozone etching treatment. Hydrogen evolution reaction (HER) measurements indicate that the surface treated with UV-ozone showed a reduction in the Tafel slope from 185 to 54 mV/dec, suggesting an increase in the amount of reactive surface to generate hydrogen.