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Solid-state batteries with Li metal anodes can offer increased energy density compared to Li-ion batteries. However, the performance of pure Li anodes has been limited by morphological instabilities at the interface between Li and the solid-state electrolyte (SSE). Composites of Li metal with other materials such as carbon and Li alloys have exhibited improved cycling stability, but the mechanisms associated with this enhanced performance are not clear, especially at the low stack pressures needed for practical viability. Here, we investigate the structural evolution and correlated electrochemical behavior of Li metal composites containing reduced graphene oxide (rGO) and Li-Ag alloy particles. The nanoscale carbon scaffold maintains homogeneous contact with the SSE during stripping and facilitates Li transport to the interface; these effects largely prevent interfacial disconnection even at low stack pressure. The Li-Ag is needed to ensure cyclic refilling of the rGO scaffold with Li during plating, and the solid-solution character of Li-Ag improves cycling stability compared to other materials that form intermetallic compounds. Full cells with sulfur cathodes were tested at relatively low stack pressure, achieving 100 stable cycles with 79% capacity retention.
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Lithium alloy anodes in the form of dense foils offer significant potential advantages over lithium metal and particulate alloy anodes for solid-state batteries (SSBs). However, the reaction and degradation mechanisms of dense alloy anodes remain largely unexplored. Here, we investigate the electrochemical lithiation/delithiation behavior of 12 elemental alloy anodes in SSBs with Li6PS5Cl solid-state electrolyte (SSE), enabling direct behavioral comparisons. The materials show highly divergent first-cycle Coulombic efficiency, ranging from 99.3% for indium to â¼20% for antimony. Through microstructural imaging and electrochemical testing, we identify lithium trapping within the foil during delithiation as the principal reason for low Coulombic efficiency in most materials. The exceptional Coulombic efficiency of indium is found to be due to unique delithiation reaction front morphology evolution in which the high-diffusivity LiIn phase remains at the SSE interface. This study links composition to reaction behavior for alloy anodes and thus provides guidance toward better SSBs.
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Control over material structure and morphology during electrodeposition is necessary for material synthesis and energy applications. One approach to guide crystallite formation is to take advantage of epitaxy on a current collector to facilitate crystallographic control. Single-layer graphene on metal foils can promote "remote epitaxy" during Cu and Zn electrodeposition, resulting in growth of metal that is crystallographically aligned to the substrate beneath graphene. However, the substrate-graphene-deposit interactions that allow for epitaxial electrodeposition are not well understood. Here, we investigate how different graphene layer thicknesses (monolayer, bilayer, trilayer, and graphite) influence the electrodeposition of Zn and Cu. Scanning transmission electron microscopy and electron backscatter diffraction are leveraged to understand metal morphology and structure, demonstrating that remote epitaxy occurs on mono- and bilayer graphene but not trilayer or thicker. Density functional theory (DFT) simulations reveal the spatial electronic interactions through thin graphene that promote remote epitaxy. This work advances our understanding of electrochemical remote epitaxy and provides strategies for improving control over electrodeposition.
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Metal negative electrodes that alloy with lithium have high theoretical charge storage capacity and are ideal candidates for developing high-energy rechargeable batteries. However, such electrode materials show limited reversibility in Li-ion batteries with standard non-aqueous liquid electrolyte solutions. To circumvent this issue, here we report the use of non-pre-lithiated aluminum-foil-based negative electrodes with engineered microstructures in an all-solid-state Li-ion cell configuration. When a 30-µm-thick Al94.5In5.5 negative electrode is combined with a Li6PS5Cl solid-state electrolyte and a LiNi0.6Mn0.2Co0.2O2-based positive electrode, lab-scale cells deliver hundreds of stable cycles with practically relevant areal capacities at high current densities (6.5 mA cm-2). We also demonstrate that the multiphase Al-In microstructure enables improved rate behavior and enhanced reversibility due to the distributed LiIn network within the aluminum matrix. These results demonstrate the possibility of improved all-solid-state batteries via metallurgical design of negative electrodes while simplifying manufacturing processes.
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Electrolytes, consisting of salts, solvents, and additives, must form a stable solid electrolyte interphase (SEI) to ensure the performance and durability of lithium(Li)-ion batteries. However, the electric double layer (EDL) structure near charged surfaces is still unsolved, despite its importance in dictating the species being reduced for SEI formation near a negative electrode. In this work, a newly developed model was used to illustrate the effect of EDL on SEI formation in two essential electrolytes, the carbonate-based electrolyte for Li-ion batteries and the ether-based electrolyte for batteries with Li-metal anodes. Both electrolytes have fluoroethylene carbonate (FEC) as a common additive to form the beneficial F-containing SEI component (e.g., LiF). However, the role of FEC drastically differs in these electrolytes. FEC is an effective SEI modifier for the carbonate-based electrolyte by being the only F-containing species entering the EDL and being reduced, as the anion (PF6-) will not enter the EDL. For the ether-based electrolyte, both the anion (TFSI-) and FEC can enter the EDL and be reduced. The competition of the two species within the EDL due to the surface charge and temperature leads to a unique temperature effect observed in prior experiments: the FEC additive is more effective in modulating SEI components at a low temperature (-40 °C) than at room temperature (20 °C) in the ether-based electrolyte. These collective quantitative agreements with experiments emphasize the importance of incorporating the effect of the EDL in multicomponent electrolyte reduction reactions in simulations/experiments to predict/control the formation of the SEI layer.
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Nonaqueous sodium-based batteries are ideal candidates for the next generation of electrochemical energy storage devices. However, despite the promising performance at ambient temperature, their low-temperature (e.g., < 0 °C) operation is detrimentally affected by the increase in the electrolyte resistance and solid electrolyte interphase (SEI) instability. Here, to circumvent these issues, we propose specific electrolyte formulations comprising linear and cyclic ether-based solvents and sodium trifluoromethanesulfonate salt that are thermally stable down to -150 °C and enable the formation of a stable SEI at low temperatures. When tested in the Na||Na coin cell configuration, the low-temperature electrolytes enable long-term cycling down to -80 °C. Via ex situ physicochemical (e.g., X-ray photoelectron spectroscopy, cryogenic transmission electron microscopy and atomic force microscopy) electrode measurements and density functional theory calculations, we investigate the mechanisms responsible for efficient low-temperature electrochemical performance. We also report the assembly and testing between -20 °C and -60 °C of full Na||Na3V2(PO4)3 coin cells. The cell tested at -40 °C shows an initial discharge capacity of 68 mAh g-1 with a capacity retention of approximately 94% after 100 cycles at 22 mA g-1.
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Iron trifluoride (FeF3), a conversion-type cathode for sodium-ion batteries (SIBs), is based on cheap and abundant Fe and provides high theoretical capacity. However, the applications of FeF3-based SIBs have been hindered by their low-capacity utilization and poor cycling stability. Herein, we report greatly enhanced performance of FeF3 in multiple types of ionic liquid (IL) electrolytes at both room temperature (RT) and elevated temperatures. The Pyr1,4FSI electrolyte demonstrated the best cycling stability with an unprecedented decay rate of only â¼0.023% per cycle after the initial stabilization and an average coulombic efficiency of â¼99.5% for over 1000 cycles at RT. The Pyr1,3FSI electrolyte demonstrated the best cycling stability with a capacity decay rate of only â¼0.25% per cycle at 60 °C. Cells using Pyr1,3FSI and EMIMFSI electrolytes also showed promising cycling stability with capacity decay rates of â¼0.039% and â¼0.030% per cycle over 1000 cycles, respectively. A protective and ionically conductive cathode electrolyte interphase (CEI) layer is formed during cycling in ILs, diminishing side reactions that commonly lead to gassing and excessive CEI growth in organic electrolytes, especially at elevated temperatures. Furthermore, the increased ionic conductivity and decreased viscosity of ILs at elevated temperatures help attain higher accessible capacity. The application of ILs sheds light on designing a protective CEI for its use in stable SIBs.
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Solid-state batteries (SSBs) with lithium metal anodes offer higher specific energy than conventional lithium-ion batteries, but they must utilize areal capacities >3 mAh cm-2 and cycle at current densities >3 mA cm-2 to achieve commercial viability. Substantial research effort has focused on increasing the rate capabilities of SSBs by mitigating detrimental processes such as lithium filament penetration and short circuiting. Less attention has been paid to understanding how areal capacity impacts lithium plating/stripping behavior in SSBs, despite the importance of areal capacity for achieving high specific energy. Here, we investigate and quantify the relationships among areal capacity, current density, and plating/stripping stability using both symmetric and full-cell configurations with a sulfide solid-state electrolyte (Li6PS5Cl). We show that unstable deposition and short circuiting readily occur at rates much lower than the measured critical current density when a sufficient areal capacity is passed. A systematic study of continuous plating under different electrochemical conditions reveals average "threshold capacity" values at different current densities, beyond which short circuiting occurs. Cycling cells below this threshold capacity significantly enhances cell lifetime, enabling stable symmetric cell cycling at 2.2 mA cm-2 without short circuiting. Finally, we show that full cells with LiNi0.8Mn0.1Co0.1O2 also exhibit threshold capacity behavior, but they tend to short circuit at lower current densities and areal capacities. Our results quantify the effects of transferred capacity and demonstrate the importance of using realistic areal capacities in experiments to develop viable solid-state batteries.
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We demonstrate the vapor-liquid-solid growth of single-crystalline i-Si, i-Si/n-Si, and SixGe1-x/SiyGe1-y nanowires via the Geode process. By enabling nanowire growth on the large internal surface area of a microcapsule powder, the Geode process improves the scalability of semiconductor nanowire manufacturing while maintaining nanoscale programmability. Here, we show that heat and mass transport limitations introduced by the microcapsule wall are negligible, enabling the same degree of compositional control for nanowires grown inside microcapsules and on conventional flat substrates. Efficient heat and mass transport also minimize the structural variations of nanowires grown in microcapsules with different diameters and wall thicknesses. Nanowires containing at least 16 segments and segment lengths below 75 nm are demonstrated.
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It is critical to understand the transformation mechanisms in layered metal chalcogenides to enable controlled synthesis and processing. Here, we develop an alumina encapsulation layer-based in situ transmission electron microscopy (TEM) setup that enables the investigation of melting, crystallization, and alloying of nanoscale bismuth telluride platelets while limiting sublimation in the high-vacuum TEM environment. Heating alumina-encapsulated platelets to 700 °C in situ resulted in melting that initiated at edge planes and proceeded via the movement of a sharp interface. The encapsulated melt was then cooled to induce solidification, with individual nuclei growing to form single crystals with the same basal plane orientation as the original platelet and nonequilibrium crystal shapes imposed by the encapsulation layer. Finally, heating platelets in the presence of antimony caused alloying and lattice strain, along with heterogeneous phase formation. These findings provide new insight into important transformation processes in layered metal chalcogenide materials.
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Despite progress in solid-state battery engineering, our understanding of the chemo-mechanical phenomena that govern electrochemical behaviour and stability at solid-solid interfaces remains limited compared to at solid-liquid interfaces. Here, we use operando synchrotron X-ray computed microtomography to investigate the evolution of lithium/solid-state electrolyte interfaces during battery cycling, revealing how the complex interplay among void formation, interphase growth and volumetric changes determines cell behaviour. Void formation during lithium stripping is directly visualized in symmetric cells, and the loss of contact that drives current constriction at the interface between lithium and the solid-state electrolyte (Li10SnP2S12) is quantified and found to be the primary cause of cell failure. The interphase is found to be redox-active upon charge, and global volume changes occur owing to partial molar volume mismatches at either electrode. These results provide insight into how chemo-mechanical phenomena can affect cell performance, thus facilitating the development of solid-state batteries.
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High-capacity alloy anode materials for Li-ion batteries have long been held back by limited cyclability caused by the large volume changes during lithium insertion and removal. Hollow and yolk-shell nanostructures have been used to increase the cycling stability by providing an inner void space to accommodate volume changes and a mechanically and dimensionally stable outer surface. These materials, however, require complex synthesis procedures. Here, using in situ transmission electron microscopy, we show that sufficiently small antimony nanocrystals spontaneously form uniform voids on the removal of lithium, which are then reversibly filled and vacated during cycling. This behaviour is found to arise from a resilient native oxide layer that allows for an initial expansion during lithiation but mechanically prevents shrinkage as antimony forms voids during delithiation. We developed a chemomechanical model that explains these observations, and we demonstrate that this behaviour is size dependent. Thus, antimony naturally evolves to form optimal nanostructures for alloy anodes, as we show through electrochemical experiments in a half-cell configuration in which 15-nm antimony nanocrystals have a consistently higher Coulombic efficiency than larger nanoparticles.
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While Li-ion batteries are known to fail at temperatures below -20 °C, very little is known regarding the low-temperature behavior of next-generation high-capacity electrode materials. The lithium metal anode is of particular interest for high-energy battery chemistries, but improved understanding of and control over its electrochemical and nanoscale interfacial behavior in diverse conditions is necessary. Here, we investigate lithium deposition/stripping, morphology evolution, and solid-electrolyte interphase (SEI) structure and properties down to -80 °C using an ether-based electrolyte (DOL/DME). As temperature is reduced, we find that the morphology of deposited lithium is significantly altered. Furthermore, cryogenic transmission electron microscopy coupled with vacuum-transfer X-ray photoelectron spectroscopy reveal that the SEI exhibits different structure, chemistry, thickness, and conductive properties at lower temperatures. These results show that Li is promising for batteries operating under extreme conditions, and the distinct nanoscale evolution of Li electrodes at different temperatures must be considered when designing high-energy batteries.
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Silicon-core-carbon-shell nanoparticles have been widely studied as promising candidates for the replacement of graphite in commercial lithium-ion batteries. Over more than 10 years of R&D, the many groups actively working in this field have proposed a profusion of distinctive nanomaterial designs. This broad variety makes it extremely challenging to establish mechanistic insight into how fundamental material structure and properties affect battery performance. In particular, the interplay between the character of the carbon encapsulation layer and the electrochemical performance of the composite is still poorly understood. In this work, we aim to address this lack of knowledge through the development of a modified chemical vapor deposition approach that enables precise control of the degree of graphitization of the carbon coating. We provide a comparison between core-shell structures maintaining identical silicon cores with different types of carbon shells, that is, graphitic carbon and amorphous carbon. A highly graphitic carbon layer is not only characterized by higher electrical conductivity but markedly favors the transport of lithium ions into the silicon core with respect to an amorphous one. This advantageous property confers better cycling stability to the composite material. We also demonstrate that the graphitic-carbon-coated particles display excellent electrochemical performance even when used as a simple "drop-in" additive in graphite-dominant anodes for current generation Li-ion batteries. Replacement of 10% by weight of graphite in the electrode composition results in an increase of 60% in the storage capacity with a first cycle Coulombic efficiency of 91% and capacity retention over 100 cycles of 86%.
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Electrochemical reactions and ionic transport underpin the operation of a broad range of devices and applications, from energy storage and conversion to information technologies, as well as biochemical processes, artificial muscles, and soft actuators. Understanding the mechanisms governing function of these applications requires probing local electrochemical phenomena on the relevant time and length scales. Here, we discuss the challenges and opportunities for extending electrochemical characterization probes to the nanometer and ultimately atomic scales, including challenges in down-scaling classical methods, the emergence of novel probes enabled by nanotechnology and based on emergent physics and chemistry of nanoscale systems, and the integration of local data into macroscopic models. Scanning probe microscopy (SPM) methods based on strain detection, potential detection, and hysteretic current measurements are discussed. We further compare SPM to electron beam probes and discuss the applicability of electron beam methods to probe local electrochemical behavior on the mesoscopic and atomic levels. Similar to a SPM tip, the electron beam can be used both for observing behavior and as an active electrode to induce reactions. We briefly discuss new challenges and opportunities for conducting fundamental scientific studies, matter patterning, and atomic manipulation arising in this context.
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MoS2 has important applications in (electro)catalysis and as a semiconductor for electronic devices. Other chemical species are commonly added to MoS2 to increase catalytic activity or to alter electronic properties through substitutional or adsorption-based doping. While groundbreaking work has been devoted to determining the atomic-scale structure of MoS2 and other layered transition-metal dichalcogenides (TMDCs), there is a lack of understanding of the dynamic processes that govern the evolution of these materials during synthesis. Here, in situ transmission electron microscopy (TEM) heating, in combination with larger length scale ex situ experiments, is used to investigate the effects of added Ni on the growth of MoS2 during the thermolysis of the solid-state (NH4)2MoS4 precursor. Low concentrations of Ni are observed to cause significant differences in the MoS2 crystallization and growth process, leading to an increase in MoS2 crystal size. This is likely a result of the altered mobility of interfaces between crystals during growth. These findings demonstrate the important role of additional elements in controlling the evolution of TMDCs during synthesis, which should be considered when designing these materials for a variety of applications.
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Although vapor-liquid-solid (VLS) growth of nanowires from alloy seed particles is common in various semiconductor systems, related wire growth in all-metal systems is rare. Here, we report the spontaneous growth of nano- and microwires from metal seed particles during the cooling of Li-rich bulk alloys containing Au, Ag, or In. The as-grown wires feature Au-, Ag-, or In-rich metal tips and LiOH shafts; the results indicate that the wires grow as Li metal and are converted to polycrystalline LiOH during and/or after growth due to exposure to H2O and O2. This new process is a simple way to create nanostructures, and the findings suggest that metal nanowire growth from alloy seeds is possible in a variety of systems.