Magnetically oriented nanosheet interlayer for dynamic regeneration in lithium metal batteries.

Lithium (Li) metal has been recognized as a promising anode to advance the energy density of current Li-based batteries. However, the growth of the solid-electrolyte interphase (SEI) layer and dendritic Li microstructure pose significant challenges for the long-term operation of Li metal batteries (LMBs). Herein, we propose the utilization of a suspension electrolyte with dispersed magnetically responsive nanosheets whose orientation can be manipulated by an external magnetic field during cell operation for realizing in situ regeneration in LMBs. The regeneration mechanism arises from the redistribution of the ion flux and the formation of an inorganic-rich SEI for uniform and compact Li deposition. With the magnetic-field-induced regeneration process, we show that a Li||Li symmetric cell stably operates for 350 h at 2 mA cm-2 and 2 mA h cm-2, ~5 times that of the cell with the pristine electrolyte. Furthermore, the cycling stability can be significantly extended in the Li||NMC full cell of 3 mA h cm-2, showing a capacity retention of 67% after 500 cycles at 1C. The dynamic Li metal regeneration demonstrated here could bring useful design considerations for reviving the operating cells for achieving high-energy, long-duration battery systems.

Densified vertically lamellar electrode architectures for compact energy storage.

As one of the most compact electrochemical energy storage systems, lithium-ion batteries (LIBs) are playing an indispensable role in the process of vehicle electrification to accelerate the shift to sustainable mobility. Making battery electrodes thicker is a promising strategy for improving the energy density of LIBs which is essential for applications with weight or volume constraints, such as electric-powered transportation; however, their power densities are often significantly restricted due to elongated and tortuous charge traveling distances. Here, we propose an effective methodology that couples bidirectional freeze-casting and compression-induced densification to create densified vertically lamellar electrode architectures for compact energy storage. The vertically lamellar architectures not only overcome the critical thickness limit for conventional electrodes but also facilitate and redistribute the lithium-ion flux enabling both high rate capability and stable cyclability. Furthermore, this proposed methodology is universal as demonstrated in various electrochemical active material systems. This study offers a facile approach that realizes simultaneous high energy and high power in high-loading battery electrodes and provides useful rationales in designing electrode architectures for scalable energy storage systems.

Vertically assembled nanosheet networks for high-density thick battery electrodes.

As one of the prevailing energy storage systems, lithium-ion batteries (LIBs) have become an essential pillar in electric vehicles (EVs) during the past decade, contributing significantly to a carbon-neutral future. However, the complete transition to electric vehicles requires LIBs with yet higher energy and power densities. Here, we propose an effective methodology via controlled nanosheet self-assembly to prepare low-tortuosity yet high-density and high-toughness thick electrodes. By introducing a delicate densification in a three-dimensionally interconnected nanosheet network to maintain its vertical architecture, facile electron and ion transports are enabled despite their high packing density. This dense and thick electrode is capable of delivering a high volumetric capacity >1,600 mAh cm-3, with an areal capacity up to 32 mAh cm-2, which is among the best reported in the literature. The high-performance electrodes with superior mechanical and electrochemical properties demonstrated in this work provide a potentially universal methodology in designing advanced battery electrodes with versatile anisotropic properties.

Interfacial chemistry in multivalent aqueous batteries: fundamentals, challenges, and advances.

As one of the most promising electrochemical energy storage systems, aqueous batteries are attracting great interest due to their advantages of high safety, high sustainability, and low costs when compared with commercial lithium-ion batteries, showing great promise for grid-scale energy storage. This invited tutorial review aims to provide universal design principles to address the critical challenges at the electrode-electrolyte interfaces faced by various multivalent aqueous battery systems. Specifically, deposition regulation, ion flux homogenization, and solvation chemistry modulation are proposed as the key principles to tune the inter-component interactions in aqueous batteries, with corresponding interfacial design strategies and their underlying working mechanisms illustrated. In the end, we present a critical analysis on the remaining obstacles necessitated to overcome for the use of aqueous batteries under different practical conditions and provide future prospects towards further advancement of sustainable aqueous energy storage systems with high energy and long durability.

Fast-Charging, Binder-Free Lithium Battery Cathodes Enabled via Multidimensional Conductive Networks.

To meet the growing demands in both energy and power densities of lithium ion batteries, electrode structures must be capable of facile electron and ion transport while minimizing the content of electrochemically inactive components. Herein, binder-free LiFePO4 (LFP) cathodes are fabricated with a multidimensional conductive architecture that allows for fast-charging capability, reaching a specific capacity of 94 mAh g-1 at 4 C. Such multidimensional networks consist of active material particles wrapped by 1D single-walled carbon nanotubes (CNTs) and bound together using 2D MXene (Ti3C2Tx) nanosheets. The CNTs form a porous coating layer and improve local electron transport across the LFP surface, while the Ti3C2Tx nanosheets provide simultaneously high electrode integrity and conductive pathways through the bulk of the electrode. This work highlights the ability of multidimensional conductive fillers to realize simultaneously superior electrochemical and mechanical properties, providing useful insights into future fast-charging electrode designs for scalable electrochemical systems.

Assembled MXene-Liquid Metal Cages on Silicon Microparticles as Self-Healing Battery Anodes.

In pursuit of higher energy density in lithium-ion batteries, silicon (Si) has been recognized as a promising candidate to replace commercial graphite due to its high theoretical capacity. However, the pulverization issue of Si microparticles during lithiation/delithiation results in electrical contact loss and increased side reactions, significantly limiting its practical applications. Herein, we propose to utilize liquid metal (LM) particles as the bridging agent, which assemble conductive MXene (Ti3C2Tx) sheets via coordination chemistry, forming cage-like structures encapsulating mSi particles as self-healing high-energy anodes. Due to the integration of robust Ti3C2Tx sheets and deformable LM particles as conductive buffering cages, simultaneously high-rate capability and cyclability can be realized. Post-mortem analysis revealed the cage structural integrity and the maintained electrical percolating network after cycling. This work introduces an effective approach to accommodate structural change via a resilient encapsulating cage and offers useful interface design considerations for versatile battery electrodes.

Scalable Fast-Charging Aligned Battery Electrodes Enabled by Bidirectional Freeze-Casting.

Over the past few years, lithium-ion batteries have been extensively adopted in electric transportation. Meanwhile, the energy density of lithium-ion battery packs has been significantly improved, thanks to the development of materials science and packing technology. Despite recent progress in electric vehicle cruise ranges, the increase in battery charging rates remains a pivotal problem in electrodes with commercial-level mass loadings. Herein, we develop a scalable strategy that incorporates bidirectional freeze-casting into the conventional tape-casting method to fabricate energy-dense, fast-charging battery electrodes with aligned structures. The vertically lamellar architectures in bidirectional freeze-cast electrodes can be roll-to-roll calendered, forming the tilted yet aligned channels. These channels enable directional pathways for efficient lithium-ion transport in electrolyte-filled pores and thus realize fast-charging capabilities. In this work, we not only provide a simple yet controllable approach for building the aligned electrode architectures for fast charging but also highlight the significance of scalability in electrode fabrication considerations.

In Situ Alloying Enabled by Active Liquid Metal Filler for Self-Healing Composite Polymer Electrolytes.

Solid inorganics, known for kinetically inhibiting polymer crystallization and enhancing ionic conductivity, have attracted significant attention in solid polymer electrolytes. However, current composite polymer electrolytes (CPEs) are still facing challenges in Li metal batteries, falling short of inhibiting severe dendritic growth and resulting in very limited cycling life. This study introduces Ga62.5In21.5Sn16 (Galinstan) liquid metal (LM) as an active liquid alternative to conventional passive solid fillers, aiming at realizing self-healing protection against dendrite problems. Compared to solid inorganics, for example silica, LM droplets could more significantly reduce polymer crystallinity and enhance Li-ion conductivity due to their liquid nature, especially at temperatures below the polymer melting point. More importantly, LMs are unraveled as dynamic chemical traps, which are capable of blocking and consuming lithium dendrites upon contact via in situ alloying during battery operation and further inhibiting dendritic growth due to the lower deposition energy barrier of the formed Li-LM alloy. As a proof of concept, by strategically designing an asymmetric CPE with the active LM filling, a solid-state Li/LiFePO4 battery achieves promising full-cell functionality with notable rate performance and stable cycle life. This active filler-mediated self-healing approach could bring new insights into the battery design in versatile solid-state systems.

Gradient Architecture Design in Scalable Porous Battery Electrodes.

Because it has been demonstrated to be effective toward faster ion diffusion inside the pore space, low-tortuosity porous architecture has become the focus in thick electrode designs, and other possibilities are rarely investigated. To advance current understanding in the structure-affected electrochemistry and to broaden horizons for thick electrode designs, we present a gradient electrode design, where porous channels are vertically aligned with smaller openings on one end and larger openings on the other. With its 3D morphology carefully visualized by Raman mapping, the electrochemical properties between opposite orientations of the gradient electrodes are compared, and faster energy storage kinetics is found in larger openings and more concentrated active material near the separator. As further verified by simulation, this study on gradient electrode design deepens the knowledge of structure-related electrochemistry and brings perspectives in high-energy battery electrode designs.

Tortuosity Engineering for Improved Charge Storage Kinetics in High-Areal-Capacity Battery Electrodes.

The increasing demands of electronic devices and electric transportation necessitate lithium-ion batteries with simultaneous high energy and power capabilities. However, rate capabilities are often limited in high-loading electrodes due to the lengthy and tortuous ion transport paths with their electrochemical behaviors governed by complicated electrode architectures still elusive. Here, we report the electrode-level tortuosity engineering design enabling improved charge storage kinetics in high-energy electrodes. Both high areal capacity and high-rate capability can be achieved beyond the practical level of mass loadings in electrodes with vertically oriented architectures. The electrochemical properties in electrodes with various architectures were quantitatively investigated through correlating the characteristic time with tortuosity. The lithium-ion transport kinetics regulated by electrode architectures was further studied via combining the three-dimensional electrode architecture visualization and simulation. The tortuosity-controlled charge storage kinetics revealed in this study can be extended to general electrode systems and provide useful design consideration for next-generation high-energy/power batteries.

A Stable Solid Polymer Electrolyte for Lithium Metal Battery with Electronically Conductive Fillers.

Electronic conduction in solid-polymer electrolytes is generally not desired, which causes leakage of electrons or energy loss, and the electronically conductive domains at electrode-electrolyte interfaces can lead to continuous decomposition of electrolytes and shorting issues. However, it is noticed in this work that in an insulating matrix, the conductive domains at certain aspects could also have positive effects on the electrolyte performance with proper control. This work evaluates the limitation and benefits of electronically conductive domains in a solid-polymer electrolyte system and discusses the approach to improve the electrolyte physicochemical properties with densified local electric field distribution, enhanced bulk dielectric property, and charge transfer. By deliberately introducing the conductive domains in a regular solid-polymer electrolyte, stable cycle life, low overpotential, and promising full cell performance could be achieved.

Building Efficient Ion Pathway in Highly Densified Thick Electrodes with High Gravimetric and Volumetric Energy Densities.

A common practice in thick electrode design is to increase porosity to boost charge transport kinetics. However, a high porosity offsets the advantages of thick electrodes in both gravimetric and volumetric energy densities. Here we design a freestanding thick electrode composed of highly densified active material regions connected by continuous electrolyte-buffering voids. By wet calendering of the phase-inversion electrode, the continuous compact active material region and continuous ion transport network are controllably formed. Rate capabilities and cycling stability at high LiFePO4 loading of 126 mg cm-2 were achieved for the densified cathode with porosity as low as 38%. The decreased porosity and efficient void utilization enable high gravimetric/volumetric energy densities of 330 Wh kg-1 and 614 Wh L-1, as well as improved power densities. The versatility of this method and the industrial compatible "roll-to-roll" fabrication demonstrate an important step toward the practical application of thick electrodes.

Tunable Porous Electrode Architectures for Enhanced Li-Ion Storage Kinetics in Thick Electrodes.

Thick electrodes, although promising toward high-energy battery systems, suffer from restricted lithium-ion transport kinetics due to prolonged diffusion lengths and tortuous transport pathways. Despite the emerging low-tortuosity designs, capacity retention under higher current densities is still limited. Herein, we employ a modified ice-templating method to fabricate low-tortuosity porous electrodes with tunable wall thickness and channel width and systematically investigate the critical impacts of the fine structural parameters on the thick electrode electrochemistry. While the porous electrodes with thick walls show diminished capability under a C-rate larger than 1.5 C, those with thinner walls could maintain ∼70% capacity under 2.5 C. The superior capacity retention is ascribed to the fast diffusion into the thin lamellar walls compared with their thicker counterparts. This study provides deeper insights into structure-affected electrochemistry and opens up new perspective of 3D porous architectural designs for high-energy and high-power electrodes.

Revealing the Solid-State Electrolyte Interfacial Stability Model with Na-K Liquid Alloy.

In this work, the Na-K liquid alloy with a charge selective interfacial layer is developed to achieve an impressively long cycling life with small overpotential on a sodium super-ionic conductor solid-state electrolyte (NASICON SSE). With this unique multi-cation system as the platform, we further propose a unique model that contains a chemical decomposition domain and a kinetic decomposition domain for the interfacial stability model. Based on this model, two charge selection mechanisms are proposed with dynamic chemical kinetic equilibrium and electrochemical kinetics as the manners of control, respectively, and both are validated by the electrochemical measurements with microscopic and spectroscopic characterizations. This study provides an effective design for high-energy-density solid-state battery with alkali Na-K anode, but also presents a novel approach to understand the interfacial chemical processes that could inspire and guide future designs.

Efficient Infrared-Light-Driven CO2 Reduction Over Ultrathin Metallic Ni-doped CoS2 Nanosheets.

Converting CO2 and H2 O into carbon-based fuel by IR light is a tough task. Herein, compared with other single-component photocatalysts, the most efficient IR-light-driven CO2 reduction is achieved by an element-doped ultrathin metallic photocatalyst-Ni-doped CoS2 nanosheets (Ni-CoS2 ). The evolution rate of CH4 over Ni-CoS2 is up to 101.8 µmol g-1 h-1 . The metallic and ultrathin nature endow Ni-CoS2 with excellent IR light absorption ability. The PL spectra and Arrhenius plots indicate that Ni atoms could facilitate the separation of photogenerated carriers and the decrease of the activation energy. Moreover, in situ FTIR, DFT calculations, and CH4 -TPD reveal that the doped Ni atoms in CoS2 could effectively depress the formation energy of the *COOH, *CHO and desorption energy of CH4 . This work manifests that element doping in atomic level is a powerful way to control the reaction intermediates, providing possibilities to realize high-efficiency IR-light-driven CO2 reduction.

Promoting Transport Kinetics in Li-Ion Battery with Aligned Porous Electrode Architectures.

Developing scalable energy storage systems with high energy and power densities is essential to meeting the ever-growing portable electronics and electric vehicle markets, which calls for development of thick electrode designs to improve the active material loading and greatly enhance the overall energy density. However, rate capabilities in lithium-ion batteries usually fall off rapidly with increasing electrode thickness due to hindered ionic transport kinetics, which is especially the issue for conversion-based electroactive materials. To alleviate the transport constrains, rational design of three-dimensional porous electrodes with aligned channels is critically needed. Herein, magnetite (Fe3O4) with high theoretical capacity is employed as a model material, and with the assistance of micrometer-sized graphine oxide (GO) sheets, aligned Fe3O4/GO (AGF) electrodes with well-defined ionic transport channels are formed through a facile ice-templating method. The as-fabricated AGF electrodes exhibit excellent rate capacity compared with conventional slurry-casted electrodes with an areal capacity of ∼3.6 mAh·cm-2 under 10 mA·cm-2. Furthermore, clear evidence provided by galvanostatic charge-discharge profiles, cyclic voltammetry, and symmetric cell electrochemical impedance spectroscopy confirms the facile ionic transport kinetics in this proposed design.

Solvent-Dependent Intercalation and Molecular Configurations in Metallocene-Layered Crystal Superlattices.

Organic-inorganic superlattices are a class of artificial structures of significant scientific and technological importance. Forming these hybrid materials can be achieved via controlled intercalation of organic molecules into inorganic layered hosts, which is a complex course involving multiple physicochemical processes. In solution phase, it is further complicated by interaction of solvent molecules with the intercalant and/or host. Here we describe an intercalation system exhibiting strong solvent-dependent kinetics and phase evolution. In revisiting intercalation of ferrocene into layered VOPO4·2H2O material by taking into account the influence of solvent, we are able to unravel molecular configurations of ferrocene molecules. An exclusive orientation of ferrocene but different arrangements among the layers are concluded in two model solvents. Resolving this complicated structure is possible thanks to a combined experimental and theoretical approach. Our study provides new insights into understanding molecular configurations and controlling intercalation kinetics in creating organic-inorganic superlattices, which may offer unprecedented properties beyond conventional materials.

Ultrafast Intercalation Enabled by Strong Solvent-Host Interactions: Understanding Solvent Effect at the Atomic Level.

Solvents play an essential role in many areas of chemistry and is the cornerstone of understanding reactivity in solution-phase reactions. Solvent effects have been widely observed in intercalation reactions; however, understanding of the influence of solvents on the thermodynamics and kinetics remains largely elusive in intercalation chemistry. Now, the solvent-dependent kinetics of ferrocene intercalation into a layered vanadyl phosphate (VOPO4 ⋅2 H2 O) host is presented, with a special focus on primary alcohols. From methanol to 1-hexnaol, the intercalation rate peaks in 1-propanol (80 times faster than the slowest case in methanol). Similar kinetics of exfoliation are also found in these solvents without ferrocene. The correlation between intercalation and exfoliation is understood at atomic level by DFT calculations, which reveal the role of pre-intercalated solvent molecules play in intralayer interactions, interlayer expansion, and layer sliding.

Visible-Light-Driven Overall Water Splitting Boosted by Tetrahedrally Coordinated Blende Cobalt(II) Oxide Atomic Layers.

Directly splitting water into H2 and O2 with solar light is extremely important; however, the overall efficiency of water splitting still remains extremely low. Two types of ultrathin semiconductor layers with the same elements and the same thicknesses were designed to uncover how different atomic arrangements influence water-splitting efficiency thermodynamically and kinetically. As an example, tetrahedrally coordinated blende and octahedrally coordinated rocksalt CoO atomic layers with nearly the same thicknesses were synthesized for the first time. The blende CoO atomic layers have a smaller Eg and abundant d-d internal transition features relative to the rocksalt CoO atomic layers, which ensure enhanced visible-light harvesting ability. Density functional theory calculations reveal that the Bader charge for Co atoms in blende CoO atomic layers is larger than that of the rocksalt CoO atomic layers, which facilitates photocarrier transfer kinetics, as verified by photoluminescence spectra and time-resolved fluorescence emission decay spectra. In situ FTIR spectra and energy calculations reveal that the *OOH dissociation step is the rate-limiting step, where the blende CoO atomic layers possess a smaller *OOH dissociation energy thanks to their higher Bader charge and stronger steric effect, as confirmed by the elongated Co-OOH bonds. The blende CoO atomic layers exhibit visible-light-driven H2 and O2 formation rates of 4.43 and 2.63 µmol g-1 h-1 , roughly 3.7 times higher than those of the rocksalt CoO atomic layers.

Carbon Dioxide Electroreduction into Syngas Boosted by a Partially Delocalized Charge in Molybdenum Sulfide Selenide Alloy Monolayers.

Structural parameters of ternary transition-metal dichalcogenide (TMD) alloy usually obey Vegard law well, while interestingly it often exhibits boosted electrocatalytic performances relative to its two pristine binary TMDs. To unveil the underlying reasons, we propose an ideal model of ternary TMDs alloy monolayer. As a prototype, MoSeS alloy monolayers are successfully synthesized, in which X-ray absorption fine structure spectroscopy manifests their shortened Mo-S and lengthened Mo-Se bonds, helping to tailor the d-band electronic structure of Mo atoms. Density functional theory calculations illustrate an increased density of states near their conduction band edge, which ensures faster electron transfer confirmed by their lower work function and smaller charge-transfer resistance. Energy calculations show the off-center charge around Mo atoms not only benefits for stabilizing COOH* intermediate confirmed by its most negative formation energy, but also facilitates the rate-limiting CO desorption step verified by CO temperature programmed desorption and electro-stripping tests. As a result, MoSeS alloy monolayers attain the highest 45.2 % Faradaic efficiency for CO production, much larger than that of MoS2 monolayers (16.6 %) and MoSe2 monolayers (30.5 %) at -1.15 V vs. RHE. This work discloses how the partially delocalized charge in ternary TMDs alloys accelerates electrocatalytic performances at atomic level, opening new horizons for manipulating CO2 electroreduction properties.