A Passivation-Free Solid Electrolyte Interface Regulated by Magnesium Bromide Additive for Highly Reversible Magnesium Batteries.

Highly reversible Mg battery chemistry demands a suitable electrolyte formulation highly compatible with currently available electrodes. In general, conventional electrolytes form a passivation layer on the Mg anode, requiring the use of MgCl2 additives that lead to severe corrosion of cell components and low anodic stability. Herein, for the first time, we conducted a comparative study of a series of Mg halides as potential electrolyte additives in conventional magnesium bis(hexamethyldisilazide)-based electrolytes. A novel electrolyte formulation that includes MgBr2 showed unprecedented performance in magnesium plating/stripping, with an average Coulombic efficiency of 99.26% over 1000 cycles at 0.5 mA/cm2 and 0.5 mAh/cm2. Further analysis revealed the in situ formation of a robust Mg anode-electrolyte interface, which leads to dendrite-free Mg deposition and stable cycling performance in a Mg-Mo6S8 battery over 100 cycles. This study demonstrates the rational formulation of a novel MgBr2-based electrolyte with high anodic stability of 3.1 V for promising future applications.

Structural Design of Electrocatalyst-Decorated MXenes on Sulfur Spheres for Lithium-Sulfur Batteries.

Lithium-sulfur batteries (LSBs) are known to be potential next-generation energy storage devices. Recently, our group reported an LSB cathode made using sulfur spheres that has been spherically templated by MXene nanosheets decorated with CoSe2 nanoparticles, forming a "loose-templating" configuration. It was postulated that the minimal restacking of the outer nanoparticle-decorated MXene layer helps to enable facile ionic transport. However, as the nanosheets do not adhere conformally to the internal sphere's surface, such a configuration can be controversial, thus requiring a more systematic understanding. In this work, we report and quantify for the first time the independent and dependent variables involved in this morphology, allowing us to identify that having smaller nanoparticles resulted in better Li+ ion transport and enhanced electrochemical performances. The optimized cathode structure exhibited an initial specific capacity of 1274 mAh/g and a 0.06% decay rate per cycle at 0.5 C over 1000 cycles in LSBs.

Uncovering the Binder Interactions with S-PAN and MXene for Room Temperature Na-S Batteries.

MXenes and sulfurized polyacrylonitrile (S-PAN) are emerging as possible contenders to resolve the polysulfide dissolution and volumetric expansion issues in sodium-sulfur batteries. Herein, we explore the interactions between Ti3C2Tx MXenes and S-PAN with traditional binders such as polyvinylidene difluoride (PVDF), poly(acrylic acid) (PAA), and carboxymethyl cellulose (CMC) in Na-S batteries for the first time. We hypothesize that the linearity and polarity of the binder significantly influence the dispersion of S-PAN over Ti3C2Tx. The three-dimensional polar CMC binder resulted in better contact surface area with both S-PAN and Ti3C2Tx. Moreover, the improved binding of the discharge products with the CMC binder effectively traps them and prevents unwanted shuttling. Consequently, the Na-S battery using the CMC binder displayed a high initial capacity of 1282 mAh/g(s) at 0.2 C and a low capacity fading of 0.092% per cycle over 300 cycles. This work highlights the importance of understanding MXene-binder interactions in sulfur cathodes.

Chloride-Free Electrolyte Based on Tetrabutylammonium Triflate Additive for Extended Anodic Stability in Magnesium Batteries.

Rechargeable magnesium batteries (RMBs) have been proposed as a promising alternative to currently commercialized lithium-ion batteries. However, Mg anode passivation in conventional electrolytes necessitates the use of highly corrosive Cl- ions in the electrolyte. Herein for the first time, we design a chloride-free electrolyte for RMBs with magnesium bis(hexamethyldisilazide) (Mg(HMDS)2) and magnesium triflate (Mg(OTf)2) as the main salts and tetrabutylammonium triflate (TBAOTf) as an additive. The TBAOTf additive improved the dissolution of Mg salts, consequently enhancing the charge-carrying species in the electrolyte. COMSOL studies further revealed desirable Mg growth in our modulated electrolyte, substantiated by homogeneous electric flux distribution across the electrolyte-electrode interface. Post-mortem chemical composition analysis uncovered a MgF2-rich solid electrolyte interphase (SEI) that facilitated exceptional Mg deposition/dissolution reversibility. Our study illustrates a highly promising strategy for synthesizing a corrosion-free and reversible Mg battery electrolyte with a widened anodic stability window of up to 4.43 V.

Mitigating Concentration Polarization through Acid-Base Interaction Effects for Long-Cycling Lithium Metal Anodes.

Lithium (Li) metal has attracted great attention as a promising high-capacity anode material for next-generation high-energy-density rechargeable batteries. Nonuniform Li+ transport and uneven Li plating/stripping behavior are two key factors that deteriorate the electrochemical performance. In this work, we propose an interphase acid-base interaction effect that could regulate Li plating/stripping behavior and stabilize the Li metal anode. ZSM-5, a class of zeolites with ordered nanochannels and abundant acid sites, was employed as a functional interface layer to facilitate Li+ transport and mitigate the cell concentration polarization. As a demonstration, a pouch cell with a high-areal-capacity LiNi0.95Co0.02Mn0.03O2 cathode (3.7 mAh cm-2) and a ZSM-5 modified thin lithium anode (50 µm) delivered impressive electrochemical performance, showing 92% capacity retention in 100 cycles (375.7 mAh). This work reveals the effect of acid-base interaction on regulating lithium plating/stripping behaviors, which could be extended to developing other high-performance alkali metal anodes.

High-Performance NiS2 Hollow Nanosphere Cathodes in Magnesium-Ion Batteries Enabled by Tunable Redox Chemistry.

Two-dimensional metal dichalcogenides have demonstrated outstanding potential as cathodes for magnesium-ion batteries. However, the limited capacity, poor cycling stability, and severe electrode pulverization, resulting from lack of void space for expansion, impede their further development. In this work, we report for the first time, nickel sulfide (NiS2) hollow nanospheres assembled with nanoparticles for use as cathode materials in magnesium-ion batteries. Notably, the nanospheres were prepared by a one-step solvothermal process in the absence of an additive. The results show that regulating the synergistic effect between the rich anions and hollow structure positively affects its electrochemical performance. Crystallographic and microstructural characterizations reveal the reversible anionic redox of S2-/(S2)2-, consistent with density functional theory results. Consequently, the optimized cathode (8-NiS2 hollow nanospheres) could deliver a large capacity of 301 mA h g-1 after 100 cycles at 50 mA g-1, supporting the promising practical application of NiS2 hollow nanospheres in magnesium-ion batteries.

High Utilization of Composite Magnesium Metal Anodes Enabled by a Magnesiophilic Coating.

Metallic magnesium is a promising high-capacity anode material for energy storage technologies beyond lithium-ion batteries. However, most reported Mg metal anodes are only cyclable under shallow cycling (≤1 mAh cm-2) and thus poor Mg utilization (<3%) conditions, significantly compromising their energy-dense characteristic. Herein, composite Mg metal anodes with high capacity utilization of 75% are achieved by coating magnesiophilic gold nanoparticles on copper foils for the first time. Benefiting from homogeneous ionic flux and uniform deposition morphology, the Mg-plated Au-Cu electrode exhibits high average Coulombic efficiency of 99.16% over 170 h cycling at 75% Mg utilization. Moreover, the full cell based on Mg-plated Au-Cu anode and Mo6S8 cathode achieves superior capacity retention of 80% after 300 cycles at a low negative/positive ratio of 1.33. This work provides a simple yet effective general strategy to enhance Mg utilization and reversibility, which can be extended to other metal anodes as well.

Spherical Templating of CoSe2 Nanoparticle-Decorated MXenes for Lithium-Sulfur Batteries.

Two-dimensional MXenes produce competitive performances when incorporated into lithium-sulfur batteries (LSBs), solving key problems such as the poor electronic conductivity of sulfur and dissolution of its polysulfide intermediates. However, MXene nanosheets are known to easily aggregate and restack during electrode fabrication, filtration, or water removal, limiting their practical applicability. Furthermore, in complex electrocatalytic reactions like the multistep sulfur reduction process in LSBs, MXene alone is insufficient to ensure an optimal reaction pathway. In this work, we demonstrate for the first time a loose templating of sulfur spheres using Ti3C2Tx MXene nanosheets decorated with polymorphic CoSe2 nanoparticles. This work shows that the templating of sulfur spheres using nanoparticle-decorated MXene nanosheets can prevent nanosheet aggregation and exert a strong electrocatalytic effect, thereby enabling improved reaction kinetics and battery performance. The S@MXene-CoSe2 cathode demonstrated a long cycle life of 1000 cycles and a low capacity decay rate of 0.06% per cycle in LSBs.

In Situ Formed Magnesiophilic Sites Guiding Uniform Deposition for Stable Magnesium Metal Anodes.

Owing to its high volumetric capacity and natural abundance, magnesium (Mg) metal has attracted tremendous attention as an ideal anode material for rechargeable Mg batteries. Despite Mg deposition playing an integral role in determining the cycling lifespan, its exact behavior is not clearly understood yet. Herein, for the first time, we introduce a facile approach to build magnesiophilic In/MgIn sites in situ on a Mg metal surface using InCl3 electrolyte additive for rechargeable Mg batteries. These magnesiophilic sites can regulate Mg deposition behaviors by homogenizing the distributions of Mg-ion flux and electric field at the electrode-electrolyte interphase, allowing flat and compact Mg deposition to inhibit short-circuiting. The as-designed Mg metal batteries achieve a stable cycling lifespan of 340 h at 1.0 mA cm-2 and 1.0 mAh cm-2 using Celgard separators, while the full cell coupled with Mo6S8 cathode maintains a high capacity retention of 95.5% over 800 cycles at 1 C.

Upcycling air pollutants to fuels and chemicals via electrochemical reduction technology.

The intensification of fossil fuel usage results in significant air pollution levels. Efforts have been put into developing efficient technologies capable of converting air pollution into valuable products, including fuels and valuable chemicals (e.g., CO2 to hydrocarbon and syngas and NOx to ammonia). Among the strategic efforts to mitigate the excessive concentration of CO2 and NOx pollutants in the atmosphere, the electrochemical reduction technology of CO2 (CO2RR) and NOx (NOxRR) emerges as one of the most promising approaches. It is even more attractive if CO2RR and NOxRR are paired with renewables to store intermittent electricity in the form of chemical feedstocks. This review provides an overview of the electrochemical reduction process to convert CO2 to C1 and/or C2+ chemicals and NOx to ammonia (NH3) with a focus on electrocatalysts, electrolytes, electrolyzer, and catalytic reactor designs toward highly selective electrochemical conversion of the desired products. While the attempts in these aspects are enormous, economic consideration and environmental feasibility for actual implementation are not comprehensively provided. We discuss CO2RR and NOxRR from the life cycle and techno-economic analyses to perceive the feasibility of the current achievements. The remaining challenges associated with the industrial implementation of electrochemical CO2 and NOx reduction are additionally provided.

Using a Chloride-Free Magnesium Battery Electrolyte to Form a Robust Anode-Electrolyte Nanointerface.

Magnesium bis(hexamethyldisilazide) (Mg(HMDS)2)-based electrolytes are compelling candidates for rechargeable magnesium batteries due to their high compatibility with magnesium metal anode. However, the usual combination of Mg(HMDS)2 with chloride salts limits their practical application due to severe corrosion of cell components and low anodic stability. Herein, we report for the first time, a chloride-free Mg(HMDS)2-based electrolyte in 1,2-dimethoxyethane. By chemically controlling the moisture content using tetrabutylammonium borohydride as a moisture scavenger, the electrolyte demonstrates outstanding electrochemical performance in magnesium plating/stripping, with an average Coulombic efficiency of 98.3% over 150 cycles, and is noncorrosive to cell components. Surface analysis and depth profiling of the magnesium metal anode reveals the formation of a robust solid electrolyte interphase at the anode-electrolyte nanointerface, which allows magnesium plating/stripping to occur reversibly. The electrolyte also demonstrates good compatibility with a copper sulfide nanomaterial cathode, which exhibits a high initial discharge capacity of 261.5 mAh g-1.

Sulfurized Cyclopentadienyl Nanocomposites for Shuttle-Free Room-Temperature Sodium-Sulfur Batteries.

A major challenge hindering the practical adoption of room-temperature sodium-sulfur batteries (NaSBs) is polysulfide dissolution and shuttling, which results in irreversible capacity decay and low Coulombic efficiencies. In this work, we demonstrate for the first time NaSBs using a ferrocene-derived amorphous sulfurized cyclopentadienyl composite (SCC) cathode. Polysulfide dissolution is eliminated via covalent bonding between the insoluble short-chain sulfur species and carbon backbone. Control experiments with a metal-free composite analogue determined that the iron species in the SCC does not have a significant role in polysulfide anchoring. Instead, the superior electrochemical performance is attributed to sulfur covalently bonded to carbon and the uniform nanoparticulate morphology of the SCC composite. In the carbonate-based electrolyte, a discharge capacity of 795 mAh g(S)-1 was achieved during early cycling at 0.2 C, and high Coulombic efficiencies close to 100% were maintained with capacity retention of 532 and 442 mAh g(S)-1 after 100 and 200 cycles, respectively.

Manipulating Redox Kinetics of Sulfur Species Using Mott-Schottky Electrocatalysts for Advanced Lithium-Sulfur Batteries.

Lithium-sulfur (Li-S) batteries suffer from sluggish sulfur redox reactions under high-sulfur-loading and lean-electrolyte conditions. Herein, a typical Co@NC heterostructure composed of Co nanoparticles and a semiconductive N-doped carbon matrix is designed as a model Mott-Schottky catalyst to exert the electrocatalytic effect on sulfur electrochemistry. Theoretical and experimental results reveal the redistribution of charge and a built-in electric field at the Co@NC heterointerface, which are critical to lowering the energy barrier of polysulfide reduction and Li2S oxidation in the discharge and charge process, respectively. With Co@NC Mott-Schottky catalysts, the Li-S batteries display an ultrahigh capacity retention of 92.1% and a system-level gravimetric energy density of 307.8 Wh kg-1 under high S loading (10.73 mg cm-2) and lean electrolyte (E/S = 5.9 µL mgsulfur-1) conditions. The proposed Mott-Schottky heterostructure not only deepens the understanding of the electrocatalytic effect in Li-S chemistry but also inspires a rational catalyst design for advanced high-energy-density batteries.

Tunable Nitrogen-Doping of Sulfur Host Nanostructures for Stable and Shuttle-Free Room-Temperature Sodium-Sulfur Batteries.

Room-temperature sodium-sulfur batteries have potential in stationary applications, but challenges such as loss of active sulfur and low electrical conductivity must be solved. Nitrogen-doped nanocarbon host cathodes have been employed in metal-sulfur batteries: polar interactions mitigate the loss of sulfur, while the conductive nanostructure addresses the low conductivity. Nevertheless, these two properties run contrary to each other as greater nitrogen-doping of nanocarbon hosts is associated with lower conductivity. Herein, we investigate the polarity-conductivity dilemma to determine which of these properties have the stronger influence on cycling performance. Lower carbonization temperatures produce more pyridinic nitrogen and pyrrolic nitrogen, which from density functional theory calculations preferentially bind discharge products (Na2S and short-chain polysulfides). Despite its lower conductivity, the highly doped composite showed better Coulombic efficiency and stability, retaining a high capacity of 980 mAh g(S)-1 after 800 cycles. Our findings represent a paradigm shift where nitrogen-doping should be prioritized in designing shuttle-free, long-life sodium-sulfur batteries.

A Replacement Reaction Enabled Interdigitated Metal/Solid Electrolyte Architecture for Battery Cycling at 20 mA cm-2 and 20 mAh cm-2.

Metal anodes represent as a prime choice for the coming generation rechargeable batteries with high energy density. However, daunting challenges including electrode volume variation and inevitable side reactions preclude them from becoming a viable technology. Here, a facile replacement reaction was employed to fabricate a three-dimensional (3D) interdigitated metal/solid electrolyte composite electrode, which not only provides a stable host structure for buffering the volume change within the composite but also prevents side reactions by avoiding the direct contact between active metal and liquid electrolyte. As a proof-of-concept demonstration, a 3D interdigitated zinc (Zn) metal/solid electrolyte architecture was fabricated via a galvanic replacement reaction between Zn metal foil and indium (In) chloride solution followed by electrochemical activation, featuring the interdigitation between metallic Zn and amorphous indium hydroxide sulfate (IHS) with high Zn2+ conductivity (56.9 ± 1.8 mS cm-1), large Zn2+ transference number (0.55), and high electronic resistivity [(2.08 ± 0.01) × 103 Ω cm]. The as-designed Zn/IHS electrode sustained stable electrochemical Zn plating/stripping over 700 cycles with a record-low overpotential of 8 mV at 1 mA cm-2 and 0.5 mAh cm-2. More impressively, it displayed cycle-stable performance with low overpotential of 10 mV under ultrahigh current density and areal capacity (20 mA cm-2, 20 mAh cm-2), which outperformed all the reported Zn metal electrodes in mild aqueous electrolyte. The fabrication of interdigitated metal/solid electrolyte was generalized to other metal pairs, including Zn/Sn and Zn/Co, which provide inspiration for next-generation Zn metal batteries with high energy density and reversibility.

Designing Nanostructured Metal Chalcogenides as Cathode Materials for Rechargeable Magnesium Batteries.

Rechargeable magnesium batteries (RMBs) are regarded as promising candidates for beyond-lithium-ion batteries owing to their high energy density. Moreover, as Mg metal is earth-abundant and has low propensity for dendritic growth, RMBs have the advantages of being more affordable and safer than the currently used lithium-ion batteries. However, the commercial viability of RMBs has been negatively impacted by slow diffusion kinetics in most cathode materials due to the high charge density and strongly polarizing nature of the Mg2+ ion. Nanostructuring of potential cathode materials such as metal chalcogenides offers an effective means of addressing these challenges by providing larger surface area and shorter migration routes. In this article, a review of recent research on the design of metal chalcogenide nanostructures for RMBs' cathode materials is provided. The different types and structures of metal chalcogenide cathodes are discussed, and the synthetic strategies through which nanostructuring of these materials can be achieved are described. An organized summary of their electrochemical performance is also presented, along with an analysis of the current challenges and future directions. Although particular focus is placed on RMBs, many of the nanostructuring concepts that are discussed here can be carried forward to other next-generation energy storage systems.

Conformal Prelithiation Nanoshell on LiCoO2 Enabling High-Energy Lithium-Ion Batteries.

The initial lithium loss in lithium-ion batteries (LIBs) reduces their energy density (e.g., 15% or higher for LIBs using a Si-based anode). Herein, we report in situ chemical formation of a conformal Li2O/Co nanoshell (∼20 nm) on LiCoO2 particles as a high-capacity built-in prelithiation reagent to compensate this initial lithium loss. We show a 15 mAh g-1 increase in overall charge capacity for the LiCoO2 with 1.5 wt % Li2O/Co in comparison to the pristine LiCoO2 in virtue of the irreversible lithium extraction from the nanoshell (4Li2O + 3Co → 8Li+ + 8e- + Co3O4, 2Li2O → 4Li+ + 4e- + O2↑). Paired with a graphite-SiO anode, a full cell using such a LiCoO2 cathode demonstrates 11% higher discharge capacity (2.60 mAh cm-2) than that using pristine LiCoO2 (2.34 mAh cm-2) at 0.1 C, as well as stable battery cycling. Moreover, the prelithiated LiCoO2 is compatible with the current battery fabrication process.

Metal/LiF/Li2O Nanocomposite for Battery Cathode Prelithiation: Trade-off between Capacity and Stability.

Lithium-ion batteries (LIBs) are currently dominating the portable electronics market and supplying power for electric vehicles and grid-level storage. However, lithium loss in the formation cycle at the anode side reduces the energy density of state-of-the-art LIBs with carbon anode materials. This situation will be even more severe for future LIBs using high-capacity Si-based anode materials. In this study, a transition metal-based nanocomposite with built-in lithium source was synthesized, featuring Fe nanodomains with a size of ∼5 nm uniformly dispersed in a hybrid Li2O and LiF matrix with intimate contact between them. The Fe/LiF/Li2O nanocomposite released a high Li-ion capacity of 550 mA h/g based on a multielectron inverse conversion reaction during the first-cycle charge process and exhibited better ambient stability than the counterpart with a pure Li2O matrix and also a lower lithium-extraction voltage and faster reaction kinetics than the counterpart with a pure LiF matrix. Serving as an additive to various cathodes (e.g., LiCoO2, LiFePO4, and LiNi1-x-yCoxMnyO2), the Fe/LiF/Li2O nanocomposite showed excellent lithium compensation effect. Using 4.8 wt % Fe/LiF/Li2O additive based on the total mass of the electrodes, a LiNi0.8Co0.1Mn0.1O2|SiO-graphite full cell with a high cathode mass loading of 20 mg/cm2 exhibited a high reversible capacity of 2.9 mA h/cm2 at 0.5 C after 100 cycles which is a 15% increase in comparison to the counterpart without the prelithiation additive. After the Fe/LiF/Li2O nanocomposite was immersed into the electrolyte and rested for 72 h, the content of iron metal in the electrolyte was negligible, indicating that this prelithiation additive was stable in the electrolyte and would not cause any side reactions, such as the shuttle of iron ions during cycling. The high "donor" Li-ion capacity, good ambient stability, and its compatibility with existing cathode materials and battery fabrication processes make the Fe/LiF/Li2O nanocomposite a promising cathode prelithiation additive to offset the initial lithium loss and improve the energy density of LIBs.

Self-gating in semiconductor electrocatalysis.

The semiconductor-electrolyte interface dominates the behaviours of semiconductor electrocatalysis, which has been modelled as a Schottky-analogue junction according to classical electron transfer theories. However, this model cannot be used to explain the extremely high carrier accumulations in ultrathin semiconductor catalysis observed in our work. Inspired by the recently developed ion-controlled electronics, we revisit the semiconductor-electrolyte interface and unravel a universal self-gating phenomenon through microcell-based in situ electronic/electrochemical measurements to clarify the electronic-conduction modulation of semiconductors during the electrocatalytic reaction. We then demonstrate that the type of semiconductor catalyst strongly correlates with their electrocatalysis; that is, n-type semiconductor catalysts favour cathodic reactions such as the hydrogen evolution reaction, p-type ones prefer anodic reactions such as the oxygen evolution reaction and bipolar ones tend to perform both anodic and cathodic reactions. Our study provides new insight into the electronic origin of the semiconductor-electrolyte interface during electrocatalysis, paving the way for designing high-performance semiconductor catalysts.

Catalytic oxidation of Li2S on the surface of metal sulfides for Li-S batteries.

Polysulfide binding and trapping to prevent dissolution into the electrolyte by a variety of materials has been well studied in Li-S batteries. Here we discover that some of those materials can play an important role as an activation catalyst to facilitate oxidation of the discharge product, Li2S, back to the charge product, sulfur. Combining theoretical calculations and experimental design, we select a series of metal sulfides as a model system to identify the key parameters in determining the energy barrier for Li2S oxidation and polysulfide adsorption. We demonstrate that the Li2S decomposition energy barrier is associated with the binding between isolated Li ions and the sulfur in sulfides; this is the main reason that sulfide materials can induce lower overpotential compared with commonly used carbon materials. Fundamental understanding of this reaction process is a crucial step toward rational design and screening of materials to achieve high reversible capacity and long cycle life in Li-S batteries.