Scalable Synthesis of High Entropy Alloy Nanoparticles by Microwave Heating.

High entropy alloy nanoparticles (HEA-NPs) are reported to have superior performance in catalysis, energy storage, and conversion due to the broad range of elements that can be incorporated in these materials, enabling tunable activity, excellent thermal and chemical stability, and a synergistic catalytic effect. However, scaling the manufacturing of HEA-NPs with uniform particle size and homogeneous elemental distribution efficiently is still a challenge due to the required critical synthetic conditions where high temperature is typically involved. In this work, we demonstrate an efficient and scalable microwave heating method using carbon-based materials as substrates to fabricate HEA-NPs with uniform particle size. Due to the abundant functional group defects that can absorb microwave efficiently, reduced graphene oxide is employed as a model substrate to produce an average temperature reaching as high as ∼1850 K within seconds. As a proof-of-concept, we utilize this rapid, high-temperature heating process to synthesize PtPdFeCoNi HEA-NPs, which exhibit an average particle size of ∼12 nm and uniform elemental mixing resulting from decomposition nearly at the same time and liquid metal solidification without diffusion. Various carbon-based materials can also be employed as substrates, including one-dimensional carbon nanofibers and three-dimensional carbonized wood, which can achieve temperatures of >1400 K. This facile and efficient microwave heating method is also compatible with the roll-to-roll process, providing a feasible route for scalable HEA-NPs manufacturing.

Amorphous-Carbon-Coated 3D Solid Electrolyte for an Electro-Chemomechanically Stable Lithium Metal Anode in Solid-State Batteries.

The use of solid-state electrolyte may be necessary to enable safe, high-energy-density Li metal anodes for next-generation energy storage systems. However, the inhomogeneous local current densities during long-term cycling result in instability and detachment of the Li anode from the electrolyte, which greatly hinders practical application. In this study, we report a new approach to maintain a stable Li metal | electrolyte interface by depositing an amorphous carbon nanocoating on garnet-type solid-state electrolyte. The carbon nanocoating provides both electron and ion conducting capability, which helps to homogenize the lithium metal stripping and plating processes. After coating, we find the Li metal/garnet interface displays stable cycling at 3 mA/cm2 for more than 500 h, demonstrating the interface's outstanding electro-chemomechanical stability. This work suggests amorphous carbon coatings may be a promising strategy for achieving stable Li metal | electrolyte interfaces and reliable Li metal batteries.

Rapid, High-Temperature, In Situ Microwave Synthesis of Bulk Nanocatalysts.

Carbon-black-supported nanoparticles (CNPs) have attracted considerable attention for their intriguing catalytic properties and promising applications. The traditional liquid synthesis of CNPs commonly involves demanding operation conditions and complex pre- or post-treatments, which are time consuming and energy inefficient. Herein, a rapid, scalable, and universal strategy is reported to synthesize highly dispersed metal nanoparticles embedded in a carbon matrix via microwave irradiation of carbon black with preloaded precursors. By optimizing the amount of carbon black, the microwave absorption is dramatically improved while the thermal dissipation is effectively controlled, leading to a rapid temperature increase in carbon black, ramping to 1270 K in just 6 s. The whole synthesis process requires no capping agents or surfactants, nor tedious pre- or post-treatments of carbon black, showing tremendous potential for mass production. As a proof of concept, the synthesis of ultrafine Ru nanoparticles (≈2.57 nm) uniformly embedded in carbon black using this microwave heating technique is demonstrated, which displays remarkable electrocatalytic performance when used as the cathode in a Li-O2 battery. This microwave heating method can be extended to the synthesis of other nanoparticles, thereby providing a general methodology for the mass production of carbon-supported catalytic nanoparticles.

Three-Dimensional, Solid-State Mixed Electron-Ion Conductive Framework for Lithium Metal Anode.

Solid-state electrolytes (SSEs) have been widely considered as enabling materials for the practical application of lithium metal anodes. However, many problems inhibit the widespread application of solid state batteries, including the growth of lithium dendrites, high interfacial resistance, and the inability to operate at high current density. In this study, we report a three-dimensional (3D) mixed electron/ion conducting framework (3D-MCF) based on a porous-dense-porous trilayer garnet electrolyte structure created via tape casting to facilitate the use of a 3D solid state lithium metal anode. The 3D-MCF was achieved by a conformal coating of carbon nanotubes (CNTs) on the porous garnet structure, creating a composite mixed electron/ion conductor that acts as a 3D host for the lithium metal. The lithium metal was introduced into the 3D-MCF via slow electrochemical deposition, forming a 3D lithium metal anode. The slow lithiation leads to improved contact between the lithium metal anode and garnet electrolyte, resulting in a low resistance of 25 Ω cm2. Additionally, due to the continuous CNT coating and its seamless contact with the garnet we observed highly uniform lithium deposition behavior in the porous garnet structure. With the same local current density, the high surface area of the porous garnet framework leads to a higher overall areal current density for stable lithium deposition. An elevated current density of 1 mA/cm2 based on the geometric area of the cell was demonstrated for continuous lithium cycling in symmetric lithium cells. For battery operation of the trilayer structure, the lithium can be cycled between the 3D-MCF on one side and the cathode infused into the porous structure on the opposite side. The 3D-MCF created by the porous garnet structure and conformal CNT coating provides a promising direction toward new designs in solid-state lithium metal batteries.

Continuous plating/stripping behavior of solid-state lithium metal anode in a 3D ion-conductive framework.

The increasing demands for efficient and clean energy-storage systems have spurred the development of Li metal batteries, which possess attractively high energy densities. For practical application of Li metal batteries, it is vital to resolve the intrinsic problems of Li metal anodes, i.e., the formation of Li dendrites, interfacial instability, and huge volume changes during cycling. Utilization of solid-state electrolytes for Li metal anodes is a promising approach to address those issues. In this study, we use a 3D garnet-type ion-conductive framework as a host for the Li metal anode and study the plating and stripping behaviors of the Li metal anode within the solid ion-conductive host. We show that with a solid-state ion-conductive framework and a planar current collector at the bottom, Li is plated from the bottom and rises during deposition, away from the separator layer and free from electrolyte penetration and short circuit. Owing to the solid-state deposition property, Li grows smoothly in the pores of the garnet host without forming Li dendrites. The dendrite-free deposition and continuous rise/fall of Li metal during plating/stripping in the 3D ion-conductive host promise a safe and durable Li metal anode. The solid-state Li anode shows stable cycling at 0.5 mA cm-2 for 300 h with a small overpotential, showing a significant improvement compared with reported Li anodes with ceramic electrolytes. By fundamentally eliminating the dendrite issue, the solid Li metal anode shows a great potential to build safe and reliable Li metal batteries.

3D-Printing Electrolytes for Solid-State Batteries.

Solid-state batteries have many enticing advantages in terms of safety and stability, but the solid electrolytes upon which these batteries are based typically lead to high cell resistance. Both components of the resistance (interfacial, due to poor contact with electrolytes, and bulk, due to a thick electrolyte) are a result of the rudimentary manufacturing capabilities that exist for solid-state electrolytes. In general, solid electrolytes are studied as flat pellets with planar interfaces, which minimizes interfacial contact area. Here, multiple ink formulations are developed that enable 3D printing of unique solid electrolyte microstructures with varying properties. These inks are used to 3D-print a variety of patterns, which are then sintered to reveal thin, nonplanar, intricate architectures composed only of Li7 La3 Zr2 O12 solid electrolyte. Using these 3D-printing ink formulations to further study and optimize electrolyte structure could lead to solid-state batteries with dramatically lower full cell resistance and higher energy and power density. In addition, the reported ink compositions could be used as a model recipe for other solid electrolyte or ceramic inks, perhaps enabling 3D printing in related fields.

Anisotropic, lightweight, strong, and super thermally insulating nanowood with naturally aligned nanocellulose.

There has been a growing interest in thermal management materials due to the prevailing energy challenges and unfulfilled needs for thermal insulation applications. We demonstrate the exceptional thermal management capabilities of a large-scale, hierarchal alignment of cellulose nanofibrils directly fabricated from wood, hereafter referred to as nanowood. Nanowood exhibits anisotropic thermal properties with an extremely low thermal conductivity of 0.03 W/m·K in the transverse direction (perpendicular to the nanofibrils) and approximately two times higher thermal conductivity of 0.06 W/m·K in the axial direction due to the hierarchically aligned nanofibrils within the highly porous backbone. The anisotropy of the thermal conductivity enables efficient thermal dissipation along the axial direction, thereby preventing local overheating on the illuminated side while yielding improved thermal insulation along the backside that cannot be obtained with isotropic thermal insulators. The nanowood also shows a low emissivity of <5% over the solar spectrum with the ability to effectively reflect solar thermal energy. Moreover, the nanowood is lightweight yet strong, owing to the effective bonding between the aligned cellulose nanofibrils with a high compressive strength of 13 MPa in the axial direction and 20 MPa in the transverse direction at 75% strain, which exceeds other thermal insulation materials, such as silica and polymer aerogels, Styrofoam, and wool. The excellent thermal management, abundance, biodegradability, high mechanical strength, low mass density, and manufacturing scalability of the nanowood make this material highly attractive for practical thermal insulation applications.

Extrusion-Based 3D Printing of Hierarchically Porous Advanced Battery Electrodes.

A highly porous 2D nanomaterial, holey graphene oxide (hGO), is synthesized directly from holey graphene powder and employed to create an aqueous 3D printable ink without the use of additives or binders. Stable dispersions of hydrophilic hGO sheets in water (≈100 mg mL-1 ) can be readily achieved. The shear-thinning behavior of the aqueous hGO ink enables extrusion-based printing of fine filaments into complex 3D architectures, such as stacked mesh structures, on arbitrary substrates. The freestanding 3D printed hGO meshes exhibit trimodal porosity: nanoscale (4-25 nm through-holes on hGO sheets), microscale (tens of micrometer-sized pores introduced by lyophilization), and macroscale (<500 µm square pores of the mesh design), which are advantageous for high-performance energy storage devices that rely on interfacial reactions to promote full active-site utilization. To elucidate the benefit of (nano)porosity and structurally conscious designs, the additive-free architectures are demonstrated as the first 3D printed lithium-oxygen (Li-O2 ) cathodes and characterized alongside 3D printed GO-based materials without nanoporosity as well as nanoporous 2D vacuum filtrated films. The results indicate the synergistic effect between 2D nanomaterials, hierarchical porosity, and overall structural design, as well as the promise of a freeform generation of high-energy-density battery systems.

Tuning the High-Temperature Wetting Behavior of Metals toward Ultrafine Nanoparticles.

The interaction between metal nanoparticles (NPs) and their substrate plays a critical role in determining the particle morphology, distribution, and properties. The pronounced impact of a thin oxide coating on the dispersion of metal NPs on a carbon substrate is presented. Al2 O3 -supported Pt NPs are compared to the direct synthesis of Pt NPs on bare carbon surfaces. Pt NPs with an average size of about 2 nm and a size distribution ranging between 0.5 nm and 4.0 nm are synthesized on the Al2 O3 coated carbon nanofiber, a significant improvement compared to those directly synthesized on a bare carbon surface. First-principles modeling verifies the stronger adsorption of Pt clusters on Al2 O3 than on carbon, which attributes the formation of ultrafine Pt NPs. This strategy paves the way towards the rational design of NPs with enhanced dispersion and controlled particle size, which are promising in energy storage and electrocatalysis.

Textile Inspired Lithium-Oxygen Battery Cathode with Decoupled Oxygen and Electrolyte Pathways.

The lithium-air (Li-O2 ) battery has been deemed one of the most promising next-generation energy-storage devices due to its ultrahigh energy density. However, in conventional porous carbon-air cathodes, the oxygen gas and electrolyte often compete for transport pathways, which limit battery performance. Here, a novel textile-based air cathode is developed with a triple-phase structure to improve overall battery performance. The hierarchical structure of the conductive textile network leads to decoupled pathways for oxygen gas and electrolyte: oxygen flows through the woven mesh while the electrolyte diffuses along the textile fibers. Due to noncompetitive transport, the textile-based Li-O2 cathode exhibits a high discharge capacity of 8.6 mAh cm-2 , a low overpotential of 1.15 V, and stable operation exceeding 50 cycles. The textile-based structure can be applied to a range of applications (fuel cells, water splitting, and redox flow batteries) that involve multiple phase reactions. The reported decoupled transport pathway design also spurs potential toward flexible/wearable Li-O2 batteries.

Universal, In Situ Transformation of Bulky Compounds into Nanoscale Catalysts by High-Temperature Pulse.

The synthesis of nanoscale metal compound catalysts has attracted much research attention in the past decade. The challenges of preparation of the metal compound include the complexity of the synthesis process and difficulty of precise control of the reaction conditions. Herein, we report an in situ synthesis of nanoparticles via a high-temperature pulse method where the bulk material acts as the precursor. During the process of rapid heating and cooling, swift melting, anchoring, and recrystallization occur, resulting in the generation of high-purity nanoparticles. In our work, the cobalt boride (Co2B) nanoparticles with a diameter of 10-20 nm uniformly anchored on the reduced graphene oxide (rGO) nanosheets were successfully prepared using the high temperature pulse method. The as-prepared Co2B/rGO composite displayed remarkable electrocatalytic performance for the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER). We also prepared molybdenum disulfide (MoS2) and cobalt oxide (Co3O4) nanoparticles, thereby demonstrating that the high-temperature pulse is a universal method to synthesize ultrafine metal compound nanoparticles.

In Situ High Temperature Synthesis of Single-Component Metallic Nanoparticles.

Nanoparticles (NPs) dispersed within a conductive host are essential for a range of applications including electrochemical energy storage, catalysis, and energetic devices. However, manufacturing high quality NPs in an efficient manner remains a challenge, especially due to agglomeration during assembly processes. Here we report a rapid thermal shock method to in situ synthesize well-dispersed NPs on a conductive fiber matrix using metal precursor salts. The temperature of the carbon nanofibers (CNFs) coated with metal salts was ramped from room temperature to ∼2000 K in 5 ms, which corresponds to a rate of 400,000 K/s. Metal salts decompose rapidly at such high temperatures and nucleate into metallic nanoparticles during the rapid cooling step (cooling rate of ∼100,000 K/s). The high temperature duration plays a critical role in the size and distribution of the nanoparticles: the faster the process is, the smaller the nanoparticles are, and the narrower the size distribution is. We also demonstrated that the peak temperature of thermal shock can reach ∼3000 K, much higher than the decomposition temperature of many salts, which ensures the possibility of synthesizing various types of nanoparticles. This universal, in situ, high temperature thermal shock method offers considerable potential for the bulk synthesis of unagglomerated nanoparticles stabilized within a matrix.

Encapsulation of Metallic Na in an Electrically Conductive Host with Porous Channels as a Highly Stable Na Metal Anode.

Room-temperature Na ion batteries (NIBs) have attracted great attention because of the widely available, abundant sodium resources and potentially low cost. Currently, the challenge of the NIB development is due primarily to the lack of a high-performance anode, while the Na metal anode holds great promise considering its highest specific capacity of 1165 mA h/g and lowest anodic potential. However, an uneven deposit, relatively infinite volume change, and dendritic growth upon plating/stripping cycles cause a low Coulombic efficiency, poor cycling performance, and severe safety concerns. Here, a stable Na carbonized wood (Na-wood) composite anode was fabricated via a rapid melt infusion (about 5 s) into channels of carbonized wood by capillary action. The channels function as a high-surface-area, conductive, mechanically stable skeleton, which lowers the effective current density, ensures a uniform Na nucleation, and restricts the volume change over cycles. As a result, the Na-wood composite anode exhibited flat plating/stripping profiles with smaller overpotentials and stable cycling performance over 500 h at 1.0 mA/cm2 in a common carbonate electrolyte system. In sharp comparison, the planar Na metal electrode showed a much shorter cycle life of 100 h under the same test conditions.

Enabling High-Areal-Capacity Lithium-Sulfur Batteries: Designing Anisotropic and Low-Tortuosity Porous Architectures.

Lithium-sulfur (Li-S) batteries have attracted much attention due to their high theoretical energy density in comparison to conventional state-of-the-art lithium-ion batteries. However, low sulfur mass loading in the cathode results in low areal capacity and impedes the practical use of Li-S cells. Inspired by wood, a cathode architecture with natural, three-dimensionally (3D) aligned microchannels filled with reduced graphene oxide (RGO) were developed as an ideal structure for high sulfur mass loading. Compared with other carbon materials, the 3D porous carbon matrix has several advantages including low tortuosity, high electrical conductivity, and good structural stability, which make it an excellent 3D lightweight current collector. The Li-S battery assembled with the wood-based sulfur electrode can deliver a high areal capacity of 15.2 mAh cm-2 with a sulfur mass loading of 21.3 mg cm-2. This work provides a facile but effective strategy to develop 3D porous electrodes for Li-S batteries, which can also be applied to other cathode materials to achieve a high areal capacity with uncompromised rate and cycling performance.

Toward garnet electrolyte-based Li metal batteries: An ultrathin, highly effective, artificial solid-state electrolyte/metallic Li interface.

Solid-state batteries are a promising option toward high energy and power densities due to the use of lithium (Li) metal as an anode. Among all solid electrolyte materials ranging from sulfides to oxides and oxynitrides, cubic garnet-type Li7La3Zr2O12 (LLZO) ceramic electrolytes are superior candidates because of their high ionic conductivity (10-3 to 10-4 S/cm) and good stability against Li metal. However, garnet solid electrolytes generally have poor contact with Li metal, which causes high resistance and uneven current distribution at the interface. To address this challenge, we demonstrate a strategy to engineer the garnet solid electrolyte and the Li metal interface by forming an intermediary Li-metal alloy, which changes the wettability of the garnet surface (lithiophobic to lithiophilic) and reduces the interface resistance by more than an order of magnitude: 950 ohm·cm2 for the pristine garnet/Li and 75 ohm·cm2 for the surface-engineered garnet/Li. Li7La2.75Ca0.25Zr1.75Nb0.25O12 (LLCZN) was selected as the solid-state electrolyte (SSE) in this work because of its low sintering temperature, stabilized cubic garnet phase, and high ionic conductivity. This low area-specific resistance enables a solid-state garnet SSE/Li metal configuration and promotes the development of a hybrid electrolyte system. The hybrid system uses the improved solid-state garnet SSE Li metal anode and a thin liquid electrolyte cathode interfacial layer. This work provides new ways to address the garnet SSE wetting issue against Li and get more stable cell performances based on the hybrid electrolyte system for Li-ion, Li-sulfur, and Li-oxygen batteries toward the next generation of Li metal batteries.

High-capacity, low-tortuosity, and channel-guided lithium metal anode.

Lithium metal anode with the highest capacity and lowest anode potential is extremely attractive to battery technologies, but infinite volume change during the Li stripping/plating process results in cracks and fractures of the solid electrolyte interphase, low Coulombic efficiency, and dendritic growth of Li. Here, we use a carbonized wood (C-wood) as a 3D, highly porous (73% porosity) conductive framework with well-aligned channels as Li host material. We discovered that molten Li metal can infuse into the straight channels of C-wood to form a Li/C-wood electrode after surface treatment. The C-wood channels function as excellent guides in which the Li stripping/plating process can take place and effectively confine the volume change that occurs. Moreover, the local current density can be minimized due to the 3D C-wood framework. Therefore, in symmetric cells, the as-prepared Li/C-wood electrode presents a lower overpotential (90 mV at 3 mA⋅cm-2), more-stable stripping/plating profiles, and better cycling performance (∼150 h at 3 mA⋅cm-2) compared with bare Li metal electrode. Our findings may open up a solution for fabricating stable Li metal anode, which further facilitates future application of high-energy-density Li metal batteries.

Conformal, Nanoscale ZnO Surface Modification of Garnet-Based Solid-State Electrolyte for Lithium Metal Anodes.

Solid-state electrolytes are known for nonflammability, dendrite blocking, and stability over large potential windows. Garnet-based solid-state electrolytes have attracted much attention for their high ionic conductivities and stability with lithium metal anodes. However, high-interface resistance with lithium anodes hinders their application to lithium metal batteries. Here, we demonstrate an ultrathin, conformal ZnO surface coating by atomic layer deposition for improved wettability of garnet solid-state electrolytes to molten lithium that significantly decreases the interface resistance to as low as ∼20 Ω·cm2. The ZnO coating demonstrates a high reactivity with lithium metal, which is systematically characterized. As a proof-of-concept, we successfully infiltrated lithium metal into porous garnet electrolyte, which can potentially serve as a self-supported lithium metal composite anode having both high ionic and electrical conductivity for solid-state lithium metal batteries. The facile surface treatment method offers a simple strategy to solve the interface problem in solid-state lithium metal batteries with garnet solid electrolytes.

A stable room-temperature sodium-sulfur battery.

High-energy rechargeable batteries based on earth-abundant materials are important for mobile and stationary storage technologies. Rechargeable sodium-sulfur batteries able to operate stably at room temperature are among the most sought-after platforms because such cells take advantage of a two-electron-redox process to achieve high storage capacity from inexpensive electrode materials. Here we report a room-temperature sodium-sulfur battery that uses a microporous carbon-sulfur composite cathode, and a liquid carbonate electrolyte containing the ionic liquid 1-methyl-3-propylimidazolium-chlorate tethered to SiO2 nanoparticles. We show that these cells can cycle stably at a rate of 0.5 C (1 C=1675, mAh g(-1)) with 600 mAh g(-1) reversible capacity and nearly 100% Coulombic efficiency. By means of spectroscopic and electrochemical analysis, we find that the particles form a sodium-ion conductive film on the anode, which stabilizes deposition of sodium. We also find that sulfur remains interred in the carbon pores and undergo solid-state electrochemical reactions with sodium ions.

The Sodium-Oxygen/Carbon Dioxide Electrochemical Cell.

Electrochemical cells that utilize metals in the anode and an ambient gas as the active material in the cathode blur the lines between fuel cells and batteries. Such cells are under active consideration worldwide because they are considered among the most promising energy storage platforms for electrified transportation. Li-air batteries are among the most actively investigated cells in this class, but long-term challenges, such as CO2 contamination of the cathode gas and electrolyte decomposition, are associated with loss of rechargeability owing to metal carbonate formation in the cathode. Remediation of the first of these problems adds significant infrastructure burdens to the Li-air cell that bring into question its commercial viability. Several recent studies offer contradictory evidence, namely, that the presence of substantial fractions of CO2 in the cathode gas stream can have significant benefits, including increasing the already high specific energy of a Li-O2 cell by as much as 200 %. In this report, we consider electrochemical processes in model Na-O2 /CO2 cells and find that, provided the electrode/electrolyte interfaces are electrochemically stable, such cells are able to deliver both exceptional energy storage capacity and stable long-term charge-discharge cycling behaviors at room temperature.