Flexible, Mechanically Robust, Solid-State Electrolyte Membrane with Conducting Oxide-Enhanced 3D Nanofiber Networks for Lithium Batteries.

Using a three-dimensional (3D) Li-ion conducting ceramic network, such as Li7La3Zr2O12 (LLZO) garnet-type oxide conductor, has proved to be a promising strategy to form continuous Li ion transfer paths in a polymer-based composite. However, the 3D network produced by brittle ceramic conductor nanofibers fails to provide sufficient mechanical adaptability. In this manuscript, we reported a new 3D ion-conducting network, which is synthesized from highly loaded LLZO nanoparticles reinforced conducting polymer nanofibers, by creating a lightweight continuous and interconnected LLZO-enhanced 3D network to outperform conducting heavy and brittle ceramic nanofibers to offer a new design principle of composite electrolyte membrane featuring all-round properties in mechanical robustness, structural flexibility, high ionic conductivity, lightweight, and high surface area. This composite-nanofiber design overcomes the issues of using ceramic-only nanoparticles, nanowires, or nanofibers in polymer composite electrolyte, and our work can be considered as a new generation of composite electrolyte membrane in composite electrolyte development.

Low Tortuous, Highly Conductive, and High-Areal-Capacity Battery Electrodes Enabled by Through-thickness Aligned Carbon Fiber Framework.

Thick electrode with high-areal-capacity is a practical and promising strategy to increase the energy density of batteries, but development toward thick electrode is limited by the electrochemical performance, mechanical properties, and manufacturing approaches. In this work, we overcome these limitations and report an ultrathick electrode structure, called fiber-aligned thick or FAT electrode, which offers a novel electrode design and a scalable manufacturing strategy for high-areal-capacity battery electrodes. The FAT electrode uses aligned carbon fibers to construct a through-thickness fiber-aligned electrode structure with features of high electrode material loading, low tortuosity, high electrical and thermal conductivity, and good compression property. The low tortuosity of FAT electrode enables fast electrolyte infusion and rapid electron/ion transport, exhibiting a higher capacity retention and lower charge transfer resistance than conventional slurry-casted thick electrode design.

Flexible, solid-state, ion-conducting membrane with 3D garnet nanofiber networks for lithium batteries.

Beyond state-of-the-art lithium-ion battery (LIB) technology with metallic lithium anodes to replace conventional ion intercalation anode materials is highly desirable because of lithium's highest specific capacity (3,860 mA/g) and lowest negative electrochemical potential (∼3.040 V vs. the standard hydrogen electrode). In this work, we report for the first time, to our knowledge, a 3D lithium-ion-conducting ceramic network based on garnet-type Li6.4La3Zr2Al0.2O12 (LLZO) lithium-ion conductor to provide continuous Li(+) transfer channels in a polyethylene oxide (PEO)-based composite. This composite structure further provides structural reinforcement to enhance the mechanical properties of the polymer matrix. The flexible solid-state electrolyte composite membrane exhibited an ionic conductivity of 2.5 × 10(-4) S/cm at room temperature. The membrane can effectively block dendrites in a symmetric Li | electrolyte | Li cell during repeated lithium stripping/plating at room temperature, with a current density of 0.2 mA/cm(2) for around 500 h and a current density of 0.5 mA/cm(2) for over 300 h. These results provide an all solid ion-conducting membrane that can be applied to flexible LIBs and other electrochemical energy storage systems, such as lithium-sulfur batteries.

Negating interfacial impedance in garnet-based solid-state Li metal batteries.

Garnet-type solid-state electrolytes have attracted extensive attention due to their high ionic conductivity, approaching 1 mS cm-1, excellent environmental stability, and wide electrochemical stability window, from lithium metal to ∼6 V. However, to date, there has been little success in the development of high-performance solid-state batteries using these exceptional materials, the major challenge being the high solid-solid interfacial impedance between the garnet electrolyte and electrode materials. In this work, we effectively address the large interfacial impedance between a lithium metal anode and the garnet electrolyte using ultrathin aluminium oxide (Al2O3) by atomic layer deposition. Li7La2.75Ca0.25Zr1.75Nb0.25O12 (LLCZN) is the garnet composition of choice in this work due to its reduced sintering temperature and increased lithium ion conductivity. A significant decrease of interfacial impedance, from 1,710 Ω cm2 to 1 Ω cm2, was observed at room temperature, effectively negating the lithium metal/garnet interfacial impedance. Experimental and computational results reveal that the oxide coating enables wetting of metallic lithium in contact with the garnet electrolyte surface and the lithiated-alumina interface allows effective lithium ion transport between the lithium metal anode and garnet electrolyte. We also demonstrate a working cell with a lithium metal anode, garnet electrolyte and a high-voltage cathode by applying the newly developed interface chemistry.

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.

Carbon Welding by Ultrafast Joule Heating.

Carbon nanomaterials exhibit outstanding electrical and mechanical properties, but these superior properties are often compromised as nanomaterials are assembled into bulk structures. This issue of scaling limits the use of carbon nanostructures and can be attributed to poor physical contacts between nanostructures. To address this challenge, we propose a novel technique to build a 3D interconnected carbon matrix by forming covalent bonds between carbon nanostructures. High temperature Joule heating was applied to bring the carbon nanofiber (CNF) film to temperatures greater than 2500 K at a heating rate of 200 K/min to fuse together adjacent carbon nanofibers with graphitic carbon bonds, forming a 3D continuous carbon network. The bulk electrical conductivity of the carbon matrix increased four orders of magnitude to 380 S/cm with a sheet resistance of 1.75 Ω/sq. The high temperature Joule heating not only enables fast graphitization of carbon materials at high temperature, but also provides a new strategy to build covalently bonded graphitic carbon networks from amorphous carbon source. Because of the high electrical conductivity, good mechanical structures, and anticorrosion properties, the 3D interconnected carbon membrane shows promising applications in energy storage and electrocatalysis fields.

Transient Behavior of the Metal Interface in Lithium Metal-Garnet Batteries.

The interface between solid electrolytes and Li metal is a primary issue for solid-state batteries. Introducing a metal interlayer to conformally coat solid electrolytes can improve the interface wettability of Li metal and reduce the interfacial resistance, but the mechanism of the metal interlayer is unknown. In this work, we used magnesium (Mg) as a model to investigate the effect of a metal coating on the interfacial resistance of a solid electrolyte and Li metal anode. The Li-Mg alloy has low overpotential, leading to a lower interfacial resistance. Our motivation is to understand how the metal interlayer behaves at the interface to promote increased Li-metal wettability of the solid electrolyte surface and reduce interfacial resistance. Surprisingly, we found that the metal coating dissolved in the molten piece of Li and diffused into the bulk Li metal, leading to a small and stable interfacial resistance between the garnet solid electrolyte and the Li metal. We also found that the interfacial resistance did not change with increase in the thickness of the metal coating (5, 10, and 100 nm), due to the transient behavior of the metal interface layer.

Transition from Superlithiophobicity to Superlithiophilicity of Garnet Solid-State Electrolyte.

All-solid-state Li-batteries using solid-state electrolytes (SSEs) offer enhanced safety over conventional Li-ion batteries with organic liquid electrolytes due to the nonflammable nature of SSEs. The superior mechanical strength of SSEs can also protect against Li dendrite penetration, which enables the use of the highest specific capacity (3861 mAh/g) and lowest redox potential (-3.04 V vs standard hydrogen electrode) anode: Li metal. However, contact between the Li metal and SSEs presents a major challenge, where a large polarization occurs at the Li metal/SSE interface. Here, the chemical properties of a promising oxide-based SSE (garnet) changed from "super-lithiophobicity" to "super-lithiophilicity" through an ultrathin coating of amorphous Si deposited by plasma-enhanced chemical vapor deposition (PECVD). The wettability transition is due to the reaction between Li and Si and the in situ formation of lithiated Si. As a result, symmetric cells composed of a Si-coated garnet-structured SSE and Li metal electrodes exhibited much smaller impedance and excellent stability upon plating/stripping cycles compared to cells using bare garnet SSE. Specifically, the interfacial resistance between Li and garnet dramatically decreased from 925 to 127 Ω cm(2) when lithiated Si was formed on the garnet. Our discovery of switchable lithiophobic-lithiophilic surfaces to improve the Li metal/SSE interface opens opportunities for improving many other SSEs.

Dry-Processable Polymer Electrolytes for Solid Manufactured Batteries.

Designing a solid-state electrolyte that satisfies the operating requirements of solid-state batteries is key to solid-state battery applications. The consensus is that solid-state electrolytes need to allow fast ion transport, while providing better interfacial compatibility and mechanical tolerance. Herein, a simple but effective strategy is proposed, combining hard and soft component polymer systems, to exploit a solid polymer electrolyte (SPE) with a 3D network via an in situ graft polymerization. The 3D structure is constructed by a hard cellulose nanocrystal (CNC) as the skeleton and a soft polyacrylonitrile (PAN) as the filler through a dry-processing method. The reported systems have several advantages, including ease of processing, only requiring using an exceedingly small amount of solvent, light weight (ρ = 1.2 g cm-3), excellent mechanical stability (tensile strength of 9.5 MPa), and high ionic conductivity (3.9 × 10-4 S cm-1, 18 °C) and migration number (tLi+ = 0.8). In particular, the high conductivity is enabled: the efficient Li+ transportation path constructed between CNC-PAN powders and abundant sulfonate radicals and hydroxyl groups on the CNC surface acts as the bridge of Li+ transition. When the CNCs are grafted onto the PAN polymer, the dipole-dipole interaction between the nitrile groups of the PAN and the hydroxyl groups of the CNCs can help to improve the mechanical stability and ionic conductivity of the SPE. Moreover, a tightly formed interface between SPE and LiFePO4 (LFP)/carbon black/SPE cathode can be achieved in an assembled solid-state battery by hot pressing, thus further enhancing the battery's performance.

Carbon Additive Manufacturing with a Near-Replica "Green-to-Brown" Transformation.

Nanocomposites containing nanoscale materials offer exciting opportunities to encode nanoscale features into macroscale dimensions, which produces unprecedented impact in material design and application. However, conventional methods cannot process nanocomposites with a high particle loading, as well as nanocomposites with the ability to be tailored at multiple scales. A composite architected mesoscale process strategy that brings particle loading nanoscale materials combined with multiscale features including nanoscale manipulation, mesoscale architecture, and macroscale formation to create spatially programmed nanocomposites with high particle loading and multiscale tailorability is reported. The process features a low-shrinking (<10%) "green-to-brown" transformation, making a near-geometric replica of the 3D design to produce a "brown" part with full nanomaterials to allow further matrix infill. This demonstration includes additively manufactured carbon nanocomposites containing carbon nanotubes (CNTs) and thermoset epoxy, leading to multiscale CNTs tailorability, performance improvement, and 3D complex geometry feasibility. The process can produce nanomaterial-assembled architectures with 3D geometry and multiscale features and can incorporate a wide range of matrix materials, such as polymers, metals, and ceramics, to fabricate nanocomposites for new device structures and applications.

Stretchable One-Dimensional Conductors for Wearable Applications.

Continuous, one-dimensional (1D) stretchable conductors have attracted significant attention for the development of wearables and soft-matter electronics. Through the use of advanced spinning, printing, and textile technologies, 1D stretchable conductors in the forms of fibers, wires, and yarns can be designed and engineered to meet the demanding requirements for different wearable applications. Several crucial parameters, such as microarchitecture, conductivity, stretchability, and scalability, play essential roles in designing and developing wearable devices and intelligent textiles. Methodologies and fabrication processes have successfully realized 1D conductors that are highly conductive, strong, lightweight, stretchable, and conformable and can be readily integrated with common fabrics and soft matter. This review summarizes the latest advances in continuous, 1D stretchable conductors and emphasizes recent developments in materials, methodologies, fabrication processes, and strategies geared toward applications in electrical interconnects, mechanical sensors, actuators, and heaters. This review classifies 1D conductors into three categories on the basis of their electrical responses: (1) rigid 1D conductors, (2) piezoresistive 1D conductors, and (3) resistance-stable 1D conductors. This review also evaluates the present challenges in these areas and presents perspectives for improving the performance of stretchable 1D conductors for wearable textile and flexible electronic applications.

3D-Printed Parahydrophobic Functional Textile with a Hierarchical Nanomicroscale Structure.

Functional textiles with superhydrophobicity and high adhesion to water, called parahydrophobic, are attracting increasing attention from industry and academia. The hierarchical (micronanoscale) surface patterns in nature provide an excellent reference for the manufacture of parahydrophobic functional textiles. However, the replication of the complex parahydrophobic micronanostructures in nature exceeds the ability of traditional manufacturing strategies, which makes it difficult to accurately manufacture controllable nanostructures on yarn and textiles. Herein, a two-photon femtosecond laser direct writing strategy with nanoscale process capability was utilized to accurately construct the functional parahydrophobic yarn with a diameter of 900 µm. Inspired by rose petals, the parahydrophobic yarn is composed of a hollow round tube, regularly arranged micropapillae (the diameter is 109 µm), and nanofolds (the distance is 800 nm) on papillae. The bionic yarn exhibited a superior parahydrophobic behavior, where the liquid droplet not only was firmly adhered to the bionic yarn at an inverted angle (180°) but also presented as spherical on the yarn (the maximum water contact angle is 159°). The fabric woven by the bionic yarn also exhibited liquid droplet-catching ability even when tilted vertically or turned upside down. Based on the excellent parahydrophobic function of bionic yarn, we demonstrated a glove that has very wide application potential in the fields of water droplet-based transportation, manipulation, microreactors, microextractors, etc.

Rapid Nanowelding of Carbon Coatings onto Glass Fibers by Electrothermal Shock.

With the rapid development of nanomanufacturing, scaling up of nanomaterials requires advanced manufacturing technology to composite nanomaterials with disparate materials (ceramics, metals, and polymers) to achieve hybrid properties and coupling performances for practical applications. Attempts to assemble nanomaterials onto macroscopic materials are often accompanied by the loss of exceptional nanoscale properties during the fabrication process, which is mainly due to the poor contacts between carbon nanomaterials and macroscopic bulk materials. In this work, we proposed a novel cross-scale manufacturing concept to process disparate materials in different length scales and successfully demonstrated an electrothermal shock approach to process the nanoscale material (e.g., carbon nanotubes) and macroscale (e.g., glass fiber) with good bonding and excellent mechanical property for emerging applications. The excellent performance and potentially lower cost of the electrothermal shock technology offers a continuous, ultrafast, energy-efficient, and roll-to-roll process as a promising heating solution for cross-scale manufacturing.

Electric Field-Induced Assembly and Alignment of Silver-Coated Cellulose for Polymer Composite Films with Enhanced Dielectric Permittivity and Anisotropic Light Transmission.

Multifarious wearable electronics with flexible touch screens have been invented for extensive outdoor activities. One challenge associated with these wearable electronics is the development of materials with both high dielectric permittivity and anisotropic light transmission, which is responsible for high touch sensitivity and screen peep-proof protection, respectively. Herein, we demonstrated a scalable approach for assembling and aligning anisotropic cellulose in a polymer matrix through the thickness direction via the assistance of an electric field to address this challenge. The alignment of silver-coated fibrillated celluloses in the polymer matrix not only significantly increases dielectric permittivity but also effectively enhances optical anisotropy. The impact of alignment degree and filler content on the dielectric and optical properties of polymer composite films has been systematically studied. The kinetics and aligning mechanisms of silver-coated fibrillated celluloses are revealed by in situ optical microscope images while an electric field is applied. We believe that this study provides a facile strategy to enhance both dielectric permittivity and optical anisotropy of polymer composite films by the alignment of embedding nanoparticles via an AC electric field, which is essential for future flexible electronics and display technology.

Ultrafast, Controllable Synthesis of Sub-Nano Metallic Clusters through Defect Engineering.

Supported metallic nanoclusters (NCs, < 2 nm) are of great interests in various catalytic reactions with enhanced activities and selectivities, yet it is still challenging to efficiently and controllably synthesize ultrasmall NCs with a high-dispersal density. Here we report the in situ synthesis of surfactant-free, ultrasmall, and uniform NCs via a rapid thermal shock on defective substrates. This is achieved by using high-temperature synthesis with extremely fast kinetics while limiting the synthesis time down to milliseconds (e.g., ∼1800 K for 55 ms) to avoid aggregation. Through defect engineering and optimized loading, the particle size can be robustly tuned from >50 nm nanoparticles to <1 nm uniform NCs with a high-dispersal density. We demonstrate that the ultrasmall NCs exhibit drastically improved activities for catalytic CO oxidation as compared to their nanoparticulated counterparts. In addition, the reported method shows generality in synthesizing most metallic NCs (e.g., Pt, Ru, Ir, Ni) in an extremely facile and efficient manner. The ultrafast and controllable synthesis of uniform, high-density, and size-controllable NCs paves the way for the utilization and nanomanufacturing of NCs for a range of catalytic reactions.

Epitaxial Welding of Carbon Nanotube Networks for Aqueous Battery Current Collectors.

Carbon nanomaterials are desirable candidates for lightweight, highly conductive, and corrosion-resistant current collectors. However, a key obstacle is their weak interconnection between adjacent nanostructures, which renders orders of magnitude lower electrical conductivity and mechanical strength in the bulk assemblies. Here we report an "epitaxial welding" strategy to engineer carbon nanotubes (CNTs) into highly crystalline and interconnected structures. Solution-based polyacrylonitrile was conformally coated on CNTs as "nanoglue" to physically join CNTs into a network, followed by a rapid high-temperature annealing (>2800 K, overall ∼30 min) to graphitize the polymer coating into crystalline layers that also bridge the adjacent CNTs to form an interconnected structure. The contact-welded CNTs (W-CNTs) exhibit both a high conductivity (∼1500 S/cm) and a high tensile strength (∼120 MPa), which are 5 and 20 times higher than the unwelded CNTs, respectively. In addition, the W-CNTs display chemical and electrochemical stabilities in strong acidic/alkaline electrolytes (>6 mol/L) when potentiostatically stressing at both cathodic and anodic potentials. With these exceptional properties, the W-CNT films are optimal as high-performance current collectors and were demonstrated in the state-of-the-art aqueous battery using a "water-in-salt" electrolyte.

Inverted battery design as ion generator for interfacing with biosystems.

In a lithium-ion battery, electrons are released from the anode and go through an external electronic circuit to power devices, while ions simultaneously transfer through internal ionic media to meet with electrons at the cathode. Inspired by the fundamental electrochemistry of the lithium-ion battery, we envision a cell that can generate a current of ions instead of electrons, so that ions can be used for potential applications in biosystems. Based on this concept, we report an 'electron battery' configuration in which ions travel through an external circuit to interact with the intended biosystem whereas electrons are transported internally. As a proof-of-concept, we demonstrate the application of the electron battery by stimulating a monolayer of cultured cells, which fluoresces a calcium ion wave at a controlled ionic current. Electron batteries with the capability to generate a tunable ionic current could pave the way towards precise ion-system control in a broad range of biological applications.

Reducing Interfacial Resistance between Garnet-Structured Solid-State Electrolyte and Li-Metal Anode by a Germanium Layer.

Substantial efforts are underway to develop all-solid-state Li batteries (SSLiBs) toward high safety, high power density, and high energy density. Garnet-structured solid-state electrolyte exhibits great promise for SSLiBs owing to its high Li-ion conductivity, wide potential window, and sufficient thermal/chemical stability. A major challenge of garnet is that the contact between the garnet and the Li-metal anodes is poor due to the rigidity of the garnet, which leads to limited active sites and large interfacial resistance. This study proposes a new methodology for reducing the garnet/Li-metal interfacial resistance by depositing a thin germanium (Ge) (20 nm) layer on garnet. By applying this approach, the garnet/Li-metal interfacial resistance decreases from ≈900 to ≈115 Ω cm2 due to an alloying reaction between the Li metal and the Ge. In agreement with experiments, first-principles calculation confirms the good stability and improved wetting at the interface between the lithiated Ge layer and garnet. In this way, this unique Ge modification technique enables a stable cycling performance of a full cell of lithium metal, garnet electrolyte, and LiFePO4 cathode at room temperature.

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.

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.