Programmable DNA Interphase Layers for High-Performance Anode-Free Lithium Metal Batteries.

Anode-free lithium (Li) metal batteries are promising candidates for advanced energy storage, attributed to their appealing characteristics such as high energy density, low cost, and convenient production. However, their major challenges lie in the poor cycling and rate performance owing to the inferior reversibility and kinetics of Li plating and stripping, which significantly hinder their real-world applications. Here, it is demonstrated that deoxyribonucleic acid (DNA), the most important genetic material in nature, can serve as a highly programmable interphase layer for innovation of anode-free Li metal batteries. It is found that the abundant base pairs in DNA can contribute transient Li-N bonds that facilitate homogeneous Li+ flux, thus resulting in excellent Li plating/stripping kinetics and reversibility even at a harsh areal current of 15 mA cm-2. The anode-free LiFePO4 full batteries based on an ultrathin (0.12 µm) and ultralight (≈0.01 mg cm-2) DNA interphase layer show high CEs (≈99.1%) over 400 cycles, corresponding to an increase of ≈186% compared with bare copper (Cu) foil. These results shed light on the excellent programmability of DNA as a new family of interphase materials for anode-free batteries, and provide a new paradigm for future battery innovation toward high programmability, high sustainability, and remarkable electrochemical performance.

A dynamically stable self-healable wire based on mechanical-electrical coupling.

The rise in wearable electronics has witnessed the advancement of self-healable wires, which are capable of recovering mechanical and electrical properties upon structural damage. However, their highly fluctuating electrical resistances in the range of hundreds to thousands of ohms under dynamic conditions such as bending, pressing, stretching and tremoring may seriously degrade the precision and continuity of the resulting electronic devices, thus severely hindering their wearable applications. Here, we report a new family of self-healable wires with high strengths and stable electrical conductivities under dynamic conditions, inspired by mechanical-electrical coupling of the myelinated axon in nature. Our self-healable wire based on mechanical-electrical coupling between the structural and conductive components has significantly improved the electrical stability under dynamic scenarios, enabling precise monitoring of human health status and daily activities, even in the case of limb tremors from simulated Parkinson's disease. Our mechanical-electrical coupling strategy opens a new avenue for the development of dynamically stable electrodes and devices toward real-world wearable applications.

A rechargeable calcium-oxygen battery that operates at room temperature.

Calcium-oxygen (Ca-O2) batteries can theoretically afford high capacity by the reduction of O2 to calcium oxide compounds (CaOx) at low cost1-5. Yet, a rechargeable Ca-O2 battery that operates at room temperature has not been achieved because the CaOx/O2 chemistry typically involves inert discharge products and few electrolytes can accommodate both a highly reductive Ca metal anode and O2. Here we report a Ca-O2 battery that is rechargeable for 700 cycles at room temperature. Our battery relies on a highly reversible two-electron redox to form chemically reactive calcium peroxide (CaO2) as the discharge product. Using a durable ionic liquid-based electrolyte, this two-electron reaction is enabled by the facilitated Ca plating-stripping in the Ca metal anode at room temperature and improved CaO2/O2 redox in the air cathode. We show the proposed Ca-O2 battery is stable in air and can be made into flexible fibres that are weaved into textile batteries for next-generation wearable systems.

A rechargeable Ca/Cl2 battery.

Rechargeable calcium (Ca) metal batteries are promising candidates for sustainable energy storage due to the abundance of Ca in Earth's crust and the advantageous theoretical capacity and voltage of these batteries. However, the development of practical Ca metal batteries has been severely hampered by the current cathode chemistries, which limit the available energy and power densities, as well as their insufficient capacity retention and low-temperature capability. Here, we describe the rechargeable Ca/Cl2 battery based on a reversible cathode redox reaction between CaCl2 and Cl2, which is enabled by the use of lithium difluoro(oxalate)borate as a key electrolyte mediator to facilitate the dissociation and distribution of Cl-based species and Ca2+. Our rechargeable Ca/Cl2 battery can deliver discharge voltages of 3 V and exhibits remarkable specific capacity (1000 mAh g-1) and rate capability (500 mA g-1). In addition, the excellent capacity retention (96.5% after 30 days) and low-temperature capability (down to 0 °C) allow us to overcome the long-standing bottleneck of rechargeable Ca metal batteries.

Ultrahigh-Rate Na/Cl2 Batteries Through Improved Electron and Ion Transport by Heteroatom-Doped Bicontinuous-Structured Carbon.

Rechargeable sodium/chlorine (Na/Cl2 ) batteries are emerging candidates for sustainable energy storage owing to their superior energy densities and the high abundance of Na and Cl elements. However, their practical applications have been plagued by the poor rate performance (e.g., a maximum discharge current density of 150 mA g-1 ), as the widely used carbon nanosphere cathodes show both sluggish electron-ion transport and reaction kinetics. Here, by mimicking the sufficient mass and energy transport in a sponge, we report a bicontinuous-structured carbon cubosome with heteroatomic doping, which allows efficient Na+ and electron transport and promotes Cl2 adsorption and conversion, thus unlocking ultrahigh-rate Na/Cl2 batteries, e.g., a maximum discharge current density of 16,000 mA g-1 that is more than two orders of magnitude higher than previous reports. The optimized solid-liquid-gas (carbon-electrolyte-Cl2 ) triple interfaces further contribute to a maximum reversible capacity and cycle life of 2,000 mAh g-1 and 250 cycles, respectively. This study establishes a universal approach for improving the sluggish kinetics of conversion-type battery reactions, and provides a new paradigm to resolve the long-standing dilemma between high energy and power densities in energy storage devices.

Unlocking Reversible Silicon Redox for High-Performing Chlorine Batteries.

Chlorine (Cl)-based batteries such as Li/Cl2 batteries are recognized as promising candidates for energy storage with low cost and high performance. However, the current use of Li metal anodes in Cl-based batteries has raised serious concerns regarding safety, cost, and production complexity. More importantly, the well-documented parasitic reactions between Li metal and Cl-based electrolytes require a large excess of Li metal, which inevitably sacrifices the electrochemical performance of the full cell. Therefore, it is crucial but challenging to establish new anode chemistry, particularly with electrochemical reversibility, for Cl-based batteries. Here we show, for the first time, reversible Si redox in Cl-based batteries through efficient electrolyte dilution and anode/electrolyte interface passivation using 1,2-dichloroethane and cyclized polyacrylonitrile as key mediators. Our Si anode chemistry enables significantly increased cycling stability and shelf lives compared with conventional Li metal anodes. It also avoids the use of a large excess of anode materials, thus enabling the first rechargeable Cl2 full battery with remarkable energy and power densities of 809 Wh kg-1 and 4,277 W kg-1 , respectively. The Si anode chemistry affords fast kinetics with remarkable rate capability and low-temperature electrochemical performance, indicating its great potential in practical applications.

Unlocking Deep and Fast Potassium-Ion Storage through Phosphorus Heterostructure.

Potassium-ion battery represents a promising alternative of conventional lithium-ion batteries in sustainable and grid-scale energy storage. Among various anode materials, elemental phosphorus (P) has been actively pursued owing to the ideal natural abundance, theoretical capacity, and electrode potential. However, the sluggish redox kinetics of elemental P has hindered fast and deep potassiation process toward the formation of final potassiation product (K3 P), which leads to inferior reversible capacity and rate performance. Here, it is shown that rational design on black/red P heterostructure can significantly improve K-ion adsorption, injection and immigration, thus for the first time unlocking K3 P as the reversible potassiation product for elemental P anodes. Density functional theory calculations reveal the fast adsorption and diffusion kinetics of K-ion at the heterostructure interface, which delivers a highly reversible specific capacity of 923 mAh g-1 at 0.05 A g-1 , excellent rate capability (335 mAh g-1 at 1 A g-1 ), and cycling performance (83.3% capacity retention at 0.8 A g-1 after 300 cycles). These results can unlock other sluggish and irreversible battery chemistries toward sustainable and high-performing energy storage.

Anode-Free Lithium Metal Batteries Based on an Ultrathin and Respirable Interphase Layer.

Anode-free lithium (Li) metal batteries are desirable candidates in pursuit of high-energy-density batteries. However, their poor cycling performances originated from the unsatisfactory reversibility of Li plating/stripping remains a grand challenge. Here we show a facile and scalable approach to produce high-performing anode-free Li metal batteries using a bioinspired and ultrathin (250 nm) interphase layer comprised of triethylamine germanate. The derived tertiary amine and Lix Ge alloy showed enhanced adsorption energy that significantly promoted Li-ion adsorption, nucleation and deposition, contributing to a reversible expansion/shrinkage process upon Li plating/stripping. Impressive Li plating/stripping Coulombic efficiencies (CEs) of ≈99.3 % were achieved for 250 cycles in Li/Cu cells. In addition, the anode-free LiFePO4 full batteries demonstrated maximal energy and power densities of 527 Wh kg-1 and 1554 W kg-1 , respectively, and remarkable cycling stability (over 250 cycles with an average CE of 99.4 %) at a practical areal capacity of ≈3 mAh cm-2 , the highest among state-of-the-art anode-free LiFePO4 batteries. Our ultrathin and respirable interphase layer presents a promising way to fully unlock large-scale production of anode-free batteries.

Phase Engineering of Metastable Transition Metal Dichalcogenides via Ionic Liquid Assisted Synthesis.

Metallic group VIB transition metal dichalcogenides (1T-TMDs) have attracted great interest because of their outstanding performance in electrocatalysis, supercapacitors, batteries, and so on, whereas the strict fabrication conditions and thermodynamical metastability of 1T-TMDs greatly restrict their extensive applications. Therefore, it is significant to obtain stable and high-concentration 1T-TMDs in a simple and large-scale strategy. Herein, we report a facile and large-scale synthesis of high-concentration 1T-TMDs via an ionic liquid (IL) assisted hydrothermal strategy, including 1T-MoS2 (the obtained MoS2 sample was denoted as MoS2-IL), 1T-WS2, 1T-MoSe2, and 1T-WSe2. More importantly, we found that IL can adsorb on the surface of 1T-MoS2, where the steric hindrance, π-π stacking, and hydrogen bonds of ionic liquid collectively induce the formation of the 1T-MoS2. In addition, DFT calculation reveals that electrons are transferred from [BMIM]SCN (1-butyl-3-methylimidazolium thiocyanate) to 1T-MoS2 layers by hydrogen bonds, which enhances the stability of 1T-MoS2, so the MoS2-IL performs with high stability for 180 days at room temperature without obvious change. Furthermore, the MoS2-IL exhibits excellent HER performance with an overpotential of 196 mV at 10 mA cm-2 in acid conditions.

Retrospective Analysis of the Accuracy of High-Frequency Ultrasound for Pancreaticobiliary Maljunction in Pediatrics at a Single Center.

Objective: To determine the clinical value of high-frequency ultrasonography (US) in the evaluation and diagnosis of pancreaticobiliary maljunction (PBM) among children. Methods: The clinical subjects consisted of 31 pediatric patients who were diagnosed with PBM from January 2015 to May 2021 in Fujian Provincial Maternity and Children's Hospital. The primary outcomes included diagnosis accuracy, imaging characteristics of each type of PBM based on JSPBM, time length of operation, and cost of service. Secondary outcomes were the serum amylase and bilirubin levels. Results: The diagnostic accuracy of US was 90.3% and comparable to the other imaging methods-MRCP (82.6%), IOC (79.2%), and ERCP (100%), respectively. The time length of operation and direct cost were significantly lower than other imaging pathways. Stenotic type (A) is associated with a high internal diameter of CBD, and dilated channel type (C) presents increased internal diameter and length of CC as well as internal diameter of PD. There were higher levels of the serum bilirubin seen in type A and of serum amylase in type C compared with others. Conclusion: High-frequency US is a safe, cost-effective, and non-invasive imaging tool for the diagnosis and evaluation of PBM in pediatrics.

Ionic liquid-hydroxide-mediated low-temperature synthesis of high-entropy perovskite oxide nanoparticles.

High-entropy perovskite oxides (HEPOs) are attracting significant attention due to their unique structures, unprecedented properties and great application potential in many fields, while available synthetic methods have many shortcomings; so it is still a challenge to develop a simple, low-cost and environment-friendly synthetic strategy for HEPOs. Herein, a novel synthetic strategy is reported for HEPOs using an ionic liquid (IL)-hydroxide-mediated technique at a low temperature and normal atmospheric pressure. The synthesized HEPOs, including Ba(FeNbTiZrTa)O3, Ba(MnNbTiZrTa)O3, Ba(FeSnTiZrTa)O3 and Ba(FeVTiZrTa)O3, exhibit a cubic structure and a dispersed nanoparticle morphology (particle size of 20-60 nm). The formation process of HEPOs in an IL-KOH system can be described as follows: first, B-site metal source compounds are dissolved in IL-KOH medium to form hydroxyl complexes; second, the complexes further dehydrate, condensate and react with Ba2+ ions to form the crystal nuclei of HEPOs under the synergistic effect of reaction temperature and basicity; third, the growth of HEPO nuclei is completed by the Ostwald ripening process. In these processes, KOH not only plays a role as a solvent, but also provides sufficient OH- concentration for the formation and condensation of B-site metal hydroxyl complexes, while the IL also makes significant contributions: first, a lower reaction temperature and lower dosage of KOH are achieved by the use of the IL; second, the IL with good dissolving ability and low surface tensions can promote the nucleation rate of HEPOs and improve the Ostwald ripening process; third, the compact adsorption of the IL on the surface of products ensures a small particle size and high dispersion of HEPO nanoparticles to a certain extent. In brief, the technique provides an innovative, low-cost, simple and nontoxic strategy for the synthesis of HEPOs, which can be extended to other high-entropy materials.

Controllable Synthesis of a Loofah-Like Cobalt-Nickel Selenide Network as an Efficient Electrocatalyst for the Hydrogen Evolution Reaction.

The rational design and construction of noble metal-free electrocatalysts featuring high efficiency and low cost are important for the hydrogen evolution reaction (HER). A significant development in the synthesis of a loofah-like Co0.6Ni0.4Se2 architecture (expressed as Co0.6Ni0.4Se2-LN) electrocatalyst on carbon cloth through a three-step method is reported. Both the ionic liquid 1-dodecyl-3-methylimidazolium acetate (IL, [C12MIm]Ac) and the molar ratio of Co to Ni play a pivotal role in the synthesis of Co0.6Ni0.4Se2-LN with 3D hierarchical architecture. Co0.6Ni0.4Se2-LN exposes abundant active sites and provides hierarchical and stable transfer channels for both electrolyte ions and electrons, which results in outstanding HER performance. Impressively, Co0.6Ni0.4Se2-LN shows a low overpotential of 163 mV at 10 mA cm-2, a small Tafel slope of 40 mV dec-1, and superior stability to continuously catalyze the generation of H2 for 40 h. This study offers a new perspective to the synthesis of high-efficiency inexpensive electrocatalysts for HER and also presents a good example for investigating the potential application of ILs in the synthesis of functional materials.

Design and Synthesis of a Reduced Graphene Oxide/Patronite Composite with Enhanced Lithium-Ion Storage Performance.

The construction of graphene-based composites is a novel electrode material design strategy and has become a promising field in new energy material research. However, the rational design principle is still poorly understood, and the synthetic technology urgently needs to be expanded. Here, a novel strategy for the synthesis of a reduced graphene oxide (rGO)/VS4 nanoparticle (NP) composite is reported using an ionic liquid (IL)-assisted hydrothermal method. The synergistic effects of graphene and IL, which include the π-cation/anion interactions of graphene, the capping agent effect of IL, and their π-π stacking interaction, are responsible for the synthesis of the composite, achieving delicate tailoring of VS4 NPs as well as their homogeneous dispersal on the surface of rGO nanosheets. The superior nanostructure of the composite results in enhanced lithium-ion storage performance, such as improved cyclic stability (1009 mA h g-1 at 0.1 A g-1 after 150 cycles and 788 mA h g-1 after 240 cycles even at 1 A g-1) and rate capability (1540 and 621 mA h g-1 at 0.1 and 2 A g-1, respectively). This strategy provides an effective new approach for designing graphene composites and is expected to be applicable in the design of other rGO/transition-metal sulfide composites for energy storage.