Backside Coating for Stable Zn Anode with High Utilization Rate.

Stable Zn anodes with high utilization rate are urgently required to promote the specific and volumetric energy densities of Zn-ion batteries for practical applications. Herein, contrary to the widely utilized surface coating on Zn anodes, this work shows that a zinc foil with a backside coated layer delivers much enhanced cycling stability even under high depth of discharge. The backside coating significantly reduces stress concentration, accelerates heat diffusion, and facilitates electron transfer, thus effectively preventing dendrite growth and structural damage at high Zn utilization. As a result, the developed anode can be stably cycled for 334 h at 85.5% Zn utilization, which outperforms bare Zn and previously reported results on surface-coated Zn foils. An NVO-based full cell also shows stable performance with high Zn utilization rate (69.4%), low negative-positive electrodes ratio (1.44), and high specific/volumetric energy densities (155.8 Wh kg-1/178 Wh L-1), which accelerates the progress toward practical zinc-ion batteries.

High intrinsic phase stability of ultrathin 2M WS2.

Metallic 2M or 1T'-phase transition metal dichalcogenides (TMDs) attract increasing interests owing to their fascinating physicochemical properties, such as superconductivity, optical nonlinearity, and enhanced electrochemical activity. However, these TMDs are metastable and tend to transform to the thermodynamically stable 2H phase. In this study, through systematic investigation and theoretical simulation of phase change of 2M WS2, we demonstrate that ultrathin 2M WS2 has significantly higher intrinsic thermal stabilities than the bulk counterparts. The 2M-to-2H phase transition temperature increases from 120 °C to 210 °C in the air as thickness of WS2 is reduced from bulk to bilayer. Monolayered 1T' WS2 can withstand temperatures up to 350 °C in the air before being oxidized, and up to 450 °C in argon atmosphere before transforming to 1H phase. The higher stability of thinner 2M WS2 is attributed to stiffened intralayer bonds, enhanced thermal conductivity and higher average barrier per layer during the layer(s)-by-layer(s) phase transition process. The observed high intrinsic phase stability can expand the practical applications of ultrathin 2M TMDs.

Bio-Inspired Trace Hydroxyl-Rich Electrolyte Additives for High-Rate and Stable Zn-Ion Batteries at Low Temperatures.

High-rate and stable Zn-ion batteries working at low temperatures are highly desirable for practical applications, but are challenged by sluggish kinetics and severe corrosion. Herein, inspired by frost-resistant plants, we report trace hydroxyl-rich electrolyte additives that implement a dual remodeling effect for high-performance low-temperature Zn-ion batteries. The additive with high Zn absorbability not only remodels Zn2+ primary solvent shell by alternating H2 O molecules, but also forms a shielding layer thus remodeling the Zn surface, which effectively enhances fast Zn2+ de-solvation reaction kinetics and prohibits Zn anode corrosion. Taking trace α-D-glucose (αDG) as a demonstration, the electrolyte obtains a low freezing point of -55.3 °C, and the Zn//Zn cell can stably cycle for 2000 h at 5 mA cm-2 under -25 °C, with a high cumulative capacity of 5000 mAh cm-2 . A full battery that stably operates for 10000 cycles at -50 °C is also demonstrated.

Liquid Metal-Based Stable and Stretchable Zn-Ion Battery for Electronic Textiles.

Electronic textiles harmoniously interact with the human body and the surrounding environment, offering tremendous interest in smart wearable electronics. However, their wide application faces challenges due to the lack of stable and stretchable power electrodes/devices with multifunctional design. Herein, an intrinsically stretchable liquid metal-based fibrous anode for a stable Zn-ion battery (ZIB) is reported. Benefiting from the liquid feature and superior deformability of the liquid metal, optimized Zn ion concentration distribution and Zn (002) deposition behavior are observed, which result in dendrite-free performance even under stretching. With a strain of 50%, the ZIB maintains a high capacity of 139.8 mAh cm-3 (corresponding to 83.0% of the initial value) after 300 cycles, outperforming bare Zn fiber-based ZIB. The fibrous ZIB seamlessly integrates with the sensor, Joule heater, and wirelessly charging device, which provides a stable power supply for human signal monitoring and personal thermal management, holding promise for the application of wearable multifunctional electronic textiles.

Sphere-Confined Reversible Zn Deposition for Stable Alkaline Aqueous Batteries.

The practical applications of alkaline zinc-based batteries are challenged by poor rechargeability with an insufficient zinc utilization ratio. Herein, a sphere-confined reversible zinc deposition behavior from a free-standing Zn anode is reported, which is composed of bi-continuous ZnO-protected interconnected and hollowed Zn microspheres by the Kirkendall effect. The cross-linked Zn network with in situ formed outer ZnO shell and inner hollow space not only inhibits side reactions but also ensures long-range conductivity and accommodates shape change, which induces preferential reversible zinc dissolution-deposition process in the inner space and maintains structural integrity even under high zinc utilization ratio. As a result, the Zn electrode can be stably cycled for 390 h at a high current density of 20 mA cm-2 (60% depth of discharge), outperforming previously reported alkaline Zn anodes. A stable zinc-nickel oxide hydroxide battery with a high cumulative capacity of 8532 mAh cm-2 at 60% depth of discharge is also demonstrated.

Functional Laminated Fiber Scaffold Based on Titanium Monoxide for Lithium Metal-Based Batteries.

Lithium metal-based rechargeable batteries are attracting increasing attention due to their high theoretical specific capacity and energy density. However, the dendrite growth leads to short circuits or even explosions and rapid depletion of active materials and electrolytes. Here, a functionalized and laminated scaffold (PVDF/TiO@C fiber) based on lithiophilic titanium monoxide is rationally designed to inhibit dendrite growth. Specifically, the bottom TiO@C fiber sublayer provides rich Li nucleation sites and facilitates the formation of stable solid electrolyte interphase. Together with the top lithiophobic PVDF sublayer, the prepared freestanding scaffold can effectively suppress the growth of Li dendrite and ensure stable Li plating/stripping. Based on the dendrite-free deposition, the Li/PVDF/TiO@ C fiber anode enables over 1000 h at a current density of 1 mA cm-2 in a symmetrical cell and delivers superior electrochemical performance in both Li || LFP and Li-S batteries. The functional laminated fiber scaffold design provides essential insights for obtaining high-performance lithium metal anodes.

Flexible Energy Storage Devices to Power the Future.

The field of flexible electronics is a crucial driver of technological advancement, with a strong connection to human life and a unique role in various areas such as wearable devices and healthcare. Consequently, there is an urgent demand for flexible energy storage devices (FESDs) to cater to the energy storage needs of various forms of flexible products. FESDs can be classified into three categories based on spatial dimension, all of which share the features of excellent electrochemical performance, reliable safety, and superb flexibility. In this review, the application scenarios of FESDs are introduced and the main representative devices applied in disparate fields are summarized first. More specifically, it focuses on three types of FESDs in matched application scenarios from both structural and material aspects. Finally, the challenges that hinder the practical application of FESDs and the views on current barriers are presented.

Ultraviolet-Assisted Printing of Flexible Solid-State Zn-Ion Battery with a Heterostructure Electrolyte.

Flexible solid-state Zn-ion batteries (ZIBs) have garnered considerable attention for next-generation power sources, but the corrosion, dendrite growth, and interfacial problems severely hinder their practical applications. Herein, a high-performance flexible solid-state ZIB with a unique heterostructure electrolyte is facilely fabricated through ultraviolet-assisted printing strategy. The solid polymer/hydrogel heterostructure matrix not only isolates water molecules and optimizes electric field distribution for dendrite-free anode, but also facilitates fast and in-depth Zn2+ transport in the cathode. The in situ ultraviolet-assisted printing creates cross-linked and well-bonded interfaces between the electrodes and the electrolyte, enabling low ionic transfer resistance and high mechanical stability. As a result, the heterostructure electrolyte based ZIB outperforms single-electrolyte based cells. It not only delivers a high capacity of 442.2 mAh g-1 with long cycling life of 900 cycles at 2 A g-1 , but also maintains stable operation under mechanical bending and high-pressure compression in a wide temperature range (-20 °C to 100 °C).

Wood-Derived Continuously Oriented Three-Phase Interfacial Channels for High-Performance Quasi-Solid-State Alkaline Zinc Batteries.

Although recently developed hybrid zinc (Zn) batteries integrate the benefits of both alkaline Zn and Zn-air batteries, the kinetics of the electrocatalytic oxygen reaction and mass transfer of the electrolyte, which are limited by the mismatched and disordered multiphase reaction's interfacial transfer channels, considerably inhibit the performance of hybrid Zn batteries. In this work, novel, continuously oriented three-phase interfacial channels at the cathode derived from the natural structure of pine wood are developed to address these challenges. A pine wood chip is carbonized and asymmetrically loaded with a hydrophilic active material to achieve the creation of a wood-derived cathode that integrates the active material, current collector, and continuously oriented three-phase reaction interfacial channels, which allows the reaction dynamics to be accelerated. Consequently, the assembled quasi-solid-state hybrid battery performs an extra charge-discharge process beyond that performed by a typical nickel (Ni)-Zn battery, resulting in a wide operating voltage range of 0.6-2.0 V and a superior specific capacity of 656.5 mAh g-1 , in addition to an excellent energy density (644.7 Wh kg-1 ) and good durability. The ≈370% capacity improvement relative to the Ni-Zn battery alone makes the hybrid battery one of the best-performing alkaline Zn batteries.

Gradient design of imprinted anode for stable Zn-ion batteries.

Achieving long-term stable zinc anodes at high currents/capacities remains a great challenge for practical rechargeable zinc-ion batteries. Herein, we report an imprinted gradient zinc electrode that integrates gradient conductivity and hydrophilicity for long-term dendrite-free zinc-ion batteries. The gradient design not only effectively prohibits side reactions between the electrolyte and the zinc anode, but also synergistically optimizes electric field distribution, zinc ion flux and local current density, which induces preferentially deposited zinc in the bottom of the microchannels and suppresses dendrite growth even under high current densities/capacities. As a result, the imprinted gradient zinc anode can be stably cycled for 200 h at a high current density/capacity of 10 mA cm-2/10 mAh cm-2, with a high cumulative capacity of 1000 mAh cm-2, which outperforms the none-gradient counterparts and bare zinc. The imprinted gradient design can be easily scaled up, and a high-performance large-area pouch cell (4*5 cm2) is also demonstrated.

3D Printed Graphene-Based Metamaterials: Guesting Multi-Functionality in One Gain.

Advanced functional materials with fascinating properties and extended structural design have greatly broadened their applications. Metamaterials, exhibiting unprecedented physical properties (mechanical, electromagnetic, acoustic, etc.), are considered frontiers of physics, material science, and engineering. With the emerging 3D printing technology, the manufacturing of metamaterials becomes much more convenient. Graphene, due to its superior properties such as large surface area, superior electrical/thermal conductivity, and outstanding mechanical properties, shows promising applications to add multi-functionality into existing metamaterials for various applications. In this review, the aim is to outline the latest developments and applications of 3D printed graphene-based metamaterials. The structure design of different types of metamaterials and the fabrication strategies for 3D printed graphene-based materials are first reviewed. Then the representative explorations of 3D printed graphene-based metamaterials and multi-functionality that can be introduced with such a combination are further discussed. Subsequently, challenges and opportunities are provided, seeking to point out future directions of 3D printed graphene-based metamaterials.

Highly Efficient All-3D-Printed Electrolyzer toward Ultrastable Water Electrolysis.

The practical application of electrochemical water splitting has been plagued by the sluggish kinetics of bubble generation and the slow escape of bubbles which block reaction surfaces at high current densities. Here, 3D-printed Ni (3DP Ni) electrodes with a rationally designed periodic structure and surface chemistry are reported, where the macroscopic ordered pores allow fast bubble evolution and emission, while the microporosity ensures a high electrochemically active surface area (ECSA). When they are further loaded with MoNi4 and NiFe layered double hydroxide active materials, the 3D electrodes deliver 500 mA cm-2 at an overpotential of 104 mV for the hydrogen evolution reaction (HER) and 310 mV for the oxygen evolution reaction (OER), respectively. An all-3D-printed alkaline electrolyzer (including electrodes, membrane, and cell) delivers 500 mA cm-2 at a remarkable voltage of 1.63 V with no noticeable performance decay after 1000 h. Such a tailored bubble trajectory demonstrates feasible solutions for future large-scale clean energy production.

Stable Zn Anodes with Triple Gradients.

Aqueous zinc-ion batteries are highly desirable for sustainable energy storage, but the undesired Zn dendrites growth severely shortens the cycle life. Herein, a triple-gradient electrode that simultaneously integrates gradient conductivity, zincophilicity, and porosity is facilely constructed for a dendrite-free Zn anode. The simple mechanical rolling-induced triple-gradient design effectively optimizes the electric field distribution, Zn2+ ion flux, and Zn deposition paths in the Zn anode, thus synergistically achieving a bottom-up deposition behavior for Zn metals and preventing the short circuit from top dendrite growth. As a result, the electrode with triple gradients delivers a low overpotential of 35 mV and operates steadily over 400 h at 5 mA cm-2 /2.5 mAh cm-2 and 250 h at 10 mA cm-2 /1 mAh cm-2 , far surpassing the non-gradient, single-gradient and dual-gradient counterparts. The well-tunable materials and structures with the facile fabrication method of the triple-gradient strategy will bring inspiration for high-performance energy storage devices.

MOF-Derived Bifunctional Co0.85Se Nanoparticles Embedded in N-Doped Carbon Nanosheet Arrays as Efficient Sulfur Hosts for Lithium-Sulfur Batteries.

Lithium-sulfur batteries possess the merits of low cost and high theoretical energy density but suffer from the shuttle effect of lithium polysulfides and slow redox kinetics of sulfur. Herein, novel Co0.85Se nanoparticles embedded in nitrogen-doped carbon nanosheet arrays (Co0.85Se/NC) were constructed on carbon cloth as the self-supported host for a sulfur cathode using a facile fabrication strategy. The interconnected porous carbon-based structure of the Co0.85Se/NC could facilitate the rapid electron and ion transfer kinetics. The embedded Co0.85Se nanoparticles can effectively capture and catalyze lithium polysulfides, thus accelerating the redox kinetics and stabilizing sulfur cathodes. Therefore, the Co0.85Se/NC-S cathode could maintain a stable cycle performance for 400 cycles at 1C and deliver a high discharge specific capacity of 1361, 1001, and 810 mAh g-1 at current densities of 0.1, 1, and 3C, respectively. This work provides an efficient design strategy for high-performance lithium-sulfur batteries with high energy densities.

Fabrication of 3D-Printed Ceramic Structures for Portable Solar Desalination Devices.

This paper proposes the fabrication process of the first fully 3D-printed ceramic core structures for portable solar desalination devices optimized to tackle water scarcity from an energy and sustainability perspective. Robocasting, a 3D printing technique, is utilized to fabricate a fully ceramic structure of an integrated solar absorber/thermal insulator/water transporter based on the two-layered structure of modified graphene on silica (MG@Silica) and the porous silica structure. Robocasting has demonstrated its flexibility in tailoring structural designs, combining nanopores and microchannels that exhibit uniform water transport delivery and thermal insulation. This portable device can be used immediately to collect fresh drinking water without an additional setup. It possesses a water evaporation rate of 2.4 kg m-2 h-1 with a drinking water production capacity of 0.5 L m-2 h-1. This novel device has shown excellent ion rejection ability, with the collected water meeting the World Health Organization (WHO) drinking water standards.

Structure-Enhanced Mechanically Robust Graphite Foam with Ultrahigh MnO2 Loading for Supercapacitors.

With the fast bloom of flexible electronics and green vehicles, it is vitally important to rationally design and facilely construct customized functional materials with excellent mechanical properties as well as high electrochemical performance. Herein, by utilizing two modern industrial techniques, digital light processing (DLP) and chemical vapor deposition (CVD), a unique 3D hollow graphite foam (HGF) is demonstrated, which shows a periodic porous structure and robust mechanical properties. Finite element analysis (FEA) results confirm that the properly designed gyroidal porous structure provides a uniform stress area and mitigates potential structural failure caused by stress concentrations. A typical HGF can show a high Young's modulus of 3.18 MPa at a low density of 48.2 mg cm-3. The porous HGF is further covered by active MnO2 material with a high mass loading of 28.2 mg cm-2 (141 mg cm-3), and the MnO2/HGF electrode still achieves a satisfactory specific capacitance of 260 F g-1, corresponding to a high areal capacitance of 7.35 F cm-2 and a high volumetric capacitance of 36.75 F cm-3. Furthermore, the assembled quasi-solid-state asymmetric supercapacitor also shows remarkable mechanical properties as well as electrochemical performance.

Recent progress on hollow array architectures and their applications in electrochemical energy storage.

The structural design of electrode materials is one of the most important factors that determines the electrochemical performance of energy storage devices. In recent years, hollow micro-/nanoarray structures have been widely explored for energy applications due to their unique structural advantages. Their complex hollow interior and shell arrays enable fast ion diffusion/transport, provide abundant active sites and accommodate volume changes. Moreover, the direct contact of hollow arrays with substrates enhances the mechanical stability during long-term cycling. To date, huge progress has been achieved in the rational design of various hollow array architectures. However, a review on this topic has been rarely reported. Herein, the multifunctional merits and typical synthetic strategies for hollow array structures are analyzed in detail. Furthermore, their applications in electrochemical energy storage (such as supercapacitors and batteries) are summarized. The development and challenges of hollow arrays in terms of substrates, technique improvement and material innovation are discussed. Finally, their applications for energy storage and conversion are prospected.

Recent Advances on Self-Supported Arrayed Bifunctional Oxygen Electrocatalysts for Flexible Solid-State Zn-Air Batteries.

Flexible solid-state Zn-air batteries have been rapidly developed benefiting from the uprising demand for wearable electronic devices, wherein the air electrode integrated with efficient bifunctional oxygen electrocatalysts plays an important role to achieve high performance. Binder-free self-supported bifunctional catalysts can provide large active surface area, fast electron transport path, easy ion diffusion, and excellent structural stability and flexibility, thus acting as promising flexible air cathodes. In this review, recent advances on the application of nanoarrayed electrocatalysts as air cathodes in flexible Zn-air batteries are reviewed. Especially, various types of bifunctional oxygen electrocatalysts, including carbonaceous material arrays, transition metal compound arrays, transition metal/carbon arrays, transition metal compound/carbon arrays, and other hybrid arrays, are discussed. The applications of flexible Zn-air batteries with two configurations (i.e., planar stacks and cable fibers) are also introduced. Finally, perspectives on the optimization of arrayed air cathodes for future development to achieve high-performance flexible Zn-air batteries are shared.

Three Dimensionally Free-Formable Graphene Foam with Designed Structures for Energy and Environmental Applications.

Three-dimensional assemblies of graphene have been considered as promising starting materials for many engineering, energy, and environmental applications due to its desirable mechanical properties, high specific area, and superior thermal and electrical transfer ability. However, little has been done to introduce designed shapes into scalable graphene assemblies. In this work, we show here a combination of conventional graphene growing technique-chemical vapor deposition with additive manufacturing. Such synthesis collaboration enables a hierarchically constructed porous 3D graphene foam with large surface area (994.2 m2/g), excellent conductivity (2.39 S/cm), reliable mechanical properties (E = 239.7 kPa), and tunable surface chemistry that can be used as a strain sensor, catalyst support, and solar steam generator.

Enlarged Interlayer Spacing in Cobalt-Manganese Layered Double Hydroxide Guiding Transformation to Layered Structure for High Supercapacitance.

Cobalt-manganese layered double hydroxide (CoMn-LDH) has been known as a highly desired cathode material used with an alkaline electrolyte. However, the layered double hydroxide structure is unstable and changes almost instantly in alkaline solution due to the instability of a manganese(III) ion. Thus, it is important to investigate the true active phase for designing efficient electrode materials. In this work, the metal-organic framework is used as a templating precursor to derive CoMn-LDH from three different manganese solutions, namely, MnSO4, Mn(NO3)2, and MnCl2. Anions in the solutions participate in the derivation process and strongly affect the layer structure, phase transformation process, and charge storage properties of the resulting materials. CoMn-LDH synthesized from manganese sulfate solution exhibits the largest interlayer spacing of 1.08 nm, and more interestingly, the layered structure can well be retained in KOH solution, while the other two synthesized from manganese chloride and nitrate solutions transform into the spinel structure. As a cathode material, it delivers a high areal capacity of 582.07 mC/cm2 at 2 mA/cm2, which is about 100% higher than those of the other two samples. The present work explores the active phase of CoMn-LDH in the alkaline electrolyte and proposes a potential mechanism of the phase transformation, which provides insights into understanding and designing of the active electrode materials for stable and high-performing supercapacitors in an alkaline environment.