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.

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.

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.

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.

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).

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.

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.

(Ni,Co)Se2 /NiCo-LDH Core/Shell Structural Electrode with the Cactus-Like (Ni,Co)Se2 Core for Asymmetric Supercapacitors.

Supercapacitors (SCs) have been widely studied as a class of promising energy-storage systems for powering next-generation E-vehicles and wearable electronics. Fabricating hybrid-types of electrode materials and designing smart nanoarchitectures are effective approaches to developing high-performance SCs. Herein, first, a Ni-Co selenide material (Ni,Co)Se2 with special cactus-like structure as the core, to scaffold the NiCo-layered double hydroxides (LDHs) shell, is designed and fabricated. The cactus-like structural (Ni,Co)Se2 core, as a highly conductive and robust support, promotes the electron transport as well as hinders the agglomeration of LDHs. The synergistic contributions from the two types of active materials together with the superior properties of the cactus-like nanostructure enable the (Ni,Co)Se2 /NiCo-LDH hybrid electrode to exhibit a high capacity of ≈170 mA h g-1 (≈1224 F g-1 ), good rate performance, and long durability. The as-assembled (Ni,Co)Se2 /NiCo-LDH//PC (porous carbon) asymmetric supercapacitor (ASC) with an operating voltage of 1.65 V delivers a high energy density of 39 W h kg-1 at a power density of 1650 W kg-1 . Therefore, the cactus-like core/shell structure offers an effective pathway to engineer advanced electrodes. The assembled flexible ASC is demonstrated to effectively power electronic devices.

Bifunctional oxygen evolution and supercapacitor electrode with integrated architecture of NiFe-layered double hydroxides and hierarchical carbon framework.

Layered double hydroxide with exchangeable interlayer anions are considered promising electro-active materials for renewable energy technologies. However, the limited exposure of active sites and poor electrical conductivity of hydroxide powder restrict its application. Herein, bifunctional integrated electrode with a 3D hierarchical carbon framework decorated by nickel iron-layered double hydroxides (NiFe-LDH) is developed. A conductive carbon nanowire array is introduced not only to provide enough anchoring sites for the hydroxide, but also affords a continuous pathway for electron transport throughout the entire electrode. The 3D integrated architecture of NiFe-hydroxide and hierarchical carbon framework possesses several beneficial effects including large electrochemical active surfaces, fast electron/mass transport, and enhanced mechanical stability. The as-prepared electrode affords a current density of 10 mA cm-2 at a low overpotential of 269 mV for oxygen evolution reaction (OER) in 1 M of KOH. It also offers excellent stability with negligible current decline even after 2000 cycles. Besides, density functional theory calculations revealed that the (110) surface of NiFe-LDH is more active than the (003) surface for OER. Furthermore, the electrode possesses promising application prospects in alkaline battery-supercapacitor hybrid devices with a capacity of 178.8 mAh g-1 (capacitance of 1609.6 F g-1) at a current density of 0.2 A g-1. The viability of the as-prepared bifunctional electrode will provide a potential solution for wearable electronics in the near future.

2D Metal-Organic Frameworks Derived Nanocarbon Arrays for Substrate Enhancement in Flexible Supercapacitors.

Direct assembling of active materials on carbon cloth (CC) is a promising way to achieve flexible electrodes for energy storage. However, the overall surface area and electrical conductivity of such electrodes are usually limited. Herein, 2D metal-organic framework derived nanocarbon nanowall (MOFC) arrays are successfully developed on carbon cloth by a facile solution + carbonization process. Upon growth of the MOFC arrays, the sites for growth of the active materials are greatly increased, and the equivalent series resistance is decreased, which contribute to the enhancement of the bare CC substrate. After decorating ultrathin flakes of MnO2 and Bi2 O3 on the flexible CC/MOFC substrate, the hierarchical electrode materials show an abrupt improvement of areal capacitances by around 50% and 100%, respectively, compared to those of the active materials on pristine carbon cloth. A flexible supercapacitor can be further assembled using two hierarchical electrodes, which demonstrates an energy density of 124.8 µWh cm-2 at the power density of 2.55 mW cm-2 .

Rational Construction of Hollow Core-Branch CoSe2 Nanoarrays for High-Performance Asymmetric Supercapacitor and Efficient Oxygen Evolution.

Metal selenides have great potential for electrochemical energy storage, but are relatively scarce investigated. Herein, a novel hollow core-branch CoSe2 nanoarray on carbon cloth is designed by a facile selenization reaction of predesigned CoO nanocones. And the electrochemical reaction mechanism of CoSe2 in supercapacitor is studied in detail for the first time. Compared with CoO, the hollow core-branch CoSe2 has both larger specific surface area and higher electrical conductivity. When tested as a supercapacitor positive electrode, the CoSe2 delivers a high specific capacitance of 759.5 F g-1 at 1 mA cm-2 , which is much larger than that of CoO nanocones (319.5 F g-1 ). In addition, the CoSe2 electrode exhibits excellent cycling stability in that a capacitance retention of 94.5% can be maintained after 5000 charge-discharge cycles at 5 mA cm-2 . An asymmetric supercapacitor using the CoSe2 as cathode and an N-doped carbon nanowall as anode is further assembled, which show a high energy density of 32.2 Wh kg-1 at a power density of 1914.7 W kg-1 , and maintains 24.9 Wh kg-1 when power density increased to 7354.8 W kg-1 . Moreover, the CoSe2 electrode also exhibits better oxygen evolution reaction activity than that of CoO.

Metal Phosphides and Phosphates-based Electrodes for Electrochemical Supercapacitors.

Phosphorus compounds, such as metal phosphides and phosphates have shown excellent performances and great potential in electrochemical energy storage, which are demonstrated by research works published in recent years. Some of these metal phosphides and phosphates and their hybrids compare favorably with transition metal oxides/hydroxides, which have been studied extensively as a class of electrode materials for supercapacitor applications, where they have limitations in terms of electrical and ion conductivity and device stability. To be specific, metal phosphides have both metalloid characteristics and good electric conductivity. For metal phosphates, the open-framework structures with large channels and cavities endow them with good ion conductivity and charge storage capacity. In this review, we present the recent progress on metal phosphides and phosphates, by focusing on their advantages/disadvantages and potential applications as a new class of electrode materials in supercapacitors. The synthesis methods to prepare these metal phosphides/phosphates are looked into, together with the scientific insights involved, as they strongly affect the electrochemical energy storage performance. Particular attentions are paid to those hybrid-type materials, where strong synergistic effects exist. In the summary, the future perspectives and challenges for the metal phosphides, phosphates and hybrid-types are proposed and discussed.

A high energy and power Li-ion capacitor based on a TiO2 nanobelt array anode and a graphene hydrogel cathode.

A novel hybrid Li-ion capacitor (LIC) with high energy and power densities is constructed by combining an electrochemical double layer capacitor type cathode (graphene hydrogels) with a Li-ion battery type anode (TiO(2) nanobelt arrays). The high power source is provided by the graphene hydrogel cathode, which has a 3D porous network structure and high electrical conductivity, and the counter anode is made of free-standing TiO(2) nanobelt arrays (NBA) grown directly on Ti foil without any ancillary materials. Such a subtle designed hybrid Li-ion capacitor allows rapid electron and ion transport in the non-aqueous electrolyte. Within a voltage range of 0.0-3.8 V, a high energy of 82 Wh kg(-1) is achieved at a power density of 570 W kg(-1). Even at an 8.4 s charge/discharge rate, an energy density as high as 21 Wh kg(-1) can be retained. These results demonstrate that the TiO(2) NBA//graphene hydrogel LIC exhibits higher energy density than supercapacitors and better power density than Li-ion batteries, which makes it a promising electrochemical power source.

Atomic-layer-deposition alumina induced carbon on porous Ni(x)Co(1-x)O nanonets for enhanced pseudocapacitive and Li-ion storage performance.

A unique composite nanonet of metal oxide@carbon interconnected sheets is obtained by atomic layer deposition (ALD)-assisted fabrication. In this nanonet structure, mesoporous metal oxide nanosheets are covered by a layer of amorphous carbon nanoflakes. Specifically, quasi-vertical aligned and mesoporous Ni(x)Co(1-x)O nanosheets are first fabricated directly on nickel foam substrates by a hydrothermal method. Then, an ALD-enabled carbon coating method is applied for the growth of carbon nanoflakes on the surface of the nanosheets. The thus formed 3D hierarchical structure of Ni(x)Co(1-x)O@carbon composite flakes have a higher surface area, better electrical conductivity and structure stability than the bare Ni(x)Co(1-x)O. The application of such composite nanomaterials is demonstrated as electrodes for a supercapacitor and a lithium-ion battery. In both tests, the composite electrode shows enhancement in capacity and cycling stability. This effective composite nanostructure design of metal oxides@carbon flakes could provide a promising method to construct high-performance materials for energy and environment applications.

Atomic layer deposition of Co3O4 on carbon nanotubes/carbon cloth for high-capacitance and ultrastable supercapacitor electrode.

Co3O4 nanolayers have been successfully deposited on a flexible carbon nanotubes/carbon cloth (CC) substrate by atomic layer deposition. Much improved capacitance and ultra-long cycling life are achieved when the CNTs@Co3O4/CC is tested as a supercapacitor electrode. The improvement can be from the mechanically robust CC/CNTs substrate, the uniform coated high capacitance materials of Co3O4 nanoparticles, and the unique hierarchical structure. The flexible electrode of CNTs@Co3O4/CC with high areal capacitance and excellent cycling ability promises great potential for developing high-performance flexible supercapacitors.

Highly stable and reversible lithium storage in SnO2 nanowires surface coated with a uniform hollow shell by atomic layer deposition.

SnO2 nanowires directly grown on flexible substrates can be a good electrode for a lithium ion battery. However, Sn-based (metal Sn or SnO2) anode materials always suffer from poor stability due to a large volume expansion during cycling. In this work, we utilize atomic layer deposition (ALD) to surface engineer SnO2 nanowires, resulting in a new type of hollowed SnO2-in-TiO2 wire-in-tube nanostructure. This structure has radically improved rate capability and cycling stability compared to both bare SnO2 nanowires and solid SnO2@TiO2 core-shell nanowire electrodes. Typically a relatively stable capacity of 393.3 mAh/g has been achieved after 1000 charge-discharge cycles at a current density of 400 mA/g, and 241.2 mAh/g at 3200 mA/g. It is believed that the uniform hollow TiO2 shell provides stable surface protection and the appropriate-sized gap effectively accommodates the expansion of the interior SnO2 nanowire. This ALD-enabled method should be general to many other battery anode and cathode materials, providing a new and highly reproducible and controllable technique for improving battery performance.

A new type of porous graphite foams and their integrated composites with oxide/polymer core/shell nanowires for supercapacitors: structural design, fabrication, and full supercapacitor demonstrations.

We attempt to meet the general design requirements for high-performance supercapacitor electrodes by combining the strategies of lightweight substrate, porous nanostructure design, and conductivity modification. We fabricate a new type of 3D porous and thin graphite foams (GF) and use as the light and conductive substrates for the growth of metal oxide core/shell nanowire arrays to form integrated electrodes. The nanowire core is Co3O4, and the shell is a composite of conducting polymer (poly(3,4-ethylenedioxythiophene), PEDOT) and metal oxide (MnO2). To show the advantage of this integrated electrode design (viz., GF + Co3O4/PEDOT-MnO2 core/shell nanowire arrays), three other different less-integrated electrodes are also prepared for comparison. Full supercapacitor devices based on the GF + Co3O4/PEDOT-MnO2 as positive electrodes exhibit the best performance compared to other three counterparts due to an optimal design of structure and a synergistic effect.

Atomic-layer-deposition-assisted formation of carbon nanoflakes on metal oxides and energy storage application.

Nanostructured carbon is widely used in energy storage devices (e.g., Li-ion and Li-air batteries and supercapacitors). A new method is developed for the generation of carbon nanoflakes on various metal oxide nanostructures by combining atomic layer deposition (ALD) and glucose carbonization. Various metal oxide@nanoflake carbon (MO@f-C) core-branch nanostructures are obtained. For the mechanism, it is proposed that the ALD Al2 O3 and glucose form a composite layer. Upon thermal annealing, the composite layer becomes fragmented and moves outward, accompanied by carbon deposition on the alumina skeleton. When tested as electrochemical supercapacitor electrode, the hierarchical MO@f-C nanostructures exhibit better properties compared with the pristine metal oxides or the carbon coating without ALD. The enhancement can be ascribed to increased specific surface areas and electric conductivity due to the carbon flake coating. This peculiar carbon coating method with the unique hierarchical nanostructure may provide a new insight into the preparation of 'oxides + carbon' hybrid electrode materials for energy storage applications.

Synthesis of free-standing metal sulfide nanoarrays via anion exchange reaction and their electrochemical energy storage application.

Metal sulfides are an emerging class of high-performance electrode materials for solar cells and electrochemical energy storage devices. Here, a facile and powerful method based on anion exchange reactions is reported to achieve metal sulfide nanoarrays through a topotactical transformation from their metal oxide and hydroxide preforms. Demonstrations are made to CoS and NiS nanowires, nanowalls, and core-branch nanotrees on carbon cloth and nickel foam substrates. The sulfide nanoarrays exhibit superior redox reactivity for electrochemical energy storage. The self-supported CoS nanowire arrays are tested as the pseudo-capacitor cathode, which demonstrate enhanced high-rate specific capacities and better cycle life as compared to the powder counterparts. The outstanding electrochemical properties of the sulfide nanoarrays are a consequence of the preservation of the nanoarray architecture and rigid connection with the current collector after the anion exchange reactions.

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.