Hierarchical Zn–Co–S Nanowires as Advanced Electrodes for All Solid State Asymmetric Supercapacitors

A facile two‐step strategy is developed to design the large‐scale synthesis of hierarchical, unique porous architecture of ternary metal hydroxide nanowires grown on porous 3D Ni foam and subsequent effective sulfurization. The hierarchical Zn–Co–S nanowires (NWs) arrays are directly employed as an electrode for supercapacitors application. The as‐synthesized Zn–Co–S NWs deliver an ultrahigh areal capacity of 0.9 mA h cm^?2 (specific capacity of 366.7 mA h g^?1) at a current density of 3 mA cm^?2, with an exceptional rate capability (≈227.6 mA h g^?1 at a very high current density of 40 mA cm^?2) and outstanding cycling stability (≈93.2% of capacity retention after 10 000 cycles). Most significantly, the assembled Zn–Co–S NWs//Fe₂O₃@reduced graphene oxide asymmetric supercapacitors with a wide operating potential window of ≈1.6 V yield an ultrahigh volumetric capacity of ≈1.98 mA h cm^?3 at a current density of 3 mA cm^?2, excellent energy density of ≈81.6 W h kg^?1 at a power density of ≈559.2 W kg^?1, and exceptional cycling performance (≈92.1% of capacity retention after 10 000 cycles). This general strategy provides an alternative to design the other ternary metal sulfides, making it facile, free‐standing, binder‐free, and cost‐effective ternary metal sulfide‐based electrodes for large‐scale applications in modern electronics.     

Metal Sulfide‐Decorated Carbon Sponge as a Highly Efficient Electrocatalyst and Absorbant for Polysulfide in High‐Loading Li2S Batteries

Owing to its high theoretical specific capacity (1166 mA h g^?1) and particularly its advantage to be paired with a lithium‐metal‐free anode, lithium sulfide (Li₂S) is regarded as a much safer cathode for next‐generation advanced lithium–sulfur (Li–S) batteries. However, the low conductivity of Li₂S and particularly the severe “polysulfide shuttle” of lithium polysulfide (LiPS) dramatically hinder their practical application in Li–S batteries. To address such issues, herein a bifuctional 3D metal sulfide‐decorated carbon sponge (3DTSC), which is constructed by 1D carbon nanowires cross‐linked with 2D graphene nanosheets with high conductivity and polar 0D metal sulfide nanodots with efficient electrocatalytic activity and strong chemical adsorption capability for LiPSs, is presented. Benefiting from the well‐designed multiscale, multidimensional 3D porous nanoarchitecture with high conductivity, and efficient electrocatalytic and absorption ability, the 3DTSC significantly mitigates LiPS shuttle, improves the utilization of Li₂S, and facilitates the transport of electrons and ions. As a result, even with a high Li₂S loading of 8 mg cm^?2, the freestanding 3DTSC‐Li₂S cathode without a polymer binder and metallic current collector delivers outstanding electrochemical performance with a high areal capacity of 8.44 mA h cm^?2.     

Silicon Nanowires and Lithium Cobalt Oxide Nanowires in Graphene Nanoribbon Papers for Full Lithium Ion Battery

Described here is the production and characterization of a scalable method to produce 3D structured lithium ion battery anodes using free‐standing papers of porous silicon nanowires (Si‐NW) and graphene nanoribbons (GNRs). Using simple filtration methods, GNRs and Si‐NWs can be entangled into a mat thereby forming Si‐NW GNR papers. This produces anodes with high gravimetric capacity (up to 2500 mA h g^?1) and high areal and volumetric capacities (up to 11 mA h cm^?2 and 3960 mA h cm?³). The compact structure of the anode is possible since the GNR volume occupies a high proportion of empty space within the composite paper. These Si‐NW/GNR papers have been cycled for over 300 cycles, exhibiting a stable life cycle. Combined with LiCoO₂ nanowires, a full battery is produced with high energy density (386 Wh kg^?1), meeting requirements for high performance devices.     

Carbon/Binder‐Free NiO@NiO/NF with In Situ Formed Interlayer for High‐Areal‐Capacity Lithium Storage

Achieving high areal capacity is a challenge for current lithium‐ion batteries (LIBs). To address this issue, nickel foam (NF), as a free‐standing skeleton suffers from long‐term poor anchor ability for active materials, resulting in detachment from conductive substrates. In addition, the weighty NF damages the overall energy density of the electrode. Herein, an in situ fabrication of interlayer strategy is proposed to effectively address these issues through constructing layer‐by‐layer a 3D structure composed of an inner conductive framework, medial NiO layer, and outer few‐layer NiO nanoflowers in turn (NiO@NiO/NF). The interlayer derived from partial oxidation of NF not only reinforces the attachment of the active layer on NF but also contributes capacity to the whole electrode, leading to excellent stability and areal capacity. When used as the anode of LIBs, ultrahigh reversible capacity of 1.98 mAh cm^?2 is delivered at 1.20 mA cm^?2. The electrode still maintains good integrity and flexibility after 1000 cycles, showing good structure stability. Compared with previous reports, NiO@NiO/NF is one of the most outstanding NiO‐based electrodes. This work proposes a feasible strategy to enhance the capacity and stability of self‐supporting electrodes, and opens a new avenue for high‐areal‐capacity anode of LIBs.     

3D Vertically Aligned Li Metal Anodes with Ultrahigh Cycling Currents and Capacities of 10 mA cm−2/20 mAh cm−2 Realized by Selective Nucleation within Microchannel Walls

Although metallic lithium is regarded as the “Holy Grail” for next‐generation rechargeable batteries due to its high theoretical capacity and low overpotential, the uncontrollable Li dendrite growth, especially under high current densities and deep plating/striping, has inhibited its practical application. Herein, a 3D‐printed, vertically aligned Li anode (3DP‐VALi) is shown to efficiently guide Li deposition via a “nucleation within microchannel walls” process, enabling a high‐performance, dendrite‐free Li anode. Moreover, the microchannels within the microwalls are beneficial for promoting fast Li⁺ diffusion, supplying large space for the accommodation of Li during the plating/stripping process. The high‐surface‐area 3D anode design enables high operating current densities and high areal capacities. As a result, the Li–Li symmetric cells using 3DP‐VALi demonstrate excellent electrochemical performances as high as 10 mA cm^?2/10 mAh cm^?2 for 1500 h and 5 mA cm^?2/20 mAh cm^?2 for 400 h, respectively. Additionally, the Li–S and Li–LiFePO₄ cells using 3DP‐VALi anodes present excellent cycling stability up to 250 and 800 cycles at a rate of 1 C, respectively. It is believed that these new findings could open a new window for dendrite‐free metal anode design and pave the way toward energy storage devices with high energy/power density.     

3D TiC/C Core/Shell Nanowire Skeleton for Dendrite‐Free and Long‐Life Lithium Metal Anode

Construction of stable dendrite‐free Li metal anode is crucial for the development of advanced Li–S and Li–air batteries. Herein, self‐supported TiC/C core/shell nanowire arrays as skeletons and confined hosts of molten Li forming integrated trilayer TiC/C/Li anode are described. The TiC/C core/shell nanowires with diameters of 400–500 nm exhibit merits of good lithiophilicity, high electrical conductivity, and abundant porosity. The as‐prepared TiC/C/Li anode exhibits prominent electrochemical performance with a small hysteresis of less than 85 mV beyond 200 cycles (3.0 mA cm^?2) as well as a very high Coulombic efficiency up to 98.5% for 100 cycles at 1.0 mA cm^?2. When the structured anode is coupled with lithium iron phosphate or sulfur cathode, the assembled full cells with trilayer TiC/C/Li anodes display enhanced capability retention and improved Coulombic efficiency. This is ascribed to the unique TiC/C matrix, which can not only provide interspace for accommodating “hostless” Li, but also afford interconnected rapid transfer paths for electrons and ions with low local current densities, leading to effective inhabitation growth of Li dendrites and lower interfacial resistance. A fresh way for construction of advanced stable Li metal anodes is provided in this work.     

A Conductive Molecular Framework Derived Li2S/N,P‐Codoped Carbon Cathode for Advanced Lithium–Sulfur Batteries

Li₂S is one of the most promising cathode materials for Li‐ion batteries because of its high theoretical capacity and compatibility with Li‐metal‐free anode materials. However, the poor conductivity and electrochemical reactivity lead to low initial capacity and severe capacity decay. In this communication, a nitrogen and phosphorus codoped carbon (N,P–C) framework derived from phytic acid doped polyaniline hydrogel is designed to support Li₂S nanoparticles as a binder‐free cathode for Li–S battery. The porous 3D architecture of N and P codoped carbon provides continuous electron pathways and hierarchically porous channels for Li ion transport. Phosphorus doping can also suppress the shuttle effect through strong interaction between sulfur and the carbon framework, resulting in high Coulombic efficiency. Meanwhile, P doping in the carbon framework plays an important role in improving the reaction kinetics, as it may help catalyze the redox reactions of sulfur species to reduce electrochemical polarization, and enhance the ionic conductivity of Li₂S. As a result, the Li₂S/N,P–C composite electrode delivers a stable capacity of 700 mA h g^?1 with average Coulombic efficiency of 99.4% over 100 cycles at 0.1C and an areal capacity as high as 2 mA h cm^?2 at 0.5C.     

A Stable Graphitic,Nanocarbon‐Encapsulated,Cobalt‐Rich Core–Shell Electrocatalyst as an Oxygen Electrode in a Water Electrolyzer

The oxygen electrode plays a vital role in the successful commercialization of renewable energy technologies, such as fuel cells and water electrolyzers. In this study, the Prussian blue analogue‐derived nitrogen‐doped nanocarbon (NC) layer‐trapped, cobalt‐rich, core–shell nanostructured electrocatalysts (core–shell Co@NC) are reported. The electrode exhibits an improved oxygen evolution activity and stability compared to that of the commercial noble electrodes. The core–shell Co@NC‐loaded nickel foam exhibits a lower overpotential of 330 mV than that of IrO₂ on nickel foam at 10 mA cm^?2 and has a durability of over 400 h. The commercial Pt/C cathode‐assisted, core–shell Co@NC–anode water electrolyzer delivers 10 mA cm^?2 at a cell voltage of 1.59 V, which is 70 mV lower than that of the IrO₂–anode water electrolyzer. Over the long‐term chronopotentiometry durability testing, the IrO₂–anode water electrolyzer shows a cell voltage loss of 230 mV (14%) at 95 h, but the loss of the core–shell Co@NC–anode electrolyzer is only 60 mV (4%) even after 350 h cell‐operation. The findings indicate that the Prussian blue analogue is a class of inorganic nanoporous materials that can be used to derive metal‐rich, core–shell electrocatalysts with enriched active centers.     

Long Cycle Life,Low Self‐Discharge Sodium–Selenium Batteries with High Selenium Loading and Suppressed Polyselenide Shuttling

The use of selenium as a cathode in rechargeable sodium–selenium batteries is hampered by low Se loading, inferior electrode kinetics, and polyselenide shuttling between the cathode and anode. Here a high‐performance sodium–selenium cell is presented by coupling a binder‐free, self‐interwoven carbon nanofiber–selenium cathode with a light‐weight carbon‐coated bifunctional separator. With this strategy, electrodes with a high Se mass loading (4.4 mg cm^?2) render high reversible capacities of 599 mA h g^?1 at 0.1C rate and 382 mA h g^?1 at 5C rate. In addition, this novel cell offers good shelf‐life with a low self‐discharge, retaining 93.4% of its initial capacity even after resting for six months. As evidenced by experimental and density functional theory analysis, the remarkable dynamic (cycle life) and static (shelf‐life) stabilities originate from the high electrical conductivity, improved Na‐ion accessibility through the 3D interconnected open channels, and highly restrained polyselenide shuttle. The results demonstrate the viability of high‐performance sodium–selenium batteries with high selenium loading.     

Electrokinetic Phenomena Enhanced Lithium‐Ion Transport in Leaky Film for Stable Lithium Metal Anodes

The application of lithium (Li) metal anodes in Li metal batteries has been hindered by growth of Li dendrites, which lead to short cycling life. Here a Li‐ion‐affinity leaky film as a protection layer is reported to promote a dendrite‐free Li metal anode. The leaky film induces electrokinetic phenomena to enhance Li‐ion transport, leading to a reduced Li‐ion concentration polarization and homogeneous Li‐ion distribution. As a result, the dendrite‐free Li metal anode during Li plating/stripping is demonstrated even at an extremely high deposition capacity (6 mAh cm^?2) and current density (40 mA cm^?2) with improved Coulombic efficiencies. A full cell battery with the leaky‐film protected Li metal as the anode and high‐areal‐capacity LiNi_0.8Co_0.1Mn_0.1O₂ (NCM‐811) (≈4.2 mAh cm^?2) or LiFePO₄ (≈3.8 mAh cm^?2) as the cathode shows improved cycling stability and capacity retention, even at lean electrolyte conditions.     

Thick Binder‐Free Electrodes for Li–Ion Battery Fabricated Using Templating Approach and Spark Plasma Sintering Reveals High Areal Capacity

The templating approach is a powerful method for preparing porous electrodes with interconnected well‐controlled pore sizes and morphologies. The optimization of the pore architecture design facilitates electrolyte penetration and provides a rapid diffusion path for lithium ions, which becomes even more crucial for thick porous electrodes. Here, NaCl microsize particles are used as a templating agent for the fabrication of 1 mm thick porous LiFePO₄ and Li₄Ti₅O₁₂ composite electrodes using spark plasma sintering technique. These sintered binder‐free electrodes are self‐supported and present a large porosity (40%) with relatively uniform pores. The electrochemical performances of half and full batteries reveal a remarkable specific areal capacity (20 mA h cm^?2), which is 4 times higher than those of 100 µm thick electrodes present in conventional tape‐casted Li–ion batteries (5 mA h cm^?2). The 3D morphological study is carried out using full field transmission X‐ray microscopy in microcomputed tomography mode to obtain tortuosity values and pore size distributions leading to a strong correlation with their electrochemical properties. These results also demonstrate that the coupling between the salt templating method and the spark plasma sintering technique turns out to be a promising way to fabricate thick electrodes with high energy density.     

Amorphous MoS3 Infiltrated with Carbon Nanotubes as an Advanced Anode Material of Sodium‐Ion Batteries with Large Gravimetric,Areal, and Volumetric Capacities

The search for earth‐abundant and high‐performance electrode materials for sodium‐ion batteries represents an important challenge to current battery research. 2D transition metal dichalcogenides, particularly MoS₂, have attracted increasing attention recently, but few of them so far have been able to meet expectations. In this study, it is demonstrated that another phase of molybdenum sulfide—amorphous chain‐like MoS₃—can be a better choice as the anode material of sodium‐ion batteries. Highly compact MoS₃ particles infiltrated with carbon nanotubes are prepared via the facile acid precipitation method in ethylene glycol. Compared to crystalline MoS₂, the resultant amorphous MoS₃ not only exhibits impressive gravimetric performance—featuring excellent specific capacity (≈615 mA h g^?1), rate capability (235 mA h g^?1 at 20 A g^?1), and cycling stability but also shows exceptional volumetric capacity of ≈1000 mA h cm^?3 and an areal capacity of >6.0 mA h cm^?2 at very high areal loadings of active materials (up to 12 mg cm^?2). The experimental results are supported by density functional theory simulations showing that the 1D chains of MoS₃ can facilitate the adsorption and diffusion of Na⁺ ions. At last, it is demonstrated that the MoS₃ anode can be paired with an Na₃V₂(PO₄)₃ cathode to afford full cells with great capacity and cycling performance.     

Artificial Solid‐Electrolyte Interphase Enabled High‐Capacity and Stable Cycling Potassium Metal Batteries

Secondary batteries based on earth‐abundant potassium metal anodes are attractive for stationary energy storage. However, suppressing the formation of potassium metal dendrites during cycling is pivotal in the development of future potassium metal‐based battery technology. Herein, a promising artificial solid‐electrolyte interphase (ASEI) design, simply covering a carbon nanotube (CNT) film on the surface of a potassium metal anode, is demonstrated. The results show that the spontaneously potassiated CNT framework with a stable self‐formed solid‐electrolyte interphase layer integrates a quasi‐hosting feature with fast interfacial ion transport, which enables dendrite‐free deposition of potassium at an ultrahigh capacity (20 mAh cm^?2). Remarkably, the potassium metal anode exhibits an unprecedented cycle life (over 1000 cycles, over 2000 h) at a high current density of 5 mA cm^?2 and a desirable areal capacity of 4 mAh cm^?2. Dendrite‐free morphology in carbon‐fiber and carbon‐black‐based ASEI for potassium metal anodes, which indicates a broader promise of this approach, is also observed.     

Direct Growth of Flower‐Like δ‐MnO2 on Three‐Dimensional Graphene for High‐Performance Rechargeable Li‐O2 Batteries

A challenge still remains to develop high‐performance and cost‐effective air electrode for Li‐O₂ batteries with high capacity, enhanced rate capability and long cycle life (100 times or above) despite recent advances in this field. In this work, a new design of binder‐free air electrode composed of three‐dimensional (3D) graphene (G) and flower‐like δ‐MnO₂ (3D‐G‐MnO₂) has been proposed. In this design, graphene and δ‐MnO₂ grow directly on the skeleton of Ni foam that inherits the interconnected 3D scaffold of Ni foam. Li‐O₂ batteries with 3D‐G‐MnO₂ electrode can yield a high discharge capacity of 3660 mAh g^?1 at 0.083 mA cm^?2. The battery can sustain 132 cycles at a capacity of 492 mAh g^?1 (1000 mAh g_carbon ^?1) with low overpotentials under a high current density of 0.333 mA cm^?2. A high average energy density of 1350 Wh Kg^?1 is maintained over 110 cycles at this high current density. The excellent catalytic activity of 3D‐G‐MnO₂ makes it an attractive air electrode for high‐performance Li‐O₂ batteries.     

Enabling High‐Energy Solid‐State Batteries with Stable Anode Interphase by the Use of Columnar Silicon Anodes

All‐solid‐state batteries (ASSBs) with silicon anodes are promising candidates to overcome energy limitations of conventional lithium‐ion batteries. However, silicon undergoes severe volume changes during cycling leading to rapid degradation. In this study, a columnar silicon anode (col‐Si) fabricated by a scalable physical vapor deposition process (PVD) is integrated in all‐solid‐state batteries based on argyrodite‐type electrolyte (Li₆PS₅Cl, 3 mS cm^?1) and Ni‐rich layered oxide cathodes (LiNi_0.9Co_0.05Mn_0.05O₂, NCM) with a high specific capacity (210 mAh g^?1). The column structure exhibits a 1D breathing mechanism similar to lithium, which preserves the interface toward the electrolyte. Stable cycling is demonstrated for more than 100 cycles with a high coulombic efficiency (CE) of 99.7–99.9% in full cells with industrially relevant areal loadings of 3.5 mAh cm^?2, which is the highest value reported so far for ASSB full cells with silicon anodes. Impedance spectroscopy revealed that anode resistance is drastically reduced after first lithiation, which allows high charging currents of 0.9 mA cm^?2 at room temperature without the occurrence of dendrites and short circuits. Finally, in‐operando monitoring of pouch cells gave valuable insights into the breathing behavior of the solid‐state cell.     

S‐Doped Graphene‐Regional Nucleation Mechanism for Dendrite‐Free Lithium Metal Anodes

Lithium metal is the most promising anode material for next‐generation batteries, owing to its high theoretical specific capacity and low electrochemical potential. However, the practical application of lithium metal batteries (LMBs) has been plagued by the issues of uncontrollable lithium deposition. The multifunctional nanostructured anode can modulate the initial nucleation process of lithium before the extension of dendrites. By combing the theoretical design and experimental validation, a novel nucleation strategy is developed by introducing sulfur (S) to graphene. Through first‐principles simulations, it is found that S atom doping can improve the Li adsorption ability on a large area around the S doping positions. Consequently, S‐doped graphene with five lithiophilic sites rather than a single atomic site can serve as the pristine nucleation area, reducing the uneven Li deposition and improving the electrochemical performance. Modifying Li metal anodes by S‐doped graphene enables an ultralow overpotential of 5.5 mV, a high average Coulombic efficiency of 99% over more than 180 cycles at a current density of 0.5 mA cm^?2 for 1.0 mAh cm^?2, and a high areal capacity of 3 mAh cm^?2. This work sheds new light on the rational design of nucleation area materials for dendrite‐free LMB.     

Long‐Life,High‐Rate Lithium–Sulfur Cells with a Carbon‐Free VN Host as an Efficient Polysulfide Adsorbent and Lithium Dendrite Inhibitor

Lithium–sulfur (Li‐S) batteries are a promising next‐generation energy‐storage system, but the polysulfide shuttle and dendritic Li growth seriously hinder their commercial viability. Most of the previous studies have focused on only one of these two issues at a time. To address both the issues simultaneously, presented here is a highly conductive, noncarbon, 3D vanadium nitride (VN) nanowire array as an efficient host for both sulfur cathodes and lithium‐metal anodes. With fast electron and ion transport and high porosity and surface area, VN traps the soluble polysulfides, promotes the redox kinetics of sulfur cathodes, facilitates uniform nucleation/growth of lithium metal, and inhibits lithium dendrite growth at an unprecedented high current density of 10 mA cm^?2 over 200 h of repeated plating/stripping. As a result, VN‐Li||VN‐S full cells constructed with VN as both an anode and cathode host with a negative to positive electrode capacity ratio of only ≈2 deliver remarkable electrochemical performance with a high Coulombic efficiency of ≈99.6% over 850 cycles at a high 4 C rate and a high areal capacity of 4.6 mA h cm^?2. The strategy presented here offers a viable approach to realize high‐energy‐density, safe Li‐metal‐based batteries.     

Fast‐Charging and Ultrahigh‐Capacity Lithium Metal Anode Enabled by Surface Alloying

Li metal anodes are going through a great revival but they still encounter grand challenges. One often neglected issue is that most reported Li metal anodes are only cyclable under relatively low current density (<5 mA cm^?2) and small areal capacity (<5 mAh cm^?2), which essentially limits their high‐power applications and results in ineffective Li utilization (<1%). Herein, it is reported that surface alloyed Li metal anodes can enable reversible cycling with ultrafast rate and ultralarge areal capacity. Low‐cost Si wafers are used and are chemically etched down to 20–30 µm membranes. Simply laminating a Si membrane onto Li foil results in the formation of Li_xSi alloy film fused onto Li metal with mechanical robustness and high Li‐ion conductivity. Symmetric cell measurements show that the surface alloyed Li anode has excellent cycling stability, even under high current density up to 25 mA cm^?2 and unprecedented areal capacity up to 100 mAh cm^?2. Furthermore, the surface alloyed Li anode is paired with amorphous MoS₃ cathode and achieves remarkable full‐cell performance.     

3D Hierarchical Porous α‐Fe2O3 Nanosheets for High‐Performance Lithium‐Ion Batteries

To develop a long cycle life and good rate capability electrode, 3D hierarchical porous α‐Fe₂O₃ nanosheets are fabricated on copper foil and directly used as binder‐free anode for lithium‐ion batteries. This electrode exhibits a high reversible capacity and excellent rate capability. A reversible capacity up to 877.7 mAh g^?1 is maintained at 2 C (2.01 A g^?1) after 1000 cycles, and even when the current is increased to 20 C (20.1 A g^?1), a capacity of 433 mA h g^?1 is retained. The unique porous 3D hierarchical nanostructure improves electronic–ionic transport, mitigates the internal mechanical stress induced by the volume variations of the electrode upon cycling, and forms a 3D conductive network during cycling. No addition of any electrochemically inactive conductive agents or polymer binders is required. Therefore, binder‐free electrodes further avoid the uneven distribution of conductive carbon on the current collector due to physical mixing and the addition of an insulator (binder), which has benefits leading to outstanding electrochemical performance.     

Densification by Compaction as an Effective Low‐Cost Method to Attain a High Areal Lithium Storage Capacity in a CNT@Co3O4 Sponge

Achieving a high areal capacity is essential for the transfer of outstanding laboratory electrode results to commercial applications and also to ensure there exists a capacity matched cathode and anode for a properly tuned battery. Despite intensive efforts, most electrode materials exhibit areal capacities lower than that of the graphite anodes (4 mA h cm^?2). An effective and low‐cost approach is reported to attain a high areal capacity via an intense densification by compacting a porous carbon nanotube sponge grafted with Co₃O₄ nanoparticles. The hybrid sponge can be compacted to a large degree (up to a tenfold densification) while still keeping its structural integrity and the 3D porous network. This method allows achieving a mass loading of up ?to 14.3 mg cm^?2 and an areal capacity of 12 mA h cm^?2 (at a current density of 200 mA g^?1) together with a gravimetric capacity of >800 mA h g^?1. This densification by compaction approach offers an effective and low‐cost strategy to develop high mass loading and areal capacity electrodes for practical energy storage systems.