Sodium-ion Hybrid Capacitors Research Articles

Ultrafast Na-Ion Storage in Amorphization Engineered Hollow Vanadium Oxide/MXene Nanohybrids for High-Performance Sodium-Ion Hybrid Capacitors.

Sodium ion hybrid capacitors (SIHCs) address the high power and energy requirements in energy storage devices but face significant challenges arising from the slow kinetics and cycling instability of the anode side. Introducing atomic disorder and employing structural engineering in anode materials proves to be effective strategies for achieving rapid charge storage. Here, it is demonstrated that N-doped MXene encapsulated amorphous vanadium oxide hollow spheres (VOx@N-MXene HSs) offer multidirectional open pathways and sufficient vacancies, enabling reversible and fast Na+ insertion/extraction. Machine learning potentials, coupled with molecular simulation techniques, confirm the presence of more abundant pores within the amorphous vanadium oxide (VOx) structure. The simulation of the charging/discharging process elucidates the authentic reaction path and structural evolutions of the VOx@N-MXene HSs, providing sufficient insight into the atomic-scale mechanisms associated with these structural superiorities. The full SIHCs devices demonstrate a high energy density of 198.3 Wh kg-1, along with a long-term cycling lifespan of 8000 cycles. This study offers valuable strategies into the intricate design and exploration of amorphous electrodes, contributing to the advancement of next-generation electrochemical energy devices.

Hollow porous Co0.85Se/MoSe2@MXene heterostructured anode for sodium-ion hybrid capacitors

Metal selenides have garnered significant attention as promising anode materials for sodium-ion hybrid capacitors (SIHCs), yet its sluggish reaction kinetics as the battery-type anodes pose a challenge for developing high power SIHCs when coupled with capacitor-type cathodes. To overcome this limitation, constructing heterostructured metal selenides anodes has emerged as a promising strategy to balance the reaction kinetics between two different types of electrodes. Herein, the hollow porous TA-Co0.85Se/MoSe2@MXene anode with multiple heterostructures for sodium storage has been engineered via facile double-etching and self-assembly approach. The well-tailored void space and abundant heterointerfaces may effectively mitigate volumetric changes and enhance structural stability. Density functional theory (DFT) calculations further reveal that the local multilevel built-in electric fields induced by the heterointerfaces can effectively accelerate charge transfer and reduce the migration energy barrier of Na+, thus boosting the reaction kinetics. The fabricated anode demonstrates superior long-term cycling performance with a reversible capacity of 414 mA h/g after 1000 cycles at 1 A/g and remarkable rate capability of 425 mA h/g at 5 A/g. Benefiting from the ingenious structure and excellent sodium storage performance, the as-built SIHCs achieves an impressive energy density of 193 W h kg−1 and high power output of 18 kW kg−1 with outstanding capacitance retention of 90 % at 2 A/g after 10,000 cycles. This study provides valuable insights into the rational design of multiple heterostructured anode materials with multilevel built-in electric fields for high-performance SIHCs.

Synergistic engineering of heteroatomic N-doping and PPy modification in flower-like vanadium sulfide anode enables stable sodium storage

Vanadium sulfide, an appealing anode candidate for sodium ion batteries (SIBs), still encounters considerable volume fluctuation and sluggish Na+ diffusion kinetics, which inevitably gives rise to unsatisfactory rate capability and severe capacity decay. Herein, we successfully designed and constructed an outstanding sodium-storage feature and exceedingly stable anode for SIBs in the form of three-dimensional flower-like architecture composing of phosphorus doped VS2 wrapped by conductive elastic polypyrrole (PPy) layer (i.e., P-VS2@PPy). Through leveraging the multifunctional synergistic effect of composition and structure, involving enhanced electronic conductivity, reduced volumetric fluctuation, accelerated charge/ion transfer efficiency, and remarkable surface-capacitive behaviors can guarantee significantly enhanced electrochemical sodium-storage ability of P-VS2@PPy composites. As a consequence,such P-VS2@PPy is endowed with desirable rate characteristic accompanied with long-period cyclic lifespan (436.7 mAh/g at 20.0 A/g after 2600 cycles), which far outperform contrastive P-VS2 and pure VS2 samples. Meticulous kinetic analysis combined with theoretical simulations conclude that phosphorus doping and PPy coating have substantial effects on strengthening ionic and electron diffusion kinetics. Thorough examination and analysis of the insertion and conversion mechanisms of P-VS2@PPy was conducted through ex situ tests, revealing superior reversible phase transformation between original VS2, intermediate NaVS2, and final Na2S/V. Additionally, a practical application test demonstrates that sodium ion full-cell and hybrid capacitor based on P-VS2@PPy anode showcase significant capacity contribution and outstanding specific energy output, capable of effortlessly lighting up a LED screen.

S/N Co-Doped Ultrathin TiO2 Nanoplates as an Anode Material for Advanced Sodium-Ion Hybrid Capacitors.

Anatase titanium dioxide (TiO2) has emerged as a potential anode material for sodium-ion hybrid capacitors (SICs) in terms of its nontoxicity, high structure stability and cost-effectiveness. However, its inherent poor electrical conductivity and limited reversible capacity greatly hinder its practical application. Here, ultrathin TiO2 nanoplates were synthesized utilizing a hydrothermal technique. The electrochemical kinetics and reversible capacity were significantly improved through sulfur and nitrogen co-doping combined with carbon coating (SN-TiO2/C). Sulfur and nitrogen co-doping generated oxygen vacancies and introduced additional active sites within TiO2, facilitating accelerated Na-ion diffusion and enhancing its reversible capacity. Furthermore, carbon coating provided stable support for electron transfer in SN-TiO2/C during repeated cycling. This synergistic strategy of sulfur and nitrogen co-doping with carbon coating for TiO2 led to a remarkable capacity of 335.3 mAh g-1 at 0.1 A g-1, exceptional rate property of 148.3 mAh g-1 at 15 A g-1 and a robust cycling capacity. Thus, the SN-TiO2/C//AC SIC delivered an impressive energy density of 177.9 W h kg-1. This work proposes an idea for the enhancement of reaction kinetics for energy storage materials through a synergistic strategy.

Zinc selenide/cobalt selenide in nitrogen-doped carbon frameworks as anode materials for high-performance sodium-ion hybrid capacitors

Zinc selenide/cobalt selenide in nitrogen-doped carbon frameworks as anode materials for high-performance sodium-ion hybrid capacitors

An Engineering Porous Spherical Carbon Cathode for High-Energy Sodium-Ion Capacitor.

Sodium-ion hybrid capacitors (SICs) are emerging as promising devices that can balance energy and power output. However, the lack of a high-capacity cathode that can match the anode has limited its further application. In this work, we develop an efficient method to prepare spherical porous carbons (SPCs) with great specific surface area and narrow pore size distribution from coal-based humic acid via spray drying and a subsequent chemical activation process. Thanks to this unique porous structure, the SPC cathode has a superb capacity of 223 F g-1 at 0.05 A g-1, as well as splendid rate performance and cycling stability. SICs constructed by an SPC cathode and hard carbon anode can exhibit a high energy density of 179.8 Wh kg-1 at 155 W kg-1 and achieved 89.4% capacity retention after 10 000 cycles at 0.5 A g-1. This outcome presents a viable approach to attaining high-capacity cathodes for constructing outstanding performance hybrid capacitors.

A novel hybrid sodium ion capacitor based on Na [Ni0.60Mn0.35Co0.05] O2 battery type cathode and presodiated D-Ti3C2Tx pseudocapacitive anode

The combination of the high-power density of supercapacitors and the high energy density of batteries makes hybrid sodium-ion capacitors (HSICs) a promising device. HSICs can provide better performance characteristics by harnessing both ion adsorption/desorption in the capacitor-type electrode and sodium-ion intercalation in the battery-type electrode. Here, the synthesis of MXene (Ti3C2Tx), a two-dimensional (2D) carbide and nitride is reported. Delaminated MXene (D-Ti3C2Tx) is a promising candidate for anode material in HSIC due to its large surface area (∼ 42 m2/g) and good electronic conductivity. Electrochemical study indicates that D-Ti3C2Tx anode exhibits a high discharge capacity of ∼213 mAh/g at a current rate of 20 mA/g. Further the presodiated D-Ti3C2Tx anode is paired with Na [Ni0.60Mn0.35Co0.05] O2 (P2-NMC) cathode to obtain the configuration of HSIC. The HSIC exhibits good specific capacitance of ∼187 F/g and specific discharge capacity of ∼110 mAh/g at a current density of 10 mA/g, according to the electrochemical analysis. A notable improvement in specific energy density (∼ 256 Wh/kg) and specific power density (∼579 W/kg) is also demonstrated by the HSIC. With P2-NMC being used as the cathode material rather than traditional activated carbon, there has been a rise in specific energy density.

Fluorine and Nitrogen Codoped Carbon Nanosheets In Situ Loaded CoFe2O4 Particles as High-Performance Anode Materials for Sodium Ion Hybrid Capacitors

Fluorine and Nitrogen Codoped Carbon Nanosheets In Situ Loaded CoFe₂O₄ Particles as High-Performance Anode Materials for Sodium Ion Hybrid Capacitors

Ultra-thin SnS2 nanosheets grown on carbon nanofibers with high-performance in sodium-ion energy storage

SnS2 with two-dimensional layered structure has great application promising in the energy storage system due to its super high theoretical capacity. However, the serious volume expansion and low intrinsic conductivity are difficult to meet the commercial application of SnS2 in sodium-ion batteries (SIBs). Herein, SnS2/CNF was successfully prepared by simple electrospinning technique and hydrothermal method. Based on the synergistic effect between ultra-thin nanosheets and carbon nanofibers (CNF), the anode material not only shortened the path of electron transport, but also accelerated the sodium ion reaction kinetics, thus showed outstanding stability and reversibility SIBs. The SnS2/CNF displayed the excellent rate properties (352 mAh g-1 at 5 A g-1) as well as stable long term cycle performance (338 mAh g-1 at 3 A g-1 after 500 cycles). Furthermore, the SnS2/CNF//AC sodium-ion hybrid capacitor (SIHCs) exhibits excellent energy density and power density of 97 Wh kg-1/54 W kg-1. The capacity retention is 81 % after 2500 cycles at 1 A g-1. The SIHCs could light up to 100 LEDs easily, which thus exhibited great practical application potential in energy storage device.

Voltage regulation toward stable cycling of sodium vanadium oxy-fluorophosphates for high-performing, mechanically robust aqueous sodium-ion hybrid capacitors

Sodium vanadium oxy-fluorophosphates (Na3V2O2x(PO4)2F3−2x, NVOPF, 0 ≤ x ≤ 1) are promising cathodes for aqueous sodium-ion hybrid capacitors (ASIHCs) due to their high theoretical capacity and operation potential. However, the extremely poor cycle life and unclear failure mechanism greatly hinder their application in ASIHCs. Here, the intrinsic capacity degradation mechanism of NVOPF is elucidated and a unique voltage regulation strategy is proposed. By slightly compressing the charge cut-off voltage to 1.0 V (vs. SCE, saturated calomel electrode), the vanadium dissolution of NVOPF nanocomposite is significantly suppressed and superior cycling stability is achieved (79.67 % after 800 cycles), among the best reported for NVOPF operating in aqueous electrolytes. Microporous zeolite-templated carbon (ZTC) with ultra-large surface area is selected as a unique capacitive anode for pairing and intentionally activated via an electrochemical oxidation, providing huge pseudocapacitance that is ∼23 times higher than pristine ZTC. Furthermore, a high-performing 2.1 V quasi-solid-state NVOPF-based ASIHC is developed by designing an electrode-compatible polyacrylamide (PAM)-17 m (mol kg−1) NaClO4 hydrogel electrolyte with high ionic conductivity and adhesiveness, which not only provides recordable cycle stability, superior rate performance and high energy/power density, but also demonstrates exceptional safety, flexibility, and robust durability against extreme conditions, including short circuit, nail penetration and mechanical damage.

Sustainable Balsa wood-derived high-rate hard carbon anodes for sodium-ion hybrid capacitors

Biomass-derived hard carbons have broad prospects toward commercialized sodium-ion batteries because of their advantages of low cost, renewability, and the diversity of precursors. Although hard carbon materials have advantages such as considerable specific capacity and good stability, the application of hard carbon materials in sodium-ion hybrid capacitors (SIHCs) is still limited by their low-rate capability. In this work, a direct carbonization method is used to prepare hard carbons derived from Balsa woods (BHCs). The best rate capability of BHCs is obtained by an optimized carbonization temperature of 1400 °C. The prepared hard carbon shows a smaller closed pore size (1.77 nm) compared to most recently reported hard carbons, which ensures their high rate capability. At the carbonization temperature of 1400 °C, BHC achieves the highest capacity of 296 mAh g−1. BHC-1400 also exhibits a high capacity retention of 54.9 % at a current density of 5 A g−1. The excellent electrochemical properties indicate that the BHCs have potential in the application of high-rate SIHCs.

Hybrid catalyst‐assisted synthesis of multifunctional carbon derived from Camellia shell for high‐performance sodium‐ion batteries and sodium‐ion hybrid capacitors

AbstractBiomass‐derived carbon as energy storage materials have gradually attracted widespread attention due to their low cost, sustainability, and inherent structural advantages. Herein, hard carbon (H‐1200) and porous carbon (PC‐800) for sodium‐ion batteries (SIBs), sodium‐ion capacitors (SICs) half cells and sodium‐ion hybrid capacitors (SIHCs) have been synthesized from the same biomass precursor of Camellia shells through different treatments. H‐1200 synthesized by directly high‐temperature carbonization possesses a rational graphitic layer structure and plentiful heteroatoms. When applied as anode for SIBs, it exhibits a reversible capacity of 365.5 mAh g–1 at 25 mA g–1 and capacity retention 89.0% after 400 cycles at 200 mA g–1. Additionally, PC‐800 prepared by catalytic carbonization of K2C2O4/CaC2O4 hybrid catalyst has a sophisticated porous structure and a high surface area of 2186.9 m2 g–1. When employed as a cathode for SICs, it delivers a maximum capacity 104.2 mAh g–1 at 100 mA g–1 and 35.0 mAh g–1 at 5 A g–1. Furthermore, the all carbon assembled SIHC (H‐1200||PC‐800) using H‐1200 as anode and PC‐800 as cathode, features a broad output voltage range (0.01 ~ 4.1 V), high energy density of 161.5 Wh kg–1, power density of 12896.1 W kg–1, and superior capacity retention of 90.32% after 10000 cycles at 10 A g–1. This research result provide a new horizon for constructing low‐cost and large‐scale production of biomass derived carbon for energy storage materials.

Nano-porous structure architectonics of MoS2 nanosheets with flexible electrode membrane for designing ultrastable sodium-ion hybrid capacitor

In the realm of large-scale energy storage, sodium-ion hybrid capacitors (SICs) have emerged as promising contenders due to their impressive fusion of high energy density and power density. However, the challenge lied in addressing the slow reaction kinetics of the Faraday battery-type anode, which was difficult to match with the capacitive-type cathode. In this work, the porous structure architecture was designed by chemically bonding retiform MoS2 nanosheets onto the interpenetrating network electrode membrane (EM) in-situ, creating an integrated electrode (CM@MoS2). The structural synergy between MoS2 and EM facilitated the optimal environment for Na+ transportation and storage, greatly enhancing the reaction kinetics. As the Faraday battery-type anodes, a remarkable reversible capacity retention rate of 94.2% was achieved even after undergoing 1000 cycles at 0.2 A g−1. Matching with capacitive-type cathode of activated carbon (AC), the assembling CM@MoS2//AC SICs also exhibited an impressive reversible capacity retention rate of 87.7% even after 10,000 cycles at 1 A g−1, and achieving 117 Wh kg−1 of the energy density at a power density of 100 W kg−1, showcasing outstanding dual-function features. The application of architectonics to Faraday battery-type anodes holds promised for providing insights and concepts for the future rational design of sodium storage materials with enhanced electrochemical properties in SICs.

Vacancy-Defect Ternary Topological Insulators Bi2Se2Te Encapsulated in Mesoporous Carbon Spheres for High Performance Sodium Ion Batteries and Hybrid Capacitors.

Ternary topological insulators have attracted worldwide attention because of their broad application prospects in fields such as magnetism, optics, electronics, and quantum computing. However, their potential and electrochemical mechanisms in sodium ion batteries (SIBs) and hybrid capacitors (SIHCs) have not been fully studied. Herein, a composite material comprising vacancy-defects ternary topological insulator Bi2Se2Te encapsulated in mesoporous carbon spheres (Bi2Se2Te@C) is designed. Bi2Se2Te with ample vacancy-defects has a wide interlayer spacing to enable frequent insertion/extraction of Na+ and boost reaction kinetics within the electrode. Meanwhile, the Bi2Se2Te@C with optimized yolk-shell structure can buffer the volume variation without breaking the outer protective carbon shell, ensuring structural stability and integrity. As expected, the Bi2Se2Te@C electrode delivers high reversible capacity and excellent rate capability in half SIB cells. Various electrochemical analyses and theoretical calculations manifest that Bi2Se2Te@C anode confirms the synergistic effect of ternary chalcogenide systems and suitable void space yolk-shell structure. Consequently, the full cells of SIB and SIHC coupled with Bi2Se2Te@C anode exhibit good performance and high energy/power density, indicating its widespread practical applications. This design is expected to offer a reliable strategy for further exploring advanced topological insulators in Na+-based storage systems.

Na2S in‐situ infiltrated in actived carbon as high‐efficiency presodiation additives for sodium ion hybrid capacitors

AbstractSodium ion hybrid capacitors (SIHC) are emerging as promising next‐generation energy storage devices with high energy/power density. Presodiation is an essential part of SIHC production due to the lack of sodium sources in the cathode and anode. However, in the current presodiation methods, electrochemical presodiation by galvanostatic current charging and discharging requires a temporary half‐cell or a complex reassembling process, which severely hinders the commercialization of SIHC. Herein, in situ synthesized Na2S infiltrated in activated carbon was used as a sodium salt additive for supplying Na+ in SIHC. Due to a low ratio of Na2S additive attributed to high theoretical specific capacity, the fabricated Na2S/activated carbon composite//HC SIHC can show a higher energy density of 129.71 Wh kg−1 than previously reported SIHC on presodiation of cathode additives. Moreover, the designed SIHC shows an excellent cycling performance of 10,000 cycles, which is attributed to the Na2S additive with the advantages of low decomposition potential and no gas generation. This work provides a novel approach for the fabrication of highly efficient Na2S additive composite cathodes for SIHC.

Unraveling high efficiency multi-step sodium storage and bidirectional redox kinetics synergy mechanism of cobalt-doping vanadium disulfide anode

Sodium-based storage devices based on conversion-type metal sulfide anodes have attracted great attention due to their multivalent ion redox reaction ability. However, they also suffer from sodium polysulfides (NaPSs) shuttling problems during the sluggish Na+ redox process, leading to “voltage failure” and rapid capacity decay. Herein, a metal cobalt-doping vanadium disulfide (Co-VS2) is proposed to simultaneously accelerate the electrochemical reaction of VS2 and enhance the bidirectional redox of soluble NaPSs. It is found that the strong adsorption of NaPSs by V-Co alloy nanoparticles formed in situ during the conversion reaction of Co-VS2 can effectively inhibit the dissolution and shuttle of NaPSs, and thermodynamically reduce the formation energy barrier of the reaction path to effectively drive the complete conversion reaction, while the metal transition of Co elements enhances reconversion kinetics to achieve high reversibility. Moreover, Co-VS2 also produce abundant sulfur vacancies and unsaturated sulfur edge defects, significantly improve ionic/electron diffusion kinetics. Therefore, the Co-VS2 anode exhibits ultrahigh rate capability (562 mA h g−1 at 5 A g−1), high initial coulombic efficiency (≈90%) and 12,000 ultralong cycle life with capacity retention of 90% in sodium-ion batteries (SIBs), as well as impressive energy/power density (118 Wh kg−1/31,250 W kg−1) and over 10,000 stable cycles in sodium-ion hybrid capacitors (SIHCs). Moreover, the pouch cell-type SIHC displays a high-energy density of 102 Wh kg−1 and exceed 600 stable cycles. This work deepens the understanding of the electrochemical reaction mechanism of conversion-type metal sulfide anodes and provides a valuable solution to the shuttling of NaPSs in SIBs and SIHCs.

3D isotropic MXene films enabling minimized polarization for enhanced sodium-ion storage performance

Electrochemical sodium-ion storage has emerged as a tantalizing avenue for advanced energy storage systems. However, the pronounced polarization poses a formidable challenge for applications at high currents and low temperatures. Herein, we propose an electrode-level isotropic porosity generation route, which includes solution design and a scalable film-forming process, to fabricate a well-designed three-dimensional (3D) Ti3C2Tx film. The resulting 3D Ti3C2Tx film exhibits a distinctive isotropic architecture featuring interconnected horizontal and vertical channels. In contrast to the compact structure, the unique 3D isotropic architecture of the Ti3C2Tx film demonstrates a remarkable reduction in polarization, which is the outcome of comprehensive Na+ kinetics enhancement of the anode side. Consequently, capacity retentions exceeding 50 % are achieved even at a current density of 20 A g−1 or sub-zero temperature (-20 °C). Furthermore, detailed analyses were conducted to elucidate the multifaceted effects of divergent pore structures on kinetic mechanisms, encompassing a thorough examination of distinct polarization effects. In addition, the assembly of a 3D Ti3C2Tx film//activated carbon sodium-ion hybrid capacitor demonstrates remarkable energy density and outstanding cycling stability. The electrode-level isotropic porosity generation route significantly enhances the electrochemical properties of MXene-based film, holding great potential for advancements in applications that can leverage this structural engineering.

Enhancing Specific Energy in Sodium-Ion Hybrid Capacitors via Quasi-Anodeless Configuration

Enhancing Specific Energy in Sodium-Ion Hybrid Capacitors via Quasi-Anodeless Configuration

Synergistically Coupling Atomic-Level Defect-Manipulation and Nanoscopic-Level Interfacial Engineering Enables Fast and Durable Sodium Storage.

Through inducing interlayer anionic ligands and functionally modifying conductive carbon-skeleton on the transition metal chalcogenides (TMCs) parent to achieve atomic-level defect-manipulation and nanoscopic-level architecture design is of great significance, which can broaden interlayer distance, optimize electronic structure, and mitigate structural deformation to endow high-efficiency battery performance of TMCs. Herein, an intriguing 3D biconcave hollow-tyre-like anode constituted by carbon-packaged defective-rich SnSSe nanosheet grafting onto Aspergillus niger spores-derived hollow-carbon (ANDC@SnSSe@C) is reported. Systematically experimental investigations and theoretical analyses forcefully demonstrate the existence of anion Se ligand and outer-carbon all-around encapsulation on the ANDC@SnSSe@C can effectively yield abundant structural defects and Na+-reactivity sites, accelerate rapid ion migration, widen interlayer spacing, as well as relieve volume expansion, thus further resolving the critical issues throughout the charge-discharge processes. As anticipated, as-fabricated ANDC@SnSSe@C anode contributes extraordinary reversible capacity, wonderful cyclic lifespan with 83.4% capacity retention over 2000 cycles at 20.0 A g-1, and exceptional rate capability. A series of correlated kinetic investigations and ex situ characterizations deeply reveal the underlying springheads for the ion-transport kinetics, as well as synthetically elucidate phase-transformation mechanism of the ANDC@SnSSe@C. Furthermore, the ANDC@SnSSe@C-based sodium ion full cell and hybrid capacitor offer high-capacity contribution and remarkable energy-density output, indicative of its great practicability.

Construction of WS2/NC@C nanoflake composites as performance-enhanced anodes for sodium-ion batteries.

The development of layered metal sulfides with stable structure and accessible active sites is of great importance for sodium-ion batteries (SIBs). Herein, a simple liquid-mixing method is elaborately designed to immobilize WS2 nanoflakes on N-doped carbon (NC), then further coat carbon to produce WS2/NC@C. In the formation process of this composite, the presence of NC not only avoids the overlap and improves the dispersion of WS2 nanoflakes, but also creates a connection network for charge transfer, where the wrapped carbon provides a stable chemical and electrochemical reaction interface. Thus, the composite of WS2/NC@C exhibits the desired Na+ storage capacity as anticipated. The reversible capacity reaches the high value of 369.8 mA h g-1 at 0.2 A g-1 after 200 cycles, while excellent rate performances and cycle life are also acquired in that capacity values of 256.7 and 219.6 mA h g-1 at 1 and 5 A g-1 are preserved after 1000 cycles, respectively. In addition, the assembled sodium-ion hybrid capacitors (SIHCs, AC//WS2/NC@C) exhibit an energy/power density of 68 W h kg-1 at 64 W kg-1, and capacity retention of 82.9% at 1 A g-1 after 2000 cycles. The study provides insight into developing layered metal sulfides with eminent performance of Na+ storage.