3D Printed High‐Loading Lithium‐Sulfur Battery Toward Wearable Energy Storage

Wearable electronic devices are the new darling of consumer electronics, and energy storage devices are an important part of them. Here, a wearable lithium‐sulfur (Li‐S) bracelet battery using three‐dimensional (3D) printing technology (additive manufacturing) is designed and manufactured for the first time. The bracelet battery can be easily worn to power the wearable device. The “additive” manufacturing characteristic of 3D printing provides excellent controllability of the electrode thickness with much simplified process in a cost‐effective manner. Due to the conductive 3D skeleton providing interpenetrating transmission paths and channels for electrons and ions, the 3D Li‐S battery can provide 505.4 mAh g^?1 specific capacity after 500 cycles with an active material loading as high as 10.2 mg cm^?1. The practicality is illustrated by wearing the bracelet battery on the wrist and illuminating the red light‐emitting diode. Therefore, the bracelet battery manufactured by 3D printing technology can address the needs of the wearable power supply.     

3D Carbon Nanotube Network Bridged Hetero‐Structured Ni‐Fe‐S Nanocubes toward High‐Performance Lithium,Sodium, and Potassium Storage

Lithium‐ion, sodium‐ion, and potassium‐ion batteries have captured tremendous attention in power supplies for various electric vehicles and portable electronic devices. However, their practical applications are severely limited by factors such as poor rate capability, fast capacity decay, sluggish charge storage dynamics, and low reversibility. Herein, hetero‐structured bimetallic sulfide (NiS/FeS) encapsulated in N‐doped porous carbon cubes interconnected with CNTs (Ni‐Fe‐S‐CNT) are prepared through a convenient co‐precipitation and post‐heat treatment sulfurization technique of the corresponding Prussian‐blue analogue nanocage precursor. This special 3D hierarchical structure can offer a stable interconnect and conductive network and shorten the diffusion path of ions, thereby greatly enhancing the mobility efficiency of alkali (Li, Na, K) ions in electrode materials. The Ni‐Fe‐S‐CNT nanocomposite maintains a charge capacity of 1535 mAh g^?1 at 0.2 A g^?1 for lithium ion batteries, 431 mAh g^?1 at 0.1 A g^?1 for sodium ion batteries, and 181 mAh g^?1 at 0.1 A g^?1 for potassium‐ion batteries, respectively. The high performance is mainly attributed to the 3D hierarchically high‐conductivity network architecture, in which the hetero‐structured FeS/NiS nanocubes provide fast Li⁺/Na⁺/K⁺ insertion/extraction and reduced ion diffusion paths, and the distinctive 3D networks maintain the electrical contact and guarantee the structural integrity.     

Mesoporous NiCo2O4 Nanowire Arrays Grown on Carbon Textiles as Binder‐Free Flexible Electrodes for Energy Storage

Binary metal oxides has been regarded as a promising class of electrode materials for high‐performance energy storage devices since it offers higher electrochemical activity and higher capacity than mono‐metal oxide. Besides, rational design of electrode architectures is an effective solution to further enhance electrochemical performance of energy storage devices. Here, the advanced electrode architectures consisting of carbon textiles uniformally covered by mesoporous NiCo₂O₄ nanowire arrays (NWAs) are successfully fabricated by a simple surfactant‐assisted hydrothermal method combined with a short post annealing treatment, which can be directly applied as self‐supported electrodes for energy storage devices, such as Li‐ion batteries, supercapacitors. The as‐prepared mesoporous NiCo₂O₄ nanowires consist of numerous highly crystalline nanoparticles, leaving a large number of mesopores to alleviate the volume change during the charge/discharge process. Electrode architectures presented here promise fast electron transport by direct connection to the growth substrate and facile ion diffusion path provided by both the abundant mesoporous structure in nanowires and large open spaces between neighboring nanowires, which ensures every nanowire participates in the ultrafast electrochemical reaction. Benefiting from the intrinsic materials and architectures features, the unique binder‐free NiCo₂O₄/carbon textiles exhibit high specific capacity/capacitance, excellent rate capability, and cycling stability.     

Inkjet Printing Flexible Thermoelectric Devices Using Metal Chalcogenide Nanowires

Development of flexible thermoelectric devices offers exciting opportunities for wearable applications in consumer electronics, healthcare, human–machine interface, etc. Despite the increased interests and efforts in nanotechnology-enabled flexible thermoelectrics, translating the superior properties of thermoelectric materials from nanoscale to macroscale and reducing the manufacturing costs at the device level remain a major challenge. Here, an economic and scalable inkjet printing method is reported to fabricate high-performance flexible thermoelectric devices. A general templated-directed chemical transformation process is employed to synthesize several types of 1D metal chalcogenide nanowires (e.g., Ag₂Te, Cu₇Te₄, and Bi₂Te_2.7Se_0.3). These nanowires are made into inks suitable for inkjet printing by dispersing them in ethanol without any additives. As a showcase for thermoelectric applications, fully inkjet-printed Ag₂Te-based flexible films and devices are prepared. The printed films exhibit a power factor of 493.8 µW m⁻¹ K⁻² at 400 K and the printed devices demonstrate a maximum power density of 0.9 µW cm⁻² K⁻², both of which are significantly higher than those reported in state-of-the-art inkjet-printed thermoelectrics. The protocols of metal chalcogenide ink formulations, as well as printing are general and extendable to a wider range of material systems, suggesting the great potential of this printing platform for scalable manufacturing of next-generation, high-performance flexible thermoelectric devices.     

Understanding Origin of Voltage Hysteresis in Conversion Reaction for Na Rechargeable Batteries: The Case of Cobalt Oxides

Conversion reaction electrodes offer a high specific capacity in rechargeable batteries by utilizing wider valence states of transition metals than conventional intercalation‐based electrodes and have thus been intensively studied in recent years as potential electrode materials for high‐energy‐density rechargeable batteries. However, several issues related to conversion reactions remain poorly understood, including the polarization or hysteresis during charge/discharge processes. Herein, Co₃O₄ in Na cells is taken as an example to understand the aforementioned properties. The large hysteresis in charge/discharge profiles is revealed to be due to different electrochemical reaction paths associated with respective charge and discharge processes, which is attributed to the mobility gap among inter‐diffusing species in a metal oxide compound during de/sodiation. Furthermore, a Co₃O₄–graphene nanoplatelet hybrid material is demonstrated to be a promising anode for Na rechargeable batteries, delivering a capacity of 756 mAh g^?1 with a good reversibility and an energy density of 96 Wh kg^?1 (based on the total electrode weight) when combined with a recently reported Na₄Fe₃(PO₄)₂(P₂O₇) cathode.     

All‐Cellulose‐Based Quasi‐Solid‐State Sodium‐Ion Hybrid Capacitors Enabled by Structural Hierarchy

Na‐ion hybrid capacitors consisting of battery‐type anodes and capacitor‐style cathodes are attracting increasing attention on account of the abundance of sodium‐based resources as well as the potential to bridge the gap between batteries (high energy) and supercapacitors (high power). Herein, hierarchically structured carbon materials inspired by multiscale building units of cellulose from nature are assembled with cellulose‐based gel electrolytes into Na‐ion capacitors. Nonporous hard carbon anodes are obtained through the direct thermal pyrolysis of cellulose nanocrystals. Nitrogen‐doped carbon cathodes with a coral‐like hierarchically porous architecture are prepared via hydrothermal carbonization and activation of cellulose microfibrils. The reversible charge capacity of the anode is 256.9 mAh g^?1 when operating at 0.1 A g^?1 from 0 to 1.5 V versus Na⁺/Na, and the discharge capacitance of cathodes tested within 1.5 to 4.2 V versus Na⁺/Na is 212.4 F g^?1 at 0.1 A g^?1. Utilizing Na⁺ and ClO₄^? as charge carriers, the energy density of the full Na‐ion capacitor with two asymmetric carbon electrodes can reach 181 Wh kg^?1 at 250 W kg^?1, which is one of the highest energy devices reported until now. Combined with macrocellulose‐based gel electrolytes, all‐cellulose‐based quasi‐solid‐state devices are demonstrated possessing additional advantages in terms of overall sustainability.     

Electrical Conductivity Adjustment for Interface Capacitive-Like Storage in Sodium-Ion Battery

Sodium-ion battery (SIB) is significant for grid-scale energy storage. However, a large radius of Na ions raises the difficulties of ion intercalation, hindering the electrochemical performance during fast charge/discharge. Conventional strategies to promote rate performance focus on the optimization of ion diffusion. Improving interface capacitive-like storage by tuning the electrical conductivity of electrodes is also expected to combine the features of the high energy density of batteries and the high power density of capacitors. Inspired by this concept, an oxide-metal sandwich 3D-ordered macroporous architecture (3DOM) stands out as a superior anode candidate for high-rate SIBs. Taking Ni-TiO₂ sandwich 3DOM as a proof-of-concept, anatase TiO₂ delivers a reversible capacity of 233.3 mAh g⁻¹ in half-cells and 210.1 mAh g⁻¹ in full-cells after 100 cycles at 50 mA g⁻¹. At the high charge/discharge rate of 5000 mA g⁻¹, 104.4 mAh g⁻¹ in half-cells and 68 mAh g⁻¹ in full-cells can also be obtained with satisfying stability. In-depth analysis of electrochemical kinetics evidence that the dominated interface capacitive-like storage enables ultrafast uptaking and releasing of Na-ions. This understanding between electrical conductivity and rate performance of SIBs is expected to guild future design to realize effective energy storage.     

Novel Cathode Materials for Na‐Ion Batteries Composed of Spoke‐Like Nanorods of Na[Ni0.61Co0.12Mn0.27]O2 Assembled in Spherical Secondary Particles

The development of high‐energy and high‐power density sodium‐ion batteries is a great challenge for modern electrochemistry. The main hurdle to wide acceptance of sodium‐ion batteries lies in identifying and developing suitable new electrode materials. This study presents a composition‐graded cathode with average composition Na[Ni_0.61Co_0.12Mn_0.27]O₂, which exhibits excellent performance and stability. In addition to the concentration gradients of the transition metal ions, the cathode is composed of spoke‐like nanorods assembled into a spherical superstructure. Individual nanorod particles also possess strong crystallographic texture with respect to the center of the spherical particle. Such morphology allows the spoke‐like nanorods to assemble into a compact structure that minimizes its porosity and maximizes its mechanical strength while facilitating Na⁺‐ion transport into the particle interior. Microcompression tests have explicitly verified the mechanical robustness of the composition‐graded cathode and single particle electrochemical measurements have demonstrated the electrochemical stability during Na⁺‐ion insertion and extraction at high rates. These structural and morphological features contribute to the delivery of high discharge capacities of 160 mAh (g oxide)^?1 at 15 mA g^?1 (0.1 C rate) and 130 mAh g^?1 at 1500 mA g^?1 (10 C rate). The work is a pronounced step forward in the development of new Na ion insertion cathodes with a concentration gradient.     

Few‐Layered SnS2 on Few‐Layered Reduced Graphene Oxide as Na‐Ion Battery Anode with Ultralong Cycle Life and Superior Rate Capability

Na‐ion Batteries have been considered as promising alternatives to Li‐ion batteries due to the natural abundance of sodium resources. Searching for high‐performance anode materials currently becomes a hot topic and also a great challenge for developing Na‐ion batteries. In this work, a novel hybrid anode is synthesized consisting of ultrafine, few‐layered SnS₂ anchored on few‐layered reduced graphene oxide (rGO) by a facile solvothermal route. The SnS₂/rGO hybrid exhibits a high capacity, ultralong cycle life, and superior rate capability. The hybrid can deliver a high charge capacity of 649 mAh g^?1 at 100 mA g^?1. At 800 mA g^?1 (1.8 C), it can yield an initial charge capacity of 469 mAh g^?1, which can be maintained at 89% and 61%, respectively, after 400 and 1000 cycles. The hybrid can also sustain a current density up to 12.8 A g^?1 (≈28 C) where the charge process can be completed in only 1.3 min while still delivering a charge capacity of 337 mAh g^?1. The fast and stable Na‐storage ability of SnS₂/rGO makes it a promising anode for Na‐ion batteries.     

Electrochemical properties of BiFeO3 nanoparticles: Anode material for sodium-ion battery application

We report on synthesis and possibilities of utilizing BiFeO₃ (BFO) nanoparticles and bulk materials as an anode component for sodium (Na) ion batteries. XRD and Raman spectroscopy measurements shows that as synthesized BFO exhibits rhombohedrally distorted perovskite structure. Cyclic voltammetry (CV) reveals that conversion redox mechanism takes place at first discharge and subsequently two alloying process. The specific capacity of BFO bulk material is seen to be 650 mAh/g at first cycle and gradually decreases to 250 mAh/g after 30 cycles (0.1 C rate). After 30 cycles, capacity fading takes place very slowly and is observed to be 180 mAh/g at 100th cycle. The discharge capacity of BFO material at different current rates is carried out and the better performance is seen at the current rates of 25 mA/g. The conversion reaction mechanism during the electrochemical reaction in BiFeO₃ is probed by combining ex-situ XRD and XPS measurements after electrochemical cycling. CV of BFO nanoparticles exhibit very stable performance. Whereas, the charge discharge curve shows similar capacity fading as the bulk BFO. High initial capacity of BiFeO₃ gives an indication that it can be utilized as an anode component for Na ion batteries after stabilizing the capacity fading.     

High-Performance Aqueous Na–Zn Hybrid Ion Battery Boosted by “Water-In-Gel” Electrolyte

Aqueous hybrid Na–Zn ion batteries (ASZIBs) are promising for large-scale energy storage due to their low cost and potential for high output voltage. However, most ASZIBs show limited discharge voltage (<2.0 V) and capacity (<100 mAh g^–1) due to inefficient usage of the dual ions. In this study, a novel large-electrochemical-window “water-in-gel” electrolyte based CuHCF-CNT/Zn Na–Zn hybrid battery is proposed, which achieves a high extraction voltage of Na ion (2.1 V vs Zn/Zn²⁺), together with a large discharge specific capacity (260 mAh g^–1) thanks to the Zn-ion insertion, delivering a superior energy density of 440 Wh kg^–1. The hybrid battery also shows a high capacity retention of 96.8% after 450 cycles. Moreover, an ultrahigh discharge capacity of 1250 mAh g^–1 is achieved when further coupled with the Zn-O₂ reaction, delivering the promising application of ion intercalation and metal–air hybrid battery.     

All-inkjet-printed dissolved oxygen sensors on flexible plastic substrates

Inkjet printing is a promising alternative manufacturing method to conventional standard microfabrication techniques for the development of flexible and low-cost devices. Although the use of inkjet printing for the deposition of selected materials for the development of sensor devices has been reported many times in literature, it is still a challenge and a potential route towards commercialization to completely manufacture sensor devices with inkjet technology. In this work is demonstrated the fabrication of a functional low-cost dissolved oxygen (DO) amperometric sensor with feature sizes in the micrometer range using inkjet printing. All the required technological steps for the fabrication of a complete electrochemical three electrodes system are discussed in detail. The working and counter electrodes have been printed using a gold nanoparticle ink, whereas a silver nanoparticle ink was used to print a pseudo-reference electrode. Both inks are commercially available and can be sintered at low temperatures, starting already at 120 °C, which allows the use of plastic substrates. In addition, a printable SU8 ink formulation cured by UV is applied as passivation layer in the sensor device. Finally, as the performance of analytical methods strongly depends on the working electrode material, is demonstrated the electrochemical feasibility of this printed DO sensor, which shows a linear response in the range between 0 and 8 mg L⁻¹ of DO, and affords a detection limit of 0.11 mg L⁻¹, and a sensitivity of 0.03 μA L mg⁻¹. The use of flexible plastic substrates and biocompatible inks, and the rapid prototyping and low-cost of the fabricated sensors, makes that the proposed manufacturing approach opens new opportunities in the field of biological and medical sensor applications.     

Rambutan‐Like Hybrid Hollow Spheres of Carbon Confined Co3O4 Nanoparticles as Advanced Anode Materials for Sodium‐Ion Batteries

Transition metal oxides, possessing high theoretical specific capacities, are promising anode materials for sodium‐ion batteries. However, the sluggish sodiation/desodiation kinetics and poor structural stability restrict their electrochemical performance. To achieve high and fast Na storage capability, in this work, rambutan‐like hybrid hollow spheres of carbon confined Co₃O₄ nanoparticles are synthesized by a facile one‐pot hydrothermal treatment with postannealing. The hierarchy hollow structure with ultrafine Co₃O₄ nanoparticles embedded in the continuous carbon matrix enables greatly enhanced structural stability and fast electrode kinetics. When tested in sodium‐ion batteries, the hollow structured composite electrode exhibits an outstandingly high reversible specific capacity of 712 mAh g^?1 at a current density of 0.1 A g^?1, and retains a capacity of 223 mAh g^?1 even at a large current density of 5 A g^?1. Besides the superior Na storage capability, good cycle performance is demonstrated for the composite electrode with 74.5% capacity retention after 500 cycles, suggesting promising application in advanced sodium‐ion batteries.     

Dendrite-Free and Long-Cycling Sodium Metal Batteries Enabled by Sodium-Ether Cointercalated Graphite Anode

Stable and dendrite-free Na metal plating–stripping is achieved on the graphite electrode. The sodium-ether cointercalated graphite exhibits ultrahigh Na deposition efficiency of 99.86% over 900 cycles at a current density of 2 mA cm⁻². The discharge process involves the [Na-ether]⁺ cointercalation and Na deposition. Density functional theory calculations demonstrate that the cointercalated graphite is critical for uniform Na deposition and stable Coulombic efficiency, which is ascribed to both the robust binding sites to Na by the diglyme molecules and a low lattice mismatch for Na growth on the cointercalated graphite. Also, a full cell consisting of Na₄Fe₃(PO₄)₂(P₂O₇) cathode and 0.5 mAh cm⁻² Na predeposited graphite anode shows excellent cycling stability. The full cell delivers a capacity of 95 mAh g⁻¹ based on the weight of cathode materials, with a high capacity retention of 91% over 300 cycles.     

Pseudocapacitive Trimetal Fe0.8CoMnO4 Nanoparticles@Carbon Nanofibers as High‐Performance Sodium Storage Anode with Self‐Supported Mechanism

Trimetal Fe_0.8CoMnO₄ (FCMO) nanocrystals with a diameter of about 50 nm perfectly embedded in N doped‐carbon composite nanofibers (denoted as FCMO@C) are successfully prepared through integrating double‐nozzle electrospinning with a drying and calcination process. The as‐prepared FCMO@C nanofibers maintain a high reversible capacity of 420 mAh g^?1 and about 90% capacity retention after 200 cycles at 0.1 A g^?1. For a long‐term cycle, the FCMO@C electrode exhibits excellent cycling stability (87% high capacity retention at 1 A g^?1 after 950 cycles). Kinetic analysis demonstrates that the electrochemical characteristics of the FCMO@C corresponds to the pseudocapacitive approach in charge storage as an anode for sodium ion batteries, which dominantly attributes the credit to FCMO nanocrystals to shorten the migration distance of Na⁺ ions and the nitrogen‐doped carbon skeleton to enhance the electronic transmission and favorably depress the volume expansion during the repeated insertion/extraction of Na⁺ ions. More significantly, a self‐supported mechanism via continuous electrochemical redox reaction of Fe, Co, and Mn can effectively relieve the volume change during charge and discharge. Therefore, this work can provide a new avenue to improve the sodium storage performance of the oxide anode materials.     

Toward Optimal Performance and In‐Depth Understanding of Spinel Li4Ti5O12 Electrodes through Phase Field Modeling

Computational modeling is vital for the fundamental understanding of processes in Li‐ion batteries. However, capturing nanoscopic to mesoscopic phase thermodynamics and kinetics in the solid electrode particles embedded in realistic electrode morphologies is challenging. In particular for electrode materials displaying a first order phase transition, such as LiFePO₄, graphite, and spinel Li₄Ti₅O₁₂, predicting the macroscopic electrochemical behavior requires an accurate physical model. Herein, a thermodynamic phase field model is presented for Li‐ion insertion in spinel Li₄Ti₅O₁₂ which captures the performance limitations presented in literature as a function of all relevant electrode parameters. The phase stability in the model is based on ab initio density functional theory calculations and the Li‐ion diffusion parameters on nanoscopic nuclear magnetic resonance (NMR) measurements of Li‐ion mobility, resulting in a parameter free model. The direct comparison with prepared electrodes shows good agreement over three orders of magnitude in the discharge current. Overpotentials associated with the various charge transport processes, as well as the active particle fraction relevant for local hotspots in batteries, are analyzed. It is demonstrated which process limits the electrode performance under a variety of realistic conditions, providing comprehensive understanding of the nanoscopic to microscopic properties. These results provide concrete directions toward the design of optimally performing Li₄Ti₅O₁₂ electrodes.     

A General Metal‐Organic Framework (MOF)‐Derived Selenidation Strategy for In Situ Carbon‐Encapsulated Metal Selenides as High‐Rate Anodes for Na‐Ion Batteries

On account of increasing demand for energy storage devices, sodium‐ion batteries (SIBs) with abundant reserve, low cost, and similar electrochemical properties have the potential to partly replace the commercial lithium‐ion batteries. In this study, a facile metal‐organic framework (MOF)‐derived selenidation strategy to synthesize in situ carbon‐encapsulated selenides as superior anode for SIBs is rationally designed. These selenides with particular micro‐ and nanostructured features deliver ultrastable cycling performance at high charge–discharge rate and demonstrate ultraexcellent rate capability. For example, the uniform peapod‐like Fe₇Se₈@C nanorods represent a high specific capacity of 218 mAh g^?1 after 500 cycles at 3 A g^?1 and the porous NiSe@C spheres display a high specific capacity of 160 mAh g^?1 after 2000 cycles at 3 A g^?1. The current simple MOF‐derived method could be a promising strategy for boosting the development of new functional inorganic materials for energy storage, catalysis, and sensors.     

Effect of the Ionic Conductivity on the Performance of Polyelectrolyte‐Based Supercapacitors

In the emerging technology field of printed electronics, circuits are envisioned to be powered with printed energy sources, such as printed batteries and printed supercapacitors (SCs). For manufacturing and reliability issues, solid electrolytes are preferred instead of liquid electrolytes. Here, a solid‐state, polyanionic proton conducting electrolyte, poly(styrenesulfonic acid) (PSS:H), is demonstrated for the first time as an effective ion conducting electrolyte medium in SCs with electrodes based on carbon nanotube (CNT) networks. The effect of the ionic conductivity in the PSS:H film of those SCs is studied at different levels of relative humidity (RH) with impedance spectroscopy, cyclic voltammetry, and galvanostatic charge‐discharge techniques. High capacitance values (85 F g^?1 at 80% RH) are obtained for these SCs due to the extremely high effective electrode area of the CNTs and the enhanced ionic conductivity of the PSS:H film at increasing RH level. The charging dynamics are primarily limited by the ionic conductivity of the electrolyte rather than a poor contact between the electrolyte and the CNT electrodes. The use of polyelectrolytes in SCs provides high mechanical strength and flexibility, while maintaining a high capacitance value, enabling a new generation of printable solid‐state charge storage devices.     

High‐Rate LiFePO4 Electrode Material Synthesized by a Novel Route from FePO4 · 4H2O

A LiFePO₄ material with ordered olivine structure is synthesized from amorphous FePO₄ · 4H₂O through a solid–liquid phase reaction using (NH₄)₂SO₃ as the reducing agent, followed by thermal conversion of the intermediate NH₄FePO₄ in the presence of LiCOOCH₃ · 2H₂O. Simultaneous thermogravimetric–differential thermal analysis indicates that the crystallization temperature of LiFePO₄ is about 437 °C. Ellipsoidal particle morphology of the resulting LiFePO₄ powder with a particle size mainly in the range 100–300 nm is observed by using scanning electron microscopy and transmission electron microscopy. As an electrode material for rechargeable lithium batteries, the LiFePO₄ sample delivers a discharge capacity of 167 mA h g^–1 at a constant current of 17 mA g^–1 (0.1 C rate; throughout this study n C rate means that rated capacity of LiFePO₄ (170 mA h g^–1) is charged or discharged completely in 1/n hours), approaching the theoretical value of 170 mA h g^–1. Moreover, the electrode shows excellent high‐rate charge and discharge capability and high electrochemical reversibility. No capacity loss can be observed up to 50 cycles under 5 C and 10 C rate conditions. With a conventional charge mode, that is, 5 C rate charging to 4.2 V and then keeping this voltage until the charge current is decreased to 0.1 C rate, a discharge capacity of ca. 134 mA h g^–1 and cycling efficiency of 99.2–99.6 % can be obtained at 5 C rate.