High‐Performance Integrated Self‐Package Flexible Li–O2 Battery Based on Stable Composite Anode and Flexible Gas Diffusion Layer

With the rising development of flexible and wearable electronics, corresponding flexible energy storage devices with high energy density are required to provide a sustainable energy supply. Theoretically, rechargeable flexible Li–O₂ batteries can provide high specific energy density; however, there are only a few reports on the construction of flexible Li–O₂ batteries. Conventional flexible Li–O₂ batteries possess a loose battery structure, which prevents flexibility and stability. The low mechanical strength of the gas diffusion layer and anode also lead to a flexible Li–O₂ battery with poor mechanical properties. All these attributes limit their practical applications. Herein, the authors develop an integrated flexible Li–O₂ battery based on a high‐fatigue‐resistance anode and a novel flexible stretchable gas diffusion layer. Owing to the synergistic effect of the stable electrocatalytic activity and hierarchical 3D interconnected network structure of the free‐standing cathode, the obtained flexible Li–O₂ batteries exhibit superior electrochemical performance, including a high specific capacity, an excellent rate capability, and exceptional cycle stability. Furthermore, benefitting from the above advantages, the as‐fabricated flexible batteries can realize excellent mechanical and electrochemical stability. Even after a thousand cycles of the bending process, the flexible Li–O₂ battery can still possess a stable open‐circuit voltage, a high specific capacity, and a durable cycle performance.     

Lithium Titanate Cuboid Arrays Grown on Carbon Fiber Cloth for High‐Rate Flexible Lithium‐Ion Batteries

High‐rate performance flexible lithium‐ion batteries are desirable for the realization of wearable electronics. The flexibility of the electrode in the battery is a key requirement for this technology. In the present work, spinel lithium titanate (Li₄Ti₅O₁₂, LTO) cuboid arrays are grown on flexible carbon fiber cloth (CFC) to fabricate a binder‐free composite electrode (LTO@CFC) for flexible lithium‐ion batteries. Experimental results show that the LTO@CFC electrode exhibits a remarkably high‐rate performance with a capacity of 105.8 mAh g^?1 at 50C and an excellent electrochemical stability against cycling (only 2.2% capacity loss after 1000 cycles at 10C). A flexible full cell fabricated with the LTO@CFC as the anode and LiNi_0.5Mn_1.5O₄ coated on Al foil as the cathode displays a reversible capacity of 109.1 mAh g^?1 at 10C, an excellent stability against cycling and a great mechanical stability against bending. The observed high‐rate performance of the LTO@CFC electrode is due to its unique corn‐like architecture with LTO cuboid arrays (corn kernels) grown on CFC (corn cob). This work presents a new approach to preparing LTO‐based composite electrodes with an architecture favorable for ion and electron transport for flexible energy storage devices.     

Ultrathin Co3O4 nanosheets highly dispersed on reduced graphene oxide: An efficient bi-functional catalyst for Li-O2 battery

Ultrathin Co₃O₄ nanosheets grown on the reduced graphene oxide (Co₃O₄/rGO) was synthesized by a simple hydrothermal method and was investigated as a cathode in a Li-O₂ battery. Benefited from the synergistic effect between Co₃O₄ and rGO, the hybrid exhibits a high initial capacity of 10,528 mAh g^?1 along with a high coulombic efficiency (84.4%) at 100 mA g^?1. In addition, the batteries show an enhanced cycling stability and after 113 cycles, the cut-off discharge voltage remains above 2.5 V. The outstanding performance is intimately related to the high surface area of rGO, which not only provide carbon skeleton for the uniform distribution of Co₃O₄ nanosheets but also facilitate the reversible formation and decomposition of insoluble Li₂O₂. The results of electrochemical tests confirm that the Co₃O₄/rGO hybrid is a promising candidate for the Li-O₂ batteries.     

Rutile TiO2 nanorod arrays directly grown on Ti foil substrates towards lithium-ion micro-batteries

Nanosized rutile TiO₂ is one of the most promising candidates for anode material in lithium-ion micro-batteries owing to their smaller dimension in ab-plane resulting in an enhanced performance for area capacity. However, few reports have yet emerged up to date of rutile TiO₂ nanorod arrays growing along c-axis for Li-ion battery electrode application. In this study, single-crystalline rutile TiO₂ nanorod arrays growing directly on Ti foil substrates have been fabricated using a template-free method. These nanorods can significantly improve the electrochemical performance of rutile TiO₂ in Li-ion batteries. The capacity increase is about 10 times in comparison with rutile TiO₂ compact layer.     

三维花状MoS2锌离子电池正极材料的设计构筑及其储能机制研究

采用水热法设计构筑三维花状二硫化钼,并利用XRD、SEM、RAMAN、TG等测试方法对产物的结构和形貌进行了表征,进而作为正极材料组装成锌离子电池并对其进行电化学测试分析,在充放电电压区间为0.2~1.2V、电流密度为1.0A/g条件下,首次放电比容量可达63.9 mAh/g,100次循环后其放电比容量保持在53.6mAh/g,容量保持率为83.9%。较高的比容量和循环稳定性使MoS_2成为有前景的锌离子电池正极材料之一。     

A Carbonyl Compound‐Based Flexible Cathode with Superior Rate Performance and Cyclic Stability for Flexible Lithium‐Ion Batteries

A sulfur‐linked carbonyl‐based poly(2,5‐dihydroxyl‐1,4‐benzoquinonyl sulfide) (PDHBQS) compound is synthesized and used as cathode material for lithium‐ion batteries (LIBs). Flexible binder‐free composite cathode with single‐wall carbon nanotubes (PDHBQS–SWCNTs) is then fabricated through vacuum filtration method with SWCNTs. Electrochemical measurements show that PDHBQS–SWCNTs cathode can deliver a discharge capacity of 182 mA h g⁻¹ (0.9 mA h cm⁻²) at a current rate of 50 mA g⁻¹ and a potential window of 1.5 V–3.5 V. The cathode delivers a capacity of 75 mA h g⁻¹ (0.47 mA h cm⁻²) at 5000 mA g⁻¹, which confirms its good rate performance at high current density. PDHBQS–SWCNTs flexible cathode retains 89% of its initial capacity at 250 mA g⁻¹ after 500 charge–discharge cycles. Furthermore, large‐area (28 cm²) flexible batteries based on PDHBQS–SWCNTs cathode and lithium foils anode are also assembled. The flexible battery shows good electrochemical activities with continuous bending, which retains 88% of its initial discharge capacity after 2000 bending cycles. The significant capacity, high rate performance, superior cyclic performance, and good flexibility make this material a promising candidate for a future application of flexible LIBs.     

Non-aqueous rechargeable Al–O2 battery with a bifunctional catalyst of carbon microspheres

Non-aqueous secondary Al-O₂ batteries have recently received much attention due to their high theoretical capacity, element richness, safety and low cost, although there are still many problems to be overcome. In this paper, a type of Al-O₂ battery using AlCl₃/[EMIm]Cl ionic liquid as electrolyte and carbon microspheres (CMs) as air electrode was considered. The batteries with CMs deliver a high specific capacity of 820 mAh g^?1 in the first cycle at the current density of 25 mA g^?1 and a low charge voltage. In addition, CMs show better redox catalytic activity for O₂ compared with super-p (SP) and the Al-O₂ batteries have two obvious oxygen reduction processes corresponding to two reductive peaks.     

Achieving Ultrahigh Energy Density and Long Durability in a Flexible Rechargeable Quasi‐Solid‐State Zn–MnO2 Battery

Advanced flexible batteries with high energy density and long cycle life are an important research target. Herein, the first paradigm of a high‐performance and stable flexible rechargeable quasi‐solid‐state Zn–MnO₂ battery is constructed by engineering MnO₂ electrodes and gel electrolyte. Benefiting from a poly(3,4‐ethylenedioxythiophene) (PEDOT) buffer layer and a Mn²⁺‐based neutral electrolyte, the fabricated Zn–MnO₂@PEDOT battery presents a remarkable capacity of 366.6 mA h g^?1 and good cycling performance (83.7% after 300 cycles) in aqueous electrolyte. More importantly, when using PVA/ZnCl₂/MnSO₄ gel as electrolyte, the as‐fabricated quasi‐solid‐state Zn–MnO₂@PEDOT battery remains highly rechargeable, maintaining more than 77.7% of its initial capacity and nearly 100% Coulombic efficiency after 300 cycles. Moreover, this flexible quasi‐solid‐state Zn–MnO₂ battery achieves an admirable energy density of 504.9 W h kg^?1 (33.95 mW h cm^?3), together with a peak power density of 8.6 kW kg^?1, substantially higher than most recently reported flexible energy‐storage devices. With the merits of impressive energy density and durability, this highly flexible rechargeable Zn–MnO₂ battery opens new opportunities for powering portable and wearable electronics.     

V2O5 Textile Cathodes with High Capacity and Stability for Flexible Lithium-Ion Batteries

Textile-based energy-storage devices are highly appealing for flexible and wearable electronics. Here, a 3D textile cathode with high loading, which couples hollow multishelled structures (HoMSs) with conductive metallic fabric, is reported for high-performance flexible lithium-ion batteries. V₂O₅ HoMSs prepared by sequential templating approach are used as active materials and conductive metallic fabrics are applied as current collectors and flexible substrates. Taking advantage of the desirable structure of V₂O₅ HoMSs that effectively buffers the volume expansion and alleviates the stress/strain during repeated Li-insertion/extraction processes, as well as the robust flexible metallic-fabric current collector, the as-prepared fabric devices show excellent electrochemical performance and ultrahigh stability. The capacity retains a high value of 222.4 mA h g⁻¹ at a high mass loading of 2.5 mg cm⁻² even after 500 charge/discharge cycles, and no obvious performance degradation is observed after hundreds of cycles of bending and folding. These results indicate that V₂O₅ HoMSs/metallic-fabric cathode electrode is promising for highly flexible lithium-ion batteries.     

Textile Inspired Lithium–Oxygen Battery Cathode with Decoupled Oxygen and Electrolyte Pathways

The lithium–air (Li–O₂) battery has been deemed one of the most promising next‐generation energy‐storage devices due to its ultrahigh energy density. However, in conventional porous carbon–air cathodes, the oxygen gas and electrolyte often compete for transport pathways, which limit battery performance. Here, a novel textile‐based air cathode is developed with a triple‐phase structure to improve overall battery performance. The hierarchical structure of the conductive textile network leads to decoupled pathways for oxygen gas and electrolyte: oxygen flows through the woven mesh while the electrolyte diffuses along the textile fibers. Due to noncompetitive transport, the textile‐based Li–O₂ cathode exhibits a high discharge capacity of 8.6 mAh cm^?2, a low overpotential of 1.15 V, and stable operation exceeding 50 cycles. The textile‐based structure can be applied to a range of applications (fuel cells, water splitting, and redox flow batteries) that involve multiple phase reactions. The reported decoupled transport pathway design also spurs potential toward flexible/wearable Li–O₂ batteries.     

Micro-sized and Nano-sized Fe_3O_4 Particles as Anode Materials for Lithium-ion Batteries

Micro-sized(1030.3±178.4 nm) and nano-sized(50.4±8.0 nm) Fe3O4 particles have been fabricated through hydrogen thermal reduction of α-Fe2O3 particles synthesized by means of a hydrothermal process.The morphology and microstructure of the micro-sized and the nano-sized Fe3O4 particles were characterized by X-ray diffraction,field-emission gun scanning electron microscopy,transmission electron microscopy and highresolution electron microscopy.The micro-sized Fe3O4 particles exhibit porous structure,while the nano-sized Fe3O4 particles are solid structure.Their electrochemical performance was also evaluated.The nano-sized solid Fe3O4 particles exhibit gradual capacity fading with initial discharge capacity of 1083.1 mAhg-1 and reversible capacity retention of 32.6% over 50 cycles.Interestingly,the micro-sized porous Fe3O4 particles display very stable capacity-cycling behavior,with initial discharge capacity of 887.5 mAhg-1 and charge capacity of 684.4 mAhg-1 at the 50th cycle.Therefore,77.1% of the reversible capacity can be maintained over 50 cycles.The micro-sized porous Fe3O4 particles with facile synthesis,good cycling performance and high capacity retention are promising candidate as anode materials for high energy-density lithium-ion batteries.     

Neutron imaging of a commercial Li-ion battery during discharge: Application of monochromatic imaging and polychromatic dynamic tomography

A commercial lithium-ion polymer battery of prismatic construction was imaged in 2D by monochromatic neutron radiography at wavelengths around a LiC₆ spectral feature. Over the range of 3-4 Å, the neutron attenuation spectra for charged and discharged batteries are distinctly different. In a real-time experiment, a battery was observed during discharge at wavelengths spanning the LiC₆ spectral feature and its disappearance monitored. No evidence of “staging” was detected in this preliminary experiment. A similar battery was imaged in 3D with a new tomographic data acquisition scheme based on the Greek golden ratio; the scheme allows convenient post-processing to establish “time windows” for 3D image reconstruction. The 3D images at 5% state of charge intervals are compromised by beam hardening, but still show some asymmetric battery volume change with discharge. Finally comments on the future of neutron imaging for battery experiments, whether at continuous sources at nuclear reactors or at pulsed spallation sources, are discussed.     

Carbon Foam-Supported VS2 Cathode for High-Performance Flexible Self-Healing Quasi-Solid-State Zinc-Ion Batteries

As the new generation of energy storage systems, the flexible battery can effectively broaden the application area and scope of energy storage devices. Flexibility and energy density are the two core evaluation parameters for the flexible battery. In this work, a flexible VS₂ material (VS₂@CF) is fabricated by growing the VS₂ nanosheet arrays on carbon foam (CF) using a simple hydrothermal method. Benefiting from the high electric conductivity and 3D foam structure, VS₂@CF shows an excellent rate capability (172.8 mAh g⁻¹ at 5 A g⁻¹) and cycling performance (130.2 mAh g⁻¹ at 1 A g⁻¹ after 1000 cycles) when it served as cathode material for aqueous zinc-ion batteries. More importantly, the quasi-solid-state battery VS₂@CF//Zn@CF assembled by the VS₂@CF cathode, CF-supported Zn anode, and a self-healing gel electrolyte also exhibits excellent rate capability (261.5 and 149.8 mAh g⁻¹ at 0.2 and 5 A g⁻¹, respectively) and cycle performance with a capacity of 126.6 mAh g⁻¹ after 100 cycles at 1 A g⁻¹. Moreover, the VS₂@CF//Zn@CF full cell also shows good flexible and self-healing properties, which can be charged and discharged normally under different bending angles and after being destroyed and then self-healing.     

Fundamental Understanding of Water‐Induced Mechanisms in Li–O2 Batteries: Recent Developments and Perspectives

Modern sustainability challenges in recent years have warranted the development of new energy storage technologies. Practical realization of the lithium–O₂ battery holds great promise for revolutionizing energy storage as it holds the highest theoretical specific energy of any rechargeable battery yet discovered. However, the complete realization of Li–O₂ batteries necessitates ambient air operations, which presents quite a few challenges, as carbon dioxide (CO₂) and water (H₂O) contaminants introduce unwanted byproducts from side reactions that greatly affect battery performance. Although current research has thoroughly explored the beneficial incorporation of CO₂, much mystery remains over the inconsistent effects of H₂O. The presence of water in both the cathode and electrolyte has been observed to alter reaction mechanisms differently, resulting in a diverse range of effects on voltage, capacity, and cyclability. Moreover, recent preliminary research with catalysts and redox mediators has attempted to utilize the presence of water to the battery's benefit. Here, the key mechanism discrepancies of water‐afflicted Li–O₂ batteries are presented, concluding with a perspective on future research directions for nonaqueous Li–O₂ batteries.     

S‐Doped Carbon Fibers Uniformly Embedded with Ultrasmall TiO2 for Na+/Li+ Storage with High Capacity and Long‐Time Stability

Building a rechargeable battery with high capacity, high energy density, and long lifetime contributes to the development of novel energy storage devices in the future. Although carbon materials are very attractive anode materials for lithium‐ion batteries (LIBs), they present several deficiencies when used in sodium‐ion batteries (SIBs). The choice of an appropriate structural design and heteroatom doping are critical steps to improve the capacity and stability. Here, carbon‐based nanofibers are produced by sulfur doping and via the introduction of ultrasmall TiO₂ nanoparticles into the carbon fibers (CNF‐S@TiO₂). It is discovered that the introduction of TiO₂ into carbon nanofibers can significantly improve the specific surface area and microporous volume for carbon materials. The TiO₂ content is controlled to obtain CNF‐S@TiO₂‐5 to use as the anode material for SIBs/LIBs with enhanced electrochemical performance in Na⁺/Li⁺ storage. During the charge/discharge process, the S‐doping and the incorporation of TiO₂ nanoparticles into carbon fibers promote the insertion/extraction of the ions and enhance the capacity and cycle life. The capacity of CNF‐S@TiO₂‐5 can be maintained at ≈300 mAh g^?1 over 600 cycles at 2 A g^?1 in SIBs. Moreover, the capacity retention of such devices is 94%, showing high capacity and good stability.     

Preparation and electrochemical properties of nano-sized SnF2 as negative electrode for lithium-ion batteries

Nanocrystalline SnF₂ was prepared via recrystallization of commercially available tin (II) fluoride. The electrochemical performance of tin fluoride as anode material for Li-ion batteries was investigated. The cyclic voltammetry of the obtained material showed occurrence of SnF₂ decomposition at first and a typical reversible alloying/de-alloying process at low potentials. Furthermore, it was found that the synthesized material delivered a high reversible capacity of 1016 mAh g^− 1 and a capacity retention of 54.8% after 30 cycles when the electrode was cycled at a current of 100 mA g^− 1.     

Co3O4 Nanosheets as Active Material for Hybrid Zn Batteries

The rapid development of electric vehicles and modern personal electronic devices is severely hindered by the limited energy and power density of the existing power sources. Here a novel hybrid Zn battery is reported which is composed of a nanostructured transition metal oxide‐based positive electrode (i.e., Co₃O₄ nanosheets grown on carbon cloth) and a Zn foil negative electrode in an aqueous alkaline electrolyte. The hybrid battery configuration successfully combines the unique advantages of a Zn–Co₃O₄ battery and a Zn–air battery, achieving a high voltage of 1.85 V in the Zn–Co₃O₄ battery region and a high capacity of 792 mAh g_Zn^?1. In addition, the battery shows high stability while maintaining high energy efficiency (higher than 70%) for over 200 cycles and high rate capabilities. Furthermore, the high flexibility of the carbon cloth substrate allows the construction of a flexible battery with a gel electrolyte, demonstrating not only good rechargeability and stability, but also reasonable mechanical deformation without noticeable degradation in performance. This work also provides an inspiring example for further explorations of high‐performance hybrid and flexible battery systems.     

C60 thin-film transistors with high field-effect mobility,fabricated by molecular beam deposition

We report performance of C₆₀ thin-film field-effect transistors and characterizations of C₆₀ thin-films on SiO₂ substrates fabricated by molecular beam deposition. Devices, fabricated and characterized under high vacuum without exposing to air, routinely showed current on/off ratios >10⁸ and field-effect mobility in the range of 0.5–0.3 cm²/V s. The obtained mobility is comparable to the highest value among n-type organic thin-film transistors and close to that derived from the photocurrent measurements on C₆₀ thin-films.The grain size of C₆₀ thin-film, condensed in an fcc solid, increases with the substrate temperature, while themobility did not exhibit a clear relation with substrate temperature.

© 2003 Elsevier Ltd. All rights reserved.     

In situ synthesis of SnO2/graphene nanocomposite and their application as anode material for lithium ion battery

SnO₂/graphene nanocomposite was prepared via an in situ chemical synthesis method. The nanocomposite was characterized by X-ray diffraction, filed emission scanning electron microscope and transmission electron microscope, which revealed that tiny SnO₂ nanoparticles could be homogeneously distributed on the graphene matrix. The electrochemical performance of the SnO₂/graphene nanocomposite as anode material was measured by galvanostatic charge/discharge cycling. The SnO₂/graphene nanocomposite showed a reversible capacity of 665 mAh/g after 50 cycles and an excellent cycling performance for lithium ion battery, which was ascribed to the three-dimensional architecture of SnO₂/graphene nanocomposite. These results suggest that SnO₂/graphene nanocomposite would be a promising anode material for lithium ion battery.     

Preparation and electrochemical properties of Cr doped LiV3O8 cathode for lithium ion batteries

Chromium was incorporated into lithium trivanadate by an aqueous reaction followed by heating at 100 °C. This Cr doped LiV₃O₈ as a cathode for lithium ion batteries exhibits 269.9 mAh g^− 1 at first discharge cycle and remains 254.8 mAh g^− 1 at cycle 100, with a charge-discharge current density of 150 mA g^− 1 in the voltage range of 1.8-4.0 V. The Cr-LiV₃O₈ cathode show excellent discharge capacity, with the retention of 94.4% after 100 cycles. These result values are higher than previous reports indicating that Cr-LiV₃O₈ prepared by our low temperature synthesis method is a promising cathode material for rechargeable lithium ion batteries. The enhanced discharge capacity and cycle stability of Cr-LiV₃O₈ cathode indicate that chromium atoms promote lithium transfer or intercalation/deintercalation during the electrochemical cycles and improve the electrochemical performances of LiV₃O₈ cathode.