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1.
In this study, hierarchically nanoporous pyropolymers (HN‐PPs) including numerous redox‐active heteroatoms are fabricated from polyaniline nanotubes by heating with KOH. In the large operating voltage range 1.0–4.8 V versus Li+/Li, HN‐PPs store amphicharges by a pseudocapacitive manner of Li‐ion (mainly <3.0 V) and electrochemical double layer formation of anion (primarily >3.0 V). Through these surface‐driven charge storage behaviors, HN‐PPs achieve a significantly high specific capacity of ≈460 mA h g?1 at 0.5 A g?1, maintaining specific capacities of 140 mA h g?1 at a high specific current of 30 A g?1 and 305 mA h g?1 after 2000 cycles at 3 A g?1. Furthermore, asymmetric energy storage devices based on HN‐PPs deliver a high specific energy of 265 W h kg?1 and high specific power of 5081 W kg?1 with long‐term cycling performance.  相似文献   

2.
A flexible and free‐standing porous carbon nanofibers/selenium composite electrode (Se@PCNFs) is prepared by infiltrating Se into mesoporous carbon nanofibers (PCNFs). The porous carbon with optimized mesopores for accommodating Se can synergistically suppress the active material dissolution and provide mechanical stability needed for the film. The Se@PCNFs electrode exhibits exceptional electrochemical performance for both Li‐ion and Na‐ion storage. In the case of Li‐ion storage, it delivers a reversible capacity of 516 mAh g?1 after 900 cycles without any capacity loss at 0.5 A g?1. Se@PCNFs still delivers a reversible capacity of 306 mAh g?1 at 4 A g?1. While being used in Na‐Se batteries, the composite electrode maintains a reversible capacity of 520 mAh g?1 after 80 cycles at 0.05 A g?1 and a rate capability of 230 mAh g?1 at 1 A g?1. The high capacity, good cyclability, and rate capability are attributed to synergistic effects of the uniform distribution of Se in PCNFs and the 3D interconnected PCNFs framework, which could alleviate the shuttle reaction of polyselenides intermediates during cycling and maintain the perfect electrical conductivity throughout the electrode. By rational and delicate design, this type of self‐supported electrodes may hold great promise for the development of Li‐Se and Na‐Se batteries with high power and energy densities.  相似文献   

3.
For the first time, environmentally friendly sulfur‐rich pyramidal MnS2 synthesized via a single‐step hydrothermal process is used as a high‐performance anode material in Li‐ion and Na‐ion batteries. The superior electrochemical performance of the MnS2 electrode along with its high compatibility with ether‐based electrolytes are analyzed in both half‐ and full‐cell configurations. The reversible capacities of ≈84 mAh g?1 and ≈74 mAh g?1 at a current density of 50 mA g?1 are retained in the Li‐ion and Na‐ion full‐cells, respectively, over 200 cycles with excellent capacity retentions. Moreover, important findings regarding activation processes in the presence of a new phase transition and protective electrolyte interphase layer are revealed using ab initio density function theory calculation and in situ potentio‐electrochemical impedance spectroscopy. The detailed complex redox mechanism of MnS2 in Li/Na half‐cells is also elucidated by ex situ X‐ray photoelectron spectroscopy.  相似文献   

4.
Potassium‐ion hybrid capacitors (PIHCs) hold the advantages of high‐energy density of batteries and high‐power output of supercapacitors and thus present great promise for the next generation of electrochemical energy storage devices. One of the most crucial tasks for developing a high‐performance PIHCs is to explore a favorable anode material with capability to balance the kinetics mismatch between battery‐type anodes and capacitor‐type cathode. Herein, a reliable route for fabricating sulfur and nitrogen codoped 3D porous carbon nanosheets (S‐N‐PCNs) is reported. Systematic characterizations coupled with kinetics analysis indicate that the doped heteroatoms of sulfur and nitrogen and the amplified graphite interlayer can provide ample structural defects and redox active sites that are beneficial for improving pseudocapacitive activity, enabling fast kinetics toward efficient potassium‐ion storage. The S‐N‐PCNs are demonstrated to exhibit superior potassium storage capability with a high capacity of 107 mAh g?1 at 20 A g?1 and long cycle stability. The as‐developed PIHCs present impressive electrochemical performance with an operating voltage as high as 4.0 V, an energy density of 187 Wh kg?1, a power density of 5136 W kg?1, and a capacity retention of 86.4% after 3000 cycles.  相似文献   

5.
The polyanion Li7V15O36(CO3) is a nanosized molecular cluster (≈1 nm in size), that has the potential to form an open host framework with a higher surface‐to‐bulk ratio than conventional transition metal oxide electrode materials. Herein, practical rechargeable Na‐ion batteries and symmetric Li‐ion batteries are demonstrated based on the polyoxovanadate Li7V15O36(CO3). The vanadium centers in {V15O36(CO3)} do not all have the same VIV/V redox potentials, which permits symmetric devices to be created from this material that exhibit battery‐like energy density and supercapacitor‐like power density. An ultrahigh specific power of 51.5 kW kg?1 at 100 A g?1 and a specific energy of 125 W h kg?1 can be achieved, along with a long cycling life (>500 cycles). Moreover, electrochemical and theoretical studies reveal that {V15O36(CO3)} also allows the transport of large cations, like Na+, and that it can serve as the cathode material for rechargeable Na‐ion batteries with a high specific capacity of 240 mA h g?1 and a specific energy of 390 W h kg?1 for the full Na‐ion battery. Finally, the polyoxometalate material from these electrochemical energy storage devices can be easily extracted from spent electrodes by simple treatment with water, providing a potential route to recycling of the redox active material.  相似文献   

6.
A new approach to intentionally induce phase transition of Li‐excess layered cathode materials for high‐performance lithium ion batteries is reported. In high contrast to the limited layered‐to‐spinel phase transformation that occurred during in situ electrochemical cycles, a Li‐excess layered Li[Li0.2Mn0.54Ni0.13Co0.13]O2 is completely converted to a Li4Mn5O12‐type spinel product via ex situ ion‐exchanges and a post‐annealing process. Such a layered‐to‐spinel phase conversion is examined using in situ X‐ray diffraction and in situ high‐resolution transmission electron microscopy. It is found that generation of sufficient lithium ion vacancies within the Li‐excess layered oxide plays a critical role for realizing a complete phase transition. The newly formed spinel material exhibits initial discharge capacities of 313.6, 267.2, 204.0, and 126.3 mAh g?1 when cycled at 0.1, 0.5, 1, and 5 C (1 C = 250 mA g?1), respectively, and can retain a specific capacity of 197.5 mAh g?1 at 1 C after 100 electrochemical cycles, demonstrating remarkably improved rate capability and cycling stability in comparison with the original Li‐excess layered cathode materials. This work sheds light on fundamental understanding of phase transitions within Li‐excess layered oxides. It also provides a novel route for tailoring electrochemical performance of Li‐excess layered cathode materials for high‐capacity lithium ion batteries.  相似文献   

7.
The design and fabrication of high‐performance all‐plastic batteries is essentially important to achieve future flexible electronics. A major challenge in this field is the lack of stable and reliable soft organic electrodes with satisfactory performance. Here, a novel all‐plastic‐electrode based Li‐ion battery with a single flexible bi‐functional ladderized heterocyclic poly(quinone), (C6O2S2)n, as both cathode and anode is demonstrated. Benefiting from its unique ladder‐like quinone and dithioether structure, the as‐prepared polymer cathode shows a high energy density of 624 Wh kg?1 (vs lithium anode) and a stable battery life of 1000 cycles. Moreover, the as‐fabricated symmetric full‐battery delivers a large capacity of 249 mAh g?1 (at 20 mA g?1), a good capacity retention of 119 mAh g?1 after 250 cycles (at 1.0 A g?1) and a noteworthy energy density up to 276 Wh kg?1. The superior performance of poly(2,3‐dithiino‐1,4‐benzoquinone)‐based electrode rivals most of the state‐of‐the‐art demonstrations on organic‐based metal‐ion shuttling batteries. The study provides an effective strategy to develop stable bi‐functional electrode materials toward the next‐generation of high performance all‐plastic batteries.  相似文献   

8.
A simple ball‐milling method is used to synthesize a tin oxide‐silicon carbide/few‐layer graphene core‐shell structure in which nanometer‐sized SnO2 particles are uniformly dispersed on a supporting SiC core and encapsulated with few‐layer graphene coatings by in situ mechanical peeling. The SnO2‐SiC/G nanocomposite material delivers a high reversible capacity of 810 mA h g?1 and 83% capacity retention over 150 charge/discharge cycles between 1.5 and 0.01 V at a rate of 0.1 A g?1. A high reversible capacity of 425 mA h g?1 also can be obtained at a rate of 2 A g?1. When discharged (Li extraction) to a higher potential at 3.0 V (vs. Li/Li+), the SnO2‐SiC/G nanocomposite material delivers a reversible capacity of 1451 mA h g?1 (based on the SnO2 mass), which corresponds to 97% of the expected theoretical capacity (1494 mA h g?1, 8.4 equivalent of lithium per SnO2), and exhibits good cyclability. This result suggests that the core‐shell nanostructure can achieve a completely reversible transformation from Li4.4Sn to SnO2 during discharging (i.e., Li extraction by dealloying and a reversible conversion reaction, generating 8.4 electrons). This suggests that simple mechanical milling can be a powerful approach to improve the stability of high‐performance electrode materials involving structural conversion and transformation.  相似文献   

9.
Covalent organic framework (COF) can grow into self‐exfoliated nanosheets. Their graphene/graphite resembling microtexture and nanostructure suits electrochemical applications. Here, covalent organic nanosheets (CON) with nanopores lined with triazole and phloroglucinol units, neither of which binds lithium strongly, and its potential as an anode in Li‐ion battery are presented. Their fibrous texture enables facile amalgamation as a coin‐cell anode, which exhibits exceptionally high specific capacity of ≈720 mA h g?1 (@100 mA g?1). Its capacity is retained even after 1000 cycles. Increasing the current density from 100 mA g?1 to 1 A g?1 causes the specific capacity to drop only by 20%, which is the lowest among all high‐performing anodic COFs. The majority of the lithium insertion follows an ultrafast diffusion‐controlled intercalation (diffusion coefficient, DLi+ = 5.48 × 10?11 cm2 s?1). The absence of strong Li‐framework bonds in the density functional theory (DFT) optimized structure supports this reversible intercalation. The discrete monomer of the CON shows a specific capacity of only 140 mA h g?1 @50 mA g?1 and no sign of lithium intercalation reveals the crucial role played by the polymeric structure of the CON in this intercalation‐assisted conductivity. The potentials mapped using DFT suggest a substantial electronic driving‐force for the lithium intercalation. The findings underscore the potential of the designer CON as anode material for Li‐ion batteries.  相似文献   

10.
Potassium ion hybrid capacitors have great potential for large‐scale energy devices, because of the high power density and low cost. However, their practical applications are hindered by their low energy density, as well as electrolyte decomposition and collector corrosion at high potential in potassium bis(fluoro‐sulfonyl)imide‐based electrolyte. Therefore, anode materials with high capacity, a suitable voltage platform, and stability become a key factor. Here, N‐doping carbon‐coated FeSe2 clusters are demonstrated as the anode material for a hybrid capacitor, delivering a reversible capacity of 295 mAh g?1 at 100 mA g?1 over 100 cycles and a high rate capability of 158 mAh g?1 at 2000 mA g?1 over 2000 cycles. Meanwhile, through density functional theory calculations, in situ X‐ray diffraction, and ex situ transmission electron microscopy, the evolution of FeSe2 to Fe3Se4 for the electrochemical reaction mechanism is successfully revealed. The battery‐supercapacitor hybrid using commercial activated carbon as the cathode and FeSe2/N‐C as the anode is obtained. It delivers a high energy density of 230 Wh kg?1 and a power density of 920 W kg?1 (the energy density and power density are calculated based on the total mass of active materials in the anode and cathode).  相似文献   

11.
Antimony (Sb) has emerged as an attractive anode material for both lithium and sodium ion batteries due to its high theoretical capacity of 660 mA h g?1. In this work, a novel peapod‐like N‐doped carbon hollow nanotube encapsulated Sb nanorod composite, the so‐called nanorod‐in‐nanotube structured Sb@N‐C, via a bottom‐up confinement approach is designed and fabricated. The N‐doped‐carbon coating and thermal‐reduction process is monitored by in situ high‐temperature X‐ray diffraction characterization. Due to its advanced structural merits, such as sufficient N‐doping, 1D conductive carbon coating, and substantial inner void space, the Sb@N‐C demonstrates superior lithium/sodium storage performance. For lithium storage, the Sb@N‐C exhibits a high reversible capacity (650.8 mA h g?1 at 0.2 A g?1), excellent long‐term cycling stability (a capacity decay of only 0.022% per cycle for 3000 cycles at 2 A g?1), and ultrahigh rate capability (343.3 mA h g?1 at 20 A g?1). For sodium storage, the Sb@N‐C nanocomposite displays the best long‐term cycle performance among the reported Sb‐based anode materials (a capacity of 345.6 mA h g?1 after 3000 cycles at 2 A g?1) and an impressive rate capability of up to 10 A g?1. The results demonstrate that the Sb@N‐C nanocomposite is a promising anode material for high‐performance lithium/sodium storage.  相似文献   

12.
Trees have an abundant network of channels for the multiphase transport of water, ions, and nutrients. Recent studies have revealed that multiphase transport of ions, oxygen (O2) gas, and electrons also plays a fundamental role in lithium–oxygen (Li–O2) batteries. The similarity in transport behavior of both systems is the inspiration for the development of Li–O2 batteries from natural wood featuring noncompetitive and continuous individual pathways for ions, O2, and electrons. Using a delignification treatment and a subsequent carbon nanotube/Ru nanoparticle coating process, one is able to convert a rigid and electrically insulating wood membrane into a flexible and electrically conductive material. The resulting cell walls are comprised of cellulose nanofibers with abundant nanopores, which are ideal for Li+ ion transport, whereas the unperturbed wood lumina act as a pathway for O2 gas transport. The noncompetitive triple pathway design endows the wood‐based cathode with a low overpotential of 0.85 V at 100 mA g?1, a record‐high areal capacity of 67.2 mAh cm?2, a long cycling life of 220 cycles, and superior electrochemical and mechanical stability. The integration of such excellent electrochemical performance, outstanding mechanical flexibility, and renewable yet cost‐effective starting materials via a nature‐inspired design opens new opportunities for developing portable energy storage devices.  相似文献   

13.
The fabrication of ultrasmall and high‐content SnO2 nanocrystals anchored on doped graphene can endow SnO2 with superior electrochemical properties. Herein, an effective strategy, involving molecular engineering of a layer‐by‐layer assembly technique, is proposed to homogeneously anchor SnO2 nanocrystals on nitrogen/sulfur codoped graphene (NSGS), which serves as an advanced anode material in lithium/sodium‐ion batteries (LIBs/SIBs). Benefiting from novel design and specific structure, the optimized NSGS for LIBs displays high initial capacity (2123.9 mAh g?1 at 0.1 A g?1), long‐term cycling performance (only 0.8% loss after 500 cycles), and good rate capability (477.4 mAh g?1 at 5 A g?1). In addition, the optimized NSGS for SIBs also delivers high initial capacity (791.7 mAh g?1 at 0.1 A g?1) and high reversible capacity (180.2 mAh g?1 after 500 cycles at 0.5 A g?1). Meanwhile, based on the detailed analysis of phase transition and electrochemical reaction kinetics, the reaction mechanisms of NSGS in LIBs and SIBs as well as the distinction in LIBs/SIBs are clearly articulated. Notably, to further explore the practical application, Li/Na+ full cells are also assembled by coupling the optimized NSGS anode with LiCoO2 and Na3V2(PO4)3/C cathodes, respectively.  相似文献   

14.
Molybdenum disulfide (MoS2), which possesses a layered structure and exhibits a high theoretical capacity, is currently under intensive research as an anode candidate for next generation of Li‐ion batteries. However, unmodified MoS2 suffers from a poor cycling stability and an inferior rate capability upon charge/discharge processes. Herein, a unique nanocomposite comprising MoS2 nanothorns epitaxially grown on the backbone of carbon nanotubes (CNTs) and coated by a layer of amorphous carbon is synthesized via a simple method. The epitaxial growth of MoS2 on CNTs results in a strong chemical coupling between active nanothorns and carbon substrate via C? S bond, providing a high stability as well as a high‐efficiency electron‐conduction/ion‐transportation system on cycling. The outer carbon layer can well‐accommodate the structural strain in the electrode upon lithium‐ion insertion/extraction. When employed as an anode for lithium storage, the prepared material exhibits remarkable electrochemical properties with a high specific capacity of 982 mA h g?1 at 0.1 A g?1, as well as excellent long‐cycling stability (905 mA h g?1 at 1 A g?1 after 500 cycles) and superior rate capability, confirming its potential application in high‐performance Li‐ion batteries.  相似文献   

15.
Orthorhombic α‐MoO3 is a potential anode material for lithium‐ion batteries due to its high theoretical capacity of 1100 mAh g?1 and excellent structural stability. However, its intrinsic poor electronic conductivity and high volume expansion during the charge–discharge process impede it from achieving a high practical capacity. A novel composite of α‐MoO3 nanobelts and single‐walled carbon nanohorns (SWCNHs) is synthesized by a facile microwave hydrothermal technique and demonstrated as a high‐performance anode material for lithium‐ion batteries. The α‐MoO3/SWCNH composite displays superior electrochemical properties (654 mAh g?1 at 1 C), excellent rate capability (275 mAh g?1 at 5 C), and outstanding cycle life (capacity retention of >99% after 3000 cycles at 1 C) without any cracking of the electrode. The presence of SWCNHs in the composite enhances the electrochemical properties of α‐MoO3 by acting as a lithium storage material, electronic conductive medium, and buffer against pulverization.  相似文献   

16.
With the rising demand for flexible and wearable electronic devices, flexible power sources with high energy densities are required to provide a sustainable energy supply. Theoretically, rechargeable, flexible Li‐O2/air batteries can provide extremely high specific energy densities; however, the high costs, complex synthetic methods, and inferior mechanical properties of the available flexible cathodes severely limit their practical applications. Herein, inspired by the structure of human blood capillary tissue, this study demonstrates for the first time the in situ growth of interpenetrative hierarchical N‐doped carbon nanotubes on the surface of stainless‐steel mesh (N‐CNTs@SS) for the fabrication of a self‐supporting, flexible electrode with excellent physicochemical properties via a facile and scalable one‐step strategy. Benefitting from the synergistic effects of the high electronic conductivity and stable 3D interconnected conductive network structure, the Li‐O2 batteries obtained with the N‐CNTs@SS cathode exhibit superior electrochemical performance, including a high specific capacity (9299 mA h g?1 at 500 mA g?1), an excellent rate capability, and an exceptional cycle stability (up to 232 cycles). Furthermore, as‐fabricated flexible Li‐air batteries containing the as‐prepared flexible super‐hydrophobic cathode show excellent mechanical properties, stable electrochemical performance, and superior H2O resistibility, which enhance their potential to power flexible and wearable electronic devices.  相似文献   

17.
Li‐rich oxide is a promising candidate for the cathodes of next‐generation lithium‐ion batteries. However, its utilization is restricted by cycling instability and inferior rate capability. To tackle these issues, three‐dimensional (3D), hierarchical, cube‐maze‐like Li‐rich cathodes assembled from two‐dimensional (2D), thin nanosheets with exposed {010} active planes, are developed by a facile hydrothermal approach. Benefiting from their unique architecture, 3D cube‐maze‐like cathodes demonstrate a superior reversible capacity (285.3 mAh g?1 at 0.1 C, 133.4 mAh g?1 at 20.0 C) and a great cycle stability (capacity retention of 87.4% after 400 cycles at 2.0 C, 85.2% after 600 cycles and 75.0% after 1200 cycles at 20.0 C). When this material is matched with a graphite anode, the full cell achieves a remarkable discharge capacity (275.2 mAh g?1 at 0.1 C) and stable cycling behavior (capacity retention of 88.7% after 100 cycles at 5.0 C, capacity retention of 84.8% after 100 cycles at 20.0 C). The present work proposes an accessible way to construct 3D hierarchical architecture assembled from 2D nanosheets with exposed high‐energy active {010} planes and verifies its validity for advanced Li‐rich cathodes.  相似文献   

18.
Remarkable improvements in the electrochemical performance of Si materials for Li‐ion batteries have been recently achieved, but the inherent volume change of Si still induces electrode expansion and external cell deformation. Here, the void structure in Si‐encapsulating hollow carbons is optimized in order to minimize the volume expansion of Si‐based anodes and improve electrochemical performance. When compared to chemical etching, the hollow structure is achieved via electroless etching is more advanced due to the improved electrical contact between carbon and Si. Despite the very thick electrodes (30 ~ 40 μm), this results in better cycle and rate performances including little capacity fading over 50 cycles and 1100 mA h g?1 at 2C rate. Also, an in situ dilatometer technique is used to perform a comprehensive study of electrode thickness change, and Si‐encapsulating hollow carbon mitigates the volume change of electrodes by adoption of void space, resulting in a small volume increase of 18% after full lithiation corresponding with a reversible capacity of about 2000 mA h g?1.  相似文献   

19.
Lithium‐ion capacitors (LICs) with capacitor‐type cathodes and battery‐type anodes are considered a promising next‐generation advanced energy storages system that meet the requirements of high energy density and power density. However, the mismatch of charge‐storage capacity and electrode kinetics between positive and negative electrodes remains a challenge. Herein, layered SnS2/reduced graphene oxide (RGO) nanocomposites are developed for negative electrodes and a 2D B/N codoped carbon (BCN) nanosheet is designed for the positive electrode. The SnS2/RGO derived from SnS2‐bonded RGO of high conductivity exhibits a capacity of 1198 mA h g?1 at 100 mA g?1. Boron and nitrogen atoms in BCN are found to promote adsorption of anions, which enhance the pseudocapacitive contribution as well as expanding the voltage of LICs. A quantitative kinetics analysis indicates that the SnS2/RGO electrodes with a dominating capacitive mechanism and a diminished intercalation process, benefit the kinetic balance between the two electrodes. With this particular structure, the LIC is able to operate at the highest operating voltage for these devices recorded to date (4.5 V), exhibiting an energy density of 149.5 W h kg?1, a power density of 35 kW kg?1, and a capacity retention ratio of 90% after 10 000 cycles.  相似文献   

20.
Herein, P′2‐type Na0.67[Ni0.1Fe0.1Mn0.8]O2 is introduced as a promising new cathode material for sodium‐ion batteries (SIBs) that exhibits remarkable structural stability during repetitive Na+ de/intercalation. The O? Ni? O? Mn? O? Fe? O bond in the octahedra of transition‐metal layers is used to suppress the elongation of the Mn? O bond and to improve the electrochemical activity, leading to the highly reversible Na storage mechanism. A high discharge capacity of ≈220 mAh g?1 (≈605 Wh kg?1) is delivered at 0.05 C (13 mAg?1) with a high reversible capacity of ≈140 mAh g?1 at 3 C and excellent capacity retention of 80% over 200 cycles. This performance is associated with the reversible P′2–OP4 phase transition and small volume change upon charge and discharge (≈3%). The nature of the sodium storage mechanism in a full cell paired with a hard carbon anode reveals an unexpectedly high energy density of ≈542 Wh kg?1 at 0.2 C and good capacity retention of ≈81% for 500 cycles at 1 C (260 mAg?1).  相似文献   

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