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1.
Cost‐effective and environment‐friendly aqueous zinc‐ion batteries (AZIBs) exhibit tremendous potential for application in grid‐scale energy storage systems but are limited by suitable cathode materials. Hydrated vanadium bronzes have gained significant attention for AZIBs and can be produced with a range of different pre‐intercalated ions, allowing their properties to be optimized. However, gaining a detailed understanding of the energy storage mechanisms within these cathode materials remains a great challenge due to their complex crystallographic frameworks, limiting rational design from the perspective of enhanced Zn2+ diffusion over multiple length scales. Herein, a new class of hydrated porous δ‐Ni0.25V2O5.nH2O nanoribbons for use as an AZIB cathode is reported. The cathode delivers reversibility showing 402 mAh g?1 at 0.2 A g?1 and a capacity retention of 98% over 1200 cycles at 5 A g?1. A detailed investigation using experimental and computational approaches reveal that the host “δ” vanadate lattice has favorable Zn2+ diffusion properties, arising from the atomic‐level structure of the well‐defined lattice channels. Furthermore, the microstructure of the as‐prepared cathodes is examined using multi‐length scale X‐ray computed tomography for the first time in AZIBs and the effective diffusion coefficient is obtained by image‐based modeling, illustrating favorable porosity and satisfactory tortuosity.  相似文献   

2.
Aqueous zinc batteries are considered as promising alternatives to lithium ion batteries owing to their low cost and high safety. However, the developments of state‐of‐the‐art zinc‐ion batteries (ZIB) and zinc–air batteries (ZAB) are limited by the unsatisfied capacities and poor cycling stabilities, respectively. It is of significance in utilizing the long‐cycle life of ZIB and high capacity of ZAB to exploit advanced energy storage systems. Herein, a bulk composite of graphene oxide and vanadium oxide (V5O12·6H2O) as cathode material for aqueous Zn batteries in a mild electrolyte is employed. The battery performance is demonstrated to arise from a combination of the reversible cations insertion/extraction in vanadium oxide and especially the electrochemical redox reactions on the surface functional groups of graphene oxide (named as pseudo‐Zn–air mechanism). Along with adjusting the hydroxyl content on the surface of graphene oxide, the specific capacity is significantly increased from 342 mAh g?1 to a maximum of 496 mAh g?1 at 100 mA g?1. The surface‐controlled kinetics occurring in the bulk composite ensure a high areal capacity of 10.6 mAh cm?2 at a mass loading of 26.5 mg cm?2, and a capacity retention of 84.7% over 10 000 cycles at a high current density of 10 A g?1.  相似文献   

3.
Rechargeable magnesium batteries (RMBs) are attractive candidates for large‐scale energy storage owing to the high theoretical specific capacity, rich earth abundance, and good safety characteristics. However, the development of desirable cathode materials for RMBs is constrained by the high polarity and slow intercalation kinetics of Mg2+ ions. Herein, it is demonstrated that 2‐ethylhexylamine pillared vanadium disulfide nanoflowers (expanded VS2) with enlarged interlayer distances exhibit greatly boosted electrochemical performance as a cathode material in RMBs. Through a one‐step solution‐phase synthesis and in situ 2‐ethylhexylamine intercalation process, VS2 nanoflowers with ultralarge interlayer spacing are prepared. A series of ex situ characterizations verify that the cathode of expanded VS2 nanoflowers undergoes a reversible intercalation reaction mechanism, followed by a conversion reaction mechanism. Electrochemical kinetics analysis reveal a relatively fast Mg‐ion diffusivity of expanded VS2 nanoflowers in the order of 10?11–10?12 cm2 s?1, and the pseudocapacitive contribution is up to 64% for the total capacity at 1 mV s?1. The expanded VS2 nanoflowers show highly reversible discharge capacity (245 mAh g?1 at 100 mA g?1), good rate capability (103 mAh g?1 at 2000 mA g?1), and stable cycling performance (90 mAh g?1 after 600 cycles at 1000 mA g?1).  相似文献   

4.
The recent trend in zinc (Zn) anode aqueous batteries has been to explore layered structures like manganese dioxides and vanadium oxides as Zn‐ion intercalation hosts. These structures, although novel, face limitations like their layered counterparts in lithium (Li)‐ion batteries, where the capacity is limited to the host's intercalation capacity. In this paper, a new strategy is proposed in enabling new generation of energy dense aqueous‐based batteries, where the conversion reactions of rock salt/spinel manganese oxides and carbon nanotube‐nested nanosized Zn electrodes are exploited to extract significantly higher capacity compared to intercalation systems. Accessing the conversion reactions allows to achieve high capacities of 750 mAh g?1 (≈30 mAh cm?2) from manganese oxide (MnO) and 810 mAh g?1 (≈30 mAh cm?2) from nanoscale Zn anodes, respectively. The high areal capacities help to attain unprecedented energy densities of 210 Wh per L‐cell and 320 Wh per kg‐total (398 Wh per kg‐active) from aqueous MnO|CNT‐Zn batteries, which allows an assessment of its viable use in a small‐scale automobile.  相似文献   

5.
Rechargeable aqueous zinc‐ion batteries (ZIBs) have been emerging as potential large‐scale energy storage devices due to their high energy density, low cost, high safety, and environmental friendliness. However, the commonly used cathode materials in ZIBs exhibit poor electrochemical performance, such as significant capacity fading during long‐term cycling and poor performance at high current rates, which significantly hinder the further development of ZIBs. Herein, a new and highly reversible Mn‐based cathode material with porous framework and N‐doping (MnOx@N‐C) is prepared through a metal–organic framework template strategy. Benefiting from the unique porous structure, conductive carbon network, and the synergetic effect of Zn2+ and Mn2+ in electrolyte, the MnOx@N‐C shows excellent cycling stability, good rate performance, and high reversibility for aqueous ZIBs. Specifically, it exhibits high capacity of 305 mAh g?1 after 600 cycles at 500 mA g?1 and maintains achievable capacity of 100 mAh g?1 at a quite high rate of 2000 mA g?1 with long‐term cycling of up to 1600 cycles, which are superior to most reported ZIB cathode materials. Furthermore, insight into the Zn‐storage mechanism in MnOx@N‐C is systematically studied and discussed via multiple analytical methods. This study opens new opportunities for designing low‐cost and high‐performance rechargeable aqueous ZIBs.  相似文献   

6.
Rechargeable aqueous Zn‐based batteries are attractive candidates as energy storage technology, but the uncontrollable Zn dendrites, low stripping/plating coulombic efficiency, and inefficient utilization of Zn metal limit the battery reliability and energy density. Herein, for the first time, a novel presodiated TiS2 (Na0.14TiS2) is proposed and investigated as an intercalated anode for aqueous Zn‐ion batteries, showing a capacity of 140 mAh g?1 with a suitable potential of 0.3 V (vs Zn2+/Zn) at 0.05 A g?1 and superior cyclability of 77% retention over 5000 cycles at 0.5 A g?1. The remarkable performance originates from the buffer phase formation of Na0.14TiS2 after chemically presodiating TiS2, which not only improves the structural reversibility and stability but also enhances the diffusion coefficient and electronic conductivity, and lowers cation migration barrier, as evidenced by a series of experimental and theoretical studies. Moreover, an aqueous “rocking‐chair” Zn‐ion full battery is successfully demonstrated by this Na0.14TiS2 anode and ZnMn2O4 cathode, which delivers a capacity of 105 mAh g?1 (for anode) with an average voltage of 0.95 V at 0.05 A g?1 and preserves 74% retention after 100 cycles at 0.2 A g?1, demonstrating the feasibility of Zn‐ion full batteries for energy storage applications.  相似文献   

7.
Rechargeable aqueous zinc‐ion batteries (ZIBs) are promising for cheap stationary energy storage. Challenges for Zn‐ion insertion hosts are the large structural changes of the host structure upon Zn‐ion insertion and the divalent Zn‐ion transport, challenging cycle life and power density respectively. Here a new mechanism is demonstrated for the VO2 cathode toward proton insertion accompanied by Zn‐ion storage through the reversible deposition of Zn4(OH)6SO4·5H2O on the cathode surface, supported by operando X‐ray diffraction, X‐ray photoelectron spectroscopy, neutron activation analysis, and density functional theory simulations. This leads to an initial discharge capacity of 272 mAh g?1 at a current density of 3.0 A g?1, of which 75.5% is maintained after 945 cycles. It is proposed that the competition between proton and Zn‐ion insertion in the VO2 host is determined by the solvation energy of the salt anion and proton insertion energetics, where proton insertion has the advantage of minimal structural distortion leading to a long cycle life. As the discharge kinetics are capacitive for the first half of the process and diffusion limited for the second half, the VO2 cathode takes the middle road possessing both fast kinetics and high practical capacities revealing a reaction mechanism that provides new perspective for the development of aqueous ZIBs.  相似文献   

8.
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   

9.
Hard carbon (HC) is the state‐of‐the‐art anode material for sodium‐ion batteries (SIBs). However, its performance has been plagued by the limited initial Coulombic efficiency (ICE) and mediocre rate performance. Here, experimental and theoretical studies are combined to demonstrate the application of lithium‐pretreated HC (LPHC) as high‐performance anode materials for SIBs by manipulating the solid electrolyte interphase in tetraglyme (TEGDME)‐based electrolyte. The LPHC in TEGDME can 1) deliver > 92% ICE and ≈220 mAh g?1 specific capacity, twice of the capacity (≈100 mAh g?1) in carbonate electrolyte; 2) achieve > 85% capacity retention over 1000 cycles at 1000 mA g?1 current density (4 C rate, 1 C = 250 mA g?1) with a specific capacity of ≈150 mAh g?1, ≈15 times of the capacity (10 mAh g?1) in carbonate. The full cell of Na3V2(PO4)3‐LPHC in TEGDME demonstrated close to theoretical specific capacity of ≈98 mAh g?1 based on Na3V2(PO4)3 cathode, ≈2.5 times of the value (≈40 mAh g?1) with nontreated HC. This work provides new perception on the anode development for SIBs.  相似文献   

10.
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   

11.
Herein, a new P2‐type layered oxide is proposed as an outstanding intercalation cathode material for high energy density sodium‐ion batteries (SIBs). On the basis of the stoichiometry of sodium and transition metals, the P2‐type Na0.55[Ni0.1Fe0.1Mn0.8]O2 cathode is synthesized without impurities phase by partially substituting Ni and Fe into the Mn sites. The partial substitution results in a smoothing of the electrochemical charge/discharge profiles and thus greatly improves the battery performance. The P2‐type Na0.55[Ni0.1Fe0.1Mn0.8]O2 cathode delivers an extremely high discharge capacity of 221.5 mAh g?1 with a high average potential of ≈2.9 V (vs Na/Na+) for SIBs. In addition, the fast Na‐ion transport in the P2‐type Na0.55[Ni0.1Fe0.1Mn0.8]O2 cathode structure enables good power capability with an extremely high current density of 2400 mA g?1 (full charge/discharge in 12 min) and long‐term cycling stability with ≈80% capacity retention after 500 cycles at 600 mA g?1. A combination of electrochemical profiles, in operando synchrotron X‐ray diffraction analysis, and first‐principles calculations are used to understand the overall Na storage mechanism of P2‐type Na0.55[Ni0.1Fe0.1Mn0.8]O2.  相似文献   

12.
Aqueous batteries are facing big challenges in the context of low working voltages and energy density, which are dictated by the narrow electrochemical window of aqueous electrolytes and low specific capacities of traditional intercalation‐type electrodes, even though they usually represent high safety, low cost, and simple maintenance. For the first time, this work demonstrates a record high‐energy‐density (1503 Wh kg?1 calculated from the cathode active material) aqueous battery system that derives from a novel electrolyte design to expand the electrochemical window of electrolyte to 3 V and two high‐specific‐capacity electrode reactions. An acid‐alkaline dual electrolyte separated by an ion‐selective membrane enables two dissolution/deposition electrode redox reactions of MnO2/Mn2+ and Zn/Zn(OH)42? with theoretical specific capacities of 616 and 820 mAh g?1, respectively. The newly proposed Zn–Mn2+ aqueous battery shows a high Coulombic efficiency of 98.4% and cycling stability of 97.5% of discharge capacity retention for 1500 cycles. Furthermore, in the flow battery based on Zn–Mn2+ pairs, more excellent stability of 99.5% of discharge capacity retention for 6000 cycles is achieved due to greatly improved reversibility of the Zn anode. This work provides a new path for the development of novel aqueous batteries with high voltage and energy density.  相似文献   

13.
Aqueous rechargeable zinc ion batteries are considered a promising candidate for large‐scale energy storage owing to their low cost and high safety nature. A composite material comprised of H2V3O8 nanowires (NWs) wrapped by graphene sheets and used as the cathode material for aqueous rechargeable zinc ion batteries is developed. Owing to the synergistic merits of desirable structural features of H2V3O8 NWs and high conductivity of the graphene network, the H2V3O8 NW/graphene composite exhibits superior zinc ion storage performance including high capacity of 394 mA h g?1 at 1/3 C, high rate capability of 270 mA h g?1 at 20 C and excellent cycling stability of up to 2000 cycles with a capacity retention of 87%. The battery offers a high energy density of 168 W h kg?1 at 1/3 C and a high power density of 2215 W kg?1 at 20 C (calculated based on the total weight of H2V3O8 NW/graphene composite and the theoretically required amount of Zn). Systematic structural and elemental characterization confirm the reversible Zn2+ and water cointercalation electrochemical reaction mechanism. This work brings a new prospect of designing high‐performance aqueous rechargeable zinc ion batteries for grid‐scale energy storage.  相似文献   

14.
Rechargeable aqueous zinc‐ion batteries (ZIBs) are appealing due to their high safety, zinc abundance, and low cost. However, developing suitable cathode materials remains a great challenge. Herein, a novel 2D heterostructure of ultrathin amorphous vanadium pentoxide uniformly grown on graphene (A‐V2O5/G) with a very short ion diffusion pathway, abundant active sites, high electrical conductivity, and exceptional structural stability, is demonstrated for highly reversible aqueous ZIBs (A‐V2O5/G‐ZIBs), coupling with unprecedented high capacity, rate capability, long‐term cyclability, and excellent safety. As a result, 2D A‐V2O5/G heterostructures for stacked ZIBs at 0.1 A g?1 display an ultrahigh capacity of 489 mAh g?1, outperforming all reported ZIBs, with an admirable rate capability of 123 mAh g?1 even at 70 A g?1. Furthermore, the new‐concept prototype planar miniaturized zinc‐ion microbatteries (A‐V2O5/G‐ZIMBs), demonstrate a high volumetric capacity of 20 mAh cm?3 at 1 mA cm?2, long cyclability; holding high capacity retention of 80% after 3500 cycles, and in‐series integration, demonstrative of great potential for highly‐safe microsized power sources. Therefore, the exploration of such 2D heterostructure materials with strong synergy is a reliable strategy for developing safe and high‐performance energy storage devices.  相似文献   

15.
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   

16.
Herein, a two‐species redox reaction of Co(II)/Co(III) and Fe(II)/Fe(III) incorporated in cobalt hexacyanoferrate (CoFe(CN)6) is proposed as a breakthrough to achieve jointly high‐capacity and high‐voltage aqueous Zn‐ion battery. The Zn/CoFe(CN)6 battery provides a highly operational voltage plateau of 1.75 V (vs metallic Zn) and a high capacity of 173.4 mAh g?1 at current density of 0.3 A g?1, taking advantage of the two‐species redox reaction of Co(II)/Co(III) and Fe(II)/Fe(III) couples. Even under extremely fast charge/discharge rate of 6 A g?1, the battery delivers a sufficiently high discharge capacity of 109.5 mAh g?1 with its 3D opened structure framework. This is the highest capacity delivered among all the batteries using Prussian blue analogs (PBAs) cathode up to now. Furthermore, Zn/CoFe(CN)6 battery achieves an excellent cycling performance of 2200 cycles without any capacity decay at coulombic efficiency of nearly 100%. One further step, a sol–gel transition strategy for hydrogel electrolyte is developed to construct high‐performance flexible cable‐type battery. With the strategy, the active materials can adequately contact with electrolyte, resulting in improved electrochemical performance (≈18.73% capacity increase) and mechanical robustness of the solid‐state device. It is believed that this study optimizes electrodes by incorporating multi redox reaction species for high‐voltage and high‐capacity batteries.  相似文献   

17.
Ni‐rich Li[NixCoyMn1?x?y]O2 (x ≥ 0.8) layered oxides are the most promising cathode materials for lithium‐ion batteries due to their high reversible capacity of over 200 mAh g?1. Unfortunately, the anisotropic properties associated with the α‐NaFeO2 structured crystal grains result in poor rate capability and insufficient cycle life. To address these issues, a micrometer‐sized Ni‐rich LiNi0.8Co0.1Mn0.1O2 secondary cathode material consisting of radially aligned single‐crystal primary particles is proposed and synthesized. Concomitant with this unique crystallographic texture, all the exposed surfaces are active {010} facets, and 3D Li+ ion diffusion channels penetrate straightforwardly from surface to center, remarkably improving the Li+ diffusion coefficient. Moreover, coordinated charge–discharge volume change upon cycling is achieved by the consistent crystal orientation, significantly alleviating the volume‐change‐induced intergrain stress. Accordingly, this material delivers superior reversible capacity (203.4 mAh g?1 at 3.0–4.3 V) and rate capability (152.7 mAh g?1 at a current density of 1000 mA g?1). Further, this structure demonstrates excellent cycling stability without any degradation after 300 cycles. The anisotropic morphology modulation provides a simple, efficient, and scalable way to boost the performance and applicability of Ni‐rich layered oxide cathode materials.  相似文献   

18.
19.
The symmetric batteries with an electrode material possessing dual cathodic and anodic properties are regarded as an ideal battery configuration because of their distinctive advantages over the asymmetric batteries in terms of fabrication process, cost, and safety concerns. However, the development of high‐performance symmetric batteries is highly challenging due to the limited availability of suitable symmetric electrode materials with such properties of highly reversible capacity. Herein, a triple‐hollow‐shell structured V2O5 (THS‐V2O5) symmetric electrode material with a reversible capacity of >400 mAh g?1 between 1.5 and 4.0 V and >600 mAh g?1 between 0.1 and 3.0 V, respectively, when used as the cathode and anode, is reported. The THS‐V2O5 electrodes assembled symmetric full lithium‐ion battery (LIB) exhibits a reversible capacity of ≈290 mAh g?1 between 2 and 4.0 V, the best performed symmetric energy storage systems reported to date. The unique triple‐shell structured electrode makes the symmetric LIB possessing very high initial coulombic efficiency (94.2%), outstanding cycling stability (with 94% capacity retained after 1000 cycles), and excellent rate performance (over 140 mAh g?1 at 1000 mA g?1). The demonstrated approach in this work leaps forward the symmetric LIB performance and paves a way to develop high‐performance symmetric battery electrode materials.  相似文献   

20.
Intercalation chemistry/engineering has been widely investigated in the development of electrochemical energy storage. Graphite, as an old intercalation host, is receiving vigorous attention again via a new halogen intercalation. Whereas, exploiting new intercalation hosts and optimizing the intercalation effect still remains a great challenge. This study fabricates a Cu2Se intercalation compound showing expanded interlayer space and nanosheet array features by using a green growth approach, in which cetyltrimethyl ammonium bromide (CTAB) is inserted into Cu2Se at an ambient temperature. When acting as an electrode material for sodium‐ion batteries, the Cu2Se–CTAB nanosheet arrays exhibit excellent discharge capacity and rate capability (426.0 mAh g?1 at 0.1 A g?1 and 238.1 mAh g?1 at 30 A g?1), as well as high capacity retention of ≈90% at 20 A g?1 after 6500 cycles. Benefiting from the porous array architecture, the transport of electrolytes is facilitated on the surface of Cu2Se nanosheets. In particular, the CTAB intercalated in the interlayer space of Cu2Se can increase its buffer space, stabilize the polyselenide shuttle, and prevent the fast growth of Cu nanoparticles during its electrochemical process.  相似文献   

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