RESUMEN
Neutrophilic superhalide-anion-triggered chalcogen conversion-based Zn batteries, despite latent high-energy merit, usually suffer from a short lifespan caused by dendrite growth and shuttle effect. Here, a superhalide-anion-motivator reforming strategy is initiated to simultaneously manipulate the anode interface and Se conversion intermediates, realizing a bipolar regulation toward longevous energy-type Zn batteries. With ZnF2 chaotropic additives, the original large-radii superhalide zincate anion species in ionic liquid (IL) electrolytes are split into small F-containing species, boosting the formation of robust solid electrolyte interphases (SEI) for Zn dendrite inhibition. Simultaneously, ion radius reduced multiple F-containing Se conversion intermediates form, enhancing the interion interaction of charged products to suppress the shuttle effect. Consequently, Zn||Se batteries deliver a ca. 20-fold prolonged lifespan (2000 cycles) at 1 A g-1 and high energy/power density of 416.7 Wh kgSe-1/1.89 kW kgSe-1, outperforming those in F-free counterparts. Pouch cells with distinct plateaus and durable cyclability further substantiate the practicality of this design.
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Graphene-based materials (GBMs) possess a unique set of properties including tunable interlayer channels, high specific surface area, and good electrical conductivity characteristics, making it a promising material of choice for making electrode in rechargeable batteries. Lithium-ion batteries (LIBs) currently dominate the commercial rechargeable battery market, but their further development has been hampered by limited lithium resources, high lithium costs, and organic electrolyte safety concerns. From the performance, safety, and cost aspects, zinc-based rechargeable batteries have become a promising alternative of rechargeable batteries. This review highlights recent advancements and development of a variety of graphene derivative-based materials and its composites, with a focus on their potential applications in rechargeable batteries such as LIBs, zinc-air batteries (ZABs), zinc-ion batteries (ZIBs), and zinc-iodine batteries (Zn-I2 Bs). Finally, there is an outlook on the challenges and future directions of this great potential research field.
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For zinc-metal batteries, the instable chemistry at Zn/electrolyte interphasial region results in severe hydrogen evolution reaction (HER) and dendrite growth, significantly impairing Zn anode reversibility. Moreover, an often-overlooked aspect is this instability can be further exacerbated by the interaction with dissolved cathode species in full batteries. Here, inspired by sustained-release drug technology, an indium-chelated resin protective layer (Chelex-In), incorporating a sustained-release mechanism for indium, is developed on Zn surface, stabilizing the anode/electrolyte interphase to ensure reversible Zn plating/stripping performance throughout the entire lifespan of Zn//V2O5 batteries. The sustained-release indium onto Zn electrode promotes a persistent anticatalytic effect against HER and fosters uniform heterogeneous Zn nucleation. Meanwhile, on the electrolyte side, the residual resin matrix with immobilized iminodiacetates anions can also repel detrimental anions (SO4 2- and polyoxovanadate ions dissolved from V2O5 cathode) outside the electric double layer. This dual synergetic regulation on both electrode and electrolyte sides culminates a more stable interphasial environment, effectively enhancing Zn anode reversibility in practical high-areal-capacity full battery systems. Consequently, the bio-inspired Chelex-In protective layer enables an ultralong lifespan of Zn anode over 2800â h, which is also successfully demonstrated in ultrahigh areal capacity Zn//V2O5 full batteries (4.79â mAh cm-2).
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Bipolar organic cathode materials (OCMs) implementing cation/anion storage mechanisms are promising for high-energy aqueous Zn batteries (AZBs). However, conventional organic functional group active sites in OCMs usually fail to sufficiently unlock the high-voltage/capacity merits. Herein, we initially report dynamically ion-coordinated bipolar OCMs as cathodes with chalcogen active sites to solve this issue. Unlike conventional organic functional groups, chalcogens bonded with conjugated group undergo multielectron-involved positive-valence oxidation and negative-valence reduction, affording higher redox potentials and reversible capacities. With phenyl diselenide (PhSe-SePh, PDSe) as a proof of concept, it exhibits a conversion pathway from (PhSe)- to (PhSe-SePh)0 and then to (PhSe)+ as unveiled by characterization and theoretical simulation, where the diselenide bonds are periodically broken and healed, dynamically coordinating with ions (Zn2+ and OTF-). When confined into ordered mesoporous carbon (CMK-3), the dissolution of PDSe intermediates is greatly inhibited to obtain an ultralong lifespan without voltage/capacity compromise. The PDSe/CMK-3 || Zn batteries display high reversibility capacity (621.4â mAh gPDSe -1), distinct discharge plateau (up to 1.4â V), high energy density (578.3â Wh kgPDSe -1), and ultralong lifespan (12 000 cycles) at 10â A g-1, far outperforming conventional bipolar OCMs. This work sheds new light on conversion-type active site engineering for high-voltage/capacity bipolar OCMs towards high-energy AZBs.
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Hydrogel electrolytes (HEs) hold great promise in tackling severe issues emerging in aqueous zinc-ion batteries, but the prevalent salting-out effect of kosmotropic salt causes low ionic conductivity and electrochemical instability. Herein, a subtle molecular bridging strategy is proposed to enhance the compatibility between PVA and ZnSO4 from the perspective of hydrogen-bonding microenvironment re-construction. By introducing urea containing both an H-bond acceptor and donor, the broken H-bonds between PVA and H2O, initiated by the SO42--driven H2O polarization, could be re-united via intense intermolecular hydrogen bonds, thus leading to greatly increased carrying capacity of ZnSO4. The urea-modified PVA-ZnSO4 HEs featuring a high ionic conductivity up to 31.2 mS cm-1 successfully solves the sluggish ionic transport dilemma at the solid-solid interface. Moreover, an organic solid-electrolyte-interphase can be derived from the in-situ electro-polymerization of urea to prohibit H2O-involved side reactions, thereby prominently improving the reversibility of Zn chemistry. Consequently, Zn anodes witness an impressive lifespan extension from 50 h to 2200 h at 0.1 mA cm-2 while the Zn-I2 full battery maintains a remarkable Coulombic efficiency (>99.7%) even after 8000 cycles. The anti-salting-out strategy proposed in this work provides an insightful concept for addressing the phase separation issue of functional HEs.
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Gradual disability of Zn anode and high negative/positive electrode (N/P) ratio usually depreciate calendar life and energy density of aqueous Zn batteries (AZBs). Herein, within original Zn2+-free hydrated electrolytes, a steric hindrance/electric field shielding-driven "hydrophobic ion barrier" is engineered towards ultradurable (002) plane-exposed Zn stripping/plating to solve this issue. Guided by theoretical simulations, hydrophobic adiponitrile (ADN) is employed as a steric hindrance agent to ally with inert electric field shielding additive (Mn2+) for plane adsorption priority manipulation, thereby constructing the "hydrophobic ion barrier". This design robustly suppresses the (002) plane/dendrite growth, enabling ultradurable (002) plane-exposed dendrite-free Zn stripping/plating. Even being cycled in ZnâZn symmetric cell over 2150â h at 0.5â mA cm-2, the efficacy remains well-kept. Additionally, ZnâZn symmetric cells can be also stably cycled over 918â h at 1â mA cm-2, verifying uncompromised Zn stripping/plating kinetics. As-assembled anode-less ZnâVOPO4 â 2H2O full cells with a low N/P ratio (2 : 1) show a high energy density of 75.2â Wh kg-1 full electrode after 842â cycles at 1â A g-1, far surpassing counterparts with thick Zn anode and low cathode loading mass, featuring excellent practicality. This study opens a new avenue by robust "hydrophobic ion barrier" design to develop long-life anode-less Zn batteries.
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Severe Zn dendrite growth and side reactions greatly limit the application of aqueous zinc-ion batteries. Herein, we design a layer of polyionic liquid (PCAVImBr) film with a tunable pore size and charge density on the Zn anode to endow homogenized distribution of an electronic field, acerated Zn2+ permeation, and inhabitation of water entry. Such an optimal combination is achieved via a polymerization induced phase separation strategy, where the enhanced cross-linking density arrests the phase separation in a shallow depth and vice versa. Furthermore, the Zn@PCAVImBr electrode has good plating/stripping reversibility, which retains a 99.6% CE efficiency after 3000 cycles. The symmetric cells can achieve a cycle life of more than 2400 h at different current densities. It is worth mentioning that the NVO//Zn@PCAVImBr full cell can still reach a 91.2% capacity retention after nearly 4000 cycles at a high current of 10 A g-1, and provides new insights for the future research of zinc-ion battery anodes.
Asunto(s)
Líquidos Iónicos , Polimerizacion , Electrónica , ZincRESUMEN
The artificial solid electrolyte interphase (SEI) plays a pivotal role in Zn anode stabilization but its long-term effectiveness at high rates is still challenged. Herein, to achieve superior long-life and high-rate Zn anode, an exquisite electrolyte additive, lithium bis(oxalate)borate (LiBOB), is proposed to in situ derive a highly Zn2+ -conductive SEI and to dynamically patrol its cycling-initiated defects. Profiting from the as-constructed real-time, automatic SEI repairing mechanism, the Zn anode can be cycled with distinct reversibility over 1800â h at an ultrahigh current density of 50â mA cm-2 , presenting a record-high cumulative capacity up to 45â Ah cm-2 . The superiority of the formulated electrolyte is further demonstrated in the Zn||MnO2 and Zn||NaV3 O8 full batteries, even when tested under harsh conditions (limited Zn supply (N/P≈3), 2500â cycles). This work brings inspiration for developing fast-charging Zn batteries toward grid-scale storage of renewable energy sources.
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Aqueous rechargeable Mg batteries (ARMBs) usually fail from severe anode passivation, alternatively, executing quasi-underpotential Mg plating/stripping chemistry (UPMC) on a proper heterogeneous metal substrate is a crucial remedy. Herein, a stable UPMC on Zn substrate is initially achieved in new hydrated eutectic electrolytes (HEEs), delivering an ultralow UPMC overpotential and high energy/voltage plateau of ARMBs. The unique eutectic property remarkably expands the lower limit of electrochemical stability window (ESW) of HEEs and undermines the competition between hydrogen evolution/corrosion reactions and UPMC, enabling a reversible UPMC. The UPMC is carefully revealed by multiple characterizations, which shows a low overpotential of 50â mV at 0.1â mA cm-2 over 550â h. With sulfonic acid-doped polyaniline (SPANI) cathodes, UPMC-based full cells show high energy/power densities of 168.6â Wh kg-1 /2.1â kWh kg-1 and voltage plateau of 1.3â V, far overwhelming conventional aqueous systems.
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The anode-cathode interplay is an important but rarely considered factor that initiates the degradation of aqueous zinc ion batteries (AZIBs). Herein, to address the limited cyclability issue of V-based AZIBs, Al2 (SO4 )3 is proposed as decent electrolyte additive to manipulate OH- -mediated cross-communication between Zn anode and NaV3 O8 â 1.5H2 O (NVO) cathode. The hydrolysis of Al3+ creates a pH≈0.9 strong acidic environment, which unexpectedly prolongs the anode lifespan from 200 to 1000â h. Such impressive improvement is assigned to the alleviation of interfacial OH- accumulation by Al3+ adsorption and solid electrolyte interphase formation. Accordingly, the strongly acidified electrolyte, associated with the sedated crossover of anodic OH- toward NVO, remarkably mitigate its undesired dissolution and phase transition. The interrupted OH- -mediated communication between the two electrodes endows Zn||NVO batteries with superb cycling stability, at both low and high scan rates.
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Developing highly efficient bifunctional catalysts for the oxygen reduction and oxygen evolution reaction (ORR/OER) can open possibilities for future zinc air batteries (ZABs). Herein, cost-effective and highly conductive few-layer ferric and nickel chloride co-intercalated graphite intercalation compounds (FeCl3 -NiCl2 -GIC) are designed as bifunctional oxygen catalysts for ZAB. The optimized few-layer FeCl3 -NiCl2 -GIC catalyst exhibits a small overpotential of 276 mV at 10 mA cm-2 for the OER and achieves a high onset potential of 0.89 V for the ORR. The theoretical analysis demonstrates the electron-rich state on the carbon layers of FeCl3 -NiCl2 -GIC during the catalytic process favors the kinetics of electron transfer and lowers the absorption energy barriers for intermediates. Impressively, the ZAB assembled with few-layer FeCl3 -NiCl2 -GIC catalyst displays a 160 h cycling stability and a high energy efficiency of 72.6%. This work also suggests the possibility of utilizing layer electronic structure regulation on graphite intercalation compounds as effective bifunctional catalysts for ZABs.
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Lithium metal batteries (LMBs) have attracted extensive attention owing to their high energy density. However, the uncontrolled volume changes and serious dendrite growth of the Li metal anode have hindered their commercialization. Herein, a three-dimensional Cu foam decorated with Au nanoparticles and conformal graphene layer was designed to tune the Li plating/stripping behaviors. The 3D-Cu conductive host anchored by lithiophilic Au nanoparticles can effectively alleviate the volume expansion caused by the continuous plating/stripping of Li and reduce the nucleation energy barrier. Notably, the conductive graphene not only facilitates the transfer of electrons, but also acts as an ionic rectifier, thereby avoiding the aggregation of local current density and Li+ ions around Au nanoparticles and enabling the uniform Li+ flux. As a result, the G-Au@3D-Cu/Li anode ensures the non-dendritic and homogeneous Li+ plating/stripping. Electrochemical results show that the symmetric G-Au@3D-Cu/Li cell delivers a low voltage hysteresis of 110â mV after 1000â h at 1â mA cm-2 . Matched with a layered LiNi0.6 Co0.2 Mn0.2 O2 cathode, the NCM622||G-Au@3D-Cu/Li full cell exhibits a long cycle life of 2000 cycles and an ultra-low capacity decay rate (0.01 % per cycle).
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Developing advanced electrode materials with enhanced charge-transfer kinetics is the key to realizing fast energy storage technologies. Commonly used modification strategies, such as nanoengineering and carbon coating, are mainly focused on electron transfer and bulk Li+ diffusion. Nonetheless, the desolvation behavior, which is considered as the rate-limiting process for charge-storage, is rarely studied. Herein, we designed a nitridation layer on the surface of Wadsley-Roth phase FeNb11O29 (FNO-x@N) to act as a desolvation promoter. Theoretical calculations demonstrate that the adsorption and desolvation of solvated Li+ is efficiently improved at FNO-x@N/electrolyte interphase, leading to the reduced desolvation energy barrier. Moreover, the nitridation layer can also help to prevent solvent cointercalation during Li+ insertion, leading to advantageous shrinkage of block area and reduced volume change of lattice cell during cycling. Consequently, FNO-x@N exhibits a high-rate capacity of 129.7 mAh g-1 with negligible capacity decay for 10â¯000 cycles.
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The capacity degredation in layered Ni-rich LiNixCoyMnzO2 (x ≥ 0.8) cathode largely originated from drastic surface reactions and intergranular cracks in polycrystalline particles. Herein, we report a highly stable single-crystal LiNi0.83Co0.12Mn0.05O2 cathode material, which can deliver a high specific capacity (â¼209 mAh g-1 at 0.1 C, 2.8-4.3 V) and meanwhile display excellent cycling stability (>96% retention for 100 cycles and >93% for 200 cycles). By a combination of in situ X-ray diffraction and in situ pair distribution function analysis, an intermediate monoclinic distortion and irregular H3 stack are revealed in the single crystals upon charging-discharging processes. These structural changes might be driven by unique Li-intercalation kinetics in single crystals, which enables an additional strain buffer to reduce the cracks and thereby ensure the high cycling stability.
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The instability of interfacial solid-electrolyte interphase (SEI) layer of metallic sodium (Na) anode during cycles results in the rapid capacity decay of sodium metal batteries (SMBs). Herein, the concept of interfacial protection engineering of Na nanoparticles (Na-NPs) is proposed first to achieve stable, dendrite-free, and long-life SMB. Employing an ion-exchange strategy, conformal Sn-Na alloy-SEI on the interface of Na-NPs is constructed, forming Sn@Na-NPs. The stable alloy-based SEI layer possesses the following three advantages: 1) significantly enhancing the transport dynamics of Na+ ions and electrons; 2) enabling the well-distributed deposition of Na+ ions to avoid the growth of dendrites; and 3) protecting the Sn@Na-NPs anode from the attack of electrolyte, thereby reducing the parasitic reaction and boosting the Coulombic efficiency of SMBs. Because of these virtues, the symmetric Sn@Na-NPs cell shows an ultralow voltage hysteresis of 0.54 V at 10 mA cm-2 after 600 h. Paired with the Na3 V2 (PO4 )2 O2 F (NaVPF) cathode, the NaVPF-Sn@Na-NPs full cell exhibits an initial discharge capacity of 89.2 mAh g-1 at 1 C and a high capacity retention of 81.6% after 600 cycles.
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Lithium shortage and the growing demand for electricity storage has encouraged researchers to look for new alternative energy-storage materials. Due to abundant potassium resources, similar redox potential to lithium metal, and low cost, potassium-ion batteries (PIBs), as one of the promising alternatives, have been applied in energy-storage research recently. However, PIBs do not have adequate competition in their electrochemical efficiency because the molar volume of potassium ions is higher than those in lithium and sodium ions. Therefore, for better application and development of PIBs, finding suitable anode and cathode materials is currently the most important task. The latest developments in electrode materials for PIBs have been outlined in depth in this review. It focuses on the structural design and synthetic methods for novel electrode materials, ingenious optimization and tuning strategies, and explains the intrinsic reaction mechanism. The effects of organic electrolytes and aqueous electrolytes on battery systems are compared and clarified. Finally, theoretical and viable insights are given to the challenges posed by the creation and practical application of PIBs in the future.
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Lithium ion batteries (LIBs) at present still suffer from low rate capability and poor cycle life during fast ion insertion/extraction processes. Searching for high-capacity and stable anode materials is still an ongoing challenge. Herein, a facile strategy for the synthesis of ultrathin GeS2 nanosheets with the thickness of 1.1â nm is reported. When used as anodes for LIBs, the two-dimensional (2D) structure can effectively increase the electrode/electrolyte interface area, facilitate the ion transport, and buffer the volume expansion. Benefiting from these merits, the as-synthesized GeS2 nanosheets deliver high specific capacity (1335â mAh g-1 at 0.15â A g-1 ), extraordinary rate performance (337â mAh g-1 at 15â A g-1 ) and stable cycling performance (974â mAh g-1 after 200â cycles at 0.5â A g-1 ). Importantly, our fabricated Li-ion full cells manifest an impressive specific capacity of 577â mAh g-1 after 50â cycles at 0.1â A g-1 and a high energy density of 361â Wh kg-1 at a power density of 346â W kg-1 . Furthermore, the electrochemical reaction mechanism is investigated by the means of ex-situ high-resolution transmission electron microscopy. These results suggest that GeS2 can use to be an alternative anode material and encourage more efforts to develop other high-performance LIBs anodes.
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The utilization of noble-metal catalysts for the hydrogen evolution reaction (HER) provides an efficient strategy for hydrogen acquisition. However, exploring catalysts with suitable hydrogen binding strength for the HER process is always of great importance, but extremely challenging. In this work, sulfur and phosphor as electron-withdrawing elements were incorporated into carbon nanotube (CNT)-supported Ru catalysts, which were prepared through a facile solution reduction reaction and post thermo treatment. Owing to the suitable electronegativity provided by P and synergistic effects of the carbon nanotubes, the RuP2 /CNT achieved a high catalytic performance as a HER electrocatalyst. This may result from the modulation effect of the electronic properties and the depressed adsorption free energy of RuP2 . Electrochemical tests present that the RuP2 /CNT composite exhibit a small overpotential of 58â mV at 10â mA cm-2 in acidic electrolyte. In a neutral or alkaline environment, the overpotential is 82 and 40â mV, respectively. The RuP2 /CNT electrode also possesses stable durability for long-time cycling, suggesting its remarkable property as promising all-pH HER catalyst.
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Sodium-ion batteries have attracted interest as an alternative to lithium-ion batteries because of the abundance and cost effectiveness of sodium. However, suitable anode materials with high-rate and stable cycling performance are still needed to promote their practical application. Herein, three-dimensional Na2 Ti3 O7 nanowire arrays with enriched surface vacancies endowed by phosphorus doping are reported. As anodes for sodium-ion batteries, they deliver a high specific capacity of 290â mA h g-1 at 0.2 C, good rate capability (50â mA h g-1 at 20 C), and stable cycling capability (98 % capacity retention over 3100 cycles at 20 C). The superior electrochemical performance is attributed to the synergistic effects of the nanowire arrays and phosphorus doping. The rational structure can provide convenient channels to facilitate ion/electron transport and improve the capacitive contributions. Moreover, the phosphorus-doping-induced surface vacancies not only provide more active sites but also improve the intrinsic electrical conductivity of Na2 Ti3 O7 , which will enable electrode materials with excellent sodium storage performance. This work may provide an effective strategy for the synthesis of other anode materials with fast electrochemical reaction kinetics and good sodium storage performance.
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In recent years, porous colloidal particles have found promising applications in catalytic fields, such as photocatalysis, electrocatalysis, industrial and automotive byproducts removal, as well as biomass upgrading. These applications are critical for alleviating the energy crisis and environmental pollution. Porous colloidal particles have remarkable specific areas and abundant reactive sites, which can significantly improve the mass/charge transport and reaction rate in catalysis. Precursor-based synthesis is among the most facile and widely-adopted methods to achieve monodisperse and homogeneous porous colloidal particles. In the current review, we briefly introduce the general catalytic applications of porous colloidal particles. The conventional precursor-based methods are reviewed to design state-of-the-art porous colloidal particles as highly efficient catalysts. The recent development of porous colloidal particles derived from metal-organic frameworks (MOFs), glycerates, carbonate precursors, and ion exchange methods are reviewed. In the end, the current concerns and future development of porous colloidal particles are outlined.