RESUMO
The poor reversibility and stability of Zn metal anode (ZMA) caused by uncontrolled Zn deposition behaviors and serious side reactions severely impeded the practical application of aqueous Zn metal battery. Herein, a liquid-dynamic and self-adaptive protective layer (LSPL) was constructed on the ZMA surface for inhibiting dendrites and by-products formation. Interestingly, the outer LSPL consists of liquid perfluoropolyether (PFPE), which can dynamically adapt volume change during repeat cycling and inhibit side reactions. Moreover, it can also decrease the de-solvation energy barrier of Zn2+ by strong interaction between C-F bond and foreign Zn2+ , improving Zn2+ transport kinetics. For the LSPL inner region, in-situ formed ZnF2 through the spontaneous chemical reaction between metallic Zn and part PFPE can establish an unimpeded Zn2+ migration pathway for accelerating ion transfer, thereby restricting Zn dendrites formation. Consequently, the LSPL-modified ZMA enables reversible Zn deposition/dissolution up to 2000 h at 1 mA cm-2 and high coulombic efficiency of 99.8% at 4 mA cm-2 . Meanwhile, LSPL@Zn||NH4 V4 O10 full cells deliver an ultralong cycling lifespan of 100 00 cycles with 0.0056% per cycle decay rate at 10 A g-1 . This self-adaptive layer provides a new strategy to improve the interface stability for next-generation aqueous Zn battery.
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The dendrite growth and parasitic reactions that occur on Zn metal anode (ZMA)/electrolyte interface hinder the development of aqueous zinc ion batteries (AZIBs) in next-generation renewable energy storage systems. Fortunately, reconstructing the inner Helmholtz layer (IHL) by introducing an electrolyte additive, is viewed as one of the most promising strategies to harvest the stable ZMA. Herein, (4-chloro-3-nitrophenyl) (pyridin-4-yl) methanone (CNPM) with quadruple functional groups is introduced into the ZnSO4 electrolyte to reshape the interface between ZMA and electrolyte and change the solvation structure of Zn2+ . Density functional theory (DFT) calculations manifest that the âCâO, âCl, âCâNâ, and âNO2 functional groups of CNPM interact with metallic Zn simultaneously and adsorb on the ZMA surface in a parallel arrangement manner, thus forming a water-poor IHL and creating well-arranged ion transportation channels. Furthermore, theoretical calculations and experimental results demonstrate that CNPM absorbed on the Zn anode surface can serve as zincophilic sites for inducing uniform Zn deposition along the (002) plane. Benefiting from the synergistic effect of these functions, the dendrite growth and parasitic reactions are suppressed significantly. As a result, ZMA exhibits a long cycle life (2900 h) and high coulombic efficiency (CE) (500 cycles) in the ZnSO4 +CNPM electrolyte.
RESUMO
Uncontrolled dendrites growth and serious parasitic reactions in aqueous electrolytes, greatly hinder the practical application of aqueous zinc-ion battery. On the basis of in situ-chemical construction and performance-improving mechanism, multifunctional fluoroethylene carbonate (FEC) is introduced into aqueous electrolyte to construct a high-quality and ZnF2 -riched inorganic/organic hybrid SEI (ZHS) layer on Zn metal anode (ZMA) surface. Notably, FEC additive can regulate the solvated structure of Zn2+ to reduce H2 O molecules reactivity. Additionally, the ZHS layer with strong Zn2+ affinity can avoid dendrites formation and hinder the direct contact between the electrolyte and anode. Therefore, the dendrites growth, Zn corrosion, and H2 evolution reaction on ZMA in FEC-included ZnSO4 electrolyte are highly suppressed. Thus, ZMA in such electrolyte realize a long cycle life over 1000â h and deliver a stable coulombic efficiency of 99.1 % after 500â cycles.
RESUMO
Lithium metal anodes (LMAs) with high energy density have recently captured increasing attention for development of next-generation batteries. However, practical viability of LMAs is hindered by the uncontrolled Li dendrite growth and infinite dimension change. Even though constructing 3D conductive skeleton has been regarded as a reliable strategy to prepare stable and low volume stress LMAs, engineering the renewable and lithiophilic conductive scaffold is still a challenge. Herein, a robust conductive scaffold derived from renewable cellulose paper, which is coated with reduced graphene oxide and decorated with lithiophilic Au nanoparticles, is engineered for LMAs. The graphene cellulose fibres with high surface area can reduce the local current density, while the well-dispersed Au nanoparticles can serve as lithiophilic nanoseeds to lower the nucleation overpotential of Li plating. The coupled relationship can guarantee uniform Li nucleation and unique spherical Li growth into 3D carbon matrix. Moreover, the natural cellulose paper possesses outstanding mechanical strength to tolerate the volume stress. In virtue of the modulated deposition behaviour and near-zero volume change, the hybrid LMAs can achieve reversible Li plating/stripping even at an ultrahigh current density of 10â mA cm-2 as evidenced by high Coulombic efficiency (97.2 % after 60â cycles) and ultralong lifespan (1000â cycles) together with ultralow overpotential (25â mV). Therefore, this strategy sheds light on a scalable approach to multiscale design versatile Li host, promising highly stable Li metal batteries to be feasible and practical.
RESUMO
Zinc metal has been naturally considered as the most anticipated anode material for zinc-ion batteries (ZIBs), given the benefits of large volume specific capacity, low electrode potential, and inexpensive cost. However, the growth of zinc dendrites and the corrosion of hydrogen evolution during the Zn2+ ion deposition process are the bottlenecks restricting the large-scale application of zinc metal. Herein, we report the modification of zinc anodes by utilizing a ball-milling clay precipitate (designated as BMC, consisting of the unetched MAX phase and the Ti3C2Tx phase) to construct a three-dimensional (3D) framework on the surface of zinc foil (Zn@BMC). Different from the close stacking of conventionally prepared MXene sheets after film formation, the BMC coating firmly adheres to the zinc surface through the binder. The abundant internal space relieves the stress during the volume change of the Zn metal and uniformizes the Zn2+ ion flux. Consequently, Zn@BMC not only achieves a stable long cycle (2000 h, 0.5 mA h cm-2) but also inhibits the side reaction of hydrogen evolution by physically separating the electrolyte and the zinc metal anode. We reckon that our research will aid in clarifying the design principles governing the interface of the zinc metal anode in ZIBs.
RESUMO
Lithium (Li) metal has been considered to be the most promising anode material for next-generation rechargeable batteries. Unfortunately, the hazards induced by dendrite growth and volume fluctuation hinder its commercialized application. Here, a three-dimensional (3D) current collector composed of a vertically aligned Cu2O nanowire that is tightly coated with a polydopamine protective layer is developed to solve the encountered issues of lithium metal batteries (LMBs). The Cu2O nanowire arrays (Cu2O NWAs) provide abundant lithiophilic sites for inducing Li nucleation selectively to form a thin Li layer around the nanowires and direct subsequent Li deposition. The well-defined nanochannel works well in confining the Li growth spatially and buffering the volume change during the repeated cycling. The PDA coatings adhered onto the outline of the Cu2O NWAs serve as the artificial solid electrolyte interface to isolate the electrode and electrolyte and retain the interfacial stability. Moreover, the increased specific area of copper foam (CF) can dissipate the local current density and further suppress the growth of Li dendrites. As a result, CF@Cu2O NWAs@PDA realizes a dendrite-free morphology and the assembled symmetrical batteries can work stably for over 1000 h at 3 mA cm-2. When CF@Cu2O NWAs@PDA is coupled with a LiFePO4 cathode, the full cells exhibit improved cycle stability and rate performance.
RESUMO
Lithium (Li) metal is deemed as an ideal and promising star anode for high energy storage but its application still is impeded due to uncontrollable Li dendrite growth and tremendous dimension change. Although the flexible and conductive three-dimensional (3D) skeleton can improve the structural and interfacial stability of Li anode, its inherently lithiophobic feature usually brings a high nucleation barrier, uneven Li+ flux, and large concentration polarization, leading to inhomogeneous Li plating/stripping. Here, we develop target material (denoted as Mo2C NPs@CC) consisting of well-distributed molybdenum carbide nanoparticles (Mo2C NPs) with intrinsic lithiophilicity serving as lithiophilic seeds implanted onto the carbon cloth, breaking the dilemma of ordinary 3D conductive skeletons. The Mo2C NPs with large Li absorption energy provide plentiful lithiophilic sites for guiding the uniform and thin Li-nuclei layer formation, thereby realizing flat Li growth and stable electrode/electrolyte interface. Moreover, the high electronic conductivity of Mo2C-modified 3D scaffolds can balance the lithiophilicity, ensuring the fast electron transport in the whole electrode, effectively lowering the local current density, and providing enough space for buffering volume change, and synergistically suppresses the growth of Li dendrites. As a result, a prolonged lifespan of 5000 cycles with low voltage hysteresis of 10 mV at current density of 2 mA cm-2 with area capacity (Ca) of 1 mA h cm-2 has been achieved, giving rational guidance for designing high-performance composite Li anodes.
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A lithium metal anode (LMA) is appealing due to its high theoretical capacity and low electrochemical potential. Unfortunately, the practical application of LMAs is restricted by the uncontrollable Li dendrite growth and tremendous volume change. Herein, lithiophilic honeycomb-like layered double hydroxide (LDH) nanosheet arrays supported on a flexible carbon cloth (NiMn-LDHs NAs@CC) are synthesized as the Li host to spatially confine the Li deposition, guiding Li growth via a conformal and uniform manner. First, the lithiophilic NiMn-LDHs NAs as nucleation seeds render the CC substance outstanding lithiophilicity and reduce the nucleation barrier. The hierarchical honeycomb-like structure then directs the oriented Li deposition and provides an open channel for fast ion transport. Finally, the CC skeleton offers a high specific surface for decreasing the inhomogeneous distribution of the current density and enough space for alleviating the volume variations, synergistically inhibiting the dendritic Li growth. As a consequence, the NiMn-LDHs NAs@CC symmetric cell exhibits a low overpotential of less than 17 mV at 2 mA cm-2 and a long lifespan of 2100 h at 3 mA cm-2. In addition, when paired with the LiNiCoMnO2 (NCM111) cathode, the NiMn-LDHs NAs@CC@Li full cell presents enhanced cycling stability and rate capability in comparison to the CC@Li full cell, implying the great potential of the NiMn-LDHs NAs@CC in stabilizing the LMA.
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Limited by the notorious Li dendrites growth and serious polysulfide shuttle effect, the development of lithium-sulfur (Li-S) batteries is stagnant. Herein, a multifunctional separator composed of Cu-based metal-organic framework (Cu-MOF) and Li-Nafion was proposed to address the above intractable issues. The Cu-MOF with homogeneous porous structure and abundant Lewis acidic sites not only promotes uniform Li+ flux, but also exhibits a strong chemical interaction with polysulfides to inhibit the shuttle effect. Moreover, the narrow pore size distribution in the Cu-MOF and negatively charged gap endowed by the -SO3- groups both act as ion sieve to facilitate the passage of Li+ and restrict the migration of polysulfide anions, synergistically mitigating the dendritic Li growth and polysulfides shuttling. As a result, the symmetric cell with MOF/Nafion separator achieves ultralong cycling stability (1000 h) and ultralow overpotential of 20 mV at a current density of 1.0 mA cm-2. Importantly, in the assembled Li-S full battery, the modified PP separator presents the superior cycle stability with capacity retention of 90% after 300 cycles at 0.5 C. Current outcomes open up a new route to design functional separators with ion permselective for realizing the dendrite-free and high-performance Li-S battery.