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1.
The progress of aqueous zinc batteries (AZBs) is limited by the poor cycling life due to Zn anode instability, including dendrite growth, surface corrosion, and passivation. Inspired by the anti-corrosion strategy of steel industry, a compounding corrosion inhibitor (CCI) is employed as the electrolyte additive for Zn metal anode protection. It is shown that CCI can spontaneously generate a uniform and ≈30 nm thick solid-electrolyte interphase (SEI) layer on Zn anode with a strong adhesion via Zn O bonding. This SEI layer efficiently prohibits water corrosion and guides homogeneous Zn deposition without obvious dendrite formation. This enables reversible Zn deposition and dissolution for over 1100 h under the condition of 1 mA cm−2 and 1 mAh cm−2 in symmetric cells. The Zn-MnO2 full cells with CCI-modified electrolyte deliver an ultralow capacity decay rate (0.013% per cycle) at 0.5 A g−1 over 1000 cycles. Such an innovative strategy paves a low-cost way to achieve AZBs with long lifespan.  相似文献   

2.
Uncontrolled transport of anions leads to many issues, including concentration polarization, excessive interface side reactions, and space charge-induced lithium dendrites at the anode/electrolyte interface, which severely deteriorates the cycling stability of lithium metal batteries. Herein, an asymmetrical polymer electrolyte modified by a boron-containing single-ion conductor (LiPVAOB), is designed to inhibit the nonuniform aggregation of free anions in the vicinity of the lithium anode through the repulsion effect improving the lithium-ion transference number to 0.63. This LiPVAOB exerts a repulsion interaction with free anions even at a long distance and a selective effect for free anions transport, which diminishes uneven aggregation of free anions at the interface and suppresses space charges-induced lithium dendrites growth. Consequently, the assembled Li||Li cell delivers an ultra-long cycle for over 5400 h. The Li||LiFePO4 cell exhibits outstanding cycle performance with a capacity retention of 93% over 4500 cycles. In particular, the assembled high-voltage Li||Li1.2Ni0.2Mn0.6O2 cell (charged to 4.8 V) exhibits good cycle stability with a high specific capacity of 245 mAh g−1. This designed polymer electrolyte provides a promising strategy for regulating ion transport to inhibit space charge-induced lithium dendrite growth for high-performance lithium metal batteries.  相似文献   

3.
The practical realization of aqueous zinc-ion batteries relies crucially on effective interphases governing Zn electrodeposition chemistry. In this study, an innovative solution by introducing an ultrathin (≈2 µm) biomass membrane as an intimate artificial interface, functioning as nature's ion-regulation skin to protect zinc metal anodes is proposed. Capitalizing on the inherent properties of natural reed membrane, including multiscale ion transport tunnels, abundant ─OH groups, and remarkable mechanical integrity, the reed membrane demonstrates efficacy in regulating uniform and rapid Zn2+ transport, promoting desolvation, and governing Zn (002) plane electrodeposition. Importantly, a unique in situ electrochemical Zn─O bond formation mechanism between the reed membrane and Zn electrode upon cycling is elucidated, resulting in a robustly adhered interface covering on the zinc anode surface, ultimately ensuring remarkable dendrite-free and highly reversible Zn anodes. Consequently, the approach achieves a prolonged cycle life for over 1450 h at 3 mA cm−2/1.5 mAh cm−2 in symmetric Zn//Zn cells. Moreover, exceptional cyclic performance (88.95%, 4000 cycles) is obtained in active carbon-based cells with an active mass loading of 5.8 mg cm−2. The approach offers a cost-effective and environmentally friendly strategy for achieving stable and reversible zinc anodes for aqueous batteries.  相似文献   

4.
With the increasing energy crisis and environmental pollution, rechargeable aqueous Zn‐based batteries (AZBs) are receiving unprecedented attention due to their list of merits, such as low cost, high safety, and nontoxicity. However, the limited voltage window, Zn dendrites, and relatively low specific capacity are still great challenges. In this work, a new reaction mechanism of reversible Mn2+ ion oxidation deposition is introduced to AZBs. The assembled Mn2+/Zn2+ hybrid battery (Mn2+/Zn2+ HB) based on a hybrid storage mechanism including Mn2+ ion deposition, Zn2+ ion insertion, and conversion reaction of MnO2 can achieve an ultrawide voltage window (0–2.3 V) and high capacity (0.96 mAh cm?2). Furthermore, the carbon nanotubes coated Zn anode is proved to effectively inhibit Zn dendrites and control side reaction, hence exhibiting an ultrastable cycling (33 times longer than bare Zn foil) without obvious polarization. Benefiting from the optimal Zn anode and highly reversible Mn2+/Zn2+ hybrid storage mechanism, the Mn2+/Zn2+ HB shows an excellent cycling performance over 11 000 cycles with a 100% capacity retention. To the best of the authors' knowledge, it is the highest reported cycling performance and wide voltage window for AZBs with mild electrolyte, which may inspire a great insight into designing high‐performance aqueous batteries.  相似文献   

5.
Aqueous zinc ion batteries (ZIBs) exhibit great potential for next-generation energy storage devices. However, significant challenges exist, including the uncontrollable formation of Zn dendrite and side reactions during zinc stripping and plating. The mechanism of Zn dendrite nucleation has yet to be fully understood. In this work, the first principles simulations are used to investigate the Zn dendrite formation process. The unintentionally adsorbed O2− and OH ions are the inducing factors for Zn dendrite nucleation and growth on the Zn (0001) plane due to significantly increased Zn diffusion barriers. A top-down method is demonstrated to suppress the dendrite using delaminated V2CTx to capture O2− and OH ions thanks to reduced Zn diffusion barriers. The experimental results revealed significantly suppressed Zn dendrite nucleation and growth, resulting in a layer-by-layer deposit/stripping of Zn. Based on the electrochemical evaluations, the V2CTx-coated Zn composite delivers a high coulombic efficiency of 99.3% at 1.0 mAh cm−2. Furthermore, the full cell achieves excellent cyclic performance of 93.6% capacity retention after 2000 cycles at 1 A g−1. This strategy has broad scalability and can be widely applied in designing metallic anodes for rechargeable batteries.  相似文献   

6.
A key challenge to apply aqueous zinc metal batteries (AZMBs) as next-generation energy storage device is to improve the rechargeability at high current densities, which is needed to circumvent slowly ion diffusion in anode and sluggish charge transfer of Zn2+. Herein, a zincophilic accordion array derived from MOF is developed as zinc host for simultaneously boosted ion diffusion and charge transfer. The designed host is prepared by etching and disproportionation reactions, the abundant zincophilic Sn sites with nano-size uniform disperse on accordion arrays nanosheets (Sn-AA). Then a composite Zn anode (Sn-AA@Zn) is obtained by compacting Sn-AA host with zinc power (Zn-P). The Sn-AA@Zn anode has an ultra-low activation energy (37.1 kJ mol−1) and nucleation overpotential (10 mV), achieving fast charge transfer of Zinc deposition. In addition, the cycle life of the symmetric cell with Sn-AA@Zn anode exceeds 13 000 cycles at 50 mA cm−2, which is 32 times than that of the Zn-P anode. And the full cell with Sn-AA@Zn anode and MnO2 cathode maintains a capacity of 122 mAh g−1 after 5000 cycles at 5 Ag−1. Hopefully, the 3D anode based on Sn-AA@Zn accordion array and Zn-P has significantly improved the rechargeability of AZMB at high current density.  相似文献   

7.
The application of lithium (Li) metal anodes in Li metal batteries has been hindered by growth of Li dendrites, which lead to short cycling life. Here a Li‐ion‐affinity leaky film as a protection layer is reported to promote a dendrite‐free Li metal anode. The leaky film induces electrokinetic phenomena to enhance Li‐ion transport, leading to a reduced Li‐ion concentration polarization and homogeneous Li‐ion distribution. As a result, the dendrite‐free Li metal anode during Li plating/stripping is demonstrated even at an extremely high deposition capacity (6 mAh cm?2) and current density (40 mA cm?2) with improved Coulombic efficiencies. A full cell battery with the leaky‐film protected Li metal as the anode and high‐areal‐capacity LiNi0.8Co0.1Mn0.1O2 (NCM‐811) (≈4.2 mAh cm?2) or LiFePO4 (≈3.8 mAh cm?2) as the cathode shows improved cycling stability and capacity retention, even at lean electrolyte conditions.  相似文献   

8.
Traditional challenges of poor cycling stability and low Coulombic efficiency in Zinc (Zn) metal anodes have limited their practical application. To overcome these issues, this work introduces a single metal-atom design featuring atomically dispersed single copper (Cu) atoms on 3D nitrogen (N) and oxygen (O) co-doped porous carbon (CuNOC) as a highly reversible Zn host. The CuNOC structure provides highly active sites for initial Zn nucleation and further promotes uniform Zn deposition. The 3D porous architecture further mitigates the volume changes during the cycle with homogeneous Zn2+ flux. Consequently, CuNOC demonstrates exceptional reversibility in Zn plating/stripping processes over 1000 cycles at 2 and 5 mA cm−2 with a fixed capacity of 1 mAh cm−2, while achieving stable operation and low voltage hysteresis over 700 h at 5 mA cm−2 and 5 mAh cm−2. Furthermore, density functional theory calculations show that co-doping N and O on porous carbon with atomically dispersed single Cu atoms creates an efficient zincophilic site for stable Zn nucleation. A full cell with the CuNOC host anode and high loading V2O5 cathode exhibits outstanding rate-capability up to 5 A g−1 and a stable cycle life over 400 cycles at 0.5 A g−1.  相似文献   

9.
Sodium-ion batteries (SIBs), based on hard carbon anodes and Na+-intercalation compound cathodes, have gained significant attention. Nonetheless, hard carbon anodes involve the storage of Na+ at a low potential, typically below 0.1 V (vs Na/Na+), which increases the risk of dendritic Na growth on the anode surface during overcharging. Herein, a safe organic/inorganic composite anode containing tetrasodium 3,4,9,10-perylenetetracarboxylate (Na4PTC) and Metallic bismuth (Bi) with a weight ratio of 7:2, which exhibits an average potential of 0.7 V (vs Na+/Na) and a capacity of 150 mAh g−1 is proposed. The electrode reaction involves a reversible coordination reaction within the organic host and alloying reactions within the metallic Bi component. Importantly, the organic component efficiently buffers the volume changes in Bi during the alloying reaction, while the metallic Bi enhances the electronic conductivity of the organic material. As a result, this composite anode shows high cycle stability and rate performance, even under high mass loadings ranging from 10 to 50 mg cm−2. Furthermore, it is demonstrated that the Na-ion full cell, consisting of the composite anode and the Na3V2O2(PO4)2F cathode, exhibits minimal capacity degradation over 100 cycles while maintaining a high areal capacity of 1.1 mA cm−2.  相似文献   

10.
Rechargeable aqueous Zn/MnO2 batteries are very attractive large‐scale energy storage technologies, but still suffer from limited cycle life and low capacity. Here the novel adoption of a near‐neutral acetate‐based electrolyte (pH ≈ 6) is presented to promote the two‐electron Mn4+/Mn2+ redox reaction and simultaneously enable a stable Zn anode. The acetate anion triggers a highly reversible MnO2/Mn2+ reaction, which ensures high capacity and avoids the issue of structural collapse of MnO2. Meanwhile, the anode‐friendly electrolyte enables a dendrite‐free Zn anode with outstanding stability and high plating/stripping Coulombic efficiency (99.8%). Hence, a high capacity of 556 mA h g?1, a lifetime of 4000 cycles without decay, and excellent rate capability up to 70 mA cm?2 are demonstated in this new near‐neutral aqueous Zn/MnO2 battery by simply manipulating the salt anion in the electrolyte. The acetate anion not only modifies the surface properties of MnO2 cathode but also creates a highly compatible environment for the Zn anode. This work provides a new opportunity for developing high‐performance Zn/MnO2 and other aqueous batteries based on the salt anion chemistry.  相似文献   

11.
The spatial distribution and transport characteristics of lithium ions (Li+) in the electrochemical interface region of a lithium anode in a lithium ion battery directly determine Li+ deposition behavior. The regulation of the Li+ solvation sheath on the solid electrolyte interphase (SEI) by electrolyte chemistry is key but challenging. Here, 1 m lithium trifluoroacetate (LiTFA) is induced to the electrolyte to regulate the Li+ solvation sheath, which significantly suppresses Li dendrite formation and enables a high Coulombic efficiency of 98.8% over 500 cycles. With its strong coordination between the carbonyl groups (C?O) and Li+, TFA? modulates the environment of the Li+ solvation sheath and facilitates fast desolvation kinetics. In addition, due to relatively smaller lowest unoccupied molecular orbital energy than solvents, TFA? has a preferential reduction to produce a stable SEI with uniform distribution of LiF and Li2O. Such stable SEI effectively reduces the energy barrier for Li+ diffusion, contributing to low nucleation overpotential, fast ion transfer kinetics, and uniform Li+ deposition with high cycling stability. This work provides an alternative insight into the design of interface chemistry in terms of regulating anions in the Li+ solvation sheath. It is anticipated that this anion‐tuned strategy will pave the way to construct stable SEIs for other battery systems.  相似文献   

12.
Herein, a new solvation strategy enabled by Mg(NO3)2 is introduced, which can be dissolved directly as Mg2+ and NO3? ions in the electrolyte to change the Li+ ion solvation structure and greatly increase interfacial stability in Li‐metal batteries (LMBs). This is the first report of introducing Mg(NO3)2 additives in an ester‐based electrolyte composed of ternary salts and binary ester solvents to stabilize LMBs. In particular, it is found that NO3? efficiently forms a stable solid electrolyte interphase through an electrochemical reduction reaction, along with the other multiple anion components in the electrolyte. The interaction between Li+ and NO3? and coordination between Mg2+ and the solvent molecules greatly decreases the number of solvent molecules surrounding the Li+, which leads to facile Li+ desolvation during plating. In addition, Mg2+ ions are reduced to Mg via a spontaneous chemical reaction on the Li metal surface and subsequently form a lithiophilic Li–Mg alloy, suppressing lithium dendritic growth. The unique solvation chemistry of Mg(NO3)2 enables long cycling stability and high efficiency of the Li‐metal anode and ensures an unprecedented lifespan for a practical pouch‐type LMB with high‐voltage Ni‐rich NCMA73 cathode even under constrained conditions.  相似文献   

13.
Lithium metal anodes are steadily gaining more attention, as their superior specific capacities and low redox voltage can significantly increase the energy density of rechargeable batteries far beyond those of current Li‐ion batteries. Nonetheless, the relevant technology is still in a premature research stage mainly due to the uncontrolled growth of Li dendrites that ceaselessly cause unwanted side reactions with electrolyte. In order to circumvent this shortcoming, herein, an ionic liquid additive, namely, 1‐dodecyl‐1‐methylpyrrolidinium (Pyr1(12)+) bis(fluorosulfonyl)imide (FSI?), for conventional electrolyte solutions is reported. The Pyr1(12)+ cation with a long aliphatic chain mitigates dendrite growth via the combined effects of electrostatic shielding and lithiophobicity, whereas the FSI? anion can induce the formation of rigid solid–electrolyte interphase layers. The synergy between the cation and anion significantly improves cycling performance in asymmetric and symmetric control cells and a full cell paired with an LiFePO4 cathode. The present study provides a useful insight into the molecular engineering of electrolyte components by manipulating the charge and structures of the involved molecules.  相似文献   

14.
Organic electrodes in aqueous batteries rely on electrochemical redox reactions for charge and discharge. The organic cathode at a discharged state can be spontaneously oxidized when exposed to air, which facilitates the development of air-charging batteries. However, polymer cathodes in aqueous rechargeable Zn-ion batteries (ARZIBs) generally show low discharge median voltage below 1 V. Herein, a new polymer cathode is reported that is prepared by electrodepositing poly(4-hydroxydiphenylamine, HDPA) onto mesoporous activated carbon and shows a relatively high discharge voltage plateau at ≈1.1 V when coupled with a Zn anode. Its self-charging performances at different conditions are investigated. Also, a high areal capacity of 3.8 mAh cm−2 of the cathode is achieved. The poly(4-HDPA) contains both amino and carbonyl groups, and the carbonyl group is found to be fully responsible for redox reaction. Further investigation suggests that both Zn2+ and H+ in the ZnSO4 electrolyte participate in the charge storage process, and the H+ plays a dominant role. The air-charging mechanism of this polymer cathode is elucidated both experimentally and theoretically. To demonstrate the practical applications, prototypes of box-shaped battery pack are air-charged to either drive a mini electric fan or light up LEDs.  相似文献   

15.
Oxygen-containing groups in carbon materials have been shown to affect the carbon anode performance of sodium ion batteries; however, precise identification of the correlation between specific oxygen specie and Na+ storage behavior still remains challenging as various oxygen groups coexist in the carbon framework. Herein, a postengineering method via a mechanochemistry process is developed to achieve accurate doping of (20.12 at%) carboxyl groups in a carbon framework. The constructed carbon anode delivers all-round improvements in Na+ storage properties in terms of a large reversible capacity (382 mAg−1 at 30 mA g−1), an excellent rate capability (153 mAg−1 at 2 A g−1) as well as good cycling stability (141 mAg−1 after 2000 cycles at 1.5 A g−1). Control experiments, kinetic analysis, density functional theory calculations, and operando measurements collectively demonstrate that carboxyl groups not only act as active sites for Na+ capacitive adsorption through suitable electrostatic interactions, but also gradually expand d-spacing by inducing a repulsive force between carbon layers with Na+ preadsorbed, and hence facilitate diffusion-controlled Na+ insertion process. This work provides a new insight in the rational tunning of oxygen-containing groups in carbon for boosting reversible Na+ storage through a synergy of adsorption and intercalation processes.  相似文献   

16.
Zinc metal batteries (ZMBs) hold great promise for large-scale energy storage in renewable solar and wind farms. However, their widespread application is hindered by poor stability and unsatisfactory low-temperature performance, attributed to issues such as dendrite formation, strong Zn2+-H2O coordination, and electrolyte freezing. Herein, a deep eutectic sol electrolyte (DESE) is proposed by mixing SiO2 nanoparticles with a solution composed of 1,3-dioxolane (DOL) and Zn(ClO4)2·6H2O for stable low-temperature ZMBs. By substituting the strong Zn2+- H2O coordination with favorable Zn2+-DOL coordination, the DESE exhibits exceptional antifreezing capability at temperatures beyond −40 °C. The formation of Si-O-Zn2+ bond near SiO2 nanoparticles further improves the low-temperature performance of the DESE by decreasing Zn2+ desolvation energy. Moreover, the SiO2 nanoparticles co-plating/co-stripping with Zn metal, forming a reversible and homogeneous SiO2-enriched interphase to protect the Zn anode from dendrite growth and interfacial side reactions. Remarkably, the DESE-based ZMB full cells exhibit significantly prolonged cycle life of 8000 cycles at 1 A g−1 at 25 °C and 700 cycles at 0.2 A g−1 at -40 °C. This work provides a promising strategy to design advanced electrolytes for practical low-temperature ZMBs.  相似文献   

17.
Narrow electrochemical stability window (1.23 V) of aqueous electrolytes is always considered the key obstacle preventing aqueous sodium‐ion chemistry of practical energy density and cycle life. The sodium‐ion water‐in‐salt electrolyte (NaWiSE) eliminates this barrier by offering a 2.5 V window through suppressing hydrogen evolution on anode with the formation of a Na+‐conducting solid‐electrolyte interphase (SEI) and reducing the overall electrochemical activity of water on cathode. A full aqueous Na‐ion battery constructed on Na0.66[Mn0.66Ti0.34]O2 as cathode and NaTi2(PO4)3 as anode exhibits superior performance at both low and high rates, as exemplified by extraordinarily high Coulombic efficiency (>99.2%) at a low rate (0.2 C) for >350 cycles, and excellent cycling stability with negligible capacity losses (0.006% per cycle) at a high rate (1 C) for >1200 cycles. Molecular modeling reveals some key differences between Li‐ion and Na‐ion WiSE, and identifies a more pronounced ion aggregation with frequent contacts between the sodium cation and fluorine of anion in the latter as one main factor responsible for the formation of a dense SEI at lower salt concentration than its Li cousin.  相似文献   

18.
Over the last 40 years, metallic lithium as an anode material has been of great interest owing to its high energy density. However, dendritic lithium growth causes serious safety issues. Awareness and understanding of the Li deposition and stripping processes have grown rapidly especially in recent years, and consequently, there have been many attempts to suppress the Li dendrites. Recent developments that have modified the electrolytes and the Li anode in order to inhibit the growth of Li dendrite and improve cycling performance are summarized. It has been shown that current density, solid‐electrolyte interphase (SEI) film, Li+ transference number, and shear modulus have significant impact on the growth behavior and the Coulombic efficiency. Various methods have been introduced to increase the surface area of the Li anode, enhance Li+ conductivity, form stable SEI film, and improve mechanical strength of electrolytes. These approaches are discussed in details, and the perspectives regarding the future use of Li anode are also outlined. It is hoped that this review will facilitate the future development of Li metal batteries.  相似文献   

19.

Plasma membrane H+-ATPase (PM H+-ATPase, EC 3.6.1.3.) is a proton pump that is necessary to promote cell growth and ion fluxes across the plasma membrane. The main goal of this study was to evaluate the role of PM H+-ATPase isoform OsA7 expression in rice growth and nitrogen (N) accumulation using three genetically engineered lineages with artificial micro RNA (amiRNA) targeting OsA7 (osa7.1, osa7.2, and osa7.3). PM H+-ATPase isoform expression in rice shoots and roots (wild-type) revealed that OsA7 is highly expressed in roots and is the most highly expressed PM H+-ATPase isoform. The three osa7 lineages had lower fresh weight, grain yield, height, and 1000-grain weight compared to control IRS plants. The hydroponic experiment comprised three NO3 levels over 30 days: 0.2 mM NO3–N, 2.0 mM NO3–N, and NO3 starvation for 3 days. The three osa7 lineages had lower PM H+-ATPase and V-H+-PPase activity as compared to the IRS plants. The root and shoot fresh weights were lower in osa7 lineages. The root/shoot ratio was lower in the osa7 lineages cultivated without nitrogen for 3 days and with 0.2 mM of NO3–N as compared to IRS, and did not change in plants cultivated with 2.0 mM NO3–N. The total N concentration did not change in the three osa7 lineages as compared to IRS. Overall, the results indicate that OsA7 is important for rice growth, grain production, and root growth, but does not affect N accumulation, highlighting the importance of other PM H+-ATPase isoforms in N uptake.

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20.
All‐solid‐state Li‐ion batteries based on Li7La3Zr2O12 (LLZO) garnet structures require novel electrode assembly strategies to guarantee a proper Li+ transfer at the electrode–electrolyte interfaces. Here, first stable cell performances are reported for Li‐garnet, c‐Li6.25Al0.25La3Zr2O12, all‐solid‐state batteries running safely with a full ceramics setup, exemplified with the anode material Li4Ti5O12. Novel strategies to design an enhanced Li+ transfer at the electrode–electrolyte interface using an interface‐engineered all‐solid‐state battery cell based on a porous garnet electrolyte interface structure, in which the electrode material is intimately embedded, are presented. The results presented here show for the first time that all‐solid‐state Li‐ion batteries with LLZO electrolytes can be reversibly charge–discharge cycled also in the low potential ranges (≈1.5 V) for combinations with a ceramic anode material. Through a model experiment, the interface between the electrode and electrolyte constituents is systematically modified revealing that the interface engineering helps to improve delivered capacities and cycling properties of the all‐solid‐state Li‐ion batteries based on garnet‐type cubic LLZO structures.  相似文献   

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