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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.
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   

3.
Uncontrolled growth of Zn dendrites is the main reason for the short-circuit failure of aqueous Zn-ion batteries. Using electrolyte additives to manipulate the crystal growth is one of the most convenient strategies to mitigate the dendrite issue. However, most additives would be unstable during cycling due to the structural reconstruction of the deposition layer. Herein, it is proposed to use 1-butyl-3-methylimidazolium cation (BMIm+ ion) as an electrolyte additive, which could steadily induce the preferential growth of (002) plane and inhibit the formation of Zn dendrites. Specifically, BMIm+ ion will be preferentially adsorbed on (100) and (101) planes of Zn anodes, forcing Zn2+ ion to deposit on the (002) plane, thus inducing the preferential growth of the (002) plane and forming a flat and compact deposition layer. As a result, the Zn anode cycles for 1000 h at10 mA cm−2 and 10 mAh cm−2 as well as a high Coulombic efficiency of 99.8%. Meanwhile, the NH4V4O10||Zn pouch cell can operate stably for 240 cycles at 0.4 A g−1. The BMIm+ ion additive keeps a stable effect on the structural reconstruction of the Zn anode during the prolonged cycling.  相似文献   

4.
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   

5.
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   

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.
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   

8.
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   

9.
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   

10.
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   

11.
While several stretchable batteries utilizing either deterministic or random composite architectures have been described, none have been fabricated using inexpensive printing technologies. In this study, the authors printed a highly stretchable, zinc‐silver oxide (Zn‐Ag2O) battery by incorporating polystyrene‐block ‐polyisoprene‐block ‐polystyrene (SIS) as a hyperelastic binder for custom‐made printable inks. The remarkable mechanical properties of the SIS binder lead to an all‐printed, stretchable Zn‐Ag2O rechargeable battery with a ≈2.5 mA h cm?2 reversible capacity density even after multiple iterations of 100% stretching. This battery offers the highest reversible capacity and discharge current density for intrinsically stretchable batteries reported to date. The electrochemical and mechanical properties are characterized under different strain conditions. The new stress‐enduring printable inks pave ways for further developing stretchable electronics for the wide range of wearable applications.  相似文献   

12.
CO2 electrochemical reduction (CO2RR) can mitigate environmental issues while providing valuable products, yet challenging in activity, selectivity, and stability. Here, a CuS-Bi2S3 heterojunction precursor is reported that can in situ reconstruct to Cu-doped Bismuth (CDB) electrocatalyst during CO2RR. The CDB exhibits an industrial-compatible current density of −1.1 A cm−2 and a record-high formate formation rate of 21.0 mmol h−1 cm−2 at −0.86 V versus the reversible hydrogen electrode toward CO2RR to formate, dramatically outperforming currently reported catalysts. Importantly, the ultrawide potential region of 1050 mV with high formate Faradaic efficiency of over 90% and superior long-term stability for more than 100 h at −400 mA cm−2 can also be realized. Experimental and theoretical studies reveal that the remarkable CO2RR performance of CDB results from the doping effect of Cu which optimizes adsorption of the *OCHO and boosts the structural stability of metallic bismuth catalyst. This study provides valuable inspiration for the design of element-doping electrocatalysts to enhance catalytic activity and durability.  相似文献   

13.
Li metal anodes are going through a great revival but they still encounter grand challenges. One often neglected issue is that most reported Li metal anodes are only cyclable under relatively low current density (<5 mA cm?2) and small areal capacity (<5 mAh cm?2), which essentially limits their high‐power applications and results in ineffective Li utilization (<1%). Herein, it is reported that surface alloyed Li metal anodes can enable reversible cycling with ultrafast rate and ultralarge areal capacity. Low‐cost Si wafers are used and are chemically etched down to 20–30 µm membranes. Simply laminating a Si membrane onto Li foil results in the formation of LixSi alloy film fused onto Li metal with mechanical robustness and high Li‐ion conductivity. Symmetric cell measurements show that the surface alloyed Li anode has excellent cycling stability, even under high current density up to 25 mA cm?2 and unprecedented areal capacity up to 100 mAh cm?2. Furthermore, the surface alloyed Li anode is paired with amorphous MoS3 cathode and achieves remarkable full‐cell performance.  相似文献   

14.
Li-CO2 batteries with a high theoretical energy density (1876 Wh kg−1) have unique benefits for reversible carbon fixation for energy storage systems. However, due to lack of stable and highly active catalysts, the long-term operation of Li-CO2 batteries is limited to low current densities (mainly <0.2 mA cm−2) that are far from practical conditions. In this work, it is discovered that, with an ionic liquid-based electrolyte, highly active and stable transition metal trichalcogenide alloy catalysts of Sb0.67Bi1.33X3 (X = S, Te) enable operation of the Li-CO2 battery at a very high current rate of 1 mA cm−2 for up to 220 cycles. It is revealed that: i) the type of chalcogenide (Te vs S) significantly affects the electronic and catalytic properties of the catalysts, ii) a coupled cation-electron charge transfer process facilitates the carbon dioxide reduction reaction (CO2RR) occurring during discharge, and iii) the concentration of ionic liquid in the electrolyte controls the number of participating CO2 molecules in reactions. A combination of these key factors is found to be crucial for a successful operation of the Li-CO2 chemistry at high current rates. This work introduces a new class of catalysts with potential to fundamentally solve challenges of this type of batteries.  相似文献   

15.
Intrinsically weak metal affinity and sluggish sodium (Na) nucleation/molten fluidic transport of conventional hosts impede the fabrication of high-capacity Na anodes. Mediating surface free energies (SFEs) of hosts and reinforcing their intermolecular attraction to viscous Na fluids can radically solve these problems. Herein, “canaled” tin oxide nanorod arrays grown on a 3D carbon cloth (CC) matrix exhibit distinct polar/nonpolar SFE components that markedly elevate the solid–liquid wettability for molten Na is reported. Such nanocanal defects render strong capillary forces for spontaneous molten Na imbibition and help to instantly activate Na─Sn alloying and Na nucleation reactions. Furthermore, sodiophilic Na15Sn4 interlayers evolved in former alloying procedures also aid in reducing Na nucleation energy barriers and guide the planar electro-deposition/dispersion, alleviating the uncontrolled Na dendrite growth. The derived Na/Na15Sn4/CC anodes can thus keep stable after 2000 h of galvanostatic cycling at 1 mA cm−2 or high-rate testing, without notable dendritic formation. The packed full cells also show superior rate capability and cyclability (capacity retention over 91.5% after all cycling at 1 C). This work provides a smart nano-engineering way to trigger a fast infusion of molten metals into hosts and synergistically facilitate Na fluidic transport, which may push forward the scalable application of Na metal batteries.  相似文献   

16.
Conventional charge storage mechanisms for electrode materials are common in widely exploited insertion/extraction processes, while some sporadic examples of chemical conversion mechanisms exist. It is perceived to be of huge potential, but it is quite challenging to develop new battery chemistry to promote battery performance. Here, an initiating and holistic deposition–dissolution battery mechanism for both cathodes and anodes is reported. A MnO2–Cu battery based on this mechanism demonstrates outstanding energy density (27.7 mWh cm?2), power density (1232 mW cm?2), high reversibility, and unusual Coulombic efficiency. It can be charged to 0.8 mAh cm?2 within 42 s and possessees a stable rate cyclability within vastly varied discharging current density (4–64 mA cm?2). Moreover, the deposition–dissolution mechanism can be universally adopted and derived such that the corresponding MnO2–Zn and MnO2–Bi batteries are successfully constructed. The material selection principle, deposition–dissolution behaviors of cathode/anode materials, and battery performance are systematically elaborated. Since the electrodeposition chemistry is capable of involving a large family of materials, for example, metal oxides as cathode materials, or metals as anode materials, the research could be a model system to open a door to explore new aqueous battery materials and chemistry.  相似文献   

17.
The manipulation of stress in high-capacity microscale alloying anode materials, which undergo significant volumetric variation during cycling, is crucial prerequisite for improved their cycling capability. In this work, an innovative structural design strategy is proposed for scalable fabrication of a unique 3D highly porous micro structured germanium (Ge) featuring micro-nano hierarchical architecture as viable anode for high-performance lithium-ion batteries (LIBs). The resultant micro-sized Ge, consisting of interconnected nanoligaments and bicontinuous nanopores, is endowed with high activity, decreased Li+ diffusion distance and alleviated volume variation, appealing as an ideal platform for in-depth understanding the relationship between structural design and stress evolution. Such a micro-sized Ge being highly porous delivers a record high initial Coulombic efficiency of 92.5%, large volumetric capacity of 2,421 mAh cm−3 at 1.2 mA cm−2, exceptional rate capability (805.6 mAh g−1 at 10 Ag−1) and cycling stability (over 90% capacity retention after 1000 cycles even at 5 A g−1), largely outperforming the reported Ge-based anodes for LIBs. Furthermore, its underlying Li storage mechanism and stress dispersion behavior are explicitly revealed by combined substantial in situ/ex situ experimental characterizations and theoretical computation. This work provides novel insights into the rational design of high-performance and durable alloying anodes toward high-energy LIBs.  相似文献   

18.
《Aquatic Botany》2001,69(2-4):217-234
Decomposition processes were investigated in the soil of a declining, more eutrophic and a healthy, less eutrophic freshwater reed (Phragmites australis (Cav.) Trin. ex Steudel) stand in the littoral zone of Rožmberk fishpond, Czech Republic. Soil and pore water were sampled five times from April to October 1998. Chemical properties, CO2 production in oxic and anoxic conditions, CH4 production, denitrifying enzyme activity (DEA) and bacterial biomass were measured under laboratory conditions in suspensions prepared from homogenised soil samples. The more eutrophic West stand was more anaerobic than the East stand, with lower redox potential, lower pH and with a higher amount of organic acids, mainly acetic and lactic acid. Mean seasonal concentrations of total nitrogen in pore water, nitrogen of amino acids and proteins, and reducing sugars were all higher in the soil at the more eutrophic stand. Higher nutrient status and more reduced conditions at the more eutrophic stand were accompanied by (i) a limitation of aerobic microbial activities (CO2 production in oxic conditions: 0.35 versus 0.54 μmol CO2 cm−3 h−1); lower DEA (4.0 versus 20.2 nmol N2O cm−3 h−1) and a lower proportion of bacteria that were active in aerobic conditions; (ii) by a prevalence of anaerobic over aerobic microbial processes; (iii) by a higher rate of methanogenesis (15.0 versus 11.5 nmol CH4 cm−3 h−1) and (iv) by an overall lower rate of microbial processes as compared to less eutrophied stand. The shift from aerobic to anaerobic microbial metabolism, and a coinciding restriction of metabolic activities at the more eutrophic stand are indicative of an elevated oxygen stress in the soil, associated with accumulation of metabolites toxic to both the micro-organisms and the reed. Possible links between eutrophication, decomposition processes in the soil and reed decline are discussed.  相似文献   

19.
Bismuth vanadate (BiVO4) is reported as a key material in photoelectrocatalysis owing to high theoretical efficiency, relatively narrow band gap of 2.4 eV, and favorable conduction band edge position for hydrogen evolution. However, the sluggish hole transport dynamics lead to slow photogenerated charge separation and transport efficiencies, which result in charge recombination due to aggregation. Herein, a novel hole transport layer of copper(I) thiocyanate (CuSCN) with the aim of significantly enhancing the efficiency of charge transport and stability of BiVO4 photoanodes is reported. The introduction of the hole transport layer could provide an appropriate intermediate energy level for photogenerated hole transfer and avoid charge recombination and trapping. After a photoassisted electrodeposition process of NiCoFe-Bi catalysis, the obtained photoanode achieves a photocurrent density of 5.6 mA cm−2 at 1.23 V versus reversible hydrogen electrode under AM 1.5 G simulated solar radiation, and an applied bias photon to current efficiency of 2.31%. With the CuSCN layer, BiVO4 photoanode presented impressive stable photocurrent during 50 h continuous illumination. Meanwhile, the unbiased tandem device of the NiCoFe-Bi/CuSCN/BiVO4 photoanode and the Si solar cell exhibit a solar-to-hydrogen efficiency of 5.75% and excellent stability for 14 h.  相似文献   

20.
Zn‐based batteries are safe, low cost, and environmentally friendly, as well as delivering the highest energy density of all aqueous battery systems. However, the application of Zn‐based batteries is being seriously hindered by the uneven electrostripping/electroplating of Zn on the anodes, which always leads to enlarged polarization (capacity fading) or even cell shorting (low cycling stability). How a porous nano‐CaCO3 coating can guide uniform and position‐selected Zn stripping/plating on the nano‐CaCO3‐layer/Zn foil interfaces is reported here. This Zn‐deposition‐guiding ability is mainly ascribed to the porous nature of the nano‐CaCO3‐layer, since similar functionality (even though relatively inferior) is also found in Zn foils coated with porous acetylene black or nano‐SiO2 layers. Furthermore, the potential application of this strategy is demonstrated in Zn|ZnSO4+MnSO4|CNT/MnO2 rechargeable aqueous batteries. Compared with the ones with bare Zn anodes, the battery with a nano‐CaCO3‐coated Zn anode delivers a 42.7% higher discharge capacity (177 vs 124 mAh g?1 at 1 A g?1) after 1000 cycles.  相似文献   

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