RESUMEN
The fine regulation of catalysts by the atomic-level removal of inactive atoms can promote the active site exposure for performance enhancement, whereas suffering from the difficulty in controllably removing atoms using current micro/nano-scale material fabrication technologies. Here, we developed a surface atom knockout method to promote the active site exposure in an alloy catalyst. Taking Cu3Pd alloy as an example, it refers to assemble a battery using Cu3Pd and Zn as cathode and anode, the charge process of which proceeds at about 1.1 V, equal to the theoretical potential difference between Cu2+/Cu and Zn2+/Zn, suggesting the electricity-driven dissolution of Cu atoms. The precise knockout of Cu atoms is confirmed by the linear relationship between the amount of the removed Cu atoms and the battery cumulative specific capacity, which is attributed to the inherent atom-electron-capacity correspondence. We observed the surface atom knockout process at different stages and studied the evolution of the chemical environment. The alloy catalyst achieves a higher current density for oxygen reduction reaction compared to the original alloy and Pt/C. This work provides an atomic fabrication method for material synthesis and regulation toward the wide applications in catalysis, energy, and others.
RESUMEN
Aqueous rechargeable zinc-based batteries hold great promise for energy storage applications, with most research utilizing zinc foils as the anode. Conversely, the high tunability of zinc powder (Zn-P) makes it an ideal choice for zinc-based batteries, seamlessly integrating with current battery production technologies. However, challenges such as contact loss, dendrite formation, and a high tendency for corrosion significantly hamper the performance enhancement of Zn-P anodes. This review provides an overview of strategies adopted from various perspectives, including zinc powder optimization, electrode engineering, and electrolyte modification, to address these issues. Additionally, it explores the limitations of existing research and offers valuable insights into potential future directions for further advancements in Zn-P anodes.
RESUMEN
The exploitation of new anion battery systems based on high-abundance oceanic elements (e.g., F-, Cl-, and Br-) is a strong supplement to the current metal cation (e.g., Li+, Na+) battery technologies. Bismuth (Bi), the rare anion-specific anode species nearest to practical application for chloride ion storage, is plagued by volume expansion and structure collapse due to limited control of its conversion behavior. Here, we reveal that a unique epitaxy-like conversion mechanism in the monocrystalline Bi nanospheres (R3m group) can drastically inhibit grain pulverization and capacity fading, which is enabled by Cl- intercalation in their interlayer space. The Bi nanosphere anode can self-evolve and transform into a rigid BiOCl nanosheet-interlaced structure after the initial conversion reaction. With this epitaxy-like conversion mechanism, the Bi anode exhibits a record-high capacity of 249 mAh g-1 (â¼1.2 mAh cm-2) at 0.25 C and sustains more than 1400 h with 20% capacity loss. Pairing this anode with a Prussian blue cathode, the full battery can deliver an ultrahigh desalination capacity of 127.1 m gCl gBi-1. Our study milestones the understanding of conversion-type anode structures, which is an essential step toward the commercialization of aqueous batteries.
RESUMEN
Quinone-based electrodes using carbonyl redox reactions are promising candidates for aqueous energy storage due to their high theoretical specific capacity and high-rate performance. However, the proton storage manners and their influences on the electrochemical performance of quinone are still not clear. Herein, we reveal that proton storage could determine the products of the enol conversion and the electrochemical stability of the organic electrode. Specifically, the protons preferentially coordinated with the prototypical pyrene-4,5,9,10-tetraone (PTO) cathode, and increasing the proton concentration in the electrolyte can improve its working potentials and cycling stability by tailoring the enol conversion reaction. We also found that exploiting Al2(SO4)3 as a pH buffer can increase the energy density of the Zn||PTO batteries from 242.8 to 284.6 Wh kg-1. Our research has a guiding significance for emphasizing proton storage of organic electrodes based on enol conversion reactions and improving their electrochemical performance.
RESUMEN
Developing efficient, robust, and cost-effective trifunctional catalysts for the hydrogen evolution reaction (HER), oxygen evolution reaction (OER) and oxygen reduction reaction (ORR) at high current density and high temperature is crucial for water splitting at industry-level conditions and ultra-high-temperature Zinc-air battery (ZAB). Herein, cobalt nanoparticles well-integrated with nitrogen-doped porous carbon leaves (Co@NPCL) by direct annealing of core-shell bimetallic zeolite imidazolate frameworks is synthesized. Benefiting from the homogeneous distribution of metallic Co nanoparticles, the conductive porous carbon, and the doped N species, the as-fabricated Co@NPCL catalysts exhibit outstanding trifunctional performances with low overpotentials at 10 mA cm-2 for HER (87 mV) and OER (276 mV), long-lasting lifetime of over 2000 h, and a high half-wave potential of 0.86 V versus RHE for ORR. Meanwhile, the Co@NPCL catalyst can serve as both cathode and anode for water splitting at industrial conduction, and exhibit a stable cell voltage of 1.87 V to deliver a constant catalytic current of 500 mA cm-2 over 60 h. Moreover, the excellent trifunctional activity of Co@NPCL enables the flexible ZAB to operate efficiently at ultra-high temperature of 70 °C, delivering 162 mW cm-2 peaks power density and an impressive stability for 4500 min at 2 mA cm-2.
RESUMEN
Aqueous zinc metal batteries are regarded as a promising energy storage solution for a green and sustainable society in the future. However, the practical application of metallic zinc anode is plagued by the thermodynamic instability issue of water molecules in conventional electrolytes, which leads to severe dendrite growth and side reactions. In this work, an ultra-thin and high areal capacity metallic zinc anode is achieved by utilizing crystalline water with a stable stoichiometric ratio. Unlike conventional electrolytes, the designed electrolyte can effectively suppress the reactivity of water molecules and diminish the detrimental corrosion on the metallic zinc anode, while preserving the inherent advantages of water molecules, including great kinetic performance in electrolytes and H+ capacity contribution in cathodes. Based on the comprehensive performance of the designed electrolyte, the 10 µm Zn||10 µm Zn symmetric cell stably ran for 1000 h at the current density of 1 mA cm-2, and the areal capacity of 1 mAh cm-2, whose depth-of-discharge is over 17.1%. The electrochemical performance of the 10 µm Zn||9.3 mg cm-2 polyaniline (PANI) full-cell demonstrates the feasibility of the designed electrolyte. This work provides a crucial understanding of balancing activity of water molecules in aqueous zinc metal batteries.
RESUMEN
Electroactive organic electrode materials exhibit remarkable potential in aqueous zinc ion batteries (AZIBs) due to their abundant availability, customizable structures, sustainability, and high reversibility. However, the research on AZIBs has predominantly concentrated on unraveling the storage mechanism of zinc cations, often neglecting the significance of anions in this regard. Herein, bipolar poly(thionine) is synthesized by a simple and efficient polymerization reaction, and the kinetics of different anions are investigated using poly(thionine) as the cathode of AZIBs. Notably, poly(thionine) is a bipolar organic polymer electrode material and exhibits enhanced stability in aqueous solutions compared to thionine monomers. Kinetic analysis reveals that ClO4 - exhibits the fastest kinetics among SO4 2-, Cl-, and OTF-, demonstrating excellent rate performance (109 mAh g-1 @ 0.5 A g-1 and 92 mAh g-1 @ 20 A g-1). Mechanism studies reveal that the poly(thionine) cathode facilitates the co-storage of both anions and cations in Zn(ClO4)2. Furthermore, the lower electrostatic potential of ClO4 - influences the strength of hydrogen bonding with water molecules, thereby enhancing the overall kinetics in aqueous electrolytes. This work provides an effective strategy for synthesizing high-quality organic materials and offers new insights into the kinetic behavior of anions in AZIBs.
RESUMEN
Attaining high reversibility of the electrodes and electrolyte is essential for the longevity of secondary batteries. Rechargeable zinc-air batteries (RZABs), however, encounter drastic irreversible changes in the zinc anodes and air cathodes during cycling. To uncover the mechanisms of reversibility loss in RZABs, we investigate the evolution of the zinc anode, alkaline electrolyte, and air electrode through experiments and first-principles calculations. Morphology diagrams of zinc anodes under versatile operating conditions reveal that the nanosized mossy zinc dominates the later cycling stage. Such anodic change is induced by the increased zincate concentration due to hydrogen evolution, which is catalyzed by the mossy structure and results in oxide passivation on electrodes and eventually leads to low true Coulombic efficiencies and short life spans of batteries. Inspired by these findings, we finally present a novel overcharge-cycling protocol to compensate for the Coulombic efficiency loss caused by hydrogen evolution and significantly extend the battery life.
RESUMEN
The dissolution of transition metal ions causes the notorious peeling of active substances and attenuates electrochemical capacity. Frustrated by the ceaseless task of pushing a boulder up a mountain, Sisyphus of the Greek myth yearned for a treasure to be unearthed that could bolster his efforts. Inspirationally, by using ferricyanide ions (Fe(CN)63-) in an electrolyte as a driving force and taking advantage of the fast nucleation rate of copper hexacyanoferrate (CuHCF), we successfully reversed the dissolution of Fe and Cu ions that typically occurs during cycling. The capacity retention increased from 5.7% to 99.4% at 0.5 A g-1 after 10,000 cycles, and extreme stability of 99.8% at 1 A g-1 after 40,000 cycles was achieved. Fe(CN)63- enables atom-by-atom substitution during the electrochemical process, enhancing conductivity and reducing volume change. Moreover, we demonstrate that this approach is applicable to various aqueous batteries (i.e., NH4+, Li+, Na+, K+, Mg2+, Ca2+, and Al3+).
RESUMEN
Organic additives with high-reduction potentials are generally applied in aqueous electrolytes to stabilize the Zn anode, while compromise safety and environmental compatibility. Highly concentrated water-in-salt electrolytes have been proposed to realize the high reversibility of Zn plating/stripping; however, their high cost and viscosity hinder their practical applications. Therefore, exploring low-concentration Zn salts, that can be used directly to stabilize Zn anodes, is of primary importance. Herein, we developed an asymmetric anion group, bi(difluoromethanesulfonyl)(trifluoromethanesulfonyl)imide (DFTFSI- )-based novel zinc salt, Zn(DFTFSI)2 , to obtain a high ionic conductivity and a highly stable dendrite-free Zn anode. Experimental tests and theoretical calculations verified that DFTFSI- in the Zn2+ solvation sheath and inner Helmholtz plane would be preferentially reduced to construct layer-structured SEI films, inhibiting hydrogen evolution and side reactions. Consequently, the Zn | | ${||}$ Zn symmetric cell with 1M Zn(DFTFSI)2 aqueous electrolyte delivers an ultralong cycle life for >2500â h outperforming many other conventional Zn salt electrolytes. The Zn | | ${||}$ Br2 battery also exhibits a long lifespan over 1200â cycles at ~99.8 % Coulombic efficiency with a high capacity retention of 92.5 %. Furthermore, this outstanding performance translates well to a high-areal-capacity Zn | | ${||}$ Br2 battery (~5.6â mAh â cm-2 ), cycling over 320â cycles with 95.3 % initial capacity retained.
RESUMEN
The main challenges faced by aqueous rechargeable nickel-zinc batteries are their comparatively low energy density and poor cycling stability. Moreover, the preparation procedures of these cathodes are complex and not easily scalable. Herein, we utilized MXene to improve the electrodeposition preparation of NiCo layered double hydroxides (LDH). Benefiting from the improved interfacial contact between nickel foam (NF) and platting solution and the enhanced ionic conductivity of platting product based on MXene additives, the resulting binder-free NiCo LDH electrode can achieve ultrahigh areal loading (~65 mg cm-2) with abundant active surface for redox reactions and maintained short transport pathway for ion diffusion and charge transfer. Furthermore, the as-fabricated alkaline NiCo LDH-based battery delivers high discharge capacity, up to 20.2 mAh cm-2 (311 mAh g-1), accompanied by remarkable rate performance (9.6 mAh cm-2 or 148 mAh g-1 at 120 mA cm-2). Due to the high structural and chemical stability of MXenes/LDH-based electrode, excellent cycling life can also be achieved with 88.6% capacity retention after 10000 cycles. In addition, ultrahigh areal energy density (31.2 mWh cm-2) and gravimetric energy density (465 Wh kg-1) can be simultaneously achieved. This work has inspired the design of advanced cathode materials to develop high-performance aqueous zinc batteries.
RESUMEN
Compared to sp2-hybridized graphene, graphdiynes (GDYs) composed of sp and sp2 carbon are highly promising as efficient catalysts for electrocatalytic oxygen reduction into oxygen peroxide because of the high catalytic reactivity of the electron-rich sp-carbon atoms. The desired catalytic capacity of GDY, such as catalytic selectivity and efficiency, can theoretically be achieved by strategically steering the sp-carbon contents or the topological arrangement of the acetylenic linkages and aromatic bonds. Herein, we successfully tuned the electrocatalytic activity of GDYs by regulating the sp-to-sp2 carbon ratios with different organic monomer precursors. As the active sp-carbon atoms possess electron-sufficient π orbitals, they can donate electrons to the lowest unoccupied molecular orbital (LUMO) orbitals of O2 molecules and initiate subsequent O2 reduction, GDY with the high sp-carbon content of 50â at % exhibits excellent capability of catalyzing O2 reduction into H2O2. It demonstrates exceptional H2O2 selectivity of over 95.0 % and impressive performance in practical H2O2 production, Faraday efficiency (FE) exceeding 99.0 %, and a yield of 83.3â nmol s-1 cm-2. Our work holds significant importance in effectively steering the inherent properties of GDYs by purposefully adjusting the sp-to-sp2 carbon ratio and highlights their immense potential for research and applications in catalysis and other fields.
RESUMEN
High iodine loading and high-temperature adaptability of the iodine cathode are prerequisites to achieving high energy density at full battery level and promoting the practical application for the zinc-iodine (Zn-I2 ) battery. However, it would aggravate the polyiodide shuttle effect when employing high iodine loading and working temperature. Here, a sustainable cationic cellulose nanofiber (cCNF) was employed to confine the active iodine species through strong physiochemical adsorption to enlarge the iodine loading and stabilize it even at high temperatures. The cCNF could accommodate dual-functionality by enlarging the iodine loading and suppressing the polyiodide shuttle effect, owing to the unique framework structure with abundant surface positive charges. As a result, the iodine cathode based on the cCNF could deliver high iodine mass loading of 14.1â mg cm-2 with a specific capacity of 182.7â mAh g-1 , high areal capacity of 2.6â mAh cm-2 , and stable cycling over 3000 cycles at 2â A g-1 , thus enabling a high energy density of 34.8â Wh kg-1 and the maximum power density of 521.2â W kg-1 at a full Zn-I2 battery level. In addition, even at a high temperature of 60 °C, the Zn-I2 battery could still deliver a stable cycling.
RESUMEN
Directly electrochemical conversion of nitrate (NO3 -) is an efficient and environmentally friendly technology for ammonia (NH3) production but is challenged by highly selective electrocatalysts. High-entropy alloys (HEAs) with unique properties are attractive materials in catalysis, particularly for multi-step reactions. Herein, we first reported the application of HEA (FeCoNiAlTi) for electrocatalytic NO3 - reduction to NH3 (NRA). The bulk HEA is active for NRA but limited by the unsatisfied NH3 yield of 0.36â mg h-1 cm-2 and Faradaic efficiency (FE) of 82.66 %. Through an effective phase engineering strategy, uniform intermetallic nanoparticles are introduced on the bulk HEA to increase electrochemical active surface area and charge transfer efficiency. The resulting nanostructured HEA (n-HEA) delivers enhanced electrochemical NRA performance in terms of NH3 yield (0.52â mg h-1 cm-2) and FE (95.23 %). Further experimental and theoretical investigations reveal that the multi-active sites (Fe, Co, and Ni) dominated electrocatalysis for NRA over the n-HEA. Notably, the typical Co sites exhibit the lowest energy barrier for NRA with *NH2 to *NH3as the rate-determining step.
RESUMEN
The rechargeable aqueous Zn||MnO2 chemistry has been extensively explored, but its electrochemical reaction mechanisms, especially in the context of MnO2/Mn2+ conversion and Zn2+/H+ intercalation chemistry, remain not fully understood. Here, we designed an amphiphilic hydrogel electrolyte, which distinguished the MnO2/Mn2+ conversion, Zn2+ intercalation, and H+ intercalation and conversion processes at three distinct discharge plateaus of an aqueous Zn||MnO2 battery. The amphiphilic hydrogel electrolyte is featured with an extended electrochemical stability window up to 3.0â V, high ionic conductivity, Zn2+-selective ion tunnels, and hydrophobic associations with cathode materials. This specifically designed electrolyte allows the MnO2/Mn2+ conversion reaction at a discharge plateau of 1.75â V. More interesting, the discharge plateaus of ~1.33â V, previously assigned as the co-intercalation of Zn2+ and H+ ions in the MnO2 cathode, are specified as the exclusive intercalation of Zn2+ ions, leading to an ultra-flat voltage plateau. Furthermore, with a distinct three-step electrochemical energy storage process, a high areal capacity of 1.8â mAh cm-2 and high specific energy of 0.858â Wh cm-2, even at a low MnO2 loading mass of 0.5â mg cm-2 are achieved. To our knowledge, this is the first report to fully distinguish different mechanisms at different potentials in aqueous Zn||MnO2 batteries.
RESUMEN
The extensively studied Prussian blue analogs (PBAs) in various batteries are limited by their low discharge capacity, or subpar rate etc., which are solely reliant on the cation (de)intercalation mechanism. In contrast to the currently predominant focus on cations, we report the overlooked anion-cation competition chemistry (Cl-, K+, Zn2+) stimulated by high-voltage scanning. With our designed anion-cation combinations, the KFeMnHCF cathode battery delivers comprehensively superior discharge performance, including voltage plateau >2.0â V (vs. Zn/Zn2+), capacity >150â mAh g-1, rate capability with capacity maintenance above 96 % from 0.6 to 5â A g-1, and cyclic stability exceeding 3000â cycles. We further verify that such comprehensive improvement of electrochemical performance utilizing anion-cation competition chemistry is universal for different types of PBAs. Our work would pave a new and efficient road towards the next-generation high-performance PBAs cathode batteries.
RESUMEN
Chalcogens, especially tellurium (Te), as conversion-type cathodes possess promising prospects for zinc batteries (ZBs) with potential rich valence supply and high energy density. However, the conversion reaction of Te is normally restricted to the Te2-/Te0 redox with a low voltage plateau at â¼0.59 V (vs Zn2+/Zn) rather than the expected positive valence conversion of Te0 to Ten+, inhibiting the development of Te-based batteries toward high output voltage and energy density. Herein, the desired reversible Te2-/Te0/Te2+/Te4+ redox behavior with up to six-electron transfer was successfully activated by employing a highly concentrated Cl--containing electrolyte (Cl- as strong nucleophile) for the first time. Three flat discharge plateaus located at 1.24, 0.77, and 0.51 V, respectively, are attained with a total capacity of 802.7 mAh g-1. Furthermore, to improve the stability of Ten+ products and enhance the cycling stability, a modified ionic liquid (IL)-based electrolyte was fabricated, leading to a high-performance Znâ¥Te battery with high areal capacity (7.13 mAh cm-2), high energy density (542 Wh kgTe-1 or 227 Wh Lcathdoe+anode-1), excellent cycling performance, and a low self-discharge rate based on 400 mAh-level pouch cell. The results enhance the understanding of tellurium chemistry in batteries, substantially promising a remarkable route for advanced ZBs.
RESUMEN
The uncontrolled zinc electrodeposition and side reactions severely limit the power density and lifespan of Zn metal batteries. Herein, the multi-level interface adjustment effect is realized with low-concentration redox-electrolytes (0.2 m KI) additives. The iodide ions adsorbed on the zinc surface significantly suppress water-induced side reactions and by-product formation and enhance the kinetics of zinc deposition. The distribution of relaxation times results reveal that iodide ions can reduce the desolvation energy of hydrated zinc ions and guide the deposition of zinc ions due to their strong nucleophilicity. As a consequence, the Zn||Zn symmetric cell achieves superior cycling stability (>3000 h at 1 mA cm-2 , 1 mAh cm-2 ) accompanied by a uniform deposition and a fast reaction kinetics with a low voltage hysteresis (<30 mV). Additionally, coupled with an activated carbon (AC) cathode, the assembled Zn||AC cell delivers a high-capacity retention of 81.64% after 2000 cycles at 4 A g-1 . More importantly, the operando electrochemical UV-vis spectroscopies show that a small number of I3 - can spontaneously react with the dead zinc as well as basic zinc saltsand regenerate iodide ions and zinc ions; thus, the Coulombic efficiency of each charge-discharge process is close to 100%.
RESUMEN
Constructing a reliable solid-electrolyte interphase (SEI) is imperative for enabling highly reversible zinc metal (Zn0 ) electrodes. Contrary to conventional "bulk solvation" mechanism, we found the SEI structure is dominated by electric double layer (EDL) adsorption. We manipulate the EDL adsorption and Zn2+ solvation with ether additives (i.e. 15-crown-5, 12-crown-4, and triglyme). The 12-crown-4 with medium adsorption on EDL leads to a layer-structured SEI with inner inorganic ZnFx /ZnSx and outer organic C-O-C components. This structure endows SEI with high rigidness and strong toughness enabling the 100â cm2 Zn||Zn pouch cell to exhibit a cumulative capacity of 4250â mAh cm-2 at areal-capacity of 10â mAh cm-2 . More importantly, a 2.3â Ah Zn||Zn0.25 V2 O5 â n H2 O pouch cell delivers a recorded energy density of 104â Wh Lcell -1 and runs for >70â days under the harsh conditions of low negative/positive electrode ratio (2.2 : 1), lean electrolyte (8â g Ah-1 ), and high-areal-capacity (≈13â mAh cm-2 ).
RESUMEN
Though massive efforts have been devoted to exploring Br-based batteries, the highly soluble Br2 /Br3 - species causing rigorous "shuttle effect", leads to severe self-discharge and low Coulombic efficiency. Conventionally, quaternary ammonium salts such as methyl ethyl morpholinium bromide (MEMBr) and tetrapropylammonium bromide (TPABr) are used to fix Br2 and Br3 - , but they occupy the mass and volume of battery without capacity contribution. Here, we report an all-active solid interhalogen compound, IBr, as a cathode to address the above challenges, in which the oxidized Br0 is fixed by iodine (I), thoroughly eliminating cross-diffusing Br2 /Br3 - species during the whole charging and discharging process. The Zn||IBr battery delivers remarkably high energy density of 385.8â Wh kg-1 , which is higher than those of I2 , MEMBr3 , and TPABr3 cathodes. Our work provides new approaches to achieve active solid interhalogen chemistry for high-energy electrochemical energy storage devices.