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Aqueous zinc (Zn) batteries have attracted global attention for energy storage. Despite significant progress in advancing Zn anode materials, there has been little progress in cathodes. The predominant cathodes working with Zn2+/H+ intercalation, however, exhibit drawbacks, including a high Zn2+ diffusion energy barrier, pH fluctuation(s) and limited reproducibility. Beyond Zn2+ intercalation, alternative working principles have been reported that broaden cathode options, including conversion, hybrid, anion insertion and deposition/dissolution. In this review, we report a critical assessment of non-intercalation-type cathode materials in aqueous Zn batteries, and identify strengths and weaknesses of these cathodes in small-scale batteries, together with current strategies to boost material performance. We assess the technical gap(s) in transitioning these cathodes from laboratory-scale research to industrial-scale battery applications. We conclude that S, I2 and Br2 electrodes exhibit practically promising commercial prospects, and future research is directed to optimizing cathodes. Findings will be useful for researchers and manufacturers in advancing cathodes for aqueous Zn batteries beyond Zn2+ intercalation.
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Aqueous zinc batteries are practically promising for large-scale energy storage because of cost-effectiveness and safety. However, application is limited because of an absence of economical electrolytes to stabilize both the cathode and anode. Here, we report a facile method for advanced zinc-iodine batteries via addition of a trace imidazolium-based additive to a cost-effective zinc sulfate electrolyte, which bonds with polyiodides to boost anti-self-discharge performance and cycling stability. Additive aggregation at the cathode improves the rate capacity by boosting the I2 conversion kinetics. Also, the introduced additive enhances the reversibility of the zinc anode by adjusting Zn2+ deposition. The zinc-iodine pouch cell, therefore, exhibits industrial-level performance evidenced by a â¼99.98% Coulombic efficiency under ca. 0.4C, a significantly low self-discharge rate with 11.7% capacity loss per month, a long lifespan with 88.3% of initial capacity after 5000 cycles at a 68.3% zinc depth-of-discharge, and fast-charging of ca. 6.7C at a high active-mass loading >15 mg cm-2. Highly significant is that this self-discharge surpasses commercial nickel-metal hydride batteries and is comparable with commercial lead-acid batteries, together with the fact that the lifespan is over 10 times greater than reported works, and the fast-charging performance is better than commercial lithium-ion batteries.
RESUMEN
Zinc-iodine (Zn-I2) batteries are gaining popularity due to cost-effectiveness and ease of manufacturing. However, challenges like polyiodide shuttle effect and Zn dendrite growth hinder their practical application. Here, we report a cation exchange membrane to simultaneously prevent the polyiodide shuttle effect and regulate Zn2+ deposition. Comprised of rigid polymers, this membrane shows superior swelling resistance and ion selectivity compared to commercial Nafion. The resulting Zn-I2 battery exhibits a high Coulombic efficiency of 99.4% and low self-discharge rate of 4.47% after 48 h rest. By directing a uniform Zn2+ flux, the membrane promotes a homogeneous electric field, resulting in a dendrite-free Zn surface. Moreover, its microporous structure enables pre-adsorption of additional active materials prior to battery assembly, boosting battery capacity to 287 mA h g-1 at 0.1 A g-1. At 2 A g-1, the battery exhibits a steady running for 10,000 cycles with capacity retention up to 96.1%, demonstrating high durability of the membrane. The practicality of the membrane is validated via a high loading (35 mg cm-2) pouch cell with impressive cycling stability, paving a way for membrane design towards advanced Zn-I2 batteries.
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Existing lithium-ion battery technology is struggling to meet our increasing requirements for high energy density, long lifetime, and low-cost energy storage. Here, a hybrid electrode design is developed by a straightforward reengineering of commercial electrode materials, which has revolutionized the "rocking chair" mechanism by unlocking the role of anions in the electrolyte. Our proof-of-concept hybrid LiFePO4 (LFP)/graphite electrode works with a staged deintercalation/intercalation mechanism of Li+ cations and PF6 - anions in a broadened voltage range, which was thoroughly studied by ex situ X-ray diffraction, ex situ Raman spectroscopy, and operando neutron powder diffraction. Introducing graphite into the hybrid electrode accelerates its conductivity, facilitating the rapid extraction/insertion of Li+ from/into the LFP phase in 2.5 to 4.0 V. This charge/discharge process, in turn, triggers the in situ formation of the cathode/electrolyte interphase (CEI) layer, reinforcing the structural integrity of the whole electrode at high voltage. Consequently, this hybrid LFP/graphite-20% electrode displays a high capacity and long-term cycling stability over 3,500 cycles at 10 C, superior to LFP and graphite cathodes. Importantly, the broadened voltage range and high capacity of the hybrid electrode enhance its energy density, which is leveraged further in a full-cell configuration.
RESUMEN
Zn electrodes in aqueous media exhibit an unstable Zn/electrolyte interface due to severe parasitic reactions and dendrite formation. Here, a dynamic Zn interface modulation based on the molecular switch strategy is reported by hiring γ-butyrolactone (GBL) in ZnCl2 /H2 O electrolyte. During Zn plating, the increased interfacial alkalinity triggers molecular switch from GBL to γ-hydroxybutyrate (GHB). GHB strongly anchors on Zn surface via triple Zn-O bonding, leading to suppressive hydrogen evolution and texture-regulated Zn morphology. Upon Zn stripping, the fluctuant pH turns the molecular switch reaction off through the cyclization of GHB to GBL. This dynamic molecular switch strategy enables high Zn reversibility with Coulombic efficiency of 99.8 % and Zn||iodine batteries with high-cyclability under high Zn depth of discharge (50 %). This study demonstrates the importance of dynamic modulation for Zn electrode and realizes the reversible molecular switch strategy to enhance its reversibility.
RESUMEN
As a burgeoning electrolyte system, eutectic electrolytes based on ZnCl2 /Zn(CF3 SO3 )2 /Zn(TFSI)2 have been widely proposed in advanced Zn-I2 batteries; however, safety and cost concerns significantly limit their applications. Here, we report new-type ZnSO4 -based eutectic electrolytes that are both safe and cost-effective. Their universality is evident in various solvents of polyhydric alcohols, in which multiple -OH groups not only involve in Zn2+ solvation but also interact with water, resulting in the high stability of electrolytes. Taking propylene glycol-based hydrated eutectic electrolyte as an example, it features significant advantages in non-flammability and low price that is <1/200 cost of Zn(CF3 SO3 )2 /Zn(TFSI)2 -based eutectic electrolytes. Moreover, its effectiveness in confining the shuttle effects of I2 cathode and side reactions of Zn anodes is evidenced, resulting in Zn-I2 cells with high reversibility at 1â C and 91.4 % capacity remaining under 20â C. After scaling up to the pouch cell with a record mass loading of 33.3â mg cm-2 , super-high-capacity retention of 96.7 % is achieved after 500â cycles, which exceeds other aqueous counterparts. This work significantly broadens the eutectic electrolyte family for advanced Zn battery design.
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Potassium-sulfur batteries hold practical promise for next-generation batteries because of their high theoretical gravimetric energy density and low cost. However, significant impediments are the sluggish K2S oxidation kinetics and a lack of atomic-level understanding of K2S oxidation. Here, for the first time, we report the catalytic oxidation of K2S on a sulfur host with Co single atoms immobilized on nitrogen-doped carbon. On the basis of combined spectroscopic characterizations, electrochemical evaluation, and theoretical computations, we show a synergistic effect of dynamic Co-S and N-K interactions to catalyze K2S oxidation. The resultant potassium-sulfur battery exhibited high capacities of 773 and 535 mAh g-1 under high current densities of 1 and 2 C, respectively. These findings provide atomic-scale insights for the rational design of highly efficient sulfur hosts.
RESUMEN
Antisolvent addition has been widely studied in crystallization in the pharmaceutical industries by breaking the solvation balance of the original solution. Here we report a similar antisolvent strategy to boost Zn reversibility via regulation of the electrolyte on a molecular level. By adding for example methanol into ZnSO4 electrolyte, the free water and coordinated water in Zn2+ solvation sheath gradually interact with the antisolvent, which minimizes water activity and weakens Zn2+ solvation. Concomitantly, dendrite-free Zn deposition occurs via change in the deposition orientation, as evidenced by in situ optical microscopy. Zn reversibility is significantly boosted in antisolvent electrolyte of 50 % methanol by volume (Anti-M-50 %) even under harsh environments of -20 °C and 60 °C. Additionally, the suppressed side reactions and dendrite-free Zn plating/stripping in Anti-M-50 % electrolyte significantly enhance performance of Zn/polyaniline coin and pouch cells. We demonstrate this low-cost strategy can be readily generalized to other solvents, indicating its practical universality. Results will be of immediate interest and benefit to a range of researchers in electrochemistry and energy storage.
RESUMEN
Aqueous Zn-ion batteries (ZIBs) are regarded as alternatives to Li-ion batteries benefiting from both improved safety and environmental impact. The widespread application of ZIBs, however, is compromised by the lack of high-performance cathodes. Currently, only the intercalation mechanism is widely reported in aqueous ZIBs, which significantly limits cathode options. Beyond Zn-ion intercalation, we comprehensively study the conversion mechanism for Zn2+ storage and its diffusion pathway in a CuI cathode, indicating that CuI occurs a direct conversion reaction without Zn2+ intercalation due to the high energy barrier for Zn2+ intercalation and migration. Importantly, this direct conversion reaction mechanism can be readily generalized to other high-capacity cathodes, such as Cu2 S (336.7â mA h g-1 ) and Cu2 O (374.5â mA h g-1 ), indicating its practical universality. Our work enriches the Zn-ion storage mechanism and significantly broadens the cathode horizons towards next-generation ZIBs.
RESUMEN
Despite being extensively explored as cathodes in batteries, sulfur (S) can function as a low-potential anode by changing charge carriers in electrolytes. Here, a highly reversible S anode that fully converts from S8 0 to S2- in static aqueous S-I2 batteries by using Na+ as the charge carrier is reported. This S anode exhibits a low potential of -0.5 V (vs standard hydrogen electrode) and a near-to-theoretical capacity of 1404 mA h g-1 . Importantly, it shows significant advantages over the widely used Zn anode in aqueous media by obviating dendrite formation and H2 evolution. To suppress "shuttle effects" faced by both S and I2 electrodes, a scalable sulfonated polysulfone (SPSF) membrane is proposed, which is superior to commercial Nafion in cost (US$1.82 m-2 vs $3500 m-2 ) and environmental benignity. Because of its ultra-high selectivity in blocking polysulfides/iodides, the battery with SPSF displays excellent cycling stability. Even under 100% depth of discharge, the battery demonstrates high capacity retention of 87.6% over 500 cycles, outperforming Zn-I2 batteries with 3.1% capacity under the same conditions. These findings broaden anode options beyond metals for high-energy, low-cost, and fast-chargeable batteries.
RESUMEN
Aqueous zinc-iodine (Zn-I2) batteries hold potential for large-scale energy storage but struggle with shuttle effects of I2 cathodes and poor reversibility of Zn anodes. Here, an interfacial gelation strategy is proposed to suppress the shuttle effects and improve the Zn reversibility simultaneously by introducing silk protein (SP) additive. The SP can migrate bidirectionally toward cathode and anode interfaces driven by the periodically switched electric field direction during charging/discharging. For I2 cathodes, the interaction between SP and polyiodides forms gelatinous precipitate to avoid the polyiodide dissolution, evidenced by excellent electrochemical performance, including high specific capacity and Coulombic efficiency (CE) (215 mAh g-1 and 99.5% at 1 C), excellent rate performance (≈170 mAh g-1 at 50 C), and extended durability (6000 cycles at 10 C). For Zn anodes, gelatinous SP serves as protective layer to boost the Zn reversibility (99.7% average CE at 2 mA cm-2) and suppress dendrites. Consequently, a 500 mAh Zn-I2 pouch cell with high-loading cathode (37.5 mgiodine cm-2) and high-utilization Zn anode (20%) achieves remarkable energy density (80 Wh kg-1) and long-term durability (>1000 cycles). These findings underscore the simultaneous modulation of both cathode and anode and demonstrate the potential for practical applications of Zn-I2 batteries.
RESUMEN
The exploration of post-Lithium (Li) metals, such as Sodium (Na), Potassium (K), Magnesium (Mg), Calcium (Ca), Aluminum (Al), and Zinc (Zn), for electrochemical energy storage has been driven by the limited availability of Li and the higher theoretical specific energies compared to the state-of-the-art Li-ion batteries. Post-Li metal||S batteries have emerged as a promising system for practical applications. Yet, the insufficient understanding of quantitative cell parameters and the mechanisms of sulfur electrocatalytic conversion hinder the advancement of these battery technologies. This perspective offers a comprehensive analysis of electrode parameters, including S mass loading, S content, electrolyte/S ratio, and negative/positive electrode capacity ratio, in establishing the specific energy (Wh kg-1) of post-Li metal||S batteries. Additionally, we critically evaluate the progress in investigating electrochemical sulfur conversion via homogeneous and heterogeneous electrocatalytic approaches in both non-aqueous Na/K/Mg/Ca/Al||S and aqueous Zn||S batteries. Lastly, we provide a critical outlook on potential research directions for designing practical post-Li metal||S batteries.
RESUMEN
Wiskott-Aldrich syndrome (WAS) is a rare X-linked recessive primary immunodeficiency disorder. Mutations in the WAS gene are considered to be the primary cause of WAS. In this work, we report a boy who presented with intracranial hemorrhage (ICH) as an initial symptom and detects a novel pathogenic synonymous mutation in his WAS gene. His mother was a carrier of the mutant gene. The mutation, located at position c.273 (c.273 G>A) in exon 2, is a synonym mutation and predicted to affect protein expression by disrupting gene splicing. This study summarizes the diagnosis and treatment process of the patient and expands the genetic spectrum of WAS.
RESUMEN
The practical implementation of aqueous zinc-ion batteries (AZIBs) encounters challenges such as dendrite growth, parasitic reactions, and severe decay in battery performance under harsh environments. Here, a novel hydrated eutectic electrolyte (HEE) composed of Zn(ClO4 )2 ·6H2 O, ethylene glycol (EG), and InCl3 solution is introduced to effectively extend the lifespan of AZIBs over a wide temperature range from -50 to 50 °C. Molecular dynamics simulations and spectroscopy analysis demonstrate that the H2 O molecules are confined within the liquid eutectic network through dual-interaction, involving coordination with Zn2+ and hydrogen bonding with EG, thus weakening the activity of free water and extending the electrochemical window. Importantly, cryo-transmission electron microscopy and spectroscopy techniques reveal that HEE in situ forms a zincophobic/zincophilic bilayer interphase by the dissociation-reduction of eutectic molecules. Specifically, the zincophilic interphase reduces the energy barrier for Zn nucleation, promoting uniform Zn deposition, while the zincophobic interphase prevents active water from contacting the Zn surface, thus inhibiting the side reactions. Furthermore, the relationships between the structural evolution of the liquid eutectic network and interfacial chemistry at electrode/electrolyte interphase are further discussed in this work. The scalability of this design strategy can bring benefits to AZIBs operating over a wide temperature range.
RESUMEN
Achieving reversible insertion/extraction in most cathodes for aqueous aluminum ion batteries (AAIBs) is a significant challenge due to the high charge density of Al3+ and strong electrostatic interactions. Organic materials facilitate the hosting of multivalent carriers and rapid ions diffusion through the rearrangement of chemical bonds. Here, a bipolar conjugated poly(2,3-diaminophenazine) (PDAP) on carbon substrates prepared via a straightforward electropolymerization method is introduced as cathode for AAIBs. The integration of n-type and p-type active units endow PDAP with an increased number of sites for ions interaction. The long-range conjugated skeleton enhances electron delocalization and collaborates with carbon to ensure high conductivity. Moreover, the strong intermolecular interactions including π-π interaction and hydrogen bonding significantly enhance its stability. Consequently, the Al//PDAP battery exhibits a large capacity of 338 mAh g-1 with long lifespan and high-rate capability. It consistently demonstrates exceptional electrochemical performances even under extreme conditions with capacities of 155 and 348 mAh g-1 at -20 and 45 °C, respectively. In/ex situ spectroscopy comprehensively elucidates its cation/anion (Al3+/H3O+ and ClO4 -) storage with 3-electron transfer in dual electroactive centers (CâN and -NH-). This study presents a promising strategy for constructing high-performance organic cathode for AAIBs over a wide temperature range.
RESUMEN
Aqueous aluminum-ion batteries (AAIBs) are considered as a promising alternative to lithium-ion batteries due to their large theoretical capacity, high safety, and low cost. However, the uneven deposition, hydrogen evolution reaction (HER), and corrosion during cycling impede the development of AAIBs, especially under a harsh environment. Here, a hydrated eutectic electrolyte (AATH40) composed of Al(OTf)3, acetonitrile (AN), triethyl phosphate (TEP), and H2O was designed to improve the electrochemical performance of AAIBs in a wide temperature range. The combination of molecular dynamics simulations and spectroscopy analysis reveals that AATH40 has a less-water-solvated structure [Al(AN)2(TEP)(OTf)2(H2O)]3+, which effectively inhibits side reactions, decreases the freezing point, and extends the electrochemical window of the electrolyte. Furthermore, the formation of a solid electrolyte interface, which effectively inhibits HER and corrosion, has been demonstrated by X-ray photoelectron spectroscopy, X-ray diffraction tests, and in situ differential electrochemical mass spectrometry. Additionally, operando synchrotron Fourier transform infrared spectroscopy and electrochemical quartz crystal microbalance with dissipation monitoring reveal a three-electron storage mechanism for the Al//polyaniline full cells. Consequently, AAIBs with this electrolyte exhibit improved cycling stability within the temperature range of -10-50 °C. This present study introduces a promising methodology for designing electrolytes suitable for low-cost, safe, and stable AAIBs over a wide temperature range.
RESUMEN
Aqueous sodium-ion batteries are practically promising for large-scale energy storage, however energy density and lifespan are limited by water decomposition. Current methods to boost water stability include, expensive fluorine-containing salts to create a solid electrolyte interface and addition of potentially-flammable co-solvents to the electrolyte to reduce water activity. However, these methods significantly increase costs and safety risks. Shifting electrolytes from near neutrality to alkalinity can suppress hydrogen evolution while also initiating oxygen evolution and cathode dissolution. Here, we present an alkaline-type aqueous sodium-ion batteries with Mn-based Prussian blue analogue cathode that exhibits a lifespan of 13,000 cycles at 10 C and high energy density of 88.9 Wh kg-1 at 0.5 C. This is achieved by building a nickel/carbon layer to induce a H3O+-rich local environment near the cathode surface, thereby suppressing oxygen evolution. Concurrently Ni atoms are in-situ embedded into the cathode to boost the durability of batteries.
RESUMEN
Aqueous Zn-ion batteries hold practical promise for large-scale energy storage because of the safety and affordability of aqueous-based electrolytes; in addition, the manufacturing process is significantly simplified by direct employment of Zn metal as an anode. However, hydrogen evolution due to near-surface water dissociation has hindered large-scale applications of them. Here, we report the suppression of the hydrogen evolution reaction via a CuN3-coordinated graphitic carbonitride (CuN3-C3N4) anticatalytic interface to achieve highly efficient aqueous Zn-ion batteries. Based on in situ gas chromatography and in situ synchrotron-based X-ray diffraction spectroscopy, we demonstrated that the hydrogen evolution reaction triggers the Zn4SO4(OH)6·xH2O formation. A combination of in situ infrared spectroscopy and density functional theory simulations has proved to stabilize near-surface H3O+ species and regulate adsorption of H* intermediates by an anticatalytic interface for hydrogen evolution reaction suppression. Consequently, the anticatalytic interface greatly improves the Coulombic efficiency of Zn plating/stripping to â¼99.7% for 5500 cycles and the cycling reversibility to over 1300 h at 1 mA cm-2 and 1 mAh cm-2. With an anticatalytic interface, the full cell shows an excellent Coulombic efficiency of 98.3% over 400 cycles at 1C. These findings provide strategic insight for targeted designing of highly efficient aqueous Zn-ion batteries.
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Progress towards the integration of technology into living organisms requires power devices that are biocompatible and mechanically flexible. Aqueous zinc ion batteries that use hydrogel biomaterials as electrolytes have emerged as a potential solution that operates within biological constraints; however, most of these batteries feature inferior electrochemical properties. Here, we propose a biocompatible hydrogel electrolyte by utilising hyaluronic acid, which contains ample hydrophilic functional groups. The gel-based electrolyte offers excellent anti-corrosion ability for zinc anodes and regulates zinc nucleation/growth. Also, the gel electrolyte provides high battery performance, including a 99.71% Coulombic efficiency, over 5500 hours of long-term stability, improved cycle life of 250 hours under a high zinc utilization rate of 80%, and high biocompatibility. Importantly, the Zn//LiMn2O4 pouch cell exhibits 82% capacity retention after 1000 cycles at 3 C. This work presents a promising gel chemistry that controls zinc behaviour, offering great potential in biocompatible energy-related applications and beyond.
RESUMEN
The poor Zn reversibility has been criticized for limiting applications of aqueous Zn-ion batteries (ZIBs); however, its behavior in aqueous media is not fully uncovered yet. Here, this knowledge gap is addressed, indicating that Zn electrodes face a O2 -involving corrosion, besides H2 evolution and dendrite growth. Differing from aqueous Li/Na batteries, removing O2 cannot enhance ZIB performance because of the aggravated competing H2 evolution. To address Zn issues, a one-off electrolyte strategy is reported by introducing the triple-function C3 H7 Na2 O6 P, which can take effects during the shelf time of battery. It regulates H+ concentration and reduces free-water activity, inhibiting H2 evolution. A self-healing solid/electrolyte interphase (SEI) can be triggered before battery operation, which suppresses O2 adsorption corrosion and dendritic deposition. Consequently, a high Zn reversibility of 99.6% is achieved under a high discharge depth of 85%. The pouch full-cell with a lean electrolyte displays a record lifespan with capacity retention of 95.5% after 500 cycles. This study not only looks deeply into Zn behavior in aqueous media but also underscores rules for the design of active metal anodes, including Zn and Li metals, during shelf time toward real applications.