Highly Reversible Positive-Valence Conversion of Sulfur Chemistry for High-Voltage Zinc-Sulfur Batteries.

Sulfur is a promising conversion-type cathode for zinc batteries (ZBs) due to its high discharge capacity and cost-effectiveness. However, the redox conversion of multivalent S in ZBs is still limited, only having achieved S0/S2- redox conversion with low discharge voltage and poor reversibility. This study presents significant progress by demonstrating, for the first time, the reversible S2-/S4+ redox behavior in ZBs with up to six-electron transfer (with an achieved discharge capacity of ∼1284 mAh g-1) using a highly concentrated ClO4 --containing electrolyte. The developed succinonitrile-Zn(ClO4)2 eutectic electrolyte stabilizes the positive-valence S compound and contributes to an ultra-low polarization voltage. Notably, the achieved flat discharge plateaus demonstrate the highest operation voltage (1.54 V) achieved to date in Zn‖S batteries. Furthermore, the high-voltage Zn‖S battery exhibits remarkable conversion dynamics, excellent cycling performance (85.7% capacity retention after 500 cycles), high efficiency (98.4%), and energy density (527 Wh KgS -1). This strategy of positive-valence conversion of sulfur represents a significant advancement in understanding sulfur chemistry in batteries and holds promise for future high-voltage sulfur-based batteries. This article is protected by copyright. All rights reserved.

Starch-mediated colloidal chemistry for highly reversible zinc-based polyiodide redox flow batteries.

Aqueous Zn-I flow batteries utilizing low-cost porous membranes are promising candidates for high-power-density large-scale energy storage. However, capacity loss and low Coulombic efficiency resulting from polyiodide cross-over hinder the grid-level battery performance. Here, we develop colloidal chemistry for iodine-starch catholytes, endowing enlarged-sized active materials by strong chemisorption-induced colloidal aggregation. The size-sieving effect effectively suppresses polyiodide cross-over, enabling the utilization of porous membranes with high ionic conductivity. The developed flow battery achieves a high-power density of 42 mW cm-2 at 37.5 mA cm-2 with a Coulombic efficiency of over 98% and prolonged cycling for 200 cycles at 32.4 Ah L-1posolyte (50% state of charge), even at 50 °C. Furthermore, the scaled-up flow battery module integrating with photovoltaic packs demonstrates practical renewable energy storage capabilities. Cost analysis reveals a 14.3 times reduction in the installed cost due to the applicability of cheap porous membranes, indicating its potential competitiveness for grid energy storage.

Inhibiting Residual Solvent Induced Side Reactions in Vinylidene Fluoride-Based Polymer Electrolytes Enables Ultra-Stable Solid-State Lithium Metal Batteries.

Residual solvents in vinylidene fluoride (VDF)-based solid polymer electrolytes (SPEs) have been recognized as responsible for their high ionic conductivity. However, side reactions by the residual solvents with the lithium (Li) metal induce poor stability, which has been long neglected. This study proposes a strategy to achieve a delicate equilibrium between ion conduction and electrode stability for VDF-based SPEs. Specifically, 2,2,2-trifluoro-N,N-dimethylacetamide (FDMA) is developed as the nonside reaction solvent for poly(vinylidene fluoride-co-hexafluoropropylene) (PVHF)-based SPEs, achieving both high ionic conductivity and significantly improved electrochemical stability. The developed FDMA solvent fosters the formation of a stable solid electrolyte interphase (SEI) through interface reactions with Li metal, effectively mitigating side reactions and dendrite growth on the Li metal electrode. Consequently, the Li||Li symmetric cells and Li||LiFePO4 cells demonstrate excellent cycling performance, even under limited Li (20 µm thick) supply and high-loading cathodes (>10 mg cm-2, capacity >1 mAh cm-2) conditions. The stable Li||LiCoO2 cells operation with a cutoff voltage of 4.48 V indicates the high-voltage stability of the developed SPE. This study offers valuable insights into the development of advanced VDF-based SPEs for enhanced lithium metal battery performance and longevity.

Polymer hetero-electrolyte enabled solid-state 2.4-V Zn/Li hybrid batteries.

The high redox potential of Zn0/2+ leads to low voltage of Zn batteries and therefore low energy density, plaguing deployment of Zn batteries in many energy-demanding applications. Though employing high-voltage cathode like spinel LiNi0.5Mn1.5O4 can increase the voltages of Zn batteries, Zn2+ ions will be immobilized in LiNi0.5Mn1.5O4 once intercalated, resulting in irreversibility. Here, we design a polymer hetero-electrolyte consisting of an anode layer with Zn2+ ions as charge carriers and a cathode layer that blocks the Zn2+ ion shuttle, which allows separated Zn and Li reversibility. As such, the Zn‖LNMO cell exhibits up to 2.4 V discharge voltage and 450 stable cycles with high reversible capacity, which are also attained in a scale-up pouch cell. The pouch cell shows a low self-discharge after resting for 28 days. The designed electrolyte paves the way to develop high-voltage Zn batteries based on reversible lithiated cathodes.

Steering sp-Carbon Content in Graphdiynes for Enhanced Two-Electron Oxygen Reduction to Hydrogen Peroxide.

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 50 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 83.3 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.

Three-dimensional simulation of the influence of different flotation media in the dissolved air flotation tank through the population balance model.

Gas-liquid flow in the dissolved air flotation (DAF) tank was studied through computational fluid dynamics through the realizable k-ε model and the population balance model (PBM) to predict the gas content of different flotation mediums (air, carbon dioxide, and chlorine) at different heights of the separation zone in the DAF tank. Simultaneously, a particular focus was placed on studying the effects of bubble aggregation and breakage on gas content. The results indicated that there were virtually no bubbles present in the region below 0.1 m of the separation zone. The gas content in the separation zone could meet the needs for gas content in the DAF tank when all these three gases were adopted as flotation medium. The introduction of models for bubble aggregation and breakage resulted in lower gas content at the bottom of the separation zone and higher gas content at the top, aligning more closely with experimental data. Due to the structural similarity and similar physicochemical characteristics of carbon dioxide and water molecules, the impact of bubble aggregation and breakage on the gas content is minimal.

Concurrent Mechanisms of Hot Electrons and Interfacial Water Molecule Ordering in Plasmon-Enhanced Nitrogen Fixation.

The participation of high-energy hot electrons generated from the non-radiative decay of localized surface plasmons is an important mechanism for promoting catalytic processes. Herein, another vital mechanism associated with the localized surface plasmon resonance (LSPR) effect, significantly contributing to the nitrogen reduction reaction (NRR), is found. That is to say, the LSPR-induced strong localized electric fields can weaken the intermolecular hydrogen bonds and regulate the arrangement of water molecules at the solid-liquid interface. The AuCu pentacle nanoparticles with excellent light absorption ability and the capability to generate strong localized electric fields are chosen to demonstrate this effect. The in situ Raman spectra and theoretical calculations are employed to verify the mechanism at the molecular scale in a nitrogen fixation process. Meanwhile, due to the promoted electron transfer at the interface by the well-ordered interfacial water, as well as the participation of high-energy hot electrons, the optimal catalyst exhibits excellent performance with an NH3 yield of 52.09 µg h-1 cm-2 and Faradaic efficiency (FE) of 45.82% at ─0.20 V versus RHE. The results are significant for understanding the LSPR effect in catalysis and provide a new approach for regulating the reaction process.

Perovskite Cathodes for Aqueous and Organic Iodine Batteries Operating Under One and Two Electrons Redox Modes.

Although conversion-type iodine-based batteries are considered promising for energy storage systems, stable electrode materials are scarce, especially for high-performance multi-electron reactions. The use of tin-based iodine-rich 2D Dion-Jacobson (DJ) ODASnI4 (ODA: 1,8-octanediamine) perovskite materials as cathode materials for iodine-based batteries is suggested. As a proof of concept, organic lithium-perovskite and aqueous zinc-perovskite batteries are fabricated and they can be operated based on the conventional one-electron and advanced two-electron transfer modes. The active elemental iodine in the perovskite cathode provides capacity through a reversible I- /I+ redox pair conversion at full depth, and the rapid electron injection/extraction leads to excellent reaction kinetics. Consequently, high discharge plateaus (1.71 V vs Zn2+ /Zn; 3.41 V vs Li+ /Li), large capacity (421 mAh g-1 I ), and a low decay rate (1.74 mV mAh-1 g-1 I ) are achieved for lithium and zinc ion batteries, respectively. This study demonstrates the promising potential of perovskite materials for high-performance metal-iodine batteries. Their reactions based on the two-electron transfer mechanism shed light on similar battery systems aiming for decent operational stability and high energy density.

Selenium-Anchored Chlorine Redox Chemistry in Aqueous Zinc Dual-Ion Batteries.

Chlorine-based batteries with Cl0 to Cl- redox reaction (ClRR) are promising for high-performance energystorage due to their high redox potential and large theoretical capacity. However, the inherent gas-liquid conversion feature of ClRR together with poor Cl fixation can cause Cl2 leakage, reducing battery reversibility. Herein, we utilize a Se-based organic molecule, diphenyl diselenide (di-Ph-Se), as the Cl anchoring agent and realize an atomic level-Cl fixation through chalcogen-halogencoordinating chemistry. The promoted Cl fixation, with two oxidized Cl0 anchoring on a single Ph-Se, and the multivalence conversion of Se contributeto a six-electron conversion process with up to 507 mAh g-1 and an average voltage of 1.51 V, as well as a high energy density of 665 Wh Kg-1 . Based on the superior reversibility of thedeveloped di-Ph-Se electrode with ClRR, a remarkable rate performance (205 mAh g-1 at 5 A g-1 ) and cycling performance (capacity retention of 77.3 % after 500cycles) are achieved. Significantly, the pouch cell delivers a record arealcapacity of up to 6.87 mAh cm-2 and extraordinary self-discharge performance. This chalcogen-halogen coordination chemistry between the Se electrode and Cl provides a new insight for developing reversible and efficientbatteries with halogen redox reactions.

Electrolyte Additives for Stable Zn Anodes.

Zn-ion batteries are regarded as the most promising batteries for next-generation, large-scale energy storage because of their low cost, high safety, and eco-friendly nature. The use of aqueous electrolytes results in poor reversibility and leads to many challenges related to the Zn anode. Electrolyte additives can effectively address many such challenges, including dendrite growth and corrosion. This review provides a comprehensive introduction to the major challenges in and current strategies used for Zn anode protection. In particular, an in-depth and fundamental understanding is provided of the various functions of electrolyte additives, including electrostatic shielding, adsorption, in situ solid electrolyte interphase formation, enhancing water stability, and surface texture regulation. Potential future research directions for electrolyte additives used in aqueous Zn-ion batteries are also discussed.

Electrochemical nitrate reduction in acid enables high-efficiency ammonia synthesis and high-voltage pollutes-based fuel cells.

Most current research is devoted to electrochemical nitrate reduction reaction for ammonia synthesis under alkaline/neutral media while the investigation of nitrate reduction under acidic conditions is rarely reported. In this work, we demonstrate the potential of TiO2 nanosheet with intrinsically poor hydrogen-evolution activity for selective and rapid nitrate reduction to ammonia under acidic conditions. Hybridized with iron phthalocyanine, the resulting catalyst displays remarkably improved efficiency toward ammonia formation owing to the enhanced nitrate adsorption, suppressed hydrogen evolution and lowered energy barrier for the rate-determining step. Then, an alkaline-acid hybrid Zn-nitrate battery was developed with high open-circuit voltage of 1.99 V and power density of 91.4 mW cm-2. Further, the environmental sulfur recovery can be powered by above hybrid battery and the hydrazine-nitrate fuel cell can be developed for simultaneously hydrazine/nitrate conversion and electricity generation. This work demonstrates the attractive potential of acidic nitrate reduction for ammonia electrosynthesis and broadens the field of energy conversion.

Molecular Engineering of a Metal-Organic Polymer for Enhanced Electrochemical Nitrate-to-Ammonia Conversion and Zinc Nitrate Batteries.

Metal-organic framework-based materials are promising single-site catalysts for electrocatalytic nitrate (NO3 - ) reduction to value-added ammonia (NH3 ) on account of well-defined structures and functional tunability but still lack a molecular-level understanding for designing the high-efficient catalysts. Here, we proposed a molecular engineering strategy to enhance electrochemical NO3 - -to-NH3 conversion by introducing the carbonyl groups into 1,2,4,5-tetraaminobenzene (BTA) based metal-organic polymer to precisely modulate the electronic state of metal centers. Due to the electron-withdrawing properties of the carbonyl group, metal centers can be converted to an electron-deficient state, fascinating the NO3 - adsorption and promoting continuous hydrogenation reactions to produce NH3 . Compared to CuBTA with a low NO3 - -to-NH3 conversion efficiency of 85.1 %, quinone group functionalization endows the resulting copper tetraminobenzoquinone (CuTABQ) distinguished performance with a much higher NH3 FE of 97.7 %. This molecular engineering strategy is also universal, as verified by the improved NO3 - -to-NH3 conversion performance on different metal centers, including Co and Ni. Furthermore, the assembled rechargeable Zn-NO3 - battery based on CuTABQ cathode can deliver a high power density of 12.3 mW cm-2 . This work provides advanced insights into the rational design of metal complex catalysts through the molecular-level regulation for NO3 - electroreduction to value-added NH3 .

Tellurium with Reversible Six-Electron Transfer Chemistry for High-Performance Zinc Batteries.

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 ∼0.59 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 Zn∥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.

Three-Electron Transfer-Based High-Capacity Organic Lithium-Iodine (Chlorine) Batteries.

Conversion-type batteries apply the principle that more charge transfer is preferable. The underutilized electron transfer mode within two undermines the electrochemical performance of halogen batteries. Here, we realised a three-electron transfer lithium-halogen battery based on I- /I+ and Cl- /Cl0 couples by using a common commercial electrolyte saturated with Cl- anions. The resulting Li||tetrabutylammonium triiodide (TBAI3 ) cell exhibits three distinct discharging plateaus at 2.97, 3.40, and 3.85 V. Moreover, it has a high capacity of 631 mAh g-1 I (265 mAh g-1 electrode , based on entire mass loading) and record-high energy density of up to 2013 Wh kg-1 I (845 Wh kg-1 electrode ). To support these findings, experimental characterisations and density functional theory calculations were conducted to elucidate the redox chemistry involved in this novel interhalogen strategy. We believe our paradigm presented here has a foreseeable inspiring effect on other halogen batteries for high-energy-density pursuit.

Reconstructing Hydrogen Bond Network Enables High Voltage Aqueous Zinc-Ion Supercapacitors.

High-voltage aqueous rechargeable energy storage devices with safety and high specific energy are hopeful candidates for the future energy storage system. However, the electrochemical stability window of aqueous electrolytes is a great challenge. Herein, inspired by density functional theory (DFT), polyethylene glycol (PEG) can interact strongly with water molecules, effectively reconstructing the hydrogen bond network. In addition, N, N-dimethylformamide (DMF) can coordinate with Zn2+ , assisting in the rapid desolvation of Zn2+ and stable plating/stripping process. Remarkably, by introducing PEG400 and DMF as co-solvents into the electrolyte, a wide electrochemical window of 4.27 V can be achieved. The shift in spectra indicate the transformation in the number and strength of hydrogen bonds, verifying the reconstruction of hydrogen bond network, which can largely inhibit the activity of water molecule, according well with the molecular dynamics simulations (MD) and online electrochemical mass spectroscopy (OEMS). Based on this electrolyte, symmetric Zn cells survived up to 5000 h at 1 mA cm-2 , and high voltage aqueous zinc ion supercapacitors assembled with Zn anode and activated carbon cathode achieved 800 cycles at 0.1 A g-1 . This work provides a feasible approach for constructing high-voltage alkali metal ion supercapacitors through reconstruction strategy of hydrogen bond network.

Spider Silk-Inspired Binder Design for Flexible Lithium-Ion Battery with High Durability.

The development of flexible lithium-ion batteries (LIBs) imposes demands on energy density and high mechanical durability simultaneously. Due to the limited deformability of electrodes, as well as the flat and smooth surface of the metal current collectors, stable/durable/reliable contact between electrode materials and the current collectors remains a challenge, in particular, for electrodes with high loading mass and heavily deformed batteries. Binders play an essential role in binding particles of electrode materials and adhering them to current collectors. Herein, inspired by spider silk, a binder for flexible LIBs is developed, which equips a cross-linked supramolecular poly(urethane-urea) to the polyacrylic acid. The binder imparts super high elastic restorability originating from the meticulously engineered hydrogen-bonding segments as well as extraordinary adhesion. The developed binder provides excellent flexibility and intact electrode morphologies without disintegration even when the electrode is largely deformed, enabling a stable cycling and voltage output even when the batteries are put under tough dynamic deformation tests. The flexible LIBs exhibit a high energy density of 420 Wh L-1 , which is remarkably higher than reported numbers. The unique binder design is greatly promising and offers a valuable material solution for LIBs with high-loading mass and flexible designs.

Completely Activated and Phase-Transformed KFeMnHCF for Zn/K Hybrid Batteries with 14 500 Cycles by an OH-Rich Hydrogel Electrolyte.

Metal hexacyanoferrates are recognized as superior cathode materials for zinc and zinc hybrid batteries, particularly the Prussian blue analog (PBA). However, PBA development is hindered by several limitations, including small capacities (<70 mAh g-1 ) and short lifespans (<1000 cycles). These limitations generally arise due to incomplete activation of redox sites and structure collapse during intercalation/deintercalation of metal ions in PBAs. According to this study, the adoption of a hydroxyl-rich (OH-rich) hydrogel electrolyte with extended electrochemical stability windows (ESWs) can effectively activate the redox site of low-spin Fe of the Kx Fey Mn1-y [Fe(CN)6 ]w ·zH2 O (KFeMnHCF) cathode while tuning its structure. Additionally, the strong adhesion of the hydrogel electrolyte inhibits KFeMnHCF particles from falling off the cathode and dissolving. The easy desolvation of metal ions in the developed OH-rich hydrogel electrolytes can lead to a fast and reversible intercalation/deintercalation of metal ions in the PBA cathode. As a result, the Zn||KFeMnHCF hybrid batteries achieve the unprecedented characteristics of 14 500 cycles, a 1.7 V discharge plateau, and a 100 mAh g-1 discharge capacity. The results of this study provide a new understanding of the development of zinc hybrid batteries with PBA cathode materials and present a promising new electrolyte material for this application.

Anion chemistry in energy storage devices.

Anions serve as an essential component of electrolytes, whose effects have long been ignored. However, since the 2010s, we have seen a considerable increase of anion chemistry research in a range of energy storage devices, and it is now understood that anions can be well tuned to effectively improve the electrochemical performance of such devices in many aspects. In this Review, we discuss the roles of anion chemistry across various energy storage devices and clarify the correlations between anion properties and their performance indexes. We highlight the effects of anions on surface and interface chemistry, mass transfer kinetics and solvation sheath structure. Finally, we conclude with a perspective on the challenges and opportunities of anion chemistry for enhancing specific capacity, output voltage, cycling stability and anti-self-discharge ability of energy storage devices.

Development of rechargeable high-energy hybrid zinc-iodine aqueous batteries exploiting reversible chlorine-based redox reaction.

The chlorine-based redox reaction (ClRR) could be exploited to produce secondary high-energy aqueous batteries. However, efficient and reversible ClRR is challenging, and it is affected by parasitic reactions such as Cl2 gas evolution and electrolyte decomposition. Here, to circumvent these issues, we use iodine as positive electrode active material in a battery system comprising a Zn metal negative electrode and a concentrated (e.g., 30 molal) ZnCl2 aqueous electrolyte solution. During cell discharge, the iodine at the positive electrode interacts with the chloride ions from the electrolyte to enable interhalogen coordinating chemistry and forming ICl3-. In this way, the redox-active halogen atoms allow a reversible three-electrons transfer reaction which, at the lab-scale cell level, translates into an initial specific discharge capacity of 612.5 mAh gI2-1 at 0.5 A gI2-1 and 25 °C (corresponding to a calculated specific energy of 905 Wh kgI2-1). We also report the assembly and testing of a Zn | |Cl-I pouch cell prototype demonstrating a discharge capacity retention of about 74% after 300 cycles at 200 mA and 25 °C (final discharge capacity of about 92 mAh).

Regulating Inorganic and Organic Components to Build Amorphous-ZnFx Enriched Solid-Electrolyte Interphase for Highly Reversible Zn Metal Chemistry.

The introduction of inorganic crystallites into a solid-electrolyte interphase (SEI) is an effective strategy for improving the reversibility of the Zn metal anode (ZMA). However, the structure-performance relationship of the SEI is not fully understood because the existing forms of its inorganic and organic components in their pristine states are not resolved. Here, a highly effective SEI is constructed for ZMA using a bisolvent electrolyte and resolved its composition/structure by cryogenic transmission electron microscopy. This highly fluorinated SEI with amorphous inorganic ZnFx uniformly distributed in the organic matrix is largely different from the common mosaic and multilayer SEIs with crystalline inorganics. It features improved structural integrity, mechanical toughness, and Zn2+ ion conductivity. Consequently, the ZMA exhibits excellent reversibility with an enhanced plating/stripping Coulombic efficiency of 99.8%. The ZMA-based full cell achieves a high Zn utilization ratio of 54% at a practical areal capacity of 3.2 mAh cm-2 and stable cycling over 1800 h during which the accumulated capacity reached 5600 mAh cm-2 . This research highlights the detailed structure and composition of amorphous SEIs for highly reversible metal anodes.