Electron-Donating Conjugation Effect Modulated Zn2+ Reduction Reaction for Separator-Free Aqueous Zinc Batteries.

Zinc-based aqueous batteries (ZABs) are attracting extensive attention due to the low cost, high capacity, and environmental benignity of the zinc anode. However, their application is still hindered by the undesired zinc dendrites. Despite Zn-surface modification being promising in relieving dendrites, a thick separator (i.e. glass fiber, 250-700 µm) is still required to resist the dendrite puncture, which limits volumetric energy density of battery. Here, we pivot from the traditional interphase plus extra separator categories, proposing an all-in-one ligand buffer layer (ca. 20 µm) to effectively modulate the Zn2+ transfer and deposition behaviors proved by in situ electrochemical digital holography. Experimental characterizations and density functional theory simulations further reveal that the catechol groups in the buffer layer can accelerate the Zn2+ reduction reaction (ZRR) through the electron-donating p-π conjugation effect, decreasing the negative charge in the coordination environment. Without extra separators, the elaborated system endows low polarization below 28.2 mV, long lifespan of 4950 h at 5 mA cm-2 in symmetric batteries, and an unprecedented volumetric energy density of 99.2 Wh L-1 based on the whole pouch cells. The concomitantly "separator-free" and "dendrite-free" conjugation effect with an accelerated ZRR process could foster the progression of metallic anodes and benefit energetic aqueous batteries.

Tandem Chemistry with Janus Mesopores Accelerator for Efficient Aqueous Batteries.

A reliable solid electrolyte interphase (SEI) on the metallic Zn anode is imperative for stable Zn-based aqueous batteries. However, the incompatible Zn-ion reduction processes, scilicet simultaneous adsorption (capture) and desolvation (repulsion) of Zn2+(H2O)6, raise kinetics and stability challenges for the design of SEI. Here, we demonstrate a tandem chemistry strategy to decouple and accelerate the concurrent adsorption and desolvation processes of the Zn2+ cluster at the inner Helmholtz layer. An electrochemically assembled perforative mesopore SiO2 interphase with tandem hydrophilic -OH and hydrophobic -F groups serves as a Janus mesopores accelerator to boost a fast and stable Zn2+ reduction reaction. Combining in situ electrochemical digital holography, molecular dynamics simulations, and spectroscopic characterizations reveals that -OH groups capture Zn2+ clusters from the bulk electrolyte and then -F groups repulse coordinated H2O molecules in the solvation shell to achieve the tandem ion reduction process. The resultant symmetric batteries exhibit reversible cycles over 8000 and 2000 h under high current densities of 4 and 10 mA cm-2, respectively. The feasibility of the tandem chemistry is further evidenced in both Zn//VO2 and Zn//I2 batteries, and it might be universal to other aqueous metal-ion batteries.

Reviving Zn0 Dendrites to Electroactive Zn2+ by Mesoporous MXene with Active Edge Sites.

Zinc metal-based aqueous batteries (ZABs) offer a sustainable, affordable, and safe energy storage alternative to lithium, yet inevitable dendrite formation impedes their wide use, especially under long-term and high-rate cycles. How the battery can survive after dendrite formation remains an open question. Here, we pivot from conventional Zn dendrite growth suppression strategies, introducing proactive dendrite-digesting chemistry via a mesoporous Ti3C2 MXene (MesoTi3C2)-wrapped polypropylene separator. Spectroscopic characterizations and electrochemical evaluation demonstrate that MesoTi3C2, acting as an oxidant, can revive the formed dead Zn0 dendrites into electroactive Zn2+ ions through a spontaneous redox process. Density functional theory reveals that the abundant edge-Ti-O sites in our MesoTi3C2 facilitate high oxidizability and electron transfer from Zn0 dendrites compared to their in-plane counterparts. The resultant asymmetrical cell demonstrates remarkable ultralong cycle life of 2200 h at a practical current of 5 mA cm-2 with a low overpotential (<50 mV). The study reveals the unexpected edge effect of mesoporous MXenes and uncovers a new proactive dendrite-digesting chemistry to survive ZABs, albeit with inevitable dendrite formation.

Shaping characteristics of excavation contours in sequential controlled fracture blasting of rock-anchored beams in Shuangjiangkou underground powerhouse.

Influences of high in-situ stress generally need to be considered when excavating deep underground caverns. The dynamic fracture behaviors of rocks under blast loads were investigated by using the rock-anchored beam excavation in underground powerhouses of Shuangjiangkou Hydropower Station in Sichuan Province, China as the engineering background. To solve the problems of the poor blasting breakage effect of rocks and the difficulty in protecting surrounding rocks during excavation, mechanical properties of granite under static and dynamic loads were investigated and the sequential controlled fracture blasting (SCFB) method was adopted during in-situ tests. Based on the Riedel-Hiermaier-Thoma constitutive model and the strength criterion, software LS-DYNA was employed to simulate the dynamic propagation of blasting-induced cracks. The contour shaping effect obtained via numerical simulation is generally consistent with the test results. The results show that SCFB can to some extent control the direction of crack initiation and rock fracture behavior of the blasthole wall cracks and the spacing of successive bursting holes is about 10 times the diameter of the blastholes when the cracks between the blastholes are shaped the best effect. Moreover, the magnitude and direction of principal in-situ stress can both affect the propagation path and length of blasting-induced cracks. The results of the research on the excavation and construction of deeply buried underground caverns have a certain reference value.

Constructing Ionic Self-Concentrated Electrolyte via Introducing Montmorillonite Toward High-Performance Aqueous Zn-MnO2 Batteries.

Aqueous zinc metal batteries are regarded as one of the most promising alternatives to lithium-ion batteries for large-scale energy storage due to the abundant zinc resources, high safety, and low cost. Herein, an ionic self-concentrated electrolyte (ISCE) is proposed to enable uniform Zn deposition and reversible reaction of MnO2 cathode. Benefitting from the compatibility of ISCE with electrodes and its adsorption on the electrode surface for guidance, the Zn/Zn symmetrical batteries exhibit the long-life cycle stability with more than 5000 and 1500 h at 0.2 and 5 mA cm-2 , respectively. The Zn/MnO2 battery also exhibits a high capacity of 351 mA h g-1 at 0.1 A g-1 and can enable a stability over 2000 cycles at 1 A g-1 . This work provides a new insight into electrolyte design for stable aqueous Zn-MnO2 battery.

High-Energy Sn-Ni and Sn-Air Aqueous Batteries via Stannite-Ion Electrochemistry.

Tin is promising for aqueous batteries (ABs) due to its multiple electrons' reactions, high corrosion resistance, large hydrogen overpotential, and excellent environmental compatibility. However, restricted to the high thermodynamic barrier and the poor electrochemical kinetics, efficient alkaline Sn plating/stripping at facile conditions has not yet been realized. Here, for the first time, we demonstrate a highly reversible stannite-ion electrochemistry and construct a novel paradigm of high-energy Sn-based ABs. Combined spectroscopic characterization, electrochemical evaluation, and theoretical computation reveal the thermodynamic merits with a low reaction energy barrier and feasible H2O participation in Sn-ion reduction as well as the kinetic merits with fastened surface charge transfer and SnO22- diffusion. The resultant alkaline Sn anode delivers a low potential of -1.07 V vs Hg/HgO, a specific capacity of 450 mA h g-1, a Coulombic efficiency of near 100%, superb rate capability at 45.5 A g-1, and excellent cycling durability without dendrite and dead Sn. As a proof of concept, we developed new high-energy Sn-based ABs, including 1.45 V Sn-Ni with 314 W h kg-1 (58 kW kg-1 and over 15,000 cycles) and 1.0 V Sn-air with 420 W h kg-1 (lifespan over 1900 h), on the basis of masses from cathode and anode active materials. The findings prove the feasibility of the alkaline Sn metal anode, and the new suite of high-energy Sn-based ABs may be of immediate benefit toward safe, reliable, and affordable energy storage.

Activating sulfur oxidation reaction via six-electron redox mesocrystal NiS2 for sulfur-based aqueous batteries.

Sulfur-based aqueous batteries (SABs) are deemed promising candidates for safe, low-cost, and high-capacity energy storage. However, despite their high theoretical capacity, achieving high reversible value remains a great challenge due to the thermodynamic and kinetics problems of elemental sulfur. Here, the reversible six-electron redox electrochemistry is constructed by activating the sulfur oxidation reaction (SOR) process of the elaborate mesocrystal NiS2 (M-NiS2). Through the unique 6e- solid-to-solid conversion mechanism, SOR efficiency can reach an unprecedented degree of ca. 96.0%. The SOR efficiency is further revealed to be closely associated with the kinetics feasibility and thermodynamic stability of the M-NiS2 intermedium in the formation of elemental sulfur. Benefiting from the boosted SOR, compared with the bulk electrode, the M-NiS2 electrode exhibits a high reversible capacity (1258 mAh g-1), ultrafast reaction kinetics (932 mAh g-1 at 12 A g-1), and long-term cyclability (2000 cycles at 20 A g-1). As a proof of concept, a new M-NiS2‖Zn hybrid aqueous battery exhibits an output voltage of 1.60 V and an energy density of 722.4 Wh kgcath-1, which opens a new opportunity for the development of high-energy aqueous batteries.

Protocol in Evaluating Capacity of Zn-Mn Aqueous Batteries: A Clue of pH.

In the literature, Zn-Mn aqueous batteries (ZMABs) confront abnormal capacity behavior, such as capacity fluctuation and diverse "unprecedented performances." Because of the electrolyte additive-induced complexes, various charge/discharge behaviors associated with different mechanisms are being reported. However, the current performance assessment remains unregulated, and only the electrode or the electrolyte is considered. The lack of a comprehensive and impartial performance evaluation protocol for ZMABs hinders forward research and commercialization. Here, a pH clue (proton-coupled reaction) to understand different mechanisms is proposed and the capacity contribution is normalized. Then, a series of performance metrics, including rated capacity (Cr ) and electrolyte contribution ratio from Mn2+ (CfM), are systematically discussed based on diverse energy storage mechanisms. The relationship between Mn (II) ↔ Mn (III) ↔ Mn (IV) conversion chemistry and protons consumption/production is well-established. Finally, the concrete design concepts of a tunable H+ /Zn2+ /Mn2+ storage system for customized application scenarios, opening the door for the next-generation high-safety and reliable energy storage system, are proposed.

Prioritizing Hetero-Metallic Interfaces via Thermodynamics Inertia and Kinetics Zincophilia Metrics for Tough Zn-Based Aqueous Batteries.

Poor thermodynamic stability and sluggish electrochemical kinetics of metallic Zn anode in aqueous solution greatly hamper its practical application. To solve such problems, to date, various zincophilic surface modification strategies are developed, which can facilitate reversible Zn plating/stripping behavior. However, there is still a lack of systematic and fundamental understanding regarding the metrics of thermodynamics inertia and kinetics zincophilia in selecting zincophilic sites. Herein, hetero-metallic interfaces are prioritized for the first time via optimizing different hetero metals (Fe, Co, Ni, Sn, Bi, Cu, Zn, etc.) and synthetic solvents (ethanol, ethylene glycol, n-propanol, etc.). Specifically, both theoretical simulations and experimental results suggest that this Bi@Zn interface can exhibit high efficiency owing to the thermodynamics inertia and kinetics zincophilia. A best practice for prioritizing zincophilic sites in a more practical metric is also proposed. As a proof of concept, the Bi@Zn anode delivers ultralow overpotential of ≈55 mV at a high rate of 10 mA cm-2 and stable cycle life over 4700 cycles. The elaborated "thermodynamics inertia and kinetics metalphilia" metrics for hetero-metallic interfaces can benchmark the success of other metal-based batteries.

A solid-to-solid metallic conversion electrochemistry toward 91% zinc utilization for sustainable aqueous batteries.

The diffusion-limited aggregation (DLA) of metal ion (Mn+) during the repeated solid-to-liquid (StoL) plating and liquid-to-solid (LtoS) stripping processes intensifies fatal dendrite growth of the metallic anodes. Here, we report a new solid-to-solid (StoS) conversion electrochemistry to inhibit dendrites and improve the utilization ratio of metals. In this StoS strategy, reversible conversion reactions between sparingly soluble carbonates (Zn or Cu) and their corresponding metals have been identified at the electrode/electrolyte interface. Molecular dynamics simulations confirm the superiority of the StoS process with accelerated anion transport, which eliminates the DLA and dendrites in the conventional LtoS/StoL processes. As proof of concept, 2ZnCO3·3Zn(OH)2 exhibits a high zinc utilization of ca. 95.7% in the asymmetry cell and 91.3% in a 2ZnCO3·3Zn(OH)2 || Ni-based full cell with 80% capacity retention over 2000 cycles. Furthermore, the designed 1-Ah pouch cell device can operate stably with 500 cycles, delivering a satisfactory total energy density of 135 Wh kg-1.

Constructing Unique Mesoporous Carbon Superstructures via Monomicelle Interface Confined Assembly.

Constructing hierarchical three-dimensional (3D) mesostructures with unique pore structure, controllable morphology, highly accessible surface area, and appealing functionality remains a great challenge in materials science. Here, we report a monomicelle interface confined assembly approach to fabricate an unprecedented type of 3D mesoporous N-doped carbon superstructure for the first time. In this hierarchical structure, a large hollow locates in the center (∼300 nm in diameter), and an ultrathin monolayer of spherical mesopores (∼22 nm) uniformly distributes on the hollow shells. Meanwhile, a small hole (4.0-4.5 nm) is also created on the interior surface of each small spherical mesopore, enabling the superstructure to be totally interconnected. Vitally, such interconnected porous supraparticles exhibit ultrahigh accessible surface area (685 m2 g-1) and good underwater aerophilicity due to the abundant spherical mesopores. Additionally, the number (70-150) of spherical mesopores, particle size (22 and 42 nm), and shell thickness (4.0-26 nm) of the supraparticles can all be accurately manipulated. Besides this spherical morphology, other configurations involving 3D hollow nanovesicles and 2D nanosheets were also obtained. Finally, we manifest the mesoporous carbon superstructure as an advanced electrocatalytic material with a half-wave potential of 0.82 V (vs RHE), equivalent to the value of the commercial Pt/C electrode, and notable durability for oxygen reduction reaction (ORR).

Hierarchical Confinement Effect with Zincophilic and Spatial Traps Stabilized Zn-Based Aqueous Battery.

Zn-based aqueous batteries (ZABs) have been regarded as promising candidates for safe and large-scale energy storage in the "post-Li" era. However, kinetics and stability problems of Zn capture cannot be concomitantly regulated, especially at high rates and loadings. Herein, a hierarchical confinement strategy is proposed to design zincophilic and spatial traps through a host of porous Co-embedded carbon cages (denoted as CoCC). The zincophilic Co sites act as preferred nucleation sites with low nucleation barriers (within 0.5 mA h cm-2), and the carbon cage can further spatially confine Zn deposition (within 5.0 mA h cm-2). Theoretical simulations and in situ/ex situ structural observations reveal the hierarchical spatial confinement by the elaborated all-in-one network (within 12 mA h cm-2). Consequently, the elaborate strategy enables a dendrite-free behavior with excellent kinetics (low overpotential of ca. 65 mV at a high rate of 20 mA cm-2) and stable cycle life (over 800 cycles), pushing forward the next-generation high-performance ZABs.

Surface-Preferred Crystal Plane for a Stable and Reversible Zinc Anode.

Aqueous zinc-ion batteries are largely restricted by the unsatisfactory performance of zinc (Zn) anodes, including their poor stability and irreversibility. In particular, the mechanism behind the electrochemical contrast caused by the surface crystal plane, which is a decisive factor of the electrochemical characteristics of the hostless Zn anode, is still relatively indistinct. Hence, new insight into a novel anode with a surface-preferred (002) crystal plane is provided. The interfacial reaction and morphology evolution are revealed by theoretical analysis and post-mortem/operando experimental techniques, indicating that Zn anodes with more exposed (002) basal planes exhibit free dendrites, no by-products, and weak hydrogen evolution, in sharp contrast to the (100) plane. These features benefit the Zn (002) anode by enabling a long cyclic life of more than 500 h and a high average coulombic efficiency of 97.71% for symmetric batteries, along with delivering long cycling stability and reversibility with life spans of over 2000 cycles for full batteries. This work provides new insights into the design of high-performance Zn anodes for large-scale energy storage and can potentially be applied to other metal anodes suffering from instability and irreversibility.