Revealing the missing puzzle piece of concentration in regulating Zn electrodeposition.

Despite achievements in suppressing dendrites and regulating Zn crystal growth, secondary aqueous Zn batteries are still rare in the market. Existing strategies mainly focus on electrode modification and electrolyte optimization, while the essential role of ion concentration in liquid-to-solid electrodeposition is neglected for a long time. Herein, the mechanism of concentration regulation in Zn electrodeposition is investigated in depth by combining electrochemical tests, post hoc characterization, and multiscale simulations. First, initial Zn electrodeposition is thermodynamically controlled epitaxial growth, whereas with the rapid depletion of ions, the concentration overpotential transcends the thermodynamic influence to kinetic control. Then, the evolution of the morphology from 2D sheets to 1D whiskers due to the concentration change is insightfully revealed by the morphological characterization and phase-field modeling. Furthermore, the depth of discharge (DOD) results in large concentration differences at the electrode-electrolyte interface, with a mild concentration distribution at lower DOD generating (002) crystal plane 2D sheets and a heavily varied concentration distribution at higher DOD yielding arbitrarily oriented 3D blocks. As a proof of concept, relaxation is introduced into two systems to homogenize the concentration distribution, revalidating the essential role of concentration in regulating electrodeposition, and two vital factors affecting the relaxation time, i.e., current density and electrode distance, are deeply investigated, demonstrating that the relaxation time is positively related to both and is more sensitive to the electrode distance. This work contributes to reacquainting aqueous batteries undergoing phase transitions and reveals a missing piece of the puzzle in regulating Zn electrodeposition.

Transforming the Electrochemical Behaviors of Cobalt Oxide from "Supercapacitator" to "Battery" by Atomic-Level Structure Engineering for Inspiring the Advance of Co-Based Batteries.

Cobalt-based electrodes receive emerging attention for their high theoretical capacity and rich valence variation ability, but state-of-the-art cobalt-based electrodes present performance far below the theoretical value. Herein, the in-depth reaction mechanisms in the alkaline electrolyte are challenged and proven to be prone to the surface-redox pseudocapacitor behavior due to the low adsorption energy to OH. Using the atomic-level structure engineering strategy after substitution metal searching, the adsorption energy is effectively enhanced, and the peak of CoOOH can be observed from in situ characterization for the first time, leading to the successful transition of charge storage behavior from "supercapacitor" to "battery". When used in a Zn-Co battery as a proof of concept, it shows comprehensive electrochemical performance with a flat discharge voltage plateau of ≈1.7 V, an optimal energy density of 506 Wh kg-1 , and a capacity retention ratio of 85.1% after 2000 cycles, shining among the reported batteries. As a practical demonstration, this battery also shows excellent self-discharge performance with the capacity retention of 90% after a 10 h delay. This work subtly tunes the intrinsic electrochemical properties of the cobalt-based material through atomic-level structure engineering, opening a new opportunity for the advance of energy storage systems.

Self-Activated Formation of Hierarchical Co3 O4 Nanoflakes with High Valence-State Conversion Capability for Ultrahigh-Capacity Zn-Co Batteries.

Cobalt-based materials are attracting increasing interest in alkaline Zn batteries due to the high theoretical capacity. However, the practical utilization is restricted by the poor microstructure and insufficient valence-state conversion. Herein, a self-activated formation of hierarchical Co3 O4 nanoflakes with high valence-state conversion capability is designed. This electrode not only exhibits the optimized microstructure with large reaction surfaces, but also shows excellent valence-state conversion capability. Consequently, this battery delivers an ultrahigh capacity of 481.4 mAh g-1 and an energy density of 818.3 Wh kg-1 based on the active material, which shines among reported Co-based materials. Besides, the capacity can retain 41.9% with even 20× current density increases, and it can operate with a capacity decay of 20% after the 1000th cycle. This strategy greatly enhances the performance and durability of integrated air electrodes, raising the attention of boundary design for other electrochemical energy conversion and storage devices.

Design of Thick Electrodes with Vertical Channels for Aqueous Batteries: Experimental and Numerical Analysis.

Developing thick electrodes with high-area loadings is a direct method for boosting the energy density. However, this approach also leads to a proportional increase in the resistance to charge transport. Optimizing the microstructure of the electrode can effectively enhance the charge transport kinetics in thick electrodes. Herein, a low-tortuosity nickel electrode with vertical channels (VC-Ni) is fabricated using a phase inversion method. A high-loading VC-Ni electrode (26.7 mg cm-2) delivers a superior specific capacity of 134.0 mAh g-1 at a 5 C rate, significantly outperforming the conventional nickel electrode (Con-Ni). Numerical simulations reveal the fast transport kinetics within the vertical channel electrodes. For the thick electrode, the VC-Ni electrode shows a substantially lower concentration gradient of OH- and H+ compared to the Con-Ni electrode. Notably, beyond a critical loading of 26.5 mg cm-2, the specific capacity initially increases with volume fraction, peaking at 50%, and then diminishes. The specific capacity increases as the channel size decreases, but the tendency to increase gradually decreases. The highest specific capacity is achieved with an inverted trapezoidal channel shape, characterized by larger pores near the separator and smaller pores near the current collector. This work is of guidance for the design of thick electrodes for high-performance aqueous batteries.

Tailoring the Electrochemical Deposition of Zn by Tuning the Viscosity of the Liquid Electrolyte.

The issues during Zn deposition in rechargeable Zn-based batteries greatly hinder cycling stability. In this work, a simple and inexpensive approach to tailor the Zn electrodeposition is proposed by tuning the viscosity of the liquid electrolyte (LE). First, the growth mechanisms of Zn deposition under different electrolyte properties are investigated by numerical simulation, from which the bottom deposition tends to fuse with each other when there are more deposition sites, and the mass-transfer coefficient is lower, thus achieving uniform deposition. Besides, the whole process of Zn deposition in charging-discharging cycling is in situ observed by an optical microscope. It is found that the cause of the poor stability in the LE is due to the uneven Zn deposition, resulting in weak bonding between the deposition and the electrode surface, which is also the reason for the formation of dead Zn. In contrast, when an appropriate amount of the polymer is added to the LE to increase the viscosity, an appropriate overpotential can be created, generating more deposition sites. In addition, the viscosity reduces the mass-transfer coefficient, making the distance from the ion to the deposition sites the main controlling factor. The Zn ions are more inclined to move in the direction of electric field lines, which results in a uniform and dense deposition layer. Furthermore, the effectiveness of this method is demonstrated in a Zn-LiFePO4 battery, from which the battery with the modified electrolyte condition still works properly even in the Zn utilization of 100% and shows a capacity retention rate (35%) of nearly twice that in the original LE condition (18%) after 10 cycles. This work provides a theoretical basis for Zn deposition and provides ideas for the future development of high-performance Zn-based batteries.