Regulating Protons to Tailor the Enol Conversion of Quinone for High-Performance Aqueous Zinc Batteries.

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.

MXene Supported Electrodeposition Engineering of Layer Double Hydroxide for Alkaline Zinc Batteries.

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.

Distinguish MnO2/Mn2+ Conversion/ Zn2+ Intercalation/ H+ Conversion Chemistries at Different Potentials in Aqueous Zn||MnO2 Batteries.

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 3.0 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 1.75 V. More interesting, the discharge plateaus of ~1.33 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 1.8 mAh cm-2 and high specific energy of 0.858 Wh cm-2, even at a low MnO2 loading mass of 0.5 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.

Halide Exchange in Perovskites Enables Bromine/Iodine Hybrid Cathodes for Highly Durable Zinc Ion Batteries.

With the increasing need for reliable storage systems, the conversion-type chemistry typified by bromine cathodes attracts considerable attention due to sizeable theoretical capacity, cost efficiency, and high redox potential. However, the severe loss of active species during operation remains a problem, leading researchers to resort to concentrated halide-containing electrolytes. Here, profiting from the intrinsic halide exchange in perovskite lattices, a novel low-dimensional halide hybrid perovskite cathode, TmdpPb2[IBr]6, which serves not only as a halogen reservoir for reversible three-electron conversions but also as an effective halogen absorbent by surface Pb dangling bonds, C─H…Br hydrogen bonds, and Pb─I…Br halogen bonds, is proposed. As such, the Zn||TmdpPb2[IBr]6 battery delivers three remarkable discharge voltage plateaus at 1.21 V (I0/I-), 1.47 V (I+/I0), and 1.74 V (Br0/Br-) in a typical halide-free electrolyte; meanwhile, realizing a high capacity of over 336 mAh g-1 at 0.4 A g-1 and high capacity retentions of 88% and 92% after 1000 cycles at 1.2 A g-1 and 4000 cycles at 3.2 A g-1, respectively, accompanied by a high coulombic efficiency of ≈99%. The work highlights the promising conversion-type cathodes based on metal-halide perovskite materials.

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.

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 kg S -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.

Quantifying Asymmetric Zinc Deposition: A Guide Factor for Designing Durable Zinc Anodes.

Zinc metal is recognized as the most promising anode for aqueous energy storage but suffers from severe dendrite growth and poor reversibility. However, the coulombic efficiency lacks specificity for zinc dendrite growth, particularly in Zn||Zn symmetric cells. Herein, a novel indicator (fD) based on the characteristic crystallization peaks is proposed to evaluate the growth and distribution of zinc dendrites. As a proof of concept, triethylenetetramine (TETA) is adopted as an electrolyte additive to manipulate the zinc flux for uniform deposition, with a corroborating low fD value. A highly durable zinc symmetric cell is achieved, lasting over 2500 h at 10 mA cm-2 and 400 h at a large discharge of depth (10 mA cm-2, 10 mAh cm-2). Supported by the low fD value, the Zn||TETA-ZnSO4||MnO2 batteries overcome the sudden short circuit and fast capacity fading. The study provides a feasible method to evaluate zinc dendrites and sheds light on the design of highly reversible zinc anodes.