Li, Na, K, Mg, Zn, Al, and Ca Anode Interface Chemistries Developed by Solid-State Electrolytes.

Solid-state batteries (SSBs) have received significant attention due to their high energy density, reversible cycle life, and safe operations relative to commercial Li-ion batteries using flammable liquid electrolytes. This review presents the fundamentals, structures, thermodynamics, chemistries, and electrochemical kinetics of desirable solid electrolyte interphase (SEI) required to meet the practical requirements of reversible anodes. Theoretical and experimental insights for metal nucleation, deposition, and stripping for the reversible cycling of metal anodes are provided. Ion transport mechanisms and state-of-the-art solid-state electrolytes (SEs) are discussed for realizing high-performance cells. The interface challenges and strategies are also concerned with the integration of SEs, anodes, and cathodes for large-scale SSBs in terms of physical/chemical contacts, space-charge layer, interdiffusion, lattice-mismatch, dendritic growth, chemical reactivity of SEI, current collectors, and thermal instability. The recent innovations for anode interface chemistries developed by SEs are highlighted with monovalent (lithium (Li+ ), sodium (Na+ ), potassium (K+ )) and multivalent (magnesium (Mg2+ ), zinc (Zn2+ ), aluminum (Al3+ ), calcium (Ca2+ )) cation carriers (i.e., lithium-metal, lithium-sulfur, sodium-metal, potassium-ion, magnesium-ion, zinc-metal, aluminum-ion, and calcium-ion batteries) compared to those of liquid counterparts.

Scaling-Up Insights for Zinc-Air Battery Technologies Realizing Reversible Zinc Anodes.

Zinc-air battery (ZAB) technology is considered one of the promising candidates to complement the existing lithium-ion batteries for future large-scale high-energy-storage demands. The scientific literature reveals many efforts for the ZAB chemistries, materials design, and limited accounts for cell design principles with apparently superior performances for liquid and solid-state electrolytes. However, along with the difficulty of forming robust solid-electrolyte interphases, the discrepancy in testing methods and assessment metrics severely challenges the realistic evaluation/comparison and commercialization of ZABs. Here, strategies to formulate reversible zinc anodes are proposed and specific cell-level energy metrics (100-500 Wh kg-1 ) and realistic long-cycling operations are realized. Stabilizing anode/electrolyte interfaces results in a cumulative capacity of 25 Ah cm-2 and Coulomb efficiency of >99.9% for 5000 plating/stripping cycles. Using 1-10 Ah scale (≈500 Wh kg-1 at cell level) solid-state zinc-air pouch cells, scale-up insights for Ah-level ZABs that can progress from lab-scale research to practical production are also offered.

Heterointerface promoted trifunctional electrocatalysts for all temperature high-performance rechargeable Zn-air batteries.

The rational design of wide-temperature operating Zn-air batteries is crucial for their practical applications. However, the fundamental challenges remain; the limitation of the sluggish oxygen redox kinetics, insufficient active sites, and poor efficiency/cycle lifespan. Here we present heterointerface-promoted sulfur-deficient cobalt-tin-sulfur (CoS1-δ/SnS2-δ) trifunctional electrocatalysts by a facile solvothermal solution-phase approach. The CoS1-δ/SnS2-δ displays superb trifunctional activities, precisely a record-level oxygen bifunctional activity of 0.57 V (E1/2 = 0.90 V and Ej=10 = 1.47 V) and a hydrogen evolution overpotential (41 mV), outperforming those of Pt/C and RuO2. Theoretical calculations reveal the modulation of the electronic structures and d-band centers that endorse fast electron/proton transport for the hetero-interface and avoid the strong adsorption of intermediate species. The alkaline Zn-air batteries with CoS1-δ/SnS2-δ manifest record-high power density of 249 mW cm-2 and long-cycle life for >1000 cycles under harsh operations of 20 mA cm-2, surpassing those of Pt/C + RuO2 and previous state-of-the-art catalysts. Furthermore, the solid-state flexible Zn-air battery also displays remarkable performance with an energy density of 1077 Wh kg-1, >690 cycles for 50 mA cm-2, and a wide operating temperature from +80 to -40 °C with 85% capacity retention, which provides insights for practical Zn-air batteries.

Supramolecular Polymer Intertwined Free-Standing Bifunctional Membrane Catalysts for All-Temperature Flexible Zn-Air Batteries.

Rational construction of flexible free-standing electrocatalysts featuring long-lasting durability, high efficiency, and wide temperature tolerance under harsh practical operations are fundamentally significant for commercial zinc-air batteries. Here, 3D flexible free-standing bifunctional membrane electrocatalysts composed of covalently cross-linked supramolecular polymer networks with nitrogen-deficient carbon nitride nanotubes are fabricated (referred to as PEMAC@NDCN) by a facile self-templated approach. PEMAC@NDCN demonstrates the lowest reversible oxygen bifunctional activity of 0.61 V with exceptional long-lasting durability, which outperforms those of commercial Pt/C and RuO2. Theoretical calculations and control experiments reveal the boosted electron transfer, electrolyte mass/ion transports, and abundant active surface site preferences. Moreover, the constructed alkaline Zn-air battery with PEMAC@NDCN air-cathode reveals superb power density, capacity, and discharge-charge cycling stability (over 2160 cycles) compared to the reference Pt/C + RuO2. Solid-state Zn-air batteries enable a high power density of 211 mW cm-2, energy density of 1056 Wh kg-1, stable charge-discharge cycling of 2580 cycles for 50 mA cm-2, and wide temperature tolerance from - 40 to 70 °C with retention of 86% capacity compared to room-temperature counterparts, illustrating prospects over harsh operations.

Heuristic Iron-Cobalt-Mediated Robust pH-Universal Oxygen Bifunctional Lusters for Reversible Aqueous and Flexible Solid-State Zn-Air Cells.

Rechargeable aqueous zinc-air cells (ZACs) promise an extremely safe and high energy technology. However, they are still significantly limited by sluggish electrochemical kinetics and irreversibility originating from the parasitic reactions of the bifunctional catalysts and electrolytes. Here, we report the preferential in situ building of interfacial structures featuring the edge sites constituted by FeCo single/dual atoms with the integration of Co sites in the nitrogenized graphitic carbon frameworks (FeCo SAs@Co/N-GC) by electronic structure modulation approach. Compared to commercial Pt/C and RuO2, FeCo SAs@Co/N-GC reveals exceptional electrochemical performance, reversible redox kinetics, and durability toward oxygen reduction and evolution reactions under universal pH environments, i.e., alkaline, neutral, and acidic, due to synergistic effect at interfaces and preferred charge/mass transfer. The aqueous (alkaline, nonalkaline, and acidic electrolytes) ZACs constructed with a FeCo SAs@Co/N-GC cathode tolerate stable operations, have significant reversibility, and have the highest energy densities, outperforming those of noble metal counterparts and state-of-the-art ZACs in the ambient atmosphere. Additionally, flexible solid-state ZACs demonstrate excellent mechanical and electrochemical performances with a highest power density of 186 mW cm-2, specific capacity of 817 mAh gZn-1, energy density of 1017 Wh kgZn-1, and cycle life >680 cycles with extremely harsh operating conditions, which illustrates the great potential of triphasic catalyst for green energy storage technologies.