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.

Bipolar Energetics and Bifunctional Catalytic Activity of a Nanocrystalline Ru Thin-Film Enable High-Performance Photoelectrochemical Water Reduction and Oxidation.

Photoelectrochemical (PEC) cells, which represent a promising technology for the production of hydrogen fuel through water splitting reactions, must meet two criteria to achieve high-performance operation: (i) a high thermodynamic open-circuit potential and (ii) a low kinetic overpotential. Herein, we achieved these criteria in both an oxygen-evolving n-Si photoanode and hydrogen-evolving p-Si photocathode by simple electrodeposition of a nanocrystalline thin film of Ru. The bifunctional electrocatalytic activity of the nanocrystalline Ru led to low overpotentials in both the acidic oxygen evolution reaction (0.27 V) and alkaline hydrogen evolution reaction (0.04 V). In addition, the nanocrystalline Ru/Si junctions influenced the interface energetics via the induction of an extrinsic electrochemical potential on the surface of the Ru nanocrystals through a redox reaction rather than the chemical potential of the electrons (work function) of bulk Ru. The nanocrystalline Ru film exhibited bipolar applicability, enabling both Ru/n-Si and Ru/p-Si junctions with high Voc values of 0.63 and 0.5 V, respectively. As a result, the n-Si photoanode in the acidic electrolyte and the p-Si photocathode in the alkaline electrolyte generated a photocurrent of 10 mA/cm2 at record values of 0.87 and 0.42 V versus the reversible hydrogen electrode, respectively. These results provide insight into the development of high-performance PEC cells based on a nanocrystalline electrocatalyst.

A semiconductor junction photoelectrochemical device without a depletion region.

Semiconductor junctions are believed to form a depletion region at the band edge of the semiconductor as the chemical potentials for electrons (work functions) are aligned to the same level. Here, we demonstrated that ultrathin Ni film (less than 4 nm thick)/Si junction-based photoelectrochemical (PEC) devices have no depletion region due to three distinct phenomena: (i) the electrostatic or electrochemical potential extrinsically charged to the electrolytic-capacitive Ni surface dominates rather than the chemical potential of electrons (work function) of the bulk Ni, (ii) the charged potential is dynamically variable depending on the reaction and is rapidly volatile so as not to be constant; therefore, (iii) the charged potential is misaligned with the chemical potential of Si under equivalent circuit conditions. Such junction PEC devices were shown to follow a novel operating principle in which the output voltage (open circuit potential) is generated by the electrochemical potential charged at the Ni surface, and not by the light-induced potential (photovoltage) in Si. In addition, due to the bipolar charging nature, the ultrathin Ni film was effective in achieving a high open circuit potential in both p-Si photocathodes (0.57 V) and n-Si photoanodes (0.45 V). These anomalous results were not explained by the classical Schottky diode model based on the equilibrium of diffusion-drift current but by establishing a new model based on the equilibrium of the diffusion-charging current without accounting for the depletion region. Our findings provide an explanation for the unexpected results of the nanostructured PEC devices and insight into a new design that can overcome conventional limitations.

Solid-State Rechargeable Zinc-Air Battery with Long Shelf Life Based on Nanoengineered Polymer Electrolyte.

Zinc-air batteries (ZABs) are vulnerable to the ambient environment (e.g., humidity and CO2 ), and have serious selfdischarge issues, resulting in a short shelf life. To overcome these challenges, a near-neutral quaternary ammonium (QA) functionalized polyvinyl alcohol electrolyte membrane (different from conventional alkali-type membranes) has been developed. QA functionalization leads to the formation of interconnected nanochannels by creating hydrophilic/-phobic separations at the nanoscale. These nanochannels selectively transport OH- ions with a reduced migration barrier, while inhibiting [Zn(NH3 )6 ]2+ crossover. Owing to the superior water retention ability and enhanced chemical stability of the membrane, the solid-state zinc-air battery (SZAB) displays outstanding flexibility, a promising cycle lifetime, and a large volumetric energy density. More importantly, the self-discharge rate of SZAB is depressed to less than 7 % per month, and the fully dehydrated SZAB could recover its rechargeability upon replenishment of the solution of NH4 Cl.

Hierarchically Designed 3D Holey C2N Aerogels as Bifunctional Oxygen Electrodes for Flexible and Rechargeable Zn-Air Batteries.

The future of electrochemical energy storage spotlights on the designed formation of highly efficient and robust bifunctional oxygen electrocatalysts that facilitate advanced rechargeable metal-air batteries. We introduce a scalable facile strategy for the construction of a hierarchical three-dimensional sulfur-modulated holey C2N aerogels (S-C2NA) as bifunctional catalysts for Zn-air and Li-O2 batteries. The S-C2NA exhibited ultrahigh surface area (∼1943 m2 g-1) and superb electrocatalytic activities with lowest reversible oxygen electrode index ∼0.65 V, outperforms the highly active bifunctional and commercial (Pt/C and RuO2) catalysts. Density functional theory and experimental results reveal that the favorable electronic structure and atomic coordination of holey C-N skeleton enable the reversible oxygen reactions. The resulting Zn-air batteries with liquid electrolytes and the solid-state batteries with S-C2NA air cathodes exhibit superb energy densities (958 and 862 Wh kg-1), low charge-discharge polarizations, excellent reversibility, and ultralong cycling lives (750 and 460 h) than the commercial Pt/C+RuO2 catalysts, respectively. Notably, Li-O2 batteries with S-C2NA demonstrated an outstanding specific capacity of ∼648.7 mA h g-1 and reversible charge-discharge potentials over 200 cycles, illustrating great potential for commercial next-generation rechargeable power sources of flexible electronics.

Planar n-Si/PEDOT:PSS hybrid heterojunction solar cells utilizing functionalized carbon nanoparticles synthesized via simple pyrolysis route.

Herein, we present a facile and simple strategy for in situ synthesis of functionalized carbon nanoparticles (CNPs) via direct pyrolysis of ethylenediaminetetraacetic acid (EDTA) on silicon surface. The CNPs were incorporated in hybrid planar n-Si and poly(3,4-etyhlenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) solar cells to improve device performance. We demonstrate that the CNPs-incorporated devices showed increased electrical conductivity (reduced series resistance) and minority carrier lifetime (better charge carrier collection) than those of the cells without CNPs due to the existence of electrically conductive sp 2-hybridized carbon at the heterojunction interfaces. With an optimal concentration of CNPs, the hybrid solar cells exhibited power conversion efficiency up to 11.95%, with an open-circuit voltage of 614 mV, short-circuit current density of 26.34 mA cm-2, and fill factor of 73.93%. These results indicate that our approach is promising for the development of highly efficient organic-inorganic hybrid solar cells.

Highly active and durable carbon nitride fibers as metal-free bifunctional oxygen electrodes for flexible Zn-air batteries.

The design of flexible, highly energetic, and durable bifunctional oxygen electrocatalysts is indispensable for rechargeable metal-air batteries. Herein we present a simple approach for the development of carbon nitride fibers co-doped with phosphorus and sulfur, grown in situ on carbon cloth (PS-CNFs) as a flexible electrode material, and demonstrate its outstanding bifunctional catalytic activities toward ORR and OER compared to those of precious metal-based Pt/C and IrO2 on account of the dual action of P and S, numerous active sites, high surface area, and enhanced charge transfer. Furthermore, we demonstrate the flexibility, suitability, and durability of PS-CNFs as air electrodes for primary and rechargeable Zn-air batteries. Primary Zn-air batteries using this electrode showed high peak power density (231 mW cm-2), specific capacity (698 mA h g-1; analogous energy density of 785 W h kg-1), open circuit potential (1.49 V), and outstanding durability of more than 240 h of operation followed by mechanical recharging. Significantly, three-electrode rechargeable Zn-air batteries revealed a superior charge-discharge voltage polarization of ∼0.82 V at 20 mA cm-2, exceptional reversibility, and continuous charge-discharge cycling stability during 600 cycles. This work provides a pioneering strategy for designing flexible and stretchable metal-free bifunctional catalysts as gas diffusion layers for future portable and wearable renewable energy conversion and storage devices.

Scalable 3-D Carbon Nitride Sponge as an Efficient Metal-Free Bifunctional Oxygen Electrocatalyst for Rechargeable Zn-Air Batteries.

Rational design of efficient and durable bifunctional oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) electrocatalysts is critical for rechargeable metal-air batteries. Here, we developed a facile strategy for fabricating three-dimensional phosphorus and sulfur codoped carbon nitride sponges sandwiched with carbon nanocrystals (P,S-CNS). These materials exhibited high surface area and superior ORR and OER bifunctional catalytic activities than those of Pt/C and RuO2, respectively, concerning its limiting current density and onset potential. Further, we tested the suitability and durability of P,S-CNS as the oxygen cathode for primary and rechargeable Zn-air batteries. The resulting primary Zn-air battery exhibited a high open-circuit voltage of 1.51 V, a high discharge peak power density of 198 mW cm-2, a specific capacity of 830 mA h g-1, and better durability for 210 h after mechanical recharging. An extraordinary small charge-discharge voltage polarization (∼0.80 V at 25 mA cm-2), superior reversibility, and stability exceeding prolonged charge-discharge cycles have been attained in rechargeable Zn-air batteries with a three-electrode system. The origin of the electrocatalytic activity of P,S-CNS was elucidated by density functional theory analysis for both oxygen reactions. This work stimulates an innovative prospect for the enrichment of rechargeable Zn-air battery viable for commercial applications such as armamentaria, smart electronics, and electric vehicles.