RESUMEN
Aqueous Zn batteries have recently emerged as promising candidates for large-scale energy storage, driven by the need for a safe and cost-effective technology with sufficient energy density and readily accessible electrode materials. However, the energy density and cycle life of Zn batteries have been limited by inherent chemical, morphological, and mechanical instabilities at the electrode-electrolyte interface where uncontrolled reactions occur. To suppress the uncontrolled reactions, we designed a crystalline polymer interphase for both electrodes, which simultaneously promotes electrode reversibility via fast and selective Zn transport through the adaptive formation of ion channels. The interphase comprises an ultrathin layer of crystalline poly(1H,1H,2H,2H-perfluorodecyl acrylate), synthesized and applied as a conformal coating in a single step using initiated chemical vapor deposition (iCVD). Crystallinity is optimized to improve interphase stability and Zn-ion transport. The optimized interphase enables a cycle life of 9500 for Zn symmetric cells and over 11,000 for Zn-MnO2 full-cell batteries. We further demonstrate the generalizability of this interphase design using Cu and Li as examples, improving their stability and achieving reversible cycling in both. The iCVD method and molecular design unlock the potential of highly reversible and cost-effective aqueous batteries using earth-abundant Zn anode materials, pointing to grid-scale energy storage.
RESUMEN
Metal-air batteries including Li-air, Na-air, Al-air, and Zn-air, have received significant scientific and technological interest for at least the last three decades. The interest stems primarily from the fact that the electrochemically active material (O2) in the cathode can in principle be harvested from the surroundings. In practice, however, parasitic reactions with reactive components other than oxygen in dry air passivate the anode, limit cycling stability of air-sensitive (e.g., Li, Na, Al) and electrolyte-sensitive (e.g., Zn) anodes, in most cases obviating the energy-density benefits of harvesting O2 from ambient air. As a compromise, so-called metal-oxygen batteries in which pure O2 is used as the active cathode material have been extensively studied but are understood to be of little practical relevance because of the large infrastructure required to produce the pure O2 stream. Here, we report on the design of solid-ion conductive chemically inert metal interphases that simultaneously protect a metal anode from parasitic reactions with electrolyte components and which facilitate rapid interfacial ion transport. Interphases composed of indium (In) are reported to be of particular interest for protecting Li and Na anodes from passivation in air whereas interphases composed of Sn are shown to prevent chemical and electrochemical corrosion of Zn anodes in alkaline electrolytes. We report further that these protections enable so-called self-sufficient metal-air batteries capable of extended cycling stability in ambient air environments.
RESUMEN
Polymers are known to adsorb spontaneously from liquid solutions in contact with high-energy substrates to form configurationally complex, but robust phases that often exhibit higher durability than might be expected from the individual physical bonds formed with the substrate. Rational control of the physical, chemical, and transport properties of such interphases has emerged as a fundamental opportunity for scientific and technological advances in energy storage technology but requires in-depth understanding of the conformation states and electrochemical effect of the adsorbed polymers. Here, we analyze the interfacial adsorption of oligomeric polyethylene glycol (PEG) chains of moderate sizes dissolved in protic and aprotic liquid electrolytes and find that there is an optimum polymer molecular weight of approximately 400â Da at which the highest columbic efficiency is achieved for both Zn and Li deposition. These findings point to a simple, versatile approach for extending the lifetime of batteries.
RESUMEN
Aqueous alkaline zinc batteries are of scientific and technological interest because of the potential they offer for cost-effective and safe storage of electrical energy. Poor electrochemical reversibility and shape change of the Zn anode, propensity of Zn to become passivated by surface oxides and hydroxide films upon prolonged exposure to the electrolyte, and electroreduction of water are well-studied but remain unsolved challenges. Here, we create and study electrochemical and transport properties of precise, spatially tunable zwitterionic polymer interphases grown directly on Zn using an initiated-chemical vapor deposition polymerization methodology. In aqueous alkaline media, spatial gradients in compositionâfrom the polymer-electrolyte interface to the solid-polymer interfaceâpromote highly reversible redox reactions at high current density (20 mA cm-2) and high areal capacity (10 mAh cm-2). Via molecular dynamics and experimental analyses, we conclude that the interphases function by regulating the distribution and activity of interfacial water molecules, which simultaneously enables fast ion transport and suppression of surface passivation and the hydrogen evolution reaction. To illustrate the practical relevance of our findings, we study aqueous Zn||NiOOH and Zn||air batteries and observe that zwitterionic polymer interphases produce extended life at high currents and high areal capacity.
RESUMEN
Aqueous zinc flow batteries (AZFBs) with high power density and high areal capacity are attractive, both in terms of cost and safety. A number of fundamental challenges associated with out-of-plane growth and undesirable side reactions on the anode side, as well as sluggish reaction kinetics and active material loss on the cathode side, limit practical deployment of these batteries. We investigated artificial interphases created using a simple electrospray methodology as a strategy for addressing each of these challenges. The effectiveness of the electrospray interphases in full cell zinc-iodine flow batteries was evaluated and reported; it is possible to simultaneously achieve high power density [115 milliwatts per square centimeter (mW/cm2)] and high areal capacity [25 milliampere hour per square centimeter (mA·hour/cm2)]. Last, we extended it to aqueous zinc-bromine and zinc-vanadium flow batteries of contemporary interest. It is again found that high power density (255 and 260 mW/cm2, respectively) and high areal capacity (20 mA·hour/cm2) can be simultaneously achieved in AZFBs.
RESUMEN
Aqueous zinc batteries are attracting interest because of their potential for cost-effective and safe electricity storage. However, metallic zinc exhibits only moderate reversibility in aqueous electrolytes. To circumvent this issue, we study aqueous Zn batteries able to form nanometric interphases at the Zn metal/liquid electrolyte interface, composed of an ion-oligomer complex. In Zn||Zn symmetric cell studies, we report highly reversible cycling at high current densities and capacities (e.g., 160 mA cm-2; 2.6 mAh cm-2). By means of quartz-crystal microbalance, nuclear magnetic resonance, and voltammetry measurements we show that the interphase film exists in a dynamic equilibrium with oligomers dissolved in the electrolyte. The interphase strategy is applied to aqueous Zn||I2 and Zn||MnO2 cells that are charged/discharged for 12,000 cycles and 1000 cycles, respectively, at a current density of 160 mA cm-2 and capacity of approximately 0.85 mAh cm-2. Finally, we demonstrate that Zn||I2-carbon pouch cells (9 cm2 area) cycle stably and deliver a specific energy of 151 Wh/kg (based on the total mass of active materials in the electrode) at a charge current density of 56 mA cm-2.
