A Seamless Metal-Organic Framework Interphase with Boosted Zn2+ Flux and Deposition Kinetics for Long-Living Rechargeable Zn Batteries.

Zn metal has received immense interest as a promising anode of rechargeable aqueous batteries for grid-scale energy storage. Nevertheless, the uncontrollable dendrite growth and surface parasitic reactions greatly retard its practical implementation. Herein, we demonstrate a seamless and multifunctional metal-organic framework (MOF) interphase for building corrosion-free and dendrite-free Zn anodes. The on-site coordinated MOF interphase with 3D open framework structure could function as a highly zincophilic mediator and ion sifter that synergistically induces fast and uniform Zn nucleation/deposition. In addition, the surface corrosion and hydrogen evolution are significantly suppressed by the interface shielding of the seamless interphase. An ultrastable Zn plating/stripping is achieved with elevated Coulombic efficiency of 99.2% over 1000 cycles and prolonged lifetime of 1100 h at 10 mA cm-2 with a high cumulative plated capacity of 5.5 Ah cm-2. Moreover, the modified Zn anode assures the MnO2-based full cells with superior rate and cycling performance.

An Ultrafast Air Self-Charging Zinc Battery.

Air self-charging power systems possess the capability of energy harvesting, conversion, and storage simultaneously. However, in general, their self-charging rate is slow and the batteries cannot be oxidized to the fully charged state due to the weak oxidizability of O2 . Herein, an ultrafast air self-charging aqueous zinc battery is designed by constructing a polyaniline@Pt/C (PANI@Pt/C) composite cathode. The introduction of Pt/C catalyst endows the redox reaction between PANI and O2 with fast reaction kinetics and extended redox potential difference. Therefore, the self-charging rate of the Zn/PANI@Pt/C batteries is effectively accelerated and they can be self-charged to fully charged state. Furthermore, the PANI can be recharged by O2 simultaneously during discharging process to compensate the consumed electrical energy, achieving prolonged energy supply. In addition, the PANI@Pt/C cathodes can be directly used as the cathodes of flexible self-charging zinc batteries due to their excellent mechanical properties. As a proof of concept, flexible soft-packaged Zn/PANI@Pt/C batteries are fabricated and displayed stable electrochemical performance and self-rechargeability even at different bending states. A route is provided here to design ultrafast chemical self-charging energy storage devices and the horizons of flexible energy storage devices are broadened.

Ethanol as Solvent Additives with Competitive Effect for High-Stable Aqueous Zinc Batteries.

Aqueous zinc-ion batteries are emerging as promising sustainable energy-storage devices. However, their cyclic stability is still a great challenge due to the inevitable parasitic reaction and dendrite growth induced by water. Herein, a cosolvent strategy based on competitive effect is proposed to address the aforementioned challenges. Ethanol with a higher Gutmann donor number demonstrates lower polarity and better wettability on the Zn surface compared with water, which endows ethanol with the ability of minimizing water activity by weakening H bonds and preferentially adsorbing on the Zn electrode. The above competitive advantages synergistically contribute to inhibiting the decomposition of free water and dendrite growth. Besides, an organic-inorganic hybrid solid-electrolyte interphase layer is in situ built based on ethanol additives, where organic matrix suppresses water corrosion while inorganic fillers promote fast Zn2+ diffusion. Consequently, the electrolyte with ethanol additives boosts a high reversibility of Zn deposition, long-term durability, as well as superior Zn2+ diffusibility in both Zn half-cells (Zn||Cu and Zn||Zn batteries) and Zn full cells (Zn||PTCDA and Zn||VO2 batteries). This work sheds light on a universal strategy to design a high-reversible and dendrite-free Zn anode for stable aqueous batteries.

Boosted H+ Intercalation Enables Ultrahigh Rate Performance of the δ-MnO2 Cathode for Aqueous Zinc Batteries.

H+ intercalation, as a critical battery chemistry, enables electrodes' high rate performance due to the fast diffusion kinetics of H+. In this work, more water molecules are introduced into δ-MnO2 by the protonation of δ-MnO2 with abundant oxygen vacancies. Benefiting from the structure with a close arrangement of water molecules in interlayers, the Grotthuss transport of proton is achieved in the energy storage of the δ-MnO2 cathode. As a result, the δ-MnO2 cathode exhibits an ultrahigh rate performance with a capacity of 368.1 mAh g-1 at 0.5 A g-1 and 83.4 mAh g-1 at 50 A g-1, which has a capacity retention of 73% after 1100 cycles at 10 A g-1. The study of the storage mechanism reveals that the Grotthuss intercalation of proton predominates the storage process, which empowers the cathode with high rate performance.

Oxygen-Deficient ß-MnO2@Graphene Oxide Cathode for High-Rate and Long-Life Aqueous Zinc Ion Batteries.

Recent years have witnessed a booming interest in grid-scale electrochemical energy storage, where much attention has been paid to the aqueous zinc ion batteries (AZIBs). Among various cathode materials for AZIBs, manganese oxides have risen to prominence due to their high energy density and low cost. However, sluggish reaction kinetics and poor cycling stability dictate against their practical application. Herein, we demonstrate the combined use of defect engineering and interfacial optimization that can simultaneously promote rate capability and cycling stability of MnO2 cathodes. ß-MnO2 with abundant oxygen vacancies (VO) and graphene oxide (GO) wrapping is synthesized, in which VO in the bulk accelerate the charge/discharge kinetics while GO on the surfaces inhibits the Mn dissolution. This electrode shows a sustained reversible capacity of ~ 129.6 mAh g-1 even after 2000 cycles at a current rate of 4C, outperforming the state-of-the-art MnO2-based cathodes. The superior performance can be rationalized by the direct interaction between surface VO and the GO coating layer, as well as the regulation of structural evolution of ß-MnO2 during cycling. The combinatorial design scheme in this work offers a practical pathway for obtaining high-rate and long-life cathodes for AZIBs.

Proton-Dominated Reversible Aqueous Zinc Batteries with an Ultraflat Long Discharge Plateau.

Aqueous zinc batteries (AZBs) are considered promising candidates for large-scale energy storage systems because of their low cost and high safety. However, currently developed AZB cathodes always suffer from the intense charge repulsion of multivalent-ion and complex multiphase electrochemistry, resulting in an insufficient cycling life and impracticable high-sloping discharge profile. Herein, we found that the synthesized ultrathin Bi2O2Se nanosheets can effectively activate stable protons storage in AZBs rather than large zinc ions. This proton-dominated cathode provides an ultraflat discharge plateau (72% capacity proportion) and exhibits long-term cyclability as 90.64% capacity retention after 2300 cycles at 1 A g-1. Further in situ synchrotron X-ray diffraction, ex situ X-ray photoelectronic spectroscopy, and density functional theory confirm the energy storage mechanism regarding the highly reversible proton insertion/extraction process. Benefiting from the proton-dominated fast dynamics, reliable energy supply (>81.5% discharge plateau capacity proportion) is demonstrated at a high rate of up to 10 A g-1 and in the frozen electrolyte below -15 °C. This work provides a potential design of high-performance electrode materials for AZBs.