RESUMO
The undesirable dendrite growth induced by non-planar zinc (Zn) deposition and low Coulombic efficiency resulting from severe side reactions have been long-standing challenges for metallic Zn anodes and substantially impede the practical application of rechargeable aqueous Zn metal batteries (ZMBs). Herein, we present a strategy for achieving a high-rate and long-cycle-life Zn metal anode by patterning Zn foil surfaces and endowing a Zn-Indium (Zn-In) interface in the microchannels. The accumulation of electrons in the microchannel and the zincophilicity of the Zn-In interface promote preferential heteroepitaxial Zn deposition in the microchannel region and enhance the tolerance of the electrode at high current densities. Meanwhile, electron aggregation accelerates the dissolution of non-(002) plane Zn atoms on the array surface, thereby directing the subsequent homoepitaxial Zn deposition on the array surface. Consequently, the planar dendrite-free Zn deposition and long-term cycling stability are achieved (5,050 h at 10.0 mA cm-2 and 27,000 cycles at 20.0 mA cm-2). Furthermore, a Zn/I2 full cell assembled by pairing with such an anode can maintain good stability for 3,500 cycles at 5.0 C, demonstrating the application potential of the as-prepared ZnIn anode for high-performance aqueous ZMBs.
RESUMO
Rechargeable aqueous Zn-I2 batteries (ZIB) are regarded as a promising energy storage candidate. However, soluble polyiodide shuttling and rampant Zn dendrite growth hamper its commercial implementation. Herein, a hetero-polyionic hydrogel is designed as the electrolyte for ZIBs. On the cathode side, iodophilic polycationic hydrogel (PCH) effectively alleviates the shuttle effect and facilitates the redox kinetics of iodine species. Meanwhile, polyanionic hydrogel (PAH) toward Zn metal anode uniformizes Zn2+ flux and prevents surface corrosion by electrostatic repulsion of polyiodides. Consequently, the Zn symmetric cells with PAH electrolyte demonstrate remarkable cycling stability over 3000 h at 1 mA cm-2 (1 mAh cm-2 ) and 800 h at 10 mA cm-2 (5 mAh cm-2 ). Moreover, the Zn-I2 full cells with PAH-PCH hetero-polyionic hydrogel electrolyte deliver a low-capacity decay of 0.008 per cycle during 18 000 cycles at 8 C. This work sheds light on hydrogel electrolytes design for long-life conversion-type aqueous batteries.
RESUMO
Weak binding and affinity between the conductive support and iodine species leads to inadequate electron transfer and the shuttle effect. Herein, redox kinetics and duration are significantly boosted by introducing a Nb2 CTX host that is classified as a layered 2D Nb-based MXene. With a facile electrodeposition strategy, initial I- ions are electrically driven to insert in the nanosized interlayers and are electro-oxidized in situ. Linear I2 is firmly confined inside and benefits from the rapid charge supply from the MXene. Consequently, an aqueous Zn battery based on a Zn metal anode and ZnSO4 electrolyte delivers an ultraflat plateau at 1.3 V, which contributes to 84.5% of the capacity and 89.1% of the energy density. Record rate capability (143 mAh g-1 at 18 A g-1 ) and lifespan (23 000) cycles are achieved, which are far superior to those of all reported aqueous MXenes and I2 -metal batteries. Moreover, the low voltage decay rate of 5.6 mV h-1 indicates its superior anti-self-discharge properties. Physicochemical analyses and density functional theory calculations elucidate that the localized electron transfer and trapping effect of the Nb2 CTX MXene host are responsible for enhanced kinetics and suppressed shuttle behavior. This work can be extended to the fabrication of other I2 -metal batteries with long-life-time expectations.