Unveiling the Synergistic Effect of Ferroelectric Polarization and Domain Configuration for Reversible Zinc Metal Anodes

Abstract

The tendency of zinc (Zn) anodes to form uncontrolled Zn electrodeposits and the occurrence of side‐reactions at Zn‐electrolyte interfaces are a fundamental barrier hampering broad applications of aqueous rechargeable Zn‐based batteries. Herein, a ferroelectric domain‐mediated strategy is proposed to manipulate the Zn plating behavior and achieve controllable Zn growth orientation by coating Zn foil with a ferroelectric tetragonal KTN (t‐KTN) layer. The ferroelectric domain of t‐KTN single crystals exhibits periodic distribution of upward and downward polarizations, corresponding to alternating positively and negatively charged surfaces. The charged ferroelectric surfaces can manipulate the transfer kinetics of Zn ions and the concentration distribution of anions via the interplay between ferroelectric dipoles and adsorbed ions. With the synergistic effect of the ferroelectric polarization and domain configurations, the well‐aligned interlamellar arrays composed of electrodeposited Zn are formed in the initial deposition process, which enable selective deposition within interlamellar arrays and eliminate the dendrite growth during the following plating process. As a result, the t‐KTN layer‐modified Zn anode enables reversible Zn plating/stripping with low voltage hysteresis for over 1200 h at 1 mA cm−2 in symmetric cells, and the assembled full cell exhibits a significantly enhanced cycling stability of over 5500 cycles at 5 A g−1.

Cellulose‐Acetate Coating by Integrating Ester Group with Zinc Salt for Dendrite‐Free Zn Metal Anodes

“…Various strategies have been proposed, such as fabricating artificial protective coating, [11] designing quasi-solid hydrogel, [12,13] alloying tactics, [14,15] using 3D conductive hosts, [16,17] and optimizing electrolytes. [18][19][20][21] Among them, constructing an artificial layer on the Zn anode is the most effective and practicable.…”

Interface Reversible Electric Field Regulated by Amphoteric Charged Protein-Based Coating Toward High-Rate and Robust Zn Anode

“…–2 . f Comparison of cumulative capacity and current density of Zn-SF with other reported Zn anodes with various coating layers (PZIL [ 13 ], TiN [ 17 ], IS [ 20 ], PFSA [ 21 ], PA [ 11 ], NaTi 2 (PO 4 ) 3 [ 50 ], graphite [ 51 ],polymer glue [ 52 ], PVB [ 53 ], CaCO 3 [ 18 ], Gel-MA [ 54 ], PI [ 22 ], t-KTN [ 26 ], PANZ [ 55 ], Ce 2 O 3 [ 24 ], MOF [ 56 ], MXene [ 19 ]) …”

“…-2 . f Comparison of cumulative capacity and current density of Zn-SF with other reported Zn anodes with various coating layers (PZIL [13], TiN [17], IS [20], PFSA [21], PA [11], NaTi 2 (PO 4 ) 3 [50], graphite [51],polymer glue [52], PVB [53], CaCO 3 [18], Gel-MA [54], PI [22], t-KTN [26], PANZ [55], Ce 2 O 3 [24], MOF [56], MXene [19]) and S11c) [58]. The exchange current density of the Zn-SF anode (9.64 mA cm −2 ) was higher than that of the bare Zn anode (4.90 mA cm −2 ), indicating a faster electrochemical reduction rate of Zn 2+ with SF-assisted desolvation.…”

“…For the stable plating/stripping process and low anodic polarization voltage, a delicate interface driving force with accelerated Zn 2+ flux on the anode surface is particularly desirable. One effective method is to regulate the interface electric field through the dielectric interface that serves as a build-in driving force [24][25][26]. Dipoles are spontaneously polarized and alternately exhibit positively and negatively charged surfaces, corresponding to the charging and discharging process [25,26].…”

“…One effective method is to regulate the interface electric field through the dielectric interface that serves as a build-in driving force [24][25][26]. Dipoles are spontaneously polarized and alternately exhibit positively and negatively charged surfaces, corresponding to the charging and discharging process [25,26]. The charged surface can achieve low anodic polarization and high rate performance by dynamically accelerating ion transport as well as adsorbing ions and homogenizing ion flux [27].…”