Inducing the Preferential Growth of Zn (002) Plane for Long Cycle Aqueous Zn‐Ion Batteries

Abstract

If the preferred growth planes are ( 105), (103), and (002), the crystal grows at an angle of 0-30° from the substrate. If the preferred growth planes are ( 101), ( 102), (112), and (114), the crystal grows at an angle of 30-70° from the substrate. And if the preferred growth planes are ( 100) and ( 110), the crystal grows at an angle of 70-90° from the substrate. [10] By density functional theory (DFT) calculation, Zhu et al. [11] revealed that the binding energies between Zn atom and the (002), (100), and (101) planes of Zn metal are different. The binding energy of (002) plane is the weakest, while that of (101) plane is the strongest, which means that Zn atoms will preferentially deposit on that crystal plane, allowing (101) plane to preferentially grow, and thus resulting in the formation of Zn dendrites. If crystal planes like (105), (103), and (002) can be induced to preferentially grow, it will make deposition layer smoother and inhibit the formation of Zn dendrites. It is worth noting that the preferential growth of ( 105), (103), and (002) planes can form a compact deposition layer to inhibit corrosion and H 2 evolution to a certain extent. [12,13] Therefore, reasonable manipulation of crystal orientation is of great significance for AZIBs.Up to now, the methods of manipulating crystal orientation in AZIBs mainly include optimizing the separator, [14,15] modifying coating layers, [16][17][18][19][20][21][22] using electrolyte additives, [11,[23][24][25][26][27][28] and processing/heating treatment of the Zn anode. [12,13,29] In the above methods, using electrolyte additives is much attractive because of its convenience and cost-effectiveness. [30][31][32] Electrolyte additives such as Mn 2+ +gelatin, SBT, OTf 2− , H 3 PO 4 , In 2 (SO 4 ) 3 , H 3 BO 3 , CTAB, SDS, TU, and PEG-8000 have been employed to induce preferential growth of specific crystal planes. [11,[23][24][25][26][27][28] Nevertheless, most of these researches require pre-preparation of Zn anodes with specific crystal planes such as (002), [11,[25][26][27][28] which makes the process complicated. And most works only focused on the orientation change of Zn crystals after a single electrodeposition. It is worth noting that almost all of these works were unable to maintain a long cycle life under the condition of high current density and large areal capacity, which may be related to the weakened effect of electrolyte additives due to the structural reconstruction of Zn anode over cycling. [11] Therefore, it is crucial to systematically Uncontrolled growth of Zn dendrites is the main reason for the short-circuit failure of aqueous Zn-ion batteries. Using electrolyte additives to manipulate the crystal growth is one of the most convenient strategies to mitigate the dendrite issue. However, most additives would be unstable during cycling due to the structural reconstruction of the deposition layer. Herein, it is proposed to use 1-butyl-3-methylimidazolium cation (BMIm + ion) as an electrolyte additive, which could steadily induce the preferential ...

Selection criteria for electrical double layer structure regulators enabling stable Zn metal anodes

“…28 Li et al recently reported that the preferential adsorption of 1-butyl-3-methylimidazolium cations on the (100) and (101) planes of Zn anodes forces Zn 2+ ions to deposit on the (002) plane, thus leading to the preferential growth of the (002) plane. 29 Despite their great progress, the cycle life of Zn anodes varies greatly depending on the selected electrolyte additives. The reason behind this phenomenon is of significance to guide the design of effective EDL structure regulators but is poorly understood yet.…”

Ion Bridging by Carbon Dioxide Facilitates Electrochemical Energy Storage at Charged Carbon–Ionic–Liquid Interfaces

“…[18b] A profound polarization process of CO 2 on the negatively electrified NDSTC surface is thus deduced. [18a,41] The pyrinidic nitrogen is nucleophilic with lone pair electrons while [EMIM] + behaves as electrophile via the C(2)-H. [54] The steric hindrance analogical to weak frustrated Lewis pairs thus creates an active region for the adsorbed CO 2. [37,52a,55] The electron-delocalized pyridinic nitrogen triggers the charge redistribution in CO 2 and the increased electron density in CO 2 oxygen atoms further induces hydrogen-bonding-like interactions with the C(2)-H. [55] The bonding and antibonding orbitals of adsorbed CO 2 thus interact with the unoccupied orbitals of electrophile and non-bonding orbitals of the nucleophile, respectively, leading to the polarization of CO 2 molecules.…”

Review of regulating Zn2+ solvation structures in aqueous zinc-ion batteries

“…Organic small molecules are used not only as co-solvents, but also as functional additives in aqueous electrolytes for ZIBs. Their working mechanisms include regulating Zn deposition by absorbing on the surface of Zn anode, breaking the original H-bonds and/or in situ construction of SEI by participation of solvation structures of Zn 2+ [18,65,[70][71][72][73][74][75][76][77][78][79][80][81][82][83][84][85][86][87][88][89]. In this section, we mainly focused on the manipulation of solvation structures by adoption of functional additives.…”