Tetrapropylammonium Hydroxide as a Zinc Dendrite Growth Suppressor for Rechargeable Aqueous Battery

Abstract

Zinc metal is widely used as an anode in various aqueous systems. However, zinc anode suffers from the dendrite formation on the surface upon cycling leading to a poor cyclability of a cell and its termination due to short circuit. In this work, the effect of tetrapropylammonium hydroxide (TPAH) was studied as an electrolyte additive for aqueous Zn//ZnCl2 + LiCl//LiFePO4 battery. TPAH additive prolongs the battery cycle life depending on its concentration (0.01–0.1 M). The better capacity retention over 350 cycles was observed for a symmetrical Zn//ZnCl2 + LiCl//Zn cell with 0.05 M TPAH whereas without additives the cell worked for only 110 cycles. The mechanism of TPAH influence on capacity retention is proposed based on the results of SEM and XRD analysis of the Zn anode and FTIR and NMR studies of the electrolyte. The XRD patterns of the negative electrode of the cell with TPAH indicates that zinc was preferentially deposited in a highly oriented (002) direction, which is more resistant against dendrite formation. These differences in deposited structure of Zn dendrites were confirmed by SEM images as well. FTIR and NMR spectra showed that TPAH decomposes to propylamine (RnN+H) and propene during cycling. TPAH also has an effect on the size and uniform distribution of Zn growth sides.

Texturing Crystal Plane of Zinc Metal via Cleavage Fracture for a Dendrite-Free Zinc Anode

“…Lessons from previous research work on the relationship between the zinc crystal plane and zinc deposition behavior point out that zinc metal with the (002) preferred plane is more resistant to dendrite growth than (100) and (101) preferred planes, which may be attributed to the lower deposition rate and electrochemical activity of the (002) plane relative to (100) and (101) planes. − However, exposing specific crystal faces on the zinc sheet surface is difficult. So far, there are only a few reports on homogeneous zinc deposition induced by constructing exposed (002) planes on zinc anodes.…”

An Overview of Challenges and Strategies for Stabilizing Zinc Anodes in Aqueous Rechargeable Zn-Ion Batteries

“…The electrochemical performance of ZIBs can also be enhanced using organic additives such as polymers [172][173][174][175][176][177][178][179][180], surfactants [181][182][183][184][185][186][187], and organic compounds [36,[188][189][190][191][192][193][194]. A summary of previous reports regarding organic additives that preserve Zn anodes was presented in Table 5.…”

“…(Reproduced with permission [194] Copyright 2022, John Wiley & Son). PVP Render less corrosion and more uniform Zn deposition on the anode Modulate the deposition of cathode without aggregations [179] PEG Inhibit Zn dendrites and side reactions [180] SDS Suppress the evolution of hydrogen and oxygen Suppress the decomposition of water Inhibit the corrosion of Zn [183] TPAH Inhibit the Zn dendrite growth [185] TMBA + Inhibit side reactions Regulate Zn uniform distribution [187] Acetonitrile Accumulate on the Zn surface to shield water molecules Suppress the HER [189] PASP Promote dendrite-free Zn deposition Resist the side reactions [193] Silk peptide Suppress dendrite formation Regulate solvation and interface [194] Vanillin Promote dendrite-free Zn deposition Suppress HER and by-products [197] NMO = polyoxometalate, GO = graphene oxide, PAM = polyacrylamide, PEO = polyethylene oxide, PVP = polyvinyl pyrrolidone, TMBA + = benzyltrimethylammonium, SDS = sodium dodecyl benzene sulfonate, TPAH = tetra propylammonium hydroxide.…”

Advanced Battery Materials Research at Nazarbayev University: Review

“…Our group developed the model of zinc based Rechargeable Aqueous Lithium-ion Battery (RAL-IB) Zn/LiCl-ZnCl 2 /LiFePO 4 with a mild acidic electrolyte [42,43]. The concept is demonstrated using LiFePO 4 cathode and Zn anode, operating in an optimized weak acidic aqueous Li + /Zn 2+ binary electrolyte.…”