Arginine Cations Inhibiting Charge Accumulation of Dendrites and Boosting Zn Metal Reversibility in Aqueous Rechargeable Batteries

Abstract

Aqueous zinc-ion batteries are regarded as one of the new promising rechargeable batteries. However, serious Zn dendrite growth causes short-circuit issues in the batteries. Herein, we report that arginine (Arg), a cationic surfactant electrolyte additive, can inhibit irregular and nonplanar dendrite growth and induce uniform Zn deposition. It shows a long cycle life (515 h) of Zn/Zn cells in the electrolyte containing Arg, which is ∼10 times longer than that of the electrolyte with no additive. The hydrolysis of Arg produces arginine cations (Arg + ), which will be preferentially adsorbed on Zn dendrites due to the tip charge accumulation effect during the Zn plating process. Arg + increases the overpotential for the nucleation of Zn dendrites and results in uniform Zn deposition. After about 350 cycles, the MnO 2 /Zn cell shows 84.59% capacity retention and 99.85% average Coulomb efficiency in the electrolyte with the additive. The low-cost and nontoxic electrolyte additive identified in this work provides a new pathway toward inducing regular Zn deposition morphology.

Amino Acid‐Induced Interface Charge Engineering Enables Highly Reversible Zn Anode

“…Simultaneously, charged Arg molecules on protrusions also play a beneficial role in the inhibition of dendrite growth through electrostatic shielding. [ 45 ] To further testify the dendrite restriction effect, symmetrical cells at various capacity (10 mAh cm −2 and 20 mAh cm −2 , respectively, Figure 3c,d) were tested, short circuit occurs rapidly for the cells in bare ZnSO 4 electrolyte (less than 30 h) due to the severe dendrite growth. On the opposite, the cell with ZnSO 4 +Arg electrolyte can support more than 200 h even at an ultra‐high areal capacity of 20 mAh cm −2 , resulted by the self‐adaptive feature and steric hindrance of Arg adsorption.…”

Strategies of regulating Zn2+solvation structures for dendrite-free and side reaction-suppressed zinc-ion batteries

“…8e and f), 208 initiating a self-adaptive zinc-electrolyte interface with a strong steric hindrance, thus effectively hindering H 2 O adsorption and guiding uniform zinc deposition. Besides arginine, 208,209 glutamate has been demonstrated to regulate the structure of hydrated zinc ions. 210…”

“…The strategies of zinc-philic additives and the corresponding electrochemical performance are summarized in Table 3. 58,87,101,207–209,211,213,216–225 These zinc-philic additives can adsorb onto the zinc anode surface via physical/chemical adsorption to form a protective layer on the anode surface, which can effectively prevent the contact between H 2 O and zinc and guide the uniform zinc deposition. Besides, the adsorbed additive molecules promote the desolvation of Zn(H 2 O) 6 2+ by removing H 2 O molecules from the solvation sheath of Zn 2+ , which can suppress the HER, corrosion, and formation of by-products and zinc dendrites.…”

Recent progress, mechanisms, and perspectives for crystal and interface chemistry applying to the Zn metal anodes in aqueous zinc‐ion batteries

“…Especially for the discharging at high rates, the "tip effect" is more likely to occur because of serious concentration polarization, resulting in severe dendrite growth in large quantities under unchecked conditions. 44,45 Likewise, other metal batteries (such as Mg Li and Al) have also suffered from a serious dendrite issue due to irregular metal ions deposition on the anode, making it inclined to reduce the Coulomb efficiency and utilization of metal ions. 46−48 Zhi et al compared the Zn dendrite with Li and Al dendrites.…”

“…When zinc continues to be deposited, more and more electrons are inclined to accumulate at the tip of the bulge, so the following zinc ions prefer to deposit over there; that is the “tip effect,” resulting in a vicious circle. Especially for the discharging at high rates, the “tip effect” is more likely to occur because of serious concentration polarization, resulting in severe dendrite growth in large quantities under unchecked conditions 44,45 …”