Undesired Reactions in Aqueous Rechargeable Zinc Ion Batteries

Verma, Vivek; Kumar, Sonal; Manalastas, William; Srinivasan, Madhavi

doi:10.1021/acsenergylett.1c00393

Cited by 213 publications

(189 citation statements)

References 102 publications

(292 reference statements)

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“…Besides, preferential dissolution of the dendrite root will lead to its detachment from the surface of Zn metal anode (ZMA), resulting in the irreversible consumption of active species. Moreover, undesirable side reactions such as hydrogen evolution reaction (HER) generate bubbles on ZMA, which influences the deposition morphology to form porous electrodeposits ( 12 , 13 ). In addition, the noncompact nature of deposited Zn creates drastic volume change to increase the risk of cell failure ( 14 ).…”

Section: Introductionmentioning

confidence: 99%

Confining Sn nanoparticles in interconnected N-doped hollow carbon spheres as hierarchical zincophilic fibers for dendrite-free Zn metal anodes

et al. 2022

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We developed a three-dimensional hybrid fiber host consisting of interconnected N-doped hollow carbon spheres embedded with Sn nanoparticles (denoted as Sn@NHCF) for Zn metal anodes in high-performance Zn metal batteries. Experimental observations and density functional theory calculation reveal that the zincophilic Sn nanoparticles and N-doped carbons enable the homogeneous Zn deposition on the interior and exterior surfaces of the hollow fibers. Moreover, the hierarchical hollow fiber network effectively reduces the structural stress during the plating/stripping process. As a result, the developed Sn@NHCF host exhibits remarkable electrochemical properties in terms of high Coulombic efficiency, low voltage hysteresis, and prolonged cycling stability without dendrite formation. Moreover, a full cell based on the designed Sn@NHCF-Zn composite anode and a V 2 O 5 cathode demonstrates superior rate capability and stable cycle life. This work provides a new strategy for the design of dendrite-free Zn anodes for practical applications.

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Section: Introductionmentioning

confidence: 99%

Confining Sn nanoparticles in interconnected N-doped hollow carbon spheres as hierarchical zincophilic fibers for dendrite-free Zn metal anodes

et al. 2022

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A Universal Additive Strategy to Reshape Electrolyte Solvation Structure toward Reversible Zn Storage

Lim

et al. 2022

Advanced Energy Materials

222

137

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Despite these attractive merits, the performance is largely limited by unstable Zn chemistry in aqueous electrolyte with mildly acidic environment. [4][5][6] The produced hydrated [Zn(H 2 O) x ] 2+ ion complex species and the free water outside the Zn 2+ -solvation sheath induce severe interfacial side reactions, including Zn corrosion and H 2 evolution, along with aggravation of nonuniform Zn deposition. [7][8][9] This inevitably results in low Coulombic efficiency (CE) and can ultimately compromise safety (e.g., battery swelling and explosion, shortcircuit failure). [10] To circumvent the problems, many attempts have been made, including Zn alloying, [11] surface modification, [12,13] structure optimization of Zn host, [14,15] adoption of Zn 2+ intercalation anode material, [16,17] and compositional design of electrolyte. [18][19][20] Among them, electrolyte design is the most expedient solution with the potential to scale up from lab to practical application, owing to its superior repeatability and diversity. Recently, super-concentrated electrolytes are explored to interrupt original solvated balance and improve Zn reversibility. [21][22][23][24] The most representative example was proposed by Wang et al., where the Zn 2+ is surrounded by bis(trifluoromethanesulfonyl) imide (TFSI -) instead of water molecules due to the formation of copious [Zn(TFSI)] + ionic pairs with close coordination. [25][26][27][28] However, a high concentration of reaction-unrelated salt or flammable organic species in the electrolyte may induce safety and reaction kinetic issues with occurring costs, going against the initial rationale behind using AZIBs. [29] As such, investigations now are focusing on developing electrolyte additives on Zn 2+ -solvation structure in dilute solutions, such as methanol, [30] polyhydric alcohols, [31,32] dimethyl sulfoxide, [33,34] and polyacrylamide. [35] Although the Zn deposition behavior is optimized, many organic additives are still plagued by limited alleviation of side reactions. [10] Meanwhile, most of them hugely increase the polarization voltage while improving the cycling stability, leading to inferior electrochemical performance under practical conditions with high current density and areal capacity. Currently, rationally developing a class of advanced multifunctional additives remains challenging and a general additive design principle is accordingly of great significance for aqueous Zn chemistry.Carbonyl-containing liquid organics, such as N-methyl-2-pyrrolidone (NMP), N,N-dimethylformamide (DMF), and acetoneThe benefits of Zn, despite many of its performance advantages (e.g., high theoretical capacity and low redox potential), are compromised by severe side reactions and Zn dendrite growth in aqueous electrolytes, due to the coordinated H 2 O within the Zn 2+ -solvation sheath and reactive free water in the bulk electrolyte. Unlike most efforts focused on costly super-concentrated electrolytes and single additive species, a universal strategy is proposed to boost Zn reversibility in dil...

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“…Side reactions caused by corrosion of Zn electrode are also an important mechanism for a battery failure of aqueous ZIBs. [ 5 ] The linear polarization experiments were conducted in a common aqueous electrolyte (2.0 m ZnSO 4 ) to analyze the corrosion behavior before and after passivation treatment. As shown in Figure 3e, compared with the untreated Zn electrode (−1.014 V), the passivated Zn electrode shows a much higher corrosion potential of −0.976 V, and a much lower corrosion current density, indicating a lower corrosion reactivity and a lower corrosion rate after passivation treatment.…”

Section: Resultsmentioning

confidence: 99%

“…[1][2][3] Primary batteries based on Zn anode (e.g., alkaline Zn-MnO 2 and Zn-Ni batteries) are centuries-old technologies and are still used in portable devices. [4,5] With their relatively low cost and a higher degree of safety, aqueous rechargeable zinc ion batteries (ZIBs) are an attractive option in the search of safe, grid-level energy storage solution for integrating renewable energy sources with the current electrical energy infrastructure. [6][7][8][9][10] Significant advances have been achieved in the exploration of cathode materials for Zn 2+ storage.…”

Section: Introductionmentioning

confidence: 99%

Chemical Passivation Stabilizes Zn Anode

Huang

2022

Advanced Materials

102

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the cycling life of ZIBs is greatly limited by the stability of Zn metal anode in aqueous electrolytes. [15][16][17] The tendency of Zn to develop dendrites during cycling can result in an inner short circuit when they pierce through the separators. On the other hand, Zn metal is thermodynamically unstable in aqueous electrolytes and is subject to corrosion in H 2 O or slightly acidic solutions. [18,19] The irreversible consumption of electrolyte and the accumulation of corrosion by-products (e.g., H 2 ) can lead to the "bloating" of battery or even a circuit failure. [20] In addition, corrosion amplifies any heterogeneity that may be present or developed on the Zn electrode, which further promotes the growth of dendrite, leading to the premature failure of batteries.To improve the stability and electrochemical reversibility of Zn metal electrode, several mitigative strategies have been reported. [21] For example, water-in-salt type of electrolytes has been used to prevent Zn corrosion due to a lower activity of bounded water molecules. [22,23] However, this results in a lower ion diffusion rate and uneconomic use of electrolytes. [24] Also, some ingenious structural designs on Zn host/substrate, for example, using high temperature annealed ZIF-8 nanoparticles as the porous host, [25] sputtering deposited quasi-isolated nano-Au particles as the heterogeneous seeds, [26] manufacturing the Zn surface with more exposed (002) crystal plane, [27] designing carbon spheres host with zincophilic sites, [28] depositing a graphene layer on stainless steel to guide the deposition of Zn, [29] show significant improvements of the inhibition of dendrite. [25][26][27][28][29][30] Nevertheless, the scalability, cost-effectiveness, and efficiency of these reported approaches can hardly be met simultaneously. Alternatively, protective layers are often inserted in between the electrode and electrolytes to improve the uniformity of Zn deposition, [31,32] but they are typically in the range of a few microns to tens of microns, which are comparable to the thickness of the electrode, thus significantly increases the volume and the mass of the electrodes, reducing the overall energy density.Here, we report that a rapid solution chemical treatment of Zn metal that results in a uniform, conformal, and robust passivation layer of ≈65 nm thick, which can drastically improve the cycling stability of Zn anode. Due to the chemical activity of Zn, it can spontaneously react with many oxidizing agents and form a dense continuous passivation layer protecting its surface. Compared to coatings made of various polymers or 2D materials, this native passivation layer has several advantages, including strong adhesion to the substrate, high homogeneity, and small thickness due to the self-limiting nature of Aqueous zinc ion batteries are an attractive option for grid-scale energy storage, which is vital to the integration of renewable energy resources with the electric energy infrastructure. The cycling stability of aqueous ZIBs is determined by the ele...

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Undesired Reactions in Aqueous Rechargeable Zinc Ion Batteries

Cited by 213 publications

References 102 publications

Confining Sn nanoparticles in interconnected N-doped hollow carbon spheres as hierarchical zincophilic fibers for dendrite-free Zn metal anodes

Confining Sn nanoparticles in interconnected N-doped hollow carbon spheres as hierarchical zincophilic fibers for dendrite-free Zn metal anodes

A Universal Additive Strategy to Reshape Electrolyte Solvation Structure toward Reversible Zn Storage

Chemical Passivation Stabilizes Zn Anode

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