Dendrites in Zn‐Based Batteries

Yang, Qi; Li, Qing; Liu, Zhuoxin; Wang, Donghong; Guo, Ying; Li, Xinliang; Tang, Yongchao; Li, Hongfei; Dong, Binbin; Chen, Zhi

doi:10.1002/adma.202001854

Cited by 784 publications

(620 citation statements)

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“…On the other hand, these Zn protrusions caused by hydrogen evolution reaction will attract more Zn 2+ flux (“tip” effect) [ 22 ] under concentrated electric field during electrochemical cycling, thus accelerating the vertical growth of Zn dendrites instead of planar growth and hydrogen production further flourish (Figure 1g). Up to now, various strategies have been evolved to prohibit the Zn dendrite growth, such as electrolyte optimization, [ 8,23–25 ] Zn surface coating, [ 9,21,26–29 ] and alloying. [ 30 ] To some extent, these strategies stabilize Zn metal, but they do not follow the original nature of Zn dendrite growth in aqueous environment, and batteries are operated with low current density and loading mass of cathode materials, far from practical implementation.…”

Section: Figurementioning

confidence: 99%

Toward Practical High‐Areal‐Capacity Aqueous Zinc‐Metal Batteries: Quantifying Hydrogen Evolution and a Solid‐Ion Conductor for Stable Zinc Anodes

et al. 2021

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environments, [7-12] where Zn deposition even during shelf time is continuously interfered by competitive hydrogen evolution through H 2 O decomposition (Zn + 2H 2 O → Zn(OH) 2 + H 2) and by consuming both the electrolyte and active Zn metal. This long-neglected problem will remarkably affect calendar life of batteries, which is equivalently important with the intensively studied cycling life of batteries. As revealed in our preliminary quantitative study shown in Figure 1a, immersing Zn in 2 m ZnSO 4 electrolyte will induce an ≈0.25 mmol h-1 cm-2 hydrogen flux. The continuous hydrogen evolution will cause local pH changes, which further induce the formation of loose and brittle Zn 4 SO 4 (OH) 6 •xH 2 O (3Zn(OH) 2 + ZnSO 4 •xH 2 O → Zn 4 SO 4 (OH) 6 •xH 2 O), as revealed in Figure 1b. [13-18] It is generally assumed that these by-products augment the tortuosity and irregularity at the electrode/electrolyte interface with physical contact surface being increased (Figure 1c-h), which will further accelerate hydrogen evolution reaction. The above issues necessitate an effective method to detect hydrogen evolution. Nevertheless, for a Zn-based battery, these assumption and hypotheses are only based on oversimplified observations of battery swelling, gas bubbles, or conducting polarization curve in the absence of Zn 2+ condition, not reflecting physical truth of battery. [19-21] Hydrogen production during electrochemical procedure and even shelf time has not been precisely quantified. Consequently, efforts to make Zn metal a valid anode material may be misdirected. Quantifying the hydrogen production on the electrode during Zn deposition is key to understanding the mechanisms leading to capacity loss and battery failure. On the other hand, these Zn protrusions caused by hydrogen evolution reaction will attract more Zn 2+ flux ("tip" effect) [22] under concentrated electric field during electrochemical cycling, thus accelerating the vertical growth of Zn dendrites instead of planar growth and hydrogen production further flourish (Figure 1g). Up to now, various strategies have been evolved to prohibit the Zn dendrite growth, such as electrolyte optimization, [8,23-25] Zn surface coating, [9,21,26-29] and alloying. [30] To some extent, these strategies stabilize Zn metal, but they do The hydrogen evolution in Zn metal battery is accurately quantified by in situ battery-gas chromatography-mass analysis. The hydrogen fluxes reach 3.76 mmol h −1 cm −2 in a Zn//Zn symmetric cell in each segment, and 7.70 mmol h −1 cm −2 in a Zn//MnO 2 full cell. Then, a highly electronically insulating (0.11 mS cm −1) but highly Zn 2+ ion conductive (80.2 mS cm −1) ZnF 2 solid ion conductor with high Zn 2+ transfer number (0.65) is constructed to isolate Zn metal from liquid electrolyte, which not only prohibits over 99.2% parasitic hydrogen evolution but also guides uniform Zn electrodeposition. Precisely quantitated, the Zn@ZnF 2 //Zn@ZnF 2 cell only produces 0.02 mmol h −1 cm −2 of hydrogen (0.53% of the Zn//Zn cell). Encouragingly, a hig...

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Section: Figurementioning

confidence: 99%

Toward Practical High‐Areal‐Capacity Aqueous Zinc‐Metal Batteries: Quantifying Hydrogen Evolution and a Solid‐Ion Conductor for Stable Zinc Anodes

et al. 2021

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“…1,2 Among various options, rechargeable aqueous Zn batteries (RAZBs) hold great promise because of advantages of metallic Zn anode including abundant resource, environmental benignancy, low cost, and high theoretical specific/volumetric capacity (820 mAh g -1 and 5855 mAh cm -3 ). [3][4][5] Moreover, compared with the flammable organic electrolytes widely adopted in lithium-ion batteries (LIBs), aqueous electrolytes intrinsically provide improved safety and their higher ionic conductivities favor high rate capability. 6,7 These features promote the recent renaissance of RAZBs with extensive researches on a variety of cathode materials, including manganese oxides, [8][9][10] Prussian blue analogues, 11,12 vanadium oxides, [13][14][15][16] and organic compounds.…”

Section: Introductionmentioning

confidence: 99%

“…[17][18][19][20] Nonetheless, state-of-the-art RAZBs are plagued by the issues associated with metallic Zn anodes, such as low plating/stripping efficiency, dendrite growth, and unstable Znelectrolyte interface along with water-induced side reactions (e.g., H 2 evolution and surface passivation). 4,21,22 To address these challenges, an efficient strategy is constructing hierarchical structures [23][24][25][26] or modification layers [27][28][29][30] on Zn anodes. Besides, electrolyte modulation is considered as a facile approach to stabilize metal anode by regulating the interface chemistry.…”

Section: Introductionmentioning

confidence: 99%

Non-concentrated aqueous electrolytes with organic solvent additives for stable zinc batteries

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“…[ 10 ] On the other hand, a much narrower thermodynamic stability window causes a higher risk of corrosion in the Zn anode. [ 11–19 ] Recent studies have described the construction of robust solid electrolyte interphases (SEIs) for Zn anodes. For example, the addition of a part of the organic electrolyte into an aqueous solution has been reported to apply dimethyl sulfoxide (DMSO) to form sulfur‐containing SEI [ 20 ] and introducing Zn 2+ conductive layers, such as ZnS [ 21 ] and ZnO [ 1 ] by pretreatment of Zn anode.…”

Section: Introductionmentioning

confidence: 99%

Calendar Life of Zn Batteries Based on Zn Anode with Zn Powder/Current Collector Structure

et al. 2021

Advanced Energy Materials

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Zn foil is widely used for studying the stability and dendrite formation behavior of Zn anodes. The reported long cycling life of rechargeable Zn batteries (RZBs) is obtained by testing a battery immediately after its fabrication neglecting the aging effects. The cycling performance demonstrated cannot, however, have practical applications. Using Zn foil as both the working electrode and current collector will cause many problems when the battery is scaled up. A Zn powder (Zn‐P)/current collector configuration is more practical. In this work, the corrosion of the Zn‐P@Cu anode‐induced cell swelling is first quantitatively studied. During the aging process of the Zn‐P@Cu electrode, hydrogen forms on the surface of Cu and the Zn‐P dissolves resulting in morphological changes. These phenomena can be attributed to galvanic corrosion between Cu and Zn. To address this issue, tin with a higher overpotential for hydrogen generation is plated on Cu surface. The results indicate that hydrogen evolution is ameliorated. With a low NP ratio (mass) of 10:7, considerably better storage and cycling performance are achieved for Zn‐P@Cu//MnO2. These results highlight the need to focus on the calendar life of RZBs and corrosion of the Zn anode.

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Dendrites in Zn‐Based Batteries

Abstract: Metal batteries (MBs, such as Zn, [1] Li, [2] Al, [3] etc.) possess a variety of advantages because they directly employ metals as

Cited by 784 publications

References 298 publications

Toward Practical High‐Areal‐Capacity Aqueous Zinc‐Metal Batteries: Quantifying Hydrogen Evolution and a Solid‐Ion Conductor for Stable Zinc Anodes

Toward Practical High‐Areal‐Capacity Aqueous Zinc‐Metal Batteries: Quantifying Hydrogen Evolution and a Solid‐Ion Conductor for Stable Zinc Anodes

Non-concentrated aqueous electrolytes with organic solvent additives for stable zinc batteries

Calendar Life of Zn Batteries Based on Zn Anode with Zn Powder/Current Collector Structure

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