Artificial N-doped Graphene Protective Layer Enables Stable Zn Anode for Aqueous Zn-ion Batteries

Hao, Yutong; Zhou, Jiahui; Wei, Guangling; Liu, Anni; Zhang, Yixin; Yang, Mei; Lu, Baoping; Luo, Man; Xie, Man

doi:10.1021/acsaem.1c01306

Cited by 52 publications

(34 citation statements)

References 53 publications

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“…The reactions often caused the formation of irreversible by‐products (such as Zn 4 SO 4 (OH) 6 ·5H 2 O), and the corresponding XRD patterns are shown in Figure 4c. [ 30 ] The well anticorrosion of ROZ@Zn foils significantly avoiding the hydrogen evolution was mainly benefited from the desolvation and barrier water effect of ROZ coating, as the result of the compact surface of the ROZ coating. As shown in Figure S11, Supporting Information, the SEM images and elemental mapping images of ROZ@Zn were characterized only in 1 µm.…”

Section: Resultsmentioning

confidence: 99%

Crystal Plane Reconstruction and Thin Protective Coatings Formation for Superior Stable Zn Anodes Cycling 1300 h

Liu

Cai

et al. 2022

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820 mAh g −1 ), which is attractive as the anode for aqueous batteries. [1] Based on these advantages, various zinc-metal batteries employing aqueous electrolyte with high safety (such as Zn-ion batteries, Zn-air batteries, and Zn-redox-flow batteries) have been intensively investigated. [2] Unfortunately, the poor chemical stability and electrochemical irreversibility of the Zn metal anode limit the practical applications of Zn rechargeable batteries. [3] Undesired side reactions and dendrite growth are two main challenges for aqueous Zn metal batteries.The nonuniform Zn 2+ flux of the interfacial layer on Zn can cause variations in the localized current density and ion depletion during cycling, thus resulting in large overpotentials and dendrite growth. [4] Continued dendrite growth can lead to penetration of the separator and cause short circuiting of cells. Moreover, nonuniform Zn plating/stripping may lead to further undesired side reactions between Zn and aqueous electrolytes. [5] To solve this problem, the interfacial coatings on the Zn surface are used to regulate Zn 2+ flux and suppress Zn dendrite growth, which finally avoids the well-known "tip effect." [6] In addition, the texture designs of the Zn metal surface play an important role in the orientation of the zinc crystal by plating. [7] Due to the smooth equipotential surface of Zn-(001) planes and the stronger adsorption energy of parallel direction between the (001) plane surface and Zn atom, the (001) crystal plane can guide plating sequentially parallel to it. [8] For example, Archer's group and Liang's group reported that the Zn foil exhibiting a preferred (001) texture by plastic deformation could suppress the rough plating/stripping landscape and promote uniform deposition along (001) planes. [9] Undesirable side reactions including chemical corrosion and hydrogen evolution mainly occurred at the interface between the Zn metal surface and electrolytes. [10] They would block the utilization of Zn, and then lead to electrolytes consumption and low Coulombic efficiency. [11] To solve this problem, various kinds of coatings have been made, which mainly include inorganic coating, polymer coating, organic, and inorganic composite coating. [12] They could block water molecules from reaching the Zn surface, and then improve the stability and reversibility of Zn metal anode. [13] However, thicker coatings were usually chosen to guarantee long-acting anticorrosion effect and retard the growth of dendrites, which meant the long route of ionic Some new insights into traditional metal pretreatment of anticorrosion for high stable Zn metal anodes are provided. A developed pretreatment methodology is employed to prefer the crystal plane of polycrystalline Zn and create 3.26 µm protective coatings mainly consisting of organic polymers and zinc salts on Zn foils (ROZ@Zn). In this process, Zn metal exhibits a surface-preferred (001) crystal plane proved by electron backscattered diffraction. Preferred (001) crystal planes and ROZ coatings can regulate ...

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Section: Resultsmentioning

confidence: 99%

Crystal Plane Reconstruction and Thin Protective Coatings Formation for Superior Stable Zn Anodes Cycling 1300 h

Liu

Cai

et al. 2022

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“…Rechargeable zinc batteries (RZBs) employing mild aqueous electrolytes hold promise for large-scale energy storage applications owing to the advantages of the metallic Zn anode, including intrinsic safety, globally abundant reserves, and high gravimetric and volumetric capacity (820 mAh g –1 and 5855 mAh cm –3 ). − Moreover, the mildly acidic aqueous electrolytes (e.g., ZnSO 4 solution) with high ionic conductivity can promote the rechargeability of traditional oxide cathode materials (e.g., MnO 2 and V 2 O 5 ), which generally suffer from severe capacity fade in strongly acidic or alkaline electrolytes. , However, state-of-the-art RZBs are hindered by the irreversibility of Zn anodes associated with side reactions and metallic dendrite formation. , Since the redox potential of Zn 2+ /Zn is −0.76 V versus the standard hydrogen electrode (SHE), water decomposition along with the hydrogen evolution reaction (HER) inevitably occurs on Zn during battery rest and operation, leading to the severe corrosion of Zn anodes . Moreover, the HER elevates the local pH value and provokes the formation of inactive byproducts (e.g., Zn(OH) 2 and Zn 4 SO 4 (OH) 6 · x H 2 O), resulting in a low Coulombic efficiency (CE) and a degradation of battery performance. − In addition, the nonuniform Zn 2+ flux originating from heterogeneous nucleation sites and concentration polarization results in rampant dendritic Zn deposition, which accelerates parasitic reactions and shortens the battery lifespan. , …”

Section: Introductionmentioning

confidence: 99%

Stabilizing Zinc Electrodes with a Vanillin Additive in Mild Aqueous Electrolytes

Zhao

Liu

Fan

et al. 2021

ACS Appl. Mater. Interfaces

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Metallic zinc (Zn) is an attractive anode material to use for building an aqueous battery but suffers from dendritic growth and waterinduced corrosion. Herein, we report the use of vanillin as a bifunctional additive in aqueous electrolyte to stabilize the Zn electrochemistry. Computational, spectroscopic, and electrochemical studies suggest that vanillin molecules preferentially absorb in parallel on the Zn surface to homogenize the Zn 2+ plating and favorably coordinate with Zn 2+ to weaken the solvation interaction between H 2 O and Zn 2+ , resulting in a compact, dendrite-free Zn deposition and a stable electrode−electrolyte interface with suppressed hydrogen evolution and hydroxide sulfate formation. In the formulated 2 M ZnSO 4 electrolyte with 5 mM vanillin, the Zn anode sustains high areal capacity (10 mAh cm −2 at 1 mA cm −2 ) and remarkable cycling stability (1 mAh cm −2 for 1000 h) in a Zn|Zn cell and high average Coulombic efficiency (99.8%) in a Zn|Cu cell, significantly outperforming the cells without vanillin. Furthermore, the vanillin additive supports stable operation of full Zn|V 2 O 5 batteries and is readily generalized to a Zn(CF 3 SO 3 ) 2based electrolyte. This work offers a facile and cost-effective strategy of electrolyte design to enable high-performance aqueous Zn batteries.

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“…It is worth mentioning that the DOD values of 4.1–41.3% in our Zn anode are much higher than those in most reported papers in full cells (Table S4). ,− Due to the use of the high-DOD Zn anode, the energy and power density at the cell level could be enhanced, and the highest energy densities achieved with MnO 2 -, AC-, and I 2 /AC-based full cells are 195.3, 52.58, and 30.73 Wh kg –1 , respectively (Figure S24).…”

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confidence: 99%

Efficient Zn Metal Anode Enabled by O,N-Codoped Carbon Microflowers

Jin

Zhang

et al. 2022

Nano Lett.

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Zinc metal anodes show great promise for cheap and safe energy storage devices. However, it remains challenging to regulate highly efficient Zn plating/stripping under a high depth of discharge (DOD). Guided by density functional theory calculation, we here synthesized an oxygen- and nitrogen-codoped carbon superstructure as an efficient host for high-DOD Zn metal anodes through rational monomer selection, polymer self-assembly, and structure-preserved carbonization. With microscale 3D hierarchical structures, microcrystalline graphitic layers, and zincophilic heteroatom dopants, a flower-shaped carbon (Cflower) host could guide Zn nucleation and growth in a heteroepitaxial mode, affording horizontal plating with a high Coulombic efficiency (CE) and long life. As a demonstration, the Cflower-hosted Zn anode was paired with both battery and supercapacitor cathodes and delivered large capacity/capacitance, fast rates, long life, and ca. 100% CE even under a high DOD, outclassing hostless Zn-based devices. As they possess cheap, scalable, and efficient features, Cflower hosts hold the potential for practical zinc-metal-based energy devices.

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Artificial N-doped Graphene Protective Layer Enables Stable Zn Anode for Aqueous Zn-ion Batteries

Cited by 52 publications

References 53 publications

Crystal Plane Reconstruction and Thin Protective Coatings Formation for Superior Stable Zn Anodes Cycling 1300 h

Crystal Plane Reconstruction and Thin Protective Coatings Formation for Superior Stable Zn Anodes Cycling 1300 h

Stabilizing Zinc Electrodes with a Vanillin Additive in Mild Aqueous Electrolytes

Efficient Zn Metal Anode Enabled by O,N-Codoped Carbon Microflowers

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