A stable fluoride-based interphase for a long cycle Zn metal anode in an aqueous zinc ion battery

Li, Yuting; Yang, Sinian; Du, Hongxia; Liu, Yuqiu; Wu, Xiuting; Yin, Caishuo; Wang, Donghui; Wu, Xun; He, Zhangxing; Wu, Xianwen

doi:10.1039/d2ta03550b

Cited by 88 publications

(55 citation statements)

References 62 publications

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“…The NTP-C@Zn symmetrical cells can maintain stable cycling within 200 h and 160 h at 10 mA cm −2 and 20 mA cm −2 , respectively, followed by significant polarization increase. The phenomenon of the voltage increasing has also been observed and reported in the previous articles [48][49][50], which is mainly attributed to the occurrence of side reactions [51]. As for the cycling performance at a low current density, a stable cycling of Zn plating/stripping lasts over 860 h with a low overpotential (20 mV) at 0.5 mA cm −2 /0.5 mAh cm −2 , as shown in Figure 8(d).…”

Section: Energy Materials Advancessupporting

confidence: 79%

Regulating Uniform Zn Deposition via Hybrid Artificial Layer for Stable Aqueous Zn-Ion Batteries

et al. 2022

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Aqueous Zn-ion batteries (ZIBs) have great potential as promising candidates for next-generation energy conversion and storage devices, benefiting from competitive theoretical capacity, low cost, and high security. However, further applications of ZIBs are impeded by dendrite generation and side reactions. Herein, considering that Zn dendrites are caused by nonuniform metal deposition, involving uneven electric field and Zn2+ ion flux, a dual-functional carbon-coated NaTi2(PO4)3 (NTP-C) artificial protective layer with large surface area is constructed onto the surface of metallic Zn to stabilize Zn anode and regulate uniform Zn deposition. Benefiting from a synergistic strategy, NTP-C coating not only takes advantages of carbon to provide abundant Zn deposition sites to homogenize nucleation, adjust electric field distribution, and reduce local current density but also utilizes the ionic channel in NTP structure to modulate the distribution of Zn2+ flux at the same time. Consequently, the NTP-C@Zn symmetrical cell exhibits a stable cycling for more than 600 h with a low polarization (18.6 mV) at 1 mA cm−2/1 mAh cm−2. Especially, the NTP-C@Zn symmetrical cell even enables a steady plating/stripping process at a harsh condition (100 mA cm−2) without short circuit, indicating a potential application of high-load electrodes or supercapacitors. Furthermore, the NTP-C@Zn//α-MnO2 full cell also displays enhanced electrochemical performance for 1200 cycles with a capacity retention of 76.6% under 5 C (~1.5 A g−1). This work provides a synergistic strategy combining two protective mechanisms and delivers new inspirations for the improvement of stable Zn anode in aqueous ZIBs.

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Section: Energy Materials Advancessupporting

confidence: 79%

Regulating Uniform Zn Deposition via Hybrid Artificial Layer for Stable Aqueous Zn-Ion Batteries

et al. 2022

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“…The surface coating layer on a zinc anode that is similar to the solid electrolyte interface of a Li anode is an effective strategy for protecting the electrode, reducing the contact area between the electrode and electrolyte, inhibiting zinc corrosion, and guiding Zn 2+ uniform deposition. , At present, the coating types that have been reported can be classified into the following categories: (1) inorganic coating layers, including Zn-based montmorillonite (MMT), ZrO 2 , TiO 2 , nano-Au particles, CaCO 3 , and CaF 2 , which can protect zinc anodes with high stability and corrosion resistance, (2) polymer coatings, such as cyanoacrylate, poly(vinyl butyral) (PVB), polyacrylonitrile (PAN), and β-polyvinylidene fluoride (β-PVDF), whose materials are flexible and cheaper, (3) metal–organic framework layer, for instance, ZIF-8, and (4) carbon nanofiber (CNF), graphene, porous carbon, graphene oxide, and other carbon-based materials. As a result of their high electronic conductivities, perfect chemical stabilities, and large specific surface areas (SSAs), carbon materials on zinc surfaces can uniformly distribute charge and regulate Zn 2+ flux to stabilize Zn anodes. ,,, In the stage of initial nucleation, Zn 2+ prefers to be deposited on substrates with an identical crystal lattice .…”

Section: Introductionmentioning

confidence: 99%

Copper Nanoparticle-Modified Carbon Nanofiber for Seeded Zinc Deposition Enables Stable Zn Metal Anode

Yang

et al. 2022

ACS Sustainable Chem. Eng.

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Challenges with the Zn anode for aqueous zinc ion batteries have hindered their practical applications, such as uncontrollable formation of the Zn dendrite and serious side reactions. Herein, we fabricate a flexible coating layer with porous and conductive carbon networks (Cu@CNFs) by a simple electrospinning method to construct a stable Zn anode. It can uniformly distribute the charge, regulate the Zn 2+ flux, and stabilize the zinc anode. Moreover, the zincopilic Cu nanoparticles (CuNPs) in the coating layer act as nucleation seeds to facilitate the homogeneous deposition of Zn and inhibit its dendrite growth. Density functional theory calculations have further demonstrated the zincophilicity of the CuNPs seeds. As a result, the Cu@CNFs-Zn anode demonstrates a lower nucleation overpotential (58.3 mV at 5.0 mA cm −2 ) and a higher Coulombic efficiency compared with bare Zn and CNFs-Zn anodes. Remarkably, the Cu@CNFs-Zn anode can provide a stable cycle over 2200 h at 1.0 mA cm −2 with a capacity of 1.0 mAh cm −2 . Moreover, the Cu@CNFs-Zn//V 2 O 5 battery achieves a superior cyclability up to 1000 cycles at 0.5A g −1 , which is attributed to the large surface areas of CNFs and the zincophilicity of the Cu@CNFs coating.

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“…51 As reported, the F atoms of Zn−F bonds can bring the imbalance of electron cloud distribution, which will accelerate the Zn 2+ diffusion and lead to fast Zn 2+ transfer kinetics. 28,29,52 Accordingly, the Zn deposition on LF@Zn is prone to occur underneath the LaF 3 coating and present a fast Zn 2+ transfer kinetics. Finite element simulation in COMSOL was further implemented to explore the effect of the LaF 3 layer through simulating the current density distribution at the anode−electrolyte interface.…”

Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

“…Surface modification is an effective way of protecting Zn anodes from dendrite growth and corrosion by reconstructing the electrolyte–anode interface. − Among the protective layers, metal fluorides were proved to be the ideal protector for Zn anodes with various kinds of strategies, including in situ formation by electrolytes, reactions with the Zn anode, artificial coatings, and so on. It has been confirmed that the F-rich interface has a relatively high ionic conductivity and can greatly improve the electrochemical stability of the Zn anode, owing to the strong electronegativity of F atoms . Although fluoride-based protective layers make sense for protecting the Zn anode, the AZMBs present low volumetric energy density and poor rate capability due to the increased Zn 2+ transport distance by the thick glass fiber separators. , It is expected to be solved by substituting and discarding the traditional glass fiber separators.…”

Section: Introductionmentioning

confidence: 99%

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Fluoride-Based Stable Quasi-Solid-State Zinc Metal Battery with Superior Rate Capability

Zhang

et al. 2023

ACS Appl. Mater. Interfaces

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Aqueous zinc metal batteries are limited in practical applications due to their short lifespans. Herein, a LaF 3 -coated Zn anode (LF@Zn) is investigated to induce the uniform Zn deposition and successfully build a separator-free quasi-solid-state zinc metal battery. The LF@Zn enables smooth and dendrite-free Zn deposition, owing to the homogeneous Zn 2+ flux regulated by the LaF 3 -based quasi-solid-state electrolyte. It can also suppress the corrosion side reactions by modulating the [Zn(H 2 O) 6 ] 2+ solvation sheath. The polarization of plating and stripping is relatively modest due to the reduced diffuse energy of desolvated Zn 2+ in the quasi-solid-state electrolyte. In a separator-free symmetric cell, the LF@Zn anode shows a significantly prolonged lifespan of over 1300 h at 2 mA cm −2 and a superior rate performance with only 156 mV at an ultrahigh current density of 50 mA cm −2 . A LF@Zn// VO 2 quasi-solid-state full cell exhibits outperforming rate capability and a long cyclic performance for up to 3000 cycles at 6.0 A g −1 . A stable Zn anode is established in this work with a fluoride-based quasi-solid-state electrolyte, opening up a new avenue for protecting metal anodes.

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A stable fluoride-based interphase for a long cycle Zn metal anode in an aqueous zinc ion battery

Abstract: Rechargeable aqueous zinc ion batteries (AZIBs) at present have attracted extensive attention as a promising energy storage system to replace the traditional lithium-ion batteries because of their high energy density,...

Cited by 88 publications

References 62 publications

Regulating Uniform Zn Deposition via Hybrid Artificial Layer for Stable Aqueous Zn-Ion Batteries

Regulating Uniform Zn Deposition via Hybrid Artificial Layer for Stable Aqueous Zn-Ion Batteries

Copper Nanoparticle-Modified Carbon Nanofiber for Seeded Zinc Deposition Enables Stable Zn Metal Anode

Fluoride-Based Stable Quasi-Solid-State Zinc Metal Battery with Superior Rate Capability

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