Zincophilic Electrode Interphase with Appended Proton Reservoir Ability Stabilizes Zn Metal Anodes

Zn metal with high specific capacity and low redox potential is deemed to be an ideal anode material for aqueous zinc-ion batteries (ZIBs). However, the serious dendrite problems induced by the uneven deposition of zinc shorten the service life and hinder the development of ZIBs. According to the nucleation and growth mechanism, the charge distribution at the anode interface is the critical factor affecting the deposition morphology. Herein, CF4 plasma technology is applied for the first time to in situ modification of the Zn anode, and then, the uniform nanoscale ZnF2 particles are formed. Due to the excellent ionic conductivity and poor electronic conductivity of ZnF2, the ion and electron distribution at the anode interface is orderly regulated, thus guiding uniform and reversible deposition behavior and restraining the dendrite growth. As a result, the Zn@ZnF2-5 anode exhibits low nucleation overpotential (16 mV), long cycle life (2500 h at 1 mA cm–2 and 1 mA h cm–2), and excellent resistance to high current density (20 mA cm–2) and high discharge depth (16%). Meanwhile, the Zn@ZnF2-5|I2@AC full battery shows remarkable cycle stability (1000 cycles) with ∼10% discharge depth of the anode. The novel and practical CF4 plasma in situ modification strategy provides a new idea for the interface modification of zinc anode.

Section: Introductionmentioning

confidence: 99%

Controllable CF₄ Plasma In Situ Modification Strategy Enables Durable Zinc Metal Anode

Zhou

et al. 2023

“…The fast development of electric vehicle, aviation, and portable electronic devices has given rise to the demand for next-generation batteries. − However, the conventional lithium-ion batteries (LIBs) fail to meet the ever-growing technical requirements because of the limited theoretical capacity. − In recent years, the Li metal anode has been recognized as an ultimate candidate due to its high specific capacity (3860 mAh g –1 ), low redox potential (−3.04 V vs SHE), and low density (0.534 g cm –3 ). , However, the application of commercial lithium-metal batteries is hampered by the unstable solid electrolyte interphase (SEI) and undesirable dendrite formation . The large volume change may lead to breakdown of the SEI.…”

Section: Introductionmentioning

confidence: 99%

Lithiophilic and Anticorrosive Cu Current Collector via Dual-Bonded Porous Polymer Coating for Stable Lithium-Metal Batteries

Chen

Lin

et al. 2023

Self Cite

Li metal is the ultimate anode material for nextgeneration high-energy-density rechargeable batteries. However, the uncontrollable growth of Li dendrites and low Coulombic efficiency (CE) prevent it from practical applications in Li metal batteries (LMBs). Here, a facile and low-cost strategy is developed to decorate a Cu current collector with a self-assembled γ-aminopropyltrimethoxysilane (γ-APS) film. The thin polymer film with nanopores promotes the formation of cobblestone-like Li deposition and suppresses Li-dendrite formation due to its low surface energy. The protecting layer not only increases the lithiophilicity of the Cu current collector but also alleviates the ambient corrosion and galvanic corrosion in practical use. Owing to these advantages, the half cell using γ-APS-Cu collectors exhibits a high average CE value of 99.2% for 100 cycles. The symmetric cell of γ-APS-Cu@Li shows an improved lifespan of 1400 h with a small voltage hysteresis of 12 mV at 0.5 mA cm −2 . The full cell assembled with LiFePO 4 (LFP) cathodes and γ-APS-Cu@Li anodes delivers a high capacity of 136 mAh g −1 after 600 cycles at 0.5C.

“…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 .…”

Section: Introductionmentioning

confidence: 99%

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

Zhang

et al. 2023

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.