Copper Hexacyanoferrate Solid‐State Electrolyte Protection Layer on Zn Metal Anode for High‐Performance Aqueous Zinc‐Ion Batteries

Liu, Yu; Li, Yuanxia; Huang, Xiaomin; Cao, Heng; Zheng, Qiaoji; Huo, Yujing; Zhao, Jianlong; Lin, Dunmin; Xu, Bingang

doi:10.1002/smll.202203061

Cited by 53 publications

(48 citation statements)

References 73 publications

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“…Usually, surface modification is realized by an artificial layer that is thin and robust, stable in electrolytes, as well as ion (electron) conductive. , Therefore, it can reduce side reactions and tolerate strain/stress caused by inhomogeneous growth. Moreover, the layer is preferably both hydrophilic and zincophilic. , Using Zn-plating process as an example, hydrophilic surface benefits electrolyte wetting and hydrated-ion desolvation. , The zincophilic surface promotes zinc-ion adsorption and uniform nucleation processes. − If all the processes occur at the same surface site, the mutual interference between them is inevitable. Moreover, it is difficult to achieve all the features at the same surface site.…”

Section: Introductionmentioning

confidence: 99%

Site-Selective Adsorption on ZnF₂/Ag Coated Zn for Advanced Aqueous Zinc–Metal Batteries at Low Temperature

et al. 2022

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Metallic Zn as a promising anode material of aqueous batteries suffers from severe parasitic reactions and notorious dendrite growth. To address these issues, the desolvation and nucleation processes need to be carefully regulated. Herein, Zn foils coated by ZnF2–Ag nanoparticles (ZnF2–Ag@Zn) are used as a model to modulate the desolvation and nucleation processes by hybrid surfaces, where Ag has a strong affinity to Zn adatoms and ZnF2 shows an intense adsorption to H2O. This selective adsorption of different species on ZnF2 and Ag reduces the mutual interference between two species. Therefore, ZnF2–Ag@Zn exhibits the electrochemical performance much better than ZnF2@Zn or Ag@Zn. Even at −40 °C, the full cells using ZnF2–Ag@Zn demonstrate an ultralong lifespan of 5000 cycles with a capacity retention of almost 100%. This work provides new insights to improve the performance of Zn metal batteries, especially at low temperatures.

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Section: Introductionmentioning

confidence: 99%

Site-Selective Adsorption on ZnF₂/Ag Coated Zn for Advanced Aqueous Zinc–Metal Batteries at Low Temperature

et al. 2022

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“…Designing artificial solid-electrolyte interphase (SEI) films on a Zn anode shows great potential to address the aforementioned issues. − Polymers with good flexibility, high ionic conductivity, and superior processability are regarded as an ideal substance for the generation of artificial SEI films. − However, most of polymer-based artificial SEI films exhibit high polarization and inferior selective access of Zn 2+ ions. Cui et al .…”

Section: Introductionmentioning

confidence: 99%

Highly Reversible Zinc Anode Enabled by a Cation-Exchange Coating with Zn-Ion Selective Channels

et al. 2022

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Rechargeable aqueous zinc-ion batteries (ZIBs) have attracted extensive attention due to their low cost and high safety. However, the critical issues of dendrite growth and side reactions on the Zn metal anode hinder the commercialization of ZIBs. Herein, we demonstrated that the formation of Zn 4 SO 4 (OH) 6 •5H 2 O byproducts is closely relevant to the direct contact between the Zn electrode and SO 4 2− /H 2 O. On the basis of this finding, we developed a cation-exchange membrane of perfluorosulfonic acid (PFSA) coated on the Zn surface to regulate the Zn plating/stripping behavior. Importantly, the PFSA film with abundant sulfonic acid groups could simultaneously block the access of SO 4 2− and H 2 O, accelerate the Zn 2+ ion transport kinetics, and uniformize the electrical and Zn 2+ ion concentration field on the Zn surface, thus achieving a highly reversible Zn plating/stripping process with corrosion-free and dendritefree behavior. Consequently, the PFSA-modified Zn anode exhibits high reversibility with 99.5% Coulombic efficiency and excellent plating/stripping stability (over 1500 h), subsequently enabling a highly rechargeable Zn-MnO 2 full cell. The strategy of the cation-exchange membrane proposed in this work provides a simple but efficient method for suppression of side reactions.

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“…On the anode side, Zn metal is the most commonly used anode material, which possesses high theoretical capacity (820 mAh g –1 ) and low electrochemical potential (−0.763 V vs SHE) . Despite the above merits, the unsatisfactory deposition/stripping Coulombic efficiency (CE), low utilization of the Zn metal anode resulting from dendrite growth, self-corrosion, and passivation issues severely deteriorate the lifespan and energy density of ZIBs. , Although many strategies including electrode structural design, , surface modification, − and Zn alloying , have been proposed to improve the electrochemical performance of Zn metal anodes, resolving these problems thoroughly is still difficult. It should be noticed that the Zn dendrites issue may be exponentially aggravated at high loading mass and high current densities, which will ruin the battery under practical conditions. , …”

Section: Introductionmentioning

confidence: 99%

Activating the Stepwise Intercalation–Conversion Reaction of Layered Copper Sulfide toward Extremely High Capacity Zinc-Metal-Free Anodes for Rocking-Chair Zinc-Ion Batteries

Wang

et al. 2021

ACS Appl. Mater. Interfaces

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Conventional zinc-ion batteries (ZIBs) are severely hindered by the inherent drawbacks of Zn metal anodes including dendrite growth, side reactions, and interface passivation. Developing intercalation-type anodes to fabricate rocking-chair ZIBs is a promising approach to overcome the above issues. However, the low capacity resulting from the limited transfer electron number of intercalation reactions impedes their practical applications. Herein, we report an effective strategy to break the capacity limit of layered CuS materials as a Zn-metal-free anode through activating its intrinsic conversion reaction. It is found that the preintercalation of cetyltrimethylammonium bromide in CuS (CuS@ CTMAB) significantly lowers the energy barrier of the conversion reaction, thus realizing a record-breaking capacity (367.4 mAh g −1 at 0.1 A g −1 ) as a Zn-metal-free anode based on the reversible conversion of Cu 2+ /Cu 0 . Theoretical calculation, ex situ microscopy, and spectroscopy results verify that the characteristic stepwise intercalation−conversion reaction route occurred in CuS@CTMAB. Moreover, the moderate structure transformation and good electronic conduction during the phase evolution process led to excellent cycling stability and high rate performance. Consequently, the rocking-chair ZIB full battery system utilizing CuS@CTMAB and Zn 2+preintercalated MnO 2 as the anode and cathode, respectively, exhibits exceptional capacity retention of 93.9% up to 8000 cycles at 2 A g −1 . Besides, the CuS@CTMAB anode is also compatible with high-voltage Prussian blue cathodes, demonstrating its outstanding practicality.

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Copper Hexacyanoferrate Solid‐State Electrolyte Protection Layer on Zn Metal Anode for High‐Performance Aqueous Zinc‐Ion Batteries

Cited by 53 publications

References 73 publications

Site-Selective Adsorption on ZnF₂/Ag Coated Zn for Advanced Aqueous Zinc–Metal Batteries at Low Temperature

Site-Selective Adsorption on ZnF₂/Ag Coated Zn for Advanced Aqueous Zinc–Metal Batteries at Low Temperature

Highly Reversible Zinc Anode Enabled by a Cation-Exchange Coating with Zn-Ion Selective Channels

Activating the Stepwise Intercalation–Conversion Reaction of Layered Copper Sulfide toward Extremely High Capacity Zinc-Metal-Free Anodes for Rocking-Chair Zinc-Ion Batteries

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Copper Hexacyanoferrate Solid‐State Electrolyte Protection Layer on Zn Metal Anode for High‐Performance Aqueous Zinc‐Ion Batteries

Cited by 53 publications

References 73 publications

Site-Selective Adsorption on ZnF2/Ag Coated Zn for Advanced Aqueous Zinc–Metal Batteries at Low Temperature

Site-Selective Adsorption on ZnF2/Ag Coated Zn for Advanced Aqueous Zinc–Metal Batteries at Low Temperature

Highly Reversible Zinc Anode Enabled by a Cation-Exchange Coating with Zn-Ion Selective Channels

Activating the Stepwise Intercalation–Conversion Reaction of Layered Copper Sulfide toward Extremely High Capacity Zinc-Metal-Free Anodes for Rocking-Chair Zinc-Ion Batteries

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Site-Selective Adsorption on ZnF₂/Ag Coated Zn for Advanced Aqueous Zinc–Metal Batteries at Low Temperature

Site-Selective Adsorption on ZnF₂/Ag Coated Zn for Advanced Aqueous Zinc–Metal Batteries at Low Temperature