Insights into the Structure Stability of Prussian Blue for Aqueous Zinc Ion Batteries

Li, Zhuxin; Liu, Tingting; Meng, Ruijin; Gao, Lujie; Zou, Yiping; Peng, Peng; Shao, Yuying; Liang, Xiao

doi:10.1002/eem2.12108

Cited by 113 publications

(64 citation statements)

References 36 publications

(46 reference statements)

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“…f) Long‐term cycling stability of Zn–I 2 batteries with starch cathodes under a high current density of 10 A g −1 . g) Literature survey of rechargeable Zn batteries: Zn 0.25 V 2 O 5 ∙nH 2 O//Zn, [ 21 ] K 1.28 Ni[Fe(CN) 6 ] 0.821 ∙2.64H 2 O//Zn, [ 22 ] LiMn 2 O 4 //Zn, [ 23 ] MnO 2 //Zn, [ 24 ] I 2 ‐NPC//Zn, [ 25 ] I 2 ‐ACC//Zn, [ 8a ] I 2 ‐C‐50//Zn, [ 8d ] H 2 O/I 2 //Zn‐BTC@Zn, [ 4a ] H 2 O/I 2 //Zn@ZIF‐8, [ 26 ] and I 2 ‐Nb 2 CTi x //Zn. [ 9 ]…”

Section: Resultsmentioning

confidence: 99%

Polyiodide Confinement by Starch Enables Shuttle‐Free Zn–Iodine Batteries

et al. 2022

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large-scale energy-storage systems. [2] Aqueous zinc-based batteries with high safety and low cost provide a new opportunity for energy storage on a large scale. [3] Among the series of zinc-based batteries, the rechargeable zinc-iodine (Zn-I 2 ) battery is promising owing to abundant reserves of iodine in seawater (55 µg L −1 ), [4] high specific capacity (211 mAh g iodine −1), [5] and high discharge potential plateau (1.38 V vs Zn/Zn 2+ ). [6] Besides, the liquid-phase conversion mechanism of I − /I 2 in cathode endows a Zn-I 2 system with excellent rate capability. [7] However, the state-of-the-art Zn-I 2 batteries are still far from satisfactory due to the challenges of intermediates dissolution as well as Zn-anode corrosion. [4a] In aqueous electrolytes, Zn-I 2 batteries present a reversible I − /I 2 redox reaction, in which polyiodide species work as the intermediate state. [7] However, highly soluble polyiodide intermediates cause the serious shuttle effect, leading to irreversible loss of active mass. Even worse, the direct reaction between shuttling polyiodide and Zn anodes will further aggravate serious Zn corrosion and consumption, leading to the low Coulombic efficiency (CE), and limited durability of Zn-I 2 batteries. Therefore, inhibiting the shuttle effect of polyiodide is of great importance to stabilize the I 2 cathode and alleviate the Zn corrosion toward high-cyclability Zn-I 2 batteries. AqueousZn-iodine (Zn-I 2 ) batteries have been regarded as a promising energy-storage system owing to their high energy/power density, safety, and cost-effectiveness. However, the polyiodide shuttling results in serious active mass loss and Zn corrosion, which limits the cycling life of Zn-I 2 batteries. Inspired by the chromogenic reaction between starch and iodine, a structure confinement strategy is proposed to suppress polyiodide shuttling in Zn-I 2 batteries by hiring starch, due to its unique double-helix structure. In situ Raman spectroscopy demonstrates an I 5 − -dominated I − /I 2 conversion mechanism when using starch. The I 5 − presents a much stronger bonding with starch than I 3 − , inhibiting the polyiodide shuttling in Zn-I 2 batteries, which is confirmed by in situ ultraviolet-visible spectra. Consequently, a highly reversible Zn-I 2 battery with high Coulombic efficiency (≈100% at 0.2 A g −1 ) and ultralong cycling stability (>50 000 cycles) is realized. Simultaneously, the Zn corrosion triggered by polyiodide is effectively inhibited owing to the desirable shuttling-suppression by the starch, as evidenced by X-ray photoelectron spectroscopy analysis. This work provides a new understanding of the failure mechanism of Zn-I 2 batteries and proposes a cheap but effective strategy to realize high-cyclability Zn-I 2 batteries.The ORCID identification number(s) for the author(s) of this article can be found under https://doi.org/10.1002/adma.202201716.

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Section: Resultsmentioning

confidence: 99%

Polyiodide Confinement by Starch Enables Shuttle‐Free Zn–Iodine Batteries

et al. 2022

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“…[1][2][3] The cathode in a ZIB is required to have an open structure enabling easy intercalation and deintercalation of Zn(II) ions, during discharging and charging processes, to maximize energy storage via diffusion and Faradaic mechanisms. A variety of crystalline transition metal oxides [6][7][8][9][10] and Prussian blue analogues [11][12][13][14] endowed with channel dimensions in excess of 1.5 Å [which is approximately twice the ionic radius of Zn(II) ion] have been deployed as cathodes in ZIBs.…”

Section: Introductionmentioning

confidence: 99%

ZnV₂O₄‐Textured Carbon Composite Contacting a ZIF‐8 MOF Layer for a High Performance Non‐Aqueous Zinc‐Ion Battery

Naskar

Deepa

2021

Batteries & Supercaps

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Non‐aqueous zinc‐ion battery (ZIB) comprising a zinc vanadate@textured carbon (ZnV2O4@TC) composite cathode and Zn‐anode demonstrates an improved Zn(II)‐ion storage response, in terms of cyclability (230 mAh g−1 after 200 cycles, 84.9 % retention) and rate capability compared to pristine ZnV2O4 (175 mAh g−1 after 200 cycles, 45.4 % retention). TC reduces the aggregation of ZnV2O4 nanoparticles, allows abundant interaction with electrolyte, affords short ion diffusion pathways, serves as electrically conducting interconnects, and buffers the volume alterations thus imparting rapid kinetics and improved cycling stability. This performance is even better by the inclusion of a ZIF‐8 metal‐organic framework (MOF) layer at the separator, facing the cathode. ZIF‐8 due to its nanoporous structure encompassing Zn−N based polyhedral clusters, efficiently confines Zn(II) ions at cathode during discharge and allows their facile diffusion through its open channels during charge thus maximizing Zn(II) ion storage capacity and reversibility and its highly crystalline robust structure also enhances the ZIB durability. This achievement is in line with the development of cost‐effective, easily implementable non‐aqueous ZIB that avoids the issues associated with aqueous electrolyte of limited potential stability window, corrosion of current collectors over time, and cell degradation and also offers long term stability and capacity.

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“…Owing to its abundant sources and environmental friendliness, aqueous batteries with monovalent (Na + and K + ) and multivalent (Mg 2+ , Zn 2+ , and Al 3+ ) cations have gained extensive attention. [2][3][4][5][6] Zinc is a nontoxic, low-cost, and earth-abundant material (about 300 times of lithium), which has a high theoretical capacity (820 mA h g −1 ). [7][8][9][10][11] Thus, aqueous zinc-ion batteries (ZIBs) using zinc as anodes have been developed rapidly in recent years.…”

Section: Introductionmentioning

confidence: 99%

Weaker Interactions in Zn²⁺ and Organic Ion‐pre‐intercalated Vanadium Oxide toward Highly Reversible Zinc‐ion Batteries

Zhang

Sun

et al. 2020

Energy & Environ Materials

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Driven by safety issues, environmental concerns, and high costs, rechargeable aqueous zinc‐ion batteries (ZIBs) have received increasing attention in recent years owing to their unique advantages. However, the sluggish kinetics of divalent charge Zn2+ in the cathode materials caused by the strong electrostatic interaction and their unsatisfactory cycle life hinder the development of ZIBs. Herein, organic cations and Zn2+ ions co‐pre‐inserted vanadium oxide ([N(CH3)4]0.77,Zn0.23)V8O20·3.8H2O are reported as the cathode for ultra‐stable aqueous ZIBs, in which the weaker electrostatic interactions between Zn2+ and organic ion‐pinned vanadium oxide can induce the high reversibility of Zn2+ insertion and extraction, thereby improving the cycle life. It is demonstrated that ([N(CH3)4]0.77,Zn0.23)V8O20·3.8H2O cathodes deliver a discharge capacity of 181 mA h g−1 at 8 A g−1 and ultra‐long life span (99.5% capacity retention after 2000 cycles). A reversible Zn2+/H+ ions (de)intercalation storage process and pseudocapacitive charge storage are characterized. The weaker interactions between organic ion and Zn2+ open a novel avenue for the design of highly reversible cathode materials with long‐term cycling stability.

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Insights into the Structure Stability of Prussian Blue for Aqueous Zinc Ion Batteries

Cited by 113 publications

References 36 publications

Polyiodide Confinement by Starch Enables Shuttle‐Free Zn–Iodine Batteries

Polyiodide Confinement by Starch Enables Shuttle‐Free Zn–Iodine Batteries

ZnV₂O₄‐Textured Carbon Composite Contacting a ZIF‐8 MOF Layer for a High Performance Non‐Aqueous Zinc‐Ion Battery

Weaker Interactions in Zn²⁺ and Organic Ion‐pre‐intercalated Vanadium Oxide toward Highly Reversible Zinc‐ion Batteries

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Insights into the Structure Stability of Prussian Blue for Aqueous Zinc Ion Batteries

Cited by 113 publications

References 36 publications

Polyiodide Confinement by Starch Enables Shuttle‐Free Zn–Iodine Batteries

Polyiodide Confinement by Starch Enables Shuttle‐Free Zn–Iodine Batteries

ZnV2O4‐Textured Carbon Composite Contacting a ZIF‐8 MOF Layer for a High Performance Non‐Aqueous Zinc‐Ion Battery

Weaker Interactions in Zn2+ and Organic Ion‐pre‐intercalated Vanadium Oxide toward Highly Reversible Zinc‐ion Batteries

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Resources

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ZnV₂O₄‐Textured Carbon Composite Contacting a ZIF‐8 MOF Layer for a High Performance Non‐Aqueous Zinc‐Ion Battery

Weaker Interactions in Zn²⁺ and Organic Ion‐pre‐intercalated Vanadium Oxide toward Highly Reversible Zinc‐ion Batteries