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Title: Zn 2+ Induced Phase Transformation of K 2 MnFe(CN) 6 Boosts Highly Stable Zinc‐Ion Storage

Journal Article · · Advanced Energy Materials
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  1. School of Advanced Materials Peking University Shenzhen Graduate School Shenzhen 518055 P. R. China
  2. Institute of Marine Biomedicine Shenzhen Polytechnic Shenzhen 518055 P. R. China
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Abstract Prussian blue analogues (PBAs), featuring an open framework for accommodating large ions and tunable valence states, have garnered wide interest in the context of aqueous zinc‐ion batteries (ZIBs). However, PBAs in ZIBs currently still suffer from low capacity and poor cycling stability due to structural instability. Here a K 2 MnFe(CN) 6 cathode achieving a very stable capacity of 100 mAh g −1 is reported in a ZIB charged/discharged to 400 cycles. Interestingly, such a stable capacity is attributed to the fact that the K 2 MnFe(CN) 6 cathode is gradually transformed to rhombohedral K 2 Zn 3 [Fe(CN) 6 ] 2 , a process that is induced by Zn 2+ insertion. The mechanism of the phase transformation is further investigated through ab initio calculations and detailed characterizations. The inserted Zn 2+ is found to induce an intense Jahn‐Teller effect of the trivalent manganese, resulting in a strong lattice distortion. Coupled with the disproportionation reaction of manganese, the MnN 6 octahedra are replaced by ZnN 4 tetrahedra and produce the new K 2 Zn 3 [Fe(CN) 6 ] 2 phase eventually. The robust structure of the resulting K 2 Zn 3 [Fe(CN) 6 ] 2 phase contains wider channels for accommodating divalent ions and thus enables highly stable and reversible storage of Zn 2+ ions. The findings of this work lead to a new understanding on the evolution of PBAs in ZIBs, and provide a promising cathode material.

Sponsoring Organization:
USDOE
Grant/Contract Number:
AC02-06CH11357
OSTI ID:
1798912
Journal Information:
Advanced Energy Materials, Journal Name: Advanced Energy Materials Journal Issue: 31 Vol. 11; ISSN 1614-6832
Publisher:
Wiley Blackwell (John Wiley & Sons)Copyright Statement
Country of Publication:
Germany
Language:
English

References (46)

Recent Advances in Zn-Ion Batteries journal August 2018
Electrochemical Activation of Manganese‐Based Cathode in Aqueous Zinc‐Ion Electrolyte journal June 2020
High-Capacity Aqueous Potassium-Ion Batteries for Large-Scale Energy Storage journal October 2016
Activating C‐Coordinated Iron of Iron Hexacyanoferrate for Zn Hybrid‐Ion Batteries with 10 000‐Cycle Lifespan and Superior Rate Capability journal June 2019
Towards High-Voltage Aqueous Metal-Ion Batteries Beyond 1.5 V: The Zinc/Zinc Hexacyanoferrate System journal September 2014
Size Engineering and Crystallinity Control Enable High‐Capacity Aqueous Potassium‐Ion Storage of Prussian White Analogues journal October 2018
Vacancy-Free Prussian Blue Nanocrystals with High Capacity and Superior Cyclability for Aqueous Sodium-Ion Batteries journal May 2015
Lattice contractions and expansions accompanying the electrochemical conversions of Prussian blue and the reversible and irreversible insertion of rubidium and thallium ions journal April 1996
An electrochemical investigation of the aging of copper hexacyanoferrate during the operation in zinc-ion batteries journal December 2016
Mixed copper-zinc hexacyanoferrates as cathode materials for aqueous zinc-ion batteries journal May 2019
Recent progress and perspectives on aqueous Zn-based rechargeable batteries with mild aqueous electrolytes journal July 2019
Fundamentals and perspectives of electrolyte additives for aqueous zinc-ion batteries journal January 2021
Hybrid Aqueous/Non-aqueous Electrolyte for Safe and High-Energy Li-Ion Batteries journal May 2018
Improving the cycle life of a high-rate, high-potential aqueous dual-ion battery using hyper-dendritic zinc and copper hexacyanoferrate journal February 2016
A rechargeable Na-Zn hybrid aqueous battery fabricated with nickel hexacyanoferrate and nanostructured zinc journal July 2016
Prussian blue nanocubes as cathode materials for aqueous Na-Zn hybrid batteries journal July 2017
The porous carbon derived from water hyacinth with well-designed hierarchical structure for supercapacitors journal October 2017
Structural-electrochemical relations in the aqueous copper hexacyanoferrate-zinc system examined by synchrotron X-ray diffraction journal November 2017
Copper hexacyanoferrate with a well-defined open framework as a positive electrode for aqueous zinc ion batteries journal January 2015
Advanced rechargeable zinc-based batteries: Recent progress and future perspectives journal August 2019
Theoretical Study of the Structural Evolution of a Na 2 FeMn(CN) 6 Cathode upon Na Intercalation journal May 2015
Before Li Ion Batteries journal November 2018
Asymmetric K/Li-Ion Battery Based on Intercalation Selectivity journal November 2017
Rechargeable Aqueous Zn–V 2 O 5 Battery with High Energy Density and Long Cycle Life journal May 2018
Recent Advances in Aqueous Zinc-Ion Batteries journal September 2018
High-Capacity Layered Magnesium Vanadate with Concentrated Gel Electrolyte toward High-Performance and Wide-Temperature Zinc-Ion Battery journal November 2020
Electrochemical Energy Storage for Green Grid journal May 2011
Aqueous Rechargeable Li and Na Ion Batteries journal September 2014
π-Back-Donation Effect of the Cyanide Ligands on the Electron Correlation and Charge Transfer in Prussian Blue RbMn[Fe(CN) 6 ] journal April 2010
Non-Prussian Blue Structures and Magnetic Ordering of Na 2 Mn II [Mn II (CN) 6 ] and Na 2 Mn II [Mn II (CN) 6 ]·2H 2 O journal January 2012
Removal of Interstitial H 2 O in Hexacyanometallates for a Superior Cathode of a Sodium-Ion Battery journal February 2015
Low-Cost High-Energy Potassium Cathode journal January 2017
Highly Reversible Open Framework Nanoscale Electrodes for Divalent Ion Batteries journal October 2013
Building aqueous K-ion batteries for energy storage journal May 2019
Highly reversible zinc metal anode for aqueous batteries journal April 2018
Tuning polaronic redox behavior in olivine phosphate journal January 2019
Electrolyte regulation enhances the stability of Prussian blue analogues in aqueous Na-ion storage journal January 2019
Issues and opportunities facing aqueous zinc-ion batteries journal January 2019
Fundamentals and perspectives in developing zinc-ion battery electrolytes: a comprehensive review journal January 2020
Sodium zinc hexacyanoferrate with a well-defined open framework as a positive electrode for sodium ion batteries journal January 2012
First principles calculation of a large variation in dielectric tensor through the spin crossover in the CsFe[Cr(CN) 6 ] Prussian blue analogue journal April 2014
Defining the contributions of permanent electrostatics, Pauli repulsion, and dispersion in density functional theory calculations of intermolecular interaction energies journal March 2016
The Jahn-Teller effect and magnetism: transition metal compounds journal April 1982
Electrical Energy Storage for the Grid: A Battery of Choices journal November 2011
Rechargeable Lithium Batteries with Aqueous Electrolytes journal May 1994
Theoretical Investigation on Electronic Properties of ZnO Crystals Using DFT-Based Calculation Method journal July 2015

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