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Reversible Multivalent (Monovalent, Divalent, Trivalent) Ion Insertion in Open Framework Materials
Author(s) -
Wang Richard Y.,
Shyam Badri,
Stone Kevin H.,
Weker Johanelson,
Pasta Mauro,
Lee HyunWook,
Toney Michael F.,
Cui Yi
Publication year - 2015
Publication title -
advanced energy materials
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 10.08
H-Index - 220
eISSN - 1614-6840
pISSN - 1614-6832
DOI - 10.1002/aenm.201401869
Subject(s) - materials science , ion , aqueous solution , divalent , electrochemistry , prussian blue , vacancy defect , kinetics , inorganic chemistry , electrode , chemistry , crystallography , organic chemistry , metallurgy , physics , quantum mechanics
The reversible electrochemical insertion of multivalent ions into materials has promising applications in many fields, including batteries, seawater desalination, element purification, and wastewater treatment. However, finding materials that allow for the insertion of multivalent ions with fast kinetics and stable cycling has proven difficult because of strong electrostatic interactions between the highly charged insertion ions and atoms in the host framework. Here, an open framework nanomaterial, copper hexacyanoferrate, in the Prussian Blue family is presented that allows for the reversible insertion of a wide variety of monovalent, divalent, and trivalent ions (such as Rb + , Pb 2+ , Al 3+ , and Y 3+ ) in aqueous solution beyond that achieved in previous studies. Electrochemical measurements demonstrate the unprecedented kinetics of multivalent ion insertion associated with this material. Synchrotron X‐ray diffraction experiments point toward a novel vacancy‐mediated ion insertion mechanism that reduces electrostatic repulsion and helps to facilitate the observed rapid ion insertion. The results suggest a new approach to multivalent ion insertion that may help to advance the understanding of this complex phenomenon.