Tunnel structured manganese oxide nanowires as redox active electrodes for hybrid capacitive deionization

Byles, Bryan W.; Cullen, David A.; More, Karren Leslie; Pomerantseva, Ekaterina

doi:10.1016/j.nanoen.2017.12.015

Tunnel structured manganese oxide nanowires as redox active electrodes for hybrid capacitive deionization

Journal Article · Mon Dec 18 00:00:00 EST 2017 · Nano Energy

DOI:https://doi.org/10.1016/j.nanoen.2017.12.015· OSTI ID:1422591

Byles, Bryan W. ^[1]; ^[2]; ^[3]; Pomerantseva, Ekaterina ^[1]

Drexel Univ., Philadelphia, PA (United States). Department of Materials Science and Engineering
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Materials Science and Technology Division
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Sciences

We report that hybrid capacitive deionization (HCDI), which combines a capacitive carbon electrode and a redox active electrode in a single device, has emerged as a promising method for water desalination, enabling higher ion removal capacity than devices containing two carbon electrodes. However, to date, the desalination performance of few redox active materials has been reported. For the first time, we present the electrochemical behavior of manganese oxide nanowires with four different tunnel crystal structures as faradaic electrodes in HCDI cells. Two of these phases are square tunnel structured manganese oxides, α-MnO₂ and todorokite-MnO₂. The other two phases have novel structures that cross-sectional scanning transmission electron microscopy analysis revealed to have ordered and disordered combinations of structural tunnels with different dimensions. The ion removal performance of the nanowires was evaluated not only in NaCl solution, which is traditionally used in laboratory experiments, but also in KCl and MgCl₂ solutions, providing better understanding of the behavior of these materials for desalination of brackish water that contains multiple cation species. High ion removal capacities (as large as 27.8 mg g^-1, 44.4 mg g^-1, and 43.1 mg g^-1 in NaCl, KCl, and MgCl₂ solutions, respectively) and high ion removal rates (as large as 0.112 mg g^-1 s^-1, 0.165 mg g^-1 s^-1, and 0.164 mg g^-1 s^-1 in NaCl, KCl, and MgCl₂ solutions, respectively) were achieved. By comparing ion removal capacity to structural tunnel size, it was found that smaller tunnels do not favor the removal of cations with larger hydrated radii, and more efficient removal of larger hydrated cations can be achieved by utilizing manganese oxides with larger structural tunnels. Extended HCDI cycling and ex situ X-ray diffraction analysis revealed the excellent stability of the manganese oxide electrodes in repeated ion removal/ion release cycles, and compositional analysis of the electrodes indicated that ion removal is achieved through both surface redox reactions and intercalation of ions into the structural tunnels. In conclusion, this work contributes to the understanding of the behavior of faradaic materials in electrochemical water desalination and elucidates the relationship between the electrode material crystal structure and the ion removal capacity/ion removal rate in various salt solutions.

View Accepted Manuscript (DOE)

Research Organization:: Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

Grant/Contract Number:: AC05-00OR22725

OSTI ID:: 1422591

Journal Information:: Nano Energy, Journal Name: Nano Energy Journal Issue: C Vol. 44; ISSN 2211-2855

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

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36 MATERIALS SCIENCE
77 NANOSCIENCE AND NANOTECHNOLOGY
Electrochemical water desalination
Hybrid capacitive deionization
Manganese oxides
Tunnel crystal structures

Tunnel structured manganese oxide nanowires as redox active electrodes for hybrid capacitive deionization

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Cited By (16)

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