Synthesis of Copper Birnessite, CuxMnOy·nH2O with Crystallite Size Control: Impact of Crystallite Size on Electrochemistry

Li, Yue Ru; Marschilok, Amy C.; Takeuchi, Esther S.; Takeuchi, Kenneth J.

doi:10.1149/2.0501602jes

Title: Synthesis of Copper Birnessite, Cu_xMnO_y·nH₂O with Crystallite Size Control: Impact of Crystallite Size on Electrochemistry

Abstract

This report describes the first detailed electrochemical examination of a series of copper birnessite samples under lithium-based battery conditions, allowing a structure/function analysis of the electrochemistry and related material properties. To obtain the series of copper birnessite samples, a novel synthetic approach for the preparation of copper birnessite, Cu_xMnO_y·nH₂O is reported. The copper content (x) in Cu_xMnO_y·nH₂O, 0.28 >= x >= 0.20, was inversely proportional to crystallite size, which ranged from 12 to 19 nm. The electrochemistry under lithium-based battery conditions showed that the higher copper content (x = 0.28) and small crystallite size (similar to 12 nm) sample delivered similar to 194 mAh/g, about 20% higher capacity than the low copper content (x = 0.22) and larger crystallite size (similar to 19 nm) material. In addition, Cu_xMnO_y·nH₂O displays quasi-reversible electrochemistry in magnesium based electrolytes, indicating that copper birnessite could be a candidate for future application in magnesium-ion batteries.

Authors:

Li, Yue Ru ^[1]; Marschilok, Amy C. ^[1]; Takeuchi, Esther S. ^[2]; Takeuchi, Kenneth J. ^[1]

Stony Brook Univ., NY (United States)
Stony Brook Univ., NY (United States); Brookhaven National Lab. (BNL), Upton, NY (United States)

Publication Date:: Tue Nov 24 00:00:00 EST 2015

Research Org.:: State Univ. of New York (SUNY), Stony Brook, NY (United States)

Sponsoring Org.:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

OSTI Identifier:: 1437949

Grant/Contract Number:: SC0008512

Resource Type:: Accepted Manuscript

Journal Name:: Journal of the Electrochemical Society

Additional Journal Information:: Journal Volume: 163; Journal Issue: 2; Journal ID: ISSN 0013-4651

Publisher:: The Electrochemical Society

Country of Publication:: United States

Language:: English

Subject:: 25 ENERGY STORAGE

Citation Formats


                    Li, Yue Ru, Marschilok, Amy C., Takeuchi, Esther S., and Takeuchi, Kenneth J. Synthesis of Copper Birnessite, CuxMnOy·nH2O with Crystallite Size Control: Impact of Crystallite Size on Electrochemistry.  United States: N. p., 2015. 
Web.  doi:10.1149/2.0501602jes.

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                    Li, Yue Ru, Marschilok, Amy C., Takeuchi, Esther S., & Takeuchi, Kenneth J. Synthesis of Copper Birnessite, CuxMnOy·nH2O with Crystallite Size Control: Impact of Crystallite Size on Electrochemistry.  United States.  https://doi.org/10.1149/2.0501602jes

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                    Li, Yue Ru, Marschilok, Amy C., Takeuchi, Esther S., and Takeuchi, Kenneth J. Tue .  
"Synthesis of Copper Birnessite, CuxMnOy·nH2O with Crystallite Size Control: Impact of Crystallite Size on Electrochemistry".  United States.  https://doi.org/10.1149/2.0501602jes.  https://www.osti.gov/servlets/purl/1437949.

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@article{osti_1437949,

  title        = {Synthesis of Copper Birnessite, CuxMnOy·nH2O with Crystallite Size Control: Impact of Crystallite Size on Electrochemistry},

  author       = {Li, Yue Ru and Marschilok, Amy C. and Takeuchi, Esther S. and Takeuchi, Kenneth J.},

  abstractNote = {This report describes the first detailed electrochemical examination of a series of copper birnessite samples under lithium-based battery conditions, allowing a structure/function analysis of the electrochemistry and related material properties. To obtain the series of copper birnessite samples, a novel synthetic approach for the preparation of copper birnessite, CuxMnOy·nH2O is reported. The copper content (x) in CuxMnOy·nH2O, 0.28 >= x >= 0.20, was inversely proportional to crystallite size, which ranged from 12 to 19 nm. The electrochemistry under lithium-based battery conditions showed that the higher copper content (x = 0.28) and small crystallite size (similar to 12 nm) sample delivered similar to 194 mAh/g, about 20% higher capacity than the low copper content (x = 0.22) and larger crystallite size (similar to 19 nm) material. In addition, CuxMnOy·nH2O displays quasi-reversible electrochemistry in magnesium based electrolytes, indicating that copper birnessite could be a candidate for future application in magnesium-ion batteries.},

  doi          = {10.1149/2.0501602jes},

  journal      = {Journal of the Electrochemical Society},

  number       = 2,

  volume       = 163,

  place        = {United States},

  year         = {Tue Nov 24 00:00:00 EST 2015},

  month        = {Tue Nov 24 00:00:00 EST 2015}

}

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Über Oxidhydroxide des vierwertigen Mangans mit Schichtengitter. 1. Mitteilung. Natriummangan (II, III)manganat(IV)
journal, January 1970

Effects of base concentration and cation on hydrothermal processes of cetyltrimethylammonium permanganate in various aqueous media
journal, January 2005

Preparative Parameters, Magnesium Effects, and Anion Effects in the Crystallization of Birnessites
journal, December 1997

Effects of Inorganic Cation Templates on Octahedral Molecular Sieves of Manganese Oxide
journal, November 1994

The synthesis of birnessite, cryptomelane, and some other oxides and hydroxides of manganese
journal, December 1971

Synthesis and characterization of sodium vanadium oxide gels: the effects of water (n) and sodium (x) content on the electrochemistry of NaxV2O5·nH2O
journal, January 2011

Crystallite Size Control and Resulting Electrochemistry of Magnetite, Fe[sub 3]O[sub 4]
journal, January 2009

Uptake of cadmium, copper, and lead by microporous synthetic Na-birnessite
journal, November 2010

Copper sorption by the edge surfaces of synthetic birnessite nanoparticles
journal, March 2015

Structure of H-exchanged hexagonal birnessite and its mechanism of formation from Na-rich monoclinic buserite at low pH
journal, May 2000

Mg rechargeable batteries: an on-going challenge
journal, January 2013

Cathode materials for magnesium and magnesium-ion based batteries
journal, March 2015

Variation of the MnO ₂ Birnessite Structure upon Charge/Discharge in an Electrochemical Supercapacitor Electrode in Aqueous Na ₂ SO ₄ Electrolyte
journal, April 2008

The High Performance of Crystal Water Containing Manganese Birnessite Cathodes for Magnesium Batteries
journal, May 2015

Thin layers formed by the oriented 2D nanocrystals of birnessite-type manganese oxide as a new electrochemical platform for ultrasensitive nonenzymatic hydrogen peroxide detection
journal, December 2018