Accessing the second electron capacity of MnO2 by exploring complexation and intercalation reactions in energy dense alkaline batteries

Yadav, Gautam G.; Wei, Xia; Huang, Jinchao; Turney, Damon; Nyce, Michael; Banerjee, Sanjoy

doi:10.1016/j.ijhydene.2018.03.061

Title: Accessing the second electron capacity of MnO₂ by exploring complexation and intercalation reactions in energy dense alkaline batteries

Abstract

MnO₂ is one of the safest and most abundant electrochemical materials available. It exhibits polymorphism, which has been exploited in many applications especially batteries. In alkaline batteries, γ-MnO₂ is widely used because its proton insertion reaction yields one e^- (1st) per Mn at high voltages. It also gives a second (2nd) e^- during dissolution-precipitation reactions that occur at lower voltages than the proton insertion; however, these 2nd e^- reactions are highly irreversible. Here in this communication, here we explore the reversibility of the 2nd e^- reactions with bismuth oxide (Bi₂O₃) and copper (Cu) additives, and cycling in specific potential regions where δ-MnO₂ is the polymorph synthesized electrochemically in-situ from γ-MnO₂. The use of Bi₂O₃ and Cu add complexation and intercalation reactions, where presence and/or electrochemical activation of both are essential for reversibility and for capacity retention (50–100%). Attaining 300–610Wh kg^-1 against a zinc anode is possible for these batteries, which could promote its use for many applications.

Authors:

Yadav, Gautam G. ^[1];

^[2]; Huang, Jinchao ^[1]; Turney, Damon ^[1]; Nyce, Michael ^[1]; Banerjee, Sanjoy ^[1]

City University of New York (CUNY), NY (United States)
ZPower, LLC, Camarillo, CA (United States); International Journal of Hydrogen Energy, Amsterdam (Netherlands)

Publication Date:: Tue Apr 03 00:00:00 EDT 2018

Research Org.:: City Univ. of New York (CUNY), NY (United States)

Sponsoring Org.:: USDOE Advanced Research Projects Agency - Energy (ARPA-E); ew York State Research and Development Authority (NYSERDA)

OSTI Identifier:: 1538352

Alternate Identifier(s):: OSTI ID: 1591668

Grant/Contract Number:: AR0000150; DE AR0000150

Resource Type:: Accepted Manuscript

Journal Name:: International Journal of Hydrogen Energy

Additional Journal Information:: Journal Volume: 43; Journal Issue: 17; Journal ID: ISSN 0360-3199

Publisher:: Elsevier

Country of Publication:: United States

Language:: English

Subject:: 08 HYDROGEN; batteries; alkaline; manganese dioxide; zinc

Citation Formats


                    Yadav, Gautam G., Wei, Xia, Huang, Jinchao, Turney, Damon, Nyce, Michael, and Banerjee, Sanjoy. Accessing the second electron capacity of MnO2 by exploring complexation and intercalation reactions in energy dense alkaline batteries.  United States: N. p., 2018. 
Web.  doi:10.1016/j.ijhydene.2018.03.061.

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                    Yadav, Gautam G., Wei, Xia, Huang, Jinchao, Turney, Damon, Nyce, Michael, & Banerjee, Sanjoy. Accessing the second electron capacity of MnO2 by exploring complexation and intercalation reactions in energy dense alkaline batteries.  United States.  https://doi.org/10.1016/j.ijhydene.2018.03.061

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                    Yadav, Gautam G., Wei, Xia, Huang, Jinchao, Turney, Damon, Nyce, Michael, and Banerjee, Sanjoy. Tue .  
"Accessing the second electron capacity of MnO2 by exploring complexation and intercalation reactions in energy dense alkaline batteries".  United States.  https://doi.org/10.1016/j.ijhydene.2018.03.061.  https://www.osti.gov/servlets/purl/1538352.

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@article{osti_1538352,

  title        = {Accessing the second electron capacity of MnO2 by exploring complexation and intercalation reactions in energy dense alkaline batteries},

  author       = {Yadav, Gautam G. and Wei, Xia and Huang, Jinchao and Turney, Damon and Nyce, Michael and Banerjee, Sanjoy},

  abstractNote = {MnO2 is one of the safest and most abundant electrochemical materials available. It exhibits polymorphism, which has been exploited in many applications especially batteries. In alkaline batteries, γ-MnO2 is widely used because its proton insertion reaction yields one e- (1st) per Mn at high voltages. It also gives a second (2nd) e- during dissolution-precipitation reactions that occur at lower voltages than the proton insertion; however, these 2nd e- reactions are highly irreversible. Here in this communication, here we explore the reversibility of the 2nd e- reactions with bismuth oxide (Bi2O3) and copper (Cu) additives, and cycling in specific potential regions where δ-MnO2 is the polymorph synthesized electrochemically in-situ from γ-MnO2. The use of Bi2O3 and Cu add complexation and intercalation reactions, where presence and/or electrochemical activation of both are essential for reversibility and for capacity retention (50–100%). Attaining 300–610Wh kg-1 against a zinc anode is possible for these batteries, which could promote its use for many applications.},

  doi          = {10.1016/j.ijhydene.2018.03.061},

  journal      = {International Journal of Hydrogen Energy},

  number       = 17,

  volume       = 43,

  place        = {United States},

  year         = {Tue Apr 03 00:00:00 EDT 2018},

  month        = {Tue Apr 03 00:00:00 EDT 2018}

}

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Title: Accessing the second electron capacity of MnO2 by exploring complexation and intercalation reactions in energy dense alkaline batteries

Abstract

Citation Formats

Operando identification of the point of [Mn2]O4 spinel formation during γ-MnO2 discharge within batteries journal, July 2016

Characterization of the Bismuth-Modified Manganese Dioxide Cathodes in Rechargeable Alkaline Cells journal, January 2002

Impact of anode substrates on electrodeposited zinc over cycling in zinc-anode rechargeable alkaline batteries journal, September 2016

Linear sweep voltametry studies on oxygen reduction of some oxides in alkaline electrolytes journal, January 2009

Nanostructured MnO2 for Li batteries journal, June 2003

Rechargeability and economic aspects of alkaline zinc–manganese dioxide cells for electrical storage and load leveling journal, February 2015

Anodic behavior of zinc in Zn-MnO2 battery using ERDA technique journal, July 2010

Synthesis of Copper Birnessite, Cu x MnO y ·nH 2 O with Crystallite Size Control: Impact of Crystallite Size on Electrochemistry journal, November 2015

Impact of Triethanolamine as an Additive for Rechargeable Alkaline Zn/MnO 2 Batteries under Limited Depth of Discharge Conditions journal, January 2017

Manganese compounds as water oxidizing catalysts for hydrogen production via water splitting: From manganese complexes to nano-sized manganese oxides journal, May 2012

Platinum/manganese oxide nanocomposites as water-oxidizing catalysts: New findings and current controversies journal, September 2015

Rapid electrochemical synthesis of δ-MnO2 from γ-MnO2 and unleashing its performance as an energy dense electrode journal, December 2017

Au–MnO2/MWNT and Au–ZnO/MWNT as oxygen reduction reaction electrocatalyst for polymer electrolyte membrane fuel cell journal, August 2009

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A conversion-based highly energy dense Cu 2+ intercalated Bi-birnessite/Zn alkaline battery journal, January 2017

Role of Bismuth and Factors Influencing the Formation of Mn[sub 3]O[sub 4] in Rechargeable Alkaline Batteries Based on Bismuth-Containing Manganese Oxides journal, January 2003

Electrochemical reactions in batteries. Emphasizing the MnO2 cathode of dry cells journal, September 1972

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Electrochemical Study of Bi[sub 2]O[sub 3] and Bi[sub 2]O[sub 2]CO[sub 3] by Means of a Cavity Microelectrode. I. Observed Phenomena and Direct Analysis of Results journal, January 2000

Hetaerolite Profiles in Alkaline Batteries Measured by High Energy EDXRD journal, November 2014

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Redox Processes at the Manganese Dioxide Electrode journal, January 1997

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Solar thermochemical ZnO/ZnSO4 water splitting cycle for hydrogen production journal, September 2017

Progress and perspectives in micro direct methanol fuel cell journal, May 2012

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Rechargeability of MnO[sub 2] in KOH Media Produced by Decomposition of Dissolved KMnO[sub 4] and Bi(NO[sub 3])[sub 3] Mixtures journal, January 1997

Study of the rechargeable manganese dioxide electrode journal, September 1995

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X-ray absorption spectroscopy of lithium insertion and de-insertion in copper birnessite nanoparticle electrodes journal, January 2016

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Title: Accessing the second electron capacity of MnO₂ by exploring complexation and intercalation reactions in energy dense alkaline batteries

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journal, July 2016

Characterization of the Bismuth-Modified Manganese Dioxide Cathodes in Rechargeable Alkaline Cells
journal, January 2002

Impact of anode substrates on electrodeposited zinc over cycling in zinc-anode rechargeable alkaline batteries
journal, September 2016

Linear sweep voltametry studies on oxygen reduction of some oxides in alkaline electrolytes
journal, January 2009

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Rechargeability and economic aspects of alkaline zinc–manganese dioxide cells for electrical storage and load leveling
journal, February 2015

Anodic behavior of zinc in Zn-MnO2 battery using ERDA technique
journal, July 2010

Synthesis of Copper Birnessite, Cu _x MnO _y ·nH ₂ O with Crystallite Size Control: Impact of Crystallite Size on Electrochemistry
journal, November 2015

Impact of Triethanolamine as an Additive for Rechargeable Alkaline Zn/MnO ₂ Batteries under Limited Depth of Discharge Conditions
journal, January 2017

Manganese compounds as water oxidizing catalysts for hydrogen production via water splitting: From manganese complexes to nano-sized manganese oxides
journal, May 2012

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journal, September 2015

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Graphene supported α-MnO2 nanocomposite cathodes for lithium ion batteries
journal, May 2016

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journal, January 2017

Role of Bismuth and Factors Influencing the Formation of Mn[sub 3]O[sub 4] in Rechargeable Alkaline Batteries Based on Bismuth-Containing Manganese Oxides
journal, January 2003

Electrochemical reactions in batteries. Emphasizing the MnO2 cathode of dry cells
journal, September 1972

Rechargeable Cells with Modified MnO[sub 2] Cathodes
journal, January 1988

Electrochemical Study of Bi[sub 2]O[sub 3] and Bi[sub 2]O[sub 2]CO[sub 3] by Means of a Cavity Microelectrode. I. Observed Phenomena and Direct Analysis of Results
journal, January 2000

Hetaerolite Profiles in Alkaline Batteries Measured by High Energy EDXRD
journal, November 2014

Rechargeable manganese oxide electrodes
journal, December 1987

Real-time materials evolution visualized within intact cycling alkaline batteries
journal, January 2014

Fabrication and electrochemical characterization of two-dimensional ordered nanoporous manganese oxide for supercapacitor applications
journal, January 2012

A calcium hydroxide interlayer as a selective separator for rechargeable alkaline Zn/MnO2 batteries
journal, August 2017

Rechargeable Zinc Alkaline Anodes for Long-Cycle Energy Storage
journal, May 2017

Redox Processes at the Manganese Dioxide Electrode
journal, January 1997

Redox Processes at the Manganese Dioxide Electrode
journal, January 1997

Rechargeability of a Chemically Modified MnO[sub 2]∕Zn Battery System at Practically Favorable Power Levels
journal, January 1993

Solar thermochemical ZnO/ZnSO4 water splitting cycle for hydrogen production
journal, September 2017

Progress and perspectives in micro direct methanol fuel cell
journal, May 2012

Rechargeable manganese oxide electrodes
journal, May 1987

CuMnOx catalysts for internal reforming methanol fuel cells: Application aspects
journal, November 2012

A highly dispersible, magnetically separable and environmentally friendly nano-sized catalyst for water oxidation
journal, March 2016

MnO2 modified multi-walled carbon nanotubes supported Pd nanoparticles for methanol electro-oxidation in alkaline media
journal, October 2010

Regenerable Cu-intercalated MnO2 layered cathode for highly cyclable energy dense batteries
journal, March 2017

Rechargeability of MnO[sub 2] in KOH Media Produced by Decomposition of Dissolved KMnO[sub 4] and Bi(NO[sub 3])[sub 3] Mixtures
journal, January 1997

Study of the rechargeable manganese dioxide electrode
journal, September 1995

Rechargeability of MnO[sub 2] in KOH Media Produced by Decomposition of Dissolved KMnO[sub 4] and Bi(NO[sub 3])[sub 3] Mixtures
journal, January 1997

X-ray absorption spectroscopy of lithium insertion and de-insertion in copper birnessite nanoparticle electrodes
journal, January 2016

The rechargeability of manganese dioxide in alkaline electrolyte
journal, October 1981

Energy Harvesting Sources, Storage Devices and System Topologies for Environmental Wireless Sensor Networks: A Review
journal, July 2018