Band diagram and rate analysis of thin film spinel LiMn2O4 formed by electrochemical conversion of ALD-grown MnO

Young, Matthias J.; Schnabel, Hans-Dieter; Holder, Aaron M.; George, Steven M.; Musgrave, Charles B.

doi:10.1002/adfm.201602773

Title: Band diagram and rate analysis of thin film spinel LiMn₂O₄ formed by electrochemical conversion of ALD-grown MnO

Abstract

Nanoscale spinel lithium manganese oxide is of interest as a high-rate cathode material for advanced battery technologies among other electrochemical applications. In this work, the synthesis of ultrathin films of spinel lithium manganese oxide (LiMn₂O₄) between 20 and 200 nm in thickness by room-temperature electrochemical conversion of MnO grown by atomic layer deposition (ALD) is demonstrated. The charge storage properties of LiMn₂O₄ thin films in electrolytes containing Li⁺, Na⁺, K⁺, and Mg²⁺ are investigated. A unified electrochemical band-diagram (UEB) analysis of LiMn₂O₄ informed by screened hybrid density functional theory calculations is also employed to expand on existing understanding of the underpinnings of charge storage and stability in LiMn₂O₄. It is shown that the incorporation of Li⁺ or other cations into the host manganese dioxide spinel structure (λ-MnO₂) stabilizes electronic states from the conduction band which align with the known redox potentials of LiMn₂O₄. Furthermore, the cyclic voltammetry experiments demonstrate that up to 30% of the capacity of LiMn₂O₄ arises from bulk electronic charge-switching which does not require compensating cation mass transport. As a result, the hybrid ALD-electrochemical synthesis, UEB analysis, and unique charge storage mechanism described here provide a fundamental framework to guide the development of future nanoscale electrode materialsmore » for ion-incorporation charge storage.« less

Authors:

Young, Matthias J. ^[1]; Schnabel, Hans-Dieter ^[2]; Holder, Aaron M. ^[3]; George, Steven M. ^[1]; Musgrave, Charles B. ^[1]

Univ. of Colorado, Boulder, CO (United States)
Leupold-Institut fur Angewandte Naturwissenschaften, Zwickau (Germany)
Univ. of Colorado, Boulder, CO (United States); National Renewable Energy Lab. (NREL), Golden, CO (United States)

Publication Date:: Thu Sep 22 00:00:00 EDT 2016

Research Org.:: National Renewable Energy Laboratory (NREL), Golden, CO (United States); Energy Frontier Research Centers (EFRC) (United States). Center for Next Generation of Materials by Design: Incorporating Metastability (CNGMD)

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

OSTI Identifier:: 1333410

Report Number(s):: NREL/JA-5K00-67263
Journal ID: ISSN 1616-301X

Grant/Contract Number:: AC36-08GO28308; AC36-99GO10337

Resource Type:: Accepted Manuscript

Journal Name:: Advanced Functional Materials

Additional Journal Information:: Journal Volume: 26; Journal Issue: 43; Journal ID: ISSN 1616-301X

Publisher:: Wiley

Country of Publication:: United States

Language:: English

Subject:: 36 MATERIALS SCIENCE; atomic layer deposition; charge storage mechanism; defect theory; ion intercalation; lithium manganese oxide

Citation Formats


                    Young, Matthias J., Schnabel, Hans-Dieter, Holder, Aaron M., George, Steven M., and Musgrave, Charles B. Band diagram and rate analysis of thin film spinel LiMn2O4 formed by electrochemical conversion of ALD-grown MnO.  United States: N. p., 2016. 
Web.  doi:10.1002/adfm.201602773.

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                    Young, Matthias J., Schnabel, Hans-Dieter, Holder, Aaron M., George, Steven M., & Musgrave, Charles B. Band diagram and rate analysis of thin film spinel LiMn2O4 formed by electrochemical conversion of ALD-grown MnO.  United States.  https://doi.org/10.1002/adfm.201602773

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                    Young, Matthias J., Schnabel, Hans-Dieter, Holder, Aaron M., George, Steven M., and Musgrave, Charles B. Thu .  
"Band diagram and rate analysis of thin film spinel LiMn2O4 formed by electrochemical conversion of ALD-grown MnO".  United States.  https://doi.org/10.1002/adfm.201602773.  https://www.osti.gov/servlets/purl/1333410.

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@article{osti_1333410,

  title        = {Band diagram and rate analysis of thin film spinel LiMn2O4 formed by electrochemical conversion of ALD-grown MnO},

  author       = {Young, Matthias J. and Schnabel, Hans-Dieter and Holder, Aaron M. and George, Steven M. and Musgrave, Charles B.},

  abstractNote = {Nanoscale spinel lithium manganese oxide is of interest as a high-rate cathode material for advanced battery technologies among other electrochemical applications. In this work, the synthesis of ultrathin films of spinel lithium manganese oxide (LiMn2O4) between 20 and 200 nm in thickness by room-temperature electrochemical conversion of MnO grown by atomic layer deposition (ALD) is demonstrated. The charge storage properties of LiMn2O4 thin films in electrolytes containing Li+, Na+, K+, and Mg2+ are investigated. A unified electrochemical band-diagram (UEB) analysis of LiMn2O4 informed by screened hybrid density functional theory calculations is also employed to expand on existing understanding of the underpinnings of charge storage and stability in LiMn2O4. It is shown that the incorporation of Li+ or other cations into the host manganese dioxide spinel structure (λ-MnO2) stabilizes electronic states from the conduction band which align with the known redox potentials of LiMn2O4. Furthermore, the cyclic voltammetry experiments demonstrate that up to 30% of the capacity of LiMn2O4 arises from bulk electronic charge-switching which does not require compensating cation mass transport. As a result, the hybrid ALD-electrochemical synthesis, UEB analysis, and unique charge storage mechanism described here provide a fundamental framework to guide the development of future nanoscale electrode materials for ion-incorporation charge storage.},

  doi          = {10.1002/adfm.201602773},

  journal      = {Advanced Functional Materials},

  number       = 43,

  volume       = 26,

  place        = {United States},

  year         = {Thu Sep 22 00:00:00 EDT 2016},

  month        = {Thu Sep 22 00:00:00 EDT 2016}

}

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Figure 1: Absolute potential diagram motivating the need for high-voltage cathode materials, showing equilibrium potential regions for anodes (green) and cathodes (red), and electrolyte stability windows (blue), with common electrochemical references shown in black.

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Title: Band diagram and rate analysis of thin film spinel LiMn2O4 formed by electrochemical conversion of ALD-grown MnO

Abstract

Citation Formats

Figures / Tables:

Improved capacity retention in rechargeable 4 V lithium/lithium-manganese oxide (spinel) cells journal, April 1994

Pourbaix-like phase diagram for lithium manganese spinels in acid journal, January 2010

Novel mixed polyanions lithium-ion battery cathode materials predicted by high-throughput ab initio computations journal, January 2011

An aqueous electrolyte, sodium ion functional, large format energy storage device for stationary applications journal, September 2012

Influence of oxalic acid on the dissolution kinetics of manganese oxide journal, November 2012

Citric acid-assisted sol–gel synthesis of nanocrystalline LiMn2O4 spinel as cathode material journal, August 2003

Electrochemical Quartz Crystal Microbalance for Insertion/Extraction of Lithium in Spinel LiMn 2 O 4 Thin Films journal, July 1999

Thermodynamic Properties of Manganese Oxides journal, July 1996

Sodium Charge Storage in Thin Films of MnO 2 Derived by Electrochemical Oxidation of MnO Atomic Layer Deposition Films journal, January 2015

Proton insertion and lithium-proton exchange in spinel lithium manganates journal, May 1997

Electronic properties of LiMn2−x Ti x O4 journal, September 2009

High Cycling Stability and Extreme Rate Performance in Nanoscaled LiMn 2 O 4 Thin Films journal, September 2015

VESTA 3 for three-dimensional visualization of crystal, volumetric and morphology data journal, October 2011

First principles computational materials design for energy storage materials in lithium ion batteries journal, January 2009

Synthesis of spinel LiMn2O4 using direct solid state reaction journal, October 2002

Charge and spin ordering in LiMn 2 O 4 journal, August 2001

Ground-state properties of multivalent manganese oxides: Density functional and hybrid density functional calculations journal, May 2007

Preparation, structure and electrochemical properties of spinel Li1−xMn2−yO4 cathode material for lithium ion batteries journal, April 2000

Atomic Layer Deposition of Spinel Lithium Manganese Oxide by Film-Body-Controlled Lithium Incorporation for Thin-Film Lithium-Ion Batteries journal, December 2013

Bulk and Surface Tunneling Hydrogen Defects in Alumina journal, August 2013

Crystalline MnO[sub 2] as Possible Alternatives to Amorphous Compounds in Electrochemical Supercapacitors journal, January 2006

Fast Li-Ion Insertion into Nanosized LiMn 2 O 4 without Domain Boundaries journal, January 2010

Nano LiMn2O4 as cathode material of high rate capability for lithium ion batteries journal, January 2012

“Inner” and “outer” active surface of RuO2 electrodes journal, January 1990

Low-Temperature Synthesis of Lithium Manganese Oxide Using LiCl-Li 2 CO 3 and Manganese Acetate Eutectic Mixture journal, November 2011

Electrochemical Impedance Spectroscopy book, February 2008

First-principles calculations for defects and impurities: Applications to III-nitrides journal, April 2004

Rechargeable Li[sub 1+x]Mn[sub 2]O[sub 4]∕Carbon Cells with a New Electrolyte Composition journal, January 1993

Electrochemistry of Manganese Dioxide in Lithium Nonaqueous Cell journal, January 1989

Hydrothermal synthesis of LiMn2O4/C composite as a cathode for rechargeable lithium-ion battery with excellent rate capability journal, September 2009

Achieving electrochemical capacitor functionality from nanoscale LiMn2O4 coatings on 3-D carbon nanoarchitectures journal, January 2013

Challenges in the development of advanced Li-ion batteries: a review journal, January 2011

Chemical potential dependence of defect formation energies in GaAs: Application to Ga self-diffusion journal, October 1991

Ceramic and polymeric solid electrolytes for lithium-ion batteries journal, August 2010

Commentary: The Materials Project: A materials genome approach to accelerating materials innovation journal, July 2013

Charge Storage in Cation Incorporated α-MnO 2 journal, February 2015

Phase-controlled synthesis of polymorphic MnO 2 structures for electrochemical energy storage journal, January 2015

Effect of substrate on the characteristics of manganese(IV) oxide thin films prepared by atomic layer deposition journal, December 2004

The reduction and oxidation behaviour of manganese oxides journal, January 1999

Growth of manganese oxide thin films by atomic layer deposition journal, November 2003

Accurate defect levels obtained from the HSE06 range-separated hybrid functional journal, April 2010

Pseudocapacitive Contributions to Electrochemical Energy Storage in TiO2 (Anatase) Nanoparticles journal, October 2007

Beyond the ability of Rietveld analysis: MEM-based pattern fitting journal, August 2004

Characterization and electrochemical performance of the spinel LiMn2O4 prepared from É›-MnO2 journal, May 2000

Polymer Electrolytes for Lithium-Ion Batteries journal, April 1998

Charge Storage Mechanism of MnO 2 Electrode Used in Aqueous Electrochemical Capacitor journal, August 2004

Batteries for lithium recovery from brines journal, January 2012

Atomic layer deposition of MnO using Bis(ethylcyclopentadienyl)manganese and H2O journal, August 2009

Highly selective lithium recovery from brine using a λ-MnO2–Ag battery journal, January 2013

Surface structure and equilibrium particle shape of the LiMn 2 O 4 spinel from first-principles calculations journal, February 2013

The Unified Electrochemical Band Diagram Framework: Understanding the Driving Forces of Materials Electrochemistry journal, August 2018

Modulation of the Optical Properties of Lithium Manganese Oxide via Li-Ion De/Intercalation journal, April 2018

Unveiling Conversion Reaction on Intercalation-Based Transition Metal Oxides for High Power, High Energy Aqueous Lithium Battery journal, October 2018

Discovery of Anion Insertion Electrochemistry in Layered Hydroxide Nanomaterials journal, February 2019

Growth behavior, work function, and band gap tuning of nanocrystalline LiMn 2 O 4 thin films journal, August 2019

Efficient Capacitive Deionization Using Thin Film Sodium Manganese Oxide journal, January 2018

Unveiling Conversion Reaction on Intercalation‐Based Transition Metal Oxides for High Power, High Energy Aqueous Lithium Battery journal, July 2021

Discovery of Anion Insertion Electrochemistry in Layered Hydroxide Nanomaterials journal, February 2019

Title: Band diagram and rate analysis of thin film spinel LiMn₂O₄ formed by electrochemical conversion of ALD-grown MnO

Improved capacity retention in rechargeable 4 V lithium/lithium-manganese oxide (spinel) cells
journal, April 1994

Pourbaix-like phase diagram for lithium manganese spinels in acid
journal, January 2010

Novel mixed polyanions lithium-ion battery cathode materials predicted by high-throughput ab initio computations
journal, January 2011

An aqueous electrolyte, sodium ion functional, large format energy storage device for stationary applications
journal, September 2012

Influence of oxalic acid on the dissolution kinetics of manganese oxide
journal, November 2012

Citric acid-assisted sol–gel synthesis of nanocrystalline LiMn2O4 spinel as cathode material
journal, August 2003

Electrochemical Quartz Crystal Microbalance for Insertion/Extraction of Lithium in Spinel LiMn ₂ O ₄ Thin Films
journal, July 1999

Thermodynamic Properties of Manganese Oxides
journal, July 1996

Sodium Charge Storage in Thin Films of MnO ₂ Derived by Electrochemical Oxidation of MnO Atomic Layer Deposition Films
journal, January 2015

Proton insertion and lithium-proton exchange in spinel lithium manganates
journal, May 1997

Electronic properties of LiMn2−x Ti x O4
journal, September 2009

High Cycling Stability and Extreme Rate Performance in Nanoscaled LiMn ₂ O ₄ Thin Films
journal, September 2015

VESTA 3 for three-dimensional visualization of crystal, volumetric and morphology data
journal, October 2011

First principles computational materials design for energy storage materials in lithium ion batteries
journal, January 2009

Synthesis of spinel LiMn2O4 using direct solid state reaction
journal, October 2002

Charge and spin ordering in ${LiMn}_{2} O_{4}$
journal, August 2001

Ground-state properties of multivalent manganese oxides: Density functional and hybrid density functional calculations
journal, May 2007

Preparation, structure and electrochemical properties of spinel Li1−xMn2−yO4 cathode material for lithium ion batteries
journal, April 2000

Atomic Layer Deposition of Spinel Lithium Manganese Oxide by Film-Body-Controlled Lithium Incorporation for Thin-Film Lithium-Ion Batteries
journal, December 2013

Bulk and Surface Tunneling Hydrogen Defects in Alumina
journal, August 2013

Crystalline MnO[sub 2] as Possible Alternatives to Amorphous Compounds in Electrochemical Supercapacitors
journal, January 2006

Fast Li-Ion Insertion into Nanosized LiMn ₂ O ₄ without Domain Boundaries
journal, January 2010

Nano LiMn2O4 as cathode material of high rate capability for lithium ion batteries
journal, January 2012

“Inner” and “outer” active surface of RuO2 electrodes
journal, January 1990

Low-Temperature Synthesis of Lithium Manganese Oxide Using LiCl-Li ₂ CO ₃ and Manganese Acetate Eutectic Mixture
journal, November 2011

Electrochemical Impedance Spectroscopy
book, February 2008

First-principles calculations for defects and impurities: Applications to III-nitrides
journal, April 2004

Rechargeable Li[sub 1+x]Mn[sub 2]O[sub 4]∕Carbon Cells with a New Electrolyte Composition
journal, January 1993

Electrochemistry of Manganese Dioxide in Lithium Nonaqueous Cell
journal, January 1989

Hydrothermal synthesis of LiMn2O4/C composite as a cathode for rechargeable lithium-ion battery with excellent rate capability
journal, September 2009

Achieving electrochemical capacitor functionality from nanoscale LiMn2O4 coatings on 3-D carbon nanoarchitectures
journal, January 2013

Challenges in the development of advanced Li-ion batteries: a review
journal, January 2011

Chemical potential dependence of defect formation energies in GaAs: Application to Ga self-diffusion
journal, October 1991

Ceramic and polymeric solid electrolytes for lithium-ion batteries
journal, August 2010

Commentary: The Materials Project: A materials genome approach to accelerating materials innovation
journal, July 2013

Charge Storage in Cation Incorporated α-MnO ₂
journal, February 2015

Phase-controlled synthesis of polymorphic MnO ₂ structures for electrochemical energy storage
journal, January 2015

Effect of substrate on the characteristics of manganese(IV) oxide thin films prepared by atomic layer deposition
journal, December 2004

The reduction and oxidation behaviour of manganese oxides
journal, January 1999

Growth of manganese oxide thin films by atomic layer deposition
journal, November 2003

Accurate defect levels obtained from the HSE06 range-separated hybrid functional
journal, April 2010

Pseudocapacitive Contributions to Electrochemical Energy Storage in TiO₂ (Anatase) Nanoparticles
journal, October 2007

Beyond the ability of Rietveld analysis: MEM-based pattern fitting
journal, August 2004

Characterization and electrochemical performance of the spinel LiMn2O4 prepared from É›-MnO2
journal, May 2000

Polymer Electrolytes for Lithium-Ion Batteries
journal, April 1998

Charge Storage Mechanism of MnO ₂ Electrode Used in Aqueous Electrochemical Capacitor
journal, August 2004

Batteries for lithium recovery from brines
journal, January 2012

Atomic layer deposition of MnO using Bis(ethylcyclopentadienyl)manganese and H2O
journal, August 2009

Highly selective lithium recovery from brine using a λ-MnO2–Ag battery
journal, January 2013

Surface structure and equilibrium particle shape of the LiMn $_{2}$ O $_{4}$ spinel from first-principles calculations
journal, February 2013

The Unified Electrochemical Band Diagram Framework: Understanding the Driving Forces of Materials Electrochemistry
journal, August 2018

Modulation of the Optical Properties of Lithium Manganese Oxide via Li-Ion De/Intercalation
journal, April 2018

Unveiling Conversion Reaction on Intercalation-Based Transition Metal Oxides for High Power, High Energy Aqueous Lithium Battery
journal, October 2018

Discovery of Anion Insertion Electrochemistry in Layered Hydroxide Nanomaterials
journal, February 2019

Growth behavior, work function, and band gap tuning of nanocrystalline LiMn ₂ O ₄ thin films
journal, August 2019

Efficient Capacitive Deionization Using Thin Film Sodium Manganese Oxide
journal, January 2018

Unveiling Conversion Reaction on Intercalation‐Based Transition Metal Oxides for High Power, High Energy Aqueous Lithium Battery
journal, July 2021

Discovery of Anion Insertion Electrochemistry in Layered Hydroxide Nanomaterials
journal, February 2019