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Title: Probing the Release and Uptake of Water in α-MnO2 · xH2O

Journal Article · · Chemistry of Materials
 [1];  [2];  [1];  [1];  [1];  [3];  [1]; ORCiD logo [1];  [1]
  1. Argonne National Lab. (ANL), Argonne, IL (United States)
  2. Argonne National Lab. (ANL), Argonne, IL (United States); Duke Univ., Durham, NC (United States)
  3. Argonne National Lab. (ANL), Argonne, IL (United States); Northwestern Univ., Evanston, IL (United States)
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Alpha-MnO2 is of interest as a cathode material for 3 V lithium batteries and as an electrode/electrocatalyst for higher energy, hybrid Li-ion/Li–O2 systems. It has a structure with large tunnels that contain stabilizing cations such as Ba2+, K+ , NH4+ , and H3O+ (or water, H2O). When stabilized by H3O+ /H2O, the protons can be ion-exchanged with lithium to produce a Li2O-stabilized α-MnO2 structure. It has been speculated that the electrocatalytic process in Li–O2 cells may be linked to the removal of lithium and oxygen from the host α-MnO2 structure during charge, and their reintroduction during discharge. In this investigation, hydrated α-MnO2 was used, as a first step, to study the release and uptake of oxygen in α-MnO2. Temperature-resolved in situ synchrotron X-ray diffraction (XRD) revealed a nonlinear, two-stage, volume change profile, which with the aide of X-ray absorption near-edge spectroscopy (XANES), redox titration, and density functional theory (DFT) calculations, is interpreted as the release of water from the α-MnO2 tunnels. The two stages correspond to H2O release from intercalated H2O species at lower temperatures and H3O+ species at higher temperature. Thermogravimetric analysis confirmed the release of oxygen from α-MnO2 in several stages during heating–including surface water, occluded water, and structural oxygen–and in situ UV resonance Raman spectroscopy corroborated the uptake and release of tunnel water by revealing small shifts in frequencies during the heating and cooling of α-MnO2. Lastly, DFT calculations revealed the likelihood of disordered water species in binding sites in α-MnO2 tunnels and a facile diffusion process.

Research Organization:
Argonne National Laboratory (ANL), Argonne, IL (United States); Energy Frontier Research Centers (EFRC) (United States). Center for Electrical Energy Storage (CEES)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
AC02-06CH11357
OSTI ID:
1389649
Journal Information:
Chemistry of Materials, Vol. 29, Issue 4; ISSN 0897-4756
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 29 works
Citation information provided by
Web of Science

References (39)

Manganese oxide minerals: Crystal structures and economic and environmental significance journal March 1999
Manganese oxides for lithium batteries journal January 1997
Structural and electrochemical studies of α-manganese dioxide (α-MnO2) journal October 1997
Effect of Crystallographic Structure of MnO 2 on Its Electrochemical Capacitance Properties journal February 2008
α-MnO2 Nanowires: A Catalyst for the O2 Electrode in Rechargeable Lithium Batteries journal June 2008
In situ high-energy synchrotron X-ray diffraction studies and first principles modeling of α-MnO 2 electrodes in Li–O 2 and Li-ion coin cells journal January 2015
Vision for Designing High-Energy, Hybrid Li Ion/Li–O 2 Cells journal October 2013
Study of the Insertion/Deinsertion Mechanism of Sodium into Na 0.44 MnO 2 journal April 2007
α-MnO2 as a cathode material for rechargeable Mg batteries journal September 2012
The High Performance of Crystal Water Containing Manganese Birnessite Cathodes for Magnesium Batteries journal May 2015
Investigation of the Mechanism of Mg Insertion in Birnessite in Nonaqueous and Aqueous Rechargeable Mg-Ion Batteries journal January 2016
Direct Observation of Reversible Magnesium Ion Intercalation into a Spinel Oxide Host journal April 2015
Alpha manganese dioxide for lithium batteries: A structural and electrochemical study journal February 1992
Synthesis, Characterization, and Structural Modeling of High-Capacity, Dual Functioning MnO 2 Electrode/Electrocatalysts for Li-O 2 Cells journal July 2012
Atomistic and First Principles: Computational Studies of LiO2 Batteries book January 2014
Evidence of reversible oxygen participation in anomalously high capacity Li- and Mn-rich cathodes for Li-ion batteries journal March 2016
Determination of Mn valence states in mixed-valent manganates by XANES spectroscopy journal May 2012
Two-dimensional detector software: From real detector to idealised image or two-theta scan journal January 1996
EXPGUI , a graphical user interface for GSAS journal April 2001
Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set journal October 1996
From ultrasoft pseudopotentials to the projector augmented-wave method journal January 1999
Projector augmented-wave method journal December 1994
Rationale for mixing exact exchange with density functional approximations journal December 1996
Electron-energy-loss spectra and the structural stability of nickel oxide: An LSDA+U study journal January 1998
Semiempirical GGA-type density functional constructed with a long-range dispersion correction journal January 2006
Improved tangent estimate in the nudged elastic band method for finding minimum energy paths and saddle points journal December 2000
First-principles calculations of the ferroelastic transition between rutile-type and CaCl 2 -type SiO 2 at high pressures journal October 2008
Improved grid-based algorithm for Bader charge allocation journal January 2007
A grid-based Bader analysis algorithm without lattice bias journal January 2009
Effect of the atmosphere on chemical composition and electrochemical properties of solid electrolyte interface on electrodeposited Li metal journal August 2011
EXAFS analysis using FEFF and FEFFIT journal March 2001
Resonance Raman and surface- and tip-enhanced Raman spectroscopy methods to study solid catalysts and heterogeneous catalytic reactions journal January 2010
The crystal structure of hollandite, the related manganese oxide minerals, and α-MnO2 journal March 1950
Nanostructured manganese oxide clusters supported on mesoporous silica as efficient oxygen-evolving catalysts journal January 2010
Lithium ion insertion and extraction reactions with Hollandite-type manganese dioxide free from any stabilizing cations in its tunnel cavity journal September 2005
MnO 2 Thin Film Electrodes for Enhanced Reliability of Thin Glass Capacitors journal July 2015
A comparison study on Raman scattering properties of α- and β-MnO2 journal August 2009
Microstructures and Spectroscopic Properties of Cryptomelane-type Manganese Dioxide Nanofibers journal July 2008
Lattice vibrations of manganese oxides journal February 2004

Cited By (5)

Self‐Limiting Galvanic Growth of MnO 2 Monolayers on a Liquid Metal—Applied to Photocatalysis journal July 2019
Charge localization and ordering in A 2 Mn 8 O 16 hollandite group oxides: Impact of density functional theory approaches journal December 2017
Lab‐Scale In Situ X‐Ray Diffraction Technique for Different Battery Systems: Designs, Applications, and Perspectives journal May 2019
In Situ Probing Multiple-Scale Structures of Energy Materials for Li-Ion Batteries journal May 2019
Hierarchical porosity via layer-tunnel conversion of macroporous δ-MnO 2 nanosheet assemblies journal January 2020

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