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Title: Silver-Containing α-MnO2 Nanorods: Electrochemistry in Na-Based Battery Systems

Journal Article · · ACS Applied Materials and Interfaces
 [1];  [2];  [2];  [2];  [2];  [1];  [1];  [3]
  1. Stony Brook Univ., NY (United States)
  2. Brookhaven National Lab. (BNL), Upton, NY (United States)
  3. Brookhaven National Lab. (BNL), Upton, NY (United States); Stony Brook Univ., NY (United States)

Manganese oxides are considered attractive cathode materials for rechargeable batteries due to the high abundance and environmental friendliness of manganese. In particular, cryptomelane and hollandite are desirable due to their ability to host cations within their octahedral molecular sieve (OMS-2) Alpha-MnO2 structure. In this work, we investigate silver containing Alpha-MnO2 structured materials (AgxMn8O16, x = 1.22, L-Ag-OMS-2 or 1.66, H-Ag-OMS-2) as host materials for Li ion and Na ion insertion/de-insertion. The results indicate a significant difference in the lithiation versus sodiation process the OMS-2 materials. Initial reduction of Ag1.22Mn8O16 to 1.0 V delivered ~370 mAh/g. Cycling of Ag1.22Mn8O16 between voltage ranges of 3.8 - 1.7 V and 3.8 - 1.3 V in a Na battery delivered initial capacities of 113 and 247 mAh/g, respectively. In contrast, Ag1.66Mn8O16 delivered only 15 mAh/g, ~0.5 electron equivalents, to 1.7 and 1.3 volts. Study of the system by electrochemical impedance spectroscopy (EIS) showed a significant decrease in charge transfer resistance from 2029 Omega to 594 Omega after 1.5 electron equivalents per Ag1.22Mn8O16 formula unit of Na ion insertion. In contrast, both Ag1.22Mn8O16 and Ag1.66Mn8O16 exhibited gradual impedance increases during lithiation. The formation of silver metal could be detected only in the sodiated material by X-ray diffraction (XRD). Thus, the impedance of Ag-OMS-2 decreases upon sodiation coincident with the formation of silver metal during the discharge process, consistent with the more favorable formation of silver metal during the sodiation process relative to the lithation process.

Research Organization:
Brookhaven National Lab. (BNL), Upton, NY (United States); Energy Frontier Research Centers (EFRC) (United States). Center for Mesoscale Transport Properties (m2M)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
SC0012704; SC0012673
OSTI ID:
1439851
Report Number(s):
BNL-113936-2017-JAAM
Journal Information:
ACS Applied Materials and Interfaces, Vol. 9, Issue 5; ISSN 1944-8244
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 35 works
Citation information provided by
Web of Science

References (51)

Evolution of Strategies for Modern Rechargeable Batteries journal June 2012
The Li-Ion Rechargeable Battery: A Perspective journal January 2013
Building better batteries journal February 2008
Materials Science and Materials Chemistry for Large Scale Electrochemical Energy Storage: From Transportation to Electrical Grid journal June 2012
Electrical energy storage for transportation—approaching the limits of, and going beyond, lithium-ion batteries journal January 2012
The Emerging Chemistry of Sodium Ion Batteries for Electrochemical Energy Storage journal February 2015
Room-temperature stationary sodium-ion batteries for large-scale electric energy storage journal January 2013
Cathode materials for magnesium and magnesium-ion based batteries journal March 2015
Challenges and Prospects of Lithium–Sulfur Batteries journal June 2012
Li–O2 and Li–S batteries with high energy storage journal January 2012
Challenges of non-aqueous Li–O2 batteries: electrolytes, catalysts, and anodes journal January 2013
Revised effective ionic radii and systematic studies of interatomic distances in halides and chalcogenides journal September 1976
Electrochemical intercalation and deintercalation of NaxMnO2 bronzes journal May 1985
Synthesis and characterization of high-temperature hexagonal P2-Na0.6 MnO2 and its electrochemical behaviour as cathode in sodium cells journal February 2002
Electrochemical and Thermal Properties of α-NaFeO 2 Cathode for Na-Ion Batteries journal January 2013
Electrochemical investigation of the P2–NaxCoO2 phase diagram journal December 2010
NaCrO 2 cathode for high-rate sodium-ion batteries journal January 2015
P2-NaxVO2 system as electrodes for batteries and electron-correlated materials journal November 2012
P2-type Nax[Fe1/2Mn1/2]O2 made from earth-abundant elements for rechargeable Na batteries journal April 2012
Study of the Insertion/Deinsertion Mechanism of Sodium into Na 0.44 MnO 2 journal April 2007
Ab Initio Study of the Sodium Intercalation and Intermediate Phases in Na 0.44 MnO 2 for Sodium-Ion Battery journal March 2012
Facile Synthesis of Nanorod-like Single Crystalline Na 0.44 MnO 2 for High Performance Sodium-Ion Batteries journal January 2015
Hydrothermal synthesis of α-MnO2 and β-MnO2 nanorods as high capacity cathode materials for sodium ion batteries journal January 2013
β-MnO2 nanorods with exposed tunnel structures as high-performance cathode materials for sodium-ion batteries journal November 2013
Electrochemistry of Hollandite α-MnO 2 : Li-Ion and Na-Ion Insertion and Li 2 O Incorporation journal June 2013
Synthesis and Electrochemistry of Silver Hollandite journal January 2010
Synthetic Control of Composition and Crystallite Size of Silver Hollandite, Ag x Mn 8 O 16 : Impact on Electrochemistry journal September 2012
The Electrochemistry of Silver Hollandite Nanorods, Ag x Mn 8 O 16 : Enhancement of Electrochemical Battery Performance via Dimensional and Compositional Control journal January 2013
Structural Defects of Silver Hollandite, Ag x Mn 8 O y , Nanorods: Dramatic Impact on Electrochemistry journal July 2015
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
The structure of K 1.33 Mn 8 O 16 and cation ordering in hollandite-type structures journal April 1986
The Reduction of Silver Vanadium Oxide in Lithium/Silver Vanadium Oxide Cells journal January 1988
Solid-State Characterization of Reduced Silver Vanadium Oxide from the Li/SVO Discharge Reaction journal December 1994
Electrochemical Reduction of Silver Vanadium Phosphorus Oxide, Ag 2 VO 2 PO 4 : The Formation of Electrically Conductive Metallic Silver Nanoparticles journal October 2009
Energy dispersive X-ray diffraction of lithium–silver vanadium phosphorous oxide cells: in situ cathode depth profiling of an electrochemical reduction–displacement reaction journal January 2013
Electrochemical reduction of silver vanadium phosphorous oxide, Ag2VO2PO4: Silver metal deposition and associated increase in electrical conductivity journal October 2010
Microwave-Assisted Synthesis of Silver Vanadium Phosphorus Oxide, Ag 2 VO 2 PO 4 : Crystallite Size Control and Impact on Electrochemistry journal March 2016
Electrochemical Reduction of Ag 0.48 VOPO 4 : A Mechanistic Study Employing X-Ray Absorption Spectroscopy and X-Ray Powder Diffraction journal January 2015
In situ visualization of Li/Ag2VP2O8 batteries revealing rate-dependent discharge mechanism journal January 2015
Electrochemical reduction of Ag 2 VP 2 O 8 composite electrodes visualized via in situ energy dispersive X-ray diffraction (EDXRD): unexpected conductive additive effects journal January 2015
Oxygen Functionalization of Multiwall Carbon Nanotubes by Microwave-Excited Surface-Wave Plasma Treatment journal April 2009
Synthesis and characterization of microporous carbon nitride journal April 2008
Microstructural Features of α-MnO[sub 2] Electrodes for Lithium Batteries journal January 1998
Effects of Cu 2+ Ions on the Structure and Reactivity of Todorokite- and Cryptomelane-Type Manganese Oxide Octahedral Molecular Sieves journal July 1999
Microwave-Assisted Hydrothermal Synthesis of Cryptomelane-Type Octahedral Molecular Sieves (OMS-2) and Their Catalytic Studies journal June 2010
Synthetic Routes to Microporous Manganese Oxides journal October 1997
Enhancement of Sodium Ion Battery Performance Enabled by Oxygen Vacancies journal June 2015
Mesoporous Manganese Oxide Nanowires for High-Capacity, High-Rate, Hybrid Electrical Energy Storage journal September 2011
Highly Ordered MnO 2 Nanopillars for Enhanced Supercapacitor Performance journal May 2013
Porous Manganese Oxide Octahedral Molecular Sieves and Octahedral Layered Materials journal April 2008
Asynchronous Crystal Cell Expansion during Lithiation of K + -Stabilized α-MnO 2 journal April 2015

Cited By (8)

Visualization of lithium-ion transport and phase evolution within and between manganese oxide nanorods journal May 2017
Capacity Retention for (De)lithiation of Silver Containing α-MnO 2 : Impact of Structural Distortion and Transition Metal Dissolution journal January 2018
Review of the Stability/Capacity Trade-off in Silver Hollandite Lithium Battery Cathodes journal January 2018
Compositional control of radionuclide retention in hollandite‐based ceramic waste forms for Cs‐immobilization journal December 2018
Silver-Containing α-MnO 2  Nanorods: Electrochemistry in Rechargeable Aqueous Zn-MnO 2 Batteries journal January 2019
Synthesis and Characterization of 2 × 4 Tunnel Structured Manganese Dioxides as Cathodes in Rechargeable Li, Na, and Mg Batteries journal January 2019
Brittle fracture to recoverable plasticity: Polytypism-dependent nanomechanics in todorokite-like nanobelts text January 2021
Brittle fracture to recoverable plasticity: Polytypism-dependent nanomechanics in todorokite-like nanobelts text January 2021