DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Inhomogeneous structural evolution of silver-containing Alpha-MnO2 nanorods in sodium-ion batteries investigated by comparative transmission electron microscopy approach

Journal Article · · Journal of Power Sources
 [1];  [2];  [2];  [3];  [4];  [5];  [3];  [6]; ORCiD logo [3]
  1. Brookhaven National Lab. (BNL), Upton, NY (United States); Seoul National Univ., Seoul (Korea, Republic of)
  2. Stony Brook Univ., NY (United States). Dept. of Chemistry
  3. Brookhaven National Lab. (BNL), Upton, NY (United States)
  4. Stony Brook Univ., NY (United States). Dept. of Chemistry, and Dept. of Materials Science and Chemical Engineering; Brookhaven National Lab. (BNL), Upton, NY (United States)
  5. Stony Brook Univ., NY (United States). Dept. of Chemistry, and Dept. of Materials Science and Chemical Engineering
  6. Seoul National Univ., Seoul (Korea, Republic of)

Alpha-MnO2 is an attractive cathode candidate for sodium-ion batteries attributed to its unique one-dimensional 2×2 tunnels for facile sodium-ion diffusion, in addition to its incomparable cost advantage. In particular, α-MnO2 shows superior rate capability with silver stabilizing ions at the center of tunnels that improve electrical conductivity. In this work, we directly compare structural transformation of silver-containing α-MnO2 nanorods (Ag1.22Mn8O16-x or L-Ag-HOL and Ag1.66Mn8O16-y or H–Ag-HOL), containing higher and lower concentrations of oxygen vacancies respectively, by transmission electron microscopy (TEM). The elaborate comparative and statistical TEM studies eliminate concerns regarding generalization errors and facilitate rational structural development of nanorods with improved functionality. It is found that sodium ions favorably diffuse through the area where oxygen vacancies are concentrated, and the samples with more silver ions and fewer oxygen vacancies (H–Ag-HOL) show more significant structural deformation with more inhomogeneous sodiation. The difference in functional electrochemistry coupled with the observed difference in inter- and intra-nanorod inhomogeneous structural evolution emphasizes the significance of the uniform electrical conductivity of the electrode. This work helps to improve the α-MnO2 electrode material for sodium-ion batteries as well as suggesting the importance of delicate statistical approaches for TEM investigations.

Research Organization:
Energy Frontier Research Centers (EFRC) (United States). Center for Mesoscale Transport Properties (m2mt); Brookhaven National Laboratory (BNL), Upton, NY (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE
Grant/Contract Number:
SC0012704
OSTI ID:
1566823
Alternate ID(s):
OSTI ID: 1778392
Report Number(s):
BNL-212113-2019-JAAM
Journal Information:
Journal of Power Sources, Vol. 435, Issue C; ISSN 0378-7753
Publisher:
ElsevierCopyright Statement
Country of Publication:
United States
Language:
English

References (33)

Sodium-Ion Batteries journal May 2012
Recycling application of waste Li–MnO 2 batteries as efficient catalysts based on electrochemical lithiation to improve catalytic activity journal January 2018
Review—Practical Issues and Future Perspective for Na-Ion Batteries journal January 2015
A phosphorene–graphene hybrid material as a high-capacity anode for sodium-ion batteries journal September 2015
The Emerging Chemistry of Sodium Ion Batteries for Electrochemical Energy Storage journal February 2015
Carbon Quantum Dots and Their Derivative 3D Porous Carbon Frameworks for Sodium-Ion Batteries with Ultralong Cycle Life journal October 2015
Hierarchical Hollow-Microsphere Metal-Selenide@Carbon Composites with Rational Surface Engineering for Advanced Sodium Storage journal November 2018
Multidimensional Evolution of Carbon Structures Underpinned by Temperature-Induced Intermediate of Chloride for Sodium-Ion Batteries journal March 2018
Electrochemistry of Hollandite α-MnO 2 : Li-Ion and Na-Ion Insertion and Li 2 O Incorporation journal June 2013
Silver-Containing α-MnO 2 Nanorods: Electrochemistry in Na-Based Battery Systems journal September 2016
α-MnO2 as a cathode material for rechargeable Mg batteries journal September 2012
Energetic Zinc Ion Chemistry: The Rechargeable Zinc Ion Battery journal December 2011
Unveiling the Structural Evolution of Ag 1.2 Mn 8 O 16 under Coulombically Controlled (De)Lithiation journal January 2018
Investigation of α-MnO 2 Tunneled Structures as Model Cation Hosts for Energy Storage journal February 2018
Probing the Release and Uptake of Water in α-MnO 2 · x H 2 O journal February 2017
Development and utility of manganese oxides as cathodes in lithium batteries journal March 2007
Asynchronous Crystal Cell Expansion during Lithiation of K + -Stabilized α-MnO 2 journal April 2015
Tunnel Structured α-MnO 2 with Different Tunnel Cations (H + , K + , Ag + ) as Cathode Materials in Rechargeable Lithium Batteries: The Role of Tunnel Cation on Electrochemistry journal January 2017
The Effect of Silver Ion Occupancy on Hollandite Lattice Structure journal January 2018
Synthetic Control of Composition and Crystallite Size of Silver Hollandite, Ag x Mn 8 O 16 : Impact on Electrochemistry journal September 2012
Deliberately Designed Atomic-Level Silver-Containing Interface Results in Improved Rate Capability and Utilization of Silver Hollandite for Lithium-Ion Storage journal December 2017
Structural Defects of Silver Hollandite, Ag x Mn 8 O y , Nanorods: Dramatic Impact on Electrochemistry journal July 2015
Visualization of lithium-ion transport and phase evolution within and between manganese oxide nanorods journal May 2017
Deconvolution of Composition and Crystallite Size of Silver Hollandite Nanorods: Influence on Electrochemistry journal January 2017
Tracking inhomogeneity in high-capacity lithium iron phosphate batteries journal February 2015
Understanding Inhomogeneous Reactions in Li-Ion Batteries: Operando Synchrotron X-Ray Diffraction on Two-Layer Electrodes journal May 2015
Synthesis and Electrochemistry of Silver Hollandite journal January 2010
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
Lithiation Mechanism of Tunnel-Structured MnO 2 Electrode Investigated by In Situ Transmission Electron Microscopy journal October 2017
Determination of manganese oxidation states in solids by electron energy-loss spectroscopy journal January 1987
Electron-energy-loss core-edge structures in manganese oxides journal July 1993
High-resolution parallel electron energy-loss spectroscopy of Mn L2,3-edges in inorganic manganese compounds journal August 1994
White lines and d -electron occupancies for the 3 d and 4 d transition metals journal April 1993

Figures / Tables (4)