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Mechanism of Zn Insertion into Nanostructured δ-MnO 2 : A Nonaqueous Rechargeable Zn Metal Battery

Journal Article · · Chemistry of Materials
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  1. Argonne National Lab. (ANL), Argonne, IL (United States)
  2. Central Michigan Univ., Mount Pleasant, MI (United States)
  3. Argonne National Lab. (ANL), Argonne, IL (United States); Univ. of Illinois, Chicago, IL (United States)
  4. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
+ Show Author Affiliations

Unlike the more established lithium-ion based energy storage chemistries, the complex intercalation chemistry of multivalent cations in a host lattice is not well understood, especially the relationship between the intercalating species solution chemistry and the prevalence and type of side reactions. Among multivalent metals, a promising model system can be based on nonaqueous Zn2+ ion chemistry. There are several examples of these systems support the use of a Zn metal anode, and reversible intercalation cathodes have been reported. Our study utilizes a combination of analytical tools to probe the chemistry of a nanostructured δ-MnO2 cathode in association with a nonaqueous acetonitrile–Zn(TFSI)2 electrolyte and a Zn metal anode. As many of the issues related to understanding a multivalent battery relate to the electrolyte–electrode interface, the high surface area of a nanostructured cathode provides a significant interface between the electrolyte and cathode host that maximizes the spectroscopic signal of any side reactions or minor mechanistic pathways. There are numerous factors affecting capacity fade and issues associated with the second phase formation including Mn dissolution in heavily cycled Zn/δ-MnO2 cells are presented including dramatic mechanistic differences in the storage mechanism of this couple when compared to similar aqueous electrolytes are noted.

Research Organization:
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Grant/Contract Number:
AC05-00OR22725; AC02-06CH11357; SC0006877
OSTI ID:
1376620
Alternate ID(s):
OSTI ID: 1371698
Journal Information:
Chemistry of Materials, Journal Name: Chemistry of Materials Journal Issue: 11 Vol. 29; ISSN 0897-4756
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English

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A Hollow-Structured Manganese Oxide Cathode for Stable Zn-MnO2 Batteries journal May 2018
Recent Advances in Zn-Ion Batteries journal August 2018
Manganese-Oxide-Based Electrode Materials for Energy Storage Applications: How Close Are We to the Theoretical Capacitance? journal August 2018
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Ultrathin Surface Coating Enables Stabilized Zinc Metal Anode journal August 2018
Noninterference Revealing of “Layered to Layered” Zinc Storage Mechanism of δ‐MnO 2 toward Neutral Zn–Mn Batteries with Superior Performance journal March 2020
ZnNi x Mn x Co 2-2 x O 4 Spinel as a High-Voltage and High-Capacity Cathode Material for Nonaqueous Zn-Ion Batteries journal May 2018
High-Performance Reversible Aqueous Zn-Ion Battery Based on Porous MnO x Nanorods Coated by MOF-Derived N-Doped Carbon journal August 2018
Mechanistic Insights of Zn 2+ Storage in Sodium Vanadates journal August 2018
Defect Engineering of Oxygen‐Deficient Manganese Oxide to Achieve High‐Performing Aqueous Zinc Ion Battery journal February 2019
A Long-Cycle-Life Self-Doped Polyaniline Cathode for Rechargeable Aqueous Zinc Batteries journal November 2018
A Long-Cycle-Life Self-Doped Polyaniline Cathode for Rechargeable Aqueous Zinc Batteries journal November 2018
Challenges and perspectives for manganese‐based oxides for advanced aqueous zinc‐ion batteries journal December 2019
Unravelling H + /Zn 2+ Synergistic Intercalation in a Novel Phase of Manganese Oxide for High‐Performance Aqueous Rechargeable Battery journal October 2019
V2O5 Nanospheres with Mixed Vanadium Valences as High Electrochemically Active Aqueous Zinc-Ion Battery Cathode journal March 2019
Visible light driven water splitting through an innovative Cu-treated-δ-MnO 2 nanostructure: probing enhanced activity and mechanistic insights journal January 2018
Pseudocapacitive layered birnessite sodium manganese dioxide for high-rate non-aqueous sodium ion capacitors journal January 2018
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A long-lifespan, flexible zinc-ion secondary battery using a paper-like cathode from single-atomic layer MnO 2 nanosheets journal January 2019
Zinc ion stabilized MnO 2 nanospheres for high capacity and long lifespan aqueous zinc-ion batteries journal January 2019
Boosting the Zn-ion storage capability of birnessite manganese oxide nanoflorets by La 3+ intercalation journal January 2019
Nonaqueous electrolyte with dual-cations for high-voltage and long-life zinc batteries journal January 2020
Rechargeable Zn–MnO 2 batteries: advances, challenges and perspectives journal January 2020
Rechargeable Zinc-Ion Battery Based on Choline Chloride-Urea Deep Eutectic Solvent journal January 2019
Layered Sodium Manganese Oxide Na2Mn3O7 as an Insertion Host for Aqueous Zinc-ion Batteries journal July 2019

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