skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Zincate-Blocking-Functionalized Polysulfone Separators for Secondary Zn–MnO2 Batteries

Journal Article · · ACS Applied Materials and Interfaces
 [1];  [1];  [1]; ORCiD logo [2];  [3];  [2];  [4]; ORCiD logo [1]
  1. Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)
  2. Urban Electric Power, Pearl River, NY (United States)
  3. City College of New York, NY (United States)
  4. Urban Electric Power, Pearl River, NY (United States); City College of New York, NY (United States)

Alkaline zinc–manganese dioxide (Zn–MnO2) batteries are well suited for grid storage applications because of their inherently safe, aqueous electrolyte and established materials supply chain, resulting in low production costs. With recent advances in the development of Cu/Bi-stabilized birnessite cathodes capable of the full 2-electron capacity equivalent of MnO2 (617 mA h/g), there is a need for selective separators that prevent zincate (Zn(OH)4)2– transport from the anode to the cathode during cycling, as this electrode system fails in the presence of dissolved zinc. In this work, we present the synthesis of N-butylimidazolium-functionalized polysulfone (NBI-PSU)-based separators and evaluate their ability to selectively transport hydroxide over zincate. We then examine their impact on the cycling of high depth of discharge Zn/(Cu/Bi–MnO2) batteries when inserted in between the cathode and anode. Initially, we establish our membranes’ selectivity by performing zincate and hydroxide diffusion tests, showing a marked improvement in zincate-blocking (DZn (cm2/min): 0.17 ± 0.04 × 10–6 for 50-PSU, our most selective separator vs 2.0 ± 0.8 × 10–6 for Cellophane 350P00 and 5.7 ± 0.8 × 10–6 for Celgard 3501), while maintaining similar crossover rates for hydroxide (DOH (cm2/min): 9.4 ± 0.1 × 10–6 for 50-PSU vs 17 ± 0.5 × 10–6 for Cellophane 350P00 and 6.7 ± 0.6 × 10–6 for Celgard 3501). We then implement our membranes into cells and observe an improvement in cycle life over control cells containing only the commercial separators (cell lifetime extended from 21 to 79 cycles).

Research Organization:
Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)
Sponsoring Organization:
USDOE National Nuclear Security Administration (NNSA); USDOE Laboratory Directed Research and Development (LDRD) Program; USDOE Office of Electricity (OE)
Grant/Contract Number:
NA0003525
OSTI ID:
1827609
Report Number(s):
SAND-2021-12123J; 700555
Journal Information:
ACS Applied Materials and Interfaces, Vol. 12, Issue 45; ISSN 1944-8244
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English

References (41)

Metal-Air Batteries with High Energy Density: Li-Air versus Zn-Air journal December 2010
Rechargeability and economic aspects of alkaline zinc–manganese dioxide cells for electrical storage and load leveling journal February 2015
Separator technologies for lithium-ion batteries journal December 2010
Material review of Li ion battery separators
  • Weber, Christoph J.; Geiger, Sigrid; Falusi, Sandra
  • REVIEW ON ELECTROCHEMICAL STORAGE MATERIALS AND TECHNOLOGY: Proceedings of the 1st International Freiberg Conference on Electrochemical Storage Materials, AIP Conference Proceedings https://doi.org/10.1063/1.4878480
conference January 2014
Battery Separators journal October 2004
Stripping Voltammetry for the Real Time Determination of Zinc Membrane Diffusion Coefficients in High pH: Towards Rapid Screening of Alkaline Battery Separators journal July 2017
Evaluation of a ceramic separator for use in rechargeable alkaline Zn/MnO2 batteries journal August 2018
Zinc Electrode Shape Change in Secondary Cells journal January 1972
Volumes of aqueous hydrogen and hydroxide ions at 0 to 200 °C journal October 2012
Rapid electrochemical synthesis of δ-MnO2 from γ-MnO2 and unleashing its performance as an energy dense electrode journal December 2017
Effect of Multiple Cation Electrolyte Mixtures on Rechargeable Zn–MnO 2 Alkaline Battery journal June 2016
Study of high-anionic conducting sulfonated microporous membranes for zinc-air electrochemical cells journal December 2008
Towards zinc-oxygen batteries with enhanced cycling stability: The benefit of anion-exchange ionomer for zinc sponge anodes journal August 2018
Effect of ZnO-Saturated Electrolyte on Rechargeable Alkaline Zinc Batteries at Increased Depth-of-Discharge journal January 2020
A calcium hydroxide interlayer as a selective separator for rechargeable alkaline Zn/MnO2 batteries journal August 2017
Rechargeable Zinc Alkaline Anodes for Long-Cycle Energy Storage journal May 2017
Interaction of zincate with additives turbidimetric, IR and Raman spectral analyses journal July 2000
Characterization and performance evaluation of lithium-ion battery separators journal December 2018
Through-Plane Conductivities of Membranes for Nonaqueous Redox Flow Batteries journal January 2015
Evaluation of the diffusion coefficient of the zincate ion using a rotating disk electrode journal March 1986
Cross‐Linked Polyvinyl Alcohol Films as Alkaline Battery Separators journal February 1983
Real-time materials evolution visualized within intact cycling alkaline batteries journal January 2014
Operando identification of the point of [Mn2]O4 spinel formation during γ-MnO2 discharge within batteries journal July 2016
Ion-Sieving Carbon Nanoshells for Deeply Rechargeable Zn-Based Aqueous Batteries journal October 2018
Intercalation and Conversion Reactions of Nanosized β-MnO 2 Cathode in the Secondary Zn/MnO 2 Alkaline Battery journal May 2018
Impact of Triethanolamine as an Additive for Rechargeable Alkaline Zn/MnO 2 Batteries under Limited Depth of Discharge Conditions journal January 2017
Rechargeable Solid-State Copper Sulfide Cathodes for Alkaline Batteries: Importance of the Copper Valence State journal January 2019
Electrospun polyetherimide nanofiber mat-reinforced, permselective polyvinyl alcohol composite separator membranes: A membrane-driven step closer toward rechargeable zinc–air batteries journal February 2016
The Secondary Alkaline Zinc Electrode journal January 1991
Rechargeable Cells with Modified MnO[sub 2] Cathodes journal January 1988
Hetaerolite Profiles in Alkaline Batteries Measured by High Energy EDXRD journal November 2014
Sealing ZnO nanorods for deeply rechargeable high-energy aqueous battery anodes journal November 2018
Design Strategy for Zinc Anodes with Enhanced Utilization and Retention: Electrodeposited Zinc Oxide on Carbon Mesh Protected by Ionomeric Layers journal October 2018
The potential use of cellophane test strips for the quick determination of food colours journal February 2015
An Operando Study of the Initial Discharge of Bi and Bi/Cu Modified MnO 2 journal January 2018
Inexpensive Cross‐Linked Polymeric Separators Made from Water‐Soluble Polymers journal February 1982
Suppression of Dendrite Formation of Zinc Electrodes by the Modification of Anion-Exchange Ionomer journal January 2012
Regenerable Cu-intercalated MnO2 layered cathode for highly cyclable energy dense batteries journal March 2017
Review—Multifunctional Separators: A Promising Approach for Improving the Durability and Performance of Li-Ion Batteries journal January 2019
A review on the separators of liquid electrolyte Li-ion batteries journal January 2007
Homogeneous Coating with an Anion-Exchange Ionomer Improves the Cycling Stability of Secondary Batteries with Zinc Anodes journal February 2018