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

Title: Macromolecular Design Strategies for Preventing Active-Material Crossover in Non-Aqueous All-Organic Redox-Flow Batteries

Journal Article · · Angewandte Chemie (International Edition)
 [1];  [2];  [2];  [2];  [3];  [3];  [4];  [2];  [3]; ORCiD logo [2]
  1. Univ. of California, Berkeley, CA (United States)
  2. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
  3. Univ. of Illinois, Urbana, IL (United States)
  4. Univ. of Michigan, Ann Arbor, MI (United States)

Intermittent energy sources, including solar and wind, require scalable, low-cost, multi-hour energy storage solutions in order to be effectively incorporated into the grid. All-Organic non-aqueous redox-flow batteries offer a solution, but suffer from rapid capacity fade and low Coulombic efficiency due to the high permeability of redox-active species across the battery's membrane. In this paper, we show that active-species crossover is arrested by scaling the membrane's pore size to molecular dimensions and in turn increasing the size of the active material above the membrane's pore-size exclusion limit. When oligomeric redox-active organics (RAOs) were paired with microporous polymer membranes, the rate of active-material crossover was reduced more than 9000-fold compared to traditional separators at minimal cost to ionic conductivity. This corresponds to an absolute rate of RAO crossover of less than 3 μmol cm-2 day-1 (for a 1.0 m concentration gradient), which exceeds performance targets recently set forth by the battery industry. Finally, this strategy was generalizable to both high and low-potential RAOs in a variety of non-aqueous electrolytes, highlighting the versatility of macromolecular design in implementing next-generation redox-flow batteries.

Research Organization:
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOD
Grant/Contract Number:
AC02-05CH11231
OSTI ID:
1379650
Journal Information:
Angewandte Chemie (International Edition), Vol. 56, Issue 6; ISSN 1433-7851
Publisher:
WileyCopyright Statement
Country of Publication:
United States
Language:
English

References (32)

Molecular Separation with Organic Solvent Nanofiltration: A Critical Review journal October 2014
Pathways to low-cost electrochemical energy storage: a comparison of aqueous and nonaqueous flow batteries journal January 2014
Polymers of intrinsic microporosity (PIMs): organic materials for membrane separations, heterogeneous catalysis and hydrogen storage journal January 2006
Exploitation of Intrinsic Microporosity in Polymer-Based Materials journal June 2010
Gas Separation, Free Volume Distribution, and Physical Aging of a Highly Microporous Spirobisindane Polymer journal April 2008
An aqueous, polymer-based redox-flow battery using non-corrosive, safe and low-cost materials journal October 2015
Understanding and controlling the chemical evolution and polysulfide-blocking ability of lithium–sulfur battery membranes cast from polymers of intrinsic microporosity journal January 2016
Azide-based Cross-Linking of Polymers of Intrinsic Microporosity (PIMs) for Condensable Gas Separation journal March 2011
Battery Separators journal October 2004
Polymers of intrinsic microporosity (PIMs): robust, solution-processable, organic nanoporous materials journal January 2004
Recent Progress in Redox Flow Battery Research and Development journal September 2012
The Chemistry of Redox-Flow Batteries journal June 2015
Redox Active Colloids as Discrete Energy Storage Carriers journal September 2016
A review of current developments in non-aqueous redox flow batteries: characterization of their membranes for design perspective journal January 2013
Inorganic solid Li ion conductors: An overview journal June 2009
Transport Property Requirements for Flow Battery Separators journal July 2015
Radical Compatibility with Nonaqueous Electrolytes and Its Impact on an All-Organic Redox Flow Battery journal April 2015
A symmetric organic-based nonaqueous redox flow battery and its state of charge diagnostics by FTIR journal January 2016
Liquid Catholyte Molecules for Nonaqueous Redox Flow Batteries journal November 2014
Evolutionary Design of Low Molecular Weight Organic Anolyte Materials for Applications in Nonaqueous Redox Flow Batteries journal October 2015
Impact of Redox-Active Polymer Molecular Weight on the Electrochemical Properties and Transport Across Porous Separators in Nonaqueous Solvents
  • Nagarjuna, Gavvalapalli; Hui, Jingshu; Cheng, Kevin J.
  • Journal of the American Chemical Society, Vol. 136, Issue 46, p. 16309-16316 https://doi.org/10.1021/ja508482e
journal October 2014
Impact of Backbone Tether Length and Structure on the Electrochemical Performance of Viologen Redox Active Polymers journal October 2016
Electrical Energy Storage for the Grid: A Battery of Choices journal November 2011
Die Chemie der Redox-Flow-Batterien journal June 2015
Polysulfide-Blocking Microporous Polymer Membrane Tailored for Hybrid Li-Sulfur Flow Batteries journal August 2015
Redox Active Polymers as Soluble Nanomaterials for Energy Storage journal September 2016
An All-Organic Non-aqueous Lithium-Ion Redox Flow Battery journal June 2012
Radical Compatibility with Nonaqueous Electrolytes and Its Impact on an All-Organic Redox Flow Battery journal April 2015
Poly(boron-dipyrromethene)—A Redox-Active Polymer Class for Polymer Redox-Flow Batteries journal May 2016
Battery Separators journal December 2004
Polymers of Intrinsic Microporosity (PIMs): Organic Materials for Membrane Separations, Heterogeneous Catalysis and Hydrogen Storage journal November 2006
An aqueous, polymer-based redox-flow battery using non-corrosive, safe, and low-cost materials journal June 2016

Cited By (15)

Engineered Transport in Microporous Materials and Membranes for Clean Energy Technologies journal January 2018
Gradient-Distributed Metal-Organic Framework-Based Porous Membranes for Nonaqueous Redox Flow Batteries journal October 2018
Porphyrin-Based Symmetric Redox-Flow Batteries towards Cold-Climate Energy Storage journal February 2018
Strategien für kostengünstige und leistungsstarke Dual‐Ionen‐Batterien journal November 2019
A pH‐Neutral, Metal‐Free Aqueous Organic Redox Flow Battery Employing an Ammonium Anthraquinone Anolyte journal September 2019
Strategies towards Low‐Cost Dual‐Ion Batteries with High Performance journal November 2019
A pH‐Neutral, Metal‐Free Aqueous Organic Redox Flow Battery Employing an Ammonium Anthraquinone Anolyte journal November 2019
Toward High‐Voltage, Energy‐Dense, and Durable Aqueous Organic Redox Flow Batteries: Role of the Supporting Electrolytes journal September 2018
Polymers of Intrinsic Microporosity in Triphasic Electrochemistry: Perspectives journal July 2019
Electrochemical Evaluation of a Napthalene Diimide Derivative for Potential Application in Aqueous Organic Redox Flow Batteries journal August 2019
Anion–π interactions in lithium–organic redox flow batteries journal January 2019
Progress in the Design of Polyoxovanadate-Alkoxides as Charge Carriers for Nonaqueous Redox Flow Batteries journal March 2019
Porphyrin-Based Symmetric Redox-Flow Batteries towards Cold-Climate Energy Storage journal February 2018
High-Performance Oligomeric Catholytes for Effective Macromolecular Separation in Nonaqueous Redox Flow Batteries journal January 2018
Preventing Crossover in Redox Flow Batteries through Active Material Oligomerization journal February 2018