skip to main content
US FlagAn official website of the United States government
dot gov icon
Official websites use .gov
A .gov website belongs to an official government organization in the United States.
https lock icon
Secure .gov websites use HTTPS
A lock ( lock ) or https:// means you've safely connected to the .gov website. Share sensitive information only on official, secure websites.

Explore Research Products in the PAR
It may take a few hours for recently added research products to appear in PAR search results.


Title: Development of high-voltage and high-energy membrane-free nonaqueous lithium-based organic redox flow batteries
Abstract Lithium-based nonaqueous redox flow batteries (LRFBs) are alternative systems to conventional aqueous redox flow batteries because of their higher operating voltage and theoretical energy density. However, the use of ion-selective membranes limits the large-scale applicability of LRFBs. Here, we report high-voltage membrane-free LRFBs based on an all-organic biphasic system that uses Li metal anode and 2,4,6-tri-(1-cyclohexyloxy-4-imino-2,2,6,6-tetramethylpiperidine)-1,3,5-triazine (Tri-TEMPO), N-propyl phenothiazine (C3-PTZ), and tris(dialkylamino)cyclopropenium (CP) cathodes. Under static conditions, the Li||Tri-TEMPO, Li||C3-PTZ, and Li||CP batteries with 0.5 M redox-active material deliver capacity retentions of 98%, 98%, and 92%, respectively, for 100 cycles over ~55 days at the current density of 1 mA/cm2and a temperature of 27 °C. Moreover, the Li||Tri-TEMPO (0.5 M) flow battery delivers an initial average cell discharge voltage of 3.45 V and an energy density of ~33 Wh/L. This flow battery also demonstrates 81% of capacity for 100 cycles over ~45 days with average Coulombic efficiency of 96% and energy efficiency of 82% at the current density of 1.5 mA/cm2and at a temperature of 27 °C.  more » « less
Award ID(s):
2112798
PAR ID:
10439624
Author(s) / Creator(s):
; ; ; ; ; ;
Publisher / Repository:
Nature Publishing Group
Date Published:
Journal Name:
Nature Communications
Volume:
14
Issue:
1
ISSN:
2041-1723
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
More Like this
  1. ; ; ; (, Advanced Energy Materials)
    Abstract Aqueous organic redox flow batteries (AORFBs) are highly attractive for large‐scale energy storage because of their nonflammability, low cost, and sustainability. (2,2,6,6‐Tetramethylpiperidin‐1‐yl)oxyl (TEMPO) derivatives, a class of redox active molecules bearing air‐stable free nitroxyl radicals and high redox potential (>0.8 V vs NHE), has been identified as promising catholytes for AORFBs. However, reported TEMPO based molecules are either permeable through ion exchange membranes or not chemically stable enough for long‐term energy storage. Herein, a new TEMPO derivative functionalized with a dual‐ammonium dicationic group,N1, N1, N1, N3, N3, 2, 2, 6, 6‐nonamethyl‐N3‐(piperidinyloxy)propane‐1,3‐bis(ammonium) dichloride (N2‐TEMPO) as a stable, low permeable catholyte for AORFBs is reported. Ultraviolet–visible (UV–vis) and proton nuclear magnetic resonance (1H‐NMR) spectroscopic studies reveal its exceptional stability and ultra‐low permeability (1.49 × 10−12 cm2 s−1). Coupled with 1,1′‐bis[3‐(trimethylammonio)propyl]‐4,4′‐bipyridinium tetrachloride ((NPr)2V) as an anolyte, a 1.35 VN2‐TEMPO/(NPr)2V AORFB with 0.5 melectrolytes (9.05 Wh L−1) delivers a high power density of 114 mW cm−2and 100% capacity retention for 400 cycles at 60 mA cm−2. At 1.0 melectrolyte concentrations, theN2‐TEMPO/(NPr)2V AORFB achieves an energy density of 18.1 Wh L−1and capacity retention of 90% for 400 cycles at 60 mA cm−2. 
    more » « less
  2. ; ; ; (, Angewandte Chemie International Edition)
    Abstract Aqueous organic redox flow batteries (AORFBs) have received increasing attention as an emergent battery technology for grid‐scale renewable energy storage. However, physicochemical properties of redox‐active organic electrolytes remain fine refinement to maximize their performance in RFBs. Herein, we report a carboxylate functionalized viologen derivative, N,N′‐dibutyrate‐4,4′‐bipyridinium,(CBu)2V, as a highly stable, high capacity anolyte material under near pH neutral conditions.(CBu)2Vcan achieve solubility of 2.1 M and display a reversible, kinetically fast reduction at −0.43 V vs NHE at pH 9. DFT studies revealed that the high solubility of(CBu)2Vis attributed to its high molecular polarity while its negative reduction potential is benefitted from electron‐donating carboxylate groups. A 0.89 V (CBu)2V/(NH)4Fe(CN)6AORFB demonstrated exceptional energy storage performance, specifically, 100 % capacity retention with a discharge energy density of 9.5 Wh L−1for 1000 cycles, power densities of up to 85 mW cm−2, and an energy efficiency of 70 % at 60 mA cm−2.(CBu)2Vnot only represents the most capacity dense viologen with pendant ionic groups and also exhibits the longest (1200 hours or 50 days) and the most stable flow battery performance to date. 
    more » « less
  3. ; ; (, Advanced Functional Materials)
    Abstract Non‐aqueous redox flow batteries can support the growing need for grid scale energy storage. Conductive and selective membranes are critical to enabling advanced flow battery technology with higher energy density and lower cost. Herein, a series of crosslinked poly(phenylene oxide)‐based membranes functionalized with phenoxyaniline tri‐sulfonate fixed charges are developed and reported. Increasing the degree of functionalization increased the theoretical ion exchange capacity (IEC) to 2.62 mEq g−1compared with a previously achieved maximum of 2.06 mEq g−1for these materials. Increasing membrane IEC increased conductivity (up to 0.41 mS cm−1) and decreased permeability (<1 × 10−9cm2s−1) based on ex situ measurements. While further improvements are still necessary for economically competitive non‐aqueous flow battery applications, these values are among the highest selectivity reported for cation exchange membranes in non‐aqueous electrolytes. In symmetric non‐aqueous electrochemical flow cell testing, current densities over 2 mA cm−2are achieved, although cell polarization is higher than expected. Long‐term cycling is performed at 1 mA cm−2with average coulombic efficiency over 99% maintained for over 70 cycles. This work reinforces that both ex situ transport properties and electrochemical cell evaluation are necessary when evaluating potential membrane materials, although reporting of both is presently uncommon in the literature. 
    more » « less
  4. ; ; ; ; ; (, Journal of Materials Chemistry A)
    Aqueous redox flow batteries using low-cost organic and inorganic active materials have received growing interest for sustainable energy storage. In this study, a low-cost, high redox potential (1.08 V vs. NHE) and high capacity ammonium bromide (NH 4 Br, 214.4 A h L −1 ) catholyte was coupled with an organic viologen anolyte to demonstrate 1.51 V high voltage (SPr) 2 V/Br − aqueous redox flow batteries under pH neutral conditions for the first time. Benefitting from the high water solubility of both the NH 4 Br catholyte and (SPr) 2 V anolyte, the newly designed (SPr) 2 V/Br − organic flow battery was operated at up to 1.5 M and an energy density of up to 30.4 W h L −1 . Using multiwall carbon nanotubes as an electrochemical additive for the Br 3 − /Br − redox couple, the highly energy dense (SPr) 2 V/Br − flow battery manifested outstanding current performance, up to 78% energy efficiency at 40 mA cm −2 current density and 227 mW cm −2 power density, the highest power density known for pH neutral organic flow batteries. 
    more » « less
  5. ; ; ; (, Angewandte Chemie International Edition)
    Abstract Redox flow batteries (RFBs) with high energy densities are essential for efficient and sustainable long‐term energy storage on a grid scale. To advance the development of nonaqueous RFBs with high energy densities, a new organic RFB system employing a molecularly engineered tetrathiafulvalene derivative ((PEG3/PerF)‐TTF) as a high energy density catholyte was developed. A synergistic approach to the molecular design of tetrathiafulvalene (TTF) was applied, with the incorporation of polyethylene glycol (PEG) chains, which enhance its solubility in organic carbonate electrolytes, and a perfluoro (PerF) group to increase its redox potential. When paired with a lithium metal anode, the two‐electron‐active(PEG3/PerF)‐TTFcatholyte produced a cell voltage of 3.56 V for the first redox process and 3.92 V for the second redox process. In cyclic voltammetry and flow cell tests, the redox chemistry exhibited excellent cycling stability. The Li|(PEG3/PerF)‐TTFbatteries, with concentrations of 0.1 M and 0.5 M, demonstrated capacity retention rates of ~94 % (99.87 % per cycle, 97.52 % per day) and 90 % (99.93 % per cycle, 99.16 % per day), and the average Coulombic efficiencies of 99.38 % and 98.35 %, respectively. The flow cell achieved a high power density of 129 mW/cm2. Furthermore, owing to the high redox potential and solubility of(PEG3/PerF)‐TTF, the flow cell attained a high operational energy density of 72 Wh/L (100 Wh/L theoretical). A 0.75 M flow cell exhibited an even higher operational energy density of 96 Wh/L (150 Wh/L theoretical). 
    more » « less
  • Citation Formats
  • MLA
  • APA
  • Chicago
  • BibTeX
  • Save / Share this Record
  • Send to Email