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: Flow battery electroanalysis 3: online kinetics measurements using ultramicroelectrodes in channel flow
Redox flow batteries are attractive for grid-scale energy storage, but ongoing work on materials discovery is hampered by the difficulty of measuring electron-transfer rates under battery-relevant conditions. We have developed an experimental approach for collecting continuous voltammetric measurements of flow battery electrolytes by placing a 3-electrode cell containing an ultramicroelectrode into the flow loop of a functioning redox flow battery. We further developed an empirical approach for extracting electron-transfer rate constants from each voltammetric cycle, thereby enabling continuous measurements as a function of state of charge and cycle time. Benchmarking these approaches with iron-based aqueous flow battery electrolytes using platinum and carbon fiber ultramicroelectrodes yielded rate constants that varied in the order Pt > electrochemically oxidized carbon > pristine carbon, in good agreement with prior work. We also found that Pt electrodes become more catalytically active upon cycling for several hours, whereas carbon fiber electrodes with and without oxidative pretreatments remained stable over the same interval. We expect these experimental approaches can be used to measure kinetics and other figures of merit for most electrodes and electrolytes of interest for redox flow batteries as well as in other systems where it is useful to evaluate the properties of a flowing electrolyte in real time.  more » « less
Award ID(s):
2015859
PAR ID:
10342104
Author(s) / Creator(s):
; ; ; ; ; ;
Date Published:
Journal Name:
Journal of Materials Chemistry A
Volume:
10
Issue:
26
ISSN:
2050-7488
Page Range / eLocation ID:
13917 to 13927
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
More Like this
  1. ; ; ; ; (, ACS ES&T Engineering)
    Climate change mitigation by decreasing worldwide CO2 emissions is an urgent and demanding challenge that requires innovative technical solutions. This work, inspired by vanadium redox flow batteries (VRFB), introduces an integrated electrochemical process for carbon capture and energy storage. It utilizes established vanadium and ferricyanide redox couples for pH modulation for CO2 desorption and absorbent regeneration. The developed process consumes electricity during the daytime─when renewable electricity is available─to desorb CO2 and charge the cell, and it can regenerate the absorbent for further CO2 absorption while releasing electricity to the grid during nighttime when solar power is unavailable. This research explores the process fundamentals and scalability potential, through an extensive study of the system’s thermodynamics, transport phenomena, kinetics, and bench-scale operations. Cyclic voltammetry (CV) was utilized to study the thermodynamics of the process, mapping the redox profiles to identify ideal potential windows for operation. The CV results indicated that an overpotential of approximately 0.3 V was required for driving redox reactions. Additionally, polarization studies were conducted to select the practical operating potential, identifying 0.5 V as optimal for the CO2 desorption cycle to provide sufficient polarity to overcome activation barriers in addition to the Nernstian potential. Mass transfer analysis balanced conductivity and desorption efficiency, with a 1:1 ratio identified as optimal for redox-active species and background electrolyte concentration. To further enhance the kinetics of the redox reactions, plasma treatment of electrode surfaces was implemented, resulting in a 43% decrease in charge transfer resistance, as measured by electrochemical impedance spectroscopy (EIS) analysis. Finally, a bench-scale operation of the system demonstrated an energy consumption of 54 kJ/mol CO2, which is competitive with other electrochemical carbon capture technologies. Besides its energy competitiveness, the process offers multiple additional advantages, including the elimination of precious metal electrodes, oxygen insensitivity in flue gas, scalability inspired by VRFB technology, and the unique ability to function as a battery during the absorbent regeneration process, enabling efficient day-night operation. 
    more » « less
  2. ; ; ; (, 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
  3. ; ; (, Journal of The Electrochemical Society)
    Chemical redox reactions between redox shuttles and lithium-ion battery particles have applications in electrochemical systems including redox-mediated flow batteries, photo-assisted lithium-ion batteries, and lithium-ion battery overcharge protection. These previous studies, combined with interest in chemical redox of battery materials in general, has resulted in previous reports of the chemical oxidation and/or reduction of solid lithium-ion materials. However, in many of these reports, a single redox shuttle is the focus and/or the experimental conditions are relatively limited. Herein, a study of chemical redox for a series of redox shuttles reacted with a lithium-ion battery cathode material will be reported. Both oxidation and reduction of the solid material with redox shuttles as a function of time will be probed using ferrocene derivatives with different half-wave potentials. The progression of the chemical redox was tracked by using electrochemical analysis of the redox shuttles in a custom electrochemical cell, and rate constants for chemical redox were extracted from using two different models. This study provides evidence that redox shuttle-particle interactions play a role in the overall reaction rate, and more broadly support that this experimental method dependent on electrochemical analysis can be applied for comparison of redox shuttles reacting with solid electroactive materials. 
    more » « less
  4. ; ; ; ; ; ; ; (, Batteries & Supercaps)
    Abstract Aqueous organic redox flow batteries are promising candidates for large‐scale energy storage. However, the design of stable and inexpensive electrolytes is challenging. Here, we report a highly stable, low redox potential, and potentially inexpensive negolyte species, sodium 3,3′,3′′,3′′′‐((9,10‐anthraquinone‐2,6‐diyl)bis(azanetriyl))tetrakis(propane‐1‐sulfonate) (2,6‐N‐TSAQ), which is synthesized in a single step from inexpensive precursors. Pairing 2,6‐N‐TSAQ with potassium ferrocyanide at pH=14 yielded a battery with the highest open‐circuit voltage, 1.14 V, of any anthraquinone‐based cell with a capacity fade rate <10 %/yr. When 2,6‐N‐TSAQ was cycled at neutral pH, it exhibited two orders of magnitude higher capacity fade rate. The great difference in anthraquinone cycling stability at different pH is interpreted in terms of the thermodynamics of the anthrone formation reaction. This work shows the great potential of organic synthetic chemistry for the development of viable flow battery electrolytes and demonstrates the remarkable performance improvements achievable with an understanding of decomposition mechanisms. 
    more » « less
  5. ; ; ; ; ; ; (, Journal of Energy Storage)
    This paper presents the development of novel rechargeable cement-based batteries with carbon fiber mesh for energy storage applications. With the increasing demand for sustainable energy storage solutions, there is a growing interest in exploring unconventional materials and technologies. The batteries featured the carbon fiber mesh, which coated with nickel oxide and iron materials as electrodes and immersed in a cement-based electrolyte, offering a unique approach to energy storage. Experimental investigations, including electrochemical impedance spectroscopy, cyclic voltammetry, charge-discharge cycling, and rate performance assessments, were conducted to evaluate the batteries' performance. Results indicated that the batteries have promising features such as high ionic conductivity of the cement-based electrolyte and stable charge-discharge behaviors over 100 cycles. Cyclic voltammetry curves demonstrated quasi-reversible redox peaks, indicative of battery-type electrochemistry. The rechargeable cement-based batteries exhibited stability in discharge capacity, efficiency, and energy density, surpassing existing literatures on cement batteries, with a maximum energy density of 7.6 Wh/ m2. Despite challenges related to efficiency and energy density, this paper envisions the practical applications for the batteries, from powering light sensors to supporting 5G base stations and meeting daily electricity needs. Integration of rechargeable cement-based batteries and clean energy sources holds significant promise for global energy storage solutions. In conclusion, this research provides valuable insights into developing rechargeable cement-based batteries, highlights their potential as sustainable energy storage solutions with opportunities for further optimization and future advancements. 
    more » « less
  • Citation Formats
  • MLA
  • APA
  • Chicago
  • BibTeX
  • Save / Share this Record
  • Send to Email