Redox‐active anthraquinone molecules represent promising anolyte materials in aqueous organic redox flow batteries (AORFBs). However, the chemical stability issue and corrosion nature of anthraquinone‐based anolytes in reported acidic and alkaline AORFBs constitute a roadblock for their practical applications in energy storage. A feasible strategy to overcome these issues is migrating to pH‐neutral conditions and employing soluble AQDS salts. Herein, we report the 9,10‐anthraquinone‐2,7‐disulfonic diammonium salt
Redox flow batteries (RFBs) are ideal for large-scale, long-duration energy storage applications. However, the limited solubility of most ions and compounds in aqueous and non-aqueous solvents (1M–1.5 M) restricts their use in the days-energy storage scenario, which necessitates a large volume of solution in the numerous tanks and the vast floorspace for these tanks, making the RFB systems costly. To resolve the low energy storage density issue, this work presents a novel way in which the reactants and products are stored in both solid and soluble forms and only the liquid with soluble ions is circulated through the batteries. Storing the active ions in solid form can greatly increase the storage energy density of the system. With a solid to liquid storage ratio of 2:1, for example, the energy density of the electrolyte of vanadium sulfate (VOSO4), an active compound used in the all-vanadium RFB, can be increased from 40 Ah l−1to 163 Ah l−1(>4X), allowing an existing 6-h RFB system to become a 24-h system with minimal modifications. To show how the concept works, an H2-V flow battery with a solid/liquid storage system is used, and its successful demonstration validates the solid-liquid storage concept.
more » « less- NSF-PAR ID:
- 10378887
- Publisher / Repository:
- The Electrochemical Society
- Date Published:
- Journal Name:
- Journal of The Electrochemical Society
- Volume:
- 169
- Issue:
- 11
- ISSN:
- 0013-4651
- Format(s):
- Medium: X Size: Article No. 110509
- Size(s):
- ["Article No. 110509"]
- Sponsoring Org:
- National Science Foundation
More Like this
-
more » « less
Abstract AQDS(NH4)2 , as an anolyte material for pH‐neutral AORFBs with solubility of 1.9m in water, which is more than 3 times that of the corresponding sodium salt. Paired with an NH4I catholyte, the resulting pH‐neutral AORFB with an energy density of 12.5 Wh L−1displayed outstanding cycling stability over 300 cycles. Even at the pH‐neutral condition, theAQDS(NH4)2 /NH4I AORFB delivered an impressive energy efficiency of 70.6 % at 60 mA cm−2and a high power density of 91.5 mW cm−2at 100 % SOC. The present AQDS(NH4)2flow battery chemistry opens a new avenue to apply anthraquinone molecules in developing low‐cost and benign pH‐neutral flow batteries for scalable energy storage. -
more » « less
Abstract Long duration storage batteries such as Redox Flow Batteries (RFBs) are promising storage system to address the energy storage requirement that our society will require in the years to come. Recent effort has been focused on the development of metal free and high energy density system such as all‐organic non‐aqueous redox flow batteries (NAORFBs). However high‐voltage NAORFBs currently use distinct anolytes and catholytes, which are separated by a membrane sensitive to osmotic pressure, resulting in rapid capacity and energy density degradation over time. To address this issue, symmetric organic redox flow batteries (SORFBs) have been proposed as an elegant solution. We have introduced dimethoxyquinacridiniums (DMQA+) ions as efficient bipolar redox molecules (BRMs) in static H‐cell conditions. In this study, we present the first application of DMQA+ions in a complete flow RFB prototype, showcasing their ability to operate with polarity reversal. Key kinetic properties were evaluated through cyclic voltammetry and DFT calculations. While coulombic and energy efficiency metrics were moderate, pegylated DMQA+demonstrated impressive capacity retention of over 99.99 % and the capability to operate under polarity inversion, making it a highly attractive choice for grid‐scale, long‐lifespan energy storage applications.
-
more » « less
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,
N 1, N 1, N 1, N 3, N 3, 2, 2, 6, 6‐nonamethyl‐N 3‐(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 0.5m electrolytes (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 1.0m electrolyte 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. -
null (Ed.)Liquid flow batteries have potential to achieve high energy efficiency as a large-scale energy storage system. However, the ion exchange membranes (IEMs) currently used in flow batteries do not have high ion selectivity and conductance at the same time, owing to the trade-off between ionic membrane resistance and ion selectivity. Here, we report a rationally designed sulfonated aromatic polymer membrane which can greatly mitigate the trade-off limitation and achieve high performance vanadium RFB. Small-angle X-ray scattering studies and density functional theory calculations indicated that the narrowly distributed aqueous ionic domain of just the right width (<7 Å) and the strong hydrogen bond interaction of vanadium species with a unique polymer side chain structure play a key role in improving the ion selectivity. Our systematic studies of the polymer structures, morphologies, and transport properties provide valuable insight that can aid in elucidating the structure–property relationship of IEMs and in establishing design criteria for the development of high-performance membranes.more » « less
-
more » « less
Ever-increasing demands for energy, particularly being environmentally friendly have promoted the transition from fossil fuels to renewable energy.1Lithium-ion batteries (LIBs), arguably the most well-studied energy storage system, have dominated the energy market since their advent in the 1990s.2However, challenging issues regarding safety, supply of lithium, and high price of lithium resources limit the further advancement of LIBs for large-scale energy storage applications.3Therefore, attention is being concentrated on an alternative electrochemical energy storage device that features high safety, low cost, and long cycle life. Rechargeable aqueous zinc-ion batteries (ZIBs) is considered one of the most promising alternative energy storage systems due to the high theoretical energy and power densities where the multiple electrons (Zn2+) . In addition, aqueous ZIBs are safer due to non-flammable electrolyte (e.g., typically aqueous solution) and can be manufactured since they can be assembled in ambient air conditions.4As an essential component in aqueous Zn-based batteries, the Zn metal anode generally suffers from the growth of dendrites, which would affect battery performance in several ways. Second, the led by the loose structure of Zn dendrite may reduce the coulombic efficiency and shorten the battery lifespan.5
Several approaches were suggested to improve the electrochemical stability of ZIBs, such as implementing an interfacial buffer layer that separates the active Zn from the bulk electrolyte.6However, the and thick thickness of the conventional Zn metal foils remain a critical challenge in this field, which may diminish the energy density of the battery drastically. According to a theretical calculation, the thickness of a Zn metal anode with an areal capacity of 1 mAh cm-2is about 1.7 μm. However, existing extrusion-based fabrication technologies are not capable of downscaling the thickness Zn metal foils below 20 μm.
Herein, we demonstrate a thickness controllable coating approach to fabricate an ultrathin Zn metal anode as well as a thin dielectric oxide separator. First, a 1.7 μm Zn layer was uniformly thermally evaporated onto a Cu foil. Then, Al2O3, the separator was deposited through sputtering on the Zn layer to a thickness of 10 nm. The inert and high hardness Al2O3layer is expected to lower the polarization and restrain the growth of Zn dendrites. Atomic force microscopy was employed to evaluate the roughness of the surface of the deposited Zn and Al2O3/Zn anode structures. Long-term cycling stability was gauged under the symmetrical cells at 0.5 mA cm-2for 1 mAh cm-2. Then the fabricated Zn anode was paired with MnO2as a full cell for further electrochemical performance testing. To investigate the evolution of the interface between the Zn anode and the electrolyte, a home-developed in-situ optical observation battery cage was employed to record and compare the process of Zn deposition on the anodes of the Al2O3/Zn (demonstrated in this study) and the procured thick Zn anode. The surface morphology of the two Zn anodes after circulation was characterized and compared through scanning electron microscopy. The tunable ultrathin Zn metal anode with enhanced anode stability provides a pathway for future high-energy-density Zn-ion batteries.
Obama, B., The irreversible momentum of clean energy.
Science 2017, 355 (6321), 126-129.Goodenough, J. B.; Park, K. S., The Li-ion rechargeable battery: a perspective.
J Am Chem Soc 2013, 135 (4), 1167-76.Li, C.; Xie, X.; Liang, S.; Zhou, J., Issues and Future Perspective on Zinc Metal Anode for Rechargeable Aqueous Zinc‐ion Batteries.
Energy & Environmental Materials 2020, 3 (2), 146-159.Jia, H.; Wang, Z.; Tawiah, B.; Wang, Y.; Chan, C.-Y.; Fei, B.; Pan, F., Recent advances in zinc anodes for high-performance aqueous Zn-ion batteries.
Nano Energy 2020, 70 .Yang, J.; Yin, B.; Sun, Y.; Pan, H.; Sun, W.; Jia, B.; Zhang, S.; Ma, T., Zinc Anode for Mild Aqueous Zinc-Ion Batteries: Challenges, Strategies, and Perspectives.
Nanomicro Lett 2022, 14 (1), 42.Yang, Q.; Li, Q.; Liu, Z.; Wang, D.; Guo, Y.; Li, X.; Tang, Y.; Li, H.; Dong, B.; Zhi, C., Dendrites in Zn-Based Batteries.
Adv Mater 2020, 32 (48), e2001854.Acknowledgment
This work was partially supported by the U.S. National Science Foundation (NSF) Award No. ECCS-1931088. S.L. and H.W.S. acknowledge the support from the Improvement of Measurement Standards and Technology for Mechanical Metrology (Grant No. 22011044) by KRISS.
Figure 1
