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KAIST research team develops a cheap and safe redox flow battery
Redox flow batteries, one of the potential replacements for the widely used lithium-ion secondary batteries, can be utilized as new and renewable energy as well as for energy storage systems (ESS) thanks to their low cost, low flammability, and long lifetime of over 20 years. Since the price of vanadium, the most widely used active material for redox flow batteries, has been rising in recent years, scientists have been actively searching for redox materials to replace it.
On March 23, a joint research team led by Professors Hye Ryung Byon and Mu-Hyun Baik from the KAIST Department of Chemistry, and Professor Jongcheol Seo from the POSTECH Department of Chemistry announced that they had developed a highly soluble and stable organic redox-active molecule for use in aqueous redox flow batteries.
The research team focused on developing aqueous redox flow batteries by redesigning an organic molecule. It is possible to control the solubility and electrochemical redox potential of organic molecules by engineering their design, which makes them a promising active material candidate with possibly higher energy storage capabilities than vanadium. Most organic redox-active molecules have low solubilities or have slow chemical stability during redox reactions. Low solubility means low energy storage capacity and low chemical stability leads to reduced cycle performance. For this research, the team chose naphthalene diimide (NDI) as their active molecule. Until now, there was little research done on NDI despite its high chemical stability, as it shows low solubility in aqueous electrolyte solutions.
Although NDI molecules are almost insoluble in water, the research team tethered four ammonium functionalities and achieved a solubility as high as 1.5M* in water. In addition, they confirmed that when a 1M solution of NDI was used in neutral redox flow batteries for 500 cycles, 98% of its capacity was maintained. This means 0.004% capacity decay per cycle, and only 2% of its capacity would be lost if the battery were to be operated for 45 days.
Furthermore, the developed NDI molecule can save two electrons per molecule, and the team proved that 2M of electrons could be stored in every 1M of NDI solution used. For reference, vanadium used in vanadium redox flow batteries, which require a highly concentrated sulfuric acid solution, has a solubility of about 1.6M and can only hold one electron per molecule, meaning it can store a total of 1.6M of electrons. Therefore, the newly developed NDI active molecule shows a higher storage capacity compared to existing vanadium devices.
*1M (mol/L): 6.022 x 1023 active molecules are present in 1L of solution
This paper, written by co-first authors Research Professor Vikram Singh, and Ph.D. candidates Seongyeon Kwon and Yunseop Choi, was published in the online version of Advanced Materials on February 7 under the title, Controlling π-π interactions of highly soluble naphthalene diimide derivatives for neutral pH aqueous redox flow batteries. Ph.D. Candidate Yelim Yi and Professor Mi Hee Lee’s team from the KAIST Department of Chemistry also contributed to the study by conducting electron paramagnetic resonance analyses.
Professor Hye Ryung Byon said, “We have demonstrated the principles of molecular design by modifying an existing organic active molecule with low solubility and utilizing it as an active molecule for redox flow batteries. We have also shown that during a redox reaction, we can use molecular interactions to suppress the chemical reactivity of radically formed molecules.”
She added, “Should this be used later for aqueous redox flow batteries, along with its high energy density and high solubility, it would also have the advantage of being available for use in neutral pH electrolytes. Vanadium redox flow batteries currently use acidic solutions, which cause corrosion, and we expect our molecule to solve this issue. Since existing lithium ion-based ESS are flammable, we must develop safer and cheaper next-generation ESS, and our research has shown great promise in addressing this.”
This research was funded by Samsung Research Funding & Incubation Center, the Institute for Basic Science, and the National Research Foundation.
Figure 1. (a) Structures of various NDI molecules. (b) Solubility of NDI molecules in water (black bars) and aqueous electrolytes including KCl electrolyte (blue bars). (c–d) Structural changes of the molecules as the developed NDI molecule stores two electrons. (c) Illustration of cluster combination and separation of NDI molecules developed during redox reaction and (d) Snapshot of the MD simulation. NDI molecules prepared from the left, formation of bimolecular sieve and tetramolecular sieve clusters after the first reductive reaction, and a single molecule with a three-dimensional structure after the second reduction.
Figure 2. Performance results of an aqueous redox flow battery using 1M of the developed NDI molecule as the cathode electrolyte and 3.1M of ammonium iodine as the anode electrolyte. Using 1.5 M KCl solution. (a) A schematic diagram of a redox flow battery. (b) Voltage-capacity graph according to cycle in a redox flow battery. (c) Graphs of capacity and coulombs, voltage, and energy efficiency maintained at 500 cycles.
2023.04.03 View 11366 -
Researchers Report Longest-lived Aqueous Flow Batteries
New technology to overcome the life limit of next-generation water-cell batteries
A research team led by Professor Hee-Tak Kim from the Department of Chemical and Biomolecular Engineering has developed water-based zinc/bromine redox flow batteries (ZBBs) with the best life expectancy among all the redox flow batteries reported by identifying and solving the deterioration issue with zinc electrodes.
Professor Kim, head of the Advanced Battery Center at KAIST's Nano-fusion Research Institute, said, "We presented a new technology to overcome the life limit of next-generation water-cell batteries. Not only is it cheaper than conventional lithium-ion batteries, but it can contribute to the expansion of renewable energy and the safe supply of energy storage systems that can run with more than 80 percent energy efficiency."
ZBBs were found to have stable life spans of more than 5,000 cycles, even at a high current density of 100 mA/cm2. It was also confirmed that it represented the highest output and life expectancy compared to Redox flow batteries (RFBs) reported worldwide, which use other redox couples such as zinc-bromine, zinc-iodine, zinc-iron, and vanadium.
Recently, more attention has been focused on energy storage system (ESS) that can improve energy utilization efficiency by storing new and late-night power in large quantities and supplying it to the grid if necessary to supplement the intermittent nature of renewable energy and meet peak power demand.
However, lithium-ion batteries (LIBs), which are currently the core technology of ESSs, have been criticized for not being suitable for ESSs, which store large amounts of electricity due to their inherent risk of ignition and fire. In fact, a total of 33 cases of ESSs using LIBs in Korea had fire accidents, and 35% of all ESS facilities were shut down. This is estimated to have resulted in more than 700 billion won in losses.
As a result, water-based RFBs have drawn great attention. In particular, ZBBs that use ultra-low-cost bromide (ZnBr2) as an active material have been developed for ESSs since the 1970s, with their advantages of high cell voltage, high energy density, and low price compared to other RFBs. Until now, however, the commercialization of ZBBs has been delayed due to the short life span caused by the zinc electrodes. In particular, the uneven "dendrite" growth behavior of zinc metals during the charging and discharging process leads to internal short circuits in the battery which shorten its life.
The research team noted that self-aggregation occurs through the surface diffusion of zinc nuclei on the carbon electrode surface with low surface energy, and determined that self-aggregation was the main cause of zinc dendrite formation through quantum mechanics-based computer simulations and transmission electron microscopy. Furthermore, it was found that the surface diffusion of the zinc nuclei was inhibited in certain carbon fault structures so that dendrites were not produced.
Single vacancy defect, where one carbon atom is removed, exchanges zinc nuclei and electrons, and is strongly coupled, thus inhibiting surface diffusion and enabling uniform nuclear production/growth. The research team applied carbon electrodes with high density fault structure to ZBBs, achieving life characteristics of more than 5,000 cycles at a high charge current density (100 mA/cm2), which is 30 times that of LIBs.
This ESS technology, which can supply eco-friendly electric energy such as renewable energy to the private sector through technology that can drive safe and cheap redox flow batteries for long life, is expected to draw attention once again.
Publication:
Ju-Hyuk Lee, Riyul Kim, Soohyun Kim, Jiyun Heo, Hyeokjin Kwon, Jung Hoon Yang, and Hee-Tak Kim. 2020. Dendrite-free Zn electrodeposition triggered by interatomic orbital hybridization of Zn and single vacancy carbon defects for aqueous Zn-based flow batteries. Energy and Environmental Science, 2020, 13, 2839-2848.
Link to download the full-text paper:http://xlink.rsc.org/?DOI=D0EE00723D
Profile: Prof. Hee-Tak Kimheetak.kim@kaist.ac.krhttp://eed.kaist.ac.krAssociate ProfessorDepartment of Chemical & Biomolecular EngineeringKAIST
2020.12.16 View 19128