Researchers have presented a novel electrode material for advanced energy storage device that is directly charged with oxygen from the air. Professor Jeung Ku Kang’s team synthesized and preserved the sub-nanometric particles of atomic cluster sizes at high mass loadings within metal-organic frameworks (MOF) by controlling the behavior of reactants at the molecular level. This new strategy ensures high performance for lithium-oxygen batteries, acclaimed as a next-generation energy storage technology and widely used in electric vehicles.
They have demonstrated ten-fold improvements in the life cycle.
Lithium-oxygen batteries in principle can generate ten times higher energy densities than conventional lithium-ion batteries, but they suffer from very poor cyclability. One of the methods to improve cycle stability is to reduce the overpotential of electrocatalysts in cathode electrodes. When the size of an electrocatalyst material is reduced to the atomic level, the increased surface energy leads to increased activity while significantly accelerating the material’s agglomeration.
As a solution to this challenge, Professor Kang from the Department of Materials Science and Engineering aimed to maintain the improved activity by stabilizing atomic-scale sized electrocatalysts into the sub-nanometric spaces. This is a novel strategy for simultaneously producing and stabilizing atomic-level electrocatalysts within metal-organic frameworks (MOFs).
Metal-organic frameworks continuously assemble metal ions and organic linkers.
The team controlled hydrogen affinities between water molecules to separate them and transfer the isolated water molecules one by one through the sub-nanometric pores of MOFs. The transferred water molecules reacted with cobalt ions to form di-nuclear cobalt hydroxide under precisely controlled synthetic conditions, then the atomic-level cobalt hydroxide is stabilized inside the sub-nanometric pores.
The di-nuclear cobalt hydroxide that is stabilized in the sub-nanometric pores of metal-organic frameworks (MOFs) reduced the overpotential by 63.9% and showed ten-fold improvements in the life cycle.
Professor Kang said, “Simultaneously generating and stabilizing atomic-level electrocatalysts within MOFs can diversify materials according to numerous combinations of metal and organic linkers. It can expand not only the development of electrocatalysts, but also various research fields such as photocatalysts, medicine, the environment, and petrochemicals.”
Advanced Science – Autogenous Production and Stabilization of Highly Loaded Sub-Nanometric Particles Within Multishell Hollow Metal-Organic Frameworks and Their Utilization for High Performance in Li-O 2 Batteries
Sub-nanometric particles (SNPs) of atomic cluster sizes have shown great promise in many fields such as full atom-to-atom utilization, but their precise production and stabilization at high mass loadings remain a great challenge. As a solution to overcome this challenge, a strategy allowing synthesis and preservation of SNPs at high mass loadings within multishell hollow metal-organic frameworks (MOFs) is demonstrated. First, alternating water-decomposable and water-stable MOFs are stacked in succession to build multilayer MOFs. Next, using controlled hydrogen bonding affinity, isolated water molecules are selectively sieved through the hydrophobic nanocages of water-stable MOFs and transferred one by one to water-decomposable MOFs. The transmission of water molecules via controlled hydrogen bonding affinity through the water-stable MOF layers is a key step to realize SNPs from various types of alternating water-decomposable and water-stable layers. This process transforms multilayer MOFs into SNP-embedded multishell hollow MOFs. Additionally, the multishell stabilizes SNPs by π-backbonding allowing high conductivity to be achieved via the hopping mechanism, and hollow interspaces minimize transport resistance. These features, as demonstrated using SNP-embedded multishell hollow MOFs with up to five shells, lead to high electrochemical performances including high volumetric capacities and low overpotentials in Li-O2 batteries.