A joint research team from Tohoku University and the University of California, Los Angeles (UCLA) has made a significant advance towards high-voltage metal-free lithium-ion batteries by using a small organic molecule: croconic acid. An open-access paper on their work is published in the journal Advanced Science.
Unlike conventional lithium-ion batteries, which depend on materials such as cobalt and lithium, organic batteries exploit naturally abundant elements such as carbon, hydrogen, nitrogen, and oxygen. In addition, organic batteries have greater theoretical capacities than conventional lithium-ion batteries because their use of organic materials renders them lightweight.
Most reported organic batteries to date, however, possess a relatively low (1-3V) working voltage. Increasing organic batteries’ voltage could lead to higher energy-density batteries.
Itaru Honma, a professor of chemistry at Tohoku University’s Institute of Multidisciplinary Research for Advanced Materials, Hiroaki Kobayashi, an assistant professor of chemistry at Tohoku University, and Yuto Katsuyama, a graduate student at UCLA, found that croconic acid, when used as a lithium-ion battery cathode material, maintains a strong working voltage of around 4 V.
While organic batteries have attracted great attention due to their high theoretical capacities, high-voltage organic active materials (> 4 V vs Li/Li+) remain unexplored. Here, density functional theory calculations are combined with cyclic voltammetry measurements to investigate the electrochemistry of croconic acid (CA) for use as a lithium-ion battery cathode material in both dimethyl sulfoxide and γ-butyrolactone (GBL) electrolytes.
DFT calculations demonstrate that CA dilitium salt (CA–Li2) has two enolate groups that undergo redox reactions above 4.0 V and a material-level theoretical energy density of 1949 Wh kg–1 for storing four lithium ions in GBL—exceeding the value of both conventional inorganic and known organic cathode materials.
Cyclic-voltammetry measurements reveal a highly reversible redox reaction by the enolate group at ≈4 V in both electrolytes. Battery-performance tests of CA as lithium-ion battery cathode in GBL show two discharge voltage plateaus at 3.9 and 3.1 V, and a discharge capacity of 102.2 mAh g–1 with no capacity loss after five cycles. With the higher discharge voltages compared to the known, state-of-the-art organic small molecules, CA promises to be a prime cathode-material candidate for future high-energy-density lithium-ion organic batteries.
Croconic acid has five carbon atoms bonded to each other in a pentagonal form, and each of the carbons is bonded to oxygen. It also has a high theoretical capacity of 638.6 mAh/g, which is much higher than the conventional lithium-ion battery cathode materials (LiCoO2 ~ 140 mAh/g).
We investigated the electrochemical behavior of croconic acid in the high-voltage range above 3 V using theoretical calculations and electrochemical experiments. We discovered that croconic acid stores lithium ions at roughly 4 V, giving a very high theoretical energy density of 1949 Wh/kg, which is larger than most inorganic and organic lithium-ion batteries.
Conceptual illustration of the work on croconic acid with multi-electron redox reaction at high voltage > 3.0 V. Katsuyama et al.
Although the theoretical capacity was not achieved in this study, the researchers are optimistic this can be enhanced by the development of stable electrolytes at high-voltage and chemical modifications to croconic acid.
Since most electrolytes cannot stand for such a strong working voltage of croconic acid, developing new electrolytes is vital. Additionally, the structures of small organic molecules, including croconic acid, can be easily modified. Appropriate structural modification can stabilize the molecule, leading to greater capacity and reversibility.
Resources
Yuto Katsuyama, Hiroaki Kobayashi, Kazuyuki Iwase, Yoshiyuki Gambe, Itaru Honma (2022) “Are Redox-Active Organic Small Molecules Applicable for High-Voltage (>4 V) Lithium-ion Battery Cathodes?” Advanced Science doi: 10.1002/advs.202200187
| Permalink | Comments (1)
The last time I looked at the periodic table, lithium was a metal so it is hard to make anything using lithium metal free. Also, if what they are proposing is not better than lithium sulfur, it will be a non-starter. Also sulfur is definitely not a metal.
Posted by: sd | 18 April 2022 at 09:07 AM
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