TMOL - Technologie Moléculaire pour des Matériaux Fonctionnels

Molecular Materials for Mg batteries – MoMa

Bottom-Up Synthetic Approach for the Design of Open Frameworks for Batteries

-

Development of host electrode materials for Mg batteries:

The global demand for advanced electrochemical energy storage continues growing, led by increasingly urgent concerns over environmental impact of fossil fuels and nuclear power plants within a power grid. Mg batteries have attracted much interest as potential power grid storage media, since magnesium is earth-abundant and its divalency (Mg2+) provides a high energy density. <br />A crucial requirement for Mg batteries is the development of host electrode materials that exhibit reversible Mg2+ intercalation. However, only a few compounds have been reported as Mg2+ intercalation hosts, and a rational strategy for the design of Mg2+ intercalation hosts is yet to be established.<br />In this MoMa project, we employed a bottom-up approach for designing open frameworks that exhibit reversible intercalation of ions, especially Mg2+ ion. The Mg2+ intercalation electrode materials we found in this project could contribute to industrial research & development of Mg batteries. Furthermore, the established methodology to design host electrode materials is tremendously versatile and can be used for exploring future electrode materials for various ion intercalation (e.g., Ca2+, Al3+).

For the development of Mg-ion intercalation hosts, it is crucial to construct nanoporous space for Mg-ion storage as well as nanoporous channels for Mg-ion diffusion. In this MoMa project, we explored an original synthetic approach based on the self-assembly of preformed functional building units to obtain molecular materials fulfilling the above-mentioned requirements. We have thus used functionalized clusters capable of multi-electron redox reactions in order to rationally design redox active polymers containing open space/channels for Mg2+ storage/diffusion. The French group (Leader: Rodrigue Lescouëzec) designed novel intercalation compounds, which consist in self-assembled cyanide-based molecular building units. The Japanese group (Leader: Masashi Okubo) studied the electrode performance of the novel compounds designed by the French group.

Using the three-dimensional open framework built of molecular clusters that are able to store multi electrons, we achieved reversible Mg-ion intercalation. The reaction voltage of the electrodes is unprecedentedly high compared to those reported previously, leading to high energy density Mg-ion batteries. More importantly, our approach, that is, a rational assembling strategy is proved to be effective for the development of electrode materials for ion storage, which can be applicable to any future battery cathode research.

We demonstrated that open frameworks built of molecular clusters operate as positive electrode materials for Mg batteries. Albeit a small capacity at present, an unprecedentedly high operating voltage contributes to the recent significant interest among battery scientists in the concept to develop Mg battery cathode. Furthermore, the new application of molecular materials found in this project strongly encourages coordination chemists pursuing practical applications of their compounds. Diverse building units of coordination complexes would allow for further improvement of the electrode performance, which greatly contributes to the next-generation battery research. The project is going on with the help of new french collaborators.

Masashi Okubo, Jérome Long, Daniel R. Talham, Rodrigue Lescouëzec
Compte Rendu Chimie, 2019, DOI: 10.1016/j.crci.2019.04.005

Plamont R., Tami J., Jimenez J.R., Benchohra A., Khaled O., Li, Y. Gontard G., Lescouëzec R. (2018) J. Coord. Chem. DOI:10.1080/00958972.2018.1442575 .
Jimenez J. R., Sugahara A., Okubo M., Yamada A., Lisnard L., Lescouëzec R.
Chem. Commun. (2018), 54, 5189; DOI: 10.1039/C8CC01374H

Flambard A., Sugahara A., De S., Okubo M., Yamada A., Lescouëzec R. (2017). Dalton Trans., 46, 15, 7637-7646.

Long J., Asakura D., Okubo M., Yamada A., Guari Y., Larionova J. (2016). Inorg.Chem., 55, 15, 7637-7646.

Wang X. F., Kurono R., Nishimura S., Okubo M., Yamada A. (2015) Chem. Eur. J., 21, 3, 1096-1101.

Li C. H., Peprah M. K., Asakura D., Meisel M. W., Okubo M., Talham D. (2015) Chem. Mater. 27, 5, 1524-1530.

Patent «Polymeric Hybrid Network comprising octametallic cage complexes and bridging ligands« EP18305031. (2018, not extended in 2019)

The global demand for advanced electrochemical energy storage continues to grow, led by increasingly urgent concerns over environmental impact of fossil fuels and nuclear power plants within the power grid. Mg batteries have attracted much interest as potential power grid storage media, since magnesium is earth-abundant and possesses a high energy density.
A crucial requirement for Mg batteries is an electrode material that exhibits Mg2+ intercalation. In general, Mg2+ intercalation is hindered by two-electron redox processes and slow Mg2+ ion diffusion in the solid.
In this project, we intend to design Mg2+ intercalation materials by assembling molecular building units in a controlled manner into open frameworks. Both tailored coordination clusters capable of multi-electron redox and rationally designed open channels for Mg2+ diffusion can efficiently contribute to the realization of new Mg2+ intercalation materials.
By exploiting the molecular chemist toolbox, the French group (Leader: Rodrigue Lescouëzec) will design novel intercalation compounds, which consist in self-assembled cyanide-based molecular building units. For example the “complex/cluster-as-ligand versus complex/cluster-as-metal” synthetic approach, which have been successfully used in tuning the functionalities of molecular materials will be explored.
The Japanese group (Leader: Masashi Okubo) will study the electrochemical Mg2+ intercalation in the novel compounds designed by the French group. The Japanese group has a strong experience in the electrochemical evaluation of the intercalation compounds.
This project is fully supported by and will benefit from a strong France-Japan international collaboration where we cooperatively apply the French molecular technology to the Japanese battery technology. The international fusion between molecular chemistry in France and battery technology in Japan will successfully contribute to the development of new research axes in the field of solid state electrochemistry, i.e., Mg2+ intercalation. Furthermore, from a practical application viewpoint, this project could accelerate the development of novel Mg2+ intercalation compounds, leading to the realization of efficient Mg batteries.

Project coordination

Rodrigue Lescouezec (UNIVERSITE PARIS 6)

The author of this summary is the project coordinator, who is responsible for the content of this summary. The ANR declines any responsibility as for its contents.

Partner

UNIVERSITE PARIS 6
The University of Tokyo Department of Chemical System Engineering, School of Engineering

Help of the ANR 205,816 euros
Beginning and duration of the scientific project: November 2014 - 36 Months

Useful links

Explorez notre base de projets financés

 

 

ANR makes available its datasets on funded projects, click here to find more.

Sign up for the latest news:
Subscribe to our newsletter