Ionic liquids to monitor the nano-structuration and the surface functionalization of material electrodes: a proof of concept applied to cobalt oxyhydroxide

Jacob Olchowka; Tiphaine Tailliez; Lydie Bourgeois; Marie Anne Dourges; Liliane Guerlou-Demourgues

doi:10.1039/c9na00171a

Ionic liquids to monitor the nano-structuration and the surface functionalization of material electrodes: a proof of concept applied to cobalt oxyhydroxide

Nanoscale Adv. 2019 Apr 10;1(6):2240-2249. doi: 10.1039/c9na00171a. eCollection 2019 Jun 11.

Authors

Jacob Olchowka^{1

2}, Tiphaine Tailliez¹, Lydie Bourgeois³, Marie Anne Dourges³, Liliane Guerlou-Demourgues^{1

2}

Affiliations

¹ CNRS, Univ. Bordeaux, Bordeaux INP, ICMCB UMR 5026 F-33600 Pessac France jacob.olchowka@icmcb.cnrs.fr.
² RS2E, Réseau Français sur le Stockage Electrochimique de l'Energie, FR CNRS 3459 F-80039 Amiens Cedex 1 France.
³ Institut des Sciences Molaires, Univ. Bordeaux, UMR 5255 F-33405 Talence France.

Abstract

This paper reports on an innovative and efficient approach based on the use of ionic liquids to govern the nano-structuration of HCoO₂, in order to optimize the porosity and enhance the ionic diffusion through the electrode materials. In this work, we show that (1-pentyl-3-methyl-imidazolium bromide (PMIMBr) and 1-ethyl-3-methylimidazolium tetrafluoroborate (EMIMBF₄)) ionic liquids (ILs) used as templates during the synthesis orientate the nanoparticle aggregation which leads to increase of the porosity and the average pore size of the electrode material. It is also demonstrated that the ILs are strongly bonded to the HCoO₂ surface, leading to surface functionalized HCoO₂ materials, also called nanohybrids. This surface tailoring stabilizes the material upon cycling and shifts the oxidation potential linked to the Co(iii)/Co(iv) redox couple to lower voltage in an alkaline 5 M KOH electrolyte. The surface and porosity optimizations facilitate the ionic diffusion through the material, improve the electron transfer ability within the electrode and lead to greatly enhanced specific capacity in both alkaline 5 M-KOH and neutral 0.5 M-K₂SO₄ aqueous electrolytes (66.7 mA h g^-1 and 47.5 mA h g^-1 respectively for HCoO₂-PMIMBr and HCoO₂-EMIMBF₄ compared to 18.1 mA h g^-1 for bare HCoO₂ in 5 M-KOH at 1 A g^-1).