Mesoporous Carbons Produced from Tannin Biomass for Lithium-Sulfur Batteries
Authors: Filho Rubens de Freitas , Santos Keiliane Silva , Marciano Aline Capelão , Gomes Igor Bolonezi , Vaz Victor Souza , Oliveira Lucas , Silva Rayane Cristian Ferreira , Pereira Sarah , Anunciação Mariana , Cardoso Luan , Justino Danielle , Gandra Fernanda , Junior Mozair , Teixeira Ana Paula de Carvalho , Pinto Paula Sevenini , Ortega Paulo , Lavall Rodrigo , Trigueiro João , Silva Glaura Goulart 
Published: August 2024

Lithium-sulfur batteries (LSBs) are promising alternatives since sulfur can provide a theoretical specific capacity of 1675 mA h g-1 when combined with lithium [1]. Thus, LSBs can achieve a theoretical energy density (2500 W h kg-1) that is much greater than that of conventional lithium-ion batteries [1]. However, several problems must be resolved to enable commercial production on a large scale, such as the formation of soluble species of lithium polysulfides [2]. Various approaches have been used to minimize this problem, including the development of carbon-based hosts capable of retaining these polysulfides. Among these, the development of cathodes based on carbon‒sulfur composites using carbon from biomass is an alternative that benefits from the possibility of obtaining materials with a modifiable surface area and porosity at low cost [2]. On this basis, this work reports the synthesis of mesoporous carbons (MCs) from tannin biomass, the incorporation of sulfur and the development of lithium-sulfur batteries. The MC sample was produced using the solvent-free method [3] and was named C. The incorporation of sulfur into mesoporous carbons was carried out using melt diffusion methodology [4]. Two quantities of sulfur were added to the carbon host by mass, and the materials were named CS1 and CS2 at ratios of 1:1 and 2:1, respectively, in relation to sulfur:MC. Coin cells (CR 2032) were assembled using the produced materials on the cathode, metallic Li on the anode and the electrolyte 1 M LiTFSI and 1% (w/v) LiNO3 in 1,2-dimethoxyethane/1,3-dioxolane (DME/DOL) and characterized by cyclic voltammetry (CV) and galvanostatic charge/discharge (GCD) cycling. The mesoporous carbon C presented a type IV isotherm characteristic of mesoporous materials, with a BET surface area of 539 m2g-1, average pore size of 7.7 nm and total pore volume of 0.747 cm3g-1. There was a decrease in the area and pore volume of the materials after sulfur incorporation, reaching 70 m2g-1 and 0.195 cm3g-1 for CS1 and 3 m2g-1 and 0.012 cm3g-1 for CS2, respectively. The sulfur contents were determined by thermogravimetric analysis (TGA) and were 39% and 61% for CS1 and CS2, respectively. The sulfur contents determined by TGA were close to those obtained by elemental analysis (CHNS), which were 45% and 63% for CS1 and CS2, respectively. The CV data showed that both cells presented cathodic and anodic potentials typical of Li-S batteries. The GCD data show that the cell containing the cathode with the material with a higher elemental sulfur content (CS 2) is stable and maintains specific capacities on the order of 550 mA h g-1 after 45 galvanostatic cycles at different current densities. However, this cell showed a more abrupt decrease in capacity at the highest rates (2C and 4C), Figure 1. Most likely, the higher sulfur content used in this sample did not result in total impregnation of the porous structure, resulting in sulfur deposition on the surface of the particles. As a result, the interparticle contact resistance in the electrodes increases, which limits the performance at higher current demands. For the cell built with the sample containing 39% S (CS1), excellent performance is obtained at high C rates. At 0.1 C, the cathode operates above 900 mA h g-1 in the initial cycles and above 550 mA h g-1 at 0.5 C, and no significant capacity drop is observed between 1 C and 2 C (≈500 mA h g-1). At 4C, a decrease in the specific capacity is noted, but the specific capacity remains above 350 mA h g-1. These results demonstrate the potential of carbon materials obtained from biomass for building high-performance Li-S batteries.

Acknowledgments: The authors thank the financial support from the Rota 2030 Program at Fundep – Brazil.

References:

[1] Chen, Y., Wang, T., Tian, H., Su, D., Zhang, Q., & Wang, G. (2021). Advances in lithium–sulfur batteries: from academic research to commercial viability. Advanced materials, 33(29), 2003666.

[2] Yang, J., Wang, G., Teixeira, A. P., Silva, G. G., Hansen, Z., Jamal, M. J. M., & Wu, Q. (2022). A biomass-based cathode for long-life lithium-sulfur batteries. Electrochemistry Communications, 140, 107325.

[3] J. Castro-Gutiérrez, A. Sanchez-Sanchez, J. Ghanbaja, N. Díez, M. Sevilla, A. Celzard, V. Fierro, Synthesis of perfectly ordered mesoporous carbons by water-assisted mechanochemical self-assembly of tannin, Green Chemistry. 20 (2018) 5123–5132.

[4] X. Ji, K.T. Lee, L.F. Nazar, A highly ordered nanostructured carbon-sulfur cathode for lithium-sulphur batteries, Nature Materials. 8 (2009) 500–506.

Figure 1