In-situ UV-Vis Spectroscopy of Trisulfur Radicals in Lithium-Sulfur Batteries

doi:10.1007/s40242-024-4027-3

Abstract

Abstract: Here we employ in-situ UV-Vis spectroscopy to monitor the sulfur redox reaction with oxygen-containing molecules as an additive, for example, biphenyl-4,4’-dicarboxylic acid (BDC). Furthermore, Raman spectrum, electron paramagnetic resonance (EPR), and electrospray ionization-mass spectrometry (ESI-MS) measurements reveal that the formation of BDC-S₃^•‒ complexes can establish the long-term stability of polysulfide radicals, change the kinetics of sulfur redox reaction, and then generate decent capacity retention and rate capability. According to the density functional theory (DFT) analysis, S₃^•‒ radicals are the underlying product of S₆^2‒ cleavage, owing to the decreased chemical energy and the increased stability of S₃^•‒ radicals through Lewis acid-base interaction. The assembled Li-S batteries with BDC additive deliver a high reversible capacity of 420 mA∙h∙g^‒1 over 200 cycles with over 98% Coulombic efficiency, under the current density of 0.2 C.

Key words: Radical, Polysulfide, In-situ UV-Vis Spectroscopy, Electrolyte additive, Lithium-sulfur battery

DOU Renju, WANG Qin, REN Xiaoyan, LU Lehui. In-situ UV-Vis Spectroscopy of Trisulfur Radicals in Lithium-Sulfur Batteries[J]. Chemical Research in Chinese Universities, 2024, 40(2): 279-286.

References

[1] Ji X., Lee K. T., Nazar L. F., Nat. Mater., 2009, 8(6), 500
[2] Deng R., Wang M., Yu H., Luo S., Li J., Chu F., Liu B., Wu F., Energy Environ. Mater., 2022, 5, 777
[3] Cheng X.-B., Zhang R., Zhao C.-Z., Zhang Q., Chem. Rev., 2017, 117, 10403
[4] Shi Z., Tian Z., Guo D., Wang Y., Bayhan Z., Alzahrani A. S., Alshareef H. N., ACS Energy Lett., 2023, 8(7), 3054
[5] Pang Q., Liang X., Kwok C. Y., Nazar L. F., Nat. Energy, 2016, 1, 16132
[6] Liu R., Wei Z., Peng L., Zhang L., Zohar A., Schoeppner R., Wang P., Wan C., Zhu D., Liu H., Wang Z., Tolbert S. H., Dunn B., Huang Y., Sautet P., Duan X., Nature, 2024, 626, 98
[7] Lin Y., Zheng J., Wang C., Qi Y., Nano Energy, 2020, 75, 104915
[8] Meng R., He X., Ong S. J. H., Cui C., Song S., Paoprasert P., Pang Q., Xu Z. J., Liang X., Angew. Chem. Int. Ed., 2023, 62(38), e202309046
[9] Steudel R., Chivers T., Chem. Soc. Rev., 2019, 48(12), 3279
[10] Shin H., Baek M., Gupta A., Char K., Manthiram A., Choi J. W., Adv. Energy Mater., 2020, 10, 2001456
[11] Zhong N., Lei C., Meng R., Li J., He X., Liang X., Small, 2022, 18, 2200046
[12] Baek M., Shin H., Char K., Choi J. W., Adv. Mater., 2020, 32, 2005022
[13] Shen Z., Gao Q., Zhu X., Guo Z., Guo K., Song X., Zhao Y., Energy Storage Mater., 2023, 57, 299
[14] Zhang G., Peng H. J., Zhao C. Z., Chen X., Zhao L. D., Li P., Huang J. Q., Zhang Q., Angew. Chem. Int. Ed., 2018, 57(51), 16732
[15] Feng S., Fu Z.-H., Chen X., Li B.-Q., Peng H.-J., Yao N., Shen X., Yu L., Gao Y.-C., Zhang R., Zhang Q., Angew. Chem. Int. Ed., 2022, 61(52), e202211448
[16] Hou T. Z., Xu W. T., Chen X., Peng H. J., Huang J. Q., Zhang Q., Angew. Chem. Int. Ed., 2017, 56(28), 8178
[17] Jin W., Zhang X., Liu M., Zhao Y., Zhang P., Energy Storage Mater., 2024, 67, 103223
[18] Lee D. J., Agostini M., Park J. W., Sun Y. K., Hassoun J., Scrosati B., ChemSusChem, 2013, 6(12), 2245
[19] Lian J., Guo W., Fu Y., J. Am. Chem. Soc., 2021, 143(29), 11063
[20] Zhang G., Zhang Z. W., Peng H. J., Huang J. Q., Zhang Q., Small Methods, 2017, 1(7), 1700134
[21] Cui Y., Fang W., Zhang J., Li J., Wu H., Sun Z., Cai Y., Zhang H., Zhang S., Nano Energy, 2024, 122, 109343
[22] Fu B., Chen J., Cao Y., Li H., Gao F., Guo D.-Y., Wang F., Pan Q., Sensor Actuat. B-Chem., 2022, 369, 132261
[23] Yang W., Yang Y., Lin D., Li H., Yang W., Guo D., Pan Q., Inorg. Chem. Front., 2020, 7, 3718
[24] Chen X., Wang F., Hyun J. Y., Wei T., Qiang J., Ren X., Shin I., Yoon J., Chem. Soc. Rev., 2016, 45(10), 2976
[25] Ren X., Wang J., Peng Z., Lu L., Chem. Sci., 2018, 9, 231
[26] Frisch M. J., Gaussian 09, Gaussian Inc., 2009
[27] Boys S. F., Bernardi F., Mol. Phys., 1970, 19, 553
[28] Lee C., Yang W., Parr R. G., Phys. Rev. B, 1988, 37, 785
[29] Lee B.-J., Zhao C., Yu J.-H., Kang T.-H., Park H.-Y., Kang J., Jung Y., Liu X., Li T., Xu W., Zuo X.-B., Xu G.-L., Amine K., Yu J.-S., Nat. Commun., 2022, 13, 4629
[30] Chaouche M., Gao X. X., Cyr M., Cotte M., Frouin L., J. Am. Ceram. Soc., 2017, 100(4), 1707
[31] Wang Q., Zheng J., Walter E., Pan H., Lv D., Zuo P., Chen H., Deng Z. D., Liaw B. Y., Yu X., Yang X., Zhang J.-G., Liu J., Xiao J., J. Electrochem. Soc., 2015, 162(3), A474
[32] Feng S., Fu Z.-H., Chen X., Li B.-Q., Peng H.-J., Yao N., Shen X., Yu L., Gao Y.-C., Zhang R., Zhang Q., Angew. Chem. Int. Ed., 2022, 61(52), e202211448
[33] Chivers T., Nature 1974, 252, 32
[34] Zou Q., Lu Y. C., J. Phys. Chem. Lett., 2016, 7(8), 1518
[35] Wujcik K. H., Wang D. R., Raghunathan A., Drake M., Pasca T. A., Prendergast, D., Balsara N. P., J. Phys. Chem. C, 2016, 120(33), 18403
[36] Zhu Y., Zuo Y., Jiao X., Manjunatha R., Ezeigwe E. R., Yan W., Zhang J., Carbon Energy, 2023, 5, e249