Ultra-Low Content Triethylammonium Chloride Facilitates Localized High-Concentration Electrolytes and Formation of Inorganic Solid Electrolyte Interface

Abstract

Localized high-concentration electrolytes offer a potential solution for achieving uniform lithium deposition and a stable solid-electrolyte interface in Lithium metal batteries. However, the use of highly concentrated salts or structure-loaded diluents can result in significantly higher production costs and increased environmental burdens. Herein, a novel localized high-concentration electrolyte is developed, comprising ultra-low content (2% by mass) triethylammonium chloride as an electrolyte additive. The stable Lewis acid structure of the triethylammonium chloride molecule allows for the adsorption of numerous solvent molecules and TFSI^– anions, intensifying the electrostatic interactions between lithium ions and anions. The chloride ions introduced by TC, along with TFSI^– anions, integrate into the solvent sheath, forming a LiCl-rich inorganic SEI and enhancing the electrochemical performance of the lithium metal anode. The improved Li||Li cell shows excellent cycling stability for over 500 h at 1 mA cm² with a 27 mV overpotential. This work provides insights into the impact of electrolyte additives on the electrode-electrolyte interface and Li-ion solvation, crucial for safer lithium metal battery development.

Keywords

electrolyte additive / lithium metal anode / solvent sheath / triethylammonium chloride

References

[1] J. Qian, W. A. Henderson, W. Xu, P. Bhattacharya, M. Engelhard, O. Borodin, J.-G. Zhang, Nat. Commun. 2015, 6, 6362.

[2] Z. Luo, X. Qiu, C. Liu, S. Li, C. Wang, G. Zou, H. Hou, X. Ji, Nano Energy 2021, 79, 105507.

[3] P. Shi, X.-Q. Zhang, X. Shen, R. Zhang, H. Liu, Q. Zhang, Adv. Mater. Technol. 2020, 5, 1900806.

[4] H. Yuan, X. Ding, T. Liu, J. Nai, Y. Wang, Y. Liu, C. Liu, X. Tao, Mater. Today 2022, 53, 173.

[5] H. Wu, H. Jia, C. Wang, J.-G. Zhang, W. Xu, Adv. Energy Mater. 2021, 11, 2003092.

[6] B. Acebedo, M. C. Morant-Miñana, E. Gonzalo, I. Ruiz de Larramendi, A. Villaverde, J. Rikarte, L. Fallarino, Adv. Energy Mater. 2023, 13, 2203744.

[7] B. Wu, C. Chen, L. H. J. Raijmakers, J. Liu, D. L. Danilov, R.-A. Eichel, P. H. L. Notten, Energy Storage Mater. 2023, 57, 508.

[8] X. Ding, Q. Zhou, X. Li, X. Xiong, Chem. Commun. 2024, 60, 2472.

[9] C. Qiu, Y. Hong, Y. Sun, Z. Li, W. Huang, J. Pan, J. Li, J. Ren, W. Zhao, D. Qin, K. Shi, Q. Liu, Appl. Phys. Lett. 2023, 122, 81601.

[10] Z. Li, C. Qiu, Y. Lin, J. Li, Y. Hong, Y. Zheng, K. Shi, Q. Liu, Ind. Eng. Chem. Res. 2022, 61, 4842.

[11] N. Sun, R. Li, Y. Zhao, H. Zhang, J. Chen, J. Xu, Z. Li, X. Fan, X. Yao, Z. Peng, Adv. Energy Mater. 2022, 12, 2200621.

[12] Q. Wang, T. Lu, Y. Liu, J. Dai, L. Guan, L. Hou, H. Du, H. Wei, X. Liu, X. Han, Z. Ye, D. Zhang, Y. Wei, H. Zhou, Energy Storage Mater. 2023, 55, 782.

[13] D. Luo, M. Li, Y. Zheng, Q. Ma, R. Gao, Z. Zhang, H. Dou, G. Wen, L. Shui, A. Yu, X. Wang, Z. Chen, Adv. Sci. 2021, 8, 2101051.

[14] C. Qiu, Y. Hong, K. Shi, Z. Wang, Z. Chen, K. Wang, K. Li, Q. Liu, Chem. Eng. Sci. 2023, 281, 119088.

[15] Z. Piao, R. Gao, Y. Liu, G. Zhou, H.-M. Cheng, Adv. Mater. 2023, 35, 2206009.

[16] S. Yuan, K. Ding, X. Zeng, D. Bin, Y. Zhang, P. Dong, Y. Wang, Adv. Mater. 2023, 35, 2206228.

[17] Y. Yamada, J. Wang, S. Ko, E. Watanabe, A. Yamada, Nat. Energy 2019, 4, 269.

[18] H. Zhang, X. Liu, H. Li, I. Hasa, S. Passerini, Angew. Chem. Int. Ed. 2021, 60, 598.

[19] Z. Yu, J. Zhang, C. Wang, R. Hu, X. Du, B. Tang, H. Qu, H. Wu, X. Liu, X. Zhou, X. Yang, G. Cui, J. Energy Chem. 2020, 51, 154.

[20] S. Zhang, B. Cheng, Y. Fang, D. Dang, X. Shen, Z. Li, M. Wu, Y. Hong, Q. Liu, Chin. Chem. Lett. 2022, 33, 3951.

[21] C. M. Efaw, Q. Wu, N. Gao, Y. Zhang, H. Zhu, K. Gering, M. F. Hurley, H. Xiong, E. Hu, X. Cao, W. Xu, J.-G. Zhang, E. J. Dufek, J. Xiao, X.-Q. Yang, J. Liu, Y. Qi, B. Li, Nat. Mater. 2023, 22, 1531.

[22] Q. Liu, Y.-H. Feng, X. Zhu, M. Liu, L. Yu, G.-X. Wei, X.-Y. Fan, X. Ji, P.-F. Wang, H. Xin, Nano Energy 2024, 123, 109389.

[23] Z. Wang, L.-P. Hou, Q.-K. Zhang, N. Yao, A. Chen, J.-Q. Huang, X.-Q. Zhang, Chin. Chem. Lett. 2024, 35, 108570.

[24] C. Zhang, S. Gu, D. Zhang, J. Ma, H. Zheng, M. Zheng, R. Lv, K. Yu, J. Wu, X. Wang, Q.-H. Yang, F. Kang, W. Lv, Energy Storage Mater. 2022, 52, 355.

[25] X.-T. Yang, C. Han, Y.-M. Xie, R. Fang, S. Zheng, J.-H. Tian, X.-M. Lin, H. Zhang, B.-W. Mao, Y. Gu, Y.-H. Wang, J.-F. Li, Small 2024, 20, 2311393.

[26] C. Chang, Y. Yao, R. Li, Z. Cong, L. Li, Z. H. Guo, W. Hu, X. Pu, J. Mater. Chem. A 2022, 10, 9001.

[27] G. H. Penner, R. Webber, L. A. O'Dell, Can. J. Chem. 2011, 89, 1036.

[28] S. Li, J. Huang, Y. Cui, S. Liu, Z. Chen, W. Huang, C. Li, R. Liu, R. Fu, D. Wu, Nat. Nanotechnol. 2022, 17, 613.

[29] M. Zhu, Z. Fan, K. Xu, Y. Fang, W. Sun, Y. Zhu, Adv. Funct. Mater. 2022, 32, 2112645.

[30] B. D. Adams, J. Zheng, X. Ren, W. Xu, J.-G. Zhang, Adv. Energy Mater. 2018, 8, 1702097.

[31] L. Tan, Q. Chen, P. Chen, X. Huang, L. Li, K. Zou, D. Liu, J. Electroanal. Chem. 2023, 928, 117063.

[32] K. Zhang, F. Wu, K. Zhang, S. Weng, X. Wang, M. Gao, Y. Sun, D. Cao, Y. Bai, H. Xu, X. Wang, C. Wu, Energy Storage Mater. 2021, 41, 485.

[33] J. Yang, X. Shi, W. Wang, Z. Liu, C. Shen, Batteries. 2023, 9, 155.

[34] T. Liu, Z. Shi, H. Li, W. Xue, S. Liu, J. Yue, M. Mao, Y.-S. Hu, H. Li, X. Huang, L. Chen, L. Suo, Adv. Mater. 2021, 33, 2102034.

[35] S. Jiao, X. Ren, R. Cao, M. H. Engelhard, Y. Liu, D. Hu, D. Mei, J. Zheng, W. Zhao, Q. Li, N. Liu, B. D. Adams, C. Ma, J. Liu, J.-G. Zhang, W. Xu, Nat. Energy 2018, 3, 739.

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2025 The Author(s). Energy & Environmental Materials published by John Wiley & Sons Australia, Ltd on behalf of Zhengzhou University.