Novel Anchored Branched Polymer Coating Layers for Enhanced Redox Kinetics in Aqueous Zinc-Ion Batteries

Abstract

The fundamental issues associated with Zn anodes prevent the commercialization of aqueous Zn ion batteries. To address this, a simple dip-coating method was used to coordinate a thin layer of branched polyethyleneimine (b-PEI) polymer onto the electrode surface. This process increases hydrophilicity and reduces interfacial resistance between the electrode and aqueous electrolyte. Consequently, electrolyte leaching from the hydrophilic polymer coating layer is prevented, charge distribution is uniform, and stable electrochemical performance is maintained over extended periods. In symmetric cell testing, the b-PEI@Zn anode exhibits a lifespan of over 1400 h (3 mA cm^–2, 1 mAh cm^–2). Furthermore, full-cell tests, the b-PEI@Zn anode demonstrates higher capacity (+26.05%) and improved stability (95.4%) compared to the bare Zn anode (0.5 A g^–1). This study presents a practical surface modification strategy for Zn anodes and underscores the potential of innovative polymer-based electrode coatings for aqueous battery applications.

Keywords

aqueous zinc-ion batteries / coordination bond / dip-coating / poly ethylenimine / zinc metal anode

References

[1] B. Obama, Science 2017, 355, 126.

[2] J. Wang, Y. Yamada, K. Sodeyama, E. Watanabe, K. Takada, Y. Tateyama, A. Yamada, Nat. Energy 2018, 3, 22.

[3] J. Liu, C. Xu, Z. Chen, S. Ni, Z. X. Shen, Green Energy Environ. 2018, 3, 20.

[4] S. Zhao, B. Han, D. Zhang, Q. Huang, L. Xiao, L. Chen, D. G. Ivey, Y. Deng, W. Wei, J. Mater. Chem. A 2018, 6, 5733.

[5] W. Sun, F. Wang, S. Hou, C. Yang, X. Fan, Z. Ma, T. Gao, F. Han, R. Hu, M. Zhu, J. Am. Chem. Soc. 2017, 139, 9775.

[6] A. L. Zhu, D. P. Wilkinson, X. Zhang, Y. Xing, A. G. Rozhin, S. A. Kulinich, J. Energy Storage 2016, 8, 35.

[7] P. Sapkota, H. Kim, J. Ind. Eng. Chem. 2009, 15, 445.

[8] S. Liu, J. Vongsvivut, Y. Wang, R. Zhang, F. Yang, S. Zhang, K. Davey, J. Mao, Z. Guo, Angew. Chem. Int. Ed. 2023, 62, e202215600.

[9] F. Yang, J. A. Yuwono, J. Hao, J. Long, L. Yuan, Y. Wang, S. Liu, Y. Fan, S. Zhao, K. Davey, Adv. Mater. 2022, 34, 2206754.

[10] J. Hao, B. Li, X. Li, X. Zeng, S. Zhang, F. Yang, S. Liu, D. Li, C. Wu, Z. Guo, Adv. Mater. 2020, 32, 2003021.

[11] J. W. Diggle, A. R. Despic, J. O. M. Bockris, J. Electrochem. Soc. 1969, 116, 1503.

[12] R. Zhang, X. R. Chen, X. Chen, X. B. Cheng, X. Q. Zhang, C. Yan, Q. Zhang, Angew. Chem. 2017, 129, 7872.

[13] X. Guo, H. Xu, Y. Tang, Z. Yang, F. Dou, W. Li, Q. Li, H. Pang, Adv. Mater. 2024, 36, 2408317.

[14] C. Li, X. Xie, S. Liang, J. Zhou, Energy Environ. Mater. 2020, 3, 146.

[15] Q. Li, Y. Zhang, X. Guo, G. Zhang, Y. Yang, M. Du, T. Lv, H. Zhou, Y. Fan, Y. Chen, Y. Wang, H. Pang, J. Colloid Interface Sci. 2024, 663, 697.

[16] Y. Li, Z. Wang, Y. Cai, M. E. Pam, Y. Yang, D. Zhang, Y. Wang, S. Huang, Energy Environ. Mater. 2022, 5, 823.

[17] G. Zhang, H. Yang, H. Zhou, T. Huang, Y. Yang, G. Zhu, Y. Zhang, H. Pang, Angew. Chem. Int. Ed. 2024, 63, e202401903.

[18] Y. Qin, P. Liu, Q. Zhang, Q. Wang, D. Sun, Y. Tang, Y. Ren, H. Wang, Small 2020, 16, 2003106.

[19] Y. Wang, Z. Wang, F. Yang, S. Liu, S. Zhang, J. Mao, Z. Guo, Small 2022, 18, 2107033.

[20] N. Guo, W. Huo, X. Dong, Z. Sun, Y. Lu, X. Wu, L. Dai, L. Wang, H. Lin, H. Liu, H. Liang, Z. He, Q. Zhang, Small Methods 2022, 6, 2200597.

[21] H. B. Jeong, D. I. Kim, G. Yoo, D. Mohan, A. Roy, M. Jung, H. S. Jeong, S. Cha, G.-H. An, P.-R. Cha, J. Hong, J. Mater. Chem. A 2024, 12, 15265.

[22] Q. Zhang, J. Luan, Y. Tang, X. Ji, H. Wang, Angew. Chem. Int. Ed. 2020, 59, 13180.

[23] H. He, H. Qin, J. Wu, X. Chen, R. Huang, F. Shen, Z. Wu, G. Chen, S. Yin, J. Liu, Energy Storage Mater. 2021, 43, 317.

[24] H. Liu, J.-G. Wang, W. Hua, L. Ren, H. Sun, Z. Hou, Y. Huyan, Y. Cao, C. Wei, F. Kang, Energy Environ. Sci. 2022, 15, 1872.

[25] J. Shin, J. Lee, Y. Kim, Y. Park, M. Kim, J. W. Choi, Adv. Energy Mater. 2021, 11, 2100676.

[26] C. Deng, X. Xie, J. Han, Y. Tang, J. Gao, C. Liu, X. Shi, J. Zhou, S. Liang, Adv. Funct. Mater. 2020, 30, 2000599.

[27] J. H. Park, M.-J. Kwak, C. Hwang, K.-N. Kang, N. Liu, J.-H. Jang, B. A. Grzybowski, Adv. Mater. 2021, 33, 2101726.

[28] X. Zheng, L. Miao, Z. Song, W. Du, D. Zhu, Y. Lv, L. Li, L. Gan, M. Liu, J. Mater. Chem. A 2022, 10, 611.

[29] X. Fan, P. Liu, B. Ouyang, R. Cai, X. Chen, X. Liu, W. Liu, J. Wang, K. Liu, ChemElectroChem 2021, 8, 3572.

[30] J.-W. Xu, Q.-L. Gao, Y.-M. Xia, X.-S. Lin, W.-L. Liu, M.-M. Ren, F.-G. Kong, S.-J. Wang, C. Lin, J. Colloid Interface Sci. 2021, 598, 419.

[31] X. Chen, W. Li, S. Hu, N. G. Akhmedov, D. Reed, X. Li, X. Liu, Nano Energy 2022, 98, 107269.

[32] W. Lu, Y. Shao, R. Yan, Y. Zhong, J. Ning, Y. Hu, Batter. Supercaps 2024, 7, e202300486.

[33] Y. Zhou, W. Wu, G. Hu, H. Wu, S. Cui, Mater. Res. Bull. 2008, 43, 2113.

[34] B. Demeneix, J. P. Behr, Advances in Genetics 2005, 53, 215.

[35] C. N. Lungu, M. V. Diudea, M. V. Putz, I. P. Grudziński, Int. J. Mol. Sci. 2016, 17, 555.

[36] L. Wightman, R. Kircheis, V. Rössler, S. Carotta, R. Ruzicka, M. Kursa, E. Wagner, J. Gene Med. 2001, 3, 362.

[37] T. Takagishi, S. Okuda, N. Kuroki, H. Kozuka, J. Polym. Sci. Polym. Chem. Ed. 1985, 23, 2109.

[38] L. Tan, C. Wei, Y. Zhang, Y. An, S. Xiong, J. Feng, Chem. Eng. J. 2022, 431, 134277.

[39] S. J. Banik, R. Akolkar, Electrochim. Acta 2015, 179, 475.

[40] Y. Wang, Q. Wang, X. Song, J. Cai, Biochem. Eng. J. 2019, 141, 163.

[41] B. Niu, Z. Li, S. Cai, D. Luo, Y. Qiao, S. Zhou, H. Li, X. He, X. Wang, Chem. Eng. J. 2022, 442, 136217.

[42] Z. Li, W. Deng, C. Li, X. Wang, Z. Zhou, Y. Li, X. Yuan, J. Hu, M. Zhang, J. Zhu, J. Mater. Chem. A 2020, 8, 17725.

[43] P. Wang, Y.-L. Zhang, K.-L. Fu, Z. Liu, L. Zhang, C. Liu, Y. Deng, R. Xie, X.-J. Ju, W. Wang, L.-Y. Chu, Mater. Adv. 2022, 3, 5476.

[44] R. Gorejová, N. Podrojková, K. Sisáková, J. Shepa, I. Shepa, A. Kovalčíková, I. Šišoláková, F. Kaľavský, R. Oriňaková, Sci. Rep. 2022, 12, 3460.

[45] W. Li, J. Wu, S. S. Lee, J. D. Fortner, Chem. Eng. J. 2017, 313, 1160.

[46] Q. Deng, S. You, W. Min, Y. Xu, W. Lin, J. Lu, C. Yang, Adv. Mater. 2024, 36, 2312924.

[47] Q. Wen, H. Fu, R.-d. Cui, H.-Z. Chen, R.-H. Ji, L.-B. Tang, C. Yan, J. Mao, K.-H. Dai, X.-H. Zhang, J.-C. Zheng, J. Energy Chem. 2023, 83, 287.

[48] A. Linsha Mali, S. S. Priya, M. R. Rekha, J. Appl. Polym. Sci. 2021, 138, 51323.

[49] J. Wu, C. Liao, T. Li, J. Zhou, L. Zhang, J.-Q. Wang, G. Li, X. Li, Nat. Commun. 2023, 14, 1149.

[50] H. J. Krusemeyer, Phys. Rev. 1959, 114, 655.

[51] M.-H. Lin, C.-J. Huang, P.-H. Cheng, J.-H. Cheng, C.-C. Wang, J. Mater. Chem. A 2020, 8, 20637.

[52] J. Yang, B. Yin, Y. Sun, H. Pan, W. Sun, B. Jia, S. Zhang, T. Ma, Nanomicro Lett. 2022, 14, 42.

[53] A. Li, Y. Hao, G. Feng, X. Zhong, Cat. Sci. Technol. 2022, 12, 1458.

[54] Y. Hao, X. Zhong, Appl. Phys. Lett. 2021, 119, 141604.

[55] Z. Chen, Z. Lv, Y. Sun, Z. Chi, G. Qing, J. Mater. Chem. B 2020, 8, 2951.

[56] F. Sagane, K.-i. Ikeda, K. Okita, H. Sano, H. Sakaebe, Y. Iriyama, J. Power Sources 2013, 233, 34.

[57] Q. Zhang, J. Luan, Y. Tang, X. Ji, S. Wang, H. Wang, J. Mater. Chem. A 2018, 6, 18444.

[58] H. Zhang, Y. Zhong, J. Li, Y. Liao, J. Zeng, Y. Shen, L. Yuan, Z. Li, Y. Huang, Adv. Energy Mater. 2023, 13, 2203254.

[59] J. Zhang, W. Huang, L. Li, C. Chang, K. Yang, L. Gao, X. Pu, Adv. Mater. 2023, 35, 2300073.

[60] H. Li, C. Xu, C. Han, Y. Chen, C. Wei, B. Li, F. Kang, J. Electrochem. Soc. 2015, 162, A1439.

[61] Y. Dong, M. Jia, Y. Wang, J. Xu, Y. Liu, L. Jiao, N. Zhang, ACS Appl. Energy Mater. 2020, 3, 11183.

[62] Z. Cai, J. Wang, Z. Lu, R. Zhan, Y. Ou, L. Wang, M. Dahbi, J. Alami, J. Lu, K. Amine, Y. Sun, Angew. Chem. 2022, 61, e202116560.

[63] F. Zhao, Z. Jing, X. Guo, J. Li, H. Dong, Y. Tan, L. Liu, Y. Zhou, R. Owen, P. R. Shearing, D. J. L. Brett, G. He, I. P. Parkin, Energy Storage Mater. 2022, 53, 638.

[64] W. Choi, H.-C. Shin, J. M. Kim, J.-Y. Choi, W.-S. Yoon, J. Electrochem. Sci. Technol. 2020,

[65] S. Khamsanga, R. Pornprasertsuk, T. Yonezawa, A. A. Mohamad, S. Kheawhom, Sci. Rep. 2019, 9, 8441.

[66] H. Pan, Y. Shao, P. Yan, Y. Cheng, K. S. Han, Z. Nie, C. Wang, J. Yang, X. Li, P. Bhattacharya, K. T. Mueller, J. Liu, Nat. Energy 2016, 1, 16039.

[67] D. I. Kim, H. B. Jeong, J. Lim, H. S. Jeong, M. K. Kim, S. Pak, S. Lee, G.-H. An, S.-S. Chee, J. P. Hong, S. Cha, J. Hong, Energy Environ. Mater. 2024,

[68] J. Huang, Z. Wang, M. Hou, X. Dong, Y. Liu, Y. Wang, Y. Xia, Nat. Commun. 2018, 9, 2906.

[69] B. Lee, H. R. Seo, H. R. Lee, C. S. Yoon, J. H. Kim, K. Y. Chung, B. W. Cho, S. H. Oh, ChemSusChem 2016, 9, 2948.

[70] H. Pan, Y. Shao, P. Yan, Y. Cheng, K. S. Han, Z. Nie, C. Wang, J. Yang, X. Li, P. Bhattacharya, Nat. Energy 2016,

[71] G. Kresse, D. Joubert, Phys. Rev. B 1999, 59, 1758.

[72] G. Kresse, J. Furthmüller, Phys. Rev. B 1996, 54, 11169.

[73] J. P. Perdew, K. Burke, M. Ernzerhof, Phys. Rev. Lett. 1996, 77, 3865.

[74] K. Mathew, V. Kolluru, S. Mula, S. N. Steinmann, R. G. Hennig, J. Chem. Phys. 2019, 151, 234101.

[75] K. Mathew, R. Sundararaman, K. Letchworth-Weaver, T. Arias, R. G. Hennig, J. Chem. Phys. 2014, 140, 084106.

[76] S. Grimme, S. Ehrlich, L. Goerigk, J. Comput. Chem. 2011, 32, 1456.

RIGHTS & PERMISSIONS

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