An Amphiphilic Molecule Induced Anion-Enrichment Interface for Next-Generation Lithium Metal Batteries
Sheng Liu
College of Materials and Chemistry & Chemical Engineering, Chengdu University of Technology, 1# Dongsanlu, Erxianqiao, Chengdu, Sichuan, 610059 P. R. China
Search for more papers by this authorYu Yan
College of Materials and Chemistry & Chemical Engineering, Chengdu University of Technology, 1# Dongsanlu, Erxianqiao, Chengdu, Sichuan, 610059 P. R. China
Institute of Fundamental and Frontier Sciences, University of Electronic Science and Technology of China, Chengdu, Sichuan, 611731 P. R. China
Search for more papers by this authorRuixin Zheng
College of Materials and Chemistry & Chemical Engineering, Chengdu University of Technology, 1# Dongsanlu, Erxianqiao, Chengdu, Sichuan, 610059 P. R. China
Search for more papers by this authorGuilei Tian
College of Materials and Chemistry & Chemical Engineering, Chengdu University of Technology, 1# Dongsanlu, Erxianqiao, Chengdu, Sichuan, 610059 P. R. China
Search for more papers by this authorXinxiang Wang
College of Materials and Chemistry & Chemical Engineering, Chengdu University of Technology, 1# Dongsanlu, Erxianqiao, Chengdu, Sichuan, 610059 P. R. China
Search for more papers by this authorCorresponding Author
Chaozhu Shu
College of Materials and Chemistry & Chemical Engineering, Chengdu University of Technology, 1# Dongsanlu, Erxianqiao, Chengdu, Sichuan, 610059 P. R. China
State Key Laboratory of Geo-Hazard Prevention and Geo-Environment Protection, Chengdu University of Technology, Chengdu, Sichuan, 610059 P. R. China
E-mail: [email protected]
Search for more papers by this authorSheng Liu
College of Materials and Chemistry & Chemical Engineering, Chengdu University of Technology, 1# Dongsanlu, Erxianqiao, Chengdu, Sichuan, 610059 P. R. China
Search for more papers by this authorYu Yan
College of Materials and Chemistry & Chemical Engineering, Chengdu University of Technology, 1# Dongsanlu, Erxianqiao, Chengdu, Sichuan, 610059 P. R. China
Institute of Fundamental and Frontier Sciences, University of Electronic Science and Technology of China, Chengdu, Sichuan, 611731 P. R. China
Search for more papers by this authorRuixin Zheng
College of Materials and Chemistry & Chemical Engineering, Chengdu University of Technology, 1# Dongsanlu, Erxianqiao, Chengdu, Sichuan, 610059 P. R. China
Search for more papers by this authorGuilei Tian
College of Materials and Chemistry & Chemical Engineering, Chengdu University of Technology, 1# Dongsanlu, Erxianqiao, Chengdu, Sichuan, 610059 P. R. China
Search for more papers by this authorXinxiang Wang
College of Materials and Chemistry & Chemical Engineering, Chengdu University of Technology, 1# Dongsanlu, Erxianqiao, Chengdu, Sichuan, 610059 P. R. China
Search for more papers by this authorCorresponding Author
Chaozhu Shu
College of Materials and Chemistry & Chemical Engineering, Chengdu University of Technology, 1# Dongsanlu, Erxianqiao, Chengdu, Sichuan, 610059 P. R. China
State Key Laboratory of Geo-Hazard Prevention and Geo-Environment Protection, Chengdu University of Technology, Chengdu, Sichuan, 610059 P. R. China
E-mail: [email protected]
Search for more papers by this authorAbstract
The electrolyte engineering enables the fabrication of robust electrode/electrolyte interphase with excellent electrochemical stability for reliable lithium (Li) metal batteries (LMBs). Herein, an amphiphilic molecule nonafluoro-1-butanesulfonate (NFSA) is employed in electrolytes to realize anion-enrichment interfacial design. The functions of such an amphiphilic molecule in the electrolyte and anode/electrolyte interphases of LMBs are elucidated via theoretical and experimental analyses. The polar lithophilic segments (-SO3-) present a capability to solvate Li+, while the perfluoroalkyl chains (-CF2CF2CF2CF3) exhibit a solvent-phobic, which alters the Li+ solvation environment in the electrolyte and thus building a favorable interphase enriched with anion-derived inorganic compositions on Li electrode. As a result, the designed electrolyte enables stable operation of the Li||Cu cells for more than 200 cycles with a cumulative irreversible capacity loss of only 2.4 mAh cm−2, and the long-term cycle life of the Li||Li cells is extended to more than 1500 h with a small overpotential (36.5 mV). Moreover, prolonged cycle life of the full cell assembled with commercial LiFePO4 cathode (over 80% capacity retention after 500 cycles at 0.5 C) is achieved even under the limiting Li source (≈5 mAh cm−2), high cathode loading (≈12 mg cm−2), and lean electrolyte (≈2.5 µL mg−1).
Conflict of Interest
The authors declare no conflict of interest.
Open Research
Data Availability Statement
The data that support the findings of this study are available from the corresponding author upon reasonable request.
Supporting Information
| Filename | Description |
|---|---|
| smll202407855-sup-0001-SuppMat.docx5.1 MB | Supporting Information |
Please note: The publisher is not responsible for the content or functionality of any supporting information supplied by the authors. Any queries (other than missing content) should be directed to the corresponding author for the article.
References
- 1M. S. Kim, Z. Zhang, P. E. Rudnicki, Z. Yu, J. Wang, H. Wang, S. T. Oyakhire, Y. Chen, S. C. Kim, W. Zhang, D. T. Boyle, X. Kong, R. Xu, Z. Huang, W. Huang, S. F. Bent, L.-W. Wang, J. Qin, Z. Bao, Y. Cui, Nat. Mater. 2022, 21, 445.
- 2X. Chen, X. Shen, T.-Z. Hou, R. Zhang, H.-J. Peng, Q. Zhang, Chem 2020, 6, 2242.
- 3J. Zhou, B. Hao, M. Peng, L. Zhang, H. Ji, J. Liu, W. Ling, C. Yan, T. Qian, Adv. Energy Mater. 2023, 13, 2204174.
- 4S. Feng, Z.-H. Fu, X. Chen, Q. Zhang, InfoMat 2022, 4, 12304.
- 5Z. Zhao, B. Nian, Y. Lei, Y. Wang, L. Shi, J. Yin, O. F. Mohammed, H. N. Alshareef, Adv. Energy Mater. 2023, 13, 2300063.
- 6Y. Feng, Y. Li, J. Lin, H. Wu, L. Zhu, X. Zhang, L. Zhang, C.-F. Sun, M. Wu, Y. Wang, Nat. Commun. 2023, 14, 3639.
- 7Z. Yu, P. E. Rudnicki, Z. Zhang, Z. Huang, H. Celik, S. T. Oyakhire, Y. Chen, X. Kong, S. C. Kim, X. Xiao, H. Wang, Y. Zheng, G. A. Kamat, M. S. Kim, S. F. Bent, J. Qin, Y. Cui, Z. Bao, Nat. Energy 2022, 7, 94.
- 8F. Wu, A. Mullaliu, T. Diemant, D. Stepien, T. N. Parac-Vogt, J.-K. Kim, D. Bresser, G.-T. Kim, S. Passerini, InfoMat 2023, 5, 12462.
- 9M. Mao, X. Ji, Q. Wang, Z. Lin, M. Li, T. Liu, C. Wang, Y.-S. Hu, H. Li, X. Huang, L. Chen, L. Suo, Nat. Commun. 2023, 14, 1082.
- 10Z. Wang, F. Qi, L. Yin, Y. Shi, C. Sun, B. An, H. M. Cheng, F. Li, Adv. Energy Mater. 2020, 10, 1903843.
- 11S. Li, J. Huang, Y. Cui, S. Liu, Z. Chen, W. Huang, C. Li, R. Liu, R. Fu, D. Wu, Nat. Nanotechnol. 2022, 17, 613.
- 12S. Huang, Y.-P. Huang, Y. Xia, J. Ding, C. Peng, L. Wang, J. Luo, X.-X. Zhang, J. Zheng, Y. Q. Gao, J. Chen, InfoMat 2023, 5, 12411.
- 13C. Zhu, C. Sun, R. Li, S. Weng, L. Fan, X. Wang, L. Chen, M. Noked, X. Fan, ACS Energy Lett. 2022, 7, 1338.
- 14X. Yuan, T. Dong, J. Liu, Y. Cui, H. Dong, D. Yuan, H. Zhang, Angew. Chem., Int. Ed. 2023, 62, 202304121.
- 15Z. Guo, X. Song, Q. Zhang, N. Zhan, Z. Hou, Q. Gao, Z. Liu, Z. Shen, Y. Zhao, ACS Energy Lett. 2022, 7, 569.
- 16L. Liu, H. Lu, C. Han, X. Chen, S. Liu, J. Zhang, X. Chen, X. Wang, R. Wang, J. Xu, H. K. Liu, S. X. Dou, W. Li, ACS Nano 2023, 17, 23065.
- 17G. Wang, M. Zhu, Y. Zhang, C. Song, X. Zhu, Z. Huang, Y. Zhang, F. Yu, G. Xu, M. Wu, H.-K. Liu, S.-X. Dou, C. Wu, InfoMat 2022, 4, 12293.
- 18X. Zheng, Z. Cao, W. Luo, S. Weng, X. Zhang, D. Wang, Z. Zhu, H. Du, X. Wang, L. Qie, H. Zheng, Y. Huang, Adv. Mater. 2023, 35, 2210115.
- 19S. Kim, J.-A. Lee, T. K. Lee, K. Baek, J. Kim, B. Kim, J. H. Byun, H.-W. Lee, S. J. Kang, J.-A. Choi, S.-Y. Lee, M.-H. Choi, J.-H. Lee, N.-S. Choi, Energy Environ. Sci. 2023, 16, 5108.
- 20Z. Piao, P. Xiao, R. Luo, J. Ma, R. Gao, C. Li, J. Tan, K. Yu, G. Zhou, H. M. Cheng, Adv. Mater. 2021, 34, 2108400.
- 21Y. Meng, D. Zhou, R. Liu, Y. Tian, Y. Gao, Y. Wang, B. Sun, F. Kang, M. Armand, B. Li, G. Wang, D. Aurbach, Nat. Energy 2023, 8, 1023.
- 22Q. Sun, Z. Cao, Z. Ma, J. Zhang, H. Cheng, X. Guo, G.-T. Park, Q. Li, E. Xie, L. Cavallo, Y.-K. Sun, J. Ming, ACS Energy Lett. 2022, 7, 3545.
- 23Y. Zhang, Y. Wu, H. Li, J. Chen, D. Lei, C. Wang, Nat. Commun. 2022, 13, 1297.
- 24L. P. Hou, Y. Li, Z. Li, Q. K. Zhang, B. Q. Li, C. X. Bi, Z. X. Chen, L. L. Su, J. Q. Huang, R. Wen, X. Q. Zhang, Q. Zhang, Angew. Chem., Int. Ed. 2023, 62, 9168
- 25Y. Zhao, T. Zhou, M. Mensi, J. W. Choi, A. Coskun, Nat. Commun. 2023, 14, 299.
- 26S. Qi, H. Wang, J. He, J. Liu, C. Cui, M. Wu, F. Li, Y. Feng, J. Ma, Sci. Bull. 2021, 66, 685.
- 27N. Li, J. You, Y. Gao, F. Qiao, Y. Yang, T. Jin, C. Shen, H. Huang, K. Xie, InfoMat 2023, 5, 12402.
- 28Q. Yang, J. Hu, J. Meng, C. Li, Energy Environ. Sci. 2021, 14, 3621.
- 29W. Zhang, Y. Lu, L. Wan, P. Zhou, Y. Xia, S. Yan, X. Chen, H. Zhou, H. Dong, K. Liu, Nat. Commun. 2022, 13, 2029.
- 30Y. Zhao, T. Zhou, T. Ashirov, M. E. Kazzi, C. Cancellieri, L. P. H. Jeurgens, J. W. Choi, A. Coskun, Nat. Commun. 2022, 13, 2575.
- 31P. Xiao, R. Luo, Z. Piao, C. Li, J. Wang, K. Yu, G. Zhou, H.-M. Cheng, ACS Energy Lett. 2021, 6, 3170.
- 32S. Yu, S. Yang, D. Cai, H. Nie, X. Zhou, T. Li, C. Liang, H. Wang, Y. Dong, R. Xu, G. Fang, J. Qian, Y. Ge, Y. Hu, Z. Yang, InfoMat 2023, 5, 12381.
- 33L. Li, G. Xu, S. Zhang, S. Dong, S. Wang, Z. Cui, X. Du, C. Wang, B. Xie, J. Du, X. Zhou, G. Cui, ACS Energy Lett. 2022, 7, 591.
- 34Q.-K. Zhang, X.-Q. Zhang, J. Wan, N. Yao, T.-L. Song, J. Xie, L.-P. Hou, M.-Y. Zhou, X. Chen, B.-Q. Li, R. Wen, H.-J. Peng, Q. Zhang, J.-Q. Huang, Nat. Energy 2023, 8, 725.
- 35L.-J. Zheng, P. Bai, W.-F. Yan, F. Li, X.-X. Wang, J.-J. Xu, Matter 2023, 6, 142.
- 36J. Lee, T. H. Lee, H. W. Jang, H. S. Park, InfoMat 2022, 4, 12268.
- 37Y. Lin, Y. Li, Z. Mai, G. Yang, C. Wang, Adv. Energy Mater. 2023, 13.
- 38Z. Wang, Z. Sun, Y. Shi, F. Qi, X. Gao, H. Yang, H. M. Cheng, F. Li, Adv. Energy Mater. 2021, 11, 2100935.
- 39J. Wang, K. Yang, S. Sun, Q. Ma, G. Yi, X. Chen, Z. Wang, W. Yan, X. Liu, Q. Cai, Y. Zhao, InfoMat 2023, 5, 12401.
- 40W. Chen, Y. Hu, W. Lv, T. Lei, X. Wang, Z. Li, M. Zhang, J. Huang, X. Du, Y. Yan, W. He, C. Liu, M. Liao, W. Zhang, J. Xiong, C. Yan, Nat. Commun. 2019, 10, 4973.
- 41T. Ma, Y. Ni, Q. Wang, J. Xiao, Z. Huang, Z. Tao, J. Chen, Energy Storage Mater. 2022, 52, 69.
- 42D. Zhang, M. Liu, J. Ma, K. Yang, Z. Chen, K. Li, C. Zhang, Y. Wei, M. Zhou, P. Wang, Y. He, W. Lv, Q.-H. Yang, F. Kang, Y.-B. He, Nat. Commun. 2022, 13, 6966.
- 43N. Piao, S. Liu, B. Zhang, X. Ji, X. Fan, L. Wang, P.-F. Wang, T. Jin, S.-C. Liou, H. Yang, J. Jiang, K. Xu, M. A. Schroeder, X. He, C. Wang, ACS Energy Lett. 2021, 6, 1839.
- 44J. Sun, T. Wang, Y. Gao, Z. Pan, R. Hu, J. Wang, InfoMat 2022, 4, 12359.
- 45Y. Gao, T. Rojas, K. Wang, S. Liu, D. Wang, T. Chen, H. Wang, A. T. Ngo, D. Wang, Nat. Energy 2020, 5, 534.
- 46Z. Yu, H. Wang, X. Kong, W. Huang, Y. Tsao, D. G. Mackanic, K. Wang, X. Wang, W. Huang, S. Choudhury, Y. Zheng, C. V. Amanchukwu, S. T. Hung, Y. Ma, E. G. Lomeli, J. Qin, Y. Cui, Z. Bao, Nat. Energy 2020, 5, 526.
- 47S. Zhong, Y. Yu, Y. Yang, Y. Yao, L. Wang, S. He, Y. Yang, L. Liu, W. Sun, Y. Feng, H. Pan, X. Rui, Y. Yu, Angew. Chem., Int. Ed. 2023, 62, 202301169.
- 48M. Cheng, Z. Xing, R. Yan, Z. Zhao, T. Ma, M. Zhou, X. Liu, S. Li, C. Cheng, InfoMat 2023, 5, 12387.
- 49G. Zhang, J. Chang, L. Wang, J. Li, C. Wang, R. Wang, G. Shi, K. Yu, W. Huang, H. Zheng, T. Wu, Y. Deng, J. Lu, Nat. Commun. 2023, 14, 1081.
- 50J. Moon, D. O. Kim, L. Bekaert, M. Song, J. Chung, D. Lee, A. Hubin, J. Lim, Nat. Commun. 2022, 13, 4538.
- 51J. Meng, M. Lei, C. Lai, Q. Wu, Y. Liu, C. Li, Angew. Chem., Int. Ed. 2021, 60, 23256.
- 52J. Shi, C. Xu, J. Lai, Z. Li, Y. Zhang, Y. Liu, K. Ding, Y. P. Cai, R. Shang, Q. Zheng, Angew. Chem., Int. Ed. 2023, 62, 20221851.
- 53Z. Huang, J.-C. Lai, S.-L. Liao, Z. Yu, Y. Chen, W. Yu, H. Gong, X. Gao, Y. Yang, J. Qin, Y. Cui, Z. Bao, Nat. Energy 2023, 8, 577.
- 54J. Huang, J. Liu, J. He, M. Wu, S. Qi, H. Wang, F. Li, J. Ma, Angew. Chem., Int. Ed. 2021, 60, 20717.
- 55C. Li, L. Gu, X. Guo, D. Samuelis, K. Tang, J. Maier, Nano Lett. 2012, 12, 1241.
- 56C. Li, L. Gu, J. Maier, Adv. Funct. Mater. 2012, 22, 1145.
- 57S. Zhang, R. Li, N. Hu, T. Deng, S. Weng, Z. Wu, D. Lu, H. Zhang, J. Zhang, X. Wang, L. Chen, L. Fan, X. Fan, Nat. Commun. 2022, 13, 5431.
- 58C. Wu, J. Hu, Q. Yang, M. Lei, Y. Yu, C. Lai, C. Li, Nano Energy 2023, 113, 108523.
- 59Z. Li, H. Rao, R. Atwi, B. M. Sivakumar, B. Gwalani, S. Gray, K. S. Han, T. A. Everett, T. A. Ajantiwalay, V. Murugesan, N. N. Rajput, V. G. Pol, Nat. Commun. 2023, 14, 868.
