Issue

Vol. 15 (2023)

Demystifying the Salt-Induced Li Loss: A Universal Procedure for the Electrolyte Design of Lithium-Metal Batteries

https://doi.org/10.1007/s40820-023-01205-3
Zhenglu Zhu
State Key Laboratory of Material Processing and Die and Mold Technology, School of Materials Science and Engineering, Huazhong University of Science and Technology, Wuhan 430074, Hubei, People’s Republic of China
Xiaohui Li
Institute of Nanoscience and Nanotechnology, School of Physical Science and Technology, Central China Normal University, Wuhan 430079, People’s Republic of China
Xiaoqun Qi
State Key Laboratory of Material Processing and Die and Mold Technology, School of Materials Science and Engineering, Huazhong University of Science and Technology, Wuhan 430074, Hubei, People’s Republic of China
Jie Ji
State Key Laboratory of Material Processing and Die and Mold Technology, School of Materials Science and Engineering, Huazhong University of Science and Technology, Wuhan 430074, Hubei, People’s Republic of China
Yongsheng Ji
Institute of New Energy for Vehicles, School of Materials Science and Engineering, Tongji University, Shanghai 201804, People’s Republic of China
Ruining Jiang
Institute of New Energy for Vehicles, School of Materials Science and Engineering, Tongji University, Shanghai 201804, People’s Republic of China
Chaofan Liang
State Key Laboratory of Material Processing and Die and Mold Technology, School of Materials Science and Engineering, Huazhong University of Science and Technology, Wuhan 430074, Hubei, People’s Republic of China
Dan Yang
Institute of New Energy for Vehicles, School of Materials Science and Engineering, Tongji University, Shanghai 201804, People’s Republic of China
Ze Yang
Institute of Nanoscience and Nanotechnology, School of Physical Science and Technology, Central China Normal University, Wuhan 430079, People’s Republic of China
Long Qie
State Key Laboratory of Material Processing and Die and Mold Technology, School of Materials Science and Engineering, Huazhong University of Science and Technology, Wuhan 430074, Hubei, People’s Republic of China
Yunhui Huang
State Key Laboratory of Material Processing and Die and Mold Technology, School of Materials Science and Engineering, Huazhong University of Science and Technology, Wuhan 430074, Hubei, People’s Republic of China

Corresponding Author: Long Qie

qie@hust.edu.cn

Nano-Micro Letters, Vol. 15 (2023), Article Number: 234

Abstract

Lithium (Li) metal electrodes show significantly different reversibility in the electrolytes with different salts. However, the understanding on how the salts impact on the Li loss remains unclear. Herein, using the electrolytes with different salts (e.g., lithium hexafluorophosphate (LiPF6), lithium difluoro(oxalato)borate (LiDFOB), and lithium bis(fluorosulfonyl)amide (LiFSI)) as examples, we decouple the irreversible Li loss (SEI Li+ and “dead” Li) during cycling. It is found that the accumulation of both SEI Li+ and “dead” Li may be responsible to the irreversible Li loss for the Li metal in the electrolyte with LiPF6 salt. While for the electrolytes with LiDFOB and LiFSI salts, the accumulation of “dead” Li predominates the Li loss. We also demonstrate that lithium nitrate and fluoroethylene carbonate additives could, respectively, function as the “dead” Li and SEI Li+ inhibitors. Inspired by the above understandings, we propose a universal procedure for the electrolyte design of Li metal batteries (LMBs): (i) decouple and find the main reason for the irreversible Li loss; (ii) add the corresponding electrolyte additive. With such a Li-loss-targeted strategy, the Li reversibility was significantly enhanced in the electrolytes with 1,2-dimethoxyethane, triethyl phosphate, and tetrahydrofuran solvents. Our strategy may broaden the scope of electrolyte design toward practical LMBs.


Highlights:
1 The loss mechanisms of irreversible Li in electrolytes with various salts (e.g., lithium hexafluorophosphate (LiPF6), lithium difluoro(oxalato)borate (LiDFOB), and lithium bis(fluorosulfonyl)amide (LiFSI)) are systemically revealed.
2 A universal procedure for the electrolyte design of Li metal batteries is proposed: (i) decouple and find the main reason for the irreversible Li loss; (ii) add the corresponding electrolyte additive.

Keywords

Li loss Universal guideline Electrolyte design Li reversibility
Zhu, Zhenglu, Xiaohui Li, Xiaoqun Qi, Jie Ji, Yongsheng Ji, Ruining Jiang, Chaofan Liang, Dan Yang, Ze Yang, Long Qie, and Yunhui Huang. 2023. “Demystifying the Salt-Induced Li Loss: A Universal Procedure for the Electrolyte Design of Lithium-Metal Batteries”. Nano-Micro Letters 15 (October):234. https://doi.org/10.1007/s40820-023-01205-3.
Download Citation
Endnote/Zotero/Mendeley (RIS)
BibTeX
References
  1. S. Nanda, A. Gupta, A. Manthiram, Anode-free full cells: a pathway to high-energy density lithium-metal batteries. Adv. Energy Mater. 11(2), 2000804 (2020). https://doi.org/10.1002/aenm.202000804
  2. Y. Zhan, P. Shi, C. Jin, Y. Xiao, M. Zhou et al., Regulating the two-stage accumulation mechanism of inactive lithium for practical composite lithium metal anodes. Adv. Funct. Mater. 32(43), 2206834 (2022). https://doi.org/10.1002/adfm.202206834
  3. R. Xu, J. Ding, X. Ma, C. Yan, Y. Yao et al., Designing and demystifying the lithium metal interface toward highly reversible batteries. Adv. Mater. 33(52), e2105962 (2021). https://doi.org/10.1002/adma.202105962
  4. Y. Liu, X. Xu, O.O. Kapitanova, P.V. Evdokimov, Z. Song et al., Electro-chemo-mechanical modeling of artificial solid electrolyte interphase to enable uniform electrodeposition of lithium metal anodes. Adv. Energy Mater. 12(9), 2103589 (2022). https://doi.org/10.1002/aenm.202103589
  5. X. Xu, X. Jiao, O.O. Kapitanova, J. Wang, V.S. Volkov et al., Diffusion limited current density: a watershed in electrodeposition of lithium metal anode. Adv. Energy Mater. 12(19), 2200244 (2022). https://doi.org/10.1002/aenm.202200244
  6. C. Niu, H. Pan, W. Xu, J. Xiao, J. Zhang et al., Self-smoothing anode for achieving high-energy lithium metal batteries under realistic conditions. Nat. Nanotechnol. 14(6), 594–601 (2019). https://doi.org/10.1038/s41565-019-0427-9
  7. Y. Ren, L. Zeng, H. Jiang, W. Ruan, Q. Chen et al., Rational design of spontaneous reactions for protecting porous lithium electrodes in lithium-sulfur batteries. Nat. Commun. 10(1), 3249 (2019). https://doi.org/10.1038/s41467-019-11168-y
  8. S. Xu, K. Chen, N.P. Dasgupta, J.B. Siegel, A.G. Stefanopoulou, Evolution of dead lithium growth in lithium metal batteries: experimentally validated model of the apparent capacity loss. J. Electrochem. Soc. 166(14), A3456–A3463 (2019). https://doi.org/10.1149/2.0991914jes
  9. J. Chen, Z. Cheng, Y. Liao, L. Yuan, Z. Li et al., Selection of redox mediators for reactivating dead li in lithium metal batteries. Adv. Energy Mater. 12(40), 2201800 (2022). https://doi.org/10.1002/aenm.202201800
  10. J. Chen, B. He, Z. Cheng, Z. Rao, D. He et al., Reactivating dead Li by shuttle effect for high-performance anode-free Li metal batteries. J. Electrochem. Soc. 168(12), 120535 (2021). https://doi.org/10.1149/1945-7111/ac42a5
  11. N. Piao, S. Liu, B. Zhang, X. Ji, X. Fan et al., Lithium metal batteries enabled by synergetic additives in commercial carbonate electrolytes. ACS Energy Lett. 6(5), 1839–1848 (2021). https://doi.org/10.1021/acsenergylett.1c00365
  12. Q. Liu, Y. Xu, J. Wang, B. Zhao, Z. Li et al., Sustained-release nanocapsules enable long-lasting stabilization of Li anode for practical Li-metal batteries. Nano-Micro Lett. 12(1), 176 (2020). https://doi.org/10.1007/s40820-020-00514-1
  13. C. Zhu, C. Sun, R. Li, S. Weng, L. Fan et al., Anion–diluent pairing for stable high-energy Li metal batteries. ACS Energy Lett. 7(4), 1338–1347 (2022). https://doi.org/10.1021/acsenergylett.2c00232
  14. Y. Huang, R. Li, S. Weng, H. Zhang, C. Zhu et al., Eco-friendly electrolytes via a robust bond design for high-energy Li metal batteries. Energy Environ. Sci. 15(10), 4349–4361 (2022). https://doi.org/10.1039/d2ee01756c
  15. Y. Yang, D.M. Davies, Y. Yin, O. Borodin, J.Z. Lee et al., High-efficiency lithium-metal anode enabled by liquefied gas electrolytes. Joule 3(8), 1986–2000 (2019). https://doi.org/10.1016/j.joule.2019.06.008
  16. Z. Wang, Y. Wang, B. Li, J.C. Bouwer, K. Davey et al., Non-flammable ester electrolyte with boosted stability against Li for high-performance Li metal batteries. Angew. Chem. Int. Ed. 61(41), e202206682 (2022). https://doi.org/10.1002/anie.202206682
  17. Y. Yao, X. Chen, C. Yan, X. Zhang, W. Cai et al., Regulating interfacial chemistry in lithium-ion batteries by a weakly solvating electrolyte. Angew. Chem. Int. Ed. 60(8), 4090–4097 (2021). https://doi.org/10.1002/anie.202011482
  18. J. Xu, J. Zhang, T.P. Pollard, Q. Li, S. Tan et al., Electrolyte design for Li-ion batteries under extreme operating conditions. Nature 614(7949), 694–700 (2023). https://doi.org/10.1038/s41586-022-05627-8
  19. X. Ren, P. Gao, L. Zou, S. Jiao, X. Cao et al., Role of inner solvation sheath within salt-solvent complexes in tailoring electrode/electrolyte interphases for lithium metal batteries. Proc. Natl. Acad. Sci. U.S.A. 117(46), 28603–28613 (2020). https://doi.org/10.1073/pnas.2010852117
  20. X. Cao, P. Gao, X. Ren, L. Zou, M.H. Engelhard et al., Effects of fluorinated solvents on electrolyte solvation structures and electrode/electrolyte interphases for lithium metal batteries. Proc. Natl. Acad. Sci. U.S.A. (2021). https://doi.org/10.1073/pnas.2020357118
  21. C.-C. Su, M. He, M. Cai, J. Shi, R. Amine et al., Solvation-protection-enabled high-voltage electrolyte for lithium metal batteries. Nano Energy 92, 106720 (2022). https://doi.org/10.1016/j.nanoen.2021.106720
  22. S. Zhang, R. Li, N. Hu, T. Deng, S. Weng et al., Tackling realistic Li+ flux for high-energy lithium metal batteries. Nat. Commun. 13, 5431 (2022). https://doi.org/10.1038/s41467-022-33151-w
  23. G. Park, K. Lee, D.-J. Yoo, J.W. Choi, Strategy for stable interface in lithium metal batteries: free solvent derived vs anion derived. ACS Energy Lett. 7(12), 4274–4281 (2022). https://doi.org/10.1021/acsenergylett.2c02399
  24. G. Yang, Y. Li, S. Liu, S. Zhang, Z. Wang et al., LiFSI to improve lithium deposition in carbonate electrolyte. Energy Storage Mater. 23, 350–357 (2019). https://doi.org/10.1016/j.ensm.2019.04.041
  25. Y. Xiao, B. Han, Y. Zeng, S. Chi, X. Zeng et al., New lithium salt forms interphases suppressing both Li dendrite and polysulfide shuttling. Adv. Energy Mater. 10(14), 1903937 (2020). https://doi.org/10.1002/aenm.201903937
  26. S. Jurng, Z.L. Brown, J. Kim, B.L. Lucht, Effect of electrolyte on the nanostructure of the solid electrolyte interphase (SEI) and performance of lithium metal anodes. Energy Environ. Sci. 11(9), 2600–2608 (2018). https://doi.org/10.1039/c8ee00364e
  27. L. Qiao, U. Oteo, M. Martinez-Ibanez, A. Santiago, R. Cid et al., Stable non-corrosive sulfonimide salt for 4-V-class lithium metal batteries. Nat. Mater. 21(4), 455–462 (2022). https://doi.org/10.1038/s41563-021-01190-1
  28. B.D. Adams, J. Zheng, X. Ren, W. Xu, J. Zhang, Accurate determination of coulombic efficiency for lithium metal anodes and lithium metal batteries. Adv. Energy Mater. 8(7), 1702097 (2017). https://doi.org/10.1002/aenm.201702097
  29. X. Zheng, L. Huang, W. Luo, H. Wang, Y. Dai et al., Tailoring electrolyte solvation chemistry toward an inorganic-rich solid-electrolyte interphase at a Li metal anode. ACS Energy Lett. 6(6), 2054–2063 (2021). https://doi.org/10.1021/acsenergylett.1c00647
  30. X. Ren, L. Zou, X. Cao, M.H. Engelhard, W. Liu et al., Enabling high-voltage lithium-metal batteries under practical conditions. Joule 3(7), 1662–1676 (2019). https://doi.org/10.1016/j.joule.2019.05.006
  31. X. Ren, L. Zou, S. Jiao, D. Mei, M.H. Engelhard et al., High-concentration ether electrolytes for stable high-voltage lithium metal batteries. ACS Energy Lett. 4(4), 896–902 (2019). https://doi.org/10.1021/acsenergylett.9b00381
  32. Y. Chen, Z. Yu, P. Rudnicki, H. Gong, Z. Huang et al., Steric effect tuned ion solvation enabling stable cycling of high-voltage lithium metal battery. J. Am. Chem. Soc. 143(44), 18703–18713 (2021). https://doi.org/10.1021/jacs.1c09006
  33. Z. Wu, R. Li, S. Zhang, L. Lv, T. Deng et al., Deciphering and modulating energetics of solvation structure enables aggressive high-voltage chemistry of Li metal batteries. Chem 9(3), 650–664 (2023). https://doi.org/10.1016/j.chempr.2022.10.027
  34. J. Ding, R. Xu, X. Ma, Y. Xiao, Y. Yao et al., Quantification of the dynamic interface evolution in high-efficiency working Li-metal batteries. Angew. Chem. Int. Ed. 61(13), e202115602 (2022). https://doi.org/10.1002/anie.202115602
  35. Z. Zhu, Z. Liu, R. Zhao, X. Qi, J. Ji et al., Heterogeneous nitride interface enabled by stepwise-reduction electrolyte design for dense Li deposition in carbonate electrolytes. Adv. Funct. Mater. 32(48), 2209384 (2022). https://doi.org/10.1002/adfm.202209384
  36. X. Zhang, X. Cheng, X. Chen, C. Yan, Q. Zhang, Fluoroethylene carbonate additives to render uniform Li deposits in lithium metal batteries. Adv. Funct. Mater. 27(10), 1605989 (2017). https://doi.org/10.1002/adfm.201605989
  37. X. Zheng, S. Weng, W. Luo, B. Chen, X. Zhang et al., Deciphering the role of fluoroethylene carbonate towards highly reversible sodium metal anodes. Research 2022, 9754612 (2022). https://doi.org/10.34133/2022/9754612
  38. S. Liu, J. Xia, W. Zhang, H. Wan, J. Zhang et al., Salt-in-salt reinforced carbonate electrolyte for Li metal batteries. Angew. Chem. Int. Ed. 61(43), e202210522 (2022). https://doi.org/10.1002/anie.202210522
Read More
Author biographies are not available.
Download this PDF file
PDF SUPPLEMENTARY FILE
Statistic
Read Counter : 2337 Download : 1732

Most read articles by the same author(s)