Issue

Vol. 15 (2023)

In Situ Formed Tribofilms as Efficient Organic/Inorganic Hybrid Interlayers for Stabilizing Lithium Metal Anodes

https://doi.org/10.1007/s40820-023-01210-6
Shaozhen Huang
State Key Laboratory of Powder Metallurgy, Central South University, Changsha 410083, People’s Republic of China
Kecheng Long
State Key Laboratory of Powder Metallurgy, Central South University, Changsha 410083, People’s Republic of China
Yuejiao Chen
State Key Laboratory of Powder Metallurgy, Central South University, Changsha 410083, People’s Republic of China
Tuoya Naren
State Key Laboratory of Powder Metallurgy, Central South University, Changsha 410083, People’s Republic of China
Piao Qing
State Key Laboratory of Powder Metallurgy, Central South University, Changsha 410083, People’s Republic of China
Xiaobo Ji
State Key Laboratory of Powder Metallurgy, Central South University, Changsha 410083, People’s Republic of China
Weifeng Wei
State Key Laboratory of Powder Metallurgy, Central South University, Changsha 410083, People’s Republic of China
Zhibin Wu
State Key Laboratory of Powder Metallurgy, Central South University, Changsha 410083, People’s Republic of China
Libao Chen
State Key Laboratory of Powder Metallurgy, Central South University, Changsha 410083, People’s Republic of China

Corresponding Author: Libao Chen

lbchen@csu.edu.cn

Nano-Micro Letters, Vol. 15 (2023), Article Number: 235

Abstract

The practical application of Li metal anodes (LMAs) is limited by uncontrolled dendrite growth and side reactions. Herein, we propose a new friction-induced strategy to produce high-performance thin Li anode (Li@CFO). By virtue of the in situ friction reaction between fluoropolymer grease and Li strips during rolling, a robust organic/inorganic hybrid interlayer (lithiophilic LiF/LiC6 framework hybridized -CF2-O-CF2- chains) was formed atop Li metal. The derived interface contributes to reversible Li plating/stripping behaviors by mitigating side reactions and decreasing the solvation degree at the interface. The Li@CFO||Li@CFO symmetrical cell exhibits a remarkable lifespan for 5,600 h (1.0 mA cm−2 and 1.0 mAh cm−2) and 1,350 cycles even at a harsh condition (18.0 mA cm−2 and 3.0 mAh cm−2). When paired with high-loading LiFePO4 cathodes, the full cell lasts over 450 cycles at 1C with a high-capacity retention of 99.9%. This work provides a new friction-induced strategy for producing high-performance thin LMAs.


Highlights:
1 The robust organic/inorganic hybrid interlayer derived from in situ formed tribofilms were fabricated by using a scalable rolling method.
2 The interlayer facilitates dendrite-free lithium metal anodes by building local de-solvation environments near the interface and inhibiting both dendrite growth and electrolytes corrosion.
3 The symmetrical cell exhibits a remarkable lifespan of 5,600 h (1.0 mA cm-2 and 1.0 mAh cm-2) and 1,350 cycles even at a harsh condition (18.0 mA cm-2 and 3.0 mAh cm-2).

Keywords

Lithium metal anode Organic/inorganic hybrid interlayers High current density Fluoropolymer grease Local desolvation environment
Huang, Shaozhen, Kecheng Long, Yuejiao Chen, Tuoya Naren, Piao Qing, Xiaobo Ji, Weifeng Wei, Zhibin Wu, and Libao Chen. 2023. “In Situ Formed Tribofilms As Efficient Organic/Inorganic Hybrid Interlayers for Stabilizing Lithium Metal Anodes”. Nano-Micro Letters 15 (October):235. https://doi.org/10.1007/s40820-023-01210-6.
Download Citation
Endnote/Zotero/Mendeley (RIS)
BibTeX
References
  1. Q. Zhao, Y. Deng, N.W. Utomo, J. Zheng, P. Biswal et al., On the crystallography and reversibility of lithium electrodeposits at ultrahigh capacity. Nat. Commun. 12(1), 6034 (2021). https://doi.org/10.1038/s41467-021-26143-9
  2. D. Lin, Y. Liu, Y. Cui, Reviving the lithium metal anode for high-energy batteries. Nat. Nanotechnol. 12(3), 194–206 (2017). https://doi.org/10.1038/nnano.2017.16
  3. X.B. Cheng, R. Zhang, C.Z. Zhao, Q. Zhang, Toward safe lithium metal anode in rechargeable batteries: a review. Chem. Rev. 117(15), 10403–10473 (2017). https://doi.org/10.1021/acs.chemrev.7b00115
  4. Z. Hai, W. Yuxuan, D. Fei, S. Lin, M. Yaohua, An artificial li-al interphase layer on Li-B alloy for stable lithium-metal anode Electrochim. Acta 304(255), 262 (2019). https://doi.org/10.1016/j.electacta.2019.03.009
  5. J.L. Gao, C.J. Chen, Q. Dong, J.Q. Dai, Y.G. Yao et al., Stamping flexible li alloy anodes. Adv. Mater. 33(11), e2005305 (2021). https://doi.org/10.1002/adma.202005305
  6. Z. Zehua, L. Bin, Multi-storey corridor structured host for a large area capacity and high rate metallic lithium anode. Electrochim. Acta 365, 137341 (2021). https://doi.org/10.1016/j.electacta.2020.137341
  7. L. Ye, M. Liao, X. Cheng, X. Zhou, Y. Zhao et al., Lithium-metal anodes working at 60 mA cm(-2) and 60 mAh cm(-2) through nanoscale lithium-ion adsorbing. Angew. Chem. Int. Ed. 60(32), 17419–17425 (2021). https://doi.org/10.1002/anie.202106047
  8. Z. Luo, S. Li, L. Yang, Y. Tian, L. Xu et al., Interfacially redistributed charge for robust lithium metal anode. Nano Energy 87, 106212 (2021). https://doi.org/10.1016/j.nanoen.2021.106212
  9. X.-B. Cheng, H.-J. Peng, J.-Q. Huang, R. Zhang, C.-Z. Zhao et al., Dual-phase lithium metal anode containing a polysulfide-induced solid electrolyte interphase and nanostructured graphene framework for lithium–sulfur batteries. ACS Nano 9(6), 6373–6382 (2015). https://doi.org/10.1021/acsnano.5b01990
  10. Y. Gao, X. Du, Z. Hou, X. Shen, Y.-W. Mai et al., Unraveling the mechanical origin of stable solid electrolyte interphase. Joule 5(7), 1860–1872 (2021). https://doi.org/10.1016/j.joule.2021.05.015
  11. Z. Wu, W. Kong Pang, L. Chen, B. Johannessen, Z. Guo, In situ synchrotron X-ray absorption spectroscopy studies of anode materials for rechargeable batteries. Batter. Supercaps. 4(10), 1547–1566 (2021). https://doi.org/10.1002/batt.202100006
  12. C. Wu, H.F. Huang, W.Y. Lu, Z.X. Wei, X.Y. Ni et al., Mg doped li–lib alloy with in situ formed lithiophilic lib skeleton for lithium metal batteries. Adv. Sci. 7(6), 1902643 (2020). https://doi.org/10.1002/advs.201902643
  13. H. Liu, J. Di, P. Wang, R. Gao, H. Tian et al., A novel design of 3d carbon host for stable lithium metal anode. Carbon Energy 4(4), 654–664 (2022). https://doi.org/10.1002/cey2.193
  14. H. Ye, S. Xin, Y.X. Yin, J.Y. Li, Y.G. Guo et al., Stable li plating/stripping electrochemistry realized by a hybrid li reservoir in spherical carbon granules with 3d conducting skeletons. J. Am. Chem. Soc. 139(16), 5916–5922 (2017). https://doi.org/10.1021/jacs.7b01763
  15. U. Makoto, U. Kohei, Recent progress in liquid electrolytes for lithium metal batteries. Curr. Opinion Electrochem. 17, 106–113 (2019). https://doi.org/10.1016/j.coelec.2019.05.001
  16. F. Zhao, P. Zhai, Y. Wei, Z. Yang, Q. Chen et al., Constructing artificial sei layer on lithiophilic mxene surface for high-performance lithium metal anodes. Adv. Sci. 9(6), e2103930 (2022). https://doi.org/10.1002/advs.202103930
  17. D. Shin, J.E. Bachman, M.K. Taylor, J. Kamcev, J.G. Park, A single-ion conducting borate network polymer as a viable quasi-solid electrolyte for lithium metal batteries. Adv. Mater. 32(10), e1905771 (2020). https://doi.org/10.1002/adma.201905771
  18. X.B. Cheng, T.Z. Hou, R. Zhang, H.J. Peng, C.Z. Zhao et al., Dendrite-free lithium deposition induced by uniformly distributed lithium ions for efficient lithium metal batteries. Adv. Mater. 28(15), 2888–2895 (2016). https://doi.org/10.1002/adma.201506124
  19. F. Wu, S. Fang, M. Kuenzel, A. Mullaliu, J.-K. Kim et al., Dual-anion ionic liquid electrolyte enables stable Ni-rich cathodes in lithium-metal batteries. Joule 5(8), 2177–2194 (2021). https://doi.org/10.1016/j.joule.2021.06.014
  20. 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
  21. J. Ryu, D.-Y. Han, D. Hong, S. Park, A polymeric separator membrane with chemoresistance and high li-ion flux for high-energy-density lithium metal batteries. Energy Storage Mater. 45, 941–951 (2022). https://doi.org/10.1016/j.ensm.2021.12.046
  22. L. Xiao, Z. Zeng, X. Liu, Y. Fang, X. Jiang et al., Stable li metal anode with “ion–solvent-coordinated” nonflammable electrolyte for safe Li metal batteries. ACS Energy Lett. 4(2), 483–488 (2019). https://doi.org/10.1021/acsenergylett.8b02527
  23. Y. Gao, Y. Zhao, Y.C. Li, Q. Huang, T.E. Mallouk et al., Interfacial chemistry regulation via a skin-grafting strategy enables high-performance lithium-metal batteries. J. Am. Chem. Soc. 139(43), 15288–15291 (2017). https://doi.org/10.1021/jacs.7b06437
  24. G. Liu, W. Lu, A model of concurrent lithium dendrite growth, sei growth, sei penetration and regrowth. J. Electrochem. Soc. 164(9), A1826–A1833 (2017). https://doi.org/10.1149/2.0381709jes
  25. C. Cui, C. Yang, N. Eidson, J. Chen, F. Han, A highly reversible, dendrite-free lithium metal anode enabled by a lithium-fluoride-enriched interphase. Adv. Mater. 32(12), e1906427 (2020). https://doi.org/10.1002/adma.201906427
  26. R.H. Wang, W.S. Cui, F.L. Chu, F.X. Wu, Lithium metal anodes: Present and future. J. Energy Chem. 48(2020), 145–159 (2020). https://doi.org/10.1016/j.jechem.2019.12.024
  27. X. Shuixin, Z. Xun, L. Chao, Y. Yi, L. Wei, Stabilized lithium metal anode by an efficient coating for high-performance Li–S batteries. Energy Storage Mater. 24(2020), 329–335 (2020). https://doi.org/10.1016/j.ensm.2019.07.042
  28. X. Zhang, T. Liu, S. Zhang, X. Huang, B. Xu et al., Synergistic coupling between Li(6.75)La(3)Zr(1.75)Ta(0.25)O(12) and poly(vinylidene fluoride) induces high ionic conductivity, mechanical strength, and thermal stability of solid composite electrolytes. J. Am. Chem. Soc. 139(39), 13779–13785 (2017). https://doi.org/10.1021/jacs.7b06364
  29. C. Szczuka, B. Karasulu, M.F. Groh, F.N. Sayed, T.J. Sherman et al., Forced disorder in the solid solution Li3P-Li2S: A new class of fully reduced solid electrolytes for lithium metal anodes. J. Am. Chem. Soc. 144(36), 16350–16365 (2022). https://doi.org/10.1021/jacs.2c01913
  30. Y. Yu, G. Huang, J.Z. Wang, K. Li, J.L. Ma et al., In situ designing a gradient li(+) capture and quasi-spontaneous diffusion anode protection layer toward long-life Li-O(2) batteries. Adv. Mater. 32(38), e2004157 (2020). https://doi.org/10.1002/adma.202004157
  31. J. Lang, Y. Long, J. Qu, X. Luo, H. Wei et al., One-pot solution coating of high quality lif layer to stabilize li metal anode. Energy Storage Mater. 16, 85–90 (2019). https://doi.org/10.1016/j.ensm.2018.04.024
  32. D. Wang, H. Liu, F. Liu, G. Ma, J. Yang et al., Phase-separation-induced porous lithiophilic polymer coating for high-efficiency lithium metal batteries. Nano Lett. 21(11), 4757–4764 (2021). https://doi.org/10.1021/acs.nanolett.1c01241
  33. Q. Yang, J. Hu, J. Meng, C. Li, C–f-rich oil drop as a non-expendable fluid interface modifier with low surface energy to stabilize a Li metal anode. Energy Environ. Sci. 14(6), 3621–3631 (2021). https://doi.org/10.1039/d0ee03952g
  34. Y.K. Lee, K.Y. Cho, S. Lee, J. Choi, G. Lee et al., Construction of hierarchical surface on carbon fiber paper for lithium metal batteries with superior stability. Adv. Energy Mater. 13(9), 2203770 (2023). https://doi.org/10.1002/aenm.202203770
  35. Y. Hu, Z. Li, Z. Wang, X. Wang, W. Chen et al., Suppressing local dendrite hotspots via current density redistribution using a superlithiophilic membrane for stable lithium metal anode. Adv. Sci. 10(12), e2206995 (2023). https://doi.org/10.1002/advs.202206995
  36. Y.-X. Song, W.-Y. Lu, Y.-J. Chen, H. Yang, C. Wu et al., Coating highly lithiophilic Zn on Cu foil for high-performance lithium metal batteries. Rare Met. 41(4), 1255–1264 (2021). https://doi.org/10.1007/s12598-021-01811-3
  37. H.-F. Huang, Y.-N. Gui, F. Sun, Z.-J. Liu, H.-L. Ning et al., In situ formed three-dimensional (3d) lithium–boron (Li–B) alloy as a potential anode for next-generation lithium batteries. Rare Met. 40(12), 3494–3500 (2021). https://doi.org/10.1007/s12598-021-01708-1
  38. Y.-S. Hu, Y. Lu, The mystery of electrolyte concentration: From superhigh to ultralow. ACS Energy Lett. 5(11), 3633–3636 (2020). https://doi.org/10.1021/acsenergylett.0c02234
  39. Z. Wang, Z. Sun, J. Li, Y. Shi, C. Sun et al., Insights into the deposition chemistry of li ions in nonaqueous electrolyte for stable li anodes. Chem. Soc. Rev. 50(5), 3178–3210 (2021). https://doi.org/10.1039/d0cs01017k
  40. A. Kusumi, Y. Sako, M. Yamamoto, Confined lateral diffusion of membrane receptors as studied by single p tracking (nanovid microscopy). Effects of calcium-induced differentiation in cultured epithelial cells. Biophys. J. 65, 2021–2040 (1993). https://doi.org/10.1016/S0006-3495(93)81253-0
  41. H. Ji, Z. Wang, Y. Sun, Y. Zhou, S. Li et al., Weakening Li+ de-solvation barrier for cryogenic Li-S pouch cells. Adv. Mater. 35(9), e2208590 (2023). https://doi.org/10.1002/adma.202208590
  42. J. Park, S. Ha, J.Y. Jung, J.H. Hyun, S.H. Yu et al., Understanding the effects of interfacial lithium ion concentration on lithium metal anode. Adv. Sci. 9(6), e2104145 (2022). https://doi.org/10.1002/advs.202104145
  43. X. Liu, J. Liu, T. Qian, H. Chen, C. Yan, Novel organophosphate-derived dual-layered interface enabling air-stable and dendrite-free lithium metal anode. Adv. Mater. 32(2), e1902724 (2019). https://doi.org/10.1002/adma.201902724
  44. X.X. Ma, X. Chen, Y.K. Bai, X. Shen, R. Zhang et al., The defect chemistry of carbon frameworks for regulating the lithium nucleation and growth behaviors in lithium metal anodes. Small 17(48), e2007142 (2021). https://doi.org/10.1002/smll.202007142
  45. P. Shi, L.-P. Hou, C.-B. Jin, Y. Xiao, Y.-X. Yao et al., A successive conversion–deintercalation delithiation mechanism for practical composite lithium anodes. J. Am. Chem. Soc. 144(1), 212–218 (2021). https://doi.org/10.1021/jacs.1c08606
  46. H. Wang, Y. Chen, H. Yu, W. Liu, G. Kuang et al., A multifunctional artificial interphase with fluorine-doped amorphous carbon layer for ultra-stable Zn anode. Adv. Funct. Mater. 32(43), 2205600 (2022). https://doi.org/10.1002/adfm.202205600
  47. S. Ye, X. Chen, R. Zhang, Y. Jiang, F. Huang et al., Revisiting the role of physical confinement and chemical regulation of 3d hosts for dendrite-free li metal anode. Nano-Micro Lett. 14(1), 187 (2022). https://doi.org/10.1007/s40820-022-00932-3
  48. L.-P. Hou, X.-Q. Zhang, B.-Q. Li, Q. Zhang, Challenges and promises of lithium metal anode by soluble polysulfides in practical lithium–sulfur batteries. Mater. Today 45, 62–76 (2021). https://doi.org/10.1016/j.mattod.2020.10.021
  49. C. Qin, D. Wang, Y. Liu, P. Yang, T. Xie et al., Tribo-electrochemistry induced artificial solid electrolyte interface by self-catalysis. Nat. Commun. 12(1), 7184 (2021). https://doi.org/10.1038/s41467-021-27494-z
Read More
Author biographies are not available.
Download this PDF file
PDF SUPPLEMENTARY FILE
Statistic
Read Counter : 2796 Download : 2082

Most read articles by the same author(s)