Suspension electrolyte with modified Li+ solvation environment for lithium metal batteries
Source abstract
Abstract
Designing a stable solid-electrolyte interphase on a Li anode is imperative to developing reliable Li metal batteries. Herein, we report a suspension electrolyte design that modifies the Li+ solvation environment in liquid electrolytes and creates inorganic-rich solid-electrolyte interphases on Li. Li2O nanoparticles suspended in liquid electrolytes were investigated as a proof of concept. Through theoretical and empirical analyses of Li2O suspension electrolytes, the roles played by Li2O in the liquid electrolyte and solid-electrolyte interphases of the Li anode are elucidated. Also, the suspension electrolyte design is applied in conventional and state-of-the-art high-performance electrolytes to demonstrate its applicability. Based on electrochemical analyses, improved Coulombic efficiency (up to ~99.7%), reduced Li nucleation overpotential, stabilized Li interphases and prolonged cycle life of anode-free cells (~70 cycles at 80% of initial capacity) were achieved with the suspension electrolytes. We expect this design principle and our findings to be expanded into developing electrolytes and solid-electrolyte interphases for Li metal batteries.
Source: europepmc · Quality: candidate unverified · Source record ↗
Research context
OpenAlex topics: Advanced Battery Materials and Technologies · Advancements in Battery Materials · Thermal Expansion and Ionic Conductivity
SciVX discovery tags are terminology-based. OpenAlex topics are source-provided classifications.
References (56)
Show source-provided references
1. Xiao, J. et al. Understanding and applying Coulombic efficiency in lithium metal batteries. Nat. Energy 5, 561–568 (2020).10.1038/s41560-020-0648-z ↗
2. Zheng, J. et al. Regulating electrodeposition morphology of lithium: towards commercially relevant secondary Li metal batteries. Chem. Soc. Rev. 49, 2701–2750 (2020).10.1039/C9CS00883G ↗
3. Liu, J. et al. Pathways for practical high-energy long-cycling lithium metal batteries. Nat. Energy 4, 180–186 (2019).10.1038/s41560-019-0338-x ↗
4. Lin, D., Liu, Y. & Cui, Y. Reviving the lithium metal anode for high-energy batteries. Nat. Nanotechnol. 12, 194–206 (2017).10.1038/nnano.2017.16 ↗
5. Wu, H., Jia, H., Wang, C., Zhang, J. G. & Xu, W. Recent progress in understanding solid electrolyte interphase on lithium metal anodes. Advanced Energy Materials 11, 2003092 (2021).10.1002/aenm.202003092 ↗
6. Zachman, M. J., Tu, Z., Choudhury, S., Archer, L. A. & Kourkoutis, L. F. Cryo-STEM mapping of solid–liquid interfaces and dendrites in lithium-metal batteries. Nature 560, 345–349 (2018).10.1038/s41586-018-0397-3 ↗
7. Li, Y. et al. Correlating structure and function of battery interphases at atomic resolution using cryoelectron microscopy. Joule 2, 2167–2177 (2018).10.1016/j.joule.2018.08.004 ↗
8. Li, Y. et al. Atomic structure of sensitive battery materials and interfaces revealed by cryo–electron microscopy. Science 358, 506–510 (2017).10.1126/science.aam6014 ↗
9. Shadike, Z. et al. Identification of LiH and nanocrystalline LiF in the solid–electrolyte interphase of lithium metal anodes. Nat. Nanotechnol. https://doi.org/10.1038/s41565-020-00845-5 (2021).10.1038/s41565-020-00845-5 ↗
10. Boyle, D. T. et al. Corrosion of lithium metal anodes during calendar ageing and its microscopic origins. Nat. Energy https://doi.org/10.1038/s41560-021-00787-9 (2021).10.1038/s41560-021-00787-9 ↗
11. Xu, K. Electrolytes and interphases in Li-ion batteries and beyond. Chem. Rev. 114, 11503–11618 (2014).10.1021/cr500003w ↗
12. Cao, X. et al. Monolithic solid–electrolyte interphases formed in fluorinated orthoformate-based electrolytes minimize Li depletion and pulverization. Nat. Energy 4, 796–805 (2019).10.1038/s41560-019-0464-5 ↗
13. Fan, X. et al. Non-flammable electrolyte enables Li-metal batteries with aggressive cathode chemistries. Nat. Nanotechnol. 13, 715–722 (2018).10.1038/s41565-018-0183-2 ↗
14. Zhang, X. Q. et al. Regulating anions in the solvation sheath of lithium ions for stable lithium metal batteries. ACS Energy Lett. 4, 411–416 (2019).10.1021/acsenergylett.8b02376 ↗
15. Yu, Z. et al. Molecular design for electrolyte solvents enabling energy-dense and long-cycling lithium metal batteries. Nat. Energy 5, 526–533 (2020).10.1038/s41560-020-0634-5 ↗
16. Yuan, S. et al. Salt-rich solid electrolyte interphase for safer high-energy-density Li metal batteries with limited Li excess. Chem. Commun. 56, 8257–8260 (2020).10.1039/D0CC02481C ↗
17. Yamada, Y., Wang, J., Ko, S., Watanabe, E. & Yamada, A. Advances and issues in developing salt-concentrated battery electrolytes. Nat. Energy 4, 269–280 (2019).10.1038/s41560-019-0336-z ↗
18. Fan, X. et al. Highly fluorinated interphases enable high-voltage Li-metal batteries. Chem 4, 174–185 (2018).10.1016/j.chempr.2017.10.017 ↗
19. Qian, J. et al. High rate and stable cycling of lithium metal anode. Nat. Commun. 6, 6362 (2015).10.1038/ncomms7362 ↗
20. Suo, L. et al. “Water-in-salt” electrolyte enables high-voltage aqueous lithium-ion chemistries. Science 350, 938–943 (2015).10.1126/science.aab1595 ↗
21. Ren, X. et al. Enabling high-voltage lithium-metal batteries under practical conditions. Joule 3, 1662–1676 (2019).10.1016/j.joule.2019.05.006 ↗
22. Chen, S. et al. High-voltage lithium-metal batteries enabled by localized high-concentration electrolytes. Adv. Mater. 30, 1706102 (2018).10.1002/adma.201706102 ↗
23. Chen, S. et al. High-efficiency lithium metal batteries with fire-retardant electrolytes. Joule 2, 1548–1558 (2018).10.1016/j.joule.2018.05.002 ↗
24. Amanchukwu, C. V., Kong, X., Qin, J., Cui, Y. & Bao, Z. Nonpolar alkanes modify lithium-ion solvation for improved lithium deposition and stripping. Advanced Energy Materials 9, 1902116 (2019).10.1002/aenm.201902116 ↗
25. Tasaki, K. et al. Solubility of lithium salts formed on the lithium-ion battery negative electrode surface in organic solvents. J. Electrochem. Soc. 156, A1019 (2009).10.1149/1.3239850 ↗
26. Huang, W., Wang, H., Boyle, D. T., Li, Y. & Cui, Y. Resolving nanoscopic and mesoscopic heterogeneity of fluorinated species in battery solid-electrolyte interphases by cryogenic electron microscopy. ACS Energy Lett. 5, 1128–1135 (2020).10.1021/acsenergylett.0c00194 ↗
27. Liu, Y. et al. Solubility-mediated sustained release enabling nitrate additive in carbonate electrolytes for stable lithium metal anode. Nat. Commun. 9, 3656 (2018).10.1038/s41467-018-06077-5 ↗
28. Wang, J. et al. Improving cyclability of Li metal batteries at elevated temperatures and its origin revealed by cryo-electron microscopy. Nat. Energy 4, 664–670 (2019).10.1038/s41560-019-0413-3 ↗
29. Lowe, J. S. & Siegel, D. J. Modeling the interface between lithium metal and its native oxide. ACS Appl. Mater. Interfaces 12, 46015–46026 (2020).10.1021/acsami.0c12468 ↗
30. Guo, R. & Gallant, B. M. Li2O solid electrolyte interphase: probing transport properties at the chemical potential of lithium. Chem. Mater. https://doi.org/10.1021/acs.chemmater.0c00333 (2020).10.1021/acs.chemmater.0c00333 ↗
31. Tan, L. et al. In-situ tailored 3D Li2O@Cu nanowires array enabling stable lithium metal anode with ultra-high coulombic efficiency. J. Power Sources 463, 228178 (2020).10.1016/j.jpowsour.2020.228178 ↗
32. Shen, C. et al. Li2O-reinforced solid electrolyte interphase on three-dimensional sponges for dendrite-free lithium deposition. Front. Chem. 6, 517 (2018).10.3389/fchem.2018.00517 ↗
33. Adams, B. D., Zheng, J., Ren, X., Xu, W. & Zhang, J. G. Accurate determination of Coulombic efficiency for lithium metal anodes and lithium metal batteries. Adv. Energy Mater. 8, 1702097 (2017).10.1002/aenm.201702097 ↗
34. Kim, M. S. et al. Langmuir–Blodgett artificial solid-electrolyte interphases for practical lithium metal batteries. Nat. Energy 3, 889–898 (2018).10.1038/s41560-018-0237-6 ↗
35. Pei, A., Zheng, G., Shi, F., Li, Y. & Cui, Y. Nanoscale nucleation and growth of electrodeposited lithium metal. Nano Lett. 17, 1132–1139 (2017).10.1021/acs.nanolett.6b04755 ↗
36. Fister, T. T. et al. Electronic structure of lithium battery interphase compounds: comparison between inelastic X-ray scattering measurements and theory. J. Chem. Phys. 135, 224513 (2011).10.1063/1.3664620 ↗
37. Ozhabes, Y., Gunceler, D. & Arias, T. A. Stability and surface diffusion at lithium-electrolyte interphases with connections to dendrite suppression. Preprint at arXiv https://arxiv.org/abs/1504.05799 (2015).
38. Lu, Y., Tu, Z. & Archer, L. A. Stable lithium electrodeposition in liquid and nanoporous solid electrolytes. Nat. Mater. 13, 961–969 (2014).10.1038/nmat4041 ↗
39. Kim, S. C. et al. Potentiometric measurement to probe solvation energy and its correlation to lithium battery cyclability. J. Am. Chem. Soc. 143, 10301–10308 (2021).10.1021/jacs.1c03868 ↗
40. Amanchukwu, C. V. et al. A new class of ionically conducting fluorinated ether electrolytes with high electrochemical stability. J. Am. Chem. Soc. 142, 7393–7403 (2020).10.1021/jacs.9b11056 ↗
41. Kamphaus, E. P. et al. Role of inorganic surface layer on solid electrolyte interphase evolution at Li-metal anodes. ACS Appl. Mater. Interfaces 11, 31467–31476 (2019).10.1021/acsami.9b07587 ↗
42. Xie, J. et al. Atomic layer deposition of stable LiAlF4 lithium ion conductive interfacial layer for stable cathode cycling. ACS Nano 11, 7019–7027 (2017).10.1021/acsnano.7b02561 ↗
43. Kim, M. S. et al. Enabling reversible redox reactions in electrochemical cells using protected LiAl intermetallics as lithium metal anodes. Sci. Adv. https://doi.org/10.1126/sciadv.aax5587 (2019).10.1126/sciadv.aax5587 ↗
44. Kim, M. S. et al. Langmuir–Blodgett artificial solid-electrolyte interphases for practical lithium metal batteries. Nat. Energy https://doi.org/10.1038/s41560-018-0237-6 (2018).10.1038/s41560-018-0237-6 ↗
45. Abraham, M. J. et al. Gromacs: high performance molecular simulations through multi-level parallelism from laptops to supercomputers. SoftwareX 1–2, 19–25 (2015).10.1016/j.softx.2015.06.001 ↗
46. Jorgensen, W. L., Maxwell, D. S. & Tirado-Rives, J. Development and testing of the OPLS all-atom force field on conformational energetics and properties of organic liquids. J. Am. Chem. Soc. 118, 11225–11236 (1996).10.1021/ja9621760 ↗
47. Dodda, L. S., De Vaca, I. C., Tirado-Rives, J. & Jorgensen, W. L. LigParGen web server: an automatic OPLS-AA parameter generator for organic ligands. Nucleic Acids Res. 45, W331–W336 (2017).10.1093/nar/gkx312 ↗
48. Doherty, B., Zhong, X., Gathiaka, S., Li, B. & Acevedo, O. Revisiting OPLS force field parameters for ionic liquid simulations. J. Chem. Theory Comput. 13, 6131–6135 (2017).10.1021/acs.jctc.7b00520 ↗
49. Benitez, L. & Seminario, J. M. Ion diffusivity through the solid electrolyte interphase in lithium-ion batteries. J. Electrochem. Soc. 164, E3159–E3170 (2017).10.1149/2.0181711jes ↗
50. Radin, M. D., Rodriguez, J. F., Tian, F. & Siegel, D. J. Lithium peroxide surfaces are metallic, while lithium oxide surfaces are not. J. Am. Chem. Soc. 134, 1093–1103 (2012).10.1021/ja208944x ↗
51. Humphrey, W., Dalke, A. & Schulten, K. VMD: Visual Molecular Dynamics. J. Mol. Graph. 14, 33–38 (1996).10.1016/0263-7855(96)00018-5 ↗
52. Allouche, A. Gabedit—a graphical user interface for computational chemistry softwares. J. Comput. Chem. 32, 174–182 (2011).10.1002/jcc.21600 ↗
53. Mortensen, J. J., Hansen, L. B. & Jacobsen, K. W. Real-space grid implementation of the projector augmented wave method. Phys. Rev. B 71, 035109 (2005).10.1103/PhysRevB.71.035109 ↗
54. Enkovaara, J. et al. Electronic structure calculations with GPAW: a real-space implementation of the projector augmented-wave method. J. Phys. Condens. Matter 22, 253202 (2010).10.1088/0953-8984/22/25/253202 ↗
55. Hjorth Larsen, A. et al. The atomic simulation environment—a Python library for working with atoms. J. Phys. Condens. Matter 29, 273002 (2017).10.1088/1361-648X/aa680e ↗
56. Perdew, J. P., Burke, K. & Ernzerhof, M. Generalized gradient approximation made simple. Phys. Rev. Lett. 77, 3865–3868 (1996).10.1103/PhysRevLett.77.3865 ↗