Application-driven design of non-aqueous electrolyte solutions through quantification of interfacial reactions in lithium metal batteries
Source abstract
Abstract
Unwanted side reactions occurring at electrode|electrolyte interfaces significantly impact the cycling life of lithium metal batteries. However, a comprehensive view that rationalizes these interfacial reactions and assesses them both qualitatively and quantitatively is not yet established. Here, by combining multiple analytical techniques, we systematically investigate the interfacial reactions in lithium metal batteries containing ether-based non-aqueous electrolyte solutions. We quantitatively monitor various nanoscale-driven processes such as the reduction and oxidation pathways of lithium salt and organic solvents, the formation of various solid-electrolyte interphase species, the gas generation within the cell and the cross-talk processes between the electrodes. We demonstrate that the consumption of lithium ions owing to the continuous decomposition of the lithium bis(fluorosulfonyl)imide salt, which dominates the interfacial reactions, results in ion depletion during the cell discharge and battery failure. On the basis of these findings, we propose an electrolyte formulation in which lithium bis(fluorosulfonyl)imide content is maximized without compromising dynamic viscosity and bulk ionic conductivity, aiming for long-cycling battery performance. Following this strategy, we assemble and test Li (20 μm thickness)||LiNi0.8Mn0.1Co0.1O2 (17.1 mg cm−2 of active material) single-layer stack pouch cells in lean electrolyte conditions (that is, 2.1 g Ah−1), which can effectively sustain 483 charge (0.2 C or 28 mA)/discharge (1 C or 140 mA) cycles at 25 °C demonstrating a discharge capacity retention of about 77%. Tailored non-aqueous electrolyte solutions are formulated using data obtained from extensive analytical measurements and analyses. These optimized electrolytes improve the cycling performance of single-layer stack lithium metal pouch cells, particularly in lean electrolyte conditions.
Source: openalex_inverted_index · Quality: baseline
Research context
OpenAlex topics: Advanced Battery Materials and Technologies · Advancements in Battery Materials · Advanced Battery Technologies Research
SciVX discovery tags are terminology-based. OpenAlex topics are source-provided classifications.
References (68)
Show source-provided references
1. Tarascon, J. M. & Armand, M. Issues and challenges facing rechargeable lithium batteries. Nature 414, 359–367 (2001).10.1038/35104644 ↗
2. 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 ↗
3. Albertus, P., Babinec, S., Litzelman, S. & Newman, A. Status and challenges in enabling the lithium metal electrode for high-energy and low-cost rechargeable batteries. Nat. Energy 3, 16–21 (2018).10.1038/s41560-017-0047-2 ↗
4. SES 50Ah Li-metal Cell Data Report (SES AI, 2022); https://cdn.prod.website-files.com/6704ef99f6a4ff8b5b7218b1/671b6665eee268960e2e8ec4_SES-50Ah-Li-Metal-Cell-Data-Report.pdf
5. Meng, Y. S. Sion Power Lithium Metal Battery Technology Assessment Report (Sion Power, 2022); https://sionpower.com/files/Shirley-Meng-Report-Sion-Power.pdf
6. Cuberg Lithium Metal Cell Technology (Cuberg, 2022); https://www.datocms-assets.com/38709/1658475133-cuberg-cell-validation-july-2022.pdf
7. Zhang, J.-G., Xu, W., Xiao, J., Cao, X. & Liu, J. Lithium metal anodes with nonaqueous electrolytes. Chem. Rev. 120, 13312–13348 (2020).10.1021/acs.chemrev.0c00275 ↗
8. Frith, J. T., Lacey, M. J. & Ulissi, U. A non-academic perspective on the future of lithium-based batteries. Nat. Commun. 14, 420 (2023).10.1038/s41467-023-35933-2 ↗
9. Qian, J. et al. High rate and stable cycling of lithium metal anode. Nat. Commun. 6, 6362 (2015).10.1038/ncomms7362 ↗
10. 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 ↗
11. Suo, L. et al. Fluorine-donating electrolytes enable highly reversible 5-V-class Li metal batteries. Proc. Natl Acad. Sci. USA 115, 1156–1161 (2018).10.1073/pnas.1712895115 ↗
12. Chen, Y. et al. Steric effect tuned ion solvation enabling stable cycling of high-voltage lithium metal battery. J. Am. Chem. Soc. 143, 18703–18713 (2021).10.1021/jacs.1c09006 ↗
13. Chen, S. et al. High-voltage lithium-metal batteries enabled by localized high-concentration electrolytes. Adv. Mater. 30, e1706102 (2018).10.1002/adma.201706102 ↗
14. 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 ↗
15. Ren, X. et al. Localized high-concentration sulfone electrolytes for high-efficiency lithium-metal batteries. Chem 4, 1877–1892 (2018).10.1016/j.chempr.2018.05.002 ↗
16. 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 ↗
17. 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 ↗
18. 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 ↗
19. Wang, H. et al. Dual-solvent Li-ion solvation enables high-performance Li-metal batteries. Adv. Mater. 33, e2008619 (2021).10.1002/adma.202008619 ↗
20. Xue, W. et al. FSI-inspired solvent and “full fluorosulfonyl” electrolyte for 4 V class lithium-metal batteries. Energy Environ. Sci. 13, 212–220 (2020).10.1039/C9EE02538C ↗
21. Huang, Y. et al. Eco-friendly electrolytes via a robust bond design for high-energy Li metal batteries. Energy Environ. Sci. 15, 4349–4361 (2022).10.1039/D2EE01756C ↗
22. Sun, C. et al. High-voltage Li metal batteries enabled by adsorption-defluorination mechanism. ACS Energy Lett. 8, 4119–4128 (2023).10.1021/acsenergylett.3c01383 ↗
23. Park, E. et al. Exploiting the steric effect and low dielectric constant of 1,2-dimethoxypropane for 4.3 V lithium metal batteries. ACS Energy Lett. 8, 179–188 (2023).10.1021/acsenergylett.2c02003 ↗
24. Liao, Y. et al. Eco-friendly tetrahydropyran enables weakly solvating “4S” electrolytes for lithium-metal batteries. Adv. Energy Mater. 13, 2301477 (2023).10.1002/aenm.202301477 ↗
25. Hou, W.-H. et al. Fluorinated carbamate-based electrolyte enables anion-dominated solid electrolyte interphase for highly reversible Li metal anode. ACS Nano 17, 17527–17535 (2023).10.1021/acsnano.3c06088 ↗
26. Fang, C. et al. Quantifying inactive lithium in lithium metal batteries. Nature 572, 511–515 (2019).10.1038/s41586-019-1481-z ↗
27. Wang, H. et al. Efficient lithium metal cycling over a wide range of pressures from an anion-derived solid-electrolyte interphase framework. ACS Energy Lett. 6, 816–825 (2021).10.1021/acsenergylett.0c02533 ↗
28. Harlow, J. E. et al. A wide range of testing results on an excellent lithium-ion cell chemistry to be used as benchmarks for new battery technologies. J. Electrochem. Soc. 166, A3031–A3044 (2019).10.1149/2.0981913jes ↗
29. Song, W. et al. A systematic study of electrolyte additive in single crystal and bimodal LiNi0.8Mn0.1Co0.1O2/graphite pouch cells. J. Electrochem. Soc. 168, 090503 (2021).10.1149/1945-7111/ac1e55 ↗
30. Xu, K. Electrolytes and interphases in Li-ion batteries and beyond. Chem. Rev. 114, 11503–11618 (2014).10.1021/cr500003w ↗
31. Wang, H. et al. Rate-dependent failure mechanisms and mitigating strategies of anode-free lithium metal batteries. ACS Appl. Mater. Interfaces 15, 12967–12975 (2023).10.1021/acsami.2c20422 ↗
32. Kim, H.-T. et al. Borate-pyran lean electrolyte-based Li-metal batteries with minimal Li corrosion. Nat. Energy 9, 57–69 (2024).
33. Xie, J. et al. Fluorobenzene-based diluted highly concentrated carbonate electrolyte for practical high-voltage lithium metal batteries. J. Power Sources 506, 230086 (2021).10.1016/j.jpowsour.2021.230086 ↗
34. Zhou, M.-Y. et al. Quantifying the apparent electron transfer number of electrolyte decomposition reactions in anode-free batteries. Joule 6, 2122–2137 (2022).10.1016/j.joule.2022.07.003 ↗
35. Ding, J.-F. et al. Non-solvating and low-dielectricity cosolvent for anion-derived solid electrolyte interphases in lithium metal batteries. Angew. Chem. Int. Ed. 60, 11442–11447 (2021).10.1002/anie.202101627 ↗
36. Niu, C. et al. High-energy lithium metal pouch cells with limited anode swelling and long stable cycles. Nat. Energy 4, 551–559 (2019).10.1038/s41560-019-0390-6 ↗
37. Chen, S. et al. High-voltage lithium-metal batteries enabled by localized high-concentration electrolytes. Adv. Mater. 30, 1706102 (2018).10.1002/adma.201706102 ↗
38. Hai, F. et al. A low-cost, fluorine-free localized highly concentrated electrolyte toward ultra-high loading lithium metal batteries. Adv. Energy Mater. 14, 2304253 (2024).10.1002/aenm.202304253 ↗
39. Haynes, W. M. CRC Handbook of Chemistry and Physics 94th edn (CRC, 2013).10.1201/b17118 ↗
40. Ko, S. et al. Electrode potential influences the reversibility of lithium-metal anodes. Nat. Energy 7, 1217–1224 (2022).10.1038/s41560-022-01144-0 ↗
41. Xie, J. et al. Engineering stable interfaces for three-dimensional lithium metal anodes. Sci. Adv. 4, eaat5168 (2018).10.1126/sciadv.aat5168 ↗
42. Zhang, H. et al. Titration mass spectroscopy (TMS): a quantitative analytical technology for rechargeable batteries. Nano Lett. 22, 9972–9981 (2022).10.1021/acs.nanolett.2c03535 ↗
43. Aiken, C. P. et al. An apparatus for the study of in situ gas evolution in Li-ion pouch cells. J. Electrochem. Soc. 161, A1548 (2014).10.1149/2.0151410jes ↗
44. Kresse, G. & Furthmüller, J. Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set. Comput. Mater. Sci. 6, 15–50 (1996).10.1016/0927-0256(96)00008-0 ↗
45. Kresse, G. & Furthmüller, J. Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set. Phys. Rev. B 54, 11169–11186 (1996).10.1103/PhysRevB.54.11169 ↗
46. Perdew, J. P., Burke, K. & Ernzerhof, M. Generalized gradient approximation made simple. Phys. Rev. Lett. 77, 3865–3868 (1996).10.1103/PhysRevLett.77.3865 ↗
47. Grimme, S., Antony, J., Ehrlich, S. & Krieg, H. A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu. J. Chem. Phys. 132, 154014 (2010).10.1063/1.3382344 ↗
48. Henkelman, G., Uberuaga, B. P. & Jónsson, H. A climbing image nudged elastic band method for finding saddle points and minimum energy paths. J. Chem. Phys. 113, 9901–9904 (2000).10.1063/1.1329672 ↗
49. Zhang, H., Qiu, L. & Hu, D. Finite-temperature dimer method for finding saddle points on free energy surfaces. J. Comput. Chem. 40, 1701–1706 (2019).10.1002/jcc.25824 ↗
50. Becke, A.-D. Density-functional thermochemistry. III. The role of exact exchange. J. Chem. Phys. 98, 5648–5652 (1993).10.1063/1.464913 ↗
51. Frisch, M. J. et al. Gaussian 09, Revision B. 01 (Gaussian Inc., 2009).
52. Marenich, A. V., Cramer, C. J. & Truhlar, D. G. Universal solvation model based on solute electron density and on a continuum model of the solvent defined by the bulk dielectric constant and atomic surface tensions. J. Phys. Chem. B 113, 6378–6396 (2009).10.1021/jp810292n ↗
53. Klamt, A. Conductor-like screening model for real solvents: a new approach to the quantitative calculation of solvation phenomena. J. Phys. Chem. 99, 2224–2235 (1995).10.1021/j100007a062 ↗
54. Klamt, A. & Eckert, F. COSMO-RS: a novel and efficient method for the a priori prediction of thermophysical data of liquids. Fluid Phase Equilib. 172, 43–72 (2000).10.1016/S0378-3812(00)00357-5 ↗
55. Ahlrichs, R., Bär, M., Häser, M., Horn, H. & Kölmel, C. Electronic structure calculations on workstation computers: the program system Turbomole. Chem. Phys. Lett. 162, 165–169 (1989).10.1016/0009-2614(89)85118-8 ↗
56. Eckert, F. & Klamt, A. C. COSMOtherm Version C3.0, Release 12.01 (COSMOlogic GmbH & Co. KG, 2013).
57. Hadj-Kali, M. K. et al. Screening of ionic liquids for gas separation using COSMO-RS and comparison between performances of ionic liquids and aqueous alkanolamine solutions. Chem. Eng Commun. 207, 1264–1277 (2020).10.1080/00986445.2019.1680363 ↗
58. Plimpton, S. Fast parallel algorithms for short-range molecular dynamics. J. Comput. Phys. 117, 1–19 (1995).10.1006/jcph.1995.1039 ↗
59. Stukowski, A. Visualization and analysis of atomistic simulation data with OVITO—the Open Visualization Tool. Model. Simul. Mater. Sci. Eng 18, 015012 (2010).10.1088/0965-0393/18/1/015012 ↗
60. 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 ↗
61. Dodda, L. S., 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 ↗
62. Nichol, A. & Ackland, G. J. Property trends in simple metals: an empirical potential approach. Phys. Rev. B 93, 184101 (2016).10.1103/PhysRevB.93.184101 ↗
63. Hoover, W. G. Canonical dynamics: equilibrium phase-space distributions. Phys. Rev. A 31, 1695–1697 (1985).10.1103/PhysRevA.31.1695 ↗
64. Siepmann, J. I. & Sprik, M. Influence of surface topology and electrostatic potential on water/electrode systems. J. Chem. Phys. 102, 511–524 (1995).10.1063/1.469429 ↗
65. Reed, S. K., Lanning, O. J. & Madden, P. A. Electrochemical interface between an ionic liquid and a model metallic electrode. J. Chem. Phys. 126, 084704 (2007).10.1063/1.2464084 ↗
66. Wang, Z., Yang, Y., Olmsted, D. L., Asta, M. & Laird, B. B. Evaluation of constant potential method in simulating electric double-layer capacitors. J. Chem. Phys. 141, 184102 (2014).10.1063/1.4899176 ↗
67. Ahrens-Iwers, L. J. V., Janssen, M., Tee, S. R. & Meißner, R. H. ELECTRODE: an electrochemistry package for atomistic simulations. J. Chem. Phys. 157, 084801 (2022).10.1063/5.0099239 ↗
68. Thorat, I. V. et al. Quantifying tortuosity in porous Li-ion battery materials. J. Power Sources 188, 592–600 (2009).10.1016/j.jpowsour.2008.12.032 ↗