Universal chemomechanical design rules for solid-ion conductors to prevent dendrite formation in lithium metal batteries
Source abstract
Abstract
Dendrite formation during electrodeposition while charging lithium metal batteries compromises their safety. Although high-shear-modulus (Gs) solid-ion conductors (SICs) have been prioritized to resolve the pressure-driven instabilities that lead to dendrite propagation and cell shorting, it is unclear whether these or alternatives are needed to guide uniform lithium electrodeposition, which is intrinsically density-driven. Here, we show that SICs can be designed within a universal chemomechanical paradigm to access either pressure-driven dendrite-blocking or density-driven dendrite-suppressing properties, but not both. This dichotomy reflects the competing influence of the SIC's mechanical properties and the partial molar volume of Li+ ([Formula: see text]) relative to those of the lithium anode (GLi and VLi) on plating outcomes. Within this paradigm, we explore SICs in a previously unrecognized dendrite-suppressing regime that are concomitantly 'soft', as is typical of polymer electrolytes, but feature an atypically low [Formula: see text] that is more reminiscent of 'hard' ceramics. Li plating (1 mA cm-2; T = 20 °C) mediated by these SICs is uniform, as revealed using synchrotron hard X-ray microtomography. As a result, cell cycle life is extended, even when assembled with thin Li anodes (~30 µm) and either high-voltage NMC-622 cathodes (1.44 mAh cm-2) or high-capacity sulfur cathodes (3.02 mAh cm-2).
Source: europepmc · Quality: candidate unverified · Source record ↗
Research context
OpenAlex topics: Advancements in Battery Materials · Advanced Battery Materials and Technologies · Advanced Battery Technologies Research
SciVX discovery tags are terminology-based. OpenAlex topics are source-provided classifications.
References (50)
Show source-provided references
1. Xu, W. et al. Lithium metal anodes for rechargeable batteries. Energy Environ. Sci. 7, 513–537 (2014).10.1039/C3EE40795K ↗
2. Tikekar, M. D., Choudhury, S., Tu, Z. & Archer, L. A. Design principles for electrolytes and interfaces for stable lithium-metal batteries. Nat. Energy 1, 16114 (2016).10.1038/nenergy.2016.114 ↗
3. 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 ↗
4. Cheng, X.-B., Zhang, R., Zhao, C.-Z. & Zhang, Q. Toward safe lithium metal anode in rechargeable batteries: a review. Chem. Rev. 117, 10403–10473 (2017).10.1021/acs.chemrev.7b00115 ↗
5. Manthiram, A., Yu, X. & Wang, S. Lithium battery chemistries enabled by solid-state electrolytes. Nat. Rev. Mater. 2, 16103 (2017).10.1038/natrevmats.2016.103 ↗
6. 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 ↗
7. Monroe, C. & Newman, J. Dendrite growth in lithium/polymer systems. J. Electrochem. Soc. 150, A1377–A1384 (2003).10.1149/1.1606686 ↗
8. Monroe, C. & Newman, J. The effect of interfacial deformation on electrodeposition kinetics. J. Electrochem. Soc. 151, A880–A886 (2004).10.1149/1.1710893 ↗
9. Ahmad, Z. & Viswanathan, V. Stability of electrodeposition at solid–solid interfaces and implications for metal anodes. Phys. Rev. Lett. 119, 056003 (2017).10.1103/PhysRevLett.119.056003 ↗
10. 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 ↗
11. Barai, P., Higa, K. & Srinivasan, V. Lithium dendrite growth mechanisms in polymer electrolytes and prevention strategies. Phys. Chem. Chem. Phys. 19, 20493–20505 (2017).10.1039/C7CP03304D ↗
12. Singh, M. et al. Effect of molecular weight on the mechanical and electrical properties of block copolymer electrolytes. Macromolecules 40, 4578–4585 (2007).10.1021/ma0629541 ↗
13. Bouchet, R. et al. Single-ion BAB triblock copolymers as highly efficient electrolytes for lithium-metal batteries. Nat. Mater. 12, 452–457 (2013).10.1038/nmat3602 ↗
14. Khurana, R., Schaefer, J. L., Archer, L. A. & Coates, G. W. Suppression of lithium dendrite growth using cross-linked polyethylene/poly(ethylene oxide) electrolytes: a new approach for practical lithium-metal polymer batteries. J. Am. Chem. Soc. 136, 7395–7402 (2014).10.1021/ja502133j ↗
15. Harry, K. J., Hallinan, D. T., Parkinson, D. Y., MacDowell, A. A. & Balsara, N. P. Detection of subsurface structures underneath dendrites formed on cycled lithium metal electrodes. Nat. Mater. 13, 69–73 (2014).10.1038/nmat3793 ↗
16. Porz, L. et al. Mechanism of lithium metal penetration through inorganic solid electrolytes. Adv. Energy Mater. 7, 1701003 (2017).10.1002/aenm.201701003 ↗
17. Cheng, E. J., Sharafi, A. & Sakamoto, J. Intergranular Li metal propagation through polycrystalline Li6.25Al0.25La3Zr2O12 ceramic electrolyte. Electrochim. Acta 223, 85–91 (2017).10.1016/j.electacta.2016.12.018 ↗
18. Maier, J. Nanoionics: ion transport and electrochemical storage in confined systems. Nat. Mater. 4, 805–815 (2005).10.1038/nmat1513 ↗
19. Croce, F., Appetecchi, G. B., Persi, L. & Scrosati, B. Nanocomposite polymer electrolytes for lithium batteries. Nature 394, 456–458 (1998).10.1038/28818 ↗
20. Liang, C. C. Conduction characteristics of the lithium iodide–aluminum oxide solid electrolytes. J. Electrochem. Soc. 120, 1289–1292 (1973).10.1149/1.2403248 ↗
21. Weinstein, L., Yourey, W., Gural, J. & Amatucci, G. Electrochemical impedance spectroscopy of electrochemically self-assembled lithium-iodine batteries. J. Electrochem. Soc. 155, A590–A598 (2008).10.1149/1.2940323 ↗
22. 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 ↗
23. Fan, L., Zhuang, H. L., Gao, L., Lu, Y. & Archer, L. A. Regulating Li deposition at artificial solid electrolyte interphases. J. Mater. Chem. A 5, 3483–3492 (2017).10.1039/C6TA10204B ↗
24. Li, H., Richter, G. & Maier, J. Reversible formation and decomposition of LiF clusters using transition metal fluorides as precursors and their application in rechargeable Li batteries. Adv. Mater. 15, 736–739 (2003).10.1002/adma.200304574 ↗
25. Budd, P. M. et al. Solution‐processed, organophilic membrane derived from a polymer of intrinsic microporosity. Adv. Mater. 16, 456–459 (2004).10.1002/adma.200306053 ↗
26. Li, C. et al. Engineered transport in microporous materials and membranes for clean energy technologies. Adv. Mater. 30, 1704953 (2018).10.1002/adma.201704953 ↗
27. Myung, S.-T. et al. Nickel-rich layered cathode materials for automotive lithium-ion batteries: achievements and perspectives. ACS Energy Lett. 2, 196–223 (2017).10.1021/acsenergylett.6b00594 ↗
28. Newman, J. & Chapman, T. W. Restricted diffusion in binary solutions. AlChE J. 19, 343–348 (1973).10.1002/aic.690190220 ↗
29. Bader, R. F. W. Atoms in Molecules: A Quantum Theory (Oxford Univ. Press, 1990).10.1093/oso/9780198551683.001.0001 ↗
30. Bader, R. F. W., Carroll, M. T., Cheeseman, J. R. & Chang, C. Properties of atoms in molecules: atomic volumes. J. Am. Chem. Soc. 109, 7968–7979 (1987).10.1021/ja00260a006 ↗
31. Ozhabes, Y., Gunceler, D. & Arias, T. A. Stability and surface diffusion at lithium–electrolyte interphases with connections to dendrite suppression. Preprint at https://arxiv.org/pdf/1504.05799.pdf (2015).
32. Perdew, J. P., Burke, K. & Ernzerhof, M. Generalized gradient approximation made simple. Phys. Rev. Lett. 77, 3865–3868 (1996).10.1103/PhysRevLett.77.3865 ↗
33. Sharada, S. M., Bligaard, T., Luntz, A. C., Kroes, G.-J. & Nørskov, J. K. SBH10: a benchmark database of barrier heights on transition metal surfaces. J. Phys. Chem. C 121, 19807–19815 (2017).10.1021/acs.jpcc.7b05677 ↗
34. Wellendorff, J. et al. Density functionals for surface science: exchange-correlation model development with Bayesian error estimation. Phys. Rev. B 85, 235149 (2012).10.1103/PhysRevB.85.235149 ↗
35. Berne, B. J., Cicotti, G. & Coker, D. F. Classical and Quantum Dynamics in Condensed Phase Simulations (World Scientific, 1998).
36. Bruce, P. G., Evans, J. & Vincent, C. A. Conductivity and transference number measurements on polymer electrolytes. Solid State Ionics 28–30, 918–922 (1988).10.1016/0167-2738(88)90304-9 ↗
37. Suo, L., Hu, Y.-S., Li, H., Armand, M. & Chen, L. A new class of solvent-in-salt electrolyte for high-energy rechargeable metallic lithium batteries. Nat. Commun. 4, 1481 (2013).10.1038/ncomms2513 ↗
38. Orilall, M. C. & Wiesner, U. Block copolymer based composition and morphology control in nanostructured hybrid materials for energy conversion and storage: solar cells, batteries and fuel cells. Chem. Soc. Rev. 40, 520–535 (2011).10.1039/C0CS00034E ↗
39. Peng, Q., Tseng, Y.-C., Darling, S. B. & Elam, J. W. Nanoscopic patterned materials with tunable dimensions via atomic layer deposition on block copolymers. Adv. Mater. 22, 5129–5133 (2010).10.1002/adma.201002465 ↗
40. Llordes, A. et al. Linear topology in amorphous metal oxide electrochromic networks obtained via low-temperature solution processing. Nat. Mater. 15, 1267–1273 (2016).10.1038/nmat4734 ↗
41. Blochl, P. E. Projector augmented-wave method. Phys. Rev. B 50, 17953–17979 (1994).10.1103/PhysRevB.50.17953 ↗
42. Kresse, G. & Joubert, D. From ultrasoft pseudopotentials to the projector augmented-wave method. Phys. Rev. B 59, 1758–1775 (1999).10.1103/PhysRevB.59.1758 ↗
43. 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 ↗
44. 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 ↗
45. Monkhorst, H. J. & Pack, J. D. Special points for Brillouin-zone integrations. Phys. Rev. B 13, 5188–5192 (1976).10.1103/PhysRevB.13.5188 ↗
46. Larsen, A. H. 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 ↗
47. Li, C. et al. A polysulfide-blocking microporous polymer membrane tailored for hybrid Li–sulfur flow batteries. Nano Lett. 15, 5724–5729 (2015).10.1021/acs.nanolett.5b02078 ↗
48. Ward, A. L. et al. Materials genomics screens for adaptive ion transport behavior by redox-switchable microporous polymer membranes in lithium–sulfur batteries. ACS Cent. Sci. 3, 399–406 (2017).10.1021/acscentsci.7b00012 ↗
49. Markevich, E., Salitra, G. & Aurbach, D. Fluoroethylene carbonates an important component for the formation of an effective solid electrolyte interphase on anodes and cathodes for advanced Li-ion batteries. ACS Energy Lett. 2, 1337–1345 (2017).10.1021/acsenergylett.7b00163 ↗
50. Aurbach, D. et al. On the use of vinylene carbonate (VC) as an additive to electrolyte solutions for Li-ion batteries. Electrochim. Acta 47, 1423–1439 (2002).10.1016/S0013-4686(01)00858-1 ↗