Extreme lithium-metal cycling enabled by a mixed ion- and electron-conducting garnet three-dimensional architecture
Source abstract
Abstract
The development of solid-state Li-metal batteries has been limited by the Li-metal plating and stripping rates and the tendency for dendrite shorts to form at commercially relevant current densities. To address this, we developed a single-phase mixed ion- and electron-conducting (MIEC) garnet with comparable Li-ion and electronic conductivities. We demonstrate that in a trilayer architecture with a porous MIEC framework supporting a thin, dense, garnet electrolyte, the critical current density can be increased to a previously unheard of 100 mA cm-2, with no dendrite-shorting. Additionally, we demonstrate that symmetric Li cells can be continuously cycled at a current density of 60 mA cm-2 with a maximum per-cycle Li plating and stripping capacity of 30 mAh cm-2, which is 6× the capacity of state-of-the-art cathodes. Moreover, a cumulative Li plating capacity of 18.5 Ah cm-2 was achieved with the MIEC/electrolyte/MIEC architecture, which if paired with a state-of-the-art cathode areal capacity of 5 mAh cm-2 would yield a projected 3,700 cycles, significantly surpassing requirements for commercial electric vehicle battery lifetimes.
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 (46)
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. Lee, H. G., Kim, S. Y. & Lee, J. S. Dynamic observation of dendrite growth on lithium metal anode during battery charging/discharging cycles. npj Comput. Mater. 8, 1–13 (2022).10.1038/s41524-021-00695-2 ↗
4. Jana, A. & García, R. E. Lithium dendrite growth mechanisms in liquid electrolytes. Nano Energy 41, 552–565 (2017).10.1016/j.nanoen.2017.08.056 ↗
5. Qian, J. et al. High rate and stable cycling of lithium metal anode. Nat. Commun. 6, 6362 (2015).10.1038/ncomms7362 ↗
6. Subramanian, K. et al. A brief review of recent advances in garnet structured solid electrolyte based lithium metal batteries. J. Energy Storage 33, 102157 (2021).10.1016/j.est.2020.102157 ↗
7. Wang, C. et al. Garnet-type solid-state electrolytes: materials, interfaces, and batteries. Chem. Rev. 120, 4257–4300 (2020).10.1021/acs.chemrev.9b00427 ↗
8. Ramakumar, S., Deviannapoorani, C., Dhivya, L., Shankar, L. S. & Murugan, R. Lithium garnets: synthesis, structure, Li+ conductivity, Li+ dynamics and applications. Prog. Mater. Sci. 88, 325–411 (2017).10.1016/j.pmatsci.2017.04.007 ↗
9. Murugan, R., Thangadurai, V. & Weppner, W. Fast lithium ion conduction in garnet-type Li7La3Zr2O12. Angew. Chem. Int. Ed. 46, 7778–7781 (2007).10.1002/anie.200701144 ↗
10. 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 (2017).10.1038/s41560-017-0047-2 ↗
11. Huo, H. et al. In-situ formed Li2CO3-free garnet/Li interface by rapid acid treatment for dendrite-free solid-state batteries. Nano Energy 61, 119–125 (2019).10.1016/j.nanoen.2019.04.058 ↗
12. Fu, K. et al. Three-dimensional bilayer garnet solid electrolyte based high energy density lithium metal–sulfur batteries. Energy Environ. Sci. 10, 1568–1575 (2017).10.1039/C7EE01004D ↗
13. Lee, S. et al. Design of a lithiophilic and electron-blocking interlayer for dendrite-free lithium-metal solid-state batteries. Sci. Adv. 8, 153 (2022).
14. Samson, A. J., Hofstetter, K., Bag, S. & Thangadurai, V. A bird’s-eye view of Li-stuffed garnet-type Li7La3Zr2O12 ceramic electrolytes for advanced all-solid-state Li batteries. Energy Environ. Sci. 12, 2957–2975 (2019).10.1039/C9EE01548E ↗
15. Alexander, G. V., Indu, M. S. & Murugan, R. Review on the critical issues for the realization of all-solid-state lithium metal batteries with garnet electrolyte: interfacial chemistry, dendrite growth, and critical current densities. Ionics 27, 4105–4126 (2021).10.1007/s11581-021-04190-y ↗
16. Basappa, R. H., Ito, T. & Yamada, H. Contact between garnet-type solid electrolyte and lithium metal anode: influence on charge transfer resistance and short circuit prevention. J. Electrochem. Soc. 164, A666–A671 (2017).10.1149/2.0841704jes ↗
17. Han, X. et al. Negating interfacial impedance in garnet-based solid-state Li metal batteries. Nat. Mater. 16, 572–579 (2016).10.1038/nmat4821 ↗
18. Alexander, G. V. et al. Electrodes-electrolyte interfacial engineering for realizing room temperature lithium metal battery based on garnet structured solid fast Li+ conductors. J. Power Sources 396, 764–773 (2018).10.1016/j.jpowsour.2018.06.096 ↗
19. Alexander, G. V., Indu, M. S., Kamakshy, S. & Murugan, R. Development of stable and conductive interface between garnet structured solid electrolyte and lithium metal anode for high performance solid-state battery. Electrochim. Acta 332, 135511 (2020).10.1016/j.electacta.2019.135511 ↗
20. Feng, W., Dong, X., Li, P., Wang, Y. & Xia, Y. Interfacial modification of Li/Garnet electrolyte by a lithiophilic and breathing interlayer. J. Power Sources 419, 91–98 (2019).10.1016/j.jpowsour.2019.02.066 ↗
21. Lou, J. et al. Achieving efficient and stable interface between metallic lithium and garnet-type solid electrolyte through a thin indium tin oxide interlayer. J. Power Sources 448, 227440 (2020).10.1016/j.jpowsour.2019.227440 ↗
22. Luo, W. et al. Reducing interfacial resistance between garnet-structured solid-state electrolyte and Li-metal anode by a germanium layer. Adv. Mater. 29, 1606042 (2017).10.1002/adma.201606042 ↗
23. Li, Y. et al. Garnet electrolyte with an ultralow interfacial resistance for Li-metal batteries. J. Am. Chem. Soc. 140, 6448–6455 (2018).10.1021/jacs.8b03106 ↗
24. Alexander, G. V., Sreejith, O. V., Indu, M. S. & Murugan, R. Interface-compatible and high-cyclability lithiophilic lithium-zinc alloy anodes for garnet-structured solid electrolytes. ACS Appl. Energy Mater. 3, 9010–9017 (2020).10.1021/acsaem.0c01430 ↗
25. Huang, Y. et al. Graphitic carbon nitride (g-C3N4): an interface enabler for solid-state lithium metal batteries. Angew. Chem. Int. Ed. 59, 3699–3704 (2020).10.1002/anie.201914417 ↗
26. Zhang, X. et al. Long cycling life solid-state Li metal batteries with stress self-adapted Li/garnet interface. Nano Lett. 20, 2871–2878 (2020).10.1021/acs.nanolett.0c00693 ↗
27. Fu, K. K. et al. Toward garnet electrolyte–based Li metal batteries: an ultrathin, highly effective, artificial solid-state electrolyte/metallic Li interface. Sci. Adv. 3, e1601659 (2017).10.1126/sciadv.1601659 ↗
28. Cui, J. et al. Melt-quenching of artificial metallic interlayer enables a resistance-free garnet/lithium interface for all-solid-state lithium-metal batteries. Energy Storage Mater. 53, 899–908(2022).10.1016/j.ensm.2022.10.002 ↗
29. Wang, C. et al. Conformal, nanoscale ZnO surface modification of garnet-based solid-state electrolyte for lithium metal anodes. Nano Lett. 17, 565–571 (2017).10.1021/acs.nanolett.6b04695 ↗
30. Xu, S. et al. Three-dimensional, solid-state mixed electron–ion conductive framework for lithium metal anode. Nano Lett. 18, 3926–3933 (2018).10.1021/acs.nanolett.8b01295 ↗
31. Liu, B. et al. 3D lithium metal anodes hosted in asymmetric garnet frameworks toward high energy density batteries. Energy Storage Mater. 14, 376–382 (2018).10.1016/j.ensm.2018.04.015 ↗
32. Xu, S. et al. All-in-one lithium-sulfur battery enabled by a porous-dense-porous garnet architecture. Energy Storage Mater. 15, 458–464 (2018).10.1016/j.ensm.2018.08.009 ↗
33. Hitz, G. T. et al. High-rate lithium cycling in a scalable trilayer Li-garnet-electrolyte architecture. Mater. Today 22, 50–57 (2019).10.1016/j.mattod.2018.04.004 ↗
34. Yang, C. et al. Continuous plating/stripping behavior of solid-state lithium metal anode in a 3D ion-conductive framework. Proc. Natl Acad. Sci. USA 115, 3770–3775 (2018).10.1073/pnas.1719758115 ↗
35. Xie, H. et al. Amorphous-carbon-coated 3D solid electrolyte for an electro-chemomechanically stable lithium metal anode in solid-state batteries. Nano Lett. 21, 6163–6170 (2021).10.1021/acs.nanolett.1c01748 ↗
36. Xu, S. et al. Three-dimensional, solid-state mixed electron-ion conductive framework for lithium metal anode. Nano Lett. 18, 3926–3933 (2018).10.1021/acs.nanolett.8b01295 ↗
37. Chen, Y. et al. Li metal deposition and stripping in a solid-state battery via Coble creep. Nature 578, 251–255 (2020).10.1038/s41586-020-1972-y ↗
38. Gao, J. et al. Rational design of mixed electronic-ionic conducting Ti-doping Li7La3Zr2O12 for lithium dendrites suppression. Adv. Funct. Mater. 31, 2001918 (2021).10.1002/adfm.202001918 ↗
39. Cheng, X., Huang, J., Qiang, W. & Huang, B. Synthesis of mixed ionic and electronic conducting garnet with doping of transition elements (Fe, Co, Ni). Ceram. Int. 46, 3731–3737 (2020).10.1016/j.ceramint.2019.10.094 ↗
40. Samson, A. J., Hofstetter, K., Wachsman, E. & Thangadurai, V. Towards mixed ionic and electronic conducting Li-stuffed garnets. J. Electrochem. Soc. 165, A2303–A2311 (2018).10.1149/2.1001810jes ↗
41. Thangadurai, V. & Weppner, W. Li6ALa2Nb2O12 (A=Ca, Sr, Ba): a new class of fast lithium ion conductors with garnet-like structure. J. Am. Ceram. Soc. 88, 411–418 (2005).10.1111/j.1551-2916.2005.00060.x ↗
42. Stockham, M. P., Dong, B., Ding, Y., Li, Y. & Slater, P. R. Evaluation of the effect of site substitution of Pr doping in the lithium garnet system Li5La3Nb2O12. Dalton Trans. 49, 10349–10359 (2020).10.1039/D0DT01497D ↗
43. Wagner, R. et al. Crystal structure of garnet-related Li-ion conductor Li7−3xGaxLa3Zr2O12: fast Li-ion conduction caused by a different cubic modification? Chem. Mater. 28, 1861–1871 (2016).10.1021/acs.chemmater.6b00038 ↗
44. Flatscher, F., Philipp, M., Ganschow, S., Wilkening, H. M. R. & Rettenwander, D. The natural critical current density limit for Li7La3Zr2O12 garnets. J. Mater. Chem. A 8, 15782–15788 (2020).10.1039/C9TA14177D ↗
45. Duan, J. et al. Lithium–graphite paste: an interface compatible anode for solid-state batteries. Adv. Mater. 31, 1807243 (2019).10.1002/adma.201807243 ↗
46. Raj, V. et al. Direct correlation between void formation and lithium dendrite growth in solid-state electrolytes with interlayers. Nat. Mater. 21, 1050–1056 (2022).10.1038/s41563-022-01264-8 ↗