Overcoming the conversion reaction limitation at three-phase interfaces using mixed conductors towards energy-dense solid-state Li–S batteries
Source abstract
Abstract
Lithium-sulfur (Li-S) all-solid-state batteries (ASSBs) hold great promise for next-generation safe, durable and energy-dense battery technology. However, solid-state sulfur conversion reactions are kinetically sluggish and primarily constrained to the restricted three-phase boundary area of sulfur, carbon and solid electrolytes, making it challenging to achieve high sulfur utilization. Here we develop and implement mixed ionic-electronic conductors (MIECs) in sulfur cathodes to replace conventional solid electrolytes and invoke conversion reactions at sulfur-MIEC interfaces in addition to traditional three-phase boundaries. Microscopic and tomographic analyses reveal the emergence of mixed-conducting domains embedded in sulfur at sulfur-MIEC boundaries, helping promote the thorough conversion of active sulfur into Li2S. Consequently, substantially improved active sulfur ratios (up to 87.3%) and conversion degrees (>94%) are achieved in Li-S ASSBs with high discharge capacity (>1,450 mAh g-1) and long cycle life (>1,000 cycles). The strategy is also applied to enhance the active material utilization of other conversion cathodes.
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 (55)
Show source-provided references
1. 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 ↗
2. Tan, D. H. S. et al. Carbon-free high-loading silicon anodes enabled by sulfide solid electrolytes. Science 373, 1494–1499 (2021).10.1126/science.abg7217 ↗
3. Xiao, Y. et al. Electrolyte melt infiltration for scalable manufacturing of inorganic all-solid-state lithium-ion batteries. Nat. Mater. 20, 984–990 (2021).10.1038/s41563-021-00943-2 ↗
4. Kamaya, N. et al. A lithium superionic conductor. Nat. Mater. 10, 682–686 (2011).10.1038/nmat3066 ↗
5. Alexander, G. V., Shi, C., O’Neill, J. & Wachsman, E. D. Extreme lithium-metal cycling enabled by a mixed ion- and electron-conducting garnet three-dimensional architecture. Nat. Mater. 22, 1136–1143 (2023).10.1038/s41563-023-01627-9 ↗
6. Jun, K. et al. Lithium superionic conductors with corner-sharing frameworks. Nat. Mater. 21, 924–931 (2022).10.1038/s41563-022-01222-4 ↗
7. Ji, X., Lee, K. T. & Nazar, L. F. A highly ordered nanostructured carbon–sulphur cathode for lithium–sulphur batteries. Nat. Mater. 8, 500–506 (2009).10.1038/nmat2460 ↗
8. Zhao, C. et al. A high-energy and long-cycling lithium–sulfur pouch cell via a macroporous catalytic cathode with double-end binding sites. Nat. Nanotechnol. 16, 166–173 (2021).10.1038/s41565-020-00797-w ↗
9. Li, Z. et al. Lithiated metallic molybdenum disulfide nanosheets for high-performance lithium–sulfur batteries. Nat. Energy 8, 84–93 (2023).10.1038/s41560-022-01175-7 ↗
10. Huang, Q. et al. Cycle stability of conversion-type iron fluoride lithium battery cathode at elevated temperatures in polymer electrolyte composites. Nat. Mater. 18, 1343–1349 (2019).10.1038/s41563-019-0472-7 ↗
11. Hua, X. et al. Revisiting metal fluorides as lithium-ion battery cathodes. Nat. Mater. 20, 841–850 (2021).10.1038/s41563-020-00893-1 ↗
12. Chung, W. J. et al. The use of elemental sulfur as an alternative feedstock for polymeric materials. Nat. Chem. 5, 518–524 (2013).10.1038/nchem.1624 ↗
13. Muench, S. et al. Polymer-based organic batteries. Chem. Rev. 116, 9438–9484 (2016).10.1021/acs.chemrev.6b00070 ↗
14. Wu, F. & Yushin, G. Conversion cathodes for rechargeable lithium and lithium-ion batteries. Energy Environ. Sci. 10, 435–459 (2017).10.1039/C6EE02326F ↗
15. Janek, J. & Zeier, W. G. Challenges in speeding up solid-state battery development. Nat. Energy 8, 230–240 (2023).10.1038/s41560-023-01208-9 ↗
16. Zhang, J. et al. Microstructure engineering of solid-state composite cathode via solvent-assisted processing. Joule 5, 1845–1859 (2021).10.1016/j.joule.2021.05.017 ↗
17. Manthiram, A., Fu, Y., Chung, S.-H., Zu, C. & Su, Y.-S. Rechargeable lithium–sulfur batteries. Chem. Rev. 114, 11751–11787 (2014).10.1021/cr500062v ↗
18. Bradbury, R. et al. Visualizing reaction fronts and transport limitations in solid-state Li–S batteries via operando neutron imaging. Adv. Energy Mater. 13, 2203426 (2023).10.1002/aenm.202203426 ↗
19. Ohno, S., Rosenbach, C., Dewald, G. F., Janek, J. & Zeier, W. G. Linking solid electrolyte degradation to charge carrier transport in the thiophosphate-based composite cathode toward solid-state lithium-sulfur batteries. Adv. Funct. Mater. 31, 2010620 (2021).10.1002/adfm.202010620 ↗
20. Zhou, J. et al. Healable and conductive sulfur iodide for solid-state Li–S batteries. Nature 627, 301–305 (2024).10.1038/s41586-024-07101-z ↗
21. Han, F. et al. High-performance all-solid-state lithium–sulfur battery enabled by a mixed-conductive Li2S nanocomposite. Nano Lett. 16, 4521–4527 (2016).10.1021/acs.nanolett.6b01754 ↗
22. Yao, X. et al. High-performance all-solid-state lithium–sulfur batteries enabled by amorphous sulfur-coated reduced graphene oxide cathodes. Adv. Energy Mater. 7, 1602923 (2017).10.1002/aenm.201602923 ↗
23. Zhang, Y. et al. High-performance all-solid-state lithium–sulfur batteries with sulfur/carbon nano-hybrids in a composite cathode. J. Mater. Chem. A 6, 23345–23356 (2018).10.1039/C8TA08420C ↗
24. Hou, L.-P. et al. Improved interfacial electronic contacts powering high sulfur utilization in all-solid-state lithium–sulfur batteries. Energy Storage Mater. 25, 436–442 (2020).10.1016/j.ensm.2019.09.037 ↗
25. Sakuda, A., Sato, Y., Hayashi, A. & Tatsumisago, M. Sulfur-based composite electrode with interconnected mesoporous carbon for all-solid-state lithium–sulfur batteries. Energy Technol. 7, 1900077 (2019).10.1002/ente.201900077 ↗
26. Shi, X. et al. Fast Li-ion conductor of Li3HoBr6 for stable all-solid-state lithium–sulfur battery. Nano Lett. 21, 9325–9331 (2021).10.1021/acs.nanolett.1c03573 ↗
27. Wang, D. et al. Realizing high-capacity all-solid-state lithium-sulfur batteries using a low-density inorganic solid-state electrolyte. Nat. Commun. 14, 1895 (2023).
28. Kwok, C. Y., Xu, S., Kochetkov, I., Zhou, L. & Nazar, L. F. High-performance all-solid-state Li2S batteries using an interfacial redox mediator. Energy Environ. Sci. 16, 610–618 (2023).10.1039/D2EE03297J ↗
29. Xu, S. et al. A high capacity all solid-state Li–sulfur battery enabled by conversion–intercalation hybrid cathode architecture. Adv. Funct. Mater. 31, 2004239 (2021).10.1002/adfm.202004239 ↗
30. Ulissi, U. et al. High capacity all-solid-state lithium batteries enabled by pyrite–sulfur composites. Adv. Energy Mater. 8, 1801462 (2018).10.1002/aenm.201801462 ↗
31. Alzahrani, A. S. et al. Confining sulfur in porous carbon by vapor deposition to achieve high-performance cathode for all-solid-state lithium–sulfur batteries. ACS Energy Lett. 6, 413–418 (2021).10.1021/acsenergylett.0c01956 ↗
32. Kim, H., Choi, H.-N., Hwang, J.-Y., Yoon, C. S. & Sun, Y.-K. Tailoring the interface between sulfur and sulfide solid electrolyte for high-areal-capacity all-solid-state lithium–sulfur batteries. ACS Energy Lett. 8, 3971–3979 (2023).10.1021/acsenergylett.3c01473 ↗
33. Zhou, G., Chen, H. & Cui, Y. Formulating energy density for designing practical lithium–sulfur batteries. Nat. Energy 7, 312–319 (2022).10.1038/s41560-022-01001-0 ↗
34. Cao, D. et al. Understanding electrochemical reaction mechanisms of sulfur in all-solid-state batteries through operando and theoretical studies. Angew. Chem. Int. Ed. 135, e202302363 (2023).
35. Xiao, Y. et al. Comparison of sulfur cathode reactions between a concentrated liquid electrolyte system and a solid-state electrolyte system by soft X-ray absorption spectroscopy. ACS Appl. Energy Mater. 4, 186–193 (2021).10.1021/acsaem.0c02063 ↗
36. Dietrich, C. et al. Lithium ion conductivity in Li2S–P2S5 glasses—building units and local structure evolution during the crystallization of superionic conductors Li3PS4, Li7P3S11 and Li4P2S7. J. Mater. Chem. A 5, 18111–18119 (2017).10.1039/C7TA06067J ↗
37. Sun, K. et al. Interaction of TiS2 and sulfur in Li–S battery system. J. Electrochem. Soc. 164, A1291–A1297 (2017).10.1149/2.1631706jes ↗
38. Dewald, G. F., Ohno, S., Hering, J. G., Janek, J. & Zeier, W. G. Analysis of charge carrier transport toward optimized cathode composites for all‐solid‐state Li–S batteries. Batteries Supercaps 4, 183–194 (2021).10.1002/batt.202000194 ↗
39. Han, F. et al. High electronic conductivity as the origin of lithium dendrite formation within solid electrolytes. Nat. Energy 4, 187–196 (2019).10.1038/s41560-018-0312-z ↗
40. Perdew, J. P., Burke, K. & Ernzerhof, M. Generalized gradient approximation made simple. Phys. Rev. Lett. 77, 3865–3868 (1996).10.1103/PhysRevLett.77.3865 ↗
41. Schwietert, T. K. et al. Clarifying the relationship between redox activity and electrochemical stability in solid electrolytes. Nat. Mater. 19, 428–435 (2020).10.1038/s41563-019-0576-0 ↗
42. Notestein, J. M. et al. Structural assessment and catalytic Consequences of the oxygen coordination environment in grafted Ti−calixarenes. J. Am. Chem. Soc. 129, 1122–1131 (2007).10.1021/ja065830c ↗
43. Cutsail, G. E. III & DeBeer, S. Challenges and opportunities for applications of advanced X-ray spectroscopy in catalysis research. ACS Catal. 12, 5864–5886 (2022).10.1021/acscatal.2c01016 ↗
44. Wang, Y. et al. Superionic conduction and interfacial properties of the low temperature phase Li7P2S8Br0.5I0.5. Energy Storage Mater. 19, 80–87 (2019).10.1016/j.ensm.2019.02.029 ↗
45. Ravel, B. & Newville, M. ATHENA, ARTEMIS, HEPHAESTUS: data analysis for X-ray absorption spectroscopy using IFEFFIT. J. Synchrotron Radiat. 12, 537–541 (2005).10.1107/S0909049505012719 ↗
46. Singh, V., Kosa, M., Majhi, K. & Major, D. T. Putting DFT to the test: a first-principles study of electronic, magnetic, and optical properties of Co3O4. J. Chem. Theory Comput. 11, 64–72 (2015).10.1021/ct500770m ↗
47. 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 ↗
48. Blöchl, P. E. Projector augmented-wave method. Phys. Rev. B 50, 17953–17979 (1994).10.1103/PhysRevB.50.17953 ↗
49. 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 ↗
50. Dronskowski, R. & Bloechl, P. E. Crystal orbital Hamilton populations (COHP): energy-resolved visualization of chemical bonding in solids based on density-functional calculations. J. Phys. Chem. 97, 8617–8624 (1993).10.1021/j100135a014 ↗
51. Deringer, V. L., Tchougréeff, A. L. & Dronskowski, R. Crystal orbital Hamilton population (COHP) analysis as projected from plane–wave basis sets. J. Phys. Chem. A 115, 5461–5466 (2011).10.1021/jp202489s ↗
52. Maintz, S., Deringer, V. L., Tchougréeff, A. L. & Dronskowski, R. Analytic projection from plane–wave and PAW wavefunctions and application to chemical-bonding analysis in solids. J. Comput. Chem. 34, 2557–2567 (2013).10.1002/jcc.23424 ↗
53. Peng, J., Wang, X., Li, H., Chen, L. & Wu, F. High-capacity, long-life iron fluoride all-solid-state lithium battery with sulfide solid electrolyte. Adv. Energy Mater. 13, 2300706 (2023).10.1002/aenm.202300706 ↗
54. Wan, T. H., Saccoccio, M., Chen, C. & Ciucci, F. Influence of the discretization methods on the distribution of relaxation times deconvolution: implementing radial basis functions with DRTtools. Electrochim. Acta 184, 483–499 (2015).10.1016/j.electacta.2015.09.097 ↗
55. Wang, D. et al. Overcoming the conversion reaction limitation at three-phase interfaces using mixed conductors towards energy-dense solid-state Li–S batteries. figshare https://doi.org/10.6084/m9.figshare.27257931 (2024).10.6084/m9.figshare.27257931 ↗