How Regiochemistry Influences Aggregation Behavior and Charge Transport in Conjugated Organosulfur Polymer Cathodes for Lithium–Sulfur Batteries
Source abstract
Abstract
For lithium-sulfur (Li-S) batteries to become competitive, they require high stability and energy density. Organosulfur polymer-based cathodes have recently shown promising performance due to their ability to overcome common limitations of Li-S batteries, such as the insulating nature of sulfur. In this study, we use a multiscale modeling approach to explore the influence of the regiochemistry of a conjugated poly(4-(thiophene-3-yl)benzenethiol) (PTBT) polymer on its aggregation behavior and charge transport. Classical molecular dynamics simulations of the self-assembly of polymer chains with different regioregularity show that a head-to-tail/head-to-tail regularity can form a well-ordered crystalline phase of planar chains allowing for fast charge transport. Our X-ray diffraction measurements, in conjunction with our predicted crystal structure, confirm the presence of crystalline phases in the electropolymerized PTBT polymer. We quantitatively describe the charge transport in the crystalline phase in a band-like regime. Our results give detailed insights into the interplay between microstructural and electrical properties of conjugated polymer cathode materials, highlighting the effect of polymer chain regioregularity on its charge transport properties.
Source: openalex_inverted_index · Quality: baseline
Research context
OpenAlex topics: Advanced Battery Materials and Technologies · Conducting polymers and applications · Organic Electronics and Photovoltaics
SciVX discovery tags are terminology-based. OpenAlex topics are source-provided classifications.
Affiliations
Research Group for Simulations of Energy Materials, Helmholtz-Zentrum Berlin für Materialien und Energie GmbH, Hahn-Meitner-Platz 1, 14109 Berlin, Germany
Theoretical Chemistry, Institute of Chemistry and Biochemistry, Freie Universität Berlin, Arnimallee 22, 14195 Berlin, Germany
Applied Theoretical Physics - Computational Physics, Physikalisches Institut, Albert-Ludwigs-Universität Freiburg, Hermann-Herder-Straße 3, 79104 Freiburg, Germany
Department Electrochemical Energy Storage, Helmholtz-Zentrum Berlin für Materialien und Energie GmbH, Hahn-Meitner-Platz 1, 14109 Berlin, Germany
Institute of Chemistry, University of Potsdam, Am Neuen Palais 10, 14469 Potsdam, Germany
Department Structure and Dynamics of Energy Materials, Helmholtz-Zentrum Berlin für Materialien und Energie GmbH, Hahn-Meitner-Platz 1, 14109 Berlin, Germany
Institute for Chemistry, Martin Luther Universität Halle-Wittenberg, Von-Danckelmann-Platz 4, 06120 Halle (Saale), Germany
Theory of Electron Dynamics and Spectroscopy, Helmholtz-Zentrum Berlin für Materialien und Energie GmbH, Hahn-Meitner-Platz 1, 14109 Berlin, Germany
Funding
Deutsche Forschungsgemeinschaft
References (100+)
Show source-provided references
1. 10.1021/cm901452z10.1021/cm901452z ↗
2. 10.1021/jz400665210.1021/jz4006652 ↗
3. 10.1016/j.rser.2015.12.00910.1016/j.rser.2015.12.009 ↗
4. 10.1021/acsami.7b0620810.1021/acsami.7b06208 ↗
5. 10.3390/en1012193710.3390/en10121937 ↗
6. Zuckerman, J. J.; Hagen, A. P. Inorganic Reactions and Methods: Oligomerization and Polymerization Formation of Intercalation Compounds ; John Wiley & Sons: New York, 1990; Vol. 17; pp 53–53.10.1002/9780470145326 ↗
7. 10.1016/j.jpowsour.2013.01.13210.1016/j.jpowsour.2013.01.132 ↗
8. 10.1021/acs.chemmater.7b0303510.1021/acs.chemmater.7b03035 ↗
9. 10.1021/acs.macromol.7b0058210.1021/acs.macromol.7b00582 ↗
10. 10.3389/fchem.2021.73213210.3389/fchem.2021.732132 ↗
11. 10.1039/D1NJ04062F10.1039/D1NJ04062F ↗
12. 10.1021/cr500062v10.1021/cr500062v ↗
13. 10.1039/D1TA08942K10.1039/D1TA08942K ↗
14. 10.1103/PhysRevApplied.18.04407210.1103/PhysRevApplied.18.044072 ↗
15. 10.1021/nn203436j10.1021/nn203436j ↗
16. 10.1002/adma.20110339210.1002/adma.201103392 ↗
17. 10.1016/j.ensm.2018.03.01710.1016/j.ensm.2018.03.017 ↗
18. 10.1002/cssc.20190312210.1002/cssc.201903122 ↗
19. 10.1002/advs.20227000810.1002/advs.202270008 ↗
20. 10.1038/ncomms827810.1038/ncomms8278 ↗
21. 10.1002/smtd.20180015610.1002/smtd.201800156 ↗
22. 10.1002/cssc.20220043410.1002/cssc.202200434 ↗
23. 10.1038/nchem.162410.1038/nchem.1624 ↗
24. 10.1039/C5RA01188D10.1039/C5RA01188D ↗
25. 10.1039/D1CP04550D10.1039/D1CP04550D ↗
26. 10.1002/cphc.20210051910.1002/cphc.202100519 ↗
27. Skotheim, T. A.; Reynolds, J. Conjugated Polymers: Theory, Synthesis, Properties, and Characterization , 3rd ed. Taylor and Francis: Boca Raton, 2006; pp 1–49.10.1201/9781420043594 ↗
28. 10.1039/c1py00171j10.1039/c1py00171j ↗
29. 10.1039/C3CS60380F10.1039/C3CS60380F ↗
30. 10.1080/1532179050047119410.1080/15321790500471194 ↗
31. 10.1021/acsnano.7b0239410.1021/acsnano.7b02394 ↗
32. 10.1039/D2CC01430K10.1039/D2CC01430K ↗
33. 10.1039/c0cp00785d10.1039/c0cp00785d ↗
34. Poelking, C.; Daoulas, K.; Troisi, A.; Andrienko, D. In P3HT Revisited – From Molecular Scale to Solar Cell Devices ; Ludwigs, S., Ed. Springer: Berlin, Heidelberg, 2014; pp 139–180.10.1007/12_2014_277 ↗
35. 10.1039/C5CP02769A10.1039/C5CP02769A ↗
36. 10.1021/acs.macromol.8b0186310.1021/acs.macromol.8b01863 ↗
37. 10.1103/PhysRevB.83.12130610.1103/PhysRevB.83.121306 ↗
38. 10.1021/jp311160y10.1021/jp311160y ↗
39. 10.1002/adfm.20130206910.1002/adfm.201302069 ↗
40. 10.1021/jacs.5b0658410.1021/jacs.5b06584 ↗
41. 10.1021/acs.jpcb.7b0151010.1021/acs.jpcb.7b01510 ↗
42. 10.1103/PhysRevMaterials.2.04560510.1103/PhysRevMaterials.2.045605 ↗
43. 10.1021/cm000421f10.1021/cm000421f ↗
44. 10.1021/jp207026s10.1021/jp207026s ↗
45. 10.1039/C6SC01599A10.1039/C6SC01599A ↗
46. 10.1038/ncomms1404710.1038/ncomms14047 ↗
47. 10.1039/C9RA09712K10.1039/C9RA09712K ↗
48. Gayen, D.; Schütze, Y.; Groh, S.; Dzubiella, J. Solvation Structure of Conjugated Organosulfur Polymers for Lithium-Sulfur Battery Cathodes. ChemRxiv , 2023. https://chemrxiv.org/engage/chemrxiv/article-details/63ea00621d2d1840636905f3 (accessed March 28, 2023)10.26434/chemrxiv-2023-k4mzz ↗
49. 10.1021/ma00207a00810.1021/ma00207a008 ↗
50. 10.1021/ma00167a03810.1021/ma00167a038 ↗
51. 10.1016/0379-6779(88)90243-310.1016/0379-6779(88)90243-3 ↗
52. 10.1149/1.209653010.1149/1.2096530 ↗
53. 10.1515/pac-2018-060210.1515/pac-2018-0602 ↗
54. 10.1021/ma00089a02210.1021/ma00089a022 ↗
55. 10.1038/srep3655410.1038/srep36554 ↗
56. 10.1002/poc.347310.1002/poc.3473 ↗
57. 10.1016/j.rser.2015.12.17710.1016/j.rser.2015.12.177 ↗
58. 10.1021/cg500234r10.1021/cg500234r ↗
59. 10.1016/j.polymer.2013.09.03710.1016/j.polymer.2013.09.037 ↗
60. 10.1038/pj.2016.8610.1038/pj.2016.86 ↗
61. 10.1016/S0379-6779(98)00315-410.1016/S0379-6779(98)00315-4 ↗
62. 10.1021/acsomega.8b0068410.1021/acsomega.8b00684 ↗
63. 10.3390/molecules2802088310.3390/molecules28020883 ↗
64. 10.1021/acs.jpcc.0c0623810.1021/acs.jpcc.0c06238 ↗
65. 10.1039/D1RA07991C10.1039/D1RA07991C ↗
66. 10.1039/C9RA02310K10.1039/C9RA02310K ↗
67. 10.1016/j.synthmet.2004.03.00510.1016/j.synthmet.2004.03.005 ↗
68. 10.1038/nmat372210.1038/nmat3722 ↗
69. 10.1016/0379-6779(87)90071-310.1016/0379-6779(87)90071-3 ↗
70. 10.1016/0032-3861(63)90026-010.1016/0032-3861(63)90026-0 ↗
71. 10.1088/0022-3719/21/23/00410.1088/0022-3719/21/23/004 ↗
72. 10.1038/s41467-020-15399-210.1038/s41467-020-15399-2 ↗
73. 10.1103/PhysRevB.71.16520210.1103/PhysRevB.71.165202 ↗
74. 10.1103/PhysRevB.70.11531110.1103/PhysRevB.70.115311 ↗
75. 10.1103/PhysRevB.98.15520710.1103/PhysRevB.98.155207 ↗
76. 10.1021/acs.chemrev.7b0008610.1021/acs.chemrev.7b00086 ↗
77. 10.1007/BF0133945510.1007/BF01339455 ↗
78. Kittel, C. Introduction to Solid State Physics , 8th ed. John Wiley & Sons: New York, 2004; pp 167–168.
79. 10.1063/1.174272310.1063/1.1742723 ↗
80. 10.1103/RevModPhys.65.59910.1103/RevModPhys.65.599 ↗
81. 10.1080/1478643690821633810.1080/14786436908216338 ↗
82. 10.1103/PhysRevB.57.1296410.1103/PhysRevB.57.12964 ↗
83. 10.1021/jp047023a10.1021/jp047023a ↗
84. 10.1021/acs.jpclett.8b0111210.1021/acs.jpclett.8b01112 ↗
85. 10.1039/C9CP04770K10.1039/C9CP04770K ↗
86. 10.1002/adfm.20150238610.1002/adfm.201502386 ↗
87. Harris, S. An Introduction to the Theory of the Boltzmann Equation , 1st ed. Dover Publications: New York, 2004; pp 121–130.
88. Ziman, J. M. Principles of the Theory of Solids , 2nd ed. Cambridge University Press: Cambridge, 1972; pp 211–230.10.1017/CBO9781139644075 ↗
89. 10.1103/PhysRevLett.109.10640510.1103/PhysRevLett.109.106405 ↗
90. 10.1002/adfm.20180368710.1002/adfm.201803687 ↗
91. 10.1021/nl500758w10.1021/nl500758w ↗
92. 10.1002/advs.20190241210.1002/advs.201902412 ↗
93. 10.1063/5.006809810.1063/5.0068098 ↗
94. 10.1021/acsami.9b2334510.1021/acsami.9b23345 ↗
95. 10.1021/jp911525d10.1021/jp911525d ↗
96. 10.1002/adma.20210300210.1002/adma.202103002 ↗
97. 10.7567/1882-0786/aaf2cf10.7567/1882-0786/aaf2cf ↗
98. 10.1038/s43246-021-00148-910.1038/s43246-021-00148-9 ↗
99. 10.1016/j.cpc.2021.10817110.1016/j.cpc.2021.108171 ↗
100. 10.1021/ja00214a00110.1021/ja00214a001 ↗