Issue

Vol. 15 (2023)

Molecular Engineering Design for High-Performance Aqueous Zinc-Organic Battery

https://doi.org/10.1007/s40820-022-01009-x
Tianjiang Sun
Key Laboratory of Advanced Energy Materials Chemistry (Ministry of Education), College of Chemistry, Haihe Laboratory of Sustainable Chemical Transformations, Renewable Energy Conversion and Storage Center, Nankai University, Tianjin 300071, People’s Republic of China
Weijia Zhang
Key Laboratory of Advanced Energy Materials Chemistry (Ministry of Education), College of Chemistry, Haihe Laboratory of Sustainable Chemical Transformations, Renewable Energy Conversion and Storage Center, Nankai University, Tianjin 300071, People’s Republic of China
Qingshun Nian
CAS Key Laboratory of Materials for Energy Conversion, Department of Materials Science and Engineering, Hefei National Laboratory for Physical Science at the Microscale, University of Science and Technology of China Hefei, Hefei 230026, Anhui, People’s Republic of China
Zhanliang Tao
Key Laboratory of Advanced Energy Materials Chemistry (Ministry of Education), College of Chemistry, Haihe Laboratory of Sustainable Chemical Transformations, Renewable Energy Conversion and Storage Center, Nankai University, Tianjin 300071, People’s Republic of China

Corresponding Author: Zhanliang Tao

taozhl@nankai.edu.cn

Nano-Micro Letters, Vol. 15 (2023), Article Number: 36

Abstract

Novel small sulfur heterocyclic quinones (6a,16a-dihydrobenzo[b]naphtho[2′,3′:5,6][1,4]dithiino[2,3-i]thianthrene-5,7,9,14,16,18-hexaone (4S6Q) and benzo[b]naphtho[2′,3′:5,6][1,4]dithiino[2,3-i]thianthrene-5,9,14,18-tetraone (4S4Q)) are developed by molecule structural design method and as cathode for aqueous zinc-organic batteries. The conjugated thioether (–S–) bonds as connected units not only improve the conductivity of compounds but also inhibit their dissolution by both extended π-conjugated plane and constructed flexible molecular skeleton. Hence, the Zn//4S6Q and Zn//4S4Q batteries exhibit satisfactory electrochemical performance based on 3.5 mol L−1 (M) Zn(ClO4)2 electrolyte. For instance, the Zn//4S6Q battery obtains 240 and 208.6 mAh g−1 of discharge capacity at 150 mA g−1 and 30 A g−1, respectively. The excellent rate capability is ascribed to the fast reaction kinetics. This system displays a superlong life of 20,000 cycles with no capacity fading at 3 A g−1. Additionally, the H+-storage mechanism of the 4S6Q compound is demonstrated by ex situ analyses and density functional theory calculations. Impressively, the battery can normally work at − 60 °C benefiting from the anti-freezing electrolyte and maintain a high discharge capacity of 201.7 mAh g−1, which is 86.2% of discharge capacity at 25 °C. The cutting-edge electrochemical performances of these novel compounds make them alternative electrode materials for Zn-organic batteries.


Highlights:


1 The conjugated thioether (–S–) bonds as connected units not only improve the conductivity of compounds but also inhibit their dissolution by both extended π-conjugated plane and constructed flexible molecular skeleton.
2 The Zn//4S6Q battery based on 3.5 M Zn(ClO4)2 electrolyte shows excellent rate capacity (208.6 mAh g−1 at 30 A g−1), superlong cycling life (> 20,000 cycles with no capacity fading), and impressive low-temperature performance (201.7 mAh g−1 at − 60 °C).
3 The H+-storage mechanism of 4S6Q compound is demonstrated by comprehensive characterizations.

Keywords

Aqueous Zn-organic battery Small sulfur heterocyclic quinones Conjugated thioether skeleton Superlong cycling life H -involved mechanism − 60 °C
Sun, Tianjiang, Weijia Zhang, Qingshun Nian, and Zhanliang Tao. 2023. “Molecular Engineering Design for High-Performance Aqueous Zinc-Organic Battery”. Nano-Micro Letters 15 (January):36. https://doi.org/10.1007/s40820-022-01009-x.
Download Citation
Endnote/Zotero/Mendeley (RIS)
BibTeX
References
  1. X. Wang, Y. Liu, Z. Wei, J. Hong, H. Liang et al., MXene-boosted imine cathodes with extended conjugated structure for aqueous zinc-ion batteries. Adv. Mater. (2022). https://doi.org/10.1002/adma.202206812
  2. J. Zhao, J. Zhang, W. Yang, B. Chen, Z. Zhao et al., “Water-in-deep eutectic solvent” electrolytes enable zinc metal anodes for rechargeable aqueous batteries. Nano Energy 57, 625 (2019). https://doi.org/10.1016/j.nanoen.2018.12.086
  3. Z. Zhao, J. Zhao, Z. Hu, J. Li, J. Li et al., Long-life and deeply rechargeable aqueous Zn anodes enabled by a multifunctional brightener-inspired interphase. Energy Environ. Mater. 12, 1938 (2019). https://doi.org/10.1039/c9ee00596j
  4. Y. Song, P. Ruan, C. Mao, Y. Chang, L. Wang et al., Metal–organic frameworks functionalized separators for robust aqueous zinc-ion batteries. Nano-Micro Lett. 14, 218 (2022). https://doi.org/10.1007/s40820-022-00960-z
  5. Y. Chen, D. Ma, K. Ouyang, M. Yang, S. Shen et al., A multifunctional anti-proton electrolyte for high-rate and super-stable aqueous Zn-vanadium oxide battery. Nano-Micro Lett. 14, 154 (2022). https://doi.org/10.1007/s40820-022-00907-4
  6. M. Wang, Y. Meng, K. Li, T. Ahmad, N. Chen et al., Toward dendrite-free and anti-corrosion Zn anodes by regulating a bismuth-based energizer. eScience. (2022). https://doi.org/10.1016/j.esci.2022.04.003
  7. J. Li, N. Luo, L. Kang, F. Zhao, Y. Jiao et al., Hydrogen-bond reinforced superstructural manganese oxide as the cathode for ultra-stable aqueous zinc ion batteries. Adv. Energy Mater. (2022). https://doi.org/10.1002/aenm.202201840
  8. K. Yang, Y. Hu, T. Zhang, B. Wang, J. Qin et al., Triple-functional polyoxovanadate cluster in regulating cathode, anode, and electrolyte for tough aqueous zinc–ion battery. Adv. Energy Mater. 12, 2202671 (2022). https://doi.org/10.1002/aenm.202202671
  9. L. Ma, S. Chen, C. Long, X. Li, Y. Zhao et al., Achieving high-voltage and high-capacity aqueous rechargeable zinc ion battery by incorporating two-species redox reaction. Adv. Energy Mater. 9, 1902446 (2019). https://doi.org/10.1002/aenm.201902446
  10. T. Sun, W. Zhang, Q. Nian, Z. Tao, Proton-insertion dominated polymer cathode for high-performance aqueous zinc-ion battery. Chem. Eng. J. 452, 139324 (2023). https://doi.org/10.1016/j.cej.2022.139324
  11. Y. Zhao, Y. Huang, F. Wu, R. Chen, L. Li, High-performance aqueous zinc batteries based on organic/organic cathodes integrating multiredox centers. Adv. Mater. 33, e2106469 (2021). https://doi.org/10.1002/adma.202106469
  12. L. Yan, Y.-e Qi, X. Dong, Y. Wang, Y. Xia, Ammonium-ion batteries with a wide operating temperature window from −40 to 80 °C. eScience. (2021). https://doi.org/10.1016/j.esci.2021.12.002
  13. Y. Ma, T. Sun, Q. Nian, S. Zheng, T. Ma et al., Alloxazine as anode material for high-performance aqueous ammonium-ion battery. Nano Res. 15, 2047 (2021). https://doi.org/10.1007/s12274-021-3777-1
  14. S. Zheng, D. Shi, D. Yan, Q. Wang, T. Sun et al., Orthoquinone–based covalent organic frameworks with ordered channel structures for ultrahigh performance aqueous zinc–organic batteries. Angew. Chem. Int. Ed. 61, e202117511 (2022). https://doi.org/10.1002/anie.202117511
  15. S. Xu, M. Sun, Q. Wang, C. Wang, Recent progress in organic electrodes for zinc-ion batteries. J. Semicond. (2020). https://doi.org/10.1088/1674-4926/41/9/091704
  16. Q. Zhao, W. Huang, Z. Luo, L. Liu, Y. Lu et al., High-capacity aqueous zinc batteries using sustainable quinone electrodes. Sci. Adv. 4, 1761 (2018). https://doi.org/10.1126/sciadv.aao1761
  17. L. Yan, Q. Zhu, Y. Qi, J. Xu, Y. Peng et al., Towards high-performance aqueous zinc batteries via a semi-conductive bipolar-type polymer cathode. Angew. Chem. Int. Ed. 61, e202211107 (2022). https://doi.org/10.1002/anie.202211107
  18. Z. Guo, Y. Ma, X. Dong, J. Huang, Y. Wang et al., An environmentally friendly and flexible aqueous zinc battery using an organic cathode. Angew. Chem. Int. Ed. 57, 11737 (2018). https://doi.org/10.1002/anie.201807121
  19. B. Häupler, C. Rössel, A.M. Schwenke, J. Winsberg, D. Schmidt et al., Aqueous zinc-organic polymer battery with a high rate performance and long lifetime. NPG Asia Mater. 8, 283 (2016). https://doi.org/10.1038/am.2016.82
  20. N. Patil, C. Cruz, D. Ciurduc, A. Mavrandonakis, J. Palma et al., An ultrahigh performance zinc-organic battery using poly(catechol) cathode in Zn(TfSi)2-based concentrated aqueous electrolytes. Adv. Energy Mater. 11, 2100939 (2021). https://doi.org/10.1002/aenm.202100939
  21. H. Zhang, D. Xu, L. Wang, Z. Ye, B. Chen et al., A polymer/graphene composite cathode with active carbonyls and secondary amine moieties for high-performance aqueous Zn-organic batteries involving dual-ion mechanism. Small 17, e2100902 (2021). https://doi.org/10.1002/smll.202100902
  22. X. Wang, J. Xiao, W. Tang, Hydroquinone versus pyrocatechol pendants twisted conjugated polymer cathodes for high-performance and robust aqueous zinc-ion batteries. Adv. Funct. Mater. 32, 2108225 (2021). https://doi.org/10.1002/adfm.202108225
  23. C. Wang, Y. Xu, Y. Fang, M. Zhou, L. Liang et al., Extended π-conjugated system for fast-charge and -discharge sodium-ion batteries. J. Am. Chem. Soc. 137, 3124 (2015). https://doi.org/10.1021/jacs.5b00336
  24. J. Xie, F. Yu, J. Zhao, W. Guo, H.-L. Zhang et al., An irreversible electrolyte anion-doping strategy toward a superior aqueous Zn-organic battery. Energy Storage Mater. 33, 283 (2020). https://doi.org/10.1016/j.ensm.2020.08.027
  25. S. Li, J. Shang, M. Li, M. Xu, F. Zeng et al., Design and synthesis of a π-conjugated n-heteroaromatic material for aqueous zinc–organic batteries with ultrahigh rate and extremely long life. Adv. Mater. (2022). https://doi.org/10.1002/adma.202207115
  26. Z. Tie, Y. Zhang, J. Zhu, S. Bi, Z. Niu, An air-rechargeable Zn/organic battery with proton storage. J. Am. Chem. Soc. 144, 10301 (2022). https://doi.org/10.1021/jacs.2c01485
  27. H. Zhang, S. Xie, Z. Cao, D. Xu, L. Wang et al., Extended π-conjugated system in organic cathode with active C=N bonds for driving aqueous zinc-ion batteries. ACS Appl. Energy Mater. 4, 655 (2021). https://doi.org/10.1021/acsaem.0c02526
  28. Z. Tie, L. Liu, S. Deng, D. Zhao, Z. Niu, Proton insertion chemistry of a zinc–organic battery. Angew. Chem. Int. Ed. 59, 4920 (2020). https://doi.org/10.1002/anie.201916529
  29. Y. Chen, J. Li, Q. Zhu, K. Fan, Y. Cao et al., Two-dimensional organic supramolecule via hydrogen bonding and π–π stacking for ultrahigh capacity and long-life aqueous zinc–organic batteries. Angew. Chem. Int. Ed. (2022). https://doi.org/10.1002/anie.202116289
  30. M.J. Frisch, G.W. Trucks, H.B. Schlegel, G.E. Scuseria, M. A. Robb et al., Gaussian 16 Rev. C.01, (Wallingford, CT, 2016)
  31. T. Lu, F. Chen, Multiwfn: A multifunctional wavefunction analyzer. J. Comput. Chem. 33, 580 (2012). https://doi.org/10.1002/jcc.22885
  32. T. Sun, Q. Nian, S. Zheng, X. Yuan, Z. Tao, Water cointercalation for high-energy-density aqueous zinc-ion battery based potassium manganite cathode. J. Power Sources 478, 228758 (2020). https://doi.org/10.1016/j.jpowsour.2020.228758
  33. T. Ma, Q. Zhao, J. Wang, Z. Pan, J. Chen, A sulfur heterocyclic quinone cathode and a multifunctional binder for a high-performance rechargeable lithium-ion battery. Angew. Chem. Int. Ed. 55, 6428 (2016). https://doi.org/10.1002/anie.201601119
  34. C. Wang, Weak intermolecular interactions for strengthening organic batteries. Energy Environ. Mater. 3, 441 (2020). https://doi.org/10.1002/eem2.12076
  35. Y. Wang, C. Wang, Z. Ni, Y. Gu, B. Wang et al., Binding zinc ions by carboxyl groups from adjacent molecules toward long-life aqueous zinc–organic batteries. Adv. Mater. 32, e2000338 (2020). https://doi.org/10.1002/adma.202000338
  36. Y. Hu, Y. Gao, L. Fan, Y. Zhang, B. Wang et al., Electrochemical study of poly(2,6-anthraquinonyl sulfide) as cathode for alkali-metal-ion batteries. Adv. Energy Mater. 10, 2002780 (2020). https://doi.org/10.1002/aenm.202002780
  37. T. Shi, G. Li, Y. Han, Y. Gao, F. Wang et al., Oxidized indanthrone as a cost-effective and high-performance organic cathode material for rechargeable lithium batteries. Energy Storage Mater. 50, 265 (2022). https://doi.org/10.1016/j.ensm.2022.05.013
  38. S. Zheng, L. Miao, T. Sun, L. Li, T. Ma et al., An extended carbonyl-rich conjugated polymer cathode for high-capacity lithium-ion batteries. J. Mater. Chem. A 9, 2700 (2021). https://doi.org/10.1039/d0ta11648c
  39. J. Hong, M. Lee, B. Lee, D.H. Seo, C.B. Park et al., Biologically inspired pteridine redox centres for rechargeable batteries. Nat. Commun. 5, 5335 (2014). https://doi.org/10.1038/ncomms6335
  40. T. Lu, Q. Chen, A simple method of identifying π orbitals for non-planar systems and a protocol of studying π electronic structure. Theor. Chem. Acc. 139, 25 (2020). https://doi.org/10.1007/s00214-019-2541-z
  41. Z. Tie, S. Deng, H. Cao, M. Yao, Z. Niu, J. Chen, A symmetric all-organic proton battery in mild electrolyte. Angew. Chem. Int. Ed. 61, e202115180 (2022). https://doi.org/10.1002/anie.202115180
  42. L.S.W. Alexander, I. Boldyrev, All-metal aromaticity and antiaromaticity. Chem. Rev. 105, 3716 (2005). https://doi.org/10.1021/cr030091t
  43. E. Hückel, Quantentheoretische beiträge zum benzolproblem. Z. Phys. 70, 204 (1931). https://doi.org/10.1007/BF01339530
  44. S. Fujii, S. Marques-Gonzalez, J.Y. Shin, H. Shinokubo, T. Masuda et al., Highly-conducting molecular circuits based on antiaromaticity. Nat. Commun. 8, 15984 (2017). https://doi.org/10.1038/ncomms15984
  45. J. Kruszewski, M.T. Krygowski, Definition of aromaticity basing on the harmonic oscillator model. Tetrahedron Lett. 36, 3839 (1972). https://doi.org/10.1016/S0040-4039(01)94175-9
  46. T. Sun, H. Du, S. Zheng, J. Shi, X. Yuan et al., Bipolar organic polymer for high performance symmetric aqueous proton battery. Small Methods 5, e2100367 (2021). https://doi.org/10.1002/smtd.202100367
  47. Y. Chen, Y.-H. Zhang, L.-J. Zhao, ATR-FTIR spectroscopic studies on aqueous LiClO4, NaClO4, and Mg(ClO4)2 solutions. Phys. Chem. Chem. Phys. 6, 5378 (2004). https://doi.org/10.1039/b311768e
  48. M. Na, Y. Oh, H.R. Byon, Effects of Zn2+ and H+ association with naphthalene diimide electrodes for aqueous Zn-ion batteries. Chem. Mater. 32, 6990 (2020). https://doi.org/10.1021/acs.chemmater.0c02357
  49. T. Sun, Q. Nian, S. Zheng, J. Shi, Z. Tao, Layered Ca0.28MnO2·0.5H2O as a high performance cathode for aqueous zinc-ion battery. Small 16, e2000597 (2020). https://doi.org/10.1002/smll.202000597
Read More
Author biographies are not available.
Download this PDF file
PDF SUPPLEMENTARY MATERIAL
Statistic
Read Counter : 2567 Download : 1916

Most read articles by the same author(s)