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Vol. 14 (2022)

Iodine Promoted Ultralow Zn Nucleation Overpotential and Zn-Rich Cathode for Low-Cost, Fast-Production and High-Energy Density Anode-Free Zn-Iodine Batteries

https://doi.org/10.1007/s40820-022-00948-9
Yixiang Zhang
State Key Laboratory of Molecular Engineering of Polymers, Department of Macromolecular Science, Fudan University, 2005 Songhu Road, Shanghai 200438, People’s Republic of China
Lequan Wang
State Key Laboratory of Molecular Engineering of Polymers, Department of Macromolecular Science, Fudan University, 2005 Songhu Road, Shanghai 200438, People’s Republic of China
Qingyun Li
State Key Laboratory of Molecular Engineering of Polymers, Department of Macromolecular Science, Fudan University, 2005 Songhu Road, Shanghai 200438, People’s Republic of China
Bo Hu
State Key Laboratory of Molecular Engineering of Polymers, Department of Macromolecular Science, Fudan University, 2005 Songhu Road, Shanghai 200438, People’s Republic of China
Junming Kang
State Key Laboratory of Molecular Engineering of Polymers, Department of Macromolecular Science, Fudan University, 2005 Songhu Road, Shanghai 200438, People’s Republic of China
Yuhuan Meng
State Key Laboratory of Molecular Engineering of Polymers, Department of Macromolecular Science, Fudan University, 2005 Songhu Road, Shanghai 200438, People’s Republic of China
Zedong Zhao
State Key Laboratory of Molecular Engineering of Polymers, Department of Macromolecular Science, Fudan University, 2005 Songhu Road, Shanghai 200438, People’s Republic of China
Hongbin Lu
State Key Laboratory of Molecular Engineering of Polymers, Department of Macromolecular Science, Fudan University, 2005 Songhu Road, Shanghai 200438, People’s Republic of China

Corresponding Author: Hongbin Lu

hongbinlu@fudan.edu.cn

Nano-Micro Letters, Vol. 14 (2022), Article Number: 208

Abstract

The anode-free design is a promising strategy to increase the energy density of aqueous Zn metal batteries (AZMBs). However, the scarcity of Zn-rich cathodes and the rapid loss of limited Zn greatly hinder their commercial applications. To address these issues, a novel anode-free Zn-iodine battery (AFZIB) was designed via a simple, low-cost and scalable approach. Iodine plays bifunctional roles in improving the AFZIB overall performance: enabling high-performance Zn-rich cathode and modulating Zn deposition behavior. On the cathode side, the ZnI2 serves as Zn-rich cathode material. The graphene/polyvinyl pyrrolidone heterostructure was employed as an efficient host for ZnI2 to enhance electron conductivity and suppress the shuttle effect of iodine species. On the anode side, trace I3− additive in the electrolyte creates surface reconstruction on the commercial Cu foil. The in situ formed zincophilic Cu nanocluster allows ultralow-overpotential and uniform Zn deposition and superior reversibility (average coulombic efficiency > 99.91% over 7,000 cycles). Based on such a configuration, AFZIB exhibits significantly increased energy density (162 Wh kg−1) and durable cycle stability (63.8% capacity retention after 200 cycles) under practical application conditions. Considering the low cost and simple preparation methods of the electrode materials, this work paves the way for the practical application of AZMBs.


Highlights:


1 The I3− additive promoted in situ formation of zincophilic Cu nanoclusters on commercial Cu foil, which achieves uniform Zn deposition with ultralow nucleation overpotential and high reversibility.
2 The Zn-rich ZnI2 cathode confined by graphene/polyvinyl pyrrolidone heterostructure shows enhanced conductivity and shuttle effect suppression, providing sufficient Zn2+ for the anode stably.
3 The assembled anode-free Zn-iodine battery exhibits attractive features for commercialization: low cost, fast production, significantly increased energy density and durable cycle stability under practical application conditions.

Keywords

Zn metal battery Zn deposition Zn-rich cathode Anode-free Energy density
Zhang, Yixiang, Lequan Wang, Qingyun Li, Bo Hu, Junming Kang, Yuhuan Meng, Zedong Zhao, and Hongbin Lu. 2022. “Iodine Promoted Ultralow Zn Nucleation Overpotential and Zn-Rich Cathode for Low-Cost, Fast-Production and High-Energy Density Anode-Free Zn-Iodine Batteries”. Nano-Micro Letters 14 (October):208. https://doi.org/10.1007/s40820-022-00948-9.
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References
  1. G. Fang, J. Zhou, A. Pan, S. Liang, Recent advances in aqueous zinc-ion batteries. ACS Energy Lett. 3(10), 2480–2501 (2018). https://doi.org/10.1021/acsenergylett.8b01426
  2. M. Song, H. Tan, D. Chao, H.J. Fan, Recent advances in Zn-ion batteries. Adv. Funct. Mater. 28(41), 1802564 (2018). https://doi.org/10.1002/adfm.201802564
  3. X. Jia, C. Liu, Z.G. Neale, J. Yang, G. Cao, Active materials for aqueous zinc ion batteries: synthesis, crystal structure, morphology, and electrochemistry. Chem. Rev. 120(15), 7795–7866 (2020). https://doi.org/10.1021/acs.chemrev.9b00628
  4. J. Cao, D. Zhang, X. Zhang, Z. Zeng, J. Qin et al., Strategies of regulating Zn2+ solvation structures for dendrite-free and side reaction-suppressed zinc-ion batteries. Energy Environ. Sci. 15(2), 499–528 (2022). https://doi.org/10.1039/d1ee03377h
  5. L.E. Blanc, D. Kundu, L.F. Nazar, Scientific challenges for the implementation of Zn-ion batteries. Joule 4(4), 771–799 (2020). https://doi.org/10.1016/j.joule.2020.03.002
  6. B. Li, X. Zhang, T. Wang, Z. He, B. Lu et al., Interfacial engineering strategy for high-performance Zn metal anodes. Nano-Micro Lett. 14, 6 (2021). https://doi.org/10.1007/s40820-021-00764-7
  7. W. Du, S. Huang, Y. Zhang, M. Ye, C.C. Li, Enable commercial zinc powders for dendrite-free zinc anode with improved utilization rate by pristine graphene hybridization. Energy Storage Mater. 45, 465–473 (2022). https://doi.org/10.1016/j.ensm.2021.12.007
  8. C. Zhang, W. Shin, L. Zhu, C. Chen, J.C. Neuefeind et al., The electrolyte comprising more robust water and superhalides transforms Zn-metal anode reversibly and dendrite-free. Carbon Energy 3(2), 339–348 (2020). https://doi.org/10.1002/cey2.70
  9. F. Ming, Y. Zhu, G. Huang, A.H. Emwas, H. Liang et al., Co-solvent electrolyte engineering for stable anode-free zinc metal batteries. J. Am. Chem. Soc. 144(16), 7160–7170 (2022). https://doi.org/10.1021/jacs.1c12764
  10. W. Yao, P. Zou, M. Wang, H. Zhan, F. Kang et al., Design principle, optimization strategies, and future perspectives of anode-free configurations for high-energy rechargeable metal batteries. Electrochem. Energy Rev. 4(3), 601–631 (2021). https://doi.org/10.1007/s41918-021-00106-6
  11. Y. Li, L. Wu, C. Dong, X. Wang, Y. Dong et al., Manipulating horizontal Zn deposition with graphene interpenetrated Zn hybrid foils for dendrite-free aqueous zinc ion batteries. Energy Environ. Mater. (2022). https://doi.org/10.1002/eem2.12423
  12. Y. Zeng, P.X. Sun, Z. Pei, Q. Jin, X. Zhang et al., Nitrogen-doped carbon fibers embedded with zincophilic cu nanoboxes for stable Zn-metal anodes. Adv. Mater. 34(18), e2200342 (2022). https://doi.org/10.1002/adma.202200342
  13. Y. An, Y. Tian, K. Zhang, Y. Liu, C. Liu et al., Stable aqueous anode-free zinc batteries enabled by interfacial engineering. Adv. Funct. Mater. 31(26), 2101886 (2021). https://doi.org/10.1002/adfm.202101886
  14. L. Lin, K. Qin, Y.S. Hu, H. Li, X. Huang et al., A better choice to achieve high volumetric energy density: anode-free lithium-metal batteries. Adv. Mater. 34(23), e2110323 (2022). https://doi.org/10.1002/adma.202110323
  15. J. Yang, B. Yin, Y. Sun, H. Pan, W. Sun et al., Zinc anode for mild aqueous zinc-ion batteries: challenges, strategies, and perspectives. Nano-Micro Lett. 14, 42 (2022). https://doi.org/10.1007/s40820-021-00782-5
  16. Y. Zhu, Y. Cui, H.N. Alshareef, An anode-free Zn-MnO2 battery. Nano Lett. 21(3), 1446–1453 (2021). https://doi.org/10.1021/acs.nanolett.0c04519
  17. G. Wang, M. Zhu, G. Chen, Z. Qu, B. Kohn et al., An anode-free Zn-graphite battery. Adv. Mater. 34(29), 2201957 (2022). https://doi.org/10.1002/adma.202201957
  18. J.B. Goodenough, How we made the Li-ion rechargeable battery. Nat. Electron. 1(3), 204–204 (2018). https://doi.org/10.1038/s41928-018-0048-6
  19. J. Wu, Q. Kuang, K. Zhang, J. Feng, C. Huang et al., Spinel Zn3V3O8: a high-capacity zinc supplied cathode for aqueous Zn-ion batteries. Energy Storage Mater. 41, 297–309 (2021). https://doi.org/10.1016/j.ensm.2021.06.006
  20. J.C. Knight, S. Therese, A. Manthiram, Chemical extraction of Zn from ZnMn2O4-based spinels. J. Mater. Chem. A 3(42), 21077–21082 (2015). https://doi.org/10.1039/c5ta06482a
  21. C. Pan, R.G. Nuzzo, A.A. Gewirth, ZnAlxCo2–xO4 spinels as cathode materials for non-aqueous Zn batteries with an open circuit voltage of ≤2 V. Chem. Mater. 29(21), 9351–9359 (2017). https://doi.org/10.1021/acs.chemmater.7b03340
  22. J. Zhang, Q. Liu, Y. Ruan, S. Lin, K. Wang et al., Monolithic crystalline swelling of graphite oxide: a bridge to ultralarge graphene oxide with high scalability. Chem. Mater. 30(6), 1888–1897 (2018). https://doi.org/10.1021/acs.chemmater.7b04458
  23. Z. Cai, Y. Ou, J. Wang, R. Xiao, L. Fu et al., Chemically resistant Cu–Zn/Zn composite anode for long cycling aqueous batteries. Energy Storage Mater. 27, 205–211 (2020). https://doi.org/10.1016/j.ensm.2020.01.032
  24. S. Xie, Y. Li, X. Li, Y. Zhou, Z. Dang et al., Stable zinc anodes enabled by zincophilic Cu nanowire networks. Nano-Micro Lett. 14, 39 (2021). https://doi.org/10.1007/s40820-021-00783-4
  25. L. Zhou, F. Yang, S. Zeng, X. Gao, X. Liu et al., Zincophilic Cu sites induce dendrite-free Zn anodes for robust alkaline/neutral aqueous batteries. Adv. Funct. Mater. 32(15), 2110829 (2021). https://doi.org/10.1002/adfm.202110829
  26. S. Liu, W. Shang, Y. Yang, D. Kang, C. Li et al., Effects of I3- electrolyte additive on the electrochemical performance of Zn anodes and Zn/MnO2 batteries. Batteries Supercaps 5(1), 202100221 (2021). https://doi.org/10.1002/batt.202100221
  27. J. Meng, Z. Yang, L. Chen, X. Zeng, H. Chen et al., The investigation on the electrochemical performance of CuI as cathode material for zinc storage. Electrochim. Acta 338, 135915 (2020). https://doi.org/10.1016/j.electacta.2020.135915
  28. T. Ghodselahi, M.A. Vesaghi, A. Shafiekhani, A. Baghizadeh, M. Lameii, XPS study of the Cu@Cu2O core-shell nanops. Appl. Surf. Sci. 255(5), 2730–2734 (2008). https://doi.org/10.1016/j.apsusc.2008.08.110
  29. J. Hao, L. Yuan, B. Johannessen, Y. Zhu, Y. Jiao et al., Studying the conversion mechanism to broaden cathode options in aqueous zinc-ion batteries. Angew. Chem. Int. Ed. 60(47), 25114–25121 (2021). https://doi.org/10.1002/anie.202111398
  30. Y. Zhang, J.D. Howe, S. Ben-Yoseph, Y. Wu, N. Liu, Unveiling the origin of alloy-seeded and nondendritic growth of Zn for rechargeable aqueous Zn batteries. ACS Energy Lett. 6(2), 404–412 (2021). https://doi.org/10.1021/acsenergylett.0c02343
  31. Q. Zhao, Y. Wang, W. Liu, X. Liu, H. Wang et al., An in-depth study of regulable zincophilic alloy matrix toward stable zinc metal batteries. Adv. Mater. Interfaces 9(7), 2102254 (2022). https://doi.org/10.1002/admi.202102254
  32. H. Meng, Q. Ran, T.Y. Dai, H. Shi, S.P. Zeng et al., Surface-alloyed nanoporous zinc as reversible and stable anodes for high-performance aqueous zinc-ion battery. Nano-Micro Lett. 14, 128 (2022). https://doi.org/10.1007/s40820-022-00867-9
  33. Z. Zhao, R. Wang, C. Peng, W. Chen, T. Wu et al., Horizontally arranged zinc platelet electrodeposits modulated by fluorinated covalent organic framework film for high-rate and durable aqueous zinc ion batteries. Nat. Commun. 12, 6606 (2021). https://doi.org/10.1038/s41467-021-26947-9
  34. J. Hao, X. Li, S. Zhang, F. Yang, X. Zeng et al., Designing dendrite-free zinc anodes for advanced aqueous zinc batteries. Adv. Funct. Mater. 30(30), 2001263 (2020). https://doi.org/10.1002/adfm.202001263
  35. X. Xie, S. Liang, J. Gao, S. Guo, J. Guo et al., Manipulating the ion-transfer kinetics and interface stability for high-performance zinc metal anodes. Energy Environ. Sci. 13(2), 503–510 (2020). https://doi.org/10.1039/c9ee03545a
  36. Z. Wang, J. Huang, Z. Guo, X. Dong, Y. Liu et al., A metal-organic framework host for highly reversible dendrite-free zinc metal anodes. Joule 3(5), 1289–1300 (2019). https://doi.org/10.1016/j.joule.2019.02.012
  37. X. Li, N. Li, Z. Huang, Z. Chen, G. Liang et al., Enhanced redox kinetics and duration of aqueous I2/I- conversion chemistry by MXene confinement. Adv. Mater. 33(8), 2006897 (2021). https://doi.org/10.1002/adma.202006897
  38. J. Ma, M. Liu, Y. He, J. Zhang, Iodine redox chemistry in rechargeable batteries. Angew. Chem. Int. Ed. 60(23), 12636–12647 (2021). https://doi.org/10.1002/anie.202009871
  39. D. Lin, Y. Li, Recent advances of aqueous rechargeable zinc-iodine batteries: challenges, solutions, and prospects. Adv. Mater. 34(23), 2108856 (2022). https://doi.org/10.1002/adma.202108856
  40. Y. Yang, S. Liang, J. Zhou, Progress and prospect of the zinc–iodine battery. Curr. Opi. Electrochem. 30, 100761 (2021). https://doi.org/10.1016/j.coelec.2021.100761
  41. Y. Gu, Y. Sun, Y. Zhang, H. Chi, W. Zhang et al., Highly efficient adsorption of copper ions by a PVP-reduced graphene oxide based on a new adsorptions mechanism. Nano-Micro Lett. 6, 80–87 (2014). https://doi.org/10.1007/bf03353772
  42. Y. Wu, P. Deng, Y. Tian, J. Feng, J. Xiao et al., Simultaneous and sensitive determination of ascorbic acid, dopamine and uric acid via an electrochemical sensor based on PVP-graphene composite. J. Nanobiotechnol. 18(1), 112 (2020). https://doi.org/10.1186/s12951-020-00672-9
  43. H. Tian, S. Zhang, Z. Meng, W. He, W.Q. Han, Rechargeable aluminum/iodine battery redox chemistry in ionic liquid electrolyte. ACS Energy Lett. 2(5), 1170–1176 (2017). https://doi.org/10.1021/acsenergylett.7b00160
  44. R. Pažout, J. Housková, M. Dušek, J. Maixner, P. Kačer, Platinum precursor of anticancer drug: a structure fixed by long intermolecular N–H···I and C–H···I hydrogen bonds. Struct. Chem. 22(6), 1325–1330 (2011). https://doi.org/10.1007/s11224-011-9826-8
  45. Y. Zhang, D. Tao, F. Xu, T. Li, A low-cost and high-performance rechargeable magnesium battery based on povidone iodine cathode. Chem. Eng. J. 427, 131592 (2022). https://doi.org/10.1016/j.cej.2021.131592
  46. W. Shang, Q. Li, F. Jiang, B. Huang, J. Song, B. Zn et al., I2 battery’s performance by coating a zeolite-based cation-exchange protecting layer. Nano-Micro Lett. 14, 82 (2022). https://doi.org/10.1007/s40820-022-00825-5
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