Issue

Vol. 14 (2022)

Fabricating Na/In/C Composite Anode with Natrophilic Na–In Alloy Enables Superior Na Ion Deposition in the EC/PC Electrolyte

https://doi.org/10.1007/s40820-021-00756-7
Hui Wang
Key Laboratory of Material Physics of Ministry of Education, School of Physics and Microelectronics, Zhengzhou University, Zhengzhou 450052, People’s Republic of China
Yan Wu
Department of Chemistry, Center of Super‑Diamond and Advanced Films (COSDAF), City University of Hong Kong, Hong Kong SAR 999077, People’s Republic of China
Ye Wang
Key Laboratory of Material Physics of Ministry of Education, School of Physics and Microelectronics, Zhengzhou University, Zhengzhou 450052, People’s Republic of China
Tingting Xu
Key Laboratory of Material Physics of Ministry of Education, School of Physics and Microelectronics, Zhengzhou University, Zhengzhou 450052, People’s Republic of China
Dezhi Kong
Key Laboratory of Material Physics of Ministry of Education, School of Physics and Microelectronics, Zhengzhou University, Zhengzhou 450052, People’s Republic of China
Yang Jiang
School of Materials Science and Engineering, Hefei University of Technology, Hefei 230009, Anhui, People’s Republic of China
Di Wu
Key Laboratory of Material Physics of Ministry of Education, School of Physics and Microelectronics, Zhengzhou University, Zhengzhou 450052, People’s Republic of China
Yongbing Tang
Shenzhen Institutes of Advanced Technology, Chinese Academy of Sciences, Shenzhen 518055, People’s Republic of China
Xinjian Li
Key Laboratory of Material Physics of Ministry of Education, School of Physics and Microelectronics, Zhengzhou University, Zhengzhou 450052, People’s Republic of China
Chun‑Sing Lee
Department of Chemistry, Center of Super‑Diamond and Advanced Films (COSDAF), City University of Hong Kong, Hong Kong SAR 999077, People’s Republic of China

Corresponding Author: Chun‑Sing Lee

apcslee@cityu.edu.hk

Nano-Micro Letters, Vol. 14 (2022), Article Number: 23

Abstract

In conventional ethylene carbonate (EC)/propylene carbonate (PC) electrolyte, sodium metal reacts spontaneously and deleteriously with solvent molecules. This significantly limits the practical feasibility of high-voltage sodium metal batteries based on Na metal chemistry. Herein, we present a sodium metal alloy strategy via introducing NaIn and Na2In phases in a Na/In/C composite, aiming at boosting Na ion deposition stability in the common EC/PC electrolyte. Symmetric cells with Na/In/C electrodes achieve an impressive long-term cycling capability at 1 mA cm−2 (> 870 h) and 5 mA cm−2 (> 560 h), respectively, with a capacity of 1 mAh cm−2. In situ optical microscopy clearly unravels a stable Na ion dynamic deposition process on the Na/In/C composite electrode surface, attributing to a dendrite-free and smooth morphology. Furthermore, theoretical simulations reveal intrinsic mechanism for the reversible Na ion deposition behavior with the composite Na/In/C electrode. Upon pairing with a high-voltage NaVPOF cathode, Na/In/C anode illustrates a better suitability in SMBs. This work promises an alternative alloying strategy for enhancing Na metal interfacial stability in the common EC/PC electrolyte for their future applications.


Highlights:


1 Na/In/C composite anode tailored with natrophilic NaIn and Na2In phases was constructed via a facile molten metal immersion method.
2 Long-term Na ion plating/stripping stability in the common ethylene carbonate/propylene carbonate electrolyte was achieved with Na/In/C anode.
3 Na ion deposition reversibility of Na/In/C anode was analyzed by in situ microscope, ab initial molecular dynamics and finite element simulations.

Keywords

EC/PC electrolyte Sodium metal batteries Na/In/C electrode Dendrite-free and smooth morphology Theoretical simulations
Wang, Hui, Yan Wu, Ye Wang, Tingting Xu, Dezhi Kong, Yang Jiang, Di Wu, Yongbing Tang, Xinjian Li, and Chun‑Sing Lee. 2021. “Fabricating Na/In/C Composite Anode With Natrophilic Na–In Alloy Enables Superior Na Ion Deposition in the EC/PC Electrolyte”. Nano-Micro Letters 14 (December):23. https://doi.org/10.1007/s40820-021-00756-7.
Download Citation
Endnote/Zotero/Mendeley (RIS)
BibTeX
References
  1. X. Zhang, K. Chen, Z. Sun, G. Hu, R. Xiao et al., Structure-related electrochemical performance of organosulfur compounds for lithium–sulfur batteries. Energy Environ. Sci. 13(4), 1076–1095 (2020). https://doi.org/10.1039/C9EE03848E
  2. L. Hencz, H. Chen, H.Y. Ling, Y. Wang, C. Lai et al., Housing sulfur in polymer composite frameworks for Li–S batteries. Nano Micro Lett. 11, 17 (2019). https://doi.org/10.1007/s40820-019-0249-1
  3. J. Wang, Z. Zhang, X. Yan, S. Zhang, Z. Wu et al., Rational design of porous N-Ti3C2 MXene@CNT Microspheres for high cycling stability in Li–S battery. Nano-Micro Lett. 12, 4 (2019). https://doi.org/10.1007/s40820-019-0341-6
  4. R. Wang, R. Wu, C. Ding, Z. Chen, H. Xu et al., Porous carbon architecture assembled by cross-linked carbon leaves with implanted atomic cobalt for high-performance Li–S batteries. Nano Micro Lett. 13, 151 (2021). https://doi.org/10.1007/s40820-021-00676-6
  5. Q. Xiong, G. Huang, X.B. Zhang, High-capacity and stable Li-O2 batteries enabled by a trifunctional soluble redox mediator. Angew. Chem. Int. Ed. 132(43), 19473–19481 (2020). https://doi.org/10.1002/ange.202009064
  6. Q. Lv, Z. Zhu, S. Zhao, L. Wang, Q. Zhao et al., Semiconducting metal–organic polymer nanosheets for a photoinvolved Li–O2 battery under visible light. J. Am. Chem. Soc. 143(4), 1941–1947 (2021). https://doi.org/10.1021/jacs.0c11400
  7. S.H. Wang, J. Yue, W. Dong, T.T. Zuo, J.Y. Li et al., Tuning wettability of molten lithium via a chemical strategy for lithium metal anodes. Nat. Commun. 10, 4930 (2019). https://doi.org/10.1038/s41467-019-12938-4
  8. C. Jin, T. Liu, O. Sheng, M. Li, T. Liu et al., Rejuvenating dead lithium supply in lithium metal anodes by iodine redox. Nat. Energy 6, 378–387 (2021). https://doi.org/10.1038/s41560-021-00789-7
  9. T. Li, J. Sun, S. Gao, B. Xiao, J. Cheng et al., Superior sodium metal anodes enabled by sodiophilic carbonized coconut framework with 3D tubular structure. Adv. Energy Mater. 11(7), 2003699 (2021). https://doi.org/10.1002/aenm.202003699
  10. M. Zhu, G. Wang, X. Liu, B. Guo, G. Xu et al., Dendrite-free sodium metal anodes enabled by a sodium benzenedithiolate-Rich protection layer. Angew. Chem. Int. Ed. 132(16), 6596–6600 (2020). https://doi.org/10.1002/ange.201916716
  11. X. Zheng, C. Bommier, W. Luo, L. Jiang, Y. Hao et al., Sodium metal anodes for room-temperature sodium-ion batteries: applications, challenges and solutions. Energy Storage Mater. 16, 6–23 (2019). https://doi.org/10.1016/j.ensm.2018.04.014
  12. M. Guo, H. Dou, W. Zhao, X. Zhao, B. Wan et al., Three dimensional frameworks of super ionic conductor for thermodynamically and dynamically favorable sodium metal anode. Nano Energy 70, 104479 (2020). https://doi.org/10.1016/j.nanoen.2020.104479
  13. T. Yang, B. Guo, W. Du, M.K. Aslam, M. Tao et al., Design and construction of sodium polysulfides defense system for room-temperature Na–S battery. Adv. Sci. 6(23), 1901557 (2019). https://doi.org/10.1002/advs.201901557
  14. H. Wang, Y. Jiang, A. Manthiram, Long cycle life, low self-discharge sodium–selenium batteries with high selenium loading and suppressed polyselenide shuttling. Adv. Energy Mater. 8(7), 1701953 (2018). https://doi.org/10.1002/aenm.201701953
  15. T. Wu, M. Jing, L. Yang, G. Zou, H. Hou et al., Controllable chain-length for covalent sulfur–carbon materials enabling stable and high-capacity sodium storage. Adv. Energy Mater. 9(9), 1803478 (2019). https://doi.org/10.1002/aenm.201803478
  16. L. Zeng, W. Zeng, Y. Jiang, X. Wei, W. Li et al., A flexible porous carbon nanofibers-selenium cathode with superior electrochemical performance for both Li-Se and Na-Se batteries. Adv. Energy Mater. 5(4), 1401377 (2015). https://doi.org/10.1002/aenm.201401377
  17. L. Wang, X. Chen, S. Li, J. Yang, Y. Sun et al., Effect of eutectic accelerator in selenium-doped sulfurized polyacrylonitrile for high performance room temperature sodium–sulfur batteries. J. Mater. Chem. A 7(20), 12732–12739 (2019). https://doi.org/10.1039/C9TA02831E
  18. L. Fan, R. Ma, Y. Yang, S. Chen, B. Lu, Covalent sulfur for advanced room temperature sodium-sulfur batteries. Nano Energy 28, 304–310 (2016). https://doi.org/10.1016/j.nanoen.2016.08.056
  19. X. Zhao, L. Yin, T. Zhang, M. Zhang, Z. Fang et al., Heteroatoms dual-doped hierarchical porous carbon-selenium composite for durable Li–Se and Na–Se batteries. Nano Energy 49, 137–146 (2018). https://doi.org/10.1016/j.nanoen.2018.04.045
  20. Z. Li, J. Zhang, Y. Lu, X.W. Lou, A pyrolyzed polyacrylonitrile/selenium disulfide composite cathode with remarkable lithium and sodium storage performances. Sci. Adv. 4(6), eaat1687 (2018). Doi: https://doi.org/10.1126/sciadv.aat1687
  21. G. Fang, Q. Wang, J. Zhou, Y. Lei, Z. Chen et al., Metal organic framework-templated synthesis of bimetallic selenides with rich phase boundaries for sodium-ion storage and oxygen evolution reaction. ACS Nano 13(5), 5635–5645 (2019). https://doi.org/10.1021/acsnano.9b00816
  22. S.M.B. Khajehbashi, L. Xu, G. Zhang, S. Tan, Y. Zhao et al., High-performance Na–O2 batteries enabled by oriented NaO2 nanowires as discharge products. Nano Lett. 18(6), 3934–3942 (2018). https://doi.org/10.1021/acs.nanolett.8b01315
  23. X. Guo, W. Zhang, J. Zhang, D. Zhou, X. Tang et al., Boosting sodium storage in two-dimensional phosphorene/Ti3C2Tx MXene nanoarchitectures with stable fluorinated interphase. ACS Nano 14(3), 3651–3659 (2020). https://doi.org/10.1021/acsnano.0c00177
  24. Y. Hu, B. Li, X. Jiao, C. Zhang, X. Dai et al., Stable cycling of phosphorus anode for sodium-ion batteries through chemical bonding with sulfurized polyacrylonitrile. Adv. Funct. Mater. 28(23), 1801010 (2018). https://doi.org/10.1002/adfm.201801010
  25. L. Li, Y. Zheng, S. Zhang, J. Yang, Z. Shao et al., Recent progress on sodium ion batteries: potential high-performance anodes. Energy Environ. Sci. 11(9), 2310–2340 (2018). https://doi.org/10.1039/C8EE01023D
  26. B. Han, Y. Zou, Z. Zhang, X. Yang, X. Shi et al., Probing the Na metal solid electrolyte interphase via cryo-transmission electron microscopy. Nat. Commun. 12(1), 3066 (2021). https://doi.org/10.1038/s41467-021-23368-6
  27. Y. Xiang, G. Zheng, Z. Liang, Y. Jin, X. Liu et al., Visualizing the growth process of sodium microstructures in sodium batteries by in-situ 23Na MRI and NMR spectroscopy. Nat. Nanotechnol. 15(10), 883–890 (2020). https://doi.org/10.1038/s41565-020-0749-7
  28. Z. Li, K. Zhu, P. Liu, L. Jiao, 3D confinement strategy for dendrite-free sodium metal batteries. Adv. Energy Mater. 2100359 (2021). Doi: https://doi.org/10.1002/aenm.202100359
  29. X. Shen, R. Zhang, X. Chen, X.B. Cheng, X. Li et al., The failure of solid electrolyte interphase on Li metal anode: structural uniformity or mechanical strength? Adv. Energy Mater. 10(10), 1903645 (2020). https://doi.org/10.1002/aenm.201903645
  30. H. Wang, Z. Tong, R. Yang, Z. Huang, D. Shen et al., Electrochemically stable sodium metal-tellurium/carbon nanorods batteries. Adv. Energy Mater. 9(48), 1903046 (2019). https://doi.org/10.1002/aenm.201903046
  31. L. Zhang, X. Xia, Y. Zhong, D. Xie, S. Liu et al., Exploring self-healing liquid Na–K alloy for dendrite-free electrochemical energy storage. Adv. Mater. 30(46), 1804011 (2018). https://doi.org/10.1002/adma.201804011
  32. A. Wang, X. Hu, H. Tang, C. Zhang, S. Liu et al., Processable and moldable sodium-metal anodes. Angew. Chem. Int. Ed. 56(39), 11921–11926 (2017). https://doi.org/10.1002/ange.201703937
  33. H. Wang, C. Wang, E. Matios, W. Li, Facile stabilization of the sodium metal anode with additives: unexpected key role of sodium polysulfide and adverse effect of sodium nitrate. Angew. Chem. Int. Ed. 130(26), 1–5 (2018). https://doi.org/10.1002/ange.201801818
  34. L. Ye, M. Liao, T. Zhao, H. Sun, Y. Zhao et al., A sodiophilic interphase-mediated, dendrite-free anode with ultrahigh specific capacity for sodium-metal batteries. Angew. Chem. Int. Ed. 131(47), 17210–17216 (2019). https://doi.org/10.1002/ange.201910202
  35. J. Zheng, S. Chen, W. Zhao, J. Song, M.H. Engelhard et al., Extremely stable sodium metal batteries enabled by localized high-concentration electrolytes. ACS Energy Lett. 3(2), 315–321 (2018). https://doi.org/10.1021/acsenergylett.7b01213
  36. Y. Zhao, L.V. Goncharova, A. Lushington, Q. Sun, H. Yadegari et al., Superior stable and long life sodium metal anodes achieved by atomic layer deposition. Adv. Mater. 29(18), 1606663 (2017). https://doi.org/10.1002/adma.201606663
  37. S. Tang, Z. Qiu, X.Y. Wang, Y. Gu, X.G. Zhang et al., A room-temperature sodium metal anode enabled by a sodiophilic layer. Nano Energy 48, 101–106 (2018). https://doi.org/10.1016/j.nanoen.2018.03.039
  38. S. Choudhury, S. Wei, Y. Ozhabes, D. Gunceler, M.J. Zachman et al., Designing solid-liquid interphases for sodium batteries. Nat. Commun. 8(1), 898 (2017). https://doi.org/10.1038/s41467-017-00742-x
  39. H. Shi, M. Yue, C.J. Zhang, Y. Dong, P. Lu et al., 3D flexible, conductive, and recyclable Ti3C2Tx MXene-melamine foam for high-areal-capacity and long-lifetime alkali-metal anode. ACS Nano 14(7), 8678–8688 (2020). https://doi.org/10.1021/acsnano.0c03042
  40. S.S. Chi, X.G. Qi, Y.S. Hu, L.Z. Fan, 3D flexible carbon felt host for highly stable sodium metal anodes. Adv. Energy Mater. 8(15), 1702764 (2018). https://doi.org/10.1002/aenm.201702764
  41. S. Lou, F. Zhang, C. Fu, M. Chen, Y. Ma et al., Interface issues and challenges in all-solid-state batteries: lithium, sodium, and beyond. Adv. Mater. 33(6), 2000721 (2020). https://doi.org/10.1002/adma.202000721
  42. Y. Lu, J.A. Alonso, Q. Yi, L. Lu, Z.L. Wang et al., A high-performance monolithic solid-state sodium battery with Ca2+ doped Na3Zr2Si2PO12 electrolyte. Adv. Mater. 9(28), 1901205 (2019). https://doi.org/10.1002/aenm.201901205
  43. D. Lei, Y.B. He, H. Huang, Y. Yuan, G. Zhong et al., Cross-linked beta alumina nanowires with compact gel polymer electrolyte coating for ultra-stable sodium metal battery. Nat. Commun. 10(1), 4244 (2019). https://doi.org/10.1038/s41467-019-11960-w
  44. J. Zhang, D.W. Wang, W. Lv, L. Qin, S. Niu et al., Ethers illume sodium-based battery chemistry: uniqueness, surprise, and challenges. Adv. Energy Mater. 8(26), 1801361 (2018). https://doi.org/10.1002/aenm.201801361
  45. X. Liu, X. Zheng, Y. Dai, W. Wu, Y. Huang et al., Fluoride-rich solid-electrolyte-interface enabling stable sodium metal batteries in high-safe electrolytes. Adv. Funct. Mater. 31(30), 2103522 (2021). https://doi.org/10.1002/adfm.202103522
  46. P.E. Blöchl, Projector augmented-wave method. Phys. Rev. B 50(24), 17953–17979 (1994). https://doi.org/10.1103/PhysRevB.50.17953
  47. J.P. Perdew, K. Burke, M. Ernzerhof, Generalized gradient approximation made simple. Phys. Rev. Lett. 77(18), 3865–3868 (1996). https://doi.org/10.1103/PhysRevLett.77.3865
  48. S. Grimme, Semiempirical GGA-type density functional constructed with a long-range dispersion correction. J. Comput. Chem. 27(15), 1787–1799 (2006). https://doi.org/10.1002/jcc.20495
  49. J. Hutter, M. Iannuzzi, F. Schiffmann, J. VandeVondele, cp2k: atomistic simulations of condensed matter systems. WIREs Comput. Mol. Sci. 4(1), 15–25 (2014). https://doi.org/10.1002/wcms.1159
  50. G. Yoon, S. Moon, G. Ceder, K. Kang, Deposition and stripping behavior of lithium metal in electrochemical system: continuum mechanics study. Chem. Mater. 30(19), 6769–6776 (2018). https://doi.org/10.1021/acs.chemmater.8b02623
  51. B. Horstmann, J. Shi, R. Amine, M. Werres, X. He et al., Strategies towards enabling lithium metal in batteries: interphases and electrodes. Energy Environ. Sci. (2021). https://doi.org/10.1039/D1EE00767J
  52. B. Lee, E. Paek, D. Mitlin, S.W. Lee, Sodium metal anodes: emerging solutions to dendrite growth. Chem. Rev. 119(9), 5416–5460 (2019). https://doi.org/10.1021/acs.chemrev.8b00642
  53. J. Liu, T. Wu, S. Zhang, D. Li, Y. Wang et al., InBr3 as a self-defensed redox mediator for Li–O2 batteries: in situ construction of a stable indium-rich composite protective layer on the Li anode. J. Power Sources 439, 227095 (2019). https://doi.org/10.1039/D1EE00767J
Read More
Author biographies are not available.
Download this PDF file
PDF SUPPLEMENTARY MATERIAL
Statistic
Read Counter : 5773 Download : 4360

Most read articles by the same author(s)

1 2 > >>