Citation: Zongyuan You, Wei Hua, Na Li, Huanyan Liu, Jian-Gan Wang. An in-depth mechanistic insight into the redox reaction and degradation of aqueous Zn-MnO₂ batteries[J]. Chinese Chemical Letters, ;2023, 34(4): 107525. doi: 10.1016/j.cclet.2022.05.039 shu

An in-depth mechanistic insight into the redox reaction and degradation of aqueous Zn-MnO₂ batteries

State Key Laboratory of Solidication Processing, Center for Nano Energy Materials, School of Materials Science and Engineering, Northwestern Polytechnical University, Shaanxi Joint Lab of Graphene (NPU), Xi'an 710072, China

wangjiangan@nwpu.edu.cn

Received Date: 19 April 2022
Revised Date: 6 May 2022
Accepted Date: 12 May 2022
Available Online: 16 May 2022

Figures(5)

Rechargeable aqueous Zn/MnO₂ batteries raise massive research activities in recent years. However, both the working principle and the degradation mechanism of this battery chemistry are still under debate. Herein, we provide an in-depth electrochemical and structural investigation on this controversial issue based on α-MnO₂ crystalline nanowires. Mechanistic analysis substantiates a two-electron reaction pathway of Mn²⁺/Mn⁴⁺ redox couple from part of MnO₂ accompanying with a reversible precipitation/dissolution of flaky zinc sulfate hydroxide (ZSH) during the discharge/charge processes. The formation of the ZSH layer is double-edged, which passivates the deep dissolution of MnO₂ upon discharging, but promotes the electrochemical deposition kinetics of active MnO₂ upon charging. The cell degradation originates primarily from the corrosion failure of metallic zinc anode and the accumulation of irreversible ZnMn₂O₄ phases on the cathode. The addition of MnSO₄ to the electrolyte could afford supplementary capacity contribution via electro-oxidation of Mn²⁺. However, a high MnSO₄ concentration will expedite the cell failure by corroding the metallic zinc anodes. The present study will shed a fundamental insight on developing new strategies toward practically viable Zn/MnO₂ batteries.
- Zinc-ion battery,
- MnO₂ cathode,
- Working mechanism,
- Degradation mechanism,
- Zinc anode
1. [1]
  B. Dunn, H. Kamath, J.M. Tarascon, Science 334 (2011) 928–935. doi: 10.1126/science.1212741
2. [2]
  Z. Yang, J. Zhang, M. Kintner-Meyer, et al., Chem. Rev. 111 (2011) 3577–3613. doi: 10.1021/cr100290v
3. [3]
  S. Chu, Y. Cui, N. Liu, Nat. Mater. 16 (2016) 16–22.
4. [4]
  J. Ming, J. Guo, C. Xia, et al., Mater. Sci. Eng. R 135 (2019) 58–84. doi: 10.1016/j.mser.2018.10.002
5. [5]
  H. Liu, J.G. Wang, Z. You, et al., Mater. Today 42 (2021) 73–98. doi: 10.1016/j.mattod.2020.08.021
6. [6]
  L.E. Blanc, D. Kundu, L.F. Nazar, Joule 4 (2020) 771–799. doi: 10.1016/j.joule.2020.03.002
7. [7]
  M. Song, H. Tan, D. Chao, et al., Adv. Funct. Mater. 28 (2018) 1802564. doi: 10.1002/adfm.201802564
8. [8]
  A. Konarov, N. Voronina, J.H. Jo, et al., ACS Energy Lett. 3 (2018) 2620–2640. doi: 10.1021/acsenergylett.8b01552
9. [9]
  B. Tang, L. Shan, S. Liang, et al., Energy Environ. Sci. 12 (2019) 3288–3304. doi: 10.1039/C9EE02526J
10. [10]
  X. Jia, C. Liu, Z.G. Neale, et al., Chem. Rev. 120 (2020) 7795–7866. doi: 10.1021/acs.chemrev.9b00628
11. [11]
  K.W. Nam, H. Kim, J.H. Choic, et al., Energy Environ. Sci. 12 (2019) 1999–2009. doi: 10.1039/C9EE00718K
12. [12]
  L. Su, L. Liu, Y. Wang, et al., Chin. Chem. Lett. 31 (2020) 2358–2364. doi: 10.1016/j.cclet.2020.03.014
13. [13]
  C. Xu, B. Li, H. Du, et al., Angew. Chem. Int. Ed. 51 (2012) 933–935. doi: 10.1002/anie.201106307
14. [14]
  M.H. Alfaruqi, V. Mathew, J. Gim, et al., Chem. Mater. 27 (2015) 3609–3620. doi: 10.1021/cm504717p
15. [15]
  Z. Hou, M. Dong, Y. Xiong, et al., Small (2020) 2001228. doi: 10.1002/smll.202001228
16. [16]
  H. Pan, Y. Shao, P. Yan, et al., Nat. Energy 1 (2016) 16039. doi: 10.1038/nenergy.2016.39
17. [17]
  W. Sun, F. Wang, S. Hou, et al., J. Am. Chem. Soc. 139 (2017) 9775–9778. doi: 10.1021/jacs.7b04471
18. [18]
  J. Wang, J.G. Wang, H. Liu, et al., Adv. Funct. Mater. 31 (2020) 2007397.
19. [19]
  X.Z. Zhai, J. Qu, J. Wang, et al., Energy Storage Mater. 42 (2021) 753–763. doi: 10.1016/j.ensm.2021.08.021
20. [20]
  X. Guo, J. Zhou, C. Bai, et al., Mater. Today Energy 16 (2020) 100396. doi: 10.1016/j.mtener.2020.100396
21. [21]
  B. Lee, H.R. Seo, H.R. Lee, et al., ChemSusChem 9 (2016) 2948–2956. doi: 10.1002/cssc.201600702
22. [22]
  J. Yang, J. Cao, Y. Peng, et al., ChemSusChem 13 (2020) 4103. doi: 10.1002/cssc.202001216
23. [23]
  N. Zhang, F. Cheng, J. Liu, et al., Nat. Commun. 8 (2017) 405–415. doi: 10.1038/s41467-017-00467-x
24. [24]
  S. Lian, C. Sun, W. Xu, et al., Nano Energy 62 (2019) 79–84. doi: 10.1016/j.nanoen.2019.04.038
25. [25]
  D. Wang, L. Wang, G. Liang, et al., ACS Nano 13 (2019) 10643–10652. doi: 10.1021/acsnano.9b04916
26. [26]
  G. Fang, C. Zhu, M. Chen, et al., Adv. Funct. Mater. 29 (2019) 1808375. doi: 10.1002/adfm.201808375
27. [27]
  J. Huang, Z. Wang, M. Hou, et al., Nat. Commun. 9 (2018) 2906. doi: 10.1038/s41467-018-04949-4
28. [28]
  J. Wang, J.G. Wang, X. Qin, et al., ACS Appl. Mater. Interfaces 12 (2020) 34949–34958. doi: 10.1021/acsami.0c08812
29. [29]
  T. Zhang, Y. Tang, G. Fang, et al., Adv. Funct. Mater. (2020) 2002711. doi: 10.1002/adfm.202002711
30. [30]
  S. Zhao, B. Han, D. Zhang, et al., J. Mater. Chem. A 6 (2018) 5733–5739. doi: 10.1039/C8TA01031E
31. [31]
  B. Lee, H.R. Lee, H. Kim, et al., Chem. Commun. 51 (2015) 9265–9268. doi: 10.1039/C5CC02585K
32. [32]
  J. Wang, J.G. Wang, H. Liu, et al., J. Mater. Chem. A 7 (2019) 13727–13735. doi: 10.1039/C9TA03541A
33. [33]
  X. Zhu, Z. Cao, W. Wang, et al., ACS Nano 15 (2021) 2971–2983. doi: 10.1021/acsnano.0c09205
34. [34]
  X.Z. Zhai, J. Qu, S.M. Hao, et al., Nano Micro Lett. 12 (2020) 56. doi: 10.1007/s40820-020-0397-3
35. [35]
  T. Sun, Q. Nian, S. Zheng, et al., Small 16 (2020) 2000597. doi: 10.1002/smll.202000597
36. [36]
  M.H. Alfaruqi, J. Gim, S. Kim, et al., J. Power Sources 288 (2015) 320–327. doi: 10.1016/j.jpowsour.2015.04.140
37. [37]
  Y. Zeng, X. Zhang, Y. Meng, et al., Adv. Mater. 29 (2017) 1700274. doi: 10.1002/adma.201700274
38. [38]
  M. Toupin, T. Brousse, D. Bélanger, Chem. Mater. 16 (2004) 3184–3190. doi: 10.1021/cm049649j
39. [39]
  Y. Hou, Y. Cheng, T. Hobson, et al., Nano Lett. 10 (2010) 2727–2733. doi: 10.1021/nl101723g
40. [40]
  G. Fang, J. Zhou, A. Pan, et al., ACS Energy Lett. 3 (2018) 2480–2501. doi: 10.1021/acsenergylett.8b01426
41. [41]
  Y. Huang, J. Mou, W. Liu, et al., Nano Micro Lett. 11 (2019) 49–56. doi: 10.1007/s40820-019-0278-9
42. [42]
  Y. Zhong, X. Xu, J. Veder, et al., iScience 23 (2020) 100943. doi: 10.1016/j.isci.2020.100943
43. [43]
  S.H. Kim, S.M. Oh, J. Power Sources 72 (1998) 150–158. doi: 10.1016/S0378-7753(97)02703-1
44. [44]
  Q. Chen, J. Jin, Z. Kou, et al., Small 16 (2020) 2000091. doi: 10.1002/smll.202000091
45. [45]
  F. Kataoka, T. Ishida, K. Nagita, et al., ACS Appl. Energy Mater. 3 (2020) 4720–4726. doi: 10.1021/acsaem.0c00357
46. [46]
  J. Huang, X. Tang, K. Liu, et al., Mater. Today Energy 17 (2020) 100475. doi: 10.1016/j.mtener.2020.100475
47. [47]
  X. Gao, H. Wu, W. Li, et al., Small 16 (2020) 1905842. doi: 10.1002/smll.201905842
48. [48]
  S.D. Han, S. Kim, D. Li, et al., Chem. Mater. 29 (2017) 4874–4884. doi: 10.1021/acs.chemmater.7b00852
49. [49]
  L. Ma, M.A. Schroeder, O. Borodin, et al., Nat. Energy 5 (2020) 743–749. doi: 10.1038/s41560-020-0674-x
50. [50]
  X. Han, H. Leng, Y. Qi, et al., Chem. Eng. J. 431 (2022) 133931. doi: 10.1016/j.cej.2021.133931
51. [51]
  J. Hao, B. Li, X. Li, et al., Adv. Mater. (2020) 2003021. doi: 10.1002/adma.202003021
52. [52]
  L. Wang, G. Fan, J. Liu, et al., Chin. Chem. Lett. 32 (2021) 1095–1110. doi: 10.1016/j.cclet.2020.08.022
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4. [4]
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An in-depth mechanistic insight into the redox reaction and degradation of aqueous Zn-MnO2 batteries

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通讯作者: 陈斌, bchen63@163.com

An in-depth mechanistic insight into the redox reaction and degradation of aqueous Zn-MnO₂ batteries