Citation: Li Hui, Liu Shuangyu, Yuan Tianci, Wang Bo, Sheng Peng, Xu Li, Zhao Guangyao, Bai Huitao, Chen Xin, Chen Zhongxue, Cao Yuliang. Electrochemical Mechanism of Na0.44MnO2 in Alkaline Aqueous Solution[J]. Acta Physico-Chimica Sinica, ;2020, 36(5): 190502. doi: 10.3866/PKU.WHXB201905027 shu

Electrochemical Mechanism of Na0.44MnO2 in Alkaline Aqueous Solution

  • Corresponding author: Cao Yuliang, ylcao@whu.edu.cn
  • Received Date: 6 May 2019
    Revised Date: 2 June 2019
    Accepted Date: 3 June 2019
    Available Online: 10 May 2019

    Fund Project: the Science and Technology Project of State Grid, China SGRIDGKJ[2017]841the National Key Research Program of China 2016YFB0901500The project was supported by the Science and Technology Project of State Grid, China (SGRIDGKJ[2017]841), the National Key Research Program of China (2016YFB0901500) and the National Natural Science Foundation of China (21875171, 21673165)the National Natural Science Foundation of China 21673165the National Natural Science Foundation of China 21875171

  • In recent years, aqueous sodium-ion batteries (ASIBs) have experienced rapid development, and a series of cathode materials for ASIBs has been widely reported. Among these, Na0.44MnO2 possesses the most promising prospects due to its low cost, non-toxic nature, simple synthesis, and structural stability. However, the reported capacity of Na0.44MnO2 in aqueous electrolyte was ~40 mAh·g−1 (less than its theoretical capacity of 121 mAh·g−1), which limits its practical applications. Recently, we developed a novel alkaline Zn-Na0.44MnO2 dual-ion battery using Na0.44MnO2 as the cathode, a Zn metal sheet as the anode, and a 6 mol L−1 NaOH aqueous solution as the electrolyte. In this system, the Na0.44MnO2 electrode presented excellent electrochemical performance with high reversible capacity (80.2 mAh·g−1 at 0.5C) and outstanding cycling stability (73% capacity retention over 1000 cycles at 10C) in alkaline aqueous electrolyte. When the negative potential window was extended to 0.3 V, the Na0.44MnO2 electrode delivered an incredibly high capacity of 345.5 mAh·g−1, which far exceeded the theoretical capacity, but the cycling performance was extremely poor. In that study, X-ray diffraction (XRD) and inductively coupled plasma-atomic emission spectrometry (ICP-AES) analyses revealed that de-intercalation of Na+ and formation of Mn(OH)2 occurred during the discharge process, but the detailed electrochemical mechanism and structural evolution of this process remained unclear. In this study, we used ICP-AES to analyze the elemental composition of discharge products at different discharge depths and found that a small amount of Na+ ions extracted from Na0.44MnO2 electrode since Discharge-120 (corresponding to the discharge capacity of 120 mAh·g−1), and the extraction rate increased gradually with increasing discharge depth. Scanning electron microscope (SEM) and XRD analyses were also carried out to characterize the morphology and phase changes of Na0.44MnO2 electrode during discharge. The results show that the discharge of Na0.44MnO2 electrode in the voltage range 1.95–0.3 V could be divided into the three following steps: (1) the potential range above 1.0 V: Na+ ions de-intercalate reversibly into the tunnel structure of Na0.44MnO2; this discharge mechanism is consistent with that in non-aqueous and neutral aqueous sodium ion batteries. (2) The initial platform region at 1.0 V: in this step, protons (H+) began to insert into the Na+-vacancies in NaxMnO2, and the tunnel structure of NaxMnO2 was still maintained. (3) Subsequent slope region: when the Na+-vacancies in the tunnel structure were fully occupied by protons, further intercalation led to intensification of charge repulsion in the crystal structure. Thus, the tunnel structure collapsed to form a new Mn(OH)2 phase, accompanied by the release of Na+ from the structure. H+ has a smaller radius than Na+; therefore, it could insert into the smaller vacancies in Na0.44MnO2, resulting in higher specific capacity. However, the insertion of H+ will also cause structural damage, which seriously worsens the cycling stability of the Na0.44MnO2 electrode.
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    1. [1]

      Fang, Y.; Zhang, J.; Xiao, L.; Ai, X.; Cao, Y.; Yang, H. Adv. Sci. 2017, 4 (5), 1600392. doi: 10.1002/advs.201600392  doi: 10.1002/advs.201600392

    2. [2]

      Fang, Y.; Chen, Z.; Xiao, L.; Ai, X.; Cao, Y.; Yang, H. Small 2018, 14 (9), 1703116. doi: 10.1002/smll.201703116  doi: 10.1002/smll.201703116

    3. [3]

      Li, F.; Zhou, Z. Small 2018, 14 (6), 1702961. doi: 10.1002/smll.201702961  doi: 10.1002/smll.201702961

    4. [4]

      Bin, D.; Wang, F.; Tamirat, A. G.; Suo, L.; Wang, Y.; Wang, C.; Xia, Y. Adv. Energy Mater. 2018, 8 (17), 1703008. doi: 10.1002/aenm.201703008  doi: 10.1002/aenm.201703008

    5. [5]

      Ding, J.; Hu, W.; Paek, E.; Mitlin, D. Chem. Rev. 2018, 118 (14), 6457. doi: 10.1021/acs.chemrev.8b00116  doi: 10.1021/acs.chemrev.8b00116

    6. [6]

      Qian, J.; Wu, C.; Cao, Y.; Ma, Z.; Huang, Y.; Ai, X.; Yang, H. Adv. Energy Mater. 2018, 8 (17), 1702619. doi: 10.1002/aenm.201702619  doi: 10.1002/aenm.201702619

    7. [7]

      Cao, Y.; Xiao, L.; Wang, W.; Choi, D.; Nie, Z.; Yu, J.; Saraf, L. V.; Yang, Z.; Liu, J. Adv. Mater. 2011, 23 (28), 3155. doi: 10.1002/adma.201100904  doi: 10.1002/adma.201100904

    8. [8]

      Kim, H.; Kim, D. J.; Seo, D. H.; Yeom, M. S.; Kang, K.; Kim, D. K.; Jung, Y. Chem. Mater. 2012, 24 (6), 1205. doi: 10.1021/cm300065y  doi: 10.1021/cm300065y

    9. [9]

      Fu, B.; Zhou, X.; Wang, Y. J. Power Sources 2016, 310, 102. doi: 10.1016/j.jpowsour.2016.01.101  doi: 10.1016/j.jpowsour.2016.01.101

    10. [10]

      Liu, Q.; Hu, Z.; Chen, M.; Gu, Q.; Dou, Y.; Sun, Z.; Chou, S.; Dou, S. X. ACS Appl. Mater. Inter. 2017, 9 (4), 3644. doi: 10.1021/acsami.6b13830  doi: 10.1021/acsami.6b13830

    11. [11]

      Whitacre, J. F.; Tevar, A.; Sharma, S. Electrochem. Commun. 2010, 12 (3), 463. doi: 10.1016/j.elecom.2010.01.020  doi: 10.1016/j.elecom.2010.01.020

    12. [12]

      Kim, D. J.; Ponraj, R.; Kannan, A. G.; Lee, H. W.; Fathi, R.; Ruffo, R.; Mari, C. M.; Kim, D. K. J. Power Sources 2013, 244, 758. doi: 10.1016/j.jpowsour.2013.02.090  doi: 10.1016/j.jpowsour.2013.02.090

    13. [13]

      Li, Z.; Young, D.; Xiang, K.; Carter, W. C.; Chiang, Y. M. Adv. Energy Mater. 2013, 3 (3), 290. doi: 10.1002/aenm.201200598  doi: 10.1002/aenm.201200598

    14. [14]

      Wang, Y.; Liu, J.; Lee, B.; Qiao, R.; Yang, Z.; Xu, S.; Yu, X.; Gu, L.; Hu, Y. S.; Yang, W.; et al. Nat. Commun. 2015, 6, 6401. doi: 10.1038/ncomms7401  doi: 10.1038/ncomms7401

    15. [15]

      Yuan, T.; Zhang, J.; Pu, X.; Chen, Z.; Tang, C.; Zhang, X.; Ai, X.; Huang, Y.; Yang, H.; Cao, Y. ACS Appl. Mater. Inter. 2018, 10 (40), 34108. doi: 10.1021/acsami.8b08297  doi: 10.1021/acsami.8b08297

    16. [16]

      Xiao, Y.; Wang, P. F.; Yin, Y. X.; Zhu, Y. F.; Yang, X.; Zhang, X. D.; Wang, Y.; Guo, X. D.; Zhong, B. H.; Guo, Y. G. Adv. Energy Mater. 2018, 8 (22), 1800492. doi: 10.1002/aenm.201800492  doi: 10.1002/aenm.201800492

    17. [17]

      Chen, Z.; Yuan, T.; Pu, X.; Yang, H.; Ai, X.; Xia, Y.; Cao, Y. ACS Appl. Mater. Inter. 2018, 10 (14), 11689. doi: 10.1021/acsami.8b00478  doi: 10.1021/acsami.8b00478

    18. [18]

      He, X.; Wang, J.; Qiu, B.; Paillard, E.; Ma, C.; Cao, X.; Liu, H.; Stan, M. C.; Liu, H.; Gallash, T.; et al. Nano Energy 2016, 27, 602. doi: 10.1016/j.nanoen.2016.07.021  doi: 10.1016/j.nanoen.2016.07.021

    19. [19]

      Luo, J. Y.; Cui, W. J.; He, P.; Xia, Y. Y. Nat. Chem. 2010, 2, 760. doi: 10.1038/nchem.763  doi: 10.1038/nchem.763

    20. [20]

      Choi, J.; Alvarez, E.; Arunkumar, T.A.; Manthiram, A. Electrochem. Solid St. 2006, 9 (5), A241. doi: 10.1149/1.2184495  doi: 10.1149/1.2184495

    21. [21]

      Manthiram, A.; Choi, J. J. Power Sources 2006, 159 (1), 249. doi: 10.1016/j.jpowsour.2006.04.028  doi: 10.1016/j.jpowsour.2006.04.028

    22. [22]

      Wang, Y. G.; Luo, J. Y.; Wang, C. X.; Xia, Y. Y. J. Electrochem. Soc. 2006, 153 (8), A1425. doi: 10.1149/1.2203772  doi: 10.1149/1.2203772

    23. [23]

      Hertzberg, B. J.; Huang, A.; Hsieh, A.; Chamoun, M.; Davies, G.; Seo, J. K.; Zhong, Z.; Croft, M.; Erdonmez, C.; Meng, Y. S.; et al. Chem. Mater. 2016, 28 (13), 4536. doi: 10.1021/acs.chemmater.6b00232  doi: 10.1021/acs.chemmater.6b00232

    24. [24]

      Pan, H.; Shao, Y.; Yan, P.; Cheng, Y.; Han, K. S.; Nie, Z.; Wang, C.; Yang, J.; Li, X.; Bhattacharya, P.; et al. Nat. Energy 2016, 1 (5), 16039. doi: 10.1038/nenergy.2016.39  doi: 10.1038/nenergy.2016.39

    25. [25]

      Sun, W.; Wang, F.; Hou, S.; Yang, C.; Fan, X.; Ma, Z.; Gao, T.; Han, F.; Hu, R.; Zhu, M.; et al. J. Am. Chem. Soc. 2017, 139 (29), 9775. doi: 10.1021/jacs.7b04471  doi: 10.1021/jacs.7b04471

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