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 Na_0.44MnO₂ in Alkaline Aqueous Solution[J]. Acta Physico-Chimica Sinica, ;2020, 36(5): 190502. doi: 10.3866/PKU.WHXB201905027 shu

Electrochemical Mechanism of Na_0.44MnO₂ in Alkaline Aqueous Solution

Li Hui ¹ ,
Liu Shuangyu ¹ ,
Yuan Tianci ² ,
Wang Bo ¹ ,
Sheng Peng ¹ ,
Xu Li ¹ ,
Zhao Guangyao ¹ ,
Bai Huitao ¹ ,
Chen Xin ¹ ,
Chen Zhongxue ³ ,
Cao Yuliang ^2,,

1.
State Key Laboratory of Advanced Power Transmission Technology, Global Energy Interconnection Research Institute Co. Ltd., Beijing 102211, P. R. China
2.
Hubei Key Laboratory of Electrochemical Power Sources, College of Chemistry and Molecular Sciences, Wuhan University, Wuhan 430072, P. R. China
3.
Key Laboratory of Hydraulic Machinery Transients, Ministry of Education, School of Power and Mechanical Engineering, Wuhan University, Wuhan 430072, P. R. China

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, Na_0.44MnO₂ possesses the most promising prospects due to its low cost, non-toxic nature, simple synthesis, and structural stability. However, the reported capacity of Na_0.44MnO₂ 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-Na_0.44MnO₂ dual-ion battery using Na_0.44MnO₂ 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 Na_0.44MnO₂ 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 Na_0.44MnO₂ 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 Na_0.44MnO₂ 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 Na_0.44MnO₂ electrode during discharge. The results show that the discharge of Na_0.44MnO₂ 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 Na_0.44MnO₂; 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 Na_xMnO₂, and the tunnel structure of Na_xMnO₂ 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 Na_0.44MnO₂, resulting in higher specific capacity. However, the insertion of H⁺ will also cause structural damage, which seriously worsens the cycling stability of the Na_0.44MnO₂ electrode.
- Sodium ion battery,
- Na_0.44MnO₂,
- Alkaline electrolyte,
- Electrochemical mechanism,
- Proton insertion
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
1. [1]
  Qing Xue , Shengyi Li , Yanan Zhao , Peng Sheng , Li Xu , Zhengxi Li , Bo Zhang , Hui Li , Bo Wang , Libin Yang , Yuliang Cao , Zhongxue Chen . Novel Alkaline Sodium-Ion Battery Capacitor Based on Active Carbon||Na_0.44MnO₂ towards Low Cost, High-Rate Capability and Long-Term Lifespan. Acta Physico-Chimica Sinica, 2024, 40(2): 2303041-0. doi: 10.3866/PKU.WHXB202303041
2. [2]
  Jianbao Mei , Bei Li , Shu Zhang , Dongdong Xiao , Pu Hu , Geng Zhang . Enhanced Performance of Ternary NASICON-Type Na_3.5−xMn_0.5V_1.5−xZr_x (PO₄)₃/C Cathodes for Sodium-Ion Batteries. Acta Physico-Chimica Sinica, 2024, 40(12): 2407023-0. doi: 10.3866/PKU.WHXB202407023
3. [3]
  Yuyao Wang , Zhitao Cao , Zeyu Du , Xinxin Cao , Shuquan Liang . Research Progress of Iron-based Polyanionic Cathode Materials for Sodium-Ion Batteries. Acta Physico-Chimica Sinica, 2025, 41(4): 2406014-0. doi: 10.3866/PKU.WHXB202406014
4. [4]
  Yu Guo , Zhiwei Huang , Yuqing Hu , Junzhe Li , Jie Xu . Recent Advances in Iron-based Heterostructure Anode Materials for Sodium Ion Batteries. Acta Physico-Chimica Sinica, 2025, 41(3): 2311015-0. doi: 10.3866/PKU.WHXB202311015
5. [5]
  Zilin Hu , Yaoshen Niu , Xiaohui Rong , Yongsheng Hu . Suppression of Voltage Decay through Ni³⁺ Barrier in Anionic-Redox Active Cathode for Na-Ion Batteries. Acta Physico-Chimica Sinica, 2024, 40(6): 2306005-0. doi: 10.3866/PKU.WHXB202306005
6. [6]
  Zhuo WANG , Xiaotong LI , Zhipeng HU , Junqiao PAN . Three-dimensional porous carbon decorated with nano bismuth particles: Preparation and sodium storage properties. Chinese Journal of Inorganic Chemistry, 2025, 41(2): 267-274. doi: 10.11862/CJIC.20240223
7. [7]
  Zhicheng JU , Wenxuan FU , Baoyan WANG , Ao LUO , Jiangmin JIANG , Yueli SHI , Yongli CUI . MOF-derived nickel-cobalt bimetallic sulfide microspheres coated by carbon: Preparation and long cycling performance for sodium storage. Chinese Journal of Inorganic Chemistry, 2025, 41(4): 661-674. doi: 10.11862/CJIC.20240363
8. [8]
  Xue Xiao , Jiachun Li , Xiangtong Meng , Jieshan Qiu . Sulfur-Doped Carbon-Coated Fe_0.95S_1.05 Nanospheres as Anodes for High-Performance Sodium Storage. Acta Physico-Chimica Sinica, 2024, 40(6): 2307006-0. doi: 10.3866/PKU.WHXB202307006
9. [9]
  Xiting Zhou , Zhipeng Han , Xinlei Zhang , Shixuan Zhu , Cheng Che , Liang Xu , Zhenyu Sun , Leiduan Hao , Zhiyu Yang . Dual Modulation via Ag-Doped CuO Catalyst and Iodide-Containing Electrolyte for Enhanced Electrocatalytic CO₂ Reduction to Multi-Carbon Products: A Comprehensive Chemistry Experiment. University Chemistry, 2025, 40(7): 336-344. doi: 10.12461/PKU.DXHX202412070
10. [10]
  Jiandong Liu , Xin Li , Daxiong Wu , Huaping Wang , Junda Huang , Jianmin Ma . Anion-Acceptor Electrolyte Additive Strategy for Optimizing Electrolyte Solvation Characteristics and Electrode Electrolyte Interphases for Li||NCM811 Battery. Acta Physico-Chimica Sinica, 2024, 40(6): 2306039-0. doi: 10.3866/PKU.WHXB202306039
11. [11]
  Feiya Cao , Qixin Wang , Pu Li , Zhirong Xing , Ziyu Song , Heng Zhang , Zhibin Zhou , Wenfang Feng . Magnesium-Ion Conducting Electrolyte Based on Grignard Reaction: Synthesis and Properties. University Chemistry, 2024, 39(3): 359-368. doi: 10.3866/PKU.DXHX202308094
12. [12]
  Hao Chen , Dongyue Yang , Gang Huang , Xinbo Zhang . Progress on Liquid Organic Electrolytes of Li-O₂ Batteries. Acta Physico-Chimica Sinica, 2024, 40(7): 2305059-0. doi: 10.3866/PKU.WHXB202305059
13. [13]
  Qianli Ma , Tianbing Song , Tianle He , Xirong Zhang , Huanming Xiong . Sulfur-doped carbon dots: a novel bifunctional electrolyte additive for high-performance aqueous zinc-ion batteries. Acta Physico-Chimica Sinica, 2025, 41(9): 100106-0. doi: 10.1016/j.actphy.2025.100106
14. [14]
  Aoyu Huang , Jun Xu , Yu Huang , Gui Chu , Mao Wang , Lili Wang , Yongqi Sun , Zhen Jiang , Xiaobo Zhu . Tailoring Electrode-Electrolyte Interfaces via a Simple Slurry Additive for Stable High-Voltage Lithium-Ion Batteries. Acta Physico-Chimica Sinica, 2025, 41(4): 2408007-0. doi: 10.3866/PKU.WHXB202408007
15. [15]
  Jiahe LIU , Gan TANG , Kai CHEN , Mingda ZHANG . Effect of low-temperature electrolyte additives on low-temperature performance of lithium cobaltate batteries. Chinese Journal of Inorganic Chemistry, 2025, 41(4): 719-728. doi: 10.11862/CJIC.20250023
16. [16]
  Zhuo Han , Danfeng Zhang , Haixian Wang , Guorui Zheng , Ming Liu , Yanbing He . Research Progress and Prospect on Electrolyte Additives for Interface Reconstruction of Long-Life Ni-Rich Lithium Batteries. Acta Physico-Chimica Sinica, 2024, 40(9): 2307034-0. doi: 10.3866/PKU.WHXB202307034
17. [17]
  Rui Yang , Hui Li , Qingfei Meng , Wenjie Li , Jiliang Wu , Yongjin Fang , Chi Huang , Yuliang Cao . Influence of PC-based Electrolyte on High-Rate Performance in Li/CrO_x Primary Battery. Acta Physico-Chimica Sinica, 2024, 40(9): 2308053-0. doi: 10.3866/PKU.WHXB202308053
18. [18]
  Lingbang Qiu , Jiangmin Jiang , Libo Wang , Lang Bai , Fei Zhou , Gaoyu Zhou , Quanchao Zhuang , Yanhua Cui . In Situ Electrochemical Impedance Spectroscopy Monitoring of the High-Temperature Double-Discharge Mechanism of Nb₁₂WO₃₃ Cathode Material for Long-Life Thermal Batteries. Acta Physico-Chimica Sinica, 2025, 41(5): 100040-0. doi: 10.1016/j.actphy.2024.100040
19. [19]
  Zhuo Wang , Xue Bai , Kexin Zhang , Hongzhi Wang , Jiabao Dong , Yuan Gao , Bin Zhao . MOF-Templated Synthesis of Nitrogen-Doped Carbon for Enhanced Electrochemical Sodium Ion Storage and Removal. Acta Physico-Chimica Sinica, 2025, 41(3): 2405002-0. doi: 10.3866/PKU.WHXB202405002
20. [20]
  Qingtang ZHANG , Xiaoyu WU , Zheng WANG , Xiaomei WANG . Performance of nano Li₂FeSiO₄/C cathode material co-doped by potassium and chlorine ions. Chinese Journal of Inorganic Chemistry, 2024, 40(9): 1689-1696. doi: 10.11862/CJIC.20240115

Get Citation

PDF

XML

Metrics

PDF Downloads(18)
Abstract views(1386)
HTML views(256)

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142

Electrochemical Mechanism of Na0.44MnO2 in Alkaline Aqueous Solution

Metrics

通讯作者: 陈斌, bchen63@163.com

Electrochemical Mechanism of Na_0.44MnO₂ in Alkaline Aqueous Solution