Citation: Qinyao Jiang, Binhao Wang, Zerui Yan, Sicheng Fan, Dafu Tang, Biwei Xiao, Qiulong Wei. Unraveling the pseudocapacitive sodium-ion storage mechanism of birnessite in organic electrolytes[J]. Chinese Chemical Letters, ;2025, 36(11): 110416. doi: 10.1016/j.cclet.2024.110416 shu

Unraveling the pseudocapacitive sodium-ion storage mechanism of birnessite in organic electrolytes

Qinyao Jiang ^a ,
Binhao Wang ^a ,
Zerui Yan ^a ,
Sicheng Fan ^a ,
Dafu Tang ^a ,
Biwei Xiao ^{b, *,} ,
Qiulong Wei ^{a, *,}

a.
Department of Materials Science and Engineering, Fujian Key Laboratory of Surface and Interface Engineering for High Performance Materials, College of Materials, Xiamen University, Xiamen 361005, China
b.
GRINM (Guangdong) Research Institute for Advanced Materials and Technology, Foshan 528051, China

xiaobiwei@grinm.com

qlwei@xmu.edu.cn

Received Date: 25 July 2024
Revised Date: 21 August 2024
Accepted Date: 5 September 2024
Available Online: 6 September 2024

Figures(5)

Earth-abundant, layered birnessite is promising cathode for electrochemical capacitors due to the presence of confined nanofluids in interlayers for rapid ion storage. Previous work has demonstrated the capacitive co-intercalation of water and K⁺ ions into birnessite in aqueous electrolytes, but in-depth quantitative investigations of the interactions between confined water and an external organic electrolyte are still lacking. In this work, we reveal the intercalation pseudocapacitance of hydrated birnessite (Na_0.4MnO₂·0.53H₂O) in sodium-based organic electrolytes via operando electrochemical quartz crystal microbalance (EQCM), and ex situ X-ray diffraction and Raman spectroscopy. The Na⁺ ions are completely desolvated at the Na_0.4MnO₂·0.53H₂O-organic electrolyte interfaces and intercalate into the interlayers, while the confined water does not co-extract. The net Na⁺ intercalation is a pseudocapacitive behavior without phase changes, displaying a high capacitive contribution of 85.6% at 1.0 mV/s. Additionally, EQCM results indicate the contributions of cation-dominated electric double layer (EDL) adsorption to the total charge storage. By replacing different solvents and anions in sodium-based organic electrolytes, we verify that Na⁺ pseudocapacitive intercalation dominates the charge storage properties.
- Pseudocapacitance,
- Sodium-ion storage,
- Interlayer confinement,
- Birnessite,
- EQCM
1. [1]
  C. Zhao, Q. Wang, Z. Yao, et al., Science 370 (2020) 708–711. doi: 10.1126/science.aay9972
2. [2]
  S.J. Shin, J.W. Gittins, C.J. Balhatchet, A. Walsh, A.C. Forse, Adv. Funct. Mater. (2023) 2308497. doi: 10.1002/adfm.202308497
3. [3]
  J. Feng, Y. Wang, Y. Xu, et al., Adv. Mater. 33 (2021) 2100887.
4. [4]
  Z. Xiong, P. Guo, Y. Yang, et al., Adv. Energy Mater. 12 (2022) 2103226.
5. [5]
  H. Chen, K. Chen, J. Yang, et al., J. Am. Chem. Soc. 23 (2024) 15751–15760. doi: 10.1021/jacs.4c01395
6. [6]
  J. Zhou, Q. Li, X. Hu, et al., Chin. Chem. Lett. 35 (2024) 109143.
7. [7]
  Y. Wang, Y. Liu, X. Huang, et al., Chin. Chem. Lett. 35 (2024) 109301.
8. [8]
  J. Ding, W. Hu, E. Paek, D. Mitlin, Chem. Rev. 14 (2018) 6457–6498. doi: 10.1021/acs.chemrev.8b00116
9. [9]
  S. Fleischmann, J.B. Mitchell, R. Wang, et al., Chem. Rev 14 (2020) 6738–6782. doi: 10.1021/acs.chemrev.0c00170
10. [10]
  G. Zhang, T. Xiong, L. Xia, et al., Batteries 12 (2022) 252. doi: 10.3390/batteries8120252
11. [11]
  W. van den Bergh, M. Stefik, Adv. Funct. Mater. 31 (2022) 2204126.
12. [12]
  C. Choi, D.S. Ashby, D.M. Butts, et al., Nat. Rev. Mater. 5 (2020) 5–19.
13. [13]
  M. Mateos, N. Makivic, Y. -S. Kim, B. Limoges, V. Balland, Adv. Energy Mater. 23 (2020) 2000332.
14. [14]
  W. Guo, C. Yu, S. Li, et al., Nano Energy 57 (2019) 459–472.
15. [15]
  T. Wang, X. Zhu, S.V. Savilov, S.M. Aldoshin, H. Xia, Funct. Mater. Lett. 14 (2021) 2130013.
16. [16]
  L. Yan, X. Li, H. Pan, ACS Appl. Mater. Interfaces 16 (2024) 26280–26287. doi: 10.1021/acsami.4c04256
17. [17]
  I.I. Misnon, R.A. Aziz, N.K.M. Zain, et al., Mater. Res. Bull. 57 (2014) 221–230.
18. [18]
  S. Boyd, R. Dhall, J.M. LeBeau, V. Augustyn, J. Mater. Chem. A 44 (2018) 22266–22276. doi: 10.1039/c8ta08367c
19. [19]
  S. Boyd, K. Ganeshan, W. -Y. Tsai, et al., Nat. Mater. 20 (2021) 1689–1694. doi: 10.1038/s41563-021-01066-4
20. [20]
  S. Kim, S. Lee, K.W. Nam, et al., Chem. Mater. 28 (2016) 5488–5494. doi: 10.1021/acs.chemmater.6b02083
21. [21]
  E. Bendadesse, A.V. Morozov, A.M. Abakumov, et al., ACS Nano 16 (2022) 14907–14917. doi: 10.1021/acsnano.2c05784
22. [22]
  S.L. Kuo, N.L. Wu, J. Electrochem. Soc. 153 (2006) A1317. doi: 10.1149/1.2197667
23. [23]
  T. Lv, L. Suo, Curr. Opin. Electrochem. 29 (2021) 100818.
24. [24]
  K.W. Nam, S. Kim, E. Yang, et al., Chem. Mater. 27 (2015) 3721–3725. doi: 10.1021/acs.chemmater.5b00869
25. [25]
  Y. Jiang, S. Tan, Q. Wei, et al., J. Mater. Chem. A 6 (2018) 12259–12266. doi: 10.1039/c8ta02516a
26. [26]
  Y. Zhao, Q. Fang, X. Zhu, et al., J. Mater. Chem. A 8 (2020) 8969–8978. doi: 10.1039/d0ta01480j
27. [27]
  W. Gu, G. Lv, L. Liao, et al., J. Hazard. Mater. 338 (2017) 428–436.
28. [28]
  S. Zhu, W. Huo, X. Liu, Y. Zhang, Nanoscale Adv. 2 (2020) 37–54. doi: 10.1039/c9na00547a
29. [29]
  C. Julien, M. Massot, R. Baddour-Hadjean, et al., Solid State Ionics 159 (2003) 345–356.
30. [30]
  M. Najdoski, V. Koleva, A. Samet, J. Phys. Chem. C 118 (2014) 9636–9646. doi: 10.1021/jp4127122
31. [31]
  A.C. Alves, J.P. Correia, T.M. Silva, M.F. Montemor, Electrochim. Acta 454 (2023) 142418.
32. [32]
  W. Zuo, X. Liu, J. Qiu, et al., Nat. Commun. 12 (2021) 4903.
33. [33]
  T. Brezesinski, J. Wang, S.H. Tolbert, B. Dunn, Nat. Mater. 9 (2010) 146–151. doi: 10.1038/nmat2612
34. [34]
  J. Jin, R. Wang, K. Yu, et al., Sep. Purif. Technol. 353 (2025) 128290.
35. [35]
  R. Wang, J. He, C. Yan, et al., Adv. Mater. 36 (2024) 2402681. doi: 10.1002/adma.202402681
36. [36]
  J. Ko, C. Lai, J. Long, et al., ACS Appl. Mater. Interfaces 12 (2020) 14071–14078. doi: 10.1021/acsami.0c02020
37. [37]
  H. Yu, M. Aakyiir, S. Xu, J.D. Whittle, D. Losic, J. Ma, Today Energy 21 (2021) 100757.
38. [38]
  X. Shan, F. Guo, D.S. Charles, et al., Nat. Commun. 10 (2019) 4975.
39. [39]
  P. Xiong, R. Ma, N. Sakai, et al., ACS Appl. Mater. Interfaces 9 (2017) 6282–6291. doi: 10.1021/acsami.6b14612
40. [40]
  H.Y. Asl, A. Manthiram, Science 369 (2020) 140–141. doi: 10.1126/science.abc5454
41. [41]
  Y.K. Hsu, Y.C. Chen, Y.G. Lin, L.C. Chen, K.H. Chen, Chem. Commun. 47 (2011) 1252–1254.
42. [42]
  Q. Zhang, M.D. Levi, Q. Dou, et al., Adv. Energy Mater. 9 (2019) 1802707.
43. [43]
  L. Wang, Y. Lu, J. Liu, et al., Angew. Chem. Int. Ed. 52 (2013) 1964–1967. doi: 10.1002/anie.201206854
44. [44]
  J. Dai, Y. Zhu, H.A. Tahini, et al., Nat. Commun. 11 (2020) 5657.
45. [45]
  L. Gao, J. Chen, Q. Chen, X. Kong, Sci. Adv. 8 (2022) eabm4606.
46. [46]
  X. Li, Z. Ao, J. Liu, et al., ACS Nano 10 (2016) 11532–11540. doi: 10.1021/acsnano.6b07522
47. [47]
  C. Wu, Y. Yang, Y. Zhang, et al., Angew. Chem. Int. Ed. 63 (2024) e202406889.
48. [48]
  L. Sheng, D. Zhu, K. Yang, et al., Nano Lett. 24 (2024) 533–540. doi: 10.1021/acs.nanolett.3c01682
49. [49]
  H. Kim, J. Hong, G. Yoon, et al., Energy Environ. Sci. 8 (2015) 2963–2969.
50. [50]
  F. Zhao, S. Zeng, L. Duan, et al., J. Phys. Chem. C 124 (2020) 28431–28436. doi: 10.1021/acs.jpcc.0c10237
51. [51]
  Y. Ando, M. Okubo, A. Yamada, M. Otani, Adv. Funct. Mater. 30 (2020) 2000820.
52. [52]
  Z. Wen, W. Fang, F. Wang, et al., Angew. Chem. Int. Ed. 63 (2024) e202314876.
53. [53]
  H. He, J. Zhou, L. Yang, et al., J. Mater. Chem. A 12 (2024) 10279–10286. doi: 10.1039/d4ta00701h
1. [1]
  Caili Yang , Tao Long , Ruotong Li , Chunyang Wu , Yuan-Li Ding . Pseudocapacitance dominated Li₃VO₄ encapsulated in N-doped graphene via 2D nanospace confined synthesis for superior lithium ion capacitors. Chinese Chemical Letters, 2025, 36(2): 109675-. doi: 10.1016/j.cclet.2024.109675
2. [2]
  Jun-Ming Cao , Kai-Yang Zhang , Jia-Lin Yang , Zhen-Yi Gu , Xing-Long Wu . Differential bonding behaviors of sodium/potassium-ion storage in sawdust waste carbon derivatives. Chinese Chemical Letters, 2024, 35(4): 109304-. doi: 10.1016/j.cclet.2023.109304
3. [3]
  Xingang Kong , Yabei Su , Cuijuan Xing , Weijie Cheng , Jianfeng Huang , Lifeng Zhang , Haibo Ouyang , Qi Feng . Facile synthesis of porous TiO₂/SnO₂ nanocomposite as lithium ion battery anode with enhanced cycling stability via nanoconfinement effect. Chinese Chemical Letters, 2024, 35(11): 109428-. doi: 10.1016/j.cclet.2023.109428
4. [4]
  Yanxue Wu , Xijun Xu , Shanshan Shi , Fangkun Li , Shaomin Ji , Jingwei Zhao , Jun Liu , Yanping Huo . Facile construction of Cu_2-xSe@C nanobelts as anode for superior sodium-ion storage. Chinese Chemical Letters, 2025, 36(6): 110062-. doi: 10.1016/j.cclet.2024.110062
5. [5]
  Huimin Liu , Kezhi Li , Xin Zhang , Xuemin Yin , Qiangang Fu , Hejun Li . SiC Nanomaterials and Their Derived Carbons for High-Performance Supercapacitors. Acta Physico-Chimica Sinica, 2024, 40(2): 2304026-0. doi: 10.3866/PKU.WHXB202304026
6. [6]
  Yuanhua Xiao , Jinhui Shou , Shiwei Zhang , Ya Shen , Junwei Liu , Dangcheng Su , Yang Kong , Xiaodong Jia , Qingxiang Yang , Shaoming Fang , Xuezhao Wang . Synergistic interlayer confinement and built-in electric field construct reconstruction-inhibited cobalt selenide for robust oxygen evolution at high current density. Chinese Chemical Letters, 2025, 36(11): 111441-. doi: 10.1016/j.cclet.2025.111441
7. [7]
  Jun Dong , Senyuan Tan , Sunbin Yang , Yalong Jiang , Ruxing Wang , Jian Ao , Zilun Chen , Chaohai Zhang , Qinyou An , Xiaoxing Zhang . Spatial confinement of free-standing graphene sponge enables excellent stability of conversion-type Fe₂O₃ anode for sodium storage. Chinese Chemical Letters, 2025, 36(3): 110010-. doi: 10.1016/j.cclet.2024.110010
8. [8]
  Yao Wang , Jun Ouyang , Huadong Yuan , Jianmin Luo , Shihui Zou , Jianwei Nai , Xinyong Tao , Yujing Liu . Impact of local amorphous environment on the diffusion of sodium ions at the solid electrolyte interface in sodium-ion batteries. Chinese Chemical Letters, 2025, 36(10): 110412-. doi: 10.1016/j.cclet.2024.110412
9. [9]
  Shengyu Zhao , Qinhao Shi , Wuliang Feng , Yang Liu , Xinxin Yang , Xingli Zou , Xionggang Lu , Yufeng Zhao . Suppression of multistep phase transitions of O3-type cathode for sodium-ion batteries. Chinese Chemical Letters, 2024, 35(5): 108606-. doi: 10.1016/j.cclet.2023.108606
10. [10]
  Xiping Dong , Xuan Wang , Zhixiu Lu , Qinhao Shi , Zhengyi Yang , Xuan Yu , Wuliang Feng , Xingli Zou , Yang Liu , Yufeng Zhao . Construction of Cu-Zn Co-doped layered materials for sodium-ion batteries with high cycle stability. Chinese Chemical Letters, 2024, 35(5): 108605-. doi: 10.1016/j.cclet.2023.108605
11. [11]
  Shengyu Zhao , Xuan Yu , Yufeng Zhao . A water-stable high-voltage P3-type cathode for sodium-ion batteries. Chinese Chemical Letters, 2024, 35(9): 109933-. doi: 10.1016/j.cclet.2024.109933
12. [12]
  Fan Wu , Shaoyang Wu , Xin Ye , Yurong Ren , Peng Wei . Research progress of high-entropy cathode materials for sodium-ion batteries. Chinese Chemical Letters, 2025, 36(4): 109851-. doi: 10.1016/j.cclet.2024.109851
13. [13]
  Xuan Wang , Peng Sun , Siteng Yuan , Lu Yue , Yufeng Zhao . P2-type low-cost and moisture-stable cathode for sodium-ion batteries. Chinese Chemical Letters, 2025, 36(5): 110015-. doi: 10.1016/j.cclet.2024.110015
14. [14]
  Liangju Zhao , Shiyu Qin , Fei Wu , Limin Zhu , Qing Han , Lingling Xie , Xuejing Qiu , Hongliang Wei , Lanhua Yi , Xiaoyu Cao . Polycarbonyl conjugated porous polyimide as anode materials for high performance sodium-ion batteries. Chinese Chemical Letters, 2025, 36(8): 110246-. doi: 10.1016/j.cclet.2024.110246
15. [15]
  Huifang Ma , Tao Xu , Saifei Yuan , Shujuan Li , Jiayao Wang , Yuping Zhang , Hao Ren , Shulai Lei . Interlayer interactions and electron transfer effects on sodium adsorption on 2D heterostructures surfaces. Chinese Chemical Letters, 2025, 36(8): 110219-. doi: 10.1016/j.cclet.2024.110219
16. [16]
  Fanjun Kong , Yixin Ge , Shi Tao , Zhengqiu Yuan , Chen Lu , Zhida Han , Lianghao Yu , Bin Qian . Engineering and understanding SnS_0.5Se_0.5@N/S/Se triple-doped carbon nanofibers for enhanced sodium-ion batteries. Chinese Chemical Letters, 2024, 35(4): 108552-. doi: 10.1016/j.cclet.2023.108552
17. [17]
  Jiaojiao Liang , Youming Peng , Zhichao Xu , Yufei Wang , Menglong Liu , Xin Liu , Di Huang , Yuehua Wei , Zengxi Wei . Boron/phosphorus co-doped nitrogen-rich carbon nanofiber with flexible anode for robust sodium-ion battery. Chinese Chemical Letters, 2025, 36(1): 110452-. doi: 10.1016/j.cclet.2024.110452
18. [18]
  Huixin Chen , Chen Zhao , Hongjun Yue , Guiming Zhong , Xiang Han , Liang Yin , Ding Chen . Unraveling the reaction mechanism of high reversible capacity CuP₂/C anode with native oxidation PO_x component for sodium-ion batteries. Chinese Chemical Letters, 2025, 36(1): 109650-. doi: 10.1016/j.cclet.2024.109650
19. [19]
  Ruofan Yin , Zhaoxin Guo , Rui Liu , Xian-Sen Tao . Ultrafast synthesis of Na₃V₂(PO₄)₃ cathode for high performance sodium-ion batteries. Chinese Chemical Letters, 2025, 36(2): 109643-. doi: 10.1016/j.cclet.2024.109643
20. [20]
  Fanjun Kong , Jing Zhang , Yuting Tang , Chencheng Sun , Chunfu Lin , Tao Zhang , Wangsheng Chu , Li Song , Liang Zhang , Shi Tao . Introducing high-valence element into P2-type layered cathode material for high-rate sodium-ion batteries. Chinese Chemical Letters, 2025, 36(8): 110993-. doi: 10.1016/j.cclet.2025.110993

Get Citation

PDF

XML

Metrics

PDF Downloads(0)
Abstract views(24)
HTML views(3)

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