Citation: Shenglong Tang, Chunlei Wang, Xiangjun Pu, Xiangkui Gu, Zhongxue Chen. Unravelling Zn²⁺ Intercalation Mechanism in TiX₂ (X = S, Se) Anodes for Aqueous Zn-Ion Batteries[J]. Acta Physico-Chimica Sinica, ;2023, 39(8): 221203. doi: 10.3866/PKU.WHXB202212037 shu

Unravelling Zn²⁺ Intercalation Mechanism in TiX₂ (X = S, Se) Anodes for Aqueous Zn-Ion Batteries

1.
Key Laboratory of Hydraulic Machinery Transients, Ministry of Education, School of Power and Mechanical Engineering, Wuhan University, Wuhan 430072, China
2.
Department of Industrial and Systems Engineering, The Hong Kong Polytechnic University, Hong Kong 999077, China

Corresponding author: Zhongxue Chen, zxchen_pmc@whu.edu.cn
Received Date: 23 December 2022
Revised Date: 25 January 2023
Accepted Date: 7 February 2023
Available Online: 14 February 2023
Fund Project: the National Natural Science Foundation of China U22A20438the National Natural Science Foundation of China 21875171

In recent years, increased attention has been paid to aqueous Zn-ion batteries (ZIBs) owing to their low cost, inherent safety, and environmental benignity, which enable them to become promising electrochemical energy storage systems for grid-scale applications. However, some critical issues in zinc metal anode, like zinc dendrites growth, corrosion, and side reactions, act as obstacles to developing aqueous ZIBs. Exploring zinc-storage anodes to replace zinc-metal anodes is proposed as an effective strategy to promote the practical application of ZIBs. Therefore, several transition metal oxides, sulfides, and conductive polymers have been intensively studied as zinc-metal-free anodes. Two-dimensional metal dichalcogenides (TMDs), especially TiX₂ (X = S, Se), are the most appealing candidates because of their sizeable interlayer space and facile 2D ion-transport channels. However, the reaction mechanism of these TiX₂ in ZIBs still needs fundamental study. In this work, density functional theory (DFT) calculations are performed to investigate the behavior of zinc intercalation reaction in TiX₂ systematically. First, the most stable interlayer configurations of zinc-intercalated TiX₂ are characterized by group theory. We define a supercell-dependent group that only involves translation and rotation operation and find that the subgroup of the group that describes the symmetry of the most stable interlayer configurations possesses the highest order. So, the most stable configuration can be fast screened out among thousands of candidates. Calculations based on a series of those stable configurations at different discharge depths reveal the low open circuit voltage (OCV) of < 0.5 V for both Zn_xTiS₂ and Zn_xTiSe₂. The density of states (DOS) result suggests the good electronic conductivity of TiX₂, and the partial density of states (PDOS) result indicates the closed-shell Ti(IV) is reduced to open-shell Ti(III), and the formation of Zn―X bonds as zinc ions intercalate into the interlayer of TiX₂. Interestingly, Bader charge analysis demonstrates that X anions also participate in the redox process during charge and discharge because X gains more negative charge than Ti as zinc intercalates into TiX₂. The climbing image nudged elastic band (CINEB) calculations reveal the low zinc ion diffusion barriers (0.333 and 0.338 eV for TiS₂ and TiSe₂, respectively). This study proves that TiX₂ is suitable as zinc intercalating anode materials for ZIBs and provides new insights into the DFT investigation of other TMDs as high-performance battery materials.
- Zn-ion battery,
- TiX₂ anode,
- First-principle calculation,
- Group theory
1. [1]
  Schmidt, O.; Hawkes, A.; Gambhir, A.; Staffell, I. Nat. Energy 2017, 2, 17110. doi: 10.1038/nenergy.2017.110 doi: 10.1038/nenergy.2017.110
2. [2]
  Li, H.; Liu, S. Y.; Yuan, T. C.; Wang, B.; Sheng, P.; Xu, L.; Zhao, G. Y.; Bai, H. T.; Chen, X.; Chen, Z. X.; et al. Acta Phys. -Chim. Sin. 2021, 37, 1907049. doi: 10.3866/PKU.WHXB201907049
3. [3]
  Wang, H. M.; Chen, S. S.; Fu, C. L.; Ding, Y.; Liu, G. R.; Cao, Y. L.; Chen, Z. X. ACS Mater. Lett. 2021, 3, 956. doi: 10.1021/acsmaterialslett.1c00043 doi: 10.1021/acsmaterialslett.1c00043
4. [4]
  Huang, J. T.; Zhou, J.; Liang, S. Q. Acta Phys. -Chim. Sin. 2021, 37, 2005020. doi: 10.3866/PKU.WHXB202005020
5. [5]
  Dong, C. R.; Xu, F.; Chen, L.; Chen, Z. X.; Cao, Y. L. Small Struct. 2021, 2, 2100001. doi: 10.1002/sstr.202100001 doi: 10.1002/sstr.202100001
6. [6]
  Yan, M. Y.; He, P.; Chen, Y.; Wang, S. Y.; Wei, Q. L.; Zhao, K. N.; Xu, X.; An, Q. Y.; Shuang, Y.; Shao, Y. Y.; et al. Adv. Mater. 2018, 30, 1703725. doi: 10.1002/adma.201703725 doi: 10.1002/adma.201703725
7. [7]
  Cai, Z.; Wang, J. D.; Sun, Y. M. eScience 2023, doi: 10.1016/j.esci.2023.100093 doi: 10.1016/j.esci.2023.100093
8. [8]
  Yang, Q.; Bang, G. J.; Guo, Y.; Liu, Z. X.; Yon, B. X.; Wang, D. H.; Huang, Z. D.; Li, X. L.; Fan, J.; Zhi, C. Y. Adv. Mater. 2019, 31, 1903778. doi: 10.1002/adma.201903778 doi: 10.1002/adma.201903778
9. [9]
  Wang, S. B.; Ran, Q.; Yao, R. Q.; Shi, H.; Wen, Z.; Zhao, M.; Lang, X. Y.; Jiang, Q. Nat. Commun. 2020, 11, 1634. doi: 10.1038/s41467-020-15478-4 doi: 10.1038/s41467-020-15478-4
10. [10]
  Zhao, Z. M.; Zhao, J. W.; Hu, Z. L.; Li, J. D.; Li, J. J.; Zhang, Y. J.; Wang, C.; Cui, G. L. Energy Environ. Sci. 2019, 12, 1938. doi: 10.1039/c9ee00596j doi: 10.1039/c9ee00596j
11. [11]
  Chen, S. S.; Zhao, D.; Chen, L.; Liu, G. R.; Ding, Y.; Cao, Y. L.; Chen, Z. X. Small Struct. 2021, 2, 2100082. doi: 10.1002/sstr.202100082 doi: 10.1002/sstr.202100082
12. [12]
  Zeng, Y. X.; Zhang, X. Y.; Qin, R. F.; Liu, X. Q.; Fang, P. P.; Zheng, D. Z.; Tong, Y. X.; Lu, X. H. Adv. Mater. 2019, 31, 1903675. doi: 10.1002/adma.201903675 doi: 10.1002/adma.201903675
13. [13]
  Zhao, D.; Chen, S. S.; Lai, Y. Y.; Ding, M. Y.; Cao, Y. L.; Chen, Z. X. Nano Energy 2022, 100, 107520. doi: 10.1016/j.nanoen.2022.107520 doi: 10.1016/j.nanoen.2022.107520
14. [14]
  Li, W.; Wang, K.; Cheng, S.; Jiang, K. Adv. Energy Mater. 2019, 9, 1900993. doi: 10.1002/aenm.201900993 doi: 10.1002/aenm.201900993
15. [15]
  Wen, Li.; Wu, Y. N.; Wang, S. L.; Shi, J. J.; Zhang, Q. X.; Zhao, B. T.; Wang, Q.; Zhu, C. J.; Liu, Z. Y.; Zheng, Y. F.; et al. Nano Energy 2022, 93, 106896. doi: 10.1016/j.nanoen.2021.106896 doi: 10.1016/j.nanoen.2021.106896
16. [16]
  Blochl, P. E. Phys. Rev. B 1994, 50, 17953. doi: 10.1103/PhysRevB.50.17953 doi: 10.1103/PhysRevB.50.17953
17. [17]
  Perdew, J. P.; Burke, K.; Ernzerhof, M. Phys. Rev. Lett. 1996, 77, 3865. doi: 10.1103/PhysRevLett.77.3865 doi: 10.1103/PhysRevLett.77.3865
18. [18]
  Sanchez, K.; Palacios, P.; Wahnon, P. Phys. Rev. B 2008, 78, 235121. doi: 10.1103/PhysRevB.78.235121 doi: 10.1103/PhysRevB.78.235121
19. [19]
  Sadeghi, S. N.; Zebarjadi, M.; Esfarjani, K. J. Mater. Chem. C 2019, 7, 7308. doi: 10.1039/c9tc00183b doi: 10.1039/c9tc00183b
20. [20]
  Grimme, S.; Antony, J.; Ehrlich, S.; Krieg, H. J. Chem. Phys. 2010, 132, 154104. doi: 10.1063/1.3382344 doi: 10.1063/1.3382344
21. [21]
  Henkelman, G.; Uberuaga, B. P.; Jonsson, H. J. Chem. Phys. 2000, 113, 9901. doi: 10.1063/1.1329672 doi: 10.1063/1.1329672
22. [22]
  Li, P.; Zheng, X. B.; Yu, H. X.; Zhao, G. Q.; Shu, J.; Xu, X.; Sun, W. P.; Dou, S. X. Energy Storage Mater. 2018, 16, 512. doi: 10.1016/j.ensm.2018.09.014 doi: 10.1016/j.ensm.2018.09.014
23. [23]
  Sun, X. Q.; Bonnick, P.; Nazar, L. F. ACS Energy Lett. 2016, 1, 297. doi: 10.1021/acsenergylett.6b00145 doi: 10.1021/acsenergylett.6b00145
24. [24]
  Zhao, C. Y.; Wang, D. S.; Lian, R. Q.; Kan, D. X.; Dou, Y. Y.; Wang, C. Z.; Chen, G.; Wei, Y. J. Appl. Surf. Sci. 2021, 540, 148314. doi: 10.1016/j.apsusc.2020.148314 doi: 10.1016/j.apsusc.2020.148314
25. [25]
  Kabiraj, A.; Mahapatra, S. Commun. Chem. 2018, 1, 81. doi: 10.1038/s42004-018-0082-3 doi: 10.1038/s42004-018-0082-3
26. [26]
  King'ori, G. W.; Ouma, C. N. M.; Amolo, G. O.; Makau, N. W. Surf. Interfaces 2021, 24, 101036. doi: 10.1016/j.surfin.2021.101036 doi: 10.1016/j.surfin.2021.101036
27. [27]
  Li, L. S.; Xu, S. Z.; Carter, E. A. Chem. Mater. 2021, 32, 10678. doi: 10.1021/acs.chemmater.0c03891 doi: 10.1021/acs.chemmater.0c03891
28. [28]
  Ran, Y. B.; Zou, Z. Y.; Liu, B. NPJ Comput. Mater. 2021, 7, 184. doi: 10.1038/s41524-021-00653-y doi: 10.1038/s41524-021-00653-y
29. [29]
  Wang, Z. Q.; Wang, D.; Zou, Z. Y. Natl. Sci. Rev. 2020, 7, 1768. doi: 10.1093/nsr/nwaa174 doi: 10.1093/nsr/nwaa174
1. [1]
  Yunyu Zhao , Chuntao Yang , Yingjian Yu . A review on covalent organic frameworks for rechargeable zinc-ion batteries. Chinese Chemical Letters, 2024, 35(7): 108865-. doi: 10.1016/j.cclet.2023.108865
2. [2]
  Lumin Zheng , Ying Bai , Chuan Wu . Multi-electron reaction and fast Al ion diffusion of δ-MnO₂ cathode materials in rechargeable aluminum batteries via first-principle calculations. Chinese Chemical Letters, 2024, 35(4): 108589-. doi: 10.1016/j.cclet.2023.108589
3. [3]
  Jie Zhou , Quanyu Li , Xiaomeng Hu , Weifeng Wei , Xiaobo Ji , Guichao Kuang , Liangjun Zhou , Libao Chen , Yuejiao Chen . Water molecules regulation for reversible Zn anode in aqueous zinc ion battery: Mini-review. Chinese Chemical Letters, 2024, 35(8): 109143-. doi: 10.1016/j.cclet.2023.109143
4. [4]
  Haixia Wu , Kailu Guo . Iodized polyacrylonitrile as fast-charging anode for lithium-ion battery. Chinese Chemical Letters, 2024, 35(10): 109550-. doi: 10.1016/j.cclet.2024.109550
5. [5]
  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
6. [6]
  Maitri Bhattacharjee , Rekha Boruah Smriti , R. N. Dutta Purkayastha , Waldemar Maniukiewicz , Shubhamoy Chowdhury , Debasish Maiti , Tamanna Akhtar . Synthesis, structural characterization, bio-activity, and density functional theory calculation on Cu(Ⅱ) complexes with hydrazone-based Schiff base ligands. Chinese Journal of Inorganic Chemistry, 2024, 40(7): 1409-1422. doi: 10.11862/CJIC.20240007
7. [7]
  Yue Qian , Zhoujia Liu , Haixin Song , Ruize Yin , Hanni Yang , Siyang Li , Weiwei Xiong , Saisai Yuan , Junhao Zhang , Huan Pang . Imide-based covalent organic framework with excellent cyclability as an anode material for lithium-ion battery. Chinese Chemical Letters, 2024, 35(6): 108785-. doi: 10.1016/j.cclet.2023.108785
8. [8]
  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
9. [9]
  Yu-Yu Tan , Lin-Heng He , Wei-Min He . Copper-mediated assembly of SO₂F group via radical fluorine-atom transfer strategy. Chinese Chemical Letters, 2024, 35(9): 109986-. doi: 10.1016/j.cclet.2024.109986
10. [10]
  Hengyi ZHU , Liyun JU , Haoyue ZHANG , Jiaxin DU , Yutong XIE , Li SONG , Yachao JIN , Mingdao ZHANG . Efficient regeneration of waste LiNi_0.5Co_0.2Mn_0.3O₂ cathode toward high-performance Li-ion battery. Chinese Journal of Inorganic Chemistry, 2025, 41(4): 625-638. doi: 10.11862/CJIC.20240358
11. [11]
  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
12. [12]
  Mianying Huang , Zhiguang Xu , Xiaoming Lin . Mechanistic analysis of Co2VO4/X (X = Ni, C) heterostructures as anode materials of lithium-ion batteries. Chinese Journal of Structural Chemistry, 2024, 43(7): 100309-100309. doi: 10.1016/j.cjsc.2024.100309
13. [13]
  Jinge Zhu , Ailing Tang , Leyi Tang , Peiqing Cong , Chao Li , Qing Guo , Zongtao Wang , Xiaoru Xu , Jiang Wu , Erjun Zhou . Chlorination of benzyl group on the terminal unit of A₂-A₁-D-A₁-A₂ type nonfullerene acceptor for high-voltage organic solar cells. Chinese Chemical Letters, 2025, 36(1): 110233-. doi: 10.1016/j.cclet.2024.110233
14. [14]
  Li Lin , Song-Lin Tian , Zhen-Yu Hu , Yu Zhang , Li-Min Chang , Jia-Jun Wang , Wan-Qiang Liu , Qing-Shuang Wang , Fang Wang . Molecular crowding electrolytes for stabilizing Zn metal anode in rechargeable aqueous batteries. Chinese Chemical Letters, 2024, 35(7): 109802-. doi: 10.1016/j.cclet.2024.109802
15. [15]
  Fuyun Chi , Man Zhang , Yiman Han , Fukui Shen , Shijie Peng , Bo Su , Yuanyuan Hou , Gang Bai . Covalent modulation of mPGES1 activity via α,β-unsaturated aldehyde group: Implications for downregulating PGE2 expression and antipyretic response. Chinese Chemical Letters, 2025, 36(4): 109913-. doi: 10.1016/j.cclet.2024.109913
16. [16]
  Xinpin Pan , Yongjian Cui , Zhe Wang , Bowen Li , Hailong Wang , Jian Hao , Feng Li , Jing Li . Robust chemo-mechanical stability of additives-free SiO₂ anode realized by honeycomb nanolattice for high performance Li-ion batteries. Chinese Chemical Letters, 2024, 35(10): 109567-. doi: 10.1016/j.cclet.2024.109567
17. [17]
  Lin Peng , Xincheng Liang , Zelong Sun , Xingfa Chen , Dexin Meng , Renshu Huang , Qian Liu , Huan Wen , Shibin Yin . Microenvironment regulation of anode-electrolyte interface enables highly stable Zn anodes. Chinese Journal of Structural Chemistry, 2025, 44(4): 100542-100542. doi: 10.1016/j.cjsc.2025.100542
18. [18]
  Xu Huang , Kai-Yin Wu , Chao Su , Lei Yang , Bei-Bei Xiao . Metal-organic framework Cu-BTC for overall water splitting: A density functional theory study. Chinese Chemical Letters, 2025, 36(4): 109720-. doi: 10.1016/j.cclet.2024.109720
19. [19]
  Mei Peng , Wei-Min He . Photochemical synthesis and group transfer reactions of azoxy compounds. Chinese Chemical Letters, 2024, 35(8): 109899-. doi: 10.1016/j.cclet.2024.109899
20. [20]
  Zihao Wang , Jing Xue , Zhicui Song , Jianxiong Xing , Aijun Zhou , Jianmin Ma , Jingze Li . Li-Zn alloy patch for defect-free polymer interface film enables excellent protection effect towards stable Li metal anode. Chinese Chemical Letters, 2024, 35(10): 109489-. doi: 10.1016/j.cclet.2024.109489

Get Citation

PDF

XML

Metrics

PDF Downloads(9)
Abstract views(1050)
HTML views(134)

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

Unravelling Zn2+ Intercalation Mechanism in TiX2 (X = S, Se) Anodes for Aqueous Zn-Ion Batteries

Metrics

通讯作者: 陈斌, bchen63@163.com

Unravelling Zn²⁺ Intercalation Mechanism in TiX₂ (X = S, Se) Anodes for Aqueous Zn-Ion Batteries