Fundamental Understanding of Hydrogen Evolution Reaction on Zinc Anode Surface: A First-Principles Study

doi:10.1007/s40820-024-01337-0

Abstract

Abstract:

Hydrogen evolution reaction (HER) has become a key factor affecting the cycling stability of aqueous Zn-ion batteries, while the corresponding fundamental issues involving HER are still unclear. Herein, the reaction mechanisms of HER on various crystalline surfaces have been investigated by first-principle calculations based on density functional theory. It is found that the Volmer step is the rate-limiting step of HER on the Zn (002) and (100) surfaces, while, the reaction rates of HER on the Zn (101), (102) and (103) surfaces are determined by the Tafel step. Moreover, the correlation between HER activity and the generalized coordination number ($\overline{CN }$) of Zn at the surfaces has been revealed. The relatively weaker HER activity on Zn (002) surface can be attributed to the higher $\overline{CN }$ of surface Zn atom. The atomically uneven Zn (002) surface shows significantly higher HER activity than the flat Zn (002) surface as the $\overline{CN }$ of the surface Zn atom is lowered. The $\overline{CN }$ of surface Zn atom is proposed as a key descriptor of HER activity. Tuning the $\overline{CN }$ of surface Zn atom would be a vital strategy to inhibit HER on the Zn anode surface based on the presented theoretical studies. Furthermore, this work provides a theoretical basis for the in-depth understanding of HER on the Zn surface.

Key words: Aqueous Zn-ion battery, Zn anode, Hydrogen evolution reaction, Coordination number, First-principles calculation

Xiaoyu Liu, Yiming Guo, Fanghua Ning, Yuyu Liu, Siqi Shi, Qian Li, Jiujun Zhang, Shigang Lu, Jin Yi. Fundamental Understanding of Hydrogen Evolution Reaction on Zinc Anode Surface: A First-Principles Study[J]. Nano-Micro Letters, 2024, 16(1): 111-.

Xiaoyu Liu, Yiming Guo, Fanghua Ning, Yuyu Liu, Siqi Shi, Qian Li, Jiujun Zhang, Shigang Lu, Jin Yi. [J]. Nano-Micro Letters, 2024, 16(1): 111-.

/ / Recommend / Download Citations

URL: https://www.qk.sjtu.edu.cn/nml/EN/10.1007/s40820-024-01337-0

https://www.qk.sjtu.edu.cn/nml/EN/Y2024/V16/I1/111

Figures/Tables 6

Fig. 1 a The surface energies of the crystal surfaces of Zn metal with different Miller indices. b The $\Delta {G}_{{{\text{H}}}^{*}}$ for H atom adsorbed at different sites of the crystal surfaces of zinc metal

Fig. 2 Hydrogen adsorption energy ($\Delta {G}_{{{\text{H}}}^{*}}$) at several crystal surfaces of the zinc anode as a function of different hydrogen coverage. The H coverage indicates the number of hydrogens absorbed per unit area

Fig. 3 The energy barriers and reaction pathways of Volmer step on several crystal surface of Zn anode. a Zn (002) surface, b Zn (100) surface, c Zn (101) surface, d Zn (102) surface, e Zn (103) surface, f the comparative Volmer reaction barriers. The insets are the structures of corresponding initial, transition, and final states. The white, red, and grey spheres are H, O, and Zn atoms, respectively. The blue spheres are the protons that are willing to adsorb at the surfaces

Fig. 4 The energy barriers and reaction pathways of Tafel step on several crystal surface of Zn anode. a Zn (002) surface, b Zn (100) surface, c Zn (101) surface, d Zn (102) surface, e Zn (103) surface, f the comparative Tafel reaction barriers. The insets are the structures of corresponding initial, transition, and final states. The white and grey spheres are H and Zn atoms, respectively

Fig. 5 The schematic diagram of the $\overline{CN }$ of Zn atom at several crystal surface of Zn anode. a Zn (002) surface, b Zn (100) surface, c Zn (101) surface, d Zn (102) surface, e Zn (103) surface, f the correlation between the hydrogen adsorption energy and the $\overline{CN }$

Fig. 6 a Schematic diagram of uneven (002) and (100) surface. b Hydrogen adsorption energy of H adsorbed on surface Zn atom with different $\overline{CN }$

References 53

1.	Z. Li, A.W. Robertson, Electrolyte engineering strategies for regulation of the Zn metal anode in aqueous Zn-ion batteries. Battery Energy 2(1), 20220029 (2023). https://doi.org/10.1002/bte2.20220029
2.	C. Nie, G. Wang, D. Wang, M. Wang, X. Gao et al., Recent progress on Zn anodes for advanced aqueous zinc-ion batteries. Adv. Energy Mater. 13(28), 2300606 (2023). https://doi.org/10.1002/aenm.202300606
3.	B. Li, X. Zhang, T. Wang, Z. He, B. Lu et al., Interfacial engineering strategy for high-performance Zn metal anodes. Nano-Micro Lett. 14, 6 (2021). https://doi.org/10.1007/s40820-021-00764-7
4.	Q. Wen, H. Fu, R.-D. Cui, H.-Z. Chen, R.-H. Ji et al., Recent advances in interfacial modification of zinc anode for aqueous rechargeable zinc ion batteries. J. Energy Chem. 83, 287-303 (2023). https://doi.org/10.1016/j.jechem.2023.03.059
5.	N.S. Alghamdi, M. Rana, X. Peng, Y. Huang, J. Lee et al., Zinc-bromine rechargeable batteries: From device configuration, electrochemistry, material to performance evaluation. Nano-Micro Lett. 15, 209 (2023). https://doi.org/10.1007/s40820-023-01174-7
6.	J.Y. Kim, G. Liu, R.E.A. Ardhi, J. Park, H. Kim et al., Stable Zn metal anodes with limited Zn-doping in MgF₂ interphase for fast and uniformly ionic flux. Nano-Micro Lett. 14, 46 (2022). https://doi.org/10.1007/s40820-021-00788-z
7.	Y. Liu, Y. Liu, X. Wu, Toward long-life aqueous zinc ion batteries by constructing stable zinc anodes. Chem. Rec. 22, e202200088 (2022). https://doi.org/10.1002/tcr.202200088
8.	H. Yu, D. Chen, T. Zhang, M. Fu, J. Cai et al., Insight on the double-edged sword role of water molecules in the anode of aqueous zinc-ion batteries. Small Struct. 3(12), 2200143 (2022). https://doi.org/10.1002/sstr.202200143
9.	D. Yao, D. Yu, S. Yao, Z. Lu, G. Li et al., Interfacial engineering boosts highly reversible zinc metal for aqueous zinc-ion batteries. ACS Appl. Mater. Interfaces 15(13), 16584-16592 (2023). https://doi.org/10.1021/acsami.2c20075
10.	L. Wang, W. Huang, W. Guo, Z.H. Guo, C. Chang et al., Sn alloying to inhibit hydrogen evolution of Zn metal anode in rechargeable aqueous batteries. Adv. Funct. Mater. 32(1), 2108533 (2022). https://doi.org/10.1002/adfm.202108533
11.	J. Chen, W. Zhao, J. Jiang, X. Zhao, S. Zheng et al., Challenges and perspectives of hydrogen evolution-free aqueous Zn-ion batteries. Energy Storage Mater. 59, 102767 (2023). https://doi.org/10.1016/j.ensm.2023.04.006
12.	C.-C. Kao, C. Ye, J. Hao, J. Shan, H. Li et al., Suppressing hydrogen evolution via anticatalytic interfaces toward highly efficient aqueous Zn-ion batteries. ACS Nano 17(4), 3948-3957 (2023). https://doi.org/10.1021/acsnano.2c12587
13.	A. Bayaguud, Y. Fu, C. Zhu, Interfacial parasitic reactions of zinc anodes in zinc ion batteries: Underestimated corrosion and hydrogen evolution reactions and their suppression strategies. J. Energy Chem. 64, 246-262 (2022). https://doi.org/10.1016/j.jechem.2021.04.016
14.	Q. Yang, L. Li, T. Hussain, D. Wang, L. Hui et al., Stabilizing interface pH by N-modified graphdiyne for dendrite-free and high-rate aqueous Zn-ion batteries. Angew. Chem. Int. Ed. 61(6), e202112304 (2022). https://doi.org/10.1002/anie.202112304
15.	Y. Gong, B. Wang, H. Ren, D. Li, D. Wang et al., Recent advances in structural optimization and surface modification on current collectors for high-performance zinc anode: Principles, strategies, and challenges. Nano-Micro Lett. 15, 208 (2023). https://doi.org/10.1007/s40820-023-01177-4
16.	J. Hao, L. Yuan, Y. Zhu, M. Jaroniec, S.-Z. Qiao, Triple-function electrolyte regulation toward advanced aqueous Zn-ion batteries. Adv. Mater. 34(44), e2206963 (2022). https://doi.org/10.1002/adma.202206963
17.	J. Yang, B. Yin, Y. Sun, H. Pan, W. Sun et al., Zinc anode for mild aqueous zinc-ion batteries: Challenges, strategies, and perspectives. Nano-Micro Lett. 14, 42 (2022). https://doi.org/10.1007/s40820-021-00782-5
18.	C. Yan, Y. Wang, X. Deng, Y. Xu, Cooperative chloride hydrogel electrolytes enabling ultralow-temperature aqueous zinc ion batteries by the hofmeister effect. Nano-Micro Lett. 14, 98 (2022). https://doi.org/10.1007/s40820-022-00836-2
19.	H. Jin, S. Dai, K. Xie, Y. Luo, K. Liu et al., Regulating interfacial desolvation and deposition kinetics enables durable Zn anodes with ultrahigh utilization of 80%. Small 18(4), e2106441 (2022). https://doi.org/10.1002/smll.202106441
20.	X. Lu, C. Zhao, A. Chen, Z. Guo, N. Liu et al., Reducing Zn-ion concentration gradient by SO₄^2--immobilized interface coating for dendrite-free Zn anode. Chem. Eng. J. 451, 138772 (2023). https://doi.org/10.1016/j.cej.2022.138772
21.	K. Wu, J. Yi, X. Liu, Y. Sun, J. Cui et al., Regulating Zn deposition via an artificial solid-electrolyte interface with aligned dipoles for long life Zn anode. Nano-Micro Lett. 13, 79 (2021). https://doi.org/10.1007/s40820-021-00599-2
22.	M. Fayette, H.J. Chang, X. Li, D. Reed, High-performance InZn alloy anodes toward practical aqueous zinc batteries. ACS Energy Lett. 7(6), 1888-1895 (2022). https://doi.org/10.1021/acsenergylett.2c00843
23.	Y. Zhang, X. Yang, Y. Hu, K. Hu, X. Lin et al., Highly strengthened and toughened Zn-Li-Mn alloys as long-cycling life and dendrite-free Zn anode for aqueous zinc-ion batteries. Small 18(17), e2200787 (2022). https://doi.org/10.1002/smll.202200787
24.	H. Meng, Q. Ran, T.-Y. Dai, H. Shi, S.-P. Zeng et al., Surface-alloyed nanoporous zinc as reversible and stable anodes for high-performance aqueous zinc-ion battery. Nano-Micro Lett. 14, 128 (2022). https://doi.org/10.1007/s40820-022-00867-9
25.	C. Han, W. Li, H.K. Liu, S. Dou, J. Wang, Principals and strategies for constructing a highly reversible zinc metal anode in aqueous batteries. Nano Energy 74, 104880 2020). https://doi.org/10.1016/j.nanoen.2020.104880
26.	Z. Zhu, H. Jin, K. Xie, S. Dai, Y. Luo et al., Molecular-level Zn-ion transfer pump specifically functioning on (002) facets enables durable Zn anodes. Small 18(49), e2204713 (2022). https://doi.org/10.1002/smll.202204713
27.	Z. Hu, F. Zhang, A. Zhou, X. Hu, Q. Yan et al., Highly reversible Zn metal anodes enabled by increased nucleation overpotential. Nano-Micro Lett. 15, 171 (2023). https://doi.org/10.1007/s40820-023-01136-z
28.	X. Song, L. Bai, C. Wang, D. Wang, K. Xu et al., Synergistic cooperation of Zn(002)texture and amorphous zinc phosphate for dendrite-free Zn anodes. ACS Nano 17(15), 15113-15124 (2023). https://doi.org/10.1021/acsnano.3c04343
29.	Y. Hao, D. Feng, L. Hou, T. Li, Y. Jiao et al., Gel electrolyte constructing Zn (002) deposition crystal plane toward highly stable Zn anode. Adv. Sci. 9(7), e2104832 (2022). https://doi.org/10.1002/advs.202104832
30.	M. Zhou, S. Guo, J. Li, X. Luo, Z. Liu et al., Surface-preferred crystal plane for a stable and reversible zinc anode. Adv. Mater. 33(21), e2100187 (2021). https://doi.org/10.1002/adma.202100187
31.	S. Hu, W.-X. Li, Sabatier principle of metal-support interaction for design of ultrastable metal nanocatalysts. Science 374(6573), 1360-1365 (2021). https://doi.org/10.1126/science.abi9828
32.	Z.W. Seh, J. Kibsgaard, C.F. Dickens, I. Chorkendorff, J.K. Nørskov et al., Combining theory and experiment in electrocatalysis: Insights into materials design. Science 355(6312), eaad4998 (2017). https://doi.org/10.1126/science.aad4998
33.	R. Parsons, The rate of electrolytic hydrogen evolution and the heat of adsorption of hydrogen. Trans. Faraday Soc. 54, 1053-1063 (1958). https://doi.org/10.1039/TF9585401053
34.	J.K. Nørskov, T. Bligaard, A. Logadottir, J.R. Kitchin, J.G. Chen et al., Trends in the exchange current for hydrogen evolution. J. Electrochem. Soc. 152, J23 (2005). https://doi.org/10.1149/1.1856988
35.	R. Kronberg, K. Laasonen, Reconciling the experimental and computational hydrogen evolution activities of Pt(111) through DFT-based constrained MD simulations. ACS Catal. 11(13), 8062-8078 (2021). https://doi.org/10.1021/acscatal.1c00538
36.	L. Kristinsdóttir, E. Skúlason, A systematic DFT study of hydrogen diffusion on transition metal surfaces. Surf. Sci. 606(17-18), 1400-1404 (2012). https://doi.org/10.1016/j.susc.2012.04.028
37.	J. Hafner, Ab-initio simulations of materials using VASP: Density-functional theory and beyond. J. Comput. Chem. 29(13), 2044-2078 (2008). https://doi.org/10.1002/jcc.21057
38.	J.P. Perdew, K. Burke, M. Ernzerhof, Generalized gradient approximation made simple. Phys. Rev. Lett. 77, 3865-3868 (1996). https://doi.org/10.1103/PhysRevLett.77.3865
39.	X.-G. Xiong, T. Yanai, Projector augmented wave method incorporated into gauss-type atomic orbital based density functional theory. J. Chem. Theory Comput. 13(7), 3236-3249 (2017). https://doi.org/10.1021/acs.jctc.7b00404
40.	G. Henkelman, B.P. Uberuaga, H. Jónsson, A climbing image nudged elastic band method for finding saddle points and minimum energy paths. J. Chem. Phys. 113(22), 9901-9904 (2000). https://doi.org/10.1063/1.1329672
41.	G. Henkelman, H. Jónsson, A dimer method for finding saddle points on high dimensional potential surfaces using only first derivatives. J. Chem. Phys. 111(15), 7010-7022 (1999). https://doi.org/10.1063/1.480097
42.	F. Calle-Vallejo, J.I. Martínez, J.M. García-Lastra, P. Sautet, D. Loffreda, Fast prediction of adsorption properties for platinum nanocatalysts with generalized coordination numbers. Angew. Chem. Int. Ed. 53(32), 8316-8319 (2014). https://doi.org/10.1002/anie.201402958
43.	R. Tran, Z. Xu, B. Radhakrishnan, D. Winston, W. Sun et al., Surface energies of elemental crystals. Sci. Data 3, 160080 2016). https://doi.org/10.1038/sdata.2016.80
44.	A. Aramata, S. Taguchi, T. Fukuda, M. Nakamura, G. Horányi, Underpotential deposition of zinc ions at single crystal electrodes and the effect of the adsorbed anions. Electrochim. Acta 44, 999-1007 (1998). https://doi.org/10.1016/S0013-4686(98)00204-7
45.	P. Lindgren, G. Kastlunger, A.A. Peterson, A challenge to the G - 0 interpretation of hydrogen evolution. ACS Catal. 10(1), 121-128 (2020). https://doi.org/10.1021/acscatal.9b02799
46.	G. Feng, F. Ning, J. Song, H. Shang, K. Zhang et al., Sub-2 nm ultrasmall high-entropy alloy nanoparticles for extremely superior electrocatalytic hydrogen evolution. J. Am. Chem. Soc. 143(41), 17117-17127 (2021). https://doi.org/10.1021/jacs.1c07643
47.	E. Skúlason, V. Tripkovic, M.E. Björketun, S. Gudmundsdóttir, G. Karlberg et al., Modeling the electrochemical hydrogen oxidation and evolution reactions on the basis of density functional theory calculations. J. Phys. Chem. C 114(42), 18182-18197 (2010). https://doi.org/10.1021/jp1048887
48.	H. Cao, Q. Wang, Z. Zhang, H.M. Yan, H. Zhao et al., Engineering single-atom electrocatalysts for enhancing kinetics of acidic Volmer reaction. J. Am. Chem. Soc. 145(24), 13038-13047 (2023). https://doi.org/10.1021/jacs.2c13418
49.	R. Kronberg, H. Lappalainen, K. Laasonen, Revisiting the Volmer-Heyrovský mechanism of hydrogen evolution on a nitrogen doped carbon nanotube: constrained molecular dynamics versus the nudged elastic band method. Phys. Chem. Chem. Phys. 22(19), 10536-10549 (2020). https://doi.org/10.1039/C9CP06474E
50.	Y. Tian, J. Hong, D. Cao, S. You, Y. Song et al., Visualizing Eigen/Zundel cations and their interconversion in monolayer water on metal surfaces. Science 377(6603), 315-319 (2022). https://doi.org/10.1126/science.abo0823
51.	D. Yuan, J. Zhao, H. Ren, Y. Chen, R. Chua et al., Anion texturing towards dendrite-free Zn anode for aqueous rechargeable batteries. Angew. Chem. Int. Ed. 60(13), 7213-7219 (2021). https://doi.org/10.1002/anie.202015488
52.	J. Zhang, W. Huang, L. Li, C. Chang, K. Yang et al., Nonepitaxial electrodeposition of (002)-textured Zn anode on textureless substrates for dendrite-free and hydrogen evolution-suppressed Zn batteries. Adv. Mater. 35(21), e2300073 (2023). https://doi.org/10.1002/adma.202300073
53.	X. Zhang, J. Li, D. Liu, M. Liu, T. Zhou et al., Ultra-long-life and highly reversible Zn metal anodes enabled by a desolvation and deanionization interface layer. Energy Environ. Sci. 14(5), 3120-3129 (2021). https://doi.org/10.1039/D0EE03898A

[1]	YU Xiaokang (俞小康), YE Jia (叶佳), WU Chunxiang (吴春祥), MA Guohong∗ (马国红). Effect of Cu Addition on the Microstructure and Mechanical Properties of U-MIG Welds on Galvanized Steel Sheets [J]. J Shanghai Jiaotong Univ Sci, 2021, 26(6): 757-764.
[2]	Yizhe Li, Yajie Li, Hao Sun, Liyao Gao, Xiangrong Jin, Yaping Li, Zhi LV, Lijun Xu, Wen Liu, Xiaoming Sun. Current Status and Perspectives of Dual-Atom Catalysts Towards Sustainable Energy Utilization [J]. Nano-Micro Letters, 2024, 16(1): 139-.
[3]	Xiang Gao, Shicheng Dai, Yun Teng, Qing Wang, Zhibo Zhang, Ziyin Yang, Minhyuk Park, Hang Wang, Zhe Jia, Yunjiang Wang, Yong Yang. Ultra-Efficient and Cost-Effective Platinum Nanomembrane Electrocatalyst for Sustainable Hydrogen Production [J]. Nano-Micro Letters, 2024, 16(1): 108-.

Please choose a citation manager

Content to export