Critical Solvation Structures Arrested Active Molecules for Reversible Zn Electrochemistry

doi:10.1007/s40820-024-01361-0

Abstract

Abstract:

Aqueous Zn-ion batteries (AZIBs) have attracted increasing attention in next-generation energy storage systems due to their high safety and economic. Unfortunately, the side reactions, dendrites and hydrogen evolution effects at the zinc anode interface in aqueous electrolytes seriously hinder the application of aqueous zinc-ion batteries. Here, we report a critical solvation strategy to achieve reversible zinc electrochemistry by introducing a small polar molecule acetonitrile to form a “catcher” to arrest active molecules (bound water molecules). The stable solvation structure of [Zn(H₂O)₆]²⁺ is capable of maintaining and completely inhibiting free water molecules. When [Zn(H₂O)₆]²⁺ is partially desolvated in the Helmholtz outer layer, the separated active molecules will be arrested by the “catcher” formed by the strong hydrogen bond N-H bond, ensuring the stable desolvation of Zn²⁺. The Zn||Zn symmetric battery can stably cycle for 2250 h at 1 mAh cm⁻², Zn||V₆O₁₃ full battery achieved a capacity retention rate of 99.2% after 10,000 cycles at 10 A g⁻¹. This paper proposes a novel critical solvation strategy that paves the route for the construction of high-performance AZIBs.

Key words: Zinc-ion battery, Critical solvation, Helmholtz layer, Arrest active molecule, Reversible zinc anode

Junjie Zheng, Bao Zhang, Xin Chen, Wenyu Hao, Jia Yao, Jingying Li, Yi Gan, Xiaofang Wang, Xingtai Liu, Ziang Wu, Youwei Liu, Lin Lv, Li Tao, Pei Liang, Xiao Ji, Hao Wang, Houzhao Wan. Critical Solvation Structures Arrested Active Molecules for Reversible Zn Electrochemistry[J]. Nano-Micro Letters, 2024, 16(1): 145-.

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URL: https://www.qk.sjtu.edu.cn/nml/EN/10.1007/s40820-024-01361-0

https://www.qk.sjtu.edu.cn/nml/EN/Y2024/V16/I1/145

Figures/Tables 5

Fig. 1 a Electroplating mechanism of Zn²⁺ in ZHA 10 electrolytes. b Electron affinity comparison of different solvated sheaths. c Comparison of N-H bond NMR spectra in different electrolytes. d Comparison of infrared spectra in different electrolytes. e Comparison of Raman spectra of C≡N bonds in different electrolytes

Fig. 2 a Solvation structure change process in 1 m Zn(CF₃SO₃)₂-H₂O-ACN_x electrolyte. The solvation effect of different mass fractions of ACN in b ACN, c H₂O, and d Zn(CF₃SO₃)₂ solvent. e Comparison binding energy of 1 m Zn(CF₃SO₃)₂-H₂O-ACN in different states. f Solvation mechanism. Zn²⁺ deposition changes in g ZHA 0, h ZHA 10, and i ZHA > 10 electrolytes

Fig. 3 Cycling comparison of symmetric cells in different electrolytes at 1 mAh cm⁻² and a 1 mA cm⁻², b 0.5 mA cm⁻². c Comparison of the rate performance of symmetric cells in ZHA 0 and ZHA 10 electrolytes. d Comparison of Coulombic efficiencies of different electrolytes for the Cu||Zn half-cell at a current density of 5 mA cm⁻². In e ZHA 0, f ZHA 10, g ZHA 30, the voltage polarization curves corresponding to the coulombic efficiency in the electrolyte. Comparison of different properties under h ZHA 0, i ZHA 10, j ZHA 30 solvation structures

Fig. 4 Comparison of a CV curve, b Tafel curve, c CA curve in ZHA 0 and ZHA 10 electrolytes. In d ZHA 0 and f ZHA 10 electrolytes Zn cross section changes under optical microscope. In e ZHA 0 and g ZHA 10 electrolytes Zn surface changes under 3D confocal laser scanning microscope. h XRD comparison after 100 cycles in different electrolytes. i In-situ Raman map of the Zn||Cu battery at 1 mA cm⁻²

Fig. 5 a CV curve, b fitted b value, c GCD curve, d ratio performance, e long cycle comparison of Zn||V₆O₁₃ battery. f Self-discharge in ZHA 10 electrolytes. g Comparison of cycling ability of Zn||V₆O₁₃ batteries using ZHA 10 electrolyte with other reported. h Soft pack battery lights up the small light

References 63

1.	X. Yu, Z. Li, X. Wu, H. Zhang, Q. Zhao et al., Ten concerns of Zn metal anode for rechargeable aqueous zinc batteries. Joule 7, 1145-1175 (2023). https://doi.org/10.1016/j.joule.2023.05.004
2.	Y. Yang, S. Guo, Y. Pan, B. Lu, S. Liang et al., Dual mechanism of ion (de)intercalation and iodine redox towards advanced zinc batteries. Energy Environ. Sci. 16, 2358-2367 (2023). https://doi.org/10.1039/d3ee00501a
3.	W. Zhou, S. Ding, D. Zhao, D. Chao, An energetic Sn metal aqueous battery. Joule 7, 1104-1107 (2023). https://doi.org/10.1016/j.joule.2023.05.024
4.	D. Wang, D. Lv, H. Peng, C. Wang, H. Liu et al., Solvation modulation enhances anion-derived solid electrolyte interphase for deep cycling of aqueous zinc metal batteries. Angew. Chem. Int. Ed. 62, 2310290 (2023). https://doi.org/10.1002/anie.202310290
5.	Z. Hu, Z. Song, Z. Huang, S. Tao, B. Song et al., Reconstructing hydrogen bond network enables high voltage aqueous zinc-ion supercapacitors. Angew. Chem. Int. Ed. 62, e202309601 (2023). https://doi.org/10.1002/anie.202309601
6.	H. Li, R. Zhao, W. Zhou, L. Wang, W. Li et al., Trade-off between zincophilicity and zincophobicity: toward stable Zn-based aqueous batteries. JACS Au 3, 2107-2116 (2023). https://doi.org/10.1021/jacsau.3c00292
7.	J. Ji, H. Wan, B. Zhang, C. Wang, Y. Gan et al., Co^2+/3+/4+-regulated electron state of Mn-O for superb aqueous zinc-manganese oxide batteries. Adv. Energy Mater. 11, 2003203 (2021). https://doi.org/10.1002/aenm.202003203
8.	Y. Zhong, X. Xie, Z. Zeng, B. Lu, G. Chen et al., Triple-function hydrated eutectic electrolyte for enhanced aqueous zinc batteries. Angew. Chem. Int. Ed. 62, 2310577 (2023). https://doi.org/10.1002/anie.202310577
9.	Z. Meng, Y. Jiao, P. Wu, Alleviating side reactions on Zn anodes for aqueous batteries by a cell membrane derived phosphorylcholine zwitterionic protective layer. Angew. Chem. Int. Ed. 62, 2307271 (2023). https://doi.org/10.1002/anie.202307271
10.	J.W. Choi, D. Aurbach, Promise and reality of post-lithium-ion batteries with high energy densities. Nat. Rev. Mater. 1, 16013 (2016). https://doi.org/10.1038/natrevmats.2016.13
11.	N. Wang, X. Chen, H. Wan, B. Zhang, K. Guan et al., Zincophobic electrolyte achieves highly reversible zinc-ion batteries. Adv. Funct. Mater. 33, 2300795 (2023). https://doi.org/10.1002/adfm.202300795
12.	Z. Xu, H. Xu, J. Sun, J. Wang, D. Zhao et al., Electrolyte strategies toward optimizing Zn anode for zinc-ion batteries. Trans. Tianjin Univ. 29, 407-431 (2023). https://doi.org/10.1007/s12209-023-00373-y
13.	Y. Ma, Q. Zhang, L. Liu, Y. Li, H. Li et al., N, N-dimethylformamide tailors solvent effect to boost Zn anode reversibility in aqueous electrolyte. Natl. Sci. Rev. 9, nwac051 (2022). https://doi.org/10.1093/nsr/nwac051
14.	L.E. Blanc, D. Kundu, L.F. Nazar, Scientific challenges for the implementation of Zn-ion batteries. Joule 4, 771-799 (2020). https://doi.org/10.1016/j.joule.2020.03.002
15.	J. Zheng, P. Shi, C. Chen, X. Chen, Y. Gan et al., Reinforced bonding of Mo-doped MnO₂ with ammonium-ion as cathodes for durable aqueous MnO₂-Zn batteries. Sci. China Mater. 66, 3113-3122 (2023). https://doi.org/10.1007/s40843-023-2448-0
16.	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
17.	W. Zhang, Y. Dai, R. Chen, Z. Xu, J. Li et al., Highly reversible zinc metal anode in a dilute aqueous electrolyte enabled by a pH buffer additive. Angew. Chem. Int. Ed. 62, 2212695 (2023). https://doi.org/10.1002/anie.202212695
18.	H. Zhang, X. Gan, Z. Song, J. Zhou, Amphoteric cellulose-based double-network hydrogel electrolyte toward ultra-stable Zn anode. Angew. Chem. Int. Ed. 62, 2217833 (2023). https://doi.org/10.1002/anie.202217833
19.	Z. Xing, Y. Sun, X. Xie, Y. Tang, G. Xu et al., Zincophilic electrode interphase with appended proton reservoir ability stabilizes Zn metal anodes. Angew. Chem. Int. Ed. 62, 2215324 (2023). https://doi.org/10.1002/anie.202215324
20.	Y. Yang, H. Hua, Z. Lv, M. Zhang, C. Liu et al., Reconstruction of electric double layer for long-life aqueous zinc metal batteries. Adv. Funct. Mater. 33, 2212446 (2023). https://doi.org/10.1002/adfm.202212446
21.	F. Yang, J.A. Yuwono, J. Hao, J. Long, L. Yuan et al., Understanding H₂ evolution electrochemistry to minimize solvated water impact on zinc-anode performance. Adv. Mater. 34, e2206754 (2022). https://doi.org/10.1002/adma.202206754
22.	H. Li, Q. Ma, Y. Yuan, R. Wang, Z. Wang et al., Mesoporous N, S-rich carbon hollow nanospheres controllably prepared from poly(2-aminothiazole) with ultrafast and highly durable potassium storage. Adv. Funct. Mater. (2023). https://doi.org/10.1002/adfm.202301987
23.	T. Wei, Y. Ren, Y. Wang, L.-E. Mo, Z. Li et al., Addition of dioxane in electrolyte promotes (002)-textured zinc growth and suppressed side reactions in zinc-ion batteries. ACS Nano 17, 3765-3775 (2023). https://doi.org/10.1021/acsnano.2c11516
24.	P. Xiong, C. Lin, Y. Wei, J.-H. Kim, G. Jang et al., Charge-transfer complex-based artificial layers for stable and efficient Zn metal anodes. ACS Energy Lett. 8, 2718-2727 (2023). https://doi.org/10.1021/acsenergylett.3c00534
25.	P. Xiong, Y. Kang, H. Yuan, Q. Liu, S.H. Baek et al., Galvanically replaced artificial interfacial layer for highly reversible zinc metal anodes. Appl. Phys. Rev. 9, 011401 (2022). https://doi.org/10.1063/5.0074327
26.	P. Xiong, Y. Zhang, J. Zhang, S.H. Baek, L. Zeng et al., Recent progress of artificial interfacial layers in aqueous Zn metal batteries. EnergyChem 4, 100076 (2022). https://doi.org/10.1016/j.enchem.2022.100076
27.	P. Xiong, Y. Kang, N. Yao, X. Chen, H. Mao et al., Zn-ion transporting, in situ formed robust solid electrolyte interphase for stable zinc metal anodes over a wide temperature range. ACS Energy Lett. 8, 1613-1625 (2023). https://doi.org/10.1021/acsenergylett.3c00154
28.	X. Feng, P. Li, J. Yin, Z. Gan, Y. Gao et al., Enabling highly reversible Zn anode by multifunctional synergistic effects of hybrid solute additives. ACS Energy Lett. 8, 1192-1200 (2023). https://doi.org/10.1021/acsenergylett.2c02455
29.	P. Sun, L. Ma, W. Zhou, M. Qiu, Z. Wang et al., Simultaneous regulation on solvation shell and electrode interface for dendrite-free Zn ion batteries achieved by a low-cost glucose additive. Angew. Chem. Int. Ed. 60, 18247-18255 (2021). https://doi.org/10.1002/anie.202105756
30.	B. Wang, R. Zheng, W. Yang, X. Han, C. Hou et al., Synergistic solvation and interface regulations of eco-friendly silk peptide additive enabling stable aqueous zinc-ion batteries. Adv. Funct. Mater. 32, 2112693 (2022). https://doi.org/10.1002/adfm.202112693
31.	J. Cao, D. Zhang, Y. Yue, R. Chanajaree, S. Wang et al., Regulating solvation structure to stabilize zinc anode by fastening the free water molecules with an inorganic colloidal electrolyte. Nano Energy 93, 106839 (2022). https://doi.org/10.1016/j.nanoen.2021.106839
32.	J. Yin, X. Feng, Z. Gan, Y. Gao, Y. Cheng et al., From anode to cell: Synergistic protection strategies and perspectives for stabilized Zn metal in mild aqueous electrolytes. Energy Storage Mater. 54, 623-640 (2023). https://doi.org/10.1016/j.ensm.2022.11.006
33.	C. Li, A. Shyamsunder, A.G. Hoane, D.M. Long, C.Y. Kwok et al., Highly reversible Zn anode with a practical areal capacity enabled by a sustainable electrolyte and superacid interfacial chemistry. Joule 6, 1103-1120 (2022). https://doi.org/10.1016/j.joule.2022.04.017
34.	D. Xie, Y. Sang, D.-H. Wang, W.-Y. Diao, F.-Y. Tao et al., Frontispiece: ZnF₂-riched inorganic/organic hybrid SEI: in situ-chemical construction and performance-improving mechanism for aqueous zinc-ion batteries. Angew. Chem. Int. Ed. 62, 2380762 (2023). https://doi.org/10.1002/anie.202380762
35.	D. Dong, T. Wang, Y. Sun, J. Fan, Y.-C. Lu, Hydrotropic solubilization of zinc acetates for sustainable aqueous battery electrolytes. Nat. Sustain. 6, 1474-1484 (2023). https://doi.org/10.1038/s41893-023-01172-y
36.	N. Wang, X. Dong, B. Wang, Z. Guo, Z. Wang et al., Zinc-organic battery with a wide operation-temperature window from - 70 to 150 °C. Angew. Chem. Int. Ed. 59, 14577-14583 (2020). https://doi.org/10.1002/anie.202005603
37.	M. Li, X. Wang, J. Hu, J. Zhu, C. Niu et al., Comprehensive H₂O molecules regulation via deep eutectic solvents for ultra-stable zinc metal anode. Angew. Chem. Int. Ed. 62, 2215552 (2023). https://doi.org/10.1002/anie.202215552
38.	S. Plimpton, Fast parallel algorithms for short-range molecular dynamics. J. Comput. Phys. 117, 1-19 (1995). https://doi.org/10.1006/jcph.1995.1039
39.	L. Martínez, R. Andrade, E.G. Birgin, J.M. Martínez, PACKMOL: a package for building initial configurations for molecular dynamics simulations. J. Comput. Chem. 30, 2157-2164 (2009). https://doi.org/10.1002/jcc.21224
40.	P. Li, B.P. Roberts, D.K. Chakravorty, K.M. Merz Jr., Rational design of particle mesh Ewald compatible Lennard-Jones parameters for +2 metal cations in explicit solvent. J. Chem. Theory Comput. 9, 2733-2748 (2013). https://doi.org/10.1021/ct400146w
41.	J.N. Canongia Lopes, A.A.H. Pádua, Molecular force field for ionic liquids composed of triflate or bistriflylimide anions. J. Phys. Chem. B 108, 16893-16898 (2004). https://doi.org/10.1021/jp0476545
42.	W.L. Jorgensen, D.S. Maxwell, J. Tirado-Rives, Development and testing of the OPLS all-atom force field on conformational energetics and properties of organic liquids. J. Am. Chem. Soc. 118, 11225-11236 (1996). https://doi.org/10.1021/ja9621760
43.	K. Momma, F. Izumi, VESTA 3 for three-dimensional visualization of crystal, volumetric and morphology data. J. Appl. Crystallogr. 44, 1272-1276 (2011). https://doi.org/10.1107/s0021889811038970
44.	W. Humphrey, A. Dalke, K. Schulten, VMD: visual molecular dynamics. J. Mol. Graph. 14, 33-38 (1996). https://doi.org/10.1016/0263-7855(96)00018-5
45.	F. Neese, The ORCA program system. Wires Comput. Mol. Sci. 2, 73-78 (2012). https://doi.org/10.1002/wcms.81
46.	T. Lu, F. Chen, Multiwfn: a multifunctional wavefunction analyzer. J. Comput. Chem. 33, 580-592 (2012). https://doi.org/10.1002/jcc.22885
47.	H. Zhao, Q. Fu, X. Luo, X. Wu, S. Indris et al., Unraveling a cathode/anode compatible electrolyte for high-performance aqueous rechargeable zinc batteries. Energy Storage Mater. 50, 464-472 (2022). https://doi.org/10.1016/j.ensm.2022.05.048
48.	Z. Hou, H. Tan, Y. Gao, M. Li, Z. Lu et al., Tailoring desolvation kinetics enables stable zinc metal anodes. J. Mater. Chem. A 8, 19367-19374 (2020). https://doi.org/10.1039/d0ta06622b
49.	Z. Luo, Y. Xia, S. Chen, X. Wu, R. Zeng et al., Synergistic “anchor-capture” enabled by amino and carboxyl for constructing robust interface of Zn anode. Nano-Micro Lett. 15, 205 (2023). https://doi.org/10.1007/s40820-023-01171-w
50.	Q. Dou, N. Yao, W.K. Pang, Y. Park, P. Xiong et al., Unveiling solvation structure and desolvation dynamics of hybrid electrolytes for ultralong cyclability and facile kinetics of Zn-Al alloy anodes. Energy Environ. Sci. 15, 4572-4583 (2022). https://doi.org/10.1039/d2ee02453e
51.	Y. Sui, X. Ji, Anticatalytic strategies to suppress water electrolysis in aqueous batteries. Chem. Rev. 121, 6654-6695 (2021). https://doi.org/10.1021/acs.chemrev.1c00191
52.	C. Li, X. Xie, S. Liang, J. Zhou, Issues and future perspective on zinc metal anode for rechargeable aqueous zinc-ion batteries. Energy Environ. Mater. 3, 146-159 (2020). https://doi.org/10.1002/eem2.12067
53.	X. Bai, Y. Nan, K. Yang, B. Deng, J. Shao et al., Zn ionophores to suppress hydrogen evolution and promote uniform Zn deposition in aqueous Zn batteries. Adv. Funct. Mater. 33, 2307595 (2023). https://doi.org/10.1002/adfm.202307595
54.	H. Wang, C. Luo, Y. Qian, C. Yang, X. Shi et al., Upcycling of phosphogypsum waste for efficient zinc-ion batteries. J. Energy Chem. 81, 157-166 (2023). https://doi.org/10.1016/j.jechem.2023.02.037
55.	Z. Zhao, J. Zhao, Z. Hu, J. Li, J. Li et al., Long-life and deeply rechargeable aqueous Zn anodes enabled by a multifunctional brightener-inspired interphase. Energy Environ. Sci. 12, 1938-1949 (2019). https://doi.org/10.1039/c9ee00596j
56.	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
57.	J. Shi, K. Xia, L. Liu, C. Liu, Q. Zhang et al., Ultrahigh coulombic efficiency and long-life aqueous Zn anodes enabled by electrolyte additive of acetonitrile. Electrochim. Acta 358, 136937 (2020). https://doi.org/10.1016/j.electacta.2020.136937
58.	C. Cui, D. Han, H. Lu, Z. Li, K. Zhang et al., Breaking consecutive hydrogen-bond network toward high-rate hydrous organic zinc batteries. Adv. Energy Mater. 13, 2301466 (2023). https://doi.org/10.1002/aenm.202301466
59.	Y. Han, F. Wang, B. Zhang, L. Yan, J. Hao et al., Building block effect induces horizontally oriented bottom Zn(002) deposition for a highly stable zinc anode. Energy Storage Mater. 62, 102928 (2023). https://doi.org/10.1016/j.ensm.2023.102928
60.	W. Li, L. Huang, H. Zhang, Y. Wu, F. Wei et al., Supramolecular mineralization strategy for engineering covalent organic frameworks with superior Zn-I₂ battery performances. Matter 6, 2312-2323 (2023). https://doi.org/10.1016/j.matt.2023.04.019
61.	M. Zhu, Q. Ran, H. Huang, Y. Xie, M. Zhong et al., Interface reversible electric field regulated by amphoteric charged protein-based coating toward high-rate and robust Zn anode. Nano-Micro Lett. 14, 219 (2022). https://doi.org/10.1007/s40820-022-00969-4
62.	L. Cao, D. Li, T. Pollard, T. Deng, B. Zhang et al., Fluorinated interphase enables reversible aqueous zinc battery chemistries. Nat. Nanotechnol. 16, 902-910 (2021). https://doi.org/10.1038/s41565-021-00905-4
63.	D. Li, L. Cao, T. Deng, S. Liu, C. Wang, Design of a solid electrolyte interphase for aqueous Zn batteries. Angew. Chem. Int. Ed. 60, 13035-13041 (2021). https://doi.org/10.1002/anie.202103390

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