ZIF-8 composited with carbon nanotubes via controllable in situ growth on magnesium anodes for improved electrochemical performance of magnesium batteries

Abstract

Magnesium-based anode materials have attracted significant attention in the energy storage domain because of their high theoretical capacities and low electrochemical potentials. However, in conventional electrolyte systems, magnesium metal electrodes dynamically generate an ion-blocking surface layer, resulting in prominent voltage polarization, which severely limits their practical applications. In this study, ZIF-8/carbon nanotubes (CNTs) coatings were used to modify the anodes of magnesium batteries. Compared with the unaltered magnesium battery, the voltage lag time of the ZIF-8/CNTs coating was shortened from 4 s before modification to 0.26 s, and the battery impedance was lowered by two orders of magnitude. The duration of the discharge platform was increased from 4 h before modification to 6–10 h, the anode utilization rate was more than doubled, and the specific energy density was significantly enhanced compared with the battery before modification. The mechanism indicates that the ZIF-8/CNTs coating can limit the infiltration of corrosive substances, extend their transmission path, and offer more effective protection to the magnesium anode. The incorporation of CNTs improves the conductivity of the battery, and it significantly improves the electrochemical performance of the magnesium battery.

Keywords

aqueous magnesium battery / ZIF-8/carbon nanotubes coating / surface modification / electrochemical performance

References

[1] Su DS, Schlögl R. Chemistry of energy conversion and storage. ChemSusChem, 2016, 94316

[2] Z.H. Yi, G.Y. Chen, F. Hou, L.Q. Wang, and J. Liang, Strategies for the stabilization of Zn metal anodes for Zn-ion batteries, Adv. Energy Mater., 11(2021), No. 1, art. No. 2003065.

[3] Lim HD, Kim DH, Park Set al.. Magnesiophilic graphitic carbon nanosubstrate for highly efficient and fast-rechargeable Mg metal batteries. ACS Appl. Mater. Interfaces, 2019, 114238754

[4] S.L. Liu, R.Z. Zhang, J.F. Mao, Y.L. Zhao, Q. Cai, and Z.P. Guo, From room temperature to harsh temperature applications: Fundamentals and perspectives on electrolytes in zinc metal batteries, Sci. Adv., 8(2022), No. 12, art. No. eabn5097.

[5] N. Guo, W.J. Huo, X.Y. Dong, et al., A review on 3D zinc anodes for zinc ion batteries, Small Meth., 6(2022), No. 9, art. No. 2200597.

[6] X.Y. Cai, Y.N. Xu, Q.Y. An, et al., MOF derived TiO₂ with reversible magnesium pseudocapacitance for ultralong-life Mg metal batteries, Chem. Eng. J., 418(2021), art. No. 128491.

[7] T. Perveen, M. Siddiq, N. Shahzad, R. Ihsan, A. Ahmad, and M.I. Shahzad, Prospects in anode materials for sodium ion batteries - A review, Renewable Sustainable Energy Rev., 119(2020), art. No. 109549.

[8] Wang F, Fan XL, Gao Tet al.. High-voltage aqueous magnesium ion batteries. ACS Cent. Sci., 2017, 3101121

[9] M. Deng, L.Q. Wang, D. Höche, et al., Corrosion and discharge properties of Ca/Ge micro-alloyed Mg anodes for primary aqueous Mg batteries, Corros. Sci., 177(2020), art. No. 108958.

[10] Canepa P, Gautam GS, Hannah DCet al.. Odyssey of multivalent cathode materials: Open questions and future challenges. Chem. Rev., 2017, 11754287

[11] Muldoon J, Bucur CB, Oliver AGet al.. Electrolyte roadblocks to a magnesium rechargeable battery. Energy Environ. Sci., 2012, 535941

[12] Liang ZM, Ban CM. Strategies to enable reversible magnesium electrochemistry: From electrolytes to artificial solid-electrolyte interphases. Angew. Chem. Int. Ed., 2021, 602011036

[13] Saha P, Datta MK, Velikokhatnyi OI, Manivannan A, Al-man D, Kumta PN. Rechargeable magnesium battery: Current status and key challenges for the future. Prog. Mater. Sci., 2014, 66: 1

[14] Shrestha N, Zillinger J, Utgikar V, Raja KS. Design strategies for anode of Mg–air batteries and hydrogen evolution reactions on Mg–RE alloys. ECS Trans., 2018, 851395

[15] F. Bella, S.D. Luca, L. Fagiolari, et al., An overview on anodes for magnesium batteries: Challenges towards a promising storage solution for renewables, Nanomaterials, 11(2021), No. 3, art. No. 810.

[16] Kumar BVR, Sathyanarayana S. The delayed action of magnesium anodes in primary batteries Part I. Experimental studies. J. Power Sources, 1983, 103219

[17] García-Ballesteros S, García-Negueroles P, Amat AM, Arques A. Humic-like substances as auxiliaries to enhance advanced oxidation processes. ACS Omega, 2022, 743151

[18] Boll F, Fadda M, Happel Met al.. Multicomponent synergistic contribution in nanoengineered nanofibers for flexible energy storage. ACS Appl. Energy Mater., 2024, 7114733

[19] E. Ravesio, G. Montinaro, G. Mincuzzi, et al., Ultrashort pulsed laser texturing of current collector for Si/C Li-ion anodes: Characterization of electrochemical performance and evolution of interface morphology, J. Energy Storage, 109(2025), art. No. 115226.

[20] Li YL, Yu XY, Zhou YJ, Lin Y, Wu Y. Nanostructured ZnO/BiVO₄ I-scheme heterojunctions for piezocatalytic degradation of organic dyes via harvesting ultrasonic vibration energy. Int. J. Miner. Metall. Mater., 2025, 322488

[21] David A, Gopal SK, Lakshmanan P, Chenbagam AS. Corrosion, mechanical and microstructural properties of aluminum 7075: Carbon nanotube nanocomposites for robots in corrosive environments. Int. J. Miner. Metall. Mater., 2023, 3061140

[22] D. Dessantis, P.D. Prima, D. Versaci, et al., Investigating sulfide-based all solid-state cells performance through P2D modelling, Chem. Eng. J. Adv., 18(2024), art. No. 100610.

[23] Cao KZ, Wang ST, He YN, Ma JH, Yue ZW, Liu HQ. Constructing Al@C–Sn pellet anode without passivation layer for lithium-ion battery. Int. J. Miner. Metall. Mater., 2024, 313552

[24] S. Sathya, C. Soosaimanickam, F. Bella, D.J. Yoo, and A.M. Stephan, Cycling performance of SiO_x–Si–C composite anode with different blend ratios of PAA-CMC as binder for lithium sulfur batteries, J. Polym. Res., 31(2024), No. 7, art. No. 205.

[25] Si HN, Zhao X, Liao QL, Zhang Y. Design and tailoring of patterned ZnO nanostructures for perovskite light absorption modulation. Int. J. Miner. Metall. Mater., 2024, 315855

[26] Tu M, Wannapaiboon S, Khaletskaya K, Fischer RA. Engineering zeolitic-imidazolate framework (ZIF) thin film devices for selective detection of volatile organic compounds. Adv. Funct. Mater., 2015, 25284470

[27] Liu CB, Zhao HC, Hou PMet al.. Efficient graphene/cyclodextrin-based nanocontainer: Synthesis and host–guest inclusion for self-healing anticorrosion application. ACS Appl. Mater. Interfaces, 2018, 104236229

[28] K. Jayaramulu, F. Geyer, A. Schneemann, et al., Hydrophobic metal–organic frameworks, Adv. Mater., 31(2019), No. 32, art. No. 1900820.

[29] J.Y. Liu, H.J. Yu, W.Z. Huang, et al., ZIF-8 modified the anode of the magnesium battery to improve the problems of voltage hysteresis and corrosion resistance, Mater. Chem. Phys., 318(2024), art. No. 129277.

[30] Chai GL, Guo ZX. Highly effective sites and selectivity of nitrogen-doped graphene/CNT catalysts for CO₂ electrochemical reduction. Chem. Sci., 2016, 721268

[31] Chinnappan A, Baskar C, Kim H, Ramakrishna S. Carbon nanotube hybrid nanostructures: Future generation conducting materials. J. Mater. Chem. A, 2016, 4249347

[32] Izadi-Najafabadi A, Yasuda S, Kobashi Ket al.. Extracting the full potential of single-walled carbon nanotubes as durable supercapacitor electrodes operable at 4 V with high power and energy density. Adv. Mater., 2010, 2235E235

[33] X.D. Sun, J.Z. Man, K. Liu, et al., Uniform lithium deposition enabled by a carbon nanotubes framework modified with nanosized ZIF-8 particles for dendrite-free lithium metal anode, Appl. Surf. Sci., 616(2023), art. No. 156474.

[34] Qiao YJ, Zhang H, Hu YXet al.. A chain-like compound of Si@CNT nanostructures and MOF-derived porous carbon as an anode for Li-ion batteries. Int. J. Miner. Metall. Mater., 2021, 28101611

[35] S.C. Lu, F. Xie, H.Y. Liu, et al., Construction and electrochemical properties of carbon nanotube composite Mn–MOFs materials electrode for high-performance flexible supercapacitors, Electrochim. Acta, 466(2023), art. No. 143063.

[36] Tan B, Wu ZF, Xie ZL. Fine decoration of carbon nanotubes with metal organic frameworks for enhanced performance in supercapacitance and oxygen reduction reaction. Sci. Bull., 2017, 62161132

[37] Lee TH, Roh JS, Yoo SY, Roh JM, Choi TH, Park HB. High-performance polyamide thin-film nanocomposite membranes containing ZIF-8/CNT hybrid nanofillers for reverse osmosis desalination. Ind. Eng. Chem. Res., 2020, 59125324

[38] L. Cheng, P.X. Yan, X.L. Yang, H.H. Zou, H. Yang, and H. Liang, High conductivity, percolation behavior and dielectric relaxation of hybrid ZIF-8/CNT composites, J. Alloy. Compd., 825(2020), art. No. 154132.

[39] Z.Y. Zhang, Z.H. Sun, S.B. Sun, et al., MXene modified anode of magnesium battery to improve the problems of voltage lag and irreversibility, J. Alloy. Compd., 960(2023), art. No. 170609.

[40] Jiang SQ, Li WD, Liu JYet al.. ZnO@ZIF-8 core-shell structure nanorods superhydrophobic coating on magnesium alloy with corrosion resistance and self-cleaning. J. Magnes. Alloys, 2023, 1193287

[41] Deng M, Höche D, Lamaka SV, Wang LQ, Zheludkevich ML. Revealing the impact of second phase morphology on discharge properties of binary Mg–Ca anodes for primary Mg–air batteries. Corros. Sci., 2019, 153: 225

[42] M. Deng, L.Q. Wang, D. Höche, et al., Clarifying the decisive factors for utilization efficiency of Mg anodes for primary aqueous batteries, J. Power Sources, 441(2019), art. No. 227201.

[43] Liu FF, Cao GQ, Ban JJet al.. Recent advances based on Mg anodes and their interfacial modulation in Mg batteries. J. Magnes. Alloys, 2022, 10102699

RIGHTS & PERMISSIONS

University of Science and Technology Beijing