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Preparation, modification and adsorption properties of spinel-type H1.6Mn1.6O4 lithium-ion sieves with spiny nanotube morphology

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Abstract

H1.6Mn1.6O4 lithium-ion sieve with spinel structure was successfully prepared by hydrothermal, high-temperature calcination and ion exchange reaction. XRD, SEM, TEM, N2 ad/desorption and FTIR methods were employed to characterize the microstructure and morphology of the synthesized materials in detail. The experimental results show that H1.6Mn1.6O4 has the characteristics of mesoporous structure and nanotube morphology with length of ∼ 10 μm and diameter of 500–700 nm, and the spiny structure was grown on the surface of the nanotube uniformly. The effect of Al3+ doping on the structure and morphology of H1.6Mn1.6O4 was studied. The results show that Al3+ doping does not change the microstructure and morphology of H1.6Mn1.6O4, but the specific surface area and pore volume are increased to a certain extent. H1.6Mn1.6O4 and H1.6Mn1.6−xAlxO4 were used as lithium-ion adsorbents to study the adsorption properties of Li+ in solution. The adsorption experiment results show that the adsorption capacity of H1.6Mn1.6O4 increased with increasing solution pH value, indicating that the strong alkaline solution with higher pH value is more favorable for Li+ adsorption. The adsorption isotherm results show that Li+ adsorption process was fitted well by Langmuir model, indicating that Li+ maybe adsorbed on the surface of manganese oxides lithium-ion sieves via a monolayer adsorption. The theoretical maximum adsorption capacity of H1.6Mn1.6O4 and H1.6Mn1.6−xAlxO4 can reach 39.54 mg/g and 40.54 mg/g, respectively. The results of adsorption kinetics show that the adsorption rate of both H1.6Mn1.6O4 and H1.6Mn1.6−xAlxO4 is fast, and the adsorption capacity of H1.6Mn1.6−xAlxO4 (24.65 mg/g) is slightly better than H1.6Mn1.6O4 (24.33 mg/g). Li+ adsorption process can be well described by the pseudo-second-order model, suggesting adsorption behavior is mainly controlled by chemical sorption. Additionally, the free energy change (ΔGΘ) was determined by Van't Hoff equation is negative, which confirms the adsorption process is spontaneous and feasible. The positive value of ΔSΘ of adsorption reaction reflects there is a certain of affinity between manganese oxides lithium-ion sieves and Li+ in solution.

Graphical Abstract

The regular spiny structure on the surface of H1.6Mn1.6O4 nanotube lithium-ion sieve was synthesized. This special morphology not only keeps the nanotube pore structure to increase the adsorption ability and also increases the outer surface area to accelerate the Li+ diffusion speed without any substrate.

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Acknowledgements

This research was supported by the Natural Science Foundation of Qinghai Province (2022-ZJ-723), “Light of the West” for Young Scholars Program of Chinese Academy of Sciences (1-13), and “Thousand Talents Program” for high-end innovation of Qinghai Provincial.

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Authors and Affiliations

  1. School of Chemistry and Chemical Engineering, Qinghai Normal University, Xining, 810008, China

    Naicai Xu, Jing Liu, Bingrong Feng, Yingming Li, Yujie Yang & ShaoJu Bian

  2. Academy of Plateau Science and Sustainability, People’s Government of Qinghai Province and Beijing Normal University, Xining, 810016, China

    Naicai Xu & ShaoJu Bian

  3. Qinghai Institute of Salt Lakes, Chinese Academy of Sciences, Xining, 810008, China

    Li Han

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  1. Naicai Xu
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Xu, N., Liu, J., Han, L. et al. Preparation, modification and adsorption properties of spinel-type H1.6Mn1.6O4 lithium-ion sieves with spiny nanotube morphology. J Mater Sci 58, 4707–4725 (2023). https://doi.org/10.1007/s10853-023-08327-4

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