Efficient Potassium Storage through Ti-O-H-O Electron Fast Track of MXene Heterojunction

doi:10.15541/jim20240130

Abstract

Abstract:

MXenes with two-dimensional layered structure are widely used in the field of potassium ion supercapacitors because of their excellent electrical properties and adjustable surface functional groups, but their limited dual-capacitor storage capacity severely retards the application of MXenes materials in electrode materials. In this work, the strategy of “Lewis acid molten salt pre-etching + liquid phase etching + in situ hydrothermal recombination” was used to prepare the Ti₃C₂-based heterojunction with Ti₃C₂ as matrix and MnO₂ coated surface to improve the storage of potassium ions in electrode materials. The connection mode, electrical properties and the change of potassium adsorption law at Ti₃C₂-based heterojunction interfaces were studied by using the first principles calculation method based on density functional theory. The results show that the maximum adsorption capacity of potassium ions in the constructed Ti₃C₂-based heterojunction is about 3 times that of Ti₃C₂. The presence of Ti-O-H-O connecting channel increases the number of free electrons in MnO₂, causing Ti₃C₂-based heterojunction exhibiting excellent electrical properties. The electrochemical test results of the three-electrode system show that, at a current density of 1 A·g^-1, Ti₃C₂-based heterojunction can provide 431 F·g^-1 specific capacitance which is much higher than 128 F·g^-1 of bare Ti₃C₂. At a voltage sweep rate of 100 mV·s^-1, the contribution of pseudocapacitance is up to 89%. In addition, the Ti₃C₂-based heterojunction exhibits lower electrochemical impedance, which improves the potassium ion transport rate and electron transfer rate. Therefore, this study demonstrates that the electrochemical performance of Ti₃C₂ matrix can be improved by constructing Ti₃C₂-based heterojunction, and the corresponding energy storage mechanism can provide a theoretical basis for the design of other MXenes-based electrode materials.

Key words: Ti₃C₂-based heterojunction, ion adsorption, kinetic analysis, potassium-ion storage, supercapacitor

CLC Number:

TQ174

CHAO Shaofei, XUE Yanhui, WU Qiong, WU Fufa, MUHAMMAD Sufyan Javed, ZHANG Wei. Efficient Potassium Storage through Ti-O-H-O Electron Fast Track of MXene Heterojunction[J]. Journal of Inorganic Materials, 2024, 39(11): 1212-1220.

Figures/Tables 7

Fig. 1 Structure and morphology characterization of Ti3C2-based heterojunction (a-c) SEM images of (a) Ti3Al-ZnC2, (b) Ti3C2 and (c) Ti3C2-based heterojunction; (d-f) XRD patterns of Ti3Al-ZnC2, Ti3C2 and Ti3C2-based heterojunction; (g) Atomic structure diagram of preparation of Ti3C2 Colorful figures are available on website

Fig. 2 Binding rules between Ti3C2-based heterojunction Colorful figures are available on website

Fig. 3 Electrochemical potassium storage performance tests of Ti3C2-based heterojunction (a) CV curves of Ti3C2 and Ti3C2-based heterojunction in a three-electrode system at a scan rate of 100 mV·s-1; (b) GCD curves of Ti3C2 and Ti3C2-based heterojunction at a current density of 1 A·g-1; (c) GCD curves of Ti3C2-based heterojunction at different current densities; (d) CV curves and (e) GCD curves of Ti3C2-based heterojunction in a double electrode system; (f) Ragone plot of energy density and power density[37⇓⇓⇓⇓⇓⇓-44]; (g, h) Schematic diagrams of two hybrid supercapacitors; (i) Practical application of Ti3C2-based heterojunction hybrid supercapacitors Colorful figures are available on website

Fig. 4 Dynamic analysis and energy storage mechanism of Ti3C2-based heterojunction (a) CV curves of Ti3C2-based heterojunction at different scanning rates; (b) Relationship between the peak current and the scanning rate at a specific potential; (c) Pseudocapacitance ratio diagram of Ti3C2-based heterojunction at 100 mV·s-1; (d) Pseudocapacitance ratio of Ti3C2-based heterojunction at different scanning rates; (e) EIS plots of Ti3C2-based heterojunction and MnO2; (f) Magnified plots of a region in (e) with inset showing corresponding equivalent circuit; (g) Schematic diagram of mechanism of pseudocapacitance changed with Mn valence Colorful figures are available on website

Fig. 5 Adsorption rule of potassium ion on Ti3C2-based heterojunction and bare Ti3C2 Colorful figures are available on website

Fig. 6 Electron band structure and state density diagrams of Ti3C2-based heterojunction (a, b) Band structure diagrams of MnO2; (c) DOS diagram of MnO2; (d) PDOS diagrams of Mn and O atoms in MnO2; (e, f) PDOS diagrams of the distribution of electron orbitals of Mn and O atoms in valence and conduction bands; (g) PDOS diagram of each atom in Ti3C2-based heterojunction; (h) PDOS diagrams of Mn and O atoms in valence band of Ti3C2-based heterojunction; (i) PDOS diagrams of Mn and O atoms in conduction band of Ti3C2-based heterojunction with inset showing the band structure diagram of Ti3C2-based heterojunction Colorful figures are available on website

Fig. 7 Differential charge density diagrams of Ti3C2-based heterojunction (a-c) 3D top views of differential charge density diagrams of three heterojunctions; (d-f) 3D differential charge density and 2D differential charge density section diagrams of (d) Ti(I), (e) Ti(Ⅱ) and (f) Ti(Ⅲ) connected heterojunction with MnO2 Colorful figures are available on website

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