First-Principles Calculation of the Desolvation Effect of Functionalized Carbon Nanotubes

This study used density functional theory (DFT)-based first-principles calculations to investigate the desolvation effect of single-walled carbon nanotubes (SWCNTs) modified with hydroxyl (-OH), carbonyl (-C=O), and carboxyl (-COOH) groups. SWCNTs have great potential as supercapacitor electrode materials due to their unique structural and electronic properties, but their practical application is limited by poor solvation-induced dispersibility and low ion transport efficiency. To solve this, this study constructed functionalized SWCNT models, simulated their interaction with lithium ion (Li+) complexes in acetonitrile (AN) solvent, and analyzed Li+ desolvation behavior, relative capacitance, and post-desolvation density of states (DOSs). The key research results are as follows: [Li(AN)]+ complete desolvation sizes differed: 5.91 Å (pristine SWCNTs), 6.26 Å (hydroxylated SWCNTs, HCNT), 6.11 Å (carbonylated SWCNTs, CNCNT; carboxylated SWCNTs, CXCNT). HCNT showed the largest relative capacitance enhancement (max 1.4× pristine), while CNCNT and CXCNT both had a max 1.3× improvement. Post-desolvation DOS analysis revealed distinct electronic property changes: HCNT-Li+ enhanced metallicity and conductivity; CNCNT-Li+ increased metallicity but reduced conductivity; and CXCNT-Li+ decreased metallicity with nearly unchanged conductivity. This study provides an atomic-scale theoretical basis for optimizing the properties of SWCNT solutions, supporting their application in high-performance supercapacitors, particularly in enhancing device energy density and cycle stability.