Controlling the Shape Anisotropy of Monoclinic Nb₁₂O₂₉ Nanocrystals Enables Tunable Electrochromic Spectral Range

Electrochromic smart windows that modulate the solar transmittance in a wide and selective spectral range can optimize building energy efficiency. However, for conventional materials such as bulk transition metal oxides, the electrochromic spectral range is constrained by their crystal structure with limited tunability. Herein, we report a method to control the shape anisotropy of monoclinic Nb₁₂O₂₉ nanocrystals and obtain a tunable electrochromic spectral range. We demonstrate the synthesis of monoclinic Nb₁₂O₂₉ nanorods (NRs), extending one-dimensionally along the b direction, and monoclinic Nb₁₂O₂₉ nanoplatelets (NPLs), extending two-dimensionally along the b and c directions. Upon electrochemical reduction accompanied by Li insertion, the NR films show increasing absorbance mostly in the near infrared region. In contrast, the NPL films show increasing absorbance in the near infrared region first followed by increasing absorbance in both visible and near infrared regions. To elucidate the influence of shape anisotropy, we used density functional theory to construct the lithiated structures of monoclinic Nb₁₂O₂₉ and in these structures we identified the presence of square planar sites and crystallographic shear sites for Li insertion. By calculating the theoretical spectra of the lithiated structures, we demonstrate that the Li insertion into the square planar sites results in absorption in the near infrared region in both NRs and NPLs due to their extension in the b direction, while the subsequent insertion of Li into the crystallographic shear sites leads to absorption in both visible and near infrared regions, which only occurs in NPLs due to their extension in the c direction.