Aluminum
batteries with aluminum as the anode and organic materials
as the cathode have continuously drawn considerable attention because
of their high theoretical energy density, natural abundance, and environmentally
benign nature. Herein, we have done an elaborate design work on the
basis of π–π conjugated organic molecule PTCDA
by a molecular engineering strategy. Introducing a sulfur atom to
replace the H atom in the aromatic ring of the PTCDA molecule to form
SPTCDA (sulfurized PTCDA) with p−π conjugated system
can reduce the energy level of the molecule. In addition, the extension
of the conjugated system makes the electrons more delocalized, which
is beneficial to the improvement of the conductivity of SPTCDA. Experimental
results show that compared with pristine PTCDA, SPTCDA has a more
stable structure and better cycle performance, rate capability, and
coulombic efficiency, as well as a higher discharge voltage plateau.
To further understand the electronic structure, operating voltage,
and correct redox mechanism, density functional theory (DFT) calculations
were performed for PTCDA and SPTCDA. The diffusion behavior of ions
on the electrode surface was also discussed. This work reveals an
important molecular structure design strategy for a carbonyl cathode,
in order to break the application limitations of this electrode material
on aluminum organic batteries.