Electronic Effect and Regiochemistry of Substitution in Pre-sodiation Chemistry.

The low oxidation potential of a pre-sodiation cathode additive intrinsically prevents decomposition of the electrolyte. Although the introduction of electron-donating substitution reduces the oxidation potential, the additional molecular weight restricts the output capacity. Herein, as theroretically predicted, the electrochemical oxidation potential of sodium carboxylate is manipulated by the electronic effect and regiochemistry of the functionality, in which the stronger electron-donating substituent, p-π conjugation, and optimized regiochemistry can dramatically lead to the lower potential originated from the elevation of the highest occupied molecular orbital level. Thus, benefiting from the para-NH2 unit accompanied by a conjugated aromatic architecture, molecularly engineered sodium para-aminobenzoate (PABZ-Na) presents a reduced oxidation plateau of 3.45 V. Triggered by the positive compensation merit, sodium-based electrochemical storage systems manifest excellent electrochemical performances. This breakthrough sheds light into the correlation between the electronic effect of the functional group and the oxidation potential of the organic additive, affording in-depth insights into the fundamental guidance of pre-sodiation chemistry.