Molecularly Compensated Pre‐Metallation Strategy for Metal‐Ion Batteries and Capacitors

The use of a sacrificial cathode additive as a pre-metallation method could ensure adequate metal sources for advanced energy storage devices. However, this pre-metallation technique suffers from the precise regulation of decomposition potential of additive. Herein, a molecularly compensated pre-metallation (Li/Na/K) strategy has been achieved through Kolbe electrolysis, in which the electrochemical oxidation potential of a metal carboxylate is manipulated by the bonding energy of the oxygen-metal (O-M) moiety. The electron-donating effect of the substituent and the low charge density of the cation can dramatically weaken the O-M bond strength, further bringing out the reduced potential. Thus, sodium acetate exhibits a superior pre-sodiation feature for sodium-ion battery accompanied with a large irreversible specific capacity of 301.8 mAh g^-1 , remarkably delivering 70.6 % enhanced capacity retention in comparison to the additive-free system after 100 cycles. This methodology has been extended to construct a high-performance lithium-ion battery and a lithium/sodium/potassium-ion capacitor.