A comparison between the electrochemical behavior of reversible magnesium and lithium electrodes

This paper describes briefly the difference between reversible lithium and magnesium electrodes. In the case of lithium, the active metal is always covered by surface films. Li dissolution-deposition is reversible only when the surface films contain elastomers and are flexible. Hence, they can accommodate the morphological changes of the electrode during the electrochemical processes without breaking down. In an ideal situation, lithium is deposited beneath the surface films, while being constantly protected in a way that prevents reactions between freshly deposited lithium and solution species. In contrast to lithium, magnesium electrodes are reversible only in solutions where surface film free conditions exist. Mg does not react with ethers, and thus, in ethereal solutions of Grignard reagents (RMgX, where R = alkyl, aryl, X = halide) and complexes of the following type: Mg(AlX_4-nR_n′ R′_n″)₂, R and R′ = alkyl groups, X = halide, A = Al, 0 < n < 4 and n′ + n″ = n, magnesium electrodes behave reversibly. However, it should be noted that the above stoichiometry of the Mg salts does not reflect the true structure of the active ions in solutions. Mg deposition does not occur via electron transfer to simply solvated Mg²⁺ ions. The behavior of Mg electrodes in these solutions is discussed in light of studies by EQCM, EIS, FTIR, XPS, STM and standard electrochemical techniques.