This
Review covers a sequence of key discoveries and technical
achievements that eventually led to the birth of the lithium-ion battery.
In doing so, it not only sheds light on the history with the advantage
of contemporary hindsight but also provides insight and inspiration
to aid in the ongoing quest for better batteries of the future. A
detailed retrospective on ingenious designs, accidental discoveries,
intentional breakthroughs, and deceiving misconceptions is given:
from the discovery of the element lithium to its electrochemical synthesis;
from intercalation host material development to the concept of dual-intercalation
electrodes; and from the misunderstanding of intercalation behavior
into graphite to the comprehension of interphases. The onerous demands
of bringing all critical components (anode, cathode, electrolyte,
solid-electrolyte interphases), each of which possess unique chemistries,
into a sophisticated electrochemical device reveal that the challenge
of interfacing these originally incongruent components often outweighs
the individual merits and limits in their own properties. These important
lessons are likely to remain true for the more aggressive battery
chemistries of future generations, ranging from a revisited Li-metal
anode, to conversion-reaction type chemistries such as Li/sulfur,
Li/oxygen, and metal fluorides, and to bivalent cation intercalations.
Measurements on anodic surface oxidation of noble metals as a function of time and electrode potential show that the initial extension and subsequent thickening of such oxide films is directly logarithmic in time. A striking feature of this behavior is that the direct logarithmic extension law already applies to increase of coverage of Pt or Au electrodes with time well below the limit of formation of one monolayer of OH or O species on the metal surface. A direct logarithmic law of oxide film growth also applies to post-monolayer growth involving early stages of quasi-three-dimensional film formation. Eventually, as the oxide film thickens, the Mott–Cabrera ‘‘high-field’’ growth mechanism can apply. However, below the monolayer level of oxide film formation, electrochemisorption of two-dimensional (2D) structures of OH or O arises so that the Mott–Cabrera mechanism cannot be applicable to that situation. It is shown that the kinetic relation for direct electrodeposition of OH or O species onto available metal surface sites also cannot lead to a log law in time for extension of a 2D film. A new treatment, based on the changing surface-potential component of the electrode-solution potential difference, due to place exchange between metal atoms in the surface and electrosorbed OH or O species on the surface, is presented and shown to give rise to a direct log law for extension of the film in time. The relation derived has features in conformity with the experimentally demonstrated characteristics of submonolayer and early post-monolayer film extension.
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