Before Li Ion Batteries

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.