Lithium ion batteries history

Lithium ion batteries were first proposed by M.S. Whittingham (Binghamton University), then at Exxon, in the 1970s. Whittingham used titanium sulfide as the cathode and lithium metal as the anode.

The electrochemical properties of the lithium intercalation in graphite were first discovered in 1982 by Rajeeva R. Agarwal and J. Robert Selman at the Illinois Institute of Technology. They obtained the activity of lithium in graphite and showed the diffusion of lithium was rapid and reversible in essence proving its rechargeability.

Lithium batteries in which the anode is made from metallic lithium pose severe safety issues. As a result, lithium-ion batteries were developed in which the anode, like the cathode, is made of a material containing lithium ions. Lithium-ion batteries came into reality when Bell Labs developed a workable graphite anode to provide an alternative to the (metallic lithium anode) lithium battery. Following groundbreaking cathode research by a team led by John Goodenough, the first commercial lithium-ion battery was released by Sony in 1991. The cells used layered oxide chemistry, specifically lithium cobalt oxide. These batteries revolutionized consumer electronics.

In 1983, Michael Thackeray, John Goodenough, and coworkers identified manganese spinel as a cathode material. Spinel showed great promise, since it is a low-cost material, has good electronic and lithium ion conductivity, and possesses a three-dimensional structure which gives it good structural stability. Although pure manganese spinel fades with cycling, this can be overcome with additional chemical modification of the material. Manganese spinel is currently used in commercial cells.


In 1989, Arumugam Manthiram and John Goodenough of the University of Texas at Austin showed that cathodes containing polyanions, eg. sulfates, produce higher voltage than oxides due to the inductive effect of the polyanion.

In late 1996, Padhi, Goodenough and coworkers identified the lithium iron phosphate (LiFePO4) and other phospho-olivines (lithium metal phosphates with olivine-structure) as cathode material for lithium ion batteries. Owing to its tremendous superiority over other cathode materials in terms of cost, safety, stability and performance, LiFePO4 is currently being used or developed for most lithium-ion batteries to power portable devices such as laptop computers and power tools. LiFePO4 is most suitable for large batteries for electric automobiles and other energy storage applications such as load saving, where safety is of utmost importance.

In 2002, Yet-Ming Chiang and his group at MIT published a paper in which they showed a dramatic improvement in the performance of Li batteries by boosting the material's conductivity by doping it with aluminium, niobium and zirconium, though at the time, the exact mechanism causing the increase became the subject of a heated debate.

In 2004, Chiang again increased performance by utilizing iron-phosphate particles less than 100 nanometres across. This miniaturized the particle density by almost 100 fold, increased the surface area of the electrode and improved the battery's ability to store and deliver energy. Commercialization of the iron-phosphate technology led to a competitive market and a patent-infringement battle between Chiang and Goodenough, two of the leading developers of the technology.