Lithium-ion batteries were first proposed by M.S. Whittingham at Binghamton University, at Exxon, in the 1970s. Whittingham used titanium(IV) sulfide as the cathode and lithium metal as the anode.
The electrochemical properties of lithium intercalated in graphite were first discovered in 1980 by Rachid Yazami et al., at the Grenoble Institute of Technology (INPG) and French National Centre for Scientific Research (CNRS) in France. They showed the reversible intercalation of lithium into graphite in a lithium/polymer electrolyte/graphite half cell. Their work was published in 1982 and 1983. It covered both thermodynamics (staging) and kinetics (diffusion) together with reversibility.
Primary lithium batteries in which the anode is made from metallic lithium pose safety issues. As a result, lithium-ion batteries were developed in which both anode and cathode are made of a material containing lithium ions. In 1981, Bell Labs developed a workable graphite anode to provide an alternative to the lithium metal battery. Following groundbreaking cathode research by a team led by John Goodenough, in 1991 Sony released the first commercial lithium-ion battery. Their cells used layered oxide chemistry, specifically lithium cobalt oxide and revolutionized consumer electronics.
In 1983, Michael Thackeray, Goodenough, and coworkers identified manganese spinel as a cathode material. Spinel showed great promise, given low-cost, good electronic and lithium ion conductivity, and three-dimensional structure which gives it good structural stability. Although pure manganese spinel fades with cycling, this can be overcome with chemical modification of the material. Manganese spinel was currently used in commercial cells.
In 1989, Goodenough and Arumugam Manthiram of the University of Texas at Austin showed that cathodes containing polyanions, e.g. sulfates, produce higher voltages than oxides due to the inductive effect of the polyanion.
In 1996, Goodenough, Akshaya Padhi and coworkers identified lithium iron phosphate (LiFePO4) and other phospho-olivines (lithium metal phosphates with olivine structure) as cathode materials. In 2002, Yet-Ming Chiang and his group at MIT showed a substantial improvement in the performance of lithium batteries by boosting the material’s conductivity by doping it with aluminum, niobium and zirconium. The exact mechanism causing the increase became the subject of a heated debate.
In 2004, Chiang again increased performance by utilizing iron-phosphate particles of less than 100 nanometers in diameter. This decreased particle density by almost one hundredfold, increased the cathode’s surface area and improved capacity and performance. Commercialization led to a competitive market and a patent infringement battle between Chiang and Goodenough.