Lithium-ion Battery - History

History

Lithium batteries were first proposed by M. S. Whittingham, now at Binghamton University, while working for Exxon in the 1970s. Whittingham used titanium(II) sulfide and lithium metal as the electrodes.

The reversible intercalation in graphite and intercalation into cathodic oxides was also discovered in the 1970s by J. O. Besenhard at TU Munich. Anmol also proposed the application as high energy density lithium cells. Electrolyte decomposition and solvent co-intercalation into graphite were severe drawbacks for long battery cycle life.

Primary lithium batteries in which the negative electrode is made from metallic lithium pose safety issues. As a result, lithium-ion batteries were developed in which both electrodes are made of a material containing lithium ions.

In 1979, John Goodenough and K Mizushima demonstrated a rechargeable cell with high cell voltage in the 4V range using lithium cobalt oxide (LiCoO₂) as the positive electrode and lithium metal as the negative electrode. This innovation provided the positive electrode material which made LIBs possible. LiCoO₂ is a stable positive electrode material which acts as a donor of lithium ions, which means that it can be used with a negative electrode material other than lithium metal. By enabling the use of stable and easy-to-handle negative electrode materials, LiCoO₂ opened a whole new range of possibilities for novel rechargeable battery systems.

In 1977, Samar Basu demonstrated electrochemical intercalation of lithium in graphite at the University of Pennsylvania. This led to the development of a workable lithium intercalated graphite electrode at Bell Labs (LiC6) to provide an alternative to the lithium metal electrode battery.

In 1980, Rachid Yazami also demonstrated the reversible electrochemical intercalation of lithium in graphite. The organic electrolytes available at the time would decompose during charging if used with a graphite negative electrode, preventing the early development of a rechargeable battery which employed the lithium/graphite system. Yazami used a solid electrolyte to demonstrate that lithium could be reversibly intercalated in graphite through an electrochemical mechanism. The graphite electrode discovered by Yazami is currently the most commonly used electrode in commercial lithium ion batteries.

In 1983, Dr. Michael Thackeray, Goodenough, and coworkers identified manganese spinel as a cathode material. Spinel showed great promise, given its 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 is currently used in commercial cells.

In 1985, Akira Yoshino assembled a prototype cell using carbonaceous material into which lithium ions could be inserted as one electrode, and lithium cobalt oxide (LiCoO₂), which is stable in air, as the other. By using materials without metallic lithium, safety was dramatically improved over batteries which used lithium metal. The use of lithium cobalt oxide (LiCoO₂) enabled industrial-scale production to be achieved easily.

This was the birth of the current lithium-ion battery.