As the inventor of the positive materials such as LiCoO2, LiMn2O4 and LiFePO4, Goodenough is famous in the lithium-ion battery field, and it is a real "father of lithium ion battery".

Recently, John B. Goodenough, 96 years old, has reviewed the history of the invention of rechargeable lithium ion batteries in the Nature Electronics journal, and points out the way for future development.

In 1970s, the oil crisis broke out in the United States. The government realized the excessive dependence on oil imports and began to develop solar energy and wind energy. Because of the intermittent characteristics of solar energy and wind energy, rechargeable batteries will eventually need to store these renewable clean energy sources.


Figure 1. schematic diagram of lithium ion batteries

Each battery has positive and negative poles, the positive and negative poles are separated by electrolytes, and the electrical energy is stored in two poles in the form of chemical energy. The chemical reactions between the two poles produce ions and electrons, ions are transferred inside the battery, and the electrons are forced to transfer outside the battery to form a circuit to generate electric energy.

In order to achieve reversible charge discharge, the key lies in the reversibility of chemical reaction.



Figure 2. Stanley Whittingham

At that time, most of the non rechargeable batteries were made of lithium negative electrode and organic electrolyte. In order to achieve rechargeable batteries, we are all working hard to invert lithium ions into layered transition metal sulfide positive electrodes. Stanley Whittingham of the Exxon Mobil Corp found that a reversible charge discharge can be achieved with layered TiS2 as a cathode material in the intercalation layer, and the product of the discharge is LiTiS2.

In 1976, the battery developed by Whittingham achieved a good initial efficiency. However, after repeated charging and discharging several times, lithium dendrites are formed inside the battery, and dendrites grow from negative electrodes to positive electrodes, forming short circuits, which may ignite electrolytes. This attempt, and the end of the failure!



Figure 3. LiCoO2

At the same time, Goodenough, transferred to the University of Oxford, is studying how much lithium can be removed from the layered LiCoO2 and LiNiO2 positive material structure. Eventually, they realized more than half of the lithium reversibly deintercalation from the cathode material.

The results of the study eventually led Asahi Kasei's Akira Yoshino to produce the first rechargeable lithium ion battery: LiCoO2 as a positive electrode and graphite carbon as a negative. The battery was successfully applied to the Sony Corp's earliest mobile phone.




Figure 4. Akira Yoshino
In order to reduce the cost and improve the security. Solid state rechargeable batteries, which use solid as electrolyte, seem to be an important direction for future development.
As early as in 1960s, European chemists were committed to inverting lithium ions into layered transition metal sulfide materials. At that time, the standard electrolytes for rechargeable batteries were mainly strong acid and strong alkaline aqueous electrolytes such as H2SO4 or KOH. Because in this type of aqueous electrolyte, H+ has good diffusivity.
At that time, the most stable rechargeable battery was layered NiOOH as cathode material and strong alkaline water electrolyte as electrolyte. H+ can be reversibly embedded in the layered NiOOH cathode to form Ni (OH) 2. The problem is that the water electrolytes limit the battery voltage, resulting in lower energy density of the battery.
In 1967, Joseph Kummer and Neill Weber of Ford motor found that Na+ had good diffusion properties in ceramic electrolytes above 300 degrees Celsius. So he invented a Na-S rechargeable battery: molten sodium as negative electrode, carbon containing molten sulfur as positive electrode and solid ceramic as electrolyte. However, the operating temperature of 300 degrees Celsius is bound to make the battery impossible to commercialize.
Nonetheless, the study opened the door to solid electrolyte and inspired the Goodenough of Lincoln Laboratory in MIT. At that time, Goodenough was studying the electrochemical work related to transition metal oxides, and focused on developing excellent sodium ion conductors based on oxides. Inspired by the above research, he and Henry Hong invented a solid state electrolyte Na1+xZr2SixP3 xO12 (NASICON). This solid electrolyte has very good sodium ion conductivity.




Figure 5. NASICON structure

In 1986, Goodenough realized the all solid state rechargeable lithium battery produced by dendrite using NASICON. At present, all solid state rechargeable lithium batteries and sodium batteries based on NASICON and other solid state electrolytes have been commercialized.

In 2015, Maria Helena Braga of the University of Oporto also demonstrated an insulated porous oxide solid electrolyte, which is comparable to the organic electrolytes used in lithium ion batteries for lithium ion and sodium ions.

All in all, all solid - state rechargeable batteries are the alternative to fossil fuels, regardless of their performance, cost or safety.