Nobel laureate Prof. John B.

Goodenough discusses lithium-ion batteries in

perspective article
The 2019 Nobel Prize in Chemistry has been awarded to Prof. John B. Goodenough
of the University of Texas, Austin, USA, Prof. M. Stanley Whittingham of Binghamton
University, USA, and Dr. Akira Yoshino of Asahi Kasei Corporation and Meijo
University, Japan "for the development of lithium-ion batteries." Prof. Goodenough
recently published a perspective article entitled "A perspective on the Li-ion
batteries" in Science China Chemistry and discussed the history, current challenges,
and promising research directions of lithium-ion batteries, the ubiquitous energy-
storage devices in electronics. I wrote a news release on the article for the journal,
which I'm posting here with slight modifications as I present a summary of the article.

[Prof. John Goodenough at the University

of Texas, Austin. Credit: University of Texas, Austin]

Before lithium-ion batteries

The research on the modern rechargeable batteries was initiated in the 1960s,
marked by the pioneering work of German scientist R. Schroeder and French
scientist J. Rouxel, who investigated the chemistry of reversible intercalation of
Li+ into transition metal disulfides (MS2). In 1976, Prof. Whittingham published the
seminal paper in Science, where he identified TiS2 as an excellent Li+ host to enable
energy storage through Li+-intercalation (Figure 1).
Figure 1. (a) Scheme of the Whittingham battery. Credit: The Royal Swedish Academy of
Sciences. (b) A Whittingham battery pack exhibited in the 1977 Chicago Automotive Show,
U.S. Credit: Chemical Reviews, The American Chemical Society.

The request for lithium-ion batteries

A fatal problem of the Whittingham battery soon arose. The anode material, Li metal,
was a troublemaker. During the charging process, Li + de-intercalated from TiS2 and
reduced to Li(0) on the Li metal surface. The deposition of Li +, however, is non-
uniform due to different nucleation energy across the metal surface, thus creating
pointy Li crystals termed Li dendrites or whiskers. Such dendrites could pierce the
separator sitting between Li metal and TiS 2 (Figure 2), trigger electrical short circuits,
ignite organic-liquid electrolytes, and cause combustion or explosions. This severe
safety concern halted the development of Li-based batteries.

Figure 2. Scheme of electric short circuit triggered by metallic lithium whiskers (dendrites).
Credit: The Royal Swedish Academy of Sciences.
 The birth of Li-ion batteries
In the 1980s, the Li-based batteries were revived by Prof. Goodenough, whose
research team proposed a battery without Li metal. Since Li metal served as a
source of Li+, the elimination of Li requires either the cathode or anode to contain
abundant Li+ ions and serve as Li+-reservoirs. In 1980, Prof. Goodenough and co-
workers demonstrated in Materials Research Bulletin a Li-containing layered oxide,
lithium cobalt oxide (LiCoO2, Figure 3a), as a potent cathode material. Since the
function of the cell relied merely on Li + (without metallic Li), it was coined the Li-ion
battery (Figure 3b). In 1987, Dr. Yoshino demonstrated the first working Li-ion
battery with a graphitic carbon anode and a LiCoO 2 cathode, which was licensed to
Sony Incorporation and eventually led to the commercialization of the Li-ion battery
in 1991. Through years of development, the cathodes in modern Li-ion batteries
have significantly been diversified, spanning from lithium iron phosphate (LiFePO 4)
to lithium nickel-manganese-cobalt oxide (NMC) and lithium nickel-cobalt-aluminum
oxide (NCA), etc.

Figure 3. (a) Layered crystal structure of LiCoO2. Credit: Wikipedia. (b) Scheme of
Goodenough's concept of a Li-ion battery using a LiCoO2 cathode. Credit: The Royal
Swedish Academy of Sciences.

The limitations of lithium-ion batteries

Modern Li-ion batteries are still facing several limitations that are calling concerted
efforts from both industry and the academy to tackle; for example:
1) flammability of organic-liquid electrolytes poses safety hazards;
2) fast charging leads to plating of metallic lithium on carbon anodes and battery
lifetime degradation; and
3) overcharging corrodes LiCoO2 and leads to explosions.
These problems demand careful and real-time monitoring of the battery's working
conditions, which significantly increases the operation and maintenance costs.
The future of lithium-ion batteries
Prof. Goodenough highlights at the end of the article that developing alternatives to
liquid electrolytes could be a promising strategy to address the challenges.
Ferroelectric amorphous oxide glasses and polymer electrolytes percolated with
liquid organic Li+ solutions are possible candidates.
For more details, please read:
John B. Goodenough and Hongcai Gao, A perspective on the Li-ion battery. Sci.
China Chem. doi: 10.1007/s11426-019-9610-3 (2019).
***

This post is contributed by Dr. Tianyu Liu at the Department of Chemistry, Virginia

Tech, USA. Tianyu Liu acknowledges the careful proofread by the editorial office
of Science China Chemistry, as well as valuable comments made by Dr. Aashutosh
Mistry of Argonne National Laboratory, U.S.