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4
Electrochemistry of Manganese Oxides

Akiya Kozawa, Kohei Yamamoto, and Masaki Yoshio

4.1
Introduction

Most primary dry cells nowadays use MnO 2 as a cathode. The total annual
world consumption of MnO 2 for dry cells exceeds 600 000 tons, about 50% being
electrolytic manganese dioxide (EMD).
9
The total world population was about 5.5 billion (5.5 × 10 ) in 1997, of whom
640 million (about 12%) were in the developed areas (USA, Japan, Western
Europe). They consume 10–15 dry cells per person in a year. In the developing
areas (China, South-East Asia, India, Africa, South America), which contain is
88% of the world population, they use only 2–3 cells per person per year. In
the USA, Japan, and Western Europe, 60–80% of the dry cells are now alkaline
MnO 2 (EMD) cells and ZnC1 2 cells using EMD. Therefore, the use of EMD
has been increasing, as shown in Figure 4.1, and in the future, for dry cells it
will grow to at least two to three times the current production, since the use
of alkaline MnO 2 cells will increase steadily in the developing countries. The
most popular dry cell sizes are AA and AAA, since portable electronic devices
are becoming smaller. Table 4.1 compares the capacity of the 1.5 V AA-size cells
on the market today. In the developed countries, a rapid growth in rechargeable
cells is taking place for various devices such as portable telephones, camcorders,
and portable computers. One big future application of rechargeable batteries is
for electric vehicles (EVs). The most promising rechargeable cells and batteries
for small portable devices are Ni–MH cells, alkaline MnO 2 cells, and Li-ion
batteries using LiCoO 2 ,LiMn 2 O 4 ,orLi 0.33 MnO 2 . In this chapter, we describe
the important properties of EMD and new methods of determination of these
properties.

Handbook of Battery Materials, Second Edition. Edited by Claus Daniel and J¨ urgen O. Besenhard.
 2011 Wiley-VCH Verlag GmbH & Co. KGaA. Published 2011 by Wiley-VCH Verlag GmbH & Co. KGaA.