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CHEMPHYSCHEM 2002, 3, 155 ± 159 ¹ WILEY-VCH-Verlag GmbH, 69451 Weinheim, Germany, 2002 1439-4235/02/03/02 $ 17.50+.50/0 155
J. O. Besenhard and M. Winter
tion of the Mg cell is quite fast, equiv- In aqueous battery systems, decomposi- themselves regard their invention as first
alently, the cell power is high,[*] which tion of the aqueous electrolyte in oxygen step to the exploration of the recharge-
again might render possible the replace- and hydrogen occurs under these con- able magnesium technology. Neverthe-
ment of the high power lead ± acid and ditions. However, this decomposition is less, the work of Aurbach's group is the
nickel ± cadmium batteries by rechargea- the key for overcharge and overdischarge greatest and most successful approach so
ble Mg systems. Another advantage of Mg protection. The oxygen, which is formed far for the realization of rechargeable
cells over conventional aqueous batteries at one electrode, diffuses through the batteries with metallic magnesium ano-
containing Pb, Cd, or Ni would be that the electrolyte to the other electrode, where des.
active materials are much more environ- recombination with hydrogen to water
mentally benign. However, the lower takes place. In essence, the oxygen
battery materials costs of Mg batteries evolved at one electrode is consumed at
Transition Metal/Lithium Oxide
(compare also Table 1 for abundance) the other; the water decomposition reac-
Nanocomposites as New
may be more than compensated by the tion is reversible. The cells and electrodes
Anode Materials in Lithium Ion
higher manufacture costs. Whereas aque- are composed in such a way that this
Batteries
ous battery systems can be assembled in reversible decomposition/recombination
air without any particular precautions, the reaction is the predominant side reaction The performance of lithium ion batteries
organohaluminate/ether electrolyte in and other detrimental side reactions, strongly depends on the type of electrode
the Mg cell is moisture sensitive and which may occur during overcharge and material. To a first approximation, proper-
exhibits a higher flammability, and thus overdischarge and which lower the per- ties such as charge storage capacity
cell manufacture demands strictly dry and formance and the safety of the battery (specific charge [Ah kg 1] or charge den-
inert atmospheric conditions. On the system, are suppressed. sity [Ah L 1]), redox potentials for lithium
other hand, nickel ± metal hydride (Ni- Nonaqueous electrolytes do not toler- insertion/deinsertion, reversibility, and cy-
MH) cells are not included in the compar- ate overcharge and overdischarge as cle life determine the choice of a certain
ison of Aurbach's group, though this there is no comparable decomposition/ material. Since the introduction of lithium
system may be the ™true competitor∫ of recombination mechanism; the over- ion cells to the market, the specific energy
the Mg battery due to higher specific charge/overdischarge reactions are irre- has increased by more than 30 %, mostly
energies and better environmental be- versible. For example, each individual cell due to the use of carbon anode materials
havior than Ni-Cd. in a lithium ion battery is managed by an with higher lithium storage capabilities.
Another handicap of the Mg battery in electronic surveillance and control sys- Many manufacturers use graphites as
comparison to aqueous systems is the tem, which also switches the current off anode materials, which typically exhibit
missing chemical overcharge/overdi- under overcharge/overdischarge condi- a maximum lithium capacity of LiC6
scharge protection. Overcharge and over- tions. This electronic control increases (339 A h kg 1 (759 A h L 1) with respect to
discharge reactions typically occur in the battery manufacture costs significant- lithiated graphite and 372 A h kg 1
larger battery units, where cells are con- ly (this may be as much as a factor of two). (837 A h L 1) with respect to unlithiated
nected in series and each cell has an In the case of a series connection of graphite). However, there is strong inter-
influence on the charge/discharge reac- rechargeable nonaqueous electrolyte mag- est in replacing carbonaceous anode
tion of its neighboring cell. As even nesium batteries, a similar electronic con- materials by those which can show even
automatically assembled cells may differ trol thus will also be needed. higher charge storage capacities. A large
in their cell capacity by 5 %, it is very In conclusion, though the cell voltage number of metals and intermetallics (™al-
likely that a ™weak∫ cell with a relatively and specific energy of rechargeable mag- loys∫), such as Al, Si, Sn, Sb, ™SnSb∫, or
smaller cell capacity may be already nesium cells are comparable to those of SnAg3 , are capable of reversible accom-
completely charged (or discharged) while the aqueous nickel systems, they do suffer modation of lithium. These lithium stor-
its ™stronger∫ neighbors are still charged from the typical problems of cells with age metals and alloys show very high
(discharged). Then, the weak cell is driven nonaqueous electrolytes. At contrast, in specific charges and charge densities (for
to undergo an overcharge (overdi- the case of nonaqueous lithium ion cells, example, 790 A h kg 1 (2020 A h L 1) for
scharge) reaction until its neighbors are these drawbacks are more than counter- Li22Sn5) and have therefore been repeat-
completely charged (discharged) as well. balanced by very high cell voltages and edly suggested as anode materials for
specific energies. Hence, the key for a lithium ion batteries. Unfortunately, the
success of magnesium batteries are better uptake and release of Li is accompanied
[*] As the ionic conductivities of the Mg electrolytes performance characteristics. Much effort by enormous volume changes (a 250 %
are typically about two orders of magnitude
lower than those of aqueous battery electrolytes,
has to be put in the improvement of the volume increase on going from Sn to
the electrolyte is made as a very thin film so that cathode material in terms of higher Li22Sn5 but only 10 % from graphite to
the Mg2 transport pathways are short, namely magnesium storage capacity and higher LiC6), which in the case of ™ordinary∫
the total electrolyte resistance is low and thus potential versus magnesium. As a matter coarse grained, bulk metal host materials
higher cell power is possible. Lead ± acid cells
cannot be operated with a thin layer electrolyte
of fact, the research and development leads to cracking and crumbling of the
as stoichiometric amounts of H2SO4 are required activities on magnesium systems are still electrode and hence renders an applica-
for the cell reaction. in their beginning stages. The authors tion in rechargeable batteries impossible.