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O 200
N 100
and/or reductive reactions of organic
50 no ESR signal compounds. For example, poly(acrylic
acid)-combined TEMPOs were
synthesized and studied as a catalytic
reagent for the oxidation of alcohols
O O25 into aldehydes and ketones. The
mV/s organic radical-based or metal-free
redox reagents have been reexamined
recently from the perspective of
green or environmentally compatible
chemical reaction processes.
n O O Why do nitroxide radical polymers
work as catalysts? Electrochemical
PTMA N N studies of these polymers have
revealed that the nitroxide center
displays reversible redox behavior
attributable to oxidation of the
nitroxide radical and reduction of the
E1/2 = 3.58 V corresponding oxoammonium form.
However, there has been no report,
except for our work, in which organic
radical polymers have been utilized as
O
ESR rganic Molecular RadicalsAn organic molecular radical the electrode-active or charge-storage
component for a secondary battery.3, 4
is a molecular entity possessing one unpaired electron A battery composed of the radical
such as CH3 and CCl3, in which the dot symbolizes polymer electrode is a so-called
2.8 an3unpaired
.2 3.6 Organic4.radicals
electron. 0 4.4appear as
often
organic radical battery here.
Voltage (Li/Li )
are also known to initiate + and propagate polymerization
Nitroxide Radical Leading
to an Organic Radical Battery
and combustion reactions. They are usually short-lived A nitroxide radical is a typical
and highly reactive, being converted to stable molecules oxygen-centered stable radical
with spin-density localization on
through dimerization or redox reactions with other the oxygen atom, and involves the
molecules, solvents, or molecular oxygen. For example, the resonance structure shown in Fig. 2
methyl radical easily forms ethane (2CH3 CH3-CH3) by that contributes to the high stability
of the radical. A nitroxide radical is
dimerization. Thus the organic molecular radicals had been also characterized by its significantly
hitherto classified as unstable and intractable materials. small molecular weight per the radical
moiety (N-O = formula weight 30)
and its compact molecular size.
However, organic radicals can commercially available and widely
be chemically modified into stable used as spin labels for monitoring The nitroxide radical displays two
compounds, existing for appreciable biomolecules and as spin traps redox couples as illustrated in Fig. 3.
lengths of time under ambient or radical scavengers of organic On the anodic side, the nitroxide
conditions. Chemical stabilization materials and biological systems. radical is oxidized to form the
is achieved via sterically protected Precursors of radical molecules are corresponding oxoammonium cation.
structures around the radical centers also produced in ton level quantities For example, an oxoammonium
or the unpaired electrons and/or by as antioxidants and as light-stabilizers phosphorus hexafluoride salt is
resonance structures involving the for plastics and commodity materials. formed in the presence of LiPF6
unpaired electrons. Based on these For example, hindered amines (and which has been isolated as a stable
chemical modifications, hundreds polyamines) and hindered phenols salt. The oxidation process of the
of stable organic radicals are now (and polyphenols) act as antioxidants radical is reversible and leads to p-
known.1 Examples are contained in to reductively remove oxygen and type doping of the radical material.
Fig. 1. Tris(pentachlorophenyl)methyl radical contaminants, yielding On the cathodic side, the nitroxide
and bis(diphenylenepropenyl)phenyl- stable radical species through the radical is reduced to the aminoxy
methyl are carbon-centered radicals. abstraction of hydrogen. In summary, anion (e.g., the lithium alcoholate
Diphenylpicrylhydrazyl (DPPH) organic molecular radicals and their amine formation in LiPF6), leading
and triphenylaminium cationic precursors have been utilized in to n-type doping of the material. Our
radicals are examples of nitrogen- commodity stuffs, and have been idea is that the anodic redox couple of
centered radicals. Oxygen-centered examined and guaranteed as nontoxic the nitroxide radical and the cathodic
species involve molecular radicals materials. couple are applicable to cathode
such as 2,4,6-tri-t-butylphenoxyl, and anode reaction of a secondary
Stable organic radicals have been lithium-ion battery, respectively.
galvinoxyl, nitronyl nitroxide, and extended to their polymeric radical
2,2,6,6-tetramethyl-1-piperidinyloxy We have synthesized a series of
analogs as well. The radical polymers nitroxide polymers: The polymer
(TEMPO).2 were studied extensively in the involves the radical moiety with a
Some stable radicals such as 1970s as redox reagents or redox high density and allows molding
TEMPO and their derivatives are resins, which catalyze the oxidative of electrodes. Figure 4 shows the
(continued on next page) FIG. 5. The radical polymer, PTMA (see text).
O
O O O O
N N
N N N O
O O
O n N
(p-type) N N
O O n n
O
n
n n e e
1
n
2 3 4 5 6 7 Charging
Mw 226 198 184 196 138 127 114
n
R4N
n N-O N-O
8 9 Cl
Mw 258 156
R4N
Theoretical capacity
(Ah/kg)
103 172 p-type polymer n-type polymer
FIG. 10. Examples of radical polymers. FIG. 11. Schematic diagram of an all-organic radical battery.