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N

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.

intermediates in photochemical and thermal reactions and Redox Couples of the

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

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charging and discharging mechanism C Cl N O
Cl
of a prototype organic radical-based Cl
O 2N

lithium-ion battery where the p-type Cl


Cl
Cl
Cl N N NO 2 C
N N
CH 2 N N
C
nitroxide radical polymer forms a Cl Cl N N O O
O 2N
cathode operated in conjunction Cl Cl Cl Cl O

with a carbon anode. During the


Cl Cl (DPPH) (TEMPO)
OCH 3
charging process, the p-type radical O
N
polymer in the cathode is oxidized C

to the oxoammonium form. During N


O O
N
O
the discharging process, the nitroxide CH 3O OCH 3
radical is regenerated by reduction of
(galvinoxyl)
the oxoammonium.
A typical example of the nitroxide FIG. 1. Stable radical molecules. In the chemical formulae the unpaired electron is indicated by a dot.
radical polymer is poly(2,2,6,6-
tetramethylpiperidinyloxy-4-yl meth-
acrylate) (PTMA, Fig. 5). This poly-
mer is a derivative of a conventional
plastic, polymethacrylate, and has a O O
TEMPO radical in the repeating unit.
PTMA is obtained by the polymeriza- N N
tion of 2,2,6,6-tetramethylpiperidine
FIG. 2. Resonance structures for a nitroxide radical.
methacrylate, a material known as
a light stabilizer, followed by the
oxidation reaction of the precursor
polymer. PTMA is also prepared by
the anionic polymerization of the
radical monomer, 4-methacryloyl-
2,2,6,6-tetramethylpiperidinyl-N-
oxy. The molecular weight of PTMA
is >104, and the radical content is
almost 100% as shown by the chemi-
cal structure of PTMA in Fig. 5. PTMA
is an amorphous polymer that exists
in a glassy state at room temperature,
with a glass transition temperature
(Tg) to change to a rubbery state
of 70C. This is comparable to that
of poly(alkyl methacrylate), which FIG. 3. Redox processes involving the nitroxide radical.
suggests that PTMA may have good
processability and molding ability.
PTMA is thermally stable at high tem-
perature: A 10% weight decrease in
e e e e
the whole polymer occurs at 263C. Charging Discharging
The radicals on the PTMA are almost
stable up to this thermal decomposi- (+) (-) (+) (-)

tion temperature of the polymer.
N-O N+ = O
This radical concentration remains
Li

Li
unchanged for over 1 year under
N-O N+ =O
ambient conditions. This polymer dis- Li Li
plays appropriate solubility in organic N-O N+ =O
Li Li
solvents and is insoluble in electrolyte
solutions such as ethylene carbonate
and diethyl carbonate with LiPF6. p-type polymer Carbon p-type polymer Carbon

Battery Fabrication FIG. 4. A lithium-ion battery based on a radical polymer cathode.


and Performance
The radical polymer PTMA itself
does not show sufficient electric
conductivity; therefore, PTMA is
O
mixed with 20-50 wt % graphite
fibers to give a cathode electrode. A N
scanning electron microscopy (SEM)
image of the composite electrode
(Fig. 6) reveals that a graphite O O
nanofiber with a diameter of 150 nm
is thoroughly covered with a thin
(50-100 nm thick) PTMA layer. Figure n
7 shows a cyclic voltammogram PTMA

(continued on next page) FIG. 5. The radical polymer, PTMA (see text).

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Nishide and Suga
(continued from previous page)
of the PTMA/carbon composite electrode. In situ
electron spin resonance (ESR) signals (also shown
in Fig. 7) support ESR-silent oxoammonium
formation on the anodic side and regeneration of
the nitroxide radical with very high concentration
on the cathodic side. The redox potential of the
PTMA electrode is 0.76 V vs. Ag/AgCl (3.58 V vs.
Li/Li +). The narrow peak separation of the redox
waves of the radical polymer even in the form of
the electrode (Fig. 7) is attributable to fast electrode
reaction kinetics, which affords the capability for
a high power rate in the charging and discharging
processes of the battery.
The test cell was fabricated by stacking the radical
polymer electrode with a separator film and lithium
metal or a graphite carbon as the anode (Fig. 4).
Ethylene carbonate containing LiPF6 was used as
the electrolyte. FIG. 6. A SEM image of the radical polymer (PTMA)/carbon composite cathode.

The charge-discharge curves for the fabricated


PTMA lithium battery display a plateau voltage
at almost 3.5 V, which agrees with the redox
potential of the PTMA radical polymer. The charge
and discharge capacities were very similar and
were 110 mAh/g based on the PTMA weight at
a current density of 0.1 mA/cm2 (1 C), which is O
close to 100% of the theoretical capacity based N
200
on the amount of PTMA present on the electrode
(111 mAh/g). The high current efficiency may 100
be ascribed to the simple one-electron transfer 50 no ESR signal
reaction in the nanometer-size polymer layer of the
electrode. 25
mV/s
There was no self-discharge in the battery
via eluting out of the radical polymer into the
electrolyte solution. At a current density of 1.0 mA/
cm2 (10 C), the charging capacity still retained ca.
95% of that at 0.1 mA/cm2 (1 C). A current density O
E1/2 = 3.58 V
of 1.0 mA/cm2 is much greater than those of N
conventional batteries, and only 5 min was needed ESR
to fully charge this battery. In another aspect (Fig.
8), almost no voltage drop and no capacity decrease 2.8 3.2 3.6 4.0 4.4
were observed during the discharging process at Voltage (Li/Li+)
a current density as high as 50 C rate. Such rapid
charging and high power discharging behavior FIG. 7. Cyclic voltammogram of the radical polymer (PTMA) as the composite
of the radical polymer battery is caused by rapid electrode.
electron-transfer of the organic radical in the
nanometer-size polymer layer (see above).
The cycle performance during charging and
discharging in the range from 3.0 to 4.0 V of the
fabricated battery has been tested; no significant
deterioration in the capacity was observed for
more than 1000 cycles. This surprisingly long
cyclability may be ascribed to the chemical 4.0
stability of the nitroxide radical, the simple one-
electron transfer reaction of the radical, and to the 1C 5 C 10 C
Voltage (V)

amorphous electrode structure. The charging and 3.5


discharging processes of this battery do not involve
any structural change in the organic polymer or
50 C
the electrode-active material, bringing about the
strikingly long cycle life.
3.0
20 C
Previously Studied Organic Batteries
Organic functional polymers have been 2.5
developed as alternatives of inorganic materials 0 20 40 60 80 100
because of their light weight, flexibility, thin C a pa c it y ( % )
film-forming ability, processability, metal-free or
benign environmental aspects, and no limitation
FIG. 8. Example of discharging curves for the organic radical battery.

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in organic resources. Organic-derived The electron-transfer rate constant now being tested, for example, as an
electrode-active battery materials for the nitroxide radical in solution is uninterruptible power supply system
have been studied since the 1980s. estimated to be on the order of >10 -1 (UPS) for the backup or shutdown of
MacInnes et al., by extending their cm/s.8 This rapid electron-transfer personal computers and computer
discovery of electrically conductive rate for the nitroxide radical redox servers during power failure.
polyacetylene, reported in 1981,5 is the most important feature in
the potential application of p- and comparison with the slow rates for Molecular Design toward
n-doping processes in polyacetylene the other organic redox couples (e.g., an All-Organic Radical Battery
to a rechargeable battery in an all- the electron-transfer rate constant of An ongoing issue with the organic
organic device design. However, 10 -8 cm/s for a disulfide redox). The radical battery is the enhancement
the achievable doping degree of diffusion coefficient (Dapp) of the of the energy density or the capacity.
polyacetylene was limited to less redox or charge transfer in the radical The theoretical capacity of PTMA
than 10% of the repeating unit due polymer layer, using the PTMA- as the cathode active material is 111
to delocalized unpaired electrons on modified electrode: Dapp = 10 -8 cm2 /s, mAh/g, which is around two-thirds of
the -conjugated backbone, which is comparable to those of previously the capacity of the cathode material
confined the energy-density of the reported redox-active polymers such (150-170 mAh/g) in conventional
battery to a low value. Relatively slow as poly(vinylferrocene) (Dapp = 10 -8 Li-ion batteries. Along with
electrochemical kinetics during the cm2 /s). The amorphous, solvated, designing the molecular structure
doping/dedoping of polyacetylene, and slightly swollen structure of the of the nitroxide derivative, we have
due to the slow diffusion of dopant radical polymer in the composite proposed and synthesized a series
ions in the polymer, also affected electrode ensures good counterion of radical polymers with a compact
battery performance deleteriously. mobility during the electrode process. molecular structure and a small
The cell voltage was not constant These features afford a high power- molecular weight per active nitroxide
and dependent on the doping degree. rate performance for the charge and site (Fig. 10). As shown in this
The chemical instability of both the discharge processes during battery diagram, some of these candidates are
virgin and doped polyacetylenes was applications. expected to display energy density or
the fatal flaw to practically applying The battery performance based on capacity beyond 200 mAh/g.
doped polyacetylene to a battery the PTMA cathode is projected on the In addition to such a high energy
device. energy and power density diagram density, it may be possible to
Some electrically conducting for conventional batteries and synthesize radical polymers with
polymers such as polythiophene, capacitors (Fig. 9). The performance intrinsic electrical conductivity (6)
polypyrrole, and polyaniline have of the radical battery is characterized which could contribute to further
also been investigated as electrode by both remarkably high power improvements of the rate property or
materials. However, their doping density and high energy density (or power density of the radical battery.
and dedoping processes do not high capacity), and they are almost
Based on our recent work, the
satisfy the requisites for a battery. comparable to those of capacitors and
radical polymer may be switched from
The fluctuation problem of the cell conventional secondary batteries,
p-type or cathode active material
voltage has not yet been solved. In respectively. By utilizing its high
to n-type or anode active material.
the late 1980s, disulfide compounds power performance and relatively
A typical example is the nitroxide-
were investigated intensively as a high capacity, the radical battery is
(continued on next page)
cathode material.6,7 However, their
rate performance remains low due
to the bimolecular redox reaction
(2RS [ RS-SR). Additionally, the
nasty odor of sulfur compounds is a
problematic practical issue. 10 0
Power density (kW/kg)

Why the Nitroxide Radical Polymer?


The organic nitroxide radical Capacitor
has the following characteristics
as an electroactive or charge
storage material for batteries. One 10
characteristic is the small molecular Radical
weight (formula weight) per active Battery
site among the redox active organic
molecules, for example, 30, 64, and
186 for N-O, S-S, and ferrocene, 1 Li-ion
respectively. That is, the specific Ni-MH
capacity as an electrode may be
enhanced by designing the molecular Secondary
structure of the nitroxide derivative. Pb b att eries
Second, the repeating unit structure 0.1
bearing a localized unpaired electron 1 10 100 1000
provides a high density of unpaired
electrons in the radical polymer, that Energy density (Wh/kg)
is, a deeply (almost quantitative)
doped state. This is in contrast to FIG. 9. Battery performance of the organic radical battery based on the PTMA
the so-called polymer electrodes cathode relative to conventional charge storage devices.
composed of -conjugated conductive
polymers.

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Nishide and Suga
(continued from previous page)

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

Theoretical capacity (+ ) (-)


(Ah/kg)
118 135 145 141 194 211 224
Cl
N-O N-O
O
R4N
N
CF 3
N O N-O Cl N-O
(n-type) O

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.

substituted polystyrenes: 4 displays The organic radical polymer has


p-type redox behavior, and polymer 8 solvent solubility and processability, About the Authors
shows n-type redox behavior. 8 bears which facilitates battery manufacture HIROYUKI NISHIDE is a Professor in the
a trifluoromethyl (CF3) group, which via a wet, printable, and rollable Department of Applied Chemistry at
acts as an electron-withdrawing process. We envision a slim and
Waseda University, Tokyo. His research
group, to stabilize the n-type redox flexible paper battery, a battery-on-
interests include the synthesis and
pair between the nitroxide radical chip, and a battery-on-package in
performance of functional polymers:
and the aminoxy anion. The redox the not-too-distant future. Current
radical polymers for battery and organic
potential (cell voltage) also may portable instruments are accelerating
be tuned via molecular design. For demands for a battery with a high magnet applications, conjugated polymers,
example, the redox potential of the capacity, high power rate, and light membranes for gas separation and proton
nitroxide radical is tuned from 0.7 V weight and the organic radical battery conduction. He is a Vice-President of the
(vs. Ag/AgCl) for PTMA to 1.0 V (vs. appears to fulfill these criteria. Society of Polymer Science, Japan (SPSJ),
Ag/AgCl) for 3. Such potential tuning and serves on the advisory boards of
is impossible for inorganic-derived References international journals such as Polymer. He
materials. These possibilities with 1. W. A. Walters, The Chemistry of Free can be reached at nishide@waseda.jp.
the radical polymers promise an all- Radicals, Oxford University Press, London
(1948). TAKEO SUGA is a research associate in
organic battery as illustrated in Fig. the Department of Applied Chemistry at
2. L. B. Volodarsky and V. A. Reznikov,
11. Molecular design and synthesis Synthetic Chemistry of Stable Nitroxides, CRC Waseda University, Tokyo. His research
are powerful strategies for organic Press, Boca Raton, FL (1993). involves the synthesis of radical polymers
functional materials including the 3. H. Nishide, S. Iwasa, Y.-J. Pu, T. Suga,
and their application to an electrode-active
organic radical polymers. K. Nakahara, and M. Satoh, Electrochim.
Acta, 50, 827 (2004). material for a secondary battery. He can be
The nitroxide radical polymer 4. K. Nakahara, S. Iwasa, M. Satoh, reached at takeosuga@toki.waseda.jp.
is completely burned to yield only Y. Morioka, J. Iriyama, and M. Suguro,
carbon dioxide, water, and a small Chem. Phys. Lett., 359, 351 (2002).
amount of nitrogen oxide, and 5. D. MacInnes, Jr., M. A. Druy, P. J. Nigrey,
undergoes thermal runaway with D. P. Nairns, A. G. MacDiarmid, and
A. J. Heeger, Chem. Commun., 317 (1981).
no odor or ash formation. The
6. S. J. Visco, C. C. Mailhe, and
radical polymers are not toxic. L. C. DeJonghe, J. Electrochem. Soc., 136,
These environmentally benign 661 (1989).
characteristics of the radical polymers 7. N. Oyama, T. Tatsuma, T. Sato, and
are strong advantages vs. metal-based T. Sotomura, Nature, 373, 598 (1995).
conventional (e.g., NiCd) or sulfur- 8. T. Suga, Y.-J. Pu, K. Oyaizu, and H. Nishide,
based battery electrodes. Bull. Chem. Soc. Jpn, 77, 2203 (2004).

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